924 resultados para thermal degradation


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The effect of temperature on the degradation of blackcurrant anthocyanins in a model juice system was determined over a temperature range of 4–140 °C. The thermal degradation of anthocyanins followed pseudo first-order kinetics. From 4–100 °C an isothermal method was used to determine the kinetic parameters. In order to mimic the temperature profile in retort systems, a non-isothermal method was applied to determine the kinetic parameters in the model juice over the temperature range 110–140 °C. The results from both isothermal and non-isothermal methods fit well together, indicating that the non-isothermal procedure is a reliable mathematical method to determine the kinetics of anthocyanin degradation. The reaction rate constant (k) increased from 0.16 (±0.01) × 10−3 to 9.954 (±0.004) h−1 at 4 and 140 °C, respectively. The temperature dependence of the rate of anthocyanin degradation was modelled by an extension of the Arrhenius equation, which showed a linear increase in the activation energy with temperature.

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We have investigated the thermal and structural properties of different commercial dental resins: Filtek(TM) Z-350, Grandio(A (R)), Tetric Ceram(A (R)), and TPH Spectrum(A (R)). The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T (g) values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T (g) values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram(A (R)) dental resin presented the higher T (g) values, activation energy of 215 +/- A 6 KJ mol(-1), and the higher degree of conversion (63%) when compared to the other resins studied herein.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Poly(3-hydroxybutyrate), PHB, has been structurally modified with maleic anhydride, MA, in the presence of triethylamine, TEA. Glass transition, melting, and crystallization temperature, obtained from DSC curves, and thermal degradation temperatures obtained from TG ones, were employed to evaluate the influence of the MA proportion on the modification in the PHB chain. According to the results, most of chain modification reactions are the 80/20 and 90/10 proportions. Observations suggest that most chain modification reactions occur when the ratio of PHB/MA is 80/20 or 90/10. This suggests that modifications of PHB in the presence of MA involve main chain scission.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Poly(3-hydroxybutyrate), PHB has been structurally modified through reaction with maleic anhydride, MA. Transesterification reaction was carried out fixing the PHB and MA and besides time and temperature the concentration of the triethylamine (used as catalyst) was changed. Glass transition, melting and crystallization temperature obtained from DSC curves and thermal degradation temperatures obtained from TG traces were used to evaluate the influence of the reaction conditions on the modification of PHB according to factorial design. on the base of the results the optimum conditions are to perform the PHB modification reaction with MA reaction at 110 degrees C for 1 h with 5% v/v triethylamine.

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High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

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

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Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.

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

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

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

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Thermal treatment (thermal rectification) is a process in which technological properties of wood are modified using thermal energy, the result of Which is often value-added wood. Thermally treated wood takes on similar color shades to tropical woods and offers considerable resistance to destructive microorganisms and climate action, in addition to having high dimensional stability and low hygroscopicity. Wood samples of Eucalyptus grandis were subjected to various thermal treatments, as performed in presence (140 degrees C; 160 degrees C; 180 degrees C) or in absence of oxygen (160 degrees C; 180 degrees C; 200 degrees C) inside a thermal treatment chamber, and then studied as to their chemical characteristics. Increasing the maximum treatment temperatures led to a reduction in the holocellulose content of samples as a result of the degradation and volatilization of hemicelluloses, also leading to an increase in the relative lignin content. Except for glucose, all monosaccharide levels were found to decrease in samples after the thermal treatment at a maximum temperature of 200 degrees C. The thermal treatment above 160 degrees C led to increased levels of total extractives in the wood samples, probably ascribed to the emergence of low molecular weight substances as a result of thermal degradation. Overall, it was not possible to clearly determine the effect of presence or absence of oxygen in the air during thermal treatment on the chemical characteristics of the relevant wood samples.

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A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

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A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3+ + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.