Estudo da influência de adições de prata na cinética de precipitação e no comportamento eletroquímico da liga Cu-6%Al

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo das propriedades ópticas de poços quânticos de InGaAsN/GaAs para aplicação em dispositivos optoeletrônicos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Investigação da reatividade e da cinética de dissolução do metacaulim em ácido sulfúrico

Um estudo da reatividade e da cinética de dissolução do metacaulim foi desenvolvido para o caulim de cobertura de papel oriundo da região do Rio Capim, Pará. O caulim foi calcinado a 600, 700, 800, 900 e 1000 ºC por 2 h para obtenção do metacaulim e posteriormente lixiviado com ácido sulfúrico em temperaturas constantes dentro do intervalo 50-95 °C ± 3 °C. Nas lixiviações foram usadas quantidades de ácido sulfúrico correspondentes a 10% acima do valor estequiométrico em relação ao alumínio presente no material. Foram coletadas amostras, com intervalos pré-determinados a cada 15 min até tempo total de 3 h, as quais foram submetidas à análise de teor de alumínio pelo método titrimétrico com EDTA. Os resultados mostraram que a reatividade do caulim calcinado diminuiu com o aumento da temperatura de calcinação e que a cinética de dissolução do alumínio do metacaulim obtido por calcinação a 700 °C seguiu os métodos de reação homogênea utilizados: método integral, método das meia-vidas e método das velocidades iniciais. Uma energia de ativação de 96,25 kJ/mol foi encontrada bem como reação de lixiviação de primeira ordem em relação ao alumínio do metacaulim e de primeira ordem em relação à concentração ácida. Pesquisas realizadas anteriormente, utilizando excesso de um dos reagentes acima de 90% e modelos de reação heterogênea, estão em consonância com os dados encontrados neste trabalho desenvolvido com excesso de apenas 10%.

Dispositivi di recupero energetico: la valvola di regolazione GreenValve del Politecnico di Milano

Oggetto della trattazione è il recupero di energia da parte di una valvola idraulica durante il processo di regolazione del flusso di corrente in un impianto. Questa valvola di regolazione, detta GreenValve, è un brevetto del Politecnico di Milano, ad opera del Prof. Ing. Stefano Malavasi coadiuvato da un gruppo di ricercatori e tesisti, tra i quali spicca il nome di Cecilia Paris. Cecilia ha incentrato il proprio lavoro sull’analisi teorica e sperimentale della “Valvola Verde”, ed è dalla sua Tesi che il suddetto elaborato trae ispirazione.

Preparação de catalisadores para reações de esterificação do ácido oleico baseados em matrizes polímericas sulfonadas POLI(1- FENILETILENO) (PS) e POLI(1-CLOROETILENO) (PVC)

Chemical modification of polymer matrices is an alternative way to change its surface properties. The introduction of sulfonic acid groups in polymer matrices alter properties such as adhesion, wettability, biocampatibility, catalytic activity, among others. This paper describes the preparation of polymeric solid acid based on the chemical modification of poly (1-fenietileno) (PS) and Poly (1-chloroethylene) (PVC) by the introduction of sulfonic acid groups and the application of these polymers as catalysts in the esterification reaction of oleic acid with methanol. The modified materials were characterized by Infrared Spectroscopy, Elemental Analysis and titration acid-base of the acid groups. All techniques confirmed the chemical changes and the presence of sulfur associated with sulfonic acid groups or sulfates. The modified polymers excellent performance in the esterification reaction of oleic acid with methanol a degree of conversion higher than 90% for all investigated polymers (modified PS and PVC (5% w / w)), with a mass ratio of oleic acid: methanol 1:10 to 100 ° C. The best performance was observed for the modified PVC catalyst (PVCS) which showed low degree of swelling during the reactions is recovered by filtration different from that observed for polystyrene sulfonate (PSS). Given these facts, the PVCS was employed as a catalyst in the esterification reaction of oleic acid in different times and different temperatures to obtain the kinetic parameters of the reaction. Experimental data show a great fit for pseudo-homogeneous model of second order and activation energy value of 41.12 kJ mol -1, below that found in the literature for the uncatalyzed reaction, 68.65 kJ mol -1 .The PVCS exhibits good catalytic activity for 3 times of reuse, with a slight decrease in the third cycle, but with a conversion of about 78%. The results show that solid polymeric acid has good chemical stability for the application in esterification reaction of commercial importance with possible application in the biodiesel production. The advantages in use of this system are the increased reaction rate at about 150 times, at these test conditions, the replacement of sulfuric acid as a catalyst for this being the most corrosive and the possibility of reuse of the polymer for several cycles.

Síntese, estudo cinético e análise microestrutural do sistema cério-níquel obtido pelo método pechini

The cerium oxide has a high potential for use in removing pollutants after combustion, removal of organic matter in waste water and the fuel-cell technology. The nickel oxide is an attractive material due to its excellent chemical stability and their optical properties, electrical and magnetic. In this work, CeO2-NiO- systems on molars reasons 1:1(I), 1:2(II) e 1:3(III) metal-citric acid were synthesized using the Pechini method. We used techniques of TG / DTG and ATD to monitor the degradation process of organic matter to the formation of the oxide. By thermogravimetric analysis and applying the dynamic method proposed by Coats-Redfern, it was possible to study the reactions of thermal decomposition in order to propose the possible mechanism by which the reaction takes place, as well as the determination of kinetic parameters as activation energy, Ea, pre-exponential factor and parameters of activation. It was observed that both variables exert a significant influence on the formation of complex polymeric precursor. The model that best fitted the experimental data in the dynamic mode was R3, which consists of nuclear growth, which formed the nuclei grow to a continuous reaction interface, it proposes a spherical symmetry (order 2 / 3). The values of enthalpy of activation of the system showed that the reaction in the state of transition is exothermic. The variables of composition, together with the variable temperature of calcination were studied by different techniques such as XRD, IV and SEM. Also a study was conducted microstructure by the Rietveld method, the calculation routine was developed to run the package program FullProf Suite, and analyzed by pseudo-Voigt function. It was found that the molar ratio of variable metal-citric acid in the system CeO2-NiO (I), (II), (III) has strong influence on the microstructural properties, size of crystallites and microstrain network, and can be used to control these properties

Estudo da sinterização de eletrólito sólido de céria dopada com gadolínia

Fuel cells are electrochemical devices that convert chemical energy in electrical energy by a reaction directly. The solid oxide fuel cell (SOFC) works in temperature between 900ºC up to 1000ºC, Nowadays the most material for ceramic electrolytes is yttria stabilized zirconium. However, the high operation temperature can produce problems as instability and incompatibility of materials, thermal degradation and high cost of the surround materials. These problems can be reduced with the development of intermediate temperature solid oxide fuel cell (IT-SOFC) that works at temperature range of 600ºC to 800ºC. Ceria doped gadolinium is one of the most promising materials for electrolytes IT-SOFC due high ionic conductivity and good compatibility with electrodes. The inhibition of grain growth has been investigated during the sintering to improve properties of electrolytes. Two-step sintering (TSS) is an interesting technical to inhibit this grain growth and consist at submit the sample at two stages of temperature. The first one stage aims to achieve the critical density in the initiating the sintering process, then the sample is submitted at the second stage where the temperature sufficient to continue the sintering without accelerate grain growth until to reach total densification. The goal of this work is to produce electrolytes of ceria doped gadolinium by two-step sintering. In this context were produced samples from micrometric and nanometric powders by two routes of two-step sintering. The samples were obtained with elevate relative density, higher than 90% using low energy that some works at the same area. The average grain size are at the range 0,37 μm up to 0,51 μm. The overall ionic conductivity is 1,8x10-2 S.cm and the activation energy is 0,76 eV. Results shown that is possible to obtain ceria-doped gadolinium samples by two-step sintering technique using modified routes with characteristics and properties necessary to apply as electrolytes of solid oxide fuel cell

Estudo da degradação térmica da madeira de Eucalyptus através de termogravimetria e calorimetria

O objetivo deste trabalho foi avaliar a degradação térmica da madeira de diferentes clones de Eucalyptus, por meio de análises termogravimétrica (TG/DTG) e de calorimetria explorat��ria diferencial (DSC), estabelecendo-se suas relações com a produção de carvão vegetal. Foram utilizados seis clones de Eucalyptus spp. aos 7,5 anos de idade, provenientes de um teste clonal pertencente a uma empresa florestal. Foram realizadas as análises TG/DTG e DSC, sob atmosfera de gás nitrogênio. As curvas TG/DTG mostraram três faixas de degradação térmica, atribuídas à secagem da madeira e à degradação de hemiceluloses e celulose. Não foi detectada faixa específica de degradação de lignina. As curvas DSC evidenciaram um pico endotérmico entre as temperaturas de 50 e 100 ºC, o que pode ser atribuído à perda de água da madeira. A liberação de calor iniciou-se em temperaturas acima de 275 ºC, para todos os clones avaliados, sendo observados dois picos exotérmicos. As análises térmicas da madeira (TG/DTG e DSC) não apresentaram variações expressivas entre os clones. Conclui-se que, através das técnicas estudadas, é possível identificar as principais fases das reações de liberação ou absorção de energia e perda de massa, que estão diretamente ligadas à qualidade do carvão vegetal.

Caracterização mecânica e térmica da borracha natural formulada e vulcanizada dos clones: GT 1, IAN 873, PB 235 e RRIM 600

Neste trabalho estudou-se o desempenho mecânico e térmico de compostos de borracha natural (Hevea brasiliensis) de 4 diferentes clones (GT 1, IAN 873, PB 235 e RRIM 600) cultivados no Estado de São Paulo, assim como de uma mistura destes clones e de uma borracha comercial, GEB-1. Estas borrachas foram formuladas e vulcanizadas com tempos de 5, 7 e 9 minutos. A caracterização foi realizada por calorimetria explorat��ria diferencial, termogravimetria, ensaios de resistência à tração, análise dinâmico-mecânica, medidas de dureza Shore A, microscopia eletrônica de varredura e espectroscopia na região do infravermelho. Os resultados permitiram concluir que o tempo de vulcanização e o tipo de clone não influenciaram na temperatura de transição vítrea (Tg) dos compostos. Os valores de Tg obtidos por DMA foram de cerca de -62 °C, e os resultados ensaios de dureza apresentaram valores próximos de 60 para todos os compostos estudados. Os ensaios de resistência à tração mostraram que o melhor desempenho mecânico foi obtido pelo clone RRIM 600. De acordo com os resultados obtidos neste trabalho, todos os clones atingiram as propriedades reportadas na literatura, podendo ser utilizados, em princípio, nas indústrias de artefatos de borracha separadamente ou na forma de mistura.

Mechanisms underlying the vasorelaxant action of the pimarane ent-8(14),15-pimaradien-3 beta-ol in the isolated rat aorta

Pimarane-type diterpenes were described to exert antispasmodic and relaxant activities. Based on this observation we hypothesized that the diterpene ent-8(14),15-pimaradien-3 beta-ol (PA-3 beta-ol) induced vascular relaxation. With this purpose, the present work investigates the mechanisms involved in the vasorelaxant effect of the pimarane-type diterpene PA-3 beta-ol. Vascular reactivity experiments, using standard muscle bath procedures, were performed in isolated aortic rings from male Wistar rats. Cytosolic calcium concentration ([Ca(2+)]c) was measured by confocal microscopy using the fluorescent probe Fluo-3AM. PA-3 beta-ol (10, 50 and 100 mu mol/l) inhibited phenylephrine and KCl-induced contraction in either endothelium-intact or denuded rat aortic rings. PA-3 beta-ol also reduced CaCl(2)-induced contraction in Ca(2+)-free solution containing KCl (30 mmol/l) or phenylephrine (0.1 mu mol/l). PA-3 beta-ol (1-300 mu mol/l) concentration dependently relaxed phenylephrine-pre-contracted rings with intact or denuded endothelium. The diterpene also relaxed KCl-pre-contracted rings with intact or denuded endothelium. Moreover, Ca(2+) mobilization study showed that PA-3 beta-ol (100 mu mol/l) and verapamil (1 mu mol/l) inhibited the increase in Ca(2+)-concentration in smooth muscle and endothelial cells induced by phenylephrine (10 mu mol/l) or KCl (60 mmol/l). Pre-incubation of intact or denuded aortic rings with N(G)-nitro-L-arginine methyl ester (L-NAME, 100 mu mol/l) and 1H-[1,2,4] Oxadiazolo[4,3-a]quinoxalin-1-one (ODQ 1 mu mol/l) produced a rightward displacement of the PA-3 beta-ol concentration-response curves. On the other hand, 7-nitroindazole (100 mu mol/l), 1400 W (1 mu mol/l), indomethacin (10 mu mol/l) and tetraethylammonium (1 mmol/l) did not affect PA-3 beta-ol-induced relaxation. Collectively, our results provide evidence that the effects elicited by PA-3 beta-ol involve extracellular Ca(2+) influx blockade. Its effects are also partly mediated by the activation of NO-cGMP pathway. (C) 2009 Elsevier B.V. All rights reserved.

ACTIVATION OF PERIPHERAL kappa/delta OPIOID RECEPTORS MEDIATES 15-DEOXY-(Delta 12,14)-PROSTAGLANDIN J(2) INDUCED-ANTINOCICEPTION IN RAT TEMPOROMANDIBULAR JOINT

This study assessed the effect of the agonist 15d-PGJ(2) administered into the rat temporomandibular joint (TMJ) on nociceptive behavioral and the anti-inflammatory potential of this prostaglandin on TMJ. It was observed that 15-deoxy-(Delta 12,14)-prostaglandin J(2) (15d-PGJ(2)) significantly reduced formalin-induced nociceptive behavior in a dose dependent manner, however injection of 15d-PGJ(2) into the contralateral TMJ failed to reduce such effects. This antinociceptive effect is dependent on peroxisome proliferator-activated receptors-gamma (PPAR-gamma) since pre-treatment with GW9662 (PPAR-gamma receptor antagonist) blocked the antinociceptive effect of 15d-PGJ(2) in the TMJ. In addition, the antinociceptive effect of 15d-PGJ(2) was also blocked by naloxone suggesting the involvement of peripheral opioids in the process. Confirming this hypothesis pre-treatment with kappa, delta, but not mu receptor antagonists significantly reduced the antinociceptive effect of 15d-PGJ(2) in the TMJ. Similarly to opioid agonists, the 15d-PGJ(2) antinociceptive action depends on the nitric oxide (NO)/guanilate cyclase (cGMP)/ATP-sensitive potassium channel blocker(K(ATP)(+)) channel pathway since it was prevented by the pre-treatment with the inhibitors of nitric oxide synthase (NOS; aminoguanidine), cGMP (ODQ), or the K(ATP)(+) (glibenclamide). In addition, 15d-PGJ(2) (100 ng/TMJ) inhibits 5-HT-induced TMJ hypernociception. Besides, TMJ treated with 15d-PGJ(2) showed lower vascular permeability, assessed by Evan`s Blue extravasation, and also lower neutrophil migration induced by carrageenan administration. Taken together, these results demonstrate that 15d-PGJ(2) has a potential peripheral antinociceptive and anti-inflammatory effect in the TMJ via PPAR-gamma activation. The results also suggest that 15d-PGJ(2) induced-peripheral antinociceptive response in the TMJ is mediated by kappa/delta opioid receptors by the activation of the intracellular L-arginine/NO/cGMP/K(ATP)(+) channel pathway. The pharmacological properties of the peripheral administration of 15d-PGJ(2) highlight the potential use of this PPAR-gamma agonist on TMJ inflammatory pain conditions. (C) 2009 IBRO. Published by Elsevier Ltd. All rights reserved.

Glutamine synthesis rate in the hyperammonaemic rat brain using simultaneous localized in vivo H-1 and N-15 MRS

Objectives: Glutamine synthetase is a critical step in the glutamate-glutamine cycle, the major mechanism of glutamate neurotransmission and is implicated in the mechanism of ammonia toxicity. 15N MRS is an alternative approach to 13C MRS in studying glutamate- glutamine metabolism. 15N MRS studies allow to measure an apparent glutamine synthesis rate (Vsyn) which reflects a combination of the glutamate- glutamine cycle activity (Vnt) and net glutamine accumulation. The net glutamine synthesis (Vsyn-Vnt) can be directly measured from 1H NMR. Therefore, the aim of this study was to perform in vivo localized 1H MRS interleaved with 15N MRS to directly measure the net glutamine synthesis rate and the apparent glutamine synthesis rate under 15N labeled ammonia infusion in the rat brain, respectively. Methods: 1H and 15N MRS data were acquired interleaved on a 9.4T system (Varian/Magnex Scientific) using 5 rats. 15NH4Cl solution was infused continuously into the femoral vein for up to 10 h (4.5 mmol/h/kg).1 The plasma ammonia concentration was increased to 0.95±0.08 mmol/L (Analox GM7 analyzer). 1H spectra were acquired and quantified as described previously.2 15N unlocalized and localized spectra were acquired using the sequence;3 and quantified using AMARES and an external reference method.4 The metabolic model used to analyze the total Gln and 5-15N labeled Gln time courses is shown on Figure 1A. Results: Glutamine concentration increased from 2.5±0.3 to 15±3.3 mmol/kg whereas the total glutamate concentrations remained unchanged (Figure 1B). The linear fit of the time-evolution of the total Gln from the 1H spectra gave the net synthesis flux (Vsyn-Vnt), which was 0.021± 0.006 mmol/min per g (Figure 1D). The 5-15N Gln peak (_271 ppm) was visible in the first and all subsequent scans, whereas the 2-15N Gln/Glu peak (_342 ppm) appeared after B1.5 h (Figure 1C). From the in vivo 5-15N Gln time course, Vsyn = 0.29±0.1 mmol/min per g and a plasma NH3 fractional enrichment of 71%±6% were calculated. Vnt was 0.26±0.1 mmol/min/g, obtained assuming a negligible Gln efflux.5 Vsyn and Vnt were within the range of 13C NMR measurements.6 Conclusion: The combination of 1H and 15N NMR allowed for the first time a direct and localized measurement of Vnt and apparent glutamine synthesis rate. Vnt is approximately one order of magnitude faster than the net glutamine accumulation.

O efeito da desativação térmica nas propriedades oxirredutoras e na atividade catalítica de catalisadores CZ e Pd-CZ

Automotive catalyst, using in Brazil since 1992, is a essential technology for vehicular emissions control. Noble metals are the active phase of these catalysts, and cerium zirconium mixed oxides (CZ), responsibles for the oxygen storage capacity (OSC), one of the most important aspect for the operational performance of the catalyst. In this context, the oxireduction properties analysis of CZ and Pd/CZ (palladium supported in CZ) system are the objective of this study, as well as, the impact of the thermal aging in the OSC. Aging consisted of treatments at 900 or 1200 °C, for 12 or 36 h, in oxidizing condition.

Influência de argilas pilarizadas na decomposição catalítica do óleo de andiroba

Amostras de esmectitas oriundas do estado do Pará, região amazônica, Brasil, foram usadas em processo de pilarização no presente estudo. As matrizes pilarizadas e natural foram caracterizadas usando DRX e analise textural usando isotermas de adsorção-desorção de nitrogênio. Os íons de intercalação (Al13, Ti, Zr) foram obtidos através de reações químicas com soluções de AlCl(3)6H2O/ NaOH, etoxido de titânio/HCl, acetato de zircônio / HCl. Os resultados obtidos com o processo de pilarização apresentaram aumento do espaçamento basal de 15,6 para 20, 64 Å e área superficial de 44 para 358 m²/g (Zr-PILC). A estabilidade térmica da argila natural foi melhorada com o processo de pilarização. O material resultante foi submetido a um processo catalítico de decomposição do óleo de andiroba em um reator de leito fixo a 673 ± 1 K. A atividade catalítica foi determinada pelo produto de decomposição resultante da reação química. Os parâmetros físico-químicos foram obtidos usando DRX, FTIR e análise textural. As argilas pilarizadas apresentaram alta acidez de Brønsted, com alta concentração de hidrocarbonetos aromáticos e baixa concentração de hidrocarbonetos alifáticos.

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates