Structure, mobility and clustering of interstitial O in La2CuO4+delta in the limit of small delta

Anelastic spectra (elastic energy absorption as a function of temperature) are reported which provide evidence that excess O in La2CuO4+delta starts forming two different types of defects already at very low concentrations, where no phase separation or changes in the type of O intercalation are believed to occur. The absorption peak with the lowest activation enthalpy, H/k(B) = 5600 K, is visible at lowest values of delta and is attributed to the hopping of single interstitial O2- ions. The second process, with a slightly slower dynamics, appears at higher values of delta and soon becomes preponderant over the former process. The latter process is proposed to be due to stable pairs of O atoms and is put in connection with the formation of partially covalent bonds between interstitial and apical oxygen; such bonds would reduce the doping efficiency of excess O at increasing delta. The geometry of the interstitial O defect is discussed. O 1998 Published by Elsevier B.V. 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.

Spectroscopic study and local coordination of polyphosphate colloidal systems

The interaction between metaphosphate chains and the metal ions Ca2+ and Eu3+ has been studied in water by Eu3+ luminescence, infrared absorption, and P-31 NMR spectroscopy. Two main families of sites could be identified for the metal ions in the aqueous polyphosphate colloidal systems: (1) cagelike sites provided by the polyphosphate chain and (2) a family which arises following saturation of cagelike sites. Occupation of this second family leads to supramolecular interactions between polyphosphate chains and the consequent destabilization of the colloidal system. In the polyphosphate-Ca2+ system, this destabilization appears as a coacervation process. Equilibrium existing between colloidal species as a function of the compositions could be reasoned based on the spectroscopic measurements. The determination of coordination numbers and the correlation of the results with the observation of coacervates show that Eu3+ luminescence properties can be used to probe in a unique way the coacervation process.

Comparative study of cogeneration systems in a chemical industry

With the large penetration of the natural gas into the Brazilian energy structure, industries such as paper mills and chemical plants are analyzing the feasibility of implementing cogeneration schemes appropriate to this fuel. The analysis of the energy demand patterns of a chemical company from the photographic sector revealed the possibility of using combined cycles or diesel engine cogeneration schemes keeping the existing compression refrigeration units and steam or gas cycle cogeneration systems with absorption refrigeration units. In terms of economic attractiveness, an analysis based on the method of the internal rate of return was performed. The results indicated that the schemes composed by reciprocating engines and combined cycle with compression chillers, as well as the gas cycle scheme with absorption chiller, present return periods of up to 3 years, showing that the investment in cogeneration could be of interest for this plant. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

Bifurcation of limit cycles from a centre in R-4 in resonance 1:N

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation by Free Vibration Method of Moisture Absorption Effects in Polyamide/Carbon Fiber Laminates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of Total Sulfur in Agricultural Samples by High-Resolution Continuum Source Flame Molecular Absorption Spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Suppression of Anderson localization of light in one-dimensional disordered photonic superlattices

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Methanol laser line assignments: evidence of four-level laser systems

The Ritz computer program, developed for facilitating the assignment of molecular Fourier transform absorption spectra and described in a previous work, determines the energy level values involved in the assigned transitions by the Rydberg-Ritz combination principle. Combining the data obtained from the analyses of high-resolution infrared (IR) and far-infrared (FIR) spectra, it is possible to predict possible FIR laser emissions of molecules. In the present work we have applied this method to the common isotopomer methanol, 12CH3 16OH, and obtained 14 proposed assignments for previously unassigned FIR laser lines. We also predict 15 possible new FIR laser emissions. For the first time, an assignment involving a four-level laser system with collisional population transfer to a slightly higher energy level is reported. © 1998 Academic Press.

Control of nonlinear absorption and amplification of light in Er3+-doped fluoroindate glass

Nonlinear absorption and amplification of a probe laser beam can be controlled by adjustment of the intensity-modulation frequency and the wavelength of a pump laser beam. A demonstration of this effect in Er3+-doped fluoroindate glass is presented. The results show maximum amplification of the probe beam (∼12%) when a pump laser emitting 16 mW of power is modulated at ∼30 Hz. In the limit of low modulation frequencies, or cw pumping, induced absorption of the probe beam is the dominant nonlinear process. © 1999 Optical Society of America.

Determination of mercury in agroindustrial samples by flow-injection cold vapor atomic absorption spectrometry using ion exchange and reductive elution

A flow-injection system with a Chelite-S® cationic resin packed minicolumn is proposed for the determination of trace levels of mercury in agroindustrial samples by cold vapor atomic absorption spectrometry. Improved sensitivity and selectivity are attained since mercuric ions are on-line concentrated whereas other potential interferents are discarded. With on-line reductive elution procedure, concentrated hydrochloric acid could be replaced by 10% w/v SnCl2, in 6 M HCl as eluent. The reversed-intermittent stream either carries the atomic mercury, to the flow cell in the forward direction or removes the residue from reactor/gas liquid separator to a discarding flask in the opposite direction. Concentration and volume of reagent, acidity, flow rates, commutation times and potential interfering species were investigated. For 120 s preconcentration time, the proposed system handles about 25 samples h-1 (50.0 500 ng l-1), consuming about 10 ml sample and 5 mg SnCl2 per determination. The detection limit is 0.8 ng l-1 and the relative standard deviation (RSD) (n = 12) of a 76.7 ng l-1 sample is about 5%. Results are in agreement with certified value of standard materials at 95% confidence level and good recoveries (97-128%) of spiked samples were found. (C) 2000 Elsevier Science B.V.

Minimization of lead and copper interferences on spectrophotometric determination of cadmium using electrolytic deposition and ion-exchange in multi-commutation flow system

A new strategy for minimization of Cu2+ and Pb2+ interferences on the spectrophotometric determination of Cd2+ by the Malachite green (MG)-iodide reaction using electrolytic deposition of interfering species and solid phase extraction of Cd2+ in flow system is proposed. The electrolytic cell comprises two coiled Pt electrodes concentrically assembled. When the sample solution is electrolyzed in a mixed solution containing 5% (v/v) HNO3, 0.1% (v/v) H2SO4 and 0.5 M NaCl, Cu2+ is deposited as Cu on the cathode, Pb2+ is deposited as PbO2 on the anode while Cd2+ is kept in solution. After electrolysis, the remaining solution passes through an AG1-X8 resin (chloride form) packed minicolumn in which Cd2+ is extracted as CdCl4/2-. Electrolyte compositions, flow rates, timing, applied current, and electrolysis time was investigated. With 60 s electrolysis time, 0.25 A applied current, Pb2+ and Cu2+ levels up to 50 and 250 mg 1-1, respectively, can be tolerated without interference. For 90 s resin loading time, a linear relationship between absorbance and analyte concentration in the 5.00-50.0 μg Cd 1-1 range (r2 = 0.9996) is obtained. A throughput of 20 samples per h is achieved, corresponding to about 0.7 mg MG and 500 mg KI and 5 ml sample consumed per determination. The detection limit is 0.23 μg Cd 1-1. The accuracy was checked for cadmium determination in standard reference materials, vegetables and tap water. Results were in agreement with certified values of standard reference materials and with those obtained by graphite furnace atomic absorption spectrometry at 95% confidence level. The R.S.D. for plant digests and water containing 13.0 μg Cd 1-1 was 3.85% (n = 12). The recoveries of analyte spikes added to the water and vegetable samples ranged from 94 to 104%. (C) 2000 Elsevier Science B.V.

Use of the internal standardization for difficult sampling by graphite furnace atomic absorption spectrometry

This work shows the potentiality of As as internal standard to compensate errors from sampling of sparkling drinking water samples in the determination of selenium by graphite furnace atomic absorption spectrometry. The mixture Pd(NO 3) 2/Mg(NO 3) 2 was used as chemical modifier. All samples and reference solutions were automatically spiked with 500 μg l -1 As and 0.2% (v/v) HNO 3 by the autosampler, eliminating the need for manual dilutions. For 10 μl dispensed sample into the graphite tube, a good correlation (r=0.9996) was obtained between the ratio of analyte absorbance by the internal standard absorbance and the analyte concentrations. The relative standard deviations (R.S.D.) of measurements varied from 0.05 to 2% and from 1.9 to 5% (n=12) with and without internal standardization, respectively. The limit of detection (LD) based on integrated absorbance was 3.0 μg l -1 Se. Recoveries in the 94-109% range for Se spiked samples were obtained. Internal standardization (IS) improved the repeatability of measurements and increased the lifetime of the graphite tube in ca. 15%. © 2004 Elsevier B.V. All rights reserved.

Determination of calcium by atomic absorption spectrophotometry applied to the preparation of alginate:chitosan complexes

Polysaccharicles, as alginate and chitosan, have been used to obtain modified release dosage forms. Alginate, due to its property of building gels during the complex formation with calcium ions, allows the building of capsules containing a core constituted by calcium alginate. This work had for objective to determine the appropriate calcium concentration for the preparation of alginate-chitosan capsules, by means of calcium quantification using atomic absorption spectrophotometry. The methodology of calcium quantification was validated through analysis of the limit of detection, precision, accuracy and recovery of the method. The capsules, containing or not the drug, were prepared by the complex coacervation/ionotropic gelification method. Calcium was quantified after samples mineralization and dilution in lantanium solution. The results showed that the amount of calcium incorporated into the capsules depends on the amount of calcium added to the medium, and this ratio increases until the concentration of 1.5% of initial calcium chloride and above this concentration there is a decrease in the proportion of calcium bonded. It was observed that the proportion of calcium that links to the polymer is inversely proportional to the amount of calcium added. The calcium amount incorporated depends on the concentration of the polymeric dispersions used as well as on the ratio between the two polymers.