Theoretical investigation of atomic and electronic structures of Ga(2)O(3)(ZnO)(6)

Transparent conducting oxides (TCO) are widely used in technological applications ranging from photovoltaics to thin-film transparent field-effect transistors. In this work we report a first-principles investigation, based on density-functional theory, of the atomic and electronic properties of Ga(2)O(3)(ZnO)(6) (GZO(6)), which is a promising candidate to be used as host oxide for wide band gap TCO applications. We identify a low-energy configuration for the coherent distribution of the Ga and Zn atoms in the cation positions within the experimentally reported orthorhombic GZO(6) structure. Four Ga atoms are located in four-fold sites, while the remaining 12 Ga atoms in the unit cell form four shared Ga agglomerates (a motif of four atoms). The Zn atoms are distributed in the remaining cation sites with effective coordination numbers from 3.90 to 4.50. Furthermore, we identify the natural formation of twin-boundaries in GZO(6), which can explain the zigzag modulations observed experimentally by high-resolution transmission electron microscopy in GZO(n) (n=9). Due to the intrinsic twin-boundary formation, polarity inversion in the ZnO tetrahedrons is present which is facilitated by the formation of the Ga agglomerates. Our analysis shows that the formation of fourfold Ga sites and Ga agglomerates are stabilized by the electronic octet rule, while the distribution of Ga atoms and the formation of the twin-boundary help alleviate excess strain. Finally we identify that the electronic properties of GZO(6) are essentially determined by the electronic properties of ZnO, i.e., there are slight changes in the band gap and optical absorption properties.

Thermal, structural and optical properties of Al(2)CoO(4)-Crocoite composite nanoparticles used as pigments

Al(2)CoO(4)-PbCrO(4) and Al(2)CoO(4)-Pb(2)CrO(5) crystalline powders in different proportions were obtained by the polymeric precursor method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of overlapping decomposition reactions due to different exothermal events, which were identified as H(2)O and NO(x) elimination and polymer pyrolysis. The X-ray diffraction patterns of the xAl(2)CoO(4)-(1 - x)PbCrO(4) and xAl(2)CoO(4)-(1 - x)Pb(2)CrO(5) mixed compounds, with x = 1, 0.75, 0.5, 0.25 and 0, were obtained in the crystalline form with their respective phases, and proved consistent with the nominal compositions. The synthesis of these two systems yielded nine different colors and shades.

Low-temperature deposition of silicon oxide and silicon nitride by reactive magnetron sputtering

In this study, oxide and nitride films were deposited at room temperature through the reaction of silicon Sputtered by argon and oxygen ions or argon and nitrogen ions at 250 and 350 W with 0.67 Pa pressure. It was observed that for both thin films the deposition rates increase with the applied RF power and decrease with the increase of the gas concentration. The Si/O and Si/N ratio were obtained through RBS analyses and for silicon oxide the values changed from 0.42 to 0.57 and for silicon nitride the Values changed from 0.4 to 1.03. The dielectric constants were calculated through capacitance-voltage curves with the silicon oxide values varying from 2.4 to 5.5, and silicon nitride values varying from 6.2 to 6.7, which are good options for microelectronic dielectrics. (c) 2008 Elsevier Ltd. All rights reserved.

Improved effective charge density in MOS capacitors with PECVD SiOxNy dielectric layer obtained at low RF power

In this work SiOxNy films are produced and characterized. Series of samples were deposited by the plasma enhanced chemical vapor deposition (PECVD) technique at low temperatures from silane (SiH4), nitrous oxide (N2O) and helium (He) precursor gaseous mixtures, at different deposition power in order to analyze the effect of this parameter on the films structural properties, on the SiOxNy/Si interface quality and on the SiOxNy effective charge density. In order to compare the film structural properties with the interface (SiOxNy/Si) quality and effective charge density, MOS capacitors were fabricated using these films as dielectric layer. X-ray absorption near-edge spectroscopy (XANES), at the Si-K edge, was utilized to investigate the structure of the films and the material bonding characteristics were analyzed through Fourier transform infrared spectroscopy (FTIR). The MOS capacitors were characterized by low and high frequency capacitance (C-V) measurements, in order to obtain the interface state density (D-it) and the effective charge density (N-ss). An effective charge density linear reduction for decreasing deposition power was observed, result that is attributed to the smaller amount of ions present in the plasma for low RF power. (C) 2008 Elsevier B.V. All rights reserved.

Numerical study of tensile tests conducted on systems with elastic-plastic films deposited onto elastic-plastic substrates

In this work, a series of two-dimensional plane-strain finite element analyses was conducted to further understand the stress distribution during tensile tests on coated systems. Besides the film and the substrate, the finite element model also considered a number of cracks perpendicular to the film/substrate interface. Different from analyses commonly found in the literature, the mechanical behavior of both film and substrate was considered elastic-perfectly plastic in part of the analyses. Together with the film yield stress and the number of film cracks, other variables that were considered were crack tip geometry, the distance between two consecutive cracks and the presence of an interlayer. The analysis was based on the normal stresses parallel to the loading axis (sigma(xx)), which are responsible for cohesive failures that are observed in the film during this type of test. Results indicated that some configurations studied in this work have significantly reduced the value of sigma(xx) at the film/substrate interface and close to the pre-defined crack tips. Furthermore, in all the cases studied the values of sigma(xx) were systematically larger at the film/substrate interface than at the film surface. (C) 2010 Elsevier B.V. All rights reserved.

Comparison of oxidation efficiency of disperse dyes by chemical and photoelectrocatalytic chlorination and removal of mutagenic activity

Degradation of Disperse Orange 1, Disperse Red 1 and Disperse Red 13 dyes has been performed using electrochemical oxidation on Pt electrode, chemical chlorination and photoelectrochemical oxidation on Ti/TiO(2) thin film electrodes in NaCl or Na(2)SO(4) medium. 100% discoloration was obtained for all tested methods after 1 h of treatment. Faster color removal was obtained by photoelectrocatalytic oxidation in 0.1 mol L(-1) NaCl pH 4.0 under UV light and an applied potential of +1.0V (vs SCE reference electrode), which indicates also values around 60% of TOC removal. The conventional chlorination method and electrochemical oxidation on Pt electrode resulted in negligible reduction of TOC removal. All dyes showed positive mutagenic activity in the Salmonella/microsome assay with the strain TA98 in the absence and presence of S9 (exogenous metabolic activation). Nevertheless, there is complete reduction of the mutagenic activity after 1 h of photoelectrocatalytic oxidation, suggesting that this process would be good option to remove disperse azo dyes from aqueous media. (C) 2008 Elsevier Ltd. All rights reserved.

Mutagenic activity removal of selected disperse dye by photoeletrocatalytic treatment

The degradation of black dye commercial product (BDCP) composed of C.I. Disperse Blue 373, C.I. Disperse Orange 37, C.I. Disperse Violet 93 dyes was investigated by photoelectrocatalysis process. The dyes have shown high mutagenic activity with Salmonella strain YG1041 and TA98 with and without S9. Samples of BCPD dye submitted to conventional chlorination and photoelectrocatalytic oxidation were compared monitoring its products by HPLC using a diode array detector, spectrophotometry UV-vis, TOC removal, and mutagenicity potency. The photoelectrocatalytic method operating with Ti/TiO(2) as anode at +1.0 V and UV illumination presented fast oxidation of test solutions containing 10 mg L(-1) of dye in 0.1 mol L(-1) NaCl pH 4.0 leading to 100% of discoloration, 67% of mineralization, and negative response to all tested Salmonella strains. The formation of Cl(aEuro cent), CL(2) (aEuro cent) on photoelectrocatalytic medium improved the efficiency of the method in relation to conventional chlorination method that promoted 100% of discoloration, but only 8% of TOC removal and more mutagenic product.

Turbulent spots in boundary layers in a free-piston shock-tunnel flow

In this paper, experiments to detect turbulent spots in the transitional boundary layers, formed on a flat plate in a free-piston shock tunnel how, are reported. Experiments indicate that thin-film heat-transfer gauges are suitable for identifying turbulent-spot activity and can be used to identify parameters such as the convection rate of spots and the intermittency of turbulence.

Boundary-layer transition measurements in hypervelocity flows in a shock tunnel

Experiments to investigate the transition process in hypervelocity boundary layers were performed in the T4 free-piston shock tunnel. An array of thin-film heat-transfer gauges was used to detect the location and extent of the transitional region on a 1500 mm long x 120 turn wide flat plate, which formed one of the walls of a duct. The experiments were performed in a Mach 6 flow of air with 6- and 12-MJ/kg nozzle-supply enthalpies at unit Reynolds numbers ranging from 1.6 x 10(6) to 4.9 x 10(6) m(-1). The results show that the characteristics typical of transition taking place through the initiation, growth, and merger of turbulent spots are evident in the heat-transfer signals. A 2-mm-high excrescence located 440 turn from the leading edge was found to be capable of generating a turbulent wedge within an otherwise laminar boundary layer at a unit Reynolds number of 2.6 x 10(6) m(-1) at the 6-MJ/kg condition. A tripping strip, located 100 mm from the leading edge and consisting of a line 37 teeth of 2 rum height equally spaced and spanning the test surface, was also found to be capable of advancing the transition location at the same condition and at the higher enthalpy condition.

Piezoresistive sensors for force mapping of hip-prostheses

The success of artificial prosthetic replacements depends on the fixation of the artificial prosthetic component after being implanted in the thighbone. The materials for fixation are subject to mechanical stresses, which originate permanent deformations, incipient cracks and even fatigue fractures. This work shows the possibility of monitoring the mechanical stress over time in prosthesis. In this way, highly sensitive silicon thin-film piezoresistive sensors were developed attached to prosthesis and their results compared with commercial strain gauge sensors. Mechanical stress-strain experiments were performed in compressive mode, during 10,000 cycles. Experimental data was acquired at mechanical vibration frequencies of 0.5 Hz, 1 Hz and 5 Hz, and sent to a computer by means of a wireless link. The results show that there is a decrease in sensitivity of the thin-film silicon piezoresistive sensors when they are attached to the prosthesis, but this decrease does not compromise its monitoring performance. The sensitivity, compared to that of commercial strain gauges, is much larger due to their higher gauge factors (-23.5), when compared to the GFs of commercial sensors (2).

Neural Electrode Array Based on Aluminum: Fabrication and Characterization

A unique neural electrode design is proposed with 3 mm long shafts made from an aluminum-based substrate. The electrode is composed by 100 individualized shafts in a 10 × 10 matrix, in which each aluminum shafts are precisely machined via dicing-saw cutting programs. The result is a bulk structure of aluminum with 65 ° angle sharp tips. Each electrode tip is covered by an iridium oxide thin film layer (ionic transducer) via pulsed sputtering, that provides a stable and a reversible behavior for recording/stimulation purposes, a 40 mC/cm2 charge capacity and a 145 Ω impedance in a wide frequency range of interest (10 Hz-100 kHz). Because of the non-biocompatibility issue that characterizes aluminum, an anodization process is performed that forms an aluminum oxide layer around the aluminum substrate. The result is a passivation layer fully biocompatible that furthermore, enhances the mechanical properties by increasing the robustness of the electrode. For a successful electrode insertion, a 1.1 N load is required. The resultant electrode is a feasible alternative to silicon-based electrode solutions, avoiding the complexity of its fabrication methods and limitations, and increasing the electrode performance.

Deuterium NMR Study of Orientational Order in Cellulosic Network Microfibers

Deuterium NMR was used to investigate the orientational order in a composite cellulosic formed by liquid crystalline acetoxypropylcellulose (A PC) and demented nematic 4'-penty1-4-cyanobiphenyl (5CB-4 alpha d(2)) with the per centage of 85% A PC by weight Three forms of the composite including electro spun microfibers, thin film and bulk samples were analyzed The NMR results initially suggest two distinct scenarios, one whet e the 503-alpha d(2), is confined to small droplets with dimensions smaller than the magnetic coherence length and the other where the 503-alpha d(2) molecules arc aligned with the A PC network chains Polarized optical microscopy (POW from thin film samples along with all the NMR results show the presence of 5CB-alpha d(2) droplets in the composite systems with a nematic wetting layer at the APC-5CB-alpha d(2) interface that experiences and order disorder transition driven by the polymer network N-I transition The characterization of the APC network I-N transition shows a pronounced subcritical behavior within a heterogeneity scenario.

Shear-induced lamellar ionic liquid-crystal foam

n a recent paper we reported an experimental study of two N-alkylimidazolium salts. These ionic compounds exhibit liquid crystalline behaviour with melting points above 50 degrees C in bulk. However, if they are sheared, a (possibly non-equilibrium) lamellar phase forms at room temperature. Upon shearing a thin film of the material between microscope slides, textures were observed that are strikingly similar to liquid (wet) foams. The images obtained from polarising optical microscopy (POM) were found to share many of the known quantitative properties of a two-dimensional foam coarsening process. Here we report an experimental study of this foam using a shearing system coupled with POM. The structure and evolution of the foam are investigated through the image analysis of time sequences of micrographs obtained for well-controlled sets of physical parameters (sample thickness, shear rate and temperature). In particular, we find that there is a threshold shear rate below which no foam can form. Above this threshold, a steady-state foam pattern is obtained where the mean cell area generally decreases with increasing shear rate. Furthermore, the steady-state internal cell angles and distribution of the cell number of sides deviate from their equilibrium (i.e. zero-shear) values.

Development of membranes for purification of liquid effluents from stainless steel pickling

Este trabalho foi desenvolvido no âmbito de um projecto europeu intitulado: “Operational demonstration of innovative and sustainable nitrate elimination in stainless steel pickling by higher power biological denitrification technique” Projecto RESP-CT-2007-00047, tendo em vista o desenvolvimento de membranas para o tratamento de efluente resultante da decapagem do aço inox. Numa fase inicial foram desenvolvidas membranas compostas assimétricas pelo método de polimerização interfacial. Estas membranas foram produzidas utilizando uma membrana comercial de suporte em polietersulfona e os filmes selectivos de poliamiada foram formados por reacção entre 1,3,5-tri(clorocarboni)benzeno (TMC) e várias dinaminas: piperazina (PIP), N-(2-aminoetil)-piperazina (EAP), 1,4-bis(3-aminopropil)-piperazina (DAPP), 6-metil-1,3,5 triazina-2,4 diamina (MTC), Isoforodiamina (IPD) e Dietilenetriamina (DET). A elaboração de membranas de TFC (thin film composite) tinha como objectivo a retenção de sais do efluente resultante da decapagem do aço inox. No entanto, chegou-se a conclusão de que o principal problema do efluente não era a retenção dos sais, mas sim a retenção da matéria orgânica. Assim, já não era necessa´ria a produção de membranas compostas, mas apenas uma membrana suporte simples de microfiltração. Numa segunda fase procedeu-se a preparação da membrana suporte pelo método da inversão de fase, tendo-se testado vários tipos de polímeros: PVC (polyvinyl chloride), PEI (Polyetherimide) e um polímero termoplástico geral. A membrana seleccionada foi a de PEI, com base na sua permeabilidade à água destilada e ao efluente resultante das águas residuais da decapagem do aço inox. Todas as membranas elaboradas durante a realização deste trabalho foram testadas na célula de Berghof a uma pressão de 4bar e com agitação. O principal prâmetro estudado foi a permeabilidade da membrana.

Molecular imprinted nanoelectrodes for ultra sensitive detection of ovarian cancer marker

The relentless discovery of cancer biomarkers demands improved methods for their detection. In this work, we developed protein imprinted polymer on three-dimensional gold nanoelectrode ensemble (GNEE) to detect epithelial ovarian cancer antigen-125 (CA 125), a protein biomarker associated with ovarian cancer. CA 125 is the standard tumor marker used to follow women during or after treatment for epithelial ovarian cancer. The template protein CA 125 was initially incorporated into the thin-film coating and, upon extraction of protein from the accessible surfaces on the thin film, imprints for CA 125 were formed. The fabrication and analysis of the CA 125 imprinted GNEE was done by using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques. The surfaces of the very thin, protein imprinted sites on GNEE are utilized for immunospecific capture of CA 125 molecules, and the mass of bound on the electrode surface can be detected as a reduction in the faradic current from the redox marker. Under optimal conditions, the developed sensor showed good increments at the studied concentration range of 0.5–400 U mL−1. The lowest detection limit was found to be 0.5 U mL−1. Spiked human blood serum and unknown real serum samples were analyzed. The presence of non-specific proteins in the serum did not significantly affect the sensitivity of our assay. Molecular imprinting using synthetic polymers and nanomaterials provides an alternative approach to the trace detection of biomarker proteins.