RESUMO O presente trabalho teve como objetivo sintetizar membranas lamelares de óxido de grafeno reduzido (rGO – reduced graphene oxide) sobre um suporte de acetato de celulose e compará-las quanto à rejeição de azul de anilina, por meio de duas metodologias de produção do rGO: redução agregante e não agregante. Inicialmente foram produzidas dispersões de óxido de grafeno (GO – graphene oxide) por uma modificação do método de Hummers, as quais passaram por tratamento termoquímico para redução do GO e foram utilizadas para deposição sobre um suporte de acetato de celulose, utilizando-se o método de filtração assistida por vácuo. Para caracterização das dispersões e membranas foram utilizadas as técnicas de difração de raios X (DRX) e microscopia eletrônica de varredura (MEV), sendo que nas membranas produzidas foram conduzidos testes de estabilidade em água. Para análise da rejeição de azul de anilina, utilizado como material a ser filtrado, os permeados de cada uma das membranas, bem como do substrato como recebido, foram analisados por espectrofotometria UV-Vis, sendo que a concentração do permeado pôde ser estimada a partir de uma curva de calibração previamente produzida. Foram observadas diferenças de estabilidade da membrana, a depender da metodologia de redução utilizada, bem como expressivo incremento de rejeição de azul de anilina em relação ao substrato como recebido de acetato de celulose.

ABSTRACT The present work aimed to synthesize lamellar membranes of reduced graphene oxide (rGO) on a cellulose acetate substrate and to compare them for the rejection of aniline blue, using two different rGO production methodologies: aggregating and non-aggregating reduction. Initially, dispersions of graphene oxide (GO) were produced by a modification of the Hummers method, which underwent thermochemical treatment to reduce GO and were used for deposition on a cellulose acetate substrate, using the vacuum-assisted filtration method. To characterize the dispersions and membranes, X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used, and stability tests in water were conducted on the produced membranes. To analyze the rejection of aniline blue, used as the material to be filtered, the permeates of each of the membranes, as well as the substrate as received, were analyzed by UV-Vis spectrophotometry, and the concentration of the permeate could be estimated from of a previously produced calibration curve. Significant differences in membrane stability were observed, depending on the reduction methodology used, as well as an expressive increase in the rejection of aniline blue in relation to the substrate as received from cellulose acetate.

RESUMO A técnica de deposição de filmes por spray destaca-se por sua versatilidade, simplicidade e eficiência. Neste trabalho, dois equipamentos de spray distintos foram empregados para produção de filmes de óxido de grafeno: o primeiro, um equipamento industrial para produção por método ultrassônico e o segundo, uma adaptação realizada com um aerógrafo, um solenoide, um circuito elétrico e um programa em linguagem C++, denominado de método convencional. Os filmes obtidos foram caracterizados com respeito à espessura, resistividade elétrica, transmitância e morfologia. As amostras produzidas pelo método convencional apresentaram menores espessuras e maiores transmitâncias, sendo, desse modo, mais adequadas para aplicações optoeletrônicas. Já as menores resistências de folha foram obtidas pelo método de spray ultrassônico. A morfologia dos filmes aponta melhor uniformidade para as amostras obtidas por meio da técnica ultrassônica. A análise comparativa dos resultados indicou que o equipamento convencional, apesar de ser muito mais simples e de baixo custo, foi capaz de alcançar resultados tão satisfatórios quanto os obtidos em um equipamento industrial de spray ultrassônico. A grande vantagem do equipamento industrial está na possibilidade de produção de várias amostras simultaneamente, enquanto o convencional adaptado tem como benefício a rapidez, possibilidade de deposição com folhas de óxido de grafeno maiores e acessibilidade da produção e operação do sistema.

ABSTRACT The spray technique for thin film deposition stands out for its versatility, simplicity and efficiency. In this work, two different spray techniques, conventional and ultrasonic, were used for the production of graphene oxide films, the first one was an industrial equipment for ultrasonic spray production and the second, an adaptation performed with an airbrush, a solenoid, a circuit electric and a program in C ++ language, called conventional spray. The films obtained were characterized with respect to thickness, electrical resistivity, transmittance and morphology. The samples produced by the conventional method presented thicknesses and transmittances more suitable for electronic applications, since the smaller sheet resistances were obtained by the ultrasonic spray method. The morphology of the films shows a better uniformity for the samples obtained by means of the ultrasonic spray technique. The comparative analysis of the results indicated that the conventional spray equipment, although much simpler and low cost, was able to achieve results as satisfactory as those obtained in an industrial ultrasonic spray equipment. The great advantage of the industrial equipment is the possibility of producing several samples simultaneously, while the conventional spray adapted has the benefit of speed, deposition possibility with larger graphene oxide sheets and accessibility of the production and operation of the system.

RESUMO Dispersões de óxido de grafeno (GO) e de óxido de grafeno reduzido (rGO) foram produzidas, respectivamente, por via química através do método de Hummers modificado e por redução do GO com adição de polímero PSS (poli (4-estirenosulfonato de sódio)) e ácido ascórbico. Amostras de GO e rGO/PSS foram caracterizadas pelas seguintes técnicas: microscopia óptica, microscopia eletrônica de varredura (MEV), espectroscopia Raman e espectroscopia de fotoelétrons excitados por raios X (XPS). A partir das dispersões foram depositados filmes finos em substratos de vidro pelos seguintes métodos: spray, dip coating e spin coating. Os filmes produzidos foram, em seguida, tratados termicamente para melhoria da aderência nos substratos e, especificamente para os filmes de GO, para redução, de modo a formar o óxido de grafeno reduzido termicamente (trGO). Os filmes foram caracterizados quanto a espessura, morfologia, transmitância e resistência de folha. Por meio das caracterizações realizadas a partir das dispersões foi possível observar folhas de grafeno pela microscopia óptica, indicando o sucesso do método de produção empregado; por meio do XPS, determinou-se a composição das amostras de GO e rGO e confirmou-se que a redução com ácido ascórbico foi efetiva; as transmitâncias obtidas mostraram-se dentro da faixa indicada para aplicação e as resistividades de algumas amostras, alcançaram valores próximos a de materiais tradicionalmente aplicados como filmes transparentes e condutores.

ABSTRACT Dispersions of graphene oxide (GO) and reduced graphene oxide (rGO) were respectively chemically produced by the modified Hummers method and by reducing GO with the addition of PSS polymer (poly (4-styrenesulfonate sodium)) and ascorbic acid. Samples of GO and rGO/PSS were characterized by the following techniques: optical microscopy, scanning electron microscopy (SEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). From the dispersions thin films were deposited on glass substrates by the following methods: spray, dip coating and spin coating. The films produced were then thermally treated to improve adhesion on substrates and, specifically for GO films, for reduction, so as to form thermally reduced graphene oxide (trGO). The films were characterized as thickness, morphology, transmittance and sheet resistance. By means of the characterizations made from the dispersions it was possible to observe graphene sheets by optical microscopy, indicating the success of the production method employed; by means of the XPS, the composition of the samples of GO and rGO was determined and confirmed that the reduction with ascorbic acid was effective; the obtained transmittances were within the range indicated for application and the resistivities of some samples reached values close to that of materials traditionally applied as transparent films and conductors.

Stainless steels are well known by their corrosion resistance. The austenitic types, in particular, are also applied as structural components in engineering systems operating at high temperatures such as nuclear reactors, petrochemical furnaces and turbines. For these applications operational temperatures may go up to 800ºC. Under constant load applications the main mechanism of failure, which would limit the material's life, is creep. In the present work creep parameters were evaluated in the high temperature interval of 600 to 800ºC for an AISI 316 austenitic stainless steel. Dislocation substructures were observed by transmission electron microscopy in creep ruptured specimens. Two distinct mechanisms of dynamic strain aging and dynamic recovery associated with different values for the power law exponent n and the Arrhenius activation energy Q for creep were verified below and above 700ºC, respectively.

RESUMO Neste trabalho foram preparadas dispersões aquosas de óxido de grafeno (GO) e óxido de grafeno reduzido (rGO), em diferentes tempos de oxidação, com o objetivo de verificar a influência do tempo de oxidação em relação às características das folhas (flakes) finais. As dispersões de GO foram preparadas pelo método de Hummers modificado utilizando os seguintes tempos de oxidação: 4 h; 1 dia; 3 dias; 7 dias e 10 dias. Em seguida, as dispersões de GO foram submetidas ao tratamento de redução com ácido ascórbico, obtendo-se o rGO. As caracterizações das amostras foram realizadas por meio das análises de espectroscopia Raman, espectroscopia de fotoelétrons excitados por raios X (XPS), microscopia eletrônica de varredura (MEV) e difração de raios X (DRX). A espectroscopia Raman mostrou a variação da relação de intensidade entre as bandas D e G (ID/IG) à medida que o tempo de oxidação foi aumentado. A análise de XPS exibiu a alteração dos percentuais de carbono (C) e oxigênio (O). Através de análise no MEV foi correlacionada a morfologia dos flakes com o aumento do tempo de oxidação. E por fim, com o auxílio de DRX, foi verificada a variação da distância interplanar.

ABSTRACT In this work aqueous dispersions of graphene oxide (GO) and reduced graphene oxide (rGO) were prepared in different oxidation times in order to verify the influence of the oxidation time on the characteristics of the final flakes. GO dispersions were prepared by the modified Hummers method, using the following oxidation times: 4 h; 1 day; 3 days; 7 days and 10 days. Afterwards the dispersions of GO were subjected to the reduction treatment with ascorbic acid, obtaining the rGO. Samples were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Raman spectroscopy showed the variation of the intensity ratio between the D and G bands (ID / IG) as the oxidation time was increased. The XPS analysis indicated the alteration of the percentages of carbon (C) and oxygen (O). The SEM analysis correlated the morphology of the flakes with the increase of the oxidation time. Finally, with the aid of XRD, the variation of the interplanar distance was verified.

RESUMO A energia solar fotovoltaica é atualmente um mercado consolidado. Entre 2010-2016, a taxa de crescimento global de instalações fotovoltaicas foi de 40%, um crescimento dificilmente alcançado por outros segmentos da indústria tecnológica. Células solares de silício responderam por 94% do mercado em 2016, enquanto a parcela referente aos filmes finos foi de 6%. Um dos materiais empregados no segmento fotovoltaico de filmes finos é o disseleneto de cobre índio e gálio (CIGS). Este trabalho apresenta os primeiros resultados de um programa colaborativo entre o Instituto Militar de Engenharia e o Florida Solar Energy Center, que visa à fabricação de células fotovoltaicas de CIGS. Os dispositivos com a configuração vidro/Mo/CIGS/CdS/ZnO/ZnO:Al/metal foram fabricados no Florida Solar Energy Center e caracterizados no Instituto Militar de Engenharia, a partir das medidas de resposta espectral e dos parâmetros fotovoltaicos extraídos das curvas corrente-tensão. A maior eficiência alcançada foi 3,8%. Os resultados mostraram que a eficiência foi basicamente limitada pelo fator de forma e pela tensão de circuito aberto. Resistências em série e paralelo foram responsáveis pelo baixo valor de FF, enquanto que a ausência do tratamento pós-deposição na presença de metais alcalinos e a quantidade de gálio insuficiente foi responsável pelo baixo Voc. Os resultados também sugerem variações na espessura da camada de CdS, causadas provavelmente pela agitação excessiva da solução precursora durante a deposição por banho químico.

ABSTRACT Photovoltaic solar energy is presently a consolidated market. The annual growth rate of global photovoltaic installations was 40% in 2010-2016, a milestone hardly achieved by any other segment of the technology industry. Silicon based technology accounted for 94% of the total production in 2016, while the market share of thin film technology was 6%. One of the materials used in the thin film photovoltaic market is copper indium gallium di-selenide (CIGS). This work presents the preliminary results of a collaborative program between Florida Solar Energy Center and Instituto Militar de Engenharia aiming the fabrication and characterization of CIGS thin film solar cells. The solar devices were fabricated at Florida Solar Energy Center with the configuration glass/Mo/CIGS/CdS/ZnO/ZnO:Al/metal and were characterized at Instituto Militar de Engenharia from the current x voltage and quantum efficiencies curves. The highest efficiency was 3.8%. The results showed that the efficiency was limited by the low values of fill factor and open circuit voltage. Parallel and series resistances limited the fill factor. The lack of the alkali post treatment and the low quantity of gallium in the CIGS film limited the open circuit voltage. The results also suggest that the thickness of the cadmium sulfide layer is nonuniform, probably due to the swirling occasioned by excessively stirring of the precursor solution during the chemical bath deposition.

This work compares the properties of CdS films deposited by CBD and CSS techniques. The influence of the deposition parameters on the properties of the films was investigated. The thickness of CBD films ranged from 80 to 100nm and was affected by the concentration of reactants in the solution. For CSS films, the thickness was controlled in the 100-300nm range, being strongly influenced by the source/substrate temperatures and pressure. Grain size in CSS films was larger than in CBD films. Transmittance of CBD and CSS films ranged from 80 to 90%, but the band gap in CSS films was narrower than in CBD films, which means that CSS films transmit less of the blue part of the solar spectrum than CBD films. However, the growth of CdS films by CSS technique may be advantageous because the CdS/CdTe device could be fully manufactured in the same system.

Unlike other thin film deposition techniques, close spaced sublimation (CSS) requires a short source-substrate distance. The kind of source used in this technique strongly affects the control of the deposition parameters, especially the deposition rate. When depositing CdTe thin films by CSS, the most common CdTe sources are: single-crystal or polycrystalline wafers, powders, pellets or pieces, a thick CdTe film deposited onto glass or molybdenum substrate (CdTe source-plate) and a sintered CdTe powder. In this work, CdTe thin films were deposited by CSS technique from different CdTe sources: particles, powder, compact powder, a paste made of CdTe and propylene glycol and source-plates (CdTe/Mo and CdTe/glass). The largest deposition rate was achieved when a paste made of CdTe and propylene glycol was used as the source. CdTe source-plates led to lower rates, probably due to the poor heat transmission, caused by the introduction of the plate substrate. The results also showed that compacting the powder the deposition rate increases due to the better thermal contact between powder particles.

CdTe thin films are used as absorber layer in CdS/CdTe solar cells. The microstructure of this absorber layer plays a fundamental role in photovoltaic conversion and can be controlled by the deposition parameters used during the film growth. In this work, CdTe thin films were deposited by the CSS method onto glass substrates previously covered with In2O3:Sn. The effects of pressure, source temperature and substrate temperature on the microstructural properties of the films were studied. The properties were mainly influenced by the pressure, the presence of oxygen in the reaction chamber, and the substrate temperature. For films deposited under an argon atmosphere, an increase in grain size and a reduction of the texture were observed as the pressure and substrate temperature were increased. The introduction of oxygen in the atmosphere led to a decrease in the deposition rate and affected the microstructure and composition of the film. Films deposited under an argon-oxygen atmosphere have smaller grains than those deposited under argon and are richer in Te. The addition of oxygen to the atmosphere apparently did not result in the formation of oxides.