Tim A. Osswald, Georg Menges
Materials Science of Polymers for Engineers
Preface to the First Edition
8
Preface to the Third Edition
10
1 Introduction
24
1.1 The 6 P’s
24
1.2 General Information
27
1.3 Identification of Polymers
34
1.4 Sustainability – The 6th P
36
References
41
2 Historical Background
42
2.1 From Natural to Synthetic Rubber
42
2.2 Cellulose and the $10,000 Idea
48
2.3 Galalith – The Milk Stone
51
2.4 Leo Baekeland and the Plastics Industry
52
2.5 Herman Mark and the American Polymer Education
55
2.6 Wallace Hume Carothers and Synthetic Polymers
58
2.7 Polyethylene – A Product of Brain and Brawn
60
2.8 The Super Fiber and the Woman Who Invented It
63
2.9 One Last Word – Plastics
65
References
68
3 Structure of Polymers
70
3.1 Macromolecular Structure of Polymers
70
3.2 Molecular Bonds and Inter-Molecular Attraction
71
3.3 Molecular Weight
72
3.4 Conformation and Configuration of Polymer Molecules
77
3.5 Arrangement of Polymer Molecules
80
3.5.1 Thermoplastic Polymers
81
3.5.2 Amorphous Thermoplastics
81
3.5.3 Semi-Crystalline Thermoplastics
83
3.5.4 Thermosets and Cross-Linked Elastomers
93
3.6 Copolymers and Polymer Blends
94
3.7 Polymer Additives
96
3.7.1 Flame Retardants
96
3.7.2 Stabilizers
98
3.7.3 Antistatic Agents
99
3.7.4 Fillers
99
3.7.5 Blowing Agents
100
References
103
4 Thermal Properties of Polymers
104
4.1 Material Properties
106
4.1.1 Thermal Conductivity
106
4.1.2 Specific Heat
112
4.1.3 Density
114
4.1.4 Thermal Diffusivity
117
4.1.5 Linear Coefficient of Thermal Expansion
118
4.1.6 Thermal Penetration
119
4.1.7 Glass Transition Temperature
120
4.1.8 Melting Temperature
120
4.2 Measuring Thermal Data
120
4.2.1 Differential Thermal Analysis (DTA)
121
4.2.2 Differential Scanning Calorimeter (DSC)
122
4.2.3 Thermomechanical Analysis (TMA)
124
4.2.4 Thermogravimetry (TGA)
125
4.2.5 Density Measurements
126
References
130
5 Rheology of Polymer Melts
132
5.1 Introduction
132
5.1.1 Continuum Mechanics
132
5.1.2 The Generalized Newtonian Fluid
134
5.1.3 Normal Stresses in Shear Flow
136
5.1.4 Deborah Number
137
5.2 Viscous Flow Models
140
5.2.1 The Power Law Model
140
5.2.2 The Bird-Carreau-Yasuda Model
142
5.2.3 The Bingham Fluid
143
5.2.4 Elongational Viscosity
143
5.2.5 Rheology of Curing Thermosets
146
5.2.6 Suspension Rheology
148
5.3 Simplified Flow Models Common in Polymer Processing
150
5.3.1 Simple Shear Flow
150
5.3.2 Pressure Flow Through a Slit
151
5.3.3 Pressure Flow through a Tube – Hagen-Poiseuille Flow
151
5.3.4 Couette Flow
152
5.4 Viscoelastic Flow Models
153
5.4.1 Differential Viscoelastic Models
153
5.4.2 Integral Viscoelastic Models
156
5.5 Rheometry
159
5.5.1 The Melt Flow Indexer
160
5.5.2 The Capillary Viscometer
160
5.5.3 Computing Viscosity Using the Bagley and Weissenberg-Rabinowitsch Equations
162
5.5.4 Viscosity Approximation Using the Representative Viscosity Method
163
5.5.5 The Cone-Plate Rheometer
164
5.5.6 The Couette Rheometer
165
5.5.7 Extensional Rheometry
166
5.6 Surface Tension
169
References
178
6 Introduction to Processing
184
6.1 Extrusion
184
6.1.1 The Plasticating Extruder
187
6.1.1.1 The Solids Conveying Zone
189
6.1.1.2 The Melting Zone
192
6.1.1.3 The Metering Zone
195
6.1.2 Extrusion Dies
196
6.1.2.1 Sheeting Dies
197
6.1.2.2 Tubular Dies
198
6.2 Mixing Processes
200
6.2.1 Distributive Mixing
202
6.2.1.1 Effect of Orientation
203
6.2.2 Dispersive Mixing
205
6.2.2.1 Break-Up of Particulate Agglomerates
205
6.2.2.2 Break-Up of Fluid Droplets
207
6.2.3 Mixing Devices
210
6.2.3.1 Static Mixers
211
6.2.3.2 Banbury Mixer
211
6.2.3.3 Mixing in Single Screw Extruders
213
6.2.3.4 Co-Kneader
215
6.2.3.5 Twin Screw Extruders
216
6.2.4 Energy Consumption During Mixing
219
6.2.5 Mixing Quality and Efficiency
220
6.2.6 Plasticization
222
6.3 Injection Molding
227
6.3.1 The Injection Molding Cycle
228
6.3.2 The Injection Molding Machine
231
6.3.2.1 The Plasticating and Injection Unit
231
6.3.2.2 The Clamping Unit
232
6.3.2.3 The Mold Cavity
234
6.4 Special Injection Molding Processes
237
6.4.1 Multi-Component Injection Molding
237
6.4.2 Co-Injection Molding
239
6.4.3 Gas-Assisted Injection Molding (GAIM)
240
6.4.4 Injection-Compression Molding
242
6.4.5 Reaction Injection Molding (RIM)
243
6.4.6 Liquid Silicone Rubber Injection Molding
246
6.5 Secondary Shaping
247
6.5.1 Fiber Spinning
247
6.5.2 Film Production
248
6.5.2.1 Cast Film Extrusion
248
6.5.2.2 Film Blowing
249
6.5.3 Blow Molding
251
6.5.3.1 Extrusion Blow Molding
251
6.5.3.2 Injection Blow Molding
253
6.5.3.3 Thermoforming
254
6.6 Calendering
256
6.7 Coating
259
6.8 Compression Molding
261
6.9 Foaming
263
6.10 Rotational Molding
265
6.11 Computer Simulation in Polymer Processing
266
6.11.1 Mold Filling Simulation
267
6.11.2 Orientation Predictions
269
6.11.3 Shrinkage and Warpage Predictions
270
References
281
7 Anisotropy Development During Processing
284
7.1 Orientation in the Final Part
284
7.1.1 Processing Thermoplastic Polymers
284
7.1.2 Processing Thermoset Polymers
292
7.2 Predicting Orientation in the Final Part
296
7.2.1 Planar Orientation Distribution Function
297
7.2.2 Single Particle Motion
299
7.2.3 Jeffery’s Model
300
7.2.4 Folgar-Tucker Model
301
7.2.5 Tensor Representation of Fiber Orientation
302
7.2.5.1 Predicting Orientation in Complex Parts Using Computer Simulation
303
7.3 Fiber Damage
308
References
314
8 Solidification of Polymers
316
8.1 Solidification of Thermoplastics
316
8.1.1 Thermodynamics During Cooling
316
8.1.2 Morphological Structure
320
8.1.3 Crystallization
321
8.1.4 Heat Transfer During Solidification
324
8.2 Solidification of Thermosets
328
8.2.1 Curing Reaction
329
8.2.2 Cure Kinetics
330
8.2.3 Heat Transfer During Cure
335
8.3 Residual Stresses and Warpage of Polymeric Parts
337
8.3.1 Residual Stress Models
340
8.3.1.1 Residual Stress Model Without Phase Change Effects
342
8.3.1.2 Model to Predict Residual Stresses with Phase Change Effects
343
8.3.2 Other Simple Models to Predict Residual Stresses and Warpage
345
8.3.2.1 Uneven Mold Temperature
347
8.3.2.2 Residual Stress in a Thin Thermoset Part
348
8.3.2.3 Anisotropy Induced Curvature Change
349
8.3.3 Predicting Warpage in Actual Parts
350
References
357
9 Mechanical Behavior of Polymers
362
9.1 Basic Concepts of Stress and Strain
362
9.1.1 Plane Stress
363
9.1.2 Plane Strain
364
9.2 Viscoelastic Behavior of Polymers
364
9.2.1 Stress Relaxation Test
365
9.2.2 Time-Temperature Superposition (WLF-Equation)
367
9.2.3 The Boltzmann Superposition Principle
368
9.3 Applying Linear Viscoelasticity to Describe the Behavior of Polymers
369
9.3.1 The Maxwell Model
370
9.3.2 Kelvin Model
371
9.3.3 Jeffrey Model
373
9.3.4 Standard Linear Solid Model
375
9.3.5 The Generalized Maxwell Model
377
9.4 The Short-Term Tensile Test
382
9.4.1 Rubber Elasticity
383
9.4.2 The Tensile Test and Thermoplastic Polymers
388
9.5 Creep Test
395
9.5.1 Isochronous and Isometric Creep Plots
399
9.6 Dynamic Mechanical Tests
400
9.6.1 Torsion Pendulum
400
9.6.2 Sinusoidal Oscillatory Test
404
9.7 Effects of Structure and Composition on Mechanical Properties
406
9.7.1 Amorphous Thermoplastics
406
9.7.2 Semi-Crystalline Thermoplastics
409
9.7.3 Oriented Thermoplastics
411
9.7.4 Crosslinked Polymers
416
9.8 Mechanical Behavior of Filled and Reinforced Polymers
418
9.8.1 Anisotropic Strain-Stress Relation
420
9.8.2 Aligned Fiber Reinforced Composite Laminates
421
9.8.3 Transformation of Fiber Reinforced Composite Laminate Properties
423
9.8.4 Reinforced Composite Laminates with a Fiber Orientation Distribution Function
425
9.9 Strength Stability Under Heat
426
References
442
10 Failure and Damage of Polymers
444
10.1 Fracture Mechanics
444
10.1.1 Fracture Predictions Based on the Stress Intensity Factor
445
10.1.2 Fracture Predictions Based on an Energy Balance
447
10.1.3 Linear Viscoelastic Fracture Predictions Based on J-Integrals
449
10.2 Short-Term Tensile Strength
451
10.2.1 Brittle Failure
451
10.2.2 Ductile Failure
455
10.2.3 Failure of Highly Filled Systems or Composites
458
10.3 Impact Strength
461
10.3.1 Impact Test Methods
467
10.3.2 Fracture Mechanics Analysis of Impact Failure
471
10.4 Creep Rupture
476
10.4.1 Creep Rupture Tests
477
10.4.2 Fracture Mechanics Analysis of Creep Rupture
480
10.5 Fatigue
480
10.5.1 Fatigue Test Methods
481
10.5.2 Fracture Mechanics Analysis of Fatigue Failure
489
10.6 Friction and Wear
491
10.7 Stability of Polymer Structures
494
10.8 Environmental Effects on Polymer Failure
496
10.8.1 Weathering
496
10.8.2 Chemical Degradation
501
10.8.3 Thermal Degradation of Polymers
503
References
507
11 Electrical Properties of Polymers
510
11.1 Dielectric Behavior
510
11.1.1 Dielectric Coefficient
510
11.1.2 Mechanisms of Dielectrical Polarization
514
11.1.3 Dielectric Dissipation Factor
517
11.1.4 Implications of Electrical and Thermal Loss in a Dielectric
520
11.2 Electric Conductivity
521
11.2.1 Electric Resistance
521
11.2.2 Physical Causes of Volume Conductivity
522
11.3 Application Problems
525
11.3.1 Electric Breakdown
525
11.3.2 Electrostatic Charge
529
11.3.3 Electrets
530
11.3.4 Electromagnetic Interference Shielding (EMI Shielding)
530
11.4 Magnetic Properties
531
11.4.1 Magnetizability
531
11.4.2 Magnetic Resonance
531
References
532
12 Optical Properties of Polymers
534
12.1 Index of Refraction
534
12.2 Photoelasticity and Birefringence
537
12.3 Transparency, Reflection, Absorption, and Transmittance
541
12.4 Gloss
547
12.5 Color
548
12.6 Infrared Spectroscopy
552
12.7 Infrared Pyrometry
553
12.8 Heating with Infrared Radiation
555
References
557
13 Permeability Properties of Polymers
558
13.1 Sorption
558
13.2 Diffusion and Permeation
560
13.3 Measuring S, D, and P
565
13.4 Corrosion of Polymers and Cracking [5]
566
13.5 Diffusion of Polymer Molecules and Self-diffusion
569
References
569
14 Acoustic Properties of Polymers
570
14.1 Speed of Sound
570
14.2 Sound Reflection
572
14.3 Sound Absorption
573
References
574
Appendix
576
Appendix I
577
Appendix II
585
Appendix III
586
Appendix IV – Balance Equations
605
Continuity Equation
605
Energy Equation for a Newtonian Fluid
605
Momentum Balance
606
Momentum Equation in Terms of t
606
Navier-Stokes Equation
606
Index
608
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