Egal, Magali (2006) Structure and properties of cellulose/NAOH aqueous solutions, gels and regenerated objects. PhD thesis Science et génie des matériaux, CEMEF - Centre de Mise en Forme des Matériaux, ENSMP p.243.

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Abstract

It has been reported that cellulose can be dissolved in aqueous sodium hydroxide solutions in a narrow range of NaOH concentrations (6-10%) and temperatures (-10°C/-4°C). Cellulose solutions obtained are not stable and gelation occurs with time and temperature increase. It has been also showed that the presence of additives, such as urea or zinc oxide, in solvent system improves the dissolution of cellulose fibres and the solution stability. In order to understand the structure of cellulose solutions in NaOH/water without or with additives, we first studied phase diagrams of solvents and then the influence of the addition of cellulose in these solvents on the DSC thermograms. We determined (i) the limit of cellulose dissolution in NaOH/water and in NaOH/urea/water and (ii) the nature of interactions occurring between cellulose chains, NaOH, urea, ZnO and water molecules. We also studied rheological properties of cellulose solutions in NaOH/water, NaOH/urea/water and NaOH/ZnO/water. The presence of additives delays gelation (in time and in temperature) but does not change its mechanism. Gelation of cellulose solutions is due to a decrease of solvent quality which favours the cellulose-cellulose interactions with the temperature increase. Finally, the study of mechanical properties, and especially the measurements of the stress at rupture of regenerated cellulose objects showed the great influence of gelation and regeneration parameters on the properties of the final products.

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Table of content

Résumé du Chapitre I Etat de l’art : La cellulose et sa dissolution dans des solutions aqueuses d’hydroxyde de sodium. CHAPTER 1.STATE OF THE ART : CELLULOSE AND ITS DISSOLUTION IN ALKALINE HYDROXIDE AQUEOUS SOLUTIONS. I.1- Cellulose: structure, morphology and treatment. I.1.1- Generalities. I.1.2- Chemical structure of cellulose. I.1.3- Crystalline structures of cellulose. I.1.3.1. Cellulose I or native cellulose. I.1.3.2. Cellulose II . I.1.3.3. Cellulose III. I.1.3.4. Cellulose IV. I.1.4- Supra-molecular structure of cellulose. I.1.4.1. Micro-fibrils. I.1.4.2. Wood and cotton cellulose fibres. I.1.5- Extraction of cellulose and activation. I.1.5.1. Manufacture of cellulosic pulp. I.1.5.2. Activation of cellulose. I.2- Cellulose dissolution in alkaline hydroxide aqueous solutions. I.2.1- Xanthation in viscose process. I.2.2- Action of alkaline hydroxide solutions on cellulose fibres. I.2.2.1. Introduction on mercerisation process and cellulose dissolution. I.2.2.2. Formation of alkali-celluloses. I.2.2.3. Hydration of alkali ions. I.2.2.4. Mechanism of mercerisation. I.2.3- Influence of additives on cellulose dissolution. I.2.3.1. Influence of zinc oxide (ZnO). I.2.3.2. Influence of urea and thiourea. I.2.3.3. Other additives. I.3- Conclusions. REFERENCES Résumé du chapitre II Matériaux et méthodes expérimentales. CHAPTER II

MATERIALS AND METHODS. II.1- Materials. II.1.1- Cellulose samples. II.1.1.1. Avicel cellulose. II.1.1.2. Borregaard cellulose. II.1.1.3. Other cellulose samples. II.1.2- Solvents and additives. II.1.2.1. Alkali hydroxides. II.1.2.2. Additives. II.1.2.3. Surfactants. II.1.3- Other components used in sponge manufacture. II.1.3.1. Reinforcing fibres. II.1.3.2. Adhesion promoters. II.1.3.3. Na2SO4,10H2O crystals. II.1.3.4. Carrageenan. II.2- Solutions preparation. II.2.1- Drying of steam exploded cellulose. II.2.2- Dissolution procedure. II.2.3- Storage. II.2.4- Filtration. II.3- Methods. II.3.1- Differential Scanning Calorimetry (DSC). II.3.1.1. Main principles. II.3.1.2. Temperature measurement. II.3.1.3. Melting temperature measurement. II.3.1.4. Melting enthalpy measurement. II.3.1.5. Calibration and experimental conditions. II.3.1.6. Software for peak deconvolution: “PeakFit 4.12”. II.3.2- X-ray diffraction. II.3.3- Rheology. II.3.3.1. Semi-dilute cellulose solution. II.3.3.2. Dilute cellulose solution. II.3.4- Microscopy. II.3.4.1. Optical Microscopy (OM). II.3.4.2. Scanning Electron Microscopy (SEM). II.3.5- Mechanical property: tensile tests

II.3.5.1. Tensile tests on films of regenerated cellulose. II.3.5.2. Tensile tests on regenerated cellulose + reinforcing fibres. II.3.5.3. Tensile tests on sponges (regenerated cellulose + fibres + porophores). II.3.6- Other methods. II.3.6.1. Density measurement. II.3.6.2. Water absorption. II.3.6.3. Shrinkage. EFERENCES Résumé du chapitre III Structure des solutions aqueuses de NaOH et de cellulose/NaOH avec et sans additifs. Limite de dissolution de la cellulose CHAPTER III STRUCTURE OF AQUEOUS NAOH AND CELLULOSE-NAOH SOLUTIONS WITH AND WITHOUT ADDITIVES. LIMIT OF CELLULOSE DISSOLUTION III.1- Bibliography: phase diagram of aqueous sodium hydroxide solution .III.1.1- Phase diagrams . III.1.1.1. Binary phase diagram III.1.1.2. Ternary phase diagram III.1.1.3. Methods for building phase diagrams. The limits of the DSC analysis .III.1.2- State of the art on the structure of NaOH aqueous solutions .III.1.2.1. Pure sodium hydroxide III.1.2.2. Sodium hydroxide hydrates III.2- Structure of cellulose solvents: NaOH/water, NaOH/urea/water and NaOH/ZnO/water III.2.1- NaOH/water binary system III.2.1.1. DSC melting thermograms of NaOH/water solutions III.2.1.2. Peak at lower temperature: melting of the eutectic mixture III.2.1.3. Peak at higher temperature III.2.1.4. Proportions between NaOH and water III.2.1.5. Conclusions on the phase diagram and structure of NaOH/water solutions . III.2.2- NaOH/urea/water ternary system .III.2.2.1. Urea/water binary phase diagram III.2.2.2. NaOH/urea/water ternary phase diagram .III.2.3- NaOH/ZnO/water ternary system III.2.3.1. Viscosity of dilute NaOH/ZnO/water solutions. III.2.3.2. NMR study III.2.3.3. DSC results III.2.3.4. Conclusions on the NaOH/ZnO/water system .III.2.4- Conclusions on the structure of cellulose solvents: NaOH/water, NaOH/ZnO/water and NaOH/urea/water III.3- Structure of cellulose solutions in NaOH/water, NaOH/ZnO/water and NaOH/urea/water III.3.1. Cellulose/NaOH/water ternary solutions III.3.1.1. DSC results on Avicel/NaOH/water III.3.1.2. Peak at low temperature. Limit of cellulose dissolution .III.3.1.3. Peak at high temperature .III.3.1.4. Influence of cellulose origin on the structure of cellulose/NaOH/water solutions .III.3.1.3. Conclusions .III.3.2. Cellulose/NaOH/urea/water solutions .III.3.2.1- DSC results on Avicel/NaOH/6%urea/water .III.3.2.2. Peak of NaOH eutectic .III.3.2.3. Peak of urea eutectic III.3.2.4. Peak of free ice melting III.3.2.5. Conclusions III.3.3. Cellulose/NaOH/ZnO/water solution .III.3.4. Conclusions on the structure of cellulose solutions in NaOH/water with and without additives .III.4- Influence of freezing on the thermal properties of the cellulose/NaOH mixtures III.5- Conclusions . REFERENCES Résumé du chapitre IV Ecoulement et gélification des solutions aqueuses de cellulose/NaOH : Influence des additifs .CHAPTER IV FLOW AND GELATION OF AQUEOUS CELLULOSE/NAOH SOLUTIONS : INFLUENCE OF ADDITIVES . IV.1. Influence of ZnO and urea on the flow behaviour of cellulose/7.6NaOH aqueous solutions IV.1.1. Influence of the presence of ZnO or urea in the solvent on the flow of cellulose/7.6NaOH aqueous solutions .IV.1.2. Conclusions IV.2- Gelation and dissolution of cellulose in the presence of ZnO IV.2.1. Influence of the preparation conditions on gelation of cellulose/7.6NaOH/water solutions in the presence of ZnO IV.2.2. Influence of ZnO concentration on gelation and cellulose dissolution .IV.2.3. Dissolution of cellulose in a solvent with a constant molar ratio ZnO:NaOH=1:10 .IV.2.4. Influence of the presence of ZnO on gelation kinetics .IV.2.5. Influence of ZnO on cellulose intrinsic viscosity .IV.2.6. Discussion on the influence of ZnO on gelation of steam exploded cellulose in 7.6NaOH aqueous solutions IV.2.7. Conclusions IV.3. Gelation and dissolution of cellulose in the presence of urea; comparison between urea and ZnO IV.3.1. Influence of the preparation conditions on cellulose dissolution and gelation in the presence of urea and of urea concentration .IV.3.2. Influence of cellulose DP and origin on the dissolution and gelation in the presence of urea and ZnO . IV.3.3. Discussion on the influence of urea on gelation and dissolution of steam exploded cellulose in 7.6NaOH aqueous solutions and comparison with the role of ZnO . IV.3.4. Conclusions IV.4. Influence of freezing on rheological properties of cellulose/NaOH aqueous solutions IV.5- Tests on gelation and dissolution of cellulose in other alkali solvents: KOH and NaOH with other additives IV.5.1. Testing cellulose dissolution in potassium hydroxide .IV.5.2. Addition of surfactants .IV.5.3. Other additives: salts and oxides IV.5.3. Conclusions IV.6. Conclusions .REFERENCES Résumé du chapitre V Propriétés mécaniques d’objets régénérés préparés à partir de solutions aqueuses de cellulose/NaOH CHAPTER V.MECHANICAL PROPERTIES OF REGENERATED OBJECTS PREPARED FROM CELLULOSE-NAOH AQUEOUS SOLUTIONS V.1. Summary on sponge preparation: viscose and NaOH processes .V.1.1. Viscose process .V.1.2. NaOH process . V.2. Properties of sponges prepared with the NaOH process .V.2.1. Wet samples made from regenerated 5cellulose/7.6NaOH aqueous solutions, without reinforcing fibres and porophores .V.2.1.1. Tensile stress results .V.2.1.2. Influence of regeneration bath parameters V.2.1.3. Influence of solution thermal treatment .V.2.1.4. Influence of additives . V.2.1.5. Conclusions V.2.2. Wet samples made from regenerated 5cellulose/7.6NaOH aqueous solutions with reinforcing fibres without porophores . V.2.2.1. Influence of added reinforcing fibres .V.2.2.2. Influence of fibres treatment on the rupture stress V.2.2.3. Influence of freezing on rupture stress and adhesion between fibres and matrix .V.2.2.4. Influence of the thermal history of fibre treatment with 8%NaOH aqueous solution on the mechanical properties of wet regenerated samples .V.2.2.5. Conclusions .V.2.3. Wet samples made from regenerated 5cellulose/7.6NaOH aqueous solutions with reinforcing fibres and porophores .V.2.3.1. Rupture stress V.2.3.2. Absorption .V.2.3.3. Shrinkage V.2.4. Conclusion on the role of the freezing step . V.3. Conclusions REFERENCES

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