Thesis (MEng)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Pulp and paper mills are being placed under increasing pressure to maximise the use of the biomass being processed for pulp, and move towards integrated biorefineries (IFBRs), where a diverse range of products can be produced and not just pulp exclusively. Extracting hemicelluloses prior to the pulping process could increase the profitability of the mills as the hemicelluloses could be used to produce a number of additional products. Hemicelluloses are a plant polysaccharides with the most abundant hemicellulose in hardwoods being xylan, with xylose being the primary monosaccharide constituent of xylan. The majority of pulps produced in the Southern Hemisphere are done with hardwoods as feedstock, typically with the Kraft process. The attraction of the concept of extracting hemicellulose prior to pulping is further augmented by the fact that hemicellulose is underutilised in the Kraft process. In the Kraft process the hemicellulose is dissolved during pulping and burned along with lignin for the production of energy, however, hemicellulose has about half the heating value when compared to that of lignin. The main objective of this study was to find a pre-extraction method that is effective in releasing xylan from Eucalyptus grandis, the most important hardwood feedstock used for pulping in the Southern Hemisphere. The method also needs to be practical in terms of integrating it into the Kraft process and should have a minimal effect on pulp yield and subsequent paper qualities. Xylan extractions from E. grandis as feedstock were carried out with white liquor, green liquor and NaOH. Green liquor is the dissolved smelt originating from the recovery boiler in the Kraft process and consists mainly sodium carbonate and sodium sulphide. White liquor’s principal components include sodium hydroxide and sodium sulphide and is used in the digesters during the pulping stage of the Kraft process. NaOH is a make up chemical used in the Kraft process. These chemicals were chosen since they are all already present within the Kraft process. The suitability of these chemicals as xylan extraction methods is further bolstered by the fact that their alkalinity may actually reduce chemical usage in pulping. This provides scope for integration of hemicellulose extraction into Kraft pulping without implementing major changes to the existing industrial process. Moreover, alkali chemicals for pre-extraction allow for minimal effect on resulting pulp and paper. In terms of the extracted product, the alkaline conditions provided by these chemicals create conditions that are suitable for a high degree of polymerisation of hemicelluloses. Xylan pre-extracted chips from selected extraction conditions were subjected to varying pulping conditions, to replicate pulp yields and properties obtained with untreated E. grandis chips when using conventional pulping. Handsheets were also produced from the pulps produced under the highest pulp yield conditions, and these were tested for pulp quality properties. Furthermore, mass balances were performed to gauge the impact that hemicellulose pre-extraction would have using green liquor, white liquor and NaOH on the sodium and sulphur balances of the mill. From the extractions performed, the highest fraction of xylan recovered was 15.15% w/w utilising 2M NaOH, at 120°C for 90 minutes extraction time. This was followed by white liquor extraction at 13.27% w/w utilising 20% AA at 140°C for 90 minutes. Green liquor extraction produced the lowest xylan recovery at 7.83% w/w with 2% TTA and 160°C with an h-factor of 800. The residues from selected extraction conditions were utilised for these pulping optimisation experiments. Selected extraction conditions used for further pulping included 2% TTA and 160°C for green liquor, 20% AA and 120°C and 140°C extraction temperature for white liquor, as well as 2M concentration and 120°C for NaOH. The highest yielding pulping conditions were achieved with a 35% reduction in pulping chemicals and 45 minutes pulping time in combination with green liquor pre-extraction, while for pulping combined with white liquor pre-extraction a 50% reduction in chemicals and 30 minute pulping time was preferred. For pulping subsequent to NaOH pre-extraction a 75% reduction in the NaOH dosage and a 45 minute pulp time was preferred. All pulp steps were performed at 170°C. Unbeaten handsheets produced from the selected pulping conditions for white liquor and green liquor extracted chips showed similar physical properties (burst, tear, tensile indices) when compared to the control (pulps from non-extracted chips). However the greater quantity of xylan removed from cellulose fibres with NaOH extraction, resulted in pulps with lower xylan contents, which affected the burst and tear indices of the handsheets formed from these pulps. An increase in tear, while a reduction in the burst index, was observed for the pulp produced from NaOH extracted chips. It was concluded that although white liquor and NaOH extraction allows for greater xylan recovery, the large chemical expenditure associated with these methods will impose significant cost impacts on the existing Kraft process. From mass balances performed, green liquor xylan extraction due to its lower alkalinity, will be more forgiving in terms of additional make up chemical costs. It also allowed for minimum effect on both the pulp and paper quality, thus making it the most practical of the pre-extraction methods. However, whether the additional make chemicals required for the green liquor extraction method will be justified by the quantity of xylan extracted will only be answered by a thorough economic assessment, which was not in the scope of this project. / AFRIKAANSE OPSOMMING: Pulp- en papiermeule word onder toenemende druk geplaas om die gebruik van die biomassa wat vir pulp verwerk word, te maksimaliseer, en om te beweeg na geïntegreerde bioraffinaderye, waar ʼn groot verskeidenheid produkte vervaardig kan word, en nie slegs uitsluitlik pulp nie. Die ekstraksie van hemisellulose voor die verpulpingsproses kan die winsgewendheid van die meule verhoog, aangesien die hemisellulose gebruik kan word vir die vervaardiging van verskeie bykomende produkte. Hemisellulose is ʼn plantpolisakkaried, met xilaan as die hemisellulose wat die oorvloedigste in hardehout gevind word, en met xilose as die primêre monosakkaried-bestanddeel van xilaan. Die meerderheid van die pulp wat in die Suidelike Halfrond geproduseer word, word met hardehout as voerstof gedoen, tipies met behulp van die Kraft-proses. Die aanloklikheid van die konsep om hemisellulose voor verpulping te win, word verder versterk deur die feit dat hemisellulose in die Kraft-proses onderbenut word. In die Kraft-proses word die hemisellulose tydens verpulping opgelos en saam met lignien verbrand vir die opwekking van energie, maar hemisellulose het egter ongeveer die helfte van die verhittingswaarde van dié van lignien. Die vernaamste doelstelling van hierdie studie was om ʼn pre-ekstraksiemetode te vind wat xilaan doeltreffend van Eucalyptus grandis, die belangrikste hardhout-voerstof wat in die Suidelike Halfrond vir verpulping gebruik word, kan vrystel. Die metode moet ook prakties wees met betrekking tot integrering met die Kraft-proses, en dit moet ʼn minimale uitwerking op pulpopbrengs en gevolglike papiergehalte hê. Xilaan-ekstraksie uit E. grandis as voerstof is uitgevoer met wit loog, groen loog en NaOH. Hierdie chemikalieë is gekies omdat hulle reeds in die Kraft-proses teenwoordig is. Die geskiktheid van hierdie chemikalieë as xilaan-ekstraksiemetodes is verder ondersteun deur die feit dat hul alkaliniteit moontlik chemiese verbruik in verpulping kan verlaag, wat ruimte vir die integrasie van hemisellulose-ekstraksie in Kraft-verpulping laat sonder om grootskaalse veranderinge aan bestaande nywerheidsprosesse te implementeer. Alkali-chemikalieë vir preekstraksie lei boonop tot ʼn minimale uitwerking op resultante pulp en papier, terwyl die alkalitoestande, met betrekking tot die geëkstraheerde produk, toestande skep wat geskik is vir ʼn hoë mate van polimerisasie van hemisellulose. Uit die ekstraksies wat uitgevoer is, is die hoogste fraksie xilaan gewin deur die gebruik van NaOH teen 15.15% w/w met 2M NaOH, teen 120 °C vir 90 minute ekstraksietyd. Dit is gevolg deur witloog-ekstraksie teen 13.27% w/w met die gebruik van 20% AA teen 140 °C vir 90 minute. Groenloog-ekstraksie het die laagste xilaan-winning teen 7.83% w/w met 2% TTA en 160°C met ʼn h-faktor van 800 voortgebring. Houtspaanders wat aan xilaan-pre-ekstraksie met groen loog onderwerp is, het pulp met kappanommers en opbrengste soortgelyk aan dié van nie-geëkstraheerde spaanders voortgebring toe die chemiese lading met 35% verlaag is, in verhouding tot dít wat vir niegeëkstraheerde spaanders gebruik is. Xilaan-pre-geëkstraheerde spaanders met wit loog het ʼn 50%-vermindering in verpulpingschemikalieë gelewer in verhouding tot houtspaanders wat aan konvensionele verpulping onderwerp is. Die chemiese reduksie van groen loog was minder as dié van wit loog weens die laer alkalilading wat tydens hemisellulose-ekstraksie voor verpulping gebruik is. Vir witloog-ekstraksie kon pulpopbrengste gehandhaaf word, alhoewel pregeëkstraheerde spaanders met wit loog ʼn neiging getoon het om pulp met laer kappanommers voort te bring. Alhoewel pulp wat uit houtspaanders gemaak is wat aan NaOH-ekstraksie onderwerp is, gelei het tot ʼn 75%-vermindering van NaOH gebruik in verhouding tot dié van konvensionele verpulping, is verwag dat geen NaOH benodig sou word nie, aangesien die houtspaanders reeds tydens xilaan-ekstraksie aan 2M NaOH blootgestel is. Voorts, in die literatuur is verpulping uitgevoer ná 2M NaOH-ekstraksie sonder dat die toevoeging van NaOH tydens verpulping nodig was [61]. Handvelle is vervaardig uit die pulp wat in die hoogste pulpopbrengs-toestande vervaardig is, en dit is vir pulpgehalte-eienskappe getoets. Die verpulpingstoestande met die hoogste opbrengs is bereik met ʼn 35%-vermindering van verpulpingschemikalieë en 45 minute verpulpingstyd in kombinasie met groenloog-pre-ekstraksie, terwyl vir verpulping met witloogpre- ekstraksie ʼn 50%-vermindering van chemikalieë en 30 minute verpulpingstyd verkies is. Vir verpulping ná NaOH-pre-ekstraksie is ʼn 75%-vermindering van die NaOH-dosis en 45 minute verpulpingstyd verkies. Alle verpulpingstappe is teen 170°C uitgevoer. Ongeklopte handvelle vervaardig uit die gekose verpulpingstoestande vir witloog- en groenloog- geëkstraheerde spaanders het soortgelyke fisiese eienskappe getoon (bars-, skeuren trek-indeks) in vergelyking met die kontrole (pulp uit nie-geëkstraheerde spaanders). Die grootste hoeveelheid xilaan is egter uit sellulose vesel met NaOH-ekstraksie verkry, wat gelei het tot pulp met laer xilaaninhoud, wat die bars- en skeur-indeks van die handvelle wat uit hierdie pulp vervaardig is, beïnvloed het. ʼn Toename in die skeur-indeks, met ʼn afname in die bars-indeks, is waargeneem vir die pulp wat uit NaOH-geëkstraheerde spaanders vervaardig is. Die gevolgtrekking is gemaak dat alhoewel witloog- en NaOH-ekstraksie groter xilaanwinning moontlik maak, die groot chemiese uitgawe geassosieer met hierdie metode ʼn aanmerklike koste-impak vir die bestaande Kraft-proses inhou. Groenloog-xilaanekstraksie sal, weens die laer alkaliniteit, meer geskik wees met betrekking tot die koste van bykomende aanvullende chemikalieë. Dit hou ook ʼn kleiner uitwerking op die pulp- en papiergehalte in, wat dit dus die praktieste van die pre-ekstraksiemetodes maak. Of die bykomende chemikalieë nodig vir die witloog- en NaOH-ekstraksies egter geregverdig kan word deur die hoeveelheid xilaan wat gewin is, kan slegs deur ʼn deeglike ekonomiese assessering beantwoord word, wat nie binne die omvang van hierdie projek geval het nie.

The recovery and recycling of the spent chemicals from the kraft pulping process are economically and environmentally essential in an integrated kraft pulp and paper mill. The recovery process can be optimised by firing high-solids black liquor in the recovery boiler. Unfortunately, due to a corresponding increase in the liquor viscosity, in many mills, black liquor is fired at reduced solids concentration to avoid possible rheological problems. Online measurement, monitoring and control of the liquor viscosity are deemed essential for the recovery boiler optimization. However, in most mills, including those in New Zealand, black liquor viscosity is not routinely measured. Four batches of black liquors having solids concentrations ranging between 47 % and 70 % and different residual alkali (RA) contents were obtained from Carter Holt Harvey Pulp and Paper (CHHP&P), Kinleith mill, New Zealand. Weak black liquor samples were obtained by diluting the concentrated samples with deionised water. The viscosities of the samples at solids concentrations ranging from 0 to 70 % were measured using open-cup rotational viscometers at temperatures ranging from 0 to 115 oC and shear rates between 10 and 2000 s-1. The effect of post-pulping process, liquor heat treatment (LHT) on the liquors’ viscosities was investigated in an autoclave at a temperature >=180 oC for at least 15 mins. The samples exhibit both Newtonian and non-Newtonian behaviours depending on temperature and solids concentration; the onsets of these behaviours are liquor-dependent. In conformity with the literature data, at high solids concentrations (> 50 %) and low temperatures, they exhibit shear-thinning behaviour with or without thixotropy but the shear-thinning/thixotropic characteristics disappear at high temperatures (>= 80 oC). Generally, when the apparent viscosities of the liquors are <= ~1000 cP, the liquors show a Newtonian or a near-Newtonian behaviour. These findings demonstrate that New Zealand black liquors can be safely treated as Newtonian fluids under industrial conditions. Further observations show that at low solids concentrations (< 50 %), viscosity is fairly independent of the RA content; however at solids concentrations > 50 %, viscosity decreases with increasing RA content of the liquor. This shows that the RA content of black liquor can be manipulated to control the viscosity of high-solids black liquors. The LHT process had negligible effect on the low-solids liquor viscosity but led to a significant and permanent reduction of the high-solids liquor viscosity by a factor of at least 6. Therefore, the incorporation of a LHT process into an existing kraft recovery process can help to obtain the benefits of high-solids liquor firing without a concern for the attending rheological problems. A variety of the existing and proposed viscosity models using the traditional regression modelling tools and an artificial neural network (ANN) paradigm were obtained under different constraints. Hitherto, the existing models rely on the traditional regression tools and they were mostly applicable to limited ranges of process conditions. On the one hand, composition-dependent models were obtained as a direct function of solids concentration and temperature, or solids concentration, temperature and shear rate; the relationships between these variables and the liquor viscosity are straight forward. The ANN-based models developed in this work were found to be superior to the traditional models in terms of accuracy, generalization capability and their applicability to a wide range of process conditions. If the parameters of the resulting ANN models can be successfully correlated with the liquor composition, the models would be suitable for online application. Unfortunately, black liquor viscosity depends on its composition in a complex manner; the direct correlation of its model parameters with the liquor composition is not yet a straight forward issue. On the other hand, for the first time in the Australasia, the limitations of the composition-dependent models were addressed using centrifugal pump performance parameters, which are easy to measure online. A variety of centrifugal pump-based models were developed based on the estimated data obtained via the Hydraulic Institute viscosity correction method. This is opposed to the traditional approaches, which depend largely on actual experimental data that could be difficult and expensive to obtain. The resulting age-independent centrifugal pump-based model was implemented online as a black liquor viscosity soft sensor at the number 5 recovery boiler at the CHHP&P, Kinleith mill, New Zealand where its performance was evaluated. The results confirm its ability to effectively account for variations in the liquor composition. Furthermore, it was able to give robust viscosity estimates in the presence of the changing pump’s operating point. Therefore, it is concluded that this study opens a new and an effective way for kraft black liquor viscosity sensor development.

The aim of this paper is to compare the subject-specific concepts and their use in two chapters dealing with the subject force in two different physics textbooks for grades 4-6. To achieve the aim, the following questions have been formulated: What subject-specific concepts are used and how often? What representations are used to clarify the subject-specific concepts? To achieve the purpose and the issues raised in the paper, the chapter will be analysed with two different content analysis. The material will then be analysed based on Vygotsky's theory of the development of scientific concepts. The results show that both chapters have about as many subject-specific concepts in comparison to the rest of the words in the chapters. One of the chapters show greater variety of representations with different contexts than the second chapter. Both chapters have used everyday contexts when the subject-specific concepts were explained, but one of the chapters show that different contexts were used depending on the subject-specific concepts.

Kraft pulping, also known as sulphate pulping is a complex process where the wood components are liberated from each other facilitated by chemical reactions. During the pulping process some dissolved and degraded compounds end up together with the spent cooking chemicals in the black liquor. In kraft pulping of hardwood, the black liquor contains substantial amounts of dissolved hemicellulose, especially xylan due to the wood composition. The xylan content is of high value due to its ability to re-deposit by adsorption on cellulose fibres and its tendency to increase pulp strength and yield. In this work, the possibility of introducing xylan rich, hardwood black liquor from the hardwood digester into the softwood digester at the process of SCA – Munksund was studied. The objective was to investigate if hardwood black liquor addition in a softwood cook can increase the yield and pulp strength. The theoretical feasibility of altering the process was investigated by a literature review and a brief process investigation. During the study a total of eight lab cooks were conducted to obtain information on how hardwood black liquor addition changes the pulp quality of regular softwood cooks. The wood chips, white liquor and hardwood black liquor used were collected at Munksund and the process conditions in the lab cooks were chosen to simulate the actual process in the Munksund mill. In addition to the cooking, chemical and physical evaluation on pulps, cooking liquors and wood chips were performed. The theoretical evaluation indicates that the process in Munksund is well suited for introducing the hardwood black liquor in to the softwood digester. The chemical analysis of the black liquors show a xylan content that is approximately four times higher in the hardwood black liquor compared to the softwood black liquor. In the kappa number range of approximately 80-90, a total yield increase of 0.4%-units was obtained for two cooks with hardwood black liquor addition compared to their corresponding reference cooks. A carbohydrate analysis showed a higher xylan content in the pulp cooked with addition of hardwood black liquor compared to the corresponding reference pulp. One pulp with hardwood black liquor addition and its corresponding reference cook were refined in an Escher Wyss lab mill. The pulp with hardwood black liquor addition exhibits an increase or retained strength for all strength evaluation tests made on handmade pulp sheets. Strength increases of approximately 5% were obtained for tensile index and ISO-Z strength for a pulp with hardwood black liquor addition.   The results conducted in this study shows that it can be possible to slightly increase both the yield and some pulp strength parameters when adding hardwood black liquor in to the softwood cook in lab scale. It is also shown that the increase in the total yield most likely depends on xylan adsorption on the cellulose fibres. The calculated increased revenue for this process change could be over 400 000 Euro per year.

In der vorliegenden Arbeit wurde der fließregulierende Effekt diverser hochdisperser Fällungskieselsäuren vom Typ SIPERNAT® (Evonik Degussa GmbH) auf die Fließeigenschaften kohäsiver Schüttgüter untersucht. Der Wirkmechanismus dieser nanostrukturierten Fließregulierungsmittel beruht bei trockenen und elektrostatisch nicht aufgeladenen Pulvern vorwiegend auf der Reduktion von van-der-Waals-Kräften durch Adsorption kleinerer Aggregate des Fließregulierungsmittels an die Oberfläche der Schüttgutpartikel und somit Vergrößerung des Abstandes bzw. Verkleinerung der Kontaktflächen zwischen den Trägerpartikeln. Durch unterschiedlich langes Mischen von Fließregulierungsmitteln mit kohäsiven Schüttgütern verändert sich sowohl die Anzahl adsorbierter Nanopartikel als auch die Größe, Größenverteilung und Form der Adsorbate, was in unterschiedlichen Fließeigenschaften der Mischungen resultiert. Zur Untersuchung des Zusammenhanges zwischen Oberflächenbelegung durch Adsorbate und Fließeigenschaften einer Mischung wurde Maisstärke, die als kohäsives Modellschüttgut fungierte, eine konstante Menge Fließregulierungsmittel zugesetzt und die Mischungen unterschiedlich langen Mischzeiten in einem Freifallmischer unterzogen. Die aus dem Mischprozeß resultierende Belegung der Maisstärkeoberfläche durch Adsorbate wurde mittels Rasterelektronenmikroskop mit anschließender bildanalytischer Auswertung (KL 300®, Carl Zeiss) charakterisiert. Die Fließeigenschaften der Mischungen wurden mit einem Zugspannungstester, einem modifizierten Auslauftrichter sowie Hausner-Faktor untersucht. Es konnte gezeigt werden, daß sich die Fließeigenschaften mit steigender Mischzeit kontinuierlich bis zum Erreichen eines Optimums verbessern. Dies wird mit der Abnahme der Adsorbatgrößen und der Zunahme der Adsorbatanzahl auf der Maisstärkeoberfläche erklärt. Bei kurzen Mischzeiten bewirken adsorbierte Fließregulierungsmittelaggregate eine Verbesserung der Fließeigenschaften durch Verhinderung direkter Kontakte zwischen den Schüttgutpartikeln. Bei weiterer Zunahme der Oberflächenbelegung werden die Fließeigenschaften durch einen Übergang von Träger-Adsorbat-Träger-Kontakten zu Träger-Adsorbat-Adsorbat-Träger-Kontakten verbessert. Eine beobachtete Verschlechterung der Fließeigenschaften nach Überschreiten der optimalen Mischzeit beruht wahrscheinlich auf einer Veränderung der dreidimensionalen Form der Adsorbate, die zu einer Vergrößerung der Kontaktflächen führt. Beim Vergleich der unterschiedlichen Messmethoden zur Ermittlung der Fließeigenschaften wurde ersichtlich, dass die Messparameter des modifizierten Auslauftrichters gut mit dem Hausner-Faktor korrelieren, während die Zugspannungsmessungen z.T. abweichende Ergebnisse lieferten. Eine genaue Analyse des Messvorgangs am Zugspannungstester zeigte, dass die Pulverproben bei der verwendeten Messmethode (Messung mit konstanter Vorlast) in Abhängigkeit von ihren Fließeigenschaften unterschiedlich stark durch den Messvorgang verdichtet werden, was Einfluss auf die gemessenen Zugspannungswerte hatte. Aus dieser Erkenntnis konnten Verbesserungsvorschläge für die Zugspannungsmessung an Schüttgütern gemacht werden. / The flow enhancing effect of different high dispersive precipitated silica (SIPERNAT®, Evonik Degussa GmbH) on cohesive bulk powder was investigated. The working mechanism of these flow regulators in dry and not highly electrified powders is based on the reduction of van der Waals forces by adsorption on the surface of the cohesive bulk particles and thus increasing the particle distance and reducing the contact area. Variation of the blending time of the cohesive bulk powder with the flow regulator causes a differing number, size, size distribution and shape of the adsorbates on the surface of the bulk powder which results in different flow properties of the mixtures. To investigate the relationship between surface coverage and flow properties, binary mixtures of corn starch and flow additive were prepared and submitted to different mixing times in a free fall mixer. The resulting surface coverage was analyzed by scanning electron microscopy with employment of an image analyzing program (KS 300®, Carl Zeiss). The flow properties of the mixtures were investigated by a tensile strength tester, a modified outflow funnel and measurement of the Hausner-Ratio. It was demonstrated, that the flow properties are improved steadily with blending time until an optimum is reached. This is explained by the increase of the number of adsorbates on the surface of the bulk particles and the diminution of the adsorbat sizes during the mixing process. At short mixing times the enhancement of flow properties is mainly due to the prevention of direct contacts between the bulk particles by adsorbates of the flow regulator. At higher surface coverage a further improvement of flow properties is caused by transition from particle-adsorbate-particle contacts into particle-adsorbat-adsorbat-particle contacts. The observed worsening of flow properties after exceeding the optimal blending time is probably caused by a flattening of the adsorbates which results in an increase of contact areas. Comparison of the different methods to assign the flow properties revealed, that the measuring parameters of the modified outflow funnel correlate well with the Hausner-Ratio, whereas the tensile strength showed in part deviant results. An analysis of the measuring procedure of the tensile strength tester showed, that the powder samples were differently consolidated by the measuring procedure in dependence on their flow properties, which influenced the tensile strength results. Based on this finding some suggestions for improvement of the measuring procedure with the tensile strength tester were made.

O uso de recursos florestais e madeireiros como cargas em matrizes poliméricas pode originar novos materiais com forte apelo ecológico e econômico. Dentre os resíduos do processamento mecânico e químico da madeira, há uma série de materiais de fácil acesso que podem ser manipulados a partir de certas técnicas de biorrefinaria, tais como a madeira, a casca de madeira, as pinhas (frutos do pinus), as acículas (folhas do pinus), a lignina residual (processo kraft) e o lodo de papel derivadas do processo químico de polpação celulósica. Tais matérias primas foram incorporadas em espumas rígidas e semi-rígidas de poliuretano (PU) processadas pelo método da expansão livre, utilizando-se uma mistura de óleo de mamona e glicerina loira como biopoliol, com vistas a obtenção de espumas quimicamente estáveis e ecologicamente corretas. A compatibilidade de algumas dessas cargas no sistema PU foi testada mediante reações induzidas na presença de isocianato e catalisador. As espumas PU foram caracterizadas por meio de técnicas de microscopia e espectroscopia, além de ensaios mecânicos, térmicos, higroscópicos, óticos, de resistência a chamas e de resistência à radiação UV. Por fim, foi avaliado o efeito de expansões sob confinamento nas propriedades morfológicas, mecânicas e térmicas do PU puro e de uma espuma carregada PU/madeira As espumas apresentaram estabilidade química e a inserção das cargas no PU puro possibilitou a obtenção de espumas com células homogêneas, melhor desempenho higroscópico, níveis similares de condutividade térmica e flamabilidade, além de maior brilho e diferentes padrões de cor. A farinha de madeira apresentou a maior afinidade com o sistema PU, seguida pela lignina kraft, resultando em espumas carregadas com células menores, mais arredondadas e com maior teor de células fechadas, além de espumas com maiores estabilidades térmica e dimensional. Todas as espumas apresentaram fotodegradações similares, marcadas por uma cor alaranjada, acompanhada por uma acentuada perda de brilho. As espumas carregadas naturalmente mais escuras foram mais resistentes à fotodegradação por serem capazes de causar um efeito contrário ao da descoloração natural do PU quando sujeito aos raios UV. O confinamento diminuiu o diâmetro médio de células da espuma PU/madeira e a anisotropia do PU puro, levando a formação de células mais homogêneas, marcadas por números de arestas rompidas e de células abertas aparentemente menores, que resultaram em maiores densidades aparentes e melhores propriedades mecânicas para espumas preparadas a 50% de confinamento e menor condutividade térmica para as espumas confinadas a 70%. / The use of forestry and wood-based resources as fillers in polymer matrices may originate new materials with strong environmental and economic appeals. Among the wastes from chemical and mechanical processing of wood, there are many materials readily available, which can be handled through biorrefinary techniques, like wood flour, wood bark, pine cones (fruits), pine needles (leaves), residual lignin (e.g. from kraft process) and paper sludge, the last two from the chemical processing of cellulosic pulp. In this thesis, such raw materials were incorporated into rigid and semi-rigid polyurethane (PU) foams prepared by the free-rising pouring method, using a mixture of castor oil and crude glycerin as a bio-based polyol in order to achieve chemically stable and eco-friendly foams. Compatibility of the fillers with the PU system was evaluated using induced reactions in the presence of isocyanate and catalyst. The PU foams were characterized by microscopy and spectroscopy techniques, as well as mechanical, thermal, hygroscopic, optical, flame resistance and UV radiation resistance tests. And the effect of rising under confinement on the morphological, mechanical and thermal properties of neat PU and wood/PU foam composites was also investigated The foams presented chemical stability and the addition of fillers into PU yielded foams with more homogeneous cells, better hygroscopic performance, similar thermal conductivities and flammabilities, as well as higher specular glosses and different colorimetric patterns. The wood flour presented the highest affinity with the PU system, followed by kraft lignin, resulting in foam composites with smaller and more rounded cells, with higher closed-cells content, and increased thermal and dimensional stabilities. All foams presented similar photodegradation behavior characterized by an orange color and a significant loss in specular gloss. The foam composites, being naturally darker, were more resistant to photodegradation, since they had an opposite effect related to natural discoloration under UV radiation. The confinement decreased cell diameter for the wood filled PU foam and the anisotropy index for neat PU foam, yielding more homogeneous cells, with fewer broken edges and open-cells, with greater apparent densities and better mechanical properties for foams prepared at 50% confinement and lower thermal conductivity for foams confined at 70%.

This bachelor’s thesis was conducted in collaboration with Arvika Kraft AB and its purpose was to improve their hydropower station that is located in Rexed. During the last couple of years this specific hydropower station has had vast amounts of mechanical problems, mainly with their gearbox. The result of this has been that the hydropower station has been stationary over long periods of time. At the same time this has resulted in that the hydropower station only opens their turbine’s vanes to 80% of its maximum capability to try to avoid the recurring mechanical problems. By only opening the turbine vanes to 80% the incoming water flow is reduced, which in turn also reduces the amount on electricity that can be produced. The goal with this bachelor’s thesis has been to find a more economically beneficial solution than the one that is present in today’s hydropower station. It should also be noted that this thesis will only look into the possibility of changing the hydropower stations gearbox and generator. The turbine will not be dealt with in this thesis. Historical- and hydrological data has been analyzed so that the efficiency and a possible increase in the production of electricity for the hydropower station in Rexed could be calculated. This result was then compared with alternative solutions that were offered by Transmissionsservice in Jönköping through several investment calculations. The concept that was the most economically beneficial for the hydropower station in Rexed was exchanging the current gearbox for the one that Transmissionsservice in Jönköping had offered. This solution resulted in an increase of the produced electricity from 2 100 MWh up to approximately 3 000 – 3 400 MWh. With a price on electricity of 300 kr/MWh it generated an increase of income of 270 000 – 390 000 kr per year. The investment of 1 500 000 kr, for the new gearbox plus installation fees, is beneficial with an IRR of 5%. From the investment calculations it can also be found that an investment up to 5 000 000 kr still is economically beneficial, since the IRR is higher than the cost of capital, for Arvika Kraft AB. Before Arvika Kraft AB decides if the investment will be made or not they should investigate the possibility of receiving a certificate for their hydropower station. By reconstructing this hydropower station they could receive this certificate, which would increase the income price of the electricity produced by 50% for 15 years (or until the year 2035 if the reconstructed after 2020). With 3 000 – 3 400 MWh of electricity produced this certificate would allow for an investment up to 8 500 000 kr and still be economically beneficial, with an IRR of 5%, for Arvika Kraft AB.

<p>This essay describes how theatre can be a tool in social work. The essay evaluates the Swed-ish KRAFT-project, a course for unemployed people with the goal to make them grow as in-dividuals by using drama exercises and performing a theatre play in front of an audience. The essay is a quantitative secondary study of the questionnaire used in the KRAFT-project. Through analysing the questionnaire the participants answered this essay tries to explain the results from a social psychological perspective. The essay also discusses how the participants’ self-concept and self-esteem could have been affected by the KRAFT-project. The discussion generates several new hypothesis concerning this issue. The results of this study can not be generalised to other projects using theatre or drama as a tool for personal development but it describes an example of how it can be used as a method in social work.</p>

<p>The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin.</p><p>Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.</p><p> </p><p>The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.</p><p> </p><p>The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.</p><p> </p><p>The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.</p>

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