2. Page iii
Concepts of Polymer Thermodynamics
Polymer Thermodynamics Library, Vol. 2
Menno A. Van Dijk
Shell Research and Technology Centre, The Netherlands
André Wakker
Shell Research and Technology Center, Belgium
Start of Citation[PU]Technomic Publishing[/PU][DP]1997[/DP]End of Citation
4. Page v
Table of Contents
Preface ix
1
Introduction 1
References 4
2
Elements of Thermodynamics of Mixtures 5
2.1 Fundamentals 5
2.1.1 The Laws of Thermodynamics 5
2.1.2 Thermodynamic Functions and Relations 5
2.1.3 Mixtures 7
2.1.4 Composition Variables 8
2.2 Phase Equilibria 11
2.2.1 Phases 11
2.2.2 Gibbs Phase Rule 12
2.2.3 Free Energy of Mixing 13
2.2.4 Phase Stability 14
2.2.5 Phase Diagrams 18
2.2.6 Multicomponent Mixtures 21
2.2.7 Crystallizable Components 23
5. 2.3 Ideal Mixtures 25
2.4 Regular Mixtures 31
2.4.1 Deviations from Ideality 31
2.4.2 Regular Mixtures 32
2.5 Solubility Parameters 33
2.5.1 Group Contribution Methods 35
2.5.2 Topological Contributions 39
2.6 Lattice Theories 45
2.6.1 Entropy of Mixing 46
2.6.2 Heat of Mixing 48
References 48
3
Basic Thermodynamics of Polymeric Mixtures 49
3.1 Polymers 49
3.1.1 Introduction 49
3.1.2 Molecular Weight Distributions 51
3.2 Single Chain Statistics 52
3.2.1 The Ideal Chain 52
3.2.2 Real Chains 56
3.2.3 A Real Chain in a Solvent 59
6. 3.2.4 A Real Chain in the Melt 60
3.3 Ideal Polymer Mixtures 61
3.3.1 Introduction 61
3.3.2 Ideal Polymeric Mixtures 61
3.3.3 Derivation of the Flory-Huggins Entropy of Mixing 62
3.3.4 Alternative Derivations 64
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Page vi
3.3.5 Huggins Correction 65
3.4 Regular Polymer Mixtures 66
3.4.1 Generalized Regular Polymer Mixtures 68
3.5 Phase Diagrams 68
3.6 The Effect of Molecular Weight Distributions 73
3.6.1 Introduction 73
3.6.2 Spinodal and Critical Point 75
3.6.2 Binodal and Flash Calculations 76
3.6.4 Example 78
References 79
7. 4
Polymer Thermodynamic Models 81
4.1 Introduction 81
4.2 Flory-Huggins Models 82
4.3 Equation-of-State Models 85
4.3.1 Key Concepts 85
4.3.1.1 Helmholtz Free
Energy 86
4.3.1.2 Corresponding
States 89
4.3.1.3
Cell Partition
Function 90
4.3.1.4 Chain Flexibility
Parameter 91
4.3.2 The Flory EoS
Theory 92
4.3.3 Hole
Models 97
4.3.3.1 Key
Concepts 97
4.3.3.2 Holes and
Huggins 100
4.4 Specific Interaction
Models 101
4.4.1 Key
Concepts 101
4.4.2 Interaction
Strengths 107
8. 4.4.3
Generalizations 109
4.5 The (n=0) Vector
Model 110
4.6 Prism
Theory 116
References 121
5
Computer Simulations 125
5.1 Introduction 125
5.2 Computer Simulations and Statistical Mechanics 127
5.2.1 Introduction 127
5.2.2 The Boltzmann
Distribution 128
5.2.3
Ensembles 130
5.3 Molecular
Dynamics 133
5.4 Monte Carlo
Simulations 134
5.5 Simulation of Small
Systems 136
5.5.1 Periodic Boundary
Conditions 137
5.6 Simulations of Polymeric
Systems 138
9. 5.6.1 Single Chain
Simulations 138
5.6.2 Simulations of Many
Chains 139
Page vii
References 142
6
Experimental Findings 145
6.1 Introduction 145
6.2 Experimental Techniques 145
6.2.1 Scattering Techniques 145
6.2.1.1 Cloud Point Methods 148
6.2.1.2 Spinodal Decomposition 152
6.2.1.3 Light Scattering 154
6.2.1.4 Dilute Polymer Solutions 160
6.2.1.5 Neutron Scattering 161
6.2.2 Heats of Mixing 163
6.2.3 Glass Transition Temperature 164
6.3 Experimental Results and Model Validations 165
6.3.1 Polymer Solutions 165
6.3.1.1 Polystyrene in Cyclohexane 165
6.3.1.2 Other Polymer Solutions 175
6.3.2 Polymer Blends 181
10. 6.3.2.1 Polystyrene in Polyvinyl Methyl Ether 181
6.3.2.2 Some Typical Polymeric Mixtures 194
References 197
List of Symbols 199
Index 205
11. Page ix
Preface
When we started our research jobs on polymer thermodynamics at the Shell research laboratory in
Amsterdam we were both new in the areas of polymers as well as thermodynamics, having just
finished theses on respectively undercooled water and microemulsions. This allowed us to have a
fresh look at the subject. Another circumstance that gave us a non-traditional approach was that our
research group was housed in an environment of thermodynamic research. Our neighbors were not
synthesizing, blending, extruding or injection molding polymers; they were doing calculations on
gas-liquid equilibria in distillation columns, measuring vapor pressures and developing equations of
state for hydrocarbon mixtures.
We had to find our way in polymer thermodynamics through many books and articles. Many of these
literature sources were either written from a very practical point of view, taking existing theories for
granted or from a very theoretical point of view, ignoring the practicalities. It took us much time and
long philosophical discussions to understand the physical meaning of the concepts that were used
and their relation to "small molecules thermodynamics". We look back with great pleasure to these
discussions, often continued after work hours and with a good glass of "Trappist". During these
discussions we gradually obtained an understanding of the various fields and 'schools' in this area
and their interrelationships. It was a fortunate circumstance that we had a first-class laser light
scattering set-up available at the laboratory. This greatly helped us to verify some of our concepts
directly on well defined model systems.
Writing this book was a great opportunity to express what we had learnt. In fact, we have set
ourselves the goal to write the book that we would have liked to have had before. No doubt we
would have found another good reason for the "Trappist". We sincerely hope that this book will
prove to be of value to many new or experienced workers in this area of research. If not for its
content then for the discussions it may provoke. When some pages may seem overloaded with
equations that is because we wished to show intermediate steps in a derivation rather then to confuse
or intimidate the reader. In several cases these intermediate steps are not trivial and imply additional
assumptions.
As we found out, writing a book is a big project which requires, in addition to a permission to
publish, good faith, critical pre-readers, general support, inspiration and patience. For this we
acknowledge with pleasure and true gratitude the following:
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12. Page x
Permission to publish all this: Shell Research
Good faith: our publisher
Critical reading of (parts of) the manuscript: Peter Hilbers and Alan Batt
Very critical reading of part of the manuscript: Eric Hendriks
General support: many friends, relatives and colleagues who
kept reminding us of our duties asking
'how the book was going'.
Inspiration: All the foregoing and in particular
all members of 'Ceetje eXtra':
Christian Houghton-Larssen,
Ferry van Dijk,
Valentijn Hommels,
and Anthony Lucassen.
Patience: our wives.
MENNO VAN DIJK
ANTDRÉ WAKKER
Start of Citation[PU]Technomic Publishing[/PU][DP]1997[/DP]End of Citation
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Index
A
Atomic index, 41
Autocorrelation function, 155
B
Binodal, 19, 24, 74, 76, 85, 148, 149, 173
Blend
miscible, 1
Boltzmann
constant, 26
distribution, 128
Bond
index, 41
rotation, 54
valence angle, 54
Born-Oppenheimer Approximation, 133
Boyle temperature, 60
Boyle-Gay-Lussac Law, 25
Bragg condition, 156
Brownian motion, 16
Building block, 1
C
Caley tree, 110