Piezooptical effects in the tellurite glasses doped by europium and gold

We present the temperature dependence of piezooptical coefficients for three samples of TeO(2)-GeO(2)-PbO glasses doped with 0.5% of Eu(2)O(3), 0.5% and 1% of Au(2)O(3), after different thermoannealing times. We have established that there exist two temperatures singularities - minima in the range 655-695 K and maxima - at 850 K. It is crucial that for the glasses annealed during 61 h, at temperatures about 850 K, the anomaly of piezooptical coefficient disappears. Simultaneously the minima within the range 655-695 K changed depending on the duration of the thermoannealing which leads to low temperature shift of the minima. Towards lower temperature the piezooptical maxima occurs around 850 K and disappears after the increase of the annealing time. It is also crucial that the values of the piezooptical coefficients decrease with the enhancement of the thermoannealing. The observed temperature dependence with the piezooptical coefficients has a good correlation with the temperature dependences of the DSC. We have found that the pure glasses and glasses doped only by Au(2)O(3) and Eu(2)O(3) possess the piezooptical coefficients one order less with respect to the samples possessing simultaneously Au(2)O(3) and Eu(2)O(3). (C) 2008 Elsevier B.V. All rights reserved.

The rheological behavior and surface charging of gelcasting alumina suspensions

Aim of this work is to investigate the effect of monomers containing either carboxylate (ammonium acrylate) or acrylamide (hydroxymethylacrylamide) functional groups on the surface charging and theological behavior of alumina suspensions. The rheological behavior was investigated by changing the concentrations of dispersant (ammonium polyacrylate) and monomers in the suspensions. The zeta potential of alumina suspensions containing each of the different monomers was measured as a function of dispersant additions. The suspension theological behavior varied significantly depending on the monomer type, which could be explained in terms of repulsive forces, pH changes and additive interactions. (C) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Eu3+ luminescence in tellurite glasses with gold nanostructures

Luminescence properties of Eu3+ doped TeO2-PbO-GeO2 glasses containing gold nanoparticles (NPs) were investigated. The emission spectra of the samples exhibited enhancement of Eu3+ luminescence due to the presence of gold NPs. The emission at 614 nm. due to the Eu3+ hypersensitive transition D-5(0)-F-7(2), is much influenced by the gold NPs and increases by approximate to 100%. for samples heat-treated at 350 degrees C during 41 h. (c) 2007 Elsevier B.V. All rights reserved.

Influence of the heat treatment on the nucleation of silver nanoparticles in Tm(3+) doped PbO-GeO(2) glasses

Nucleation of silver nanoparticles (NPs) in Tm(3+) doped PbO-GeO(2) (PGO) glass is reported. The influence of the heat treatment on the nucleation of silver NPs is studied by means of transmission electron microscopy and optical spectroscopy. Two heat treatment procedures were applied in order to compare their performance. Observation of infrared-to-visible frequency upconversion (UC) luminescence of Tm(3+) ions is reported and correlated with the heat-treatment procedure. Enhancement of the UC emission for samples heat treated during various time intervals is attributed to the increased local field in the vicinity of the NPs. Quenching of the UC signal was also observed and correlated with the growth of NPs amount and size.

Effect of Charge Asymmetry on Adsorption and Phase Separation of Polyampholytes on Silica and Cellulose Surfaces

The relation between the properties of polyampholytes in aqueous solution and their adsorption behaviors on silica and cellulose surfaces was investigated. Four polyampholytes carrying different charge densities but with the same nominal ratio of positive to negative segments and two structurally similar polyelectrolytes (a polyacid and a polybase) were investigated by using quartz crystal microgravimetry using silica-coated and cellulose-coated quartz resonators. Time-resolved mass and rigidity (or viscoelasticity) of the adsorbed layer was determined from the shifts in frequency (Delta f) and energy dissipation (Delta D) of the respective resonator. Therefore, elucidation of the dynamics and extent of adsorption, as well as the conformational changes of the adsorbed macromolecules, were possible. The charge properties of the solid Surface played a crucial role in the adsorption of the studied polyampholytes, which was explained by the capability of the surface to polarize the polyampholyte at the interface. Under the same experimental conditions, the polyampholytes had a higher nominal charge density phase-separated near the interface, producing a soft, dissipative, and loosely bound layer. In the case of cellulose substrates, where adsorption was limited, electrostatic and polarization effects were concluded to be less significant.

Anodic porous alumina structural characteristics study based on SEM image processing and analysis

The present work reports the porous alumina structures fabrication and their quantitative structural characteristics study based on mathematical morphology analysis by using the SEM images. The algorithm used in this work was implemented in 6.2 MATLAB software. Using the algorithm it was possible to obtain the distribution of maximum, minimum and average radius of the pores in porous alumina structures. Additionally, with the calculus of the area occupied by the pores, it was possible to obtain the porosity of the structures. The quantitative results could be obtained and related to the process fabrication characteristics, showing to be reliable and promising to be used to control the pores formation process. Then, this technique could provide a more accurate determination of pore sizes and pores distribution. (C) 2008 Elsevier Ltd. All rights reserved.

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.

Electron beam induced second-harmonic generation in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles

Electron beam induced second harmonic generation (SHG) is studied in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles with concentrations that are controlled by the heat-treatment of the samples. The SHG is observed at T = 4.2 K using a p-polarized laser beam at 1064 nm. Enhancement of the SHG is observed in the samples that are submitted to electron beam incidence. The highest value of the nonlinear susceptibility, 2.08 pm/V, is achieved for the sample heat-treated during 72 h and submitted to an electron beam current of 15 nA. The samples that were not exposed to the electron beam present a susceptibility of a parts per thousand 0.5 pm/V.

DSC estimation of structural and textural parameters of SBA-15 silica using water probe

The aim of this study was to use DSC and X-ray diffraction measurements to determine the pore size and pore wall thickness of highly ordered SBA-15 materials. The DSC curves showed two endothermic events during the heating cycle. These events were due to the presence of water inside and outside of mesopores. The results of pore radius, wall thickness and pore volume measurements were in good agreement with the results obtained by nitrogen adsorption measurement, XRD and transmission electron microscopy.

Evaluation of Some Biological Aspects of the Presence of Abrasive Silica and Thickening Silica in Basic Formulations of Dentifrices

The aim of this study was to evaluate some biological characteristics and toxicity of basic formulations of dentifrices containing such substances, and to compare them with two existing products in market which also contains silic in their formulations. In this way, it was evaluated some biological parameters: weight of the animals, oral toxicity, hematological parameters, urinary analysis, and histological evaluation. The thrombocytes were also statistically at normal levels. The glutamate-pyruvate transaminase (TGP) showed normal aspect in 5 of the tested groups, as in control. Meanwhile, the oxalacetic transaminase (AST) in one group had a small increase in the control group. Regarding urine, in exception the rats of one group, the rats of the 4 other experimental groups showed leukocytosis urinary statistically higher than the control group. The histological evaluation of the animals showed that specimens from liver, stomach, kidney and submandibular gland presented normal aspects for these organs, without significant characteristics related to inflammatory infiltrates in any of the 6 samples tested in their respective groups.

Differences in both matrix metalloproteinase 9 concentration and zymographic profile between plasma and serum with clot activators are due to the presence of amorphous silica or silicate salts in blood collection devices

Matrix metalloproteinases (MMPs) are promising diagnostic tools, and blood sampling/handling alters MMP concentrations between plasma and serum and between serum with and without clot activators. To explain the higher MMP-9 expression in serum collected with clot accelerators relative to serum with no additives and to plasma, we analyzed the effects of increasing amounts of silica and silicates (components of clot activators) in,citrate plasma, serum, and huffy coats collected in both plastic and glass tubes from 50 healthy donors, and we analyzed the effects of silica and silicate on cultured leukemia cells. The levels of MMP-2 did not show significant changes between glass and plastic tubes, between serum and plasma, between serum with and without clot accelerators, or between silica and silicate treatments. No modification of MMP-9 expression was obtained by the addition of silica or silicate to previously separated plasma and serum. Increasing the amounts of nonsoluble silica and soluble silicate added to citrate and empty tubes prior to blood collection resulted in increasing levels of MMP-9 relative to citrate plasma and serum. Silica and silicate added to buffy coats and leukemia cells significantly induced MMP-9 release/secretion, demonstrating that both silica and silicate induce the release of pro- and complexed MMP-9 forms. We recommend limiting the misuse of serum and avoiding the interfering effects of clot activators. (c) 2007 Elsevier Inc. All rights reserved.

Thermal Cycling Stability of Silica Membranes for Gas Separation

Hydrogen is being seen as an alternative energy carrier to conventional hydrocarbons to reduce greenhouse gas emissions. High efficiency separation technologies to remove hydrogen from the greenhouse gas, carbon dioxide, are therefore in growing demand. Traditional thermodynamic separation systems utilise distillation, absorption and adsorption, but are limited in efficiency at compact scales. Molecular sieve silica (MSS) membranes can perform this separation as they have high permselectivity of hydrogen to carbon dioxide, but their stability under thermal cycling is not well reported. In this work we exposed a standard MSS membrane and a carbonised template MSS (CTMSS) membrane to thermal cycling from 100 to 450°C. The standard MSS and carbonised template CTMSS membranes both showed permselectivity of helium to nitrogen dropping from around 10 to 6 in the first set of cycles, remaining stable until the last test. The permselectivity drop was due to small micropore collapse, which occurred via structure movement during cycling. Simulating single stage membrane separation with a 50:50 molar feed of H2:CO2, H2 exiting the permeate stream would start at 79% and stabilise at 67%. Higher selectivity membranes showed less of a purity drop, indicating the margin at which to design a stable membrane separation unit for CO2 capture.

Nanocomposite Nafion-Silica membranes for direct methanol fuel cells

Commercially available proton exchange membranes such as Nafion do not meet the requirements for high power density direct methanol fuel cells, partly due to their high methanol permeability. The aim of this work is to develop a new class of high-proton conductivity membranes, with thermal and mechanical stability similar to Nafion and reduced methanol permeability. Nanocomposite membranes were produced by the in-situ sol-gel synthesis of silicon dioxide particles in preformed Nafion membranes. Microstructural modification of Nafion membranes with silica nanoparticles was shown in this work to reduce methanol crossover from 7.48x10-6 cm2s^-1 for pure Nafion® to 2.86 x10-6 cm2s^-1 for nanocomposite nafion membranes (Methanol 50% (v/v) solution, 75 degrees C). Best results were achieved with a silica composition of 2.6% (w/w). We propose that silica inhibits the conduction of methanol through Nafion by blocking sites necessary for methanol diffusion through the polymer electrolyte membrane. Effects of surface chemistry, nanoparticle formation and interactions with Nafion matrix are further addressed.

Molecular sieve silica membranes for H2/CO separation

Efficient separation of fuel gas (H2) from other gases in reformed gas mixtures is becoming increasingly important in the development of alternative energy systems. A highly efficient and new technology available for these separations is molecular sieve silica (MSS) membranes derived from tetraethyl-orthosilicate (TEOS). A permeation model is developed from an analogous electronic system and compared to transport theory to determine permeation, selectivity and apparent activation of energy based on experimental values. Experimental results for high quality membranes show single gas permselectivity peaking at 57 for H2/CO at 150°C with a H2 permeation of 5.14 x 10^-8 mol.m^-2.s^-1.Pa^-1. Higher permeance was also achieved, but at the expense of selectivity. This is the case for low quality membranes with peak H2 permeation at 1.78 x 10-7 mol.m-2.s-1.Pa-1 at 22°C and H2/CO permselectivity of 4.5. High quality membranes are characterised with positive apparent activation energy while the low quality membranes have negative values. The model had a good fit of r-squared of 0.99-1.00 using the experimental data.

Molecular Sieve Silica (MSS) Membranes for Gas Separation and Reaction Processes

Weakly branched silica films formed by the two-step sol-gel process allow for the formation of high selectivity membranes for gas separation. 29Si NMR and gas permeation showed that reduced crosslinking leads to He/CH4 selectivity improvement from 300 to 1000. Applied in membrane reactor for cyclohexane conversion to benzene, conversions were achieved at 14 fold higher than a conventional reactor at 250°C. Hydrothermal stability studies showed that carbon templating of silica is required for hydrothermally stable membranes. From our work it was shown that with correct application of chemistry, practical membrane systems can be built to suit gas separation (e. g. hydrogen fuel) and reactor systems.