Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transitions metal ions in dynamic N2 and CO2 atmospheres

Thermal stability and thermal decomposition of succinic acid, sodium succinate and its compounds with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA) in nitrogen and carbon dioxide atmospheres and TG-FTIR in nitrogen atmosphere. On heating, in both atmospheres the succinic acid melt and evaporate, while for the sodium succinate the thermal decomposition occurs with the formation of sodium carbonate. For the transition metal succinates the final residue up to 1180 ºC in N2 atmosphere was a mixture of metal and metal oxide in no simple stoichiometric relation, except for Zn compound, where the residue was a small quantity of carbonaceous residue. For the CO2 atmosphere the final residue up to 980 ºC was: MnO, Fe3O4, CoO, ZnO and mixtures of Ni, NiO and Cu, Cu2O.

Faster for the master! : exploring issues of religious expression and alternative Christian identity within the Finnish Christian metal music scene

Populärkulturen har i dagens läge kommit att utgöra en allt mer viktig och central inspirationskälla för allt fler människors konstruktion av den egna religiösa identiteten även inom traditionella och institutionella kristna sammanhang. Denna avhandling belyser denna utveckling i ljuset av den finländska kristna metallmusik-kulturen - en sällsynt stark sammanblanding av protestantisk kristendom och en utpräglad och kontroversiell populärmusikform och dess kultur. Fokus riktas framför allt på hur den kristna metallmusik-kulturen blir meningsfull för sina medlemmar genom de sätt på vilka den konstrueras diskursivt, dvs. genom de sätt på vilka den representeras och talas om bland sina egna anhängare. Den diskursiva konstruktionen av den kristna metallmusik-kulturen utforskas på ett såväl bredare transnationellt som ett finländskt nationellt plan. Studien redogör även för den kristna metalmusikens och -kulturens huvudsakliga verbala, visuella och estetiska kännetecken. Uppbyggnaden och spridningen av dagens transnationella kristna metallmusik-kultur undersöks även i ljuset av det teoretiska konceptet scene. Avhandlingens centrala argument är att den kristna metallmusikscenen erbjuder sina medlemmar en mängd resurser för skapandet av ett alternativt och komplementärt religiöst uttrycksätt, religiös praxis och en alternativ kristen identitet.

Mening genom (kristen) metal

Kirja-arvio

Atomic level phenomena on transition metal surfaces

In this study we discuss the atomic level phenomena on transition metal surfaces. Transition metals are widely used as catalysts in industry. Therefore, reactions occuring on transition metal surfaces have large industrial intrest. This study addresses problems in very small size and time scales, which is an important part in the overall understanding of these phenomena. The publications of this study can be roughly divided into two categories: The adsorption of an O2 molecule to a surface, and surface structures of preadsorbed atoms. These two categories complement each other, because in the realistic case there are always some preadsorbed atoms at the catalytically active surfaces. However, all transition metals have an active d-band, and this study is also a study of the in uence of the active d-band on other atoms. At the rst part of this study we discuss the adsorption and dissociation of an O2 molecule on a clean stepped palladium surface and a smooth palladium surface precovered with sulphur and oxygen atoms. We show how the reactivity of the surface against the oxygen molecule varies due to the geometry of the surface and preadsorbed atoms. We also show how the molecular orbitals of the oxygen molecule evolve when it approaches the di erent sites on the surface. In the second part we discuss the surface structures of transition metal surfaces. We study the structures that are intresting on account of the Rashba e ect and charge density waves. We also study the adsorption of suphur on a gold surface, and surface structures of it. In this study we use ab-initio based density functional theory methods to simulate the results. We also compare the results of our methods to the results obtained with the Low-Energy-Electron-Difraction method.

Modelos de transferência de metal pesado na cana-de-açúcar adubada com composto de lixo urbano

A pesquisa aborda a reciclagem do composto de lixo urbano (CLU) como fertilizante alternativo na cana-de-açúcar e como solução social e ambiental ao acúmulo de resíduos sólidos nos centros urbanos. Utilizou-se da modelagem matemática para conhecer a dinâmica dos metais pesados, visando ao estabelecimento de critérios e procedimentos para o uso seguro do CLU, limitado pela quantidade desses elementos. Foram construídos modelos compartimentais a partir de dados de experimentos em condições controladas e parcialmente validados com dados de campo. Esse modelo descreveu a transferência de metais pesados no sistema solo-raiz-parte aérea para a cana-de-açúcar. Pôde-se concluir, pelas condições desta pesquisa, que o metal mais preocupante foi o níquel, pois demora, aproximadamente, três anos para ser atenuado no solo e chega em maior quantidade na parte aérea. Quanto aos fatores argila, óxidos e pH do solo, notou-se que, nos solos de maior poder tampão, a passagem da maioria dos metais foi mais lenta. Esse modelo pode tornar-se importante aliado na definição de leis de utilização do CLU, visando à não-contaminação ambiental, redução no acúmulo de lixo e de custos de produção.

Horizontal pressures in cylindrical metal silos and comparison with different international standards

The focus of this research was to evaluate the horizontal pressures on a cylindrical metal silo of corrugated walls and flat bottom with 1.82m diameter and 5.4m high, and to compare the values with those obtained theoretically by the ISO 11697, EP 433 and AS 3774 standards. The silo was symmetrically filled and constant speed with wheat cv. soft red for two different height/diameter ratios (H/D) and was unloaded through three orifices with a diameter of 71.6mm, one concentric and two eccentrics. Horizontal pressures were measured on the walls of the silo at three positions using hydraulic type pressure cells. The results showed that shortly after the start of the unloading, there was a mass flow above the quota of H/D = 1.2, whereas below this quota funnel flow occurred. It can be said that the EP 433 standard was more appropriate to predict horizontal pressures in silos in H/D ratio = 1.0, with eccentric unloading. For the H/D ratio = 1.5, AS 3774 standard was the one that produced values closer to the experimental.

Development of simple and efficient synthetic strategies for production of fine chemicals of pharmaceutical relevance : metal-mediated allylation combined with applied catalysis

Den snart 200 år gamla vetenskapsgrenen organisk synteskemi har starkt bidragit till moderna samhällens välfärd. Ett av flaggskeppen för den organiska synteskemin är utvecklingen och produktionen av nya läkemedel och speciellt de aktiva substanserna däri. Därmed är det viktigt att utveckla nya syntesmetoder, som kan tillämpas vid framställningen av farmaceutiskt relevanta målstrukturer. I detta sammanhang är den ultimata målsättningen dock inte endast en lyckad syntes av målmolekylen, utan det är allt viktigare att utveckla syntesrutter som uppfyller kriterierna för den hållbara utvecklingen. Ett av de centralaste verktygen som en organisk kemist har till förfogande i detta sammanhang är katalys, eller mera specifikt möjligheten att tillämpa olika katalytiska reaktioner vid framställning av komplexa målstrukturer. De motsvarande industriella processerna karakteriseras av hög effektivitet och minimerad avfallsproduktion, vilket naturligtvis gynnar den kemiska industrin samtidigt som de negativa miljöeffekterna minskas avsevärt. I denna doktorsavhandling har nya syntesrutter för produktion av finkemikalier med farmaceutisk relevans utvecklats genom att kombinera förhållandevis enkla transformationer till nya reaktionssekvenser. Alla reaktionssekvenser som diskuteras i denna avhandling påbörjades med en metallförmedlad allylering av utvalda aldehyder eller aldiminer. De erhållna produkterna innehållende en kol-koldubbelbindning med en närliggande hydroxyl- eller aminogrupp modifierades sedan vidare genom att tillämpa välkända katalytiska reaktioner. Alla syntetiserade molekyler som presenteras i denna avhandling karakteriseras som finkemikalier med hög potential vid farmaceutiska tillämpningar. Utöver detta tillämpades en mängd olika katalytiska reaktioner framgångsrikt vid syntes av dessa molekyler, vilket i sin tur förstärker betydelsen för de katalytiska verktygen i organiska kemins verktygslåda.

Feasibility study of metal to polymer hybrid joining

The increasing demand for lightweight components has led to a huge exploitation of non-metallic materials such as polymers, fibers and elastomers in industrial and manufacturing processes. Recent trends towards cost effectiveness, weight reduction and production flexibility in industrial production and manufacturing processes has led to a growing interest in hybrid components where two or more dissimilar materials coexist to achieving specifically optimized characteristics. The importance of this research is to serve as a bridge to understanding the theories behind various joining techniques and the adaptation of the process for metal to polymer hybrid joints. Moreso, it helps companies to select the most productive and yet economical joining process for realization of lightweight metal to polymer hybrid components. This thesis is a literature review analyzing various materials that has been published on various joining methods for metal to polymer hybrid joints on the feasibility and eventual realization of the joint between these dissimilar materials. This study is aimed at theoretically evaluating the feasibility of joining processes between metal and plastic components by exploiting exhaustively joining and welding sources.

Sorption of metal ions to wood, pulp and bark materials

Ett huvudmål med denna avhandling var att erhålla ny information om växelverkan mellan metalljoner i vattenfas och träbaserade material såsom olika pappersmassor, ved och bark. Material av gran, tall och björk har studerats. En ny känslig kolonnkromatografisk metod utvecklades för bestämning av affinitetsordningar för 17 olika metalljoner. Av dessa bands trevärt järn och de mycket toxiska tungmetallerna bly, koppar och kadmium starkast till de studerade materialen. Växelverkan i dessa tvåfas system sker som jonbyte, huvudsakligen via komplexbildning av metalljoner till funktionella grupper i den fasta fasen. Vattenfasens pH är den viktigaste parametern som bestämmer totala halten av metalljoner som binds till materialen. Resultatet i denna avhandling kan delvis betraktas som grundforskning. En ny kunskap om metalljoners förekomst och kemiska reaktioner i dessa system är även av stor ekonomisk och ekologisk, betydelse, när man strävar till allt mera slutna system i moderna massafabriker. Avhandlingen visar också att trädbark har stor potential för biosorption av tungmetaller t.ex. från avfallsvatten. Trädbark har nästan lika stor bindningskapacitet som dyra syntetiska jonbytare.

Advanced welding technologies used for arctic metal structures

Rapid depletion of easy-to-access fossil fuel, predominantly, oil and gas resources has now necessitated increase in need to develop new oil and gas sources in ever more remote and hostile environments. This is necessary in order to explore more oil and gas resources to meet rapidly rising long-term energy demand in the world, both at present and in the nearest future. Arctic is one of these harsh environments, where enormous oil and gas resources are available, containing about 20% of the world total oil and gas, but the environmental conditions are very harsh and hostile. However, virtually all the facilities required for the exploration and development of this new energy source are constructed with metals as well as their alloys and are predominantly joined together by welding processes and technologies. Meanwhile, due to entirely different environment from the usual moderate temperate region, conventional welding technologies, common metals and their alloys cannot be applied as this Arctic environment demand metals structures with very high toughness and strength properties under extremely low temperature. This is due to the fact that metals transit from ductility to brittleness as the temperature moves toward extreme negative values. Hence, this research work investigates and presents the advanced welding technologies applicable to Arctic metal structures which can give satisfactory weldments under active Arctic service conditions. .

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ≥ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore® membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

Krigaren och transvestiten : gestaltningar av mörker och maskuliniteter i finländsk black metal

Avhandlingen undersöker gestaltningar av mörker och maskuliniteter i den finländska black metal-scenen. Normativa hegemoniska och normbrytande subversiva gestaltningar av maskuliniteter bland de mest aktiva anhängarna av den finländska black metal-scenen undersöks som uttryck för återkommande, kulturella mönster. Mönstren analyseras med hjälp av teorier om hegemonisk maskulinitet, heteronormativitet, genusperformativitet, subversivitet och protestmaskulinitet. Queerteori och (kritisk) mansforskning som har sina ursprung i feministisk forskning utgör avhandlingens teoretiska underlag. Begreppen stil och ideologi aktualiseras i en diskussion kring hur mörker, ett begrepp som är av centralt värde inom den finländska black metal-scenen, kan förstås och uttryckas av scenmedlemmarna. Mörkret, som ofta ideologimässigt består av antikristliga element, inom den finländska scenen i regel förknippade med satanism, uttrycks genom låttexter, det visuella och det musikaliska, vilka tillsammans utgör black metal-stilen.

From War Pigs to Unsung Heroes: The Criticism and Justification of War in Metal Lyrics

Tässä tutkimuksessa käsitellään heavy metal -kappaleiden sanoitusten sisältöä. Tutkimusmateriaaliin on valittu yksi teema, sota, jonka avulla avataan sanoitusten sisältöä ja merkitystä. Metallimusiikki alakulttuurina on tyylillisesti ja temaattisesti spesifi, ja sillä on omat musiikilliset tavoitteensa. Tässä tutkimuksessa tarkastellaan erityisesti sitä miten sotaa kritisoidaan tai perustellaan heavy rock -sanoituksissa. Tutkimusmateriaalini koostuu 29 englanninkielisen kappaleen sanoituksesta vuosilta 1970–2012. Edustettuina on useita ajanjaksoja sekä maita. Yhdistävänä tekijänä on englannin kielen lisäksi se, että kaikki sanoitukset käsittelevät modernia länsimaista sodankäyntiä. Tekstit valittiin sen perusteella, että niissä ilmeni positiivinen tai negatiivinen näkökulma sotaan. Tutkimus nojaa Theo van Leeuwenin legitimaatioteoriaan, joka puolestaan pohjautuu diskurssianalyysiin. Legitimaatioteoria käsittää neljä strategiaa, jotka voivat joko kritisoida tai perustella sosiaalisia käytänteitä. Ne ovat auktoriteetteihin vetoaminen, moraalinen arviointi, järkeistäminen ja mytopoeesi. Yksi tavoitteistani tutkimuksessani on selvittää legitimaatioteorian toimivuutta omassa materiaalissani. Käytän metodina lähilukua, joka mahdollistaa niiden sanojen ja ilmaisujen identifioimisen, jotka ovat näkökulmaltaan joko positiivisesti tai negatiivisesti sotaan suhtautuvia. Analyysini kannalta tärkeitä ovat sekä kieli- että kulttuurikonteksti, sillä ne määrittelevät sanojen merkityksen. Analyysin perusteella kävi ilmi, että esimerkit jakautuivat eri strategioiden välille hyvin epätasaisesti. Auktoriteetteihin vetoamisen strategiasta löytyi vain yksi esimerkki, kun taas moraalisen arvioinnin esimerkkejä oli neljätoista. Lisäksi kaikkia legitimaatioteorian alaryhmiä ei löytynyt materiaalista ollenkaan. Osalla alaryhmistä oli useita esiintymiä, mutta osalla vain yksi. Esimerkkien epätasaista jakautumista selittää mm. se, että tutkimuksen materiaalin kannalta kaikki alakategoriat eivät ole relevantteja. Jotta tutkimustuloksista saataisiin edustavampi, laajempi otanta olisi tarpeen. Legitimaatioteorian soveltuvuutta sanoituksien yhteydessä tulisi tutkia laajemmin.