This thesis forms part of a project with the objective of developing and implementing a novel, wood-based, process for the industrial production of cellulose textile fibres. This new process should not only be cost effective but also have far less environmental impact then current processes. Natural and man-made fibres are usually plagued with problems (e.g. economic and environmental) and are unsuitable in meeting growing demands. The focus of this thesis was therefore to investigate the dissolution of cellulose derived from various pulps in novel aqueous solvent systems.             It was shown that cellulose could be dissolved in a NaOH/H2O solvent at low temperatures (<0°C) and that such an alkaline solvent can be improved regarding the solubility, stability and rheological properties of the cellulose dopes formed if different additives (salts or amphiphilic molecules) are used. The effect of different kinds of pretreatment (individually and combined) and the influence of pulp properties on cellulose accessibility and dissolution were also evaluated. These pretreatments affected, as expected, some characteristic properties of the pulps mainly by reducing the DP but also, for example, changing the composition of the carbohydrates. Not only did the pretreatment affect the solubility it also increased the stability of the cellulose dopes, resembling the effect of chemical additives to the NaOH system. According to multivariate data analysis it was established that, of the pulp properties analyzed, only the composition of carbohydrates and the DP had a significant influence on the solubility of the pulps used in this study. Finally, it was emphasized that the dissolution of cellulose pulps seemed to be controlled by a very complex interaction between both kinetic and thermodynamic parameters. / CelluNova

Pionnier dans sa façon d’approcher la prise en charge des malades, le Pennsylvania Hospital for the Insane, construit à la fin des années 1830 dans la campagne proche de Philadelphie, fut dirigé de 1840 à 1883 par Thomas Kirkbride. A travers la culture visuelle de l’établissement, et tout particulièrement l’usage systématique qui y fut fait des spectacles de projection à la lanterne magique, cette thèse propose de relier l’entreprise thérapeutique du Dr. Kirkbride à la riche tradition artistique et photographique de Philadelphie. Dans cette tradition nous retiendrons en particulier les frères Frederick et William Langenheim, pionniers des procédés négatif-positif aux Etats-Unis. A travers l’analyse d’un tableau commandé au peintre Benjamin West, la première partie s’ouvre sur le Pennsylvania Hospital, situé au cœur de Philadelphie, et pose les éléments de la préhistoire de l’image au Pennsylvania Hospital for the Insane. La deuxième partie met en avant différentes facettes de « l’image renversée » présentée par le nouvel établissement et s’appuie notamment sur le projet culturel développé au cours de la période 1841-1859. La troisième partie s’attache plus particulièrement à l’évolution des espaces verts proposés aux patients. La collection de plaques de lanterne magique, telle une fenêtre ouverte sur l’extérieur, est au cœur de cette partie. Cette collection d’objets constitue non seulement un ensemble exceptionnel par son ampleur, la diversité des techniques d’images sur verre utilisées, et la longue période de sa constitution, mais témoigne aussi de pratiques culturelles novatrices. / The Pennsylvania Hospital for the Insane was built in the late 1830's in the countryside near Philadelphia. It was directed from 1840 to1883 by Thomas Kirkbride, who made ita pioneer in the humane treatment of the mentally ill. This thesis connects thetherapeutic work of Dr. Kirkbride to the rich artistic and photographic traditions of Philadelphia by examining the visual culture of the institution, with special attention to the systematic use of magic lantern shows. Frederick and William Langenheim,innovators in the negative-positive process in the United States, are especially important to this history. By focusing on a painting that was commissioned from Benjamin West, the first part opens the thesis in the heart of Philadelphia, at the Pennsylvania Hospital,and explores the background period leading up to the use of images at the Pennsylvania Hospital for the Insane. The second part details various aspects of the "reverse image"presented by the new hospital in the country and focuses on the cultural projectdeveloped during the period from 1841 to 1859. The third part looks closely at the development of outdoor spaces for the use of the patients. The collection of magic lantern slides, like a window open to the outside, is at the heart of this section. This collection of objects is exceptional due to its large scale, to the variety of techniques used in making the glass slides, and to the long period of its creation. It also bears witness to the innovative cultural practices which it records.

<p> I viskosprocessens inledande merceriseringssteg behandlas cellulosa (dissolvingmassa) med natriumhydroxid (NaOH) varvid cellulosan omvandlas till alkalicellulosa. Därpå följer en sulfidering med koldisulfid (CS₂) som omvandlar alkalicellulosa till natriumxantogenat. Xantatet löses i en alkalisk lösning och en trögflytande vätska, viskos, bildas. Vid tillverkning av spinnviskos är sista steget i processen en surgörning där koldisulfiden spjälkas av och cellulosan återbildas i form av en tråd. Vid tillverkning av högviskös viskos (Freudenberg HP) sker regenereringen i basisk miljö men vid förhöjd temperatur (100°C), och återbildningen av cellulosa ger då en cellulosabaserad bädd. Genom att öka dissolvingmassans reaktivitet skulle förbrukningen av koldisulfid i sulfideringssteget kunna minskas. Med en ökad reaktivitet menas att fler hydroxylgrupper på cellulosan blir tillgängliga för vidare reaktioner med natriumhydroxid och koldisulfid. Detta skulle kunna möjliggöras med en enzymatisk förbehandling av massan.</p><p>Det första delmålet i projektet var att producera en viskos med hög viskositet i laboratorieskala. Projektets andra mål var att undersöka effekterna av en enzymatisk behandling, med enzymet Carezyme^®, på massans viskositet och reaktivitet.</p><p>En studie gjordes för att se hur olika tider i viskosprocessens andra steg, pressteget, påverkade cellulosahalten och luthalten för alkalicellulosa. Resultaten tydde på att en längre presstid gav en högre cellulosahalt upp till en viss tidpunkt. Vid 195 sekunder avklingade kurvan och effekten av en längre presstid minskade. Resultatet visade också på att mängden lut i alkalicellulosaprovet var relativt konstant och att luthalten inte påverkas nämnvärt av pressningen.</p><p>Vidare genomfördes försök kring viskosprocessens sulfideringssteg. Det fanns under projektets gång stora svårigheter i att uppnå samma höga nivå på gammatalet vid produktion av viskos i laborativ skala (52-58 %) som vid produktion i fabriksskala (68-70 %). Gammatalet är ett mått på hur väl koldisulfid har reagerat med cellulosa under sulfideringen. I ett försök att öka gammatalet satsades en större mängd koldisulfid, med förhoppningen att kunna kompensera för den relativt stora andel koldisulfid som befann sig i gasfas under reaktionen och som därmed inte var aktiv under sulfideringen. Den ökade mängden koldisulfid resulterade dock inte i en ökning av gammatalet. I ett annat försök tillsattes en svag natriumhydroxidlösning direkt till sulfideringskärlet vid avslutad reaktion, utan att någon effekt på gammatalet kunde påvisas. Det undersöktes även om ett ökat förhållande mellan luthalt och cellulosahalt i alkalicellulosan kunde ge någon positiv effekt på gammatalet. Denna förändring gav dock inget ökat gammatal.   </p><p>Dissolvingmassaprover behandlades med enzymet Carezyme^® för att kunna studera dess inverkan på massans reaktivitet och viskositet.  Resultaten visade på en tydlig nedgång i viskositet med högre koncentrationer av enzym. Reaktiviteten på den enzymbehandlade massan ökade i jämförelse med den obehandlade massan. Då viskos producerades med en enzymbehandlad massa kunde ingen effekt av enzymbehandlingen noteras, med avseende på gammatalet.</p><p> </p> / <p>In the first step of the conventional viscose process, called mercerization, cellulose (dissolving pulp) is treated with sodium hydroxide (NaOH) in which the cellulose is converted to alkali cellulose. Alkali cellulose is then treated with carbon disulphide (CS₂) to be converted into a sodium xanthate.  This xanthate is dissolved in an alkali solution and a viscous liquid, called viscose, is formed. The last step in the process is an acidification where the carbon disulphide is splinted off and the cellulose is regenerated in the shape of threads. When producing high viscosity viscose (Freudenberg HP) the regeneration takes place in an alkaline environment and the re-formation of cellulose gives a cellulosic based bed. By increasing the reactivity of the dissolving pulp the amount of carbon disulphide could be reduced, compared at the same degree of substitution. An increase in reactivity means that a larger amount of hydroxyl groups on the cellulose molecule are available to react with sodium hydroxide and carbon disulphide. This could be enabled by an enzymatic pretreatment of the pulp prior to the mercerization step.</p><p>The first aim of this project was to produce a high viscosity viscose in a laboratory scale, comparable to the viscose quality that is produced by Freudenberg HP. The second aim of the project was to investigate the effects of an enzymatic treatment (with the enzyme named Carezyme^®) on the viscosity and reactivity of the dissolving pulp. </p><p>A study was made to examine the influence of the time in the pressing step (after the mercerization) on the cellulose and sodium hydroxide content in the alkali cellulose. The results indicated a linear correlation between the cellulose content and the pressing time up to 195 seconds. At this point the correlation declined and the effects of a longer pressing time decreased. The results also showed that the amount of lye in the alkali cellulose sample was nearly constant and therefore not effected by the pressing time.</p><p>Tests were also carried out concerning the sulphidation step in the process. During the whole project there were difficulties in reaching the same gamma value of the viscose in a laboratory scale (52-58 %) compared to large-scale production (68 - 70%). The gamma value is a measurement of the degree of substitution for carbon disulphide on the cellulose backbone. In one attempt to enhance the gamma value the carbon disulphide charge was increased. The expectation was to compensate for the relatively high amounts of inactive carbon disulphide expected to be found in the gaseous phase in the reactor. However, this did not result in a higher gamma value. In another experiment a weak solution of sodium hydroxide was added directly to the sulphidation vessel after the reaction was completed, but no change in the gamma value was obtained. It was also investigated if an increased relation between the cellulose- and sodium hydroxide content in the alkali cellulose could affect the gamma value positively.  Unfortunately, this modification did not give an increased gamma value.</p><p>Samples of dissolving pulp were treated with the enzyme Carezyme^® to see its impact on viscosity and reactivity of the pulp. The results showed a distinct loss in viscosity with an increased enzyme concentration. The reactivity of the pulp increased compared to the untreated pulp. No effects of the enzymatic treatment could be seen on the final viscose when it was produced from an enzyme treated pulp.</p>

<p>Various chemical properties can be used to characterise dissolving pulp. The quality of the pulp must be carefully controlled to ensure that it meets the requirements for its intended use and the further processes to be applied. If it is to be used to prepare viscose, or other cellulose derivatives, the key prop-erties of the pulp are its accessibility and reactivity. The studies described in this thesis investigated the potential utility of multivariate analysis of chemi-cal and spectral data for determining the properties of dissolving pulp. Dis-solving pulps produced by a two-stage sulfite process, both in the laboratory and a factory were produced pulps for this purpose. The analyses showed that pulp with high reactivity had short cellulose chains, low molecular weight, low polydispersity, low hemicellulose content, high content of ace-tone-extractable compounds, and high surface charge compared to pulp with low reactivity. Important chemical properties of the pulp, such as viscosity and alkali resistance, were successfully predicted from near infrared spectra. Predicting the reactivity, or the viscose filterability, of the pulp was more complex. Several chemical methods for analyzing the reactivity of the pulp were examined. The influence of the cellulose structure at the supermolecu-lar level on the reactivity of the pulp was explored by multivariate analysis of solid state 13C nuclear magnetic resonance spectra. Structural variables considered included: differences in hydrogen bonding, contents of hemicel-lulose, amorphous cellulose and crystalline cellulose I and II. Pulps with high reactivity have higher contents of cellulose I and amorphous cellulose than pulps with low reactivity, which have higher contents of cellulose II and hemicellulose.</p>

Various chemical properties can be used to characterise dissolving pulp. The quality of the pulp must be carefully controlled to ensure that it meets the requirements for its intended use and the further processes to be applied. If it is to be used to prepare viscose, or other cellulose derivatives, the key prop-erties of the pulp are its accessibility and reactivity. The studies described in this thesis investigated the potential utility of multivariate analysis of chemi-cal and spectral data for determining the properties of dissolving pulp. Dis-solving pulps produced by a two-stage sulfite process, both in the laboratory and a factory were produced pulps for this purpose. The analyses showed that pulp with high reactivity had short cellulose chains, low molecular weight, low polydispersity, low hemicellulose content, high content of ace-tone-extractable compounds, and high surface charge compared to pulp with low reactivity. Important chemical properties of the pulp, such as viscosity and alkali resistance, were successfully predicted from near infrared spectra. Predicting the reactivity, or the viscose filterability, of the pulp was more complex. Several chemical methods for analyzing the reactivity of the pulp were examined. The influence of the cellulose structure at the supermolecu-lar level on the reactivity of the pulp was explored by multivariate analysis of solid state 13C nuclear magnetic resonance spectra. Structural variables considered included: differences in hydrogen bonding, contents of hemicel-lulose, amorphous cellulose and crystalline cellulose I and II. Pulps with high reactivity have higher contents of cellulose I and amorphous cellulose than pulps with low reactivity, which have higher contents of cellulose II and hemicellulose.

<p>Cellulosans tillgänglighet och reaktivitet är nyckelparametrar vid framställning av regenererad cellulosa och cellulosaderivat. Det är välkänt att på grund av cellulosans kristallina struktur är tillgängligheten begränsad för lösningsmedel och olika reagens. Till exempel kan en inhomogen substitution av hydroxylgrupperna i cellulosakedjan resultera i cellulosaderivat av sämre kvalitet. Baserat på detta har en del av arbetet i denna studie fokuserat på att förbättra cellulosans tillgänglighet och reaktivitet genom att studera effekten av olika enzymatiska behandlingar med monokomponent endoglukanaser. Resultaten visar att närvaron av en cellulosabindande domän fyller en viktig funktion för att öka cellulosans reaktivitet, men strukturen för den katalytiska domänen visade sig ha den största inverkan på cellulosans tillgänglighet. I kompletterande studier har även effekten av en mekanisk förbehandling i kombination med enzymatisk behandling utvärderats. Kombinationen av förbehandlingarna resulterade i en positiv effekt, cellulosans reaktivitet kunde ökas i större omfattning.</p><p>I dag används huvudsakligen dissolvingmassor som råvara vid framställning av cellulosaregenerat och cellulosaderivat. Kraven för dessa s.k. specialmassor är högt cellulosainnehåll samt lågt hemicellulosa- respektive lignininnehåll. På grund av dessa specifika krav är produktionskostnaderna för dessa massor högre än konventionella sulfatmassor. Den andra delen av studien har därför fokuserat på möjligheten att använda dessa sulfatmassor som dissolvingmassa. Det har visats att kombinationen av enzymatiska behandlingar med monokomponent endoglukanas och xylanas följt av ett alkaliskt steg kan resultera i massor där kraven uppfylls med avseende på cellulosans reaktivitet, och cellulosa- respektive hemicellulosainnehåll.</p> / <p>The accessibility and reactivity of cellulose are key parameters on the manufacturing of cellulose derivatives and regenerated cellulose. It is well known that, due to the crystalline structure of cellulose, the accessibility of solvents and reagents is limited. For instance, an inhomogeneous substitution of the hydroxyl groups of the cellulose chain might lead to the production of derivatives of low quality. As a consequence, part of this work has focused on improving the accessibility and reactivity on cellulose by studying the effect of different monocomponent endoglucanases. It has been demonstrated that the presence of the cellulose-binding domain plays an important role on the enhancement of cellulose reactivity; however, the structure of the catalytic domain has been showed to have the highest influence on this parameter. Furthermore, the influence of mechanical treatment prior to enzymatic treatment has been examined. The combination of pretreatments showed a positive effect enhancing to a larger extent the cellulose reactivity.</p><p>Currently, dissolving-grade pulps are commonly used for the production of cellulose derivatives and regenerated cellulose. The requirements for these so-called “special pulps” are a high cellulose content and a low hemicelluloses and lignin content. As a result of these specific demands, the production costs of these pulps are higher than those of common kraft pulps. The second part of this work, therefore, has been focused on the study on the viability of converting kraft pulps into dissolving pulps. It has been demonstrated that the combination of enzymatic treatments using a monocomponent endoglucanase and a xylanase together with the addition of an alkaline step could fulfil the requirements of a commercial dissolving pulp in terms of cellulose reactivity and cellulose and hemicellulose content.</p>

Different pulps were chemically (nitren) and biologically (enzyme) treated in order to improve the chemical accessibility and dissolution capacity in cold NaOH. The treatments effect on the pulp properties was accessed by studying the changes on their chemical and macromolecular structure and by analyzing the dissolution performance in cold NaOH.The nitren treatment has the effect of removing a large part of the xylan present in a dissolving pulp and is also removing mannans. Increasing the nitren concentrations will extract also cellulose and decrease its mean molar mass. These extractions are favorable for the dissolution in cold NaOH–water, being more effective with higher nitren concentrations. A maximum of 44.7% increase on the dissolution yield was achieved.The new enzymatic treatment shows a higher efficiency on promoting fibers accessibility to NaOH ions, (directly correlated with the enzymatic load), allowing a maximum increase of 150% on the dissolution yield. A slight decrease of the average molar mass was also seen. The different pulps reacted differently to the treatments, showing that the pulping pretreatments have an influence on the enzymatic efficiency. Using a mixture of enzymes and endoglucanase showed that the synergistic effect of these two enzymes is more effective on cellulose activation.Both nitren and enzymatic treatments are improving the pulp chemical accessibility mostly by modifying the structure of the primary wall and S1 wall. This promotes the swelling of these wood cell structures, allowing the access of the NaOH solvating ions into fiber regions not accessible on the original pulp. The nitren is disassembling the fiber surface with extraction of hemicelluloses and degrading the cellulosic structure.The use of this enzyme on the cellulose pulps activation towards dissolution in cold NaOH is of great importance. It presents a high potential in both technical, with further development and industrial implementation, and fundamental research fields, with further studies on mechanisms of cellulose activation.The work was performed in Cemef - Mines ParisTech, Sophia Antipolis, France, and TI / Hamburg University, Germany and financed by Sappi, Tembec, Lenzing, Viskase and Spontex and had support from EPNOE (European Polysaccharide Network of Excellence). / Different pulps were chemically (nitren) and biologically (enzyme) treated in order to improve the chemical accessibility and dissolution capacity in cold NaOH. The treatments effect on the pulp properties was accessed by studying the changes on their chemical and macromolecular structure and by analyzing the dissolution performance in cold NaOH.The nitren treatment has the effect of removing a large part of the xylan present in a dissolving pulp and is also removing mannans. Increasing the nitren concentrations will extract also cellulose and decrease its mean molar mass. These extractions are favorable for the dissolution in cold NaOH–water, being more effective with higher nitren concentrations. A maximum of 44.7% increase on the dissolution yield was achieved.The new enzymatic treatment shows a higher efficiency on promoting fibers accessibility to NaOH ions, (directly correlated with the enzymatic load), allowing a maximum increase of 150% on the dissolution yield. A slight decrease of the average molar mass was also seen. The different pulps reacted differently to the treatments, showing that the pulping pretreatments have an influence on the enzymatic efficiency. Using a mixture of enzymes and endoglucanase showed that the synergistic effect of these two enzymes is more effective on cellulose activation.Both nitren and enzymatic treatments are improving the pulp chemical accessibility mostly by modifying the structure of the primary wall and S1 wall. This promotes the swelling of these wood cell structures, allowing the access of the NaOH solvating ions into fiber regions not accessible on the original pulp. The nitren is disassembling the fiber surface with extraction of hemicelluloses and degrading the cellulosic structure.The use of this enzyme on the cellulose pulps activation towards dissolution in cold NaOH is of great importance. It presents a high potential in both technical, with further development and industrial implementation, and fundamental research fields, with further studies on mechanisms of cellulose activation.The work was performed in Cemef - Mines ParisTech, Sophia Antipolis, France, and TI / Hamburg University, Germany and financed by Sappi, Tembec, Lenzing, Viskase and Spontex and had support from EPNOE (European Polysaccharide Network of Excellence).

Cellulosans tillgänglighet och reaktivitet är nyckelparametrar vid framställning av regenererad cellulosa och cellulosaderivat. Det är välkänt att på grund av cellulosans kristallina struktur är tillgängligheten begränsad för lösningsmedel och olika reagens. Till exempel kan en inhomogen substitution av hydroxylgrupperna i cellulosakedjan resultera i cellulosaderivat av sämre kvalitet. Baserat på detta har en del av arbetet i denna studie fokuserat på att förbättra cellulosans tillgänglighet och reaktivitet genom att studera effekten av olika enzymatiska behandlingar med monokomponent endoglukanaser. Resultaten visar att närvaron av en cellulosabindande domän fyller en viktig funktion för att öka cellulosans reaktivitet, men strukturen för den katalytiska domänen visade sig ha den största inverkan på cellulosans tillgänglighet. I kompletterande studier har även effekten av en mekanisk förbehandling i kombination med enzymatisk behandling utvärderats. Kombinationen av förbehandlingarna resulterade i en positiv effekt, cellulosans reaktivitet kunde ökas i större omfattning. I dag används huvudsakligen dissolvingmassor som råvara vid framställning av cellulosaregenerat och cellulosaderivat. Kraven för dessa s.k. specialmassor är högt cellulosainnehåll samt lågt hemicellulosa- respektive lignininnehåll. På grund av dessa specifika krav är produktionskostnaderna för dessa massor högre än konventionella sulfatmassor. Den andra delen av studien har därför fokuserat på möjligheten att använda dessa sulfatmassor som dissolvingmassa. Det har visats att kombinationen av enzymatiska behandlingar med monokomponent endoglukanas och xylanas följt av ett alkaliskt steg kan resultera i massor där kraven uppfylls med avseende på cellulosans reaktivitet, och cellulosa- respektive hemicellulosainnehåll. / The accessibility and reactivity of cellulose are key parameters on the manufacturing of cellulose derivatives and regenerated cellulose. It is well known that, due to the crystalline structure of cellulose, the accessibility of solvents and reagents is limited. For instance, an inhomogeneous substitution of the hydroxyl groups of the cellulose chain might lead to the production of derivatives of low quality. As a consequence, part of this work has focused on improving the accessibility and reactivity on cellulose by studying the effect of different monocomponent endoglucanases. It has been demonstrated that the presence of the cellulose-binding domain plays an important role on the enhancement of cellulose reactivity; however, the structure of the catalytic domain has been showed to have the highest influence on this parameter. Furthermore, the influence of mechanical treatment prior to enzymatic treatment has been examined. The combination of pretreatments showed a positive effect enhancing to a larger extent the cellulose reactivity. Currently, dissolving-grade pulps are commonly used for the production of cellulose derivatives and regenerated cellulose. The requirements for these so-called “special pulps” are a high cellulose content and a low hemicelluloses and lignin content. As a result of these specific demands, the production costs of these pulps are higher than those of common kraft pulps. The second part of this work, therefore, has been focused on the study on the viability of converting kraft pulps into dissolving pulps. It has been demonstrated that the combination of enzymatic treatments using a monocomponent endoglucanase and a xylanase together with the addition of an alkaline step could fulfil the requirements of a commercial dissolving pulp in terms of cellulose reactivity and cellulose and hemicellulose content. / QC 20101117

Submitted in fulfillment of the requirements for the degree of Doctor of Technology: Chemistry, Durban University of Technology, Durban, South Africa, 2015. / This thesis forms part of the Council for Scientific and Industrial Research, Forestry and Forest Products Research Centre (CSIR-FFP) biorefinery project which aims at developing and implementing novel industrial processes production of cellulose textile fibres. The focus of this study is to investigate the dissolution of South African Eucalyptus raw (unbleached) and final (bleached) dissolving pulp and saw dust wood in an ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [Emim][OAc] and the co-solvents [dimethylsulfoxide (DMSO)] or [dimethylformamide (DMF)] mixtures, to obtain regenerated cellulose by the further addition of water and acetone. The IL/co-solvent mixtures were able to dissolve the raw and final pulp samples at 120 ˚C for 6 hours whereas the sawdust wood dissolved in 10 hours. The IL/DMF mixture gave higher cellulose recoveries of 41.88 % for the raw pulp, 49.89 % for the final pulp sample and 32.50 % for sawdust wood while the IL/DMSO mixture gave a recovery of 15.25 % for the raw pulp sample, 36.25 % for the final pulp sample and 17.83 % for the sawdust wood sample. The regenerated cellulose materials were characterized by Fourier Transformer Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR), Scanning Electron Microscopy (SEM), Thermo gravimetric Analysis (TGA) and Powder X-Ray Diffraction (pXRD), and compared with a standard microcrystalline of cellulose. It was observed that the FTIR and NMR spectra of the regenerated cellulose and MCC were similar which then indicates that no chemical reaction occurred during the dissolution and regeneration process of cellulose. SEM and X-ray diffraction (XRD) patterns of the results showed that after dissolution the cellulose I (native form), the crystalline structure was completely converted into cellulose II (amorphous) structure, and this was due to the removal of lignin and decrease in cellulose crystallinity. TGA results showed that the regenerated cellulose samples have higher char yields compared to the MCC which is due to the IL remaining in the regenerated cellulose. It was also observed that the addition of the co-solvents decreased the viscosity of the IL mixture, facilitating dissolution of the cellulose that led to additional swelling and reduction of the recalcitrant nature of the cellulose crystalline structure and intermolecular interactions. This led to increased accessibility and dissolution of the cellulose. The findings in this study have the potential to bring ILs closer to applications for biomass technology in particular for an economically viable dissolution method for biomass because ILs have a benefit of being easily separated from the anti-solvent, which provides a simple solution for IL recycle ability and re-use. The novel aspect of this study is: . This is the first study in the South African context to examine the influence of the lignin on the dissolution and regeneration of Eucalyptus sawdust wood and dissolving pulp. / D

Single stage and two-stage sodium sulfite cooking were carried out on either spruce, pine or pure pine heartwood chips to investigate the influence of several process parameters on the initial phase of such a cook down to about 60 % pulp yield. The cooking experiments were carried out in the laboratory with either a lab-prepared or a mill-prepared cooking acid and the temperature and time were varied. The influences of dissolved organic and inorganic components in the cooking liquor on the final pulp composition and on the extent of side reactions were investigated. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. A better understanding of the delignification mechanisms during bisulfite and acid sulfite cooking was obtained by analyzing the lignin carbohydrate complexes (LCC) present in the pulp when different cooking conditions were used. It was found that using a mill-prepared cooking acid beneficial effect with respect to side reactions, extractives removal and higher stability in pH during the cook were observed compared to a lab-prepared cooking acid. However, no significant difference in degrees of delignification or carbohydrate degradation was seen.  The cellulose yield was not affected in the initial phase of the cook however; temperature had an influence on the rates of both delignification and hemicellulose removal. It was also found that the  corresponding activation energies increased in the order:  xylan, glucomannan, lignin and cellulose. The cooking temperature could thus be used to control the cook to a given carbohydrate composition in the final pulp. Lignin condensation reactions were observed during acid sulfite cooking, especially at higher temperatures. The LCC studies indicated the existence of covalent bonds between lignin and hemicellulose components with respect to xylan and glucomannan. LCC in native wood showed the presence of phenyl glycosides, ϒ-esters and α-ethers; whereas the α-ethers  were affected during sulfite pulping. The existence of covalent bonds between lignin and wood polysaccharides might be the rate-limiting factor in sulfite pulping. / The sulfite pulping process is today practised in only a small number of pulp mills around the globe and the number of sulfite mills that use sodium as the base (cation) is less than five. However, due to the increasing interest in the wood based biorefinery concept, the benefits of sulfite pulping and especially the sodium based variety, has recently gained a lot of interest. It was therefore considered to be of high importance to further study the sodium based sulfite process to investigate if its benefits could be better utilized in the future in the production of dissolving pulps. Of specific interest was to investigate how the pulping conditions in the initial part of the cook (≥ 60 % pulp yield) should be performed in the best way. Thus, this thesis is focused on the initial phase of sodium based single stage bisulfite, acid sulfite and two-stage sulfite cooking of either 100 % spruce, 100 % pine or 100 % pine heartwood chips. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and cooking time were varied. Activation energies for different wood components were investigated as well as side reactions concerning the formation of thiosulfate. LCC (Lignin carbohydrates complexes) studies were carried out to investigate the influence of different cooking conditions on lignin carbohydrate linkages.