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Some problems concerning the evaluation of non-isothermal kinetic parameters
Solid-gas decompositions from thermogravimetric data
The validity of isoconversional methods used to evaluate the activation energy is discussed. The authors have shown that the Flynn-Wall-Ozawa and Friedman methods give results that agree with each other only if the activation energy does not change with the degree of conversion. A criterion for the reaction mechanism as expressed by the differential conversion function is suggested too.
Using DSC technique, the chemical interaction in Bi2O3+MO2 mixtures resulting the Bi12MO20 phase, (M=Ti, Ge and Si) was monitored. Kinetic parameters for the primary stage of interaction were yielded by the non-isothermal method of kinetic evaluation of experimental heat flux DSC curves. The model of three-dimensional diffusion according to Jander was fitted as the best in a statistical sense.
Abstract
Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E a (activation energy) and A (pre-exponential factor) and the compensation parameter (S p) were determined. The apparent activation energies obtained from different methods showed a very good agreement.
Abstract
A number of 15 [Fe(Diox#x00B7;H)2L2] type chelates and [Fe(Diox)3(BOR)2] clathrochelates (Diox#x00B7;H2 — dimethylglyoxime, glyoxime, propoxime, nyoxime, furyl-dioxime; L-pyridine, alkyl-pyridine derivatives, diethyl-phenyl-phosphine, diethyl-p-tolyl-phosphine) were obtained and characterized by means of far and middle FTIR and Mössbauer spectroscopic methods. Some structural problems were discussed on the basis of the optical data.The DSC measurements show the higher thermal stability of the clathrochelates without O—HO intramolecular hydrogen bonds (with asymmetric octahedral structure), as compared to the [Fe(Diox#x00B7;H)2L2] trans, symmetric chelates containing O—HO bonds. The kinetic parameters of the thermal decomposition of the complexes have been derived using the nomogram method.
Non-isothermal kinetics of degradation of ultra-high molecular mass polyethene composite materials
Part I. Composite materials with fiber monocrystals
Abstract
In the present work, the Coats-Redfern method was used to determine the kinetic parameters and the possible reaction mechanism of the thermal degradation of ultra-high molecular mass polyethene and its composites with fiber monocrystals in static air at three different heating rates − 6, 10 and 16 K min−1. The analysis of the results obtained showed that the thermal degradation process of pure ultra-high molecular mass polyethene corresponded to a diffusion controlled reaction (three-dimentional diffusion, mechanism D3), while its composites with fiber monocrystals degraded by two concurrent mechanisms (diffusion one D3 and A1,F1 mechanism). The fiber monocrystals used increased the thermal stability of the composite materials obtained. The values of the activation energy, frequency factor, the changes of entropy, enthalpy and Gibbs energy for the active complex of the composites were calculated.
Abstract
The kinetic parameters for the thermal degradation of high impact polystyrene (HIPS) in presence of some metal oxides exhibit reaction rate compensation effect. In thermal degradation of HIPS in presence of transition metal oxides different active centers act simultaneously as reaction sites and macroradicals are formed through random chain scission, disproportion or cyclization. Some oxides retard the polymer degradation through crosslinking and cyclization by the interaction of macroradicals with the double bond in butadiene.
Abstract
The thermal dehydration and decomposition of Zn(BF4)2·6H2O have been studied by TG, DTA and DSC analyses. It is found that the dehydration occurs in two steps. Following the experimental results a thermal decomposition scheme of the compound under investigation is proposed. The enthalpies of dehydration have been determined as well as the formal kinetic parameters are presented.