Polymers: Chemistry and Physics of Modern Materials, Third Edition, 3rd Edition (Paperback) book cover


Chemistry and Physics of Modern Materials, Third Edition, 3rd Edition

By J.M.G. Cowie, Valeria Arrighi

CRC Press

520 pages | 268 B/W Illus.

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Paperback: 9780849398131
pub: 2007-07-27
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Extensively revised and updated to keep abreast of recent advances, Polymers: Chemistry and Physics of Modern Materials, Third Edition continues to provide a broad-based, high-information text at an introductory, reader-friendly level that illustrates the multidisciplinary nature of polymer science. Adding or amending roughly 50% of the material, this new edition strengthens its aim to contribute a comprehensive treatment by offering a wide and balanced selection of topics across all aspects of the chemistry and physics of polymer science, from synthesis and physical properties to applications.

Although the basics of polymer science remain unchanged, significant discoveries in the area of control over molecular weight, macromolecular structure and architecture, and the consequent ability to prepare materials with specific properties receive extensive mention in the third edition. Expanded chapters include controlled radical polymerizations, metallocene chemistry, and the preparation of block and graft copolymers, as well as multiarmed and dendritic structures. Reflecting the growth of polymer applications in industry, the book presents detailed examples to illustrate polymer use in electronic, biological, and medical settings. The authors introduce new understandings of rheological behavior and replace old and outmoded methods of polymer characterization with new and up-to-date techniques. Also new to this edition are a series of problems at the end of each chapter that will test whether the reader has understood the various points and in some cases expand on that knowledge. An accompanying solutions manual is also available for qualifying course adoptions.

Offering the highest quality, comprehensive coverage of polymer science in an affordable, accessible format, Polymers: Chemistry and Physics of Modern Materials, Third Edition continues to provide undergraduate and graduate students and professors with the most complete and current coverage of modern polymer science.


". . . continues the tradition of a well-known respected textbook . . ."

– Mark Moloney, Chemistry Research Laboratory, University of Oxford, in Reviews, June 2008, Vol. 9, No. 16, Issue 1

Table of Contents


Birth of a Concept

Some Basic Definitions

Synthesis of Polymers


Average Molar Masses and Distributions

Size and Shape


The Glass Transition Temperature Tg and the Melting Temperature Tm

Elastomers, Fibers, and Plastics

Fiber-Forming Polymers


Thermosetting Polymers


Step-Growth Polymerization

General Reactions

Reactivity of Functional Groups

Carothers Equation

Control of the Molar Mass

Stoichiometric Control of Mn


Molar Mass Distribution in Linear Systems

Average Molar Masses

Characteristics of Step-Growth Polymerization

Typical Step-Growth Reactions

Ring Formation

Nonlinear Step-Growth Reactions

Statistical Derivation

Comparison with Experiment


Thermosetting Polymers

Free-Radical Addition Polymerization

Addition Polymerization

Choice of Initiators

Free-Radical Polymerization


Chain Growth


Steady-State Kinetics

High-Conversion Bulk Polymerizations

Chain Transfer

Inhibitors and Retarders

Activation Energies and the Effect of Temperature

Thermodynamics of Radical Polymerization

Heats of Polymerization

Polymerization Processes

Features of Free-Radical Polymerization

Controlled Radical Polymerization

Nitroxide-Mediated Polymerizations

Atom Transfer Radical Polymerization (ATRP

Reverse ATRP

Degenerative Chain Transfer Reaction (DT)

Reversible Addition Fragmentation Chain Transfer (RAFT)

CRP of Vinyl Chloride

The Kinetics of CRP Processes

Application to Experimental Data

Ionic Polymerization

General Characteristics

Cationic Polymerization

Propagation by Cationic Chain Carriers


General Kinetic Scheme

Energetics of Cationic Polymerization

Telechelic Polymers via Cationic Polymerization

Cationic Ring Opening Polymerization

Stable Carbocations

Anionic Polymerization

Living Polymers

Kinetics and Molar Mass Distribution in Living Anionic Systems

Metal Alkyl Initiators

Solvent and Gegen Ion Effects

Anionic Ring-opening Polymerization

Linear Copolymers and Other Architectures

General Characteristics

Composition Drift

The Copolymer Equation

Monomer Reactivity Ratios

Reactivity Ratios and Copolymer Structure

Monomer Reactivities and Chain Initiation

Influence of Structural Effects on Monomer Reactivity Ratios

The Q-e Scheme

Alternating Copolymers

Block Copolymer Synthesis

Graft Copolymer Synthesis

Statistical and Gradient Copolymers

Complex Molecular Architectures


Polymer Stereochemistry




Geometric Isomerism

Conformation of Stereoregular Polymers

Factors Influencing Stereoregulation

Homogeneous Stereospecific Cationic Polymerizations

Homogeneous Stereoselective Anionic Polymerizations

Homogeneous Diene Polymerization


Polymerization Reactions Initiated by Metal Catalysts and Transfer Reactions

Polymerization Using Ziegler-Natta Catalysts

Nature of Catalyst

Nature of Active Centers

Bimetallic Mechanism

Monometallic Mechanism


Ring-Opening Metathesis Polymerization (ROMP)

Monocyclic Monomers

Bicyclo- and Tricyclomonomers


Living Systems

Group Transfer Polymerization (GTP)

Aldol Group Transfer Polymerization

Metallocene Catalysts

Concluding Remarks

Polymers in Solution

Thermodynamics of Polymer Solutions

Ideal Mixtures of Small Molecules

Nonideal Solutions

Flory-Huggins Theory: Entropy of Mixing

Enthalpy Change on Mixing

Free Energy of Mixing

Limitations of the Flory-Huggins Theory

Phase Equilibria

Flory-Krigbaum Theory

Location of the Theta Temperature

Lower Critical Solution Temperatures

Solubility and the Cohesive Energy Density

Polymer-Polymer Mixtures

Kinetics of Phase Separation

Polymer Characterization - Molar Masses


Molar Masses, Molecular Weights, and SI Units

Number-Average Molar Mass Mn

End-Group Assay

Colligative Properties of Solutions

Osmotic Pressure

Light Scattering

Dynamic Light Scattering


Gel Permeation Chromatography


Polymer Characterization - Chain Dimensions, Structures, and Morphology

Average Chain Dimensions

Freely Jointed Chain Model

Short-range Effects

Chain Stiffness

Treatment of Dilute Solution Data

Nuclear Magnetic Resonance (NMR)

Infrared Spectroscopy

Thermal Analysis

Wide-Angle and Small-Angle Scattering


The Crystalline State and Partially Ordered Structures


Mechanism of Crystallization

Temperature and Growth Rate


Thermodynamic Parameters

Crystalline Arrangement of Polymers

Morphology and Kinetics


Kinetics of Crystallization

Block Copolymers

Historical Development of Polymer Liquid Crystals

Liquid Crystalline Phases

Identification of the Mesophases

Lyotropic Main-Chain Liquid Crystalline Polymers

Thermotropic Main-Chain Liquid Crystal Polymers

Side-Chain Liquid Crystalline Polymers

Chiral Nematic Liquid Crystal Polymers

The Glassy State and Glass Transition

The Amorphous State

The Glassy State

Relaxation Processes in the Glassy State

Glass Transition Region

Theoretical Treatments

Dependence of Tg on Molar Mass

Structural Relaxation and Physical Aging

Rheology and Mechanical Properties

Introduction to Rheology

The Five Regions of Viscoelastic Behavior

The Viscous Region

Mechanical Properties

Mechanical Models Describing Viscoelasticity

Linear Viscoelastic Behavior of Amorphous Polymers

Dynamic Mechanical and Dielectric Thermal Analysis

Time-Temperature Superposition Principle

Dynamic Viscosity

A Molecular Theory for Viscoelasticity

The Reptation Model

The Elastomeric State

General Introduction

Experimental Vulcanization

Properties of Elastomers

Thermodynamic Aspects of Rubberlike Elasticity

Nonideal Elastomers

Distribution Function for Polymer Conformation

Statistical Approach

Swelling of Elastomeric Networks

Network Defects

Resilience of Elastomers

Structure-Property Relations

General Considerations

Control of Tm and Tg

Relation between Tm andTg

Random Copolymers

Dependence of Tm andTg on Copolymer Composition

Block Copolymers


Crystallinity and Mechanical Response

Application to Fibers, Elastomers, and Plastics


Aromatic Polyamides


Elastomers and Cross-Linked Networks


High-temperature Speciality Polymers

Carbon Fibers

Concluding Remarks

Polymers for the Electronics Industry


Polymer Resists for IC Fabrication

The Lithographic Process

Polymer Resists


Electron Beam Sensitive Resists

X-ray and Ion Sensitive Resists

Electroactive Polymers

Conduction Mechanisms

Preparation of Conductive Polymers



Polyheterocyclic Systems


Poly(Phenylene Sulfide)



Photonic Applications

Light-Emitting Polymers

Nonlinear Optics

Langmuir-Blodgett Films

Optical Information Storage

Thermorecording on Liquid Crystalline Polymers


Subject Categories

BISAC Subject Codes/Headings:
SCIENCE / Chemistry / Physical & Theoretical
TECHNOLOGY & ENGINEERING / Textiles & Polymers