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Abstract  

The thermal decomposition of strontium acetate hemihydrate has been studied by TG-DTA/DSC and TG coupled with Fourier transform infrared spectroscopy (FTIR) under non-isothermal conditions in nitrogen gas from ambient temperature to 600°C. The TG-DTA/DSC experiments indicate the decomposition goes mainly through two steps: the dehydration and the subsequent decomposition of anhydrous strontium acetate into strontium carbonate. TG-FTIR analysis of the evolved products from the non-oxidative thermal degradation indicates mainly the release of water, acetone and carbon dioxide. The model-free isoconversional methods are employed to calculate the E a of both steps at different conversion α from 0.1 to 0.9 with increment of 0.05. The relative constant apparent E a values during dehydration (0.5<α<0.9) of strontium acetate hemihydrate and decomposition of anhydrous strontium acetate (0.5<α<0.9) suggest that the simplex reactions involved in the corresponding thermal events. The most probable kinetic models during dehydration and decomposition have been estimated by means of the master plots method.

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Abstract  

The thermal polymerization kinetics of dimethacrylate monomers was studied by differential calorimetry using non-isothermal experiments. The kinetic analysis compared the following procedures: isoconversional method (model-free method), reduced master curves, the isokinetic relationship (IKR), the invariant kinetic parameters (IKP) method, the Coats-Redfern method and composite integral method I. Although the study focused on the integral methods, we compared them to differential methods. We saw that even relatively complex processes (in which the variations in the kinetic parameters were only slight) can be described reasonably well using a single kinetic model, so long as the mean value of the activation energy is known (E). It is also shown the usefulness of isoconversional kinetic methods, which provide with reliable kinetic information suitable for adequately choosing the kinetic model which best describes the curing process. For the system studied, we obtained the following kinetic triplet: f(α)=α0.6(1−α)2.4, E=120.9 kJ mol−1 and lnA=38.28 min−1.

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Abstract  

The thermal decomposition of magnesium hydrogen phosphate trihydrate MgHPO4 · 3H2O was investigated in air atmosphere using TG-DTG-DTA. MgHPO4 · 3H2O decomposes in a single step and its final decomposition product (Mg2P2O7) was obtained. The activation energies of the decomposition step of MgHPO4 · 3H2O were calculated through the isoconversional methods of the Ozawa, Kissinger–Akahira–Sunose (KAS) and Iterative equation, and the possible conversion function has been estimated through the Coats and Redfern integral equation. The activation energies calculated for the decomposition reaction by different techniques and methods were found to be consistent. The better kinetic model of the decomposition reaction for MgHPO4 · 3H2O is the F 1/3 model as a simple n-order reaction of “chemical process or mechanism no-invoking equation”. The thermodynamic functions (ΔH*, ΔG* and ΔS*) of the decomposition reaction are calculated by the activated complex theory and indicate that the process is non-spontaneous without connecting with the introduction of heat.

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Abstract  

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 Málek and Koga, SB kinetic model (Šesták-Berggren) is the most appropriate to describe the decomposition of CB1, CB2, FO and FA.

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Abstract  

The thermo-oxidative degradation of poly(vinyl alcohol) (PVA) has been investigated by TG+DTG+DTA simultaneous analysis performed in static air atmosphere, at four heating rates, namely 3, 5, 10 and 15 K min−1. TG, DTG and DTA curves showed that, in the temperature range 25–700°C, four successive processes occur. The first process consisting in the loss of physical adsorbed water is followed by three processes of thermal and/or thermo-oxidative degradations. The processing of the non-isothermal data corresponding to the second process (the first process of thermo-oxidation) was performed by using Netzsch Thermokinetics — A Software Module for Kinetic Analysis. The dependence of the activation energy evaluated by Friedman’s isoconversional method on the conversion degree shows that the investigated process is complex one. The mechanism of this process and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression Program and checked for quasi-isothermal experimental data. It was pointed out that the first process of thermo-oxidation of PVA consists in three consecutive steps having Avrami-Erofeev kinetic model. The obtained results can be used for prediction of the thermal lifetime of PVA corresponding to a certain temperature of use and an endpoint criterion.

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Abstract  

The thermal decomposition of aluminum phosphate monohydrate AlPO4·H2O-H4 was investigated in air using TG-DTG/DTA. The AlPO4·H2O-H4 decomposes in one step and final decomposition product (AlPO4) was studied by X-ray powder diffraction, FTIR and FT-Raman spectroscopy. The activation energies of dehydration reaction of AlPO4·H2O-H4 were calculated through the isoconversional methods of Ozawa and Kissinger-Akahira-Sunose (KAS), and the possible conversion functions have been estimated through the comparative methods. The activation energy calculated for the decomposition of AlPO4·H2O-H4 by different methods and techniques were found to be consistent. The kinetic model that better described the reaction of dehydration for AlPO4·H2O-H4 was the Fn model as simple n-order reaction and the corresponding function is f(α)=(1-α)2.75 and g(α)=-[1-(1-a)-1.75/(1.75)].

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Studies on energetic compounds

Part 40. Kinetics of thermal decomposition of some bis(propylenediamine)metal perchlorate complexes

Journal of Thermal Analysis and Calorimetry
Authors: G. Singh and D. K. Pandey

Bis(propylenediamine)metal perchlorate (BPMP) complexes like [M(pn)2](ClO4)2 (where M=Cr, Mn, Ni, Cu, Zn and pn=propylenediamine) have been prepared and characterized by gravimetric methods, infrared and elemental analysis. Thermal properties have been studied using simultaneous thermogravimetry-differential thermal analysis in atmospheres of nitrogen and air to examine the effect of atmospheric change on thermal decomposition of these complexes. Changing of the atmosphere does not cause any measurable changes in the decomposition of complexes. However, as indicated by thermoanalytical techniques, the thermal stability of present complexes decreases in the order: [Cr(pn)2](ClO4)2>[Mn(pn)2](ClO4)2>[Zn(pn)2](ClO4)2>[Ni(pn)2](ClO4)2>[Cu(pn)2](ClO4)2. Isothermal thermogravimetry, over the temperature range of decomposition has been done for all the complexes. An analysis of the kinetics of thermal decomposition was made using a model fitting procedure as well as an isoconversional method, independent of any model. The results of both kinetic approaches have been discussed critically. The explosion delay (D E) was measured to investigate the trend of rapid thermal analysis.

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Abstract  

The nitrate complexes of copper, nickel and zinc with diethylenetriamine (dien) i.e. [Cu(dien)2](NO3)2, [Ni(dien)2](NO3)22H2O and [Zn(dien)2](NO3)2 have been prepared and characterised. Thermal studies were undertaken using TG-DTG, DSC, ignition delay (t id) and ignition temperature (IT) measurements. Impact sensitivity was measured using drop mass technique. The kinetic parameters for both non-isothermal and isothermal decomposition of the complexes were evaluated by employing Coats-Redfern (C-R) method and Avrami-Erofeev (A-E) equations (n=2 and 3), respectively. The kinetic analysis, using isothermal TG data, was also made on the basis of model free isoconversional method and plausible mechanistic pathways for their decomposition are proposed. Rapid process was assessed by ignition delay measurements. All these complexes were found to be insensitive towards impact of 2 kg mass hammer up to the height limit (110 cm) of the instrument used. The heat of reaction (?H) for each stage of decomposition was determined using DSC.

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Abstract  

Thermal decomposition of extra-virgin olive oil (EVOO) was investigated by thermogravimetry (TG) and derivative thermogravimetry (DTG) up to 550°C at different heating rates (from 5 to 12.5°C min−1). The thermal degradation study of four unsaturated or saturated esterified C18 fatty acids with glycerol (i.e., glyceryl-tristearate (C18:0),-trioleate (C18:1),-trilinoleate (C18:2) and-trilinolenate (C18:3)) was also carried out under the same experimental conditions. A deconvolution procedure applied only to the first two overlapping steps of EVOO and C18:1 enabled the activation energy of decomposition to be determined both by the Kissinger and the Ozawa-Flynn-Wall isoconversional method for the two deconvoluted steps of EVOO and C18:1, as well as for the only single step of the other three C18 triglycerides. Practically constant activation energy for the first deconvoluted step of EVOO and C18:1 and for the single step of C18:0 was found in good agreement with the results obtained with the Kissinger method, while a similar increasing trend was observed for the second decomposition step of EVOO and C18:1 and for the single steps of C18:2 and C18:3 triglycerides.

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Abstract  

3-Deoxy-D-erythro-hexos-2-ulose bis (thiosemicarbazone) (I) readily obtained from d-glucose reacts with copper acetate hydrate to give the corresponding chelate (II). The complex (II) was acetylated to give the corresponding tri-O-acetyl derivative (III). The (I), (II), and (III) were used as optically active curing agents for diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, and the cure reaction was studied by the non-isothermal DSC method. The maximum exothermic temperature (T p) of curing of DGEBA-(III) system shifted about 313 K toward lower temperature in comparison with the T p of DGEBA/(II) system. The average E a values obtained by using Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), and isoconversional methods for non-isothermal curing of DGEBA-(I), DGEBA-(II), and DGEBA-(III) systems are 95.8, 135.5, and 85.8 kJ mol−1, respectively. The higher reactivity of (III) toward epoxide groups can be due to better solubility of the (III) in DGEBA as a result of acetylation of hydroxyl groups.

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