Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2005. / 199 leaves single sided printed, preliminary pages i-vii and numbered pages 1-191. Includes bibliography, list of figures and tables. Digitized using a Hp Scanjet 8250 Scanner to pdf format (OCR). / ENGLISH ABSTRACT: This study provided scientific proof of the precipitation of iron and other metal species in the HAL circuit at the Mineral Separation Plant of Namakwa Sands. Iron and aluminium hydroxides were the most abundant precipitate complexes that formed in the HAL circuit. Sulphates formed bridges with the iron complexes. It was found that precipitation of iron in the HAL circuit was a function of the pH, ferric ion concentration and temperature of the process water. Experimental work provided abundant evidence that the precipitated iron hydroxide and other species adsorb to the surfaces of zircon and rutile mineral particles due to opposite zeta potentials of the mineral particles and iron hydroxide. These adsorbed species altered the electrostatic potential of the mineral surfaces, which reduced the electrostatic separation efficiency of these minerals. It was determined that an improvement of 7% could be expected if the precipitation and attachment of iron could be minimised. Based on the experimental results, conceptual processes were developed and iterative simulations were set up to determine the optimum solution that would maximise the removal of dissolved iron. This solution would ensure clean mineral surfaces free of any adsorbed precipitates. This process circuit was constructed in May to August 2004 at a total capital cost of R4.8m and removed 99.97% of the total dissolved iron prior to caustic addition. Prime zircon recoveries were increased by 3-7%. / AFRIKAANSE OPSOMMING: Hierdie studie het wetenskaplike bewyse gelewer dat yster en ander spesies neerslae vorm in die HAL proses van die Mineraal Skeidings Aanleg van Namakwa Sands. Yster- en aluminium hidroksiede was die vernaamste neerslag komplekse wat gevorm het in die HAL proses. Sulfaat spesies het verbindings gevorm met die yster komplekse. Die neerslag van yster was ‘n funksie van pH, ferric ioon konsentrasie en temperatuur van die proses water. Eksperimentele werk het genoegsame bewyse gelewer dat die yster hidroksied neerslag en ander spesies adsorbeer op die oppervlaktes van sirkoon en rutiel minerale weens teenoorgestelde zeta potensiale van die mineraal partikels en yster hidroksiede. Hierdie geadsorbeerde spesies het die elektrostatiese potentiaal van die mineraal oppervlaktes verander wat sodoende die elektrostatiese skeidingsvermoë van hierdie minerale verminder het. ‘n Verbetering van 7% in elektrostatiese skeiding van sirkoon en rutiel minerale kan verwag word indien die neerslag en adsorbsie van yster minimiseer word. Konseptuele prosesse, gebasseer op die eksperimentele resultate, is ontwikkel. Itteratiewe simulasies is opgestel om die optimum proses te bepaal wat sodoende die maksimum verwydering van die opgeloste yster sou verseker. Hierdie oplossing sou skoon mineraal oppervlaktes, vry van enige geadsorbeerde neerslae, verseker. Hierdie prosesaanleg was opgerig in Mei tot Augustus 2004 teen ‘n kapitaalkoste van R4.8m en dit het 99.97% van die totale opgeloste yster verwyder voordat natrium hidroksied bygevoeg is. Primêre sirkoon opbrengste het sodoende toegeneem met 3-7%.

Nesse trabalho foram fabricados filmes finos de TiO2 por RF magnetron sputtering reativo sobre substrato de silício (1 0 0). A pressão parcial do oxigênio na câmara foi variada de 5 a 100% em relação ao argônio. Após a deposição os filmes foram submetidos a tratamento térmico em atmosfera de oxigênio. A estequiometria dos filmes e o perfil de profundidade foram obtidos por RBS. A estrutura cristalina foi obtida por XRD. As propriedades ópticas foram obtidas por interferometria e reflectância e as elétricas por meio das curvas C-V. Os valores de espessura dos filmes sem tratamento térmico aumentaram aproximadamente 41% com o aumento do oxigênio na câmara de deposição. Essa variação está ligada ao aumento da eficiência do sputtering do alvo. Os índices de refração dos filmes sem tratamento térmico se mantiveram dentro de um intervalo de aproximadamente 2,3 a 2,4. A diminuição do band gap com o tratamento térmico é consequência da mudança de fase cristalográfica de anatase para rutila. A estequiometria TiOx dos filmes antes do tratamento térmico apresentaram valores de x entre 2,0 e 2,4. A espessura em TFU dos filmes aumentou com o percentual de oxigênio na câmara. As amostras que receberam tratamento térmico apresentaram difusão de titânio na interface do substrato e incorporação de oxigênio no filme. Os valores da constante dielétrica aumentaram com o percentual de oxigênio na câmara, em contraposição com o efeito do tratamento térmico que diminuiu o valor. Todos os resultados observados são coerentes do ponto de vista da mudança de fase anatase rutila e aumento do percentual de oxigênio na câmara. / In this work thin films of TiO2 were produced by reactive RF magnetron sputtering on silicon substrate (1 0 0). The oxygen partial pressure in the chamber was varied from 5 to 100% in relation to argon. After deposition the films were submitted to thermal treatment under an oxygen atmosphere. The stoichiometry of the films and the depth profile were obtained by RBS. The crystal structure was obtained by XRD. Its optical properties were obtained by interferometry and reflectance and the electrical were obtained by means of the C-V curves. The thickness values of films without heat treatment increased approximately 41% with the increase of oxygen in the deposition chamber. This variation is linked to the increased sputtering efficiency of the target. The refractive indexes of films without heat treatment remained within a range of about 2.3 to 2.4. The decrease of the band gap with the heat treatment is a consequence of the change of crystallographic phase from anatase to rutile. The TiOx stoichiometry of the films before the heat treatment showed values of x between 2.0 and 2.4. The TFU thickness of the films increased with the percentage of oxygen in the chamber. The samples that received heat treatment shows diffusion of titanium at the interface of the substrate and incorporation of oxygen in the film. The values of the dielectric constant increased with the percentage of oxygen in the chamber, as opposed to the effect of the thermal treatment that decreased the value. All the results observed are consistent from the point of view of the anatase - rutile phase transition and the increase in the oxygen percentage in the chamber.

Quartz is one of the most common minerals in the Earth\'s crust, and is an important constituent of many metamorphic rocks. Because of the correlation between the dynamic recrystallization mechanisms and temperature, it is possible to understand the relationship between deformation and metamorphism evolution with the investigation of quartz, its textures, crystallographic orientation and its trace elements composition. Recently, thermometer calibrations were proposed based on the relationship between c-axis fabric open angle. Studies show that trace elements are also reliable indicators for geothermometers, especially on rocks without metamorphic index minerals,, such as in quartzites. With these calibrations it is possible to investigate the metamorphic-deformational evolution and compare to the metamorphic evolution of associated rocks containing diagnostic paragenesis and P-T conditions, allowing the full picture of establishment of the relationship between deformation and metamorphism. The aim of this research is to evaluate the c-axis thermometer, using data from Universal Stage and Electron Backscatter Diffraction (EBSD), as well as trace elements thermometry, Ti-in-quartz and Zr-in-rutile. The study was conducted on quartzites of the Carrancas Group, on Serra da Estância, Serra do Pombeiro and Serra de Carrancas, which P-T conditions of metamorphism were established with great precision in previous works. The study area is located in the southern region of Minas Gerais, near the cities of Carrancas, Itutinga, Itumirim and Lavras. Temperatures obtained by the c-axis thermometer were confronted with previously processed data and produced different results for each method, Universal Stage and EBSD. The Universal Stage produced a temperature that fits very well with metamorphic peak from previously calculated temperatures, and it seems to be a very reliable, cheap and relatively fast method. The stereograms made with EBSD data produced blurred girdles. It is not clear if the acquired data was either made properly or if this is a result of superimposed events of deformations, as suggested by petrography. The Zr-in-rutile thermometer partially agrees with the thermobarometry results of the literature, because at temperatures below 600 °C, it does not activate the zircon to participate on cation exchange reactions with other minerals, so the Zr concentration on rutile is considered to be from the source rock, and not related to deformation or metamorphism. The Ti-in-quartz was not a reliable thermometer for this case study. The temperatures are higher than the expected and the hypothesis is that the quartz grains might not have enough energy to exchange cations with rutile and zircon during the deformation and metamorphism caused by shear zones on Carrancas klippe. For further investigation, it is interesting to use cathodoluminescence that might map the Ti concentration zones on quartz grains to identify portions with different Ti concentrations and investigate their relationship with possible recrystallization textures. / O quartzo é um dos minerais mais comuns na crosta terrestre e é um constituinte importante de muitas rochas metamórficas. Devido à correlação entre os mecanismos dinâmicos de recristalização e a temperatura, é possível entender a relação entre a deformação e a evolução do metamorfismo com a investigação do quartzo, suas texturas, orientação cristalográfica e sua composição de elementos traços. Recentemente, calibrações de termômetros foram propostas com base na relação entre o ângulo de abertura do eixo-c. Estudos mostram que elementos traços também são indicadores confiáveis para geotermômetros, especialmente em rochas sem índices de minerais metamórficos, como os quartzitos. Com estas calibrações é possível investigar a evolução metamórfico-deformacional e comparar com a evolução metamórfica de rochas associadas contendo paragênese diagnóstica e condições de P-T, permitindo o quadro completo do estabelecimento da relação entre deformação e metamorfismo. O objetivo desta pesquisa é avaliar os termômetros de eixo-c, utilizando dados de Platina Universal e de Electron Backscatter Diffraction (EBSD), e temperatura de elementos traço, Ti-em-quartzo e Zr-em-rutilo. O estudo foi realizado nos quartzitos do Grupo Carrancas, na Serra da Estância, Serra do Pombeiro e Serra de Carrancas, cujas condições de metamorfismo da P-T foram estabelecidas com grande precisão em trabalhos anteriores. A área de estudo está localizada na região sul de Minas Gerais, próximo às cidades de Carrancas, Itutinga, Itumirim e Lavras. As temperaturas obtidas pelo termômetro do eixo c foram confrontadas com dados previamente processados e produziram resultados diferentes para cada método de Platina Universal e EBSD. Os dados de platina produziram temperaturas que se encaixam muito bem com o pico metamórfico de temperaturas previamente calculadas, e parece ser um método muito confiável, barato e relativamente rápido. Os estereogramas feitos com os dados do EBSD produziram guirlandas pouco nítidas. Não está claro se os dados adquiridos foram feitos adequadamente ou se isso é resultado de eventos sobrepostos de deformações, como sugerido pela petrografia. O termômetro de Zr-em-rutilo concordam parcialmente com os resultados de termobarometria da literatura, porque em temperaturas abaixo de 600 ° C, os minerais de zircão não são ativados para participar de reações de troca de cátions com outros minerais, portanto a concentração de Zr no rutilo é considerada como sendo da rocha fonte, e não relacionadas à deformação ou metamorfismo. O Ti-em-quartzo não foi um termômetro confiável para este estudo de caso. As temperaturas são superiores às esperadas e a hipótese é de que os grãos de quartzo podem não ter energia suficiente para trocar cátions com rutilo e zircão durante a deformação e metamorfismo causados por zonas de cisalhamento na klippe Carrancas. Para investigações posteriores, é interessante utilizar catodoluminescência para que seja possível mapear as zonas de concentração de Ti em grãos de quartzo e assim identificar porções com diferentes concentrações de Ti e investigar sua relação com possíveis texturas de recristalização.

Quartz is one of the most common minerals in the Earth\'s crust, and is an important constituent of many metamorphic rocks. Because of the correlation between the dynamic recrystallization mechanisms and temperature, it is possible to understand the relationship between deformation and metamorphism evolution with the investigation of quartz, its textures, crystallographic orientation and its trace elements composition. Recently, thermometer calibrations were proposed based on the relationship between c-axis fabric open angle. Studies show that trace elements are also reliable indicators for geothermometers, especially on rocks without metamorphic index minerals,, such as in quartzites. With these calibrations it is possible to investigate the metamorphic-deformational evolution and compare to the metamorphic evolution of associated rocks containing diagnostic paragenesis and P-T conditions, allowing the full picture of establishment of the relationship between deformation and metamorphism. The aim of this research is to evaluate the c-axis thermometer, using data from Universal Stage and Electron Backscatter Diffraction (EBSD), as well as trace elements thermometry, Ti-in-quartz and Zr-in-rutile. The study was conducted on quartzites of the Carrancas Group, on Serra da Estância, Serra do Pombeiro and Serra de Carrancas, which P-T conditions of metamorphism were established with great precision in previous works. The study area is located in the southern region of Minas Gerais, near the cities of Carrancas, Itutinga, Itumirim and Lavras. Temperatures obtained by the c-axis thermometer were confronted with previously processed data and produced different results for each method, Universal Stage and EBSD. The Universal Stage produced a temperature that fits very well with metamorphic peak from previously calculated temperatures, and it seems to be a very reliable, cheap and relatively fast method. The stereograms made with EBSD data produced blurred girdles. It is not clear if the acquired data was either made properly or if this is a result of superimposed events of deformations, as suggested by petrography. The Zr-in-rutile thermometer partially agrees with the thermobarometry results of the literature, because at temperatures below 600 °C, it does not activate the zircon to participate on cation exchange reactions with other minerals, so the Zr concentration on rutile is considered to be from the source rock, and not related to deformation or metamorphism. The Ti-in-quartz was not a reliable thermometer for this case study. The temperatures are higher than the expected and the hypothesis is that the quartz grains might not have enough energy to exchange cations with rutile and zircon during the deformation and metamorphism caused by shear zones on Carrancas klippe. For further investigation, it is interesting to use cathodoluminescence that might map the Ti concentration zones on quartz grains to identify portions with different Ti concentrations and investigate their relationship with possible recrystallization textures. / O quartzo é um dos minerais mais comuns na crosta terrestre e é um constituinte importante de muitas rochas metamórficas. Devido à correlação entre os mecanismos dinâmicos de recristalização e a temperatura, é possível entender a relação entre a deformação e a evolução do metamorfismo com a investigação do quartzo, suas texturas, orientação cristalográfica e sua composição de elementos traços. Recentemente, calibrações de termômetros foram propostas com base na relação entre o ângulo de abertura do eixo-c. Estudos mostram que elementos traços também são indicadores confiáveis para geotermômetros, especialmente em rochas sem índices de minerais metamórficos, como os quartzitos. Com estas calibrações é possível investigar a evolução metamórfico-deformacional e comparar com a evolução metamórfica de rochas associadas contendo paragênese diagnóstica e condições de P-T, permitindo o quadro completo do estabelecimento da relação entre deformação e metamorfismo. O objetivo desta pesquisa é avaliar os termômetros de eixo-c, utilizando dados de Platina Universal e de Electron Backscatter Diffraction (EBSD), e temperatura de elementos traço, Ti-em-quartzo e Zr-em-rutilo. O estudo foi realizado nos quartzitos do Grupo Carrancas, na Serra da Estância, Serra do Pombeiro e Serra de Carrancas, cujas condições de metamorfismo da P-T foram estabelecidas com grande precisão em trabalhos anteriores. A área de estudo está localizada na região sul de Minas Gerais, próximo às cidades de Carrancas, Itutinga, Itumirim e Lavras. As temperaturas obtidas pelo termômetro do eixo c foram confrontadas com dados previamente processados e produziram resultados diferentes para cada método de Platina Universal e EBSD. Os dados de platina produziram temperaturas que se encaixam muito bem com o pico metamórfico de temperaturas previamente calculadas, e parece ser um método muito confiável, barato e relativamente rápido. Os estereogramas feitos com os dados do EBSD produziram guirlandas pouco nítidas. Não está claro se os dados adquiridos foram feitos adequadamente ou se isso é resultado de eventos sobrepostos de deformações, como sugerido pela petrografia. O termômetro de Zr-em-rutilo concordam parcialmente com os resultados de termobarometria da literatura, porque em temperaturas abaixo de 600 ° C, os minerais de zircão não são ativados para participar de reações de troca de cátions com outros minerais, portanto a concentração de Zr no rutilo é considerada como sendo da rocha fonte, e não relacionadas à deformação ou metamorfismo. O Ti-em-quartzo não foi um termômetro confiável para este estudo de caso. As temperaturas são superiores às esperadas e a hipótese é de que os grãos de quartzo podem não ter energia suficiente para trocar cátions com rutilo e zircão durante a deformação e metamorfismo causados por zonas de cisalhamento na klippe Carrancas. Para investigações posteriores, é interessante utilizar catodoluminescência para que seja possível mapear as zonas de concentração de Ti em grãos de quartzo e assim identificar porções com diferentes concentrações de Ti e investigar sua relação com possíveis texturas de recristalização.

Made available in DSpace on 2017-07-21T20:42:40Z (GMT). No. of bitstreams: 1 Renata Martins Silva.pdf: 2842741 bytes, checksum: 00c605c84616c33c3c08c2e35031efa1 (MD5) Previous issue date: 2013-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Was synthesized particulate material based on containing a small amount of bismuth compounds and molybdenum with satisfactory reproducibility. The material was produced starting from a composition of 99% (mol %) of rutile TiO2 and 1% of MoO3, which were previously mixed and calcined at 1200ºC. The composition studied consisted of 99.8% of the above mixture and 0.2% of bismuth subnitrate hexahydrate, Bi5O(OH)9 NO3)4.6H2O. This powder mixture [(99.8% of TiO2+MoO3 and 0.2% of Bi5O(OH)9 (NO3)4.6H2O)] was homogenized and calcined in tubular furnace at 1200ºC using four different heating rates: 1, 30, 40 e 60 °C/min. The ascalcined powder was characterized by X-ray diffraction (XRD) for identification of the phases resulting, scanning electron microscopy (SEM) to evaluate the microstructure and degree of gglomeration of powders and particle size was estimated by laser scattering technique. The color properties were expressed as CIEL*a*b* coordinates. X-ray patterns indicated the presence of TiO2, Bi2O3, γ-Bi2MoO6, Bi2Ti2O7, Bi2Ti4O11 depending on the heating rate. The yellow color was attributed to the presence of α-Bi2O3, Bi2MoO6 e Bi2Ti2O7. The different heating rates showed no relevant influence on the powder morphology, but the particle size of the powder was suitable for using the material as an inorganic pigment. / Foi sintetizado um material particulado a base de TiO2, contendo uma pequena quantidade de compostos de bismuto e de molibdênio apresentando boa reprodutibilidade. O material foi produzido a partir de uma composição de 99% (mol%) de rutilo TiO2 e 1% de MoO3, previamente misturados e calcinado a 1200 °C. A composição estudada consistia de 99,8% da mistura acima e 0,2% de subnitrato de bismuto hexahidratado, Bi5O(OH)9 (NO3)4.6H2O. Esta mistura em pó [(99,8% de TiO2 + MoO3 e 0,2% de Bi5O(OH)9 (NO3) 4.6H2O)], foi homogeneizada e calcinada em forno tubular a 1200 ºC, utilizando-se quatro taxas de aquecimento diferentes: 1, 30, 40 e 60 °C /min. O pó calcinado foi caracterizado por difração de raios X (DRX) para identificação das fases resultantes, por microscopia eletrônica de varredura (MEV) para avaliação da microestrutura e grau de aglomeração dos pós, o tamanho de partículas foi estimado por espectroscopia de fotocorrelação (PCS) e as propriedades colorimétricas através das coordenadas CIEL*a*b* . O DRX indicou a presença das fases TiO2, α-Bi2O3, γ-Bi2MoO6, Bi2Ti2O7, Bi2Ti4O11 sendo estas dependentes das taxas de aquecimento utilizadas. A cor amarela foi atribuída à presença de α-Bi2O3, -Bi2MoO6 e Bi2Ti2O7. As taxas de aquecimento diferentes não apresentaram nenhuma influência relevante sobre a morfologia do pó, porém o tamanho de partícula do pó mostrou-se adequado para a utilização do material, como um pigmento inorgânico.

O objetivo desta Dissertação foi analisar o efeito do tratamento térmico de alívio de tensões pós-soldagem sobre a microestrutura e comportamento mecânico de soldas produzidas com arame tubular rutílico AWS E-81T1 Ni1. Foi soldada uma junta com 60 mm de espessura, na posição vertical e progressão ascendente. Esta junta foi dividida em três partes, sendo uma mantida como soldada e as outras duas tratadas termicamente por 6 horas em diferentes temperaturas, 585 °C e 650 °C. Avaliou-se o efeito do tratamento térmico sobre as propriedades mecânicas por meio de ensaio de dureza, tração e impacto Charpy-V. A caracterização microestrutural foi realizada por microscopia óptica e microscopia eletrônica de varredura. As observações experimentais mostraram uma diminuição da tenacidade ao impacto no material tratado termicamente, com uma tendência para uma queda maior com o aumento da temperatura do tratamento térmico. Este comportamento pode ser atribuído principalmente à precipitação e crescimento de carbonetos. Não foi observada a presença de mecanismos de fratura intergranular. Provavelmente o metal de solda estudado não possuía nível de impurezas suficiente para a ativação deste mecanismo. / The objective of this Dissertation was to analyze the effect of postweld heat treatment on microstructure and mechanical behavior of welds obtained by flux cored wire AWS E-81T1 Ni1. It was welded a joint with 60 mm thickness, on vertical position and ascendant progress. This joint was divided in three parts, one maintained as welded and two others heat treated for 6 hours on different temperatures, 585 °C and 650 °C. The effect of the heat treatment on mechanical properties was evaluated by means of hardness, tensile and impact Charpy-V tests. The characterization of the microstructure was undertaken utilizing optical and scanning electron microscopy. The experimental results revealed a decrease of impact toughness in heat treated material, with a tendency to a low impact toughness for high heat treatment temperature. This behavior may principally be attributed to an increase precipitation and growth of carbides. No intergranular fracture mechanism was observed. Probably the level of impurities in the weld metal studied was not high enough to provoke such phenomena.

Interfaces between semiconductors and adsorbed molecules form a central area of research in surface science, occurring in many different contexts. One such application is the so-called Dye-Sensitized Solar Cell (DSSC) where the nanostructured dye-semiconductor interface is of special interest, as this is where the most important ultrafast electron transfer process takes place. In this thesis, structural and electronic aspects of these interfaces have been studied theoretically using quantum chemical computations applied to realistic dye-semiconductor systems. Periodic boundary conditions and large cluster models have been employed together with hybrid HF-DFT functionals in the modeling of nanostructured titanium dioxide. A study of the adsorption of a pyridine molecule via phosphonic and carboxylic acid anchor groups to an anatase (101) surface showed that the choice of anchor group affects the strength of the bindings as well as the electronic interaction at the dye-TiO2 interface. The calculated interfacial electronic coupling was found to be stronger for carboxylic acid than for phosphonic acid, while phosphonic acid binds significantly stronger than carboxylic acid to the TiO2 surface. Atomistic and electronic structure of realistic dye-semiconductor interfaces were reported for RuII-bis-terpyridine dyes on a large anatase TiO2 cluster and perylene dyes on a periodic rutile (110) TiO2 surface. The results show strong influence of anchor and inserted spacer groups on adsorption and electronic properties. Also in these cases, the phosphonic acid anchor group was found to bind the dyes significantly stronger to the surface than the carboxylic acid anchor, while the interfacial electronic coupling was stronger for the carboxylic anchor. The estimated electron injection times were twice as fast for the carboxylic anchor compared to the phosphonic anchor. Moreover, the electronic coupling was affected by the choice of spacer group, where unsaturated spacer groups were found to mediate electron transfer more efficiently than saturated ones.

Transition metal oxides having high dielectric constants and wide band gaps find very important and interesting technological applications in surface physics. In particular, titania is the most commonly used material in heterogeneous catalysis because of its stable and flat surfaces. Having Ti cations at different charge states within the system brings about various novel electronic properties which are mainly surface related. Adsorption of catalytically important or chemically useful molecules on titania surfaces are investigated, electronic energy bands and charge densities are calculated from first principles using the density functional theory in the GGA scheme. The comparisons with the leading theories and existing experimental data are maid.

Theoretical methods can be used to describe surface chemical reactions in detail and with sufficient accuracy. Advances, especially in density functional theory (DFT) method, enable to compare computational results with experiments. Quantum chemical calculations employing ONIOM DFT/B3LYP/6-31G**-MM/UFF cluster method provided in Gaussian 03 are conducted to investigate water adsorption on rutile (110), and water and ammonia adsorption on anatase (001) surfaces of titanium dioxide. Water and ammonia adsorption on anatase (001) surface is studied by also performing PW:DFT-GGA-PW91 periodic DFT method by using VASP code and the results are compared with the results of ONIOM method. The results obtained by means of ONIOM method indicate that dissociative water adsorption on rutile (110) surface is not favorable due to high activation barrier, whereas on anatase (001) surface, it is favorable since molecular and dissociative water adsorption energies are calculated to be -23.9 kcal/mol and -58.12 kcal/mol. Moreover, on anatase (001) surface, dissociative ammonia adsorption is found energetically more favorable than molecular one (-37.17 kcal/mol vs. -23.28 kcal/mol). Thermodynamic functions at specific experimental temperatures for water and ammonia adsorption reactions on anatase (001) surface are also evaluated. The results obtained using periodic DFT method concerning water adsorption on anatase (001) surface indicate that dissociative adsorption is more favorable than molecular one (-32.28 kcal/mol vs. -14.62 kcal/mol) as in ONIOM method. On the same surface molecular ammonia adsorption energy is computed as -25.44 kcal/mol. The vibration frequencies are also computed for optimized geometries of adsorbed molecules. Finally, computed adsorption energy and vibration frequency values are found comparable with the values reported in literature.

This thesis presents surface science studies, investigating several aspects of titanium dioxide at the atomic scale. The greater part of this work is devoted to the preparation by chemical vapor deposition (CVD) of titanium(IV) tetraisopropoxide (TTIP) of ultrathin TiO2 or TiOx films on Au(111). Four ordered structures were growth and characterized. It was also demonstrated how the morphology of the film (wetting film vs island) can be tailored. The acquired knowledge about the CVD process was exploited to load nano porous gold with titania, enhancing its catalytic activity. The reactivity towards water adsorption of the titania structures on Au(111) was also investigated. Finally, part of this work concerned the studying of the behavior of water on the stoichiometric rutile TiO2(110) surface, combining the experiments with density-functional theory (DFT) calculations and (kinetic) Monte Carlo simulations. The main experimental techniques used in this work are low-energy electron diffraction (LEED), scanning tunneling microscopy (STM) and photoelectron spectroscopy (PES).