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Extrusion Foaming of Bioplastics for Lightweight Structure in Food Packaging

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Extrusion Foaming of Bioplastics for Lightweight Structure in Food Packaging EXTRUSION FOAMING OF BIOPLASTICS FOR LIGHTWEIGHT STRUCTURE IN FOOD PACKAGING A thesis submitted for the degree of Doctor of Philosophy by Sitthi Duangphet School of Engineering and Design Brunel University December 2012 i Abstract This thesis reports the systematic approaches to overcome the key drawbacks of the pure PHBV, namely low crystallisation rate, tensile strength, ductility, melt viscosity, thermal stability and high materials cost. The physical, mechanical, thermal, and rheological properties of the pure PHBV were studied systematically first to lay a solid foundation for formulation development. The influence of blending with other biopolymers, inclusion of filler, and chain extender additives in terms of mechanical properties, rheology, thermal decomposition and crystallization kinetics were then followed. Creating lightweight structures by foaming is considered to be one of the effective ways to reduce material consumption, hence the reduction of density and morphology of PHBV-based foams using extrusion foaming technique were studied comprehensively in terms of extrusion conditions (temperature profiles, screw speed and material feeding rate) and the blowing agent content. The material cost reduction was achieved by adding low-cost filler (e.g. CaCO3) and reduction of density by foaming. The thermal instability was enhanced by incorporation of chain extender (e.g. Joncryl) and blending with a high thermal stability biopolymer (e.g. PBAT). The polymer blend also improved the ductility. Adding nucleation agent enhanced the crystallization rate to reduce stickiness of extruded sheet. The final formulation (PHBV/PBAT/CaCO3 composite) was successfully extruded into high quality sheet and thermoformed to produce prototype trays in an industrial scale trial. The effect of the extrusion conditions (temperature profiles, screw speed and material feeding rate) and the blowing agent content are correlated to the density reduction of the foams. 61 and 47 % density reduction were achieved for the commercial PHBV and the PHBV/PBAT/CaCO3 composite respectively and there exists further scope for more expansion if multiple variable optimisation of the conditions are carried out. ii Table of Contents Abstract ............................................................................................................................. i Table of Contents ........................................................................................................... ii List of Tables ................................................................................................................. vii List of Figures ................................................................................................................. ix List of Abbreviations ................................................................................................. xviii Acknowledgements ....................................................................................................... xxi Chapter 1. General Introduction .................................................................................. 1 1.1 Background ................................................................................................................ 1 1.2 Scope of the research .................................................................................................. 3 1.3 Layout of the thesis .................................................................................................... 4 Chapter 2. Literature Review ........................................................................................ 6 2.1 Food packaging ........................................................................................................... 6 2.1.1 Requirements for food packaging ..................................................................... 6 2.1.1.1 General properties of food packaging ..................................................... 8 2.1.1.2 Safety of food packaging ...................................................................... 10 2.1.1.3 Environmental compatibility ................................................................. 11 2.1.2 Food packaging design to meet requirements ................................................. 12 2.1.3 Plastics in food packaging .............................................................................. 14 2.1.3.1 Bioplastics in food packaging ............................................................... 15 2.2 Bioplastic materials and composites ......................................................................... 16 2.2.1 Classification of bioplastics ............................................................................ 16 iii 2.2.1.1 Extracted from natural polymers ........................................................... 18 2.2.1.2 Synthetic bioplastics.............................................................................. 23 2.2.1.3 Polymers synthesized by microorganisms ............................................ 27 2.2.2 Bioplastic blends and composites. .................................................................. 31 2.2.3 Test methods for biodegradability of bioplastics ............................................ 33 2.2.4 Growth of bioplastic market. .......................................................................... 34 2.3 Bioplastic foams ........................................................................................................ 36 2.3.1 Introduction to foams ...................................................................................... 36 2.3.2 Polymer foaming technologies ........................................................................ 38 2.3.2.1 Principles of foaming ............................................................................ 38 2.3.2.2 Foam structure and properties ............................................................... 45 2.3.2.3 Foaming processes ................................................................................ 53 Chapter 3. Materials and Experimental Details......................................................... 61 3.1 Raw materials and additives …. ............................................................................... 61 3.1.1 PHBV……………………………………………………. ............................. 61 3.1.2 PBAT... ........................................................................................................... 61 3.1.3 Chain extender…. ........................................................................................... 62 3.1.4 Blowing agent… ............................................................................................. 62 3.1.5 Calcium carbonate ........................................................................................... 62 3.1.6 Other additives.................................................................................................62 3.2 Extrusion ................................................................................................................... 63 3.2.1 The extrusion facilities………………………………………………….. ...... 63 3.2.2 Extrusion compounding ................................................................................. 65 3.2.2.1 Pure PHBV with antioxidant and nucleation agents ............................. 65 3.2.2.2 PHBV and PBAT compounds ............................................................... 66 iv 3.2.2.3 PHBV with chain extender.................................................................... 66 3.2.2.4 PHBV with calcium carbonate .............................................................. 66 3.2.3 Extrusion foaming ........................................................................................... 67 3.2.3.1 Foaming of PHBV (ENMATTM Y1000P) … ....................................... 67 3.2.3.2 Foaming of PHBV composites ............................................................. 68 3.3 Characterisations ....................................................................................................... 69 3.3.1 Differential scanning calorimetry (DSC) ........................................................ 69 3.3.2 Thermal gravimetric analysis (TGA) .............................................................. 70 3.3.3 Rheological characterisation ........................................................................... 70 3.3.3.1 Sample preparation................................................................................ 70 3.3.3.2 Complex viscosity measurement .......................................................... 70 3.3.4 Mechanical testing .......................................................................................... 71 3.3.5 Characterisation of the foamed samples ......................................................... 71 3.3.5.1 Scanning electron microscopy (SEM) .................................................. 71 3.3.5.2 Density measurement ............................................................................ 71 Chapter 4. General Properties of PHBV..................................................................... 72 4.1 Crystallization behaviour .......................................................................................... 72 4.1.1 Effect of boron nitride on crystallization behaviour of PHBV ....................... 72 4.1.2 Effect of thermal treatment on crystallization behaviour ................................ 78 4.2 Rheological behaviour .............................................................................................
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