The degradation of cellulose found in wood is one of the most important degradation processes for the carbon flux on earth. The degradation is performed by microorganisms that typically use enzymes. Since the cellulose in wood is crystalline and embedded in other polymers, making it inaccessible and durable, the enzymatic methods of cellulose degradation is also complex. In this thesis, the action of some of these enzymes, called cellulases, have been studied both fundamentally and for industrial purposes. By using model cellulose films and a quartz crystal microbalance it was found that endoglucanases not only depolymerize but also swell model cellulose films. Most probably, this contributes to the synergy seen between endoglucanases and exoglucanases. When an pulp fibers were pre--treated with endoglucanases and beaten subsequently, the fibers became more swollen than reference fibers. The effects of beating enzyme pre--treated fibers were investigated, indicating that endoglucanases improves the fiber/fiber interaction but also alters the behavior of the fibers in the beating process to become more susceptible to the beating. The second part of the thesis has been focused on the use of an albino fungi in order to decrease the amount of wood extractives in wood chips prior to thermo mechanical pulp production. The fungus decreased the most troublesome component, the triglycerides, by more than 90 percent in two weeks without any detrimental effects on pulp properties. On the contrary, pulp strength and optical properties were improved. / QC 20101117

This thesis reports on an investigation of the mechanisms of edge wicking in retortable paperboard. Retortable board is used for packaging preserved food, a process which requires that the package and its contents be sterilised by exposure to high temperature steam for up to three hours. The board used must thus have higher water repellence than traditional liquid packaging. Water vapour that condenses on the cut edges on the outside of the board causes particular concern. The paperboards studied were made from refined and unrefined bleached softwood kraft pulp and from refined unbleached softwood kraft pulp in one or two plies with different sizing levels and structures. Samples of each of the boards were immersed in a water bath at 95 °C. Other samples from the same boards were exposed to a combination of saturated steam at 130 °C and condensed steam in a special apparatus developed for this purpose. The board samples were placed on a cooling plate to simulate the temperature gradient when a container of cold food is sterilised with heated steam. Still other samples were exposed to heated steam in the absence of condensation by hanging them freely in the apparatus. The extent of edge wicking in the boards was determined by gravimetric measurements and also by near-infrared (NIR) spectroscopy, a technique that yields more information about the moisture content profiles and the mechanisms of liquid sorption. The moisture content profiles of boards exposed to saturated steam in the absence of condensation show more uniform water uptake. This phenomenon can be explained by rapid vapour phase transport throughout the pore structure, followed by slower water uptake in the fibres. By contrast, in samples exposed to both heated steam and condensed steam, there was both liquid sorption in the fibre network and rapid vapour phase transport of the steam. The moisture content in those samples was much higher close to the edge and lower behind the liquid frontier. The edge wicking of high temperature water was greatest in board that was not fully sized, in low density board, and in board made from unrefined pulp. The greater edge wicking in board made from unbleached pulp can be accounted for in terms of its greater swelling potential. In the low density board and the board made from unrefined pulp, the lumens at the unsized edge and the weaker bonding strength are suggested to affect the results. Capillary sorption takes place in lumens and delaminated bonds at the edge and then any further propagation takes place entirely by fibre diffusion. Capillary sorption may also be important in damaged areas where broken fibre-fibre bonds are exposed to liquid. The weaker bonded area in low density board therefore also contributes to water sorption. Edge wicking in the boards placed on the cooling plate and exposed to a combination of saturated and condensed steam was of a different nature. For these samples, density was not an important factor. The difference is due to the different mechanism at work in this case, where the relative area of the edge exposed to condensed steam was larger in the high density boards than in the low density boards. In the high density boards, condensed steam was sorbed in the structure by diffusion in the fibre structure, whereas in low density boards, the dominant effect was vapour phase transport in the void spaces followed by water uptake in the fibres. / QC 20101125

The presteaming of wood chips is an important step in the chemical pulping industry. It removes the air from within wood chips, allowing the cooking liquor to better impregnate wood chips, which leads to a more uniform cooking process, and lowers the amount of rejects. When steaming at atmospheric pressure, it is important that the temperature of the wood chips reach 100ᴼ C, as otherwise there will be an equilibrium leaving some air left inside. Having poorly steamed chips in a process could cause severe problems when it comes to reaching the targeted kappa number, or having the adequate retention time in the digester. There are a few different ways in which the wood chips are presteamed within the industry, however, there is little experimental data regarding the heating time of wood chips that can be used when designing these systems. Most studies have mainly focused on the air removal, or improvement of the impregnation step, and the few studies that have included the heating of the wood chips were limited to only one type of wood chip, or failed to specify the experimental details. Therefore, handmade wood chips pine and birch, two tree species commonly found in Sweden, were steamed in an ATEX designed digester with a steam jacket. The wood chips had thermocouples inside them and the temperature and time was recorded, and the effect of different parameters on the heating could thus be studied.The results revealed that there could be more than a minute in average time difference between wood chips of different thicknesses, both for birch and pine, although the difference in heating time was more linearly correlated to thickness for the birch chips. Pine chips of different thickness were also studied when the pressure inside the digester was allowed to build up, which showed that it is mainly thicker chips that have reduced heating time under such circumstances, as the thinner chips stop heating for a while when the steam condensates on colder surroundings. When comparing heartwood and sapwood chips, it was noted that the difference in heating time could be around 1 minute at most for pine, but only a few seconds for birch. This was most likely due to the pine heartwood and sapwood having distinct moisture contents, 25 % and 58 % respectively, while it was 41% and 42 % in birch heartwood and sapwood. Birch and pine chips wee also steamed together, however, the difference in heating time was only a few seconds on average. When comparing these experimental results with simulation data of the steaming of wood chips, it fit rather well when it came to the general heating time. However, the effect of increased moisture content had a much larger impact in the simulations, which predicted that more moist wood chips would need several minutes more steaming time, while the experiments only showed at difference of, at most, around 1 minute. When comparing with old experimental data, that has been the basis for the design of older steaming processes, it gave very distinct results, where the effect of thickness did not have as big of an impact as in the old data. No further comparison could be made, however, as the experimental conditions for the old experimental data were not known. Based on these results, it was noted that a steaming time of at least 5 minutes would be needed to ensure that even the largest and more moist chips could reach 100ᴼ C in this system. Finally, the condensate from the handmade birch and pine chips was analyzed. It revealed the presence of low molecular weight compounds like methanol, formic acid and acetic acid. Common metal ions were also present,although the amount of sodium ions clearly surpassed the rest. The pH of the pine condensate was measured and it was very high, which implies that the condensate was contaminated. / Basning av flis är ett viktigt steg inom kemisk massaindustri. Det avlägsnar luft från flisens insida vilket gör att impregneringen av luten blir bättre, vilket i sin tur leder till en jämnare kokning och färre rejekt. När basningen sker vid atmosfärstryck är det viktigt att flisen når en temperatur på 100ᴼ C, annars kommer det finna ett jämviktstillstånd där lite luft blir kvar på insidan. Att ha otillräckligt basad flis i en process skulle kunna orsaka stora problem när det gäller att nå önskade kappatal, eller att ha en önskad retentionstid i kokaren.Basningen görs på ett par olika sätt inom industrin, men det finns väldigt lite experimentell data tillgänglig angående flisens upvärmning, som skulle kunna användas när dessa system designas. De flesta vetenskapliga studier har fokuserat på luftborttagningen eller på förbättringar av impregneringssteget, medan de få studier som inkluderat mätningar av temperaturen ofta varit begränsade till ett slags trä, eller så har de inte inkluderat detaljer kring experimentet. Därför basades handgjorda flisbitar av björk och tall från Sverige i en ATEX-designad kokare med en ångjacka. Flisen hade termoelement inuti och temperaturen samt tiden kunde avläsas, vilket gjorde det möjligt att studera effekten av olika parametrar. Resultaten visade att det kunde skilja mer än en minut i uppvärmningstid mellan flisbitar av olika tjocklekar, både för tall och björk, även fast skillnaden i uppvärmningstid var mer linjärt relaterad till tjockleken för björkflisen. Tallflisen studerades också när trycket inuti kokar tilläts stiga vilket visade att det de tjockare flisbitarnas uppvärmningstid som kortas ned mest, eftersom de tunnare flisbitarna slutar värmas upp när ångan börjar kondensera på kallare ytor runt omkring. När flis av splintved och kärnved jämfördes visade det sig att skillnaden i uppvärmningstid kunde vara omkring 1 minut för tall, men endast ett par sekunder för björk. Detta beror troligtvis på att kärnveden och splintveden i tall hade stora skillnader i fukthalt, 25 % respektive 58 %, medan det för björk var 41 % och 42%. Björkflis och tallflis basades även tillsammans men det skillde bara ett fåtal sekunder i genomsnitt i uppvärmningstid. När den experimentella datan jämfördes med data från simuleringar visade det sig att de stämmer väl överens när det gäller uppvärmningstiden i allmänhet. Å andra sidan förutspådde simuleringsdatan att en ökad fukthalt skulle leda till flera minuters skillnad i uppvärmningstid, medan endast 1 minuts skillnad uppmättes. När jämförelser gjordes med gammal experimentell data som använts som grund för tidigare processers design, var resultaten ganska olika eftersom den gamla datan visade en större effekt av ökad tjocklek än den som uppmättes.Tyvärr kunde inte fler jämförelser göras eftersom detaljerna kring experimentet bakom den gamla datan inte var kända. Slutligen analyserades även kondensatet från de handgjorda flisbitarna av tall och björk. Det visade att det fanns små mängder av små polära organiska ämnen, såsom metanol, myrsyra och ättiksyra. Vanliga metalljoner detekterades också, där mängden natrium var klart större än övriga metalljoner. Tallkondensatets pH mättes och det visade sig vara väldigt högt, något som tyder på att det troligtvis var förorenat.

In-plane properties of paperboard have always been of interest to paper mechanical researchers. The reason for this is that they play a large role for the usability of the paperboard throughout its lifespan.  Tensile properties are crucial when the board is fed through printing and converting machines at high speeds in the beginning of its life. While compressive properties are essential in the later use of e.g. packages. In this thesis some methods for evaluating in-plane properties are reinvestigated. In Paper A the tensile test was investigated with focus on sample size and strain distributions. Three different multiply paperboards were examined with varying sample sizes using speckle photography. Different strain behaviour was found for different sample sizes. This difference was dependent on the length to width ratio of the sample and was caused by the activation of strain zones in the sample. These zones were of a constant size and therefore occupied different amounts of the total sample area. Paper B investigates the mechanism that causes failure in the short span compression test (SCT). Three different multiply paperboards were examined, this time chosen to have distinctly different through-thickness profiles. The boards were characterized and the data was used to simulate a SCT test with the three different boards. The simulation was conducted with a finite element model consisting of layers of continuum elements with cohesive interfaces in-between. From the model it was concluded that the main mechanism for failure in SCT is delamination that was caused by shear damage. / <p>QC 20130603</p>

In this work, the formation of polyelectrolyte complexes (PECs) has been studied using a jet mixing method not previously used for mixing polyelectrolytes. The PECs were formed from two weak polyelectrolytes, i.e., polyacrylic acid (PAA) and polyallylamine hydrochloride (PAH), with different mixing times, and the results were compared with those for PECs formed using the conventional polyelectrolyte titration method.   The adsorption behaviour of the formed PECs on silicon oxide substrates and pulp fibres was analysed, and the results were compared with those for polyelectrolyte multilayers (PEMs) prepared from the same two polyelectrolytes.   The results indicated that by using the jet mixer, the size of the formed PECs could be controlled, which was not the case with the polyelectrolyte titration method. The PECs produced by jet mixing were also found to be smaller than those produced by polyelectrolyte titration. From these results, a two-step mechanism for the formation of PECs was suggested: initial precomplex formation, which is a fast and diffusion-controlled process, followed by a reconformation process, during which the vigorous mixing in the jet mixer can partially limit secondary aggregation.   When the complexes were adsorbed to silicon oxide or pulp fibre surfaces, adsorption studies indicated that it was impossible to reach the same adsorption levels for PECs as for PEMs. This was explained in terms of free energy, entropical, reasons rather than to any geometric limitation of the surface. Despite the smaller amount of polyelectrolyte adsorbed from the PEC treatment than from the PEM treatment of pulp fibres, the PEC treatment had the greatest effect on paper strength per adsorbed amount of polymer. This was thought to be because the three-dimensional structure of the PECs, versus the smoother structure of PEMs, allows for the formation of multiple contact points between the macroscopically rough fibres and increased molecular contact area.   In the adsorption experiments, it was also found that net cationic complexes can adsorb to both anionic and cationic substrates. This phenomenon was explained by the occurrence of anionic patches on the surface of the net cationic PECs and the ability of the PECs, formed from weak polyelectrolytes, to partially change charge upon exposure to a surface of the same charge as the complex itself, due to a change of the degree of dissociation of the polyelectrolytes constituting the complex. / QC 20101102

The interdependency between filler retention and paper formation is well-known, where a high retention is accompanied by impaired formation. A challenge for today’s papermakers is to increase the competitiveness for uncoated and coated fine paper, by improving the formation at the same level of retention. Over the years, the use and the demands of retention aids have increased as a consequence of a higher system closure, increased machine speeds and increased filler content. The knowledge of whether some retention aid systems are more or less detrimental to paper formation than other systems, is very limited. The insuffiency of knowledge is, however, also true for other chemical, mechanical and interacting factors, which influence the retention/formation relationship in a complex manner. In order to investigate the retention/formation relationship (features, retention aids, dosage points, etc.), a pilot-scale fourdrinier former (R/F-machine) has been developed. The R/F-machine provides a short circulation of the white water and controlled experimental conditions and is appropriate for cost-effective investigations. Moreover, the R/F-machine has been designed to have a short residence time to chemical equilibrium and the machine has also shown high reproducibility in the results. This licentiate thesis presents the R/F-machine and examines, during constant experimental conditions, the retention/formation relationships for some different retention aid systems. Three single-component cationic polyacrylamides with varying molecular weights and two polyacrylamide-based microparticulate systems with varying microparticles were examined. The retention aid systems were investigated on the R/F-machine, for a fine paper stock (90 % bleached hardwood and 10 % bleached softwood) with addition of 25 % filler (based on total solids content). The results showed that the retention/formation relationship was not dependent on the retention aid system used. All systems showed the same relationship between retention and formation. On the other hand, the various retention aid systems provided different effects considering their retention performance. / QC 20101118

Papper uppvisar betydande tidsberoende mekaniska egenskaper som krypning och spänningsrelaxation. Det är känt att krypningen hos pappret påverkar till exempel en wellpapplådas förmåga att bära last under lång tid. En möjlighet att tillverka papper som kryper långsammare är därför önskvärd. Polyelektrolyter används ofta för att öka styrkan hos papper, och skulle kanske också kunna användas till att minska papprets krypning. Inverkan av polymera additiv på pappers krypegenskaper är emellertid knapphändigt beskrivet i litteraturen. Existerande studier har visat att polymera additiv inte påverkar krypningen hos starka papper och att fiberväggarna och fiber/fiber fogarna har fundamentalt olika betydelse för krypegenskaperna. Avsikten med denna avhandling var att undersöka hur adsorberade polyelektrolyter påverkar krypegenskaperna hos pappret. Ett av huvudsyftena var att studera om adsorptionen av en katjonisk polyelektrolyt – polyallylamin – endast till fiberytan eller tvärs hela fiberväggen ger olika effekt på krypningen hos papper tillverkade av dessa fibrer. En ny teknik där polyelektrolyten märks med en fluorescerande markör gör det möjligt att visualisera var i fibern de adsorberade molekylerna befinner sig. Resultaten visar att adsorption vid låg jonstyrka under kort tid bara ger adsorption till de yttre delarna av fiberväggen. Hög jonstyrka och lång adsorptions tid resulterar å andra sidan i adsorption tvärs hela fiberväggen. Med hjälp av denna teknik blev det också möjligt att klarlägga vilken inverkan polyelektrolytens läge i fiberväggen har på de slutgiltiga arkens mekaniska egenskaper. Krypprovning av de tillverkade arken visade tydligt att polyallylamin som endast adsorberat till fibrernas yttre delar minskade krypningen vid både 50 % och 90 % relativ luftfuktighet. Den uppnådda effekten visade sig dock bero på vilken typ av fibrer arken tillverkades av. Adsorption av katjoniserad stärkelse till fibrernas yta gav ingen nämnvärd effekt på arkens krypegenskaper, detta trots att stärkelse gav lika hög arkstyrka som polyallylamin. När polyallylamin adsorberades tvärs igenom fibrerväggen ökade krypningen vid 90 % relativ luftfuktighet väsentligt. Detta föreslås bero på att den adsorberade polyelektrolyten avsväller fibrerna vilket ger färre fiber/fiber kontakter och därmed en sämre fördelning av mekanisk last i arken. Det var emellertid inte möjligt att dra några definitiva slutsatser angående mekanismerna bakom de observerade skillnaderna i krypegenskaper. / Paper materials exhibit a significant time-dependent mechanical behaviour, such as creep and stress-relaxation. It is known that the creep of the paper affects the performance of corrugated boxes. The production of a paper having a lower creep rate is therefore desirable. Polyelectrolytes commonly used to increase the strength of paper could be an alternative for improving the creep properties. The influence of polymeric additives on the creep properties of paper is, however, poorly described in the literature. Published studies have shown that polymeric additives do not affect the creep behaviour of fully efficiently loaded paper sheets and that the fibre cell walls and the fibre/fibre joints have fundamentally different effects on the creep behaviour. The aim of the present thesis was to examine the influence of adsorbed polyelectrolytes on the creep behaviour of paper sheets made from the modified fibres. One of the main objectives was to establish whether there is a difference in effect on creep properties between adsorbing a cationic polyelectrolyte – polyallylamine – to the fibre surfaces or throughout the fibre cell walls. A technique which includes the labelling of polyelectrolytes with a fluorescent dye and microscopy of single fibres provided a visual record of the localisation of the adsorbed polyelectrolyte. This method showed that a low ionic strength and a short adsorption time resulted in adsorption of the polyelectrolyte only to the external parts of the fibres. A high ionic strength and a long adsorption time on the other hand, resulted in adsorption throughout the fibre walls. This made it possible to study the relationship between the mechanical properties of the sheets and the localisation of the adsorbed polyelectrolyte. Creep testing of the sheets showed that the adsorption of polyallylamine to the exterior parts of fibres decreased the creep at both 50% and 90% RH. The effect depended, however, on the type of fibre used. Adsorption of cationic starch to the fibres gave no significant reduction in creep rate, despite the fact that starch and polyallylamine had similar effect on the paper strength. When polyallylamine was adsorbed into the fibre cell walls, the creep at 90% RH increased. It is suggested that this was due to a deswelling of the fibres by the adsorbed polyelectrolyte, which resulted in fewer fibre/fibre contact points and hence a less efficient distribution of stresses in the sheet. It was not, however, possible to draw any definitive conclusions about the mechanisms behind the observed differences in creep behaviour. / QC 20101105

Papper är ett mycket mångsidigt material. Trots detta finns det ett flertal egenskaper som begränsar papperets användbarhet. Ett av de större problemen med cellulosa- och lignocellulosafibrer är att de sänker sin fria energi genom att sorbera vatten, och denna sorption förändrar papperets dimensioner. Detta fenomen kallas vanligtvis för bristfällig dimensionsstabilitet och uppträder i form av registerfel vid flerfärgstryck eller som krullning, buckling och vågiga papperskanter vid utskrift, kopiering och lagring, eller med en vidare definition som förkortad livslängd hos lådor på grund av mekanosorptivt kryp. Avsikten med denna avhandling har varit att studera och kvantifiera vilka egenskaper som styr, och hur de påverkar, den vatteninducerade dimensionsförändringen som sker hos ett fibernätverk, samt hur dess dimensionsstabilitet kan förbättras. Detta har studerats både genom att ändra fiberns fuktsorptionsegenskaper och genom att förändra adhesionen och kontaktgraden mellan fibrerna i fiber-fiberfogarna. Fogegenskaperna har också varierats genom att tillverka laboratorieark torkade under inspänning samt ark torkade fritt för att minimera mängden inbyggda spänningar i arket. Blekt kraftmassa har behandlats med polyelektrolytmultilager (PEM) för att förbättra adhesionen mellan fibrerna och för att öka kontaktgraden mellan fibrerna i fogen. Kontaktgraden har även minskats genom förhorning av fibrerna före arkformning. För de ark som fick torka fritt gav PEM-behandlingen en ökad hygroexpansionskoefficient, det vill säga dimensionsförändringen normaliserad mot förändringen i fuktinnehåll, vid samma förändring i relativ luftfuktighet medan förhorningen minskade hygroexpansionskoefficienten något. Om arken emellertid torkades under inspänning observerades ingen skillnad i hygroexpansionskoefficient mellan de olika fibermodifieringarna. Detta tolkades som ett resultat av en ökad kontaktzon och en större utbredning ut ur fogens plan, när arken torkades utan inspänning. En utbredning som medför att en större del av fiberns transversella expansion överförs som expansion i pappersplanet. Fibrernas fuktsorptionsegenskaper förändrades genom natriumperjodatoxidering av 1,4-glukanernas C2-C3-bindning. Detta skapade sannolikt tvärbindningar i fiberväggen som förbättrade fiberväggens tålighet både genom att låsa fibrillerna närmare varandra och genom att ta bort potentiella adsorptionssäten som annars är tillgängliga för vattenadsorption. Perjodatoxidationen minskar också fibrernas kristallinitet och således frigjorde oxidationen hydroxylgrupper där vattenmolekyler kan adsorbera. Detta innebar att oxidationen både minskade och ökade interaktionen mellan vatten och fibervägg, men dock på olika strukturell nivå. Tvärbindningarna visade sig också märkbart reducera sorptionshastigheten när arken utsattes för en förändrad luftfuktighet så länge de inte tidigare utsatts för relativa luftfuktigheter nära mättnad. Som ett resultat av den lägre förändringen i fuktinnehåll vid en förändring i luftfuktighet från 20 till 85 % RF minskade dimensionsförändringens amplitud för de tvärbundna arken upp till 30 %. Emellertid uppvisade de tvärbundna arken en högre hygroexpansionskoefficeint, vilket innebär att de blev mer känsliga för absoluta förändringar i fuktinnehåll. / Paper is a very versatile material. Nevertheless, there are several factors limiting its usefulness, and one of the major issues is that cellulosic and ligno-cellulosic fibres lower their free energy by sorbing water and this water changes the dimensions of the paper. This phenomenon is usually referred to as a lack of dimensional stability and is often evident as misregister during multicolour printing or curl, cockle and wavy edges during printing, copying and storage or, with a wider definition, also as a shortened life-time of boxes during storage due to mechano-sorptive creep. The work described in this thesis aims to study and quantify the importance of the different mechanisms causing water-induced dimensional changes in a fibre network and to investigate how to improve the dimensional stability of ligno-cellulosic materials. This has been done both by altering the fiber properties such as the moisture sorptivity and by changing the adhesion and degree of contact within the fibre-fibre joints. The properties of the fibre-fibre joints have been varied by drying laboratory sheets both under restraint and freely to minimise the generation of built-in stresses. Bleached kraft fibres were treated using the polyelectrolyte multilayer (PEM) technique to improve the adhesion between the fibres and to increase the molecular contact within the joints. In contrast, the degree of contact was impaired by hornifying the fibres before sheet preparation. For sheets allowed to dry freely, the PEM-treatment increased the hygroexpansion coefficient, i.e. the dimensional movement normalised with respect to the change in moisture content, when subjected to changes in relative humidity whereas the hornification process resulted in a slightly lowered hygroexpansion coefficient. However, when the sheets were dried under restraint, the different joint and fibre modifications led to no difference in hygroexpansion coefficient. This was interpreted as being a result of an increase in the total contact zone between the fibres when the sheets were dried under restraint, with a greater extension in the outof- plain direction of the joint resulting in a transfer of a larger part of the transverse swelling to the in-plane expansion. The sorptivity of the fibres was changed by oxidising the C2-C3 bond of the 1,4- glucans with periodate. This most likely created covalent cross-links in the fibre wall both improved the integrity of the fibre wall by locking adjacent fibril lamellae to each other and also removed possible sites for water sorption onto the cellulose surfaces. Periodate oxidation also led to a decrease in the crystallinity of the cellulose within the fibres, making more cellulose hydroxyl groups available for the adsorption of water molecules. This means that the oxidation both decreased and increased the interaction between the fibre wall and moisture but, on two different structural levels. The crosslinks significantly reduced the sorption rate when the papers was subjected to changes in relative humidity, as long as the fibres were not subjected to humidities close to saturation. The smaller change in moisture content when the relative humidity was changed between 20 and 85 % RH meant that the dimensional stability of the crosslinked sheets was increased. On the other hand, the hygroexpansion coefficient was increased in the case of papers made from fibres with the highest degree of oxidation, i.e. the sheets became more sensitive to absolute changes in moisture content. / QC 20101117

No description available.

This thesis explores how to use the dry nanoporous structure of cellulosic fibres in new types of composite materials. A large effort was also given on how to correctly characterize the structure of fibres where the wet structure has been preserved also in the dry state. Delignified wood fibres have an open fibrillar structure in their water-swollen state. In the present work, this open fibrillar structure was preserved in the dry state by performing a liquid exchange procedure and the samples were thereafter carefully dried with Ar(g). The samples of never-dried TEMPO-oxidized dissolving pulp had a specific surface area of 130 m2/g in the dry state, as measured using the Brunauer, Emmet, and Teller (BET) Nitrogen gas adsorption method. This open structure was also revealed using field emission scanning electron microscopy (FE-SEM). The water-swollen and dry open structures were thoroughly characterized for various pulps. A new method for determining the pore size of water-swollen delignified cellulosic fibres is presented. By combining the results from solid state nuclear magnetic resonance NMR, measuring the specific surface area [m2/g] in the water-swollen state, with fibre saturation point (FSP), measuring the pore volume of fibres in water-swollen state [mass water/mass fibre], the average pore size can be determined without the need of assuming a certain pore geometry. The dry nanoporous structure was then used as a scaffold for in-situ polymerization, to demonstrate how the properties of the fibrils in the fibre wall can be exploited without the need to disintegrate the fibre wall. Both poly(methylmethacrylate) (PMMA) and poly(butylacrylate) (PBA) were successfully used as the polymeric matrix, and both nanocomposites (i.e., fibre/PMMA and fibre/PBA) had a fibre content of approximately 20 w%. The structure of the composites was characterized using SEM and Atomic Force Microscopy (AFM) operated in the phase imaging mode. The AFM results indicate that the cellulose aggregates and polymeric matrix were successfully mixed on a nanoscale, creating a nanocomposite of interpenetrating polymer molecules and cellulose fibrils, rather than a microcomposite, when using microscopic cellulose fibres. The water absorption capacity of the nanocomposites was reduced significantly, indicating that almost all nanopores in the fibre wall were successfully filled with matrix polymer. The mechanical properties were investigated, showing the importance of nanosized reinforcement compared to fibres of micrometer size. / <p>QC 20121011</p>