Prediction of polymer properties / Jozef Bicerano.

Format:

Book

Author/Creator:

Bicerano, Jozef, 1952-

Contributor:

Rosengarten Family Fund.

Series:

Plastics engineering (Marcel Dekker, Inc.) ; 65.

Plastics engineering ; 65

Language:

English

Subjects (All):

Polymers.

Physical Description:

xviii, 756 pages, 4 unnumbered pages of plates : illustrations (some color) ; 26 cm.

Edition:

Third edition, revised and expanded.

Place of Publication:

New York : Marcel Dekker, [2002]

Summary:

Highlighting a broad range multiscale modeling and methods for anticipating the morphologies and the properties of interfaces and multiphase materials, this reference covers the methodology of predicting polymer properties and its potential application to a wider variety of polymer types than previously thought possible. A comprehensive source, the book features discussions of the interplay between thermodynamic and kinetic factors in multiphase materials, analytical and numerical methods for predicting thermoelastic and transport properties of multiphase materials, mechanical properties under large deformation, and influence of interfaces via simulations.

Contents:

A. Properties of polymers 1

B. Group contribution techniques 4

1. Basic technique 4

2. An extension 6

C. Topological technique 7

1. Topology and geometry 7

2. Graph theory and connectivity indices 8

3. Nature and scope of the new approach 9

D. Interconversion between mole, weight and volume fractions 15

E. Outline of the remaining chapters of this book 16

Chapter 2. Topological Method for Structure-Property Correlations 22

A. Review of connectivity index calculations for simple molecules 22

B. Extension of connectivity index calculations to polymers 27

C. General forms of the correlations in terms of connectivity indices 46

D. Backbone and side group portions of the connectivity indices 51

E. Shortest path across the backbone of a polymeric repeat unit 54

F. Extensions for the calculation of some conformation-related properties 55

Chapter 3. Volumetric Properties 57

1. Definitions and phenomenology 57

2. Simple empirical relationships 61

3. Synopsis of further treatment of volumetric properties 65

B. Correlation for the van der Waals volume 66

1. Development of the correlation 66

2. Nature of the correction terms used in the correlations 74

3. Examples of the predictive use of the correlation 77

C. Correlation for the molar volume at room temperature 78

D. Final equations for temperature dependences of volumetric properties 86

2. Polymers with T[subscript g greater than or equal]298K 87

3. Polymers with T[subscript g]<298K 88

E. Pressure-volume-temperature relationships 88

F. Effects of crystallinity 95

Chapter 4. Thermodynamic Properties 102

1. Thermophysical properties 102

2. Thermodynamic properties 103

3. Heat capacity 106

B. Improvements in the ability to predict the heat capacities of polymers 110

C. Rotational degrees of freedom of the backbone and the side groups 112

D. Correlation for the heat capacity of "solid" polymers at room temperature 115

E. Correlation for the heat capacity of "liquid" polymers at room temperature 120

F. Correlation for the change in the heat capacity at the glass transition 126

G. Equations for thermodynamic properties as functions of temperature 132

Chapter 5. Cohesive Energy and Solubility Parameter 135

1. Cohesive energy 135

2. Components of the cohesive energy 136

3. Solubility parameter 137

4. Components of the solubility parameter 142

5. Improvements in the ability to predict the cohesive energies and solubility parameters of polymers 144

B. Correlation for the Fedors-type cohesive energy 146

C. Correlation for the van Krevelen-type cohesive energy 151

D. Solubility parameter calculations 158

E. Correlation for dispersion component of the molar attraction constant 162

Chapter 6. Transition and Relaxation Temperatures 169

1. Operational definition of the glass transition 169

2. Practical importance and common methods for measurement of T[subscript g] 170

3. Key physical aspects of the glass transition 173

4. Fundamental theoretical considerations concerning the glass transition 174

5. Quantitative structure-property relationships for T[subscript g] 175

6. Detailed simulations of the glass transition 177

7. Comprehensive list of factors determining T[subscript g] 179

8. Outline of remainder of this chapter 182

B. Correlation for the glass transition temperature 182

2. The structural parameters 187

3. The correlation 198

C. Effects of number-average molecular weight 211

D. Effects of plasticization 217

E. Effects of crosslinking 219

1. A correlation 219

2. Other developments 226

F. Effects of tacticity 228

G. Secondary relaxations 231

H. Crystalline melting temperature 234

1. Homopolymers 234

2. Copolymers and crosslinked polymers 239

I. T[subscript m]/T[subscript g] as indicator of intrinsic crystallizability 241

J. Roles of T[subscript g] and T[subscript m] in determining the crystallization kinetics 245

2. Overall rate for isothermal crystallization 245

3. Overall rate for non-isothermal crystallization 248

4. Nucleation 249

5. Isothermal crystal growth rate from existing nuclei 252

Chapter 7. Surface Tension and Interfacial Tension 261

A. Surface tension 261

1. Total surface tension 261

2. Components of surface tension 266

B. Interfacial tension 269

C. Adhesion 272

D. Improvements in the ability to predict surface tension and interfacial tension 273

E. Approximate "master curve" as a function of reduced temperature 274

F. Correlation for the molar parachor 276

G. Frontiers of interfacial modeling 283

Chapter 8. Optical Properties 292

1. Types of optical properties 292

2. Refractive index and molar refraction 293

3. Optical losses 296

4. Stress-optic coefficient 298

B. Improvements in the ability to predict the refractive indices of polymers 301

C. Correlation for the refractive index at room temperature 302

D. Example of application: specific refractive index increments of solutions 310

E. Calculation of the molar refraction 317

Chapter 9. Electrical Properties 324

B. Correlation for the dielectric constant at room temperature 330

C. Calculation of the molar polarization 336

D. Calculation of the effective dipole moment 339

E. Dissipation factor 343

F. Dielectric strength 353

Chapter 10. Magnetic Properties 358

B. Correlation for the molar diamagnetic susceptibility 360

Chapter 11. Mechanical Properties 368

A. Stress-strain behavior of polymers 368

B. Small-strain behavior: moduli, compliances, and Poisson's ratio 371

1. Definitions and phenomenology 371

2. Structure-property relationships for glassy polymers 375

b. Correlations by Seitz for the elastic moduli 375

c. Bulk modulus via molar Rao function 379

d. Shear modulus via molar Hartmann function 386

e. Thermosets 393

3. Structure-property relationships for rubbery polymers 394

a. Shear modulus 394

b. Bulk modulus and Young's modulus 398

4. Effects of anisotropy (orientation) 400

C. Large-strain behavior: failure mechanisms 401

1. Phenomenology 401

a. General mechanisms 401

b. Toughening by incorporating another phase 411

2. Structure-property relationships for the brittle fracture stress 414

3. Structure-property relationships for the yield stress of thermoplastics 416

4. Attempts to model rate dependence of yield stress of thermoplastics 419

5. Structure-property relationships for the crazing stress 421

6. Stress-strain curves of elastomers 424

7. Ductile thermoplastics at large extension ratios 431

8. Thermoset resins 433

b. Yield stress 436

c. Fracture toughness 437

d. Residual stresses 441

9. Effects of anisotropy (orientation) 444

D. Creep, stress relaxation, fatigue and durability 445

E. Improvements in the ability to predict the mechanical properties 453

Chapter 12. Properties of Polymers in Dilute Solutions 464

2. Steric hindrance parameter 466

3. Characteristic ratio 467

4. Persistence length 468

5. Radius of gyration 469

6. Statistical chain (Kuhn) segment length 470

7. Intrinsic viscosity under theta conditions 471

8. Intrinsic viscosity away from theta conditions 473

9. Solution viscosity at small but finite concentrations 478

B. Correlation for the steric hindrance parameter 482

1. Definitions of the fitting variables 482

2. Development of the correlation 483

C. Calculation of the characteristic ratio 488

D. Correlation for the molar stiffness function 491

Chapter 13. Shear Viscosity 499

B. Dependence of melt zero-shear viscosity on average molecular weight 502

1. Dependence on critical molecular weight 502

2. A correlation for the critical molecular weight 503

3. Alternative correlation for critical molecular weight 504

C. Dependence of melt zero-shear viscosity on temperature 505

1. General

relationships 505

2. Estimation of E[subscript [eta infinity] without using group contributions 508

D. Dependence of melt zero-shear viscosity on hydrostatic pressure 519

E. Melt zero-shear viscosity: summary, examples and possible refinements 520

F. Combined effects of shear rate and polydispersity on melt viscosity 525

G. Zero-shear viscosity of concentrated polymer solutions 528

H. Shear viscosity of dispersions of solid particles in fluids 532

Chapter 14. Thermal Conductivity and Thermal Diffusivity 543

2. Temperature dependence of the thermal conductivities of amorphous polymers 546

3. Thermal conductivities of amorphous polymers at room temperature 548

4. Improvements in the ability to predict the thermal conductivities of polymers 549

B. Direct correlation for the thermal conductivity at room temperature 550

Chapter 15. Transport of Small Penetrant Molecules 555

1. Definitions and major industrial applications 555

2. The solution-diffusion mechanism 556

3. Theories, simulations and empirical correlations 561

B. Correlations for the permeability at room temperature 564

Chapter 16. Thermal Stability 576

2. Measurement of thermal and thermooxidative stability 576

3. Mechanisms of weight loss during degradation 578

4. Effects of structure on thermal and thermooxidative stability 580

a. Qualitative summary of trends 580

b. Reactive molecular dynamics simulations 581

c. Quantitative structure-property relationships 583

B. Correlation for the molar thermal decomposition function 585

Chapter 17. Extensions, Generalizations, Shortcuts, and Possible Directions for Future Work 598

B. Examples of designer correlations 600

1. Glass transition temperatures of a family of polyimides 600

2. Glass transition temperatures of polyesters 601

3. Fedors-type cohesive energies of hydrocarbon polymers 603

4. Glass transition temperatures of hydrogenated styrenic polymers 607

C. Combination of new correlations and group contributions 608

1. Calculation of group contributions from the new correlations 608

2. Combined use of new correlations and group contributions 611

D. Calculation of the properties of alternating copolymers 612

E. Calculation of the properties of random copolymers 614

F. A software package implementing the key correlations 617

G. Utilization to provide input parameters for other types of methods 621

H. Possible directions for future work 622

Chapter 18. Detailed Examples 627

B. Polystyrene 627

C. Random copolymers of styrene and oxytrimethylene 641

Chapter 19. Morphologies of Multiphase Materials 649

A. Materials and morphologies 649

B. Interplay between thermodynamic and kinetic factors 655

C. Prediction of morphologies 657

1. Introductory remarks 657

2. Methods and examples of their use 657

3. Common themes 668

Chapter 20. Properties of Multiphase Materials 675

B. Analytical expressions 676

1. Thermoelastic properties 676

2. Transport properties 689

C. Numerical simulations 691

1. Thermoelastic and transport properties 691

2. Mechanical properties under large deformation 694

a. Overview of various methods 694

b. Understanding the influence of interfaces via simulations 696

A. Terms starting with a lower-case letter of the Latin alphabet 706

B. Terms starting with a capital letter of the Latin alphabet 710

C. Terms starting with a lower-case letter of the Greek alphabet 718

D. Terms starting with a capital letter of the Greek alphabet 722

Appendix Repeat Unit Molecular Weights 724.

Notes:

Includes bibliographical references and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Rosengarten Family Fund.

ISBN:

0824708210

OCLC:

49942235