3rd Edition

Polymers Chemistry and Physics of Modern Materials, Third Edition

By J.M.G. Cowie, Valeria Arrighi Copyright 2007
    520 Pages 268 B/W Illustrations
    by CRC Press

    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.

    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



    J.M.G. Cowie, Valeria Arrighi

    ". . . 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