Circular Spectropolarimetric Studies of DQ White Dwarfs

This thesis summarizes studies of a class of white dwarfs (WDs) called DQ WDs. White dwarfs are the remnants of ordinary stars like our Sun that have run out of nuclear fuel. WDs are classified according to the composition of their atmosphere and DQ WDs have an atmosphere made of helium and carbon. The carbon comes in either atomic or molecular form and in some cases the strong spectral absorption features cover the entire optical wavelength region. The research presented here utilizes spectropolarimetry, which is an observational technique that combines spectroscopy and polarization. Separately these allow to study the composition of a target and the inhomogeneous distribution of matter in the target. Put together they form a powerful tool to probe the physical properties in the atmosphere of a star. It is espacially good for detecting magnetic fields. The papers in this thesis describe efforts to do a survey of DQ white dwarfs with spectropolarimetry in order to search for magnetic fields in them. Paper I describes the discovery of a new magnetic cool DQ white dwarf, GJ841B. Initial modeling of molecular features on DQ WDs showed inconsistencies with observations. The first possible solution to this problem was stellar spots on these WDs. To investigate the matter, two DQ WDs were monitored for photometric variability that could arise from the presence of such spots. Paper II summarizes this short campaign and reports the negative results. Paper III reports observations of the rest of the objects in our survey. The paper includes the discovery of polarization from another cool DQ white dwarf, bringing the total of known magnetic cool DQs to three. Unfortunately the model used in this thesis cannot, in its present state, be used to model these objects nor are the observations of high enough spectroscopic resolution to do so.

Tiedon jakaminen kolmen ammattikorkeakoulun strategisessa liittoumassa. Case: Federation of Universities of Applied Sciences.

Ammattikorkeakoulut ovat suurten rakenteellisten ja rahoituksellisten muutosten edessä. Rahoitus tulee jatkossa tutkintojen määrään painottuen nykyisen opiskelija-määrän sijaan ja tämä pakottaa ammattikorkeakoulut etsimään keinoja toiminnan tehostamiseksi, joista korkeakoulujen muodostamat liittoumat ovat yksi väline. Tämän tutkimuksen aiheena on tiedon jakaminen kolmen ammattikorkeakoulun muo-dostamassa strategisessa liittoumassa. Tutkimus toteutettiin kvantitatiivisena tutkimuksena, jonka empiirinen osuus toteutet-tiin kyselylomakkeella Hämeen, Lahden ja Laurea-ammattikorkeakoulujen toimijoilta keräten. Vastauksia saatiin 79, vastausprosentin ollessa 62,2 %. Tutkimustulosten perusteella FUASin johdon toimilla, organisaation rakenteella, organisaation kulttuu-rilla ja työilmapiirillä on positiivinen vaikutus tiedon jakamiseen. Lisäksi toimijoiden välinen luottamus ja avoimuus sekä motivaatio parantavat tiedon jakamista FUAS-ammattikorkeakoulujen välillä. Tiedon jakamisesta palkitseminen ja oman edun ta-voittelu eivät vaikuttaneet tilastollisesti merkittävästi FUASissa tapahtuvaan tiedon jakamiseen.

Puolueiden keskustelutilaisuuksista mediatapahtumiksi. Television vaaliohjelmat ja niihin liittynyt sanomalehtijulkisuus 1960-luvulta 1980-luvulle

Tässä tutkimuksessa tarkastellaan television vaaliohjelmia ja niihin liittynyttä sanomalehtijulkisuutta 1960-luvun alusta 1980-luvun lopulle. Tarkastelun kohteena ovat sekä eduskunta- että presidentinvaalien vaaliohjelmat. Tutkimusaineisto koostuu Yleisradion hallinto- ja ohjelmaneuvostojen pöytäkirjoista, vaaliohjelmien televisiotallenteista sekä vaaliohjelmia käsittelevistä sanomalehtikirjoituksista. Lehtiaineisto on kerätty Helsingin Sanomista, Ilta-Sanomista, Iltalehdestä, Aamulehdestä, Kansan Uutisista, Suomenmaasta sekä Suomen Sosialidemokraatista. Sanomalehtiaineistoa on täydennetty Yleisradion leikearkistoon kerätyillä lehtileikkeillä. Tutkimuksessa on analysoitu toisaalta television vaaliohjelmien kehitystä ja toisaalta vaaliohjelmiin liittynyttä sanomalehtikirjoittelua. Television vaaliohjelmien kehityksen osalta tutkimuksessa on kuvattu, millä tavoin vaaliohjelmia on eri aikoina tehty ja millaisia poliittisia kiistoja niiden tekemiseen on liittynyt. Sanomalehtiaineiston analyysissa on tarkasteltu sitä, mihin seikkoihin vaaliohjelmia käsittelevissä kirjoituksissa on kiinnitetty huomiota, millä tavoin lehdet ovat suhtautuneet ohjelmien toteutukseen ja millainen rooli ohjelmilla on nähty olleen vaalikampanjoinnissa. Väitöskirjan näkökulma on historiallinen, mikä merkitsee ajallisten kontekstien keskeisyyttä analyysissa. Tutkimuksessa on kiinnitetty huomiota sekä poliittisessa kulttuurissa että mediamaisemassa tapahtuneisiin muutoksiin. Vaaliohjelmat olivat 1960-luvulla tarkkaan säänneltyjä puolueiden välisiä keskustelutilaisuuksia, joissa toimittajilla ei ollut näkyvää roolia. Ohjelmien toteutuksesta vastasivat puoluemandaateilla toimineet Yleisradion ohjelma- ja hallintoneuvoston jäsenet, joten ohjelmien toteutuksen yksityiskohdista vastasivat puolueet. Puolueet riitelivät usein vaaliohjelmien toteutuksesta, mikä osoittaa, että puolueille television vaaliohjelmat olivat tärkeitä poliittisia foorumeita jo 1960-luvulta lähtien. Vaaliohjelmat jakautuivat kahteen erilaiseen ohjelmaformaattiin; vaalitentteihin ja suureen vaalikeskusteluun. Vaalitenteissä kunkin puolueen edustajat olivat vuorollaan ”altavastaajina”, joille muiden puolueiden edustajat esittivät kysymyksiä. Suuri vaalikeskustelu oli perinteisempi paneelikeskustelu, jossa poliitikot selvittivät vuorotellen kantojaan ajankohtaisiin poliittisin kysymyksiin. 1970-luvun puolivälissä vaalitenttien toteutuksessa tapahtui suuria muutoksia, kun toimittajat syrjäyttivät poliitikot vaalitenttien kyselijöinä. Suuri vaalikeskustelu säilyi ennallaan. Sanomalehtien suhtautuminen vaaliohjelmiin oli 1960- ja 1970-luvuilla huomattavasti pidättyvämpää kuin poliitikkojen. Sanomalehdistön näkökulmasta television vaaliohjelmien tärkeimpänä tehtävänä oli puolueiden poliittisten linjausten esittely. Vaaliohjelmia käsittelevissä teksteissä esiteltiin pääasiassa poliitikkojen ohjelmissa pitämiä puheenvuoroja. Puoluelehdissä puheenvuorojen sisältöä arvioitiin aatteellisista lähtökohdista, sitoutumattomissa sanomalehdissä neutraalimmin. Vaaliohjelmien toteutukseen liittynyt kritiikki kohdistui toisaalta poliitikkojen puoluepropagandaan, toisaalta poliitikkojen liialliseen varovaisuuteen. Sanomalehtien suhtautuminen vaaliohjelmiin säilyi ennallaan myös 1970-luvulla, jolloin vaaliohjelmia alettiin tehdä toimittajavetoisesti. Ainoa muutos liittyi vaaliohjelmakritiikkiin, joka kohdistui nyt poliitikkojen ohella myös toimittajiin, joiden katsottiin olleen ohjelmissa liian hyökkääviä. Suurin muutos vaaliohjelmiin liittyneessä kirjoittelussa tapahtui 1980-luvulla. Vaaliohjelmia käsitteleviä kirjoituksia julkaistiin sanomalehdistössä monikertainen määrä 1970-lukuun verrattuna. Samalla myös vaaliohjelmia käsittelevien kirjoitusten näkökulmat alkoivat muuttua, kun ohjelmin visuaalinen ulottuvuus alkoi olla yhä näkyvämmin esillä sanomalehtiin laadituissa analyyseissa. Lehdet alkoivat teettää säännöllisesti erilaisia tutkimuksia poliitikkojen pärjäämisestä ohjelmissa ja kirjoittaa vaalikeskusteluiden voittajista ja häviäjistä. Lisäksi lehtijutuissa arvioitiin poliitikkojen esiintymistä ja vaaliohjelmista välittyviä vaikutelmia. Vuoden 1982 presidentinvaaleissa uusista näkökulmista kirjoittivat erityisesti iltapäivälehdet, mutta vuosikymmenen jälkipuoliskolla samankaltaisia lähestymistapoja omaksuivat myös Helsingin Sanomat ja Aamulehti. Niiden vaaliohjelmia käsittelevissä uutisissa kiinnitettiin yhä useammin huomiota poliitikkojen esiintymiseen, pukeutumiseen ja tunnetiloihin. Puoluelehtien suhtautuminen vaaliohjelmiin säilyi kuitenkin ennallaan, ja myös vaaliohjelmakritiikki säilyi suurelta osin muuttumattomana. 1980-luvun aikana television vaaliohjelmat muuttuivat lehdistön käsittelyssä puolueiden tavoitteita esittelevistä keskustelutilaisuuksista poliitikkojen ja puolue johtajien henkilökohtaisia ominaisuuksia mittaaviksi esiintymiskokeiksi ja suuriksi mediatapahtumiksi, joiden katsottiin toisinaan jopa ratkaisseen vaalin tuloksen. Nostaessaan television vaaliohjelmat kampanjajournalisminsa ytimeen, sanomalehdet vahvistivat television poliittista roolia.

Greenhouse gas emissions from peat and biomass-derived fuels, electricity and heat — Estimation of various production chains by using LCA methodology

More discussion is required on how and which types of biomass should be used to achieve a significant reduction in the carbon load released into the atmosphere in the short term. The energy sector is one of the largest greenhouse gas (GHG) emitters and thus its role in climate change mitigation is important. Replacing fossil fuels with biomass has been a simple way to reduce carbon emissions because the carbon bonded to biomass is considered as carbon neutral. With this in mind, this thesis has the following objectives: (1) to study the significance of the different GHG emission sources related to energy production from peat and biomass, (2) to explore opportunities to develop more climate friendly biomass energy options and (3) to discuss the importance of biogenic emissions of biomass systems. The discussion on biogenic carbon and other GHG emissions comprises four case studies of which two consider peat utilization, one forest biomass and one cultivated biomasses. Various different biomass types (peat, pine logs and forest residues, palm oil, rapeseed oil and jatropha oil) are used as examples to demonstrate the importance of biogenic carbon to life cycle GHG emissions. The biogenic carbon emissions of biomass are defined as the difference in the carbon stock between the utilization and the non-utilization scenarios of biomass. Forestry-drained peatlands were studied by using the high emission values of the peatland types in question to discuss the emission reduction potential of the peatlands. The results are presented in terms of global warming potential (GWP) values. Based on the results, the climate impact of the peat production can be reduced by selecting high-emission-level peatlands for peat production. The comparison of the two different types of forest biomass in integrated ethanol production in pulp mill shows that the type of forest biomass impacts the biogenic carbon emissions of biofuel production. The assessment of cultivated biomasses demonstrates that several selections made in the production chain significantly affect the GHG emissions of biofuels. The emissions caused by biofuel can exceed the emissions from fossil-based fuels in the short term if biomass is in part consumed in the process itself and does not end up in the final product. Including biogenic carbon and other land use carbon emissions into the carbon footprint calculations of biofuel reveals the importance of the time frame and of the efficiency of biomass carbon content utilization. As regards the climate impact of biomass energy use, the net impact on carbon stocks (in organic matter of soils and biomass), compared to the impact of the replaced energy source, is the key issue. Promoting renewable biomass regardless of biogenic GHG emissions can increase GHG emissions in the short term and also possibly in the long term.

Terpenoid transformations over gold catalysts

Nowadays biomass transformation has a great potential for the synthesis of value-added compounds with a wide range of applications. Terpenoids, extracted from biomass, are inexpensive and renewable raw materials which often have a biological activity and are widely used as important organic platform molecules in the development of new medicines as well as in the synthesis of fine chemicals and intermediates. At the same time, special attention is devoted to the application of gold catalysts to fine chemical synthesis due to their outstanding activity and/or selectivity for transformations of complex organic compounds. Conversion of renewable terpenoids in the presence of gold nanoparticles is one of the new and promising directions in the transformation of biomass to valuable chemicals. In the doctoral thesis, different kinds of natural terpenoids, such as α-pinene, myrtenol and carvone were selected as starting materials. Gold catalysts were utilized for the promising routes of these compounds transformation. Investigation of selective α-pinene isomerization to camphene, which is an important step in an industrial process towards the synthesis of camphor as well as other valuable substrates for the pharmaceutical industry, was performed. A high activity of heterogeneous gold catalysts in the Wagner-Meerwein rearrangement was demonstrated for the first time. Gold on alumina carrier was found to reach the α-pinene isomerization conversion up to 99.9% and the selectivity of 60-80%, thus making this catalyst very promising from an industrial viewpoint. A detailed investigation of kinetic regularities including catalyst deactivation during the reaction was performed. The one-pot terpene alcohol amination, which is a promising approach to the synthesis of valuable complex amines having specific physiological properties, was investigated. The general regularities of the one-pot natural myrtenol amination in the presence of gold catalysts as well as a correlation between catalytic activity, catalyst redox treatment and the support nature were obtained. Catalytic activity and product distribution were shown to be strongly dependent on the support properties, namely acidity and basicity. The gold-zirconia (Au/ZrO2) catalyst pretreated under oxidizing atmosphere was observed to be rather active, resulting in the total conversion of myrtenol and the selectivity to the corresponding amine of about 53%. The reaction kinetics was modelled based on the mechanistic considerations with the catalyst deactivation step incorporated in the mechanism. Carvone hydrogenation over a gold catalyst was studied with the general idea of investigating both the activity of gold catalysts in competitive hydrogenation of different functional groups and developing an approach to the synthesis of valuable carvone derivatives. Gold was found to promote stereo- and chemoselective carvone hydrogenation to dihydrocarvone with a predominant formation of the trans-isomer, which generally is a novel synthetic method for an industrially valuable dihydrocarvone. The solvent effect on the catalytic activity as well as on the ratio between trans- and cis-dihydrocarvone was evaluated.

Mitigation possibilities to Greenhouse gas emissions from power production in India

Global warming is assertively the greatest environmental challenge for humans of 21st century. It is primarily caused by the anthropogenic greenhouse gas (GHG) that trap heat in the atmosphere. Because of which, the GHG emission mitigation, globally, is a critical issue in the political agenda of all high-profile nations. India, like other developing countries, is facing this threat of climate change while dealing with the challenge of sustaining its rapid economic growth. India’s economy is closely connected to its natural resource base and climate sensitive sectors like water, agriculture and forestry. Due to Climate change the quality and distribution of India’s natural resources may transform and lead to adverse effects on livelihood of its people. Therefore, India is expected to face a major threat due to the projected climate change. This study proposes possible solutions for GHG emission mitigation that are specific to the power sector of India. The methods discussed here will take Indian power sector from present coal dominant ideology to a system, centered with renewable energy sources. The study further proposes a future scenario for 2050, based on the present Indian government policies and global energy technologies advancements.

Modelling of hydrogen stratification and gas mixing in containment using the APROS code

Hydrogen stratification and atmosphere mixing is a very important phenomenon in nuclear reactor containments when severe accidents are studied and simulated. Hydrogen generation, distribution and accumulation in certain parts of containment may pose a great risk to pressure increase induced by hydrogen combustion, and thus, challenge the integrity of NPP containment. The accurate prediction of hydrogen distribution is important with respect to the safety design of a NPP. Modelling methods typically used for containment analyses include both lumped parameter and field codes. The lumped parameter method is universally used in the containment codes, because its versatility, flexibility and simplicity. The lumped parameter method allows fast, full-scale simulations, where different containment geometries with relevant engineering safety features can be modelled. Lumped parameter gas stratification and mixing modelling methods are presented and discussed in this master’s thesis. Experimental research is widely used in containment analyses. The HM-2 experiment related to hydrogen stratification and mixing conducted at the THAI facility in Germany is calculated with the APROS lump parameter containment package and the APROS 6-equation thermal hydraulic model. The main purpose was to study, whether the convection term included in the momentum conservation equation of the 6-equation modelling gives some remarkable advantages compared to the simplified lumped parameter approach. Finally, a simple containment test case (high steam release to a narrow steam generator room inside a large dry containment) was calculated with both APROS models. In this case, the aim was to determine the extreme containment conditions, where the effect of convection term was supposed to be possibly high. Calculation results showed that both the APROS containment and the 6-equation model could model the hydrogen stratification in the THAI test well, if the vertical nodalisation was dense enough. However, in more complicated cases, the numerical diffusion may distort the results. Calculation of light gas stratification could be probably improved by applying the second order discretisation scheme for the modelling of gas flows. If the gas flows are relatively high, the convection term of the momentum equation is necessary to model the pressure differences between the adjacent nodes reasonably.

Towards sustainable Iron- and steelmaking with economic optimization

The iron and steelmaking industry is among the major contributors to the anthropogenic emissions of carbon dioxide in the world. The rising levels of CO2 in the atmosphere and the global concern about the greenhouse effect and climate change have brought about considerable investigations on how to reduce the energy intensity and CO2 emissions of this industrial sector. In this thesis the problem is tackled by mathematical modeling and optimization using three different approaches. The possibility to use biomass in the integrated steel plant, particularly as an auxiliary reductant in the blast furnace, is investigated. By pre-processing the biomass its heating value and carbon content can be increased at the same time as the oxygen content is decreased. As the compression strength of the preprocessed biomass is lower than that of coke, it is not suitable for replacing a major part of the coke in the blast furnace burden. Therefore the biomass is assumed to be injected at the tuyere level of the blast furnace. Carbon capture and storage is, nowadays, mostly associated with power plants but it can also be used to reduce the CO2 emissions of an integrated steel plant. In the case of a blast furnace, the effect of CCS can be further increased by recycling the carbon dioxide stripped top gas back into the process. However, this affects the economy of the integrated steel plant, as the amount of top gases available, e.g., for power and heat production is decreased. High quality raw materials are a prerequisite for smooth blast furnace operation. High quality coal is especially needed to produce coke with sufficient properties to ensure proper gas permeability and smooth burden descent. Lower quality coals as well as natural gas, which some countries have in great volumes, can be utilized with various direct and smelting reduction processes. The DRI produced with a direct reduction process can be utilized as a feed material for blast furnace, basic oxygen furnace or electric arc furnace. The liquid hot metal from a smelting reduction process can in turn be used in basic oxygen furnace or electric arc furnace. The unit sizes and investment costs of an alternative ironmaking process are also lower than those of a blast furnace. In this study, the economy of an integrated steel plant is investigated by simulation and optimization. The studied system consists of linearly described unit processes from coke plant to steel making units, with a more detailed thermodynamical model of the blast furnace. The results from the blast furnace operation with biomass injection revealed the importance of proper pre-processing of the raw biomass as the composition of the biomass as well as the heating value and the yield are all affected by the pyrolysis temperature. As for recycling of CO2 stripped blast furnace top gas, substantial reductions in the emission rates are achieved if the stripped CO2 can be stored. However, the optimal recycling degree together with other operation conditions is heavily dependent on the cost structure of CO2 emissions and stripping/storage. The economical feasibility related to the use of DRI in the blast furnace depends on the price ratio between the DRI pellets and the BF pellets. The high amount of energy needed in the rotary hearth furnace to reduce the iron ore leads to increased CO2 emissions.

Yrittäjyyskasvatus Oulun seudun ammattiopistossa

Tämä tutkimus käsittelee yrittäjyyskasvatusta Oulun seudun ammattiopistossa. Tutki-muksen tavoitteena on selvittää koetaanko ulkoisen yrittäjyyden opettaminen tärkeäksi ja onko sen integroiminen ammattiaineisiin onnistunut. Tutkimuksessa selvitetään myös opiskelijoiden halukkuutta toimia yrittäjänä tulevaisuudessa työmarkkinoilla sekä miten OSAOn strategiaan kirjatut yrittäjyyden tavoitteet ovat toteutuneet. Tutkimuksen teoreettinen viitekehys rakentuu kahdesta keskeisestä käsitteestä: Yrittäjyyskasvatus ja ulkoinen yrittäjyys. Tutkimuksen kohdeorganisaationa oli Oulun seudun ammattiopisto ja tarkemmin 2. ja 3. vuosikurssin opiskelijat ja opetushenkilöstö. Tutkimuksen empiirinen aineisto kerättiin sähköisellä Webropol-ohjelmistolla. Otokseen kuului noin 4000 opiskelijaa ja 577 opettajaa. Tutkimus edustaa kvantitatiivista tutkimusmenetelmää. Tutkimukseen vastasi 568 opiskelijaa ja 239 opettajaa. Tutkimuksen luotettavuuden kannalta määriä voidaan pitää riittävinä. Suurin osa kysymyksistä oli väittämiä, joiden vastausvaihtoehtona käytettiin Likertin viisiportaista asteikkoa. Tutkimuksen eri osiot käsittelivät ulkoisen yrittäjyyden tärkeyttä ammatillisella toisella asteella, yrittäjyyden integroimisen onnistumista ammattiaineisiin, OSAOn ilmapiiriä yrittäjyydestä sekä opiskelijoiden halua työskennellä tulevaisuudessa yrittäjänä. Saatujen vastauksien perusteella ulkoisen yrittäjyyden opettaminen koetaan tärkeäksi ammatillisella toisella asteella. Yrittäjyyden integroimista ammatillisiin aineisiin ei voida pitää täysin onnistuneena ja tähän nousi syyksi tavoitteiden uupuminen tutkinnon perusteissa. OSAOn ilmapiiri koettiin ulkoista yrittäjyyttä tukevaksi. Opiskelijat suhtautuivat myönteisesti siihen, että he voisivat tulevaisuudessa työskennellä yrittäjänä.

Lakisääteiset hitsaustyöt ja niiden laadunhallinta

Tässä diplomityössä selvitettiin UPM Kaukaan tehtailla esiintyviin lakisääteisiin hitsauskohteisiin liittyvää lainsäädäntöä ja lainsäädännön vaikutusta hitsaukselle. Lakisääteisiä hitsauskohteita ovat räjähdysvaaralliset tilat, painelaitteet, kemikaaliputkistot, kemikaalisäiliöt, maakaasulaitteet sekä kantavat teräsrakenteet. Diplomityössä selvitettiin lisäksi hitsauksen laadunhallintaa huomioiden korjaushitsaustyöt sekä uuden rakentaminen. Lakisääteet tuovat hitsauksen suorittamiselle usein tarkasti määritellyt velvoitteet koskien esimerkiksi dokumentointia, hitsaushenkilöstön pätevyyksiä, materiaaleja ja niin edelleen. Lakisääteet lisääntyvät jatkuvasti ja soveltamisalueet laajenevat, jolloin asioiden ylläpitäminen vaatii jatkuvaa seurantaa. Työssä luotiin ohjeistus koskien yleisesti hitsausta ja lisäksi käyttäjän ja omistajan velvoitteita koskevat ohjeet painelaitteista, maakaasulaitteista ja kemikaalilaitteista. Hitsauksen yleisohje koskee jokaista hitsaustapahtumaa korjaushitsauksesta uuden rakentamiseen. Ohje soveltuu lisäksi sopimusliitteeksi hitsaustyön tilauksissa.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.

Esimies osaamisen mahdollistajana

Tämän pro gradu -tutkielman tavoitteena oli esitellä ja analysoida osaami-sen johtamista sekä tuottaa käytännön suosituksia Alko Oy:n myymälöiden lähiesimiehille heidän henkilökuntansa osaamisen kehittämiseksi. Tämän lisäksi tutkimuksessa pyrittiin kerätyn aineiston avulla luomaan ymmärrys siitä, miten osaamisen johtamiset keinot vaikuttavat asiakastyytyväisyyteen. Tutkimus toteutettiin vertailevana tapaustutkimuksena ja tutkimusaineistoa kerättiin sekä kvantitatiivisella että kvalitatiivisella tutkimusmenetelmällä. Kohdeyrityksen myyjille lähetettiin kyselylomake heidän esimiestensä osaamisen johtamisen toimista, ja kyselystä saadun tiedon syventämiseksi haastateltiin kahdeksaa myymäläpäällikköä osaamisen johtamisen teemoista. Tutkimuksen perusteella pystyttiin muodostaman käsitys siitä, mistä osaa-misen johtaminen koostuu ja miten paremman ja heikomman osaamisen omaavien myymälöiden esimiesten toimet eroavat toisistaan. Vastausten perusteella saatiin myös ymmärrys niistä osa-alueista, joita kohdeyrityksen esimiesten toiminnassa pitäisi pyrkiä kehittämään. Osaamisen kehittämisen perustan muodostavat esimiehen oma esimerkki ja oppimiseen kannustava ilmapiiri. Esimies, joka onnistuu suuntaamaan henkilökuntansa oppimisen tukemaan organisaation tavoitteita, osaa henkilökohtaistaa yhtiön strategian sopimaan jokaisen toimenkuvaan. Oppimisen tukemisessa vaaditaan esimieheltä vahvaa henkilökunnan tuntemusta, tavoitteiden asettamista ja niiden toteutumisen seurantaa. Tutkimus osoitti esimiesten olevan pääsääntöisesti innostuneita työstään ja onnistuvan osaamisen suuntaamisen toimissa hyvin. Esimiehet voisivat kehittää toimintaansa ottamalla oman henkilökuntansa mukaan toiminnan suunnitteluun ja vastuuttamalla heitä myymälän toiminnan ja oman ammattitaitonsa jatkuvaan kehittämiseen.

Glädje i vårdandets värld

The present study is made in the context of basic research within the field of caring science. The overall aim is to uncover and make joy visible as an idea in the world of caring. The core of caring has historically always been to alleviate suffering and to serve life and health in a spirit of love and mercy. This study has a comprehensive direction focusing on history of ideas and culminates in a pattern of ideas contenting joy in the world of caring. Knowledge formation is based on creating understanding, wholeness and meaning with regard to the knowledge related to a context. For that a hermeneutical approach is used throughout the study. In order to understand joy more deeply, the original idea, the essence and expression, the concept of 'joy' and the related concepts of 'glad' and 'light' are examined in etymological dictionaries and in Swedish, English and Latin dictionaries. To support the interpretation classical texts containing philosophers’ thoughts about joy are used. Joy as an idea glimpses forth and is presented in the form of seven-fold pattern of ideas. Through the meaning-nuances of synonyms a realization of joy could be discerned and anchored in the heart. The seven-fold pattern form the background and represent a guide for the hermeneutic reading of joy, as it appears in the stories about caring for the years 1900–1933. The historical sources consist of the trade magazine Svensk sjukskötersketidning, books containing stories about caring, archival materials and textbooks on nursing. The result culminates in the seven-fold pattern of ideas contenting what makes joy active as caring. The true heart's pure joy - love, joy is a proof of love. The ardent heart's deep joy - joy of living, joy inspires and generates strength. The bearing heart's radiant joy - generosity, joy is a gift to the other with the promise of help. The inviting heart's sparkling joy – communion, joy invites communion. The elated heart's exhilarated joy - integration, joy enables the human to forget his or her suffering and approach to what he or she wants to be. The atmospheric heart's solemn joy - dignifying, joy creates a mood and an atmosphere where people perceive themselves dignified. The peaceful heart's great joy - rescuing, a joy turns out when the human has received what may be requested of what is good, is eluded from what is evil and is contented with his or her living lot. It is hoped that this basic research will open up for a vision that can contribute to joys further attention in the world of caring and be articulated there.

Testing FCM technique for the wind energy scenarios in Finland

In the latter days, human activities constantly increase greenhouse gases emissions in the atmosphere, which has a direct impact on a global climate warming. Finland as European Union member, developed national structural plan to promote renewable energy generation, pursuing the aspects of Directive 2009/28/EC and put it on the sharepoint. Finland is on a way of enhancing national security of energy supply, increasing diversity of the energy mix. There are plenty significant objectives to develop onshore and offshore wind energy generation in country for a next few decades, as well as another renewable energy sources. To predict the future changes, there are a lot of scenario methods developed and adapted to energy industry. The Master’s thesis explored “Fuzzy cognitive maps” approach in scenarios developing, which captures expert’s knowledge in a graphical manner and using these captures for a raw scenarios testing and refinement. There were prospects of Finnish wind energy development for the year of 2030 considered, with aid of FCM technique. Five positive raw scenarios were developed and three of them tested against integrated expert’s map of knowledge, using graphical simulation. The study provides robust scenarios out of the preliminary defined, as outcome, assuming the impact of results, taken after simulation. The thesis was conducted in such way, that there will be possibilities to use existing knowledge captures from expert panel, to test and deploy different sets of scenarios regarding to Finnish wind energy development.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.