Le projet expérimental international ITER vise à tester la faisabilité de la fusion nucléaire en tant que source d'énergie. Le banc d'essai sera un tokamak où le deutérium et le tritium seront fusionnés et des ions d'hélium et des neutrons énergétiques seront produits. Une partie de l'énergie produite sera déposée dans la zone divertor. Afin de préserver le divertor en tungstène d'ITER, il est envisagé d‘injecter de l'azote au niveau du divertor afin de rayonner plus uniformément la charge d'énergie. Ce mode opérationnel soulève plusieurs questions. Tout d'abord, comment la rétention du combustible de fusion (deutérium et tritium) dans les premières parois de tokamak sera-t-elle affectée? En particulier, est-ce que l'azote implanté agira comme une barrière à la désorption pour le tritium? Deuxièmement, à quelle production d'ammoniac peut-on s‘attendre due aux processus réactifs sur les matériaux des premières parois? Cette thèse présente une étude approfondie de l'interaction du tungstène avec le deutérium et l'azote, avec l‘examen de plusieurs facteurs clés: la rétention de l'azote et du deutérium en fonction de la fluence; l'évolution dynamique de la rétention d‘atomes de deutérium après l'implantation; l'influence de l'azote pré-implanté sur la rétention de deutérium; et la détermination quantitative de l‘ammoniac produit après une implantation séquentielle d‘azote et de deutérium dans le tungstène. Une attention particulière est donnée à l'identification précise des mécanismes de piégeage pour chacune des deux espèces de gaz (azote et deutérium) dans le tungstène. / The international experimental project ITER aims to test the feasibility of nuclear fusion as an energy source. The test bed will be a tokamak reactor where deuterium and tritium will be fused and energetic helium ions and neutrons will be released. A part of the produced energy will be exhausted in the divertor area of the tokamak. In order to preserve the tungsten divertor of ITER, it is envisioned to use nitrogen injection above the divertor in order to radiate more evenly the incident power loads. This operational plan raises several issues. Firstly, how the retention of fusion fuel (deuterium and tritium) in the tokamak first walls will be affected? In particular, does the implanted nitrogen act as a desorption barrier for tritium? Secondly, how much production of ammonia can be expected from reactive processes on the first wall materials? This thesis presents an extensive study of the interaction of tungsten with deuterium and nitrogen, with several key factors being investigated: the nitrogen and deuterium retention as a function of fluence; the dynamic evolution of retained deuterium atoms after implantation; the influence of the pre-implanted nitrogen on deuterium retention; and the amounts of ammonia that are produced on tungsten after sequential implantation of nitrogen and deuterium. A special focus is directed towards identifying the exact trapping mechanisms for each of the two gas species (nitrogen and deuterium) in tungsten.

In today's "silicon age" in which we live, field-effect transistors (FET) are the workhorse of virtually all modern-day electronic gadgets. Although silicon currently dominates most of these electronics, layered 2D transition metal dichalcogenides (TMDCs) have great potential in low power optoelectronic applications due to their indirect-to-direct band gap transition from bulk to few-layer and high on/off switching ratios. TMDC WSe2 is studied here, mechanically exfoliated from CVT-grown bulk WSe2 crystals, to create a few-layered ambipolar FET, which transitions from dominant p-type behavior to n-type behavior dominating as temperature decreases. A high electron mobility μ>150 cm2V-1s-1 was found in the low temperature region near 50 K. Temperature-dependent photoconduction measurements were also taken, revealing that both the application of negative gate bias and decreasing the temperature resulted in an increase of the responsivity of the WSe2 sample. Besides TMDCs, Group III-VI van der Waals structures also show promising anisotropic optical, electronic, and mechanical properties. In particular, mechanically exfoliated few-layered InSe is studied here for its indirect band gap of 1.4 eV, which should offer a broad spectral response. It was found that the steady state photoconduction slightly decreased with the application of positive gate bias, likely due to the desorption of adsorbates on the surface of the sample. A room temperature responsivity near 5 AW-1 and external quantum efficiency of 207% was found for the InSe FET. Both TMDC’s and group III-VI chalcogenides continue to be studied for their remarkably diverse properties that depend on their thickness and composition for their applications as transistors, sensors, and composite materials in photovoltaics and optoelectronics.

Neste trabalho foram obtidos filmes de óxido de tungstênio pelo método sol-gel modificado, tendo como precursor o tungstato de sódio dihidratado (Na2WO4.2H2O) e como agente estruturante o surfactante cloreto de dodeciltrimetilamônio (DTAC). O comportamento dos sistemas em meio aquoso foi avaliado por medidas de pH, condutividade e viscosidade. Foram avaliadas duas metodologias de obtenção dos filmes de óxido de tungstênio: a primeira consistiu na obtenção de filmes de tungstato de sódio, através de sistemas contendo 10 mmol.L-1 de Na2WO4.2H2O em diferentes concentrações de DTAC, por casting, e conversão do tungstato de sódio a óxido de tungstênio pela acidificação dos filmes; a segunda metodologia consistiu na conversão dos sistemas aquosos contendo 20 mmol.L-1 de Na2WO4.2H2O, em diferentes concentrações de DTAC, em ácido tungstico, obtenção dos filmes por spin coating e, calcinação em presença de ar. Os filmes foram obtidos em substratos de silício (100) recobertos com dióxido de silício e avaliados por Difração de Raios-X, Espectrometria de retroespalhamento Rutherford, Espectroscopia Raman, Microscopia Eletrônica de Varredura e ensaios fotocatalíticos. As alterações na concentração precursor e agente estruturante não afetaram significativamente o pH e a viscosidade dos sistemas precursores. A determinação da concentração micelar crítica (cmc) do DTAC, obtida através da condutividade, foi de 13 mmol.L-1 e 9,88 mmol.L-1 para os sistemas contendo 10 e 20 mmol.L-1 de Na2WO4.2H2O, respectivamente. Em ambas metodologias o produto final foi o óxido de tungstênio em forma de disco e placas. As espessuras dos filmes obtidos na primeira metodologia variaram de 4 a 5 μm e as estruturas tiveram diâmetros médios de 4,37 μm e 114 nm. Na segunda metodologia as espessuras foram de 0,5-1,0 μm e as estruturas obtidas tiveram diâmetros médios em torno de 95-103 nm. Os filmes obtidos apresentaram atividade fotocatalítica, uma vez que duplicaram a velocidade da reação de degradação do corante alaranjado de metila em relação ao sistema sem o filme. / In this work tungsten oxide films have been obtained bymodified sol-gel method, with sodium tungstate dehydrate (Na2WO4.2H2O) as the precursor and the cationic surfactant dodecyltrimethylammonium chloride (DTAC) as structuring agent.The behavior in aqueous media of precursor/structuring agent systems was characterized by pH, conductivity and viscosity measurements. Two methods for obtaining tungsten oxide films were evaluated: the first consisted in obtaining sodium tungstate films from the systems containing 10 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations, by casting, converting the sodium tungstate to tungsten oxide; the second method consisted in the conversion of the aqueous systems containing 20 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations to tungstic acid, obtaining the films by spin coating and, posteriorly, calcination in the presence of air. The films were obtained on silicon substrate (100) with a 50 nm layer of silicon dioxide and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, Raman spectroscopy, Scanning Electron Microscopy and photocatalytic tests. The precursor concentration and structuring agent do not affect significantly the pH and the viscosity of the precursor systems in aqueous media.The values of critical micelle concentration (CMC) of DTAC, obtained by the conductivity, were of13 mmol.L-1 and 9,88 mmol.L-1, for the systems containing 10 and 20 mmol.L-1 de Na2WO4.2H2O, respectively.In both adopted methods the final product is the tungsten oxide, with nano and micrometric structures in the form of discs and plates. The thickness of the films obtained in the first method varied from 4 to 5 μm and the structures presented an average diameter around 4,37 μm and 114 nm. The thickness of the films obtained with the second methodvariedfrom0,5to 1 μm and the structures presented an average diameter from 95 to103 nm.The obtained tungsten oxide films presented photocatalytic activity, since doubled the reaction rate of methyl orange dye degradation with respect to the system without the film.

Orientador: Prof. Dr. Humberto Naoyuki Yoshimura / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / O cobalto tem restrições quanto à instabilidade de preço e potencial carcinogênico. O objetivo deste trabalho foi verificar a viabilidade técnica de preparação de compósitos de carbeto de tungstênio (WC) com matriz de intermetálico Fe3Al, em substituição ao ligante cobalto, processados por moagem de pós elementares e consolidação pela técnica de spark plasma sintering (SPS). Também se investigou o efeito da adição de boro no desenvolvimento microestrutural e propriedades mecânicas do compósito WC-Fe3Al. Pós de WC, Fe, Al e Fe-B, com composições WC-10% Fe3Al e WC-10% (Fe3Al-3% B), % em massa, foram moídos em moinho vibratório por tempos de 10 min a 50 h. As misturas de pós foram sinterizadas em um forno SPS utilizando matriz de grafita, com taxa de aquecimento média de 86 ºC/min, a 1150 ºC por 8 min, com pressão de 30 MPa. Foram empregadas técnicas de análise granulométrica, análises térmicas, determinação de densidade, difração de raios X, microscopia óptica convencional e a laser, microscopia eletrônica de varredura acoplada com espectrometria por dispersão de energia, dureza Vickers, tenacidade à fratura pelo método da indentação e ensaio de flexão em três pontos. A moagem causou a diminuição do tamanho das partículas, mas não resultou na formação direta do intermetálico por mechanical alloying mesmo após 50 h de moagem. O aumento no tempo de moagem foi benéfico na melhoria da homogeneidade de dispersão dos grãos de WC na matriz intermetálica. A sinterização por SPS foi eficiente tanto na densificação do compósito, resultando em densidades relativas superiores a 95%, como na formação do intermetálico Fe3Al, considerando a baixa temperatura e curto tempo de consolidação empregados. Também foi formada a fase Fe3AlC0,5 nos compósitos. Os compósitos apresentaram elevadas propriedades mecânicas com valores de até 14,1 GPa de dureza, 25,9 MPa.m½ de tenacidade à fratura, KIc, e 1764 MPa de resistência à flexão. Os resultados de propriedades mecânicas foram correlacionados com as características das matérias-primas, processamento e microestrutura. Os resultados indicaram que os compósitos WC-Fe3Al desenvolvidos têm potencial de substituir, ao menos em parte, os metais duros WC-Co. / Cobalt has restrictions on price instability and potential carcinogenicity. The objective of this study was to verify the technical feasibility of preparation of tungsten carbide (WC) composites with intermetallic Fe3Al matrix, replacing the cobalt binder, processed by milling of elemental powders and consolidating by the spark plasma sintering (SPS) technique. The effects of boron addition on the microstructure development and mechanical properties of WC-Fe3Al composite were also investigated. Powders of WC, Fe, Al and Fe-B, with compositions of WC-10% Fe3Al and WC-10% (Fe3Al-3% B), in mass%, were milled in a vibration mill for times of 10 min to 50 h. The powder mixtures were sintered in a SPS furnace using graphite die, with average heating rate of 86 ºC/min, at 1150 ºC for 8 min, with pressure of 30 MPa. Particle size analysis, thermal analyzes, determination of density, X-ray diffraction, conventional light and laser microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy, Vickers hardness, fracture toughness by indentation method, and three-point flexural test were employed. Milling caused the reduction of particle size, but did not result in the direct formation of intermetallic by mechanical alloying, even after 50 h of milling. The increase in milling time was beneficial in improving the dispersion homogeneity of WC grains in the intermetallic matrix. The sintering by SPS was efficient in the composite densification, resulting in densities higher than 95%, as well in the formation of the intermetallic Fe3Al, considering the low-temperature and short-time used for consolidation. The phase Fe3AlC0.5 was also formed in the composite. The composites presented high mechanical properties with values up to 14.1 GPa in hardness, 25.9 MPa.m½ in fracture toughness, KIc, and 1764 MPa in flexural strength. The results of mechanical properties were correlated to the characteristics of the raw materials, processing and microstructure. The results indicated that the developed WC-Fe3Al composites have potential to replace, at least in part, the WC-Co hardmetals.

One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis investigates the charge-carrier dynamics of two 1D nanomaterials, single-walled carbon nanotubes (CNTs) and tungsten-oxide nanowires (WOxNWs), with the goal of better understanding the nature of their optoelectronic responses, and how nanomaterial geometry and morphology influence these responses. We do this using terahertz time-domain spectroscopy (THz-TDS) and optical pump - terahertz probe time-domain spectroscopy (OPTP). Firstly, we discuss how to properly analyse and interpret the data obtained from these experiments when measuring 1D nanomaterials. While the data obtained from THz-TDS is fairly straight-forward to analyse, OPTP experimental data can be far from trivial. Depending on the relative size of the sample geometry compared to the probe wavelength, various approximations can be used to simplify the extraction of their ultrafast response. We present a general method, based on the transfer matrix method, for evaluating the applicability of these approximations for a given multilayer structure, and show the limitations of the most commonly used approximations. We find that these approximations are only valid in extreme cases where the thickness of the sample is several orders of magnitude smaller or larger than the wavelength, which highlight the danger originating from improper use of these approximations. We then move on to investigate how the charge-carrier dynamics of our CNTs is influenced by nanotube length and density. This is done through studying the nature of the broad THz resonance observed in finite-length CNTs, and how the nanotube length and density affects this resonance. We do this by measuring the conductivity spectra of thin films comprising bundled CNTs of different average lengths in the frequency range 0.3-1000 THz and temperature interval 10-530 K. From this we show that the observed temperature-induced changes in the terahertz conductivity spectra depend strongly on the average CNT length, with a conductivity around 1 THz that increases/decreases as the temperature increases for short/long tubes. This behaviour originates from the temperature dependence of the electron scattering rate, which results in a subsequent broadening of the observed THz conductivity peak at higher temperatures and a shift to lower frequencies for increasing CNT length. Finally, we show that the change in conductivity with temperature depends not only on tube length, but also varies with tube density. We record the effective conductivities of composite films comprising mixtures of WS2 nanotubes and CNTs vs CNT density for frequencies in the range 0.3-1 THz, finding that the conductivity increases/decreases for low/high density films as the temperature increases. This effect arises due to the density dependence of the effective length of conducting pathways in the composite films, which again leads to a shift and temperature dependent broadening of the THz conductivity peak. Next, we investigate the conflicting reports regarding the ultrafast photoconductive response of films of CNTs, which apparently exhibit photoconductivities that can vastly differ, even in sign. Here we observe explicitly that the THz photoconductivity of CNT films is a highly variable quantity which correlates with the length of the CNTs, while the specific type of CNT has little influence. Moreover, by comparing the photo-induced change in THz conductivity with heat-induced changes, we show that both occur primarily due to heat-generated modification of the Drude electron relaxation rate, resulting in a broadening of the plasmonic resonance present in finite-length metallic and doped semiconducting CNTs. This clarifies the nature of the photo-response of CNT films and demonstrates the need to carefully consider the geometry of the CNTs, specifically the length, when considering them for application in optoelectronic devices. We then move on to consider our WOxNWs. We measure the terahertz conductivity and photoconductivity spectra of thin films compromising tungsten-oxide (WOx) nanowires of average diameters 4 nm and 100 nm, and oxygen deficiencies WO2.72 and WO3 using THz-TDS and OPTP. From this we present the first experimental evidence of a metal-to-insulator transition in WOx nanowires, which occurs when the oxygen content is increased from x=2.72 -> 3 and manifests itself as a massive drop in the THz conductivity due to a shift in the Fermi level from the conduction band down into the bandgap. Furthermore we present the first experimental measurements of the photoexcited charge-carrier dynamics of WOx nanowires on a picosecond timescale and map the influence of oxygen-content and nanowire diameter. From this we show that the decay-dynamics of the nanowires is characterized by a fast decay of < 1 ps, followed by slow decay of 3-10 ps, which we attribute to saturable carrier trapping at the surface of the nanowires.

Made available in DSpace on 2014-10-09T12:41:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:03Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:08/10721-9

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Made available in DSpace on 2014-10-09T12:26:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:56Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:06/58686-1

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O presente trabalho tem por objetivo principal explorar a produção, a dispersão e a consolidação de zircônia (óxido de zircônio – ZrO2), em sua forma hidratada, obtida a partir do tungstato de zircônio (ZrW2O8), em meio alcalino e em condições de temperatura de até 100°C. A produção dos materiais particulados foi realizada sob diferentes condições experimentais (concentração de NaOH, tempo e temperatura) de modo a investigar como as características cristalográficas, morfológicas, químicas e térmicas dos pós produzidos são afetadas e, com base nesses resultados, buscou-se inferir o mecanismo pelo qual o ZrW2O8, pó micrométrico e insolúvel em água, originou partículas nanométricas de zircônia em condições brandas de síntese. Neste trabalho também se explorou a dispersão das partículas de zircônia, no momento de sua síntese, com o uso de trietanolamina (TEOA) como surfactante, de modo a obter soluções coloidais estáveis que pudessem ser ultracentrifugadas visando à obtenção de corpos de zircônia transparentes de forma controlada. Verificou-se, de um modo geral, que os materiais particulados produzidos sem a adição de TEOA são compostos por aglomerados de nanopartículas constituídas majoritariamente por Zr e O, com partículas primárias de tamanho próximo a 5 nm e cristalitos inferiores a 3 nm. Os pós apresentaram uma estrutura cristalina semelhante à da ZrO2 cúbica (ou de uma mistura de fases tetragonal e cúbica dependendo da condição de síntese), que formam aglomerados de elevada área superficial, mesoporosidade e capacidade para adsorção de água e dióxido de carbono em diferentes sítios superficiais. O mecanismo da síntese parece ser constituído, primeiramente, por uma reação química de substituição entre os tetraedros de WO4 e íons hidroxila, com posterior solubilização de parte da estrutura, pelo excesso de hidroxilas no meio, formando íons zircônio coloidais que polimerizam/condensam para a formação de núcleos cristalinos para posterior crescimento, em um processo facilitado por nucleação heterogênea e supersaturação. Além disso, a presença de tungstênio remanescente em todas as amostras parece ser um fator importante para a estabilização do tamanho e da estrutura cristalina dos materiais produzidos. A utilização de TEOA no processo de síntese permitiu a obtenção de corpos amarelados e transparentes, por ultracentrifugação, semelhantes a géis, que podem ser entendidos como um híbrido contendo material orgânico e WOx/ZrO2. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2016-05-11T19:20:51Z No. of bitstreams: 1 Tese Marjore Antunes.pdf: 13646783 bytes, checksum: f9ad9dd04536ebae6f6140e93117a8d1 (MD5) / Made available in DSpace on 2016-05-11T19:20:51Z (GMT). No. of bitstreams: 1 Tese Marjore Antunes.pdf: 13646783 bytes, checksum: f9ad9dd04536ebae6f6140e93117a8d1 (MD5) Previous issue date: 2016-05-11 / Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul, FAPERGS / The aim of the present work is to explore the production, dispersion and consolidation of zirconia (zirconium oxide – ZrO2), in its hydrous form, obtained from zirconium tungstate (ZrW2O8) in alkaline medium using temperatures up to 100°C. The production of particulate materials was carried out under different experimental conditions (NaOH concentration, time and temperature) in order to investigate how the crystallographic, morphological, chemical and thermal characteristics of the powders are affected and, based on these results, it was possible to infer the mechanism by which micrometric ZrW2O8 powder, water insoluble, yielded nanosized zirconia particles under mild synthesis conditions. This work also explored the dispersion of zirconia particles using triethanolamine (TEOA) as a surfactant, to obtain stable colloidal solutions which could be ultracentrifuged in order to obtain transparent zirconia bodies. It was found, generally, that the particulate materials produced without the addition of TEOA are composed of agglomerated nanoparticles composed mainly of Zr and O, with primary particle sizes near 5 nm having crystallites of less than 3 nm. The powders had a similar crystalline structure to cubic ZrO2 (or a mixture of tetragonal and cubic phases depending on the synthesis conditions), which create high surface area agglomerates with mesoporosity and capacity for water and carbon dioxide adsorption onto different surface sites. The mechanism of synthesis seems to be related to a chemical reaction of substitution between WO4 tetrahedra and hydroxyl ions, with subsequent solubilization of some portions of the structure due to the hydroxyl groups excess in the medium, originating colloidal zirconium ions which polymerize/condense to form crystal nuclei for further growth, in a process facilitated by heterogeneous nucleation and supersaturation. Furthermore, the presence of the remaining tungsten in all samples seems to be an important factor for stabilizing the size and crystalline structure of the materials produced. The use of TEOA in the synthesis process was responsible for the production of yellowish and transparent bodies by ultracentrifugation, similar to gels, which can be understood as a hybrid containing organic material and WOx/ZrO2.