During kraft cooking a significant part of the wood material, especially lignin and hemicelluloses, is degraded and dissolved in the cooking liquor, rendering a broad range of degradation products with different molecular mass and functional groups. The main part of this thesis has been devoted to clarify the role of these dissolved wood components (DWC) during kraft cooking. The investigations have covered their influence on e.g. the delignification rate, pulp yield, point of defibration, unbleached pulp c olour and pulp bleachability, i.e. the amount of bleaching chemicals consumed per kappa number or lignin unit to reach a certain brightness. Both softwood (Picea Abies) and hardwood (Eucalyptus urograndis) have been studied. During kraft cooking, many reactions occur simultaneously. Therefore emphasis has been put on separating the effects of hydroxide ions, hydrogen sulphide ions, sodium ions and DWC. This has been enabled by the use of a so called constant-composition-cooking technique, which enables the use of almost constant concentrations of the cooking chemicals during the cook and also results in a very low concentration of DWC in the cooking liquor. The presence of DWC has been controlled by the addition of industrial black liquor. To further scrutinise the role of DWC, the effect of different molecular mass fractions were studied and representative model substances were used to clarify the origin of the observed effects. A kinetic study showed that the delignification rate was significantly affected by the presence of DWC in the cooking liquor and resulted in a rate increase in the part of the cook where the bulk phase dominates and a decreased delignification rate when the residual phase dominates. The increase in delignification rate was dependent on the concentration of DWC and was observed in softwood as well as hardwood kraft cooks. The rate increasing effect was investigated further by the use of ultra- and nanofiltra tion. This way the DWC was divided into fractions with different molecular mass distributions. The results showed that the increase in delignification rate related more strongly to the content of free phenolic groups in the DWC than on the total amount of DWC. By cooking in the presence of representative model substances the effect was further clarified. Aromatic structures with free phenolic groups gave a rate increasing effect while no visible effect could be seen from other structures. This supports the finding that the delignification rate relates to the amount of free phenols in the cooking liquor and shows that the phenolic functionality take active part in the delignification reactions. Free phenolic groups in the degraded lignin may explain a large part of the rate increasing effect seen from the presence of DWC. Further, the presence of DWC increased the point of defibration in a eucalyptus kraft cook and made it possible to terminate the cook at a higher kappa number with the same amount of reject. By terminating the cook at a higher kappa number it was possible to noticeably increase the fully bleached pulp yield. The content of hexenuronic acids (HexA) in the eucalyptus pulp depends on the H-factor and increases with delignification, providing that the bulk phase still dominates. Therefore, by increasing the rat e of delignification and terminating the cook at a higher kappa number it was possible to significantly decrease the amount of HexA in the pulp. The presence of DWC causes a darkening of the unbleached pulp. Bleachability in a D(EOP)DD sequence was negatively affected by the presence of DWC during pulping of softwood, while no effect was seen on the bleachability of hardwood / QC 20100920

In previous studies on suction box dewatering, three mechanisms were identified that determine the dry content of a web, viz. web compression, displacement of water by air and rewetting. In the present work, the relative importance of the three mechanisms was investigated through direct measurement of the web deformation, the dry content changes during and after the suction pulse, the air flow through the fibre network and the saturation of the web after the suction pulse. Suction pressure, suction time and rewetting time were varied. The experiments were done with chemical and mechanical pulp webs of various grammages. It was found that a large web deformation took place during the suction pulse, particularly at its beginning. Compression dewatering was found to be the most dominant dewatering mechanism. Displacement dewatering started after most of the web compression had occurred. Its contribution to the increase in dry content was most pronounced for higher suction pressures, longer suction times and for chemical pulp webs. A surprisingly large expansion of the web was observed immediately after the suction pulse. This expansion was the effect of rewetting. This rewetting strongly reduced the dry content of the web if the web had not been immediately separated from the forming fabric at the end of the suction pulse. Under the conditions studied, the decrease in dry content amounted to the order of 3 to 6 %. Rewetting was smaller for longer suction times and higher suction pressures. A considerable air flow through the web occurred under these conditions. This air flow apparently moved water from the forming fabric into the suction box, thus making less water available for rewetting. Rewetting for mechanical pulp webs was more pronounced and took place faster than for chemical pulps. The use of a membrane on top of the web during suction box dewatering proved to be advantageous for reducing the air flow through the web. However, under the conditions investigated, the dry content could not be improved. Although the web compression was increased when using a membrane, especially at a higher suction pressure, rewetting after the suction pulse had an even larger negative impact on the dry content, which, as a result, was lower. / QC 20100924

In conventional viscose manufacturing, a large amount of carbondisulfide is consumed. This amount has to be decreased to keep the production cost down and to reduce the environmental impact. The purpose with this work was to show if an enzyme treatment of a dissolving pulp could increase the degree of substitution in the viscose so that the amount of carbon disulfide consumed in the process could be decreased. Previous investigations by Kvarnlöf (2007), Engström et.al. (2006) and Henriksson et.al. (2005) has shown that the reactivity of a dissolving pulp (the cellulose raw material) increased when it was pre-treated with endoglucanase (enzyme). Kvarnlöf (2007) also showed that the amount of carbon disulfide that is needed to produce an ordinary viscose (in this work a more viscous viscose has been investigated) could be reduced with one third because of the enzyme treatment.   In this thesis, viscose has been manufactured in a laboratory where the process has been adapted to look like the industrial as far as possible. Analyses were done on the viscose viscosity and degree of substitution. A reference curve was made with the percentage carbon disulfide load versus the viscose gamma number (degree of substitution). Then it was investigated how an enzyme treatment of the dissolving pulp affected the viscose. After the enzyme treatment, the manufacturing process for viscose was done in the exact same way as when the reference tests were done. The enzyme used in this thesis was Carezyme which contents endoglucanase. Then the results from the analyses of the viscose manufactured from enzyme treated dissolving pulp and the reference curve was compared. A positive result would have been that viscose manufactured with enzyme treatment gets a higher gamma number than viscose, with the same load of carbon disulfide, manufactured in the regular way.   The results showed that the degree of substitution had no effect at all; the viscose that has been manufactured from enzyme treated dissolving pulp resulted in gamma numbers on or very close to the reference curve. The only effect that could be shown was a decrease in viscosity, which unfortunately was an unwanted effect. The enzyme treatment has also hampered the process, where shorter fibres among other things have given poorer dewatering properties. Analyses on the viscose manufactured in the laboratory showed that it didn't have the same characteristics as viscose manufactured in a plant. / I den konventionella tillverkningsprocessen för viskos förbrukas stora mängder koldisulfid. Denna mängd behöver minskas, både för att hålla nere produktionskostnaderna men också för att minska miljöpåverkan. Syftet med arbetet var att undersöka om en enzymbehandling av en dissolvingmassa kunde öka substitutionsgraden så att koldisulfid-förbrukningen skulle kunna minskas. Det har i flera tidigare undersökningar av Kvarnlöf (2007), Engström m.fl. (2006) och Henriksson m.fl. (2005) visats att reaktiviteten hos en dissolvingmassa (råvaran i viskosprocessen) ökar när den förbehandlats med endoglukanas (enzym). Kvarnlöf (2007) visade dessutom att mängden koldisulfid som behövdes för att tillverka spinnviskos (i detta examensarbete har en viskösare viskos undersökts) kunde minskas med en tredjedel tack vare enzymbehandlingen.   I detta examensarbete har viskos tillverkats i laboratoriet där processen har anpassats så att den liknar den industriella så mycket som möjligt. Analyser gjordes på viskosens viskositet och substitutionsgrad. En referenskurva tillverkades där den procentuella koldisulfid-satsningen plottades mot viskosens gammatal (substitutionsgraden). Därefter undersöktes hur en enzymbehandling av dissolvingmassan påverkade den färdiga viskosen. Efter enzymbehandlingen av dissolvingmassan utfördes tillverkningsprocessen precis som vanligt för att man skulle kunna se effekterna av enzymet. Enzymet som användes i arbetet var enzympreparationen Carezyme som innehåller endoglukanas. Sedan jämfördes resultaten från analyserna av viskosen tillverkad från enzymbehandlad dissolvingmassa med referensvärdena. Ett positivt resultat hade varit att enzymbehandlad viskos hade ett högre gammatal än viskos tillverkad på vanligt sätt utan enzymförbehandling men med samma koldisulfidsats.   Resultaten visar att substitutionsgraden inte har påverkats alls, dvs. den viskos som tillverkats från enzymbehandlad dissolvingmassa fick gammatal som låg på eller mycket nära referenskurvan. Den enda effekt av enzymet som kunde visas var en viskositetssänkning, vilket inte var något som eftersträvades. Processen har dessutom försvårats av enzymsteget, där kortare fibrer bl.a. gav sämre avvattningsegenskaper. Viskosanalyser har visat att viskosen som tillverkats på laboratoriet inte har samma egenskaper som viskos tillverkad på fabrik.

Papers are coated in order to improve the properties of the surface, to improve printability and to include new functionalities like barriers properties. Typical coating formulation contains a high number of components, some are made from minerals and others are manufactured from petroleum. The barrier properties of today's paper based packages are plastics and/or aluminum             foil. Environmentally friendly substitutie of these nonrenewable materials are needed.  Nanocellulose is a promising material                 and of a growing interest as an alternative to petroleum-based materials, since nanocellulose films/coatings have been shown to have excellent mechanical and barrier properties.   This project aimed to evaluate nanocellulose in combination with minerals in paper coatings. The project had two approaches. One was to evaluate the barrier properties of MFC coatings with mineral included. The second part was about coatings for           printing matters, and evaluation of the possibility to replace petroleum-based binders in the coating color with MFC. Barrier properties were evaluated by measuring the air permeability of the coatings. The properties of the coating affecting the         printability in offset printing examined was the surface energy, the gloss, the roughness of the coatings, the strength and the offset ink setting.   Carboxymethylated nanocellulose formed denser films and had superior barrier properties compared with enzymatically pretreated nanocellulose. Adding of minerals did not affect the barrier properties of the MFC coatings to a significant extent.         Therefore, minerals cannot be added to enhance the barrier but it can be added to reduce the cost of the coating process without losing any barrier properties.                                 The print quality depends on how the ink interacts with the coating. These coatings did have a relatively high surface energy, which is preferable for printing with waterborne ink. It was also shown that the absorption abilities increased when the amount of MFC was increased. However, offset printing demands high surface strength and addition of MFC in the coating color                     drastically decreased the strength. This means that the coatings produced in this work are not strong enough and thereby not           suitable for offset printing. However other printing technologies put lower demand on surface strength and are still possible.

<p>One of the major cost factors in mechanical pulp production is the electrical energy input. Much of the research in this field has therefore been devoted to an understanding of the mechanisms in the refining process and, consequently, to find ways of reducing the electrical energy consumption. Shear and compression are probably the main types of fibre deformation occurring in refiners for collapsing and fibrillating the fibres into a suitable pulp. In current refiners, the repeated mechanical action of the bars on the fibres consumes large amounts of energy in a treatment of mechanical fibres that is almost random.</p><p>Fundamental studies of the deformation of wood have indicated that a combination of shearing and compression forces is highly beneficial in terms of fibre deformation with a low energy demand. Pure compression is able to permanently deform the fibre but requires a substantial amount of work, while pure shearing, although being much less energy demanding, does not lead to any permanent deformations. A more suitable application of the shear and compression forces on the wood fibres during the refining process could be a way to develop fibres at a lower energy demand. These ideas have been studied in this work trying to find new ways of saving energy in the mechanical pulping process.</p><p>The first paper in this thesis discusses the way of producing wood shavings and the introduction of shear/compression deformations in these, as well as the potential benefits of using them instead of wood chips as raw material for TMP production. With the shaving process, high deformations in the wood cells were achieved by the shear and compression forces. This led to energy savings of about 25% at a given tensile index, when compared to traditional chips. The quality of the pulp produced from wood shavings was found to be better than that of the pulp produced from wood chips, when it came to strength properties (except for tear index) and optical properties at comparable energy levels.</p><p>Another way of reducing energy consumption in refining involving a limited shear combined with compression forces for the mechanical treatment of both wood chips and coarse fibres was also studied. This work shows that such a kind of treatment resulted in a high degree of fibre collapse at low energy demands. The thick-walled transition fibres could even be permanently deformed. Furthermore, refining trials, utilising shear and compression pre-treated chips, showed that the strength properties, except for tear index, along with the optical properties of a TMP could be improved and the electrical energy consumed could be reduced by approx. 100 kWh/tonne, when compared to untreated chips.</p><p>The results from the pilot trials described in this work could be used as a starting point for further implementation in the industry, in order to identify the most efficient way of producing mechanical pulp with a lower consumption of electrical energy.</p>

The aim of this thesis is to use differential analysis and finite volume method (FVM) to model and analyze a continuous pulp digester in order to create a detailed picture of the flow behaviour and chemical reactions in the digester. This information will be used to optimize wood chip flow and reactions and to diagnose and avoid faults such as hang-ups and channelling. As digesters increase in size, the importance of control of the liquor flow in the wood chip bed also increases. Pulping reactors are often faced with production disturbances that cause reduced fibre quality, non-uniform chemical reactions and damaging channelling phenomena. The models that are proposed in this thesis aim to consider the fluid dynamics, thermodynamics and chemical reactions together in order to create a model with more detail than has been previously reported. The digester is of the continuous type and has a circular cross-section, with a height of 60 m and a diameter that increases stepwise from 6 m at the top to 7 m at the bottom. The geometry of the digester, including an internal pipe with three different diameters, three inlet flows at three levels of the digester, inlets and outlets at the top and bottom, and a number of peripheral circulation pipes connected to the screens at three levels, is represented in simulations by a 2D axisymmetric model constructed in Gambit. The interactions between the two phases - the wood chips and the alkaline liquor - are studied using the finite volume method (FVM). Eulerian and Mixture numerical methods are evaluated for solving a mass transfer multiphase model with a porous matrix, species transport and reaction system in FLUENT. Variable porosity is used to model channelling in the digester. Comparisons of the results of simulations with real digester data indicate that the multiphase model, with the species transport and mass transfer modules accurately predict the pulping chemical reactions inside the digester and are able to evaluate pulp quality. The species transport model with reaction scheme is able to predict the mass balance equation and stoichiometry of the pulping reaction. The porous media scheme complements this approach to give a more complete view of pulp production, including the effect of faults in the process. The approaches to the FVM described in this thesis enable an accurate view of the pulping process which can contribute to improved control and optimization of the process. / CFD modellering av hydrodynamiska och kemiska reaktioner i massakokare Huvudsyftet med denna avhandling har varit att utveckla en numerisk modell som kan användas för att simulera och styra massatillverkningsprocessen. En finit volym metod har tillämpats, med hjälp av CFD (Computational Fluid Dynamics) programmet FLUENT. Även om den kontinuerliga sulfatprocessen är den dominerande kemiska massaprocessen, så är vår kunskap om vad som händer i kokaren med avseende på hydraulik och de kemiska reaktionerna på en relativt låg nivå. Anledningen är att det är mycket svårt att ta ett prov från vilken punkt som helst i kokaren för att göra olika mätningar. Speciellt, hängningar och kanalbildning i kokaren är inte väl förstådd trots att dessa fenomen orsakar betydande produktions- och kvalitetsförluster. Det finns varken en entydig förklaring till eller lösning för hur man skall kunna undvika hängning och kanalbildningar ännu. Genom CFD-simuleringar som utvecklats i denna avhandling kan vi simulera vad som kan antas hända, och hur dessa fenomen kan upptäckas genom att mäta temperaturer, tryck och Kappatal i olika positioner. CFD-modellerna kan beskriva vad som kan hända i kokaren och indirekt skapa en bild av massaprocessen. Förhoppningsvis kan simuleringarna också användas för att undersöka hur man kan motverka störningarna. Storleken på kokare ökar kontinuerligt för att tillgodose högre produktionstakt men storleksökningen gör det samtidigt ännu svårare att hantera kemiska processer inne i kokaren. Det finns både satsvis- och kontinuerliga kokare, men de modernaste är kontinuerliga kokare. Dessa har ofta komplicerade cirkulationsloopar för att kunna hålla rätt förhållande med avseende på temperatur och kemikaliekoncentrationer i olika delar av kokaren.  Problemen med kokare är bland annat ojämn fördelning av vätskeflödet genom flisen, trycket från flispelaren, fliskomprimering, flisrörelse i olika riktningar, heterogena träflisformer (och storlek på bitarna), tvättningseffektivitet, swing mellan olika vedkvaliteter och hängningar av flis längs väggarna. I denna avhandling har en matematisk 3-D modell utvecklats där alla dessa faktorer och fenomen undersöks för att förbättra kunskapen om flödet och de kemiska processerna som gör det möjligt för oss att hantera och optimera produktionen. Genom att simulera olika driftproblem och jämföra simuleringarna med processdata kan vi försöka analysera kemiska processen inne i kokaren. För att kunna kombinera en verklighetsnära simulering med en rimlig tid för att lösa problemet har en Axisymetrisk 2-D struktur använts. Det betyder att man antar att kokaren ser likadan ut i alla riktningar från centrum och utåt.

As paradas planejadas gerais nas indústrias papeleiras, normalmente realizadas anualmente, são fundamentais devido ao processo produtivo e estratégicas para a competitividade no setor. Face à sofisticação dos equipamentos e instalações, denotando intervenções complexas e de grande porte, altos custos e riscos potenciais de acidentes e danos ambientais, procura-se uma caracterização desses eventos como grandes empreendimentos. Esses, fazem parte da estratégia de manutenção definida para a planta fabril, sendo gerenciados pela equipe de manutenção que atua voltada a disponibilidade, confiabilidade, qualidade e produtividade. Neste sentido, este trabalho desenvolve uma sistemática de manutenção para o gerenciamento e controle das paradas planejadas gerais em processos de produção de celulose e papel, com a finalidade de facilitar e promover o sucesso na execução de todas as atividades e etapas envolvidas. Para isso, contextualiza-se o setor e as paradas planejadas; são revisados os principais conceitos, técnicas, práticas e ferramentas características à gestão da manutenção, qualidade e conhecimento; são estudadas abordagens específicas voltadas aos processos de produção contínua; é verificada uma prática empresarial do setor e; finalmente, é proposta uma sistemática fundamentada nestas pesquisas. Como principais benefícios observam-se: a sinergia entre as equipes de manutenção e operação; a valorização da manutenção na gestão do processo produtivo; a competitividade do negócio; a otimização dos recursos e as alavancagens de produtividade. / The general planned stops within the paper industries, once in the year as a rule, are due to the productive process and competitiveness strategies in that business sector. Current sofistified equipments and facilities call for complex and significant interventions. Because high costs involved and potential risks of both accidents and environmental nature damage, those events are characterized as important projects. They are part of the strategy defined for the manufacturing plant, thus being managed by the maintenance team focusing availability, reliability, quality and productivity. In view of such scenario, this paper develops a maintenance system addressing the management and control of planned stops within the cellulose pulp and paper production processes. The scope is to facilitate and promote the success when carrying out all the activities involved. Therefore, the context of the sector and planned stops is discussed; the main concepts, techniques, practices and tools specific to the management of maintenance, quality and knowledge are reviewed; approaches specific to the continuous production processes are studied; business practices within the sector are analyzed, and, finally, a systemic approach proposal is made grounded on the preceding research. The most important benefits observed were: the achievement of synergy among the maintenance and production teams; the true understanding of the maintenance value in the productive process; the business competitiveness; resources optimization as well as productivity boosting.

<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>

This thesis examines the formation of Polyelectrolyte Multilayers (PEM) on cellulose fibres as a new way of influencing the fibre surface and the adhesion between wood fibres. The aim of the study was to enhance the fundamental understanding of the adsorption mechanisms behind the formation of Polyelectrolyte Multilayers on cellulose fibres; to study how the properties of the layers can be influenced and to show how the properties of the layers influence the adhesion between the fibres and the strength of paper sheets made from the PEM treated fibres. Different polyelectrolyte systems are known to form PEMs with different properties, and in this work two different polymer systems were extensively studied: poly(dimethyldiallylammonium chloride) (PDADMAC) / poly(styrene sulphonate) (PSS), which are both strong polylectrolytes (i.e. are highly charged over a wide range of pH) and poly allylaminehydrochloride (PAH) /poly acrylic acid (PAA), which are both weak polyelectorlytes (i.e. sensitive to pH changes). PEMs were also formed from PAH/ poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS), in order to form electrically conducting PEMs on fibres and PEM-like structures were formed from polyethylene oxide (PEO) and polyacrylic acid (PAA). In order to study the influence of the PEM on adhesion and paper strength, fibres were treated and used to form sheets which were physically tested according to determine the tensile index and strain at break. Both these systems were studied using different molecular mass fractions. High molecular mass PDADMAC/PSS (&gt;500k/1000k) had a significantly greater influence as a function of the number of layers than low molecular mass PDADMAC/PSS (30k/80k). In contrast, sheets made from high molecular mass PAH/PAA (70k/240k) showed a significantly lower increase in strength than sheets made from low molecular PAH/PAA investigated earlier. Both these systems had a greater influence on paper strength when the cationic polyelectrolyte was adsorbed in the outermost layer. The amount of polyelectrolytes adsorbed on the fibres was determined using polylectrolyte titration (PET) and destructive analytical methods. Adsorption to model surfaces of silicon oxide was studied before the adsorption on fibres, in order to understand the influence on PEM properties of parameters such as salt concentration and adsorption time. Adhesion studies of surfaces coated with PAH/PAA using AFM, showed an increase in adhesion as a function of the number of adsorbed layers. The adhesion was higher when PAH was adsorbed in the outermost layers. Individual fibres were also partly treated using a Dynamic Contact Angle analyser (DCA) and were studied with regard to their wettability. In general, the wettability was lower when the cationic polymer was outermost. The level of adhesion and paper strength are discussed in terms of rigidity and wettability and the PEMs demonstrating a large number of free chain ends, a large chain mobility and a low wettability was found to have the greatest influence to adhesion and paper strength. / QC 20100823

Mechanical pulping for producing pulps from softwood suitable for printing grade papers, like news, is a highly energy-intensive process consuming around 2000 kWh/t in electrical energy. Due to increasing energy costs and environmental issues there is a high demand for decreasing this energy consumption. The mechanical treatment of wet wood pieces in a refiner, in the mechanical pulp plant, is a complex mechanical loading. This is a process occurring between rotating discs at high speed and temperatures of 140 °C - 160 °C, where by means of shear and compression forces the fibres are separated and then made flexible, fibrillated and collapsed for good bonding ability. In this process also fines are created giving the optical properties of the paper. In mechanical pulping only a fraction of the applied energy is used for the structural changes of the wood material. Thus fundamental studies of the loading modes of wood under refining conditions and in particular under combined shear and compression loading are desired to gain more information regarding the possibility of affecting the mechanical pulping in an energy efficient way. The possibilities to study the behaviour of wood under a combined shear and compression load were in this thesis investigated using two methods: the Iosipescu shear test and the Arcan shear test. In both apparatus different combinations of shear and compression load were achieved by different rotations of the shear test device itself. Measurements with the Iosipescu device on a medium density fibreboard showed good agreement between experimental results and numerical simulations. Finite element analysis on wood showed, however, that with the use of a homogeneous material in the model the level of strain reached would be ten times smaller than experimentally measured. This fact is probably due to the honeycomb structure of the wood cells that allows for different local deformations that could not be represented by a continuous material model. Thus to study the deformations on the fibre level of wood an experimental equipment that uses smaller samples was needed. With a modified Arcan shear device such deformations under combined shear and compression load and in pure compression were possible showing different deformation patterns. During pure compression the cell walls bend in a characteristic “S” shape, independently of the shape of the fibre cells and their cell wall thickness. Under combined shear and compression, however, mainly the corners of the fibre cells deform giving a “brick” shape to the cells. In a second deformation performed in compression, the fibre cells follow the same deformation pattern as given by the first deformation type whether in compression or in combined shear and compression. The interpretation is that permanent defects in the cells themselves are introduced already in the first load cycle of the wood samples. The energy used under the different loading conditions showed that the first deformation required the largest amount of energy, for all loading conditions. The deformation in compression required larger amounts of energy than the deformation in combined loads. For subsequent deformations less energy was needed for compression if a combined load had preceded it. Due to the fact that less energy is needed to start to deform wood in combined load than under compression load, the application of a combined load as a first cycle may thus be a way to permanently deform fibres using less energy. To investigate the critical parameters determining the permanent deformation of cells, a finite element model of a network of twelve cells was developed. Special care was given to the material properties to study how the variation of the fibril angle in the different layers affects the deformation pattern of the wood fibres under the different loading conditions. The model shows that whether modelled as homogeneous linear isotropic material or as an orthotropic material defined for every layer of the cells wall, no difference in the deformation of the network of the fibres was achieved. It is probable that the deformation type is more determined by the geometry of the fibres themselves than by their material properties / QC 20101005