<p>In the wish to replace oil-based chemicals and materials with such based on biodegradable and renewable resources, this work has been performed. In a biorefinary concept, waste birch bark from paper pulp mills and timber production has been evaluated as a potential source for polyesters. </p><p>In the present thesis investigations are made on synthesis of epoxy-functionalized polyesters from the birch outer bark aliphatic suberin ω-hydroxy fatty acid, <em>cis</em>-9,10-epoxy-18-hydroxyoctadecanoic acid. Studies of accessibility and reactivity of cellulose have been performed as a first step to enable covalent attachment or grafting of the epoxy-functionalized polyesters to cellulose.<em> </em></p><p><em>Candida antarctica</em> lipase B (Novozym 435) is reported to be an efficient catalyst for condensation polymerization of <em>cis</em>-9,10-epoxy-18-hydroxyoctadecanoic acid to form poly(9,10-epoxy-18-hydroxyoctadecanoic acid) with high molecular weight (M_w). Performed in toluene in the presence of molecular sieves a M_w of 20000 (reaction time 68 h, M_w/M_n 2.2) was obtained. Performed in bulk without any drying agent a M_w of 15000  was obtained at a much shorter reaction time (reaction time 3h, M_w/M_n 2.2). Further the same lipase has been used for succesful co-polymerizations of <em>cis</em>-9,10-epoxy-18-hydroxyoctadecanoic acid with lactones. By combining condensation and ring-opening polymerization, epoxy-functionalized linear polyesters and cyclic oligomers have been synthesized. For example, co-polymerization of <em>cis</em>-9,10-epoxy-18-hydroxy-octadecanoic acid and ε-caprolactone performed in toluene in the presence of molecular sieves gave mainly cyclic oligomers, especially at shorter reaction times. Co-polymerization performed in bulk gave linear polyesters with a M_wof35000 (reaction time 24 h, M_w/M_n6), irrespective molecular sieves were added or not. </p><p>The epoxy-functionalized polyesters could be used for surface modification of pulp fibres and cellulose fibrils, which further can be used for production of new valuable composite materials with improved features. Knowledge of how different processing conditions affect the structure of cellulose is an important tool in the work to achieve successful grafting of produced polyesters to cellulose fibres/fibrils. CP/MAS ¹³C-NMR spectroscopy has been used to study structural changes caused by the dissolving pulp process. An irreversible increase in average fibril aggregate width from raw pulp to final pulp during the process is shown. This increase in aggregate width could negatively influence the reactivity of the cellulose.</p><p> </p><p> </p>

<p>Graphic paper is experiencing severe competition from other materials and, most of all, from other media. This means there is a great need to improve paper quality while reducing raw material and production costs. Polyelectrolyte multilayer (PEM) treatment (i.e., consecutively adding cationic and anionic polyelectrolytes to the charged surface of wood fibres and fines, to form layers of these polyelectrolytes on the fibres/fines) has in recent years been found to offer great potential both to introduce new properties and to improve the mechanical properties of papers made of the treated fibres.</p><p>The main objective of this thesis was to develop a strategy for the PEM treatment of cationic and anionic starch to improve the mechanical properties of paper made of thermomechanical pulp (TMP), since PEM treatment of fibres has displayed great potential to improve the mechanical properties of sheets made of chemical pulp. Mechanical pulp, however, has a large fine material content. Since the fine material is highly charged, polyelectrolyte consumption would be unacceptably high if the entire pulp were PEM treated, so we applied PEM treatment only to a fibre fraction of the pulps in most trials in the present work. The polyelectrolytes used for PEMs have so far mostly been well-defined, expensive ones unsuitable for use in standard paper grades; to develop a more economically realistic alternative, we used cationic and anionic starches.</p><p>PEM formation on SiO₂ surfaces from three differently charged cationic and anionic starches was first evaluated at three different salt levels using quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The starch combinations displaying the highest potential for stable PEM formation at higher salt concentrations were then evaluated on an entire TMP pulp, as well as on a fraction of the pulp to reduce the amount of starch needed for PEM formation.</p><p>The results indicate that it is possible to form PEMs from cationic and anionic starch on a SiO₂ surface. The charge density, salt concentration, and combination of starches all influenced PEM formation. PEM formation on mechanical fibres produced large improvements in the mechanical properties of the sheets made of the treated fibres, and the tensile index, stretch-at-break, Z-strength, and Scott bond values all increased. Fractionating the pulp and PEM treating only a fraction of the pulp, the long fibre and middle fraction, produced large decreases in the amount of starch needed and large improvements in the mechanical properties of the sheets when no fine material was subsequently added. As untreated fine material was subsequently added, the improvement in mechanical properties decreased. PEM formation produced almost no reduction in formation and only a slight increase in sheet density.</p> / <p>Grafiskt papper är under hård konkurrens från andra material och, framför allt, andra media.  På grund av detta finns det ett stort behov av att förbättra papperskvalitén samtidigt som råmaterial- och produktionskostnader sänks. Polyelektrolyt-multiskikt (multiskikt) på massa (dvs. växelvis adsorption av katjoniska och anjoniska polyelektrolyter till träfibrer och finmaterial) har på senare år visat sig ha bra potential både för att ge nya egenskaper och för att förbättra de mekaniska egenskaperna hos papper gjorda av behandlad fiber.</p><p>Huvudsyftet med denna avhandling var att utveckla en strategi för multiskiktsbehandling med katjonisk och anjonisk stärkelse för att förbättra de mekaniska egenskaperna hos papper gjort av behandlad termomekanisk massa (TMP). Multiskiktsbehandling av fiber har visat stor potential för att ge förbättrade mekaniska egenskaper till ark gjorda av behandlad kemisk massa. Mekanisk massa innehåller dock en stor andel högladdat finmaterial som kan öka mängden polyelektrolyt som krävs för multiskiktsbehandling, därför multiskiktsbehandlas bara en fraktion av massan i de flesta experiment i detta arbete. De polyelektrolyter som använts för multiskikt har hittills mest varit väldefinierade och dyra, och därmed opassande för användning i vanliga papperskvalitéer. För att utveckla ett mer realistiskt alternativ så användes katjonisk och anjonisk stärkelse i detta arbete.</p><p>Multiskiktsuppbyggnad på SiO₂-ytor av tre katjoniska och tre anjoniska stärkelser med olika laddningsdensitet utvärderades först vid tre olika saltnivåer genom att använda kvartskristal‑mikrogravimetri (QCM-D) och reflektometri (SPAR). Stärkelsekombinationerna som uppvisade störst potential för en stabil multiskiktsuppbyggnad på högre saltkoncentrationer blev sedan utvärderade på en hel TMP-massa, men även på en fraktion av massan för att minska mängden stärkelse som krävdes för multiskiktsuppbyggnad.</p><p>Resultaten visar på att det är möjligt att bygga upp multiskikt av katjonisk och anjonisk stärkelse på en SiO₂-yta. Laddningsdensiteten, saltkoncentrationen och kombinationen av stärkelser var faktorer som påverkade multiskiktsuppbyggnaden. Multiskiktsuppbyggnad på mekaniska fibrer gav stora förbättringar av de mekaniska egenskaperna hos ark gjorda av behandlad fiber, och dragindex, töjning, Z-styrka och Scott bond-värde ökade. Fraktionering av massan och multiskiktsbehandling av endast en del av massan, långfiber- och mellanfraktion, innebar att mycket mindre stärkelse behövdes och gav stora förbättringar av de mekaniska egenskaperna hos arken om inget obehandlat finmaterial tillsattes efteråt. Då obehandlat finmaterial tillsattes så blev förbättringarna hos de mekaniska egenskaperna mindre. Multiskitsuppbyggnad gav nästan ingen reduktion av formationen och endast en liten ökning i arkdensitet.</p>

Studies on strength delivery and related fields have so far concentrated on finding the locations in the mill where fibres are damaged and what the damages consist of. However, fibres will invariably encounter mechanical stresses along the fibreline and in this thesis a new concept is introduced; the vulnerability of fibres to mechanical treatment. It is hypothesised that fibres with different properties have different abilities to withstand the mechanical forces they endure as they are discharged from the digester and transported through valves, pumps and various washing and bleaching equipment. In the thesis, results are presented from trials where pulps with significantly different hemicellulose compositions were high-intensity mixed at pH 13, 70°C and 10% pulp consistency and pulp strength evaluated. By varying alkalinity and temperature, pulps with different carbohydrate composition could be obtained. High alkali concentration and low temperature resulted in high glucomannan content and low xylan content, whereas cooking at low alkali concentration and high temperature rendered a pulp with low glucomannan and high xylan content. The high alkalinity pulp was stronger, determined as tear index at given tensile index. The pulp viscosity was also higher for this pulp. However, when the pulps were subjected to high-intensity mixing, the high alkalinity pulp lost in tear strength and the re-wetted zero-span tensile strength was substantially reduced. The pulp cooked at high alkalinity was thus interpreted as being more vulnerable to mechanical treatment than the pulp obtained by cooking at low alkalinity. Another pair of pulps was manufactured at high and low sodium ion concentrations, but otherwise with similar chemical charges. The pulp obtained by cooking at low sodium ion concentration became stronger, evaluated as tear index at a given tensile index and the curl index was substantially lower, 8% compared to 12% for the pulp cooked at a high sodium ion concentration. The viscosity was 170 ml/g higher for the pulp manufactured at low sodium ion concentration. When the pulps were subjected to high-intensity mixing, the tear strength of the pulp manufactured at high sodium ion concentration was reduced. The re-wetted zero-span tensile index decreased also after mixing. The pulp obtained by cooking at higher sodium ion concentration was thus interpreted as being more vulnerable to mechanical treatment than the pulp manufactured at lower sodium ion concentration. In the thesis, two reasons for the low strength delivery of industrially produced pulps compared to laboratory-cooked pulps are put forward. Since the ionic strength of mill cooking liquor systems is much higher than is normally used in laboratory cooking, this can partly explain the difference in strength between mill- and laboratory-cooked pulp. A higher sodium ion concentration was shown in this thesis work to give a pulp of lower strength. Secondly, it is suggested that the difference in retention time of the black liquor in laboratory cooking and continuous mill cooking systems can explain the difference in tensile strength between laboratory-cooked and mill-produced pulp. The black liquor in a continuous digester has a longer retention time in the digester than the chips. This gives a longer time for the dissolved xylan to degrade and, as a consequence, the xylan deposited on the mill pulp fibres will be more degraded than the xylan deposited on the laboratory-cooked pulp fibres. In the thesis, results are also presented from studies using different strength-enhancing chemicals. The fibre surfaces of bleached never-dried and once-dried pulp were modified by the polyelectrolyte multilayer technique using cationic and anionic starch. Although the pulps absorbed the same amount of starch, the never-dried pulp reached a higher tensile index than the once-dried pulp. When the starch-treated never-dried pulp was dried and reslushed it still had higher tensile index than the never-dried untreated pulp. The starch layers were thus able to counteract part of the hornification effect. The never-dried starch treated pulps were subsequently dried, reslushed and beaten. Pulp with starch layers had a better beatability evaluated as the tensile index obtained after given number of PFI revolutions than dried untreated pulp. Hence, there is a potential to increase the tensile index of market pulp by utilising the polyelectrolyte multilayer technique before drying. Addition of CMC to bleached mill pulp and laboratory-cooked pulp increased the tensile strength to the same degree for both pulps. CMC addition had a straightening effect on the fibres, the shape factor increased and this increased the zero-span tensile strength also. / QC 20100519

Wood fibres is a type of natural fibres suitable for composite applications. The abundance of wood in Swedish forests makes wood-fibre composites a new and interesting application for the Swedish pulp and paper industry. For large scale production of composites reinforced by wood fibres to be realized, the mechanical properties of the materials have to be optimized. Furthermore, the negative effects of moisture, such as softening, creep and degradation, have to be limited. A better understanding of how design parameters such as choice of fibres and matrix material, fibre modifications and fibre orientation distribution affect the properties of the resulting composite material would help the development of wood-fibre composites. In this thesis, focus has been on the fibre-matrix interface, wood-fibre hygroexpansion and resulting mechanical properties of the composite. The importance of an efficient fibre-matrix interface for composite properties is well known, but the determination of interface properties in wood-fibre composites is difficult due to the miniscule dimensions of the fibres. This is a problem also when hygroexpansion of wood fibres is investigated. Instead of tedious single-fibre tests, more straightforward, macroscopic approaches are suggested. Halpin-Tsai’s micromechanical models and laminate analogy were used to attain efficient interface characteristics of a wood-fibre composite. When Halpin-Tsai’s model was replaced by Hashin’s concentric cylinder assembly model, a value of an interface parameter could be derived from dynamic mechanical analysis. A micromechanical model developed by Hashin was used also to identify the coefficient of hygroexpansion of wood fibres. Measurements of thickness swelling of wood-fibre composites were performed. Back-calculation through laminate analogy and the micromechanical model made it possible to estimate the wood-fibre coefficient of hygroexpansion. Through these back-calculation procedures, information of fibre and interface properties can be gained for ranking of e.g. fibre types and modifications. Dynamic FT-IR (Fourier Transform Infrared) spectroscopy was investigated as a tool for interface characterization at the molecular level. The effects of relative humidity in the test chamber on the IR spectra were studied. The elastic response of the matrix material increased relative to the motion of the reinforcing cellulose backbone. This could be understood as a stress transfer from fibres to matrix when moisture was introduced to the system, e.g. as a consequence of reduced interface efficiency in the moist environment. The method is still qualitative and further development is potentially very useful to measure stress redistribution on the molecular level. / QC20100714

The chemical interactions between the main wood components i.e., cellulose, hemicelluloses and lignin are of fundamental importance for understanding the chemical aspects of wood formation and its reactivity during fibre processing e.g during chemical pulping of wood. Future progress in the development of new high value products from wood will greatly depend on a detailed knowledge of how the fibre elements interact with each other in the biological material. The existence of covalent bonds between lignin and carbohydrates (LCC) has been one of the most controversial issues in the field of wood chemistry. Only until recently, the existence of such bonds has in its entirety been shown by way of indirect analyses, normally suffering from low yields obtained at rather drastic conditions. Furthermore, previous studies on LCC have been targeted on studying the specific lignin carbohydrate linkage and less emphasis has been put on the whole LCC networks. Detailed structural studies of entire LCC are therefore of importance in understanding the chemistry involved in wood formation and wood reactivity. The aim of this study was to isolate intact LCC from wood and corresponding chemical pulps made from it in quantitative yield and to clarify their detailed chemical structure. For the first time, a method for the quantitative analysis of lignin-carbohydrate complexes (LCCs) in softwood is presented and it could be concluded that no carbohydrate-free lignin was present in these wood fibres. From mildly ball-milled wood, all lignin was isolated as LCCs in a sequence involving a partial enzymatic hydrolysis of cellulose, subsequent swelling and quantitative dissolution, into 4 major fractions; a galactoglucomannan-lignin-pectin LCC (GalGlcMan-L-P) containing ~8% of the wood lignin, a glucane LCC (Glc-L) containing ~4% of the wood lignin, a xylan-lignin-glucomannan network LCC (Xyl-L-GlcMan) (with a predominance of xylan over glucomannan) containing ~40% of the wood and a glucomannan-lignin-xylan network LCC (GlcMan-L-Xyl) (with a predominance of glucomannan over xylan) containing ~48% of the wood lignin. From unbleached kraft pulps, 85 - 90% of residual lignin was found to be chemically bonded to carbohydrates. The effect of the degree of delignification on the LCC types during kraft pulping and during subsequent oxygen stage was studied in order to understand the role of LCC for the stability of residual lignin. For both processes, high delignification rates were observed for the xylan-rich LCC and cellulose-rich LCC fractions, whereas the glucomannan-rich LCC was relatively stable. After a severe oxygen stage, almost all the residual lignin was isolated in the latter complex. Thioacidolysis in combination with gas chromatography was used to determine the content of β-O-4 structures in the lignin. Periodate oxidation and methanol determinations were used to quantify the phenolic hydroxyl groups, whereas size exclusion chromatography (SEC) of the thioacidolysis fractions was used to monitor any differences between the original molecular size distribution and that after the delignification processes. Major differences between the various LCC fractions were observed, clearly indicating that two different forms of lignin are present in the wood fibre wall. These forms are linked to glucomannan and xylan respectively. The xylan linked lignin was found to consist largely of β-O-4 structures indicating a rather linear coupling mode, whereas the glucomannan linked lignin was more heterogeneous with respect to the known lignin inter-unit linkage types. Based on these findings, a modified arrangement of the fibre wall polymers is suggested. From acid sulfite pulp (Kappa number 11) residual lignin was isolated at ~80% yield on LCC basis. About 60% was linked to xylan, 30% to glucomannan and 10% to glucans. These values differ greatly from those obtained for softwood pulped to a similar kappa number by the Kraft method. Model compound studies indicated that the benzyl ether type of LC linkage were likely to survive cleavage at the acidic sulfite pulping conditions / QC 20101026

<p>Xylan is the main hemicellulose in birch, eucalyptus, and most other hardwood species. During kraft pulping a series of chemical reactions and physical processes involving xylan take place. The processes studied in this thesis are the following: dissolution, degradation, redeposition onto the fibres, side group conversion, and cleavage of side groups off the xylan back bone. The side group in native xylan consists of methylglucuronic acid, which is mainly converted into hexenuronic acid during kraft cooking. Hexenuronic acid affect the pulp in terms of increased brightness reversion and deteriorated bleachability. The kinetics of the side group cleavage and conversion reactions were analysed using various analytical tools. The study revealed that the most commonly used methods for methylglucuronic acid measurements are not as accurate as has been claimed in the literature. A modification of two of the methods was suggested and evaluated.</p><p>A common practice used to minimise the hexenuronic acid content involves use of a high cooking temperature. The kinetic study showed that the degree of substitution of pulp xylan is only slightly affected by temperature, and that the observed effects are likely to be more associated with the xylan content of the pulp than with the hexenuronic acid content of the xylan. For the dissolved xylan, however, the degree of substitution showed a high temperature dependency and moreover it was always higher than in the pulp.</p><p>Xylan itself is known to have the capacity to increase the strength of the manufactured pulp. This knowledge was applied by exchanging cooking liquors between birch kraft cooks, in which a high amount of xylan is dissolved, and spruce cooks, which contain very small amounts of native xylan. This seems like an attractive alternative for softwood kraft cooking, since both the tensile strength and stiffness increased significantly. The magnitude of the strength increase was correlated with the molecular weight of the added xylan and with the increased surface charge of the fibres.</p>

<p>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.</p><p>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.</p><p>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.</p><p>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.</p><p>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.</p>

<p>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.</p><p>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.</p><p>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.</p><p>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.</p>

<p>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.</p><p>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.</p><p>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.</p><p>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).</p><p>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.</p>

<p>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.</p><p>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.</p><p>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.</p><p>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.</p><p>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.</p> / <p>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.</p><p>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.</p><p>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.</p><p>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.</p><p>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.</p>