Electronic and magnetic properties of Ti and Fe on graphene

The structural, electronic and magnetic properties of Fe and Ti atomic wires and the complete covering when adsorbed on graphene are presented through ab initio calculations based on density functional theory. The most stable configurations are investigated for Fe and Ti in different concentrations adsorbed on the graphene surface, and the corresponding binding energies are calculated. The results show a tendency of the Ti atoms to cover uniformly the graphene surface, whereas the Fe atoms form clusters. The adsorption of the transition metal on the graphene surface changes significantly the electronic density of states near the graphene Fermi region. In all arrangements studied, a charge transfer is observed from the adsorbed species to the graphene surface due to the high hybridizations between the systems.

Effect of Ti-C and Cr Additions on Magnetic Properties of Nanocrystalline (Pr,Nd)-Fe-B Alloys

The addition of both Ti-C and Cr as grain refiners in Nd-Fe-B nanocomposites substantially increases the coercive field Hc. This motived our investigation of the effect of Ti-C and Cr on Pr-Fe-B nanocomposites. Melt-spun ribbons of composition (Pr(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0; 0.25; 0.5; 0.75; 1) and (Nd(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0.5 and 1) were produced for study. For a Pr nanocomposite with 1% Cr, Hc = 12.5 kOe. However, the energy product was limited to 13.6 MGOe by the remanence value. Rietveld analysis of X-ray spectra showed the ribbons to consist of predominantly hard (similar to 70 wt%) R(2)Fe(14)B, the soft phase being (similar to 30 wt%) alpha-Fe. Mossbauer measurements at 300 K are consistent with a reduced hyperfine field for the hard magnetic phase due to the Cr addition. Analysis of transmission electron microscopy images showed the Pr nanocomposite with 1% Cr to have an increased average grain size.

Optical and dielectric relaxor behaviour of Ba(Zr(0.25)Ti(0.75))O(3) ceramic explained by means of distorted clusters

In this work, Ba(Zr(0.25)Ti(0.75))O(3) ceramic was prepared by solid-state reaction. This material was characterized by x-ray diffraction and Fourier transform Raman spectroscopy. The temperature dependent dielectric properties were investigated in the frequency range from 1 kHz to 1 MHz. The dielectric measurements indicated a diffuse phase transition. The broadening of the dielectric permittivity in the frequency range as well as its shifting at higher temperatures indicated a relaxor-like behaviour for this material. The diffusivity and the relaxation strength were estimated using the modified Curie-Weiss law. The optical properties were analysed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements at room temperature. The UV-vis spectrum indicated that the Ba(Zr(0.25)Ti(0.75))O(3) ceramic has an optical band gap of 2.98 eV. A blue PL emission was observed for this compound when excited with 350 nm wavelength. The polarity as well as the PL property of this material was attributed to the presence of polar [TiO(6)] distorted clusters into a globally cubic matrix.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Preparation and characterization of Cd(2)Nb(2)O(7) thin films on Si substrates

Thin Cd(2)Nb(2)O(7) films were grown on single-crystal p-type SiO(2)/Si substrates by the metallo-organic decomposition (MOD) technique. The films were investigated by X-ray diffraction, X-ray energy-dispersive spectroscopy, and field emission scanning electron microscopy, and showed a single phase (cubic pyrochlore), a crack-free spherical grain structure, and nanoparticles with a mean size of about 68 nm. A Cauchy model was also used in order to obtain the thickness and index of refraction of the stack layers (transparent layer/SiO(2)/Si) by spectroscopic ellipsometry (SE). The dielectric constant (K) of the films was calculated to be about 25 from the capacitance-voltage (C-V) measurements. (c) 2008 Elsevier Ltd. All rights reserved.

Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.

Major- and trace-element composition of olivine, perovskite, clinopyroxene, Cr-Fe-Ti oxides, phlogopite and host kamafugites and kimberlites, Alto Paranaiba, Brazil

An integrated whole-rock petrographic and geochemical study has been carried out on kamafugites and kimberlites of the Late Cretaceous Alto Paranaiba igneous province, in Brazil, and their main minerals, olivine, clinopyroxene, perovskite, phlogopite, spinels and ilmenite. Perovskite is by far the dominant repository for light lanthanides, Nb, Ta, Th and U, and occasionally other elements, reaching concentrations up to 3.4 x 10(4) chondrite values for light lanthanides and 105 chondrite for Th. A very strong fractionation between light and heavy lanthanides (chondrite-normalized La/Yb from similar to 175 to similar to 2000) is also observed. This is likely the first comprehensive dataset on natural perovskite. Clinopyroxene has variable trace-element contents. likely due to the different position of this phase in the crystallization sequence; Sc reaches values as high as 200 ppm whereas the lanthanides show very variable enrichment in light over heavy REE, and commonly show a negative Eu anomaly. The olivine, phlogopite (and tetra-ferriphlogopite), Cr-Ti oxide and ilmenite are substantially barren minerals for lanthanides and most other trace elements, with the exception of Ba, Cs and Rb in mica, and V, Nb and Ta in ilmenite. Estimated mineral/whole-rock partition coefficients for lanthanides in perovskite are similar to previous determinations, though much higher than those calculated in experiments with synthetic compositions, testifying once more to the complex behavior of these elements in a natural environment. The enormous potential for exploitation of lanthanides, Th, U and high-field-strength elements in the Brazilian kamafugites, kimberlites and related rocks is clearly shown.

Sequential IRMPD of XGe(OEt)(4)(-) ions: Gas-phase synthesis of novel oxy-germanium anions

The gas-phase ion/molecule reactions of F(-) and EtO(-) with Ge(OEt)(4) yield readily and exclusively pentacoordinated complexes XGe(OEt)(4)(-) (X = F, EtO) at pressures in the 10(-8) T range as observed by FT-ICR techniques. These hypervalent species are prone to undergo sequential fragmentations induced by infrared multiphoton excitation that lead to a variety of germyl and germanate anions. In the case of FGe(OEt)(4)(-), three primary competitive channels are observed in the IRMPD process that can be identified as (EtO)(3)GeO(-), F(EtO)(2)GeO(-) and (EtO)(3)Ge(-). Ab initio calculations have been carried out to characterize the primary fragmentation paths induced by IRMPD and the most favorable structure of the resulting anions. The gas-phase acidity of a number of these germanium-containing ions have been estimated by bracketing experiments and by theoretical calculations. Germanate anions such as (EtO)(3)GeO(-) undergo some interesting reactions with H(2)S to give rise to anions such as (EtO)(3)GeS(-) and (EtO)(2)Ge(OH)S(-). (C) 2010 Elsevier B.V. All rights reserved.

The gas-phase alcoholysis of protonated homoleptic alkoxysilanes

Tetra-alkoxysilanes are common and useful reagents in sol-gel processes and understanding their reactivity is important in the design of new materials. The mechanism of gas-phase reactions that mimic alcoholyis of Si(OMe)(4) (usually known as TMOS) under acidic conditions have been studied by Fourier transform ion cyclotron resonance techniques and density functional calculations at the B3LYP/6-311+G(d,p) level. The proton affinity of TMOS has been estimated at 836.4 kJ mol(-1) and protonation of TMOS gives rise to an ionic species that is best represented as trimethoxysilyl cations associated with a methanol molecule. Protonated TMOS undergoes rapid and sequential substitution of the methoxy groups in the gas-phase upon reaction with alcohols. The calculated energy profile of the reaction indicates that the substitution reaction through an S(N)2 type mechanism may be more favorable than frontal attack at silicon. Furthermore, the sequential substitution reactions are promoted by a mechanism that involves proton shuttle from the most favorable protonation site to the oxygen of the departing group mediated by the neutral reagent molecule.

Structural and electrochemical characteristics of Mg((55-x))Ti(x)Ni((45-y))Pt(y) metal hydride electrodes

In recent years, Mg-Ni-based metastable alloys have been attracting attention due to their large hydrogen sorption capacities, low weight, low cost, and high availability. Despite the large discharge capacity and high activity of these alloys, the accelerated degradation of the discharge capacity after only few cycles of charge and discharge is the main shortcoming against their commercial use in batteries. The addition of alloying elements showed to be an effective way of improving the electrode performance of Mg-Ni-based alloys. In the present work, the effect of Ti and Pt alloying elements on the structure and electrode performance of a binary Mg-Ni alloy was investigated. The XRD and HRTEM revealed that all the investigated alloy compositions had multi-phase nanostructures, with crystallite size in the range of 6 nm. Moreover, the investigated alloying elements demonstrated remarkable improvements of both maximum discharge capacity and cycling life. Simultaneous addition of Ti and Pd demonstrated a synergetic effect on the electrochemical properties of the alloy electrodes. Among the investigated alloys, the best electrochemical performance was obtained for the Mg(51)Ti(4)Ni(43)Pt(2) composition (in at.%), which achieved 448 mAh g(-1) of maximum discharge capacity and retained almost 66% of this capacity after 10 cycles. In contrast, the binary Mg(55)Ni(45) alloy achieved only 248 mAh g(-1) and retained 11% of this capacity after 10 cycles. (C) 2010 Elsevier By. All rights reserved.

Leakage current, ferroelectric and structural properties in Pb(1-x)Ba(x)TiO(3) thin films prepared by chemical route

Single-phase perovskite structure Pb(1-x)Ba(x)TiO(3) thin films (x = 0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO(2)/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature Suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage Current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively. (C) 2008 Elsevier Ltd. All rights reserved.

Os efeitos da tecnologia de informação (TI) nas variáveis estratégicas organizacionais da indústria bancária : estudo comparativo entre alguns países da América

A área bancária é um dos setores que mais têm investido em tecnologia de informação (TI), tendo seus produtos e serviços fundamentalmente apoiados por essa tecnologia. Apesar de complexo, mostra-se necessário e importante identificar e avaliar os possíveis efeitos de sua aplicação nas organizações, de forma a poder-se comprovar se os altos investimentos em TI fazem diferença. Nesta dissertação, comparam-se as percepções dos executivos dos bancos argentinos, uruguaios, chilenos, norte-americanos e brasileiros, quanto ao impacto proporcionado pela TI nas variáveis estratégicas das organizações bancárias. O estudo é uma pesquisa survey descritiva, que utilizou como instrumento de coleta de dados o questionário desenvolvido por MAÇADA & BECKER (2001). Para tal, foram realizados testes de validação (primeiramente, com os dados dos três países latino-americanos de língua hispânica e, depois, com os dados dos cinco países envolvidos na pesquisa). Com a realização deste estudo, obtiveram-se, como principais resultados, quatro importantes achados: (1) a Competitividade, os Produtos e Serviços e os Tomadores de Recursos Financeiros (clientes) são as variáveis estratégicas mais afetadas pela TI; Preços e Estrutura de Custos e Capacidade são as variáveis estratégicas menos afetadas pela TI; (2) os executivos dos bancos argentinos e uruguaios, e norte-americanos e uruguaios apresentam percepções muito semelhantes, quanto ao impacto de TI nas organizações bancárias às quais pertencem, enquanto as amostras brasileira e norte-americana apresentam as percepções mais distintas entre si; (3) não há diferença entre executivos de TI e de outras áreas funcionais quanto à percepção dos impactos de TI nas variáveis estratégicas; e (4) o impacto da TI na Competitividade está significativamente relacionado com os impactos da TI nos Tomadores de Recursos Financeiros, Governos e Países, Produtos e Serviços e Estrutura de Custos e Capacidade. A pesquisa apontou, ainda, as variáveis estratégicas mais afetadas pela TI nos setores bancários argentino, uruguaio e chileno. Espera-se que este estudo sobre o impacto de TI nas organizações constitua-se, para os executivos bancários, em ferramenta que possibilite apoiar no planejamento de TI e avaliar a sua utilização, bem como sirva de suporte para a realização de futuras pesquisas sobre esta temática.

Formação e estabilidade térmica de nanocavidades produzidas pela implantação de He em Si

Nesta tese são apresentados os resultados de um estudo sistemático à respeito da formação e evolução térmica de nanocavidades de He em Si cristalino. O efeito da formação de nanocavidades de He no aprisionamento de impurezas em Si foi estudado inicialmente em distintas condições de fluência, temperatura e direção de implantação. Após as implantações, as amostras foram tratadas termicamente a 800°C e analisadas por espectroscopia de retroespalhamento Rutherford em condição de canalização (RBS/C), análise de detecção por recuo elástico (ERDA), espectroscopia por emissão de íons secundários (SIMS) e microscopia eletrônica de transmissão (TEM). Os resultados experimentais mostraram que implantações de He a temperatura ambiente (Ti=Tamb) levam à formação de defeitos numa região intermediária entre a superfície e a camada onde as bolhas se formam (Rp/2), sendo 5x1015He+cm-2 a fluência mínima para a observação do fenômeno. Sua origem foi atribuída à formação de pequenas cavidades nesta região. O mesmo não é observado em implantações a Ti=350°C devido ao efeito do recozimento dinâmico dos defeitos. Estes resultados mostraram a necessidade de um estudo mais profundo a respeito dos efeitos da temperatura de implantação (Ti) na formação de bolhas em Si. Este estudo foi feito a partir de implantações de He no intervalo de temperatura entre -196°C e 350°C, sendo a fluência e a energia de implantação de 2x1016He+cm-2 e 40keV respectivamente. O efeito da proximidade à superfície foi estudado com implantações a 15keV. As amostras foram analisadas pelas mesmas técnicas referidas anteriormente. Para o caso de implantações feitas a 40keV com TiTamb pequenas bolhas são formadas durante a implantação juntamente com defeitos estendidos do tipo {311}. A formação destes defeitos é atribuida ao mecanismo de formação das bolhas baseado na emissão de átomos auto-intersticiais de Si. Distintos regimes são observados após recozimento entre 400°C e 800°C por 600s. Para Ti≤250°C observa-se a dissolução do sistema de cavidades e defeitos devido à interação mutua entre os sistemas. Para Ti>250°C cavidades esféricas e anéis de discordância são observados após recozimentos a 800°C. Finalmente, se observou que a energia de implantação (15keV) não afeta a morfologia do sistema de bolhas e defeitos formados. Porém a perda de He é cinco vezes menor que no caso de amostras implantadas a 40 keV na mesma fluência. Um mecanismo baseado na difusão aumentada por danos de irradiação é sugerido neste trabalho.

Obtenção e caracterização de filmes finos de (Ti,Al) do tipo multicamadas para aplicação em matrizes

Existe, por parte da comunidade industrial e científica, uma incessante procura por revestimentos protetores mais resistentes a ambientes cada vez mais agressivos, como aquele encontrado pelas ferramentas de injeção de alumínio. Uma das tendências que surge para aumentar a vida útil destas ferramentas é a de produzir filmes finos compostos por diversas camadas, cada qual tendo sua função especifica; um exemplo deste tipo de revestimento é aquele composto por camada de adesão, camada intermediária e camada de trabalho. Neste trabalho, foi proposto estudar a utilização do nitreto de titânio e alumínio (Ti,Al)N, tanto como camada intermediária quanto de trabalho, uma vez que este apresenta alta dureza, grande resistência ao desgaste e superior resistência à oxidação. Para a camada intermediária, foram depositados filmes finos tipo multicamadas (TixAl1-x)N/(TiyAly-1)N, (Ti,Al)N/TiN e (Ti,Al)N/AlN, com variação na estrutura cristalina e na espessura das camadas individuais, pois dependendo da quantidade de alumínio adicionado ao sistema, o (Ti,Al)N apresenta mudanças em algumas de suas propriedades, como estrutura cristalina, dureza e resistência mecânica. Os filmes finos monolíticos de (Ti,Al)N e suas multicamadas foram depositadas por magnetron sputtering reativo e caracterizados quanto ao crescimento cristalino, estequiometria, espessura das camadas individuais, dureza e módulo de elasticidade. Na segunda parte deste trabalho, a fim de avaliar a camada de trabalho, é apresentada uma nova técnica de caracterização in-situ, que avalia as reações químicas que ocorrem entre o alumínio e os materiais selecionados. Foram comparados entre si o aço AISI H13, os revestimentos nitreto de titânio, nitreto de cromo, e três diferentes composições de (Ti,Al)N, a fim de verificar qual material apresenta o comportamento mais inerte em contato ao alumínio a altas temperaturas. Para tanto, foram utilizadas as técnicas de calorimetria diferencial de varredura (DSC) e difração de raios X (XRD).

Influence of the Substitutional Solute on the Mechanical Properties of Ti-Nb Binary Alloys for Biomedical Use

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)