I.M. Ward FRS, P.D. Coates, M. Dumoulin
Solid Phase Processing of Polymers
Foreword
8
Contents
10
1 Introduction
22
1.1 Key Scientific Issues
22
1.1.1 The chemical structure of the polymer and its degrees of regularity
22
1.1.2 The effect of plastic deformation, the concept of the true stress-true strain curve
24
1.1.3 Structural considerations: molecular understanding of plastic deformation
29
References
31
2 Deformation Mechanisms and Morphology of Crystalline Polymers
32
2.1 Introduction
32
2.2 Macroscopic Phenomena
32
2.3 Cracks, Crazing and Brittleness
33
2.4 Segregation-Induced Brittleness
36
2.5 Cold Drawing
37
2.6 Morphological Factors
38
2.7 Microscopic Observations
40
2.8 Electron Microscopy
41
2.9 The Deformation of Banded Spherulites
43
2.10 Lamellar Deformation
45
2.11 Memory Retention in Cold Drawing
46
2.12 Ordering Within Fibres
48
2.13 Disentanglement
50
2.14 Overview
50
References
51
3 Characterization of Orientation
54
3.1 Molecular Orientation and Its Definition
54
3.2 Birefringence
62
3.2.1 Biaxially oriented polyethylene terephthalate (PET) film
67
3.2.2 PET orientation and relaxation monitoring
68
3.3 Vibrational Spectroscopy
70
3.3.1 General
70
3.3.2 Transmission infrared spectroscopy
70
3.3.3 Attenuated total reflection (ATR) infrared spectroscopy
79
3.3.4 External reflection infrared spectroscopy
81
3.3.5 Photoacoustic infrared spectroscopy
84
3.3.6 Raman spectroscopy
85
3.4 Other Spectroscopic Techniques
86
3.4.1 Fluorescence
86
3.4.2 Nuclear magnetic resonance (NMR) spectroscopy
88
3.5. X-Ray Diffraction
90
3.5.1 General
90
3.5.2 Amorphous orientation from X-Ray diffraction
95
3.5.3 Synchrotron X-Ray diffraction
97
3.6 Ultrasonic and Other Techniques
98
References
100
4. Solid State Processing of Fibers
106
4.1 Introduction
106
4.1.1 Background
106
4.1.2 Common polymers used in man made fibers
106
4.2 Overview of Fiber Processing
107
4.3 The Liquid State
110
4.4 The Spinning Process
111
4.4.1 Spinning technology
111
4.4.2 Modelling the spinning process
115
4.4.3. Development of structure during melt spinning
120
4.4.4 Development of structure during solution spinning
122
4.4.5 Development of structure during liquid crystalline spinning
123
4.5 The Drawing Process
123
4.5.1 Drawing technology
124
4.5.2 Modelling the drawing process
126
4.5.3 Development of structure during drawing of flexible chain polymers
131
4.6 The Heat Treating Process
134
4.6.1 Heat treating technology
134
4.6.2 Development of structure during the heat treating of flexible chain polymers
135
4.6.3 Development of structure during the heat treating of rigid chain polymers
135
4.7 Fiber Structure: Multiphase Models
136
4.8 General Process-Structure-Property Relationships
137
4.9 Other Textile Processes
138
4.10 Special Processes
139
4.10.1 Gel spinning and superdrawing
139
4.10.2 Protein fibers
139
4.11 Conclusions: what do you want to make - what really matters
140
References
140
5 High Modulus Fibres
141
5.1 Melt Spun Polyethylene, Polypropylene and Polyoxymethylene (Polyacetal) Fibres
141
5.1.1 Introduction
141
5.1.2 The tensile drawing behaviour of polyethylene
144
5.1.3 Tensile drawing of polypropylene and polyoxymethylene
149
5.1.4 The structure of ultra high modulus polymers
149
5.1.5 Fibre strength
151
5.1.6 Other mechanical properties
157
5.1.7 Thermal properties
168
5.1.8 Surface treatment
169
5.1.9 Applications of melt spun PE fibres
170
5.1.10 Composites
170
5.1.11 Hot compaction
171
References
173
5.2 Aramid Fibres
176
5.2.1 Historical introduction
176
5.2.2 Heat- and flame-resistant meta-aramid fibres
178
5.2.3 High-tenacity high-modulus fibres from anisotropic solution
180
5.3.3 High-tenacity high-modulus aramid fibres from isotropic solutions
189
References
191
5.3 Fibres Based on Ultra-High Molecular Weight Polyethylene - Processing and Applications
193
5.3.1 Introduction
193
5.3.2 The ultimate stiffness and strength of flexible polymers
200
5.3.3 Chain-extension, on the borderline between solid and melt
203
5.3.4 Properties and applications of polyethylene fibres
220
5.3.5 Limiting properties of polyethylene fibres
225
5.3.6 Conclusions
231
References
231
6 Development of Molecular Orientation During Biaxial Film Tentering of PET
235
6.1 Introduction
235
6.2 Definitions, Materials and Experimental Characterisation Techniques
238
6.2.1 Quantitative characterisation of orientation
238
6.2.2 Experimental techniques: Characterization of the crystalline phase
239
6.3 First Stretching Process
242
6.3.1 Normal sequence
242
6.3.2 Inverse sequence
249
6.3.3 Comparison between constant rate and constant force drawing of amorphous samples
251
6.4 Transverse Stretching of One-Way Drawn Samples
252
6.4.1 Transverse stretching in the normal sequence
252
6.4.2 Transverse stretching in the inverse sequence
259
6.4.3 Comparison between constant rate and constant force transverse drawing
263
6.5 High Temperature Annealing
265
6.5.1 Influence of annealing time
267
6.5.2 Influence of the annealing temperature
271
6.6 Conclusions
275
References
276
7. Rolling and Roll-Drawing of Semi-Crystalline Thermoplastics
279
7.1 Introduction
279
7.1.1 Why orient polymers?
279
7.1.2 Orientation processes and solid state deformation of semi-crystalline polymers
280
7.2 Rolling and Roll-drawing
283
7.2.1 Introduction
283
7.2.2 Roll-drawing of semi-crystalline polymers
284
7.2.3 Structure development
285
7.2.4 Mechanical properties
287
7.3 A Case Study: PET
289
7.3.1 Orientation of PET
289
7.3.2 Relaxation and recovery during rolling
290
7.4 Roll-Drawing ofPET
300
7.4.1 Roll-drawing of amorphous PET
301
7.4.2 Roll-drawing of semi-crystalline PET
303
7.4.3 Properties
312
References
315
8 Planar Deformation of Thermoplastics
317
8.1 Introduction
317
8.2 Concepts
319
8.2.1 Synergistic effect
319
8.2.2 Orientation texture
320
8.2.3 Order-disorder transition
321
8.3 Physical Properties Induced By Planar Deformation
322
8.3.1 Polyethylene
322
8.3.2 Polypropylene
325
8.3.3 Higher poly-1-olefine
329
8.3.4 Poly(ethylene terephthalate)
329
8.3.5 Polyimide
330
8.3.6 Other thermoplastics
331
8.4 Analytical Approaches for Planar Deformation
331
8.4.1 Ductility and draw efficiency
331
8.4.2 Trirefringence
332
8.4.3 X-ray analysis
333
8.4.4 Spectroscopy
334
8.4.5 Neutron scattering
335
8.4.6 Elastic recovery
335
8.4.7 Gas permeation
336
8.4.8 Mechanical tests
338
8.4.9 Multiple regression analysis
342
References
345
9 Solid State Extrusion and Die Drawing
349
9.1 Ram Extrusion
349
9.2 Hydrostatic Extrusion
351
9.2.1 Introduction
351
9.2.2 The mechanics of the hydrostatic extrusion process
353
9.2.3 Hydrostatic extrusion as a possible engineering operation
358
9.2.4 Hydrostatic extrusion of pressure annealed polyethylene
359
9.2.5 Hydrostatic extrusion of filled polymers
362
9.2.6 Other properties of hydrostatically extruded materials
365
9.3 Die-Drawing
366
9.3.1 The die-drawing process
366
9.3.2 Die-drawing of tube
372
9.3.3 Development of the continuous die-drawing process
378
9.3.4 Mechanics of the die-drawing process
382
9.3.5 Properties of die-drawn products
383
9.3.6 Applications of die-drawn materials
385
References
386
10. Mathematical Modelling
389
10.1 Constitutive Equations
389
10.1.1 Phenomenological equations
389
10.1.2 Constitutive relations incorporating the deformation of a molecular network
394
10.2 Numerical Modelling of Forming Processes
400
10.2.1 Elastic constitutive behaviour
401
10.2.2 Rate dependent constitutive behaviour
413
References
423
Index
425
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