Thermodynamics of Polymer Blends (Polymer Thermodynamics Library , Vol 1)

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Start of Citation[PU]Technomic Publishing[/PU][DP]1997[/DP]End of Citation

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Start of Citation[PU]Technomic Publishing[/PU][DP]1997[/DP]End of Citation

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Start of Citation[PU]Technomic Publishing[/PU][DP]1997[/DP]End of Citation

Table of Contents

Pagev

Preface

ix

1

J.

Basic Principles o f Thermodynamics of Polymer Solutions 1.1 The M a i n Thermodynamic Characteristics o f Solution 1.2 Regular Solutions. Hildebrand-Scatchard Equation — 1 . 3 Phase Equilibrium in Solutions. Binodals and Spinodals 1.4 The Flory-Huggins Theory 1.4.1 Entropy of M i x i n g 1.4.2 The Heat and Free Energy o f M i x i n g 1.5 Dilute Solutions o f Polymers — 1 . 6 Phase Separation In Polymer Solutions References 2 Statistical Theories of Polymer Solutions ~ " 2 . 1 The Theory by Prigogine-Patterson 2.2 The Role of Various Contributions o f the M i x i n g Parameters 2.3 Effect of Solvent Chain Length on the Interaction Parameters " " 2 . 4 N e w Flory Theory 2.5 M o d i f i c a t i o n of the N e w F l o r y Theory

1 2 4 9 10 U 13 \6 30 33 34 42 44 48 55

2.6 N e w Huggins Theory

59

2.7 Sanchez-Lacombe Theory

65

2.7.1 Equation of State

65

"2.7.2 Mixtures of Liquids

67

2.7.3 Free Energy and C h e m i c a l Potential

69

2.7.4 Functions of M i x i n g

70

2.7.5 Phase Stability and Spinodal

71

2.8 Some Experimental Results of Thermodynamic Properties o f Polymer

73

Solutions References

77

3 Thermodynamics o f Polymer M i x i n g 3.1 Binary Mixtures 3.1.1 Application o f the Theory of Regular Solutions to Thermodynamics of Polymer M i x i n g ^ .1.2 Application o f N e w Statistical Theories for Describing Thermodynamic Properties o f Polymer Mixtures 3.1.3 The Application o f the N e w Huggins Theory 3.1.4 The Sanchez-Lacombe Theory 3.1.4.1 Chemical Potentials ~i. 1.4.2 The Stability of Phase and Spinodal 3.1.4.3 Criterion of M i s c i b i l i t y o f Polymer-polymer M i x t u r e _ 3 . 2 Experimental Data on Thermodynamic Properties o f Binary Polymer Mixtures 3.2.1 Phase Behavior o f Binary Polymer Mixtures

81 81 83 88 98 101 102 104 107 110 112

Page vi 3.2.2 Concentration and Temperature Dependencies o f Parameters o f T h e r m o d y n a m i c Interactions in the Mixtures of Oligomers and Polymer Homologues 3.2.3 Influence o f Various Factors on the M i s c i b i l i t y

128

143

3.2.3.1 Deuteration and Tacticity o f Polymers

143

3.2.3.2 Branching of Chains

144

3.2.3.3 Effect o f Pressure

144

^ S . 2 . 3 . 4 Asymmetry o f the Length o f Statistical Segment 3.2.4 Possible Errors in Estimating the M i s c i b i l i t y o f Mixtures Obtained from Solutions in a C o m m o n Solvent 3.3 M i s c i b i l i t y of Polymers at the Interface with Solid

148 148 _L5J_

3.3.1 Phase Diagrams o f F i l l e d Polymer Mixtures

151

3.3.2 Phase Separation in T h i n F i l m s of Polymer Mixtures at the Interface

155

with S o l i d 3.3.3 Thermodynamic Interaction Parameters in F i l l e d Polymer Mixtures 3.3.4 O n the E q u i l i b r i u m and Non-equilibrium Compatibilization of Polymer Mixtures 3.4 Ternary Polymer Systems "3.4.1 Ternary Systems Polymer-polymer-solvent 3.4.2 Ternary Polymer-polymer-polymer Systems 3.5 Thermodynamics o f Formation of Stable Dispersion in Binary Polymer

161 167 169 169 185 205

Mixtures References 4 Homopolymer-copolymer and Copolymer-copolymer Blends " " 4 . 1 M e a n - f i e l d Binary Interaction M o d e l s 4.1.1 M i s c i b i l i t y W i n d o w s —A.2 Effect of the Sequence Distribution in Copolymer on the Phase Behavior o f Homopolymer-copolymer Mixtures —A3 The Dependence o f the Phase Behavior of Copolymer Mixtures o f Various Compositions on the Sequence Distribution —AA

210 227 227 230 235 239

The Effect of the Sequence Distribution in Copolymer and Its Compatibilizing Effect in M i x t u r e of T w o Immiscible Polymers AA 1 Mixtures o f Homopolymers with Homologue Series of Polymers of Another Chemical Nature 4.5 Ternary Mixtures

251

4.6 M o d i f i e d Theories of the Equation-of-state

264

References

271

5 Mechanism and Kinetics of Phase Separation in Polymer Solutions and Blends 5.1 Nucleation and Growth

243

259

275 275

5.2 Spinodal Mechanism o f Phase Separation

277

5.3 Application o f the Theory of Spinodal Decomposition to Polymeric Systems

283

Page vii _ _ 5 . 4 Some Experimental Results on Kinetics of Phase Separation in Solutions and Mixtures of Polymers 5.5 Factors Influencing the Kinetics o f Phase Separation

299 320

5.5.1 Tacticity

32J.

5.5.2 Effects of A d d i t i o n o f Diblock-copolymers

323

5.5.3 Spinodal Decomposition Near S o l i d Surface

328

"5.5.4 Shear-induced Phase Separation " 5 . 6 Phase Separation Accompanying Reactions of Polymer B l e n d Formation

329 334

5.6.1 Spinodal Decomposition in IPNs

334

5.6.2 Nucleation and Growth During I P N Formation

340

5.6.3 Some Features of Microphase Structure of IPNs References 6

35J. 356 363

Interface in D e m i s i n g Solutions and Polymer Mixtures 6.1 Vrij-Roebersen Theory —

364

6.2 Kammer's Theory

371

6.3 The Theory by Helfand

374

6.4 The Theory by Nose

380

—

6.5 Sanchez-Lacombe Theory

381

6.6 Other Theories o f Polymer-polymer Interface

391

6.7 Scaling Principle in Describing the Interface

397

6.8 Some Experimental Data on the Interfacial Properties o f Polymer Blends

400

—

6.8.1 Interfacial Tension

400

6.8.2 The Interfacial W i d t h and Interfacial Profiles

401

6.9 Surface Segregation in Polymer Mixtures

406

6.9.1 Surface Segregation Near the Interface with S o l i d

408

6.10 Segregation o f Block-copolymers at the Interface Between

412

Homopolymers References

428

Nomenclature

435

Index

443

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