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Nano- and Micromechanics of Polymers - Structure Modification and Improvement of Properties
Table of Contents
6
Preface
12
List of Abbreviations
16
I Aim and methods
20
1 General Importance of Polymers and Trends
22
1.1 Relevance of Polymeric Materials
22
1.2 Materials Science Aspects
24
1.3 Molecular and Supramolecular Structures
26
1.3.1 Molecular Structures
26
1.3.2 Supramolecular Structures, Morphology
32
1.4 Polymer Modification
40
1.4.1 Copolymers
41
1.4.2 Polymer Blends
43
1.4.3 Particulate Composites
47
1.4.4 Short Fiber Reinforced Polymers
49
1.4.5 Conclusions
50
2 Methods and Investigation Techniques
54
2.1 Methods of Structure and Morphology Analysis
54
2.1.1 Macroscale Methods
54
2.1.1.1 X-Ray Diffraction Techniques (WAXS, SAXS)
54
2.1.1.2 Other Scattering Techniques
58
2.1.1.3 Spectroscopic Techniques and Thermal Methods
59
2.1.2 Local, Microscopic Methods
68
2.1.2.1 Optical Microscopy (OM)
69
2.1.2.2 Confocal Scanning Optical Microscopy
71
2.1.2.3 Scanning Electron Microscopy (SEM)
71
2.1.2.4 Transmission Electron Microscopy (TEM)
75
2.1.2.5 Atomic Force Microscopy (AFM)
78
2.1.2.6 Comparison of Microscopic Techniques
80
2.2 Methods of Nano- and Micromechanical Analysis
82
2.2.1 Macroscale Methods
82
2.2.1.1 Scattering (Diffraction) Methods
82
2.2.1.2 Interference Optics
83
2.2.1.3 Spectroscopic Techniques (Rheo-Optical Methods)
83
2.2.1.4 Other Techniques
85
2.2.2 Local (Microscopic) Methods
85
2.2.2.1 Overview
85
2.2.2.2 In-Situ Microscopy
89
2.3 Mechanical “Micro-Testing”
99
2.3.1 Mechanical Testing of Micro-Sized Specimens
101
2.3.2 Microindentation Tests
103
2.3.2.1 Imaging Method
103
2.3.2.2 Basic Aspects of Microindentation: Contact Geometry
104
2.3.2.3 Depth Sensing Measurements
105
II General mechanisms of deformation and fracture
114
3 Deformation Phenomena and Mechanisms
116
3.1 Basic Types of Mechanical Behavior
116
3.2 Influence of Specimen Size
122
3.3 Deformation Mechanisms
127
3.4 Molecular Parameters and Mechanisms
129
3.4.1 Molecular Mobility and Entanglements
129
3.4.2 Molecular Micro-Mechanisms
134
4 Crazing
138
4.1 The Phenomenon of „Craze“
138
4.2 Characteristics of Crazes
140
4.3 Variety of Craze Structures
144
4.4 Craze Initiation
153
4.4.1 Formation of Pre-Crazes
154
4.4.2 Transformation of Pre-Crazes into Fibrillated Crazes
159
4.5 Craze Growth and Fracture
161
4.5.1 Length Growth
161
4.5.2 Thickness Growth
162
4.5.3 Craze Fracture
164
4.6 Factors Influencing Craze Initiation and Growth
166
4.7 Structure Initiated Crazes
172
5 Fracture Phenomena and Mechanisms
178
5.1 Overview
178
5.2 Principles of Brittle Fracture of Polymers
179
5.3 Stress Concentrations at Particles and Voids
184
5.3.1 Soft Particles
185
5.3.2 Hard Particles
189
5.3.3 Thermal Stresses
189
5.3.4 Energetic Effects
191
5.3.5 Stress Concentration Effects in Different Particle/Void Arrangements
192
5.3.5.1 Particle/Void Size
192
5.3.5.2 Particle/Void Distance
193
5.4 Toughness Enhancing Mechanisms
194
5.5 Fracture Surface Analysis and Damage Analysis
197
III Main groups of polymer materials
202
6 Amorphous Polymers
204
6.1 Overview
204
6.2 Amorphous Homopolymers
207
6.2.1 Polystyrol (PS)
207
6.2.1.1 Deformation Characteristics
207
6.2.1.2 Modification of Crazes
212
6.2.2 Polymethylmethacrylate (PMMA)
215
6.2.3 Polyvinylchloride (PVC)
217
6.2.4 Polycarbonate (PC)
218
6.2.5 Other Amorphous Homopolymers
223
6.3 Copolymers
223
6.3.1 Styrene-Acrylonitrile-Copolymers (SAN)
223
6.3.2 Cyclic Olefin Copolymers (COC)
224
6.4 Comparison of Crazes
228
6.5 Resins, Thermosets
230
7 Semicrystalline Polymers
234
7.1 Overview
234
7.2 General Deformation Mechanisms
237
7.2.1 Brittle Behavior
238
7.2.1.1 Initiation of Brittle Fracture by Morphological Defects
238
7.2.1.2 Brittle Fracture of Low Molecular Weight Materials
240
7.2.1.3 Brittle Fracture at Low Temperatures
243
7.2.1.4 Environmental Stress Crazing/Cracking
243
7.2.1.5 Physical Ageing
244
7.2.2 Craze-Like Mechanisms
244
7.2.2.1 Crazing at Low Temperatures
244
7.2.2.2 Crazing at Brittle Fracture Above Tg,am
245
7.2.2.3 Environmental Crazing
247
7.2.2.4 Crazing under Plastic Deformation
249
7.2.2.5 Formation of Chevron Pattern
251
7.2.3 Ductile Behavior
254
7.2.3.1 Plastic Deformation of Spherulites
254
7.2.3.2 Deformation on the Amorphous/Lamellar Level
256
7.2.3.3 Strain Hardening and Self-Reinforcement
261
7.2.4 Deformation of Crystals and Lamellae
261
7.2.5 Self-Reinforcement and High Strength Materials
263
7.2.5.1 Oriented Structures by Melt Processing
263
7.2.5.2 Oriented Structures by Solution(Gel)-Spinning
265
7.3 Examples
266
7.3.1 Polyethylenes
266
7.3.1.1 Influence of Molecular Weight
266
7.3.1.2 Influence of Chain Architecture: Branching
269
7.3.1.3 Influence of Processing
273
7.3.2 Polypropylenes
274
7.3.2.1 Influence of Molecular Weight
274
7.3.2.2 Crystalline Modification
277
7.3.2.3 Influence of the Deformation Temperature
284
7.3.2.4 Additional Effects
286
7.3.3 Polyamides
287
7.3.4 Polyurethanes
289
7.3.5 Polyethylene Terephthalate (PET)
289
7.3.6 Syndiotactic Polystyrene
290
7.3.7 Fluoropolymers: PTFE, PVDF
292
7.3.8 Comparison of different polymers
293
8 Polymer Blends
300
8.1 Overview
300
8.2 Thermoplastic/Thermoplastic Blends
303
8.2.1 Blend Formation
303
8.2.2 Morphology
303
8.2.3 Micromechanical Properties
304
8.2.3.1 Blends of Amorphous Polymers
304
8.2.3.2 Blends of Amorphous and Semicrystalline Polymers
308
8.2.3.3 Blends of Semicrystalline Polymers
313
8.3 Rubbers and Elastomers
318
8.3.1 Overview
318
8.3.2 Typical Morphology
321
8.3.3 Micromechanical Behavior
324
8.4 Inclusion Yielding
328
9 Rubber Toughened Polymers
334
9.1 Overview
334
9.2 Morphology
336
9.3 Basic Micromechanical Mechanisms
339
9.3.1 Survey of Micromechanical Behavior
339
9.3.2 Rubber Particle Volume Content
347
9.3.3 Rubber Particle Modulus
350
9.3.4 Grafting Influence (Interfacial Bonding)
351
9.3.5 Particle Size
352
9.3.6 Additional Factors
359
9.4 Disperse Systems
361
9.4.1 Disperse Systems with Amorphous Matrix
361
9.4.2 Disperse Systems with Semicrystalline Matrix
370
9.5 Rubber Network Systems
379
10 Composites
388
10.1 Overview
388
10.2 Particle-Reinforced Polymer Composites
389
10.2.1 Morphology of Particle-Filled Polymers
389
10.2.2 Micromechanical Effects
391
10.2.2.1 Composites with a Tough Matrix (PE, PP)
391
10.2.2.2 Composites with a Stiff Matrix
402
10.2.2.3 Conclusion
403
10.3 Nanoparticle Polymer Composites
404
10.3.1 Overview and General Dependences
404
10.3.2 Micromechanical Effects in Different Classes of Nanocomposites
408
10.3.2.1 Zero-Dimensional Filler Nanoparticles (POSS)
408
10.3.2.2 One-Dimensional Carbon Nanotubes (CNT)
409
10.3.2.3 Two-Dimensional Layered Particles
414
10.3.2.4 Three-Dimensional Filler Particles
418
10.4 Fiber-Reinforced Polymer Composites
424
10.4.1 Overview
424
10.4.2 General Micromechanical Effects
425
11 Nanostructured Polymers
434
11.1 Overview
434
11.2 Block Copolymers
435
11.2.1 Introduction
435
11.2.2 Diversity in Morphologies and Properties
436
11.2.3 Micromechanical Behavior of Block Copolymers
443
11.2.4 Functional BCPs and Nanocomposites
455
11.2.5 Microdeformation Behavior in Block Copolymer/Polystyrene Blends
459
11.2.5.1 Blends Containing Macrophase-Separated PS Particles
459
11.2.5.2 Blends with Oriented Layers
460
11.2.5.3 Blends with Droplet Morphologies
462
11.2.6 Microhardness vs. Micromechanical Mechanisms
465
11.2.7 Mechanism of Chevron Formation
468
11.3 Coextruded Multilayered Polymers
470
11.3.1 Overview of Microlayered Composites and Coextrusion Technology
470
11.3.2 Structure-Property Correlations in Multilayered Composites Comprising Amorphous Polymers
476
11.3.3 Multilayered Crystalline/Amorphous Polymer Combinations
487
11.3.4 Multilayered Crystalline/Crystalline Polymer Combinations
494
11.4 Nanofibers
496
11.4.1 Overview
496
11.4.2 Electrostatic Spinning (Electrospinning)
497
11.4.3 Typical Fiber Structures
498
11.4.3.1 Fibers with Porous Structures
498
11.4.3.2 Fibers with Beads and Ribbon-Like Structures
499
11.4.3.3 Fibers with Helical and Twisted Structures
500
11.4.3.4 Fibers with Rough Surfaces
501
11.4.3.5 Fibers with Core Sheath Structures
502
11.4.4 Mechanical Properties of Polystyrene (PS) Nanofibers
503
11.4.5 Nanofibers – Nanocomposites
507
11.5 Conclusions
508
12 Special Forms and Applications
520
12.1 Overview, Special Forms
520
12.2 Hot Compacted Oriented Films/Fibers
522
12.2.1 Overview
522
12.2.2 Hot Compacted Oriented Fibers
524
12.2.3 Hot Compacted Oriented Films
528
12.2.4 Conclusions
531
12.3 Biomedical Polymers
531
12.3.1 UHMWPE
533
12.3.1.1 Morphology and Properties of UHMWPE
533
12.3.1.2 Application of UHMWPE in Hips and Knee Joints
538
12.3.2 Polymethylmethacrylate (PMMA)
545
12.3.3 Bioresorbable Polymers
548
12.3.4 Bone Substitutes
551
12.3.5 Electrospun Nanofibers
554
12.3.5.1 Nanofibrous Scaffolds for Tissue Engineering of Skin
554
12.3.5.2 Dentistry Applications
555
12.3.5.3 Scaffolds for Bone Tissue Engineering
557
12.4 Biopolymers
558
Index
576
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