INTEGRATION OF FUNDAMENTAL POLYMER SCIENCE AND TECHNOLOGY

The proceedings of an international meeting on polymer science and technology held at Rolduc Abbey, Limburg, The Netherlands, 14-18 April

1985

INTEGRA TI ON OF FUNDAMENTAL

POLYMER SCIENCE AND TECHNOLOGY

Edited by

L. A. KLEINTJENS

DSM Central Research, Geleen, The Netherlands

and

P. J. LEMSTRA

Eindhoven University of Technology, The Netherlands

ELSEVIER APPLIED SCIENCE PUBLISHERS LONDON and NEW YORK

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WITH 43 TABLES AND 359 ILLUSTRATIONS

© ELSEVIER APPLIED SCIENCE PUBLISHERS LTD 1986 Softcover reprint of the hardcover 1st edition 1986

British Library Cataloguing in Publication Data

Integration of fundamental polymer science and technology. I. Polymers and polymerization I. Kleintjens, L. A. II. Lemstra, P. J. 547.7 QD381

Library of Congress Cataloging in Publication Data

Integration of fundamental polymer science and technology.

Bibliography: p. Includes index. I. Polymers and polymerization-Congresses.

I. Kleintjens. L. A. II. Lemstra. P. A. TP108l.l56 1986 668.9 85-27465

ISBN-13: 978-94-010-8359-1 e-ISBN-13: 978-94-009-4185-4

DOl: 10.1007/978-94-009-4185-4

The selection and presentation of material and the opinions expressed in this publication are the sole responsibility of the authors concerned.

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v

FOREWORD

'Integration of Fundamental Polymer Science and Technology' is a theme that admits of countless variations. It is admirably exemplified by the scientific work of R. Koningsveld and C. G. Vonk, in whose honour this meeting was organized. The interplay between 'pure' and 'applied' is of course not confined to any particular subdiscipline of chemistry or physics (witness the name IUPAC and IUPAP) but is perhaps rarely so intimate and inevitable as in the macromolecular area. The historical sequence may vary: when the first synthetic dye was prepared by Perkin, considerable knowledge of the molecular structure was also at hand; but polymeric materials, both natural and synthetic, had achieved a fair practical technology long before their macromolecular character was appreciated or established.

Such historical records have sometimes led to differences of opinion as to whether the pure or the applied arm should deserve the first place of honour. The Harvard physiologist Henderson, as quoted in Walter Moore's Physical Chemistry, averred that 'Science owes more to the steam engine than the steam engine owes to Science'. On the other hand, few would dispute the proposition that nuclear power production could scarcely have preceded the laboratory observations of Hahn and Strassmann on uranium fission. Whatever history may suggest, an effective and continuous working relationship must recognize the essential contributions, if not always the completely smooth meshing, of both extremes. An outsider gains the impression that this principle must have long been firmly recognized at DSM in order to have enabled Koningsveld and Vonk to make the broadly impressive contributions that are here recognized. The vagaries of the market-place have led in many industrial establishments to painful fluctuations in fundamental research effort, generally to no useful ultimate purpose. The papers assembled in this volume could, in our view, achieve no more desirable goal than to create strong impressions that might contribute to the stabilization of long-range research programmes.

(As a frivolous aside, we may recall that a similar question, regarding the relative importance ofwords and music, has long plagued opera-lovers and has inspired some pithy replies. When asked whether text or musical score

VI

was more important to his light operas with Sullivan, W. S. Gilbert answered by the single word 'Yes!' Actually, the science/technology dualism itself has been musically addressed by the composer Koningsveld in the second movement, 'Contrasts: Polypenteneamer and Phantom Networks', of his Polymer Music, Op. 2.)

The programme of the Rolduc meeting was divided into a number of areas, several of which (Thermodynamics, Blends, Morphology) embrace directly the major research interests of the honorees. The other major sections (Diffusion and Barriers, Processing and Rheology, Chain Dynamics, Characterization and Solution Behaviour, New Developments) round out a full picture of modern polymer research and its technological spinoffs. Readers of this volume, as well as attendants at the Rolduc gathering, owe thanks to DSM for its sponsorship, and above all a debt of profound gratitude to Drs P. Lemstra and L. Kleintjens and their helpers for organizing the meeting and for their herculean efforts during its actual course. They have set an example which one hopes will inspire many followers.

WALTER H. STOCKMAYER

Dartmouth College Hanover, New Hampshire, USA

Vll

PREFACE

In April 1985, Ron Koningsveld and Chris Vonk of DS M Central Research retired after a lifetime devoted to the transfer of fundamental polymer science to technology. For his work on the integration of academic and industrial research, the University of Bristol awarded the degree of Doctor of Science honoris causa to Ron Koningsveld. announced during the conference and presented on 9 July. The simultaneous retirement stimulated the idea of organizing an international discussion meeting on the theme 'Integration of Fundamental Polymer Science and Technology'.

The aim of the meeting was to stimulate discussions between both academic and industrial polymer scientists and processing engineers. About 250 participants took part in the conference, which was held in Rolduc Abbey, a well-preserved medieval monument in the rural province of Limburg, The Netherlands.

In close consultation with the advisory committee, Sir Geoffrey Allen (London), Sir Charles Frank (Bristol), Professor G. Smets (Louvain), Professor W. Beek (Rotterdam) and Professor G. Menges (Aachen), the organizing committee, encouraged by honorary chairman A. H. de Rooij (Research Director of DSM), composed a programme consisting of the following topics: Thermodynamics/(Co)polymer Blends; Diffusion/Barrier Properties; Chain Mobility/Morphology; Processing; Polymer Networks; and Speciality Polymers. Each topic was introduced by invited academic or industrial experts, after which contributed papers and posters were presented.

All active participants were asked to submit a paper for this book. The editors are not to be held responsible for the scientific contents or views which are expressed herein, but we are convinced that the reader will enjoy some of the controversial opinions presented in this volume.

We thank all contributors to this volume and we hope that the 'Rolduc Polymer Meeting' will become an established event with the aim of the transfer of polymer science to technology.

L.A. K. P. J. L.

ix

CONTENTS

Foreword

Preface

Part 1: Thermodynamics

Thermodynamics and Engineering Needs R. Koningsveld

Statistics of Surface Contact Distributions A. f. Staverman

v

VB

3

19

Polymer Melt and Glass: Thermodynamic and Dynamic Aspects 34 R. Simha

A Fresh Look at Solutions of Polymer Mixtures 46 K. Sole

Polymer-Polymer Interactions and Phase Diagrams of Compatible Polyblends by Gas-Chromatography . 52

S. Klotz, H. Grater and H.-f. Cantow

Application of the Mean-Field Lattice-Gas Model to PartialIy-Miscible Polymer Systems 56

L. A. Kleintjens

Liquid-Liquid Phase Separation in Mixtures of Statistical Co-polymers 67

R. Van der Haegen

Characterization of Industrial Polymers and Polymer Mixtures by Turbidimetric Measurements at the Lower Critical Solution Temperature

Phi-Thi Tu-Anh, H. Phuong-Nguyen and G. Delmas 77

x

Part II: Characterization/Solution Behaviour

Characterization of Copolymers: Chromatographic Cross-Frac-tionation Analysis of Styrene-Acrylonitrile Copolymers 85

G. Glockner, J. H. M. van den Berg, N. L. J. Meijerink and Th. G. Scholte

CPF: A New Method for Large Scale Fractionation 99 H. Geerissen, J. Roos and B. A. Wolf

Flow Birefringence of Associations of Polymers in Solution 103 D. DuPuis and C. Wolff

Theoretical Calculation of Diffusion Coefficient and Viscosity of Star Polymers in Solution . 108

J. J. Freire, A. Rey and J. Garcia de la Torre

A Photon Correlation Spectroscopy Investigation of Precipitation Polymerization in Liquid Vinyl Chloride 112

F. M. Willmouth, D. G. Rance and K. M. Henman

Part III: Blends

The Role of Specific Interactions in Polymer Miscibility 119 D. J. Walsh

Relation of Interdiffusion and Self-Diffusion in Polymer Mixtures 128 H. Sillescu

Crystallization and Melting Studies on Poly(ethylene oxide)/ Poly(tnethyl methacrylate) Mixtures 132

G. C. Alfonso and T. P. Russell

Specific Intermolecular Interactions in Polymer Blends 138 J. M. G. Cowie

Thermal and Morphological Analysis of PolY(e-caprolactam)-Poly(etherester) Mixtures 148

E. Gattiglia, E. Pedemonte and A. Turturro

Xl

Isochrone Viscoelastic Functions via Activation Energy of Flow: Charge Transfer Compatibilized Polyblends 152

M.-J. Brekner, H. A. Schneider and H.-J. Cantow

Modification of Thermosetting Resins by Thermoplastics 156 C. B. Bucknall, P. Davies and I. K. Partridge

The Toughness Behavior of Emulsion ABS: Effect of Rubber Concentration and Acrylonitrile Content on the Deformation Modes 160

D. Maes, G. Groeninckx, N. Aile and J. Ravenstijn

Part IV: Networks

Thermodynamics of Casein Gels and the Universality of Network Theories 167

M. Gordon

Crosslinking Theory Applied to Industrially Important Polymers 177 K. Dusek

Reversible and Irreversible Deformation of Van der Waals Networks . 188

H. G. Kilian

Photo polymerization of Diacrylates 198 J. G. Kloosterboer, G. M. M. van de Hei and G. F. C. M. Lijten

Simulation Model for Densely Cross-Linked Networks Formed by Chain-Reactions 204

H. M. J. Boots

Nonlinear Viscoelasticity of EPDM Networks B. J. R. Scholtens and P. J. R. Leblans

Some Comments on the Thermodynamics of Swelling M. Nagy

Thermoreversible Gelation of Vinyl Polymers H. Berghmans and W. Stoks

213

218

Xll

Static and Dynamic Lightscattering of Thermoreversible Gelling iota-Carrageenan 230

H.-U. ter Meer and W. Burchard

Effects of Poly(acrylamide) on the Solution and Gel Properties of Water-Gelatin System 234

A. Turturro, A. Shoushtarizadehnaseri, E. Pedemonte, S. Franco and A. Vallarino

Compatibility and Viscoelasticity of Mixed Biopolymer Gels 238 A. H. Clark and S. B. Ross-Murphy

Halato-Telechelic Polymers as Models ofIon-Containing Polymers and Thermoreversible Polymer Networks 242

R. Jerome

Ion-Containing Networks: Structural Modifications Induced by Lithium Ions 246

J. F. Le Nest, 1. P. Cohen-Addad, A. Gandini, F. Defendini and H. Cheradame

Ion-Containing Networks: Recent Results Concerning Transport Properties . 250

A. Gandini, J. F. Le Nest, M. Leveque and H. Cheradame

Part V: Diffusion/Barrier Properties

Diffusion of Gases and Liquids in Glassy and Semi-Crystalline Polymers 259

H. L. Frisch

Tntnsport Regulated Electrochemical Reactions 10 Polyimide Films. 265

S. Mazur and S. Reich

Processing of Barrier Film by Coextrusion . 273 F. Hensen

Xlll

Part VI: Chain Dynamics

Single-Chain Dynamics in Polymer Characterization 293 W. H. Stockmayer

Non-Ideal Statistics and Polymer Dynamics 296 P. F. MijnliefJ and R. J. J. Jongschaap

Computation and Display of Polymer Chain Behaviour 300 R. F. T. Stepto

Deuteron-NMR Studies of Molecular Motions in Solid Polymers 304 H. W. Spiess

A Two-Dimensional NMR Study of Very Slow Molecular Motions in Polymers 308

A. P. M. Kentgens, A. F. de Jong, E. de Boer and W. S. Veeman

Transitions and Mobile Phases by NMR Normal Alkanes and Polyethylene 313

M. Moiler, D. Emeis and H.-J. Cantow

Morphology and Chain Dynamics of Polymers as Reflected from Polymer-Dye Interactions 317

C. D. Eisenbach

Emission Spectroscopy and the Molecular Mobility of Polyepoxide Networks . 321

E. W. Meijer and R. J. M. Zwiers

Mobility of Sidegroups in Polydimethylsiloxane . 326 H.-H. Grapengeter, B. Alefeld and R. Kosfeld

Glass Transitions in Unsymmetrically Substituted Siloxanes 331 R. Kosfeld, M. Hess and Th. Uhlenbroich

Part VII: Processing/Rheology

From Molecular Models to the Solution of Flow Problems 337 L. E. Wedgewood and R. B. Bird

xiv

Transient-Network Theories: New Developments and Applications 346 R. J. J. Jongschaap and H. Kamphuis

Rheological Properties of a LDPE Melt in Transient Uniaxial Elongational Flow, Described with a Special Type of Constitutive Equation 351

P. J. R. Leblans, J. Sampers and H. C. Booij

Physical Background of Mould Filling With and Without Crystallization 356

H. Janeschitz-Kriegl, G. Krobath and S. Liedauer

On the Mathematical Modelling of the Injection Moulding Process 361 C. W. M. Sitters and J. F. Dijksman

Mixing Processes in Polymer Processing 367 Z. Tadmor

Blending of Incompatible Polymers 381 A. K. Van der Vegt and J. J. Elmendorp

Polymer Reactions During Melt-Processing 390 S. M. Aharoni

Assessing Rubber Processing Aids Effectiveness 394 J. L. Leblanc .

Plastics Processing 398 G. Menges

Part VIII: Structure and Morphology

Some Facets of Order in Crystalline Polymers as Revealed by Polyethylene 425

A. Keller

Investigation of the Crystallization Process of Polymers by Means of Neutron Scattering 456

E. W. Fischer

xv

Lamellar Organization in Polymer Spherulites 466 D. C. Bassett

Considerations on the Crystallization with Chain Folding in Polymers 471

C. G. Vonk

Chain Mobility in Phase Transformations of Inorganic Polymers 480 J. H. Magill

Ultra-Drawing of High-Molecular-Weight Polyethylene Cast from Solution. IV. Effect of Annealing/Re-crystallization 508

C. W. M. Bastiaansen, P. Froehling, A. J. Pijpers and P. J. Lemstra

Microhardness of Semicrystalline Polymers 517 F. J. Balta Calleja and H. G. Kilian

Model Calculations for W AXS Profiles from the Polymer Crystalline Particle Size Distribution 527

G. Bodor and D. Hoffmann

Infrared Spectroscopy on PET Yarns 536 H. M. Heuvel and R. Huisman

Interaction Between Crystallization and Orientation 551 H. G. Zachmann and R. Gehrke

Neutron Scattering of Poly(ethylene terephthalate) 563 J. W. Gilmer, D. Wiswe, H. G. Zachmann, J. Kugler and E. W. Fischer

The Similarity Between Cellulose and Aramid Fibres 567 M. G. Northolt

Crystalline Order in Nylon 4,6 573 R. J. Gaymans, D. K. Doeksen and S. Harkema

Pulsed EPR Study of the Trapping Process of Radicals III

Polyethylene 577 C. P. Keijzers, H. C. van Lieshout, A. A. K. Klaassen and E. de Boer

XVI

Analysis of Filled Rubbers Using SAXS 581 R. J. Young, D. Al-Khudhairy and A. G. Thomas

SAXS Studies of Semi-Crystalline Polymer Blends Using Synchrotron Radiation 585

M. Vandermarliere, C. Riekel, M. Koch, G. Groeninckx and H. Reynaers

Ultra-Drawing of Polypropylene 589 A. Peguy and R. St-John Manley

Spinning of Fibers from Cellulose Solutions in Amine Oxides 593 I. Quenin, H. Chanzy, M. Paillet and A. Peguy

Part IX: New Developments

Future Trends in Polymer Chemistry . 599 G. Smets

Recent Investigations of Interpenetrating Polymer Networks 611 K. C. Frisch

Polymers with Metal-like Conductivity: Structure, Properties and Applications 620

G. Wegner

The Mechanical Properties of Polypyrrole Plates 630 D. Bloor, R. D. HerclifJe, C. G. Galiotis and R. J. Young

High Modulus Flexible· Polymers 634 I. M. Ward

Radiation Treatment of Polymers 648 A. Charlesby

High Precision Replication of Laservision Video Discs Using UV-Curable Coatings. 663

G. J. M. Lippits and G. P. Metis

xvii

Fast Curing Low-Modulus Coatings for High-Strength Optical Fibres 669

D. J. Broer and G. N. Mol

Replication of High Precision Aspherical Lenses Using UV-Curable Coatings 673

R. J. M. Zwiers and G. C. M. Dortant