Authors:Alexandra Ioiţescu, Gabriela Vlase, T. Vlase, and N. Doca
The kinetics of thermal decomposition
under non-isothermal conditions was studied. The TG/DTG curves were obtained
at five heating rates: 5, 7, 10, 12 and 20 K min–1.
The kinetic analysis was performed by means of three methods: Friedman,
Budrugeac–Segal and NPK by Sempere and Nomen. An important dependence
of the activation energy vs. the conversion
degree was observed and also a compensation effect. The decomposition consists
of water loss and is due to the elimination of crystallization water and an
intermolecular condensation, respectively.
A new procedure for the prediction of the isothermal behaviour of the solid-gas system from non-isothermal data is suggested.
It bypasses the use of various approximations of the temperature integral that ground the integral methods of prediction.
The procedure was checked for: (1) simulated data corresponding to a first order reaction; (2) experimental data obtained
in the isothermal and non-isothermal decompositions of ammonium perchlorate. For the simulated data, a very good agreement
between calculated isotherms and those evaluated by means of the suggested procedure was obtained. A satisfactory agreement
(errors in time evaluation corresponding to a given degradation lower than 18%, for 0.10a0.37 and lower than 10% for 0.37a0.70)
was obtained for the experimental data corresponding to the decomposition of ammonium perchlorate. In this last case, the
mentioned differences between experimental and calculated data can be due both to the inherent errors in the evaluation of
the decomposition isotherms and to the dependence of the activation energy on the conversion degree.
A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order
kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach.
The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures.
An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use
of DSC trace data. A value of 89.120.32 kJ mol-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation
energy corresponding to the ordering process as influenced by quenching temperature was also assessed.
Authors:C. Păcurariu, R. Lazău, I. Lazău, R. Ianoş, and T. Vlase
The influence of the specific surface area on the crystallization processes of two silica gels with different specific surface
areas has been investigated in non-isothermal conditions using DTA technique. The activation energies of the crystallization
processes were calculated using four isoconversional methods: Ozawa-Flynn-Wall, Kissinger-Akahira-Sunose, Starink and Tang.
It has been established that, the decrease of the surface area from S=252.62 m2 g−1, in the case of sample GS2, to S=2.52 m2 g−1, in the case of sample GS1, has determined a slight increase of the activation energy of the crystallization process of the
gels. Regardless of the isoconversional method used, the activation energy (Eα) decreases monotonously with the crystallized fraction (α), which confirms the complex mechanism of gels crystallization.
It has been proved that the Johnson-Mehl-Avrami model cannot be applied for the crystallization processes of the studied silica
Summary The thermal behavior of KH2PO4, NaH2PO4 and Na2HPO4 under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedman’s differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.
Authors:T. Vlase, Gabriela Vlase, N. Doca, and C. Bolcu
Summary Due to the criticism of the non-isothermal kinetic at a single heating rate, in the last period, data obtained at different heating rates are processed by means of elevated methods like Friedman’s (FD) differential-isoconversional method or the one suggested by Budrugeac and Segal (BS). The non-parametric kinetics (NPK) method, suggested by Serra, Nomen and Sempere offers two major advantages: the possibility of separation of two or more steps of a complex decomposition reaction; and the possibility of discrimination between the conversion, with regard to the temperature functions of a rate equation. Comparative data of FD, BS and modified version of NPK method are presented for decomposition of three compounds used as polyisocyanate stabilizer.
A kinetic study of the crystallization of poly(ethylene oxide) (PEO) and of a blend of PEO+poly(bisphenol A-co-epichlorohydrin)
(PBE) was performed by using DSC in a non-isothermal program at constant cooling rates. The curves obtained were analyzed
by the Kissinger, Ozawa and Friedman methods, with determination of the kinetic parameters in each case. As a consequence
of the presence of PBE, the kinetic parameters were altered, leading to the conclusion that PBE has some influence on the
crystallization of PEO, modifying its mechanism.