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Abstract  

Thermogravimetric techniques have been used to study the kinetics of thermal deamination of tris(ethylenediamine)nickel(II) sulphate. The complex was synthesized and characterized by various chemical and spectral techniques. Thermal decomposition studies were carried at different heating rates (5, 10, 15 and 20°C min−1) in dynamic air. The complex undergoes a four-stage decomposition pattern. The stages are not well resolved. Decomposition path can be interpreted as a two-stage deamination, and a two-stage decomposition. Reaction products at each stage were separated and identified by means of IR and XRD. The morphology of the complex and the residue were studied by means of SEM. Final residue of the decomposition was found to be crystalline NiO. The deamination kinetics was studied using model-free isoconversional methods viz., Friedman, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods. It is observed that the activation energy varies with the extent of conversion; indicating the complex nature of the deamination reaction.

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Summary  

The paper contains an analysis of the used of Diefallah's composite integral method of kinetic parameters evaluation. It is shown that the application of this method should be preceded by the application of an isoconversional method through which the dependence of the activation energy, E, on the conversion degree,a, should be established. If Edepends ona, Diefallah's composite integral method leads to erroneous results. If Edoes not depend ona, the true kinetic model should be comprised in the pre-established set of kinetic models. These observations were checked for two sets of non-isothermal data, namely: (a) the TG curves corresponding to the dehydration of CaC2O4H2O; (b) the TG curves corresponding to the thermal decomposition of polyvinyl chloride (PVC).

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Abstract  

There is an increasing concern with the environmental problems associated with the increasing CO2, NOx and SOx emissions resulting from the rising use of fossil fuels. Renewable energy, mainly biomass, can contribute to reduce the fossil fuels consumption. Biomass is a renewable resource with a widespread world distribution. Pistachio is available in large quantities in Gaziantep region in Turkey. Pistachio shell has a good energy potential for exploitation through pyrolysis and gasification. This study deals with the thermal degradation characteristics of in different particle sizes pistachio shell and its kinetics. Thermal degradation analysis have been done by using a thermogravimetric analyzer from room temperature to 800°C in N2 atmosphere at different heating rates (5, 10, 15 and 20°C min−1). TG and DTG curves exhibited two distinct degradation zones. Kinetic parameters were calculated by using Coats-Redfern method and model-free isoconversional Flynn-Wall-Ozawa (FWO) kinetic method.

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Abstract  

The possibility to determine the kinetic parameters for temperature programmed reduction of Cu/Fe3O4 using only one TPR profile is analyzed. The same data are analyzed both by Friedman’s iso-conversional method and another one previously derived and published by the authors. One shows that taking into account the experimental restrictions of Monti and Baiker, the Friedman’s method, although gives values of the activation energy smaller than the real values, indicates a very similar dependence of these on the reduction degree. On the basis of some synthetic data one shows that the errors are very large when these recommendations are neglected, being possible to determine a false dependence on the degree of reduction.

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Summary By applying an advanced isoconversional method to DSC data one can evaluate a dependence of the effective activation energy (the temperature coefficient of the growth rate) on the relative extent of melt crystallization. The conversion dependence can further be converted into a temperature dependence and parameterized in terms of the Hoffman-Lauritzen equation. For poly(ethylene terephthalate) (PET) we observe a transition from regime I to II. Poly(ethylene oxide) (PEO) crystallization appears to begin in regime II and then undergoes 2 consecutive changes that however cannot be clearly interpreted as regime III. The K g and sse parameters obtained for regime I and II (PET) and regime II (PEO) are consistent with the respective parameters reported for isothermal crystallization.

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Abstract  

A new method of the multiple rate iso-temperature was used to define the most probable mechanism g(α) of a reaction; the iterative iso-conversional procedure has been employed to estimate apparent activation energy E a, the pre-exponential factor A was obtained on the basis of E a and g(α). In this new method, the thermal analysis kinetics triplet of dehydration of calcium oxalate monohydrate is determined, which apparent activation energy E a is 82.83 kJ mol-1, pre-exponential factor A is 1.142105-1.235105 s-1, the most probable mechanism belongs to phase boundary reaction Rn with integral form g(α)=1-(1-α)n and differential form f(α)=n(1-α)1-(1/n), where accommodation factor n=2.40-1.40.

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Abstract  

Kinetics of thermosetting polymers curing is difficult to study by isothermal methods based on the differential scanning calorimetry (DSC) technique. The difficulty is due to the low sensitivity of the equipment for total reaction heat measurements during high temperature process. The aim of this paper is to display the equivalence between a dynamic model, the Ozawa method, and an isothermal isoconversional fit, which allows predicting the isothermal behavior of the resol resins cure through dynamic runs by DSC. In this work, lignin–phenol–formaldehyde and commercial phenol–formaldehyde resol resins were employed. In addition, the isothermal kinetic parameters for both resins were performed by means of transformation of the data obtained from the dynamic Ozawa method.

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Abstract  

Thermal behavior of nitroguanidine (NQ) has been investigated by TG/DSC-MS-FTIR simultaneous analysis performed under both isothermal and nonisothermal conditions. The isothermal test at 230 °C indicated that the release of gas products can be divided into several stages. The processing of the non-isothermal data, namely 5, 10, 15, and 20 K/min, was performed by using Netzsch Thermokinetics. The dependence of the activation energy evaluated by Friedman’s isoconversional method on the conversion degree shows that the investigated process is complex one, and can be divided into three parts. The mechanism of the process and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression Program. The kinetic results was used to simulate the thermal decomposition of NQ under isothermal condition at 210 °C. The simulated curve is in agreement with the tested curve. The obtained results were also used for prediction of the thermal lifetime of NQ corresponding to a certain temperature.

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Abstract  

The thermo-oxidative degradation of a parchment recent manufactured from a goat skin has been investigated by TG/DTG, DSC simultaneous analysis performed in static air atmosphere, at six heating rates in the range 3–15 K min−1. At the progressive heating in air atmosphere, the investigated material exhibits three main successive processes occurring with formation of volatile products, namely the dehydration followed by two thermo-oxidative processes. The processing of the non-isothermal data corresponding to the first process of thermo-oxidation was performed by using Netzsch Thermokinetics—a Software Module for Kinetic Analysis. The dependence of activation energy, evaluated by isoconversional methods suggested by Friedman, and Ozawa, Flynn and Wall, on the conversion degree and the relative high standard deviations of this quantity show that the investigated process is a complex one. The mechanism and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression program. Three mechanisms, one consisting in four successive steps and two others in five successive steps, exhibit the best F-test Fit Quality for TG curves. It was also used the previously suggested criterion, according to which the most probable process mechanism correspond to the best agreement between E FR = E FR (α) (E FR is the activation energy evaluated by isoconversional method suggested by Friedman; α is the conversion degree) obtained from non-isothermal experimental data and activation energy values, E iso, obtained by applying the differential method to isothermal data simulated using non-isothermal kinetic parameters. According to this last criterion, the most probable mechanism of parchment oxidation consists in four successive steps. The contribution of the thermo-oxidation process in the parchment damage by natural aging is discussed.

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Non-isothermal model-free predictions

Application to the formation of yttria from yttrium trifluoroacetate

Journal of Thermal Analysis and Calorimetry
Authors: Hichem Eloussifi, Jordi Farjas, Pere Roura, and Mohamed Dammak

transformation. Isoconversional model-free methods analyze the evolution of a given parameter at a given degree of transformation, α. The main advantages of using kinetic data from the isoconversional methods is twofold: (a) there is common agreement that

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