Composites Materials for Food Packaging
Insight to Modern Food Science Series

The novel insights, as well as the main drawbacks of each engineered composites material is extensively evaluated taking into account the strong relationship between packaging materials, environmental and reusability concerns, food quality, and nutritional value.

Composites, by matching the properties of different components, allow the development of innovative and performing strategies for intelligent food packaging, thus overcoming the limitations of using only a single material.

The book starts with the description of montmorillonite and halloysite composites, subsequently moving to metal-based materials with special emphasis on silver, zinc, silicium and iron. After the discussion about how the biological influences of such materials can affect the performance of packaging, the investigation of superior properties of sp² carbon nanostructures is reported. Here, carbon nanotubes and graphene are described as starting points for the preparation of highly engineered composites able to promote the enhancement of shelf-life by virtue of their mechanical and electrical features.

Finally, in the effort to find innovative composites, the applicability of biodegradable materials from both natural (e.g. cellulose) and synthetic (e.g. polylactic acid ? PLA) origins, with the aim to prove that polymer-based materials can overcome some key limitations such as environmental impact and waste disposal.

Preface xv

1 Montmorillonite Composite Materials and Food Packaging 1
Aris E. Giannakas and Areti A. Leontiou

1.1 Introduction 1

1.2 Polymer/MMT-Based Packaging Materials 6

1.2.1 Polyethylene(PE)/MMT-Based Packaging Materials 8

1.2.2 Polystyrene(PS)/MMT-Based Packaging Materials 11

1.2.3 Polypropylene (PP)/MMT-Based Composites for Food Packaging 13

1.2.4 Poly(ethylene)terephthalate(PET)/MMT-Based Packaging Materials 16

1.3 Biopolymers and Protein/MMT-Based Packaging Materials 18

1.3.1 Starch/MMT-Based Packaging Materials 19

1.3.2 Cellulose/MMT-Based Packaging Materials 25

1.3.3 Chitosan/MMT Composite Materials 29

1.3.4 PLA/MMT-Based Packaging Materials 34

1.3.5 Protein /MMT-Based Packaging Materials 37

1.4 Ag⁺-Cu²⁺-Zn²⁺/MMT-Based Composites Packaging Materials 39

1.4.1 Ag⁺/MMT-Based Packaging Materials 40

1.4.2 Cu²⁺/MMT-Based Packaging Materials 42

1.4.3 Fe²⁺/MMT-Based Composites 44

1.5 Metal Oxide/MMT-Based Packaging Materials 45

1.6 Natural Antioxidants/MMT Composite Materials for Food Packaging 49

1.7 Enzyme/MMT-Based Composites Packaging Materials 56

1.8 Conclusion 60

References 61

2 Halloysite Containing Composites for Food Packaging Applications 73
Raluca Nicoleta Darie –Niţă and Cornelia Vasile

2.1 Halloysite 74

2.1.1 Molecular and Crystalline Structure 74

2.1.2 Properties 77

2.1.3 Surface Modification of HAL 78

2.1.3.1 Modification of the External Surface 79

2.1.3.2 Modification by Click Chemistry 80

2.2 Nanocomposites Containing HAL 80

2.2.1 HAL Containing Non-Degradable Synthetic Polymeric Nanocomposites for Food Packaging Applications 81

2.2.1.1 Processing Strategies 81

2.2.1.2 Polyolefins/HNTs Nanocomposites 83

2.2.1.3 Polystyrene/HNTs Nanocomposites 94

2.2.1.4 Polyamide/HNTs Nanocomposites 95

2.2.1.5 PET/HNTs Nanocomposites 97

2.2.1.6 Elastomers(Rubbers)/HNTs Nanocomposites 97

2.2.1.7 Epoxy/HNTs Nanocomposites 98

2.2.2 HAL-Containing Degradable Polymeric Bionanocomposites for Food Packaging 98

2.2.2.1 Preparation of HNT-Containing Degradable Nanocomposites 99

2.2.2.2 Properties of HNT-Containing Degradable Nanocomposites 101

2.2.2.3 Polyvinyl Alcohol (PVOH)/HNT 101

2.2.2.4 Polyalkanoates/HNT Nanocomposites 106

2.2.2.5 PLA/Halloysite Biocomposites 106

2.2.2.6 Polysaccharide-HNT Composites 107

2.2.2.7 Lignocellulose/Wood Fibers/HAL Clay Composites 109

2.2.2.8 Polysaccharides/HAL Clay Composites 110

2.2.2.9 Proteins/HNT Biocomposites 111

2.2.2.10 Natural Rubber/HNTs Composites 111

2.3 Conclusion 112

References 112

3 Silver Composite Materials and Food Packaging 123 

Amalia I. Cano, Amparo Chiralt and Chelo González-Martínez

3.1 Silver and Silver Compounds as Active Agents 124

3.1.1 History and Background 124

3.1.2 Chemical Species of Silver 125

3.1.3 Silver in Polymeric Matrices for Food Packaging Purposes 130

3.1.3.1 Different Methodologies to Incorporate Silver and Silver Species into Packaging Materials 130

3.1.3.2 Functional Characterization of Silver-Enriched Packaging Materials 131

3.1.4 Current Legislation Applied to Silver Composite Materials Used for Food Packaging 144

3.2 Conclusions 144

References 145

4 Zinc Composite Materials and Food Packaging 153
R. Venkatesan, T. Thendral Thiyagu and N. Rajeswari

4.1 Introduction 153

4.2 Food Packaging 154

4.3 Polymers in Food Packaging 154

4.4 Nanotechnology 156

4.5 Nano-Fillers 156

4.6 Classification of Nano-fillers 157

4.7 ZnO Nanoparticles 157

4.7.1 Advantages of ZnO Nanoparticles 157

4.7.2 Limitations of ZnO Nanoparticles 158

4.8 Composites 159

4.8.1 Classification of Composites 159

4.8.1.1 Metal Matrix Composites 159

4.8.1.2 Ceramic Matrix Composites 159

4.8.1.3 Polymer Matrix Composites 159

4.8.2 Components of Composites 159

4.8.2.1 Matrix 159

4.8.2.2 Fillers 160

4.8.2.3 Nanocomposites 160

4.8.3 Preparation of Nanocomposites 161

4.8.3.1 Solution Casting 161

4.8.3.2 In Situ Polymerization 162

4.8.3.3 Melt Extrusion 162

4.8.4 Properties of Nanocomposites 163

4.8.4.1 Mechanical Properties 163

4.8.4.2 Thermal Properties 163

4.8.4.3 Barrier Properties 163

4.8.4.4 Antimicrobial Properties 164

4.8.5 Applications of Nanocomposites 164

4.8.6 ZnO-Based Composites in Food Packaging 164

4.8.6.1 Preparation of ZnO Composites 166

4.8.6.2 Morphology of the ZnO Composites 167

4.8.6.3 Mechanical Properties of ZnO Composites 167

4.8.6.4 Barrier Properties of ZnO Composites 169

4.9 Conclusions 171

References 172

5 Silicium-Based Nanocomposite Materials for Food Packaging Applications 175
Tanja Radusin, Ivan Ristić, Branka Pilić, Donatella Duraccio and Aleksandra Novaković

5.1 Introduction 176

5.2 Nanosilica/Polymer Composites 178

5.2.1 Composite Preparation 179

5.2.1.1 Blending 179

5.2.1.2 Sol–Gel Process 181

5.2.1.3 In Situ Polymerization 181

5.3 Characterization of Polymer/Nancomposites 181

5.3.1 Morphology 182

5.3.2 Physical–Chemical Properties 184

5.3.2.1 Thermal Properties 184

5.3.2.2 Mechanical Properties 186

5.3.2.3 Crystallization of Polymer/Silica Nanocomposites 187

5.3.3 Barrier Properties 195

5.3.4 Optical Properties 196

5.3.5 Antimicrobial Properties 196

5.4 Conclusion 198

References 198

6 Nanoiron-Based Composite Oxygen Scavengers for Food Packaging 209
Zenon Foltynowicz

6.1 Introduction 210

6.1.1 The Effect of Oxygen on Packed Products 210

6.1.2 The Need of Oxygen Scavengers 211

6.2 Characteristics of Oxygen Scavengers 212

6.2.1 Types and Classification of Oxygen Absorbers 212

6.2.2 Iron-Based Oxygen Scavengers 213

6.2.3 The Factors Influences the Efficiency of Iron-Based Oxygen Scavengers 214

6.3 Nanomaterials and Nanoiron 216

6.3.1 Nanomaterials Property 216

6.3.2 Nanoiron Property 216

6.3.3 Nanoiron Preparation 217

6.4 Nanoiron-Based Composite Oxygen Scavengers 219

6.4.1 Why Nanoiron? 219

6.4.2 Nanoiron with Specific Properties 221

6.4.3 Composite Oxygen Scavengers Based on Nanoiron 223

6.4.4 Safety of the Use of Composite Oxygen Scavengers Based on Nanoiron 226

References 227

7 Carbon Nanotubes (CNTs) Composite Materials and Food Packaging 235
Dan Xu

7.1 Introductions on Carbon Nanotubes 236

7.2 Polymer/CNTs Composite Materials 236

7.2.1 Modification of CNTs 237

7.2.2 Fabrication Method 238

7.2.3 Properties 238

7.3 Safety Issues of CNTs and Polymer/CNTs Composites 243

7.3.1 Toxicity of CNTs 243

7.3.2 Migration of CNTs from Polymer/CNTs Composites 243

7.4 Outlook 244

References 244

8 Polymer/Graphene Nanocomposites for Food Packaging 251
Steven Merritt, Chaoying Wan, Barbara Shollock, Samson Patole and David M. Haddleton

8.1 Polymers for Food Packaging 251

8.2 Polymers for Steel Can Packaging 252

8.3 Water Permeation and Anticorrosion of Polymer Coatings 253

8.4 Polymer–Food Interactions 255

8.5 Polymer/Clay Nanocomposites 255

8.6 Polymer/Graphene Nanocomposites 257

8.6.1 Graphene and its Derivatives for Food Packaging 257

8.6.2 Biodegradable Polymer/Graphene Nanocomposites 259

8.6.3 Synthetic Polymer/Graphene Nanocomposites 262

8.7 Summary and Outlook 263

References 264

9 Biodegradability and Compostability of Food Nanopackaging Materials 269
Tomy J. Gutiérrez

9.1 Introduction 269

9.2 Biodegradability and Compostability 270

9.3 Biodegradability and Compostability of Food Nanopackaging Materials 274

9.3.1 Biodegradability and Compostability of Food Nanopackaging Made from Biopolymers 276

9.3.2 Biodegradability and Compostability of Food Nanopackaging Made from Nanoclays 277

9.3.3 Biodegradability and Compostability of Food Nanopackaging Made from Bionanocomposites 279

9.3.3.1 Biodegradability and Compostability of Food Nanopackaging Made from Bionanocomposites – Biopolymers/Nanoclays 281

9.3.3.2 Biodegradability and Compostability of Food Nanopackaging Made from Bionanocomposites - Biopolymer/ Nanocellulosic Materials 287

9.4 Conclusion 288

Conflicts of Interest 290

Acknowledgments 290

References 290

10 Nanocellulose in Food Packaging 297
Paula Criado, Farah M. J. Hossain, Stéphane Salmieri and Monique Lacroix

10.1 Antimicrobial Effectiveness of Biopolymeric Films/Coatings Containing Cellulose Nanostructures 298

10.1.1 Biopolymeric Films Containing CNCs 298

10.1.2 Bioactive Films Containing CNFs 305

10.1.3 Nanostructured Bio-Based Bacterial Cellulose (BC)-Containing Films 306

10.2 Physicochemical Properties of Bio-Nanocomposites Materials Reinforced with CNC 307

10.3 Enhancement of the Mechanical Properties of Polymers with CNC 308

10.4 Enhancement of the Barrier Properties of Polymers with CNC 309

10.5 Research Works on CNC as Biodegradable Reinforcement and Barrier Component 310

10.5.1 Grafting of Cellulose Nanocrystals for Food Packaging 312

10.5.2 TEMPO-Mediated Oxidation of Nanocellulose 312

10.5.3 Functionalization of Nanocellulose via TEMPO-Mediated Oxidation 313

10.5.4 Cationization of Nanocellulose with Antimicrobial Purposes 314

10.5.5 Esterification 316

10.5.6 Non-Covalent Surface Chemical Modification 317

10.5.7 Polymerization of Bioactive Compounds onto Nanocellulose Surface 318

10.6 Conclusion 319

References 320

11 Nanocellulose in Combination with Inorganic/Organic Biocides for Food Film Packaging Applications – Safety Issues Review 331
Kelsey L O’Donnell, Gloria S. Oporto and Noelle Comolli

11.1 Introduction 332

11.1.1 Typical Polymers and Processes Used to Prepare Flexible Films in the Packaging Industry 332

11.1.2 Current Organic and Inorganic Antimicrobial Materials (Biocides) Used in Packaging and Correlating Processing Conditions 334

11.1.3 Release of Active Components (Biocides) From Packaging Films – Tentative Mechanisms 336

11.2 Nanocellulose in Flexible Film Food Packaging 336

11.2.1 Current Forms of Cellulose Used in Packaging 336

11.2.2 Nanocellulose in Flexible Film Food Packaging 337

11.2.3 Nanocellulose in Combination with Organic and Inorganic Antimicrobial Materials 339

11.2.4 Nanocelulose in Combination with Copper and Benzalkounium Chloride – West Virginia University (WVU) Preliminary Results 341

11.2.4.1 Nanocellulose - Copper/Zinc: Synergistic Effect (Preliminary Experiments) 342

11.2.4.2 Nanocellulose - Benzalkonium Chloride (BZK) (Preliminary Experiments) 342

11.3 Health and Environmental Toxicity Evaluations of Active Antimicrobial Packaging 343

11.3.1 General Toxic Evaluations on Packaging Materials (In Vivo, In Vitro Testing) – the United States 344

11.3.2 General Toxic Evaluations on Packaging Materials (In Vivo, In Vitro Testing) – Europe 345

11.3.3 Specific Toxic Evaluation on Cellulosic and Nanocellulosic Materials 348

References 350

12 Composite Materials Based on PLA and its Applications in Food Packaging 355
Jesús R. Rodríguez-Núñez, Tomás J. Madera-Santana, Heidy Burrola-Núñez and Efrén G. Martínez-Encinas

12.1 Introduction 356

12.2 Synthesis of Polylactic Acid 356

12.3 Reinforcing Agents 359

12.3.1 Natural Fibers and Fillers 360

12.3.2 Synthetic Fibers and Fillers 366

12.4 Surface Modification of Fibers and Fillers 366

12.4.1 Physical Methods (Corona, Plasma, Irradiation Treatments) 367

12.4.2 Chemical Methods (Alkaline, Acetylation, Maleation, Silane, Enzymatic Treatment) 368

12.5 Nanostructures in the PLA Matrix 370

12.6 Processing Techniques 371

12.6.1 Processing Technologies of PLA Composites 372

12.6.1.1 Compression Molding 372

12.6.1.2 Extrusion 374

12.6.1.3 Injection Molding 375

12.6.1.4 Extrusion or Injection Blow Molding 377

12.6.1.5 Calendering, Cast Film, and Sheet 378

12.6.1.6 Thermoforming 379

12.6.1.7 Foaming PLA 379

12.7 Properties Related to Packaging Applications 381

12.7.1 Physical Properties 382

12.7.2 Mechanical Properties 384

12.7.3 Thermal Properties 385

12.7.4 Functional Properties 387

12.8 Recyclability of PLA 388

12.9 Biodegradation of PLA 389

12.10 Future Tendencies 390

References 391

13 Nanomaterial Migration from Composites into Food Matrices 401
Victor Gomes Lauriano Souza, Regiane Ribeiro-Santos, Patricia Freitas Rodrigues, Caio Gomide Otoni, Maria Paula Duarte, Isabel M. Coelhoso and Ana Luisa Fernando

13.1 Introduction 402

13.2 Nanotechnology in the Food Industry 403

13.2.1 Nanoparticle Characterization Techniques 403

13.2.2 Nanoparticle Characterization in Food Matrices 406

13.2.3 Nanomaterial Migration from Composites into Food Matrices: Case Studies 407

13.3 Nanoparticle Toxicology 413

13.3.1 Toxicological Tests 415

13.3.2 Toxicological Studies of ENMs Used in the Food Packaging Industry 417

13.3.3 Ecotoxicology of ENMs 419

13.4 Migration Assays and Current Legislation 420

13.4.1 Food Contact Nanomaterials 424

13.5 Conclusion 426

Acknowledgments 427

References 427

Index 437

Giuseppe Cirillo received his PhD in 2008 from the University of Calabria Italy where he is currently in a post-doctoral position. His research interests are in the development of functional polymers with tailored biological activity (antioxidant, antimicrobial, anticancer, chelating), the design of smart hydrogels for drug delivery, the study of the activity of innovative functional foods and nutraceuticals, and the synthesis and functionalization of carbon nanotubes-based devices for biomedical applications. He is the author and co-author of more than 100 publications, including four edited books with Wiley-Scrivener.

Marek A. Kozlowski has 47 years' experience in polymer chemistry and technology and is Professor Emeritus from Wroclaw University of Technology, Poland. He is the author of 360 papers and patents, holder of several national and international prizes and honours and is a member of IUPAC WP 4.1. His research interests include polymer blends and composites of pre-designed properties, in particular the interrelations between structure, processing and properties of multiphase systems. He is an Expert of the United Nations Industrial Development Organization and evaluator of proposals submitted to the European Community R&D Programs.

Umile Gianfranco Spizzirri obtained his PhD in 2005 from the University of Calabria. He is currently a member of the Technical Staff at the Department of Pharmacy, Nutrition and Health Science of the same university. His research activities are mainly related to the polymer chemistry and technology for the preparation of stimuli-responsive drug delivery system, functional polymers for food industry, and new analytical methodologies for the food quality and safety assessment. He is the author and co-author of more than 100 publications, including three edited books with Wiley-Scrivener.