Polymer Physics

by Rubinstein, Michael; Colby, Ralph H.

• ISBN13: 9780198520597
• ISBN10: 019852059X
• Format: Hardcover
• Copyright: 2003-08-07
• Publisher: Oxford University Press

Summary

Polymer Physics thoroughly details the fundamental concepts of polymer melts, solutions, and gels in terms of both static structure and dynamics. It goes beyond other introductory polymer texts, deriving the essential tools of the physical polymer chemist or engineer without skipping any steps. The book is divided into four parts. Part One summarizes the necessary concepts of a first course on polymers and covers the conformations of single polymer chains. Part Two deals with the thermodynamics of polymer solutions and melts, including chain conformations in those states. Part Three applies the concepts of Part Two to the formation and properties of polymer networks. Part Four explains the essential aspects of how polymers move in both melt and solution states. The text assumes a working knowledge of calculus, physics, and chemistry, but no prior knowledge of polymers. It is ideal for upper-level undergraduate and first-year graduate courses in Condensed Matter Physics, Soft Materials, and Polymers. Features Presents established results in an easily accessible way Emphasizes physical insight rather than mathematical rigor Provides detailed experimental sections at the end of each chapter Includes more than 200 illustrations and 350 exercises

Table of Contents

Introduction	1	(49)
History of polymer science	1	(1)
Polymer microstructure	2	(3)
Homopolymers and heteropolymers	5	(2)
Fractal nature of polymer conformations	7	(5)
Types of polymeric substances	12	(4)
Polymer liquids	12	(3)
Polymer solids	15	(1)
Liquid crystal polymers	15	(1)
Molar mass distributions	16	(10)
Binary distributions	19	(1)
Linear condensation polymers	20	(5)
Linear addition polymers	25	(1)
Molar mass measurements	26	(12)
Measuring Mn by osmotic pressure	26	(3)
Measuring Mw by scattering	29	(4)
Intrinsic viscosity	33	(2)
Size exclusion chromatography	35	(3)
Summary	38	(11)
Problems	39	(6)
Bibliography	45	(4)
I Single chain conformations
Ideal chains	49	(48)
Flexibility mechanisms	49	(2)
Conformations of an ideal chain	51	(3)
Ideal chain models	54	(6)
Freely rotating chain model	55	(2)
Worm-like chain model	57	(2)
Hindered rotation model	59	(1)
Rotational isomeric state model	59	(1)
Radius of gyration	60	(6)
Radius of gyration of an ideal linear chain	62	(1)
Radius of gyration of a rod polymer	63	(1)
Radius of gyration of an ideal branched polymer (Kramers theorem)	64	(2)
Distribution of end-to-end vectors	66	(4)
Free energy of an ideal chain	70	(8)
Scaling argument for chain stretching	72	(2)
Langevin dependence of elongation on force	74	(4)
Pair correlations of an ideal chain	78	(1)
Measurement of size by scattering	79	(9)
Scattering wavevector	79	(2)
Form factor	81	(2)
Measuring R2g by scattering at small angles	83	(2)
Debye function	85	(3)
Summary of ideal chains	88	(9)
Problems	90	(6)
Bibliography	96	(1)
Real chains	97	(40)
Excluded volume and self-avoiding walks	98	(6)
Mayer f-function and excluded volume	98	(4)
Flory theory of a polymer in good solvent	102	(2)
Deforming real and ideal chains	104	(9)
Polymer under tension	104	(3)
Polymer under compression	107	(3)
Adsorption of a single chain	110	(3)
Temperature effects on real chains	113	(8)
Scaling model of real chains	113	(2)
Flory theory of a polymer in a poor solvent	115	(2)
Temperature dependence of the chain size	117	(2)
Second virial coefficient	119	(2)
Distribution of end-to-end distances	121	(1)
Scattering from dilute solutions	122	(3)
Summary of real chains	125	(12)
Problems	127	(6)
Bibliography	133	(4)
II Thermodynamics of blends and solutions
Thermodynamics of mixing	137	(34)
Entropy of binary mixing	137	(3)
Energy of binary mixing	140	(6)
Equilibrium and stability	146	(4)
Phase diagrams	150	(4)
Mixtures at low compositions	154	(5)
Osmotic pressure	155	(2)
Polymer melts	157	(2)
Experimental investigations of binary mixtures	159	(4)
Summary of thermodynamics	163	(8)
Problems	165	(5)
Bibliography	170	(1)
Polymer solutions	171	(28)
Theta solvent	171	(2)
Poor solvent	173	(3)
Good solvent	176	(7)
Correlation length and chain size	176	(5)
Osmotic pressure	181	(2)
Semidilute theta solutions	183	(3)
Correlation length	183	(1)
Osmotic pressure	184	(2)
The Alexander -- de Gennes brush	186	(1)
Multichain adsorption	187	(2)
Measuring semidilute chain conformations	189	(1)
Summary of polymer solutions	190	(9)
Problems	191	(5)
Bibliography	196	(3)
III Networks and gelation
Random branching and gelation	199	(54)
Introduction	199	(7)
Percolation around us	202	(3)
Percolation in one dimension	205	(1)
Branching without gelation	206	(7)
Hyperbranched polymers	206	(5)
Regular dendrimers	211	(2)
Gelation: concepts and definitions	213	(2)
Mean-field model of gelation	215	(12)
Gel point	216	(1)
Sol and gel fractions	217	(1)
Number-average molar mass below the gel point	218	(1)
Weight-average molar mass below the gel point	219	(1)
Molar mass distribution	220	(4)
Size of ideal randomly branched polymers	224	(3)
Scaling model of gelation	227	(14)
Molar mass distribution and gel fraction	227	(4)
Cutoff functions	231	(3)
Size and overlap of randomly branched polymers	234	(3)
Vulcanization universality class	237	(4)
Characterization of branching and gelation	241	(3)
Summary of branching and gelation	244	(9)
Problems	247	(5)
Bibliography	252	(1)
Networks and gels	253	(56)
Thermodynamics of rubbers	253	(2)
Flory construction	255	(1)
Unentangled rubber elasticity	255	(9)
Affine network model	255	(4)
Phantom network model	259	(4)
Finite extensibility	263	(1)
Entangled rubber elasticity	264	(10)
Chain entanglements and the Edwards tube model	264	(4)
The Mooney--Rivlin model	268	(1)
Constrained fluctuations models	269	(5)
Swelling of polymer gels	274	(6)
Swelling in θ-solvents	276	(1)
Swelling in athermal solvents	277	(1)
Swelling in good solvents	278	(2)
Networks in the gelation regime	280	(2)
Linear viscoelasticity	282	(12)
Stress relaxation after a step strain	284	(1)
The Boltzmann superposition principle	285	(1)
Steady shear	286	(2)
Creep and creep recovery	288	(2)
Oscillatory shear	290	(4)
Summary of networks and gels	294	(15)
Problems	295	(10)
Bibliography	305	(4)
IV Dynamics
Unentangled polymer dynamics	309	(52)
Rouse model	311	(1)
Zimm model	312	(2)
Intrinsic viscosity	314	(5)
Relaxation modes	319	(6)
Rouse modes	319	(4)
Zimm modes	323	(2)
Semidilute unentangled solutions	325	(5)
Modes of a semiflexible chain	330	(4)
Bending energy and dynamics	330	(3)
Tensile modulus and stress relaxation	333	(1)
Temperature dependence of dynamics	334	(7)
Time--temperature superposition	334	(5)
Transition zone of polymer melts	339	(1)
Short linear polymer melts	340	(1)
Randomly branched polymers	341	(4)
Dynamic scattering	345	(5)
Summary of unentangled dynamics	350	(11)
Problems	352	(8)
Bibliography	360	(1)
Entangled polymer dynamics	361	(62)
Entanglements in polymer melts	361	(2)
Reptation in polymer melts	363	(4)
Relaxation times and diffusion	363	(1)
Stress relaxation and viscosity	364	(3)
Reptation in semidilute solutions	367	(7)
Length scales	367	(2)
Entanglement concentration	369	(1)
Plateau modulus	370	(1)
Relaxation times and diffusion	370	(2)
Stress relaxation and viscosity	372	(2)
Dynamics of a single entangled chain	374	(13)
Chain in an array of fixed obstacles	374	(2)
Entangled star polymers	376	(4)
H-polymers and combs	380	(1)
Monomer displacement in entangled linear melts	381	(2)
Tube length fluctuations	383	(4)
Many-chain effects: constraint release	387	(4)
Relaxation times and diffusion	388	(1)
Stress relaxation	389	(2)
Computer simulations in polymer physics	391	(11)
Molecular dynamics	392	(3)
Monte Carlo	395	(7)
Summary of entangled dynamics	402	(21)
Problems	403	(19)
Bibliography	422	(1)
Notations	423	(10)
Index	433