Introduction to Physical Polymer Science

by Sperling, Leslie H.

• ISBN13: 9780471706069
• ISBN10: 047170606X
• eBook ISBN(s): 9780471757115
• Edition: 4th
• Format: Hardcover
• Copyright: 2005-12-07
• Publisher: Wiley-Interscience
• More Book Details

Summary

An Updated Edition of the Classic Text Polymers constitute the basis for the plastics, rubber, adhesives, fiber, and coating industries. The Fourth Edition of Introduction to Physical Polymer Science acknowledges the industrial success of polymers and the advancements made in the field while continuing to deliver the comprehensive introduction to polymer science that made its predecessors classic texts. The Fourth Edition continues its coverage of amorphous and crystalline materials, glass transitions, rubber elasticity, and mechanical behavior, and offers updated discussions of polymer blends, composites, and interfaces, as well as such basics as molecular weight determination. Thus, interrelationships among molecular structure, morphology, and mechanical behavior of polymers continue to provide much of the value of the book. Newly introduced topics include: * Nanocomposites, including carbon nanotubes and exfoliated montmorillonite clays * The structure, motions, and functions of DNA and proteins, as well as the interfaces of polymeric biomaterials with living organisms * The glass transition behavior of nano-thin plastic films In addition, new sections have been included on fire retardancy, friction and wear, optical tweezers, and more. Introduction to Physical Polymer Science, Fourth Edition provides both an essential introduction to the field as well as an entry point to the latest research and developments in polymer science and engineering, making it an indispensable text for chemistry, chemical engineering, materials science and engineering, and polymer science and engineering students and professionals.

Author Biography

Trained as a chemist, L. H. SPERLING is Professor Emeritus of both Chemical Engineering and Materials Science and Engineering at Lehigh University in Bethlehem, Pennsylvania. He remains active in consulting, speaking, and writing.

Table of Contents

Preface to the Fourth Edition	xv
Preface to the First Edition	xvii
Symbols and Definitions	xix
1 Introduction to Polymer Science	1	(28)
1.1 From Little Molecules to Big Molecules	2	(2)
1.2 Molecular Weight and Molecular Weight Distributions	4	(4)
1.3 Major Polymer Transitions	8	(2)
1.4 Polymer Synthesis and Structure	10	(8)
1.5 Cross-Linking, Plasticizers, and Fillers	18	(1)
1.6 The Macromolecular Hypothesis	19	(1)
1.7 Historical Development of Industrial Polymers	20	(1)
1.8 Molecular Engineering	21	(1)
References	22	(1)
General Reading	22	(2)
Handbooks, Encyclopedias, and Dictionaries	24	(1)
Web Sites	24	(1)
Study Problems	25	(1)
Appendix 1.1 Names for Polymers	26	(3)
2 Chain Structure and Configuration	29	(42)
2.1 Examples of Configurations and Conformations	30	(1)
2.2 Theory and Instruments	31	(5)
2.3 Stereochemistry of Repeating Units	36	(6)
2.4 Repeating Unit Isomerism	42	(3)
2.5 Common Types of Copolymers	45	(2)
2.6 NMR in Modern Research	47	(4)
2.7 Multicomponent Polymers	51	(4)
2.8 Conformational States in Polymers	55	(1)
2.9 Analysis of Polymers during Mechanical Strain	56	(2)
2.10 Photophysics of Polymers	58	(5)
2.11 Configuration and Conformation	63	(1)
References	63	(2)
General Reading	65	(1)
Study Problems	65	(2)
Appendix 2.1 Assorted Isomeric and Copolymer Macromolecules	67	(4)
3 Dilute Solution Thermodynamics, Molecular Weights, and Sizes	71	(74)
3.1 Introduction	71	(2)
3.2 The Solubility Parameter	73	(6)
3.3 Thermodynamics of Mixing	79	(6)
3.4 Molecular Weight Averages	85	(2)
3.5 Determination of the Number-Average Molecular Weight	87	(4)
3.6 Weight-Average Molecular Weights and Radii of Gyration	91	(12)
3.7 Molecular Weights of Polymers	103	(7)
3.8 Intrinsic Viscosity	110	(7)
3.9 Gel Permeation Chromatography	117	(13)
3.10 Mass Spectrometry	130	(4)
3.11 Instrumentation for Molecular Weight Determination	134	(1)
3.12 Solution Thermodynamics and Molecular Weights	135	(1)
References	136	(3)
General Reading	139	(1)
Study Problems	140	(2)
Appendix 3.1 Calibration and Application of Light-Scattering Instrumentation for the Case Where P(theta) = 1	142	(3)
4 Concentrated Solutions, Phase Separation Behavior, and Diffusion	145	(52)
4.1 Phase Separation and Fractionation	145	(5)
4.2 Regions of the Polymer–Solvent Phase Diagram	150	(3)
4.3 Polymer—Polymer Phase Separation	153	(19)
4.4 Diffusion and Permeability in Polymers	172	(12)
4.5 Latexes and Suspensions	184	(2)
4.6 Multicomponent and Multiphase Materials	186	(1)
References	186	(4)
General Reading	190	(1)
Study Problems	190	(2)
Appendix 4.1 Scaling Law Theories and Applications	192	(5)
5 The Amorphous State	197	(42)
5.1 The Amorphous Polymer State	198	(1)
5.2 Experimental Evidence Regarding Amorphous Polymers	199	(12)
5.3 Conformation of the Polymer Chain	211	(6)
5.4 Macromolecular Dynamics	217	(10)
5.5 Concluding Remarks	227	(1)
References	227	(3)
General Reading	230	(1)
Study Problems	230	(2)
Appendix 5.1 History of the Random Coil Model for Polymer Chains	232	(4)
Appendix 5.2 Calculations Using the Diffusion Coefficient	236	(1)
Appendix 5.3 Nobel Prize Winners in Polymer Science and Engineering	237	(2)
6 The Crystalline State	239	(86)
6.1 General Considerations	239	(6)
6.2 Methods of Determining Crystal Structure	245	(3)
6.3 The Unit Cell of Crystalline Polymers	248	(8)
6.4 Structure of Crystalline Polymers	256	(4)
6.5 Crystallization from the Melt	260	(11)
6.6 Kinetics of Crystallization	271	(19)
6.7 The Reentry Problem in Lamellae	290	(9)
6.8 Thermodynamics of Fusion	299	(6)
6.9 Effect of Chemical Structure on the Melting Temperature	305	(2)
6.10 Fiber Formation and Structure	307	(4)
6.11 Tit Hierarchical Structure of Polymeric Materials	311	(1)
6.12 How Do You Know It's a Polymer?	312	(2)
References	314	(6)
General Reading	320	(1)
Study Problems	320	(5)
7 Polymers in the Liquid Crystalline State	325	(24)
7.1 Definition of a Liquid Crystal	325	(1)
7.2 Rod-Shaped Chemical Structures	326	(1)
7.3 Liquid Crystalline Mesophases	326	(5)
7.4 Liquid Crystal Classification	331	(7)
7.5 Thermodynamics and Phase Diagrams	338	(3)
7.6 Mesophase Identification in Thermotropic Polymers	341	(1)
7.7 Fiber Formation	342	(2)
7.8 Comparison of Major Polymer Types	344	(1)
7.9 Basic Requirements for Liquid Crystal Formation	345	(1)
References	346	(1)
General Reading	347	(1)
Study Problems	348	(1)
8 Glass–Rubber Transition Behavior	349	(78)
8.1 Simple Mechanical Relationships	350	(5)
8.2 Five Regions of Viscoelastic Behavior	355	(11)
8.3 Methods of Measuring Transitions in Polymers	366	(9)
8.4 Other Transitions and Relaxations	375	(2)
8.5 Time and Frequency Effects on Relaxation Processes	377	(4)
8.6 Theories of the Glass Transition	381	(16)
8.7 Effect of Molecular Weight on Tg	397	(2)
8.8 Effect of Copolymerization on Tg	399	(5)
8.9 Effect of Crystallinity on Tg	404	(4)
8.10 Dependence of Tg on Chemical Structure	408	(2)
8.11 Effect of Pressure on Tg	410	(2)
8.12 Damping and Dynamic Mechanical Behavior	412	(3)
8.13 Definitions of Elastomers, Plastics, Adhesives, and Fibers	415	(1)
References	415	(5)
General Reading	420	(1)
Study Problems	420	(3)
Appendix 8.1 Molecular Motion near the Glass Transition	423	(4)
9 Cross-liked Polymers and Rubber Elasticity	427	(80)
9.1 Cross-links and Networks	427	(3)
9.2 Historical Development of Rubber	430	(2)
9.3 Rubber Network Structure	432	(2)
9.4 Rubber Elasticity Concepts	434	(3)
9.5 Thermodynamic Equation of State	437	(2)
9.6 Equation of State for Gases	439	(3)
9.7 Statistical Thermodynamics of Rubber Elasticity	442	(8)
9.8 The "Carnot Cycle" for Elastomers	450	(3)
9.9 Continuum Theories of Rubber Elasticity	453	(6)
9.10 Some Refinements to Rubber Elasticity	459	(10)
9.11 Internal Energy Effects	469	(3)
9.12 The Flory–Rehner Equation	472	(1)
9.13 Gelation Phenomena in Polymers	473	(5)
9.14 Gels and Gelation	478	(1)
9.15 Effects of Strain on the Melting Temperature	479	(1)
9.16 Elastomers in Current Use	480	(8)
9.17 Summary of Rubber Elasticity Behavior	488	(1)
References	489	(5)
General Reading	494	(1)
Study Problems	495	(2)
Appendix 9.1 Gelatin as a Physically Cross-linked Elastomer	497	(4)
Appendix 9.2 Elastic Behavior of a Rubber Band	501	(2)
Appendix 9.3 Determination of the Cross-link Density of Rubber by Swelling to Equilibrium	503	(4)
10 Polymer Viscoelasticity and Rheology	507	(50)
10.1 Stress Relaxation and Creep	507	(8)
10.2 Relaxation and Retardation Times	515	(14)
10.3 The Time–Temperature Superposition Principle	529	(4)
10.4 Polymer Melt Viscosity	533	(5)
10.5 Polymer Rheology	538	(9)
10.6 Overview of Viscoelasticity and Rheology	547	(1)
References	548	(2)
General Reading	550	(1)
Study Problems	550	(2)
Appendix 10.1 Energy of Activation from Chemical Stress Relaxation Times	552	(1)
Appendix 10.2 Viscoelasticity of Cheese	553	(4)
11 Mechanical Behavior of Polymers	557	(56)
11.1 An Energy Balance for Deformation and Fracture	557	(3)
11.2 Deformation and Fracture in Polymers	560	(25)
11.3 Crack Growth	585	(3)
11.4 Cyclic Deformations	588	(5)
11.5 Molecular Aspects of Fracture and Healing in Polymers	593	(8)
11.6 Friction and Wear in Polymers	601	(2)
11.7 Mechanical Behavior of Biomedical Polymers	603	(3)
11.8 Summary	606	(1)
References	607	(3)
General Reading	610	(1)
Study Problems	611	(2)
12 Polymer Surfaces and Interfaces	613	(74)
12.1 Polymer Surfaces	614	(1)
12.2 Thermodynamics of Surfaces and Interfaces	615	(4)
12.3 Instrumental Methods of Characterization	619	(25)
12.4 Conformation of Polymer Chains in a Polymer Blend Interphase	644	(2)
12.5 The Dilute Solution–Solid Interface	646	(6)
12.6 Instrumental Methods for Analyzing Polymer Solution Interfaces	652	(7)
12.7 Theoretical Aspects of the Organization of Chains at Walls	659	(8)
12.8 Adhesion at Interfaces	667	(8)
12.9 Interfaces of Polymeric Biomaterials with Living Organisms	675	(2)
12.10 Overview of Polymer Surface and Interface Science	677	(2)
References	679	(4)
General Reading	683	(1)
Study Problems	684	(2)
Appendix 12.1 Estimation of Fractal Dimensions	686	(1)
13 Multicomponent Polymeric Materials	687	(70)
13.1 Classification Schemes for Multicomponent Polymeric Materials	688	(4)
13.2 Miscible and Immiscible Polymer Pairs	692	(1)
13.3 The Glass Transition Behavior of Multicomponent Polymer Materials	693	(5)
13.4 The Modulus of Multicomponent Polymeric Materials	698	(8)
13.5 The Morphology of Multiphase Polymeric Materials	706	(4)
13.6 Phase Diagrams in Polymer Blends (Broad Definition)	710	(11)
13.7 Morphology of Composite Materials	721	(2)
13.8 Nanotechnology-Based Materials	723	(5)
13.9 Montmorillonite Clays	728	(8)
13.10 Fracture Behavior of Multiphase Polymeric Materials	736	(5)
13.11 Processing and Applications of Polymer Blends and Composites	741	(7)
References	748	(5)
General Reading	753	(1)
Study Problems	754	(3)
14 Modern Polymer Topics	757	(65)
14.1 Polyolefins	757	(5)
14.2 Thermoset Polymer Materials	762	(3)
14.3 Polymer and Polymer Blend Aspects of Bread Doughs	765	(4)
14.4 Natural Product Polymers	769	(4)
14.5 Dendritic Polymers and Other Novel Polymeric Structures	773	(6)
14.6 Polymers in Supercritical Fluids	779	(3)
14.7 Electrical Behavior of Polymers	782	(4)
14.8 Polymers for Nonlinear Optics	786	(3)
14.9 Light-Emitting Polymers and Electroactive Materials	789	(5)
14.10 Optical Tweezers in Biopolymer Research	794	(1)
14.11 The 3-D Structure and Function of Biopolymers	795	(12)
14.12 Fire Retardancy in Polymers	807	(4)
14.13 Polymer Solution-Induced Drag Reduction	811	(3)
14.14 Modern Engineering Plastics	814	(1)
14.15 Major Advances in Polymer Science and Engineering	815	(2)
References	817	(5)
General Reading	822	(1)
Study Problems	823	(4)
Index	827