Introduction to polymers:
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| Main Authors: | , |
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| Format: | Book |
| Language: | English |
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Boca Raton, Fla. [u.a.]
CRC Press
2011
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| Edition: | Third edition |
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XX, 668 Seiten Illustrationen, Diagramme |
| ISBN: | 0849339294 9780849339295 |
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| 245 | 1 | 0 | |a Introduction to polymers |c Robert J. Young and Peter A. Lovell |
| 250 | |a Third edition | ||
| 264 | 1 | |a Boca Raton, Fla. [u.a.] |b CRC Press |c 2011 | |
| 300 | |a XX, 668 Seiten |b Illustrationen, Diagramme | ||
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| 650 | 4 | |a Polymerization | |
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| _version_ | 1804145681522229248 |
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| adam_text | Titel: Introduction to polymers
Autor: Young, Robert J
Jahr: 2011
Contents
Preface to the Third Edition...........................................................................................................xix
PART I Concepts, Nomenclature and Synthesis of Polymers
Chapter 1 Concepts and Nomenclature.........................................................................................3
1.1 The Origins of Polymer Science and the Polymer Industry..............................3
1.2 Basic Definitions and Nomenclature.................................................................4
1.2.1 Skeletal Structure.................................................................................4
1.2.2 Homopolymers.....................................................................................6
1.2.3 Copolymers..........................................................................................6
1.2.4 Classification of Polymers....................................................................9
1.3 Molar Mass and Degree of Polymerization.....................................................10
1.3.1 Molar Mass Distribution....................................................................11
1.3.2 Molar Mass Averages.........................................................................12
Problems.....................................................................................................................14
Further Reading.........................................................................................................14
General Historical and Introductory Reading..................................................14
Macromolecular Nomenclature.......................................................................14
Chapter 2 Principles of Polymerization......................................................................................15
2.1 Introduction.....................................................................................................15
2.2 Classification of Polymerization Reactions.....................................................15
2.3 Monomer Functionality and Polymer Skeletal Structure................................16
2.4 Functional Group Reactivity and Molecular Size: The Principle of
Equal Reactivity..............................................................................................18
Problems.....................................................................................................................18
Further Reading.........................................................................................................19
Chapter 3 Step Polymerization...................................................................................................21
3.1 Introduction.....................................................................................................21
3.2 Linear Step Polymerization.............................................................................21
3.2.1 Polycondensation................................................................................23
3.2.1.1 Synthesis of Polyesters, Polyamides and Polyethers by
Polycondensation................................................................23
3.2.1.2 Synthesis of Engineering and High-Performance
Polymers by Polycondensation...........................................24
3.2.1.3 Synthesis of Conducting Polymers by Polycondensation ...24
3.2.1.4 Synthesis of Polysiloxanes by Polycondensation................27
3.2.2 Polyaddition........................................................................................29
3.2.2.1 Synthesis of Linear Poly urethanes and Polyureas by
Polyaddition........................................................................29
3.2.2.2 Other Polymers Prepared by Polyaddition..........................30
vj Contents
3.2.3 Theoretical Treatment of Linear Step Polymerization.......................31
3.2.3.1 Carothers Theory................................................................31
3.2.3.2 Statistical Theory................................................................34
3.2.3.3 Kinetics of Step Polymerization.........................................37
3.2.4 Ring Formation..................................................................................38
3.2.5 Linear Step Polymerization Processes...............................................39
3.3 Non-Linear Step Polymerization.....................................................................41
3.3.1 Network Polymers..............................................................................42
3.3.1.1 Formaldehyde-Based Resins...............................................42
3.3.1.2 Epoxy Resins......................................................................44
3.3.1.3 Network Polyurethanes.......................................................45
3.3.2 Gelation Theory.................................................................................46
3.3.2.1 Carothers Theory of Gelation.............................................46
3.3.2.2 Statistical Theory of Gelation.............................................47
3.3.2.3 Validity of the Carothers and Statistical Theories of
Gelation...............................................................................48
3.3.3 Dendrimers.........................................................................................49
3.3.3 1 Synthesis of Dendrimers.....................................................50
3.3.3.2 Applications of Dendrimers................................................53
3.3.4 Hyperbranched Polymers...................................................................55
3.3.4.1 Synthesis of Hyperbranched Polymers by Non-Linear
Step Polymerization............................................................56
Problems.....................................................................................................................57
Further Reading.........................................................................................................60
General Reading..............................................................................................60
Dendrimers......................................................................................................60
Hyperbranched Polymers................................................................................60
Chapter 4 Radical Polymerization..............................................................................................61
4.1 Introduction to Radical Polymerization..........................................................61
4.2 The Chemistry of Conventional Free-Radical Polymerization.......................62
4.2.1 Initiation.............................................................................................62
4.2.2 Propagation.........................................................................................65
4.2.3 Termination........................................................................................66
4.2.4 Chain Transfer....................................................................................67
4.2.4.1 Chain Transfer with Small Molecules................................67
4.2.4.2 Chain Transfer to Polymer..................................................68
4.3 Kinetics of Conventional Free-Radical Polymerization..................................68
4.3.1 Rate of Polymerization.......................................................................71
4.3.2 Number-Average Degree of Polymerization......................................74
4.3.3 Features of the Steady-State Equations for Rp and (^,)0.....................75
4.3.4 Diffusion Constraints on Rates of Propagation and Termination......75
4.3.5 Effects of Chain Transfer...................................................................77
4.3.5.1 Determination of Transfer Constants.................................78
4.3.6 Catalytk Chain Transfer....................................................................79
4.3.7 Inhibition and Retardation.................................................................81
4.3.8 Molar Mass Distribution....................................................................82
4.3.9 Determination of Individual Rate Coefficients..................................85
4.3.9.1 Determination of/and kt....................................................85
Contents vii
4.3.9.2 Early Approaches to Determining kp and kt.......................86
4.3.9.3 Modern Approaches to Determining kp and kt...................87
4.3.10 Effects of Temperature.......................................................................88
4.3.10.1 Ceiling Temperature...........................................................89
4.4 Free-Radical Polymerization Processes..........................................................91
4.4.1 Bulk Polymerization...........................................................................91
4.4.2 Solution Polymerization.....................................................................91
4.4.3 Suspension Polymerization................................................................92
4.4.4 Emulsion Polymerization...................................................................93
4.4.4.1 Particle Nucleation (Interval I)...........................................94
4.4.4.2 Particle Growth (Intervals II and III).................................94
4.4.4.3 Simple Kinetics of Emulsion Polymerization.....................95
4.4.4.4 Benefits and Applications of Emulsion Polymerization.....97
4.4.4.5 Miniemulsion Polymerization............................................97
4.4.4.6 Microgels............................................................................98
4.4.5 Strategies for Performing Polymerization Processes.........................98
4.5 Reversible-Deactivation ( Living ) Radical Polymerizations..........................98
4.5.1 Nitroxide-Mediated Radical Polymerization...................................101
4.5.1.1 Kinetics of Nitroxide-Mediated Radical Polymerization... 102
4.5.1.2 Side Reactions in Nitroxide-Mediated Radical
Polymerization..................................................................104
4.5.2 Atom-Transfer Radical Polymerization............................................105
4.5.2.1 Kinetics of ATRP.............................................................106
4.5.2.2 Initiators, Transition Metals and Ligands for ATRP........107
4.5.2.3 Alternative Strategies for Initiation of ATRP...................108
4.5.3 Reversible-Addition-Fragmentation Chain-Transfer Radical
Polymerization..................................................................................109
4.5.3.1 Kinetics ofRAFT Polymerization....................................109
4.5.3.2 RAFT Agents....................................................................111
4.6 Non-Linear Radical Polymerizations............................................................113
4.6.1 Non-Linear Radical Polymerizations Involving Crosslinking
Monomers.........................................................................................113
4.6.2 Non-Linear Radical Polymerizations Involving Unsaturated
Polymers...........................................................................................116
4.6.2.1 Crosslinking of Unsaturated Resins.................................116
4.6.2.2 Branching and Crosslinking during Polymerization of
1,3-Dienes.........................................................................117
Problems...................................................................................................................118
Further Reading.......................................................................................................120
General Reading............................................................................................120
Emulsion Polymerization..............................................................................120
Reversible-Deactivation Radical Polymerization..........................................120
Chapter 5 Ionic Polymerization................................................................................................123
5.1 Introduction to Ionic Polymerization.............................................................123
5.2 Cationic Polymerization................................................................................123
5.2.1 Conventional Cationic Polymerizations...........................................123
5.2.1.1 Initiation of Cationic Polymerization...............................124
5.2.1.2 Propagation in Cationic Polymerization...........................125
viii Contents
5.2.1.3 Termination and Chain Transfer in Cationic
Polymerization..................................................................125
5.2.1.4 Kinetics of Conventional Cationic Polymerization..........126
5.2.1.5 Effect of Temperature.......................................................127
5.2.1.6 Solvent and Counter-Ion Effects.......................................128
5.2.1.7 Practical Considerations...................................................128
5.2.2 Reversible-Deactivation (Living) Cationic Polymerizations............129
5.2.2.1 Initiation Systems for Reversible-Deactivation
Cationic Polymerization...................................................129
5.2.2.2 Kinetics of Reversible-Deactivation Cationic
Polymerizations................................................................131
5.2.2.3 Practical Considerations...................................................131
5.3 Anionic Polymerization.................................................................................131
5.3.1 Polymerization of Styrene in Liquid NH3 Initiated by KNH2.........131
5.3.2 Polymerization without Termination?Living Anionic
Polymerization..................................................................................133
5.3.2.1 Organometallic Initiators for Living Anionic
Polymerization..................................................................133
5.3.2.2 Electron Transfer Initiation for Living Anionic
Polymerization..................................................................134
5.3.2.3 Kinetics of Living Anionic Polymerization.....................134
5.3.2.4 Molar Mass Distributions of Polymers Produced by
Living Polymerization......................................................135
5.3.2.5 Deactivation of Carbanionic Living Polymers.................138
5.3.2.6 Solvent and Counter-Ion Effects in Living Anionic
Polymerizations................................................................139
5.3.2.7 Practical Considerations for Living Anionic
Polymerization..................................................................140
5.4 Group-Transfer Polymerization.....................................................................141
5.4.1 MechanismofGTP..........................................................................142
5.4.2 Practical Considerations and Uses of GTP......................................143
5.4.3 Aldol GTP........................................................................................145
Problems...................................................................................................................146
Further Reading.......................................................................................................146
Chapter 6 Stereochemistry and Coordination Polymerization.................................................147
6.1 Introduction to Stereochemistry of Polymerization...................................... 47
6.2 Tacticity of Polymers.....................................................................................147
6.3 Geometrie Isomerism in Polymers Prepared from Conjugated Dienes........150
6.4 Ziegler-Natta Coordination Polymerization.................................................152
6.4.1 Ziegler-Natta Catalysts....................................................................152
6.4.2 Propagation: Monomer Insertion at Group I?III Metal-Carbon
Bonds................................................................................................153
6.4.3 Propagation: Monomer Insertion at Transition Metal-Carbon
Bonds................................................................................................154
6.4.4 Propagation: Mechanistic Overview................................................l55
6.4.5 Termination of Chain Growth..........................................................156
6.4.6 Kinetics............................................................................................156
6.4.7 Practical Considerations...................................................................157
Contents ix
6.5 Metallocene Coordination Polymerization....................................................158
6.5.1 Metallocene Catalysts......................................................................159
6.5.2 Mechanism of Polymerization with Zirconocene:MAO Catalysts ... 159
6.5.3 Control of Propagation Stereochemistry with Zirconocenes...........161
6.5.4 Kinetics of Metallocene Polymerization..........................................162
6.5.5 Other Metallocene and Metallocene-Related Catalysts...................163
6.5.6 Practical Considerations...................................................................165
Problems...................................................................................................................166
Further Reading.......................................................................................................166
Chapter 7 Ring-Opening Polymerization.................................................................................169
7.1 Introduction to Ring-Opening Polymerization..............................................169
7.2 Cationic Ring-Opening Polymerization........................................................171
7.2.1 Cationic Ring-Opening Polymerization of Epoxides.......................171
7.2.2 Cationic Ring-Opening Polymerization of Lactones....................... 174
7.2.3 Cationic Ring-Opening Polymerization of Lactams........................175
7.2.4 Cationic Ring-Opening Polymerization of Cyclic Siloxanes...........176
7.3 Anionic Ring-Opening Polymerization.........................................................178
7.3.1 Anionic Ring-Opening Polymerization of Epoxides.......................178
7.3.2 Anionic Ring-Opening Polymerization of Lactones........................179
7.3.3 Anionic Ring-Opening Polymerization of Lactams........................180
7.3.4 Anionic Ring-Opening Polymerization of Cyclic Siloxanes...........182
7.4 Free-Radical Ring-Opening Polymerization.................................................183
7.5 Ring-Opening Metathesis Polymerization....................................................185
7.5.1 Chemistry of ROMP........................................................................185
7.5.2 Applications of ROMP.....................................................................188
Problems...................................................................................................................188
Further Reading.......................................................................................................189
General Reading............................................................................................189
Free-Radical Ring-Opening Polymerization.................................................189
Ring-Opening Metathesis Polymerization....................................................189
Chapter 8 Specialized Methods of Polymer Synthesis.............................................................191
8.1 Introduction...................................................................................................191
8.2 Solid-State Topochemical Polymerization....................................................191
8.3 Polymerization by Oxidative Coupling.........................................................193
8.3.1 Polymerization of Phenols by Oxidative Coupling..........................193
8.3.2 Polymerization of Aniline, Pyrrole and Thiophene by Oxidative
Coupling...........................................................................................194
8.4 Precursor Routes to Intractable Polymers.....................................................197
8.5 Supramolecular Polymerization (Polyassociation)........................................199
Problems...................................................................................................................203
Further Reading.......................................................................................................203
General Reading............................................................................................203
Synthesis of Conducting Polymers................................................................204
Supramolecular Polymerization....................................................................204
Chapter 9 Copolymerization.....................................................................................................205
9.1 Introduction...................................................................................................205
9.2 Step Copolymerization..................................................................................205
Contents
9.3 Chain Copolymerization...............................................................................206
9.3.1 Copolymer Composition Equation...................................................206
9.3.2 Monomer Reactivity Ratios and Copolymer Composition/
Structure...........................................................................................208
9.3.3 Copolymer Composition Drift.........................................................210
9.3.4 Evaluation of Monomer Reactivity Ratios.......................................211
9.3.5 Free-Radical Copolymerization.......................................................212
9.3.5.1 The Q-e Scheme..............................................................213
9.3.6 Reversible-Deactivation Radical Copolymerization........................214
9.3.7 Ionic Copolymerization....................................................................215
9.3.8 Ziegler-Natta Coordination Copolymerization...............................216
9.3.9 Metallocene Coordination Copolymerization..................................216
9.3.10 Other Types of Chain Copolymerization.........................................217
9.4 Block Copolymer Synthesis...........................................................................217
9.4.1 Synthesis of Segmented and Alternating Copolymers by Step
Polymerization..................................................................................217
9.4.2 Synthesis of Block Copolymers by Sequential Polymerization.......219
9.4.2.1 Synthesis of Block Copolymers by Living Anionic
Polymerization..................................................................219
9.4.2.2 Synthesis of Block Copolymers by Reversible-
Deactivation (Living) Cationic Polymerization................220
9.4.2.3 Synthesis of Block Copolymers by Reversible-
Deactivation (Living) Radical Polymerization.................221
9.4.2.4 Synthesis of Block Copolymers by Other Methods of
Living Polymerization......................................................223
9.4.2.5 Synthesis of Block Copolymers by Active-Centre
Transformation..................................................................224
9.4.3 Synthesis of Block Copolymers by Coupling of Polymer Chains.... 226
9.4.3.1 Synthesis of Block Copolymers by Click-Coupling of
Homopolymer Chains.......................................................227
9.4.4 Synthesis of Non-Linear Block Copolymers....................................228
9.5 Graft Copolymer Synthesis...........................................................................229
9.5.1 Synthesis of Graft Copolymers by Polymerization from a
Backbone Polymer............................................................................229
9.5.2 Synthesis of Graft Copolymers by Copolymerization with
Macromonomers...............................................................................231
9.5.3 Synthesis of Graft Copolymers by Coupling of Polymer Chains
to a Backbone Polymer.....................................................................232
Problems............................................ 233
Further Reading............................................... 233
PART II Characterization of Polymers
Chapter 10 Theoretical Description of Polymers in Solution.....................................................237
10.1 Introduction............................................... 237
10.2 Thermodynamics of Polymer Solutions........................................................237
10.2.1 Thermodynamics of Ideal Solutions................................................238
10.2.2 FJory-Huggins Theory.....................................................................239
Contents xi
10.2.3 Partial Molar Quantities and Chemical Potential............................245
10.2.4 Dilute Polymer Solutions..................................................................247
10.2.5 The Solubility Parameter Approach.................................................250
10.3 Chain Dimensions.........................................................................................253
10.3.1 Freely-Jointed Chains.......................................................................253
10.3.2 Effects of Bond Angle and Short-Range Steric Restrictions...........256
10.3.3 Effects of Long-Range Steric Interactions: Chains with
Excluded Volume.............................................................................259
10.4 Frictional Properties of Polymer Molecules in Dilute Solution....................262
10.4.1 Frictional Coefficients of Polymer Molecules..................................262
10.4.2 Hydrodynamic Volume and Intrinsic Viscosity in the
Non-Draining Limit.........................................................................263
10.4.3 Diffusion of Polymer Molecules in the Non-Draining Limit..........264
10.4.4 Solution Behaviour of Polyelectrolytes............................................265
Problems...................................................................................................................267
Further Reading.......................................................................................................268
Chapter 11 Number-Average Molar Mass..................................................................................269
11.1 Introduction to Measurements of Number-Average Molar Mass..................269
11.2 Membrane Osmometry..................................................................................269
11.2.1 Osmosis and Chemical Potential......................................................269
11.2.2 Measurement of Osmotic Pressure...................................................273
11.3 Vapour Pressure Osmometry.........................................................................275
11.4 Ebulliometry andCryoscopy.........................................................................277
11.5 End-Group Analysis......................................................................................278
11.6 Effects of Low Molar Mass Impurities upon M?...........................................279
Problems...................................................................................................................279
Further Reading.......................................................................................................280
Chapter 12 Scattering Methods..................................................................................................281
12.1 Introduction...................................................................................................281
12.2 Static Light Scattering...................................................................................281
12.2.1 Light Scattering by Small Molecules...............................................281
12.2.2 Light Scattering by Liquids and Solutions of Small Molecules.......284
12.2.3 Light Scattering by Large Molecules in Solution............................286
12.2.4 Effect of Molar Mass Dispersity......................................................288
12.2.5 Static Light Scattering Measurements.............................................290
12.2.6 Light Scattering by Multicomponent Systems.................................291
12.3 Dynamic Light Scattering.............................................................................291
12.4 Small-Angle X-Ray and Neutron Scattering.................................................294
Problems...................................................................................................................2%
Further Reading.......................................................................................................297
Chapter 13 Frictional Properties of Polymers in Solution..........................................................299
13.1 Introduction...................................................................................................299
13.2 Dilute Solution Viscometry...........................................................................299
13.2.1 Intrinsic Viscosity............................................................................299
13.2.2 Interpretation of Intrinsic Viscosity Data........................................300
13.2.3 Measurement of Solution Viscosity..................................................303
xii Contents
13.3 Ultracentrifugation........................................................................................306
Problems...................................................................................................................307
Further Reading.......................................................................................................308
Chapter 14 Molar Mass Distribution..........................................................................................309
14.1 Introduction...................................................................................................309
14.2 Fractionation..................................................................................................309
14.2.1 Phase-Separation Behaviour of Polymer Solutions..........................310
14.2.2 Theory of Fractionation by Phase Separation of Dilute Polymer
Solutions...........................................................................................313
14.2.3 Procedures for Fractionation............................................................317
14.3 Gel Permeation Chromatography..................................................................318
14.3.1 Separation by Size Exclusion...........................................................318
14.3.2 Calibration and Evaluation of Molar Mass Distributions................319
14.3.3 Universal Calibration.......................................................................321
14.3.4 Porous Gels and Eluants for GPC....................................................322
14.3.5 Practical Aspects of GPC.................................................................323
14.4 Field-Flow Fractionation...............................................................................325
14.4.1 FFF Techniques................................................................................326
14.4.2 Theory of Solute Separation by FFF................................................327
14.4.3 Applications of FFF.........................................................................331
14.5 Mass Spectroscopy........................................................................................331
14.5.1 Mass Spectra of Polymers................................................................332
14.5.2 Methods of Soft Ionization for Polymers.........................................333
14.5.2.1 Electrospray Ionization.....................................................334
14.5.2.2 Matrix-Assisted Laser Desorption/Ionization..................334
14.5.3 Time-of-Flight Mass Spectroscopy..................................................335
14.5.3.1 Principles of MALDI Time-of-Flight Mass
Spectrometry.....................................................................335
14.5.3.2 Evaluation of Molar Mass Distribution from Time-of-
Flight Mass Spectra..........................................................337
14.5.4 Molar Mass Distributions Obtained by MALDI Mass
Spectroscopy....................................................................................339
Problems...................................................................................................................340
Further Reading.......................................................................................................340
General Reading............................................................................................340
Field-Flow Fractionation...............................................................................341
Mass Spectroscopy........................................................................................341
Chapter 15 Chemical Composition and Molecular Microstructure...........................................343
15.1 Introduction...................................................................................................343
15.2 Principles of Spectroscopy............................................................................343
15.2.1 Uses of Electromagnetic Radiation in Polymer Science..................344
15.2.2 The Beer-Lambert Law for Absorption of Electromagnetic
Radiation..........................................................................................346
15.3 Ultraviolet and Visible Light Absorption Spectroscopy................................347
15.3.1 Applications of UV-vis Spectroscopy in Polymer Science..............348
15.3.2 Practical Aspects of UV-vis Spectroscopy.......................................350
Contents
15.4 Infrared Spectroscopy...................................................................................351
15.4.1 Applications of IR Spectroscopy in Polymer Science......................352
15.4.2 Practical Aspects of IR Spectroscopy..............................................354
15.5 Raman Spectroscopy.....................................................................................355
15.5.1 Applications of Raman Spectroscopy in Polymer Science..............356
15.5.2 Practical Aspects of Raman Spectroscopy.......................................358
15.6 Nuclear Magnetic Resonance Spectroscopy.................................................358
15.6.1 Analysis of Molecular Structure and Composition by NMR
Spectroscopy....................................................................................363
15.6.2 Analysis of End Groups and Branch Points by NMR
Spectroscopy..................................................................................363
15.6.3 Determination of Molecular Microstructure by NMR
Spectroscopy....................................................................................365
15.6.3.1 Determination of Tacticity................................................365
15.6.3.2 Determination of Repeat Unit Sequence Distributions
in Copolymers...................................................................371
15.6.4 Other Uses of NMR Spectroscopy in Polymer Science...................372
15.6.5 Practical Aspects of NMR Spectroscopy.........................................374
15.7 Mass Spectroscopy........................................................................................374
15.7.1 Elucidation of Structural Features by Mass Spectroscopy..............375
15.7.2 Other Uses of Mass Spectroscopy in Polymer Science....................377
Problems...................................................................................................................377
Further Reading.......................................................................................................379
General Reading............................................................................................379
Vibrational Spectroscopy...............................................................................379
Nuclear Magnetic Resonance Spectroscopy..................................................379
Mass Spectroscopy........................................................................................379
PART III Phase Structure and Morphology of Bulk Polymers
Chapter 16 The Amorphous State...............................................................................................383
16.1 Introduction...................................................................................................383
16.1.1 Structure in Amorphous Polymers...................................................383
16.2 The Glass Transition......................................................................................384
16.2.1 Thermodynamics of the Glass Transition........................................385
16.2.2 Free Volume.....................................................................................387
16.3 Factors Controlling the Tg..............................................................................388
16.3.1 Chemical Structure..........................................................................388
16.3.2 Copolymerisation.............................................................................389
16.3.3 Molecular Architecture....................................................................391
16.3.4 Film Thickness.................................................................................392
16.4 Macromolecular Dynamics...........................................................................392
16.4.1 The Rouse-Bueche Theory..............................................................393
16.4.2 The de Gennes Reptation Theory....................................................394
Problems...................................................................................................................3%
Further Reading.......................................................................................................397
xjv Contents
Chapter 17 The Crystalline State................................................................................................399
17.1 Introduction...................................................................................................399
17.1.1 Crystallinity in Polymers.................................................................399
17.1.2 Crystal Structure and Unit Cell........................................................400
17.2 Determination of Crystal Structure...............................................................400
17.2.1 X-Ray Diffraction.............................................................................400
17.2.1.1 Polymer Single Crystals....................................................401
17.2.1.2 Semi-Crystalline Polymers...............................................402
17.2.2 Polymer Crystal Structures..............................................................404
17.2.3 Factors Determining Crystal Structure............................................404
17.2.3.1 Polyethylene......................................................................406
17.2.3.2 Polytetrafluoroethylene.....................................................407
17.2.3.3 Vinyl Polymers.................................................................407
17.2.3.4 Polyamides........................................................................408
17.3 Polymer Single Crystals................................................................................408
17.3.1 Solution-Grown Single Crystals.......................................................408
17.3.2 Solid-State Polymerized Single Crystals.........................................412
17.4 Semi-Crystalline Polymers............................................................................412
17.4.1 Spherulites........................................................................................413
17.4.2 Degree of Crystallinity.....................................................................415
17.4.3 Crystal Thickness and Chain Extension..........................................417
17.4.4 Crystallization with Orientation.......................................................420
17.4.5 Polymer Fibres..................................................................................421
17.5 Liquid Crystalline Polymers..........................................................................421
17.5.1 Classes of Liquid Crystals................................................................421
17.5.2 Polymer Liquid Crystals...................................................................423
17.5.2.1 Thermotropic Systems......................................................423
17.5.2.2 Lyotropic Systems.............................................................424
17.6 Defects in Crystalline Polymers....................................................................425
17.6.1 Point Defects....................................................................................425
17.6.2 Dislocations......................................................................................426
17.6.3 Other Defects....................................................................................428
17.7 Crystallization...............................................................................................428
17.7.1 General Considerations....................................................................428
17.7.2 Overall Crystallization Kinetics......................................................430
17.7.3 Molecular Mechanisms of Crystallization.......................................432
17.8 Melting...........................................................................................................435
17.8.1 Differential Scanning Calorimetry..................................................435
17.8.2 Melting of Polymer Crystals............................................................439
17.8.3 Factors Affecting Tm.........................................................................440
17.8.3.1 Chemical Structure...........................................................440
17.8.3.2 Molar Mass and Brandung..............................................443
17.8.3.3 Copolymers.......................................................................444
17.8.4 Relationship between Tm and Tg........................................................444
Problems.................................................................. 445
Further Reading....................................................................... 447
Chapter 18 Multicomponent Polymer Systems...........................................................................449
18.1 Introduction...............................................................................................449
18.2 Polymer Blends...........................................................................................449
Contents
18.2.1 Thermodynamics of Polymer Blends...............................................449
18.2.2 Phase Behaviour...............................................................................452
18.2.3 Glass Transition Behaviour..............................................................455
18.2.4 Compatibilization of Polymer Blends..............................................455
18.3 Block Copolymers.........................................................................................456
18.3.1 Thermodynamics of Block Copolymer Phase Behaviour................457
18.3.2 Morphology of Block Copolymers...................................................459
18.3.2.1 Transmission Electron Microscopy..................................459
18.3.2.2 Small-Angle X-Ray Scattering.........................................461
18.3.3 Thermoplastic Elastomers................................................................462
Problems...................................................................................................................463
Further Reading.......................................................................................................465
PART IV Properties of Bulk Polymers
Chapter 19 Elastic Deformation..................................................................................................469
19.1 Introduction...................................................................................................469
19.2 Elastic Deformation.......................................................................................469
19.2.1 Stress................................................................................................469
19.2.2 Strain................................................................................................471
19.2.3 Relationship between Stress and Strain...........................................473
19.3 Elastic Deformation of Polymers...................................................................476
19.3.1 Deformation of a Polymer Chain.....................................................477
19.3.2 Polymer Crystal Moduli...................................................................479
19.3.3 Elastic Deformation of Semi-Crystalline Polymers.........................482
Problems...................................................................................................................484
Further Reading.......................................................................................................486
Chapter 20 Viscoelasticity..........................................................................................................487
20.1 Introduction...................................................................................................487
20.2 Viscoelastic Mechanical Models...................................................................487
20.2.1 Maxwell Model................................................................................489
20.2.2 Voigt Model......................................................................................490
20.2.3 Standard Linear Solid......................................................................492
20.3 Boltzmann Superposition Principle...............................................................492
20.4 Dynamic Mechanical Testing........................................................................494
20.5 Frequency Dependence of Viscoelastic Behaviour.......................................499
20.6 Transitions and Polymer Structure................................................................501
20.7 Time-Temperature Superposition.................................................................503
20.8 Effect ofEntanglements................................................................................505
20.9 Non-Linear Viscoelasticity............................................................................508
Problems...................................................................................................................508
Further Reading.......................................................................................................509
Chapter 21 Elastomers................................................................................................................511
21.1 Introduction...................................................................................................511
21.1.1 General Considerations....................................................................511
xvi Contents
21.1.2 Vulcanization...................................................................................512
21.1.3 Mechanical Behaviour......................................................................514
21.2 Thermodynamics of Elastomer Deformation................................................514
21.3 Statistical Theory of Elastomer Deformation................................................518
21.3.1 Entropy of an Individual Chain........................................................519
21.3.2 Deformation of the Polymer Network..............................................519
21.3.3 Limitations and Use ofthe Theory..................................................521
21.3.3.1 Entanglements...................................................................523
21.3.3.2 Chain Ends........................................................................523
21.4 Stress-Strain Behaviour of Elastomers.........................................................524
21.5 Factors Affecting Mechanical Behaviour......................................................526
21.5.1 Swelling............................................................................................526
21.5.2 Strain-Induced Crystallization.........................................................529
Problems...................................................................................................................529
Further Reading.......................................................................................................530
Chapter 22 Yield and Crazing.....................................................................................................531
22.1 Introduction...................................................................................................531
22.2 Phenomenology of Yield...............................................................................531
22.2.1 Definitions........................................................................................531
22.2.2 Necking and the Considere Construction.........................................533
22.2.3 Rate and Temperature Dependence..................................................534
22.3 Yield Criteria.................................................................................................535
22.3.1 Tresca Yield Criterion......................................................................536
22.3.2 Von Mises Yield Criterion................................................................536
22.3.3 Pressure-Dependent Yield Behaviour..............................................537
22.4 Deformation Mechanisms.............................................................................540
22.4.1 Theoretical Shear Stress...................................................................540
22.4.2 Shear Yielding in Glassy Polymers..................................................542
22.4.2.1 Stress-Induced Increase in Free Volume..........................543
22.4.2.2 Application of the Eyring Theory to Yield in Polymers.....543
22.4.2.3 Molecular Theories of Yield.............................................544
22.4.3 Plastic Deformation of Polymer Crystals.........................................545
22.4.3.1 Slip....................................................................................545
22.4.3.2 Dislocation Motion...........................................................546
22.4.3.3 Twinning.........................Z.Z.........................................547
22.4.3.4 Martensitic Transformations.............................................548
22.4.4 Plastic Deformation of Semi-Crystalline Polymers.........................549
22.5 Crazing.......................................................................................................550
22.5.1 Craze Yielding.....................ZZ Z ZZZZZZZZZZZZZZ...............550
22.5.2 Craze Criteria................................. _................................................552
22.5.3 Crazing in Glassy Polymers.............................................................553
Problems........................................................ .....................554
Further Reading............................................ .............................. .....................555
Chapter 23 Fracture and Toughening............................... .....................557
23.1 Introduction..................................... ............557
23.2 Fundamentals of Fracture..........................................................................557
23.2.1 Theoretical Tensile Strength ...ZZZZZZZZ...Z...................................557
Contents
23.2.2 Molecular Failure Processes............................................................559
23.2.2.1 Bond Rupture....................................................................559
23.2.2.2 Effect of Molar Mass........................................................560
23.3 Mechanics of Fracture...................................................................................561
23.3.1 Brittle Fracture and Flaws................................................................561
23.3.2 Linear Elastic Fracture Mechanics..................................................565
23.3.2.1 Definitions.........................................................................565
23.3.2.2 Fracture Mechanics Testing..............................................566
23.3.2.3 Crack Propagation in Poly(Methyl Methacrylate)............568
23.3.3 Tearing of Elastomers......................................................................570
23.3.4 Ducti le Fracture................................................................................573
23.4 Fracture Phenomena......................................................................................576
23.4.1 Ductile-Brittle Transitions...............................................................576
23.4.2 Impact...............................................................................................578
23.4.3 Fatigue..............................................................................................579
23.4.4 Environmental Fracture...................................................................582
23.5 Toughened Polymers.....................................................................................582
23.5.1 Mechanical Behaviour of Rubber-Toughened Polymers..................583
23.5.2 Mechanisms of Rubber-Toughening.................................................585
23.5.2.1 Transmission Electron Microscopy..................................585
23.5.2.2 Volume Change Measurements........................................587
Problems...................................................................................................................587
Further Reading.......................................................................................................588
Chapter 24 Polymer Composites.................................................................................................591
24.1 Introduction to Composite Materials.............................................................591
24.2 Matrix Materials............................................................................................592
24.3 Types of Reinforcement.................................................................................593
24.3.1 Particles............................................................................................593
24.3.2 Fibres................................................................................................594
24.3.2.1 Glass Fibres.......................................................................594
24.3.2.2 Carbon Fibres...................................................................595
24.3.2.3 High-Modulus Polymer Fibres.........................................597
24.4 Composite Composition................................................................................597
24.5 Particulate Reinforcement.............................................................................597
24.5.1 Packing Geometries.........................................................................598
24.5.2 Elastic Deformation..........................................................................598
24.5.3 Fracture............................................................................................600
24.6 Fibre Reinforcement......................................................................................602
24.6.1 Composite Geometry.......................................................................602
24.6.1.1 Fibre Packing....................................................................602
24.6.1.2 Fibre Arrangements..........................................................603
24.6.2 Continuous Fibres.............................................................................604
24.6.2.1 Axial Stiffness..................................................................604
24.6.2.2 Transverse Stiffness..........................................................605
24.6.3 Discontinuous Fibres........................................................................606
24.6.3.1 Elastic Stress Transfer......................................................607
24.6.3.2 Experimental Determination of Fibre Stress
Distributions.....................................................................610
xviii Contents
24.6.4 Fracture............................................................................................612
24.6.4.1 Continuous and Aligned Fibres........................................612
24.6.4.2 Discontinuous Fibres........................................................613
24.7 Nanocomposites.............................................................................................614
24.7.1 Nanoparticles....................................................................................614
24.7.1.1 Carbon Black....................................................................614
24.7.1.2 Nanosilica.........................................................................616
24.7.2 Nanoplatelets....................................................................................617
24.7.2.1 Clays.................................................................................617
24.7.2.2 Graphene...........................................................................618
24.7.3 Carbon Nanotubes............................................................................619
Problems...................................................................................................................622
Further Reading.......................................................................................................622
Chapter 25 Electrical Properties.................................................................................................623
25.1 Introduction to Electrical Properties.............................................................623
25.2 Dielectric Properties......................................................................................623
25.2.1 Molecular Polarizability...................................................................623
25.2.2 Dielectric Measurements..................................................................624
25.2.3 Dielectric Relaxations......................................................................628
25.2.4 Dielectric Breakdown.......................................................................630
25.3 Conduction in Polymers................................................................................630
25.3.1 Measurement of Conductivity..........................................................630
25.3.2 Conducting Composites...................................................................632
25.3.3 Ionic Conduction..............................................................................634
25.3.4 Inherently Conducting Polymers......................................................635
25.3.5 Polyacetylene....................................................................................635
25.3.5.1 Structure of Polyacetylene................................................635
25.3.5.2 Preparation of Conducting Polyacetylene.........................636
25.3.5.3 Electronic Structure of Doped Polyacetylene...................638
25.4 Polymer Electronics.......................................................................................640
25.4.1 Polymer-Based Light-Emitting Diodes............................................640
25.4.2 Polymer-Based Solar Cells...............................................................641
25.4.3 Polymer-Based Transistors...............................................................641
25.4.4 Polymer-Based Sensors....................................................................642
Problems..................................... 543
Further Reading......................... 544
Answers to Problems......................................... 545
Index....................................................................... ......................653
|
| any_adam_object | 1 |
| author | Young, Robert J. 1948- Lovell, Peter A. |
| author_GND | (DE-588)123056632 |
| author_facet | Young, Robert J. 1948- Lovell, Peter A. |
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| discipline | Chemie / Pharmazie Physik |
| edition | Third edition |
| format | Book |
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| id | DE-604.BV037391997 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T23:23:19Z |
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| isbn | 0849339294 9780849339295 |
| language | English |
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| spelling | Young, Robert J. 1948- Verfasser (DE-588)123056632 aut Introduction to polymers Robert J. Young and Peter A. Lovell Third edition Boca Raton, Fla. [u.a.] CRC Press 2011 XX, 668 Seiten Illustrationen, Diagramme txt rdacontent n rdamedia nc rdacarrier Polymers Polymerization Polymere (DE-588)4046699-1 gnd rswk-swf 1\p (DE-588)4151278-9 Einführung gnd-content Polymere (DE-588)4046699-1 s DE-604 Lovell, Peter A. Verfasser aut HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=022544863&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk |
| spellingShingle | Young, Robert J. 1948- Lovell, Peter A. Introduction to polymers Polymers Polymerization Polymere (DE-588)4046699-1 gnd |
| subject_GND | (DE-588)4046699-1 (DE-588)4151278-9 |
| title | Introduction to polymers |
| title_auth | Introduction to polymers |
| title_exact_search | Introduction to polymers |
| title_full | Introduction to polymers Robert J. Young and Peter A. Lovell |
| title_fullStr | Introduction to polymers Robert J. Young and Peter A. Lovell |
| title_full_unstemmed | Introduction to polymers Robert J. Young and Peter A. Lovell |
| title_short | Introduction to polymers |
| title_sort | introduction to polymers |
| topic | Polymers Polymerization Polymere (DE-588)4046699-1 gnd |
| topic_facet | Polymers Polymerization Polymere Einführung |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=022544863&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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