CONTENTS
1 INTRODUCTION 1
2 STATIC PROPERTIES OF POLYMERS 8
2.1 The random flight model 8
2.1.1 The freely jointed model 8
2.1.2 General random flight models 9
2.1.3 Distribution of the end-to-end vector 11
2.2 Te Gaussian chain 14
2.3 Chain conformation under an external field 17
2.3.1 The Green function 17
2.3.2 Example-chain confined in a box 19
2.4 Scattering function 21
2.5 Excluded volume effect 24
2.5.1 Introduction 24
2.5.2 Model of the excluded volume chain 25
2.5.3 Theoretical approaches 27
2.6 Scaling 32
Appendix 2.1 Gaussian distribution functions 35
Appendix 2.11 Differential equation for G(R, R'; N) 40
Appendix 2.III Perturbation calculation for the excluded
volume effect 41
References 43
3 BROWNIAN MOTION 46
3.1 Introduction 46
3.2 The Smoluchowski equation 46
3.2.1 Diffusion of particles 46
3.2.2 Diffusion in phase space 50
3.2.3 Irreversibility of the Smoluchowski equation 51
3.3 The Langevin equation 52
3.4 Time correlation function and response function 55
3.4.1 Time correlation function 55
3.4.2 Microscopic expression for the time correlation function 56
3.4.3 Fluctuation dissipation theorem 58
3.5 Brownian motion in a harmonic potential 62
3.5.1 Smoluchowski equation 62
3.5.2 Langevin equation 63
3.6 Interacting Brownian particles 65
viii CONTENTS
3. 7 Microscopic basis of viscoelasticity 69
3. 7. I Introduction 69
3.7.2 Constitutive equation 70
3.7.3 The Smoluchowski equation for a system in macroscopic
flow 71
3.7.4 Expression for the stress tensor 72
3.7.S Principle of virtual work 75
3.8 Systems with rigid constraints 76
3.8.1 Introduction 76
3.8.2 The method of generalized coordinates 77
3.8.3 The method of Lagrangian multipliers 79
3.8.4 Elastic stress and viscous stress 80
3.8.5 Variational formulation 82
Appendix 3.I Eigenfunctions of the Smo)uchowski equation 83
Appendix 3.II Relationship between the Langevin equation
and the Smoluchowski equation 85
Appendix 3. III The Oseen tensor 88
References 89
4 DYNAMICS OF FLEXIBLE POLYMERS IN DILUTE
SOLUTION 91
4.1 The Rouse model 91
4. 1.1 Dynamics of a polymer with localized interaction 91
4.1.2 Normal coordinates 94
4.2 The Zimm model 97
4.2.1 Zimm model in 8 conditions 97
4.2.2 Zimm model in good solvent 100
4.3 Dynamical scaling 103
4.4 Dynamic light scattering 105
4.5 Viscoelasticity 108
4.5.1 Introduction 108
4.5.2 Microscopic expression for the stress tensor 110
4.5.3 Calculation of the intrinsic viscosity 112
4.5.4 Intrinsic moduli 114
4.6 Variational bounds for the transport coefficients 116
4.6.1 Introduction 116
4.6.2 Bounds for the intrinsic viscosity 116
4.6.3 Bounds for the diffusion constant 119
4.7 Birefringence 121
4.7.1 Birefringence of polymer solutions 121
4.7.2 Molecular expression for birefringence 122
4.7.3 Flow birefringence 127
CONTENTS ix
Appendix 4.I The Verdier-Stockmayer model 129
Appendix 4.11 Derivation of the normal modes 131
Appendix 4.III Dynamic structure factor 132
Appendix 4.IV Polarizability tensor of a Gaussian chain 135
References 137
5 MANY CHAIN SYSTEMS 140
5.1 Semidilute and concentrated solutions 140
5.2 Gaussian approximation for concentration fluctuations 143
5.2.1 Collective coordinates 143
5.2.2 Pair correlation function 147
5.2.3 Osmotic pressure 148
5.2.4 Size of a single chain 149
5.3 Scaling theorystatics 152
5.4 Topological interaction in polymer dynamics 156
5.4.1 Entanglement effect 156
5.4.2 Rigorous approach 158
5.4.3 The tube model 160
5.5 Dynamics of concentration fluctuations 161
5.5.1 Kinetic equation 161
5.5.2 Dynamic light scattering 164
5.5.3 Form birefringence 166
5.6 Scaling theory
dynamics 169
5.7 Effective medium theory 172
5.7.1 Failure of the scalar field description 172
5.7.2 Hydrodynamic screening 173
5.7.3 Effective medium theory 174
5.7.4 Example 176
Appendix 5.I Transformation to collective coordinates 180
Appendix 5.II Osmotic pressure in concentrated solution 182
Appendix 5.III Perturbation calculation of (R?) 183
References 184
6 DYNAMICS OF A POLYMER IN A FIXED NETWORK 188
6.1 Tube model 188
6.1.1 Tube model in crosslinked systems 188
6.1.2 Tube model in uncrosslinked systems 189
6.2 Reptation 191
