Effect of ultrastructural features on mechanical properties of softwood fiber

The main objective of this study was to develop mathematical model capable to describe the effect of ultrastructural features on the longitudinal modulus of elasticity of softwood fiber. Another objective was to identify, based on ultrastructural features, a potential explanatory factor for the mechanical difference between Norway spruce and Scots pine fibers and to demonstrate its influence utilizing developed modelling tools. According to the literature, the main difference between the pine and spruce fibers is the pit structure, which is clearly different in these fibers. The spruce fiber contains a lot of tiny pits, whereas the pits of the pine fiber are larger and the total number of them is smaller. The effect of the pits on the longitudinal modulus of elasticity of fiber is studied with both the analytical and the numerical model. The results show that, although the spruce fiber seems to contain clearly more pits, larger pits appearing in the pine fiber turn out to have a stronger influence on the longitudinal modulus of elasticity of the fiber. The effect of local variation of microfibril angle which occurs near the pits seems to be minor. Moreover, the results suggest that spruce fibers may have higher ultimate strength due to the more uniform straining behavior.

Pressurized hot water flow-through extraction of birch wood

Effective processes to fractionate the main compounds in biomass, such as wood, are a prerequisite for an effective biorefinery. Water is environmentally friendly and widely used in industry, which makes it a potential solvent also for forest biomass. At elevated temperatures over 100 °C, water can readily hydrolyse and dissolve hemicelluloses from biomass. In this work, birch sawdust was extracted using pressurized hot water (PHWE) flow-through systems. The hypothesis of the work was that it is possible to obtain polymeric, water-soluble hemicelluloses from birch sawdust using flow-through PHW extractions at both laboratory and large scale. Different extraction temperatures in the range 140–200 °C were evaluated to see the effect of temperature to the xylan yield. The yields and extracted hemicelluloses were analysed to obtain sugar ratios, the amount of acetyl groups, furfurals and the xylan yields. Higher extraction temperatures increased the xylan yield, but decreased the molar mass of the dissolved xylan. As the extraction temperature increased, more acetic acid was released from the hemicelluloses, thus further decreasing the pH of the extract. There were only trace amounts of furfurals present after the extractions, indicating that the treatment was mild enough not to degrade the sugars further. The sawdust extraction density was increased by packing more sawdust in the laboratory scale extraction vessel. The aim was to obtain extracts with higher concentration than in typical extraction densities. The extraction times and water flow rates were kept constant during these extractions. The higher sawdust packing degree decreased the water use in the extractions and the extracts had higher hemicellulose concentrations than extractions with lower sawdust degrees of packing. The molar masses of the hemicelluloses were similar in higher packing degrees and in the degrees of packing that were used in typical PHWE flow-through extractions. The structure of extracted sawdust was investigated using small angle-(SAXS) and wide angle (WAXS) x-ray scattering. The cell wall topography of birch sawdust and extracted sawdust was compared using x-ray tomography. The results showed that the structure of the cell walls of extracted birch sawdust was preserved but the cell walls were thinner after the extractions. Larger pores were opened inside the fibres and cellulose microfibrils were more tightly packed after the extraction. Acetate buffers were used to control the pH of the extracts during the extractions. The pH control prevented excessive xylan hydrolysis and increased the molar masses of the extracted xylans. The yields of buffered extractions were lower than for plain water extractions at 160–170 °C, but at 180 °C yields were similar to those from plain water and pH buffers. The pH can thus be controlled during extraction with acetate buffer to obtain xylan with higher molar mass than those obtainable using plain water. Birch sawdust was extracted both in the laboratory and pilot scale. The performance of the PHWE flow-through system was evaluated in the laboratory and the pilot scale using vessels with the same shape but different volumes, with the same relative water flow through the sawdust bed, and in the same extraction temperature. Pre-steaming improved the extraction efficiency and the water flow through the sawdust bed. The extracted birch sawdust and the extracted xylan were similar in both laboratory and pilot scale. The PHWE system was successfully scaled up by a factor of 6000 from the laboratory to pilot scale and extractions performed equally well in both scales. The results show that a flow-through system can be further scaled up and used to extract water-soluble xylans from birch sawdust. Extracted xylans can be concentrated, purified, and then used in e.g. films and barriers, or as building blocks for novel material applications.

Intensification of hemicellulose hot-water extraction from spruce wood by parameter tuning

The growing population on earth along with diminishing fossil deposits and the climate change debate calls out for a better utilization of renewable, bio-based materials. In a biorefinery perspective, the renewable biomass is converted into many different products such as fuels, chemicals, and materials, quite similar to the petroleum refinery industry. Since forests cover about one third of the land surface on earth, ligno-cellulosic biomass is the most abundant renewable resource available. The natural first step in a biorefinery is separation and isolation of the different compounds the biomass is comprised of. The major components in wood are cellulose, hemicellulose, and lignin, all of which can be made into various end-products. Today, focus normally lies on utilizing only one component, e.g., the cellulose in the Kraft pulping process. It would be highly desirable to utilize all the different compounds, both from an economical and environmental point of view. The separation process should therefore be optimized. Hemicelluloses can partly be extracted with hot-water prior to pulping. Depending in the severity of the extraction, the hemicelluloses are degraded to various degrees. In order to be able to choose from a variety of different end-products, the hemicelluloses should be as intact as possible after the extraction. The main focus of this work has been on preserving the hemicellulose molar mass throughout the extraction at a high yield by actively controlling the extraction pH at the high temperatures used. Since it has not been possible to measure pH during an extraction due to the high temperatures, the extraction pH has remained a “black box”. Therefore, a high-temperature in-line pH measuring system was developed, validated, and tested for hot-water wood extractions. One crucial step in the measurements is calibration, therefore extensive efforts was put on developing a reliable calibration procedure. Initial extractions with wood showed that the actual extraction pH was ~0.35 pH units higher than previously believed. The measuring system was also equipped with a controller connected to a pump. With this addition it was possible to control the extraction to any desired pH set point. When the pH dropped below the set point, the controller started pumping in alkali and by that the desired set point was maintained very accurately. Analyses of the extracted hemicelluloses showed that less hemicelluloses were extracted at higher pH but with a higher molar-mass. Monomer formation could, at a certain pH level, be completely inhibited. Increasing the temperature, but maintaining a specific pH set point, would speed up the extraction without degrading the molar-mass of the hemicelluloses and thereby intensifying the extraction. The diffusion of the dissolved hemicelluloses from the wood particle is a major part of the extraction process. Therefore, a particle size study ranging from 0.5 mm wood particles to industrial size wood chips was conducted to investigate the internal mass transfer of the hemicelluloses. Unsurprisingly, it showed that hemicelluloses were extracted faster from smaller wood particles than larger although it did not seem to have a substantial effect on the average molar mass of the extracted hemicelluloses. However, smaller particle sizes require more energy to manufacture and thus increases the economic cost. Since bark comprises 10 – 15 % of a tree, it is important to also consider it in a biorefinery concept. Spruce inner and outer bark was hot-water extracted separately to investigate the possibility to isolate the bark hemicelluloses. It was showed that the bark hemicelluloses comprised mostly of pectic material and differed considerably from the wood hemicelluloses. The bark hemicelluloses, or pectins, could be extracted at lower temperatures than the wood hemicelluloses. A chemical characterization, done separately on inner and outer bark, showed that inner bark contained over 10 % stilbene glucosides that could be extracted already at 100 °C with aqueous acetone.

Local Binary Patterns in Focal-Plane Processing. Analysis and Applications

Feature extraction is the part of pattern recognition, where the sensor data is transformed into a more suitable form for the machine to interpret. The purpose of this step is also to reduce the amount of information passed to the next stages of the system, and to preserve the essential information in the view of discriminating the data into different classes. For instance, in the case of image analysis the actual image intensities are vulnerable to various environmental effects, such as lighting changes and the feature extraction can be used as means for detecting features, which are invariant to certain types of illumination changes. Finally, classification tries to make decisions based on the previously transformed data. The main focus of this thesis is on developing new methods for the embedded feature extraction based on local non-parametric image descriptors. Also, feature analysis is carried out for the selected image features. Low-level Local Binary Pattern (LBP) based features are in a main role in the analysis. In the embedded domain, the pattern recognition system must usually meet strict performance constraints, such as high speed, compact size and low power consumption. The characteristics of the final system can be seen as a trade-off between these metrics, which is largely affected by the decisions made during the implementation phase. The implementation alternatives of the LBP based feature extraction are explored in the embedded domain in the context of focal-plane vision processors. In particular, the thesis demonstrates the LBP extraction with MIPA4k massively parallel focal-plane processor IC. Also higher level processing is incorporated to this framework, by means of a framework for implementing a single chip face recognition system. Furthermore, a new method for determining optical flow based on LBPs, designed in particular to the embedded domain is presented. Inspired by some of the principles observed through the feature analysis of the Local Binary Patterns, an extension to the well known non-parametric rank transform is proposed, and its performance is evaluated in face recognition experiments with a standard dataset. Finally, an a priori model where the LBPs are seen as combinations of n-tuples is also presented

Spatiotemporal Features of Coastal Waters in Southwest Finland

In coastal waters, physico-chemical and biological properties and constituents vary at different time scales. In the study area of this thesis, within the Archipelago Sea in the northern Baltic Sea, seasonal cycles of light and temperature set preconditions for intra-annual variations, but developments at other temporal scales occur as well. Weather-induced runoffs and currents may alter water properties over the short term, and the consequences over time of eutrophication and global changes are to a degree unpredictable. The dynamic characteristics of northern Baltic Sea waters are further diversified at the archipelago coasts. Water properties may differ in adjacent basins, which are separated by island and underwater thresholds limiting water exchange, making the area not only a mosaic of islands but also one of water masses. Long-term monitoring and in situ observations provide an essential data reserve for coastal management and research. Since the seasonal amplitudes of water properties are so high, inter-annual comparisons of water-quality variables have to be based on observations sampled at the same time each year. In this thesis I compare areas by their temporal characteristics, using both inter-annual and seasonal data. After comparing spatial differences in seasonal cycles, I conclude that spatial comparisons and temporal generalizations have to be made with caution. In classifying areas by the state of their waters, the results may be biased even if the sampling is annually simultaneous, since the dynamics of water properties may vary according to the area. The most comprehensive view of the spatiotemporal dynamics of water properties would be achieved by means of comparisons with data consisting of multiple annual samples. For practical reasons, this cannot be achieved with conventional in situ sampling. A holistic understanding of the spatiotemporal features of the water properties of the Archipelago Sea will have to be based on the application of multiple methods, complementing each other’s spatial and temporal coverage. The integration of multi-source observational data and time-series analysis may be methodologically challenging, but it will yield new information as to the spatiotemporal regime of the Archipelago Sea.

Continuous Counter-current Solvent Extraction of Magnesium and Calcium from Lithium-rich Brine

Solvent extraction of calcium and magnesium impurities from a lithium-rich brine (Ca ~ 2,000 ppm, Mg ~ 50 ppm, Li ~ 30,000 ppm) was investigated using a continuous counter-current solvent extraction mixer-settler set-up. The literature review includes a general review about resources, demands and production methods of Li followed by basics of solvent extraction. Experimental section includes batch experiments for investigation of pH isotherms of three extractants; D2EHPA, Versatic 10 and LIX 984 with concentrations of 0.52, 0.53 and 0.50 M in kerosene respectively. Based on pH isotherms LIX 984 showed no affinity for solvent extraction of Mg and Ca at pH ≤ 8 while D2EHPA and Versatic 10 were effective in extraction of Ca and Mg. Based on constructed pH isotherms, loading isotherms of D2EHPA (at pH 3.5 and 3.9) and Versatic 10 (at pH 7 and 8) were further investigated. Furthermore based on McCabe-Thiele method, two extraction stages and one stripping stage (using HCl acid with concentration of 2 M for Versatic 10 and 3 M for D2EHPA) was practiced in continuous runs. Merits of Versatic 10 in comparison to D2EHPA are higher selectivity for Ca and Mg, faster phase disengagement, no detrimental change in viscosity due to shear amount of metal extraction and lower acidity in stripping. On the other hand D2EHPA has less aqueous solubility and is capable of removing Mg and Ca simultaneously even at higher Ca loading (A/O in continuous runs > 1). In general, shorter residence time (~ 2 min), lower temperature (~23 °C), lower pH values (6.5-7.0 for Versatic 10 and 3.5-3.7 for D2EHPA) and a moderately low A/O value (< 1:1) would cause removal of 100% of Ca and nearly 100% of Mg while keeping Li loss less than 4%, much lower than the conventional precipitation in which 20% of Li is lost.

Excavation-drier method of energy-peat extraction reduces long-term climatic impact

Climatic impacts of energy-peat extraction are of increasing concern due to EU emissions trading requirements. A new excavation-drier peat extraction method has been developed to reduce the climatic impact and increase the efficiency of peat extraction. To quantify and compare the soil GHG fluxes of the excavation drier and the traditional milling methods, as well as the areas from which the energy peat is planned to be extracted in the future (extraction reserve area types), soil CO2, CH4 and N2O fluxes were measured during 2006–2007 at three sites in Finland. Within each site, fluxes were measured from drained extraction reserve areas, extraction fields and stockpiles of both methods and additionally from the biomass driers of the excavation-drier method. The Life Cycle Assessment (LCA), described at a principal level in ISO Standards 14040:2006 and 14044:2006, was used to assess the long-term (100 years) climatic impact from peatland utilisation with respect to land use and energy production chains where utilisation of coal was replaced with peat. Coal was used as a reference since in many cases peat and coal can replace each other in same power plants. According to this study, the peat extraction method used was of lesser significance than the extraction reserve area type in regards to the climatic impact. However, the excavation-drier method seems to cause a slightly reduced climatic impact as compared with the prevailing milling method.

VAP-1 as drug target in inflammation : structural features determining ligand interactions

Vascular adhesion protein-1 (VAP-1), which belongs to the copper amine oxidases (CAOs), is a validated drug target in inflammatory diseases. Inhibition of VAP-1 blocks the leukocyte trafficking to sites of inflammation and alleviates inflammatory reactions. In this study, a novel set of potent pyridazinone inhibitors is presented together with their X-ray structure complexes with VAP-1. The crystal structure of serum VAP-1 (sVAP-1) revealed an imidazole binding site in the active site channel and, analogously, the pyridazinone inhibitors were designed to bind into the channel. This is the first time human VAP-1 has been crystallized with a reversible inhibitor and the structures reveal detailed information of the binding mode on the atomic level. Similarly to some earlier studied inhibitors of human VAP-1, the designed pyridazinone inhibitors bind rodent VAP-1 with a lower affinity than human VAP-1. Therefore, we made homology models of rodent VAP-1 and compared human and rodent enzymes to determine differences that might affect the inhibitor binding. The comparison of the crystal structures of the human VAP-1 and the mouse VAP-1 homology model revealed key differences important for the species specific binding properties. In general, the channel in mouse VAP-1 is more narrow and polar than the channel in human VAP-1, which is wider and more hydrophobic. The differences are located in the channel leading to the active site, as well as, in the entrance to the active site channel. The information obtained from these studies is of great importance for the development and design of drugs blocking the activity of human VAP-1, as rodents are often used for in vivo testing of candidate drugs. In order to gain more insight into the selective binding properties of the different CAOs in one species a comprehensive evolutionary study of mammalian CAOs was performed. We found that CAOs can be classified into sub-families according to the residues X1 and X2 of the Thr/Ser-X1-X2-Asn-Tyr-Asp active site motif. In the phylogenetic tree, CAOs group into diamine oxidase, retina specific amine oxidase and VAP-1/serum amine oxidase clades based on the residue in the position X2. We also found that VAP-1 and SAO can be further differentiated based on the residue in the position X1. This is the first large-scale comparison of CAO sequences, which explains some of the reasons for the unique substrate specificities within the CAO family.

Utilizing hemicelluloses – the first step : controlled extraction with hot water

Människor utnyttjar ofta kemi mångsidigt i sitt vardagliga liv utan att närmare tänka på detaljerna. Nuförtiden kan man framställa en ökande mängd av produkter ur förnybara råmaterial och en av de mest mångsidiga nybara råmaterialet i Norden är barrträd. Den lyriska lägerelden eller spiselden och möbler av ved samt papper är en väsentlig del av vardagen. Också livsmedel och läkemedel kan innehålla föreningar ur ved. Ved som råmaterial består av tre huvudkomponenten: cellulosa, som är uppbyggd av druvsockermolekyler är en långkedjad, oförgrenad polymer; lignin, som sammanhåller fibrerna i vedmaterialet som lim samt hemicellulosor, som ofta är uppbyggda av olika sockerarter och är en förgrenad polymer. Följaktligen består vedmaterialet av 70 % socker. I detta arbete har vi koncentrerat på i hemicellulosa och dess extraktion ur gran, samt bestämning av hemicellulosans egenskaper. Den slutliga målsättningen i forskningen var att skapa nya produkter ur gran. Forskning i extraktionens hemligheter eller hur hemicellulosa kan effektivt extraheras i den önskade formen kräver nya typers experimentellasanläggningar och experiment samt matematisk modellering. Den långkedjade hemicellulosan är lämplig för att användas t.ex. i skyddshinnor eller i livsmedel. Medel- och småmolekylär hemicellulosa kan användas som utgångsämne för framställning av bränslen, smörjmedel, sockersyror och alkoholer, av vilka xylitol är mest känd för alla pga hälsobefrämjande effekter. Det är utomordentligt viktigt ur miljöns och energiekonomins synvinkel att sträva efter effektivering av utnyttjandet av den värdefullaste och största naturtillgången, skogen i vårt land, med alla möjliga sätt. Resultaten av denna forskning utnyttjar avsevärt den växande, nya, på skogen baserande biobaseradeindustrin, som framställer nya spetsprodukter samt skapar nya arbetsplatser. ----------------------------------------------------- Ihmiset hyödyntävät usein huomaamattaan kemiaa monipuolisesti jokapäiväisessä elämässä. Nykyään kasvava määrä tuotteista kyetään valmistamaan uusiutuvista raaka-aineista ja yksi monipuolisimmista uusiutuvista luonnonvaroistamme pohjolassa ovat havupuut. Tunnelmallinen nuotio tai takkatuli ja puiset huonekalut sekä paperi ovat olennainen osa arkea. Myös elintarvikkeet ja lääkkeet voivat sisältää puusta peräisin olevia yhdisteitä. Puu materiaalina koostuu rakenteeltaan pääosin kolmesta osasta; selluloosasta, joka on rypälesokerista koostuva pitkäketjuinen haaroittumaton polymeeri, ligniinistä, joka toimii puun koossa pitävänä liima-aineena ja hemiselluloosasta, joka on useista eri sokereista rakentunut haaroittunut polymeeri. Näin ollen puusta 70 % on sokeria. Tässä työssä olemme keskittyneet hemiselluloosaan ja sen uuttamiseen kuusesta, sekä ominaisuuksien kartoittamiseen. Tutkimusaiheen lopullinen tavoite on luoda uusia tuotteita kuusesta. Uuton salojen tutkiminen eli miten hemiselluloosa saadaan tehokkaasti uutettua halutunlaisena vaatii uudenlaisia koelaitteistoja ja kokeita, sekä matemaattista mallintamista. Suurikokoinen hemiselluloosa on sopivaa käytettäväksi esimerkiksi suojakalvoissa tai elintarvikkeissa. Keskikokoista ja pienimolekyylistä hemiselluloosaa voidaan käyttää lähtöaineena valmistettaessa polttoaineita, voiteluaineita, sokerihappoja ja sokerialkoholeja, joista xylitoli on terveysvaikutustensa vuoksi kaikille tuttu. Niin ympäristömme kuin myös energiataloutemme kannalta on ensiarvoisen tärkeää pyrkiä kaikin keinoin tehostamaan maallemme arvokkaan, sekä luonnonvaroistamme yhden suurimman, metsän, vastuullista hyödyntämistä. Tämän tutkimuksen tulokset hyödyntävät merkittävästi maahamme nousevaa uutta metsään pohjautuvaa biojalostusteollisuutta, joka valmistaa uusia huipputuotteita sekä luo työpaikkoja.

The role of product features on buyer-supplier collaboration in packaging industry

The thesis presents the study relative to the collaboration between suppliers and buyers in packaging industry with the impact of product features. The main purpose of this study is to examine the importance of product characteristics on collaboration to develop better packaging and to figure out how buyer-supplier collaboration in the supply chain perspectives is conducted and managed in packaging industry. The theoretical part reviewed some basic frameworks of collaboration including the scopes and levels of collaboration, risks as well as powers of collaboration, relationship and some key factors for successful collaboration. Followed by the overviews of packaging industry with the main issues related to product characteristics in packaging. By using the qualitative method, secondary data consisting of articles, reports, websites and primary data through interviewing some well-known packaging companies and case companies are collected in the thesis. The empirical result emphasized the importance of product features’ analysis in packaging industry since it plays a central role in the materials, design process, production and innovation with the role of collaboration. Collaboration in packaging is vital for packaging companies to survive and grow in the competitive environment. Finally, some key factors for effective collaboration were summarized based on the perspectives of packaging companies. It is highly recommend building a long-run collaboration with their customers due to undeniable benefits With increasingly importance of collaboration in packaging industry, further studies may be conducted.