Cuissinat, Céline (2006) Swelling and dissolution mechanisms of native cellulose fibres. PhD thesis Sciences et Génie des Matériaux, ENSMP - CEMEF Centre de Mise en Forme des Matériaux, ENSMP p.160.

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Abstract

Cellulose is a natural polymer, which belongs to polysaccharide family. Cellulose offers numerous product development opportunities but cellulose is difficult to process: it can not be melted. Thus cellulose must be either solubilised or derivetised. This is the main reason that pushed us to study and understand the swelling and dissolution mechanisms of native cellulose fibres (cotton, wood, sisal, abaca, hemp, flax and ramie). Data obtained with cotton and wood samples without outer layers, and cellulose derivatives allow us further information. The chemical agents, investigated as solvent or swollen agents, are aqueous (N-methylmorpholine N-oxide – water with various water content, or sodium hydroxide – water – additives) or ionic liquids. We identified five modes describing the behaviour of cellulose native fibres dipped in chemical agents:

Mode 1: fast dissolution by disintegration into fragments

Mode 2: large swelling by ballooning, and dissolution

Mode 3: large swelling by ballooning, and no dissolution

Mode 4: homogeneous swelling, and no dissolution

Mode 5: no swelling, and no dissolution

Despite the morphological differences between the different types of vegetal fibres or cellulose derivatives, they all follow the same modes of swelling and dissolving. We can distinguish different zones with one fibre during the ballooning. The three main components are the followings: the balloons, the membrane (surrounded the balloons with helicoidal feature) and the unswollen section. Each of these parts undergoes a typical swelling and dissolution behaviour. The components of the balloon membrane are the primary wall, plus part of the secondary wall. The membrane is the most difficult part to dissolve. Cellulose inside the balloons is not only swollen, but dissolved. The swelling and dissolution mechanisms of native cellulose fibres are not determined by the chemical nature of chemicals tested as solvent systems. Even if the quality of solvent plays a major role concerning the induced mechanisms, the key parameter is the morphological architecture of native cellulose fibres.

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Table of content

Table of contents

Résumé francophone.

Introduction

Chapter 1: Bibliography.

Résumé francophone.

Introduction

Table of contents

I. The fibre structure

I.1 Cellulose molecule

I.2.Supermolecular structure

I.3. Ultrastructure

I.4.Conclusion on the fibre structure

II. Structure of plant cell walls

II.1. Biosynthesis of cellulose

II.2. The cell wall constituents

II.3. The cell wall structure

II.4. Conclusion on the structure of plant cell walls

III. Swelling and dissolution of cellulose fibres

III.1. Dissolution mechanisms of dissolution

III.2. Important classes of cellulose solvents systems

III.3. Accessibility of cellulose fibres

III.4. Conclusion on cellulose dissolution

Chapter 2: Swelling and dissolution mechanisms of native cellulose fibres, part I: free floating cotton and wood fibres in N-methylmorpholine-N-oxide – water mixtures

Chapter 3: Swelling and dissolution mechanisms of native cellulose fibres, part II: free floating cotton and wood fibres in NaOH – water – additives systems

Chapter 4: Swelling and dissolution mechanisms of native cellulose fibres, part III: enzymatically – treated cotton and wood fibres in aqueous systems

Chapter 5: Swelling and dissolution mechanisms of native cellulose fibres, part IV: free floating cotton and wood fibres in ionic liquids

Chapter 6: Swelling and dissolution mechanisms of native cellulose fibres, part V: free floating plant fibres in aqueous systems

Chapter 7: Swelling and dissolution mechanisms of native cellulose fibres, part VI: free floating cellulose derivatives in aqueous systems and ionic liquids

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