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<p>Dynamic (or 2D) FT-IR spectroscopy in combination withpolarized IR irradiation has been used in this work to studywood polymer orientation and interactions on theultrastructural level in wood fibers in the native state aswell as the effects of different pulping processes. The woodpolymer interactions were studied under both dry and humidconditions.</p><p>The matrix of lignin and hemicelluloses located between thewell-ordered cellulose fibrils in the wood cell wall of sprucewas here shown to be more highly ordered than has earlier beenrevealed. It was confirmed that glucomannan is orientedparallel to the cellulose fibrils and is highly coupled to it.The lignin was also shown to have a main orientation in thestructure although this is probably not as strong as that ofglucomannan. The orientation of the lignin may derive from thefact that the polysaccharides act as templates during thelignification of the cell wall. This organization implies thatnot only the cellulose but also the lignin and thehemicelluloses have different mechanical properties in thelongitudinal and cross-fiber directions.</p><p>The ability to gain molecular information on the stresstransfer in polymers with dynamic FT-IR spectroscopy made itpossible to verify experimentally earlier molecularcalculations on the stress transfer within the cellulose chain.It was also possible to show, on the molecular level, thedominant importance of the cellulose fibrils for the stresstransfer in the longitudinal direction of pulp fibers,including lignin-rich mechanical pulp fibers. The glucomannanof softwood fibers was also shown to participate in the stresstransfer in the fiber direction indicating a close associationwith the cellulose, whereas the xylan showed no dynamicresponse. Already under dry conditions, the lignin was shown tohave a more viscoelastic response than the polysaccharidesduring the loading of pulp fibers and it was thus able to moveindependently of the cellulose.</p><p>The enhanced spectral resolution obtained with dynamic FT-IRspectroscopy made it possible to study the crystalstructure/chain order of cellulose in pulp fibers. Thepossibility of following changes in the relative cellulose Iallomorph composition of pulp fibers was demonstrated for somechemical pulps.</p><p>Dynamic FT-IR experiments under humid conditions and ofelevated temperatures made it possible to study the softeningof the biopolymers in their native environment. This was alsodemonstrated for some different pulps, and this may be apromising tool for obtaining viscoelastic information on themolecular level in composite systems such as wood fibers.</p><p><b>Keywords:</b>cellulose, cooperation, crystallinity, dynamictest, glucomannan, hardwood, holocellulose, humidity, infraredspectroscopy, kraft pulp, lignin, mechanical pulp, orientation,polarised light, softwood, strain, sulphite pulp,viscoelasticity, xylan</p>

Les pâtes à dissoudre, composées à 95% de cellulose, sont la matière première pour la production de fibres cellulosiques régénérées (viscose, Lyocell…) et de dérivés cellulosiques (ester, éther ou nitrate de cellulose). En tant qu’alternative aux matériaux issus de ressources pétrolières, ces produits connaissent actuellement un fort regain d’intérêt. Ainsi, la production de pâte à dissoudre devrait croître fortement au cours de la prochaine décennie. L’objectif de cette thèse est de proposer des procédés de conversion d’une pâte papetière de résineux en pâte à dissoudre. Pour cela les hémicelluloses présentes dans les pâtes kraft papetières doivent être extraites. Trois méthodes d’extraction d’hémicelluloses ont ainsi été étudiées : (1) une extraction alcaline à froid (CCE) dans des conditions non conventionnelles, (2) un procédé se divisant en deux étapes successives : un stade acide à haute température (150°C) suivie d’une extraction alcaline à chaud (AHCE) et (3) une hydrolyse enzymatique par trois enzymes commerciales (une xylanase, une mannanase, une cellulase). Les deux premières méthodes ont permis de produire des pâtes avec des caractéristiques proches des pâtes à dissoudre commerciales. Cependant, dans les trois voies d’extraction étudiées, l’extraction d’hémicelluloses n’a jamais atteint 100%. Des prétraitements des pâtes (raffinage, explosion à la vapeur, oxydation TEMPO) ont alors été testés pour améliorer l’extraction des hémicelluloses. De nouvelles séquences de purification basées sur la combinaison d’une étape de raffinage suivie d’une extraction alcaline à froid (CCE) peuvent être ainsi imaginées. La dernière partie de ces travaux de thèse s’est intéressée au gonflement des pâtes à dissoudre. Les travaux ont abouti à la création d’une nouvelle méthode simple et rapide de caractérisation du gonflement des fibres de pâte cellulosique. Cette méthode de mesure peut être, dans certaines conditions, considérée comme une mesure alternative de la réactivité des pâtes à dissoudre habituellement caractérisée par le test Fock. / Dissolving pulps, which are composed of 95% cellulose, are the raw materials for the production of regenerated cellulose fibres for textile application and for the production of cellulose derivatives. These products are alternatives to oil based materials. A growing demand in such products is expected in the next decades. Therefore, additional capacities in the production of wood dissolving pulp must be created. The purpose of this work is to develop hemicellulose removal processes with the aim to convert a softwood kraft paper pulp into a dissolving pulp. Three extraction methods were tested: (1) A cold caustic extraction process (CCE) performed under conventional and unconventional conditions; (2) A process consisting in an acid stage at high temperature (up to 150°C) followed by a hot caustic extraction (A-HCE); (3) An enzymatic hydrolysis using xylanase, mannanase, and cellulase. Conversion was quite successful with the two first processes. However, 100% of hemicellulose removal was never reached. In order to improve the hemicellulose extraction efficiency, several pre-treatments were tested (refining, steam explosion, TEMPO oxidation). The addition of a refining stage allows a reduction of the NaOH concentration during CCE extraction without affecting the hemicellulose extraction efficiency. The last part of this thesis work focus on the dissolving pulp swelling. A new and rapid test for the characterization of fibre swelling was developed. This method was used as an approach to the assessment of dissolving pulp reactivity in the viscose process in place of the Fock’s method.

Cavalcanti, BN. Resposta de fibroblastos de polpa humanos frente a substâncias liberadas por capeadores pulpares diretos [Tese de Doutorado]. São Paulo: Faculdade de Odontologia da USP; 2003. RESUMO O objetivo do presente estudo foi o de avaliar os efeitos citotóxicos de substâncias liberadas durante a aplicação de materiais utilizados em capeamento pulpar direto, sobre fibroblastos de polpa dentária humana. Utilizou-se para o experimento meios condicionados pelas substâncias a serem testadas, divididas nos grupos a seguir: grupo I: controle (meio de cultivo sem condicionamento); grupo II: cimento de hidróxido de cálcio; grupo III: adesivo dentinário; grupo IV: ácido ortofosfórico a 37%. O condicionamento foi realizado, colocando-se meio de cultivo fresco sobre os materiais de modo que a presa (grupo II), polimerização (grupo III) ou o contato direto (grupo IV) liberassem substâncias para esse meio de cultivo. Esse meio era colocado sobre as células durante todo o experimento, excetuando-se o grupo IV, onde o contato foi feito por um período de 15 segundos, conforme recomendações clínicas. Posteriormente foram realizadas contagens em hemocitômetro pelo método de exclusão por azul de Trypan, que cora somente as células mortas. As contagens foram realizadas em períodos de 0, 6, 12 e 24 horas para o experimento de viabilidade celular (curto prazo), onde se avaliou o percentual de células vivas sobre o total de células, e em períodos de 1, 3, 5 e 7 dias para o experimento de sobrevivência celular, no qual se avaliou o número absoluto de células vivas. Observou-se que as substâncias liberadas pelo adesivo dentinário são citotóxicas em qualquer período, diminuindo consideravelmente a viabilidade celular e afetando suas curvas de crescimento. Aquelas liberadas pelo ácido ortofosfórico a 37% provocam diminuição da viabilidade somente nos primeiros momentos do contato com as células, enquanto as substâncias liberadas durante a presa do hidróxido de cálcio não são citotóxicas em nenhum momento. / The purpose of the present study was to evaluate the cytotoxic effects of substances leached during the use of direct pulp capping materials, on human pulp fibroblasts. There were used cell culture mediums conditioned by the test materials, as follows: group I: control (fresh medium without conditioning); group II: calcium hydroxide cement; group III: bonding system; group IV: 37% orthophosphoric acid. The medium conditioning was made, pouring the fresh conditioning medium on the materials, in order that its setting (group II), polymerization (group III) or the direct contact (group IV) would be able to leach substances to this culture medium. These conditioned mediums were put on the cells for the entire experiment, excepting the group IV, in which the mediums were put in contact with the cells for 15 seconds, following clinical recommendations. Cell counting was performed in hemocytometer, using the Trypan blue exclusion method, which mark only the dead cells. These counting was made at experimental times of 0, 6, 12 and 24 hours for the cell viability assay (short term), where it is evaluated the percentage of live cells on the total number of cells, and at experimental times of 1, 3, 5 and 7 days for the survival assay, in which is evaluated the absolute number of live cells. It was observed that the substances leached by the bonding system are cytotoxic at all experimental times, decreasing significantly the cell viability and affecting its growing rate. Those leached by the 37% orthophosphoric acid decreased the cell viability only at the first contact with the cells, and the substances leached during the setting of the calcium hydroxide cement are not cytotoxic.

The purpose of this thesis was to analyse the supply of pulp and paper products in the three major producing provinces of Canada, namely British Columbia, Ontario and Quebec. A translog restricted profit function and its first partial derivatives were estimated using the iterative seemingly unrelated regressions procedure. Derived demand equations for energy, fibre, labour and supply equations for net market pulp, newsprint and 'other paper and paperboard", (net market pulp and 'all paper and paperboard' for British Columbia) were obtained with net supplies as a function of each input and output price. The success of the model in representing the industry was mixed. Derived demand own price elasticities were, in almost all cases, negative as expected a priori. Negative own price elasticities were also found in many end product supply functions suggesting a misspecification of the supply relationship. The unexpected supply function results bring up questions about the degree of competitiveness in pulp and paper markets, and thus the validity of using the perfectly competitive market assumption in empirical studies. Finally the model was evaluated in the context of using the results in a spatial equilibrium model of the North American pulp and paper sector. / Forestry, Faculty of / Graduate

In this report, the washing efficiency of chemi-thermomechanical pulp (CTMP) from Norway spruce (Picea abies) was investigated when adjusting the temperature and pH during washing as well as implementing different number of wash steps. Concurrent effects of having a high pH and temperature were also examined. CTMP pulp has many uses, one of which is for the manufacturing of packaging board. Lately, this end product has seen a precipitous increase due to the increasing demand of an environmentally friendly alternative within the food packaging sector. A notorious problem associated with all mechanical pulps is how extractives are to a large extent still present after the pulping process, especially unsaturated lipids which are subject to oxidation. This results in the formation of odorous aldehydes that can be easily transferred into the food product, thus contaminating it by altering the perception of taste and odor. This is a frequent problem faced by the status quo liquid board industry. Washing is thus employed late downstream to lower the final wood resin content. Here, available literature has been collated for some basic introductory subjects such as softwood anatomy, wood resin and structures. All of this is described with a focus on softwood, leading up to a thorough breakdown of P. abies. Mechanical pulping and relevant deresination methods for CTMP production are also described, including washing. The objective of this thesis is to evaluate the trends of the final resin concentration as the chosen parameters are altered during washing. The pulp was provided by Rottneros Mill and their industrial process was simulated by using a Büchner funnel for washing. A Soxhlet extractor was used for determining the final extractive contents. It was found that the implementation of additional wash steps reduced the final resin content (1–4 wash steps). The same was found with increasing temperature (60, 70, 80 and 90 °C). The implementation of a fourth wash step seemed to be more efficient at higher temperatures. No conclusions could be drawn from altering the pH due to scattered data points with high uncertainties (pH 7, 8 and 9). The results are limited in terms of significance and are also subject to bias. / I denna rapport undersöktes tvätteffektiviteten av kemitermomekanisk massa (CTMP, chemi-thermomechanical pulp) tillverkad från gran (Picea abies) och hur den påverkas vid justeringar av temperatur, pH och antal tvättsteg. Ytterligare undersöktes förekomsten av eventuella samverkande effekter vid högre temperatur och pH. CTMP-massa har många användningsområden, däribland vid produktion av vätskekartong. På sistone har efterfrågan av vätskekartong ökat markant som ett svar på en allt större strävan efter ett mer miljövänligt alternativ inom matförpackningssektorn. Ett välkänt problem associerat med mekanisk massatillverkning är den stora mängden exktraktivämnen som kvarhålls i den färdiga massan. En viss del av dessa extraktivämnen utgörs av fleromättade fetter vilket är benägna att genomgå oxidation. Detta leder i sin tur till bildandet av flyktiga aldehyder som kan föras vidare till matprodukten och ge dem förändrad smak och lukt; ett problem som dagens vätskekartongproducenter står inför. Tillgänglig litteratur har sammanställts, där en inledande teoridel beskriver koncept såsom anatomi, strukturer och extraktivämnen hos barrved. Teoridelen övergår därefter till att ge en mer detaljerad beskrivning av P. abies och dess extraktivinnehåll. Ytterligare beskrivs mekanisk massatillverkning över lag och metoder för att eliminera extraktivämnen under produktionen av CTMP-massa (inklusive tvättning). Syftet med detta examensarbete är att utvärdera de trender i den slutliga extraktivhalten då de valda parametrarna justeras under tvättning. Massan tillhandahölls av Rottneros Bruk och deras tvättningsprocess simulerades med hjälp av en Büchner-tratt. En Soxhlet-extraktor användes för att utvärdera den slutliga extraktivhalten. Det visade sig att vid varje insättning av ett ytterligare tvättsteg (1–4 tvättsteg) gav en lägre extraktivhalt hos CTMP-massan. Desamma gällde vid ökande temperatur (60, 70, 80 and 90 °C). Implementering av ett fjärde tvättsteg tycks vara mer effektivt vid högre temperaturer. Det kunde dock inte dras några slutsatser huruvida pH påverkade tvättningen då dessa mätvärden fick stor spridning med höga osäkerheter (pH 7, 8 och 9). Resultaten besitter begränsad signifikans och kan även ha blivit utsatta för bias.

Syftet med detta examensarbete var att öka reaktiviteten hos förhydrolyserad kraftmassa genom att använda tidigare förhydrolysat och svavelsyra under förhydrolysen. Först bestämdes den kemiska sammansättningen av två olika vedråvaror (Acacia crassicarpa och Eucalyptushybrider) för att observera och korrelera med förhydrolysprocessen. Därefter studerades effekten av att för förhydrolyskraftkokning använda vatten, förhydrolysat och svavelsyra med olika koncentration under förhydrolysen vilket korrelerades med avlägsnandet av pentosan, utbyte, viskositet, kappanummer och ljushet. Därefter valdes en av vardera syrabaserad förhydrolyskraftmassa att blekas helt till dissolvingmassa för bestämning av Fock-reaktivitet, vilket jämfördes mot den vattenbaserade förhydrolysen som referens. Den slutliga kvaliteten på de olika förhydrolyskraftmassorna studerades också. Detta examensarbete visade att användandet av förhydrolysat och svavelsyra kan ge högre Fock-reaktivitet jämfört med vatten under liknande processförhållanden. Däremot gav syrabaserad förhydrolyskraftmassa lägre utbyte än vattenbaserad förhydrolyskraftmassa. Syrabaserad förhydrolyskraftkokning gav även lägre pentosanhalt, lägre halt extraktivämnen och lägre viskositetsvärden. Förhydrolysatbaserad förhydrolyskraftmassa hade värden mellan de som uppvisades av vattenbaserade- och svavelsyrabaserade förhydrolyskraftmassor. Dessutom hade förhydrolyskraftmassor från Eucalyptushybrider högre Fock-reaktivitet, lägre pentosanhalt, lägre halt extraktivämnen och högre viskositet än förhydrolyskraftmassor från Acacia crassicarpa. / The worldwide demand for dissolving pulp has been increasing significantly in Asia which is majorly produced from prehydrolysis kraft pulping and most of the prehydrolysis kraft pulp are consumed in viscose rayon production. Thus, it is interesting to have research in the process of prehydrolysis kraft pulping to make it a cleaner and more sustainable production. One of the most important qualities of prehydrolysis kraft pulp in viscose rayon is reactivity, which can lead to less chemical consumption and lower production cost. The aim of this research project is to increase the reactivity of prehydrolysis kraft pulp by using prehydrolysate and sulfuric acid during prehydrolysis cooking. Firstly, the wood chemical composition of two different hardwood species (Acacia crassicarpa and Eucalyptus hybrids) were determined and correlated with the prehydrolysis kraft pulping process. Secondly, prehydrolysis kraft cooking using water, prehydrolysate, and sulfuric acid with different concentration during prehydrolysis were studied and correlated with pentosan removal, yield, viscosity, kappa number, and brightness. Later, one of each acid based prehydrolysis kraft pulping were chosen to be proceed to fully bleached dissolving pulp for determining Fock reactivity which was compared to water prehydrolysis kraft pulping as the reference. The final quality of different prehydrolysis kraft pulps were also studied. From this research project, it showed that prehydrolysate and sulfuric acid prehydrolysis kraft pulp improved the Fock reactivity as compared to water prehydrolysis in similar pulping condition. However, acid based prehydrolysis kraft pulping gave lower yield than water prehydrolysis kraft pulping. Acid based prehydrolysis kraft cooking provided lower pentosan and extractive content, but lower viscosity values. Meanwhile, the prehydrolysate kraft pulp had the intermediate values between water and sulfuric acid prehydrolysis kraft pulping. In addition, Eucalyptus hybrids prehydrolysis kraft pulping had higher Fock reactivity, lower pentosan content, lower extractives, and higher viscosity than Acacia crassicarpa. To conclude, the more acidic prehydrolysis increased Fock reactivity with lower pulp yield, pentosan, extractive and viscosity.

MBL 3 Research Report / This study investigated the economic significance of using bagasse as a source of raw material for pulp and paper manufacturing. The study also compared this issue with the currently undergoing practices of cogeneration, where bagasse is burnt in the sugar mill boilers to produce steam and generate electricity.

Submitted in complete fulfilment for Masters Degree in Technology: Biotechnology, Durban University of Technology, 2013. / A comparative thermostability analysis of different partially purified xylanases from Rhodothermus marinus, Bacillus halodurans, Thermomyces lanuginosus and Pulpzyme HC was studied using differential scanning fluorometry (DSF), fluorescence spectroscopy and circular dichroism (CD). The R. marinus xylanase was found to have an optimum temperature and pH of 90oC and 6 respectively while the B. halodurans xylanase was optimally active at 70oC and a broad range of alkaline pH of 8 - 10. The commercially available xylanase from T. lanuginosus showed optimal activity at 50oC and pH 7 while the Novozyme xylanase Pulpzyme HC showed optimal activity at 60oC and pH 7. Fluorescence spectroscopy monitored the microenvironment and fluorescence emission of Trp residues. In their native folded state, Trp are generally located in the core of the protein but during unfolding they become exposed. The fluorescence changes as the enzyme undergoes denaturation due to conformational changes and exposure of Trp residues. Differential scanning fluorometry (DSF) monitors thermal unfolding of proteins in the presence of a fluorescent dye such as Spyro Orange. A wide range of buffers were tested for their ability to increase the xylanase stability. T. lanuginosus had the greatest increase in melting temperature with 0.73M Bis Tris pH 6.5 and peaked highest at 78°C. The B. halodurans xylanase exhibited high pH stability (pH 4-10) and exhibited very little change in melting temperature, from 74°C-77°C over the twenty four different conditions. The R. marinus xylanase had no increase in melting temperature showing a maximum melting temperature of 90oC. Circular dichroism (CD) measures unequal absorption of right- and left-handed circularly polarized light by the molecule. The xylanase from R. marinus exhibited the lowest ΔG of 34.71kJ at 90°C as was expected. The B. halodurans xylanase showed a much higher ΔG of -52.71 at its optimum temperature of 70°C when compared with the xylanases from R. marinus and T. lanuginosus. When comparing the three xylanases activities at 70°C, it can be seen that the B. halodurans xylanase exhibited a lower relative activity then both R. marinus and T. lanuginosus xylanases. All three techniques offered different information on the structure and function relationship. Fluorescence spectroscopy, the change in conformation due to fluorescence emission as a result of increased temperature and salt concentrations. DSF, optimal conditions for increased stability and activity at higher temperatures and CD, conformational changes, the fraction of folded protein and change in Gibbs free energy over a range of temperature. / National Research Foundation

Mondi Dynäs is a pulp and paper producer in the north of Sweden close to the town Kramfors. Last year Mondi Dynäs produced 231,404 tons of Kraft paper. In order to increase their production to 300,000 tons of paper per year this study was done in order to investigate how the increased biomass flow would affect the generation of steam along with the steam and condensate balance. This study started with a mapping of the current steam and condensate balance for one winter period January – Mars and one summer period July – September 2015. The resulting balance is used as reference period for the development of the future steam and condensate scenario where Mondi Dynäs will achieve the targeted production of 300,000 tons of paper per year. The future model shows that the future production of paper will give an abundance of biomass since the generation of steam will be more than sufficient. For the winter period the venting of steam over roof could be derived to 11.9 tons per hour and 34.4 tons per hour during the summer period. This can be compared to the current situation where the winter period gave an average steam blow out of 8.7 tons per hour and for the summer period 13.1 tons per hour. To utilize the accumulated energy from these energy streams, three different scenarios was studied. The first scenario were a future installation of a backpressure turbine along with a condensing turbine section. The new turbine would be attached to the highest pressure level at 65.5 bar and have a backpressure exhaust at 20 bar which will give a power of 7.6 MWe. The second scenario included the implementation of a new condensing turbine with the current system design for the steam network and boilers. This turbine would be attached to the 3.5 bar network and give the electricity power of 1.9 MWe. The third scenario included the installation of a new bark dryer. This would give Mondi Dynäs the possibility to sell bark to an external actor on the energy market. From derived figures in the future scenario model it would be possible to sell 108,144 MWh of bark while running the bark boiler. Mondi Dynäs AB is recommended to add a new condensing turbine to their steam network. The new turbine would be able to produce 1.9 MWe and need a cooling water flow of 190 tons of water per hour. Derived figures for the investment shows a NPV of 0.6 MEUR and the IRR value of 31 %