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Development of New Barrier Materials Using Microfibrillated Cellulose

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Development of New Barrier Materials Using Microfibrillated Cellulose THÈSE Pour obtenir le grade de DOCTEUR DE LA COMMUNAUTE UNIVERSITE GRENOBLE ALPES Spécialité : Matériaux, Mécanique, Génie Civil, Electrochimie Arrêté ministériel : 7 août 2006 Présentée par Sébastien RAYNAUD Thèse dirigée par Alain DUFRESNE, et codirigée par David GUERIN préparée au sein du Laboratoire Génie des Procédés Papetiers dans l'École Doctorale Ingénierie - Matériaux, Mécanique, Energétique, Environnement, Procédés, Production (I-MEP2) Développement de nouveaux matériaux barrières utilisant des microfibrilles de cellulose Thèse soutenue publiquement le 14 Février 2017 devant le jury composé de : Dr. Jose-Maria LAGARON Directeur de recherche, Spanish National Research Council, président Dr. Hélène ANGELLIER-COUSSY Maître de conférences, Université de Montpellier II, rapporteur Pr. Yves GROHENS Professeur, Université de Bretagne Sud, rapporteur Dr. Laurent HEUX Directeur de recherche CNRS, Université Grenoble Alpes, membre Pr. Alain DUFRESNE Professeur, Université Grenoble Alpes, membre Dr. David GUERIN Ingénieur de recherche, Centre Technique du Papier, membre Homies help homies. Always. - Finn Remerciements Merci. À mes encadrants, Pr. Alain Dufresne et Dr. David Guérin, ainsi qu'aux membres du jury Dr. Jose-Maria Lagaron, Dr. Hélène Angellier-Coussy, Pr. Yves Grohens, et Dr. Laurent Heux. Aux autres, aussi. Du CTP, du LGP2, ainsi que de ni l'un ni l'autre. Ça fait assez sobre, comme ça, mais je suis vraiment reconnaissant envers pas mal de personnes. Bonne lecture ! 5 Table of Contents LIST OF ABBREVIATIONS .............................................................................................................................. 11 GENERAL INTRODUCTION ............................................................................................................................ 15 CHAPTER I: LITERATURE REVIEW .................................................................................................................. 19 I.1. IN THE CONTEXT OF BARRIER FOOD PACKAGING ............................................................................................... 22 I.1.1. Protecting food from spoilage ......................................................................................................... 22 I.1.2. Permeability .................................................................................................................................... 23 I.1.2.1. Theory of mass transfer .......................................................................................................................... 23 I.1.2.2. Measuring gas permeability ................................................................................................................... 24 I.1.3. Different materials for different barriers ........................................................................................ 26 I.1.4. Processes for producing paper-based barrier packaging ................................................................ 27 I.1.4.1. Extrusion coating and lamination ........................................................................................................... 28 I.1.4.2. Water-based coating .............................................................................................................................. 29 I.1.5. Life cycle of food packages .............................................................................................................. 30 I.1.6. Perspectives ..................................................................................................................................... 31 I.2. MICROFIBRILLATED CELLULOSE (MFC) .......................................................................................................... 33 I.2.1. Cellulose and nanocellulose ............................................................................................................ 33 I.2.2. Production of microfibrillated cellulose ........................................................................................... 34 I.2.2.1. Mechanical defibrillation ........................................................................................................................ 35 I.2.2.2. Pre-treatment of the pulp ...................................................................................................................... 36 I.2.3. Applications ..................................................................................................................................... 36 I.2.4. Properties of MFC suspensions ........................................................................................................ 38 I.2.4.1. Degree of fibrillation .............................................................................................................................. 38 I.2.4.2. Rheology ................................................................................................................................................. 39 I.2.5. Properties of MFC films ................................................................................................................... 40 I.2.5.1. Production of MFC films ......................................................................................................................... 40 I.2.5.2. Structure of MFC films ............................................................................................................................ 41 I.2.5.3. Mechanical properties ............................................................................................................................ 42 I.2.5.4. Barrier properties ................................................................................................................................... 43 I.2.5.4.1. Oxygen barrier ................................................................................................................................... 43 I.2.5.4.2. Water vapour barrier ......................................................................................................................... 44 I.2.6. MFC layer for paper coating applications ....................................................................................... 44 I.2.6.1. MFC as top-layer ..................................................................................................................................... 44 I.2.6.1.1. MFC top-layer obtained by casting or handsheet former .................................................................. 44 I.2.6.1.2. MFC top-layer obtained by a coating process .................................................................................... 45 I.2.6.2. Multi-layer structure with application to coating ................................................................................... 46 I.2.7. Conclusion on microfibrillated cellulose .......................................................................................... 47 I.3. MFC-BASED NANOCOMPOSITES .................................................................................................................. 49 I.3.1. MFC as filler in a hydrosoluble matrix ............................................................................................. 49 I.3.1.1. Poly(vinyl alcohol) (PVOH) ...................................................................................................................... 49 I.3.1.2. Properties of PVOH:MFC films ................................................................................................................ 50 I.3.1.3. Application to paper coating .................................................................................................................. 51 I.3.1.3.1. Viscosity of MFC-comprising coating colours ..................................................................................... 51 I.3.1.3.2. Barrier of composite coatings ............................................................................................................ 51 I.3.1.3.3. Improvement of the layer quality ...................................................................................................... 52 I.3.1.4. Other uses of MFC in a coating colour.................................................................................................... 53 I.3.2. Polymer-Clay composites ................................................................................................................ 53 7 I.3.2.1. Structure of layered silicates (clays) ....................................................................................................... 53 I.3.2.2. Barrier properties of polymer-clay composites ...................................................................................... 55 I.3.2.3. PVOH:clay composites ............................................................................................................................ 56 I.3.2.4. MFC:clay composites .............................................................................................................................. 58 I.3.2.5. PVOH:MFC:clay composites ................................................................................................................... 60 I.3.3. Alternatives to PVOH and clays ....................................................................................................... 61 I.3.4. Conclusion on MFC-based nanocomposites .................................................................................... 62 I.4. CROSSLINKING ........................................................................................................................................
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