Thickening and Gelling Agents for Food To Tim

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Edited by

ALANIMESON Technical Sales FMC Corporation (UK) Ltd Food lngredients Division Leicester

m SPRINGER-SCIENCE+BUSINESS MEDIA, B.V. First edition 1992 Reprinted 1994, 1996 Second edition 1997 © 1992, 1997 Springer Science+Business Media Dordrecht Originally published by Chapman & Hali in 1997 Softcover reprint of the hardcover 2nd edition 1997 Typeset in 10/12pt Times New Roman by Best-set Typesetter Ltd, Hong Kong

ISBN 978-1-4613-5921-0 ISBN 978-1-4615-2197-6 (eBook) DOI 10.1007/978-1-4615-2197-6 Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the UK Copyright Designs and Patents Act, 1988, this publication may not be reproduced, siored, or transmitted, in any form or by any means, without the prior permission in writing of the publishers, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries conceming reproduction outside the terms stated here should be sent to the publishers at the London address printed on this page. The publisher makes no representation, express or implied, with regard to the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any errors or omissions that may be made.

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

Library of Congress Catalog Card Number: 96-86550

8 Printed on acid-free text paper, manufactured in accordance with ANSI/ NISO Z39.48-1992 (Permanence of Paper) Contents

List of contributors xi Preface xiii Preface to the first edition xv

1 Agar 1 R. ARMISEN 1.1 Introduction 1 1.2 Raw materials 2 1.3 Production 5 1.4 Agars obtained from various agarophytes 7 1.5 Chemical composition 8 1.5.1 Agarose 8 1.5.2 Agaropectin 10 1.6 Agar gelation 10 1.7 Synergies and incompatibilities of agar 14 1.8 Applications 15 1.8.1 Food applications 15 1.8.2 Regulations for agar in foods 17 1.8.3 Other applications of agar 18 References 20

2 Alginates 22 E.ONS0YEN 2.1 Introduction 22 2.2 Manufacture 22 2.2.1 Raw materials 22 2.2.2 Commercial alginates 23 2.3 Chemical composition 24 2.3.1 General 24 2.3.2 Configuration 24 2.3.3 Alginate biosynthesis 25 2.3.4 Block structure analysis 26 2.4 Functional properties 27 2.4.1 Viscosity 27 2.4.2 Gelation 29 2.4.3 Gel strength 32 2.5 Gel formation techniques 32 2.5.1 General 32 2.5.2 Diffusion setting, neutral pH 32 2.5.3 Diffusion setting, acid pH 33 2.5.4 Internal setting, neutral and acid pH 33 2.5.5 Combined setting 33 2.5.6 Setting by cooling 33 2.5.7 Algina te/pectin gels 34 vi CONTENTS

2.6 Alginate processes for food production 34 2.6.1 General 34 2.6.2 Appropriate food raw materials 36 2.6.3 Commercial alginate gel restructured products 36 2.6.4 Examples of production formats 38 2.6.5 Alginate products for the bakery industry 38 2.7 Thickening and stabilising 40 2.7.1 Thickening 40 2.7.2 Stabilising 41 2.7.3 Thickening/stabilising with propylene glycol alginate 41 2.8 Film formation 42 2.9 Summary 42 References 44

3 Carrageenan 45 W.R. THOMAS

3.1 Introduction 45 3.2 Raw materials 45 3.3 Manufacturing 47 3.4 Regulation 48 3.5 Functional properties 49 3.6 Synergism with food ingredients 54 3.7 Food applications 56 References 59

4 Cellulose derivatives 60 D. ZECHER and T. GERRISH

4.1 Introduction 60 4.2 Manufacture 60 4.3 MC and MHPC: chemistry and properties 62 4.4 HPC: chemistry and properties 67 4.5 CMC: chemistry and properties 70 4.6 Major commercial applications in food products 75 4.6.1 Introduction 75 4.6.2 Frozen desserts 75 4.6.3 Fruit juice-based drinks and products 78 4.6.4 Bakery products 79 4.6.5 Dairy products 80 4.6.6 Structured, extruded and coated products 81 4.6.7 Miscellaneous food applications 82 4.6.8 Future developments 83 References 83

5 Exudate gums 86 M.V. WAREING

5.1 Introduction 86 5.2 Gum arabic 86 5.2.1 Introduction 86 5.2.2 Manufacture 88 5.2.3 Chemical composition 90 5.2.4 Functional properties 91 5.2.5 Applications 96 5.2.6 Future developments 99 CONTENTS Vll

5.3 Gum tragacanth 100 5.3.1 Introduction 100 5.3.2 Manufacture 101 5.3.3 Chemical composition 102 5.3.4 Functional properties 103 5.3.5 Applications 105 5.3.6 Future developments 109 5.4 Gum karaya 109 5.4.1 Introduction 109 5.4.2 Manufacture 110 5.4.3 Chemical composition 111 5.4.4 Functional properties 112 5.4.5 Applications 114 5.4.6 Future developments 116 References 116

6 Gellan gum 119 W. GIBSON and G.R. SANDERSON

6.1 Introduction 119 6.2 Manufacture 119 6.3 Chemical composition 119 6.4 Functional properties 121 6.4.1 Hydration 121 6.4.2 Solution properties 122 6.4.3 Gel formation 124 6.4.4 Gel properties 126 6.4.5 Gum combinations 134 6.5 Regulatory status 136 6.6 Applications 137 6.7 Future developments 140 References 142

7 Gelatin 144 1. POPPE

7.1 Introduction 144 7.2 Gelatin: definition 144 7.3 Collagen 145 7.4 Collagen-gelatin transformation 146 7.5 Gelatin manufacture 146 7.5.1 Pretreatment 147 7.5.2 Extraction and post-extraction processing 147 7.5.3 Commercial gelatin 149 7.6 Chemical structure 150 7.6.1 Composition 150 7.6.2 Isoelectric point 151 7.6.3 Molecular weight and molecular weight distribution 151 7.7 Functional properties 152 7.7.1 Gelation mechanism 152 7.7.2 Gel strength 152 7.7.3 Melting point 154 7.7.4 Setting point 154 7.7.5 Viscosity 155 7.7.6 Turbidity 155 7.7.7 Colour 156 7.7.8 Colloid protection 156 viii CONTENTS

7.8 Uses of gelatin in the food industry 156 7.8.1 Confectionery 158 7.8.2 Dairy products 161

7.8.3 Meat industry 164 7.8.4 Hydrolysed gelatin applications 166 7.8.5 Miscellaneous applications 166 References 167

8 Konjac gum 169 W.R. THOMAS

8.1 Introduction 169 8.2 Raw materials 169 8.3 Manufacturing 170 8.4 Regulation 172 8.5 Chemical structure 172 8.6 Functional properties 174 8.6.1 Thickening agent 174 8.6.2 Gelling agent: thermally reversible gels 175 8.6.3 Thermally stable gels 176 8.7 Dietary fibre 176 8.8 Food applications 177 Additional reading 178

9 Microcrystalline cellulose 180 A.P. IMESON and W. HUMPHREYS

9.1 Introduction 180 9.2 Raw materials 180 9.3 Manufacturing process 181 9.4 Chemical composition 184 9.5 Physical and functional properties 186 9.6 Interactions with other food ingredients 190 9.7 Applications in foods 190 9.7.1 Dressings, sauces and spreads 192 9.7.2 Processed cheese 193 9.7.3 Frozen desserts and ice cream 194 9.7.4 Dairy products 195 9.7.5 Meat products 196 9.7.6 Powdered cellulose 196 9.7.7 Bakery fillings, toppings and coatings 196 9.8 Legislation and nutrition 197 9.9 Future developments 197 References 197

10 Modified starches 199 A. RAPAILLE and J. VANHEMELRIJCK

10.1 Introduction 199 10.1.1 Sources 199 10.1.2 Availability 199 10.1.3 Quantities 199 10.2 Chemical composition 200 10.2.1 Structure of starch 200 CONTENTS IX

10.2.2 Principal properties of native starches 201 10.3 Starch manufacturing process 201 10.3.1 Basic separation processes 201 10.3.2 Starch modification types and techniques 203 10.4 Physical and sensory properties of native and modified starches 206 10.4.1 Pasting characteristics 206 10.4.2 Viscosity stability to heat, acid and shear 207 10.4.3 Sensory and textural properties 210 10.5 Preparation and use 213 10.5.1 Optimal preparation conditions for starch pastes 213 10.5.2 Influence of other food components 214 10.6 Major commercial applications 214 10.6.1 Confectionery 215 10.6.2 Canned and bottled foods 217 10.6.3 Frozen foods 218 10.6.4 Dairy desserts 218 10.6.5 Food powders 225 10.6.6 Bakery products 226 10.6.7 Miscellaneous 228 Further reading 229

11 Pectins 230 C.D. MAY

11.1 Occurrence and sources of pectin 230 11.2 Chemical nature of pectin 232 11.3 Pectin manufacture 233 11.4 Modification of pectin 234 11.5 Properties of pectin 235 11.5.1 Solubility and viscosity 235 11.5.2 Degradation 236 11.6 Gelation: high methoxyl pectins 236 11.7 Gelation: low methoxyl pectins 238 11.8 Interaction with other polymers 240 11.9 Physiological properties: dietary fibre 240 11.10 Legal status 241 11.11 lams and jellies: traditional high-sugar products 241 11.12 lams and jellies: reduced sugar 244 11.13 Fruit products for bakery applications 246 11.13.1 Bake-stable products 247 11.13.2 Glazes 248 11.14 Fruit preparations 250 11.15 Desserts 251 11.15.1 Water-based desserts 251 11.15.2 Dairy desserts 252 11.16 Confectionery 254 11.17 Savoury products 258 11.18 Low-calorie drinks 259 11.19 Dairy drinks 259 11.19.1 Yoghurt drinks 259 11.19.2 Whey drinks 259 11.19.3 Milk/juice blends 259 11.20 Other food uses and potential uses 260 References 260

12 Seed gums 262 J.E. FOX x CONTENTS

12.1 Introduction 262 12.2 Galactomannans 262 12.2.1 Locust bean gum 263 12.2.2 Guar gum 266 12.2.3 Tara gum 267 12.3 Chemical structure 269 12.4 Properties 270 12.4.1 Solubility 270 12.4.2 Viscosity 272 12.4.3 Interaction with other hydrocolloids 275 12.4.4 Stability 275 12.4.5 Interaction with protein 276 12.5 Applications of galactomannans 276 12.5.1 Milk-based products 277 12.5.2 Desserts 279 12.5.3 Mayonnaises 279 12.5.4 Dressings and ketchups 280 12.5.5 Sterilised soups and sauces 280 12.5.6 Deep-frozen foods 281 12.5.7 Other uses 281 12.6 Conclusion 281 References 282

13 Xanthan gum 284 B. URLACHER and O. NOBLE

13.1 Introduction 284 13.2 Process 284 13.3 Molecular structure 286 13.4 Xanthan gum in solution 289 13.4.1 Rheological properties 289 13.4.2 Stability and compatibility 291 13.5 Solution preparation and use 296 13.6 Gum associations 300 13.6.1 Xanthan-galactomannan interactions 300 13.6.2 Xanthan-glucomannan (konjac flour-gum interactions) 306 13.6.3 Xanthan-starch interactions 307 13.7 Applications 307 13.7.1 Dressings 307 13.7.2 Sauces, gravies, relishes and canned soups 309 13.7.3 Dairy products 309 13.7.4 Whipped creams and mousses 309 13.7.5 Instant mixes: drinks, soups and desserts 309 13.7.6 Bakery products 310 13.7.7 Syrups, toppings and fillings 310 13.7.8 Pet foods 310 13.7.9 Fruit preparations 311 References 311 Index 312 Contributors

Rafael Armisen Hispanagar SA, Calle Lopez Bravo, 98 Poligono Indus• trial Villalonquejar, Apartado Postal 392, 09080 Burgos, Spain John E. Fox G.c. Hahn & Co., Aegidienstr 22, D-23552 Lubeck 1, Germany Timothy C. Gerrish Hercules Inc., Research Centre, 500 Hercules Road, Wilmington, Delaware 19808-1599, USA William Gibson The NutraSweet KeIco Company, A Unit of Monsanto pIc, Waterfield, Tadworth, Surrey, KT20 5HQ, UK William Humphreys FMC Europe NV, Food Ingredients Division, Tech• nical Center, Avenue E Mounier 83 B2, 1200 Brussels, Belgium Alan P. Imeson FMC Corporation (UK) Ltd, Food Ingredients Division, 3C Harcourt Way, Meridian Business Park, Leicester, LE3 2WP, UK Colin D. May Citrus Colloids Ltd, Pomona Place, Hereford, HR4 ODA, UK Olivier Noble Rhone Poulenc Recherches, 52 Rue de la Haie Coq, 93308 Aubervilliers Cedex, France Edvar Onsoyen Pronova Biopolymer a.s, PO Box 494, N-3002 Drammen, Norway Jan Poppe Systems Bio-Industries Benelux NV, Meulestedekaai 81, B-9000 Gent, Belgium Andre Rapaille Cerestar, Eridania Beghin-Say Vilvoorde Research & Development Centre, Havenstraat 84, 1800 Vilvoorde, Belgium George R. Sanderson The NutraSweet KeIco Company, A Unit of Monsanto Company, PO Box 23576, 8355 Aero Drive, San Diego, Califor• nia 92123-1718, USA William R. Thomas FMC Corporation, Food Ingredients Division, Box 8, Princeton, New Jersey 08543, USA Brice Urlacher Rhone-Poulence Mayhall, Sonnenwiesenstrasse 18, Postfach 862, CH-8280 Kreuzlingen, Switzerland xii CONTRIBUTORS

Joast Vanhemelrijck Cerestar, Eridania-Beghin Say Vilvoorde Research & Development Centre, Havenstraat 84, B-1800 Vilvoorde, Belgium Mark V. Wareing Arthur Branwell & Co Ltd., Bronte House, 58-62 High Street, Epping, Essex, CM16 4AE, UK David C. Zecher Hercules Inc., Research Center, 500 Hercules Road, Wilmington, Delaware 19808-1599, USA Preface

The sucess of the first edition of Thickening and Gelling Agents for Food underlined the keen interest in functional food ingredients. In this second edition, the text has been completely revised and updated to reflect the current market trends. New chapters have been included to broaden the scope of materials used by the food technologist. Agar and konjac gum (flour), probably the most traditional gelling and thickening agents, but most widely utilised in the Far East, have been given greater prominence. Microcrystalline cellulose, a relatively new food stabiliser used widely in the USA, has been included. The preparation of traditional products using formulations suited to bulk food processings is described while new areas focus on low fat and low calorie foods where there is an even greater demand for controlling the stability, viscosity, gelation and mouthfeel using a broad range of thickening and gelling agents. Recent legislative changes in the USA and EC impact the use of additives including gellan gum, konjac flour, carrageenan, tara gum and microcrystal• line cellulose: some changes have increased the number of additives ap• proved for foods, while others allow a broader range of materials to be used in foods. The detailed information on products, properties and applications given in this second edition will enable these highly functional thickening and gelling agents to be used to full advantage. A. I. Preface to the first edition

Thickening and gelling agents are invaluable for providing high quality foods with consistent properties, shelf stability and good consumer appeal and acceptance. Modern lifestyles and consumer demands are expected to increase the requirements for these products. Traditionally, starch and gelatin have been used to provide the desired textural properties in foods. Large-scale processing technology places greater demands on the thickeners and gelling agents employed. Modified starches and specific qualities of gelatin are required, together with exudate and seed gums, seaweed extracts and, most recently, microbial polysac• charides, to improve product mouthfeel properties, handling, and stability characteristics. These hydrocolloids have been established as valuable food additives as a result of extensive practical experience with different prod• ucts. Nevertheless, the last few years have produced much additional re• search data from sophisticated new analytical methods. Information on the fine structure of these complex molecules has given a tremendous insight into the three-dimensional conformation of hydrocolloids and their behav• iour in solution. Critical components within the biopolymer have been identified which provide particular thickening, suspending, stabilising, emulsifying and gelling properties. Contributions for this book have been provided by senior development managers and scientists from the major hydrocolloid suppliers in the US and Europe. The wealth of practical experience within this industry, together with chemical. structural and functional data, has been collated to provide an authoritative and balanced view of the commercially signifi• cant thickening and gelling agents in major existing and potential food applications. This is a highly practical manual directed to all people involved in the many diverse aspects of food production. Formulation and development technologists, technical managers, process engineers, production personnel, ingredient purchasers and marketing managers will be able to identify the most appropriate products for preparing high quality foods with consistent properties. This concise, modern review of hydrocolloid developments will be in• valuable as a teaching resource and reference text for all academic and training courses involved with food preparation, production and research.

A. I.