UV-visible absorption characteristics of TEOS-derived and Cr-doped silica sonogels aged in different pH solutions and heat treated up to 600 degrees C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl3.6H(2)O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600degreesC and analyzed by UV-visible absorption spectroscopy. Cr3+ is the preferable oxidation state of the chromium ion in the gels annealed up to 250-300degreesC, in the case of aging in solutions of pH=5 and 11. A high UV absorption below similar to320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below similar to250degreesC, in the case of aging in solutions of pH=1 and 2. These absorption bands have not been assigned. Above 300degreesC up to 600degreesC, Cr5+, and possibly Cr6+, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.

Relationship between the optical gap and the optical-absorption tail breadth in amorphous GaAs

We study the relationship between the optical gap and the optical-absorption tail breadth for the case of amorphous gallium arsenide (a-GaAs). In particular, we analyze the optical-absorption spectra corresponding to some recently prepared a-GaAs samples. The optical gap and the optical-absorption tail breadth corresponding to each sample is determined. Plotting the optical gap as a function of the corresponding optical-absorption tail breadth, we note that a trend, similar to that found for the cases of the hydrogenated amorphous silicon and hydrogenated amorphous germanium, is also found for the case of a-GaAs. The impact of alloying on the optical-absorption spectrum associated with a-GaAs is also briefly examined. (C) 2004 American Institute of Physics.

Determination of selenium in nutritionally relevant foods by graphite furnace atomic absorption spectrometry using arsenic as internal standard

A method has been developed for the direct determination of Se in nutritionally relevant foods by graphite furnace atomic absorption spectrometry. Tungsten/rhodium carbide coating on the integrated platform of a transversely heated graphite atomizer or W coating with co-injection of Pd(NO3)(2) were used as a permanent modifiers. Samples and reference solutions were spiked with 500 mu g L-1 As and absorbance variations due to changes in experimental conditions were minimized. For 20 mu L aqueous analytical solutions delivered into the graphite tube, analytical curves in the 5.0-40 mu g L-1 with good linear correlation were established. Pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. The optimized heating program (temperature, ramp time, hold time) of the graphite tube of the Perkin-Elmer SIMAA 6000 atomic absorption spectrometer was: dry steps (110 degrees C, 5 s, 10 s; 130 degrees C, 15 s, 15 s); air-assisted pyrolysis step (600 degrees C, 20 s, 40 s; 20 degrees C, 1 s, 40 s); pyrolysis step (1300 degrees C, 10 s, 20 s); atomization step (2100 degrees C, 0 s, 4 s); clean step (2550 degrees C, 1 s, 5 s). The method was applied for Se determination in coconut water, coconut milk, soybean milk, cow milk, tomato juice, mango juice, grape juice and drinking water samples and four standard reference materials and results were in agreement at 95% confidence level. The lifetime of the tube was 500 firings and the relative standard deviations of measurements of typical samples containing 25 mu gL(-1) Se were 3.0% and 6.0% (n = 12) with and without internal standardization, respectively. The limits of detection were in the 0.35 mu g L-1-0.7 mu g Se L-1 range. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 98-109% range. (c) 2004 Elsevier Ltd. All rights reserved.

High current-density anodic electro-dissolution in flow-injection systems for the determination of aluminium, copper and zinc in non-ferroalloys by flame atomic absorption spectrometry

An automatic Procedure with a high current-density anodic electrodissolution unit (HDAE) is proposed for the determination of aluminium, copper and zinc in non-ferroalloys by flame atonic absorption spectrometry, based on the direct solid analysis. It consists of solenoid valve-based commutation in a flow-injection system for on-line sample electro-dissolution and calibration with one multi-element standard, an electrolytic cell equipped with two electrodes (a silver needle acts as cathode, and sample as anode), and an intelligent unit. The latter is assembled in a PC-compatible microcomputer for instrument control, and far data acquisition and processing. General management of the process is achieved by use of software written in Pascal. Electrolyte compositions, flow rates, commutation times, applied current and electrolysis time mere investigated. A 0.5 mol l(-1) HNO3 solution was elected as electrolyte and 300 A/cm(2) as the continuous current pulse. The performance of the proposed system was evaluated by analysing aluminium in Al-allay samples, and copper/zinc in brass and bronze samples, respectively. The system handles about 50 samples per hour. Results are precise (R.S.D < 2%) and in agreement with those obtained by ICP-AES and spectrophotometry at a 95% confidence level.

Local order around of germanium atoms in Ga10Ge25S65 glass by EXAFS

Irreversible photoexpansion effect has been observed in amorphous Ga10Ge2S65 glasses when its surface was exposed to light with energy greater than the band gap, 3.52 eV. A volume change of about 5% was reached in bulk samples by controlling illumination time and the laser power density. To understand the atomic scale processes of the photoexpansion effect, extended X-ray absorption fine structure (EXAFS) spectroscopy has been used as a local probe of the germanium environment in the glass samples before and after illumination. Modifications are observed in the average coordination shell around Ge atoms in the illuminated sample compared to the non-illuminated one. For the non-illuminated sample, the Ge coordination shell is described by a distorted tetrahedron of sulfur atoms at around 2.20 Angstrom. After illumination, the EXAFS signal can be explained by introducing an additional contribution to this average environment. Based on an analysis of the EXAFS data we proposed a two-shell model of 0.5 oxygen atoms at 2.01 Angstrom and 3.6 sulfur atoms at a 2.20 Angstrom. The existence of Ge-O bonds in the glass after illumination was confirmed by infrared measurements. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effects of leucine supplemented diet on intestinal absorption in tumor bearing pregnant rats

Background: It is known that amino acid oxidation is increased in tumor-bearing rat muscles and that leucine is an important ketogenic amino acid that provides energy to the skeletal muscle.Methods: To evaluate the effects of a leucine supplemented diet on the intestinal absorption alterations produced by Walker 256, growing pregnant rats were distributed into six groups. Three pregnant groups received a normal protein diet (18% protein):pregnant (N), tumor-bearing (WN), pair-fed rats (Np). Three other pregnant groups were fed a diet supplemented with 3% leucine (15% protein plus 3% leucine):leucine (L), tumor-bearing (WL) and pair-fed with leucine (Lp). Non pregnant rats (C), which received a normal protein diet, were used as a control group. After 20 days, the animals were submitted to intestinal perfusion to measure leucine, methionine and glucose absorption.Results: Tumor-bearing pregnant rats showed impairment in food intake, body weight gain and muscle protein content, which were less accentuated in WL than in WN rats. These metabolic changes led to reduction in both fetal and tumor development. Leucine absorption slightly increased in WN group. In spite of having a significant decrease in leucine and methionine absorption compared to L, the WL group has shown a higher absorption rate of methionine than WN group, probably due to the ingestion of the leucine supplemented diet inducing this amino acid uptake. Glucose absorption was reduced in both tumor-bearing groups.Conclusions: Leucine supplementation during pregnancy in tumor-bearing rats promoted high leucine absorption, increasing the availability of the amino acid for neoplasic cells and, mainly, for fetus and host utilization. This may have contributed to the better preservation of body weight gain, food intake and muscle protein observed in the supplemented rats in relation to the non-supplemented ones.

Local order around tungsten atoms in tungstate fluorophosphate glasses by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO3-BaF2,-WO3 glasses and the results were compared with crystalline references Na2WO4 and WO3. XANES measurements at the W-L-1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO3. Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO3. With increasing WO3 concentration, it was found that R-2 decreases from 1.96 to 1.92 angstrom whereas R-3 increases from 2.07 to 2.12 angstrom. (c) 2005 Elsevier B.V. All rights reserved.

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Influence of moisture absorption on mechanical behaviour of composites

Because of their application that normally demands high mechanical strength combined with low weight, the fibre/matrix interface became an important parameter concerning structural life. The problem of moisture absorption in materials has received attention in experimental studies on a composite systems as well as from a theorical point of view. The fibre/matrix interface plays an important role in the structural behaviour of composites due to the fact that load transfer from matrix to reinforce occurs at the interface. In this case the study of compatibility of fibre/matrix/environmental is essential to ensure a product that attend structural objectives, many times without failure possibilities. The composite used in this investigation is the carbon fibre/matrix epoxy composite, which was immersed in sea water standard during 94 days at 60 degrees C, submitted to tensile and compressive tests to study the influence of moisture absorption on mechanical behaviour. The interface was investigated through fracture surface analysis by SEM and a strong interface and a good adhesion fibre/matrix was observed.

POTASSIUM FERTILIZATION, ROOT MORPHOLOGY AND POTASSIUM ABSORPTION BY SOYBEAN

A greenhouse experiment studied the effect of potassium fertilization on soybean (Glycine max L. Merrill) root morphology and on K absorption by six soybean cultivars of different maturation groups and growth habits. The Plants were grown up to 70 days after plant emergence, in pots containing 6.0 kg of soil. In the absence of K, no significant difference in K absorption was observed among the cultivars or in root length and surface, but root mean radius was correlated to K absorption. Differences in K absorption were not associated with root characteristics in the presence of K fertilization. Physiological adjustments in K uptake, as well as K availability in the soil, were more important in soybean nutrition than were morphological adjustments in the root system. The results were not associated with plant growth habit or with maturation group.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

Evaluation of hygrothermal effects on the shear properties of Carall composites

Fiber metal laminates are the frontline materials for aeronautical and space structures. These composites consists of layers of 2024-T3-aluminum alloy and composite prepreg layers. When the composite layer is a carbon fiber prepreg, the fiber metal laminate, named Carall, offers significant improvements over current available materials for aircraft structures. While weight reduction and improved damage tolerance characteristics were the prime drivers to develop this new family of materials, it turns out that they have additional benefits, which become more and more important for today's designers, such as cost reduction and improved safety. The degradation of composites is due to environmental effects mainly on the chemical and/or physical properties of the polymer matrix leading to loss of adhesion of fiber/resin interface. Also, the reduction of fiber strength and stiffness are expected due to environmental degradation. Changes in interface/interphase properties leads to more pronounced changes in shear properties than any other mechanical properties. In this work, the influence of moisture in shear properties of carbon fiber/epoxy composites and Carall have been investigated by using interlaminar shear (ILSS) and Iosipescu tests. It was observed that hygrothermal conditioning reduces the Iosipescu shear strength of CF/E and Carall composites due to the moisture absorption in these materials. (c) 2006 Elsevier B.V. All rights reserved.

Determination of vanadium in human hair slurries by electrothermal atomic absorption spectrometry

This work describes an analytical procedure for vanadium determination in human hair slurries by electrothermal AAS using longitudinal heating (LHGA) and transversal heating (THGA) graphite furnace atomizers. The samples were powdered using cryogenic grinding and the hair slurries containing 0.2% (m/v) were prepared in three different media for determination of vanadium: 0.14 mol L-1 HNO3, 0.1% (v/v) Triton X-100 and 0.1% (v/v) water soluble tertiary amines (CFA-C, pH 8). The limits of detection (LOD), limits of quantification (LOQ), and characteristic masses obtained were 0.28, 0.95 mu g L-1 and 35 pg (LHGA) and 0.34, 1.13 mu g L-1 and 78 pg (THGA), respectively. The accuracy of the analytical results obtained by the proposed procedure in both equipments was confirmed by a paired t-test at the 95% confidence level and compared with a conventional procedure based on acid digestion. (c) 2006 Elsevier B.V. All rights reserved.

Nanoscale processing of polyaniline and phthalocyanines for sensing applications

Nanostructured polyaniline-modified electrodes were fabricated via the electrostatic layer-by-layer (LbL) technique where polyaniline (PANI) was assembled with one of three tetrasulfonated metallic phthalocyanines, viz. iron (FeTsPc), nickel (NiTsPc) and copper (CuTsPc). The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the 800 run absorption band due to PANI. Infrared spectroscopy in the transmission mode suggested specific interactions between PANI and the phthalocyanines, such as those between SO3- groups from the phthalocyanines and the protonated NH group from PANI. The films were employed to detect dopamine (DA) using cyclic voltammetry. In the presence of dopamine the PANI-based LbL films showed additional redox peaks at ca. 230 and 190 mV the oxidation peak increased linearly with the concentration of DA in the electrolytic solution. Films comprising PANI/FeTsPc were able to distinguish between DA and ascorbic acid (AA), which acts as a natural interferent in biological fluids. (c) 2005 Elsevier B.V. All rights reserved.