Colloids and Interfaces with Surfactants and Polymers An Introduction

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1 Colloids and Interfaces with Surfactants and Polymers An Introduction Colloids and Interfaces with Surfactants and Polymers An Introduction J. W. Goodwin ß 2004 John Wiley & Sons, Ltd ISBN: (HB) ISBN: (PB)

2 Scanning electron micrographs of some colloidal particles: (a) A film of printing ink showing well-dispersed titanium dioxide pigment (3400). (b) Sodium kaolinite (china clay) particles in an open card-house aggregate (9100). (c) Dried polystyrene latex showing how the order in a concentrated dispersion is maintained on drying (9100). (d) Coagulated bimodal latex mixture after shear processing showing densely packed, uniform aggregates (700). Reproduced with permission from Modern Aspects of Colloidal Dispersions edited by Ottewill and Rennie. Copyright (1998) Kluwer Academic Publishers.

3 Colloids and Interfaces with Surfactants and Polymers An Introduction Jim W. Goodwin Interfacial Dynamics Corporation Portland, Oregon, USA

4 Copyright ß 2004 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (þ44) (for orders and customer service enquiries): Visit our Home Page on or All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to the Publisher should be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England, or ed to permreq@wiley.co.uk, or faxed to (þ44) This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the Publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought. Other Wiley Editorial Offices John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA , USA Wiley-VCH Verlag GmbH, Boschstr. 12, D Weinheim, Germany John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada M9W 1L1 Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Library of Congress Cataloging-in-Publication Data Goodwin, James W. (James William) Colloids and interfaces with surfactants and polymers: an introduction / Jim Goodwin. p. cm. Includes bibliographical references and index. ISBN (Cloth : alk. paper) ISBN (Paper : alk. paper) 1. Colloids. 2. Surface active agents. 3. Surface chemistry. 4. Polymers. I. Title. QD549.G dc British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN: (Cloth) (Paperback) Typeset in 10/12 pt Times by Kolam Information Services Pvt. Ltd, Pondicherry, India Printed and bound in Great Britain by TJ International, Padstow, Cornwall This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production.

5 Contents Preface ix Chapter 1 The Nature of Colloids 1 1 INTRODUCTION 1 2 COLLOIDS IN ACTION 4 3 CONCENTRATED COLLOIDAL DISPERSIONS 8 4 INTERFACES 12 5 SURFACTANTS 20 6 SOLUTION POLYMERS 24 7 SUMMARY 25 REFERENCES 26 Chapter 2 Macromolecules and Surfactants 27 1 INTRODUCTION 27 2 MACROMOLECULAR DEFINITIONS 27 3 CONFORMATIONS IN DILUTE SOLUTIONS 29 4 THE FLORY HUGGINS THEORY OF POLYMER SOLUTIONS 32 5 POLYMER SOLUTION PHASE BEHAVIOUR 36 6 POLYMERS AT SURFACES 39 7 POLYMER CHARACTERIZATION 42 8 SURFACTANTS IN SOLUTION 46 REFERENCES 58 Chapter 3 Interactions between Colloidal Particles 61 1 INTRODUCTION 61 2 INTERMOLECULAR ATTRACTION 63 3 COMPLEX NUMBER MANIPULATION 68 4 DISPERSION FORCES BETWEEN PARTICLES 71 5 RETARDED DISPERSION FORCES 78 6 THE GENERAL OR LIFSHITZ THEORY OF DISPERSION FORCES BETWEEN PARTICLES 79 7 SUMMARY AND CALCULATION GUIDE 81

6 vi Colloids and Interfaces with Surfactants and Polymers 8 CALCULATION STRATEGY 82 9 THE DEPLETION INTERACTION 87 REFERENCES 93 Chapter 4 Forces of Repulsion 95 1 INTRODUCTION 95 2 ELECTROSTATIC INTERACTIONS 95 3 THE ORIGINS OF SURFACE CHARGE 96 4 THE INTERACTION BETWEEN DIFFUSE DOUBLE LAYERS THE INTERACTION BETWEEN TWO SPHERES THE EFFECT OF PARTICLE CONCENTRATION STERIC INTERACTIONS CALCULATION STRATEGY 123 REFERENCES 125 Chapter 5 The Stability of Dispersions INTRODUCTION THE STABILITY OF CHARGE-STABILIZED COLLOIDS THE DVLO THEORY MECHANISMS OF AGGREGATION HETERO-COAGULATION AND HETERO-FLOCCULATION THE RATE OF COAGULATION AGGREGATION IN FLOWING DISPERSIONS 143 REFERENCES 150 Chapter 6 The Wetting of Surfaces by Liquids INTRODUCTION THE CONTACT ANGLE METHODS FOR THE MEASUREMENT OF CONTACT ANGLE CONTACT ANGLE HYSTERESIS SPREADING CURVED SURFACES CAPILLARITY TEMPERATURE EFFECTS 171 REFERENCES 176 Chapter 7 Emulsions and Microemulsions INTRODUCTION EMULSIFICATION STABILITY OF EMULSIONS MICROEMULSIONS 187 REFERENCES 193

7 Contents vii Chapter 8 Characterization of Colloidal Particles INTRODUCTION PARTICLE SIZE MICROSCOPY ZONAL METHODS SCATTERING METHODS ANALYSIS OF SCATTERED RADIATION NEUTRON REFLECTION DYNAMIC LIGHT SCATTERING CHARACTERIZATION OF THE ELECTRICAL PROPERTIES OF PARTICLES VISCOSITIES OF DISPERSIONS 232 REFERENCES 238 Chapter 9 Concentrated Dispersions INTRODUCTION THE STRUCTURE OF CONCENTRATED DISPERSIONS RHEOLOGY LINEAR VISCOELASTICITY OF COLLOIDAL DISPERSIONS PHENOMENOLOGY 259 REFERENCES 279 Index 281

8 Preface We take for granted the behaviour of colloidal systems from a very early age and as we are formerly taught the various scientific disciplines, the nature of colloids is rarely mentioned. This is surprising as it impacts on so many products that we use everyday. The processing and delivery of the correct properties is often dependent on the material being in the colloid state and yet few courses cover the subject in depth, if at all. As a result, many scientific workers have to acquire their knowledge piecemeal while working on other problems. An introductory text is what is most used in this situation. Specialist texts are often left on the shelf as we search for attempts to solve a particular problem. This present text covers a little more ground than some of the older introductory volumes that are still available but I have attempted to help the reader in the more complicated regions by providing a strategy for any calculations. Some derivations are outside the scope of an introduction, but, where they are straightforward, they are included in order to help readers gain as much insight as possible. None of the mathematics is at a high level. The references are mainly to specialist volumes in the area. This is not to discourage the reading of the original work but it is because the general volumes are more readily available in many libraries and often help to put the work in context. There will inevitably be some areas that are neglected, as with any introductory volume. This is in part due to what areas are perceived to be currently most generally needed and the composition of this volume has been governed by the questions which are currently asked when discussing problems in industry. I would like to acknowledge with gratitude the help and encouragement of all of my previous colleagues in the Department of Physical Chemistry at the University of Bristol, UK, especially Professors Ron Ottewill and Brian Vincent, the past and current holders of the Leverhulme Chair in that Department and also to Dr Paul Reynolds, the manager of the Bristol Colloid Centre. Jim Goodwin Portland, Oregon, 2003

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