Dissertations / Theses on the topic 'Wood pulp fibre'

Knowledge of the ultrastructural arrangement within wood fibres is important for understanding the mechanical properties of the fibres themselves, as well as for understanding and controlling the ultrastructural changes that occur during pulp processing. The object of this work was to explore the use of atomic force microscopy (AFM) in studies of the cell wall ultrastructure and to see how this structure is affected in the kraft pulp fibre line. This is done in order to eventually improve fibre properties for use in paper and other applications, such as composites. On the ultrastructural level of native spruce fibres (tracheids), it was found that cellulose fibril aggregates exist as agglomerates of individual cellulose microfibrils (with a width of 4 nm). Using AFM in combination with image processing, the average side length (assuming a square cross-section) for a cellulose fibril aggregate was found to be 15–16 nm although with a broad distribution. A concentric lamella structure (following the fibre curvature) within the secondary cell wall layer of native spruce fibres was confirmed. These concentric lamellae were formed of aligned cellulose fibril aggregates with a width of about 15 nm, i.e. of the order of a single cellulose fibril aggregate. It was further found that the cellulose fibril aggregates had a uniform size distribution across the fibre wall in the transverse direction. During the chemical processing of wood chips into kraft pulp fibres, a 25 % increase in cellulose fibril aggregate dimension was found, but no such cellulose fibril aggregate enlargement occurred during the low temperature delignification of wood into holocellulose fibres. The high temperature in the pulping process, over 100 ºC, was the most important factor for the cellulose fibril aggregate enlargement. Neither refining nor drying of kraft or holocellulose pulp changed the cellulose fibril aggregate dimensions. During kraft pulping, when lignin is removed, pores are formed in the fibre cell wall. These pores were uniformly distributed throughout the transverse direction of the wood cell wall. The lamellae consisting of both pores and matrix material (“pore and matrix lamella”) became wider and their numeral decreased after chemical pulping. In holocellulose pulp, no such changes were seen. Refining of kraft pulp increased the width of the pore and matrix lamellae in the outer parts of the fibre wall, but this was not seen in holocellulose. Upon drying of holocellulose, a small decrease in the width of the pore and matrix lamellae was seen, reflecting a probable hornification of the pulp. Refining of holocellulose pulp led to pore closure probably due to the enhanced mobility within the fibre wall. Enzymatic treatment using hemicellulases on xylan and glucomannan revealed that, during the hydrolysis of one type of hemicellulose, some of the other type was also dissolved, indicating that the two hemicelluloses were to some extent linked to each other in the structure. The enzymatic treatment also decreased the pore volume throughout the fibre wall in the transverse direction, indicating enzymatic accessibility to the entire fibre wall. The results presented in this thesis show that several changes in the fibre cell wall ultrastructure occur in the kraft pulp fibre line, although the effects of these ultrastructural changes on the fibre properties are not completely understood.
QC 20101012

The aim of this thesis was to study the fibre surface properties of Birch (Betula ssp.), Eucalyptus (E. urograndis and E. globulus) and Spruce (Picea Abies) pulps bleached using two different methods: ECF (Elementary Chlorine Free) and TCF (Totally Chlorine Free). The hardwood pulps were subjected to a hot acidic stage prior to ECF bleaching in order to remove hexenuronic acid. The effect of prolonged storage (ageing) on the fibre surface properties was studied for all of the pulps.

The characteristics of the fibre surfaces were determined by measuring the dynamic contact angle of single fibres (DCA) and by using Electron Spectroscopy for Chemical Analysis (ESCA) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS). The correlation between the fibre surface properties and the sizing efficiency of the hardwood pulps were evaluated by measuring the amount of alkyl ketene dimer (AKD) needed to reach a certain water absorption level(measured as Cobb₆₀).

The birch pulp was more hydrophilic than the eucalyptus pulps, thus requiring more AKD to reach a certain water absorption value, and also had a lower DCA. The introduction of a hot acidic stage (A stage) in the ECF bleaching sequence applied to the hardwood pulps (i.e. A/D(EP)DD versus D(EP)DD) lowered, as expected, the total fibre charge due to the removal of hexenuronic acids groups (HexA). According to the DCA measurements all of the pulps became more hydrophilic after the A/D(EP)DD bleaching than after the D(EP)DD bleaching sequence. The sizing ability of the pulps, measured as the AKD demand to a certain Cobb₆₀ value, showed that the AKD demand was more or less the same for the eucalyptus pulps regardless of the bleaching sequence used. The birch pulp, on the other hand, required somewhat less AKD in the A/D(EP)DD sequence than in the D(EP)DD.

The AKD demand to a certain Cobb₆₀ value decreased further for the bleached birch and E. globulus pulps after ageing due to an increase in the fibre surface hydrophobicity. ESCA analysis revealed an increase of surface extractives on the pulps after ageing, which was also supported by ToF-SIMS analysis. It was concluded that there was an increase in fatty acids, fatty acid salts and possibly even sterols and glycerides on the fibre surfaces due to ageing. A migration of these components from the interior of the fibre wall to the fibre surface during ageing was verified in this study.

The TCF and ECF bleached softwood pulps also showed differences in their fibre surface properties that were tangible and thereby measurable. The dynamic contact angle was highest for the TCF bleached softwood fibres, i.e. these were more hydrophobic. Although changes caused by ageing were much more pronounced for the ECF fibres, all pulps became more hydrophobic upon ageing.

The hydrophobicity of pulp fibres can be determined using DCA, which is a rather rapid and economically viable analysis. Using this information, a paper/board mill can base its sizing strategy on scientific findings.

The ageing effects seen on the fibre surfaces in the form of the migration of extractives might be an important parameter from an industrial point of view, especially when pulps are stored and/or transported for a long time period. Nowadays it is quite common for pulps to be shipped around the world and subjected to warm and humid conditions. It is therefore probable that the properties of the pulp change in such a way that the papermaking process requires adjustment.

Cellulosans tillgänglighet och reaktivitet är nyckelparametrar vid framställning av regenererad cellulosa och cellulosaderivat. Det är välkänt att på grund av cellulosans kristallina struktur är tillgängligheten begränsad för lösningsmedel och olika reagens. Till exempel kan en inhomogen substitution av hydroxylgrupperna i cellulosakedjan resultera i cellulosaderivat av sämre kvalitet. Baserat på detta har en del av arbetet i denna studie fokuserat på att förbättra cellulosans tillgänglighet och reaktivitet genom att studera effekten av olika enzymatiska behandlingar med monokomponent endoglukanaser. Resultaten visar att närvaron av en cellulosabindande domän fyller en viktig funktion för att öka cellulosans reaktivitet, men strukturen för den katalytiska domänen visade sig ha den största inverkan på cellulosans tillgänglighet. I kompletterande studier har även effekten av en mekanisk förbehandling i kombination med enzymatisk behandling utvärderats. Kombinationen av förbehandlingarna resulterade i en positiv effekt, cellulosans reaktivitet kunde ökas i större omfattning.

I dag används huvudsakligen dissolvingmassor som råvara vid framställning av cellulosaregenerat och cellulosaderivat. Kraven för dessa s.k. specialmassor är högt cellulosainnehåll samt lågt hemicellulosa- respektive lignininnehåll. På grund av dessa specifika krav är produktionskostnaderna för dessa massor högre än konventionella sulfatmassor. Den andra delen av studien har därför fokuserat på möjligheten att använda dessa sulfatmassor som dissolvingmassa. Det har visats att kombinationen av enzymatiska behandlingar med monokomponent endoglukanas och xylanas följt av ett alkaliskt steg kan resultera i massor där kraven uppfylls med avseende på cellulosans reaktivitet, och cellulosa- respektive hemicellulosainnehåll.

The accessibility and reactivity of cellulose are key parameters on the manufacturing of cellulose derivatives and regenerated cellulose. It is well known that, due to the crystalline structure of cellulose, the accessibility of solvents and reagents is limited. For instance, an inhomogeneous substitution of the hydroxyl groups of the cellulose chain might lead to the production of derivatives of low quality. As a consequence, part of this work has focused on improving the accessibility and reactivity on cellulose by studying the effect of different monocomponent endoglucanases. It has been demonstrated that the presence of the cellulose-binding domain plays an important role on the enhancement of cellulose reactivity; however, the structure of the catalytic domain has been showed to have the highest influence on this parameter. Furthermore, the influence of mechanical treatment prior to enzymatic treatment has been examined. The combination of pretreatments showed a positive effect enhancing to a larger extent the cellulose reactivity.

Currently, dissolving-grade pulps are commonly used for the production of cellulose derivatives and regenerated cellulose. The requirements for these so-called “special pulps” are a high cellulose content and a low hemicelluloses and lignin content. As a result of these specific demands, the production costs of these pulps are higher than those of common kraft pulps. The second part of this work, therefore, has been focused on the study on the viability of converting kraft pulps into dissolving pulps. It has been demonstrated that the combination of enzymatic treatments using a monocomponent endoglucanase and a xylanase together with the addition of an alkaline step could fulfil the requirements of a commercial dissolving pulp in terms of cellulose reactivity and cellulose and hemicellulose content.

Abstract Plant fibres are an important part of modern daily life. The most obvious consumer products manufactured from them are paper, cardboard and the fibreboards used in the construction and furniture industries. Plants producing a woody stem are the most widely used raw materials for these fibre products but fibres originating from other plants, i.e. non-wood fibres, are used too. One of the most promising potential non-wood fibre resource categories is that of grasses, of which the cereals are the most important plants grown worldwide. A huge amount of straw is generated as an agricultural by-product annually, but the amount used as an industrial raw material is low because it contains components that are detrimental either to processability or to product quality. The purpose of pulp fractionation is to divide pulp into fractions with distinct properties. Industrially feasible fractionation methods are pressure screening, hydrocyclone fractionation and flotation. In pressure screening, separation is based on a mechanical barrier and particles are fractionated according to their dimensions, while a hydrocyclone fractionates particles according to their density and specific surface area and flotation fractionates particles according to their surface chemistry. These methods are traditionally used for removing impurities from pulp but numerous reports on pulp fractionation can also be found. Previous fractionation experiments were performed using wood-based pulps, whereas no previous studies are available concerning the fractionation of pulps manufactured using grasses. The aim of the present work was to determine whether it is possible to fractionate wheat straw pulp by methods that are feasible on an industrial scale. The experimental part was concerned with wheat straw pulp fractionation by pressure screening, hydrocyclone fractionation and flotation. The results show that all these fractionation methods were able to divide the wheat straw pulp into fractions with different cell properties and cell types, e.g. distinct cell lengths, cell wall thicknesses or surface chemistries. Likewise, fractionation can be used to remove detrimental components or to optimize pulp properties according to their end use or to optimize pulp processing sequences. Due to the uniform structure of grasses, it is likely that the results can be generalized to other grasses than that employed here
Tiivistelmä Kasvisoluja sisältävät tuotteet ovat laajalti mukana ihmisten jokapäiväisessä elämässä. Kaikista näkyvimpiä tuotteita ovat paperi- ja kartonkituotteet sekä rakennus- ja huonekaluteollisuuden käyttämät kuitulevyt. Perinteisesti kasvikuidut näihin tuotteisiin on saatu puuvartisista kasveista, mutta raaka-aineena käytetään muitakin kasveja, niin kutsuttuja non-wood kasveja. Yksi potentiaalinen kasviryhmä teollisuuden raaka-aineeksi ovat heinäkasvit. Muun muassa tärkeimmät viljakasvit ovat heinäkasveja, ja maatalouden sivutuotteina syntyy korsimateriaalia maailmanlaajuisesti huomattava määrä. Heinäkasvien teollinen hyödyntäminen on kuitenkin vähäistä sillä ne sisältävät komponentteja, jotka haittaavat materiaalin prosessointia tai ovat lopputuotteen ominaisuuksia heikentäviä. Kuitususpension fraktioinnin tarkoituksena on jakaa suspensio kahteen tai useampaan jakeeseen, joiden kuituominaisuudet tai solukoostumus ovat erilaiset. Teollisesti käytettävissä olevia fraktiointilaitteita ovat painelajitin, hydrosykloni ja flotaatio: painelajittimessa erottuminen perustuu mekaaniseen esteeseen ja partikkelit erottuvat pääasiassa partikkelin dimensioiden perusteella, hydrosyklonissa erottuminen tapahtuu partikkelien tiheyden ja ominaispinta-alan mukaan kun taas flotaatiolla voidaan erottaa pintakemialtaan erilaisia partikkeleita. Näitä laitteita on perinteisesti käytetty epäpuhtauksien poistamiseen kuitususpensiosta, mutta laitteiden käyttöä puusta valmistettujen massojen fraktiointiin on tutkittu laajasti. Heinäkasveista valmistettujen massojen fraktiointiin näitä menetelmiä ei ole sovellettu. Tämän tutkimuksen tarkoituksena oli selvittää vehnämassan sisältämien solujen fraktiointia teollisuuden käyttöön soveltuvilla menetelmillä. Työn kokeellisessa osassa fraktiointiin vehnäsellua painelajittimella, hydrosyklonilla ja flotaatiolla. Työn tulokset osoittavat, että kaikki tutkitut fraktiointimenetelmät pystyvät jakamaan vehnämassan jakeisiin, joilla on erilaiset solujen ominaisuudet sekä solukoostumukset. Fraktioinnin avulla on mahdollista tuottaa jakeita, joiden kuitupituudet, seinämäpaksuudet sekä pintakemia eroavat. Näin ollen massasta voidaan poistaa jokin haitallinen solujae, tai vaihtoehtoisesti fraktiointia voidaan käyttää optimoitaessa massan ominaisuuksia lopputuotteen ominaisuuksien parantamiseksi, tai optimoitaessa massan prosessointia. Koska heinäkasvit ovat rakenteeltaan samanlaisia, ovat tulokset hyvin todennäköisesti yleistettävissä muidenkin heinäkasvien fraktiointiin

Dissolving-grade pulps are commonly used for the production of cellulose derivatives and regenerated cellulose. To obtain products of high quality, these so-called "special" pulps must fulfill certain requirements, such as high cellulose content, low hemicellulose content, a uniform molecular weight distribution and high cellulose reactivity. Most, if not all, of the commercial dissolving pulps accomplish these demands to a certain extent. Nevertheless, achieving high cellulose accessibility as well as solvent and reagent reactivity is not an easy task due to the compact and complex structure presented by the cellulose. In the first part of this work, three commercial monocomponent endoglucanases were investigated with the purpose of enhancing the cellulose accessibility and reactivity of a hardwood dissolving pulp. A monocomponent endoglucanase with a cellulose-binding domain (CBD) was shown to significantly improve the cellulose reactivity. The positive effect of this enzyme on dissolving-grade pulps was also observed on paper-grade pulps. The main focus of the forest industry is the production of paper-grade pulps. Paper-grade pulps are mostly produced by the kraft process. In contrast, dissolving-grade pulps are produced by the sulfite and prehydrolysis kraft processes due to the high purity required for these pulps. The kraft process is known for being the most efficient process in terms of energy and chemical recovery, which makes the production costs of paper-grade pulps lower than those of sulfite dissolving-grade pulps. Besides, the production of dissolving pulps present, among others, higher capital and chemical costs than paper-grade pulps. Therefore, the viability of converting paper-grade pulps into dissolving pulps is brought into a question. However, this task is not simple because paper-grade pulps contain a lower cellulose content and a higher hemicellulose content than dissolving pulps. They also present lower cellulose reactivity and an inhomogeneous molecular weight distribution. As a consequence, the second part of this work focused on the study of the feasibility of converting kraft pulps into dissolving pulps. Several sequences of treatments of hardwoods and non-wood pulps were investigated. The best sequence for each suitable pulp was developed, and the parameters involved were optimized. After several attempts, it was demonstrated that pulps from birch, eucalypt and sisal fulfill the requirements of a commercial dissolving pulp for the viscose process after being subjected to a sequence of treatments that included two commercial enzymes, a xylanase and a monocomponent endoglucanase, and alkali extraction steps.
QC 20101201

Passage of fibres suspended in water through apertures of dimensions greater than a fibre length and less than a fibre diameter has been examined at flow conditions approximating those in a pulp screen (large velocity parallel to the wall upstream of the aperture compared to the flow velocity within the aperture). Fibre behaviour was characterized in terms of three components: penetration of the leading tip into the aperture, rotation of the fibres on the downstream edge of the aperture, and fibre bending. Dimensionless numbers for each of these factors were derived from simple mass and force balances of fibres at an aperture entry. Experimental measurements of the magnitude of fibre passage were made on a single aperture located in a flow channel and in multiple apertures in a device simulating a commercial pulp screen in cross-section. For stiff fibres, it was found that fibre passage changed greatly with the ratio of fibre length to aperture width (L/W). When L/W was less than 2, the relationship between fibre passage and aperture velocity was approximately an exponential curve. The passage data correlated well with the penetration parameter. On the other hand, when L/W > 2, up to measured values of L/W = 6, the relationship between fibre passage and aperture velocity corresponded to a cumulative probability distribution curve. This latter behaviour, and the absence of a correlation with penetration and rotation parameters, was ascribed to contact between the tip of the rotating fibre and the upstream wall of the aperture. This was confirmed by experimental observations. Flexible long (L/W > 2) fibres showed behaviour between the two cases described above. The above observations were found to hold qualitatively for elevated concentrations up to a crowding factor of 4, multiple apertures, and the presence of pulses induced by a rotor of the type found in pulp screens. Accordingly, it appears that the findings are likely to hold in pulp pressure screens. An implication of this finding is that long stiff fibres may be best separated from short ones by choosing an aperture size such that L/W > 2 for the long fibre fraction and < 2 for the short fibre fraction.
Applied Science, Faculty of
Chemical and Biological Engineering, Department of
Graduate

Wood pulp fibers are a unique reinforcing material as they are non-hazardous, renewable, and readily available at relatively low cost compared to other commercially available fibers. Today, pulp fiber-cement composites can be found in products such as extruded non-pressure pipes and non-structural building materials, mainly thin-sheet products. Although natural fibers have been used historically to reinforce various building materials, little scientific effort has been devoted to the examination of natural fibers to reinforce engineering materials until recently. The need for this type of fundamental research has been emphasized by widespread awareness of moisture-related failures of some engineered materials; these failures have led to the filing of national- and state-level class action lawsuits against several manufacturers. Thus, if pulp fiber-cement composites are to be used for exterior structural applications, the effects of cyclical wet/dry (rain/heat) exposure on performance must be known. Pulp fiber-cement composites have been tested in flexure to examine the progression of strength and toughness degradation. Based on scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM), energy dispersive spectroscopy (EDS), a three-part model describing the mechanisms of progressive degradation has been proposed: (1) initial fiber-cement/fiber interlayer debonding, (2) reprecipitation of crystalline and amorphous ettringite within the void space at the former fiber-cement interface, and (3) fiber embrittlement due to reprecipitation of calcium hydroxide filling the spaces within the fiber cell wall structure. Finally, as a means to mitigate kraft pulp fiber-cement composite degradation, the effects of partial portland cement replacement with various supplementary cementitious materials (SCMs) has been investigated for their effect on mitigating kraft pulp fiber-cement composite mechanical property degradation (i.e., strength and toughness losses) during wet/dry cycling. SCMs have been found to be effective in mitigating composite degradation through several processes, including a reduction in the calcium hydroxide content, stabilization of monosulfate by maintaining pore solution pH, and a decrease in ettringite reprecipitation accomplished by increased binding of aluminum in calcium aluminate phases and calcium in the calcium silicate hydrate (C-S-H) phase.

Thesis (Ph.D)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Sujit Banerjee; Committee Member: Frances Walsh; Committee Member: Peter Ludovice; Committee Member: Timothy Patterson; Committee Member: Yulin Deng. Part of the SMARTech Electronic Thesis and Dissertation Collection.

The surfaces of well characterised microfibrils from Ventricaria and Micrasterias denticulata (M.d.), wood sections, kraft pulp fibres and paper have been examined with both atomic force microscopy (AFM) and Tapping Mode atomic force microscopy (TM-AFM), under ambient conditions in both air and water. Artifacts and limitations inherent to these techniques in the study of microfibrils, pulp fibres and paper are discussed. AFM images of the surface of the highly crystalline cellulose microfibrils, Ventricaria and M.d., were obtained at molecular resolution under ambient conditions; the molecular images showed periodicities along the microfibril axis that correspond to those of the fibre and glucose unit repeat distances of cellulose, respectively. Images of the section surface of Black Spruce (Picea mariana) wood clearly show features of the underlying cell wall structure. The apparent lamellation, with periodicities from tens or nanometers down to 15 nm, were observed in radial sections of the middle secondary wall (S2). However, transverse sections of the same S2 layer did not show a lamellation independent of the knife direction. AFM images of unbeaten and beaten unbleached kraft pulp fibre surfaces indicate the orientation of the component microfibrils; fibrillar material attached to the surface of the beaten fibres was readily observed. Images from the scale of the fibre web down to the microfibril level in air and water show the dimensional changes of the paper surface and fibres. However, little or no change was seen at the microfibril level. The dimensions of the lamella in wood sections and the size of the microfibrils at both the surface of pulp fibres and the fibrillated material indicate that microfibrils as small as 1.5 nm across are present.

The thesis comprises three parts: Existing methods for characterisation of fibre crosssections have been improved, and new methods have been developed. These methods have then been applied to study the effects of wood characteristics and the pulping process on mechanical pulp fibres. Links have been established between fibre structure and paper properties such as surface smoothness and light scattering coefficient.

New methods, based on SEM-images and image analysis, are described for providing cross-sectional fibre dimensions for large fibre populations, for wood tracheids (app. 60 000 tracheids in a wood trunk) and for processed pulp fibres (app. 1000 fibres per sample). The methods are suited e.g. for evaluation of changes in the fibre cross-sections from wood to the finished paper, or for mapping of fibre parameters within and between growth rings in a wood trunk. The treatment of data is discussed, showing how one may examine the changes in different groups of fibres (earlywood fibres, latewood fibres, split fibres) throughout a process.

It is known from the literature that groundwood-based paper is superior to TMP-based paper with respect to printability. Fibres from SGW and PGW-pulp were found to be much more split in the longitudinal direction than TMP-fibres at comparable freeness. Intact groundwood fibres had thicker walls than intact TMP-fibres, but nevertheless super calendered hand sheets made from groundwood fibres were less roughened by moistening than were TMP-based sheets. Both for groundwood pulps and for TMPpulps, it was shown that reduced fibre wall thickness and increased fibre splitting was beneficial for improved surface smoothness and opacity.

Latewood defibrate easier than earlywood during refining. In the case of grinding, there was no particular preference for earlywood or latewood to be defibrated. Reject refining of groundwood reject was, however, found to be very important for defibration of latewood-containing shives. Pulps made from a raw material with more compact fibres (high wall area to lumen area ratio) were found to defibrate easier, and contain less shives. It was found that refining tends to reduce wall thickness most on thickwalled parts of the fibre, thus causing a reduction of the wall thickness variation around the perimeter.

Earlywood fibres were found to be preferentially split during refining. Most fibre splitting occurs during the primary stage, while the fibres are firmly attached to chips or fibre bundles. Latewood fibre wall thickness decreases considerably more than earlywood fibre wall thickness during refining. It seems that choosing an appropriate raw material is more effective than using excessive energy on reducing the wall thickness of thickwalled fibres. Earlywood fibres became more flattened during refining compared to latewood fibres, possibly due to repeated compressions and relaxations in the refiner.

The energy consumption to a given freeness was found to be considerably larger for Scots Pine than for Norway Spruce. However, the fibre transverse dimensions did not differ much between Norway Spruce and Scots Pine. Pine pulps were far less developed than spruce pulps at similar energy level. A possible explanation for the large energy consumption may be that redistribution of extractives at the fibre surface could reduce friction in the refiner. This hypothesis should be further explored.

The results in this study improve the knowledge of which fibre parameters that matter for surface smoothness and opacity of wood-containing publication paper. Further, this study elucidates how important fibre parameters such as wall thickness and fibre splitting are altered during a refining process. The results may be utilized to identify possible ways of modifying the TMP-process in order to produce paper with improved surface smoothness and opacity.

Procuring hardwood pulpwood during the winter months for a pulp mill in the Southeast can be difficult. Saturated soils and low soil strength make logging difficult or impossible on many sites, forcing companies to store large volumes of hardwood pulpwood in woodyards for retrieval during wet weather. Hardwood fiber readily available in large volumes on ground that is operable during wet periods at a location near the pulp mill could provide a valuable alternative wood source. Thus, the objectives of this study are to 1) develop a decision model for a manager to use to determine the feasibility of strategically located, intensively-managed, short-rotation hardwood fiber farms as pulp mill furnish, 2) use the model to estimate wood costs for a hypothetical eastern cottonwood plantation, and 3) use the model to determine if a fiber farm grown on drier, upland sites (â greenâ inventory) could be used to reduce woodyard winter inventories and economically supply a nearby pulp mill during a wood shortage, thus reducing high cost, emergency â spot marketâ wood purchases. The decision model is incorporated in a spreadsheet and includes all the costs typical for a fiber farm. The model is tested using current establishment and management costs from the literature and yields from an experimental fiber farm in the southeast. Under current yields, delivered costs from the fiber farm averages $71/ton. With potential increased yields that could occur with genetic improvements and operational optimizations, delivered cost for fiber farm wood could be reduced to $56/ton. In comparison, the highest cost wood purchased by the three cooperating pulp mills during the study period was $50.23/ton. The net present values of a fiber farm as â greenâ inventory were determined using actual wood cost and inventory levels from three cooperating southeastern pulp mills. For the â greenâ inventory analysis, all three pulp mills would have lowered their overall wood cost using a fiber farm (with higher yield) as â greenâ inventory, primarily by reducing the amount of wood required as dry inventory on woodyards. Savings accrued during â dryâ years offset the higher cost of hardwood plantation deliveries. A sensitivity analysis was performed to determine the optimal size fiber farm for one of the cooperating pulp mills and indicated that 800 acres would be the most beneficial.
Ph. D.

A new technique for measuring the water content of fiber is presented. Tritiated water is added to a pulp/water suspension whereupon the tritium partitions between the bulk water and the pulp. Through this technique a fiber:water partition coefficient is developed, Kpw. This thesis will cover the development of the Kpw procedure and three different case studies. The first study involves comparing Kpw to traditional methods of fiber water content. The procedure provides a value of ten percent for the tightly bound water content of unrefined hardwood or softwood kraft fiber, either bleached or unbleached. If this water is assumed to cover the fiber surface as a monolayer, then an estimate of the wet surface area of fiber can be obtained. This estimate compares well to independent measurements of surface area. Kpw has also been found to be valuable in furthering the understanding of refining. Based on the study, it is proposed that refining occurs in three discrete stages. First, refining removes the primary cell wall and S1 layer while beginning to swell the S2 layer. Next, internal delamination occurs within the S2 layer. Finally, fiber destruction occurs at high refining levels. By using Kpw, the three stages of refining are clearly recognized. Lastly, Kpw is used to study the effect of hornification on bleached softwood kraft fiber. The recycling effects at three refining levels were characterized by Kpw and followed closely the findings of the refining study. At low and high refining levels, the impact of recycling was minimal according to Kpw results, but at 400 mL csf the impact of recycling was much more pronounced. This could be attributed to the closing of internal delaminations within the fiber.

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.

One of the main interests in commercial methane production is to maximize the gas yield, and it is thus appealing to use material with relative high methane potential. However, such material often results in process instability whereas ammonia inhibition is common. Removal of ammonia through adsorption is a fairly unexplored method in the field of biogas production, and could prove to be cost-effective.The adsorption capacity of pulp fibres from the paper making industry were investigated through batch adsorption experiments. Additionally, the fibres effect on small scale batch digesters in terms of methane production and cellulase activity was explored. Overall, the adsorption capacity of the pulp fibres was low, whereas Kraft hardwood had the highest adsorption capacity in both an aqueous ammonium solution and digester fluid at 11±3 and 60±20 mg g-1, respectively. The initial total ammonium nitrogen concentration had the highest effect on the adsorption capacity with a positive correlation. The pulp fibres seemingly had no effect on the ammonia inhibited anaerobic digestion systems. However, the cellulase activity was higher after day 5 in the anaerobic digestion systems with a high ammonia concentration.In essence, the overall results showed that the adsorption of the fibres was relatively low and most likely not suitable as a material to prevent ammonia inhibition in an AD.

This research project originated from interest in assessing the potential of enzyme technology (particularly laccase-based systems) for the biomodification of sisal specialty fibres by using environmentally friendly processes. This doctoral work focused on two different research lines, namely: biobleaching and enzymatic functionalization of sisal pulp fibres. The study was started by assessing the use of natural, potentially cost-effective phenolic compounds as substitutes for expensive, potentially toxic laccase mediators. The tendency of natural phenols to either promote delignification or couple onto pulp was examined with a view to assessing their potential for either bleaching or functionalizing sisal fibres. In the biobleaching study, totally chlorine free (TCF) sequences were implemented in order to compare the efficiency of a selected natural mediator and a well-known synthetic mediator, both in the presence and absence of a xylanase pre-treatment. The effluents resulting from each stage in the sequence were analysed with a view to assessing the environmental impact of the laccase treatments ¿a scarcely explored aspect of biobleaching sequences. The xylanase stage proved highly efficient in reducing the HexA content of sisal fibres and in boosting the bleaching effect of the laccase treatments. The proposed TCF sequences provided high-cellulose sisal pulp with brightness above 80% ISO and a reduced HexA content; also, they exhibited improved performance and a reduced impact on effluent properties relative to the use of the synthetic mediator. Two different approaches to fibre functionalization were explored, namely: lignin modification (biografting) and cellulose modification (laccase¿TEMPO oxidation). Biografting of phenolic compounds was for the first time studied in sisal pulp. Covalent binding of the originally assayed phenolic compounds to sisal fibres during the laccase treatment was exposed by a novel analytical approach based on pyrolysis-GC/MS. The phenolic compound showing the highest tendency to couple to fibres was selected to investigate biografting under different reaction conditions and to evaluate the extent of phenol coupling via various pulp properties. Biografting efficiency was enhanced by refining the fibres prior to the enzyme treatment, which provided improved strength-related properties in the resulting paper. The use of the laccase-TEMPO system to oxidatively modify cellulose and improve strength-related properties in sisal pulp was for the first time evaluated as an environmentally friendly alternative to existing halide-based systems. The first part of this study revealed that the laccase¿TEMPO system considerably improved wet strength in sisal pulp by effect of the formation of a substantial amount of aldehyde groups in cellulose chains that facilitated inter-fibre bonding through hemiacetal linkages. The influence of process variables on various properties of the oxidized fibres and resulting paper was assessed by using a three-variable statistical plan. The conditions maximizing functionalization and the improvement in paper strength properties were used to design treatments of increased efficiency that exposed the potential of laccase¿TEMPO oxidation for biorefining pulp fibres. Analytical methods including pyrolysis-GC/MS, polyelectrolyte titration, conductimetric titration, carbohydrate determination by HPLC, fibre morphology analysis by SEM and thermogravimetry were used to both characterize the raw material and gain a better understanding of the reaction mechanisms behind the different laccase-based treatments. Some of the analyses were performed by collaborating research groups at IRNAS (Seville, Spain) and the Department of Chemical Engineering of the University of Huelva (Spain). Also, part of this doctoral work was conducted at the Institute of Paper Science and Technology of the Georgia Institute of Technology (Atlanta, USA).

Phlebia radiata est un basidiomycete du groupe des champignons de la pourriture blanche, seuls microorganismes connus capables de degrader totalement la lignine du bois. A l'aide de la microscopie electronique a transmission associee a des techniques cytochimiques, nous avons pu mettre en evidence differents modes de degradation provoques par le champignon au cours de l'attaque d'echantillons de bouleau et de peuplier: il peut soit attaquer selectivement la lignine, en provoquant un amincissement progressif des parois secondaires des fibres et / ou en degradant les lamelles mitoyennes, soit degrader simultanement tous les constituants du bois, en perforant les parois et / ou en degradant specifiquement la couche s1 de la paroi. Une etude originale utilisant des anticorps diriges contre des lignines synthetiques nous a permis de visualiser la distribution heterogene des lignines au sein des differentes couches des parois cellulaires. Il apparait que la nature de la lignine a une influence sur le type de degradation. P. Radiata produit des enzymes ligninolytiques, lignine-peroxydases, manganese-peroxydases et laccases, que nous avons localisees au cours de la degradation du bois, grace a des marquages immunocytochimiques. Afin de suivre les enzymes ligninolytiques a un stade tres precoce de leur formation, une approche en biologie moleculaire utilisant des sondes arn a ete engagee pour localiser les arnm codant pour une lignine-peroxydase et pour une laccase de p. Radiata. Ce champignon, comme les autres champignons de la pourriture blanche, presente, par sa capacite a delignifier le bois, un interet potentiel pour l'industrie papetiere. Nous avons montre que la mnp isolee provoque une defibrillation de pates kraft ecrues. Par ailleurs, l'ion manganese complexe a un acide organique, agit egalement en defibrillant les pates. Il apparait que le complexe mniii-oxalate est plus efficace que le complexe mniii-pyrophosphate a blanchir la pate kraft

An in-depth investigation is carried out to characterise the damage accumulation mechanisms and fatigue growth in single wood pulp fibres, which may be thought of as concentrically-layered, filamentary composite tubes that are approximately: 1-3 mm long, 20-40 $ mu$m in cross-section. The novel experimental methodology principally consists of the in situ apparatuses, on the one hand, which comprise the in-house designed and built single-fibre tensiometer, in conjunction with the confocal laser scanning microscope (CLSM) and, on the other, the computer hardware and periphery. The tensiometer's prime components, the loading jaws, are specifically designed to best emulate the force actions to which wood pulp fibres are subjected while between the discs of mechanical refiners (viz.: cyclic shear, radial compression and tension); and incorporate a mechanical fixation mechanism to ensure proper mounting of the single fibres. Moreover, the CLSM, which functions by scanning a diffraction-limited spot of light relative to the specimen in a raster-type scan, is a powerful tool for obtaining qualitative information on the morphology of fractured surfaces and structural behaviour of the fibres being fatigued, as well as providing accurate visual records of the history of crack propagation. The entire fully-automated set-up is controlled, in real time, via a computer algorithm specifically written for displacement-control fatigue-testing, while making efficient utilisation in terms of execution time, memory allocation, signal conversion and data acquisition.
The engendered conclusions may be summed up as follows. From a litany of tenuously-oriented microcracks, dominant macrocracks propagate along the axis of the fibre which may sharply deflect in the presence of natural bias (e.g. pits in the fibre wall). The material property degradation characteristics further include: volumetric expansion due to internal fibrillation in the cell wall, extensive external fibrillation, gradual delamination of the layers and partial peeling-off of the cell wall material. Cumulative damage due to cyclic shear is shown to be the most significant, further supported by the high structural collapsibility of the fibre wall layers. The mechanisms of fracture are either due to the development of transverse cracks at regions of high stress concentration (such as bordered pits), or owing to the gradual slippage of the fibre wall layers.

In this project, a numerical model describing the reaction mechanism and the mass and energy transport in wood pyrolysis is studied. The applicability of the model in predicting actual biomass pyrolysis assessed by comparing the model to TGA experimental measurements. The comparison to experiments is done in relation to the mass loss characteristics of chips of varying sizes. The mass loss is of interest as it is a variable necessary in the coupling of reactor and particle models. Three reaction models were simulated and results compared to experimental data, namely, the reaction model developed by Park et al. [Combustion and Flame 157 (2010) 481-494], a simple multicomponent parallel reaction model, and a competitive reaction model. The model of Park et al. did not fit with the experimental data as it underestimates the char yield. The parallel reaction model, which is based on hemicellulose and cellulose decomposition to char and volatiles, also did not agree with the experiments even when fitting the parameters to the data. The downward trend of char yield with increasing temperature suggests there exists competition between the volatiles and char in wood pyrolysis. The proposed competitive reaction model which consists of a hemicellulose reaction to volatiles and a cellulose reaction to volatiles and char is in good agreement with the experimental data. The mass loss characteristics in the experimental temperature range is fairly predicted within reasonable accuracy.

The present study investigates the thermochemical conversion of spruce wood and its extracted components by thermogravimetric analysis. The extracted components are two pulps, three xylan-lignin samples and one lignin sample; they were produced by the kraft cooking method with different cooking times. The study involves characterization of the biomass through proximate analysis and pyrolysis. A qualitative comparison between the thermal behaviours of the extracted components and wood is also performed. The study showed that the thermal behaviour of the biomass was highly influenced by the content of cellulose and lignin in the samples. Compounds rich in cellulose produced large quantities of volatiles and had a higher rate of pyrolysis compared to compounds rich in lignin, which produced more char and had a slower rate of pyrolysis. It was also shown that, the amount of char is not solely depending on the amount of the lignin; the structure of the compound also plays a role. On the other hand, the original wood sample showed some deviations regarding the trends in volatile and char production and these deviations were attributed to component interactions. Both cellulose and lignin rich compounds had an increase in thermal stability with increasing cooking time. For the pulps the increase in thermal stability is believed to be caused by increase in crystallinity, while for the lignin rich samples is believed to be caused by the increase in lignin content and structural changes in the compounds. The results also show that although changes are introduced in the cooking process, the extracted component still retain properties exhibited by the source biomass.

Mercury contamination is an environmental issue with high priority due to its high toxicity. In addition to the atmospheric deposition, several lakes and rivers in Sweden are contaminated as a result from wood and pulp-fiber industries which stretches back 200 years. In Luleå, Sweden, a former groundwood industry, Karlshäll, has contributed to mercury pollution in the sediments of Notviken, a small bay connected to Luleå River and the Bothnian Sea, through release of process water. Industrial release of chemicals and wood pulp have resulted in a special type of sediment called fiber banks. The fiber banks contain high levels of organic matter and very little oxygen which contributes to large gas emissions from the fiber banks, gas ebullition. There is no generally accepted method for examining how mercury contaminants are spread through gas ebullition. The aim of this thesis was to review and find methods for that purpose. Through the literature review several types of methods emerged. Some of them were useful for measuring volumes of gas, whereas others were better designed for collecting gas and analysing it for concentration of elements. There are pros and cons with all methods but the one considered most useful in the case of Karlshäll would be Skarp’s method with active and passive sampling. The passive part includes setting up tents over the fiber bank with a known area, and then calculate the volumes of gas which migrate up through the water during a certain amount of time. The active sampling consists of stirring the fiber bank sediment with a stick and then gather the ascending gas bubbles in a Teflon-bag. The Teflon bag is thereafter sent to a chemical environmental laboratory for analysis of the concentration of elements. This method is the only one of the ones reviewed in this thesis which have been tested in Sweden at sites with gas- ebullition facilitated mercury transport. Although, Varadharajan et al’s (2011) sampling device with automation could be applicable if a long-term, high frequency monitoring programme would be used at Karlshäll. In addition, a sampling device with an integrated carbon-absorption-tube collector for trapping gaseous Hg would be beneficial if the samples can’t handle a long-distance transportation. Thus, the samples could be sent to a local laboratory instead. However, this type of device is not yet invented and would need further studies to develop.
Kvicksilverföroreningar är ett stort miljöproblem som räknas till de särskilt farliga ämnena vilka skall fasas ut för att nå miljömålet giftfri miljö. Föroreningarna är mycket giftiga för djur och miljö och det kvicksilver som redan spridits ansamlas och stannar kvar under lång tid i mark, vatten och biota. Utöver den atmosfäriska depositionen så är floder, älvar och sjöar i Sverige förorenade med kvicksilver, ett resultat av en 200-årig industri för tillverkning av pappersmassa och träfiber där kvicksilver varit en del i tillverkningsprocessen.  I Luleå fanns det ett träsliperi kallat Karlshäll mellan åren 1912–1962 som släppte ut orenat processvatten innehållandes kvicksilver tillsammans med rester av träfiber till den närliggande viken, Notviken, som är ett inlopp från Lule älv. Industriella utsläpp av kemikalier och träfiber har resulterat i bildandet av en viss typ av bottensediment, kallad fiberbank. Fiberbankarna innehåller höga nivåer av organiskt material i kombination med lite syre vilket bidrar till stora gasutsläpp från fiberbankarna, gasavgång. Det finns ingen vedertagen metod för att undersöka hur kvicksilverföroreningarna sprids genom gasavgång. Syftet med denna uppsats är att undersöka och hitta metoder som kan undersöka kvicksilverföroreningarnas spridning via gasavgång. Genom en litteraturstudie och intervju med en entreprenör inom miljöteknik framträdde flertalet olika metoder för att kunna kvantifiera eller mäta kvicksilver i gas från fiberbankar. Några av dem var användbara för att mäta volymer av gas. Andra metoder lämpade sig bättre för att samla in gas för analys av koncentrationer av olika ämnen.  Även om alla metoder i viss mån lämpar sig för att undersöka gasavgång från sediment ansågs Jonny Skarps metod som inkluderade både aktiv och passiv provtagning med gasfällor och teflonpåsar vara den mest passande för fiberbankar likt den i Karlshäll. Den passiva metoden innefattar installation av tält över en känd area på sedimentbotten och sen beräkna mängden gas som bubblar upp under en viss tid. Den aktiva insamlingsmetoden bygger på att sediment störs med ett spetsigt föremål, exempelvis ett lod, så att gasbubblor släpper från sedimentet och samlas in med hjälp av en teflon- påse. Teflon-påsen skickas sedan till ett kemiskt laboratorium i Göteborg för analys av innehållet i gasen. Båda dessa provtagningssätt kunde tillsammans mäta mängden kvicksilver ifrån gasen samt volymen av gasen. Denna metod är den enda av de som undersökts i denna uppsats som testats i Sverige på platser med kvicksilver som avgått i gasform från fiberbankar. Dock så är Varadharajan med fleras (2011) automatiserade gas-insamlare ett bra alternativ ifall en hög frekvens av provtagning är nödvändig i kombination med en lång insamlingstid. Denna skulle kunna kombineras med en insamlingsmetod av gasbubblor där det lokala kemilaboratoriet kan analysera innehållet. I detta fall krävs att ett kolfiber-rör är en del av mätinstrumentet. Dock finns det ännu inte något sådant instrument och fler studier behövs för att utveckla ett sådant.

The regular transmittance of light or similar radiation through a flowing suspension of particles fluctuates because of the random occurrence of particles in the beam.In the work presented here, a theory for this fluctuating behaviour with the emphasison dispersions of mm-length slender cylindrical particles having circular crosssections is given. The particles in question are wood pulp fibres, which as a first approximation are considered to have a cylinder shape. Four possible measurementprinciples are described theoretically and experimentally. The four principles are for the measurement of concentration, length distribution characterized as lengthclasses, mean length, and mean width. The usefulness in industrial process monitoring of two of these principles is exemplified with pulp measurements. In order to estimate model errors, numerical simulations were used. Although other techniques such as image analysis may compete, the technique presented here is attractive because of the simplicity of the measurement device used.
QC 20100806

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

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009.
Committee Chair: Ragauskas, Arthur; Committee Member: Bunz, Uwe; Committee Member: Cairney, John; Committee Member: Collard, David; Committee Member: Singh, Preet. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Abstract The wood industries to this day use almost exclusively petroleum derived adhesives that are based mainly on the reaction of formaldehyde with urea, melamine or phenol. These adhesives have low cost and good adjustable properties which makes it hard for bio-based alternatives to compete. Phenol formaldehyde (PF), as an example of a synthetic adhesive, has been in use for over 100 years. In some parts of the world, legislation around formaldehyde is changing, and there is an increasingly voluntary awareness about the toxicity and unsustainability of formaldehyde. Industries realize that raw materials from oil is unstainable. The latter is currently a driving factor behind research on alternatives to amino based adhesives. Also, consumer interest in healthy and sustainable products, such as emitting less formaldehyde indoors, increases the need for bio based adhesives. Cellulose contained in plant cell walls is a renewable, abundant and nontoxic resource. During the last decades, many innovations have been achieved around cellulose and this trend does not seem to be slowing down. Cellulose shows excellent mechanical properties, high strength, high elastic modulus as well as having a low density. Research about cellulose reinforced adhesives has been increased the last years. This thesis studied the enhancement of phenol formaldehyde adhesive with Crystalline Nano Cellulose (CNC) at 5wt% and 10wt% loading levels for producing plywood boards. Indecisive results when using CNC higher than 3wt%, especially with PF resin, have been reported by other authors. In this thesis, European standards were applied. EN 314 was applied to test the panels shear strength. Three (3) treatment classes were selected, indoor room condition as well as pre-treatments 5.1.1 and 5.1.3. Other properties measured were modulus of elasticity, thickness swelling, formaldehyde emissions. Results showed a shear strength increase for all pre-treatment classes. 10wt% CNC mixture with phenol formaldehyde in water bath, pre-treatment (5.1.1) for 24h showed the highest increase in shear strength (+73,9%). The 10 wt% CNC mixture panels also showed the highest wood fibre failure of all panel types produced. A decrease in MOE has been observed with 10 wt% CNC compared to the 5 wt% CNC panels. Formaldehyde emissions tests were inconclusive, but since less PF was used, there was a general reduction in emissions. The 5 wt% CNC panels were superior in terms of modulus of elasticity and swelling and also showed improved shear strength.

This thesis describes an investigation into the flow behaviour of particulate solids and capsules in wood pulp fibre suspensions. Emphasis is placed on measuring pipe friction loss and stability of solids-fibre slurries and fibre-capsule mixtures in straight horizontal pipes. It is shown that low concentrations (1-3 %v) of wood pulp fibre form a structured carrier fluid with ability to support particles while behaving like a liquid of low viscosity. At moderate flow velocities fibres damp turbulence and friction losses become lower than water. If solids are preferentially injected into the fibre suspension as a central core, or in a capsule as dry solids, pipe friction loss is reduced further, as is pipe wear. At very low fibre concentrations (<1%v), fibres reduce the friction loss of conventional solid-water mixtures and act as a drag reducing additive. The network strength properties of five wood fibre suspensions are reported and their application to slurry flow is discussed. Settling data for particulate solids, coherent dense-phase cores and capsules are presented and various mechanisms of support are described. Two flow techniques for transporting coarse and dense-phase particle suspensions are proposed, along with strategies for injecting solid particulates into a pipeline. Pipe friction loss data are presented for solids-fibre mixtures of wood chips (7-15 mm), coarse (+2-10 mm) and fine (+0.5-1.0 mm) coal, sand (+0.32-2.0 mm), iron ore (+0.05-0.28 mm), and cylindrical capsules (loaded with dry solids) flowing in 54, 79 and 101.6 mm diameter PVC pipes. Some pipe friction loss data are presented for solids transported as a central core supported by an annulus of fibre suspension. The key flow parameters are also optimized and a preliminary cost comparison is made. Coarse coal suspensions (up to 4O %v) with fibre concentrations of 0.7 to 1.0 percent have been shown to exhibit friction losses about 40 percent below that of the equivalent coalwater slurry. Adding 0.8 percent fibre to water is shown to reduce capsule friction head loss up to 50 percent.

Lodgepole pine stands harbour a major commercial significance in British Columbia. The lodgepole pine forests not only make up half of the British Columbia Interior annual harvest, but are also highly utilized and acceptable for lumber and pulp production. Unfortunately, mature lodgepole pine stands have been surmounted by outbreaks of mountain pine beetle, which is the most destructive insect to pine. In addition, mountain pine beetle epidemic outbreaks can last for numerous years depending on climatic factors; damaging vast areas of lodgepole pine forests and making long term planning for timber supply and integrated resource management arduous. Currently, the loss of lodgepole pine due to mountain pine beetle infestation is substantial, and as an attempt to battle the crisis, abundant volumes have been harvested. However, previous work has concurred that wood from dead trees affect product quality, which is the primary concern for the pulp and paper industry. Currently, there is a lack of information on the mechanism and effects of mountain pine beetle on pulp fibre quality. In order to fully utilize the mountain pine beetle killed resource, it is crucial to understand how the pine beetle impacts fibre quality. As a result, the present investigation evaluates the effects of mountain pine beetle killed wood on wood morphology, chemistry and pulping properties. Prior to experimental analysis, a dead (infested by mountain pine beetle) and sound standing lodgepole pine tree were harvested from the same site and segregated into sapwood and heartwood at different positions of the tree. Moisture content and density analysis demonstrated that infested sapwood and heartwood exhibited significantly reduced moisture content and lowered density, as tree height increased. The chemical analysis indicated that infested sapwood contained less extractives, lignin and carbohydrates when compared to sound sapwood. These results are likely due to the mountain pine beetle and subsequent blue stain fungi infestation. Extractive content typically increased with tree height whereas, the carbohydrate content tended to decrease. In general, no clear trend was apparent for the heartwood chemical analysis. Consequently, the permeability analysis demonstrated that infested sapwood was more permeable than sound sapwood; while sound heartwood was more permeable than infested heartwood. These results are likely due to the fact that fungal hyphae were present in infested sapwood and numerous aspirated pits were found in infested heartwood as observed from the microscopic analysis. Moreover, the chip quality analysis revealed that the infested wood typically generated more fines than sound wood; however, tree height did not appear to affect chip quality. Similarly, the pulp quality analysis demonstrated that the infested wood had a lower kappa number, generated a higher pulp yield and consumed less alkali compared to sound wood. The changes in pulp quality can be attributed to the changes in wood chemistry. Additionally, paper quality analyses revealed that paper from the infested wood had lower burst and tensile indices and higher tear strengths. Paper quality from the infested wood was also more porous, less smooth and less dense. The fibre quality analysis suggest that differences in paper quality made from infested wood may be due to the original fibre attributes rather than the effect of pine beetle or blue stain fungi, in that the results indicated that the infested wood fibres were longer and coarser. Clearly, mountain pine beetle infested wood affects wood quality, however, the differences between sound and infested wood are not so significant that the beetle killed resource cannot be utilized.

The health problems associated with asbestos and its related products necessitated in finding alternative resource of fibres. Over the last two decades natural fibre (mainly wood pulp fibre) has emerged as the most acceptable alternative reinforcement for fibre cement products. The first three chapters of this study describe in some depth the preparation and properties of natural fibres, the methods of incorporating such fibres into cements and mortars, the theoretical principles of fibre reinforcement, the properties obtained from these natural fibre (mainly wood pulp fibre) reinforced cement composites and their applications as commercial products, especially as the main alternatives to asbestos reinforced cement materials. Chapter four and five discuss fabrication and performance characterisation of the resulting composites.

Considerable research has been done to reduce water consumption by recycling the process water. The goal is to achieve zero liquid discharge or "closed-cycle" mill operation. However, there are still some problems due to the presence of some materials that are not needed in the pulping process and which tend to accumulate in the system and create operational problems. These materials mostly are metal ions that are known as Non-Process Elements (NPEs). They originate mainly from wood, and also from process water and the makeup lime. Therefore, understanding the interaction of these harmful metal ions with the fiber is needed to manage these metals in a closed-cycle pulp mill. Fibers have many functional groups such as: carboxyl acid, phenolic hydroxyl, hexenuronic acid, polysaccharide acids and catechol groups. These groups create a negatively charged fibre when they dissociate in water. Hence, fibres can interact with the metal ions like iron, manganese and copper electrostatically, chemically or both. The focus of this work is the interaction of iron with wood fibres. Pulp samples from British Columbia interior and coastal mills were investigated. Metal ion concentration on the fiber at various pulping stages was determined. The sampling points at the pulp mill were taken after brown stock washer, after oxygen delignification, and at various stages of the bleaching processes. It was found that fibre from a coastal mill has a higher iron concentration compared with fibre from an interior mill. The water used in transporting the log might introduce iron into the wood so that pulp from coastal mill would have more iron. It was also found that iron concentration in the fiberline did not change much because iron form precipitates and trapped inside the fiber mat. Metal ion removal methods using a combination of acid washing and chelation in four-washing stages was developed. A chelating agent (DTPA) was able to increase the iron removal substantially. The fiber properties such as the water retention value (WRV) and the charge properties were determined for the metal ion partitioning prediction. The fiber saturation point was found to increase as the pH increase due to swelling for all samples. Two charged groups were able to represent the fiber charge on the fiber, one charge group dissociates at acidic condition and the other one dissociates at alkaline condition. The origin of these two functional groups was not identified. The acidic charge group might probably contain carboxyl acid bound to lignin (pK[sub A]»5-6) and uronic acid (pK[sub B]~3-4). The alkaline charge group might be the phenolic hydroxyl bound to lignin. It was also found that the charge content decreases down the fiberline as the lignin content decreases. Partitioning experiments were conducted whereby we measured the iron concentration on the fiber and in the surrounding liquor. The fibres were previously acid washed with a chelating agent to "free" them from the metals. The results indicated that iron strongly stayed on the fiber even at acidic conditions where the fibre did not contribute any charge to attract the metal ion. SEM & EDX analysis confirmed the presence of iron precipitates on the fiber and trapped inside the fiber mat so that these precipitates become the fibre phase belonging. Iron might probably form complexes with the anionic group in the water, especially the hydroxyl group. A partitioning model based on Donnan equilibrium was used to compare equilibrium concentration of iron in fibre and the surrounding liquor. The model calculated values were not found to be in agreement with experiment data probably due to iron-compound precipitation. It should be noted that the model was able to predict manganese and copper partitioning, although the predictions were slightly lower than the experimental data especially at higher pH (pH > 7). Manganese and copper containing precipitates were encountered at pH 7 but not at pH 5. Manganese and copper data were obtained in another study in our laboratory. It can be concluded that the iron interaction with the charge groups on the wood fibres is not a chemical binding interaction, but due to the iron-compound precipitates which are trapped inside the fibre web. Hence, a strong water soluble ligand like those chelating agents can bind the metal ions from the suspension so that the harmful metal ions can be removed from the suspension.

The bonding of fibres in paper is influenced by environmental changes (e.g. moisture) that may cause unstable fibres to move. These movements include cell-wall swelling, fibre lifting and/or puffing that break inter-fibre bonds and lead to reduced strength and surface roughness. Fibre puffing is defined as the expansion of the lumen area as result of changes in the environment. Puffing was investigated through image analysis of scanning electron micrographs. Detailed images were obtained with samples that were embedded in resin and then etched. Puffing of fibres was then quantified by calculating the ratio of lumen area to fibre area. Stability of softwood and hardwood fibres was studied in this way, and to simulate printing, handsheets were calendered and rewetted. This method was later validated against commercial sheets. Compared to softwood, hardwood fibres were more stable and most of the handsheet properties were retained after rewetting. Mannanase and/or endoglucanase treatments resulted in improved fibre stability by increasing fibre bonding, fibrillation or fibre collapse. Mannanase improved handsheet smoothness and strength as well as fibre stability, but endoglucanase was less effective. The effect of the enzymes was more difficult to observe on hardwood fibres, because even untreated fibres were more stable under moist conditions. Thin-walled fibres such as earlywood were less stable than latewood fibres, but it responded better to mannanase treatment. Thick-walled fibres (latewood), on the other hand, were more difficult to improve with enzymes. The potential of enzymes to improve fibre stability of commercial pulp was tested on chemi-thermo-mechanical pulp (CTMP) and bleached CTMP. Enzyme treatment improved fibrillation and reduced beating energy of bleached CTMP. Mannanase again resulted in the most improved fibre stability. On rejects, a lack of response to enzymes was overcome by pre-treating the pulp with alkaline peroxide. This study provided new insights into the stability of fibres with different morphology. It was also demonstrated that fibre stability can be improved with enzyme treatment and it is expected that this knowledge could have significant commercial value.
Dissertation (PhD)--University of Pretoria, 2010.
Microbiology and Plant Pathology
unrestricted

The metal ions of Mn and Cu interact with the lignocellulosic matrix of pulp fibres and their presence is detrimental in pulp processing. The design of suitable strategies for effective management of metals requires understanding the behaviour of these NPEs in kraft pulp suspensions. The present study is focused on the characterization of kraft pulps and provides experimental data for chemical interactions of metals with wood fibres. Kraft pulps from two different geographic locations were studied. Also, the pulps were collected from different processing stages (chemical environment). Metal profile of pulps was obtained and their removal efficiency using an acid assisted chelation process was studied. Fibre properties like Fibre Saturation Point (FSP) and fibre charge essential for understanding metal partitioning behavior were determined. Metal partitioning between fibre and bulk solution (pH ) was carried out by introducing various concentrations of Mn and Cu and the effect of pH on partitioning behaviour was studied. SEM and EDX of the pulp samples were conducted to investigate the precipitation of metals in the pulp suspension. The Mn and Cu concentration in the pulp was maximum in the BSW stage pulp and gradually decreased down the processing stages. Maximum of 59 ppm and 71 ppm of Mn was found in coastal and interior mills respectively. Cu was found in very small quantity of 2 ppm and 1 ppm in coastal and interior mill samples. The removal efficiency using acid assisted chelation was studied. It is seen that Mn removal is about 90% with both the pulps. However, the low concentrations of Cu limited the analytical precision of removal efficiency. The FSP of the pulps increased with the increase in pH and reached a plateau at about pH=9. Potentiometric titration data was used for charge determination and it was seen that at any given pH the charge on the unbleached pulp was higher when compared to bleached pulp. Also fibre charge tends to increase with increasing pH. Partitioning experiments showed that the fibres do not get saturated with Mn even at high concentrations (600 ppm). However there is a gradual increase in Mn in the bulk phase while the change is limited in the fibre phase. Fibres did not get saturated with high concentration of Cu (20 ppm). Finally, the SEM micrographs and EDX analysis employed helped in detecting Mn and Cu precipitates in the pulp at pH=7. The experimental data and values from partitioning prediction model agreed. However; the model may not hold good for pH>7 due to precipitation of Mn and Cu.

The purpose of this research work was to develop novel continuous bio-composite fibres with a combination of wood pulp or lignin and synthetic polymers, using continuous electrospinning and extrusion processes. The electrospun composite fibres have potential application in filtration, wound dressing, non-woven fabrics and support of thin polymeric separation membranes. Lignin fibres could be used for the development of carbon fibres. Two types of polyethylene oxide electronspun composite fibres (300-600 nm in diameter) were formulated using treated and untreated wood fibre. The optimum polymer solution concentration (7 wt.%) and addition of 5 wt.% wood pulp were found to produce uniform composite fibres. Superior dispersion and orientation were obtained with acetylated wood pulp as compared to untreated fibres. Similarly, wood pulp and nylon 6,6 based bio-composite fibres were generated successfully by electrospinning process. In this study solution concentration was found to be a critical parameter in regulating the diameter of fibres. Bio-composite fibres were developed from wood pulp and polypropylene (PP) by an extrusion process and subsequently characterized by various techniques. Tensile properties of composite fibres were improved by addition of maleated polypropylene (MAPP) and wood pulp. Fourier transform infrared spectroscopy provided the nature of chemical interaction between wood pulp reinforcement and PP matrix. Scanning electron microscopy results revealed that MAPP treatment was effective in increasing reinforcing fibre-matrix compatibility. X-ray computed tomography showed that the fibre becomes more aligned along the length axis possibly due to compression and die geometry of the extruder. Finally, blended lignin fibres (hardwood lignin/polyethylene oxide) were successfully developed by an extrusion process. Softening temperature and glass transition temperature of lignin were measured by differential scanning calorimetry which was helpful in selecting an optimal temperature profile for the extrusion process. Rheological studies provided information about the viscosity of hardwood lignin which was useful in producing lignin fibres.