Physical Chemistry of Macromolecules Book

Introduction to macromolecules     1
What is a macromolecule?     1
The discovery of macromolecules     2
The structure of macromolecules in solution     3
The remarkable properties of pure bulk polymers     6
Building new materials using macromolecules     8
Suggestions for further reading     10
Describing polymer structure     11
Introduction     11
Geometric structure of macromolecules     12
Bond probability distributions     13
Rotational isomeric state approximation     14
Mean-squared end-to-end distance     17
Statistics of the random coil     20
Chain flexibility and the persistence length     23
Measuring polymer structure     25
Introduction     25
Polymer composition and sequence distribution     25
NMR spectroscopy of polymers     26
Measuring local conformations of polymers     27
Vibrational spectroscopy     30
Conformational statistics of n-hexane     31
Global measures of the chain structure     31
Light scattering from dilute polymer solutions     32
The macromolecular basis of rubber elasticity     35
Introduction     35
The thermodynamics of ideal-rubber elasticity     36
The statistical theory of rubber elasticity     38
Thermoelastic inversion point     40
The force of extension of real rubber     40
Structure and properties of polymers in dilute solution     43
Introduction     43
The structure of macromolecules in dilute solution     44
Flory theory of chain expansion     47
Thermodynamics of two component solutions     48
Osmotic pressure     49
Flory theory of the second virial coefficient     51
Light scattering from two-component solutions     53
Flory theory of light scattering in dilute solution     54
Diffusion of particles in solution     57
Kirkwood theory of macromolecular friction     59
Concentration fluctuations and mutual diffusion     62
The viscosity of dilute polymer solutions     65
The effect of molecular-weight polydispersity     68
Structure and properties of polymers in semidilute solution     75
Introduction     75
The remarkable behavior of semidilute solutions     76
Microscopic theory of semidilute solutions      78
Viscosity in semidilute solutions     81
Structure near overlap     82
Structure and properties of polymers in concentrated solution     83
Introduction     83
Flory-Huggins theory of concentrated solutions     84
The thermodynamics of swollen rubber: gels     89
Light scattering from concentrated solutions     90
Real solutions and the Flory-Orwoll theory     90
Diffusion in concentrated solutions     94
Viscoelasticity in concentrated polymer solutions     95
Structure and properties of polymers in the pure amorphous liquid state     99
Introduction     99
Free volume and viscosity     100
Viscosity of low-molecular-weight chain liquids     100
Phenomenology of the glass transition     101
Temperature and pressure dependence of relaxation near the glass transition     105
Structure and properties of rodlike polymers in solution     111
Introduction     111
Characterization of rodlike polymers in solution     111
Second osmotic virial coefficient     114
Thermodynamics of rodlike polymer solutions     114
Structure and properties of polyelectrolyte chains in solution      119
Introduction     119
Structure of linear polyelectrolyte chains in dilute solution     119
Thermodynamics of polyelectrolyte solutions     124
Viscosity of polyelectrolyte solutions     126
References     129
Index     131