POLYMER SCIENCE AND TECHNOLOGY Volume 6

PERMEABILITY OF PLASTIC FILMS AND COATINGS TO , , AND POLYMER saENCE AND TECHNOLOGY

Editorial Board:

William J. Bailey C. A. J. Hoeve University of Maryland Texas A&M University College Park, Maryland College Station, Texas Yoichi Ishida J. P. Berry Osaka University Rubber and Plastics Research Association Toyonaka, Osaka, Japan of Great Britain Frank E. Karasz Shawbury University of Massachusetts Shrewsbury, England Amherst, Massachusetts

A. T. DiBenedetto O.ias Solomon The University of Connecticut Poly technical Institute of Bucharest Storrs, Connecticut Bucharest, Romania

Volume 1 • STRUCTURE AND PROPERTI ES OF POLYMER FI LMS Edited by Robert W. Lenz and Richard S. Stein. 1972

Volume 2. WATER-SOLUBLE POLYMERS Edited by N. M. Bikales. 1973

Volume 3 • POLYMERS AND ECOLOGICAL PROBLEMS Edited by James Guillet. 1973

Volume 4. RECENT ADVANCES IN POLYMER BLENDS, GRAFTS, AND BLOCKS Edited by L. H. Sperling. 1974

Volume 5. ADVANCES IN POLYMER FRICTION AND WEAR (Parts A and B) Edited by Lieng-Huang Lee .1974

Volume 6. PERMEABILITY OF PLASTIC FILMS AND COATINGS TO GASES, VAPORS, AND LIQUIDS Edited by Harold B. Hopfenberg. 1974

A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher. POLYMER SCIENCE AND TECHNOLOGY Volume 6

PERMEABILITY OF PLASTIC FILMS AND COATINGS TO GASES, VAPORS, AND LIQUIDS

Edited by Harold B. Hopfenberg Department of Chemical Engineering School of Engineering North Carolina State University Raleigh, North Carolina

PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data

Borden Award Symposium, Los Angeles, 1974. Permeability of plastic films and coatings to gases, vapors, and liquids.

(Polymer science and technology; v. 61 "Proceedings of the Borden Award Symposium of the Division of Organic Coatings and Plastics Chemistry of the American Chemical Society, honoring Professor Vivian T. Stannett." 1. Plastic films-Permeability-Congresses. 2. Plastics-Permeability-Congresses. I. Hopfenberg, Harold B., ed. II. Stan nett, Vivian. III. Americim Chemical Society. Division of Organic Coatings and Plastics Chemistry. TPl183.F5B67 1974 668.4'95 74-23823 ISBN-13: 978-1-4684-2879-7 e-ISBN-13: 978-1-4684-2877-3 DOl: 10.10071978-1-4684-2877-3

Proceedings of the Borden Award Symposium of the Division of Organic Coatings and Plastics Chemistry of the American Chemical Society, honoring Professor Vivian T. Stan nett, held at Los Angeles, California, April, 1974.

© 1974 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1974

A Division of Plenum F\Jblishing Corporation 227 West 17th Street, New York, N.Y. 10011

United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd. 4a Lower John Street, London, W1 R 3PD, England

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherWise, without written permission from the Publisher Foreword

The subject of this book has a long and venerable history. The first definitive description of the mechanism of permeation of small molecules through polymer films was presented by Sir Thomas Graham in 1866 in a study of gases in rubber membranes. He called the process "colloidal " and his picture is similar to that which we are still using, known as the - diffusion model. The dissolves at one interface followed by diffusion through the membrane and evaporation at the other surface, exposed to lower . In this remarkable paper many of the concepts of permeability which we know today are presented for the first time. In particular a correlation was demonstrated between the permea• bility and the boiling point of the penetrating gas. The effect of on the gas permeability was correctly related to in• creased "diffusion" due to the "increasing softness" of the rubber with increasing temperature. This overcomes the decrease in solu• bility due to the decreasing "ease of condensation" at higher temp• eratures. The nonporous nature of rubber and its similarity to a was pointed out, and the reduced of gases with crosslinking demonstrated. Finally the potential value of rubber membranes for gas separations was pointed out and quantitatively demonstrated. Many of the chapters of this book are concerned with just these approaches.

The subject was placed on a quantitative basis by Wroblewski in 1879 who showed that the solubility of gases in rubber obeyed Henry's Law, i.e. the solubility is proportional to the of the gas. He also first applied Ficks Diffusion Law and combined it with Henry's Law and the known dependence of the permeation rate on the area and thickness of the membrane to derive the now familar expression

J where J is the amount of gas passing through unit area of the mem• brane per second, PI and P2 the partial of the permeating gas at both sides of the membrane, ~ the thickness, D the diffusion constant and S the Henry's Law solubility coefficient.

v vi FOREWORD

Daynes in 1919 extended Wroblewski's equation to non-steady state conditions and showed that the solubility and diffusion co• efficients could both be determined by measuring the increase of pressure with time starting with no gas initially in the film or at the downstream side of the membrane. Daynes used his method to determine the and diffusivities of a number of gases in natural rubber at various temperature. His values are in ex• cellent agreement with those obtained today using more refined and sophisticated equipment. The "time lag method" of Daynes was further developed and effectively used by Barrer from 1937 onwards in a long series of elegant experiments leading to much new information about the mechanism of gas permeability in high polymers. Substan• tial further advances have been made since then both in the theory, methods of measurement, and the various factors influencing the permeability of polymer films to gases.

It must be confessed, however, that a complete understanding of the relative importance of these factors does not exist at the present time and much more work is still needed.

When the transport process is extended to water and organic molecules, the mechanisms of solution and diffusion are much more complete. In particular, interactions between the polymer and the penetrant become important. In addition, at least in the case of water, non-ideal mixing or clustering of the penetrant can occur. In spite of the complications most separation procedures based on membranes involve water and organic molecules, rather than gases, as penetrants and substantial advances have been made in this field.

The symposium, so ably arranged by Professor Hopfenberg and the proceedings of which constitute this book clearly reflect the present status of our knowledge in the various areas outlined above. Most of the chapters are written by the acknowledged leaders in the field and it will be evident, on reading this book, that spectacular advances have been made in our knowledge of transport processes. Equally important is the fact that successful industrial and medical developments have been made based on this knowledge. It is my belief that all those interested in this field will learn much from reading this volume which will form the basis for many further successful developments in the field.

To end on a more personal note, I would like to thank Professor Hopfenberg for organizing such a fine symposium, and the contri• butors, many of whom have been personal friends and colleagues for many years.

v. T. STANNETT Raleigh, North Carolina September, 1974 Preface

In 1952 T.A.P.P.I. and the U.S. Army Quartermaster Corps sponsored the research of Professor Vivian Stannett and Professor Michael Szwarc to characterize and explain the permeation properties of polyethylene and other films and barrier coatings. Their papers, describing their early work, became the keystone of the emerging research in the 1950's and 1960's dealing with the explanation and exploitation of small molecule transport in polymers.

More important than Stannett's accumulation of data was his stimulation of developing scientists. Stannett and Szwarc's student, Charles E. Rogers - of Rogers, Stannett and Szwarc fame is now Professor Charles E. Rogers at Case Western Reserve University. Professor H. L. Frisch was part of the exciting and productive group of faculty at Syracuse University with Professor Stannett during Stannett's early involvement in membrane processes. Professor Alan Rembaum was conducting his graduate work with Professor Szwarc at the same time.

Stannett was the associate director of the Camille Dreyfus Laboratory while Anton Peterlin was the Director. Dr. Joel Williams worked at the Dreyfus Lab and received his Ph.D. under Stannett's direction. Koje Yasuda and Bob Kesting received their Ph.D.'s under Stannett's direction. Dr. Yasuda has continued his research in this area at the Camille Dreyfus Laboratory and Dr. Kesting has done pioneering and creative work in the development of novel reverse osmosis membranes.

The incestuous development of this explosively growing field is rather intriguing and this autocatalytic growth of people and ideas forms the basis not only of the research area but moreover the contents of this book.

While Stannett was on Sabbatical leave in Paris in 1958, Alan Michaels, then a Professor at M.I.T., visited Stannett to discuss Vivian's work. Michael's interest in polymers, an extension of his important earlier work in colloid and surface science, was further stimulated by his Paris discussion with viii PREFACE

Stannett regarding transport in polyethylene. Michael's first work in the area was an extension of Stannett's early work with poly• ethylene.

One of Michael's early students was Wolf R. Vieth, now Head of the Department of Chemical and Biochemical Engineering at Rutgers. Dr. James Barrie of Imperial College, London, England, who has worked with Professor R. M. Barrer for many years, spent his Sabbatical in Michael's lab working with Vieth, among others. Mike Lysaght worked for Michaels at the Amicon Corporation and Dr. N. S. Schneider was a Visiting Professor at M.I.T. while Michaels was developing his large reserach program in membrane phenomena.

Professor Allan Hoffman was a colleague of Michaels at M.I.T. and at Amicon Corporation and preceded Vivian in his Sabbatical position in Paris. Professor Donald Paul studied undergraduate chemical engineering at North Carolina State University where I have been teaching and researching and enjoying since 1967.

For my part, Alan Michaels inspired my graduate research program and remains a close colleague. Gerald Gordon was the demanding graduate assistant in charge of my senior chemical engineering lab at M.I.T. Morris Salame was a stimulating, happy, and hardworking classmate.

Vivian Stannett has been my best friend and closest colleague since I joined him at North Carolina State University in 1967 as a consequence of recommendations to Vivian and myself by Hoffman and Schneider that our colleagueship would be both constructive and pleasant. Hoffman and Schneider were right and I am forever gratefUl for their prescience and kindness. Professor Ralph McGregor, an Englishman who studied under Professor Peters as did John Petropoulos and Peter Roussis, is also a member of the faculty of North Carolina State University. Mitch Jacques is part of the next generation; he is one of a group of talented and imaginative students that have worked with me at North Carolina State University.

In any event, for Vivian and myself, science is facilitated and made enjoyable by cooperative interactions between people and the people mentioned here have contributed steadily to the broad research area of membrane science and to this book. Of course there are many, many more scientists doing equally creditable research in the field. Although there are seventy-five contributors to this book, it is clear that these well known scientists are only a fraction of the large and growing group of international researchers in the field.

Professor Stannett was early but more importantly he gave counsel and support to everyone who sought his help. He remains PREFACE ix first in colleagueship and the ability to provide stimulation and support to his colleagues. The Borden Award which he received, recognizes his pre-eminence, not only as a researcher, but as a stimulating and inspiring leader who helped define this broad area and contributes steadily to its still explosive growth.

HAROLD B. HOFFENBERG Raleigh, North Carolina August 1974 Contents

PART I - FUNDAMENTALS

Interaction Between Penetration Sites in Diffusion through Thin Membranes • 3 Stephen Prager and H. L. Frisch

, Steady State Transport Phenomena in Non-Ideal Permeant-Polymer Systems A. Peterlin Diffusive Transport in Swollen Polymer Membranes 35 D. R. Paul

Generalized Dual Sorption Theory 49 Wolf R. Vieth and Mary A. Amini

'Diffusion in Glassy Polymers • T. K. Kwei and Tsuey T. Wang

,Super Case II Transport of Organic Vapors in Glassy Polymers 73 C. H. M. Jacques, H. B. Hopfenberg and V. Stannett

, Correlations between Entropic and Energetic Parameters for Diffusion in Polymers R. McGregor

)Formal Theory of Diffusion through Membranes 113 R. M. Barrer l Polyethylene-Nylon 6 Graft Copolymers I. Mechanical Properties and Permeability Characteristics of Copolymers Prepared by Anionic and Cationic Initiated Processes 125 M. Matzner, D. L. Schober, R. N. Johnson, L. M. Robeson and J. E. McGrath

xi xii CONTENTS

The Influence of Drawing on the Transport Properties of Gases and Vapors in Polymers 137 Joel Williams

Modification of Polymer Membrane Permeability by Graft Copolymerization 155 C. E. Rogers, S. Yamada and M. I. Ostler

The Sorption and Diffusion of Water in Polyurethane Elastomers J. A. Barrie, A. Nunn and A. Sheer

Water Transport in Hydrophilic Polyurethanes • 183 J. L. Illinger, N. S. Schneider and F. E. Karasz ( -Effect of Thickness on Permeability 197 Sun-Tak Hwang and Karl Kammermeyer

Effects of Stereoregularity and Polymer Size on the Diffusion of Benzene in Polyvinyl Acetate 207 W. R. Brown and G. S. Park

-A Discussion of Theoretical Models of Anomalous Diffusion of Vapors in Polymers 219 J. H. Petropoulos and P. P. Roussis

Transport Behavior of Asymmetric Cellulose Acetate Membranes in Dialysis and Hyperfiltration • 233 W. Pusch

PART II - INDUSTRIAL MEMBRANE AND BARRIER FILM APPLICATIONS

.J The Effect of Transport Phenomena on the of a Plastic Carbonated Beverage Bottle G. A. Gordon and P. R. Hsia

"The Use of Low Permeation Thermoplastics in Food and Beverage Packaging • 275 Morris Salame CONTENTS xiii

Experimental Support of "Dual Sorption" in Glassy Polymers 285 Paul J. Fenelon

Transport Properties of Oriented Poly(Vinyl Chloride) 301 Thomas E. Brady, Saleh A. Jabarin and Gerald W. Miller

.J~arrier Properties of Earth Lining for . Pollution Control 321 Kenneth J. Brzozowski and Charles A. Kumins

Spontaneous Polymerization of 4-Vinyl Pyridine for Hollow Fiber Ion Exchangers • 331 A. Rembaum, S. P. S. Yen and C. Robillard

Particle Collection from Aqueous Suspensions by Permeable Hollow Fibers 343 Daniel P. Y. Chang and Sheldon K. Friedlander

Separation of Hydrocarbons by Selective Permeation through Polymeric Membranes 357 Mort Fels and Norman N. Li

Thin-Film Composite Membrane Performance in a Spiral-Wound Single-Stage Reverse Osmosis Seawater Pilot Plant • 375 R. L. Riley, G. R. Hightower. C. R. Lyons and M. Tagami

The Evolution of Phase Inversion Membranes 389 R. E. Kesting

PART III - MEMBRANE MODERATED BIOMEDICAL DEVICES

Therapeutic Systems for Controlled Administration of Drugs: A New Application of Membrane Science • 409 Alan S. Michaels

Permeability Studies with Hemodialysis Membranes 423 Elias Klein, J. K. Smith and F. F. Holland xiv CONTENTS

Preparation and Application of Radiation-Grafted Hydrogels as Biomaterials • 441 A. S. Hoffman, G. Schmer, T. A. Horbett, B. D. Ratner, L. N. Teng, C. Harris, W. G. Kraft, B. N. L. Khaw, T. T. Ling and T. P. Mate

Improvement of Blood Compatibility of Membranes by Discharge Polymerization 453 H. Yasuda, M. O. Bumgarner and L. G. Mason Biomedical Applications of Anisotropic Membranes 459 Michael J. Lysaght and Cheryl A. Ford Contributors 469 Index 475