Kinetic model of poly(3-hydroxybutyrate) thermal degradation from experimental non-isothermal data

The non-isothermal data given by TG curves for poly(3-hydroxybutyrate) (PHB) were studied in order to obtain a consistent kinetic model that better represents the PHB thermal decomposition. Thus, data obtained from the dynamic TG curves were suitably managed in order to obtain the Arrhenius kinetic parameter E according to the isoconversional F-W-O method. Once the E parameters is found, a suitable logA and kinetic model (f(alpha)) could be calculated. Hence, the kinetic triplet (E +/- SD, logA +/- SD and f(alpha)) obtained for the thermal decomposition of PHB under non-isothermal conditions was E=152 +/- 4 kJ mol(-1), logA=14.1 +/- 0.2 s(-1) for the kinetic model, and the autocatalytic model function was: f(alpha)=alpha(m)(1-alpha)(n)=alpha(0.42)(1-alpha)(0.56).

Study of the thermal behavior of the transition phase of Co(II)-diclofenac compound by non-isothermal method

The Co(II)-diclofenac complex was evaluated by simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC). The DTA curve profile shows one exothermic peak because of the transition phase of the compound between 170 and 180 A degrees C, which was confirmed by X-ray powder diffractometry. The transition phase behavior was studied by DSC curves at several heating rates of a sample mass between 1 and 10 mg in nitrogen atmosphere and in a crucible with and without a lid. Thus, the kinetic parameters were evaluated using an isoconversional non-linear fitting proposed by Capela and Ribeiro. The results show that the activation energy and pre-exponential factor for the transition phase is dependant on the different experimental conditions. Nevertheless, these results indicate that the kinetic compensation effect shows a relationship between them.

Efeito do creep feeding sobre o desempenho de bezerros e a eficiência reprodutiva de primíparas Nelore, em pastejo

Avaliou-se o efeito da suplementação de bezerros em sistema de creep feeding, em pastagens de Brachiaria brizantha, durante o período de amamentação, sobre o ganho médio diário (GMD), peso à desmama (PD) e taxa de gestação, em delineamento inteiramente ao acaso, utilizando 102 vacas Nelore (primíparas de baixa condição corporal ao início da estação de monta) e seus bezerros, divididos em dois grupos: T1 (n=52), não tratado e T2 (n=50), tratado com suplemento à base de 20% de PB e 75% de NDT. O consumo médio diário estimado no período foi 0,61kg de suplemento/bezerro/dia. Observaram-se diferenças entre T1 e T2 quanto ao PD (P<0,01) e GMD (P<0,05), com valores, respectivamente, de 155,10±2,72 e 163,80±2,53kg; e 0,59±0,015 e 0,64±0,014kg. A taxa de gestação não foi influenciada pelos tratamentos (P>0,05). A suplementação em creep feeding pode aumentar o GMD e o PD de bezerros Nelore, sem alterar a taxa de gestação de primíparas que iniciam a estação de monta com baixa condição corporal.

Níveis de feno de alfafa e forma física da ração no desempenho de cordeiros em creep feeding

Com o objetivo de avaliar o desempenho de cordeiros em creep feeding e confinados, foram realizados dois experimentos. No primeiro, 32 cordeiros ¾ mestiços Suffolk foram criados em creep feeding, desmamados aos 56 dias de idade e, em seguida, confinados. Os cordeiros receberam os seguintes tratamentos: 1. sem suplementação; 2. suplementação com ração à base de milho e soja; 3. ração à base de milho e soja com 15% de feno de alfafa; 4. ração à base de milho e soja com 30% de feno de alfafa. Após o desmame, os cordeiros suplementados foram confinados, recebendo a mesma ração do creep feeding até atingirem de 30 a 32 kg de peso vivo. No segundo experimento, foram utilizados 32 cordeiros ¾ mestiços Suffolk, alimentados em creep feeding, recebendo ração farelada ou peletizada até os pesos de abate: 26 e 28 kg. As dietas eram isoprotéicas (21% PB) e isoenergéticas (2,9 Mcal EM/kg MS). Os animais suplementados na fase de aleitamento obtiveram ganho de peso de 147,4g/dia a mais, quando comparados aos não suplementados. Não houve efeito dos níveis de feno de alfafa na ração sobre o desempenho dos animais. Entretanto, no confinamento, a máxima eficiência de ganho de peso esperada para os machos, conforme a análise de regressão, situou-se em 18,7% de inclusão de feno de alfafa na ração. A ração peletizada propiciou maior desenvolvimento dos animais, quando comparada à ração farelada. Os machos que receberam ração peletizada atingiram os pesos de abate de 26 e 28 kg aos 55 e 60 dias de idade, respectivamente.

Comparação de sistemas de avaliação de dietas para bovinos no modelo de produção intensiva de carne. II - Creep feeding

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

Non-isothermal kinetic for lyophilized leachate from sanitary landfill and composting usine

Leachate samples from a sanitary landfill of Araraquara city and composting usine of Vila Leopoldina, São Paulo, Brazil were lyophilized to remove the water content. TG/DTG curves at different heating rates were recorded. The second step of the thermal decomposition of leachate from the Araraquara landfill (CB1), from the composting usine from Vila Leopoldina (CB2) from the organic phase extracted (FO) and aqueous phase (FA) were all kinetically evaluated using the non-isothermal method.By Flynn-Wall isoconversional method the following values were obtained: E=234 +/- 3.65 kJ mol(-1) and logA=29.7 +/- 0.58 min(-1) for CB1; E=129 +/- 1.66 kJ mol(-1) and logA=11.8 +/- 0.10 min(-1) for CB2; E=51.6 +/- 1.35 kJ mol(-1) and logA=6.09 +/- 0.09 min(-1) for FO and E=76.91 +/- 6.33 kJ mol(-1) and logA=8.88 +/- 0.7 min(-1) for FA with 95% confidence level. Applying the procedures of Malek and Koga, SB kinetic model (Sestak-Berggren) is the most appropriate to describe the decomposition of CB1, CB2, FO and FA.

Crystallization kinetic of fluoro-zirconate glasses by non-isothermal analysis

Fluoride glasses have been extensively studied due to their high transparency in the infrared wavelength. The crystallization kinetics of these systems has been studied using DTA and DSC techniques. Most of the experimental data is frequently investigated in terms of the Johnson-Mehl-Avrami (JMA) model in order to obtain kinetic parameters.In this work, DSC technique has been used to study the crystallization of fluorozirconate glass under non-isothermal conditions. It was found that JMA model was not fit to be applied directly to these systems, therefore, the method proposed by Malek has been applied and the Sestak-Berggren (SB) model seems to be adequate to describe the crystallization process.

Non-isothermal kinetic applied to thermal decomposition of commercial alkyd varnish

Samples of commercial alkyd resin varnish were spread in a film form on slides, dried at room temperature and exposed to solar radiation from one day up to seven months.Thermogravimetric measurements have been done. Based on the TG data, the Flynn-Wall isoconversional method was applied. The activation energy varied between 176-154 kJ mol(-1) and logA was between 15.5-12.9 min(-1) for A, B and C samples at 95% confidence level.

Molecular dynamics simulation on devitrification: Isothermal devitrification and thermodynamics of PbF2 glasses

The vitrification and devitrification features of lead fluoride are investigated by means of molecular dynamic simulations. The influence of heating rate on the devitrification temperature as well as the dependence of the glass properties on its thermal history, i.e., the cooling rate employed, is identified. As expected, different glasses are obtained when the cooling rates differ. Diffusion coefficient analysis during heating of glass and crystal, indicates that the presence of defects on the glassy matrix favors the transition processes from the ionic to a superionic state, with high mobility of fluorine atoms, responsible for the high anionic conduction of lead fluoride. Nonisothermal and isothermal devitrification processes are simulated in glasses obtained at different cooling rates and structural organizations occurring during the heat treatments are clearly observed. When a fast cooling rate is employed during the glass formation, the devitrification of a single crystal (limited by the cell dimensions) is observed, while the glass obtained with slower cooling rate, allowing relaxations and organization of various regions on the glass bulk during the cooling process, devitrifies in more than one crystalline plane. (C) 2004 American Institute of Physics.

Isothermal structural evolution of SnO2 monolithic porous xerogels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Non-isothermal kinetic of oxidation of tungsten carbide

Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant atmosphere. The oxidation of WC to WO3 tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal condition, could be evaluated to the oxidation of WC to heating rate below 15 degrees C min(-1) or low flow of air (10 mL min(-1)). The reaction is governed by nucleation and growth at 5 to 10 degrees C min(-1) then the tendency is to be autocatalytic, JMA and SB, respectively.

Titanium(IV)-EDTA complex - Kinetics of thermal decomposition by non-isothermal procedures

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)-ethylenediaminetetraacetate complex. Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E=172.4 +/- 9.7 and 205.3 +/- 12.8 kJ mol(-1), and pre-exponential factor: logA = 16.38 +/- 0.84 and 18.96 +/- 1.21 min(-1) at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively.From E and logA values, Dollimore and Malek methods could be applied suggesting PT (Prout-Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.

Tin(II)-EDTA complex: kinetic of thermal decomposition by non-isothermal procedures

Tin on the oxide form, alone or doped with others metals, has been extensively used as gas sensor, thus, this work reports on the preparation and kinetic parameters regarding the thermal decomposition of Sn(II)-ethylenediaminetetraacetate as precursor to SnO2. Thus, the acquaintance with the kinetic model regarding the thermal decomposition of the tin complex may leave the door open to foresee, whether it is possible to get thin film of SnO2 using Sn(II)-EDTA as precursor besides the influence of dopants added.The Sn(II)-EDTA soluble complex was prepared in aqueous medium by adding of tin(II) chloride acid solution to equimolar amount of ammonium salt from EDTA under N-2 atmosphere and temperature of 50degreesC arising the pH similar to 4. The compound was crystallized in ethanol at low-temperature and filtered to eliminate the chloride ions, obtaining the heptacoordinated chelate with the composition H2SnH2O(CH2N(CH2COO)(2))(2).0.5H(2)O.Results from TG, DTG and DSC curves under inert and oxidizing atmospheres indicate the presence of water coordinated to the metal and that the ethylenediamine fraction is thermally more stable than carboxylate groups. The final residue from thermal decomposition was the SnO2 characterized by X-ray as a tetragonal rutile phase.Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E-a = 183.7 +/- 12.7 and 218.9 +/- 2.1 kJ mol(-1), and pre-exponential factor: log A = 18.85 +/- 0.27 and 19.10 +/- 0.27 min(-1), at 95% confidence level, could be obtained, regarding the loss of coordinated water and thermal decomposition of the carboxylate groups, respectively. The E-a and logA also could be obtained applying isoconventional Wall-Flynn method on the TG curves.From E-a and log A values, Dollimore and Malek procedures could be applied suggesting R3 (contracting volume) and SB (two-parameter model) as the kinetic model to the loss of coordinated water (177-244degreesC) and thermal decomposition of the carboxylate groups (283-315degreesC), respectively. Simulated and experimental normalized DTG and DSC curves besides analysis of residuals check these kinetic models. (C) 2003 Elsevier B.V. All rights reserved.

Influência do escoamento estático (CREEP) na dureza do amálgama. Efeito de ligas e regióes de medida.

The authors studied the CREEP of 5 amalgam alloys (1 conventional and 4 with high cooper) by the application os static load of 36 MPa in 478 mm specimens, 7 days old. After CREEP test, the samples were included in acrylic resin and Vickers hardness determined by three penetrations for each portion (cervical, medium and occlusal). Samples not submitted to the creep test was used with control. They concluded that no statistic difference was found in creep test but in Vickers test all the studied materials showed different hardness averages. The load application to samples increased the hardness of all the studied materials.