Nanocomposites with Biodegradable Polymers

Nanocomposites with Biodegradable Polymers Synthesis, Properties and Future Perspectives Edited by Vikas Mittal Polymer Engineer, BASF Polymer Research, Ludwigshafen, Germany Current address (2011): The Petroleum Institute, Chemical Engineering Department, Abu Dhabi, UAE OXFORD UNIVERSITY PRESS

Contents List of contributors xv 1 Bio-nanocomposites: future high-value materials 1 Vikas MITTAL 1.1 Introduction to polymer nanocomposites 1 1.2 Biopolymers or biodegradable polymers 6 1.3 Bio-nanocomposites 7 1.4 References 23 2 Biodegradation of polymeric systems 28 In-Joo CHIN and Shogo UEMATSU 2.1 Biodegradable polymers and their composites 29 2.1.1 Mechanisms of biodegradation 29 2.1.2 Biodegradation of PLA and its nanocomposites 30 2.1.3 Biodegradation of PBS and its composites 34 2.1.4 Biodegradation of PCL 37 2.1.5 Biodegradation of PHB 38 2.2 Biodegradation tests under controlled composting conditions 40 2.2.1 Introduction 40 2.2.2 Test method for biodegradation of plastics under controlled composting conditions 41 2.2.3 Specifications of ISO 14855-1 and ISO 14855-2 42 2.2.4 Preparation of mature compost 44 2.2.5 ph of compost 45 2.2.6 Water activity (Aw) 46 2.2.7 Test equipment 48 2.2.8 Biodegradation of test materials 49 2.2.9 Conclusion 51 2.3 Acknowledgements 51 2.4 References 51 3 Biodegradable thermoplastic starch/poly(vinyl alcohol) nanocomposites with layered silicates 58 Katherine M. DEAN, Eustathios PETINAKIS and Long YU 3.1 Introduction 58 3.2 Materials and processing of thermoplastic starch/pvoh nanocomposites 60 3.3 Microstructure and chemistry of the thermoplastic starch/pvoh nanocomposites 62 3.3.1 XRD analysis of the structures 62

viii Contents 3.3.2 TEM analysis of the structures 65 3.3.3 Fourier transform infrared spectroscopy (FTIR) analysis ofthe structures 65 3.4 Mechanical properties of the thermoplastic starch/pvoh nanocomposites 67 3.5 Conclusions 68 3.6 Acknowledgements 69 3.7 References 69 4 Bio-nanocomposites with non-cellulosic biofillers 71 Peter R. CHANG, Jin HUANG and Ning LIN 4.1 Introduction 71 4.2 Manufacture of non-cellulosic nano-sized biofiller 72 4.2.1 Extraction of starch nanocrystal 72 4.2.2 Extraction of chitin nanowhisker 74 4.2.3 Organization of supramolecular lignin complex 75 4.2.4 Artificial nano-sized filler from biomass 75 4.3 Chemical modification of non-cellulosic biofiller 76 4.3.1 Chemical derivation of non-cellulosic biofiller 76 4.3.2 'Graft to' modification of non-cellulosic biofiller 78 4.3.3 'Graft from' modification of non-cellulosic biofiller 79 4.4 Processing of bio-nanocomposites with non-cellulosic biofiller 80 4.4.1 Solution blending and subsequent moulding of bio-nanocomposites 80 4.4.2 Compounding of nano-sized biofiller with reactive polymer matrix 81 4.4.3 Post-treatment of moulded bio-nanocomposites 82 4.4.4 Manufacturing of structural bio-nanocomposite materials 83 4.4.5 Thermoforming of polymer-grafted polysaccharide nanocrystals 85 4.4.6 Direct nanoscaffold formation from chitin whiskers 85 4.5 Mechanical properties of bio-nanocomposites with non-cellulosic biofiller 86 4.5.1 Effects of structure and loading level of biofiller 86 4.5.2 Effects of chemical modification of biofillers 87 4.5.3 Effects of processing conditions 89 4.5.4 Reinforcement mechanism of biofiller 89 4.6 Other properties of bio-nanocomposites with non-cellulosic biofiller 90 4.6.1 Thermal properties of bio-nanocomposites 90 4.6.2 Swelling behaviour of bio-nanocomposites 93 4.6.3 Barrier properties of bio-nanocomposites 94 4.7 Conclusion and prospects 95 4.8 References 96 5 Biodegradable poly(butylene succinate)/multi-walled carbon nanotube nanocomposites 101 Y. F. SHIH and R.J.JENG 5.1 Introduction 101 5.1.1 Biodegradable poly(butylene succinate) 101 5.1.2 Carbon nanotubes 102 5.1.3 Modifications of carbon nanotubes 102

Contents ix 5.1.4 Biodegradable polymer/cnts composites 104 5.1.5 Thermal degradation kinetics of PBS/CNTs composites 105 5.2 Experimental 105 5.2.1 Materials 105 5.2.2 Instruments 106 5.3 Results and discussion 106 5.3.1 Characterization of the organically grafted CNTs 106 5.3.2 DSC analysis of the PBS/CNTs nanocomposites 107 5.3.3 Mechanical properties of the PBS/CNTs nanocomposites 107 5.3.4 Electrical properties of the PBS/CNTs nanocomposites 111 5.3.5 Morphology of PBS/CNTs nanocomposites 112 5.3.6 Thermal degradation kinetics of PBS/CNTs nanocomposites 113 5.4 Conclusion 118 5.5 References 118 6 Biodegradable nanocomposites from cellulosic plastics and cellulosic fibre 123 Manju MISRA, Ozgur SEYDIBEYOGLU, Dipa RAY, Kunal DAS and Amar MOHANTY 6.1 Introduction to nanocomposites and biodegradable materials 123 6.2 Biobased and biodegradable materials 124 6.3 The importance of plant materials 126 6.4 Cellulosic plastics 127 6.4.1 Cellulose esters 127 6.4.2 Chitin 132 6.4.3 Chitosan 133 6.5 Cellulosic fibres (micron and nanoscale) 137 6.5.1 Cellulose nanowhiskers 140 6.5.2 Microfibrillated cellulose 145 6.5.3 Bacterial cellulose 149 6.6 Processing cellulose nanocomposites 155 6.7 Characterization of cellulose nanocomposites 157 6.8 Future perspectives 158 6.9 Concluding remarks 159 6.10 Acknowledgements 159 6.11 References 159 7 Silica/alginate bio-nanocomposites 166 Thibaud CORADIN 7.1 Introduction 166 7.2 Alginate-based materials 167 7.3 Design of silica/alginate biocomposites 169 7.3.1 The composite approach 170 7.3.2 The hybrid approach 171 7.3.3 The IPN approach 173 7.3.4 Scaling down of the procedures 173

x Contents 7A Physical and chemical properties of silica/alginate nanocomposites 174 7.4.1 Mechanical and thermal stability 174 7.4.2 Chemical stability 175 7.5 Applications 177 7.5.1 Enzymatic biocatalysts 177 7.5.2 Cell-based bioreactors 178 7.5.3 Artificial organs 179 7.5.4 Drug delivery systems 181 7.6 Extensions and perspectives 182 7.6.1 Other alginate-based bio-nanocomposites 182 7.6.2 Bases for further partnership 183 7.7 References 184 8 Bio-based elastomers from soy oil and nanoclay 189 Lin ZHU and Richard P. WOOL 8.1 Introduction 189 8.2 Experimental 192 8.2.1 Preparation of clay/elastomer elastomer hybrid 192 8.2.2 Characterization 193 8.3 Results and discussion 193 8.3.1 Organic modifier selection 193 8.3.2 Morphology 194 8.3.3 Mechanical properties 196 8.3.4 Crosslink density and network perfection 198 8.3.5 Thermal stability and glass transition temperature 201 8.3.6 Biodegradability 203 8.3.7 Biocompatibility 204 8.4 Conclusions 206 8.5 References 206 9 Gelatine-based bio-nanocomposites 209 Francisco M. FERNANDES, Margarita DARDER, Ana I. RUIZ, Pilar ARANDA and Eduardo RUIZ-HITZKY 9.1 Introduction 209 9.2 Gelatine composite materials 210 9.2.1 Gelatine, from the kitchen to the operating table 210 9.2.2 Gelatine, between collagen and synthetic polymers 211 9.2.3 Structural gelatine composites 213 9.2.4 Functional gelatine composites 214 9.3 Silica and silicate-based gelatine nanocomposites 216 9.3.1 Silica-based gelatine nanocomposites 216 9.3.2 Layered silicate-based nanocomposites 218 9.3.3 Fibrous silicate-based nanocomposites 220 9.4 Gelatine nanocomposites based on other inorganic solids 221 9.5 Gelatine in three-component nanocomposite systems 224 9.6 Future perspectives 226

Contents xi 9.7 Acknowledgements 226 9.8 References 226 10 Bio-nanocomposites based on starch 234 Fengwei XIE, Peter J. HALLEY and Luc AVEROUS 10.1 Introduction 234 10.2 Processing techniques 235 10.2.1 Solution intercalation 235 10.2.2 Melt intercalation 236 10.3 Starch-based bio-nanocomposites 236 10.3.1 Starch bio-nanocomposites filled by layered clays 236 10.3.2 Starch bio-nanocomposites filled by whiskers 248 10.3.3 Starch bio-nanocomposites filled by starch nanocrystals 250 10.3.4 Starch bio-nanocomposites filled by other types of nanofillers 250 10.4 Bio-nanocomposites based on other starch-based matrices 252 10.5 Applications 253 10.6 Summary 253 10.7 References 253 11 Soy protein-based polymer nanocomposites 261 Jin HUANG, Ning LIN, Yun CHEN, Peter R. CHANG and Jiahui YU 11.1 Introduction 261 11.2 Soy protein-based nanocomposites filled with inorganic nanofillers 262 11.2.1 Soy protein nanocomposites filled with layered silicates 262 11.2.2 Soy protein nanocomposites filled with spherical Si02 nanoparticles 264 11.2.3 Soy protein nanocomposites filled with carbon nanotube 265 11.2.4 In situ synthesis of soy protein/inorganic nanocrystal nanocomposites 266 11.3 Soy protein-based composites filled with organic nanofillers 267 11.3.1 Soy protein filled with polysaccharide nanocrystals 267 11.3.2 Soy protein filled with artificial nanoparticles 268 11.3.3 Soy protein filled with self-assembled nanoparticles 270 11.3.4 Soy protein filled with lignin nanophase 271 11.4 Structure-property relationship of soy protein-based nanocomposites 273 11.4.1 Interfacial interaction between nanofillers and soy protein matrix 273 11.4.2 Entanglement and penetration of polymer matrix with hollow nanoparticles 274 11.4.3 Self-organization organization of nanofillers in soy protein matrix 275 11.4.4 Co-continuous phase mediated with polymer chains on nanoparticles 277 11.4.5 In situ formed nanostructure in soy protein matrix 278

xii Contents 11.5 Conclusion and prospects 278 11.6 References 279 12 Biodegradable nanocomposites based on poly(hydroxyalkanoates) 283 Narendra K. SINGH and Pralay MAITI 12.1 Introduction 283 12.2 Preparation of poly(hydroxyalkanoate) nanocomposites 286 12.2.1 Solution casting method 286 12.2.2 Melt extrusion technique 286 12.2.3 In situ polymerization 286 12.3 Characterization of poly(hydroxyalkanoate) nanocomposites 287 12.3.1 Nanostructure 287 12.3.2 Microstructure 290 12.4 Properties 292 12.4.1 Mechanical properties 292 12.4.2 Thermal properties 301 12.4.3 Gas barrier properties 312 12.4.4 Biodegradation 314 12.5 Processing 320 12.5.1 Melt rheology and structure-property relationship 320 12.6 Uses 321 12.7 Conclusion 321 12.8 Acknowledgements 322 12.9 References 322 13 Bio-nanocomposites using bio-based epoxy resins 329 Mitsuhiro SHIBATA 13.1 Introduction 329 13.2 Bio-based epoxy resin/montmorillonite nanocomposites 332 13.2.1 Layered silicates as fillers of bio-nanocomposites 332 13.2.2 Preparation and morphology of PGPE-PL/MMT nanocomposites 332 13.2.3 Properties of PGPE-PL/MMT composites 333 13.3 Bio-based epoxy resin/microfibrillated cellulose nanocomposites 336 13.3.1 Microfibrillated cellulose as reinforcing fibres of bio-nanocomposites 336 13.3.2 Preparation of GPE/TA/MFC and SPE/TA/MFC 337 13.3.3 Properties of GPE-TA/MFC and SPE-TA/MFC 337 13.4 Bio-based epoxy resin/self-assembled hydroxystearic acid nanocomposites 341 13.4.1 Self-assembled suplamolecular fibres as reinforcing fibres of bio-nanocomposites 341 13.4.2 Preparation and characterization of photo-cured ESO/HSA nanocomposites 341 13.4.3 Mechanical properties of photo-cured ESO/HSA nanocomposites 344 13.5 References 345

Contents xiii 14 Bio-nanocomposites for food packaging applications 348 Caisa JOHANSSON 14.1 Background 348 14.2 Food packaging requirements 348 14.2.1 Paper-based packaging laminates 349 material 350 14.2.2 Self-supporting packaging 14.3 Industrial manufacture of bio-nanocomposite food packaging 351 14.4 Bio-nanocomposites 352 14.4.1 Nanosized components in bio-nanocomposites 352 14.4.2 Poly(lactic acid)-based nanocomposites 354 14.4.3 Polycaprolactone-based nanocomposites 355 14.4.4 Polyhydroxyalkanoate-based nanocomposites 356 14.4.5 Starch-based nanocomposites 356 14.4.6 Chitosan-based nanocomposites 357 14.4.7 Other classes of bio-nanocomposites 358 14.5 Costs and commercial availability of bio-nanocomposite components 359 14.6 Potential risks related to bio-nanocomposites in food packaging 360 14.6.1 Contamination and migration 360 14.7 Antimicrobial functionality in bio-nanocomposites 361 14.8 Environmental aspects of bio-nanocomposites 362 14.9 References 364 15 Conductive biopolymer nanocomposites for sensors 368 Jean-Francois FELLER, Bijandra KUMAR and Mickael CASTRO 15.1 Introduction 368 15.2 Conductive biopolymer nanocomposite (CPC) transducer development 369 15.2.1 Choice and association of materials for conductive biopolymer composite development 369 15.2.2 Conductive biopolymer nanocomposite architecture design 371 15.2.3 Conductive biopolymer nanocomposite transducer characterization 376 15.2.4 Instrumentation and tests 378 15.2.5 Principle of conductive biopolymer nanocomposite 15.2.6 Properties of conductive biopolymer nanocomposite resistive resistive sensors 379 transducers 382 15.2.7 Principle of conductive biopolymer nanocomposite electrochemical biosensors 390 15.2.8 Applications 391 15.3 Conclusion 391 15.4 References 391 16 Commercial aspects associated with bio-nanocomposites 400 Sunil P. LONKAR, A. Pratheep KUMAR and R. P SINGH 16.1 Introduction 400 16.2 Classification of bio-nanocomposites 401 16.2.1 Nanocomposites of biodegradable polymers 401 16.3 Commercial preparation, processing and challenges 407

xiv Contents 16.3.1 Method of preparation 407 16.3.2 Compounding of bio-nanocomposites 408 16.3.3 Thermosetting methods 409 16.3.4 Scale-up/challenges 409 16.3.5 Methods for improving the properties 410 16.4 Energy consumption 410 16.5 Commercial aspects of bio-nanocomposites: the importance 411 16.6 Future perspectives 414 16.7 Summary/conclusions 415 16.8 References 415 Index 421