Mathematical modeling of laboratory scale three-phase fixed bed reactors

Detta arbete fokuserar på modellering av katalytiska gas-vätskereaktioner som genomförs i kontinuerliga packade bäddar. Katalyserade gas-vätskereaktioner hör till de mest typiska reaktionerna i kemisk industri; därför behandlas här packade bäddreaktorer som ett av de populäraste alternativen, då kontinuerlig drift eftersträvas. Tack vare en stor katalysatormängd per volym har de en kompakt struktur, separering av katalysatorn behövs inte och genom en professionell design kan den mest fördelaktiga strömningsbilden upprätthållas i reaktorn. Packade bäddreaktorer är attraktiva p.g.a. lägre investerings- och driftskostnader. Även om packade bäddar används intensivt i industri, är det mycket utmanande att modellera. Detta beror på att tre faser samexisterar och systemets geometri är komplicerad. Existensen av flera reaktioner gör den matematiska modelleringen även mera krävande. Många förenklingar blir därmed nödvändiga. Modellerna involverar typiskt flera parametrar som skall justeras på basis av experimentella data. I detta arbete studerades fem olika reaktionssystem. Systemen hade studerats experimentellt i vårt laboratorium med målet att nå en hög produktivitet och selektivitet genom ett optimalt val av katalysatorer och driftsbetingelser. Hydrering av citral, dekarboxylering av fettsyror, direkt syntes av väteperoxid samt hydrering av sockermonomererna glukos och arabinos användes som exempelsystem. Även om dessa system hade mycket gemensamt, hade de också unika egenskaper och krävde därför en skräddarsydd matematisk behandling. Citralhydrering var ett system med en dominerande huvudreaktion som producerar citronellal och citronellol som huvudprodukter. Produkterna används som en citrondoftande komponent i parfymer, tvålar och tvättmedel samt som plattform-kemikalier. Dekarboxylering av stearinsyra var ett specialfall, för vilket en reaktionsväg för produktion av långkedjade kolväten utgående från fettsyror söktes. En synnerligen hög produktselektivitet var karakteristisk för detta system. Även processuppskalning modellerades för dekarboxylerings-reaktionen. Direkt syntes av väteperoxid hade som målsättning att framta en förenklad process att producera väteperoxid genom att låta upplöst väte och syre reagera direkt i ett lämpligt lösningsmedel på en aktiv fast katalysator. I detta system förekommer tre bireaktioner, vilka ger vatten som oönskad produkt. Alla dessa tre reaktioner modellerades matematiskt med hjälp av dynamiska massbalanser. Målet med hydrering av glukos och arabinos är att framställa produkter med en hög förädlingsgrad, nämligen sockeralkoholer, genom katalytisk hydrering. För dessa två system löstes ämnesmängd- och energibalanserna simultant för att evaluera effekter inne i porösa katalysatorpartiklar. Impulsbalanser som bestämmer strömningsbetingelser inne i en kemisk reaktor, ersattes i alla modelleringsstudier med semi-empiriska korrelationsuttryck för vätskans volymandel och tryckförlust och med axiell dispersionsmodell för beskrivning av omblandningseffekter. Genom att justera modellens parametrar kunde reaktorns beteende beskrivas väl. Alla experiment var genomförda i laboratorieskala. En stor mängd av kopplade effekter samexisterade: reaktionskinetik inklusive adsorption, katalysatordeaktivering, mass- och värmeöverföring samt strömningsrelaterade effekter. En del av dessa effekter kunde studeras separat (t.ex. dispersionseffekter och bireaktioner). Inverkan av vissa fenomen kunde ibland minimeras genom en noggrann planering av experimenten. På detta sätt kunde förenklingar i modellerna bättre motiveras. Alla system som studerades var industriellt relevanta. Utveckling av nya, förenklade produktionsteknologier för existerande kemiska komponenter eller nya komponenter är ett gigantiskt uppdrag. Studierna som presenterades här fokuserade på en av den teknisk-vetenskapliga utfärdens första etapper.

Drivers and barriers of mobile travel and tourism service adoption : a study of individual perceptions and business model development in a travel and tourism context

The Travel and Tourism field is undergoing changes due to the rapid development of information technology and digital services. Online travel has profoundly changed the way travel and tourism organizations interact with their customers. Mobile technology such as mobile services for pocket devices (e.g. mobile phones) has the potential to take this development even further. Nevertheless, many issues have been highlighted since the early days of mobile services development (e.g. the lack of relevance, ease of use of many services). However, the wide adoption of smartphones and the mobile Internet in many countries as well as the formation of so-called ecosystems between vendors of mobile technology indicate that many of these issues have been overcome. Also when looking at the numbers of downloaded applications related to travel in application stores like Google Play, it seems obvious that mobile travel and tourism services are adopted and used by many individuals. However, as business is expected to start booming in the mobile era, many issues have a tendency to be overlooked. Travelers are generally on the go and thus services that work effectively in mobile settings (e.g. during a trip) are essential. Hence, the individuals’ perceived drivers and barriers to use mobile travel and tourism services in on-site or during trip settings seem particularly valuable to understand; thus this is one primary aim of the thesis. We are, however, also interested in understanding different types of mobile travel service users. Individuals may indeed be very different in their propensity to adopt and use technology based innovations (services). Research is also switching more from investigating issues of mobile service development to understanding individuals’ usage patterns of mobile services. But designing new mobile services may be a complex matter from a service provider perspective. Hence, our secondary aim is to provide insights into drivers and barriers of mobile travel and tourism service development from a holistic business model perspective. To accomplish the research objectives seven different studies have been conducted over a time period from 2002 – 2013. The studies are founded on and contribute to theories within diffusion of innovations, technology acceptance, value creation, user experience and business model development. Several different research methods are utilized: surveys, field and laboratory experiments and action research. The findings suggest that a successful mobile travel and tourism service is a service which supports one or several mobile motives (needs) of individuals such as spontaneous needs, time-critical arrangements, efficiency ambitions, mobility related needs (location features) and entertainment needs. The service could be customized to support travelers’ style of traveling (e.g. organized travel or independent travel) and should be easy to use, especially easy to take into use (access, install and learn) during a trip, without causing security concerns and/or financial risks for the user. In fact, the findings suggest that the most prominent barrier to the use of mobile travel and tourism services during a trip is an individual’s perceived financial cost (entry costs and usage costs). It should, however, be noted that regulations are put in place in the EU regarding data roaming prices between European countries and national telecom operators are starting to see ‘international data subscriptions’ as a sales advantage (e.g. Finnish Sonera provides a data subscription in the Baltic and Nordic region at the same price as in Finland), which will enhance the adoption of mobile travel and tourism services also in international contexts. In order to speed up the adoption rate travel service providers could consider e.g. more local initiatives of free Wi-Fi networks, development of services that can be used, at least to some extent, in an offline mode (do not require costly network access during a trip) and cooperation with telecom operators (e.g. lower usage costs for travelers who use specific mobile services or travel with specific vendors). Furthermore, based on a developed framework for user experience of mobile trip arrangements, the results show that a well-designed mobile site and/or native application, which preferably supports integration with other mobile services, is a must for true mobile presence. In fact, travel service providers who want to build a relationship with their customers need to consider a downloadable native application, but in order to be found through the mobile channel and make contact with potential new customers, a mobile website should be available. Moreover, we have made a first attempt with cluster analysis to identify user categories of mobile services in a travel and tourism context. The following four categories were identified: info-seekers, checkers, bookers and all-rounders. For example “all-rounders”, represented primarily by individuals who use their pocket device for almost any of the investigated mobile travel services, constituted primarily of 23 to 50 year old males with high travel frequency and great online experience. The results also indicate that travel service providers will increasingly become multi-channel providers. To manage multiple online channels, closely integrated and hybrid online platforms for different devices, supporting all steps in a traveler process should be considered. It could be useful for travel service providers to focus more on developing browser-based mobile services (HTML5-solutions) than native applications that work only with specific operating systems and for specific devices. Based on an action research study and utilizing a holistic business model framework called STOF we found that HTML5 as an emerging platform, at least for now, has some limitations regarding the development of the user experience and monetizing the application. In fact, a native application store (e.g. Google Play) may be a key mediator in the adoption of mobile travel and tourism services both from a traveler and a service provider perspective. Moreover, it must be remembered that many device and mobile operating system developers want service providers to specifically create services for their platforms and see native applications as a strategic advantage to sell more devices of a certain kind. The mobile telecom industry has moved into a battle of ecosystems where device makers, developers of operating systems and service developers are to some extent forced to choose their development platforms.

Model-based estimation of liquid flows in the blast furnace hearth and taphole

This thesis presents a set of methods and models for estimation of iron and slag flows in the blast furnace hearth and taphole. The main focus was put on predicting taphole flow patterns and estimating the effects of various taphole conditions on the drainage behavior of the blast furnace hearth. All models were based on a general understanding of the typical tap cycle of an industrial blast furnace. Some of the models were evaluated on short-term process data from the reference furnace. A computational fluid dynamics (CFD) model was built and applied to simulate the complicated hearth flows and thus to predict the regions of the hearth exerted to erosion under various operating conditions. Key boundary variables of the CFD model were provided by a simplified drainage model based on the first principles. By examining the evolutions of liquid outflow rates measured from the furnace studied, the drainage model was improved to include the effects of taphole diameter and length. The estimated slag delays showed good agreement with the observed ones. The liquid flows in the taphole were further studied using two different models and the results of both models indicated that it is more likely that separated flow of iron and slag occurs in the taphole when the liquid outflow rates are comparable during tapping. The drainage process was simulated with an integrated model based on an overall balance analysis: The high in-furnace overpressure can compensate for the resistances induced by the liquid flows in the hearth and through the taphole. Finally, a recently developed multiphase CFD model including interfacial forces between immiscible liquids was developed and both the actual iron-slag system and a water-oil system in laboratory scale were simulated. The model was demonstrated to be a useful tool for simulating hearth flows for gaining understanding of the complex phenomena in the drainage of the blast furnace.

Visual customer segmentation and behavior analysis : a SOM-based approach

Ett ämne som väckt intresse både inom industrin och forskningen är hantering av kundförhållanden (CRM, eng. Customer Relationship Management), dvs. en kundorienterad affärsstrategi där företagen från att ha varit produktorienterade väljer att bli mera kundcentrerade. Numera kan kundernas beteende och aktiviteter lätt registreras och sparas med hjälp av integrerade affärssystem (ERP, eng. Enterprise Resource Planning) och datalager (DW, eng. Data Warehousing). Kunder med olika preferenser och köpbeteende skapar sin egen ”signatur” i synnerhet via användningen av kundkort, vilket möjliggör mångsidig modellering av kundernas köpbeteende. För att få en översikt av kundernas köpbeteende och deras lönsamhet, används ofta kundsegmentering som en metod för att indela kunderna i grupper utgående från deras likheter. De mest använda metoderna för kundsegmentering är analytiska modeller konstruerade för en viss tidsperiod. Dessa modeller beaktar inte att kundernas beteende kan förändras med tiden. I föreliggande avhandling skapas en holistisk översikt av kundernas karaktär och köpbeteende som utöver de konventionella segmenteringsmodellerna även beaktar dynamiken i köpbeteendet. Dynamiken i en kundsegmenteringsmodell innefattar förändringar i segmentens struktur och innehåll, samt förändringen av individuella kunders tillhörighet i ett segment (s.k migrationsanalyser). Vardera förändringen modelleras, analyseras och exemplifieras med visuella datautvinningstekniker, främst med självorganiserande kartor (SOM, eng. Self-Organizing Maps) och självorganiserande tidskartor (SOTM), en vidareutveckling av SOM. Visualiseringen anteciperas underlätta tolkningen av identifierade mönster och göra processen med kunskapsöverföring mellan den som gör analysen och beslutsfattaren smidigare. Asiakkuudenhallinta (CRM) eli organisaation muuttaminen tuotepainotteisesta asiakaskeskeiseksi on herättänyt mielenkiintoa niin yliopisto- kuin yritysmaailmassakin. Asiakkaiden käyttäytymistä ja toimintaa pystytään nykyään helposti tallentamaan ja varastoimaan toiminnanohjausjärjestelmien ja tietovarastojen avulla; asiakkaat jättävät jatkuvasti piirteistään ja ostokäyttäytymisestään kertovia tietojälkiä, joita voidaan analysoida. On tavallista, että asiakkaat poikkeavat toisistaan eri tavoin, ja heidän mieltymyksensä kuten myös ostokäyttäytymisensä saattavat olla hyvinkin erilaisia. Asiakaskäyttäytymisen monimuotoisuuteen ja tuottavuuteen paneuduttaessa käytetäänkin laajalti asiakassegmentointia eli asiakkaiden jakamista ryhmiin samankaltaisuuden perusteella. Perinteiset asiakassegmentoinnin ratkaisut ovat usein yksittäisiä analyyttisia malleja, jotka on tehty tietyn aikajakson perusteella. Tämän vuoksi ne monesti jättävät huomioimatta sen, että asiakkaiden käyttäytyminen saattaa ajan kuluessa muuttua. Tässä väitöskirjassa pyritäänkin tarjoamaan holistinen kuva asiakkaiden ominaisuuksista ja ostokäyttäytymisestä tarkastelemalla kahta muutosvoimaa tiettyyn aikarajaukseen perustuvien perinteisten segmentointimallien lisäksi. Nämä kaksi asiakassegmentointimallin dynamiikkaa ovat muutokset segmenttien rakenteessa ja muutokset yksittäisten asiakkaiden kuulumisessa ryhmään. Ensimmäistä dynamiikkaa lähestytään ajallisen asiakassegmentoinnin avulla, jossa visualisoidaan ajan kuluessa tapahtuvat muutokset segmenttien rakenteissa ja profiileissa. Toista dynamiikkaa taas lähestytään käyttäen nk. segmenttisiirtymien analyysia, jossa visuaalisin keinoin tunnistetaan samantyyppisesti segmentistä toiseen vaihtavat asiakkaat. Visualisoinnin tehtävänä on tukea havaittujen kaavojen tulkitsemista sekä helpottaa tiedonsiirtoa analysoijan ja päättäjien välillä. Visuaalisia tiedonlouhintamenetelmiä, kuten itseorganisoivia karttoja ja niiden laajennuksia, käytetään osoittamaan näiden menetelmien hyödyllisyys sekä asiakkuudenhallinnassa yleisesti että erityisesti asiakassegmentoinnissa.

Stop bugging me! : diversity in appearance of warning coloration

In nature, many animals use body coloration to communicate with each other. For example, colorations can be used as signals between individuals of the same species, but also to recognise individuals of other species, and if they may comprise a threat or not. Many animals use protective coloration to avoid predation. The two most common strategies of protective coloration are camouflage and aposematism. Camouflaged animals have coloration that minimises detection, usually by matching colours or structures in the background. Aposematic animals, on the other hand, signal to predators that they are defended. The defence can be physical structures, such as spikes and hairs, or chemical compounds that make the animal distasteful or even deadly toxic. In order for the warning signal to be effective, the predator has to recognise it as such. Studies have shown that birds for example, that are important visual predators on insects, learn to recognise and avoid unpalatable prey faster if they contrast the background or have large internal contrasts. Typical examples of aposematic species have conspicuous colours like yellow, orange or red, often in combination with black. My thesis focuses on the appearance and function of aposematic colour patterns. Even though researchers have studied aposematism for over a century, there is still a lot we do not know about the phenomenon. For example, as it is crucial that the predators recognise a warning signal, aposematic colorations should assumingly evolve homogeneously and be selected for maximal conspicuousness. Instead, there is an extensive variation of colours and patterns among warning colorations, and it is not uncommon to find typical cryptic colours, such as green and brown in aposematic colour patterns. One hypothesis to this variation is that an aposematic coloration does not have to be maximally signalling in order to be effective, instead it is sufficient to have distinct features that can be easily distinguished from edible prey. To be maximally conspicuous is one way to achieve this, but not the only way. Another hypothesis is that aposematic prey that do not exhibit maximal conspicuousness can exploit both camouflage and aposematism in a distance-dependent fashion, by being signalling when seen close up but camouflaged at a distance. Many prey animals also make use of both strategies by shifting colour at different ecological conditions such as seasonal variations, fluctuations in food resources or between life stages. Yet another explanation for the variation may be that prey animals are usually exposed to several predator species that vary in visual perception and tolerance towards various toxins. The aim with this thesis is, by studying their functions, to understand why aposematic warning signals vary in appearance, specifically in the level of conspicuousness, and if warning coloration can be combined with camouflage. In paper I, I investigated if the colour pattern of the aposematic larva of the Apollo butterfly (Parnassius apollo) can switch function with viewing distance, and be signalling at close range but camouflaged at a distance, by comparing detection time between different colour variants and distances. The results show that the natural coloration has a dual distance-dependent function. Moreover, the study shows that an aposematic coloration does not have to be selected for maximal conspicuousness. A prey animal can optimise its coloration primarily by avoiding detection, but also by investing in a secondary defence, which presence can be signalled if detected. In paper II, I studied how easily detected the coloration of the firebug (Pyrrhocoris apterus), a typical aposematic species, is at different distances against different natural backgrounds, by comparing detection time between different colour variants. Here, I found no distance-dependent switch in function. Instead, the results show that the coloration of the firebug is selected for maximal conspicuousness. One explanation for this is that the firebug is more mobile than the butterfly larva in study I, and movement is often incompatible with efficient camouflage. In paper III, I investigated if a seasonal related colour change in the chemically defended striated shieldbug (Graphosoma lineatum) is an adaptation to optimise a protective coloration by shifting from camouflage to aposematism between two seasons. The results confirm the hypothesis that the coloration expressed in the late summer has a camouflage function, blending in with the background. Further, I investigated if the internal pattern as such increased the effectiveness of the camouflage. Again, the results are in accordance with the hypothesis, as the patterned coloration was more difficult to detect than colorations lacking an internal pattern. This study shows how an aposematic species can optimise its defence by shifting from camouflage to aposematism, but in a different fashion than studied in paper I. The aim with study IV was to study the selection on aposematic signals by identifying characteristics that are common for colorations of aposematic species, and that distinguish them from colorations of other species. I compared contrast, pattern element size and colour proportion between a group of defended species and a group of undefended species. In contrast to my prediction, the results show no significant differences between the two groups in any of the analyses. One explanation for the non-significant results could be that there are no universal characteristics common for aposematic species. Instead, the selection pressures acting on defended species vary, and therefore affect their appearance differently. Another explanation is that all defended species may not have been selected for a conspicuous aposematic warning coloration. Taken together, my thesis shows that having a conspicuous warning coloration is not the only way to be aposematic. Also, aposematism and camouflage is not two mutually exclusive opposites, as there are prey species that exploit both strategies. It is also important to understand that prey animals are exposed to various selection pressures and trade-offs that affect their appearance, and determines what an optimal coloration is for each species or environment. In conclusion, I hold that the variation among warning colorations is larger and coloration properties that have been considered as archetypically aposematic may not be as widespread and representative as previously assumed.

Probabilistic contact preferences in protein-ligand and protein-protein complexes

Modeller för intermolekulär växelvärkan utnyttjas brett inom biologin. Analys av kontakter mellan proteiner och läkemedelsforskning representerar typiska tillämpningsområden för dylika modeller. En modell som beskriver sådana molekylära växelverkningar kan utformas med hjälp av biofysisk teori, vilket tenderar att resultera i ytterst tung beräkningsbörda även för enkla tillämpningar. Ett alternativt sätt att formulera modeller är att utnyttja stora databaser som innehåller strukturmätningar gjorda med hjälp av till exempel röntgendiffraktion. Då man använder sig av empiriska mätdata direkt, möjliggör en statistisk modell att osäkerheten och inexaktheten i datat tas till hänsyn på ett adekvat sätt, samtidigt som beräkningsbördan håller sig på en rimligare nivå jämfört med kvantmekaniska metoder som i princip borde ge de optimala resultaten. I avhandlingen utvecklades en 3D modell för numerisk undersökning av intermolekulär växelverkan baserad på Bayesiansk statistik. Modellens syfte är att åstadkomma prognoser för det hurdana eller vilka molekylstrukturer prefereras i en given kontext, d.v.s. är mer sannolika inom ramen för interaktion. Modellen testades i essentiella molekyläromgivningar - en liten molekyl vid sin bindningsplats hos ett protein och en gränsyta mellan proteinerna i ett komplex. De erhållna numeriska resultaten motsvarar väl experimentella resultat som tidigare rapporterats i litteraturen, exempelvis kvalitativa bindningsaffiniteter och kemisk kännedom av vissa aminosyrors rumsliga förmågor att utgöra bindningar. I avhandlingen gjordes ytterligare preliminära tester av den statistiska ansatsen för modellering av den centrala molekylära strukturella anpassningsbarheten. I praktiken är den utvecklade modellen ämnad som ett led i en mer omfattande analysmetod, så som en s.k. farmakofor modell. Molekyylivuorovaikutusten mallintamista hyödynnetään laajasti biologisten kysymysten tarkastelussa. Tyypillisiä esimerkkejä sovelluskohteista ovat proteiinien väliset kontaktit ja lääkesuunnittelu. Vuorovaikutuksia kuvaavan mallin lähtökohta voi olla molekyyleihin liittyvä teoria, jolloin soveltamiseen liittyvä laskenta saattaa olla erityisen raskasta, tai suuri havaintojoukko joka on saatu aikaan esimerkiksi mittaamalla rakenteita röntgendiffraktio menetelmällä. Tilastollinen malli mahdollistaa havaintoaineistossa olevan epätarkkuuden ja epävarmuuden huomioimisen, samalla pitäen laskennallisen kuorman pienempänä verrattuna periaatteessa parhaan tuloksen antavaan kvanttimekaaniseen mallinnukseen. Väitöstyössä kehitettiin bayesiläiseen tilastotieteeseen perustuva 3D malli molekyylien välisten vuorovaikutusten laskennalliseen tarkasteluun. Mallin tehtävä on tuottaa ennusteita sen suhteen, minkä tai millaisten molekyylirakenteiden väliset kompleksit ovat etusijalla, toisin sanoen todennäköisempiä, vuorovaikutustilanteessa. Työssä kehitetyn menetelmän toimivuutta testattiin käyttötarkoituksen suhteen olennaisissa molekyyliympäristöissä - pieni molekyyli sitoutumiskohdassaan proteiinissa sekä rajapinta kahden proteiinin välilllä proteiinikompleksissa. Saadut laskennalliset tulokset vastasivat hyvin vertailuun käytettyjä kirjallisuudesta saatuja kokeellisia tuloksia, kuten laadullisia sitoutumisaffiniteetteja, sekä kemiallista tietoa esimerkiksi tiettyjen aminohappojen avaruudellisesta sidoksenmuodostuksesta. Väitöstyössä myös alustavasti testattiin tilastollista lähestymistapaa tärkeän molekyylien rakenteellisen mukautuvuuden mallintamiseen. Käytännössä malli on tarkoitettu osaksi jotakin laajempaa analyysimenetelmää, kuten farmakoforimallia.

Regioselective modification of galactose-containing polysaccharides in aqueous media

Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.

Coping with international atrocities through criminal law : a study into the typical features of international criminality and the reflection of these traits in international criminal law

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I hälsans spelrum : lek på vårdandets scen

With caring science as its foundation and by means of the perioperative dialogue, the intended contribution and overall aim of this present thesis is to describe what play is and could be in the caring reality, an ideal model. The perioperative dialogue is the nurse anaesthetists’ pre-, intra- and post-operative dialogues with the children they care for in connection with anesthesia. The thesis is composed according to Schopenhauer’s notion that the road to science presupposes the world seen as performances, and has an all-pervading hermeneutic approach. The performances of the thesis are: the performance of all performances, the empirical performance, the transcendental performance and the universal performance. The performance of all performances originates in the theoretical perspective of the thesis and describes what play and its characteristics are. This performance is realized through the hermeneutic interpretation of the etymology and original meaning of the word play along with texts from caring science, philosophy, anthropology and the history of religion. The empirical performance originates in four empirical studies where caring is organized as a perioperative dialogue. In study I, the material was collected with the help of participating observations and semi-structured interviews, in study II, with the help of the critical incident method and in study III, with the help of conversation interviews. In study IV, play develops into a clinical caring science research method. The research participants consist of children with special needs, children with a pronounced fear of anaesthesia, parents of children with severe autism and nurse anaesthetists. The empirical performance relates in what way play manifests in a perioperative child context by interpreting the results from the empiric in the light of the characteristics of play. The transcendental performance is enacted in the playhouse of health and presents a picture of the essence of play, the playing. In the playhouse of health, the light, winged movement of play is actualized when what was previously too difficult, too heavy and pinioned instead is as easy as anything. The eye of love and compassion knows the art of deciphering the secret script where the Other’s holiness resides, even if mere glimpses of it appear. The universal performance depicts three caring acts where the entrance consists of entering play, the ideal of which is realized in the unmasked openness face to face, that which protects the playing human being against encroachment and an unwanted audience. In the second caring act, entering play plays on to the finely-tuned interplay between human beings in the winged play of beauty and dignity. In the third caring act, the world’s deepest plays are staged on the stage of caring, in the sense that the innermost being of each individual, the universal will joins in and allows individuals to live as playing human beings who are at home with themselves and the world. The captivating, graceful and friendly play works from within itself, as long as it illumined by the light of claritas can play undisturbed on the stage of caring where it – like an unclouded mirror of its own ideal watches over children’s health.

Structure-related magnetic fabric studies : implications for deformed and undeformed Precambrian rocks

The aim of this thesis research was to gain a better understanding of the emplacement of rapakivi granite intrusions, as well as the emplacement of gold-bearing hydrothermal fluids in structurally controlled mineralizations. Based on investigations of the magnetic fabric, the internal structures could be analysed and the intrusion mechanisms for rapakivi granite intrusions and respectively different deformation stages within gold-bearing shear and fault zones identified. Aeromagnetic images revealed circular structures within the rapakivi granite batholiths of Wiborg, Vehmaa and Åland. These circular structures represent intrusions that eventually build up these large batholiths. The rapakivi granite intrusions of Vehmaa, Ruotsinpyhtää within the Wiborg batholith and Saltvik intrusions within the Åland batholith all show bimodal magnetic susceptibilities with paramagnetic and ferromagnetic components. The distribution of the bimodality is related to different magma batches of the studied intrusions. The anisotropy of magnetic susceptibility (AMS) reveals internal structures that cannot be studied macroscopically or by microscope. The Ruotsinpyhtää and Vehmaa intrusions represent similar intrusion geometries, with gently to moderately outward dipping magnetic foliations. In the case of Vehmaa, the magnetic lineations are gently plunging and trend in the directions of the slightly elongated intrusion. The magnetic lineations represent magma flow. The shapes of the AMS ellipsoids are also more planar (oblate) in the central part of the intrusion, whereas they become more linear (prolate) near the margin. These AMS results, together with field observations, indicate that the main intrusion mechanism has involved the subsidence of older blocks with successive intrusion of fractionated magma during repeated cauldron subsidence. The Saltvik area within the Åland batholith consists of a number of smaller elliptical intrusions of different rapakivi types forming a multiple intrusive complex. The magnetic fabric shows a general westward dipping of the pyterlite and eastward dipping of the contiguous even-grained rapakivi granite, which indicates a central inflow of magma batches towards the east and west resulting from a laccolitic emplacement of magma batches, while the main mechanism for space creation was derived from subsidence. The magnetic fabric of structurally controlled gold potential shear and fault zones in Jokisivu, Satulinmäki and Koijärvi was investigated in order to describe the internal structures and define the deformation history and emplacement of hydrothermal fluids. A further aim of the research was to combine AMS studies with palaeomagnetic methods to constrain the timing for the shearing event relative to the precipitation of ferromagnetic minerals and gold. All of the studied formations are dominated by monoclinic pyrrhotite. The AMS directions generally follow the tectonic structures within the formations. However, internal variations in the AMS direction as well as the shapes of the AMS ellipsoids are observed within the shear zones. In Jokisivu and Satulinmäki in particular, the magnetic signatures of the shear zone core differ from the margins. Furthermore, the shape of the magnetic fabric in the shear zone core of Jokisivu is dominated by oblate shapes, whereas the margins exhibit prolate shapes. These variations indicate a later effect of the hydrothermal fluids on the general shear event. The palaeo-magnetic results reveal a deflection from the original Svecofennian age geomagnetic direction. These results, coupled with correlations between the orientation of the NRM vectors and the magnetic and rock fabrics, imply that the gold-rich hydrothermal fluids were emplaced pre/syntectonically during the late stages of the Svecofennian orogeny.

Improvement of wet and dry web properties in papermaking by controlling water and fiber quality

Pappersindustrin står inför många utmaningar och bör uppfylla krav som ställs av t.ex. marknadstrender och slutanvändare. Snabbare och effektivare processer ställer även större krav på pappersbanans mekaniska egenskaper. Avbrott i produktionen sker inte enbart pga. låg styrka utan orsaken kan även vara en för låg spänning i pappersbanan. De flesta problemen sker vid våtpressen och/eller i början av torkpartiet då papprets torrhalt är 30-70 %. Spänningen hålls inte konstant efter töjning, utan sjunker pga. papprets relaxering, som till största delen sker då pappret flyttas från pressen till torkpartiet. Ur forskningssynvinkel öppnar en smidigt fungerande verksamhet med potentiella energibesparingar upp möjligheterna för förbättring av befintliga processer. I detta arbete undersöktes hur olika faktorer inverkar på fibernätverkets avvattning, initiala våtstyrka och relaxering samt också på slutproduktens mekaniska egenskaper och ytegenskaper. I första delen ändrades processvattnets egenskaper, såsom pH, konduktivitet och ytspänning. Ytspänningen varierades genom tillsatts av ett nonjoniskt ytaktivt ämne, s.k. surfaktant. Fiberegenskaperna modifierades också. Fibern maldes antingen genom en mild eller genom en hård process. Effekten av finmaterial undersöktes genom att tillsätta finmaterial till den ursprungliga massan eller genom att avlägsna finmaterialet från den malda massan. I den sista delen användes en hemicellulosa, som finns i stora mängder i gran, som tillsatsmedel. Förutom naturliga galaktoglukomannaner (GGM), tillverkades också en katjoniserad, en karboximetylerad samt en iminerad, amfifil GGM. Dessa användes i pappersmassa eller sprayades på ytan av ett nybildat ark. Resultaten, som erhölls i denna avhandling, bildar en värdefull kunskapsbas, som kan användas för kontroll och reglering av pappersmaskinens körbarhet och papperskvalitet.

Composite artistry in the Book of Numbers : a study in biblical narrative conventions

The present thesis discusses the coherence or lack of coherence in the book of Numbers, with special regard to its narrative features. The fragmented nature of Numbers is a well-known problem in research on the book, affecting how we approach and interpret it, but to date there has not been any thorough investigation of the narrative features of the work and how they might contribute to the coherence or the lack of coherence in the book. The discussion is pursued in light of narrative theory, and especially in connection to three parameters that are typically understood to be invoked in the interpretation of narratives: 1) a narrative paradigm, or ‘story,’ meaning events related to each other temporally, causally, and thematically, in a plot with a beginning, middle, and end; 2) discourse, being the expression plane of a narrative, or the devices that an author has at hand in constructing a narrative; 3) the situation or languagegame of the narrative, prototypical examples being factual reports, which seeks to depict a state of affairs, and storytelling narratives, driven by a demand for tellability. In view of these parameters the present thesis argues that it is reasonable to form four groups to describe the narrative material of Numbers: genuine narratives (e.g. Num 12), independent narrative sequences (e.g. Num 5:1-4), instrumental scenes and situations (e.g. Num 27:1-5), and narrative fragments (e.g. Num 18:1). These groups are mixed throughout with non-narrative materials. Seen together, however, the narrative features of these groups can be understood to create an attenuated narrative sequence from beginning to end in Numbers, where one thing happens after another. This sequence, termed the ‘larger story’ of Numbers, concerns the wandering of Israel from Sinai to Moab. Furthermore, the larger story has a fragmented plot. The end-point is fixed on the promised land, Israel prepares for the wandering towards it (Num 1-10), rebels against wandering and the promise and is sent back into the wilderness (Num 13-14), returns again after forty years (Num 21ff.), and prepares for conquering the land (Num 22-36). Finally, themes of the promised land, generational succession, and obedience-disobedience, operate in this larger story. Purity is also a significant theme in the book, albeit not connected to plot in the larger story. All in all, sequence, plot, and theme in the larger story of Numbers can be understood to bring some coherence to the book. However, neither aspect entirely subsumes the whole book, and the four groups of narrative materials can also be understood to underscore the incoherence of the work in differentiating its variegated narrative contents. Numbers should therefore be described as an anthology of different materials that are loosely connected through its narrative features in the larger story, with the aim of informing Israelite identity by depicting a certain period in the early history of the people.

On Bayesian predictive modeling : with applications on the analysis of chromatography data in forensic investigations

Med prediktion avses att man skattar det framtida värdet på en observerbar storhet. Kännetecknande för det bayesianska paradigmet är att osäkerhet gällande okända storheter uttrycks i form av sannolikheter. En bayesiansk prediktiv modell är således en sannolikhetsfördelning över de möjliga värden som en observerbar, men ännu inte observerad storhet kan anta. I de artiklar som ingår i avhandlingen utvecklas metoder, vilka bl.a. tillämpas i analys av kromatografiska data i brottsutredningar. Med undantag för den första artikeln, bygger samtliga metoder på bayesiansk prediktiv modellering. I artiklarna betraktas i huvudsak tre olika typer av problem relaterade till kromatografiska data: kvantifiering, parvis matchning och klustring. I den första artikeln utvecklas en icke-parametrisk modell för mätfel av kromatografiska analyser av alkoholhalt i blodet. I den andra artikeln utvecklas en prediktiv inferensmetod för jämförelse av två stickprov. Metoden tillämpas i den tredje artik eln för jämförelse av oljeprover i syfte att kunna identifiera den förorenande källan i samband med oljeutsläpp. I den fjärde artikeln härleds en prediktiv modell för klustring av data av blandad diskret och kontinuerlig typ, vilken bl.a. tillämpas i klassificering av amfetaminprover med avseende på produktionsomgångar.

Extremfall, stjärnelever och verktygsskramlare : en diskursanalytisk studie av lärares tal om studerande som behöver särskilt stöd

The groups within Finnish vocational upper secondary education and training (VET) are often heterogeneous with respect to the student's need for support in their studies. According to the national core curricula, Special Education Needs (SEN) students should in the first place, get their education in the same group as everyone else. This dissertation aims to clarify and create an understanding about how the ideals and intention of equality in education is constructed in communication among teachers in VET in the Swedish-speaking parts of Finland. Through this understanding it should be possible to highlight a potential which could ultimately contribute to a positive development of a more inclusive education within VET. The epistemological platform of the study is to be found within the post structuralist philosophy of language that is considered as subsumed in a social constructionist thinking. The data has been collected through focus group discussions in groups of 3–6 participants (teachers) in seven schools in Finnish-Swedish VET. The analyses are based on a discursive psychological analysis combined with an analysis based on Michel Foucault's concepts with an emphasis on the subject, government and power. Four discourser where identified in the analysis of teachers' constructions of the educational assignment in relation to SEN students. The most dominant was discussing the educational assignment as a pragmatic project i.e. as a matter of transmission of knowledge. The discourse included both interpretative repertoires where the heterogeneous group was constructed as self-evident and possible to manage as well as a constructed as an impossible project. The educational assignment was also constructed as a holistic project, as part of a democratic project, and as a labor market project. Each discourse contains both including as well as excluding features in relation to SEN students. The development of an inclusive practice can and should therefore include elements from all of them. Three discourses were identified in the analysis concerning teachers' versions of SEN students: students with difficulties and problems; students who do not use or do not have ability and students who are irresponsible and lack the will to study. Within the various discourses and interpretative repertoires were both constructs when teachers described a concern and kindness in relation to the individual SEN student and constructions where teachers mainly expressed fears that other students in the group would be negatively affected by students in need of special support. Results from the third research question conclude the results from the two others, the analysis is done out of a government perspective. In the material use of different government techniques are identified: disciplinary power through direct reprimands; pastoral power by a desire of insight in order to promote the opportunities for consultation and the use of bio-power that primarily focuses on what is best for the population and whose tool racism results in a legitimation of the exclusion of SEN students. The conclusion is that teachers in VET need to pay attention to inclusive and exclusive elements identified in various discourses.

The pH-dependent phase distribution of wood pitch components in papermaking processes

Wood contains only a very small amount of lipophilic extractives, commonly known as wood pitch. The pitch is known to cause severe problems in papermaking processes. The amount of pitch in process waters can be decreased by seasoning of the raw material prior to pulping, pulp washing, removal of pitch by flotation, adsorption of pitch onto various mineral surfaces, and retention of pitch to the fibre material by cationic polymers. The aim of this study was to determine the influence of pH on some of the methods used for pitch control. Experiments were performed using laboratory-made wood pitch emulsions with varying pH, salt concentration, hemicellulose concentration and pitch composition. These emulsions were used to study the phase distribution of resin and fatty acids, the colloidal stability of pitch with and without steric stabilisation by galactoglucomannans, and the interactions between wood pitch and mineral particles. Purification of unbleached and peroxidebleached mill process water was performed by froth flotation in combination with a foaming agent. The distribution of resin and fatty acids (RFAs) between colloidal pitch droplets and the water phase was very dependent on pH. At pH 3, almost all of the RFAs were attached to the pitch droplets, while increasing the pH led to increasing concentration of dissolved RFAs in the water phase. The presence of salt shifted the release of RFAs towards higher pH, while lower ratio of neutral pitch in the emulsion resulted in release of RFAs at lower pH. It was also seen that the dissolution and adsorption of RFAs at sudden pHchanges takes place very quickly. Colloidal pitch was more stable against electrolyte-induced aggregation at higher pH, due to its higher anionic charge. The concentration of cationic polymers needed to aggregate colloidal pitch also increased with increasing pH. The surface characteristics of solid particles, such as amount of charged groups, were very important for understanding their interactions with colloidal wood pitch. Water-soluble galactoglucomannans stabilised the colloidal pitch sterically against aggregation, but could not completely prevent interactions between wood pitch and hydrophilic particles. Froth flotation of unbleached and peroxidebleached process water showed that the pitch could be removed more effectively and selectively at low pH, compared to at neutral pH. The pitch was removed more effectively, using lower concentrations of foaming agent, from peroxide-bleached water than from unbleached water. The results show that pH has a major impact on various pulping and papermaking processes. It determines the anionic charge of the colloidal pitch and the solubility of certain pitch components. Because of this, the pH influences the effectiveness of pitch retention and removal of pitch. The results indicate that pitch problems could be diminished by acknowledging the importance of pH in various papermaking processes.