Authors:M. Kobelnik, Giseli Bernabé, C. Ribeiro, J. Capela, and F. Fertonani
Non-isothermal decomposition of iron (III)-diclofenac anhydrous salt was investigated by thermogravimetry (TG) under different
conditions in opened and closed α-alumina pans under nitrogen atmosphere. To estimate the activation energy of decomposition,
the Capela and Ribeiro isoconversional method was applied. The results show that due to the lid cover different activation
energies were obtained. From these curves a tendency can be seen where the plots maintain the same profile for closed lids
and almost run parallel to each other. Independently of the different experimental conditions no remarkably different results
have been obtained.
In this study, the temperature-heating rate diagram of the main crystallization process of two metallic glasses, Fe74Ni3.5Mo3B16Si3.5 and Fe41Ni38Mo3B18, was obtained from one experimental differential scanning calorimetry (DSC) scan and the knowledge of their activation energy
as determined by an isoconversional method. A good concordance was observed between the diagram curves obtained by calculation
(isoconversional approach) and the experimental data, which verifies the reliability of the method and the validity of the
kinetic approach in these alloys.
Authors:R. López-Fonseca, I. Landa, M. A. Gutiérrez-Ortiz, and J. R. González-Velasco
Summary Non-isothermal thermogravimetric data were used to evaluate the Arrhenius parameters (activation energy and the pre-exponential factor) of the combustion of two carbonaceous materials, selected as diesel soot surrogates. The paper reports on the application of model-free isoconversional methods (Flynn-Wall-Ozawa and Kissinger methods) for evaluating the activation energy of the combustion process. On the other hand, by means of the compensation relation between E and lnA, which was established by the model-dependent Coats-Redfern method, the value of the pre-exponential factor was estimated from the known value of the model-independent activation energy.
Authors:G. Singh, B. Baranwal, I. Kapoor, D. Kumar, C. Singh, and R. Fröhlich
Three hexamethylenetetramine (HMTA) metal nitrate complexes such as [M(H2O)4(H2O-HMTA)2](NO3)·4H2O (where M=Co, Ni and Zn) have been prepared and characterized by X-ray crystallography. Their thermal decomposition have been studied
by using dynamic, isothermal thermogravimery (TG) and differential thermal analysis (DTA). Kinetics of thermal decomposition
was undertaken by applying model-fitting as well as isoconversional methods. The possible pathways of thermolysis have also
been proposed. Ignition delay measurements have been carried out to investigate the response of these complexes under condition
of rapid heating.
The paper presents a non-isothermal kinetic study of the decomposition of Zn acetate-based gel precursors for ZnO thin films,
based on the thermogravimetric (TG) data. The evaluation of the dependence of the activation energy (E) on the mass loss (Δm) using the isoconversional methods (Friedman (FR), Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS)) has been presented
in a previous paper. It was obtained that the sample dried at 125°C for 8 h exhibits the activation energy independent on
the heating rate for the second decomposition step. In this paper the invariant kinetic parameter (IKP) method is used for
evaluating the invariant activation parameters, which were used for numerically evaluation of the function of conversion.
The value of the invariant activation energy is in a good agreement with those determined by isoconversional methods. In order
to determine the kinetic model, IKP method was associated with the criterion of coincidence of the kinetic parameters for
all heating rates. Finally, the following kinetic triplet was obtained: E=91.7 (±0.1) kJ mol−1, lnA(s−1)=16.174 (±0.020) and F1 kinetic model.
Authors:N. Doca, Gabriela Vlase, T. Vlase, and G. Ilia
The thermal behavior of Cd2+ and Co2+ phenyl-vinyl-phosphonates was studied using two different experimental strategies: the coupled TG-EGA (FTIR) technique by
decomposition in nitrogen respectively air, and the kinetic analysis of TG data obtained in dynamic air atmosphere at four
heating rates. In nitrogen two decomposition steps were observed: the loss of crystallization water, respectively the decomposition
of the phenyl-vinyl radical. In air, the same dehydration was observed as the first step, but the second one is a thermooxidation
of the organic radical with formation of the pyrophosphoric anion.
The kinetic analysis of the TG non-isothermal data was performed by the isoconversional methods suggested by Friedman and
Flynn, Wall and Ozawa, as well as by the non-parametric (Sempere-Nomen) method. All processes put in evidence in TG curves
exhibit strong changes of the activation energy values with the conversion degree, which mean that these processes are complex
ones. Assuming that each of these processes consists in two steps, the application of non-parametric method leads to average
values of the activation energy close to the average values of this parameter obtained by isoconversional methods.
The activation energies of the same process are often reported to have different values, which are usually explained by the
differences in experimental conditions and sample characteristics. In addition to this type of uncertainty, which is associated
with the process (ΔEprocess) there is an uncertainty related to the method of computation of the activation energy (ΔEmethod). For a method that uses fitting single heating rate data to various reaction models, the value of ΔEmethod) method is large enough to explain significant differences in the reported values of the activation energy. This uncertainty
is significantly reduced by using multiple heating rate isoconversional methods, which may be recommended for obtaining reference
values for the activation energy.
The thermal decomposition of three new reagent cyclohexylamine-p-tolylglyoxime (L1H2), tertiarybutyl amine-p-tolylglyoxime (L2H2) and secondary butylamine-p-tolylglyoxime (L3H2 and their Co-complexes were studied by both isothermal and nonisothermal methods. As expected, the complex structure of Co-complexes,
different steps with different activation energies were realized in decomposition process. Model-fitting and model-free kinetic
approaches were applied to nonisothermal and isothermal data. The kinetic triplet (f(α), A and E) related to nonisothermal model-fitting method can not be meaningfully compared with values obtained from isothermal method.
The complex nature of the multi-step process of the studied compounds was more easily revealed using a wider temperature range
in nonisothermal isoconversional method.
Authors:S. Vyazovkin, J. Stone, and N. Sbirrazzuoli
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 Kg and sse parameters obtained for regime I and II (PET) and regime II (PEO) are consistent with the respective parameters reported for isothermal crystallization.
Authors:Josiane de Lima Souza, Marcelo Kobelnik, Clóvis Ribeiro, Jorge Capela, and Marisa Crespi
Poly(3-hydroxybutyrate), PHB, has been structurally modified through reaction with hydroxy acids (HA) such as tartaric acid
(TA) and malic acid (MA). The crystallization kinetic of the samples was evaluated by isoconversional method through nonlinear
fitting to obtain the estimation for activation energy (Ea) and pre-exponential (A) values. The thermal behavior of the crystallization temperature, 44.8 and 58.9 °C at 5 °C/min, and results obtained to the
average activation energy, 73 ± 9 kJ mol−1 and 63 ± 1 kJ mol−1, to PHB/MA and PHB, respectively, are suggesting that malic acid may be deriving plasticizer units from its own PHB chain.
PHB/TA show increase in the medium value of Ea, 119 ± 2 kJ mol−1 and Tc = 48.2 °C (at 5 °C/min), indicating that tartaric acid is probably interacts in different way to the of PHB chain (Ea=73 ± 9 kJ mol−1, Tc = 44.8 °C at 5 °C/min).