Contents

Preface to the Revised Edition

Preface to the First Edition

1. Introduction

1.1 INTRODUCTION

1.2 INTERMOLECULAR INTERACTIONS

1.3 STRUCTURAL ORGANIZATION

1.4 DYNAMICS

1.5 PHASE TRANSITIONS

1.6 ORDER PARAMETERS

1.7 SCALING LAWS

1.8 POLYDISPERSITY

1.9 EXPERIMENTAL TECHNIQUES FOR INVESTIGATING SOFT MATTER

1.10 COMPUTER SIMULATION

FURTHER READING

2 Polymers

2.1 INTRODUCTION

2.2 SYNTHESIS

2.3 POLYMER CHAIN CONFORMATION

2.4 CHARACTERIZATION

2.5 POLYMER SOLUTIONS

2.6 AMORPHOUS POLYMERS

2.7 CRYSTALLINE POLYMERS

2.8 PLASTICS

2.9 RUBBER

2.10 FIBRES

2.11 POLYMER BLENDS AND BLOCK COPOLYMERS

2.12 DENDRIMERS AND HYPERBRANCHED POLYMERS

2.13 POLYELECTROLYTES

2.14 ELECTRONIC AND OPTO-ELECTRONIC POLYMERS

FURTHER READING

QUESTIONS

3 Colloids

3.1 INTRODUCTION

3.2 TYPES OF COLLOIDS

3.3 FORCES BETWEEN COLLOIDAL PARTICLES

3.4 CHARACTERIZATION OF COLLOIDS

3.5 CHARGE STABILIZATION

3.6 STERIC STABILIZATION

3.7 EFFECT OF POLYMERS ON COLLOID STABILITY

3.8 KINETIC PROPERTIES

3.9 SOLS

3.10 GELS

3.11 CLAYS

3.12 FOAMS

3.13 EMULSIONS

3.14 FOOD COLLOIDS

3.15 CONCENTRATED COLLOIDAL DISPERSIONS

FURTHER READING

QUESTIONS

4 Amphiphiles

4.1 INTRODUCTION

4.2 TYPES OF AMPHIPHILE

4.3 SURFACE ACTIVITY

4.4 SURFACTANT MONOLAYERS AND LANGMUIR-BLODGETT FILMS

4.5 ADSORPTION AT SOLID INTERFACES

4.6 MICELLIZATION AND THE CRITICAL MICELLE CONCENTRATION

4.7 DETERGENCY

4.8 SOLUBILIZATION IN MICELLES

4.9 INTERFACIAL CURVATURE AND ITS RELATIONSHIP TO MOLECULAR STRUCTURE

4.10 LIQUID CRYSTAL PHASES AT HIGH CONCENTRATIONS

4.11 MEMBRANES

4.12 TEMPLATED STRUCTURES

FURTHER READING

QUESTIONS

5 Liquid Crystals

5.1 INTRODUCTION

5.2 TYPES OF LIQUID CRYSTALS

5.3 CHARACTERISTICS OF LIQUID CRYSTAL PHASES

5.4 IDENTIFICATION OF LIQUID CRYSTAL PHASES

5.5 ORIENTATIONAL ORDER

5.6 ELASTIC PROPERTIES

5.7 PHASE TRANSITIONS IN LIQUID CRYSTALS

5.8 APPLICATIONS OF LIQUID CRYSTALS

FURTHER READING

QUESTIONS

6 Biological Soft Matter

6.1 INTRODUCTION

6.2 LIPID MEMBRANES

6.3 DNA

6.4 PROTEINS

6.5 POLYSACCHARIDES AND GLYCOPROTEINS

6.6 MACROMOLECULAR ASSEMBLIES

FURTHER READING

QUESTIONS

Numerical Solutions to QUESTIONS

Index

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Library of Congress Cataloguing-in-Publication Data

Hamley, Ian W.

Introduction to soft matter: synthetic and biological self-assembling materials / Ian W. Hamley. – Rev. ed.

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-51609-6 (cloth)

1. Polymers–Textbooks. 2. Colloids–Textbooks. 3. Micelles–Textbooks. 4. Liquid crystals–Textbooks. I. Title.

QD381.H37 2007

547′.7-dc22          2007025456

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 978-0-470-51609-6 (H/B)

978-0-470-51610-2 (P/B)

Preface to the Revised Edition

The field of soft matter science remains an exciting and fast developing one. Since the first edition of this book there have been advances in several areas and I felt it appropriate to update the book to reflect this. Several other books in the field have also been published recently (as cited in the revised bibliography sections herein), although most, fortunately, do not overlap too much with mine! The main addition to this text is a new chapter on Biological Soft Matter, which adds significantly to the rather cursory discussion of proteins and DNA in the previous edition and introduces some quite cutting-edge topics. I have also added new sections to Chapter 2 on advanced polymeric materials to discuss dendrimers, polyelectrolytes, and electronic and optoelectronic polymers, albeit briefly. The section about the thermodynamics of micellization in Chapter 4 has also been revised. I thank my students who have sat my Physical Chemistry of Soft Matter courses over the years in various guises for critical comments on the previous treatment, and John Wiley & Sons, Ltd for supporting me in this endeavour.

Ian W. Hamley
School of Chemistry,
University of Reading, UK

Preface to the First Edition

This book is largely intended to provide an introduction to colloid chemistry, but I have used the term ‘soft matter’ to indicate a unified subject that includes aspects of liquid crystal and polymer science not found in existing textbooks on colloid chemistry. General textbooks of physical chemistry either do not cover colloid chemistry at all or fail to give it the space it deserves. There are fewer than a handful of recent books that give a broad coverage of the physical chemistry of soft materials, and these are written at an advanced level. For both these reasons, and also given that existing introductory colloid chemistry texts are mostly getting rather long in the tooth, I felt that a new book in the area offering up-to-date and unified coverage, would be valuable both to students and researchers.

The book has been written primarily for undergraduates taking physical chemistry courses. In Leeds it is a companion book to the final year module ‘Physical Chemistry of Condensed Matter’. I hope it will also be of interest to students of physics and materials science taking courses on colloids, polymers, soft condensed matter or complex fluids. It should also serve as a useful introduction and reference for researchers in these areas.

I wish to thank my editors at Wiley for assistance in the production of the book.

IWH
School of Chemistry,
University of Reading, UK

1

Introduction

1.1 INTRODUCTION

Mankind has exploited matter in technology through the ages. For many millenia, we relied on materials like wood or metals that were subject to minimal processing to provide useful objects. It is only within a few minutes of midnight on the proverbial human evolutionary clock that materials have been engineered for ultimate applications based on a deep understanding of molecular properties. Considering substances that have been engineered in a controlled or tailored manner, the nineteenth century was the age of iron and steel. The twentieth century saw the development of new types of engineered materials, especially polymers, which in the form of plastics have, in many applications, usurped many of the traditional ‘hard’ materials. This is not to forget the emergence of an important class of inorganic material, semiconductors, in the second half of this century. These are, of course, the basis for the second industrial revolution, that of information technology. However, it seems fair to say that many properties of hard matter are now well understood whereas we are still on the learning curve with soft matter. For example, inspired by nature, we are only just beginning to be able to engineer complex structures formed by biopolymers or to exploit nanotechnology to make devices based on self-organization of polymers. In our new millennium it seems safe to predict the continued importance of soft materials, engineered in ways we can as yet only dream of.

The idea of a unified approach to ‘soft materials’ has only gained ground recently. It is an interdisciplinary subject, taking in aspects of physics, chemistry and materials science, but also of biochemistry or (chemical, mechanical) engineering in specific cases. A consequence of this interdisciplinarity is that, unfortunately, the subject is not considered in conventional textbooks on physics, physical chemistry or materials science, often being neglected entirely or covered in an inadequate manner. The purpose of this book is to ‘fill the gap’, by providing an up-to-date introductory summary of the thermodynamics and dynamics of soft materials. In each of the six chapters, the basic physical chemistry is covered first, prior to an outline of applications. The material is presented in a coherent fashion across the book. Equations have been kept to the minimum number that capture important relationships. Derivations are included, where they illustrate thermodynamical or statistical mechanical principles in action. The derivation of the Flory–Huggins theory in Section 2.5.6 or of the thermodynamics of micellar equilibria in Section 4.6.5 are good examples. Soft materials are important in many products, such as detergents, paints, plastics, personal care products, foods, clays, plastics and gels. Such uses of soft materials are exemplified throughout this book.

In this book we consider soft materials under the headings of polymers (Chapter 2), colloids (Chapter 3), amphiphiles (Chapter 4), liquid crystals (Chapter 5) and biological soft materials (Chapter 6). The distinctions between these systems are often not strong. For example, amphiphiles in solution and some aspects of polymer science are often considered in books on colloid chemistry. However, here we treat them separately since they are technologically important enough to merit detailed consideration on their own. The chapter on liquid crystals is in fact focused on one class of material, thermotropic liquid crystals, where phase transitions are thermally driven. However, a different class of liquid crystal phase is formed in amphiphile solutions, where concentration is also a relevant variable. These are termed lyotropic liquid crystal phases and are discussed in Chapter 4.

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