Foreword ...................................................... х,м
Preface ........................................................ *v
About the Author .............................................. x'x
Chapter 1 Introduction to Polymer Blends ....................... 1
Learning Objectives ............................................. 1
1.1 History of Polymer Blends .................................. 2
1.2 Flory-Huggin's Solution Theory—and Beyond .................. 4
1.3 Miscible Polymer Blends .................................... 7
1.4 Partially Miscible Polymer Blends .......................... 8
1.5 Natural Polymers ........................................... 9
1.5.1 Primary Structure .................................. 10
1.5.2 Secondary Structure ................................ 11
1.5.3 Tertiary Structure ................................. 12
1.5.4 Quaternary Structure ............................... 13
1.6 Polymer Alloys ............................................ 16
1.7 Summary ................................................... 18
Exercises ...................................................... 20
References ..................................................... 21
Chapter 2 Equation of State Theories for Polymers ............. 23
Learning Objectives ............................................ 23
2.1 Small Molecules and Large Molecules ....................... 23
2.1.1 Kinetic Representation of Pressure ................. 24
2.1.2 Derivation of Ideal Gas Law ........................ 25
2.1.3 Van der Waals Cubic Equation of State .............. 27
2.1.4 Virial Equation of State ........................... 28
2.1.5 Redlich and Kwong Equation of State and Soave
Modification ....................................... 28
2.2 PVT Relations for Polymeric Liquids ....................... 30
2.3 Tait Equation ............................................. 30
2.4 Flory, Orwoll, and VRIJ (FOV) Model ....................... 32
2.5 Prigogine Square-Well Cell Model .......................... 35
2.6 Lattice Fluid Model of Sanchez and Lacombe ................ 37
2.7 Negative Coefficient of Thermal Expansion ................. 44
2.7.1 Historical Note .................................... 45
2.7.2 Violation of Second Law of Thermodynamics .......... 46
2.7.3 Proposed Isentropic Expansivity .................... 47
2.7.4 Measurements of Volume Expansivity Not Isobaric .... 49
2.8 Summary ................................................... 49
Problems ....................................................... 50
Review Questions ............................................... 54
References ..................................................... 55
Chapter 3 Binary Interaction Model ............................ 57
Learning Objectives ............................................ 57
3.1 Introduction .............................................. 57
3.2 Compositional Window of Miscibility: Copolymer-
Homopolymer ............................................... 59
3.3 Compositional Window of Miscibility: Copolymers with
Common Monomers ........................................... 60
3.4 Compositional Window of Miscibility: Terpolymer System
with Common Monomers ...................................... 62
3.5 Compositional Window of Miscibility: Terpolymer and
Homopolymer System without Common Monomers ................ 64
3.6 Spinodal Curve from В Values and EOS ...................... 65
3.7 Copolymer/Homopolymer Blends of AMS-AN/PVC ................ 67
3.8 Copolymer/Homopolymer Blends of AMS-AN with Other
Copolymers ................................................ 68
3.9 Intramolecular Repulsion as Driving Force for
Miscibility-Mean Field Approach ........................... 75
3.10 Summary ................................................... 80
Exercises ...................................................... 81
Problems ....................................................... 82
References ..................................................... 85
Chapter 4 Keesom Forces and Group Solubility Parameter
Approach ....................................................... 87
Learning Objectives ............................................ 87
4.1 Hildebrandt Solubility Parameter .......................... 87
4.2 Hansen Three-Dimensional Solubility Parameter ............. 89
4.3 Specific Interactions ..................................... 89
4.3.1 Experimental Determination of Equilibrium Rate
Constants .......................................... 94
4.3.2 Phase Behavior of Miscible Blends with Keesom
Interactions ....................................... 95
4.4 Summary ................................................... 98
Exercises ...................................................... 99
Review Questions .............................................. 103
References .................................................... 104
Chapter 5 Phase Behavior ..................................... 105
Learning Objectives ........................................... 105
5.1 Introduction ............................................. 105
5.2 LCST and UCST ............................................ 108
5.2.1 Case I LCST ....................................... 108
5.2.2 Case II UCST ...................................... 108
5.3 Circular Envelope in Phase Diagram ....................... 110
5.3.1 Case III Circular Phase Envelope UCST and LCST .... 110
5.3.2 Case IV Circular Phase Envelope LCST and UCST .......... 110
5.4 Hourglass Behavior in Phase Diagrams ..................... 114
5.4.1 Case V LCST and UCST Hourglass Behavior ........... 114
5.5 Molecular Architecture ................................... 106
5.6 Summary .................................................. 109
Exercises ..................................................... 120
Problems ...................................................... 121
References .................................................... 122
Chapter 6 Partially Miscible Blends .......................... 123
Learning Objectives ........................................... 123
6.1 Commercial Blends That Are Partially Miscible ............ 124
6.2 Entropy Difference Model (ΔΔSm) .......................... 124
6.3 Estimates of Change in Entropy of Mixing at Glass
Transition, ΔΔSm ......................................... 129
6.4 Copolymer and Homopolymer Blend .......................... 131
6.5 Sequence Distribution Effects on Miscibility ............. 134
6.6 Summary .................................................. 137
Nomenclature .................................................. 138
Subscripts .................................................... 139
Superscripts .................................................. 139
Greek ......................................................... 139
Exercises ..................................................... 139
References .................................................... 140
Chapter 7 Polymer Nanocomposites ............................. 143
Learning Objectives ........................................... 143
7.1 Introduction ............................................. 143
7.2 Commercial Products ...................................... 143
7.3 Thermodynamic Stability .................................. 144
7.4 Vision and Realities ..................................... 145
7.5 Fullerenes ............................................... 145
7.6 Carbon Nanotubes (CNTs) .................................. 147
7.7 Morphology of CNTs ....................................... 148
7.8 Nanostructuring Operations ............................... 151
7.9 Polymer Thin Films ....................................... 153
7.10 Nanostructuring from Self-Assembly of Block Copolymers ... 154
7.11 Intercalated and Exfoliated Nanocomposites ............... 155
7.12 Summary .................................................. 162
Exercises ..................................................... 163
References .................................................... 165
Chapter 8 Polymer Alloys ..................................... 167
Learning Objectives ........................................... 167
8.1 Introduction ............................................. 167
8.2 PC/ABS Alloys ............................................ 168
8.3 Nylon/ABS Alloys ......................................... 170
8.4 PVC Alloys ............................................... 171
8.5 Polyolefin Alloys ........................................ 173
8.6 Natural Polymer Alloy .................................... 174
8.7 Summary .................................................. 176
Exercises ..................................................... 177
References .................................................... 177
Chapter 9 Binary Diffusion in Polymer Blends ................. 179
Learning Objectives ........................................... 179
9.1 Introduction ............................................. 179
9.2 Diffusion Phenomena ...................................... 180
9.3 Fick's First and Second Laws of Diffusion ................ 181
9.4 Skylab Diffusion Demonstration Experiments ............... 183
9.5 Bulk Motion, Molecular Motion, and Total Molar Flux ...... 184
9.6 Stokes-Einstein Equation for Dilute Solutions ............ 186
9.6.1 Diffusion in Concentrated Solutions ............... 190
9.7 Diffusion in Solids ...................................... 191
9.7.1 Mechanisms of Diffusion ........................... 191
9.7.2 Diffusion in Porous Solids ........................ 193
9.8 Diffusion Coefficients in Polymers ....................... 194
9.9 Transient Diffusion ...................................... 195
9.9.1 Fick Molecular Diffusion - Semi-Infinite Medium ... 196
9.10 Damped Wave Diffusion and Relaxation ..................... 198
9.11 Periodic Boundary Condition .............................. 205
9.12 Summary .................................................. 208
Problems ...................................................... 209
Review Questions .............................................. 215
References .................................................... 216
Chapter 10 Copolymer Composition .............................. 219
Learning Objectives ........................................... 219
10.1 Introduction ............................................. 219
10.2 Composition for Random Copolymers ........................ 221
10.3 Composition of Random Terpolymers ........................ 224
10.4 Reactivity Ratios ........................................ 227
10.5 Multicomponent Copoly merization-n Monomers .............. 229
10.6 Summary .................................................. 239
Problems ...................................................... 239
Review Questions .............................................. 240
References .................................................... 241
Chapter 11 Sequence Distribution of Copolymers ................ 243
Learning Objectives ........................................... 243
11.1 Dyad and Triad Probabilities in Copolymer ................ 243
11.2 Dyad and Triad Probabilities in Terpolymers .............. 249
11.3 Sequence Alignment in DNA and Protein Sequences .......... 259
11.3.1 Global Alignment of a Pair of Sequences ........... 261
11.3.1.1 Algorithm 1 Global Alignment ............. 262
11.3.2 Dynamic Programming ............................... 265
11.3.3 Analysis of Time and Space Efficiency ............. 266
11.3.4 0(n) Space Solution by Dynamic Array .............. 266
11.3.5 Subquadratic Algorithms for Longest Common
Subsequence ....................................... 266
11.3.5.1 Algorithm 2: Length of Longest
Increasing Subsequence ................... 267
11.3.5.2 Algorithm 3: Find and Print the Longest
Common Subsequence of S and T ............ 267
11.3.6 Greedy Algorithms for Pairwise Alignment .......... 268
11.3.6.1 Algorithm 4: Tool for Aligning Very
Similar DNA Sequences .................... 269
11.3.7 Other Methods for Pairwise Alignment .............. 271
11.3.8 Grading Functions during Global Alignment ......... 271
11.4 Summary .................................................. 271
Problems ...................................................... 271
Review Questions .............................................. 272
References .................................................... 273
Chapter 12 Reversible Polymerization .......................... 275
Learning Objectives ........................................... 275
12.1 Heat Effects during Polymerization ....................... 286
12.2 Ceiling Temperature during Reversible Polymerization ..... 290
12.3 Subcritical Oscillations during Thermal Polymerization ... 294
12.3.1 Thermal Initiation by Diels-Alder Dimerization .... 295
12.3.2 Four Reactions in a Circle ........................ 299
12.3.3 General Case of n Reactions in Circle ............. 300
12.4 Thermal Terpolymerization of Alphamethyl-Styrene,
Acrylonitrile, and Styrene ............................... 300
12.4.1 Experimental ...................................... 301
12.4.2 Results ........................................... 302
12.5 Reversible Copolymerization .............................. 304
12.5.1 Copolymer Composition ............................. 304
12.5.2 Heat of Copolymerization .......................... 308
12.6 Summary .................................................. 309
Problems ...................................................... 311
Review Questions .............................................. 313
References .................................................... 313
Appendix A: Maxwell's Relations ............................... 315
Appendix B: Five Laws of Thermodynamics ....................... 319
Appendix C: Glass Transition Temperature ...................... 331
Appendix D: Statistical Distributions ......................... 335
Index ......................................................... 343
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