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Karsa 1.1.1 Introduction 1.1.2 Properties and other criteria influencing surfactant choice 1.1.3 Surfactant applications 1.1.4 Conclusion Appendix: Application guide 1.2 Surfactant market overview: importance in different industries Joel Houston 1.2.1 Introduction 1.2.2 Consumer 1.2.3 Industrial 1 1 1 3 5 7 8 14 14 14 21 The Basic Theory Hatice Gecol 2.1 Molecular structure of surfactants 2.2 Surface activity 2.2.1 Surface tension 2.2.2 Interfacial tension 2.2.3 Surface and interfacial tension reduction 2.2.4 Test methods for surface and interfacial tension measurements 2.3 Self-assembled surfactant aggregates 2.3.1 Micelles and critical micelle concentration 2.3.2 Aggregate structures and shapes 2.4 Adsorption of surfactants at surfaces 2.4.1 Adsorption at liquid–gas and liquid–liquid interfaces 2.4.2 Adsorption at liquid–solid interface 24 24 26 26 28 28 31 32 33 35 38 38 39 vi 3 4 Contents Acknowledgement References 43 43 Applied Theory of Surfactants Peter Schmiedel and Wolfgang von Rybinski 3.1 Introduction 3.2 Detergency 3.2.1 Fundamental processes 3.2.2 Basic formulae of detergents and cleansers 3.2.3 Adsorption at the solid–liquid interface 3.2.4 Surface tension and wetting 3.2.5 Interplay of surfactants with other detergent ingredients 3.3 Phase behaviour of surfactants 3.3.1 Introduction 3.3.2 Surfactant phases 3.3.3 Impact of the phase behaviour on detergency 3.4 Emulsions 3.4.1 Introduction 3.4.2 Emulsion types 3.4.3 Breakdown of emulsions 3.5 Foaming and defoaming 3.5.1 Introduction 3.5.2 Stabilising effects in foams 3.5.3 Correlation of foamability with interfacial parameters 3.5.4 Foam control 3.6 Rheology of surfactant solutions 3.6.1 Introduction 3.6.2 Rheological terms 3.6.3 Rheological behaviour of monomeric solutions and non-interacting micelles 3.6.4 Entanglement networks of rod-like micelles 3.6.5 The rheological behaviour of bilayer phases References 46 46 47 47 48 48 54 60 62 62 62 66 69 69 70 74 76 76 77 78 81 82 82 83 Anionic Surfactants John Hibbs 4.1 Sulphonates 4.1.1 Alkylbenzene sulphonates 4.1.2 α-Olefin sulphonates 4.1.3 Paraffin sulphonates 4.1.4 Sulphonated methyl esters 4.1.5 Sulphonated fatty acids 4.1.6 Sulphosuccinates 4.2 Sulphates 4.2.1 Alkyl sulphates 4.2.2 Alkyl ether sulphates 4.3 Phosphate esters 83 84 86 88 91 92 93 102 104 106 108 110 113 113 118 122 Contents vii 4.4 Carboxylates 4.4.1 Soap 4.4.2 Ether carboxylates 4.4.3 Acyl sarcosinates 4.4.4 Alkyl phthalamates 4.4.5 Isethionates 4.4.6 Taurates References 124 124 126 127 128 129 130 132 5 Non-ionic Surfactants Paul Hepworth 5.1 Introduction 5.2 General alkoxylation reactions 5.3 Alkyl phenol ethoxylates 5.4 Fatty alcohol ethoxylates 5.5 Polyoxethylene esters of fatty acids 5.6 Methyl ester ethoxylates 5.7 Polyalkylene oxide block co-polymers 5.8 Amine ethoxylates 5.9 Fatty alkanolamides 5.10 Amine oxides 5.11 Esters of polyhydric alcohols and fatty acids 5.12 Glycol esters 5.13 Glycerol esters 5.14 Polyglycerol esters 5.15 Anhydrohexitol esters 5.16 Polyoxyalkylene polyol esters 5.17 Alkyl poly glucosides 5.18 Gemini surfactants References 133 133 133 135 136 139 140 141 142 143 144 145 146 146 146 147 148 149 150 151 6 Other Types of Surfactants 6.1 Cationics J.

1.1 History and applications of surfactants David R.

Farn Copyright © 2006 by Blackwell Publishing Ltd Chapter 1 What Are Surfactants?

xiv Preface Acknowledgements The Editor would like to thank the authors of each chapter or section for their time and effort in contributing to this book which provides a state-of-the-art review of the surfactant industry.

Surfactants are not new: the oldest surfactant is soap which dates back well over 2000 years although the modern surfactant industry has developed essentially since the Second World War, utilising the expansion of the petrochemical industry as one of its main sources of raw materials.

Chapter 1 covers the development of the industry and elaborates on the importance of surfactants in modern day living and the very many areas where they find application.

C446 2006 541 .33–dc22 2005017738 A catalogue record for this title is available from the British Library Set in 10/12pt Minion & Optima by Tech Books, New Delhi, India Printed and bound in India by Replika Press Pvt, Ltd, Kundli The publisher’s policy is to use permanent paper from mills that operate a sustainable forestry policy, and which has been manufactured from pulp processed using acid-free and elementary chlorine-free practices.

Bernstein Chem Law UK, MWB Business Exchange, 494 Midsummer Boulevard, Central Milton Keynes, MK9 2EA, UK G.

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