Detta arbetes syfte är att utveckla en metod som konsekvent kan hitta skillnader mellan olika cellulosaråvarors reaktivt vid syntetiseringen av cellulosaacetat med ättiksyraprocessen.  Detta undersöktes genom att förändra reaktionsparameterna mängd adderad svavelsyrakatalysator och temperatur. För att kunna mäta skillnader mellan råvarorna så användes utbytesmätningar. De egenskaper hos cellulosaråvarorna som antogs ha relevans för mätningarna var råvarornas polymeriseringsgrad (DP) och deras cellulosahalt. Detta arbete kunde inte komma fram till en definitiv metod som visade signifikanta skillnader mellan de cellulosaråvaror som användes men förslag för att förbättra metoden som användes i arbetet föreslås. / The purpose of this work is to develop a method that can consistently find differences between different cellulose raw materials reactively in the synthesis of cellulose acetate with the acetic acid process. This was investigated by changing the reaction parameters amount of added sulfuric acid catalysis and temperature. In order to measure differences between the raw materials, exchange measurements were used. The properties of the cellulose raw materials that were assumed to be relevant for the measurements were the degree of polymerization of the raw materials (DP) and their cellulose content. This work could not come up with a definitive method that showed significant differences between the cellulose raw materials used but suggestions for improving the method used in the work are proposed.

Studiens syfte var att undersöka vilken effekt cellulosakedjornas polymerisationsgrad (D.P.) har på styrkan i nanofibrillerad cellulosafilm (NFC-film). Detta är av intresse på grund av tidigare studier som indikerar att både filmstyrkan och töjningen hos NFC-film ökar med ett ökande D.P. hos materialet som NFC produceras ifrån, samt att starkare NFC-filmer önskas tas fram. En ökad styrka och töjning hos NFC-filmer är viktigt för att kunna utöka användningsområdet för filmen, t.ex. inom applikationer som beständiga displayers eller till förpackningar. I denna studie framställdes NFC system genom att först hydrolysera ett bomullsmaterial med högt D.P. till olika grader. Bomullen karboxymetylerades därefter för att sedan homogeniseras till NFC. Avslutningsvis, framställdes filmer baserade på de olika NFC systemen, vars mekaniska egenskaper undersöktes för att utvärdera effekten av D.P. Dragtesten som utfördes på filmerna visade på att dragindexet (TSI) var det som påverkades mest markant av D.P. variationen. Det tycktes finnas en kritisk gräns för D.P. ≤ 2600, under vilken styrkan sjunker medan en icke nämnvärd förändring av styrkan sker över gränsen. / The purpose of this study was to investigate the effect of the degree of polymerization (D.P.) of cellulose on the strength of nanofibrillated cellulose film (NFC-film). The interest to investigate this effect is based on earlier studies, which have shown results that indicate on an increasing strength and strain for the films with an increasing D.P. of the material from which the NFC is produced. The desire to produce stronger NFC-films is also a reason for the study. Both an increased strength and strain are desired in the NFC-films, because it would expand the possible use of the films, for example as displays and in packaging applications. In this study, the NFC systems were prepared by first hydrolyzing the cotton linters, which had a high D.P., to different degrees. Then the cotton systems were carboxymetylated and homogenized. Finally, the films were prepared from the different NFC systems, whose mechanical properties were studied to evaluate the effect of D.P. The tensile tests that were performed on the films showed that the tensile strength index (TSI) was most significantly affected by the D.P. variation. There seemed to be a critical limit for D.P. at ≤ 2600, below which the strength decreases while a non-significant change in strength occurred above.

<p>In recent years, antibacterial surfaces have been a subject of increased interest. Especiallyinteresting are non-leaching, contact-active surfaces that physically disrupts the bacterialcell using immobilised cationic polymers. Thus the risks of bacterial resistance and discharge of hazardous biocides is minimised. The assembly of such surfaces is elaborate andusually involves organic solvents. Here, polyelectrolyte multilayers (PEM) are proposed as an effective surface modification method, with an overall goal of producing antibacterial cellulose fibres. The PEM process is based on physical adsorption of oppositely charged polymers in aqueous solutions. Multilayers were formed with the bactericidal polymer polyvinylamine (PVAm) and polyacrylic acid. PVAm compounds with hydrophobic modificationswere applied as well, as they possess increased antibacterial activity in solution.</p><p>In this work, the multilayer formation was studied on model surfaces of silicone oxide and glass in order to obtain fundamental knowledge of the polymer system. QCM-D and reflectometry, which detect total mass including bound water and polymer mass only, respectively, were used to analyse the layer formation. Salt-concentrations were varied at 1, 10 or 100 mM NaCl. A stepwise multilayer formation with exponential-like polymer adsorption but with decreasing water content for each layer was seen at all salt concentrations.A higher salt concentration resulted in an increased adsorbed mass. No significant differences in adsorption between the modified and unmodified PVAm could be detected. AFM imaging applied to multilayers having nine layers showed large surface aggregates under high salt conditions for the C6-modified PVAm. Dynamic light scattering showed that the polymer occurred as single molecules in solution; hence it was concluded that theaggregation is surface-associated.</p><p>The multilayers were then tested for bacterial growth inhibition. The relative bacterial inhibition was time-dependent, as the surface was saturated with bacteria over time. After two hours, a maximal inhibition of 99 % could be observed for the multilayers. After eight hours, a moderate inhibition of less than 40 % was detected. Using multilayers affected the results positively compared to single layers. After three layers, though, no further reductionwas seen. Viability staining of the surface-adhered bacteria revealed that the adhered bacteria had intact membranes. Therefore, the microbiological properties of the multilayers can at this point be described more as growth-inhibiting by bacterial adhesion effectsthan as biocidal. However, this work has shown the importance of combining surface characterisation and microbial testing to understand the bacteria-surface interaction.</p> / Biointeractive fibres

I och med de ändringar som trädde i kraft 1993/94 då funktionskrav för konstruktioner infördes istället för de enskilda materialens egenskaper lade grunden till att det numer är möjligt att bygga byggnader som kräver en hög grad av brandskydd i trä och andra material baserade på brännbart material. Denna ändring innebar bland annat att nya och innovativa produkter hade chans att etablera sig på den svenska marknaden, såsom isolering tillverkad av returpapper och träfiber. I och med träets naturliga förmåga att till viss grad motstå brand, bland annat genom att bilda ett skyddande kolskikt, i kombination med tillsats av flamskyddsmedel som försvårar antändning ytterligare resulterar i att dessa material numer har möjlighet att konkurrera mot obrännbara material gällande brandsäkerhet i byggnader. De testmetoder som idag avgör en produkts brandklass sker under kontrollerade former med temperaturer som inte motsvarar en fullt utvecklad brand. Detta medför att det utifrån ett materials brandklass, eller s.k. euroklass, inte går att förutse materialets brandmotstånd under en fullt utvecklad brand. Inte heller under ett så kallat Room Corner Test, som ska motsvara brandens tidiga skede, har det visat sig att euroklassen inte alltid motsvarar de krav som ställs för att förhindra vidare förbränning och övertändning. Däremot går det att utifrån euroklass se mönster i dess klassificering och förmåga att sprida glödbrand.

Paper is a network material composed of a great number of fibers that interact with each other through fiber joints. In order to make a clear statement regarding observed changes being made in paper, it is vital to determine the structural level of paper that is being affected by chemical modifications. Polyelectrolytes having a wide range in molecular properties have been synthesized to investigate the adsorption behavior of cationic polyelectrolytes to cellulosic fibers. The interaction with the porous cell wall of cellulosic fibers is governed by the molecular properties of the polyelectrolyte. More specifically, polyelectrolytes having a low charge density are able to penetrate into the fiber cell wall, while high charge density polyelectrolytes are restricted to the exterior fiber surface. The molecular mass also influences the extent to which adsorption occurs within the cell wall, although this is typically only pronounced for low charge density polyelectrolytes. High charge density polyelectrolytes are generally restricted to the fiber surface due to strong Coulombic interactions between charged groups along the molecular backbone, which create a stiff molecular conformation. These results were confirmed by fluorescent labeling techniques, which allow the polyelectrolytes to be tracked inside the cell wall by confocal laser scanning microscopy. This approach was also used to demonstrate the effect of an electrolyte, which screens the Coulombic interactions and facilitates penetration into the cell wall. However, a considerable difference in the adsorption behavior of polyelectrolytes having similar molecular mass is still observed at high electrolyte concentration, where the electrostatic contributions are negligible. These differences are a consequence of a diffusion process that occurs on a longer times scale. Although polyelectrolyte adsorption to cellulosic fibers reaches a pseudo-equilibrium at short times, a driving force into the cell wall exists due to the bulk charge of the fiber. The time scale of this diffusion process depends on the polyelectrolyte properties, and was observed to persist for over 3 months. As the extent to which these polyelectrolytes penetrate into the cell wall has been ascertained, and the fibers can be crosslinked to different degrees in the cell wall or at the surface. Cationic acetal dextran was prepared as a model crosslinking agent, as the molecular mass, charge density and degree of acetal substitution can readily be controlled during synthesis. A considerable effect on the tensile properties and fracture toughness was observed for crosslinked paper, which could be attributed to either the fibers or the fiber joints. Crosslinking acted to stiffen the fibers and the fiber joints, which influenced the transfer of applied stresses through the paper structure. Changes in the material behavior at high relative humidity could be improved by crosslinking the fibers at the correct the structural level. / QC 20100811

Pulp- and papermills expend vast amounts of water in order to produce pulp, paper and cardboard. Hence, they alsocreate vast amounts of waste water which has to be cleaned before it can be released into the receiving body of water. Insuch a wastewater treatment plant, tremendous amounts of energy are expended by the aeration in the biologicalcleaning process. This aeration is necessary to supply the microorganisms that shall decompose organic material withoxygen, which they need for their metabolism. The transfer of oxygen from the gas phase to the liquid phase isprimarily inhibited by surface-active substances in the waste water like resin acids or fatty acids. The purpose of thisthesis has been to determine if the surface-active substances can be removed by means of chemical pre-precipitationbefore the waste water enters the biological cleaning step. Thus, the efficiency of the aeration shall be improved.In the laboratory, aeration tests were performed for plain water, water with added surface-active substances and CTMPwastewaterfrom Stora Enso Skoghalls Bruk. The test for water with added surface-active substances showed clearlythat these substances have a big influence on the aeration efficiency, which was impaired considerably compared withplain water.In order to determine how chemical precipitation influences the content of surface-active substances, screening trialswere performed with the CTMP waste water. The concentration of surface-active substances was estimated bymeasuring the surface tension of the waste water. The surface tension sinks with increasing concentration of thesesubstances. 250 ml CTMP-wastewater was precipitated with three different chemicals: PAX-XL60, PGA and AVR. Inorder to determine the optimal dosing as well as the optimal pH-value for goal-oriented precipitation of the surfaceactivesubstances, the precipitation was performed with different pH-values between 4 and 8 as well as for differentdoses of the precipitation chemicals. It was discovered that the optimal pH-value for precipitation with PAX-XL60 is7,5 while the precipitation with PGA had the optimal pH-value of 6. The optimal dosage for PAX-XL60 was 10 g/cm3,while the optimal dosage for PGA could not be determined because of the small waste water volume used in thescreening trials. The screening trials showed that the surface tension increased after precipitation with both PAX-XL60and PGA which leads to the assessment that the concentration of surface-active substances has decreased.Precipiation- and aeration trials in big lab-scale were performed at pH 7,5 and the optimal dosage of PAX-XL60. ForPGA, the precipitation and aeration trials were performed at pH 6 and the lowest dosage of the screening trials. Theaeration trials showed that precipitated CTMP-wastewater could be aerated more energy efficient than the samewastewater without precipitation.Calculations showed that energy costs can be reduced by nearly 90% by using the tested precipitation chemical PAXXL60respectively nearly 65% by using the tested precipitation chemical PGA according to the lab-scale trials. Thecosts for the chemicals are not included.

This thesis will show the possibility for the development and use of an on-line model for application to continuous digesters for pulp production. The model is developed by using a program called Dymola (Dynamic Modeling Laboratory). What makes the Dymola software so well suited is that the program solves equations simultaneously. The model is a further development from the Purdue model [Bhartiya et al, 2003]. The main difference between this model and the Purdue model however, is the dynamics in the model. The dynamics are very important when you use the model for control purposes because the cooking process has long dead and retention times. The main purpose of this model is to use it for the advanced control of continuous digesters as well as giving the operators a better understanding of what happens in the cooking process when changes are made. The model will also be used for diagnostic purposes. Advanced control in this case is Model Predicted Control (MPC). The MPC will control the quality of the pulp “kappa” number and the chemical consumption during digestion. This thesis describes the model and results are shown for applications of on-line diagnosis in three pulp mills in South Africa. Real time process data from the pulp mills is fed into the model and a simulation is performed. Thereafter, the results from the simulation are compared to the actual measured data for a number of key variables. By comparing the simulation results to the real process data and following the trends of the deviations between the two, different types of faults and upsets can be detected in both the process and sensors. / KKS project:Use of physical models combined with statistical models for improved digester control

Det här examensarbetet utfördes på Innventia på uppdrag av Bioisolator. Bioisolator är ett SME-företag, (SME = små och medelstora företag) som saluför ett cellulosabaserat material för beklädnad av väggar och tak. Bioisolator har utvecklat ett nytt och unikt byggnadsmaterial för ljudisolering, Acustica Spackel. Materialet acustica kan appliceras och monteras på alla ytor och har en rad andra egenskaper såsom att vara värmeisolerande, fukt- och mögelresistent med mera. Appliceringen sker för hand, med hjälp av spackel, vilket är en tidskrävande och slitsam process. För att hitta olika metoder som kan vara mer tidseffektivare och med mindre ansträngning, utvecklades det här examensarbetet. För att undersöka olika metoder och se vilka som är tillgängliga, har en litteraturstudie tagits fram där olika alternativa metoder presenterades och beskrivits närmare, se avsnitt om litteraturstudien s.10. Två olika huvudmetoder upphittades inför granskning och jämförelse, dessa är tapetmetod och sprejningsmetod. För var och respektive metod upphittades ett antal olika procedurer som samlades i en tabell i avsnitt om litteraturstudien. Av sprejningsmetoden valdes skruvpumpen och elmyggan och av tapetmetoden valdes StratEx att prövas inför det praktiska försöket i detta examensarbete. Resultatet blev att skruvpumpen inte funkade för ändamålet, medan elmyggan funkar, dock med lite justeringar i acustica massa såsom bortföring av flakesen, som är små runda plastikliknande former som kan täppa till i slangen vid sprutningen. StratEx försöket är inte färdigt än eftersom de försök som utfördes i detta projekt anses vara otillräckliga för att kunna fastställa något med säkerhet. Bioisolator, som medverkade under vissa moment, blev nöjda med det erhållna resultatet, de testade elmygga metoden med godkända resultat. / This thesis was done at Innventia and commissioned by Bioisolator. Bioisolator is an SME, small and medium sized company which markets cellulose-based materials for covering walls and ceilings. Bioisolator has developed a new and unique building material, Acustica Spackel, for sound insulation. The material acustica can be applied and mounted on any surface and has other characteristics as well, such as being heat-insulating and being resistant to moisture, mold, etc. This application is done by hand using a spatula, which is both time-consuming and exhausting. The aim of this method is to compare different methods and find the one that is more time efficient and requires less effort. To investigate different methods and see what's on the market, a literature study was done in which various alternative methods were presented and described in more detail. Two main methods were used for examination and comparison; these are the wallpaper method and the spraying method. For each respective method, different procedures were given and gathered in a table. From the spraying method, screw pump and elmyggan were chosen and from the wallpaper method, Stratex was chosen, to be tested for the practical attempt in this thesis. The result was that the screw pump was not suitable for this purpose. A few adjustments such as: in acustica pulp such as removal of flakesen, which are small circular plastic-like shapes which can clog the tubing, for the elmyggan was deemed more suitable. The StratEx trial is not finished yet because the experiments which were carried out in this project are considered to be insufficient to establish with certainty. Bioisolator, participated in certain moments, was satisfied with the result obtained; they tested the method elmygga then at home with approved results.

Med rapsfrön som en eftertraktad produkt från raps kvarstår rapshalm, vilket anses vara en avfallsprodukt. Dock är rapshalmen en god källa till biopolymerer och kan spela en potentiell roll som råvara till materialframställning. Det övergripande målet med detta examensarbete var att fullständigt separera lignin och cellulosa från varandra i den halmrest som återstår efter hydrotermisk extraktion av rapshalm vilket delprojekt 1 har behandlat. Den huvudmetod som har tillämpats under projektet var alkalisk delignifiering, med bestämd tid, temperatur och koncentrationen NaOH. Två prover av halmrester valdes för behandling i detta projekt varav den första har extraherats med närvaro av bikarbonat som buffertlösning medan den andra har extraherats vid en högre temperatur. Ytterligare metoder för att erhålla lignin och cellulosa var ligninfällning och defibrering. Av den erhållna cellulosamassan framställdes papper. De erhållna produkterna med kolhydratanalys (IC), askhalt (TGA), och bestämning av funktionella grupper (FTIR). Cellulosamassan analyserades med SEM och ljusmikroskopi. De framställda pappersarken analyserades med dragprovning för bestämning av mekaniska egenskaper. Det totala utbytet av lignin inte så högt, en tredjedel av ligninmängden i rapshalm. Det första provet gav ett högre utbyte än det andra, däremot gav det andra ett mer ligninrikt utbyte. Fibermassan från det andra provet hade en högre halt cellulosa. Mikroskopianalyser visade att fibrerna inte frilagts fullständigt från varandra, med kvarvarande biomassa som bibehåller sin originalstruktur. Mängden frilagda fibrer var högre i det första provet samt fiberstrukturen på de spiralformade fibrerna höll kvar sin primära form. Enligt resultaten från dragprovningsanalysen hade papperet från det första provet en signifikant högre brottgräns och E-modul än det andra. / The oil rich seeds from the rapeseed are products of interest, which leaves the straws as a waste product. Rapeseed straw is a good source of biopolymers which have potential as material resources. The overall aim of this degree project was to fully separate lignin from cellulose in pretreated straws. The main method applied was delignification with alkali under specified conditions including time, temperature, and the concentration of sodium hydroxide. Two samples of preextracted straw were chosen. The first sample was extracted in the presence of a buffer while the second was extracted at a higher temperature. Other methods were also used, such as kraft lignin precipitation for a better yield of lignin, and defibration of the cellulosic fibre mass. Paper sheets were made from the obtained fibre mass. The products were analyzed with a variety of analytic methods, including IC, TGA, and FTIR. The straws and the cellulosic mass were further analyzed with SEM and optical microscopy. The obtained paper materials were analyzed mechanically by tensile testing. The total yield of lignin was not so high, about a third of the total lignin content in the rapeseed straw. The first sample gave a higher than the second sample, however the second sample gave a more lignin rich yield. The obtained fibre mass in the second sample had a considerably higher content of cellulose. Microscopy analyses showed that the fibres did not fully separate, and there were remains of biomass in their current structure. The amount of separated fibres were higher in the first sample as well as the spiral-shaped fibres maintained their structure. The results from the tensile test showed that the paper prepared from the first sample had a significantly higher tensile strength than the paper obtained from the second sample.

Restprodukter är i fokus för vidareförädling. Restprodukter från jordbruk och skogsindustri innehåller en stor mängd fibrer och detta arbete undersöker restprodukternas kvalitativa egenskaper samt om det finns potential för att använda dem i cellulosaindustrin. Restprodukter som samlades in var vetehalm, rapshalm, vetekli, betfor, ensilage, grot, primärslam, sågspån samt fiberrejekt. En litteraturstudie utfördes om varje restprodukt för att få en bättre förståelse av vad de består av och hur de uppstår. Genom att extrahera holocellulosa från restprodukterna analyserades de kvalitativa egenskaperna som fibrerna har. För minsta möjliga förändring av fibrernas form och dimensioner användes en macereringsmetod för att extrahera holocellulosa från restmaterialen. Metoder som användes för att analysera de kvalitativa egenskaperna hos restprodukterna var viskositets bestämning, titreringar och gravimetriska analyser. Med dessa metoder kunde massutbyten, askhalter, massviskositeter, perättiksyra- och väteperoxidhalter avgöras för de extraherade holocellulosamassorna. För att undersöka om de extraherade holocellulosamassorna kan användas i cellulosaindustrin testades två typer av processer. Den ena var aerogelproduktionen och den andra en kompressionsgjutning för produktionen av biokompositer med hög styrka. Det visade sig att fiberrejekt gav störst holocellulosautbyte jämfört med de andra restprodukterna. Analyserna gav resultatet att sågspån hade de fibrer med högst polymerisationsgrad medan vetekli och betfor hade de fibrer med lägst polymersiationsgrad. Upplösningen av holocellulosamassans fibrer gick inte att utföra då testprovet hade antingen för hög massviskositet eller för hög andel hemicellulosa som förhindrar att lösningsmedlet löser upp fibrerna. Kompressionsgjutning av holocellulosamassan från vetehalm var lyckat då det gick att förädla den mjuka massan till en massa med mer styvhet. Kompressionsgjutning av holocellulosamassorna kan vara ett alternativ för att producera material för additiv tillverkning (3D-printing). / By-products are in focus for further processing. Residues from agriculture and forest industry contain a large amount of fiber, and this work investigates the qualitative properties of residues and whether there is potential for using them in the cellulose industry. By-products collected were wheat straw, rapeseed straw, wheat bran, betfor, silage, branches, primary sludge, sawdust and fiber rejects. A literature study was conducted around each by-product to get a better understanding of what they consist of and how they occur. By extracting holocellulose from the by-products, the qualitative properties of the fibers were analyzed. For the slightest change in the shape and dimensions of fibers, a maceration method was used to extract holocellulose from the by-products. Methods used to analyze the qualitative properties of the by-products were viscosity, titrations and gravimetric analyzes. With these methods, mass exchanges, ash levels, mass viscosities, peracetic acid and hydrogen peroxide levels could be determined for the extracted holocellulose masses. To investigate whether the extracted holocellulose masses can be used in the cellulosic industry, two types of processes were tested. One was aerogel production and the other a compression mold to produce high strength biocomposites. It was found that the fiber rejects yielded the greatest holocellulose exchange compared to the other residues. The analyzes gave the result that sawdust had the fibers with the highest degree of polymerization while wheat bran and betfor had the fibers with the lowest degree of polymerization. The dissociation of the holocellulose mass could not be performed because the test sample had either a too high mass viscosity or a too high a proportion of hemicellulose which prevents the solvent from dissolving the fibers. Compression molding of the holocellulose mass from wheat straw was successful as it was possible to make the soft pulp a lot more rigid. Compression molding of the holocellulose masses may be an alternative for producing additive manufacturing materials (3D printing).