David R. Salem
Structure Formation in Polymeric Fibers
Contributors
7
Contents
9
Preface
18
1 Variations on a Theme of Uniaxial Orientation: Introductory Remarks on the Past, Present and Future of Fiber Formation
20
2 Structure Formation During Melt Spinning
24
2.1 Concepts and Theories
26
2.1.1 Introduction
26
2.1.2 An Engineering Analysis of the Process
28
2.2 Experimental Observations and Discussion
48
2.2.1 Polyolefins
48
2.2.2 Polyesters
71
2.2.3. Polyamides
86
2.2.4 Other Homopolymers
94
2.2.5 Copolymers Developed for Specialty Applications
96
2.2.6 Polymer Blends and Bicomponent Fibers
102
2.3 Concluding Remarks
106
Acknowledgments
106
2.4 References
106
3 Advances in the Control of Spinline Dynamics for Enhanced Fiber Properties
114
3.1 Introduction
114
3.2 Moving Beyond Imposed Limits as Take-Up Speeds Increase
114
3.2.1 The Dominant Forces
114
3.2.2 Cooling and Crystallization
118
3.2.3 Transient Effects
120
3.3 Recent Development Efforts and Achievements
122
3.3.1 Theoretical Tensile Strengths and the Potential for Vast Improvements
122
3.3.2 The Ideal One-Step Spinning Process
122
3.3.3 Patented Advances in Fiber Melt Spinning
124
3.4 The Preferred Route to Judicious Control of Spinline Dynamics
128
3.4.1 Judicious Control via Radical Change
128
3.4.2 The Response of Spinline Dynamics
128
3.4.3 Unprecedented As-Spun Fiber Properties
130
3.4.4 The Concept of Extended Chains and Enhanced Molecular Connectivity
132
3.5 Potential Applications and Future Development
134
3.6 References
136
4 Draw-Induced Structure Development in Flexible-Chain Polymers
138
4.1 Introduction
138
4.2 Overview of Stress-Strain-Structure Relationships
140
4.2.1 Modes of Deformation
140
4.2.2 Constant Extension Rate Deformation
142
4.2.3 Constant Force Deformation
152
4.3 Orientation-Induced Crystallization
154
4.3.1 General Concepts
154
4.3.2 The Case of Poly(ethylene terephthalate)
156
4.3.3 Other Polymers
170
4.4 Theory and Modeling
172
4.4.1 Stress-Strain-Orientation Behavior
172
4.4.2 Crystallization
181
4.4.3 Molecular Dynamics Simulations
182
4.5 Morphology
184
4.5.1 Range of Order
184
4.5.2 Three Phase Models
184
4.6 Structure-Property Relationships
186
4.6.1 Tensile Modulus, Strength, Yield, and Elongation at Break
188
4.6.2 Dimensional Stability
190
4.6.3 Penetrant Diffusion
190
4.7 High Performance Fibers
192
4.7.1 Apolar Polymers
192
4.7.2 Polar Polymers
194
4.8 References
198
5 Basic Aspects of Solution(Gel)-Spinning and Ultra-Drawing of Ultra-High Molecular Weight Polyethylene
205
5.1 Introduction
207
5.2 The Ultimate Stiffness and Strength of Flexible Polymers
208
5.2.1 The Ultimate Tensile Modulus
208
5.2.2 The Ultimate Tensile Strength
208
5.2.3 Infinite vs. Finite Chains
208
5.2.4 Chain Alignment, Orientation vs. Extension
210
5.3 Chain Orientation and Chain Extension
214
5.3.1 The Single Chain
214
5.3.2 An Ensemble of Chains
216
5.4 Drawing of Polyethylene in the Solid-State
218
5.4.1 Solid-State Drawing of Polyethylenes
218
5.4.2 Solution(Gel)-Crystallized Polyethylene
220
5.4.3 Solvent-Free Processing of UHME-PE; Nascent Reactor Powders
222
5.4.4 Modeling of the Drawing Behavior
230
5.4.5 Drawing Behavior of Other Polymer Systems
236
5.5 Properties of Polyethylene Fibers, 1-D vs. 3-D
238
5.5.1 Tensile Strength (1-D)
238
5.5.2 Polyethylene Fibers in Composites (3-D)
240
5.5.3 Miscellaneous Properties of UHMW-PE Fibers
240
5.6 Concluding Remarks
240
5. 7 List of Symbols and Abbreviations
242
5.8 References
242
6 Electrospinning and the Formation ofNanofibers
244
6.1 Introduction
245
6.2 Electrospinning Process
246
6.2.1 Jet Initiation and the Diameter of a Single Jet
248
6.2.2 Bending Instability and Elongation of the Jet
248
6.2.3 Diameter of Nanofibers
252
6.2.4 Observations of Electrospinning of Polyethylene oxide Solutions: Length ofthe Straight Segment, Flow Rate of the Solution, Current and Voltage
254
6.3 Nanofibers and Their Unique Properties
256
6.3.1 Beaded Nanofibers
256
6.3.2 Electrospun Poly (p-phenylene terephthalamide)
256
6.3.3 Composites with Nanofiber Reinforcement
258
6.3.4 Elastomeric Poly(styrene-butadiene-styrene) Nanofibers, Phase Miscibility
260
6.3.5 Carbon Nanofibers
260
6.3.6 Nanofibers for Biomedical, Filtration, Agricultural, and Outer-Space Applications
264
6.4 Acknowledgements
264
6.5 References
264
7 Fibers from Liquid Crystalline Polymers
266
7.1 Introduction: Liquid Crystalline Phases
266
7.2 Rheology in Liquid Crystalline Polymers
268
7.3 Fibers from Liquid Crystalline Polymers
273
7.4 Structure Formation and Properties of Liquid Crystalline Polymer Fibers from the Lyotropic Liquid Crystalline State
276
7.4.1 Molecular Parameters, Fiber Spinning, and Heat Treatments
278
7.4.2 PPTA Fiber Structure, Morphology, and Properties
280
7.4.3 PBZT and PBO Fiber Structure, Morphology, and Properties
286
7.5 Structure Formation and Properties of Liquid Crystalline Polymer Fibers from the Isotropic Solution State
290
7.5.1 Molecular Parameters, Fiber Spinning, and Heat Treatments
292
7.5.2 Organo-Soluble Aromatic Polyimide Fiber Structure, Morphology,and Properties
294
7.5.3 Technora Fiber Structure, Morphology, and Properties
300
7.6 Structure Formation and Properties of Liquid Crystalline Polymer Fibers from the Thermotropic State
302
7.6.1 Molecular Parameters, Fiber Spinning, and Heat Treatments
302
7.6.2 HBA/PET Copolyester Fiber Structure, Morphology, and Properties
304
7.6.3 HBA/HNA Copolyester Fiber Structure, Morphology, and Properties
307
7.6.4 Ekonol® Copolyester Fiber Structure, Morphology, and Properties
308
7.7 Concluding Remarks
308
7.8 References
308
8 Solvent Spun Cellulose Fibers
316
8.1 Structure and Properties
316
8.1.1 Introduction
316
8.1.2 Cellulose Structure
316
8.2 Fiber Formation
320
8.2.1 Introduction
320
8.2.2 Liquid Crystalline State
326
8.2.3 Direct Dissolution of Cellulose
328
8.2.4 Fiber Extrusion and Properties
340
8.3 Concluding Remarks
344
8.4 References
344
9 Carbon Fibers
349
9.1 Formation and Structure
349
9.1.1 Introduction
349
9.1.2 Carbon Fibers from PAN Precursors
350
9.1.3 Carbon Fibers from Pitch Precursors
356
9.2 Structure and Properties
358
9.2.1 Tensile Modulus
358
9.2.2 Tensile and Compressive Strength
358
9.2.3 The Structure of Carbon Fibers
360
9.2.4 Failure Mechanisms
368
9.2.5 Disorder in Carbon Fibers
372
9.2.6 Structure-Property Relations
374
9.3 References
376
10 Fibers from Electrically Conductive Polymers
378
10.1 Introduction
378
10.1.1 Polymer Conductivity
380
10.1.2 Measurement of Polymer Conductivity
386
10.1.3 Processing of Conductive Polymers
388
10.1.4 Fiber Formation
392
10.2 Fiber Formation from Emeraldine Base Polyaniline
392
10.2.1 Solution Spinning of Emeraldine Base Fiber
396
10.2.2 PANI Fiber Properties
404
10.2.3 Viscoelastic Characterization of PANI Spin Dopes
406
10.2.4 Thermal Characteristics of LEB PANI Fibers
412
10.3 Conclusion
412
10.4 Future Trends
414
10.5 References
414
11 Fibers from Polymer Blends and Copolymers
416
11.1 Introduction
416
11.2 Polymer Blends
418
11.2.1 Introduction
418
11.2.2 Miscibility
418
11.2.3 Multi-Phase Blends
420
11.2.4 Blends of Thermoplastics and Thermotropic Liquid Crystalline Polymers
420
11.3 Bicomponent Fibers
422
11.4 Fibers from Polymer Blends
424
11.5 Thermoplastic Fibers Reinforced with Thermotropic Liquid Crystalline Polymers
426
11.5.1 Fibers Produced via Simultaneous Melting of Blend Components
426
11.5.2 Fibers Generated Using the Dual Extrusion Process
428
11.5.3 Post Processing of Fibers Generated Using the Dual Extrusion Process
437
11.6 Copolymers
438
11.7 Elastomeric Fibers
440
11.8 References
442
12 Thermomechanical Processing: Structure and Properties
444
12.1 Introduction
444
12.2 Commercial Practice*
446
12.2.1 General Comments
446
12.2.2 Consumer Textiles
446
12.2.3 Tire Cord and Other Industrial Applications
450
12.3 Phenomenology of Thermomechanical Treatments
452
12.3.1 Mechanical Behavior During Processing; Creation of Internal Stress; Heat-Setting
452
12.3.2 The Development of Orientation of the Crystalline and Amorphous Substituents
460
12.4 Fiber Structure
460
12.4.1 Basic Structure
460
12.4.2 Crystal Transformation During Heat-Treatment
462
12.4.3 The Oriented Mesophase
462
12.5 Kinetics of Structure Development During Heat-Treatment
464
12.5.1 Effect of Orientation on the Crystallization Rate
464
12.5.2 In Situ Studies
466
12.5.3 Treat and Quench Investigations
466
12.6 Some Final Remarks
472
12.7 References
474
13 Microstructure Characterization
476
13.1 Wide Angle X-Ray Diffraction Analysis of Fibers
476
13.1.1 Introduction
476
13.1.2 Degree of Crystallinity
478
13.1.3 Degree of Orientation
480
13.1.4 Crystallite Size
480
13.1.5 Crystal Structure Determination
482
13.1.6 Aperiodic Scatter from Fibers of Random Copolymers
484
13.1.7 Transesterification in Blends of Copoly(HBA/HNA)
488
13.1.8 Non-Linearity and Distortions
490
13.1.9 References
492
13.2 Small-Angle Scattering
494
13.2.1 Introduction
494
13.2.2 Characteristics of SAS
496
13.2.3 Instrumentation
498
13.2.4 Data Analysis
499
13.2.5 Applications
504
13.2.6 Concluding Remark
511
13.2.7 References
511
13.3 Density, Birefringence, and Polarized Fluorescence
512
13.3.1 Crystallinity from Density
512
13.3.2 Molecular Orientation from Birefringence
514
13.3.3 Molecular Orientation from Polarized Fluorescence
516
13.3.4 References
524
13.4 Spectroscopic Methods: Infrared, Raman, and Nuclear Magnetic Resonance
526
13.4.1 Introduction
526
13.4.2 Infrared
528
13.4.3 Raman
532
13.4.4 Nuclear Magnetic Resonance
534
13.4.5 References
538
14 Fiber Formation and the Science of Complexity
540
14.1 Introduction
540
14.2 A Historical Account of Structural Complexity
542
14.2.1 The Early Fringed Micelle Models
542
14.2.2 The Common Working Model
548
14.2.3 Alternative Continuous Models
552
14.2.4 Other Complexities
554
14.3 The Science of Complexity
556
14.3.1 Far-from-Equilibrium
556
14.3.2 Characterizing Structure: Computer Graphics
556
14.3.3 Polymer Dynamics
558
14.3.4 Fractals
560
14.3.5 Kinetics of Nonhomogeneous Processes
560
14.3.6 Nonlinear Irreversible Thermodynamics
562
14.3.7 Chaos Theory
562
14.4 The Possible Role of Quantum Theory
564
14.4.1 Quantum Effects
564
14.4.2 Melt-Spun Fiber Formation
566
14.4.3 Clusters and Quantized Energy Levels
566
14.5 Conclusion: Scientific and Engineering Opportunity
568
14.6 References
570
Index
573
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