PROPERTIES OF POLYMERS THEIR CORRELATION WITH CHEMICAL STRUCTURE;

THEIR NUMERICAL ESTIMATION AND PREDICTION FROM ADDITIVE GROUP CONTRIBUTIONS

Third, completely revised edition

By

D.W. VÄN KREVELEN

Professor-Emeritus, University of Technology, Delft, The Netherlands

and

Former President of AKZO Research and Engineering N.V., Arnhem, The Netherlands

ELSEVIER AMSTERDAM - LAUSANNE - N E W YORK - O X F O R D - S H A N N O N - TOKYO

1990

CONTENTS

From the preface to the first edition (1972) vii From the preface to the second edition (1976) ix Preface to the third edition xi Acknowledgements xv

Part I. General introduction: A bird's-eye view of polymer science and engineering

Chapter 1. Polymer properties 3 Approach and Objective 3 Bibliography 5

Chapter 2. Typology of polymers 7 A. Polymer structure 8 B. Molecular mass and molecular mass distribution 16 C. Phase transitions in polymers 22 D. Morphology of solid polymers 29 E. Polymerie liquid crystals 34 F. Multiple component polymer Systems 36 G. Relaxation phenomena 38 Appendix I. Milestones in the history of polymer science 40 Appendix II. Chronological development of commercial polymers 43 Bibliography 45

Chapter 3. Typology of properties 49 A. The coneept "Polymer properties" 49 B. Physical quantities and their units 52 C. Categories of physical quantities 53 D. Dimensionless groups of quantities 54 E. Types of molar properties 57 F. Additive molar funetions 60 Bibliography 66

Part II. Thermophysical properties of polymers

Chapter 4. Volumetrie properties 71

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A. Fundamental quantities of mass and volume 72 B. Standard molar volumes at room temperature (298 K) 76 C. Thermal expansion 88 D. Isothermal compression - Equations of State 101 Bibliography 106

Chapter 5. Calorimetric properties 109 A. Heat capacity 109 B. Latent heat of crystallization and fusion (melting) 118 C. Enthalpy and entropy 123 Bibliography 127

Chapter 6. Transition temperatures 129 A. The glass transition temperature 130 B. The crystalline melting point 151 C. Relationship between glass transition temperature and melting point of

polymers 166 D. Relationship between T , Tm and other transition temperatures 169 E. Transitions in thermotropic liquid crystal polymers 172 Appendix I. Rules of thumb for substituting a H-atom by a group X 180 Appendix IL Similarities and differences between Yg and Ym 182 Bibliography 186

Chapter 7. Cohesive properties and solubility 189 A. Cohesive energy 190 B. Solubility 200 C. Internal pressure 220 Bibliography 224

Chapter 8. Interfacial energy properties 227 A. Surface energy of liquids and melts 228 B. Surface energy of solid polymers 231 C. General expression for the interfacial tension 236 D. Polymer adhesion 239 Bibliography 240

Chapter 9. Limiting viscosity number (intrinsic viscosity) and related properties of very dilute Solutions 243 A. Molecular dimensions of the conformational State 244 B. The limiting viscosity number (intrinsic viscosity) 247 C. Interrelationships of "limiting" diffusive transport quantities 278 Bibliography 282

Part III. Properties of polymers in fields of force

XIX

Chapter 10. Optical properties 287 A. Optical properties in general 287 B. Light refraction 290 C. Reflection 297 D. Birefringence (and optical rotation) 298 E. Light scattering 307 F. Absorption 313 G. Optical appearance properties 313 Bibliography 318

Chapter 11. Electrical properties 321 A. Dielectric polarization 321 B. Static electrification and conductivity 329 C. Ultimate electrical properties 339 Bibliography 340

Chapter 12. Magnetic properties 343 A. Magnetic susceptibility (Magnetic inductive capacity) 343 B. Magnetic resonance 347 Bibliography 363

Chapter 13. Mechanical properties of solid polymers 367 A. Elastic parameters 367 B. Rubber elasticity 384 C. Viscoelasticity 388 D. Ultimate mechanical properties 412 E. Mechanical properties of uniaxially oriented polymers (fibers) 423 Bibliography 435

Chapter 14. Acoustic properties 439 A. Sound propagation and absorption 440 B. Additive molar functions for sound propagation 442 C. Sonic absorption 449 Bibliography 453

Part IV. Transport properties of polymers

Chapter 15. Rheological properties of polymer melts 457 A. Modes of deformation and definition of viscosity 458 B. Newtonian shear viscosity of polymer melts 462 C. Non-Newtonian shear viscosity of polymer melts 474 D. Extensional viscosity of polymer melts 486

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E. Elastic effects in polymer melts 487 F. Rheological properties of liquid crystal polymer melts 491 Appendix I. Flow of polymer melts through narrow tubes and capillaries 493 Appendix II. Analysis of flow in processing Operations 494 Bibliography 497

Chapter 16. Rheological properties of polymer Solutions 499 A. Dilute polymer Solutions 500 B. Concentrated polymer Solutions 505 C. Extensional deformation of polymer Solutions 520 D. Solutions of lyotropic liquid crystal polymers 521 Bibliography 522

Chapter 17. Transport of thermal energy 525 Thermal conductivity 525 , Bibliography 532 Appendix 533

Chapter 18. Properties determining mass transfer in polymeric Systems 535 A. Permeation of simple gases 535 B. Permeations of a more complex nature 561 C. Dissolution of polymers as a case of permeation 577 D. Bibliography 582

Chapter 19. Crystallization and recrystallization 585 A. Crystallinity, nucleation and growth 585 B. Spherulitic crystallization of polymers from the melt 588 C. Induced crystallization of flexible polymeric molecules by pressure and stress 603 D. Extended chain crystallization of flexible polymer chains 609 E. Extended chain crystallization of rigid macromolecules 618

Bibliography 620

Part V. Properties determining the chemical stability and breakdown of polymers

Chapter 20. Thermochemical properties 627 A. Thermodynamics and kinetics 627 B. Calculation of the free enthalpy of reaction from group contributions 629 C. Thermodynamics of free radicals 635 Bibliography 638

Chapter 21. Thermal decomposition 641 A. Thermal degradation 641 B. Char formation 649 C. Kinetics of thermal degradation 652

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Bibliography 653

Chapter 22. Chemical degradation 655 Bibliography 660

Part VI. Polymer properties as an integral concept

Chapter 23. Intrinsic properties in retrospect 663 A. Reference values of intrinsic properties expressed as a function of additive

quantities 664 B. Effect of structural groups on properties 666 C. Dependence of intrinsic properties on process variables 668 D. Outlook 671

Chapter 24. Processing properties 673 A. Classification of processes 673 B. Some important processing properties 674 C. Implementation of processing research 691 Bibliography 692

Chapter 25. Product properties (I): Mechanical behaviour and failure 695 A. Failure mechanisms in polymers 696 B. Deformation properties 698 C. Toughness and endurance 705 D. Hardness 713 E. Friction and wear 716 F. The mechanical shortcomings of homogeneous materials and the need for

composites 719 Bibliography 723

Chapter 26. Product properties (II): Environmental behaviour and failure 725 A. Thermal end use properties 725 B. Flammability of polymers 727 C. Environmental decay of polymers in liquids 736 Bibliography 743

Chapter 27. An illustrative example of end use properties: Article properties of textile products 745 A. Aesthetic properties 745 B. Use or Performance properties 747 C. Maintenance or care properties 753 D. Integral evaluation of fibre polymers, fibres and yarns by the criteria men-

tioned (profile method) 754 Bibliography 756

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Part VII. Comprehensive tables

I. International System of units (SI) 761 II. Survey of conversion factors 763

III. Values of some fundamental constants 773 IV. Physical constants of the most important solvents 774 V Physical properties of the most important polymers 790

VI. Published data on "high Performance" polymers 804 VII. Code Symbols for the most important polymers 808

VIII. Trade names and generic names 811 IX. Survey of group contributions in additive molar quantities 816

Indexation

Symbol index 827 Author index 847 Subject index 861