Fuel for nuclear reactors with an increased thermal conductivity offers the potential for lower fuel operating temperatures and reduced fission gas release rates. Uranium dioxide (UO2) based composites offer a method of achieving a higher thermal conductivity. Silicon carbide (SiC) and molybdenum (Mo) have been identified as potential candidates for use in a composite fuel material. Uranium dioxide composites were manufactured with the inclusion of whiskers and granules of SiC up to a 30 vol% loading. The manufacturing route used was based on the current process employed to commercially manufacture UO2 fuel, by reductive sintering. Composites containing Mo were manufactured via spark plasma sintering and included loadings of up to 10 vol% Mo. The composites were characterised on their microstructural properties and where appropriate the thermal conductivity was determined by laser flash analysis. The composites containing SiC achieved low densities, 95%TD. The microstructure contained channel like structures of Mo, due to the use of an agglomerated UO2 precursor powder. An increased thermal conductivity was determined for the molybdenum composites. At the maximum measurement temperature of 800°C the increase was found to be 68% in the 10 vol% composites compared to UO2.

Abstract Density functional theory (DFT) is a well-established tool for calculating the properties of materials. The volume of DFT-related publications doubles every 5–6 years, which has resulted in the appearance of continuously growing open material databases, containing information on millions of compounds. Furthermore, the results of DFT computations are frequently coupled with experimental ones to strengthen the computational findings. In this thesis, several applications of DFT related to physics and chemistry are discussed. The conductivity between MoS₂ and transition metal nanoparticles is evaluated by calculating the electronic structure of two different models for the nanoparticles. Chemical bonding of Ni to the MoS₂ host is proven by the system’s band alignment. To meet the demand for cleaner fuel, the applicability of the (103) edge surface of molybdenum disulfide in relation to the early stages of the hydrodesulfurization (HDS) reaction is considered. The occurrence of the (103) edge surface of molybdenum disulfide in the XRD patterns is explained. A method for calculating oxidation states based on partial charges using open materials databases is suggested. We estimate the applicability of the method in the case of mixed valence compounds and surfaces, showing that DFT calculations can be used for the estimation of oxidation states. / Tiivistelmä Tiheysfunktionaaliteoria (density functional theory, DFT) on yleisesti käytetty työkalu laskennallisessa materiaalitutkimuksessa. DFT:llä tuotettujen julkaisujen määrä kaksinkertaistuu 5–6 vuoden välein, minkä johdosta käytettävissä on jatkuvasti kasvava määrä avoimia materiaalitietokantoja, joihin on talletettu miljoonien yhdisteiden ominaisuuksia. DFT-laskujen tuloksia täydennetään myös usein kokeellisilla tuloksilla. Tässä työssä tarkastellaan tiheysfunktionaaliteorian sovelluksia fysiikassa ja kemiassa. MoS₂:n ja metallisten nanopartikkelien välistä johtavuutta on tutkittu mallintamalla erilaisia nanopartikkeleita. Nikkelin ja MoS₂:n välinen kemiallinen sidos selittyy systeemin energiavöiden kohdistumisella. MoS₂:n (103)-pinnan soveltuvuutta rikinpoistoreaktion varhaisissa vaiheissa on tutkittu tarkoituksena löytää uusia menetelmiä puhtaan polttoaineen tuottamiseksi. Myös (103)-pinnan esiintyminen röntgendiffraktiokuvissa selitetään. Työssä on myös esitetty menetelmä hapetustilojen laskemiseksi tietokannoista löytyvien laskettujen varausjakaumien avulla. Menetelmän soveltuvuutta on tarkasteltu erilaisille yhdisteille ja pinnoille. Tämä tarkastelu osoittaa, että DFT-tuloksia voidaan käyttää hapetustilojen laskemiseen.

ALENCAR, Rafael Silva. Estudo de fônons em nanotubos de carbono e dissulfeto de molibdênio: efeito do acoplamento entre camadas. 2016. 116 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2016. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2016-07-04T18:55:57Z No. of bitstreams: 1 2016_tese_rsalencar.pdf: 15208196 bytes, checksum: 0879a7d3b08f7d02d899e3d78888e828 (MD5) / Approved for entry into archive by Edvander Pires (edvanderpires@gmail.com) on 2016-07-04T18:56:56Z (GMT) No. of bitstreams: 1 2016_tese_rsalencar.pdf: 15208196 bytes, checksum: 0879a7d3b08f7d02d899e3d78888e828 (MD5) / Made available in DSpace on 2016-07-04T18:56:56Z (GMT). No. of bitstreams: 1 2016_tese_rsalencar.pdf: 15208196 bytes, checksum: 0879a7d3b08f7d02d899e3d78888e828 (MD5) Previous issue date: 2016 / In this work we present the studies on Double (DWCNTs) and Triple Wall Carbon Nanotubes, on molybdenum disulfide in the bulk form and on few layer of MoS_2 under hydrostatic high pressure conditions. Theoretical calculations were performed in collaboration to support the experimental results. For the DWCNTs samples, changes in the G-band frequency vs. pressure plot and the disappearance of the radial breathing modes (RBM) between 2 GPa and 5 GPa indicate the beginning and ending of the radial collapse of the nanotubes. Theoretical calculations based on Density-Functional Tight-Binding (DFTB) shown that the collapse pressure (P_c) for DWCNTs follows a d^{-3}_{in} law, in excellent agreement with the experimental results. The P_c dependence on number of tube-walls and on the inter-wall distance is also investigated. For the TWCNTs samples, pressure screening effects are observed for the innermost tubes of TWCNTs similar to what has been already found for DWCNTs. However, using the RBM pressure coefficients in conjunction with the histogram of the diameter distribution, we were able to separate the RBM Raman contribution related to the intermediate tubes of TWCNTs from that related to the inner tubes of DWCNTs. By combining Raman spectroscopy and high pressure measurements, it was possible to identify these two categories of inner tubes even if the two tubes exhibit the same diameters, since their pressure response is different. Furthermore, it was possible to observe similar RBM profiles of the innermost tubes of TWCNTs using different resonance laser energies but also under different pressure conditions. This is attributed to changes in the electronic transition energies caused by small pressure-induced deformations. Theoretical calculations based on ab initio were performed for support the experimental results. By using Raman spectroscopy, it was possible to estimate the displacement of the optical energy levels with pressure. For the exfoliated MoS_2 samples, we studied the effect of the stacking on the E^1_{2g} and A_{1g} vibrational modes at high pressures. New components for both modes were observed with increasing pressure. It was also observed that the pressure coefficient of the E^1_{2g} mode decreases exponentially with MoS_2 thickness is increased, differently of the A_{1g} mode and the new components, which do not present a significant dependence on the variation of the number of layers. These results were attributed to deformations in the MoS_2 structure induced by a biaxial strain (dependent on the number of layers), resulting from the deformation of the SiO_2 substrate. Such adhesion decreases with the increasing of the MoS_2 thickness due to the increasing on the unbinding regions between MoS_2 and SiO_2. As result, a higher pressure is needed to improve the adhesion and consequently, a higher pressure is required to achieve the biaxial strain. For the MoS_2 microcrystalline powder, except for the B_{1u}, E^2_{2g}, E_{1g}, E^1_{2g} and A_{1g} modes, the behavior of all other modes was studied for the first time in high pressure conditions. For all modes, a linear variation of the Raman frequency and positive pressure coefficient was observed. Moreover, the differences in the behavior of the intensity profiles of the A_{1g}, 2LA(M) and A_{2u} modes in resonance and off-resonance were attributed to variations in the energy of direct optical transitions induced by pressure. / Nesta Tese apresentamos os estudos de espectroscopia Raman em condições extremas de pressão hidrostática realizados em nanotubos de carbono de parede dupla (DWCNTs) e tripla (TWCNTs), em dissulfeto de molibdênio na forma bulk e em poucas camadas. Cálculos teóricos foram usados para dar suporte aos resultados experimentais. Para as amostras de DWCNTs, as mudanças no coeficiente de pressão da banda G e o desaparecimento dos modos de respiração radial (RBMs) entre 2 GPa e 5 GPa foram interpretados como um indicativo do início e fim do colapso radial dos nanotubos de carbono (CNTs). Os cálculos teóricos usando Tight-Binding baseado no Funcional da Densidade (DFTB) mostraram que a pressão de colapso (P_c) para os DWCNTs segue uma lei de potência do tipo d^{-3}_{in}, em excelente acordo com os resultados experimentais. A dependência de P_c em relação ao número de paredes do tubo, como também a distância inter-paredes também foram investigadas. Para a amostra contendo TWCNTs, através da análise dos coeficientes de pressão dos modos RBMs em conjunto com o histograma da distribuição de diâmetros da amostra, foi possível separarmos as contribuições dos RBMs nos espectros Raman relacionados aos tubos internos dos TWCNTs e DWCNTs, embora possuam a mesma distribuição de diâmetro, a resposta das propriedades vibracionais à pressão são diferentes. Adicionalmente, foi possível observar perfis de intensidades semelhantes para os modos RBMs dos tubos mais internos dos TWCNTs usando diferentes energias de LASER, mas sob diferentes condições de pressão. Atribuímos este resultado à mudanças nas energias de transições eletrônicas causadas por pequenas deformações estruturais nos nanotubos induzidas pela pressão. Cálculos teóricos baseados em ab initio foram realizados para dar suporte às interpretações dos resultados experimentais. Para as amostras de MoS_2 esfoliadas, estudamos o efeito do empilhamento nos modos vibracionais E^1_{2g} e A_{1g} em altas pressões. Novas componentes para esses modos foram observadas com o aumento da pressão. Foi também observado que o coeficiente de pressão do modo E^1_{2g} diminui exponencialmente com o aumento do número de camadas, diferentemente do modo A_{1g} e das novas componentes, que não apresentam uma dependência significativa com a variação da espessura do MoS_2. Atribuímos estes resultados às deformações estruturais do MoS_2 induzidas por uma tensão biaxial (dependente da adesão entre SiO_2 e MoS_2) resultante da deformação do substrato de SiO_2. O aumento do número de camadas diminui a adesão entre o MoS_2 e o SiO_2 devido ao aumento da porcentagem de regiões em não-contato com o substrato, e como consequência, uma pressão mais elevada é necessária para aumentar a adesão, resultando no aumento da pressão para deformar a estrutura do MoS_2. Para o pó microcristalino de MoS2, com exceção dos modos B_{1u}, E^2_{2g}, E1g, E^1_{2g} e A_{1g}, o comportamento de todos os outros modos foi também estudado em condições de altas pressões hidrostáticas. Todos os modos apresentaram uma variação linear de suas frequências Raman com a pressão e coeficientes de pressão positivos. Além disso, as diferenças no comportamento dos perfis de intensidade dos modos A_{1g}, 2LA(M) e A_{2u} em ressonância e fora de ressonância foram interpretados como sendo devido às variações nas energias das transições ópticas direta induzidas pela pressão.

Les aciers inoxydables sont de plus en plus utilisés comme renfort du béton dans lesconstructions marines et côtières, afin de prévenir la corrosion induite par les ions chloruresqui pénètrent dans le béton poreux. L’ajout de molybdène dans les aciers inox contribue àaugmenter leur résistance à la corrosion par piqure lorsqu’ils sont utilisés dans desenvironnements acides et neutres. Cependant, le rôle du Mo sur la corrosion par piqûre desaciers en milieu alcalin chloruré reste à ce jour flou et peu étudié. Par conséquence, lacompréhension de l’action du Mo dans la résistance à la corrosion en milieu alcalin est doncd'une importance majeure. Cela permettra l'optimisation de la composition finale des alliagesinoxydables en vue des applications potentiels comme renfort dans le béton. Ainsi, cette thèsevise à étudier l'effet de l'addition du Mo sur les propriétés de corrosion par piqûre des aciersinoxydables austénitiques, ferritiques et surtout lean duplex en milieu alcalin. Finalement, lerôle du Mo sur les aciers inoxydables a été discuté en termes de leur résistance à la corrosionlocalisée, cinétique de repassivation et propriétés de passivation dans plusieurs milieuxagressifs, mais surtout dans une solution chlorurée synthétique qui simule les environnementsporeux du béton (solution de pH10 avec des ions carbonates et chlorures). / The use of stainless steels (SS) as concrete reinforcement is becoming increasinglypopular in coastal and marine constructions in order to prevent corrosion induced by chlorideions penetrating into the concrete. However, the influence of Mo addition on pitting corrosionresistance of these steels is not fully understood in alkaline chloride conditions although thiselement is widely associated to an increasing corrosion resistance in acidic and neutralenvironments. Therefore, understanding Mo mechanism on corrosion resistance in alkalineconditions is hence of major importance for the setting of optimized alloy composition. ThisPhD work aims to study the effect of Mo addition on pitting corrosion properties of austenitic,ferritic and mainly lean duplex stainless steels in alkaline media, which simulates the concreteenvironment. As far as the role of Mo is concerned, it will be discussed in terms of, pittingcorrosion resistance, repassivation kinetics, and passivation properties from acidic to alkalineconditions.

Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2017-02-21T16:57:31Z No. of bitstreams: 1 TeseTML.pdf: 9976156 bytes, checksum: 2b00da954b5187d6f10e5593523581c0 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-03-14T20:24:10Z (GMT) No. of bitstreams: 1 TeseTML.pdf: 9976156 bytes, checksum: 2b00da954b5187d6f10e5593523581c0 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-03-14T20:24:20Z (GMT) No. of bitstreams: 1 TeseTML.pdf: 9976156 bytes, checksum: 2b00da954b5187d6f10e5593523581c0 (MD5) / Made available in DSpace on 2017-03-14T20:33:50Z (GMT). No. of bitstreams: 1 TeseTML.pdf: 9976156 bytes, checksum: 2b00da954b5187d6f10e5593523581c0 (MD5) Previous issue date: 2016-08-25 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The increasing demand for oil and oil derived products contributed to the alarming increase in the gaseous pollutants emissions in general and mainly contributed to the increase in carbon monoxide (CO) emissions in the worldwide. Besides being delivered on fossil fuels burning processes, a large amount of CO is also generated during the oil refining process, especially in the fluid catalytic cracking unit (FCC). In order to reduce the costs associated to the CO oxidation catalysts many efforts have been devoted to substitution of noble metals by non-noble transition metals, such as cobalt oxides and manganese oxides. However, the biggest challenge for this replacement is to keep the activity of these catalysts in the presence of interfering agents, such as SO2 and H2O, which might deactivate the catalysts or even inhibit the CO oxidation reaction. In this context, the aim of this study is to evaluate the activity of cobalt and/or manganese catalysts, promoted or not by molybdenum and supported on mesoporous molecular sieve type SBA-15 in the CO oxidation reaction in the presence of SO2 (450 ppm) and H2O (10% V/V). These catalysts were prepared by three different methods: (i) impregnation, (ii) deposition-precipitation using microwave and (iii) one-pot. It is noteworthy that the catalysts prepared by the methods of deposition-precipitation and one-pot represents a major breakthrough regarding to green synthesis methods, since they allowed representative savings of energy and water. It was found that the one-pot and deposition-precipitation methods yielded catalysts with high dispersion of the active phase and quite active in CO oxidation reaction. Furthermore, analysis of XRD, Raman, EPR, UV-Vis, XPS and H2-TPR revealed that the one-pot method yielded better dispersion of the molybdenum species over the SBA-15 support, which provided excellent resistance to the cobalt and/or manganese catalysts to SO2 and H2O poisoning. Moreover, the catalysts promoted by molybdenum and prepared by the deposition-precipitation method were composed by cobalt or manganese molybdates, as indicated by XRD, Raman, UV-Vis and XPS techniques, which are less active in the CO oxidation reaction. The catalysts promoted by molybdenum and prepared by the impregnation method possessed a smaller dispersion of the promoter, with the formation of molybdenum oxide, and thus reducing the resistance of these catalysts in the presence of the interfering agents. / A crescente demanda por petróleo e seus derivados contribuiu para o alarmante aumento das emissões de poluentes gasosos de um modo geral e principalmente contribuiu para o aumento das emissões do monóxido de carbono (CO) em todo o mundo. Além de ser emitido em processos de queima de combustíveis fósseis, grande quantidade de CO também é gerada durante o processo de refino do petróleo, principalmente na unidade de craqueamento catalítico em leito fluido (FCC). Com o objetivo de reduzir os custos associados aos catalisadores de oxidação do CO diversos esforços têm sido dedicados para a substituição dos metais nobres por metais de transição não nobres, tais como óxidos de cobalto e óxidos de manganês. Entretanto, o maior desafio para esta substituição é manter a atividade destes catalisadores na presença dos agentes interferentes, SO2 e H2O, que atuam desativando estes catalisadores ou mesmo inibindo a reação de oxidação do CO. Neste contexto, o objetivo geral deste trabalho é avaliar a atividade de catalisadores de cobalto e/ou manganês, modificados ou não por molibdênio e suportados em peneira molecular mesoporosa tipo SBA-15 na reação de oxidação do CO na presença de SO2 (450 ppm) e H2O (10 % V/V). Estes catalisadores foram preparados por três diferentes métodos: (i) impregnação, (ii) deposição-precipitação utilizando micro-ondas e (iii) one-pot. Vale ressaltar que os catalisadores preparados pelos métodos de deposição-precipitação e one-pot representam um grande avanço no que se diz respeito a métodos verdes de síntese, pois permitiram grande economia de energia e de água. Foi constatado que os métodos one-pot e deposição-precipitação renderam catalisadores com elevada dispersão das fases ativas e bem ativos na reação de oxidação do CO. Além disso, as análises de DRX, Raman, EPR, UV-Vis, XPS e H2-RTP revelaram que o método one-pot rendeu a melhor dispersão das espécies de molibdênio sobre o suporte de SBA-15, que conferiu excelente resistência aos catalisadores de cobalto e/ou manganês ao envenenamento por SO2 e H2O. Por outro lado, os catalisadores modificados por molibdênio e preparados pelo método de deposição-precipitação foram compostos por molibdatos de cobalto ou manganês, conforme indicado pelas técnicas de DRX, Raman,UV-Vis e XPS, fase menos ativa na reação de oxidação do CO. Além disso, os catalisadores preparados pelo método de impregnação e modificados por molibdênio possuíram menor dispersão do metal promotor, com formação de óxido de molibdênio, e, reduzindo assim, a resistência destes catalisadores na presença dos agentes interferentes.

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Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-11-12T09:53:58Z No. of bitstreams: 0 / Made available in DSpace on 2015-11-12T09:53:58Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP