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Sebastião V. Canevarolo Jr.
Polymer Science
A Textbook for Engineers and Technologists
Contents
14
Preface
8
About the Author
10
Foreword
12
1 General Introduction
26
1.1 History
26
1.2 Polymer Concept
30
1.2.1 Reactive Double Bonds
31
1.2.2 Reactive Functional Groups
32
1.3 Terminology
32
1.4 Sources of Raw Materials
33
1.4.1 Natural Products
33
1.4.2 Mineral Coal
34
1.4.3 Petroleum
35
1.5 Problems
36
2 Polymer Molecular Structure
38
2.1 Molecular Forces in Polymers
38
2.1.1 Primary or Intramolecular Bonds
38
2.1.1.1 Ionic or Electrovalent Bonds
38
2.1.1.2 Coordinate Bonds
39
2.1.1.3 Metallic Bonds
39
2.1.1.4 Covalent Bonds
39
2.1.2 Secondary or Intermolecular Bonds
41
2.1.2.1 Van der Waals Forces
42
2.1.2.2 Hydrogen Bonds
44
2.1.3 Summary
46
2.2 Monomer Functionality
46
2.3 Types of Chains
48
2.3.1 Linear Chain
48
2.3.2 Branched Chain
49
2.3.2.1 Random Chain Architecture
49
2.3.2.2 Star or Radial Chain Architecture
49
2.3.2.3 Comb Chain Architecture
50
2.3.3 Cross-linked Chain
50
2.4 Copolymer
52
2.4.1 Random Copolymer
52
2.4.2 Alternating Copolymer
52
2.4.3 Block Copolymer
53
2.4.4 Graft Copolymer
53
2.5 Classification of Polymers
54
2.5.1 Chemical Structure
54
2.5.1.1 Carbon Chain Polymers
55
2.5.1.2 Heterogeneous Chain Polymers
59
2.5.2 Method of Preparation
62
2.5.2.1 Addition Polymers
62
2.5.2.2 Condensation Polymers
62
2.5.3 Mechanical Behavior
63
2.5.3.1 Plastics
63
2.5.3.2 Elastomers
64
2.5.3.3 Fibers
65
2.5.4 Mechanical Performance
65
2.5.5 Commodity Thermoplastics
65
2.5.6 Special Thermoplastics
65
2.5.7 Engineering Thermoplastics
65
2.5.8 Special Engineering Thermoplastics
66
2.6 Configuration of Polymer Chains
66
2.6.1 Polymer Chaining
66
2.6.1.1 Head-to-Tail Chaining
67
2.6.1.2 Head-to-Head (or Tail-to-Tail) Chaining
67
2.6.1.3 Mixed Chaining
67
2.6.2 Isomerism in Dienes
68
2.6.3 Tacticity
71
2.6.3.1 Isotactic Polymer
71
2.6.3.2 Syndiotactic Polymer
71
2.6.3.3 Atactic Polymer
72
2.7 Conformation of Polymer Chains
73
2.7.1 Random Coil
74
2.7.2 Planar Zig-Zag
75
2.7.3 Helical
76
2.7.4 Mnemonic Rule
77
2.8 Problems
78
3 Polymers in Solution
80
3.1 Technological Importance
80
3.2 Conformation of the Polymer Chain in Solution
80
3.2.1 Free Joined Chain Model
81
3.2.2 Free Tetrahedral Rotation Chain Model
82
3.2.3 Restricted Movement Chain Model
83
3.2.4 Characteristic Ratio
84
3.2.5 Expansion Factor
86
3.3 Theta Condition
86
3.4 The Excluded Volume
90
3.5 Polymer Solubility
93
3.5.1 Basic (Empirical) Rules of Polymer Solubility
94
3.5.2 Effect of Polymer Chain Type on Solubility
94
3.5.3 Cohesive Energy Density in Polymers, CED
95
3.5.4 Hildebrand Solubility Parameter
96
3.5.5 Generalized or Hansen Solubility Parameter
97
3.5.6 Methods for Determining the Solubility Parameter
105
3.5.6.1 Molar Attraction Constant, G
105
3.5.6.2 Solvent Swelling
106
3.5.7 Polymer Fractionation
106
3.5.7.1 Addition of a Non-Solvent
107
3.5.7.2 Evaporation of the Solvent
107
3.5.7.3 Temperature Reduction
107
3.6 Problems
113
4 Polymer Solid-State Morphology
114
4.1 Introduction
114
4.2 Morphological Models of Polymer Crystallization
115
4.2.1 Fringed Micelle Model
115
4.2.2 Folded Chains, Lamellae, or Single Crystal Model
116
4.3 Molecular Chain Packing
118
4.4 Crystalline Structures Derived from the Crystallization Process
120
4.4.1 Spherulitic Crystallization Structure
120
4.4.2 Shish-Kebab Crystallization Structure
123
4.5 Interlamellar Links
124
4.6 Unit Cells of Some Semi-Crystalline Polymers
125
4.6.1 Polyethylene (PE)
125
4.6.2 Polypropylene (PP)
128
4.6.3 Polyhexamethylene Adipamide (Nylon 6,6)
129
4.6.4 Polyethylene Terephthalate (PET)
130
4.7 Crystallinity Degree
131
4.7.1 Determination of the Degree of Crystallinity from the Specific Volume
132
4.7.2 Determination of the Degree of Crystallinity from the Density
133
4.7.3 Determination of the Degree of Crystallinity from the Melt Enthalpy
136
4.7.4 Determination of the Degree of Crystallinity from Specific Heat
138
4.8 Factors That Alter the Degree of Crystallinity
139
4.8.1 Polymer Structural Factors
139
4.8.1.1 Chain Linearity
139
4.8.1.2 Tacticity
139
4.8.1.3 Side Chain Group
139
4.8.1.4 Configuration around Double Bonds
140
4.8.1.5 Polarity
140
4.8.1.6 Stiffness or Flexibility of the Main Chain
141
4.8.1.7 Copolymerization
141
4.8.2 External Factors
141
4.8.2.1 Impurities and Additives
141
4.8.2.2 Nucleating and Clarifying Agents
142
4.8.2.3 Polymeric Second Phase
142
4.8.3 Processing Conditions
142
4.8.3.1 Shear Rate
142
4.8.3.2 Cooling Rate
143
4.9 Problems
143
5 Polymer Synthesis
144
5.1 Introduction
144
5.2 Classification of the Polymerization Processes
144
5.2.1 Number of Monomers
144
5.2.2 Type of Chemical Reaction
145
5.2.3 Polymerization Kinetics
145
5.2.4 Type of Physical Arrangement Methods
145
5.3 Step Polymerization
146
5.3.1 Characteristics of Step Polymerization
146
5.3.2 Some Factors Affecting Step Polymerization
147
5.3.2.1 Reaction Time and Temperature
147
5.3.2.2 Catalyst
147
5.3.2.3 Non-Equimolar Addition of the Reagents
147
5.3.2.4 Functionality of the Third Reagent
148
5.3.2.5 Ways of Stopping Step Polymerization
148
5.4 Chain Polymerization
149
5.4.1 Free-Radical Chain Polymerization
150
5.4.1.1 Initiation
150
5.4.1.2 Propagation
151
5.4.1.3 Termination
151
5.4.2 Inhibitors and Retarders
155
5.5 Ionic Polymerization
156
5.5.1 Cationic Polymerization
156
5.5.1.1 Initiation
156
5.5.1.2 Propagation
156
5.5.1.3 Termination
157
5.5.2 Anionic Polymerization
157
5.5.2.1 Initiation
158
5.5.2.2 Propagation
158
5.5.2.3 Termination
158
5.6 Ring-Opening Polymerization
159
5.7 Copolymerization
160
5.8 Methods of Polymerization According to the Physical Arrangement
161
5.8.1 Bulk Polymerization
161
5.8.2 Solution Polymerization
162
5.8.3 Suspension Polymerization
162
5.8.4 Emulsion Polymerization
162
5.9 Degradation
164
5.9.1 Depolymerization
164
5.9.2 Chain Scission
164
5.9.2.1 Nylon Hydrolysis
165
5.9.2.2 Thermo–Mechanical Degradation of Polypropylene
165
5.9.2.3 Thermo–Mechanical Degradation of Polyethylene
167
5.9.3 Loss of Side Groups
168
5.10 Problems
169
6 Polymer Molecular Weight and Distribution
172
6.1 Introduction
172
6.2 Types of Average Molecular Weights
173
6.2.1 Number Average Molecular Weight (?)
173
6.2.2 Weight Average Molecular Weight (?)
174
6.2.3 Viscosity Average Molecular Weight (?)
174
6.2.4 z-Average Molecular Weight (?)
175
6.3 Methods for Measuring Average Molecular Weights
176
6.3.1 Number Average Molecular Weight
176
6.3.1.1 Chain-End Analysis
176
6.3.1.2 Colligative Properties
176
6.3.2 Weight Average Molecular Weight
178
6.3.2.1 Light Scattering
178
6.3.2.2 Ultracentrifugation
179
6.3.3 Viscosity Average Molecular Weight
180
6.3.3.1 Viscosimetry of Dilute Polymer Solutions
180
6.3.4 z-Average Molecular Weight
185
6.4 Molecular Weight Distribution Curve
185
6.4.1 Size Exclusion Chromatography (SEC)
190
6.5 Most Probable Molecular Weight Distribution Function
194
6.5.1 Polycondensation with Linear Chains
194
6.5.2 Chain Polymerization
197
6.5.2.1 Chain Transfer Termination
197
6.5.2.2 Combination Termination
197
6.5.2.3 Polymerization without Termination
197
6.6 Molecular Weight and Chain Length
198
6.7 Molecular Weight Fractioning Principles
201
6.7.1 Precipitation from a Polymer Solution
201
6.7.2 Preparative Size Exclusion Chromatography (Prep-SEC)
202
6.8 Problems
202
7 Polymer Thermal Behavior
204
7.1 Characteristic Transition Temperatures in Polymers
204
7.1.1 Glass Transition Temperature or Tg
204
7.1.2 Crystalline Melting Temperature or Tm
205
7.1.3 Crystallization Temperature or Tc
208
7.1.4 Other Transition Temperatures sub-Tg
209
7.2 Free Volume Theory
210
7.3 Flory’s Theory for the Reduction of the Melt Temperature
213
7.3.1 Effect of the Diluent on Tm
214
7.3.2 Effect of the Polymer Molecular Weight in its Tm
216
7.3.3 Effect of the Comonomer Content in the Copolymer’s Tm
217
7.4 Engineering Polymer Temperatures
217
7.5 Main Experimental Techniques for the Determination of Transition Temperatures
218
7.5.1 Differential Scanning Calorimetry, DSC
218
7.5.2 Dynamic-Mechanical Thermal Analysis, DMTA
221
7.5.3 Vicat and HDT Softening Temperatures
223
7.6 Effect of the Chemical Structure on Tg and Tm
224
7.6.1 Structural Symmetry of the Main Chain
225
7.6.2 Rigidity/Flexibility of the Main Chain
226
7.6.3 Polarity of the Main Chain
228
7.6.4 Steric Effect of the Main Chain Side Group
230
7.6.4.1 Side Group Volume
231
7.6.4.2 Side Group Length
231
7.6.5 Residual Double Bond Isomerism
232
7.6.6 Copolymerization
233
7.6.6.1 Homogeneous, Miscellaneous, or Single-Phase Systems
233
7.6.6.2 Heterogeneous, Immiscible, or Polyphasic Systems
236
7.6.7 Polymer Molecular Weight
238
7.6.8 Branching
240
7.7 Influence of External Factors on Tg and Tm
241
7.8 Summary of the Factors Affecting Crystallinity, Tg, and Tm
242
7.9 Problems
243
8 Polymer Crystallization Kinetics
244
8.1 Crystal Nucleation
244
8.1.1 Nucleation Rate
246
8.2 Crystal Growth
246
8.3 Total Isothermal Crystallization
249
8.4 Avrami’s Isothermal Crystallization Kinetics Theory
250
8.4.1 Measuring Crystallization Kinetics via Dilatometry
251
8.4.2 Measuring Crystallization Kinetics via Differential Scanning Calorimetry (DSC)
254
8.5 Isothermal Crystallization Rate
259
8.6 Equilibrium Melting Temperature
260
8.7 Problems
261
9 Polymer Mechanical Behavior
262
9.1 Introduction
262
9.2 Polymer Viscoelasticity
263
9.2.1 Linear Viscoelasticity Models
264
9.2.1.1 Maxwell Model
266
9.2.1.2 Voigt Model
267
9.2.1.3 Combined Maxwell–Voigt Model
268
9.2.2 Creep and Stress Relaxation
268
9.2.3 Rubber Elasticity
271
9.3 Considerations upon Polymer Mechanical Testing
274
9.3.1 Testing Recording Stress–Strain Curves
274
9.3.2 Testing under Impact
278
9.4 Fracture Characteristics
280
9.4.1 Brittle Fracture Mechanism
280
9.4.2 Ductile Fracture Mechanism in Toughened Systems
281
9.4.2.1 Shear Yielding
281
9.4.2.2 Crazing
282
9.5 Parameters Affecting Polymer Mechanical Behavior
282
9.5.1 Chemical Structure
282
9.5.2 Degree of Crystallinity
283
9.5.3 Molecular Weight
284
9.5.4 Molecular Orientation
285
9.5.4.1 Peterlin Molecular Reorientation Model
285
9.5.4.2 Characterization of Molecular Orientation via Dichroic Ratio in Polarized Infrared
286
9.5.5 Copolymerization
289
9.5.6 Plasticization
289
9.5.7 Elastomer Toughening
292
9.5.8 Fiber Reinforcing
293
9.6 Superposition Principles
294
9.6.1 Boltzmann Stress Superposition Principle
294
9.6.2 Time–Temperature Superposition Principle
295
9.7 Reptation Theory
297
9.8 Polymer Physical States
298
9.9 Physico–Chemical Methods for Polymer Transformation
300
9.9.1 Physical Methods
300
9.9.1.1 Orientation
300
9.9.1.2 Plasticization
301
9.9.1.3 Solubilization
301
9.9.1.4 Foaming
301
9.9.1.5 Reinforcing
302
9.9.1.6 Toughening
302
9.9.2 Chemical Methods
302
9.9.2.1 Mastication
302
9.9.2.2 Cross-linking
303
9.9.2.3 Grafting
303
9.9.2.4 Oxidation
303
9.10 Problems
303
10 Experiments in Polymer Science
306
10.1 Identification of Plastics and Rubbers
306
10.1.1 Objective
306
10.1.2 Introduction
306
10.1.3 Materials
308
10.1.4 Equipment
308
10.1.5 Method
308
10.1.6 Results
309
10.2 Observation of Polymer Solubilization
311
10.2.1 Objective
311
10.2.2 Introduction
311
10.2.3 Materials
312
10.2.4 Equipment
312
10.2.5 Method
312
10.2.6 Results
313
10.2.7 Questions
313
10.3 Observation of the Precipitation of a Polymer Solution
314
10.3.1 Objective
314
10.3.2 Introduction
314
10.3.3 Materials
314
10.3.4 Equipment
315
10.3.5 Method
315
10.3.6 Results
316
10.3.7 Questions
317
10.4 Identification of Polymers by Infrared Absorption Spectroscopy
318
10.4.1 Objective
318
10.4.2 Introduction
318
10.4.3 Materials
321
10.4.4 Equipment
321
10.4.5 Method
321
10.4.6 Results
321
10.4.7 Questions
322
10.5 Characterization of Polymers by Infrared Absorption Spectroscopy
322
10.5.1 Introduction
322
10.5.2 Determination of Cis/Trans/Vinyl Isomer Concentration in Polybutadiene
323
10.5.2.1 Objective
323
10.5.2.2 Materials
323
10.5.2.3 Equipment
323
10.5.2.4 Method
324
10.5.2.5 Results
324
10.5.3 Quantification of the Components in a Binary Polymer Blend
326
10.5.3.1 Objective
326
10.5.3.2 Materials
326
10.5.3.3 Equipment
326
10.5.3.4 Method
326
10.5.3.5 Results
327
10.5.3.6 Questions
329
10.6 Characterization of Polymer Molecular Orientation via the IR Dichroic Ratio
329
10.6.1 Objective
329
10.6.2 Introduction
329
10.6.3 Materials
330
10.6.4 Equipment
330
10.6.5 Method
330
10.6.6 Results
332
10.6.7 Questions
333
10.7 Observation of the Spherulitic Crystallization in Polymers
333
10.7.1 Objective
333
10.7.2 Introduction
333
10.7.3 Materials
334
10.7.4 Equipment
334
10.7.5 Method
334
10.7.6 Results
336
10.7.7 Supplementary Activities
336
10.8 Determination of the Degree of Crystallinity by Density Measurements
338
10.8.1 Objective
338
10.8.2 Introduction
338
10.8.3 Materials
339
10.8.4 Equipment
340
10.8.5 Preparation of the Liquid Mixture Having the Same Density as the Sample
340
10.8.6 Pycnometry
340
10.8.7 Results
341
10.8.8 Questions
343
10.9 Determination of the Degree of Crystallinity by Differential Scanning Calorimetry (DSC)
343
10.9.1 Objective
343
10.9.2 Introduction
343
10.9.3 Materials
344
10.9.4 Equipment
344
10.9.5 Method
344
10.9.6 Results
345
10.9.7 Questions
345
10.10 Free-Radical Bulk Polymerization of Methyl Methacrylate
346
10.10.1 Objective
346
10.10.2 Introduction
346
10.10.3 Materials
347
10.10.4 Equipment
347
10.10.5 Method
347
10.10.6 Results
348
10.10.7 Questions
348
10.10.8 Supplementary Activities
348
10.11 Determination of the Viscosity Average Molecular Weight
349
10.11.1 Objective
349
10.11.2 Introduction
349
10.11.3 Materials
350
10.11.4 Equipment
350
10.11.5 Method
350
10.11.6 Results
352
10.11.7 Questions
353
10.12 Determination of the Melt Flow Index (MFI)
353
10.12.1 Objective
353
10.12.2 Introduction
354
10.12.3 Materials
354
10.12.4 Equipment
354
10.12.5 Method
355
10.12.6 Results
356
10.12.7 Questions
356
10.13 Determination of Vicat Softening Temperature
356
10.13.1 Objective
356
10.13.2 Introduction
356
10.13.3 Materials
357
10.13.4 Equipment
357
10.13.5 Method
358
10.13.6 Results
358
10.13.7 Questions
359
10.14 Determination of Cross-linking Density in Vulcanized Rubbers
359
10.14.1 Objective
359
10.14.2 Introduction
359
10.14.3 Materials
360
10.14.4 Equipment
360
10.14.5 Method
360
10.14.6 Results
361
10.14.7 Questions
361
11 Further Reading
362
12 Appendix A
366
12.1 Terminology
366
12.2 Abbreviations
373
13 Appendix B
376
Index
388
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