Préparation et caractérisation de matériaux cellulosiques ultra poreux.

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Gavillon, Roxane (2007) Préparation et caractérisation de matériaux cellulosiques ultra poreux. Doctorat Sciences et Génie des Matériaux, ENSMP - CEMEF Centre de Mise en Forme des Matériaux, ENSMP p.235.

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Résumé

Nous avons préparé de nouveaux matériaux ultraporeux, appelés Aérocellulose, à partir de solutions de cellulose dans la N-méthyl-morpholine-N-oxyde (NMMO) ou dans des solutions aqueuses d’hydroxyde de sodium, suivie d’une étape de régénération puis d’un séchage supercritique.

Les propriétés rhéologiques des solutions cellulose-NaOH-eau préparées ont été étudiées. Le temps, la température et l’augmentation de la concentration de cellulose conduisent à la formation d’un gel irréversible. L’ajout d’urée retarde la gélification et améliore la qualité du solvant.

Nous avons déterminé les cinétiques de régénération de la cellulose des gels physiques de cellulose et nous les avons comparées à celle des solutions de cellulose-NMMO-eau. La concentration en cellulose, le type et la température du bain non-solvant sont les principaux paramètres qui gouvernent la diffusion du solvant de la solution de cellulose vers le bain de régénération et donc la structure finale du matériau.

Les Aérocelluloses ont une porosité ouverte, supérieure à 90%, avec un diamètre de pores moyen de quelques centaines de nanomètres. Les propriétés mécaniques du matériau dépendent des paramètres de préparation.

L’Aérocellulose a été évaluée dans diverses applications. Nous avons créé des structures composites cellulose-particules inorganiques. Nous avons pyrolysé les Aérocelluloses afin d’obtenir des structures carbonées poreuses. Les Aérocelluloses carbonées utilisées dans les piles primaires au lithium ainsi que les Aérocelluloses carbonées platinées testées comme support catalytique pour les électrodes dans les piles à combustibles conduisent à des résultats prometteurs.

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Table des Matières

Résumé du travail de thèse

General introduction

Chapter I: Cellulose, its processing and preparation of porous cellulose materials

Introduction

1.1Cellulose: main aspects on structure and properties

1.2 Generalities

1.3 Chemical structure of cellulose

1.4 Structure and organisation of micro fibrils

1.5 Polymorphs of cellulose

1.5.1 Cellulose I

1.5.2 Cellulose II

1.5.3 Cellulose III

1.5.4 Cellulose IV

2 Cellulose processing

2.1 Cellulose solvents

2.2 Main ways of cellulose processing

2.2.1 Viscose process

2.2.2 Lyocell process

2.2.3 NaOH process

2.3 Regeneration

3 Porosity of cellulose materials

3.1 Porosity of regenerated fibres

3.2 Porous cellulose membranes

3.3 Nanoporous cellulose-based materials

3.3.1 Generalities on aerogels and supercritical drying

3.3.2 Cellulose-based porous materials

Conclusions

References

Chapter II: Cellulose-NaOH solutions: preparation and rheological properties

Introduction

1 Bibliography: Cellulose-NaOH aqueous solutions: structure, properties and influence of additives

1.1 Effect of NaOH on cellulose fibres: the mercerisation process

1.2 Crystalline structures of Na- cellulose

1.3 Dissolution of cellulose in the aqueous 7-10%NaOH solution

1.4 Gelation of cellulose-NaOH aqueous solutions

1.5 Use of additives

2 Experimental

2.1 Materials

2.1.1 Cellulose

2.1.2 Solvents

2.2 Methods

2.2.1 Preparation of cellulose/NaOH/urea/water solutions

2.2.2 Rheological tools

3 Results and discussion

3.1 Steady-state flow of cellulose-NaOH solutions

3.2 Gelation of cellulose/NaOH/water solutions

3.2.1 Influence of temperature on gelation time

3.2.2 Influence of cellulose origin and concentration on gelation temperature

3.2.3 Influence of urea concentration on gelation

Conclusions

References

Chapter III: Kinetics of cellulose regeneration from cellulose-NaOH-water gels and comparison with cellulose-NMMO-water solutions

Abstract

Introduction

1 Experimental section

1.1 Materials

1.2 Methods

2 Results and discussion

2.1 Analysis of experimental data: choice of the approach

2.2 Influence of cellulose concentration on diffusion of NaOH from Avicel-NaOH-water gels and of NMMO from Solucell-NMMO solutions

2.3 Influence of water regenerating bath temperature

2.4 Influence of regenerating bath type

Conclusions

References

Chapter IV: Microstructural properties of Aerocellulose

Introduction

1 Materials and Methods

1.1 Materials

1.1.1 Cellulose solutions and gels

1.1.2 Additives

1.1.3 Regenerating bath

1.2 Methods

1.2.1 CO2 supercritical drying

1.2.2 Measurements of the porosity: a brief review of methods and theoretical approaches

1.2.3 Mercury Porosimetry

1.2.4 Electron microscopy

2 Results and discussion. Aerocellulose microstructure: influence of cellulose characteristics and preparation conditions

2.1 Example of Aerocellulose microstructure

2.2 Influence of gelation conditions

2.3 Influence of cellulose concentration

2.4 Influence of pulp properties

2.5 Influence of surfactant addition

2.6 Influence of the regenerating bath

2.6.1 Water regenerating bath: influence of temperature

2.6.2 Influence of the nature of the regenerating bath

Conclusions

References

Chapter V: Mechanical properties of Aerocellulose

Introduction

1 Bibliography: Mechanical properties of foams and aerogels

1.1 Mechanical properties of foams

1.2 Mechanical properties of aerogels

2 Material and Methods

2.1 Materials

2.1.1 Aerocellulose from NaOH route

2.1.2 Aerocellulose from NMMO route

2.2 Methods

3 Results and discussion: mechanical properties of Aerocellulose and influence of the preparation parameters

3.1 Examples of Aerocellulose mechanical properties

3.2 Effect of the displacement rate

3.3 Influence of cellulose concentration

3.4 Influence of pulp properties

3.5 Influence of additives

3.5.1 Influence of surfactant concentration

3.5.2 Influence of fibres addition: attempts to reinforce Aerocellulose

3.6 Influence of water regenerating bath temperature

3.7 Structure-properties correlations

Conclusions

References

Chapter VI: Application of Aerocellulose and of its carbonised form

Introduction

1 Example of Aerocellulose application

1.1 Preparation of Aerocellulose composite beads

1.2 Characterisation of Aerocellulose composite beads

1.2.1 Characterisation of powders

1.2.2 Wet cellulose composite beads

1.2.3 Aerocellulose composite beads

2 Carbonised Aerocellulose and its applications

2.1 Preparation and microstructural properties of carbonised Aerocellulose

2.1.1 Preparation of carbonised Aerocellulose

2.2 Microstructural characterisations

2.2.1 Comparison of organic and pyrolysed Aerocellulose

2.2.2 Influence of Aerocellulose preparation and pyrolysis parameters on microstructural properties of carbonised Aerocellulose

2.3 Electrochemical applications

2.3.1 Carbonised Aerocellulose for primary lithium battery Li/SOCl2

2.3.2 Proton exchange membrane fuel cell application

Conclusions

References

General conclusions

Perspectives

Statistiques de consultation

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