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The effect of high pressure (7.7 GPa) densification on the absorption and near-infrared emission of Nd-doped lithium, sodium and potassium disilicate glasses was investigated. Judd-Ofelt parameters O¿ (¿ = 2, 4 and 6) were calculated from the absorption spectra, before and after densification of glasses, indicating that the irreversible structural changes induced by pressure increased the symmetry of the Nd-O bonding. Density and refractive index of the glasses also increased, probably related to the close packing of SiO4 tetrahedra during densification. The magnitude of the splitting due to the Stark effect was larger for potassium silicate, before and after densification. The radiative transition probabilities of the hypersensitive transition for sodium and potassium silicate increased after densification while the radiative lifetime decreased. For lithium silicate, the opposite behavior was observed. The experimental results corroborate the influence of alkali ion and densification on the luminescence properties of Nd-doped alkali silicate glasses

TiO2/SiO2 nanoparticles with 3, 5, and 10 molar percent of silica, were synthesized by hydrothermal method and characterized by SEM, TEM, N2 adsorption-desorption isotherms, X-ray diffraction, and Raman and UV-Vis spectroscopy. While pristine TiO2 thermally treated at 500°C presents a surface area of 36 m2g-1(±10 m2g-1), TiO2/SiO2 containing 3, 5, and 10 molar percent of silica present surface areas of 93, 124, and 150 m2g-1(±10 m2g-1), respectively. SiO2is found to form very small amorphous domains well dispersed in the TiO2 matrix. X-ray diffraction and Raman spectroscopy data show that anatase-to-rutile phase transition temperature is delayed by the presence of SiO2, enabling single-anatase phase photoanodes for DSSCs. According to the I×V measurements, photoanodes with 3% of SiO2 result in improved efficiency, which is mainly related to increasedsurface area and dye loading. In addition, the results suggest a gain in photocurrent related to the passivation of defects by SiO2

A pressure cell with an anvil made of sapphire and the other made of tungsten carbide, was constructed to process thin film samples using a high power Nd:YAG pulsed laser, in a regime of ultrafast quenching rate and confined geometry. The sapphire anvil worked as the optical window to the laser beam and also as a good thermal conductor substrate. Thin films of amorphous carbon deposited over copper substrate were processed under pressure by Nd:YAG laser pulses. This process induces the formation of a high temperature region at the sample surface during a very short time interval of the order of the 8 ns laser pulse duration. To avoid the complete evaporation of the film, an external pressure of about 0.5 to 1.0 GPa was applied, confining the sample. With the aid of the nanosecond pulsed laser, absorbed on a very thin film sample, this specially designed apparatus provides the means to produce ultrafast quenching as the formation of a plume is suppressed and heat dissipation is accelerated by the high thermal conductivity of the copper substrate and sapphire anvil. The processed samples were analyzed by microRaman spectroscopy and the results indicated the formation of polyynic carbyne structures, as revealed by the presence of a characteristic Raman peak at about 2150 cm-1. Another set of Raman peaks observed at 996, 1116, and 1498 cm-1, also appeared when the amorphous carbon film was processed with a sequence of more than three consecutive laser pulses. These peaks, whose general aspect is very similar to that of polyacethylene (CnHn), could be ascribed to the cumulenic carbyne structure, stabilized by some dispersed copper atoms.

A modification of the one dimensional A ° ngstro¨m’s method that employs photothermal radiometry has been used to determine the longitudinal thermal diffusivity of three thin long bars of chemical vapor deposited diamond. Long bar specimens permit us to use a simple one-dimensional treatment that employs a linear least squares fitting procedure on both magnitude and phase data as a function of position, provided that the condition for ignoring end effects is fulfilled. Any differences in diffusivities obtained from magnitude data and from phase data can be attributed to surface heat losses; the values of diffusivity obtained with the two types of data showed no significant difference. The diffusivities obtained agree reasonably well with the mean values calculated from measurements made by several other laboratories on the same specimens. The heat source was the beam of an argon-ion laser focused onto the specimen surface either with a cylindrical lens to form a line focus or with a spherical lens to form a point focus. The differences in diffusivities obtained when a line source was used and when a point source was used were not statistically significant. A theoretical calculation indicates that the measurements on the specimen were made sufficiently far from the heat source for the one-dimensional treatment to be valid whether the line source or the point source were used: either source is expected to give the same result as was observed experimentally. A point source is preferable because the optical configuration of the experiment is simpler and larger signals are obtainable.

Neste trabalho são apresentados resultados experimentais sobre a variação do índice de refração em altas pressões para três grupos de materiais cerâmicos: fluoretos ( LiF, CaF2, MgF2), óxidos (A1203, c-Zr02, m-Zr02) e materiais superduros (c-BN, 3C-SiC e diamante). Estes resultados foram obtidos através de um método interferométrico, em conjunto com a câmara de pressão do tipo bigornas de diamante, que permitiu atingir pressões da ordem de 10 GPa. Resultados anteriores, quando encontrados, limitam-se à região de baixa pressão, até cerca de 0,7 GPa. Para todos os compostos estudados, a variação do índice de refração observada foi praticamente linear com a pressão. Para os fluoretos, o índice de refração aumenta com a pressão, enquanto que, para os demais compostos, o índice de refração diminui com a pressão, com exceção de uma das componentes no caso da zircônia monoclínica birrefringente. A análise dos resultados, segundo a abordagem clássica de Lorentz-Lorenz, em termos de entidades individuais polarizáveis, permitiu determinar o comportamento da polarizabilidade dos átomos, a, durante a variação do volume para todos os compostos. Obteve-se uma dependência praticamente linear, a qual pôde ser representada por um parâmetro constante para cada material. No caso dos fluoretos, altamente iônicos, a variação relativa da polarizabilidade foi pequena comparada aos demais casos, consistente com a imagem dos íons como esferas pouco deformáveis. No caso dos óxidos, que apresentam certo grau de covalência, o oxigênio mostrou-se bastante deformável e sensível à estrutura cristalina. Para a zircônia monoclínica, inclusive, a anisotropia das interações interatômicas provocou uma deformação do tipo elipsoidal no oxigênio durante a aplicação de pressão, responsável por comportamentos distintos das duas componentes medidas do índice de refração: uma aumentou e a outra diminuiu com a pressão. Para os materiais superduros, apesar de ser discutível a validade do conceito de polarizabilidade nestes casos, obteve-se um comportamento também linear, sem discrepâncias significativas devidas ao caráter fortemente covalente destes materiais. Os resultados para a(V) foram usados para testar modelos semi-empíricos sobre a dependência da polarizabilidade dos ânions com a distância interatômica. A análise feita permitiu concluir que os modelos testados são satisfatórios apenas para os fluoretos, provavelmente devido ao caráter iônico e à pequena deformabilidade do flúor. Os modelos que consideram que os elétrons responsáveis pela polarização estejam distribuidos numa casca esférica, conduzem a melhores resultados do que os que consideram estes elétrons distribuidos numa cavidade esférica. Para os materiais superduros, foi possível determinar uma correlação entre os comportamentos da carga transversal efetiva e da polarizabilidade eletrônica durante a variação da pressão: o aumento da carga transversal efetiva contribui para a redução da polarizabilidade devido à concentração da nuvem eletrônica, tendo como consequência, um decréscimo relativamente acentuado no índice de refração, como ocorre para o 3C-SiC. Por outro lado, a diminuição da carga transversal efetiva tem um efeito contrário sobre a redução da polarizabilidade, atenuando o decréscimo no índice de refração com a pressão, como acontece para o c-BN. O diamante, por ser um cristal homopolar, tem carga transversal efetiva nula e representa uma situação intermediária entre o c-BN e o 3C-SiC. De acordo com uma visão delocalizada do cristal, os resultados obtidos para os materiais superduros foram utilizados para testar modelos propostos na literatura, relacionando o índice de refração à banda de energia proibida do material. Nenhum dos modelos descreve, simultaneamente, a relação entre os comportamentos destes dois parâmetros durante a variação de pressão, para os três casos estudados. Entretanto, a análise feita permitiu concluir que, em princípio, estes modelos são aplicáveis a materiais sob pressão apenas quando a energia da radiação incidente é pequena comparada à banda de energia proibida. O método interferométrico utilizado pode ser usado para medir a pressão em câmaras com janelas óticas, apresentando uma sensibilidade significativamente maior do que a da técnica de fluorescência do rubi. In this work we present experimental results for the variation of the refractive index in high pressures for three groups of ceramic materiais: fluorides (LiF, CaF2, MgF2), oxides (A1203, c-Zr02, m-Zr02) and superhard materiais (c-BN, 3C-SiC and diamond). These results were obtained using an interferometric method in the diamond anvil cell, that enables pressures up to 10 GPa. Previous results present in the literature, exist only for few cases and for the low pressure range, up to 0,7 GPa. For ali the compounds, the observed variation of the refractive index was almost linear: for the fluorides, it increases with pressure and, for the other compounds, it decreases with pressure, except for one of the components in the case of the monoclinic zirconia. The analysis of the results following the classical Lorentz-Lorenz approach in terms of individual and polarizable entities, allows the determination of the volume dependence of the electronic polarizability, a, for ali the compounds. An almost linear relationship was obtained, well represented by a constant parameter for each material. In the case of the highly ionic fluorides, the relative variation of the polarizability is smaller than for the other cases, consistent with the ionic picture of nearly "hard spheres". In the case of oxides, the oxygen ion was deformable and sensitive to the crystalline structure. For the monoclinic zirconia, the anisotropic interatomic interactions induce an elipsoidal deformation in the oxygen ion during the pressure variation, that is responsible for the distinct behaviors of both components of the refractive index: one increases and the other decreases with pressure. For the superhard materiais, despite the conception of electronic polarizability in covalent material is a subject of discussion, a linear behavior was obtained for the volume dependence of the polarizability, without any discrepancy due to the strong covalent character of these materials. The obtained results for a(V) were used to test semi-empirical models relating the anion electronic polarizability and the interatomic distance. The models were satisfactory only for the fluorides, probably due to the ionic caracter and to the small deformability of the fluorine ion. The models considering that the electrons responsible for the polarization are in a spherical shell, give better results than the models considering the electrons confined to a spherical cavity. For the superhard materiais, it was possible to find a correlation between the variations of the transverse effective charge and the electronic polarizability with pressure: the increase of the transverse effective charge contributes to the reduction of the polarizability due to the concentration of the electronic cloud, resulting in an strong decrease of the refractive index, as is the case for 3C-SiC. On the other hand, the decrease of the transverse effective charge has an opposite effect over the reduction of the polarizability, and the decrease of the refractive index is less pronounced, as is the case for c-BN. Since diamond is a homopolar crystal, there is no transverse effective charge, representing an intermediate situation. Following a delocalized picture of the crystal, the obtained results for the superhard materiais were used to test proposed models found in the literature, relating the refractive index and the energy band gap of the material. It was found that none of them simultaneously describes the behavior of these parameters during the pressure variation for the three studied materiais. The analysis of the results allows the conclusion that these models could be valid for a given material under pressure only when the value of the incident energy is not dose to the band gap energy of the material. The interferometric method can be used for pressure calibration in high pressure cells with an optical window, showing higher sensitivity than the technique of the ruby fluorescence.

The pressure dependence of the refractive index of monoclinic and yttria-stabilized cubic zirconia was measured up to 3 and 8 GPa, respectively, using an interferometric method with the diamond-anvil cell. The experimental results show a practically linear behavior for both crystalline structures. For cubic zirconia, the refractive index remains practically constant under pressure, while for the biaxial monoclinic phase, one component of the refractive index decreases and the other component increases with pressure, despite the rather isotropic lattice compression in the corresponding crystalline directions. The behavior of the electronic polarizability of the oxygen ion was investigated through the LorentzLorenz relation, yielding the following Mueller parameters: for the cubic phase A0= 1.02, and for the monoclinic phase A0=1.05 for the component nearly parallel to the b direction, and A0=0.85 for the component in the direction of the projection of the "a" axis on the sample plane. In the case of monoclinic zirconia, the behavior of the polarizability under pressure is about 20% more anisotropic than the compression of the respective lattice parameters, indicating a distinct effect of the interatomic interactions over the oxygen íons for the two directions under consideration.

O presente trabalho envolve medidas do índice de refração no MgO como função de pressão, através de um micro-interferômetro deste material, colocado no interior de uma camara de alta pressão do tipo bigornas de diamante. In this work we measured the pressure dependence of the refractive index of MgO. A micro-interferometer of this material was inserted into a diamond anvil cell.

Este trabalho explora a utilização do algoritmo genético de minimização global por Evolução Diferencial (ED) como método de determinação de parâmetros de potenciais interatômicos (PIs) usados no cálculo de propriedades físicas de materiais. Dois compostos foram utilizados como estudo de caso: a berlinita (AlPO4) e a fase cúbica do tungstato de zircônio ( -ZrW2O8 ). Em ambos os casos, o potencial interatômico considerado foi uma combinação de potenciais de Buckingham, covalente exponencial e harmônico de três corpos, além do modelo casca-caroço de Dick-Overhauser para os átomos de oxigênio. Os parâmetros livres do potencial foram ajustados de modo a fornecer estimativas para os parâmetros de rede, posições atômicas e constantes elásticas de ambas as estruturas que mais se aproximassem dos valores experimentais. O algoritmo de evolução diferencial foi capaz de encontrar potenciais que melhor reproduzem as propriedades atérmicas em ambos os casos, quando comparados com PIs previamente publicados. Os potenciais encontrados para a fase cúbica do tungstato de zircônio foram aplicados à cálculos de dinâmica de rede para avaliar a influência da temperatura no seu parâmetro de rede. O algoritmo de ED encontrou um conjunto de parâmetros para potenciais com modelos analíticos relativamente simples, porém capaz de descrever com razoável precisão a expansão térmica negativa do -ZrW2O8 em baixas temperaturas. A evolução diferencial mostrouse um método capaz de explorar exaustivamente o espaço de parâmetros, o que indica que as limitações encontradas na descrição da estrutura possam ser superadas com a adição de termos ao PI ou com o uso de outra forma analítica. This work explores the use of the genetic algorithm differential evolution (DE) for global minimization as a method for determining the interatomic potential (IP) parameters used in the calculation of physical properties of materials. Two compounds were used as a case study: Berlinite (AlPO4) and the cubic phase of zirconium tungstate ( -ZrW2O8 ). In both cases, the IP was built as a combination of Buckingham, covalent exponential, and three body harmonic potentials, together with the Dick-Overhauser core-shell model for the oxygen atoms. The free parameters of the potential were adjusted to estimate the lattice parameters, atomic positions and elastic constants of both structures that were closest to experimental values. The DE algorithm was able to find potentials that are better in describing the athermal properties for both compounds when compared to previously published IPs. The potentials found for the cubic phase of zirconium tungstate were applied in lattice dynamics calculations in order to assess the temperature influence in the lattice parameter. The DE found a relatively simple IP, but capable of describing the negative thermal expansion of -ZrW2O8 at low temperatures with reasonable precision. The DE has shown to be a method capable to exhaustively explore the parameter space of the PI, which indicates that the limitations found in describing the zirconium tungstate structure modifications as a function of temperature can be surpassed with additional terms in the potential or with another, more complex, analytical form.

Neste trabalho, amostras de oxido de grafite (GO), sintetizadas pelo metodo de Hummers modificado, foram investigadas com enfase no efeito de altas pressoes aplicadas tanto simultaneamente a tratamentos termicos quanto aplicadas a temperatura ambiente. A estrutura do GO e semelhante a do precursor de grafite, exceto por um aumento nas distancias interplanares devido a grupos funcionais adicionais, tais como grupos hidroxilas, epoxis, carbonilas e carboxilas, os quais se encontram distribuıdos aleatoriamente nos esqueletos de carbono. Os experimentos foram realizados na regiao de estabilidade termodinamica do grafite e do diamante (2,5 e 7,7 GPa) usando camaras do tipo toroidal e temperaturas de 300, 600, 900, 1200 e 1500 ◦C por 15 minutos. Alem disso, amostras de GO foram submetidas a tratamento termico a 1500 ◦C por 15 minutos a pressao ambiente, em atmosfera nao oxidante. As amostras obtidas foram caracterizadas por espectroscopia Raman, de absorcao no infravermelho (FT-IR), de fotoeletrons excitados por raios X (XPS), difracao de raios X (DRX) e microscopia eletronica de transmissao (MET). Os resultados obtidos mostram que a distancia interplanar d para as amostras processadas em 2,5 GPa sofre uma reducao partindo de 7,5 ˚A, valor registrado para a amostra virgem, para 3,425 ˚A apos a pirolise a 1500 ◦C, ainda superior ao do grafite tıpico (3,35 ˚A). Ja para a amostra processada a 7,7 GPa e 1500 ◦C, o valor de d atinge 3,351 ˚A, bem pr´oximo ao valor esperado para uma estrutura grafıtica bem organizada, indicando que uma pressao mais elevada tenderia a eliminar os defeitos estruturais de forma mais eficiente. Analises de microscopia eletronica de transmissao indicam que na amostra processada em 2,5 GPa e 1500 ◦C foi possıvel notar a coexistencia de dois padroes distintos. Alem da presenca de folhas, que agora representam o GO reduzido termicamente, ou seja, com parte dos grupos oxigenados eliminados de suas bordas e espacos intercamadas, e possıvel observar tambem a presenca de pequenos graos, possivelmente grafıticos. Ja a amostra processada em 7,7 GPa e 1500 ◦C apresentou uma grande concentracao de graos, consistente com a maior cristalinidade observada atraves da an´alise dos difratogramas de raios X. Alem disso, ao analisar a amostra tratada a 1500 ◦C a pressao ambiente e atmosfera nao oxidante, nao foi possıvel observar a presenca dos graos grafıticos, apenas de folhas de GO reduzido, o que seria um indicativo de que as altas pressoes favoreceriam a grafitizacao atraves do mecanismo de recristalizacao. In this work, samples of graphite oxide (GO), synthesized by the modified Hummers method, were investigated with emphasis on the effect of high pressures applied both simultaneously to thermal treatments and applied at room temperature. GO structure is similar to that of the graphite precursor, except for an increase in interplanar spacings due to additional functional groups, such as hydroxyl groups, epoxides, carbonyls and carboxyl groups, which are randomly distributed in the carbon backbones. The experiments were carried out in the thermodynamic stability region of graphite and diamond (2.5 and 7.7 GPa) using toroidal chambers and temperatures of 300, 600, 900, 1200 and 1500 ◦C for 15 minutes. In addition, GO samples were heat-treated at 1500 ◦C for 15 minutes at ambient pressure in a non-oxidizing atmosphere. The samples obtained were characterized by Raman spectroscopy, infrared absorption spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the value of interplanar spacing d for the samples processed in 2.5 GPa is reduced from 7.5 ˚A, value recorded for the pristine sample, to 3.425 ˚A after the pyrolysis at 1500 ◦C, still higher than the value registered for the typical graphite (3.35 ˚A). For the sample processed at 7.7 GPa and 1500 ◦C, the value of d reaches 3.351 ˚A, very close to the expected value for a well-organized graphite structure, indicating that a higher pressure would tend to eliminate structural defects more efficiently. Transmission electron microscopy analysis indicates that in the sample processed at 2.5 GPa and 1500 ◦C it was possible to note the coexistence of two distinct patterns. Besides the presence of sheets, which now represent the thermally reduced GO, this is, with part of the oxygenated groups eliminated of its edges and interlayer spaces, it is also possible to observe the presence of small grains, possibly of the graphitic type. Whereas the sample processed at 7.7 GPa and 1500 ◦C showed a high grain concentration, consistent with the higher crystallinity observed by X-ray diffraction analysis. Furthermore, on analyzing the heat-treated sample at 1500 ◦C at ambient pressure and non-oxidizing atmosphere, it was not possible to observe the presence of the graphitic grains, only of reduced GO sheets, which would be indicative of the high pressures would favor the graphitization through the recrystallization mechanism.

Pontos quânticos de carbono (C-dots) luminescentes na região do azul-verde aprisionados em matriz de sílica foram produzidos por um processo novo, baseado na pirólise de grupos contendo carbono dispersos nas bordas dos grãos de dimensões nanométricas de sílica (AEROSIL) previamente sinterizados a frio sob alta pressão, onde nenhuma técnica de passivação foi exigida. A análise de difração de elétrons de área selecionada (SAED – Selected Area Electron Diffraction) e espectroscopia de perda de energia de elétrons (EELS – Electron Energy Loss Spectroscopy) confirmaram a formação de C-dots contendo átomos de carbono com ligações do tipo sp2. Foram investigados diferentes valores de pressão (2,5, 4 e 7,7 GPa) para sinterização a frio e diferentes temperaturas de pirólise, a partir de 500 até 900°C. Resultados de análise térmica revelaram pequena perda de massa durante a pirólise das amostras, praticamente independente da pressão utilizada na sinterização. Espectroscopia na faixa do infravermelho revelou alterações nas bandas de aborção na faixa correspondente aos modos de vibração de CH2 e CH3, dependentes da temperatura e da pressão utilizadas. Os espectros de fotoluminescência (FL) foram fortemente dependentes do comprimento de onda de excitação e observou-se uma intensidade de emissão mais elevada no intervalo entre 500-550 nm para a amostra sinterizada a frio em 7,7 GPa e tratada termicamente a 800°C para excitação em 460 nm. Também foi investigado a contribuição da matriz de silica após a sinterização. Quantum dots in the blue-green region embedded in a silica matrix were produced by a new process based on the pyrolysis of groups containing carbon dispersed on the edges of the grain of nanosized silica (AEROSIL) previously sintered under high pressure, where no passivation technique was required. The Selected Area Electron Diffraction (SAED) and Electron Energy Loss Spectroscopy (EELS) confirmed the formation of Cdots containing carbon atoms with sp2 bonds. Different pressure values (2,5, 4 and 7,7 GPa) were investigated for cold sintering and the pyrolsys was in the temperature range from 500 to 900°C. Results of thermal analysis revealed a small loss of mass during the pyrolysis of the samples, practically independent of the sintering pressure. Infrared spectroscopy revealed changes in the absorption bands in the range corresponding to the CH2 and CH3 vibration modes, depending on the temperature and pressure conditions. Photoluminescence (PL) spectra were strongly dependent on the excitation wavelength and a higher emission intensity was observed in the range 500-550 nm for the sample sintered at 7.7 GPa and pyrolysed at 800°C for excitation at 460 nm. The contribution of the silica matrix after sintering was also investigated.