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Landolt-Börnstein Numerical Data and Functional Relationships in Science and Technology New Series / Editor in Chief: W. Martienssen

Group IV: Physical Chemistry Volume 11

Ternary Alloy Systems Phase Diagrams, Crystallographic and Thermodynamic Data critically evaluated by MSIT® Subvolume D Iron Systems Part 4 Selected Systems from Cu-Fe-Si to Fe-N-U Editors G. Effenberg and S. Ilyenko

Authors Materials Science and International Team, MSIT®

ISSN

1615-2018 (Physical Chemistry)

ISBN

978-3-540-78643-6 Springer Berlin Heidelberg New York

Library of Congress Cataloging in Publication Data Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie Editor in Chief: W. Martienssen Vol. IV/11D4: Editors: G. Effenberg, S. Ilyenko At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology. Tables chiefly in English. Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title: Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik. Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag Includes bibliographies. 1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables. I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910. III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology. QC61.23 502'.12 62-53136 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. Springer is a part of Springer Science+Business Media springeronline.com © Springer-Verlag Berlin Heidelberg 2008 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Product Liability: The data and other information in this handbook have been carefully extracted and evaluated by experts from the original literature. Furthermore, they have been checked for correctness by authors and the editorial staff before printing. Nevertheless, the publisher can give no guarantee for the correctness of the data and information provided. In any individual case of application, the respective user must check the correctness by consulting other relevant sources of information. Cover layout: Erich Kirchner, Heidelberg Typesetting: Materials Science International Services GmbH, Stuttgart Printing and Binding: AZ Druck, Kempten/Allgäu

SPIN: 1210 2334

63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

Editors: Associate Editor:

Günter Effenberg Svitlana Ilyenko Oleksandr Dovbenko

MSI, Materials Science International Services GmbH Postfach 800749, D-70507, Stuttgart, Germany http://www.matport.com

Authors: Materials Science International Team, MSIT® The present series of books results from collaborative evaluation programs performed by MSI and authored by MSIT®. In this program data and knowledge are contributed by many individuals and accumulated over almost twenty years, now. The content of this volume is a subset of the ongoing MSIT® Evaluation Programs. Authors of this volume are:

Christian Bätzner, Stuttgart, Germany

Tatiana Pryadko, Kyiv, Ukraine

Gabriele Cacciamani, Genova, Italy

James Robinson, Manchester, UK

Lesley Cornish, Randburg, South Africa

Lazar Rokhlin, Moscow, Russia

Olga Fabrichnaya, Freiberg, Germany

Elena Semenova, Kyiv, Ukraine

Mireille Harmelin, Paris, France

Larysa Shcherbak, Chernivtsi, Ukraine

Volodymyr Ivanchenko, Kyiv, Ukraine

Athanasios Stamou, Volos, Greece

Kostyantyn Korniyenko, Kyiv, Ukraine

Vasyl Tomashik, Kyiv, Ukraine

Viktor Kuznetsov, Moscow, Russia

Lyudmilla Tretyachenko, Kyiv, Ukraine

Nathalie Lebrun, Lille, France

Mikhail Turchanin, Kramatorsk, Ukraine

Evgeniya Lysova, Moscow, Russia

Tamara Velikanova, Kyiv, Ukraine

Hans Leo Lukas, Stuttgart, Germany

Andy Watson, Leeds, U.K.

Pierre Perrot, Lille, France

Institutions The content of this volume is produced by MSI, Materials Science International Services GmbH and the international team of materials scientists, MSIT®. Contributions to this volume have been made from the following institutions:

The Baikov Institute of Metallurgy, Academy of Sciences, Moscow, Russia

Moscow State University, Department of General Chemistry, Moscow, Russia

Chernivtsi National University, Chemical Department, Chernivtsi, Ukraine

MSI, Materials Science International Services GmbH, Stuttgart, Germany

Donbass State Mechanical Engineering Academy, Kramatorsk, Ukraine

School of Chemical and Metallurgical Engineering, The University of the Witwatersrand, DST/NRF Centre of Excellence for Strong Material, South Afrika

I.M. Frantsevich Institute for Problems of Materials Science, National Academy of Sciences, Kyiv, Ukraine Institute for Semiconductor Physics, National Academy of Sciences, Kyiv, Ukraine

Technische Universität Bergakademie Freiberg, Institut für Werkstoffwissenschaft, Freiberg, Germany

G.V. Kurdyumov Institute for Metal Physics, National Academy of Sciences, Kyiv, Ukraine

Universita di Genova, Dipartimento di Chimica, Genova, Italy

Manchester Materials Science Centre University of Manchester and UMIST, Manchester, UK

Universite de Lille I, Laboratoire de Métallurgie Physique, Villeneuve d’ASCQ, France

Max-Planck-Institut für Metallforschung, Institut für Werkstoffwissenschaft, Pulvermetallurgisches Laboratorium, Stuttgart, Germany

University of Leeds, Department of Materials, School of Process, Environmental and Materials Engineering, Leeds, UK University of Thessaly, Volos, Greece

Preface

The sub-series Ternary Alloy Systems of the Landolt-Börnstein New Series provides reliable and comprehensive descriptions of the materials constitution, based on critical intellectual evaluations of all data available at the time and it critically weights the different findings, also with respect to their compatibility with today’s edge binary phase diagrams. Selected are ternary systems of importance to alloy development and systems which gained in the recent years otherwise scientific interest. In one ternary materials system, however, one may find alloys for various applications, depending on the chosen composition. Reliable phase diagrams provide scientists and engineers with basic information of eminent importance for fundamental research and for the development and optimization of materials. So collections of such diagrams are extremely useful, if the data on which they are based have been subjected to critical evaluation, like in these volumes. Critical evaluation means: there where contradictory information is published data and conclusions are being analyzed, broken down to the firm facts and re-interpreted in the light of all present knowledge. Depending on the information available this can be a very difficult task to achieve. Critical evaluations establish descriptions of reliably known phase configurations and related data. The evaluations are performed by MSIT®, Materials Science International Team, a group of scientists working together since 1984. Within this team skilled expertise is available for a broad range of methods, materials and applications. This joint competence is employed in the critical evaluation of the often conflicting literature data. Particularly helpful in this are targeted thermodynamic and atomistic calculations for individual equilibria, driving forces or complete phase diagram sections. Conclusions on phase equilibria may be drawn from direct observations e.g. by microscope, from monitoring caloric or thermal effects or measuring properties such as electric resistivity, electro-magnetic or mechanical properties. Other examples of useful methods in materials chemistry are massspectrometry, thermo-gravimetry, measurement of electro-motive forces, X-ray and microprobe analyses. In each published case the applicability of the chosen method has to be validated, the way of actually performing the experiment or computer modeling has to be validated as well and the interpretation of the results with regard to the material’s chemistry has to be verified. Therefore insight in materials constitution and phase reactions is gained from many distinctly different types of experiments, calculation and observations. Intellectual evaluations which interpret all data simultaneously reveal the chemistry of the materials system best. An additional degree of complexity is introduced by the material itself, as the state of the material under test depends heavily on its history, in particular on the way of homogenization, thermal and mechanical treatments. All this is taken into account in an MSIT® expert evaluation. To include binary data in the ternary evaluation is mandatory. Each of the three-dimensional ternary phase diagrams has edge binary systems as boundary planes; their data have to match the ternary data smoothly. At the same time each of the edge binary systems A-B is a boundary plane for many other ternary A-B-X systems. Therefore combining systematically binary and ternary evaluations increases confidence and reliability in both ternary and binary phase diagrams. This has started systematically for the first time here, by the MSIT® Evaluation Programs applied to the Landolt-Börnstein New Series. The degree of success, however, depends on both the nature of materials and scientists! The multitude of correlated or inter-dependant data requires special care. Within MSIT® an evaluation routine has been established that proceeds knowledge driven and applies both, human based expertise and electronically formatted data and software tools. MSIT® internal discussions take place in almost all evaluation works and on many different specific questions the competence of a team is added to the work of individual authors. In some cases the authors of earlier published work contributed to the knowledge

base by making their original data records available for re-interpretation. All evaluation reports published here have undergone a thorough review process in which the reviewers had access to all the original data. In publishing we have adopted a standard format that presents the reader with the data for each ternary system in a concise and consistent manner, as applied in the “MSIT® Workplace Phase Diagrams Online”. The standard format and special features of the Landolt-Börnstein compendium are explained in the Introduction to the volume. In spite of the skill and labor that have been put into this volume, it will not be faultless. All criticisms and suggestions that can help us to improve our work are very welcome. Please contact us via [email protected]. We hope that this volume will prove to be as useful for the materials scientist and engineer as the other volumes of Landolt-Börnstein New Series and the previous works of MSIT® have been. We hope that the Landolt Börnstein Sub-series, Ternary Alloy Systems will be well received by our colleagues in research and industry. On behalf of the participating authors we want to thank all those who contributed their comments and insight during the evaluation process. In particular we thank the reviewers - Hans Leo Lukas, Marina Bulanova, Paola Riani, Lazar Rokhlin, Anatolii Bondar, Yong Du, Olga Fabrichnaya, Artem Kozlov, K.C. Hari Kumar, Viktor Kuznetsov, Ludmila Tretyachenko and Tamara Velikanova. We all gratefully acknowledge the dedicated scientific desk editing by Oleksandra Berezhnytska and Oleksandr Rogovtsov.

Günter Effenberg, Svitlana Ilyenko and Oleksandr Dovbenko

Stuttgart, November 2007

Foreword Can you imagine a world without iron and steel? No? I can’t either. The story of mankind is intimately linked to the discovery and successful use of metals and their alloys. Amongst them iron and steel - we could define steel as ‘a generally hard, strong, durable, malleable alloy of iron and carbon, usually containing between 0.2 and 1.5 percent carbon, often with other constituents such as manganese, Chromium, nickel, molybdenum, copper, tungsten, Cobalt, or silicon, depending on the desired alloy properties, and widely used as a structural material’, have shaped our material world. The story of iron takes us back to the period of the Hittite Empire around 1300 BC, when iron started to replace bronze as the chief metal used for weapons and tools. Until today the story remains uncompleted and the social and economic impact of the iron and steel industry is now beyond imagination. In the year 2005 1.13 billion tons of crude steel were produced. Compared to 2004 this is an increase of 6.8%. That same year the steel production in China increased from 280.5 to almost 350 million tons. Concerning stainless steel: according to the International Stainless Steel Forum (ISSF), the global production forecast for 2006 now stands at 27.8 million metric tons of stainless crude steel, up 14.3% compared to 2005. An English poem from the 19th century tells us Gold is for the mistress Silver for the maid Copper for the craftsman Cunning at his trade Good said the baron Sitting in his hall But iron, cold iron Is master of them all It is still actual and true. The list of different steel grades and related applications is impressive and still growing: low carbon strip steels for automotive applications, low carbon structural steels, engineering steels, stainless steels, cast irons, and, more recently: dual phase steels, TRIP-steels, TWIP-steels, maraging steels, … The list of applications seems endless: a wide range of properties from corrosion resistance to high tensile strength is covered. These properties depend on the percentage of carbon, the alloying elements, and increasingly on the thermo-mechanical treatments that aim at optimizing the microstructure. Yet many potential improvements remain unexplored, also due to the increasing complexity of the new steel grades. For instance, a recently patent protected new die steel for hot deformation has the following composition specifications: C 0.46 – 0.58; Si 0.18 – 0.40; Mn 0.45 – 0.75, Cr 0.80 – 1.20; Ni 1.30 – 1.70; Mo 0.35 – 0.65; V 0.18 – 0.25; Al 0.01 – 0.04; Ti 0.002 – 0.04; B 0.001 – 0.003; Zr 0.02 – 0.04; Fe remaining.

Although many properties of steel are directly related to non-equilibrium states, it remains a fact that the equilibrium state creates the reference frame for all changes that might occur in any material - and consequently would effect its properties in use - that is actually not in its thermodynamic equilibrium state. This is what these volumes in the Landolt-Börnstein series stand for: they have collected the most reliable data on the possible phase equilibria in ternary iron based alloys. Therefore this first volume of data, as well as the other ones in a series of four to appear, is of immeasurable value for metallurgists and materials engineers that improve the properties of existing steels and develop new and more complex steel grades. It is about materials, it is about quality of life. The well-recognized quality label of MSIT®, the Materials Science International Team, also applies to the present volume of the Landolt-Börnstein series. It should be available for every materials engineer, scientist and student.

Prof. Dr. ir. Patrick Wollants Chairman - Department of Metallurgy and Materials Engineering Katholieke Universiteit Leuven Belgium

Contents IV/11D4 Ternary Alloy Systems Phase Diagrams, Crystallographic and Thermodynamic Data Subvolume D Iron Systems Part 4 Selected Systems from Cu-Fe-Si to Fe-N-U Introduction Data Covered ................................................................................................................................... XIII General............................................................................................................................................. XIII Structure of a System Report ........................................................................................................... XIII Introduction.............................................................................................................................. XIII Binary Systems ........................................................................................................................ XIII Solid Phases .............................................................................................................................XIV Quasibinary Systems................................................................................................................. XV Invariant Equilibria ................................................................................................................... XV Liquidus, Solidus, Solvus Surfaces........................................................................................... XV Isothermal Sections................................................................................................................... XV Temperature – Composition Sections ....................................................................................... XV Thermodynamics....................................................................................................................... XV Notes on Materials Properties and Applications....................................................................... XV Miscellaneous ........................................................................................................................... XV References............................................................................................................................. XVIII General References ..........................................................................................................................XIX

Ternary Systems Cu – Fe – Si (Copper – Iron – Silicon)................................................................................................. 1 Cu – Fe – Ti (Copper – Iron – Titanium) ........................................................................................... 15 Fe – H – Mn (Iron – Hydrogen – Manganese) ................................................................................... 32 Fe – H – Mo (Iron – Hydrogen – Molybdenum)................................................................................ 42 Fe – H – Ni (Iron – Hydrogen – Nickel) ............................................................................................ 50 Fe – H – O (Iron – Hydrogen – Oxygen) ........................................................................................... 65 Fe – H – P (Iron – Hydrogen – Phosphorus)...................................................................................... 72 Fe – H – Si (Iron – Hydrogen – Silicon) ............................................................................................ 76 Fe – H – V (Iron – Iron – Vanadium)................................................................................................. 82 Fe – La – Si (Iron – Lanthanum – Silicon)......................................................................................... 87 Fe – Mg – O (Iron – Magnesium – Oxygen)...................................................................................... 96 Fe – Mg – S (Iron – Magnesium – Sulphur) .................................................................................... 127 Fe – Mg – Si (Iron – Magnesium – Silicon)..................................................................................... 135 Fe – Mn – N (Iron – Manganese – Nitrogen)................................................................................... 148 Fe – Mn – Ni (Iron – Manganese – Nickel) ..................................................................................... 162 Fe – Mn – O (Iron – Manganese – Oxygen) .................................................................................... 178

Fe – Mn – P (Iron – Manganese – Phosphorus) ............................................................................... 200 Fe – Mn – S (Iron – Manganese – Sulfur)........................................................................................220 Fe – Mn – Si (Iron – Manganese – Silicon) ..................................................................................... 246 Fe – Mn – Ti (Iron – Manganese – Titanium).................................................................................. 280 Fe – Mn – V (Iron – Manganese – Vanadium) ................................................................................ 291 Fe – Mn – Zr (Iron – Manganese – Zirconium) ............................................................................... 303 Fe – Mo – N (Iron – Molybdenum – Nitrogen)................................................................................ 311 Fe – Mo – Ni (Iron – Molybdenum – Nickel) .................................................................................. 321 Fe – Mo – O (Iron – Molybdenum – Oxygen) ................................................................................. 341 Fe – Mo – Si (Iron – Molybdenum – Silicon) .................................................................................. 355 Fe – N – Nb (Iron – Nitrogen – Niobium) ....................................................................................... 371 Fe – N – Ni (Iron – Nitrogen – Nickel)............................................................................................ 381 Fe – N – Si (Iron – Nitrogen – Silicon)............................................................................................ 398 Fe – N – Ti (Iron – Nitrogen – Titanium) ........................................................................................ 409 Fe – N – U (Iron – Nitrogen – Uranium) .........................................................................................421

Introduction

1

Introduction Data Covered The series focuses on light metal ternary systems and includes phase equilibria of importance for alloy development, processing or application, reporting on selected ternary systems of importance to industrial light alloy development and systems which gained otherwise scientiﬁc interest in the recent years. General The series provides consistent phase diagram descriptions for individual ternary systems. The representation of the equilibria of ternary systems as a function of temperature results in spacial diagrams whose sections and projections are generally published in the literature. Phase equilibria are described in terms of liquidus, solidus and solvus projections, isothermal and quasibinary sections; data on invariant equilibria are generally given in the form of tables. The world literature is thoroughly and systematically searched back to the year 1900. Then, the published data are critically evaluated by experts in materials science and reviewed. Conﬂicting information is commented upon and errors and inconsistencies removed wherever possible. It considers those, and only those data, which are ﬁrmly established, comments on questionable ﬁndings and justiﬁes re-interpretations made by the authors of the evaluation reports. In general, the approach used to discuss the phase relationships is to consider changes in state and phase reactions which occur with decreasing temperature. This has inﬂuenced the terminology employed and is reﬂected in the tables and the reaction schemes presented. The system reports present concise descriptions and hence do not repeat in the text facts which can clearly be read from the diagrams. For most purposes the use of the compendium is expected to be self-sufﬁcient. However, a detailed bibliography of all cited references is given to enable original sources of information to be studied if required. Structure of a System Report The constitutional description of an alloy system consists of text and a table/diagram section which are separated by the bibliography referring to the original literature (see Fig. 1). The tables and diagrams carry the essential constitutional information and are commented on in the text if necessary. Where published data allow, the following sections are provided in each report: Introduction

The opening text reviews brieﬂy the status of knowledge published on the system and outlines the experimental methods that have been applied. Furthermore, attention may be drawn to questions which are still open or to cases where conclusions from the evaluation work modiﬁed the published phase diagram. Binary Systems

Where binary systems are accepted from standard compilations reference is made to these compilations. In other cases the accepted binary phase diagrams are reproduced for the convenience of the reader. The selection of the binary systems used as a basis for the evaluation of the ternary system was at the discretion of the assessor. Solid Phases

The tabular listing of solid phases incorporates knowledge of the phases which is necessary or helpful for understanding the text and diagrams. Throughout a system report a unique phase name and abbreviation is allocated to each phase.

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2

Introduction

Fig. 1.

Structure of a system report

Phases with the same formulae but different space lattices (e.g. allotropic transformation) are distinguished by: – small letters (h), high temperature modiﬁcation (h2 > h1) (r), room temperature modiﬁcation (1), low temperature modiﬁcation (l1 > l2) – Greek letters, e.g., ε, ε' – Roman numerals, e.g., (I) and (II) for different pressure modiﬁcations. In the table “Solid Phases” ternary phases are denoted by * and different phases are separated by horizontal lines. Quasibinary Systems

Quasibinary (pseudobinary) sections describe equilibria and can be read in the same way as binary diagrams. The notation used in quasibinary systems is the same as that of vertical sections, which are reported under “Temperature – Composition Sections”.

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Fig. 2.

Typical reaction scheme

Introduction

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Introduction

Invariant Equilibria

The invariant equilibria of a system are listed in the table “Invariant Equilibria” and, where possible, are described by a constitutional “Reaction Scheme” (Fig. 2). The sequential numbering of invariant equilibria increases with decreasing temperature, one numbering for all binaries together and one for the ternary system. Equilibria notations are used to indicate the reactions by which phases will be – decomposed (e- and E-type reactions) – formed (p- and P-type reactions) – transformed (U-type reactions) For transition reactions the letter U (Übergangsreaktion) is used in order to reserve the letter T to denote temperature. The letters d and D indicate degenerate equilibria which do not allow a distinction according to the above classes. Liquidus, Solidus, Solvus Surfaces

The phase equilibria are commonly shown in triangular coordinates which allow a reading of the concentration of the constituents in at.%. In some cases mass% scaling is used for better data readability (see Figs. 3 and 4). In the polythermal projection of the liquidus surface, monovariant liquidus grooves separate phase regions of primary crystallization and, where available, isothermal lines contour the liquidus surface (see Fig. 3).

Fig. 3.

Hypothetical liqudus surface showing notation employed

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Fig. 4.

5

Hypotheticcal isothermal section showing notation employed

Isothermal Sections

Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see Fig. 4). Temperature – Composition Sections

Non-quasibinary T-x sections (or vertical sections, isopleths, polythermal sections) show the phase ﬁelds where generally the tie lines are not in the same plane as the section. The notation employed for the latter (see Fig. 5) is the same as that used for binary and quasibinary phase diagrams. Thermodynamics

Experimental ternary data are reported in some system reports and reference to thermodynamic modeling is made. Notes on Materials Properties and Applications

Noteworthy physical and chemical materials properties and application areas are brieﬂy reported if they were given in the original constitutional and phase diagram literature.

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Fig. 5.

Introduction

Hypothetical vertical section showing notation employed

Miscellaneous

In this section noteworthy features are reported which are not described in preceding paragraphs. These include graphical data not covered by the general report format, such as lattice spacing – composition data, p-T-x diagrams, etc. References

The publications which form the bases of the assessments are listed in the following manner: [1974Hay] Hayashi, M., Azakami, T., Kamed, M., “Effects of Third Elements on the Activity of Lead in Liquid Copper Base Alloys” (in Japanese), Nippon Kogyo Kaishi, 90, 51–56 (1974) (Experimental, Thermodyn., 16) This paper, for example, whose title is given in English, is actually written in Japanese. It was published in 1974 on pages 51–56, volume 90 of Nippon Kogyo Kaishi, the Journal of the Mining and Metallurgical Institute of Japan. It reports on experimental work that leads to thermodynamic data and it refers to 16 cross-references. Additional conventions used in citing are: # to indicate the source of accepted phase diagrams * to indicate key papers that signiﬁcantly contributed to the understanding of the system. Standard reference works given in the list “General References” are cited using their abbreviations and are not included in the reference list of each individual system.

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General References [C.A.] Chemical Abstracts – pathways to published research in the world's journal and patent literature – http://www.cas.org/ [Curr. Current Contents – bibliographic multidisciplinary current awareness Web resource – http:// Cont.] www.isinet.com/products/cap/ccc/ [E] Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York (1965) [G] Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin [H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958) [L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A., Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermodynamic Data of Binary Alloys, Subvol. a: Ac–Au ... Au–Zr (1991); Springer-Verlag, Berlin. [Mas] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986) [Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) [P] Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys, Pergamon Press, New York, Vol. 1 (1958), Vol. 2 (1967) [S] Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York (1969) [V-C] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, ASM, Metals Park, Ohio (1985) [V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Index of alloy systems

1

Index of alloy systems Index of Ternary Iron Alloy Systems Cu-Fe-Si to Fe-Ti-Y Cu–Fe–Si (Copper – Iron – Silicon) Cu–Fe–Ti (Copper – Iron – Titanium) Fe–H–Mn (Iron – Hydrogen – Manganese) Fe–H–Mo (Iron – Hydrogen – Molybdenum) Fe–H–Ni (Iron – Hydrogen – Nickel) Fe–H–O (Iron – Hydrogen – Oxygen) Fe–H–P (Iron – Hydrogen – Phosphorus) Fe–H–Si (Iron – Hydrogen – Silicon) Fe–H–V (Iron – Hydrogen – Vanadium) Fe–La–Si (Iron – Lanthanum – Silicon) Fe–Mg–O (Iron – Magnesium – Oxygen) Fe–Mg–S (Iron – Magnesium – Sulfur) Fe–Mg–Si (Iron – Magnesium – Silicon) Fe–Mn–N (Iron – Manganese – Nitrogen) Fe–Mn–Ni (Iron – Manganese – Nickel) Fe–Mn–O (Iron – Manganese – Oxygen) Fe–Mn–P (Iron – Manganese – Phosphorus) Fe–Mn–S (Iron – Manganese – Sulfur) Fe–Mn–Si (Iron – Manganese – Silicon) Fe–Mn–Ti (Iron – Manganese – Titanium) Fe–Mn–V (Iron – Manganese – Vanadium) Fe–Mn–Zr (Iron – Manganese – Zirconium) Fe–Mo–N (Iron – Molybdenum – Nitrogen) Fe–Mo–Ni (Iron – Molybdenum – Nickel) Fe–Mo–O (Iron – Molybdenum – Oxygen) Fe–Mo–Si (Iron – Molybdenum – Silicon) Fe–N–Nb (Iron – Nitrogen – Niobium) Fe–N–Ni (Iron – Nitrogen – Nickel) Fe–N–Si (Iron – Nitrogen – Silicon) Fe–N–Ti (Iron – Nitrogen – Titanium) Fe–N–U (Iron – Nitrogen – Uranium) Fe–Ti–Y (Iron – Titanium – Yttrium)

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Cu–Fe–Si

1

Copper – Iron – Silicon Nathalie Lebrun, Pierre Perrot, Mireille Harmelin

Introduction Fe and Si are known for hardening Cu alloys due to the precipitation of iron silicides [1927Cor] and the Cu-Fe-Si alloys are commonly formed during melting in treatment process of domestic wastes incinerators [1999Hin]. The phase diagram presented by [1949Jae] takes into account the previous determination of [1933Rol] in the iron rich corner and [1934Han] in the copper rich corner. The actual knowledge of the ternary diagram rests on a thorough investigation by [1953Vog, 1999Hin] of the Cu-Fe-FeSi-Cu3Si domain, which precises the shape of the miscibility gap in the ternary liquid. The miscibility gap was investigated theoretically by [1991But]. A comprehensive review may be found in [1979Cha, 1992Rag, 2002Rag]. Calphad assessments of the Cu-Fe-Si system have been carried out by [1997Oht, 1999Hin, 2003Mie] near the Cu-Fe border (< 40 mass% Si). Experimental works are listed in Table 1. Binary Systems After [Mas2], the liquidus and solidus phase boundaries in the Fe rich portion of the Fe-Si phase diagram were measured by [2005Mec] and thermodynamically reassessed by [1998Mie]. The DTA measurements done by [2005Mec] reveal a signiﬁcant shift compared to [Mas2] in the solidus and liquidus curves in the range between 20 and 25 at.% Si (11.17 and 14.36 mass% Si), suggesting that the A2-B2 (and perhaps B2-D03) ordering transition occurs in large part through the two-phase temperature regions. Since these careful experimental data are identical to those used by [1998Mie] for his thermodynamic assessment, these data are retained in the present evaluation. Nevertheless, a more sophisticated thermodynamic treatment of the ordering transition is necessary for a better accuracy of the Fe-Si diagram in the range from 20 to 35 at.% Si (11.17 to 21.31 mass% Si). Cu-Fe is accepted from [2007Tur]. A metastable miscibility gap in the liquid phase exists. Cu-Si, based on the compilation of [1986Ole] is accepted from [2002Leb]. Solid Phases The binary solid compounds are listed in Table 2. Only one ternary metastable compound has been reported. The lattice parameters of Cu rich ternary single-phase alloys (up to 5 Fe, 5 Cu at.%) were reported by [1943And] for alloys quenched from various temperatures between 1025 and 800°C. Si decreases the Fe solubility in solid Cu [1934Han, 1943And]. Although [1933Rol] proposes an increase of Cu solubility in solid Fe, more recent studies [1997Oht] show also a decrease of the Cu solubility in solid Fe. The solubility of Cu in FeSi and FeSi2 phases is estimated less than 0.2 at.% [1997Yam]. Quasibinary Systems Cu3Si-FeSi section is found to be quasibinary with a eutectic point at 847°C and 2 mass% Fe [1953Vog]. Recent experimental data [2002Was] predict the existence of a liquid miscibility gap along this quasibinary section. Consequently the section has been modiﬁed taking into account this liquid miscibility gap. The temperature of 1400°C has been chosen since at 1450°C the liquid miscibility gap closes itself and at 1350°C the FeSi+L phase ﬁeld was found by [2003Mie]. The critical temperature of this two-liquid domain was estimated to be 1632°C [1999Hin]. The not well know boundaries have been indicated as dashed lines in Fig. 1. The eutectic position has been moved to be in agreement with the accepted isothermal sections at 1100 and 900°C. The vertical section FeSi2-Cu3Si was constructed by [1975Abr] and claimed to be quasibinary. It presents a eutectic at 800°C towards 82 mol% Cu3Si. However, this section cannot be quasibinary because the transformation of βFeSi2 into αFeSi2 occurs following a peritectoid reaction at 982°C accompanied with a change in composition as shown in Table 2. Landolt-Börnstein New Series IV/11D4

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2

Cu–Fe–Si

Invariant Equilibria The ﬁrst experimental study was reported by [1953Vog, 1979Cha] who detected four ternary U reactions in the Cu rich corner of the Cu-Fe-Si system. Three of these reactions are accepted in the present evaluation, their details are given in Table 3. The σ phase, wrongly labelled Fe3Si2 by [1953Vog] corresponds actually to the composition Fe5Si3. The temperatures of these ternary reactions are located between 900°C and 1100°C. Further experimental investigations are needed to determine precisely these reaction temperatures. The reaction (αFe)+FeSi ⇌ L+Fe5Si3 indicated by [1953Vog] has been rejected since no three-phase ﬁeld (αFe) +FeSi+Fe5Si3 is indicated on the accepted isothermal sections below 916°C. More recently, from the isothermal sections constructed by [1999Hin], a ternary reaction of the U type may be supposed between 1450 and 1350°C: (γFe)+L1 ⇌ (αFe)+L2. No information is available regarding the compositions of the phases involved. Additional ternary reactions proposed by [1992Rag] are only speculative and the deduced reaction scheme for the Fe-FeSi-Cu3Si-Cu region could not be accepted. Liquidus, Solidus and Solvus Surfaces The ﬁrst experimental results on the liquidus surface was reported by [1934Han] in the Cu rich corner showing the isothermal lines and the saturation curve between the (Cu) and (γFe) phases. Later [1953Vog] investigated the liquidus surface for the FeSi-Cu3Si-Cu region and suggested the existence of four ternary U reactions. After the review of [1979Cha], [1992Rag] reassessed critically the liquidus surface and speculated others ternary reactions without experimental ﬁndings. The dominant feature of this liquidus surface is the liquid miscibility gap that closes on itself. Two critical points have been measured at 1425°C (62 mass% Fe, 36.5 mass% Cu, 1.5 mass% Si) and 1110°C (18 mass% Fe, 70 mass% Cu, 12 mass% Si) [1953Vog]. From heat capacity measurements, [2002Was] deduced the liquid miscibility gap in the Cu rich corner at 1500°C and suggested a wider region of the two-liquid domain than the one measured by [1953Vog]. Liquid miscibility gap has been also calculated by [2002Wan], who extrapolated the two-liquid region up to 1727°C using thermodynamic assessment of experimental data obtained in the 800–1000°C temperature range. At 1800°C, the two-liquid region does not exist [2002Was]. [1999Hin] estimated the critical temperature of the two liquid region at 1632°C. Considering the disagreement about the miscibility gap and the location of the ternary reactions, the liquidus surface proposed by [1953Vog] could not be accepted. Further careful experimental data on the entire system are needed. Isothermal Sections The Fe rich corner of the Cu-Fe-Si system was ﬁrst investigated by [1933Rol]. At room temperature, the solubility of Cu in Fe was found to increase with increasing Si content. The boundary was determined passing through about 1% Cu, 3% Si and 5% Cu, 16% Si (mass%). [1934Han] examined the Cu rich corner below 1100°C and reported that at temperatures between 1100 and 800°C, the solubility of Fe in Cu is decreased by the presence of Si. The equilibrium of (Cu) and (Fe) in the presence of Si has been measured by [1981Has] on one tie-line at 1000°C (xCu = 0.030, xSi = 0.057 for the α phase and xCu = 0.039, xSi = 0.046 for the γ phase), and at 1300°C (xCu = 0.041, xSi = 0.050 for the γ phase and xCu = 0.055, xSi = 0.042 for the liquid phase). A more thorough investigation of the (αFe)-(Cu) or (γFe)-(Cu) equilibria was carried out between 800 and 1000°C by [2002Wan]. At high temperature, a liquid miscibility gap is located near the Cu-Fe side. At 1450°C, it closes on itself and silicon stabilizes it with decreasing temperature. Large discrepancies are pointed out regarding the width of this miscibility gap. The maximum of the Si composition was estimated to be about 13 mass% by [1953Vog] whereas the computed data estimate this maximum around 30 mass% at 1450°C [1997Oht, 1999Hin, 2002Wan]. A wider miscibility gap at 1450°C was predicted by [2003Mie] with a maximum at 35 mass% Si. Recently, [2002Was] performed heat capacity measurements at 1800°C and extrapolated the liquid miscibility gap in the Fe rich corner (< 30 mass% Cu, < 50 at.% Si) at 1500°C. A wider liquid miscibility gap suggested in [2002Was] is in quite good agreement with the computed results of [2003Mie]. Consequently the work done by [2003Mie] is preferred. Nevertheless, further experimental studies on the liquid miscibility gap are needed. DOI: 10.1007/978-3-540-78644-3_3 # Springer 2008

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Cu–Fe–Si

3

The isothermal sections at 1450, 1350, 1250 and 1100°C are taken from the more recent calculations [2003Mie] and are depicted in Fig. 2 (1450°C), Fig. 3 (1350°C) and Fig. 4 (1100°C). The isothermal section at 1250°C is reported because of its complete similarity with the one calculated at 1350°C. Only the phase ﬁelds located along the Cu-Fe system up to 10 mass% Si were calculated by [2003Mie]. Consequently, some ﬁelds are shown by dashed lines at 1100°C. The isothermal sections calculated at 1000°C and 900°C by [2003Mie] are in disagreement with the binary system Fe-Si since the Fe5Si3 phase has not been taken into account in the thermodynamic assessment. The 900°C isothermal section calculated by [2002Wan] is preferred selected and reproduced in Fig. 5. Small modiﬁcations have been done regarding the maximum of the Fe composition of the liquid region in agreement with the quasibinary system FeSi-Cu3Si. Others isothermal sections at lower temperature have been established by [1934Han, 1943And, 1953Vog] in the Cu rich corner. The isothermal sections of [1934Han] do not include all the known Cu-Si intermediate phase and the phase rule is not obeyed. The isothermal sections presented by [1943And] in the Cu rich corner are in good agreement with the accepted binary systems. Nevertheless, some discrepancies are observed at 875°C compared to the one established at 900°C by [2002Wan]. The three-phase ﬁeld L+(Cu)+Fe5Si3 is absent in [2002Wan]. Further experimental investigations are needed at low temperature. Consequently, these isothermal sections are not accepted in the present evaluation. Temperature – Composition Sections A number of vertical sections have been determined for this system: at 0.5 and 2 mass% Fe [1943And], at 20, 40 and 65 mass% Cu, 10 mass% Fe and 10 mass% Si, and along FeSi-Cu [1953Vog]. The vertical sections determined by [1943And] are in contradiction with the isothermal section at 900°C constructed by [2002Wan]. A two-phase ﬁeld FeSi+(Cu) (which is absent in [1943And]) was experimentally measured by [2002Wan] at 900°C. The vertical sections proposed by [1953Vog] could not be accepted due to their discrepancies with the isothermal sections, in particular the absence of Fe2Si, and the deeper liquid miscibility gap compared to the more recent experimental work done by [2002Was]. [1975Abr] constructed a vertical section FeSi2-Cu3Si which cannot be quasibinary do to the composition change of the two FeSi2 phases in the binary system. A eutectic between αFeSi2 and η,Cu3Si was found at 82 mol% Cu3Si. At higher temperatures [1975Abr] stipulated the existence of a two-phase ﬁelds L+βFeSi2 above 960°C and L+αFeSi2 below 960°C. The accepted isothermal sections at 1100°C, 1350°C do not conﬁrm their existence. Moreover, the liquid miscibility gap should exist along this vertical section. Consequently, this vertical section is not retained in this assessment. Further experimental data are needed. Thermodynamics The interaction coefﬁcients of Cu and Si in liquid alloys, deﬁned, in the iron rich alloys, as e(Si)Cu = ∂ ln fCu /∂ (mass% Si), where fCu = (mass% Cu in pure Fe)/(mass% Cu in alloy) at constant copper activity, has been evaluated as e(Si)Cu = + 0.027 at 1600°C by [1974Sig]. Si in liquid Fe increases the activity coefﬁcient of Cu, thus decreases its solubility under an imposed copper activity. The interaction coefﬁcient e(Cu)Si = ∂ ln fSi /∂ (mass% Cu) was calculated e(Cu)Si = + 0.014 at the same conditions. The excess Gibbs energy of a φ phase, in which φ represents any of the α, γ and liquid solutions were evaluated by [1997Oht, 1999Hin, 2003Mie] using the following model: Gxs(φ) = Gxs(Cu,Fe,φ) + Gxs(Cu,Mn,φ) + Gxs(Fe,Mn,φ) + Gxs(Cu,Fe,Mn,φ) The binary terms for a φ phase are given by a Redlich-Kister expansion: Gxs(i, j, φ) = xi xj Σk L(k, φ)(xi – xj) k The ternary term is given by Gxs(Cu,Fe,Mn,φ) = xCu xjFe xMn A(φ). The ternary interaction parameters A (φ) proposed by [1997Oht] and [1999Hin] are the same if φ = γ. For the liquid phase, [1997Oht] gives A(L) = 0. The ternary terms calculated by [1999Hin] are supported by its experimental determination of the two-liquid domain: A (α) = – 237300 + 100 T A (γ) = – 187300 + 100 T A (L) = 19000 – 22.5 T Landolt-Börnstein New Series IV/11D4

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4

Cu–Fe–Si

More elaborate expressions for these ternary terms have been proposed by [2003Mie]. The value accepted above for A(L) was later conﬁrmed by [2002Was] who measured the heat content of the Cu-Fe-Si alloys at 1800°C in order to evaluate the energy needed to melt the metallic phase generated in the melting treatment process of domestic waste incineration residue. The heat content HT – H298 is shown at 1800°C in Fig. 6 and at 1500°C in Fig. 7. The values of HT – H298 on both ﬁgures are given in kJ·mol–1. An input energy of 50 to 65 kJ·mol–1 is necessary to melt the metallic phase generated by the incineration of domestic waste and keep it at 1500°C. Notes on Materials Properties and Applications Experimental works are gathered in Table 4. Cu is considered as the most promising alternative to Al based alloys for integration materials in silicon based integrated circuits. However, Cu reacts easily with Si to form the brittle compound Cu3Si even at temperatures as low as 200°C. The presence of Fe lowers the coefﬁcient of thermal expansion of the Cu-Si matrix and forms the FeSi2 compound at the expanse of the brittle Cu3Si at the Cu-Si interface [2001Lee]. A small amount of Fe affects strongly the annealing behavior such as recovery, anneal hardening and recrystallization of cold worked Cu-Si alloys [1965Ued]. Cu-Fe alloys (1.5 to 2.5 mass% Fe) possess a higher tensile strength and a better conductibility than pure Cu. The presence of Si (1 mass% Si) causes an increase in the strength and an increase in the electrical resistivity [1983Str] because of the formation of Fe3Si precipitates. The presence of Si increases the evaporation rate of Cu [2003Ono] owing to the strong afﬁnity between Fe and Si. At 1800°C, the activity coefﬁcient of Cu at inﬁnite dilution increases from γCu = 9.5 in pure liquid iron to a maximum γCu = 17.8 in Fe added with 20 at.% Si. A further increase of Si content decreases γCu because of the strong afﬁnity between Si and Cu. As a consequence, its vapor pressure and its vaporization rate decrease with the Si content above 20 at.% Si. In pure Si at 1800°C, the Cu activity coefﬁcient is only γCu = 0.16. Cu is considered as a tramp element in ferrous scraps which causes an adverse effect in the mechanical properties of steel products such as its hot workability. Several processes have been proposed for extracting Cu from the Fe-Cu recycling scraps. One is to use the miscibility gap which appears at addition of C or Si, which cause a separation between a Cu rich and a Fe rich phase [2004Wan]. The addition of less than 1 at.% B [2005Yam] makes possible an undercooling, thus, a phase separation in the metastable liquid domain. The vaporization processes are also considered as suitable for removal of Cu from iron alloys. Cu vaporizes at high temperatures (1800°C) and the presence of Si enhances the vaporization rate [2003Ono]. Miscellaneous The fcc metastable phase of an approximate composition Fe63Cu27Si10 has been obtained by bombarding iron rich Cu-Fe-Si multilayers made by depositing alternately pure elements in a high vacuum system [1992Liu] with Xe ions (1015 to 1016 Xe·cm–2 under 200 keV). Another phase reﬂecting sharp diffraction spots with 12-fold symmetry was also observed. The sharp incommensurate diffraction pattern bore a close relationship with the fcc metastable phase. βFeSi2 is known as an excellent high temperature thermoelectric material. Unfortunately, its preparation from the liquid goes through the eutectic transformation L ⇌ FeSi + αFeSi2 followed by the synthesis of βFeSi2 below 1255°C. Cu additions are quite effective to accelerate the βFeSi2 transformation rate [1997Yam]. The process is two orders shorter with small amount of Cu added. At 600°C, the time for complete βFeSi2 formation is 8 ·103 s [1999Yam]. Similar observations were made by [2001Nog] when Cu is added to the thermoelectric material Fe0.91Mn0.01Siy (y = 2, 2.5) synthesized by spark plasma sintering. Cu has also been shown to promote the eutectoid reaction αFeSi2 ⇌ βFeSi2 + (Si). The viscosity of Cu-Fe-Si liquid alloys has been measured in the composition range 0 to 5 mass% Cu and 10–20 mass% Si, which corresponds to the mean composition of alloys formed in the municipal wastes incinerators [2001Was]. The viscosity is in the range of 5 to 7 mPa·s, which is approximately twice that of pure Cu at the same temperature. Radioactive Cu and Fe ions implanted under 60 keV in Si single crystal at room temperature occupy lattice sites around 50 pm from substitutional positions [2006Wah], and are released by annealing at 300–600°C.

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Landolt-Börnstein New Series IV/11D4

Cu–Fe–Si Table 1.

5

Investigations of the Cu-Fe-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1933Rol]

Optical microscopy, solubility measurements

900°C, < 20 mass% Cu, < 20 mass% Si in Fe (Iron rich corner)

[1934Han]

Optical microscopy, solubility measurements

800–1100°C, < 8 mass% Fe, < 8 mass% Si (copper rich corner)

[1943And]

X-ray diffraction (XRD), chemical analysis

< 1025°C, Cu, <10 at.% Fe, < 10 at.% Si

[1953Vog]

Optical microscopy, thermal analysis

600–1500°C, Cu-Fe-FeSi-Cu3Si domain

[1975Abr]

XRD, thermal analysis, metallography

600–1200°C, FeSi2-Cu3Si quasibinary section

[1981Has]

Diffusion couple experiment, α-γ equilibrium

1000–1300°C, < 6 at.% Si, < 6 at.% Cu (Fe rich corner)

[1999Hin]

Optical microscopy, electron probe microanalysis

1250–1450°C, the whole diagram

[2002Wan]

SEM, electron dispersive X-ray analysis

800–1000°C, < 25 mass% Si, (αFe) + (Cu) equilibrium

[2002Was]

Drop calorimetry, heat content measurements

1500–1800°C, < 50 at.% Cu, < 25 at.% Si

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αFe) (Ferrite) < 912°C

cI2 Im 3m W

a = 286.65

pure Fe at 25°C [Mas2, V-C2] dissolves up to 10 at.% Si at 500°C [Mas2]. Dissolves 1.4 at.% Cu at 847°C [2007Tur] at 1390°C [V-C2] dissolves up to 19.5 at.% Si at 1280°C [Mas2]. Dissolves 5.6 at.% Cu at 1487°C [2007Tur]

(δFe) 1538–1394

a = 293.15

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, > 13 GPa [Mas2]

(Si) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

at 25°C [Mas2]. 0 to 0.003 at.% Cu [2002Leb]. Practically no solubility for Fe [Mas2].

(γFe,Cu)

cF4 Fm 3m Cu

a = 364.67

at 915°C [V-C2, Mas2]. Dissolves 14.2 at.% Cu at 1425°C [2007Tur]. Dissolves up to 3.8 at.% Si at 1150°C [2005Mec]

(γFe) (Austenite) < 1394–912

(continued) Landolt-Börnstein New Series IV/11D4

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Cu–Fe–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

(Cu) < 1084.62

Lattice Parameters [pm]

Comments/References

a = 361.46

pure Cu at 25°C [Mas2] melting point [2007Tur] dissolves up to 4.6 at.% Fe at 1096°C [2007Tur] and 11.25 at.% Si at 842°C [2002Leb] below critical temperature: γ - paramagnetic, Fe enriched

FeSi < 1410

cP8 P213 FeSi

a = 451.7 ± 0.5

at 300°C [V-C2, Mas2]

Fe2Si 1212–1040

cP2 Pm 3m CsCl or hP6 P 3m1 Fe2Si

a = 282

66 at.% Si [Mas2, V-C2]

Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.9 ± 0.5 c = 472.0 ± 0.5

38.4 at.% Si [V-C2, Mas2]

βFeSi2(h) 1220–937

tP3 P4/mmm βFeSi2

a = 269.01 c = 513.4

69.5 to 73.5 at.% Si [Mas2, V-C2]

αFeSi2(r) < 982

oC48 Cmca αFeSi2

a = 986.3 ± 0.7 b = 779.1 ± 0.6 c = 783.3 ± 0.6

66.7 at.% Si [Mas2, V-C2]

α1, Fe3Si

cF16 Fm 3m BiF3

a = 565

10 to 30 at.% Si [Mas2, V-C2]

α2, Fe3Si

cP2 Pm 3m CsCl

-

10 to 22 at.% Si [Mas2]

κ, Cu7Si 842–552

hP2 P63/mmc Mg

β, Cu6Si 853–787

cI2 Im 3m W

δ, Cu5Si(h) 824–711

t**

a = 405.2 ± 0.2 c = 508.55 ± 0.3

11.05 to 14.5 at.% Si [2002Leb] at 12.75 at.% Si

a = 256.05 c = 418.46

14.2 to 16.2 at.% Si [2002Leb] at 14.9 at.% Si

a = 285.4

17.6 to 19.6 at.% Si [2002Leb] sample annealed at 700°C

a = 881.5 c = 790.3

(continued)

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Cu–Fe–Si

7

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

ε, Cu15Si4 < 800

cI76 I 43d Cu15Si4

a = 961.5

21.2 at.% Si [V-C2]

η, Cu3Si(h2) 859–558

hR* R 3m or t**

23.4 to 24.9 at.% Si [2002Leb] a = 402.2 c = 243.7 a = 726.7 c = 789.2

[V-C2]

η’, Cu3Si(h1) 620–467

hR* R 3m

a = 699.98 c = 731.52

23.2 to 25.1 at.% Si [2002Leb]

η”, Cu3Si(r) < 570

o**

a = 767.6 b = 700 c = 2194

23.3 to 24.9 at.% Si [2002Leb]

Cu5Si

t**

a = 647 c = 873

at 17 at.% Si metastable [2002Leb]

* Fe63Cu27Si10 c**

a = 423

metastable [1992Liu]

Table 3.

Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (mass%) Cu

Fe

Si

-

-

-

L1 + (γFe) ⇌ (αFe) + L2

1450–1350

U1

-

L + (γFe) ⇌ (Cu) + (αFe)

1068

U2

L (γFe) (Cu) (αFe)

93.5 7.5 96 2

1.5 92.0 0.5 96.5

5 0.5 3.5 1.5

L + (αFe) ⇌ Fe5Si3+ (Cu)

900–1068

U3

L (αFe) Fe5Si3 (Cu)

91.5 5 0 95

1 79 76.8 0.2

7.5 16 23.2 4.8

L + Fe5Si3 ⇌ FeSi + (Cu)

900–1068

U4

L Fe5Si3 FeSi (Cu)

91.4 0 0 95

1 76.8 66.5 0.1

7.6 23.2 33.5 4.9

L ⇌ FeSi + Cu3Si

847

e

L FeSi Cu3Si

84.5 0 87.16

2.0 66.54 0

13.5 33.46 12.84

Landolt-Börnstein New Series IV/11D4

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8 Table 4.

Cu–Fe–Si Investigations of the Cu-Fe-Si Materials Properties

Reference

Method/Experimental Technique

Type of Property/Conditions

[1930Cor]

Hardness and resistivity

< 900°C, < 2.5 mass% Fe, < 1 mass% Si

[1965Ued]

XRD, micrographic observation, hardness measurements

2.8 mass% Si, < 0.3 mass% Fe, cold rolled then annealed (< 800°C)

[1983Str]

Transmission Electron Microscopy (TEM), Mössbauer

< 950°C, < 2.5 mass% Fe, < 1 mass% Si, hardening

[1992Liu]

Energy dispersive spectroscopy, Scanning Electron Microscopy (SEM)

77 and 298 K, bombardment of Xe ions on thin layer

[1997Yam, 1999Yam]

Electron probe microanalysis, SEM, backscattered electrons

600–1050°C, FeSi2 + Cu (< 1 at.% Cu), synthesis of pure βFeSi2

[2001Cas]

Auger electron spectroscopy, low energy electron diffraction

Fe/Cu/Si thin layers (between 1 and 50 monolayers of Fe)

[2001Lee]

XRD, SEM, EPMA, DTA (microstructural analysis)

Cu + 50 vol% Si + 0 to 10 mass% Fe, compacted powders

[2001Nog]

XRD, electrical resistivity, seebeck coefﬁcient

< 800°C, Fe0.91Mn0.09Si2.5 + Cu (< 20 mass% Cu)

[2001Was]

Viscosity measurements

1250–1400, < 3 mass% Cu, < 20 mass% Si

[2004Wan]

Thermal analysis, optical microscopy

1800°C, 50Cu-50Fe + 1 to 2 mass% Si, two liquids observations

[2005Yam]

XRD, SEM, EPMA, Differential Scanning Calorimetry (DSC)

1000–1800°C, 30 to 70 at.% Cu, 10 at.% Si, < 1 at.% B

[2006Wah]

XRD, activation analysis

Cu and Fe implanted in Si single crystal, then annealed (300–900°C)

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Cu–Fe–Si

Fig. 1. Cu-Fe-Si.

Landolt-Börnstein New Series IV/11D4

9

FeSi-Cu3Si quasibinary section

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Fig. 2. Cu-Fe-Si.

Cu–Fe–Si

Isothermal section at 1450°C

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Cu–Fe–Si

Fig. 3. Cu-Fe-Si.

Landolt-Börnstein New Series IV/11D4

11

Isothermal section at 1350°C

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Fig. 4. Cu-Fe-Si.

Cu–Fe–Si

Isothermal section at 1100°C

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Cu–Fe–Si

Fig. 5. Cu-Fe-Si.

Landolt-Börnstein New Series IV/11D4

13

Isothermal section at 900°C

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Fig. 6. Cu-Fe-Si.

Cu–Fe–Si

Heat content (H1773 – H298) in kJ·mol–1 of the liquid alloys at 1500°C

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Cu–Fe–Si

Fig. 7. Cu-Fe-Si.

Landolt-Börnstein New Series IV/11D4

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Heat content (H2073 – H298) in kJ·mol–1 of the liquid alloys at 1800°C

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16

Cu–Fe–Si

References [1927Cor] Corson, M.G., “Copper Hardened by New Method. What the Corson Alloys Are - Stronger Cable Wire Possible - Many Uses Suggested - Silicon-Aluminum and Silver-Silicon Alloys”, Trans. Amer. Inst. Min. Met. Eng., Inst. Metals Div., 421–424 (1927) (Experimental, Mechan. Prop., Phase Diagram, Phase Relations, 0) [1930Cor] Corson, M.G., “Systems of Copper Alloys with Phase and Variable Limits. Their Use for Copper Hardening” (in French), Rev. Metall., 27, 194–213 (1930) (Experimental, Mechan. Prop., Phase Relations, 6) [1933Rol] Roll, F., “Inﬂuence of Ni and Si on the Solubilities in the Fe-Cu System in the Solid State” (in German), Z. Anorg. Chem., 212, 61–64 (1933) (Phase Diagram, Phase Relations, Experimental, 15) [1934Han] Hanson, D., West, E.G., “The Constitution of Copper-Iron-Silicon Alloys”, J. Inst. Met., 54, 229–253 (1934) (Experimental, Phase Diagram, Phase Relations, 9) [1943And] Andersen, A.G.H., Kingsbury, A.W., “Phase Diagram of the Copper-Iron-Silicon System from 90 to 100 % Copper”, Trans. Am. Inst. Mining Metallurgy Pet. Engineering, 152, 38–47 (1943) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 21) [1949Jae] Jaenecke, E., “Cu-Fe-Si” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag Heidelberg, 660–661 (1949) (Phase Diagram, Phase Relations, Review, 2) [1953Vog] Vogel, R., Horstmann, D., “The Diagram of State Iron-Iron Silicide-Copper Silicide-Copper” (in German), Arch. Eisenhuettenwes., 24(9), 435–440 (1953) (Experimental, Phase Diagram, Phase Relations, Morphology, 6) [1965Ued] Ueda, J., Yamane, T., “A Note on the Effect of Iron on the Annealing Behavior of a Cold Rolled Copper-Silicon Alloy”, Trans. Jpn. Inst. Met., 6(3), 154–158 (1965) (Experimental, Mechan. Prop., Morphology, 7) [1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 (1974) (Review, Thermodyn., Calculation, 249) [1975Abr] Abrikosov, N.Kh., Petrova, L.I., “Preparation of Crystals of the Low-Temperature Modiﬁcation of FeSi2”, Inorg. Mater., 11(2), 184–186 (1975), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 11(2), 223–225 (1975) (Phase Diagram, Phase Relations, Crys. Structure, Experimental, 7) [1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., “Cu-Fe-Si” in “INCRA Monograph. Series 6. Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metall Systems”, Univ. Wisconsin-Milwaukee, U.S.A., 492–497 (1979) (Crys. Structure, Phase Diagram, Phase Relations, Review, Thermodyn., 6) [1981Has] Hasebe, M., Nishizawa, T., “Further Study on Phase Diagram of The Iron-Copper System”, Calphad, 5(2), 105–108 (1981) (Experimental, Phase Relations, Calculation, 4) [1983Str] Stroz, D., Panek, T., Morawiec, H., “Inﬂuence of the Addition of a Third Element to the Precipitation Process in Cu-Fe Alloys”, Mater. Sci. Engineering, 58(1), 43–53 (1983) (Experimental, Mechan. Prop., 20) [1986Ole] Olesinski, R.W., Abbaschian, G.J., “The Cu-Si (Copper-Silicon) System”, Bull. Alloy Phase Diagrams, 7(2), 170–178 (1986) (Phase Diagram, Phase Relations, Crys. Structure, Thermodyn., Review, #, 230) [1991But] Butt, M.T.Z., Bodsworth, C., “Liquid Immiscibility in Ternary Metallic Systems”, Mater. Sci. Technol., 7(9), 795–802 (1991) (Theory, Phase Relations, Review, 39) [1992Liu] Liu, B.X., Shang, C.H., Liu, C.H., “Metastable Phases Formed in Fe-Cu-Si Multilayered Films by Ion Irradiation”, J. Mater. Res., 7(1), 85–88 (1992) (Crys. Structure, Experimental, 24) [1992Rag] Raghavan, V., “The Cu-Fe-Si (Copper-Iron-Silicon) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 6B, 759–767 (1992) (Crys. Structure, Phase Diagram, Phase Relations, Review, 6) [1997Oht] Ohtani, H., Suda, H., Ishida, K., “Solid/Liquid Equilibria in Fe-Cu Based Ternary Systems”, ISIJ Int., 37(3), 207–216 (1997) (Calculation, Phase Relations, Review, Thermodyn., 47)

DOI: 10.1007/978-3-540-78644-3_3 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Cu–Fe–Si [1997Yam]

[1998Mie] [1999Hin]

[1999Yam]

[2001Cas]

[2001Lee]

[2001Nog]

[2001Was]

[2002Leb]

[2002Rag] [2002Wan]

[2002Was]

[2003Mie] [2003Ono]

[2004Wan]

[2005Mec]

[2005Yam]

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17

Yamauchi, I., Suganuma, A., Okamoto, T., Ohnaka, I., “Effect of Copper Addition on the β-phase Formation Rate in FeSi2 Thermoelectric Materials”, J. Mater. Sci., 32(17), 4603– 4611 (1997) (Experimental, Kinetics, Phase Relations, Electr. Prop., 17) Miettinen, J., “Reassessed Thermodynamic Solution Phase Data for Ternary Fe-Si-C System”, Calphad, 22(2), 231–256 (1998) (Calculation, Assessment, Thermodyn., 36) Hino, M., Nagasaka, T., Washizu, T., “Phase Diagram of Fe-Cu-Si Ternary System Above 1523 K”, J. Phase Equilib., 20(3), 179–186 (1999) (Calculation, Experimental, Phase Diagrams, Phase Relations, 13) Yamauchi, I., Nagase, T., Ohnaka, I., “Temperature Dependence of β-Phase Transformation in Cu Added Fe2Si5 Thermoelectric Material”, J. Alloys Compd., 292, 181–190 (1999) (Experimental, Kinetics, Phase Relations, 10) Castrucci, P., Gunnella, R., Bernardini, R., Montecchiari, A., Carboni, R., De Crescenzi, M., “Epitaxy of Fe/Cu/Si(111) Ultrathin Films: an Auger Electron Diffraction Study”, Surf. Sci., 482(2), 916–921 (2001) (Experimental, Morphology, 18) Lee, Y.-F., Lee, S.-L., Huang, C.-H., Lee, C.K., “Effects of Fe Additive on Properties of Si Reinforced Copper Matrix Composites Fabricated by Vacuum Inﬁltration”, Powder Met., 44(4), 339–343 (2001) (Morphology, Electr. Prop., Phys. Prop., Experimental, 15) Nogi, K., Kita, T., “Inﬂuence of Copper Addition to α-Fe2Si5 on Thermoelectric Properties of Iron-Silicides Produced by Spark-Plasma Sintering”, Mater. Trans., 42(5), 862–869 (2001) (Morphology, Electr. Prop., Phys. Prop., Experimental, 14) Washizu, T., Nagasaka, T., Hino, M., “Viscosity of Liquid Fe-Cu-Si Alloy Formed in New Melting Process for Domestic Waste Incineration Residue”, Mat. Trans., 42(3), 471–477 (2001) (Experimental, Transport Phenomena, 28) Lebrun, N., Dobatkina, T., Kuznetsov, V., “Cu-Si (Copper-Silicon)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 20.12505.1.20, (2002) (Crys. Structure, Phase Diagram, Assessment, 23) Raghavan, V., “Cu-Fe-Si (Copper-Iron-Silicon)”, J. Phase Equilib., 23(3), 267–270 (2002) (Phase Diagram, Phase Relations, Review, 9) Wang, C.P., Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in Fe-Cu-X (X: Co, Cr, Si, V) Ternary Systems”, J. Phase Equilib., 23(3), 236–245 (2002) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 38) Washizu, T., Nagasaka, T., Hino, M., “Heat Content of Liquid Fe-Cu-Si Alloys Formed in the Melting Treatment Process of Domestic Waste Incineration Residue”, Z. Metallkd., 93(4), 281–287 (2002) (Phase Relations, Thermodyn., Experimental, 22) Miettinen, J., “Thermodynamic Description of the Cu-Fe-Si System at the Cu-Fe Side”, Calphad, 27(4), 389–394 (2003) (Assessment, Phase Diagram, Phase Relations, Thermodyn., 26) Ono-Nakazato, H., Taguchi, K., Usui, T, “Estimation of the Evaporation Rate of Copper and Tin from Molten Iron-Silicon Alloy”, ISIJ Int., 43(7), 1105–1107 (2003) (Thermodyn., Kinetics, Calculation, 14) Wang, C.P., Liu, X.J., Takaku, Y., Ohnuma, I., Kainuma, R., Ishida, K., “Formation of Core-Type Macroscopic Morphologies in Cu-Fe Base Alloys With Liquid Miscibility Gap”, Metall. Mater. Trans. A, 35A(4), 1243–1253 (2004) (Calculation, Experimental, Morphology, Phase Relations, Thermodyn., 31) Meco, H., Napolitano, R.E., “Liquidus and Solidus Boundaries in the Vinicity of OrderDisorder Transitions in Fe-Si System”, Scripta Mater., 52, 221–226 (2005) (Experimental, Calculation, Phase Diagram, Phase Relations, Thermodyn., 30) Yamauchi, I., Irie, T., Sakaguchi, H., “Metastable Liquid Separation in Undercooled Fe-Cu and Fe-Cu-Si Melts Containing a Small B Concentration and Their Solidiﬁcation Structure”, J. Alloys Compd., 403, 211–216 (2005) (Experimental, Morphology, Phase Relations, 10)

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DOI: 10.1007/978-3-540-78644-3_3 # Springer 2008

18 [2006Wah]

[2007Tur]

[Mas2] [V-C2]

Cu–Fe–Si Wahl, U., Correia, J.G., Rita, E., Araujo, J.P., Soares, J.C., “Fe and Cu in Si: Lattice Sites and Trapping at Implantation-Related Defects”, Nucl. Instrum. Methods Phys. Res./ B, 253, 167–171 (2006) (Experimental, Crys. Structure, Electronic Structure, 23) Turchanin, M., Agraval, P., “Cu-Fe (Copper-Iron)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 20.11107.1 (2007) (Phase Diagram, Crys. Structure, Thermodyn., Assessment, 31) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_3 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Cu–Fe– Ti

1

Copper – Iron – Titanium Tamara Velikanova, Mikhail Turchanin

Introduction Practical interest in the Cu-Fe-Ti system results from the hydrogen storage capacity of the alloys, the possibility to obtain amorphous materials by ultrarapid quenching, the high-strength Cu based alloys by precipitation hardening, and the promising application of diffusion bonding of titanium and iron parts using copper as an interlayer. A partial liquidus surface of the Cu-Fe-Ti system was ﬁrst published by [1968Tak]. Later a number of experimental works [1970Kha, 1971Kha, 1971Zak, 1993Min] were devoted to the study of phase relationships in the Cu rich corner of the system. The results of [1968Tak, 1970Kha, 1971Kha, 1971Zak] were critically reviewed by [1979Dri, 1979Cha, 1992Rag]. Phase structures along the line TiCu1–xFex at 900°C were studied by [1989Wu] using Mössbauer spectroscopy. Experimental investigations of the TiCu-TiFe [1993Ali] and Ti2Cu-TiFe [1994Ali2] sections as well as the Ti-TiCu-TiFe [1994Ali1] part of the phase diagram were stimulated by the discovery of glass formation by ultrarapid quenching of liquid alloys. An isothermal section at 850°C of the whole Cu-Fe-Ti system was established by [1995Bee] using a special diffusion technique supplemented by conventional equilibration of alloys. Five ternary phases were reported to exist as equilibrium phases at 850°C. The results of [1993Ali, 1994Ali1, 1994Ali2, 1995Bee] were critically reviewed by [2002Rag]. Thermodynamic properties only for liquid alloys were investigated by [2006Abd]. The experimental investigations of phase relationships and thermodynamic properties of phases in the Cu-Fe-Ti system are summarized in Table 1. Binary Systems The binary systems Cu-Fe and Cu-Ti are accepted from [2007Tur] and [2002Ans] respectively. The Fe-Ti binary phase diagram is taken from [Mas2]. Solid Phases The crystal structure data of solid phases are listed in Table 2. Five ternary phases, denoted as τ1, τ2, τ3, τ4 and τ5, were reported to exist in the system at 850°C by [1995Bee]. They were found in the experiments which combined a method of diffusion couples and the traditional methods of investigation of equilibrated alloys. Two of the ternary phases with unknown crystal structure, τ4 and τ5, were reported to have no isostructural compounds in the related binary systems. The ternary τ1, τ2 and τ3 phases are reported to be based on the TiCu2, Ti2Cu3 and Ti3Cu4 binary phases, respectively. A continuous composition range of τ2 from Ti2Cu3 to Ti0.4Fe0.17Cu0.43 is not excluded (it is shown by a dashed line in Fig. 10) after [1995Bee]. The formation of the ternary phases τ2, τ3 and τ5 in the diffusion interfaces are conﬁrmed in the work of [2005Kun] by the SEM-BSE method at the temperatures 850 and 900°C. However, at 950°C Cu-Fe-Ti and Cu-Ti based intermetallics were not found [2005Kun]. According to the results from the diffusion couple experiments supported by conventionally equilibrated alloys, TiFe dissolves up to 38 at.% Cu at 850°C [1995Bee]. This value is in excellent agreement with the value 37.5 at.% reported by [1989Wu] for alloys annealed 100 h at 900°C. [1994Ali1], however, deduced a much lower value of 25 at.% at 930°C from the study of alloys annealed for 50 h at 900°C. In view of this discrepancy, further investigations are needed to obtain a more precise value. The solubilities of Fe in Ti2Cu and TiCu were measured to be about 2 at.% Fe [1995Bee] and about 1 at.% Fe [1989Wu], respectively, via diffusion couple experiments. The homogeneity ranges of the ternary phases are given in Table 2. For all of them the variation of the Ti content is very small. For (Fe1–xCux)Ti [1994Ali1] reported a maximal Ti content of about 54 at.% Ti, whereas [1995Bee] has drawn it with less than 51 at.% Ti. The drawings of [1995Bee] agree much better with Schreinemakers’ rule than those of [1994Ali1]. Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_4 # Springer 2008

2

Cu–Fe– Ti

Cu decreases the solubility of Ti in (γFe) and Fe decreases the solubility of Ti in (Cu). Substitution of Cu by Fe and Ti atoms leads to an expansion of the cubic lattice of the Cu based solid solution as shown in Fig. 1 [1970Kha]. At the same time, substitution of the Fe atoms by Cu in TiFe leads to an expansion of its cubic lattice as it was found by [1989Wu, 1995Bee]. Figure 2 demonstrates the linear dependence of the lattice parameter of the CsCl type structure of TiFe solid solution as a function of the Fe content after [1989Wu]. Quasibinary Systems According to [1994Ali1], the TiFe-TiCu section is a quasibinary system with a eutectic composition of 5 at. % Fe and a eutectic temperature of 930°C. This statement is not compatible with the liquidus proposed by the same authors for the TiFe-Ti-TiCu region and the corresponding reaction scheme. There the abovementioned eutectic temperature is not a maximal one on the monovariant line of the equilibrium L ⇌ TiFe + TiCu, which is a prerequisite for a true quasibinary system. Because of the same reason, the Cu-TiFe2 section can not be quasibinary, as it was proposed by [1970Kha], notwithstanding on the reported constant solidus temperature for the alloys along this section. The corresponding vertical sections are given in the section “Temperature-Composition Sections” of this assessment. There was no tie line found by [1970Kha, 1971Zak] with a maximal temperature on the solidus surface (Cu) + TiFe2. The solidus temperature of this phase ﬁeld decreases continuously from 1080°C at the L + (γFe) ⇌ (Cu) + TiFe2 equilibrium with increasing Ti content. Invariant Equilibria Invariant equilibria are studied systematically only for the Ti rich alloys in the TiFe-Ti-TiCu region by [1994Ali1]. The results [1994Ali1] are given in the reaction scheme in Fig. 3. Outside this region an invariant reaction L + (γFe) ⇌ (Cu) + TiFe2 at 1080°C is reported by [1970Kha]. Liquidus and Solidus Surfaces The liquidus and solidus surface projections for the Ti rich part of the system and TiFe+Ti+TiCu region, reported by [1994Ali1], are given in Figs. 4 and 5, respectively. The ﬁrst liquidus isotherms of the region TiFe-Ti-TiCu were reported by [1968Tak], based on direct thermal analysis. A eutectic reaction L ⇌ (βTi) + TiFe + Ti2Cu at the Ti content of about 65 at.% and at 950°C was proposed. These data are close to those of [1994Ali1], but do not coincide. The supposed eutectic temperature is lower than that of the incongruent U1 process, but it is higher than the temperature of the quasibinary TiFe-TiCu eutectic after [1994Ali1]. Taking into account this circumstance the above mentioned ternary eutectic could be realized only if a quasibinary TiFe-Ti2Cu eutectic exists in the system above 950°C. Although the latter is not excluded, the data of such kind so far are not available. Isotherms of the solidus surface of the Cu rich region (95 to 100 mass% Cu) were reported by [1971Zak] indicating also the L + (βTi) + TiFe + Ti2Cu four-phase ﬁeld. The Cu corner of the solidus surface is shown in Fig. 6, with the four-phase equilibrium L + (Cu) + Ti2Fe + TiFe tentatively added. The equilibria involving τ3 and τ2 are questionable because the temperature intervals of their stability are not known. The solidus temperatures were determined by [1971Zak] using metallographic investigation of alloys tempered in steps of 20°C and subsequently water quenched. Thus, the data precision can be estimated to be ±10°C. Isothermal Sections Isothermal sections at 900, 850 and 650°C for the TiFe-Ti-TiCu part of the system reported by [1994Ali1] are given in Figs. 7, 8, and 9, respectively. The alloys prepared by arc-melting were heat treated in the following process: at 900°C for 50 h and water quenched, 850°C for 100 h and water quenched, 650°C for 150 h and followed by air-cooling. Because the homogenization temperature is rather close to the solidus, one can suppose that equilibrium was achieved. No ternary compounds are found in the Ti corner of the system. The phase relations at 850°C in the entire composition range were measured by [1995Bee] using diffusion couples. Most of the critical conclusions were conﬁrmed by conventional equilibration of alloys. Annealing times and phases found are well documented. The isothermal section at 850°C is given in Fig. 10 DOI: 10.1007/978-3-540-78644-3_4 # Springer 2008

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Cu–Fe– Ti

3

after [1995Bee]. Five ternary phases are found to exist at 850°C. A “ternary” τ1 phase, which is isostructural with the binary TiCu2, is treated by [1995Bee] as a solid solution of TiCu2 stabilized in the ternary system by some addition of Fe at a lower temperature than it is stable in the Cu-Ti binary system. The crystal structures of the phases τ2 and τ3 are closely related to Ti2Cu3 and Ti3Cu4, respectively. It is not excluded that the τ2 phase forms a continuous solid solution with the binary Ti2Cu3 phase, which is indicated in Fig. 10 by a thick dashed line. The τ4 and τ5 phases are without doubt true ternary compounds. The topology of the phase equilibria in the TiFe-Ti-TiCu region after [1995Bee] agrees qualitatively with that of [1994Ali1]. However, there is a noticeable difference concerning the compositions of the phases in the ternary equilibria, especially the solubility of Cu in TiFe after [1995Bee] is much larger and agrees very well with [1989Wu], whereas the Ti content of TiFe after [1994Ali1] reaches a maximum of about 55 at.%, but less than 51 at.% after [1995Bee]. Although the results of [1995Bee] are supported by those of [1989Wu], this question needs further experimental veriﬁcation. In agreement with both [1994Ali1] and [1995Bee], the alloy Fe-8Cu-2Ti (mass%) compacted by sintering at 1350°C was found to be in the two-phase region of TiFe2+(αFe) [1999Pie]. Three isothermal sections at 900, 850 and 650°C in the Cu corner of the ternary system have been determined [1970Kha, 1971Kha, 1971Zak]. The isothermal sections at 900 and 650°C are given in Figs. 11, 12 with some corrections mainly according to the accepted binary phase diagrams. [1992Rag] in his review published a partial isothermal section from Cu-Fe up to 40 at.% Ti at 851°C based on the experimental data of [1970Kha]. Equilibrium between TiFe2 and Cu4Ti assumed in this section is in contradiction to [1995Bee] who assumed equilibria between TiFe2 and (Cu) as well as between TiCu and (Cu). Therefore the isothermal section proposed by [1992Rag] can not be accepted. Temperature – Composition Sections Five temperature-composition sections for the TiFe-Ti-TiCu part are published by [1993Ali, 1994Ali1, 1994Ali2]. Four of them are: at Fe:Cu = 3:1, Fe:Cu = 1:1, Fe:Cu = 1:3 [1994Ali1] and TiCu-TiFe [1993Ali]. The vertical section TiCu-TiFe is given in Fig. 13. It is treated by [1993Ali] as a quasibinary system of eutectic type (with eutectic temperature 930°C), which is not reasonable because its temperature is less than the temperature of the adjoining invariant equilibrium L + Ti2Fe ⇌ TiFe + TiCu of 950°C according to [1994Ali1]. In Fig. 13 this vertical section is given after data of [1993Ali] with minor correction made to account for the above remark: the three-phase ﬁeld is added in the section. The vertical section Cu-TiFe2 is given in Fig. 14. According to [1970Kha] the section coincides with the line Cu-TiFe2, where the TiFe2 phase is of congruent composition. Therefore the section is considered by the authors to be a quasibinary system. However, no temperature maximum is shown on the solidus of the (Cu) + TiFe2 two-phase ﬁeld in the vertical section at 95 mass% Cu by [1971Kha], which must exist in the case of a quasibinary L ⇌ (Cu) + TiFe2 equilibrium. The section Cu-TiFe2 given in Fig. 14 differs from that of [1970Kha] by adding the three-phase ﬁeld L + (Cu) + TiFe2 according to the above remark. Thermodynamics Experimental information on the thermodynamic properties of ternary phases is available only for liquid alloys. In [2006Abd], the mixing enthalpy of liquid alloys was investigated at 1600°C and xTi < 0.6 by high temperature calorimetry. The investigation was carried out along three sections at xFe/xCu = 1/3, xFe/xCu = 1, and xFe/xCu = 3. The experiments show that the integral mixing enthalpy has negative values for alloys with xTi > 0.2. The maximum mixing enthalpy is related with the Cu-Fe binary system, the value is 10.8 kJ·mol–1 at xFe = 0.42 [2007Tur], its minimum value reaches –20.9 kJ·mol–1 at xTi = 0.47 in the binary Fe-Ti system [2006Abd]. The isotherm of integral mixing enthalpy at 1600°C according to [2006Abd] is shown in Fig. 15. The thermodynamic properties of the liquid phase were modeled by the ideal associated solution model, assuming a set of associates: TiCu, Ti2Cu, TiFe2, TiFe, and TiFeCu3. Notes on Materials Properties and Applications According to [1970Kha] the microhardness of alloys at 95 mass% Cu has a minimum at the composition of the crossing point with the Cu-Ti2Fe section. At the same composition the electrical conductivity shows a Landolt-Börnstein New Series IV/11D4

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Cu–Fe– Ti

maximum value. The microhardness of alloys along the Cu-TiFe2 section quenched from 650, 800, 850 and 900°C [1970Kha] is shown in Fig. 16. Mechanical properties of Cu alloys doped by Ti and Fe depending on the conditions of homogenization, quenching, preliminary deformation and ﬁnal thermal treatment, are reported by [1983Hae]. The microhardness of alloys along the TiCu-TiFe section was studied by [1993Ali]. The microhardness of an annealed alloy at the eutectic composition Cu45Ti50Fe5 was found as 4000 MPa. An amorphous alloy of the same composition shows a microhardness value of 6100 MPa along with an ultimate strength of 2300 MPa. A study on electrical conductivity and Hall constant [1993Ali] demonstrates the change in electrical conductivity during the crystallization process of amorphous alloys. Two dilute alloys of the compositions Cu-0.8Fe-0.4Ti (at.%) and Cu-0.4Fe-0.4Ti (at.%) were studied in the temperature range from 500 to 950°C by electrical conductivity measurements. The electrical conductivities of the two alloys are much higher than theoretical values calculated assuming all the elements to be dissolved. The dependence of electrical conductivity on aging temperature was employed to evaluate the activation energy for the decomposition of the Cu matrix, which was found to be about 200 kJ·mol–1. Mechanical properties of an arc-melted alloy of the Ti-15Fe-15Cu (mass%) composition were studied by [2005Lou]. The alloy shows a good combination of compressive mechanical properties: Young’s modulus of 121 GPa, compressive fracture strength of 1.61 GPa, 0.2% yield strength of 1.53 GPa, and 8% ductility. An addition of B in small quantities (0.5 at.%) increases mechanical strength of the alloy up to 2.47 GPa, but decreases ductility. An addition of Cu improves ductility of the corresponding Fe-Ti binary alloy. The experimental investigations of the Cu-Fe-Ti materials properties are summarized in Table 3. Miscellaneous Amorphous alloys were obtained by rapid quenching of melt. Fully amorphous ribbons of composition Cu100–x–yFexTiy were formed for alloys with 0 ≤ x ≤ 10 and 40 ≤ y ≤ 60 (at.%) [1988Dun]. Amorphous alloys Cu100–xFexTi50 with 0 ≤ x ≤ 20 (at.%) were prepared by melt spinning at cooling rates of 106 K·s–1 [1993Ali]. The crystallization behavior of amorphous alloys was investigated in the above-mentioned works. The hydrogenation behavior of the amorphous Cu45Fe5Ti50 alloy was studied by [1988Dun]. The sintering process of Fe-8Cu-2Ti (mass%) compacts was studied by DTA [1999Pie]. Three different liquid phases formed and disappeared by interdiffusion during heating the compacts up to 1350°C. Diffusion bonding was carried out between commercially pure titanium and stainless steel using copper as interlayer in the temperature range of 850–950°C in vacuum [2005Kun]. The presence of different reaction layers in the diffusion zone was exhibited in the study. The occurrence of different intermetallic compounds such as Ti2Cu, TiCu, Ti2Cu3, Ti3Cu4, TiFe, TiFe2, τ2, τ3, and τ5 was conﬁrmed by X-ray diffraction. A maximum bond strength of 318 MPa was obtained for the couple bonded at 900°C due to a better coalescence of mating surfaces. With rise of the joining temperature to 950°C, the bond strength decreased due to the formation of brittle Fe-Ti based intermetallics. At a lower joining temperature of 850°C, the bond strength was also lower due to incomplete coalescence of mating surfaces. Mössbauer spectra of different alloys of the ternary Cu-Fe-Ti system were studied by [1971Win, 1988Dun, 1989Wu].

Table 1.

Investigations of the Cu-Fe-Ti Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1968Tak]

Thermal analysis, measurements of microhardness

Partial liquidus surface

[1970Kha]

Optical microscopy, X-ray analysis, differential thermal analysis, measurements of microhardness, measurements of electrical conductivity, magnetic metallography

95 to 100 mass% Cu and 650 to 1100°C

(continued) DOI: 10.1007/978-3-540-78644-3_4 # Springer 2008

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Cu–Fe– Ti

5

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1971Kha]

magnetic metallography, magnetic susceptibility measurements

95 to 100 mass% Cu and 650°C

[1971Zak]

Optical microscopy, X-ray analysis, differential thermal analysis, measurements of microhardness, measurements of electroconductivity, magnetic metallography

95 to 100 mass% Cu and 650 to 1100°C

[1989Wu]

Mössbauer spectroscopy, X-ray analysis, EPMA, SEM

Phase structures of TiCu1–xFex alloys at x = 0.1–0.6

[1993Ali]

Optical microscopy, X-ray analysis, EPMA, differential thermal analysis, durometerical analysis, measurements of microhardness, measurements of electrical conductivity and Hall constant

TiCu-TiFe section

[1993Min]

Electrical conductivity measurements, TEM, SEM, STEM EDX microanalysis, ﬁeld ion microscopy, atom probe microanalysis

Cu 0.8Fe-0.4Ti (at.%) and Cu-0.4Fe-0.4Ti (at.%) at 500 to 950°C

[1994Ali1]

Optical microscopy, X-ray analysis, differential thermal analysis

Ti-TiCu-TiFe portion at 650 to 900°C

[1994Ali2]

Optical microscopy, X-ray analysis, EPMA, thermal analysis, measurements of microhardness

Ti2Cu-TiFe section at 900 to 1300°C

[1995Bee]

Diffusion “sandwich” couples technique, optical microscopy, SEM, EPMA, X-ray analysis

Isothermal section at 850°C

[1999Pie]

Differential thermal analysis

Sintering Fe-8Cu-2Ti (mass%) at RT to 1350°C

[2005Kun]

Optical microscopy, X-ray analysis, SEM, mechanical properties testing

Diffusion bonding of Ti/Cu/Fe multilayers

[2005Lou]

X-ray analysis, SEM, mechanical properties measurements, compressive mechanical testing, density measurements

Ti-15Fe-15Cu (mass%) at RT

[2006Abd]

High temperature calorimetry

Liquid alloys at 1600°C and xTi < 0.6

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

(Cu), TixFeyCu1–x–y < 1095

cF4 Fm 3m Cu

Lattice Parameters [pm]

a = 361.46

Comments/References

at y = 0 and 885°C x = 0.08 [2002Ans] at x = 0 and 1095°C y = 0.05 [2007Tur] at x = 0 y = 0 and 25°C [V-C2, Mas2] (continued)

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Cu–Fe– Ti

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

γ, TixFe1–x–yCuy 1487–847 (γFe) 1394–912

cF4 Fm 3m Cu

α, TixFe1–x–yCuy < 1538

cI2 Im 3m W

(δFe) 1538–1394 (αFe) < 912 (βTi), Ti1–x–yFexCuy 1668–595

Lattice Parameters [pm]

a = 364.68

at x = 0 and 1417°C y = 0.135 [2007Tur] at y = 0 and 1150°C x = 0.008 [Mas2] at x = 0 y = 0 and 915°C [V-C2, Mas2]

a = 293.15

at x at x at y at x

a = 286.65

at x = 0 y = 0 and 25°C [V-C2, Mas2]

cI2 Im 3m W

a = 330.65 (αTi), Ti1–x–yFexCuy < 882

TiFe, Ti1–xFex–yCuy < 1317

hP2 P63/mmc Mg

a = 295.06 c = 468.35

cP2 Pm 3m CsCl a = 297.6 to 298.6

TiFe2, Ti1–xFex–yCuy < 1427

TiCu4, Ti1–xCux < 885

hP12 P63/mmc MgZn2 oP20 Pnma ZrAu2

Comments/References

a = 478.5 c = 779.9

= = = =

0 and 1487°C y = 0.058 0 and 847°C y = 0.016 [2007Tur] 0 and 1289°C x = 0.10 [Mas2] 0 y = 0 and 1390°C [V-C2, Mas2]

at x/y = 3 and 1040°C y + x = 0.18 [1994Ali1] at x/y = 1 and 990°C y + x = 0.17 [1994Ali1] at x/y = 1/3 and 1050°C y+x=0.14 [1994Ali1] at x = 0 and 1005°C y = 0.135 [2002Ans] at y = 0 and 1085°C x = 0.22 [Mas2] pure Ti(h) at T > 882°C [Mas2] at x = 0 and 790°C y = 0.016 [2002Ans] at y = 0 and 700°C x = 0.0005 [Mas2] pure Ti(l) at 25°C [Mas2] at 850°C y = 0 to 0.38 [1995Bee] at 930°C y = 0 to 0.25 [1993Ali] at y = 0 and 1085°C x = 0.475 to 0.503 [Mas2] at y = 0 and x = 0.47 to 0.50 [V-C2] at 850°C y = 0 to 0.02 [1995Bee] at y = 0 x = 0.646 to 0.724 [Mas2] at y = 0 and x = 0.717 [V-C2] x = 0.780 to 0.809 [2002Ans]

a = 452.5 b = 434.1 c = 1295.3

[V-C2]

(continued)

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Cu–Fe– Ti

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

TiCu2, Ti0.33FexCu0.67–x 890–870

oC12 Cmm2 VAu2

7

Lattice Parameters [pm]

Comments/References

[2002Ans]

a = 436.3 b = 797.7 c = 447.8

at x = 0 [V-C2]

τ1, Ti0.33FexCu0.67–x

oC12 Amm2

at 850°C x = 0.01 to 0.025 [1995Bee]

Ti2Cu3, Ti0.4FexCu0.6–x < 875

tP10

[2002Ans]

P4/nmm Ti2Cu3

a = 313 c = 1395

at x = 0 [V-C2]

τ2, Ti0.4FexCu0.6–x Ti3Cu4, Ti0.43FexCu0.57–x < 925

at 850°C x = 0.05 to 0.17 [1995Bee] tI14 I4/mmm Ti3Cu4

[2002Ans] a = 313.0 c = 1994

at x = 0 [V-C2]

τ3, Ti0.43FexCu0.57-x TiCu, Ti1–xFeyCux–y < 982

Ti2Cu, Ti0.67FexCu0.33–x < 1012

at 850°C x = 0.21 to 0.24 [1995Bee] tP4 P4/nmm TiCu

at 930°C y = 0 to 0.03 [1993Ali] at y = 0 x = 0.48 to 0.52 [2002Ans] at y = 0 [V-C2]

a = 310.8 to 311.8 c = 588.7 to 592.1

tI6 I4/mmm MoSi2

[2002Ans] at 850°C x = 0 to 0.02 [1995Bee] a = 295.3 c = 1073.4

at x = 0 [V-C2]

* τ4, Ti0.37FexCu0.63–x

-

-

at 850°C x = 0.05 to 0.07 [1995Bee]

* τ5, Ti0.45FexCu0.55–x

-

-

at 850°C x = 0.04 to 0.05 [1995Bee]

Table 3.

Investigations of the Cu-Fe-Ti Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1970Kha]

Measurements of microhardness and electrical conductivity

Microhardness, electrical conductivity

[1983Hae]

SEM, mechanical testing

Mechanical properties

[1988Dun]

Weight measurements

Hydrogen absorption of amorphous alloys (continued)

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Cu–Fe– Ti

Reference

Method/Experimental Technique

Type of Property

[1993Ali]

Tensile testing machine, measurements of electrical conductivity and Hall constant at heating

Ultimate tensile strength, microhardness, electrical resistively and Hall constant of amorphous alloys

[1993Min]

Electrical measurements with a Sigmatest apparatus

Electrical conductivity

[2005Kun]

Tensile testing machine

Bond strength, ultimate tensile strength, breaking strain

[2005Lou]

Mechanical properties testing Archimedian method

Young's modulus, compressive fracture strength, yield strength, ductility, density

Fig. 1. Cu-Fe-Ti. Lattice parameters of the (Cu) solid solution vs TiFe2 content in the alloys quenched from 900 and 650°C

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Fig. 2. Cu-Fe-Ti. Lattice parameters of the TiFe solid solution vs Fe content

Fig. 3. Cu-Fe-Ti. Partial reaction scheme Landolt-Börnstein New Series IV/11D4

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Fig. 4. Cu-Fe-Ti. Partial liquidus surface projection, Ti corner

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Fig. 5. Cu-Fe-Ti. Partial solidus surface projection, Ti corner

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Cu–Fe– Ti

Fig. 6. Cu-Fe-Ti. Partial solidus surface projection, Cu corner

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Fig. 7. Cu-Fe-Ti. Partial isothermal section at 900°C, Ti corner

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Fig. 8. Cu-Fe-Ti. Partial isothermal section at 850°C, Ti corner

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Fig. 9. Cu-Fe-Ti. Partial isothermal section at 650°C, Ti corner

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Fig. 10. Cu-Fe-Ti.

Cu–Fe– Ti

Isothermal section at 850°C

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Fig. 11. Cu-Fe-Ti.

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Partial isothermal section at 900°C, Cu corner

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Cu–Fe– Ti

Fig. 12. Cu-Fe-Ti. Partial isothermal section at 650°C, Cu corner

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Fig. 13. Cu-Fe-Ti. Temperature - composition section TiCu-TiFe

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Cu–Fe– Ti

Fig. 14. Cu-Fe-Ti. Partial temperature- composition section Cu-TiFe2

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Fig. 15. Cu-Fe-Ti. Integral mixing enthalpy of liquid alloys at 1600°C in kJ·mol–1

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Fig. 16. Cu-Fe-Ti. Microhardness of Cu-TiFe2 alloys, quenched from 650, 800, 850 and 900°C

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References [1968Tak] Takeuchi, Y., Watanabe, M., Yamabe, S., Wada, T., “Titanium- and Zirconium Eutectic Solders” (in German), Metall, 22, 8–15 (1968) (Phase Diagram, Experimental, 11) [1970Kha] Khan, M.G., Zakharov, A.M., Zakharov, M.V., “Study of the Ternary Cu-Fe-Ti Phase Diagram” (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., 13(1), 104–109 (1970) (Phase Diagram, Experimental, 8) [1971Win] Window, B., “Mössbauer Studies of Iron in Copper Alloys”, J. Phys. F: Met. Phys., 1, 533–538 (1971) (Crys. Structure, Experimental, 20) [1971Kha] Khan, M.G., Zakharov, M.V., Zakharov, A.M., Zikeeva, V.N., “Identiﬁcation of a Phase Based on Fe in Cu-Rich Alloys of the Cu-Fe-Ti Ternary System” (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., 14(4), 98–99 (1971) (Phase Diagram, Experimental, 2) [1971Zak] Zakharov, M.V., Zakharov, A.M., Khan, M.G., “The Cu Corner of the Ternary Cu-Fe-Ti System” (in Russian) in “Diagrammy Sostoyaniya Metallichskikh Sistem”, Mater. 4th Vses. Soveshch., 1969, Ageev, N.V., (Ed.), 139–141 (1971) (Phase Diagram, Experimental, 3) [1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., “Cu-Fe-Ti” in “INCRA Monograph. Series 6. Phase Diagrams and Thermodynamic Properties of Ternary Copper-Metall Systems”, Uni. Wisconsin-Milwaukee, USA, 501–503 (1979) (Phase Diagram, Review, 3) [1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, Rokhlin, L.L., Turkina, N.I., “Cu-Fe-Ti” (in Russian) in “Binary and Multicomponent Copper-Base System”, Nauka, Moscow, 119–120 (1979) (Phase Diagram, Review, 1) [1983Hae] Haeussler, D., Daut, H.H., “Electron-Microscopic Investigations in Dispersion Hardened Copper” (in German), Freib. Forsch. B, Metall. Werkstofftech., B234, 77–85 (1983) (Morphology, Mechan. Prop., Experimental, 3) [1988Dun] Dunlap, R.A., Stroink, G., Stadnik, Z.M., Dini, K., “Properties of As-Quenched and Hydrogenated Copper-Iron-Titanium Alloys”, Mater. Sci. Eng., 99, 543–546 (1988) (Morphology, Phys. Prop., Experimental, 10) [1989Wu] Wu, C., Li, J., “Phase Structure of the TiCu1–xFex System”, Metall. Trans. A, 20A, 981–985 (1989) (Crys. Structure, Experimental, 8) [1992Rag] Raghavan, V., “The Cu-Fe-Ti (Copper-Iron-Titanium) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Institut of Metals, Calcutta, 6B, 776–780 (1992) (Crys. Structure, Phase Diagram, Phase Relations, Review, 7) [1993Ali] Alisova, S.P., Lutskaya, N.V., Budberg, P.B., Bychkova, E.I., “Phase Constitution of the TiCu-TiNi-TiCo (TiFe) Systems in the Equilibrium and Metastable States”, Russ. Metall. (Engl. Transl.), (3), 205–212 (1993), translated from Izv. Ros. Akad. Nauk, Metally, 3, 222–229 (1993) (Phase Diagram, Experimental, 16) [1993Min] Mineau, L., Hamar-Thibault, S.J., Allibert, C.H., “Precipitation in Cu-Rich Cu-Fe-Ti Ternary Alloys - a Continuous Process?”, Phys. Status Solidi A, 137, 87–100 (1993) (Phase Diagram, Crys. Structure, Experimental, 22) [1994Ali1] Alisova, S.P., Kovneristyi, Yu.K., Budberg, P.B., Lutskaya, N.V., “The Ti-TiFe-TiCu System”, Russ. Metall. (Engl. Transl.), (2), 122–125 (1994), translated from Izv. Ros. Akad. Nauk, (2), 157–161 (1994) (Phase Diagram, Experimental, 6) [1994Ali2] Alisova, S.P., Lutskaya, N.V., Kobylkin, A.N., Budberg, P.B., “TiFe-Ti2Cu Section of the Ti-Fe-Cu System. Conditions of the Formation of Ti2Fe Compound”, Russ. Metall., (5), 121–123 (1994), translated from Izv. Ros. Akad. Nauk, (5), 170–172 (1993) (Phase Diagram, Experimental, 8) [1995Bee] van Beek, J.A., Kodentsov, A.A., van Loo, F.J.J., “Phase Equilibria in the Cu-Fe-Ti System at 1123 K”, J. Alloys Compd., 217, 97–103 (1995) (Phase Relations, Phase Diagram, Experimental, 16) [1999Pie] Pieczonka, T., Kaysser, W.A., Petzow, G., “Transient Liquid Phase Sintering of Fe-Cu-Ti Compacts”, J. Mater. Proces. Technology, 92, 21–24 (1999) (Phase Relations, Experimental, 28) [2002Rag] Raghavan, V., “Cu-Fe-Ti (Copper-Iron-Titanium)”, J. Phase Equilib., 23(2), 172–174 (2002) (Crys. Structure, Phase Relations, Review, 9)

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[2005Kun]

[2005Lou]

[2006Abd]

[2007Tur]

[Mas2] [V-C2]

Cu–Fe– Ti Ansara, I., Ivanchenko, V., “Cu-Ti (Copper-Titanium)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmBH, Stuttgart; Document ID: 20.11457.1.20, (2002) (Crys. Structure, Phase Diagram, Assessment, 26) Kundu, S., Ghosh, M., Laik, A., Bhanumurthy, K., Kale, G.B., Chatterjee, S., “Diffusion Bonding of Commercially Pure Titanium to 304 Stainless Steel Using Copper Interlayer”, Mater. Sci. Eng. A, 407, 154–160 (2005) (Crys. Structure, Morphology, Experimental, 16) Louzguine-Luzgin, D.V., Louzguina-Luzgina, L.V., Inoue, A., “Investigation of the Structure and Properties of Hypereutectic Ti-based Bulk Alloys”, Mater. Res. Soc. Symp. Proc., 842, 133–138 (2005) (Crys. Structure, Mechan. Prop., Morphology, Phase Relations, Experimental, 16) Abdulov, A.R., Turchanin, M.A., Agraval, P.G., “Application of Ideal Associated Solution Model for Prediction of Glass Formation Composition Intervals in Ternary Liquid Alloys” (in Russian), Metallofiz. Noveishie Tekhnol., 28, 1247–1256 (2006) (Thermodyn., Experimental, Calculation) Turchanin, M., Agraval, P., “Cu-Fe (Copper-Iron)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart, Document ID: 20.11107.1 (2007) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assessment, Phys. Prop., #, 36) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–H–Mn

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Iron – Hydrogen – Manganese Volodymyr Ivanchenko, Tetyana Pryadko

Introduction The solubility of hydrogen in molten Fe-Mn alloys was measured by [1961Mae] (1620°C and 101 kPa, to 8 mass% Mn), [1963Wei] (1592°C and 101 kPa, to 10 mass% Mn), [1970Fuk, 1970Kat] (at 1600°C to 3 mass% Mn) and [1975Bes] (at 1500, 1600 and 1700°C, to 12 mass% Mn), as listed in Table 1. Theories of hydrogen solubility were detailed in [1965Bur, 1967Bur] and the experimental data were reviewed by [1977Bes] and [1981Sch]. The hydrogen-induced phase transformation of the fcc γ phase was studied by [1978Pon, 1982Ant1, 1982Ant2, 1986Usu, 1993Aik1, 1993Aik2]. Hydrogen saturation increases with the temperature of the ε→γ transformation at high pressures [1978Pon]. It was shown that the hydrogen solubility is higher in the ε phase than in the γ phase regardless of the route of hydrogenation. [1993Aik1, 1993Aik2] studied the hcp ε phase in an Fe-21 at.% Mn alloy in order to compare the stability of the γ and ε phases in a two-phase alloy subjected to cathodic hydrogen charging in an aqueous solution. They showed that the hcp ε phase can always be stabilized more easily than the fcc γ phase, not only in a hydrogen-gas atmosphere at high pressures, as in the case studied by [1978Pon] and [1982Ant2], but also in an aquas solution under cathodic polarization. The effect of hydrogen on the magnetic properties and electroresistivity of an Fe-22.4 at.% Mn alloy was studied by [1982Ant1]. [1991Bol] proposed a theory for the calculation of the distribution coefﬁcients of hydrogen between tetrahedral and octahedral interstices in Fe based alloys. The results of the calculations are in contradiction with the observation that hydrogen is not found in the tetrahedral interstices. The solubility and mobility of hydrogen in solid Fe-Mn alloys were studied experimentally by [1965Sch], and [1966Bur], as discussed by [1977Kar]. Investigations of phase relations in the Fe-H-Mn system, structures and thermodynamics are listed in Table 1. Binary Systems The assessed hydrogen-pressure-temperature Fe-H phase diagram (up to 10 GPa) is taken from [2003Fuk], who accepted the results of [1982Ant2] and [2002Ant]. The Fe-H system under a hydrogen pressure of 10 MPa is accepted from [2002Zin]. The phase relations in this diagram are similar to those of [1990San]. The accepted H-Mn phase diagram is taken from [2002Fuk] that has been established over a wide range of p(H2) (to 7.6 GPa), and T (to 1000°C). A new phase was found, ε’, which has a dhcp structure. This leads to the appearance of a third triple point γ-ε-ε’ at a hydrogen pressure of 3.5 GPa and temperature of 700°C. The curves below 3 GPa have been reproduced from [1996Ant], where the temperature of the ε→γ transition increases linearly with pressure. A fourth triple point, δ+γ+L, was included, but only qualitatively. The Fe-Mn phase diagram is accepted from [2004Wit]. Solid Phases The crystal structures of the unary and binary phases are presented in Table 2. No ternary phase of a crystal structure type different from those of the unary and binary phases was reported. In the Fe-H system within the studied T-p interval, there are 4 different phases, having the bcc, fcc, hcp and dhcp lattice, that are based on the α and γ phases of pure iron and the high pressure ε phase. Studies showed that hydrogen and deuterium occupy octahedral interstices in the close packed iron lattices of both the ε and ε’ phases. Deuterium randomly occupies octahedral interstices in the hcp iron lattice of the ε-FeD0.42. In this respect, the ε phase in the Fe-H(D) system is unlike the non-stoichiometric hcp phases TcH and MnD. The ε hydride, having a hcp iron lattice, is formed as an intermediate metastable phase in the course of the transformation of (αFe) to the stable ε’ hydride at high pressures and elevated temperatures [1998Ant, 2003Fuk, Landolt-Börnstein New Series IV/11D4

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2005Fuk]. The ε’ hydride, having a dhcp iron lattice, is thermodynamically stable at high hydrogen pressures [1991Bad, 1998Ant]. The composition of the ε’ phase is close to the stoichiometry FeH or FeD, and its metal lattice contains many stacking faults [1998Ant]. Hydrogen or deuterium atoms in this phase occupy all available octahedral interstitial sites in the metal lattice. The fcc γ phase is characterized by the formation of superabundant vacancies [2003Fuk, 2005Hir]. Both ε and ε’ hydrides are unstable at ambient conditions and rapidly decompose to (αFe) and molecular hydrogen. In the H-Mn system, there are 5 different phases: the primary solid solutions based on the α and β allotropic modiﬁcations of manganese containing only a few atomic percent of hydrogen, a hydride based on the γ fcc modiﬁcation of manganese and the hydrides with hcp ε and dhcp ε’ metal lattices. The fcc manganese hydride MnHx with x ≈ 0.41 forms at high hydrogen pressures and can be considered as an interstitial solid solution of hydrogen in the γ modiﬁcation of manganese. The dissolved hydrogen expands the crystal lattice of (γMn) at a rate of dVa/dx ≈ 1.85 Å3/H atom, which is typical of transition metal hydrides [1998Fed]. Under high pressures of hydrogen, manganese forms ε hydrides [1975Pon] with the H/Mn atomic ratio x ranging from 0.65 to 0.96 [1978Bel]. In the ε manganese hydrides MnHx with x ≥ 0.83, hydrogen atoms are randomly distributed over octahedral interstices in the hcp metal lattice (a deﬁcient NiAs type structure) [1987Iro]. At x = 0.65, hydrogen forms a superstructure, presumably of the anti-CdI2 type [1987Iro]. The dhcp ε’ phase was found to exist [2002Fuk] in the region where the structure was previously thought to be hcp [1996Ant, 2002Ant]. The crystallographic data presented by [2002Fuk] indicate that in the course of the εv→⊊ε’⊊→⊊γ phase transitions, both the atomic volume and the spacing between close-packed planes are nearly conserved, and only their stacking sequence is changed: ε (ABAB…) → ε’ (ABAC...) → γ (ABCABC…). There is also a peculiar feature in the kinetics of the phase transitions. The transition between the ε hcp and ε’ dhcp phases is reversible and very fast: transitions in both directions were completed in less than 1 min in the course of stepwise changes of temperature across the phase boundary. In contrast, the ε → γ and ε’ → γ transitions were irreversible. Once the fcc structure has been formed, the reverse transition to the hcp and dhcp structures was sluggish and incomplete. Liquidus, Solidus and Solvus Surfaces The solubility of hydrogen in an Fe-Mn melt at 1620°C and 101 kPa was ﬁrst measured by [1961Mae], who reported that alloying with Mn decreases the hydrogen solubility from 24 in pure Fe to 9 ppm (mass) at 8 mass% Mn. [1963Wei] found that alloying with Mn increased the hydrogen solubility at 1592°C and 101 kPa from 24.7 ppm for pure Fe to 25.7 ppm (mass) for the Fe-10 mass% Mn alloy. Later, [1970Fuk, 1970Kat] expressed the composition dependence of the hydrogen solubility as {H}alloy = {H}Fe/ 10(–0.0014 XMn) following studies at 1600°C and up to 3 mass% Mn using a sampling method. Their results are in good agreement with [1963Wei], but the results of [1963Wei, 1970Fuk, 1970Kat] are in disagreement with data of the later work of [1971Blo, 1975Bes]. [1971Blo] and [1975Bes] are consistent with each other and show a more drastic increase in the hydrogen solubility with Mn addition (from 25.6 for pure Fe to 30.5 ppm (mass) for the Fe-10 mass% Mn alloy [1975Bes]). The interaction parameters for Mn with hydrogen in liquid Fe, εMn H , presented in the review [1977Bes] (i.e. the slope of hydrogen solubility vs the Mn content), are: –0.30 calculated from data of [1963Wei], –0.73 from [1970Fuk, 1970Kat], –1.9 from [1975Bes], and –2.0 from [1971Blo]. In order to make a choice between the data of [1963Wei, 1970Fuk, 1970Kat] and [1971Blo, 1975Bes], the linear relationship between the logarithm of hydrogen solubility and the ratio of the metals can be derived (log {Halloy} = xFe·log {HFe} + xMn·log {HMn}, where {Halloy}, {HFe} and {HMn} are solubility of hydrogen in a Fe-Mn alloy and pure Fe and Mn). However, there are no reliable data for H solubility in Mn at 1600°C and 101 kPa. [1967Bur] extrapolated the data of [1937Sie] for the H-Mn system at 1350–1450 to 1600°C in order to describe the H solubility in the Fe-Mn melt from 0 to 100% Fe. However, there may be some error in the extrapolation leading to incorrect results. Burylev obtained an expression that was inconsistent with the earlier work [1965Bur] (the latter described well the experimental data of [1963Wei]), which turned out to be in better agreement with the later experimental data of [1971Blo, 1975Bes] rather than those of [1963Wei]. Thus, there would seem to be no way to chose unambiguously between the 1600°C liquidus isotherm of [1963Wei] and [1970Fuk, 1970Kat] or that of [1975Bes], which is close to [1971Blo]. DOI: 10.1007/978-3-540-78644-3_5 # Springer 2008

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3

In order to calculate the solvus isotherm at 1000°C, [1966Bur] proposed the equation logVHFe-Mn {ccm/100 g} = 0.73 + 0.78·xMn, which was derived using the H solubility in Fe and Mn in accordance with the later work of [1984Fro] ({H}Fe = 0.027 at.%, VHFe = 5.348 ccm/100g; and {H}Mn = 0.156 at.%, VHMn = 32 ccm/100g). [1965Sch] showed that alloying with Mn increases the solubility of hydrogen at 900 and 1000°C. The dependence of hydrogen solubility on the Mn content is not monotonous between 400 and 800°C, and in the temperature interval from 400 to 600°C and from 5 to 9 mass% Mn, the solubility of hydrogen is independent of the Mn content. The hydrogen saturation raises the temperature of the ε→γ transformation at high pressures [1978Pon]. The solubility of hydrogen in the ε phase, formed in the Fe-22 mass% Mn alloy at 280°C and 2 GPa hydrogen, is close to 0.1 H/Me, which is more than 3 times higher than in the γ phase formed in this alloy [1978Pon]. The hydrogen solubility was shown to be higher in the ε phase than in the γ phase irrespective of the route of hydrogenation. [1993Aik1, 1993Aik2] studied the hcp ε phase in an Fe-21Mn (at.%) alloy in order to compare the stability of the γ and ε phases in the two-phase alloy subjected to cathodic hydrogen charging in an aqueous solution and showed that the hcp ε phase can always be stabilized more easily than the fcc γ phase, not only in a hydrogen-gas atmosphere at high pressure, as in the case studied by [1978Pon] and [1982Ant2], but also in an aqueous solution under cathodic polarization. Isothermal Sections The isothermal section of the Fe-H-Mn system at 3 GPa and 600°C is given in Fig. 1. It is constructed using the data related to the solubility of hydrogen in the γ phase of pure iron as a function of temperature and hydrogen pressure [2005Hir, 2005Fuk], the p-T phase diagrams of the Fe-H [2003Fuk] and Mn-H [2002Fuk] systems and data relating to the solubility of hydrogen in the γ and ε phases in the Fe-22 mass% Mn alloy at 2 GPa and 350°C [1978Pon]. Because the section was constructed for pressures of 3 GPa, the experimentally derived data for the hydrogen solubility in the γ and ε phases of [1978Pon] pﬃﬃﬃﬃﬃﬃﬃﬃ were increased by 3=2. Thermodynamics There are few thermodynamic data on the Fe-H-Mn system. The speciﬁc activity coefﬁcient of hydrogen in liquid Fe-H-Mn alloys was evaluated by [1981Sch] as: log γHMn = (– 489.75·xMn + 138.73·xMn2/T) + (0.0695·xMn – 0.0243·xMn2), where xMn is the mole fraction of Mn in the melt. Notes on Materials Properties and Applications [1967Kod, 1968Kod] studied the effect of plastic deformation and annealing on the hydrogen permeability of ferromagnetic austenite (Fe-36 mass% Mn) over the temperature interval of 300 to 600°C and a hydrogen pressure of 101 kPa. It was shown that hydrogen permeability in the deformed alloy is more sensitive to point defects and pile-ups, and also to free dislocations. They excluded the role of short-range order, which varies considerably with plastic deformation and may have considerable inﬂuence on hydrogen mobility. [1982Ant1] reported that at 250°C and pH2 3 GPa, an isomorphic phase transition ε1 →⊊ε2 took place leading to an uneven rise in the hydrogen solubility, up to 0.4 H/Me. At this hydrogen content, the Fe77.6Mn22.4 becomes ferromagnetic. The high-temperature corrosion of Fe-Mn alloys in hydrogensulphide/hydrogen atmospheres was studied by [1984Sme]. A mechanism of hardening or softening of Fe-Mn alloys with hydrogen was studied by [1988Kim]. Literature data concerning investigations of the material properties of Fe-H-Mn alloys are listed in Table 3. Miscellaneous Alloying with Mn lowers the mobility of hydrogen in solid Fe-Mn alloys. The rate is at a maximum when the Mn content is higher than 8 mass% [1965Sch]. According to calculations performed by [2006Ela], Mn can form hydrides, which contributes to the impurity distribution between the liquid and gas phases. Landolt-Börnstein New Series IV/11D4

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Fe–H–Mn

[2006Ela] studied the removal of impurities from Fe by hydrogen plasma arc melting. It was shown that by using a gas mixture of Ar + 30 vol% H2, the Mn content could be reduced from 11.1 mass ppm to 0.31 mass ppm.

Table 1.

Investigations of the Fe-H-Mn Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1961Mae]

Saturation of liquid alloys by hydrogen in Sieverts’ type apparatus

1620°C, < 8 mass% Mn, liquid

[1963Wei]

Saturation of liquid alloys by hydrogen in Sieverts’ type apparatus

1592°C, < 10 mass% Mn, liquid

[1965Sch]

Effusion method and hot extraction method

400–1000°C, up to 14 mass% Mn

[1970Fuk] [1970Kat]

Sampling method

1600°C, < 3 mass% Mn, liquid

[1978Pon]

X-ray diffraction, electroresistivity at high temperatures and high pressures

Up to 250°C,in inert medium (silicone) pressure up to 2 GPa, hydrogen pressure up to 2.33 GPa, γ→ε and ε→γ transformations in the Fe-22 mass% Mn alloy

[1982Ant1]

X-ray diffraction, electroresistivity and spontaneous magnetization at high pressures of hydrogen

250°C, up to 7 GPa of hydrogen pressure, antiferromagnetic-ferromagnetic transition in Fe-22.4 at.% Mn - H alloy

[1993Aik1] [1993Aik2]

X-ray diffraction, the specimens were cathodically charged with hydrogen at 17°C, using a bath of 0.1 N H2SO4, poisoned with a small amount of As2O3, the current density was 500 A·cm–2

21.3 mass% Mn alloy annealed at 1000°C after that quenched in ace water, ε and γ phases saturated with hydrogen

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(βH) < – 259.34

hP2 P63/mmc Mg

a = 377.6 c = 616.2

[Mas2] triple point

(αH) < – 271.9

cF4 Fm 3m Cu

a = 533.8

[Mas2]

(δFe)(h2) 1538–1394

cI2 Im 3m W

a = 293.15

at 1390°C [V-C2, Mas2]

(continued)

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Fe–H–Mn

5

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αFe)(r) < 912

cI2 Im 3m W

a = 286.65

Pure Fe at 25°C [Mas2]

a a a a

Metastable in Fe-Mn binary system, quenched from the γ phase region 10.9 at.% Mn, [2000Mar] 12.2 at.% Mn, [2000Mar] 14.5 at.% Mn, [2000Mar] 16.9 at.% Mn, [2000Mar]

α’(Mn,Fe) = = = =

287.4 287.55 287.6 287.8

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]

(δMn)(h3) 1246–1138

cI2 Im 3m W

a = 308.0

Pure Mn, at 1138°C [Mas2]

γ, (γMn,γFe)

cF4 Fm 3m Cu

a = 357.6+0.122 xMn

0 ≤xMn ≤ 50 [2000Mar]

a = 386.0

Pure Mn, at 1100°C [Mas2]

a = 364.67

Pure Fe, at 915°C [V-C2, Mas2]

(γMn)(h2) 1138–1100 (γFe)(h1) 1394–912 γ’MnHx

tI2 P14/mmm

a = 267.0 c = 377.6

x = 0.41, at 27°C [1998Fed]

β, MnHx

cP20 P4132 βMn

a = 634.2

x = 0.08, at room temperature [1996Ant]

(βMn)(h1) 1100–727 α, MnHx (αMn)(r) < 727 ε, (Mn,Fe)Hx ε, (Mn,Fe) ε, MnHx

a = 631.52 Pure Mn, at 727°C [Mas2]

cI58 I 43/mmc αMn

a = 894.03

x = 0.073, 27°C [2002Ant]

a = 891.26

Pure Mn, at 25°C [Mas2]

hP2 P63/mmc Mg

Metastable in Fe-Mn binary system 18.5 at.% Mn [1993Oka]

a = 253.3 c = 408.8 a = 266.8 c = 433.0

x = 0.65 [1978Bel] (continued)

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Fe–H–Mn

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

a = 269.2 c = 435.5 a = 269.4 c = 435.7 a = 269.7 c = 436.8

x = 0.83, at –153°C [2002Ant] x = 0.86, at room temperature [1996Ant] x = 0.94 [1978Bel]

ε’, FeHx(I)

hP4 P63/mmc Nd

a = 267.9 c = 877.0

x = 1, at –183°C [2002Ant]

ε’, MnHx(I)

hP4 P63/mmc Nd

a = 271.3 c = 886.2

5.2 GPa, at 760°C [2002Fuk]

Table 3.

Investigations of the Fe-H-Mn Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1967Kod]

Hydrogen permeability using membrane technique, microhardness, volume resistivity, X-ray line broadening

Inﬂuence of plastic deformation on the hydrogen permeability

[1968Kod]

Hydrogen permeability using membrane technique, microhardness, X-ray line broadening

Inﬂuence of plastic deformation on the hydrogen permeability

[2006Ela]

GDMS was used for precise analysis of impurity content in specimens before and after plasma arc melting

Reﬁning of iron

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Fe–H–Mn

Fig. 1. Fe-H-Mn.

Landolt-Börnstein New Series IV/11D4

7

Isothermal section at 3 GPa and 600°C

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8 References [1937Sie] [1961Mae]

[1963Wei] [1965Bur] [1965Sch] [1966Bur] [1967Bur] [1967Kod]

[1968Kod]

[1970Fuk]

[1970Kat] [1971Blo] [1975Bes]

[1975Pon]

[1977Bes]

[1977Kar]

[1978Bel]

[1978Pon]

[1981Sch]

Fe–H–Mn

Sieverts, A., Moritz, H., “Manganese and Hydrogen” (in German), Z. Phys. Chem., Abt. A, 180, 249–263 (1937) (Phase Diagram, Phase Relations, Experimental, 5) Maekawa, S., Nakagawa, Y., “The Effect of Some Alloying Elements on the Solubility of Hydrogen in Liquid Iron” (in Japanese), Nippon Kinzoku Gakkai-shi, 25(9), 577–580 (1961) (Phase Relations, Thermodyn., Experimental, 6) Weinstein, M., Elliott, J.F., “Solubility of Hydrogen in Liquid Iron Alloys”, Trans. Met. Soc. AIME, 227, 382–393 (1963) (Phase Relations, Thermodyn., Calculation, Experimental, 27) Burylev, B.P., “Solubility of Hydrogen in Liquid Iron Alloys” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., 8(2), 17–22 (1965) (Phase Relations, Thermodyn., Calculation, 13) Schwarz, W., Zittter H., “Solubility and Diffusion of Hydrogen in Iron Alloys” (in German), Arch. Eisenhuettenwes., 36(5), 343–349 (1965) (Phase Relations, Experimental, 16) Burylev, B.P., “Solubility of Hydrogen in Solid Iron Alloys”, Russ. J. Phys. Chem., 40(4), 442–445 (1966) (Phase Relations, Calculation, 12) Burylev, B.P., “Solubility of Gases in Molten Mn-base Alloys” (in Russian), Izvest. Vyssh. Ucheb. Zaved., Chern. Met., (4), 5–11 (1967) (Phase Relations, Calculation, 17) Kodes, Ye.S., Geld, P.V., Goltsov, V.A., “Effect of Plastic Deformation and Annealing on the Hydrogen Permeability of Ferromanganese Austenite”, Phys. Met. Metallogr., 24, 144–149 (1967), translated from Fiz. Met. Metalloved., 24(3), 528–534 (1967) (Experimental, Electr. Prop., Mechan. Prop., Transport Phenomena, 10) Kodes, E.S., Goltsov, V.A., Geld, P.V., “Solubility and Rate of Permeation of H in Fe-Ni and Fe-Mn Austenitic Alloys” (in Russian), Tr. Uralsk. Politekhn. Inst., 167, 20–25 (1968) (Experimental, Mechan. Prop., Transport Phenomena, 10) Fukuda, S., Sugiyama, T., Furukawa, T., Kato, E., “Solubility of Hydrogen in Liquid Iron Alloys”, Rep. Casting Research Lab./Waseda Univ., (21), 35–46 (1970) (Phase Relations, Thermodyn., Experimental, 22) Kato, E., Fukuda, S., Sugiyama, T., Furukawa, T., “Solubility of Hydrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 56, 521–535 (1970) (Experimental, 28) Blossey, R.G., Pehlke, R.D., “Molubility of Hydrogen in Liquid Fe-Co-Ni Alloys”, Metallurg. Trans., 2(11), 3157–3161 (1971) (Phase Relations, Thermodyn., 27) Bester, H, “Kinetic of the Hydrogen Exchange Between the Gas Phase and Liquid Iron as well as his Binary Alloys”, Dr.-Ing. Diss. Techn. Hochsch. Aachen, (1975), as quoted by [1977Bes] Ponyatovskii, E.G., Belash, I.T., “Production and Physical-Chemical Properties of Manganese Hydride” (in Russian), Dokl. Acad. Nauk SSSR, 224 (3), 607–608 (1975) (Crys. Structure, Phase Relations, Experimental, 1) Bester, H., Lange, K.W., “H Solubility in Fe and in Liquid Fe-Mn, Fe-Cr, and Fe-Si Alloys” (in German), Stahl u. Eisen, 97, 1037–1039 (1977) (Phase Relations, Thermodyn., Experimental, 53) Karamysheva, G.A., Men, A.N., “Calculation of the Concentration-Dependence of Hydrogen Solubility in Binary Alloys Using the Cluster Component Method”, Russ. Metall. (Engl. Transl.), (2), 82–83 (1977), translated from Izv. Akad. Nauk SSSR, Met., (2), 95–96 (1977) (Calculation, Interface Phenomena, 5) Belash, I.T., Ponomarev, V.K., Tissen, V.G., Afonnikova, N.S., Shekhman, V.Sh., Ponyatovskii, E.G., “Ferromagnetism in Mn-H and Mn-D System” (in Russian), Fiz. Tverd. Tela, 20(2), 422–427 (1978) (Crys. Structure, Phase Relations, Experimental, 24) Ponyatovskiy, Y.G., Antonov, V.Y., Belash, I.T., “Inﬂuence of Hydrogen Pressure up to 23 kBars on Temperature of ε-γ Transformation in Fe-22 % Mn Alloy”, (in Russian), Fiz. Met. Metalloved., 46 (5), 1090–1092 (1978) (Phase Relations, Experimental, Electr. Prop., 7) Schuermann, E., Kaettlitz, W., “Equivalent Effect of the Alloying Elements on the Concentration- and Temperature-Dependent Hydrogen Solubility in Iron-Rich Ternary and Multicomponent Melts” (in German), Arch. Eisenhuettenwes., 52(8), 295–301 (1981) (Phase Relations, Thermodyn., Calculation, 20)

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Fe–H–Mn [1982Ant1]

[1982Ant2]

[1984Fro] [1984Sme]

[1986Usu]

[1987Iro]

[1988Kim]

[1990San] [1991Bad]

[1991Bol]

[1993Aik1]

[1993Aik2]

[1993Oka]

[1996Ant]

[1998Ant]

[1998Fed]

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Antonov, V.E., Belash, I.T., Georgieva, I.Ya., Degtyareva, V.F., Thiessen, V.G., Shalimova, A.V., “Magnetization of Solid Solutions of Hydrogen in HCP Fe+22.4 at.% Mn Alloy”, Sov. Phys. - Solid State, 24(4) 554–558 (1982), translated from Fiz. Tverd. Tela, 24(4), 975–981 (1982) (Crys. Structure, Phase Relations, Experimental, Magn. Prop., Electr. Prop., 23) Antonov, V.E., Belash, I.T., Ponyatovski, E.G., “T-p Phase Diagram of the Fe-H System at Temperatures to 450°C and Pressures to 6.7 GPa”, Scr. Metall., 16(2), 203–208 (1982) (Phase Relations, Phase Diagram, Electr. Prop., Magn. Prop., Experimental, 15) Fromm, E., Jehn, H., “Solubility Hydrogen in the Elements”, Bull. Alloy Phase Diagrams, 5(3), 323–326 (1984) (Phase Relations, Review, 2) Smeltzer, W.W., Jackson, P.R.S., “The High-Temperature Corrosion of Fe-Mn and Fe-Mn-Al Alloys in Hydrogen-Sulphide Hydrogen Atmospheres”, CIM Bull., 77(866), 52 (1984) (Abstract) Usui, M., Asano, S., “Hydrogen Induced Transformation in FCC Fe-Mn Alloys” (in Japanese), J. Jpn. Inst. Met., 50(11), 943–949 (1986) (Crys. Structure, Phase Relations, Experimental, 10) Irodova, A.V., Glazkov, V.P., Somenkov, V.R., Shilstein, S.Sh., Antonov, V.E., Ponyatovskii, E.G., “Neutron Diffraction Study of Antiferromagnetic Ordering in Manganese Hydrides”, Sov. Phys. Solid State, 29(8) 1562–1568 (1987) (Crys. Structure, Phase Relations, Experimental, Magn. Prop., 6) Kimura, T., Matsui, H., Kimura, H., “Effect of Hydrogen on the Mechanical Properties of Iron-Based Alloys” in “Strength of Metals and Alloys, (ICSMA8)”, Proceedings of the 8th International Conference, Pergamon, Oxford, Vol. 2, 541–546 (1988) (Morphology, Mechan. Prop., Experimental, 5) San-Martin, A., Manchester, F.D., “Fe-H (Iron-Hydrogen)”, Bull. Alloy Phase Diagr., 11(2), (1990) (Phase Diagram, Crys. Structure, Phase Relations, Assessment, #, 91) Badding, J.V., Hemley, R.J., Mao, H.K., “High-Pressure Chemistry of Hydrogen in Metals: In Situ Study of Iron Hydride”, Science, 253(5018), 421–424 (1991) (Crys. Structure, Morphology, Phase Relations, Experimental, 33) Bol’shov, L.A., “Hydrogen Localization in FCC Lattices of Alloys of Iron with Chromium, Manganese, Cobalt, and Nickel”, Russ. Metall.,(2), 165–169 (1991), translated from Izv. Akad. Nauk SSSR. Met., (2), 165–169 (1991) (Phase Relations, Thermodyn., Calculation, 6) Aikawa, T., Nishino, Y., Asano, S., “Preferential Absorption of Hydrogen in the ε Phase in Fe-Mn Alloys” (in Japanese), J. Jpn. Inst. Met., 57(4), 484–388 (Crys. Structure, Phase Relations, Experimental, 25) Aikawa, T., Nishino, Y., Asano, S., “Stabilization of the HCP Epsilon phase in an Fe-21 % Mn Alloy Subjected to Cathodic Hydrogen Charging”, Scr. Metall. Mater., 29(1) 135–137 (1993) (Crys. Structure, Phase Relations, Experimental, 16) Okamoto, H., “Fe-Mn (Iron-Manganese)” in “Phase Diagram of Binary Iron Alloys”, Okamoto, H. (Ed.), ASM International, Materials Park, OH, 9, 203–213 (1993) (Crys. Structure, Phase Diagram, Thermodyn., Assessment, #, 91) Antonov, V.E., Antonova, T.E., Chirin, N.A., Ponyatovskii, E.G., Baier, M., Wagner, F.E., “T-p Phase Diagram of the Mn-H System at Pressures to 4.4 GPa and Temperatures to 1000°C”, Scr. Mater., 34(8), 1331–1336 (1996) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, #, 15) Antonov, V.E., Kornell, K., Fedotov, V.K., Kolesnikov, A.I., Ponyatovsky, E.G., Shiryaev, V.I., Wipf, H., “Neutron Diffraction Investigation of the dhcp and hcp Iron Hydrides and Deuterides”, J. Alloy Compd., 264, 214–222 (1998) (Crys. Structure, Phase Relations, Experimental, #, 24) Fedotov, V.K., Antonov, V.E., Kolesnikov, A.I., Beskrovnyi, A.I., Grosse, G., Wagner, F.E., “Neutron Diffraction Investigation of γ Manganese Hydride”, Solid State Commun., 107(12), 787–790 (1998) (Crys. Structure, Phase Relations, Experimental, #, 21)

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10 [2000Mar]

[2002Ant]

[2002Fuk]

[2002Zin]

[2003Fuk]

[2004Wit]

[2005Fuk]

[2005Hir]

[2006Ela]

[Mas2] [V-C2]

Fe–H–Mn Marinelli, P., Baruj, A., Fernandez Guillermet, A., Sade, M., “Lattice Parameters of Metastable Structures in Quenched Fe-Mn Alloys. Part I: Experimental Techniques, bcc and fcc Phases”, Z. Metallkd., 91(11), 957–962 (2000) (Crys. Structure, Experimental, Phase Relations, 38) Antonov, V.E., “Phase Transformations, Crystal and Magnetic Structures of High-Pressure Hydrides of d-Metals”, J. Alloys Compd., 330–332, 110–116 (2002) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, 46) Fukai, Y., Haraguchi, T., Shinomiya, H., Mori, K., “Constitution of the Mn-H System at High Hydrogen Pressure”, Scr. Mater., 46(9), 679–684 (2002) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, #, 25) Zinkevich, M., Mattern, N., Handstein, A., Gutﬂeisch, O., “Thermodynamics of Fe-Sm, Fe-H, and H-Sm Systems and its Application to the Hydrogen-DisproportionationDesorption-Recombination (HDDR) Process for the System Fe17Sm2-H2”, J. Alloys Compd., 339, 118–139 (2002) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 101) Fukai, Y., Mori, K., Shinomiya, H., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys Under High Hydrogen Pressures”, J. Alloys Compd., 348,105–109 (2003) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, #, 42) Witusiewicz, W.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diffus., 25(4), 346–354 (2004) (Phase Diagram, Thermodyn., Assessment, 34) Fukai, Y., “The Structure and Phase Diagram of M-H Systems at High Chemical PotentialsHigh Pressure and Electrochemical Synthesis”, J. Alloys Compd., 404–406, 7–15 (2005) (Electrochemistry, Interface Phenomena, Phase Diagram, Review, Thermodyn., 40) Hiroi, Y., Fukai, Y., Mori, K., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys Revisited”, J. Alloys Compd., 404–406, 252–255 (2005) (Crys. Structure, Phase Relations, Phase Diagram, Experimental, #, 23) Elanski, D., Lim, J.-W., Mimura, K., Isshiki, M., “Impurity Removal from Fe, Cr, Ti, and V Metals by Hydrogen Plasma arc Melting and Thermodynamic Estimation of Hydride and Sulﬁde Formation”, J. Alloys Compd., 421(1–2), 209–216 (2006) (Calculation, Phase Diagram, Phase Relations, 8) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–H–Mo

1

Iron – Hydrogen – Molybdenum Kostyantyn Korniyenko

Introduction The constitution of the ternary Fe-H-Mo system is of great interest, primarily in relation to the use of Fe-Mo alloys for hydrogen permeation applications. On the whole, hydrogen has the unique property of being able to diffuse through certain metals at a rapid rate, and attempts have been made to exploit this property in the thermally regenerative cell system. The use of a permeable metal diaphragm as an electrode in fused salt systems alleviates some of the problems associated with porous metal gas electrodes, namely, concentration polarization and “ﬂooding” of the electrode with either electrolyte or gas. Although iron and some iron alloys have proved to be compatible with a lithium hydride cell environment, their use as a hydrogen diffusion diaphragm-electrode limits the cell current density and therefore restricts the practical application of such a cell [1965Hei]. The dissolution of hydrogen in iron-molybdenum alloys was studied experimentally by [1934Sie] and has been reviewed by [1938Kub]. Subsequent studies of phase equilibria in the ternary Fe-H-Mo system have been concentrated mainly on the inﬂuence of molybdenum additions on the hydrogen solubility of liquid iron [1961Mae, 1964Gun, 1967Ban, 1967Som, 1970Fuk, 1970Kat, 1972Ngi, 1976Zhi]. A mathematical method of calculating the solubility of hydrogen in Fe-Mo alloys has been presented by [1966Bur]. A list of the investigations of phase relations, crystal structures and thermodynamics as well as the techniques employed are presented in Table 1. Binary Systems The Fe-H system under a hydrogen pressure of 0.1 MPa is accepted from [Mas2], which is based on the results of [1990San]. Later, this system was investigated carefully by [2003Fuk] up to hydrogen pressures of 10 GPa, temperatures up to 1500°C (Fig. 1). A drastic reduction in the melting point to 800°C owing to the dissolution of hydrogen was observed at a hydrogen pressure of 3 GPa. In comparison to the p-T phase diagram of pure iron, the α-γ-ε triple point of Fe at 8.4 GPa and 430°C was shifted to 5 GPa and 260°C. The hydrogen solubility in (γFe) and (αFe) under high pressure and its correlation with superabundant vacancy formation were reported by [2005Hir]. The Fe-Mo and H-Mo systems are accepted from [Mas2]. Solid Phases No ternary intermetallic phases have been found in the Fe-H-Mo ternary system. Crystallographic data relating to the known unary and binary phases and their compositions and temperature ranges of stability are listed in Table 2. Investigations of hydrogen solubility in solid Fe-Mo binary alloys were carried out by [1934Sie]. The data obtained were reproduced in the review of [1938Kub] in relation to the phase equilibria in the Fe-Mo binary system. The temperature dependence of this solubility for the alloys with different compositions is shown in Fig. 2; the solubility increases with increasing temperature. The most drastic increase in hydrogen solubility is observed for iron rich alloys. It should be noted that as the constitution of the Fe-Mo system was later revised, information about hydrogenation of Fe-Mo alloys is in need of amendment. A formula for calculating the solubility of hydrogen in solid iron-molybdenum alloys has been proposed by [1966Bur]. The calculated results were compared with the experimental data given by [1934Sie] for 1100 and 1000°C, and satisfactory agreement was observed. Isothermal Sections Knowledge of the phase relationships in the Fe-H-Mo system is limited since all investigations have been carried out on samples having a high concentration of iron. Isothermal sections of the Fe-H-Mo system have Landolt-Börnstein New Series IV/11D4

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Fe–H–Mo

not been constructed. Information in the literature relates to the solubility of hydrogen in liquid iron-based Mo-containing alloys [1961Mae, 1964Gun, 1967Ban, 1967Som, 1970Fuk, 1970Kat, 1972Ngi]. The published data are quite contradictory. [1964Gun, 1967Ban, 1967Som, 1970Kat, 1972Ngi] have reported a decrease in the solubility of hydrogen with increasing molybdenum content. However, [1961Mae, 1976Zhi] reported a contrary tendency for hydrogen solubility, it increasing with increasing molybdenum contents up to about 6 mass% (or 3.58 at.%) at 1600°C. [1981Sch] formulated a mathematical model on the basis of published experimental data, and used this to construct isotherms of hydrogen solubility at temperatures of 1605 and 1540°C. However, a number of the experimental data used were in contradiction with their original articles. Thermodynamics The effect of molybdenum on the activity of hydrogen in liquid iron alloys has been widely studied experimentally [1961Mae, 1964Gun, 1965Bag, 1967Ban, 1967Som, 1970Fuk, 1970Kat, 1972Ngi]. On the whole, the results obtained by applying both the Sieverts’ method [1964Gun, 1965Bag, 1967Ban, 1967Som, 1970Fuk, 1970Kat, 1972Ngi] and the samples method [1961Mae, 1970Fuk, 1970Kat] show that Mo additions increase the values of log fHMo. The interaction parameters for hydrogen in liquid Fe-Mo alloys obtained by various investigators are compiled in Table 3. The thermodynamic aspects of hydrogen solubility in liquid Fe-Mo alloys are discussed in relation to electronic structure [1963Wei, 1972Ngi] or based on an H– coordinate structure [1965Bag]. A mathematical description of the concentration- and temperature-dependent speciﬁc activity coefﬁcients γHX in the iron rich Fe-H-X melts has been presented by [1981Sch], in particular, for the case of X = Mo. It was found that log γHMo at 1600°C decreases to about –0.04 on increasing the Mo content up to 20 at.%. The calculated enthalpy of dissolution ΔHHMo and entropy of dissolution ΔSHMo also decreased on increasing the molybdenum content up to 20 at.% - to about –1.5 kJ·mol–1 and –0.02 kJ·mol–1·K–1, respectively. Notes on Materials Properties and Applications The possibilities of using Fe-Mo alloys hydrogen absorbents are of great interest, and the conditions required to realize these possibilities are need in experimental veriﬁcation. The main goal of the physical property investigations of Fe-H-Mo alloys reported in the literature [1967Kod, 1991Rie] was to establish the effects of the hydrogenation of steels on properties. It was shown by [1967Kod] that plastic deformation (in compression, Vickers hardness tester using a load of 20 kg) of a Fe based alloy with a Mo content of 0.42 mass% and a total content of C, Si, Mn, P, S and Cr of 0.544 mass% leads to a substantial increase in the activation energy and pre-exponential factor in the expression for the temperature dependence of hydrogen permeability. Also, the effect of deformation and annealing on the electrical resistance of alloys gradually heated to and cooled from 800°C was studied. These measurements were carried out using a standard potentiometric method on 1.0–1.5 mm diameter wire specimens deformed by drawing to 25–30% reduction. Two stages of recovery of the hydrogen permeability parameters were identiﬁed. The ﬁrst stage corresponds to quite an intense recovery of hydrogen permeability and electrical resistivity parameters which terminates at 300–320°C. It was postulated that the recovery of hydrogen permeability under these conditions is associated mainly with the variation in the vacancy structure of the alloy. In the second stage, above 600°C, a marked reduction in hardness was observed (from about 1.59 GPa at 600°C to about 1.18 GPa at 700°C). In the author’s opinion, this change is associated with the variation in the dislocation structure whose inﬂuence on the diffusion of hydrogen is weaker than that of the vacancy structure. Mechanical tests were also carried out by [1991Rie] during the study of the effect Mo on hydrogen permeation, diffusion, solubility and its distribution on different binding states in the Fe-based alloys. The fracture behavior of the alloys affected by hydrogen in different binding states were tested under constant elongation rate conditions, and no speciﬁc effect of molybdenum was observed. It was concluded that crack initiation and fracture progress depend ﬁrst of all on the external hydrogen activity and the grain size of the material, not on the total hydrogen content. Fine crystalline iron alloys of higher strength proved to be less sensitive to hydrogen damage than coarse grain weak structures.

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Miscellaneous Diffusion and permeation characteristics of hydrogen in Fe-Mo alloys are presented in [1952Cha, 1965Hei, 1967Kod, 1976Zhi, 1991Hag, 1991Rie, 1992Hag]. [1952Cha] studied iron-based alloys containing 0.98, 2.36 or 10.36 mass% Mo as well as C, Si, Mn, P, S and Ni with a total content up to 0.77 mass%. The specimens were heated to 1000°C and degassed for 1 h, after which they were soaked in pure hydrogen for 2 h before the system was pumped out. Permeation rates at various temperatures, both on heating and cooling, were then measured. It was concluded that molybdenum has no appreciable effect on the permeation rate of hydrogen in iron. So, activation energies for permeation were quite similar: 69.14, 71.23 and 64.11 kJ·mol–1 for alloys with 0.98, 2.36 and 10.36 mass% Mo, respectively. The hydrogen permeation of Fe-Mo alloys with molybdenum contents of 5.04 or 10 mass% (3.22 and 6.07 at.% Mo, respectively) was studied by [1965Hei] over a temperature range of 350–800°C and a hydrogen pressure of 101300 Pa. Activation energies were calculated from the experimental data for the alloys with 2.97 and 6.07 at.% Mo as 39.69 ± 0.59 kJ·mol–1 and 40.19 ± 0.80 kJ·mol–1, respectively. The application of iron diaphragm electrodes in lithium hydride cells under heavy current loads has resulted in current densities which were 1.5 times greater than those obtainable from data on the permeability of hydrogen through an iron diaphragm with a hydrogen pressure of 101300 Pa across the diaphragm. [1976Zhi] reported that a molybdenum content of up to 3.11 mass% (or about 1.83 at.%) in steels has little effect on the permeation coefﬁcient of hydrogen. At the same time, with increasing Mo content, the activation energy of diffusion essentially increases. The diffusion coefﬁcients of hydrogen in iron-based alloys with Mo contents from 0.51 to about 3.35 at.% annealed at 900°C for 3 h in vacuum and then slowly furnace cooled have been measured by [1991Hag, 1992Hag] using an electrochemical permeation method between 10 and 40°C. The temperature and alloy composition dependence of the diffusion coefﬁcients have been discussed in relation to simple trapping models. It was concluded that the diffusivity of hydrogen is lowered by alloying, and this is caused by the interstitial hydrogen sites around the substitutional atoms acting as trapping sites. The diffusion behavior of hydrogen in the alloys is strongly inﬂuenced by the elastic interaction between hydrogen and the alloying atoms. [1991Rie] investigated the effect of Mo on the binding states of hydrogen in iron and the fracture behavior of iron alloys reporting that no speciﬁc effects of molybdenum were observed.

Table 1.

Investigations of the Fe-H-Mo Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1934Sie]

Sieverts’ method (apparatus consists of the reaction chamber, the gas-measuring system and the gas-puriﬁcation equipment)

300–1100°C; 1.2–83.7 at.% Mo

[1961Mae]

Sampling method (Tamman furnace as the melting apparatus; sampler consisting of a quartz tube attached with a rubber bulb; tin fusion technique; streaming by pure hydrogen)

1600°C; < 6 mass% ( 3.58 at.%) Mo

[1964Gun]

Sieverts’ method

1550, 1600, 1650°C; < 10 mass% ( 6.07 at.%) Mo

[1965Bag]

Sieverts’ method

1600°C; ≤ 30 mass% ( 19.97 at.%) Mo

[1967Ban]

Sieverts’ method

1550–1670°C; ≤ 30 mass% ( 19.97 at.%) Mo

[1967Kod]

Induction melting, hydrogen permeability measurements, X-ray powder diffraction

250–750°C; 0.42 mass% Mo (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1967Som]

Sieverts’ method

1540 - 1605°C; ≤ 30 mass% ( 19.97 at.%) Mo

[1970Fuk]

Sieverts’ method, sampling method

1550–1600°C; ≤ 12 mass% ( 7.35 at.%) Mo

[1970Kat]

Sieverts’ method, sampling method

1550–1600°C; ≤ 12 mass% ( 7.35 at.%) Mo

[1972Ngi]

Sieverts’ method

1550–1600°C, 6664–13329 Pa pressure; ≤ 16 mass% ( 9.98 at.%) Mo

[1976Zhi]

Hydrogen stream technique (step annealing and cooling of the specimens)

300–800°C; 0.54, 1.27 and 1.83 at.% Mo

[1991Hag]

Electrochemical permeation technique

10–40°C; Fe with addition of 0.51 to 3.35 at.% Mo

[1991Rie]

Electrochemical permeation technique

Fe rich corner

[1992Hag]

Electrochemical permeation technique, X-ray diffraction

10–40°C; Fe with addition of 0.51 to 3.35 at.% Mo

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) (h2) 1538–1394

cI2 Im 3m W

a = 293.15

pure Fe, T = 1390°C [V-C2, Mas2] dissolves 0.0696 at.% H at 1536°C, 0.1MPa [1990San, Mas2] dissolves 1.6 at.% H at 1460°C, 1.8 GPa [2003Fuk] in the Fe-Mo binary system joins with the (αFe) [Mas2]

(γFe) (h1) (austenite) 1394–912

cF4

a = 364.67

pure Fe, T = 912°C [V-C2, Mas2]

(αFe) (r) (ferrite) < 912

Fm 3m Cu

cI2

dissolves 0.0466 at.% H at 1394°C, 0.1MPa [1990San, Mas2] dissolves 10.7 at.% H at 680°C, 2.5 GPa; 41.1 at.% H at 680°C, 6 GPa [2005Hir] dissolves 1.7 at.% Mo at 1140°C [Mas2] a = 286.65

pure Fe, T = 25°C [V-C2]

Im 3m W

dissolves 24.4 at.% Mo at 1449°C [Mas2] (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(εFe) ≥ 1.3·105 bar

hP2 P63/mmc Mg

a = 246.8 c = 396.0

pure Fe, T = 25°C, 13 GPa [Mas2] high-pressure modiﬁcation

(βH) < –259.34

hP2 P63/mmc Mg

a = 377.6 c = 616.2

[V-C2, Mas2]

(αH) < –271.9

cF4 Fm 3m Cu

a = 533.8

[V-C2, Mas2]

(Mo) < 2623

cI2 Im 3m W

a = 314.70

T = 25°C [Mas2] dissolves 31.3 at.% Fe at 1611°C [Mas2]

σ, MoFe 1611–1235

tP30 P42/mnm σCrFe

a = 921.8 c = 481.3

μ, Mo6Fe7 < 1370

hR39 R 3m W6Fe7

a = 475.46 c = 2571.6

R, Mo2Fe3 1488–1200

hR159 R 3 Mo3Cr2Co5

λ, MoFe2 < 927

Table 3.

hP12 P63/mmc MgZn2

43.3 to 57.1 at.% Fe [Mas2] [V-C2] 56 to 61 at.% Fe [Mas2] [V-C2] 61.5 to 66.1 at.% Fe [Mas2]

a = 1091.0 c = 1935.4 a = 1095.6 c = 1935.3

Mo1.9Fe3.1, at 1250 to 1490°C [V-C2] annealed at 1250°C [V-C2] 66.7 at.% Fe [Mas2] C14 structure [V-C2]

a = 475.5 c = 776.7

Interaction Parameters for Hydrogen in Liquid Fe-Mo Alloys

Reference

Method/ Experimental Technique

εHMo

Temperature [°C]

Composition/ Range Studied

[1961Mae] [1964Gun]

Sampling method Sieverts’ method

– 0.013 + 0.0030 + 0.0029 + 0.0028 + 0.0029 (the average)

1600 1550 1600 1650 1550–1650

< 6 mass% ( 3.58 at.%) Mo < 10 mass% ( 6.07 at.%) Mo

(continued)

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Fe–H–Mo

Reference

Method/ Experimental Technique

εHMo

Temperature [°C]

Composition/ Range Studied

[1965Bag]

Sieverts’ method

+ 0.0022

1600

< 30 mass% ( 19.97 at.%) Mo

[1967Ban]

Sieverts’ method

+ 0.0014

1550–1670

< 30 mass% ( 19.97 at.%) Mo

[1967Som]

Sieverts’ method

+ 0.0009

1540–1605

< 30 mass% ( 19.97 at.%) Mo

[1970Fuk, 1970Kat]

Sieverts’ method Sampling method

+ 0.0048 + 0.0107

1550–1600 1600

< 5 mass% ( 2.97 at.%) Mo < 12 mass% ( 7.35 at.%) Mo

[1972Ngi]

Sieverts’ method

+ 0.0029

1550–1600 (6664–13329 Pa pressure)

< 10 mass% ( 6.07 at.%) Mo

Fig. 1. Fe-H-Mo.

The Fe-H phase diagram

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Fig. 2. Fe-H-Mo.

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Hydrogen solubility in the Fe-Mo alloys at different temperatures and atmospheric pressure

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Fe–H–Mo

References [1934Sie] Sieverts, A., Bruenig, K., “Absorptive Ability of the Iron-Molybdenum Alloys for Hydrogen and Nitrogen” (in German), Arch. Eisenhuettenwes., 7(11), 641–645 (1934) (Phase Diagram, Phase Relations, Experimental, *, 15) [1938Kub] Kubaschewki, O., “Absorption of Gases in the Metals” (in German), Z. Elektrochem., 44(2), 152–167 (1938) (Phase Relations, Review, Interface Phenomena, 187) [1952Cha] Chang, P.L., Bennett, W.D.G., “Diffusion of Hydrogen in Iron and Iron Alloys at Elevated Temperatures”, J. Iron Steel Inst., 170, 205–213 (1952) (Morphology, Experimental, Interface Phenomena, Kinetics, 19) [1961Mae] Maekawa, S., Nakagawa, Y., “The Effect of Some Alloying Elements on the Solubility of Hydrogen in Liquid Iron” (in Japanese), Nippon Kinzoku Gakkai-shi, 25(9), 577–580 (1961) (Phase Relations, Thermodyn., Experimental, *, 6) [1963Wei] Weinstein, M., Elliott, J.F., “Solubility of Hydrogen in Liquid Iron Alloys”, Trans. AIME, 227, 382–393 (1963) (Phase Relations, Thermodyn., Calculation, Experimental, Review, Theory, Electronic Structure, 27) [1964Gun] Gunji, K., Ono, K., Aoki, Y., “The Effect of Various Elements on the Solubility of Hydrogen in Liquid Pure Iron”, Trans. Nat. Res. Inst. Met. (Jpn.), 6(5), 209–213 (1964), translated from J. Jpn. Inst. Met., 28, 64–68 (1964) (Phase Relations, Thermodyn., Experimental, Review, *, 7) [1965Bag] Bagshaw, T., Engledow, D., Mitchell, A., “Solubility of Hydrogen in Some Liquid Iron-Based Alloys”, J. Iron Steel Inst., 203, 160–165 (1965) (Crys. Structure, Phase Relations, Thermodyn., Calculation, Experimental, Theory, 28) [1965Hei] Heinrich, R.R., Johnson, C.E., Crouthamel, C.E., “Hydrogen Permeation Studies. I. Armco Iron and Iron-Molybdenum Alloys”, J. Electrochem. Soc., 112(11), 1067–1070 (1965) (Morphology, Experimental, Interface Phenomena, 12) [1966Bur] Burylev, B.P., “Solubility of Hydrogen in Solid Iron Alloys”, Russ. J. Phys. Chem. (Engl. Transl.), 40(4), 442–445 (1966) (Phase Relations, Thermodyn., Calculation, 12) [1967Ban] Ban-ya, S., Fuwa, T., Ono, K., “Solubility of Hydrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 53(2), 101–116 (1967) (Phase Relations, Thermodyn., Experimental, Review, *, 18) [1967Kod] Kodes, E.S., Gel’d, P.V., “Recovery of Hydrogen Permeability of Ferritic Alloys of Iron with Molybdenum and Nickel”, Sov. Mater. Sci., 3(6), 478–482 (1967), translated from Fiz.-Khim. Mekh. Mater., 3(6), 656–662 (1967) (Crys. Structure, Experimental, Electr. Prop., Interface Phenomena, Mechan. Prop., 11) [1967Som] Someno, M., Nagasaki, K., Kadoi, K., “Solubility of Hydrogen in Liquid Iron and in Some Liquid Binary Iron Alloys” (in Japanese), J. Jpn. Inst. Met., 31, 729–734 (1967) (Phase Relations, Thermodyn., Experimental, Review, *, 27) [1970Fuk] Fukuda, S., Sugiyama, T., Furukawa, T., Kato, E., “Solubility of Hydrogen in Liquid Iron Alloys”, Rep. Casting Research Lab./Waseda Univ., (21), 35–46 (1970) (Phase Relations, Thermodyn., Calculation, Experimental, Review, *, 22) [1970Kat] Kato, E., Fukuda, S., Sugiyama, T., Furukawa, T., “Solubility of Hydrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 56, 521–535 (1970) (Phase Relations, Thermodyn., Experimental, *, 28) [1972Ngi] Ngia, N., Yavoyskiy, V.I., Kosterev, L.B., Afanas’yev, M.I., “Hydrogen Solubility in Binary Iron-Base Alloys”, Russ. Metall. (Engl. Transl.), (4), 11–15 (1972), translated from Izv. Akad. Nauk SSSR, Met., (4), 18–22 (1972) (Phase Relations, Thermodyn., Experimental, *, 19) [1976Zhi] Zhitenev, V.I., Ryabov, R.A., Geld, P.V., “Diffusion Coefﬁcient and Solubility of Hydrogen in Solid Solutions of Molybdenum in Iron” (in Russian), Fiz. Met. Metalloved., 41, 650–652 (1976) (Phase Relations, Experimental, Interface Phenomena, 8) [1981Sch] Schuermann, E., Kaettlitz, W., “Equivalent Effect of the Alloying Elements on the Concentration- and Temperature-Dependent Hydrogen Solubility in Iron-Rich Ternary and Multicomponent Melts” (in German), Arch. Eisenhuettenwes., 52(8), 295–301 (1981) (Phase Relations, Thermodyn., Calculation, Review, *, 20)

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Fe–H–Mo [1990San] [1991Hag]

[1991Rie]

[1992Hag]

[2003Fuk]

[2005Hir]

[Mas2] [V-C2]

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San Martin, A., Manchester, F.D., “The Fe-H (Iron-Hydrogen) System”, Bull. Alloy Phase Diagrams, 11(2), 173–184 (1990) (Phase Diagram, Thermodyn., Review, #, 91) Hagi, H., “Effect of Substitutional Alloying Elements (Al, Si, V, Cr, Mn, Co, Ni, Mo) on Diffusion Coefﬁcient of Hydrogen in α-Iron”, J. Jpn. Inst. Met., 55(12), 1283–1290 (1991) (Crys. Structure, Morphology, Experimental, Interface Phenomena, 23) cited from abstract Riecke, E., Johnen, B., “Effect of Mo, V, Nb, Ti, Zr and their Carbides on the Binding States of Hydrogen in Iron and the Fracture Behaviour of the Iron Alloys”, Werkstoffe und Korrosion, 42(12), 626–636 (1991) (Morphology, Phase Relations, Experimental, Review, Theory, Interface Phenomena, Mechan. Prop., 18) cited from abstract Hagi, H., “Effect of Substitutional Alloying Elements (Al, Si, V, Cr, Mn, Co, Ni, Mo) on Diffusion Coefﬁcient of Hydrogen in α-Iron”, Mater. Trans. JIM, 33 (5), 472–479 (1992) (Crys. Structure, Morphology, Experimental, Interface Phenomena, 33) Fukai, Y., Mori, K., Shinomiya, H., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys under High Hydrogen Pressures”, J. Alloys Compd., 348, 105–109 (2003) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, #, 42) Hiroi, T., Fukai, Y., Mori, K., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys Revisited”, J. Alloys Compd., 404–406, 252–255 (2005) (Crys. Structure, Phase Relations, Experimental, *, 23) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–H–Ni

1

Iron – Hydrogen – Nickel Vasyl Tomashik, Larysa Shcherbak, Olga Fabrichnaya

Introduction The diffusion of hydrogen in Fe-Ni alloys is of great technological importance, especially for the design of controlled thermonuclear reactors [1973Dre]. Therefore, the main trends in the experimental and theoretical investigations of this system were the study of hydrogen dissolution and its diffusion and permeability in the Fe-Ni alloys. Hysteresis loops involving H absorption/desorption are notable in this ternary system [2002Ant, 2004Zag]. The ﬁrst experimental results concerning the Fe-H-Ni ternary system were obtained more than 50 years ago [1952Kur], where the dissolution of hydrogen in Fe-Ni alloys, containing up to 20 mass% Ni, was investigated. The dissolution of hydrogen in such alloys at different temperatures and alloy compositions was investigated mainly using Sieverts’ method by [1957Izm, 1960Bus, 1961Mae, 1963Wei, 1964Gun, 1965Bag, 1965Bur, 1965Sch, 1966Bag, 1966Noz, 1966Sch1, 1966Sch2, 1968Dus, 1968Gol, 1969Lip, 1971Bec, 1971Blo, 1971Way, 1972Ngi, 1974Boo, 1974Pet, 1974Shv, 1975Dag, 1976Pet, 1976Sta, 1977Pet, 1977Pon, 1990Mat]. The experimental results of [1952Kur] indicated maximum hydrogen solubility at 4 mass% Ni: increasing the Ni content up to 20 mass% results in only a negligible decrease in the solubility. Later investigations showed that the hydrogen solubility in Fe-Ni alloys increases with increasing Ni content. An empirical formula for the level of hydrogen solubility in solid Fe-Ni alloys at 1200 and 1400°C was proposed by [1966Bur]. The temperature dependence of hydrogen solubility in Fe-Ni alloys within the temperature range from 1400 to 1800°C can be expressed by log10{H} = A/T + B [1976Pet, 1977Pet] over the whole composition range. It was shown than the hydrogen solubility depends essentially on the alloy composition and the level of disorder [1969Sim]. The equations for the hydrogen solubility and its diffusion coefﬁcient in an FeNi3 alloy were obtained using the energies of the Fe(Ni)-H bond [1970Vyk]. The hydrogen solubility in the Fe-Ni alloys at 1150°C was calculated using the method of cluster components without correlation in the solution by [1977Kar]. The data obtained coincide with the experimental results of [1965Sch]. A statistical model of hydrogen solubility in Fe melts was proposed and the hydrogen solubility in Fe-Ni alloys at 1600°C and 0.1 MPa was calculated by [1984Fro1] which practically coincides with the data of [1966Sch1]. Diffusion regularities of hydrogen in the Fe-Ni alloys at different temperatures and pressures were studied by [1956Shc, 1973Dre, 1965Sch, 1967Dus, 1969Gol, 1969Sim, 1971Bec, 1972Dre, 1974Shv, 1979Sig]. The permeability of hydrogen in Fe-Ni alloys was investigated by [1967Fra, 1969Gol, 1969Sim, 1971Bec, 1974Shv, 1976Gol]. Between 0 and 40 mass% Ni the dominant factor in controlling the value of the permeability is the reduction of the mole fraction of the α phase in the alloy [1971Bec]. Some thermodynamic properties of the Fe-H-Ni alloys have been investigated both experimentally and theoretically by [1960Bus, 1961Mae, 1963Wei, 1964Gun, 1966Bag, 1966Noz, 1966Sch1, 1966Sch2, 1971Bec, 1971Blo, 1972Ngi, 1973Bar, 1974Boo, 1974Pet, 1974Shv, 1976Sta]. Details of the experimental studies are reported in Table 1. Binary Systems The Fe-Ni and Fe-H systems were taken from the MSIT Binary Evaluation Program [2007Kuz] and [Mas2], respectively. The solubility of H in solid and liquid Fe and Ni are accepted from [1984Fro2], corrected by [2006Tom]. These data may be used up to a H2 pressure of 50 MPa. [2002Ant] reported the stability of the FeH hydride phase ε’-FeH at pressures of 3.5–7 GPa. It must be pointed out that the H-Ni diagram given by [Mas2] for a hydrogen pressure of 50 MPa cannot be accepted, because it gives a eutectic composition of 0.036 at.% H at 1406°C whereas the actual composition would be 2.14 at.% H at the same temperature. The solubility of hydrogen in liquid Ni at ambient pressure has Landolt-Börnstein New Series IV/11D4

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2

Fe–H–Ni

also been reviewed by [1987Sch]. The best H-Ni phase diagram available to date is that given in [2002Shi] determined experimentally up to 800°C and a 5 GPa pressure of hydrogen. The H-Ni solid solution exhibits a miscibility gap, with a critical point, evaluated by [2004Fuk], of around 360°C, 1.4 GPa and 50 at.% H. Solid Phases Ternary compounds were not found in the Fe-H-Ni system at the standard temperature and pressure [2005Ide]. According to the data of [1972Bar, 1973Bar] the ternary solid solutions similar to the nickel hydrides are formed in this system at up to about 25 at.% Fe under high pressures (up to 3 GPa). [1976Miz] indicated that hydrides of Ni rich Fe-Ni alloys could be prepared by cathodic saturation. The decomposition of these hydrides at room temperature became faster with the increase of Fe content and sample preparation for an alloy above 10 at.% Fe was difﬁcult. The increase of the lattice parameter due to the hydride formation became smaller and the hydrogen content decreases with the increase of the Fe concentration. The obtained hydrides were not microscopically homogeneous and coexist with non-hydrogenated phase. Crystallographic data of the unary and binary compounds are shown in the Table 2. The observed decrease in the lattice parameters of the Fe0.2Ni0.8Hx solid solutions suggests that the samples with x ≈ 0.8 and 0.63 were inhomogeneous [2002Ant]. The Fe0.2Ni0.8D0.63 sample appeared inhomogeneous throughout. The solubility of hydrogen in the Fe-Ni alloys at medium (400–1000°C) and low (70°C) temperatures according to the data of [1965Sch] and [1971Bec] is shown in Figs. 1 and 2, respectively. Solubility of hydrogen in the Fe-Ni alloys has been investigated both in solid states at 400–1000°C with the step of 100°C up to 12 mass% Ni by [1965Sch], at temperatures of 650, 600, 500, 400 and 300°C and compositions up to 11 at.% Ni by [1974Shv], at 70°C by [1971Bec]. The results of [1965Bag, 1966Bag] indicate an inﬂexion on the solubility curve at about 69 at.% Ni, coinciding with a minimum in the liquidus of the Ni-Fe binary system and a peak in the Curie temperature-composition relationship. Anomalous changes of the hydrogen solubility in the Fe-Ni alloys, containing 18.9 and 24.85 mass% Fe, were determined within the temperature range from 450 to 500°C [1968Gol]: the solubility increases for 20 and 65 % for the ﬁrst and the second alloy respectively. The hydrogen solubility in the Fe-Ni alloys at 20°C is stopped at the adding more than 30 mass% Fe [1969Lip]. According to the data of [1990Zag] there is an order-disorder phase transition in the case of the alloy (24.85 mass% Fe + 75.15 mass% Ni) + H at 500°C (Kurnakov temperature). The appearance of long-range atomic order in this alloy should enhance the hydrogen solubility. [1990Mat] also noted that the ordering of this alloy leads to the increasing of hydrogen solubility. Sieverts’ law is obeyed at the hydrogen solubility in liquid Fe-Ni alloys up to 0.101 MPa pressures [1963Wei]. Isothermal Sections Solubility of hydrogen in the Fe-Ni alloys has been investigated in liquid alloys at 1400–1800°C by [1976Pet, 1977Pet], 1600°C by [1965Bag], [1971Blo] and [1974Pet], 1592°C up to 23 mass% Ni by [1963Wei]. The solubility of hydrogen in the Fe-Ni alloys at 1400–1700°C according to [1966Sch1] is presented in Fig. 3. Two fcc phases γ and β (hydride phase) with different hydrogen contents can be in equilibrium at room temperature in the H-Ni system under suitable conditions of electrolytic charging or under high hydrogen pressure [1982Sak]. In the Fe-H-Ni system the boundary between γ and β phases disappears for Fe contents above about 26 at.%. Phase diagram at 25°C from [1982Sak] is presented in Fig. 4. The γ ↾ β ﬁrst order transition for the alloy containing 10 at.% Fe ends at the critical point with coordinates 250 < Tcr < 300°C and 1.6 MPa < pcr < 1.9 MPa [1976Pon1]. Critical temperature decreases linearly with Fe content increasing within the interval from 5 to 15 at.% Fe. Thermodynamics The Gibbs energies of formation of the Ni-Fe hydrides at room temperature forming at the pressure up to 3 GPa were calculated by [1973Bar]. The calculations were based on hydrogen pressure data of decomposition reaction. For the alloys containing from 1.20 to 36.5 at.% Fe the Gibbs energy of formation was calculated to be within the interval from 23.9 ± 0.2 to 50.2 ± 0.5 kJ·mol–1 H2 according to [1973Bar]. DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

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Fe–H–Ni

3

The heat of the hydrogen dissolution in the Fe-Ni alloys increases from 24.3 to 26.0 kJ·g-at–1 H in the concentration range 1.5–9 at.% Ni and then decreases to 23.4 kJ·g-at–1 H at 12 at.% Ni according to [1974Shv]. According to [1976Sta] the thermodynamic properties of dissolved hydrogen are not dependent upon the state of order of the Fe-Ni alloys and also invariant to the magnetic transformation. From the experimental data on solubility of hydrogen in Fe-Ni alloys at 1400, 1500–1550, 1600 and 1700°C Schenk [1966Sch1] determined ﬁrst order interaction parameters εNiH in Fe solution and εFeH in Ni solution using Wagner’s formalism for concentrations of Fe up to 10 at.%, Ni up to 5 at.%. The parameters εNiH were calculated to be equal to –0.28, –0.23, –0.21 and –0.16 at the above mentioned temperatures, respectively [1966Sch1]. These data are in reasonable agreement with other determinations at 1600°C (εNiH = 0.000 [1963Wei, 1974Boo]; εNiH = –0.2 [1965Bag]; εNiH = –0.385 [1966Noz]; εNiH = –0.5 ± 0.3 [1971Blo]; εNiH = –0.534 [1964Gun]; εNiH = –0.12 [1960Bus]; εNiH = –0.606 up to 15 mass% Ni [1972Ngi]; εNiH = –0.16 [1974Pet]). The value εNiH = –4.6 obtained for concentrations up to 6 mass% Ni [1961Mae] seems to be erroneous. The ﬁrst order interaction parameters εFeH in Ni solutions are equal 0.78 and 1.2 at 1400 and 1500–1700°C respectively [1966Sch1]. These data are in reasonable agreement with other measurements (εFeH = +1.17 up to 20 mass% Ni [1966Bag]; εFeH = +0.5 ± 0.3 [1971Blo]; εFeH = +0.91 at 1600°C [1974Pet] for dilute solutions). The value of εFeH = +0.009 [1960Bus] seems to be too low. The heat of hydrogen solution in Fe-Ni alloys is given in Fig. 5 [1971Bec]. The concentration dependence of the activity coefﬁcients of hydrogen with respect to the third component in Fe-Ni alloys at 1400, 1550 and 1700°C are shown in Figs. 6 and 7 [1966Sch1]. The thermodynamic calculations of the hydrogen solubility in the Fe-Ni alloys at 1600°C [1965Bur] practically coincide with the experimental results of [1960Bus, 1963Wei, 1965Bag, 1966Bag]. Notes on Materials Properties and Applications [2006Ara] indicated that the Fe0.7Ni0.3 alloy is one of the best media to store hydrogen. The hydrogen is detrimental to the Fe-Ni alloys quality [1973Dre]. An inﬂuence of a plastic deformation with the next annealing on the hydrogen solubility in the Fe-Ni alloy containing 40 mass% Ni was not found [1968Kod]. The corrosion rate and hydrogen permeability, hence, susceptibility to hydrogen embrittlement, pass through a minimum at about 50 mass% Ni [1971Bec]. [1976Gol] noted that the hydrogen permeability and the diffusion rate decrease within the temperature interval from 250 to 850°C at the Fe addition to Ni. Anomalous behavior of thermal expansion and Young’s modulus of the Fe-Ni alloys containing 32.9 and 75.0 at.% Ni (Invar alloys) was faded with hydrogenation [1983Har]. This change corresponds to the disappearance of the characteristic weak ferromagnetic states of such alloys. According to [1976Miz], [1976Pon2] and [2002Ant] the hydrides of Ni rich Fe-Ni alloys were ferromagnetic at low temperatures and TC rose with the increase of Fe concentration. The value of dTC/dp increases at the hydrogen pressure increasing and become positive at p ≈ 1.5 MPa [1976Pon2]. The spontaneous magnetization of the Fe0.2Ni0.8Hx solid solutions at 124 K decreases approximately linearly from 1.1 μB per metal atom at x = 0 to 0.6 μB at x = 1 [1978Ant, 2002Ant]. The increasing of hydrogen concentration in the Fe-H-Ni alloys as its pressure increases leads to the TC increasing [1978Ant]. At the hydrogen pressure above 1.5 MPa TC of the Fe0.675Ni0.325-H begins to grow and reaches about 700 K at 5.0 MPa. There is a sharp analogy in the inﬂuence of the plastic deformation and cathodic hydrogenation on the internal friction parameters [1980Bar]. Electric resistance of Ni-Fe alloys at 25°C and pressures up to 3 GPa hydrogen pressure was measured “in situ” by [1973Bar]. The maximum of electric resistance was observed in alloys with concentrations of 16 at.% Fe at hydrogen pressure above 2 GPa. Further increase of hydrogen pressure had small inﬂuence on resistance of alloys. Miscellaneous Isothermal absorption relationships between H2 and D2 gas pressure and hydrogen or deuterium content of a Fe0.2Ni0.8 alloy is given in Fig. 8 [2002Ant]. The bcc Fe-Ni alloys containing 70–80 mass% Fe showed extreme instability when electrolytic charging was stopped [1971Way].

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4

Fe–H–Ni

The hydrogen solubility in Ni rich Fe-Ni alloys exhibits the same kind of solubility anomaly associated with the presence of grain boundaries which has been observed in pure Ni [1976Sta]. The hydrogen impurity presumably promotes ordering of the alloy by introducing stresses into the lattice [1968Dus]. The diffusion coefﬁcient of hydrogen in the Fe-Ni alloys was found to remain constant up to 0.04 at.% Ni [1973Dre]. A drop by a factor 3 occurs between 0.04 and 0.15 at.% Ni and from 0.15 to 5 at.% Ni the diffusion coefﬁcient decreases slightly within the bcc structure. In the two-phase bcc-fcc region a decrease of about 3 orders of magnitude was observed, while in the disordered fcc structure the diffusion coefﬁcient was found to be nearly independent of the composition. The effect of long-range order was determined and it was shown that the diffusion coefﬁcient exhibits an increase of a factor of about 4 at the composition Ni3Fe [1973Dre]. The concentration dependence of the diffusion coefﬁcient of hydrogen in the Fe-Ni alloys at room temperature and 350, 650 and 1050°C was determined by [1965Sch]. [1980Bar] indicated that the diffusion coefﬁcients of hydrogen at the degassing temperature for the Fe-Ni alloy, containing 3 mass% Ni, are equal 1.93·10–9 cm2·s–1 at 250 K and for the alloy, containing 1.5 mass% Ni, 2.98·10–9 cm2·s–1 at 288 K. According to the data of [1971Bec], the diffusion coefﬁcient falls from ≈10–4 cm2·s–1 for pure Fe to ≈10–10·cm2·s–1for 40 mass% Ni in the alloy. Thereafter it rises slightly to that of pure Ni. The hysteresis which exists in the case of the nickel hydride disappeared in the ternary high-pressure Fe-H-Ni phase, containing 17 at.% Fe [1973Bar]. The hydrogen diffusion rate increases with increasing the Ni content and reaches a maximum at 6 mass% Ni [1956Shc]. The next increasing of Ni content leads to its decreasing with a minimum at 74 mass% Ni and the increasing of the diffusion rate at higher Ni content. It has been found that in the case of Fe-Ni specimens having the ability to form ordered structures there is no linear relationship between the logarithm of diffusion coefﬁcient and the reciprocal of the absolute temperature [1967Dus]. Ordered solid solutions, and particularly those with a long-range order, manifest much higher activation energy values for the hydrogen diffusion than unordered ones. [1972Dre] indicated that the diffusion coefﬁcient of hydrogen varies with the alloy composition even within a homogeneous structure. Generally, the diffusion of hydrogen occurs faster within bcc structures than fcc ones. A continuous decrease of the diffusion coefﬁcient within the mixed bcc + fcc phase toward the fcc structure results from a change in crystal structure. The diffusivity increases by a factor of four from a completely disordered to ordered structure close to 75 at.% Ni [1972Dre]. The diffusion rate of the hydrogen in the alloys, inclined to an ordering, changes with the composition and temperature nonlinearly [1969Sim]. The activation energies of the hydrogen diffusion and permeability in FeNi3 alloy as well as the dissolution enthalpy are the same for the ordered and disordered samples [1969Gol]. Introduction of Fe into Ni reduces the hydrogen absorption [1971Bar]. The height of an internal friction peak due to hydrogen in the Fe1–xNix (x = 0.35–1.0) alloys did not show a monotonic change versus the increasing Ni content and depends strongly on the alloy composition [2005Ide]. There is a general decrease in the rate constant of hydrogen absorption as the amount of Fe in the alloy decreases except in the region between 65 and 75 at.% Fe, where an increase in the rate penetration is observed [1967Fra]. The peculiarities of hydrogen absorption by the alloy C-Fe-Ni, containing 0.38 mass% C and 23.29 mass% Ni, was investigated by [1975Dag]. It was shown that the absorbed hydrogen quantity for austenite is within the interval from 2 to 4 cm3/100 g as for the martensite its value could reach 9 cm3/100 g. A large hysteretic peak was observed in the internal friction spectrum of the single-phase Fe50Ni50 alloy corresponds to hydrogen degassing from the (γFe,Ni) solid solution [2004Zag]. A new low temperature relaxation peak with the activation enthalpy of 0.41 ± 0.04 eV is also observed in such spectrum of the hydrogen-charged Fe50Ni50 alloy. It is presumably related to the relaxation of H-H pairs or H-Fe complexes in the Ni rich regions of the ordered Fe-Ni solid solution. Degassing of hydrogen from these regions is probably responsible for a minor small additional hysteretic peak. The temperature of (αFe)/(γFe) transition for the Fe-Ni alloys containing 10, 20 and 30 at.% Ni is lower in the hydrogen atmosphere in comparison with inert medium [1977Pon]. This difference reaches about 45°C at 2.2 MPa and 30 at.% Ni. The hydrogen dissolution in the (γFe) phase leads to its stabilization. The hydrogen dissolution reduces the vacancy formation in the Fe-Ni alloys [1972Bru]. A signiﬁcant feature of the alloy containing 74.94 at.% Ni is a hysteresis loop within the temperature range 510–570°C, i.e. near the order-disorder transition temperature, on the temperature dependence hydrogen solubility [1968Dus]. Lattice dynamics of the Fe0.7Fe0.3-H system was discussed by [2006Ara]. DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

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Fe–H–Ni Table 1.

5

Investigations of the Fe-H-Ni Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1952Kur]

Measuring of hydrogen absorbed

1590–1685°C/(Fe + up to 20 mass% Ni) + H2

[1956Shc]

Gas volumetric technique

200–600°C/(Fe-Ni) + H2 up to 10.1 MPa

[1957Izm]

Vacuum melting method

1650°C/(Fe + up to 11 at.% Ni) + H2

[1960Bus]

Sieverts’ method

1600°C/(Fe-Ni) + H2

[1961Mae]

Sieverts’ method

1600 and 1620°C/(Fe-Ni) + H2

[1963Wei]

Sieverts’ method

1592°C/(Fe + up to 23 mass% Ni) + H2

[1965Bag]

Sieverts’ method

1600°C/(Fe-Ni) + H2

[1965Sch]

Effusion method

350–1000°C/up to 12 mass% Ni

[1966Bag]

Sieverts’ method

1600°C/(Fe-Ni) + H2

[1966Noz]

Sieverts’ method

1488–1672°C/(Fe-Ni) + H2

[1966Sch1]

Sieverts’ method

900–1680°C/(Fe-Ni) + H2

[1967Dus]

Pressure measurements

400–800°C/(Fe-Ni) + H2

[1967Fra]

Chemical analysis

25°C/(Fe-Ni) + H2

[1968Dus]

Thermovolumetric method

300–800°C/(Fe-Ni) + H2

[1968Gol]

Pressure measurements

300–800°C/(Ni + 9.35, 18.9 and 24.85 mass% Fe) + H2

[1969Gol]

Pressure measurements

300–850°C/Ni3Fe

[1969Lip]

Cathodic saturation method

20°C/(Fe-Ni) + H2

[1969Sim]

Hot extraction method

300–800°C/Ni + 9.35, 18.9 and 24.85 mass% Fe + H2

[1971Bar]

XRD, mass-spectrometry, electric resistance measurement

25°C/(Fe-Ni) + H2 up to 2.5 GPa

[1971Bec]

Electrochemical method

27–90°C/(Fe-Ni) + H2

[1971Blo]

Sieverts’ method

1600°C/(Fe-Ni) + H2 at 0.101 MPa

[1971Way]

XRD

20°C/Fe-H-Ni

[1972Bar]

Pressure and electrical resistance measurements

25°C/(Fe-Ni alloys with 0.23, 0.50, 1.2, 5.5, 9.8 and 15.6 at.% Fe) + H2 up to 2.5 MPa

[1972Ngi]

Sieverts’ method

1550–1600°C/(Fe-Ni) + H2 at 6.67–13.33 kPa

[1973Bar]

Electric resistance measurements, XRD, mass-spectrometry

25°C/(Fe-Ni) + H2 up to 3 GPa

[1973Dre]

Electrochemical and gas volumetric technique, metallography

25 and 58°C/(Fe-Ni) + H2

[1974Boo]

Pressure measurements

1600°C/(Fe-Ni) + H2 at 0.101 MPa (continued)

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6

Fe–H–Ni

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1974Shv]

Diffusion and penetration methods

300–650°C/Fe + 1.5–12 at.% Ni + H2

[1976Gol]

Berrer’ method

250–850°C/(Fe-Ni at 3.27, 4.75 and 8.98 at.% Fe) + H2

[1976Miz]

XRD, Mössbauer spectroscopy

Room temperature/(Fe-Ni alloys up to 10 at.% Fe) + H2

[1976Pet, 1977Pet]

“Hot volume” method

1400–1800°C/(Fe-Ni) + H2

[1976Pon1, 1976Pon2]

Electroconductivity and magnetic permeability measurements

Up to 520°C/(Fe-Ni at 5, 10, 15, 32.5 and 36 at.% Fe) + H2 up to 2.3 MPa

[1976Sta]

Pressure measurements

300–1050°C/Fe-H-Ni

[1977Pon]

XRD, magnetic permeability measurements

Up to 650°C/(Fe-Ni at 10, 20, 25, 28 and 30 at.% Ni) + H2 up to 2.3 MPa

[1978Ant]

XRD, magnetization measurements

80–220 K/(Fe-Ni at 10, 20, 40, 60, 66.1 and 67.5 at.% Fe) + H2 up to 7.0 MPa

[1980Bar]

Internal friction measurements

80–673 K/(Fe + 1.5 or 3 mass% Ni) + H2

[1983Har]

Gas volumetric method

173–623 K/(Fe + 32.9 or 75.0 at.% Ni) + H2

[1982Sak]

XRD, cathodic saturation

25°C/Fe-H-Ni

[2002Ant]

XRD, neutron diffraction, Mössbauer spectroscopy

250 and 350°C/Fe0.2Ni0.8 + H2(D2) up to 7 GPa

[2004Zag]

Neutron scattering and internal friction measurements

50–500 K/Fe50Ni50 + H2

[2005Ide]

Gas-equilibrating method, XRD

1000°C/Fe1–xNix (x = 0.35–1.0) + H2

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

pure Fe at 1390°C [V-C2, Mas2] dissolves 3.8 at.% Ni at 1517°C

γ, (γFe,Ni) < 1517 (γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [V-C2, Mas2] dissolves 10 at.% H at 700°C and 6 GPa H2 pure Ni at 25°C [Mas2] below critical temperature: γ1 - paramagnetic, Fe enriched γ2 - ferromagnetic, Ni enriched

(Ni) < 1455

a = 352.40

(continued) DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

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Fe–H–Ni

7

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αFe) < 912

cI2 Im 3m W

a = 286.65 a = 291.6

at 25°C [Mas2] dissolves 4.6 at.% Ni at 495°C FeHx at 900–1200°C [2002Ant]

(βH) < –259.34

hP2 P63/mmc Mg

a = 377.6 c = 616.2

[Mas2] triple point

(αH) < –271.9

cF4 Fm 3m Cu

a = 533.8

[Mas2]

γ’, FeNi3 < 517

cP4 Pm 3m AuCu3

a = 355.50

[V-C2, Mas2]

γ’’, FeNi metastable

tP4 P4/mmm AuCu

a = 357.9

metastable [V-C2, Mas2] [V-C2] metastable ordering temperature 320°C at 51.2 at.% Ni [1984Ros]

β, (Ni1–xFex)H1–y NiH

cF8 Fm 3m NaCl

Ni2H

hP3 P3m1 Ni2H

a = 374.0 a = 266 c = 433

x < 0.25, y < 0.333 [V-C2] [V-C2]

metastable

implicit from [2004Fuk]

ε’-FeH(I)

hP4 P63/mmc

a = 269.6 c = 877.0

[2002Ant] 3.5–7 GPa, 25–400°C

ε-FeH0.42

hP2 P63/mmc Mg

a = 258.3 c = 417.6

[2002Ant] metastable

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8

Fig. 1. Fe-H-Ni.

Fe–H–Ni

Solubility of hydrogen in Fe-Ni alloys containing up to 11 mass% Ni at 400–1000°C

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Landolt-Börnstein New Series IV/11D4

Fe–H–Ni

Fig. 2. Fe-H-Ni.

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9

Solubility of hydrogen in Fe-Ni alloys at 70°C

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10

Fig. 3. Fe-H-Ni.

Fe–H–Ni

Solubility of hydrogen in Fe-Ni alloys at 1400–1700°C

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Fe–H–Ni

Fig. 4. Fe-H-Ni.

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11

Isothermal section at room temperature

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12

Fig. 5. Fe-H-Ni.

Fe–H–Ni

Heat of hydrogen dissolution in Fe-Ni alloys as a function of composition

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Fe–H–Ni

Fig. 6. Fe-H-Ni.

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13

Concentration dependence of the hydrogen coefﬁcient of activity in Fe-Ni alloys at 1400°C

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14

Fig. 7. Fe-H-Ni. 1700°C

Fe–H–Ni

Concentration dependence of the hydrogen coefﬁcient of activity in the Fe-Ni melts at 1550 and

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Fe–H–Ni

15

Fig. 8. Fe-H-Ni. Isothermal absorption relationships between H2 and D2 gas pressure and hydrogen or deuterium content of a Fe0.2Ni0.8 alloy

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DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

16 References [1952Kur]

[1956Shc]

[1957Izm] [1960Bus]

[1961Mae]

[1963Wei] [1964Gun]

[1965Bag] [1965Bur] [1965Sch] [1966Bag] [1966Bur] [1966Noz]

[1966Sch1]

[1966Sch2]

[1967Dus] [1967Fra]

[1968Dus]

[1968Gol]

[1968Kod]

Fe–H–Ni

Kurochkin, K.T., Yavoyskiy, V.I., Gel’d, P.V., “Inﬂuence of the Alloying Elements on the Hydrogen Solubility in Liquid Steel” (in Russian) in “Proizvodstvo Stali”, SverdlovskMoscow, 73–90 (1952) (Experimental, Phase Relations, 16) Scherbakova, A.A., “Hydrogen Diffusion through Iron and Binary Iron-Chromium and Iron-Nickel Alloys at High Pressures and Temperatures” (in Russian), Zh. Prikl. Khim., 29(6), 879–884 (1956) (Experimental, Interface Phenomena, 6) Izmanova, T.A., Klyachko, Yu.A., “Hydrogen in some Iron Alloys” (in Russian), Khim. Nauka i Promyshl., 2(4), 528–529 (1957) (Experimental, Phase Relations, 3) Busch, T., Dodd, R.A., “The Solubility of Hydrogen and Nitrogen in Liquid Alloys of Iron, Nickel, and Cobalt”, Trans. Met. Soc. AIME, 218, 488–490 (1960) (Experimental, Phase Relations, 16) Maekawa, S., Nakagawa, Y., “The Effect of some Alloying Elements on the Solubility of H in Liquid Fe” (in Japanese), Nippon Kinzoku Gakkai Shi, 25, 577–580 (1961) (Experimental, Phase Relations, Thermodyn., 6) Weinstein, M., Elliott, J.F., “Solubility of Hydrogen in Liquid Iron Alloys”, Trans. Met. Soc. AIME, 227, 382–393 (1963) (Experimental, Phase Relations, 27) Gunji, K., Ono, K., Aoki, Y., “The Effect of Various Elements on the Solubility of Hydrogen in Liquid Pure Iron”, Trans. Nat. Res. Inst. Met. (Jpn.), 6(5), 209–213 (1964) (Calculation, Phase Relations, 7) Bagshaw, T., Engledow, D., Mitchell, A., “Solubility of Hydrogen in Some Liquid IronBased Alloys”, J. Iron Steel Inst., 203, 160–165 (1965) (Experimental, Phase Relations, 28) Burylev, B.P., “Solubility of Hydrogen in Liquid Iron Alloys” (in Russian), Izv. Vyssh. Uchebn. Zaved., Chern. Met., (2), 17–22 (1965) (Calculation, Phase Relations, 13) Schwarz, W., Zittter, H., “Solubility and Diffusion of Hydrogen in Iron Alloys” (in German), Arch. Eisenhuettenwes., 36(5), 343–349 (1965) (Experimental, Phase Relations, #, *, 16) Bagshaw, T., Mitchell, A., “Solubility of Hydrogen in Some Liquid Alloys of Nickel”, J. Iron Steel Inst., 204, 87–90 (1966) (Experimental, Phase Relations, 18) Burylev, B.P., “Hydrogen Solubility in Solid Iron Alloys” (in Russian), Zh. Fiz. Khim., 40(4), 822–825 (1966) (Calculation, Phase Relations, 12) Nozaki, H., Ban-ya, S., Fuwa, T., Matoba, S., Ono, K., “Effect of Carbon, Silicon, Phosphorus and Nickel on the Solubility of Hydrogen in Liquid Iron” (in Japanese), Tetsu to Hagane, 52(13), 1823–1833 (1966) (Experimental, Phase Relations, Thermodyn., 17) Schenck, H., Lange, K.W., “Research on the Solubility of Hydrogen in Iron, Nickel, Cobalt, Copper and in their Binary Nickel Alloys” (in German), Arch. Eisenhuettenw., 37(9), 739–748 (1966) (Experimental, Phase Relations, Thermodyn., #, *, 54) Schenck, H., Lange, K.W., “An Application of the Hydrogen Solubility to the Physical and Thermodynamic Description of the Solvents” (in German), Z. Metallkd., 57(5), 378–384 (1966) (Experimental, Phase Relations, Thermodyn., 34) Dus, R., Smialowski, M., “Diffusion of Hydrogen in f.c.c. Alloys of Nickel with Iron” Acta Metall., 15, 1611 (1967) (Experimental, Phase Relations, 17) Franklin, T.C., Hudson, P.E., “Absorption of Electrolytic Hydrogen by Nickel and IronNickel Alloys”, J. Electrochem. Soc., 114(6), 568–572 (1967) (Experimental, Interface Phenomena, 21) Dus, R., “The Einstein Temperature of Hydrogen Atoms Dissolved in Ordered and Disordered Fe-Ni Alloys”, Bull. Acad. Polon. Sci., 16(7), 371–376 (1968) (Experimental, Phase Relations, 9) Gol’tsov, V.A., Gel’d, P.V., Simakov, Yu.P., Shteinberg, M.M., Vykhodets, V.B., “Effect of Ordering on the Solubility of Hydrogen in Ni-Fe Alloys” (in Russian) in “Diffuzionniye Procesy v Metalakh”, Naukova Dumka, Kiev, 92–94 (1968) (Experimental, Phase Relations, 3) Kodes, E.S., Gol’tsov, V.A., Gel’d, P.V., “Solubility and Rate of Hydrogen Permeation in Iron-Nickel and Iron-Manganese Austenitic Alloys”, Tr. Uralsk. Politekhn. Inst., (167), 20–25 (1968) (Experimental, Mechan. Prop., 10)

DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–Ni [1969Gol]

[1969Lip]

[1969Sim]

[1970Vyk]

[1971Bar]

[1971Bec]

[1971Blo] [1971Way] [1972Bar] [1972Bru]

[1972Dre]

[1972Ngi]

[1973Bar]

[1973Dre]

[1974Boo]

[1974Pet]

[1974Shv]

[1975Dag]

Landolt-Börnstein New Series IV/11D4

17

Gol’tsov, V.A., Vykhodets, V.B., Gel’d, P.V., Simakov, Yu.P., “Effect of Ordering on the Diffusion Velocity and Penetration of Hydrogen into Ni3Fe Alloy” (in Russian), Fiz.-Khim. Mekh. Mater., 5(5), 597–601 (1969) (Experimental, Phase Relations, Mechan. Prop., 18) Lipets, T.V., Vert, Zh.L., Tverdovsky, I.P., “Solubility of Hydrogen in Alloys of Nickel with Iron and Cobalt” (in Russian), Zh. Fiz. Khim., 43(5), 1331–1333 (1969) (Experimental, Phase Relations, 14) Simakov, Yu.P., “The Diffusion and Solubility of Hydrogen in Nickel-Iron Alloys” (in Russian), Sbornik Nauchn. Tr. Permsk. Politekhn. Inst., (51), 87–95 (1969) (Experimental, Phase Relations, Interface Phenomena, 6) Vykhodets, V.P., Gol’tsov, V.A., Gel’d, P.V., “Diffusion and Solubility of Hydrogen in Ordering Alloys of the Cu3Au Type” (in Russian), Ukr. Fiz. Zhur., 15(1), 107–110 (1970) (Calculation, Phase Relations, 9) Baranowski, B., Filipek, S., “Electrical Resistance of Ni/Fe Alloys at High Pressures of Gaseous Hydrogen”, Roczn. Chem., 45(7–8), 1353–1354 (1971) (Experimental, Phase Relations, Electr. Prop., 5) Beck, W., Bockris, J.O’M., Genshaw, M.A., Subramanyan, P.K., “Diffusivity and Solubility of Hydrogen as a Function of Composition in Fe-Ni Alloys”, Metall. Trans., 2(3), 883–888 (1971) (Experimental, Phase Relations, #, *, 20) Blossey, R.G., Pehlke, R.D., “Solubility of Hydrogen in Liquid Fe-Co-Ni Alloys”, Metall. Trans., 2, 3157–3161 (1971) (1972) (Experimental, Phase Relations, Thermodyn., 26) Wayman, M.L., Smith, G.C., “Hydride Formation in Nickel-Iron Alloys”, J. Phys. Chem. Solids, 32(1), 103–108 (1971) (Experimental, Phase Relations, 21) Baranowski, B., “Thermodynamics of Metal/Hydrogen Systems at High Pressures”, Ber. Bunsen-Gesellschaft Phys. Chem., 76(8), 714–724 (1972) (Experimental, Phase Relations, 51) Brusetti, R., Chambron, W., “Vacancy Defects from Tempering in Iron-Nickel Alloy with 70 % Nickel. Inﬂuence of Hydrogen” (in French), J. Phys. Chem. Solids, 33(5), 993–1003 (1972) (Experimental, Interface Phenomena, 18) Dresler, W., Frohberg, M., “The Inﬂuence of the Structure of Binary Systems - Particularly Iron-Nickel - on the Diffusion Coefﬁcient of Hydrogen”, Ber. Bunsen-Gesellschaft Phys. Chem., 76(8), 826 (1972) (Experimental, Interface Phenomena, 0) Ngia, N., Yavoiskiy, V.I., Kosterev, L.B., Afanas’yev, M.I., “Hydrogen Solubility in Binary Iron-Base Alloys”, Russ. Metall. (Engl. Transl.), (4), 11–15 (1977), translated from Izv. Akad. Nauk SSSR, Met., (4), 18–24 (1972) (Experimental, Phase Relations, Thermodyn., 19) Baranowski, B., Filipek, S., “Investigation on the Nickel-Iron-Hydrogen System within a Wide Range of Hydrogen Pressures. Part I. Electric Resistance at 25°C”, Roczn. Chem., 47(11), 2165–2177 (1973) (Experimental, Phase Relations, Electr. Prop., Thermodyn., 22) Dresler, W., Frohberg, M.G., “Diffusion Coefﬁcient of Hydrogen in the System Iron-Nickel at 25 and 58°C”, J. Iron Steel Inst., 211, 298–302 (1973) (Experimental, Interface Phenomena, 13) Boorstein, W.M., Pehlke, R.D., “Measurement of Hydrogen Solubility in Liquid Iron Alloys Employing a Constant Volume Technique”, Metall. Trans., 5(2), 399–405 (1974) (Experimental, Phase Relations, 29) Petrushevsky, M.S., Gel’d, P.V., Abramycheva, I.E., “Short-Range Order and Thermodynamics of the Interaction of Hydrogen with Liquid Fe-Ni-Co Alloys” (in Russian), Tr. Uralsk. Politekhn. Inst., 231, 80–85 (1974) (Calculation, Phase Relations, Thermodyn., 8) Shvetsov, N.I., Levchenko, V.L., Ryabov, R.A., “Hydrogen Solubility in Iron-Nickel Alloys” (in Russian), Tr. Uralsk. Politekhn. Inst., 231, 140–141 (1974) (Experimental, Phase Relations, Thermodyn., 3) Dagbert, C., Galland, J., Azou, P., Bastien, P., “Temperature Inﬂuence on Hydrogen Behavior in Iron-Nickel Alloy” (in French), Compt Rend. Acad. Paris, B, 281(18), 437–441 (1975) (Experimental, Interface Phenomena, 6)

MSIT®

DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

18 [1976Gol]

[1976Miz] [1976Pet]

[1976Pon1]

[1976Pon2]

[1976Sta] [1977Kar]

[1977Pet]

[1977Pon]

[1978Ant]

[1979Sig]

[1980Bar]

[1982Sak]

[1983Har]

[1984Fro1] [1984Fro2] [1984Ros] [1987Sch]

Fe–H–Ni Gol’tsov, V.A., Latyshev, V.V., “Effect of Magnetic Ordering on the Permeability, Diffusion and Solubility of Hydrogen in Nickel-Iron Alloys” (in Russian), Fiz.-Khim. Mekh. Mater., 12(5), 28–32 (1976) (Experimental, Phase Relations, Magn. Prop., 15) Mizutani, T., Shinjo, T., Takada, T., “Mössbauer Study of Ni-Fe Hydrides”, J. Phys. Soc. Jpn., 41(3), 794–797 (1976) (Experimental, Phase Relations, Magn. Prop., 13) Petrushevsky, M.S., Gel’d, P.V., Abramycheva, I.E., Kostina, T.K., “Investigation of the Hydrogen Solubility in the Liquid Fe-Co-Ni Alloys” (in Russian), Dokl. Akad. Nauk SSSR, 227(2), 337–340 (1976) (Experimental, Phase Relations, 7) Ponyatovskii, E.G., Antonov, V.E., Belash, I.T., “On the Critical Phenomena in the Ni-Fe-H System at High Hydrogen Pressures” (in Russian), Dokl. Akad. Nauk SSSR, 230, 649–651 (1976) (Experimental, Phase Relations, Electr. Prop., Magn. Prop., 8) Ponyatovskii, E.G., Antonov, V.E., Belash, I.T., “Effect of Hydrogen Pressure up to 20 kbar on the Curie Point of Fe-Ni Alloys in the Invar Region” (in Russian), Fiz. Tverd. Tela, 18(12), 3661–3665 (1976) (Experimental, Electr. Prop., Magn. Prop., 19) Stafford, S.W., McLellan, R.B., “The Thermodynamic Properties of the Fe-Ni-H Ternary System”, Acta Metall., 24, 553–558 (1976) (Experimental, Thermodyn., Phase Relations, 53) Karamysheva, G.A., Men’, A.N., “Calculation of the Concentration-Dependence of Hydrogen Solubility in Binary Alloys Using the Cluster Component Method”, Russ. Metall. (Engl. Transl.), (2), 82–83 (1977), translated from Izv. Akad. Nauk SSSR, Met., (2), 95–96 (1977) (Calculation, Phase Relations, 5) Petrushevsky, M.S., Gel’d, P.V., Abramycheva, I.E., Kostina, T.K., “Investigation and Calculation of the Hydrogen Solubility in the Liquid Fe-Co-Ni Alloys” (in Russian), Izv. Vyssh. Uchebn. Zaved., Chern. Met., (10), 5–9 (1977) (Experimental, Phase Relations, 7) Ponyatovskii, E.G., Antonov, V.E., Belash, I.T., “The Effect of Hydrogen Pressure up to 23 kbar on the Temperature of the αγ Transformation in the Iron-Nickel Alloys” (in Russian), Fiz. Met. Metalloved., 44(5), 1038–1043 (1977) (Experimental, Phase Relations, 13) Antonov, V.E., Belash, I.T., Degtyareva, V.F., Ponomarev, B.K., Ponyatovskii, E.G., Tissen, V.G., “Magnetic Properties of the Hydrogen Solutions in the Nickel-Iron Alloys” (in Russian), Fiz. Tverd. Tela, 20(9), 2680–2686 (1978) (Experimental, Magn. Prop., 13) Sigrist, P., Feichtinger, H.K., Marincek, B., “A New Method for the Determination of Diffusion Coefﬁcients and Solubilities of Gases in Liquid Metals and Alloys” (in German) in “Gases in Metals (Proc. Conf.)”, Darmstadt, 1979, Deutsche Gesellschaft Metallkde, Oberursel, Germany, 15–22 (1979) (Calculation, Experimental, Interface Phenomena, 11) Barmin, N.I., Kodes, E.S., Nefedov, V.M., Ryabov, R.A., Geld, P.V., “Investigation of Hydrogen Behavior in Alloys of Iron with Nickel” (in Russian), Zh. Fiz. Khim., 54(11), 2895–2898, (1980) (Experimental, Mechan. Prop., 7) Sakamoto, Y., Yuwasa, K., Hirayama, K., “X-Ray Investigation of the Absorption of Hydrogen by Several Palladium and Nickel Solid Solution Alloys”, J. Less-Common Met., 88, 115–124 (1982) (Experimental, Crys. Structure, Phase Diagram, Phase Relations, #, 22) Harada, S., “Thermal-Expansion Coefﬁcient and Youngs Modulus of Hydrogenated FCC Fe-Ni Invar-Alloys”, J. Phys. Soc. Jpn., 52(4), 1306–1310 (1983) (Experimental, Mechan. Prop., 14) Frohberg, M.G., Anik, S., “Prediction of Hydrogen Solubility in Binary Iron Melts” (in German), Arch. Eisenhuttenwes., 55(2), 45–48 (1984) (Calculation, Phase Relations, 20) Fromm, E., Jehn, H., “Hydrogen in Elements”, Bull. Alloys Phase Diagrams, 5(3), 323–326 (1984) (Review, Phase Relations, 3) Rossiter, P.L., Jago, R.A., “Towards a True Fe-Ni Phase Diagram”, Mater. Res. Soc. Symp. Proc., 21, 407–411 (1984) (Review, Phase Diagram, *, 26) Schuermann, E., Sittard, M., Voelker, R., “Equivalent Inﬂuence of Alloying Elements on the Nitrogen and Hydrogen Solubility in Liquid Ternary and Multicomponent Nickel-Base Alloys” (in German), Z. Metallkd., 78(6), 457–466 (1987) (Review, Phase Diagram, Phase Relations, Thermodyn., 53)

DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–Ni [1990Mat]

[1990Zag]

[2002Ant]

[2002Shi] [2004Fuk]

[2004Zag]

[2005Ide]

[2006Ara] [2006Tom]

[2007Kuz]

[Mas2] [V-C2]

Landolt-Börnstein New Series IV/11D4

19

Matysina, Z.A, Milyan, M.I., “Connection of Some Phase Transformations with Alloy Phase Diagrams”, Russ. Metall. (Engl. Transl.), (2), 171–183 (1990), translated from Izv. Akad. Nauk SSSR, Met., (2), 175–188 (1990) (Review, Phase Relations, 48) Zaginaychenko, S.Yu., Matysina, Z.A., Milyan, M.I., “Solubility of Interstitial Impurities in Alloys”, Phys. Met. Metallogr., 70, 60–64 (1990), translated from Fiz. Met. Metalloved., (9), 63–67, (1990) (Calculation, Phase Relations, 20) Antonov, V.E., Baier, M., Dorner, B., Fedotov, V.K., Grosse, G., Kolesnikov, A.I., Ponyatovsky, E.G., Schneider, G., Wagner, F.E., “High-Pressure Hydrides of Iron and its Alloys”, J. Phys., Condens. Matter, 14, 6427–6445 (2002) (Experimental, Review, Phase Relations, #, 46) Shizuku, Y., Yamamoto, S., Fukai, Y., “Phase Diagram of the Ni-H System at High Hydrogen Pressures”, J. Alloys Compd., 336(1–2), 159–162 (2002) (Phase Diagram, Experimental, *, #, 19) Fukai, Y., Yamamoto, S., Harada, S., Kanazawa, M., “The Phase Diagram of the Ni-H System Revisited”, J. Alloys Compd., 372(1–2), L4–L5 (2004) (Phase Diagram, Experimental, #, 14) Zagorodniy, K., Shivanyuk, V., Toebbens, D., Danilkin, S., Gavriljuk, V., “Hydrogen-Caused Phase Transformations, Relaxation and Hysteretic Phenomena in FCC Alloys Fe55Cr25Ni20 and Fe50Ni50”, Scr. Mater., 50(12), 1467–1470 (2004) (Experimental, Phase Relations, 13) Ide, N., Naito, T., Asano, S., “Internal Friction Peak in FCC Fe-Cr-Ni Alloys HydrogenCharged by Gas-Equilibration Method”, Jpn. J. Appl. Phys., 44(11), 8088–8090 (2005) (Experimental, Morphology, Phase Relations, 11) Arasi, C.K., Balaguru, R.J.B., Raj, S.A.C., Lawrence, N., “Lattice Dynamics of the Ni0.3Fe0.7-H System”, Phys. Scri., 73(1), 11–16 (2006) (Experimental, Mechan. Prop., 14) Tomashik, V., Perrot, P., “Copper-Hydrogen-Nickel”, MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 10.16213.1.20, (2006) (Crys. Structure, Phase Diagram, Assessment, 45) Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2007) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, 41) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

MSIT®

DOI: 10.1007/978-3-540-78644-3_7 # Springer 2008

Fe–H–O

1

Iron – Hydrogen – Oxygen Pierre Perrot

Introduction H2-H2O, as well as CO-CO2 atmospheres have been widely used to investigate the equilibria between iron and its oxides [1940Wib] because these atmospheres allow the determination of oxygen potentials with an accuracy which cannot be obtained with any other method such as electrochemistry or calorimetry. This happy result is easily explained by the afﬁnity of oxygen towards iron, which is about the same as its afﬁnity towards H2 or CO. The Fe-O phase diagram, widely accepted since [1945Dar, 1946Dar] has been conﬁrmed by numerous and very precise experimental determinations, so, the works dealing with equilibria of iron oxides under H2-H2O atmospheres will not be taken into account in this report. For the same reason, the equilibria between iron, its oxides and hydroxides in aqueous solution will be presented from the only Pourbaix’ work [1963Pou]. On the other hand, the reaction of water vapor with liquid iron plays an important role in several steelmaking processes since the water content in the highly postcombusted gas may be as high as 30%. The main experimental results related to Fe-H2O reactions are gathered in Table 1. Binary Systems The Fe-H system under 0.1 MPa of hydrogen pressure is accepted from [1990San]. The Fe-H system has been carefully investigated by [2003Fuk] up to 10 GPa of hydrogen pressure and 1500°C. The hydrogen solubility in iron under low hydrogen pressures (up to 1 MPa) is given in [1980Fro]. The Fe-O system accepted by [Mas2], mainly from the fundamental work of [1945Dar, 1946Dar] has been carefully assessed by [1991Sun, 1995Kow]. The main compound of interest in the H-O system is H2O characterized by its oxidizing properties towards Fe. Mixtures H2-H2O are often used as a source of imposed oxygen potential. Solid Phases Numerous solid phases have been reported in the Fe-H-O system. They are often metastable and ill deﬁned. The main solid phases, whose existence is widely recognized are presented in Table 2. Iron oxides Fe3O4 (magnetite) and Fe2O3 (hematite) are stable at room temperature whereas iron hydroxides Fe(OH)2 and Fe(OH)3 are metastable, lose water with formation of FeOOH (goethite) as an intermediate compound, Fe3O4 and Fe2O3 as ﬁnal products. Gaseous Fe(OH)2 has been proposed as an intermediate species which forms during the formation of Fe3O4 by Fe oxidation under water vapor at 500°C [1973Sur]. Temperature – Composition Sections The phases in equilibrium under H2-H2O atmospheres are namely (αFe), (γFe), Fe1–xO, Fe3O4, L1 (liquid metal) and L2 (liquid oxide). Fe2O3 cannot be stable under such atmospheres, because it is reduced into Fe3O4 under pure water vapor. The stability domains of these phases are shown in Fig. 1, mainly from [1958Eds], and slightly modiﬁed to take into account the well accepted observation that the wuestite composition in equilibrium with iron between 1000°C and its melting point of 1380°C is Fe0.947O [1945Dar, 1970Gra]. Thermodynamics Information on the reactions between iron and water vapor may be found in [1980Fro, 1989Oet, 2003Per]. The solubility of water vapor in liquid iron may be described by the equilibrium: H2O (gas) ⇌ 2 {H}Fe + {O}Fe ΔrG° = 203130 + 1.72 T. In this expression, the reference states are the gaseous water under the standard pressure p° = 0.1 MPa and the elements (H or O) dissolved in liquid iron under the concentration c° = 1 mass%. It is in agreement with the expression proposed by [1989Rag] for the following Landolt-Börnstein New Series IV/11D4

MSIT®

DOI: 10.1007/978-3-540-78644-3_8 # Springer 2008

2

Fe–H–O

equilibrium: H2O (gas) ⇌ H2 (gas) + {O}Fe ΔrG° = – 134600 + 61.65 T. The reference states are the same (p° = 0.1 MPa for the gases and c° = 1 mass% for the solute). The oxygen solubility in solid iron in equilibrium with H2O-H2 atmospheres may be expressed by the following expressions [1976Kru]: In (γFe): log10 (cO / at.%) = log10(pH2O/pH2) + 0.26 – (3720/T ) (912–1394°C) In (δFe): log10 (cO / at.%) = log10(pH2O/pH2) + 1.17 – (4740/T ) (1394–1538°C) In liquid Fe: log10 (cO / at.%) = log10(pH2O/pH2) + 3.55 – (6750/T ) (1538–1700°C) In the three preceding expressions, cO represents the oxygen content of the iron, in at.%; it must be pointed out that these expressions may be used only for H2-H2O atmospheres corresponding to the iron domain shown in Fig. 1. The Fe-Fe3O4 equilibrium temperature depends on the total pressure [1984Fuk]. It increases by 400°C when the pressure goes from 0.1 MPa to 20 GPa. Notes on Materials Properties and Applications Water vapor acts as a decarburizing agent in steels [1994Nag] by reacting with iron droplets containing carbon according to the reaction H2O ⇌ 2 {H} + {O}. Dissolved oxygen reacts with C to form CO. This reaction is thermodynamically favorable and can cause a substantial hydrogen pick up in the steel. H2 has been proposed for the direct reduction of iron ores with the aim to reduce CO2 emissions due to the blast furnace-basic oxygen furnace route. A promising way is the hydrogen plasma smelting route [2005Pla]. αFeOOH (goethite) is used as a pigment [2005Kre] with color ranging from lemon yellow to dark brown. Miscellaneous The kinetics of oxidation of αFe with water vapor was investigated at 500°C by [1973Sur] and at 800–1000°C by [1970Gra]. The mechanism of Fe3O4 oxide layer growth is better described by a chemical transport model via a gaseous species such as Fe(OH)2 than by a diffusion model. The oxide layer is non protective and the kinetics of the layer growth tends to be linear with time. The potential-pH diagrams (Pourbaix’ diagram) of iron in aqueous solution [1963Pou] are shown in Figs. 2 and 3. The diagram shown in Fig. 2 is the stable diagram in which the solid phases involved are Fe, Fe3O4 and Fe2O3. Figure 3 gives the metastable diagram in which the solid phases involved are Fe, Fe(OH)2 and Fe(OH)3. In a neutral or basic medium, hydroxides appear ﬁrst, then transform into oxy-hydroxides such as FeOOH, then in stable oxides Fe3O4 and Fe2O3. In both diagrams, the dashed lines delimit the stability domain of water under atmospheric pressure. Above the upper line, whose equation is E/ Volt = 1.23 – 0.06 pH, water is oxidized into gaseous oxygen. Below the lower line whose equation is E/Volt = – 0.06 pH, water is reduced into hydrogen. The stability domain of the main aqueous species (Fe++, Fe+++ in acidic medium and HFeO2– in basic medium) depends on its concentration. The values (0, –2, –4, –6) shown on the curves represent log10 (ci/mol·L–1), where ci represents the concentration of the considered species (Fe++, Fe+++ or HFeO2–). The potential at equilibrium Fe/Fe(OH)2 does not depend on the pressure whereas the potential at equilibrium H2/H+ decreases when the pressure increases. Below 74 MPa of hydrogen pressure, E(H2/H+) > E{Fe/Fe(OH)2} so that water corrodes iron, even in a reducing medium. Above 74 MPa, E(H2/H+) < E{Fe/Fe(OH)2} so that iron acts as a noble metal and is not more corroded by water in a reducing medium and at pH > 7.

Table 1.

Investigations of the Fe-H-O Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1958Eds]

Oxide equilibria under H2-H2O atmospheres

400–1600°C, Fe, FeO, Fe3O4 and liquid domains

[1965Bur]

Hydrogen solubility in liquid iron

1600°C (continued)

DOI: 10.1007/978-3-540-78644-3_8 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–O

3

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1970Gra]

Thermogravimetry

800–1000°C, Fe under H2-H2O atmospheres

[1973Sur]

Thermogravimetry

500°C, Fe under H2-H2O atmospheres

[1984Fuk]

XRD, micrography

< 1000°C, Fe under H2-H2O atmospheres, p < 20 GPa

[1987Ito]

XRD, ionic and electronic conductivity measurements

25°C. Preparation of HFe11O17,H2O par ion exchange

[1994Nag]

Thermogravimetry, chemical analysis, kinetics

1400–1600°C, H2O gas on liquid iron or steel, 10 to 30 kPa of H2O

[2005Kre]

XRD, FTIR (Fourier Transform Infrared, Mössbauer)

25°C, αFeOOH (Goethite)

[2005Pla]

MEB analysis

2.104 K, Ar-H2 plasma smelting of iron ores

[2005Was]

Anomalous X-ray scattering

αFeOOH

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2, V-C2] (A2 structure)

(αFe) < 912 (γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [Mas2, V-C2]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2] Triple point α-γ-ε at 8.4 GPa, 430°C

Fe1–xO (Wuestite) 1422–569

cF8 Fm 3m NaCl

a = 431.0 a = 429.3

0.05 < x < 0.12 [1991Sun] x = 0.05 x = 0.12

Fe3O4 (I) < 580

oP56 Pbcm Fe3O4 I

a = 1186.8 b = 1185.1 c = 1675.2

[V-C2]

Fe3O4 (h) (Magnetite) 1596–580

cF56

a = 839.6

at 25°C

Fd 3m MgAl2O4

a = 854.5

at 1000°C [V-C2] inverse Spinel (continued)

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4

Fe–H–O

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

αFe2O3 (Hematite) < 1451

hR30 R 3c αAl2O3 (Corundum)

a = 503.42 c = 1374.83

Melts at 1892°C under O2 pressure

βFe2O3

cI80 Ia 3 Mn2O3

a = 939.3

metastable phase [V-C2]

γFe2O3 (Maghemite)

cF56 Fd 3m MgAl2O4

a = 834

metastable phase [1989Rag]

αFeOOH (Goethite)

oP16 Pbnm

a = 460.8 b = 995.6 c = 302.1

[2005Kre] Loses 0.5 H2O at 136°C to give αFe2O3

βFeOOH (Akaganeite)

mI* C2/m

a = 1489.6 b = 303.4 c = 1060.0 β = 135.13°

βFeO1–x(OH)1+xClx [1991Pos]

γFeOOH (Lepidocrocite)

oC16 Cmcm

a = 307.2 b = 1251.6 c = 387.3

[2001Zhu] Loses 0.5 H2O by heating to give γFe2O3

Fe(OH)2

-

-

metastable

Fe(OH)3

-

-

metastable

HFe11O17,H2O

hP64 P63/mmc βAl2O3

a = 593.1 c = 2383

[1987Ito] decomposes at 400°C

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Fe–H–O

Fig. 1. Fe-H-O.

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Stability domains of solid and liquid phases under H2-H2O atmospheres

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6

Fig. 2. Fe-H-O.

Fe–H–O

Stable potential - pH diagram in aqueous solution at 25°C

DOI: 10.1007/978-3-540-78644-3_8 # Springer 2008

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Fe–H–O

Fig. 3. Fe-H-O.

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7

Metastable potential - pH diagram in aqueous solution at 25°C

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8

Fe–H–O

References [1940Wib] Wiberg, M., “On the Reduction of Iron Oxides with Carbon Oxides, Water or Methane” (in Swedish), Jernkontorets Ann., 124(5), 179–212 (1940) (Experimental, Morphology, Phase Relations, Thermodyn., 38) [1945Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. I- The Wuestite Field and Related Equilibria”, J. Am. Chem. Soc., 67, 1398–1412 (1945) (Experimental, Phase Diagram, Phase Relations, Thermodyn., *, 26) [1946Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. II- Equilibria and Thermodynamics of Liquid Oxides and Other Phases”, J. Am. Chem. Soc., 68, 798–816 (1946) (Experimental, Phase Diagram, Phase Relations, Thermodyn., *, 24) [1958Eds] Edstroem, J.O., “Some Chemical Reactions Involved in Pelletizing and Iron Ore Reduction” (in Swedish), Jernkontorets Ann., 142, 401–466 (1958) (Crys. Structure, Experimental, Phase Relations, 40) [1963Pou] Pourbaix, M., “Atlas of Electrochemical Equilibria at 25°C” (in French), Gauthier-Villlars (Ed.), Paris, “Iron”, Sect. 12-1, 307–329 (1963) (Thermodyn., Phase Relations, Review, 18) [1965Bur] Burylev, B.P., “Solubility of Hydrogen in Liquid Iron Alloys” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., 8(2), 17–22 (1965) (Experimental, Phase Relations, Thermodyn., 13) [1970Gra] Grabke, H.J., Best, K.J., Gala, A., “Oxydation Reaction of Metal and Oxide under CO2-CO and H2O-H2 Mixtures” (in German), Werkstoffe und Korrosion, 21, 911–916 (1970) (Phase Relations, Thermodyn., Kinetics, 22) [1973Sur] Surmann, P.L., “The Oxidation of Iron at Controlled Oxygen Partial Pressures – I. Hydrogen/ Water Vapour”, Corros. Sci., 13(2), 113–124 (1973) (Experimental, Kinetics, Morphology, Thermodyn., 10) [1976Kru] Krueger, J., Kunze, H.D., Schuermann, E., “Gas and Carbon in Metals” (in German), Fromm, E., Gebhardt, E. (Eds.), Springer-Verlag, Berlin, 518–613 (1976) (Review, Phase Relations, Thermodyn., 241) [1980Fro] Fromm, E., Hoerz, G., “Hydrogen, Nitrogen, Oxygen, and Carbon in Metals”, Int. Mater. Rev., (5/6), 269–312 (1989) (Kinetics, Phase Diagram, Thermodyn., Review, 255) [1984Fuk] Fukai, Y., “The System Iron-Water-Hydrogen under High Pressure” (in Japanese), Nippon Kinzoku Gakkai Kaiho, 23(5), 369–372 (1984) (Experimental, Phase Relations, Thermodyn., 20) [1987Ito] Ito, S., Kubo, N., Nariki, S., Yoneda, N., “Ion Exchange in Alkali Layers of Potassium β-Ferrite ((1+x)K2O·11Fe2O3) Single Crystals”, J. Am. Ceram. Soc., 70(2), 874–879 (1987) (Crys. Structure, Experimental, 29) [1989Oet] Oeters, F., “Metallurgy of the Steel Production” (in German), Springer-Verlag, 503 pp. (1989) (Phase Diagrams, Phase Relations, Thermodyn., Review, 723) [1989Rag] Raghavan, V., “The Fe-H-O (Iron-Hydrogen-Oxygen) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 5, 140 (1989) (Phase Relations, Review, Thermodyn., 5) [1990San] San Martin, A., Manchester, F.D., “The Fe-H (Iron-Hydrogen) System”, Bull. Alloys Phase Diagrams, 11(2), 173–184 (1990) (Phase Diagram, Phase Relations, Review, Thermodyn., 86) [1991Pos] Post, E., Buckwald, V.F., “Crystal Structure Reﬁnement of Akaganeite”, Amer. Mineralogist, 76, 272–277 (1991) (Crys. Structure, Experimental, 17) [1991Sun] Sundman, B., “An Assessment of the Fe-O System”, J. Phase Equilib., 12(1), 127–140 (1991) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 53) [1994Nag] Nagasaka, T., Fruehan, R.J., “Kinetics of the Reaction of H2O Gas with Liquid Iron”, Metall. Mater. Trans., B, 25B(2), 245–253 (1994) (Kinetics, Experimental, 21) [1995Kow] Kowalski, M., Spencer, P.J., “Thermodynamic Reevaluation of the Cr-O, Fe-O and Ni-O Systems: Remodelling the Liquid, BCC and FCC Phases”, Calphad, 19(3), 229–243 (1995) (Assessment, Phase Diagram, Phase Relations, Thermodyn., Review, 47) [2001Zhu] Zhukhlistov, A.P., “Crystal Structure of Lepidocrocite FeO(OH) from the ElectronDiffractometry Data”, Crystallography Rept., 46(5), 730–733 (2001), translated from Kristallografiya, 46(5), 805–808 (2001) (Crys. Structure, Experimental, 14) DOI: 10.1007/978-3-540-78644-3_8 # Springer 2008

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Fe–H–O [2003Fuk]

[2003Per]

[2005Kre]

[2005Pla] [2005Was]

[Mas2] [V-C2]

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9

Fukai, Y., Mori, K., Shinomiya, H., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys under High Hydrogen Pressures”, J. Alloys Compd., 348, 105–109 (2003) (Phase Diagram, Phase Relations, Experimental, 42) Perrot, P., Foct, J., “Gases other than Hydrogen in Iron and Steels” (in French) Techniques de l’Ingenieur, Ser. Metalllurgie, M-4275, 1–23 (2003) (Phase Relations, Thermodyn., Review, 127) Krehula, S., Music, S., Popovic, S., “Inﬂuence of Ni-dopant on the Properties of Synthetic Goethite”, J. Alloys Compd., 403, 368–375 (2005) (Crys. Structure, Experimental, Magn. Prop., Optical Prop., 30) Plaul, J.F., Krieger, W., Baeck, E., “Reduction of Fine Ores in Argon-Hydrogen Plasma”, Steel Res. Int., 76(8), 548–554 (2005) (Experimental, Kinetics, Phase Relations, 14) Waseda, Y., Suzuki, S., Saito, M., “Atomic-scale Structure in α-FeOOH Particles Estimated from the Anomalous X-ray Scattering Data with Reverse Monte Carlo Simulation”, J. Alloys Compd., 401, 24–28 (2005) (Calculation, Crys. Structure, Experimental, 16) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

MSIT®

DOI: 10.1007/978-3-540-78644-3_8 # Springer 2008

Fe–H–P

1

Iron – Hydrogen – Phosphorus Pierre Perrot

Introduction Hydrogen and phosphorus are known to play an important role in steelmaking because of their deleterious effect on the mechanical behavior of the steels. Hydrogen causes embrittlement and phosphorus worsens the situation because of the existence of a low melting (977°C) ternary eutectic in the C-Fe-P system. Most of the investigations, gathered in Table 1, have been directed towards the inﬂuence of P on the hydrogen solubility in Fe. Binary Systems The Fe-H system under 0.1 MPa of hydrogen pressure is accepted from [1990San]. The Fe-P diagram is mainly accepted from [2002Per]. The main hydrogen phosphide is the gaseous PH3, an endothermal compound which has never been reported in steelmaking. Solid Phases Solid phases are shown in Table 2. No ternary hydrides are known. Isothermal Sections Phosphorus reduces slightly the hydrogen solubility in liquid iron [1963Wei, 1966Noz, 1981Sch, 1988Rag] in agreement with the calculations of [1993Din]. Figure 1 shows the hydrogen solubility in liquid Fe-P alloys measured at four temperatures by [1981Sch]. Thermodynamics The Wagner ﬁrst order interaction parameter eH(P) has been experimentally determined at 1592°C by [1963Wei], between 1450 and 1620°C in liquid (Fe,P) alloys by [1966Noz]. It is deﬁned by eH(P) = {∂ log10 fP/∂ (% P)} where (% P) represents the phosphorus content of the alloy expressed in mass% and fP the activity coefﬁcient of P in the alloy deﬁned by fP = (% P in pure iron)/(% P in the alloy). It is calculated from the solubility measurements at constant temperature and hydrogen pressure and has been measured at eH(P) = 0.01 in the temperature range 1450–1620°C for less than 6 mass% P in the alloy. The interaction coefﬁcient may also be deﬁned by ɛH(P) = {∂ ln γP/∂ xP}, where xP is the mole fraction of P in the liquid alloy and γP = (xP in pure iron)/(xP in the alloy). The careful investigation of [1981Sch] leads to ɛH(P) = – 0.4495 + (3166/T ) between 1420 and 1610°C for less than 1 at.% P in good agreement with the preceding relation. This experimental result contradicts the calculation of [1999Din], based on the Miedema’s model of the heat of formation of binary alloys, which proposes ɛH(P) = 15.7. However, it must be pointed out that the Miedema’s model can hardly be extrapolated to non metallic elements. Notes on Materials Properties and Applications Fe-P alloys sintered in H2 or N2 form soft magnetic materials whose use is promising in micromotors [2001Chi].

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DOI: 10.1007/978-3-540-78644-3_9 # Springer 2008

2 Table 1.

Fe–H–P Investigations of the Fe-H-P Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1963Wei]

Hydrogen solubility measurements, Sievert’s method

1592°C, < 1 mass% P, < 0.1 MPa of H2 pressure

[1966Noz]

Hydrogen solubility measurements, Sievert’s method

1450–1670°C, < 6 mass% P, < 0.1 MPa of H2 pressure

[1981Sch]

Hydrogen solubility measurements, Sievert’s method

1420–1610°C, xP < 0.20, < 0.1 MPa of H2 pressure

[2001Chi]

Magnetization curves, hardness measurements

Fe-P (< 1 mass% P) powders sintered. Soft magnetic material preparation

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(P) (red) < 417

c*66

a = 1131

sublimation at 1 bar. Stable form of P. Triple point at 576°C, > 36.3 bar; triple point at 589.6°C at 1 atm [Mas2, V-C2]

(P) (white) < 44.14

c** P (white)

a = 718

common form of P [Mas2, V-C2]

(P) (black)

oC8 Cmca P (black)

a = 331.36 b = 1047.8 c = 437.63

at 25°C [Mas2, V-C2]

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

pure Fe at 1390°C [V-C2, Mas2] dissolves up to 4.52 at.% P at 1048°C at 1394°C pure Fe at 25°C [Mas2, V-C2]

(αFe) < 912°C

a = 286.65

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [Mas2, V-C2] dissolves up to 0.5 at.% P at 1150°C

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2] triple point α-γ-ε at 8.4 GPa, 430°C

Fe3P < 1166

tI32 I 4 Ni3P

a = 910.8 c = 445.5

at 25°C [Mas2, V-C2]

a = 917.4 c = 453.0

at 678°C [1990Oka] (continued)

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Fe–H–P

3

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

Fe2P < 1370

hP9 P 62m Fe2P

a = 586.4 c = 346.0

33.3–34 at.% P [V-C2]

Fe2P (HP)

oP12 Pnma Co2Si

a = 577.5 b = 357.1 c = 664.1

at 800°C under 8 GPa [V-C2]

FeP < 1370

oP8 Pna21 AsCo or oP8 Pnma MnP

a = 519.3 b = 579.2 c = 309.9

[2002Per]

a = 520.8 b = 316.0 c = 581.2

[V-C2]

FeP2

oP6 Pnnm FeS2 (marcasite)

a = 497.29 ± 0.07 b = 565.68 ± 0.08 c = 272.30 ± 0.04

[V-C2]

FeP4

mP30 P21/c FeP4

a = 461.9 ± 0.1 b = 1367.0 ± 0.2 c = 700.2 ± 0.1 β = 101.48°

[V-C2]

Fe4P (HP)

oC20 C2221

a = 500.5 ± 0.1 b = 1021.3 ± 0.3 c = 553.0 ± 0.1

at 1100°C under 6 GPa [V-C2]

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Fig. 1. Fe-H-P.

Fe–H–P

Hydrogen solubility in Fe-P liquid alloys under 1 atm H2

DOI: 10.1007/978-3-540-78644-3_9 # Springer 2008

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Fe–H–P

5

References [1963Wei] Weinstein, M., Elliott, J.F., “Solubility of Hydrogen in Liquid Iron Alloys”, Trans. Met. Soc. AIME, 227, 382–393 (1963) (Calculation, Experimental, Thermodyn., 27) [1966Noz] Nozaki, H., Ban-ya, S., Fuwa, T., Matoba, S., Ono, K., “Effect of Carbon, Silicon, Phosphorus and Nickel on the Solubility of Hydrogen in Liquid Iron” (in Japanese), Tetsu to Hagane, 52(13), 1823–1833 (1966) (Experimental, Phase Relations, Thermodyn., 17) [1981Sch] Schuermann, E., Kaettlitz, W., “Equivalent Effect of the Alloying Elements on the Concentration- and Temperature-Dependent Hydrogen Solubility in Iron-Rich Ternary and Multicomponent Melts” (in German), Arch. Eisenhuettenwes., 52(8), 295–301 (1981) (Calculation, Experimental, Phase Relations, Thermodyn., 20) [1988Rag] Raghavan, V., “The Fe-H-P (Iron-Hydrogen-Phosphorus) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, Vol. 3, 80 (1988) (Review, Phase Relations, Thermodyn., 3) [1990Oka] Okamoto, H., “The Fe-P (Iron-Phosphorus) System”, Bull. Alloy Phase Diagrams, 11(4), 404–412 (1990) (Phase Diagram, Phase Relations, Review, 89) [1990San] San Martin, A., Manchester, F.D., “The Fe-H (Iron-Hydrogen) System”, Bull. Alloys Phase Diagrams, 11(2), 173–184 (1990) (Phase Diagram, Phase Relations, Review, Thermodyn., 86) [1993Din] Ding, X., Wang, W., Han, Q., “Thermodynamic Calculation of Fe-P-H System Melt”, Acta Metall. Sin. (China), 29(12), B527–B532 (1993) (Calculation, Theory, Thermodyn., 7) [1999Din] Ding, X., Fan, P., Wang, W., “Thermodynamic Calculation for Alloy Systems”, Metall. Trans B, 30B(2), 271–277 (1999) (Thermodyn., Theory, 18) [2001Chi] Chistyakov, V.K., Dorogina, G.A., Korobka, O.B., “Inﬂuence of a Protective Medium on the Magnetic and Mechanical Properties of Materials of the Iron - Phosphorus System”, Powder Metall. Met. Ceram., 40(9–10), 526–532 (2001) (Experimental, Magn. Prop., Mechan. Prop., 19) [2002Per] Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, Diagrams as Published in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 20.16107.1.20, (2002) (Phase Diagram, Phase Relations, Crys. Structure, 23) [Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) [V-C2] Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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DOI: 10.1007/978-3-540-78644-3_9 # Springer 2008

Fe–H–Si

1

Iron – Hydrogen – Silicon Pierre Perrot

Introduction Fe-Si alloys, in presence of H do not form hydrides, but interstitial solid solutions which play an important role in steelmaking because of undesirable effects in the embrittlement of steel products. On the other hand, alloying Si in iron increases the activation energy of H diffusion. Most of the investigations have been directed towards the H solubility measurements in Fe-Si melts. The main experimental results are gathered in Table 1. Binary Systems The Fe-Si system, accepted from [Mas2], has been later assessed by [1999Liu]. The Fe-H system under 0.1 MPa of hydrogen pressure is accepted from [1990San]. The hydrogen solubility in liquid iron may be expressed by [1984Fro]: log10xH = 0.5 log10 (pH2/Pa) – 4.44 – (1720/T) The Fe-H system has been carefully investigated by [2003Fuk] up to 10 GPa of hydrogen pressure and 1500°C. The hydrogen solubility in liquid Si under 0.1 MPa of hydrogen pressure is 0.087 at.% at 1414°C according to [Mas2], value which does not agree the experimental value of 0.020 at.% at 1600°C reported by [1981Sch] and accepted by [1984Fro]. Solid Phases The solid phases are presented in Table 2. No ternary compounds are known. Isothermal Sections A number of investigations [1977Bes] on the solubility of H in liquid Fe-Si alloys are reported. [1970Fuk], using a Sievert’s method, reported ﬁrst order Wagner interaction parameters to be positive (eHSi = 0.03 at 1600°C), indicating that Si increases the activity coefﬁcient of H in the melt and decreases its solubility at a given H2 pressure. The solubility of hydrogen in liquid Si decreases also with the iron content. At 1600°C, the minimum of solubility is observed at 0.02 at.% H in a liquid melt containing 60 at.% Si [1971Gel, 1971Pet, 1973Gel], value justiﬁed by a theoretical model proposed by [1984Fro]. The minimum of hydrogen solubility corresponds to a maximum for the enthalpy of hydrogen dissolution in liquid alloys as shown in Table 3 [1971Kos, 1977Bes]. The H solubility in Fe-Si liquid alloys measured at 1500, 1600 and 1700°C under 0.1 MPa of hydrogen pressure is shown in Fig. 1 for xSi < 0.25 [1981Sch]. The hydrogen solubility calculated at 1600°C by a statistical model at 1600°C in the whole composition range [1984Fro] is shown in Fig. 2. The solubility of H in solid alloys, investigated by [1971Rya] between 300 and 700°C, decreases with the silicon content of the alloy. Thermodynamics The Wagner ﬁrst order interaction parameter, deﬁned by eH(Si) = {∂ log10 fSi/∂ (% Si)}, where (% Si) represents the silicon content of the alloy expressed in mass% with fSi = (% Si in pure iron)/(% Si in the alloy), has been early experimentally determined at eH(Si) = 0.030 ± 0.08 [1970Fuk, 1971Kos, 1972Ngi]. A more precise value eH(Si) = 0.0286 at 1600°C was measured by [1974Boo], which corresponds to ɛH(Si) = 3.81 [1977Bes]. The interaction coefﬁcient ɛH(Si) is deﬁned by: ɛH(Si) = {∂ ln γSi/∂ xSi}, where xSi is the mole fraction of Si in the liquid alloy and γSi = (xSi in pure iron)/(xSi in the alloy). The careful investigation of [1981Sch] leads to ɛH(Si) = – 0.4467 + (3498/T) between 1500 and 1700°C for less than 1 at.% Si in agreement with the preceding relation and in contradiction with the probably too high values ɛH(Si) = 4.20 proposed by [1973Gel] at 1600°C and ɛH(Si) = 8.0 calculated by [1999Din] on the basis of Miedema’s model for the estimation of the heat of formation of binary alloys. Landolt-Börnstein New Series IV/11D4

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Fe–H–Si

Notes on Materials Properties and Applications Hydrogen plays an important role in environmental embrittlement of Fe-Si alloys. These alloys may be hardened of softened by hydrogen depending on the temperature and compositions [1988Kim] whereas high purity iron is always softened by hydrogen. Miscellaneous Hydrogen diffusion in metallic glasses gives an insight on the glass structure. So, H diffusion in Fe-Si alloys presents a deviation from Arrhenius’ law [1999Eli] which is explained by the temperature dependence of the short range order in Fe-Si alloy. The reﬁning effect of Hydrogen Plasma Arc Melting (HPAM) was investigated for impurities in Fe [2006Ela]. Under 5.3 kPa of H, the Si content of Fe has been decreased from 3.5 to 0.9 ppm whereas, under 100 kPa (1 bar) of H, the Si content decreases from 3.5 to 0.6 ppm. The removal degree of impurities seems lower under H than under Ar plasma.

Table 1.

Investigations of the Fe-H-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1970Fuk]

Hydrogen solubility in liquid alloys, Sievert’s method

1550–1600°C, < 2.5 mass% Si

[1971Gel]

Hydrogen solubility in liquid alloys

1500–1700°C, 0 to 100 % Si, 0.1 MPa of H2 pressure

[1971Kos]

Hydrogen solubility in liquid alloys, hot volume method

1415–1610°C, 0 to 100 % Si, 0.1 MPa of H2 pressure

[1971Pet]

Hydrogen solubility in liquid alloys

1415–1600°C, 0 to 100 % Si, 0.1 MPa of H2 pressure

[1971Rya]

Hydrogen absorption isotherms

300–700°C, < 6 mass% Si

[1972Ngi]

Hydrogen solubility in liquid alloys, Sievert’s method

1550–1700°C, < 10 mass% Si, 0.1 MPa of H2 pressure

[1974Boo]

Hydrogen solubility in liquid alloys, constant volume method

1560–1800°C, < 12 mass% Si, 0.1 MPa of H2 pressure

[1981Sch]

Hydrogen solubility in liquid alloys, Sievert’s method

1500–1700°C, < 25 mol% H2, 0.1 MPa of H2 pressure

[1988Kim]

Hardness measurements

< 5 mass% Si

[2006Ela]

Hydrogen plasma arc melting, Si impurities removal in Fe

2000–2300°C, 5.3 and 100 kPa of H pressure

DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

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Fe–H–Si Table 2.

3

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αFe) (Ferrite) < 912°C

cI2 Im 3m W

a = 286.65

pure Fe at 25°C [Mas2, V-C2] dissolves up to 10 at.% Si at 500°C [Mas2]. at 1390°C [V-C2, Mas2] dissolves up to 19.5 at.% Si at 1280°C [Mas2].

(δFe) 1538–1394

a = 293.15

(γFe) (Austenite) < 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [V-C2, Mas2]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, > 13 GPa [Mas2]

(Si) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

at 25°C [Mas2]. Practically no Fe solubility [Mas2].

FeSi < 1410

cP8 P213 FeSi

a = 451.7 ± 0.5

at 300°C [V-C2, Mas2]

Fe2Si 1212–1040

cP2 Pm 3m CsCl or hP6 P 3m1 Fe2Si

a = 282

66 at.% Si [Mas2, V-C2]

Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.9 ± 0.5 c = 472.0 ± 0.5

38.4 at.% Si [V-C2, Mas2]

βFeSi2(h) 1220–937

tP3 P4/mmm βFeSi2

a = 269.01 c = 513.4

69.5 to 73.5 at.% Si [Mas2, V-C2]

αFeSi2(r) < 982

oC48 Cmca αFeSi2

a = 986.3 ± 0.7 b = 779.1 ± 0.6 c = 783.3 ± 0.6

66.7 at.% Si [Mas2, V-C2]

α1, Fe3Si

cF16 Fm 3m BiF3

a = 565

10 to 30 at.% Si [Mas2, V-C2]

α2, Fe3Si

cP2 Pm 3m CsCl

-

10 to 22 at.% Si [Mas2]

Landolt-Börnstein New Series IV/11D4

a = 405.2 ± 0.2 c = 508.55 ± 0.3

MSIT®

DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

4 Table 3.

Fe–H–Si Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mole of atoms [J, mol, K]

Comments

H ⇌ {H} in pure Fe

1600

ΔH = – 187000 ΔS = – 0.6

[1971Kos]

H ⇌ {H} in Fe65Si35

1600

ΔH = – 119000 ΔS = – 6.2

[1971Kos]

H ⇌ {H} in Fe50Si50

1600

ΔH = – 65500 ΔS = – 29

[1971Kos]

H ⇌ {H} in Fe33Si67

1600

ΔH = – 56500 ΔS = – 27

[1971Kos] ΔH is maximum

H ⇌ {H} in pure Si

1600

ΔH = – 106500 ΔS = – 35.5

[1971Kos]

Fig. 1. Fe-H-Si. pressure

Hydrogen solubility in Fe-Si liquid alloys at 1500, 1600 and 1700°C under 0.1 MPa of hydrogen

DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–Si

Fig. 2. Fe-H-Si.

Landolt-Börnstein New Series IV/11D4

5

Hydrogen solubility in Fe-Si liquid alloys at 1500, 1600 and 1700°C in the whole composition range

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DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

6

Fe–H–Si

References [1970Fuk] Fukuda, S., Sugiyama, T., Furukawa, T., Kato, E., “Solubility of Hydrogen in Liquid Iron Alloys”, Rep. Casting Research Lab./Waseda Univ., (21), 35–46 (1970) (Calculation, Experimental, Phase Relations, Thermodyn., 22) [1971Gel] Geld, P.V., Kostina, T.K., Baum, B.A., Kurochkin, K.T., “Thermodynamic Characteristics of the Dissolution of Hydrogen in Binary Alloys of Fe, Co, Ni, and Cr with Si”, Russ. J. Phys. Chem., 45(8), 1134–1136 (1971), translated from Zh. Fiz. Khim., 45(8), 1999–2003 (1971) (Experimental, Thermodyn., 2) [1971Kos] Kostina, T.K., Baum, B.A., Kurochkin, K.T., Geld, P.G., “Solubility of Hydrogen in Liquid of Iron-Silicon Alloys”, Russ. J. Phys. Chem., 45(4), 453–455 (1971), translated from Zh. Fiz. Khim., 45(4), 813–816 (1971) (Experimental, Phase Relations, Thermodyn., 13) [1971Pet] Petrushevskiy, M.S., Geld, P.V., Baum, B.A., Kostina, T.K., “Calculation of the Solubility of Hydrogen in Fe-Si and Mn-Si Melts”, Russ. Metall., (2), 38–42 (1971), translated from Izv. Akad. Nauk SSSR, Met., (2), 59–64 (1971) (Thermodyn., Experimental, Phase Relations, 13) [1971Rya] Ryabov, R.A., Saliy, V.I., Tesler, M.L., Geld, P.V., “Diffusion and Solubility of Hydrogen in Solid Solutions of the Fe-Si System” (in Russian) in “Metody Opred. Gazov v Metal. Splavakh”, Moscow, 77–79 (1971) (Experimental, Phase Relations, 6) [1972Ngi] Ngia, N., Yavoyskiy, V.I., Kosterev, L.B., Afanas’yev, M.I., “Hydrogen Solubility in Binary Iron-Base Alloys”, Russ. Metall., (4), 11–15 (1972), translated from Izv. Akad. Nauk SSSR, Met., (4), 18–22 (1972) (Experimental, Phase Relations, Thermodyn., 19) [1973Gel] Geld, P.V., Baum, B.A., Petrushevsky, M.S., Kostina, T.K., Kurochkin, K.T., “Solubility of Hydrogen in Melts of 3d-transition Metals with Silicon” (in Russian) in “Vzaimodeistvie Gazov s Metal.”, Trudi 3 Sov. Yaponskogo Simp. Fiz.-Khim. Osn. Met. Protsessov, Nauka, Moscow, 173–181 (1973) (Calculation, Review, Phase Relations, 10) [1974Boo] Boorstein, W.M., Pehlke, R.D., “Measurement of Hydrogen Solubility in Liquid Iron Alloys Employing a Constant Volume Technique”, Metall. Trans., 5(2), 399–405 (1974) (Calculation, Experimental, Phase Relations, 29) [1977Bes] Bester, H., Lange, K.W., “Hydrogen Solubility in Iron and in Liquid Fe-Mn, Fe-Cr, and Fe-Si Alloys” (in German), Stahl Eisen, 97, 1037–1039 (1977) (Thermodyn., Phase Relations, Review, 53) [1981Sch] Schuermann, E., Kaettlitz, W., “Equivalent Effect of the Alloying Elements on the Concentration- and Temperature-Dependent Hydrogen Solubility in Iron-Rich Ternary and Multicomponent Melts” (in German), Arch. Eisenhuettenwes., 52(8), 295–301 (1981) (Calculation, Experimental, Phase Relations, 20) [1984Fro] Frohberg, M.G., Anik, S., “The Prediction of Hydrogen Solubility in Binary Iron Melts” (in German), Arch. Eisenhuettenwes., 55(2), 45–48 (1984) (Calculation, Phase Relations, Thermodyn., 20) [1988Kim] Kimura, T., Matsui, H., Kimura, H., “Effect of Hydrogen in the Mechanical Properties of Iron Based Alloys” in “Strength of Metals and Alloys”, Proc 8th Int. Conf. ISCMA, Pergamon Press, Oxford, 541–546 (1988) (Experimental, Mechan. Prop., 5) [1990San] San Martin, A., Manchester, F.D., “The Fe-H (Iron-Hydrogen) System”, Bull. Alloys Phase Diagrams, 11(2), 173–184 (1990) (Phase Diagram, Phase Relations, Review, Thermodyn., 86) [1999Din] Ding, X., Fan, P., Wang, W., “Thermodynamic Calculation for Alloy System”, Metall. Mater. Trans B, 30B(2), 271–277 (1999) (Thermodyn., Theory, 17) [1999Eli] Eliaz, N., Fuks, D., Eliezer, D., “A New Model for the Diffusion Behaviour in Metallic Glasses”, Acta Mater., 47(10), 2981–2989 (1999) (Theory, Transport Phenomena, Interface Phenomena, 47) [1999Liu] Liu, Z.-K., Chang, Y.A., “Thermodynamic Assessment of the Al-Fe-Si System”, Met. Mat. Trans. A, 30A(4), 1081–1095 (1999) (Thermodyn., Assessment, Phase Diagrams, Phase Relations, 56) [2003Fuk] Fukai, Y., Mori, K., Shinomiya, H., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys under High Hydrogen Pressures”, J. Alloy Compd., 348, 105–109 (2003) (Phase Diagram, Phase Relations, Experimental, 42) DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–Si [2006Ela]

[Mas2] [V-C2]

Landolt-Börnstein New Series IV/11D4

7

Elanski, D., Lim, J.-W., Mimura, K., Isshiki, M., “Impurity Removal from Fe, Cr, Ti, and V Metals by Hydrogen Plasma Arc Melting and Thermodynamic Estimation of Hydride and Sulﬁde Formation”, J. Alloys Compd., 421, 209–216 (2006) (Thermodyn., Experimental, Calculation, Phase Relations, 8) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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DOI: 10.1007/978-3-540-78644-3_10 # Springer 2008

Fe–H–V

1

Iron – Hydrogen – Vanadium Pierre Perrot

Introduction Vanadium metal inside a bcc structure is a promising hydrogen storage material with a high capacity because it can absorb hydrogen up 50 at.% under 0.1 MPa of hydrogen pressure at temperature not higher than 400°C [2002Yuk]. Unfortunately, hydrogen is hardly released and iron makes easier the hydrogen release. Most investigations have been directed towards the solubility of H in Fe-V melts. The main experimental results are gathered in Table 1. Binary Systems The Fe-H diagram under 0.1 MPa H2 is accepted from [1990San]. The Fe-H system has been carefully investigated by [2003Fuk] up to 10 GPa of hydrogen pressure and 1500°C. The hydrogen solubility in vanadium under pressures lower than 0.1 MPa was measured by [1938Kub] and an equilibrium diagram under 0.1 MPa H2 and up to 425°C was proposed by [1982Smi] and reproduced by [Mas2], diagram accepted in the present report. An extension of the H-V diagram up to the vanadium melting point was presented by [1992Oka], but this diagram cannot be accepted, because too much thermodynamically improbable features are involved. A H-V phase under 5 GPa of H2 was proposed by [2005Fuk]. The Fe-V system, is accepted from the assessment of [1984Smi] reproduced in [Mas2]. Solid Phases The solid phases are presented in Table 2. Vanadium may dissolve up to 50 at.% H above 170°C under 0.1 MPa of hydrogen pressure. Below 175°C, vanadium hydrides, namely β1, β2, γ and δ are formed. No ternary hydrides are known. Isothermal Sections The hydrogen solubility in α(Fe,V) alloys investigated by [1954Kri] from 411 to 900°C, was found to decrease with the increase of temperature and vanadium content of the alloy. The same trend was observed α alloys by [1974Egu]. The existence of a minimum in the hydrogen solubility on Fe-V alloy is thus probable. In the liquid state [1962Yak, 1981Sch], the hydrogen solubility in (Fe,V) alloys increases with increasing the V content. The hydrogen solubility in Fe-V alloys (< 25 at.% V) between 1550 and 1650°C is shown in Fig. 1. Thermodynamics The Wagner ﬁrst order interaction parameter, deﬁned by eH(V) = {∂ log10 fV/∂ (% V)} where (% V) represents the vanadium content of the alloy expressed in mass% with fV = (% V in pure iron)/(% V in the alloy), has been early experimentally determined at eH(V) = – 0.0074 ± 0.0001 between 1500 and 1600°C [1964Gun] and as eH(V) = 0.0087 – (28.9/T ) between 1550 and 1700°C [1967Ban]. An expression of the interaction coefﬁcient εH(V) deﬁned by: εH(V) = {∂ ln γV/∂ xV} where xV is the mole fraction of V in the liquid alloy and γV = (xV in pure iron)/(xV in the alloy) has been proposed by [1981Sch]: εH(V) = 0.2419 – (1704/T ) between 1550 and 1650°C for less than 20 at.% V in agreement with the preceding relation. In solid (V,Fe) alloys (< 1 at.% Fe) εH(Fe) = 4.8 at 927°C [1999Bal], which means that Fe decreases the H solubility in V, in agreement with the observation of [1974Egu].

Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

2

Fe–H–V

Notes on Materials Properties and Applications Hydrogen plays an important role in environmental embrittlement of Fe-V alloys. These alloys may be hardened or softened by hydrogen depending on the temperature and compositions [1988Kim] whereas high purity iron is always softened by hydrogen. Vanadium absorbs easily hydrogen [2002Yuk]. At 70°C, the isobaric plateau forms under 0.1 Pa of hydrogen pressure, so that hydrogen is not easily released. The presence of 3 at.% Fe raises the plateau up to 1 Pa of hydrogen pressure. Miscellaneous Hydrogen pick-up lowers the superconducting transition of Fe-V alloys [1979Ohl, 1981Ohl] and increases the saturation magnetization [2002Uzd]. In non magnetic Fe-V alloys (< 20 at.% Fe), absorption of H generates local magnetic moments and a superparamagnetic contribution. H follows V in Fe-V alloys and the H distribution in rapidly quenched alloys is correlated with Fe segregation [2001Hom], a result which is in agreement with the decreasing of H solubility when the iron content of the alloy increases.

Table 1.

Investigations of the Fe-H-V Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1954Kri]

Hydrogen solubility measurements in solid alloys

400–900°C, < 50 at.% V, 0.1 MPa of H2 pressure

[1962Yak]

Hydrogen solubility measurements in liquid alloys

1560°C, < 10 mass% V, 0.1 MPa of H2 pressure

[1964Gun]

Hydrogen solubility in liquid alloys by the hot volume method

1500–1650°C, < 35 mass% V, 0.1 MPa of H2

[1967Ban]

Hydrogen solubility measurements in liquid alloys

1548–1672°C, < 60 mass% V, 0.1 MPa of H2

[1974Egu]

Hydrogen solubility measurements in solid Fe-V alloys

600–1200°C, < 10 at.% Fe, 0.1 MPa of H2 pressure

[1979Ohl, 1981Ohl]

Cp measurements, Cu-tabletting method

5–15 K, V2H, VH, VH2, V0.9Fe0.1Hn (n < 1)

[1981Sch]

Hydrogen solubility measurements in liquid alloys

1550–1650°C, < 25 at.% V, 0.1 MPa of H2 pressure

[1988Kim]

Hardness measurements

< 5 mass% V

[1992Ost]

Mössbauer at 4.2 K

Magnetic behavior

[1999Bal]

Hydrogen solubility measurements in solid Fe-V alloys

927°C, < 1 at.% Fe, 0.1 MPa of H2 pressure

[2001Hom]

Tritium radioluminography, X-ray dispersive micrography

V0.95Fe0.05Hn, H distribution in alloys

[2002Uzd]

Faraday’ balance

Saturation magnetization measures

[2002Yuk]

Coulometric titration, hydrogen absorption measurements

V0.97Fe0.03Hn

DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–H–V Table 2.

3

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

α, (αδFe,V) (δFe) 1538–1394 (αFe) < 912 (V) < 1910

cI2 Im 3m W

a = 293.15

1394°C [Mas2]

a = 286.65

at 25°C [Mas2]

a = 302.40

pure V at 25°C [Mas2] (A2 structure) dissolves up to 50 at.% H above 220°C [1982Smi] > 180, limit of H solubility into V under 0.1 MPa H2 [1982Smi]

a = 303.7 (γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [Mas2] dissolves up to 1.3 at.% V at 1180°C

σ, FeV < 1252

tP30 P42/mnm σCrFe

a = 886.5 to 901.5 c = 460.5 to 464.2

29.6 to 60.1 at.% V [1984Smi]

β2, V2H (h) < 205

tF6 (?)

a ≈ 447 c ≈ 300

31 to 50 at.% H [1982Smi]

a = 600.12 ± 0.03 c = 661.88 ± 0.09

at 28°C [V-C2]

mC6 C2/m AuTe2 or mC6 Cm V 2H

a ≈ 447 b ≈ 300 c ≈ 447 β ≈ 92° a = 445.66 ± 5 b = 300.22 ± 2 c = 447.60 ± 5 β = 95.61 ± 1°

31 to 45 at.% H [1982Smi] No superconductivity [1981Ohl]

δ, V3H2 < – 70

mC10

a ≈ 452 b ≈ 302 c ≈ 692 β ≈ 77°

40 at.% H [1982Smi]. Structure closely related to β1, V2H. Probably ordered β1, V2H.

VH2 < – 15

cF12 Fm 3m CaF2

a = 427.1

< – 15°C under 0.1 MPa H2 [1982Smi] Superconductor [1981Ohl]

or tI24 I41/amd V 2H β1, V2H (r) < 175

Landolt-Börnstein New Series IV/11D4

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at 28°C [V-C2]

DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

4

Fe–H–V

Fig. 1. Fe-H-V. Hydrogen solubility in liquid Fe-V alloys under 0.1 MPa H2

DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–H–V References [1938Kub] [1954Kri]

[1962Yak]

[1964Gun]

[1967Ban] [1974Egu]

[1979Ohl]

[1981Ohl]

[1981Sch]

[1982Smi]

[1984Smi] [1988Kim]

[1990San]

[1992Oka] [1992Ost]

[1999Bal]

[2001Hom]

[2002Uzd]

Landolt-Börnstein New Series IV/11D4

5

Kubaschewki, O., “Absorption of Gases into the Metals” (in German), Z. Elektrochem., 44(2), 152–167 (1938) (Phase Relations, Review, 187) Krivoglaz, M.A., “Solubility in Homogeneous Alloys” (in Russian), Zh. Tekh. Fiz., 24(6), 1077–1089 (1954) (Crys. Structure, Experimental, Phase Relations, Experimental, Thermodyn., 11) Yakushev, A.M., Yavoiskii, V.I., “Effect of V and B on the Solubility of H in Liquid Fe” (in Russian), Izv. Vyssh. Ucheb. Zaved., Chern. Met., (1), 52–56 (1962) (Experimental, Phase Relations, 5) Gunji, K., Ono, K., Aoki, Y., “The Effect of Various Elements on the Solubility of Hydrogen in Liquid Pure Iron”, Trans. Natl. Res. Inst. Metals, 6(5), 209–213 (1964), translated from J. Jpn. Inst. Met., 28, 64–68 (1964) (Experimental, Phase Relations, Thermodyn., 7) Ban-ya, S., Fuwa, T., Ono, K., “Solubility of Hydrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 53(2), 101–116 (1967) (Experimental, Phase Relations, Thermodyn., 18) Eguchi, T., Morozumi, S., “Inﬂuence of Alloying Elements on the Solubility of Hydrogen in Vanadium” (in Japanese), J. Jpn. Inst. Met., 38, 1025–1030 (1974) (Experimental, Phase Relations, Thermodyn., 24) Ohlendorf, D., Wicke, E., Obermann, A., “Low Temperature Speciﬁc Heat and Magnetic Properties of Fe-V and V-Fe-H Alloys”, J. Phys. Chem. Solids, 40(11), 849–856 (1979) (Experimental, Thermodyn., Magn. Prop., 25) Ohlendorf, D., Severin, H.G., Wicke, E., “Heat Capacity Measurements of Pulverized Metal Hydrides between 1.5 and 15 K by Means of the Cu-Tabletting Method”, Z. Phys. Chem., 128(2), 137–146 (1981) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 9) Schuermann, E., Kaettlitz, W., “Equivalent Effect of the Alloying Elements on the Concentration- and Temperature-Dependent Hydrogen Solubility in Iron-Rich Ternary and Multicomponent Melts” (in German), Arch. Eisenhuettenwes., 52(8), 295–301 (1981) (Experimental, Phase Relations, Thermodyn., 20) Smith, J.F., Peterson, D.T., “The H-V (Hydrogen-Vanadium) System”, Bull. Alloys Phase Diagrams, 3(1), 55–60 (1982) (Phase Diagram, Phase Relations, Crys. Structure, Thermodyn., Review, #, 49) Smith, J.F., “The Fe-V (Iron-Vanadium) System”, Bull. Alloys Phase Diagrams., 5(2), 184–194 (1984) (Phase Diagrams, Phase Relations, Crys. Structure, Thermodyn., Review, #, 99) Kimura, T., Matsui, H., Kimura, H., “Effect of H in the Mechanical Properties of Iron Based Alloys” in “Strength of Metals and Alloys”, Proc. 8th Int. Conf. ISCMA, Pergamon Press, Oxford, 541–546 (1988) (Experimental, Mechan. Prop., 5) San Martin, A., Manchester, F.D., “The Fe-H (Iron-Hydrogen) System”, Bull. Alloys Phase Diagrams, 11(2), 173–184 (1990) (Phase Diagram, Phase Relations, Review, Thermodyn., 86) Okamoto, H., “H-V (Hydrogen-Vanadium)”, J. Phase Equilib., 13(6), 679 (1992) (Phase Diagram, Phase Relations, Review, 6) Ostrasz, A., Szuskiewicz, M., “Study of the Inﬂuence of Hydrogen Absorption on the Magnetic Properties of V-Fe-H Alloys by Low Temperature Mössbauer Spectrometry” Hyperfine Interactions, 68, 369–372 (1992) (Experimental, Magn. Prop., Electronic Structure, 6) Balabaeva, R.F., Vasil’eva, I.A., Sukhushina, I.S., Alekseev, I.V., “Thermodynamic Properties and Stability of Nb, Ti, Zr, Hf Intermetallics with Small Content of Transition Metals and Hydrogen (Nitrogen)” (in Russian), Zh. Fiz. Khim., 73(8), 1345–1347 (1999) (Calculation, Phase Relations, Thermodyn., 6) Homa, H., Satoh, H., Misawa, T., Ohnishi, T., “Observation of H Distribution in V-5 at.% Fe Alloys by Tritium Radioluminography”, J. Jpn. Inst. Met., 65(3), 163–166 (2001) (Crys. Structure, Experimental, 11) Uzdin, V., Labergerie, D., Westerhoff, K., Zabel, H., Hjovarsson, B., “Evolution of Atomic Magnetic Moments in Fe-V Multilayers with Hydrogen Loading”, J. Magn. Magn. Mat., 240, 481–484 (2002) (Experimental, Magn. Prop., 15) MSIT®

DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

6 [2002Yuk]

[2003Fuk]

[2005Fuk]

[Mas2] [V-C2]

Fe–H–V Yukawa, H., Teshima, H., Yamashita, D., Ito, S., Yamaguchi, S., Morinaga, M., “Alloying Effects on the Hydriding Properties of V at Low Hydrogen Pressures”, J. Alloys Compd., 337, 264–268 (2002) (Phase Relations, Thermodyn., Experimental, 7) Fukai, Y., Mori, K., Shinomiya, H., “The Phase Diagram and Superabundant Vacancy Formation in Fe-H Alloys under High Hydrogen Pressures”, J. Alloy Compd., 348, 105–109 (2003) (Phase Diagram, Phase Relations, Experimental, 42) Fukai, Y., “The Structure and Phase Diagrams of M-H Systems at High Chemical Potential, High Pressure and Electrochemical Synthesis”, J. Alloys Compd., 404/406, 7–15 (2005) (Phase Diagrams, Phase Relations, Thermodyn., Review, 40) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_11 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–La–Si

1

Iron – Lanthanum – Silicon Gabriele Cacciamani

Introduction Phase equilibria in the Fe-La-Si system are not well known: one of the boundary binary phase diagrams (La-Si) is not reported in literature and, in the ternary, only one isothermal section [1972Bod] and one sub-solidus section [1996Lia] have been experimentally investigated. A summary of the experimental works carried out on crystal structures, phase equilibria and thermodynamics is reported in Table 1. In the last ten years, attention of researchers has been mainly attracted by the peculiar properties of the La (Fe1–xSix)13 ternary phase which shows large magnetic moment, high magnetocaloric effect and giant isotropic magnetostriction. Binary Systems The Fe-La and Fe-Si binary systems are accepted from [Mas2]. La-Si phase diagram is not known, but six La-Si intermediate phases are known in literature. Solid Phases Crystal structure data of the Fe-La-Si phases are summarized in Table 2. Six ternary phases have been identiﬁed in the system. Four of them (τ1, τ2, τ5 and τ6) show appreciable solution ranges at constant La composition. The relation between τ5 and τ6 is still not clear. In previous studies one phase was found with NaZn13 cubic structure [1968Kry] and/or a pseudo-cubic variant with tetragonal symmetry [1969Bod]. More recently a tetragonal structure has been reﬁned and two separate composition ranges have been determined by [1994Tan] but temperature ranges of stability of the two phases and the transition mechanism between them have not been clearly identiﬁed La(FexSi1–x)2 has been cited by [1985Hul] while discussing structural properties of BaAl4 derivative Mooser-Pearson phases. Isothermal Sections The Fe-La-Si isothermal section at 600°C is reported in Fig. 1, based on the experimental results by [1972Bod] (also reported by [1992Rag]) modiﬁed in order to be consistent with the accepted binary systems. The sub-solidus section obtained by [1996Lia] is shown in Fig. 2. It was determined by analyzing samples homogenized at 900°C and then cooled down into the furnace. According to [2001Rag] it may be supposed that the equilibria reported are those stable at about room temperature. Thermodynamics The enthalpy of mixing of ternary Fe-La-Si alloys has been measured at 1645°C by calorimetry at Fe/Si equiatomic ratio, between 0 and 45 at.% La by [1983Esi] and at Fe/Si 1/3 ratio by [1982Esi]. The minimum enthalpy of mixing (–22.7 kJ·mol–1) was found at Fe/Si equiatomic ratio and 30 at.% La. Notes on Materials Properties and Applications La(FexSi1–x)2 is a Pauli paramagnet [1974Nar] with a temperature-independent susceptibility of about 3·10–6 emu·g–1. LaFe2Si2 is also a Pauli paramagnet. Low temperature magnetic susceptibility has been measured by [1975Fel] while effective magnetic moment has been measured by [2000Ger]. Low temperature speciﬁc heat has been measured by [2003Svo, 2005Svo].

Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

2

Fe–La–Si

The by far most studied Fe-La-Si phase is La(Fe1–xSix)13 (τ6). It shows important magnetocaloric effect (MCE), a Curie temperature of about 242 K at x = 0.185 [2000Zha] and it is magnetically soft enough to be a magnetic refrigerant. The magnetic entropy change was studied by several authors: according to [2000Zha], at x = 0.185, TC = 242 K and ΔS = –3.2 J·(kg·K)–1 upon a 2 T magnetic ﬁeld; according to [2001Hu], at x = 0.123, TC = 208 K and ΔS reaches –19.2 J·(kg·K)–1 under a ﬁeld of 5 T, which exceeds that of most other materials with a reversible magnetic transition in the same temperature range. Magnetic entropy change at various compositions has been also investigated by [2002Wen]. Thermal expansion coefﬁcient has been measured at x = 0.1 in the 85 to 413 K temperature range by [2003Cha1]: they found a variation from 3.6·10–6 to 1.2·10–5 K–1 between 143 and 233 K and no structural transformation in the same temperature range. In [2003Cha2] a theoretical discussion of the stability of the R(TX)13 NaZn13 type phases is presented while in [2006Fuj2] the entropy change mechanism is discussed. The interplay between structural and magnetic properties has been studied by [2003Wan]. Giant magnetovolume (MVE) and MCE effects in hydrogenated La(Fe1–xSix)13 have been investigated by [2002Fuj1, 2002Fuj2, 2002Fuj3, 2003Fuj, 2004Fuj2, 2005Fuj, 2005Man, 2006Fuk1, 2006Fuk2, 2006Med]. MVE has also been investigated by X-ray diffraction in high magnetic ﬁeld by [2004Fuj1]. Mössbauer spectroscopy was used by [2004Ham] in order to investigate the site preference of Fe/Si substitution and explain its effect on magnetic properties (Si substitution decreases magnetization while rising the Curie temperature). Structure and magnetic properties in melt-spun ribbons have been investigated by [2005Yan]. The effect of Fe partial substitution by Co has been considered by [2003Liu, 2005Ily] while partial substitution of La by Ce has been considered by [2006Fuj1].

Table 1.

Investigations of the Fe-La-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1967Ram]

XRD

La2FeSi3

[1968Kry]

XRD

cubic La(Fe1–xSix)13

[1969Bod]

XRD

pseudo-cubic La(Fe1–xSix)13

[1969May]

XRD, Mössbauer spectroscopy

La(FexSi1–x)2

[1970Bod]

XRD

LaFeSi

[1972Bod]

XRD, LOM

isothermal section at 600°C

[1978Ros]

XRD

LaFe2Si2

[1982Esi]

Calorimetry

1640°C, liquid at Fe/Si 3/1, up to 45 at.% La

[1983Esi]

Calorimetry

1645°C, liquid at Fe/Si 1/1, up to 45 at.% La

[1994Tan]

XRD

tetragonal La(Fe1–xSix)13

[1996Lia]

XRD

sub-solidus section

[1997Mor]

XRD, DTA

La(FexSi1–x)2

[1998Wel]

XRD

LaFeSi

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–La–Si Table 2.

3

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67 a = 357.3

(αFe) < 912

cI2 Im 3m W

Comments/References

connected to αFe in Fe-Si, dissolves up to 19.5 at.% Si at 1390°C [Mas2] dissolves up to 3.8 at.% Si [Mas2] at 915°C [Mas2]

a = 286.65 a = 286.0

connected to δFe in Fe-Si, dissolves up to 19.5 at.% Si at 1390°C [Mas2] at 10 at.% Si [V-C2]

(β’La)

cF4 Fm 3m Cu

a = 517

at 25°C, 2.0 GPa [Mas2]

(γLa) 918–865

cI2 Im 3m W

a = 426

[Mas2]

(βLa) 865–310

cF4 Fm 3m Cu

a = 530.3

[Mas2]

(αLa) < 310

hP4 P63/mmc αLa

a = 377.40 c = 1217.1

at 25°C [Mas2]

(δSi)

hP4 P63/mmc αLa

a = 380 c = 628

at 25°C, 16 GPa → 1 atm [Mas2]

(γSi)

cI16 Im 3m γSi

a = 663.6

at 25°C, 16 GPa [Mas2]

(βSi)

tI4 I41/amd βSn

a = 468.6 c = 258.5

at 25°C, 9.5 GPa [Mas2]

(αSi) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

at 25°C [Mas2]

α2, Fe-Si ≲ 1280

cP2 Pm 3m CsCl

α1, Fe-Si ≲ 1240

cF16 Fm 3m BiF3

10 to 22 at.% Si

a = 565

10 to 30 at.% Si [V-C2] (continued)

Landolt-Börnstein New Series IV/11D4

MSIT®

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

4

Fe–La–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

Fe2Si ∼1212–∼1040

hP6 P 3m1

a = 405.2 c = 508.5

[V-C2]

Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.6 c = 471.8

[V-C2]

FeSi < 1410

cP8 P213 FeSi

a = 451.7

[V-C2]

βFeSi2 (h) 1220–937

tP3 P4/mmm βFeSi2

a = 268.4 c = 512.8

69.5 to 73 at.% Si [V-C2]

αFeSi2 (r) < 982

oC48 Cmca αFeSi2

a = 986.3 b = 779.1 c = 783.3

[V-C2]

LaSi2 (h)

tI12 I41/amd Th2Si

a = 431.8 c = 1384

[V-C2]

LaSi2 (r)

oI12 Imma Gd2Si3

a = 427 b = 419 c = 1394

[V-C2]

LaSi

oP8 Pnma FeB

a = 840.4 ± 0.5

[V-C2]

La5Si4

tP36 P41212 Zr5Si4

a = 804 c = 1543

[V-C2]

La3Si2

tP10 P4/mbm U3Si2

a = 788.5 c = 443.4

[V-C2]

La5Si3

tI32 I4/mcm Cr5B3

a = 794.9 c = 1407

at La rich boundary

a = 795.0 c = 1404

at Si rich boundary [V-C2]

a = 406.2 ± 0.3 c = 7117.9 ± 0.5

[1970Bod]

a = 409.8 c = 713.3

(reﬁnement) [1998Wel]

* τ1, LaFeSi

tP6 P4/nmm Cu2Sb CeFeSi

b = 401.0 ± 0.3 c = 605.9 ± 0.3

(continued)

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–La–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

* τ2, La(FexSi1–x)2 (also denoted as La5Fe2Si8 or La2FeSi3)

hP3 P6/mmm AlB2

Lattice Parameters [pm]

a = 406.9 c = 410.1 a = 409.7 c = 433.1 a = 409.2 c = 437.0

5

Comments/References

x = 0.15–0.25 at x = 0.25 [1967Ram] at x = 0.15 [1967Ram] at x = 0.2 [1969May]

* τ3, LaFeSi2

oC16 Cmcm CeNiSi2

a = 418.4 ± 0.3 b = 1724 ± 1 c = 405.8 ± 0.3

[V-C2]

* τ4, LaFe2Si2 < 1547

tI10 I4/mmm BaAl4 (ThCu2Si2) CeGa2Al2

a = 405.3 c = 1015.3

[1978Ros]

a = 404.9 c = 1014.7

[1997Mor]

tI56 I4/mcm

a = 799.4 to 795.4 c = 1166.3 to 1172.0

at x = 0.25–0.38 [1996Lia]

a = 793.2 c = 1167.7

at x = 0.31, after annealing at 900°C (reﬁnement) [1994Tan]

a = 1148.7 to 1143.9 a = 1148.62 a = 1154.36

at x = 0.11–0.20 [1996Lia]

* τ5, La(Fe1–xSix)13(h?)

LaFe9Si4 (NaZn13 derivative) * τ6, La(Fe1–xSix)13(r)

cF112 Fm 3c NaZn13

a = 1147.86 a = 1152.89 a = 1143.4

Landolt-Börnstein New Series IV/11D4

MSIT®

at x = 0.19, T = 298 K (reﬁnement) at x = 0.19, T = 85 K (reﬁnement) sharp decrease of the lattice parameter at about 190 K [2003Cha2] at x = 0.11 and T = 193 K at x = 0.11 and T = 185 K (reﬁnement) [2003Wan] at x = 0.19 [2004Ham]

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

6

Fig. 1. Fe-La-Si.

Fe–La–Si

Isothermal section at 600°C

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–La–Si

Fig. 2. Fe-La-Si.

Landolt-Börnstein New Series IV/11D4

7

Sub-solidus section

MSIT®

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

8 References [1967Ram] [1968Kry]

[1969Bod]

[1969May] [1970Bod]

[1972Bod]

[1974Nar] [1975Fel]

[1978Ros]

[1982Esi]

[1983Esi]

[1985Hul] [1992Rag]

[1994Tan] [1996Lia]

[1997Mor]

[1998Wel]

Fe–La–Si

Raman, A., “Structural Data of Some Rare-Earth Alloys.”, Naturwissenschaften, 54, 560 (1967) (Crys. Structure, Experimental, 0) Krypyakevych, P.I., Zarechniuk, O.S., Gladyshevskiy, E.I., Bodak, O.I., “Ternary Compounds of the NaZn13-Type” (in German), Z. Anorg. Chem., 358, 90–96 (1968) (Crys. Structure, Experimental, Phase Relations, 26) Bodak, O.I., Gladyshevskiy, E.I., “Ternary Compounds of the NaZn13 and Related Types in the (La, Ce, Pr, Nd, Sm, Eu, Gd)-Ni-Si and (La, Ce)-(Fe, Co)-Si Systems”, Dop. Akad. Nauk Ukrain. RSR, Ser. A, Fiz-Mat. Tekh. Nauki, (12), 1125–1129 (1969) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 3) Mayer, I., Tassa, M., “Rare-Earth-Iron(Cobalt, Nickel)-Silicon Compounds”, J. LessCommon Met., 19, 173–177 (1969) (Crys. Structure, Experimental, 9) Bodak, O.I., Gladyshevskiy, E.I., Krypyakevych, P.I., “Crystal Structure of Ce-Fe Silicide and Similar Compounds” (in Russian), Zhur. Strukt. Kim., 11(2), 305–310 (1970) (Crys. Structure, Electronic Structure, Experimental, 20) Bodak, O.I., Gladyshevskiy, E.I., “The Lanthanum-Iron-Silicon System”, Visn. Lviv. Derzh. Univ., Ser. Khim., 14, 29–34 (1972) (Phase Diagram, Phase Relations, Crys. Structure, Experimental, 12) Narasimhan, K.S.V.L., Steinﬁnk, H., “Magnetic Investigations on AlB2 Type Structures”, J. Solid State Chem., 10, 137–141 (1974) (Crys. Structure, Experimental, Magn. Prop., 10) Felner, I., Mayer, I., Grill, A., Schieber, M., “Magnetic Ordering in Rare-earth Fe Silicides and Germanides of the RFe2X2 Type”, Solid State Commun., 16, 1005–1009 (1975) (Crys. Structure, Experimental, Magn. Prop., 17) Rossi, D., Marazza, R., Ferro, R., “Lattice Parameters of Some ThCu2Si2-Type Phases in Ternary Alloys of Rare Earths with Cobalt (or Iron) and Silicon (or Germanium)”, J. Less-Common Met., 58(2), 203–207 (1978) (Crys. Structure, Experimental, 10) Esin, Yu.O., Ermakov, A.F., Valishev, M.G., Gel`d, P.V., Levin, E.S., “Enthalpies of Formation of the Liquid Alloys of the System Fe3Si with Yttrium and Lanthanum” (in Russian), Zh. Fiz. Khim., 56(10), 2619–2620 (1982) (Experimental, Thermodyn., 5) Esin, Yu.O., Ermakov, A.F., Valishev, M.G., Geld, P.V., Levin, E.S., “Enthalpy of Formation of Liquid Alloys of Iron Monosilicide with Yttrium and Lanthanum”, Russ. Metall., (3), 49–50 (1983) (Experimental, Thermodyn., 5) Hullinger, F., “Mooser-Pearson Phases Among the BaAl4-Type Derivations”, Helv. Phys. Acta, 58, 216–225 (1985) (Crys. Structure, Review, 47) Raghavan, V., “The Fe-La-Si (Iron-Lanthanum-Silicon) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 6B, 936–939 (1992) (Crys. Structure, Phase Diagram, Phase Relations, Review, 10) Tang, W.-H., Liang, X.-K., Chen, X.-L., Rao, G.-H., “Structure of LaFe9Si4 Intermetallic Compound”, J. Appl. Phys., 76(7), 4095–4098 (1994) (Crys. Structure, Experimental, 13) Liang, J., Rao, G., Tang, W., Zhao, Y., Guo, Y., Yan, X., Zhang, Y., Cheng, X., Xie, S., Chen, X., Yu, Y., Tian, J., Liang, J., “Phase Relations of R-T-M Ternary System, Crystal Structure and Magnetic Properties of R(T, M) Compounds (R = Light Rare Earth; T = Co, Fe; M = Al, Si) (I)”, Prog. Nat. Sci., 6(6), 641–650 (1996) (Experimental, Phase Diagram, Phase Relations, 6) Morozkin, A.V., Seropegin, Yu.D., Gribanov, A.V., Barakatova, J.M., “Analysis of the Melting Temperatures of RT2 Compounds (MgCu2 structure) (R = Rare Earth, T = Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) and RT2X2 Compounds (R = La, Ce, Sm, Er; T = Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Pt; X = Si, Ge)”, J. Alloys Compd., 256, 175–191 (1997) (Crys. Structure, Experimental, Thermodyn., 74) Welter, R., Ijjaali, I., Venturini, G., Malaman, B., “X-Ray Single Crystal Reﬁnement on Some CeFeSi Type RTX Compounds (R = RE Elements; T = Mn, Fe, Co, Ru; X = Si, Ge). Evolution of the Chemical Bonds”, J. Alloys Compd., 265, 196–200 (1998) (Crys. Structure, Experimental, 16)

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–La–Si [2000Ger]

[2000Zha]

[2001Hu]

[2001Rag] [2002Fuj1]

[2002Fuj2]

[2002Fuj3]

[2002Wen]

[2003Cha1]

[2003Cha2]

[2003Fuj]

[2003Liu]

[2003Svo]

[2003Wan]

[2004Fuj1]

[2004Fuj2]

Landolt-Börnstein New Series IV/11D4

9

Gerasimov, E.G., Gavilko, V.S., Zaikov, N.K., Podgornykh, S.M., Korolev, A.V., Pirogov, A.N., “Magnetic State of Fe Atoms in La(Fe1–xVx)2Si2 (0 ≤ x ≤ 0.5) Compounds”, Phys. Met. Metallogr., 90(3), 231–238 (2000) (Crys. Structure, Experimental, Magn. Prop., 7) Zhang, X.X., Wen, G.H., Wang, F.W., Wang, W.H., Yu, C.H., Wu, G.H., “Magnetic Entropy Change in Fe-Based Compound LaFe10.6Si2.4”, Appl. Phys. Lett., 77(19), 3072–3074 (2000) (Crys. Structure, Experimental, Magn. Prop., 17) Hu, F.-X., Shen, B.-G., Sun, J.-R., Cheng, Z.-H., Rao, G.-H., Zhang, X.-X., “Inﬂuence of Negative Lattice Expansion and Metamagnetic Transition on Magnetic Entropy Change in the Compound LaFe11.4Si1.6”, Appl. Phys. Lett., 78(23), 3675–3677 (2001) (Crys. Structure, Experimental, Magn. Prop., 22) Raghavan, V., “Fe-La-Si (Iron - Lanthanum - Silicon)”, J. Phase Equilib., 22(2), 158–159 (2001) (Crys. Structure, Phase Relations, Review, 4) Fujita, A., Fujieda, S., Fukamichi, K., “Giant Magnetovolume and Magnetocaloric Effects in Itinerant-Electron Metamagnetic La(FexSi1–x)13 Compounds” (in Japanese), Materia Japan, 41, 269–275 (2002) (Phys. Prop., 47) Fujita, A., Fujieda, S., Fukamichi, K., Mitamura, H., Goto, T., “Itinerant-Electron Metamagnetic Transition and Large Magnetovolume Effects in La(FexSi1–x)13 Compounds”, Phys. Rev. B: Condens. Matter, 65(1), 014410–1–6 (2002) (Experimental, Magn. Prop., Phase Relations, 31) Fujieda, S., Fujita, A., Fukamichi, K., “Large Magnetocaloric Effect in La(FexSi1–x)13 Itinerant-Electron Metamagnetic Compounds”, Appl. Phys. Lett., 81(7), 1276–1278 (2002) (Experimental, Magn. Prop., Thermodyn., 17) Wen, G.H., Zheng, R.K., Zhang, X.X., Wang, W.H., Chen, J.L., Wu, G.H., “Magnetic Entropy Change in LaFe13–xSix Intermetallic Compounds”, J. Appl. Phys., 91(10), 8537–8539 (2002) (Crys. Structure, Experimental, Phys. Prop., 14) Chang, H., Liang, J.-K., Shen, B.-G., Yang, L.-T., Wang, F., Chen, N.-X., Rao, G.-H., “Thermal Expansion Coefﬁcients of LaFe11.7Si1.3”, J. Phys. D: Appl. Phys., 36(2), 160–163 (2003) (Crys. Structure, Experimental, Magn. Prop., Phys. Prop., 11) Chang, H., Chen, N., Liang, J., Rao, G., “Theoretical Study of Phase Forming of NaZn13 Type Rare-Earth Intermetallics”, J. Phys.: Condens. Matter, 15, 109–120 (2003) (Calculation, Crys. Structure, Phase Relations, 28) Fujita, A., Fujieda, S., Hasegawa, Y., Fukamichi, K., “Itinerant-Electron Metamagnetic Transition and Large Magnetocaloric Effects in La(FexSi1–x)13 Compounds and Their Hydrides”, Phys. Rev. B: Condens. Matter, 67(10), 104416–1–12 (2003) (Experimental, Magn. Prop., Phase Relations, Thermodyn., 38) Liu, X.B., Altounian, Z., “Effect of Co Content on Magnetic Entropy Change and Structure of La(Fe1–xCox)11.4Si1.6”, J. Magn. Magn. Mater., 264, 209–213 (2003) (Crys. Structure, Experimental, Magn. Prop., Thermodyn., 12) Svoboda, P., Vejpravova, J., Honda, F., Santava, E., Schneeweiss, O., Komatsubara, T., “The Analisis of the Speciﬁc Heat of RFe2Si2 Compounds”, Physica B, 328(1–2), 139–141 (2003) (Crys. Structure, Experimental, Thermodyn., 6) Wang, F., Wang, G.-J., Hu, F., Kurbakov, A., Shen, B., Cheng, Zh., “Strong Interplay Between Structure and Magnetism in the Giant Magmetocaloric Intermetallic Compound LaFe11.4Si1.6: a Neutron Diffraction Study”, J. Phys.: Condens. Matter, 15(30), 5269–5278 (2003) (Crys. Structure, Experimental, Phys. Prop., 24) Fujita, A., Fukamichi, K., Koyama, K., Watanabe, K., “X-ray Diffraction Study in High Magnetic Fields of Magnetovolume Effect in Itinerant-Electron Metamagnetic La (Fe0.88Si0.12)13 Compound”, J. Appl. Phys., 95(11), 6687–6689 (2004) (Crys. Structure, Experimental, Magn. Prop., Phase Relations, Phys. Prop., 20) Fujieda, S., Hasegawa, Y., Fujita, A., Fukamichi, K., “Thermal Transport Properties of Magnetic Refrigerants La(FexSi1–x)13 and Their Hydrides, and Gd5Si2Ge2 and MnAs”, J. Appl. Phys., 95(5), 2429–2431 (2004) (Crys. Structure, Experimental, Phase Relations, Transport Phenomena, 20)

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DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

10 [2004Ham]

[2005Fuj]

[2005Ily]

[2005Man]

[2005Svo]

[2005Yan]

[2006Fuj1]

[2006Fuj2]

[2006Fuk1]

[2006Fuk2]

[2006Med]

[Mas2] [V-C2]

Fe–La–Si Hamdeh, H.H., Al-Ghanem, H., Hikal, W.M., Taher, S.M., Ho, J.C., Anh, D.T.K., Thuy, N.P., Duc, N.H., Thang, P.D., “Mössbauer Spectroscopic Evaluation of Chemical and Electronic Distributions in La(Fe0.81Si0.19)13”, J. Magn. Magn. Mater., 269(3), 404–409 (2004) (Crys. Structure, Experimental, Magn. Prop., 17) Fujita, A., Fukamichi, K., “Control of Large Magnetocaloric Effects in Metamagnetic La (FexSi1–x)13 Compounds by Hydrogenation”, J. Alloys Compd., 404–406, 554–558 (2005) (Crys. Structure, Experimental, Interface Phenomena, Magn. Prop., 30) Ilyn, M., Tishin, A.M., Hu, F.X., Gao, J., Sun, J.R., Shen, B.G., “Magnetocaloric Properties of the LaFe11.7Si1.3 and LaFe11.2Co0.7Si1.1 Systems”, J. Magn. Magn. Mater., 290–291(1), 712–714 (2005) (Experimental, Magn. Prop., Phase Relations, Thermodyn., 12) Mandal, K., Gutﬂeisch, O., Yan, A., Handstein, A., Mueller, K.-H., “Effect of Reactive Milling in Hydrogen on the Magnetic and Magnetocaloric Properties of LaFe11.57Si1.43”, J. Magn. Magn. Mater., 290–291(1), 673–675 (2005) (Experimental, Magn. Prop., Phase Relations, Thermodyn., 8) Svoboda, P., Mihalik, M., Mihalik, M., Vejpravova, J., Rusz, J., “Speciﬁc Heat Analysis of Heavy REFe2Si2 Compounds”, J. Magn. Magn. Mater., 290–291(1), 609–611 (2005) (Crys. Structure, Experimental, Magn. Prop., Thermodyn., 6) Yan, A., Mueller, K.-H., Gutﬂeisch, O., “Structure and Magnetic Entropy Change of MeltSpun LaFe11.57Si1.43 Ribbons”, J. Appl. Phys., 97(3), 036102–1–3 (2005) (Crys. Structure, Experimental, Magn. Prop., Thermodyn., 17) Fujieda, S., Fujita, A., Fukamichi, K., Hirano, N., Nagaya, S., “Large Magnetocaloric Effects Enhanced by Partial Substitution of Ce for La in La(Fe0.88Si0.12)13 Compound”, J. Alloys Compd., 408–412, 1165–1168 (2006) (Crys. Structure, Experimental, Magn. Prop., 18) Fujita, A., Fukamichi, K., “Enhancement of Isothermal Entropy Change Due to Spin Fluctuations in Itinerant-Electron Metamagnetic La(Fe0.88Si0.12)13 Compound”, J. Alloys Compd., 408–412, 62–65 (2006) (Experimental, Magn. Prop., Thermodyn., 21) Fukamichi, K., Fujita, A., Fujieda, S., “Large Magnetocaloric Effects and Thermal Transport Properties of La(FeSi)13 and Their Hydrides”, J. Alloys Compd., 408–412, 307–312 (2006) (Crys. Structure, Electr.Prop., Experimental, Magn. Prop., Thermodyn., 30) Fukamichi, K., Fujita, A., Fujieda, S., “Application of Large Magnetocaloric Effects in Itinerant-Electron Metamagnets to Cooling Systems”, Mat. Sci. Forum, 512, 137–144 (2006) (Experimental, Magn. Prop., Thermodyn., 20) de Medeiros, L.G. Jr., de Oliveira, N.A., “Magnetocaloric Effect in La(FexSi1–x)13 Doped with Hydrogen and Under External Pressure”, J. Alloys Compd., 424(1–2), 41–45 (2006) (Calculation, Crys. Structure, Magn. Prop., Thermodyn., 18) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_12 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mg–O

1

Iron – Magnesium – Oxygen Nathalie Lebrun, Olga Fabrichnaya

Introduction Knowledge of the phase equilibria in the Fe-Mg-O system is important in the ﬁelds of ceramics, metallurgy and petrology. For example, magnesiowüstite (Fe,Mg)O is a constituent of the lower mantle of the Earth. In geophysics, phase equilibria between magnesiowüstite and other minerals and their elastic properties at high pressures are important for the calculation of the seismic proﬁle of the Earth. Interest in this ternary system also arises from the electrical and magnetic properties of magnesioferrite MgFe2O4 (spinel structure). In addition, the melting behavior of compositions in the MgO-FeO-Fe2O3 region provide a basis for evaluating the performance of magnesite bricks subjected to iron-oxide attack in steel making furnaces. The Fe-Mg-O ternary system has been studied extensively, in particular in the FeO-MgO-Fe2O3 region. [1931Rob] ﬁrst attempted to determine the phase relationships in FeO-MgO-Fe2O3 from dissociation measurements in air at one atmosphere and below 1000°C. The temperature was measured using an optical pyrometer and the compositions were determined by chemical analysis. [1954Ric] investigated the reversible dissociation of ferric oxide in the FeO-MgO-Fe2O3 region as a function of temperature in air between 800 and 1500°C. Thermogravimetry was used to determine the loss of oxygen and the composition was checked by Xray and microscopic analysis. [1955Woo] also investigated the phase relations in this ternary subsystem in air from 700 up to 1650°C using the same experimental procedure as [1954Ric]. [1960Pal] studied the dissociation as a function of pressure (1 to 0.01 bar) and temperature (1000 to 1300°C) in the ferrite region. [1962Phi] equilibrated samples in sealed tubes, which were then quenched and the resulting phase assemblages studied by X-ray analysis and microscopic examinations. Isothermal sections between 1400 to 1800°C were constructed from the results that were then used to draw the liquidus surface. However, the oxygen partial pressure in these experiments was not known. [1965Kat] used thermogravimetry at 1160°C and various oxygen pressures and also constructed an isothermal section at 1160°C. [1965Ole] determined the isothermal section for 1400°C from oxidation measurements made at various pressures from 1 to 10–13 bar. Using X-ray analysis and microscopic investigation, they studied the concentration dependence of the lattice parameter of magnesioferrite solid solutions. [1967Spe] also used thermogravimetry to determine phase equilibria at 1300°C as function of the fugacity of oxygen. [1968Rei] studied the equilibria between the solid phases and oxygen by thermogravimetry in air and temperatures up to 1000°C. [1970Ber] established the phase relationships at 850°C under various oxygen pressures using chemical analysis and X-ray diffraction. [1980Shi] established a partial isothermal section at 1000°C by measuring the emf of galvanic cells incorporating a solid electrolyte. [1961Phi] used a quenching method to determine the phase relationships in MgO-Fe2O3 in air at temperatures between 1600 and 1800°C. This method consisted of annealing the samples in air in the furnace until equilibrium was established between the gaseous and solid phases. The samples were then quenched to room temperature. Compositions were deduced from X-ray analysis and microscopic examination. The MgO rich region of MgO-Fe2O3 system was studied by high-temperature XRD by [2003Hon], in air and temperatures between 25 and 1400°C. [1935Bow] ﬁrst reported measurement of the refractive index of FeO-MgO solid solutions revealing a continuous solid solution, named magnesiowüstite. [1961Sch1] measured the solidus curve of this solid solution in air between 1520 and 1750°C. [1953Sha] determined the activities of MgO and FeO in magnesiowüstite solid solutions at 600, 900 and 1060°C and measured their lattice parameters using X-ray diffraction. A continuous variation in the lattice parameter was observed in agreement with [1970Aub, 1970Ber]. [1997Byg] used EDX to study cation diffusivities in the MgO-FeO system over the temperature range 1200–1330°C in order to understand the interdiffusion of iron and magnesium in the oxide lattice. [1961Sch2] established oxidation curves for different mixtures of Fe2O3 and MgO at 800, 900 and 1000°C from which the activities of MgO and FeO were deduced along with an isothermal section of the Fe-Mg-O system at 900°C. [1957Flo] investigated the effect of MgO on the oxidation state of iron oxide at 1400–1500°C. [1962Hah] determined the activities of FeO in magnesiowüstite solid solutions between Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

2

Fe–Mg–O

1100 and 1300°C. The oxide samples were equilibrated with pure metallic iron in atmospheres of known oxygen partial pressures, and the compositions were checked by X-ray analysis. [1962Hah] calculated the activity of MgO. [1965Tre1] calculated the activities of Fe3O4 and MgFe2O4 and γFe2O3 by a statistical method. [1965Tre2] calculated the activity of Fe3O4 by consideration of phase equilibria involving magnesiowüstite, accepting the activity of FeO in magnesiowüstite from the experimental data of [1963Gor]. [1970Aub, 1970Ber, 1972Bal] determined the activities of FeO at 850°C from oxidation data obtained from chemical analysis. [1983Dav] calculated the activities of MgO and FeO using regular and subregular thermodynamic models for the mixing of the two components. [1987Sre] studied the activity-composition relationships of the magnesiowüstite solid solution in equilibrium with metallic iron in the temperature range 777–1127°C. [1970Ber, 1980Shi] estimated the activities of Fe3O4 and MgFe2O4 in the spinel solid solution from oxidation measurements. Using thermoelectric coefﬁcient measurements, [1984Tre] determined the cation distributions from 600 to 1300°C and calculated the activities of Fe3O4 and MgFe2O4. [2002Kat] determined activities in spinel solid solutions by an emf method at 887–1117°C. [1984Dob] calculated the activities in the Fe-Mg-O system from oxygen activity data. [1966Ole] evaluated the thermodynamic properties of solid solutions with the spinel structure, MgxFe3–xO4 (x ≤ 1), from phase equilibrium data. [1974Sah] studied the reduction of magnesiowüstite over the temperature range 1050–1350°C using CO2/H2 mixtures. [1977Tri] established a schematic O2 partial pressure-composition phase diagram for the Fe3O4-MgFe2O4 system at 1000°C consistent with [1975Zal]. [1978Lyk] determined the fugacity from FeO to Fe0.504Mg0.496O1.13 at 800, 900, 1000 and 1100°C. [1988Lue] studied the oxidation kinetics of Mg0.99Fe0.01O in air over the temperature range 873 to 1176°C. [1988Rom] studied the reversible decomposition of MgFe2O4 in an (Fe,Mg)O solid solution during cooling and heating in an inert atmosphere and in air. [1967Guz] studied the system (MgO)0.07MgFe2On (3.06 ≤ n ≤ 4.00) by the emf method using a solid electrolyte and calculated the thermodynamics of the formation of magnesium ferrite from its component oxides at 900–1100°C under standard conditions. [1958Bry] measured the equilibrium between Fe3+ and Fe2+ ions in wüstite containing various amounts of magnesium oxide at various partial pressures (10–6.71 to 10–3.1 bar) and 1400°C. Using both calorimetric and volumetric methods, [1967Alc] measured the variation in the Fe3+/Fe2+ ratio in magnesiowüstites containing 0–20 mol% of iron oxide, which had been brought to equilibrium with known oxygen pressures. The temperature range for the measurements was 900–1200°C. [1965Rig] and [1969Bla] used microscopy to study the diffusion of FeO in MgO. [1963Gor] investigated the dependence on composition of the dissociation pressure of oxygen in spinel solid solutions MgxFe3–xO4 (x ≤ 0.5) at temperatures between 800 and 1100°C and determined the free energy of formation of MgxFe3–xO4 (x ≤ 0.5) solid solutions at 860, 960 and 1060°C. [1978Cor] studied the redox behavior of Fe2+ in solid solutions with MgO by ESR and X-ray diffraction techniques. [1972Rez] measured the electrical conductivity of MgFe2O4 at 27°C. [1974Kra] measured the magnetization of a single crystal of magnesiowüstite, which was prepared by annealing MgO single crystals in magnesiowüstite powder containing (Fe)/(Fe+Mg) = 0.22 at 1400°C for 15 days in a CO/CO2 atmosphere (p(O2) = 10–9 bar). A Foner-type vibrating sample magnetometer was used to measure the magnetization. The Fe-Mg-O ternary system was reviewed by [1964Lev, 1981Rot, 1989Rag1, 2000Leb]. Using the sublattice model, subsolidus phase equilibria in the FeO-MgO-Fe2O3 system were calculated by [1998Fab]. The solidus and liquidus of the FeO-MgO system were calculated by [2000Fab] using the same model. [1993Wu] preformed a critical assessment and optimization of the thermodynamic properties and phase diagram of the FeO-MgO system using the modiﬁed quasichemical model for the liquid phase and simple polynomial excess Gibbs energy terms for magnesiowüstite. The modiﬁed quasichemical model for the liquid phase was also applied by [2004Jun1]. [2002Dec, 2004Jun1] were able to describe phase relations in the Fe-Mg-O system by modeling magnesiowüstite MgO-FeO-FeO1.5 using a simple polynomial expansion while the magnesioferrite (spinel) phase was modeled using the compound energy formalism. The thermodynamic assessment by [2004Jun1] reproduces all of the available thermodynamic and phase equilibrium data within their uncertainty limits. The Fe-Mg-O system is of interest for geological applications, and therefore, elastic and thermal properties and high temperature transformations have been studied at high temperature and pressures [2001And, 2001Dub, 2002Jac, 2002Zha, 2003Lin, 2004Kon, 2004Lev, 2005Wes, 2005Jac, 2006Kan1, 2006Kan2]. Table 1 lists the experimental and theoretical studies of the Fe-Mg-O system occurring after 1998. DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

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Binary Systems The Fe-Mg binary system is accepted from [Mas2]. The phase diagram is consistent with the version presented by [1982Kub] except for some small details; the γFe/δFe transition temperature ([1982Kub] at ∼ 1392°C, [Mas2] at ∼ 1356°C) and monotectic temperature ([1982Kub] at ∼ 1515°C, [Mas2] at ∼1526°C). Extensive miscibility gaps exist both in the liquid and solid states. The estimated solubility of liquid Mg in liquid Fe under 25 bar of argon is given by [1982Kub] as log(at.% Mg) = – 11.250/T(K) + 5.31. The solid solubility of Mg in solid Fe is negligible. The solubility of Fe in liquid Mg increases from 0.0026 at.% at the eutectic temperature of 650°C to ∼ 1.6 at.% at 1600°C. The Fe-O phase diagram is accepted from [Mas2]. The thermodynamic parameters of the Fe-O system have been assessed by [1991Sun] and [2002Dec]. Both thermodynamic assessments are in very good agreement with [Mas2]. The assessment of [2002Dec] is used in the work of [2004Jun1] reproducing most of experimental data in the Fe-Mg-O ternary system. The stoichiometric composition FeO is outside the range of wüstite. In the Fe rich part, wüstite coexists with (αFe) from 570 to 912°C, with (γFe) from 912 to 1371°C, and with the liquid from 1371 to 1424°C. In the oxygen rich part, it coexists with Fe3O4 between 570 and 1429°C, which are the temperature limits of its stable range. At high pressures, the Fe rich boundary shifts towards the composition of stoichiometric FeO and reaches a maximum value of x = 0.98 at 10 GPa, while with a further increase in pressure, x slightly decreases to a value of 0.96 at 20 GPa. At higher pressures, the wüstite composition remains practically constant [1984McC]. The Mg-O phase diagram was accepted from [1993Hal]. Periclase MgO is practically stoichiometric, and a very small amount of oxygen can be dissolved in solid and liquid Mg. Solid Phases FexO wüstite has a defect structure in which the ratio Fe/O deviates from simple stoichiometry [1965Kat]. For this reason, FeO is indicated in quotation marks throughout this assessment. The wüstite and MgO periclase form a continuous series of solid solutions (magnesiowüstite) [1931Rob, 1935Bow, 1945Jay, 1946Pet]. [1970Aub, 1970Ber, 1980Sim] measured the lattice parameter of magnesiowüstite at various compositions of MgO. The lattice parameter of “FeO” varies from 428.7 pm at its upper limit of oxidation to 431.0 pm at its lower limit. The results are consistent with [1953Sha]. The eutectoid decomposition temperature of magnesiowüstite is lowered with increasing Mg content [1968Rei, 1971Gur]. The calculated temperature of dissociation of magnesiowüstite with respect to composition as presented by [2004Jun1] is shown in Fig. 1. The non-stoichiometry in magnesiowüstite decreases with increasing Mg substitution [1970Ber, 1971Gur, 1987Sre]. [1970Ber] and [1977Tri] determined the solubility range of magnesiowüstite in the ternary system at 850°C and 1000°C in terms of the ratio O/Fe and Mg/(Mg+Fe). Figures 2a and 2b show the variation of Fe+3/O ratio and log(pO2) with respect to Fe/(Mg+Fe) ratio for magnesiowüstite in equilibrium with iron as calculated by [2004Jun1]. The results are in agreement with experimental data [1987Sre, 1965Kat, 1980Sim] and [1953Sha, 1973Maj 1974Sah, 1987Sre, 1991Wis]. Figures 3a and 3b show the nonstoichiometry of magnesiowüstite by the variation in Fe+3 content with respect to log(pO2) for different temperatures and Mg/(Mg+Fe) ratios as presented by [2004Jun1]. The calculations are in a good agreement with the experimental results of [1958Bry], [1965Kat], [1967Alc], [1967Spe], [1975Val1], [1970Lyk] and [1987Sre]. [1980Sim] measured the lattice parameters of magnesiowüstite and concluded that deviations from Vegard’s law could be due to the presence of Fe+3 cations. All the solid phases in the MgO-FeO-Fe2O3 ternary system contain cations that are smaller than the oxygen ion. The ionic arrangement in these oxides generally consists of hexagonal or cubic close-packed oxygen lattices in which the cations ﬁll the interstitial tetrahedral or octahedral holes [1968Rei]. MgFe2O4 and Fe3O4 form a continuous series of solid solutions of the spinel structure [1931Rob, 1943Whi, 1954Ric, 1955Woo, 1977Tri, 1980Shi]. At room temperature, both end members, MgFe2O4 and Fe3O4, have inverse spinel structures [1932Bar, 1983One]. The octahedral sites are occupied by Mg+2/Fe+2 and Fe3+ ions, whereas the tetrahedral sites are occupied mainly by Fe3+ ions [1968Rei]. With increasing temperature, the degree of inversion decreases for both end-members. Cationic distributions between tetrahedral and octahedral cites in spinel were investigated by [1984Tre] and [1989Nel]. Both sets of experimental results are in reasonable agreement with the calculation of [2004Jun1] for 1000°C, presented in Fig. 4. The spinel in the phase diagram is, however, not limited by the line of MgFe2O4-Fe3O4. When the Landolt-Börnstein New Series IV/11D4

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temperature is raised, the spinel phase expands, being enriched with oxygen [1961Sch2, 1963Gor]. At the Fe3O4 end, the spinel ﬁeld has some extension to the oxygen rich side. This width decreases with increasing Mg content, becoming negligible at the composition MgFe2O4 [1955Woo, 1966Ole]. The MgFe2O4 spinel is practically stoichiometric [1955Woo, 1960Pal, 1968Rei, 1966Sch, 1998Kan]. The Fe2O3 hematite is considered to be a stoichiometric phase. Table 2 lists crystallographic data for the solid phases. Quasibinary Systems The solidus in the “FeO”-MgO system has been studied extensively [1931Rob, 1935Bow, 1954Ric, 1955Woo, 1961Sch1]. According to [2004Jun1], the reported liquidus data are very scattered, possibly owing to the difﬁculty in quenching very ﬂuid slags. The phase diagram of the “FeO”-MgO system was calculated by [1978Kau], [1993Wu], [2000Fab] and [2004Jun1] using different models for the solid and liquid solutions. The phase diagram calculated by [2004Jun1] is presented in Fig. 5. Based on the experimental data of [1931Rob, 1954Ric, 1955Woo], the Fe2O3-MgO “quasibinary” phase diagram has been constructed by [1961Phi]. However, it is not really quasibinary; the investigation was carried out under a constant oxygen partial pressure of 0.21 atm. The bulk oxygen content in the solid phases increases with Fe/Mg ratio. Therefore, the phase diagram of the Fe2O3-MgO system will be presented in a chapter “Temperature – Composition Section”. The liquidus of the Fe3O4-MgO system was determined experimentally by [1932War] for compositions up to 60 mass% MgO. No change in the slope of liquidus line was reported by [1932War]. Therefore, the position of the peritectic formation of spinel is impossible to deduce from these data. The complete phase relationships in the Fe3O4-MgO quasibinary system are available only through the thermodynamic calculations of [1978Kau]. The phase diagram of the Fe3O4-MgO section is not presented here because the calculations of [1978Kau] are found to be in contradiction with experimental data for the rest of the Fe-Mg-O ternary system (see Temperature – Composition Section). Therefore, these calculations are not recommended in the present evaluation. Liquidus, Solidus and Solvus Surfaces [1962Phi] determined a hypothetical liquidus surface for the MgO-FeO-Fe2O3 system based only on the data taken from the isothermal sections containing liquidus isotherms at 1400, 1500, 1600, 1700 and 1800°C. Because of the uncertainties in this liquidus surface, it has not been reproduced in this assessment. No four phase invariant reaction has been found. The univariant liquidus line starting from the peritectic reaction at 1711°C (in air) on the Fe2O3-MgO vertical section ends at the peritectic reaction of 1424°C of the Fe-O binary system. A three-phase equilibrium Lm + Lo + magnesiowüstite (where Lo-oxide liquid. Lm - metallic liquid) starting at the critical point continues down to the solidiﬁcation temperature of iron. Another three-phase equilibrium, Fe2O3 + spinel + Lo, starting presumably from the MgO-Fe2O3 edge, ends at the eutectic reaction at high oxygen pressure between Fe3O4 and Fe2O3. Isothermal Sections The calculated isothermal section for the Fe-Mg-O system at 1200°C and 1 bar total pressure is presented in Fig. 6, taken from the work of [2004Jun1]. Numerous isothermal sections have been established for the partial ternary system FeO-MgO-Fe2O3 at a variety of temperatures and oxygen partial pressures: 850°C [1970Ber, 1977Tri], 1000°C [1960Pal, 1977Tri, 1980Shi], 1100°C [1960Pal], 1160°C [1965Kat, 1967Spe, 1974Sah, 1998Fab], 1200°C [1960Pal], 1300°C [1960Pal, 1967Spe], 1400°C [1962Phi, 1965Ole, 1967Spe], 1500°C [1962Phi], 1600°C [1962Phi], 1700°C [1962Phi] and 1800°C [1962Phi]. Others have determined phase relationships at temperatures up to 1400°C [1968Rei], up to 1650°C [1955Woo] and up to 1500°C [1954Ric] from dissociation curves. The calculated isothermal sections of the MgO-FeO-Fe2O3 system along with oxygen isobars at 1160, 1300 and 1400°C [2004Jun1] are presented in Figs. 7 to 9. The calculated isobars in the magnesiowüstite phase ﬁeld at 1300 and 1400°C are in good agreement with the experimental data of [1967Spe] and [1958Bry] DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

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respectively. However, the slope of the two isobars (log p(O2) = –7 and –6) in the magnesiowüstite + spinel two-phase region determined by [1967Spe] is steeper than that calculated by [2004Jun1]. Figures 10 to 13 show phase diagrams calculated over the temperature range of 1500 to 1800°C. Experimentally determined phase assemblages given by [1962Phi] are in agreement with the calculations of [2004Jun1] at all studied temperatures. [1988Sch] equilibrated molten MgO-FeO-Fe2O3 slags and gas mixtures of known oxygen potentials in MgO crucibles at 1600°C. Also, the calculations of oxygen partial pressure by [2004Jun1] are in agreement with the experimental data, while the calculated MgO content in the liquid is less than obtained experimentally. Temperature – Composition Sections The calculated phase diagram of the Fe2O3-MgO system given by [2004Jun1] shown in Fig. 14 is in agreement with the experimental data of [1931Rob, 1954Ric, 1955Woo, 1961Phi, 1968Rei, 2003Hon]. However, no experimental data on phase relations are available for temperatures above 1800°C. The only intermediate compound encountered is the spinel phase MgFe2O4, which melts at 1711°C (in a good agreement with experimental value of 1713 ± 5°C given by [1961Phi]) through a peritectic reaction between liquid and magnesiowüstite. At this isobaric invariant, the liquid, magnesioferrite and the magnesiowüstite phases contain approximately 68, 60, and 38 mol% iron oxide (calculated as Fe2O3), respectively. Based on their dissociation data for temperatures up to 1500°C, [1954Ric] found, that the extension of the magnesiowüstite homogeneity range towards the spinel phase boundary is very restricted up to 1500°C. This is in contradiction with [1931Rob] and [1961Phi]. The solid solubility of MgFe2O4 in MgO reported by [1931Rob] was conﬁrmed by [1955Woo]. The phase diagram of the Fe2O3-MgO system calculated by [1978Kau] is different from the experimental diagram determined by [1961Phi]. The dissociation curves for MgO-Fe2O3 mixtures in air for increasing temperatures are shown in Fig. 15, as calculated by [2004Jun1]. The calculated results are in good agreement with the experimental data of [1954Ric, 1955Woo, 1967Wil]. Mixtures containing less than 50% of MgO are reduced to spinel with increasing temperature, while mixtures with a MgO content higher than 50% are reduced to magnesiowüstite. The phase diagram of the MgO-FeO-Fe2O3 system under air is presented in Fig. 16, taken from [2004Jun1]. This diagram is another representation of that for the MgO-Fe2O3-O2 system under air. Potential Diagrams Phase diagrams showing oxygen partial pressure against metal ratio calculated by [2004Jun1] are presented in Figs. 17 to 21. The oxygen partial pressures along the phase boundaries were determined by gas equilibration [1955Woo, 1960Pal, 1962Hah, 1965Kat, 1967Spe] or by an emf technique [1973Maj, 1987Sre], except for the study by [2000Kan] where it was determined by measurement of electrical conductivity and thermoelectric power. All experimental data are reproduced in the calculation of [2004Jun1] within experimental error limits. Thermodynamics Review of the thermodynamic measurements for the end members of the magnesioferrite and magnesiowüstite solid solutions and Fe2O3 can be found in [1973Bar, 1979Sek, 1991Sun, 2004Fab, 2004Jun1]. The enthalpy of formation of MgFe2O4 at 970 K (697°C) was measured by solution calorimetry [1968Nav] and found to be consistent with values derived from the gas equilibration data of [1970Ber] measured at 850°C and the emf data of [1965Tre3] but different from that resulting from the emf study of [1967Guz] and data derived from reduction isotherms and phase analysis [1977Tri]. The activities of “FeO” and MgO in “FeO”-MgO solid solutions have been studied extensively by the gas equilibration method and the emf technique [1953Sha, 1961Sch2, 1962Hah, 1970Aub, 1970Ber, 1972Bal, 1973Abb, 1973Maj, 1977Tri, 1983Dav, 1984Dob, 1987Sre]. Deviation from ideality is observed for the “FeO”-MgO solid solution owing to the attractive interaction of Mg2+ and Fe2+ in the lattice [1977Tri]. The results of [1970Aub, 1970Ber, 1972Bal] are in good agreement with those of [1953Sha, 1961Sch2, 1962Hah, 1987Sre]. [1973Abb] and [1973Maj] derived activity values for the magnesiowüstite solid solution from emf measurements performed at 800 and 1100°C. Positive deviations from ideal behavior, Landolt-Börnstein New Series IV/11D4

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decreasing with temperature, were observed. The observed deviations from ideality at 1100°C are lower than those obtained by [1962Hah]. The latest data for the activity of FeO, MgO and Fe2/3O from [1987Sre] are presented in Fig. 22. These data are in good agreement with other investigations, and the presence of Fe+3 is taken into account. Solid solutions between MgFe2O4 and Fe3O4 are not ideal, although the deviation from ideality is comparatively small [1966Ole, 1980Shi, 1984Dob]. This small positive departure from ideal behavior was indicated by [1963Gor] who calculated the Gibbs energy of formation of magnesioferrite - magnetite solid solutions of MgxFe3–xO4 with 0 < x ≤ 0.5. [1980Shi] determined the activities of Fe3O4 and MgFe2O4 via a galvanic cell. The results were conﬁrmed by [1984Tre] who calculated the activity of Fe3O4 at 1000°C from a consideration of cation distribution. However, these results disagree with those of [1965Tre2], who found an almost ideal solution since the activities were considered to be independent if the phase was in equilibrium with metallic iron or with the spinel phase. From the studies undertaken by [1970Ber, 1977Tri], larger positive deviations from ideality were found, most probably owing to uncertainties in the position of the homogeneity boundaries of solid solutions of MgO in wüstite. The emf measurements of [2002Kat] indicated positive deviation from ideal behavior in spinel solid solutions at 1000°C. The values obtained lie approximately between the results of [1980Shi] and [1977Tri]. The data of [2002Kat] are presented in Fig. 23. [1978Lyk] used the regular ionic solution model to describe the thermodynamic properties of magnesiowüstite. The equilibrium partial pressure of oxygen and the homogeneity ranges of magnesiowüstite were calculated and compared with experimental data [1970Lyk]. [1983Dav] parameterized the deviations from ideal mixing for magnesiowüstite solid solutions using regular and subregular thermodynamic mixing models. [1980Gor] calculated the interaction parameter between Mg and O in liquid iron from the Mg solubility in liquid iron and constants for the deoxidation equilibrium of Mg in liquid iron. [1997Ito] studied experimentally the deoxidation equilibrium at 1600 and 1750°C, and the relationship between the concentration of magnesium and oxygen was obtained. The experimental data are in good agreement with calculations made using a thermodynamic model incorporating ﬁrst and second order interaction parameters. A modiﬁed Wagner formalism was used by [2004Jun2] to model deoxodation equilibria in steel for 15 metals including Mg. The Calphad method was used by [1993Wu] to model the liquidus and solidus lines in the MgO-FeO system using a Redlich-Kister solution model for the solid phase and a quasichemical model for the liquid. [1998Fab] applied the Calphad method in the derivation of thermodynamic parameters for the solid phases and to calculate phase diagrams for the Fe-Mg-O system. However, the calculated phase boundaries deviated from the experimental data of [1967Spe] and [1958Bry]. Liquidus and solidus lines of the FeO-MgO system were calculated by [2000Fab]. The Calphad-type assessment of [2002Dec] incorporated the compound energy formalism for the spinel phase, simple polynomial expansions for magnesiowüstite and the modiﬁed quasichemical model for liquid phase. The modeling was found to reproduce most of the available experimental data within uncertainty limits. The same models were used by [2004Jun1]. In the work of [2004Jun1], the thermodynamic parameters of the Fe-Mg-O system were reassessed and a number of phase diagrams were produced showing good agreement with available experimental data. The calculated activity for magnesiowüstite and magnesioferrite were not presented in the work of [2004Jun1]. Therefore, activity data are recommended from other sources, which are in good agreement with other available experimental data. Notes on Materials Properties and Applications The phases observed in the Fe-Mg-O system are constituent minerals of the Earth. Magnesioferrite is observed at relatively low pressures in the Earth’s crust, while magnesiowüstite is a constituent of the low mantle where pressures are above 26 GPa. At these pressures, the (Mg,Fe)2SiO4 phase with the spinel structure decomposes to a mixture of the (Mg,Fe)SiO3 phase with the perovskite structure and magnesiowüstite. In order to interpret seismological data, the elastic properties, thermal expansion and seismic wave velocities of magnesiowüstite have been studied experimentally. A review of these data is presented in [1989Duf, 1992Ita, 1993Sax, 2004Fab]. Recently, volumetric measurements of magnesiowüstite at high temperatures and pressures have been performed using energy dispersive synchrotron XRD by [2002Zha, 2005Jac, 2005Wes] to derive thermal and elastic properties. [2002Jac] used ultrasonic interferometry at high pressure and temperature to determine the elastic constants of magnesiowüstite. [2006Tom] deformed DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

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magnesiowüstite with a composition of xMg/(xFe+xMg) = 0.1, 0.25 and 0.4 at room temperature and pressures up to 37, 16 and 18 GPa. Elastic constants were calculated and elastic anisotropy was observed. [2004Lev] studied the behavior of MgFe2O4 spinel by synchrotron XRD at high pressures and temperatures and derived elastic properties and thermal expansion. [1965Ole] observed an increase in the electrical resistance of spinel solid solutions with reciprocal temperature. The electrical conductivity at 27°C is 4.6·10–2 Ω–1·cm–1and it increases with time [1972Rez]. This has been attributed to a re-ordering of the cations. The electronic conduction is explained by the electronic exchange of Fe3+ and Fe2+ on octahedral sites. The magnetic susceptibility of magnesiowüstite was studied between 120 and 293 K and for total Fe contents in the range of 0–6.6 mol% FeO by [1975Val2], and at 78–460 K and up to 20 mol% of FeO by [1980Bra]. [1974Kra] measured the magnetization of a magnesiowüstite single crystal. [1972Rez] measured the electrical conductivity of MgFe2O4 at 27°C. [1999Har] measured the magnetic susceptibility of MgFe2O4. It was shown that the Curie temperature of MgFe2O4 is very sensitive to Fe+3 and Mg+2 distributions between octahedral and tetrahedral sites within the spinel structure. The magnetic properties of MgFe2O4 were also measured by [1999Cro]. [1964Gro] studied strengthening of MgO by Fe. It was demonstrated that this effect is due to the presence of Fe+3 in contrast to Fe+2. [1974Sin1, 1974Sin2] determined edge and screw dislocation velocities for Fe+3 doped MgO (90 and 150 ppm of Fe+3) as a function of temperature and stress, and estimated the activation energy for edge and screw dislocations. [1988Wol] measured the creep resistance of a magnesiowüstite single crystal at 1300–1500°C, 20–70 MPa applied stress and oxygen partial pressure in the range of 10–4-102 Pa. The thermal conductivity of MgO containing 300, 3000 and 7500 ppm Fe was measured by [1971Mor]. It was shown that the thermal conductivity is reduced with Fe content and has a minimum at 80 K for highly doped samples (1 mass% Fe). [2000Kan] measured the electrical conductivity and thermoelectric power of the Fe-Mg-O system as a function of oxygen partial pressure at 1100–1300°C and Mg/(Mg+Fe) ratio in the range 0–0.4. The compositional dependence of electrical conductivity of magnesiowüstite was studied by [1971Gur] at 800–1000°C. Experimental studies of properties are summarized in Table 3. Miscellaneous [1954Ric] investigated the inﬂuence of temperature and composition on the rate of dissolution of ferric oxide in mixtures of “FeO”, MgO and Fe2O3. It was found that the oxygen loss is completely reversible; the rates of oxidation and dissolution are relatively rapid. [1988Lue] determined the kinetics of the internal oxidation of (Mg,Fe)O solid solutions and found that a two-phase region of (Mg,Fe)O and MgFe2O4 grows inward from the original surface under oxidizing conditions. The diffusion of “FeO” into MgO occurs by the counterdiffusion of Mg2+ with Fe2+ and Fe3+ ions through a relatively rigid oxygen lattice [1965Rig]. The diffusion coefﬁcient increases exponentially with cation vacancy concentration [1969Bla]. [1997Byg] calculated the interdiffusion coefﬁcients at different temperatures (1200, 1250, 1300 and 1330°C). Results are in good agreement with those of [1969Bla] but are lower than values obtained by [1965Rig]. This difference has been attributed to the difference in the oxygen partial pressures which would in turn affect the vacancy concentrations in the oxide samples. Assuming that the diffusion of oxygen is negligible, the interdiffusion can be considered to occur essentially by cationic transport. [2003Yam] measured interdiffusivities in magnesiowüstite at high temperatures and pressures. Diffusion proﬁles were measured across the interface between MgO and (Fe0.5Mg0.5)O samples by microprobe analysis. [1954Hen] studied the decomposition kinetics of Fe2O3 in the presence of MgO at 783–1020°C. [1978Cor] studied the effect of electronic structure on the redox behavior of the guest specie Fe2+ in the magnesium oxide solid solution and showed that Fe2+ is oxidized to Fe3+ in the temperature range 500–700°C. The formation of MgFe2O4 is eventually observed. [1980Vla] used the electron paramagnetic resonance method to study the mechanism of the solid state reaction taking place between MgO and Fe2O3. [1990Bec] used Mössbauer spectroscopy to investigate the kinetics of the oxidation of magnesiowüstite to spinel. [1999Har] studied the kinetics of non-convergent cation ordering in MgFe2O4 by measuring the Curie Landolt-Börnstein New Series IV/11D4

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temperature of synthetic samples as a function of isothermal annealing time. [1999Cro] prepared spinel MgFe2O4 by self-propagating high-temperature synthesis from iron, iron(III) oxide and Mg oxide. The reaction was carried out in air, under an oxygen atmosphere and in the presence of an external magnetic ﬁeld of 1.1 T. The inversion parameter of spinel was inﬂuenced by the external ﬁeld. Samples were characterized by XRD, EDXA, SEM, FTIP, Mössbauer spectroscopy and vibrating sample magnetometry. [2001Dub] found that magnesiowüstite solid solutions dissociate to Fe rich and Mg rich components at T > 1000 K (727°C) and P > 80 GPa. [2001Boi] found that under lithospheric conditions, periclase could dissolve a limited amount of FeO. Mineral and synthetic samples were studied by microprobe analysis, XRD and SEM. [2003Lin] studied magnesiowüstite at 86 GPa and 1000 K (727°C) using a laser-heated diamond anvil cell combined with synchrotron XRD. It was shown that the addition of Mg to FeO stabilizes the cubic structure at very high pressures that correspond to those at the boundary between the lower mantle and the Earth’s core. [2005Jac] studied wüstite and magnesiowüstite under lower mantle pressures by synchrotron XRD. It was found that wüstite Fe0.93O transformed to a rhombohedral structure at 23 GPa while (Mg0.73Fe0.27)O remained cubic at pressures of 51 GPa. The elastic properties of both phases were determined by [2005Jac]. [2006Lin] studied the electronic transition of Fe in magnesiowüstite by synchrotron Mössbauer and XRD spectroscopy under high pressure. Contrary to [2003Lin, 2004Kon, 2005Jac], where the rhombohedral phase was found only in Fe rich magnesiowüstite, [2006Kan1] discovered the transformation of cubic (Mg0.8Fe0.2)O to the rhombohedral phase at 35 GPa and room temperature, using XRD, Mössbauer and XANES spectroscopy in situ experiments. [2006Zha] presented shock-compression data for magnesiowüstite for pressures up to 130 GPa. The volume change for (Mg0.6Fe0.4)O is consistent with a cubic to NiAs structural transition. It is possible that contradictions between the different experimental results relating to the transformation of magnesiowüstite can be explained by the fact that this transformation may occur under non-hydrostatic conditions. [2006Kan2] presented high-pressure Mössbauer and X-ray emission spectra for (Mg0.8Fe0.2)O. [2001And, 2004Lev] studied the crystal structure of MgFe2O4 at high pressure, and it was indicated that spinel MgFe2O4 transforms to the orthorhombic CaMn2O4 structure at pressures between 5 and 17.7 GPa and temperatures above 1800 K (1527°C). At lower temperatures, the spinel decomposes to an oxide mixture. [2005Ant] investigated the unit cell parameters of MgFe2O4 by synchrotron radiation at 25–982°C and normal pressure. A linear dependence was observed below and above 581°C. The discontinuity in the cell parameters at 581°C coincides with maximum cation ordering. An exothermic peak was also observed at 550°C by TG-DSC measurements. [1998Ber] studied the defect structure of divalent Mg-doped αFe2O3 by Rietveld structure reﬁnement of XRD data. It was shown that Mg+2 occupied vacant interstitial sites and adjacent octahedral Fe+3 sites in the corundum related structure. This result was conﬁrmed by neutron powder diffraction studies [2000Ber]. [2000Ber] also measured the magnetic properties of Mg-doped αFe2O3 and Mössbauer spectra. [1997Fon] measured optical and magneto-optical polar Kerr spectra for Fe3O4 doped by Mg+2. [2000Vas] performed a thermodynamic analysis of molecular beam epitaxial growth of MgO(s) and MgO/Fe(001) layers from ﬂow balance at the growth surface, taking into account condensation, evaporation and growth ﬂows. Predominance diagrams were proposed where the domains for the formation of the different phases were predicted. The geometric structure of MgO deposited on Fe(001) under ultra high vacuum by electron evaporation was studied by surface XRD by [2001Mey]. An interface layer of FeO between the substrate and the growing MgO was indicated. [2004Shi] studied the contact angle between liquid Fe and a MgO substrate at 1600°C and oxygen partial pressures in the range 5.2·10–4-1·10–9 atm. [2002Mer] studied the electron density of MgO and (Mg0.963Fe0.037)O by a maximum entropy method and multipole reﬁnements. Single crystal XRD and Mössbauer spectroscopy were used in the investigations. [2005Gat] studied the three-dimensional structure of nanocrystalline MgFe2O4 by synchrotron XRD. The catalytic activity of iron oxide and magnesium oxide solid solutions for N2O decomposition was studied by [1975Sch, 1975Val2, 1977Cor].

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Fe–Mg–O Table 1.

9

Investigations of the Fe-Mg-O Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1999Cro]

XRD, EDXA, SEM, FTIP, Mössbauer spectroscopy

MgFe2O4, self-propagating synthesis at 950–1050°C

[2000Fab]

Calphad

Solidus/liquidus in FeO-MgO system

[2000Kan]

Electric conductivity and thermoelectric power measurements

1100–1300°C, p(O2) = 0.21–10–16 atm x (Mg)/(x(Mg)+x(Fe)) = 0–0.4

[2001And]

In situ XRD in diamond anvil cell

MgFe2O4, T < 1727°C, p < 60 GPa

[2001Boi]

Microprobe analysis, XRD, SEM-WDS

Magnesiowüstite with FeO content of 5, 23 and 8.22 mol%

[2001Dub]

Diamond anvil cell, XRD

T > 727°C, p = 40–80 GPa (Mg0.8Fe0.2)O and (Mg0.5Fe0.5)O

[2002Dec]

Calphad

Phase diagrams in the whole composition range at 800–1800°C and p(O2) = 10–20 1 atm

[2002Kat]

emf

887–1117°C, MgFe2O4-Fe3O4

[2003Hon]

High-temperature XRD

25–1400°C, air, MgO 100–80 mol%

[2003Yam]

Microprobe

Interdiffusivities in magnesiowüstite

[2004Jun1]

Calphad

Phase diagrams in the whole composition range at 800–1800°C and p(O2) = 10-20 - 1 atm

[2004Jun2]

emf

887–1117°C, MgFe2O4-Fe3O4

[2004Kon]

In situ XRD in diamond anvil cell, synchrotron radiation

(MgxFe1–x)O, x = 0–0.2, T = 0–1800°C, p < 140 GPa

[2004Lev]

Synchrotron XRD in diamond anvil cell

MgFe2O4, 25–2227°C, p < 60 GPa

[2005Jac]

Synchrotron XRD in diamond anvil cell

(Mg0.73Fe0.27)O, p < 51 GPa

[2005Wes]

Synchrotron XRD in multi-anvil press

(Mg0.64Fe0.36)O, T = 1900°C, p = 26.7 GPa

[2006Kan1]

Synchrotron XRD, X-ray absorption spectroscopy, Mössbauer spectroscopy in diamond anvil cell

(Mg0.8Fe0.2)O, p < 60 GPa, 25°C

[2006Kan2]

Mössbauer spectroscopy in diamond anvil cell

(Mg0.8Fe0.2)O, p < 100 GPa, 25°C

[2006Lin]

Synchrotron Mössbauer, X-ray emission spectroscopy in diamond anvil cell

(Mg0.75Fe0.25)O, p < 100 GPa

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Fe–Mg–O

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) (h2) 1538–1356

cI2 Im 3m W

a = 293.15

at 1390°C [Mas2]

(γFe) (h1) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [Mas2]

(αFe) (r) < 912

cI2 Im 3m W

a = 286.65

at 25°C [Mas2]

(Mg) < 650

hP2 P63/mmc Mg

a = 320.94 c = 521.01

at 25°C [V-C2]

αFe2O3 (hematite) < 1457

hR30 R 3c Al2O3

a = 503.42 c = 1374.83

∼60 at.% O [V-C2]

γFe2O3

cF56 Fd 3m MgAl2O4

a = 834

low temperature or metastable [1989Rag2]

(Fe1–x–yMgx)O magnesiowüstite (MW) MgO (periclase) < 2827 ± 30 Fe1–yO (wüstite) 1424–570

cF8 Fm 3m NaCl

(Mg1–xFex)Fe2O4+y spinel (magnesioferrite) Fe3O4 (magnetite) < 1596

cF56 Fd 3m MgAl2O4

MgFe2O4 < 1713 ± 5

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0≤x≤1

a = 421.12

[V-C2, Mas2, 1993Hal]

a = 435.35

at 1000°C [V-C2]

a = 841.1 a = 838.65 a = 839.46

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57.1 to 58.0 at.% O at 200°C [V-C2] [1961Phi] at 1100°C and 53.1 mol% Fe2O3 [1960Pal] at 1100°C and 49.0 mol% Fe2O3 [1960Pal]

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Fe–Mg–O Table 3.

11

Investigations of the Fe-Mg-O Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1964Gro]

Microhardness measurement

Strengthening of MgO by Fe+3 doping

[1965Ole]

Electrical conductivity measurements

Electrical resistance for (MgO)0.092-MgFe2O4 and MgFe2O4

[1971Gur]

Conductometry

Electroconductivity of magnesiowüstite 800–1160°C and Mg/(Mg+Fe) = 0.05–0.5

[1972Rez]

Bridge-method

Electroconductivity of MgFe2O4 spinel at 27°C

[1974Kra]

Foner-type magnetometer

Magnetization of (Fe0.157Mg0.843)O at 77 K

[1974Sin1]

Yield stress measurements

Edge and screw dislocation velocities in MgO doped with 90 ppm Fe+3

[1974Sin2]

Yield stress measurements

Edge and screw dislocation velocities in MgO doped with 150 ppm Fe+3

[1975Val2]

Magnetic measurements

Magnetic susceptibility (Fe0.066Mg0.934)O at 120–293 K

[1980Bra]

Faraday method

Magnetic susceptibility of magnesiowüstite, up to 20 mol% FeO at 78–460 K

[1988Wol]

Uniaxial compression

Creep of (Mg,Fe)O single crystal, 70–11900 ppm Fe, at 1300–1500°C, 20–70 MPa stress, p(O2)=10–4-10–2 Pa

[1999Cro]

Magnetometer

Magnetic properties for MgFe2O4

[1999Har]

Magnetic property study

Magnetic susceptibility of MgFe2O4 at 200–400 K

[2000Kan]

DC four-probe and pulse techniques

Electric conductivity and thermal power

[2001And]

In situ XRD in diamond anvil cell

Elastic constants for MgFe2O4 spinel and high-pressure phase of CaMn2O4 structure

[2002Jac]

Ultrasonic interferometry

Elastic constants of magnesiowüstite

[2002Zha]

Energy-dispersive synchrotron XRD in large-volume high-pressure apparatus

Elastic constants (Mg0.6Fe0.4)O

[2004Lev]

Synchrotron XRD in diamond anvil cell

Elastic constants and thermal expansion of MgFe2O4

[2005Jac]

Synchrotron XRD in diamond anvil cell

Elastic properties (Mg0.73Fe0.27)O

[2005Wes]

Synchrotron XRD in multianvil press

Unit cell volume, elastic constants, thermal expansion for (Mg0.64Fe0.36)O

[2006Lon]

Deformation experiments

Mechanical properties of (Mg,Fe)O

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Fig. 1. Fe-Mg-O.

Fe–Mg–O

Calculated temperature of dissociation of magnesiowüstite into spinel and Fe

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Fe–Mg–O

Fig. 2a. Fe-Mg-O.

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13

Calculated Fe+3/O vs Fe/(Fe + Mg) ratio in magnesiowüstite in equilibrium with metallic iron

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14

Fig. 2b. Fe-Mg-O.

Fe–Mg–O

Calculated oxygen partial pressure for the equilibrium between magnesiowüstite and metallic iron

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Fe–Mg–O

15

Fig. 3a. Fe-Mg-O. Calculated nonstoichiometry of magnesiowüstite as a function of oxygen partial pressure at various temperatures and Mg/(Mg + Fe) ratios

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Fe–Mg–O

Fig. 3b. Fe-Mg-O. Calculated nonstoichiometry of magnesiowüstite as a function of oxygen partial pressure at various temperatures and Mg/(Mg + Fe) ratios

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Fe–Mg–O

17

Fig. 4. Fe-Mg-O. Calculated cation distribution in the Fe3O4-MgFe2O4 spinel solid solution at 1000°C. (O)–octahedral sites, (T) – tetrahedral sites

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Fig. 5. Fe-Mg-O.

Fe–Mg–O

Calculated phase diagram of the MgO-FeO system in equilibrium with metallic Fe

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Fe–Mg–O

Fig. 6. Fe-Mg-O.

Landolt-Börnstein New Series IV/11D4

19

Calculated isothermal section at 1200°C and ptot=1 bar

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Fig. 7. Fe-Mg-O.

Fe–Mg–O

Calculated FeO-MgO-Fe2O3 isothermal section at 1160°C with log(pO2) isobars

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Fe–Mg–O

Fig. 8. Fe-Mg-O.

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21

Calculated FeO-MgO-Fe2O3 isothermal section at 1300°C with log(pO2) isobars

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22

Fig. 9. Fe-Mg-O.

Fe–Mg–O

Calculated FeO-MgO-Fe2O3 isothermal section at 1400°C with log(pO2) isobars

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Fe–Mg–O

23

Fig. 10. Fe-Mg-O. Calculated FeO-MgO-Fe2O3 isothermal section at 1500°C

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Fig. 11. Fe-Mg-O.

Fe–Mg–O

Calculated FeO-MgO-Fe2O3 isothermal section at 1600°C

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Fe–Mg–O

Fig. 12. Fe-Mg-O.

Landolt-Börnstein New Series IV/11D4

25

Calculated FeO-MgO-Fe2O3 isotherm at 1700°C

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Fig. 13. Fe-Mg-O.

Fe–Mg–O

Calculated FeO-MgO-Fe2O3 isotherm at 1800°C

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Fe–Mg–O

Fig. 14. Fe-Mg-O.

Landolt-Börnstein New Series IV/11D4

27

Calculated phase diagram of the MgO-Fe2O3-O2 system in air

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Fe–Mg–O

Fig. 15. Fe-Mg-O. Calculated dissociation curves of MgO-Fe2O3 initial mixtures in air with increasing temperature

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Fe–Mg–O

Fig. 16. Fe-Mg-O.

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29

Calculated dissociation curves of MgO-FeO-Fe2O3 system in air

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Fig. 17. Fe-Mg-O.

Fe–Mg–O

Calculated phase diagram at 1000°C log(pO2) vs Mg/(Mg+Fe) ratio

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Landolt-Börnstein New Series IV/11D4

Fe–Mg–O

Fig. 18. Fe-Mg-O.

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31

Calculated phase diagram at 1100°C log(pO2) vs Mg/(Mg+Fe) ratio

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Fig. 19. Fe-Mg-O.

Fe–Mg–O

Calculated phase diagram at 1200°C log(pO2) vs Mg/(Mg+Fe) ratio

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Fe–Mg–O

33

Fig. 20. Fe-Mg-O. Calculated phase diagram at 1300°C log(pO2) vs Mg/(Mg+Fe) ratio

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Fig. 21. Fe-Mg-O.

Fe–Mg–O

Calculated phase diagram at 1500°C log(pO2) vs Mg/(Mg+Fe) ratio

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Landolt-Börnstein New Series IV/11D4

Fe–Mg–O

Fig. 22. Fe-Mg-O. 1400°C

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35

Activity-composition relations for FeO, Fe2/3O and MgO in equilibrium with metallic iron at

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Fig. 23. Fe-Mg-O.

Fe–Mg–O

Activity-composition in the Fe3O4-MgFe2O4 system in equilibrium with Fe2O3 at 1000°C

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Fe–Mg–O References [1931Rob]

[1932Bar] [1932War]

[1935Bow] [1943Whi] [1945Jay]

[1946Pet]

[1953Sha]

[1954Hen]

[1954Ric]

[1955Woo]

[1957Flo] [1958Bry]

[1960Pal]

[1961Phi]

[1961Sch1]

[1961Sch2]

[1962Hah]

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37

Roberts, H.S., Merwin, H.E., “The System MgO-FeO-Fe2O3 in Air at One Atmosphere”, Amer. J. Sci., 21(122), 145–157 (1931) (Experimental, Phase Diagram, Phase Relations, *, #, 15) Barth, T.F.W., Posnijak, E., “Spinel Structures: with and without Variate Atom Equipoints”, Z. Kristallogr., 82, 325–341 (1932) (Experimental, Structure, 10) Wartenberg, H.V., Prophet, E., “Melting Diagrams of Maximumﬁreproof Oxides. V. Systems with MgO” (in German), Z. Anorg. Chem., 208, 369–379 (1932) (Experimental, Phase Relations, 21) Bowen, N.L., Schairer, J.F., “The System MgO-FeO-SiO2” (in German), Amer. J. Sci., 29(170), 151–217 (1935) (Experimental, Phase Diagram, Phase Relations, *, #, 47) White, J., “The Physical Chemistry of Open-hearth Slags”, J. Iron Steel Inst., 148, 579–625 (1943) (Phase Diagram, Phase Relations, Review, 195) Jay, A.H., Andrews, K.W., “Note on Oxyde Systems Pertaining to Steel-Making Furnace Slags. FeO-MnO, FeO-MgO, CaO-MnO, MgO-MnO”, J. Iron Steel Inst., London, 152, 15–18 (1945) (Crys. Structure, Experimental, 7) Pettersson, H., “Investigations of the Solubility in the Solid State in the Binary Systems of the Oxides CaO, MnO, MgO and FeO”, Jernkontorets Ann., 130(12), 653–663 (1946) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 19) Shashkina, A.V., Gerasimov, Y.L., “Equilibrium of FeO-MgO Solid Solution with Hydrogen and Activities of Solution Components” (Russian), Zh. Fiz. Khim., 27, 399–410 (1953) (Experimental, Thermodyn., 6) Henrich, G., “Over the Inﬂuence of the Gas Atmosphere and the Compacting Pressure on Reaction in the Solid State” (in German), Z. Elektrochem., 58(3), 183–196 (1954) (Experimental, 40) Richards, R.G., White, J., “Phase Relationships of Iron-Oxide-Containing Spinels. II Relations in the Systems Fe-Cr-O, Fe-Mg-O, Fe-Al-Cr-O, Fe-Al-Cr-Mg-O”, Trans. Brit. Ceram. Soc., 53(7), 422–459 (1954) (Experimental, Phase Diagram, Phase Relations, *, #, 11) Woodhouse, D., White, J., “Phase Relationships of Iron Oxide-containing Spinels: III. Further Investigations on the System Fe-Mg-O and Fe-Mg-Cr-O, and General Relationships in the System Fe-Mg-Cr-Al-O”, Trans. Brit. Ceram. Soc., 54(6), 333–366 (1955) (Experimental, Phase Diagram, Phase Relations, *, #, 10) Flood, H., Hill, D.G., “The Redox Equilibrium in Iron Oxide Spinels and Related Systems”, Z. Elektrochem., 61(1), 18–24 (1957) (Experimental, 16) Brynestad, J., Flood, H., “The Redox Equilibrium in Wüstite and Solid Solutions of Wüstite and Magnesium Oxide”, Z. Elektrochem., 62(9), 953–958 (1958) (Experimental, Thermodyn., 14) Paladino, A.E., “Phase Equilibria in the Ferrite Region of the System FeO-MgO-Fe2O3”, J. Am. Ceram. Soc., 43(4), 183–191 (1960) (Experimental, Phase Diagram, Phase Relations, 9) Philips, B.L., Somiya, S., Muan, A., “Melting Relations of Magnesium Oxide-Iron Oxide Mixtures in Air”, J. Am. Ceram. Soc., 44(4), 167–169 (1961) (Experimental, Phase Relations, *, #, 6) Von Schenck, H., Pfaff, W., “The System FeO-MgO and Distribution Equilibria with Liquid Iron from 1520 to 1750°C”, Arch. Eisenhüttenw., 32(11), 741–751 (1961) (Experimental, Phase Relations, Thermodyn., *, #, 49) Von Schmahl, N.G., Frisch, B., Stock, G., “Equilibrium investigations at Magnesiowüstite and Magnesioferrite” (in German), Arch. Eisenhttenw., 32, 297–302 (1961) (Experimental, Thermodyn., 17) Hahn, W.C., Muan, A., “Activity Measurements in Oxide Solid Solutions: The System FeO-MgO in the Temperature Interval 1100 to 1300°C”, Trans. AIME, 224, 416–420 (1962) (Experimental, Thermodyn., 5)

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38 [1962Phi]

[1963Gor] [1964Gro] [1964Lev] [1965Kat] [1965Ole]

[1965Rig] [1965Tre1]

[1965Tre2]

[1965Tre3]

[1966Ole]

[1966Sch] [1967Alc] [1967Guz]

[1967Spe]

[1967Wil]

[1968Nav] [1968Rei] [1969Bla] [1970Aub]

Fe–Mg–O Philips, B., Muan, A., “Phase Equilibria in the System MgO-FeO-Fe2O3 in the Temperature Range 1400 to 1800°C”, J. Am. Ceram. Soc., 45(2), 588–591 (1962) (Experimental, Phase Relations, Phase Diagram, *, #, 18) Gordeev, I.V., Tret'yakov, Y.D., “Thermodynamics of Solid Solutions of Magnesium Ferrite with Magnetite”, Russ. J. Inorg. Chem., 8(8), 943–947 (1963) (Experimental, Thermodyn., 21) Groves, G.W., Fine, M.E., “Solid Solution + Precipitation Hardening in Mg-Fe-O Alloys”, J. Appl. Phys., 35(12), 3587–3593 (1964) (Experimental, Mechan. Prop., 14) Levin, E.M., Robbins, C.R., McMurdie, H.F., Phase Diagrams for Ceramists, Am. Ceram. Soc., Columbus, Ohio, 54–56 (1964) (Phase Diagram, Phase Relations, Review, 4) Katsura, T., Kimura, S., “Equilibria in the System FeO-Fe2O3-MgO at 1160°C”, Bull. Chem. Soc. Jap., 38(10), 1664–1670 (1965) (Experimental, 16) Oleinikov, N.N., Saksonov, Y.G., Tret"yakov, Y.D., “A Study of Phase Equilibria in the MgO-FeO-Fe2O3 System at 1400°C”, Inorg. Mater., 1(2), 227–233 (1965), translated from Zh. Neorg. Mater., 1(2), 246–253 (1965) (Experimental, Phase Relations, 21) Rigby, E.B., Cutler, I.B., “Interdiffusion Studies of the System FexO-MgO”, J. Am. Ceram. Soc., 48, 95–99 (1965) (Experimental, Interface Phenomena, Phase Relations, 13) Tret"yakov, Yu.D., Oleinikov, N.N., “Activity of the Components of Solid Solution with a Spinel Structure in the Iron-Magnesium-Oxygen System”, Inorg. Mater. (Engl. Trans.), 1(2), 234–236 (1965) (Thermodyn., Experimental, 8) Tret"yakov, Yu.D., “Methods for Estimating the Thermodynamic Properties of Ferrites and Solid Solutions of Ferrites with Magnetite”, Inorg. Mater., 1, 221–226 (1965) translated from Izv. Ak. Nauk SSSR, Neorg. Mater., 1, 240–245 (1965) (Experimental, Thermodyn., 16) Tret"yakov, Yu.D., Schmalzried, H., “Thermodynamics of Spinel Phase (Chromite, Ferrite, Aluminate)” Ber. Bunsen-Ges. Phys. Chem., 69, 396–402 (1965) (Experimental, Thermodyn., 50) Oleinikov, N.N., Tretyakov, Yu.D., “Thermodynamic Properties of Solid Solutions with Spinel Structure in the System Iron-Magnesium-Oxygen”, Inorg. Mater., 2, 131–135 (1966) translated from Izv. Akad. Nauk. SSSR, Neorg. Mater., 2(1), 155–160 (1966) (Experimental, Thermodyn., 7) Schmalzried, H., Tretjakow, J.D., “Irregularity in Ferrite”, Ber. Bunsenges Phys. Chem., 70, 180–188 (1966) as quoted in [2001Jun1] Alcock, C.B., Iyengar, G.N., “A Study of the Oxidation-Reduction Equilibria of Dilute Magnesiowüstite”, Proc. Brit. Ceram. Soc., 87, 219–229 (1967) (Experimental, Thermodyn., 10) Guzei, A.S., Lavrent'ev, V.I., Bulgakova, T.I., “The Study of the Thermodynamic Properties of Magnesium Ferrite by the emf Method Using a Solid Electrolyte”, Inorg. Mater., 3, 767–772 (1967) translated from Izv. Ak. Nauk SSSR, Neorg. Mater., 3(5), 860–867 (1967) (Experimental, Thermodyn., 19) Speidel, D.H., “Phase Equilibria in the System MgO-FeO-Fe2O3: The 1300°C Isothermal Section and Extrapolations to Other Temperatures”, J. Am. Ceram. Soc., 50(5), 243–248 (1967) (Experimental, Phase Diagram, Phase Relations, *, #, 12) Willshee, J.C., White, J., “An Investigation of Equilibrium Relationships in the System MgO-FeO-Fe2O3 up to 1750°C in Air”, Trans. Brit. Ceram. Soc., 66, 541–555 (1967) as quoted in [2001Jun1] Navrotsky, A., Kleppa, O.J., “Thermodynamics of Formation of Simple Spinels”, J. Inorg. Nucl. Chem., 30, 479–498 (1968) (Experimental, Thermodyn., 30) Reijen, P., “Phase Equilibria in the System MgO-FeO-Fe2O3”, Phillips Res. Rep., 23, 151–188 (1968) (Experimental, Phase Relations, Thermodyn., 34) Blank, S.L., Pask, J.A., “Diffusion of Iron and Nickel in Magnesium Oxide Single Crystals”, J. Am. Ceram. Soc., 52, 669–675 (1969) (Experimental, 33) Aubry, J., Berthet, A., Duchene, R., Etienne, H., Evrard, O., Jeannot, F., Gleitzer, C., Offroy, C., Perrot, P., “Stabilization of Iron Monoxide by Formation of Solid Solution” (in French), Ann. Chim., 5, 299–308 (1970) (Experimental, Thermodyn., 45)

DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mg–O [1970Ber] [1970Lyk] [1971Gur]

[1971Mor]

[1972Bal]

[1972Rez]

[1973Abb] [1973Bar]

[1973Maj] [1974Kra] [1974Sah] [1974Sin1] [1974Sin2]

[1975Sch]

[1975Val1]

[1975Val2]

[1975Zal]

[1977Cor]

[1977Tri] [1978Cor]

Landolt-Börnstein New Series IV/11D4

39

Berthet, A., Perrot, P., “Equilibria in the Fe-Mg-O System at 850°C”, Mem. Sci. Rev. Met., 67(11), 747–753 (1970) (Experimental, Phase Relations, Thermodyn., 19) Lykasov, A.A., Kozheurov, V.A., “Equilibrium Oxygen Pressures over Magnesiowustite” Izv. Vyssh. Ucheb. Zaved., Chern. Metall., 13, 5–8 (1970) (Experimental, Thermodyn.) Gurevich, S.Yu., Lykasov, A.A., Mikhaylov, G.G., “Investigation of the Boundaries of the Wustite Region in the Fe-Mg-O System” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., 14(8), 28–31 (1971) (Electr. Prop., Experimental, Phase Diagram, Phase Relations, 12) Morton, I.P., Lewis, M.F., “Effect of Iron Impurities on Thermal Conductivity of Magnesium Oxide Single Crystals Below Room Temperature”, Phys. Rev. B, 3(2), 552–559 (1971) (Calculation, Experimental, 34) Balesdent, D., Evrard, O., Gleitzer, C., “Extension of Darken's Method to Heterogeneous Systems for the Calculation of the Activities” (in French), Rev. Chim. Miner., 9(1), 233–144 (1972) (Experimental, Thermodyn., 5) Rezlescu, N., Cuciureanu, E., Ioan, C., Luca, E., “Time Variation of the Electrical Conductivity in Spinel Ferrites”, Phys. Status Solidi A, 11(1), 351–9 (1972) (Experimental, Electr. Prop., 9) Abbattista, F., Borroni Grassi, G., Maja, M., “Activity of the Wuestite in (Fe,Mg)Ox Solid Solutions” (in Italian), Metall. Ital., (9), 485–488 (1973) (Experimental, 20) Barin, I., Knacke, O., Thermochemical Properties of Inorganic Substances, Springer-Verlag, Berlin, Heidelberg, New York, Verlag Stahleisen m.b.H., Düsseldorf, 292–295, 441, 462 (1973) (Thermodyn., Review, 7) Maja, M., Abbattista, F., “Thermodynamics Characteristic of the Magnesia-Wuestite System” (in Italian), Metall. Ital., 65(10), 565–570 (1973) (Experimental, Thermodyn., 18) Krawitz, A., Cohen, J.B., “Phase Relations at Low Temperatures in the Fe-Mg-O System”, J. Am. Ceram. Soc., 57(4), 186–189 (1974) (Experimental, Phase Relations, 22) Saha, P., Biggar, G.M., “An Investigation of Magnesiowüstite as a Calibrant of Oxygen Fugacy”, Indian J. Earth Sci., 1(2), 131–140 (1974) (Experimental, 7) Singh, R.N., Coble, R.L., “Dynamic Dislocation Behavior in Iron-doped Magnesium-Oxide Crystals”, J. Appl. Phys., 45(3), 990–995 (1974) (Experimental, Thermodyn., 11) Singh, R.N., Coble, R.L., “Dynamic Dislocation Behavior in Iron-Doped Magnesium-Oxide Crystals Containing Dislocation Dipoles”, J. Appl. Phys., 45(12), 5129–5135 (1974) (Experimental, Mechan. Prop., 16) Schiavello, M., Valigi, M., Pepe, F., “Structure and Catalytic Activity of Iron-Oxide and Magnesium-Oxide Solid-Solutions. 2. Catalytic Activity for N2O Decomposition”, J. Chem. Soc., Faraday Trans. 1, 71, 1642–1648 (1975) (Experimental, Thermodyn., 19) Valet, P.-M., Pluschkell, W., Engell, H.-J., “Equilibria Between MgO-FeO-Fe2O2 Solid Solutions and Oxygen” (in German), Arch. Eisenhuettenwes., 46(6), 383–388 (1975) (Calculation, Experimental, Phase Relations, 40) Valigi, M., Pepe, F., Schiavello, M., “Structure and Catalytic Activity of Iron-Oxide and Magnesium-Oxide Solid-Solutions. Structural and Magnetic Investigations”, J. Chem. Soc., Faraday Trans. 1, 71, 1631–1641 (1975) (Experimental, Crys. Structure, Magn. Prop., 27) Zalazinskii, A.G., Balakirev, V.F., Barkhatov, V.P., Chufarov, G.I., “Oxygen PressureComposition Diagram in the Mg-Fe-O System” (in Russian), Zh. Fiz. Khim., 49(6), 1551–1552 (1975) (Experimental, Thermodyn., 8) Cordischi, D., Pepe, F., Schiavello, M., Valigi, M., “Structure and Catalytic Activity of IronOxide and Magnesium-Oxide Solid-Solutions. 3. ESR Characterization”, J. Chem. Soc., Faraday Trans. 1, 73, 62–70 (1977) (Experimental, Thermodyn., 10) Trinel-Dufour, M.C., Perrot, P., “Thermodynamic Study of the Solid Solutions of the System Fe-Mg-O” (in French), Ann. Chim., 2, 309–318 (1977) (Experimental, Thermodyn., 21) Cordischi, D., Gazzoli, D., Valigi, M., “Redox Behavior of Mn, Fe and Cr in Solid Solution in Magnesium Oxide by ESR and X-Ray Diffraction Techniques”, J. Solid State Chem., 24, 371–379 (1978) (Experimental, 17)

MSIT®

DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

40 [1978Kau] [1978Lyk]

[1979Sek] [1980Bra]

[1980Gor]

[1980Shi]

[1980Sim]

[1981Rot] [1980Vla]

[1982Kub] [1983Dav]

[1983One]

[1984Dob]

[1984McC]

[1984Tre]

[1987Sre]

[1988Lue] [1988Rom]

Fe–Mg–O Kaufman, L., Nesor, H., “Calculation of Quasibinary and Quasiternary Oxide Systems - I”, Calphad, 2, 35–53 (1978) (Thermodyn., Theory, *, #, 30) Lykasov, A.A., Tarvid, L.S., “Use of the Theory of Ionic Regular Solutions for Describing the Thermodynamic Properties of Magnesiowüstite”, Izv. Vyssh. Ucheb. Zaved., Chern. Metall., 10, 9–12 (1978) (Experimental, Thermodyn., 9) Sekine, K., Yamaguchi, T., “Thermodynamics of Ferrite Systems” (in Japanese), Yogyo Kyokai Shi, 87(1009), 443–452 (1979) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 60) Brach, B.Ya., Bobrysheva, N.P., Belozerskii, G.N., “Nature of Interactions between iron Atoms in Solid Solutions of the Systems FeO - MgO, FeO(1+x) - MgO, Fe3O4 - MgAl2O4, α-Fe2O3 - Al2O3”, Inorg. Mater., 16(1), 65–68 (1980), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 16(1), 84–87 (1980) (Experimental, Magn. Prop., 8) Gorobets, A.P., “Investigation Into the Thermodynamics of the Deoxidation of Iron by a Magnesium Solution” (in Russian), Metall. Koksokhim, 69, 34–37 (1980) (Thermodyn., Experimental, 8) Shishkov, V.I., Lykasov, A.A., Il"ina, A.F., “Activity of the Components of Iron-Magnesium Spinel”, Russ. J. Phys. Chem., 54(3), 440–441 (1980) translated from Zh. Fiz. Khim., 54(3), 766–767 (1980) (Experimental, Phase Relations, Thermodyn., *, #, 3) Simons, B., “Composition-Lattice Parameter Relationship of the Magnesiowuestite Solid Solution Series”, Carnegie Inst. Washington, Yearbook, 79, 376–380 (1980) (Crys. Structure, Experimental, 13) Roth, R.S., Negas, T., Cook, L.P., Phase Diagrams for Ceramists, Am. Ceram. Soc., Columbus, Ohio, 34–34 (1981) (Phase Diagram, Phase Relations, Review, 7) Vlasova, M.V., Kakazei, N.G., Ristich, M.M., “Radiospectroscopic Investigation of Solid Phase Interaction in the System MgO-Fe2O3”, Inorg. Mater., 17(5), 598–602 (1981) (Experimental, 16) Kubaschewski, O., “Iron-Magnesium” in “Iron-Binary Phase Diagram”, Springer-Verlag, Berlin, 59–60 (1982) (Review, Phase Diagram, Phase Relations, 7) Davies, P.K., Navrotsky, A., “Quantitative Correlations of Deviations from Ideality in Binary and Pseudobinary Solid Solutions”, J. Solid State Chem., 46, 1–22 (1983) (Thermodyn., Theory, 96) O’Neill, H.S.C., Navrotsky, A., “Simple Spinels: Crystallographic Parameters, Cation Radii, Lattice Energies, and Cation Distribution”, Am. Mineral., 68, 181–194 (1983) (Crys. Structure, Review, Theory, Thermodyn., 49) Dobrovinskiy, P.Y., Mesnyankina, C.L., Men", A.N., “The Registration of Mutual Solubility of Phases in Thermodynamic of Phase Equilibria”, Zh. Fiz. Khim., 58, 2326–2328 (1984) (Experimental, Thermodyn., 4) Mc Cammon, C.A., Liu, L., “The Effect of Pressure and Temperature on Nonstoichiometric Wustite FexO: The Iron rich Phase Boundary”, Phys. Chem. Miner., 10, 106–113 (1984) (Experimental, 48) Trestman-Matts, A., Dorris, S.E., Mason, T.O., “Thermoelectric Determination of Cation Distributions in Fe3O4-MgFe2O4”, J. Am. Ceram. Soc., 67, 69–74 (1984) (Experimental, Thermodyn., 39) Srecec, I., Ender, A., Woermann, E., Gans, W., Jacobsson, E., Eriksson, G., Rosen, E., “Activity-Composition Relations of the Magnesiowustite Solid Solution Series in Equilibrium with Metallic Iron in the Temperature Range 1050–1400 K”, Phys. Chem. Miner., 14, 492–498 (1987) (Experimental, Thermodyn., 15) Luecke, W., Kohlstedt, D.L., “Kinetics of the Internal Oxidation of (Mg, Fe) Solid Solution”, J. Am. Ceram. Soc., 71(1), 189–195 (1988) (Experimental, Theory, 21) Romanovskii, L.B., Terekhin, V.A., “Transformation of Magnesium Iron Oxide (MgFe2O4) into Magnesium Oxide-Iron Oxide (MgO-FeO) Solid Solution on Cooling and Heating” (in Russian), Ukr. Khim. Zh. (Russ. Ed.), 54(1), 107–109 (1988) (Experimental, Phase Relations, 8)

DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mg–O [1988Sch]

[1988Wol] [1989Duf] [1989Nel]

[1989Rag] [1989Rag2] [1990Bec]

[1991Sun] [1991Wis] [1992Ita] [1993Hal] [1993Sax]

[1993Wu]

[1997Byg] [1997Fon]

[1997Ito] [1998Ber]

[1998Fab]

[1998Kan] [1999Cro]

Landolt-Börnstein New Series IV/11D4

41

Schurmann, E., Kolm, I., “Effect of the Iron(III) Oxide Contents in Steelmaking Slag on the Magnesia Solubility at Different Oxygen Partial Pressure on the Gas-Slag Equilibrium”, Steel Res., 59, 185–191 (1988) as quated in [2004Jun1] Wolfenstine, J., Kohlstedt, D.L., “Creep of (Mg, Fe)O Single Crystals”, J. Mater. Sci., 23(10), 3550–3557 (1988) (Experimental, Mechan. Prop., 42) Duffy, T.S., Anderson, D.L., “Seismic Velocities in Mantle Minerals and the Mineralogy of Upper Mantle”, J. Geophys. Res . 94, 1989, 1895–1912 (Review, Phys. Prop., 89) Nell, J., Wood, B.J., Mason, T.O., “High Temperature Cation Distribution Fe3O4-MgAl2O4MgFe2O4-FeAl2O4 Spinel from Thermopower and Conductivity Measurements”, Am. Mineral., 74, 339–351 (1989) as quoted in [2004Jun1] Raghavan, V., “The Fe-Mg-O System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., Calcutta, 5, 170–180 (1989) (Review, Phase Relations, Phase Diagram, 19) Raghavan, V., “The Fe-O System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. of Met., Calcutta, 5, 5–8 (1989) (Phase Diagram, Crys. Structure, Review, 3) Becker, K.D., “Spectroscopic in Situ Investigations of Solids at High Temperatures: A Mössbauer and Optical Spectroscopy Study of Diffusion and of the Kinetics of Solid State Reactions”, Solid State Ionics, Diffusion & Reactions, 39(1–2), 27–35 (1990) (Experimental, Kinetics, 29) Sundman, B., “An Assessment of the Fe-O System”, J. Phase Equilib., 12(1), 127–140 (1991) (Thermodyn., Assessment, *, #, 53) Wiser, N.M., Wood, B.J., “Experimental Determination of Activities in Fe-Mg Olivine at 1400 K”, Contrib. Mineral. Petrol., 108, 146–153 (1991) (Experimental, Thermodyn., 27) Ita, J., Stixrude, L., “Petrology, Elasticity and Composition of the Mantle Transition Zone”, J. Geophys. Res. – Solid Earth, 97B, 6849–6866 (1992) (Review, Phys. Prop., 178) Hallstedt, B., “The Magnesium-Oxygen System”, Calphad, 17(3), 281–286 (1993) (Phase Relations, Thermodyn., Theory, *, #, 8) Saxena, S.K., Chatterjee, N., Fei, Y., Chen, G., Thermodynamic Data on Oxides and Silicates: an Assessed Data Set Based on Thermochemistry and High Pressure Phase Equilibrium, Springer Verlag, Berlin, New-York, Heidelberg, pp. 428 (1993) (Review, Thermodyn.) Wu, P., Eriksson, G., Pelton, A.D., “Critical Evaluation and Optimization of the Thermodynamic Properties and Phase Diagrams of the CaO-FeO, CaO-MgO, CaO-MnO, FeO-MgO, FeO-MnO, and MgO-MnO Systems”, J. Am. Ceram. Soc., 76(8), 2065–2075 (1993) (Phase Diagram, Phase Relations, Thermodyn., Review, *, #, 73) Bygden, J., Jacobsen, A., Sichen, D., Seethraman, S., “Interdiffusion Studies in the System MgO-FeO”, Z. Metallkd., 88(5), 433 (1997) (Experimental, 17) Fontijn, W.F.J., van der Zaag, P.J., Devillers, M.A.C., Brabers, V.A.M., Metselaar, R., “Optical and Magneto-Optical Polar Kerr Spectra of Fe3O4 and Mg2+- or Al3+-Substituted Fe3O4”, Phys. Rev. B, 56(9), 5432–5442 (1997) (Experimental, 42) Itoh, H., Hino, M., Ban-ya, S., “Deoxidation Equilibrium of Magnesium in Liquid Iron” (in Japanese), Tetsu to Hagane (J. ISIJ), 83(10), 623–628 (1997) (Experimental, 13) Berry, F.J., Bohorquez, A., Greaves, C., McManus, J., Moore, E.A., Mortimer, M., “Structural Characterization of Divalent Magnetism-Doped α-Fe2O3”, J. Solid State Chem., 140, 428–430 (1998) (Crys. Structure, Experimental) Fabrichnaya, O., “The Assessment of Thermodynamic Parameters for Solid Phase in the Fe-Mg-O and Fe-Mg-Si-O Systems”, Calphad, 22(1), 85–125 (1998) (Thermodyn., Assessment, 61) Kang, S.-H., Yoo, H.-J., “Composition (x) Dependence of Nonstoichiometry (δ) in Ferrite Spinel (MgxFe1–x)3–δO4”, J. Solid State Chem., 139, 128–134 (1998) (Experimental, 23) Cross, W.B., Afﬂeck, L., Kuznetsov, M.V., Parkin, I.P., Pankhurst, Q.A., “Self-Propagating High-Temperature Synthesis of Ferrites MFe2O4 (M = Mg, Ba, Co, Ni, Cu, Zn); Reactions in an External Magnetic Field”, J. Mater. Chem., 9, 2545–2552 (1999) (Crys. Structure, Experimental, Magn. Prop., 26)

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DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

42 [1999Har]

[2000Ber]

[2000Fab]

[2000Kan] [2000Leb]

[2000Vas]

[2001And]

[2001Boi]

[2001Dub]

[2001Mey]

[2002Dec]

[2002Jac]

[2002Kat]

[2002Mer]

[2002Zha] [2003Hon]

Fe–Mg–O Harrison, R.J., Putnis, A., “Determination of the Mechanism of Cation Ordering in Magnesioferrite (MgFe2O4) from the Time- and Temperature-Dependence of Magnetic Susceptibility”, Phys. Chem. Miner., 26, 322–332 (1999) (Crys. Structure, Experimental, Kinetics, Magn. Prop., 39) Berry, F.J., Greaves, C., Helgason, O., McManus, J., Palmer, H.M., Williams, R.T., “Structural and Magnetic Properties of Sn-, Ti-, and Mg-substituted α-Fe2O3: a Study by Neutron Diffraction and Mössbauer Spectroscopy”, J. Solid State Chem., 151, 157–162 (2000) (Crys. Structure, Experimental, Magn. Prop., 16) Fabrichnaya, O.B., “Thermodynamic Modelling of Melting in the System FeO-MgO-SiO2O2 at Pressure of 1 bar”, Calphad, 24(2), 113–131 (2000) (Thermodyn., Phase Relations, Phase Diagram, Calculation, 24) Kang, S-H., Chang, S-H., Yoo, H-I., “Phase Stability in the System Mg-Fe-O”, J. Solid State Chem., 149, 33–40 (2000) (Crys. Structure, Experimental, Phase Relations, 29) Lebrun, N., “Iron-Magnesium-Oxygen”, MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 10.10323.1.20, (2000) (Crys. Structure, Phase Diagram, Assessment, 53) Vassent, J.L., Marty, A., Gilles, B., Chatillon, C., “Thermodynamic Analysis of Molecular Beam Epitaxy of MgO(s). II. Epitaxial Growth of MgO Layers on Fe(001) Substrates”, J. Cryst. Growth, 219(4), 444–450 (2000) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 13) Andrault, D., Bolfan-Casanova, N., “High-Pressure Phase Transformation in the MgFe2O4 and Fe2O3-MgSiO3 Systems”, Phys. Chem. Miner., 28, 211–217 (2001) (Crys. Structure, Experimental, 26) Boiocchi, M., Caucia, F., Merli, M., Prella, D., Ungaretti, L., “Crystal-Chemical Reason for the Immiscibility of Periclase and Wuestite under Lithospheric P, T Conditions”, Eur. J. Mineral, 13(5), 871–881 (2001) (Crys. Structure, Experimental, Morphology, Phase Relations, 36) Dubrovinsky, L., Dubrovinskaia, N., Annersten, H., Halenius, E., Harryson, H., “Stability of (Mg0.5Fe0.5)O and (Mg0.8Fe0.2)O Magnesiowüstite in the Lower Mantle”, Eur. J. Mineral, 13(5), 857–861 (2001) (Crys. Structure, Experimental, Phase Relations, 22) Meyerheim, H.L., Popescu, R., Krischner, J., Jedrecy, N., Sauvage-Simkin, M., Heinrich, B., Pinchaux, R., “Geometrical and Compositional Structure at Metal-Oxide Interfaces: MgO on Fe(001)”, Phys. Rev. Lett., 87(7), 076102–1-4 (2001) (Crys. Structure, Experimental, Magn. Prop., 25) Decterov, S.A., Jung, I.-H., Pelton, A.D., “Thermodynamic Modeling of the FeO-Fe2O3MgO-SiO2 System”, J. Am. Ceram. Soc., 85(12), 2903–2910 (2002) (Calculation, Phase Diagram, Phase Relations, 68) Jacobsen, S.D., Spetzler, H.A., Reichmann, H.J., Smyth, J.R., Mackwell, S.J., Angel, R.J., Bassett, W.A., “Gigahertz Ultrasonic Interferometry at High P and T: New Tools for Obtaining a Thermodynamic Equation of State”, J. Phys. Condens. Matter., 14(44), 11525–11530 (2002) (Experimental, Thermodyn., 11) Katayama, I., Iseda, A., “Thermodynamic Study of Spinel-Type Solid Solutions of the Fe3O4-MgFe2O4 Coexisting with Fe2O3 by Emf Method”, Scand. J. Metall., 31(6), 374–378 (2002) (Experimental, Thermodyn., 12) Merli, M., Pavese, A., Ranzini, M., “Study of the Electron Density in MgO, (Mg0.963Fe0.037) O and Cu2O by the Maximum Entropy Method and Miltipole Reﬁnements: Comparison between Methods”, Phys. Chem. Miner., 29(7), 455–464 (2002) (Crys. Structure, Electronic Structure, Experimental, 38) Zhang, J., Kostak, P., “Thermal Equation of State of Magnesiowüstite”, Phys. Earth Planet. Interiors, 129, 301–311 (2002) (Crys. Structure, Experimental, Magn. Prop., 31) Honda, T., Kaneko, S., “Phase Relations in the MgO-Rich Region of the System MgOFe2O3”, J. Ceram. Soc. Jpn., 111(11), 841–847 (2003) (Electronic Structure, Phase Diagram, Phase Relations, 19)

DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mg–O [2003Lin]

[2003Yam] [2004Fab]

[2004Jun1]

[2004Jun2]

[2004Kon]

[2004Lev]

[2004Shi]

[2005Ant]

[2005Gat]

[2005Jac]

[2005Wes]

[2006Kan1]

[2006Kan2]

[2006Lin]

[2006Lon]

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Lin, J.F., Heinz, D.L., Mao, H.K., Hemley, R.J., Devine, J.M., Li, J., Shen, G.Y., “Stability of Magnesiowüstite in Earths Lower Mantle”, Proc. Nat. Acad. Sci. USA, 100(8), 4405–4408 (2003) (Experimental, Thermodyn., 35) Yamazaki, D., Irifune, T., “Fe-Mg Interdiffusion in Magnesiowüstite up to 35 GPa”, Earth Planet. Sci. Letters, 216(3), 301–311 (2003) (Experimental, Phys. Prop., 35) Fabrichnaya, O., Saxena, S.K., Richet, P., Westrum, E.F., Thermodynamic Data, Model and Phase Diagrams in Multicomponent Oxide Systems, Springer Verlag, Berlin, Heidelberg, pp. 198 (2004) (Review, Phase Diagram, Phase Relations, Thermodyn., 479) Jung, I.-H., Decterov, S.A., Pelton, A.D., “Critical Thermodynamic Evaluation and Optimization of the Fe-Mg-O System”, J. Phys. Chem. Solids, 65(10), 1683–1695 (2004) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., 81) Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in Steel”, Metall. Mater. Trans. B, 35b(3), 493–507 (2004) (Calculation, Theory, Thermodyn., 100) Kondo, T., Ohtani, E., Hirao, N., Yagi, T., Kikegawa, T., “Phase Transitions of (Mg, Fe)O at Megabar Pressures”, Phys. Earth Planet. Interiors, 143–144, 201–213 (2004) (Crys. Structure, Experimental, Optical Prop., Phase Relations, 30) Levy, D., Diella, V., Dapiaggi, M., Sani, A., Gemmi, M., Pavese, A., “Equation of State, Structural Behaviour and Phase Diagram of Synthetic MgFe2O4, as a Function of Pressure and Temperature”, Phys. Chem. Miner., 31(2), 122–129 (2004) (Crys. Structure, Experimental, Phase Relations, 38) Shibata, H., Jiang, X., Valdez, M., Cramb, A.W., “The Contact Angle Between Liquid Iron and Single Crystal Magnesium Oxide Substrate at 1873 K”, Metall. Mater. Trans. B, 35B(1), 179–181 (2004) (Interface Phenomena, Experimental, 13) Antao, S.M., Hassan, I., Parise, J.B., “Cation Ordering in Magnesioferrite, MgFe2O4, to 982°C Using in Situ Synchrotron X-Ray Powder Diffraction”, Am. Mineral., 90(1), 219–228 (2005) (Calculation, Crys. Structure, Experimental, Thermodyn., 38) Gateshki, M., Petkov, V., Pradhan, S.K., Vogt, T., “Structure of Nanocrystalline MgFe2O4 from X-ray Diffraction, Rietveld and Atomic Pair Distribution Function Analysis”, J. Appl. Crystallogr., 38(5), 772–779 (2005) (Crys. Structure, Experimental, Magn. Prop., 46) Jacobsen, S.D., Lin, J.-F., Angel, R.J., Shen, G.Y., Prakapenka, V.B., Dera, P., Mao, H.-K., Hemley, R.J., “Single-Crystal Synchrotron X-ray Diffraction Study of Wüstite and Magnesiowüstite at Lower-Mantle Pressures”, J. Synchrotron Radiation, 12, 577–583 (2005) (Crys. Structure, Experimental, Kinetics, 38) Van Westrenen, W., Li, J., Fei, Y., Frank, M.R., Hellwig, H., Komabayashi, T., Mibe, K., Minarik, W.G., Van Orman, J.A., Watson, H.C., Funakoshi, K.-I., Schmidt, M.W., “Thermoelastic Properties of (Mg0.64Fe0.36)O Ferropericlase Based on in Situ X-Ray Diffraction to 26.7 GPa and 2173K”, Phys. Earth Planet. Interiors, 151(1–2), 163–176 (2005) (Crys. Structure, Experimental, Mechan. Prop., Thermodyn., 42) Kantor, I., Dubrovinsky, L., McCammon, C., Kantor, A., Pascarelli, S., Aquilanti, G., Crichton, W., Mattesini, M., Ahuja, R., Almeida, J., Urusov, V., “Pressure-Induced Phase Transition in Mg0.8Fe0.2O Ferropericlase”, Phys. Chem. Miner., 33, 35–44 (2006) (Calculation, Experimental, Phase Relations, Kinetics, 53) Kantor, I.Y., Dubrovinsky, L.S., McCammon, C.A., “Spin Crossover in (Mg, Fe)O: a Mössbauer Effect Study with an Alternative Interpretation of X-ray Emission Spectroscopy Data”, Phys. Rev. B, 73(B), 100101 (2006) (Experimental, Crys. Structure, Electronic Structure, Kinetics, 14) Lin, J.-F., Gavriliuk, A.G., Struzhkin, V.V., Jacobsen, S.D., Sturhahn, W., Hu, M.Y., Chow, P., Yoo, C.S., “Pressure-Induced Electronic Spin Transition of Iron in Magnesiowüstite-(Mg,Fe) O”, Phys. Rev. B, 73, 113107 (2006) (Experimental, Phys. Prop., 28) Long, M.D., Xiao, X.H., Jiang, Z.T., Evans, B., Karato, S., “Lattice Preferred Orientation in Deformed Polycrystalline (Mg, Fe)O and Implications for Seismic Anisotropy in D”, Phys.

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[2006Tom]

[2006Zha]

[Mas2] [V-C2]

Fe–Mg–O Earth Planet. Interiors, 156(1–2), 75–88 (2006) (Crys. Structure, Experimental, Mechan. Prop., 36) Tommaseo, C.E., Devine, J., Merkel, S., Speziale, S., Wenk, H.-R., “Texture Development and Elastic Stresses in Magnesiowüstite at High Pressure”, Phys. Chem. Miner., 33, 84–97 (2006) (Crys. Structure, Experimental, Kinetics, Mechan. Prop., 54) Zhang, L., Gong, Z.-Z., “Shock Compression and Phase Transitions of Magnesiowüstite (Mg, Fe)O up to Earths Lowermost Mantle Conditions”, Chin. Phys. Lett., 23(11), 3049–3051 (2006) (Experimental, Mechan. Prop., 21) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_13 # Springer 2008

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Fe–Mg–S

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Iron – Magnesium – Sulfur Ludmyla Tretyachenko

Introduction Investigation of the phase relations in the Fe-Mg-S system was started because some compositions of the MgS-FeS system were found to be constituents of meteorites (niningerite [1971Ski] as well as keilite [2002Shi, 2007Kei]). Niningerite is unknown in terrestrial rocks. The phase relations in the MgS-FeS section were mostly studied [1971Ski, 1973Kur, 1984McC, 1984Osb, 2006And]. Electronic structure of MgS-FeS compositions has been investigated by [2000Far, 2001Ste, 2002Far, 2002Kra, 2004Kra]. The equilibria between Mg and S in liquid Fe have been studied by [1992Han, 1995Zho, 1997Han]. Desulfurization of molten iron with magnesium has been investigated by [1978Nas, 1979Iro, 2007Yan]. A mechanism of resulfurization of liquid Fe with MgS has been studied by [2005Yan, 2007Yan]. Phase equilibria in the MgS-FeS section at high pressure were studied experimentally and calculated from thermodynamic data by [1984McC]. Samples along the MgS-FeS section were prepared of mixtures of pure elements [1973Kur, 1984McC, 2000Far, 2004Kra] or MgS and FeS preliminary prepared [1971Ski, 1984Osb, 2006And] by reactions during heating in sealed evacuated silica glass tubes at appropriate temperatures mostly followed by quenching in cold water. Earlier works [1971Ski] and [1973Kur] on the phase reactions in the Fe-Mg-S system (FeS-MgS section) were reviewed by [1988Rag]. A more complete review was presented by [2000Tre]. Experimental investigations on the phase relations and the structure of phases in the Fe-Mg-S system are listed in Table 1. Binary Systems The Fe-Mg phase diagram is given in [1982Kub1]. The Fe-S phase diagram is taken from [Mas2], where it is shown according to [1982Kub2]. The Mg-S phase diagram is not determined. The MgS compound melts congruently at 1927°C [1989And]. Solid Phases Ternary compounds are not found. Data on the binary compounds and solid solutions on their base are given in Table 2. Extended ternary solid solutions with the NaCl type (B1) crystal structure were found only for MgS [1971Ski, 1973Kur, 1984McC, 1984Osb, 2000Far, 2006And]. The solid solutions (Mg1–xFex)S extend up to 75 mol% FeS at ∼1250°C [2006And]. Concentration dependence of the (Mg1–xFex)S lattice parameters was determined by [1971Ski, 1973Kur, 1984McC, 1984Osb] and found to be linear. The equation a = 520.4 – 0.1299x was proposed by [1984McC] for the concentration dependence of the lattice parameter of (Mg1–xFex)S. [2006And] revealed a positive deviation from the Vegards’ law. The MgS solubility in FeS was found to be below 0.1 mol% up to 1000°C [1971Ski]. The maximum solubility was determined to be 2 mol% MgS at ∼1200°C [2006And]. Quasibinary Systems Taking into account that the congruent melting of FeS takes place at 52 at.% S (FeS1.08) and the results of [2006And] obtained for the FeS-MgS and FeS1.03-MgS sections, the FeS1.08-MgS section can be considered as the quasibinary one of the peritectic type. The peritectic reaction L + MgS ⇌ γFeS takes place at ∼1200°C, the peritectic point is located at 2 ± 0.5 mol% MgS. The solubility of MgS in γFeS does not exceed ∼1 mol% but FeS dissolves in MgS up to ∼75 mol%. Landolt-Börnstein New Series IV/11D4

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Fe–Mg–S

Invariant Equilibria The presence of Fe in as-cast MgS-FeS samples rich in FeS evidenced the existence of a three-phase region MgS + γFeS + (γFe) below the solidus surface [2006And]. Taking into account a eutectic melting at 1070°C in similar compositions reported by [1971Ski], the invariant equilibrium MgS + L ⇌ γFeS + (γFe) at ∼1070°C can be assumed to take place in the ternary system. Temperature – Composition Sections The section FeS-MgS is shown in Fig. 1 according to [2006And] with some corrections taking into account that the congruent melting point of FeS corresponds to 52 at.% S rather than 50 at.% S. The peritectic reaction MgS + L ⇌ γFeS was found to take place in this section at 1197°C. Eutectic type grains of iron were observed in as-cast samples containing ∼3–4 mol% FeS. The samples annealed at 497 and 897°C for 1300 and 740 h respectively did not contain the Fe grains. A eutectic melting at 1070°C in samples containing Fe was observed also by [1971Ski]. The Fe phase grains were not revealed in FeS1.03-MgS samples [2006And]. The peritectic temperature in this section was determined as 1200°C. The solvus line determined by [1971Ski, 1984McC] is consistent with that shown by [2006And]. [1973Kur] determined the solubility of FeS in MgS to be 50 mol% at 900°C, that is lower than the values found in other works. [1984McC] assumed that this may be caused by too slow quenching from a high temperature. A dependence of the MgS solid solutions composition on the quenching rate was studied by [1971Ski]. The FeS phase in samples quenched from a high temperature and examined by means of XRD at room temperature was shown to be the low temperature modiﬁcation of this sulﬁde, αFeS (troilite) [1971Ski] in spite it is well established that in pure FeS the troilite αFeS is not stable above 138°C. Polymorphic transitions of FeS were revealed in the MgS-FeS section by means of DTA at 312°C (γFeS/ βFeS) and 132°C (βFeS/αFeS) [2006And]. Thermodynamics Thermodynamic data were derived from the FeS-MgS solid solutions to calculate the phase diagram at high pressure [1984McC]. The values of ΔG0 (0, 1000°C) and ΔV (0, 25°C) have been determined to be –4.1 kJ·mol–1 and –1.4 cm3·mol–1 respectively. The equilibrium between magnesium and sulfur in liquid iron at 1600°C has been studied by [1992Han, 1995Zho, 1997Han] using the vapor-liquid equilibrium method. The solubility product for MgS has been measured to be K′MgS = 2.36·10–4 and the equilibrium constant has been obtained to be KMgS = 2.0·10–4 for the reaction MgS(s) = {Mg} + {S}. Notes on Materials Properties and Applications The microhardness of the Fe and MgS solid solutions in the samples annealed at 897°C for 740 h measured under a load of 0.4 N by [2006And] is shown in Fig. 2. Magnesium can be used as a desulfurizing agent for molten iron [1978Nas, 1979Iro, 1997Han, 2005Yan, 2007Yan]. Desulfurization kinetics was studied by [1979Iro, 2005Yan, 2007Yan]. [2007Yan] studied a mechanism of resulfurization and proposed methods of its prevention. Miscellaneous The FeS-MgS phase diagram was determined at high pressures using samples with compositions close to the phase boundary between the single-phase MgS (NaCl type) region and the two-phase MgS + FeS (NiAs type) region [1984McC]. The single-phase MgS sample (50 mol% FeS) and the two-phase MgS + FeS one (80 mol% FeS) were used. Experiments were carried out at 1000°C at high pressures up to 6.0 GPa. The obtained samples have been studied by means of XRD. The phase diagram of FeS-MgS determined from the high pressure experiments is shown in Fig. 3. The most notable feature of the phase diagram is a considerable displacement of the MgS phase boundary towards MgS at high pressure and a pressure insensitivity of the composition of the FeS phase. DOI: 10.1007/978-3-540-78644-3_14 # Springer 2008

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The composition of the MgS/(MgS + FeS) phase boundary in the FeS-MgS system at high pressure and 1000°C has been calculated from the thermodynamic data derived from the solid solution. In the calculation FeS (NiAs type) was assumed to be a pure phase stable at 1000°C from 0.1 to 6.0 GPa. Nonstoichiometry of FeS was neglected. A good agreement was found between the experimental results and the calculated curve. So, the analysis, which predicts exsolution of FeS (NiAs type) from MgS (NaCl type) at high pressure, was shown to be valid. Mössbauer spectra of (Mg1–xFex)S at 78 and 300 K have been obtained by [1973Kur]. The Mössbauer spectra obtained for these solid solutions at 4.2 and 298 K, as well as for this phase quenched from high pressure, have been discussed by [1984McC]. Mössbauer spectra of (Mg,Fe)S solid solutions within the composition range 8.4 to 50.0 mol% FeS quenched from 1000°C have been obtained at 300 K and discussed by [1984Osb]. X-ray absorption near-edge structure (XANES) spectra were used to analyze an evolution of local electronic structure of (Mg1–xFex)S solid solutions [2000Far, 2001Ste, 2002Far, 2002Kra, 2004Kra]. The XANES spectra were obtained experimentally and calculated theoretically. It was shown that in the (Mg1–xFex)S solid solutions FeS changes its structure from NiAs type (B8) to NaCl type (B1) under the inﬂuence of the MgS matrix at x below 0.68 (the samples were annealed at 1000°C). The S K-edge XANES spectrum of the hypothetical cubic B1 type FeS phase was derived from the spectrum of Mg0.375Fe0.625S by [2000Far]. The lattice parameters of the hypothetical B1 type FeS was evaluated by means of extrapolation to be a = 508.4 pm for the linear concentration relationship and a = 504.5 pm for the second-order polynomial [2006And]. Table 1.

Investigations of the Fe-Mg-S Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/ Phase Range Studied

[1971Ski]

XRD, light microscopy, EMPA

600–1000°C; MgS-FeS

[1973Kur]

XRD, Mössbauer spectroscopy (78 and 300 K)

Quenching from 900°C, 0 to 70 mol% FeS

[1984Osb]

XRD, Mössbauer spectroscopy (78 and 300 K)

Quenching from 1000°C, 8.39 to 50 mol% FeS

[1984McC]

XRD, Mössbauer spectroscopy (4.2 and 298 K), experiments at high pressures (up to 6 GPa), calculation

1000°C, (Mg1–xFex)S, 0 ≤ x ≤ 0.67

[1992Han]

Vapor - molten metal equilibrium method

1600°C, MgS in molten Fe

[1995Zho]

Vapor - liquid equilibrium method

1600°C, MgS in molten Fe

[1997Han]

Vapor - liquid equilibrium method

1600°C, MgS in molten Fe

[2000Far]

XRD, X-ray absorption spectroscopy

1000°C (annealed and quenched), (Mg1–xFex)S, 0 ≤ x ≤ 1

[2001Ste]

X-ray absorption spectroscopy, calculation

(Mg1–xFex)S, 0 ≤ x ≤ 0.68

[2002Far]

X-ray absorption spectroscopy

(Mg1–xFex)S

[2002Kra]

X-ray absorption spectroscopy, calculation

(Mg1–xFex)S

[2004Kra]

X-ray absorption spectroscopy

(Mg1–xFex)S

[2006And]

Microscopy, XRD, microhardness measurement, DTA, melting temperature determination by means of visual polythermal analysis (VPTA) (incipient melting)

up to 2227°C, MgS-FeS, MgS-FeS1.03

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4 Table 2.

Fe–Mg–S Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) 1538–1394

cI12 Im 3m W

a = 293.15

at 1390°C [Mas2]

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [Mas2]

(αFe) < 912

cI2 Im 3m W

a = 286.65

at 25°C [Mas2]

(Mg) < 650

hP2 P63/mmc Mg

a = 320.94 c = 521.07

[Mas2]

(βS) 115.22–95.5

mP64 P21/c βS

a = 1102 b = 1096 c = 1090 β = 96.7

at 103°C [Mas2, V-C2]

(αS) < 95.5

oF128 Fddd αS

a = 1046.4 b = 1286.60 c = 2448.60

at 25°C [Mas2, V-C2]

γFeS (h1) 1188–315

hP4 P63/mmc NiAs

βFeS (h2) 315–∼60

αFeS (r) < 138

hP24 P 62c FeS

hP6 P63/mmc FeS

a = 344.36 c = 587.59 a = 345.59 to 344.40 c = 577.89 to 587.00 a = 344.7 ± 0.5 c = 588 ± 1

a = 596.3 c = 1175.4 a = 586.1 c = 1157.7 a = 599.8 c = 1171 a = 597 c = 1173 a = 345.59 ± 0.05 c = 577.89 ± 0.05

50 to 55 at.%, congruent melting at 52 at.% S [Mas2] [V-C2] for FexS, x = 0.94 to 1 (given as NiS type) [V-C2] at 6 GPa, 1000°C in two-phase (80FeS-20MgS) (mol%) composition [1984McC] troilite [Mas2, 1982Kub2] at 21°C, p = 0.1 MPa [V-C2] at 21°C, p = 3.33 GPa [V-C2] at 120°C [V-C2] [2006And] in Fe0.94S [V-C2]

(continued) DOI: 10.1007/978-3-540-78644-3_14 # Springer 2008

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Fe–Mg–S

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

FeS (I)

oP8 Pnma MnP

FeS (mackinawite)

tP4 P4/nmm PbO

βFeS2 (h) 743–∼425

cP12 Pa3 FeS2

αFeS2 (r) ≲ 425

oP6 Pnnm FeS2

(Mg1–xFex)S

cF8 Fm 3m NaCl

MgS (niningerite) < 1927

Lattice Parameters [pm]

a = 582.5 b = 346.8 c = 693.5 a = 565 b = 331.6 c = 663.1 a = 571.6 b = 334.7 c = 669.4

Comments/References

50 to ∼52 at.% S [Mas2] at 50 at.% S [Mas2] at 190°C [V-C2]

at 21°C, p = 6.35 GPa [V-C2]

at 21°C, p = 4.15 GPa [V-C2]

a = 368 c = 504

at 17°C [V-C2]

a = 541.8

pyrite [V-C2, Mas2, 1982Kub2]

a = 443.6 b = 541.6 c = 338.1

a = 520 a = 520.20 to 511.16 a = 520.3±0.2 to 515 a = 519.5 to 513.5 a = 519.6 a = 514.6 a = 512.7

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MSIT®

marcasite [V-C2]

[1971Ski, 1973Kur, 1984Osb, 1984McC, 2000Far, 2006And] 0 ≤ x ≤ 0.75 at 1200°C [2006And] [V-C2, 1989And] 0 ≤ x ≤ 0.67 [1971Ski] 0 ≤ x ≤ 0.6 [1973Kur] 0.0839 ≤ x ≤ 0.5, quenched from 1000°C [1984Osb] at x = 0 [2006And] at x = 0.35 [2006And] at x = 0.58 [2006And]

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Fig. 1. Fe-Mg-S.

Fe–Mg–S

The FeS-MgS section

DOI: 10.1007/978-3-540-78644-3_14 # Springer 2008

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Fig. 2. Fe-Mg-S. Concentration dependence of microhardness of the phases in the FeS-MgS samples annealed at 897°C: a - FeS; b – MgS

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Fig. 3. Fe-Mg-S.

Fe–Mg–S

Phase diagram of the FeS-MgS determined from high-pressure experiments at 1000°C

DOI: 10.1007/978-3-540-78644-3_14 # Springer 2008

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Fe–Mg–S References [1971Ski]

[1973Kur]

[1978Nas] [1979Iro] [1982Kub1] [1982Kub2] [1984McC]

[1984Osb]

[1988Rag]

[1989And] [1992Han]

[1995Zho]

[1997Han] [2000Far]

[2000Tre]

[2001Ste]

[2002Far]

[2002Kra]

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Skinner, B.J., Luce, F.D., “Solid Solutions of the Type (Ca, Mg, Mn, Fe)S and Their Use as Geothermometers for the Enstatite Chondrites”, Am. Mineral., 56, 1269–1296 (1971) (Crys. Structure, Experimental, 19) Kurash, V.V., Kulikov, G.A., Makarov, E.S., “Investigation of the Isomorphism of Mg and Fe in the Niningerite MgS - Troilite FeS System” (in Russian), Geokhimiya, (8), 1266–1267 (1973) (Crys. Structure, Experimental, Phase Relations, 2) Nashiwa, H., Ueda, S., Yamaguchi, S., Nagao, N., “Desulfurization of Hot Metal With Magnesium”, Proc. Annu. Meet.-Int. Magnesium Assoc., (35), 19–23 (1978) (Experimental, 4) Irons, G.A., “Desulphurization Kinetics of Molten Iron by Magnesium Vapour”, Diss. Abstr. Int., 39B, 4535 (1979) (Experimental, Kinetics, 0) Kubaschewski, O., “Iron – Magnesium” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, Verlag Stahleisen, Duesseldorf, 59–60 (1982) (Phase Diagram, Review, #, 7) Kubaschewski, O., “Iron – Sulfur” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, Verlag Stahleisen, Duesseldorf, 364–365 (Phase Diagram, Review, #, 20) McCammon, C.A., Jackson, I., Ringwood, A.E., Cashion, J.D., “The Binary Systems FeSMgS and FeS-MnS: Mössbauer Spectroscopy of the B1 Solid Solutions and High Pressure Phase Equilibria”, Phys. Chem. Miner., 11, 182–193 (1984) (Calculation, Crys. Structure, Electronic Structure, Experimental, Phase Diagram, #, 39) Osborne, M.D., Fleet, M.E., “Mössbauer Investigation of Niningerite Solid Solutions (Mg, Fe)S”, Phys. Chem. Miner., 10, 245–249 (1984) (Crys. Structure, Electronic Structure, Experimental, Phase Relations, 23) Raghavan, V., “The Fe-Mg-S (Iron-Magnesium-Sulphur) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., Calcutta, 2, 153 (1988) (Crys. Structure, Review, Phase Relations, 3) Andreev, O.V., Kertman, A.V., Kislovskaya, T.M., “The MgS-La2S3 System” (in Russian), Zh. Neorgan. Khim., 34, 2913–2915 (1989) (Crys. Structure, Experimental, Phase Diagram, 11) Han, Q., Zhang, X., Wang, P., Chen, D., Wang, C., “Thermodynamic Behavior of Alkaline Earth Elements in Molten Iron and Nickel” (in Chinese), Beijing Keji Daxue Xuebao (Univ. Sci. Technol. Bejing), 14, 85–93 (1992) (Experimental, Review, Thermodyn., 37) Zhou, D., Han, Q., “Investigation of Equilibrium Between Magnesium and Sulfur in Liquid Iron” (in Chinese), Beijing Keji Daxue Xuebao (Univ. Sci. Technol. Bejing), 17, 576–579 (1995) (Experimental, Thermodyn., 8) Han, Q., Zhou, D., Xiang, C., “Determination of Dissolved Sulfur and Mg-S, Mg-O Equilibria in Molten Iron”, Steel Res., 68, 9–14 (1997) (Calculation, Experimental, Thermodyn., 13) Farrell, S.P., Fleet, M.E., “Evolution of Local Electronic Structure in Cubic Mg1–xFexS by S K-edge XANES Spectroscopy”, Solid State Commun., 113, 69–72 (2000) (Electronic Structure, Experimental, Phase Relations, 21) Tretyachenko, L., Bondar, A., Tretyachenko, C., “Iron – Magnesium – Sulfur” in “Ternary Alloys”, Ed. Effenberg, G., Weinheim (FRG); VCH., Vol. 17, 558–563 (2000); MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg, G., (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 10.24243.1.20 (1992) (Assessment, Crys. Structure, Phase Diagrams, 9) Stekhin, I.E., Soldatov, A.V., Farrel, S.P., Fleet, M.E., “Electronic Structure Investigation of Mg1–xFexS Solid Solution: X-ray Absorption Study” (Abstract), J. Synchrotron Rad., 8, 238–239 (2001) (Calculation, Electronic Structure, Experimental, 8) Farrell, S.P., Fleet, M.E., Stekhin, I.E., Kravtsova, A., Soldatov, A.V., Liu, X., “Evolution of Local Electronic Structure in Alabandite and Niningerite Solid Solutions {(Mn,Fe)S, (Mg, Mn)S, (Mg,Fe)S} Using Sulfur K- and L-Edge XANES Spectroscopy”, Am. Mineral., 87, 1321–1332 (2002) (Electronic Structure, Experimental, 59) Kravtsova, A.N., Stekhin, I.E., Soldatov, A.V., Liu, X., Fleet, M.E., “B1 Phase of FeS in Mg1–xFexS Solid Solution: X-ray Absorption Study”, Phys. Status Solidi B, 234, R4–R5 (2002) (Calculation, Electronic Structure, Experimental, Phase Relations, 4) MSIT®

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[2004Kra]

[2005Yan]

[2006And]

[2007Kei]

[2007Yan]

[Mas2] [V-C2]

Fe–Mg–S Shimizu, M., Yoshida, H., Mandarino, J.A., “The New Mineral Species Keilite, (Fe,Mg)S, the Iron-Dominant Analogue of Niningerite”, Can. Mineral., 40, 1687–1692 (2002) (Review, 18) Kravtsova, A.N., Stekhin, I.E., Soldatov, A.V., Liu, X., Fleet, M.E., “Electronic Structure of MS (M = Ca, Mg, Fe, Mn): X-Ray Absorption Analysis”, Phys. Rev. B, 69, 134109–1-12 (2004) (Calculation, Electronic Structure, Experimental, Phase Relations, 62) Yang, J., Kuwabara, M., Teshigawara, T., Sano, M., “Mechanism of Resulfurization in Magnesium Desulfurization Process of Molten Iron”, ISIJ Int., 45, 1607–6015 (2005) (Experimental, Kinetics, 25) Andreev, O.V., Solov’eva, A.V., Burkhanova, T.M., “MgS-FeS Phase Diagram”, Russ. J. Inorg. Chem. (Engl. Transl.), 51, 1826–1828 (2006), translated from Zh. Neorg. Khimii, 51, 1938–1941 (2006) (Experimental, Phase Diagram, #, 9) Keil, K., “Occurrence and Origin of Keilite, (Fe > 0.5, Mg < 0.5)S, in Enstatite Chondrite Impact-Melt Rocks and Impact-Melt Breccias”, Chemie der Erde (Geochemistry), 67, 37–54 (2007) (Experimental, Morphology, Phase Relations, 52) Yang, Y., Kuwabara, M., Sakai, T., Uchida, N., Liu, Z.Z., Sano, M, “Simultaneous Desulfurization and Deoxidation of Molten Steel with in Situ Produced Magnesium Vapor”, ISIJ Int., 47, 418–426 (2007) (Experimental, Abstract, 26) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_14 # Springer 2008

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Fe–Mg–Si

1

Iron – Magnesium – Silicon Nathalie Lebrun, Christian Baetzner, Athanasios Stamou, James Robinson, Lazar Rokhlin

Introduction The Fe-Mg-Si system alloys were studied in a number of the works, Table 1. A great part of them was devoted to the Fe-Mg-Si phase diagram. [1954Zwi] presented an equilibrium liquidus surface obtained from thermal analysis, metallography and Debye-Scherrer patterns in the silicon rich composition range. The part of the diagram which was not investigated experimentally, was presented schematically [1954Zwi]. He stipulated that the primary crystallization of the ﬁeld FeSi phase occupies the largest part of the liquidus surface. [1970Gui, 1971Gui] determined at 1454.5°C the extent of the miscibility gap between iron rich and magnesium rich liquids. The magnesium solubility was measured at lower silicon levels (5 to 17 mass% Si) in the iron rich region and the solubility of iron in the magnesium rich liquid. Measurements have been performed with a new technique for vapor pressure measurements. A series of melts was made from high purity materials. Preliminary experiments have been done to determine the time needed to establish the equilibrium and led to a good reproducibility after ﬁve minutes of measurements. The proﬁle of the miscibility gap was constructed from a standard polynomial regression program. The tie-lines have also been reported. [1967Tka] measured the dependence of the solubility of iron and silicon in liquid magnesium at 800°C on the annealing time. [1967Rod, 1990Nor] determined liquidus curves in the magnesium rich corner. The solubility of iron in magnesium has been examined at 800°C by measuring the solubility rate constant and the diffusion coefﬁcient of iron in magnesium [1967Rod]. [1990Nor] determined the solubility at 670, 710 and 750°C. For this last study [1990Nor], alloys were prepared from 15 kg melts to which the required amount of Si was added at 780°C. The concentration of Si has been reduced to 10 ppm by cooling the melt to 670°C and decanting metal from the top of the melt bath before alloying. The melt was then saturated with iron by adding 50 g FeCl3. Samples were taken at 760, 720 and 680°C before and after 1.5 h holding periods. At each sampling, molten alloy taken from the top of the melt was cast in three ways: in a standard disc mould, in a OKI mould for remelting and spun on a water-cooled brass wheel to form 0.3–1.0 mm thick strips. The OKI samples were reheated to the original sampling temperature and centrifuged during cooling and solidiﬁcation. The standard discs were examined by atomic absorption spectroscopy. The melt-spun and the centrifuged samples were analyzed by electron microprobe. The solubility of magnesium in the iron rich liquid has been measured at 1600°C with a micro-oven (molybdenum heater) in an atmosphere of puriﬁed argon (2–5 atmospheres) [1984Age]. The iron alloys of mass 8 g have been melted from special purity iron powder and magnesium of purity not less than 99.9 mass%. A theoretical estimate has been made which accounted for the experimental data. [1996Li] determined experimentally effect of Si on the solubility of Mg vapor in liquid Fe at 1600°C. In the experiments iron, magnesium and silicon taken in the respective quantities were placed into crucibles which were sealed in a molybdenum reaction chamber and heated in the furnace at 1600°C for 4 h. The chamber was then taken out from the furnace and immediately quenched into ice water. The Fe ingots obtained were cleaned and analyzed for Mg and Si. By their contents effect of Si on solubility of Mg in liquid Fe was established. The iron of high purity (99.94435%) was used in the experiments. The Mg vapor partial pressure was estimated to be pMg = 0.41 bar. [2000Pie] established the phase equilibria in the Fe-Mg-Si system at 727°C and constructed the isothermal section of the phase diagram at this temperature. In this investigation the studied Fe-Mg-Si alloys were prepared by annealing the powder mixtures of Fe, Mg and Si under Ar at the atmosphere pressure at 727°C and cooled then down to room temperature. The phase equilibria in the system were determined by characterization of the phases by optical microscopy, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. [2003Loe] established the phase relations in the Fe-Mg-Si system at 800 and 1000°C by identifying phases in some ternary alloys equilibrated at these temperatures and by the results of the diffusion couple experiments. Landolt-Börnstein New Series IV/11D4

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[1992Rag] presented a review on the Fe-Mg-Si phase diagram which contained the reaction scheme, the partial liquidus surface projection and the isothermal section at 1455°C. This review was supplemented by the isothermal section at 727°C [2000Pie] in the next review [2002Rag]. Binary Systems The three binary systems Fe-Mg, Fe-Si and Mg-Si are accepted from [Mas2]. Mg-Si and Fe-Mg are based on the compilations of [1984Nay] and [1985Nay], respectively. Solid Phases Based on the available data no ternary phases exist in this system. The data on the crystallography of the stable binary solid phases are summarized in Table 2. According to [2003Loe], the binary phases FeSi and FeSi2 dissolve at 800°C up to 0.03 at.% Mg and 0.05 at.% Mg, respectively. Solubility of Fe in Mg2Si at 800°C amounts to 0.3 at.%. The binary phase Fe5Si3 dissolves up to ∼0.5 and ∼1.1 at.% Mg at 800 and 1000°C, respectively. Quasibinary Systems The FeSi-Mg2Si quasibinary system was reported by [1992Rag] based on [1954Zwi]. For the respective three-phase invariant reaction the eutectic type was assumed by [1992Rag] with the eutectic composition close to Mg2Si and eutectic temperature of ∼1110°C. The eutectic type of this three-phase invariant reaction contradicts the accepted binary system Mg-Si [Mas2] with the melting point of Mg2Si being 1085°C. Therefore, the more correct type of the invariant reaction is peritectic, L + FeSi ⇌ Mg2Si, as it was assumed in the review [2000Leb] with the peritectic point being close to Mg2Si and, respectively, peritectic temperature being some above 1085°C. There is not enough experimental data to construct reliably the FeSi-Mg2Si section and it may turn out to be quasibinary only in a limited concentration and temperature range because of a possible crossing with the miscibility gap (L1+L2) extended from the binary Fe-Mg into the ternary system. Invariant Equilibria The invariant equilibria deduced from the liquidus projection [1954Zwi] are presented in the reaction scheme given in Fig. 1. The temperatures of the two ternary reactions determined from the liquidus projection [1954Zwi] were estimated in accordance with the binary Mg-Si system as 1000°C for the transition reaction U (L + FeSi ⇌ Mg2Si + βFeSi2) and < 945.6°C for the eutectic reaction E (L ⇌ (Si) + βFeSi2 + Mg2Si). In addition, the quasibinary peritectic reaction p1: L + FeSi ⇌ Mg2Si is suggested to be slightly above 1085°C based on [1954Zwi, 1992Rag] and the binary Mg-Si phase diagram [Mas2]. Characteristics of the invariant equilibria in the ternary system are described in Table 3. Liquidus, Solidus and Solvus Surfaces A partial liquidus surface represented in Fig. 2 is based on the work of [1954Zwi]. The author detected three regions of primary crystallization: FeSi, (Si) and the intermediate phase βFeSi2. Primary crystallization ﬁeld of the FeSi phase occupies the largest part of the liquidus surface. The isotherms of the liquidus surface reported in Fig. 2 in the silicon rich region were constructed from [1954Zwi] and from the binary phase diagrams given by [Mas2]. The liquidus isotherm at 1454.4°C deduced from [1971Gui], [1970Gui] is also shown in Fig. 2. Because of the unknown impact of the miscibility gap [1971Gui] on the ternary system, the schematic isothermal liquidus proposed by [1954Zwi] has been rejected up to 50 mass% Si. Four binary eutectic reactions were not mentioned by [1954Zwi]: e4 at 1203°C (l ⇌ Fe2Si + FeSi) for the system Fe-Si, e8 at 637.6°C (l ⇌ (Mg) + Mg2Si) for the system Mg-Si, e7 at 649°C (l ⇌ (Mg) + αFe) and e1 at 1526°C (l1 ⇌ l2 + δFe) for the system Mg-Fe. These reactions certainly lead to the formation of one or several ternary reactions unknown to all of the authors. Because of the lack of information, no double saturation lines have been drawn from the eutectic reactions e1, e2, e5, e7 and e8 (compare question mark in Fig. 2). DOI: 10.1007/978-3-540-78644-3_15 # Springer 2008

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3

[1984Age, 1985Age] have determined the solubility of magnesium in binary alloys of iron with silicon in the iron rich liquid below 9.45 mass% Si at 1600°C. The results showed that the concentration of silicon used has no effect on the solubility of magnesium. However, [1996Li] revealed some solubility decrease of Mg vapor in liquid Fe at 1600°C when Si was added. The isotherm of the Mg solubility in liquid Fe containing Si at 1600°C after the results of the [1996Li] experiments is shown in Fig. 3. No solubility of iron and silicon in liquid magnesium at 800°C depending on the annealing time [1967Tka] are given here because no equilibrium state was reached for iron at the end of the measurements. [1967Rod, 1990Nor] measured liquidus curves in the magnesium rich corner. Liquidus curves were obtained at 670, 710 and 750°C from [1990Nor] and at 800°C from [1967Rod]. The solubility of iron in magnesium at 800°C [1967Rod] is not in agreement with the temperature of the liquidus curve for the Fe-Mg binary. There is a discrepancy between the value of about 0.017 at.% Fe at 800°C [1967Rod] and the value of only 4.10–3 at.% at the other temperatures [1990Nor]. At ﬁrst sight, the experimental results from [1967Rod] seem to be less reliable. Therefore, the data [1990Nor] were opted as preferable and reproduced in Fig. 4. Isothermal Sections The miscibility curve deduced from [1971Gui] was reported in Figs. 2 and 5 at 1454.4°C. The tie lines in Fig. 5, illustrate the respective compositions of equilibrated liquid phases (L1 and L2). The line slopes indicate that the critical point of the miscibility gap lies near the summit of the curve. The part of the curve up to 30 mass% Si was drawn as a dashed line because of missing experimental results. The imprecise determination of the critical point position has been attributed to the nearly identical densities of the two liquids which were indiscernible with the experimental technique used in the study of [1971Gui]. In Fig. 6 the isothermal section of the phase diagram at 727°C is shown after [2002Rag] who used the work [2000Pie] to construct the section. In Fig. 7 the isothermal section at 800°C is shown after [2003Loe]. For a better view the Fe rich part of the section is shown enlarged in Fig. 8 [2003Loe]. In Fig. 9 the Fe rich part of the isothermal section at 1000°C is shown [2003Loe]. Thermodynamics On the basis of a quasiregular solution [1984Age, 1985Age] calculated the thermodynamic interaction parameters which describe the effect of silicon on the solubility of magnesium metal in liquid iron. From emf measurements of liquid Fe-Mg-Si alloys at 1350°C the activities of the components were calculated by the Darken-Wagner method [1966Lep]. The melts investigated exhibit both positive and negative deviations from Raoult’s law. Thermodynamic properties of the melts were approximated by regular solutions [1966Lep]. The effects of silicon on the solubility of Mg in liquid iron at 1600°C were studied by a vapor-molten Fe equilibration method and the interaction coefﬁcient εMgSi = –10.90 was calculated in terms of the Margules-Wagner equation [1996Li]. Notes on Materials Properties and Applications The Fe-Mg-Si phase diagram is important for industrial production of primary magnesium and magnesium alloys because Fe and Si are the main impurities in them. Increase of impurities of Fe and Si decreases corrosion resistance of Mg base commercial alloys and decreases their plasticity. One of the main origins of the Fe and Si impurities in Mg base commercial alloys is the primary Mg. Another important origin of the Fe impurity in Mg base commercial alloys and also in primary Mg is the mild steel of crucibles where the Mg products are commonly melted during preparation [1990Nor, 2000Pie, 2002Pie]. The Fe-Mg-Si phase diagram is of great importance also for treatment of cast iron for spheroidization of graphite inclusions. The treatment is performed by addition of Mg into liquid cast iron, and because of high inclination of Mg to burning and high Mg vapor pressure it is reasonable to use alloys of Mg with high contents of Si close to Mg2Si compound and Fe. These alloys have high melting temperature [1954Zwi, 1975Dan, 1993Sol, 1996Li, 2003Kob]. Another importance of the Fe-Mg-Si phase diagram is related to technology of siliconizing surface of mild steels. This technology is used for hardening surface of steels and can be performed by dip of the steel pieces into Mg-Si melts [1993Sai, 1997Sai1, 1997Sai2, 2002Pie]. Landolt-Börnstein New Series IV/11D4

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Miscellaneous The crystalline Fe-montmorillonite (Na0.3Fe1.73+Mg0.3Si4O10(OH)2·H2O) was reported to be synthesized hydrothermally for 24 h at 100 and 200°C using the Fe-Mg-Si system. In [1998Sug] the thermoelectric material Mg2Si-FeSi2 was prepared by mechanical alloying and spark plasma sintering. Table 1.

Investigations of the Fe-Mg-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1954Zwi]

DTA, optical microscopy, X-ray diffraction

Below liquidus surface (<1500°C)/0–50 at.% Fe, 0–100 at.% Mg, 0–50 at.% Si/Mg-FeSi-Si

[1966Lep]

emf measurements

1399–1350°C/ 7.3–69 at.%Fe, 2.9–58.8 at.% Mg, 11.6–69.7 at.% Si/LFe, LMg, (αFe,δFe), FeSi

[1967Rod]

Chemical analysis

700–800°C/Mg containing 0.002–0.59 mass% Si, 0.018–0.16 mass% Fe/liquid Mg

[1967Tka]

Dissolution of Si and Fe in liquid Mg/ chemical analysis of the samples

750–800°C/Mg containing 0.002–0.06 mass% Si, 0, 11 mass% Fe/liquid Mg

[1970Gui]

Sampling from the melts/chemical analysis, vapor pressure measurements

1450–1510°C, up to 15 atm/0–95%Fe, 0–95%Mg, 5–34%Si/LMg, LFe

[1971Gui]

Sampling from the melts/chemical analysis, vapor pressure measurements

1450–1510°C, up to 15 atm/0–95 mass% Fe, 0–95 mass% Mg, 5–34 mass% Si/LMg, LFe

[1984Age]

Saturation of Fe-Si melts by the Mg vapor/ determination of Mg contents by atomic absorption spectroscopy

1600°C, 2–5 atm over vapor pressure of Mg/ up to 9.45 mass% Si, up to 1.1 mass% Mg, remainder Fe/liquid Fe

[1985Age]

Calculation of the Mg activity coefﬁcient and interaction parameter in Fe-Si alloys/theory of quasi-regular solutions

1600°C/up to ∼10 mass% Si, up to solubility of Mg in liquid Fe, remainder Fe/liquid Fe

[1990Nor]

Sampling from the Mg rich melts/chemical analysis by atomic absorption spectroscopy

680–750°C/0–0.027 at.% Fe, 0–0.75%Si, remainder Mg, liquid Mg

[1996Li]

Saturation of liquid Fe by Mg vapor/ chemical analysis by atomic absorption spectroscopy after quenching of melts

1600°C, Mg vapor pressure 0.41 bar/0.0184–0.0321 at.% Mg, (0.6–4.6)·10–4 at.% Si, remainder Fe/liquid Fe

[2000Pie]

Heating for equilibrium of the Fe-Mg-Si powder mixtures and growth of reaction zones of diffusion couples/X-ray powder diffraction, optical metallography, scanning electron microscopy, electron probe microanalysis

727°C/0–100 at.% Fe, 0–100 at.% Mg, 0–100 at.% Si/Fe, liquid Mg, Si, Mg2Si, α1, α2, FeSi, βFeSi2

[2003Loe]

Investigation of the alloys prepared by melting and diffusion couples/chemical analysis, electron dispersive microanalysis, scanning electron microscope, X-ray analysis, optical metallography

800°C, 1000°C/0–100 at.% Fe, 0–100 at.% Mg, 0–100 at.% Si/Mg2Si, α1, FeSi, Fe5Si3, FeSi2

DOI: 10.1007/978-3-540-78644-3_15 # Springer 2008

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Fe–Mg–Si Table 2.

5

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(Mg) < 650

hP2 P63/mmc Mg

a = 320.94 c = 521.07

at 25°C [Mas2]

(Si) < 1414

cF8 Fd 3m C(diamond)

a = 534.06 a = 543.088

at 25°C [Mas2] at 20°C, 99.999 at.% purity [V-C2]

(αδFe)

cI2 Im 3m W

(δFe)(h2) < 1538 (αFe)(r) < 912

[Mas2] a = 293.15

at 1390°C [V-C2, Mas2]

a = 286.65

at 25°C [V-C2, Mas2]

(γFe)(h1) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [Mas2, V-C2]

α2 ≲ 1280

cP2 Pm 3m CsCl

a = ∼281

Ordered (αδFe), ∼10 to 22 at.% Si [Mas2, V-C2]

α1 ≲ 1250

cF16 Fm 3m BiF3

a = ∼560.8

Ordered (αδFe), ∼10 to 30 at.% Si [Mas2]

FeSi < 1410

cP8 P213 FeSi

a = 451.7 ± 0.5

at 300°C [V-C2]

Fe2Si(h) 1212–1040

hP6 P 3m1 Fe2Si

a = 405.2 ± 0.2 c = 508.55 ± 0.03

[Mas2, V-C2]

Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.6 c = 471.8

[V-C2]

βFeSi2(h) 1220–937

tP3 P4/mmm βFeSi2

a = 269.01 c = 513.4

69.5 to 73.5 at.% Si [Mas2, V-C2]

αFeSi2 (r) < 982

oC48 Cmca αFeSi2

a = 986.3 ± 0.7 b = 779.1 ± 0.6 c = 783.3 ± 0.6

[V-C2]

Mg2Si < 1085

cF12 Fm 3m CaF2

a = 634.7 ± 0.4

[V-C2]

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6 Table 3.

Fe–Mg–Si Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (at.%) Fe

Mg

Si

L + FeSi ⇌ Mg2Si

> 1085

p1

L FeSi Mg2Si

∼0 ∼50 ∼0.3

∼66.7 ∼0.03 ∼66.7

∼33.3 ∼50 ∼33.3

L + FeSi ⇌ Mg2Si + βFeSi2

ca. 1000

U

L FeSi Mg2Si βFeSi2

∼3 ∼50 ∼0.3 ∼33.3

∼42 ∼0.03 ∼66.7 ∼0.05

∼55 ∼50 ∼33.3 ∼66.7

L ⇌ (Si) + βFeSi2 + Mg2Si

< 945.6

E

L (Si) βFeSi2 Mg2Si

∼2 ∼0 ∼33.3 ∼0.3

∼43 ∼0 ∼0.05 ∼66.7

∼55 ∼100 ∼66.7 ∼33.3

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Fig. 1. Fe-Mg-Si.

Partial reaction scheme

Fe–Mg–Si

Landolt-Börnstein New Series IV/11D4

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Fig. 2. Fe-Mg-Si.

Fe–Mg–Si

Tentative partial liquidus surface

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Fe–Mg–Si

Fig. 3. Fe-Mg-Si.

Landolt-Börnstein New Series IV/11D4

9

The effect of Si on the Mg solubility in liquid iron at 1600°C

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Fig. 4. Fe-Mg-Si.

Fe–Mg–Si

Joint solubility of Fe and Si in liquid Mg at 670, 710 and 750°C

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Fe–Mg–Si

Fig. 5. Fe-Mg-Si.

Landolt-Börnstein New Series IV/11D4

11

Isothermal section at 1454°C

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Fig. 6. Fe-Mg-Si.

Fe–Mg–Si

Isothermal section at 727°C

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Fe–Mg–Si

Fig. 7. Fe-Mg-Si.

Landolt-Börnstein New Series IV/11D4

13

Isothermal section at 800°C

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Fig. 8. Fe-Mg-Si.

Fe–Mg–Si

Fe rich part of the isothermal section at 800°C

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Fe–Mg–Si

Fig. 9. Fe-Mg-Si.

Landolt-Börnstein New Series IV/11D4

15

Fe rich part of the isothermal section at 1000°C

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Fe–Mg–Si

References [1954Zwi] Zwicker, V., “Reactions of Some Magnesium - Alloys with Cast Iron Melts” (in German), Z. Metallkd., 45, 31–35 (1954) (Phase Diagram, Experimental, *, #, 13) [1966Lep] Lepinskikh, B.M., Sryvalin, I.T., Tikhomorov, A.A., “Thermodynamic Properties of IronSilicon-Magnesium Alloys”, Russ. J. Phys. Chem., 40(7), 840–842 (1966) (Thermodyn., 9) [1967Rod] Rodyakin, V.V., Andreyev, A.E., Tkalich, V.S., “On the Solubility of Iron in Magnesium”, Russ. Metall., 23–24 (1967) abridged translated from Izv. Akad. Nauk. SSSR, Met., (3), 63–64 (1967) (Experimental, 1) [1967Tka] Tkalich, V.S., Andreev, A.E., Rodyakin, V.V., “The Effect of the Si on the Solubility of Fe in Mg” (in Russian), Vses. Nauchn. Issled. i Proekt. Inst. Titana, (1), 190–195 (1967) (Experimental, 8) [1970Gui] Guichelaar, P.J., Trojan, P.K., McCluhan, T., Flin, R.A., “New Techniques for the Vapour Pressure Measurement Applied to the Fe-Si-Mg System”, J. Metals, 22(12), 19A (1970) (Experimental, Abstract, 0) [1971Gui] Guichelaar, P.J., Trojan, P.K., Mccluhan, T., Flinn, R.A., “A New Techniques for Vapor Pressure Measurement Applied to the Fe-Si-Mg System”, Metal. Trans., 2(12), 3305–3313 (1971) (Experimental, Phase Diagram, *, #, 16) [1975Dan] Dang-Moon, W., Soo-Young, K., “Study on the Relation Between Graphite Spheroidization and Amount of Additional Fe-Si-Mg in Spheroidal Graphite Cast Iron” (in Korean), J. Korean Inst. Met., 13(4), 407–414 (1975) (Morphology, Experimental, 12) [1984Age] Ageev, Yu.A., Archugov, S.A., “Solubility of Mg in Some Molten Binary Iron-Base Alloys”, Russ. Metall., 72–74 (1984), translated from Izv. Akad. Nauk. SSSR, Met., (3), 78–80 (1984) (Experimental, Thermodyn., Theory, 6) [1984Nay] Nayeb-Hashemi, A.A., Clark, J.B., “The Magnesium-Silicon System”, Bull. Alloy Phase Diagrams, 5(6), 584–592 (1984) (Phase Diagram, Thermodyn., Review, 49) [1985Age] Ageev, Yu.A., Archugov, S.A., “Solubility of Alkaline Earth Metals in Liquid Iron and its Alloys”, Russ. J. Phys. Chem., 59(4), 488–490 (1985), translated from Zh. Fiz. Khim., 59, 838–841 (1985) (Experimental, Theory, Thermodyn., 13) [1985Nay] Nayeb-Hashemi, A.A., Clark, J.B., “The Iron-Magnesium System”, Bull. Alloy Phase Diagrams, 6(3), 235–238 (1985) (Phase Diagram, Thermodyn., Review, 27) [1990Nor] Normann, H.H., Thoresen, H., Tibballs, J.E., Simensen, C.J., “Impurities and Mg - Base Phase Diagrams” in “Advanced Aluminium and Magnesium Alloys”, Proc. Conf. Light Metals, Amsterdam, 823–828 (1990) (Experimental, *, 7) [1992Rag] Raghavan, V., “The Fe-Mg-Si (Iron-Magnesium-Silicon) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Institut of Metals, Calcutta, 6B, 942–947 (1992) (Crys. Structure, Phase Diagram, Phase Relations, Review, 4) [1993Sai] Saikawa, H., Matsumoto, M., Minegishi, T., Morozumi, S., “Mineralization of the Surface of Iron Alloys by Siliconizing in a Molten Magnesium Bath Containing Silicon Compounds”, J. Mater. Sci. Lett., 12, 157–159 (1993) (Mechan. Prop., Morphology, Experimental, 0) [1993Sol] Solntsev, K.A., Shifrin, V.D., Miroshnichenko, O.N., Serkhovets, S.I., “A Study of HighSilicon Structural Constituents of Magnesium Iron Cast in Metal Molds”, Russ. Metall., (4), 89–92 (1993) (Morphology, Experimental, 5) [1996Li] Li, X., Song, B., Han, Q., “Thermodynamic Properties of Liquid Fe-Mg-Al and Fe-Mg-Si Dilute Ternary Solutions”, J. Phase Equilib., 17(1), 21–23 (1996) (Experimental, Thermodyn., 11) [1997Sai1] Saikawa, H., Ono, T., Minegishi, T., Morozumi, S., “Siliconizing of Iron by Molten Mg-Si Alloy Bath”, Tetsu to Hagane (Iron Steel Inst. Jpn.), 83(7), 437–441 (1997) (Experimental, Phase Relations, 13) [1997Sai2] Saikawa, H., Ono, T., Minegishi, T., Morozumi, S., “Siliconizing of Iron and Steel by Molten Magnesium Bath with Silicon Carbide Powder”, Tetsu to Hagane (Iron Steel Inst. Jpn.), 83(7), 442–447 (1997) (Experimental, Kinetics, Morphology, Phase Relations, 7) [1998Sug] Sugiyama, A., Kobayashi, K., Ozaki, K., Nishio, T., Matsumoto, A., “Preparation of Functionally Graded Mg2Si-FeSi2 Thermoelectric Material by Mechanical Alloying Pulsed Current DOI: 10.1007/978-3-540-78644-3_15 # Springer 2008

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Fe–Mg–Si

[1999Nag]

[2000Leb]

[2000Pie]

[2002Pie]

[2002Rag] [2003Kob]

[2003Loe]

[Mas2] [V-C2]

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Sintering Process” (in Japanese), J. Jpn. Inst. Met., 62(11), 1082–1087 (1998) (Morphology, Experimental, 3) Nagase, T., Iwasaki, T., Ebina, T., Hayashi, H., Onodera, Y., Dutta, N.C., “Hydrothermal Synthesis of Fe-Montmorillonite in Si-Fe-Mg System”, Chem. Lett. (4), 303–304 (1999) (Morphology, Crys. Structure, Experimental, 9) Lebrun, N., Baetzner, C., Stamou, A., Robinson, J., “Iron-Magnesium-Silicon”, MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 10.15873.2.20, (2000) (Crys. Structure, Phase Diagram, Phase Equilibria, Assessment, 11) Pierre, D., Peronnet, M., Bosselet, F., Viala, J.C., Bouix, J., “Solid-Liquid Phase Equilibria at 727°C in the Ternary System Fe-Mg-Si”, J. Phase Equilib., 21(1), 78–86 (2000) (Experimental, Kinetics, Phase Relations, 21) Pierre, D., Peronnet, M., Bosselet, F., Viala, J.C., Bouix, J., “Chemical Interaction Between Mild Steel and Liquid Mg-Si Alloys”, Mater. Sci. Eng. B, 94, 186–195 (2002) (Morphology, Phase Diagram, Phase Relations, Calculation, Experimental, Kinetics, 26) Raghavan, V., “Fe-Mg-Si (Iron-Magnesium-Silicon)”, J. Phase Equilib., 23(2), 175–176 (2002) (Phase Relations, Review, 6) Kobayashi T., Maruyama T., “Thermal Decomposition Behaviour of Expandable Pattern Including Blended Metal or Alloy Powder in Evaporative Pattern Casting Process of Cast Iron”, Mater. Trans., 44(11), 2396–2403, (2003) (Experimental, Kinetics, 13) Loefﬂer, F., “Investigations in the Ternary Systems Fe-Si-Mg and Fe-Si-Ti: Phase Equilibria and Mechanical Behaviour of Selected Alloys” (in German), Fortschritt-Berichte VDI. Reihe 5: Grund- und Werkstoffe/Kunststoffe, 5(676), 1–106 (2003) (Phase Relations, Phase Diagram, Experimental, Interface Phenomena, 95) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–Mn–N

1

Iron – Manganese – Nitrogen Lazar Rokhlin, Evgeniya Lysova

Introduction The Fe-Mn-N system has raised much interest because Mn is a key element in the preparation of High Nitrogen Steels (HNS). Indeed, the presence of Mn in Fe increases the nitrogen solubility in the steel and the increase is not limited by the manganese nitride precipitation. Different experimental works were reviewed by [1984Rag, 1987Rag, 1993Rag] and thermodynamically assessed by [1993Qiu2]. In the detailed review [1987Rag] the partial isothermal sections of the Fe-Mn-N phase diagram at 500 and 550°C, the solubility of N in the liquid Fe-Mn alloys, the solubility of N in Fe-Mn solid austenite and Fe-Mn ferrite were presented. The isothermal sections were reproduced from the experimental work of [1975Raw, 1984Bur]. The N solubility in liquid Fe-Mn was assessed by [1993Qiu2] from the experimental determinations of [1960Peh, 1961Bee, 1961Dod, 1974Gri, 1982Ish, 1984Lee, 1986Wad, 2001Kim]; the N solubility in the solid Fe-Mn phases: austenite and ferrite, was assessed from [1963Mor, 1963Sch1, 1963Sch2, 1975Gra, 1983Ko] and [1962Enr, 1973Pip, 1975Raw, 1980Bra], respectively. In the next review, [1993Rag] updated [1987Rag] using the experimental work of [1991Sat] on the N solubility in the Fe-Mn alloys. Moreover, a new isothermal section of the Fe-Mn-N phase diagram at 700°C was presented. A thermodynamic assessment of the ternary system was presented by [1993Qiu2] which reproduces with a rather agreement the experimental data about the solubilities and which takes into account the nitrogen pressures. The main experimental investigations of the Fe-Mn-N phase diagram are presented in Table 1. Binary Systems The Fe-Mn system has been recently reassessed and the Calphad description was updated by [2004Wit]. This new reevaluation of the phase equilibria leads to consistently better ﬁts to the available experimental data. Consequently, the Fe-Mn system is accepted from [2004Wit]. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). The Fe-N phase diagram in the solid state is accepted from the review of [1987Wri]. The Calphad assessment carried out by [1991Fri] and justiﬁed by the model proposed by [1994Fer] gives an insight on the phase equilibria under high nitrogen pressures. The Mn-N system at high temperatures is accepted from the reevaluation of [1993Qiu1], which takes into account the nitrogen pressure. The nitrogen solubility in pure Mn may be expressed by [1967Bur]: log10 (mass% N) = – 1.457 + (3010/T ) + 0.5 log10 (pN2/bar) (1246–1600°C). Solid Phases No ternary compound was reported in the Fe-Mn-N system. Other solid phases are given in Table 2. The nitrides Mn4N and Fe4N have the same cP5 cubic structure with parameters close enough to suggest the formation of a continuous solid solution Mn4(1–x)Fe4xN. Actually, a complete solid solution can not be observed because of the mismatch in the stability domains of both nitrides. Mn4N reacts with Fe4N by giving Fe and Mn nitrides with higher nitrogen content. In [1959Juz] the lattice parameter measurements were extended up to x = 0.56. At higher Fe content dissolved in Mn4N, the lattice parameter remains constant. However, the Curie point of Mn4N continues to decrease with addition of Fe up to the highest values x = 0.72 used in the experiments. The solubility of Mn in Fe4N was reported by [2004Pad].

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Liquidus Surface Using thermodynamic calculation, [1993Qiu2] presents the partial liquidus surface of the Fe-Mn-N phase diagram near the Fe corner for different values of the N2 pressure. Projection of the liquidus surface with the respective isothermal and isobaric curves is shown in Fig. 1. Isothermal Sections The partial isothermal section of the Fe-Mn-N phase diagram at 500°C and 0.1 MPa of N2 pressure is presented in Fig. 2 after [1987Rag], mainly from experimental data [1984Bur]. The homogeneity ranges of the binary Mn-N phases are taken from [Mas2]. Figure 3 shows the solubility of nitrogen in Fe-Mn ferrite at 550°C, experimentally determined by [1975Raw] and reproduced by [1987Rag]. Figures 4 and 5 show the nitrogen solubility at various temperatures in the Fe-Mn austenite and at 1550°C in the liquid phase, respectively [1987Rag]. The solubility curves for austenite and liquid at 1550°C are well reproduced by thermodynamic calculations of [1993Qiu2]. The nitrogen solubility in liquid alloys deviates from the Sievert’s law above 0.1 MPa of N2 pressure [1963Sch2, 1990Siw, 1991Sat]. However, it may be shown that Sievert’s law is better obeyed with nitrogen fugacities rather than with nitrogen pressures. Temperature – Composition Sections The temperature-composition section Mn4N-Fe4N, calculated under 0.1 MPa of N2 pressure [1993Qiu2] is presented in Fig. 6. Thermodynamics The interaction coefﬁcients between Mn and N in liquid iron at 1600°C, (< 20 mass% Mn) were ﬁrst evaluated as eN(Mn) = {∂ log10 fN/∂ (mass% Mn)} = – 0.020 at 1600°C by [1960Mae, 1960Peh, 1982Ish] and as –0.023 at 1400–1650°C by [1961Bee, 1991Sat], with fN = (mass% N in pure Fe)/(mass% N in alloy). A temperature dependent expression, usable around 1600°C was proposed by [1977Lin]: in the iron rich liquid alloys: eN(Mn) = 0.022 – 73/T = – 0.016 at 1600°C Around 1600°C, eN(Mn)< 0: Mn increases the nitrogen solubility in iron whereas eN(Fe) > 0 [1961Dod]: Fe decreases the nitrogen solubility in manganese. A statistical model of the nitrogen-metal interaction in iron based liquid alloys has been developed by [1994Tan]. The interaction coefﬁcient between Mn and N in γ austenite has been investigated by [1963Mor], which propose, eN(Mn) = –0.034, –0.037 and –0.041 at 1250, 1150 and 1050°C, respectively. By using mole fractions instead of mass%, the interaction parameter in the γ austenite may be expressed by: εN(Mn) = {∂ lnγN/∂ xMn} = (8.2 – 2100/T ) ± 0.5 [1975Gra] in the temperature range 900–1100°C with γN = (xN in pure Fe)/(xN in alloy). This last expression agrees with the evaluation of [1975Kik] εN(Mn) = – 9.0 at 1100°C and with the experimental measurements of [1983Ko]: εN(Mn) = – 10.34 at 1000°C. Mn up to 0.75 mass% seems to have little effect on the nitrogen solubility in (αFe) [1962Enr], an observation which is conﬁrmed by the low value of the interaction parameter εN(Mn) = + 0.21 proposed in the temperature range 450–550°C by [1975Gra]. Notes on Materials Properties and Applications The alloys (Mn,Fe)4N were reported to be ferrimagnetic [1959Juz]. However, a ferromagnetic order was observed for MnFe3N and calculations carried out by [2004Pad] showed that a high spin ferromagnetic state is the stable phase at low temperatures. Aiming to investigate the precipitation phenomenon in the Fe-Mn-N alloys the change of internal friction in them with increasing temperature and strength of coercivity ﬁeld were measured [1962Enr, 1966Nac1, 1966Nac2, 2002Bli].

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[1974Ste] investigated the internal friction in the Fe-Mn-N alloys containing 0–2 mass% Mn and 0.0007– 0.0011 mass% N in limits from –53 to 252°C at ∼1 Hz using the torsion pendulum method. The obtained results give a procedure for determining the nitrogen content in the Fe-Mn-N alloys. [1975Tsu] investigated the strain aging of Fe-Mn-N polycrystalline specimens and showed, that strain aging takes place in two stages corresponding to different change of the yield point with ageing time. Authors explained the yield point behavior during the strain aging of the alloys by an increase of the average distance between pinning points in screw dislocations. [1976Sal] studied the low frequency friction spectrum in Fe-Mn-N alloys and stress relaxation at constant strain in limits of the –4 to 150°C temperature range. The obtained results are connected with motion of single nitrogen atoms around single manganese atoms, and two types of motion of single nitrogen atoms around a manganese atom pair. [1998Gav] examined inﬂuence of 0.2 mass% N on vibration damping and mechanical properties of Fe13.7Mn (mass%) alloy. The damping measurements were conducted at the torsion deformation amplitude of (0.2–8.0)·10–4 at frequency of 1–2 Hz. Presence of nitrogen resulted in increase of damping and strength properties of the alloy, especially the ultimate strength. The favorable nitrogen effects are attributed to the strengthening of austenite and higher mobility of the austenite/martensite. [1999Ari] has investigated the effect of 0.26 mass% N on the shape memory behavior of a Fe-Mn based shape memory alloy. Addition of nitrogen increased the strength of the alloy and suppressed the shape memory effect by approximately to 80%. [2002Lee] has examined the effects of 0.015–0.05 mass% N on the damping capacity and austenite/martensite transformation in the Fe-16Mn (mass%) alloy. Increase in Ms (Martensite start temperature) with N content was pointed out and explained by decrease in stacking fault energy (SFE) of austenite (γ). The damping capacity of the alloys decreases when increasing nitrogen content. [2006Che] studied the electronic structure and magnetism of Fe4–xMnxN compounds by a periodic quantum-mechanical calculation based on density functional theory. The results showed that ferromagnetic ordered phase is stable when Fe is substituted by Mn on cube corner sites, whereas the antiferromagnetic phase is energetically favored when Mn substitutes for Fe on face-centered sites. Details of the properties investigations are presented in Table 3. Miscellaneous [1967Cho1] measured the rates of N absorption into liquid iron containing 0–4.3 mass% Mn at 1600°C and [1979Cho] investigated the kinetics of nitrogen desorption in liquid Fe-Mn alloys with 1.1–6.8 mass% Mn at 1600°C and 0.1 mm Hg pressure. [1968Roy] investigated the high temperature strengthening mechanism in a dilute Fe-∼1.5Mn-0.01N (mass%) alloy by using the Mössbauer effect. The Mössbauer spectrum observed was interpreted as evidence of the Fe-Mn-N chains formation in the Fe base solid solution. In [1973Kun] effect of Mn on the diffusion coefﬁcient of nitrogen in Fe-Mn melted alloys at 1550–1700°C was investigated. Actually increase of Mn contents up to about 15 mass% did not result in any change of the N diffusion coefﬁcient. However, [1981Ers] reported about decrease of the nitrogen mobility in melted Fe-Mn alloys at 1600°C with increasing Mn contents up to 8 mass% Mn. Prolonged mechanical milling of a mixture of Fe and Mn nitrides [1989Roc] leads to oversaturated solid solutions and metastable phases. [1978Sos] established the linear increase of the γ solid solution lattice parameter in the Fe-18Mn (mass%) alloys with increasing N contents up to about 2.3 mass%. [1982Gar] presented the detailed diffraction data used for identiﬁcation of a nitrogen rich orthorhombic phase which is considered as a M3N type nitride formed during decomposition of the Fe-Mn-N alloys with low N content. In [1992Vol] structure and breakdown of the Fe-Mn alloys prepared by hot extrusion of powders were studied. The alloys contained 4 to 32 mass% Mn and 0.0002–0.01915 mass% N, because the powders were obtained by atomizing in the nitrogen atmosphere. Distribution of the N atoms and other gas impurities on the grain boundaries of the alloys and dependence of it on temperature were established. The change of the breakdown mechanism of the alloys with increasing temperature is attributed to the change of the impurity distribution. Landolt-Börnstein New Series IV/11D4

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In [1999Sum] neutron-spectroscopy investigation of the Fe-Mn-N alloys containing 17–35 mass% Mn was studied aiming to estimate interaction between Mn and N atoms in Fe-Mn solid solution. Investigation showed weak interaction between each of the atom kinds as compared with Cr-N interaction. [2000Gou] provided a realistic diffusion - precipitation model, which describes the volume diffusion of nitrogen in ferrite and the simultaneous precipitation of ﬁne scale alloying element nitrides in the diffusion zone. Theoretical calculations were in good agreement with experimental measurements. Table 1.

Investigations of the Fe-Mn-N Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1960Mae]

Nitrogen solubility in liquid alloys, sampling method

1500–∼1700°C, < 4 mass% Mn < 0.1 MPa of N2 pressure

[1960Peh]

Nitrogen solubility in liquid alloys, Sievert’s method

1606°C, < 6 mass% N, 0.1 MPa of N2 pressure

[1961Dod]

Nitrogen solubility in liquid alloys, Sievert’s method

1550°C, 0–100 mass% Mn, 0.1 MPa of N2 pressure

[1961Bee]

Nitrogen solubility in liquid alloys, sampling method

1400–1650°C, 0–100 mass% Mn, 0.1 MPa of N2 pressure

[1962Enr]

Nitrogen solubility in α alloys, internal friction measurements

200–350°C, 0.15 to 0.75 mass% Mn, 0.1 MPa of N2 pressure

[1963Mor]

Nitrogen solubility in γ alloys, chemical analysis

1050–1250°C, < 6 mass% Mn, H2-N2 atmospheres (5% H2)

[1963Sch1]

Nitrogen solubility in γ alloys, sampling method

700–1200°C, < 9.5 mass% Mn, 0.1 MPa of N2 pressure

[1963Sch2]

Nitrogen solubility in γ alloys, sampling method

1000°C, 0–100 mass% Mn, 0.1 to 6.4 MPa of N2 pressure

[1966Bai]

XRD, electron diffraction, nitride precipitation investigation

450–650°C, 1.6 mass% Mn, (0.040 to 0.063) mass% N

[1966Nac2]

Nitrogen solubility in α alloys, internal friction measurements

585°C, 0.45 to 2.01 mass% Mn

[1968Nem]

Nitrogen solubility in liquid alloys, sampling method

1550°C, 26 to 76 mass% Mn, 0.1 MPa N2

[1974Gri]

Nitrogen solubility in liquid alloys, sampling method

1550–2100°C, 3.6 to 59.2 mass% Mn, 25 to 101 kPa N2

[1975Gra]

Nitrogen solubility in γ alloys, sampling method

900–1100°C, 3.4 to 45 mass% Mn, 1 to 95 kPa N2

[1975Raw]

Fe4N solubility in α alloys, sampling method

450–550°C, < 4 mass% Mn, H2-NH3 atmospheres

[1978Sos]

XRD, lattice parameters measurements

25°C, 18 mass% Mn, < 2.3 mass% N

[1982Gar]

XRD, identiﬁcation of the nitrogen rich orthorhombic phase

25°C, 4.2 mass% Mn, 0.5 to 0.9 mass% N (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1982Ish]

Nitrogen solubility in liquid alloys, sampling method

1540–1680°C, < 9 mass% Mn, 0.1 MPa N2

[1983Ko]

Nitrogen solubility in γ alloys, sampling method

867–1265°C, < 15 at.% Mn, 0.104 MPa N2

[1984Lee]

Nitrogen solubility in liquid alloys, levitation melting method

1489–1998°C, < 15 mass% Mn, 0.1 MPa of N2 pressure

[1985Bas]

Nitrogen solubility in γ under high pressures, XRD, TEM

1000–1070°C, 7 and 18 mass% Mn, < 120 MPa N2

[1986Wad]

Nitrogen solubility in liquid alloys, levitation melting method

1489–1998°C, 3.8–15.8 mass% Mn, 0.1 MPa of N2 pressure

[1990Siw]

Nitrogen solubility in liquid alloys, sampling method

1600°C, 18 mass% Mn, 0.125 to 1.0 MPa of N2pressure

[1991Sat]

Nitrogen solubility in liquid alloys under high pressure

1600°C, 18–28 mass% Mn, < 10 MPa of N2 pressure

[1994Kun]

Nitrogen solubility in γ alloys, sampling method

1000–1200°C, 6.26 to 18.21 mass% Mn, 98.7 kPa N2 + 2.6 kPa H2

[1995Nec]

Nitrogen solubility in γ alloys under high pressure

900–1200°C, < 18 mass% Mn, 3 to 348 MPa of N2 pressure

[2001Kim]

Nitrogen solubility in liquid alloys, sampling method

1350–1550°C, 0.1 MPa of N2 pressure

[2003Gou1, 2003Gou2]

TEM, metallography, electron diffraction

570°C, 1.62 mass% Mn nitrided in bath salt; a new θ′ phase

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group Prototype

(δFe) 1538–1394

cI2 Im 3m W

γ, (γFe,γMn) < 1473

cF4 Fm 3m Cu

(γFe) 1394–912 (γMn) 1138–1100

Lattice Parameters [pm]

a = 293.15

Comments/References

dissolves up to 10.5 at.% Mn, pure Fe at 1390°C [V-C2, Mas2] continuous solid solution, dissolves up to 11.3 at.% N [Mas2]

a = 364.67

pure Fe at 915°C [Mas2, V-C2]

a = 386.0

pure Mn [Mas2] (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group Prototype

(αFe) < 912

cI2 Im 3m W

(δMn) 1246–1138

cI2 Im 3m W

(βMn) 1155–727 (αMn) < 727 γ′, Mn4(1–x)Fe4xN γ′, Mn4N < 890

cP20 P4132 βMn cI58 I 43m αMn

Mn2N

hP12 P6322 Mn12N5 hP3 P63/mmc -

Comments/References

a = 286.65

dissolves 3 at.% Mn and 0.4 at.% N, pure Fe at 25°C [Mas2, V-C]

a = 308.0

dissolves up to 8.85 at.% Fe and ∼2 at.% N, pure Mn [Mas2]

a = 631.2

dissolves up to 34 at.% Fe and ∼4 at.% N, pure Mn [Mas2]

a = 891.26

dissolves 29.7 at.% Fe and ∼0.5 at.% N, pure Mn at 25°C[Mas2]

cP5 Pm 3m Fe4N

γ′, Fe4N < 680 ζ Mn12N5

Lattice Parameters [pm]

solid solution stable at both ends (x < 0.3 and x∼1 at 900°C [1984Bur] a = 383.4 to 387.7

17.4 to 21.6 at.% N [Mas2], [1987Rag]

a = 387.6 a = 378.7

at 20.45 at.% N 19.3 to 20 at.% N [Mas2]

-

∼ 29 at.% N [Mas2]

a = 281.6 c = 453.4

32.6 at.% N [Mas2] at 32.6 at.% N [V-C2]

Mn2N

oP12 Pbcn PbO2

η, Mn6N4 ≲ 710

tI* I4/mmm -

θ, Mn6N5 ≲ 580

hP* P6/mmm

θ′

tP* P42/mmc -

∼33 at.% N [Mas2]

a = 421.1 c = 409.5 a = 420.5 c = 404.2 a = 421.1 c = 414.5 a = 287.6 c = 575.2

from ∼38 to 41 at.% N [Mas2] [1987Rag] at 39.1 at.% N [V-C2] from ∼ 45.8 to 49 at.% N [Mas2] [2003Gou1] Metastable phase [2003Gou1]

(continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group Prototype

εFe3N < 580

hP3 P63 22 Fe3N

Fe2(1 –x)Mn2x N < 500

oP12 Pbcn Fe2N

7

Lattice Parameters [pm]

Comments/References

from 15.8 to 33.2 at.% N [1987Rag] εFe5.23N

a = 259.7 c = 434.1 a = 278.7 c = 444.8

εFe2N x < 0.30 [1984Bur]

a = 551.2 b = 482.0 c = 441.6

at 25°C for x = 0 [1987Wri]

α′, Fe16N2

tI* I4/mmm -

a = 572.0 c = 629.2

Ordered fcc structure, metastable [1987Rag]

α′, Fe-N (Martensite)

cI2 Im 3m W bct -

-

from 0 to 2.5 at.% N [Mas2]

a = 284.4 c = 310.0

from 2.7 to 9.5 at.% N [Mas2]

Table 3.

Investigations of the Fe-Mn-N Materials Properties

Reference

Method/Experimental Technique

Type of Property/Conditions

[1959Juz]

XRD, Curie temperature, saturation magnetization

< 400°C, magnetic properties of the solid solution (Fe1–xMnx)4N

[1962Enr]

Internal friction measurements

Kinetics of nitrogen precipitation from (αFe).

[1966Bai]

Normal ageing tests, tensile properties and hardness

450–600°C, 1.0 to 1.6 mass% Mn, 0.008 to 0.063 mass% N.

[1966Nac1]

Damping behavior

< 200°C, < 1.5 mass% Mn, < 0.07 mass% N

[1966Nac2]

Damping behavior, Mn precipitation

585°C, < 2 mass% Mn, < 0.08 mass% N

[1967Cho2]

Creep resistance under stress change

450°C, 0.24 to 0.50 mass% Mn, 0.034 to 0.046 mass% N

[1974Ste]

Nitrogen determination by internal friction measurements

– 52 to + 252°C, < 2 mass% Mn, < 0.001 mass% N

[1975Tsu]

Electrical resistivity and recovery of yield point

Ageing of polycrystalline Fe-Mn-N alloys

[1976Sal]

Internal friction, stress relaxation at constant strain

– 40 to + 150°C, 3.6 mass% Mn (continued)

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Fe–Mn–N

Reference

Method/Experimental Technique

Type of Property/Conditions

[1981Ers]

Nitrogen diffusion in liquid alloy, volumetric method

1600°C, < 7 mass% Mn, diffusion coefﬁcient

[1989Roc]

XRD, SEM, Mössbauer

Mechanical alloying Fe4N + Mn mixtures, annealing at 190°C

[1998Gav]

XRD, internal friction, nitrogen inﬂuence on damping behavior,

< 497°C, 13.7 mass% Mn, 0.2 mass% N, mechanical properties

[1999Ari]

Shape memory effect, thermodynamic modeling

0.26 mass% N, effect of nitrogen on shape memory effect

[2002Bli]

Amplitude - dependent internal friction technique

Dependence of internal friction on strain amplitude

[2002Lee]

XRD, dilatometry, damping behavior

16 mass% Mn, < 0.05 mass% N, γ → ε martensitic transformation

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Fig. 1. Fe-Mn-N.

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The calculated liquidus projection together with isobaric lines (dashed curves)

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Fig. 2. Fe-Mn-N.

Fe–Mn–N

Partial isothermal section at 500°C

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Fig. 3. Fe-Mn-N.

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Solubility of N in Fe-Mn ferrite at 550°C

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Fig. 4. Fe-Mn-N.

Fe–Mn–N

Solubility of N in Fe-Mn austenite at 1000 and 1200°C

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Fig. 5. Fe-Mn-N.

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Solubility of N in liquid Fe-Mn alloys under 0.1 MPa of N2 pressure

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Fig. 6. Fe-Mn-N.

Fe–Mn–N

The temperature - composition section Mn4N - Fe4N

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Fe–Mn–N References [1959Juz]

[1960Mae]

[1960Peh]

[1961Bee] [1961Dod] [1962Enr] [1963Mor]

[1963Sch1]

[1963Sch2]

[1966Bai] [1966Nac1]

[1966Nac2]

[1967Bur] [1967Cho1]

[1967Cho2] [1968Nem]

[1968Roy]

[1973Kun]

[1973Pip]

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15

Juza, R., Deneke, K., Puff, H., “Ferromagnetism of Solid Solutions of Mn4N with Cr, Fe, and Ni” (in German), Z. Elektrochem., 63, 551–557 (1959) (Experimental, Thermodyn., Magn. Prop., 11) Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron Alloys. I. Solubility of Nitrogen in Liquid Iron and Effect of Carbon, Silicon and Manganese on the Solubility” (in Japanese), Tetsu to Hagane, 46, 748–753 (1960) (Experimental, Phase Relations, Thermodyn., 14) Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans. AIME, 218, 1088–1101 (1960) (Experimental, Thermodyn., Phase Relations, 32) Beer, S.Z., “Solubility of Nitrogen in Molten Iron-Manganese Alloys”, Trans. AIME, 221, 2–8 (1961) (Electrical Prop., Experimental, Phase Relations, 14) Dodd, R.A., Gokcen, N.A., “Solubility of Nitrogen in Liquid-Iron Manganese Alloys”, Trans. AIME, 221, 233–236 (1961) (Experimental, Phase Relations, Theory, Thermodyn., 9) Enrietto, J.F., “The Solubility and Precipitation of Nitrides in α-Iron Containing Manganese”, Trans. AIME, 224, 43–48 (1962) (Experimental, Phase Relations, Morphology, 12) Mori, T., Shimmyo, K., Ichise, E., Morooka, A., “Effects of Alloying Elements on the Activity of Nitrogen in Austenite. I. Effects of Chromium and Manganese”, Mem. Fac. Eng. Kyoto Univ., 25, 164–174 (1963) (Experimental, Calculation, 11) Schenck, H., Frohberg, M.G., Reinders, F., “Contribution to the Study of the Solubility of N in Fe Alloys over the Temperature Range from 700 to 1200°C” (in German), Stahl Eisen, 83(2), 93–99 (1963) (Experimental, Phase Relations, 26) Schenck, H., Frohberg, M.G., Kranz, W., “The Solubility of N in Fe-Mn Alloys at 1000°C and Pressures up to 65 Atmospheres” (in German), Arch. Eisenhuettenwes., 34, 825–830 (1963) (Experimental, Theory, Thermodyn., 33) Baird, J.D., “Precipitation of Nitrides in Iron-Manganese-Nitrogen Alloys”, J. Iron Steel Inst., 204(11), 1122–1130 (1966) (Experimental, Phase Relations, 18) Nacken, M., Kuhlmann, U., “Effect of Manganese Content on the Damping Behaviour of Nitrogen-Containing Iron Alloys” (in German), Arch. Eisenhuettenwes., 37, 235–243 (1966) (Kinetics, Thermodyn., 20) Nacken, M., Kuhlmann, U., “Effect of Manganese Content on the Precipitation Behaviour of Nitrogen-Containing Ferrous Alloys” (in German), Arch. Eisenhuettenwes., 37, 331–339 (1966) (Kinetics, Thermodyn., 23) Burylev, B.P., “Solubility of Gases in Molten Mn-base Alloys” (in Russian), Izv. Vyssh. Ucheb. Zaved. Chern. Met., (4), 5 (1967) (Theory, Calculation, 7) Choh, T., Inouye, M., “On the Rate of Absorption of Nitrogen in Liquid Iron and Iron Alloys, Containing Carbon, Silicon, Manganese and Chromium” (in Japanese), Tetsu to Hagane, 53(12), 1393–1406 (1967) (Experimental, Kinetics, 26) Choubey, R., Nijhawan, B.R., “Effects of Stress Changes on Creep Resistance of Fe-Mn-N Alloys”, J. Iron Steel Inst, 205(5), 554–555 (1967) (Mechan. Prop., Experimental, 6) Nemchenko, V.P., Malkin, I.P., Popel, S.I., “To the Thermodynamic of the Solution of the Nitrogen in the Melts of Fe-Cr, Fe-Mn and Fe-Cr-Mn” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., (12), 5–8 (1968) (Calculation, Experimental, Thermodyn., 9) Roy, R.B., Solly, B., Wappling, R., “An Investigation of High Temperature Strengthening Mechanism in a Dilute Fe-Mn-N Alloy by Means of Mössbauer Effect” (in German), Z. Metallkd., 59(7), 563–566 (1968) (Experimental, Mechan. Prop., 7) Kunze, H.D., “Effect of the Elements Chromium, Manganese, Cobalt, Nickel, Molybdenum and Tungsten on the Diffusion of Nitrogen in Liquid Iron Alloys” (in German), Arch. Eisenhuettenwes., 44(2), 71–80 (1973) (Experimental, Kinetics, Thermodyn., 50) Pipkin, N.J., Roberts, W., Speirs, D.L., Grieveson, P., Jack, K.H., “Effect of Substitutional Alloying Elements on the Activity Coefﬁcients and Behaviour of Interstitial Solutes in Iron” in “Chemical Metallurgy of Iron and Steel”, Proc. Int. Symp. Metallurgical Chemistry. MSIT®

DOI: 10.1007/978-3-540-78644-3_16 # Springer 2008

16

[1974Gri]

[1974Ste] [1975Gra]

[1975Kik] [1975Raw]

[1975Tsu] [1976Sal]

[1977Lin] [1978Sos]

[1979Cho]

[1980Bra] [1981Ers]

[1982Gar] [1982Ish] [1983Ko] [1984Bur]

[1984Lee] [1984Rag] [1985Bas]

Fe–Mn–N Applications in Ferrous Metallurgy, Iron and Steel Inst., London, 351–352 (1973) (Morphology, Thermodyn., 7) Grigorenko, G.M., Pomarin, Yu.M., Lakomsky, V.I., Sherevera, A.V., “The Inﬂuence of Temperature on the Solubility of Nitrogen in Iron-Manganese Melts”, Russ. Metall., (6), 9–13 (1974), translated from Izv. Akad. Nauk SSSR, Met., (6), 11–15 (1974) (Kinetics, Phase Relations, Thermodyn., 20) Stephenson, E.T., “Determination of Total Nitrogen Solution Fe-Mn-N Alloys by Internal Friction”, Metall. Trans., 5(9), 1987–1992 (1974) (Experimental, Calculation, 24) Grabke, H.J., Iyer, S.K., Srinivasan, S.R., “The Solubility of Nitrogen in Austenitic IronManganese and Iron-Chromium Alloys”, Z. Metallkd., 66, 286–292 (1975) (Experimental, Phase Relations, Thermodyn.,13) Kikuchi, M., Tanaka, R., “Activity of Nitrogen in Austenitic Steels” (in Japanese), Tetsu to Hagane, 61(13), 2892–2903 (1975) (Phase Relations, Thermodyn., 46) Rawlings, R., Hatherley, P.G., “Iron-Manganese-Nitrogen Ferrite: The Activity of Nitrogen and the Solubility of Manganese Nitrides”, Met. Sci., 9, 97–103 (1975) (Crys. Structure, Phase Relations, Thermodyn., 34) Tsunoyama, K., Suzuki, H., “Strain Aging of Fe-Mn-N Alloy” (in Japanese), J. Jpn. Inst. Met., 39(8), 836–840 (1975) (Experimental, Mechan. Prop., 21) Salzbrenner, R.J., Carpenter, C.H., “Anelastic Relaxations in the Fe-Mn-N System”, Physica Status Solidi A, 36(1), 117–126 (1976) (Experimental, Phase Relations, Mechan. Prop., Calculation, 26) Lin, R.Y., Chang, Y.A., “Activity-Coefﬁcient of Nitrogen in Binary-Liquid Metal-Alloys”, Metall. Trans. B, 8B(2), 293–300 (1977) (Calculation, Thermodyn., Review, 72) Soshnikov, V.I., Omelchenko, A.V., Georgieva, I.V., Bashchenko, A.P., “Nitrogen Inﬂuence on Lattice - Parameter of Iron - Manganese Alloy Austenite” (in Russian), Fiz. Met. Metalloved., 45(5), 1120 (1978) (Crys. Structure, Experimental, 7) Chon, T., Moritani, T., Inouye, M., “Kinetics of Nitrogen Desorption of Liquid - Iron, Liquid Fe-Mn and Fe-Cu Alloys under Reduced Pressures”, Trans. Iron Steel Inst. Jpn., 19(4), 221–230 (1979) (Experimental, Kinetics, 48) Brandes, E.A., Flint, R.F., “Mn-Fe-N” in “Manganese Phase Diagrams”, Manganese Centre, Paris, 113 (1980) (Phase Diagram, Review, 2) Ershov, G.S., Kasatkin, A.A., “Inﬂuence of Alloying Elements on the Diffusion of Nitrogen in Liquid Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, Thermodyn., 13) Garwood, R.D., “Cementite - Type (D011) Orthorhombic Phase in Tempered Fe-Mn-N Alloys”, Met. Sci., 16(12), 587–590 (1982) (Crys. Structure, Experimental, 12) Ishii, F., Banya, S., Fuwa, T., “Solubility of Nitrogen in Liquid Iron Alloys”, Tetsu to Hagane, 68(10), 1551–1559 (1982) (Experimental, Phase Relations, Thermodyn., 43) Ko, C., McLellan, R.B., “Thermodynamics of Ternary Nitrogen Austenites”, Acta Metall., 31(11), 1821–1827 (1983) (Experimental, Phase Relations, Thermodyn., 26) Burdese, A., Firrao, D., Rolando, P., Rosso, M., “About the Iron-Manganese-Nitrogen System” (in Italian), Chim. Ind., 66(7–8), 456–460 (1984) (Experimental, Phase Relations, Thermodyn., 44) Lee, S-W., Young H-Y., “Effect of Mn on the Nitrogen Solubility in Iron Melt” (in Korean), J. Korean Inst. Met., 22(9), 789–793 (1984) (Experimental, Thermodyn., 18) Raghavan, V., “The Fe-Mn-N (Iron-Manganese-Nitrogen) System”, Trans. Indian Inst. Met., 37(3), A-F (1984) (Phase Diagram, Phase Relations, Review, 30) Bashchenko, A.P., Izotov, V.I., Omelchenko, A.V., Soshnikov, V.I., Shcherbedinskii G.V., “Alloying Iron and its Alloys with Nitrogen Under High Pressure”, Russ. Metall., (4), 169–174 (1985), translated from Izv. Akad. Nauk SSSR, Met., (4), 173–178 (1985) (Crys. Structure, Morphology, Thermodyn., 13)

DOI: 10.1007/978-3-540-78644-3_16 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–N [1986Wad] [1987Rag]

[1987Wri]

[1989Roc]

[1990Siw]

[1991Fri] [1991Sat]

[1992Vol]

[1993Qiu1] [1993Qiu2] [1993Rag] [1994Fer]

[1994Kun] [1994Tan]

[1995Nec]

[1998Gav]

[1999Ari] [1999Sum]

[2000Gou]

[2001Kim]

Landolt-Börnstein New Series IV/11D4

17

Wada, H., Lee, S.W., Pehlke, R.D., “Nitrogen Solubility in Liquid Fe and Fe-Mn Alloys”, Met. Trans. B, 17B(1), 238–239 (1986) (Experimental, Phase Relations, Thermodyn., 17) Raghavan, V., “The Fe-Mn-N (Iron-Manganese-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Metals, Delhi, 1, 183–189 (1987) (Crys. Structure, Phase Diagram, Phase Relations, Review, 26) Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase Diagams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Thermodyn., Review, *, #, 126) Rochegude, P., Foct, J., “Behaviour of Nitrogen During Mechanical Alloying at Solid Solutions and Iron Nitrides”, Compt. Rend. Acad. Sci. Paris, Ser. 2, 309, 1545–1549 (1989) (Experimental, Phase Relations, 9) Siwka, J., Tochowicz, S., “Nitrogen Solubility in Liquid Iron Alloys Containing High Amounts of Chromium and Manganese in Hyperbaric Conditions”, Arch. Metall., 35(3), 449–461 (1990) (Experimental, Phase Relations, 26) Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 36) Satir-Kolorz, A.H., Feichtinger, H.K., “On the Solubility of Nitrogen in Liquid Iron and Steel Alloys Using Elevated Pressure”, Z. Metallkd., 82(9), 689–697 (1991) (Experimental, Calculation, Phase Relations, 24) Volynova, T.F., Sidorova, I.B., Emelyanova, I.Z., “State of the Boundaries and Features of the Fracture of Powder - Metallurgical Iron - Manganese Alloys”, Metal Sci. Heat Treat., 34(11–12), 693–699 (1992) (Experimental, Mechan. Prop., 4) Qiu, C., Fernandez-Guillermet, A., “A Thermodynamic Evaluation of the Mn-N System”, Z. Metallkd., 84(1), 11–22 (1993) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 54) Qiu, C., “A Thermodynamic Evaluation of the Fe-Mn-N System”, Metall. Trans. A, 24A, 629–645 (1993) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 49) Raghavan, V., “Fe-Mn-N (Iron-Manganese-Nitrogen)”, J. Phase Equilib., 14(5), 629 (1993) (Phase Diagram, Phase Relations, Review, 8) Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System using the Compound-Energy Model with Prediction of the Vibrational Entropy”, Z. Metallkd., 85(3), 154–163 (1994) (Phase Diagrams, Phase Relations, Theory, Assessment, 75) Kunze, J., Rothe, I., “Solubility of Nitrogen in Austenitic FeCrMn Alloys”, Steel Research, 65(8), 331–337 (1994) (Calculation, Experimental, Thermodyn., 25) Tanaka, T., Gokcen, N.A., Iida, T., Morita, Z.-I., “Thermodynamic Relationship Between the Enthalpy Interaction Parameter and the Entropy Interaction Parameter in Liquid IronNitrogen Based Ternary Alloys”, Z. Metallkd., 85, 696–700 (1994) (Theory, Thermodyn., 17) Nechaev, Yu.S., Omelchenko, A.V., “Solubility of Molecular Nitrogen in Austenite”, Russ. J. Phys. Chem., 69(9), 1408–1413 (1995), translated from Zh. Fiz. Khim., 69(9), 1556–1561 (1995) (Experimental, Phase Relations, 23) Gavriljuk, V.G., Yakovenko, P.G., Ullakko, K., “Inﬂuence of Nitrogen on Vibration Damping and Mechanical Properties of Fe-Mn Alloys”, Scr. Mater., 38(6), 931–935 (1998) (Experimental, Mechan. Prop., 7) Ariapour, A., Yakubsov, I., Perovic, D.D., “Effect of Nitrogen on Shape Memory Effect of a Fe-Mn-based Alloy”, Mater. Sci. Eng. A, 262(1–2), 39–49 (Experimental, Mechan. Prop., 24) Sumin, V.V., Chimid, G., Rashev, Ts., Saryivanov, L., “The Neutron-Spectroscopy Proof of the Strong Cr-N Interactions in Nitrogen Stainless Steels”, Mater. Sci. Forum, 318–320, 31–40 (1999) (Crys. Structure, Electronic Structure, Experimental, 11) Goune, M., Belmonte, T., Fiorani, G.M., Chomer, S., Michel, H., “Modelling of Diffusion Precipitation in Nitrided Alloyed Iron”, Thin Solid Films, 377, 543–549 (2000) (Interface Phenomena, Calculation, Phase Relations, 27) Kim, E.J., You, B.D., Pak, J.J., “Nitrogen Solubility in Liquid Manganese and Ferromanganese Alloys”, Metall. Mater. Trans. B, 32B(4), 659–668 (2001) (Experimental, Thermodyn., 22)

MSIT®

DOI: 10.1007/978-3-540-78644-3_16 # Springer 2008

18 [2002Bli]

[2002Lee]

[2003Gou1]

[2003Gou2]

[2004Pad] [2004Wit]

[2006Che] [2007Wit] [Mas2] [V-C2]

Fe–Mn–N Bliznuk, V.V., Glavatska, N.I., Soederberg, O., Lindroos, V.K., “Effect of Nitrogen on Damping, Mechanical and Corrosive Properties of Fe-Mn Alloys”, Mater. Sci. Eng. A, 338, 213–218 (2002) (Experimental, Interface Phenomena, Mechan. Prop., Phase Relations, 10) Lee, Y.K., “Effects of Nitrogen on γ -ɛ Martensitic Transformation and Damping Capacity of Fe-16%Mn-X%N Alloys”, J. Mater. Sci. Lett., 21(15), 1149–1151 (2002) (Experimental, Mechan. Prop., 15) Goune, M., Belmonte, T., Redjaimia, A., Weisbecker, P., Fiorani, J.M., Mochel, H., “Thermodynamic and Structure Studies on Nitrided Fe-1.62%Mn and Fe-0.56%V Alloys”, Mater. Sci. Eng. A, 351, 23–30 (2003) (Calculation, Crys. Structure, Experimental, Phase Relations, 22) Goune, M., Redjaimia, A., Belmonte, T., Michel, H., “Identiﬁcation and Characterization of a Novel Mn-N Nitride Formed in Fe-Mn-N Alloy”, J. Appl. Crystallogr., 36(1), 103–108 (2003) (Crys. Structure, Experimental, Mechan. Prop., Phase Relations, 26) Paduani, C., “Electronic Structure and Magnetic Properties of MnFe3N”, J. Appl. Phys., 96(3), 1503–1506 (2004) (Calculation, Electronic Structure, Magn. Prop., 6) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Calculation, Thermodyn., #, 34) Chen, L., “Electronic Structure and Magnetism of Fe4–xMnxN Compounds”, J. Appl. Phys., 100(11), 13717 (2006) (Electronic Structure, Magn. Prop., Calculation, 20) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson′s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_16 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–Ni

1

Iron – Manganese – Nickel Nathalie Lebrun, Pierre Perrot

Introduction Mn and Ni are important constituents of steels, so, the Fe-Mn-Ni ternary system raised much interest. [1909Jae, 1913Par] gave a ﬁrst insight to the general shape of the liquidus surfaces which has largely been conﬁrmed in more recent works [1985Koc, 1994Rag] and reproduced in the reviews of [1983Riv, 1988Ray]. There is a remarkable consistency between the data of [1913Par] and those related to binary systems determined half a century later. A more recent determination of the liquidus was carried out by [1997Sch]. A stability domain for the phases α, γ and ε is shown by [1980Bra], but the conditions of pressure and quenching are not given, so that the diagram cannot be used. No Calphad assessment exists for the whole systems, but partial data have been gathered [1998Mie, 2000Mie]. Main experimental data are reported in Table 1. Binary Systems Using new experimental thermodynamic data, the Fe-Mn system has been recently reassessed and the Calphad description was updated by [2004Wit]. This new reevaluation of the phase equilibria leads to consistently better ﬁts to the available experimental data. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). Consequently, the Fe-Mn system is accepted from [2004Wit]. The Fe-Ni and Mn-Ni phase diagrams are taken from [2007Kuz] and [2007Wat], respectively. In a thermodynamic assessment of the Mn-Ni binary carried out by [2005Guo], the two intermetallic phases η’MnNi and η”MnNi are considered as a unique phase. Solid Phases All the data on unary, binary and ternary phases are indicated in Table 2. The γ’(MnxFe1–x)Ni3 solid solution, ordered below 525°C with a L12 structure (AuCu3 type) presents a maximum in the Young’s modulus and in the order-disorder transition temperature, [1966Ibr, 1967Yeg] together with a minimum in the electrical conductivity around x ∼ 0.5 [1966Ibr] and an anomaly in the thermal capacity and in the saturation magnetization [1966Ibr], which is an indication of a short-range ordering of Fe and Mn around x ∼ 0.5 in addition to the long-range order of the L12 (AuCu3) type which superimposes in the whole composition range. Liquidus, Solidus and Solvus Surfaces The liquidus surface has been experimentally determined by [1913Par, 1985Koc], critically reinterpreted by [1997Sch] and calculated, together with the solidus surface, by [1985Koc], reproduced in [1994Rag]. But this last calculation does not match well with the accepted binary systems and can not be taken into account. Figure 1 presents the liquidus projection from [1997Sch], slightly modiﬁed to take into account the accepted binary systems. The peritectic monovariant lines have also been added. Figure 2 represents the liquidus line in the Fe rich corner of the diagram, calculated by [1998Mie] and showing the primary crystallization ﬁelds of the α and γ solutions. Isothermal Sections The α-γ equilibria in the Fe rich corner were calculated by [1989Har] at 850, 750, 650 and 550°C. Some of these partial isotherms are shown in Figs. 3a and 3b. The same equilibria, calculated at 700°C by [1995Tan] Landolt-Börnstein New Series IV/11D4

MSIT®

DOI: 10.1007/978-3-540-78644-3_17 # Springer 2008

2

Fe–Mn–Ni

using a central atom model differ from the preceding one by the shape of the (α+γ) domain which is shrunk along the Mn/Ni = 1 line, which does not agree with the experimental observations [2002Mun]. The shape of the (α+γ)/γ border at 550°C (Fig. 3b) is very similar to the shape of the same border calculated at 450°C by [2002Mun] and conﬁrmed by microscopic observations, which increases the degree of conﬁdence which may be attributed to the calculations of [1989Har]. Figure 4 shows the whole Fe-Mn-Ni diagram calculated at 450°C by [2004Mun]. This diagram has been widely modiﬁed to take into account the non stoichiometry of the intermetallic compounds and the non existence of the Mn3Ni and MnNi2 phases at 450°C. Thermodynamics Mn activities have been measured by a Knudsen effusion cell [1964Smi] at 1059°C in the whole concentration range. Fe and Ni activities were calculated by integration of the Gibbs-Duhem equation through the ternary system. In the γ ﬁeld, Mn-Ni alloys present a strong negative departure from ideality, departure which decreases as Fe replaces Ni in the solid solution. Expressions of the Gibbs energy for the liquid and γ phases were presented by [1987Dan] using a subregular model with ternary interaction parameters, but the calculated liquidus surface agree poorly with the experimental one. The existence of a metastable miscibility gap island in the α(Fe,Mn,Ni) alloy was postulated [1970Suz] to explain the age hardening observed in martensitic alloys before their decomposition into a biphased (α + γ) stable state. The miscibility gap was deduced by combination of the energy parameters related to the three binary systems, but was not conﬁrmed by further studies. Careful investigation on the Fe-12Ni-6Mn (mass%) alloy [1981Ray] explain age hardening by the precipitation of the η’MnNi in the matrix, a tetragonal compound whose ratio c/a lies close to unity. Notes on Materials Properties and Applications Main experimental works are reported in Table 3. Mn is known to decrease the Curie temperature of Fe-Ni alloys [1969Col] and increase the atomic magnetic moment of alloys in which the atomic ratio Ni:Fe = 4:1 up to a maximum observed at 5.0 at.% Mn in the alloy. However, Mn in Ni3Fe alloy increases the Curie temperature up to a maximum of 2.5 at.% Mn in the alloy [1991Gan]. Such an ordering explains the difﬁculty of cold rolling Ni3Fe alloys containing more than 0.5 at.% Mn. The atomic magnetic moment μB = 1.074 for Ni80Fe20 increases up to 1.107 for Ni76Fe19Mn5, decreases down to 1.033 for Ni72Fe19Mn10. For atomic ratios Ni:Fe = 3:2 and 2:3, Mn decreases the atomic magnetic moment. Mn was also shown to lower the degree of long range atomic order in Ni3Fe [1987Bab1]. Neutron scattering on Ni3Fe1–xMnx shows that Fe and Mn are randomly arranged on the site. When x rises, the order-disorder transition is replaced by a second order phase transition [1987Bab2]. The magnetic phase diagram has been investigated along the 50 at.% Fe section by [1974Ett, 1985Der], at 15 and 20 at.% Mn by [1981Men], at 72 at.% Fe by [1990Dub], at a ratio Fe/Ni = 65/45 and < 30 at.% Mn by [1992Wul, 1995Hoe] and in the whole composition range by [1976Men]. The magnetic moment in the Fe-Mn-Ni alloys is calculated by [1990Jep] and a statistical theory of the magnetic ordering in Fe-Mn-Ni alloys was developed by [1990Her]. The experimental magnetic diagram [1976Men, 1990Jep, 1995Hoe] is represented in Fig. 5. Both magnetic orderings (ferro + antiferro) exist at low temperature around the transition. The heat capacity was shown to present a maximum near the concentration for which the alloys looses its long range ferromagnetic behavior [1975Lev], but on both sides of this concentration, the heat capacity variations are weak. A spin glass state has been observed [1983Der, 1984Der, 1985Der, 1986Der] below 100 K in the concentration range corresponding to the ferromagnetic-antiferromagnetic transition. Invar behavior is characterized by a minimum of the linear expansion coefﬁcient observed around 35 at.% Ni [1977Zak]. The Invar anomaly is connected to the ferromagnetic properties of the alloy, a minimum in the expansion coefﬁcient corresponding to a maximum in the magnetic moment. The Invar effect disappears when the Mn content of the alloys exceeds 10 at.%. Characteristics of the antiferromagnetic alloys (Mn: Fe = 2:3) are well described by electron concentration [1971Col]. Linear spontaneous magnetostriction and Neel temperature decrease with the Ni content.

DOI: 10.1007/978-3-540-78644-3_17 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–Ni

3

Miscellaneous [2006Li] investigated the microstructural evolution of 36 mass% Ni austenitic steel under severe plastic deformation using the accumulative roll-bonding process at 500°C. During the mechanical deformation, a grain subdivision process occurs leading to ultraﬁne grain formation. The structure formed is found ﬁner and straighter than that formed in ferrite steel deformed under similar conditions. Fe-Mn-Ni alloys are reported to show a remarkable age hardening behavior [2002Mun, 2006Ned] attributed to the precipitation of ηMnNi particles. However, they suffer grain boundary embrittlement depending on the ageing process. The possible causes of that effect are discussed by [2004Wil] which concludes that Mn is a major embrittlement cause of its own right due to its afﬁnity towards N, S and P which segregate towards the grain boundaries before the austenitization, a point of view defended earlier by [1983Ray]. Fe-Mn-Ni presents a martensitic transformation which may be athermal (or burst type) or isothermal [2000Rag]. An athermal transformation starts abruptly at a well deﬁned Ms (martensite start) temperature. The amount of martensite formed at Ms varies from a few percent to 50%. An athermal transformation is observed in alloys containing between 20 and 30 at.% Ni. In an isothermal transformation, the Ms point is not well deﬁned and the transformation occurs in a narrow temperature range or after some ﬁnite incubation time during isothermal holding. Fe-Mn-Ni alloys are typical for presenting an isothermal martensitic transformation. In Fe containing 23 at.% Ni, the nature of the transformation is very sensible to the Mn content between 3 and 4 at.% Mn [1998Pal, 1999Cha, 2000Cha]. A hydrostatic pressure or a magnetic ﬁeld [2000Kak] may also change the nature of the transformation. For Fe72Ni24Mn4 (in at.%) alloy, which exhibits an isothermal martensitic transformation under the room temperature, a static magnetic ﬁeld (up to 3.2 MA·m–1) lowers the nose temperature of the TTT curve together with the incubation time whereas a hydrostatic pressure (up to 0.5 GPa) increases the nose temperature of the TTT curve together with the incubation time [2001Kak]. There is a strong correlation between the magnetic behavior and the nature of the austenite-martensite transformation [2002Ayd]. The Fe alloy with 10 mass% Ni and 10 mass% Mn, austenitic in the quenched state from 1100°C, presents a Ms point at –20°C [1967Bou]. By heating, the martensite-austenite transformation is observed between 450 (As point) and 640°C. The antiferromagnetic alloy Fe72Mn22Ni6 presents a Ms point at 47°C [1988Dub1] and a Neel temperature at 85°C [1988Dub2]. Whereas the austenitic phase is paramagnetic, the martensitic phase may be ferro- or antiferromagnetic [2005Akt]. Alloys with 3 to 7 mass% Ni and 11 to 15 mass% Mn present high damping capacity under frequencies as low as 0.2 kHz, a shape memory behavior and superelasticity [1995Wat] which is attributed to the austenitemartensite transformation. The best property is observed for the 5Ni-15Mn (in mass%) alloy. (Fe,Mn,Ni) alloys have been electrodeposited from a mixture of sulfates or chloride [1980Sri]. The structure of the layer is α or γ and the composition depends strongly on the temperature (10–60°C) and on the pH (2-8) imposed. A deposit with a minimum internal stress can be obtained using a high bath temperature, a low cathode current density, a low pH and a rough cathode surface.

Table 1.

Investigations of the Fe-Mn-Ni Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1913Par]

Thermal analysis

1100–1450°C, liquidus and solidus surfaces (whole diagram)

[1954Kur]

Thermal analysis, dilatometry, microscopic investigations

< 800°C, phase equilibria in the solid state (whole diagram)

[1964Smi]

Knudsen effusion cell, Mn vapor pressure measurements

1059°C, the whole system, Mn activity measured, Fe and Ni activities calculated

[1975Lev]

Magnetization, heat capacity measurements

< 0°C, Fe / Mn = 86 / 14, 15 to 40 at.% Ni (invar alloys) (continued)

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Fe–Mn–Ni

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1983Der]

Magnetic transitions, heat capacity measurements

5–90 K, 50 at.% Fe

[1984Der]

Magnetic transitions, heat capacity measurements

80–320 K, 20 at.% Mn, spin glass state

[1985Koc]

Thermal analysis

1000–1500°C, liquidus and solidus surfaces (whole diagram)

[1986Der]

Magnetic transitions, heat capacity measurements

5–20 K, 15 at.% Mn, 45 to 65 at.% Fe, spin glass state

[1986Gom]

Neutron diffraction, long range atomic order determination

15 to 75 at.% Ni, 10 to 70 at.% Fe

[1987Bab1, 1987Bab2]

Neutron diffraction, long range atomic order determination

Ni3Fe1–xMnx (x < 0.3), order-disorder transition

[1987Dan]

Calorimetry (temperature not given)

Integral mixing enthalpy of the liquid in the whole composition range

[1988Dub1]

Diffuse neutron scattering on single crystal

Fe72Mn22Ni6 (in at.%), martensitic transformation

[1988Gom]

Neutron diffraction

400°C, phase diagram

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αδFe,δMn)

cI2 Im 3m W

(αFe) (Ferrite) < 912

Lattice Parameters [pm]

Comments/References

a = 286.65

(δFe) 1538–1394

a = 293.15

(δMn) 1246–1138

a = 308.13

pure Fe at 25°C [Mas2, V-C2] dissolves 5 at.% Mn at 527°C [2004Wit], dissolves up to 4.6 at.% Ni at 495°C [2007Kuz] at 1390°C [V-C2, Mas2] dissolves 10 at.% Mn at 1474.5°C [2004Wit], dissolves up to 3.8 at.% Ni at 1517°C [2007Kuz] pure Mn at 1137°C [2007Wat] dissolves up to 12.2 at.% Fe at 1236.6°C [2004Wit]. Dissolves 6 at.% Ni [2007Wat] (continued)

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Fe–Mn–Ni

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α’ (Martensite)

tI4 I4/mmm -

(εFe)

hP2 P63/mmc Mg

γ, (γFe,γMn,Ni)

cF4 Fm 3m Cu

(γFe) (Austenite) 1394–912 (γMn) 1138–1100 (Ni) < 1455 (Fe0.65Ni0.35)1–xMnx

Lattice Parameters [pm]

5

Comments/References

metastable phase obtained by quenching from austenite a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2] triple point α-γ-ε at 8.4GPa, 430°C

a = 364.67

at 915°C [V-C2, Mas2]. Complete solubility with (γMn) [2004Wit] and Ni [2007Kuz] pure Mn at 1097°C [2007Wat]. Complete solubility with (γFe) [2004Wit] and (Ni) [2007Wat]. [Mas2]. Complete solubility with (γFe) [2007Kuz] and (γMn) [2007Wat] x < 0.12, invar alloy [1986Huc]

a = 386.26 a = 352.40 a = 358.3 ± 0.5

(βMn) 1100–727

cP20 P4132 βMn

a = 631.52

[Mas2]. Dissolves up to 32.9 at.% Fe [2004Wit]. Dissolves up to 18 at.% Ni [2007Wat].

(αMn) < 727

cI58 I 43m (αMn)

a = 891.26

pure Mn at 25°C [Mas2]. Dissolves up to 35.2 at.% Fe [2004Wit]. Dissolves up to 9 at.% Ni [2007Wat].

φ, Mn3Ni < 430

tF*

a = 369.8 c = 369.2

75 at.% Mn [2007Wat] antiferromagnetic

ε, Mn2Ni 720–560

-

-

31.5–35.5 at.% Ni [2007Wat]

η, MnNi 911–675

cP2 Pm 3m CsCl

a = 374.5 ± 0.5 a = 297.7

45–52 at.% Ni [1991Gok] at 50 at.% Ni, 750°C [2007Wat]

η’, MnNi 775–620

tP4 P4/mmm AuCu

a = 373.1 c = 363.2

47–55.5 at.% Ni [2007Wat] at 50 at.% Ni [2007Wat] L10 structure

η”, MnNi < 480

t** -

γ’, MnNi3

cP4

-

∼ 46–54 at.% Ni [2007Wat] Antiferromagnetic [1991Gok] L12 structure (continued)

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Fe–Mn–Ni

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

< 520

Pm 3m AuCu3

Lattice Parameters [pm]

Comments/References

71–85 at.% Ni [2007Wat] at 75 at.% Ni [2007Wat]

a = 358.9

γ’Fe0.5Mn0.5Ni3 < 525

a = 356.2

γ’, FeNi3 < 517

a = 354.7

Fe-Mn ordering [1966Ibr]

63 to 85 at.% Ni [2007Kuz]

ζ,MnNi2 710-580

t** -

-

64–68.5 at.% Ni [2007Wat]

ζ’, MnNi2 < 440

t** -

-

∼ 66.7–73 at.% Ni [2007Wat]

γ”, FeNi

tP4 P4/mmm AuCu

a = 357.9 c = 357.9

L10 structure [V-C2]. Metastable ordering temperature 320°C at 51.2 at.% Ni [2007Kuz]

Table 3.

Investigations of the Fe-Mn-Ni Materials Properties

Reference

Method/Experimental Technique

Conditions/Type of Property

[1950Kra]

Dilatometry, hardness, tensile strength, TTT curves

< 950°C, < 17 mass% Mn, < 5 mass% Ni, α/γ transformations

[1957Rav]

Dilatometry, electrical conductivity

< 900°C, MnxFe1–x Ni3 (x < 0.03), orderdisorder transitions

[1966Ibr]

XRD, dilatometry, Young’s modulus, tensile strength, electrical conductivity, saturation magnetization

< 800°C, MnxFe1–x Ni3 (0 < x < 1), orderdisorder transitions

[1967Bou]

XRD, dilatometry, hardness measurements

< 650°C, Fe + 10 mass% Mn + 10 mass% Ni, phase transitions

[1967Yeg]

XRD, dilatometry, Young’s modulus

< 750°C, MnxFe1–x Ni3 (0 < x < 1), orderdisorder transitions, ordering kinetics

[1968Min]

Electrical resistance

< 1000°C, MnxFe1–x Ni3 (0 < x < 1), diffusion, kinetics of ordering

[1969Col]

Curie temperature, saturation magnetization

77–840 K, the whole concentration range

[1969Pan]

Neutron diffraction, resistivity, Yield point, magnetization

700°C, Ni3Mn0.95Fe0.05, kinetics of ordering (continued)

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Fe–Mn–Ni

7

Reference

Method/Experimental Technique

Conditions/Type of Property

[1970Gom]

Neutron diffraction, saturation magnetization

(Ni3Fe)1–xMnx (0.01 < x < 0.05), Mn inﬂuence on ordering

[1971Col]

Expansion, magnetostriction, Neel temperature

< 300°C, Mn / Fe = 2 / 3, < 25 at.% Ni, invar anomaly

[1974Ett]

Mössbauer, antiferromagnetic-ferromagnetic transitions

< 500°C, 50 at.% Fe, 10 to 41 at.% Ni, magnetic phase diagram

[1976Men]

Antiferromagnetic-ferromagnetic transitions

< 800°C, the whole composition range, magnetic phase diagram

[1977Jo]

Nuclear magnetic resonance (NMR)

Magnetic state of Mn diluted in (Fe,Ni) alloys

[1977Sch]

Inelastic neutron scattering, time of ﬂight method

25 and 225°C, Fe60Mn30.5Ni9.5 (in at.%) alloy

[1977Zak]

Dilatometry

4.2–300 K, 35 at.% Ni, < 20 at.% Mn Invar behavior

[1979Che]

Resistivity, saturation magnetization

4.2–90 K, 8.6 mass% Mn + 1.1 mass% Fe annealed 1 h at 900°C

[1980Bar]

Mössbauer, magnetic anisotropy

500–625°C, Fe85Ni10Mn5 (in at.%)

[1980Geo]

Dilatometry, strain gauge, electrical resistivity, martensitic transformation

Fe70+xNi30–2xMnx (x < 3) quenched from 1100–1150°C, then annealed 2 to 30 min at 200-650°C

[1981Men]

Antiferromagnetic-ferromagnetic transitions

< 800°C, 15 and 20 at.% Mn, magnetic phase diagram

[1981Ray]

Scanning and transition electron microscopy (SEM and TEM), neutron diffraction, hardness measurements

Fe-12Ni-6Mn (in mass%), age hardening, mechanism investigation

[1983Zol]

Magnetic susceptibility, magnetostriction (100-300 kOe)

77–900 K, Fe70+xNi30–2xMnx (x < 3)

[1984Kaj]

Martensitic transformation, optical microscopy at 143 K

Fe-23Ni-3.9Mn (in mass%), austenetized at 1250°C, water quenched then observed at 143 K

[1985Der]

Magnetic susceptibility, magnetostriction, elastic modulus, dilatometry

4.2–1000 K, 50 at.% Fe, magnetic phase diagram, spin glass state

[1986Huc]

Mössbauer

(Fe0.65Ni0.35)1–xMnx (x < 0.12) invar behavior

[1987Sin]

Optical microscopy, TEM, martensitic transformation

500–600°C, 19.8 mass% Ni, 5.2 mass% Mn

[1988Dub2]

Neutron scattering on single crystal, magnetic susceptibility

Fe72Mn22Ni6 (in at.%), magnetic ordering near the Neel temperature

[1990Dub]

Neutron scattering on single crystal, magnetization

4.2–800 K, 72 at.% Fe, magnetic ordering, martensitic transitions (continued)

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8

Fe–Mn–Ni

Reference

Method/Experimental Technique

Conditions/Type of Property

[1991Gan]

DTA, XRD, electrical conductivity, Curie temperatures

< 700°C, 20 to 26 at.% Fe, < 5 at.% Mn, magnetic ordering

[1991Wat]

SEM, tensile strength

3 to 7 at.% Ni, 11 to 15 a % Mn, damping properties

[1992Wul]

Magnetization, Curie temperature

4–280 K, Fe / Ni = 65 / 35, < 30 at.% Mn, magnetic diagram

[1995Hoe]

Electrical resistivity, Mössbauer

4–280 K, Fe / Ni = 65 / 35, < 30 at.% Mn, spin glass state

[1995Wat]

Dilatometry, hardness, stress-strain diagram

3 to 7 mass% Ni, 11 to 15 mass% Mn, damping effect

[1996Heo]

SEM, electrical resistivity on age hardened alloy

400–550°C, 8 mass% Mn, 7 mass% Ni, Mn segregation

[1998Pal]

XRD (Rietveld reﬁnement), microhardness

77 and 143 K, 23 at.% Ni, 3.8 at.% Mn, martensitic transformation

[1999Cha]

XRD (Rietveld reﬁnement), SEM, microhardness

140 to 250 K, 23 at.% Ni, 3.3 at.% Mn, martensitic transformation

[2000Cha]

XRD (Rietveld reﬁnement), SEM, microhardness

77 to 200 K, 23 at.% Ni, 3.6 at.% Mn, martensitic transformation

[2000Kak, 2001Kak]

SEM, electrical resistivity, hydrostatic pressure (< 1 GPa)

77 to 210 K, Fe72Ni24Mn4 (in at.%), martensitic transformation

[2002Ayd]

SEM, Mössbauer at 77 K

30 mass% Ni, 0.2 mass% Mn, martensitic transformation

[2002Mun, 2004Mun]

TEM, HR-TEM (high spatial resolution TEM), selected area electron diffraction (SAED), X-Ray energy dispersive spectroscopy (EDS)

8 mass% Mn, 7 mass% Ni annealed at 1200°C, then aged 0.5 to 48 h at 450°C, ageing behavior, precipitation of austenite particles at grain boundaries

[2002Tsu]

Magnetization curves, magnetic torque curves

Ni-Fe/Mn82Ni18 thin layers on MgO substrate, exchange anisotropy of ferroantiferromagnetic bilayers

[2005Akt]

TEM, Mössbauer, magnetic properties of the martensite

Fe-25Ni-5Mn and Fe-34.5Ni-10Mn (in mass%), austenitized at 1100°C then quenched at 77 K

[2005Bel]

Stress-strain curbes, electron backscattered diffraction (EBSD)

Ni-30 Fe-0.02 Mn-0.01 C (in mass%), hot rolled at 1000–1200°C

[2006Gor]

Magnetization curves, magneto-optical indicator ﬁlm (MOIF) technique

Fe50Mn50/Ni81Fe19 thin layers, exchange anisotropy of ferro-antiferromagnetic bilayers

[2006Li]

FEG-SEM (ﬁeld emission gun SEM), EBSD

36 mass% Ni, accumulative roll bonding deformation at 500°C

[2006Ned]

FEG-TEM (ﬁeld emission gun TEM), HREDS, SAED

Fe-10Ni-7Mn (mass%), aged at 480°C

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Fe–Mn–Ni

Fig. 1. Fe-Mn-Ni.

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9

Liquidus surface projection

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Fig. 2. Fe-Mn-Ni.

Fe–Mn–Ni

The Fe rich corner of the liquidus surface

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Fe–Mn–Ni

Fig. 3a. Fe-Mn-Ni.

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11

The α/γ equilibrium in the Fe rich corner 650°C

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Fig. 3b. Fe-Mn-Ni.

Fe–Mn–Ni

The α/γ equilibrium in the Fe rich corner 550°C

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Fe–Mn–Ni

Fig. 4. Fe-Mn-Ni.

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13

Calculated isothermal section at 450°C

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Fig. 5. Fe-Mn-Ni.

Fe–Mn–Ni

The magnetic phase diagram

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Fe–Mn–Ni References [1909Jae] [1913Par]

[1950Kra]

[1954Kur]

[1957Rav] [1964Smi]

[1966Ibr]

[1967Bou]

[1967Yeg]

[1968Min]

[1969Col] [1969Pan]

[1970Gom]

[1970Suz] [1971Col] [1974Ett] [1975Lev]

[1976Men]

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15

Jänecke, E., “Ternary Alloys of Cu, Ag, Au; Cr, Mn; Fe, Co, Ni; Pd, Pt Metals” (in German), Z. Phys. Chem., 67, 668–688 (1909) (Experimental, Phase Diagram, Phase Relations, 22) Parravano, N., “The Ternary Alloys of Iron - Nickel - Manganese, Nickel - Manganese Copper, Iron - Manganese - Copper Systems” (in German), Z. Metallkd., 4, 171–203 (1913), reproduced in Int. Z. Metallography, 4, 187–202 (1913) (Experimental, Phase Diagram, Phase Relations, 14) Kramer, I.R., Toleman, S.L., Haswell, W.T., “Iron-Manganese and Iron-Manganese-Nickel Alloys”, Trans. Amer. Soc. Met., 42, 1260–1294 (1950) (Experimental, Phase Relations, Magn. Prop., Kinetics, 4) Kurnakov, N.N., Troneva, M.Ya, “The Iron-Manganese-Nickel System Investigation” (in Russian), Izv. Sekt. Fiz.-Khim. Anal., 24, 132–147 (1954) (Experimental, Magn. Prop., Morphology, Phase Diagram, Phase Relations, 17) Ravdel, M.P., Selissky, Ya.P., “Transitions in Ternary Ni3Fe Solid Solutions” (in Russian), Dokl. Akad. Nauk SSSR, 115(2), 319–321 (1957) (Experimental, Morphology, 5) Smith, J.H., McCabe, C.L., Paxton, H.W., “Manganese Vapor Pressures in Equilibrium with Manganese-Iron-Nickel Solid Solutions”, J. Phys. Chem., 68(6), 1345–1354 (1964) (Experimental, Phase Relations, Thermodyn., 37) Ibragimov, E.A., Selissky, Ya.P., Sorokin, M.N., “Investigation of the Effects of Ordering on Ternary Ni-Fe-Mn Solid Solutions”, Russ. Metall., (5), 82–87 (1966), translated from Izv. Akad. Nauk SSSR, Met., (5), 152–157 (1966) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 3) Bourgeot, J., Manenc, J., “Structure of an Fe-Mn-Ni Alloy” (in French), Mem. Scient. Revue Metall, 64(11), 1006–1007 (1967) (Experimental, Phase Relations, Crys. Structure, Magn. Prop., 6) Yeganyan, I.L., Selisskiy, Ya.P., “Atomic Ordering Effects in Binary Solid Solutions (Ni3Fe, Mn)”, Phys. Met. Metallogr., 23(2), 195–197 (1967), translated from Fiz. Met. Metalloved., 23(2), 369–371 (1967) (Crys. Structure, Magn. Prop., Experimental, 5) Minaeva, G.G., Panin, V.E., Fadin, V.P., Pyabyshkina, F.A., Zhukova, V.M., “The Effect on the Ordering Kinetics of Alloying Ni3Mn Alloy with Co and Fe” (in Russian) in “Diffuzionnye Protsessy v Metallakh”, Naukova Dumka, Kiev, 84–88 (1968) (Experimental, Kinetics, Electr. Prop., 12) Colling, D.A., “Intrinsic Magnetization of Fe-Ni-Mn Alloys”, J. Appl. Phys., 40(3), 1379–1381 (1969) (Experimental, Magn. Prop., 6) Panin, V.E., Prushinsky, V.V., Fadin, V.P., Novak, L.I., “Effect of Alloying a Ni3Mn Alloy with a Third 3d-Transition Element on Ordering Kinetics”, Sov. Phys., Doklady, 14(11), 1119–1122 (1970), translated from Dokl. Akad. Nauk SSSR, 189(1), 84–87 (1969) (Crys. Structure, Experimental, Kinetics, 15) Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of Ni3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, Magn. Prop., 6) Suzuki, T., “Metastable Miscibility Gap Island in Fe-Ni-Mn Ternary Martensitic Alloys”, Trans. Jpn. Inst. Met., 11(4), 257–263 (1970) (Calculation, Thermodyn., Magn. Prop., 21) Colling, D.A., Mathur, M.P., “Invar Behavior in Antiferromagnetic Fe-Mn-(Ni) Alloys”, J. Appl. Phys., 42(13), 5699–5703 (1971) (Experimental, Magn. Prop., 27) Ettwig, H.H., Pepperhoff, W., “On Magnetism of γ-Fe-Ni-Mn Alloys”, Phys. Status Solidi A, 23(1), 105–111 (1974) (Experimental, Magn. Prop., Crys. Structure, 18) Levesque, B., Caudron, R., Costa, P., “Low Temperature Speciﬁc Heat of Ni1–x(Mn0.14Fe0.86)x Alloys”, Proceedings of the International Conference on Low Temperature Physics, 3, 246–249 (1975) (Magn. Prop., Thermodyn., Experimental, 6) Menshikov, A.Z., Kazantsev, V.A., Kuzmin, N.N., “Magnetic State of Fe-Ni-Mn Alloys” (in Russian), Zh. Eksp. Teor. Fiz., 71, 648–656 (1976) (Experimental, Magn. Prop., 26)

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16 [1977Jo]

[1977Sch] [1977Zak]

[1979Che]

[1980Bar]

[1980Bra] [1980Geo]

[1980Sri] [1981Men]

[1981Ray] [1983Der]

[1983Ray] [1983Riv]

[1983Zol]

[1984Der]

[1984Kaj] [1985Der]

Fe–Mn–Ni Jo, T., “Magnetic State of Mn Atom in Ferromagnetic Ni-Fe-Mn and Ni-Mn Alloys: Local Environment Effect”, Physica B/C, 86–88(pt.2), 747–748 (1977) (Experimental, Magn. Prop., 4) Schreiber, J., Matz, W., “Antiferromagnons in Fe-Mn-Ni Alloys”, Physica B/C, 86–88(pt.1), 272–274 (1977) (Experimental, Magn. Prop., 5) Zakharov, A.I., Basargin, O.V., Menshikov, A.Z., Kalinin, V.M., “Temperature-Coefﬁcient of Linear Expansion of Fe-Ni-Mn Alloys”, Phys. Met. Metallogr., 43(5), 182–185 (1977), translated from Fiz. Met. Metallov., 43(5), 1103–1105 (1977) (Experimental, Magn. Prop., 12) Cherenkov, V.A., Rogel`berg, I.L., Beylin, V.M., “Low-Temperature Resistivity Anomalies in Nickel-Manganese, Nickel-Manganese-Cobalt (or Iron) Alloys”, Phys. Met. Metallogr., 47(4), 168–170 (1979), translated from Fiz. Met. Metalloved., 47(4), 865–867 (1979) (Experimental, Electr. Prop., Magn. Prop., 12) Barton, J., Kansy, J., Panek, T.J., “Inﬂuence of Mn and Ni on the Magnetic-Properties of FeNi-Mn Alloys”, Phys. Status Solidi A, 62(2), 407–412 (1980) (Experimental, Magn. Prop., Morphology, 12) Brandes, E.A., Flint, R.F., “Mn-Fe-Ni” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 114 (1980) (Phase Diagram, Phase Relations, Review, 3) Georgieva, I.Ya., Matyushenko, L.A., “Effect of Heat Treatment on the Kinetics of the TwoStage Martensitic Transformation in Fe-Ni-Mn and Fe-Ni-Mo Alloys”, Met. Sci. Heat Treat., 22(5-6), 311–314 (1980), translated from Metallov. Term. Obrab. Metal., SSSR, 22(5), 3–5 (1980) (Experimental, Kinetics, Phase Relations, 7) Srivastava, S.C., “Electrodeposition of Ternary Alloys: Developments in 1972 - 1978”, Surf. Technol., 10, 237–257 (1980) (Electrochemistry, Magn. Prop., Review, 121) Menshikov, A.Z., Burlet, P., Chamberod, A., Tholence, J.L., “Magnetic Phase Diagram of γ-FeNiMn Alloys with a Mixed Exchange Interaction”, Solid State Commun., 39(10), 1093–1095 (1981) (Experimental, Magn. Prop., Phase Relations, 14) Ray, R.K., “Structure and Properties of an Fe-Ni-Mn Alloy”, Z. Metallkd., 72(3), 203–210 (1981) (Crys. Structure, Morphology, Magn. Prop., Experimental, 16) Deryabin, A.V., Rimlyand, V.I., Larionov, A.P., “Low-temperature Speciﬁc Heat of Fe-Ni-Cr and Fe-Ni-Mn Alloys”, Sov. Phys., Solid-State, 25(7), 1109–1111 (1983), translated from Fiz. Tverd. Tela, 25(7), 1921–1925 (1983) (Experimental, Thermodyn., 23) Ray, R.K., “Strenghtening Mechanisms in a Fe-11 Mn-6.5 Ni Alloy”, Arch. Eisenhuettenw., 54(12), 513–518 (1983) (Experimental, Magn. Prop., 15) Rivlin, V.G., Raynor, G.V., “Phase Equilibriums in Iron Ternary Alloys 9: Critical Review of Constitution of Ternary Systems Fe-Mn-X (X = Ti, V, Cr, Co, Ni, Cu)”, Int. Met. Rev., 28(1), 23–64 (1983) (Phase Diagram, Phase Relations, Review, 68) Zolotarevskiy, I.V., Snezhnoy, V.L., Sheyko, L.M., “Magnetostriction of the Austenite of Iron-Nickel-Manganese Alloys and the Martensitic Transformation Induced by a Strong Magnetic Field”, Phys. Met. Metallogr., 55(3), 115–121 (1983), translated from Fiz. Met. Metallov., 55(3), 548–553 (1983) (Experimental, Magn. Prop., Phase Relations, 20) Deryabin, A.V., Menshikov, A.Z., Larionov, A.P., Kazantsev, V.K., “Heat Capacity of FexNi80–xMn20 Alloys”, Phys. Met. Metallogr., 57(3), 182–185 (1984), translated from Fiz. Met. Metalloved., 57(3), 614–616 (1984) (Experimental, Magn. Prop., Thermodyn., 12) Kajuwara, S., “Continuous Observation of Isothermal Martensite Formation in Fe-Ni-Mn Alloys”, Acta Metall., 32(3), 407–413 (1984) (Experimental, Morphology, Thermodyn., 16) Deryabin, A.V., Tkov, A.V., Kazantsev, V.K., Shvetsov, B.N., “Magnetic Phase Diagram, Thermal and Magnetoelastic Properties of Alloys of System Fe50Ni50–xMnx”, Phys. Met. Metallogr. 59(3), 52–56 (1985), translated from Fiz. Met. Metalloved., 59(3), 476–480 (1985) (Experimental, Magn. Prop., Phase Relations, 11)

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Fe–Mn–Ni [1985Koc]

[1986Der]

[1986Gom]

[1986Huc] [1987Bab1]

[1987Bab2]

[1987Dan]

[1987Sin]

[1988Dub1]

[1988Dub2]

[1988Gom]

[1988Ray] [1989Har]

[1990Dub]

[1990Her]

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Kocherzhinskii, Yu.A., Kulik, O.G., Turkevich, V.Z., “Melting Diagram of the Fe-Mn-Ni System”, Russ. Metall., (4), 204–207 (1985), translated from Izv. Akad. Nauk SSSR, Met., (4), 210–213 (1985) (Experimental, Calculation, Phase Diagram, Phase Relations, 4) Deryabin, A.V., Kourov, N.I., Larionov, A.P., Menshikov, A.Z., “On the Nature of the Low Temperature Heat Capacity Maximum in the Range of the Ferro-Antiferromagnetic Transition in Iron-Nickel-Manganese Alloys”, Phys. Met. Metallogr., 62(1), 83–88 (1986), translated from Fiz. Met. Metalloved., 62(1), 95–100 (1986) (Experimental, Kinetics, Thermodyn., 27) Gomankov, V.I., Kleynerman,V.I., Tret’yakov, B.N., Zaytsev, A.I., “The Coexistence of Ni3(FeMn) and Ni(FeMn) Superlattices in the Iron-Nickel-Manganese System”, Phys. Met. Metallogr., 61(6), 93–96 (1986), translated from Fiz. Met. Metalloved., 61(6), 1136–1139 (1986) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, Review, Theory, Thermodyn., 7) Huck, B., Saurenbach, F., Hesse, J., “Investigation of Spin Structure in FCC Fe-Ni-Mn”, Hyperfine Interact., 28(1–4), 479–482 (1986) (Electronic Structure, Experimental, 11) Babayev, Z.M., Matysina, Z.A., Mekhrabov, A.O., “Ordering Temperatures and Order Parameters of Alloy Ni3Fe with Impurity Mn or Cr”, Phys. Met. Metallogr., 64(1), 191–194 (1987), translated from Fiz. Met. Metalloved., 64(1), 202–205, (1987) (Experimental, Theory, Phase Relations, 11) Babayev, Z.M., Valiyev, E.Z., Menshikov, A.Z., Mekhrabov, A.O., “Atomic Ordering in Ni3(Fe1–xMnx) Alloys”, Phys. Met. Metallogr., 64(4), 124–127 (1987), translated from Fiz. Met. Metalloved., 64(4), 762–766 (1987) (Crys. Structure, Experimental, 9) Danilenko, V.M., Turkevich, V.Z., “Thermodynamic Properties of Alloys, and Constitution Equilibrium Diagram of the Fe-Ni-Mn System”, Russ. Metall. (4) 210–212 (1987), translated from Izv. Akad. Nauk SSSR, Met., (4), 209–211 (1987) (Phase Diagram, Phase Relations, Thermodyn., Experimental, 7) Singh, J., Wayman, C.M., “Formation of Secondary Austenite During the α’-γ Transformation in an Fe-Ni-Mn Alloy”, Mater. Sci. Eng., 93, 227–233 (1987) (Experimental, Morphology, Phase Relations, 16) Dubinin, S.F., Mikhaylov, Yu.N., Sidorov, S.K., “Diffuse Scattering of Neutrons in the PreMartensitic Range of Alloys Fe72Mn22Ni6”, Phys. Met. Metallogr., 65(4), 188–190 (1988), translated from Fiz. Met. Metalloved., 65(4), 823–824, (1987) (Experimental, Phase Relations., 1) Dubinin, S.F., Mikhaylov, Yu.N., Skorobogatov, V.P., Sidorov, S.K., “Critical Effects in the Antiferromagnetic Crystal Fe72Mn22Ni6 with Unstable Lattice”, Phys. Met. Metallogr., 66(2), 67–74 (1988), translated from Fiz. Metal. Metalloved., 66(2), 283–291 (1988) (Experimental, Phase Relations, 11) Gomankov, V.I., Zaitzev, A.I., Kleinerman, V.I., “Diagram of Structural States of Alloys of the System Ni-Fe-Mn”, Russ. Metall., (2) 196–200 (1988), translated from Izv. Akad. Nauk SSSR, Met., (2), 204–208 (1988) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) Raynor, G.V., Rivlin, V.G., “Fe-Mn-Ni” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 361–362 (1988) (Phase Diagram, Phase Relations, Review, 5) Hari Kumar, K.C., Raghavan, V., “The bcc-fcc Equilibrium in Ternary Iron Alloys - III”, J. Alloy Phase Diagrams, 5(3), 201–220 (1989) (Calculation, Phase Diagram, Phase Relations, 28) Dubinin, S.F., Mikhaylov, Yu.N., Skorobogatov, V.P., “Magnetic and Structural Transformations in Fe72MncNi28–c Alloys”, Phys. Met. Metallogr., 69(6), 64–68 (1990), translated from Fiz. Met. Metalloved., 69(6), 69–73 (1990) (Experimental, Magn. Prop., Phase Diagram, Phase Relations, 12) Herman, F., Jepsen, O., “Electron and Magnetic Structure of the Ternary fcc Mn-Fe-Ni System. II. Disordered Alloys and Ferromagnetic-Antiferromagnetic Interfaces”, Phys. Rev. B,

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[1990Jep]

[1991Gan]

[1991Gok]

[1991Wat]

[1992Wul]

[1994Rag] [1995Hoe]

[1995Tan]

[1995Wat]

[1996Heo]

[1997Sch] [1998Mie]

[1998Pal]

[1999Cha]

[2000Cha]

[2000Kak]

Fe–Mn–Ni 41(10), 6811–6819 (1990) (Electronic Structure, Experimental, Magn. Prop., Phase Relations, 17) Jepsen, O., Herman, F., “Electronic and Magnetic-Structure of the Ternary fcc Mn-Fe-Ni System. 1. Ordered Compounds”, Phys. Rev. B, 41(10), 6801–6810 (1990) (Electronic Structure, Experimental, Magn. Prop., 39) Ganguli, B., Meherotra, V., Gupta, K.P., “Measurement of Order-Disorder Transition Temperature of Some Ni-Fe-Mn Alloys”, Trans. Indian Inst. Met., 44(2), 187–189 (1991) (Crys. Structure, Electric Prop., Magn. Prop., Experimental, 3) Gokcen, N.A., “Mn-Ni (Manganese-Nickel)” in “Phase Diagrams of Binary Nickel Alloys”, Nash, P. (Ed.), ASM Int., Materials Park, OH, 199–206 (1991) (Crys. Structure, Phase Diagram, Phase Relations, Review, 47) Watanabe, S., Sato, S., Nakagami, I., Nagashima, S., “Damping Behavior of Fe-Ni-Mn Alloys” (in Japanese), Tetsu to Hagane, 77(2), 306–313 (1991) (Experimental, Morphology, Magn. Prop., 17) Wulfes, A., Bottger, C.H., Hesse, J., Sievert, J., Ahlers, H., “Magnetic Phase Diagram of the Reentrant Spin Glass System (Fe0.65Ni0.35)1–xMnx”, J. Magn. Magn. Mater., 104–107(III), 2069–2071 (1992) (Abstract, Magn. Prop., Phase Diagram, Phase Relations, 11) Raghavan, V., “Fe-Mn-Ni (Iron-Manganese-Nickel)”, J. Phase Equilib., 15(6), 617–618 (1994) (Phase Diagram, Phase Relations, Review, 14) Hoefer, A., Fricke, M., Boettger, C., Hesse, J., “Resistivity of (Fe0.65Ni0.35)1–xMnx versus Ferro- and Antiferromagnetic Re-Entrant Spin Glass Transitions”, Phys. Solid State A, 148, 551–564 (1995) (Electr. Prop., Magn. Prop., Phase Relations, Experimental, 22) Tanaka, T., Aaronson, H.I., Enomoto, M., “Calculations of α/γ Phase Boundaries in Fe-CX1-X2 Systems from the Central Atoms Model”, Metall. Mater. Trans. A, 26A(3), 535–545 (1995) (Calculation, Phase Diagrams, Phase Relations, Thermodyn., 27) Watanabe, S., Sato, S., Miura, K., “An Unique Feature of Mechanical Property of IronNickel-Manganese Alloy”, J. Mat. Proc. Tech., 53(1–2), 467–476 (1995) (Experimental, Magn. Prop., 14) Heo, N.H., “Theory of Nonequilibrium Segregation in an Fe-Mn-Ni Ternary Alloy and a Ductile-Brittle-Ductile Transition”, Acta Mater., 44(7), 3015–3023 (1996) (Experimental, Magn. Prop., Thermodyn., 25) Schuermann, E., Djurdjevic, M., Nedeljkovic, L., “Liquid Equilibria in the Fe-Ni-Mn System”, Steel Res., 68(12), 512–515 (1997) (Assessment, Phase Diagram, 7) Miettinen, J., “Approximate Thermodynamic Solution Phase Data for Steels”, Calphad, 22(2), 275–300 (1998) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., 83) Pal, H., Chanda, A., De, M., “Characterisation of Microstructure of Isothermal Martensite in Fe-23Ni-3.8Mn by Rietvield Method”, J. Alloys Compd., 278, 209–215 (1998) (Crys. Structure, Phase Relations, 25) Chanda, A., Pal, H., De, M., Kajiwara, S., Kikuchi, T., “Characterisation of Microstructure of Isothermal Martensite Formed at Low Temperature in Powder of Fe-23Ni-3.3Mn Alloy by Rietveld Method”, Mater. Sci. Eng. A, 265A, 110–116 (1999) (Experimental, Crys. Structure, Morphology, Magn. Prop., Phase Relations, 15) Chanda, A., De, M., Kajiwara, S., “Characterisation of Microstructure of Isothermally Transformed Martensite in Low Temperature in Powder and Bulk State of Fe-23Ni-3.6Mn (mass%) Alloy by Rietveld`s Method”, Jpn. J. Appl. Phys., 39(2A), 539–544 (2000) (Experimental, Crys. Structure, Morphology, Magn. Prop., Phase Relations, 25) Kakeshita, T., Saburi, T., Shimizu, K., “Kinetics of Martensitic Transformations in Some Ferrous and Non-Ferrous Alloys”, Philos. Mag. B, 80B(2), 171–181 (2000) (Experimental, Kinetics, Phase Relations, 36)

DOI: 10.1007/978-3-540-78644-3_17 # Springer 2008

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Fe–Mn–Ni [2000Mie]

[2000Rag]

[2001Kak]

[2002Ayd]

[2002Mun]

[2002Tsu]

[2004Mun]

[2004Wil]

[2004Wit]

[2005Akt]

[2005Bel]

[2005Guo] [2006Gor]

[2006Li] [2006Ned]

[2007Kuz]

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Miettinen, J., Howe, A.A., “Estimation of Liquidus Temperatures for Steels Using Thermodynamic Approach”, Ironmaking Steelmaking, 27(3), 212–227 (2000) (Calculation, Phase Relations, Thermodyn., 53) Raghavan, V., “The Martensitic Transformation in Fe-Ni and Fe-Ni-X Alloys at Subzero Temperatures”, Trans. Indian Inst. Met., 53(6), 597–603 (2000) (Review, Phase Relations, Kinetics, 44) Kakeshita, T., Katsuyama, J., Fukuda, T., Saburi, T., “Time-Dependent Nature of Displacive Transformations in Fe-Ni and Fe-Ni-Mn Alloys Under Magnetic Field and Hydrostatic Pressure”, Mater. Sci. Eng. A, 312A(1–2), 219–226 (2001) (Experimental, Kinetics, Phase Relations, 12) Aydin, A., Guler, E., Aktas, H., Gungunes, H., “Mössbauer Studies on Athermal Martensite Formation in an Fe-Ni-Mn Alloy”, Bull. Mater. Sci., 25(5), 359–360 (2002) (Electronic Structure, Experimental, 10) Mun, S.-H., Watanabe, M., Li, X., Oh, K.H., Williams, D.B., Lee, H.-C., “Precipitation of Austenite Particles at Grain Boundaries During Aging of Fe-Mn-Ni Steel”, Metall. Mater. Trans. A, 33A(4), 1057–1067 (2002) (Experimental, Morphology, Phase Diagram, 34) Tsunoda, M., Konoto, M., Takahashi, M., “Magnetic Anisotropy of Antiferromagnet in Exchange Coupled Ni-Fe/Mn-Ni Epitaxial Bilayers”, Phys. Status Solidi A, 189A(2), 449–457 (2002) (Experimental, Magn. Prop., 12) Mun, S.-H., Heo, Y.U., Watanabe, M., Williams, D.B., Lee, H.-C., “Discussion of “Precipitation of Austenite Particles at Grain Boundaries During Aging of Fe-Mn-Ni Steel”. Authors’ Reply”, Metall. Mater. Trans. A, 35A(1), 355–356 (2004) (Experimental, Morphology, Phase Diagram, Phase Relations, 13) Wilson, E.A., “Discussion of “Precipitation of Austenite Particles at Grain Boundaries During Aging of Fe-Mn-Ni Steel””, Metall. Mater. Trans. A, 35A(1), 352–355 (2004) (Morphology, 18) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Phase Relations, Calculation, Thermodyn., #, 34) Akturk, S., Durlu, T.N., “The Magnetic Properties of Martensitic Phase in Fe-Ni-Mn Alloys: Mössbauer Spectroscopy Observation”, J. Mater. Sci., 40(22), 6023–6026 (2005) (Electronic Structure, Experimental, Magn. Prop., Morphology, 13) Beladi, H., Hodgson, P.D., Barnett, M.R., “Mapping the Hot Deformation Microstructure of Ni-30Fe Alloy”, ISIJ Int., 45(12), 1893 (2005) (Experimental, Mechan. Prop., Magn. Prop., Morphology, 16) Guo, C., Du, Z., “Thermodynamic Optimization of the Mn-Ni System”, Intermetallics, 13(5), 525–534 (2005) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 42) Gornakov, V.S., Nikitenko, V.I., Shapiro, A.J., Shull, R.D., Yangund, F.Y., Chien, C.L., “Switching of Domains and Domain Walls in Fe50Mn50/Ni81Fe19 Bilayers with non-180° Ferromagnetic Domains”, Phys. Met. Metallogr., 101(Sup.1), S51–S55 (2006) (Experimental, Magn. Prop., Morphology, 10) Li, B.L., Tsuji, N., Minamino, Y., “Microstructural Evolution in 36%Ni Austenitic Steel during the ARB Process”, Mat. Sci. Forum, 512, 73–78 (2006) (Experimental, Morphology, 10) Nedjad, S.H., Ahmadabadi, M.N., Mahmudi, R., Furuhara, T., Maki, T., “Analytical Transmission Electron Microscopy Study of Grain Boundary Precipitates in an Fe-Ni-Mn Maraging Alloy”, Mater. Sci. Eng. A, 438A, 288–291 (2006) (Electronic Structure, Experimental, 7) Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenbrg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2007) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, 41)

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20 [2007Wat]

[2007Wit] [Mas2] [V-C2]

Fe–Mn–Ni Watson, A., Wagner, Z., E. Lysova, E. Rokhlin, L., “Mn-Ni (Manganese-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenbrg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2007) (Phase Diagram, Phase Relations, Crys. Structure, 13) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_17 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–O

1

Iron – Manganese – Oxygen Pierre Perrot

Introduction The Fe-Mn-O system has raised very soon a huge interest because manganese is a useful element generally found in iron ores. Mn has a beneﬁcial effect on the plasticity of steels, decreases the stacking fault energy, increases the nitrogen solubility and gives a shape memory effect. Mn being easily oxidized gives non metallic inclusions in iron [1981Mik] and their conditions of formation have ben well explored. [1929Sch] showed that MnO has for effect to stabilize iron oxides, thus making harder their reduction by CO. The ﬁrst FeO-MnO tentative diagram, found in [1930Ben] presents a miscibility gap in the solid state which is considered as doubtful by the author and has not been conﬁrmed since, although [1943Whi, 1964Lev] reproduce it in their reviews. [1937Wen] presents a Fe-FeO-MnO phase diagram accepted today, phase diagram without any miscibility gap, a fact which has been deﬁnitively proved by X-Ray diffraction [1946Pet]. Later, this system was investigated with respect to melting, reﬁning and corrosion of stainless steels. The main experimental investigations on phase equilibria and thermodynamics are gathered in Table 1. An assessment of the reactions occurring in the liquid phases may be found in [1993Tur]. No Calphad assessment were carried out. Binary Systems Using new experimental thermodynamic data, the Fe-Mn system has been recently reassessed and the Calphad description was updated by [2004Wit]. This new reevaluation of the phase equilibria leads to consistently better ﬁts to the available experimental data. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). Consequently, the Fe-Mn system is accepted from [2004Wit]. The Fe-O system is accepted from [Mas2], which reproduces the fundamental work of [1945Dar, 1946Dar]. Two careful assessment may be found in [1991Sun, 1995Kow]. They reproduce well the experimental equilibria and differ by the description of the (Fe,O) liquid solution. The Mn-O binary system is accepted from [2007Fen]. Solid Phases The solid phases are presented in Table 2. Wüstite Fe1–xO gives a complete solid solution “manganowüstite” (Fe1– yMny)1–xO whose x, the departure from stoichiometry decreases when y, the Mn content, increases [1967Sch1]. For y > 0.5, the manganowüstites in equilibrium with iron are stoichiometric [1970Aub]. For pure Fe1–xO, 0.05 < x < 0.12, whereas for pure Mn1–xO, 0 < x < 0.05. The lattice parameter of manganowüstite in equilibrium with a metallic phase (reduced side of the solid solution) and with a spinel phase (oxidized side of the solid solution), measured by [1968Oki] is shown in Fig. 1. Magnetite βFe3O4 (inverse spinel) gives also a complete spinel solid solution with βMn3O4 (normal spinel). In the iron rich part, whose composition can be represented by β(Fe1–yMny)Fe2O4 (0 < y < 1), the structure is of the type “disordered spinel” because Mn2+ ions which have a preference for tetrahedral sites [1969Baf] replace the Fe2+ ions in the octahedral sites of the spinel structure. However, [1985Tay] presents wrongly MnFe2O4 as inverse. A model of the cations distribution amongst the sites of the spinel structure, based on site preference energy, may be found in [1979Pel, 1983ONe, 2003Mue]. These iron rich spinels may be easily obtained by mixing Fe2O3 and MnO2 at 950°C under a (CO2 + 1% CO) atmosphere whereas the mixing under pure CO2 leads to the bixbyite (Fe,Mn)2O3 solid solution. The crystal parameter of the spinel solution β(Fe1–yMny)Fe2O4 (0 < y < 1) increases linearly with the Mn content [1984Pun, 1995All, 2005Zin] according to the Vegard’s law. Landolt-Börnstein New Series IV/11D4

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Fe–Mn–O

The non stoichiometry of the Mn ferrite MnFe2O4 has been investigated by [1983Tsu] at 1150°C and by [1998Bon] between 400 and 900°C under various oxygen pressures. Below 3 Pa O2, the parameter remains constant at 861.2 pm, corresponding to the stoichiometric spinel. Between 3 and 300 Pa O2, the crystal parameter decreases down to 850.5 pm corresponding to the hyperstoichiometric, metal defective spinel. Above 300 Pa O2, the hematite phase forms and the parameter of the remaining spinel increases, which corresponds to an increase of the Mn content of the spinel. Below 550°C, and at high oxygen partial pressure, MnFe2O4 oxidizes into MnFe2O4+δ metastable. A value of δ = 0.5 corresponds to the γ(Mn0.5Fe)2O3 metastable phase [1998Bon]. As a consequence, it is hard to deﬁne an upper limit of stability for MnFe2O4 at low temperatures. In the manganese rich part of the solid solution, whose composition may be represented by Mn(Fe1–yMny)2O4 (0 < y < 1), the spinel solid solution is direct [1986Maz], with the Mn2+ ions in the tetrahedral sites and the Mn3+ and Fe3+ ions in the octahedral sites. The Mn rich part of the solid solution is tetragonally deformed [1969Wic, 1971Bra, 1973Hol, 1995Bat] as shown in Fig. 2. The origin of the tetrahedral distortion of the lattice for the Mn rich spinels is the effort of Mn3+ ions to remove their orbitally degenerated ground state (3d4) [2000Pol]. This is the cooperative Jahn-Teller effect on Mn3+ ions in octahedral sites which provokes a lowering of the symmetry of their surroundings. The cubic-tetragonal transition varies from 200°C when y = 0.5 to 1171°C when y = 1, which corresponds to Mn3O4. At 940°C, the cubic spinel Mn2.54Fe0.46O4 is in equilibrium with the tetragonal spinel Mn2.73Fe0.27O4 [1973Hol]. The Mn rich spinel are stable under oxygen pressures higher than those generated by pure CO2. The spinel solid solutions may be metal defective (Fe1–yMny)3(1–x)O4 under higher oxygen pressures [1969Wic]. The departure from stoichiometry of these spinels increases with temperature and with iron content. The lattice parameter of some spinel (0.27 < y < 0.32), investigated by [1974Tan], increases with the oxygen pressure when x < 0, presents a maximum which corresponds to the stoichiometric composition (x = 0), then decreases, which corresponds to x > 0 (the ratio O/Metal in the spinel is then higher than 4/3). The valences of the elements (Fe2+, Fe3+, Mn2+, Mn3+) in the spinel phase have been discussed in [1967Sch2]. αFe2O3 (stable under the form of hematite) and αMn2O3 (stable under the form of bixbyite) present limited solubility, although Mn2O3 may dissolve Fe2O3 up to 50 mol% at 800°C and 70 mol% at 1020°C. γMn2O3 decomposes slowly at 1000°C to give Mn3O4 through αMn2O3 as an intermediate phase. The solid solutions γ(Fe1–yMny)2O3 (y > 0.45) prepared by co-precipitation in aqueous medium [1990Pat] decomposes at lower temperatures to give MnFe2O4 and Mn2O3 which transforms into Mn3O4 at 1000°C. Quasibinary Systems The αFe2O3-βMn2O3 quasibinary system under 0.21 kPa of oxygen pressure (air atmosphere), established by [1969Wic] and reproduced in [1980Bra] is shown in Fig. 3. At higher temperatures, αFe2O3 and βMn2O3 are not stable. Under air atmosphere, αFe2O3 loses oxygen and gives βFe3O4 at 1380°C and βMn2O3 transforms into αMn3O4 at 977°C. Above 1380°C, the solid phase in equilibrium with the liquid, is always the β(Fe,Mn)3O4 spinel solid solution [1958Hoo]. It is not clear whether or not the liquid phase is in the same oxidation state as the solid. At lower temperatures (< 877°C), Mn and Fe are in the state of oxidation +3 and the only stable solid solutions are the manganese rich (Mn,Fe)2O3 and iron rich (Fe,Mn)2O3 solid solutions. Between 877 and 1380°C, the (Fe,Mn)2O3 solid solutions may be in equilibrium with the (Fe,Mn)3O4 spinel solutions [1962Mua]. Metastable equilibria may easily been observed [1996Gol] by sintering pellets of Fe2O3-Mn2O3 mixtures under 10 MPa followed by quenching, annealing or slow cooling. The FeO-MnO quasibinary diagram in equilibrium with the (Fe,Mn) metallic phase, experimentally determined by [1977Oet] and calculated by [1993Wu] is presented in Fig. 4, and the metallic phase in equilibrium with the solid manganowüstite (MW) or with the liquid oxide (L2) is shown. The manganowüstite (Fe1–yMny)1–xO in equilibrium with the metallic phase is characterized by x = 0.05 for y = 0. When the Mn content increases, x decreases and becomes 0 for y ∼ 0.5. For y > 0.5 the manganowüstite is stoichiometric (x = 0).

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–O

3

Liquidus Surface [1989Rag] presents a tentative liquidus projection which is not reproduced in this report because the tie lines suggested are not credible. Actually, experimental data are scarce and the position of the invariant points are unknown. The two-liquid domain (Fe+FeO) originated along the Fe-O side continues through the diagram up to the Mn-O side, but the tie lines (Fe,Mn)-(Fe,Mn)O have never been determined. As Mn is more easily oxidized than Fe, it is probable that Mn goes preferentially in the liquid oxide phase and Fe in the metallic phase. Isothermal Sections The oxygen solubility in liquid iron ﬁrst investigated by [1950Hil] was shown to decrease with the manganese content. However, it is not clear wether the oxygen solubility in the Fe-Mn alloys present a minimum [1973Buz, 1976Jan]. [1981Ave] carried out oxygen solubility measurements between 1600 and 1700°C under H2-H2O atmospheres and claimed the existence of a minimum in the oxygen solubility towards 5 mass% Mn, but without a convincing experimental evidence. More credible are the results presented by [1987She] which, through oxygen solubility measurements towards the Mn rich end of the alloy, show the presence of a minimum of solubility at 0.015 mass% O in a Fe + 9.6 mass% Mn at 1600°C under 0.1 MPa of oxygen pressure. The oxygen solubility shown in Fig. 5 from [2000Tak] represent the oxygen content of the liquid alloys in equilibrium with the (Fe,Mn)O liquid slag in the iron rich corner or with the manganowüstite solid solution in the manganese rich corner. Calculations carried out by [1998Lee, 2004Jun] did not take into account the existence of a minimum. The isothermal section at 1600°C, mainly from [1977Oet] is represented in Fig. 6 and shows the isobaric curve 0.1 MPa O2 proposed by [1950Gur] and reproduced by [1964Lev]. The tie lines in the two-phase domain manganowüstite (Fe,Mn)O - spinel (Fe,Mn)3O4, were investigated at 1300°C [1967Sch1], 1200°C [1993Sub, 1994Sub], 1150°C [1967Sch1], 1000°C [1965Tre, 1975Duq, 2005Zin], 987°C [1968Oki] and 700°C [1984Pun]. Figure 7 gives isothermal section at 1300°C [1967Sch1, 1989Rag]. Figure 8 taken from [1967Sch1], gives the position of each tie line together with the oxygen pressure at equilibrium at 1300 and 1150°C. The potential diagram taking into account the equilibria between the solid solutions (metal, manganowüstite, spinel, hematite and bixbyite) at 900°C is shown in Fig. 9 from [1979Pel]. Oxygen pressure at equilibrium has been measured by equilibration with a CO-CO2 [1967Sch1] or with a CO2-H2 [1968Oki, 1984Pun] atmosphere. Figure 10 represents the manganowüstite ﬁeld at 1150°C together with the isobaric curves [1967Sch1]. Under higher oxygen pressures, manganowüstite oxidizes into spinel. Under lower oxygen pressures, manganowüstite is reduced into a metallic phase constituted mainly from iron. Thermodynamics The thermodynamic quantities of formation of MnFe2O4 from its oxides [1979Sek] are given in Table 3 together with the enthalpy of dissolution of O2 in the spinel solid solution [1974Tan] and the Gibbs energy of dissolution of MnO in liquid iron [1991Mik, 2003Per]. Heat capacities of MnFe2O4, Mn1.5Fe1.5O4 and Mn2FeO4 which belong to the solid solution (Fe1–yMny)3O4, measured between 200 and 740 K by [1981Nai], are presented in Table 4. The ferrimagnetic-paramagnetic transition, observed around 550 K (180 ± 10°C) for these three compounds is characterized by a λ shape accident in the heat capacity vs temperature curves and the transition entropy was evaluated at 55 ± 5 J·K–1·mol–1 for each compound, with a slight tendency to decrease with the Mn content of the spinel solid solution. The activities of FeO in the manganowüstite solid solutions in equilibrium with Fe has been evaluated from the oxygen pressures at equilibrium Fe/(Fe1–yMny)1–xO, the oxygen pressures being generated by CO-CO2 atmospheres [1929Sch, 1971Ono, 1990Fra], H2-H2O atmospheres [1970Aub, 1970Bul, 1991Ban], H2-CO2 atmospheres [1968Oki] or measured from the emf of a solid electrolyte cell [1965Tre]. Authors agree to propose a slight positive departure towards ideality, which is conﬁrmed by the calculations of [1983Dav] based on the volume mismatch between FeO and MnO. The FeO-MnO solid solution is described by a regular model with an energy parameter α = 5250 J·mol–1 at 1150°C. For calculating the FeO-MnO diagram in equilibrium with a (Fe,Mn) alloy, [1993Wu] supposes the liquid ideal (α = 0) and proposes α = 6126 J·mol–1 Landolt-Börnstein New Series IV/11D4

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4

Fe–Mn–O

between 1380 and 1850°C, in good agreement with the experimental diagram. A thorough investigation [1972Bal] showed that, for a given ratio Fe/Mn of the solid solution, the FeO activity decreases with the departure from stoichiometry. The liquid (Fe,Mn)O solution in equilibrium with iron behaves quasi ideally at 1500°C [1991Ban]. The manganowüstites in equilibrium with a spinel phase behaves ideally. Activities of FeO and MnO inside the manganowüstite ﬁeld have been calculated by [1988Lyk, 1990Fra] from the oxygen potential vs composition experimental curves. Surprisingly, [1997Pet] calculates, for the manganowüstite, spinel and hematite solid solutions, a strong negative departure from ideality. Such a result may be explained, as pointed out by the authors [1996Gol, 1997Pet], by a non equilibrium state and an ill controlled oxygen pressure. A thermodynamic model has also been proposed [1993Tyu] for the spinel solid solution. The activities of Fe3O4 in the spinel solid solution have been also evaluated from the oxygen pressures at equilibrium spinel/manganowüstite under various CO-CO2 gaseous atmosphere [1967Sch1, 1971Ono, 1990Fra], H2-CO2 atmospheres [1983Ter] or from oxygen pressure at the spinel/corundum equilibrium measured directly [1970Roe, 1971Ono, 1988Yoo] provided that oxygen pressures lie above 1 kPa. For instance, the upper domain of stability of the spinel (Mn0.482Fe0.518)Fe2O4, that is the oxygen pressure at equilibrium spinel-bixbyite, measured by [1988Yoo] in the temperature range 1000–1200°C is given by: log10 (pO2/bar) = (11.7 ± 0.6) – (1.87 ± 0.08) / T The spinel solid solutions present a large positive departure from ideal behavior [1979Sek, 1990Fra]. The interaction coefﬁcients of Mn and O in liquid iron at 1600°C, (< 2 mass% Mn) have been evaluated by [1966Sch, 1974Sig, 1991Mik] as: eO(Mn) = {∂ log10 fO / ∂ (mass% Mn)} = – 0.021 at 1600°C, with fO = {(mass% O in pure Fe) / (mass% O in alloy)}, as eO(Mn) = – 0.040 ± 0.005 by [1967Buz], as eO(Mn) = – 0.054 by [1981Mik] and as eO(Mn) ∼ 0 by [1972Mat, 1976Jan] at the same temperature. Actually, Mn in liquid Fe increases slightly the oxygen solubility and the value accepted by [2003Per] is eO(Mn) = – 0.025. [1981Ave] pointed out the difﬁculties arising in the measurements at high temperatures because of the easy volatilization of Mn but presents interaction parameters in good agreement with the preceding ones. [2000Tak, 2002Hin] showed that the value eO(Mn) = – 0.037, although less precise at inﬁnite dilution, may be used up to 20 mass% Mn. On the other hand, [1970Nis] used the oxygen distribution between solid and liquid alloy to calculate eO(Mn) = – 1.83 in the (δFe). Mn increases strongly the oxygen solubility in (δFe). Notes on Materials Properties and Applications The main experimental works are summarized in Table 5. Mn may be used as deoxidizer in steelmaking [1972Mat]. Although it is not so strong than Al or Si, it has many beneﬁcial effects on the plasticity of steel and it represents, with Ni, the main constituent of High Nitrogen Steels. Mn increases the plasticity of steels but decreases the machinability [2004Umi] because the formation of oxide ﬁlms with high melting temperatures reduces the lubriﬁcation effects. The spinel solid solution (Fe1–yMny)Fe2O4 may be used as soft magnetic material [1993Alc] and used in the fabrication of components such as high density magnetic core or read/write heads for high speed tapes or magnetic recording [2005Pad]. MnFe2O4 may be prepared by solid state reaction between MnCO3 and Fe2O3 [2001Der] at 900–1100°C. Li2O may be added under the form of LiNO3 as dopant for stimulating the ferrite formation. The activation energy for the ferrite formation goes down from 174 kJ·mol–1 without catalyst to 117 kJ·mol–1 with the addition of 3.5 mol% Li2O. Mechanical alloying of αFe2O3 (hematite) and βMn2O3 (bixbyite) forms βFeMnO3, a ferrimagnetic insulator with a magnetic moment of 2.8 μB per formula unit and a Curie temperature around 40 K [2000Sei]. The size of the crystals lie between 10 and 20 nm. Mechanical alloying of MnO + Fe2O3 mixtures forms MnFe2O4, but a prolonged milling time may induce a reduction due to metallic iron originating from ball debris, thus transforming MnFe2O4 into manganowüstite [2005Pad]. Mechanical alloying of (1–y) Fe2O3 + y Mn2O3 (y > 0.3) forms only bixbyite like crystals [2004Med] whereas the mixture (1–y)Fe + y Mn2O3 gives a spinel phase for y > 0.6 and a manganowüstite phase for y < 0.6. Nanosized particles may also be obtained [2001Mur] from the displacement reaction: 2 FeCl3 + 4 MnO → MnFe2O4 + 3 MnCl2

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5

activated by high energy ball milling. The spontaneous magnetization of the nanopowder obtained is lower than that of the bulk and decreases with the nanoparticle size. Below 50 K, the coercitivity increases sharply with the decreasing temperature. Colloid nanocrystals (Fe,Mn)3O4 have been prepared [2002Sar] by chemical precipitation of FeCl2+FeCl3+MnCl2 in basic aqueous medium (pH > 12). The MnFe2O4 nanocrystals synthesized by radiofrequency plasma torch [2006Swa] exhibit a cuboctahedral morphology having only (111) and (110) surfaces. A new phase MnFe2O4–δ (δ unknown), disordered spinel characterized by a ratio c/a < 1 has been prepared by reacting MnO2 + Fe2O3 at 1200°C [2001Hu]. Its Curie temperature is TC ∼ 400°C (the Curie temperature of the normal cubic spinel is ∼ 280–297°C) and it possesses a negative magnetoresistance. Miscellaneous The electrical conductivity of MnFe2O4 sintered at 1250°C, measured at 100–200°C [1972Rez] was shown to decrease with time, a behavior attributed to a redistribution of metallic ions on the tetrahedral and octahedral sites. The Curie point lies at about 300°C, and seems to shift towards 350°C through the oxidation process of MnFe2O4 [1986Maz]. The Fe3+ of the maghemite γFe2O3 may be substituted by Mn3+ or Mn2+. The substitution by Mn2+ introduces vacancies [1984Gil] which are ordered if the substitution rate is low. Metal Ceramic microstructures may be obtained by partial reduction of (Fe1–yMny)O manganowüstites [1995Sub]. The presence of refractory oxides (Al2O3, Cr2O3, ZrO2, alkaline earth oxides) as dopants enhances the rate of the metal precipitation during the reduction. The precipitation of the metallic phase, a rich iron alloy, occurs mainly in grain boundaries if Al2O3 or Cr2O3 are present as dopants. Table 1.

Investigations of the Fe-Mn-O Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1929Sch]

Reduction isotherm under CO-CO2 atmospheres

600–800°C, Fe2O3-MnO mixtures

[1930Ben]

Thermal analysis, metallography

1300–1650°C, Mn-O and FeO-MnO phase diagrams

[1937Wen]

Thermal analysis, metallography

1300–1650°C, Fe-FeO-MnO phase diagram

[1946Pet]

X-ray diffraction

FeO-MnO solid solution

[1950Gur]

Isobaric curves determination by weight loss measurements

1600°C, Fe2O3-FeO-MnO, < 0.1 MPa of oxygen pressure

[1950Hil]

Oxygen solubility measurements, chemical analysis

1550–1650°C, < 2 mass% Mn, < 0.2 mass% O

[1958Hoo]

Thermal analysis, X-ray diffraction

< 1600°C, Fe3O4-Mn3O4 phase diagram

[1962Mua]

Thermal analysis, X-ray diffraction

800–1585°C, Fe-Mn-O phase diagram under 0.21 kPa O2

[1965Tre]

Powder sintering, X-ray diffraction, EMF measurements

1000°C, from 10 nPa to 10 mPa of oxygen pressure

[1967Sch1]

XRD, chemical analysis and thermogravimetry

1000–1300°C, CO-CO2 atmospheres, spinel + manganowüstite ﬁeld (continued)

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6

Fe–Mn–O

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1968Oki]

XRD, chemical analysis, Neel temperatures measurements

987°C, equilibrium Fe-(Fe,Mn)O-(Fe,Mn) Fe2O4 under CO2-H2

[1969Wic]

XRD, chemical analysis

< 1400°C, Fe3O4-Mn3O4 solid solutions under air atmosphere

[1970Aub]

XRD, chemical analysis

< 1000°C, (Fe,Mn)1–xO solid solutions under H2-H2O atmospheres

[1970Bul]

XRD, chemical analysis

969–1000°C, (Fe1–yMny)O (0.2 < y < 0.5) under H2-H2O atmospheres

[1970Nis]

Oxygen distribution between solid and liquid alloys

1534–1600°C, < 1.6 mass% Mn, < 0.2 mass% O

[1970Roe]

XRD, thermogravimetry

1000–1400°C, spinel-corundum equilibrium, 1 to100 kPa O2

[1971Bra]

XRD, crystal parameters, thermal expansion, conductivity

< 1400°C, (Fe1–yMny)3O4, cubic-tetragonal transition

[1971Ono]

Thermogravimetry

800–1300°C, Fe-(Fe,Mn)O-(Fe,Mn)3O4-(Fe, Mn)2O3 equilibria

[1973Hol]

XRD, cubic-tetragonal equilibrium

940°C, (Fe1–yMny)3(1–x)O4,

[1974Tan]

XRD, crystal parameters vs oxygen pressure

1200–1350°C, (Fe1–yMny)3(1–x)O4, 0.27 < y < 0.32, 1 Pa to 100 kPa O2

[1975Duq]

XRD, thermogravimetry, electrical conductivity

1000°C, 0 to 100 mass% Mn, 10–18 < pO2 / bar < 1

[1976Jan]

EMF from ZrO2(CaO) coated with ThO2(Y2O3) cell

1600°C, < 20 mass% Mn, < 0.2 mass% O

[1977Oet]

Thermal analysis, equilibrium measurements

1370–1875°C, CO-CO2 atmospheres, equilibrium alloy-manganowüstite

[1979Kop]

XRD, EMF and solubility measurements

1600°C, < 10 mass% Mn, < 0.2mass% O

[1981Ave]

Oxygen analysis in alloys under H2-H2O (< 40 % H2O)

1600–1700°C, < 9 mass% Mn, < 0.2 mass% O,

[1981Mik]

Chemical analysis, solubility measurements

1525–1600°C, < 10 mass% Mn, < 0.2 mass% O, 0.1 MPa O2

[1981Nai]

Calorimetry, Curie temperature measurements

200–740 K, (Fe1–yMny)3O4 (y = 0.33, 0.50, 0.67)

[1983Ter]

Thermogravimetry, EMF with stabilized ZrO2 as solid electrolyte

880–1000°C, (Fe1–yMny)3O4 under CO2-H2 atmospheres

[1983Tsu]

Thermogravimetry, electrical conductivity

950–1120°C, Fe/Mn = 2, O2 pressure between 0.1 Pa and 0.1 MPa

[1984Pun]

Thermogravimetry

700°C, (Fe,Mn)3O4-(Fe,Mn)2O3 tie lines under CO2-H2 atmospheres (continued)

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7

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1987She]

Chemical analysis, solubility measurements

1600°C, < 87 mass% Mn, < 0.2 mass% O, 0.1 MPa O2

[1990Fra]

Thermogravimetry

1000°C, (Fe1–yMny)1–xO under CO-CO2 atmospheres

[1991Ban]

Chemical analysis, metal-slag equilibria

1450–1500°C, < 20 mass% MnO, H2-H2O atmospheres

[1992Sub, 1993Sub]

Thermogravimetry, electrical conductivity

1000–1200°C, (Fe1–yMny)1–xO under COCO2 or N2-O2 atmospheres

[1995All]

XRD, lattice parameters measurements

25°C, β(Fe1–xMnx)Fe2O4 spinel solid solution (0 < x < 1)

[1995Bat]

XRD, electrical conductivity, Mössbauer

(Fe1–yMny)3O4 prepared by coprecipitation (0.35 < y < 1)

[1996Gol, 1997Pet]

High temperature XRD

600–1400°C, sintered Fe2O3-Mn2O3 samples, then annealed or quenched

[1998Bon]

XRD, Mössbauer, saturation magnetization, coulometry

400–900°C, (MnFe2)1–xO4, 10-20 < pO2 / bar < 0.21

[2000Tak, 2002Hin]

ERD, IR spectroscopy analysis, solubility measurements

1550–1650°C, < 24 mass% Mn, < 0.2 mass% O

[2005Zin]

XRD, chemical analysis

1000°C, manganowüstite-spinel equilibrium under H2-H2O

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) 1538 – 1394

cI2 Im 3m W

a = 293.15

at 1390°C [V-C2, Mas2]. Dissolves 10 at.% Mn at 1474.5°C [2004Wit]

(δMn) 1246 – 1138

cI2 Im 3m W

a = 308.0

[Mas2]. Dissolves 12.2 at.% Fe at 1236.6°C [2004Wit]

(αFe) (Ferrite) < 912

cI2 Im 3m W

a = 286.65

pure Fe at 25°C [Mas2, V-C2]. Dissolves 5 at.% Mn at 527°C [2004Wit]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, > 13 GPa [Mas2]

(continued)

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8

Fe–Mn–O

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

γ(Fe,Mn)

cF4 Fm 3m Cu

(γFe) (Austenite) 1394–912 (γMn) 1138–1087

Lattice Parameters [pm]

Comments/References

a = 364.67

at 915°C [V-C2, Mas2]

a = 386.0

[Mas2]

(βMn) 1087–707

cP20 P4132 βMn

a = 631.52

[Mas2]

(αMn) < 707

cI58 I 43m (αMn)

a = 891.26

pure Mn at 25°C [Mas2]

(Fe,Mn)O (Manganowüstite)

cF8 Fm 3m NaCl

Fe1–xO (Wüstite) 1422–569 MnO < 1850 Fe3O4 (r) < 580

oP56 Pbcm Fe3O4 I

β(Fe,Mn)3O4

cF56 Fd 3m MgAl2O4 Inverse spinel

βFe3O4 (h) (Magnetite) 1597–580 β(Fe1–xMnx)Fe2O4

βMnFe2O4 βMn3O4 1680–1171

Disordered spinel

Normal spinel Normal spinel

actually (Fe,Mn)1-xO with x < 0.12 a = 431.0 a = 429.3 a = 444.5

x = 0.05 x = 0.12 [2007Fen]. Actually Mn1–xO (x < 0.1 at 1200°C [1993Sub]

a = 1186.8 b = 1185.1 c = 1675.2

[V-C2]

spinel solid solution

a = 854.5 a = 839.6

at 1000°C [2007Fen] at 25°C [1995All]

a a a a a a

x = 0.2 [1995All] x = 0.4 [1995All] x = 0.6 [1995All] x = 0.8 [1995All] x = 1 [1995All] at 1200°C [2007Fen]

= = = = = =

841.9 844.6 847.0 849.5 850.2 862.6

(continued)

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Fe–Mn–O

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

αMn(Fe1–yMny)2O4

tI28 I41/amd αMn3O4 (Hausmannite)

αMn3O4 (r) < 1171 MnFe2O4–δ

-

(Fe,Mn)2O3

hR30 R 3c αAl2O3 (Corundum)

αFe2O3 (Hematite) < 1451 αMn2O3 < 2330 β(Fe,Mn)2O3 βFe2O3

γFe2O3 (Maghemite) γMn2O3

Comments/References

distorted spinel with c/a > 1 (y > 0.475) [1995Bat] a = c = 854.1 a = 824.3 c = 918.4 a = 815.5 c = 948.4

y = 0.475 [1995Bat] y = 0.710 [1995Bat]

a = 919.03 c = 893.96

distorted spinel with c/a < 1 [2001Hu]

y = 1 [1995Bat]

sesquioxide solid solution

a = 503.42 ± 0.03 c = 1374.83 ± 0.04

dissolves 10 mol% Mn2O3 at 1000°C metastable phase

cI80 Ia 3 βMn2O3 (Bixbyite)

βFeMnO3 βMn2O3 (Bixbyite) γ(Fe,Mn)2O3

Lattice Parameters [pm]

9

cF56 Fd3m MgAl2O4

a = 939.3 ± 0.2

[V-C2]

a = 940.7 a = 940.8

[2000Sei] stable dissolves up to 70 mol% Fe2O3 at 1000°C [1969Wic] metastable phase [1989Rag]

a = 834

[1989Rag] maghemite tetrahedrally distorted [1990Pat]

αMnO2 (Pyrolusite)

tP6 P42/mnm TiO2

a = 439.83 c = 287.30

[1989Rag]. Many polymorphs are known

βMnO2 (Cryptomelane)

tI24 I4/m -

a = 981.5 b = 284.7

[1989Rag] diaspore like structure

γMnO2 (Ramsdellite)

oP12 Pnma -

a = 927.0 b = 286.6 c = 453.3

[1989Rag] disordered diaspore like structure

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10 Table 3.

Fe–Mn–O Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mol of atoms [J, mol, K]

Comments

MnO + Fe2O3 ⇌ MnFe2O4

25 25 25–900

ΔrH° = – 16 300 ΔrS° = 5.02 ΔrCp = – 30.0 + 0.0269 T + 1.56·106 T –2

[1979Sek]

1/2 O2 ⇌ {O} dissolved in (Fe1–yMny)3O4

1200–1350

ΔrH° = – 314000 (for y = 0.27) ΔrH° = – 331000 (for y = 0.30) ΔrH° = – 308000 (for y = 0.33)

[1974Tan]

MnO ⇌ {Mn} + {O} dissolved in liquid Fe

Table 4.

1500–1800

[2005Zin]

ΔrG° = 245250 – 108.74 T Standard state: 1 mass% in liquid Fe

[2003Per]

Thermodynamic Properties of Single Phases

Phase

Temperature Range [°C]

Property, per mole of atoms [J, mol, K]

Comments

(1/7)(MnFe2O4)

27 467

Cp = 23.49 Cp = 27.61

[1981Nai]

(1/7)(Mn1.5Fe1.5O4)

27 467

Cp = 23.29 Cp = 27.56

[1981Nai]

(1/7)(Mn2FeO4)

27 467

Cp = 23.57 Cp = 27.50

[1981Nai]

Table 5.

Investigations of the Fe-Mn-O Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1953Gal]

Magnetic moment measurement

25°C, Fe3O4-Mn2FeO4 solid solution

[1967Mar]

Magnetic hysteresis curves

< 400°C, Mn0.2Fe2.8O4

[1967Sch2]

Chemical analysis

Determination of Mn2+ and Mn3+ in manganese ferrites

[1969Baf]

XRD, neutron diffraction

Distribution of Mn2+ and Mn3+ ions in the spinel structure

[1972Rez]

Electrical conductivity vs time

MnFe2O4 sintered at 1250°C

[1978Sid]

XRD, SEM (Scanning Electron Microscopy)

Segregation of Mn in (Fe,Mn)Fe2O4 (< 1 at.% Mn)

[1984Gil]

IR spectrometry

Order-disorder transition in γFe2O3 substituted by MnO

[1985Tay]

XRD, dilatometry

–182–480°C (91–753 K), MnFe2O4, thermal expansion (continued)

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Reference

Method/Experimental Technique

Type of Property

[1986Maz]

XRD, electrical conductivity, Curie point

25–400°C, MnFe2O4, inﬂuence of the preparation conditions

[1988Yoo]

Conductivity, thermoelectric power measurements

1000–1200°C, (Mn0.482Fe0.518)Fe2O4, 10-14 < pO2 / bar < 1

[1990Pat]

XRD, IR spectroscopy

< 1000°C, γ(Fe1–yMny)2O3 (y > 0.45), preparation and decomposition

[1995Sub]

SEM, Chemical Analysis

Preparation of metal (Fe) ceramic (Fe1–yMny)O structures

[2000Sei]

XRD, SEM, magnetic moment, Curie temperature, Mössbauer

MnFeO3 prepared by mechanical alloying

[2001Der]

XRD, DTA

< 1100°C, MnCO3 + Fe2O3 (+LiNO3 as dopant), synthesis of MnFe2O4

[2001Hu]

XRD, thermal magnetic analysis, magnetoresistance

1200°C, MnO2 + Fe2O3 → new tetragonal ferrite MnFe2O4–δ

[2001Mur]

XRD, TEM, spontaneous magnetization, coercitivity

MnFe2O4 from displacement reaction activated by high energy ball milling

[2002Sar]

XRD, EDX, TEM, electron diffraction, magnetization

Colloids (Fe,Mn)3O4 precipitated in aqueous medium (pH > 12)

[2004Med]

XRD, Mössbauer, magnetization

(Fe1–yMny)2O3 (0.3 < y < 0.9) and {(1-y) Fe+yMn2O3} ball milled

[2004Umi]

Metallography, hardness

< 1.5 mass% Mn, machinability investigations

[2005Pad]

XRD, X-ray ﬂuorescence analysis

MnO + Fe2O3 ball milled, preparation of MnFe2O4 nanocrystalline

[2006Swa]

High Resolution TEM,

MnFe2O4 nanocrystals synthesized by radiofrequency plasma torch

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12

Fig. 1. Fe-Mn-O.

Fe–Mn–O

Crystal parameter of the manganowüstite (Fe1–yMny)1–xO

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Fig. 2. Fe-Mn-O.

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Crystal parameters of the solid solutions α(Fe,Mn)3O4 (Hausmannite) and β(Fe,Mn)3O4 (Spinel)

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Fig. 3. Fe-Mn-O.

Fe–Mn–O

The Fe2O3-Mn2O3 quasibinary system under air atmosphere

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Fig. 4. Fe-Mn-O. The FeO-MnO quasibinary system in equilibrium with a metallic phase. L1: liquid metal, L2: liquid oxide, MW: manganowüstite

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16

Fig. 5. Fe-Mn-O. mass%)

Fe–Mn–O

Oxygen solubility in liquid (Fe,Mn) alloys under 0.1 MPa of oxygen pressure (solubility in

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Fig. 6. Fe-Mn-O.

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Isothermal section at 1600°C showing, in the L2 domain, the isobaric curve 0.1 MPa O2

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Fig. 7. Fe-Mn-O.

Fe–Mn–O

Isothermal section at 1300°C

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Fig. 8. Fe-Mn-O.

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Oxygen pressure for the equilibrium Spinel (Sp) – Manganowüstite (MW) at 1300 and 1150°

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Fig. 9. Fe-Mn-O.

Fe–Mn–O

Oxygen pressure for the equilibrium Spinel (Sp) – Manganowüstite (MW) at 987 and 700°C

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Fig. 10. Fe-Mn-O.

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The manganowüstite (MW) ﬁeld at 1150°C with isobaric curves given in log10 (pO2 / bar)

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22 References [1929Sch]

[1930Ben] [1937Wen] [1943Whi] [1945Dar]

[1946Dar]

[1946Pet]

[1950Gur]

[1950Hil]

[1953Gal]

[1958Hoo] [1962Mua] [1964Lev] [1965Tre]

[1966Sch]

[1967Buz]

[1967Mar] [1967Sch1]

[1967Sch2]

Fe–Mn–O

Schenck, R., Franz, H., Willeke, H., “Investigations of Equilibrium of the Reduction, Oxidation and Carbonization Processes of Iron” (in German), Z. Anorg. Allg. Chem., 184, 1–38 (1929) (Experimental, Phase Relations, 7) Benedicks, C., Loefquist, H., “The Binary System Mn-O”, Non-Metallic Inclusions in Iron and Steel., 72–73 (1930) (Experimental, Morphology, Phase Diagram, Phase Relations, 2) Wentrup, H., “The Phase Diagram of Sulﬁde Inclusions in Steel” (in German), Techn. Mitt. Krupp, 5, 131–152 (1937) (Morphology, Phase Diagram, Experimental, Phase Relations, 27) White, J., “The Physical Chemistry of Open-Hearth Slags”, J. Iron Steel Inst., London, 148, 579–694 (1943) (Phase Diagram, Phase Relations, Review, 195) Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. I. The Wuestite Field and Related Equilibria”, J. Am. Chem. Soc., 67, 1398–1412 (1945) (Experimental, Phase Diagram, Thermodyn., *, 26) Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. II. Equilibria and Thermodynamics of Liquid Oxides and Other Phases”, J. Am. Chem. Soc., 68, 798–816 (1946) (Experimental, Phase Diagram, Thermodyn., *, 24) Pettersson, H., “Investigations of the Solubility in the Solid State in the Binary Systems of the Oxides CaO, MnO, MgO and FeO” (in Swedish), Jernkontorets Ann., 130(12), 653–663 (1946) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 19) Gurry, R.W., Darken, L.S., “The Composition of CaO-FeO-Fe2O3 and MnO-FeO-Fe2O3 Melts at Several Oxygen Pressures in the Vicinity of 1600°C”, J. Am. Chem. Soc., 72, 3906–3910 (1950) (Experimental, Phase Relations, Phase Diagrams, 10) Hilty, D.C., Crafts, W., “Solubility of Oxygen in Liquid Iron Containing Silicon and Manganese”, Trans. Am. Inst. Min. Metall. Eng., 188, 425–436 (1950) (Phase Relations, Experimental, 18) Gal’perin, F., “Magnetic Moments and the Crystal Structure of Ferromagnetic Metals and Alloys” (in Russian), Dokl. Akad. Nauk SSSR, 88, 643–644 (1953) (Crys. Structure, Magn. Prop., Experimental, 11) Van Hook, H.J., Keith, M.L., “The System Fe3O4-Mn3O4”, Am. Mineral., 43, 69–83 (1958) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 20) Muan, A., Somiya, S., “The System Iron Oxide - Manganese Oxide in Air”, Amer. J. Sci., 260, 230–240 (1962) (Experimental, Phase Diagram, Phase Relations, 16) Levin, E.M., Robbins, C.R., McMurdie, H.F., Phase Diagrams for Ceramists, Am. Ceram. Soc., Columbus, Ohio, 1, Fig. 70–74 (1964) (Phase Diagram, Phase Relations, Review, 2) Tret`yakov, Yu.D., Saksonov, Yu.G., Gordeev, I.V., “Phase Diagram of the System Fe3O4Mn3O4-MnO-FeO at 1000°C and Thermodynamic Properties of the Coexisting Phases”, Inorg. Mater., 1(3), 382–386 (1965) (Crys. Structure, Thermodyn., Experimental, Phase Diagram, 10) Schenck, H., Steinmetz, E., “Activity, Standard Condition and Coefﬁcient of Activity” (in German), Stahleisen-Sonderberichte, Duesseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Thermodyn., Review, 161) Buzek, Z., Schindlerova, V., Macoszek, M., “The Inﬂuence of Cr, Mn, V, Si, Ti, Al, Zr, Ce and Ca on the Activity and Solubility of Oxygen in Liquid Iron” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 13(2–3), 175–193 (1967) (Thermodyn., Review, Phase Relations, 26) Marais, A., Porte, M., “Special Barkhausen Jumps in Ferrites” (in French), Compt. Rend. Acad. Sci. Paris, Ser. A B, 265B(1), 12–15 (1967) (Magn. Prop., Experimental, 7) Schwerdtfeger, K., Muan, A., “Equilibria in the System Fe-Mn-O Involving (Fe, Mn)O and (Fe, Mn)3O4 Solid Solutions”, Trans. Met. Soc. AIME, 239, 1114–1119 (1967) (Phase Diagram, Phase Relations, Thermodyn., Experimental, 44) Schwerdtfeger, K., “Measurement of Oxygen Activity in Iron, Iron-Silicon, Manganese, and Iron-Manganese Melts Using Solid Electrolyte Galvanic Cells”, Trans. Nat. Res. Inst. Met. (Jpn.), 239, 1267–1281 (1967) (Electrochemistry, Experimental, Thermodyn., 30)

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–O [1967Sch2]

[1968Oki]

[1969Baf]

[1969Wic]

[1970Aub]

[1970Bul]

[1970Nis]

[1970Roe]

[1971Bra]

[1971Ono]

[1972Bal]

[1972Mat]

[1972Rez]

[1973Buz]

[1973Hol]

[1974Sig] [1974Tan]

Landolt-Börnstein New Series IV/11D4

23

Schnitt, G., Funke, A., “Remarks to the Chemical Analysis of Two Valence Iron and Three Valence Manganese in Manganese Containing Ferrites” (in German), Z. Anal. Chem., 230 (5), 338–344 (1967) (Electronic Structure, Experimental, Phase Relations, 6) Okinaka, H., Kosuge, K., Kachi, S., “Phase Diagram of (Fe, Mn)O at 1260K”, J. Japan. Soc. Powder Met., 8, 295–301 (1968) (Phase Diagram, Thermodyn., Experimental, Phase Relations, 21) Bafﬁer, N., Huber, M., “Determination of Distribution in a Four-cation Mixed Spinel by X-ray and Neutron Diffraction” (in French), Compt. Rend. Acad. Sci. Paris, Ser. C, 268(17), 1521–1524 (1969) (Crys. Structure, Experimental, 6) Wickhalm, D.G., “The Chemical Composition of Spinels in the System Fe3O4-Mn3O4”, J. Inorg. Nucl. Chem., 31, 313–320 (1969) (Crys. Structure, Phase Diagrams, Experimental, 12) Aubry, J., Berthet, A., Duchene, R., Etienne, H., Evrard, O., Jeannot, F., Gleitzer, C., Offroy, C., Perrot, P., “Stabilization of Iron Monoxide by Formation of Solid Solutions” (in French), Ann. Chim., 5, 299–308 (1970) (Experimental, Phase Diagram, Phase Relations, 45) Bulgakova, T.I., Rozanov, A.G., “Phase Equilibria in the Ferrite Region of the Mn-Fe-O System”, Russ. J. Phys. Chem., 44(3), 385–388 (1970), translated from Zh. Fiz. Khim., 44(3), 693–699, (1970) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 15) Nishikawa, K., Kusano, A., Ito, K., Sano, K., “The Effect of Alloying Elements on the Solubility of Oxygen in δ -Iron”, Trans. Iron Steel Inst. Jpn., 10, 83–88 (1970), translated from Tetsu to Hagane, 55, 1193–1198 (1969) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 17) Roethe, A., Roethe, K.-P., Jerschkewitz, H.-G., “Equilibrium Measurements in the Me3O4 Phase in the Fe-Mn-O Ternary System” (in German), Z. Anorg. Chem., 378(1), 1–13 (1970) (Experimental, Phase Relations, Phase Diagrams, Thermodyn., 21) Brabers, V.A.M., “Cation Migration, Cation Valencies and the Cubic-Tetragonal Transition in MnxFe3-xO4”, J. Phys. Chem. Solids, 32, 2181–2191 (1971) (Crys. Structure, Experimental, 40) Ono, K., Ueda, T., Ozaki, T., Ueda, Y., Yamaguchi, A., Moriyama, J., “Thermodynamic Study of the Fe-Mn-O System” (in Japanese), Nippon Kinzoku Gakkai-Si, 35(8), 757–763 (1971) (Experimental, Phase Diagrams, Phase Relations, Thermodyn., 27) Balesdent, D., Evrard, O., Gleitzer, C., “Extension of the Darken’s Method to Heterogeneous Systems for the Calculation of the Activities” (in French), Rev. Chim. Miner., 9(1), 233–244 (1972) (Thermodyn., Calculation, Review, 5) Mathew, P.M., Kapoor, M.L., Frohberg, M.G., “Thermodynamics of the Deoxidation of Fe by Mn” (in German), Arch. Eisenhuettenwes., 43(5), 389–396 (1972) (Calculation, Phase Relations, Thermodyn., 26) Rezlescu, N., Cuciureanu, E., Ioan, C., Luca, E., “Time Variation of the Electrical Conductivity in Spinel Ferrites”, Phys. Status Solidi A, 11(1), 351–359 (1972) (Electr. Prop., Kinetics, Experimental, 9) Buzek, Z., “Effect of Alloying Elements on the Solubility and Activity of Oxygen and Sulphur in Liquid Iron at 1600°C”, Int. Symp. Metall. Chem. - Appl. Ferrous Metall., Sheffield, July 1971, Iron and Steel Inst., London, 173–177 (1973) (Thermodyn., Phase Relations, Review, 8) Holba, P., Khilla, M.A., Krupicka, S., “On the Miscibility Gap of Spinels MnxFe3–xO4+y”, J. Phys. Chem. Solids, 34, 387–395 (1973) (Crys. Structure, Phase Diagram, Experimental, 18) Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 (1974) (Review, Thermodyn., 249) Tanaka, T., “Lattice Constant and Nonstoichiometric of Mn-Fe Ferrites”, Jpn. J. Appl. Phys., 13(8), 1235–1237 (1974) (Crys. Structure, Experimental, Thermodyn., 17)

MSIT®

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

24 [1975Duq]

[1976Jan]

[1977Oet]

[1978Sid]

[1979Kop]

[1979Pel]

[1979Sek]

[1980Bra] [1981Ave]

[1981Mik]

[1981Nai] [1983Dav]

[1983ONe]

[1983Ter]

[1983Tsu]

[1984Gil]

[1984Pun]

Fe–Mn–O Duquesnoy, A., Couzin, J., Gode, P., “Isothermal Representation of Ternary Phase Diagrams A-B-O. Study of the System Mn-Fe-O” (in French), Compt. Rend. Acad. Sci. Paris, 281C, 107–109 (1975) (Experimental, Phase Diagram, Phase Relations, 6) Janke, D., Fischer, W.A., “Equilibrium of Chromium and Manganese with Oxygen in Iron Melts at 1600°C” (in German), Arch. Eisenhuettenwes., 47(3), 147–151 (1976) (Experimental, Thermodyn., Phase Relations, 23) Oeters, F., Koch, K., Scheel, R., Noelle, U., “Investigation of the Equilibria in the System FeMn-O” (in German), Arch. Eisenhuettenwes., 48(9), 475–480 (1977) (Experimental, Phase Diagram, Phase Relations, 11) Sidhu, P.S., Gilkes, R.J., Posner, A.M., “The Synthesis and Some Properties of Co, Ni, Zn, Cu, Mn and Cd Substituted Magnetites”, J. Inorg. Nucl. Chem., 40, 429–435 (1978) (Crys. Structure, Morphology, Experimental, 39) Kopitsa, N.M., Vladimirov, L.P., “Interaction Between Manganese and Oxygen in Iron Melts with Different Carbon Contents”, Russ. J. Phys. Chem., 53(3), 337–339 (1979) translated from Zh. Fiz. Khim., 5(3), 596–599 (1979) (Experimental, Phase Relations, Thermodyn., 11) Pelton, A.D., Schmalzried, H., Sticher, J., “Thermodynamics of Mn3O4-Co3O4, Fe3O4Mn3O4, and Fe3O4-Co3O4 Spinels by Phase Diagram Analysis”, Ber. Bunsen-Ges. Phys. Chem., 83, 241–252 (1979) (Phase Diagram, Calculation, Thermodyn., Phase Relations, 29) Sekine, K., Yamaguchi, T., “Thermodynamics of Ferrite Systems” (in Japanese), Yogyo Kyokai Shi, 87(1009), 443–452 (1979) (Phase Diagram, Phase Relations, Thermodyn., Review, 60) Brandes, E.A., Flint, R.F., “Mn-Fe-O” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 115 (1980) (Phase Diagram, Phase Relations, Review, 4) Averbukh, S.M., Smirnov, L.A., “Equilibrium between Manganese and Oxygen in Molten Iron”, Steel USSR, (3), 123–126 (1981), translated from Izv. Vys. Ucheb. Zav., Chern. Metall., (3), 18–23 (1981) (Experimental, Phase Relations, Thermodyn, 15) Mikhailov, G.G., Tankleskaya, N.M., “A Procedure for Calculating the Diagram of Phase Equilibrium in the Fe-Mn-O System during Solidiﬁcation of Melts”, Steel USSR, (6), 313–315 (1981), translated from Izv. Vys. Ucheb. Zav., Chern. Metall., (6), 5–9 (1981) (Phase Relations, Review, 8) Naito, K., Inaba, H., Yagi, H., “Heat Capacity Measurements of MnxFe3–xO4”, J. Solid State Chem., 36, 28–35 (1981) (Experimental, Magn. Prop., Thermodyn., 45) Davies, P.K., Navrotsky, A., “Quantitive Correlations of Deviations from Ideality in Binary and Pseudobinary Solid Solutions”, J. Solid State Chem., 46, 1–22 (1983) (Review, Theory, 96) O’Neill, H.S.C., Navrotsky, A., “Simple Spinels: Crystallographic Parameters, Cation Radii, Lattice Energies, and Cation Distribution”, Am. Mineral., 68, 181–194 (1983) (Crys. Structure, Review, Theory, Thermodyn., 49) Terayama, K., Ikeda, M., Taniguchi, M., “Phase Equilibria in the Mn-Fe-O System in CO2-H2 Mixtures”, Trans. Jpn. Inst. Met., 24(7), 514–517 (1983) (Experimental, Phase Relations, Thermodyn., 14) Tsuji, T., Asakura, Y., Yamashita, T., Naito, K., “Phase Equilibria of the Mn-Fe-O System (Fe/Mn = 2)”, J. Solid State Chem., 50(3), 273–280 (1983) (Experimental, Phase Relations, Thermodyn., 11) Gillot, B., “Study by Infrared Absorption Spectra of the Factors Inﬂuencing the OrderDisorder Transformation in γ Vacancy Ferrites Obtained from the Oxidation of Ferrous Spinels” (in French), Mater. Chem. Phys., 10(4), 375–384 (1984) (Crys. Structure, Optical Prop., Experimental, 17) Punge-Witteler, B., “Phase Equilibria between Spinel and Wustite in the Iron-ManganeseOxygen System at 700°C at 1 bar” (in German), Z. Phys. Chem. (Munich), 142(2), 239–248 (1984) (Experimental, Crys. Structure, Phase Diagrams, Phase Relations, Thermodyn., 22)

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–O [1985Tay] [1986Maz]

[1987She]

[1988Lyk]

[1988Yoo]

[1989Rag]

[1990Fra]

[1990Pat]

[1991Ban]

[1991Mik]

[1991Sun] [1992Sub]

[1993Alc]

[1993Sub]

[1993Tur]

[1993Tyu]

[1993Wu]

Landolt-Börnstein New Series IV/11D4

25

Taylor, D., “Thermal Expansion Data. VI. Complex Oxides, AB2O4, the Spinels”, Br. Ceram. Trans. J., 84(4), 121–127 (1985) (Calculation, Crys. Structure, Review, 99) Mazen, S.A., Sabran, B.A., “Thermal Effect on Formation and Conduction Mechanism of MnFe2O4”, Thermochim. Acta, 105, 1–8 (1986) (Crys. Structure, Magn. Prop., Experimental, 13) Shevtsov, V.E., Merker, E.E., Luzgin, V.P., “Thermodynamics of Oxygen Solutions in IronManganese Melts” (in Russian), Izv. Vys. Ucheb. Zav., Chern. Metall., (7), 1–3 (1987) (Experimental, Phase Relations, Thermodyn., 8) Lykasov, A.A., Pavlovaskaya, M.S., “Thermodynamic Properties of Manganowustite”, Russ. J. Phys. Chem., 62(5), 602–605 (1988), translated from Zh. Fiz. Khim., 62(5), 1188–1193 (1988), (Experimental, Theory, Thermodyn., 6) Yoo, H.-I., Tuller, H.L., “In situ Phase Equilibria Determination of a Manganese Ferrite by Electrical Means”, J. Mater, Res., 3(3), 552–556 (1988) (Experimental, Phase Relations, Electr. Prop., Thermodyn., 16) Raghavan, V., “The Fe-Mn-O System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 5, 181–192 (1989) (Phase Diagram, Phase Relations, Crys. Structure, Review, 34) Franke, P., Dieckmann, R., “Termodynamics of Iron Manganese Mixed Oxides at High Temperatures”, J. Phys. Chem. Solids, 51(1), 49–57 (1990) (Phase Diagrams, Phase Relations, Thermodyn. Experimental, 51) Pattanayak, J., Sitakara Rao, V., Maiti, H.S., “Effect of Iron Concentration on the Thermal behaviour of γ-Mn2O3”, Thermochim. Acta, 160, 233–242 (1990) (Crys. Structure, Experimental, 15) Ban-ya, S., Hino, M., Yuge, N., Kikuchi, I., “Activity Measurement of the Constituents in FeO-MnO Slag Equilibrated with Iron” (in Japanese), Tetsu to Hagane, 77(9), 1419–1425 (1991) (Experimental, Thermodyn., 25) Mikhailov, G.G., Lopatko, N.N., “Phase Equilibria in Iron-Based Melts on Interaction of Oxygen with Manganese, Vanadium, and Chromium”, Russ. Metall., (2), 7–11 (1991), translated from Izv. Akad. Nauk SSSR, Met., (2), 11–15, (1991) (Phase Relations, Thermodyn., Review, 10) Sundman, B., “An Assessment of the Fe-O System”, J. Phase Equilib., 12(2), 127–140 (1991) (Phase Diagram, Thermodyn., Assessment, 53) Subramanian, R., Dieckmann, R., “Limits of the Thermodynamic Stability of Cobalt-IronManganese Mixed Oxides at 1200°C”, J. Am. Ceram. Soc., 75(1), 382–391 (1992) (Phase Relations, Thermodyn., 40) Alcock, C.B., “Thermodynamic and Transport Properties of Electroceramic Oxide Systems”, J. Alloys Compd., 197, 217–227 (1993) (Phys. Prop., Magn. Prop., Transport Phenomena, Review, 28) Subramanian, R., Dieckmann, R., “Nonstoichiometry and Thermodynamics of the Solid Solution (Fe, Mn)1–ΔO at 1200°C”, J. Phys. Chem. Solids, 54(9), 991–1000 (1993) (Experimental, Phase Relations, Thermodyn., 27) Turkdogan, E.T., “Synchronising Free Energy Data on Reactions in Liquid Fe-Mn-O and Solid Mn-S-O”, Ironmaking and Steelmaking, 20(6), 469–475 (1993) (Assessment, Thermodyn., 35) Tyurin, A.G., “Thermodynamics of Molecular and Ionic Solutions”, Russ. Metall., (2), 39–47 (1993), translated from Izv. Ross. Akad. Nauk, Met., (2), 48–56 (1993) (Theory, Thermodyn., 35) Wu, P., Eriksson, G., Pelton, A.D., “Critical Evaluation and Optimization of the Thermodynamic Properties and Phase Diagrams of the CaO-FeO, CaO-MgO, CaO-MnO, FeO-MgO, FeO-MnO, and MgO-MnO Systems”, J. Am. Ceram. Soc., 76(8), 2065–2075 (1993) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 73)

MSIT®

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

26 [1994Sub]

[1995All]

[1995Bat]

[1995Kow]

[1995Sub]

[1996Gol]

[1997Pet]

[1998Bon]

[1998Lee]

[2000Pol] [2000Sei]

[2000Tak]

[2001Der]

[2001Hu]

[2001Mur]

[2002Hin]

Fe–Mn–O Subramanian, R., Dieckmann, R., Eriksson, G., Pelton, A., “Model Calculations of Phase Stabilities of Oxide Solid Solutions in the Co-Fe-Mn-O System at 1200°C”, J. Phys. Chem. Solids, 55(5), 391–404 (1994) (Calculation, Thermodyn., Phase Diagram, Phase Relations, 56) Allen, G.C., Hallam, K.R., Jutson, J.A., “X-ray Diffraction Studies of Solid Solutions of Cr-, Mn-, Fe-, Co-, and Ni-containing Transition Metal Spinel Oxides”, Powder Diffr., 10(3), 214–220 (1995) (Crys. Structure, Experimental, 8) Battault, T., Legros, R., Rousset, A., “Structural and Electrical Properties of Iron Manganite Spinels in Relation with Cationic Distribution”, J. Eur. Ceram. Soc., 15, 1141–1147 (1995) (Crys. Structure, Electrical Prop., Electronic Structure, Experimental, 25) Kowalski, M., Spencer, P.J., “Thermodynamic Revaluation of the Cr-O, Fe-O and Ni-O Systems: Remodelling the Liquid, BCC and FCC Phases”, Calphad, 19(3), 229–243 (1995) (Assessment, Phase Diagram, Phase Relations, Thermodyn., Review, 47) Subramanian, R., Üstündag, E., Sass, S.L., Dieckmann, R., “Metal-Ceramic Microstructure Control in Partial Reduction Reactions in the Model System Fe-Mn-O by Doping”, Mater. Sci. Eng. A, A195, 51–63 (1995) (Experimental, Morphology, Phase Relations, Phase Diagram, Thermodyn., 33) Golikov, Yu.V., Petrova, S.A., Zakharov, R.G., Antonov, A.V., Balakirev, V.F., “Equilibrium and Unstable States of the Fe-Mn-O System in Air”, Russ. J. Inorg. Chem., 41(9), 1510–1513 (1996), translated from, Dokl. Ross. Akad. Nauk, 344(6), 770–772 (1995) (Experimental, Phase Relations, 19) Petrova, S.A., Golikov, Yu.V., Zakharov, R.G., Balakirev, V.F., “Heterogeneous Equilibria in the Fe-Mn-O System in Air”, Russ. J. Phys. Chem., 71(2), 184–186 (1997), translated from Zh. Fiz. Khim., 71(2), 240–242 (1997) (Experimental, Phase Relations, Thermodyn., 10) Bonsdorf, G., Schafer, K., Teske, K., Langbein, H., Ullmann, H., “Stability Region and Oxygen Stoichiometry of Manganese Ferrite”, Solid State Ionics, 110, 73–82 (1998) (Electronic Structure, Experimental, Phase Diagram, Phase Relations, 19) Lee, B.-J., “Thermodynamic Calculation for Stability of Oxides in Steel Systems” (in Korean), J. Korean Inst. Met., 36(2), 217–224 (1998) (Calculation, Thermodyn., Phase Relations, 57) Pollert, E., “Inﬂuence of Mn3+ Ions on Ordering in Magnetic Oxides”, Int. J. Inorg. Mater., 2, 661–670 (2000) (Crys. Structure, Theory, Review, 18) Seifu, D., Kebede, A., Oliver, F.W., Hoffman, E., Hammond, E., Wynter, C., Aning, A., Takacs, L., Siu, I.-L., Walker, J.C., Tessema, G., Seehra, M.S., “Evidence of Ferrimagnetic Ordering in FeMnO3 Produced by Mechanical Alloying”, J. Magn. Magn. Mater., 212, 178–182 (2000) (Crys. Structure, Experimental, Magn. Prop., Morphology, Nano, 13) Takahashi, K., Hino, M., “Equilibrium between Dissolved Mn and O in Molten High-Manganese Steel”, High Temp. Mater. Proc., 19(1), 1–10 (2000) (Experimental, Phase Relations, Thermodyn., 28) Deraz, N.A.M., El-Shobaky, G.A., “Solid-Solid Interaction Between Ferric Oxide and Manganese Carbonate as Inﬂuenced by Lithium Oxide Doping”, Thermochim. Acta, 375, 137–145 (2001) (Crys. Structure, Experimental, Transport Phenomena, 37) Hu, J., Qin, H., Wang, Y., Zhang, S., Wang, Z., “Magnetic Properties and Magneto-Transport in MnFe2O4–δ with Tetragonal Structure”, J. Mater. Sci. Lett., 20, 1531–1532 (2001) (Crys. Structure, Experimental, Magn. Prop., 5) Muroi, M., Street, R., McCormick, P.G., Amighian, J., “Magnetic Properties of Ultraﬁne MnFe2O4 Powders Prepared by Mechanochemical Processing”, Phys. Rev. B, 63(18), 184414_1–7 (2001) (Crys. Structure, Experimental, Magn. Prop., 28) Hino, M., Takahashi, K., Itoh, T., Kikuchi, I., Nagasaka, T., “Equilibrium Between Liquid Iron and FeO-containing Solid Solution”, Scand. J. Metall., 31(3), 169–177 (2002) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 64)

DOI: 10.1007/978-3-540-78644-3_18 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–O [2002Sar]

[2003Mue] [2003Per] [2004Jun]

[2004Med]

[2004Umi]

[2004Wit]

[2005Pad]

[2005Zin]

[2006Swa]

[2007Fen]

[2007Wit] [Mas2] [V-C2]

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Saravanan, P., Alam, S., Kandpal, L.D., Mathur, G.N., “Effect of Substitution of Mn Ion on Magnetic Properties of Fe3O4 Nanocrystallites”, J. Mater. Sci. Lett., 21(14), 1135–1137 (2002) (Crys. Structure, Experimental, Morphology, Magn. Prop., 15) Mueller-Buschbaum, H., “The Crystal Chemistry of AM2O4 Oxometallates”, J. Alloys Compd., 349(1–2), 49–104 (2003) (Crys. Structure, Electronic Structure, Review, 476) Perrot, P., Foct, J., “Gases other than Hydrogen in Iron and Steels” (in French), Techniques de l’Ingenieur, M4275, 1–23 (2003) (Thermodyn., Kinetics, Phase Relations, Review, 127) Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in Steel”, Metall. Mater. Trans. B, 35B(3), 493–507 (2004) (Theory, Thermodyn., Review, 100) de Medeiros, S.N., Luciano, A., Cotica, L.F., Santos, I.A., Paesano, A.Jr., da Cunha, J.B.M., “Structural and Magnetic Characterization of the Ball-Milled αFe2O3-Mn2O3 and αFeMn2O3 Systems”, J. Magn. Magn. Mater., 281, 227–233 (2004) (Crys. Structure, Electronic Structure, Magn. Prop., Experimental, 15) Umino, M., Sera, T., Ikenaga, Y., Okada, Y., Murakami, R., Tubakino, S., “Role of Alloying Elements on Machinability of Plastic-molding Steels”, Z. Metallkd., 95(2), 109–114 (2004) (Mechan. Prop., Morphology, Experimental, 13) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Calculation, Thermodyn., #, 34) Padella, F., Alvani, C., La Barbera, A., Ennas, G., Liberatore, R., Varsano, F., “Mechanosynthesis and Process Characterization of Nanostructured Manganese Ferrite”, Mater. Chem. Phys., 90(1), 172–177 (2005) (Morphology, Nano, Experimental, Phase Relations, 27) Zinovik, E.V., Zinovik, M.A., “Hydrogen Reduction of Cu-Mn-Fe-O Spinel Solid Solutions”, Inorg. Mater., 41(3), 272–278 (2005), translated from Neorg. Mater., 41(3), 332–338, (2005) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, Thermodyn., 14) Swaminathan, R., Willard, M.A., McHenry, M.E., “Experimental Observations and Nucleation and Growth Theory of Polyhedral Magnetic Ferrite Nanoparticles Synthesized using an RF Plasma Torch”, Acta Mater., 54(3), 807–816 (2006) (Experimental, Morphology, Nano, Phase Relations, Theory, 37) Fenstad, J., Perrot, P., “Mn-O (Manganese-Oxygen)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published, (2007) (Crys. Structure, Thermodyn., Phase Diagram, Phase Relations, Review, #, 87) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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1

Iron – Manganese – Phosphorus Kostyantyn Korniyenko

Introduction Phase relationships in the Fe-Mn-P system are of great interest, in the ﬁrst instance because of the importance of manganese as an alloying element in steels. Another important aspect is related to the use of phosphorus as a glass-formation promoting element in the production of iron-based amorphous alloys. Recently, considerable research effort has been focused on nanocrystalline materials produced by controlled crystallization of amorphous alloys, and Fe-Mn-P amorphous alloys are candidate materials for this application. However, current knowledge of the constitution of the Fe-Mn-P system is lacking. Experimental studies of phase equilibria were undertaken long ago [1952Vog]. The reaction scheme, liquidus surface projection and isothermal section at 20°C of the partial Mn-Mn2P-Fe2P-Fe system as well as a series of vertical sections were proposed. More recently, information on the solubility of manganese in iron at different temperatures was presented in [1965Kan2], and phase contents of as-cast alloys in [1993Vav, 1997Vav, 1999Vav]. In parallel with the studies of the ternary system, the constitution of the Fe-Mn binary system was revised and new crystal structures for the ternary solid solutions have been determined. Therefore, a reinvestigation of the Fe-Mn-P system using modern physico-chemical analysis techniques is necessary. Publications devoted to experimental study of the phase relations, crystal structures and thermodynamics are listed in Table 1 together with the techniques used. The ﬁrst studies of crystal structure of ternary alloys were focused on the phases present in alloys of compositions along the Mn3P-Fe3P and Mn2P-Fe2P sections, and were carried out by [1948Now]. The crystal structures of the unary, binary and ternary phases of the Fe-Mn-P system are given also in [1952Vog, 1969Fru, 1969Rog, 1973Mae, 1973Nag, 1973Suz, 1977Got, 1981Maa, 1986Fje, 2000Bro, 2003Bal, 2003Liu]. Data on thermodynamic properties, mainly on the activity of phosphorus in liquid iron with manganese additions, were obtained experimentally by [1969Sch, 1972Sha, 1980Kun, 1983Yam, 1984Ban, 1995Zai, 1996Zai, 1998Zai]. Reviews of the literature deal with information on phase equilibria in the Fe-Mn-P system [1965Kan1, 1965Kan2, 1980Bra, 1988Rag, 1999Vav], crystal structures [1948Now, 1988Rag, 1999Vav] and thermodynamics [1974Sig, 1984Ban]. A database of thermodynamic model parameters for liquid Fe-based alloys containing Mn and P was proposed by [1995Bou] and a model of mass action concentrations for the Fe-Mn-P melt was presented by [2000Zha]. Binary Systems The Fe-P boundary binary system is accepted from [2002Per] and the Fe-Mn system is accepted from the recent assessment by [2004Wit]. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). The Mn-P boundary system is fairly well determined and is accepted from [Mas2]. However, there is some uncertainty relating to the reactions involving (δMn), (γMn) and (βMn) with liquid at virtually pure Mn. According to [Mas2], there are two invariant reactions that seem to take place at the transformation temperatures between pure (δMn) and (γMn), and between pure (γMn) and (βMn), 1138 and 1100°C, respectively. According to the article from where these data are taken [1950Ber], these temperatures are 1143 and 1072°C. From the data points given on the phase diagram presented by [1950Ber], it would seem that these relate again to the transformation temperatures of pure Mn, and the differences between these values and the accepted values being to due a reassessment of pure Mn. Therefore, it is not possible to be able to determine the nature of these binary invariants from these data, and they are thus classed as degenerate. Solid Phases Crystallographic data for the known unary, binary and ternary phases of the Fe-Mn-P system are listed in Table 2. Information concerning the phase relationships is incomplete; only one report of the joint solubility Landolt-Börnstein New Series IV/11D4

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of two of the components in the third has been presented (related to the (αFe)-based solid solution) [1965Kan2]. However, the isomorphous Mn2P- and Fe2P-based phases (Fe2P-type structure) have been found to form a continuous series of solid solutions (M2P) at high temperatures [1948Now, 1952Vog]. At lower temperatures in the (Mn1–yFey)2P composition range, a ternary phase (labeled as τ1) with an orthorhombic structure appears at compositions of 0.38 ≤ x ≤ 0.69 in alloys annealed at 850–900°C [1969Fru, 1969Rog]. The lattice parameters presented for this phase in Table 2 have been estimated from the ﬁgures given in the original publications. In the same work, it was also reported that the orthorhombic τ1 and hexagonal M2P phases are separated by very narrow two-phase regions. The stoichiometry of the τ1 phase centers around MnFeP (x = 0.5) and has the Co2Si structure prototype. The τ1 phase was also obtained by [1973Nag] but in somewhat different temperature and composition ranges (Table 2). Later, the crystal structures of the M2P and the τ1 phases were investigated in more detail by [1973Mae, 1973Suz, 1981Maa, 1991Sjo]. In particular, the ﬁrst band structure calculations of the MnFeP compound indicated that the crystallographic position, rather than the type of metallic atom that occupies each position, determines the electronic and magnetic properties. The Mn3P and Fe3P phases are isomorphous (Ni3P structure type) but they have not been reported as forming a continuous series of solid solutions. At the same time, the solubility of the third component in both phases is quite large. A number of diverse solubility values have been presented [1977Got, 2000Bro, 2003Liu] but they probably correspond to different temperatures. Lattice parameters of the Mn3P- and Fe3P-based solid solutions are presented in Table 2 and have been estimated from ﬁgures given in [1977Got]. Included in the same work is evidence of another ternary phase that occurs at a composition lying between the Mn3P- and Fe3P-based solid solutions. However, according to [1988Rag], an ordered orthorhombic phase lying in this section cannot be considered as a true ternary phase. But in the present evaluation this phase is accepted (denoted as τ2, (Mn1–yFey)3P, (Table 2)) because its structure differs from that of other unary and binary phases participating in the phase equilibria in the Fe-Mn-P system. More work on the temperature and composition ranges and crystal structures are needed for conﬁrmation. The crystal structures of the FeP and MnP phases belong to the same MnP type structure type. The crystal structure of the FeP phase was studied by [1986Fje] with additions of manganese of only up to 10 at.%, but the existence of a continuous series of solid solutions between these two phases is possible. Further study of the complete MnP-FeP section is necessary. [1972Sel] determined that in pure FeP, the z-value of the position of the P atoms is 0.296, being considerably shifted from the value of 0.25 demanded by the mirror plane in the Pnma space group. Thus the mirror plane disappears and the space group transforms to the subgroup Pna21 with the same symmetry elements, except for this mirror plane. Mössbauer effect measurements and physico-chemical analysis revealed that annealing amorphous Fe-Mn-P alloys leads to the formation of a nanocrystalline structure [2003Bal]. However, information about phase equilibria in the Fe-Mn-P ternary system involving the stable binary Mn3P2 phase is absent. According to the data of [1965Kan2], the solubility of phosphorus in (αFe) decreases from 4.4 at.% (2.5 mass%) in the absence of manganese, to 3.0 at.% (1.6 mass%) at 4.0 at.% (3.8 mass%) Mn. With temperature decreasing from 1000 to 800°C, the solubility of P in (αFe) containing 1 at.% Mn decreases from 4.0 to 2.0 at.%. Quasibinary Systems [1948Now] reported the quasibinary character of the Mn2P-Fe2P section from their X-ray diffraction studies. The phase diagram of the Mn2P-Fe2P system was constructed by [1952Vog] on the basis of thermal and chemical analyses coupled with metallographic examination. The section is shown in Fig. 1 with amendment of the melting temperature of the Fe2P (1350°C in [1952Vog]) by 1370°C [Mas2]. Corresponding corrections to the liquidus curves were also carried out. Approximate phase boundaries of the τ1 phase were plotted using the data of [1969Fru, 1969Rog], which had been obtained from the study of alloys annealed at 850–900°C. The quasibinary character of the Mn2P-Fe2P section enables triangulation of the ternary Fe-Mn-P system along this line and to consider the phase equilibria in the Mn-Mn2P-Fe2P-Fe partial system independently of the more P rich part of the ternary system.

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Invariant Equilibria Table 3 presents the temperatures, types of reactions and the available compositions of the phases taking part in the invariant equilibria in the partial Mn-Mn2P-Fe2P-Fe system. The information, together with the partial reaction scheme shown in Fig. 2, are based mainly on the data of [1952Vog] who presented information on the invariant reactions and liquidus surface. Corrections have been made in accordance with the accepted boundary binary systems. As a consequence, because the accepted Fe-Mn system [Mas2] shows (γMn) and (γFe) forming a continuous series of solid solutions in contrast to the earlier version of the phase diagram accepted by [1952Vog], the number of four-phase invariant equilibria involving the liquid phase has decreased by one. The invariant reaction involving the liquid, γ, M2P and Fe3P phases given by [1952Vog] as of transition U type is in error. Reanalysis of their data indicates that this reaction should really be of the decomposition E type. In the review of [1988Rag], two additional solid state transition reactions were proposed to account for the ordering reaction in the Mn2P-Fe2P section, but this has not been conﬁrmed experimentally. Liquidus, Solidus and Solvus Surfaces Figure 3 shows the liquidus surface projection of the partial Mn-Mn2P-Fe2P-Fe system. It is based principally on the data of [1952Vog] (reproduced similarly in the review of [1980Bra]) with some modiﬁcations similar to those were carried out by [1988Rag]. Therefore, in comparison with the original source material, the peritectic reaction L + (γFe) ⇌ (γMn) does not take place as (γFe) and (γMn) form a continuous series of solid solutions, and therefore a common ﬁeld of primary crystallization exists on the liquidus surface. Other changes were made in accordance with the boundary binary systems and invariant equilibria (see “Binary Systems” and “Invariant Equilibria” sections). The crystallization path of rapidly quenched alloys of compositions Mn5.04Fe86.5P8.46, Mn4.80Fe83.2P12.0 and Mn9.8Fe81.6P8.6 (in at.%) was studied by [1993Vav], and the obtained results are in a good agreement with the accepted liquidus surface. Information on the liquid-solid equilibria in the Fe-Mn-P system is incomplete, especially with regard to the solidus and solvus surfaces and the liquidus surface in the P rich range of the diagram. Further experimental investigations of these aspects are necessary. Isothermal Sections An isothermal section of the Mn-Mn2P-Fe2P-Fe partial system at a temperature of 20°C was presented by [1952Vog], based on the results of their own experimental investigations. [1988Rag] attempted to revise this section for 25°C using later data regarding phase relations at room temperature of the boundary binary and ternary systems. A nominal width of about 1 at.% was assumed by [1988Rag] for the two-phase regions between the hexagonal (Mn2P and Fe2P) and the orthorhombic (τ1) phases on the Fe2P-Mn2P section. According to the variant of the Fe-Mn system accepted by [1952Vog], at 20°C the (γFe) solid solution region extends from about 29 to 61 at.% Mn, but according to the Fe-Mn phase diagram accepted by [1988Rag], this region was replaced by (γFe,γMn). The compilation of the data of [1952Vog] and [1988Rag] with corrections according to the accepted boundary binary systems is presented in Fig. 4. From the data of [2004Wit] concerning the Fe-Mn system it follows that at 25°C a wide two-phase region α + (αMn) stretches from the iron apex up to about 80 at.% Mn, at the same time the γ phase does not exist at this temperature in the binary system. Because in the ternary Fe-Mn-P system three-phase ﬁelds with the participation of the γ phase exist [1952Vog], we suppose that the γ phase is stabilized in the ternary system by phosphorus. Therefore the γ single-phase ﬁeld and the attendant three-phase ﬁeld α + γ + (αMn) are plotted in Fig. 4. [1965Kan1] studied phosphides isolated electrolytically from ternary Fe-P-M alloys containing 2.5 mass% P in order to clarify the phase relationships between the phosphide phases and the iron phase in these systems and also to determine the phosphide-forming tendency of alloying elements in steel. It was observed that manganese has a weak tendency to combine with phosphorus in steel, because no phosphide phases, except the Fe3P phase were found in the ternary Fe-Mn-P alloys. It was reported that at 800°C, on increasing the manganese concentration in steel from 1.80 to 4.87 mass%, its concentration in the Fe3P phase correspondingly increases from 5.7 to 13.3 mass%. Landolt-Börnstein New Series IV/11D4

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Phase contents of a number of different Fe-Mn-P alloys annealed at different temperatures were presented in [1997Vav, 1998Vav, 1999Vav]. In particular, in rapidly quenched and annealed (at 500°C for 10 minutes) alloys of the compositions (in at.%) Mn4.7Fe77.1P18.2 and Mn9.3Fe72.5P18.2, the presence of the α and (MnxFe1–x)3P phases, and the α, (MnxFe1–x)3P and M2P phases, respectively, was established. In [1998Vav], the same information was reproduced but a different value of annealing temperature (770 K or 497°C) was reported. Rapid quenching and annealing (400°C for 10 min) of these two alloys resulted in the presence of the α and (MnxFe1–x)3P phases as well as the paramagnetic γ phase [1997Vav]. Temperature – Composition Sections A series of temperature-composition sections has been constructed by [1952Vog] based on the results of their experimental investigations. The temperature-composition section at 95 mass% Fe and phosphorus contents up to 4 mass% (Mn5.08Fe94.92-Mn0.98Fe92.03P6.99 in at.%) is presented in Fig. 5, with corrections in accordance with the accepted Fe-Mn phase diagram (existence of the α + γ two-phase region at the room temperature). The temperature-composition section at 90 mass% Fe proposed by [1952Vog] is incorrect because the phosphorus content is in error (up to 21.5 mass%). Moreover, at the Fe-Mn system side it contradicts the binary system accepted by [1952Vog]. Also the temperature-composition sections at 50 and 10 mass% Fe and at 1 mass% P do not comply with the accepted Fe-Mn binary system. The temperature-composition sections at 12 and 6 mass% P (Mn80.52P19.48-Fe80.27P19.73 and Mn89.83P10.17-Fe89.68P10.32 in at.%, respectively) do not agree with the accepted invariant reaction U2. Thermodynamics The effect of manganese on the activity coefﬁcient of phosphorus in liquid iron alloys at different temperatures was investigated by [1969Sch, 1983Yam, 1984Ban] and also by [1972Sha, 1980Kun] (cited in [1995Zai]). It was concluded by [1969Sch] that the addition of Mn (up to 16 mol%) to liquid Fe-P alloys at 1550°C does not inﬂuence on the activity of phosphorus and therefore the interaction parameter εPMn = 0. Knudsen cell - mass spectrometry measurements carried out at 1600°C by [1983Yam] demonstrated that the vapor pressure of manganese in liquid iron was high. However, during the experiment, the inside wall of the ion source became severely contaminated by Mn vapor making accurate determinations impossible. Later, the vapor pressure of phosphorus in liquid Fe-Mn-P alloys with manganese contents of up to 19.3 mass% was measured by [1984Ban] by a transportation method at the lower temperature of 1400°C. The results were treated using the interstitial solution model of J. Chipman. The effect of manganese on the activity coefﬁcient of phosphorus in liquid iron was determined by assuming the manganese dissolves substitutionally. A value of εPMn = – 7.17 ± 1.16 at 1400°C was obtained for the interaction parameter. The set of experimental data obtained by [1984Ban] was optimized in [1995Bou], and satisfactory agreement between the calculated and experimental data was found. [1993Din] calculated the activity interaction parameter between Mn and P in liquid Fe at 1600°C. The value derived of εPMn = – 5.03 differs from the experimental value cited in [1988The] (– 7.2). [1972Sha] measured the activity of phosphorus in Fe-Mn-P melts containing 0.8 to 30.7 at.% P and 1.7 to 2.0 at.% Mn using the emf technique. The electrolyte used was a synthetic slag containing 41.18 at.% CaO, 39.87 at.% SiO2, 9.20 at.% Al2O3, 2.64 at.% B2O3 and 1.27 at.% P2O5. A melt containing 30.7 at.% P and 1.8 at.% Mn was used as the reference electrode. It was assumed that, in view of the low concentration of iron and manganese ions in the slag, the potential was controlled by phosphorus transfer between the alloy and the electrolyte. Based on consideration of Henry’s law, [1972Sha] concluded that in calculations for low-phosphorus alloys (0.8 at.% of P) the mole fraction of phosphorus can be used instead of its activity. In the determination of the activity of Mn at 1500°C, [1980Kun] used the same technique and an electrolyte with a similar composition: 40.85 at.% CaO, 43.26 at.% SiO2, 8.34 at.% Al2O3, 2.31 at.% B2O3 and 1.46 at.% MnO. Knudsen-cell mass-spectrometry was used by [1995Zai, 1996Zai, 1998Zai] to investigate the thermodynamic properties of liquid alloys in the temperature range from 1029 to 1428°C (1302 to 1701 K). The concentrations of iron, manganese and phosphorus of the alloys studied were in the ranges from 20.5 to 73.8, from 22 to 69.5 and from 15.2 to 36.5 at.%, respectively. The thermodynamic properties of the melts DOI: 10.1007/978-3-540-78644-3_19 # Springer 2008

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were approximated by application of the associated-solution model. For adequate representation of the experimental data it was necessary to take into account binary associates formed by iron and manganese atoms with phosphorus, the ternary associative complex FeMnP and excess terms describing the interactions between the monomer species. The thermodynamic characteristics of the binary associates were found to agree with the values established earlier from the experimental data for binary systems within the limits of experimental error. The obtained molar Gibbs free energies and enthalpies of formation from the liquid components at 1377°C are presented in Figs. 6 and 7, respectively, in the form of isovalue lines. These lines are asymmetric, and the extrema are displaced from the phosphorus corner towards the binary Fe-Mn side and from the Fe-P side towards the Mn-P side. The entropy is negative for most of the concentration triangle. It becomes positive only in the regions close to the corners of the triangle. [1974Sig] collected and assessed literature data on the thermodynamic behavior of dilute solute elements (including manganese and phosphorus) in liquid iron. A non-equilibrium thermodynamic model that describes the effect of solute grain boundary segregation on grain boundary cohesion was proposed by [1984Lee] for iron based ternary systems, in particular, for the Fe-Mn-P system. This model directly and simply predicts the effect of alloying elements on impurity-induced grain boundary embrittlement. According to the model, Mn enhances impurity-induced grain boundary embrittlement in a Fe ternary system. The equilibrium segregation of phosphorus at austenite grain boundaries in a Mn10Fe89P1 (mass%, in at.% – Mn10.07Fe88.15P1.78) alloy was modeled by [1989Paj]. The segregation was described using the Langmuir-McLean equation, and a value for the free energy of phosphorus segregation ΔGoP was estimated as 47 kJ·mol–1. The activation energy of crystallization of Mn4.7Fe77.1P18.2 and Mn9.8Fe72.5P18.2 (in at.%) amorphous alloys was estimated by [1999Vav, 2000Vav] using the Kissinger method, in terms of the variation in crystallization temperature (Tc) as a function of heating rate in the range 3.75 to 40°C·min–1. For these two alloys, the values of the activation energy obtained were 230 ± 6 and 137 ± 6.5 kJ·mol–1, respectively. Based on the phase diagrams and the coexistence theory of the structure of metallic melts involving compound formation, models for mass action concentrations for the Fe-Mn-P melt have been formulated in [2000Zha]. The calculated mass action concentrations agree well with the corresponding measured activities, and this in turn shows that the deduced model can reﬂect the structural characteristics of the melt concerned and that there is no phosphorus saturation of the melt. Notes on Materials Properties and Applications Fe-Mn-P and related alloys (complicated manganese-containing steels and ferromanganese alloys) ﬁnd wide practical applications in various ﬁelds of modern technology. Another important aspect of their use is related to the application of phosphorus as a glass forming element for the production of iron based amorphous alloys. However, the preparation of Fe-P master alloys involves a number of practical difﬁculties, and the addition of some transition metals, in particular manganese, can help in the preparation of alloys suitable for amorphization [1997Vav]. Material property investigations are listed in Table 4. On the whole, magnetic and mechanical properties have been studied in some detail. It has been observed that very small substitutions of manganese in Fe2P induce metamagnetism [1969Fru, 1969Rog]. The τ1 phase was reported to demonstrate antiferromagnetic properties with a Néel temperature of 320 K [1973Nag] or 340 K [1973Suz]. It was shown by [1993Vav, 1997Vav, 1998Vav, 1999Vav] that the embrittlement of iron based Fe-Mn-P alloys is governed by the amount of α phase precipitating during crystallization. The ﬁrst band structure calculations of the MnFeP compound were carried out by [1991Sjo]. It was found that the crystallographic position, rather than the type of metallic atoms that occupy these positions, determines the electronic and magnetic properties. Miscellaneous The lattice and grain boundary tracer diffusion coefﬁcients D*PL and P*P of phosphorus in the Mn0.38Fe99.45P0.17 and Mn2.11Fe97.78P0.11 (at.%) alloys were measured by [1983Mat]. There is a break in each of the D*PL – 1/T and P*P – 1/T lines at temperatures near and below the Curie temperature, respectively. It was considered that these anomalous breaks were caused by magnetic transformations taking place in the bulk and at grain boundaries. It was shown that alloying with manganese increased D*PL and P*P. Landolt-Börnstein New Series IV/11D4

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[1984Lee] studied the effect of manganese on phosphorus grain boundary segregation. Their experimental results showed that after aging for 300 hours, maximum P grain boundary segregation occurs at the aging temperature of 550°C. It was concluded that manganese possesses a much lower grain boundary segregation enrichment ratio than P. Equilibrium segregation of phosphorus at the grain boundaries of austenite was studied by [1989Paj] in a Mn10Fe89P1 (mass%, in at.% - Mn10.07Fe88.15P1.78) alloy equilibrated at temperatures between 750 and 1200°C before rapid quenching. It was shown that manganese increased the level of phosphorus segregation. It was suggested that the level of phosphorus segregation is enhanced by manganese because manganese intensiﬁes the additional segregation of phosphorus during quenching. It was established by [1993Vav, 1997Vav, 1998Vav, 1999Vav] that alloys of the Fe-Mn-P system have a tendency to amorphization at concentrations between 15.1 and 21.2 at.% P and between 4.7 and 9.3 at.% Mn at cooling rates of 105 to 106 K/sec. The viscosity of Mn4.7Fe77.1P18.2 and Mn9.3Fe72.5P18.2 (at.%) alloys after melt homogenization for 1 h at 1150–1200°C and for an additional 0.5 h at the set temperature was measured by [2000Vav].

Table 1.

Investigations of the Fe-Mn-P Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1948Now]

X-ray diffraction

Mn3P-Fe3P and Mn2P-Fe2P sections

[1952Vog]

Melting in Tamman furnace (sintered corundum crucibles), thermal analysis, optical microscopy, chemical analysis

≤ 1500°C, Mn-Mn2P-Fe2P-Fe partial system

[1965Kan1]

Electrolytical isolation, X-ray diffraction, chemical analysis

1000°C, 800°C, 2.5 mass% P in the alloys

[1965Kan2]

X-ray diffraction, chemical analysis

1100–700°C, ≤ 4 at.% P

[1969Fru]

X-ray diffraction (Seeman-Bohlin camera), Mössbauer spectroscopy

Mn2P-Fe2P section

[1969Rog]

X-ray diffraction (Seeman-Bohlin camera), Mössbauer spectroscopy

Mn2P-Fe2P section

[1969Sch]

Equilibrium P (vapor) – molten Fe with Mn additions

1550°C

[1972Sha]

Emf measurements in a liquid electrolyte

1550°C, 1.7 to 2.0 at.% Mn, 0.8 to 30.7 at.% P

[1973Mae]

X-ray powder diffraction, Mössbauer spectroscopy

900°C, MnFeP

[1973Nag]

X-ray powder diffraction (Debye-Scherrer technique)

Mn2P-Fe2P section

[1973Suz]

X-ray powder diffraction, neutron powder diffraction, Mössbauer spectroscopy

MnFeP

[1977Got]

X-ray powder diffraction

Mn3P-Fe3P section

[1980Kun]

Emf measurements in a liquid electrolyte

1500°C, 0.7 to 10.8 at.% Mn, 1.1 to 32.5 at.% P

[1981Maa]

X-ray powder diffraction, Mössbauer spectroscopy

Mn0.7Fe1.3P (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1983Yam]

Melting, Knudsen cell-mass spectrometry

1600°C

[1984Ban]

Transportation method

εPMn in liquid phase, 1400°C, ≤ 19.3 mass% Mn

[1986Fje]

X-ray powder diffraction, neutron diffraction

50 at.% P, 40 to 50 at.% Fe

[1993Vav]

Arc melting, quenching, X-ray diffraction, differential thermal analysis

8.46 to 21.2 at.% P, 4.60 to 9.80 at.% Mn

[1995Zai]

Knudsen effusion and cell-mass spectrometry, X-ray diffraction, chemical analysis

1428–1029°C, 20.5 to 73.8 at.% Fe, 2.2 to 69.5 at.% Mn, 15.2 to 36.5 at.% P

[1996Zai]

Arc melting, Knudsen effusion and cell-mass spectrometry

1428–1029°C, 20.5 to 73.8 at.% Fe, 2.2 to 69.5 at.% Mn, 15.2 to 36.5 at.% P

[1997Vav]

Arc melting, X-ray diffraction, thermal analysis, TEM, electron diffraction, Mössbauer spectroscopy

≤ 10 at.% Mn

[1998Vav]

Mössbauer spectroscopy, differential thermal analysis, X-ray diffraction

4.7 and 9.3 at.% Mn, 18.2 at.% P

[1998Zai]

Knudsen effusion and cell-mass spectrometry, X-ray diffraction, chemical analysis

1428–1029°C, 20.5 to 73.8 at.% Fe, 2.2 to 69.5 at.% Mn, 15.2 to 36.5 at.% P

[1999Vav]

Mössbauer spectroscopy, differential thermal analysis

4.7 and 9.3 at.% Mn, 18.2 at.% P

[2000Bro]

X-ray diffraction, neutron diffraction, Mössbauer spectroscopy

25 at.% P, 0 to 18.75 at.% Mn

[2003Bal]

Mössbauer spectroscopy, physico- chemical analysis techniques

Amorphous Fe-Mn-P alloys

[2003Liu]

X-ray powder diffraction, neutron powder diffraction, Mössbauer spectroscopy, chemical analysis

880°C, 25 at.% P

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αδFe)

cI2 Im 3m W

Lattice Parameters [pm]

Comments/References

dissolves 10 at.% Mn at 1473°C, 3 at.% Mn at ∼400°C [Mas2], dissolves 4.55 at.% P at 1048°C, 4 at.% P at 1000°C [2002Per] dissolves 3 at.% P at 4 at.% Mn, 1000°C [1965Kan2] (continued)

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8

Fe–Mn–P

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

(δFe) (h2) 1538–1394 (αFe) (r) (ferrite) < 912 γ, (Mn1–xFex)

Lattice Parameters [pm]

Comments/References

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2]

a = 386

0 ≤ x ≤ 1, dissolves 0.56 at.% P at x = 1 and 1150°C [Mas2] pure Mn, at > 1100°C [Mas2]

a = 364.67

pure Fe at 915°C

cF4 Fm 3m Cu

(γMn) 1138–1100 (γFe) (h1) (austenite) 1394–912

[Mas2]

(δMn) 1246–1138

cI2 Im 3m W

a = 308

pure Mn, at > 1138°C [Mas2] dissolves 9 at.% Fe at 1235°C [Mas2]

(βMn) 1100–727

cP20 P4132 βMn

a = 631.52

pure Mn, at > 727°C [Mas2] dissolves 29.88 at.% Fe at 700°C [Mas2]

(αMn) < 727

cI58 I 43m αMn

a = 891.26

pure Mn, at 25°C [Mas2] dissolves 29.7 at.% Fe at 700°C [Mas2]

(P) (red) < 417

c*66

a = 1131

sublimation at 1 bar. Stable form of P. Triple point at 576°C, > 36.3 bar; triple point at 589.6°C at 1 atm [Mas2, V-C2]

(P) (white) < 44.14

c** P (white)

a = 718

common form of P [Mas2, V-C2]

(P) (black)

oC8 Cmca P (black)

a = 331.36 b = 1047.8 c = 437.63

T = 25°C [Mas2, V-C2]

(continued)

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Fe–Mn–P

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

(MnxFe1–x)3P

tI32 I 4 Ni3P

Lattice Parameters [pm]

MnxFe1–xP

a = 913.10 c = 451.40 a = 910.46 c = 446.34 a = 910.8 c = 445.5 a = 910.81 c = 446.06 oP8 Pnma MnP

FeP < ∼ 1370

FeP2

FeP4

oP6 Pnnm FeS2 (marcasite) mP30 P21/c FeP4

Comments/References

0 ≤ x ≤ 0.3 [1977Got] a = 911.0 to 911.7 c = 446.77 to 450.0 a = 911.16 to 911.44 c = 446.77 to 449.70

Fe3P < 1166

9

a = 520.20 b = 310.82 c = 580.58 a = 519.81 b = 309.48 c = 580.10 a = 519.69 b = 309.41 c = 580.02 a = 520.92 b = 311.35 c = 581.73 a = 520.30 b = 310.60 c = 581.11 a = 519.1 b = 309.9 c = 579.2 a = 519.3 b = 579.3 c = 309.9 a = 497.29 b = 565.68 c = 272.30 a = 461.9 b = 1367.0 c = 700.2 β = 101.48°

at x = 0.1 to 0.3, after quenching from ∼ 1300°C [1977Got] at x = 0.05 to 0.25, in the alloys annealed at 950°C and slowly cooled [2000Bro] x = 0.15, 247°C [2000Bro] x = 0.15, 10 K [2000Bro] 25 at.% P at x = 0 [2002Per] after annealing at 950°C [2000Bro] 0 ≤ x ≤ 0.2 [1986Fje] x = 0.1, 20°C [1986Fje]

x = 0.1, 100 K [1986Fje]

x = 0.1, 10 K [1986Fje]

x = 0.2, 20°C [1986Fje]

x = 0.2, 10 K [1986Fje]

at x = 0 [P]

at x = 0 [2002Per], space group Pna21 66 to 67 at.% P [2002Per] at 66.7 at.% P [2002Per] 80 at.% P [2002Per] [2002Per]

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10

Fe–Mn–P

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

(Mn1–xFex)3P

tI32 I 4 Ni3P

Mn3P < 1105

Lattice Parameters [pm]

a = 918.0 to 915.4 c = 457.2 to 454.8 a = 917.12 to 913.91 c = 456.45 to 455.20 a = 918.1 c = 456.8 a = 918.26 c = 456.85

M2P, (Mn1–xFex)2P

Mn2P < 1327 a = 607.4 c = 345.4 a = 608.1 c = 346.0 a = 604.54 to 598.0 c = 346.2 to 347.5 Fe2P < 1370 a = 586.4 c = 346.0 a = 587.5 to 589.4 c = 346.3 to 346.9 -

MnP < 1147

oP8 Pnma MnP

0 ≤ x ≤ 0.33 [2003Liu] at x = 0.1 to 0.3, after quenching from ∼ 1300°C [1977Got] at x = 0.1 to 0.33, annealing at 880°C [2003Liu] 25 at.% P [V-C2]

[2003Liu] 0 ≤ x ≤ 1 at high temperature [1948Now, 1952Vog]

hP9 P 62m Fe2P

Mn3P2 1090 - 1002

Comments/References

-

0 ≤ x ≤ 0.38 after annealing at 850-900°C [1969Fru, 1969Rog] at x = 0 [P] at x = 0 after annealing at 850-900°C [1969Fru, 1969Rog] at x = 0.1 to 0.38 after annealing at 850-900°C [1969Fru, 1969Rog] 0.69 ≤ x ≤ 1 after an nealing at 850-900°C [1969Fru, 1969Rog] at x = 1 [2002Per] at x = 0.9 after annealing at 850-900°C [1969Fru, 1969Rog] 40 at.% P [Mas2]

a = 525 b = 317 c = 591.7

50 at.% P [Mas2] [1988Rag]

(continued)

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Fe–Mn–P

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

* τ1, (Mn1–yFey)2P

oP12 Pnma Co2Si

11

Lattice Parameters [pm]

Comments/References

0.38 ≤ y ≤ 0.69 (25.3 to 46 at.% Fe, 33.3 at.% P), annealing at 850–900°C [1969Fru, 1969Rog] 21.7 to 45 at.% Fe, 33.3 at.% P, heating at 1000∼1100°C for 48 h and slow cooling [1973Nag]

MnFeP

* τ2, (Mn1–yFey)3P

a = 595.3 b = 356.7 c = 673.9

at x = 0.5 (33.3 at.% Fe), annealing at 850-900°C [1969Fru, 1969Rog]

a = 596.6 to 590.0 b = 357.8 to 356.0 c = 676.5 to 670.0

at x = 0.38 to 0.69 (25.3 to 46 at.% Fe, 33.3 at.% P), annealing at 850-900°C [1969Fru, 1969Rog] 0.3 ≤ y ≤ 0.7, quenched from ∼ 1300°C [1977Got]. Existence needs further conﬁrmation

oI*

0.4 ≤ x ≤ 0.6 [1977Got]

a = 918 to 914.5 b = 858.3 to 855 c = 486.5 to 483

Table 3.

Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (at.%) Fe

Mn

P

L + α ⇌ γ + Fe3P

1025

U1

L

∼ 75.1

∼ 8.0

∼ 16.9

L + Fe3P ⇌ γ + M2P

1015

U2

L

∼ 65.0

∼ 18.2

∼ 16.8

L + (βMn) ⇌ γ + Mn3P

958

U3

L

∼ 35.0

∼ 50.0

∼ 15.0

L ⇌ M2P + Mn3P + γ

955

E?

L

∼ 40.4

∼ 44.2

∼ 15.4

Table 4.

Investigations of the Fe-Mn-P Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1969Fru]

Magnetic measurements (thermomagnetic balance)

Curie temperatures, magnetic moment, magnetization

[1969Rog]

Magnetic measurements (thermomagnetic balance)

Curie temperatures, magnetic moment, magnetization (continued)

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Fe–Mn–P

Reference

Method/Experimental Technique

Type of Property

[1973Nag]

Magnetic measurements (Weiss-Forrer type magnetometer, Bozorth pendulum type magnetometer)

Magnetic susceptibility, Néel and Curie temperatures, magnetic moment, magnetization

[1973Suz]

Magnetic measurements (magnetometer with a differential transformer, pendulum type magnetometer)

Magnetic susceptibility, Néel and Curie temperatures, magnetic moment

[1977Got]

Magnetic measurements (sample vibrating magnetometer; magnetic balance)

Magnetization, saturation magnetic moment, magnetic transition points

[1979Iwa]

Magnetic measurements

Magnetization, magnetic susceptibility

[1984Lee]

Bend and tension tests (Instron universal testing machine), SEM, Auger spectroscopy

Yield stress, grain boundary segregation, embrittlement and strength, hardness, tensile fracture stress, elongation

[1986Fje]

Magnetic measurements

Magnetic susceptibility, Néel temperatures, magnetic moments

[1990Bac]

Magnetic measurements, neutron diffraction

Magnetic susceptibility, magnetic ordering temperature

[1993Vav]

Electrical resistivity measurements, mechanical properties tests

Electrical resistivity, microhardness, plasticity to bending

[1997Vav]

Magnetic measurements

Effective magnetic ﬁeld

[1997Zho]

Mechanical tests

Effect of Mn additions on the P embrittlement of the Fe grain boundary

[1998Vav]

Mechanical properties tests, electrical resistivity measurements

Brittle temperature, electrical resistivity

[1999Vav]

Mechanical properties tests, magnetic measurements

Microhardness, plasticity, effective magnetic ﬁeld, chemical shift

[2000Bro]

Magnetization measurements (vibrating sample magnetometer (VSM); quantum design MPMS 5.5T SQUID magnetometer)

Magnetization, Curie temperatures, magnetic moments

[2000Vav]

Rapid quenching, X-ray diffraction, thermal analysis, Mössbauer spectroscopy; viscosity measurements (rotational oscillations of a quartz beaker ﬁlled with the melt

Kinematic viscosity

[2001Vav]

Mechanical properties tests

Structural hardening

[2003Liu]

Magnetization measurements (quantum design MPMS 5.5T SQUID magnetometer)

Magnetization, Néel temperatures, intensity of magnetic reﬂections, density of states

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Fe–Mn–P

13

Fig. 1. Fe-Mn-P. The Mn2P-Fe2P phase diagram

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Fe–Mn–P

Fig. 2. Fe-Mn-P.

Reaction scheme

14

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Fe–Mn–P

15

Fig. 3. Fe-Mn-P. Partial liquidus surface projection

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Fe–Mn–P

Fig. 4. Fe-Mn-P. Partial isothermal section at 25°C

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Fe–Mn–P

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Fig. 5. Fe-Mn-P. Temperature-composition section at 95 mass% Fe, 0 to 4 mass% P (Mn5.08Fe94.92Mn0.98Fe92.03P6.99 in at.%)

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Fe–Mn–P

Fig. 6. Fe-Mn-P. Lines of constant molar Gibbs free energy of formation from melts at 1377°C

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Fe–Mn–P

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Fig. 7. Fe-Mn-P. Lines of constant molar enthalpy of formation from melts at 1377°C

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20 References [1948Now] [1950Ber] [1952Vog]

[1955Sul] [1965Kan1]

[1965Kan2]

[1969Fru]

[1969Rog]

[1969Sch]

[1972Sel] [1972Sha]

[1973Mae] [1973Nag] [1973Suz] [1974Sig] [1977Got]

[1979Iwa]

[1980Bra] [1980Kun]

[1981Maa]

Fe–Mn–P

Nowotny, H., Henglein, E., “Study of Ternary Alloys with Phosphorus” (in German), Monatsh. Chem., 79, 385–393 (1948) (Crys. Structure, Phase Relations, Experimental, Review, *, 18) Berak, J., Heumann, T., “The Phosphorus-Manganese System” (in German), Z. Metallkd., 41, 19–23 (1950) (Phase Diagram, Phase Relations, Experimental) as quoted by [1955Sul] Vogel, R., Berak, J., “The Iron-Phosphorus-Manganese System” (in German), Arch. Eisenhuettenwes., 23(5–6), 217–223 (1952) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Experimental, *, 14) Sully, A.H., Manganese, Butterworth Scientiﬁc Publications, London, 295pp. (Crys. Structure, Phase Diagram, Phase Relations, Review, Phys. Prop.) Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Iron, Phosphorus and Other Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159–165 (1965) (Morphology, Phase Diagram, Phase Relations, Experimental, Review, *, 24) Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α- and γ-Iron” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166–170 (1965) (Phase Relations, Experimental, Review, *, 20) Fruchart, R., Roger, A., Senateur, J.P., “Crystallographic and Magnetic Properties of Solid Solutions of the Phosphides M2P, M = Cr, Mn, Fe, Co, and Ni”, J. Appl. Phys., 40(3), 1250–1257 (1969) (Crys. Structure, Experimental, Magn. Prop., 45) Roger, A., Senateur, J.-P., Fruchart, R., “Crystallographic and Magnetic Properties of Solid Solutions Among the Phosphides Ni2P - Co2P - Fe2P - Mn2P and Cr2P” (in French), Ann. Chim. (Paris), 4(2), 79–91 (1969) (Crys. Structure, Experimental, Magn. Prop., 44) Schenck, H., Steinmetz, E., Gitizad, H., “Activity of Phosphorus in the Molten Iron and its Control by Nickel, Manganese and Chromium” (in German), Arch. Eisenhuettenwes., 40(8), 597–602 (1969) (Thermodyn., Experimental, 24) Selte, K., Kjekshus, A., “Structural and Magnetic Properties of FeP”, Acta Chem. Scand., Ser. A, 26(3), 1276–1277 (1972) (Crys. Structure, Experimental, Magn. Prop., 17) Shabdenov, B.A., Kunaev, A.M., Ilieva, A.A., “Thermodynamic Properties of Phosphorus in Liquid Metallic Alloys” (in Russian), Khim. Khim. Tekhnol. (Alma-Ata), 13, 228–233 (1972) (Thermodyn., Experimental) as quoted by [1995Zai] Maeda, Y., Takashima, Y., “Mössbauer Studies of FeNiP and Related Compounds”, J. Inorg. Nucl. Chem., 35(6), 1963–1969 (1973) (Crys. Structure, Experimental, Electronic Structure, 12) Nagase, S., Watanabe, H., Shinohara, T., “Magnetic Properties of the System Fe2P-Mn2P”, J. Phys. Soc. Jpn., 34(4), 908–910 (1973) (Crys. Structure, Experimental, Magn. Prop., 11) Suzuki, T., Yamaguchi, Y., Yamamoto, H., Watanabe, H., “Magnetic Structure of FeMnP”, J. Phys. Soc. Jpn., 34(4), 911–916 (1973) (Crys. Structure, Experimental, Magn. Prop., 12) Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 (1974) (Thermodyn., Review, 249) Goto, M., Tange, H., Tokunaga, T., Fujii, H., Okamoto, T., “Magnetic Properties of the (Fe1–xMx)3P Compounds”, Japan. J. Appl. Phys., 16(12), 2175–2179 (1977) (Crys. Structure, Experimental, Magn. Prop., 16) Iwata, N., Fujii, H., Okamoto, T., “Magnetic Properties of (Mn,Cr)P and (Mn,Fe)P Compounds”, J. Phys. Soc. Jpn., 46(3), 778–783 (1979) (Morphology, Experimental, Theory, Magn. Prop., 11) cited from abstract Brandes, E.A., Flint, R.F., “Mn-Fe-P” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 116 (1980) (Phase Diagram, Phase Relations, Review, *, 1) Kunaev, A.M., Shabdenov, B.A., Beisembaev, B.B., Omarov, N.G., “A Study of the Thermodynamic Behavior of Manganese in Iron-Phosphorus-Manganese Melts” (in Russian), Vestn. Akad. Nauk Kaz. SSR, (7), 43–46 (1980) (Thermodyn., Experimental) as quoted by [1995Zai] Maaref, S., Madar, R., “Crystal Chemistry of M12P7 Phases in Relation with the M2P Phosphides”, J. Solid State Chem., 40, 131–135 (1981) (Crys. Structure, Experimental, Theory, 11)

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Fe–Mn–P [1983Mat]

[1983Yam]

[1984Ban]

[1984Lee]

[1986Fje]

[1988Rag]

[1988The]

[1989Paj]

[1990Bac]

[1991Sjo]

[1993Din]

[1993Vav]

[1995Bou]

[1995Zai]

[1996Zai]

[1997Vav]

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21

Matsuyama, T., Hosokawa, H., Suto, H., “Tracer Diffusion of P in Iron and Iron Alloys”, Trans. Jpn. Inst. Met., 24(8), 589–594 (1983) (Morphology, Experimental, Interface Phenomena, Kinetics, Magn. Prop., 14) Yamada, K., Kato, E., “Effect of Dilute Concentrations of Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo on the Activity Coefﬁcient of P in Liquid Iron”, Trans. Iron Steel Inst. Jpn., 23(1), 51–55 (1983) (Thermodyn., Calculation, Experimental, 16) Ban-Ya, S., Maruyama, N., Kawase, Y., “Effects of Ti, V, Cr, Mn, Co, Ni, Cu, Nb, Mo and W on the Activity of Phosphorus in Liquid Iron” (in Japanese), Tetsu to Hagane, 70(1), 65–72 (1984) (Thermodyn., Calculation, Experimenta1, Review, 21) Lee, D.Y., Barrera, E.V., Stark, J.P., Marcus, H.L., “The Inﬂuence of Alloying Elements on Impurity Induced Grain Boundary Embrittlement”, Metallurg. Trans. A. (Phys. Met. and Mater. Sci.), 15A(7), 1415–1430 (1984) (Morphology, Thermodyn., Calculation, Experimental, Interface Phenomena, Mechan. Prop., 41) Fjellvaeg, H., Kjekshus, A., Andresen, A.F., “Structural and Magnetic Properties of Mn1–tFetP (0.80 ≤ t ≤ 1.00)”, Acta Chem. Scand., Ser. A, A40, 227–229 (1986) (Crys. Structure, Experimental, Magn. Prop., 15) Raghavan, V., “The Fe-Mn-P (Iron-Manganese-Phosphorus) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 3, 91–99 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, Review, #, 11) “The 19th Committee on Steelmaking, The Japan Society for the Promotion of Science”, Steelmaking Data Sourcebook, Gordon and Bresch Science Publishers, 280 (1988) (Morphology, Thermodyn., Review) as quoted by [1993Din] Paju, M., Grabke, H.J., “Segregation of Phosphorus in Austenite in Fe-P and Fe-10Mn-P Alloys”, Mater. Sci. Technol., 5(2), 148–154 (1989) (Morphology, Thermodyn., Experimental, Interface Phenomena, 33) cited from abstract Bacmann, M., Fruchart, D., Chenevier, B., Fruchart, R., Puertolas, J.A., Rillo, C., “Magnetic Phase Diagram of the (Fe1–xMnx)2P System”, J. Magn. Magn. Mater., 83(1–3), 313–314 (1990) (Morphology, Abstract, Phase Relations, Experimental, Magn. Prop., 13) Sjostrom, J., Jarlborg, T., “Band Structures and Magnetic Properties in the Iron Phosphide Compounds, FeMnP, FeCrP and FeVP”, J. Magn. Magn. Mater., 98(1–2), 85–91 (1991) (Crys. Structure, Calculation, Electronic Structure, Magn. Prop., 15) cited from abstract Ding, X., Wang, W., Han, Q., “Thermodynamic Calculation of Fe-P-j System Melt”, Acta Metall. Sin. (China), 29(12), B527–B532 (1993) (Thermodyn., Calculation, Phase Relations, Theory, 7) Vavilova, V.V., Kovneristyi, YuK., Levintov, M.B., “Phase Equilibrium and Tendency to Amorphization in Alloys of the System Fe-P-Mn”, Inorg. Mater. (Engl. Trans.), 29(6), 883–887 (1993), translated from Neorg. Mater., 29(6), 770–773 (Morphology, Phase Relations, Experimental, Electr. Prop., Mechan. Prop., *, 10) Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467–484 (1995) (Phase Relations, Thermodyn., Calculation, Review, Theory, 85) Zaitsev, A.I., Dobrokhotova, ZhV., Litvina, A.D., Mogutnov, B.M., “Thermodynamic Properties of Iron-Manganese-Phosphorus Melts”, Inorg. Mater. (Engl. Trans.), 31(9), 1064–1072 (1995), translated from Neorg. Mater., 31(9), 1164–1173 (1995) (Phase Relations, Thermodyn., Experimental, 36) Zaitsev, A.I., Litvina, A.D., Shelkova, N.E., Mogutnov, B.M., “Thermodynamic Properties of {xFe+yMn+(1–x–y)Si} (l) and {xFe+yMn+(1–x–y)P} (l)”, J. Chem. Thermodyn., 28, 285–306 (1996) (Thermodyn., Experimental, 66) Vavilova, V.V., Kovneristyi, Y.K., “Preparation and Thermal Stability of Fe-P-M (M = Mo, V, Nb, Mn, Si) Amorphous Alloys”, Inorg. Mater. (Engl. Trans.), 33(3), 275–281 (1997), translated from Neorg. Mater., 33(3), 333–339 (1997) (Phase Diagram, Phase Relations, Thermodyn., Experimental, Electr. Prop., Magn. Prop., 15)

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22 [1997Zho]

[1998Vav]

[1998Zai]

[1999Vav]

[2000Bro]

[2000Vav]

[2000Zha]

[2001Vav]

[2002Per]

[2003Bal]

[2003Liu]

[2004Wit]

[2007Wit] [Mas2] [V-C2]

Fe–Mn–P Zhong, L., Wu, R., Freeman, A.J., Olson, G.B., “Effects of Mn Additions on the P Embrittlement of the Fe Grain Boundary”, Phys. Review B. (Condens. Mater.), 55(17), 11133–11137 (1997) (Morphology, Calculation, Electronic Structure, Mechan. Prop., 14) cited from abstract Vavilova, V.V., Kovneristyi, YuK., Palii, N.A., “Correlation between the Annealing-induced Embrittlement of Fe-P-M (M = V, Mn, Si) Amorphous Alloys and the Content of α -Fe Precipitates”, Inorg. Mater. (Engl. Trans.), 34(6), 566–570 (1998), translated from Neorg. Mater., 34(6), 692–696 (1998) (Crys. Structure, Morphology, Phase Relations, Experimental, Electr. Prop., Mechan. Prop., 17) Zaitsev, A.I., Litvina, A.D., Shelkova, N.E., Mogutnov, B.M., “Association in Ternary Metallic Melts Fe-Mn-Si, Fe-Cr-P and Fe-Mn-P”, Thermochim. Acta, 314, 307–315 (1998) (Phase Relations, Thermodyn., Calculation, Experimental, 31) Vavilova, V.V., Baldokhin, Y.V., “Mössbauer Study of Rapidly Quenched Fe-P-E Alloys (E = V, Nb, Mo, Mn, Si)”, Russ. Metall. (Engl. Transl.), (1), 122–132 (1999) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Experimental, Review, Magn. Prop., Mechan. Prop., 20) Broddefalk, A., James, P., Liu, H.-P., Kalska, B., Anderson. Y., Granberg, P., Nordblad, P., Haeggstroem, L., Eriksson, O., “Structural and Magnetic Properties of (Fe1–xMnx)3P (x < 0.25)”, Phys. Rev. B, 61(1), 413–421 (2000) (Crys. Structure, Calculation, Experimental, Magn. Prop., 25) Vavilova, V.V., Baldokhin, Y.V., Kovneristyi, Y.K., Matveev, V.M., “Fe-P-M (M = Si, Mn, V) Alloys: Viscosity in the Liquid State and Tendency to Amorphization”, Inorg. Mater. (Engl. Trans.), 36(7), 703–708 (2000), translated from Neorg. Mater., 36(7), 845–851 (2000) (Morphology, Thermodyn., Calculation, Experimental, Kinetics, Phys. Prop., 13) Zhang, J., Zhu, R., “Thermodynamic Properties of Mn-P and Fe-Mn-P Melts”, J. Univ. Sci. Technol. Beijing, 7(1), 10–13 (2000) (Phase Diagram, Phase Relations, Thermodyn., Calculation, 6) cited from abstract Vavilova, V.V., Kovneristyi, Y.K., Palii, N.A., “Physico-Chemical Properties of Amorphous and Crystalline Fe-P-Mn and Fe-P-Mn-V Alloys”, Inorg. Mater., 37(2), 166–169 (2001) (Morphology, Experimental, Mechan. Prop., 5) cited from abstract Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 20.16107.1.20, (2002) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assessment, Phys. Prop., #, 23) Baldokhin, Y.V., Vavilova, V.V., Kolotyrkin, P.Y., Kovneristyi, Y.K., Palii, N.A., Solomatin, A.S., “Nanoscale Crystallization in Amorphous Fe-P-Mn Alloys”, Inorg. Mater., 39(6), 562–567 (2003) (Crys. Structure, Morphology, Experimental, 8) cited from abstract Liu, H.-P., Andersson, Y., James, P., Satula, D., Kalska, B., Haeggstroem, L., Eriksson, O., Broddefalk, A., Nordblad, P., “The Antiferromagnetism of (Fe1–xMnx)3P, x ≥ 0.67, Compounds”, J. Magn. Magn. Mater., 256, 117–128 (2003) (Crys. Structure, Phase Relations, Calculation, Experimental, Electronic Structure, Magn. Prop., 26) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354, (2004) (Phase Diagram, Phase Relations, Thermodyn., Assessment, Calculation, 34) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_19 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

1

Iron – Manganese – Sulfur Vasyl Tomashik, Hans-Leo Lukas

Introduction Numerous studies of the Fe-Mn-S ternary system have been done since 1913 [1913Roe] because of its importance in understanding desulfurization of molten steels and the formation of sulﬁdes in the solidiﬁcation process [1976Hil2, 1980Bra, 1988Rag, 2000Oht]. The ﬁrst experimental results concerning this system were included in the review of [1949Jae]. A critical assessment of the Fe-Mn-S system has been published by [1988Rag], which includes the literature up to 1983. The literature up to 2000 is discussed in [2004Rag]. The present assessment takes into account all available data. Most of the studies of this ternary system have been completed in the Fe-FeS-MnS-Mn part of the composition triangle. The FeS-MnS system is described by a phase diagram of the eutectic type with the eutectic temperature reported between 1110 and 1181°C and eutectic composition of 6 and 10 mol% MnS [1913Roe, 1928Shi, 1964Cha, 1971Ski, 1976Man, 1978Fis2, 1980Ito]. The existence of a ternary compound Fe3Mn2S5, reported by [1913Roe] with a melting temperature of 1365°C, was not conﬁrmed by the later investigations. This composition corresponds to the FexMn1–xS solid solutions which crystallize in the cubic structure of MnS extending at 700°C up to the composition Fe0.6Mn0.4S [1971Bru]. The phase diagram of the quasibinary FeS-MnS system at 1000°C and high pressures was determined by [1984McC]. The ﬁrst experimental results on the mutual solubility of FeS and MnS were obtained by [1928Shi, 1964Cha, 1966Kie, 1969Sal]. The data of [1928Shi] were included in the review of [1964Kul]. Later the mutual solubility was investigated by [1971Ski]. Much work has been done in studying the liquidus of the Fe-FeS-MnS-Mn part of the Fe-Mn-S system [1933Vog, 1934Mey, 1937Vog, 1937Wen, 1971Tur, 1972Kor, 1975Big, 1975Ito2, 1975Sch, 1975Tur, 1976Man, 1980Ito, 1983Uto]. The phase relations in the Fe-Mn-S system at 1330 and 1615°C were investigated by [1971San] and included in the review of [1980Bra]. Phase diagrams calculated from thermochemical data are given by [1976Hil1, 1978Uhr, 1976Hil2, 1981Nis, 1998Mie, 1998Val, 2000Oht]. Isothermal sections of the Fe-Mn-S system at 1610, 1600, 1330, 1300, 1200, 1100, 950, 800°C were constructed by [1963Kan, 1971Nak, 1971Ski, 1973Kir, 1975Sch, 1978Fis2]. Some polythermal sections of the Fe-Mn-S system were constructed by [1933Vog], [1937Vog] and [1975Ito2]. The solid solubility of S in (γFe) at 1000, 1200 and 1335°C in the presence of 0.37, 0.40, 1.07, 1.16 and 1.30 mass% Mn was determined by [1955Tur1, 1955Tur2]. The presence of Fe in Mn melts leads to decreasing of the S solubility [1973Das]. Chemical compositions of sulﬁdes in Fe-Mn-S ternary alloys containing between 0.01 and 1.0 mass% S and 0.01 to 1.5 mass% Mn within the temperature range 800 to 1500 were calculated by [1976Eﬁ]. The equilibrium in the interaction FeS + Mn ⇌ MnS + Fe at 1600°C is shifted to the formation of MnS [1934Mey]. According to [1968Ska] FexMn1–xS solid solutions are formed during cooling Fe-Mn-S alloys containing 2.60 or 1.88 mass% Mn and 0.051 or 0.78 mass% S, respectively. [1971Nak] reports in the equilibrium (γFe)-FeS-MnS at 1300°C the compositions of the phases to be Fe0.988Mn0.012S, Fe0.642Mn0.358S and (γFe), containing 0.15 mass% Mn and 0.009 mass% S. Thermodynamic properties of solid and liquid alloys in the Fe-Mn-S ternary system were investigated by [1952She, 1955Tur1, 1966Sch, 1967Bro, 1969Ban, 1969Sch, 1970Nis, 1973Buz, 1973Das, 1974Sig, 1977Fis, 1995Bou, 1998Val]. Table 1 lists the numerous experimental works on the phase equilibria, crystal structures and thermodynamics of the Fe-Mn-S system. Binary Systems The binary systems are accepted as calculated from the dataset of [1998Mie]. The Fe-Mn dataset is adopted from [1989Hua], Fe-S and Mn-S were assessed in the work of [1998Mie]. Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

2

Fe–Mn–S

A newer calculation of the Fe-Mn system by [2004Wit] differs only within the accuracy of the experimental knowledge. The binary systems given by [Mas2] agree fairly well with those of [1998Mie]. Solid Phases Crystallographic data of solid phase are given in Table 2. The solid solubility of S in (γFe) at 1000, 1200 and 1335°C was found to be 0.013, 0.031 and 0.046 mass%, respectively [1955Tur1]. In the presence of 0.37, 1.07 and 1.30 mass% Mn the S solubility is 0.0018, 0.0007 and 0.0006 mass%, respectively, at 1200°C (0.0019 and 0.007 mass% S at 0.40 and 1.16 mass% Mn respectively [1955Tur2]) and increases up to 0.0058, 0.0031 and 0.0018 mass% at 1335°C [1955Tur1]. The effect of Mn on the S solubility in Fe at 1600°C is shown in Fig. 1 [1973Buz]. The solubility of MnS in FeS and FeS in MnS at 600, 700, 800, 900 and 1000°C is equal to 5.0, 6.0, 6.6, 7.0, 7.4 and 53.6, 58.8, 64.6-65.0, 68.0-68.8, 73.6-73.8 mol%, respectively [1971Ski]. The mutual solubilities of FeS and MnS signiﬁcantly depend on the S vapor pressure [1980Nis]. The Fe content in rambergite (FexMn1–xS) varies between 0.1 and 6 at.% for different samples [2001Eri]. FeS and other binary sulphides are in equilibrium with the Fe phase in the Fe-Mn-S system [1963Kan]. Quasibinary Systems By comparing the locations of the solvus at the MnS side of the quasibinary FeS-MnS phase diagram of [1928Shi] with own results, [1971Ski] concluded that the temperatures reported by [1928Shi] may be overestimated. [1976Man] reported the eutectic temperature to be 1110°C and the eutectic composition to be about 7.5 mol% MnS. Although [1928Shi] stated that FeS in their studies was stoichiometric, [1976Man] found some metal-deﬁciency in FeS. More reliable eutectic temperatures and eutectic compositions in the system Fe1–xS-MnS are 1110°C and about 10 mol% MnS respectively, proposed in the review of [1988Rag] (Fig. 2, dashed lines). A calculation using the dataset of [1998Mie] gives a higher eutectic temperature of 1181°C but the eutectic compositions are nearly the same (Fig. 2, solid lines). This may be an artefact of modelling the phases P and Q to be restricted to strictly stoichiometric 50 at.% S. The lattice parameters of the FexMn1–xS solid solutions based on MnS can be expressed by the equation a = 522.4 - 0.1653 mol% FeS (pm) [1984McC]. The phase diagram of the FeS-MnS system determined at 1000°C in high-pressure experiments is illustrated in Fig. 3 [1984McC]. The maximum concentration of MnS in FeS decreases from 7.4 mol% at 0.1 MPa to 5.4 mol% at 3.5 GPa, and remains relatively constant to at least 7 GPa. The limiting solubility of FeS in MnS appears to change dramatically between 6 and 7 GPa. It is likely that the discontinuity is caused by a high-pressure phase transition. [1988Rag] indicated the Fe-MnS section to be also quasibinary, but precise experimental data on this section are not available. The quasibinary character can be only an approximation as the monotectic maximum L1 ⇌ Fe + Q and the eutectic maximum L2 ⇌ Fe + Q may be somewhat off this plane and there is no reason, why both these three-phase maxima should be exactly in the same plane. In calculations using the dataset of [1998Mie] the monotectic appears in the plane going from Fe1.04Mn48.96S50 to Fe90.12Mn9.88 and the eutectic in the plane from Fe0.57Mn49.43S50 to Fe99.0Mn1.0. Invariant Equilibria A reaction scheme for the Fe-FeS-MnS-Mn part of the Fe-Mn-S system is given in Fig. 4, calculated from the dataset of [1998Mie]. The calculated phase compositions are given in Table 3. The deviation of the sulfur content from stoichiometry in the P phase is neglected in the dataset of [1998Mie], thus the composition of sulfur in P and Q appears always as exactly 50 at.% in Table 3. The three different miscibility gaps of liquid were ﬁrst time mentioned by [1976Hil1], their temperatures and phase compositions must be taken as tentative as not enough experimental data are available. The parts below U4 agree with the reaction scheme assessed in the review of [1988Rag], except U4 itself, where [1988Rag] gave the reaction: (δFe) + L ⇌ Q + γ, whereas the calculation yields: (δFe) + Q ⇌ L + γ. [1988Rag] as a consequence postulated a minimum of the three-phase ﬁeld (δFe) + Q + γ between U2 and U4. The three-phase equilibria along the sequence p2-U5-U2-U4-e4 containing the two phases γ and (δFe) describe mainly the transformation DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

3

(δFe) ⇌ γ, the third phases participate only with very small amounts in this transformation. Both modiﬁcations of Fe are very dilute with respect to S and Mn, and the S content in both phases decreases monotonically along this sequence and the Mn content increases monotonically. Due to Henry’s law thus also the temperature must change monotonically and a minimum is very unlikely. The congruent formation of (βMn) from γ in the Fe-Mn binary system results in a pair of γ + (βMn) + Q phase ﬁelds at ∼ 1150°C. The order-disorder transitions in Fe1–xS at lower temperatures and the transitions in (S) are not considered separately in the reaction scheme. Regarding the sulfur rich part of the system [1988Rag] indicated that there are literature data suggesting a transition reaction P + L ⇌ Q + FeS2 just below the Fe-S peritectic temperature of 743°C, by which pyrite comes into two-phase equilibrium with the Q phase. [1988Rag] assumed the maxima e1 and e3 to be exactly on the line Fe-MnS. Thermodynamically there is no reason for this assumption and the calculation gives deviations, for e1 much more than for e3. Liquidus, Solidus and Solvus Surfaces A liquidus surface of the Fe-FeS-MnS-Mn part of the Fe-Mn-S system was constructed by [1988Rag] using the experimental results of [1933Vog, 1934Mey, 1937Vog, 1937Wen, 1971Tur, 1972Kor, 1975Big, 1975Ito2, 1975Sch, 1975Tur, 1976Man, 1980Ito, 1983Uto]. The main features, especially those proved by experimental data agree with the liquidus surface calculated from the dataset of [1998Mie] shown in Fig. 5a. The isotherms are drawn in 100°C steps up to 2000°C. Above this temperature in the Mn corner appears the gas phase (at 0.1 MPa pressure). Parts of this liquidus projection are shown enlarged in rectangular coordinates in Figs. 5b to 5d. A liquid miscibility gap that originates on the Mn-MnS side dominates this region. The eutectic through, L + γ + Q, starting near the Mn corner at e5 runs around the liquidus boundary of the miscibility gap. In the calculated liquidus surface it is interrupted by reaction U3 and ends at U6. Contrary to the calculation and to some of the earlier studies including that of [1975Sch], [1988Rag] assumed that the miscibility gap does not reach and interrupt this eutectic through at any point. There is a temperature maximum e3 at 1510°C on the Fe-MnS quasibinary section, however not exactly on the join FeMnS. A number of early reports give the invariant reaction U6 as a ternary eutectic. However, the results of [1976Man] and [1980Ito] conﬁrm the earlier ﬁnding of [1937Vog] that this reaction is transition [1988Rag]. According to thermochemical calculations there are three miscibility gaps in the Fe-FeS-MnS-Mn subsystem [1976Hil1]. These authors calculated the locus of the critical points of the miscibility gaps. This calculation is not directly implemented in Thermo-Calc. Figure 5 does not show this locus, but the univariant lines of three-phase equilibria containing two or three different liquids, thus the results of [1976Hil1] and Fig. 5 are difﬁcult to compare. The calculated liquidus surface near the Fe corner is shown in Fig. 6, it agrees well with a diagram given by [1975Big]. Isothermal Sections The calculated isothermal section at 1600°C is given in Fig. 7. The diagram reported by [1975Sch] agrees well at the metal rich side but shows a signiﬁcantly lower S concentration in the sulﬁdic melt. The scatter of the experimental data however is even larger and thus this problem cannot be solved. Furthermore [1975Sch] shows only a single critical point at 4.5 at.% Mn and 33.5 at.% S instead of the two calculated ones. The calculated isothermal sections at 1500, 1400, 1300, 1200, 1100 and 1000°C are given in Figs. 8 to 13. In the two-phase ﬁelds, where the direction of tie-lines is an important information, some calculated tie lines are drawn. This is the ﬁeld L + Q in Figs. 7 and 8 and γ + Q in Figs. 10 to 13. In Fig. 14 the composition of FexMn1–xS (Q) in equilibrium with γ alloys is shown in more detail at 1100, 1200 and 1300°C from [1988Rag] due to [1978Fis1]. Figure 15 shows an isothermal section at 800°C according to [1971Ski] and [1988Rag], showing the homogeneity range of Fe1–xMnxS1+y (P). Temperature – Composition Sections Five polythermal sections of the Fe-Mn-S system from the S corner to the Fe-Mn binary system and one section from Mn to the Fe-S binary system were constructed by [1933Vog]. [1937Vog] constructed 4 polythermal sections: 97Fe3Mn (mass%) - S, 94Fe6Mn (mass%) - S, 90Fe10Mn (mass%) - S and 80Fe20Mn Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

4

Fe–Mn–S

(mass%) - S. Some vertical sections were calculated by [2000Oht] and it was shown that the obtained phase boundaries agree well with the experimental data points from [1937Vog], although the conﬁguration of the phase ﬁelds is different from that drawn by [1937Vog]. An Fe1–xS-MnS section “in equilibrium with excess Fe” has been investigated by [1975Ito1, 1975Ito2, 1976Man, 1978Fis2, 1980Ito]. Figure 16 gives this FeS-MnS ﬁgure calculated from the dataset of [1998Mie]. Figure 16 is not really a T-c section but a projection of the univariant lines of the three-phase ﬁelds containing iron (α or γ) and any two of the three phases L, P or Q, projected from the S corner onto the Fe-Mn plane. The invariant horizontal at 1005°C corresponds to the four-phase equilibrium U6. Thermodynamics The activity coefﬁcient of sulfur in Fe-Mn-S alloys decreases with increasing Mn content. The magnitude of this effect varies with temperature and Mn content of the alloy [1952She, 1955Tur1, 1955Tur2, 1966Sch, 1969Ban, 1969Sch, 1970Nis, 1973Buz]. The ﬁrst order interaction coefﬁcients are eMnS = –0.025 and εMnS = –5.7 at 1600°C and up to 5 mass% Mn [1952She] and εSMn = –0.048 at 1600°C [1974Sig] (eMnS = –0.017 and εMnS = –3.86 at 1600°C and up to 3.5 mass% Mn [1966Sch, 1969Sch]; eMnS = –0.026 and interaction parameter θMnS is equal –5.87 at 1550°C and up to 8 at.% Mn [1969Ban, 1974Sig]; eMnS = –0.021 and εMnS = –4.76 at 1600°C and at 0.5-20 mass% S [1973Buz]). [1998Val] notes that eMnS = –0.024 and eSS = 0.0087 at 1487°C. The temperature dependence of eMnS at 1200–1600°C can be expressed by the equation eMnS = –215/T + 0.097 [1955Tur1]. The calculated values of eSMn reproduce the experimental data satisfactorily and can be expressed at the temperatures 1230–1930°C by the equation eSMn = –420683.7/T + 218.5 [1995Bou]. [1970Nis] reports a very strong interaction between Mn and S in δFe around 1500°C: eMnS = –0.58, valid up to 0.15 mass% Mn. The second order interaction coefﬁcient rMnS is equal zero [1974Sig]. According to the data of [1952She] up to and possibly beyond 5 mass% Mn the activity coefﬁcient f MnS is independent on the S content. The ﬁrst order interaction coefﬁcient eFeS is equal to 0.008 between 1300 and 1500°C and up to 22 mass% Fe [1973Das]. [1977Fis] equilibrated (Fe,Mn)-sulﬁde solid solutions with a gas phase of H2/H2S mixtures and measured the ratio p(H2S)/p(H2), which is proportional to the S-activity. Thermochemical data on the Fe-Mn-S system are summarized on a single sulfur potential diagram by [1967Bro], which allows to predict the solubility of S in liquid and solid Fe-Mn alloys. Thermodynamic datasets to calculate phase diagrams of the Fe-FeS-MnS-Mn partial system were assessed by [1976Hil2, 1998Mie, 2000Oht]. Notes on Materials Properties and Applications Mn has a favorable inﬂuence on the hot workability of steel [1955Tur1, 1960Mch, 1971Tur, 1976Hil2]. Without Mn hot-shortness may occur in steel containing more than 0.01 mass% S. Presence of Mn appreciably reduces the S solubility. The amount of sulﬁde inclusions formed during cooling from 1200–1300°C is almost negligible as MnS inclusions, which may also contain some ferrous sulﬁde are already solid before solidiﬁcation starts. There is a limiting Mn content for each S concentration, above which no hot-short cracks appear in the steel [1960Mch]. Mn does not inﬂuence the distribution of sulﬁde inclusions but inﬂuences their dimensions and chemical compositions. The sulﬁde inclusions become smaller and contain more MnS with increasing Mn content [1960Mch]. The hot-short range varies with the type of steel, particularly with the Mn/S ratio [1971Tur]. Cold and hot fragility of Fe-Mn-S alloys is related to the formation of sulﬁdes depleted by Mn which have a low melting temperature [1973Wyj]. Outside the critical range of Mn content these sulﬁdes are replaced by intragranular sulﬁdes enriched in Mn and such alloys are ductile in the cold state and forgeable in the hot state. Electric resistance of the FexMn1–xS solid solutions decreases with increasing x up to x = 0.6 [1971Bru]. In the ﬁeld of the NiAs type hexagonal structure at 90–100 at.% Fe the solid solutions have a metallic conductivity like pure FeS. According to [1978Shi] the viscosity of FeS-MnS melts at 1300–1400°C slightly increases with increasing MnS content. The coefﬁcients of self-diffusion of the ions in such melts were estimated using experimental data. It was shown that most probably the particle responsible for the viscous ﬂow is the S–2 ion. DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

5

MnS is not hardened measurably by dissolved FeS [1964Cha]. Excess FeS will, however, increase the hardness of the sulﬁde by the formation of a two-phase microstructure. Miscellaneous Sulﬁdes of the MnS type are common non-metallic inclusions in steel [1966Kie]. The change in physical properties of the sulﬁde phase due to solid solution can be rather large. The change in composition of the steel matrix around MnS inclusions due to diffusion phenomena of solute atoms may also inﬂuence the deformation properties of the steel. [1969Sal] indicates that MnS inclusions in Fe-Mn-S alloys occur either as isolated inclusions or in groups, particularly in the interdendritic interstices. According to [2004Liu] MnS is nucleated more easily in γFe rather than in αFe and MnS precipitation in γFe can be suppressed by rapid cooling. The particles of MnS are usually larger than 100 nm. [1975Tur] indicates that aside from the precipitation of minute MnS inclusions along the interdendritic regions, there are larger particles of MnS with diameters of approximately 20 μm which contain one or two pieces of Fe particles. According to [1937Wen] decreasing of the ratio Mn/S in Fe-Mn-S alloys containing 0.31–2.0 mass% Mn and 0.27–2.03 mass% S, leads to increasing of the number of inclusions. Sulﬁdes are formed in the alloys by S transfer from a synthetic slag to a surrounding Fe-Mn matrix at 1100 to 1450°C [1971His]. The Mn concentration in the matrix decreases rapidly. The region of precipitation of sulﬁde particles widens with increasing of time and temperature and with decreasing of initial Mn matrix concentration. Sulﬁde precipitates coagulate to larger particles during repeated solution and precipitation. As a result, there appears a zone without precipitates in the neighborhood of the slag/Me interface. The shapes and locations of the precipitates are affected by the oxygen concentration of the alloy. Si in the alloy prevents somewhat the S transfer and the precipitation of sulﬁdes [1971His]. [1971Kor] notes that during oxidation of Fe containing 0.34 mass% Mn and 150 ppm sulfur depletion of Mn and accumulation of S occurs in the metal near the scale/metal interface. These changes of the Mn and S concentrations lead to the formation of liquid oxysulﬁde near the surface at 900°C. The control of morphology of MnS inclusions plays an important role in the ﬁeld of ferrous metallurgy [2000Oht]. In S-lean melts the morphology of secondary MnS inclusions formed during solidiﬁcation after primary crystallization of the Fe phase can be classiﬁed under the following three categories [1995Oik]: a) globular or droplet shaped MnS resulting from a monotectic reaction; b) rod-like MnS formed by an eutectic reaction, or c) a ﬁsh-bone type MnS formed as a result of an irregular eutectic reaction. It was found that the corrosion kinetics of the Fe-Mn alloys in pure S vapor (101.3 kPa) at 700–1000°C can be divided into four groups, depending on the alloy concentration [1980Nis]. The ﬁrst group, up to 11 mass % Mn, has a constant rate. The second group, up to ∼ 63 mass% Mn has an exponentially decreasing rate of corrosion with increasing Mn content. In the third group, ∼ 63-80 mass% Mn alloys, the corrosion rate does not follow the parabolic law and the corrosion rates become constant above 80 mass% Mn. According to [1987Pap] the sulﬁdation kinetics are parabolic in most cases for the alloys containing from 20.3 to 99.95 mass% Mn, but two different diffusion processes affect this kinetics. In the sulﬁdation at 700 and 800°C the diffusion of Mn atoms in the alloy is the rate-determining step and an interlocked scale/alloy interface is observed. At 900°C there is a transition to rate-control by the diffusion of Mn in the sulﬁde scale connected with transition from rugged to a planar scale/alloy interface. Steady-state parabolic kinetics were always observed after an initial period of the sulﬁdation of the Fe + 27 mass% Mn alloy at the temperatures 700–900°C in ﬂowing H2S/H2/N2 atmospheres corresponding to equilibrium S pressures of 8 Pa [1990Sou]. The deviation of the S-content from stoichiometry of MnS based solid solutions FexMn1–xS is very narrow (about 10–3) but in FeS based solid solutions it increases approximately by 2 orders [1973Bru, 1980Nis]. The results of a qualitative analysis of sulﬁde inclusions in Fe-Mn-S alloys indicate that even at Mn:S ratios up to 5:1 such inclusions are the MnS based FexMn1–xS solid solutions containing from 28 to 52 mass% Mn, from 3.5 to 25 mass% Fe and from 25 to 32 mass% S [1971Ska]. It was found by Mössbauer measurements on Fe0.975Mn0.025S that Mn impurities profoundly affect both, the crystallographic and the spin rotation transitions of FeS [2005Nam].

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DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

6 Table 1.

Fe–Mn–S Investigations of the Fe-Mn-S Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1913Roe]

DTA, metallography

Up to 1620°C/FeS-MnS

[1928Shi]

DTA, metallography, chemical analysis

Up to 1610°C/FeS-MnS

[1933Vog]

DTA, metallography

Up to 1500°C/Fe-FeS-MnS-Mn

[1934Mey]

Chemical analysis

1600°C/FeS + Mn

[1933Vog]

DTA, metallography, chemical analysis

Up to 1600°C/Fe-FeS-MnS-Mn

[1937Wen]

Metallography

Up to 1600°C/Fe-Mn-S at 0.31-2.0 mass% Mn and 0.27–2.03 mass% S

[1952She]

Equilibration with H2S/H2 gas and chemical analysis

Up to 1600°C/(Fe-Mn) + H2S/H2 up to 8.2 mass% Mn

[1955Tur1]

Equilibration with H2S/H2 gas and chemical analysis

1200–1600°C/(Fe-Mn) + H2S/H2 up to 1.3 mass% Mn

[1955Tur2]

Equilibration with H2S/H2 gas and chemical analysis

1200–1600°C/(Fe-Mn) + H2S/H2 at 0.4 or 1.16 mass% Mn

[1960Mch]

Metallography, chemical analysis

1520 and 1600°C/Fe-Mn-S at 0.20-0.30 mass% S and up to 3 mass% Mn

[1963Kan]

XRD, chemical analysis

Fe-Mn-S

[1964Cha]

Microhardness measurements

Up to 1600°C/FeS-MnS

[1966Kie]

XRD, EPMA, microhardness measurements

1150°C/FeS-MnS

[1966Sch, 1969Sch]

Chemical analysis

1600°C/Fe-Mn-S up to 3.5 mass% Mn

[1968Ska]

EPMA

Fe + 2.60 or 1.88 mass% Mn + 0.051 or 0.78 mass% S

[1969Ban]

Chemical analysis

1550°C/Fe-Mn-S

[1969Sal]

Chemical analysis

Fe-Mn-S

[1970Nis]

Chemical analysis

1600°C/Fe-Mn-S up to 0.15 mass% Mn

[1971Kor]

EPMA

900–1300°C/Fe-Mn-S

[1971Nak]

EPMA, metallography

1300°C/γFe-FeS-MnS up to 9.3 mass% Mn

[1971San]

EPMA, levitation melting

1330 and 1615°C/Fe-Mn-S

[1971Ska]

EPMA, TEM

(Fe + 1.88 or 2.6 mass% Mn)-S

[1971Ski]

XRD, EPMA

600–1000°C/FeS-MnS (continued)

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

7

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1973Bru]

TGA, XRD

600–900°C/FexMn1–xS

[1973Buz]

XRD, EPMA

1600°C/Fe-Mn-S

[1973Das]

Chemical analysis

1300°C/Fe-Mn-S up to 22 mass% Fe

[1973Kir]

EPMA, metallography

1190–1380°C/Fe-Mn-S

[1973Wyj]

EPMA, metallography, SEM

Fe + 0.05-0.50 mass% Mn + 0.25–0.30 mass% S

[1975Big]

DTA, SEM

Up to 1650°C/Fe-Mn-S

[1976Man]

XRD, EPMA, DTA, metallography

Up to 1160°C/Fe-FeS-MnS-Mn

[1977Fis]

XRD, EPMA, metallography, vapor pressure measurements

1100–1400°C/Fe-Mn-S

[1978Fis1]

Chemical analysis, metallography

1100–1300°C/(Fe-Mn) + H2S/H2 up to 0.39 mass% Mn

[1978Fis2]

EPMA, chemical analysis, metallography

1100–1300°C/Fe-Mn-S

[1980Ito]

X-ray microanalysis, chemical analysis

670–1500°C/Fe-Mn-S

[1980Nis]

XRD, EPMA, TGA, metallography

670–1500°C/Fe-Mn-S

[1983Uto]

Metallography, chemical analysis, X-ray microanalysis

1600°C/Fe-Mn-S

[1984McC]

XRD,EPMA, Mössbauer spectroscopy

Up to 1000°C/FeS-MnS

[1987Pap]

TGA, SEM, chemical analysis, X-ray EDA, metallography

700, 800 and 900°C/(Fe + 27 mass% Mn) + H2S/ H2/N2

[1990Sou]

TGA, XRD, chemical analysis, X-ray EDA

700, 800 and 900°C/(Fe-Mn) + H2S/H2 at 20.3, 29.9, 40.6, 50 and 99.95 mass% Mn

[1995Oik]

SEM, metallography

Fe + 1 mass% Mn + 0.3 mass% S and Fe + 2.5 mass% Mn + (1–1.7) mass% S

[2000Kim]

XRD, Mössbauer spectroscopy

77–600 K/Fe0.975Mn0.025S

[2001Eri]

XRD, EPMA

Room temperature/Fe0.05Mn0.95S

[2004Liu]

TEM, EDS

Up to 800°C/Fe-Mn-S

[2005Nam]

XRD, Mössbauer spectroscopy

77–600 K/Fe0.975Mn0.025S

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8 Table 2.

Fe–Mn–S Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe)1538–1394

cI2 Im 3m W

a = 293.15

dissolves up to 10 at.% Mn pure Fe at 1390°C [V-C2, Mas2]

γ, (γFe,γMn) (γFe) 1394–912 (γMn) 1138–1100

cF4 Fm 3m Cu

a = 364.67

continuous solid solution at 915°C [Mas2]

a = 386.0

[Mas2]

α, (αFe) < 912

cI2 Im 3m W

a = 286.65

dissolves up to 3 at.% Mn, up to 0.033 at.% S pure Fe at 25°C [Mas2].

(δMn) 1246–1138

cI2 Im 3m W

a = 308.0

dissolves up to 9 at.% Fe pure Mn [Mas2].

(βMn) 1100–727

cP20 P4132 βMn

a = 631.52

dissolves up to 35 at.% Fe pure Mn [Mas2]

(αMn) < 727

cI58 I 43m αMn

a = 891.26

dissolves up to 35 at.% Fe pure Mn at 25°C [Mas2]

(βS) 115.22–95.5

mP64 P21/c βS

a = 1102 b = 1096 c = 1090 β = 96.7°

[Mas2]

(αS) < 95.5

oF128 Fddd αS

a = 1046.4 b = 1286.60 c = 2448.60

pure S at 25°C [Mas2]

P, γFeS

hP4 P63/mmc NiAs

a = 344.36 ± 0.05 c = 587.59 ± 0.05

[V-C2, Mas2]

βFeS 315–∼60

hP24 P 62c FeS, troillite

Fe0.975Mn0.025S

a = 596.3 ± 0.1 c = 1175.4 ± 0.1 a = 586.1 c = 1157.7 ± 0.1 a = 599.8 ± 1.1 c = 1171 ± 1 a = 596.7 ± 0.2 c = 1172 ± 5

mineral troillite at 21°C [V-C2, Mas2] at 21°C and 3.33 GPa [V-C2, Mas2] at 120°C [V-C2, Mas2] [2000Kim, 2005Nam] (continued)

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Fe–Mn–S

9

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

αFeS < 138

hP6 P63/mmc FeS

a = 345.59 ± 0.05 c = 577.89 ± 0.05

[V-C2, Mas2]

FeS(I)

oP8 Pnma MnP

a = 582.5 ± 0.2 b = 346.8 ± 0.1 c = 693.5 ± 0.6 a = 571.6 ± 0.9 b = 334.7 ± 0.3 c = 669.4 ± 0.9 a = 565 ± 1 b = 331.6 ± 0.3 c = 663.1 ± 0.8

at 190°C [V-C2]

at 21°C and 4.15 GPa [V-C2]

at 21°C and 6.35 GPa [V-C2]

FeS (mackinawite)

tP4 P4/nmm PbO

a = 376.8 c = 503.9

mineral mackinawite [V-C2]

αFeS2 ≲ 444.5

oP6 Pnnm FeS2 (marcasite)

a = 444.1 b = 542.5 c = 338.7 a = 446.4 b = 544 c = 339 a = 443 ± 2 b = 550 ± 4 c = 342 ± 4 a = 446 b = 538 c = 335 a = 446 b = 540 c = 336

mineral marcasite [V-C2, Mas2, 1982Kub] at 327°C [V-C2]

at p = 16.8 GPa [V-C2]

at p = 29.1 GPa [V-C2]

at p = 33.4 GPa [V-C2]

βFeS2 < 743

cP12 Pa 3 FeS2 (pyrite)

Fe2S3

tP80 P43212

a = 1053 c = 1001

[V-C2]

Fe3S4

cF56 Fd 3m Al2MgO4

a = 987.6 ± 0.2

mineral greigite [V-C2]

Fe3S4 (smythite)

hR21 R 3m Fe3S4

a = 347 ± 2 c = 3450 ± 20

mineral smythite [V-C2]

a= a= a= a=

541.79 ± 0.11 534.8 ± 0.2 529.3 ± 0.2 525.5 ± 0.2

mineral pyrite [Mas2, 1982Kub] [V-C2, Mas2] at 1.57 GPa [V-C2] at 2.87 GPa [V-C2] at 3.85 GPa [V-C2]

(continued)

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10

Fe–Mn–S

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

Fe7S8

hP45 P3121 Fe7S8

a = 686.52 ± 0.06 c = 1704.6 ± 0.2

metastable phase, mineral pyrrhotite-3C [V-C2]

Q, MnS < 1655 Fe0.65Mn0.35S

cF8 Fm 3m NaCl

a = 522.26

mineral alabandite [V-C2], dissolves up to 65 mol% FeS [1966Kie] [1966Kie] [1984McC]

MnS

hP4 P63mc ZnS

a = 398.8 c = 643.3 a = 398.2 ± 0.2 c = 644.5 ± 0.3

[V-C2] mineral rambergite [2001Eri]

MnS

cF8 F 43m ZnS

a = 559

high temperature phase [V-C2]

MnS2

cP12 Pa 3 FeS2

a= a= a= a=

mineral mauerite, at 20°C [V-C2] at 110°C [V-C2] at 200°C [V-C2] at 252°C [V-C2]

Fe0.05Mn0.95S

a = 513.0 a = 511.66

610.16 611.09 611.80 612.24

a = 607 a = 598 a = 587

Table 3.

at p = 2.13 GPa [V-C2] at p = 7.35 GPa [V-C2] at p = 12.3 GPa [V-C2]

Invariant Equilibria

Reaction or Critical Tie Line

Type

Temperature [°C]

Phase

Composition (at.%) Fe

Mn

S

L1, L3 - L2

c1

1829

L1, L3 L2

70.1 9.7

7.6 40.7

22.3 49.6

L2 ⇌ L1 + Q

e1

1672

L2 L1 Q

1.1 88.9 0.6

49.2 9.8 49.4

49.7 1.3 50.0

L1 + L2 ⇌ L3 + Q

U1

1548

L1 L2 L3 Q

83 14 58 9

1 36 7 41

16 50 35 50

L1 ⇌ (δFe) + Q

e3

1510

L1 (δFe) Q

96.5 98.14 1.0

2.6 1.83 49.0

0.9 0.03 50.0 (continued)

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

Reaction or Critical Tie Line

Type

11

Temperature [°C]

Phase

Composition (at.%) Fe

Mn

S

L1 + (δFe) ⇌ γ + Q

U2

1472

L1 (δFe) γ Q

87.4 90.6 90.5 0.2

12.3 9.4 9.5 49.8

0.3 0.007 0.004 50.0

L2, L3 − Q

c2

1437

L2, L3 Q

33.4 15.5

17.9 34.5

48.7 50.0

L1 + Q ⇌ L3 + (δFe)

U3

1369

L1 Q L3 (δFe)

84.4 12.4 62.9 99.75

0.3 37.6 2.8 0.05

15.3 50.0 34.3 0.20

(δFe) + Q ⇌ L3 + γ

U4

1363

(δFe) Q L3 γ

99.75 12.6 62.2 99.87

0.05 37.4 2.9 0.05

0.20 50.0 34.9 0.08

L3 + (δFe) ⇌ L1 + γ

U5

1362

L3 (δFe) L1 γ

68.6 99.77 81.8 99.88

1.2 0.03 0.3 0.03

30.2 0.20 17.9 0.09

L1, L3 − γ

c3

1357

L1, L3 γ

76.31 99.89

0.33 0.02

23.36 0.09

L1 ⇌ (δMn) + γ + Q

E1

1233

L1 (δMn) γ Q

12.4 12.25 13.15 0.0005

87.5 87.69 86.80 49.9995

0.1 0.06 0.05 50.0

L3 ⇌ P + Q, Gas

D1/e6

1181

L3 P Q Gas

45.80 46.24 39.15 0.0000

4.22 3.76 10.85 0.0000

49.98 50.0 50.0 100.0

L3 + Q ⇌ γ + P

U6

1005

L3 Q γ P

55.4 37.7 99.98 46.7

0.8 12.3 0.00 3.3

43.8 50.0 0.02 50.0

γ+P⇌α+Q

U7

916

γ P α Q

99.99 47.0 99.96 36.5

0.0000 3.0 0.0000 13.5

0.01 50.0 0.04 50.0

(βMn) ⇌ (αMn) + γ, Q

D2

700

(βMn) (αMn) γ Q

31.9 31.0 39.4 0.0

68.1 69.0 60.6 50.0

0.000 0.000 0.000 50.0 (continued)

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12

Reaction or Critical Tie Line γ ⇌ α + (αMn), Q

Fe–Mn–S

Type

D3

Temperature [°C]

Phase

248

γ α (αMn) Q

Composition (at.%) Fe

Mn

56.4 96.7 34.1 0.0

43.6 3.3 65.9 50.0

S 0.000 0.000 0.000 50.0

Fig. 1. Fe-Mn-S. Boundary of the homogeneity range of liquid Fe at 1600°C

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Fe–Mn–S

13

Fig. 2. Fe-Mn-S. Quasibinary system FeS-MnS. Full lines calculated from the dataset of [1998Mie], dashed lines as assessed by [1988Rag]

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14

Fe–Mn–S

Fig. 3. Fe-Mn-S. Composition - pressure diagram of the quasibinary system MnS-FeS at 1000°C

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15

Fig. 4. Fe-Mn-S.

Reaction scheme, calculated from the dataset of [1998Mie]

Fe–Mn–S

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16

Fig. 5a. Fe-Mn-S.

Fe–Mn–S

Calculated liquidus surface of the partial system Fe-Fes-MnS-Mn with isotherms up to 2000°C

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

Fig. 5b. Fe-Mn-S.

Landolt-Börnstein New Series IV/11D4

17

Enlarged part of the liquid surface between Fe and FeS from 0 to 10 at.% Mn

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18

Fig. 5c. Fe-Mn-S.

Fe–Mn–S

Enlarged part of liquidus surface along the Fe-Mn edge

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S

Fig. 5d. Fe-Mn-S.

Landolt-Börnstein New Series IV/11D4

19

Enlarged part of liquidus surface between 40 and 50 at.% S

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20

Fe–Mn–S

Fig. 6. Fe-Mn-S. Calculated liquidus surface of the Fe corner

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21

Fig. 7. Fe-Mn-S. Calculated isothermal section at 1600°C

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22

Fe–Mn–S

Fig. 8. Fe-Mn-S. Calculated isothermal section at 1500°C

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Fe–Mn–S

23

Fig. 9. Fe-Mn-S. Calculated isothermal section at 1400°C

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24

Fe–Mn–S

Fig. 10. Fe-Mn-S. Calculated isothermal section at 1300°C

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Fe–Mn–S

Fig. 11. Fe-Mn-S.

Landolt-Börnstein New Series IV/11D4

25

Calculated isothermal section at 1200°C

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26

Fig. 12. Fe-Mn-S.

Fe–Mn–S

Calculated isothermal section at 1100°C

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Fe–Mn–S

Fig. 13. Fe-Mn-S.

Landolt-Börnstein New Series IV/11D4

27

Calculated isothermal section at 1000°C

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28

Fig. 14. Fe-Mn-S.

Fe–Mn–S

Compositions of coexistent phases γ and Q at 1100, 1200 and 1300°C

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Fe–Mn–S

Fig. 15. Fe-Mn-S.

Landolt-Börnstein New Series IV/11D4

29

Isothermal section at 800°C

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30

Fig. 16. Fe-Mn-S.

Fe–Mn–S

Phase diagram of the sulﬁdes P and Q in equilibrium with γ

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S References [1913Roe]

[1928Shi]

[1933Vog]

[1934Mey]

[1937Vog]

[1937Wen] [1949Jae]

[1952She] [1955Tur1]

[1955Tur2]

[1960Mch]

[1963Kan]

[1964Cha] [1964Kul] [1966Kie]

[1966Sch]

[1967Bro] [1968Ska]

[1969Ban]

Landolt-Börnstein New Series IV/11D4

31

Roehl, G., “About Sulﬁde Inclusions in Iron and Steel: A Contribution to the Theory of Desulphurization of Irons” (in German), Stahl Eisen, 33(14), 565–567 (1913) (Experimental, Phase Diagram, Phase Relations, 3) Shibata, Z., “The Equibrium Diagram of the Iron Sulphide-Manganese Sulphide System”, Tech. Rep. Tohoku Imp. Univ., 7, 279–289 (1928) (Experimental, Phase Diagram, Phase Relations, 10) Vogel, R., Baur, H., “The Iron-Iron Sulphide-Manganese Sulﬁde-Manganese System” (in German), Arch. Eisenhuettenwes., 6(11), 495–500 (1933) (Experimental, Phase Relations, Phase Diagram, #, *, 6) Meyer, O., Schulte, F., “The Equilibrium FeS + Mn = MnS + Fe at High Temperatures” (in German), Arch. Eisenhuettenwes., 8, 187–195 (1934) (Experimental, Phase Relations, Phase Diagram, 21) Vogel, R., Hotop, W., “The Phase Diagram of the Iron-Iron Sulphide-Manganese SulhpideManganese System” (in German), Arch. Eisenhuettenwes., 11(1), 41–54 (1937) (Experimental, Phase Diagram, Phase Relations, #, *, 13) Wentrup, H., “Formation of Sulphide Inclusions in Steel” (in German), Techn. Mitt. Krupp, 5, 131–152 (1937) (Review, Morphology, 27) Jänecke, E., “S-Fe-Mn” (in German) in “Kurzgefasstes Handbuch Aller Legierungen”, Winter Verlag, Heidelberg, 722–724 (1949) (Review, Crys. Structure, Phase Diagram, Phase Relations, 5) Sherman, C.W., Chipman, J., “Activity of Sulphur in Liquid Iron and Steel”, J. Metals, 4, 597–602 (1952) (Experimental, Phase Relations, Thermodyn., 12) Turkdogan, E.T., Ignatowicz, S., Pearson, J., “The Solubility of Sulphur in Iron and IronMangannese Alloys”, J. Iron Steel Inst., 180, 349–354 (1955) (Experimental, Phase Relations, Thermodyn., 10) Turkdogan, E.T., Ignatowicz, S., Pearson, J., “Solid Solubility of Sulfur in Iron and IronManganese Alloys” (in French), Rev. Metall., 52(9), 725–730 (1955) (Experimental, Phase Relations, 7) Mchedlishvili, V.A., Lyubimova, A.M., Samarin, A.M., “The Manganese Function at the Elimination of the Unfavourable Sulfur Effect on the Steel Quality” (in Russian), Gos. Nauchno-Tekhn. Izd. Literatury po Chern. i Tsvet. Metall, Moscow, 56pp. (1960) (Experimental, Phase Relations, Morphology, 37) Kaneko, H., Nishizawa, T., Tamaki, K., “Study on Phase Diagrams of Sulphides in Steels” (in Japanese), Nippon Kinzoku Gakkai Shi, 27(7), 312–319 (1963) (Experimental, Phase Relations, 23) Chao, H.C., Van Vlack, L.H., Oberin, F., Thomassen, L., “Hardness of Inclusion Sulﬁdes”, Trans. Am. Soc. Met., 57, 885–891 (1964) (Experimental, Phase Relations, Phase Diagram, 5) Kullerud, G., “Review and Evaluation of Recent Research on Geologically Signiﬁcant SulﬁdeType Systems”, Fortschritte Mineral., 41(2), 221–270 (1964) (Review, Phase Diagram, 109) Kiessling, R., Westman, C., “Sulphide Inclusions and Synthetic Sulphides of the (Mn, Me)S Type”, J. Iron Steel Inst., 204, 377–379 (1966) (Experimental, Phase Relations, Crys. Structure, Morphology, 19) Schindlerova, V., Buzek, Z., “Effect of Aluminium, Titanium, Manganese, Zirconium and Cerium on the Solubility and Activity of Sulfur in Molten Iron at 1600°C” (in Czech), Hutnicke Listy, 21(3), 169–175 (1966) (Experimental, Thermodyn, 14) Brown, J.R., “Sulphur Potentials in Iron and in Iron-Manganese Alloys”, J. Iron Steel Inst., 205, 154–157 (1967) (Calculation, Thermodyn., 22) Skala, J., Riman, R., “The Inﬂuence of Certain Elements on the Chemical Composition of Iron Sulphides” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 14(3), 115–122 (1968) (Experimental, Phase Relations, Morphology, 0) Ban-ya, Sh., Chipman, J., “Sulfur in Liquid Iron Alloys: II. Effects of Alloying Elements”, Trans. Met. Soc. AIME, 245(1), 133–143 (1969) (Experimental, Thermodyn., 18) MSIT®

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32 [1969Sal] [1969Sch]

[1970Nis]

[1971Bru]

[1971His]

[1971Kor]

[1971Nak]

[1971San]

[1971Ska]

[1971Ski]

[1971Tur]

[1972Kor]

[1973Bru]

[1973Buz]

[1973Das]

[1973Kir]

[1973Wyj]

Fe–Mn–S Salter, W.J.M., Pickering, F.B., “Composition and Constitution of Nonmetallic Inclusions in 1 % C-Cr Steels”, J. Iron Steel Inst., 207(7), 992–1002 (1969) (Experimental, Phase Relations, 26) Schindlerova, V., Buzek, Z., “The Effect of Aluminium, Titanium, Manganese, Zirconium and Cerium on the Solubility and Activity of Sulfur in Molten Iron at 1600°C” (in German), Freiberger Forschungshefte, 117B, 43–58 (1969) (Experimental, Phase Relations, Thermodyn., 14) Nishikawa, K., Ito, K., Sano, K., “The Effect of the Alloying Elements on the Solubility of Sulfur in δ -Iron” (in Japanese), Tetsu to Hagane, 56, 1467–1476 (1970) (Experimental, Thermodyn., 16) Brusq Le, H., Delmaire, J.-P., Marion, F., “About Electric Properties of the FeS, CoS and NiS Sulﬁdes at High Temperatures. Comparison with the MnS Sulﬁde” (in French), C. R. Acad. Sci. Paris, C273(2), 139–142 (1971) (Experimental, Electr. Prop., 7) Hisada, H., Ito, K., Sano, K., “On the Solid State Reactions Between Mn-Fe Alloy and Synthetic Sulﬁde Inclusion”, Trans. Iron Steel Inst. Jpn., 11(2), 142–143 (1971) (Experimental, Phase Relations, Morphology, 0) Kor, G.J.W., Turkdogan, E.T., “Sulﬁdes and Oxides in Fe-Mn Alloys: Part II. Precipitation of Solid Sulﬁdes and Liquid Oxysulﬁdes During Oxidation of Iron Alloys”, Metall. Trans., 2(6), 1571–1578 (1971) (Experimental, Phase Relations, Morphology, 18) Nakao, H., Kirkaldy, J.S., “Thermodynamics and Kinetic Reactions in the γ-Fe-FeS-MnS System at 1300°C” (in Russian), in “Fiz. Khim. Osn. Proizvod. Stali”, Moscow, Nauka, 32–40 (1971) (Experimental, Phase Relations, 23) Sano, N., Iwata, M., Hosoda, H., Matsushita Y., “Phase Relations of Fe-Mn-S System at 1330 and 1615°C”, (in Japanese), Tetsu to Hagane, 57, 1984–1989 (1971) (Experimental, Phase Diagram, 7) Skala, I., Riman, R., “The Elements Inﬂuence on the Composition of the Sulﬁde Inclusions in Iron” (in Russian) in “Fiz.-Khim. Osnovy Proizvodstva Stali”, Moscow, Nauka, 216–220 (1971) (Experimental, Phase Relations, Morphology, 0) Skinner, B.J., Luce, F.D., “Solid Solutions of the Type (Ca, Mg, Mn, Fe)S and their Use as Geothermometers for the Enstatite Chondrites”, Am. Mineral., 56(7–8), 1269–1296 (1971) (Experimental, Phase Relations, 19) Turkdogan, E.T., Kor, G.J.W., “Sulphides and Oxides in Fe-Mn Alloys. Part I. Phase Relations in the Fe-Mn-S-O System”, Metall. Trans., 2(6), 1561–1570 (1971) (Review, Experimental, Phase Relations, 10) Kor, G.J.W., Turkdogan, E.T., “Sulphides and Oxides in Fe-Mn Alloys. Part III. Formation of Oxysulphides During Freezing of Steel”, Metall. Trans., 3(5), 1269–1278 (1972) (Calculation, Phase Relations, 19) Brusq Le, H., Delmaire, J. P., “Determination of the Regions of Stability of the Cubic and Hexagonal Solid Solutions (Mn,Fe)S as a Function of Sulfur Pressure and Temperature” (in French), Compt. Rend. Acad. Sci. Paris, Ser. C, 276(7), 603–605 (1973) (Experimental, Phase Relations, 6) Buzek, Z., “Effect of Alloying Elements on the Solubility and Activity of Oxygen and Sulphur in Liquid Iron at 1600°C”, Int. Symp. Metall. Chem. - Appl. Ferrous Metall., Shefﬁeld, July 1971, Iron and Steel Inst, London, 173–177 (1973) (Experimental, Review, Crys. Structure, *, 8) Dashevsky, V.Ya., Kashin, V.I., “Solubility and Activity of Sulfur in Manganese and its Alloys” (in Russian), Izv. Akad. Nauk SSSR, Met., (5), 85–88 (1973) (Experimental, Thermodyn., Phase Relations, 2) Kirkaldy, J.S., Nakao, H., Clark, I.S.R., Smith, P.N., “An Investigation of the Phase Constitution of Fe-Mn-S in the Vicinity of 1300°C. Paper I”, Canad. Metall. Quart., 12(1), 45–51 (1973) (Experimental, Phase Diagram, Phase Relations, 14) Wyjadlowski, J., Boos, J.-Y., Poyet, P., Goux, C., “Inﬂuence of Manganese on the Nature of Sulphides and the Cold and Hot Brittleness of Iron-Sulfur-Manganese Alloys with High Purity” (in French), C. R. Acad. Sci. Paris, C, 276(5), 383–386 (1973) (Experimental, Interface Phenomena, Mechan. Prop., 4)

DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–S [1974Sig] [1975Big] [1975Ito1]

[1975Ito2] [1975Sch]

[1975Tur] [1976Eﬁ]

[1976Hil1]

[1976Hil2]

[1976Man]

[1977Fis]

[1978Fis1]

[1978Fis2]

[1978Shi]

[1978Uhr]

[1980Bra] [1980Ito]

[1980Nis]

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33

Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 (1974) (Review, Thermodyn., 249) Bigelow, L.K. Flemings, M.C., “Sulphide Inclusions in Steel”, Metall. Trans. B, 6, 275–283 (1975) (Experimental, Phase Diagram, Phase Relations, 24) Ito, I., Kamazawa, T., Matsubara, I., “The Fe-Mn-S Phase Diagram. I. Three-Phase Regions” (in Japanese), Tetsu to Hagane, 61, 503 (1975) (Experimental, Phase Relations, Phase Diagram, 0) Ito, I., Kamazawa, T., “The Fe-Mn-S Phase Diagram. II. The eutectic reaction L⇌ Fe + FeS + Q” (in Japanese), Tetsu to Hagane, 61, 504 (1975) (Experimental, Phase Diagram, Phase Relations, 0) Schuermann, E., Stroesser, H.J., “A Study of the Melting Equilibria in the Partial Diagram Fe-FeS-Mn-MnS” (in German), Arch. Eisenhuettenwes., 46, 761–766 (1975) (Experimental, Phase Diagram, Phase Relations, 20) Turkdogan, E.T., “Discussion of “Sulphide Inclusions in Steel” ”, Metall. Trans. B, 6, 663–664 (1975) (Experimental, Phase Diagram, Phase Relations, Morphology, 3) Eﬁmov, V.A., Nakonechnyi, N.F., Lesnikova, E.V., Ishchuk, N.Ya., “The Chemical Composition of Sulphides in the Fe-Mn-S System” (in Russian), Izv. Akad. Nauk SSSR, Met., (1), 201–205 (1976) (Calculation, Phase Relations, 5) Hillert, M., Staffansson, L.-I., “On the Interaction between Three Liquid Miscibility Gaps in a Reciprocal System”, Acta Metall., 24, 1079–1082 (1976) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 5) Hillert, M., Staffansson, L.-I., “A Thermodynamic Analysis of the Phase Equilibria in the Fe-Mn-S System”, Metall. Trans. B, 7, 203–211 (1976) (Theory, Phase Relations, Phase Diagram, Thermodyn., 23) Mann, G.S., Van Vlack, L.H., “FeS-MnS Phase Relationships in the Presence of Excess Iron”, Metall. Trans. B, 7, 469–475 (1976) (Experimental, Phase Relations, Phase Diagram, 23) Fischer, M. Schwerdtfeger, K., “Thermodynamics of the System Fe-Mn-S. I. Activities in Iron Sulﬁde-Manganese Sulﬁde Solid Solutions in the Temperature Range 1100 to 1400°C”, Metall. Trans., 8, 467–470 (1977) (Experimental, Thermoyn., Phase Relations, 14) Fischer, M., Schwerdtfeger, K., “Thermodynamics of the System Fe-Mn-S: Part II. Solubility of Sulfur and Manganese in γ -Iron Coexisting with Sulﬁde in the Temperature Range 1100 to 1300°C”, Metall. Trans. B, 9, 631–634 (1978) (Experimental, Phase Relations, 12) Fischer, M., Schwerdtfeger, K., “Thermodynamics of the System Fe-Mn-S: Part III. Equilibria Inlvolving Solid and Liquid Phases in the Temperature Range 1100 to 1300°C”, Metall. Trans. B, 9, 635–641 (1978) (Experimental, Thermodyn., Phase Relations, Phase Diagram, 15) Shibanova, L.N., Lepinskikh, B.M., Vostryakov, A.A., “Transport Characteristics of Melts FeS-MnS, FeS-MnO and FeS-Cr2O3” (in Russian), Izv. Akad. Nauk SSSR, Neorg. Mater., 14(6), 1036–1039 (1978) (Experimental, Transport Phenomena, 8) Uhrenius, B., “A Compendium of Ternary Iron-base Phase Diagrams”, Hardenability Concepts with Applications to Steel, (Eds.): Doane, D.V., Kirkaldy, J.S., Proc. Symp. Held Sheraton-Chicago Hotel, Oct. 24–26, 1977, Metall. Soc. AIME Heat Treat. Com./Amer. Soc Met. Activ. Phase Trans., 28–81 (1978) (Phase Diagram, Phase Relations, Thermodyn., Calculation, 53) Brandes, E.A., Flint, R.F., “Mn-Fe-S” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 117–117 (1980) (Review, Crys. Structure, Phase Relations, Phase Diagram, 3) Ito, Y., Yonezawa, N., Matsubara, K., “The Composition of Eutectic Conjugation in the Fe-Mn-S System”, Trans. Iron Steel Inst. Jpn., 20, 19–25 (1980), translated from Tetsu to Hagane, 65(3), 1979, 391–398 (Experimental, Phase Relations, Phase Diagram, 21) Nishida, K., Narita, T., Tani, T., Sasaki, G., “High-Temperature Sulﬁdation of Fe-Mn Alloys”, Oxid. Met., 14(1), 65–83 (1980) (Experimental, Phase Diagram, Phase Relations, Interface Phenomena, 16)

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DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

34 [1981Nis]

[1982Kub] [1983Uto]

[1984McC]

[1987Pap]

[1988Rag]

[1990Sou] [1995Bou]

[1995Oik]

[1998Hua] [1998Mie]

[1998Val]

[2000Kim]

[2000Oht]

[2001Eri] [2004Liu]

[2004Rag] [2004Wit]

Fe–Mn–S Nishizawa, T., Hasebe, M., “Computer Calculation of Phase Diagrams of Iron Alloys” (in Japanese), Tetsu to Hagane, 67(14), 2086–2097 (1981) (Review, Phase Relations, Phase Diagram, Thermodyn., 110) Kubaschewski, O., “Iron-Sulfur” in “Iron - Binary Phase Diagrams”, Springer-Verlag, New York, 125–128 (1982) (Review, Phase Diagram, #, 20) Utochkin, Yu.I., Mendelev, V.A., Grigoryan, V.A., Vestfal, S.V., “Experimental Study of Lamination in Metallurgical System” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., (7), 5–8 (1983) (Experimental, Phase Relations, 5) McCammon, C.A., Jackson, I., Ringwood, A.E., Cashion, J.D., “The Binary Systems FeSMgS and FeS-MnS: Mössbauer Spectroscopy of the B1 Solid Solutions and High-Pressure Phase Equilibria”, Phys. Chem. Miner., 11(4), 182–193 (1984) (Experimental, Electronic Structure, Crys. Structure, Phase Relations, Phase Diagram, #, *, 39) Papaiacovou, P., Schmidt, H.P., Erhart, H., Grabke, H.J., “High Temperature Sulﬁdation of Fe-Mn Alloys and Mn in H2-H2S”, Werkst. Korros., 38(9), 498–506, (1987) (Experimental, Interface Phenomena, 20) Raghavan, V., “Fe-Mn-S (Iron-Maganese-Sulphur) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met., Calcutta, 2, 154–173 (1988) (Review, Phase Relations, Phase Diagram, #, *, 47) Southwell, G., Young, D.J., “Sulﬁdation Behavior of a Binary Fe-Mn Alloy”, Oxid. Met., 34 (3–4), 161–172, (1990) (Experimental, Interface Phenomena, 16) Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Trans., B, 26, 467–484 (1995) (Calculation, Thermodyn., 85) Oikawa, K., Ohtani, H., Ishida, K., Nishizawa, T., “The Control of the Morphology of MnS Insclusions in Steel during Solidiﬁcation”, ISIJ Int., 35(4), 402–408 (1995) (Experimental, Phase Relations, 20) Huang, W., “An Assessment of the Fe-Mn System”, Calphad, 13, 243–252 (1989) (Assessment, Calculation, Thermodyn., 35) Miettinen, J., Hallstedt, B., “Thermodynamic Assessment of the Fe-FeS-MnS-Mn System”, Calphad, 22(2), 257–273 (1998) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 29) Valeev, R.G., Tanklevskaya, N.M., Mikhaylov, G.G., “Phase Equilibria in the Fe-Mn-S System at the Temperatures of the δ-Iron Existence” (in Russian), Izv. Vyssh. Uchebn. Zaved. Chern. Metall., (3), 72–73 (1998) (Calculation, Phase Relations, Phase Diagram, Thermodyn., 4) Kim, E.C., “Crystallographic and Magnetic Properties of Iron Sulﬁdes Doped with 3d Transition Metals”, J. Mater. Sci. Letter., 19, 693–694 (2000) (Experimental, Crys. Structure, Magn. Prop., 8) Ohtani, H., Oikawa, K., Ishida, K., “Optimization of the Fe-Rich Fe-Mn-S Ternary Phase Diagram”, High Temp. Mater. Proces., 19(3–4), 197–210, (2000) (Calculation, Phase Diagram, Phase Relations, Thermodyn., #, *, 28) Eriksson, L., Kalinowski, M.P., “Mn1–xFexS, x = 0.05, an Example of an Anti-Wurtzite Structure”, Acta Crystallogr., Sect. E, E57(11), i92–i93 (2001) (Experimental, Crys. Structure, 10) Liu, Z., Kobayashi, Y., Nagai, K., “Crystallography and Precipitation Kinetics of Copper Sulﬁde in Strip Casting Low Carbon Steel”, ISIJ Int., 44(9), 1560–1567 (2004) (Experimental, Crys. Structure, Morphology, 37) Raghavan, V., “Fe-Mn-S (Iron-Manganese-Sulfur)”, J. Phase Equilib. Diffus., 25(4), 371–372 (2004) (Review, Phase Diagram, Phase Relations, #, *, 11) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Calculation, Thermodyn., #, 34)

DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–S [2005Nam]

[Mas2] [V-C2]

Landolt-Börnstein New Series IV/11D4

35

Nam, H.D., Kim, E.C., Han, J.S., “Mössbauer Study of Iron Sulﬁdes Doped with 3d-transition Metals”, Solid State Commun., 135(5), 327–329 (2005) (Experimental, Crys. Structure, Electronic Structure, Phase Relations, 8) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

MSIT®

DOI: 10.1007/978-3-540-78644-3_20 # Springer 2008

Fe–Mn–Si

1

Iron – Manganese – Silicon Nathalie Lebrun

Introduction Being driven by the potential in industrial application as shape memory material, the Fe-Mn-Si based alloys have attracted intensive studies and considerable achievements were made in past decades. For example, Fe-Mn-Si alloys have recently brought out a promising potential to be used as tighteners or pipe couplings at a large scale [2005Wan]. Addition of Cr or Ni to the Fe-Mn-Si alloys improves their Shape Memory Effect (SME) and corrosion resistance [2005Lin]. A martensite transformation can occur if the alloy is cooled down to below the Ms (martensite start) temperature of the martensitic transformation (γFe) → (εFe), or, if a stress is applied even at temperature above Ms. On the other hand, a reverse martensitic transformation (εFe) → (γFe) can take place if the alloy is heated above the As (austenite start) temperature and presents non-thermoelastic property. The iron disilicide αFeSi2 is also a promising material for photovoltaics, optoelectronics and thermoelectrics. It is a semiconductor that presents a p-type conduction with different doping additives as for example Mn [2005Jia]. Fe-Mn-Si has superior features such as good formability, excellent workability, low electrical resistivity, chemical stability, high oxidation resistance, low cost of raw material and nontoxicity. It is also a thermoelectric good candidate for use up to 927°C. But compared with the traditional Ni-Ti and Cu based shape memory alloys, the recoverable strain and recovery stress of Fe-Mn-Si alloys are quite low which limit their practical applications [2000Dai]. That is why several works on thermomechanical treatment, change of composition, doping process were done in order to improve the shape memory properties of Fe-Mn-Si alloys. A comprehensive review on SME regarding the Fe-Mn-Si system is done by [2000Hsu]. [1988Ray] and [1994Rag] present a complete review of the Fe-Mn-Si ternary system. All experimental and thermodynamic optimization works are reported in Table 1. Binary Systems Using new experimental thermodynamic data, the Fe-Mn system has been recently reassessed and the Calphad description was updated by [2004Wit]. This new reevaluation of the phase equilibria leads to consistently better ﬁts to the available experimental data. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). Consequently, the Fe-Mn system is accepted from [2004Wit]. After [Mas2], the liquidus and solidus phase boundaries in the Fe rich portion of the Fe-Si phase diagram was measured by [2005Mec] and thermodynamically reassessed by [1998Mie]. The DTA measurements done by [2005Mec] reveal a signiﬁcant shift compared to [Mas2] in the solidus and liquidus curves in the range between 20 and 25 at.% Si, suggesting that the A2-B2 (and perhaps B2-D03) ordering transition occurs in large part through the two-phase temperature regions. Since these careful experimental data are identical to those used by [1998Mie] for its thermodynamic assessment, these data are retained in this report. Nevertheless, a more sophisticated thermodynamic treatment of the ordering transition is necessary for a better accuracy of the Fe-Si diagram in the range from 20 to 35 at.% Si. No new phase diagram has been available in the literature regarding the Mn-Si binary system and it has been accepted from [Mas2]. Solid Phases All the data on unary, binary and ternary phases are indicated in Table 2. Several ternary compounds have been reported in the literature. [1937Vog] and [1973Ish] detected respectively the Mn5Fe12Si11 and Mn3Fe5Si2 compounds which are not retained in this assessment since later works did not conﬁrm their existence. Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

2

Fe–Mn–Si

[1964Gup] found a ternary phase Mn77Fe4Si19, called τ, at 1000°C with a non stoichiometric composition. The crystal structure of τ has been precisely characterized by [1977Sho] and the corresponding parameters and others characteristics are reported in Table 2. The unit cell is presented as a superstructure containing 2 · 110 atoms with the c axis repeat equal to (873.4 ± 0.1) · 2 pm. A complete solid solution is observed between FeSi and MnSi [1956Gla1, 1957Tav, 1958Aro, 1962Gla, 1968Set], Mn5Si3 and Fe5Si3 [1956Gla1, 1958Aro, 1962Gla, 1968Set] and α2Fe3Si and αMn3Si [1956Gla2, 1962Gla]. The lattice parameters of the cubic compound Mn1–xFexSi (0 ≤ x ≤ 1) vary linearly [1968Sid, 1958Aro, 1996Spo]. Using density-functional theory, [2003Luo] noticed a transition from an insulator for x = 1 to a metallic state with long range magnetic order at the Mn rich side. The lattice parameters of the compound (Mn1–xFex)5Si3 (0 ≤ x ≤ 1) ﬁrst display an approximately linear increase as Mn is initially substituted by Fe [1958Aro, 1972Joh, 1973Bin, 1976Sud] with ∼2.2 pm/Mn atom for a and 1.7 pm/Mn atom for c at room temperature [2004Can]. In the Fe rich region, [1973Bin] reported a helical spin structure for Mn2Fe3Si3 with a spiral period of 3000 pm along the c axis and a collinear c axis ferromagnetic alignment for MnFe4Si3. This spiral structure also exists for the Mn1.5Fe3.5Si3 below –213°C with an estimated turn angle of 24° between successive planes along the axis of the spiral [2004Can]. In the (Mn1–xFex)5Si3 series, Mn and Fe atoms occupy preferably the 6(g) (FeII or MnII) and/or the 4(d) (FeI or MnI) sites respectively with small amount of disorder [1972Joh, 1973Bin]. In the MnFe4Si3 phase, splitting is observed regarding some magnetic peaks. [1970Nar] concluded that essentially all the ﬁrst iron going to be substituted into Mn5Si3 go preferentially into the single crystallographic 4(d) sites with a slightly distorted octahedral array of silicon. For all the others compounds Mn3Fe2Si3, Mn2Fe3Si3 and MnFe4Si3, the 4(d) and 6(g) sites are occupied with an increasing occupation probability of the 6(g) with increasing Fe content [1970Nar]. The analysis of spin echo spectra of Mn in Fe3Si shows that Mn atoms prefer the Fe site (FeI) with eight ﬁrst-neighbor Fe atoms [1974Bab, 1974Bur]. This result was recently conﬁrmed by [2002AlN] using a theoretical Mössbauer study of the order-disorder phenomena in the (Mn1–xFex)3Si (x = 0, 0.967, 0.917, 0.833) leading to a split into a number of sextets [1975Pic, 1977Ver, 2002AlN] separated by about 40-45 kOe (3.2 to 3.6 MA·m–1) of the low magnetic ﬁeld component [2002AlN]. As Mn concentration increases, the probability of the existence of Fe atoms decreases indicating that the Mn atoms are substituted on the Fe sites [1977Ver]. The corresponding structure is a L12 structure [1974Yoo, 1977Yoo] instead of D03 structure found by [1956Gla1, 1956Gla2]. Higher Mn doping induces additional atomic disorder in the form of a partial occupation of FeII sites (surrounded by four Fe atoms) and SiII (surrounded by four Si atoms) sites. This ordering effect leads to a break on the concentration curve of the lattice parameter when half of the atoms is substituted in sublattice FeII and SiII by Mn atoms [1975Ver, 1977Yoo]. The solubility limit for 3d transition metal is found to be x = 0 in (Mn1–xFex)3Si alloys [1977Nic]. In the (Mn1–xFex)3Si series, the MnFe2Si compound was particularly investigated. [1956Gla1, 1956Gla2] ﬁrst measured the lattice parameter of this intermetallic compound and found a D03 type structure. [1976Zie] conﬁrmed the value of the lattice parameter and concluded that the structure is L12 type together with some preferential D03 Fe-Mn disorder. The solubility ranges of the other binary phases in to the ternary system are rather limited. The (βMn) phase exhibits a large homogeneity range with a maximum estimated to be 43.9 at.% Fe and 16.5 at.% Si at 1000°C [1966Bar]. The homogeneity range of (αFe) is found to be maximum at 10-12 at.% Mn and 10 at.% Si at 1000°C [1968Set]. [1962Wit] and [1962Gla] suggest that the βFeSi2 phase exhibits a solubility range up to 25 mol% MnSi2 (i.e. 8.3 at.% Mn, 25 at.% Fe and 66.7 at.% Si) and 10 mol% MnSi2 (i.e. 3.33 at.% Mn, 30 at.% Fe and 66.67 at.% Si), respectively. [1962Wit] measured the lattice parameters going from 268.5 to 269.0 pm for a and 512.3 to 511.8 pm for c. Unfortunately no temperature is indicated. The lattice parameters of the binary βFeSi2 phase are slightly lower than that accepted in this assessment and reported in Table 2. Finally, the maximum of the solubility of this phase inside the ternary is found at about 1120°C at 6.8 at.% Mn, 27.2 at.% Fe and 66.0 at.% Si [1974Abr]. The βFeSi2 structure presents two crystallographically non equivalent sites for Fe and Si (FeI, FeII, SiI, SiII). Using ﬁrst principles pseudopotential calculations based on Generalized Gradient Approximation (GGA) density function theory, [2002Tan] calculated the total

DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

3

energy of substitution of Mn dopant at the FeI and FeII sites and concluded that the dopant Mn prefers the FeI site. The MnSi1.75–x presents a solubility range with an upper limit of 26.1 at.% Mn, 11.2 at.% Fe and 62.7 at.% Si at 1000°C [1968Fli]. This result conﬁrms the assumption of [1962Wit] who also suggested the existence of this binary phase inside the ternary. [1962Gla] found a limit of 31.67 at.% Mn, 1.67 at.% Fe and 66.66 at.% Si with no indication of the temperature. Finally, the maximum of the solubility of this phase inside the ternary is found by [1974Abr] at about 1120°C and 26.9 at.% Mn, 9.0 at.% Fe and 64.1 at.% Si. The lattice parameters vary from 552.5 to 548.3 pm for a and 6555 to 9517.2 pm for c at 1000°C [1962Wit]. The lattice parameter c of the binary MnSi1.75–x phase is higher than that accepted in this assessment and reported in Table 2. ν, Mn4Si and R, Mn6Si present smaller solubilities which extend at 1000°C up to 1.5 at.% Fe [1964Gup] and 5 at.% [1968Set] Fe, respectively. Mn5Si2, considered as a metastable phase in the Mn-Si binary system, could be stabilized by Fe substitution. The (Mn,Fe)5Si2 is absent for the Fe content higher than 34 mass% at 750°C [1964Sen]. [1999Guo] presented the description of crystallographic approach of (γFe) → (εFe) martensitic transformation in Fe-Mn-Si based alloys. A set of crystallographic formulas was deduced by introducing shufﬂe and shear probability into Wechsler-Lieberman-Read theory. It was concluded that Bain distortion does not occur and the normal vector of simple shear corresponds to {111} of the (γFe) structure. The amplitude of the shufﬂe direction on (0001)hcp plane is very small and within the unit cell. Quasibinary Systems Three quasibinary sections were proposed by [1937Vog]: FeSi - MnSi, Mn5Fe12Si11 - Mn5Si3 and FeSi Mn5Fe12Si11. A continuous solid solution is observed between FeSi and MnSi [1937Vog, 1956Gla1, 1957Tav]. A minimum of the liquidus curve is measured at 1260°C and 50 mass% MnSi, i.e. 50.00 mass% Mn, 16.26 mass% Fe and 33.74 mass% Si (37.88 at.% Mn, 12.12 at.% Fe and 50.00 at.% Si). A solid-solid transformation detected by [1937Vog] between 1150 and 1230°C may be explained by the crystallization of the Mn5Si3 phase involved in a eutectic reaction L ⇌ Mn5Si3 + MnSi reported in the binary Mn-Si system. This is certainly due to a shift of the composition of the alloys. Consequently this solid-solid transformation is not retained. The MnSi-FeSi quasibinary section is shown in Fig. 1. The quasibinary sections Mn5Fe12Si11-Mn5Si3 and FeSi-Mn5Fe12Si11 are not retained in the present evaluation since the existence of the ternary compound Mn5Fe12Si11 is doubtful. Invariant Equilibria Four ternary reactions of the U type were determined by [1937Vog]: L + (γMn) ⇌ (βMn) + (γFe) at 1120°C, L + (βMn) ⇌ Mn3Si + (γFe) at 1020°C, L + Mn3Si ⇌ Mn5Si3 + (γFe) at 1010°C and L + FeSi ⇌ (αFe) + (γFe) at 1160°C. These ternary reactions measured by [1937Vog] are not in agreement regarding the phases involved in various binary reactions. Later, [1938Jae] reviewed the ternary system based on the experimental data of [1937Vog]. The ternary reaction found at 1010°C by [1937Vog] becomes a eutectic ternary reaction in the review of [1938Jae]: L ⇌ (γFe) + Mn3Si + Mn5Si3. This leads to a new invariant reaction at 1060°C [1949Jae]: L + (δFe) ⇌ (γFe) + Mn5Si3. The reaction measured at 1160°C then becomes in the work of [1938Jae]: L + FeSi ⇌ (δFe) + Mn5Si3 with a reaction temperature at 1030°C [1949Jae]. [1938Jae] deduced these new ternary reactions from more recent binaries than those used by [1937Vog] but they are not in agreement with the binary phase diagrams accepted in this assessment. Later [1988Ray] assessed the ternary system and proposed other reactions in good agreement with the accepted binary systems. However, [1988Ray] suggested a large existence of the Mn9Si2 which is in fact the ν (Mn4Si) compound. A smaller primary crystallization ﬁeld has been suggested in this assessment based on experimental data. The ternary reactions of [1988Ray] involving this compound have been replaced and a new ternary reaction L + ν + (βMn) ⇌ (Mn,Fe)3Si is proposed. On the other hand, the ternary reactions proposed by [1988Ray] regarding the βFeSi2 and the MnSi1.75–x could not been retained since they are not based on experimental data. Compositions and temperatures of all the ternary reactions are indicated in

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Table 3. Compositions data of the ternary reactions U2, U3 and U5 have been taken from the experimental work of [1937Vog]. The ternary reaction L ⇌ (γFe) + Mn3Si + Mn5Si3 proposed by [1938Jae] could not be retained in this assessment since the (Mn,Fe)3Si phase has a continuous solid solution whatever the temperature. This reaction has been replaced by the existence of a minimum involving the (Mn,Fe)3Si and the (γMn,γFe) phases. The reaction scheme is reported in Fig. 2. Liquidus, Solidus and Solvus Surfaces A partial liquidus surface has been presented by [1937Vog] in the Mn-Fe-MnFe-FeSi portion of the ternary system. This liquidus presents four ternary U type reactions and two maxima L ⇌ (αFe) + (γFe) and L ⇌ MnSi + Mn5Si3. Large disagreement is observed with the accepted binary Fe-Si system. In [1938Jae] version, one ternary reaction is eliminated as well as the two maxima. [1938Jae] proposed a new liquidus surface based on the work of [1937Vog] and new version of binary systems which differ from those retained in this assessment. Nevertheless large discrepancies are also noticed with the binaries accepted in this assessment. Later [1988Ray] assessed the liquidus surface which has been widely modiﬁed to be in agreement with the binaries. Nevertheless, the homogeneity range of the ν phase suggested by [1988Ray] is in contradiction with the small homogeneity range of this phase observed inside the ternary at 1000°C, i.e. 60°C lower than the in congruent melting temperature of this phase. Consequently the region of crystallization for this compound is taken narrower as indicated in Fig. 3. The Si rich corner is not complete since the ternary reactions involving βFeSi2 and MnSi1.75–x are unknown (question marks on the liquidus surface drawing). The isothermal lines are drawn from the measured data of [1937Vog]. Slight modiﬁcations were done regarding these curves to be in agreement with the accepted binaries. The partial liquidus surface is depicted in Fig. 3. Isothermal Sections An experimental partial isothermal section at 400°C was constructed by [1937Vog] in the Mn-Fe-MnFeFeSi part of the ternary system. Inconsistencies are observed with the binary Mn-Si and Fe-Si systems. The ν (Mn4Si) and R (Mn6Si) phases are missing on the isothermal section. Later [1938Jae] proposed a new version of this isothermal section along the Fe-Si binary system without the ternary compound suggested by [1937Vog] and using more recent versions of the binary systems. A Fe3Si2 phase was mentioned by these authors. This phase is certainly the η (Fe5Si3) which does not exist at 400°C according to the accepted Fe-Si binary system. Consequently these two versions of the isothermal section at 400°C could not be retained in this assessment. The Fe rich region of the isothermal section at 700°C has been studied by [1973Ish] showing the (γFe) (αFe) tie lines in the iron corner with Mn and Si varying up to 30 at.%. Using a Central Atoms Model, [1995Tan] calculated the (γFe)/(αFe) phase boundaries in the Fe rich corner (1 to 5 at.% Si and 1 to 12 at.% Mn) showing a good agreement with the experimental data. These results are in agreement with those thermodynamically assessed by [1993For]. Slight change has been done taking into account the homogeneity range of the (Mn,Fe)3Si phase in agreement with the accepted binaries. Moreover the η (Fe5Si3) phase has not been taken into account to be in agreement with the accepted Fe-Si binary system. Consequently, a new three-phase equilibrium has been added involving the Mn5Si3, (Mn,Fe)Si and (Mn,Fe)3Si phases. The maximum limits of the homogeneity ranges of MnSi1.75–x and αFeSi2 are estimated from the measurement at 1000°C assuming that it does not really change with variation of temperature of 300°C. Results of this compilation are presented in Fig. 4. The uncertain phase boundaries are indicated as dashed lines. The partial isothermal section at 900°C in the Fe rich corner has been experimentally investigated with Mn and Si content up to 30 mass% (30.34 at.% Mn and 46.01 at.% Si). [1973Ish] measured the tie lines (αFe) (γFe) and (αFe) - (βMn). Later [1991Lan] investigated the same region and included the (Mn,Fe)3Si phase, also suggested by [1968Set] at 1000°C. Since this last result is in agreement with the binary system Fe-Si, the phase relations proposed by [1991Lan] are retained in this assessment, whereas the results of [1973Ish] are rejected. The data of [1991Lan] in the Fe rich corner are compiled with the calculated isotherm done by [1993For] in the Mn rich part and are shown in Fig. 5. Slight modiﬁcation has been done regarding the homogeneity range of the (Mn,Fe)3Si, (αFe), (βMn), (γFe) and ν phases to be in agreement with the accepted binaries and are shown as dashed lines on the drawing. The maximum limit of the homogeneity DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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ranges of MnSi1.75–x and αFeSi2 are estimated from the isotherm at 1000°C. The uncertain phase boundaries are indicated as dashed lines. From the composition curves of the lattice parameters along the FeSi-MnSi and Fe5Si3-Mn5Si3 sections at 950°C, the composition of the two phases (Mn1–xFex)Si and (Mn1–xFex)5Si3 in equilibrium which each other was obtained by [1958Aro] and the tie lines in the two-phase region were estimated. [1964Gup] investigated the partial isothermal section at 1000°C in the range Mn30Fe70-Mn10Fe90 and up to 20 at.% Si. The homogeneity range of the ternary phase τ was measured. At the high Fe content, τ is found to be in equilibrium with the (βMn) and Mn3Si phases, whereas at lower Fe content an additional phase ν is found in equilibrium with τ. The ternary phase τ was not found by [1966Bar] who experimentally investigated the (βMn)/(Mn,Fe)3Si phase boundaries along the Mn-Fe binary system with increasing Si up to 30 at.%. Using the measured data of [1964Gup], [1966Bar] redrawn the isothermal section showing a large homogeneity range of the (βMn) phase. Later [1968Set] proposed a complete isothermal section where the solubility of MnSi1.75–x, ﬁrst suggested by [1968Fli], was taken into account. However, only schematic phase relations have been proposed in the Fe rich corner involving (αFe), (γFe) and Fe3Si phases. More recently, [1973Ish] determined the tie lines between these phases in the Fe rich ternary region with Mn and Si being up to 30 at.%. Unfortunately, [1973Ish] did not consider the (Mn,Fe3)Si phase which exists along the binary edge as a consequence of an order-disorder transition. Consequently, these last results could not be retained in this assessment. Recently, [1993For] thermodynamically assessed the isothermal section using the experimental data of [1966Bar]. An agreement is observed between experimental and calculated data. However the results on the Fe rich corner are not retained here since the βFe2Si phase does not exist at 1000°C in the accepted binary Fe-Si system and the (Mn,Fe)3Si phase was considered as stoichiometric. Finally, the isothermal section suggested by [1968Set] in the Mn rich corner is retained taking into account the phase boundaries (βMn)/(Mn,Fe)3Si experimentally determined by [1966Bar]. Moreover, the homogeneity ranges of the ν phase and the ternary phase τ are added from the good quality experimental work done by [1964Gup]. In agreement with the Mn-Si binary system, the homogeneity range of the Mn3Si phase is slightly modiﬁed on the drawing compared to the one proposed by [1968Set]. The solubility ranges of the βFeSi2 and MnSi1.75–x are deduced from the vertical section measured by [1974Abr]. The compiled isotherm is reproduced in Fig. 6. Temperature – Composition Sections Six isopleths have been constructed by [1937Vog] in the Fe-Mn-MnSi-FeSi region. Large discrepancies are observed with the accepted binary systems. [1937Vog] reported the Fe3Si2 phase which is in fact the η phase which does not exist below 825°C. Moreover the βFe2Si, η, ν, R, and (δMn) phases were not considered. This leads to large discrepancies on the solid-solid transformations involving these phases. Consequently, the isopleths of [1937Vog] can not be retained in this assessment. Using the liquidus data of [1937Vog], [1993For] thermodynamically reassessed these isopleths. These calculated results are in agreement with the accepted isothermal section at 1000°C for the two isopleths at xMn/xFe = 7.76 and 2.14 with Si varying from 0 to 35 mass% (0 to about 51 at.%). On the contrary, large discrepancies are noticed between the accepted isothermal section at 1000°C and the isopleths calculated by [1993For] at xMn/xFe = 0.837, 0.439, 0.176 and 0.0873 and 2.14 with Si varying from 0 to 35 mass%. The large homogeneity range of the (Mn,Fe)Si3 phase was not considered in the calculation and the (αFe) and the (βMn) phases have larger homogeneity ranges in [1993For] compared to the experimental data of [1966Bar, 1968Set]. Consequently, only the two ﬁrst isopleths of [1993For] are accepted in this assessment and are depicted in Figs. 7 and 8. A better agreement is observed between the experimental liquidus data of [1937Vog] and the calculation for the Mn rich part of the isopleths of [1993For], except the isopleths at xMn/xFe = 0.176 and 0.0873. The ﬁt of the liquidus curve is less satisfactory at high Si content. The phase boundary (βMn)/(βMn) + (Mn,Fe) Si3 is changed in agreement with the measured values of [1966Bar] at 1000°C and the homogeneity range of (Mn,Fe)3Si phase is considered in agreement with the accepted binary Mn-Si phase diagram. [1938Jae] assessed the Fe-Mn-Si ternary system and suggested an isopleth along Fe5Si3-Mn5Si3 over the temperature range 1000–1400°C which is not quasibinary since the Fe5Si3 phase only crystallizes between 825 and 1060°C. A continuous solid solution has been suggested between Fe5Si3 and Mn5Si3 which is reliable since the two phases have the same crystal structure and close lattice parameter values. This feature has Landolt-Börnstein New Series IV/11D4

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been conﬁrmed later in the review of [1956Gla1]. The ternary compound Mn5Fe12Si11 found by [1937Vog] was not taken into account and [1938Jae] suggested an equilibrium between liquid, FeSi and Mn5Si3 at the same composition. Unfortunately the isopleth proposed by [1938Jae] is not retained since large discrepancies (more than 50°C) are observed regarding the melting temperature of the L + (Mn,Fe)Si region at the Fe5Si3 composition compared to the one accepted in the binary Fe-Si. Moreover the variation of the composition along this section is not clear. Indeed the composition Mn5Fe12Si11 mentioned by [1938Jae] along the vertical section does not correspond to the Mn composition on the axis. From tie lines determinations in the temperature range 700–1000°C between (αFe), (γFe) and Fe3Si, [1973Ish] constructed the isopleth at xMn/xSi = 1 which is not in agreement with the accepted isothermal sections. Consequently this isopleth is rejected. The system MnSi1.75–x-FeSi2 is of eutectic type [1974Abr]. The eutectic corresponds to the composition 21.2 mass% Mn, 14.1 mass% Fe and 64.7 mass% Si (13.12 at.% Mn, 8.58 at.% Fe and 78.30 at.% Si) and occurs at 1125°C. Ambiguities arise from a more detailed interpretation of this isopleth. In the text, the results are discussed in terms of mol% FeSi2 whereas the axis composition of the diagram is expressed as mass% FeSi2. Large discrepancies are observed at the binary edge with the accepted Mn-Si and Fe-Si phase diagrams. In the diagram proposed by [1974Abr], the MnSi phase is absent at the MnSi1.72 composition and the αFeSi2 does not appear as a single phase. Finally, this vertical section is not retained in this assessment. Thermodynamics [1998Zai] used an ideal associated solution model for the description of the activities of the three components of the Fe-Mn-Si liquid alloys in the temperature range 1162–1536°C and the composition range xMn ≤ 60 at.%. The experimental activities can be described by this model if the ternary complex MnFeSi is considered. The calculated ln(γMn) values deduced from this model are in good agreement with the experimental data obtained in the same work but are higher than the values measured by [1978Gee] and only in qualitative agreement with the measured data of [1979Ari]. [1996Zai1] pointed out that a possible reason for these discrepancies could be found in the experimental method used by [1978Gee] where the gas carrier was not saturated with Mn vapor and the oxidation of Si to SiO with oxygen contained in the carrier gas. Consequently the calculation of [1997Li2] and [1993For] using the uniﬁed interaction parameter model (UIPM) and the substitutional solution model respectively, are not retained in this assessment since these works are based on the experimental data of [1978Gee]. The activity data measured by [1996Zai1, 1996Zai2, 1998Zai] seem to be more reliable and less scattered. Consequently, these more recent experimental data are retained in this assessment. The corresponding silicon, manganese and iron isoactivity lines are depicted in Figs. 9, 10 and 11, respectively. The isoactivity lines of silicon are close to the secants connecting the Fe-Si and Mn-Si binary sides. There is a tendency for silicon to decrease the activity coefﬁcient of Mn as pointed out by [1987Bal, 1993For, 1995Bou]. The corresponding ﬁrst-order interaction parameter in the liquid was measured to be εMn(Si)(liq) = 4.9 by [1987Bal] where εMn(Si)(liq) = ∂ln γMn/∂ xSi and γMn = (xMn in pure Fe)/(xMn in the solution). The ﬁrst-order parameters of Mn and Si were measured in the (δFe) phase: εMn(Si)(δ) = εSi(Mn)(δ) = – 13±2 at 1527°C [1981Fuj]. [1984Bon] investigated experimentally the mixing enthalpy of liquid Fe-Mn-Si alloys (xFe/xSi = 8/2, 7/3, 4/6 and 3.5/6.5) at 1687°C showing large negative values due to strong attractive interactions Fe-Si and Mn-Si of the donor-acceptor type. Later [1988Sud, 1989Bon] completed by the measurement of the mixing enthalpy of liquid alloys at 1572°C along the Mn-FeSi and Fe-MnSi sections. [1980Bob] measured the mixing enthalpy in liquid alloys at 1527°C along the Mn5Si3-Fe5Si3 line showing a minimum enthalpy of –2.6 kJ·mol–1 at 45 mol% Mn5Si3. Some results are reported in Table 4. Using an associated-solution model which assumes the existence of some binary and one ternary complexes (MnFeSi) in the melts, the molar Gibbs energy and enthalpies of formation of Fe-Mn-Si liquid alloys have been calculated by [1996Zai1, 1996Zai2, 1998Zai]. The optimal value of the molar energy of formation for the ternary complex MnFeSi found by [1998Zai] is reported in Table 5. The enthalpy of formation data are in agreement with the values calculated by [1958Bon, 1960Bon] at 1327°C and [1984Bon] at 1687°C for three cross sections Fe70Si30 - Mn28.9Fe49.7Si21.4, Fe40Si60 - Mn33.7Fe26.5Si39.8 and Mn64.9Fe35.1 Mn29.4Fe24.8Si45.8. For the cross section Fe80Si20 - Mn25.5Fe59.6Si14.9 agreement is seen only for alloys DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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at high manganese content. [1988Sud] found higher heat effect of mixing than in [1996Zai1, 1996Zai2] and [1984Bon]. These discrepancies could be explained by the non-controlled oxidation of silicon in samples studied by [1988Sud]. Moreover, the results of [1958Bon] are in only qualitative agreement with the data of [1996Zai1, 1996Zai2] since the thermodynamic properties were predicted from the binary subsystems. In conclusion, the data of [1996Zai1, 1996Zai2] are retained in this assessment and their corresponding lines with the same Gibbs energy are shown in Fig. 12. Using a thermodynamic model introducing magnetic contributions from binaries, [1997Li1] evaluated the Gibbs energy of the (γFe) and (εFe) phases for the Fe rich alloys with 30 mass% Mn and 6 mass% Si (28.65 at.% Mn and 11.21 at.% Si). A decrease of these energies is observed in the temperature range 627°C to –73°C with G(γFe) < G(εFe). For the Fe alloy with 28.2 mass% Mn and 5.49 mass% Si (27.07 at.% Mn and 10.31 at.% Si), the measured critical driving force ΔGC for the reverse (α’Fe) → (γFe) transformation is estimated to be 68 J·mol–1 by [1997Li1] at As = 168°C (441 K), temperature calculated by [1997And]. This measured value of ΔGC is not in agreement with the calculated critical driving force of [1997Li1] for the Fe alloys with 30 mass% Mn and 6 mass% Si estimated to be ΔGC = 142 J·mol–1 at As = 157°C (430 K), temperature calculated by [1998Cot1]. A better agreement is observed between the experimental and calculated data of [1997And] using calorimetry technique and Thermocalc software with the thermodynamic description of [1993For]. Despite the fact that the surface of the alloy is probably oxidized, the measured values of [1997And] are preferred here. [1980Smi] measured the heat capacity for (Mn1–xFex)3Si (0.47 ≤ x ≤ 0.8) at temperature lower than 187°C. The magnetic contribution to the heat capacity was deduced and has been estimated to be 4.3 and 4.8 J·(mol ·K)–1 for x = 0.75 and 0.58, respectively. These values are quite reasonably in agreement with those calculated from a molecular ﬁeld approximation by the same authors. The entropy associated with magnetic ordering SF and reordering SR were derived. For example, the values regarding the MnFe2Si compound is found to be SR = 3.2 J·(mol·K)–1 and SF = 3.4 J·(mol ·K)–1 with a uncertainty of 10–20 %. SF decreased signiﬁcantly with the increase of the concentration x whereas SR is more or less constant. [1980Smi] concluded that the re-ordering transition at TR plays a more signiﬁcant role in the establishment of the magnetic state than a simple realignment of the magnetic moment as suggested by [1977Yoo]. The total magnetic entropy Sm is considerably lower than the 3Rln2 = 17.3 J·(mol·K)–1 for the 3 N magnetic spins with S = ½ [1980Smi, 1988Mil]. Notes on Materials Properties and Applications There exist three deformation stages in the Fe-Mn-Si alloys when an increasing stress is applied: (a) elastic deformation of (γFe); (b) formation of a stress induced martensite; (c) plastic deformation of (γFe). The martensitic reaction (γFe) → (εFe) is classiﬁed as a semi-thermoelastic transformation since the dislocation can move reversibly upon heating and the thermal hysteresis is as high as 100°C. The reverse martensite transformation (εFe) → (γFe) can also be assisted by intensive strain and occurs at a temperature far below the normal As temperature [1996Zha]. Moreover the nucleation process of the (εFe) phase does not strongly depend on soft modes [1999Hsu]. The parent austenite (γFe) phase transforms into martensite phase (εFe) by the formation and overlap of a stacking fault mechanism with low stacking fault energy based on the reversible motion of Schockley partial dislocation [2000Jin1, 2000Hsu, 2001Wan1, 2001Wan2]. The martensite start temperature does not markedly vary with the grain size of the (γFe) phase and there does not show a considerable lowering of the elastic modulus during the (γFe) → (εFe) transformation [2000Hsu]. Tension-compression asymmetry was observed in Fe-Mn-Si alloys strained by bending. [2005Sta] concluded that formation and reversion of stress-induced martensite occurs more readily in tension than in compression. Moreover, irreversible plastic deformation is more pronounced in the compression region, contributing to reduced shape memory. Tensile stress should be better for shape memory than compressive stress. The shape memory effect (SME) is associated with this stress-induced martensitic transformation by a predeformation at a temperature between Ms and Md [2005Wan] with increase of Si content in the alloy. The SME could improve by a decrease of the critical stress for inducing martensite, an increase of the amount of martensite and a strengthening of austenite [2000Dai, 2000Hsu]. The shape recovery rate in Fe-Mn-Si alloys is proportional to the volume of reversible martensite before recovery which can be estimated as the area covering an internal friction peak. Landolt-Börnstein New Series IV/11D4

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The good SME strongly depends on the composition of the alloys. Fe-Mn-Si alloys, which contain 28–34 mass% Mn and 4–6.5 mass% Si (27.26-32.30 at.% Mn and 7.62-12.08 at.% Si), exhibit a nearly perfect SME [2005Wan]. [2000Jin1] concluded that stacking fault energy, related to the critical driving force ΔGC, increases with addition of Mn (low SME) and decreases with the addition of Si (high SME) linearly as followed ΔGC = 215.23 + 7.923 {mass% Mn} – 46.38 {mass% Si} (in J·mol–1) leading to a linear evolution of the martensite start temperature as follows: Ms = 284.7 – 7.857 {mass% Mn} + 46.0 {mass% Si} (in K). Finally, the stacking fault energy of the (γFe) phase can be expressed as 180.54 + 7.923 {mass% Mn} – 46.38 {mass% Si} (in J·mol–1) [2000Jin2]. These three equations are only available within the composition range 24 < Mn < 32 and 4 < Si < 6 (in mass%). The linear evolution of Ms suggested by [2000Jin1] is not in agreement with the ﬁndings of [1998Cot1, 1999Cot] which stipulated that small additions of Si (less than 5 mass%) increase both Ms and Md temperatures, but further Si additions start to progressively decrease them at sufﬁciently high Mn contents [1990Sad]. These last results are qualitatively in fairly agreement with those reported by [1993For]. However various differences do exist: the lines for equal Ms and As are essentially parallel in the work done by [1998Cot2], while some of the Ms lines calculated by [1993For] signiﬁcantly approach each other at high Mn contents. These isolines calculated by [1998Cot2] would be preferred since a complete thermodynamic description of the martensitic transformation and its reverse transformation upon heating has been done considering the magnetic contribution which was not taken into account in the work done by [1993For]. Moreover, [1993For] considered the Resistance to Start Transformation Energy ΔGC (critical driving force) as independent of composition and equal to 50 J·mol–1. The experimental values of Ms and As measured by [1996Zha] for a Fe alloy with 29.44 mass% Mn and 6.2 mass% Si (28.07 at.% Mn and 11.56 at.% Si) and [1995Ron] for a Fe alloy with 29.9 mass% Mn and 6.0 mass% Si (28.56 at.% Mn and 11.21 at.% Si) are in general agreement with the calculated values of [1998Cot2] but 30°C lower than the calculated temperatures. Ms and As were estimated to be about 27°C and 127°C [1996Zha], and 34°C and 129°C [1995Ron] respectively instead of the respective calculated values 57°C and 157°C [1998Cot2]. The SME is also inﬂuenced by the machining of the materials. For example, Wire Electro-Discharge Machining (WEDM) surface of Fe alloy with 30 mass% Mn and 6 mass% Si present slight degradation of shape recovery due to the depression of the re-cast layer [2005Lin]. Deformation of the Fe alloy with 30.7 mass% Mn and 6.54 mass% Si (29.17 at.% Mn and 12.16 at.% Si) produced a complete SME in a wide temperature range (–269°C to 127°C) [1986Sat]. [1996Mat] compared the SME on hot rolled sheets for Fe alloy with 28 mass% Mn and 6 mass% Si (26.75 at.% Mn and 11.21 at.% Si) between mid-thickness and near surface layers. It was concluded that a maximum of shape recovery strain is obtained for specimen with a tensile axis parallel to the rolling direction (RD) or the transverse direction of the RD in the plane of the surface layer, i.e. axis preferentially oriented to <110>. The room temperature prestrained materials lead to lower SME due to the increase of the gap between the reverse starting and ﬁnishing martensite temperature As and Af. As the strain is increasing, the Af is greatly increased whereas the As keeps constant [1995Ron]. For example the shape recovery ratio decreases from 53 to 35% with increase strain from 2.4 to 6.2%. [1995Ron] suggested that a larger driving force ΔGC is required to reverse the stress-induced (εFe) martensite. Consequently the deformed specimen must be heated to higher temperature in order to obtain a better SME. The SME properties can also be improved by the repeated deformation and the number of heating cycles leading to an increase of the martensite start temperature. This training effect has been studied by [1993Wat] who found the major recovery of the SME at a temperature lower by 30°C after 13 deformation-heating cycles on Fe alloy with 31 mass% Mn and 6 mass% Si (29.60 at.% Mn and 11.21 at.% Si). The homogenization of the internal structure is improved during the cycles and is achieved by introduction of the (εFe) phase distributed in ﬁne structure which favors the SME. The addition of Al, Nb or Ti at about 1 mass% favors the ferrite formation and signiﬁcantly reduces the austenite stability resulting in duplex microstructure in austenite and ferrite. Austenite stabilizing additions of Ni or Mn are then necessary. Nevertheless, too many alloying additions are detrimental to the shape memory behavior. This decrease of the shape memory with addition of Ni and/or Mn is the results of a suppression in the temperature Ms [2007Sta]. On the contrary, carbon, nitrogen and rare earth elements were found to improve shape memory effect in Fe-Mn-Si alloys [2000Dai, 2000Hsu, 2005Wan]. The stacking fault energy of the (γFe) phase is then reduced and thus favors the SME.

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9

Several works show that the transition antiferromagnetic → paramagnetic of the (γFe) phase characterized by the Neel temperature TN(γFe) strongly affected the SME and the martensitic transformation [2000Wu, 2000Hsu]. In fact, the amount of (εFe) is related to Ms and (Ms–TN) [1996Qin]. For example in the Fe alloy with 30.30 mass% Mn and 6.10 mass% Si (28.91 at.% Mn and 11.39 at.% Si), the TN(γFe), equal to 27°C [1999Jin, 2000Wu], is slightly below the martensitic temperature Ms (Ms – TN(γFe) = 30°C) and the martensitic transformation is then distinctly suppressed [2000Wu]. These values are slightly different from those reported by [2000Hsu] (TN(γFe) = 20°C) and [1999Che] (TN(γFe) = 6°C) with Ms – TN(γFe) = 50°C and a stacking fault probability Psf estimated to be 2.73·10–3 [2000Hsu]. [1995Ron] found TN(γFe) = 24°C with Ms – TN(γFe) = 10°C for a Fe alloy with 29.9 mass% Mn and 6.0 mass% Si. A systematic investigation of the martensite transformation temperature and their inﬂuence on the SME has been carried out by [1996Qin] on Fe alloy with 27.77–32.01 mass% Mn and 4.10–6.10 mass% Si (27.01–30.54 at.% Mn and 7.80–11.38 at.% Si). It was concluded that a decrease of the Ms– TN(γFe) quantity with increasing Mn and Si content leads to a higher quality of the SME: Ms– TN(γFe) = 52°C with a SME of 35% for Fe with 27.77 mass% Mn and 4.10 mass% Si to Ms– TN(γFe) = 23°C with a SME of 82% for Fe alloys with 32.01 mass% Mn and 6.10 mass% Si. Finally, SME increases rapidly when Ms–TN(γFe) becomes positive [1986Sat]. Upon further cooling below TN(γFe), the martensitic transition could still occur, but the amount of the (εFe) phase formed is rather small and leads to a decrease of the area of the internal friction peak. With (Ms–TN) being smaller, the martensite transformation is suppressed, the pre-existing (α’Fe) martensite phase becomes smaller and the SME is good [1996Qin]. Contrary to the assumptions done by [2000Hsu, 2000Wu], [1999Che] concluded that, even when Ms is lowered below TN, martensite can also be induced to a great extent from the paramagnetic or the antiferromagnetic parent phase at different temperatures by application of stress. The alloy composition evidently affects the TN(γFe) temperature while the Neel temperature for the (εFe) phase TN(εFe) is little affected [1999Jin]. Addition of Si to Fe-Mn alloys lowers TN(γFe) [1986Mur], increases the susceptibility [1996Qin, 1998Qin, 2000Wu] and leads to a higher and sharper peak of the magnetic susceptibility at TN [1996Qin]. [2000Wu] found that when Mn content is 30 mass% and Si content is in the range 0–6 mass% the TN(γFe) temperature reduces about 25°C with increasing 1 mass% Si. These results are not in agreement with the empirical equations of [1999Jin] deduced from thermodynamic consideration of the antiferromagnetic (γFe) → (α’Fe) for Fe with 24–32 mass% Mn and 0–6 mass% Si (24.30– 30.55 at.% Mn and 0–11.21 at.% Si). It was also pointed out that when Si content is about 6 mass% (11.21 at.%) and Mn content is in the range of 25–35 mass% (23.90–33.40 at.%), the increase of the TN(γFe) is about 7°C with increasing 1 mass% Mn content [2000Wu]. TN of Mn rich (MnxFe1–x)Si alloys (x > 0.9) decreases rapidly as x is decreased [1987Gel]. The addition of rare earth elements to Fe-Mn-Si also gives lower TN(γFe) values [1999Hsu, 2000Wu]. In conclusion, the occurrence of the transformation (γFe) → (α’Fe) in Fe-Mn-Si based alloys is determined by the chemical driving force, the magnetic structure of the parent phase (γFe) and the external stress applied [1999Che]. An increase of the electrical resistance is observed during the martensitic transformation in Fe alloy with 30 mass% Mn and 6 mass% Si (28.65 at.% Mn and 11.21 at.% Si) whereas a decrease is noticed during the reverse martensitic transformation [1996Zha]. These results are in agreement with those of [1996Qin] for Fe alloys ranging from 27.77 mass% Mn and 4.10 mass% Si (27.01 at.% Mn and 7.80 at.% Si) to 32.01 mass% Mn and 6.10 mass% Si (30.54 at.% Mn and 11.38 at.% Si). This behavior was also observed in [1993Wat] showing a higher resistivity for powder alloys (31 mass% Mn and 6 mass% Si or 29.60 at.% Mn and 11.21 at.% Si) after 13 deformation-heating cycles. The hardness is not homogenous in the wire electro-discharge machining (WEDM) surface of the Fe alloys with 30 mass% Mn and 6 mass% Si (28.65 at.% Mn and 11.21 at.% Si). The hardness near the outer surface can reach 550 Vickers (5396 MPa), whereas for depth more than 50 μm the value is about 225 Vickers (2207 MPa) [2005Lin]. On bulk samples, the mechanical strength is improved after annealing for iron alloys containing about 20–30 mass% Mn (18.45–27.63 at.% Mn) and up to 10 mass% Si (18.02 at.% Si). The best mechanical performance was optimum for a Fe alloy with 25 mass% Mn and 2 mass% Si (24.82 at.% Mn and 3.88 at.% Si) after a plastic deformation [1976Zvi]. After deformation at 1000°C by rolling of 20%, this alloy gives a yield point of 85 kg·mm–2 (833.6 MPa) and an ultimate strength of 105 kg·mm–2 (1029.7 MPa). Landolt-Börnstein New Series IV/11D4

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Fe–Mn–Si

The magnetic phase diagram and magnetocaloric properties of the system Fe-Mn-Si have been investigated [2004Can, 2002Son]. MnFe2Si: This cubic compound has a saturation magnetic moment of 2.33 μB [1983Bus]. MnFe4Si3: This compound orders ferromagnetically [1970Nar] just below 27°C and the moments are aligned at approximately 40° to the c axis with higher values (1.4 μB and 2.5 μB for the 4d and 6g sites) than the site moments for Fe5Si3 [2004Can]. From the fact that the total magnetic moment of this compound is higher than in Fe5Si3, [2002Son] concluded that the Mn moments are coupled parallel to the Fe moments. A considerable magnetic-entropy change is observed around room temperature, the maximum value being 4 J·kg–1·K–1 for a ﬁeld change of 5 T. This relatively high value has been attributed by [2002Son] to the large value of the Mn moment when forced into a ferromagnetic arrangement. Mn1.5Fe3.5Si3: [2004Can] noticed that its magnetic structure is similar to that of MnFe4Si3 at –123°C with lower moments for 4d and 6g sites (0.9 μB and 1.9 μB). The Curie temperature is –8°C. The transition from the spiral to ferromagnetic phase is accompanied by a small increase in the cell volume suggesting that magnetoelastic effects may play a role. Mn2Fe3Si3: Magnetic order occurs below –196°C with however a higher Curie point (–23°C) than the previous components and the presence of a low temperature transition at –223°C [1973Bin]. Both of these ﬁndings are in contrast with neutron diffraction studies done by [2004Can]. This more recent investigation leads to the conclusion that the magnetic structure of Mn2Fe3Si3 seems to be an incommensurate antiferromagnet since a continuous increase of the intensity of the magnetic peak is observed between –265°C and –123°C. The magnetic entropy changes are positive, but the change in magnetic order with changing magnetic ﬁeld (0 to 5 T) is rather low [2002Son]. Mn3Fe2Si3: Two transitions have been observed with the ﬁrst corresponding to a paramagnetic to antiferromagnetic ordering at –148°C followed by a successive transition below –228°C [2002Son, 2004Can]. Between these two transitions, the antiferromagnetic phase [1970Nar] has a hexagonal cell [1973Bin]. The high temperature phase corresponds to a commensurate antiferromagnet with an ordering wave vector {1/2, 0, 0}. The lower transition is probably based on a spin reorientation of the moments from the hexagonal axis to a low temperature planar conﬁguration [2002Son]. The Curie temperature is located at 57°C [1973Bin]. At –196°C the saturation moment was measured to be 0.3 μB [1973Bin]. Mn4FeSi3: At temperatures between –203°C and –178°C, its magnetic structure is of the same type as that of the low temperature phase of Mn3Fe2Si3 below –223°C with a saturation moment at –196°C to be 1.4 μB [1973Bin]. No ﬁeld-induced magnetic phase transition has been observed [2002Son]. The Curie temperature of this antiferromagnetic phase [1970Nar] is located at 53°C [1973Bin]. The atomic magnetic moments of the (Mn1–xFex)Si (0 ≤ x ≤ 1) were calculated by [2003Luo] varying from –0.13μB (Mn0.5Fe0.5Si) to 0.55μB (Mn0.75Fe0.25Si) and from 0μB (Mn0.125Fe0.875Si) to 1.44μB (Mn0.75Fe0.25Si) for the Fe and Mn ions respectively. The calculated magnetic moment of the Mn ion is signiﬁcantly less than 3μB expected for the Mn4+ conﬁguration while Fe ions have a positive or a negative magnetic moment. Moreover it was found that for x < 0.875, the alloys start to show ferromagnetic order. These results are in agreement with the experiments of [1996Spo]. Indeed, [1996Spo] measured the magnetic transition temperature at about –244°C for MnSi and observed its decreasing down to –251°C if 2 at.% of Mn are substituted by Fe. The effect of Mn substitution on magnetic and thermal properties of (MnxFe1–x)3Si have been studied by [1998Muk] (0.4 ≤ x ≤ 0.6), [1977Yoo] (0 ≤ x ≤ 0.75) and [1976Sid] (0 ≤ x ≤ 0.67). Addition of Mn leads to an increase of the Debye temperature and an increase of the electron-magnetic contribution to the thermal expansion and the entropy [1988Mil]. On the contrary, the dilution of Fe atoms in Fe3Si by Mn atoms reduces the Curie temperature [1974Yoo, 1976Zie, 1988Mil]. Otherwise the magnon contribution to thermal expansion decreases with addition of Mn. [1976Lut, 1976Sid] demonstrated that series of transitions exist in these alloys leading to: 1) a ferromagnetic solution for alloys from Fe3Si to Mn0.99Fe2.01Si; 2) a ferromagnetic solution for alloys from Mn0.99Fe2.01Si to Mn2.01Fe0.99Si; 3) an antiferromagnetic solution for alloys from Mn2.01Fe0.99Si to Mn3Si. In the ferromagnetic solution, positive exchange interactions of Fe-Mn and Fe-Fe exist. At high Mn content the antiferromagnetic order is established because of the strong negative interaction of Mn-Mn type. In the intermediate solutions, a complex ferromagnetic structure is observed with a competition between the positive and negative interactions as described above. Various limits of this complex intermediate state were suggested Mn24.75Fe50.25Si25.00-Mn50.25Fe24.75Si25.00 [1976Sid], DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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11

Mn15Fe60Si25-Mn43.75Fe31.25Si25.00 [1998Muk], Mn18.75Fe56.25Si25.00-Mn43.75Fe31.25Si25.00 [1977Yoo] and Mn15Fe60Si25.00-Mn50.25Fe24.75Si25.00 [1976Lut]. The magnetic reordering temperature TR is very sensitive to the sample condition (ageing, heat treatment, magnetic ﬁeld) [1991Mil]. [1976Nic] showed that the Mn atoms which substituted the Fe atoms on the FeI sites have a magnetic moment which increased from 0 to 2.2 μB. This effect produced a decrease in the average moment of the other Fe sites from 1.35 μB at x = 0.87 to 0 μB at x = 0.75. [1991Mil] found that a long range ordering can be suppressed in Mn0.8Fe2.2Si compound in applied magnetic ﬁeld of about 0.4 T. Moreover low ﬁelds (1 to 2 mT) strongly inﬂuence the bulk magnetization. The (MnxFe1–x)5Si3 phase also presents a magnetic transition. Two transformations occur at low temperature characterized by the rearrangement of the antiferromagnetic ordering at TR and the transition to a paramagnetic state at TN [1976Sud]. A rapid decrease of the Curie temperature TC is observed for the Fe5Si3 rich alloys. [1976Sud] noticed that replacement of Mn atoms by Fe atoms weakly affects the temperatures TR for x > 0 [1977Yoo, 1980Smi] and TN. Agreement had been observed regarding the measured data of TR from [1977Yoo] and [1980Smi]. From magnetic hyperﬁne ﬁelds, [1972Joh] suggested that the relative magnitudes of the moments for FeI and FeII sites are the same for the entire series. Changes on magnetic properties of Fe alloy with 6.5 mass% Si and Mn addition less than 0.20 mass% (6.59 at.% Mn and 0.4 at.% Si), are fairly small [1976Nar, 1978Nar], except in the case of the maximum permeability (at 0.15 mass% Mn and annealing at 900°C for 20 h). The non-doped semiconducting material αFeSi2 usually presents p-type conduction over a wider range of Si/Fe ratios, but n-type conduction has sometimes been reported in the stoichiometric or Si excess conditions. [2005Jia] observed an evolution of the conduction to n-type during the eutectoid decomposition of a Mn-added αFe2Si5 alloy. This change is caused by the abundant Fe vacancies acting as donors in the supersaturated αFeSi2(Si) solution, which is a metastable state of the αFeSi2 phase which appeared in the eutectoid reaction βFeSi2 ⇌ αFeSi2 + Si and can be eliminated by further annealing. A small amount of excess silicon in αFeSi2 based thermoelectric materials Mn0.08Fe0.92Six (1.9 ≤ x ≤ 2.5) increases the thermoelectric sensitivity with a maximum Seebeck coefﬁcient of 315 μV·K–1 for x = 2.0 at 150°C [2003Che]. However a large amount of excess silicon deteriorates the thermoelectric properties due to the high thermal conductivity of silicon. Compared to the undoped αFeSi2, the electrical conductivity of p-type Mn0.08Fe0.92Six (1.9 ≤ x ≤ 2.5) is greatly enhanced. This electrical conductivity increases with increasing pressureless sintering temperature, i.e. density, whereas the Seebeck coefﬁcient becomes lower. The optimum thermoelectric properties of the Mn0.1Fe0.9Si2 alloy were obtained for a sintering temperature at about 400–600°C. The best Seebeck coefﬁcient S of 380 μV·K–1 at 400–600°C was obtained for coarse powders Mn0.1Fe0.9Si2 sintered at 1150°C for 2 h and annealed at 800°C [1999Cho, 2001Cho]. The highest power factor P = S2 / ρ of 1.7·10–3 W·mK–2 was obtained at 500°C [1999Cho]. The p-type conduction of the Mn doped αFeSi2 (αMnxFe1–xSi2 with x = 0.01, 0.03, 0.06 and 0.1) is revealed by an exponential growth of the Hall coefﬁcient with decreasing temperature down to about –103°C to –153°C with a well pronounced maximum which is a characteristic sign of the presence of a conduction in a band formed by shallow impurity levels. This feature is similar to that observed in the p-type αFeSi2. However the obtained values for the activation energies of the shallow ε1 and deep ε2 acceptor levels are higher in αMnxFe1–xSi2 (x = 0.01, 0.03, 0.06 and 0.1) (ε1 = 90 to 135 meV, ε2 = 219 to 299 meV) than those determined for the undoped αFeSi2 (ε1 = 70 meV, ε2 = 120 meV) [2000Aru]. The electrical resistivities of melt-spun and levitation-melted Mn doped Fe2Si5 alloys decrease with increasing temperature since an increasing number of carriers are thermally excited. The electrical conductivity of the melt-spun sample is lower than the one of the levitation-melted counterparts due to enhanced carrier scattering and hence reduced carrier mobility. The n-type conduction of the Mn doped βFeSi2, called Fe2Si5 by [2003Zhu], is revealed by a negative polarity of the Hall coefﬁcient and a higher electrical conductivity than the non doped βFeSi2. The hardness and the electrical resistivity has been measured along the quasibinary system MnSi-FeSi showing a maximum for the two properties: at 50 mass% FeSi (17 at.% Mn and 66 at.% Si) for the electrical resistivity and about 35 mass% FeSi (22 at.% Mn and 66 at.% Si) for the hardness [1957Tav]. It was found that carbon impurity has a light inﬂuence on the position of the maximum of the electrical resistance but its strongly affects the composition curve of the hardness with a maximum at 55 mass% FeSi (15 at.% Mn and 66 at.% Si).

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Fe–Mn–Si

After appropriate oxydation, the alloys with 22.7–23.2 mass% Mn, 67.3 mass% Fe and 10-9.5 mass% Si (20.93–21.48 at.% Mn and 18.03–17.21 at.% Si) have very good corrosion resistance in sulfuric acid at room temperature. Corrosion resistance can also be enhanced by addition of Cr to Fe-Mn-Si alloys [1990Ots]. All experimental data regarding works on material properties are reported in Table 6.

Table 1.

Investigations of the Fe-Mn-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1937Vog]

Thermal analysis and optical microscopy

400–1500°C, alloys in the Mn-Fe-MnSi-FeSi ternary area

[1956Gla2]

X-ray diffraction

400°C, Mn3–xFexSi (0 ≤ x ≤ 1)

[1958Aro]

X-ray diffraction

950°C, alloys along FeSi-MnSi and Mn5Si3Fe5Si3

[1962Gla]

X-ray diffraction and microstructure method

MnSi2-FeSi2, MnSi-FeSi, Mn5Si3-Fe5Si3, Mn3SiFe3Si

[1964Gup]

X-ray diffraction

1000°C, Mn30Fe70-Mn10Fe90 (at.%) and up to 20 at.% Si

[1964Sen]

X-ray diffraction

750°C, (Mn,Fe)5Si2 with 34 mass% Fe

[1966Bar]

X-ray diffraction

1000°C, Mn-Fe with Si up to 30 at.%.

[1968Sid]

X-ray diffraction

Annealed for 72 h between 890–1050°C, MnSiFeSi

[1968Fli]

X-ray diffraction

Annealing at 1000°C for 50 h, 53Mn47Si35.5Mn16.4Fe-46.1Si (mass%)

[1968Set]

X-ray diffraction

1000°C, Fe-Mn-Si

[1970Nar]

X-ray diffraction, Mössbauer spectroscopy

–268.8 to 25°C, Mn5–xFexSi3 with 1 ≤ x ≤ 5

[1972Joh]

X-ray diffraction, Mössbauer spectroscopy

Annealed at 950 and then at 750°C, Mn5–xFexSi3 with 0 ≤ x ≤ 5

[1973Bin]

Neutron diffraction

Annealed 3 days at 950°C / Mn5–iFexSi3 with x = 0, 1, 2, 3 and 4

[1973Ish]

X-ray diffraction and thermodynamic calculation

700–1000°C, Fe-Fe1–x(Mn,Si)x with x ≤ 30 at.%.

[1974Abr]

Thermal and microstructural analysis

900–1250°C, MnSi1.72-FeSi2

[1974Bab]

Neutron and X-ray diffraction

Annealed for 50 h at 950°C, (MnxFe1–x)3Si with 0≤x≤1

[1974Bur]

Spin-echo spectroscopy

Annealed for 2 h at 600°C, Mn0.005Fe0.745Si0.25 and Mn0.01Fe0.76Si0.23

[1974Yoo]

Neutron and X-ray diffraction

MnxFe3–xSi with 0 ≤ x ≤ 2 (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1975Pic]

Neutron diffraction

Annealed for 1 h at 600°C, MnxFe3–xSi with 0 ≤ x ≤ 0.1

[1975Ver]

X-ray diffraction

900°C, (MnxFe1–x)3Si with 0 ≤ x ≤ 1

[1976Sud]

X-ray diffraction

Annealed for 100 h at 947°C, (MnxFe1–x)5Si3 with 0 ≤ x ≤ 1

[1976Zie]

X-ray and neutron powder diffraction measurements

MnFe2Si

[1977Ver]

Mössbauer and neutron diffraction measurements

–195°C and 27°C, (MnxFe1–x)3Si with x = 0, 0.05, 0.10, 0.15, 0.20 and 0.25

[1977Sho]

X-ray diffraction

Mn77Fe4Si19 (at.%)

[1977Yoo]

Neutron and X-ray diffraction

MnxFe3–xSi with 0.75 ≤ x ≤ 3

[1978Gee]

Vapor transport method

1427°C, Fe-Mn-Si

[1980Bob]

High-temperature calorimeter

1527°C, Mn5Si3-Fe5Si3

[1980Smi]

Calorimetry

–269 to 187°C, MnxFe3–xSi with 0.6 ≤ x ≤ 1.6

[1979Ari]

Vapor transport method

1560°C, Fe-Mn-Si with 0.1 < xMn < 20 and 1 < xSi < 20 (at.%)

[1981Fuj]

Electric resistance furnace, EPMA

1515–1534°C, Fe-Mn0-2.62Si0-1.990

[1984Bat]

High-temperature calorimeter

1926, 1953 and 1994°C, Fe-Mn0.0192-0.0258Si0.0040-0.0195

[1984Bon]

High-temperature calorimeter

1687°C, Fe-Mn-Si alloys with xFe:xSi =0.8:0.2, 0.7:0.3, 0.4:0.6 and 0.35:0.65

[1987Bal]

Evaporation measurements

1500°C, Fe-Mn alloys with 3.14 mass% Si

[1988Mil]

Microprobe analysis, X-ray diffraction, capacitance dilatometer

–73 to 27°C, MnFe2Si

[1988Sud]

Calorimetry

1572°C, Mn-FeSi

[1989Bon]

Thermodynamic measurements

1572°C, Mn-FeSi and Fe-MnSi

[1991Lan]

Electron microprobe analysis

900°C, Fe alloys with Mn and Si up to 35 and 12 mass%

[1992For, 1993For]

Thermodynamic models

527–1527°C, Fe-Mn-Si with xMn/xFe = 7.76, 2.14, 0.837, 0.439, 0.176 and 0.0873 with Si from 0 to 35 (in mass%)

[1996Zai1, 1996Zai2, 1998Zai]

Knudsen effusion technique, mass spectrometry analysis of evaporated species

1162–1536°C, liquid Fe-Mn-Si alloys with x(Fe) ≥ 0, x(Si) ≤ 1 and 0 ≤ x(Mn) ≤ 0.6 (at.%)

[1997And]

X-ray, DSC and dilatometer measurements

–73–227°C, Fe-(28.0-28.3)Mn(1.99-7.01)Si (mass%)

[1997Li1]

Substitutional solution model

627 to –73°C, Fe-30Mn6Si (mass%) (continued)

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Fe–Mn–Si

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1997Li2]

Uniﬁed interaction parameter model

1400°C, Fe-Mn-Si

[2004Can]

Neutron diffraction

Annealed at 952°C for 5 d and water quenched, Mn5–xFexSi3 (x = 4, 3.5, 3, 2, 1)

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αFe,δFe)

cI2 Im 3m W

(αFe) (Ferrite) < 912

(δFe) 1538–1394

(εFe)

Comments/References

a = 286.65

pure Fe at 25°C [Mas2, V-C2]. Dissolves 5 at.% Mn at 527°C [2004Wit]. Dissolves up to 10 at.% Si at 500°C [Mas2]. pure Fe at 1390°C [V-C2, Mas2] Dissolves 10 at.% Mn at 1474.5°C [2004Wit]. Dissolves up to 19.5 at.% Si at 1280°C [Mas2].

a = 293.15

hP2 P63/mmc Mg

(δMn) 1246–1138

cI2 Im 3m W

γ, (γFe,γMn)

cF4 Fm 3m Cu

(γFe) 1394–912

Lattice Parameters [pm]

(γMn) 1138–1087

metastable martensite obtained by quenching γ(Fe,Mn) alloys [1990Sad] a = 254.34 a = 412.12

Fe-30 mass% Mn-6 mass% Si, (aγ = 360.05) [1999Guo]

a = 308.0

pure Mn [Mas2]. Dissolves up to 12.2 at.% Fe at 1236.6°C [2004Wit]. Dissolves 2 at.% Si [Mas2]

a = 364.67

pure Fe at 915°C [V-C2, Mas2]. Complete solubility with (γMn). Dissolves up to 3.8 at.% Si at 1150°C [2004Wit] pure Mn [Mas2] Complete solubility with (γFe). Dissolves up to 2.8 at.% Si [Mas2]

a = 386.0

(βMn) 1087–707

cP20 P4132 βMn

a = 631.52

pure Mn [Mas2] Dissolves up to 32.9 at.% Fe [2004Wit]. Dissolves up to 16.7 at.% Si [Mas2].

(αMn) < 707

cI58 I 43m (αMn)

a = 891.26

pure Mn at 25°C [Mas2]. Dissolves up to 35.2 at.% Fe [2004Wit]. Dissolves up to 6 at.% Si [Mas2]. (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αSi) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

at 25°C [Mas2] Practically no solubility for Fe and Mn [Mas2].

(δSi)

hP4 P63/mmc αLa

a = 380 c = 628

at 25°C, 16 GPa [Mas2]

(γSi)

cI16 Im 3m γSi

a = 663.6

at 25°C, 16 GPa [Mas2]

(βSi)

tI4 I41/amd βSn

a = 468.6 c = 258.5

at 25°C, 9.5 GPa [Mas2]

(Mn1–xFex)Si

cP8 P213 FeSi

FeSi < 1410

a = 451.7 ± 0.5

0≤x≤1 x = 1 and at 25°C [1996Spo] x = 0 and at 25°C [1996Spo] 33.36 to 34.46 at.% Si [Mas2] at 300°C [V-C2, Mas2]

MnSi < 1276

a = 455.8

49.5 to 50.2 at.% Si [Mas2] at 10 K [V-C2]

(Mn1–xFex)5Si3 η, Fe5Si3 1060–825 Mn5Si3 < 1300

β, Fe2Si 1212–1040

hP16 P63/mcm Mn5Si3

cP2 Pm 3m CsCl or hP6 P 3m1 Fe2Si

a = 448.8 a = 456.0

0≤x≤1 a = 675.9 ± 0.5 c = 472.0 ± 0.5 a = 691.0 c = 481.4 a = 688.40 ± 0.06 c = 478.76 ± 0.08 a = 686.02 ± 0.06 c = 475.98 ± 0.09 a = 683.22 ± 0.09 c = 474.26 ± 0.11 a = 681.78 ± 0.04 c = 473.60 ± 0.05 a = 680.04 ± 0.05 c = 472.98 ± 0.08

[V-C2]

a = 281

[V-C2] 19.93 to 21.31 at.% Si [Mas2]

a = 405.2 ± 0.2 c = 508.55 ± 0.03

[V-C2]

[V-C2] for Mn4FeSi3 [1972Joh] for Mn3Fe2Si3 [1972Joh] for Mn2Fe3Si3 [1972Joh] for Mn1.5Fe3.5Si3 [1972Joh] for MnFe4Si3 [1972Joh]

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Fe–Mn–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

βFeSi2(h) 1220–937

tP3 P4/mmm βFeSi2

a = 269.01 c = 513.4

αFeSi2(r) < 982

oC48 Cmca αFeSi2

a = 986.3 ± 0.7 b = 779.1 ± 0.6 c = 783.3 ± 0.6

(Mn1–xFex)3Si(h)

cF16 Fm 3m BiF3

α1, Fe3Si < 1247

Lattice Parameters [pm]

a = 572.2 a = 566.0 ± 0.1 to 572.1 ± 0.3

a = 566.25 (Mn1–xFex)3Si(r) α2, Fe3Si < 1284 αMn3Si < 677

a = 281.8 ± 0.1 a = 285.8 ± 0.1 oI186 Immm Mn4Si

Mn4Si7

tP44 P 4c2 Mn4Si7

Mn5Si2 < 850

tP56 P41212 Mn5Si2

R, Mn6Si < 880

hR159 R 3 Co5Cr2Mo3

Mn6Si7

hR39 R 3m Fe7W6

66.7 at.% Si [Mas2, V-C2]

10 to 30 at.% Si [Mas2] [V-C2] 25 to 25.6 at.% Si [Mas2] [V-C2] for 0.75 ≤ x ≤ 3. Two linear variations with composition with a break at x = 1.8 [1977Yoo] MnFe2Si [1976Zie] 0≤x≤1

cP2 Fm 3m CsCl

ν, Mn4Si < 1060

53.4 to 57.38 at.% Si [Mas2] Fe0.87Si2.13 [V-C2]

0≤x≤1

a = 565.0

βMn3Si 1070–677

Comments/References

a = 1699.2 ± 0.4 b = 2863.4 ± 0.7 c = 465.6 ± 0.1 a = 552.5 ± 0.1 c = 1746.3 ± 0.3

a = 890.97 ± 0.02 c = 871.53 ± 0.03 a = 886.6 ± 0.1 c = 865.5 ± 0.1 a = 1087.1 ± 0.5 c = 1918.0 ± 0.9 a = 470 ± 0.1 c = 2561 ± 0.5

10 to 22 at.% Si [Mas2] [1956Gla2] 25 to 25.6 at.% Si [Mas2] [1956Gla2] 16.2 to 18.75 at.% Si [Mas2] [V-C2]

[V-C2]

at 28.6 at.% Si [Mas2] [V-C2] for (Mn,Fe)5Si2 with 34 mass% Fe at 750°C [1964Sen] 12 to 17.75 at.% Si [Mas2] [V-C2] [V-C2]

(continued)

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Fe–Mn–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

MnSi1.75–x < 1155

tP120 P 4n2 Mn11Si19

Mn15Si26

tI164 I 42d Mn15Si26

a = 553.1 c = 6531.1

[V-C2]

Mn27Si47

tP296 P 4n2 Mn27Si47

a = 553 c = 11790

[V-C2]

τ, Mn77Fe4Si19

mC110 C2 Mn77Fe4Si19

a = 1336.2 ± 0.1 b = 1164.5 ± 0.1 c = 873.4 ± 0.1 β = 90.53 ± 0.01

[1977Sho] from Mn74.5Fe6.0Si19.5 to Mn80.2Fe0.8Si19.0 at 1000°C [1964Gup]

Table 3.

Lattice Parameters [pm]

17

Comments/References

63 to 63.4 at.% Si [Mas2] [V-C2]

a = 552 c = 4820

Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (at.%) Fe

Mn

Si

L+(δFe) ⇌ α1, γ

1284

D1

L

69.36

12.59

18.05

L+ α1 ⇌ (Mn,Fe)3Si+γ

1200
U1

L

65.37

10.79

23.84

L+(Mn,Fe)Si ⇌ β+(Mn,Fe)5Si3

1100
U2

L (Mn,Fe)Si β (Mn,Fe)5Si3

58.38 44.26 64.24 51.86

7.70 5.26 3.58 8.27

33.92 50.48 32.18 39.87

L+β ⇌ (Mn,Fe)5Si3+(Mn,Fe)3Si

∼ 1100

U3

L β (Mn,Fe)5Si3 (Mn,Fe)3Si

57.55 64.69 47.48 63.89

12.43 4.21 13.26 10.16

30.02 31.10 39.26 25.95

L+(βMn)+ν ⇌ (Mn,Fe)3Si

1040
P1

L

79.00

2.13

18.87

L+(βMn) ⇌ (Mn,Fe)3Si+γ

1020

U5

L (βMn) (Mn,Fe)3Si γ

35.48 31.36 25.20 39.37

44.08 51.99 46.79 44.31

20.44 16.65 28.01 16.32

L ⇌ (Mn,Fe)3Si+γ

< 1020

e9

L

47.56

27.57

24.87

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18 Table 4.

Fe–Mn–Si Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mol of atoms [kJ, mol, K]

Comments

0.1 Mn+0.9 Fe0.5Si0.5 ⇌ Mn0.1Fe0.45Si0.45

1572

ΔHmix = –7.4 ± 0.7

[1989Bon]

0.2 Mn+0.8 Fe0.5Si0.5 ⇌ Mn0.2Fe0.4Si0.4

1572

ΔHmix = –11.6 ± 1.5

[1989Bon]

0.3 Mn+0.7 Fe0.5Si0.5 ⇌ Mn0.3Fe0.35Si0.35

1572

ΔHmix = –16.6 ± 1.5

[1989Bon]

0.4 Mn+0.6 Fe0.5Si0.5 ⇌ Mn0.4Fe0.3Si0.3

1572

ΔHmix = –21.5 ± 2.0

[1989Bon]

0.5 Mn+0.5 Fe0.5Si0.5 ⇌ Mn0.5Fe0.25Si0.25

1572

ΔHmix = –25.0 ± 2.0

[1989Bon]

0.1 Fe+0.9 Mn0.5Si0.5 ⇌ Fe0.1Mn0.45Si0.45

1572

ΔHmix = –7.4 ± 0.4

[1989Bon]

0.2 Fe+0.8 Mn0.5Si0.5 ⇌ Fe0.2Mn0.4Si0.4

1572

ΔHmix = –13.6 ± 0.6

[1989Bon]

0.3 Fe+0.7 Mn0.5Si0.5 ⇌ Fe0.3Mn0.35Si0.35

1572

ΔHmix = –19.6 ± 0.9

[1989Bon]

0.4 Fe+0.6 Mn0.5Si0.5 ⇌ Fe0.4Mn0.3Si0.3

1572

ΔHmix = –25.5 ± 1.0

[1989Bon]

0.5 Fe+0.5 Mn0.5Si0.5 ⇌ Fe0.5Mn0.25Si0.25

1572

ΔHmix = –29.4 ± 1.5

[1989Bon]

0.015 Mn+0.8 Fe+0.2 Si ⇌ Fe0.8Mn0.015Si0.2

1687

ΔHmix = –16.3

[1984Bon]

0.255 Mn+0.8 Fe+0.2 Si ⇌ Fe0.8Mn0.255Si0.2

1687

ΔHmix = –18.1

[1984Bon]

0.013 Mn+0.7 Fe+ 0.3Si ⇌ Fe0.7Mn0.013Si0.3

1687

ΔHmix = –32.0

[1984Bon]

0.289Mn+0.7 Fe+0.3 Si ⇌ Fe0.7Mn0.289Si0.3

1687

ΔHmix = –29.9

[1984Bon]

0.049Mn+0.4 Fe+0.6 Si ⇌ Fe04Mn0.013Si0.6

1687

ΔHmix = –32.6

[1984Bon]

0.337Mn+0.4 Fe+0.6 Si ⇌ Fe0.4Mn0.337Si0.6

1687

ΔHmix = –34.8

[1984Bon]

0.010Mn+0.35 Fe+0.65 Si ⇌ Fe0.35Mn0.010Si0.65

1687

ΔHmix = –33.0

[1984Bon]

0.294 Mn+0.35 Fe+0.65 Si ⇌ Fe0.35Mn0.294Si0.65

1687

ΔHmix = –36.0

[1984Bon]

Table 5. Phase MnFeSi

Table 6.

Thermodynamic Properties of Single Phases Temperature Range [°C]

Property, per mole of atoms [J, mol, K]

Comments

1162–1536

ΔfG = –105509 –15.31·T

[1996Zai1, 1998Zai]

0

Investigations of the Fe-Mn-Si Materials Properties

Reference

Method/Experimental Technique

Conditions/Type of Property

[1957Tav]

Resistance and hardness measurements

Alloys along MnSi-FeSi, electrical resistivity and hardness

[1970Nar]

X-ray diffraction, Mössbauer spectroscopy, vibrating sample magnetometer, Faraday method

Mn5–xFexSi3 with 1 ≤ x ≤ 5, magnetic moment, Curie and Neel temperatures, susceptibility, magnetization (continued)

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Fe–Mn–Si

19

Reference

Method/Experimental Technique

Conditions/Type of Property

[1972Joh]

X-ray diffraction, Mössbauer spectroscopy, vibration sample magnetometer

Mn5–xFexSi3 with 0 ≤ x ≤ 5, magnetic hyperﬁne ﬁeld, magnetization, magnetic moment, susceptibility

[1973Bin]

Neutron diffraction and Sucksmith balance

Mn5–xFexSi3 with x = 0, 1, 2, 3 and 4, magnetic saturation moment

[1974Yoo]

Vibrating sample magnetometer, Sucksmith ring balance, neutron diffraction

MnxFe3–xSi (0 ≤ x ≤ 2), magnetization, Curie TC and ordering TR temperatures

[1976Lut]

Adiabatic calorimeter, absolute quartz dilatometer, high frequency resonance method

(MnxFe1–x)3Si (0 ≤ x ≤ 0.45), Curie TC and Neel TN temperatures

[1976Nic]

X-ray, magnetization and NMR techniques

MnxFe3–xSi (0 ≤ x ≤ 1), magnetic moment, hyperﬁne ﬁeld

[1976Sid]

Vibrating sample magnetometer, pendulum balance, Mössbauer spectroscopy, neutron diffraction

(MnxFe1–x)3Si with 0 ≤ x ≤ 1, magnetization, average magnetic moment, susceptibility

[1976Sud]

Magnetization, heat capacity and thermal expansion measurements

(Mn1–xFex)5Si3 with 0 ≤ x ≤ 1, ordering TR, Neel TN and Curie TC temperatures, thermal expansion coefﬁcient, magnetization

[1976Zie]

Vibrating sample magnetometer, modiﬁed Sucksmith ring balance, neutron diffraction

MnFe2Si, spontaneous magnetization, magnetic susceptibility, magnetic moment

[1976Zvi]

Dilatometer, tensile tests, X-ray diffraction

Fe-(20-30)Mn(0-10)Si (mass%), strength, hardness, susceptibility

[1977Nic]

Vibrating sample magnetometer

MnxFe3–xSi, saturation magnetization

[1977Yoo]

Four terminal potentiometric technique Curie temperature, saturation magnetization,

MnxFe3–xSi with 0.75 ≤ x ≤ 3.0, resistivity, magnetic moment

[1978Nar]

Tensile tests, ﬂuxmeter, strain gauge technique, vibrating sample magnetometer

Fe alloys with 6.6 mass% Si and 0.01, 0.12 and 0.2 mass% Mn, tensile strength, saturation magnetization

[1983Bus]

Polar Kerr rotation measurements, vibrating sample magnetometer

MnFe2Si, saturation moment

[1986Sat]

Tensile tests, Faraday magnetic balance, Neel temperature, magnetic susceptibility, yield stress

Fe-(21.2-32)Mn(0.99-6.54) (mass%), martensitic transformations

[1986Mur]

Tensile tests yield stress, Neel temperature

Fe-(25-35)Mn-(0-6)Si (mass%), martensitic transformation

[1987Gel]

Thermal expansion and magnetic susceptibility measurements

MnyFe1-ySi (0 ≤ y ≤ 1), thermal expansion coefﬁcient

[1988Mil]

Microprobe analysis, X-ray diffraction, capacitance dilatometer

–73 to 27°C, MnFe2Si (continued)

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20

Fe–Mn–Si

Reference

Method/Experimental Technique

Conditions/Type of Property

[1990Ots]

Tensile test, vibrating sample magnetometer, electric resistance measurements, yield stress

Fe-(11-3)Mn(5-6)Si with 0 to 13 mass% Cr and 0 to 8 mass% Ni, martensitic transformations

[1990Sad]

Elongation stress, dilatometric measurements, yield stress

Fe-(24-35)Mn(2-9)Si, martensitic transformation and austenitization

[1991Mil]

Vibrating sample magnetometer, threeterminal capacitance dilatometer

Mn0.8Fe2.2Si, thermal expansion

[1991Lan]

Corrosion tester

(22.7–23.2)Mn67.3Fe(10–9.5)Si (mass%), ultimate tensile strength, corrosion resistance

[1993Wat]

Micro Vickers hardness tester, tensile strain tests, shrinkage fraction measurement

Fe-31Mn6Si (mass%) powder deformedheated 13 times, critical resolved shear stress, strain and electrical resistance

[1995Ron]

Electrical resistance, magnetic susceptibility measurements, TEM

Fe-29.9Mn-6.0Si (mass%) prestrained, shape memory effect

[1996Mat]

Tensile prestrain tests, thermomechanical treatment

Fe-28Mn-6Si-5Cr-0.03C (mass%) hot rolled shape memory recovery

[1996Qin]

Magnetic balance, metallography, Neel temperature, magnetic susceptibility, electrical resistivity

Fe-(27.77-32.01)Mn-(4.10-6.10)Si, martensitic transformation and austenitization

[1996Spo]

Soft X-ray emission spectroscopy, XRD, electrical resistivity

Mn1–xFexSi with (0 ≤ x ≤ 1) (at.%), magnetic transition temperature

[1996Zha]

Electrical resistance measurements, XRD analysis, electrical resistance

Fe-29.44Mn-6.2Si (mass%) hot forged and hot rolled, martensitic transformation and austenitization

[1998Cot1]

Dilatometric measurement

Fe-(15–35)Mn-(0–6.5)Si (mass%), martensitic transformation and austenitization

[1998Muk]

Density, thermal, susceptibility measurements, linear thermal expansion, Debye temperature,

MnxFe3–xSi (1.2 ≤ x ≤ 1.8) homogenized one week at 800°C, Grüneisen parameters

[1999Che]

DMA and DME analysis, Neel temperature, internal friction, elastic modulus

Fe-30 mass% Mn-6 mass% Si-5 mass% Cr, forged and rolled, martensitic transformation and austenitization

[2000Aru]

Van der Pauw’s technique, alternating current magnetic method, resistivity and Hall coefﬁcient measurements

MnxFe1–xSi2 (x = 0.01, 0.03, 0.06 and 0.1) powder cold pressing and sintered and then annealed at 800°C for 48 hours

[2000Dai]

Tensile and bending methods

Fe-29.7Mn5.5Si and Fe-18.1Mn5.5Si forged, stress, residual strain

[2000Wu]

Electrostatic audio-frequency internal friction measurements

Fe-30.30Mn6.10Si (mass%), hot-forged and hot-rolled, internal friction, elastic modulus, martensitic and Neel temperatures (continued)

DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

21

Reference

Method/Experimental Technique

Conditions/Type of Property

[2000Jin1, 2000Jin2]

X-ray diffraction proﬁle analysis, fourprobe electrical resistance method

Fe-(23.37-30.3)Mn(5.87-6.06)Si (in mass%), hot-forged and hot-rolled, martensitic start temperature

[1999Cho, 2001Cho]

Thermoelectric electromotive force measurements, Seebeck coefﬁcient, electrical conductivity

Mn0.1Fe0.9Si2 powders sintered at 1150–1190°C under 230 MPa, annealed at 800 or 865°C for 100 hours

[2002Son]

Quantum magnetometer

FexMn5–xSi3 (x = 0, 1, 2, 3, 4, 5) annealed at 952°C for 5 days, ac-susceptibility, magnetization, magnetic-entropy

[2003Che]

Thermal diffusion and Hall measurements, Seebeck coefﬁcient and electrical conductivity experiments

Mn0.08Fe0.92Six (1.9 ≤ x ≤ 2.5), hot pressed (50 MPa at 975°C) annealed 800°C, thermal conductivity

[2003Zhu]

Seebeck coefﬁcient, electrical resistivity

Mn0.14Fe1.86Si5, cold pressed under 860 MPa, sintered at 1150°C and annealed at 800°C

[2004Can]

Curie temperature and magnetic moment measurements

Annealed at 952°C for 5 days and water quenched, Mn5–xFexSi3 (x = 4, 3.5, 3, 2, 1)

[2005Jia]

Seebeck coefﬁcient measurements

Mn2.36Fe27.14Si70.5 (at.%) alloy annealed at 550°C, Hall coefﬁcient, electrical resistivity

[2005Lin]

Microvickers tester, bending test

Fe-30Mn6Si (mass%) alloy, hardness

[2005Sta]

SEM, bending strain, shape memory effect

Fe, 11 mass% Mn, 4.5 mass% Si, 10 mass% Cr, austenitized at 1000°C

[2007Sta]

X-ray diffraction, tensile strength, hardness, SEM observations,

Fe, 12 to 18 mass% Mn, 4 to 4.5 mass% Si, 10 mass% Cr, austenizing treatment at 1000°C, then annealing 500–800°C.

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22

Fig. 1. Fe-Mn-Si.

Fe–Mn–Si

Quasibinary section FeSi-MnSi

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Landolt-Börnstein New Series IV/11D4

23

Fig. 2. Fe-Mn-Si.

Reaction scheme

Fe–Mn–Si

Landolt-Börnstein New Series IV/11D4

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24

Fig. 3. Fe-Mn-Si.

Fe–Mn–Si

Liquidus surface projection

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

Fig. 4. Fe-Mn-Si.

Landolt-Börnstein New Series IV/11D4

25

Isothermal section at 700°C

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26

Fig. 5. Fe-Mn-Si.

Fe–Mn–Si

Isothermal section at 900°C

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

Fig. 6. Fe-Mn-Si.

Landolt-Börnstein New Series IV/11D4

27

Isothermal section at 1000°C

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28

Fig. 7. Fe-Mn-Si.

Fe–Mn–Si

Vertical section at xMn/xFe = 7.76

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

Fig. 8. Fe-Mn-Si.

Landolt-Börnstein New Series IV/11D4

29

Vertical section at xMn/xFe = 2.14

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30

Fig. 9. Fe-Mn-Si.

Fe–Mn–Si

Silicon isoactivity lines in liquid alloys at 1427°C

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

Fig. 10. Fe-Mn-Si.

Landolt-Börnstein New Series IV/11D4

31

Manganese isoactivity lines in liquid alloys at 1427°C

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32

Fig. 11. Fe-Mn-Si.

Fe–Mn–Si

Iron isoactivity lines in liquid alloys at 1427°C

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si

Fig. 12. Fe-Mn-Si.

Landolt-Börnstein New Series IV/11D4

33

Lines of constant molar Gibbs free energy of formation in liquid alloys at 1427°C, in kJ·mol–1

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DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

34 References [1937Vog]

[1938Jae] [1949Jae] [1956Gla1]

[1956Gla2]

[1957Tav]

[1958Aro]

[1958Bon]

[1960Bon]

[1962Gla]

[1962Wit]

[1964Gup]

[1964Sen]

[1966Bar]

[1968Fli]

[1968Set]

[1968Sid]

[1970Nar]

Fe–Mn–Si

Vogel, R., Bedarff, H., “The Iron-Manganese-Silicon System” (in German), Arch. Eisenhuettenwes., 10(12), 581–586 (1937) (Experimental, Morphology, Phase Diagram, Phase Relations, 5) Jänecke, E., Vogel, R., “The Iron-Manganese-Silicon System” (in German), Arch. Eisenhuettenwes., 11(8), 409–412 (1938) (Phase Diagram, Phase Relations, Review, 2) Jänecke, E., “Fe-Mn-Si” (in German), Kurzgefasstes Handbuch aller Legierungen, Winter Verlag, Heidelberg, 650–651 (1949) (Review, Phase Diagram, 2) Gladyshevskii, E.I., Cherkahsin, E.E., “Solid Solutions on the Basis of Metallic Compounds”, Russ. J. Inorg. Chem., 1(6), 288–295 (1956), translated from Zh. Neorg. Khim., 1(6), 1394–1401 (1956) (Crys. Structure, Phase Diagram, Review, 4) Gladyshevsky, E.I., Kripyakevich, P.I., Kuz’ma, Yu.B., “X-Ray Investigations of Some Alloys of the Transition Metals with Silicon” (in Russian), Fiz. Met. Metalloved., 2(3), 454–456 (1956) (Crys. Structure, Experimental, 11) Tavadze, F.N., Doliashvili, K.A., “Microstructure and Certain Properties of the FeSi-MnSi-C Alloy System” (in Russian), Soobsh. Akad. Nauik Gruz. SSR, 18, 211–216 (1957) (Electr. Prop., Experimental, Morphology, 5) Aronsson, B., “An Investigation of the Me3Si3-MeSi Region of the Mn-Fe-Si and Some Related Systems”, Acta Chem. Scand., 12, 308–313 (1958) (Experimental, Crys. Structure, Phase Relations, 22) Bonnier, E., “About the Estimation on Free Energy Diagram of the Ternary System Fe-MnSi at 1600 K” (in French), Compt. Rend. Acad. Sci., 246(18), 2617–2619 (1958) (Calculation, Thermodyn., 8) Bonnier, E., Caboz, R., “About the Estimation on Free Enthalpy of Mixing for some Liquid Metal Ternary Alloys” (in French), Compt. Rend. Acad. Sci., 250(3), 527–529 (1960) (Theory, 4) Gladyshevskii E.L., “Crystal Structure of Compounds and Phase Equilibria in Ternary Systems of Two Transition Metals and Silicon”, Powder Metall. Met. Ceram., (4), 262–265 (1962) translated from Poroshk. Metall., (4), 46–49 (1962) (Crys. Structure, Experimental, Phase Diagram, 17) Wittmann, A., Burger, K.O., Nowotny, H., “Investigations in the Ni-Al-Si Ternary System as well as Mono- and Disilicide Systems of Several Transition Metals” (in German), Monatsh. Chem., 93, 674–680 (1962) (Review, Crys. Structure, 20) Gupta, K.P., “New Phases in the Manganese-Silicon and Iron-Manganese-Silicon System”, Trans. Met. Soc. AIME, 230, 253–254 (1964) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 6) Senateur, J.P., Fruchart, R., “The Existence of a Silicide of Mn, Mn5Si2, and its Relation to the Carbides Mn5C2 and Fe5C2” (in French), Compt. Rend. Acad. Sci. Paris, 258(3), 1524–1525 (1964) (Crys. Structure, Experimental, 8) Bardos, D.I., Malik, R.K., Spiegel, F.X., Beck, P.A., “β Mn Phases in Ternary Systems of Transition Elements with Silicon, Germanium, or Tin”, Trans. Met. Soc. AIME, 236, 40–48 (1966) (Experimental, Phase Diagram, Phase Relations, 33) Flieher, G., Voellenkle, H., Nowotny, H., “New Compounds with the TiSi2 Structure” (in German), Monatsh. Chem., 99(6), 2408–2415 (1968) (Crys. Structure, Experimental, Phys. Prop., 14) Setz, S., Nowotny, H., Benesovsky, F., “Investigations in the Systems Mn-(V, Re, Fe)-Si” (in German), Monatsh. Chem., 99, 2004–2015 (1968) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 29) Sidorenko, A.F., Dmitriev, E.A., Apasova, E.A., “Crystal Lattice Constants in Some Quasibinary Alloys Based on FeSi” (in Russian), Tr. Uralsk. Politekhn. Inst., (167), 124–127 (1968) (Crys. Structure, Experimental, 3) Narasimhan, K.S.V.L., Reiff, W.M., Steinﬁnk, H., Collins, R.L., “Magnetism and Bonding in a D88 Structure: Mössbauer and Magnetic Investigation of the System Mn5Si3-Fe5Si3”,

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Fe–Mn–Si

[1972Joh]

[1973Bin]

[1973Ish]

[1974Abr]

[1974Bab]

[1974Bur] [1974Yoo] [1975Pic] [1975Ver]

[1976Lut]

[1976Nar]

[1976Nic]

[1976Sid]

[1976Sud]

[1976Zie] [1976Zvi]

[1977Nic]

Landolt-Börnstein New Series IV/11D4

35

J. Phys. Chem. Solids, 31, 1511–1524 (1970) (Crys. Structure, Experimental, Magn. Prop., 23) Johnson, V., Weiher, J.F., Frederick, C.G., Rogers, D.B., “Magnetic and Mössbauer Effect Studies of Mn5Si3:Fe5Si3 Solid Solutions”, J. Solid State Chem., 4, 311–323 (1972) (Crys. Structure, Experimental, Magn. Prop., 27) Binczycka, H., Dimitrijevic, Z., Gajic, B., Szytula, A., “Atomic and Magnetic Structure of Mn5–xFexSi3”, Phys. Status Solidi A, 19, K13–K17 (1973) (Crys. Structure, Experimental, Mechan. Prop., 10) Ishida, K., Shibuya, K., Nishizawa, T., “γ Loops in Fe-Mn-V, Fe-Mn-Mo, and Fe-Mn-Si Systems” (in Japanese), J. Jpn. Inst. Met., 37, 1305–1312 (1973) (Experimental, Kinetics, Thermodyn., 22) Abrikosov, N.Kh., Ivanova, L.D., Petrova, L.I., “The System MnSi1.72-FeSi2”, Inorg. Mater., 10(12), 1907–1908 (1974), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 10(12), 2226–2227 (1974) (Experimental, Phase Diagram, Phase Relations, 12) Babanova, E.N., Sidorenko, F.A., Geld, P.V., Basov, N.I., “Ordering of (Fe1–xMnx)3Si Solid Solutions”, Phys. Met. Metallogr., 38(3), 122–126 (1974), translated from Fiz. Met. Metalloved., 38(3), 586–590 (1974) (Crys. Structure, Experimental, 5) Burch, T.J., Litrenta, T., Budnick, J.I., “Hyperﬁne Studies of Site Occupation in Ternary Systems”, Phys. Rev. Letters, 33(7), 421–424 (1974) (Crys. Structure, Experimental, 12) Yoon, S., Booth, J.G., “Structural and Magnetic Properties of Fe3–xMnxSi Alloys”, Phys. Letters, 48A(5), 381–382 (1974) (Crys. Structure, Experimental, Magn. Prop., 4) Pickart, S., Litrenta, T., Burch, T., Budnick, J.I., “Site Preference of Dilute Transition Metal Solutes in Fe3Si”, Phys. Lett. A, 53A(4), 321–323 (1975) (Crys. Structure, Experimental, 4) Vereshchagin, YuA., Babanova, E.N., Sidorenko, F.A., “Procedure for Synthesis, Homogeneity Regions and Lattice Spacings of (Fe1–xMx)3Si (M = Mn, Co, Ni) Solid Solutions with a D03 Structure” (in Russian), Fiz. Metody Issled. Tverdogo Tela, 1, 40–42 (1975) (Crys. Structure, Experimental, 9) Lutskaya, L.F., Kalishevich, G.I., Geld, P.V., “Magnetic Phase Diagram of (Fe1–xMnx)3Si Solid Solutions”, Sov. Phys. Solid State, 18(6), 1011–1012 (1976), translated from Fiz. Tverd. Tela, 18(6), 1738–1740 (1976) (Experimental, Magn. Prop., 6) Narita, K., Enokizono, M., “Effects of Ni, Al, and Mn Addition on the Mechanical and Magnetic Properties of 6.5% Si-Fe Sheets”, IEEE Trans. Magn., 12(6), 873–873 (1976) (Abstract, 0) Niculescu, V., Raj, K., Budnick, J.I., Burch, T.J., Hines, W.A., Menotti, A.H., “Relating Structural, Magnetisation and Hyperﬁne Field Studies to a Local Environment Model in Fe3–xVxSi and Fe3–xMnxSi”, Phys. Rev. B, 14(9), 4160–4176 (1976) (Crys. Structure, Magn. Prop., Thermodyn., 26) Sidorenko, F.A., Vereshchagin, Yu.A., Babanova, E.N., Ryzhenko, B.V., Geld, P.V., “Magnetic Transitions in Mutual Solid Solutions of the Lower Iron and Manganese Silicides”, Sov. Phys.- JETP, 43(2), 225–331 (1976), translated from Zhur. Eksp. i Teor. Fiz., 70, 628–638 (1976) (Crys. Structure, Experimental, Magn. Prop., 11) Sudakova, N.P., Kuznetsov, S.I., Mikhelson, A.V., Sychev, N.I., Geld, P.V., “Magnetic Transitions in Mn-Fe Silicide Solid Solutions”, Sov. Phys.-Dokl., 21(5), 273–275 (1976), translated from Dokl. Akad. Nauk SSSR, 228, 582–585 (1976) (Experimental, Magn. Prop., 12) Ziebeck, K.R.A., Webster, P.J., “The Antiferromagnetic and Ferromagnetic Properties of Fe2MnSi”, Philos. Mag., 34(6), 973–982 (1976) (Crys. Structure, Experimental, Magn. Prop., 17) Zvigintseva, G.E., Logunov, V.Ya., “Phase Transformations and Mechanical Properties of Fe-Mn-Si Alloys”, Russ. Metall., (4), 169–172 (1976), translated from Izv. Akad. Nauk SSSR, Met., (4), 197–200 (1976) (Experimental, Mechan. Prop., 11) Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in Fe3–xTxSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Magn. Prop., 17)

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DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

36 [1977Sho] [1977Ver]

[1977Yoo]

[1978Gee] [1978Nar]

[1979Ari] [1980Bob]

[1980Smi]

[1981Fuj]

[1983Bus]

[1984Bat]

[1984Bon]

[1986Mur]

[1986Sat] [1987Bal]

[1987Gel]

[1988Mil] [1988Ray] [1988Sud]

Fe–Mn–Si Shoemaker, C.B., Shoemaker, D.P., “The Crystal Structure and Superstructure of the K Phase, Mn77Fe4Si19”, Acta Crystallogr., 33B, 743–754 (1977) (Crys. Structure, Experimental, 14) Vereshchagin, Yu.A., Sidorenko, F.A., Ryzhenko, B.V., Babanova, E.N., Geld, P.V., “Peculiarities of Filling Unequivalent Sites in the Quasi-Binary Solid Solutions with L21 Lattice” (in Russian), Ukrain. Fiz. Zhur., 22(9), 1472–1476 (1977) (Crys. Structure, Experimental, 11) Yoon, S., Booth, J.G., “Magnetic Properties and Structures of Some Ordered (FeMn)3Si Alloys”, J. Phys. F: Met. Phys., 7(6), 1079–1095 (1977) (Crys. Structure, Experimental, Magn. Prop., 19) Gee, R., Rosenqvist T., “Activities in Liquid Fe-Mn-Si Alloys”, Scandin. J. Metall., 7(1), 38–41 (1978) (Experimental, Thermodyn., 10) Narita, K., Enokizono, M., “Effect of Nickel and Manganese Addition on Ductility and Magnetic Properties of 6.5 % Silicon-Iron Alloy”, IEEE Trans. Magn., 14(4), 258–262 (1978) (Experimental, Magn. Prop., Mechan. Prop., Morphology, Phase Relations, 5) Arita, M., Saint Pierre, R., “Activity Measurements in Liquid Fe-Mn-Si Alloys at 1833K”, Trans. Iron Steel Inst. Jpn., 19, 374–376 (1979) (Experimental, Thermodyn., 14) Bobrov, N.P., Sudakova, N.P., Kuznetsov, S.I., Esin, Y.O., Sintez, I, “About Thermodynamics of Alloys of Fe5Si3-Mn5Si3 System” (in Russian), Svoistya Beskiscorod. Neorgan. Materialov, Sverdlovsk, 52–54 (1980) (Experimental, Thermodyn., 5) Smith, T.F., Bristow, G.K., Boughton, C.V., Hudson, P.R.W., “Speciﬁc Heat Capacity of Fe3–xMnxSi Compounds”, J. Phys. F, Metal Phys., 10, 2867–2873 (1980) (Experimental, Thermodyn., 8) Fujisawa, T., Imaoka, K., Sakao, H., “Activities of Manganese and Silicon in δ -Iron at Solid-Liquid Equilibrium Temperatures”, Trans. Iron Steel Inst. Jpn., 21, 559–567 (1981) (Experimental, Phase Relations, Thermodyn., 68) Buschow, K.H.J., Van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of Metals Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1–22 (1983) (Experimental, Magn. Prop., Optical Prop., 23) Batalin, G.I., Sudavtsova, V.S., Bondarenko, T.P., Ul’yanov, V.I., “Heat of Mixing of Mn, Si, Al, Ti in rich Iron and its Alloys” (in Russian), Ukr. Khim. Zh., 50, 582–585 (1984) (Experimental, Calculation, Thermodyn., 4) Bondarenko, T.P., Sudavtsova, V.S., Batalin, G.I., Ulyanov, V.I., “Enthalpies of Mixing for Liquid Fe-Si-Mn Alloys”, Russ. Metall., (3), 75–76 (1984), translated from Izv. Akad. Nauk SSSR, Metall., (3), 81–82 (1984) (Calculation, Experimental, Thermodyn., 3) Murakami, M., “Effect of Alloying Content, Phase and Magnetic Transformation on the Shape Memory Effect of Fe-Mn-Si Alloys” (in Japanese), Tetsu To Hagane,, 72(13), 1574–1574 (1986) (Experimental, Magn. Prop., Mechan. Prop., 0) Sato, A., Yamaji, Y., Mori, T., “Physical Properties Controlling Shape Memory Effect in Fe-Mn-Si Alloys”, Acta Metall., 34(2), 287–294 (1986) (Experimental, Magn. Prop., 30) Balkavoi, Yu.V., Aleev, R.A., Manokhin, A.A., “Inﬂuence of Carbon, Silicium and Vanadium on the Activity of Mn in Fe” (in Russian), Izv. V.U.Z. Chern. Metall., (9), 128–129 (1987) (Calculation, Thermodyn., Experimental, 3) Geld, P.V., Povzner, A.A., Kortov, S.V., Krentsis, R.P., “Thermal Expansion and Weak Itinerant Magnetism in Fe1–yMnySi and Fe1–xCoxSi Solid Solutions”, Sov. Phys. -Dokl., 32(12), 1006–1008 (1987), translated from Dokl. Akad. Nauk SSSR, 297, 1359–1363, (1987) (Experimental, Thermodyn., Magn. Prop., 10) Miles, J.R., Smith, T.F., Finlayson, T.R., “Thermal Expansion of Fe2MnSi”, Aust. J. Phys., 41, 781–790 (1988) (Experimental, Thermodyn., Magn. Prop., 24) Raynor, G.V., Rivlin, V.G., “Fe-Mn-Si” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 363–377 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Review, 20) Sudavtsova, V.S., Batalin, G.I., Bondarenko, T.P., “The Enthalpies of Formation of Liquid Ferrosilicon-Manganese {(FeSi)-Mn} Alloys”, Russ. J. Phys. Chem., 62, 702–703 (1988), translated from Zh. Fiz. Khim., 62, 1383–1385 (1988) (Experimental, Thermodyn., 5)

DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si [1989Bon]

[1990Ots]

[1990Sad]

[1991Lan]

[1991Mil] [1992For]

[1993For]

[1993Wat] [1994Rag] [1995Bou]

[1995Ron]

[1995Tan]

[1996Mat]

[1996Qin]

[1996Spo]

[1996Zai1]

[1996Zai2]

[1996Zha]

Landolt-Börnstein New Series IV/11D4

37

Bondarenko, T.P., Sudavtsova, V.S., “Thermochemical Properties in Melts of (MnSi)-Fe, (FeSi)-Mn” (in Russian), Ukr. Khim. Zh., 55(1), 23–24 (1989) (Experimental, Thermodyn., 7) Otsuka, H., Yamada, H., Maruyama, T., Tanahashi, H., Matsuda, S., Murakami, M., “Effects of Alloying Additions on Fe-Mn-Si Shape Memory Alloys”, ISIJ Int., 30(8), 674–679 (1990) (Experimental, Mechan. Prop., Magn. Prop., 19) Sade, M., Halter, K., Hornbogen, E., “Transformation Behaviour and One-Way Shape Memory Effect in Fe-Mn-Si Shape Memory Alloys”, J. Mater. Sci. Lett., 9, 112–115 (1990) (Experimental, Magn. Prop., 8) Langhong, L., Tianxiang, Z., Yaoxiao, Z., “Development of Fe3Si Alloys” in “High-Temp. Ordered Intermetallic Alloys IV ”, Mater. Res. Soc. Symp. Proc., 213, 833–838 (1991) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, Phys. Prop., 8) Miles, J.R., Smith, T.F., Finlayson, T.R., “Thermodynamic Study of the Magnetic Ordering of Fe3–xMnxSi Alloys”, Int. J. Thermoph., 12(4), 617–626 (1991) (Experimental, Magn. Prop., 11) Forsberg, A., Agren, J., “Thermodynamics, Phase Equilibria and Martensitic Transformation in Fe-Mn-Si Alloys” in “Shape-Memory Materials and Phenomena - Fundamental Aspects and Applications”, Mater. Res. Soc., Symp. Proc., Pittsburg, PA, USA, 246, 289–295 (1992) (Phase Diagram, Phase Relations, Thermodyn., 24) Forsberg, A., Agren, J., “Thermodynamic Evaluation of the Fe-Mn-Si System and the γ/ε Martensitic Transformation”, J. Phase Equilib., 14(3), 354–363 (1993) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 29) Watanabe, Y., Mori, Y., Sato, A., “Training Effect in Fe-Mn-Si Shape-Memory Alloys”, J. Mater. Sci., 28, 1509–1514 (1993) (Experimental, Mechan. Prop., 9) Raghavan, V., “Fe-Mn-Si (Iron-Manganese-Silicon)”, J. Phase Equilib., 15(6), 619–620 (1994) (Phase Diagram, Phase Relations, Review, 13) Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B(3), 467–484 (1995) (Phase Relations, Theory, Thermodyn., 85) Rong, L.J., Li, Y.Y., Shi, S.X., “An Electron Microscopy Study of the Reverse Transformation Behaviour of Stress-Induced Martensite in an Fe-Mn-Si Alloy”, Mater. Lett., 24, 143–146 (1995) (Experimental, Mechan. Prop., 12) Tanaka, T., Aaronson, H.I., Enomoto, M., “Calculations of α/γ Phase Boundaries in Fe-CX1-X2 Systems from the Central Atoms Model”, Metall. Mater. Trans. A, 26A(3), 535–545 (1995) (Calculation, Phase Relations, Thermodyn., 27) Matsumura, O., Furusako, S., Furukawa, T., Otsuka, H., “Formation of Surface Texture and Anisotropy of Shape Memory Effect in an Fe-Mn-Si Alloy”, ISIJ Int., 36(8), 1103–1108 (1997) (Experimental, Mechan. Prop., 18) Qin, Z., Yu, M., Zhang, Y., “Neel Transition and γ -ɛ Transformation in Polycrystalline FeMn-Si Shape Memory Alloys”, J. Mater. Sci., 31(9), 2311–2315 (1996) (Electr. Prop., Experimental, Morphology, Phys. Prop., Thermodyn., 19) Spolenak, R., Bauer, E., Müller, H., Kirchmayr, H., Blaha, P., Mohn, P., Schwarz, K., “(Fe,Mn) Si: Transitions from a Magnetic to a Nonmagnetic State and from Metallic to Semiconducting Behaviour”, J. Magn. Magn. Mat., 157–158, 715–716 (1996) (Theory, Magn. Prop., 8) Zaitsev, A.I., Litvina, A.D., Shelkova, N.E., Mogutnov, B.M., “Thermodynamic Properties of {xFe+yMn+(1–x–y)Si}(I) and {xFe+yMn+(1–x–y)P(I)”, J. Chem. Thermodyn., 28, 285–306 (1996) (Experimental, Thermodyn., 66) Zaitsev, A.I., Mogutnov, B.M., “The Thermodynamic Properties of Iron-Manganese-Silicon Melts”, Russ. J. Phys. Chem., 70(4), 554–561 (1996), translated from Zh. Fiz. Khim., 70(4), 599–606 (1996) (Experimental, Kinetics, Phys. Prop., Thermodyn., 34) Zhao, Z.T., Liu, T., Liu, G.W., Ma, R.Z., “Reverse Martensite Transformation Induced by Strain in Fe-Mn-Si Alloy”, J. Mater. Sci. Lett., 15(16), 1427–1428 (1996) (Crys. Structure, Electr. Prop., Experimental, Phase Relations, 5)

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38 [1997And] [1997Li1] [1997Li2]

[1998Cot1]

[1998Cot2]

[1998Mie]

[1998Muk] [1998Qin]

[1998Zai]

[1999Che]

[1999Cho]

[1999Cot]

[1999Guo]

[1999Hsu] [1999Jin]

[2000Aru]

[2000Dai] [2000Hsu] [2000Jin1]

Fe–Mn–Si Andersson, M., “Enthalpy Change of the ε→γ Transformation in Fe-Mn-Si Alloys”, Scand. J. Metall., 26, 139–144 (1997) (Experimental, Thermodyn., 10) Li, L., Hsu, T.Y., “Gibbs Free Energy Evaluation of the fcc(γ ) and hcp(ε) Phases in the Fe-Mn-Si Alloys”, Calphad, 21(3), 443–448 (1997) (Calculation, Thermodyn., 17) Li, H., Morris, A., “Evaluation of Uniﬁed Interaction Parameter Model Parameters for Calculating Activities of Ferromanganese Alloys: Mn-Fe-C, Mn-Fe-Si, and Mn-Fe-C-Si Systems”, Metall. Mater. Trans. B, 28B(4), 553–562 (1997) (Thermodyn., Calculation, 41) Cotes, S., Fernandez-Guilermet, A., Sade, M., “Phase Stability and FCC/HCP Martensitic Transformation in Fe-Mn-Si Alloys Part 1: Experimental Study and Systematics of the Ms and As Temperatures”, J. Alloys Compd., 278, 231–238 (1998) (Experimental, Phase Relations, 28) Cotes, S., Fernandez-Guillermet, A., Sade, M., “Phase Stability and fcc/hcp Martensitic Transformation in Fe-Mn-Si Alloys: Part II. Thermodynamic Modeling of the Driving Forces and the Ms and As Temperatures”, J. Alloys Compd., 280, 168–177 (1998) (Theory, Phase Relations, Thermodyn., 17) Miettinen, J., “Reassessed Thermodynamic Solution Phase Data for Ternary Fe-Si-C System”, Calphad, 22(2), 231–256 (1998) (Calculation, Assessment, Thermodyn., Phase Relations, 36) Mukherjee, G.D., Bansal, C., Chatterjee, A., “Thermal Expansion Study of Fe-Mn-Si Alloys”, Physica B, 254, 223–233 (1998) (Experimental, Theory, Magn. Prop., 33) Qin, Z., Zhang, Y., “Mössbauer Effect Study of Antiferromagnetic Fe-Mn-Si Alloys”, Hyperfine Interact., 116, 225–235 (1998) (Crys. Structure, Electronic Structure, Experimental, 20) Zaitsev, A.I., Litvina, A.D., Shelkova, N.E., Mogutnov, B.M., “Association in Ternary Metallic Melts Fe-Mn-Si, Fe-Cr-P and Fe-Mn-P”, Thermochim. Acta, 314, 307–315 (1998) (Experimental, Phase Relations, Thermodyn., 31) Chen, S., Chung, C.Y., Yan, C., Hus, T.Y., “Effect of f.c.c. Antiferromagnetism on Martensitic Transformation in Fe-Mn-Si Based Alloys”, Mater. Sci. Eng. A, A264, 262–268 (1999) (Experimental, Mechan. Prop., 28) Cho, W.-S., Choi, S.-W., Park, K., “Microstructure and Thermoelectric Properties of p-type Fe0.9Mn0.1Si2 Compounds Prepared by Pressureless Sintering”, Mater. Sci. Eng. B, B68, 116–122 (1999) (Experimental, Phase Relations, Electr. Prop., 28) Cotes, S., Fernandez-Guillerment, A., Sade, M., “Gibbs Energy Modelling of the Driving Forces and Calculation of the FCC/HCP Martensitic Transformation Temperatures in Fe-Mn and Fe-Mn-Si Alloys”, Mat. Sci. Eng. A, A275, 503–506 (1999) (Calculation, Thermodyn., 21) Guo, Z., Rong, Y., Chen, S., Hsu, T.Y., “Crystallography of fcc(γ)→hcp(ε) Martensitic Transformation in Fe-Mn-Si Based Alloys”, Scr. Mater., 41(2), 153–158 (1999) (Theory, Phase Relations, 15) Hsu, T.Y., Zhuyao, X., “Martensitic Transformation in Fe-Mn-Si Based Alloys”, Mater. Sci. Eng. A, A273–275, 494–497 (1999) (Theory, Phys. Prop., Phase Relations, 40) Jin, X.J., Hsu, T.Y., “Thermodynamic Consideration of Antiferromagnetic Transition on fcc (γ )-hcp(ε) Martensitic Transformation in Fe-Mn-Si Shape Memory Alloys”, Mater. Chem. Phys., 61, 135–138 (1999) (Calculation, Phase Relations, 19) Arushanov, E., Schoen, J.H., Tani, J.-I., Kido, H., “Transport Properties of β-Fe1–xMnxSi2 Alloys”, Phys. Status Solidi A, 181A, 185–191 (2000) (Crys. Structure, Electr. Prop., Experimental, 17) Dai, P., “Effect of Solution Hardening on the Shape Memory Properties of Fe-Mn-Si based Alloys”, J. Mater. Sci. Lett., 19, 111–113 (2000) (Experimental, Mechan. Prop., 9) Hsu, T.Y., “Fe-Mn-Si Based Shape Memory Alloys”, Mater. Sci. Forum, 327–328, 199–206 (2000) (Review, Experimental, Magn. Prop., 62) Jin, X., Hsu, T.Y., “Prediction of Martensitic Transformation Start Temperature Ms in FeMn-Si Shape Memory Alloys”, Mater. Sci. Forum, 327–328, 219–222 (2000) (Experimental, Phase Relations, 14)

DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–Mn–Si [2000Jin2] [2000Wu]

[2001Cho]

[2001Wan1] [2001Wan2]

[2002AlN]

[2002Son]

[2002Tan]

[2003Che]

[2003Luo] [2003Zhu]

[2004Can]

[2004Wit]

[2005Jia]

[2005Lin]

[2005Mec]

[2005Sta] [2005Wan]

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39

Jin, X., Jihua, Z., Hsu, T.Y., “Thermodynamic Calculation of Stacking Fault Energy in Fe-MnSi Shape Memory Alloys”, Mater. Design, 21, 537–539 (2000) (Theory, Thermodyn., 19) Wu, X., Hsu, T.Y., “Effect of the Neel Temperature, TN, on Martensitic Transformation in Fe-Mn-Si-Based Shape Memory Alloys”, Mater. Charact., 45(2), 137–142 (2000) (Experimental, Phase Relations, 20) Cho, W.-S., “Thermodynamic Properties of Fe0.9Mn0.1Si2 Thermoelectric Materials Prepared by Presureless Sintering”, Key Eng. Mater., 189–191, 315–321 (2001) (Crys. Structure, Electr. Prop., Experimental, Phys. Prop., 10) Wan, J., Chen, S., Hsu, T.Y., “The Stability of Transition Phases in Fe-Mn-Si Based Alloys”, Calphad, 25(3), 355–362 (2001) (Calculation, Thermodyn., 21) Wan, J., Chen, S.P., Hsu, T.Y., “Group Theory Analyses of Transition Structures Related to the γ→ε Transformation in Fe-Mn-Si Based Alloys”, Mater. Chem. Phys., 71, 90–93 (2001) (Theory, Phase Relations, 16) Al-Nawashi, G.A., Mahmood, S.H., Lehlooh, A.-F.D., Saleh, A.S., “Mössbauer Spectroscopic Study of Order-Disorder Phenomena in Fe3–xMnxSi”, Physica B, 321, 167–172 (2002) (Crys. Structure, Theory, Electronic Structure, 11) Songlin, D., Tegus, O., Brueck, E., Klaasse, J.C.P., de Boer, F.R., Buschow, K.H.J., “Magnetic Phase Transition and Magnetocaloric Effect in Mn5–xFexSi3”, J. Alloys Compd., 334, 249–252 (2002) (Experimental, Magn. Prop., Phase Relations, 6) Tani, J.I., Kido, H., “First Principle Calculation of the Geometrical and Electronic Structure of Impurity-Doped β-FeSi2 Semiconductors”, J. Solid State Chem., 163, 248–252 (2002) (Calculation, Crys. Structure, Phys. Prop., 23) Chen, H.Y., Zhao, X.B., Lu, Y.F., Mueller, E., Mrotzek, A., “Microstructures and Thermoelectric Properties of Fe0.92Mn0.08Six Alloys Prepared by Rapid Solidiﬁcation and Hot Pressing”, J. Appl. Phys., 94(10), 6621–6626 (2003) (Crys. Structure, Electr. Prop., Experimental, Morphology, Thermodyn., 30) Luo, S.J., Yao, K.L., Liu, Z.L., “On the Magnetic Phase Transition in FexMn1–xSi”, J. Magn. Magn. Mater., 265, 167–171 (2003) (Crys. Structure, Theory, Magn. Prop., 18) Zhu, T.-J., Zhao, X.B., Lu, L., “Preparation and Thermoelectric Properties of Melt-Spun Fe2Si5 Based Alloys”, Mater. Sci. Forum, 437–438, 471–474 (2003) (Electr. Prop., Experimental, Phase Relations, 7) Candini, A., Moze, O., Kockelmann, W., Cadogan, J.M., Brueck, E., Tegus, O., “Revised Magnetic Phase Diagram for FexMn5–xSi3 Intermetallics”, J. Appl. Phys., 95(11), 6819–6821 (2004) (Crys. Structure, Experimental, Magn. Prop., Phase Relations, 14) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Calculation, Thermodyn., #, 34) Jiang, J.X., Matsugi, K., Sasaki, G., Yanagisawa, O., “Conduction Type Evolution During Eutectoid Decomposition of Mn-Added α-Fe2Si5 Alloy”, Scr. Mater., 53(6), 707–711 (2005) (Crys. Structure, Electr. Prop., Experimental, Phase Relations, 22) Lin, H.C., Lin, K.M., Chen, Y.S., Chu, C.L., “The Wire Electro-Discharge Machining Characteristics of Fe-30Mn-6Si and Fe-30Mn-6Si-5Cr Shape Memory Alloys”, J. Mat. Proc. Tech., 161(3), 435–439 (2005) (Crys. Structure, Experimental, Morphology, Phase Relations, Phys. Prop., 17) Meco, H., Napolitano, R.E., “Liquidus and Solidus Boundaries in the Vicinity of OrderDisorder Transitions in Fe-Si System”, Scr. Mater., 52, 221–226 (2005) (Experimental, Calculation, Phase Diagram, Thermodyn., 30) Stanford, N., Dunne, D., “Martensitic Surface Relief in an Fe-Mn-Si-based Alloy Strained by Bending“, Scr. Mater., 53, 739–744 (2005) (Experimental, Mechan. Prop., 8) Wan, J., Chen, S., “Martensitic Transformation and Shape Memory Effect in Fe-Mn-Si Based Alloys”, Curr. Opin. Solid State Mater. Sci., 9, 303–312 (2005) (Theory, Phase Relations, 56)

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40 [2007Sta]

[2007Wit] [Mas2] [V-C2]

Fe–Mn–Si Stanford, N., Dunne, D.P., Monaghan, B.J., “Austenite Stability in Fe-Mn-Si-Based Shape Memory Alloys”, J. Alloys Compd., 430(1–2), 107–115 (2007) (Calculation, Crys. Structure, Experimental, Mechan. Prop., Morphology, Phase Relations, 25) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_21 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mn–Ti

1

Iron – Manganese – Titanium Volodymyr Ivanchenko, Tetyana Pryadko

Introduction In spite of the practical application of the Fe-Mn-Ti alloys in the development of high strength austenitic steels and nickel free ferritic steels for cryogenic applications, as well as for the development of new Ti based structural alloys and materials for hydrogen storage, the experimental data on the phase equilibria in this system are incomplete and partly contradictory. The liquidus surface of the Fe-Mn-Ti system has been investigated by [1958Mur1] for the Ti contents app. 20 to 100 at.% and reproduced in [1983Riv, 1988Ray]. The 1000°C isothermal section in the same composition region has been presented by [1958Mur2]. Based on these results [1988Ray] presented the content of the ternary (βTi) ﬁeld as a function of temperature for the temperature range 600–1000°C. The effect of alloying with Fe on the stability of (αMn), (βMn) and TiMn4 phases has been studied by [1969Pan] and reproduced in [1980Bra]. The phase compositions and variation of the cell parameters of the Laves phase (Ti1–yMny)Fe2 with 0 ≤ y ≤ 0.17 have been presented by [1972Mar]. An important contribution was made in the works of [1979Dew, 1979Kau] by a direct experimental investigation of the system, mainly to establish the boundaries of the TiFe phase but providing evidence with regard to the Ti rich boundary of the Ti(Mn,Fe)2 phase and the general nature of the equilibria. Solid phase equilibria of the Fe-Mn-Ti system at 1000°C near the Fe-Mn border were presented by [1988Ray] according to [1969Pan]. The ﬁelds of primary separation in this composition region were constructed by [1988Ray] from the data of [1969Pan]. [1990Har] computed the α-γ equilibrium in the Fe rich alloys at 1150, 1050, 950 and 850°C using the sublattice model for TiFe2 and the magnetic single-lattice model for the solution phases. The isothermal sections in the Fe rich part of the phase diagram at 1150 and 850°C have been presented by [1994Rag] according to [1990Har]. Experimental studies of the phase equilibria, thermodynamics and crystal structures are listed in Table 1. Binary Systems The Fe-Ti, Fe-Mn, and Mn-Ti are taken from [Mas2], [2004Wit], and [Mas2], respectively. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). Solid Phases A complete solid solution forms between TiFe2 and MnFe2. A substantial solid solubility of Mn in TiFe suggests a general replacement of the Fe atoms by Mn atoms up to a limit of approximately 26 at.% Mn [1979Dew]. [1979Dew] reported about the existence of a phase with the composition 54.8Ti-35.9Mn (at.%) at 1000°C. According to [1979Dew] it could be derived from the Mn-Ti ρ phase or it could be an entirely new ternary phase. Crystal structures of the phases in the Fe-Mn-Ti system are presented in Table 2. Quasibinary Systems The quasibinary section TiMn2-TiFe2 is given in Fig. 1 in accordance with [2007Iva]. The melting and freezing points reported by [2007Iva] are lower than the values presented by [1958Mur1]. They are, however, in good agreement with [1988Ray], who omitted the isothermal curves at 1450 and 1500°C presented by [1958Mur1], because they contradict the accepted melting point of TiFe2. Invariant Equilibria Four-phase invariant equilibria in the Fe-Mn-Ti ternary system are presented in Table 3 in accordance with a tentative liquidus surface projection of the partial Ti-TiMn2-TiFe2 system constructed by [1988Ray] using Landolt-Börnstein New Series IV/11D4

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experimental data of [1958Mur1, 1979Dew]. A reaction scheme for the partial Ti-TiMn2-TiFe2 system shown in Fig. 2 is taken from [1988Ray]. Liquidus, Solidus and Solvus Surfaces A liquidus surface of the partial system up to 85 mass% Ti is given in Fig. 3 according to [1958Mur1, 1983Riv, 1988Ray], with some corrections. The freezing temperatures of the alloys located along the TiMn2-TiFe2 section measured by [2007Iva] are accepted. They have been obtained using a more precise technique of measurements and are in a better accordance with the freezing point of TiFe2. On the surface of primary separation of the ternary Laves phase only the 1400 and 1350°C isothermal lines are retained from [1958Mur1] and [1988Ray]. Other isothermal lines are excluded as appearing at much too high temperatures compared with [2007Iva]. The primary crystallization ﬁelds near the Fe-Mn border are given in Fig. 3 according to a hypothetical construction of [1988Ray]. Using thermal analysis and metallographic and electrical resistance techniques [1958Mur2] derived the position of the (βTi) border at various temperatures, shown in Fig. 4 after minor adjustments for compliance with the accepted binary diagrams. Isothermal Sections The 1000°C isothermal section has been investigated by [1958Mur2] in the area from app. 20 to 100 mass% Ti (22 to 100 (at.%)). A remarkable feature of this section is the complete solid solution (Fe,Mn)2Ti (λ phase). A substantial solubility of Mn in FeTi is also shown, suggesting a general replacement of the Fe atoms by Mn atoms up to a limit of approximately 20 mass% Mn (19 at.% Mn), with a tolerance for a moderate excess or deﬁcit of Ti [1988Ray]. Another version of the 1000°C isothermal section has been proposed by [1979Dew]. Using electron-probe microanalysis [1979Dew] determined at 1000°C a phase with the composition 51.5Ti-38.7Mn (mass%) (55Ti-9.5Fe-36Mn (at.%)). According to [1979Dew] this phase could be derived from the binary Mn-Ti ρ-phase or it could be a new true ternary phase. In the present evaluation we consider it as a ternary extension of the ρ-phase. The electron-probe microanalysis results [1979Dew] show that the Ti rich boundary of the λ phase ﬁeld bends sharply towards the Ti corner of the diagram when the Fe content decreases to approximately 20 mass% (14 at.%). There are some differences between the diagram of [1979Dew] and that due to [1958Mur2]. The maximum solid solubility of Fe and Mn in (Ti) is substantially higher (32 at.% solute) in [1979Dew] than that in [1958Mur2]. A two-phase equilibrium λ+(βTi) exists in contrast to the equilibrium between FeTi and ρ as presented by [1958Mur2]. Thus, the nature of the equilibria at 1000°C established by [1958Mur2] and by [1979Dew] differs. The electron-probe microanalysis work of [1979Dew] seem to be very carefully carried out and the proposed equilibria may be preferred. Therefore the results of [1979Dew] are accepted and shown in Fig. 5 for the Ti rich area in the version of [1988Rag] who has added a tentative tie triangle ρ+λ+(βTi). The solid phase equilibria in the Ti poor area at 1000°C have been investigated by [1969Pan] and [1972Mar]. In [1972Mar] no mention was made of the heat treatment, and, as it was pointed out by [1988Ray], it must be assumed that the results refer to the constitution of the “as-prepared” specimens, in which the equilibrium is doubtful. Therefore this work is not considered in the present evaluation. The Ti poor area is shown in Fig. 5 mainly from [1969Pan], but after some modiﬁcations described below. The shape and the extension of the λ phase shown by [1969Pan] do not agree with that of [1958Mur2] and [1979Dew] and therefore it has been changed in Fig. 5 to bring it in compliance with the latter works. This change resulted in a small shift of the λ corners of the adjacent tie triangles. The homogeneity range of the R phase along the Mn-Ti axis is reduced to bring it in accord with the accepted binary Mn-Ti system. Also a small violation of the Schreinmaker rule has been eliminated in Fig. 5 at the (αFe) corner of the (αFe) +(αMn)+(γFe) tie triangle. The phase denoted as X in [1969Pan] has been interpreted by [1988Ray] as a ternary extension of the TiMn3 phase. This is accepted here. A tie triangle λ+R+TiMn3 is speculatively added in Fig. 5 (marked with a question mark) to merge the Ti rich and Ti poor parts from different works. In fact, this seems to be the only alternative conﬁguration considering all the phases taking part in equilibria

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in this area. In Fig. 5 all the compositions of the binary phases along the binary axes are adjusted to the binary phase diagrams accepted in the present evaluation. Comparison of the 1000°C section calculated by [1979Dew] with the assessed diagram in Fig. 5 reveals the following discrepancies: ternary extensions of the TiFe, (αMn) and (αδFe) phases are much smaller in the calculated diagram; calculation showed an equilibrium (γFe) + λ, which is not established experimentally; λ phase is calculated without a homogeneity range along the binary axis; the ρ phase is not revealed by the calculation. Accept for the above the agreement is good, in particular in the Ti rich region. The isothermal sections at 1150 and 850°C in the Fe corner are shown in Fig. 6 and Fig. 7 from the computations of [1990Har]. Thermodynamics The effect of Ti on the activity coefﬁcient of Mn in Fe-Mn-Ti alloys was analyzed by [1995Bou] who concludes that the presence of Ti leads to a small increase in the activity coefﬁcient of Mn. In liquid Fe, the interactions between Mn and Ti atoms should be similar to those between Ti atoms. Notes on Materials Properties and Applications The Fe-Mn-Ti system is the basis for the development of precipitation strengthened austenitic [1950Cra, 1979Cha] and nickel-free ferritic steels for cryogenic applications [1971Man, 1978Hwa]. Fe and Mn are well known as beta-stabilizers in the titanium industry. Alloying with Fe and Mn in the amount up to 5 mass% Mn and 2 mass% Fe raises the tensile strength but with sacriﬁce in ductility [1950Cra]. Inﬂuence of Mn on sintering process in the Fe-Ti system has been studied by [1985Kiv], and volume changes in sintering of Fe-Mn-Ti compacts were presented. New composite TiMn2-TiFe were developed by the traditional liquid phase sintering [1985Kiv] and by mechanical alloying [2003Cho] with the aim of developing materials with a hydrogen capacity storage. Experimental data regarding works on material properties are summarized in Table 4. Miscellaneous Magnetic phase diagram of the Ti(MnxFe1–x)2 system with x ≤ 0.6 is presented in Fig. 8 according to [2005Yam]. An icosahedral crystal of the Ti61Fe30Mn7Si2 composition has been grown [1992Zha] by electron beam smelting. Unlike most icosahedral phases, the 5-fold axis is the direction of the most rapid growth.

Table 1.

Investigations of the Fe-Mn-Ti Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1958Mur2]

XRD (X-ray diffraction), optical microscopy, electrical resistance

1000°C for 100 h and quenched in water, < 85 mass% Ti

[1969Pan]

XRD, optical microscopy, chemical analysis

1000°C for 72 h and quenched in water, < 30 at.% Ti

[1972Mar]

EPMA (electron probe microanalysis), X-ray diffraction

As cast, λ, (Ti1–xMnx)Fe2 (x < 0.17)

[1979Dew]

EPMA, SEM (scanning electron microscopy)

1000°C, the whole diagram by calculation and experiment

[2007Iva]

XRD, thermal analysis

1325–1450°C, TiMn2-TiFe2 joint

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Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

(αTi) < 882

hP2 P63/mmc Mg

a = 295.06 c = 468.35

αβδ, (Ti,Mn,Fe) (βTi) 1670–882

cI2 Im 3m W

(δMn)(h3) < 1246 (δFe) 1538–1394 (αFe) < 912

Comments/References

pure Ti at 25°C [Mas2] a = 330.65

pure Ti at 25°C [Mas2]

a = 308.0

pure, at >1138°C [Mas2]

a = 293.15 a = 286.65

pure Fe at 1390°C [V-C2, Mas2] pure Fe at 25°C [Mas2]

a = 386.0

pure Mn, at 1100°C [Mas2]

a = 364.67

pure Fe at 915°C [V-C2, Mas2]

γ, (Mn,Fe) (γMn)(h2) < 1138 (γFe) 1394–912

cF4 Fm 3m Cu

(βMn)(h1) < 1100

cP20 P4132 βMn

a = 631.52

pure Mn, at 727°C [Mas2]

(αMn)(r) < 727

cI58 I 43m αMn

a = 891.26

pure Mn, at 25°C [Mas2]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]

(ωTi)HP

hP3 P6/mmm ωTi

a = 462.5 c = 281.3

at 25°C [Mas2]

TiFe < 1317

cP2 Pm 3m CsCl

a = 298.8 to 297.7

48–50.2 at.% Fe [Mas2]

λ, Ti(Mn,Fe)2

hP12 P63/mmc MgZn2

Laves Phase a = 483.03–5.7 xFe [2007Iva] c = 792.28–16.3 xFe xFe: mole fraction Fe

TiFe2 < 1424

a = 480.4 to 477.7 c = 784.9 to 780.7

65.2–72.8 at.% Fe, annealed at 1000°C [Mas2]

TiMn2 < 1325

a= 485.7 to 481.8 c= 801.7 to 87.9

64–70 at.% Mn, at 1310°C [1976Sve] (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

ρ, βTiMn ≲ 1200

-

-

52 at.% Mn [1961Wat, 1962Wat] 48–52 at.% Mn, [2004Iva]

ϕ, αTiMn ≲ 950

tP30 P42/mnm CrFe

a = 888 c = 454.2

[Mas2], [V-C2]

TiMn3 < 1250

oP* P212121

a = 481.2 c = 789.5

75.5 at.% Mn, at 1000°C [Mas2]

R, TiMn4 1230–930

hR159 R 3m Co5Cr2Mo3

a = 1100.03 c = 1944.6

[V-C2], [Mas2]. Phase referred to as TiMn5 in [V-C2]. Prototype given as ∼δ(Mo,Ni) in [Mas2]

Table 3.

Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (at.%) Fe

Mn

Ti

L + λ ⇌ TiFe + ρ

∼ 1100

U1

L

∼17

∼23

∼60

L ⇌ (βTi) + TiFe + ρ

∼ 1050

E1

L

∼16

∼18

∼66

L + (αδFe) ⇌ (γFe) +γ

∼ >1000

U2

L

∼72

∼12

∼16

L + (γFe) + λ ⇌ TiMn4

?

P1

L

∼28

∼52

∼20

L + λ + TiMn4 ⇌ TiMn3

?

P2

L

∼15

∼64

∼21

L + (γFe) ⇌ TiMn4 + (δMn)

?

U3

L

∼12

∼76

∼12

Table 4.

Investigations of the Fe-Mn-Ti Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1950Cra]

Tensile tests, hardness measurements

Tensile strength, elongation, Vickers hardness

[1971Man]

Tensile tests, hardness measurements

Tensile strength, elongation, Vickers hardness

[1978Hwa]

Tensile tests at cryogenic temperatures, Auger electron spectroscopy, SEM

Tensile strength, elongation

[1979Cha]

Optical microscopy, EDAX, X-ray diffraction, TEM, precipitation strengthening

Annealed 1.5 h at 1150°C, then water quenched and at 700–900°C 20 and 28 mass% Mn, 2 mass% Ti

[1985Kiv]

XRD, speciﬁc surface and volume change measurements

1050–1250°C, TiFe0.8Mn0.2, shrinkage under sintering (continued)

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Reference

Method/Experimental Technique

Type of Property

[1992Zha]

XRD, TEM, EDS (electron dispersive X-ray spectroscopy)

Ti61Fe30Mn7Si2, electron beam melting, icosahedral crystal

[2003Cho]

XRD, EDS, hydrogen adsorption by the Sievert’s method

Ball milled, then annealed 1H at 800°C, hydrogen storage

[2005Yam]

XRD, Magnetization, 55Mn nuclear magnetic resonance (NMR)

4.2–300 K, Ti(Fe1–xMnx)2 (x < 0.6), magnetic ordering

Fig. 1. Fe-Mn-Ti. Quasibinary section TiMn2-TiFe2

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Fig. 2. Fe-Mn-Ti. Partial reaction scheme

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Fig. 3. Fe-Mn-Ti. Liquidus surface projection

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Fig. 4. Fe-Mn-Ti. Solid solubility of Fe and Mn in (βTi) at 1000–600°C

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Fig. 5. Fe-Mn-Ti. Isothermal section at 1000°C

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Fig. 6. Fe-Mn-Ti. Computed isothermal section at 1150°C

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Fig. 7. Fe-Mn-Ti. Computed isothermal section at 850°C

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Fig. 8. Fe-Mn-Ti. Magnetic phase diagram of the Ti(Fe1–xMnx)2 system

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14 References [1950Cra] [1958Mur1]

[1958Mur2]

[1961Wat] [1962Wat]

[1969Pan]

[1971Man]

[1972Mar]

[1976Sve]

[1978Hwa]

[1979Cha]

[1979Dew]

[1979Kau]

[1980Bra] [1983Riv]

[1985Kiv]

[1986Cen]

Fe–Mn–Ti

Craighead, C.M., Simmons, G.W., Eastwood, L.W., “Ternary Alloys of Titanium”, Trans. Met. Soc. AIME, 188, 514–538 (1950) (Experimental, Morphology, Mechan. Prop., 1) Murakami, Y., Yukawa, Y., Enjyo, T., “Investigation of the Ti-Rich Ti-Fe-Mn Alloy System. II. On Liquidus Surface of the Ti-Fe-Mn System” (in Japanese), Nippon Kinzoku Gakkai-Shi, 22, 265–269 (1958) (Crys. Structure, Experimental, Morphology, Phase Relations, Phys. Prop., 2) Murakami, Y., Enjyo, T., “Investigation of the Ti-Rich Ti-Fe-Mn Alloy System III. On the Solid Equilibrium Relation in Ti-Fe-Mn System” (in Japanese), Nippon Kinzoku Gakkai Shi, 22, 328–332 (1958) (Experimental, Morphology, Phase Diagram, Phase Relations, Phys. Prop., 3) Waterstrat, R.M., “Identiﬁcation of Intermediate Phase in the Manganese-Titanium System”, Trans. Metall. Soc. AIME, 221(8), 686–690 (1961) (Experimental, Phase Relations, 11) Waterstrat, R.M., Das, B.N., Beck, P.A., “Phase Relationships in the Titanium-Manganese”, Trans. Metall. Soc. AIME, 224(6), 512–518 (1962) (Crys. Structure, Experimental, Phase Diagram, 17) Panigrahy, P.C., Gupta, K.P., “Some Observations on α-Mn, β-Mn, and R Phases in the Mn-Ti-Fe and Mn-Ti-Co Systems”, Trans. Met. Soc. AIME, 245, 1533–1536 (1969) (Crys. Structure, Phase Relations, Experimental, #, 13) Manenc, J., “Study of Hardening of Ferritic and Martensitic Fe-Mn-Ti Alloys” (in French), Mem. Scient. Rev Metallurg., 68(11), 761–769 (1971) (Phase Relations, Experimental, Mechan. Prop., 7) Marandel, J., Schmitt, B., Gantois, M., “Structure and Composition of Certain Laves Phases and Observation of the Fe-Mn-Ti” (in French), Compt. Rend. Acad. Sci. Paris, 275C, 1479–1481 (1972) (Crys. Structure, Phase Relations, Experimental, 3) Svechnikov, V.N., Petkov, V.V., “Laves Phase in Alloys of Mn with Transition Metals of Groups IVA-VA” (in Russian), Izv. Akad. Nauk Ukr. SSR Metallofiz., 64, 24–29 (1976) (Crys. Structure, Experimental, 7) Hwang, S.K., “The Cryogenical Properties and the Intergranular Brittleness in Fe-12%Mn(0.2%Ti) Ferritic Alloy System”, J. Korean Inst. Met., 16(5), 420–427 (1978) (Phase Realtions, Experimental, Mechan. Prop., 19) Chang, K.M., Morris, J.W., Jr., “Precipitation Strengthened Austenitic Fe-Mn-Ti Alloys”, Metallurg. Trans., A, 10A(9), 1377–1387 (1979) (Crys. Structure, Phase Relations, Experimental, Mechan. Prop., 14) Dew-Hughes, D., Kaufman, L., “Ternary Phase Diagrams of the Manganese-Titanium-Iron and the Aluminum-Titanium-Iron Systems: a Comparison of Computer Calculations with Experiment”, Calphad, 3(3), 175–203 (1979) (Phase Diagram, Thermodyn., Calculation, #, 23) Kaufman, L., Dew-Hughes, D., “Illustration of Ternary Diagram Synthesis Mn-Ti-Fe and AlTi-Fe” in “Calculation of Phase Diagrams and Thermochemistry of Alloy Phases”, Div. Basic Energy Sci., Nat. Sci. Found., Washington, 46–71 (1979) (Phase Diagram, Thermodyn., Calculation, 23) Brandes, E.A., Flint, R.F., “Mn-Fe-Ti” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 121 (1980) (Phase Relations, 1) Rivlin, V.G., Raynor, G.V., “Phase Equilibriums in Iron Ternary Alloys 9: Critical Review of Constitution of Ternary Systems Fe-Mn-X (X = Ti, V, Cr, Co, Ni, Cu)”, Int. Met. Rev., 28(1), 23–64 (1983) (Phase Diagram, Phase Relations, Review, 68) Kivalo, L.I., Skorokhod, V.V., “Inﬂuence of Manganese on Sintering Process in the Ti-Fe System. 1. Volume Changes in Sintering of Ti-Fe-Mn Compacts”, Sov. Pow. Metall. Met. Ceram., 24(12), 914–917 (Crys. Structure, Phase Relations, Experimental, Interface Phenomena, Kinetics, Transport Phenomena, 70) Cenzual, K., Parthe, E., Waterstrat, R.M., “Zr21Re25, a New Rhombohedral Structure Type Containing 12 Å-Thick Inﬁnite MgZn2 (Laves)-Type Columns”, Acta Crystallogr. C, 42C, 261–266 (1986) (Crys. Structure, Experimental, Phase Relations, 24)

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Fe–Mn–Ti [1988Ray]

[1990Har]

[1992Zha]

[1994Rag] [1995Bou]

[2003Cho]

[2004Iva]

[2005Yam]

[2007Iva]

[2007Wit] [Mas2] [V-C2]

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Raynor, G.V., Rivlin, V.G., “Fe-Mn-Ti” in “Phase Diagrams Ternary Iron Alloys”, Inst. Metals, London, 4, 378–388 (1988) (Phase Diagram, Phase Relations, Review, Assessment, *, 7) Hari Kumar, K.C., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys-IV”, J. Alloy Phase Diagram, 6(1), 31–49 (1990) (Phase Diagram, Thermodyn., Calculation, Review, #) as quoted by [1994Rag] Zhang, X., Kelton, K.F., “Vertex Growth of a Ti-Mn-Fe Icosahedral Phase”, Scr. Metall. Mater., 26(3), 393–398 (1992) (Crys. Structure, Experimental, Morphology, Phase Relations, 23) Raghavan, V., “Fe-Mn-Ti (Iron-Manganese-Titanium)”, J. Phase Equilib., 15(6), 620–621 (1994) (Phase Diagram, Review, 3) Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467–484 (1995) (Phase Relations, Theory, Thermodyn., 85) Choi, M.J., Hong, H.S., Lee, K.S., “Electrochemical Characteristics of the Composite Metal Hydride of TiFe and TiMn2 Synthesized by Mechanical Alloying”, J. Alloys Compd., 358, 306–311 (2003) (Crys. Structure, Electrochem., Experimental, 15) Ivanchenko, V.G., Gavrylenko, I.S., Pogorelaya, V.V., Nychyporenko, V.I., Pryadko, T.V., “Investigation of Phase Equilibria in Alloys of the Ti-Mn System” (in Ukrainian), Metallurgy and Processing of Metals (Metaloznavstvo ta Obrobka Metaliv), 4, 16–20 (2004) (Crys. Structure, Experimental, Phase Relations, Phase Diagram, 14) Yamada, Y., Nakamura, K., Kitagawa, K., Obara, G., Nakamura, T., “Magnetic Properties of C14 Laves Phase Ti(Fe1–xTx)2 with T = Mn, Co and Ni (x<0:6)”, J. Magn. Magn. Mater., 285 (1–2), 28–38 (2005) (Crys. Structure, Experimental, Magn. Prop., Optical Prop., 10) Ivanchenko, V., Dekhtyarenko, V., Kosorukova, T., “Phase Equilibria on the TiMn2-TiFe2 Polythermal Section”, Abstracts of X International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, Ukraine, 17–20 September, 48 (2007) (Crys. Structure, Phase Diagram, Experimental, Abstract, #, 2) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–Mn–V

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Iron – Manganese – Vanadium Lesley Cornish, Andy Watson

Introduction The Fe-Mn-V system is important for steels; Mn is a solid solution strengthener and vanadium is useful to combine with carbon or/and nitrogen to form carbides, nitrides and/or carbonitrides, which can be used to pin grain boundaries, and hence produce steels with a ﬁner grain size. The control of grain size is vital in rolling, and knowledge of the effects of additions to steels is vital for improving productivity. Vanadium is beneﬁcial in promoting ﬁne, mainly nitride, precipitates which give dispersion strengthening. Additionally, since both the Fe-V and Mn-V systems form the σ phase, which imparts deleterious mechanical properties, knowledge of the stability range of this phase is important so that its precipitation can be avoided in commercial steels. There have been few experimental studies of the ternary system. The σ phase and its stability in the Fe-Mn-V system was ﬁrst studied by [1957Dar]. Electrolytic grade Fe and Mn were vacuum induction melted with V chips in alumina crucibles and portions of the cast material were homogenized at 1000°C. XRD and metallographic analysis revealed a continuous series of solid solutions of the σ phase across the system. An early investigation of the phase relationships of the system was made by [1973Ish] who studied alloys containing up to 8 at.% Mn and 6 at.% V at 900, 1000, 1100 and 1200°C to derive the boundaries of the ‘γ-loop’ and to obtain stabilizing parameters. The ordering effects of the δ’ CsCl phase were investigated by [1975Hag] using DTA and XRD. Four partial isothermal sections were determined by [1992Bud]. Compositions for study were selected lying along three lines of constant Mn:V ratio (3:1, 1:1 and 1:3) across the phase diagram. The samples were prepared by arc-melting on a water-cooled copper hearth under argon using Armco iron (∼99% purity), and electrolytic grade Mn and V, with a total purity in excess of 99.95%. The samples were analyzed using metallography, X-ray diffraction, chemical analysis and hardness tests. The system was assessed by [1991Hua1] using the Calphad technique. The calculated phase diagrams agree well with the experimental work of [1957Dar]. Ordering of the δ’ phase was not included in the modeling because of the difﬁculty in extending the binary phase description into the ternary system without there being any experimental data available for the optimization. Substitutional solution models were used for all except for the σ phase. The magnetic terms for the Mn-V system were set to zero owing to a lack of data, and similarly, no ternary interactions were included in the modeling. The σ phase was modeled with three sublattices: (Fe,Mn)8:V4:(Fe,Mn,V)18, and some of the parameters were estimated from experimental data [1978Hil]. The system has been reviewed by [1980Bra, 1983Riv, 1988Ray, 1994Rag]. The experimental works are summarized in Table 1. Binary Systems The binary Fe-Mn system has been assessed by [1989Hua] and the calculated diagram is very similar in appearance to that given in [Mas2]. The main difference between the two is a predicted eutectoid decomposition of the γ phase to (αFe) and (αMn) occurring at 247.9°C (521 K). The system has been reassessed more recently, however, incorporating new experimental information on thermodynamic properties [2004Wit]. There are slight differences in the positions of the phase boundaries, and the agreement with experimental Fe rich phase equilibria is improved over the earlier assessment. The γ phase exists as a continuous series of solid solutions right across the phase diagram. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ⇌ (δMn) + (γMn,γFe). The phase diagram of [2004Wit] is accepted here. The Fe-V system has been assessed by [1991Hua2] but [2006Oka] has reported recent work by [2005Ust] who studied the extent of the σ phase in the binary Fe-V system using XRD and electron microscopy. They Landolt-Börnstein New Series IV/11D4

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suggest that the σ phase decomposes below about 650°C accompanied by phase separation of the δ (bcc) phase. However, in the phase diagram shown by [2006Oka], there would seem to be a narrow strip of single phase bcc between the σ phase and the region of phase separation. As pointed out by [2006Oka], this would seem to be unlikely, the sigma phase most probably decomposing eutectoidally to give Fe rich and V rich bcc phases, much like in the Cr-Fe system. As this remains uncertain, the feature has been ignored in the present work. The version of the phase diagram give in [Mas2] is accepted here. The binary Mn-V system is characterized by a wide series of solid solutions based on (V) and (δMn). The σ phase has a homogeneity range of approximately 8 at.% at 600°C, which extends to about 18 at.% at 1020°C, but as pointed out by [1982Smi], the width of the phase ﬁeld is not well deﬁned. The system was assessed by [1991Hua1] resulting in a phase diagram that is somewhat different to the version given in [Mas2], particularly with respect to the congruent transformation of the σ phase. The version given by [1982Smi] (reproduced in [Mas2]) shows a transformation from the σ phase and eutectoid decomposition of (V,δMn), the shapes of which are unlikely. The assessment of [1991Hua1] gives a congruent transformation of the σ phase that is more symmetrical and occurring at a higher temperature resulting in a more reasonable looking eutectoid reaction. The result is in better agreement with the experimental information in this region of the diagram. This version of the phase diagram is also preferred by [1992Oka] and is accepted here. The ordered phase indicated in the diagram of [Mas2] was not modeled in the work of [1991Hua1]. Solid Phases No ternary phases have been found in this system. The major feature of the phase diagram is the presence of a continuous σ phase ﬁeld stretching across the diagram between the Fe-V and the Mn-V edge binary systems [1957Dar]. The lattice parameters of the σ phase in the Fe-V and Mn-V systems are very close to each other, so it should be no surprise that there is a continuous series of solid solutions between them. The binary terminal solid solutions dissolve appreciable amounts of the third element resulting in phase ﬁelds that penetrate deep into the ternary system. [1975Hag] demonstrated the presence of the δ’ CsCl type superlattice and also that the order-disorder transition temperature, Tc, of the δ’ VMn superlattice was increased by the addition of Fe. An estimated value for the Tc of the FeV superlattice, which is not measurable because of the intervention of σ, was extrapolated to be between 850 and 880°C. Table 2 gives crystallographic details of the solid phases. Liquidus, Solidus and Solvus Surfaces According to the work of [1992Bud], a study of the liquidus surface has been undertaken by [1990Ban], but unfortunately, these results are not available. In any case, it is unlikely that the liquidus surface would show any distinguishing features as there are only 2 binary invariant reactions taking place and both lie in the FeMn system. It is expected that a monovariant line would extend from the binary L + (δFe) ⇌ (γMn,γFe) peritectic into the ternary system, eventually encountering the lower temperature L ⇌ (δMn) + (γMn,γFe) eutectic reaction in the same binary system. The nature of this monovariant reaction would therefore switch from peritectic to eutectic at some unknown composition in the ternary system. Using the thermodynamic model parameters from [1991Hua1] and the updated parameters for the Fe-Mn system from [2004Wit] a liquidus surface has been calculated, and is shown in Fig. 1. It should be stressed, however, that there has been no experimental conﬁrmation for this liquidus surface. Isothermal Sections [1957Dar] made one of the earliest studies of the solid phase equilibria in the system. Using manganese and iron of electrolytic grade, and vanadium chips with an impurity content of 0.25%, samples were prepared by vacuum induction melting using recrystallized alumina crucibles. Weight losses of the ingots were less that 1 mass%, and the compositions were obtained by chemical analysis. XRD was carried out on crushed samples after they had been homogenized for “a prolonged period” at 1000°C in evacuated and sealed fused quartz tubes, followed by quenching in water by breaking the submerged tubes. Identiﬁcation of the σ phase was achieved using metallography, with XRD being used for conﬁrmation. Since the σ-containing specimens exhibited a certain degree of cracking, this was an aid to interpretation, however the other phases DOI: 10.1007/978-3-540-78644-3_23 # Springer 2008

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in the specimens were not identiﬁed. This enabled the extent of the σ phase ﬁeld to be determined. [1973Ish] studied equilibria in the Fe rich corner of the phase diagram at 900, 1000, 1100 and 1200°C (up to 8 at.% Mn and 6 at.% V) using X-ray microanalysis of annealed samples. The phase boundaries were found to agree well with the calculated sections of [1991Hua1], which were based mainly on the extrapolation of the thermodynamic descriptions of the binary systems into the ternary, but with some adjustment of the model parameters of the σ phase to give agreement with the experimental data of [1957Dar]. The experimental data of [1973Ish] are compared with the calculated phase boundaries for 900, 1000, 1100 and 1200°C in Figs. 2 to 5 indicating the level of agreement. Full isothermal sections calculated for 800, 1000 and 1200°C are given in Figs. 6 to 8. Alterations have been made where necessary to ensure agreement with the accepted binary phase diagrams. The binary Mn-V system given by [Mas2] shows the existence of an ordered CsCl type phase, denoted δ’, although its exact location in the phase diagram is not clear, as indicated by dotted lines in the Figure. [1975Hag] used DTA and XRD to study the order/disorder transition in ternary alloys. They found that the addition of Fe raised the critical temperature of the ordering. Using their experimental data, they were able to derive thermodynamic interaction parameters for the order/disorder reaction and produce a set of isotherms, which are reproduced in Fig. 9. The results were also shown in [1980Bra]. Partial isothermal sections (from 40 mass% Fe) were determined for 600, 800, 1000 and 1200°C by [1992Bud]. Armco Fe and electrolytic Mn and V were arc-melted on a water-cooled copper hearth under argon. Alloys were annealed at 1200, 1000, 800 and 600°C for times between 24 and 250 h depending on the heat treatment temperature. The alloys were investigated by XRD, microstructural and chemical analysis and hardness measurement. However, in the partial isothermal sections shown, there is no evidence of the σ phase, which is known to exist across the diagram, certainly at the lower temperatures. Temperature – Composition Sections An experimental section for xMn/xV = 1 at high Fe contents was determined by [1973Ish] which showed a closed γ loop. Their own thermodynamic calculations gave a slightly smaller loop and later calculations by [1991Hua1] did not show any closure at all. Introducing a small ternary interaction parameter for the bcc δαﬄ phase (–10kJ·mol–1) enabled a closed loop to be produced, but then it was found that the ﬁt of the calculated phase boundaries to the experimental data suffered. However, [1991Hua1] suggested that observing small amounts of the second phase would be experimentally challenging as some of the observed compositions were essentially on the δ/δ+γ phase boundary. The experimentally determined γ loop is depicted in Fig. 10. A vertical section was produced by [1992Bud] at a Mn content of 10 mass%, but as this does not agree with the phase ﬁelds or the peritectic temperature shown in the accepted Fe-Mn phase diagram, and therefore it is not reproduced here. Thermodynamics From the experimentally determined δ/γ phase boundaries, [1973Ish] derived a series of thermodynamic parameters and showed that for low alloy contents, they could be used to derive the phase relationships. For higher alloying contents however, there were no reliable relationships. From their order-disorder transition studies, [1975Hag] derived interaction parameters for the δ phase Fe-Mn (200 ± 300), Fe-V (–4520 ± 60) and Mn-V (–4440). Using Hamiltonian cluster models, [1977Bra] calculated the extent of the σ phase in the ternary system but found that the ﬁt to the available experimental data was poor. It was acknowledged that there may be issues with the simplicity of the cluster model employed, and they also stated that data was required for the different bandwidths in the metal, charge transfer, magnetic and temperature effects, as well as the need to include of all the phases in the calculations. [1987Bal] studied the effect of vanadium on the activity of the manganese in dilute Fe-alloys (Fe3.14 mass% Mn) at 1873 K (1600°C) using a continuous weighing technique. They found that the evaporation rate constant for Mn decreased from 11.5·10–3 to 7·10–3 cm·s–1 leading to a pairwise interaction coefﬁcient of εVMn of 1.55. Landolt-Börnstein New Series IV/11D4

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Notes on Materials Properties and Applications Since the Fe-Mn-V system is important for steels, mechanical property measurement such as hardness testing has been used to identify useful steel compositions. As well as avoiding the σ phase, which is detrimental to the mechanical properties of steel thus limiting the amounts of V and Mn in a given material, alloys with more than 50 mass% (Mn + V) were also found to be embrittled by the precipitation of the δ phase (αFe) [1992Bud]. A beneﬁcial martensitic transformation occurred in alloys where (Mn + V) was between 10 and 12 mass%. [1981Kho] studied the elasticity modulus of Fe-Mn dispersion hardened alloys and the effects of V additions as an aging accelerator. The maximum strength of a Fe-Mn Elinvar alloy (Fe-28.8% Mn-1.9% V-0.5% C) was achieved after aging at 650–750°C Miscellaneous In a study involving the effects of a variety microalloying additions to steel, [2004Li] showed the beneﬁcial affects of both V and Mn in controlling the grain size of thin slab cast product. The addition of P promotes the stability of amorphous Fe-Mn alloys. The processes occurring in amorphous Fe-P-Mn-V alloys at elevated temperatures, up to the crystallization temperature, were studied by [2001Vav, 2004Vav]. Results from internal friction measurements and XRD were used to evaluate the activation energy of defect migration and the particle size of the crystalline phases precipitating in the alloys during annealing. Increasing the vanadium content of amorphous Fe-P-Mn-V alloys increases the energy of defect migration reducing the particle size of the precipitating phases. The dissolution of Mn and V was found to inhibit the growth of Fe3P particles during annealing. Table 1.

Investigations of the Fe-Mn-V Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1957Dar]

Metallography, XRD

Isothermal section at 1000°C, 10–60 mass% V, extent of σ phase stability

[1973Ish]

Thermodynamic analysis, X-ray microanalysis

Partial isothermal sections at 800°C–1200°C, up to 8 at.% Mn and 6 at.% V

[1975Hag]

XRD, DTA

Partial isothermal sections at 500°C–900°C, 50 at.% V with 5, 10, 15, 20, 25, 30, 40 at.% Fe, as well as 50V:50Fe, measurement of Tc related to ordering of bcc phase

[1977Bra]

Cluster model calculation

1000°C, extent of σ phase stability

[1991Hua1]

Thermodynamic modeling by the Calphad technique

Complete system

[1992Bud]

Metallography, XRD, chemical analysis, hardness and microhardness

Isothermal sections at 600°C, 800°C, 1000°C and 1200°C, from 40 mass% Fe, (Mn, Fe) + (αFe)

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Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

δ, (δαFe, δMn,V)

cI2 Im 3m W

(δFe) 1538–1394 (V) < 1910 (δMn) 1246–1138 (αFe) < 912 γ, (γMn,γFe) (γFe) 1394–912 (γMn) 1138–1100

cF4 Fm 3m Cu

Lattice Parameters [pm]

Comments/References

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

a = 302.4

pure V [Mas2]

a = 308.0

pure Mn [Mas2]

a = 286.65

pure Fe at 25°C [Mas2]

a = 364.67

pure Fe at 915°C [V-C2, Mas2]

a = 386.0

pure Mn [Mas2]

δ’

cP2 Pm 3m CsCl

a = 291.0

VMn. Metastable in Fe-V system

(αMn)

cI58 I 43m αMn

a = 891.26

[Mas2]

(βMn)

cP20 P 4132 βMn

a = 631.52

[Mas2]

σ

tP30 P42/mnm σCrFe

σVFe < 1252 σVMn < 1058

a = 896.5 c = 463.3 a = 898.5 c = 462.1

[Mas2] [V-C2] [1991Hua1, V-C2]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]

Martensite

tI4 I4/mmm

-

[Mas2]

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Fig. 1. Fe-Mn-V.

Fe–Mn–V

Calculated liquidus surface projection

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Fig. 2. Fe-Mn-V.

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Calculated boundaries for (δFe)/γ(Fe) at high Fe contents, at 900°C

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Fig. 3. Fe-Mn-V.

Fe–Mn–V

Calculated boundaries for (δFe)/γ(Fe) at high Fe contents, at 1000°C

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Fig. 4. Fe-Mn-V.

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Calculated boundaries for (δFe)/γ(Fe) at high Fe contents, at 1100°C

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Fig. 5. Fe-Mn-V.

Fe–Mn–V

Calculated boundaries for (δFe)/γ(Fe) at high Fe contents, at 1200°C

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Fig. 6. Fe-Mn-V.

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Calculated isothermal section at 800°C

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Fig. 7. Fe-Mn-V.

Fe–Mn–V

Calculated isothermal section at 1000°C

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Fig. 8. Fe-Mn-V.

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Calculated isothermal section at 1200°C

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Fig. 9. Fe-Mn-V.

Fe–Mn–V

Calculated order-disorder transition temperatures

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Fig. 10. Fe-Mn-V.

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Vertical section at xMn/xV = 1 at high Fe content

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16 References [1957Dar] [1973Ish]

[1975Hag]

[1977Bra] [1978Hil] [1980Bra] [1981Kho]

[1982Smi] [1983Riv]

[1987Bal]

[1988Ray] [1989Hua] [1990Ban]

[1991Hua1] [1991Hua2] [1992Bud]

[1992Oka] [1994Rag] [2001Vav]

[2004Li]

Fe–Mn–V

Darby, J.B., Beck, P.A., “σ Phase in Certain Ternary Systems with Vanadium”, Trans. A.I.M. E., 209, 69–72 (1957) (Phase Diagram, Experimental, 8, #) Ishida, K., Shibuya, K. and Nishizawa, T., “γ -Loops in Fe-Mn-V, Fe-Mn-Mo and Fe-Mn-Si Systems” (in Japanese), J. Jpn. Inst. Met., 37(2), 1305–1312 (1973) (Phase Diagram, Thermodyn., Calculation, Experimental, 22) Hagiwara, M., Seki, J., Suzuki, T., “CsCl type Superlattice Formation in V-Fe-Mn, Fe-V-Cr and V-Mn-Cr Ternary Alloys” (in Japanese), J. Jpn. Inst. Met., 39(4), 402–408 (1975) (Thermodyn., Experimental, Phys. Prop., 27) Brauwers, M, “Occurrence of the σ Phase Computed from a Cluster Model”, J. Phys. F: Met. Phys., 7(6), 921–927 (1977) (Calculation, 17) Hillert, M., Jarl, M., “A model for alloying in ferromagnetic metals”, Calphad, 2(3), 227–238 (1978) cited by [1991Hua1] Brandes, E.A., Flint, R.F., “Mn-Fe-V” in “Manganese Phase Diagrams”, Manganese Centre, Paris, France, 122 (1980) (Phase Relations, Review, 1) Khomenko, O.A., Khil'kevich, I.F., “Characteristics of `Nonmagnetic' Dispersion-hardened Fe-Mn-Elinvar”, Met. Sci. Heat Treat., 23(3–4), 211–214 (1981) (Phase Relations, Mechan. Prop., 8) Smith, J.F., Carlson, O.N., “The Mn-V (Manganese-Vanadium) System”, Bull. Alloy Phase Diagrams, 2(4), 469–478 (1982) (Crys. Structure, Phase Diagram, Thermodyn., Review, 19) Rivlin, V.G., Raynor, G.V., “Phase Equilibriums in Iron Ternary Alloys 9: Critical Review of Constitution of Ternary Systems Fe-Mn-X (X = Ti, V, Cr, Co, Ni, Cu)”, Int. Met. Rev., 28(1), 23–64 (1983) (Phase Diagram, Phase Relations, Review, 68) Balkovoy, Yu.V., Aleev, R.A., Manohin, A.A., “Inﬂuence of Carbon, Silicon and Vanadium on the Activity of the Manganese in Iron” (in Russian), Izv. Vyss. Uchebn. Zaved., Chern. Metall., 9, 128–129 (1987) (Experimental, Thermodynamics, 1) Raynor, G.V., Rivlin, V.G., “Fe-Mn-V” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London, 388–392 (1988) (Review, #,2) Huang, W., “Assessment of the Fe-Mn System”, Calphad, 13(3), 243–252 (1989) (Phase Diagram, Thermodyn., Assessment, 35) Bannykh, O.A., Budberg, A.P., Potemkin, A.Ya., “Special Features of the Interaction of the Components in Ternary Fe-Mn-V” in “Problems in Establishing the Optimum Structure of Aviation Materials”, Sergo Ordzhonikidze Aviation Inst, Moscow (1990) cited by [1992Bud]. Huang, W., “A Thermodynamic Analysis of the Mn-V and Fe-Mn-V Systems”, Calphad, 15 (2), 195–208 (1991) (Phase Diagram, Assessment, Calculation, #, *, 23) Huang, W., “A Thermodynamic Evaluation of the Fe-V-C System”, Z. Metallkd., 82(5), 391–401 (1991) (Phase Diagram, Thermodyn., Assessment, Calculation, 54) Budberg, A., Potemkin, A.Ya., “Phase Structure of Alloys of the Iron - Manganese Vanadium System over the Temperature Range 600–1200°C”, Isv. Akad. Nauk SSR, Met., 5, 133–136 (1992) (Experimental, Phys. Prop., 1 #) Okamoto, H., “Mn-V (Manganese-Vanadium)”, J. Phase. Equilib., 13(5), 575 (1992) (Crys. Structure, Phase Diagram, Review, 8) Raghavan, V., “Fe-Mn-V (Iron-Manganese-Vanadium)”, J. Phase Equlib., 15(6), 621–622 (1994) (Review, 2) Vavilova, V.V., Kovneristyi, Y.K., Palii, N.A., “Physicochemical Properties of Amorphous and Crystalline Fe-P-Mn and Fe-P-Mn-V Alloys”, Inorg. Mater., 37(2), 166–169 (2001) (Phase Relations, Experimental, Thermodyn., 5) Li, Z., Wilson, J.A., Crowther, D.N., Mitchell, P.S., Craven, A.J., Baker, T.N., “The Effects of Vanadium, Niobium, Titanium and Zirconium on the Microstructure and Mechanical Properties of Thin Slab Cast Steels”, ISIJ Int., 44(6), 1093–1102 (2004) (Crys. Structure, Experimental, Morphology, 35)

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[2004Wit]

[2005Ust]

[2006Oka] [2007Wit] [Mas2] [V-C2]

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Vavilova, V.V., Vygovskii, D.A., Kalinin, Y.E., Kovneristyi, Y.K., Palii, N.A., “Inelastic Properties of Amorphous and Nanocrystalline Fe-P-Mn-V Alloys”, Inorg. Mater., 40(8), 815–821 (2004) (Phase Relations, Experimental, Thermodyn., 13). Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Phase Diagram, Thermodyn., Assessment, Calculation, Experimental, 34) Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”, J. Alloys Compd., 398, 133–138 (2005) (Crys. Structure, Phase Diagram, Experimental, 9) Okamoto, H., “Fe-V (Iron-Vanadium)”, J. Phase Equilib. Diff., 27(5), 542 (2006) (Review, Phase Diagram, 3) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–Mn–Zr

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Iron – Manganese – Zirconium Nathalie Lebrun, Pierre Perrot

Introduction The main interest in the Fe-Mn-Zr alloys rests in its use as hydrogen storage material. The experimental works done on this system deal mainly with its hydrogen storage capacity: characteristics hydrogen content vs imposed hydrogen pressures, thermodynamics related to the hydrogen absorption. The only part of the diagram investigated is the vertical section ZrMn2-ZrFe2. The entire ternary diagram has never been investigated and no Calphad assessment is known. Main experimental works are reported in Table 1. Binary Systems Using new experimental thermodynamic data, the Fe-Mn system has been recently reassessed and the Calphad description was updated by [2004Wit]. This new reevaluation of the phase equilibria leads to consistently better ﬁts to the available experimental data. Consequently, the Fe-Mn system is accepted from [2004Wit]. There is however, a typographical error in [2004Wit] in that the Mn rich invariant reaction involving the liquid phase is given as a peritectic type reaction in the table of invariants. This reaction should be denoted as eutectic, as conﬁrmed by [2007Wit], and have been written as L ↾ (δMn) + (γMn,γFe). The Fe-Zr binary system is accepted from [2002Ste]. The Mn-Zr system is accepted from [1999Sch]. It presents a non stoichiometry for the ZrMn2 compound which is lower than that reported by [Mas2]. Solid Phases All the data on unary, binary and ternary phases are indicated in Table 2. The Laves phases ZrMn2 and ZrFe2 give a solid solution Zr(Mn1–xFex)2 whose structure varies from C14 (x < 0.6) to C15 (x > 0.8) [1968Kan]. For 0.6 < x < 0.8 [1972Pet], reproduced by [1992Rag], proposes a two-phase domain C14 + C15. Actually, it is more probable that the solid solution presents a C36 structure (hP24, P63/ mmc, MgNi2 type), a transition already observed in ZrFe2 based solid solutions [1973Sve] such as (Nb1–xZrx)Fe2. A strong argument comes from the fact that the iron magnetic moment of the solid solution grows monotonically from 0 to 1.2 μB when x varies from 0.5 to 1 [1968Kan]. X-ray investigations carried out by [1971Kan] conﬁrm the existence of the C36 phase. The pattern diffraction of Zr(Mn0.3Fe0.7)2 is similar to that of Nb0.4Zr0.6Fe2 and may be indexed as a six hexagonal layer structure. It is not clear whether the transitions C14-C36 and C36-C15 are of the ﬁrst or second order. The crystal parameters of the solid solutions Zr(Mn1–xFex)2 are plotted in Fig. 1 according to the data of [1999Sch] and [2004Li]. As the C14-C36 and C36-C15 transitions have not been formally recognized, the domain between the C14 and C15 regions is indicted by a question mark. Quasibinary Systems [1972Pet] presents a phase diagram through the quasibinary ZrMn2-ZrFe2 section, which is questionable, because he proposes for ZrMn2 a melting point at 1570°C, which is 120°C higher than the accepted value and a two-phase domain around 20 mol% ZrMn2, which contradicts the observations of [1971Kan]. Based on the phase diagram proposed by [1972Pet], it is probable that the liquidus and the solidus lines of the ZrMn2-ZrFe2 phase diagram present a cigar like shape between 1673 and 1450°C, the respective melting points of ZrFe2 and ZrMn2. The phase equilibria are shown in Fig. 2. The liquidus line, mainly from the DTA experiment carried out by [1972Pet], has been modiﬁed to take into account the accepted melting point of ZrMn2. Thermodynamics The molar partial enthalpy of dissolution of H2 in ZrMnFeHy (1 < y < 2.5) was measured by [2000Pra] from the isobaric curves and found at ΔdHH = +9.25 ± 0.25 kJ·(mol⊊H)–1 and its molar partial entropy of Landolt-Börnstein New Series IV/11D4

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Fe–Mn–Zr

dissolution at ΔdSH = +26 ± 1.0 J·(mol⊊H)–1·K–1. The partial replacement of Fe by Co gives, for ZrMnFe0.75Co0.25Hy (1 < y < 1.5) ΔdHH = – 9.3 ± 0.5 kJ·(mol⊊H)–1 and ΔdSH = – 36.8 ± 0.6 J·(mol⊊H)–1·K–1. This effect is due to the contraction of the lattice induced by the substitution of Fe by Co [2000Pra]. Notes on Materials Properties and Applications Zr based Laves phases such as the Zr(Fe,Mn)2 solid solution have attracted much attention as hydrogen storage materials [2004Li]. ZnMn2 is a representative member of the series, which absorbs hydrogen up to the composition of ZrMn2H4 [1984Pou]. However, its hydrides are too stable so that further partial substitutions (Zr by Ti and Mn by Fe) are needed to provide materials stable within a wide range of hydrogen pressures. For instance the ZrMn2.7 compound presents, on the hydrogen pressure - hydrogen content curve, a plateau at 0.03 MPa of hydrogen pressure for 20°C and at 0.5 MPa of hydrogen pressure for 150°C. These plateaus are raised when substituting Mn by Fe [1986Uch], by Fe and Co [2000Pra, 2000Ram, 2002Man2] or by Fe and Ni [2002Man1] in the solid solution. For the ZrMn1.11Fe1.22 compound, the respective positions of the plateaus are: 1 MPa of hydrogen pressure at 20°C and at 5 MPa of hydrogen pressure at 150°C. The crystal structure remains unchanged upon hydrogenation [2003Dor], but the relation between the volume change induced by hydrogenation and the hydrogen uptake is not linear. The reducing power of Zr combined with the hydrogen storage capacity of the ternary alloy have been used to reduce HTO (tritiated water) to HT (tritiated hydrogen) at 400–600°C with a conversion efﬁciency of 90 % for residence time of the order of the second [1995Ghe, 1997Ghe]. The conversion rate is greater than 6 μmol·min–1·(g of alloy)–1. The oxygen to alloy mole ratio may be as high as 2.6 without signiﬁcant loss of efﬁciency. The HT/HTO conversion efﬁciency may go up to 99% with a working temperature of 800–900°C. The main experimental investigations on material properties are gathered in Table 3. Miscellaneous The inﬂuence of Mn on the magnetic properties of (Fe,Zr) alloys have been widely investigated [1987Nic, 1994Sri, 1997She, 2001Per2, 2006Per]. The amorphous Fe90Zr10 alloy presents a ferromagnetic transition at 230 K followed by the loss of long range order into a spin glass like state at 12 K [1987Nic]. The substitution of Fe by Mn up to 10 at.% Mn (Fe90–xMnxZr10, with x < 10) decreases the spin freezing temperature. The Curie temperature decreases from 230 K (for x = 0) down to 150 K (for x = 12) and the spin freezing temperature increases from 35 K (for x = 0) up to 65 K (for x = 12) [1997She, 2001Per3, 2002Per]. Hydrogenation enhances the magnetization of the materials [1987Zha], probably as a consequence of the expansion of the lattice. By lowering temperature, the amorphous alloy Fe80Mn10Zr10 presents a paramagnetic-ferromagnetic transition which depends on the applied ﬁeld, then, by further cooling, a transition, observed at 40 K from the ferromagnetic state to a new state referred as a “reentrant spin glass phase” [2001Per1, 2002Per] which is characterized by the vanishing of the ferromagnetic order. Some features of this new phase look like spin glass state, but its true nature is not well established. The substitution of Mn by B in the amorphous Fe82Mn82–xBxZr10 (x < 8) increases the Curie temperature (368 K for x = 8) [2005Uly]. A paramagnetic state in the amorphous matrix is observed together with a superparamagnetic state due to nanoparticles embedded in the matrix.

Table 1.

Investigations of the Fe-Mn-Zr Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1972Pet]

XRD, differential thermal analysis

900–1675°C, Zr(FexMn1–x)2 (0 < x < 1), quasibinary section

[1984Pou]

XRD, hydrogen absorption, hydrogen intake - pressure characteristics

23–190°C, ZrMn2.8, ZrMn2Fe0.8, ZrMn2Fe1.2, < 5 MPa H2, partial quantities of H2 dissolution (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[2000Pra]

XRD, hydrogen absorption, hydrogen intake - pressure characteristics

30–100°C, ZrMnFe and ZrMnFe0.7Co0.3, < 3 MPa H2, partial quantities of H2 dissolution

[2000Ram]

XRD, hydrogen absorption, hydrogen intake - pressure characteristics

30–100°C, ZrMnFe1–xCox (x = 0.2, 0.3, 0.5), < 0.1 MPa H2, partial quantities of H2 dissolution

[2002Man1]

XRD, hydrogen absorption, hydrogen intake - pressure characteristics

30–100°C, ZrMnFe1–xNix (x < 0.6), < 4 MPa H2

[2002Man2]

XRD, hydrogen absorption, hydrogen intake - pressure characteristics

30–100°C, ZrMnFe1–xCox (x < 0.6), < 4 MPa H2

[2003Dor]

XRD, volume change upon hydrogenation

25°C, Zr(FexMn1–x)2 (x < 1)

[2004Li]

XRD, calorimetry, hydrogen absorption

25°C, Zr(FexMn1–x)2 (x < 0.8), < 0.1 MPa H2

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

αδ(Fe,Mn)

cI2 Im 3m W

(δFe) 1538–1394 (δMn) 1246–1138

Comments/References

a = 293.15

pure Fe at 1390°C [V-C2, Mas2] Dissolves 10 at.% Mn at 1474.5°C [2004Wit] [Mas2] Dissolves up to 12.2 at.% Fe at 1236.6°C [2004Wit] and 1.25 at.% Zr at 1155°C [1999Sch] pure Fe at 25°C [Mas2, V-C2]. Dissolves 5 at.% Mn at 527°C [2004Wit]

a = 308.0

(αFe) (Ferrite) < 912 (εFe)

Lattice Parameters [pm]

a = 286.65

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, > 13 GPa [Mas2]

(continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

γ(Fe,Mn)

cF4 Fm 3m Cu

(γFe) (Austenite) 1394–912 (γMn) 1138–1100

Lattice Parameters [pm]

Comments/References

a = 364.67

pure Fe at 915°C [V-C2, Mas2] Complete solubility with (γMn) [2004Wit] [Mas2] complete solubility with (γFe) [2004Wit]. Dissolves 0.5 at.% Zr at 1120°C [1999Sch]

a = 386.0

(βMn) 1100–727

cP20 P4132 βMn

a = 631.52

[Mas2]. Dissolves up to 32.9 at.% Fe [2004Wit] and 1.7 at.% Zr at 1140°C [1999Sch]

(αMn) < 727

cI58 I 43m (αMn)

a = 891.26

pure Mn at 25°C [Mas2]. Dissolves up to 35.2 at.% Fe [2004Wit] and 1.25 at.% Zr at 730°C [1999Sch]

(βZr) 1855–863

cI2 Im 3m W

a = 360.90

[Mas2] dissolves up to 4.2 at.% Fe at 928°C [2002Ste] and 10.2 at.% Mn at 1090°C [1999Sch]

(αZr) < 863

hP2 P63/mmc Mg

a = 323.16 c = 514.75

[Mas2] dissolves up 10.2 at.% Mn at 1090°C [1999Sch]

Zr3Fe < 851

oC16 Cmcm BRe3

a = 332 b = 1100 c = 882.0

from 74.8 to 75.4 at.% Zr [2002Ste]

Zr2Fe 951–780

tI12 I4/mcm Al2Cu

a = 638 c = 560

from 66.7 to 67.2 at.% Zr (C16 structure) [2002Ste]

ZrFe2 (C15) < 1673

cF24 Fd 3m MgCu2

a = 702 to 709

from 27.5 to 34.5 at.% Zr [2002Ste], Laves phase. Dissolves up to 30 mol% ZrMn2 [1968Kan, 2004Li] at 33.3 at.% Zr (ZrFe2) [2004Li] at 33.3 at.% Zr and 20.0 at.% Mn (x = 0.7) [2004Li]

Zr(FexMn1–x)2 (x > 0.7)

a = 707.0 a = 708.5

ZrFe2 (C36) 1345–1240 ± 10

hP24 P63/mmc MgNi2

a = 495 c = 1614

from 26.5 to 27 at.% Zr [2002Ste] Laves phase

Zr6Fe23 1482–1175 ?

cF116 Fm 3m Th6Mn23

a =1169

metastable, from 20.6 to 21.6 at.% Zr [2002Ste] sometimes labelled ZrFe3 (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

ZrMn2 (C14) < 1450

hP12 P63/mmc MgZn2

Zr(FexMn1–x)2 (x < 0.5) Zr1–y(FexMn1–x)2 (x < 0.5, y < 0.07)

Table 3.

5

Lattice Parameters [pm]

Comments/References

28 to 40 at.% Zr [1999Sch] Laves phase. Dissolves up to 60 mol% ZrFe2 [1968Kan, 2004Li] at 28.1 at.% Zr [1999Sch]

a = 499.7 c = 820.7 a = 502.6 c = 825.8 a = 506.8 c = 830.2 a = 501.3 c = 819.6 a = 498.4 c = 817.1

at 33.3 at.% Zr [1987Zha, 1999Sch] at 40.0 at.% Zr [1999Sch] at 33.3 at Zr and 33.3 at.% Fe (x = 0.5) [2004Li] x = 0.40, y = 0.07 [1987Zha]

Investigations of the Fe-Mn-Zr Materials Properties

Reference

Method/Experimental Technique

Conditions, Type of Property

[1968Kan]

Saturation magnetization, magnetic moment measurements

Zr(Mn1–xFex)2, (0 < x < 1), evolution from C14 to C15 structure with composition

[1971Kan]

XRD, magnetic moment, Curie temperature

77–500 K, Zr(Mn1–xFex)2, (0 < x < 1), structural and magnetic evolution

[1986Uch]

XRD, hydrogen intake vs hydrogen pressure characteristics

20–250°C, ZrMn2.7, ZrMn2.0Fe0.8, ZrMn1.22Fe1.11, ZrMn1.11Fe1.22

[1987Nic]

XRD, magnetic susceptibility, Curie temperature

4.2–120 K, amorphous Fe90–xMnxZr10 (x < 22 at.% Mn), spin glass behavior

[1987Zha]

XRD, effective magnetic moment, magnetization, Curie temperature

4.2–273 K, ZrMn2, ZrMn2.8, ZrMn2Fe0.8 and hydrogenated products, spin glass state

[1993Sou]

XRD, SEM, neutron diffraction, EDX

1000°C, ZrMn1.6Fe0.4 and hydrogenated products

[1994Sri]

Electrical conductivity, magnetization, Curie temperature

4.2–300 K, amorphous Fe90–xMnxZr10 (x < 12 at.% Mn)

[1995Ghe, 1997Ghe]

Activation analysis, reduction of tritiated water

400–600°C, composition not given, tritium recuperation

[1997She]

XRD, magnetic moment, Curie temperature, magnetization

1.5–1200 K, amorphous Fe90–xMnxZr10 (x < 15 at.% Mn), spin glass behavior

[2001Per1]

XRD, magnetic susceptibility under alternative current

12–300 K, amorphous Fe80Mn10Zr10, reentrant spin glass state

[2001Per2]

XRD, spontaneous magnetization, zero ﬁeld and low ﬁeld susceptibility

12–300 K, amorphous Fe90–xMnxZr10 (x < 8), critical exponents determination (continued)

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Reference

Method/Experimental Technique

Conditions, Type of Property

[2001Per3]

Low ﬁeld susceptibility under alternative current

77–300 K, amorphous Fe90–xMnxZr10 (x < 16), critical exponents determination

[2002Per]

Magnetization, high ﬁeld susceptibility, coercivity

4.2–300 K, amorphous Fe90–xMnxZr10 (x < 12), spin glass behavior

[2005Uly]

Magnetization, electron spin resonance, Curie temperatures

Amorphous Fe82Mn6–xBxZr10 (x < 8), superparamagnetism, nanoparticles

[2006Per]

Magnetization, magnetic susceptibility, coercivity

4.2–300 K, amorphous Fe90–xMnxZr10 (x < 16 at.% Mn), reentrant magnetic transition

Fig. 1. Fe-Mn-Zr. Crystal parameters of the solid solutions Zr(Fe,Mn)2

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Fig. 2. Fe-Mn-Zr. The ZrMn2-ZrFe2 quasibinary system

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8 References [1968Kan]

[1971Kan]

[1972Pet]

[1973Sve]

[1984Pou]

[1986Uch]

[1987Nic]

[1987Zha]

[1992Rag]

[1993Sou]

[1994Sri]

[1995Ghe]

[1997Ghe]

[1997She]

[1999Sch] [2000Pra]

[2000Ram]

Fe–Mn–Zr

Kanematsu, K., “Magnetism and Crystal Structures of Zirconium Compounds with Laves Structure”, J. Appl. Phys., 39(2), 465–466 (1968) (Crys. Structure, Experimental, Magn. Prop., 2) Kanematsu, K., “Magnetic Moment in Laves Phase Compounds. II. Zr(Fe1–xMnx)2 and Zr (Fe1–xCox)2”, J. Phys. Soc. Jpn., 31(5), 1355–1360 (1971) (Crys. Structure, Experimental, Magn. Prop., 8) Petkov, V.V., “Examination of Laves Phases in the Zr(Fe, Co, Ni)2-ZrMn2 Systems”, Russ. Metall., (5), 113–115 (1972), translated from Izv. Akad. Nauk SSSR, Met., (5), 155–157 (1972) (Crys. Structure, Experimental, Phase Diagram, 8) Svechnikov, V.N., Kocherzhinsky, Yu.A., Markiv, V.Ya., Pet’kov, V.V., “Laves Phases in Transition Metal Systems of the IV-VII Groups of Periodic Systems” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika, 46, 35–45 (1973) (Experimental, Phase Diagram, Review, 74) Pourarian, F., Sinha, V.K., Wallace, W.E., “Hydrogen Sorption Properties of Nonstoichiometric ZrMn2-Based Systems”, J. Less-Common Met., 96, 237–248 (1984) (Experimental, Phase Relations, 16) Uchida, M., Bjurstroem, H., Suda, S., Matsubara, Y., “On the Equilibrium Properties of Some ZrMn2-Related Hydride-Forming Alloys”, J. Less-Common Met., 119, 63–74 (1986) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 16) Nicolaides, G.K., Hadjipanayis, G.C., Rao, K.V., “Effect of Mn on the Collapse of “Ferromagnetic” Order in Melt-Spun Fe90Zr10 Amorphous Alloys”, J. Appl. Phys., 61(8), 3642 (1987) (Abstract, Magn. Prop., 0) Zhang, L.Y., Pedziwiatr, A.T., Pourarian, F., Wallace, W.E., “Inﬂuence of Hydrogen on the Magnetic Properties of Hyperstoichiometric ZrMn2T0.5 (T = Fe, Co, Ni and Cu)”, J. Magn. Magn. Mater., 68, 309–313 (1987) (Experimental, Magn. Prop., 9) Raghavan, V., “The Fe-Mn-Zr (Iron-Manganese-Zirconium) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Institute of Metals, Calcutta, 6B, 982–983 (1992) (Crys. Structure, Phase Diagram, Review, 5) Soubeyroux, J.L., Pontonnier, L., Miraglia, S., Isnard, O., Fruchart, D., Akiba, E., Hayakawa, H., Fujitani, S., Yonezu, I., “Crystal Structure and Microstructure Analysis of Alloys Zr(Mn1–xMx)2Hy with M = V, Fe, Ni, Co, Al and their Hydrides”, Z. Phys. Chem. (Munich), 179, 181–198 (1993) (Crys. Structure, Experimental, 12) Srinivas, V., Nigam, A.K., Chandra, G., Lawther, D.W., Yewondwossen, M., Dunlap, R.A., “Electrical Transport in Amorphous Fe-Mn-Zr Alloys”, J. Appl. Phys., 76(10/2), 6501–6503 (1994) (Experimental, Electr. Prop., Magn. Prop., 6) Ghezzi, F., Shmayda, W.T., Venkataramani, N., Bonizzoni, G., “Efﬁcient HTO Reduction Using a Zr-Fe-Mn Alloy”, Fusion Eng. Design., 28, 367–372 (1995) (Experimental, Kinetics, 8) Ghezzi, F., Shmayda, W.T., Bonizzoni, G., “An Experimental Investigation of the Efﬁciency of HTO Reduction by Zr-Fe-Mn Getter Alloy”, Fusion Technol., 31(1), 75–105 (1997) (Experimental, Kinetics, Review, 50) Shen, B., Guo, H., Zhang, J., Zhan, W., Zhao, J., “Magnetic Properties and Crystallization of Amorphous Fe90–xMnxZr10 Alloys with x = 0–15”, Mater. Sci. Eng. A, 226A–228A, 668–671 (1997) (Experimental, Magn. Prop., 15) Schlesinger, M.E., “The Mn-Zr (Manganese-Zirconium) System”, J. Phase Equilib., 20(1), 79–83 (1999) (Crys. Structure, Phase Diagram, Review, 42) Prakash, M., Ramaprabhu, S., “Hydrogen Absorption Studies in ZrMnFe0.7Co0.3”, Int. J. Hydrogen Energy, 25, 871–878 (2000) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 15) Ramaprabhu, S., “Structure and Hydrogen Solubility Studies on ZrMnFe1–xCox (x = 0.2, 0.3 and 0.5) Alloys”, Int. J. Hydrogen Energy, 25, 879–889 (2000) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 14)

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[2001Per2]

[2001Per3]

[2002Man1]

[2002Man2]

[2002Per]

[2002Ste]

[2003Dor]

[2004Li]

[2004Wit]

[2005Uly]

[2006Per] [2007Wit] [Mas2] [V-C2]

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Perumal, A., Srinivas, V., Rao, V.V., Dunlap, R.A., “Dynamics of Magnetic Susceptibility in Amorphous Fe80Mn10Zr10”, J. Alloys Compd., 326, 288–291 (2001) (Experimental, Magn. Prop., 6) Perumal, A., Srinivas, V., Kim, K.S., Yu, S.C., Rao, V.V., Dunlap, R.A., “Correction to Scaling Critical Exponents and Amplitudes for Amorphous Fe-Mn-Zr Alloys”, J. Magn. Magn. Mater., 233(3), 280–289 (2001) (Experimental, Phase Relations, Magn. Prop., 26) Perumal, A., Srinivas, V., Rao, V.V., Dunlap, R.A., “Low Field ac Response in Mn Substituted Amorphous Fe-Zr Alloys”, Mater. Sci. Eng. A, 304A–306A, 1004–1007 (2001) (Experimental, Magn. Prop., 12) Mani, N., Sivakumar, R., Ramaprabhu, S., “Hydrogen Storage Properties of ZrMnFe1–xNix (x = 0.2, 0.4, 0.5 and 0.6) Alloys”, J. Alloys Compd., 337, 148–154 (2002) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 16) Mani, N., Kesavan, T.R., Ramaprabhu, S., “Study of Hydrogen Absorption by ZrMnFe1–xCox (x = 0.2, 0.4, 0.5 and 0.6) Alloys”, J. Phys.: Condens. Matter, 14(15), 3939–3949 (2002) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 15) Perumal, A., Srinivas, V., Kim, K.S., Yu, S.C., Rao, V.V., Dunlap, R.A., “Magnetic Properties of Amorphous Fe90–xMnxZr10 (0 < x < 12) Alloys”, Phys. Rev. B, 65B(6), 064428_1–064428_15 (2002) (Experimental, Magn. Prop., 59) Stein, F., Sauthoff, G., Palm, M., “Experimental Determination of Intermetallic Phases, Phase Equilibria, and Invariant Reaction Temperatures in the Fe-Zr System”, J. Phase Equilib., 23(6), 480–494 (2002) (Crys. Structure, Experimental, Phase Relations, Phase Diagram, Morphology, 88) Dorogova, M., Hirata, T., Filipek, S.M., “Hydrogen-Induced Volume Changes in ZrCr2 and Pseudo-Binary Compounds of ZrCr2, ZrMn2 and ZrV2”, Phys. Status Solidi A, 198A(1), 38–42 (2003) (Crys. Structure, Experimental, 13) Li, G., Nishimiya, N., “Phase Relations of Zr(FexMn1–x)2-H2 Systems Studied by XRD and Isothermal Calorimetry Measurements”, J. Alloys Compd., 375, 205–211 (2004) (Crys. Structure, Thermodyn., Experimental, 18) Witusiewicz, V.T., Sommer, F., Mittemeijer, E.J., “Reevaluation of the Fe-Mn Phase Diagram”, J. Phase Equilib. Diff., 25(4), 346–354 (2004) (Experimental, Phase Diagram, Calculation, Thermodyn., #, 34) Ulyanov, A.N., Yu, S.C., Kang, Y.M., Yoo, S.I., “High Temperature Superparamagnetism in Boron Substituted Fe-Zr-Mn Alloys”, IEEE Trans. Magn., 41(10), 3265–3267 (2005) (Experimental, Magn. Prop., Nano, 12) Perumal, A., “Study of Magnetic Properties of Amorphous Fe-Mn-Zr Alloys”, Proc. Indian Natl. Sci. Acad., Part A, 72A(1), 43–48 (2006) (Experimental, Magn. Prop., 20) Witusiewicz, V.T., private communication to MSI, (2007) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–Mo–N

1

Iron – Molybdenum – Nitrogen Vasyl Tomashik

Introduction The Fe-Mo-N ternary system was investigated already since ﬁfty years but not much is known about the phase relationships of this system [1984Rag, 1987Rag1]. The solubilities of nitrogen in liquid and solid Fe-Mo alloys were measured by [1958Kas, 1960Mae, 1960Peh, 1963Sch, 1968Uda, 1973Pip, 1973Sak1, 1973Sak2, 1975Bel, 1981Yos]. All available data on nitrogen solubility in Fe rich alloys were evaluated by [1970Kun]. It was established that for alloys containing between 3 and 10 mass% Mo the solubility is independent on temperature within the interval 1500 to 1900°C. At 1700°C the solubility appears to increase approximately as a linear function of Mo content up to 10 mass% Mo [1958Kas]. Nitrogen solubility was found to obey Sieverts’ law for Fe-Mo alloys [1960Peh]. In arc-melted samples the nitrogen solubility appears about 20% higher than in levitation melted ones, most probably due to cracking the N2 molecules in the arc and the resulting non-equilibrium content of free N atoms in the gas. In a low nitrogen-content atmosphere (0.14 vol% N2 + Ar) the inﬂuence of Mo on the solubility of nitrogen is quite anomalous [1968Uda]. At higher N2 contents (3 or 5 vol% N2 + Ar) it is inﬂuenced by the alloying Mo in a manner similar to the equilibrium solubility found by levitation melting. The formation of a two-dimensional surface compound MoN was found on the (100) surfaces of a Fe-Mo single crystal, containing 3.5 mass% Mo [1997Bar]. This compound is epitaxed to the bcc (100) surface. It was found that this compound consists of a double Mo and a single N layer [1997Bar, 1998Vil]. The thickness of the MoN surface compound is about 230 pm [1997Bar]. [1973Sak1] and [1973Sak2] reported data on the (αFe)/((αFe) + Fe8N) and (αFe)/((αFe) + Fe4N) phase boundaries between 100 and 450°C in alloys containing up to 1.26 mass% Mo. The ternary compounds Fe3Mo3N [1957Eva, 1997Pan], Fe7Mo13N4 [1957Eva], (Fe0.8Mo0.2)MoN2 [1995Bem] and FeMoN2 [1998Pan] were found in this system. Thermodynamic properties of solid and liquid alloys in the Fe-Mo-N ternary system were investigated by [1958Kas, 1960Mae, 1960Peh, 1963Sch, 1968Uda, 1973Pip, 1973Sak1, 1973Sak2, 1983Pul2, 1991Sat, 1994Tan]. Table 1 lists the numerous experimental works on phase equilibria, crystal structure and thermodynamics of the Fe-Mo-N system. Binary Systems The Fe-Mo, Fe-N and Mo-N binary system are accepted from [Mas2]. Solid Phases Crystallographic data of all unary, binary and ternary compounds are listed in Table 2. The solubility of nitrogen in Fe-Mo alloys is increased by the presence of Mo [1958Kas, 1960Mae, 1960Peh, 1968Uda, 1973Pip, 1973Sak1, 1973Sak2, 1975Bel, 1981Yos]. According to [1975Huf] nitrided alloys contain a stoichiometric phase MoN and no mixed metal nitrides containing Fe were detected. The solubility of nitrogen in Fe- Mo alloy, containing up to 25 mass% Mo, at 1200–1600°C obeys Sieverts’ law up to 1 MPa N2 pressure [1963Sch, 1991Sat]. The alloy, containing 2.9 at.% Mo, dissolves 2.5 at.% of nitrogen at 580°C [1972Dri]. An analysis of the data of [1981Yos] by [1984Rag, 1987Rag1] gave the following empirical equation for the nitrogen solubility at 101.3 kPa N2 up to 1200°C: log(mass% N) = – 1046/T – 1.58 + (– 55/T + 0.064)(mass% Mo). At temperatures above 1200°C this equation gives lower solubilities than those found experimentally by [1981Yos].

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Fe–Mo–N

From evaluation of all available published data on nitrogen solubility in Fe rich alloys at various temperatures and nitrogen partial pressures [1970Kun] concluded, that the nitrogen solubility at constant temperature (log(mass% NT)), the heat of solution (H ’) and the entropy of solution (S ’) of nitrogen are practically linearly independent irrespective of melt composition. The following semiempirical equation was proposed for determination of nitrogen solubility: log (mass% NT) = 12log p(N2) – 1.290 – H’/4.575 (1/T – 1/3746). The solubility of nitrogen at 0.1 MPa pressure in Fe-Mo alloys at 1606 and 2240 ± 50°C according to [1958Kas, 1960Peh, 1968Uda] is shown in Fig. 1. The concentration dependence of the lattice parameter of the Fe-Mo-N solid solutions at 23°C can be expressed by a (nm) = (2.4 ± 0.1)·10– 4(at.% Mo) [1983Pul2]. The (αFe)/((αFe) + Fe8N) and (αFe)/((αFe) + Fe4N) phase boundaries computed from the results of [1973Sak1, 1973Sak2] by [1984Rag, 1987Rag1] are shown in Figs. 2 and 3. The limiting solubility of nitrogen in ferrite generally increases with increasing Mo content and increasing temperature. At the overlapping temperature range 200 to 350°C, where both, Fe8N and Fe4N, can form, the solubility in the matrix in equilibrium with the metastable precipitate Fe8N is larger than in that with the stable Fe4N. Ternary compounds Fe3Mo3N [1957Eva, 1997Pan], Fe7Mo13N4 [1957Eva], (Fe0.8Mo0.2)MoN2 [1995Bem] and FeMoN2 [1998Pan] are formed in the Fe-Mo-N ternary system. Fe3Mo3N has a η1 carbide structure with a cubic unit cell. Fe7Mo13N4 is also cubic and has the βMn type atom arrangement. (Fe0.8Mo0.2) MoN2 and FeMoN2 are hexagonal [1995Bem]. Thermodynamics Molybdenum has a pronounced negative effect on the activity coefﬁcient of nitrogen in liquid Fe (eMoN = – 0.013 at 1600–1700°C up to 7 mass% Mo [1960Mae, 1991Sat]; eMoN = – 0.011 at 1600°C up to 10.25 mass % Mo [1960Peh]; eMoN = – 0.05 at 1200°C at 0.56 at.% Mo [1960Peh]; eMoN = – 0.0051 at 2140–2240°C up to 8 mass% Mo and eMoN = – 0.0079 at 3.04 kPa of N2 up to 8 mass% Mo [1968Uda]; eMoN = – 0.19 ± 0.06 at 400–535°C up to 4 mass% Mo). According to [1973Pip] eMoN = – 260/T + 0.13 in the temperature range 400 to 500°C. According to the calculation of [1994Tan] εMoN = – 6.2. The interaction parameters are: eMoN = 0.13 and rMoN = 7.9·10– 5 [1991Sat]. ðxS Þ=k ) of nitrogen in Fe-Mo-N solid solutions are i ) and excess entropies (S Partial energies (E i – 435.9 ± 21.1 kJ·mol–1 and 9.7 ± 1.1 at 3.1 at.% Mo, – 436.7 ± 19.1 kJ·mol–1 and 10.1 ± 0.9 at 4.2 at.% Mo and – 440.0 ± 22.3 kJ·mol–1 and 10.7 ± 0.9 at 5.3 at.% Mo, respectively [1981Yos]. Assessed values of enthalpy and entropy interaction parameters are equal ηMoN = – 183 kJ·mol–1 and σMoN = – 46.1 J·(mol·K) –1 [1994Tan]. The addition of Mo decreases the heat of solution of Fe8N and Fe4N in (αFe) [1973Sak1, 1973Sak2]. The activity coefﬁcient of nitrogen in liquid Fe decreases with decreasing Mo content [1958Kas].

Notes on Materials Properties and Applications In general, nitrogen is unwanted in Fe-Mo alloys [1991Sat]. During solidiﬁcation by the involved decrease of solubility the gas may segregate and, depending on the boundary conditions, nitrogen bubbles can be produced. This may lead to reﬁnishing operations or waste of work pieces. In some special cases, however, nitrogen is used as an alloying element. Investigations of some Fe-Mo-N material properties are given in Table 3. Fe3Mo3N shows metallic behavior [1997Pan]. Changes in the temperature coefﬁcient of electric resistance at 120 K corroborate a magnetic phase transition. The material shows paramagnetic behavior and orders antiferromagnetically at a Neel temperature, TN = 120 K. The magnetic susceptibility displays a maximum for (Fe0.8Mo0.2)MoN2 at 20 K and four-probe conductivity measurements indicate poor metallic conductivity with a very small temperature dependence [1995Bem]. Ultraﬁne FeMoN2 is Pauli-paramagnetic in the temperature range 77–300 K having a magnetic susceptibility of 2.3·10–4 emu·g–1 at room temperature [1998Pan]. This compound exhibits also metallic behavior.

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Fe–Mo–N

3

Damping measurements on nitrided Fe alloys with Mo contents between 0.7 and 4 mass% were carried out by [1966Koe]. The effects of nitrogen content, heat treatment and degree of deformation on the formation of various maximum damping values were discussed. Miscellaneous The rate of total nitridization of Fe-Mo alloys is controlled by the diffusion of the nitrogen [1973Kun]. Diffusion coefﬁcients of the nitrogen in such alloys depending on the Mo content at different temperatures are given in Fig. 4. According to [1973Pip] Mo increases the precipitate density at the nitriding of the Fe-Mo alloys. The results of [1972Dri] show that the early stages of precipitation of a nitride from ferrite are associated with the formation of zones, as indicated by the appearance of side bands in the XRD patterns. According to [1975Bel] the Mo nitrides are not formed in the nitrated layer. But according to [1975Huf] the nitrided alloys contain precipitates of the stoichiometry MoN and no ternary compounds were detected. [1987Mor] noted that since the value of the standard Gibbs energy of Mo2N formation at 1600°C in liquid iron alloys is positive this nitride can not be precipitated in such alloys under normal conditions. The hardening of the diffusion layers of the Fe-Mo alloys is determined by the quantity of dissolved nitrogen [1975Bel]. Mo was found to segregate to interfaces in such alloys [1983Pul1]. Segregation of Mo is partly reduced by the formation of clusters or precipitates between nitrogen and solute atoms. It was found that the presence of small concentrations of bulk dissolved nitrogen in Fe-Mo alloys, containing 2 and 3.5 mass% Mo, induce a strong synergetic segregation (cosegregation) of Mo and N [1998Vil, 2001Vil]. This effect is strongest for (100)-oriented alloy, where an epitaxially stabilized MoN surface compound is formed [1998Vil]. The rate of Mo segregation is only slightly enhanced by the presence of nitrogen [1999Vil]. The diffusion parameters of Mo in the ﬁrst 20 layers of a Fe matrix were determined as D = 7·10–3 m2·s–1 and E = 290 kJ·mol–1. Fe3Mo3N was synthesized through an intermediate nitride having WC type structure by nitridation of a FeMoO4 precursor at 700°C [1997Pan] by ammonolysis of this precursor as well as by plasma nitridation of oxide precursors [1999Jac]. This compound is thermally stable up to 360°C [1997Pan]. The layered ternary nitride (Fe0.8Mo0.2)MoN2 could be synthesized in a single-step reaction by ammonolysis of Fe2(MoM4)3·8H2O [1995Bem]. This nitride decomposes by heating it in oxygen to 700°C, where the products of the oxidation were identiﬁed as Fe2O3 and MoO3. FeMoN2 is formed when Fe3Mo3N is heat treated at 300°C under ﬂowing NH3 for 6 h [1998Pan]. The crystallite size was found to be 12 nm.

Table 1.

Investigations of the Fe-Mo-N Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1957Eva]

XRD

Room temperature/Fe3Mo3N and Fe7Mo13N4

[1958Kas]

Sieverts’ method, N-solubility

1500–1900°C/Fe-Mo-N up to 10 mass% Mo

[1960Mae]

Sieverts’ method, N-solubility

1600–1750°C/Fe-Mo-N up to 7 mass% Mo

[1960Peh]

Sieverts’ method, N-solubility

1600°C/Fe-Mo-N up to 10.25 mass% Mo

[1963Sch]

Chemical analysis, N-solubility

1200°C/Fe-Mo-N at 0.56 at.% Mo

[1968Uda]

Levitation melting, chemical analysis arc melting, N-solubility

2140–22400°C/(Fe-Mo) up to 8 mass% Mo + N2/Ar

[1970Kun]

Calculation

1400–1800°C/Fe-Mo-N (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1972Dri]

XRD, microhardness measurements, gravimetry

580°C/Fe-Mo-N at 2.9 at.% Mo

[1973Kun]

Steady-state method, N-solubility

1550–1700°C/Fe-Mo-N

[1973Pip]

XRD, metallography

400–500°C/Fe-Mo-N

[1973Sak1]

Internal-friction technique

100–250°C/(Fe-Mo) at 0.65 and 0.92 mass% Mo + NHs/H2

[1973Sak2]

Internal-friction technique

250–450°C/(Fe-Mo) at 0.36, 0.65, 0.92 and 1.26 mass% Mo + NH3/H2

[1975Bel]

XRD, microhardness measurements, metallography

450–1000°C/(Fe-Mo) at 1.05, 1.82, 3.02 and 5.0 mass% Mo + N2

[1975Huf]

TEM, Mössbauer spectroscopy

400–600°C/(Fe-Mo) at 0.28 and 2.97 at.% Mo + NH3/H2

[1981Yos]

Chemical analysis, elastic properties measurements

660–1372°C/(Fe-Mo) at 3.1, 4.2 and 5.3 at.% Mo + N2

[1983Pul1]

SEM, AES

Room temperature/(Fe-Mo) at 2.4 at.% Mo + N2

[1983Pul2]

TEM, spectroscopic analysis

400–535°C/Fe-Mo-N up to 4 mass% Mo

[1991Sat]

Chemical analysis, N-solubility at elevated pressure

1600°C/Fe-Mo-N up to 25 mass% Mo

[1995Bem]

XRD, TGA, SEM, chemical analysis, crystal structure determination

Up to 700°C/(Fe0.8Mo0.2)MoN2

[1997Bar]

XPD, XPS, LEED, surface structure

620°C/Fe-Mo-N at 3.5 mass% Mo

[1997Pan]

XRD, DTA, SEM, chemical analysis, magnetic and electrical resistivity measurements, Mössbauer spectroscopy

Up to 700°C/Fe3Mo3N

[1998Pan]

XRD, morphology, Mössbauer spectroscopy

Up to 300°C/FeMoN2

[1998Vil]

XRD, AES, LEED, chemical analysis

500–900°C/Fe-Mo-N at 3.5 mass% Mo

[1999Jac]

XRD, TGA, neutron diffraction, chemical analysis, crystal structure determination

Room temperature/Fe3Mo3N

[1999Vil]

AES, surface segregation

500–600°C/Fe-Mo-N at 3.5 mass% Mo

[2001Vil]

AES, surface segregation

517–602°C/Fe-Mo-N at 2 mass% Mo

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Fe–Mo–N Table 2.

5

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(αδFe) (δFe) 1538–1394 (αFe) < 912

cI2 Im 3m W

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2] dissolves up to 25 at.% Mo at 1449°C

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [V-C2, Mas2]

(Mo) < 2623

cI2 Im 3m W

a = 314.70

at 25°C [Mas2]

MoFe (σ phase) 1611–1235

tP30 P42/mnm CrFe

a = 921.8 ± 0.2 c = 481.3 ± 0.2

[Mas2, V-C2] contains 43–57 at.% Mo

MoFe2 (λ phase) < 927

hP12 P63/mmc MgZn2

a = 474.5 c = 773.4

[Mas2, V-C2]

Mo6Fe7 (μ phase) < 1370

hR39 R 3m W6Fe7

a = 475.46 ± 0.05 c = 2571.6 ± 0.3

[Mas2, V-C2] contains 39–44 at.% Mo

Mo2Fe3 (R phase) 1488–1200

hR159 R 3 Co5Cr2Mo3

a = 1095.6 c = 1935.3

[Mas2, V-C2] contains 33.9–38.5 at.% Mo

α”Fe16N2

tI* I4/mmn

a = 572 c = 629

ordered fcc structure, metastable [1987Rag2]

γ’Fe4N < 680

cP5 Pm 3m Fe4N

a = 378.7

19.4 to 20.6 at.% N. Ordered fcc structure [1987Rag2]

ε Fe3N < 580

hP10 P6322 Fe3N

a = 469.96 ± 0.03 c = 438.04 ± 0.03 a = 471.8 c = 438.8 a = 479.1 c = 441.9

ζFe2N < 500

oP12 Pbcn Fe2N

a = 551.2 b = 482.0 c = 441.6

15.8 to 33.2 at.% N [1987Rag2] εFe3N at RT [1999Lei] εFe3N1.10 [2001Lei] Lattice parameters decrease slightly with decrease in nitrogen content [2001Lei] εFe3N1.39 [2001Lei] at 25°C [1987Rag2]

(continued)

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Fe–Mo–N

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

MoN ?

hP16 P63/mmc MoN

a = 572.5 c = 560.8

[Mas2, V-C2]

βMo2N < 850

tI12 I41/amd Mo2N

a = 420.0 c = 801.0

[Mas2, V-C2] contains 28.7-35 at.% N

Mo3N2 ?

cP8 Pm 3m Mo3N2

a = 416.5

[Mas2, V-C2]

* τ1, Fe3Mo3N

cF112 Fd 3m W3Fe3C

a = 1108.0 ± 1.5 a = 1106.7 a = 1108.59 ± 0.03

[1957Eva] Stable in air up to 560°C [1997Pan] [1999Jac]

* τ2, Fe7Mo13N4

cP24 P4132 βMn

a = 669.84 ± 0.36

[1957Eva]

* τ3, (Fe0.8Mo0.2) MoN2

hP8 P 31c Fe0.8Mo1.2N2

a = 285.62 ± 0.01 c = 1099.97 ± 0.04

Stable in oxygen up to 700°C [1995Bem]

* τ4, FeMoN2

hP2 P 6m2 WC

a = 284.3 c = 273.5

[1998Pan]

Table 3.

Investigations of the Fe-Mo-N Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1966Koe]

Torsion pendulum

Damping

[1995Bem]

Four-probe conductivity measurements, magnetometry

Electric conductivity and magnetic susceptibility for (Fe0.8Mo0.2)MoN2

[1997Pan]

Four-probe conductivity measurements, magnetometry, AC susceptibility measurements

Electric conductivity, magnetic susceptibility, temperature coefﬁcient of resistance and Neel temperature for Fe3Mo3N

[1998Pan]

Magnetometry, AC susceptibility measurements, resistivity study

Magnetization, magnetic susceptibility, and temperature coefﬁcient of resistance for FeMoN2

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Fig. 1. Fe-Mo-N. Solubility of nitrogen at 0.1 MPa pressure in Fe-Mo alloys at 1606 and 2240 ± 50°C

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Fe–Mo–N

Fig. 2. Fe-Mo-N. (αFe)/((αFe) + Fe4N) phase boundaries at 125, 175 and 225°C

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Fe–Mo–N

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Fig. 3. Fe-Mo-N. (αFe)/((αFe) + Fe8N) phase boundaries at 250, 350 and 450°C

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Fe–Mo–N

Fig. 4. Fe-Mo-N. Diffusion coefﬁcients of nitrogen in Fe-Mo alloys depending on the Mo content at different temperatures

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Fe–Mo–N References [1957Eva] [1958Kas] [1960Mae]

[1960Peh]

[1963Sch]

[1966Koe]

[1968Uda]

[1970Kun]

[1972Dri] [1973Kun]

[1973Pip]

[1973Sak1]

[1973Sak2]

[1975Bel]

[1975Huf] [1981Yos]

[1983Pul1]

[1983Pul2]

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Evans, D.A., Jack, K.H., “Interstitial Alloys with the Structure of β -Manganese”, Acta Crystallogr., 10, 769–770 (1957) (Experimental, Crys. Structure, 2) Kashyap, V.C., Parlee, N., “Solubility of Nitrogen in Liquid Iron and Iron Alloys”, Trans. Met. Soc. AIME, 212, 86–91 (1958) (Experimental, Phase Relations, *, 19) Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron Alloys. II. Effect of Niickel, Cobalt, Molybdenum, Chromium and Vanadium on the Solubility in Liquid Iron”, Tetsu to Hagane, 46(9), 972–976 (1960) (Experimental, Phase Relations, Thermodyn., 8) Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans Met. Soc. AIME, 218(6), 1088–1101 (1960) (Experimental, Phase Relations, Thermodyn., *, 32) Schenck, H., Frohberg, M.G., Reinders, F., “Contribution to the Study of the Solubility of Nitrogen in the Iron Alloys over the Temperature Range from 700 to 1200°C” (in German), Stahl u. Eisen, 83(2), 93–99 (1963) (Experimental, Phase Relations, Thermodyn., 36) Koester, W., Horn, W., “Damping Investigation on Nitrided Iron-Molybdenum and IronVanadium Alloys” (in German), Arch. Eisenhuettenwes., 37(3), 245–252 (1966) (Experimental, Morphology, Thermodyn., 22) Uda, M., Wada, T., “Solubility of Nitrogen in Arc-Melted and Levitation-Melted Iron and Iron Alloys”, Trans. Nat. Res. Inst. Met. (Jpn.), 10(2), 79–91 (1968) (Experimental, Phase Relations, Thermodyn., *, 40) Kunze, H.-D., Schuermann, E., Parlee, N.A.D., “Inﬂuence of Temperature and Equivalent Effect of Added Elements on the Solubility, Activity and Activity Coefﬁcient of Nitrogen in Liquid Iron”, Met. Trans., 1(1), 281–290 (1970) (Calculation, Phase Relations, Thermodyn., 45) Driver, J.H., Unthank, D.C., Jack, K.H., “Substitutional-Interstitial G.P. Zones in Nitrided FeMo Alloys”, Philos. Mag., 26(5), 1227–1231 (1972) (Experimental, Phase Relations, 8) Kunze, H.-D., “Effect of the Elements Chromium, Manganese, Cobalt, Nickel, Molybdenum and Tungsten on the Diffusion of Nitrogen in Liquid Iron Alloys” (in German), Arch. Eisenhuettenwes., 44(2), 71–80 (1973) (Experimental, Kinetics, 50) Pipkin, N.J., Roberts, W., Speirs, D.L., Grieveson, P., Jack, K.H., “Effect of Substitutional Alloying Elements on the Activity Coefﬁcients and Behaviour of Interstitial Solutes in Iron”, Internat. Symposium on Metallurgical Chemistry - Applications to Ferrous Metall., 351–352 (1973) (Experimental, Phase Relations, 7) Sakamoto, M., Imai, Y., “Effects of Cobalt, Nickel, Molybdenum and Tungsten on the Solubility of Fe16N2 in α-Iron”, J. Jpn. Inst. Met., 37(7), 708–714 (1973) (Experimental, Phase Relations, Thermodyn., *, #, 9) Sakamoto, M., Masumoto, T., Imai, Y., “The Effect of Cobalt, Molybdenum and Tungsten on the Solubility of Fe4N in α-Iron”, J. Jpn. Inst. Met., 37(3), 343–349 (1973) (Experimental, Phase Relations, Thermodyn., *, #, 19) Belotsky, A.V., Nikitina, O.V., Permayakov, V.G., “Structure and Some Properties of the Nitrided Layer in Iron-Molybdenum Alloys” (in Russian), Izv. Akad. Nauk SSSR, Met., (1), 112 (1975) (Experimental, Phase Relations, Mechan. Prop., 9) Huffman, G.P., Podgurski, H.H., “Mössbauer Study of Nitrided Fe-Mo and Fe-Ti Alloys”, Acta Metall., 23(11), 1367–1379 (1975) (Experimental, Phase Relations, 21) Yoshihara, M., McLellan, R.B., “Thermodynamics of Body-Centered Cubic Iron- MolybdenumNitrogen Solid Solutions”, Acta Metall., 29(3), 471–478 (1981) (Experimental, Thermodyn., *, 12) Pulkkinen, R.E.E., Laehdeniemi, M., “Grain-Boundary Segregation in Bright Nitrided α-Irons Alloyed with Chromium, Molybdenum and Silicon”, J. Mater. Sci., 18(11), 3421– 3426 (1983) (Experimental, Morphology, 12) Pulkkinen, R., “The Activity Coefﬁcients of Nitrogen in α -Irons Alloyed with Chromium, Molybdenum and Silicon”, Scand. J. Metall., 12, 87–92 (1983) (Experimental, Crys. Structure, Thermodyn., 24)

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12 [1984Rag] [1987Mor] [1987Rag1]

[1987Rag2]

[1991Sat]

[1994Tan]

[1995Bem]

[1997Bar]

[1997Pan]

[1998Pan]

[1998Vil]

[1999Jac]

[1999Lei]

[1999Vil]

[2001Lei]

[2001Vil] [Mas2] [V-C2]

Fe–Mo–N Raghavan, V., “The Fe-Mo-N (Iron-Molybdenum-Nitrogen) System”, Trans. Indian Inst. Met., 37(4), 308–312, (1984) (Review, Crys. Structure, Phase Diagram, Phase Relations, *, #, 23) Morita, Z., Tanaka, T., Yanai, T., “Equilibrium of Nitride Forming Reactions in Liquid Iron Alloys”, Metall. Trans., B, 18B(3), 195–202 (1987) (Review, Phase Relations, Thermodyn., 29) Raghavan, V., “The Fe-Mo-N (Iron- Molybdenum- Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Techn., Delhi, 1, 191–194 (1987) (Review, Crys. Structure, Phase Diagram, Phase Relations, *, #, 20) Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) Satir-Kolorz, A.H., Feichtinger, H.K., “On the Solubility of Nitrogen in Liquid Iron and Steel Alloys Using Elevated Pressure”, Z. Metallkd., 82(9), 689–697 (1991) (Experimental, Phase Relations, Thermodyn., 24) Tanaka, T., Gokcen, N.A., Iida, T., Morita, Z.-I., “Thermodynamic Relationship between the Enthalpy Interaction Parameter and the Entropy Interaction Parameter in Liquid Iron-Nitrogen Based Ternary Alloys”, Z. Metallkd., 85(10), 696–700 (1994) (Calculation, Thermodyn., 17) Bem, D.S., Olsen, H.P., zur Loye, H.-C., “Synthesis and Electronic and Magnetic Characterization of the Ternary Nitride (Fe0.8Mo0.2)MoN2”, Chem. Mater., 7(10), 1824–1828 (1995) (Experimental, Crys. Structure, Magn. Prop., 46) Baraldi, A., Brena, B., Cocco, D., Comelli, G., Lizzit, S., Paolucci, G., Baumann, P., Scheuch, V., Uebing, C., “The Structure of the MoN Surface Compound on Fe-3.5%Mo-N (100) Studied by X-Ray Photoelectron Diffraction: First Results from ELETTRA”, Vacuum, 48(3–4), 351–355, (1997) (Experimental, Crys. Structure, Interface Phenomena, 34) Panda, R.N., Gajbhiye, N.S., “Electronic and Magnetic Properties of Fe3Mo3N”, J. Alloys Compd., 256(1–2), 102–107 (1997) (Experimental, Crys. Structure, Magn. Prop., Morphology, 25) Panda, R.N., Gajbhiye, N.S., “Chemical Synthesis and Magnetic Properties of Nanocrystalline FeMoN2”, J. Cryst. Growth, 191(1–2), 92–96, (1998) (Experimental, Crys. Structure, Morphology, 15) Viljoen, E.C., Uebing, C., “Effect of Nitrogen and Sulphur on the Segregation of Molybdenum on Single Crystalline Fe3.5%Mo-N,S Alloys”, Surf. Sci., 410(1), 123–131, (1998) (Experimental, Interface Phenomena, 24) Jackson, S.K., Layland, R.C., zur Loye, H.-C., “The Simultaneous Powder X-Ray and Neutron Diffraction Reﬁnement of Two η-Carbide Type Nitrides, Fe3Mo3N and Co3Mo3N, Prepared by Ammonolysis and by Plasma Nitridation of Oxide Precursors”, J. Alloys Compd., 291(1–2), 94–101 (1999) (Experimental, Crys. Structure, 25) Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe3N: Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys Compd., 288(1–2), 79–87 (1999) (Experimental, Crys. Structure, 40) Viljoen, E.C., Jordaan, W.A., Uebing, C., du Plessis, J., “The Effect of N on the Segregation Kinetics of Mo in a Fe-3.5%Mo-N(100) Single Crystal Studied by Constant Temperature Heating Method”, Mater. Sci. Forum, 294–296, 461–464 (1999) (Experimental, Interface Phenomena, 10) Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316, 21–38 (2001) (Experimental, Crys. Structure, 47) Viljoen, E.C., Jordaan, W.A., du Plessis, J., “On the Determination of Ternary Segregation Parameters”, Vacuum, 61(2–4), 141–144, (2001) (Experimental, Interface Phenomena, 5) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_25 # Springer 2008

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Fe–Mo–Ni

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Iron – Molybdenum – Nickel Volodymyr Ivanchenko, Tetyana Pryadko

Introduction Magnetically soft alloys of the Fe-Ni system are used extensively in instrument fabrication owing to a favorable combination of a number of properties: single-phase alloys in a stable condition over a wide concentration range, an absence of allotropic transformations which can cause development of internal stresses, and the existence of ordering with the possibility of controlling the degree of ordering through alloying. However, alloys of the Fe-Ni system have low strength and wear resistance which limit their use, for example as magnetic recording head material. One of the most widespread methods for improving the mechanical properties of these alloys is by alloying with a third element, such as Mo, in order to form solid solutions and to impart an improvement in mechanical properties [1992Sos]. The Fe-Mo-Ni system is the basis for the development of new permanent magnetic materials with excellent magnetic shielding performance up to 4.2 K. Alloys of the Fe-Mo-Ni system exhibit high ductility. The constitutional diagram was ﬁrst examined by [1934Koe], reproduced by [1949Jae], then by [1952Das] at 1200°C, diagram reproduced by [1973Wad]. Primary crystallization ﬁelds, and the resultant equilibria in the solid state after solidiﬁcation were critically evaluated by [1984Ray, 1988Ray] which pointed out that knowledge of the binary systems Fe-Mo and Mo-Ni upon which the interpretation of the equilibria was based, was at that time seriously incomplete. Isothermal sections between 800 and 1250°C, and vertical sections were investigated by [1989Oda, 1990Gan] and the results reviewed by [1994Rag] who constructed the Fe-Mo-Ni reaction scheme from the solidiﬁcation range down to 900°C. [1993Goz] reported about the melting temperature and the composition of a new γ+σ+τ ternary eutectic. [1997Sch] carried out isothermal holding tests in the two-phase region between liquidus and solidus. The liquidus line deﬁning the threephase equilibrium (αδ+γ+L) was obtained from the intersecting points of the isotherms on the γ and αδ liquidus surfaces. [1997Sch] extrapolated their results to obtain a liquidus projection for the Fe“Mo2Fe3”-MoNi-Ni region. The data that [1997Sch] assumed for the Fe-Mo intermediate phases, and the liquid-solid equilibria are obsolete and do not agree with the accepted binary diagrams. Based on these results and on the known liquidus lines in the three boundary binary systems, as well as on the known concentration ﬁelds of the MoFe3-MoNi solid solutions, the melting equilibria were developed. To obtain the homogeneity region of the γ phase, series of specimens in which the concentration of Mo slightly exceeded the estimated solubility range for γ austenite were prepared and studied by [1989Gol]. The experimental examination has been combined with the Calphad method with the aim to get consistent phase diagrams. But there are serious discrepancies between calculations and experimental data of the previous authors [1952Das, 1953Das, 1980Loo]. The isothermal section at 1100°C was determined by [2006Yan]. It does not agree with the results of [1980Loo] and [1992Fri] due to a very low solubility of Ni in the μ phase and an absence of a ternary phase. The undercooling of Fe-Mo-Ni alloys under different cooling rates was studied by [1994ElM]. Investigations of the Fe-Mo-Ni phase relations, structures and thermodynamics are listed in Table 1. Binary Systems The Fe-Mo system is accepted from [Mas2]. The Fe-Ni and Mo-Ni systems are accepted from [2007Kuz] and [1991Sin], respectively. It should be noted, that some ternary diagrams in the present evaluation are accepted from the thermodynamic calculations of [1992Fri] and are based on the following binaries: FeMo from [1984Gui], Mo-Ni from [1990Fri], and Fe-Ni from [1990Xin]. The calculated Fe-Ni and Mo-Ni phase diagrams are practically the same as those accepted by us. In Fe-Mo the main difference between the calculated [1984Gui] and evaluated [Mas2] diagrams is in the temperature of the peritectoid formation of MoFe2. In other respects these two phase diagrams are nearly the same.

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Fe–Mo–Ni

Solid Phases The effect of Mo on the ordered phase FeNi3 was studied by [1951Che, 1968Art, 1970Gom]. Using neutron-diffraction techniques [1970Gom] found that solution of Mo in FeNi3 caused a remarkable decrease in the long-range-order parameter S. Along the compositional line representing the formula (Fe,Mo)Ni3, which runs from 75.9Ni-24.lFe (mass%) on the Fe-Ni axis, the order parameter S decreases from unity to 0.8 at 3.2 mass% Mo, 21.9 mass% Fe, and falls to zero at approximately 6.4 mass% Mo, 19.7 mass% Fe. These results are in general agreement with studies of [1951Che, 1968Art]. In accordance with [1980Loo], an approximated composition of the ternary phase τ is Mo53Fe11Ni36 (7.9Fe-65.lMo-27Ni, mass%). Crystal structure data of the unary, binary and ternary phases are presented in Table 2. Invariant Equilibria A reaction scheme has been derived by [1994Rag] who used the results of computations of [1992Fri]. Since the computed temperatures of most of the invariant reactions were not reported by [1992Fri], they must be regarded only as tentative values. The reaction scheme shown in Fig. 1 is taken mainly from [1994Rag], however the temperatures of the invariant reactions E1, U11 and P2 have been modiﬁed to be consistent with the isothermal sections accepted in the present evaluation, see section “Isothermal Sections” below. Liquidus, Solidus and Solvus Surfaces A liquidus projection has been computed by [1992Fri]. As the experimental data on the liquid equilibria at that time were scarce, the computed liquidus projection should be considered as tentative. It is given in Fig. 2. [1997Sch] extrapolated the results of their experimental study of the liquidus surface in the Fe rich corner to obtain the liquidus surface in the Fe-Ni-Fe3Mo2-MoNi subsystem. Since it did not included equilibria with the σ and R phases and was in contradiction with the results of [1993Goz], who reported the formation of the γ + σ + τ ternary eutectic with the melting point of 1312°C and the composition of 16.5Fe-34.5Mo-49Ni (at.%), results of the extrapolations obtained by [1997Sch] are omitted. The way of formation of this eutectic may be derived from [1992Fri], if the reaction sequence of L + σ⇌(Mo) + τ → L + (Mo)⇌MoNi + τ → L + τ⇌MoNi + γ would be replaced by the sequence: L + MoNi⇌(Mo) + γ → L + (Mo)⇌σ + γ → L⇌γ + σ + τ. Since this assumption needs experimental veriﬁcation, the liquidus projection calculated by [1992Fri] as well as the reaction scheme constructed by [1994Rag] are not changed. The spinodal region was determined in Fe-Mo-Ni ternary alloys at 450 and 500°C within a composition range 10 to 16 at.% Mo and 2 to 14 at.% Ni by [1992Sat]. Isothermal Sections Constitutional diagrams proposed by [1934Koe] are in contradiction with the accepted binary phase diagrams. Therefore neither the high-temperature nor the low-temperature phase diagrams are reproduced in the present evaluation. The isothermal section at 1270°C was computed by [1992Fri] and given in Fig. 3. This section is in good agreement with the isothermal section at 1200°C presented by [1952Das]. The major features of the latter are the extensive γ solid solution, the considerable solid solubility of Ni in Mo6Fe7, and the existence, between μ and MoNi, of the ternary compound τ. The 1200°C isothermal section from [1952Das] is shown in Fig. 4 after small modiﬁcations to bring it in agreement with the accepted binary phase diagrams. A very close location of the γ corners of the τ + MoNi + γ and τ + μ + γ triangles presented by [1952Das] seems to be improbable. Therefore in Fig. 4 they are slightly separated. [1952Das] found τ to be in equilibrium with γ and μ, thus preventing μ from coexisting with MoNi. [1980Loo], however, with a τ composition slightly richer in Mo than that given by [1952Das], proposed that at 1100°C a two-phase region μ + MoNi is established, thus preventing equilibrium between τ and γ. In this connection, an alloy containing 9Fe-56.5Mo-34.5Ni (mass%) (12Fe-44Mo-44Ni (at.%)) was identiﬁed unambiguously by [1980Loo] as containing the μ, δ, and γ phases, so that the equilibria summarized in Fig. 5 appear to be well established. [1984Ray, 1988Ray] noted that, assuming the more Mo rich composition for τ, the equilibrium described at DOI: 10.1007/978-3-540-78644-3_26 # Springer 2008

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1100°C by [1980Loo] may be derived from that proposed at 1200°C by [1952Das] by the univariant reaction τ + γ ⇌ μ + MoNi and it is not impossible that such a reaction should occur within the temperature interval involved. This assumption is conﬁrmed by the results of computation of the isothermal sections at 1270°C (Fig. 3) and 950°C (Fig. 6) performed by [1992Fri]. [1991Goz] and [1992Fri] showed that τ was stable at 1000°C. [1991Goz] did not ﬁnd τ at 850°C and below. [1992Fri] found τ to be stable at 950°C, with a decreased range of homogeneity. The computed isothermal section at 950°C by [1992Fri] validated by the experimental results indicates that τ becomes unstable just below 950°C and decomposes through a ternary eutectoid reaction (E3). [1989Oda] presented the isothermal section at 800°C, it is redrawn from [1994Rag] in Fig. 7. The isothermal section at 1100°C presented by [2006Yan] is characterized by an unlikely low μ phase region and by an absence of the ternary phase. For this reason it is not included in the present evaluation. Temperature – Composition Sections The temperature-composition section presented by [1957Bec] at a constant Fe content of 70 mass% is doubtful whether it represents equilibrium state and is in contradiction with the results of [1952Das] and [1980Loo]. [1984Ray, 1988Ray] assumed that [1957Bec] mistook some non-equilibrium constituent for Fe2Mo. This assumption, combined with the postulate that Fe2Mo forms by the peritectoid reaction (P2) eliminates the wide γ + Fe2Mo + μ area presented on the polythermal section, given by [1957Bec] and leads to the observed sequence of phase ﬁelds below the peritectoid transformation αδ + μ, αδ + μ + Fe2Mo, αδ + Fe2Mo, αδ + γ + Fe2Mo, γ + Fe2Mo, γ + Fe2Mo + μ, γ + μ). The hypothetical polythermal section proposed by [1984Ray, 1988Ray] is shown in Fig. 8, however the temperature of the P2 transformation is shown below 950°C to be consistent with the isothermal section at 950°C from [1992Fri]. Thermodynamics [1983Kub] measured calorimetrically the heats of formation of ternary alloys in the temperature range of 900 to 1050°C. These results are presented in Table 3. Thermodynamic evaluation of the Fe-Mo-Ni system was performed by [1992Fri]. Based on the mixing volumes of alloys in the boundary binary systems [1993Leo] made an attempt to estimate mixing volume of the γ phase in ternary alloys. Notes on Materials Properties and Applications The effect of composition and heat treatment on mechanical properties of Fe-Mo-Ni alloys was studied by [1975Roa, 1978Ish, 1980Nos]. The Fe-Mo-Ni maraging steels have evoked a great deal of interest in the aerospace and aeronautical industries where they are used for missile framework and in landing chassis and in various other industries such as those manufacturing extrusion trains for light alloys, injection moulds for plastics, storage tanks for liquid gas, mechanical parts subjected to low temperatures, etc. [1977Ser]. Fe-Ni-Mo steels (Fe-13Ni-3Mo (mass%)) are used for cryogenic service [1978Ish]. Magnetically soft iron-nickel alloys containing 76–80% Ni have maximum magnetic permeability in weak ﬁelds. They are used for the fabrication of magnetic screens, small transformers, relays, sound-recorder heads, pulse transformers, and other contactless magnetic elements. The most widely used is the alloy 79NM, in which added molybdenum increases the speciﬁc electrical resistance, substantially raises the initial magnetic permeability and decreases its sensitivity to cooling rate, but in doing so lowers the magnetic induction [2001Vla]. An alloy containing 34.5 mass% Ni and 2 mass% Mo, exhibited permeability of 55000 at 25°C [1973Pfe]. The permeability and saturation magnetization of this alloy are comparable to nickel-iron alloys in the higher nickel range. The speciﬁc resistivity of the investigated alloy has the signiﬁcantly higher value of 0.9 Ωαﬄ m. The obtained Curie temperature of 160°C is comparable with that of highly permeable ferrites. The achieved level of characteristics permits recommending alloys for production of precise instrument engineering parts, electronic devices and other facilities of automation and computer engineering. The electrodeposition of alloys has been gaining in importance owing to its practical utility in modern technology for special items which cannot be produced in any other way. Recent efforts have been directed to preparing Landolt-Börnstein New Series IV/11D4

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magnetic alloys which are of great interest in the sophisticated electronics industry related to rocketry, computers, space technology etc. Strain-insensitive magnetic foil of Fe-Mo-Ni alloy electrodeposited from a sulfamate bath has been reported to contain 18 mass% Fe, 9 mass% Mo and 73 mass% Ni with a coercive force of 0.05 Oe (~ 4 A·m–1) and a magnetic ﬂux of 8200 G [1980Sri]. New, ductile, and cobalt-free magnet alloys based on the Fe-Mo-Ni system have been developed for potential substitution of some Co-Fe base magnet alloys. The new alloys are very ductile and can be processed into thin tape or ﬁne wire. A Fe-20Mo-5Ni (mass%) alloy can be processed to exhibit magnetic properties of Br ≈ 10500 G, Hc ≈ 210 Oe (~16 800 A·m–1), and (BH)max ≈ l.l MGOe which are comparable to those of Vicalloy I (52Co38Fe-10V). A Fe-7 mass% Mo-5 mass% Ni alloy exhibits high remanence, square-loop, anisotropic magnet properties of Br ≈ 19200 G, Hc ≈ 30 Oe (~ 2 400 A·m–1), and Br/Bs ≈ 0.97 which are superior to those of classical Fe-Co-Ni magnetic alloys. The new Fe-Mo-Ni alloys consist of abundant elements and could substitute for some of the Co-Fe base magnet alloys which contain large amounts of expansive and strategic cobalt [1981Jin, 1984Tie]. Ni-14.5 mass% Fe-4.5 mass% Mo has excellent magnetic shielding performance at 4.2 K. It is required for superconducting quantum interference devices (SQUID) to avoid inﬂuences of electromagnetic noises [1984Suz]. [1988Mag] reported, that plastic deformation of Fe-20 mass% Mo-5 mass% Ni before annealing raises Br as well as Hc at higher degrees of deformation owing to the formation of a crystallographic texture and diminution in size of precipitates of the intermetallic phase. Miscellaneous The effect of alloying with Mo on the driving force of the martensitic transformation was examined by [2000Rag]. The atomic ordering in the FeNi3 alloyed with Mo was studied by [1968Ega, 1969Yeg1, 1969Yeg2, 1979Wen] by measuring temperature dependences of resistivity, saturation magnetization and temperature and composition dependencies of the Young modulus (E). It was shown that alloying with Mo leads to a depression of E with a minimum at 3.8 at.% Mo. At the Mo content below this value Mo atoms take part in ordering, due to the formation of a three-component superstructure [1969Yeg1]. The magnetic properties and hardness of Fe-Mo-Ni alloys has been studied by [1979Wen]. The paramagnetic-magnetically ordered transition and the effect of Mo content on the magnetic properties of martensite phase in Fe-30% Ni-x% Mo alloys have been investigated by in [2006Yas] AC susceptibility and Mössbauer spectroscopy. The results show that martensitic transformation temperature (Ms) indicates the magnetic transition from paramagnetic to magnetically ordered state. It is found that volume fraction of thermally induced martensite and Ms temperature decreased with the increasing Mo content [2006Yas]. Opportunities of the production of Fe-Mo-Ni alloys by means of powder metallurgy including mechanical milling were studied by [1986Rod, 1986Sar, 2001Vla, 2004Chi, 2004She]. Nanocrystalline and amorphous Fe40Ni38B18 Mo4, Fe49Ni46Mo5 and Fe42Ni40B18 alloys were synthesized by ball milling to study the effect of boron and molybdenum on the milling process and on the magnetic properties of Fe-Ni based alloys [2005Du]. [1969Yed] studied an maraging Fe-16.8Ni-5Mo (mass%) alloy and showed that under aging of martensite at 300–650°C the Laves phase Mo(Fe,Ni)2 is formed in the forms of dispersed particles. The rise of carbon content in Fe-Mo-Ni austenitic steel as well as rise of the austenitizing temperature leads to a decrease of the Ms (Martensite start) temperature [1996Gol, 1998Gol, 2000Gol]. Structural evolution of the alloy Fe10Ni-10Mo (mass%) by returning to a lower temperature from the point As was studied by [1975Kno]. The nuclear gamma resonance (NGR) has been used to study the inﬂuence of annealing on the ﬁne atomic structure of the austenite of alloys Fe-(28-36) % Ni with additions of Mo and Si. Below 500°C treatment reduces the hyperﬁne magnetic ﬁeld on the iron nucleus. A comparison of these results with known neutron diffraction and Mössbauer data leads to the conclusion that annealing at 300–500°C causes redistribution of the alloying atoms with formation of regions enriched with nickel and molybdenum atoms. After treatment at temperatures above 500°C the hyperﬁne magnetic ﬁeld in those alloys has increased, which could either be due to a breakdown of concentration heterogeneities, or precipitation of a second phase [1980Rod]. A series of solidiﬁcation experiments with different heat extraction methods were performed on an iron alloy 12 mass% Ni and 10 mass% Mo by [1994ELM]. The undercooling during the solidiﬁcation process was measured as a function of the cooling rate. An undercooling of 550°C was achieved at a cooling rate of 7000 K·s–1. This undercooling is far below the solidus curve in the ternary phase diagram. DOI: 10.1007/978-3-540-78644-3_26 # Springer 2008

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Redistribution of alloying elements under aging in the Fe-16Ni-5Mo (mass%) alloy was studied by [1973Gru, 1980Fra]. The changes in the ﬁne atomic structure of austenitic alloys Fe-(28-36) at.% Ni with additions of Mo were studied by NGR after annealing in the range 200–800°C, and the activation energy of the processes occurring below 500°C determined [1980Rod]. The main processes which take place in Fe-16 mass% Ni-6 mass% Mo at the early stages of decomposition of the supersaturated solid solution, ﬁlling of Cottrell atmospheres, formation of concentration inhomogeneities of molybdenum and their transformation into particles of a strengthening phase were investigated by [1987Val]. A quantitative analysis of the 57Fe hyperﬁne ﬁeld distribution P(H) has been performed in quenched bcc disordered Fe-Mo-Ni alloys in order to determine the matrix depletion of Ni and Mo atoms that occurs after aging [1995Dje]. The small atomic fraction assigned to the precipitates, observed on the Mössbauer spectra after a 72-h aging at 450°C of Fe78.3Ni18.3Mo3.4 and Fe79.3Ni15.0Mo5.7 alloys, is corroborated by the small volume fraction of the nanocrystalline precipitates revealed by transmission electron microscopy (TEM). The two precipitated phases, (Fe-Ni)3Mo and ω (Fe-Ni)7Mo2, detected by TEM are consistent with the Mössbauer approach, with an overall Fe to (Ni,Mo) atomic ratio twice smaller for Fe79.3Ni15.0Mo5.7 than for Fe78.3Ni18.3Mo3.4, giving evidence for an evolution to depleted-Fe species. Table 1.

Investigations of the Fe-Mo-Ni Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1934Koe]

Thermal analysis, Brinell hardness

1200, 800°C, Fe-Mo Fe3-MoNi-Ni, primary crystallization ﬁelds

[1952Das] [1953Das]

Light microscopy, XRD (X-ray diffraction)

1200°C, < 70 at.% Mo, isothermal section from the analysis of 105 alloys

[1957Bec]

Light microscopy, XRD

< 1350°C, 70 mass% Fe, 0-20 mass% Ni, isothermal sections

[1968Art]

Resistivity, Young modulus, XRD

Ni3(Fe,Mo) annealed at 800°C then cooled at the rate of 10°C·h–1

[1969Geo1, 1969Geo2]

Optical microscopy, ballistic magnetometry

24.3 mass% Ni-5.2 mass% Mo, annealing at 1260°C, then quenched. Martensitic transformation at (77–293 K)

[1969Mir]

Magnetometer, DTA, thermodynamic calculations

1100°C, 9.6 at.% Ni, < 3 at.% Mo

[1969Yed]

TEM and electron microdiffraction

16.8 mass% Ni, 5 mass% Mo, cooling in air from 1000°C, then aged at 300–650°C. Austenitization

[1969Yeg1]

Young modulus, saturation magnetization

75 at.% Ni, 17.1-24.3 at.% Fe, annealing at 250–600°C. Ordering in (Mo,Fe)Ni3

[1969Yeg2]

Resistivity, Young modulus

350–400°C, (Mo1–xFex)Ni3, ordering

[1970Cou]

TEM, electron microdiffraction

Ageing between 100 and 570°C, Fe-19 at.% Ni-5 at.% Mo, α→γ transformation

[1970Yed]

X-ray diffraction, Vickers hardness, resistivity

15.8 to 16.5 mass% Ni, < 7.8 mass% Mo. Annealed at 1000°C, then aged at 410–500°C. Austenitization (continued)

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Fe–Mo–Ni

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1970Gom]

Neutron diffraction

Mox(FeNi3)1–x, x = 0.01–0.05, temperature not given, superstructure in FeNi3

[1973Gru]

Nuclear gamma resonance

16 mass% Ni, 5 mass% Mo Quenching from 1000°C, then aged at 420°C, redistribution of Mo atoms

[1974Gen]

Nuclear gamma resonance

12.2 at.%Ni, 6.2 at.% Mo quenched from 1000°C and aged at 450°C. Austenitization

[1975Kno]

XRD, dilatometry, DTA

10 mass% Ni, 10 mass% Mo, homogenized at 1200°C then quenched, α-γ transformation

[1976Cou]

Mössbauer spectroscopy

Fe-19 at.% Ni-3 at.% Mo, α→γ transformation

[1977Ser]

Dilatometry, DTA thermo magnetometry, thermoresistivity, XRD, small angle X-ray scattering, SEM, optical microscopy.

Fe-Mo-Ni alloys with mass% Mo up to 20 and mass% Ni up to 21.66 were prepared by sintering at 1400°C, αδ, μ, martensite

[1980Geo]

X-ray diffraction, dilatometry, temperature dependence of resistivity

Water quenching from 1150 and 1100°C, aging at 200–650°C for 2–30 min and up to 120 h, Fe70+xNi30–2xMox (x=0.5, 1, 1.5, 2, 2.5), γ→α transformation

[1980Loo]

Diffusion couple technique, optical microscopy, EPMA, X-ray diffraction

1100°C, phase equilibria Mo-FexNi1–x, structure of the τ phase

[1980Zam]

NGR, internal friction, optical microscopy, TEM, magnetometry

Quenching from 1150°C followed by tempering at 350, 450, 550, and 600°C for 1–300 h, Fe-24 mass% Ni-5 mass% Mo, γ→α

[1982Nik]

Optical microscopy, magnetic measurements using ballistic magnetometer

25.5 mass% Ni, 4.5 mass% Mo annealing at 1150°C then aged at 400–600°C. Kinetics of martensite transformation

[1983Sat]

TEM, X-ray diffraction, Vickers hardness

(12–18) at.% Mo, (2–14) at.% Ni, homogenized at 1000°C, hot-rolled at 1100°C, annealed at 1300–1350°C then quenched

[1987Val]

Method of positron lifetime measurement using positron source 22Na on a mylar substrate with activity of 2·108 Bq

16 mass% Ni, 6 mass% Mo, quenched from 950°C, heated at 100–550°C for 30 min, early stages of decomposition of supersaturated solid solution

[1989Gol]

XRD, DTA, EPMA, calculations

1550–1650°C, solid-liquid equilibria

[1989Oda]

Optical microscopy, SEM, EDAX, XRD

800–1250°C, 50 at.% Mo, diffusion couple

[1990Gan]

Optical microscopy, EMPA

1000°C, diffusion couple

[1991Goz]

Metallography, XRD, SEM, EDAX

700–1200°C, Fe-40 mass% Mo, 60 mass% Ni (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1992Fri]

Diffusion couple, optical microscopy, SEM, EDAX, XRD

Liquidus surface and isothermal sections at 950 to 1270°C

[1992Sat]

Hardness measurements, optical microscopy

< 16 at.% Ni, < 40at.%Mo, 450–600°C, spinodal decomposition

[1993Goz]

SEM, DTA, XRD

16.5 at.% Fe, 34.5 at.% Mo, 1300°C for 10 h, rapidly cooled to 1000°C and quenched

[1993Leo]

XRD

XNi=0.93, 0.90, 0.87, 0.84, 0.81, 0.78; XMo/(XFe+XMo) = from 0 to 1

[1994ELM]

Differential thermal analysis (DTA), optical microscopy, EPMA

Fe-12 mass% Ni-9.5 mass% Mo, inﬂuence of the cooling rate

[1995Dje]

Mössbauer, EPMA, TEM, inﬂuence of the cooling rate on the Mo segregation

20 to 30 at.% Ni, 3 to 5 at.% Mo, x = 0.2– 0.3, annealed at 1400°C, cold-rolled, aged at 450°C and cooled

[1996Gol]

Internal friction in the ultrasonic and hertz frequency spans, induction magnetometric analysis, DTA, mechanical tests

Fe-24.5Ni-5Mo (mass%) annealed at 1150°C, then quenched and aged at 350–600°C. Kinetics of martensitic transformation

[1997Sch]

Isothermal holding tests in the liquid + solid region, EPMA

1450–1530°C, partial liquidus surface

[1998Gol, 2000Gol]

Temperature dependent and amplitude dependent internal friction in temperature interval from 100 to 900 K

Fe-24.5Ni-5Mo (mass%) annealed at 900–1150°C then quenched. Martensitic transformations

[2006Yan]

Diffusion triple, EMPA

Fe-Mo-Ni, 1100°C

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

αδ, (αδFe,Mo)

cI2 Im 3m W

(δFe) 1538–1394 (αFe) < 912 (αMo) < 2623

Lattice Parameters [pm]

Comments/References

a = 293.15

dissolves up to 24.4 at.% Mo at 1449°C and 5.5 at.% Ni at 1514°C pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2]

a = 314.7

pure Mo at 25°C [Mas2] dissolves up to 35 at.% Fe at 1611°C and 3 at.% Ni at 1362°C 0.9 at.% Ni [1991Sin] ~20 at.% Fe [1982Fer]

a = 314.5 a = 311.8

(continued)

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8

Fe–Mo–Ni

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

γ, (γFe,Ni)

cF4 Fm 3m Cu

(γFe) 1394–912

Lattice Parameters [pm]

Comments/References

a = 364.67

pure Fe at 915°C [Mas2] dissolves up to 2 at.% Mo at 1100°C pure Ni at 25°C [Mas2] dissolves up to 28 at.% Mo at 1317°C

a = 352.40 (Ni) < 1455 (εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]

λ, MoFe2 < 927

hP12 P63/mmc MgZn2

a = 474.4 c = 772.5

33.3 at.% Mo [Mas2]

R, Mo2Fe3 1488–1200

hR159 R 3 Co5Cr2Mo3

μ, Mo6Fe7 < 1370

hR39 R 3m Fe7W6

σ, MoFe 1611–1235

tP30 P42/mnm σCrFe

FeNi3 < 517

cP4 Pm 3m AuCu3

a = 355.23

63–85 at.% Ni [2007Kuz]

FeNi

tP2 P4/mmm AuCu

a = 357.9 c = 357.9

Metastable [2007Kuz]

MoNi < 1362

oP56 P212121 MoNi

MoNi3 < 910

oP8 Pmmm βCu3Ti

a = 506.4 b = 422.4 c = 444.8

75.1–75.6 at.% Ni [1991Sin]

MoNi4 < 870

tI10 I4/m MoNi4

a = 572.7 c = 356.6

80.1–80.6 at.% Ni [1991Sin]

MoNi2 (m)

oI6

a = 1091.0 c = 1935.4 a = 475.1 c = 2568

a = 921.8 c = 481.3

a = 910.8 ± 0.5 b = 910.8 ± 0.5 c = 885.2 ± 0.5

pﬃﬃﬃ a = 2p2ﬃﬃﬃa (fcc) b = 3 2a (fcc) c = a (fcc)

33.9–38.5 at.% Mo [1992Rag] [V-C2] 39.0–44.0 at.% Mo [1982Fer]

42.9–56.7 at.% Mo [Mas2] 50 at.% Mo [1992Rag]

46–48 at.% Ni [1991Sin] [V-C2]

Metastable 66.7 at.% Ni [1991Sin] (continued)

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Fe–Mo–Ni

9

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

MoNi3 (m)

tI8 I4/mmm Al3Ti

-

Metastable 75 at.% Ni [1991Sin]

MoNi4 (m)

cF4

-

Metastable 80 at.% Ni [1991Sin]

Mo6Ni17 (m)

o**

a = 5.5 a (MoNi3) b = b (MoNi3) c = c (MoNi3)

Metastable 77 at.% Ni [1991Sin]

* τ, Mo53Fe11Ni36

o**

a = 909.1 b =1700.2 c = 479.5

[1980Loo]

Table 3.

Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mol of atoms [kJ, mol, K]

Comments

0.4556Fe + 0.1213Ni + 0.4231Mo→μ

900

ΔmixH = 0.715

[1983Kub]

0.1519Fe + 0.3637Ni + 0.4844Mo→τ

1000

ΔmixH = 1.347

[1983Kub]

850

ΔmixH = 0.985

[1983Kub]

1000

ΔmixH = 2.180

[1983Kub]

0.080Fe + 0.425Ni + 0.495Mo→ (MoNi) 0.10Fe + 0.80Ni + 0.10Mo→γ

Table 4.

Investigations of the Fe-Mo-Ni Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1972Bor]

Ballistic method

Magnetic properties and texture of hot rolled Fe-Mo-Ni industrial alloys

[1973Pfe]

Ballistic method, Thompson bridge method

Permeability, Curie temperature, magnetostriction coefﬁcient, speciﬁc resistivity

[1975Roa]

SEM, Vickers hardness, Instron machine

Hardness and tensile properties of Hastelloy B in temperature interval from room to 1200°C

[1978Ish]

SEM, tensile test

Mechanical properties of the welded specimens at ambient and low temperatures

[1980Nos]

XRD, TEM, mechanical tests

Ni-22.3Mo-5.9Fe (at.%) single crystal quenching from 1100°C, then aged at 700°C, formation of ordered MoNi2 (continued)

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10

Fe–Mo–Ni

Reference

Method/Experimental Technique

Type of Property

[1981Jin]

Magnetic permeability, saturation magnetization

Magnetic properties

[1983Sat]

SEM, standard ballistic technique, dilatometry, electrical resistivity

Magnetic, heat and electrical properties

[1984Luz]

Measurements of HC, magnetization and remanent magnetization

Magnetic properties of Fe-20Mo-5Ni (mass%)

[1984Tie]

Yield strength, coercitivity, saturation magnetization

20 mass% Ni, 4 to 6 mass% Mo, Cobalt free semi hard magnet

[1988Mag]

Optical microscopy, TEM, X-ray diffraction, ballistic method in solenoid

coercive force HC, residual induction Br, energy product (BH)m

[2004She]

XRD, SEM, TEM, grain size, coercitivity

15 mass% Fe, 5 mass% Mo, high energy ball milling, soft magnetic material

[2005Cha]

Light microscopy, SEM, mechanical tests: tensile and axial fatigue tests on a servohydraulic frame.

The microstructure and mechanical properties of sintered Fe-0.85 mass% Mo-Ni steels

[2005Du]

XRD, DSC, SEM, TEM, coercitivity, saturation magnetization

Fe49Ni46Mo5 (in at.%), mechanical alloying, Nanostructured magnetic material

[2006Yas, 2007Yas]

AC magnetic susceptibility, Mössbauer spectroscopy, TEM

Fe, 30 mass% Ni, < 5 mass% Mo annealed at 1100°C and quenched. Martensitic transformations

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Fig. 1a. Fe-Mo-Ni.

Reaction scheme, part 1

Fe–Mo–Ni

Landolt-Börnstein New Series IV/11D4

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Fe–Mo–Ni

Fig. 1b. Fe-Mo-Ni.

Reaction scheme, part 2

12

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Fe–Mo–Ni

Fig. 2. Fe-Mo-Ni.

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13

Computed tentative liquidus projection

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14

Fig. 3. Fe-Mo-Ni.

Fe–Mo–Ni

Isothermal section at 1270°C

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Fe–Mo–Ni

Fig. 4. Fe-Mo-Ni.

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15

Isothermal section at 1200°C

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Fig. 5. Fe-Mo-Ni.

Fe–Mo–Ni

Computed isothermal section at 1100°C

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Fe–Mo–Ni

Fig. 6. Fe-Mo-Ni.

Landolt-Börnstein New Series IV/11D4

17

Computed isothermal section at 950°C

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Fig. 7. Fe-Mo-Ni.

Fe–Mo–Ni

Isothermal section at 800°C

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Fe–Mo–Ni

Fig. 8. Fe-Mo-Ni.

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19

Hypothetical equilibria involving α, γ, μ and Fe2Mo phases at 70 mass% Fe

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20 References [1934Koe] [1949Jae] [1951Che] [1952Das]

[1953Das]

[1957Bec]

[1968Art]

[1968Ega]

[1969Geo1]

[1969Geo2]

[1969Mir]

[1969Yed]

[1969Yeg1]

[1969Yeg2]

[1970Cou]

[1970Yed]

Fe–Mo–Ni

Köster, W., “The Iron-Molybden-Nickel System” (in German), Arch. Eisenhuettenwes., 8, 169–171 (1934) (Experimental, Phase Diagram, Phase Relations, 5) Jänecke, E., “Ni-Fe-Mo” (in German) in “Kurzgefasstes Handbuch Aller Legierungen”, Winter Verlag, Heidelberg, 640–641 (1949) (Phase Diagram, Phase Relations) Chevenard, P., Josso, E., (in French), Compt. Rend. Acad. Sci. Paris, 233, 539–541 (1951), as quoted in [1984Ray] Das, D.K., Rideout, S.P., Beck, P.A., “Intermediate Phases in the Mo-Fe-Co, Mo-Fe-Ni and Mo-Ni-Co Ternary Systems”, Trans. AIME, 194(10), 1071–1075 (1952) (Crys. Structure, Experimental, Morphology, Phase Diagram, 23) Das, D.K., Beck, P.A., “Survey of Portions of the Iron-Nickel-Molybdenum and Cobalt-IronMolybdenum Ternary Systems at 1200°C”, Nat. Adv. Com. Aeronautic, Techn. Note, 2896, 1–56 (1953) (Crys. Structure, Experimental, Morphology, Phase Diagram, 15) Bechtoldt, C.J., Vacher, H.C., “Phase Diagram Study of Alloys in the Fe-Cr-Mo-Ni System”, J. Res. Nat. Bur. Stand., 58(1), 7–19 (1957) (Crys. Structure, Experimental, Morphology, Phase Diagram, 29) Artsishevskaya, L.F., Ibragimov, E.A., Selissky, Ya.P., Sorokin, M.N., “Investigation of the Atomic Ordering in Ni-Fe-Cr and Ni-Fe-Mo Alloys.”, Russian Met. (4), 102–107 (1968), translated from Izv. Akad. Nauk SSSR, Met., (4), 158–164 (1968) (Crys. Structure, Phase Relations, Electr. Prop., Mechan. Prop., 21) Eganyan, I.L., Selissky, Ya.P., “Investigation of the Effects of Atomic Ordering in Ternary Solid Solutions on the Basis of Ni3Fe Alloyed by VI Group Elements - Chromium, Molybdenum, Tungsten” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika, (20), 100–104 (1968) (Crys. Structure, Phase Relatiuons, Physical Prop., Experimental, 3) Georgieva, I.Ya., Izotov, V.I., Nikitina, I.I., Khandarov, P.A., “Structural Singularities of Athermic and Isothermic Martensite in an Fe-Ni-Mo Alloy” (in Russian), Fiz. Met. Metalloved., 27(6) 1129–1130 (1969) (Morphology, Phase Relations, Experimental, 6) Georgieva, I.Ya., Nikitina, I.I., “Isothermal and Athermal Martensite Transformation in Fe-Ni-Mo Alloy”, Dokl. Akad. Nauk SSSR, 186(1), 85–88 (1969) (Morphology, Phase Relations, Experimental, 6) Mirzayev, D.A., Shteynbeg, M.M., Goykhenberg, Yu.N., “Inﬂuence of Manganese, Chromium and Molybdenum on Martensitic Transformation in Alloys on Iron-Nickel Base”, Phys. Met. Metallogr., 28(1), 162–169 (1969), translated from Fiz. Met. Metalloved., 28 (1), 152–159, 1969 (Phase Relations, Thermodyn., Experimental, Calculation, 12) Yedneral, A.F., Perkas, M.D., “Structural Changes in Martensite of an Fe-Ni-Mo Alloy as a Result of Ageing”, Phys. Met. Metallogr., 28(5), 101 (1969), translated from Fiz. Met. Metalloved., 28(5), 862–871, (1969) (Morphology, Phase Relations, Experimental, 11) Yeganyan, I.L., Selisskiy, Ya.P., “A Study of the Effects of Atomic Ordering in Ternary Solid So1utions of Cr, Mo, and W in Ni3Fe”, Phys. Met. Metallogr., 27(2), 18–25 (1969), translated from Fiz. Met. Metalloved., 27(2), 210–218 (Phase Relations, Phys. Prop., Experimental, 8) Yeganyan, I.L., Selissky, Ya.P., “ΔE Effect in the Ni3(Fe,Cr) and Ni3(Fe,Mo) Alloys”, Phys. Met. Metallogr., 27(4), 199–201 (1969), translated from Fiz. Met. Metalloved., 27(4), 763– 764, 1969 (Phase Relations, Phys. Prop., Experimental, 5) Courrier, R., “Kinetic Study of the Isothermal Transformation of the Martensite During Ageing of a Ternary Alloy with 76% Fe, 19% Ni and 5% Mo” (in French), Compt. Rend. Acad. Sciences, Serie C, 271(25) 1514–1517 (1970) (Crys. Structure, Morphology, Phase Relations, Experimental, Kinetics, 12) Yedneral, A.F., Perkas, M.D., “Investigation of Kinetics of Ageing of Martensite in Fe-NiMo Alloys” (in Russian), Fiz. Met. Metalloved., 30(2), 418–425 (1970) (Crys. Structure, Phase Relations, Experimental, Kinetics, Electr. Prop., Mechan. Prop., 17)

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Fe–Mo–Ni [1970Gom]

[1972Bor]

[1973Gru]

[1973Pfe]

[1973Wad] [1974Gen]

[1975Roa]

[1975Kno]

[1976Cou]

[1977Ser]

[1978Ish]

[1979Wen]

[1980Fra]

[1980Geo]

[1980Loo]

[1980Nos]

Landolt-Börnstein New Series IV/11D4

21

Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of Ni3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, Magn. Prop., 6) Borodkina, M.M., Pesin, V.S., Smirnova, L.G., Sosnin, V.V., Starostin, Yu.V., “Magnetic Properties and Texture of Thin Strips of Nickel-Iron-Molybdenum Alloys” (in Russian), Fiz. Met. Metalloved., 33(6), 1188–1194 (1972) (Morphology, Magn. Prop., Experimental, 12) Gruzin, P.L., Rodionov, Yu.L., Li, Yu.A., Edneral, A.F., Zhukov, O.P., Perkas, M.D., “Redistribution of Alloying Elements During the Recovery in Maraging Fe-Ni-Mo and Fe-Ni-Co-Mo Alloys” (in Russian), Fiz. Met. Metalloved. (in Russian), 36(2), 423–427 (1973) (Phase Relations, Experimental, 10) Pfeifer, F., Cremer, R., “Highly Permeable Nickel-Iron-Molybdenum Alloys Containing 33 to 37% Nickel” (in German), Z. Metallkd., 64(5), 362–365 (1973) (Phase Relations, Magn. Prop., Experimental, 9) Wada, T., “Iron-Molybdenum-Nickel” in “Metals Handbook”, Lyman, T. (Ed), ASM, Metals Park, Ohio, 8, 431–431 (1973) (Phase Diagram, Review, 1) Genin, J.M., Lecaer, G., Maitrepi, P., Thomas, B.J., “Mössbauer Study of Precipitation in Fe-Ni-Mo and Fe-Ni-Co-Mo Maraging Alloys”, Scr. Metall., 8(1), 15–22 (1974) (Electronic Structure, Phase Relations, Experimental, 17) Roan, D.-Y., Brooks, C.R., “The Effect of Ageing on the Mechanical Properties of a NickelMolybdenum-Iron Alloy (Hastelloy B)”, Metal. Trans. A, 6A(9), 1829–1831 (1975) (Morphology, Mechan. Prop., Experimental, 7) Knosp, B., Lepine, G., Cizeron, G., “Structural Evolution of the Alloy Fe-10Ni-10Mo by Returning to a Lower Temperature from the Point As” (in French), Scr. Metall., 9(9), 901– 906 (1975) (Crys. Structure, Phase Relations, Experimental, Kinetics, 7) Courrier, R., “Study of the Structure Changes of Maraging Alloy Fe-19 at.% Ni-3 at.%Mo” (in French), Mem. Sci. Rev. Metall., 73(2), 101–116 (1976) (Phase Relations, Experimental, Kinetics, 26) Servant, C., Lacombe, P., “Structural Transformations Produced During Tempering of Fe-NiCo-Mo Alloys”, J. Mater. Sci., 12, 1807–1826 (1977) (Experimental, Morphology, Phase Diagram, 42) Ishikawa, K., Maruyama, N., “Fracture and Strength of MIG Welded Fe-13%Ni-3%Mo Alloy for Cryogenic Service”, Cryogenics, 18(10), 585–589 (1978) (Morphology, Experimental, Mechan. Prop., 11) Wenchong, X., Junjian, W.,. Xiujin, S., Zhihua, L., “An Investigation of Magnetic Ni-Fe-Mo and Ni-Fe-Nb Alloys” (in Chinese), Acta Metall. Sin., 15(2), 252–258 (1979) (Morphology, Phase Relations, Experimental, Mechan. Prop., 8) cited from abstract Frackowiak, J.E., Morawiec, H., Panek, T.J., Uhlig, M.R., “Mössbauer Effect Study of K-effect in Ni-Fe-Mo Alloy”, J. Phys. Colloq., 41(C-1) C1373–1374 (1980) (Phase Relations, Experimental, Magn. Prop., 6) Georgieva, I.Ya., Matyushenko, L.A., “Effect of Heat Treatment on the Kinetics of the TwoStage Martensitic Transformation in Fe-Ni-Mn and Fe-Ni-Mo Alloys”, Met. Sci. Heat Treat., 22(5–6), 311–313 (1980), translated from Metall. Term. Obrab. Met., 22(5), 3–5 (1980) (Phase Relations, Experimental, Kinetics, Electr. Prop., 7) Van Loo, F.J.J., Bastin, G.F., Vrolijk, J.W.G.A., Hendricks, J.J.M., “Phase Relations in the Systems Fe-Ni-Mo, Fe-Co-Mo and Ni-Co-Mo at 1100°C”, J. Less-Common Met., 72, 225–230 (1980) (Crys. Structure, Experimental, Kinetics, Phase Diagram, 11) Nosova, G.I., Polyakova, N.A., “Phase Composition, Strength Parameters and Dislocation Structure of Alloy Ni-Mo-Fe”, Phys. Met. Metallogr., 50(5), 168–171 (1980), translated from Fiz. Met. Metalloved., 50(5), 1090–1093 (1980) (Crys. Structure, Morphology, Phase Relations, Experimental, Mechan. Prop., 9)

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22 [1980Rod]

[1980Sri] [1980Zam]

[1981Jin] [1982Fer] [1982Nik]

[1983Kub]

[1983Sat]

[1984Gui]

[1984Luz]

[1984Ray]

[1984Suz]

[1984Tie] [1985Xin] [1986Rod]

[1986Sar]

[1987Val]

Fe–Mo–Ni Rodionov, Y.L., Isfandiyarov, G.G., Zambrzhitskiy, V.N., “Inﬂuence of Annealing on the Redistribution of Atoms in the Austenite of Fe-Ni-Mo and Fe-Ni-Si”, Phys. Met. Metallogr., 49(2), 94–100 (1980), translated from Fiz. Metal. Metalloved., 49(2), 335–341 (1980) (Crys. Structure, Experimental, 8) Srivastava, S.C., “Electrodeposition of Ternary Alloys: Developments in 1972–1978”, Surf. Technol., 10, 237–257 (1980) (Electrochemistry, Magn. Prop., Review, 121) Zambrzhitskiy, V.N., Maksimova, O.P., Gruzin, P.L., Rodionov, Y.L., Utevskiy, L.M., Isfandiyarov, G.G., Pankova, M.N., Seleznev, V.N., “Annealing Inﬂuence on Austenite Structure and Martensite-Transformation in Iron-Nickel-Molybdenum Alloy with Isothermal Transformation Kinetics” (in Russian), Fiz. Met. Metalloved., 49(4), 776–787 (1980) (Morphology, Phase Relations, Experimental, Kinetics, 20) Jin, S., Tiefel, T.H., “New Ductile Fe-Mo-Ni Magnet Alloys”, J. Appl. Phys., 52(3), 2503– 2505 (1981) (Experimental, Magn. Prop., 7) Fernandez-Guillermet, A., “The Fe-Mo (Iron-Molybdenum) System”, Bull. Alloy Phase Diagrams, 3(3), 359–367 (1982) (Crys. Structure, Phase Diagram, Review, 40) Nikitina, I.I., Rozhkova, A.S., “Martensite γ-α Transformations in Fe-Ni-Mo Alloys with Various Purity Degrees” (in Russian), Fiz. Met. Metalloved., 53(6), 1138–1142 (1982) (Morphology, Phase Relations, Kinetics, Magn. Prop., Experimental, 14) Kubaschewski, O., Hoster, T., “Enthalpy of Formation and Transformation in Binary and Ternary Systems of the Metals Iron, Cobalt, Nickel and Molybdenum” (in German), Z. Metallkd., 74(9), 607–609 (1983) (Experimental, Phase Diagram, Thermodyn., 8) Sato, S., Urushikara, F., Suzuki, T., “Effect of Nickel Addition on the Phase Decomposition of Iron-Molybdenum Alloys”, Scr. Metall., 17, 1391–1394 (1983) (Crys. Structure, Morphology, Phase Diagram, Experimental, 11) Guillermet, A.F., Consejo National de Investigationes Cientiﬁcas y Tecnicas, Centro Atomico Bariloche, San Carlos de Bariloche, Argentina, personal communication, 1984, as quoted in [1992Fri] Luzhinskaya, M.G., Shilova, N.F., Shur, Ya.S., “Investigation of Magnetization Reversal Processes in Fe-Mo-Ni Alloy” (in Russian), Fiz. Met. Metalloved., 57(4), 821–824 (1984) (Morphology, Experimental, Magn. Prop., 3) Raynor, G.V., Rivlin, V.G., “Phase Equilibria in Iron Ternary Alloys. XV. Critical Evaluation of Ternary Alloys of Iron and Molybdenum with Cobalt, Chromium, Manganese, and Nickel”, Int. Metall. Rev., 29(5), 329–375 (1984) (Assessment, Phase Diagram, Review, 70) Suzuki, Y., Horikoshi, E., Niwa, K., “Magnetic Properties and Ferromagnetic Shielding of Ni-Mo-Fe Alloys at Cryogenic Temperatures”, Fujitsu Sci. Tech. J., 20(2), 167–177 (1984) (Phase Relations, Experimental, Magn. Prop., 7) Tiefel, T.H., Jin, S., “Microduplex Fe-Ni-Mo Semihard Magnet Alloys”, J. Appl. Phys., 55(6), 2112–2114 (1984) (Phase Relations, Experimental, Magn. Prop., 3) Xing, Z.S., Gohil, D.D, Dinsdale, A.T., Chart, T.G., DMA(A)103, Report National Physics Laboratory, London (1985) as quoted in [1992Fri] Rodzinak, D., “Contact Fatigue of Materials Produced by Powder Metallurgy”, Met. Mater., 24(1), 50–56 (1986), translated from Kovove Mater., 24(1), 102–113 (1986) (Morphology, Experimental, Mechan. Prop., 22) Sarkisyan, L.E., “Structure and Properties of Iron-Nickel Powder Metallurgy Alloys”, Sov. Powder Met.-Metal Cer., 25(11), 931–936 (1986), translated from Poroshk. Metall., Ukr. SSR, 25(11), 79–84 (1986) (Morphology, Experimental, Electr. Prop., Magn. Prop., Phys. Prop., 4) Valuyev, N.P., Zhikharev, A.N., Moysh, Yu.V., Perkas, M.D., Rusanenko, V.V., Shcherbedinskiy, G.V., “Position Lifetime Investigation of the Early Stages of Ageing of Martensite of an Fe-Ni-Mo Alloy”, Phys. Met. Metallogr. 64(5), 117–120 (1987), translated from Fiz. Met. Metalloved., 64(5), 957–960 (1987) (Phase Relations, Experimental, Kinetics, 8)

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Fe–Mo–Ni [1988Mag]

[1988Ray] [1989Gol]

[1989Oda]

[1990Fri] [1990Gan]

[1991Goz]

[1991Sin]

[1992Fri]

[1992Rag]

[1992Sat]

[1992Sos]

[1993Goz]

[1993Leo]

[1994ElM] [1994Rag] [1995Dje]

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23

Magat, L.M., Makarova, G.M., Lapina, T.P., Belozerov, Ye.V., Maykov, V.G. et. al., “Inﬂuence of Plastic Deformation and Alloying on the Magnetic Properties and Structure of Alloys for Permanent Magnets Based on the Fe-Mo-Ni System”, Phys. Met. Metallogr., 65(6), 28– 33 (1988), translated from Fiz. Met. Metalloved., 65(6), 1075–1080 (1988) (Crys. Structure, Experimental, Magn. Prop., Morphology, 3) Raynor, G.V., Rivlin, V.G., “Fe-Mo-Ni” in “Phase Diagrams of Ternary Iron Alloys”, Inst. Metals, London, 4, 392–397 (1988) (Phase Diagram, Phase Relations, Review, 13) Golczewski, J.A., Lukas, H.L., Bamberger, M., Dirnfeld S.F., Gozlan, E., Klodt, J., Prinz, B., “Phase Diagrams of the Ni-Fe-Mo and Ni-Cr-Mo Ternary Systems-Experiments and Thermodynamic Calculations as a Basis of Superalloy Development” in “Adv. Mater. Processes”, Proc. 1st Eur. Conf., 1, 365–370 (1989) (Thermodyn., Experimental, Calculation, Phase Diagram, 7) Odagiri, S., “Phase Diagram of the Fe-Rich Side in the Fe-Mo-Ni System” (in Japanese), Nippon Kogyo Daigaku Kenkyu Hokoku, 79(1), 91–94 (1989) (Crys. Structure, Morphology, Phase Diagram, Experimental), as quoted in [1994Rag] Frisk, K., “A Thermodynamic Evaluation of the Mo-Ni System”, Calphad, 14(3), 311–320 (1990) (Thermodyn., Calculation, Assessment, #) as quoted in [1992Fri] Gan, W., Jin, Z., “Phase Equilibria in the Mo-Ni-Co and Mo-Ni-Fe System at 1000°C”, J. Less-Common Met., 160, 29–33 (1990) (Crys. Structure, Morphology, Phase Diagram, Experimental, 5) Gozlan, E., Bamberger, M., Dirnfeld, S.F., Prinz, B., Klodt, J., “Topologically Close-Packed Precipitations and Phase Diagrams of Ni-Mo-Cr and Ni-Mo-Fe and of Ni-Mo-Fe with Constant Additions of Chromium”, Mater. Sci. Eng. A, 141, 85–95 (1991) (Crys. Structure, Experimental, Morphology, Phase Diagram, 12) Singleton, M.F., Nash, P., “Mo-Ni (Molybdenum-Nickel)” in “Phase Diagrams of Binary Nickel Alloys”, Nash P., (Ed.), ASM Intl., Materials Park, OH, 207–212 (1991) (Crys. Structure, Phase Diagram, Thermodyn., Assessment, #, 48) Frisk, K., “An Experimental and Theoretical Study of the Phase Equilibria in the Fe-Mo-Ni System”, Metall. Trans. A, 23A(2), 639–649 (1992) (Crys. Structure, Morphology, Phase Diagram, Thermodyn., Experimental, #, 26) Raghavan, V., “The Fe-Mo (Iron-Molybdenum) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 6A, 36–36 (1992) (Crys. Structure, Phase Diagram, Review, 1) Sato, S., Urushihara, F., Suzuki, T., “Metastable Miscibility Gap of Fe-Mo-Ni Ternary Alloy System” (in Japanese), J. Jpn. Inst. Met., 56(4), 378–383 (1992) (Experimental, Phase Diagram, Thermodyn., 20) Sosnin, V.V., Glezer, A.M., Zhigalina, O.M., “Structure and Properties of Microcrystalline Alloys of the System Ni-Fe-Nb(Mo)”, Met. Sci. Heat Treat., 34(3–4), 195–202 (1992) (Crys. Structure, Morphology, Phase Relations, Experimental, 12) Gozlan, E., Dirnfeld, S.F., Bamberger, M., Klodt, J., Prinz, B., “Liquid/Solid Equilibrium and Segregation Behavior of Ni-Fe-Mo-Cr Alloys”, Z. Metallkd., 84, 776–780 (1993) (Morphology, Phase Diagram, Phase Relations, Experimental, 9) Leonov, V.V., Nikiforov, G.A., Bel’mach, E.Yu., “Relationships of Mixing Volumes in Binary and Ternary Ni-Fe-Mo Alloys”, Russ. Metall., (1) 41–44 (1993), translated from Dokl. Ross. Akad. Nauk, Metally, (1) 49–52 (1993) (Crys. Structure, Thermodyn., Experimental, 3) El-Mahallawy, N., Taha, M., Fredriksson, H., “Rapid Solidiﬁcation of Fe-Ni-Mo Alloys”, Mater. Sci. Eng. A, 179, 587–591 (1994) (Thermodyn., Experimental, 6) Raghavan, V., “Fe-Mo-Ni (Iron Molybdenum-Nickel)”, J. Phase Equilib., 15(6), 622–626 (1994) (Phase Relations, Phase Diagram, Review, 7) Djega-Mariadassou, C., Bessais, L., Servant, C., “Nanocrystalline Precipitates Formed by Aging of BCC Disordered Fe-Ni-Mo Alloys”, Phys. Rev. B: Condens. Matter, 51(14), 8830–8840 (1995) (Crys. Structure, Thermodyn., Experimental, Phys. Prop., 16)

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24 [1996Gol]

[1997Sch] [1998Gol]

[2000Gol]

[2000Rag]

[2001Vla]

[2003Rag] [2004Chi]

[2004She]

[2005Cha]

[2005Du]

[2006Yan]

[2006Yas]

[2007Yas]

[2007Kuz]

[Mas2] [V-C2]

Fe–Mo–Ni Golovin, S.A., Golovin, I.S., “Inelastic Effects and Martensite Transformations in Fe-Ni-Mo Alloys” (in Russian), Fiz. Met. Metalloved., 82(2), 71–81 (1996) (Phase Relations, Experimental, Kinetics, 23) Schürmann, E., Djurdjevic, M., Nedeljikovic, L., “Melting Equilibria in the Iron-Rich Corner of the Fe-Ni-Mo System”, Steel Research, 68, 383–387 (1997) (Phase Relations, Experimental, 8) Golovin, S.A., Sergantova, G.V., Troitsky, I.V., “Internal Friction in Fe-Ni-Mo Steels” (in Russian), Izv. Akad. Nauk., Ser. Fiz., 62(7), 1369–1376 (1998) (Phase Relations, Experimental, Kinetics, 19) Golovin, S.A., “Diffusive and Dislocational Anelasticity in Alloyed Austenite of Fe-Ni-Mo Steels”, Bull. Russ. Acad. Sci., Physics, 64(9), 1336–1341 (2000) (Phase Relations, Experimental, Kinetics, 14) Raghavan, V., “The Martensitic Fransformation in Fe-Ni and Fe-Ni-X Alloys at Subzero Temperatures”, Trans. Indian Inst. Met., 53(6), 597–603 (2000) (Phase Relations, Theory, Kinetics, 44) Vlasova, O.V., Panasyuk, O.A., Maslyuk, V.A., “Sintered Metals and Alloys/Preparation and Properties of Magnetically Soft Powder Metallurgy Alloy 79NM”, Powder Metall. Met. Ceram., 40(9–10), 497–500 (2001) (Phase Relations, Experimental, Magn. Prop., 3) Raghavan, V., “Fe-Mo-Ni (Iron-Molybdenum-Nickel)”, J. Phase Equilib., 24(3), 267–268 (2003) (Crys. Structure, Phase Diagram, Review, 8) Chicinas, I., Pop, V., Isnard, O., “Synthesis of the Supermalloy Powders by Mechanical Alloying”, J. Mater. Sci., 39(16–17), 5305–5309 (2004) (Crys. Structure, Morphology, Phase Relations, Experimental, 16) Shen, Y., Hng, H.H., Oh, J.T., “Synthesis and Characterization of High-Energy Ball Milled Ni-15%Fe-5%Mo”, J. Alloys Compd., 379(1–2), 266–271 (2004) (Morphology, Experimental, Thermodyn., Phys. Prop., 24) Chawla, N., Deng, X., “Microstructure and Mechanical Behavior of Porous Sintered Steels”, Mater. Sci. Eng. A, 390(1–2), 98–112 (2005) (Morphology, Phase Relations, Thermodyn., Experimental, Kinetics, Mechan. Prop., Phys. Prop., 33) Du, S.W., Ramanujan, R.V., “Mechanical Alloying of Fe-Ni Based Nanostructured Magnetic Materials”, J. Magn. Magn. Mater., 292, 286–298 (2005) (Crys. Structure, Morphology, Experimental, Magn. Prop., Nano, 27) Yan, F., Richu, W., Danhua, W., Qingyong, L., Shengming, W., “Determination of Isothermal Sections of the Ni-Fe-Mo Ternary System at 1373 K” (in Chinese), Rare Met. (China), 35(8), 1228–1230 (2006) (Phase Relations, Phase Diagram, Experimental, 8) Yasar, E., Gungunes, H., Kilic, A., Durlu, T.N., “Effect of Mo on the Magnetic Properties of Martensitic Phase in Fe-Ni-Mo Alloys”, J. Alloys Compd., 424, 51–54 (2006) (Crys. Structure, Morphology, Phase Relations, Experimental, Magn. Prop., 22) Yasar, E., Gungunes, H., Akturk, S., Durlu, T.N., “New Observations on the Formation of Athermal Martensite in Fe-Ni-Mo Alloys”, J. Alloys Compd., 428, 125–129 (2007) (Crys. Structure, Experimental, Morphology, Phase Relations, 30) Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, Binary Evaluation Program as Published in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; to be published, (2007) (Phase Diagram, Phase Relations, Crys. Structure, 41) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

DOI: 10.1007/978-3-540-78644-3_26 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–Mo–O

1

Iron – Molybdenum – Oxygen Pierre Perrot

Introduction The Fe-Mo-O system presents an interest because it appears in the preparation of ferromolybdenum alloys by metallothermic reduction of MoO2. Some Fe-Mo oxides have also important industrial applications by forming a protective coating over molybdenum steels. On an another hand, the molybdate Fe2(MoO4)3 is the active component in Fe-Mo based oxidation catalysts. Iron and molybdenum oxides are “easily reduced” oxides, which means that equilibria between solid phases are easily obtained under H2-H2O or CO-CO2 atmospheres. Such atmospheres give access not only to the phase compositions, but to the oxygen potential at equilibrium with an accuracy better than that obtained from electromotive force measurements. The main experimental investigations on phase equilibria and thermodynamics are gathered in Table 1. No Calphad assessment was carried out. Binary Systems The Fe-Mo binary system is accepted from the thermodynamical assessment carried out by [1982Fer] and reproduced in [Mas2]. The Fe-O system is accepted from [Mas2], which reproduces the fundamental work of [1945Dar, 1946Dar]. Two careful assessments may be found in [1991Sun, 1995Kow]. They reproduce well the experimental equilibria and differ by the description of the (Fe,O) liquid solution. The Mo-O binary system is accepted from [1980Bre]. Between MoO2 and MoO3 several oxides of the general formula MonO3n–m have been prepared. For m = 1, oxides with n = 4, 8, 9, 14 are known; for m = 2, oxides with n = 18 to 22 have been prepared; for m = 3, oxides with n = 12, 17 and 26 exist; for m = 4, Mo17O57 is known. These oxides are stable with respect to the (MoO2 + MoO3) mixture, but it is not clear whether all of them belong to the stable phase diagram. Their structure is derived from the ReO3 type structure. Mo4O11, the most stable of these oxides, disproportionates into MoO2 + liquid at 818 ± 7°C. The oxides Mo8O23 and Mo9O26 are probably stable. Solid Phases The compounds whose existence is widely recognized are presented in Table 2. There is no solid solutions between iron and molybdenum oxides. The wüstite has been reported to dissolve up to 3 at.% Mo at 1140°C [1972Abe]. Several oxides are known: MoFeO0.33 (τ1) phase of the “high speed steel” structure, Ti2Ni like according to [1967Hol] and MoFeOx (τ2) (0.4 < x < 1), known as the Hägg compound may be obtained by mixing one metal with the oxide of the other metal [1954Sch1, 1954Sch2]. τ2 is widely non stoichiometric, but with an oxygen content which never exceeds 33 at.% which corresponds to the ideal formula MoFeO. MoFe2O4 (τ3) is an inverse spinel which gives a solid solution with magnetite Fe3O4. The crystal parameter of the solid solution (MoxFe1–x)Fe2O4 presents a break in the slope for x = 0.18 [1993Mor]. The iron (II) molybdate (IV) Mo3Fe2O8 (τ4) has been reported by [1956McC, 1957McC] and was later recognized as the mineral Kamiokite. MoFeO4 (τ5) is easily obtained by solid state reaction between FeO and MoO3 oxides at 500°C [1925Tam]. The iron (III) molybdate (VI) Fe2(MoO4)3 (τ6) may be obtained by oxidation of Mo3Fe2O8 (τ4) with the intermediate formation of MoFeO4 (τ5). The compounds in which molybdenum is hexavalent (MoFeO5 (τ5), Fe2(MoO4)3 (τ6) and MoO3) are liquid at 1100°C whereas the compounds in which molybdenum is tetravalent (MoFe2O4 (τ3), Mo3Fe2O8 (τ4) and MoO2) have a melting point higher than 1100°C. Single crystals of the τ3, τ4, τ5 and τ6 compounds may be grown by chemical transport reaction [1993Mor], from the hot zone at 1050°C to the cold zone at 1000°C, using TeCl4 as transporting agent. Besides τ1 and τ2, another low valence compound, namely Mo4Fe2O7 (τ7) has been described by [2001Hai]. Discovered by serendipity on the occasion of synthesis of NaMo4O6 in steel crucible, it may be obtained by sintering Fe + Mo + MoO3 powders at 1200°C. Below 200 K, it presents a ferrimagnetism due to the different magnetic moments of iron in two different crystallographic sites. τ7 phase is probably metastable, it has not been introduced in the phase diagrams presented. Landolt-Börnstein New Series IV/11D4

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2

Fe–Mo–O

Quasibinary Systems The Fe2O3-MoO3 quasibinary system determined by [1959Jae] is shown in Fig. 1. The oxygen pressure at equilibrium is not determined because it depends on the composition of the mixture and a more informative diagram would show isobaric lines. The quasibinary systems MoFeO4-MoO3 and Fe2(MoO4)3-MoFeO4 are shown in Figs. 2 and 3, respectively. The melting points of solid phases given by [1959Jae] being 10°C lower than the accepted ones, the position of the eutectic shown in Figs. 1, 2 and 3 have been raised by 10°C. Isothermal Sections The phase equilibria in the solid state, that is below 800°C, are shown in Fig. 4. The equilibria in the triangle FeO-MoO2-O are taken from [1959Jae, 1972Sch]; the reduced part of the diagram (FeO-MoO2-Mo-Fe domain) is accepted from [1989Rag]. This diagram may also be used at 900°C, but it must be pointed out that, at 900°C, MoO3 becomes liquid with a vapor pressure of the order of 0.1 MPa. The phase equilibria, investigated at 1000°C by [1981Kle, 1993Mor] are represented in Fig. 5. The oxidized part of the diagram (MoO2-τ4-τ3-O region) is from [1993Mor], but it must be pointed out that, at 1000°C, Fe2(MoO4)3 (τ6) (which melts at 965°C) and MoO3 are liquid and the vapor pressure of MoO3 exceeds 0.1 MPa. The phase diagram proposed at 900 and 1000°C by [1981Kle, 1994Koy] differs by the nature of the phases in equilibrium with τ3 and τ4. According to [1983Kle], (Fe) and μ phases are in equilibrium with Mo3Fe2O8 (τ4) below 916°C and with MoFe2O4 (τ3) above 916°C. That temperature is the inversion temperature of the equilibrium: τ4 + (Fe) ⇌ τ3 + μ. Below 916°C, τ4 is in equilibrium with (Fe); above 916°C, τ3 is in equilibrium with μ. The same observation was reported by [1994Koy] with an invariant temperature of 957°C. The phase equilibria in the triangle MoO2-FeO-Fe3O4, investigated at 1140°C by [1972Abe] under CO2-H2 atmospheres, corresponding to 10–12.7 < pO2/bar < 10–7.8, is shown in Fig. 6. The spinel solid solution (Mo1–xFex)Fe2O4 is in equilibrium with Mo3Fe2O8 (τ4) in its τ3 rich part (0.36 < x < 1) and with a liquid phase of undetermined composition in its Fe3O4 rich part (0 < x < 0.36). The phase equilibria at 1600°C, experimentally determined by [1970Tho] is shown in Fig. 7, after slight modiﬁcations to take into account the accepted Fe-Mo diagram, particularly the presence of the σ phase which decomposes into (Mo) + L1 above 1611°C. Thermodynamics The thermodynamic quantities related to the formation from the oxides of MoFe2O4 (τ3), MoFeO4 (τ5) and to the phase transition of Fe2(MoO4)3 (τ6) are given in Table 3; the thermodynamic quantities related to single phases are given in Table 4. The Gibbs energy of formation of τ3, τ4, τ5 and τ6 together with that of μ, Mo0.42Fe0.58 phases are accepted from [2003Koy] because they are internally consistent, being obtained from the same equipment. Some older measurements are presented for comparison. The enthalpy of formation of τ5 from its elements, measured at –1053.5 kJ·mol–1 by [2003Koy] in the temperature range 839–1066°C must be compared to an earlier experimental value of –1063 kJ·mol–1 reported earlier by [1984Kag] at 25°C. On another hand, the Gibbs energy of formation of τ3 and τ4 proposed by [2003Koy] are in good agreement with the earlier measurements of [1981Kle] obtained also from electromotive force measurements in the same temperature range. The activities of Fe3O4 in the spinel solid solution have been evaluated at 900°C [1972Sch] and at 1200°C [1975Kat] from the oxygen pressures at equilibrium spinel/wüstite under various CO-CO2 or H2-CO2 gaseous atmospheres. The activities of Fe3O4 in the spinel present a small negative departure from ideal behavior at 900°C and an ideal behavior at 1200°C. The activity of MoFe2O4 were calculated by integration of the Gibbs-Duhem equation. The interaction coefﬁcients of Mo and O in liquid iron at 1600°C, (< 20 mass% Mo) have been evaluated by [1965Tan] by equilibrating liquid alloys under H2-H2O atmospheres: eO(Mo) = {∂ log10 fO/∂ (mass% Mo)} = 0.0025 at 1600°C, with fO = {(mass% O in pure Fe)/(mass% O in alloy)}. An higher value eO(Mo) = 0.007 at 1600°C was measured by [1971Fis] from emf measurements, with stabilized zirconia used as solid electrolyte. The most probable value eO(Mo) = 0.0035 at 1600°C is proposed in more recent evaluations [1966Sch, 1974Sig, DOI: 10.1007/978-3-540-78644-3_27 # Springer 2008

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Fe–Mo–O

3

2003Per] in which the liquid alloy is equilibrated with oxygen. This positive value, not far from zero, means that Mo decreases slightly the oxygen solubility in Fe. Notes on Materials Properties and Applications The main experimental works are summarized in Table 5. When a Mo steel is heated in air at high temperature, the surface is coated by a layer composed of τ3, τ4 and τ5 which prevents further oxidization of the steel. The spinel τ3,MoFe2O4 exhibits a weak spontaneous magnetization (0.15 to 0.20 μB·mol–1) below the Neel temperature of 348 K (75°C) [1972Abe], with an unexplained change of sign below 160 K. The molybdate τ6 is widely used for its catalytic properties. For instance, its catalyses the selective oxidation of methanol into formaldehyde, the ammoxidation of propylene into acrylonitrile [1979Che] or the oxidation of propane into formaldehyde [2003Tay]. It has been claimed that the ability of τ6 to incorporate MoO3, inducing a possible non stoichiometry, is important for its catalytic properties. However, [1981Mas] found no evidence of a possible excess of MoO3 in the structure. The linear thermal expansion coefﬁcient α = (1/ℓ)(∂ℓ/∂T)P of τ6 was measured by [2002Tya]. For the low temperature modiﬁcation, monoclinic, α = 9.74 · 10–6 K–1; for the high temperature modiﬁcation, after the monoclinic-orthorhombic transition, α = – 14.82 · 10–6 K–1 < 0, a feature attributed to the bending of the Fe-Mo-O bonds. Miscellaneous The partition coefﬁcient of Mo between Mo saturated liquid slag and liquid metal in the Fe-Mo-Si-O system ranges from 0.34 at 0 % SiO2 and 1600°C to less than 0.01 at silica saturated [1970Tho], which means that SiO2 in the slag displaces Mo from the slag to the metal. The partition coefﬁcient increases with temperature. The reduction of MoFe2O4 by H2, carried out by [2002Mor] between 850 and 1050°C, leads to MoFe2 in one step with an activation energy of 173.5 kJ·mol–1. The electrical conductivity and magnetic susceptibility of τ4, measured by [1982Str] below room temperature show that τ4 presents an antiferromagnetic ordering at 59.5 K. τ4 presents also a strong anisotropy. For H || c (magnetic ﬁeld parallel to the c axis), μeff = 5.8 ± 0.3 μB per Fe atoms; for H⊥ c (magnetic ﬁeld perpendicular to the c axis), μeff = 4.4 ± 0.2 μB per Fe atom. The ratio of the electrical resistivities σ⊥ c / σ || c varies from ∼ 40 at room temperature to ∼ 300 at 150 K. Below 140 K, resistivity cannot be measured because the resistances are of the order of 10 GΩ.

Table 1.

Investigations of the Fe-Mo-O system Phase Relations, Structures, Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1925Tam]

XRD, calorimetry

< 600°C, FeO + MoO3

[1954Sch1, 1954Sch2]

XRD, solid-state reaction

MoFeO0.33 and MoFeOx structures (0.4 < x < 1)

[1956McC, 1957McC]

XRD, solid-state reaction

Fe2Mo3O8 prepared from 3 Fe2O3 +4 Mo + 5 MoO3 at 1150°C

[1959Jae]

XRD, equilibria measurements under H2-H2O atmospheres

800–1100°C, FeO-Fe3O3-MoO3-MoO2 phase equilibria

[1965Tan]

Oxygen solubility in (Fe,Mo) liquid alloy, chemical analysis

1550–1700°C, < 20 mass% Mo, H2-H2O atmospheres

[1968Sle]

XRD, pressure, phase transitions

FeMoO4, < 700°C, < 300 MPa (continued)

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Fe–Mo–O

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1970Tho]

XRD, thermal analysis

1600–1800°C, the Fe-Mo-O phase diagram, O2 pressure undetermined

[1971Fis]

EMF, stabilized ZrO2 as solid electrolyte

1600°C, < 23 mass% Mo, < 0.1 mass% O

[1972Abe]

XRD, thermogravimetry, chemical analysis

1140°C, MoO2-FeO-Fe3O4 diagram, CO2-H2 atmospheres

[1972Sch]

XRD, thermogravimetry, chemical analysis

900°C, Fe-Mo-O diagram, CO-CO2 atmospheres

[1975Kat]

XRD, thermogravimetry, chemical analysis

1200°C, tie lines in the spinel-wüstite twophase domain

[1981Kle]

XRD, EMF, ThO2 stabilized with Y2O3 as solid electrolyte

900–1000°C, Fe-Mo-MoO2-Fe3O4 diagram

[1981Mas]

XRD, DSC

< 600°C, Fe2(MoO4)3, crystal structure, polymorphic transition

[1993Mor]

XRD, IR spectroscopy, thermal analysis

1000°C, Fe-Mo-O diagram, single crystal growth

[1994Koy]

XRD, EMF, ZrO2 stabilized with Y2O3 as solid electrolyte

900–1200°C, Fe-Mo-O diagram

[2003Koy]

EMF, ZrO2 stabilized with Y2O3 as solid electrolyte

767–1193°C, Gibbs energy of formation of Mo-Fe oxides

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αFe,δFe) (δFe) 1538–1394

cI2 Im 3m W

(αFe) (Ferrite) < 912

Lattice Parameters [pm]

Comments/References

a = 293.15

pure Fe at 1390°C [V-C2, Mas2] Dissolves 24.4 at.% Mo at 1449°C [1982Fer] pure Fe at 25°C [Mas2] Dissolves 13.4 at.% Mo at 1200°C [1982Fer]

a = 286.65

(Mo) < 2623

cI2 Im 3m W

a =314.70

[Mas2]. Dissolves 31.3 at.% Fe at 1611°C [1982Fer]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, > 13 GPa [Mas2]

(continued)

DOI: 10.1007/978-3-540-78644-3_27 # Springer 2008

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Fe–Mo–O

5

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(γFe) (Austenite) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [Mas2] Dissolves 1.7 at.% Mo at 1140°C [1982Fer]

λ, MoFe2 < 927

hP12 P63/mmc MgZn2

a = 474.4 c = 772.5

[1982Fer]

R, Mo2Fe3 1488–1200

hR159 R 3 Co5Cr2Mo3

μ, Mo6Fe7 < 1370

hR39 R 3m Fe7W6

σ, MoFe 1611–1235

tP30 P42/mnm σCrFe

FeO (Wüstite) 1422–569

33.9 to 38.5 at.% Mo [1982Fer] a = 1091.0 ± 0.3 c = 1935.4 ± 0.5

[V-C2] 39.0 to 44.0 at.% Mo [1982Fer]

a = 474.8 ± 0.2 c = 257.0 ± 0.2 a = 478.0 ± 0.2 c = 258.4 ± 0.2

at 39.0 at.% Mo [1981Kle] at 44.0 at.% Mo [1981Kle]

a = 921.8 c = 481.3

42.9 to 56.7 at.% Mo [1982Fer]

cF8 Fm 3m NaCl

a = 431.0 a = 429.3

actually Fe1–xO with 0.05 < x < 0.12 x = 0.05 x = 0.12

αFe3O4 (r) < 580

oP56 Pbcm Fe3O4 I

a = 1186.8 b = 1185.1 c = 1675.2

[V-C2]

αFe2O3 (Hematite) < 1457

hR30 R 3c αAl2O3 (Corundum)

a = 503.42 ± 0.03 c = 1374.83 ± 0.04

[V-C2]

βFe2O3

cI80 Ia 3 βMn2O3 (Bixbyite)

metastable phase a = 939.3 ± 0.2 [V-C2]

γFe2O3 (Maghemite)

cF56 Fd 3m MgAl2O4

a = 834

metastable phase [1989Rag]

Mo3O

cF16 Fm 3m Anti-BiF3

a = 554.9

low temperature phase, probably metastable [1980Bre]

MoO2 < 2300

mP12 P21/c VO2

a = 560.7 ± 0.1 b = 486.0 ± 0.1 c = 562.4 ± 0.1 β = 120.94°

[V-C2]

(continued) Landolt-Börnstein New Series IV/11D4

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Fe–Mo–O

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

αMo4O11

mP60 P21/a

a = 2454 b = 543.9 c = 670.1 β = 94.28°

[1989Rag]

βMo4O11 < 818 ± 7

oP60 Pna21 Mo4O11

a = 2449 b = 675.2 c = 545.7

[1989Rag] Disproportionates into MoO2 + Liquid [1980Bre]

Mo17O47

oP128 Pba2 Mo17O47

a = 2161.5 b = 1963.2 c = 395.1

[1980Bre] probably metastable

Mo8O23 < 780

mP62 P2/c Mo8O23

a = 1340 b = 404 c = 1680 β = 106.1°

[1989Rag] Disproportionates into Mo4O11 + MoO3 [1980Bre]

Mo9O26

mP70 P2/c Mo9O26

a = 1445 b = 403.0 c = 1675 β = 96.0°

[1989Rag]

Mo18O52

aP140 P 1 Mo18O52

a = 814.5 b = 1189 c = 1966 α = 95.47° β = 90.39° γ = 109.97°

[1980Bre] probably metastable

MoO3 < 804

oP16 Pnma MoO3

a = 1385.5 b = 369.64 c = 396.28

[1989Rag]

* τ1, MoFeO0.33

cF112 Fd 3m Ti2Ni

a = 1094 ± 1

[1954Sch2, 1989Rag] probably metastable

* τ2, MoFeOx

hP3 P63/mmc Fe2N

a = 275 c = 432

0.4 < x < 1 [1989Rag] probably metastable Hägg type structure [1954Sch1]

spinel (sp) τ3, MoFe2O4

cF56 Fd 3m MgAl2O4

a = 849.9 ± 0.1

inverse spinel [1993Koe]

a = 840.4 ± 0.1

Mo0.18Fe2.82O4, break in the slope [1993Mor] at 1000°C at 25°C

βFe3O4 (h) (Magnetite) 1597–580

a = 854.5 a = 839.6

(continued)

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Fe–Mo–O

7

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

* τ4, Mo3Fe2O8 (Kamiokite)

hP26 P63mc Zn2Mo3O8

a = 577.32 ± 0.06 c = 1005.42 ± 0.11

[1957McC, 1982LeP]

a = 572.39 ± 0.02 c = 1005.48 ± 0.02

[1993Koe]

* τ5, βMoFeO4 1068–400

mC12 C2/m αMnMoO4

a = 980.5 b = 895.0 c = 766.0 β = 114.05°

[1968Sle, 1989Rag]

* τ5´, αMoFeO4 < 400

mC12 C2/m αCoMoO4

a = 1029.0 b = 939.4 c = 707.2 β = 106.31°

[1989Rag]

* τ5(I), γMoFeO4

aP6 Structure related to monoclinic NiWO4

a = 494.43 b = 570.06 c = 470.78 α = 92.32° β = 90.27° γ = 89.33°

[1972Sle] High pressure modiﬁcation (300 MPa, 600°C) [1968Sle]

* τ6, βFe2(MoO4)3 965–513

oP68 Pnca -

a = 933.0 ± 0.3 b = 1286.8 ± 0.5 c = 924.2 ± 0.3

at 546°C paraelastic [1981Mas, 1993Koe]

* τ6´, αFe2(MoO4)3 < 513

mP136

a = 1573.7 ± 0.8

at 22°C

P21/a -

b = 923.1 ± 0.5 c = 1822.4 ± 0.9 β = 125.46 ± 0.02°

Pale green crystal, ferroelastic [1979Che, 1981Mas]

oI52 Imma Sc0.75Zn1.25Mo4O7

a = 601.8 ± 0.1 b = 578.2 ± 0.1 c = 1690.1 ± 0.5

[2001Hai] probably metastable

* τ7, Mo4Fe2O7

Table 3.

Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mol of atoms [kJ, mol, K]

Comments

MoO2 + 2FeO ⇌ τ3

900

ΔrH° = – 3.4 ± 3.4

[1972Sch]

MoO3 + FeO ⇌ τ5

500

ΔrH° = – 56.5

[1925Tam]

ΔfH° = – 1063 (Experimental) ΔfH° = – 1084 (Calculated)

[1984Kag]

ΔtrH° = 1.866 ± 0.084

[1981Mas]

Mo + Fe + 2O2 ⇌ τ5 τ6´, αFe2(MoO4)3 ⇌ τ6, βFe2(MoO4)3

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8 Table 4.

Fe–Mo–O Thermodynamic Properties of Single Phases

Phase

Temperature Range [°C]

Property, per mole of molecules [kJ, mol, K]

Comments

τ3, MoFe2O4

900–1050

ΔfG° = – 1081.7 + 0.2667 T (± 2.6 kJ·mol–1)

[1981Kle]

τ3, MoFe2O4

970–1193

ΔfG° = – 1174 + 0.342 T (± 1 kJ·mol–1)

[2003Koy]

τ4, Mo3Fe2O8

900–1050

ΔfG° = – 2267.8 + 0.6165 T (± 4.5 kJ·mol–1)

[1981Kle]

τ4, Mo3Fe2O8

839–1066

ΔfG° = – 2347 + 0.6814 T (± 1 kJ·mol–1)

[2003Koy]

τ5, MoFeO4

25

H298 – H0 = 20.58 S°298 = 129.30

[1988Bag]

τ5, MoFeO4

839–1066

ΔfG° = – 1053.5 + 0.2983 T (± 0.4 kJ·mol–1)

[2003Koy]

τ6, Mo3Fe2O12

767–872

ΔfG° = – 2993 + 0.9105 T (± 2 kJ·mol–1)

[2003Koy]

μ, Mo0.42Fe0.58

889–950

ΔfG° = – 18.7 + 0.01117 T (± 0.1 kJ·mol–1)

[2003Koy]

Table 5.

Investigations of the Fe-Mo-O Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1982Str]

Magnetic susceptibility, electric conductivity

τ4, Mo3Fe2O8, < 300 K, anisotropy, antiferromagnetic ordering

[1993Koe]

XRD (Rietveld reﬁnement), Mössbauer

Bond valence, bond length, clusters in the Mo-Fe oxides

[2001Hai]

XRD, magnetic measurements (Faraday magnetometer)

τ7, Mo4Fe2O7, crystal structure and ferrimagnetic properties

[2002Mor]

XRD, thermogravimetry, reduction of MoFe2O4 by H2

800–1050°C, preparation of MoFe2, activation energy determination

[2002Tya]

XRD, thermodilatometry

25–800°C, phase transition and thermal expansion of Fe2(MoO4)3

[2003Ehr]

Neutron powder diffraction, magnetization

Fe2(MoO4)3

[2003Tay]

XRD, Raman spectroscopy, surface measurement (BET)

300-500°C, Fe2(MoO3)3, catalytic properties

[2006Ha]

XRD, TEM, ﬁeld emission SEM

Fe-Mo nanoparticles preparation

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Fe–Mo–O

Fig. 1. Fe-Mo-O.

Landolt-Börnstein New Series IV/11D4

9

The MoO3-Fe2O3 quasibinary system

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10

Fig. 2. Fe-Mo-O.

Fe–Mo–O

The MoO3-τ5,MoFeO4 quasibinary system

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Landolt-Börnstein New Series IV/11D4

Fe–Mo–O

Fig. 3. Fe-Mo-O.

Landolt-Börnstein New Series IV/11D4

11

The τ5,MoFeO4- τ6,Fe2(MoO4)3 quasibinary system

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12

Fig. 4. Fe-Mo-O.

Fe–Mo–O

The phase equilibria in the solid state (T < 800°C)

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Fe–Mo–O

Fig. 5. Fe-Mo-O.

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13

Isothermal section at 1000°C

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14

Fig. 6. Fe-Mo-O.

Fe–Mo–O

Partial isothermal section at 1140°C. Values give log10(pO2/bar)

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Fe–Mo–O

Fig. 7. Fe-Mo-O.

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15

Isothermal section at 1600°C

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16 References [1925Tam] [1945Dar]

[1946Dar]

[1954Sch1]

[1954Sch2] [1956McC] [1957McC] [1959Jae] [1965Tan]

[1966Sch]

[1967Hol] [1968Sle] [1970Tho]

[1971Fis]

[1972Abe] [1972Sch]

[1972Sle] [1974Sig] [1975Kat]

[1979Che] [1980Bre]

Fe–Mo–O

Tammann, G., “Chemical Reaction between two Powdered Crystals” (in German), Z. Anorg. Allg. Chem., 149, 21–98 (1925) (Phase Relations, Kinetics, Experimental, 41) Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. I. The Wuestite Field and Related Equilibria”, J. Am. Chem. Soc., 67, 1398–1412 (1945) (Experimental, Phase Diagram, Thermodyn., *, 26) Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. II. Equilibria and Thermodynamics of Liquid Oxides and Other Phases”, J. Am. Chem. Soc., 68, 798–816 (1946) (Experimental, Phase Diagram, Thermodyn., *, 24) Schoenberg, N., “On the Existence of Metallic Ternary Oxides Me’Me’’O with the Metal Atoms in Hexagonal Close-Packing”, Acta Chem. Scand., 8(4), 630–632 (1954) (Crys. Structure, Experimental, 5) Schoenberg, N., “On the Existence of Ternary Transition Metal Oxides”, Acta Chem. Scand., 8(6), 932–936 (1954) (Crys. Structure, Experimental, 13) McCarroll, W.H., Ward, R., Katz, L., “Ternary Oxides of Tetravalent Molybdenum”, J. Am. Chem. Soc., 78, 2909–2910 (1956) (Crys. Structure, Experimental, 3) McCarroll, W.H., Katz, L., Ward, R., “Some Ternary Oxides of Tetravalent Molybdenum”, J. Am. Chem. Soc., 79, 5410–5414 (1957) (Crys. Structure, Experimental, 13) Jäger, W., Rahmel, A., Becker, K., “The Ternary System Iron-Molybdenum-Oxygen” (in German), Arch. Eisenhuettenwes., 30, 435–439 (1959) (Crys. Structure, Experimental, Phase Diagram, 22) Tankins, E.S., Thomas, M.K., Erthal, J.F., Williams, F.S., “The Activity of Oxygen in Liquid Fe-Mo and Fe-W Alloys”, Trans. Am. Soc. Met., 58(3), 245–252 (1965) (Experimental, Phase Relations, Thermodyn., 10) Schenck, H., Steinmetz, E., “Activity, Standard Conditions and Coefﬁcients of Activity” (in German), Stahleisen-Sonderberichte, Duesseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Phase Relations, Thermodyn., Review, 161) Holleck, H., Thuemmler, F., “Investigations on the Formation of Metalloid-Stabilized Zr-Rich Transition” (in German), J. Nucl. Mater., 23, 88–94 (1967) (Crys. Structure, Review, 12) Sleight, A.W., Chamberland, B.L., “Transition Metal Molybdates of the Type AMoO4”, Inorg. Chem., 7(8), 1672–1675 (1968) (Crys. Structure, Experimental, 10) Thorne, J.K., Dahl, J.M., Van Vlack, L.H., “Partition Coefﬁcient of Molybdenum in the Fe-Mo-Si-O System”, Metall. Trans., 1(8), 2125–2132 (1970) (Experimental, Phase Diagram, Phase Relations, 9) Fischer, W.A., Janke, D., “The Activity of Oxygen in Iron Melts Containing Molybdenum, Tungsten, Niobium or Tantalum” (in German), Arch. Eisenhuettenwes., 42(10), 695–698 (1971) (Thermodyn., Experimental, 15) Abe, M., “Phase Equilibrium Relations in the MoO2-FeO-Fe3O4 System at 1140°C”, Mater. Res. Bull., 7, 1443–1453 (1972) (Experimental, Phase Diagram, Phase Relations, 14) Schmahl, N.G., Dillenburg, H., “Phase Equilibria and Thermodynamics of the Ternary Systems Fe-Mo-O and Fe-W-O” (in German), Z. Physik. Chemie. Neue Folge, 77, 113–126 (1972) (Experimental, Phase Diagram, Thermodyn., 40) Sleight, A.W., “Accurate Cell Dimensions for ABO4 Molybdates and Tungstates”, Acta Crystallogr., B28, 2899–2902 (1972) (Crys. Structure, Experimental, 19) Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310 (1974) (Review, Thermodyn., 249) Katsura, T., Wakihara, M., Hara, S.I., Sugihara, T., “Some Thermodynamic Properties in Spinel Solid Solutions with the Fe3O4 Component”, J. Solid State Chem., 13(1–2), 107–113 (1975) (Experimental, Phase Diagram, Thermodyn., 11) Chen, H., “The Crystal Structure and Twining Behaviour of Ferric Molybdate, Fe2(MoO4)3”, Mater. Res. Bull., 14, 1583–1590 (1979) (Crys. Structure, Experimental, 7) Brewer, L., Lamoreaux, R.H., “The Mo-O System (Molybdenum-Oxygen)”, Bull. Alloys Phase Diagrams, 1(2), 85–89 (1980) (Crys. Structure, Thermodyn., Assessment, #, 12)

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Fe–Mo–O [1981Kle]

[1981Mas] [1982Fer] [1982LeP] [1982Str] [1983Kle]

[1984Kag]

[1988Bag]

[1989Rag]

[1991Sun] [1993Koe]

[1993Mor]

[1994Koy]

[1995Kow]

[2001Hai]

[2002Mor]

[2002Tya]

[2003Ehr]

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Kleykamp, H., Schauer, V., “Phase Equilibria and Thermodynamics in the Fe-Mo and Fe-Mo-O Systems”, J. Less-Common Met., 81(2), 229–238 (1981) (Experimental, Phase Diagram, Thermodyn., 35) Massarotti, V., Flor, G., Marini, A., “Crystal Data for Ferric Molybdate: Fe2(MoO4)3”, J. Appl. Crystallogr., 14, 64–65 (1981) (Crys. Structure, Experimental, 9) Fernandez-Guillermet, A., “The Fe-Mo (Iron-Molybdenum) System”, Bull. Alloy Phase Diagrams, 3(3), 359–367 (1982) (Assessment, Crys. Structure, Thermodyn., #, 40) Le Page, Y., Strobel, P., “Structure of Iron Molybdenum (IV) Oxide Fe2Mo3O8”, Acta Crystallogr., 38B(4), 1265–1267 (1982) (Crys. Structure, Experimental, 7) Strobel, P., “Growth and Physical Properties of Single Crystals of Fe2(II)Mo3(IV)O8”, J. Solid State Chem., 42, 242–250 (1982) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 26) Kleykamp, H., “Experimental Aspects of Solid Galvanic Cell Methods for Thermodynamic Studies on Alloys”, Ber. Bunsen-Ges. Phys. Chem., 87(9), 777–781 (1983) (Phase Diagram, Thermodyn., Theory, 32) Kaganyuk, D.S., Perepelitsa, A.P., “Estimating the Enthalpy of Formation for Compounds of MR(EO4)2 Type”, Inorg. Mater., 20(4), 566–571 (1984), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 20(4), 653–658 (1984) (Thermodyn., Calculation, 14) Bagdavadze, D.I., Tsagareishvili, D.Sh., Tskhadaya, R.A., Gvelesiani, G.G., “Method of Computation of Enthalpy Increment of Crystalline Inorganic Compounds in the 0-298.15 K Temperature Range” (in Russian), Izv. Akad. Nauk Gruz. SSR, Ser. Khim, 14(3), 199–206 (1988) (Calculation, Thermodyn., Review, 8) Raghavan, V., “The Fe-Mo-O System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 5, 193–204 (1989) (Crys. Structure, Phase Diagram, Phase Relations, Review, 15) Sundman, B., “An Assessment of the Fe-O System“, J. Phase Equilib., 12(1), 127–140 (1991) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 53) König, U., Morgenstern, T., Försterling, G., “A Study of Structural Crystallography on Ternary Metal Oxides in the System Fe-Mo-O”, Mater. Sci. Forum, 133–136, 687–692 (1993) (Crys. Structure, Electronic Structure, Experimental, 7) Morgenstern, T., Lienhardt, J.L., Reichelt, J.L., König, U., Opperman, H., “Investigations on the Ternary Systems Fe-Mo-O and Ni-Mo-O”, Mater. Sci. Forum, 133–136, 627–632 (1993) (Phase Diagram, Crys. Structure, Transport Phenomena, Experimental, 7) Koyama, K., Harada, T., “Phase Diagram of the Fe-Mo-O System at 1173 K similar to 1473 K”, J. Jap. Inst. Metals, 58(12), 1401–1407 (1994) (Phase Diagram, Thermodyn., Experimental, 14) Kowalski, M., Spencer, P.J., “Thermodynamic Revaluation of the Cr-O, Fe-O and Ni-O Systems: Remodelling the Liquid, BCC and FCC Phases”, Calphad, 19(3), 229–243 (1995) (Assessment, Phase Diagram, Thermodyn., Review, 47) Hainz, M., Boller, H., “GaMgMo4O7 and Fe2Mo4O7 - Two Low Valent Molybdenum Oxides with a Fully Ordered Sc0.75Zn1.25Mo4O7 Type Structure”, J. Alloys Compd., 317–318, 132–135 (2001) (Crys. Structure, Experimental, Magn. Prop., 9) Morales, R., Arvanitidis, I., Sichen, D., Seetharaman, S., “Reduction of the Fe2MoO4 by Hydrogen Gas”, Metall. Mater. Trans. B, 33b(4), 589–594 (2002) (Experimental, Kinetics, Morphology, 23) Tyagi, A.K., Achary, S.N., Mathews, M.D., “Phase Transition and Negative Thermal Expansion in A2(MoO4)3 System (A = Fe3+, Cr3+ and Al3+)”, J. Alloys Compd., 339, 207–210 (2002) (Crys. Structure, Phys. Prop., Experimental, 14) Ehrenberg, H., Bramnik, K.G., Müssig, E., Buhrmeister, T., Weitzel, H., Ritter, C., “The Ferrimagnetic Structure of Fe2Mo3O12: Dependence of the Fe-O-O-Fe Superexchange Coupling on Geometry”, J. Magn. Magn. Mater., 261, 353–359 (2003) (Crys. Structure, Magn. Prop., Experimental, 5)

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18 [2003Koy]

[2003Per] [2003Tay]

[2006Ha]

[Mas2] [V-C2]

Fe–Mo–O Koyama, K., Morishita, M., Harada, T., Maekawa, N., “Determination of Standard Gibbs Energies of Formation of Fe2Mo3O12, Fe2Mo3O8, Fe2MoO4, and FeMoO4 of the Fe-Mo-O Ternary System and μ-Phase of the Fe-Mo Binary System by Electromotive Force Measurement Using a Y2O3-Stabilized ZrO2 Solid Electrolyte”, Metall. Mater. Trans B, 34B, 653–659 (2003) (Thermodyn., Experimental, 15) Perrot, P., Foct, J., “Gases other than Hydrogen in Iron and Steels” (in French), Techniques de l’IngJnieur M4275, 1–23 (2003) (Thermodyn., Kinetics, Phase Relations, Review, 127) Taylor, S.H., Hutchings, G.J., Palacios, M.-L., Lee, D.F., “The Partial Oxidation of Propane to Formaldehyde Using Uranium Mixed Oxide Catalysts”, Catal. Today, 81, 171–178 (2003) (Catalysis, Experimental, Interface Phenomena, 9) Ha, J.K., Cho, K.K., “Characterization of Fe-Mo Alloyed Nanoparticles Synthesized by Chemical Vapor Condensation Process”, Mat. Sci. Forum, 510–511, 466–469 (2006) (Crys. Structure, Experimental, Morphology, Nano, 7) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–Mo–Si

1

Iron – Molybdenum – Silicon Elena Semenova

Introduction The constitution of the Fe-Mo-Si system has been of interest since 1955, owing to the presence of the MoSi2 compound in the Mo-Si binary system. This compound is known to have high melting point and excellent oxidation resistance, serving as a basis for high temperature structural applications. The Fe rich ternary Fe-Mo-Si alloys were considered by the researches in the following decades as prospective for the development of materials with soft magnetic characteristics, greater hardenability, better mechanical properties. In order to investigate the solubility of iron in MoSi2, [1956Fit] studied the phase relationships in the FeMo-Si ternary system in the region of up to about 40 at.% Mo. The results were presented as an isothermal section at 1400°C. From this section, it can be seen that up to 10 at.% Fe can be dissolved in αMoSi2. Two ternary phases were also presented in this section, one of which having close to equiatomic composition. A number of the binary phases shown in the section, such as β, η, α and ζα, should not be observed at 1400°C if the Fe-Si phase diagram as presented by [Mas2] is taken into account. [1961Vog] studied the constitution of the Fe-Mo-Si system in the Fe-Mo-MoSi2-FeSi region at the temperature of the liquid-solid transformation. Six vertical sections were constructed from which [1961Vog] derived the liquidus surface projection. A ternary phase of the MoFe2Si2 composition was found. The microhardness of some alloys was also measured. [1985Ray, 1988Ray], in their thorough assessment of the work of [1961Vog], removed some of the discrepancies in the liquidus projection that arose through conﬂicts with more recent data relating to the binary systems and proposed hypothetical reactions for the uninvestigated region of the system. Along with the work of [1956Fit] and [1961Vog], the assessment also reviewed the studies reported by [1960Gla, 1962Gla, 1963Bar, 1965Sko, 1966Sko, 1968Gla, 1969Kar]. All of these publications concern the phase relationships in the solid state of the ternary system. [1960Gla, 1962Gla, 1963Bar] studied alloys with compositions lying along the 33 at.% Mo section to investigate the possibility of the formation of a ternary Laves phase. The existence of this phase, with a crystal structure of the MgZn2 type, was shown at an equiatomic composition as single phase; it being found as a second phase in other alloys along the 33 at.% Mo section up to the composition MoFeSi. The phase was interpreted by [1963Bar] as a solid solution of Si in the binary MoFe2 phase. [1969Tes] considered the electronic and structural factors leading to the formation of a Laves phase of this type. [1965Sko] investigated whether a phase with a crystal structure similar to the R phase was present in the Fe-Mo-Si system and reported that the Mo5Fe3Si2 ternary phase, having the hexagonal crystal structure attributed to R type phases, was observed in as cast alloys. The intermediate ternary phases forming in the Fe-Mo-Si system and their relationship with other phases of the system were studied at 800°C by [1966Sko, 1968Gla]. The existence of the Mo5Fe3Si2 [1965Sko] and MoFe2Si2 [1961Vog] ternary phases was conﬁrmed. The Mo3FeSi and (Mo0.17Fe0.33)5Si3 ternary phases were found for the ﬁrst time. An isothermal section for the Fe-Mo-Si system at 800°C was constructed. [1998Yi] examined the possibility of modifying the crystal structure and microstructure of MoSi2 by alloying with transition elements, including iron, in an attempt to improve mechanical properties. Compositions of the Fe-Mo-Si system that are enriched in iron are also of practical interest [1969Kar, 1988Nak, 1988Kum, 2002You, 1998Mie]. [1969Kar] reported on the substantial hardening observed after ageing alloys in the Fe corner of the system at 550–750°C. [1988Nak] studied the effects of rapid quenching on the suppression of ordering of the α phase. Taking into account the importance of information regarding the inﬂuence of alloying element on the stability of the γ phase during heat treatment, [1988Kum] used a subregular solution model with a contribution to the Gibbs energy from magnetic ordering to calculate the effect of Mo and Si on the stability of the γ phase in the ternary Fe-Mo-Si system at various temperatures. [2002You] studied the effect of Si additions on sintering and mechanical properties, as well as the effect of composition and cooling rate on sinter hardening characteristics of Fe-1.5 mass% Mo powders. Landolt-Börnstein New Series IV/11D4

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Fe–Mo–Si

[1998Mie] performed a Calphad optimization of thermodynamic parameters for the iron rich part of the ternary system based on the information given in the review of [1988Ray]. The wettability of a MoSi2 substrate by an iron melt was investigated by [1966Yas]. The review of the phase equilibria in the Fe-Mo-Si by [1994Rag] is unfortunately incomplete and so does not add any new information. Data on the temperature and composition ranges used in the investigations described above, as well as the experimental techniques employed, are summarized in Table 1. Binary Systems The Fe-Si and Mo-Si phase diagrams are accepted from [1982Kub] and [Mas2] respectively. The temperatures of the two invariant reactions in the Mo-Si system, l ⇌ Mo5Si3 + βMoSi2 (αMoSi2) and βMoSi2 ⇌ αMoSi2, are the same at 1900°C. The βMoSi2 ⇌ αMoSi2 degenerate reaction can be of metatectic or peritectic type depending on whether it precedes or follows the eutectic reaction. Some uncertainties are observed in the representation of the Fe-Mo phase diagram given by [Mas2] in the region of the α phase. [Mas2], citing [1982Gui2] (which is essentially the same work as presented in [1982Gui1]), presents what looks like a eutectic reaction l ⇌ α + R at 1449°C in the Fe rich region of the phase diagram (although this feature is by no means clear) but without any indication as to the composition of the phases. It is worth noting that the text indicates that the Fe rich liquidus falls to a minimum with the addition of Mo, contradicting the phase diagram presented in the accompanying ﬁgure. In the original Calphad assessment work [1982Gui1, 1982Gui2], experimental evidence is cited of a peritectic reaction taking place at 1449°C and a minimum in the liquidus and solidus occurring at a temperature of 1448°C. It is also indicated that ‘The agreement is excellent’ between calculated and experimentally determined phase boundaries. A later modeling of the system by the same author (cited in 1988And]) gives an invariant temperature of ‘1724 K’; 2 degrees higher than in the earlier work, ensuring a peritectic formation of the (αFe) phase; although this is higher than the experimental measurement quoted in [1982Gui1, 1982Gui2]. It is clear that this part of the diagram is in much need of conﬁrmation, but in the meantime, the version given in [1982Gui2] is accepted here. Solid Phases The crystallographic data on the solid phases of the Fe-Mo-Si system are listed in Table 2. There are reports of four ternary phases present in the system. The work of [1960Gla, 1961Vog, 1962Gla, 1963Bar, 1956Fit, 1966Sko, 1968Gla, 1969Tes] refer to the presence of a ternary Laves type phase at an alloy of equiatomic composition, but it is considered here to be an extended solid solution of Si in the binary MoFe2 Laves phase over a considerable range of Si content. The experimental data of [1963Bar] and [1956Fit] suggest that the λ1 phase of the MoFeSi composition still exists at 1200 and 1400°C, respectively, even though it decomposes at 927°C in the Fe-Mo binary system. The τ1 ternary phase forms at 1440°C and has the composition of 34.5Mo-42.5Fe-23 Si (mass%) (18.54Mo-39.24Fe-42.22 Si (at.%)) according to [1961Vog]. Its existence was conﬁrmed at 800°C by [1966Sko, 1968Gla]. [1966Sko] noted that its range of homogeneity at 800°C was insigniﬁcant, and it was found by [1961Vog] at subsolidus temperatures. The ternary phase observed by [1966Sko] at 800°C having the Mo3FeSi composition did not have a noticeable homogeneity range. Two other ternary phases with compositions of Mo2Fe2Si and Mo2Fe3Si observed by [1961Vog] were interpreted by [1966Sko] as ternary extensions of intermediate phases in the Fe-Mo binary system. While the Mo2Fe2Si phase was attributed to the endpoint of the σ phase in the ternary system, the Mo2Fe3Si phase, which forms congruently [1961Vog], was assumed to be related to the phase known at that time as Mo2Fe3. This was later shown by [Mas2] to be the R phase, and Si additions enable its temperature stability range to be increased to 1610°C [1961Vog]. The ternary phase with the composition Mo5Fe3Si2 found at 800°C by [1965Sko, 1966Sko] has a crystal structure similar to that of the R phase of the binary Fe-Mo system. In a critical analysis of the available ternary phase equilibrium data, [1985Ray] suggested that the Mo5Fe3Si2 phase was the same phase as the binary R phase, stabilized by Si additions to lower temperatures and higher Mo concentrations than it is in the binary system. The Mo10Fe52Si38 phase ﬁrst observed by [1966Sko] was assumed to be a solid solution, based on the η binary phase stabilized by Mo to lower temperatures. DOI: 10.1007/978-3-540-78644-3_28 # Springer 2008

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3

All intermediate phases of the Fe-Si and Mo-Si system dissolve about 2-4 at.% of the third component at 800°C [1966Sko]. The exception is the MoSi2 phase for which [1998Yi] found little solubility for Fe. [1969Kar] reported that additions of Si decreased the Mo solubility in the α phase, but without indicating an absolute value. The phase strengthening of this alloy at ≤800°C occurs mainly by the precipitation of the λ1 phase with a small amount of the μ phase. This statement given by [1969Kar] seems to be unlikely, it being in contradiction with the data of [1966Sko, 1968Gla] which would suggest that the μ phase cannot be in equilibrium with the α phase at these temperatures. Quasibinary Systems According to [1961Vog], the FeSi-MoSi2 section of the Fe-Mo-Si ternary system is quasibinary of eutectic type. Taking into account that the eutectic point is at the same time a saddle point on the ternary liquidus, and that the components of the FeSi-MoSi2 section melt congruently, this section can be considered as a true quasibinary, at least at subsolidus temperatures. It is constructed here (Fig. 1) based on the melting points of the FeSi and MoSi2 phases taken from [Mas2], the coordinates of the eutectic point from [1961Vog] and information on their mutual solubility [1966Sko, 1998Yi]. Invariant Equilibria According to [1961Vog], there are 8 invariant four-phase reactions with the participation of liquid occurring in the Fe-Mo-MoSi2-FeSi part of the ternary system. Taking into consideration the constitution of the Fe-Si system, where two eutectic reactions, l ⇌ ε + β and l ⇌ β + α, are shown, [1985Ray, 1988Ray] added one more invariant equilibrium of the transition type (U7), in which the ε, β, α phases and liquid are involved. In agreement with the version of Mo-Si phase diagram given in [Mas2], where the βMoSi2 ⇌ αMoSi2 transformation is shown, it is necessary to assume the existence of an invariant four-phase reaction resulting from the low-temperature modiﬁcation of the MoSi2 compound, L + βMoSi2 ⇌ αMoSi2 + Mo5Si3. According to [1961Vog, 1985Ray, 1988Ray], the R phase forms in the ternary system congruently at 1610°C and the composition of 49Mo-42Fe-9Si (mass%) (47.5Mo-32.26Fe-20.24Si (at.%)). Therefore the maximum temperature on the monovariant line between the primary crystallization ﬁelds of the R and σ phases (1605°C, at the approximate composition of 50.5Mo-42Fe-7.5Si (mass%)) should correspond to the eutectic reaction L ⇌ σ + R, on the contrary to the peritectic reaction L + σ ⇌ R reported by [1985Ray, 1988Ray]. All of these reactions are listed in Table 3 together with the compositions of the liquid phase involved. Five temperature maxima were determined experimentally in the Fe-Mo-MoSi2-FeSi part of the ternary system by [1961Vog]. These ﬁve reactions are also included in Table 3. A reaction scheme for the system is derived in Figs. 2a, b. It contains, along with the above mentioned invariant reactions in the ternary system, two more reactions assumed by [1985Ray, 1988Ray] for the composition region not investigated by [1961Vog]. As these are hypothetical they are drawn with dashed lines. Based on the liquidus surface given by [1961Vog] and the boundary binary phase diagrams, and keeping in mind the constitution of the isothermal section at 800°C, [1988Ray] deduced the sequence of reactions that could proceed in the solid state. This is reasonable speculation that is consistent with the available experimental data relating to the liquidus surface and the alloy constitution at 800°C, proposing the probable scheme for the transition from a high to a low temperature state in the system. However it cannot be unconditionally accepted because of the lacking data on the high-temperature constitution of the system. Liquidus, Solidus and Solvus Surfaces The projection of the liquidus surface for the Fe-Mo-MoSi2-FeSi part of the ternary system was derived by [1961Vog] using experimental data for alloys located along certain vertical sections. According to [1961Vog], the τ1 phase forms by the peritectic reaction l + Mo5Si3 ⇌ τ1 at 1440°C. Nothing is known about the formation of the τ2 phase [1966Sko, 1968Gla]. If it forms from the solid, the liquidus projection of the system as shown by [1961Vog] for the Fe-Mo-MoSi2-FeSi region will remain unchanged. The projection was modiﬁed by [1985Ray] to conform with more recent versions of the binary diagrams, which coincide with those accepted here. An updated version of the liquidus surface of the system for the whole composition range is shown in Fig. 3. It includes the hypothetical invariant lines (dashed lines) separating Landolt-Börnstein New Series IV/11D4

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Fe–Mo–Si

the ﬁelds of primary crystallization of the ε, βMoSi2, ζα and (Si) phases which were added by [1985Ray, 1988Ray]. Dashed lines separating tentatively the primary crystallization ﬁelds of βMoSi2 and αMoSi2 phases have also been added. The solidus and liquidus temperatures, (∼1045 and 1180°C, respectively, obtained by [2002You] for a sintered alloy of composition Fe-1.5Mo-3Si (mass%) can be considered as underestimated, as do not agree with those measured by [1961Vog] for alloys of similar composition. Isothermal Sections The isothermal section at 800°C constructed by [1966Sko] and reproduced in [1968Gla] is shown in Fig. 4 with small corrections related to the lack of solubility of iron in αMoSi2 in accordance with the work of [1998Yi]. The solubility range of the τ2 phase is shown as taken from the drawing in [1966Sko], however most likely it does not have a noticeable range of homogeneity as follows from the experiment data of [1966Sko]. Figures 5a to 5d present a set of the isothermal sections in the Fe rich corner at 950, 1050, 1150 and 1250°C calculated by [1988Kum]. Although the locations of the α and γ phase boundaries on the Fe-Mo and Fe-Si binary sides somewhat differ from those in [Mas2] the sections give a notion as to the variation of the γ/α+γ and α/α+γ phase boundaries with changing temperature. A probable isothermal section of the Fe-Mo-Si phase diagram at room temperature was estimated and presented by [1988Ray]. Temperature – Composition Sections Six vertical sections were constructed by [1961Vog] based on experimental data. Two of them, FeSi-Mo5Si3 and Fe75Si25-τ1, are shown in Figs. 6 and 7 with some modiﬁcations relating to the stoichiometry of the most thermostable silicide (Mo5Si3 instead of Mo3Si) and the homogeneity range of the ε phase. Other sections constructed by [1961Vog] are not shown here since they pass through phases whose composition changes substantially with temperature and therefore may lie out of the plane of the section at temperatures other than those studied (e.g. μ or R phases). Thermodynamics [1998Mie] performed a Calphad optimization of thermodynamic parameters describing the liquid, α and γ phases of the iron rich part of the Fe-Mo-Si system in order to calculate phase equilibria in multicomponent steels. Data used in the assessment were taken from the review given by [1988Ray]. The temperatures of two invariant equilibria involving the liquid and α phases; L + R ⇌ α + τ and L ⇌ τ1 + α + ε, were calculated by [1998Mie] to be 1188 and 1135°C, which are reasonably close to the experimental values of 1186 and 1170°C, respectively, given by [1961Vog]. Notes on Materials Properties and Applications The microhardness of the τ1 phase was measured to be HV 1080 (10.59 GPa) and that of the ternary R phase in a Mo2Fe3Si alloy was about HV 1180 (11.57 GPa) [1961Vog]. The hardness of a Fe-Mo-2.5Si (mass%) alloy increased to HV 190 (1.863 GPa) [1969Kar] on increasing the Mo concentration from 3 to 10 mass%; the hardness of aged specimens increasing noticeably. High silicon alloys containing around 6 mass% Si are well known as excellent soft magnetic materials [1988Nak]. Using iron single crystals containing 5.5 mass% Si and 0.5-1.5 mass% Mo, [1988Nak] examined the effect of quenching on the magnetic anisotropy and saturation magnetization. The latter was found to decrease with increasing Mo concentration while the magnetic anisotropy decreased with increasing quench temperature. The behavior of the anisotropy was attributed to the degree of ordering in the alloys. An addition of 3 mass% Si to Fe-1.5Mo powder increases ultimate tensile strength up to 445 MPa, hardness up to HV 10 (0.098 GPa) as well as an improvement in the three point bend strength. These improvements in the mechanical properties are due to solid solution strengthening, enhanced α phase sintering and activated liquid phase sintering. All three properties increase with temperature [2002You]. Elongation was shown to decrease on increasing the Si content from 2 to 5 mass%. This was mainly related by [2002You] to an embrittling effect caused by Si. Complete wetting of a MoSi2 substrate by molten iron was observed by [1966Yas]. DOI: 10.1007/978-3-540-78644-3_28 # Springer 2008

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Miscellaneous The effective radius of silicon in the ternary Laves phase alloys was shown by [1963Bar] to be about 118 pm, which is noticeably smaller than its atomic radius of 134 pm. Comparing the α phase lattice parameter of two aged alloys, Fe-10Mo (mass%) and Fe-10Mo-1Si (mass%) [1969Kar] reported that Si addition resulted in a decrease in the lattice parameter. Additions of Mo suppress the ordering of the α solid solution in the ternary system [1966Sko]. On increasing the Si content (2–5 mass%) in Fe-1.5Mo (mass%) alloy powder and increasing the temperature of sintering (1140–1250°C), shrinkage increases, and sintering under vacuum results in higher densities than sintering under pure hydrogen [2002You]. The Fe-1.5Mo-3Si-1.2C (mass%) composition exhibits high sintered density and good mechanical properties. A single stage compaction and sintering process have been developed.

Table 1.

Investigations of the Fe-Mo-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1961Vog]

A Tamman furnace melting, thermal analysis with cooling rate of 20–50°C·min–1, metallography, microhardness

Fe-FeSi-MoSi2-Mo 1650-1200°C

[1962Gla]

Melting in corundum crucibles, X-ray, microstructure analysis

Fe-Mo-Si

[1963Bar]

Arc melting, XRD, metallography

Mo(Fe1–xSix), where x = 0.165; 0.330; 0.5 1200°C

[1965Sko]

X-ray

30Fe-50Mo-20Si (at.%)

[1966Sko]

Electric-arc furnace melting, X-ray, microstructure analysis

Fe-Mo-Si at 800°C

[1966Yas]

Technique of superincumbent drop, metallography, chemical analysis

Fe-MoSi2

[1968Gla]

Arc furnace melting, microstructure and X-ray analysis

Fe-Mo-Si 800°C

[1969Kar]

X-ray, metallography, microhardness, TEM, photocolorimetry

Fe-(2.65-10.5)Mo-(0-3)Si (mass%) 0–800°C

[1988Nak]

X-ray analysis, vibrating sample magnetometry, a torque meter

Magnetic anisotropy, saturation magnetization Fe-(0.5-1.5)Mo-5.5Si 700–1100°C

[1998Yi]

Arc melting, metallography, EPMA, XRD, EDS, TEM

Fe5Mo29Si66

[1998Mie]

Calphad assessment

Fe-7.5Mo-16.5Si (mass%) Fe-6.5Mo-18.5Si (mass%)

[2002You]

Sintering, DTA, optical microscopy, microhardness, dilatometry, hardness, ultimate tensile strength, three point bend strength

Fe-1.5Mo-(2, 3, 5)Si (mass%)

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Fe–Mo–Si

Table 2:

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, MoxFe1–x–Siy

cI2 Im 3m W

(αFe) ≤912 (δFe) 1538–1394 (Mo) < 2623

cI2 Im 3m W

γ, MoxFe1–x–ySiy

cF4 Im 3m Cu

(γFe) 1394–912

Lattice Parameters [pm]

Comments/References

a = 286.65

at x = 0, 0 ≤ y ≤ 0.0195 at y = 0, 0 ≤ x ≤ 0.244; 0.687 ≤ x ≤ 1 at x + y = 1, 0 ≤ y ≤ 0.04 [Mas2, 1982Gui2] pure Fe at 25°C [Mas2]

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

a = 314.70 a = 311.8

at 25°C [Mas2] at ∼20 at.% Fe [1982Gui2]

a = 364.67

at x = 0, 0 ≤ y ≤ 0.038 at y = 0, 0 ≤ x ≤ 0.017 pure Fe at 915°C [Mas2]

(Si) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

at 25°C [V-C2, Mas2]

λ1, MoFe2 < 927

hP12 P63/mmc MgZn2

a = 475.5 c = 776.7 γ = 120° a = 473.7 c = 772.7 a = 474.0 c = 768.8 a = 476.6 c = 760.1

at 33.3 at.% Mo [V-C2, Mas2] dissolves about 33.3 at.% Si [1956Fit, 1960Gla, 1962Gla, 1963Bar, 1966Sko] 66.7Fe-Mo-16.5Si with 4% of other phase

R, Mo2Fe3 1488–1200

hR159 R 3 Cr2Mo3Co5

a = 1095.6 c = 1935.3 a = 1106 c = 1994 μ, Mo6Fe7 < 1370

hR39 R 3m W6Fe7

a = 475.1 c = 256.8 γ = 120°

66.7Fe-Mo-16.5Si single phase 66.7Fe-Mo-16.5Si with 5% of other phase at 1200°C [1963Bar] from 33.9 to 38.5 at.% Mo [Mas2] forms in the ternary system congruently at 1610°C and 49Mo-42Fe-9Si (mass%) (47.5Mo-32.26Fe-20.24Si (at.%)) [1961Vog] [V-C2] Mo5Fe3Si2 [1965Sko] from 39.0 to 44.0 at.% Mo [Mas2] for Fe saturated alloy [1982Gui2] dissolves about 16.6 at.% Si at subsolidus temperature [1961Vog] and 13.5 at.% Si at 800°C [1966Sko] (continued)

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Lattice Parameters [pm]

7

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

σ, MoFe 1611–1235

tP30 P42/mmm CrFe

β, Fe2Si 1212–∼1040

cP2 Pm 3m CsCl

a = 281

[V-C2, Mas2] dissolves 2 to 4 at.% Mo at 800°C [1966Sko]

α1, Fe3Si ≲1235

cF16 Fm 3m Fe3Bi

a = 565

[V-C2] from ∼11 at.% Si at 500°C to ∼30.5 at.% Si at 1040°C [Mas2] dissolves 2 to 4 at.% Mo at 800°C [1966Sko]

α2, Fe-Si ≲ 1280

cP2 Pm 3m CsCl

-

[1982Kub] from ∼10 at.% Si at 500°C to ∼23 at.% Si at 1235°C [1982Kub] dissolves 2 to 4 at.% Mo at 800°C [1966Sko]

η, Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.9 ± 0.5 c = 472.0 ± 0.5

[V-C2] at 37.5 at.% Si [Mas2]

a = 676.4 c = 472.4

(Mo0.17Fe0.83)Si3 [1966Sko, 1968Gla]

a = 921.8 c = 481.3

Comments/References

from 42.9 to 56.7 at.% Mo [Mas2] at 50 at.% Mo [1982Gui2] dissolves about 20 at.% Si at subsolidus temperature [1961Vog]

ε, FeSi < 1410

cP8 P213 FeSi

a = 451.7

[V-C2] at ∼50 at.% Si [Mas2] dissolves from 2 to 4 at.% Mo at 800°C [1966Sko]

ζα, FeSi2 (h) 1220–937

tP3 P4/mmm βFeSi2

a = 268.4 c = 512.8

[V-C2] from 70 to 73 at.% Si at ∼1210°C [Mas2]

ζβ, FeSi2 (r) < 982

oC48 Cmca αFeSi2

a = 986.3 ± 0.7 b = 779.1 ± 0.6 c = 783.3 ± 0.6

at 66.7 at.% Si [V-C2, Mas2] dissolves from 2 to 4 at.% Mo at 800°C [1966Sko]

Mo3Si < 2025

cP8 Pm 3m Cr3Si

a = 489.7

[V-C2, Mas2] dissolves 2 to 4 at.% Fe at 800°C [1966Sko]

Mo5Si3 < 2180

tI32 I4/mcm Si3W5

a = 964.7 c = 491.5

βMoSi2 2020–1900

hP9 P6222 CrSi2

a = 464.2 ± 0.5 c = 652.9 ± 0.5 γ = 120°

∼37 to ∼40 at.% Si at 1900°C [Mas2] [V-C2, Mas2] dissolves 2 to 4 at.% Fe at 800°C [1966Sko] [V-C2, Mas2] does not dissolve Fe [1998Yi] (continued)

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Fe–Mo–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

αMoSi2 < 1900

tI6 I4/mmm MoSi2

a = 320.6 b = 784.6

[V-C2, Mas2] dissolves 2 to 4 at.% Fe at 800°C [1966Sko] does not dissolve Fe [1998Yi]

* τ1, MoFe2Si2 < 1440

o*

a = 494 ± 5 b = 1288 ± 5 c = 1541 ± 5

[1961Vog, 1966Sko, 1968Gla] forms at 1440°C and 34.5Mo-42.5Fe23Si (mass%) (18.54Mo-39.24Fe-42.22Si (at.%))

* τ2, Mo3FeSi

tI56 I 4c2 Mo3CoSi

a = 1269.7 ± 0.5 c = 489.1 ± 0.5

at 800°C [1966Sko, 1968Gla]

Table 3.

Invariant Equilibria

Reaction

T [°C]

Type

Phase

Composition (at.%) Fe

Mo

Si

L + βMoSi2 ⇌ αMoSi2 + Mo5Si3

< 1900

U1

L

∼0

∼46

∼54

l + (Mo) ⇌ σ

∼1630

p2

l

∼39

∼40

∼21

L + (Mo) ⇌ Mo3Si + σ

∼1620

U2

L

∼40

∼37

∼23

l⇌R+σ

∼1605

e3

l

∼49

∼34

∼17

L + σ ⇌ Mo3Si + R

∼1575

U3

L

∼41

∼33

∼26

L + Mo3Si ⇌ R + Mo5Si3

∼1550

U4

L

∼42

∼30

∼28

l + Mo5Si3 ⇌ τ1

1440

p5

l

45

13

42

l ⇌ ε + βMoSi2

1390

e6

l

44

4

52

L + Mo5Si3 ⇌ R + τ1

1356

U5

L

48

15

37

L + Mo5Si3 ⇌ τ1 + αMoSi2

1342

U6

L

42

11

47

l ⇌ τ1 + ε

1340

e7

l

45

8

47

L ⇌ τ1 + αMoSi2 + ε

1331

E1

L

44

9

47

∼1190

U7

L

∼66

∼2

∼32

L + R ⇌ τ1 + α

1186

U8

L

∼67

∼4

∼29

L ⇌ α + τ1 + ε

1170

E2

L

∼65

∼3

∼32

L+β⇌α+ε

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Fig. 1. Fe-Mo-Si.

Landolt-Börnstein New Series IV/11D4

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The FeSi-MoSi2 quasibinary section

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Fe–Mo–Si

Fig. 2a. Fe-Mo-Si.

Reaction scheme, part 1

10

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Fig. 2b. Fe-Mo-Si.

Reaction scheme, part 2

Fe–Mo–Si

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Fig. 3. Fe-Mo-Si.

Fe–Mo–Si

Liquidus surface projection

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Fig. 4. Fe-Mo-Si.

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Isothermal section at 800°C

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Fig. 5a. Fe-Mo-Si.

Fe–Mo–Si

Calculated isothermal section in the Fe rich region at 950°C

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Fig. 5b. Fe-Mo-Si. Calculated isothermal section in the Fe rich region at 1050°C

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Fig. 5c. Fe-Mo-Si.

Fe–Mo–Si

Calculated isothermal section in the Fe rich region at 1150°C

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Fig. 5d. Fe-Mo-Si. Calculated isothermal section in the Fe rich region at 1250°C

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Fig. 6. Fe-Mo-Si.

Fe–Mo–Si

FeSi-Mo5Si3 vertical section

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Fig. 7. Fe-Mo-Si.

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Fe75Si25-Fe2MoSi2 vertical section

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20 References [1956Fit] [1960Gla]

[1961Vog] [1962Gla]

[1963Bar] [1965Sko]

[1966Sko]

[1966Yas]

[1968Gla]

[1969Kar]

[1969Tes]

[1982Gui1] [1982Gui2]

[1982Kub]

[1985Ray] [1988And] [1988Kum] [1988Nak]

[1988Ray]

Fe–Mo–Si

Fitzer, E., “MoSi2 as a High-Temperature Material” (in German), Plansee Seminar, 2, 56–78 (1956) (Phase Relations, Experimental, 25) Gladyshevskii, E.I., Kuzma, Yu.B., “Crystal Structure of Ternary Phases in the Systems Mo (W)-Fe (Co, Ni)-Si”, J. Struct. Chem. 1(1), 57–62 (1960), translated from Zh. Strukt. Khim., 1(1), 66–71 (1960) (Crys. Structure, Experimental, 11) Vogel, R., Gerhardt, R., “Fe-Mo-Si” (in German), Arch. Eisenhuettenwes., 32(1), 47–56 (1961) (Morphology, Phase Diagram, Experimental, #, 9) Gladyshevskii, E.I., “Crystal Structure of Compounds and Phase Equilibria in Ternary Systems of Two Transition Metals and Silicon”, Sov. Powder Metall. Met. Ceram., (4), 262–265 (1962) (Crys. Structure, Experimental, 17) Bardos, A.M., Bardos, D.I., Beck, P.A., “The Effective Atomic Radius of Si in Ternary Laves Phase Alloys”, Trans. Metall. Soc. AIME, 227, 991–993 (1963) (Crys. Structure, Experimental, 12) Skolozdra, R.V., Yarmolyuk, Ya.P., Gladyshevsky, E.I., “Compounds of R-Phase Type in the Systems Mo-Fe(Co, Ni)-Si(Ge)”, Zh. Strukt. Khim., 6, 473–474 (1965) (Crys. Structure, Experimental, 7) Skolozdra, R.V., Gladyshevskiy, E.I., “The Molybdenum-Iron-Silicon System”, Russ. Metall., 2(8), 1237–1242 (1966), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 2(8), 1448–1453 (1966) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Experimental, 17) Yasinskaya, G.A., “The Wetting of Refractory Carbides, Borides, and Nitrides by Molten Metals” (in Russian), Poroshk. Metall. (Kiev), 43 (7), 53–55 (1966) (Experimental, Interface Phenomena, 5) Gladyshevsky, E.I., Kuzma, Yu.B., Kripyakevich, P.I., Skolozdra, R.V., Voroshilov, Yu.V., “Phase Equilibria in Some Ternary Systems Containing a Transition Metal” in “Diagrammy Sostoyaniya Metallicheskih Sistem”, Nauka, Moscow, 70–79 (1968) (Crys. Structure, Phase Relations, Experimental, 25) Kardonskiy, V.M., “Ageing of Fe-Mo and Fe-Mo-Si Alloys”, Phys. Met. Metallogr. (Engl. Transl.), 27(5), 127–131 (1969), translated from Fiz. Met. Metalloved., 27(5), 890–894 (1969) (Crys. Structure, Morphology, Phase Relations, Phase Relations, Experimental, Mechan. Prop., 18) Teslyuk, M.Yu., “Intermetallic Compounds with Structure of Laves Phases” (in Russian), Nauka, Moscow, 1–138 (1969) (Crys. Structure, Phase Diagram, Phase Relations, Review, Theory, 312) Guillermet, A.F., “An Assessment of the Fe-Mo System”, Calphad, 6(2), 127–140 (1982) (Phase Diagram, 39) Guillermet A.F., “The Fe-Mo (Iron-Molybdenum) System”, Bull. Alloy Phase Diagrams, 3(3), 359–367 (1982) (Crys. Structure, Phase Diagram, Assessment, Thermodyn., Calculation, Phys. Prop., 40) Kubaschewski, O., “Iron-Silicon” in “Iron Binary Phase Diagrams”, Springer-Verlag, Berlin, Heidelberg New York Verlag Stahleisen m.b.H. Düsseldorf, 136–139 (1982) (Phase Diagram, Review, #, *, 23) Raynor, G.V., Rivlin, V.G., “Critical Evaluation of Constitution of Iron-Molybdenum-Silicon Alloys”, Inter. Met. Rev., 30(2), 68–84 (1985) (Phase Diagram, Assessment, 31) Andersson, J.-O., “A Thermodynamic Evaluation of the Fe-Mo-C System”, Calphad, 12(1), 9–23, (1988) (Phase Diagram, Thermodyn., Assessment, 45) Kumar, K.C.H., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys”, J. Alloy Phase Diagrams, 4(1), 53–71 (1988) (Phase Relations, Phase Diagram, Thermodyn., Calculation, 27) Nakamura, H., Tsuya, N., Saito, Y., Katsumata, Y., Harada, Y., “Effect of the Addition of a Third Element in a High Silicon-Iron Alloy”, J. Appl. Phys., 64(10), 5682–5683 (1988) (Crys. Structure, Experimental, Magn. Prop., 3) Raynor, G.V., Rivlin, V.G., “Fe-Mo-Si” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Met. London, 398–413 (1988) (Phase Diagram, Assessment, 9)

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Fe–Mo–Si [1994Rag] [1998Mie] [1998Yi]

[2002You]

[Mas2] [V-C2]

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Raghavan, V., “Fe-Mo-Si (Iron-Molybdenum-Silicon)”, J. Phase Equilib., 15(6), 626 (1994) (Phase Diagram, Review, 2) Miettinen, J., “Approximate Thermodynamic Solution Phase Data for Steels”, Calphad, 22 (2), 275–300 (1998) (Phase Diagram, Thermodyn., Assessment, Calculation, 98) Yi, D., Lai, Z., Li, C., Akselsen O.M., Ulvensoen, J.H., “Ternary Alloying Study of MoSi2”, Metall. Mater. Trans. A, 29A, 119–129 (1998) (Crys. Structure, Morphology, Phase Relations, Experimental, 29) Yousefﬁ, M., Wright, C. S., Jeyacheya, F. M., “Effects of Silicon Addition and Process Conditions Upon α-Phase Sintering, Sinter Hardening, and Mechanical Properties of Fe-1.5Mo Powder”, Powder Metall., 45(1), 53–66 (2002) (Morphology, Phase Relations, Experimental, Phys. Prop., 16) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–N–Nb

1

Iron – Nitrogen – Niobium Viktor Kuznetsov

Introduction The interest to the Fe-N-Nb system stems mainly from the fact that N and Nb are used as components of microalloyed steels with (carbo)nitride strengthening. Therefore attention of investigators was focussed mainly on the solubility of nitrogen and niobium nitrides in both liquid [1960Peh, 1965Eva, 1971Mor, 1975Pom, 1986Mor, 1988Jun] and solid Fe [1962Smi, 1968Mor, 1971Koy, 1973Gul, 1989Bal]. The reviews may be found in [1985Ven, 1987Mor, 2003Rag]. A proper investigation of the phase relations was performed only by Holleck et al. [1967Hol, 1977ElS]; see also the reference book [1984Hol]. They discovered the ternary η phase with composition Nb4–xFe2+xN, which is stable at 1200°C and N2 pressure of 10–8 bar. This phase was found also by [1985Lue] as a product of treatment of the NbFe alloy by H2 gas, containing traces of N2. [1970Rob] found two more ternary phases (but not η) with compositions close to Nb4FeN4 and Nb2FeN2 in the products of nitridation of two Fe-Nb alloys by the ﬂow of ammonia and ammonia + hydrogen mixtures at 650 and 850°C. The results were used to estimate thermodynamic properties of those phases and to predict possible phase equilibria under high N2 activities (up to 5000 atm). Thermodynamic data for activities and heat of solution of N in both solid and liquid phases were derived in virtually all the works that determined N solubility. Brief reviews of Wagner interaction parameter eNbN for melt may be found in [1985Ven] and [1987Mor]. Solubility product of Nb nitrides in liquid was determined by [1965Eva], and in solid Fe by [1962Smi, 1968Mor, 1971Koy, 1989Bal]. Calphad-type analyses were performed both separately for liquid phase [1994Qiu] and fcc phase [1989Bal] and for the whole system [1998Zaj, 2001Lee]. The latter calculation reﬁnes the results of the former one from a perspective of using the calculation results in multicomponent systems, in particular Fe-Nb-Ti-C-N. Many descriptions of the binary and ternary systems were revised from this point of view. Both assessments provide seemingly equally good description of the experimental data for the ternary system itself. Unfortunately, both do not include the η phase, so their results are valid only in the low Nb region. The experimental investigations of the phase relations, thermodynamics and structures of phases are summarized in Table 1. Binary Systems The Fe-N binary is accepted from [Mas2]. The Fe-Nb binary is generally accepted from [1993Bej] with a small correction. We rejected the Nb3Fe2 phase which is claimed by the authors to be metastable. As noted by [1985Lue], this phase is most probably stabilized by nitrogen and/or oxygen. The accepted version is presented in Fig. 1. For the N-Nb system the result of the computer assessment by [1996Hua] seems to be sufﬁcient for the purpose of this review, though in principle phase relations may be more complicated, especially at lower temperatures [2000Len]. The version of [1996Hua] however is able to account for all the results obtained in the ternary system. It is accepted and presented in Fig. 2. Solid Phases Crystallographic data for the solid phases are presented in Table 2. The ternary η phase, denoted further as τ1, was found by [1967Hol] at the Nb4Fe2N composition and independently by [1985Lue] at the composition of Nb3Fe3N. Its equilibria with the binary phases were studied by [1977Els]. The compositions found by [1967Hol] and [1985Lue] are the ends of the homogeneity region as found by [1977Els]. This phase has the well-known “high-speed steel carbide” Fe3W3C type structure. Both [1977Els] and [1985Lue] found this phase to exist even at very low N2 pressure (∼10–8 bar).

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The phases τ2 (Nb4FeN4) and τ3 (Nb2FeN2), found by [1970Rob], exist only at high N2 pressure (about 2500 to 5000 bar) and probably in the presence of oxygen [1985Ven]. Their existence is tentatively accepted after [1985Ven], but their relations to other phases of the system are quite unclear. The solubility of the third components in the binary compounds was not investigated in much detail, but seems to be negligible. Liquidus, Solidus and Solvus Surfaces The only data for the liquid-solid equilibria are the measurements of the N solubility in Fe-Nb melts. The Nb content being less than about 10 mass%, melts are in equilibrium with N2 gas [1960Peh, 1975Pom]. The solubility of nitrogen in equilibrium with N2 gas at 1 atm is given in Fig. 3. It obeys Sievert’s law for all the compositions studied up to at least p(N2) = 1 atm. Starting from some Nb content depending on the N2 pressure the melt is in equilibrium with NbN1–x. Unfortunately the conditions for precipitation of Nb nitride are known very poorly. Most data suggest that at 1600°C and p(N2) = 1 atm this limit is at about 10 mass% Nb, but [1960Peh] indicates a possible precipitation of NbN yet at 5 mass% Nb at 1606°C. No studies of temperature or pressure dependence of this limit seem to exist, excepting [1965Eva], but in their ﬁgure 1 the pressure units used are not speciﬁed. Their results for NbN1–x solubility also correspond to an unspeciﬁed N2 pressure and cannot be reported here. The composition of precipitating NbN1–x was determined by [1965Eva, 1971Mor, 1986Mor, 1988Jun]. With some scatter the results obtained at p(N2) = 1 atm group nearly x ≈ 0.1, which correspond to the N rich limit of this phase in the accepted version of the N-Nb binary system at about 1600°C; at lower N2 pressures it tends to shift to the N poorer side [1988Jun]. Isothermal Sections Figure 4 presents the isothermal section at 1200°C and N2 pressure of 10–8 bar after [1977Els], modiﬁed by accounting for the ﬁrmly established equilibrium between the (γFe) phase and NbN1–x. This required a replacement of the tie line ε–N2(gas), given in the original ﬁgure as uncertain, by a narrow two-phase region (γFe)+NbN1–x. On the other hand, the tie line ε–NbN1–x is retained, as no η phase were observed in equilibrium with (γFe) solid solutions. Figures 5 to 7 present the solubility of N in Fe-Nb austenite at N activities of 0.25 to 1 atm1/2 respectively at 1300, 1200 and 1100°C, taken from [1989Bal]. These results are expressed by [1989Bal] also in the form of the solubility product of NbN: log(mass% Nb·mass% N) = 3.82 – 9940/T. It is valid for the austenite phase in the full region of its existence. The proposed ternary sections at high N2 activities (up to 5000 atm) and unspeciﬁed temperature (probably 500 to 700°C), compiled by [1985Ven] from the data of [1970Rob], can not be accepted here, as they seem to be based on imprecise estimations of thermodynamic properties of the τ2 and τ3 phases (see Thermodynamics section below). Moreover, those sections do not account for the τ1 phase that is deﬁnitely stable at least at lower N2 pressures [1967Hol, 1977ElS, 1985Lue]. Thermodynamics The values of the Wagner interaction parameter eNNb = ∂logfN/∂ (mass% Nb) in liquid Fe measured by different authors are in good accord. The equation eNNb = –235/T – 0.055 is most commonly accepted [1985Ven]. It is valid for the temperatures 1600 to 2100°C and Nb content up to ∼18 mass% (∼11 at.%). The values of the modiﬁed Wagner interaction parameter εNNb = ∂lnfN/∂XNb (all concentration units are mole fractions) in the austenite phase were extracted by [1989Bal] from their values of the solubility product of NbN. They are found to be –70 ± 8 at 1200°C and –52 ± 6 at 1300°C. Estimation of thermodynamic properties of the phases τ2 and τ3 made by [1970Rob] (the procedure used is described also in [1985Ven]) are based on an arbitrarily estimated value of Δf H of NbFe2 which differs from the actual value by ∼40%. So, these results, as well as based on them estimations of the phase equilibria, are not accepted here.

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Notes on Materials Properties and Applications [1975Ana] found that additions of NbN inhibit austenite grain growth, increasing the temperature at which the process occurs. NbN proved to be more effective than VN. [1995Wu] found signiﬁcant increase of abrasive-wear and corrosion resistance of Nb containing steel after plasma nitridation at 500°C. Miscellaneous [1971Koy] determined the inﬂuence of Mn, Si, Cr, and Ni on the solubility product of NbN in austenite phase at 1100 to 1250°C. [1973Gul] compared the NbN solubility in Fe obtained by electron microscopy and by electrochemical isolation of nitride. The former technique appeared to be more sensitive. [1976Kre] performed a very detailed comparison of several techniques of quantitative determining Nb nitrides and carbonitrides in Fe alloys including comparing the data obtained in two laboratories. [1977Eng] studied kinetics of nitride precipitation in alloys with 0.061% and 0.12% niobium at 550 to 600°C by methods of anelastic damping, resistance, hardness and yield stress. [1981Ers] measured diffusion coefﬁcient and activation energy of diffusion of N in Fe-Nb melts; Nb addition is found to decrease the diffusivity of N in Fe. [1999Bal] estimated theoretically the value of the Wagner interaction parameter εNFe in the Nb based bcc phase at 1200°C; no comparison with experimental data was performed. [2003Sho] performed a detailed statistical treatment of the Fe-N-Nb ternary fcc phase. Authors treated the p-T-C data of [1989Bal] and draw some considerations about interstitial positions preferred by N atoms in the structure.

Table 1.

Investigations of the Fe-N-Nb Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1960Peh]

Sieverts’ method

Melt, 0 to 8 mass% Nb, 1600 to 1700°C, 0.01 to 1 atm N2

[1962Smi]

Chemical analysis of N content in alloys equilibrated with N2 gas, metallography, XRD to estimate composition of NbN1–x

Fcc phase, 0 to 0.92 mass% Nb, 1191 to 1336° C, 1 atm of (N2 + 1% H2) gas mixture

[1965Eva]

Deviation from Sieverts’ law for measuring N solubility, XRD to estimate composition of NbN1–x

Melt, 8 to 18 mass% Nb, 1550 to 1700°C, not speciﬁed pressure of N2

[1967Hol]

Not speciﬁed (probably XRD)

Nb4Fe2N composition

[1968Mor]

Chemical analysis, XRD

Fcc phase and NbN extracted from samples with up to 0.92 mass% Nb, 1000 to 1300°C

[1970Rob]

XRD, chemical analysis

Nitridation of alloy with gross composition 86 mass% Nb with ammonia at 650°C and with 78 mass% Nb by 1:1 mixture of NH3 and H2 at 850°C

[1971Mor]

Equilibration of alloy with N2 gas, XRD to estimate composition of NbN1–x

Melt, up to 30 mass% Nb, 1873 to 1973 K

[1973Gul]

XRD, electron microscopy (comparing results of the two methods)

750 to 1350°C, 0.04 to 0.12 mass% Nb (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1975Pom]

Sieverts’ method

Melt, 1800 to 2100°C, 3.7 to 9.7 mass% Nb, 0.16 to 1.0 atm N2

[1977Els]

XRD, chemical analysis, metallography

1200°C, composition region Nb-NbN-NbFe2

[1977Eng]

Measurements of anelastic damping, resistance, hardness and yield stress

0.061 to 0.12 mass% Nb, 550 to 600°C

[1981Ers]

Rate of absorption of N2 gas

1600°C, up to 8 mass% Nb, diffusion coefﬁcient of N in liquid

[1985Lue]

XRD, chemical analysis

Treatment of alloy FeNb with H2 containing about 0.05 vol% N2 at 1000 to 1200°C

[1986Mor]

XRD of NbN1–x extracted from solidiﬁed sample nitridated in liquid state

Composition of NbN1–x precipitated from alloys with 11.5 to 14.3 mass% Nb at 1813 K and p(N2) = 1 atm

[1988Jun]

XRD of NbN1–x extracted from solidiﬁed sample nitridated in liquid state

Composition of NbN1–x precipitated from alloys with 10 to 20 mass% Nb at 1813 K and p(N2) = 0.2 to 0.6 bar

[1989Bal]

Dynamic gas equilibration, N content by dynamic weight change

Fcc phase, 0.005 to 0.92 mass% Nb, 1100 to 1300°C, p(N2) = 40 to 760 mm Hg

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [V-C2, Mas2]

(αFe) < 912

cI2 Im 3m W

a = 286.65

pure Fe at 25°C [Mas2]

(Nb) < 2469

cI2 Im 3m W

a = 330.04

pure Fe at 25°C [Mas2]

ε, NbFe2 < 1630

hP12 P63/mmc MgZn2

a = 481.7 c = 267.3

32 to 37 at.% Nb [1993Bej] [V-C2] (continued)

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Fe–N–Nb

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

μ, Nb19Fe21 < 1520

hR39 R 3m Fe7W6

Nb2N1–x < 2585

hP9 P 31m V 2N

NbN1–x < 2070

* τ1, Nb4–xFe2+xN

cF8 Fm 3m NaCl

cF112 Fd 3m W3Fe3C

Lattice Parameters [pm]

a = 492.6 c = 268.0

a = 526.3 c = 496.5

5

Comments/References

48 to 52 at.% Nb [1993Bej] [V-C2] temperature region at p(N2) = 1 atm; 0 ≤ x ≤ 0.14 [1996Hua] at x = 0.08 [V-C2]

a = 439.4 a = 437.7 a = 436.2

temperature region at p(N2) = 1 atm; 0 ≤ x ≤ 0.3 [1996Hua] at x ≈ 0 [V-C2] at x = 0.1 [V-C2] at x = 0.16 [V-C2]

a = 1133 a = 1134.7

0 ≤ x ≤ 1 [1967Hol, 1977ElS, 1985Lue] at x = 0 [1967Hol] at x = 1 [1985Lue]

* τ2, Nb4FeN4

h**

a = 519.2 c = 1036

obtained at 650°C in NH3 atmospherea [1970Rob, 1985Ven]

* τ3, Nb2FeN2

-

-

obtained at 850°C in atmosphere of 1:1 NH3+H2 mixturea; diffraction pattern could not be indexed [1970Rob, 1985Ven]

a

note: not stable under ordinary N2 pressures

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Fig. 1. Fe-N-Nb.

Fe–N–Nb

The Fe-Nb phase diagram

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Fe–N–Nb

Fig. 2. Fe-N-Nb.

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The calculated N-Nb phase diagram at 1 atm N2. Dashed lines are N2 isobars [1996Hua]

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Fig. 3. Fe-N-Nb.

Fe–N–Nb

The nitrogen solubility in Fe-Nb alloys in equilibrium with N2 gas (p = 1 atm) at 1600°C

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Fig. 4. Fe-N-Nb.

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Isothermal section at 1200°C

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Fig. 5. Fe-N-Nb. Solubility limit of N in Fe-Nb austenite phase at 1300°C with superimposed N isoactivity lines. Values are p(N2)1/2

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Fig. 6. Fe-N-Nb. Solubility limit of N in Fe-Nb austenite phase at 1200°C with superimposed N isoactivity lines. Values are p(N2)1/2

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Fig. 7. Fe-N-Nb. Solubility limit of N in Fe-Nb austenite phase at 1100°C with superimposed N isoactivity lines. Values are p(N2)1/2

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Fe–N–Nb

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References [1960Peh] Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans. Metall. Soc. AIME, 218, 1088–1101 (1960) (Experimental, Thermodyn., *, #, 32) [1962Smi] Smith, R.P., “The Solubility of Niobium (Columbium) Nitride in γ-Iron”, Trans. Met. Soc. AIME, 224, 190–191 (1962) (Phase Relations, Experimental, 8) [1965Eva] Evans, D.B., Pehlke, R.D., “Equilibria of Nitrogen with Refractory Metals Titanium, Zirconium, Columbium, Vanadium, and Tantalum in Liquid Iron”, Trans. Met. Soc. AIME, 233, 1620–1624 (1965) (Experimental, Phase Relations, Thermodyn., 14) [1967Hol] Holleck, H., Thuemmler, F., “Ternary Complex Carbides, Nitrides, and Oxides with Partially Completed Ti2Ni Structure” (in German), Monatsh. Chem., 98, 133–134 (1967) (Phase Relations, Experimental, *, 1) [1968Mor] Mori, T., Tokizane, M., Yamaguchi, K., Sunami, E., Nakazima, Y., “Thermodynamic Properties of Nb Carbides and Nitrides in Steels” (in Japanese), Tetsu to Hagane, 54, 763 (1968) (Phase Relations, Experimental, 13) [1970Rob] Roberts, W., “Precipitation in Fe-N, Fe-Si-N, and Fe-Nb-N Alloys”, Thesis, Univ. Newcastle upon Tyne, England, (1970) as quoted by [1985Ven] [1971Koy] Koyama, S., Ishii, T., Narita, K., “The effects of Mn, Si, Cr, and Ni on the Reaction of Solution and Precipitation of NbN in Iron Austenite” (in Japanese), J. Jpn. Inst. Met., 35, 698–705 (1971) (Experimental, Phase Relations, Thermodyn., 16) [1971Mor] Morita, Z., Hachisuka, K., Iwanaga, Y., Adachi, A., “The Solubility of Nitrogen and the Equilibrium of Nb-nitride Forming Reaction in Liquid Fe-Nb Alloys” (in Japanese), J. Jpn. Inst. Met., 35, 831–839 (1971) (Experimental, Phase Relations, Crys. Structure, 25) [1973Gul] Gulyaev, A.P., Anashenko, V.N., Karchevskaya, N.I., Larina, O.D., Matrosov, Yu.I., “Solubility of Vanadium and Niobium Nitrides in Iron”, Met. Sci. Heat Treat., 15, 643–645 (1973), translated from Metalloved. Term. Obrab. Met., (8), 6–8 (1973) (Experimental, Phase Relations, 4) [1975Ana] Anashenko, V.N., Karchevskaya, N.I., Fonshtein, N.M., “Mechanism of Grain Growth in Fe-V-N and Fe-Nb-N Alloys”, Metal Science and Heat Treatment, 17, 881–883 (1975), translated from Metalloved. Term. Obrab. Met., 17(10), 62–64 (1975) (Morphology, Experimental, 6) [1975Pom] Pomarin, Yu.M., Grigorenko, G.M., Lakomskiy, V.I., “Solubility of Nitrogen in Liquid Iron Alloys with Vanadium or Niobium”, Russ. Metall., (5), 61–65 (1975), translated from Izv. Akad. Nauk SSSR, Met., (5), 74–77 (1975) (Experimental, Phase Relations, Thermodyn., *, #, 15) [1976Kre] Kretschmer, M., de Boer, J., “The Solubility of NbN in Austenite” (in German), Hoesch. Ber. Forsch. Entwicklwerke, 11, 88–91 (1976) (Phase Relations, Experimental, 5) [1977Els] El-Shabat, M.L., Holleck, H., “Phase Equilibria in the Nb-(Fe, Co, Ni)-N Systems” (in German) in “Kernforschungszentrum Karlsruhe, Annual Report” 124–134 (1977) (Phase Diagram, Phase Relations, Morphology, Experimental, *, #, 21) [1977Eng] Engell, H-J., Grabke, J., “Study of the Formation of Precipitates in Fe-V-N and Fe-Nb-N Alloys at 550°C to 600°C”, Arch. Eisenhuettenwes., 48, 335–339 (1977) (Experimental, Calculation, Kinetics, 4) [1981Ers] Ershov, G.S., Kasatkin, A.A., “Inﬂuence of Alloying Elements on the Diffusion of Nitrogen in Liquid Iron” (in Russian), Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, 13) [1984Hol] Holleck H., “Binary and Ternary Carbide and Nitride Systems of Transition Metals” (in German), Gebrueder Borntraeger, Berlin-Stuttgart, 1984, Sec. 3.2.4 (Phase Diagram, Review, 33) [1985Lue] Lue, F.X., Jack, K.H., “The Occurrence of High-speed Steel Carbide-type η Phases in the Fe-Nb System”, J. Less-Common Met., 114, 123–127 (1985) (Phase Relations, Experimental, *, 12) [1985Ven] Venkatadri, A.S., Ramaswamy, V., “The Iron-Niobium-Nitrogen System”, J. Alloy Phase Diagrams, 1, 19–26 (1985) (Phase Diagram, Thermodyn., Review, 24) [1986Mor] Morita, Z., Kita, Y., Jung, W-G., Yanai, T., “Direct Determination of the Structure of Niobium Nitride in Equilibrium with Liquid Fe-Nb-N Alloy by High Temperature X-ray Diffractometry”, Trans. Jpn. Inst. Met., 27, 167–175 (1986) (Experimental, Crys. Structure, Phase Relations, 13) Landolt-Börnstein New Series IV/11D4

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14 [1987Mor] [1988Jun]

[1989Bal]

[1993Bej] [1994Qiu] [1995Wu]

[1996Hua]

[1998Zaj]

[1999Bal]

[2000Len] [2001Lee]

[2003Rag] [2003Sho] [Mas2] [V-C2]

Fe–N–Nb Morita, Z., Tanaka, T., Yanai, T., “Equilibria of Nitride Forming Reactions in Liquid Iron Alloys”, Metall. Trans. B, 18B, 195–202 (1987) (Review, Thermodyn., 29) Jung, W-G., Kita, Y., Tanaka, T., Morita, Z., “Structure and Thermodynamics of Niobium Nitride in Equilibrium with Liquid Fe-Nb-N Alloy”, Trans. Jpn. Inst. Met., 29, 718–726 (1988) (Experimental, Phase Relations, Crys. Structure, 32) Balasubramanian, K., Kirkaldy, J.S., “Experimental Investigation of the Thermodynamics of Fe–Nb–N Austenite and Nonstoichiometric Niobium Nitride (1373–1673 K)”, Canad. Metall. Quart., 28, 301–315 (1989) (Experimental, Calculation, Phase Diagram, Thermodyn., *, #, 28) Bejarano, J.M.G., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobium Phase Diagram”, Z. Metallkd., 84, 160–164 (1993) (Phase Diagram, Experimental, *, #, 6) Qiu, C., “Thermodynamic Analysis and Evaluation of the Nitrogen Solubility in Liquid Nb and Fe-Nb Alloys”, Z. Metallkd., 85, 222–227 (1994) (Calculation, Thermodyn., 25) Wu, W.P., Lange, K.W., Janke, D., “Wear and Corrosion Resistance of a Plasma-nitrided PM Tool Steel Alloyed with Niobium”, Surf. Coating Technol., 200, 5229–5236 (1995) (Mechan. Prop., Interface Phenomena, Experimental, 16) Huang, W., “Thermodynamic Assessment of the Nb-N System”, Metall. Mater. Trans. A, 27A, 3591–3600 (1996) (Phase Diagram, Phase Relations, Thermodyn., Assessment, Calculation, *, #, 60) Zajac, S., Jansson, B., “Thermodynamics of the Fe-Nb-C-N System and the Solubility of Niobium Carbonitrides in Austenite”, Metall. Mater. Trans. B, 29B, 163–176 (1998) (Assessment, Calculation, Phase Relations, Thermodyn., *, 33) Balabaeva, R.F., Vasil’eva, I.A., Sukhushina, I.S., Alekseev, I.V., “Thermodynamic Properties and Stability of Nb, Ti, Zr, Hf Intermetallics with Small Content of Ttransition Metals and Hydrogen (Nitrogen)” (in Russian), Zh. Fiz. Khim., 73, 1345–1347 (1999) (Calculation, Thermodyn., 6) Lengauer, B., Bohn, M., Wollein, B., Lisak, K., “Phase Reactions in the Nb-N System below 1400°C”, Acta Mater., 48, 2633–2638 (2000) (Phase Relations, Experimental, 14) Lee, B.-J., “Thermodynamic Assessment of the Fe-Nb-Ti-C-N System”, Metall. Mater. Trans. A, 32A, 2423–2439 (2001) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., *, 90) Raghavan, V., “Fe-N-Nb (Iron-Nitrogen-Niobium)”, J. Phase Equilib., 24, 68–69 (2003) (Phase Diagram, Review, 7) Shohoji, N., Monteiro Dias, M.C., “Statistical Thermodynamic Approach to Austenitic Fe1–yNbyNx System”, Mater. Sci. Technol., 19, 429–434 (2003) (Theory, Thermodyn., 28) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–N–Ni

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Iron – Nitrogen – Nickel Pierre Perrot

Introduction Fe-N-Ni system has raised much interest because of the capacity of Fe-Ni alloys, under ammonia, to pick up nitrogen, giving a lot of phases, in which the N/(Fe+Ni) ratio may be as high as 0.5. In these phases, generally metastable, the interstitial N atoms are ordered. Ni is an important constituent of stainless steels and nitriding is a good mean to induce hardening. An extensive review of the phase equilibria may be found in [1984Rag, 1987Rag1]. A Calphad assessment of the ternary system has been carried out by [1991Fri]. More recent experimental investigations on phase equilibria and thermodynamics are gathered in Table 1. Binary Systems The well known Fe-Ni system is accepted from [1991Swa]. The Fe-N phase diagram in the solid state is accepted from the review of [1987Wri]. The Calphad assessment carried out by [1991Fri] and justiﬁed by the model proposed by [1994Fer] give an insight on the phase equilibria under high nitrogen pressures. The N-Ni phase diagram, accepted from [1991Wri], has been thermodynamically assessed by [1991Fri]. The nitrogen solubility in pure liquid Ni at 1600°C, recognized as very low [1960Bus], has been evaluated at 0.001 ± 0.001 mass% N at 1600°C [1960Hum], in good agreement with the value 0.0013 mass% proposed by [1973Ben, 1987Sch] and 0.0019 mass% at 2000°C [1968Wad]. Solid Phases The solid phases are presented in Table 2. Solid nitrides are easily obtained by reacting Fe-Ni alloys under a NH3 current [1949Hah, 1952Sch]. The nitrogen uptake reaches a maximum at 800°C, which is easily explained by the decomposition of NH3 in two steps. In the ﬁrst step: NH3 → N + 1.5 H2 the nitrogen potential in the gaseous phase is governed by the N atoms and the nitrides are easily formed. The second step 2 N → N2 occurs so rapidly above 800°C that NH3 behaves like a mixture (N2 + 3 H2) with a very weak nitridizing power. Iron and nickel nitrides γ’ (Fe4N), ε (Fe3N), ζFe2N and Ni3N are stable. γ’Ni4N, isotypic with γ’ (Fe4N) appears with reaction products between NH3 and Ni between 150 and 250°C; β,Ni4N appears with reaction products between NH3 and Ni between around 260°C. Both modiﬁcations of Ni4N are metastable. The nickel rich solid solutions, metastable, may be prepared by decomposing oxalates under H2-NH3 atmospheres [1999Dia, 1999Li]. The metastable martensite α’ has a composition between Fe and Fe8N [2001Mij] which transforms into the metastable α”Fe16N2 phase. It appears below 200°C by volume diffusion of nitrogen in the α’ martensite [1999Boe]. The solid solutions Fe4–xNixN of γ’Fe4N structure is stable under H2-NH3 atmospheres for 0 ≤ x ≤ 3.33. They can be obtained by thermal decomposition (< 700°C) of coprecipitated oxalates under H2-NH3 atmospheres [1995Li1, 1995Li2]. The atmosphere must be richer in NH3 and the temperature must be lower when the Ni content of the γ’ phase increases, which means that the nickel rich nitrides are stable under higher nitrogen potentials. Ordered γ’Fe3NiN has an antiperowskite structure in which Ni occupy the corners of the cube. Ordered γ’FeNi3N is more difﬁcult to obtain [1996Dia] because of the Ni preference for the corners of the cube. The nickel nitride Ni3N (actually Ni3N1.16) is obtained by reacting Ni or NiO at 500°C under NH3-H2 atmospheres. The solubility of Fe3N in Ni3N seems very low [1960Arn]. The nitride εFe3N is widely non stoichiometric. The hexagonal Fe sublattice loses its symmetry as it takes up N atoms and transforms into that of orthorhombic ζFe2N. Fe in εFe3N may be replaced by Ni up to the composition εFe2.2Ni0.8N [2005Gaj, 2006Gaj]. However, the reaction of NH3 on Ni3Fe between 200 and 450°C [1962Ter] gives successively γ’Ni3FeN, then a hexagonal phase (Ni0.75Fe0.25)3N and a tetragonal phase (Ni0.75Fe0.25)2N. These two last phases are probably metastable. The nickel azide NiN6 is formed by reaction of aqueous HN3 with

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metallic Ni. The metastable nitride Ni2N is observed in ﬁlms prepared by sputtering Ni in N2 + Ar plasmas. The phase Ni3N2 has been reported, but its existence is questionable [1991Wri]. The ternary nitride FeNiN has been prepared [1960Arn] by nitriding the γ’ phase whose ratio Fe / Ni ∼ 1 at 350°C under a NH3 stream. Isothermal Sections In the liquid state, the nitrogen solubility decreases with Ni content of the alloy [1958Kas, 1960Bus, 1960Hum, 1968Wad, 1972Pom, 1973Lak, 1975Koj, 1977Wad, 1982Ish, 1991Sat] and increases with temperature. If iron dissolves 0.0439 mass% N at 1600°C [1960Hum, 1960Peh], the solubility decreases to 0.030 mass% in the Fe-15 mass% Ni alloy [1960Peh]. The nitrogen solubility in various Fe-Ni liquid alloys is shown in Fig. 1. The results of [1968Wad, 1977Wad] have been preferred to those of [1972Pom, 1973Lak] because they agree better with the accepted nitrogen solubilities in pure metals. The solubilities measured by [1968Wad] extrapolated at 1600°C agree with the solubilities measured by [1960Hum] and with those measured by [1975Koj] below 30 mass% Ni. For higher Ni contents, it is probable that the solubilities be too high. [1975Koj] proposes a solubility of 35 ppm in pure Ni at 1600°C instead of 13 ppm [1973Ben]. A careful investigation on the nitrogen solubility in Ni rich liquid alloys [2001Abd] conﬁrms the value of 13 ppm. The liquid (Fe,Ni) alloys obey the Sievert’s law at least up to 5 MPa [1991Sat, 2003Kow]. The following empirical expression for the nitrogen solubility in liquid alloys may be used: log10 (mass% N) = – 1.352 – 0.01534 · (mass% Ni) + 0.5 log10 (pN2/0.1 MPa). This expression, close to that proposed by [1984Rag] agrees with the calculations carried out by [1986Lin] and with the results of [2001Abd, 2003Kow] for the Ni rich alloys. The decrease of the nitrogen solubility due to Ni has also been observed in the austenitic γ phase [1961Wri, 1963Sch, 1983Ko2, 1987Tum, 1990Fei, 1990Sma, 1995Nec]. The nitrogen solubility at 1000°C in γ austenite decreases from 0.026 mass% N in pure Fe to 0.012 mass% N in Fe-25 mass% Ni. When the Ni content of the γ austenite exceeds 70 mass%, the N solubility goes down to 0.0005 mass% or less. A more precise determination of the nitrogen solubility in 5 γ(Fe,Ni) alloys has been carried out [1963Sch] between 900 and 1250°C. The results are reproduced in Fig. 2a. [1964Flo] reported, for the solubility of nitrogen at 1430°C in a Fe-20 mass% Ni alloy, a value of 0.01 mass%. An extrapolation of the preceding curves would lead to a solubility of 0.012 mass%. The nitrogen solubility in γ(Fe,Ni) austenites up to 350 MPa of nitrogen pressure (that is 960 MPa of nitrogen fugacity at 1000°C) has been measured by [1995Nec] between 900 and 1100°C. The results are reproduced at 1000°C in Fig. 2b. [1990Fei] proposes a new method, based on a temperature gradient, to determine in one run, the nitrogen solubility. Its results for two alloys (10 and 20 mass% Ni) are slightly lower than the preceding ones. A statistical model describing the nitrogen solubility in γ(Fe,Ni) alloys has been proposed by [1975Sri] and thermodynamic functions of γ austenites deduced from solubility measurements were derived by [1983Ko1, 1990Zag]. The nitrogen solubility in α ferrite, very low (3·10–5 mass% N at 800°C under 0.1 MPa N2) decreases with the presence of Ni [1968Ima, 1973Sak]. Under high nitrogen potentials, (αFe) may absorb a higher amount of nitrogen, and the nitrogen uptake stops when (αFe) is in equilibrium with Fe4N. Fig. 3 shows the solubility of Fe4N in α(Fe,Ni) alloys up to 5 at.% Ni in the alloy, solubility deduced from internal friction measurements [1968Ima, 1973Sak]. The solubility of Fe4N in α(Fe,Ni) alloys increases with temperature and decreases when the Ni content of the alloy increases. Above 592°C, α(Fe,Ni) is no more in equilibrium with Fe4N, but with the γ phase, and the N content of the α phase decreases when the temperature increases. The isothermal sections at 500°C and 700°C, based on the diagrams calculated by [1991Fri] are reported in Figs. 4 and 5, respectively. The isothermal section at 500°C has been modiﬁed to take into account the fact that the γ’Fe4–xNixN solid solution is experimentally stable for 0 < x < 3.3 instead of 0 < x < 1 as supposed in the assessment. It must be pointed out that [1991Fri] makes the hypothesis of a complete miscibility between εFe3N and Ni3N, which has never been proved experimentally and does not agree with the observations of [1960Arn]. Temperature – Composition Sections The nitrogen solubilities in Fe-Ni alloys under the high nitrogen potentials generated by H2-NH3 atmospheres below 800°C has been investigated by [1970Atk]. For a given nitrogen potential in the gaseous phase, the nitrogen activity coefﬁcient increases and the nitrogen solubility decreases when the nickel DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

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content of the alloy increases. Fig. 6 shows the nickel inﬂuence on the shape of the γ ﬁeld: the (α+γ)/γ and γ/(γ+ε) borders shift towards the low nitrogen border when the nickel content increases. Thermodynamics The enthalpies and Gibbs energies of dissolution of N in solid and liquid alloys are presented in Table 3. The interaction coefﬁcients between Ni and N in liquid iron at 1600°C, (< 20 mass% Ni) were ﬁrst evaluated as eN(Ni) = (∂ log10 fN/∂ (mass% Ni)) = + 0.011 at 1600°C by [1960Hum, 1960Peh, 1982Ish, 1991Sat] and as +0.007 at 1600–1700°C by [1960Mae], with fN = (mass% N in pure Fe) / (mass% N in alloy). A temperature dependent expression, usable around 1600°C was proposed by [1977Lin] in the iron rich liquid alloys: εN(Ni) = (∂ ln γN/∂ xNi) = –2.87 + 10700/T ± 0.5, with γN = (xN in pure Fe)/(xN in alloy). In the nickel rich liquid alloys, [2001Abd] proposes: eN(Fe) = (∂ log10 fN/∂ (mass% Fe))= – 0.0144 at 1600°C, with fN = (mass% N in pure Ni)/(mass% N in alloy). At 1550°C, [2003Kow] measures eN(Fe) = – 0.0163. A temperature dependent expression of εN(Fe) may be used: εN(Fe) = (∂ ln γN/∂ xFe) = 8.92 – 23300/T ± 2, with γN = (xN in pure Ni)/(xN in alloy). Around 1600°C, εN(Ni) > 0: Ni decreases the nitrogen solubility in iron, whereas εN(Fe) < 0: Fe increases the nitrogen solubility in nickel. A more complete discussion on the nitrogen solubility in nickel rich alloys may be found in [1987Sch] and a statistical model of the nitrogen-metal interaction in iron based liquid alloys has been developed by [1994Tan]. The interaction coefﬁcient between Ni and N in γ austenite has been investigated by [1969Hec], which propose, in the temperature range 600–1200°C the following expression: eN(Ni) = – 0.0056 + 32.4/T. This expressions agrees well with the experiment carried out at 1100 and 1200°C by [1990Sma]. By using mole fractions instead of mass%, the interaction parameter in the γ austenite may be expressed by: εN(Ni) =(∂ ln γN/∂ xNi) = – 1.4 + 7900/T, with γN = (xN in pure Fe)/(xN in alloy). This last expression is close to that proposed by [1975Kik]: εN(Ni) = – 1.6 + 8020/T. Notes on Materials Properties and Applications The main experimental investigations are reported in Table 4. Fe4N is a ferromagnetic compound whose Curie temperature (488°C) does not change by introducing Ni4N in solid solution up to the composition Fe3NiN [1955Wie]. Its magnetic moment at saturation, measured at 4.2 K is 2.2 µB per metallic atom, which is very close to that of pure iron, decreases by substituting Ni for Fe [1960Goo, 1998Che, 1999Dia]. In addition, γ’Fe4N presents a very high corrosion resistance [1996Yan] and a good mechanical ductility [1998Kon] which are improved by the presence of Ni in the solid solution. These characteristics give to the solid solutions based on γ’Fe4N a high potential for high density magnetic recording materials [1998Che, 2002Pan]. Fe3NiN presents a strong decrease of magnetization with pressure (the magnetization disappears above 53 MPa), which indicates an Invar-like behavior [1991Mat, 1992Moh] conﬁrmed by thermal expansion measurements. The linear thermal expansion coefﬁcient, although small (αl = 5.4·10–6·K–1), is not as close to zero than that of the Invar alloy Fe65Ni35, which means that the negative magnetic contribution to the thermal expansion (αmag = – 8.6 · 10–6·K–1) does not annihilate totally the positive phonon contribution (αph = + 14.0 · 10–6·K–1). Surface hardening may be obtained by nitriding austenitic steels based on Fe-Ni [1984Bel]. Miscellaneous The presence of Ni in (αFe) up to 5 mass% Ni has a weak inﬂuence on the nitrogen diffusion coefﬁcient [1968Ima] which may be expressed by: DN/cm2·s–1 = 0.0022 exp (– 9 060/T). The nitrogen diffusion coefﬁcient in γ(Fe,Ni) alloys, measured by [1978Gra] between 900 and 1100°C, may be expressed by: D = Do exp (– E/RT ). For pure Fe, Do = 0.70 cm2·s–1, E = 166 kJ·mol–1 For the (Fe + 10 mass% Ni) alloy: Do = 0.56 cm2·s–1, E = 160 kJ·mol–1 For the (Fe + 20 mass% Ni) alloy: Do = 0.132 cm2·s–1, E = 134 kJ·mol–1 Landolt-Börnstein New Series IV/11D4

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The nitrogen diffusion coefﬁcients in the liquid alloys were measured at 1600°C for the whole composition range by [1973Ben, 1975Koj], in the Fe rich alloys by [1981Ers] and between 1550 and 1700°C by [1973Kun, 1979Sig] in the Fe rich alloys. If authors agree to acknowledge an increase of the diffusion coefﬁcients with the nickel content, they differ about the slope of the curve. The results are shown in Fig. 7. A difference of several order of magnitude between the nitrogen diffusion coefﬁcient in pure Fe and in pure Ni is questionable, so, measurements of [1975Koj] which agree with those of [1973Kun, 1979Sig, 1981Ers] are more credible. Mechanical alloying is a powerful technique to make superalloys, metastable phases. Ball milling of a mixture γ’Fe4N + Ni in stoichiometric proportions leads to the hexagonal, metastable phase εFe3NiN [1989Roc] without nitrogen loss. Annealing at 190°C gives the stable γ’Fe3NiN. Table 1.

Investigations of the Fe-N-Ni Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1949Hah, 1952Sch]

XRD, thermal analysis

300–1000°C, Fe-Ni alloys under NH3 atmospheres

[1958Kas, 1960Bus]

Nitrogen solubility measured by the Sievert’s method

1600–1800°C, < 20 mass% Ni, < 0.1 MPa of N2 pressure

[1960Arn]

XRD, magnetic measurement

< 800°C, preparation of Fe4–xNixO4 (0 < x < 3.33) and FeNiN

[1960Hum]

Nitrogen solubility measured by the Sievert’s method

1550–1800°C, 0-100 mass% Ni, < 0.1 MPa of N2 pressure

[1960Mae]

Nitrogen solubility measured by the Sievert’s method

1600–1700°C, < 5 mass% Ni, < 0.1 MPa of N2 pressure

[1960Peh]

Nitrogen solubility measured by Sievert’s and sampling methods

1600°C, < 15 mass% Ni, < 0.1 MPa of N2 pressure

[1961Wri]

Nitrogen solubility measured by sampling method

918–1217°C, 0-100 mass% Ni, 0.1 MPa of N2 pressure

[1963Sch]

Nitrogen solubility measured by sampling method

900–1250°C, < 25 mass% Ni, 0.1 MPa of N2 pressure

[1964Flo]

Nitrogen solubility measured by chemical analysis

1430°C, 20 mass% Ni, 0.1 MPa of N2 pressure

[1968Ima, 1973Sak]

Nitrogen solubility deduced from internal friction measurements

200–800°C, < 5 mass% Ni, 0.1 MPa of N2 pressure

[1968Wad]

Nitrogen solubility measured by chemical analysis

1780–2200°C, 0-100 mass% Ni, 0.1 MPa of N2 pressure

[1969Hec]

Nitrogen activities determination from transport reaction

600–1200°C, < 35 mass% Ni, < 2.2 MPa of N2 pressure

[1970Atk]

Equilibrium of alloys under H2-NH3 and chemical analysis

660–810°C, < 15 mass% Ni, high N potentials (H2-NH3)

[1972Pom]

Nitrogen solubility measured by chemical analysis after quenching

1600–2600°C, 0, 21.5, 59.0 and 100 mass% Ni, < 0.1 MPa (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1973Lak]

Nitrogen solubility measured by chemical analysis after quenching

1600–2600°C, 0, 21.5, 59.0 and 100 mass% Ni, < 0.1 MPa

[1975Kik]

Nitrogen solubility measured by sampling method

900–1250°C, < 25 mass% Ni, 0.1 MPa of N2 pressure

[1975Koj]

Nitrogen solubility and nitrogen diffusion coefﬁcient

1600°C, 0–100 mass% Ni, 0.1 MPa of N2 pressure

[1977Wad]

Nitrogen solubility measured by the Sievert’s method

1450–1700°C, < 20 mass% Ni, 0.1 MPa of N2 pressure

[1982Ish]

Nitrogen solubility measured by the Sievert’s method

1540–1680°C, < 15 mass% Ni, 0.1 MPa of N2 pressure

[1983Ko2]

Nitrogen solubility measured by the sampling method

867–1275°C, < 15 mass% Ni, 0.1 MPa of N2 pressure

[1987Tum]

Nitrogen solubility measured by the sampling method

900–1200°C, < 30 mass% Ni, 0.1 MPa of N2 pressure

[1989Roc]

XRD, SEM, Mössbauer

Mechanical alloying of γ’Fe4N + Ni mixtures, annealing at 190°C

[1990Fei]

Nitrogen solubility measured by a new thermal gradient method

800–1600°C, < 20 mass% Ni, 0.1 MPa of N2 pressure

[1990Sma]

Nitrogen solubility measured by the sampling method

1100–1200°C, < 25 mass% Ni, 0.1 MPa of N2 pressure

[1991Sat]

Nitrogen solubility measured by the Sievert’s method

1600°C, < 25 mass% Ni, < 5 MPa of N2 pressure

[1995Li1, 1995Li2]

XRD, DSC, Mössbauer, thermal decomposition of oxalates

< 700°C, H2-NH3 atmospheres, preparation of (Fe4–xNix)N (x < 2.4),

[1995Nec]

Nitrogen solubility under pressures, sampling method

900–1100°C, < 30 mass% Ni, 3 to 348 MPa of N2 pressure

[2001Abd]

Nitrogen solubility in Ni rich liquid alloys, Sieverts’ method

1600°C, > 80 mass% Ni, 0.1 MPa of N2 pressure

[2003Kow]

Nitrogen solubility under pressures, sampling method

1550°C, 20 to 90 mass% Ni, < 2.5 MPa of N2 pressure

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Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (Fe,Ni) (δFe) 1538–1394 (αFe) (Ferrite) < 912

cI2 Im 3m W

γ, (Fe,Ni) (Austenite) (γFe) 1394–590 (Ni) < 1455

cF4 Fm 3m Cu

α’ (Martensite)

tI6 I4/mmm ThH2

Lattice Parameters [pm]

Comments/References

a = 293.15

pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2, V-C2] dissolves up to 0.4 at.% N at 590°C.

a = 364.67

pure Fe at 915°C [Mas2, V-C2] dissolves up to 10.3 at.% N at 650°C [Mas2]

a = 352.40

α (ferrite) sursaturated with N, obtained from quenched austenite [1999Boe] a = 286.0 c = 314.5

saturated martensite (Fe8N) [2001Mij]

α”Fe16N2

tI* I4/mmn

a = 572 c = 629

ordered fcc structure, metastable [1987Rag2]

γ’, Fe4N < 680

cP5 Pm 3m Fe4N

a = 378.7

19.4 to 20.6 at.% N [1987Rag2] Dissolves Ni4N up to Fe0.7Ni3.3N [1960Arn] [1955Wie, 1960Sta] [1962Ter] Metastable [1999Dia] Metastable [1999Li]

γ’Fe3NiN γ’FeNi3N γ’Fe0.4Ni3.6N γ’Ni4N ε, Fe3N < 580

a= a= a= a= hP10 P6322 Fe3N

379 376.6 374.7 374.5

a = 469.96 ± 0.03 c = 438.04 ± 0.03 a = 471.8 c = 438.8 a = 479.1 c = 441.9 a = 277.9 c = 443.8 a = 275.7 c = 443.4

εFe3–xNixN

15.8 to 33.2 at.% N [1987Rag2] εFe3N at RT [1999Lei] εFe3N1.10 [2001Lei] lattice parameters decrease slightly with decrease in nitrogen content [2001Lei] εFe3N1.39 [2001Lei] x = 0 (εFe3N)[2006Gaj] x = 0.8 (εFe2.2Ni0.8N) [2006Gaj]

ζFe2N < 500

oP12 Pbcn Fe2N

a = 551.2 b = 482.0 c = 441.6

at 25°C [1987Rag2]

βNi4N

t**

a = 372 c = 728

metastable [1991Wri] (continued)

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni

7

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

Ni3N

hP* P6322 or P312

a = 460.7 c = 430.4

actually Ni3N1.16 [1960Goo] stable [1991Wri]

Ni2N

tI6

a = 280 c = 366

[1991Wri]

NiN6 < 252

-

-

azide decomposes [1991Wri]

FeNiN

tP3 P4/mmm FeNiN

a = 283.0 c = 371.3

[V-C2]

Fe3NiN

cP5 Pm 3m CaTiO3

a = 379.0

ordered structure of γ’Fe3NiN [1960Sta] (antiperowskite [1991Mat])

FeNi3N

cP5 Pm 3m Fe3AlC

a = 375.72

ordered structure of γ’FeNi3N (antiperowskite [1996Dia])

Table 3.

Thermodynamic Data of Reaction or Transformation

Reaction or Transformation

Temperature [°C]

Quantity, per mol of atoms [kJ, mol, K]

Comments

Fe4N ⇌ 4 Fe + {N} (in (αFe))

500

ΔrH° = + 23.5

[1968Ima]

½ N2 ⇌ {N} (in αFe95Ni5)

500

ΔrH° = + 38

[1968Ima]

ΔrH° = – 460 ± 2

[1983Ko2]

N (gas) ⇌ {N} (in γ(Fe,Ni)) (< 15 at.% Ni) ½ N2 ⇌ {N} (in Liquid Fe)

2000

ΔrH° = 5.6

[1972Pom]

½ N2 ⇌ {N} (in Liquid Fe79Ni21)

2000

ΔrH° = 7.8

[1972Pom]

½ N2 ⇌ {N} (in Liquid Fe41Ni59)

2000

ΔrH° = 23.0

[1972Pom]

½ N2 ⇌ {N} (in Liquid Fe22Ni78)

1600

ΔrH° = 90.0 ΔrG° = 91.0

[2001Abd]

½ N2 ⇌ {N} (in Liquid Ni)

1600

ΔrH° = 17.6 ΔrG° = 96.6

[2001Abd]

Landolt-Börnstein New Series IV/11D4

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DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

8 Table 4.

Fe–N–Ni Investigations of the Fe-N-Ni Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1955Wie]

XRD, micrography, saturation magnetization

Fe3NiN, magnetic structure, curie temperature,

[1960Goo]

XRD, saturation magnetization

Fe3–xNixN1+δ (0 < x < 3.3, 0 < δ < 0.2) Ni3N1.16, FeNiN

[1960Sta]

XRD, crystal parameters

Fe3–xNixN1+δ (0 < x < 1, 0 < δ < 0.2)

[1962Ter]

Neutron diffraction

200–450°C, Ni3Fe under NH3. Formation of (Ni, Fe)nN phases

[1973Ben]

Diffusion coefﬁcient of nitrogen in liquid Fe-Ni alloys

1600°C, 0-100 mass% Ni

[1973Kun]

Diffusion coefﬁcient of nitrogen in liquid Fe-Ni alloys

1550–1700°C, < 0–35 mass% Ni

[1978Bab]

Electron diffraction, electron microscopy

29 at.% Ni, hardening by nitride precipitation

[1978Gra]

Diffusion coefﬁcient of nitrogen in liquid γ(Fe,Ni) alloys

900–1100°C, < 20 mass % Ni

[1979Sig]

Diffusion coefﬁcient of nitrogen in liquid Fe-Ni alloys

1550–1700°C, < 30 mass% Ni

[1981Ers]

Diffusion coefﬁcient of nitrogen in liquid Fe-Ni alloys

1600°C, < 7 mass% Ni

[1984Bel]

XRD

30 mass% Ni, diffusion layers in surface hardened steels

[1991Mat, 1992Moh]

Ab initio band structure calculations

Fe3NiN, magnetic and electronic structure

[1996Dia]

XRD, Mössbauer

FeNi3N, ordering determination

[1996Yan]

XRD, Mössbauer

γ’Fe4–xNixN (x < 2.4)

[1998Che]

DTA, Mössbauer, magnetization

γ’Fe4–xNixN (x < 2.4)

[1998Kon]

Band structure calculations

γ’Fe4–xNixN (0 < x < 4), density of states, electronic structure

[1999Boe]

XRD, dilatometry, hardness

γ’Fe4N pure and substituted, kinetics of phase transformations

[1999Dia]

XRD, vibrating sample magnetometer

77 and 298 K, γ’Fe4–xNixN (0 < x < 3.6)

[1999Li]

XRD, Mössbauer

γFe1–xNixN and γ’Fe4–xNixN (x < 3.12) comparison of magnetic structures

[1999Pan]

XRD, SEM, Mössbauer, saturation magnetization

Synthesis of nanocrystalline γ(Fe1–xNix)Nδ (δ < 0.003, 0 < x < 1) (continued)

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni

9

Reference

Method/Experimental Technique

Type of Property

[2001Mij]

XRD, SEM, Mössbauer

Epitaxial (Ni,Fe) bilayers, 200–300°C, H2-NH3 atmospheres

[2002Pan]

XRD, SEM, Mössbauer

Nanocrystalline γ’Fe4–xNixN (0.2 < x < 0.8)

[2005Gaj]

XRD, SEM, Mössbauer

Nanocrystalline εFe3–xNixN (0 < x < 0.8)

[2006Gaj]

XRD, Rietveld analysis, TEM, SEM

εFe3–xNix+N, nanostructured particles

Fig. 1. Fe-N-Ni.

Landolt-Börnstein New Series IV/11D4

Nitrogen solubility in liquid (Fe,Ni) alloys under 0.1 MPa of N2

MSIT®

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

10

Fig. 2a. Fe-N-Ni.

Fe–N–Ni

Nitrogen solubility in γ(Fe,Ni) alloys under 0.1 MPa of N2

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni

11

Fig. 2b. Fe-N-Ni. Nitrogen solubility in γ(Fe,Ni) alloys at 1000°C under various N2 pressure

Landolt-Börnstein New Series IV/11D4

MSIT®

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

12

Fig. 3. Fe-N-Ni.

Fe–N–Ni

Nitrogen solubility in α(Fe,Ni) alloys in equilibrium with Fe4N

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni

Fig. 4. Fe-N-Ni.

Landolt-Börnstein New Series IV/11D4

13

Partial isothermal section at 500°C

MSIT®

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

14

Fig. 5. Fe-N-Ni.

Fe–N–Ni

Partial isothermal section at 700°C

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni

Fig. 6. Fe-N-Ni.

Landolt-Börnstein New Series IV/11D4

15

Ni effect on the shape of the γ ﬁeld. The values represent the molar ratio 100 Ni/(Fe + Ni)

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DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

16

Fig. 7. Fe-N-Ni.

Fe–N–Ni

Nitrogen diffusion coefﬁcient in liquid (Fe,Ni) alloys at 1600°C

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ni References [1949Hah] [1952Sch] [1955Wie]

[1958Kas] [1960Arn]

[1960Bus]

[1960Goo]

[1960Hum] [1960Mae]

[1960Peh]

[1960Sta] [1961Wri]

[1962Ter]

[1963Sch]

[1964Flo] [1968Ima]

[1968Wad]

[1969Hec]

[1970Atk]

Landolt-Börnstein New Series IV/11D4

17

Hahn, H., Mühlberg, H., “The Iron-Nickel-Nitrogen System” (in German), Z. Anorg. Chem., 259, 121–134 (1949) (Crys. Structure, Phase Relations, Experimental, 15) Schlüter, W., Mühlberg, H., “The Fe-N-Ni System” (in German), Stahl Eisen, 72(4), 197–198 (1952) (Crys. Structure, Phase Relations, Review, 2) Wiener, G.W., Berger, J.A., “Structure and Magnetic Properties of some Transition Metal Nitrides”, Trans. AIME, 203, 360–368 (1955) (Crys. Structure, Experimental, Morphology, Magn. Prop., 16) Kashyap, V.C., Parlee, N., “Solubility of Nitrogen in Liquid Iron and Iron Alloys”, Trans. Met. Soc. AIME, 212, 86–91 (1958) (Experimental, Phase Relations, 19) Arnott, R.J., Wold, A., “The Preparation and Crystallography of FeNiN and the Series Fe4–xNixN”, J. Phys. Chem. Solids, 15, 152–156 (1960) (Crys. Structure, Phase Relations, Experimental, 11) Busch, T., Dodd, R.A., “The Solubility of Hydrogen and Nitrogen in Liquid Alloys of Iron, Nickel, and Cobalt”, Trans. Met. Soc. AIME, 218, 488–490 (1960) (Experimental, Phase Relations, 16) Goodenough, J.B., Wold, A., Arnott, R.J., “Interpretation of the Magnetic and Crystallographic Properties of Several Iron, Nickel, and Iron-Nickel-Nitrides”, J. Appl. Phys., 31(5), 342S-343S (1960) (Calculation, Crys. Structure, Magn. Prop., 5) Humbert, J.C., Elliott, J.F., “The Solubility of Nitrogen in Liquid Fe-Cr-Ni Alloys”, Trans. Metall. Soc. AIME, 218, 1076–1088 (1960) (Phase Relations, Experimental, Thermodyn., 13) Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron Alloys. II. Effect of Nickel, Cobalt, Molybdenum, Chromium and Vanadium on the Solubility in Liquid Iron” (in Japanese), Tetsu to Hagane, 46(9), 972–976 (1960) (Experimental, Phase Relations, Thermodyn., 8) Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans. Metall. Soc. AIME, 218, 1088–1101 (1960) (Experimental, Phase Relations, Thermodyn., 32) Stadelmaier, H.H., Fraker, A.C., “Nitrides of Iron with Nickel, Palladium, and Platinum”, Trans. Metall. Soc. AIME, 218, 571–572 (1960) (Crys. Structure, Experimental, 1) Wriedt, H.A., Gonzalez, O.D., “The Solubility of Nitrogen in Solid Iron-Nickel Alloys Near 1000°C”, Trans. Met. Soc. AIME, 221, 532–535 (1961) (Experimental, Phase Relations, Thermodyn., 10) Terao, N., “Transformation of Metallic Lattices by Insertion of Nitrogen Atoms. II. Nitriding of Ni-Fe Alloy” (in French), J. Phys. Soc. Jpn. (Supplement), 17(B-II), 242–245 (1962) (Crys. Structure, Experimental, 2) Schenck, H., Frohberg, M.G., Reinders, F., “Contribution to the Study of the Solubility of N in Fe Alloys Over the Temperature Range from 700 to 1200°C” (in German), Stahl Eisen, 83 (2), 93–99 (1963) (Experimental, Phase Relations, 26) Floridis, T.P., Chilcott, W.R., “Solubility of Nitrogen in Solid Iron Alloys at High Temperatures.”, Trans. ASM, 57, 360–361 (1964) (Experimental, Phase Relations, 3) Imai, Y., Masumoto, T., Sakamoto, M., “Effect of Ni on the Solubility and Diffusion of N in α-Fe.”, Sci. Rep. Research Inst. Tohoku Univ., 20A, 1–13 (1968), translated from J. Japan Inst. Met., 31, 1095 (1967) (Experimental, Kinetics, Phase Relations, 18) Wada, H., Gunji, K., Wada, T., “Solubility of Nitrogen in Molten Fe-Ni and Fe-Cr Alloys”, Trans. Iron Steel Inst. Japan, 8, 329–336 (1968), translated from J. Jpn. Inst. Met., 32, 933–938 (1968) (Experimental, Phase Relations, Thermodyn., 18) Heckler, A.J., Peterson, J.A., “The Effect of Nickel on the Activity of Nitrogen in Fe-Ni-N Austenite”, Trans. Metall. Soc. AIME, 245, 2537–2541 (1969) (Experimental, Phase Relations, Thermodyn., 13) Atkinson, D., Bodsworth, C., “Thermodynamic Properties of Nitrogen in Austenitic Iron and Iron-Nickel Alloys.”, J. Iron Steel Inst., 208, 587–593 (1970) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 19) MSIT®

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

18 [1972Pom]

[1973Ben]

[1973Kun]

[1973Lak]

[1973Sak]

[1975Kik] [1975Koj]

[1975Sri] [1977Lin] [1977Wad]

[1978Bab]

[1978Gra] [1979Sig]

[1981Ers]

[1982Ish]

[1983Ko1] [1983Ko2] [1984Bel]

Fe–N–Ni Pomarin, Yu.M., Grigorenko, G.M., Lakomskiy, V.I., Torkhov, G.F., Sherevera, A.V., “Nitrogen Solubility in Iron-Nickel Melts”, Russ. Metall., (4), 19–22 (1972), translated from Izv. Akad. Nauk SSSR, Met., (4), 32–35 (1972) (Experimental, Phase Relations, Thermodyn., 12) Benner, B.R., Parlee, N.A.D., “The Rates of Absorption of Nitrogen in the Stagnant Liquid Fe-Co and Fe-Ni Alloy Systems at 1600°C”, Met. Trans., 4, 370–373 (1973) (Experimental, Interface Phenomena, Kinetics, 20) Kunze, H.-D., “Effect of the Elements Chromium, Manganese, Cobalt, Nickel, Molybdenum and Tungsten on the Diffusion of Nitrogen in Liquid Iron Alloys” (in German), Arch. Eisenhuettenwes., 44(2), 71–80 (1973) (Experimental, Interface Phenomena, 50) Lakomsky, V.I., Grigorenko, G.M., Torkhov, G.F., Pomarin, Yu.M., “Effect of Cr and Ni on the Solubility of N in Fe Alloys at High Temperatures” (in Russian), Vzaimodeistvie Gazrov Metal., 125–134 (1973) (Experimental, Phase Relations, Thermodyn., 18) Sakamoto, M., Imai, Y., “Effects of Co, Ni, Mo, and W on the Solubility of Fe16N2 in α-Iron” (in Japanese), J. Jpn. Inst. Met., 37, 708–714 (1973) (Experimental, Kinetics, Phase Relations, Thermodyn., 9) Kikuchi, M., Tanaka, R., “Activity of Nitrogen in Austenitic Steels” (in Japanese), Tetsu to Hagane, 61(13), 2892–2903 (1975) (Experimental, Phase Relations, Thermodyn., 46) Kojima, Y., Inouye, M., Yamada, Y., “Solubility and Diffusivity of Nitrogen in Liquid IronNickel and Iron-Cobalt Alloys at 1600°C”, Trans. Iron Steel Inst. Jpn., 15, 599–605 (1975), translated from Tetsu to Hagane, 61, 195–201 (1975) (Experimental, Phase Relations, Transport Phenomena, Kinetics, 35) Srinivasan, S.R., Grabke, H.J., “Interpretation of Thermodynamic Data of Fe-Ni-C and FeNi-N Alloys”, Scr. Met., 9(4), 387–390 (1975) (Calculation, Phase Relations, Thermodyn., 5) Lin, R.Y., Chang, Y.A., “Activity-Coefﬁcient of Nitrogen in Binary-Liquid Metal-Alloys”, Metall. Trans. B, 8B(2), 293–300 (1977) (Calculation, Thermodyn., Review, 72) Wada, H., Pehlke, R.D., “Nitrogen Solution and Titanium Nitride Precipitation in Liquid FeCr-Ni Alloys.”, Metall. Trans. B, 8B(5), 443–450 (1977) (Experimental, Phase Relations, Thermodyn., 26) Babenko, N.P., Gavrilova, A.V., Kosolapov, G.F., Tyapkin, Y.D., “Crystal Structure of IronNickel Austenite with High Nitrogen Content Alloyed by Nitride Formers”, Phys. Met. Metallogr., 46(5), 90–97 (1978), translated from Fiz. Met. Metallov., 46(5), 1004–1011 (1978) (Crys. Structure, Electronic Structure, Experimental, 15) Grabke, H.J., Petersen, E.M., “Diffusivity of Nitrogen in Fe-Ni Alloys”, Scripta Metall., 12 (12), 1111–1114 (1978) (Experimental, Kinetics, Transport Phenomena, 15) Sigrist, P., Feichtinger, H.K., Marincek, B., “A New Method for the Determination of Diffusion Coefﬁcients and Solubilities of Gases in Liquid Metals and Alloys” (in German) in “Gases in Metals”, Proc. Conf., Darmstadt, West Germany, 1979, Deutsche Gesellschaft Metallkde, 15–22 (1979) (Transport Phenomena, Experimental, 11) Ershov, G.S., Kasatkin, A.A., “Inﬂuence of Alloying Elements on the Diffusion of Nitrogen in Liquid Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, Kinetics, 13) Ishii, F., Banya, S., Fuwa, T., “Solubility of Nitrogen in Liquid Iron Alloys”, Tetsu to Hagane, 68(10), 1551–1559 (1982) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 43) Ko, C., McLellan, R.B., “Thermodynamics of Ternary Nitrogen Austenites”, Acta Metall., 31 (11), 1821–1827 (1983) (Calculation, Thermodyn., 26) Ko, C., McLellan, B., “Thermodynamics of Ternary Fe-Ni-N-Austenites”, J. Phys. Chem. Solids, 44(7), 685–689 (1983) (Experimental, Thermodyn., 13) Belotskiy, A.V., Danil`chenko, V.E., Kodorn`yu, D., “Crystal Structure of Diffusion Layers of Nitrided Iron-Nickel Single Crystals”, Phys. Met. Metallogr., 58(4), 162–169 (1984), translated from Fiz. Met. Metallov., 58(4), 804–811 (1984) (Crys. Structure, Experimental, 7)

DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–N–Ni [1984Rag] [1986Lin]

[1987Rag1]

[1987Rag2]

[1987Sch]

[1987Tum]

[1987Wri]

[1989Roc]

[1990Fei]

[1990Sma] [1990Zag]

[1991Fri] [1991Mat]

[1991Sat]

[1991Swa]

[1991Wri]

[1992Moh]

[1994Fer]

Landolt-Börnstein New Series IV/11D4

19

Raghavan, V., “The Fe-N-Ni (Iron-Nitrogen-Nickel) System”, Trans. Indian Inst. Met., 37(4), 302–307 (1984) (Crys. Structure, Phase Diagram, Review, 37) Lin, J.-C., Schmid, R., Chang, Y.A., “Comparison of Solution Models for Nonmetallic Solutes in Binary Liquid Alloys: Nitrogen in Fe-Cr and Fe-Ni”, Metall. Trans. B, 17B, 785–789 (1986) (Calculation, Phase Relations, 21) Raghavan, V., “The Fe-N-Ni (Iron-Nitrogen-Nickel) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Techn., Delhi, 1, 195–202 (1987) (Crys. Structure, Phase Diagram, Review, 33) Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) Schürmann, E., Sittard, M., Voelker, R., “Equivalent Inﬂuence of an Alloying Element X on the Hydrogen and Nitrogen Solubility in Ternary and Multicomponent Nickel Based Liquid Alloys” (in German), Z. Metallkd., 78(6), 457–466 (1987) (Calculation, Thermodyn., Review, 53) Tuma, H., Ciznerova, M., Protiva, K., “Activity and Solubility of Nitrogen in the Fe-Ni-N System with up to 30 % Ni at 900–1200°C”, Metallic Materials, 25(1), 25–28 (1987) translated from Kovove Mat. 25(1), 52–59 (1987) (Phase Relations, Experimental, Thermodyn., 10) Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase Diagrams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Thermodyn., Review, *, #, 126) Rochegude, P., Foct, J., “Behaviour of Nitrogen During Mechanical Alloying at Solid Solutions and Iron Nitrides”, Compt. Rend. Acad. Sci. Paris, Ser. 2, 309, 1545–1549 (1989) (Phase Relations, Electronic Structure, Crys. Structure, 9) Feichtinger, H., Zheng, X.-H., Rennhard, C., “Measurements of Nitrogen Solubility in Iron and Iron-Nickel Alloys, Using a New Temperature Gradient Method”, Steel Res., 61(1), 26–29 (1990) (Experimental, Phase Relations, Thermodyn., 16) Small, W.M., “Analysis of Nitrogen Solubility in Austenitic Fe-Cr and Fe-Ni Alloys”, Scr. Metall. Mater., 24(1), 107–110 (1990) (Experimental, Phase Relations, Thermodyn., 13) Zaginaychenko, S.Yu., Matycina, Z.A., Milyan, M.I., “Solubility of Interstitial Impurities of Alloys”, Phys. Met. Metallogr., 70, 60–64 (1990), translated from Fiz. Metal. Metalloved., 70 (9), 63–67, (1990) (Calculation, Phase Relations, 20) Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase Diagram, Assessment, Thermodyn., 36) Matar, S., Mohn, P., Demazeau, G., Schwarz, K., “The Electronic and Magnetic Properties of NiFe3N”, J. Magn. Magn. Mater., 101, 251–252 (1991) (Electronic Structure, Magn. Prop., Calculation, 8) Satir-Kolorz, A.H., Feichtinger, H.K., “On the Solubility of Nitrogen in Liquid Iron and Steel Alloys Using Elevated Pressure”, Z. Metallkd., 82(9), 689–697 (1991) (Phase Relations, Thermodyn., Experimental, 24) Swartzendruber, L., Itkin, V.P., Alcock, C.B., “Fe-Ni (Iron-Nickel)” in “Phase Diagrams of Binary Nickel Alloys”, ASM Ed., Materials Park, OH, 110–132 (1991) (Assessment, Crys. Structure, Phase Diagram, Thermodyn., Review, #, 254) Wriedt, H.A., “N-Ni (Nitrogen-Nickel)” in “Phase Diagrams of Binary Nickel Alloys”, ASM Ed., Materials Park, OH, 213–218 (1991) (Crys. Structure, Phase Diagram, Thermodyn., Review, #, 50) Mohn, P., Schwarz, K., “Calculated Electronic and Magnetic Structure of the Nitrides NiFe3N and PdFe3N”, Phys. Rev. B, 45(8), 4000–4007 (1992) (Calculation, Electronic Structure, Experimental, Magn. Prop., 27) Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System Using the Compound-Energy Model with Prediction of the Vibrational Entropy” Z. Metallkde, 85(3), 154–163 (1994) (Phase Diagrams, Theory, Assessment, 75)

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DOI: 10.1007/978-3-540-78644-3_30 # Springer 2008

20 [1994Tan]

[1995Li1]

[1995Li2] [1995Nec]

[1996Dia]

[1996Yan]

[1998Che] [1998Kon]

[1999Boe]

[1999Dia]

[1999Lei]

[1999Li]

[1999Pan]

[2001Abd]

[2001Lei]

[2001Mij]

[2002Pan]

[2003Kow]

Fe–N–Ni Tanaka, T., Gokcen, N.A., Iida, T., Morita, Z.-I., “Thermodynamic Relationship Between the Enthalpy Interaction Parameter and the Entropy Interaction Parameter in Liquid Iron-Nitrogen Based Ternary Alloys”, Z. Metallkd., 85, 696–700 (1994) (Theory, Thermodyn., 17) Li, F., Yang, J., Xue, D., Zhou, R., “X-ray Diffraction and Mössbauer Studies of the (Fe1–xNix)4N Compounds (0 ≤ x ≤ 0.6)”, J. Magn. Magn. Mater., 151, 221–224 (1995) (Crys. Structure, Phase Relations, Electronic Structure, Experimental, 14) Li, F., Yang, J., Xue, D., Zhou, R., “Preparation of the Single Phase γ’-(Fe1–xNix)4N Compounds (0 ≤ x ≤ 0.6)”, J. Mater. Sci., 30, 4857–4860 (1995) (Experimental, Phase Relations, 10) Nechaev, Yu.S., Omelchenko, A.V., “Solubility of Molecular Nitrogen in Austenite”, Russ. J. Phys. Chem., 69(9), 1408–1413 (1995), translated from Zh. Fiz. Khim., 69(9), 1556–1561 (1995) (Experimental, Phase Relations, 23) Diao, X.G., Li, F.S., Zhao, Z.J., Zhou, S.Q., “Preparation and Characterization of γ’Ni3FeN”, J. Mater. Sci. Lett., 15(18), 1590–1591 (1996) (Crys. Structure, Electronic Structure, Experimental, 7) Yang, J., Xue, D., Zhou, R., Li, F., “Effects of Nitrogen in the (Fe1–xNix)4N Compounds (x < 0.6)”, Phys. Status Solidi A, 153, 307–312 (1996) (Crys. Structure, Electronic Structure, Experimental, 12) Chen, Z.Y., Li, F.S., “Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording”, Hyperfine Interact., 112(1–4), 101–106 (1998) (Experimental, Electronic Structure, Magn. Prop., 14) Kong, Y., Li, F., “Linear Mufﬁn-Tin Orbital Calculation of Local Electronic and Magnetic Properties in (Fe1–xNix)4N (0 < x < 1)”, Phys. Rev. B, 57, 970–977 (1998) (Electronic Structure, Magn. Prop., Calculation, 31) Boettger, A., Mittemeijer, E.J., “Phase Transformations in Iron-Nitrogen Martensites; Role of Elastic Strain Energies”, Mater. Sci. Forum, 318–320, 61–70 (1999) (Kinetics, Mechan. Prop., Experimental, 15) Diao, X.G., Takeuchi, A.Y., Garcia, F., Scorzelli, R.B., Rechenberg, H.R., “Magnetic Properties of Perovskite-type Fe-Ni Nitrides γ’(Fe1–xNix)4N (0 < x < 0.9)”, J. Appl. Phys., 85(8), 4485–4487 (1999) (Crys. Structure, Magn. Prop., Experimental, 13) Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe3N: Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys Compd., 288(1–2), 79–87 (1999) (Experimental, Crys. Structure, 40) Li, F.S., Zhao, Z.J., Diao, X.G., Xue, D.S., “A Comparative Study of the Structural and Magnetic Properties of γFe1–xNix Alloys and their Nitrides γ’(Fe1–xNix)4N”, Phys. Status Solidi A, 174, 255–262 (1999) (Crys. Structure, Electronic Structure, Magn. Prop., Experimental, 17) Panda, R.N., Gajbhiye, N.S., “Magnetic Properties of Nanocrystalline γ (Fe,Ni)-N Nitride Systems”, J. Appl. Phys., 86(6), 3295–3302 (1999) (Crys. Structure, Magn. Prop., Electronic Structure, Experimental, 54) Abdulrahman, R.F., Hendry, A., “Solubility of Nitrogen in Liquid Nickel-Based Alloys”, Metall. Mater. Trans. B, 32B, 1103–1112 (2001) (Phase Relations, Thermodyn., Experimental, 14) Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316, 21–38 (2001) (Experimental, Crys. Structure, 47) Mijiritskii, A.V., Boerma, D.O., “Phase Transformations in Epitaxial Ni/Fe Bilayers Upon Low-Temperature Gaseous Nitriding”, Phys. Rev. B, 64(3), 035410-1/11 (2001) (Crys. Structure, Morphology, Kinetics, Experimental, 51) Panda, R.N., Balaji, G., Gajbhiye, N.S., “Enhancement of Hyperﬁne Fields for Iron Atoms in γ′-Fe4-xNixN (0.2 < x < 0.8) Compounds”, Hyperfine Interact., 141–142, 187–191 (2002) (Electronic Structure, Experimental, 11) Kowanda, C., Speidel, M.O., “Solubility of Nitrogen in Liquid Nickel and Binary Ni-Xi Alloys (Xi = Cr, Mo, W, Mn, Fe, Co) under Elevated Pressure”, Scr. Mater., 48(8), 1073–1078 (2003) (Experimental, Phase Relations, Thermodyn., 31)

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[2006Gaj]

[Mas2] [V-C2]

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Gajbhiye, N.S., Bhattacharyya, S., “Mössbauer Studies of εFe3-xNixN and γ′Fe4–yNiyN Nanoparticles”, Hyperfine Interact., 165, 147–151 (2005) (Electronic Structure, Experimental, Nano, 10) Gajbhiye, N.S., Bhattacharyya, S., Synthesis and Structural Investigation of ε-Fe3–xNixN (0 < x < 0.8) Nanoparticles”, Prog. Cryst. Growth Charact. Mater., 52, 132–141 (2006) (Experimental, Crys. Structure, Morphology, Nano, 16) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–N–Si

1

Iron – Nitrogen – Silicon Pierre Perrot

Introduction Silicon and Nitrogen are unavoidable constituents of steels and the great afﬁnity between both elements leads to the formation of Si3N4, a phase often present in electrical steels, to the detriment of their mechanical and magnetic properties. On the other hand, coherent precipitation of Si3N4 may improve the creep properties of mild steels. Interactions between Si and N in steels are of importance and it is the reason why most experimental works, gathered in Table 1, made on the Fe-N-Si system deals with the solubility of N or Si3N4 in the solid or liquid Fe-Si solutions. Reviews of the phase equilibria may be found in [1984Rag, 1987Rag1, 1992Rog, 1993Rag, 1994McH]. Binary Systems The well known Fe-Si system, accepted from [Mas2] has been thermodynamically assessed by [1991Lac]. The problem of the existence of two ordered phases in the α domain has been raised by [1992Rog], but the experimental work of [2005Ust] gives strong arguments for the stability of both α1 and α2 ordered phases. The Fe-N phase diagram in the solid state is accepted from the review of [1987Wri]. The Calphad assessment carried out by [1991Fri] and justiﬁed by the model proposed by [1994Fer] give an insight on the phase equilibria under high nitrogen pressures. The Si-N phase diagram is accepted from the thermodynamical assessment of [2003Ma]. Solid Phases The solid phases are presented in Table 2. Iron nitrides γ’Fe4N, εFe3N and ζFe2N are stable only under high nitrogen potentials, obtained for instance with H2-NH3 atmospheres at temperatures not higher than 800°C whereas Si3N4 is more easily obtained and has a much wider stability domain. Si3N4 presents two modiﬁcations whose stabilities are very near. In presence of Fe, the metastable modiﬁcation of Si3N4 forms above 1150°C [1994Kum, 2001Vla]. Isothermal Sections The nitrogen solubility in various Fe-Si liquid alloys under 0.1 MPa N2 was ﬁrst shown to increase with the Si content of the alloy up to 2 mass% Si [1947Kar] at 1600°C, then to decrease with higher silicon content, because of the precipitation of Si3N4. This behavior was not conﬁrmed by further measurements [1958Fed, 1960Mae, 1960Peh, 1979Lee, 1982Ish]: the presence of Si decreases the nitrogen solubility in iron and, the precipitation of Si3N4 may be observed only for higher Si content of the melt (for instance, higher than 24 mass% Si at 1600°C). Figure 1 shows the phase equilibria in the iron rich corner at 1600°C under various nitrogen pressures. It comes mainly from [1987Rag1], but the slope of the tie lines in the two-phase region has been modiﬁed because they must converge toward the Si3N4 representative point. The meeting point of the liquidus line with the isobaric curve 105 Pa has been shifted toward higher silicon composition (39 at.%Si instead of 31 at.% Si) to be coherent with the experiment conﬁrmed by the calculations of [1991Ric] whose results are shown in Fig. 2. At a ﬁxed temperature and nitrogen pressure, liquid (Fe,Si) alloys precipitate Si3N4 if their silicon content exceeds a value which can be read on the isobaric curve. The silicon content beyond which Si3N4 precipitates increases with the temperature and decreases when the nitrogen pressure increases. The Fe-N-Si phase diagram has been determined by [1987Wei] at 900 and 1150°C. At 900°C, Si3N4 is in equilibrium with all the solid stable phases of the Fe-Si binary system, namely α, α2, α1, Fe5Si3, FeSi and FeSi2 (r). At 1150°C, Si3N4 is in equilibrium with α (7 to 10 at.% Si), Fe2Si, FeSi and FeSi2 (h). In presence of α (< 7 at.% Si), Si3N4 decomposes in N and Si which gives a solid solution with iron up to 7 at.% Si. The Fe-N-Si diagram at 1150°C is shown in Fig. 3. The experiments have been Landolt-Börnstein New Series IV/11D4

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carried out under evacuated quartz tubes, that is under an unknown nitrogen potential, imposed by the system. Actually, Si3N4 may be in equilibrium with α under high nitrogen potential. The lower limit of the nitrogen potential at equilibrium α-Si3N4 increases when the Si content of the α phase decreases. Pure Fe may be in equilibrium with Si3N4 under an inﬁnite nitrogen potential, which means that pure Fe reacts with Si3N4 to give an α (Fe,Si) solid solution whose composition depends on the imposed nitrogen potential. The solubility of nitrogen in γ (Fe,Si) alloys seems roughly independent of the Si content of the alloy [1951Dar, 1986Kun]. However, the measurements are not easy because of the small extent of the γ ﬁeld. Measurements under H2-NH3 atmospheres [1957Raw, 1957Tur] shows a decrease of the N solubility when increasing the Si content of the alloy. The solubility of nitrogen in α (Fe,Si) alloys in equilibrium with γαﬄ (Fe,Si) or with γ’Fe4N decreases when the Si content of the alloy increases [1955Cor, 1955Lea, 1961Raw, 1963Sch, 1986Kun, 1993Pul]. The precipitation of Si3N4, even under low nitrogen potentials was experimentally observed by [1957Tur]. The results of these authors agree qualitatively because of the difﬁculty, pointed out by [1958Fry] to separate N dissolved in the steel from N precipitated as Si3N4. For instance, at 900°C under 0.1 MPa N2, the nitrogen solubility in a Fe-Si alloy (3 ± 0.1 mass% Si), was measured at 0.0019 mass% N by [1955Cor] which claims no Si3N4 above 700°C, at 0.0011 mass% N in equilibrium with Si3N4 by [1958Fry], at 0.0017 mass% N by [1963Pea], at 0.0093 mass% N by [1969Fie] and at 0.0025 by [1970Mil]. At 1200°C, the nitrogen solubility in the same conditions was measured at 0.0025 mass% N by [1957Tur] and at 0.0030 mass% N by [1969Fie]. The various methods for analyzing N in Fe-Si alloys (chemical analysis, vacuum fusion, isotope dilution) were discussed by [1963Pea]. The possibility of a nitrogen supersaturation in the α phase was also investigated by [1958Sey] which presents a partial isothermal section at 900°C showing the two-phase equilibrium α(Fe,Si)-Si3N4. The iron rich corner of the Fe-N-Si diagram at 600, 800 and 1000°C is shown in Fig. 4. Thermodynamics The interaction coefﬁcients of Si and N in liquid iron at 1600°C, (< 4% Si) were ﬁrst evaluated by [1960Mae, 1960Peh] as eN(Si) = {∂ log10 fN/∂ (mass% Si)} = 0.048, with fN = [(mass% N in pure Fe)/ (mass% N in alloy)], indicating that Si decreases the nitrogen solubility in steels. A more recent evaluation by [1979Lee] gives eN(Si) = 0.057, which corresponds to εN(Si) = {∂ ln γN/∂ xSi} = 7.1, with γN = {(xN in pure Fe)/(xN in alloy)}. [1982Ish] proposes eN(Si) = 0.060. The interaction coefﬁcient of Si and N in α iron at 500°C, (< 2% Si) was measured by [1973Pip] as eN(Si) = 0.5 ± 0.1, which is a very high, hardly credible value, even if [1993Pul] deduces eN(Si) = 0.4 ± 0.1 from lattice measurements. [1986Kun] proposes the following expressions for the interaction coefﬁcients: in the α ﬁeld eN(Si) = 0.010 + (138/T) for T > 1188 K; eN(Si) = – 0.571 + (828/T) for T < 1188 K; in the γ ﬁeld eN(Si) = – 0.110 + (274/T) for 1253 < T/K < 1573. Theoretical discussion of the nitrogen solubility in alloys may be found in [1970Kun] which proposes general equations for the iron rich solutions. The equation of the solvus in equilibrium with Si3N4 is discussed in [1971Rob, 1990Zag]. It is not possible to use the simpliﬁed expression (xSi)3(xN)4 = const. for the solvus, because the activity coefﬁcients of Si and N are strongly dependent on the silicon content of the solution. [1997Mon] develops a statistical thermodynamic model of the solutions FeSixNy which reproduces the decrease of y when x increases under a given nitrogen potential. Notes on Materials Properties and Applications The main experimental investigations are reported in Table 3. N is known to improve the mechanical properties of steels by increasing its hardness and tensile strength and silicon nitride based ceramics are among the most promising materials for structural applications. The sinterability, microstructure and fracture toughness of (FeSi + Si3N4) composites sintered at 1675°C under 60 MPa of hydrostatic pressure, then annealed at 1700°C under 0.2 MPa of N2 have been investigated by [1994Dua]. A density of 99% of the theoretical density and a tendency to increase the K1c (fracture toughness) with the increase of the Si content was reported. The semiconducting phase FeSi2 (r) has been studied as a material for thermoelectric conversion owing to its large Seebeck coefﬁcient, low electrical resistivity and chemical stability. The electronic structure of FeSi1.875N0.125 in which N substitutes Si has been calculated [2002Tan], but it is not clear whether such a compound may be stable. DOI: 10.1007/978-3-540-78644-3_31 # Springer 2008

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Miscellaneous The nitrogen diffusion was investigated in solid [1955Cor, 1955Lea] and liquid [1981Ers] alloys. Although N seems strongly associated with Si in alloys, the nitrogen diffusion coefﬁcient in Fe-Si alloys (< 3 mass% Si) seems independent from the Si content in the solid alloy. In the liquid alloys (up to 8 mass% Si), the presence of Si has for effect to decrease the nitrogen diffusion coefﬁcient and to increase the activation energy of the diffusion. 0.05 at.% N in a Fe0.99Si0.01 matrix reduces by 10% the mobility of the ferrite-austenite interface [2002Kop]. The contact angle between Si3N4 and liquid Fe has been evaluated at 90° by [1966Yas]. The coefﬁcient of mass transfer of gaseous N2 into liquid Fe-Si alloys increases from ∼0.035 cm·s–1 for pure Fe to ∼0.05 cm·s–1 for Fe + 2 mass% Si [1967Cho]. Si reduces the poisonous effect due to adsorption of dissolved oxygen on the molten surface, even if the oxygen content of the alloy is very low (0.002 mass% O).

Table 1.

Investigations of the Fe-N-Si Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1947Kar]

Nitrogen solubility in liquid FeSi alloys

1560–1870°C, < 25 mass% Si, < 0.1 MPa of N2 pressure

[1951Dar]

Nitrogen solubility in γ FeSi alloys, sampling method

930–1350°C, < 5 mass% Si, < 0.03 mass% N, 0.1 MPa N2

[1955Cor]

Nitrogen solubility in α FeSi alloys, sampling method

502–605°C, 0 and 2.83 mass% Si, H2-NH3 atmospheres

[1955Lea]

Nitrogen solubility in α FeSi alloys, internal friction method

250–1000°C, 0 and 2.83 mass% Si, H2-NH3 atmospheres

[1957Raw]

Nitrogen solubility in α and γFeSi alloys, sampling method

700–1000°C, < 2 mass% Si, H2-NH3 atmospheres

[1957Tur]

Nitrogen solubility in α and γFeSi alloys, sampling method

< 1350°C, < 2.83 mass% Si, H2-NH3 and H2-N2 atmospheres

[1958Fed]

Nitrogen solubility in liquid FeSi alloys, sampling method

1580°C, < 25 mass% Si, < 0.1 MPa of N2 pressure

[1958Fry]

Nitrogen solubility in γFeSi alloys, sampling method

800–1100°C, 3.25 mass% Si, 0.1 MPa of N2 pressure

[1958Sey]

Nitrogen solubility in αFeSi alloys, sampling method

750–1000°C, < 12 mass% Si, < 0.1 MPa of N2 pressure

[1959Boo]

XRD, SEM, nitriding and annealing

600–800°C, 3 mass% Si, new phase Si3N4 (structure not given)

[1960Mae]

Nitrogen solubility in liquid FeSi alloys, Sievert’s method

1500–1700°C, < 4 mass% Si, < 0.1 MPa of N2 pressure

[1960Peh]

Nitrogen solubility in liquid alloys, Sievert’s and sampling method

1606°C, < 10 mass% Si, < 0.1 MPa of N2 pressure

[1961Raw]

Nitrogen solubility in α FeSi alloys, internal friction method

600–900°C, < 2 mass% Si, H2-NH3 atmospheres (continued)

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Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1963Sch]

Nitrogen solubility in γ FeSi alloys, Sievert’s method

1000–1200°C, < 1.5 mass% Si, < 0.1 MPa of N2 pressure

[1963Tur]

Solubility of Si3N4 in molten Fe-Si alloys to determine Si activities

1400–1600°C, 0.1 MPa of N2 pressure

[1969Fie]

Nitrogen solubility in α FeSi alloys, sampling method

900–1200°C, 3.1 mass% Si, < 0.6 MPa of N2 pressure

[1970Mil]

Nitrogen solubility in α FeSi alloys, sampling method

800–1050°C, < 8 mass% Si, < 0.1 MPa of N2 pressure

[1973Pip]

Nitrogen solubility in α FeSi alloys, sampling method

400–590°C, < 2 mass% Si, H2-NH3 atmospheres

[1979Lee]

Nitrogen solubility in liquid FeSi alloys, sampling method

1550–1650°C, < 11 mass% Si, 0.1 MPa of N2 pressure

[1982Ish]

Nitrogen solubility in liquid FeSi alloys, sampling method

1540–1680°C, < 3 mass% Si, < 0.1 MPa of N2 pressure

[1986Kun]

Nitrogen solubility in α and γ FeSi alloys, sampling method

< 1300°C, < 3 mass% Si, < 0.1 MPa of N2 pressure

[1987Wei]

XRD on powder mixed in evacuated quartz tubes

900–1150°C, phase equilibria in the SiSi3N4-Fe triangle

[1993Pul]

Nitrogen solubility in α FeSi from lattice dilatation

400–535°C, < 6 mass% Si, H2-NH3 atmospheres

[1994Kum]

XRD, SEM, DTA

< 1200°C, Si + Fe (< 1.5 mass% Fe) nitridized. Transitions in Si3N4

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αFe,δFe)

cI2 Im 3m W

(δFe) 1538–1394 (αFe) < 912 γ, (γFe) (Austenite) 1394–590

cF4 Fm 3m Cu

Lattice Parameters [pm]

Comments/References

a = 293.15

dissolves up to 0.4 at.% N at 590°C and 29.8 at.% Si at 1200°C pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2, V-C2]

a = 364.67

at 915°C [Mas2, V-C2] dissolves up to 10.3 at.% N at 650°C [1987Rag2] and 3.5 at.% Si at 1150°C (continued)

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Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(Si) < 1414

cF8 Fd 3m C (diamond)

a = 543.06

[Mas2] dissolves 0.012 at.% N at 1414°C [2003Ma]

α1Fe3Si

cF16 Fm 3m BiF3

a = 565.54

α ordered structure (D03 structure) [1987Rag1]

α2Fe3Si

cP2 Pm 3m CsCl

a = 281.00

α ordered structure [1987Wei]

Fe2Si 1212–1050

hP6 P 3m1 Mn5Si3

a = 450.52 c = 508.55

33 to 34.5 at.% Si [1992Rog]

Fe5Si3 1060–825

hP16 P63/mcm Mn5Si3

a = 675.52 c = 471.74

38 at.% Si [1992Rog]

FeSi < 1410

cP8 P213 FeSi

a = 448.44

49.5 to 51 at.% Si B20 structure [1987Wei]

βFeSi2 (h) (β-leboite) (Also labelled Fe2Si5) 1220–937

tP3

69.5 to 73 at.% Si [1987Rag1]

P4/mmm βFeSi2

a = 268.72 c = 512.81

69.5 at.% Si [1987Rag1, 1987Wei]

a = 269.37 c = 513.9

73.0 at.% Si [1987Rag1] 66.7 at.% Si [1987Wei]

αFeSi2 (r) (α-leboite) < 982

oC48

a = 987.89

Cmca αFeSi2

b = 780.38 c = 784.08

α”Fe16N2

tI* I4/mmn

a = 572 c = 629

ordered fcc structure, metastable [1987Rag2]

γ’Fe4N < 680

cP5 Pm 3m Fe4N

a = 378.7

19.4 to 20.6 at.% N. Ordered fcc structure [1987Rag2]

ε, Fe3N < 580

hP10 P6322 Fe3N

a = 469.96 ± 0.03 c = 438.04 ± 0.03 a = 471.8 c = 438.8

15.8 to 33.2 at.% N [1987Rag2] εFe3N at RT [1999Lei] εFe3N1.10 [2001Lei] lattice parameters decrease slightly with decrease in nitrogen content [2001Lei] (continued)

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Fe–N–Si

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

a = 479.1 c = 441.9

εFe3N1.39 [2001Lei]

ζFe2N < 500

oP12 Pbcn Fe2N

a = 551.2 b = 482.0 c = 441.6

at 25°C [1987Rag2]

βSi3N4 < 1877 (0.1 MPa N2) ≲ 5000 (10 GPa N2)

hP14 P63/m Si3N4

a = 760.6 ± 0.3 c = 290.9 ± 0.2

stable phase [2003Ma]

αSi3N4

hP28 P 31c αSi3N4

a = 781.8 c = 559.1

metastable, probably stabilized by O [1984Rag] or Fe [1994Kum]

Table 3.

Investigations of the Fe-N-Si Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1967Cho]

Coefﬁcient of mass transfer of N through the liquid surface

1600°C, inﬂuence of Si on the N transfer

[1978Vla]

XRD, SEM, martensitic transformation investigation

5.6 at.% Si, 0.10-0.15 at.% N, annealed 500°C, then cooled

[1979Ben]

XRD, EPMA (Electron Probe Microanalysis)

800–1000°C, diffusion couples between Si3N4 and various steels

[1981Ers]

Diffusion coefﬁcient of N in liquid alloys, volumetric method

1600°C, < 8 mass% Si, 0.1 MPa of N2 pressure

[1983Pul]

Auger electron spectroscopy, Si segregation at the interface

500°C, 3.6 at.% Si (1.85 mass%), H2-NH3 atmospheres

[1994Dua]

XRD, SEM, density, hardness measurements

1500–1700°C, mixtures (Fe,Si) alloys + Si3N4 sintered under 60 MPa

[2000Har]

XRD, grain orientation

Cold rolled and nitridized Fe + 3 mass% Si

[2001Vla]

XRD, SEM, IR spectroscopy, kinetics

1000–1500°C, nitridizing Fe-Si alloys (73 and 88 mass% Si)

[2002Kop]

Dilatometry, mobility of the α/γ interface

750–1000°C, 1 at.% Si, H2-NH3 atmospheres

[2006Chu]

DTA, thermogravimetry, EPMA, surface measurements (BET method)

< 1350°C, 80 mass% Si, combustion synthesis under N2 atmospheres (1 to 10 MPa of N2)

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Fig. 1. Fe-N-Si.

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The iron rich corner at 1600°C under various nitrogen pressures

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Fig. 2. Fe-N-Si. pressures

Fe–N–Si

Compositions of the Fe-Si alloys in equilibrium with Si3N4 under various temperatures and nitrogen

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Fig. 3. Fe-N-Si.

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Isothermal section at 1150°C

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Fig. 4. Fe-N-Si.

Fe–N–Si

The iron rich corner under 0.1 MPa N2 at various temperatures

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Fe–N–Si References [1947Kar]

[1951Dar]

[1955Cor]

[1955Lea]

[1957Raw] [1957Tur]

[1958Fed]

[1958Fry] [1958Sey]

[1959Boo] [1960Mae]

[1960Peh]

[1961Raw] [1963Pea] [1963Sch]

[1963Tur]

[1966Yas]

[1967Cho]

[1969Fie]

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Karnaukhov, M.M., Morozov, A.N., “Kinetics of Nitrogen Dissolution in Liquid Iron and its Alloys with Silicon” (in Russian), Izv. Akad. Nauk SSSR, (Tekhn.), (6), 735–747 (1947) (Experimental, Kinetics, Phase Relations, 14) Darken, L.S., Smith, R.P., Filer, E.W., “Solubility of Gaseous Nitrogen in γ Iron and the Effect of Alloying Constituents-Aluminium Nitride Precipitation”, Trans. Am. Inst. Min. Met. Eng., 191, 1174–1179 (1951) (Experimental, Morphology, Phase Relations, 12) Corney, N.S., Turkdogan, E.T., “The Effect of Alloying Elements on the Solubility of Nitrogen in Iron”, J. Iron Steel Inst., 180, 344–348 (1955) (Experimental, Thermodyn., Phase Relations, 14) Leak, D.A., Thomas, W.R., Leak, G.M., “Diffusion and Solubility of Nitrogen in SiliconIron”, Acta Metall., 3, 501–507 (1955) (Crys. Structure, Experimental, Kinetics, Phase Relations, 21) Rawlings, R., “The Effect of Silicon on the Solubility of Nitrogen in α and γ Iron”, J. Iron Steel Inst., 185, 441–449 (1957) (Experimental, Phase Relations, 12) Turkdogan, E.T., Ignatowicz, S., “Solubility of Nitrogen and Formation of Silicon Nitride in Iron-Silicon Alloys”, J. Iron Steel Inst., 185, 200–206 (1957) (Experimental, Phase Relations, 11) Fedotov, V.P., Samarin, A.M., “The Solubility of Nitrogen in Liquid Iron and in Iron-Silicon Melts”, Sov. Phys.- Dokl., 3(5), 1019–1021 (1958), translated from Dokl. Akad. Nauk SSSR, 122(4), 597–599 (1958) (Experimental, Phase Relations, 6) Fryxell, R.E., Galitzine, N., Gardner, F.S., “Behaviour of Nitrogen in 3% Silicon-Iron”, J. Iron Steel Inst., 189, 327–332 (1958) (Experimental, Morphology, Phase Relations, 21) Seybolt, A.U., “Studies on the Metallurgy of Silicon-Iron. I. Silicon Nitrides. II. Anomaly in the α Solid Solution”, Trans. Met. Soc. AIME, 212, 161–167 (1958) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 16) Booker, G.R., Norbury, J., “A New Nitride Precipitate in Iron-Silicon Alloys”, Nature, 184, 1311–1312 (1959) (Crys. Structure, Experimental, Morphology, 4) Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron alloys. I. Solubility of Nitrogen in Liquid Iron and Effect of Carbon, Silicon and Manganese on the Solubility” (in Japanese), Tetsu to Hagane, 46, 748–753 (1960) (Experimental, Phase Relations, Thermodyn., 14) Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans. Metall. Soc. AIME, 218, 1088–1101 (1960) (Experimental, Phase Relations, Thermodyn., 32) Rawlings, R., Robinson, P.M., “The Solubility of Silicon Nitride in Ferrite”, J. Iron Steel Inst., 197, 306–308 (1961) (Experimental, Phase Relations, Thermodyn., 15) Pearce, M.L., “The Analysis and Solubility of Nitrogen in Silicon-Iron”, Trans. Met. Soc. AIME, 227, 1393–1400 (1963) (Experimental, Phase Relations, 40) Schenck, H., Frohberg, M.G., Reinders, F., “Contribution to the Study of the Solubility of N in Fe Alloys Over the Temperature Range from 700 to 1200°C” (in German), Stahl Eisen, 83 (2), 93–99 (1963) (Experimental, Phase Relations, 26) Turkdogan, E.T., Grieveson, P., Beisler, J.F., “Kinetic and Equilibrium Considerations for Silicon Reaction between Silicate Melts and Graphite-Saturated Iron”, Trans. Met. Soc. AIME, 227, 1258–1265 (1963) (Experimental, Phase Relations, Thermodyn., 29) Yasinskaya, G.A., “The Wetting of Refractory Carbides, Borides, and Nitrides by Molten Metals” (in Russian), Poroshk. Metall. (Kiev), 43(7), 53–55 (1966) (Experimental, Mechan. Prop., 5) Choh, T., Inouye, M., “On the Rate of Absorption of Nitrogen in Liquid Iron and Iron Alloys Containing Carbon, Silicon, Manganese and Chromium” (in Japanese), Tetsu to Hagane, 53 (12), 1393–1406 (1967) (Experimental, Transport Phenomena, 26) Fiedler, H.C., “The Behavior of Nitrogen in 3.1 pct Si-Fe”, Trans. Met. Soc. AIME, 245, 941–945 (1969) (Phase Relations, Morphology, Experimental, 18) MSIT®

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12 [1970Kun]

[1970Mil]

[1971Rob] [1973Pip]

[1978Vla]

[1979Ben]

[1979Lee]

[1981Ers]

[1982Ish] [1983Pul]

[1984Rag] [1986Kun] [1987Rag1]

[1987Rag2]

[1987Wei]

[1987Wri]

[1990Zag]

[1991Fri]

Fe–N–Si Kunze, H.D., Schürmann, E., Parlee, N.A., “Inﬂuence of Temperature and Equivalent Effect of Added Elements on the Solubility, Activity, and Activity Coefﬁcient of Nitrogen in Liquid Iron”, Metall. Trans., 1, 281–290 (1970) (Calculation, Phase Relations, Thermodyn., 45) Milinskaya, I.N., Tomilin, I.A., “Solubility of Nitrogen in the Iron-Silicon Alloys” (in Russian), Izv. Akad. Nauk SSSR, Fiz., 34(2), 255–261 (1970) (Experimental, Phase Relations, Thermodyn., 16) Roberts, W., “The Solubility of Silicon Nitride in α-Iron”, Jernkontorets Ann., 155, 285–287 (1971) (Calculation, Phase Relations, Thermodyn., 16) Pipkin, N.J., Roberts, W., Speirs, D.L., Grieveson, P., Jack, K.H., “Effect of Substitutional Alloying Elements on the Activity Coefﬁcients and Behaviour of Interstitial Solutes in Iron” in “Chemical Metallurgy of Iron and Steel”, Proc. Int. Symp. Metallurgical Chemistry. Applications in Ferrous Metallurgy, Iron Steel Inst., London, 351–352 (1973) (Experimental, Phase Relations, Morphology, Thermodyn., 7) Vlasova, E.N., Molotilov, B.V., “b.c.c. - f.c.c. Martensitic Transformation in Iron-SiliconNitrogen Alloys”, Phys. Met. Metallogr., 45(2), 112–118 (1978), translated from Fiz. Met. Metallov., 45(2), 360–366 (1978) (Crys. Structure, Phase Relations, Experimental, 3) Bennett, M.J., Houlton, M.R., “Interaction Between Silicon-Nitride and Several Iron, Nickel and Molybdenum-Based Alloys”, J. Mater. Sci., 14(1), 184–196 (1979) (Experimental, Phase Relations, Morphology, 6) Leewis, K.G., McLean, A., “Thermodynamics of Nitrogen Dissolution in Liquid Iron-Silicon Alloys”, Canad. Metall. Quart., 18, 333–340 (1979) (Experimental, Phase Relations, Thermodyn., 18) Ershov, G.S., Kasatkin, A.A., “Inﬂuence of Alloying Elements on the Diffusion of Nitrogen in Liquid Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, Thermodyn., 13) Ishii, F., Banya, S., Fuwa, T., “Solubility of Nitrogen in Liquid Iron Alloys”, Tetsu to Hagane, 68(10), 1551–1559 (1982) (Experimental, Phase Relations, Thermodyn., 43) Pulkkinen, R.E.E., Lahdeniemi, M., “Grain-boundary Segregation in Bright Nitrided α -Irons Alloyed with Chromium, Molybdenum and Silicon”, J. Mater. Sci., 18(11), 3421–3426 (1983) (Experimental, Transport Phenomena, Morphology, 12) Raghavan, V., “The Fe-N-Si (Iron-Nitrogen-Silicon) System”, Trans. Indian Inst. Met., 37(6), 665–670 (1984) (Crys. Structure, Phase Diagram, Phase Relations, Review, 27) Kunze, J., Pungun, O., Friedrich, K., “Solubility of Nitrogen in Fe-Si Alloys”, J. Mater. Sci. Lett., 5(8), 815–818 (1986) (Experimental, Phase Relations, Thermodyn., 21) Raghavan, V., “The Fe-N-Si (Iron-Nitrogen-Silicon) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Techn., Delhi, 1, 203–205 (1987) (Crys. Structure, Phase Diagram, Phase Relations, Review, 26) Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) Weitzer, F., Schuster, J.C., “Phase Diagrams of the Ternary Systems Mn, Fe, Co, Ni-Si-N”, J. Solid State Chem., 70(2), 178–184 (1987) (Experimental, Phase Diagram, Phase Relations, 35) Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase Diagrams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Thermodyn., Phase Relations, Review, *, #, 126) Zaginaychenko, S.Yu., Matycina, Z.A., Milyan, M.I., “Solubility of Interstitial Impurities of Alloys”, Phys. Met. Metallogr., 70, 60–64 (1990), translated from Fiz. Metal. Metalloved., (9), 63–67 (1990) (Calculation, Phase Relations, 20) Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 36)

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Fe–N–Si [1991Lac] [1991Ric]

[1992Rog]

[1993Pul]

[1993Rag] [1994Dua]

[1994Fer]

[1994Kum] [1994McH] [1997Mon]

[1999Lei]

[2000Har]

[2001Lei]

[2001Vla]

[2002Kop]

[2002Tan]

[2003Ma]

[2005Ust]

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Lacaze, J., Sundman, B., “An Assessment of the Fe-C-Si System”, Metall. Trans., A, 22A (10), 2211–2223 (1991) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 53) Richter, H.J., Herrmann, M., “Thermodynamic Calculations of Heterogeneous Equilibria in the System Si-Fe-N-O and Si-Fe-N”, J. Mater. Sci. Letters, 10(13), 783–785 (1991) (Calculation, Phase Relations, Thermodyn., 10) Rogl, P., Schuster, J.C., “Fe-Si-N (Iron-Silicon-Nitrogen)” in “Phase Diagrams of Ternary BN and SiN Systems”, Materials Informations Soc., Materials Park, Ohio, 152–155 (1992) (Phase Diagram, Phase Relations, Thermodyn., Review, 21) Pulkkinen, R., “The Activity Coefﬁcients of Nitrogen in α-Irons Alloyed with Chromium, Molybdenum and Silicon”, Scand. J. Metall., 12(2), 87–92 (1993) (Crys. Structure, Phase Relations, Thermodyn., 24) Raghavan, V., “Fe-N-Si (Iron-Nitrogen-Silicon)”, J. Phase Equilib., 14(5), 631 (1993) (Phase Diagram, Phase Relations, Review, 6) Duailibi, J.Fh., Bressiani, J.C., “Effect of Iron Silicon Addition in the Sintering Behavior of Silicon-Nitride”, Key Eng. Mater., 89–91, 253–257 (1994) (Experimental, Mechan. Prop., Morphology, 17) Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System using the Compound-energy Model with Prediction of the Vibrational Entropy”, Z. Metallkd., 85(3), 154–163 (1994) (Phase Diagrams, Phase Relations, Theory, Assessment, 75) Kumar, B., Sen, S.K., “Differential Thermal Analysis of Iron-Containing Silicon-Nitride”, Key Eng. Mater., 89–91, 405–409 (1994) (Experimental, Phase Relations, 12) McHale, A.E., “XII. Silicon Plus Nitrogen Plus Metal”, Phase Diagrams for Ceramists, 10, 48–49, Fig. 8718 (1994) (Phase Diagram, Review, 2) Monteiro-Dias, M.C., Shohoji, N., “A Theory of Suppressed Nitrogen Solubility in Fe-Z-N Ternary Alloy Systems in the Relatively High Range of Concentration of Z (Z = Si or C)”, Mater. Chem. Phys., 50(3), 275–279 (1997) (Theory, Phase Relations, Thermodyn., 20) Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe3N: Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys Compd., 288(1–2), 79–87 (1999) (Experimental, Crys. Structure, Magn. Prop., 40) Harase, J., Shimizu, R., “Inﬂuence of Cold Rolling Reduction on the Grain Boundary Character Distribution and Secondary Recrystallization in Nitrided Fe 3% Si Alloy”, J. Magn. Magn. Mater., 215, 89–91 (2000) (Experimental, Morphology, Phase Relations, Kinetics, 5) Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316, 21–38 (2001) (Experimental, Crys. Structure, 47) Vlasova, M.V., Lavrenko, V.A., Dyubova, L.Y., Gonzalez-Rodriguez, J.G., Kakasey, M.G., “Nitriding of Ferrosilicon Powders”, J. Mater. Synthes. Proces., 9(3), 111–117 (2001) (Experimental, Kinetics, 22) Kop, T.A., Sietsma, J., Van Der Zwaag, S., “The Inﬂuence of Nitrogen on the Austenite/Ferrite Interface Mobility in Fe-1 at.% Si”, Mater. Sci. Eng. A, A323, 403–408 (2002) (Experimental, Transport Phenomena, 11) Tani, J.-I., Kido, H., “Geometrical and Electronic Structures of β-FeSi1.875X0.125 (X = B, Al, N or P)”, Jpn. J. Appl. Phys. 1, 41(11A), 6426–6429 (2002) (Crys. Structure, Electronic Structure, Calculation, 21) Ma, X., Li, Ch., Wang, F., Zhang, W., “Thermodynamic Assessment of the Si-N System”, Calphad, 27(4), 383–388 (2003) (Assessment, Phase Diagram, Phase Relations, Thermodyn., 31) Ustinovshchikov, Yu.I., Sapegina, I.V., “Ordering of Fe-Si Phases”, Inorg. Mater., 41(1), 24–31 (2005), translated from Neorg. Mater., 41(1), 28–35 (2005) (Crys. Structure, Experimental, Phase Relations, 15)

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14 [2006Chu]

[Mas2] [V-C2]

Fe–N–Si Chukhlomina, L.N., Maksimov, Yu.M., Kitler, V.D., Vitushkina, O.G., “Mechanism and Features of Nitriding of Ferrosilicon in the Combustion Regime”, Combustion, Explosion and Shock Waves, 42(3), 309–316 (2006) (Experimental, Kinetics, Morphology, 8) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–N–Ti

1

Iron – Nitrogen – Titanium Pierre Perrot

Introduction Titanium exhibits a strong afﬁnity for non metallic elements (C, N, O, S) and its presence in steels gives rise to a multiplicity of effects. The Fe-N-Ti ternary system is of great interest to clarify the interplay of precipitations in steels. Experimental investigations on phase equilibria and thermodynamics, mainly related to the nitrogen solubilities in liquid, α and γ phases are gathered in Table 1. No experimental ternary phase diagram is known. The only information on the ternary system comes from the thermodynamic assessment been carried out by [1991Oht2, 1998Jon] whereas [1999Dum2, 2001Lee] uses the available solubility measurements to evaluate the iron rich corner of the diagram. A review on the phase equilibria in the Fe-N-Ti system may be found in [1992Rag, 2003Rag]. Binary Systems The Fe-Ti system has been carefully reviewed by [1981Mur] and thermodynamically assessed by [1998Dum]. The Fe-N phase diagram in the solid state is accepted from the review of [1987Wri1]. The Calphad assessment carried out by [1991Fri] and justiﬁed by the model proposed by [1994Fer] give an insight on the phase equilibria under high nitrogen pressures. The N-Ti phase diagram in the solid state given by [Mas2] is reproduced from the extensive review of [1987Wri2]. It is accepted with the exception of the region surrounding the subnitride domain, around the δ’Ti2N3 and Ti2N phases. Indeed, [1991Len] shows, by diffusion experiment that δ’Ti2N3 is metastable and present a diagram in which appears two new stable phases Ti4N3–x and Ti3N2–x. The accepted diagram, showing the new equilibria is reproduced in [1993Oka]. The Calphad assessment carried out by [1991Oht1, 1999Dum1] takes only into account the Ti2N subnitride. A more complex assessment [1996Zen] takes into account the 3 subnitrides Ti4N3, Ti3N2 and Ti2N. Solid Phases The solid phases are shown in Table 2. TiN is a very stable nitride which may be obtained under very low nitrogen potential. Fe2TiN is an intermediate phase which may be prepared as a thin layer on a FeTi alloy (< 2 mass% Ti) at 400–575°C under a 92H2-8NH3 atmosphere [1976Jac] whose nitrogen potential does not allow the iron nitridation. The TiN2 phase, not shown in the table, was described by [1981Pod] as the result of the adsorption of one N per mole of TiN at the interface α(Fe,Ti)-TiN. A more extensive investigation of [1986Ric] shows that, under the same atmosphere, α(Fe,Ti) supersaturates before the precipitation of TiN. Guinier-Preston zones are formed, in which the ratio N/Ti may take any value between 1 and 3. Above 0.5 at.% Ti, Guinier-Preston zones may have the ideal composition Fe4TiN3. Below 0.5 at.% Ti, Ti-N monolayers include Fe to give platelets of composition Fe1–xTixN. The excess of N, in a less stable environment, may be easily reduced by H2. Once the ratio N/Ti = 1, the nitrogen cannot be removed by reduction. Fe may replace Ti in the TiN lattice [1996Kir], and a homogeneous layer of the Fe0.25Ti0.75N composition has been obtained. The diffusion experiment carried out by [1999Pop] shows that TiN may incorporate Fe in its lattice. The metastable phase α”Fe16N2 seems to be stabilized by the addition of 3 to 10 at.% of Ti [1997Wan] which replace Fe in the α” lattice. Liquidus Surface No experimental determination of the liquidus are known. The projection shown in Fig. 1 has been calculated by [1998Jon]. The primary crystallization ﬁeld of TiN predominates owing to the very high stability of TiN. The dashed lines represent the isobaric curves, labelled in log10(p/Pa) which may be interpreted as the pressure needed in order to prevent the system from loosing nitrogen before melting.

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Fe–N–Ti

Isothermal Sections The nitrogen solubility in liquid (Fe,Ti) alloys has been widely investigated as shown in Table 1. Ti enhances the nitrogen solubility in liquid iron, but the increase of the nitrogen dissolved in the melt is limited by the precipitation of TiN which is observed as soon as the solubility product {mass% Ti}{mass% N} (0.002 at 1600°C according to [1995Kun]) be reached. The solubility product of TiN in liquid Fe has been evaluated by [1963Mor, 1965Eva, 1974Fra, 1978Mor, 1987Mor] and the various expressions are in good agreement. An acceptable expression may be that proposed by [1995Kun]: log10 {mass% Ti}{mass% N} = (– 17040/T) + 6.40. The solubility of N in Fe-Ti liquid alloys at 1600, 1700 and 1800°C under various nitrogen pressure is shown in Fig. 2, from [1965Eva, 1978Mor, 1995Bou]. The isobaric curves shown at 1600 and 1700°C are labelled in kPa. The reaction of nitrogen generated by H2-NH3 atmospheres at 400–600°C on α(Fe,Ti) alloys [1981Pod] gives four different species of nitrogen in the alloy: N tightly bound under the form of TiN, nitrogen adsorbed at the α-TiN interface, nitrogen dissolved in the ferrite matrix and nitrogen in the iron nitride phase (γ’Fe4N) observed when the nitrogen potential in the gaseous phase exceeds a threshold limit. The nitrogen solubility in ferrite α(Fe,Ti) is enhanced relative to that of pure Fe, but is limited by the precipitation of TiN. The nitrogen solubility in γ(Fe,Ti) alloys (< 0.3 mass% Ti) was investigated by [1985Wad, 1991Kun, 1998Ino]. Titanium, up to 0.007 mass%, increases slightly the nitrogen solubility. For higher Ti content, TiN precipitates. The solubility product of TiN in (γFe), proposed by [1998Ino] is expressed by: log10 {mass% Ti}{mass% N} = (– 14890/T) + 4.35 The solubility product calculated by this relation is 10–5.75 at 1200°C, to be compared with 10–5.86 accepted by [1999Dum2] in its evaluation of the Fe rich corner of the diagram. The nitrogen solubility in γFe is given by: log10 (mass% N) = 0.5 log10 (pN2/bar) + {(539 ± 17)/T} – (2.00 ± 0.01) At 1100°C, (γFe) dissolves 0.025 mass% N under 1 bar (0.1 MPa) of N2 and TiN precipitates when the Ti content of the alloy is higher than 0.00054 mass%. [1991Kun] measured the solubility product of TiN in (δFe) between 1420 and 1510°C: log10 {mass% Ti}{mass% N} = (– 17200/T) + 5.56 Due to the lack of experimental information with the exception of the nitrogen solubilities in α, γ and liquid phases, the isothermal sections have been calculated. The isothermal sections at 800, 1200 and 1600°C, presented in Figs. 3, 4, and 5, respectively, are mainly from [1991Oht2] slightly modiﬁed to take into account the nonstoichiometry of the binary compounds and the solubility of N into (γFe) according to the accepted Fe-N diagram. Although the exact shape of the TiN phase ﬁeld has never been determined, the calculated diagram agrees with the existence of the solid solution Fe0.25Ti0.75N synthesized by [1996Kir]. [1998Jon] presents also isothermal sections at 1200 and 1600°C without solubility of Fe in TiN and by introducing Fe2N, which does not agree with the accepted N-Ti binary system. Temperature – Composition Sections The vertical section at 0.5 mass% Ti, calculated by [1991Oht2], is shown in Fig. 6. It looks like the binary Fe-N calculated by [1991Fri] with an enlarged α domain. The easy precipitation of TiN appears clearly. The isobaric curves have not been calculated, but the nitrogen potentials (0.1 MPa at 1600°C and 0.044 mass% N) increase strongly with the N content. Below 800°C, they may be obtained with H2-NH3 atmospheres, but above this temperature, there is no known mean to impose such high nitrogen potentials. The original diagram [1991Oht2] has been modiﬁed near its rich iron border because the three-phase domain (α + γ + TiN) did not end on the left hand side of the diagram, which is thermodynamically improbable. Thermodynamics The interaction coefﬁcient between N and Ti in liquid iron has been calculated by [1960Mae] from solubility measurements and found eN(Ti) = (∂ log10 fN / ∂ mass% Ti) = – 0.63 at 1700°C where fN = (mass% N in pure Fe/mass% N in the alloy). Such a value, which may seem very negative is conﬁrmed by the measurements of [1961Rao] (–0.93 at 1600°C), [1963Mor] (–0.18 at 1580°C), [1965Eva] (–0.53 at 1600°C DOI: 10.1007/978-3-540-78644-3_32 # Springer 2008

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Fe–N–Ti

3

and –0.27 at 1750°C) and [1978Mor] (–0.60 at 1600°C and –0.44 at 1700°C). A good compromise is the expression proposed by [1987Mor]: eN(Ti) = (–5700/T) + 2.45. Ti presents a great afﬁnity for nitrogen and the presence of Ti in Fe increases the nitrogen solubility up to a solubility limit which is very quickly reached. Above 0.3 mass% Ti in liquid Fe at 1600°C under 0.1 MPa N2, TiN precipitates and the amount of N dissolved in the liquid alloy decreases. Notes on Materials Properties and Applications Main experimental investigations are gathered in Table 3. The effect of Ti on steels have since long been recognized mainly because of the hardening by precipitation of Ti. Nitrogen dissolves in ferrite and TiN precipitates without inducing dislocations [1981Pod], which enhances the mechanical properties (hardness, yield strength) of the steel, a behavior which is not observed with TiC. Nitridizing of steel improve the mechanical properties of the surface and the main techniques use phase vapor deposition, plasma deposition, reactive magnetron sputtering [1996Kir, 1998Kir, 2001Cho] or a pulsed laser technique [2006Lac] which may be used at room temperature. The interaction of N with Ti dispersed in the Fe matrix has been calculated using the Density Functional Theory [2003Kam] whom result agrees well with experimental lattice parameters, Mössbauer spectroscopy and internal friction data. The TiN inclusions in a steel matrix have a shape which, experimentally, is cuboidal or rectangular, which agree with the calculations of [2004Eno]. The larger particles (few μm size) are formed from the liquid phase and the smaller ones (0.1–0.2 μm size) are precipitated from the austenite after the solidiﬁcation. TiN is an important material with applications including wear and resistant corrosion coatings, diffusion barriers and decorative coatings. TiN coatings sputtered by reactive magnetron may incorporate Fe [1996Kir] in the Ti sublattice of the structure.The stress generated by the misﬁt between the coefﬁcient of thermal expansion of the coating and that of the substrate, the microhardness and the defect density of the coating [1998Kir] may be lowered by heat treatment. The stress reduction is governed by the migration of the excess nitrogen. Nanoparticles Fe-TiN composites have been prepared by dc arc-plasma [2002Sak]. The crystal parameter of Fe increases from 286.65 pm for pure Fe to 287.10 for the nanomaterial, which is an indication of incorporation of Ti and N in the Fe lattice. On the other hand, the crystal parameter of the TiN phase remains constant at 424.4 pm. Mechanical alloying [2001Pop] may also be used to obtain supersaturated or metastable phases. Miscellaneous The nitrogen diffusion was investigated in the solid [1991Che] and liquid [1981Ers] alloys. In liquid alloys, Ti has for effect to increase the nitrogen diffusion coefﬁcient and to decrease the activation energy of the diffusion. In solid alloys, Ti increases the activation energy, which is explained by the trapping of N atoms by Ti. In pure (αFe), the N diffusion coefﬁcient is given by: DN/cm2·.s–1 = 0.005 exp(–9260/T), which corresponds to an activation energy of 77 kJ·mol–1. In a Fe added with 0.77 at.% Ti, the N diffusion coefﬁcient is given by: DN/cm2·s–1 = 0.0089 exp(–9900/T), which corresponds to an activation energy of 82.3 kJ·mol–1. The presence of 0.08 mass% Ti in liquid Fe at 1600°C increases by a factor 1.5 the rate of dissolution of N2 by comparison with pure Fe [1995Ono].

Table 1.

Investigations of the Fe-N-Ti Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1960Mae]

Nitrogen solubility in liquid (Fe,Ti) alloys, Sievert’s method

1600–1700°C, < 0.3 mass% Ti, 0.1 MPa of N2 pressure

[1961Rao]

Nitrogen solubility in liquid (Fe,Ti) alloys, Sievert’s method

1600°C, < 0.8 mass% Ti, < 0.1 MPa of N2 pressure (continued)

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Fe–N–Ti

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1963Mor]

Nitrogen solubility in liquid (Fe,Ti) alloys, Sievert’s method

1580–1675°C, < 0.3 mass% Ti, 0.1 MPa of N2 pressure

[1965Eva]

Nitrogen solubility in liquid (Fe,Ti) alloys, Sievert’s method

1600–1750°C, < 0.3 mass% Ti, 0.1 MPa of N2 pressure

[1974Fra]

Nitrogen solubility in liquid (Fe,Ti) alloys, Sievert’s method

1550–1650°C, < 0.5 mass% Ti, < 0.1 MPa of N2 pressure

[1976Jac]

SEM, X-Ray and electron diffraction,

400–575°C, < 2 mass% Ti, H2-NH3 atmospheres

[1978Mor]

Nitrogen solubility in liquid (Fe,Ti) alloys, sampling method

1600–1700°C, < 0.5 mass% Ti, < 0.1 MPa of N2 pressure

[1981Pod]

Nitrogen reaction on α(Fe,Ti) alloys, thermogravimetry, hardness

400–600°C, < 2.1 at.% Ti, H2-NH3 atmospheres

[1985Wad]

Nitrogen solubility in γ (Fe,Ti) alloys, SEM, chemical analysis

1000–1290°C, < 0.3 mass% Ti, < 0.1MPa of N2 pressure

[1991Kun]

Nitrogen solubility in δ (Fe,Ti) alloys, sampling method

1420–1510°C, < 0.2 mass% Ti, 50 and 90 kPa of N2 pressure

[1995Kun]

Zone melting, Secondary Ion Mass Spectroscopy (SIMS)

1420–1510°C, < 1 mass% Ti. N distribution between δ and liquid

[1998Ino]

Solubility product of TiN in γ(Fe,Ti) alloys, diffusion couple technique

1200–1350°C, < 0.5 mass% Ti, < 0.1 MPa of N2 pressure

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

α, (αFe,δFe)

cI2 Im 3m W

(δFe) 1538–1394 (αFe) < 912

Lattice Parameters [pm]

Comments/References

a = 293.15

dissolves up to 0.4 at.% N at 590°C and 10 at.% Ti at 1289°C pure Fe at 1390°C [V-C2, Mas2]

a = 286.65

pure Fe at 25°C [Mas2, V-C2]

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

pure Fe at 915°C [Mas2, V-C2] Dissolves up to 10.3 at.% N at 650°C [1987Wri1] and 0.8 at.% Ti at 1150°C [1998Dum]

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]. Triple point α-γ-ε at 8.4 GPa, 430°C (continued)

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Landolt-Börnstein New Series IV/11D4

Fe–N–Ti

5

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(βTi) 1970–882

cI2 Im 3m W

a = 330.65

[Mas2] dissolves up to 22 at.% Fe at 1085°C and up to 6.2 at.% N at 2020°C

(αTi) < 882

hP2 P63/mmc Mg

a = 295.06 c = 468.35

[Mas2] dissolves up to 0.05 at.% Fe at 595°C [1998Dum] and 23 at.% N at 1050°C

TiFe < 1317

cP2 Pm 3m CsCl

a = 298.80

from 49.7 to 52.5 at.% Ti [1981Mur]

TiFe2 < 1427

hP12 P63/mmc MgZn2

a = 478.57 c = 779.9

26.5 at.% Fe at 1000°C [1981Mur] from 26.5 to 35.2 at.% Ti.

α”(Fe,Ti)16N2

tI* I4/mmn

a = 623 c = 632

10 at.% Ti [1997Wan]

a = 572 c = 629

ordered fcc structure, metastable [1987Wri1]

a = 378.7

19.4 to 20.6 at.% N [1987Rag]. Ordered fcc structure [1987Wri1]

α”Fe16N2 γ’, Fe4N < 680

cP5 Pm3m Fe4N

ε, Fe3N < 580

hP10 P6322 Fe3N

a = 469.96 ± 0.03 c = 438.04 ± 0.03 a = 471.8 c = 438.8 a = 479.1 c = 441.9

15.8 to 33.2 at.% N [1987Rag] εFe3N at RT [1999Lei] εFe3N1.10 [2001Lei] Lattice parameters decrease slightly with decrease in nitrogen content [2001Lei] εFe3N1.39 [2001Lei]

ζFe2N < 500

oP12 Pbcn Fe2N

a = 551.2 b = 482.0 c = 441.6

at 25°C [1987Wri1]

Ti2N < 1080

tP6 P42/mnm Anti-TiO2 (rutile)

a = 494.14 c = 303.75

[1987Sun]

Ti3N2 1103–1066

hR54 R3m Ta2VC2

a = 298.09 ± 0.04 c = 2166.42 ± 0.85

[1986Len1] stable [1991Len]

Ti4N3 1291–1078

hR24 R3m V3C3

a = 297.95 c = 2896.5

[1986Len2] stable [1991Len] (continued)

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6

Fe–N–Ti

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

δ’Ti2N3 < 800

tI12 I41/amd ThSi2

a = 419.8 c = 859.1

∼38 at.% N [1992Rag] Metastable [1991Len]

TiN < 3290 (10 MPa N2) < 3000 (0.1 MPa N2)

cF8 Fm 3m NaCl

a = 424.4

28 to > 50 at.% N at 50 at.% N [1992Rag]

* Fe2TiN

tF*

a = 425 c = 388

[1976Jac]

Table 3.

Investigations of the Fe-N-Ti Materials Properties

Reference

Method/Experimental Technique

Type of Property

[1970Sza]

XRD, internal friction, heat treatment

< 1000°C, < 0.6 mass% Ti, interstitial N – Titanium interactions

[1981Ers]

Diffusion coefﬁcient of N in liquid alloys, volumetric method

1600°C, < 7 mass% Ti, 0.1 MPa of N2 pressure

[1986Ric]

SEM, electron and X-Ray diffraction, internal friction, adsorption

400–750°C, < 2 at.% Ti, H2-NH3 atmospheres. Guinier-Preston zones

[1987Sun]

SEM, TEM, XRD, metallography

Ti0.94Fe0.06 and Ti0.825Fe0.06N0.015, < 800°C, 0.1 MPa N2, martensitic transition

[1991Che]

Auger electron spectroscopy, nitrogen diffusion coefﬁcient

400–600°C, 0.77 at.% Ti, 80 H2 – 20 NH3 atmospheres

[1995Ono]

Isotopic exchange reaction

1600–1750°C, 0.08 mass% Ti, 0.1 MPa of N2 pressure, kinetics of dissolution

[1996Kir]

Reactive magnetron sputtering, Mössbauer, XRD stress analysis

(Ti,Fe)N sputtered on various substrates (Cu,Si), Hard coating

[1997Wan]

TEM, X-Ray and electron diffraction, sputtering

α”(Fe,Ti)16N2 sputtered on NaCl. Thermal stability investigation (< 800°C)

[1998Kir]

XRD, Mössbauer, glow discharge optical spectroscopy

(Ti,Fe)N sputtered on various substrates stress decrease after heat treatment

[1999Pop]

XRD, electron probe microanalysis

1300°C, diffusion couple TiN-Fe

[2000Che]

Mössbauer, TEM, HR-TEM (High Resolution TEM)

Precipitation of TiN in cold rolled nitridized Fe0.94Ni0.04Ti0.02 alloys

[2001Cho]

XRD, TEM, saturation magnetization, permeability, coercitivity

Thin ﬁlms Fe92.3Ti2.1N5.6 obtained by reactive magnetron sputtering (continued)

DOI: 10.1007/978-3-540-78644-3_32 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–N–Ti

7

Reference

Method/Experimental Technique

Type of Property

[2001Pop]

Mössbauer

Fe + TiN, mechanical alloying, formation of metastable phases

[2002Sak]

XRD, TEM, Mössbauer, H2 adsorptiondesorption measurements

Fe + TiN composite nanomaterial with high speciﬁc surface

[2006Lac]

XRD, SEM, HR-TEM, AFM (Atomic Force Microscopy), hardness

TiN deposit at room temperature by the pulsed laser technique

Fig. 1. Fe-N-Ti. Liquidus projection in the TiN primary crystallization ﬁeld. Full lines: isothermal curves (temperatures in °C). Dashed lines: isobaric curves. The pressures are given in log10 (p/Pa)

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8

Fe–N–Ti

Fig. 2. Fe-N-Ti. Solubility of TiC in liquid iron at 1600, 1700 and 1800°C showing some isobaric curves. Pressures are given in kPa

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Landolt-Börnstein New Series IV/11D4

Fe–N–Ti

9

Fig. 3. Fe-N-Ti. The isothermal section at 800°C

Landolt-Börnstein New Series IV/11D4

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10

Fe–N–Ti

Fig. 4. Fe-N-Ti. The isothermal section at 1200°C

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Landolt-Börnstein New Series IV/11D4

Fe–N–Ti

11

Fig. 5. Fe-N-Ti. The isothermal section at 1600°C

Landolt-Börnstein New Series IV/11D4

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12

Fe–N–Ti

Fig. 6. Fe-N-Ti. Vertical section at 0.5 mass% Ti

DOI: 10.1007/978-3-540-78644-3_32 # Springer 2008

MSIT®

Landolt-Börnstein New Series IV/11D4

Fe–N–Ti References [1960Mae]

[1961Rao]

[1963Mor]

[1965Eva]

[1970Sza] [1974Fra]

[1976Jac] [1978Mor]

[1981Ers] [1981Mur] [1981Pod]

[1985Wad]

[1986Len1] [1986Len2] [1986Ric]

[1987Mor]

[1987Rag]

[1987Sun]

[1987Wri1]

Landolt-Börnstein New Series IV/11D4

13

Maekawa, S., Nakagawa, Y., “Solubility of N in Liquid Fe and Fe Alloys” (in Japanese), Tetsu to Hagane, 46(11), 1438–1441 (1960) (Experimental, Phase Relations, Thermodyn., 8) Rao, M.M., Parlee, N., “The Solubility of N in Liquid Fe-V and Fe-Ti Alloys and the Equilibrium in Reaction xTi + N = TixN (⋆)” (in French), Mem. Sci. Rev. Met., 58(1), 52–60 (1961) (Experimental, Phase Relations, 6) Morozov, A.N., Isaev, V.F., Korolev, L.G., “Conditions of Nitride Formation and Solubility of N in Alloys of Fe with Al, Ti and V” (in Russian), Izv. Akad. Nauk SSSR, Met., (4), 141–144 (1963) (Experimental, Phase Relations, Thermodyn., 6) Evans, D.B., Pehlke, R.D., “Equilibria of Nitrogen with Refractory Metals Titanium, Zirconium, Columbium, Vanadium, and Tantalum in Liquid Iron”, Trans. Met. Soc. AIME, 233, 1620–1624 (1965) (Experimental, Phase Relations, Thermodyn., 14) Szabo-Miszenti, G., “Internal Friction in the Fe-N-Ti Alloys”, Acta Metallurg., 18(5), 477–484 (1970) (Electronic Structure, Experimental, 22) Frage, N.R., Gurevich, Yu.G., Tomilov, V.I., “Solubility of N in the Fe-Ti System” (in Russian), Izv. VUZ Chern. Metall, (6), 13–15 (1974) (Experimental, Phase Relations, Thermodyn., 9) Jack, D.H., “The Structure of Nitrided Iron-Titanium Alloys”, Acta Metall., 24, 137–146 (1976) (Crys. Structure, Morphology, Phase Relations, Thermodyn., Experimental, 37) Morita, Z., Kunisada, K., “Solubility of Nitrogen and Equilibrium of Titanium Nitride Forming Reaction in Liquid Fe-Ti Alloys”, Trans. Iron Steel Inst. Jpn., 18, 648–654 (1978), translated from Tetsu to Hagane, 63, 1663–1671 (1977) (Experimental, Phase Relations, Thermodyn., 27) Ershov, G.S., Kasatkin, A.A., “Inﬂuence of Alloying Elements on the Diffusion of Nitrogen in Liquid Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, 13) Murray, J.L., “The Fe-Ti (Iron-Titanium) System”, Bull. Alloy Phase Diagrams, 2(3), 320–334 (1981) (Phase Diagram, Crys. Structure, Thermodyn., Review, 124) Podgurski, H.H., Davis, F.N., “Thermochemistry and Nature of Nitrogen Absorption in Nitrogenated Fe-Ti Alloys”, Acta Metall., 29, 1–10 (1981) (Experimental, Phase Relations, Thermodyn., 16) Wada, H., Pehlke, R.D., “Nitrogen Solubility and Nitride Formation in Austenitic Fe-Ti Alloys”, Metall. Trans. B, 16B, 815–822 (1985) (Experimental, Morphology, Phase Relations, Thermodyn., 16) Lengauer, W., “The Crystal Structure of η-Ti3N2: An Additional New Phase in the Ti-N System”, J. Less-Common Met., 125, 127–134 (1986) (Crystal Structure, Experimental, 19) Lengauer, W., Ettmayer, P., “The Crystal Structure of a New Phase in the Titanium-Nitrogen System”, J. Less-Common Met., 120, 153–159 (1986) (Crystal Structure, Experimental, 24) Rickerby, D.S., Henderson, S., Hendry, A., Jack, K.H., “Structure and Thermochemistry of Nitrided Iron-Titanium Alloys”, Acta Metall., 34(9), 1687–1699 (1986) (Crys. Structure, Morphology, Experimental, Phys. Prop., 29) Morita, Z., Tanaka, T., Yanai, T., “Equilibria of Nitride Forming Reactions in Liquid Iron Alloys”, Metall. Trans. B, 18B, 195–202 (1987) (Assessment, Phase Relations, Thermodyn., Review, 29) Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst. Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7) Sundararaman, D., Mohandas, E., Raghunathan, V.S., Ranganathan, S., “Phase Transformations in Ti-6 a/o Fe and Ti-6 a/o Fe-1.5 a/o N Alloys”, Trans. Indian Inst. Met., 40(3), 249–257 (1987) (Crys. Structure, Electronic Structure, Experimental, Morphology, 21) Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase Diagrams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Thermodyn., Review, *, #, 126) MSIT®

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14 [1987Wri2]

[1991Che]

[1991Fri] [1991Kun] [1991Len]

[1991Oht1] [1991Oht2] [1992Rag]

[1993Oka] [1994Fer]

[1995Bou]

[1995Kun]

[1995Ono]

[1996Kir]

[1996Zen]

[1997Wan]

[1998Dum] [1998Ino] [1998Jon]

Fe–N–Ti Wriedt, H.A., Murray, J.L., “The N-Ti (Nitrogen-Titanium) System”, Bull. Alloy Phase Diagrams, 8(4), 378–388 (1987) (Crys. Structure, Phase Diagrams, Thermodyn., Review, 56) Chen, Y.-X., Zhang, J., Ziliang, W., “Trapping of Nitrogen by Titanium Atoms in α -Fe”, Scr. Metall. Mater., 25(6), 1405–1408 (1991) (Experimental, Morphology, Transport Phenomena, 7) Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase Diagram, Assessment, Thermodyn., 36) Kunze, J., “Solubility of Titanium Nitride in Delta Iron”, Steel Res., 62(10), 430–432 (1991) (Experimental, Phase Relations, Calculation, Thermodyn., 13) Lengauer, W., “The Titanium-Nitrogen System: A Study of Phase Reactions in the Subnitride Region by Means of Diffusion Couples”, Acta Metall. Mat., 39(12), 2985–2996 (1991) (Experimental, Phase Diagram, Phase Relations, 21) Ohtani, H., Hillert, M., “A Thermodynamic Assessment of the Ti-N System”, Calphad, 14(3), 289–306 (1991) (Assessment, Review, Phase Diagram, Phase Relations, Thermodyn., 15) Ohtani, H., Hillert, M., “A Thermodynamic Assessment of the Fe-N-Ti System”, Calphad, 15(1), 41–52 (1991) (Assessment, Phase Diagram, Phase Relations, Thermodyn., 19) Raghavan, V., “The Fe-N-Ti (Iron-Nitrogen-Titanium) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Metals, Calcutta, 6B, 1014–1020 (1992) (Crys. Structure, Phase Diagram, Phase Relations, Review, 16) Okamoto, H., “N-Ti (Nitrogen-Titanium)”, J. Phase Equilib., 14(4), 536 (1993) (Phase Diagram, Review, 8) Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System Using the Compound-energy Model with Prediction of the Vibrational Entropy” Z. Metallkde, 85(3), 154–163 (1994) (Phase Diagrams, Theory, Assessment, 75) Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467–484 (1995) (Phase Relations, Theory, Thermodyn., Review, 85) Kunze, J., Beyer, B., Oswald, S., Gruner, W., “Thermodynamic Data of the Formation of Titanium Nitride in Iron”, Steel Research, 66(4), 161–166 (1995) (Experimental, Theory, Phased Relations, Thermodyn., 28) Ono, H., Morita, K., Sano, N., “Effect of Ti, Zr, V and Cr on the Rate of Nitrogen Dissolution into Molten Iron”, Met. Mat. Trans. B, 26B(5), 991–995 (1995) (Experimental, Kinetics, Interface Phenomena, 11) Kirsten, A., Pietzsch, C., Oettel, H., “Mössbauer Investigations of (Ti,Fe)N Hard Coatings”, Thin Solid Films, 288(1–2), 198–201 (1996) (Crys. Structure, Mechan. Prop., Electronic Structure, Experimental, 10) Zeng, K., Schmid-Fetzer, R., “Critical Assessment and Thermodynamic Modeling of the TiN System”, Z. Metallkd., 87(7), 540–554 (1996) (Assessment, Calculation, Phase Diagram, Thermodyn., 72) Wang, H.Y., Jiang, E.Y., “Enhancement of the Thermal Stability of Fe16N2 by Ti Addition”, J. Phys. Condens. Matter, 9, 2739–2743 (1997) (Experimental, Crys. Structure, Phase Relations, 10) Dumitrescu, L.F.S., Hillert, M., Saunders, N., “Comparison of Fe-Ti Assessments”, J. Phase Equilib., 19(5), 441–448 (1998) (Review, Assessment, Phase Diagram, Thermodyn., 48) Inoue, K., Ohnuma, I., Ohtani, H., Ishida, K., Nishizawa, T., “Solubility Product of TiN in Austenite” ISIJ Int., 38(9), 991–997 (1998) (Experimental, Phase Relations, Thermodyn., 23) Jonsson, S., “Assessment of the Fe-Ti-C System, Calculation of the Fe-Ti-N System, and Prediction of the Solubility Limit of Ti(C,N) in Liquid Fe”, Metall. Mater. Trans. B, 29B, 371–384 (1998) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., 53)

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Fe–N–Ti [1998Kir]

[1999Dum1]

[1999Dum2] [1999Lei]

[1999Pop]

[2000Che]

[2001Cho]

[2001Lee]

[2001Lei]

[2001Pop]

[2002Sak]

[2003Kam]

[2003Rag] [2004Eno]

[2006Lac]

[Mas2] [V-C2]

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Kirsten, A., Pietzsch, C., Oettel, H., “Point Defects in (Ti,Fe)N Hard Coatings, a Mössbauer Study”, Fresenius’ Z. Anal. Chem., 361(6–7), 649–651 (1998) (Crys. Structure, Electronic Structure, Experimental, 12) Dumitrescu, L.F.S., Hillert, M., Sundman, B., “A Reassessment of Ti-C-N Based on a Critical Review of Available Assessments of Ti-N and Ti-C”, Z. Metallkd., 90(7), 534–541 (1999) (Assessment, Phase Relations, Thermodyn., 38) Dumitrescu, L.F.S., Hillert, M., “Reassessment of the Solubility of TiC and TiN in Fe”, ISIJ Int., 39(1), 84–90 (1999) (Assessment, Calculation, Phase Relations, Thermodyn., 39) Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe3N: Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys Compd., 288(1–2), 79–87 (1999) (Experimental, Crys. Structure, 40) Popov, V.V., “Diffusion Interaction of Carbides, Nitrides and Carbonitrides with Iron and Steels”, Metallofizika Nov. Tekhnol., 21(2), 99–103 (1999) (Experimental, Phase Relations, Transport Phenomena, 11) Chechenin, N.G., Bronsveld, P.M., Chezan, A., Craus, C.B., Boerma, D.O., De Hosson, J.T. M., Niesen, L., “TEM Study of Ti-N and Cr-N Precipitate Formation in Iron Alloys”, Phys. Status Solidi A, 177(1), 117–125 (2000) (Electronic Structure, Crystal Structure, Experimental, 19) Choi, H.W., Kim, K.H., Kim, J., Han, S.H., Kim, H.J., “The Effect of Cr Addition on Structure and Corrosion Resistance in FeTiN Nanocrystalline Soft Magnetic Thin Films”, IEEE Trans. Magn., 37(4), 1773–1775 (2001) (Crys. Structure, Experimental, Magn. Prop., 8) Lee, B.-J., “Thermodynamic Assessment of the Fe-Nb-Ti-C-N System”, Metall. Mater. Trans. A, 32A, 2423–2439 (2001) (Assessment, Phase Diagram, Phase Relations, Thermodyn., 90) Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316, 21–38 (2001) (Experimental, Crys. Structure, 47) Popovich, T.A., Arestov, O.V., Popovich, A.A., Kuchma, A.S., “Mössbauer Study of Mechanical Alloying Fe-Ti and Fe-Ti-N Alloys”, J. Mater. Sci. Technol., 17(1), 1–2 (2001) (Phase Relations, Experimental, 2) Sakka, Y., Okuyama, H., Uchikoshi, T., Ohno, S., “Synthesis and Characterization of Fe and Composite Fe-TiN Nanoparticles by dc arc-Plasma”, J. Alloys Compd., 346(1-2), 285–291 (2002) (Crys. Structure, Experimental, Kinetics, Interface Phenomena, Morphology, 27) Kamminga, J.-D., Klaver, T.P.C., Nakata, K., Thijsse, B.J., Janssen, G.C.A.M., “The Interaction of N with Atomically Dispersed Ti, V, Cr, Mo, and Ni in Ferritic Steel”, J. Comp.-Aided Mater. Design, 10(1), 1–11 (2003) (Crys. Structure, Electronic Structure, Theory, 34) Raghavan, V., “Fe-N-Ti (Iron-Nitrogen-Titanium)”, J. Phase Equilib., 24(1), 70–72 (2003) (Phase Diagram, Phase Relations, Review, 12) Enomoto, M., Yang, Z.-G., Nagano, T., “Calculation of the Equilibrium Shape of TiN Particles in Iron”, ISIJ Int., 44(8), 1454–1456 (2004) (Calculation, Morphology, Interface Phenomena, 15) Lackner, J.M., “Growth Structures and Phase Formation in Industrially Room-Temperature Pulsed Laser Deposited FCC Ti-Based Nitride Coatings”, Mat. Sci. Forum, 513, 85–104 (2006) (Crys. Structure, Experimental, Mechan. Prop., Morphology, 77) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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Fe–N–U

1

Iron – Nitrogen – Uranium Vasyl Tomashik

Introduction The investigations of this ternary system are devoted only to the phase diagram of the quasibinary system Fe-UN [1962Kat, 1963Bri, 1966Pri, 1971Guh, 1974Imo]. According to the thermodynamic calculations UN does not react with Fe. The solid-solid reactions of Fe with UN were investigated at elevated temperatures by [1962Kat, 1966Pri]: UN samples showed no signs of reaction after 500 h at 1000°C. [1963Bri] indicated that the system Fe-UN was found to be of simple eutectic type and the eutectic contains 48.5 mass% Fe and crystallizes at 1430 ± 10°C. The later investigations showed that the eutectic temperature is equal to 1395 ± 5°C, eutectic composition being at 49 mass% Fe [1971Guh]. [1974Imo] conﬁrmed that Fe and UN are compatible under the following conditions: at 1000°C in 0.4-33.3 kPa of nitrogen, and at 1400°C in 44 kPa of nitrogen. As the lattice parameter of UN remained unchanged it was suggested that the solubility of Fe in UN is very small. By heating a mixed powder of Fe and UN at 1400°C in a vacuum of 0.013 Pa for 5 h, UFe2 was formed, but the reaction did not occur at 1220°C by heating for 25 h [1974Imo]. Powdered UFe2 interacts with UN at 1000°C in 40 kPa of nitrogen for 5 h forming U2N3 and Fe [1974Imo]: 4UFe2 + 3N2 ⇌ 2U2N3 + 8Fe. Thus there seem to exist as equilibrium the next reactions: UN + 2Fe ⇌ UFe2 + 1/2N2 (1) and/or 2U2N3 + 8Fe ⇌ 4UFe2 + 3N2 (2). The equilibrium pressure for the reaction (1) was estimated to be 0.003 Pa at 1220°C and 0.133 Pa at 1400°C. Therefore the formation of UFe2 is practically impossible below 1400°C and the liquid appears in the Fe-UN quasibinary system at higher temperature [1971Guh]. Investigations of the system are listed in Table 1. Binary Systems Binary systems Fe-N, Fe-U and N-U are accepted from [Mas2]. Solid Phases There are no data about existence of ternary compounds in the Fe-N-U system. Crystallographic data of all unary phases and binary compounds are listed in Table 2. Quasibinary Systems The Fe-UN system was constructed using the data of [1963Bri] and [1971Guh] and it is seen that this quasibinary system is of simple eutectic type with no evidence of solid solubility (Fig. 1). Invariant Equilibria The temperature of 1395°C and the liquid composition of 49 mass% Fe (68.44Fe-15.79U(at.%)) are accepted from [1971Guh] for the three-phase invariant eutectic reaction L ⇌ UN + (γFe). Notes on Materials Properties and Applications Dispersions of UN in Fe have been examined as potential fuel elements for high-temperature nuclear applications [1963Bri]. To localize ﬁssion-product damage it is usually required that the structure consists essentially of discrete particles of the uranium compounds dispersed in a metallic uranium-free matrix.

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2 Table 1.

Fe–N–U Investigations of the Fe-N-U Phase Relations, Structures and Thermodynamics

Reference

Method/Experimental Technique

Temperature/Composition/Phase Range Studied

[1962Kat]

XRD, metallography

1000°C/Fe-UN

[1963Bri]

XRD, metallography

1250–1900°C/Fe-UN

[1966Pri]

Metallography

400–1350°C/Fe-UN

[1971Guh]

XRD, metallography

Fe-UN

[1974Imo]

XRD, measurements of equilibrium pressures of nitrogen

up to 1400°C/Fe-UN

Table 2.

Crystallographic Data of Solid Phases

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

(εFe)

hP2 P63/mmc Mg

a = 246.8 c = 396.0

at 25°C, 13 GPa [Mas2]

(δFe) 1538–1394

cI2 Im 3m W

a = 293.15

at 1390°C [V-C2, Mas2]

(γFe) 1394–912

cF4 Fm 3m Cu

a = 364.67

at 915°C [V-C2, Mas2]

(αFe) < 912

cI2 Im 3m W

a = 286.65

at 25°C [Mas2]

(γU) 1135–776

cI2 Im 3m W

a = 352.4

[Mas2]

(βU) 776–668

tP30 P42/mnm βU

a = 1075.9 c = 565.6

[Mas2]

(αU) < 668

oC4 Cmcm αU

a = 285.37 b = 586.95 c = 495.48

at 25°C [Mas2]

Fe2N ≲ 500

hP9 P 31m V2N

a = 478.7 c = 441.8

[V-C2, Mas2]

Fe3N

hP4 P63/mmc NiAs

a = 270.5 c = 437.6

[V-C2] Mineral siderazot (continued)

DOI: 10.1007/978-3-540-78644-3_33 # Springer 2008

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Fe–N–U

3

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

Fe4N

cP5 Pm 3m TiCaO3

a = 389.6 ± 0.2

[V-C2] Mineral roaldite

Fe4N < 680

cF8 Fm 3m NaCl

a = 379.0 ± 0.1

[V-C2, Mas2]

Fe5N2 (ε-phase)

hP4 P63/mmc NiAs

a = 274.42 ± 0.04 c = 440.25 ± 0.11

[V-C2]

Fe8N ?

tI18 I4/mmm Fe8N

a = 572.0 c = 629.2

[V-C2]

Fe2U < 1228

cF24 Fd 3m MgCu2

a = 706.29

[V-C2, Mas2]

FeU6 < 795

tI28 I4/mcm MnU6

a = 1024.99 ± 0.01 c = 525.00 ± 0.01 a = 1025.36 ± 0.01 c = 524.84 ± 0.01 a = 1026.25 ± 0.01 c = 524.58 ± 0.01 a = 1027.24 ± 0.01 c = 524.36 ± 0.01 a = 1028.63 ± 0.01 c = 524.10 ± 0.01 a = 1030.22 ± 0.01 c = 523.86 ± 0.01

at 20 K at 50 K at 100 K at 150 K at 220 K at 295 K [V-C2, Mas2]

UN < 2805

cF8 Fm 3m NaCl

a = 488.87 ± 0.03

[V-C2, Mas2]

UN(hp)

hR* R 3m ?

a = 316.9 ± 0.4 c = 864.0 ± 1.4

high-pressure phase at 34 GPa [V-C2]

UN2

cF12 Fm 3m CaF2

a = 529.9

[V-C2, Mas2]

βU2N3 1352–940

hP5 P 3m1 La2O3

a = 369.77 ± 0.01 c = 583.3 ± 0.1

[V-C2, Mas2]

(continued)

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DOI: 10.1007/978-3-540-78644-3_33 # Springer 2008

4

Fe–N–U

Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters [pm]

Comments/References

αU2N3 < 1132

cI80 Ia 3 Mn2O3

a = 1068.4 ± 0.1

[V-C2, Mas2]

U4N7

cI96 Ia 3 U4N7

a = 1062.8 ± 0.1

[V-C2]

Fig. 1. Fe-N-U.

Phase diagram of the quasibinary system Fe-UN

DOI: 10.1007/978-3-540-78644-3_33 # Springer 2008

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Landolt-Börnstein New Series IV/11D4

Fe–N–U

5

References [1962Kat] Katz, S., “High Temperature Reactions between Refractory Uranium Compounds and Metals”, J. Nucl. Mater., 6(2), 172–181 (1962) (Experimental, Phase Relations, Thermodyn., 21) [1963Bri] Briggs, G., Guha, J., Barta, J., White, J., “Systems of UC, UC2, and UN with Transition Metals”, Trans. Brit. Ceram. Soc., 62, 221–246 (1963) (Experimental, Morphology, Phase Diagram, Phase Relations, 18) [1966Pri] Price, D.E., Moak, D.P., “The Compatibility of Uranium Nitride with Potential Cladding Metals”, Trans. Amer. Nucl. Soc., 9, 418 (1966) (Experimental, Phase Relations, 0) [1971Guh] Guha, J.P., “Phase Equilibrium Relationships in the System UN-UC-Fe”, J. Nucl. Mater., 41, 187–194 (1971) (Experimental, Phase Diagram, Phase Relations, 15) [1974Imo] Imoto, S., Namba, S., “Thermodynamics Applied to Compatibility of UN with Ni, Cr and Fe”, J. Nucl. Mater., 51, 106–111 (1974) (Experimental, Phase Relations, Thermodyn., 20) [Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) [V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

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DOI: 10.1007/978-3-540-78644-3_33 # Springer 2008