Paint & Coating Industry November 2011

November 2011 VOLUME 27, NUMBER 11

INSIDE Smart Coating for Corrosion Protection

Paint

Coatings Industry

A New Era in Superwetters Nanotechnological Barbwire

Globally Serving Liquid and Powder Formulators and Manufacturers

Emerging Technologies

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CONTENTS PAINT & COATINGS INDUSTRY, VOLUME 27, NUMBER 11

November 2011

FEATURES 20 Advances in the Chemistry of Melamine Acrylate Oligomers, 26 32 38 41 42 62 68 78

Bomar Specialties Integrated Tinting Systems for a Low-VOC Future, CPS Color Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes, Cytec Industries Inc. Formulation Optimization Utilizing DOE Mixture Statistics, OMGroup Paint and Coatings Additives A New Way to Produce Antimicrobial Coatings, AM Coatings Innovation and Sustainability Highlighted at ABRAFATI 2011 A New Era in Superwetters for Waterborne and UV-Curable Coatings and Inks, Dow Corning Corp. A Multifunctional Coating for Autonomous Corrosion Control, NASA Innovation Drives Compact Paint Process for Waterborne Automotive OEM Coatings, PPG Industries

Seção Especial em Português 44 Ponto de Vista 46 Desempenho Superior de Películas Secas de Revestimentos por meio 50 56 60

do Controle da Liberação de IPBC, Ashland Specialty Ingredients Tecnologia de Poliuretanos Bicomponentes à Base de Água para Vernizes Automotivos Aplicações, Perstorp Novo aditivo umectante de substratos para Produtos adesivos à base de água com baixo teor de VOC, Troy Corporation Produtos

62

ONLINE FEATURES

w w w. pcimag.com Lubricious Medical Coatings Resist Particle Shedding During Use, Bayer MaterialScience LLC Custom Oven Solution Divides to Conquer Aerospace Manufacturer’s Increased Capacity Challenge, Carbolite Technical Breakthrough on Ceramic Coating, GMM Development Limited Green Manufacturing Practices in America Can Help Profits, Will Help Planet, Fabricators & Manufacturers Association Pigment Discovery Expanding Into New Colors – Including Orange, Oregon State University Peroxide-Resistant Coating for Cleanroom Renovation, European Industrial Paint Centre

DEPARTMENTS 6 8 12 14 18 86 88 90

Viewpoint Industry News Calendar of Events Company News Names in the News Products Classifieds Advertiser Index/Masthead

ON THE COVER: Cover photo courtesy of www.photos.com.

BUSINESS TOOLS 82 Emerging Technologies 86 Supplier Showcases PCI - PAINT & COATINGS INDUSTRY (ISSN 0884-3848) is published 12 times annually, monthly, by BNP Media, 2401 W. Big Beaver Rd., Suite 700, Troy, MI 48084-3333. Telephone: (248) 362-3700, Fax: (248) 362-0317. No charge for subscriptions to qualified individuals. Annual rate for subscriptions to nonqualified individuals in the U.S.A.: $115.00 USD. Annual rate for subscriptions to nonqualified individuals in Canada: $149.00 USD (includes GST & postage); all other countries: $165.00 (int’l mail) payable in U.S. funds. Printed in the U.S.A. Copyright 2011, by BNP Media. All rights reserved. The contents of this publication may not be reproduced in whole or in part without the consent of the publisher. The publisher is not responsible for product claims and representations. Periodicals Postage Paid at Troy, MI and at additional mailing offices. POSTMASTER: Send address changes to: PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. Canada Post: Publications Mail Agreement #40612608. GST account: 131263923. Send returns (Canada) to Pitney Bowes, P.O. Box 25542, London, ON, N6C 6B2. Change of address: Send old address label along with new address to PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. For single copies or back issues: contact Ann Kalb at (248) 244-6499 or [email protected].

Audited by BPA Worldwide

Printed in the U.S.A.

V I EWPOINT

Brazil Set for Growth I recently had a very interesting telephone conversation with David P. Nick, President and CEO of DPNA International, Inc. In the course of talking about this month’s ABRAFATI event in Sao Paulo, Brazil, Dave educated me on the BRICS alliance. I often read about the fast-growing economies and coatings growth in Brazil, Russia, India, China and South Africa (the BRICS countries), but I did not realize that these countries have formed a trade alliance unlike anything else. BRICS is not a formal trading bloc, but rather a loose economic alliance not based on currency, politics or traditional trading guidelines. Each of these countries has something the others want. To name a few, Brazil has land, oil and agriculture products; Russia, oil and gas; China, an enormous work force and the need for oil and gas; India has extensive IT knowledge and resources; and South Africa has precious metals and diamonds, and is the gateway to Africa. Rather than establishing trade agreements based in dollars

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NOVEMBER 2011 | W W W . P C I M A G . C O M

or euros, these countries have created barter agreements. For example, China might agree to build a highway system in South Africa, complete with funding, a labor force and equipment, in exchange for a multi-year contract to develop the country’s coal or metal resources. Such an alliance has the potential to make these countries’ continued growth something real and sustainable. It isn’t dependent on what happens in Europe or the United States. According to Nick, “BRICS represents a collective shift in economic power from the G-7 developed countries to the developing world, and many other countries are eager to join the club.” I look forward to reading more about BRICS and watching its development in the coming years. Despite a recent press release from ABRAFATI (Brazilian Coatings Manufacturers Association) that indicates that coatings growth in Brazil diminished this year compared to the 10% growth in 2010, the future looks bright. The overall growth of the coatings industry in Brazil this year should be 1.3% (due to the questionable international economic climate and a hesitation to remodel or build), reaching 1.377 billion liters, whereas a 4% expansion of sales is expected in 2012. In an effort to foster economic and social development, the Brazilian government has launched a housing program, Minha Casa Minha Vida 2, and has extended the IPI tax reduction. According to Dilson Ferreira, Executive President of ABRAFATI, “It is important to stress that, in addition to the great events that we will have until 2022 (including the 2014 FIFA World Cup and the 2016 Summer Olympics), which will ensure a sustainable growth, the structural reasons that stimulate sales will still be present for many years to come. Among these factors, the most noteworthy are investments in housing and infrastructure, the amplification of segments related to oil exploration and distribution, the strengthening of the internal market and the growth of the middle class.” In an effort to reach this growing market and the attendees at the upcoming ABRAFATI event, PCI introduces our first Portuguese supplement in this issue, which will be distributed at the show. We hope our Portuguese readers will find this information helpful and informative, and that we will be able to provide further supplements like this in the future.

By Kristin Johansson, Editor | PCI

Markets:

Architectural Coatings

Industrial Coatings

Container Automotive

Civil Aerospace Engineering

Coatings Technologies:

SolventBorne Coatings

WaterBorne Coatings

Powder Coatings

Surface/Substrate:

Wood

Brick

Concrete

Marine & Maintenance

UV Coatings

Metal

Stucco

High Solids Coatings

Vinyl

Plastic

Brenntag understands change is normal for the Coatings Industry. As the Coatings Industry has evolved through the years, Brenntag’s Paint and Coatings Team continues to provide our customers with the products and services to stay competitive in the marketplace. Whether you face different markets, technologies, or substrate applications, Brenntag’s Paint and Coatings Team can help you to adapt and make change work to your advantage.

Brenntag offers a complete specialty and industrial product portfolio, technical assistance with product development, formulations and applications know-how, superior logistics with versatile blending and re-packaging capabilities, and last, but not least, commitment to quality and safety. Change demands innovation and creativity. Brenntag Understands. Brenntag North America, Inc. (610) 926-6100 Ext: 3858 [email protected] brenntagnorthamerica.com

The Glocal® Chemical Distributor.

I NDUSTRY NEWS

Research Firm Predicts Market for Green Chemistry to Reach $98.5 Billion BOULDER, CO – According to a new report from Pike Research, the market for green chemistry represents an opportunity that will grow from $2.8 billion in 2011 to $98.5 billion by 2020. “Green chemistry markets are currently nascent, with many technologies still at laboratory or pilot scale,” said Pike Research President Clint Wheelock. “And many production-scale green chemical plants are not expected to be running at capacity for several more years. However, most green chemical companies are targeting large, existing chemical markets, so adoption of these products is limited less by market development issues than by the ability to feed

extant markets at required levels of cost and performance.” Pike Research forecasts that green alternatives in the polymer sector will

School of Polymers Honors Industry Leader HATTIESBURG, MS – The University of Southern Mississippi School of Polymers and High Performance Materials, Hattiesburg, MS, honored and memorialized the late Sidney Lauren, a leader in the coatings industry, on September 23 with the dedication of the Sidney Lauren Memorial Learning Center. The center is made possible by a donation from the Coatings Industry Education Foundation (CIEF). The CIEF has been a generous contributor of scholarships to polymer science students for more than a quarter of a century, including many who graduated from Southern Miss. The event included an opening ceremony, a brief history of the long-standing relationship between the CIEF and Southern Miss, an overview of Sidney Lauren’s life and work by the Lauren children, presentation of the donation, acknowledgement of individual CIEF Sidney Lauren Memorial Scholarship recipients, a demonstration of the new Sidney Lauren Online Learning Center, and an announcement of the first annual “Sidney Lauren Memorial Lecture” to be held at the Annual Waterborne Symposium in February 2012.

Use of Gold in Inks and Pastes on the Rise GLEN ALLEN, VA – Industry analyst firm NanoMarkets has released a new report, Printed Gold: Gold Inks and Pastes Market, 2011. The report examines the market for gold inks and pastes in the electronics and solar industries. It discusses both the gold pastes used in traditional applications, such as wire bonding and brazing, and a new breed of ink-based gold nanoparticles. These next-generation inks are expected to find uses in MEMS, data storage and computer memory, “green” electronics, photovoltaics (PV), and sensors. NanoMarkets estimates that the total volume of gold consumed by gold inks and pastes for electronics and PV applications will reach 13.7 metric tons by 2016. Although the gold pastes market is mature, NanoMarkets sees an opportunity for nanopastes, which would serve traditional thick-film markets but could provide significantly lower processing 8



NOVEMBER 2011 | W W W . P C I M A G . C O M

represent the highest penetration level (5.7 percent) within the total chemical market, as it is somewhat more developed than the other key sectors. The special, fine and commodity chemical sectors are more nascent and will enjoy somewhat lower penetration rates during the forecast period. The three major themes driving the green chemistry movement forward are: waste minimization in the chemical production process, replacement of existing products with less-toxic alternatives and a shift to renewable (non-petroleum) feedstocks. For additional information about the report, Green Chemistry, visit, www.pikeresearch.com.

costs. According to the report, the main new business opportunities will come mainly from novel applications using nano-inks. One of these opportunities may come from printing a thin layer of gold nanoparticles on optical disks, such as CDs and DVDs, which could greatly increase the amount of information being stored. Gold nanorods, in particular, have been noted as a material that can help provide new technology strategies for optical information storage. A printed layer of gold nanoparticles may also help to boost the efficiency of solar panels. In this context, NanoMarkets notes, printing has taken on a growing role in PV in recent years. The report also notes that the market for gold inks and pastes will be driven not just by the rise of alternative energy sources but also by environmental regulation. For more information about this report, visit www.nanomarkets.net.

ASTM Releases New Standards W. CONSHOHOCKEN, PA – A new ASTM guide standardizes a useful, fast and easy technique for collecting infrared spectra of nonaqueous liquid paints right out of the can. The new standard, ASTM D 7588, Guide for FT-IR Fingerprinting of a Non-Aqueous Liquid Paint as Supplied in the Manufacturer’s Container, is under the jurisdiction of Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials, which is part of ASTM International Committee D01 on Paint and Related Coatings, Materials and Applications. The new guide will be useful for quality, formula and process control, failure analysis, chemical identification, and compositional and raw material comparisons. A new standard, ASTM G 207, Test Method for Indoor Transfer of Calibration from Reference to Field Pyranometers, was developed by Subcommittee G03.09 on Radiometry, part of ASTM International Committee G03 on Weathering and Durability. ASTM G 207 facilitates calibration of solar sensors used in accelerated testing under simulated sunlight and outdoor weathering

AEROSOL® Surfactant – APE Free Sulfosuccinate Technologies and Customized Low VOC Wetting Agents Cytec offers a range of APE free sulfosuccinate surfactants for use in emulsion polymerisation. For acrylic, vinyl acrylic and styrene acrylic latex systems these water soluble highly effective surfactants offer: s0RIMARYORSOLEEMULSIlCATION s%XCELLENTPRE EMULSIONSTABILITY s#LEANROBUSTREACTIONKINETICSWITHHIGHCONVERSION s%XCELLENTMECHANICALSTABILITY s-INIMALGRITANDCOAGULUMINTHElNALLATEXnIMPROVING OPERATIONALEFlCIENCIES s4HEABILITYTOOPTIMIZELATEXFORMULATIONSFORDESIREDSOLIDS PARTICLESIZEANDVISCOSITY These latexes can subsequently be formulated into architectural coatings imparting: s%NHANCEDGLOSS s%XCELLENTHIDINGPOWER s'OODBLOCKRESISTANCE s'OODSCRUBRESISTANCE s2EQUIREDRHEOLOGY In addition Cytec offers a range of wetting agents for the formulation chemist offering: s&AST DYNAMIC DEEPWETTING s,OWFOAMINGVERSIONS s,OW6/#VERSIONS s#USTOMIZEDPRODUCTS 0LEASECONTACT#YTECFORTECHNICALSERVICEADVICEIFYOUHAVEANY unsolved issues with architectural coatings.

Email: [email protected] I Worldwide Contact Info: www.cytec.com ©2010 Cytec Industries Inc. All rights Reserved .

I NDUSTRY NEWS tests as well as performance monitoring of solar energy conversion systems.

AAMA Releases New Standard SCHAUMBURG, IL – The American Architectural Manufacturers Association (AAMA) has published a new standard,

AAMA 633-11, Voluntary Specification, Performance Requirements and Test Procedures for Exterior Stain Finishes on Wood, Cellulosic Composites and Fiber-Reinforced Thermoset Window and Door Components. The standard covers factory-applied coatings intended for service in exterior environ-

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Hydraulic Institute Releases New Test Standard PARSIPPANY, NJ – The Hydraulic Institute (HI) announced that both the Centrifugal Pump Test Standard (ANSI/HI 1.6 − 2000) and the Vertical Pump Test Standard (ANSI/HI 2.6 − 2000) have been superseded by the newly released Standard for Rotodynamic Pumps for Hydraulic Performance Acceptance Tests, (ANSI/HI 14.6 − 2011). The new test standard contains significant updates and is considered the new global reference for testing centrifugal and vertical pumps.

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WIENER NEUDORF, Austria – The Directory of Paint Manufacturers Central and Eastern Europe (CEE) 2011 has been released and is now available for purchase. The report, authored by Dr. Josef H. Jilek, contains country information, paint and coatings statistics, production capacity, export and import data, production ranges, and major coatings producers. Visit www.chem4cee.com/index. php?publications for more information.

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ST. AUGUSTINE, FL – The 2012 SSCT Annual Meeting will take place March 11-14, 2012, at the Renaissance Resort at World Golf Village, St. Augustine, FL. The theme of the meeting is “Blast Off Into the Ever-Evolving, Ever-Challenging World of Coatings.” The Southern Society for Coatings Technology is currently seeking technical speakers for this event. Any interested parties should e-mail Ursula Thomas at [email protected].

ECOAT 2012 to Take Place in Orlando ORLANDO, FL – ELECTROCOAT 2012 will take place April 11-12, 2012, at the Rosen Centre Hotel in Orlando, FL. The event is an educational conference for everyone involved in the electrocoat business and for people interested in learning about electrocoating. Visit www.electrocoat.org/conference for additional information. 

We are thinking about the same thing you are… How to make your products greener and their performance pure gold. Our customers come to us to help them stay ahead of competitive pressures by helping to re-formulate existing products and innovate new ones – meeting “green” goals while preserving and even enhancing performance. We call it Greenability. You’ll call it genius.  Another fine result of the Innovation Principle – . Let us help you work through the formula for Greenability.

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C ALENDAR Meetings, Shows and Educational Programs NOV. 21-23 ABRAFATI São Paulo, Brazil www.abrafati2011.com.br

DEC. 7 3rd Vietnam International Coatings Exhibition Ho Chi Minh City, Vietnam

13-17 Waterborne Symposium New Orleans www.psrc.usm.edu/waterborne

22 Paint & Coatings Basics Hampton, UK www.pra-world.com

7-8 ASTM International Committee G02 on Wear and Erosion New Orleans www.astm.org

22-24 Smart Coatings Orlando, FL www.smartcoatings.org

22-23 Adhesives for Wind and Solar Technology Berlin www.european-coatings.com 23-25 ChinaCoat 2011 Shanghai www.chinacoat.net 24-25 Automotive Coatings Berlin www.european-coatings.com 29-DEC. 1 Radiation Curing Technology Hampton, UK www.pra-world.com

28-31 11th International Paint, Resin, Coatings & Composites Fair Tehran, Iran www.ipcc.ir/

MARCH 11-14 SSCT 2012 Annual Technical Meeting St. Augustine, FL www.ssct.org 11-15 Pittcon 2012 Orlando, FL www.pittcon.org

2012 JAN. 30-FEB. 2 SSPC 2012 Tampa, FL www.sspc.org

FEB. 6-10 Polymers and Coatings Introductory Short Course San Luis Obispo, CA www.polymerscoatings.calpoly. edu

13-14 Professional Paint Formulation Hampton, UK www.pra-world.com 27-29 WESTEC 2012 Los Angeles www.westeconline.com

APRIL 3 PSCT Technical Symposium Horsham, PA www.psct.org 11-12 ELECTROCOAT 2012 Orlando, FL www.electrocoat.org 15-17 ASC Spring Convention Denver, CO www.ascouncil.org 17-20 PaintExpo Karlsruhe, Germany www.paintexpo.com 18-20 The Chemistry, Physics & Mechanics of Adhesion Science Stewart-Newburgh, NY www.mstconf.com

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C O M PA N Y NEWS

Arkema Coating Resins Introduces New Trademark CARY, NC – Arkema Coating Resins has announced a new trademark that will be applied to the company’s waterborne emulsion polymer products sold worldwide. The new name, ENCOR™ Polymers, will be used for both current and new products sold for use in architectural and industrial coatings, traffic paints, specialty coatings, pressure-sensitive adhesives, sealants, construction products, graphics arts, and floor maintenance products.

JNS Smithchem to Represent German Companies PATERSON, NJ – JNS Smithchem LLC has been appointed the sales representative covering northern New Jersey, New York and the New England states for Keim Additec Surface GmbH and Silcona GmbH. Keim Additec Surface GmbH, Kirchberg, Germany, is a manufacturer of specialty wax additives and surface conditioners featuring zero-VOC and APEO-free products. Its sister company, Silcona GmbH, is a supplier of high-performance additives for

ENCOR Polymers will principally replace the UCAR trademark now applied to many of the company’s waterborne emulsion products, as well as the Craymul® and Esi-Cryl® trademarks acquired with the purchase of the coating resins businesses of Cook Composites and Polymers and Cray Valley. Other Arkema Coating Resins trademarks, including SNAP™ Structured Nano-Acrylic Polymers and EnVia™, will continue to be used in all geographies. wetting and surface modifications in environmentally friendly coating systems. The U.S. subsidiary company, KEIM-ADDITEC Surface USA LLC, has offices in Wilmette, IL.

Evonik Lays Foundation for Two Innovation Centers ESSEN, Germany – Klaus Engel, Chairman of the Executive Board of Evonik Industries, has laid the foundation stones for two research and development centers at the company’s Essen, Germany, site.

C O M PA N Y N E W S

One center is for new, environmentally friendly additives and special binders for the coatings industry. The other center is for products for the cosmetics industry. In total, the group is set to invest some €31 million in the two building complexes. The innovation center for the coatings industry is to be completed at the end of 2012.

Archway Sales to Distribute for AkzoNobel ST. LOUIS, MO – AkzoNobel Performance Additives has appointed Archway Sales Inc., St. Louis, MO, as its distributor for the Louisiana, Texas, Oklahoma and New Mexico markets.

Color-Logic Appoints Upper Midwest Representative PPG to Supply Coatings Used in New Caterpillar Plant PITTSBURGH – Caterpillar Inc. has selected PPG Industries’ industrial coatings business as the sole heavy-duty equipment coatings supplier for a new motor grader assembly plant in North Little Rock, AK. In addition to serving as a single-source coatings supplier, PPG is providing on-site technical and product approval support, and in-plant training of paint-line operators through its Knowledge College service in coating application technologies.

Perstorp Doubles Caprolactone Capacity PERSTORP, Sweden – Perstorp has doubled production capacity of its Capa™ caprolactone plant in Warrington, England. The company’s second Capa stream is based on the same proprietary technology as its first stream.

WEST CHESTER, OH – Color-Logic has named MSM Color as its manufacturers’ representative for Minnesota, western Wisconsin, Iowa, North Dakota, South Dakota, Nebraska, Kansas and the Kansas City, MO, area.

AP Plastics to Distribute for Sulzer Mixpac USA PEABODY, MA – AP Plastics LLC, now an affiliate of Adhesives Packaging Specialties, is a recognized distributor for Sulzer of Salem, NH. Under this agreement, AP Plastics will develop and promote the sale of Sulzer’s product line throughout North America for its static mixers, cartridges, dispensing guns, dual syringes and accessories.

Croda Expands Esters Plant in North America EDISON, NJ – Croda Inc. announced the official opening of its new facility for the production of lubricant esters at its Atlas Point manufacturing site in New Castle, DE. The Atlas Point manufacturing site will now be able to manufacture lubricantquality esters, targeting growth in high-end lubricant applications. Food-grade esters for lubricant base fluids and additives

Arkema Coating Resins delivers innovative products and targeted support that allow you to capitalize on amazing new opportunities. For example, our SNAP™ 720 Structured Nano-Acrylic Polymer uses advanced particle morphology design to offer formulators excellent gloss and adhesion plus outstanding block resistance and film hardness in a no or low VOC architectural coating. If you haven’t already tried this 100% acrylic binder, it’s definitely worth looking into.

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Dow Announces Capacity Expansions MIDLAND, MI – The Performance Monomers business of The Dow Chemical Co. (Dow) announced a 15-percent increase in capacity for the production of 2-ethylhexyl acrylate at its Hahnville, LA, facility. Dow has increased its propylene glycol capacity by an additional 10 kilotons per annum (KTA) at its Stade, Germany, plant. Dow’s Performance Monomers business announced that capacity for the production of crude acrylic acid (CAA) at its Böhlen, Germany, facility has expanded by 25 percent. The additional CAA at Böhlen will be used to increase butyl acrylate and glacial acrylic acid production at the site. The Performance Monomers business also announced a 10-percent increase in capacity for the production of glycidyl methacrylate at its Freeport, TX, facility.

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COLOMBES, France – Cray Valley Resins, a business that is now part of Arkema Coating Resins, was awarded the Ringier Technology Innovation prize for its Synaqua® 4804 alkyd emulsion. This waterborne paint binder is an innovative alkyd emulsion that helps produce top-quality gloss paint with application characteristics very close to those of solvent paint.

Clariant Receives Paint & Pintura Awards SÃO PAULO, Brazil – Technology innovation, differentiated services and strong customer relationships have secured Clariant a hat trick of awards in the Brazilian paint and varnish industry’s Paint & Pintura awards for 2011. In addition to achieving Best Supplier in the categories Emulsions, Pigment Dispersions and Organic Pigments, Clariant was also elected the Master Top 10 Company for the third year in a row.

Ecology Coatings Nominated for U.S. Green Chemistry Challenge WARREN, MI – Ecology Coatings Inc. has been nominated for the U.S. Green Chemistry Challenge 2012. This program recognizes chemical technologies that incorporate the principles of green chemistry into their design, manufacture and use. Ecology Coatings was nominated based on its GRAS (generally regarded as safe) coatings, which reduce toxic chemicals contained in food packaging products.

BASF Receives Design Award for Automotive Color Innovation

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NOVEMBER 2011 | W W W . P C I M A G . C O M

SOUTHFIELD, MI – BASF Coatings has been honored with a design award for XFine®, its unique automotive color innovation. The German Design Council selected the paint manufacturer as a winner of the 2011 Automotive Brand Contest, the first international brand and design competition for the automotive industry. XFine has also been nominated for the 2012 German Design Award.

Univar Acquires Brazilian Distributor REDMOND, WA/SÃO PAULO, Brazil – Chemical distributor Univar Inc. has acquired Arinos Química Ltda. (Arinos). Arinos is a leading chemical distributor in Brazil, providing both specialty and commodity chemicals as well as highvalue services. 

The new Z-line of performance additives aims to provide improvements to customers developing environmentally sustainable green coatings. As the demand for "green" coatings continues to rise at a furious pace, Troy’s Z-line offers formulators enhanced performance in making greener coatings possible without adding undesirable components such as VOCs or HAP’s. With the Z designed products, Troy continues its commitment to assist industry in addressing the need for performance products that are environmentally responsible and yet economically viable. Contact your Troy Sales Representative for information on the Z-line of Troy performance additives or visit www.troycorp.com.

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N AMES IN THE NEWS  Watson Standard

 BYK-Gardner has named Rae Roby Regional

has appointed Cynthia Blomquist EH&S Manager. Wesley E. Horton was appointed Assistant Director of Manufacturing, and Richard Newman was appointed Process & Maintenance Engineer.

 Nubiola has hired Jeff Cayce as Technical Sales Manager, Coatings.  Dow Coating Materials has appointed Michael

Cauchi

Lewis West Coast Sales Manager.

 Plasticolors Inc. has appointed Andrew Locy Chemist within the Coatings Technical Group. Margaret Dvorak has been appointed Product Development Specialist.

 BASF Automotive Refinish has named Vitor

Roby

Margaronis Marketing Director for BASF Coatings, North America.

 Tim Miller has been appointed President of Flame Control Coatings. Ryan Najmulski was hired as the new Marketing Manager.

 Bruce Rose has been appointed Product Manager for UCT’s silanes, silicones and platinum catalysts.

Sales Manager for the Michigan and Northern Ohio Region. Sam Cauchi, Sales Manager for Canada, is now responsible for covering all of Canada. Sheila White has been named the company’s new Customer Care Center Manager for North America. Mary Llewellyn, of the company’s Customer Care Center, will be Margaronis responsible for all of Canada and will be working with Cauchi. Scott Richeson, also a team member in the Customer Care Center, will work with Andy Stummer covering the Mid-Atlantic USA territory. Sandrine Letendre, one of the newest members of the Customer Care Center, will handle the West Coast USA area and work with Ed Smyth. Patrick Weaver, another new member of the Customer Care Center, will handle the White Southwest USA area and work with Joe Daniels. Corey Cohen joins BYK-Gardner USA as Applications Specialist to the company’s applications staff, and Josh Egbert joins BYK-Gardner USA as the Service Administrator.

 JNS Smithchem LLC has appointed John P. Sari Regional Sales Manager. Sari will be responsible for growing the company’s customer and supplier base in southern New Jersey, Pennsylvania, Delaware, Maryland and Virginia. 

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Advances in the Chemistry of

Melamine Acrylate Oligomers

M

elamine formaldehyde (MF) resins are widely used in industry. They belong to a class of amino resins that are used as crosslinkers for thermoset coatings. MF resins co-react with polyester, alkyd, epoxy, polyurethane and acrylic resins to impart hardness, durability, chemical resistance and heat resistance to many industrial coatings.1,2 Such mixtures of resins are cured at high temperatures. MF resins are prepared by the reaction of melamine and formaldehyde under basic conditions, followed by acidic etherification with an alcohol. The triazine ring has six

reactive groups that can be used to prepare oligomers with unsaturated reactive groups. Melamine acrylates (MAs) have both acrylic and either hydroxyl or alkoxy groups. These acrylates undergo photopolymerization (UV cure) by a free radical mechanism due to the presence of the acrylate group. The hydroxyl or alkoxy groups can be cured by condensation. In this article, we report on new UV-curable MA oligomers, present their properties as viscous liquids and their outstanding properties as cured MAs (thin films). The melamine acrylates are designated as BMA or XMA.

Structures of the Prepared MAs FIGURE 1 | Generic structures of prepared O

MAs.4

O N

O N

N

N

O

N

O

N O

O

O

O

O

N O

XMA-220

BMA-222

O

O

N

O

N O

O N O O

O

O

N O

O

O

XMA-224 S

O

N

O

O

O N

O

O

N

OH

O

N O

O

O

O

O S

O

O

S

XMS-224

LS XMA-222

TABLE 1 | Residual formaldehyde in BMA-2223 after acid neutralization and prepared with a standard and a proprietary catalyst.

Free formaldehyde, wt.%a a

Standard Catalyst

Proprietary Catalyst

1.0 %

0.025%

Determination error is 15%

The generic structures of monoacrylate XMA-220, triacrylate BMA-222,3 pentaacrylate XMA-224, MA with a grafted photoinitiator (PI) LS® XMA-222, and a sulfide group containing XMS-224 are presented in Figure 1. Unfortunately, almost all melamine resins have the unpleasant odor of formaldehyde.2 Much effort is devoted to reducing the formaldehyde content in MF resins.2 Mineral or organic acid is used in a standard dark cure (condensation) of MF resins, which is accompanied by demethylolation and by an additional release of formaldehyde. An acid-catalyzed reaction of MF resins with the formation of MA also leads to the evolution of formaldehyde. The addition of a proprietary base terminates equilibrium reactions in acidic solutions containing melamine and, therefore, brings to a halt any further evolution of formaldehyde. The remaining free formaldehyde is stripped. Moreover, we selected a catalytic system that results in a clear (not a turbid) resin. For this discussion, BMA-222 (Figure 1) is selected as an example. One can see a dramatic difference in the level of formaldehyde before and after neutralization (Table 1). According to many users, BMA-222 does not have a formaldehyde odor. In addition to reducing free formaldehyde in the final liquid resin, the neutralizing agent leads to an increase in the shelf stability of BMA. It is known that acid induces further condensation of MF resins, which leads to an increase in viscosity (d) and eventually

By Ahmet Nebioglu, Ph.D., Director of Applied Technology | Bomar Specialties, Torrington, CT; and Igor V. Khudyakov, Ph.D., D.Sc. IVK contributed to this paper prior to joining Solutia Inc., Fieldale, VA, as a Senior Chemist. 20



NOV EMBER 2011 | W W W . P C I M A G . C O M

MA oligomers can be used as additives to strengthen films of urethane acrylates. We prepared a number of formulations in order to observe the effect of MA addition on the mechanical properties of a flexible (“soft”) cured oligomer BR-304.3 These formulations are listed in Table 4. Formulations MA0, B10, B20, X10 and X20 contain 30 wt.% of IBOA and 2.0% of Irgacure 184. L0 and L10 were prepared to estimate the effect of LS XMA-222 addition on the UV cure of urethane acrylate.

to gelation. This condensation is prohibited in BMA/ XMA due to lack of free acid. LS XMA-222 (Figure 1) utilizes grafted PI LS oligomers, and formulations with them do not require an addition of PI, as they are self-initiated.5,6

Physical Properties of the Liquid and Cured MAs

7000 6000 5000 4000 3000 2000 1000 0

4

XMA-220 BMA-222 XMA-224

Elongation-at-Break (%)

FIGURE 2 | Tensile strength and elongation-at-break of MA formulations. All individual MAs were diluted with 50 wt.% of a common diluent, isobornyl acrylate IBOA. Irgacure 184 (2.0%) was added to the formulations. Determination error of the values can be seen in the figure. Tensile Strength (psi)

Synthesized BMA/XMA oligomers have relatively low Mw (< 2,000 g/mol) and a relatively low d. We observed that BMA cures faster than urethane acrylates of the same functionality under similar conditions, and BMA requires a much lower amount of PI for it to cure. In particular, we cured trifunctional urethane acrylate BR-1443 and trifunctional BMA with PI Irgacure 184. The oligomers were of comparable Mw, and each oligomer was diluted twice with a common diluent tripropyleneglycol diacrylate TRPGDA (Table 2). The striking difference between BMA-222 and BR-144 in this example is the concentration of PI: BMA222 can be cured with an extremely low concentration of a common PI (Irgacure 184). It is an order of magnitude lower than the concentration of PI required for the urethane acrylate cured under our experimental conditions (Table 2). The mechanical properties of the MA oligomeric films are presented in Figure 2. Pentaacrylate XMA-224 (Figures 1 and 2) has the highest tensile strength, probably due to a high crosslink density expected for the cured multifunctional monomers/oligomers. Also, as expected, monoacrylate XMA-220 (Figure 1) has the lowest tensile strength and the largest elongation-at-break among the studied XMA/ BMA (Figure 2). MA oligomers are widely used in UV-curable wood coatings. Emission of volatile and extractable byproducts during UV curing is a problem for furniture, ink and food applications. Much effort is devoted by both academia and industry to develop non-migrating PIs.5,8,9 MAs can be a good choice to get films with low extractables due to their efficient cure response at low PI concentrations. It was mentioned previously that BMA-222 can be cured into tack-free films with even 0.1% of PI, and Irgacure 2959 in particular. The latter PI is approved by the Food and Drug Administration. MA with a grafted Irgacure 2959 (LS XMA-222, Figure 1) demonstrates negligible leaching of the PI. We prepared two formulations with the goal of comparing PI extractability: one with LS XMA-222 (named F1) and the other with a dissolved Irgacure 2959, named F2 (Table 3). F1 and F2 have approximately the same concentration of free/grafted PI, namely 2%. Cured pieces of films F1 and F2 of the same shape and mass were each kept in the same volume of THF for 72 h. We measured only the leached PI and byproducts of PI photolysis by GC-MS analysis of the two supernatants. It follows from the data in Table 3 that the extractable concentration from the F1 film is essentially lower than that from the F2 film. There are reasons to expect much lower extractable concentrations considering that MA oligomers can be cured with a very low concentration of PI, namely [PI] << 2%, cf. above.

50 45 40 35 30 25 20 15 10 0 XMA-220 BMA-222 XMA-224

TABLE 2 | Properties of trifunctional melamine acrylate and trifunctional urethane acrylate diluted with 50 wt.% of TRPGDA at 25 º C. BMA-2223

BR-1443

100 14.1 15.2 77D 0.1

1050 25.2 10.6 82D 2.0

cPa

Viscosity d, Tensile modulus, MPaa,7 Elongation-at-break, %a Durometer hardnessa Irgacure 184, wt.%b a b

Determination error is 15% These and all other samples in this work were cured in air with Fusion D bulb, 300 W/in.

TABLE 3 | Formulations prepared for PI extractability analysis from the cured films. Formulation

F1, wt. %

F2, wt. %

25 25 50 -

48 50 2.0

170

900

LS XMA-222 BMA-222 TRPGDA Irgacure 2959 Extracted PI and its byproducts, ppma a

Determination error is 10%.

TABLE 4 | Urethane and melamine acrylate formulations. BR-3043 IBOA Irgacure 184 BMA-222 XMA-224 Irgacure 2959 LS XMA-222

MA0

B10a

B20a

X10b

X20b

L0c

L10c

68d 30 2 -

58 30 2 10 -

48 30 2 20 -

58 30 2 10 -

48 30 2 20 -

60 30

60 30 10

9.2 0.8 -

a

B denotes BMA-222; numbers represent concentration of BMA-222 (wt.%) in a formulation. X denotes XMA-224; numbers represent concentration of XMA-224 (wt.%) in a formulation. c L denotes LS XMA-222; numbers represent concentration of LS XMA-222 (wt.%) in a formulation. b

PA I N T & C O A T I N G S I N D U S T R Y



21

Advances in the Chemistry of Melamine Acrylate Oligomers

The mechanical properties of formulations listed in Table 4 are compared in Figures 3 and 4. One can see a determination error of the values on these figures. Figure 4 also presents the overall conversion j of acrylate groups in the formulation. Conversion was estimated by using IR spectroscopy to measure acrylate groups prior and after cure.21 Films prepared from MA0 (does not contain any MA oligomer) have the lowest tensile strength and modulus, and the highest elongation-at-break (Figures 3 and 4). Addition of just 10% of MA oligomer increases the tensile strength of the films six times or more (Figure 3). This increase could be attributed to the increased crosslink density. Further increase of MA concentration does not lead to an increase of tensile strength but to an essential increase of the tensile modulus. Pentafunctional XMA224 has the highest modulus as expected. A 10% addition of either BMA-222 or XMA-224 leads to an increase of j (Figure 4). Further increase of concentration of BMA-222 or XMA-224 leads to a decrease of j, probably due to early vitrification during photopolymerization.10,11

FIGURE 3 | Tensile strength and elongation-at-break of the films for formulations in 1800 1600 1400 1200 1000 800 600 400 200 0

Elongation-at-Break (%)

Tensile Strength (psi)

Table 4.

MA0 B10 B20 X10 X20 L0 L10

350 300 250 200 150 100 50 0

MA0 B10 B20 X10 X20 L0 L10

16 14 12 10 8 6 4 2 0

% Conversion

Tensile Modulus (ksi)

FIGURE 4 | Tensile modulus and acrylate groups conversion (j) in the films, for formulations in Table 4.

MA0 B10 B20 X10 X20 L0 L10

70 60 50 40 30 20 10 0

MA0 B10 B20 X10 X20 L0 L10

TABLE 5 | Refractive index of melamine acrylates.

a b

Oligomer

MA

Thiol

nD20 a (Oligomer)

nD20 a,b (Film)

XMA-224 X-1 X-2 X-3 X-4 X-5

XMA-224 XMA-224 XMA-224 XMA-224 XMA-224 XMA-224

Thiophenol 2-Mercaptothiazoline 2-Mercaptobenzothiazole Triphenylmethanethiol p-Thiocresol

1.512 1.566 1.589 1.593 1.600 1.555

1.521 1.578 1.605 1.610 1.620 1.565

Determination error of nD20 is ± 0.002. Oligomers were UV cured with 1.0% of Darocur 1173.

22



NOV EMBER 2011 | W W W . P C I M A G . C O M

The film L10 cured by the grafted PI of LS XMA-222 (Table 4, Figure 1) demonstrates a higher tensile strength and larger elongation-at-break compared to the same values of the film L0 (Table 4) cured with the same dissolved PI. Modulus and j of L0 and L10 were similar to each other (Figure 4). This fact means that LS XMA-222 assists cure of L10, strengthening the forming film. In concluding this section we note that structure property relationships for oligomers and formulations with oligomers are rather complex. The knowledge of only an oligomer structure and a formulation composition allows only reasonable expectations, which should be either confirmed or revised in the experiments.

Refractive Index of MAs High-refractive-index (n D) materials are often obtained with inorganic/organic hybrid systems. However, to produce a transparent coating, metal oxide particles should be formed in situ at high temperatures (>300 ºC). To the best of our knowledge, the highest reported refractive index organic polymer is n D20 =1.757.12 The polymer was not UV cured but was cast from a solvent, which is accompanied by VOCs. There is commercial interest in coatings with high n D20, which can be obtained at mild conditions at ambient temperatures and with low or zero VOCs. Therefore, UV-cured, high-n D20 coatings attract much attention of researchers.13 Besides all the known advantages of UVcurable formulations, UV cure leads to increased n D20 due to an increase in molecular polarizability through molecular orientation and volume shrinkage. Polymers containing aromatic groups and highly polarizable atoms such as nitrogen, sulfur, phosphorus, bromine and iodine show relatively high nD20.14,15 Among these heavy atoms, sulfur-containing polymers are of particular interest due to their low color, raw material availability and variety of mechanical properties of the formed films. MA oligomers have relatively high nD20 of 1.5 by themselves due to a high concentration of (hetero)aromatic groups and nitrogen atoms (Table 5). The Michael addition reaction of thiols, RS-H to electron-deficient vinyl groups in maleimides16 and acrylates,17 is well documented. The nucleophilic character of thiols, RS-H, allows the synthesis of C-S bond-containing products with a high yield. In order to increase nD20 of MA oligomers, we synthesized the thiol adducts of XMA-224 (Figure 1) by a reaction of aromatic thiols with acrylate groups. As expected, the new thiolmodified MAs have higher nD20 (Table 5). We also prepared a number of adducts of XMA-224, gradually increasing initial relative concentration of thiophenol. As anticipated, an increase in thiol concentration led to an increased nD20 of the adduct. However, a thiol addition to acrylates consumes the acrylate groups available for UV cure, and hence decreases the tensile strength and toughness of the cured coatings. Therefore, there is a tradeoff between the strength/toughness of the films and nD20. All of the thiol-modified MAs (Table 5) yield transparent, colorless films after UV cure. The cure of oligomers leads to a 1-5% increase of nD20 (Table 5). Thiol structure essentially affects nD20 of the adducts (Table 5). We were able to get the n D20 of modified melamine acrylate oligo-

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Advances in the Chemistry of Melamine Acrylate Oligomers

mers up to 1.62 (X-4 in Table 5). As projected, n D20 of the oligomer and of the cured film increases as the number of aromatic groups in the thiol increases (X-2 vs. X-5 in Table 5). Furthermore, alkyl groups usually lead to lower n D20 of polymers due to a decrease in polarizability.13,14 In fact, X-5, which has a similar structure to X-1 except for the presence of the methyl substituent in thiol, has a lower n D20 (Table 5). X-1 oligomer is particularly interesting for industrial application due to its relatively low cost of raw materials, low color and low (for oligomers) viscosity of ~5,000 cP at room temperature. Table 6 presents compositions of four UV-curable formulations denoted as F1 – F4. Fi are based on X-1. Mechanical properties of the cured films Fi are also presented in Table 6. MAs with high n D20 can be used in protective coatings for plastics and in antireflective coatings for a wide variety of substrates.

Thermostability of MAs Resistance to high temperatures is a valuable property of protective coatings in a number of applications. We ran TGA experiments on two MA oligomers and on one urethane acrylate BR-344. Table 7 presents the results. It follows from the data in Table 7 that the studied MA oligomers are rather resistant toward high temperatures and obviously are more resistant than urethane acrylates. (The carbamate fragment is the known weakest link in all of the polyurethanes.) It is not surprising that MAs are used as additives to impart high temperature resistance to many industrial coatings.

TABLE 6 | Formulations Fi containing XMS-224 and mechanical properties of the corresponding films at 25 º C. F1

F2

F3

99

69

49

-

-

-

-

49

IBOA,wt.%

-

30

-

-

TRPGDA, wt.%

-

-

50

50

X-1, wt.% XMA-224, wt.%

Darocur 1173, wt.%

1

1

1

1

5400

400

150

100

Tensile strengtha, psi

87

270

399

6700

Elongation at breaka ,%

8

30

5

3.3

Tensile modulusa, psi

1.2

2.9

51

320

Durometer hardnessa

74A

73A

54A

85A

d a, cP

a

F4

Determination error is 10%.

TABLE 7 | Results of TGA study on three cured oligomers.a XMA-224b

BMA-222b

BR-3443

ºCc

290

239

209

Temperature of 5.0% of the mass loss, ºCc

295

290

251

Temperature of 2.0% of the mass loss,

a Each of the three oligomers was diluted with 30 wt.% of IBOA. 2.0% of Irgacure 184 was added to formulations. Conditions of cure are presented in Table 2. b Reference Figure 1 for the structure. c Determination error is ± 1 ºC.

24



NOV EMBER 2011 | W W W . P C I M A G . C O M

Summary Melamine resins are well known in the coatings industry. Many melamine acrylates are used as protective coatings, as release coatings for reusable plywood,18 etc. In particular, BMA-222 is used in the furniture industry. We prepared a series of UV-curable MAs with different acrylate functionalities, which undergo fast photoplymerization with a low concentration of PI. Although the MF has been functionalized, the resin MA still possesses much of the melamine properties. One can purposefully alter the melamine acrylate mechanical properties by varying functionalities of MA or using mixtures of MAs with other oligomers. In our opinion, X-1 (Table 5) is the most interesting among the entire synthesized melamine acrylates. It has low viscosity, can be synthesized from readily available commercial raw materials, and its formulations produce colorless films. PI-grafted MA demonstrates negligible leaching from the cured coating in THF. We synthesized five oligomers by addition of thiols to acrylate groups of MA. The most valuable property of the new sulfur-containing oligomers is their high n D20. These oligomers will find applications in antireflective coatings. 

References 1

Webster, G. Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints: Prepolymers and Reactive Diluents for UV and EB Curable Formulations; Wiley: New York, 1997. 2 Wicks, Z.W.; Jones, F.N.; Pappas, S.P.; Wicks, D.A. Organic Coatings Science and Technology; Wiley: New York, 2007, ch.7. 3 http://www.bomarspecialties.com 4 Nebioglu, A., Leon, J.A., Khudyakov, I.V. RadTech USA, Chicago, 2008. 5 Khudyakov, I.V., Turro, N.J. Photochemistry and UV Curing: New Trends, Fouassier, J.P., Ed., Research Singpost: India, 2006, ch. 21. 6 Allen, N.S., Marin, M.C., et al. J. Photochem. Photobiol. A. 1999, 126, 135. 7 Pa (pascal) is an SI unit of pressure, of tensile strength, of tensile modulus. However, such non-SI units as psi and ksi are often used in the coatings industry. 145 psi = 1 MPa. 1 ksi stands for 1000 psi or 1 kPa = 145 ksi. In this work we use all three units. 8 Carlini, C., Angiolini L. Adv. Polym. Sci. 1995, 123, 127. 9 Schwalm, R. UV Coatings Basics, Recent Developments and New Applications; Elsevier: Amsterdam, 2007, ch. 5. 10 Nebioglu, A., Soucek, M.D. J. Polym. Sci. Pol. Chem. 2006, 44, 6544. 11 Dušek, K., Galina, H., Mikes, J. Polym. Bull. 1980, 3, 19. 12 Sadayori, N., Hotta. Y. U.S. Patent Application Publication 20040158021A1, 2004. 13 Morford, R.; Shih, W.; Dachsteiner, J. Proceedings of SPIE 2006, 6123. 14 Groh, W., Zimmermann, A. Macromolecules 1991, 24, 6660. 15 Olshavsky, M., Allcock, H. R. Macromolecules 1997. 30, 4179. 16 Houseman, B.T., Gawalt, E.S., Mrksich, M. Langmuir 2003, 19, 1522. 17 Ludolf, N.P., Tirelli, N., Cerritalli, S., Cavlli, L; Hubbell, J.A. Bioconjugate Chem. 2001, 12, 6536. 18 Hall, R.P. US Patent 3,899,611, 1975.

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Cut your Milling Costs without sacrificing © 2011, 3M. All Rights Reserved. 3M is a trademark of 3M.

performance.

Introducing 3M™ Micro Milling Media ZGC* For years Yttria-Stabilized Zirconia beads have been the standard for high-energy micro milling. Now there’s a product with all the performance of Yttria-Stabilized Zirconia, but at a fraction of the price—3M™ Micro Milling Media ZGC. What does this mean for your milling operations? Now, not only can you cut your milling costs, but you can also afford to use higher performing media to make smaller particle sizes in less time. For more information and to purchase 3M micro milling media, go to www.3M.com/ZGC. *Notice: This experimental product has not been introduced or commercialized for general sale, and is subject to change or withdrawal without notice.

ITS)SERIES

Integrated Tinting

Systems

for a Low-VOC Future

P

This article is Part 1 of a four-part series on converting to an integrated tinting system.

aint manufacturers face many conflicting demands. Their clients have come to expect instant availability of high-quality, highperforming, reliable paints in every imaginable color. At the same time, ever-tightening VOC regulations need to be observed in a very competitive market environment. What appears like an impossible proposition is actually an excellent time to think about tinting systems more generally and to put one’s business on a stronger footing. As paint manufacturers are urged by regulatory bodies to convert their tinting systems to lowVOC colorant technology, they are also given an opportunity to rethink their set-up and make significant changes. Conversions are best managed in a comprehensive way, applying the principles of integrated tinting system design. For best results, paint producers need to understand both the benefits of integrated tinting and their own business needs. Working in partnership with a complete tinting

Gloss Level 60º

FIGURE 1 | Gloss level of a silk alkyd paint with various colorant types and levels. 50 45 40 35 30 25 20 15 10 5 0

systems solutions provider, they will be able to convert to a customized system that mitigates the above challenges while keeping total cost of ownership low. There has been a concern with volatile organic compounds (VOCs) for many years, as some are known to cause potential harm to human health and/or the environment. VOC levels in paint are therefore carefully regulated but, so far in the United States, the contribution made by VOC-containing colorants has not been taken into account. With new legislation announced by the South Coast Air Quality Management District (SCAQMD) this is set to change. From January 1, 2014, VOC levels in colorants must not exceed 50 g/L for all architectural and water-based industrial coatings.1 Paint manufacturers now have less than two years to prepare for the changes. Many currently underestimate what the conversion to low-VOC colorants might mean to their business. Research published by the SCAQMD2 has shown that very few paint manufacturers have given any thought at all to the changes, and of those who did, only a quarter are really aware of its implications. The majority of the respondents, particularly small- and medium-sized companies, admitted to not knowing what to expect in terms of time needed for the conversion, overall cost and training involved, or whether their existing dispensing equipment would be compatible with low-VOC colorants.

Traditional Tinting Systems

0 v% Colorant Load (reference)

7 v% Universal Colorant Load

7 v% Alkyd Colorant Load

15 v% Alkyd Colorant Load

TEST PROCEDURE: SFS-EN ISO 2813 (1999)

The first step is to understand exactly what a tinting system does and the different types of tinting systems. Tinting systems for paints, designed to deliver the exact shade of color to customers, are based on standardized components, including colorants, dispensing and mixing equipment, control software and a color formula database designed to match the selected color marketing tools. Most paint manufacturers aim to offer the broadest possible range of coating formulations and products to

By Martijn Kunnen, Head of Sales, Colorants EMEA and Total Solutions CE; and Sven Heutz, Sales & Service Manager | CPS Color, Sittard, The Netherlands 26



NOV EMBER 2011 | W W W . P C I M A G . C O M

The Conversion Question Conversion to a low- or zero-VOC colorant system is the only option due to legislation. However, the key is to select a new tinting system that will deliver the best possible long-term results for the individual business needs; in other words, to convert to an integrated tinting system. Such a system is more than the sum of its parts. It is a comprehensive approach to tinting system design that is customized to meet the business objectives of the individual paint manufacturer. Design of such systems requires thorough analysis of the manufacturer’s current business

model and future objectives. It also demands intimate technical knowledge of all tinting system components to optimize and fine tune the performance of each element: colorants, dispensing and mixing equipment, control software and a color formula database design.

The Best of Both Worlds For one business we examined alkyd coatings technologies, an important business segment for this paint producer. Therefore, a customized colorant set was selected to combine the advantages of a single universal system with those of a dual system. Water-based colorants are paired with a selection of UV-resistant, high-performance colorants plus economical colorants for the universal and solvent-based ranges. Such a system may, for example, consist of 24 colorants in total: 10 water-based, six universal and eight solvent-based ones. Colorants that are only needed in small quantities are set up as universal colorants. They can be used with both water-based and solvent-based systems, increasing their consumption. Since color formulas contain only minor amounts of

FIGURE 2 | Dry time variability for a high-gloss alkyd tinted with different colorants and levels. 600 500 Drying Time (min.)

serve the diverse needs of their customers. In an effort to become more efficient, they adopted a universal colorant system for tinting a broad variety of products: from water-based latex architectural coatings to solventborne industrial maintenance coatings. Such systems typically consist of 12 universal colorants. While this works well in terms of offering a broad range of products at the point of sale, the paints’ quality may not always be entirely satisfactory due to the contribution of water from the universal colorants. Users of alkyd paints, for example, have a high demand for deep colors that can require a large colorant load. Introducing too much water into an alkyd product, however, can impair workability and application characteristics of the paint. Here, a solvent-based colorant would achieve a better result (Figures 1 and 2). For example, 15% of a solvent-based colorant in a silk alkyd paint can be handled without a problem, while the addition of only 7% universal colorant will significantly reduce the gloss level of the coating (Figure 1). However a high-gloss alkyd paint with 7% universal colorant may require a longer drying time (Figure 2). One way around this problem is to operate a dual system, which is one that consists of two sets of colorants, one water-based, one solvent-based. This ensures maximum compatibility with the base paint – but it can lead to problems with the colorants themselves. Doubling the number of colorants means that the consumed quantity of colorant declines by half on average. Some colorants, such as violet-red or magenta, are only used in very small amounts to less than one liter per year. This means they remain in their canisters for too long and may start to thicken or deteriorate, causing problems within the dispenser (Figure 3). The picture becomes clear: whether single or dual, users of traditional, water-based, universal colorant systems either face limitations in terms of paint quality and characteristics, or experience adverse effects on colorant and equipment quality. If they replace their current lines with corresponding ones stripped of VOCcontaining additives, they may well conform to incoming regulation, but the other difficulties will remain. What’s more, a simple “pour-over” is set to introduce further issues, as companies already experimenting with such a solution reported in the AQMD colorant survey. Half of them reported problems with clogged and dried-up nozzle tips, and some experienced variable viscosity and lack of compatibility in terms of gloss, water sensitivity and other features. Generally, low-VOC colorants are known to pose challenges with storage, mold growth and surface drying.

400 300 200 100 0

7 v% 0 v% Universal Colorant Load Colorant Load (reference)

15 v% Alkyd Colorant Load

Test Procedure: ASTM 5895 – 01e1

FIGURE 3 | Variable rates of consumption for different colorants in an average tinting system. 16% 14% 12% 10% 8% 6% 4% 2% 0%

t n LC C r a e e e e H HC id LC it HC id g be nt HC LC LC le e w Ox low Wh ed Ox ran Um age ack lack Red Vio Gre lue lue o l w el B R l O l d B B M B Ye llo Y Re Ye

PA I N T & C O A T I N G S I N D U S T R Y



27

Integrated Tinting Systems for a Low-VOC Future

magenta or violet, their impact on the performance characteristics of the final product is minimal. It is important to integrate rules into the color formula database to ensure that only compatible colorants can be chosen with a selected product. Silicate and silicone-based paints, for instance, can only be tinted with water-based and universal colorants. While unlimited amounts of solvent-based colorants can be added to alkyd-based products, universal colorants may only be added in small amounts. This helps define the perfect balance between cost/performance and consumption of each individual colorant (Figure 4).

stics, including abrasiveness and speed of sedimentation or drying, could have a negative effect on the lifetime of pumps, valves or other mechanical parts. The right dispensing technology or even a combination of different technologies should be carefully considered. Further, it is important to select the optimal canister sizes and determine suitable stirring and recirculation needs for each individual colorant (see sidebar). This will help ensure that the colorant remains fresh in the canister, which will help minimize maintenance interventions.

The Formula of Color An Integrated Concept The challenge of a comprehensive, advanced tinting system extends beyond combining the colorants and color formulas. Proper configuration of the entire tinting system, including dispensing equipment, must be considered. Customization of a dispenser begins with an analysis of the retailer’s business model and average tinted sales volume. This will determine the speed requirements to properly serve the end-user customer. Once that is determined, the dispenser type must be carefully matched to properly support the colorant technology and established set of colorants. The behavior of the colorants over time within the dispenser must be also considered. Their various characteri-

Creating an accurate formula database is a critical part of integrated tinting system performance. The correct color formula rules ensure that the appropriate colorants are selected to achieve desired performance characteristics; for instance, UV-resistant colorants are used with exterior products. They minimize the overall formulation cost and optimize colorant consumption between all single colorants, meaning each single colorant should achieve a reasonable turnover to overcome technical problems. Through this process, a small selection of the color formulas may turn out to be more expensive than they previously were. However, the overall improved performance of the system will balance this out in the end. Maintenance costs and down times will be minimized as throughput of slow-moving colorants is improved. Lower total cost of ownership and superior tinting system performance are the ultimate objective of integrated tinting solutions.

Responsible Service Service is another key part of the tinting process that should not be overlooked. As integrated tinting systems are designed to fine tune all tinting components, it is important that the service provider be well versed in both the mechanics of the equipment and the characteristics of the colorant set. True tinting system support is best provided by a global network of trained specialists in colorants and system technology, who are able to modify existing systems and provide consultative assistance in case of problems. Choosing a partner who is responsible for the performance of all components of an integrated tinting system is a true competitive advantage. Consistent monitoring of color shade, strength and rheology during the production process results in assured color accuracy and reproducibility.

FIGURE 4 | Dual system vs. combined system.

n te ico ica Sil Sil

tex La

lic

ry Ac

d lky d ne lky il A A O ha il et m O r u i d lyu ng Lo Me Po

Water

Solvent

Consultative Services When setting up a truly integrated tinting system, it is important to make the right strategic business decisions throughout the design phase that create a sustainable, competitive advantage for the paint manufacturer. By working with a partner, capable of understanding all aspects of tinting system design, paint manufacturers can be assured that their business priorities will be achieved. Once implemented, only a supplier with comprehensive capabilities will be responsible for the long-term functionality of the complete integrated tinting system.

BINDER TECHNOLOGIES Water-based Water-based

28



Solvent-based Universal

Solvent-based

NOV EMBER 2011 | W W W . P C I M A G . C O M

Environmental Regulations – Not Just for Southern California As with many environmental legislative trends, what starts in Southern California quickly makes its way across the country. Is your company ready to implement upcoming

Painting is a cinch ...

With a paint that works with you! Introducing Eastman Optifilm™ additive OT1200 Extends open time, for improved wet edge and workability in paint Today’s paint has less workability time making it difficult to easily fix or paint over a mistake. Eastman Optifilm™ additive OT1200 — the newest addition to Eastman’s Optifilm portfolio — enables formulators to create low-VOC paints with improved open time and wet edge without negatively affecting other properties. OT1200 performs under a wide range of application conditions. The result is compliant paints with significantly improved workability and easier cleanup. For more information on Eastman Optifilm™ additive OT1200, visit us at www.eastman.com/optifilmOT1200 or call 1.800.EASTMAN for a free sample.

From the Eastman Optifilm™ family of products. Enabling performance, aesthetics, and compliance in architectural paints.

Eastman and Optifilm are trademarks of Eastman Chemical Company. © Eastman Chemical Company, 2011.

Integrated Tinting Systems for a Low-VOC Future

Come to King for Rheology Modifiers K-STAY Attributes: ®

K-STAY

x

Liquid Thixotropes

x x x x

For use in pigmented solventborne systems Highly efficient - low use levels Excellent sag control and pigment suspension Easy handling - pourable Alternative to discontinued Ircogel® products1 NEW K-STAY® 511 For Pigmented Solventborne Systems

K-STAY 511 0.2% K-STAY 511

0.4% K-STAY 511

Panel: Sag control with 0.2% and 0.4% dosage of K-STAY 511 - Polyester Can/Coil Coating

NEW K-STAY® 555 For Pigmented Solventborne Systems 3% Ircogel® 955

3% K-STAY 555

K-STAY 555

Comparison: 3% K-STAY 555 to 3% Ircogel 955 Polyester Bake Enamel

K-STAY® 501 For Pigmented Solventborne Systems K-STAY 501

Fumed Silica

Organo-Clay

changes to environmental legislation? The questions below will help to determine your own business readiness. If you are like many paint producers, you will find several questions difficult to answer. That is when a comprehensive tinting solutions provider can consult with you to design a system that will serve your company for years to come. • Are you currently conducting research and development on near zero-VOC colorants? • What is the timeframe to complete development and testing of a new near zero-VOC colorant system? • Do you have the technical resources in terms of lab personnel and equipment to complete a colorant technology conversion? • What are the steps involved in a colorant technology conversion to near zero-VOC colorants? • Will you need to adapt your color formula database or color formulation parameters to optimize performance of a new colorant system? • What is the expected timeframe to implement a change-over from glycol-containing to near zero-VOC colorant technology? • Will a near zero-VOC colorant system be compatible with your current, installed base of dispensing equipment? • What issues do you expect to experience in your point-of-sale operations as a result of a conversion to near zero-VOC technology? • What is the cost associated with retrofitting existing tinting equipment to meet the requirements of a near zero-VOC colorant system? • Is it preferable to invest in new dispensing equipment to avoid problems in the field, such as frequent mistints and maintenance downtime? • What is the one-time cost associated with a colorant technology conversion? The second article will delve deeper into the area of colorant technology to find new ways to deliver a sustainable advantage for your business. We will explore the colorant options beyond the traditional, commoditized, 12 colorant set, including highstrength colorants and colorants for specialized applications such as façade coatings. 

For additional information, contact Bart Wilbanks, Technical Account Manager, Colorants, CPS Color, at 800-728-8408 or 704-588-8408 ext. 240.

K-STAY 501

References 1

Comparison: K-STAY 501 to fumed silica and organo-clay Thixotropes at recommended use levels - Polyester/HMMM Coating

1

Ircogel® is a registered trademark of Lubrizol Advanced Materials, Inc. 2

New VOC Content Requirements for Colorants – passed June 3, 2011. PAR 1113 would establish VOC content limits for colorants effective Jan 1, 2014. The VOC content limit for colorants used to tint architectural coatings, excluding maintenance coatings would be 50 g/L. The VOC content limit for colorants used to tint waterborne industrial maintenance would also be 50 g/L. The VOC content limit for colorants used to tint solventborne industrial maintenance coatings would be 600 g/L. AQMD Colorant Survey 2010, Re: Proposed amended rule 1113.

Visit Us At

www.kingindustries.com Email: [email protected] Phone: 203-866-5551

Visit ads.pcimag.com 30



NOV EMBER 2011 | W W W . P C I M A G . C O M

Follow PCI on Facebook at www.facebook.com/PCIfan on Twitter at http://twitter.com/PCIMag and on Linkedin at www.linkedin.com

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes Influence on Paint Properties

W

aterborne acrylic latexes can be prepared via batch, seeded, in situ seeded and continuous polymerization. In this investigation, the seeded process was used for the preparation of nano-size seeds with a target average particle size of Dn ≤ 50 nm. These nano-size seeds were then used for the preparation of ultrafine full latexes via a semi-batch process with a target average particle size of Dn ≤ 100 nm. Surfactant concentrations were optimized to ensure minimal grit and coagulum and clean reactions with the final surfactant concentration of 0.45 parts per hundred of monomer (phm) in the final latex. Additionally, these ultrafine dispersions were evaluated for latex film appearance, gloss, adhesion and water pick-up performance. Finally, the dispersions were utilized to prepare semigloss paints to illustrate the effect of particle size on select paint properties (i.e., appearance, gloss, block and adhesion).

Introduction Waterborne coatings are applied on wood, metal, plastics, flooring and paper substrates to improve their aesthetics and provide protection from light, salt, heat and moisture. The key ingredients in a coating formulation are the pigment and binder. Pigments impart opacity, durability, anticorrosion and rust inhibition to the coating; the latex binder forms a film and holds pigment, filler and other components together, and additionally protects the substrate. The binder also contributes to the gloss, blocking and adhesion of the film. Surfactants play a critical role in binder preparation and are used to control particle size, reaction kinetics and latex stability.1,2 However, surfactants can negatively impact the block, scrub, adhesion and gloss properties of the coating, so it is generally desired to utilize minimal levels of surfactant and nano-size particles to circumvent these issues. Our investigations focused on screening various surfactants for making ultrafine latexes and determining the impact of these surfactants and latexes on paint properties.

Surfactant Selection A surfactant is a key ingredient in latex preparation. Four types of surfactants were selected for the acrylic seed and ultrafine full blown (FB) latex preparations. The benchmark surfactant utilized in the experiment was DowFax 2A1™ (DPOS). DPOS was selected as a control, as it is claimed in the literature to generate ultrafine particles at low surfactant use levels and offer excellent colloidal stability. Three types of AEROSOL® surfactants from Cytec Industries (i.e. sulfosuccinamates, monoester sulfosuccinates and diester sulfosuccinates) were also evaluated. The products included AEROSOL 22 (tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, 22), AEROSOL 18P (disodium Noctadecyl sulfosuccinamate, 18P), AEROSOL A-102 (disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid, A-102), AEROSOL EF-800 (proprietary sulfosuccinate surfactant mixture, EF-800), AEROSOL MA-80 (sodium dihexyl sulfosuccinate, MA-80) and AEROSOL OT-75 (sodium bis (2-ethylhexyl) sulfosuccinate, AEROSOL OT-75). Table 1 gives an overview of the various surfactants, select properties and features.

Experimental Results and Discussion Seed Preparation and Characterization Acrylic seed batches of 20% solids were prepared via a batch process (Table 2). This seed recipe was elected with goals of achieving a Tg ~14 °C binder, and seed particle size target was 40 to 50 nm at 5 phm surfactant use. The deionized water and surfactant solution were heated to 82 °C and mixed with an A310 impeller. At 50 °C bath temperature, the monomer solution was charged to the reactor. At a 75 ºC bath temperature, the initiator was charged and the agitation speed was increased from 200 rpm to 320 rpm. Following 1.5 h of reaction, the batch temperature was dropped to 40 °C. The seed was drummed out and filtered through a finer mesh filter for grit. All seed latexes achieved the desired conversion to 20% solids and evidenced nil to very minimal grit.

By Azhar Awan, Senior TS&D Scientist, and Dave Vanzin, TS&D Manager Americas, Cytec Industries Inc., Stamford, CT 32



NOV EMBER 2011 | W W W . P C I M A G . C O M

TABLE 1 | Surfactant properties and characteristics. Type

Critical Micelle Concentration (% weight)

Surface Tension (dynes/cm)

Alkyl diphenyl oxide disulfonate

0.03

34

Sulfosuccinamate

0.04

36

AEROSOL 18P AEROSOL A-102

Sulfosuccinamate Monoester sulfosuccinate

0.06 0.1

40 29

AEROSOL EF-800

Monoester sulfosuccinate

0.03

31

AEROSOL MA-80

Diester sulfosuccinate

1.5

28

AEROSOL OT-75

Diester sulfosuccinate

0.12

26

Surfactant DPOS AEROSOL 22

Seed particle sizes are detailed in Figure 1. AEROSOL 18P produced seed particles of 37 nm and exhibited no obvious negative process artifacts (i.e., minimal aggregates, grit and coagulation). The fine seed particles, narrow size distribution and clean process attributable to AEROSOL 18P could possibly be explained as follows: (a) the use level of 5 phm is sufficient for the seed particle full coverage; (b) the AEROSOL 18P diffusion rate fits quite well with the seed particle formation and its growth; and/or (c) the molecule anchored well and was not easily displaced when the seeds were mixed and sheared during polymerization. The AEROSOL 22 also yielded a small seed particle of 47 nm. Additionally, no coagulum and grit were observed. It is speculated that AEROSOL 22 has less affinity for the monomer droplets and poor pre-emulsion stability but possesses a higher affinity for the particle and its stability. AEROSOL A-102 yielded a seed particle size of 49 nm. AEROSOL A-102 offers a stable pre-emulsion, and this is highly desirable for various EP process schemes where reaction ingredients are charged from a single line and tank. This better emulsion stability means that AEROSOL A-102 has a stronger affinity for the acrylic monomers. Therefore, at any given time during polymerization, it is less available for particle protection and stability. Seed particles prepared with DPOS were 50 nm, and there was no reactor build-up or grit observed. The AEROSOL EF-800 surfactant produced seed particles of 55 nm, which was greater than the desired size. The pre-emulsion stability was poor compared to DPOS but better than AEROSOL 18P and AEROSOL 22. The larger size particles and build-up on the reactor blades are probably attributable to the lower affinity of this surfactant for the acrylic seed particles. The AEROSOL OT-75 surfactant yielded a final seed particle size of 55 nm. It is hypothesized that the larger size seed attributed to AEROSOL OT-75 limits its availability to support the stability and growth of the primary particle. This higher emulsion stability and more solubility within polymer particle core could mean that AEROSOL OT-75 possesses limited ability to support particle nucleation and its growth. The AEROSOL MA-80 was selected to facilitate the preparation of larger size particles, yielding a seed particle size of 72 nm. One could expect that due to its high

Features Ultrafine particle size, water resistance and colloidal stability Small particle size, excellent salt tolerance, mechanical stability Emulsifier and dispersant Sole emulsifier, excellent stability Sole emulsifier, imparts excellent stability, high tolerance for water-sensitive polymers Dynamic surface properties, costabilizer/ emulsifier Excellent co-emulsifier, outstanding wetting and dispersing properties

CMC, AEROSOL MA-80 would be expected to produce bigger size particles.

Ultrafine Full Blown Latex Preparation and Characterization The amount of the seed for the FB latex for AEROSOL 18P and other seed batches was calculated using Table 3, and for AEROSOL 18P it was 66.5 grams. The FB latex theoretical average particle size was 85 nm. The surfactant

TABLE 2 | Pure acrylic latex seed recipe. Reaction Ingredients

Amount (g)

Butyl acrylate (BA) Methyl methacrylate (MMA) Acrylic acid (AA) Deionized water (DI Water) Surfactant (phm) Ammonium persulfate (APS) DI water for catalyst Total Seed solids (%)

23.6 15.0 0.7 144.0 5.0 0.4 15.0 203.7 ~20

FIGURE 1 | Seed batches particle size and particle size distributions from various surfactants. 72.6 Seed Particle Size (nm) Seed Particle Std (nm) 55.1 50.4

49

47.3 37

12.6

11.9

D

PO

S

AE

RO

SO

L

22 R AE

O

SO

L

18

P

A

O ER

SO

L

A-

10

2

AE

RO

SO

15.7

15.1

12.7

9.8

L

EF

-8

00

AE

RO

SO

PA I N T & C O A T I N G S I N D U S T R Y

L

M

A-

80



33

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes

TABLE 3 | Seed calculation methodology for the preparation of FB latexes. 18P seed average Dn particle size (nm) FB latex target particle size (nm) Total solids (%) Seed amount (g) Surfactant level for FB latex (PHM) Theor. volume growth factor (about) Total polymer (g) Total polymer volume (ml) Seed polymer volume (ml) Seed polymer (g) Seed solids (%) SAA from seed (g) Monomer added for Fb latex (g) Monomer added for Fb latex (ml)

37 83 45.0 66.5 0.44 11.3 142.6 101.9 9.0 12.6 19.0 0.63 130.0 92.9

TABLE 4 | Recipe used for FB latex preparations. Reaction Ingredients

Amount (g)

Seed (19-20%) solids BA MMA AA DI water Sodium bicarbonate APS DI water for APS Total ingredients Solids (%)

~ 60.00 55.00 70.00 2.70 110.00 0.35 0.90 10.00 249.30 45

TABLE 5 | Latex characterizations. Surfactants Used

DPOS

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL 22 18P A-102 EF-800 MA-80

Surfactant level 0.45 (phm) Measured solids (%) 45.0 Conversions (%) 100.0 pH 4.75 Mean particle size 110 (nm) std± 16 Latex film thickness T - 2.5 mil wet Adhesion 8 Viscosity (cP) 25 Freeze/thaw F stability (cycles)

0.45

0.45

0.45

0.45

0.45

44.7 99.9 4.5

45.0 100.0 4.2

45.0 100.0 5

48.0 100.0 4.5

46.0 100.0 3.9

87

88

125

93

bimodal

23

23

15

25

B/T

T

T

T

T

10 12

10 30

10 33

10 22

10 40

F

3

1

F

F

T: Transparent, B/T: Bluish/Transparent; and F: Failed

TABLE 6 | Water intake properties. Surfactant Used for the Seed

Films Immersed for 30 min in Water

Films Immersed for 1 h in Water

Films Immersed for 4 h in Water

DPOS AEROSOL 22 AEROSOL 18P AEROSOL A-102 AEROSOL EF-800 AEROSOL MA-80

Nil Nil Nil Nil Nil Nil

Nil Nil Nil At the edges At the edges Hazy

Hazy Hazy Hazy Hazy Hazy Hazy

34



NOV EMBER 2011 | W W W . P C I M A G . C O M

from seed was 0.6 g, and this overall amount was used in each batch and was 0.45 phm. The FB latex recipe is given in Table 4. Initially, DI water was added to the seed and the seed gently mixed. After DI water addition, the seed was then mixed for 2 more min and charged to the reactor. After the seed solution charge, the process conditions for the FB latex were similar to the seed preparation with the exception that the monomers were charged over 2.5 h. Latex characterizations are given in Table 5. The theoretical and experimental solids are in good agreement. Batches were rated Pass/Fail, with Pass designating minimal coagulum, grit and residual monomers, and Fail designating that coagulum, grit or residual monomers exceeded polymerization process norms. The AEROSOL OT 75 batch was the only failure, as it coagulated during polymerization. The control latex prepared from DPOS yielded a particle size of 110 nm. Latexes prepared from the AEROSOL 22 and AEROSOL 18P sulfosuccinimate surfactants evidenced particle sizes of 87 and 88 nm respectively, and grit, coagulum and reactor build-up were low (AEROSOL 22 was 0 and AEROSOL 18P was 0.4 g). The particle sizes of latexes prepared from the sulfosuccinate surfactants AEROSOL A-102 and AEROSOL EF-800 were 125 and 93 nm, respectively, and additionally, these products evidenced 0 and 2 g coagulum. The AEROSOL MA-80 surfactant-based latex produced a particle size of 180 nm with some fine particles. The viscosity of all the final latexes was below ~50 cps, which is desired by latex and paint producers as this facilitates easy transfer, addition and mixing. To assess surfactant influence on latex properties, film drawdowns were prepared on Leneta paper. The films were 2.5 mils wet and were initially dried for 1 min at room temperature and then placed in an oven at 107 °C for 5 min. The AEROSOL 22 was continuous and transparent, and the AEROSOL MA-80 film was hazy and continuous. All films based on the other surfactants evidenced some degree of mud cracking (i.e. leaf type morphology). Latex film adhesion to glass and Leneta paper was investigated per ASTM D 7234-05, and all films evidenced excellent adhesion. The surfactant influence on the freeze/thaw (F/T) stability of the latex was assessed. Only the latex based on the 18P passed the desired 3 F/T cycles.

Latex Water Uptake Latexes used as binders in exterior paints require good water resistance, and surfactants can greatly influence water intake. To assess various surfactants’ influence on this property, 1 mil dry films were prepared on glass, and film samples were dried at 107 °C for 5 min and then aged overnight in a controlled humidity and temperature room (CHT-50% humidity at 24 °C). The glass panels were then submerged into a water bath and observed and monitored over a 4-h period. Results are shown in Table 6. The good to excellent water resistance properties of these latexes could be due to: (a) lower surfactant use; (b) surfactant and polymer compatibility and (c) ultrafine particles.

Latex Gloss Properties Dry latex films (1 mil) were prepared on Leneta paper.

FIGURE 2 | Gloss properties at 20°, 60° and 85°.

FIGURE 4 | Semigloss paint gloss – latexes prepared from various surfactants.

120

100 90

80

80

 

60

   Paint Gloss

Film Gloss

100

40 20

70 60

Paint 20º gloss

50

Paint 60º gloss

40 30

0 20º gloss 60º gloss 85º gloss

  AEROSOL    AEROSOL    AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22 63 59.5 64 67 13   86 82.7 73 83 55 97 96.8 90 90 89.5

DPOS 59 86 81

Paint 85º gloss

20 10 0 D

FIGURE 3 | Semigloss paint block – latexes prepared from various surfactants.

PO

S

AE

RO

SO

L

22

R AE

O

SO A

L

18

O ER

P

SO

Paint  block  "0" no  block,  and "10"  perfect  block 

L

AE

A-

10

RO

2

SO

L

EF

AE

-8

RO

00

SO

L

M

A-

80

10

in a CTR room. Paint films were continuous and their surfaces smooth. These paint films were then tested for block, gloss and adhesion properties.

9

9 8

8

Paint Block Performance

7 6

6

5 4 3 2

2

2 1

1 0 DPOS

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22

The films were dried 60 s at RT, and then dried in an oven above 90 °C for 5 min. Films were aged in the CHT room. For each film, 20°, 60° and 85° angle gloss was measured (Figure 2). The AEROSOL 18P and AEROSOL 22 surfactants yielded the best overall results and were closely followed by AEROSOL A-102, EF-800 and DPOS products. The AEROSOL MA-80 latex did yield a smooth and continuous film. However, it also yielded the poorest 20° gloss performance, and this lower gloss is attributable to large latex particle size.

Semigloss Paint Preparation – Attributes and Properties The latex pH was raised to 8 and the latex was added to the semigloss grind to prepare paints (51.7 % solids and 24% PVC). Paint films, 2.5 mil wet and 1 mil dry, on Leneta paper and glass surfaces were prepared. Paint films were then conditioned for 1 day and for 1 week

Coupons were prepared and used for block resistance properties at 24 °C and 40 °C. Block performance is rated on a scale of 0 to 10, with 0 meaning no separation and 10 meaning complete separation. The data is presented in Figure 3. Paints prepared from AEROSOL 18P and AEROSOL 22 showed the best performances and these were followed by DPOS-containing latex. The block property associated with the AEROSOL MA-80, AEROSOL EF-800 and AEROSOL A-102 was poor. It is hypothesized that AEROSOL 18P and 22 are more compatible in the polymer matrix.

Paint Gloss Properties Paint gloss can be influenced from various components of the paint formulation. To assess the influence of surfactant type and amount, as well as latex particle size on paint gloss, gloss was measured (Figure 4). The 20°, 60° and 85° gloss evidenced similar ranges. Thus, the latex particle size between 80 nm and 120 nm had no apparent effect on paint gloss properties.

Paint Adhesion Properties Semigloss paint adhesion was measured via ASTM D 7234-05 cross-hatch method. Adhesion performance is rated on a scale of 0 to 10, with 0 meaning no adhesion and 10 meaning nothing was removed. After 8 days of CRT conditioning, both the sulfosuccinamates (AEROSOL 18P and AEROSOL 22) and sulfosuccinates (AEROSOL A-102, AEROSOL EF-800 and AEROSOL MA-80) surfactant-containing paints exhibited excellent adhesion. The adhesion of the DPOS control was also good, but slightly lower (Figure 5). PA I N T & C O A T I N G S I N D U S T R Y



35

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes

Conclusions and Summary Nano-size seeds of ≤ 50 nm and 20% solids were successfully prepared utilizing AEROSOL 22, AEROSOL 18P, AEROSOL A-102 and DPOS surfactants. A semi-continuous polymerization process was successfully exploited to

FIGURE 5 | Semigloss paint adhesion – latexes prepared from various surfactants. 12

  Paint Adhesion Rating 10

prepare ultrafine (nano) latexes of ) 100 nm at ultralow (0.45 phm) surfactant use levels with AEROSOL 22, 18P, A-102 and EF-800. 18P latex also offered better F/T stability opposite to DPOS. These ultrafine latex films evidenced excellent aesthetics, gloss, adhesion and low water intake. Latexes of both less or greater than 100 nm particle size offered excellent suitability with and compatibility towards the semigloss paint grind. Paint film surfaces were smooth and glossy, and cross-hatch adhesion performance was also exceptional. Paints prepared from AEROSOL 22 and AEROSOL 18P-based latexes also yielded excellent block resistance properties. 

References

8

1

6 2

4 2

For more information, e-mail [email protected].

0 DPOS

36



Daniels, E.S.; Sudol, E.D.; El-Aasser,M.S. Polymer Latexes, Preparation, Characterizations, and Applications, ACS Symposium Series, 492, ACS, Washington, DC 1992. Lovell, P. In Emulsion Polymerization and Emulsion Polymers, El-Aasser, M.S; and Lovell, P., Eds., John Wiley & Sons London, 1997.

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22

NOV EMBER 2011 | W W W . P C I M A G . C O M

This article was presented at the 38th Annual Waterborne Symposium in New Orleans, LA.

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Formulation Optimization Utilizing DOE Mixture Statistics

M

aintaining maximum color development throughout the production process for cellulose acetate butyrate/acrylic-based automotive refinish formulations with high-strength carbon black has always been an issue. Formulators have found that the order of addition can impact the final color of the applied coating. For this reason, it is imperative that the grind formulation provides the highest possible color strength, as it is likely to lose some color development in the course of processing. This problem can be studied using the traditional scientific approach of isolating independent variables and examining their impact on the desired properties. However, when this is done, it quickly becomes apparent that something is being missed. One by one, the optimal

TABLE 1 | Generic automotive refinish black basecoat formulation. Grind

Weight %

CAB 381-2 Toluene Borchi Gen 0451 FW200

2.15 42.95 5.48 8.53

Letdown

Weight %

Acryloid A-21 100% Santicizer 160 n-Butyl acetate Isopropanol MIBK

10.20 1.30 13.39 11.50 4.50 100.00

TABLE 2 | Constraints for factors in mixture DOE. Low

Constraint

High

3.00 81.50 10.50

A: CAB 381-2 B: Toluene C: Gen 0451 A+B+C

6.00 86.50 12.50 100.00

amount of each formulation component is empirically determined through experimentation, but when these components are combined at the determined ratios, the results are far less desirable than predicted. When evaluating Borchi® Gen 0451 pigment dispersant in CAB/TPA automotive refinish applications, this phenomenon was experienced. Laboratory trials to evaluate Borchers® dispersants produced inconclusive and even conflicting results. The problem lies in the fact that the separate components could have interactions with each other with respect to the desired properties. For example, when the formulator changes the level of dispersant in the grind formulation, the loading of the other components is also changed. If all the components have interactions with the responses, how can you conclude that changes in the desired properties are due only to the change in dispersant level – even if the ratio for the other components remains constant? If one plans traditional experiments, altering the ratios of each component individually and in combination with the other components, the number of trials adds up quickly, and this approach is simply not feasible. There is a powerful statistical approach that is well suited for formulation optimization. It is a subset to the design of experiment (DOE) technique called mixture statistics. This statistical technique is designed to allow the experimenter to account for all component interactions, and calculate a formulation that is most likely to maximize the desired properties.1 Unfortunately, a common response to the mere mention of DOE is skepticism and resistance. It is true that a traditional factorial DOE is very limited in value when applied to formulation development. However, a DOE need not be the all-encompassing, labor-intensive exercise that many have encountered. In fact, the proper application of DOE methods should minimize the amount of time and resources needed to achieve the desired goals.2-4

The Formulation To illustrate the use of mixture statistics, a generic automotive refinish black basecoat formulation was

By Kip A. Howard, Research and Development Laboratory Manager | OMGroup Paint and Coatings Additives, Westlake, OH 38



NOV EMBER 2011 | W W W . P C I M A G . C O M

A: CAB 381-2 %

B: Toluene %

C: Gen 0451 %

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

6.00 3.33 3.00 4.65 5.44 6.00 4.98 4.00 5.44 4.00 3.00 3.00 4.65 3.00 3.80 4.25

83.50 85.55 86.50 84.01 82.76 81.50 84.52 83.50 82.76 83.50 85.02 86.50 84.01 85.02 84.36 85.25

10.50 11.11 10.50 11.33 11.80 12.50 10.50 12.50 11.80 12.50 11.98 10.50 11.33 11.98 11.84 10.50

TABLE 4 | Measured responses for mixture DOE grind formulation trials.

Run

60° Gloss

L*

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

92.65 104.35 98.35 108.50 98.30 98.55 96.05 106.15 98.55 103.35 98.20 100.10 104.90 103.25 95.65 94.90

24.38 27.04 24.90 27.67 25.07 25.27 24.34 27.48 25.63 27.91 25.05 25.85 26.50 26.46 24.29 24.51

TABLE 5 | Constraints for mixture optimization calculation. Name A: CAB 381-2 B: Toluene C: Gen 0451 60° gloss L*

Goal

Limit

Limit

Is in range Is in range Is in range Maximize Minimize

3.00 81.50 10.50 92.65 24.29

6.00 86.50 12.50 108.50 27.91

TABLE 6 | Calculated optimal grind formulations based on DOE mixture results. CAB 381-2 Toluene

5.25 82.25

Borchi Gen 0451

12.50

60° Gloss L* Desirability

102.47 25.23 0.68

FIGURE 1 | 3-D surface of L* as a function FIGURE 2 | 3-D surface of 60° gloss as a of the three factors. function of the three factors. 34 32 30 28 26 24 22

60º Gloss

Run

L*

TABLE 3 | Grind formulation mixture design.

C (10.500)

B (86.500)

A (3.000)

A (8.000)

120 115 110 105 100 95 90

A (8.000) C (10.500)

B (81.500) C (15.500)

B (81.500) B (86.500)

A (3.000)

C (15.500)

chosen (Table 1). Design Expert ® by Stat-Ease, Inc. was used to develop the mixture DOE. This project focused on optimizing the grind formulation for maximum color development and gloss.

Mixture DOE Three components were included in the mixture, keeping the level of carbon black constant for each trial: A: CAB resin; B: Toluene; C: Borchi Gen 0451. In a mixture DOE, all of the components are varied based on a statistical model, with the total adding up to a predetermined constant (in this case, 100 parts or percent). However, it is not useful to include trials that are not feasible. For instance, one would not want to include trials where the level of CAB resin is higher than the maximum soluble amount. These are called constraints. The constraints for the grind mixture DOE are listed in Table 2. The responses (desired properties) were defined as R1: 60° Gloss, and R2: L* value. Using the quadratic design model, the trials were generated as listed in Table 3. Each of these trials was used to disperse 12.66% carbon black and processed simultaneously for 2 h on a LAU DAS-200 disperser. The resulting paint samples were drawn down at 5 mils wet thickness and allowed to dry for 12 h at 25 °C, 50% relative humidity. The drawdowns were then measured for color and 60° gloss; the results can be found in Table 4. After analyzing the results, it was determined that this mixture has A:B:C interactions for each component, confirming the theory that complex synergies exist in this formulation. After selecting a model that best fit our data and accounted for these interactions (in this instance the cubic model), we generated a visual representation of our three-component mixture with respect to each response (Figures 1 and 2). Examining these graphs, it was apparent that our responses had conflicting optimal formulations. Mixtures that maximized gloss also minimized color strength and vice versa. The goal now was to find the optimum formulation that provided the best color strength in combination with the best gloss. The good news was that we had all the data necessary to accomplish this. The optimum grind formulation could now be calculated by choosing the constraints found in Table 5. The Design Expert software then interpolated 40 additional responses based on the model, and provided the suggested optimized formulation (Table 6). PA I N T & C O A T I N G S I N D U S T R Y



39

Formulation Optimization Utilizing DOE Mixture Statistics

TABLE 7 | Optimized grind formulation validation test results. L*

60° Gloss

26.19

104.25

Validation The calculated optimal formulation from Table 6 was produced and tested using the same methodology as our trial grinds to validate the predicted responses by our model; the results are located in Table 7.

Conclusions The use of mixture statistics with formulation development is valuable because it provides a clear, concise path to obtain an optimum formula within a practical number of trials. However, this technique can also provide a complete understanding of interactions that exist between all of the ingredients with respect to the desired properties. Limitations of the formulation are also characterized, preventing the formulator from setting specification goals that are unachievable using current raw materials and processes. This information provides additional value to the time and resources expended developing the formulation that traditional trial work simply does not offer. 

References 1

2

3

4

Experimenting with Mixtures, Chemtech, Nov., 1979, pp 702-710. Jameel, Feroz and Hershenson, Susan. Formulation and Process Development Strategies for Manufacturing Biopharmaceuticals, John Wiley and Sons, 2010 pp. 320-327. Anderson, M.J. and Whitcomb, P.J. Mixture DOE Uncovers Formulations Quicker, Rubber and Plastics News, October 21, 2002.2. Scheffe, H. Experiments with Mixtures, J. of the Royal Society Series B, Vol. 20, No. 2, 1958, pp. 344-360.3.

E-mail [email protected] for more information, or visit www.omgi.com or www.borchers.com. The author would like to thank the following individuals for their contributions: Mary Hopkins, Nicholas Schady, Susan Vicha and Timothy Armistead.

Find On-Demand Webinars at webinars.pcimag.com or www.borchers.com. Visit ads.pcimag.com 40



NOV EMBER 2011 | W W W . P C I M A G . C O M

A New Way to Produce

Antimicrobial Coatings

A

nti ntimicrobial t i miicro obi bial a l coa coatings oati tin ti i ng ngs are used used d in i n many y applications, varying applications s, va vary ryin ry i ng from antifouling paints, coatings used in hospitals and on medical equipment, to algaecidal and fungicidal coatings in and around the house. A growing problem in our world is that, for reasons of health and the environment, more and more biocides are being prohibited, and at the same time, bacteria are becoming more resistant. AM Coatings has developed a unique and worldwide patented technology under the name of AM Inside®. This technology provides safe and durable protection against bacteria, algae, molds and fungi. Coatings with this new technology do not contain biocides. AM Inside operates differently than traditional antimicrobial coatings – mechanically rather than chemically. By using a double polymerization process, an antimicrobial binding agent is fabricated. This binding agent has a very special property, creating a kind of “nanotechnological barbwire” surface, during the curing process. When a microbe (or any micro-organism) comes in contact with this surface, its cell wall is punctured like a balloon, so the microbe dies (Figure 1). Apart from being completely safe for humans and the environment, this mechanical action has another big advantage: microbes will not become resistant to this kind of control, a phenomenon that appears to become a growing problem, for instance with the notorious MRSA infection in hospitals. Traditional antimicrobial coatings contain biocides that are gradually released (leach out). The resulting toxins then enter the microbe and kill it. Although this is an effective process, there are a few important drawbacks, which can be avoided by using this new technology. • Standard biocides may pose a health risk1 and may be environmentally hazardous.2 This is why application of these biocides is increasingly being restrained and subjected to strict and costly admission requirements. • Because the active ingredients leach out, these chemicals have only a short life span.3 The effects diminish in

FIGURE 1 | Schematic illustration of the anti-bacterial function of AM Inside.

Kille

Bacteria

d Bac

teria

Leakage of Cell Components

FIGURE 2 | Tomato test after 38 days.

Without Coating

Silver-Based Biocide

AM Inside

due course because the biocide concentration diminishes. • The direct surroundings are contaminated with higher concentrations of biocides. AM Inside technology has been proven, based on American ASTM E 2149 and Japanese JIS Z 2801 standard test methods. Practically, the technology has been proven as well. Figure 2 shows a tomato that did not deteriorate, decay or mold inside a beaker coated with AM Inside, even after 38 days. The other two beakers (one without a coating and one coated with a silver-based biocide), show clear deterioration.

Summary AM Coatings’ technology is not harmful to humans or animals; it can be applied everywhere and without special precautions. No special labeling or costly and time-consuming registration and admission procedures are required. AM Inside grafted on the polymer is made with common and widely available raw materials, and all are REACHcompliant. It is non-leaching, meaning there is no negative environmental impact and no loss of effectiveness. AM Inside is effective against a wide number of strains of bacteria including MRSA. Because it works mechanically, it is impossible to build up resistance against it. Waterborne paints based on this technology possess enhanced low-odor and nonbleeding properties, and are just as green and sustainable as common, unmodified paints not containing additional antimicrobial components. AM Coatings is expanding its range of binders modified with the technology, serving other coating applications and non-coatings segments. For more information, and to view an animated video on how this technology works, visit www.amcoatings.com and www.am-inside.com. 

References

AM Inside

1

2

Surface

3

The Role of Antimicrobial Silver Nanotechnology, Medical Device & Diagnostic Industry Magazine, August 2005. Chai, Joyce S. Water Conditioning & Purification Avoiding the Silver Lining, 12/2008. Anti-infective catheters: A difficult search for effective slow delivery systems.

By Hossein Mahmoud, Inventor and Director | AM Coatings, Ede, The Netherlands. PA I N T & C O A T I N G S I N D U S T R Y



41

Innovation and Sustainability Highlighted at

ABRAFATI 2011

A

BR AFAT BRAFATI BRAF ATII 2011 2011 will wil illl be held hel eld d from from NovemNov ovem em ber 21 - 23 at Transamerica Expo Center, in São Paulo, Brazil. The most important event in the coatings sector in Latin America will gather the 12th International Exhibition of Coatings Industry Suppliers and the 12th International Coatings Congress. Solutions to the future demands of the coatings industry will be highlighted both in the Congress and the Exhibition, which will present and discuss paths and trends in terms of raw materials, products, processes, technologies, applications, environmental impact and many other areas. Over 200 companies have already confirmed their participation in the Exhibition. The favorable growth perspectives for the Brazilian and Latin American coatings industry in the coming years are stimulating suppliers, who see ABRAFATI 2011 as an excellent opportunity to expand their businesses. As a result of the investments in oil exploitation, infrastructure improvement, preparation for the Soccer World Cup and the Olympic Games, it is estimated that the Brazilian market will double its current size in a few years. This will probably be the most international of the event’s editions, with significant presence of European, North American and Asian companies.

12th International Coatings Congress At the International Coatings Congress, experts will present ongoing research and recent developments, which open new possibilities for the formulation, production or use of coatings. Environmental aspects will be a highlight because of the growing relevance of the theme for society and for the future of the coatings industry. As with every edition of the Congress, many studies on technologies, raw materials and innovative processes will be presented under the form of lectures or posters addressing how to improve the performance of coatings,

costs produce add functionalities add func fu ncti tion onal alit litie ies to them, the hem m reduce red educ ucee co cost sts an and d pr prod oduc ucee le less impact on the environment. The Congress includes 72 oral presentations, the Poster Session and two special seminars, one on radiation-cure technology, and one on environmental and safety issues. The entire program is available at www.abrafati.com.br. One of the highlights of ABRAFATI 2011 are the Plenary Sessions, which offer comprehensive and privileged perspectives on key issues in the coatings chain. These sessions will be presented by professionals with a broad range of expertise and a tangible record of accomplishments.

Plenary Sessions November 21 – 1st Plenary (8:30 a.m. - 9:30 a.m.) The Performance of the Coatings Industry in 2011 and the Brazilian Scenario for the Decade Antonio Carlos de Oliveira Chairman of the Executive Board of ABRAFATI, Director of the division of DuPont Automotive Systems in Latin America, General Operation Manager of DuPont Performance Coatings Brazil November 21 – 2nd Plenary (6:00 p.m. - 7:00 p.m.) Coatings and Raw Materials: Perspectives on the Global Market John Klier Global Research and Development Director of Dow Coating Materials November 22 – 3rd Plenary (8:30 a.m. - 9:30 a.m.) Automotive Coatings and the Environment Lewis E. Manring Vice-President of Technology of DuPont Performance Coatings November 23 – 4th Plenary (8:30 a.m. - 9:30 a.m.) The Coatings Global Market: Dimension, Tendencies and Key Themes Louis McCulloch Specialized consultant in the coatings industry, with over 30 years as an executive in companies in the sector, former editor of The Coatings Agenda. 

ABRAFATI 2011 November 21 - 23, 2011 Exhibition: 7:00 a.m. to 4:00 p.m. Coatings Congress: 10:00 a.m. to 8:00 p.m. Location: Transamérica Expo Center, São Paulo, Brazil Information and registration: www.abrafati2011.com.br

42



NOV EMBER 2011 | W W W . P C I M A G . C O M

Novembro 2011

Paint

Coatings Industry

Biocida com Liberação Controlada Agente Umidificador para Adesivos Tecnologia de Poliuretano à Base de Água

P O N TO D E V I S TA

Brasil posicionado para o crescimento Recentemente, tive uma conversa telefônica muito interessante com David P. Nick, Presidente e CEO da DPNA International Inc. Durante a conversa sobre o evento da ABRAFATI realizado esse mês em São Paulo, Brasil, Dave me falou sobre a aliança dos países do BRIC. Eu sempre leio bastante sobre as economias em rápido crescimento e a expansão do setor de revestimentos no Brasil, Rússia, Índia, China e África do Sul (países do BRICS), mas eu não sabia que esses países tinham formado uma aliança comercial sem precedentes. O BRICS não é um bloco comercial formal, mas uma aliança econômica flexível, não baseada numa moeda, em política ou em diretrizes comerciais tradicionais. Cada um desses países tem alguma coisa que os outros querem. Para citar algumas delas, o Brasil tem terra, petróleo e produtos agrícolas; a Rússia tem petróleo e gás, a China tem uma mão de obra imensa e necessidade de petróleo e gás; a Índia tem amplo conhecimento e recursos de TI e a África do Sul tem metais preciosos e diamantes e é a porta para a África. Mais do que estabelecer acordos comerciais MOINHO HORIZONTAL PÉROLA PACOTE DE SELO MECÂNICO MULTILANGUAGE PLC CONTROLE DIFERENTES MATERIAIS DE CONSTRUÇÃO

PRODUÇÃO EM LOTES PROJETO SIMPLE, ROBUSTO TODA A CONSTRUÇÃO DE AÇO OPERAÇÃO AUTOMATIZADA AMPLA VARIEDADE TAMANHO

PROCESSAMENTO PERSONALIZADO DEIXE NOSSOS ESPECIALISTAS AJUDÁ-LO COM A SUA DISPERSÃO PROJETOS, APRESENTADA MOSTRA QUE VOCÊ PRECISA E COMECE AGORA

baseados em dólares ou euros, esses países criaram acordos de permutas. A China, por exemplo, pode concordar em construir um sistema rodoviário na África do Sul, incluindo o financiamento, mão-deobra e equipamentos, em troca de um contrato plurianual para o desenvolvimento dos recursos relacionados a metais ou carvão do país. Essa aliança pode tornar o crescimento contínuo desses países em algo real e sustentável. Ela não depende do que acontece na Europa ou nos Estados Unidos. De acordo com Nick, o BRICS representa uma transferência coletiva do poder econômico dos países desenvolvidos do G-7 para o mundo em desenvolvimento, e muitos outros países estão ansiosos para entrar para o clube. Espero ler mais sobre a BRICS e acompanhar o seu progresso nos próximos anos. Mesmo com a publicação recente de um informativo da ABRAFATI (Associação Brasileira de Fabricantes de Tintas) afirmando que o crescimento do setor de revestimentos caiu 10% no Brasil em relação à 2010, o futuro parece promissor. O crescimento total do setor de tintas no Brasil deve ser de 1,3% (devido ao clima econômico internacional questionável e a dúvida sobre reformar ou construir), alcançando 1.377 bilhões de litros, com expectativa de crescimento das vendas na ordem de 4% em 2012. Numa tentativa de promover o desenvolvimento econômico e social, o governo brasileiro lançou o programa habitacional Minha Casa, Minha Vida 2 e prorrogou a redução do IPI. De acordo com Dilson Ferreira, presidente executivo da ABRAFATI, “é importante frisar que, além dos grandes eventos que teremos até 2022 (como a Copa do Mundo da Fifa em 2014 e as Olimpíadas em 2016), que garantirão o crescimento sustentável, os aspectos estruturais que estimulam as vendas estarão presentes por muitos anos. Entre esses fatores, os mais notáveis são o investimento em habitação e infraestrutura, a ampliação dos segmentos relacionados à exploração e distribuição de petróleo, o fortalecimento do mercado interno e o crescimento da classe média.” Na tentativa de alcançar esse mercado em crescimento e os participantes do evento da ABRAFATI, a PCI apresenta o nosso primeiro suplemente em português nesta edição, que será distribuída na feira. Esperamos essas informações sejam úteis e esclarecedoras para os leitores da edição em português e que possamos publicar mais suplementos como esse no futuro.

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Inovação para Todos

Há mais de uma década, a Celanese é líder no desenvolvimento de emulsões para tintas amigáveis às pessoas e ao meio-ambiente. Na América do Sul, estamos atualmente tornando mais fácil a formulação de tintas decorativas de alto desempenho e com atributos amigáveis que todos possam apreciar. Venha nos visitar na Abrafati 2011 onde você poderá saber mais sobre as emulsões EcoVAE® para tintas com baixa emissão VOC, baixo odor, e livre de Alquilfenóis Etoxilados. Venha conhecer nossa tecnologia de emulsões e os recursos que a Celanese pode oferecer para inovar a forma de produzir tintas decorativas na América Latina. Venha nos visitar na

ABRAFATI Stand 176

Ligue agora: +55 11 8653 0490 www.Celanese-Emulsions.com/Brasil

Em todo o mundo…seu futuro é nosso foco.

Desempenho Superior de por meio do Controle da

B

iocidas são necessários para evitar a deterioração microbial de vários revestimentos industriais. As duas principais aplicações dos biocidas são (a) evitar a deterioração do produto em estado molhado durante o armazenamento e transporte (proteção na lata) e (b) garantir um desempenho duradouro do revestimento (proteção da película seca).1 Ao secar, tanto as tintas à base de água como de solvente ficam vulneráveis à formação de colônias de fungos e/ou algas. O crescimento de micro-organismos na película seca não somente afeta a aparência do revestimento (descoloração), mas também compromete o seu desempenho (biodegradação). Pode haver penetração de fungos nos revestimentos, causando trincas, bolhas e perda da adesão, levando à deterioração ou corrosão do substrato. Colônias de algas, que parecem crescer mais rapidamente sobre substratos porosos, como estuco, cimento e tijolos, ocluem água. O congelamento e degelo dessa água presa podem causar trincas ou aumentar a permeabilidade do revestimento, levando a defeitos. A presença de água pode também estimular a formação de colônias de outros micro-organismos que, por sua vez, podem causar biodegradação.2 O tipo de micro-organismo que consegue colonizar o revestimento depende de vários fatores, como teor de umidade da superfície, presença de nutrientes, substrato e composição do revestimento.3 A fim de ser mais eficaz, o biocida precisa estar presente na interface do revestimento. Isso faz com que ele seja suscetível à lixiviação por água. O controle da liberação do biocida por meio do encapsulamento pode garantir que uma concentração mínima de biocida seja sempre mantida na superfície da interface, prolongando a vida útil do revestimento. Além disso, essa liberação controlada pode reduzir a quantidade de biocida liberada no meio-ambiente ao longo do tempo. Este artigo descreve a liberação controlada de IPBC (3-iodo2-propinil butilcarbamato). Consegue-se uma proteção duradoura da superfície por meio da absorção entre o biocida e o portador.4,5 Isso faz com que o biocida se torne resistente à FIGURA 1 | Lixiviação Cumulativa de IPBC em películas. 14 13

IPBC

% IPBC

12 11

Fungitrol® 940CR

10 9 8 7

1

3

15

48

Hours Horas

lixiviação. O IPBC encapsulado foi liberado mais lentamente do que o não encapsulado, conforme medido por métodos analíticos e microbiológicos. O biocida encapsulado também ficou mais resistente à degradação ambiental causada pelos raios UV e pelo calor. Além disso, testes de exposição ao ar livre realizados com tintas que contêm IPBC encapsulado comprovaram uma melhor proteção da película seca.

Experimento Preparação da Amostra de Película de Tinta

IPBC encapsulado e não encapsulado foram injetados em vários níveis às amostras de tinta. Foram feitas aplicações de cima para baixo, formando películas de 3 mils em papel cartão apropriado (Lanetta), seguidas da secagem em temperatura ambiente por, pelo menos, 24 horas.

Medições do IPBC IPBC Presente na Água Lixiviada Amostras de tinta foram preparadas, conforme descrito acima, com 10.000 ppm de IPBC. As películas das tintas foram suspensas em 100 ml de água com agitação constante. A água lixiviada foi coletada em intervalos diferentes de tempo e o seu teor de IPBC foi analisado com um espectroscópio GC UV-Vis. A concentração de IPBC foi determinada por meio de uma curva IPBC padrão a uma absorvência máxima de 224-228 nm. Quantificação do IPBC em Películas de Tinta usando EFRX As amostras de tinta preparadas conforme descrito acima, contendo 2.000 ppm de IPBC, sofreram lixiviação em vários intervalos de tempo com uma taxa de lixiviação de 1 litro por hora. As amostras foram secas por, pelo menos 24 horas. O equipamento de fluorescência de raios X (FRX) Epsilon 5 foi usado para analisar o teor de iodo nas amostras.6 Uma curvapadrão de IPBC foi desenvolvida com concentrações diferentes de IPBC, sendo linear até 4.000 ppm de IPBC. A correlação linear não dependia da formulação da tinta usada para criar a película. Linhas de base de cada película de tinta foram obtidas antes e após a lixiviação. Medições Delta Y As amostras de tinta contendo 1.000 ppm de IPBC foram preparadas conforme descrito acima. As amostras foram colocadas em uma unidade QUV sob lâmpadas UVB por 24 horas. O índice de amarelamento (IA) foi medido com um espectrofotômetro (CM2500d da Konica Minolta) dentro de 1 hora após as películas serem retiradas da unidade QUV (ASTM E 313 – 10 – Método Padrão para Cálculo dos Índices de Amarelamento (IA) e Brancura para Medição Instrumental das Coordenadas de Cor). O Delta Y foi determinado subtraindo-se o IA da amostra tratada com biocida menos a amostra de controle não tratada após exposição no QUV.

Por Raman Premachandran, Cientista Sênior II, e Karen Winkowski, Diretora Técnica Sênior, Produtos Químicos de Desempenho & Biocidas Industriais | Ashland Specialty Ingredients, unidade comercial da Ashland Inc., Wayne, NJ

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Películas Secas de Revestimentos Liberação de IPBC Ensaio Acelerado de Fungos A norma ASTM D 5590 (Determinação da Resistência de Películas de Tinta e Revestimentos Afins à Degradação por Fungos em Placa de Ágar em 4 semanas ) foi usada para medir a eficácia de vários tratamentos biocidas nas películas de tinta. As amostras de tinta foram preparadas, conforme descrito acima, adicionando-se, porém, 500 ppm de IPBC às amostras. As amostras foram lixiviadas, conforme descrito acima, e inoculadas com uma suspensão de fungos mistos contendo Aspergillus niger (ATCC 6275) e Penicillium funiculosum (ATCC 11797), com concentração final de 107 esporos/ml. Em seguida, as placas foram incubadas por 28 dias a 28°C e 85% UR. O crescimento de fungos na superfície da amostra pintada foi classificado numa escala de 0-4, na qual “0” representava zero crescimento; 1 representava traços de crescimento (<10%); 2 representava pouco crescimento (<10-30%); 3 representava crescimento moderado (30-60%) e 4 representava grande crescimento (60% até a cobertura completa). Teste em Painéis ao Ar Livre Amostras de tinta foram preparadas contendo 3.000 ppm de IPBC (encapsulado e não encapsulado). O substrato usado foi madeira de um tipo de tuia (thuya plicata). Cada painel foi pintado com pincel, com uma demão de primer no lado liso da superfície e uma demão de tinta de alumínio na parte interna. O painel foi dividido em três seções iguais de 30 cm. O centro serviu como controle e recebeu duas demãos de tinta sem fungicida. O lado esquerdo e o direito receberam duas demãos de tinta tratada com fungicida. Após secarem, os painéis foram virados para o norte a um ângulo de 90°.

Resultados e Discussão

A liberação controlada de IPBC nas películas de tintas foi investigada de várias formas. As películas foram colocadas na água e o lixiviado foi retirado em vários intervalos de tempo. A quantidade de IPBC lixiviado foi medida com um espectroscópio UV. A Figura 1 mostra o teor cumulativo de IPBC no lixiviado. O encapsulamento do IPBC (IPBC CR) reduziu a quantidade de IPBC lixiviado da película. A fim de medir a quantidade de IPBC que permaneceu na superfície da tinta, o método não destrutivo de fluorescência de raio X (FRX) foi usado. Como mostra a Figura 2, a quantidade de IPBC que permaneceu na película foi maior para o IPBC encapsulado. A quantidade de IPBC liberada também dependia das propriedades intrínsecas e da composição da tinta. Neste exemplo, a tinta com brilho mostrou níveis mais altos de retenção de IPBC do que a tinta fosca. Também foram aplicados ensaios microbiológicos para demonstrar a liberação controlada de IPBC. Os ensaios de proteção da superfície foram conduzidos de acordo com a norma ASTM D 5590. Nesse ensaio acelerado de 4 semanas, o nível de crescimento de fungos na amostra foi medido após 28 dias de incubação. Como mostra a Tabela 1, o biocida encapsulado (IPBC CR) conferiu uma proteção duradoura à superfície da amostra (nível 0) após a lixiviação intensa.

Alguns testes também foram realizados ao ar livre. Painéis de madeira contendo IPBC encapsulado e não encapsulado foram expostos ao ar livre. Uma tinta acrílica “quick-fail” para exteriores foi usada nesses ensaios. Após 18 meses de exposição, as amostras foram examinadas para verificação do grau de degradação da superfície da tinta. Conforme mostra a Figura 3, a amostra que continha o biocida encapsulado apresentou a menor degradação superficial. Outros experimentos foram conduzidos para demonstrar que o IPBC encapsulado apresenta menor amarelamento quando exposto à luz ultravioleta. As amostras de tinta contendo biocidas diferentes a 1.000 ppm foram expostas à radiação UV (lâmpadas UVB, 24h). Conforme mostra a Figura 4, o biocida encapsulado ficou menos suscetível ao amarelamento após a exposição aos raios UV/calor nas duas tintas testadas. FIGURA 2 | IPBC na superfície da película 24 horas após lixiviação. IPBC naon superfície película IPBC the Film da Surface

Estudos da Eficácia

65 60 55 IPBC IPBC Fungitrol 940CR

50 45 40 35 30

Fosca Flat

Com Brilho Gloss

FIGURA 3 | Exposição em painel externo de teste (tinta acrílica para exteriores formulada para testar falhas rapidamente – 18 meses de exposição.

Fungitrol Fungitrol 940CR 940CR IPBC IPBC Controle Control

0

20

40

60

80

100

%%Degradação superficial Surface Defacement

TABELA 1 | Taxas de crescimento na superfície das amostras após 28 dias.

Dispersão Aquosa/Controle Controle (sem biocida) IPBC CR IPBC

0h 4 0 0

48 h 4 0 2

Lixiviação 72 h 4 0 4

PA I N T & C O AT I N G S I N D U S T RY

96 h 4 0 4

47

Desempenho Superior da Película Seca de Revestimentos por meio da Liberação Controlada de IPBC

confere à molécula uma proteção extra contra os processos de degradação ambiental (como degradação por raios UV e calor), aumentando ainda mais a proteção da película. O IPBC CR é oferecido pela ISP como uma dispersão de 40% de IPBC sob o nome comercial Fungitrol® 940CR. Q

FIGURA 4 | Proteção contra amarelamento. 12

Delta Y

10

Referências

8

1

6

Fungitrol 940CR IPBC

4 2 0

Estireno Styrene acrílico acrylic

Acrílico Acrylic

Conclusões

A liberação controlada de IPBC por meio do microencapsulamento em um portador inorgânico foi demonstrada por ensaios analíticos e microbiológicos. Os mecanismos de liberação controlada mantêm uma concentração mínima de biocida na interface do revestimento por um período mais longo, evitando o crescimento de fungos. O resultado é uma vida útil mais longa do revestimento, dada a mesma concentração inicial de biocida. Como alternativa, níveis mais baixos de biocida poderiam ser usados para obter a mesma vida útil. O portador inorgânico

Woods, W.B. Industrial Biocides for Use in Coatings, Australian Coatings Journal 2000, No.6, 6. 2 Wright, I.C. The Deterioration of Paint Films by Algae and Lichens, Biodeterioration, VI, 1986, 637. 3 Bussjaeger, S.; Daisey, G.; Simmons, R.; Spindel, S,; and Williams, S. Mildew and Mildew Control for Wood Surfaces, Journal Of Coatings Technology 1999, 71, No.890, 67. 4 Alkan,M.; Karada¸ M.; Mehmet Do˘gan, S. Özkan Demirba, S. Adsorption of CTAB onto perlite samples from aqueous solutions, Journal of Colloid and Interface Science 2005, 291, 309–318 5 Malina, R; Ligia, T; Maria, C; Ana B, Adrianac, R; Corina, B; Adrian, C; Maria, Z. Sol-Gel Materials with Pesticide Delivery Properties, Journal of Environmental Protection 2010, Vol 1, No 3. 6 http://www.panalytical.com; Refer to Articles on XRF by Pananlytical for metal and iodine determination.

Este artigo foi apresentado no 38° Annual Waterborne Symposium, em fevereiro de 2011, em New Orleans.

A Cytec Coating Resins fornece produtos inovadores que vão além da imaginação de nossos clientes. Somos pioneiros no desenvolvimento e na produção de soluções para tintas e revestimentos de alto desempenho. Com nossa linha de resinas e aditivos, nossos clientes conseguem gerar mudanças sustentáveis nos setores em que atuam.

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48 NOVEMBRO 2011 | W W W . P C I M A C . C O M

A nova linha Z de aditivos de alto desempenho foi desenvolvida para nossos clientes que desenvolvem tintas e películas ecológicas e sustentáveis. Com o aumento vertiginoso da demanda por tintas e películas “verdes” a linha Z da Troy oferece aos formuladores a possibilidade de desenvolver tintas e películas mais ecológicas, sem a adição de componentes indesejáveis, tais como compostos orgânicos voláteis e poluentes atmosféricos danosos. Com os produtos da linha Z, a Troy FRQWLQXD¿HODRVHXFRPSURPLVVRGHDMXGDURVHWRUDDWHQGHUDGHPDQGDSRUSURGXWRVGHDOWRGHVHPSHQKRTXH sejam ambientalmente corretos e economicamente viáveis. Entre em contato com o seu representante de vendas da Troy para obter mais informações sobre a linha Z de aditivos de alto desempenho da Troy ou visite www.troycorp.com.

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Tecnologia de Poliuretanos Bicomponentes à Base de Água para

Vernizes Automotivos

A

química dos poliuretanos já está bem estabelecida para revestimentos de alto desempenho. Esse sucesso ao longo dos anos é devido às propriedades sem igual conferidas pelas principais características dos poliuretanos, ou seja, alta resistência a solventes e resistência mecânica (equilíbrio entre dureza/ flexibilidade), ótima adesão sobre vários substratos, rápida formação de película e secagem em temperatura ambiente, além da excelente resistência a intempéries na ausência de estruturas aromáticas na composição do polímero. Essas características fazem dos revestimentos à base de poliuretano os candidatos ideais em campos de aplicação que requeiram uma película com aparência e resistência superior, tais como repintura de automóveis e OEM. Nas últimas décadas, os sistemas à base de solvente têm dominado o mercado. No entanto, as normas mais estritas que regulam as emissões de VOC na maioria dos países levaram os fabricantes de tintas e os fornecedores de matérias primas a desenvolverem tecnologias alternativas para substituir os PU à base de solventes, tecnologias essas que causem menos danos ao meio ambiente, mas ofereçam o mesmo desempenho. Portanto, os revestimentos de poliuretano à base de água (sistemas mono ou bicomponentes), que surgiram no final dos anos 80, são atualmente usados em numerosas aplicações.

Poliuretanos Bicomponentes à Base de Água: um Desafio Técnico Sistemas de poliuretano bicomponente à base de água representam um verdadeiro desafio técnico, que, há 30 anos, parecia impossível de ser vencido. Nos sistemas de poliuretanos bicomponente à base de água, um endurecedor poliisocianato desbloqueado é disperso num meio aquoso contendo uma emulsão de um aglutinante poli-hidroxilado (poliol). A mistura é aplicada com ferramentas convencionais (como nos sistemas à base de TABELA 1 | Reatividade comparada dos grupos isocianato com grupos OH.1

OH Primária 2-4

OH Secundária 1

OH Terciária 0,01

Água 0,4

FIGURA 1 | Representação esquemática (a) da aplicação e formação de película de uma sistema de poliuretanto bicomponente à base de água; (b) da dispersão do endurecedor poliisocianato na fase aquosa com uma emulsão de poliol; (c) da evaporação da água e do solvente com coalescência de partículas; (d) da rede polimérica e formação da película.

Emulsificação do poliisocianato para obter poliol

Evaporação da água e coalescência de partículas

Rede polimérica de ligações cruzadas

solventes) e a rede de polímeros se desenvolve após a remoção da água e dos (co)solventes (Figura 1). O desafio consiste em evitar reações indesejadas entre a fase poliisocianato e a água durante um período “razoável” de tempo, ou seja, tempo suficiente para que o aplicador possa preparar a formulação e aplicá-la. Felizmente, com polióis primários contendo grupos funcionais OH, a reatividade dos grupos NCO é maior do que com água, conforme visto na Tabela 1, o que limita essa questão. A emulsificação do endurecedor pode ser obtida por meio da mistura com alto cisalhamento de um poliisocianato hidrofóbico convencional. No entanto, esse método requer um equipamento específico; uma alternativa preferível é modificar o poliisocianato com um sistema surfactante apropriado para obter uma “emulsificação espontânea” quando este é adicionado a um meio aquoso. A emulsificação espontânea ocorre quando dois líquidos imiscíveis são colocados juntos e uma emulsão é obtida sem a necessidade de energia extra (agitação e temperatura), conforme mostrado na Figura 2. Ainda não se sabe muito sobre os mecanismos responsáveis pela emulsificação espontânea de uma fase oleosa para água e várias pesquisas ainda estão sendo feitas para elucidar os processos e parâmetros envolvidos. Acredita-se que a emulsificação espontânea de uma solução orgânica aconteça por meio da organização do surfactante em estruturas com duas camadas (fase lamelar e vesículas), que leva à formação de uma emulsão quando desestabilizadas.2 Apesar das modernas tecnologias por trás dos revestimentos à base de água usados atualmente, como nos primers e tintas de base usadas no setor automotivo, elas ainda se limitam aos vernizes, sendo que poucos sistemas comerciais estão disponíveis. Isso é, em parte, devido às limitações dos primeiros sistemas desenvolvidos: baixa taxa de formação de película devido à evaporação da água, endurecedores sensíveis à água, defeitos nas superfícies (pequenos pontos, microespuma, etc.).3 No entanto, com as novas gerações de matérias primas, particularmente os poliisocianatos hidrofílicos, é possível eliminar a maioria dessas deficiências e desenvolver sistemas de alto desempenho, que realmente conseguem concorrer com os sistemas convencionais de solventes em termos das propriedades necessárias para o uso final. O objetivo deste artigo é comparar as propriedades obtidas com as diferentes gerações de vernizes à base de solvente usados no setor de tintas automotivas (melamina acrílica e poliuretanos bicomponentes à base de solvente, desenvolvidos para aplicações de OEM e repintura automotiva).

Experimental Formulação e Preparação do Revestimento

A Tabela 2 descreve os tipos diferentes de vernizes estudados e as condições de cura. O Verniz A é um sistema acrílico/melamina comercial de catálise ácida. Os Vernizes B (sistema de forneio de alta temperatura) e C (sistema de forneio de baixa temperatura) correspondem aos sistemas de poliuretano bicomponente à base de solventes, desenvolvidos, respectivamente, para

Por Philippe Barbeau e Rolf Klucker | Perstorp, França; Jean-Luc Loubet e Sophie Pavan | Ecole Centrale de Lyon, França

50

NOVEMBRO 2011 | W W W . P C I M A C . C O M

Aplicações aplicações de OEM e repintura automotiva. Neste estudo, o Verniz B será considerado referência em termos de resistência à abrasão: na verdade, trabalhos anteriores em nosso laboratório mostraram que, com o Verniz B, a perda de brilho após o teste de lavagem de carros permaneceu abaixo de 20% após 1500h sob condições de intemperismo avançadas (Weather-Ometer). O Verniz D (sistema de forneio de baixa temperatura) é baseado numa formulação bicomponente à base de água, especificamente desenvolvida para atender às necessidades de repintura automotiva (viscosidade, cinética de secagem e propriedades de uso final), conforme demonstramos na discussão a seguir. As características do poliisocianato usado nos sistemas de poliuretano são apresentadas na Tabela 3. Easaqua XD401 é um polisiocianato hidrofílico (estrutura híbrida baseada em derivados de HDI/IPDI), especificamente desenvolvido para melhorar as propriedades de secagem de sistemas bicomponentes à base de água.4 Para a formulação do verniz à base de poliuretano bicomponente, a relação NCO/OH foi ajustada para 1,05 para os sistemas à base de solvente (Vernizes B e C) e 1,2 para o Verniz D (sistema à base de água). Todos os vernizes foram aplicados com uma pistola de pressão (DeVilbiss SRI) sobre base comercial “preto ônix” (espessura da película seca = 12-14 μm). Sistemas de tintas foram aplicados sobre substratos metálicos (painéis de alumínio QPanel), previamente desengraxados e pintados com um primer bicomponente de superfície à base de solvente (EPS = 35 a 40 μm). Técnicas experimentais Todos os sistemas curados foram armazenados à temperatura de 23°C e 50% de umidade relativa antes do teste. Os seguintes testes foram realizados: t

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Jacksonville. O ensaio de nanoindentação determina as características mecânicas do material próximo à superfície (módulo elástico, dureza). Os indentadores usados nesse ensaio são uma pirâmide de diamante do tipo Berkovich, com ângulo de face de 115°. Tanto o ensaio de nanoindentação como o de nanorisco foi realizado com um Nanoindentador XP da MTS. Os ensaios de nanorisco seguiram um procedimento de carga em rampa usando o aumento normal da carga aplicada de 20 μN para 160 μN, com velocidade de risco de 1 μm/s, usando um indentador esférico (R = 7 μm). O comprimento total dos riscos foi de 500 μm. Tradicionalmente, coleta-se os perfis de altura antes e depois do risco. A profundidade de penetração durante o risco é registrada após subtrair-se a topografia do revestimento intacto. O risco remanescente é visualizado posteriormente com um microscópio ótico. 5

Neste estudo, ensaios de nanoindentação e nanorisco foram realizados em sistemas “frescos” (armazenados por 1 mês a 23°C e 50% UR) e em sistemas antigos (após 1500h de intemperismo acelerado usando um Weather-Ometer.

FIGURA 2 | Emulsificação comparativa de um endurecedor poliisocianato em água. À esquerda, um poliisocianato hidrofóbico convencional; à direita, um poliisocianato modificado quimicamente (sistema “autoemulsionável”).

Poliisocianato hidrofóbico

TABELA 2 | Descrição e composição dos vernizes.

Verniz A

Verniz B

Verniz C

Verniz D

Melamina acrílica comercial

Poliuretano bicomponente à base de solvente para OEM

Poliuretano bicomponente à base de solvente para repintura

Poliuretano bicomponente à base de água para repintura

Natureza do poliol

NA

Poliol acrílico

Poliol acrílico

Poliol acrílico (emulsão em água)

Natureza do endurecedor

Melamina butilada

HDI trimer (Tolonate HDT 90)

HDI trimer (Tolonate HDT 90)

Derivado híbrido HDI/ IPDI hidrofílico (Easaqua XD401)

Condições de cura

30 min a 140°C

30 min a 140°C

30 min a 60°C

30 min a 60°C

Descrição do sistema

TABELA 3 | Características dos endurecedores poliisocianato usados nas formulações dos poliuretanos.

Referência

Natureza

Teor de Sólidos

% NCO

Poliisocianato Tolonate HDT 90 hidrofóbico

90% em acetado de butila

19,8

Easaqua X D 401 Poliisocianato hidrofóbico

90% em acetado de butila

16

P A I N T

& C O AT I N G S I N D U S T RY

51

Poder de Cobertura

Tecnologia de Poliuretanos Bicomponentes à Base de Água para Vernizes Automotivos

TABELA 4 | Propriedades mecânicas, óticas e químicas dos vernizes, analisadas 7 dias após a cura a 23°C e 50% UR.

Os formuladores preferem HIWHITE ® para incrementar o poder de cobertura e opacidade em tintas, com custo-benefício efetivo como extensor de dióxido de titânio sem sacrificar o brilho e a aparência. Estas cargas especializadas também melhoram as propriedades mecânicas e funcionais em coatings e outros sistemas com cargas.

Teste Ensaio de dureza Persoz Ensaio de impacto reverso Brilho MEC, fricção dupla

Verniz A

Verniz B

Verniz C

Verniz D

230

345

311

302

<10

100

100

100

94

94

99

94

200

200

200

200

TABELA 5 | Propriedades mecânicas determinadas pelo ensaio de nanoindentação antes e após o intemperismo acelerado.

Visite-nos na ABRAFATI em nossa estande na rua 1 / B

Amostras “frescas” H E’* (GPa) (MPa) (H/E)

®

CARGAS MINERAIS SINTÉTICAS

Verniz A Verniz B Verniz C Verniz D

2,3 3,3 3,6 3,2

81 142 163 141

0,035 0,043 0,045 0,044

Amostras envelhecidas (após 1500 horas de intemperismo acelerado). n

E’* (GPa)

H (MPa)

(H/E)

n

8,7 10,5 10,7 10,5

2,6 3,6 3,8 3,8

105 165 175 177

0,040 0,046 0,046 0,047

8 12,2 11,7 11,9

FIGURA 3 | Evolução da relação H/E dos quatros diferentes vernizes.

Amostras “frescas” Amostras envelhecidas

Verniz A

Verniz B

Verniz C

Verniz D

Resultados e Discussão Propriedades Gerais e Acabamento Final

Bom equilíbrio das propriedades mecânicas (dureza/ flexibilidade), suavidade e brilho controlados do acabamento e alta resistência química são requisitos essenciais para vernizes automotivos. A Tabela 4 mostra as características mecânicas e óticas de diferentes formulações de vernizes, assim como a sua resistência a solventes, medida por meio do teste MEC com fricção dupla. Os resultados mostram que os três sistemas de vernizes à base de poliuretano exibem desempenho semelhante em termos de dureza mecânica, flexibilidade (resistência a impactos), aspecto visual e resistência a solventes. Em particular, não se vê diferenças entre os vernizes à base de solvente e aqueles à base de água. No entanto, o Verniz A (sistema acrílico/ melamina) gera menor dureza/ flexibilidade. Esse comportamento é característico de uma rede de ligações cruzadas heterogênea no caso do Verniz A.

Para obter maiores Informações,visite nosso portfólio completo de produtos:

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ESPECIALIDADES EM SOLUÇÕES MINERAIS DE EXCELENTE DESEMPENHO

Resistência à abrasão/ riscos

Em aplicações automotivas, o dano relacionado à resistência à abrasão/ riscos é um dos problemas visuais mais importantes do ponto de vista dos clientes, estando relacionado ao desempenho do revestimento. A resistência à abrasão/ riscos só é realmente garantida pela camada de verniz. O comportamento do material de polímero durante a ocorrência do risco é um fenômeno complexo, sendo que ferramentas específicas,

2

FIGURA 4 | Evolução do índice viscoplástico (n) dos quatros diferentes vernizes.

Índice viscoplástico n

tais como a nanoindentação, são necessárias para analisar e entender o desempenho geral. As propriedades mecânicas dos quatros vernizes diferentes medidos pelos ensaios de nanoindentação antes e depois do intemperismo acelerado são mostradas na Tabela 5. Nessa tabela, E’* corresponde ao módulo elástico reduzido do revestimento dado por E' E'* = 1 – υ onde E’ é o módulo elástico do material e Y é o coeficiente de Poisson. H corresponde ao valor de dureza medido com um indentador Berkovich à taxa de carga de 3,10-2 s-1. Os valores de E’* e H são dados para uma profundidade de indentação de 1 μm. Os valores da relação H/E também são dados. H/E representa a tensão limite na qual a deformação é causada pelo indentador. Quanto mais alto o valor de H/E, mais o material resiste à deformação plástica durante a indentação mecânica e o risco. Finalmente, n é o índice viscoplástico da lei de Norton-Hoff que relaciona a dureza à taxa de tensão. H (1/n) 1/n =1: o material exibe um comportamento viscoso puro. 1/n = 0: o material é puramente plástico (não há influência da taxa de tensão na determinação da dureza). Conforme demonstrado por Bertrand-Lambotte6, n indica a capacidade do material de se recuperar de riscos dúcteis: quanto menor o valor de n, mais rapidamente os riscos dúcteis se recuperarão. A resistência dos vernizes à deformação plástica e sua capacidade de recuperar-se de riscos dúcteis (H/E e fatores n) são mostrados nas Figuras 3 e 4, respectivamente. Os resultados mostram que o Verniz A (sistema acrílico/ melamina) exibe um módulo elástico menor e menor dureza, além de H/E e valores de n menores do que os sistemas de poliuretano. O fato de o Verniz A

Amostras “frescas” Amostras envelhecidas

Verniz A

Verniz B

Verniz C

Verniz D

exibir menor dureza e módulo elástico é consistente com o valor de dureza Persoz obtidos anteriormente. O valor baixo de H/E indica que o Verniz A exibe menor resistência à deformação plástica durante a ocorrência do risco. Por outro lado, o menor valor de n (índice viscoplástico) sugere uma maior capacidade de se recuperar de riscos dúcteis. Esse comportamento está, sem dúvida, relacionado ao movimento das cadeias macromoleculares nas condições de teste, indicando uma transição vítrea ampla, consistente com uma rede polimérica mais heterogênea em comparação aos poliuretanos.

Con la avanzada tecnología ANTAROL™ y FOAM BLAST® de Emerald, el control de espuma parece un juego de niños.

Ojalá eliminar las burbujas fuera tan fácil como hacerlas.

Un efectivo control de la espuma es necesario para ayudar a evitar defectos antiestéticos y problemas de procesamiento en recubrimientos, tintas, adhesivos y una amplia variedad de otros usos finales industriales. La introducción de formulaciones de mayor rendimiento, combinadas con regulaciones ambientales más estrictas que exigen menores niveles de COV, indica que las soluciones de control de espuma que alguna vez funcionaron pueden ya no ser el problema. Es por eso que Emerald sigue invirtiendo en avanzadas tecnologías para garantizar que nuestros desespumantes y productos antiespuma respondan a todos los desafíos de procesamiento actuales. Nuestros desespumantes ANTAROL™ y FOAM BLAST® tienen un historial comprobado en el suministro de control de espuma persistente, confiable y duradero en numerosos mercados industriales alrededor del globo. Seguimos ampliando nuestro portafolio para ofrecer productos que respondan no sólo a los requerimientos actuales, sino también a los de mañana. Esto incluye productos fabricados a partir de recursos renovables, desespumantes con pocos COV o ninguno. Nadie hace un mejor trabajo en lo que se refiere a resolver aun los más duros problemas de control de espuma. Emerald Specialties Group – Emerald Latin America, SRL Contactos de ventas:

Para mayor información sobre estos productos y otros de Emerald, como las dispersiones Hilton Davis® 0-VOC y Black Shield™, las siliconas funcionales MASIL®, los plastificantes sin ftalatos Kalama™ K-Flex®, epoxis especializados CVC y más, visite:

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FOAM BLAST® es una marca comercial registrada de Emerald Performance Materials, LLC. Antarol ™ es una marca registrada de Emerald Performance Materials, LLC.

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53

Tecnologia de Poliuretanos Bicomponentes à Base de Água para Vernizes Automotivos

É interessante notar que todos os sistemas de poliuretano exibem novamente propriedades mecânicas semelhantes às determinadas pela nanoindentação. No caso das amostras “frescas”, o Verniz C mostrou uma dureza e um módulo elástico levemente mais altos do que o Vernizes B e D, exibindo, porém, valores semelhantes de n e H/E. Após o intemperismo acelerado, todos os vernizes tendem a se endurecer levemente. Esse comportamento provavelmente se deve ao envelhecimento físico da rede polimérica. O formato e a morfologia dos riscos realizados nos diferentes sistemas de vernizes antes do envelhecimento é mostrado na FIGURA 5 | Morfologia dos riscos observados nos vernizes “frescos”.

Verniz A

Verniz B

Verniz C

Verniz D

TABELA 6 | Comprimento da deformação plástica antes do aparecimento da primeira trinca durante o risco (indentador esférico, R = 7 μm, 1μm/s.

Amostras “frescas” Verniz A Verniz B Verniz C Verniz D

Amostras envelhecidas (após 1500 horas de intemperismo acelerado). 62 ± 6 145 ± 25 181 ± 25 141 ± 2

144 ± 34 267 ± 34 424 ± 27 199 ± 22

Figura 5. Todos os sistemas apresentam, no início da ocorrência do risco (para forças/ profundidades baixas de indentação) um tipo de comportamento dúctil que passa para frágil em profundidades maiores de indentação. A transição dúctil/ frágil é regida por critérios de tamanho e energia: em outras palavras, uma trinca aparecerá no material se a energia imposta a ele ultrapassar a energia necessária para desenvolver uma nova superfície (conforme a abordagem de Griffith). Essa trinca se propagará se o tamanho característico da amostra for, pelo menos, duas vezes a dimensão do domínio plástico induzido no começo da deformação, conforme demonstrado por Puttick.5,6 A transição dúctil/ frágil é vista claramente nas figuras que mostram as primeiras “espinhas de peixe” ao longo do sulco do risco. A ausência da transição para frágil é, obviamente, uma propriedade essencial em termos de resistência a riscos, pois ela afeta a função de proteção dos vernizes (os pontos de fratura permitirão a entrada de agentes químicos no sistema de revestimento, podendo causar delaminação, reações hidrolíticas, etc.). A fim de quantificar o desempenho do verniz na presença de riscos, mostramos na Tabela 6 o comprimento do risco plástico, em μm, antes do aparecimento da primeira trinca para cada verniz, antes e após o envelhecimento. Antes do envelhecimento, a classificação dos diferentes sistemas, em termos de resistência a fraturas frágeis, é a seguinte: Verniz C > Verniz B > Verniz D > Verniz A. Após o intemperismo acelerado, observa-se uma diminuição da resistência a fraturas frágeis em todos os sistemas. Esse fenômeno é consistente com o “endurecimento” observado nas medições da nanoindentação, sendo mais pronunciados nos Vernizes A e C. Enquanto os resultados do Verniz A são, até um certo ponto, esperados e devidos à menor estabilidade da rede acrílico/ melamina em condições de intemperismo acelerado (em comparação aos poliuretanos), a diminuição, no caso do Verniz C, é mais surpreendente. No entanto, C ainda exibe um desempenho um pouco melhor entre os sistemas testados, mesmo após um envelhecimento acelerado. Os Vernizes B e D mostram o mesmo desempenho, o que é particularmente interessante, considerando-se o excelente desempenho do Verniz B, obtido no teste de lavagem de carro.

Resistência ao intemperismo e à corrosão ácida TABELA 7 | Resistência do verniz aos raios UV e à corrosão por ácido.

Verniz A

Verniz B

Verniz C

Verniz D

Retenção do brilho (20°) após 1500 horas no WOM

Referência

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Retenção do brilho (20°) após 4 meses em Jacksonville).

NM

NM

NM

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O interesse no aperfeiçoamento técnico dos vernizes automotivos concentrou-se, no passado recente, na durabilidade frente às condições ambientais e, particularmente, na resistência à corrosão (causada tanto pela chuva ácida em regiões industrializadas quanto por elementos naturais, como fezes de aves). A resistência à corrosão está altamente ligada à densidade das ligações cruzadas da rede polimérica e também à estabilidade hidrofílica do revestimento.

TABELA 8 | Exposição em Jacksonville – condições atmosféricas registradas.

Período de exposição Temp. máx. (média.) Temp. mín. (média) Temp. (média) Umidade relativa Luz do sol - Céu - Claro - Parcialmente nublado - Nublado Chuvoso

82,0˚F [27,8˚C] 63,8˚F [17,7˚C] 73,2˚F [22,9˚C] 39445 min. 55% 25 d 42 d 31 d 23,1” [587 mm]

Ago. 88,8˚F (-2,1) 73,2˚F (+0,5) 81,0˚F (+0,2) 78% 17350 min. 70% 2d 15 d 14 d 16,83” (+9,96)

Set. 86,2˚F (1,0) 69,5˚F (-0,6) 77,9˚F (+0,1) 75% 13572 min. 61% 4d 18 d 8d 5,84” (-2,06)

Out. 78,5˚F (-0,6) 57,4˚F (-2,3) 68,2˚F (-1,2) 11193 min. 51% 12 d 16 d 3d 1,62” (-2,24)

(): Desvio comparado ao valor médio do período de referência 1971-2000

54 NOVEMBRO 2011 | W W W . P C I M A C . C O M

Nov. 69,7˚F (-3,3) 45,7˚F (-5,2) 57,7˚F (-4,0) 70% 10257 min. 54% 14 d 8d 8d 1,01” (-1,33)

Em nosso estudo, a resistência dos diferentes sistemas de vernizes ao intemperismo e à exposição aos raios UV foi determinada analisando-se a retenção do brilho após 1500 horas em condições aceleradas (Weather-Ometer). Quanto à resistência à corrosão por ácido, algumas amostras foram enviadas a Jacksonville, Flórida, por 14 semanas, e a retenção do brilho foi anotada (somente os Vernizes C e D foram testados). Os resultados são mostrados na Tabela 7. As condições atmosféricas registradas em Jacksonville durante o teste são descritas na Tabela 8. Em relação à retenção do brilho, os resultados obtidos mostram um bom desempenho em termos de resistência aos raios UV para todos os sistemas estudados (observe que todos os sistemas contêm estabilizadores da luz UV). Quanto à resistência à corrosão por ácido, o desempenho dos sistemas de poliuretano com forneio em baixa temperatura (C e D) é, obviamente, bom. É interessante observar que o Verniz D (à base de água) tem melhor desempenho que o Verniz C, pois quase nenhuma degradação visual é vista após quase 4 meses em ambiente ácido.

5

Roche S.; Pavan S.; Loubet J.L.; Barbeau P.; Magny B. Progress in Organic Coatings 2003, Vol. 47, p. 37-48.

Este artigo foi apresentado no “The Waterborne Simposium, Advances in Sustainable Coatings Technology, 2010”. O simpósio foi patrocinado pela Faculdade de

6

Bertrand-Lambotte P. “Sur les mécanismes de rayures des vernis de f inition automobile”, PhD report (2001), 143.

Polímeros e Materiais de Alto Desempenho da Universidade de Mississipi do Sul.

Ponte estaiada - São Paulo

Conclusão

Os sistemas de poliuretano bicomponente à base de água já estão no mercado há 10 anos. As opções de matérias primas especialmente desenvolvidas para essa tecnologia evoluíram para atender às necessidades dos formuladores e usuários finais. Este estudo demonstra que os vernizes de poliuretano bicomponente à base de água podem ser uma opção tecnológica em aplicações de vernizes automotivos para combinar os requisitos desejados (resistência à abrasão/riscos, acabamento final, etc.) com a preocupação com o desenvolvimento sustentável.

O Brasil é a inspiração da CPS Color para criar linhas de colorantes ecologicamente corretas e equipamentos com alto desempenho. E foram estes produtos, aliados à uma

Referências 1

CPS Color. Colorantes inspirados no Brasil. Qualidade inspirada na sua empresa.

“Waterborne & Solvent-Based Surface Coatings and their Applications”, ISBN 0471 078868, Volume III: Polyurethanes, chapter I, P. Ardaud, E.Charrière-Perroud, C.Varron, edited by P. Thomas, published in 1998 by SITA Technology Ltd.

2

Shahidzadeh N.; Bonn D.; Meunier J.; Nabavi M.; Airiau M.; Morvan M. Langmuir 2000, 16, 9703-9708.

3

Vandervoorde P., van de Watering P., Double liaison, n° 514, 25-30.

4

Olier P.; Dubecq M.; Barbeau P.; Charriere E. European Coatings Journal 2005, 4.

rede de serviços com excelente custo-benefício, que transformaram a empresa em líder mundial no mercado de soluções tintométricas. É por isso que a CPS Color é a escolha certa para quem procura qualidade, precisão, baixíssimo consumo de energia e as melhores opções de manutenção. CPS Color. Colorindo o Brasil.

Central de Relacionamento CPS Color +55 [11] 3643.1620 +55 [11] 3643.1621

P A I N T Colorantes SaŰo Paulo.indd 1

www.cpscolor.com.br www.cpscolor.com

& C O AT I N G S I N D U S T RY

55 14/10/11 19:08

Novo aditivo umectante de substratos para

Produtos adesivos à base de água com baixo teor de VOC

O

molhamento completo do substrato deve ocorrer para obtermos uma forte aderência. Aditivos umectantes eficazes reduzem a tração na superfície, permitindo a cobertura completa do substrato. Aditivos umectantes eficazes são importantes principalmente para superfícies de baixa energia que, de outra forma, resistiriam à cobertura. Além disso, se um substrato estiver contaminado, as partículas contaminantes de baixa energia repelem o adesivo, provocando falhas na superfície e pouca aderência. Quando um aditivo umectante eficaz está presente, os adesivos molham eventuais agentes contaminantes e substratos de baixa energia criando, desta forma, uma aderência forte e sem obstruções. O aditivo multifuncional Troysol™ LAC da Troy Corp. oferece excelente molhamento de superfícies de baixa energia e contaminadas, promovendo uma forte aderência. No entanto, de-vido aos regulamentos do governo e à demanda dos clientes por produtos ecológicos e ambientalmente corretos, a Troy lançou o Troysol ZLAC. O ZLAC, que não contém alquifenóis etoxilados, é a versão sem VOC do tradicional produto LAC. Ele oferece o mesmo molhamento excelente que o LAC tradicional, mas também permite a formulação de produtos adesivos aquosos com baixo teor de VOC. O ZLAC é um aditivo umectante multifuncional sem silício, que melhora o molhamento do substrato, o fluxo e nivelamento do sistema, a aderência, o brilho e a uniformidade da cor em revestimentos à base de água, polímeros em emulsão, tintas e adesivos.

Inicialmente foi testada a capacidade do Troysol ZLAC de reduzir a tensão superficial, essencial para a umidificação completa de substratos de baixa energia. A Figura 1 mostra como o ZLAC conseguiu reduzir a tensão superficial da água com a utiTABELA 1 | Tensão superficial de TABELA 2 | Energia superficial de solventes comuns solventes comuns

Tensão superficial (dina/cm) Água Etilenoglicol Propilenoglicol Xileno Dipropilenoglicol monometial éter Tolueno Propilenoglicol n-butil éter Butanol

72,7 48,4 40,1 36,0 29,0 28,4 26,3 24,6

Energia superficial (dina/cm) Poliéster Poliéster, tratado Cloreto de polivinila Polietileno Polietileno, tratado Polipropileno orientado Polipropileno orientado tratado

48 54 42 32 42 30 38

Formulações A: Copolímero acrílico ASP taquificado.

% por peso

Reduzindo a Tensão Superficial Uma alta tensão superficial faz com que a água não molhe totalmente a maioria dos substratos. Um bom exemplo dessa alta tensão superficial é quando um alfinete de metal flutua na água. FIGURA 1 | Troysol ZLAC reduz com eficácia a tensão superficial da água.

Flexbond® 165 Aquatac® 6085 Mergal® K10N (preservativo) Troykyd® D11 (desespumante) Água

79,0 15,0 0,2 0,3 5,5

B: Copolímero acrílico ASP taquificado com espessante de uretano.

Tensão dina/cm Surfacesuperficial, Tension, dynes/cm

% por peso 80

Synthebond™ E 2050 Tacolyn™ 3179 H C Acrysol™ 2020NPR Mergal K10N (preservativo) Troykyd D11 (desespumante)

70 60 50 40

C: Copolímero acrílico PSA.

30 20 10 0

83,7 14,6 1,2 0,2 0,3

% por peso

00

0.1 0.3 0,1 0,3 % ZLAC em água % ZLAC in Water

0.5 0,5

Acronal® A 220 Collacral® VAL Mergal K10N (preservativo) Troykyd D11 (desespumante)

98,3 1,2 0,2 0,3

Por Dr. Izzy Colon, Vice-Presidente/ Gerente Geral da Divisão de Aditivos; Vice-Presidente de Ciências & Tecnologia | Troy Corporation, Florham Park, NJ

56 NOVEMBRO 2011 | W W W . P C I M A C . C O M

perfeito acabamento

Fórmulas vencedoras para resinas e revestimentos Descubra nosso mais recente Easaqua™ X L 600 para revestimentos de poliuretano à base de água, além de nossa linha de produtos para dispersão e blocos de construção para dispersões de poliuretano na Abrafati 2011. Como líder global em produtos químicos especiais, podemos ajudá-lo a atingir desempenho excepcional nos revestimentos de poliuretano. Temos a expertise e experiência para satisfazer suas necessidades, sejam de revestimentos à base de água, amigáveis ao meio ambiente, resinas UV, de alta teor de sólidos e em pó, ou cross-linkers de poliisocianato e polióis policaprolactonas. Temos uma fórmula vencedora o aguardando na Abrafati 2011 (21 a 24 de novembro). Visite-nos no estande nº 204 do Centro de Exposições Transamérica em São Paulo, Brasil.

www.perstorp.com

Molhamento completo com Troysol ZLAC

O rastejamento (crawling) foi evidente com o diol acetilênico etoxilado.

7 6 5 4 Troysol ZLAC Troysol LAC

3 2 1 0

00

7

7

6

6

5 4 Troysol ZLAC Troysol LAC

3 2 1 0

00

0,2 0,3 0.2 0.3 Level % Use Níveis de%uso

0,4 0.4

lização de apenas 0,1% do produto. A Tabela 1 lista os valores de tensão superficial de solventes comuns utilizados em formulações adesivas. As tecnologias adesivas tradicionais são baseadas em solventes com tensão superficial baixa. Adesivos à base de água, ao contrário, precisam de aditivos umectantes para reduzir a tensão superficial. O uso de aditivos umectantes melhora a cobertura de substratos com energia superficial baixa (Tabela 2). Um adesivo com tensão superficial alta na fase líquida terá baixa capacidade umectante nos substratos de baixa energia, provocando crateras e/ou forte rastejamento (crawling). O ZLAC, no entanto, reduz a tensão superficial da água de forma eficaz para 25 dinas/cm, fazendo com que adesivos à base de água se espalhem nos substratos de baixa energia. A Figura 2 mostra um teste de molhamento em um filme siliconado. A formulação, que contém ZLAC, promove uma cobertura completa, enquanto outras formulações contendo diol acetilênico etoxilado, um aditivo umectante comum, apresentou forte rastejamento (crawling) nas mesmas concentrações.

Ensaio de Resistência ao Descolamento Ensaios de resistência ao descolamento são úteis para determinar a força da ligação adesiva entre dois materiais. Para avaliar a força de aderência conferida pelas propriedades de molhamento do Troysol ZLAC e LAC, foram realizados testes de resistência ao descolamento com três formulações comuns de adesivos sensíveis à pressão (ASP) (veja a barra lateral). O seguinte procedimento foi usado para avaliar a resistência ao descolamento (Descolamento a 180° de acordo com o Método de Teste 101-D da PSTC). t
Aplique o adesivo sobre um substrato de tereftalato de polietileno (PET) não tratado; t
Coloque o substrato revestido sobre painéis de aço inoxidável após o tempo de espera de 24 horas; t
Use o medidor de ruptura TT-1000 da ChemInstruments para medir a resistência ao descolamento. 58 NOVEMBRO 2011 | W W W . P C I M A C . C O M

0,2 0,3 0,4 0.2 0.3 0.4 Levelde % uso %Use Níveis

FIGURA 5 | Resistência ao descolamento a 180º de ASP com Formulação A, B e C. 180° Strength, Resistência aoPeel descolamento lbs/linear inchlinear a 180º, libras/polegada

Resistência aoPeel descolamento 180° Strength, a 180º, libras/polegada lbs/linear inchlinear

FIGURA 3 | Resistência ao descolamento a 180º de ASP com Formulação A.

FIGURA 4 | Resistência ao descolamento a 180º de ASP com Formulação B. 180° Peel Strength, Resistência ao descolamento lbs/linear inch linear a 180º, libras/polegada

FIGURA 2 | O Troysol ZLAC possibilita o molhamento completo em substratos de baixa energia.

5 4

Formulation Formulação AA

3

Formulação BB Formulation Formulação CC Formulation

2 1 0

00 0,05 0,1 0,2 0.05 0.1 0.2 % Níveis deZLAC uso Troysol Troysol Use LevelZLAC %

O Troysol ZLAC foi analisado juntamente com a versão LAC nas formulações A e B. A versão ZLAC também foi analisada separadamente, com uma quantidade muito baixa de uso, entre 0,05% a 0,2% (peso do aditivo em relação à formulação total), nas formulações A, B e C para determinar as mais baixas concentrações em que a resistência máxima ao descolamento foi obtida.

Resultados e Conclusões Os dados do teste mostram que o molhamento promovido pela versão ZLAC aumenta a resistência ao descolamento dos adesivos sensíveis à pressão e é equivalente ao desempenho superior oferecido pelo produto LAC tradicional (Figuras 3 e 4). Ambos os aditivos melhoraram o molhamento do substrato e aumentaram a resistência ao descolamento, promovendo, desta forma, maior aderência e maior integridade da película. Além disso, baixas concentrações, entre 0,05% a 0,1% promoveram um aumento substancial da aderência nas formulações A, B e C (Figura 5). O uso do aditivo Troysol ZLAC sem VOC mostrou grande eficácia no molhamento de substratos, equivalente ao uso do Troysol LAC em aditivos sensíveis à pressão aplicados sobre substratos de baixa energia. O ZLAC atende à demanda por aditivos umectantes mais ambientalmente corretos na formulação de adesivos e seladores. Com ele, os formuladores podem obter películas sem defeitos, com uma excelente aparência superficial e ótima aderência, sem a ajuda de compostos orgânicos voláteis (VOC). Para mais informações, acesse www.troycorp.com Robert Miller, Dale Lyman e Sheila Belding da Troy Corp. contribuíram para essa matéria. Flexbond® é uma marca registrada da Ashland Inc; Aquatac® é uma marca registrada da Arizona Chemical; Synthebond® é uma marca registrada da Hexion; Tacolyn® uma marca registrada da Eastman; Acrysol® é uma marca registrada da Dow Chemical Co; Acronol® and Collacral® são marcas registradas da BASF Corp; e Troysol™, Mergal® and Troykyd® são marcas registradas da Troy Technology. Esta matéria foi publicada originalmente na edição de fevereiro de 2011 da revista Adhesives and Sealants Industry.

JEFFAMINE® AMINES SÉRIE D DA HUNTSMAN. Sua flexibilidade se adapta a uma vasta gama de aplicações. Aminas bifuncionais JEFFAMINE® da Huntsman também têm leve coloração, baixa viscosidade e pressão de vapor, contêm alto teor de amina primária, e é miscível em diversos solventes. Essas características, juntamente com sua cadeia linear, colocam esta família de aminas em uma posição destacada. Esta é a razão pela qual os componentes da série D são amplamente utilizados como agentes de cura para Epoxy em revestimentos, compostos e laminados. E também tão populares para muitas outras aplicações, como modificadores de polímeros, poliamidas, adesivos, demulsificantes, lubrificantes e aditivos para combustíveis, metalworking e poliuréias. © 2011 Huntsman. JEFFAMINE é marca registrada da Huntsman em um ou mais países.

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Acesse ads.pcimag.com 60 NOVEMBRO 2011 | W W W . P C I M A C . C O M

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A New Era in Superwetters for Waterborne and UV-Curable Coatings and Inks

T

he growth today in waterborne and radiation-cured coatings and inks far exceeds that of its solventborne equivalents. The need for lower VOCs, “greener” materials, improved food safety and reduced economics (inventory reduction and faster production speeds) all contribute to this growth, and this in turn increases the need for superwetters. Why? As formulators transition from solventborne coatings and inks to create healthier, safer and more eco-friendly systems, performance requirements bring to light issues and disadvantages associated with waterborne and radiationcurable systems. In particular, many of the surfactant packages utilized have the negative effect of stabilizing foam from air incorporation during coatings production and application. In addition, in waterborne coatings specifically, the inherent high surface tension of water creates the potential to cause surface defects such as craters and poor wetting on substrates. With the growth of waterborne and radiation-curable coatings and inks comes the development of more binder systems, and formulators find they require a wider portfolio

TABLE 1 | Commercially available wetting surfactants used to benchmark superwetters. Competitor

Chemistry

1 2 3-5, 7-9 6 10-15

Ace ylenic diol in solution t Silicon yether co-polymer in solution e pol Silicone polyether co-polymer Silicon yether co-polymer (Gemini) e pol Fluorosurfactants

TABLE 2 | Hydrophilicity and reactivity (end capping) of the four superwetters. Product Name Dow Corning 67 Additive Dow Corning 500W Additive Dow Corning 501W Additive Dow Corning 502W Additive

HLB_EO

End-Capped

11.5 10.7 10.6 13.2

OH OAc OMe OH

TABLE 3 | Static surface tension of superwetters at 0.1% by weight in water. Product Name

Static Surface Tension (mN/m)

Water only Dow Corning 67 Additive Dow Corning 500W Additive Dow Corning 501W Additive Dow Corning 502W Additive

71.0 21.1 22.0 20.5 22.4

of wetting additives to choose from when developing new formulations. No one, universal solution is suitable across a wide range of formulations and substrates because inconsistent performance; lack of regulatory compliance; poor pH stability; poor performance in demanding, high-speed applications; and cost all bring the formulator problems. In the coating and ink industries, silicone materials have been developed and used for many years to improve the surface appearance and properties of many systems, including wetting, but this technology has also suffered from inconsistent performance. Dow Corning has recently launched four 100% silicone polyether co-polymers with good compatibility in waterborne and radiation-curable systems to provide good substrate wetting consistently over a wide range of formulations, pH ranges and substrates. This article describes an application study comparing the performance of these four unique silicone polyether co-polymer superwetters to commercially available surfactants on the market (acetylenic diols and silicone polyether copolymers, including Gemini surfactants) (Table 1).

Superwetters The new superwetters are 100% silicone polyether copolymers, consisting of a hydrophobic, methylated, shortchain silicone backbone with pendant hydrophilic ethylene oxide chains. The ethylene oxide chains are endcapped with hydrophilic organic groups such as hydroxy, methoxy or acetoxy. In this study they were evaluated in aqueous solution, a waterborne polyurethane-based wood parquet lacquer coating, waterborne acrylic-based flexo gravure ink and in UV acrylate coatings (Table 2). These new superwetters are low-viscosity and lowmolecular-weight materials, and so are easy to incorporate into coatings and inks. They migrate quickly to, and pack efficiently at, the coating surface, giving rise to low surface tension required to achieve good wetting performance. Static surface tension measurements were conducted with 0.1% by weight aqueous solutions at room temperature. The equilibrium surface tension was measured with a Krüss K10T tensiometer and a platinum Wilhelmy plate. For this test method, a platinum plate is immersed in the test liquid and the force required to remove the plate from the solution is taken as a measure of the surface tension of the liquid. The superwetters provide excellent static surface reduction (Table 3). While the ethylene oxide content (HLB) doesn’t influence the surface tension directly in water,

By Gwang Su, Lee (LEKS) | Dow Corning Korea Ltd.; Vicky James | Dow Corning Europe SA, Seneffe, BL; and Akinaga, Keiichi | Dow Corning Toray, Ltd. 62



NOV EMBER 2011 | W W W . P C I M A G . C O M

With the addition of surfactants to a formulation comes the risk of foam stabilization, and the impact on foaming was evaluated by measuring foam height after high-speed shearing.

Surface Tension (mN/m)

Dow Corning 67 Additive Dow Corning 500W Additive Dow Corning 501W Additive Dow Corning 502W Additive Competitor 2 Competitor 3 Competitor 4 Competitor 5 Competitor 6 Competitor 7 Competitor 8 Competitor 9

60 50 40 30 20 10 0

DST (1 Hz)

Low speed

DST (10 Hz) DST (5 Hz)     High speed

FIGURE 2 | Dynamic surface tension of all surfactants at pH 11 (0.4% by weight in water).

Surface Tension (mN/m)

70

pH11, after 1 month   ageing

65 60 55 50 45 40 35 30 25 20

0

200

400 600 800 Surface Age (ms)

Competitor 8 Competitor 6 Competitor 7 Competitor 9 Competitor 2 Competitor 3 Competitor 4 Competitor 5 Dow Corning 67 Additive Dow Corning 501W Additive Dow Corning 502W Additive Dow Corning 500W Additive

1000

FIGURE 3 | Surface appearance in the waterborne wood parquet coatings shown in Tables 4 and 5. 9 8 7 6 5 4 3 2 1 0

pet

itor 9

PUD-based wood coating Acrylic-based wood coating

Com

In this part of the application study, each surfactant was compared at 0.2% by weight in each formulation. The following properties were evaluated to compare performance: 1. Surface appearance by visual assessment of surface defects (wetting and leveling); 2. Slip (coefficient of friction).

70

Con tro l D 500ow Co W A rnin ddi g tive D 501ow Co W A rnin ddi g tive D 502ow Co W A rnin dd g Dow itive 67 ACornin ddi g Com tive pet itor 1 Com pe t itor 2 Com pet itor 3 Com pet itor 4 Com pet itor 5 Com pet itor 6 Com pet itor 7 Com pet itor 8

Benefits of Superwetters

FIGURE 1 | Dynamic surface tension, 0.2% by weight surfactants in water.

Visual Assessment (1=poor, 10=excellent)

this can affect the solubility and therefore performance of the surfactant in a coating or ink formulation. Therefore, having a range of HLB values allows the formulator to choose the right product for a given formulation. While static surface tension will give a theoretical indication of how much a surfactant can reduce the surface tension of a given solution to achieve good wetting, Dynamic Surface Tension (DST) is more reflective of reallife performance in a coating or ink application process, as this measures how quickly a surfactant migrates to the air/liquid interface to do its work. Figure 1 shows DST results of the superwetters and competitor surfactants at 0.2% by weight in water. DST is measured by using a bubble tensiometer that bubbles air through the test liquid at an increasing rate, during which the maximum pressure that is required to form a bubble is measured. As the bubble rate increases from 1 bubble per second to 10, the time to create the new interface (liquid/air) decreases. All of the superwetters perform well at low to medium application speeds, as indicated by low DST at 1 and 5 Hz. In particular, Dow Corning® 502W Additive and competitor additive 7 maintain their very low DST at high speed. This gives an indication that both products will be useful for wetting in high-speed applications and challenging conditions such as spraying. However, this test is only an indication and does not reflect real-life performance in all cases, and we will see later that while the performance of Dow Corning 502W is supported with consistent application data, this is not the case for the competitor 7 additive. High-pH paints are most common in the decorative market, and here, long-term stability of a wetting additive is key. Figure 2 shows the DST performance of the surfactants at pH 11 after 1 month aging. Long-term performance of Dow Corning 500W Additive at pH 11 was achieved after 1 month aging, providing low surface tension consistently. This allows the formulator to use it in high-pH formulations with confidence of long-term wetting performance at the end-use stage. The data indicates that this additive achieves long-term performance at high pH due to the stability of the non-reactive acetoxy-end capped group.

FIGURE 4 | Surface appearance of a waterborne polyurethane acrylic wood parquet lacquer with and without Dow Corning 67 Additive (added at 0.2% by weight in the total formulation). No additive

With Dow Corning 67 Additive 0.2% by weight

Performance in Waterborne Polyurethane and Acrylic Wood Parquet Lacquer Formulations The two typical wood coating formulations shown in Tables 4 and 5 were used to evaluate the performance of the superwetters. The first is based on a polyurethane dispersion, the second on an acrylic dispersion. PA I N T & C O A T I N G S I N D U S T R Y



63

A New Era in Superwetters

In Figure 3, we can see the assessment of these wood coatings on glass with both the superwetters and competitive surfactants 1-7. Glass is used as the substrate since this is the standard substrate used in the industry to evaluate wood coatings. The wetting performance of the superwetters is high, with only some small differences between the products. Comparing these to competitive additives 1-7, we can see that the wetting performance of the superwetters is, for the most part, better than the com-

Performance in UV-Curable Formulations

FIGURE 5 | Surface appearance and dynamic coefficient of friction in waterborne UV-curable coating at 0.2 % by weight in the total formulation. PVC Dynamic COF

0.5 0.4 0.3

COF

10 9 8 7 6 5 4 3 2 1 0

0.2 0.1

Con tro l Dow 500 Co W A rnin ddi g tive D 501 ow Co W A rnin ddi g tive D 502 ow Co W A rnin dd g Dow itive 67 ACorni ddi ng tive Com pet itor 1 Com pet itor 2 Com pet itor 3 Com pet itor 4 Com pet itor 5 Com pet itor 6 Com pet itor 7 Com pet itor 8 Com pet itor 9

0

FIGURE 6 | Wetting (by droplet diameter) and dynamic coefficient of friction with Dow Corning 57 and 67 Additives in solventless UV-curable coating at 0.2% by weight in the total formulation. 1 9   Wetting (droplet 0.9 8 diameter on 0.8 PVC mm) 7 0.7 Dynamic CoF 6 0.6 5 0.5 4 0.4 3 0.3 2 0.2 1 0.1 0 0 Dow Corning 57 Dow Corning 67 Control Additive Additive (No additive)

NOV EMBER 2011 | W W W . P C I M A G . C O M

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Appearance CoF(μK) 1

COF

Visual Assessment

flexographic ink on PET at 0.2 % by weight in the total formulation. PET substrate

Dow Corning’s new superwetters can be used in radiationcured coatings, whether in waterborne, solventborne or solventless delivery systems. Figure 5 demonstrates the performance of a waterborne, radiation-curable coating on PVC, a low-energy and difficult-to-wet substrate. Again the superwetter family shows consistent performance for wetting, and there is little or no impact on the slip properties of the coating. No negative impact on slip can of course be critical to some applications, such as flooring coatings, but where increased slip is required this can be modified using another additive from the Dow Corning additives portfolio. This is demonstrated in Figure 6, where the performance of Dow Corning 67 Additive has been compared to Dow Corning 57 Additive in a solventless UV-curable coating. In this formulation we can see that the 67 Additive gives the superior wetting performance with no impact on slip (coefficient of friction), while the 57 Additive gives a lower wetting performance but with a dramatic decrease in slip. This differentiation in slip performance between the superwetters and other additives gives formulators the choice to customize their formulation to suit the end application.

Performance in Waterborne Flexographic Ink In this example on PET (Figure 7), another low-energy substrate that is very difficult to wet, Dow Corning 500W and 501W Additives excel in performance, an indication that the non-reactive end capping is influencing the performance. The coefficient of friction remains unchanged;

TABLE 4 | Waterborne polyurethane acrylic wood parquet lacquer formulation. Ingredients NeoPac® E-106: Aromatic(anionic) urethane acrylic copolymer dispersion Butyl diglycol Aquacer® 593: Wax emulsion (modified polypropylene) Total

FIGURE 7 | Surface appearance and dynamic coefficient of friction of waterborne

10 9 8 7 6 5 4 3 2 1 0

petition. More importantly perhaps is that performance is consistent across both formulations, and while some competitive additives perform well in one formulation, performance is poor in the other. The old adage, “seeing is believing”, is certainly true in the case of the superwetter performance. Figure 4 shows the wetting performance of the waterborne polyurethane acrylic wood parquet lacquer with and without a superwetter; in this example Dow Corning 67 Additive is shown.

Percent by Weight 91 4 5 100

TABLE 5 | Waterborne acrylic wood parquet lacquer formulation. Ingredients Joncryl® 8383: semi-translucent emulsion and self-crosslinking acrylic polymer emulsion Texanol Aquacer 593: Wax emulsion (modified polypropylene) Total

Percent by Weight 91 6 3 100

A New Era in Superwetters

FIGURE 8 | Surface appearance of superwetters versus fluorosurfactants in waterborne wood parquet coatings. Comparison is made at 0.1 and 0.2% by weight in the total formulation. 10 9 8 7 6 5 4 3 2 1 0

0.1% addition 0.2% addition

Fluorosurfactants

Con tro l Dow 500 Co W A rnin ddi g tive Dow 501 Co W A rnin ddi g tive Dow 502 Co W A rnin ddi g tive Dow 67 ACorni ddi ng tive Com pet itor 10 Com pet itor 11 Com pet itor 12 Com pet itor 13 Com pet itor 14 Com pet itor 15

While constantly under scrutiny for their bio persistence, fluorocarbon-based surfactants are still used in coatings and inks today. Effective at very low addition levels, they are also high in cost. As an addition to this study, we have evaluated six commercial fluoro-based surfactants (competitors 10-15) versus the superwetters. Figure 8 demonstrates the performance at 0.1 and 0.2% by weight to the total formulation in the waterborne polyurethane-based lacquer shown in Table 4. While a higher addition level of the superwetters is required to give the same performance as the fluorosurfactants, on a cost-in-use basis they can be competitive, exemplified here with both Dow Corning 500W and 67 Additives.

• A higher addition level of the Dow Corning Superwetters is required to give the same performance as the fluorosurfactants. • However on a cost-in-use basis they can be competitive, exemplified here with both Dow Corning 500W Additive and Dow Corning 67 Additive.

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16.00  14.00  12.00  10.00  8.00  6.00  4.00  2.00  0.00  WA

Foam Height (mm)

FIGURE 9 | Foaming and surface appearance in waterborne flexographic gravure ink at 0.2% by weight in the total formulation.

FIGURE 10 | Foaming in waterborne flexographic gravure ink at 0.4% by weight Dow Corning 67 Additive and Dow Corning 62 or 65 Additive in the total formulation. 25.00

Foam Height (mm)

20.00 15.00 10.00

While the addition of surfactants achieves wetting on difficult-to-wet substrates, they potentially also have a negative effect on foam behavior of inks and coatings in some cases, leading to foam stabilization during production and application at high shear. This is true for all types of chemistries used. The effect of these surfactants on the foaming property of a waterborne flexographic gravure ink was measured by evaluating foam height after high-speed shearing. In Figure 9 we can see that some foam stabilization is evident with both the superwetters and competitive additives. Where the surfactant does the best job it unfortunately results in the highest amount of foam – but conversely, low foam stabilization cannot compensate for poor wetting! Important to the formulator is that this foam can be controlled. Figure 10 clearly demonstrates that with addition of Dow Corning defoamers at only 0.1% by weight to the total formulation, we see a reduction of foaming.

Conclusion Dow Corning’s superwetters are effective in providing consistent coating performance in a wide range of formulations. In particular, our 500W Additive provides excellent performance with high pH stability, and our 502W Additive is especially suitable for very high-speed printing and challenging spray applications. Coatings formulators can select superwetters based on their different performance needs to get consistent product performance.  Aquacer ® is a registered trademark of BYK Additives and Instruments. NeoPac® is a registered trademark of DSM Neoresins+. Joncryl® is a registered trademark of BASF. Texanol® is a registered trademark of Eastman. M.R. Porter, Blackie. Handbook of Surfactants, USA; Chapman & Hall, New York. Owen, MJ, The Surface Activity of Silicones: A Short Review, I&EC Prod. Res. Dev., 10 (1980), 97. 7. W.H. Pushaw III. Handbook of Coatings Additives, (L.J. Calbo, ed.), Marcel Dekker, Inc., New York, 1987, p.271. 8. Carbinol Functional silicon-based technologies for coatings, Donna Perry, Vicky James, Gerald Witucki. 9. http://www.chinasilicone.com/Modified-polyether-trisiloxane.html 10. ht t p : //w w w.c o smet ic sa ndt oi let r ie s.c om /for mu lat i ng /i ng r e d ient /su r fac tant/114203679.html

1. 2. 3. 4. 5. 6.

0.00 Control Dow Corning 67 Additive (0.4%)



Foam Stabilization

References

5.00

66

this can be particularly important in printing applications where high slip results in difficulties in stacking printed items. Again, if a reduction in the slip properties is required, this can be adjusted using a customized slip additive such as Dow Corning’s 57 or 51 Additive. This differentiation in slip performance between the superwetters and these other additives gives formulators the choice to customize their formulation to suit the end application.

Dow Corning 65 Additive (0.1%) Dow Corning 67 Additive (0.4%)

Dow Corning 62 Additive (0.1%) Dow Corning 67 Additive (0.4%)

NOV EMBER 2011 | W W W . P C I M A G . C O M

A Multifunctional Coating for

Autonomous Corrosion Control

N

early all metals and their alloys are subject to corrosion that causes them to lose their structural integrity or other functionality. It is essential to detect corrosion when it occurs, and preferably at its early stage, so that action can be taken to avoid structural damage or loss of function of metals and their alloys. Because corrosion is mostly an electrochemical process, pH and other electrochemical changes are often associated with it, so it is expected that materials that are pH or otherwise electrochemically responsive can be used to detect and control corrosion. The authors developed a smart coating with a controlled-release system that uses pH-triggered release microcapsules for early detection of corrosion and for corrosion protection. This article describes the relation between pH and corrosion, the design of pH-sensitive microcapsules and their

FIGURE 1 | The electrochemical cell set up between anodic and cathodic sites on an iron surface undergoing pitting corrosion. Porous cap O2 + H2O Passive film

O2 + H2O

CI-

OH-

e-

Fe(OH)3

CI-+ H2O Fe(OH)2

e-

+CI-+ H+

Fe2+

Acid chloride pit electrolyte Iron

synthesis, as well as selected test results of the smart coating with pH-sensitive microcapsules for corrosion indication and inhibition.

Corrosion and pH Corrosion is largely an electrochemical phenomenon, because, in most cases, it involves the transfer of electrons between a metal surface and an aqueous electrolyte solution. For instance, when iron corrodes in near neutral environments, the typical electrochemical reactions are: Cathodic reaction: O2 + 2H2O +4e – N 4 OH– Anodic reaction: Fe N Fe2+ + 2e – In the case of localized corrosion, such as pitting corrosion as shown in Figure 1, the anodic reaction happens in a confined area, the metal ions produced are precipitated as solid corrosion products, such as iron(II) oxide, Fe(OH)2, (often further oxidized to iron(III) oxide, Fe(OH)3), which covers the mouth of the pit. This covering traps the solution in the pit and allows the buildup of hydrogen ions, H+. The overall effect is that, while localized corrosion happens, the anode area often has an acidic pH and the cathode has an alkaline pH.1 Besides pitting, crevice corrosion and dissimilar metal corrosion result in pH changes as illustrated by the simple demonstration shown in Figure 2, where a universal pH indicator was used to show the pH changes that occur during corrosion of a metal, such as steel. In this demonstration, most of the steel was exposed to agar gel while a strip in the middle was wrapped in copper tape. The color change of the pH indicator shows that the exposed steel tends to be acidic (yellow color) while the strip wrapped in the copper tape tends to be basic (purple color) due to the oxygen reduction reaction and the release of the hydroxide ion, OH-. Since pH and other electrochemical changes are often associated with corrosion, it is expected that materials that are pH or otherwise electrochemically responsive can be used to detect and control corrosion. Various pH and

By Luz M. Calle | NASA, Kennedy Space Center, FL; and Wenyan Li, Jerry W. Buhrow and Scott T. Jolley | ASRC Aerospace, Kennedy Space Center, FL 68



NOV EMBER 2011 | W W W . P C I M A G . C O M

electrochemically responsive materials as well as their potential applications in smart coatings for corrosion control can be found in our previous review.2 A self-healing coating is another new development in material design that is important to corrosion control.3,4,5

FIGURE 2 | pH changes associated with corrosion.

Acidic

pH-Sensitive Microcapsules The authors developed a controlled-release system that combines the advantages of corrosion sensing and protection by using pH-triggered release microcapsules for early corrosion detection and protection.2,6,7,8 The key component of this technology is a pH-sensitive microcapsule with a wall designed to break down and release the encapsulated contents in response to the pH of the cathodic site of localized corrosion (Figure 3).

Slightly Acidic

5h

1h

3 days

Neutral Slightly Basic

Smart Coating Based On pH-Sensitive Microcapsules Microencapsulation is a versatile approach because it can be used to encapsulate an unlimited number of materials, in both solid and liquid phase, and even in the gas phase when entrapped in aerogel. It is possible to incorporate microcapsules into composites or coatings. For corrosion applications, various compounds, such as corrosion indicators, inhibitors, self-healing agents and dyes can be encapsulated. These microcapsules can be incorporated into various coating systems for corrosion detection, protection and self-repair of mechanical coating damage (Figure 4). The versatility of the design is of special interest in corrosion-inhibition applications. Almost all corrosion inhibitors are chemically active reagents. Very often, the reactivity that makes them effective corrosion inhibitors also causes them to be environmentally unfriendly, such as in the case of chromates. Because of this, research for new and environmentally friendly corrosion inhibitors is an on-going effort in the corrosion protection industry. After a new inhibitor is developed, it usually takes a long time to incorporate it into a paint formulation. A smart coating that includes encapsulated inhibitors and releases them on demand when corrosion starts can shorten this long reformulation process for new inhibitors by simply changing the core content of the microcapsules. The pH controlled-release microcapsule design has, in addition to all the advantages of the regular microcapsule design, the true controlled-release function for corrosion applications. Regular microcapsules release their contents when they are mechanically broken; pHsensitive microcapsules release their contents when corrosion occurs. Mechanical damage in a coating is one of the important causes for corrosion of the base metal. However, many coating defects, such as air bubbles, uneven thickness, permeation, porosity or edge effects, will also result in poor corrosion protection of the coating and allow corrosion to occur. pH-sensitive microcapsules will release their content for corrosion detection or protection regardless of the corrosion cause.

0h

Basic

FIGURE 3 | The key component of the smart coating system: pH-sensitive microcapsules.

Microcapsule containing pH indicator (inhibitor, self healing agents) OH-

The shell of the microcapsule breaks down under basic pH (corrosion) conditions OH-

pH indicator changes color and is released from the microcapsule when corrosion starts FIGURE 4 | Smart coating with pH-sensitive microcapsules for corrosion detection and protection applications. 1. Corrosion indicators 2. Corrosion inhibitors 3. Healing agents O2 + H2O Incorporated into coating

OH-

Fe2+ e

Corrosion Mechanical damage causes capsule causes capsule to rupture to rupture OH-

Chemistry of the pH-Sensitive Microcapsules The chemistry of the pH-sensitive microcapsules is basecatalyzed ester hydrolysis. The polymeric walls of the microcapsules include a crosslinking agent that has one

Ruptured microcapsule: - indicates corrosion - protects metal from corrosion - repairs damaged area

Fe2+ e-

PA I N T & C O A T I N G S I N D U S T R Y



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A Multifunctional Coating for Autonomous Corrosion Control

or more ester and mercapto groups. A typical crosslinker is pentaerythritol tetrakis (3-mercaptopropionate or PTT), a tetra-functional molecule. Since this crosslinker is not a good film former, other prepolymers or monomers are needed to provide the structural integrity of the microcapsule wall. Examples of film-forming monomers and prepolymers include urea formaldehyde and melamine formaldehyde monomers and prepolymers.

FIGURE 5 | Microcapsule breakdown in basic solution. a

h

l

k

j

i

e

d

c

b

g

f

n

m

FIGURE 6 | Schematic representation of the steps involved in the interfacial polymerization of an oil-in-water microemulsion for making oil core microcapsules. Oil is shown in yellow and water in blue. Capsule with Surfactant Prepolymer polymer wall Oil

Water

Addition of oil and prepolymer

Mixing

Polymerization

FIGURE 7 | Schematic representation of the steps involved in the interfacial polymerization of a water-in-oil microemulsion to synthesize water core microcapsules. Oil is shown in yellow and water in blue. Prepolymer Surfactant

Capsule with polymer wall

Water

Oil

Oil

Addition of water

70



Mixing

Polymerization

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Capsule wall breakdown under basic conditions can be observed visually. Figure 5 shows such breakdown occurring in response to exposure to a small amount of water containing sodium hydroxide, NaOH, (pH 12). Soon after the NaOH solution was added, the solution starts to penetrate the microcapsule wall, as indicated by the color change inside the microcapsules (Frames b-d). In Frame e, the microcapsule begins to slowly release its contents (as evidenced by the small droplet that begins to form on the bottom left quadrant of the frame). The content continues to be released until (Frame i) it dissipates into the solution. The microcapsule wall eventually collapses as shown, in Frames j through n.

Encapsulation Process Encapsulation Methods pH-sensitive microcapsules are the key component of the smart coatings. Several methods such as spray drying, emulsion polymerization, interfacial polymerization, as well as in-situ polymerization have been used to synthesize pH-sensitive microcapsules. Interfacial polymerization is illustrated in Figure 6 as an example. There are two main steps involved in the interfacial polymerization process: microemulsion formation and microcapsule wall formation. This technique can be used to form both oil (or hydrophobic) core and water (or hydrophilic) core microcapsules. Figure 6 shows a schematic representation of the steps involved in forming oil core microcapsules: the microemulsion is formed by adding the oil phase (with prepolymer, shown in yellow) to the water phase (with surfactant, shown in blue) and mixing; the last step is the formation of the microcapsule wall (shown in green) by interfacial polymerization. Figure 7 shows a schematic representation of the steps involved in forming water core microcapsules: in this case, the microemulsion is formed by adding water (shown in blue) to the oil (with prepolymer and the surfactant, shown in yellow) followed by mixing; the last step is the formation of the microcapsule wall (shown in green) by interfacial polymerization. These two illustrations involve the use of oil, or hydrophobic solvent-soluble wall-forming prepolymer. A similar process has been developed to use water-soluble wall-forming materials by dissolving the wall-forming prepolymer in the water phase and the catalyst in the oil phase. The reaction at the interface will form the capsule. In situ polymerization is also used to form pH-sensitive microcapsules. The in situ polymerization process is similar to interfacial polymerization; their difference is the location where the polymerization reaction occurs. For interfacial polymerization, reaction occurs at the interface; the polymerization reaction occurs in the continuous phase for in situ polymerization and the polymer is formed through the reaction deposits at the interface to form the capsule wall. Spray drying involves dispersing the wall-forming prepolymer and substance to be encapsulated (the core material) into a continuous phase (water for instance). The mixture is sprayed into a mist and in a hot gas flow where the liquid droplets are dried into solid particles. In the process, the core material is encapsulated inside the wall materials.

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A Multifunctional Coating for Autonomous Corrosion Control

size solid core microcapsules and as a useful method for drying microcapsules into a free-flowing powder form without forming clusters.

FIGURE 8 | Oil core microcapsules of different sizes.

Microcapsule Synthesis 50 μm

FIGURE 9 | SEM images of the water core microcapsule.

1 μm NASA 10/22/2009 X 3,000 0.30kV SEI GB_HIGH WD 3mm

1 μm NASA 10/22/2009 X 7,000 0.30kV SEI GB_HIGH WD 3mm

Interfacial polymerization and in situ polymerization are the main approaches used by the authors for microcapsule synthesis. Spray drying has been used to synthe-

Different active core contents have been encapsulated, including corrosion indicators, corrosion inhibitors, dye and self-healing agents. Both water core microcapsules and oil core microcapsules were synthesized using the methods described above. To tailor these processes for encapsulating corrosion inhibitors and indicators, various indicators and inhibitors were selected and tested for their indicating and inhibiting efficiency respectively. The solubility and dispersibility of the active compounds were surveyed or tested to find a suitable method for their encapsulation. An active compound that can be dissolved or dispersed in a hydrophobic solvent, such as oil, can be encapsulated into oil core microcapsules. Normally, oil core microcapsules are used for encapsulating oil-soluble materials but not water-soluble materials, such as salts or polar molecules. However, these materials can still be encapsulated by dissolving them first into a polar co-solvent and adding the resultant solution to the oil phase. Alternatively, a surfactant can be added to the oil phase. This will dissolve or disperse the polar or water-soluble reagents into the oil

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phase. The oil-in-water emulsion can then be formed and the interfacial reaction can be used to encapsulate these reagents into the oil core of the microcapsules. Similarly, if a compound can be dissolved or dispersed in water, with or without the aid of a co-solvent, or a surfactant, it is possible to encapsulate it into water core microcapsules. For example, phenolphthalein does not dissolve in water, but ethanol can be used as a co-solvent to dissolve a moderate amount of the indicator in water, making it possible to encapsulate it into water core microcapsules. Various compounds of interest for corrosion control applications have been encapsulated into oil core microcapsules. These compounds include: corrosion indicators such as phenolphthalein, phenol red, and fluorescein; dyes such as Rhodamine B; healing agents such as epoxy and polysiloxane; and various solvents, such as chlorobenzene, which can be used as a healing agent. Various corrosion inhibitors and indicators have been encapsulated into water core microcapsules, such as the corrosion indicator phenolphthalein, and corrosion inhibitors sodium molybdate (Na2MoO4), cerium nitrate (Ce(NO3)3), sodium phosphate (NaH2PO4), calcium metaborate, and phenylphosphonic acid. Af ter a microcapsule formula is developed, an optimization process usually follows to obtain microcapsules of suitable size and desired properties for its appli-

FIGURE 10 | SEM images of a water core microcapsule obtained by using a transmission electron detector.

100 nm NASA 10/22/2009 X 35,000 30.0kV TED SEM WD 5 mm

100 nm NASA 10/22/2009 X 80,000 30.0kV TED SEM WD 5 mm

cation. The capsule size can be controlled by adjusting the emulsion formula or by varying the mixing speed of the mixer during the emulsion formation. These methods can be used to obtain microcapsules of a desired size within a narrow range of distribution. Sizes from 200 nm to 200 μm (micron) can be obtained, with a typical size from about 1 to 5 μm. Oil core microcapsules of various sizes are shown in Figure 8. The SEM images in Figure 9 show capsules of spherical shape with less than 1 +m in diameter size. The capsule wall thickness is about 50-100 nm as shown in the micro-

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A Multifunctional Coating for Autonomous Corrosion Control

graphs of the microcapsules obtained using a transmission electron detector (Figure 10).

Experimental Microcapsules were incorporated into different commercially available coatings in order to test their corrosion indication and inhibition functions. Preliminary results of these tests are presented below.

FIGURE 11 | Corrosion indication test results. Initial

30 sec

2 min

3 min

5 min

20 min

30 min

1h

2h

5h

Corrosion Indication Tests Corrosion indication can be incorporated into the coating by encapsulating a corrosion indicator into pH-sensitive microcapsules. Figure 11 shows the results from the salt immersion test of steel panels coated with a clear urethane coating containing 10% of microcapsules with corrosion indicator. The panels were scribed and observed for visual changes over time. It was observed that the indicator signaled the onset of corrosion in the scribe about 1 minute after immersion, which is considerably earlier than the 2 hours for the appearance of the typical rust color. In addition to early corrosion detection, another potential application of the smart coating is to detect hidden corrosion, for example on structural bolts. Bolts tend to corrode on the hidden shaft area before visible corrosion is seen on the bolt head or nut. Often, the head and nut are in pristine condition, even when significant corrosion has occurred on the shaft. There is no method to identify the degree of corrosion without removing the bolt from service. A coating that changes color on the bolt head or nut when corrosion starts would greatly speed up the inspection process.

Corrosion Inhibition Tests

20 h

48 h

74 h

116 h

139 h

FIGURE 12 | Six-month salt fog test results of selected coating systems. B1-1

B1-2

B1-3

Test panels coated with Carboline Carbomastic 15 FC epoxy mastic containing water core microcapsules with an inhibitor were tested using a salt fog chamber, for approximately 6 months, following the ASTM B 117 standard method. Panels were evaluated for both rust grades (ASTM D 610) and scribe ratings (ASTM D 1654). Several coating systems were tested; the coating containing 10% phenylphosphonic acid microcapsule performed the best. The corrosion ratings of these panels are shown in Table 1 in comparison with the controls. After six months of salt fog testing, the control showed blisters and corrosion under the paint, while the phenylphosphonic acid (PA) microcapsule-containing panel showed no sign of corrosion. In order to evaluate the scribe areas, the coating around these areas on the panels was scraped off for easy observation (Figure 12). It was found that the PA microcapsule-containing coating showed much better adhesion than the control.

Summary A multifunctional smart coating for the autonomous control of corrosion is being developed using pH-sensitive microcapsules. The microcapsules are designed specifically to detect the pH changes that are associated with the onset of corrosion and respond autonomously

TABLE 1 | Rust grade and scribe rating of Carbomastic 15 FC experimental coatings. Control Carbomastic 15 FC B7-1

B7-2

B7-3

Carbomastic 15 FC Coating Systems Control

10% Phenylphosphonic Acid Water Core Capsules in Carbomastic 74



NOV EMBER 2011 | W W W . P C I M A G . C O M

10% (w/v) phenylphosphonic acid microcapsule

Rust Grade

Scribe Rating

1

5

5

2

10

5

3

6

5

1

10

5

2

10

5

3

10

5

Sample #

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A Multifunctional Coating for Autonomous Corrosion Control

to indicate its presence early, to control it by delivering corrosion inhibitors, and to deliver self healing or film-forming agents capable of repairing mechanical damage to the coating. Various pH-sensitive microcapsules with hydrophobic or hydrophilic cores were synthesized through interfacial polymerization reactions in an emulsion. The microencapsulation process was optimized to obtain monodispersed microcapsules in a size range suitable for incorporation into commercially available coatings. The microcapsules can be obtained in suspension or in free-flowing powder form. Preliminary results from salt fog testing of panels coated with commercially available coatings in which the microcapsules and particles were incorporated indicate that microcapsules and particles can be used to detect corrosion before visible rust appears and to deliver corrosion inhibitors. Current work is focused on optimizing the concentration of indicator in the microcapsules or particles as well as on optimizing the release properties of the microcapsules and particles when incorporated into coatings of interest. Encapsulation methods for selfhealing agents and film-forming compounds are being developed to incorporate the self-healing function into the multifunctional coating. 

References 1

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Maile, F. J.; Schauer, T.; and Eisenbach, C.D. Evaluation of Corrosion and Protection of Coated Metals with Local Ion Concentration Technique (LICT), Progress in Organic Coatings 38, 111 (2000). Li, W. and Calle, L.M. pH and Electrochemical Responsive Materials for Corrosion Control Applications (Invited), NACE Corrosion 2008, New Orleans, LA, March 2008. Kessler, M.R. Self-Healing: A New Paradigm in Material Design, Proc. IMechE Vol. 221 Part G: J. Aerospace Engineering, page 479-495 (2007). Andersson, Magnus; Wilson, Gerald O.; White, Scott R. Evaluation of Self-Healing Polymer Chemistries for Application in Anti-Corrosion Coatings, American Coatings Conference 2008 at Charlotte, NC (June 2-4, 2008). Cho, Soo Hyoun, PhD Thesis “Polydimethylsiloxane-Based SelfHealing Composite and Coating Materials”, University of Illinois at Urbana-Champaign, Urbana IL (2006). Li, W. and Calle, L.M. Controlled Release Microcapsules for Smart Coatings, NACE Corrosion 2007, Paper 07228, Nashville, TN, March 2007. Li, W. and Calle, L.M. A Smart Coating for the Early Detection and Inhibition of Corrosion, Proceeding of the Smart Coatings 2007, p.191, Orlando, Florida, February 2007. Calle, L.M. and Li, W. Coatings and Methods for Corrosion Detection and/or Reduction, U.S. Patent No. 7,790,225, U.S. Patent and Trademark Office, September 7, 2010.

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nnovation that improves quality and lowers total applied cost is one of the hallmarks of the intensely competitive global automotive coatings business. Environmental and productivity demands are driving new technologies into the conservative world of automotive original equipment manufacturer (OEM) coatings. New compact process technologies – such as the B1:B2 compact process from PPG Industries – that are water-based and improve productivity are being rapidly adopted by global OEMs.

FIGURE 1 | Global compact process projections. 80

Solventborne CP Plants

Waterborne CP Plants

Number of Plants

70 60 50 40 30 20 10 0

98 99 00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 Calendar Year

Note: PPG Projection

Cool

Clean, Pretreated Body in White

Bake Rinse Cycle

E-Coat

Primer Bake Primer Application Sealer + Gel Bake

Primer Sanding

Inspection

Cool

BC Interior Application

Bake

Cool

FIGURE 2 | Traditional painting process.

E-Coat Sanding

Basecoat Application

Clearcoat Application Basecoat Dehydration

Source: PPG Industries Pictorial representation: not to scale

Interest in condensing, or compacting, the automotive paint process is growing globally. The key driver for the trend is that it allows the automobile manufacturers to reduce and lean their processing footprints and increase their processing efficiency. Compact process footprints lower manufacturing costs, lower energy consumption and lower environmental emissions. Inherent in the attainment of these benefits is the requirement that the automotive manufacturers, equipment suppliers and paint suppliers all work together to enable the automotive manufacturer to implement the necessary layout, process control and paint formulation to be successful. In addition to compact process layouts, another global trend within the automotive coating business is the transition from solvent-based topcoat systems to water-based topcoat systems. In North America and Europe, many OEMs have already converted their assembly plants to water-based primers and basecoat layers in order to lower VOC emissions. This trend is now expanding to Asia, especially in China, where OEMs are moving forward with water-based primer and basecoat systems. Driven by the combination of these two increasing and global trends, OEMs and paint suppliers have increased cooperation and strategic relationships to develop new painting processes. Numerous waterbased compact processes have been retrofitted into existing facilities, as well as designed into new manufacturing plants around the world (Figure 1). PPG has developed and successfully launched its waterbased B1:B2 technology for compacted processes. In the traditional automotive paint process, the application of the pretreatment and electrocoat is followed by a primer layer that is cured. After the primer layer, basecoat and clearcoat layers are applied and cured (Figure 2). PPG’s B1:B2 technology enables the automotive manufacturer to reduce the number of steps necessary to paint a vehicle by eliminating the dedicated primer booth and its related processing. The B1 and B2 layers are applied wet-on-wet, and afterwards the vehicle then continues through the process as it would in a traditional process layout (Figure 3). Automated equipment is recommended for the application of both the B1 and B2 layers, due to the need for application consistency within the painting of one vehicle, as well as the need for consistent application from one vehicle to the next. The placement of the painting of the interior door checks, engine compartment and trunk (interior spray) with a basecoat is also a consideration when designing a compacted process. In a traditional process, this application

By Debbie Linn, Global Compact Process Product Manager | PPG Industries, Pittsburgh, PA 78



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Innovation Drives Compact Paint Process for Waterborne Automotive OEM Coatings FIGURE 3 | Waterborne B1:B2 compacted painting process.

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Inspection



Bake

B2 Application

Clearcoat Application Basecoat Dehydration

Source: PPG Industries Pictorial representation: not to scale

is completed between the primer and basecoat layers. Similarly, in a compacted process design, this operation should occur between the B1 and B2 layers. Positioning the interior spray application between the B1 and B2 application allows for efficient use for the topcoat booth space and the elimination of overspray concerns. If the interior spray occurs after the B1 application, this allows time for the B1 layer to air flash before the application of the B2 layer. Color-keyed (gray, white, red, charcoal) B1s can be used in this compacted process. Although not recommended, the B1:B2 technology has been utilized with compacted processes where the interior spraying has occurred prior to the B1 application. In some instances the existing topcoat booth could not be retrofitted. In these situations, color-specific B1s were used in the compacted process. The B1s were shaded to match the B2 basecoats to avoid any overspray color issues. The primary directive for PPG researchers is to preserve the key characteristics of the entire layering system and make a conversion to a compacted system invisible to the end consumer. Understanding the science behind the key design attributes (field performance, layer synergy, environmental compliance and appearance) is critical to the success of the B1:B2 technology development. PPG’s B1 layers are developed to have primer-type properties (like filling and chip resistance), as well as provide adequate light opacity to the system to provide delamination protection and field performance. The B2 layers are developed to provide the final color shade and also add addi-

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B2 Interior Application

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tional light opacity. The B1 and B2 layers protect the electrocoat layer, which is the corrosion barrier for the vehicle, from the damaging wavelengths of light that may penetrate the topcoat system. Film build ranges for the B1 and B2 layers are established during the development process, and it is very important that these ranges are capable and maintained within the compacted process application. This is critical to prevent damaging wavelengths from penetrating to the electrocoat layer, which can lead to delamination of coating layers. In 2004, the first generation of PPG’s waterborne B1:B2 was successfully launched in Europe. In January 2010, the second generation of B1:B2 waterborne paint technology was successfully launched in the United States at the BMW assembly plant in Spartanburg, SC and is still currently in production. This marks the first use of a waterborne compact process in a U.S. automotive manufacturing plant. As the global expansions of compacted processes are forecasted, PPG is positioning the water-based B1:B2 technology as a solution for automotive manufacturers worldwide. PPG continues to support the expansion with technology and experience from Europe and North America and with waterborne paint manufacturing capabilities within Asia. Water-based B1:B2 technology allows manufacturers to reduce the footprint of a paint shop, reduce energy consumption, lower environmental emissions and increase overall process efficiency.  For more information, visit www.ppg.com.

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E-Sperse® RS-series reactive surfactants offer better performance properties such as smaller particle size, better mechanical stability, and much improved water resistance of the coating than when standard, non-reactive emulsifiers are used. Enhanced coating properties are the result of the reactive surfactant being incorporated into the backbone of the polymer chain; therefore, less free surfactant remains in the coating that can cause coating defects, reduced adhesion, and moisture sensitivity. Thus any coating for architectural, decking, environmental, metal coating or other industrial applications where reduced water sensitivity and better adhesion properties are needed would benefit from the use of E-Sperse® RS-series products. E-Sperse® RS-series surfactants are currently available in nonionic, anionic-sulfate, and anionic-phosphate ester forms. Customization of RS products for your polymer system is quite possible since product line development is ongoing.

To date, the most effective and economical method to prevent ship biofouling is the application of an antifouling paint that releases a biocidal compound. With the worldwide ban on tributyltin (TBT), marine coatings manufacturers have looked to copper as a substitute. Now this too is coming under increased regulatory pressure in certain locals. At the same time, there has been a continued record rise in the price of copper over the last years, making copper a less desirable option for fouling control from an economical perspective. ECONEA® is a unique, metal-free antifouling agent developed by Janssen PMP for the next generation of marine antifouling paints for ships and other marine structures.

Key Features and Benefits: • • • • • • • • •

Cost-effective alternative to copper; Superior broad spectrum of activity against hard fouling; Excellent longevity, low leaching; As effective as copper at about one tenth the amount in the paint; Unsurpassed static performance; Consistent performance in seawater and freshwater; Short half-life in aquatic environment; Supported under regulatory schemes worldwide; Enabling technology (improved colour retention, fit for use on aluminium, weight savings, light and bright colours, lower VOC etc.).

For additional information and sample requests, please contact us.

Tel: 864/277.1620 [email protected] www.ethox.com

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NOVEMBER 2011 | W W W . P C I M A G . C O M

www.janssenpmp.com 609/730.2609

ADVERTORIAL

ADDITIVES

COAT I N G S

OMG

Deft Incorporated

Borchi® OXY – Coat 1101: A Next Generation VOC-Free Curing Agent

Environmentally friendly corrosionresistant pretreatments

Are you having trouble drying your coatings based on renewable resins and lower VOCs? The challenges to the formulator to achieve the desired curing properties of typical solvent-based coatings while meeting the established VOC requirements have been difficult. OMG has responded to this challenge by creating Borchi® OXY – Coat 1101.

D ef t I nc or p orat e d, located in Irvine, CA, has created a new line of envi ronmentally f r iend ly c or ro sionresistant pretreatments and conversion coatings for aluminum and ferrous substrates used in aerospace and industrial applications. These pretreatments have eliminated the need for traditional hexavalent chromium and other hazardous heavy metal pretreatments used to provide corrosion resistance. While these new pretreatments and conversion coatings provide corrosion resistance, they also provide adhesion promotion where alternative adhesion promoters show little or no corrosion resistance. Currently, the F-15 fighter jet program at Warner Robins AFB, Georgia, has been successfully utilizing a Deft nonchrome pretreatment and conversion coating since 2010. This pretreatment (RECC 1015) and conversion coating (RECC 3021) used in conjunction with Deft’s non-chrome primer (02GN093) have vaulted the F-15 group to be the first to successfully implement a complete non-chrome coating system on an aircraft without sacrificing the necessary properties that they require in substrate (2000 and 7000 series aluminums) protection. On the industrial side, Freightliner Corporation, located in Gastonia, NC, has successfully implemented a Deft ferrous pre-conditioner (RECC 3016) and conversion coating (RECC 3012) for ferrous and aluminum substrates. This dip tank process has been utilized since 2009 for 1000, 3000, 5000, and 6000 series aluminums as well as being used for ferrous substrates such as cold rolled and galvanized steel and for zinc and magnesium substrates. Deft Incorporated continues to strive to be the environmental leader in providing coatings for a cleaner and safer environment. For more information, contact 1-800-5443338 or visit www.deftfinishes.com.

Borchi® OXY – Coat 1101 is a zero % VOC, cobalt-free additive designed to dry paint. This next-generation technology provides the solution for those in the coatings industry looking to break new ground. Borchi® OXY – Coat 1101 is designed for all coatings that dry by oxidation, e.g. alkyds, vegetable oils, epoxy esters, polybutadiene, etc. Compared to traditional cobalt-based paint driers, Borchi® OXY – Coat 1101 shows improved drying activity, color performance and excellent results under adverse conditions. Borchi® OXY – Coat 1101 demonstrates enhanced properties compared to cobalt; and is dissolved in water. When looking for performance, Borchi® OXY – Coat 1101 outclasses traditional paint driers. Key properties of Borchi® OXY – Coat 1101: • Zero VOC • Cobalt-free • Highly effective in waterborne oxidatively curing systems • Exceptional under adverse conditions • Enhanced whitening over cobalt and manganese carboxylates • High activity at low use levels

www.borchers.com

www.deftfinishes.com PAINT & COATINGS INDUSTRY



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ADVERTORIAL

R E S I N S / P O LY M E R S

R E S I N S / P O LY M E R S

AGC Chemicals America, Inc.

Esstech Inc.

Introducing Lumiflon FEVE Water Dispersion Resins!

Introducing EXOTHANE™ Elastomers – Optimizing the Mechanical Properties of Photocurable Formulations

For over 30 years, LUMIFLON – the fluoroolefin vinyl ether (FEVE) copolymer resin developed by AGC Chemicals in 1982 – has been an industry leader in ultra-weatherable resins. LUMIFLON resins offer many advantages, including the ability to cure at both elevated and ambient temperatures. LUMIFLON’s excellent pigment compatibility makes possible its wide gloss range and broad color palette. Because LUMIFLON dramatically extends the lifespan of bridges and other structures while reducing or even eliminating the need for recoating, even its solvent-based formulations offer significant sustainability advantages. Yet in addition to those solvent-based products, the chemistry of FEVE resins enables a wide range of resins to be manufactured, including powder coated and water-based resins. In recent years, in response to increasing environmental impact awareness and regulation, AGC Chemicals has developed water-based versions of its LUMIFLON FEVE resins that offer the same properties and outstanding performance as the traditional solvent-based formula. The latest development in water-based resins is the company’s new water dispersion resin, LUMIFLON FD-1000. Pigmented coatings based on these dispersions offer weatherability, durability, gloss retention, and water resistance comparable to the traditional solvent-based FEVE coatings. These water dispersion resins can be formulated to meet the most stringent VOC regulations in the country.

EXOTHANE™ Elastomers represent the most recent advances in Esstech’s urethane chemistry. These versatile materials offer performance enhancements across a broad range of demanding formulations. The enhanced properties of the EXOTHANE Elastomers include low volumetric shrinkage, low shrinkage stress, high percent elongation, high hardness and low color. • Exothane 8, low-color urethane, creates a “soft” yet tough polymer with high elongation; • Exothane 9, increases fracture toughness of formulations, very low viscosity and low color; • Exothane 10, low shrinkage, good conversion and enhanced toughness; • Exothane 24, high crosslink capacity, low in color and viscosity and very high Shore D hardness; • Exothane 26, high flexibility when cured, has the ability to re-adhere at lower tensile strength; • Exothane 32, very low in color and viscosity, provides improved flexibility. The EXOTHANE Elastomers can modify formulations without having to use non-reactive additives. Contact us to discuss your unique application and request samples at www. esstechinc.com.

About Esstech Esstech, Inc. is a focused team with significant experience developing unique chemistries to meet the needs of various industries and applications. Their current catalog consists of monomers, oligomers and adhesion promoters.

Get the free mobile app at

LUMIFLON® 610-423-4300 [email protected] www.LumiflonUSA.com 84



NOVEMBER 2011 | W W W . P C I M A G . C O M

http://gettag.mobi

www.EsstechInc.com [email protected] 610-521-3800

EQUIPMENT

LANGGUTH AMERICA Ltd. Label ALL containers on ONE machine! Langguth offers the E510 Inline Combination Labeler for both pressure sensitive and cold glue labels, accepting multiple body labels, lid labels, print & apply, and full wrap roll-on. Virtually all common containers – round can, tapered pail, and F-style –will run on Langguth’s easy changeover inline labeler.

For very high speed applications Langguth’s E520 Rotary Combination labeler integrates a hot melt label station for cut labels, while maintaining flexibility for cold glue and pressure sensitive. The labeler delivers significant adhesive savings when running high speed cut labels, and, quickly changes over to other formats. The Rotary E520 is an excellent choice for aerosol, cone top, F-style, gallon and even tapered cans. 80 years of Langguth innovation go into every machine. Our standard designs encompass banana shaped labels, complex tapers, 3 dimensional adjustable label magazines, and, of course a robust frame intended for decades of 24/7 production. What is your toughest problem today? Maybe Langguth developed an answer years ago.

The ECKART effect – the 3rd dimension for surfaces. The ECKART effect is impressive. LUXAN glass pearl pigments provide all applications with a special touch and a value-added appeal. Extraordinary pearlescent effects are the height of luxury and distinction – guaranteeing the most positive of reactions. The LUXAN pigments exhibit outstanding brightness and reflecting power that lead to distinct flashy and clear color stylings.

http://www.langguth-america.com/A/Pail/Pail_Labeling_E510.html

Visit our website for videos showing our labelers in action.

- LABELING MACHINES - AUTOMATION - PAIL HANDLING SYSTEMS

A sensational look with improved product performance – that’s the ECKART effect. For further information, please contact: ECKART America Corporation · 4101 Camp Ground Road Louisville, Kentucky 40211 · USA · Tel +1502 775-4241 Fax +1502 775-4249 · Toll-free 877 754 0001 [email protected] · www.eckart.net

RELIABLE LABELING SYSTEMS SINCE 1932

Phone: 519-888-0099 Fax: 519-888-0029 [email protected] www.langguth-america.com Visit ads.pcimag.com PAINT & COATINGS INDUSTRY



85

P RODUCTS  Grinding Media

 Mixer

3M: 3M™ Micro Milling Media ZGC

CHARLES ROSS & SON CO.: The Planetary Dual Disperser features four agitators – two planetary stirrers and two high-speed shafts – all rotating on their own axes while orbiting the mix vessel on a common axis. Shear levels and flow patterns in the PDDM are easily fine tuned because the stirrers and dispersers are independently driven and controlled. Call 800/243.7677.

high-density (5.8 g/cc) grinding media are as strong and as wear resistant as yttria-stabilized zirconia beads. Due to a nanocrystalline microstructure (~50-100 nm), these micro beads feature low friction, smooth surfaces and excellent sphericity. Available in 50, 75 and 100 microns, they are ideal for use in the milling of pigments, inks, dyes, and coatings. Call 800/367.8905.

 Pigment

 Viscometer

magenta of quinacridone chemistry with good light and weather fastness properties. The pigment can be combined with opaquegrade pigments (orange and red) to produce solid shades or effect pigments to produce metal-effect shades. E-mail [email protected].

ATS RHEOSYSTEMS: The Black Pearl Viscometer is a highperformance rotational viscometer capable of both steady shear and yield stress testing. It comes standard with built-in Peltier temperature control for all measuring systems. Cone and plate, parallel plate, and concentric cylinder measuring systems are included. E-mail [email protected].

 Dust-Collection System

 Resin

BLASTRAC: Designed for multipurpose uses and built mainly of

PFLAUMER BROTHERS, INC.: Teraspartic® 277 and 292 are amine-functional resins used for polyurea polyaspartic coatings for concrete, metal, wood and other substrates. They are sterically hindered aliphatic amines that react with polyisocyanates to form high-gloss, weather-resistant coatings with good film build and rapid cure rates. Visit www.pflaumer.com. 

CAPPELLE PIGMENTS NV: Lysopac Red 2230C is a clean-shade

durable steel, the BDC-1330DBP is tough, damage resistant and constructed for professional use. It offers high performance with relatively low energy consumption and has a quick release-andattach dust bin that easily dismounts for debris disposal with a capacity of 143 lbs. Visit www.blastrac.com.

SUPPLIER SHOWCASES

THINGK AC 2403 THINGK Alberdingk Y Solvent free Polyurethane dispersions Y Renewable Polyurethane dispersions Y Solvent free Waterborne UV dispersions Y Very Low VOC Self Crosslinking multiphase emulsions

It’s easy! Use Colorstream® pigments from EMD Chemicals to create astonishing ‘color travel’ effects ...to keep you at the top of your game. That's what's in it for you. EMD Chemicals

EMD Chemicals 888.367.3275 | [email protected] www.emdchemicals.com

www.AlberdingkUSA.com/AC2403TechBulletin.pdf

“Welcome to Our World”

100 Eames St. Wilmington, MA 01887 ph: 978-988-0880 fax: 978-658-3366 www.allcoattech.com [email protected]

86

What’s the secret to amazing color travel effects?



AllUthane 30522 is a solvent-free, water-based aliphatic polyurethane dispersion. It has excellent adhesion to a variety of substrates making it suitable for formulating low-VOC coatings for metal, wood and plastic substrates. The polymer exhibits exceptional toughness and has superb abrasion and chemical resistance making it ideal for challenging interior or exterior applications. For product and application information call: Kurt Bimmler at 978-988-0880, ext-311 or email [email protected]

NOVEMBER 2011 | W W W . P C I M A G . C O M

Powder Coatings – Foundation for the Novice Formulator This book presents a logical, methodical approach to building a successful powder coating. Not only are the basics of resin, pigment and additive choices covered, but also the philosophy of constructing a product that meets your customer’s needs both practically and economically. A clear concise explanation of manufacturing and quality control is also covered. Available in book or CD format. Contact [email protected] for ordering information.

www.pcimag.com MORE information. MORE resources. MORE ways to do your job better.

C LASSIFIEDS EQUIPMENT

EQUIPMENT

FOR SALE!

HOCKMEYER

IN-STOCK 400-GALLON PLANETARY DISPERSER!

EQUIPMENT CORPORATION A leader in the grinding and dispersion industries New & Used Equipment Dispersers • Mills • Mixers • Tank & Tote Washers • Particle Size Analysis • Vessels

• Stainless Steel • Change Can Design • Vacuum Construction • Jacketed Mix Can

Visit us at www.hockmeyer.com or call us at 252-338-4705

1-800-243-ROSS

USA Tel: 631-234-0500 • Fax: 631-234-0691

www.mixers.com [email protected]

Wanted to purchase: Used Dispersers & Mixers

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RECRUITMENT SERVICES Specializing in paint/coatings industry. Seeking passionate, high-impact professionals for nationwide positions. Send your resume in confidence to: Spencer M. Hermann

SEARCHLIGHT PARTNERS 28052 Camino Capistrano, Suite 209 Laguna Niguel, CA 92677 (949)429-8813 • [email protected]

PRODUCTS & SERVICES Focus Pigment (Taiwan)

Manufacturer of Organic Pigments Aluminum Paste

Resin-Coated Aluminum Paste Waterborne Aluminum Paste Aluminium Powder Metallic Aluminum Paste Leafing Aluminum Paste Email: [email protected] Website:www.focuspigment.com We are seeking distributors

www.bladedepot.biz

484-684-6986 [email protected]

POSITIONS AVAILABLE Hempel (USA), Inc. COATINGS ADVISOR & QUALITY CONTROL MANAGER The Hempel Group is a leader in the production and sales of protective coatings in the marine, container, yacht, decorative & protective markets. Stainless IT

Stainless ITT

CONN Blade®s

The Most Efficient & Aggressive Available

RECRUITMENT SERVICES Paint & Coatings Industry Executive Search

UHMW Poly

www.connblade.com

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NOVEMBER 2011 | W W W . P C I M A G . C O M

Coating Advisors Will manage projects & advise customers on proper use and application of Hempel technologies and coating systems. QC Manager Will manage quality activities and personnel in our QC lab and will perform quantitative testing. For more information, visit the POSITIONS AVAILABLE page at www.pcimag.com/classifieds Send resumes to [email protected]

Asia PaciÄc Coatings Show 2012 Balai Sidang Jakarta Convention Centre, Indonesia 19 – 20 September 2012 THE LEADING COATINGS EVENT IN SOUTH EAST ASIA & THE PACIFIC RIM BOOK YOUR STAND TODAY Contact: Kez Chen Tel: +44 (0)1737 855 107 Email: [email protected] Jeff Montgomery Tel: +44 (0)1737 855 078 Email: [email protected]

www.coatingsgroup.com Organised by:

Sponsored by: www.polymerspaintcolourjournal.com

C LASSIFIEDS POSITIONS AVAILABLE TECHNICAL SALES & MARKETING DIRECTOR Young and growing international special effects pigment company seeks Technical Sales & Marketing Director to run US & Canadian markets, consisting of direct accounts and distributors. Significant growth opportunity.

POSITIONS AVAILABLE

CUSTOM MANUFACTURING

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Toll Converting & Packaging

Visit the POSITIONS AVAILABLE page at www.pcimag.com/classifieds for Qualification/Education requirements and application instructions.

• ISO 9001:2008, FDA-EPA-ATF Reg. Facility • 2 plants in N. Texas • Epoxy, urethane, solvent, water-based • High speed dispersion, vacuum processing • Adductions, advancements, prepolymer • Small, medium and large batch • Packaging: tankwagon, totes, drums, pails, gallons, quarts, pints and smaller

Andrea Kropp Ph: (810) 688-4847 Fax: (248) 502-1048 Email: [email protected]

Paint Process Engineer - Visit this link for complete details: www.eisenmann.us.com/careers/paintprocessengineer.html

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www.quadrantchemical.com [email protected] 200 Industrial Blvd., McKinney, TX 75069 972-864-0865 x 25 / 972-542-0072

AD INDEX 3M . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 www.3M.com/ZGC AGC Chemicals America, Inc. . . . . . . . . . 84 www.lumiflonUSA.com Alberdingk Boley, Inc. . . . . . . . . . . . . . . . . 86 www.AlberdingkUSA.com AllCoat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 www.allcoattech.com American Coatings Show 2012 . . . . . . . 79 www.american-coatings-show.com Arch Chemicals . . . . . . . . . . . . . . . . . . . . . . 67 www.archbiocides.com/proxelbzplus Arkema Emulsion Systems . . . . . . . . . 14-15 www.arkemacoatingresins.com/SNAP Asia Pacific Coatings Show 2012 . . . . . . 89 www.coatingsgroup.com Brenntag North America . . . . . . . . . . . . . . 7 www.brenntagnorthamerica.com Burgess Pigment . . . . . . . . . . . . . . . . . . . . . 65 www.burgesspigment.com BYK USA Inc. . . . . . . . . . . . . . . . . . . . . . . . . 11 www.byk.com Celanese Emulsion Polymers . . . . . . . . . . 45 www.Celanese-Emulsions.com/Brasil CINIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 www.cinic.com CLEARopinion . . . . . . . . . . . . . . . . . . . . . . . 81 www.myclearopinion.com CMC Argentina, LTD . . . . . . . . . . . . . . . . .44 www.cmcmilling.com www.spechem.com.ar Conn and Co. . . . . . . . . . . . . . . . . . . . . . . . . 10 www.connblade.com CPS Color. . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 www.cpscolor.com Cytec Industries Inc.. . . . . . . . . . . . 9, 48, 76 www.cytec.com DeFelsko Corp. . . . . . . . . . . . . . . . . . . . . . . . 18 www.defelsko.com Deft Incorporated . . . . . . . . . . . . . . . . . . . . 83 www.deftfinishes.com Eastman Chemical Company . . . . . . . . . 29 www.eastman.com/optifilmOT1200 Eckart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 www.eckart.net Elcometer . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 www.elcometer.com EMD Chemicals Inc. . . . . . . . . . . . . . . . . . . 86 www.emdchemicals.com Emerald Performance Materials . . . . . . . 53 www.emeraldmaterials.com Esstech, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . 84 www.EsstechInc.com Ethox Chemicals, LLC. . . . . . . . . . . . . . . . . 82 www.ethox.com

Evonik Degussa . . . . . . . . . . . . . . . . . . . . . . 23 www.evonik.com/colortrend GEO Specialty Chemicals . . . . . . . . . . . . . 60 www.geosc.com Heubach. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 www.heubachcolor.com Huntsman . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 www.huntsman.com ISP Performance Chemicals . . . . . . . . . . . . 4 www.ispcoatings.com/water Janssen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 www.janssenpump.com King Industries . . . . . . . . . . . . . . . . . . . . . . 30 www.kingindustries.com Langguth America Ltd. . . . . . . . . . . . . . . . 85 www.langguth-america.com LANXESS Corporation. . . . . . . . . . . . . . . . 13 www.mpp.us.lanxess.com Mason Color Works, Inc. . . . . . . . . . . . . . . 77 www.masoncolorpigments.com Micro Powders, Inc. . . . . . . . . . . . . . . . . . . 91 www.micropowders.com Mitsubishi Gas Chemical America, Inc. . . . . . . . . . . . . . . . . . . . . . . . . 31 www.aromaticchemicals.com Munzing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 www.munzing.com OM Group . . . . . . . . . . . . . . . . . . . . 72-73, 83 www.omgi.com www.borchers.com Perstorp . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 www.perstorp.com Reichhold. . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 www.Reichhold.com Ross, Charles and Son . . . . . . . . . . . . . . . . 71 www.PowderInjection.com Sartomer . . . . . . . . . . . . . . . . . . . . . . . . . . . .40 www.sartomer.com SiLi / Sigmund Linder GMBH . . . . . . . . . . 16 www.www.sili.eu Siltech Corporation. . . . . . . . . . . . . . . . . . . . 6 www.siltechcorp.com Sun Chemical Performance Pigments . . 61 www.sunchemical.com Troy Corporation. . . . . . . . . . . . . . . . . .17, 49 www.troycorp.com Unimin Corp. . . . . . . . . . . . . . . . . . . . . . . . . 52 www.BrilliantAdditions.com Univar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 www.univarcorp.com Wacker Chemical Corporation . . . . . .3, 80 www.wacker.com/e-business.com www.wacker.com/interior-paints

Visit ads.pcimag.com 90



NOVEMBER 2011 | W W W . P C I M A G . C O M

PUBLISHING/SALES STAFF Publisher/ Donna M. Campbell East Coast Sales Tel: 610/650.4050 • Fax: 248/502.1091 E-mail: [email protected] Midwest/ Lisa Guldan West Coast Sales Tel: 630/882.8491 E-mail: [email protected] China Media Rep. Arlen Luo Tel: 0086-10-88579899 E-mail: [email protected] Europe Regional Uwe Riemeyer Manager Tel: 49 (0)202-271690 E-mail: [email protected] Inside Sales Manager Andrea Kropp Tel: 810/688.4847 E-mail: [email protected] Production Manager Brian Biddle Tel: 847/405.4104 • Fax: 248/244.3915 E-mail: [email protected]

EDITORIAL STAFF Editor Kristin Johansson Tel: 248/641.0592 • Fax: 248/502.2094 E-mail: [email protected] Technical Editor Darlene R. Brezinski, Ph.D. E-mail: [email protected] Associate Editor Karen Parker Tel: 248/229.2681 E-mail: [email protected] Art Director Clare L. Johnson

OPERATIONS STAFF Single Copy Sales Ann Kalb E-mail: [email protected] Reprint Manager Jill L. DeVries 248/244.1726 E-mail: [email protected] For subscription information or service, please contact Customer Service at: Tel: 847/763.9534 or Fax: 847/763.9538 or e-mail [email protected]

Visit us: ABRAFATI Booth #97/110 & CHINA COAT Booth #3A09-10

Relentlessly working for YOUR perfect solution

Münzing. Solving your foam issues by providing the broadest range of defoamer chemistries and unlimited technical assistance to the coatings and printing ink industry. While we may deal in complex science, what we do is very simple. We make your job easier. By conducting unlimited, rigorous testing with the broadest range of defoamer chemistries, we’ll develop precisely the defoaming additive that solves your problem. It’s this kind of unyielding commitment to the needs of coating and printing ink formulators everywhere that has gotten us to where we are today. Practically on speed dial at some of the largest, and smallest, coating and printing ink R&D labs around the world.

The Industry Standard in Defoamers DEE FO® XRM-1537A DEE FO® XRM-1547A DEE FO® 3010E/50 DEE FO® 97-3 DEE FO® PI-12

DEE FO® PI-30 DEE FO® PI-35 DEE FO® PI-40 DEE FO® PI-45 DEE FO® PI-75

AGITAN® 299 AGITAN® 350 AGITAN® 760 AGITAN® 771

To try our AGITAN and DEE FO defoamers and take advantage of our unlimited technical service, call

1-800-524-0055

www.munzing.com I [email protected]