Cellulose and Cellulose Derivatives in the Food Industry: Fundamentals and Applications

Cellulose and its derivatives can be found in many forms in nature and is a valuable material for all manner of applications in industry. This book is authored by an expert with many years of experience as an application engineer at renowned cellulose processing companies in the food industry. All the conventional and latest knowledge available on cellulose and its derivatives is presented. The necessary details are elucidated from a theoretical and practical viewpoint, while retaining the focus on food applications. This book is an essential source of information and includes recommendations and instructions of a general nature to assist readers in the exploration of possible applications of cellulose and its derivatives, as well as providing food for thought for the generation of new ideas for product development. Topics include gelling and rheological properties, synergistic effects with other hydrocolloids, as well as nutritional and legal aspects. The resulting compilation covers all the information and advice needed for the successful development, implementation, and handling of cellulose–containing products.

Preface XV List of Abbreviations XVII 1 General Overview of Food Hydrocolloids 1 1.1 Introduction to the World of Hydrocolloids 1 1.2 Plant Extracts 2 1.2.1 Agar 2 1.2.2 Alginates and PGA 6 1.2.3 Carrageenan 10 1.2.4 Pectins 16 1.2.5 Native and Modified Starches 21 1.2.6 Furcellaran 27 1.2.7 Larch Gum 28 1.3 Seed Flours 29 1.3.1 Guar Gum 29 1.3.2 Locust Bean Gum (Carob) 32 1.3.3 Tara Gum 34 1.3.4 Tamarind Seed Gum 36 1.3.5 Konjac Gum 37 1.4 Exudates 39 1.4.1 Acacia Gum/Gum Arabic 39 1.4.2 Tragacanth 43 1.4.3 Karaya Gum 45 1.4.4 Ghatti Gum 48 1.5 Bacterial Polysaccharides 50 1.5.1 Xanthan 50 1.5.2 Others 53 1.6 Overview Tables for the Most Important Cellulose Derivatives 60 1.7 Commercial Development – Global Market 65 References 68 2 Rheology of Food Hydrocolloids 69 2.1 Introduction to Rheology, Rheometry, and Visco–Elasticity 69 2.2 Definitions 69 2.3 Basic Data 72 2.4 Different Types of Flow Behaviour 72 2.5 Structures of Polymers with Shear–Thinning Flow Behaviour 78 2.6 Causes of Shear–Thickening of Products 80 2.7 Factors that Influence Rheological Behaviour 81 2.8 Viscosity Measurement of Thickening Hydrocolloid Solutions 82 2.9 Characterization of Gels 83 2.10 Viscosimeters and Rheometers 85 2.11 Relationship between Rheology and Sensory 88 References 90 3 Cellulose 91 3.1 Introduction, History and Development 91 3.1.1 Introduction 91 3.1.2 Historical Origin 92 3.1.3 Industrial Development from the Beginning to Today 92 3.1.4 Current Data for Cellulose Processing 94 3.2 Raw Materials and Biological Origin 95 3.2.1 Occurrence 95 3.2.2 Potential Sources for Natural Cellulosic Fibres 95 3.2.3 Wood as Cellulose Supplier 96 3.2.3.1 Tree Wood and Perennial Plants 96 3.2.3.2 Annual Plants 99 3.2.4 Bacterial Cellulose 100 3.2.5 Biosynthesis 101 3.2.6 Biological Composition 103 3.2.6.1 Cotton Fibres 107 3.2.6.2 Wood Fibres 107 3.2.7 Explanation for Industrial Derivatization 107 3.3 Manufacture of Pulp 109 3.3.1 Purification of Natural Cellulose Sources 109 3.3.2 Cotton Linters 109 3.3.3 Wood 110 3.4 Chemical Composition and Structure 111 3.4.1 Molecular Structure 111 3.4.1.1 Basic Structure 111 3.4.1.2 Differences between Cellulose and Starch 113 3.4.1.3 Structural Anomalies 114 3.4.1.4 Chain Length and Molecular Weight 115 3.4.2 Secondary Structure 117 3.4.2.1 Lattice Structure and Crystallization 118 3.4.2.2 Hydrogen Bonding 126 3.4.2.3 Chain Stiffness of the Cellulose Molecule 127 3.4.3 Supramolecular Structure of Native Cellulose Fibres 127 3.5 Rheology 129 3.5.1 Dissolution Behaviour 129 3.5.2 Gelation and Behaviour with Other Ingredients 130 3.6 Stability 130 3.6.1 Physical Properties 130 3.6.2 Stability in Food Products 131 3.6.3 Chemical Reactions 131 3.6.4 Possibilities for Degradation 134 3.7 Analysis and Rheometry 135 3.7.1 Qualitative Analysis 135 3.7.2 Quantitative Determination 136 3.7.3 Characterization of Structure of Cellulose Fibres 136 3.7.4 Viscosity Measurement 137 3.8 Synergies with Other Hydrocolloids 137 3.9 Application in Food Products 137 3.10 Non–food Applications 138 3.11 Options for Derivatization of Cellulose 138 3.12 Nutritional Properties 138 3.13 Legislation 140 References 141 4 Microcrystalline Cellulose 143 4.1 General Manufacturing Process 143 4.1.1 Powdered MCC 144 4.1.2 Colloidal MCC 145 4.1.2.1 Principle of the Colloidal MCC Process 145 4.1.2.2 Co–processing with Other Hydrocolloids 145 4.1.2.3 Physical Modification with Other Functional Substances (‘Alloying Concept’) 147 4.2 Chemistry 148 4.3 Rheology 148 4.3.1 Dissolution Behaviour 148 4.3.2 Gelation and Behaviour with Other Ingredients 149 4.3.3 Special Behaviour of Colloidal MCC with Guar Gum 150 4.4 Stability 151 4.5 Rheometry 155 4.6 Preparation of MCC Dispersions in Food 155 4.6.1 Key Factors 155 4.6.2 Instruction and Testing 156 4.7 Synergies with Other Hydrocolloids 157 4.8 Functions and Properties of MCC 158 4.8.1 Powdered MCC 158 4.8.2 Specialist Powdered MCC 158 4.8.3 Colloidal MCC 159 4.9 Food Applications with Typical Formulations 159 4.9.1 Baked Goods, Snacks, and Fillings 161 4.9.2 Dairy Products – Ice Cream, Desserts, and Cheese Preparations 163 4.9.3 Whipping Creams – Dairy and Vegetable Fat Based 166 4.9.4 Confectionery 169 4.9.5 Beverages (RTD) 171 4.9.6 Soups, Sauces, Salad Dressings, Marinades, and Spreads 176 4.9.7 Meat Products 180 4.9.8 Applications for Powdered Cellulose 180 4.10 Non–food Applications 181 4.11 Nutritional Properties 181 4.12 Legislation 182 References 183 5 Fundamentals of Water–Soluble Cellulose Ethers and Methylcellulose 185 5.1 Manufacturing Process of Cellulose Ethers 185 5.1.1 General Principles 185 5.1.2 Production of the Monoether Methylcellulose 188 5.2 Chemistry 190 5.3 Rheology 191 5.3.1 General Swelling and Dissolution Behaviour of Cellulose Ethers 191 5.3.1.1 Factors of Influence 191 5.3.1.2 Stages of Swelling to Dissolution 194 5.3.2 Dissolution Behaviour of the Monoether Methylcellulose 196 5.3.2.1 Suitable Solvents 196 5.3.2.2 Physicochemical Data 197 5.3.2.3 Molecular Weight and Viscosity 198 5.3.2.4 Rheological Profile – Factors Influencing the Cold Viscosity 198 5.3.2.5 Surface Activity of Aqueous Solutions 204 5.3.2.6 Mixtures and Blending for Viscosity Adjustment 206 5.3.2.7 Available Solid Forms of MC 208 5.3.3 Gelation of Methylcellulose 208 5.3.3.1 Basics and Relationships 208 5.3.3.2 Influence of Solvent on Gelation 214 5.3.3.3 Mechanism and Cause of Heat–Induced Gelation 216 5.3.3.4 Non–thermal Gelation 218 5.3.3.5 Difference between Methylcellulose and HPMC 218 5.3.3.6 Gel Strength of Different Food Binders 219 5.3.4 Dispersion and Hydration 219 5.3.5 Technique of Delayed Hydration 222 5.3.6 Functional Properties Resulting from Methylation 223 5.3.7 Behaviour of Methylcellulose with Other Ingredients 224 5.3.8 Methylcellulose and HPMC for Fat Reduction in Coatings 230 5.3.9 Emulsifying Properties of Methylcellulose 233 5.4 Stability 235 5.4.1 Storage Stability of Cellulose Ethers 235 5.4.2 Microbiological Stability 236 5.4.3 Process Stability after Hydration 237 5.5 Rheometry 241 5.5.1 Analytical Procedures to Define Substitution of MC 241 5.5.2 Determination of the Molecular Weight 242 5.5.3 Methods of Identification and Quantitative Determination 242 5.6 Synergies with Other Hydrocolloids 242 5.7 Food Applications with Typical Formulations 243 5.7.1 Bakery Products 244 5.7.1.1 Functions and Overview 244 5.7.1.2 Typical Formulations 245 5.7.2 Fillings 248 5.7.2.1 Functions and Overview 248 5.7.2.2 Typical Formulations 248 5.7.3 Glazes, Predusts, Coatings, and Batters 248 5.7.3.1 Functions and Overview 248 5.7.3.2 Typical Formulations 250 5.7.4 Reformed and Extruded Products 250 5.7.4.1 Functions and Overview 250 5.7.4.2 Typical Formulations 252 5.7.5 Soups and Sauces, Salad Dressings, and Marinades 252 5.7.5.1 Functions and Overview 252 5.7.5.2 Starch–Methylcellulose Synergism in Sauces 256 5.7.5.3 Traditional Soups, Sauces, Toppings 256 5.7.5.4 Emulsions 258 5.7.6 Confectionery and Desserts 260 5.7.7 Meat and Fish Products 260 5.7.8 Pet Food and Animal Feed 260 5.8 Non–food Applications 263 5.9 Nutritional Properties 271 5.10 Legislation 272 References 273 6 Ethylcellulose 275 6.1 Manufacturing 275 6.2 Chemistry 276 6.3 Rheology 277 6.3.1 Physicochemical Parameters 277 6.3.2 Dissolution Behaviour 278 6.3.2.1 Solubility in Water 278 6.3.2.2 Suitable Solvents 279 6.3.2.3 Viscosity–Concentration Relationships 281 6.3.2.4 Blending 283 6.3.3 Gelation and Behaviour with Other Ingredients 286 6.3.3.1 Overview 286 6.3.3.2 Compatibility with Resins 287 6.3.3.3 Compatibility with Plasticizers 291 6.3.4 Physical Properties 295 6.3.5 Temperature and Viscosity 298 6.3.6 Films 298 6.3.6.1 Selection of Solvent 298 6.3.6.2 Selection of Plasticizer 299 6.4 Stability 299 6.5 Rheometry 305 6.6 Synergies with Other Hydrocolloids 305 6.7 Food Applications with Typical Formulations 306 6.7.1 Overview of Functions 306 6.7.2 Coating and Encapsulation with Ethylcellulose 308 6.8 Non–food Applications 308 6.9 Nutritional Properties 315 6.10 Legislation 316 References 318 7 Hydroxypropylcellulose 319 7.1 Manufacturing 319 7.2 Chemistry 319 7.3 Rheology 321 7.3.1 Physicochemical Parameters and Properties 321 7.3.2 Dissolution Behaviour 322 7.3.2.1 Suitable Solvents 322 7.3.2.2 Dissolution Curves in Water and Aqueous Alcohol Mixtures 325 7.3.2.3 Surface and Interfacial Tension 326 7.3.3 Gelation and Behaviour with Other Ingredients 327 7.4 Stability 329 7.4.1 Process Stability 329 7.4.2 Hygroscopicity 331 7.4.3 Polymer Degradation 331 7.4.4 Combustion 332 7.4.5 Thermoplasticity and Film Formation 332 7.5 Rheometry 333 7.6 Synergies with Other Hydrocolloids 333 7.7 Food Applications with Typical Formulations 334 7.7.1 Foam Products 334 7.7.2 Films and Coatings 335 7.8 Non–food Applications 339 7.9 Nutritional Properties 339 7.10 Legislation 339 References 341 8 Hydroxypropylmethylcellulose 343 8.1 Manufacturing 343 8.2 Chemistry 344 8.3 Rheology 345 8.3.1 Dissolution Behaviour 345 8.3.2 Gelation of Hydroxypropylmethylcellulose 347 8.3.3 Behaviour of HPMC with Other Ingredients 348 8.4 Stability 350 8.5 Rheometry 351 8.6 Synergies with Other Hydrocolloids 352 8.7 Food Applications with Typical Formulations 352 8.7.1 Foams 352 8.7.2 Films and Coatings with HPMC 354 8.7.2.1 Overview 354 8.7.2.2 Typical Formulations 354 8.7.3 Fillings 356 8.7.4 Bakery Products with HPMC 358 8.7.4.1 Traditional Baked Goods 358 8.7.4.2 Gluten–Free Products 361 8.7.5 Chilled and Frozen Dairy Products and Desserts 363 8.7.5.1 Functions and Overview 363 8.7.5.2 Typical Formulations 364 8.7.6 Confectionery 366 8.7.7 Reformed Products with HPMC 368 8.7.8 Soups, Sauces, Salad Dressings, and Marinades 370 8.7.9 Beverages 372 8.7.9.1 Functions and Overview 372 8.7.9.2 Typical Formulations 372 8.7.10 Flavour Concentrates 372 8.7.10.1 Functions and Overview 372 8.7.10.2 Typical Formulations 374 8.8 Non–food Applications 375 8.9 Nutritional Properties 375 8.10 Legislation 375 References 376 9 Methylethylcellulose 379 9.1 Manufacturing 379 9.2 Chemistry 380 9.3 Rheology 381 9.3.1 Dissolution Behaviour 381 9.3.2 Gelation and Behaviour with Other Ingredients 382 9.4 Stability 382 9.5 Rheometry 383 9.6 Synergies with Other Hydrocolloids 383 9.7 Food Applications with Typical Formulations 384 9.8 Non–food Applications 384 9.9 Nutritional Properties 385 9.10 Legislation 385 References 385 10 Sodium Carboxymethylcellulose 387 10.1 Manufacturing 387 10.2 Chemistry 388 10.3 Rheology 390 10.3.1 Dissolution Behaviour 390 10.3.1.1 General Correlations 390 10.3.1.2 Physicochemical Parameters and Properties 394 10.3.1.3 Rheological Profiles and CMC Design 394 10.3.1.4 Shear–Thinning of Polymer Solutions 395 10.3.1.5 Relationship between DS, DP, and Flow Characteristics of CMC 396 10.3.1.6 Effect of Shear on CMC Solutions 396 10.3.1.7 Influence of Solvent Mixtures 400 10.3.1.8 Effect of Dissolved Substances on the Viscosity 402 10.3.1.9 Blends of CMC Types 403 10.3.2 Gelation of Carboxymethylcellulose 404 10.3.3 Behaviour of CMC with Other Ingredients 408 10.4 Stability 422 10.4.1 Microbiological Attacks 422 10.4.2 Chemical Degradation 423 10.4.3 Functional Stability 423 10.4.4 Films of CMC 431 10.5 Rheometry 433 10.6 Synergies of Cellulose Gum with Other Hydrocolloids 434 10.6.1 Behaviour with Other Thickeners 434 10.6.2 Interactions with Traditional Gelling Agents 434 10.7 Functional Properties of Carboxymethylcellulose 435 10.8 Use of Purified CMC in Regulated Applications 436 10.9 Food Applications with Typical Formulations 438 10.9.1 Bakery and Cereal Products 438 10.9.2 Dairy Products – Ice Cream, Desserts, and Cheese Preparations 441 10.9.3 Syrups and Fillings 444 10.9.4 Beverages (RTD, Concentrates, Emulsions) 445 10.9.5 Soups, Sauces, Salad Dressings, and Marinades 451 10.9.6 Meat Products 455 10.9.6.1 Scalded/Boiled Emulsified Meat Products – Sausages 455 10.9.6.2 Injection Brines 458 10.9.6.3 Sausage Casings 459 10.9.7 Pet Food and Animal Feed 460 10.9.8 Wine 461 10.9.8.1 Summary 461 10.10 Non–food Applications 464 10.10.1 Applications for Standard Grades of CMC – Overview 464 10.10.2 Technical and Regulated CMC Applications 466 10.10.3 General Overview for Use of CMC 471 10.11 Nutritional Properties 473 10.12 Legislation 473 10.12.1 European Union 473 10.12.2 Other Countries (Non–EU) 476 References 477 11 Crosslinked Sodium Carboxymethylcellulose 479 11.1 Manufacturing Process 479 11.2 Chemistry 479 11.3 Rheology 480 11.3.1 Dissolution Behaviour 480 11.3.2 Gelation and Behaviour with Other Ingredients 481 11.4 Stability 481 11.5 Rheometry 481 11.6 Synergies with Other Hydrocolloids 481 11.7 Food Applications with Typical Formulations 482 11.8 Non–food Applications 482 11.9 Nutritional Properties 482 11.10 Legislation 483 References 483 12 Enzymatically Hydrolysed Carboxymethylcellulose 485 12.1 Manufacturing Process 485 12.2 Chemistry 485 12.3 Rheology 487 12.3.1 Dissolution Behaviour 487 12.3.2 Gelation and Behaviour with Other Ingredients 487 12.4 Stability 487 12.5 Rheometry 488 12.6 Synergies with Other Hydrocolloids 488 12.7 Food Applications with Typical Formulations 489 12.8 Non–food Applications 489 12.9 Nutritional Properties 489 12.10 Legislation 490 Reference 490 13 Nanocellulose 491 13.1 Definition and Summary 491 13.2 Commercial Products 491 13.3 History and Terminology 492 13.4 Manufacturing Process 493 13.4.1 Nanocellulose/MFC 493 13.4.2 Cellulose Nanowhiskers 493 13.4.3 New Biotechnological Production Methods 494 13.5 Chemistry and Rheometry 496 13.5.1 Molecular Structure 496 13.5.2 Dimensions and Crystallinity 496 13.6 Rheology 497 13.6.1 Dissolution Behaviour 497 13.6.2 Viscosity and Gelation 498 13.7 Stability 498 13.8 Synergies with Other Substances 501 13.8.1 Reason for Interactions and Options 501 13.8.2 Chemical Modification 501 13.8.3 Bioactivity 502 13.9 Food Applications 503 13.10 Non–food Applications 503 13.11 Nutritional Properties and Toxicity 505 13.12 Safety Aspects 505 13.12.1 Conclusion 506 13.13 Regulatory Aspects in Europe 506 References 506 Index 511

Starting in 2003, Tanja Wuestenberg worked for 10 years as application manager at Dow Wolff Cellulosics (now Dow Company), where she became passionate about cellulose and cellulose derivatives and their multifunctional properties. She studied food technology at the University of Applied Sciences Fulda (Germany) and obtained her diploma as food engineer in 1998. Thereafter, Tanja Wuestenberg worked as development engineer in the food industry for many years and held positions at the Fraunhofer Institute for Process Engineering and Packaging (IVV) and Sensient Food Ingredients. Furthermore, she headed the European Technical Center at National Starch & Chemical in Hamburg (Germany) for several years. Tanja Wuestenberg is an expert in the application of cellulose ethers and the development of innovative cellulose–based products. She published several brochures on hydrocolloids and a cellulose book in German language.