Influence of Ag additions on the activation energy for the reverse eutectoid reaction in Cu-Al alloys

The eutectoid transformation may be defined as a solid-state diffusion-controlled decomposition process of a high-temperature phase into a two-phase lamellar aggregate behind a migrating boundary on cooling below the eutectoid temperature. In substitutional solid solutions, the eutectoid reaction involves diffusion of the solute atoms either through the matrix or along the boundaries or ledges. The effect of Ag on the non-isothermal kinetics of the reverse eutectoid reaction in the Cu-9 mass%Al, Cu-10 mass%Al, and Cu-11 mass%Al alloys were studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The activation energy for this reaction was obtained using the Kissinger and Ozawa methods. The results indicated that Ag additions to Cu-Al alloys interfere on the reverse eutectoid reaction, increasing the activation energy values for the Cu-9 mass%Al and Cu-10 mass%Al alloys and decreasing these values for the Cu-11 mass%Al alloy for additions up to 6 mass%Ag. The changes in the activation energy were attributed to changes in the reaction solute and in Ag solubility due to the increase in Al content.

Electrochemical reduction of disperse orange 1 textile dye at a boron-doped diamond electrode

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

Kinetic parameters for thermal decomposition of microcrystalline, vegetal, and bacterial cellulose

Cellulose can be obtained from innumerable sources such as cotton, trees, sugar cane bagasse, wood, bacteria, and others. The bacterial cellulose (BC) produced by the Gram-negative acetic-acid bacterium Acetobacter xylinum has several unique properties. This BC is produced as highly hydrated membranes free of lignin and hemicelluloses and has a higher molecular weight and higher crystallinity. Here, the thermal behavior of BC, was compared with those of microcrystalline (MMC) and vegetal cellulose (VC). The kinetic parameters for the thermal decomposition step of the celluloses were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and at heating rates of 5, 10, and 20 A degrees C/min, the E(alpha) and B(alpha) terms could be determined and consequently the pre-exponential factor A(alpha) as well as the kinetic model g(alpha). The pyrolysis of celluloses followed kinetic model g(alpha) = [-ln(1 - alpha)](1.63) on average, characteristic for Avrami-Erofeev with only small differences in activation energy. The fractional value of n may be related to diffusion-controlled growth, or may arise from the distributions of sizes or shapes of the reactant particles.

Reação de precipitação de Ag na liga Cu-8%Al-6%Ag

A reação de precipitação de prata na liga Cu-8%Al-6%Ag foi estudada usando medidas de variação da microdureza com a temperatura e o tempo de envelhecimento, difratometria de raios X (DRX), calorimetria exploratória diferencial (DSC), microscopia eletrônica de varredura (MEV). Os resultados obtidos indicaram que o mecanismo da reação de precipitação da prata é um processo controlado pela difusão da prata e a velocidade desta reação atinge um máximo em torno de 500°C.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

A SAXS study of kinetics of aggregation of TEOS-derived sonogels at different temperatures

The kinetics of aggregation of tetraethoxysilane (TEOS)-derived silica sols, produced by acid-catalyzed and ultrasound-stimulated hydrolysis, were studied by 'in situ' measurements of small-angle X-ray scattering (SAXS) at the temperatures 40 degreesC, 60 degreesC and 70 degreesC. The results were analyzed in terms of the evolution with time (t) of the SAXS intensity probing the mass fractal characteristics of the system, the average radius of gyration (Rc,) of the clusters and the number of primary particles per cluster. The aggregation process yields mass fractal structures which exhibit a scattering exponent (alpha) practically equal to 2, in the probed length scale range (5.3 nm < 1/q < 0.22 nm), beneath and even far beyond the gel point. This suggests that a is a direct measure of the real mass fractal dimension (D) of the structure. The precursor sol (pH = 2) exhibits I nm mean sized clusters with mass fractal dimension D similar to 1.9. Increasing the pH to 4.5, the cluster mean size and the number of primary particles per cluster increase but the system keeps a more opened structure (D similar to 1.4). In the first aggregation stages, D increases up to similar to2 by incorporating primary particles to the clusters without changing their mean size. From this stage, the aggregation progresses following a thermally activated scaling law well described by R-G similar tot(1/D) in all cases. This is indicative of a diffusion-controlled cluster-cluster aggregation process. The activation energy of the process was found to be 91.7 kJ/mol. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

In Situ and Simultaneous UV-vis/SAXS and UV-vis/XAFS Time-Resolved Monitoring of ZnO Quantum Dots Formation and Growth

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

Atividade comparada da cefepima, cefpiroma e amicacina em amostras bacterianas hospitalares

The objective of this study was to evaluate the in vitro activity of cefepime, cefpirome and amikacin against the most prevalent nosocomial bacteria. Initially a prospective study was designed to compare the bacterial susceptibility to the three drugs using 1,022 pathogenic strains. The strains were isolated from hospitalized patients of the Hospital das Clinicas - Faculdade de Medicina de Botucatu, SP, from March to December of 1996, by using the Bauer-Kirby susceptibility diffusion controlled method. The activity of cefepime by the Kirby-Bauer method was significantly higher (χ2, p ≤ 0.05) than cefpirome and amikacin for the following bacteria: P. aeruginosa (72% x 56% x 64%, respectively), Enterobacter cloacae (98% x 88% x 80%) and total strains (79.5% x 74.3% x 76.8%). Cefpirome exhibited higher activity than cefepime only to Enterococcus faecalis (42% x 23%). In the 12 other bacterial groups studied the sensibility of the three drugs was similar (χ2, p ≥ 0.05). The minimal inhibitory concentration (MIC) for 127 bacterial strains - Enterobacter cloacae (12), Citrobacter sp (15), Pseudomonas aeruginosa (50), Acinetobacter baumannii (12), BGNF others (22) and Enterococcus faecalis (16)-from the same origin previously described and isolated during 1997, was determined by E-test. Ranges of MIC intervals, MIC(50%), MIC(90%) and the proportion of the sensitive bacterial strains were determined and permitted the following analysis: the activity of cefepime against Gram-negative bacteria was 2 or more times higher than that of cefpirome and amikacin, specially when CIM(90%) was considered; the activity of cefpirome was higher only against E. faecalis. This information must be considered in the rational use of antibiotic, specially in patients with nosocomial infections.

Non-isothermal study of the devitrification kinetics of fluoroindate glasses

The understanding of the kinetics of devitrification of a glass is important for anticipating its stability in a particular purpose, such as fiber-drawing processes. The crystallization kinetics of (BaF2)16(ZnF2)20(SrF 2)20(NaF)2 (GaF3)5(InF3)36(GdF 3)1 glass prepared by quenching were studied by differential scanning calorimetry (DSC). Avrami's exponent (n) obtained by a non-isothermal method was 4.3 for a solid and 2.4 for a powdered sample. According to the classical interpretation of n, these magnitudes correspond to an interface-controlled crystal growth and a diffusion-controlled crystal growth, respectively. The activation energies for crystallization (E) was 62 ± 1 kJ/mol for solid glass and 245 ± 2 kJ/mol for powdered glass. These results are discussed in terms of glass particle size. © 2000 Elsevier Science B.V. All rights reserved.

Electrogravimetric Analysis by Quartz-Crystal Microbalance on the Consumption of the Neurotransmitter Acetylcholine by Acetylcholinesterase

Electrogravimetric analysis was performed on the consumption of the neurotransmitter Acetylcholine (ACh) by Acetylcholinesterase (AChE) in situ and in real time. Michaelis-Menten assumption was achieved by using an enzyme micro-reactor in which the total enzyme was anchored in a quartz crystal microbalance chip (QCM-chip) with a strategically engineered self-assembled monolayer (SAM) of alkanethiols, which can prevent diffusion-controlled or spatially restricted kinetics. The real-time frequency changes indicated the rate of the products formation from enzymatic reaction. The QCM-chip was tested showing that it could demonstrate AChE inhibition by physostigmine. © 2013 Copyright Taylor and Francis Group, LLC.

Structure and kinetics of formation of APTS/GPTS-derived organic/inorganic hybrids

The structure and the kinetics of formation of APTS/GPTS-derived organic/inorganic hybrids were studied in situ by small-angle-X-ray scattering. The data were interpreted in terms of a process of primary particles formation and growth of mass-fractal clusters. At the very early stage, the population of the nonfractal primary particles (D = 3) increases with time. As the mass-fractal clusters appear (D < 3) as a result of the aggregation process, the radius of gyration, Rg, of the clusters increases on average. At advanced stages of aggregation, the clusters grow in a mechanism in which the number of particles per clusters increases while the number of clusters diminishes with time, in such a way that the correlation volume of the clusters, Vc, fulfills the relationship Vc â̂ R g D, in agreement with a mass-fractal character of the clusters. These results supporting a cluster-cluster aggregation process, together with the typically very low value found for the mass-fractal dimension D, are in favor of a diffusion-controlled cluster aggregation mechanism. © 2013 American Chemical Society.

Determination of tetradifon in brazilian green bell pepper by differential pulse voltammetry

Tetradifon, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to green bell pepper crops. In this context, in this work, a reliable and sensitive method for determination of tetradifon in Brazilian green bell pepper samples involving a differential pulse voltammetry (DPV) technique on a glassy carbon electrode is proposed. The electrochemical behavior of tetradifon as followed by cyclic voltammetry (CV) suggests that its reduction occurs via an irreversible five–electron transfer vs. Ag|AgCl, KCl 3 M reference electrode. Very well–resolved diffusion controlled voltammetric peaks have been obtained in a supporting electrolyte solution composed of a mixture of 40% dimethylformamide (DMF), 30% methanol, and 30% NaOH 0.3 mol L−1 at −1.43, −1.57, −1.73, −1.88, and −2.05 V. The proposed DPV method has a good linear response in the 3.00 – 10.0 μmol L−1 range, with a limit of detection (L.O.D) of 0.756 μmol L−1 and 0.831 μmol L−1 in the absence and in the presence of the matrix, respectively. Moreover, improved L.O.D results (0.607 μmol L−1) have been achieved in the absence of DMF from the supporting electrolyte solution. Recovery has been evaluated in five commercial green bell pepper samples, and recovery percentages ranging from 91.0 to 109 have been obtained for tetradifon determinations. The proposed voltammetric method has also been tested for reproducibility, repeatability, and potential interferents, and the results obtained for these three analytical parameters are satisfactory for electroanalytical purposes.

Estudo da cinética de precipitação de Ag na liga Cu-7% Al-4% Ag

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)