L'objectif de ce travail était d'étudier de manière approfondie l'effet de l'indium dans des catalyseurs trimétalliques de reformage catalytique à base de platine, étain et indium. Des catalyseurs ont ainsi été synthétisés selon différents protocoles de préparation et de multiples caractérisations (spectroscopies Mössbauer d'étain, XANES, EXAFS, IR-CO, MEBT, chimisportion du CO, TPR et TPD) ont été mises en oeuvre afin d'élucider l'impact de l'indium sur la nature des phases métalliques présentes au sein du catalyseur. Il a ainsi été montré que la nature des sites métalliques dépend de la méthode d'introduction de l'indium. Quand l'indium est précipité avec la source d'alumine des alliages de type PtxSn sont obtenus alors que lorsque les métaux sont imprégnés sur la surface de l'alumine des espèces subsitutionnelles Pt-Sn sont formées. Il a aussi été montré que l'augmentation de la teneur en indium entraine une augmentation de la concentration atomique d'étain dans les alliage PtxSn et un remplacement de l'étain par l'indium dans les espèces substitutionnelles. Nous avons également réussi à préparer des catalyseurs avec des quantités élevées d'alliage Pt3Sn sur la base des connaissances acquises sur l'impact de l'indium et en déposant l'étain par une réaction organométallique contrôlée de surface. D'un point de vue catalytique, les tests de reformage du n-heptane mettent en évidence l'impact positif de l'indium puisque les catalyseurs à base de Pt-Sn-In sont moins sélectifs pour les réactions parasites d'hydrogénolyse et d'hydrocraquage et plus sélectifs pour l'isomérisation que les catalyseurs à base de Pt-Sn. / This work consists of a detailed study on the effect of indium in alumina supported trimetallic PtSnIn-based naphtha reforming catalysts. These catalysts were reproduced using different preparation protocols and the indium effect was investigated using 119Sn Mössbauer spectroscopy, XANES, EXAFS spectroscopies, IR-CO, STEM, CO chemisorption, TPR and TPD. It appears that the nature of the metallic active centres depends on the method with which indium was introduced. When co-precipitating the indium precursor with the Al source, PtxSn alloys were formed, whereas when metals were impregnated on the surface, substitutional Pt-Sn alloys were observed. Increasing the In content in the frst type of catalysts leads to an increase in the Sn concentration in PtxSn alloys, whereas a gradual replacement of Sn by indium in susbstitutinal alloys is observed in the second type of catalysts. These results allowed preparing catalysts with high Pt3Sn alloy contents using the effect of indium in catalysts prepared by Sn organometallic controlled surface reactions (CSR). From a catalytic point of view, n-heptane reforming tests show that trimetallic PtSnIn-based catalysts are less selective to hydrogenolysis and hydrocracking reactions, and highly selective to isomerisation, compared to the bimetallic PtSn-based catalyst.

Neste trabalho foram soldadas 4 amostras de rodas para veículos comerciais pelo processo de soldagem Tandem-MIG. Para cada amostra foram utilizados parâmetros de soldagem diferentes de modo a se obter formatos de cordão de solda distintos. O objetivo do trabalho foi avaliar a influência desses formatos de cordão de solda no desempenho em fadiga. Para os materiais utilizados, SAE1010AA e SAE1015A, foram realizados os seguintes ensaios: análise de composição química, análise micrográfica, levantamento das curvas tensão x deformação, medidas de microdureza Vickers e levantamento das curvas SN pelo método de flexão alternada (R=-1). Através da composição química constatou-se que ambos os aços são de baixo carbono e atendem o especificado pela norma SAEJ403. Através da análise micrográfica foi verificado que as fases presentes foram ferrita e perlita, e o tamanho médio de grão foi de 11,2 ?m para os dois materiais. O aço SAE1010AA apresentou limite de escoamento médio de 265,2 MPa, limite de resistência de 384,8 MPa e alongamento médio de 43,9%. Já o aço SAE1015AA apresentou limite de escoamento médio de 260,1 MPa, limite de resistência de 407,3 MPa e alongamento de 41,9%. Para os dois materiais, o limite de resistência à fadiga (2.10-6 ciclos) foi de 225 MPa. Foi realizada a caracterização das 4 amostras soldadas. Através das curvas SN observou-se que o limite de resistência à fadiga para as amostras soldadas apresentou redução para valores entre 180 e 160 MPa. Com os mapas de microdureza Vickers levantados foi possível perceber as diferenças de microdureza obtidas de acordo com os parâmetros de soldagem utilizados e consequentemente com as microestruturas formadas. Com as imagens obtidas na análise micrográfica observou-se a formação de microestruturas com formatos e tamanhos diversos tanto nas regiões da zona termicamente afetada das amostras como na região de solidificação do cordão de solda. Finalmente, com a realização da análise via MEV, constatou-se que todas as trincas por fadiga iniciaram na superfície dos corpos de prova. Foram observadas estrias de fadiga, com maior e menor intensidade de acordo com cada amostra, ao longo da região de fratura. Além disso, foi observada a geração de múltiplas trincas por fadiga em duas amostras. / In this study four samples of commercial vehicle wheels were welded using the Tandem-MIG process. For each sample different welding parameters were used to get different kinds of weld bead shape. The aim of this study was to evaluate the influence of these weld bead shapes in fatigue performance. For the SAE1010AA and SAE1015AA materials the following tests were performed: chemical composition analysis, microstructure characterization, SN curves by alternating bending method (R=-1). Through analyzing chemical composition, it was found that both materials are low carbon steel and they meet the SAE J403 standard. In microstructure characterization, ferrite and perlite microstructure were found, with an average grain size of 11,2 ?m for both steels. The SAE1010AA showed an average yield strength of 265,2 MPa, an average tensile strength of 384,8 MPa, and alongation of 43,9%. The SAE1015AA showed an average yield strength of 260,1 MPa, an average tensile strength of 407,3 MPa, and alongation of 41,9%. For both materials, the fatigue limit (2.10-6 ciclos) was 225 MPa. The characterization of the four samples was done. In SN curves the fatigue limit for welded samples showed a reduction to values of between 180 and 160 MPa. In the Vickers microhardness test, it was possible to notice the differences between the microhardness obtained in accordance with welding parameters used and, consequently, the microstructure formed. In microstructure analysis, different kinds and sizes of microstructure were observed to have formed in both the heat-affected zone and the welded zone. Finally, through MEV analysis, all fatigue cracks were seen to have begun on the surface of the samples. Fatigue estriaton, with major and minor intensity depending on the sample, was observed along the fracture region. Furthermore, the beginning of multiple fatigue cracks were seen in two samples.

L’agriculture urbaine et périurbaines, bien que très pratiquée partout dans le monde est parfois mis en difficulté à travers l’utilisation de fertilisants nocifs. L’objectif général de cette thèse est de mener une étude du risque de la contamination du système sol-plante par les composés organométalliques du Pb Hg et Sn, dans un contexte d’agriculture urbaine caractérisé par l’utilisation des débris de combustion (DC) d’ordures ménagères issus des décharges urbaines, pour fertiliser les sols maraîchers. Dans cet objectif, les espèces Lactuca sativa, Amaranthus hybridus et Corchorus olitorius ont été cultivées sur des sols amendés par les DC, comme le font les agriculteurs in situ. Les sols amendés et non amendés ont été échantillonnés et les légumes ont été récoltés à quatre stades de leur croissance. Les métaux tels que le plomb (Pb), le mercure (Hg) et l’étain (Sn) ont été analysés sous leurs formes inorganiques et organiques par ICP-MS et GC-ICP-MS respectivement. Les résultats obtenus révèlent la présence du mono méthylmercure (MMeHg) dans les sols et dans les plantes avec des concentrations variant respectivement d’une valeur non détectée (nd) à 172 ng/g et de 7,8 ng/g à 34,7 ng/g. Le tétra éthyl Plomb (TEtPb) se révèle être le composé organoplombique (COP) le plus représenté dans les sols avec des concentrations variant de 18,4 ng/g à 44612 ng/g. Alors que c’est plutôt le mono éthyl plomb (MEtPb) qui est le COP le plus représenté dans les plantes, avec des concentrations variant de 0,78 ng/g à 56,9 ng/g. Les composés organostannique (COT) ont également été identifiés dans les sols et dans les plantes avec une prédominance du dibutyl étain (DBT) dans le sol, et du mono phényl étain (MPhT) dans la plante. Le suivi de l’accumulation de ces organométalliques par les plantes à différents stades de leur croissance, révèle globalement une diminution des quantités de polluants accumulées dans la plante entre le 1er stade de croissance et le stade de maturité. Les résultats des facteurs d’absorptions (Fa) ont mis en évidence le caractère phytodisponible des formes organométalliques dans le sol à l’exception du DBT. Ils ont aussi révélé les aptitudes hyper accumulatrices de A. hybridus et L. sativa vis-à-vis du TBT. Les résultats combinés des Fa, des facteurs de translocation et des rapports de mobilité entre le sol et les feuilles ont permis de mettre en évidence une translocation aisée ou facilitée des formes éthylées (TEtPb), butylées (TBT) et phénylées (MPhT) des racines vers les feuilles. Des trois espèces de plantes, C. olitorius se révèle être l’espèce la plus accumulatrice de MMeHg, de COP et COT. Mais au vue des doses d’expositions journalières (DEJ) à ces polluants toxiques par ingestion de ces légumes, c’est la consommation de L. sativa qui présente le plus grand danger pour le consommateur. D’ailleurs la consommation de ce légume donne une DEJ de MPhT qui est supérieure à la dose journalière admissible (DJA) des composés phénylées de l’étain. / Urban and suburban agriculture though widely practiced all over the world, sometimes faces difficulties due to the use of poor fertilizers. The objective of this thesis is to study the contamination risks of the soil-plant system by organometallic compounds (Pb, Hg and Sn), in a particular context of urban and suburban agriculture. To meet this goal, the species Lactuca sativa, Amaranthus hybridus and Corchorus olitorius were cultivated on soils amended with combustion debris (CD), like the farmers do in situ. The amended and non-amended soils are sampled and vegetables harvested at maturity on one hand, and at different stages of their growth on the other. The samples are treated, then the inorganic and organics forms of Pb, Hg and Sn are analyzed by ICP-MS and GC-ICP-MS respectively. The results obtained reveal the presence of mono methylmercury (MMeHg) in the soils and in the plants with concentrations respectively varying between nd to 171.567 ng/g and 7.83 ng/g to 34.72 ng/g. Tetra ethyl lead (TEtPb) is the most represented organo lead compounds (OLC) in the soils with concentrations ranging from 18.45 ng/g to 44611.959 ng/g respectively. Whereas in the plants, mono ethyl lead (MEtPb) is the most represented OLC with concentrations ranging from 0.78 ng/g to 56.90 ng/g. OTC were equally identified in the soils as well as in the plants with a predominance of dibutyl tin (DBT) in soil, and mono phenyltin (MPhT) in plants. Amongst the three plant species, C. olitorius turns out to be the species which accumulates MMeHg, OLC and OTC most. But in view of the of daily exposure doses (DED) to these toxic pollutants by ingestion of these vegetables, it is the consumption of L. sativa which presents the greatest danger. Moreover, consumption of this vegetable gives a DED of MPhT which is higher than its acceptable daily intake. The follow up of the accumulation of these organometallics by plants at different stages of their growth, revealed that the quantities of pollutants accumulated, decrease in the plant between first stage of growth and the maturity stage. The results of the absorption factors (Fa) have allowed to underline of phyto availability character of organometallics forms in soil, except for DBT. They have also revealed hyper accumulator abilities of A. hybridus and L. sativa for TBT. The combined results of Fa, translocation factor (Ft) and reports of mobility between the soil and the leaves (Rm (f/s)) have allowed to underline the facilitated translocation of ethylated (TEtPb), butylated (TBT) and phenylated (MPhT) forms, from the roots to the leaves.

Neste trabalho foram soldadas 4 amostras de rodas para veículos comerciais pelo processo de soldagem Tandem-MIG. Para cada amostra foram utilizados parâmetros de soldagem diferentes de modo a se obter formatos de cordão de solda distintos. O objetivo do trabalho foi avaliar a influência desses formatos de cordão de solda no desempenho em fadiga. Para os materiais utilizados, SAE1010AA e SAE1015A, foram realizados os seguintes ensaios: análise de composição química, análise micrográfica, levantamento das curvas tensão x deformação, medidas de microdureza Vickers e levantamento das curvas SN pelo método de flexão alternada (R=-1). Através da composição química constatou-se que ambos os aços são de baixo carbono e atendem o especificado pela norma SAEJ403. Através da análise micrográfica foi verificado que as fases presentes foram ferrita e perlita, e o tamanho médio de grão foi de 11,2 ?m para os dois materiais. O aço SAE1010AA apresentou limite de escoamento médio de 265,2 MPa, limite de resistência de 384,8 MPa e alongamento médio de 43,9%. Já o aço SAE1015AA apresentou limite de escoamento médio de 260,1 MPa, limite de resistência de 407,3 MPa e alongamento de 41,9%. Para os dois materiais, o limite de resistência à fadiga (2.10-6 ciclos) foi de 225 MPa. Foi realizada a caracterização das 4 amostras soldadas. Através das curvas SN observou-se que o limite de resistência à fadiga para as amostras soldadas apresentou redução para valores entre 180 e 160 MPa. Com os mapas de microdureza Vickers levantados foi possível perceber as diferenças de microdureza obtidas de acordo com os parâmetros de soldagem utilizados e consequentemente com as microestruturas formadas. Com as imagens obtidas na análise micrográfica observou-se a formação de microestruturas com formatos e tamanhos diversos tanto nas regiões da zona termicamente afetada das amostras como na região de solidificação do cordão de solda. Finalmente, com a realização da análise via MEV, constatou-se que todas as trincas por fadiga iniciaram na superfície dos corpos de prova. Foram observadas estrias de fadiga, com maior e menor intensidade de acordo com cada amostra, ao longo da região de fratura. Além disso, foi observada a geração de múltiplas trincas por fadiga em duas amostras. / In this study four samples of commercial vehicle wheels were welded using the Tandem-MIG process. For each sample different welding parameters were used to get different kinds of weld bead shape. The aim of this study was to evaluate the influence of these weld bead shapes in fatigue performance. For the SAE1010AA and SAE1015AA materials the following tests were performed: chemical composition analysis, microstructure characterization, SN curves by alternating bending method (R=-1). Through analyzing chemical composition, it was found that both materials are low carbon steel and they meet the SAE J403 standard. In microstructure characterization, ferrite and perlite microstructure were found, with an average grain size of 11,2 ?m for both steels. The SAE1010AA showed an average yield strength of 265,2 MPa, an average tensile strength of 384,8 MPa, and alongation of 43,9%. The SAE1015AA showed an average yield strength of 260,1 MPa, an average tensile strength of 407,3 MPa, and alongation of 41,9%. For both materials, the fatigue limit (2.10-6 ciclos) was 225 MPa. The characterization of the four samples was done. In SN curves the fatigue limit for welded samples showed a reduction to values of between 180 and 160 MPa. In the Vickers microhardness test, it was possible to notice the differences between the microhardness obtained in accordance with welding parameters used and, consequently, the microstructure formed. In microstructure analysis, different kinds and sizes of microstructure were observed to have formed in both the heat-affected zone and the welded zone. Finally, through MEV analysis, all fatigue cracks were seen to have begun on the surface of the samples. Fatigue estriaton, with major and minor intensity depending on the sample, was observed along the fracture region. Furthermore, the beginning of multiple fatigue cracks were seen in two samples.

In this study the anchorage of Sn (IV) complexes on silica gel to obtain heterogeneous catalysts with potential activity in transesterification was investigated. The Sif-DMTDU e Sif-TBTU catalysts were synthesized and anchored on silica modified with trimethoxysilane, and Si-TBTM e o Si-DBTDM were anchored without silica modification. The complexes formation was confirmed by spectroscopy in the mid-infrared region, optical atomic emission spectrometry, nitrogen physisorption and determination of the surface area of the catalyst by BET method, thermogravimetry and scanning transmission electron microscopy. The Si-DBTDM showed the largest tin content in silica, 17.3 %, followed by Sif-DMTDU with 12.0 %, Si-TBTM with 7.4 % and 5.0% for Sif-TBTU. The heterogenized compounds and their homogeneous equivalents, were tested for the transesterification of ethyl acetate in order to examine the catalytic behavior in this type of reaction. The transesterification were performed in vials, in order to convert the ethyl acetate in methyl acetate. The reaction products were characterized by gas chromatography. All homogeneous and heterogeneous catalysts tested, exhibit catalytic activity at the conditions employed. The reactivity order for homogeneous catalysts was DBTDM> DMTDU> TBTU> TBTM. When these species are heterogenized, the same order of reactivity was observed, but is necessary more time to achieve the same catalytic activity observed in the case of the homogeneous complex. In reuse and leaching tests, is observed the loss of Sn (IV) of the silica matrix, but the catalysts remained active for up to 10 reaction cycles, which represents 20 hours of reaction. The SIf-DMTDU and Si-DBTDM catalysts were more active than Sif TBTU and Si-TBTM, however Sif-TBTU was more advantageous, since from 4º reuse it showed the highest activity. Finally, at the conditions studied, the use of the complex base Sn (IV) anchored on silica proved to be very promising in the transesterification reaction. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foi investigada a ancoragem de complexos de Sn(IV), em sílica gel, a fim de obter catalisadores heterogêneos, com potencial atividade na reação de transesterificação. Os catalisadores Sif-DMTDU e Sif-TBTU foram sintetizados e ancorados em sílica modificada com trimetoxissilano, enquanto o Si-TBTM e o Si-DBTDM foram ancorados sem a necessidade de modificar a superfície da sílica. A formação dos complexos foi confirmada por espectroscopia na região do infravermelho médio, espectrometria ótica de emissão atômica, fisissorção de nitrogênio e determinação da área superficial dos catalisadores pelo método de BET, termogravimetria e microscopia eletrônica de varredura e de transmissão. O Si-DBTDM apresentou o maior teor de estanho na sílica, 17,3 %, seguido do Sif-DMTDU que apresentou 12,0 %, Si-TBTM que apresentou 7,4 % e o Sif-TBTU 5,0 %. Os compostos heterogeneizados e seus respectivos homólogos foram testados na transesterificação do acetato de etila, com o intuito de analisar o comportamento catalítico nesse tipo de reação. As reações de transesterificação foram realizadas em frascos tipo vial, visando à conversão do acetato de etila em acetato de metila. Os produtos reacionais obtidos foram caracterizados através da cromatografia gasosa. Todos os catalisadores homogêneos e heterogêneos testados apresentaram atividade catalítica e, nas condições empregadas, a ordem de reatividade para os catalisadores homogêneos foi DBTDM>DMTDU>TBTU>TBTM. Quando tais espécies foram heterogeneizadas, a mesma ordem de reatividade foi observada, porém houve necessidade de um maior tempo reacional para atingir a mesma atividade catalítica observada no caso dos complexos homogêneos. Nos testes de reuso e lixiviação, foi possível observar a perda de Sn(IV) da matriz de sílica, porém os catalisadores se mantiveram ativos por até 10 ciclos reacionais, o que representa 20 horas de reação. Os catalisadores Sif-DMTDU e Si-DBTDM foram mais ativos que o Sif-TBTU e Si-TBTM, no entanto o Sif-TBTU foi mais vantajoso, uma vez que a partir do 4° reuso ele apresentou as maiores atividades. Por fim, nas condições estudadas, o uso de complexos a base de Sn(IV) ancorados em sílica mostrou-se bastante promissor na reação de transesterificação.

In Yoshii et al., we described a new method for measuring extragalactic distances based on dust reverberation in active galactic nuclei (AGNs), and we validated our new method with Cepheid variable stars. In this Letter, we validate our new method with Type Ia supernovae (SNe Ia) that occurred in two of the AGN host galaxies during our AGN monitoring program: SN 2004bd in NGC 3786 and SN 2008ec in NGC 7469. Their multicolor light curves were observed and analyzed using two widely accepted methods for measuring SN distances, and the distance moduli derived are m= 33.47 +/- 0.15 for SN 2004bd and 33.83 +/- 0.07 for SN 2008ec. These results are used to obtain independently the distance measurement calibration factor, g. The g value obtained from the SN Ia discussed in this Letter is gSN= 10.61 +/- 0.50, which matches, within the range of 1s uncertainty, gDUST = 10.60, previously calculated ab initio in Yoshii et al. Having validated our new method for measuring extragalactic distances, we use our new method to calibrate reverberation distances derived from variations of Ha emission in the AGN broad-line region, extending the Hubble diagram to z approximate to 0.3 where distinguishing between cosmologies is becoming possible.

The long-lived fission product 126Sn (105 years) (Weast (1972)) is of substantial interest in the context of nuclear waste disposal in deep underground repositories. However, the prevalent redox state, the aqueous speciation as well as the reactions at the mineral-water interface under the expected anoxic conditions are a matter of debate. Therefore, in this PhD thesis I present work on the reactions of SnII with three Fe-bearing minerals as a function of pH, time, and SnII loading under anoxic condition with O2 level < 2 ppmv. The first mineral, goethite, contains only trivalent Fe (FeIIIOOH), the second, magnetite, contains both FeII and FeIII (FeIIFeIII2O4), and the third, mackinawite (FeIIS), contains only divalent Fe. The uptake behavior of the three mineral surfaces was investigated by batch sorption studies. Tin redox state was investigated by Sn-K X-ray absorption near-edge structure (XANES) spectroscopy, and the local, molecular structure of the expected Sn surface complexes and precipitates was studied by extended X-ray absorption fine-structure (EXAFS) spectroscopy. Selected samples were also investigated by transmission electron microscopy (TEM) to elucidate the existence and nature of secondary, Fe- and /or Sn containing solids, and by Mössbauer spectroscopy to study FeII and FeIII in the minerals. Based on the such-obtained molecular-level information, surface complexation models (SCM) were fitted to the batch sorption data to derive surface complexation constants. In the presence of the FeIII-bearing minerals magnetite and goethite, I observed a rapid uptake and oxidation of SnII to SnIV. The local structure determined by EXAFS showed two Sn-Fe distances of about 3.15 and 3.60 Å in line with edge and corner sharing arrangements between octahedrally coordinated SnIV and the Fe(O,OH)6 octahedra at the magnetite and goethite surfaces. While the respective coordination numbers suggested formation of tetradentate inner-sphere complexes between pH 3 and 9 for magnetite, bidentate inner-sphere complexes (single edge-sharing (1E) and corner-sharing (2C)) prevail at the goethite surface at pH > 3, with the relative amount of 2C increasing with Sn loading. The interfacial electron transfer between sorbed SnII and structural FeIII potentially leads to dissolution of FeII and transformation to secondary FeII/FeIII oxide minerals. There is no clear evidence to confirm the reductive dissolution in the Sn/ magnetite system, Rietveld refinement of XRD patterns, however, indicates an increase of FeII/FeIII ratio in the magnetite structure. For the Sn/goethite system, dissolved FeII increased with SnII loading at the lowest pH investigated, indicative of reductive dissolution. At pH >5, spherical and cubic particles of magnetite were observed by TEM, and their number increased with SnII loading. Based on previous finding, this secondary mineral transformation of goethite should proceed via dissolution and recrystallization. The molecular structure and oxidation state of sorbed Sn were then used to fit the batch sorption data of magnetite and goethite with SCM. The sorption data on magnetite were fit with the diffuse double layer model (DLM) employing two different complexes, the first ( = -14.97±0.35) prevailing from pH 2 to 9, and the second ( = -17.72±0.50), which forms at pH > 9 by co-adsorption of FeII, thereby increasing sorption at this high pH. The sorption data on goethite were fitted with the charge distribution–multisite complexation model (CD-MUSIC). Based on the EXAFS-derived presence of two different bidentate inner-sphere complexes ((≡FeOH)(≡Fe3O)Sn(OH)3 (1E) and (≡FeOH)2Sn(OH)3) (2C)), sorption affinity constants of 15.5 ±1.4 for the 1E complex and of 19.2 ±0.6 for the 2C complex were obtained. The model is not only able to predict sorption across the observed pH range, but also the transition from a roughly 50/50 distribution of the two complexes at 12.5 µmol/g Sn loading, to the prevalence of the 2C complex at higher loading, in line with the EXAFS data. The retention mechanism of SnII by mackinawite is significantly dependent on the solution pH, reflecting the transient changes of the mackinawite surface in the sorption process. At pH <7, SnII is retained in its original oxidation state. It forms a surface complex, which is characterized by two short (2.38 Å) Sn-S bonds, which can be interpreted as the bonds towards the S-terminated surface of mackinawite, and two longer Sn-S bonds (2.59 Å), which point most likely towards the solution phase, completing the tetragonal SnS4 innersphere sorption complex. Precipitation of SnS or formation of a solid solution with mackinawite could be excluded. At pH > 9, SnII is completely oxidized by an FeII/FeIII (hydr)oxide, most likely green rust, forming on the surface of mackinawite. Six O atoms at 2.04 Å and 6 Fe atoms at 3.29 Å demonstrate a structural incorporation by green rust, where SnIV substitutes for Fe in the crystal structure. The transition between SnII and SnIV and between sulfur and oxygen coordination takes place between pH 7 and 8, in accordance with the transition from the mackinawite stability field to more oxidized Fe-bearing minerals. The uptake processes of SnII by mackinawite are largely in line with the uptake processes of divalent cations of other soft Lewis-acid metals like Cd, Hg and Pb. Very different Sn retention mechanisms were hence active, including oxidation to SnIV and formation of tetradentate and bidentate surface complexes of the SnIV hydroxo moieties on goethite and magnetite, and in the case of mackinawite a SnII sulfide species forming a bidentate surface complex at low pH, and structural incorporation of SnIV by an oxidation product, green rust, at high pH. In all three mineral systems and largely independent on the retention mechanisms, inorganic SnII was strongly retained, with Rd values always exceeding 5, across the relatively wide pH range relevant for the near and far-field of nuclear waste respositories. For the goethite and magnetite systems, the retention could be well modeled with surface complexation models based on the molecular structural data. This is an important contribution to the safety case for future nuclear waste repositories, since such SCMs provide reliable means for predicting the radioactive dose released by 126Sn from nuclear waste into the biosphere across a wide range of physicochemical conditions typical for the engineered as well as natural barriers.

A supernova (SN) is the explosive destruction of a star. Via a luminous outpouring of radiation, the SN can rival the brightness of its SN host galaxy for months or years. In the past decade, astronomical surveys regularly observing the sky to deep limiting magnitudes have revealed that core collapse SNe (the demises of massive stars) are sometimes preceded by eruptive episodes by the progenitor stars during the years before the eventual SN explosion. Such SNe tend to show strong signatures of interaction between the SN ejecta and the circumstellar medium (CSM) deposited by the star before the SN explosion, likely by mass-loss episodes like the ones we have started to observe regularly. The complex CSM resolved around certain giant stars in our own galaxy and the eruptions of giant stars like η Car in the 19th century can be seen in this context. As the SN ejecta of an interacting SN sweep up the CSM of the progenitor, radiation from this process offers observers opportunity to scan the late mass loss history of the progenitor. In this thesis, interacting SNe and eruptive mass loss of their progenitors is discussed. The SN iPTF13z (discovered by the intermediate Palomar Transient Factory, iPTF) is presented. This transient was followed with optical photometry and spectroscopy during 1000 days and displayed a light curve with several conspicuous re-brigthenings ("bumps"), likely arising from SN ejecta interacting with denser regions in the CSM. Around 200 days before discovery, in archival data we found a clear precursor outburst lasting &gt;~ 50 days. A well-observed (but not necessarily well understood) event like SN 2009ip, which showed both precursor outbursts and a light curve bump, makes an interesting comparison object. The embedding of the (possible) SN in a CSM makes it hard to tell if a destructive SN explosion actually happened. In this respect, iPTF13z is compared to e.g. SN 2009ip but also to long-lived interacting SNe like SN 1988Z. Some suggestions for future investigations are offered, to tie light curve bumps to precursor events and to clarify the question of core collapse in the ambiguous cases of some interacting SNe.

Thermoelectric devices with the ability to convert rejected heat into electricity are widely used in nowadays technology. Several studies have been done to improve the efficiency of these devices. However, because of the strong correlation between thermoelectric properties (electrical conductivity, Seebeck coefficient, and thermal conductivity including lattice and electron counterpart), improving ZT has always been a challenging task. In this study, thermal conductivity of group IV-based binary and ternary alloys such as SiGe, SiSn, GeSn, and SiGeSn has been studied. Phonon Boltzmann Transport Equation has been solved in the relaxation time approximation including intrinsic and extrinsic (in the presence of boundary and interfaces in the low-dimensional material) scattering mechanisms. Full phonon dispersion based on the Adiabatic Bond Charge model has been calculated for Si, Ge, and Sn. Virtual crystal approximation has been adapted to calculate the dispersion of SiGe, SiSn, GeSn, and SiGeSn. Two approaches have been introduced to reduce the lattice thermal conductivity of the materials under study. First, alloying results in a significant reduction of thermal conductivity. But, this reduction has been limited by the mass disorder scattering in the composition range of 0.2 to 0.8. Second, nanostructuring technique has been proposed to further reduce the thermal conductivity. Our study shows that, due to the atomic mass difference which gives rise to the elastic mass scattering mechanism, SiSn has the lowest thermal conductivity among the other materials under study. SiSn achieved the thermal conductivity of 1.18 W/mK at 10 nm at the Sn composition of 0.18, which is the experimentally stable state of SiSn. The results show that SiSn alloys have the lowest conductivity (3 W/mK) of all the bulk alloys, more than two times lower than SiGe, attributed to the larger difference in mass between the two constituents. In addition, this study demonstrates that thin films offer an additional reduction in thermal conductivity, reaching around 1 W/mK in 20 nm SiSn, GeSn, and ternary SiGeSn films, which is close to the conductivity of amorphous SiO$_2$. This value is lower than the thermal conductivity of SiGe at 10 nm which is 1.43 W/mK. Having lattice thermal conductivity reduced, electron transport has been studied by solving Boltzmann Transport Equation under low electric field including elastic and inelastic scattering mechanisms. Rode's iterative method has been applied to the model for obtaining perturbation of distribution function under a low electric field. This study shows that nanostructuring and alloying can reduce $\kappa_{ph}$ without significantly changing the other parameters. This is because of the phonon characteristics in solids in which MFP of phonons is much larger than those of electrons, which gives us the possibility of phonons confinement without altering electrons transport. Thermoelectric properties of SiGe in the bulk and nanostructure form have been studied to calculate ZT in a wide range of temperatures. The results demonstrate that ZT reaches the value of 1.9 and 1.58 at the temperatures of 1200 K and 1000 K respectively, with the Ge composition of 0.2 and carrier concentration of 5$\times$10$^{19}$ cm$^{-3}$ at 10 nm thickness. This model can be applied to SiSn and other binary and ternary alloys, to calculate the improved ZT. Hence, we conclude that group IV alloys containing Sn have the potential for high-efficiency TE energy conversion.

Las aleaciones de titanio con microestructura ß destacan sobre todo por sus buenas propiedades específicas, su resistencia a la corrosión y por su bajo módulo elástico que las hacen muy apropiadas para su utilización como biomaterial en implantología ya que reducen de forma drástica fenómenos indeseados como el apantallamiento de tensiones. Existen grandes dificultades para procesar este tipo de aleaciones pero la pulvimetalurgia convencional se muestra como una de las mejores opciones. Unido a la mezcla elemental de polvos se aprovecha la gran reactividad del titanio para obtener aleaciones homogéneas a pesar del carácter refractario de los principales aleantes betágenos del titanio. Pero esta gran reactividad entorpece el procesado ya que se debe tener especial cuidado para no contaminar u oxidar el material. En este trabajo se ha desarrollado una serie de aleaciones de titanio tipo ß procesadas por pulvimetalurgia y mezcla elemental de polvos. Se ha utilizado el niobio como principal elemento de aleación betágeno, y se ha incluido pequeños contenidos de estaño estudiándose la influencia de éste como tercer elemento en la aleación. En primer lugar se ha optimizado el procesado logrando un nivel de repetitividad y homogeneidad muy alto. Se ha estudiado las microestructuras obtenidas para comprender el comportamiento mecánico de las mismas así como su comportamiento frente a la corrosión simulando las solicitaciones requeridas como biomaterial. Se ha puesto especial hincapié en la determinación del módulo elástico por diferentes métodos de modo que permita un mayor acercamiento a la modificación del mismo mediante aleación, y todo ello comparado con los resultados alcanzados por otros investigadores. Los resultados obtenidos muestran que las aleaciones desarrolladas mediante la adición de 2 y 4 % de estaño a aleaciones base Ti 30Nb, así como la técnica de procesado seleccionada son una gran alternativa, desde el punto de vista de propiedades, y económicamente viable. / Devesa Albeza, F. (2013). Desarrollo y caracterización de aleaciones Ti-Nb-Sn obtenidas por vía pulvimetalúrgica [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/28211