This paper presents a comprehensive analysis of the thermal stability and decomposition mechanisms of IPN hydrogels based on polyvinyl alcohol (PVA) and a copolymer network of poly(ethylene glycol) diacrylate–poly(ethylene glycol) methacrylate (PEGDA–PEGMA). Using thermogravimetric analysis (TGA/DTG) and multi-approach kinetic analysis (Friedman and Ozawa–Flynn–Wall isoconversion methods, nonparametric kinetics, Shestaka-Berggren model), the influence of composition on the processes of dehydration, thermal destruction, and the distribution of activation energy by degrees of conversion was investigated. The constructed three-dimensional kinetic “landscapes” made it possible to identify characteristic features of the behavior of various samples, including differences in the rate and mechanisms of destruction. It was found that an increase in the content of PVA enhances moisture binding and shifts the Tmax of dehydration to higher temperatures, while an increase in the concentration of PEGDA forms a denser network that limits moisture retention and accelerates thermal decomposition. Calculation of diffusion coefficients using the Fick model showed a decrease in D with an increase in network density, which reflects an increase in resistance to moisture mass transfer. The combination of the data obtained demonstrates the multistage nature of thermal destruction and allows for the targeted selection of hydrogel compositions for biomedical, environmental, and materials science applications, including drug delivery systems, sorbents and heat-resistant coatings.
2 October 2021 in Russian Journal of Physical Chemistry A
The thermal decomposition of polyethylene glycol fumarate–acrylic acid copolymer is investigated at different rates of heating. It is shown that increasing the rate of heating raises the temperature of the onset of decomposition. The kinetic parameters of decomposition are calculated using the integral Kissinger–Akahira–Sunose procedure. It is found that at different degrees of conversion, the activation energies are very close: E = 205–227 kJ/mol. The effect the composition of the copolymer has on the results from kinetic calculations is shown. The Coates–Redfern approach is used to determine the pre-exponential factor and the model of thermal decomposition. Calculated thermogravimetric curves are constructed and compared to experimental ones.
For the first time, the kinetics of isothermal curing and thermal degradation of polyethylene glycol maleate (pEGM)–based systems and their composites with mineral fillers were investigated in the presence of a benzoyl peroxide/N,N-Dimethylaniline redox-initiating system. DSC analysis revealed that the curing process at 20 °C can be described by the modified Kamal autocatalytic model; the critical degree of conversion (αc) decreases with increasing content of the unsaturated polyester pEGM and in the presence of fillers. In particular, for unfilled systems, αc was 0.77 for pEGM45 and 0.60 for pEGM60. TGA results demonstrated that higher pEGM content and the incorporation of fillers lead to increased thermal stability and residual mass, along with a reduction in the maximum decomposition rate (dTGₘₐₓ). Calculations using the Kissinger–Akahira–Sunose and Friedman methods also confirmed an increase in the activation energy of thermal degradation (Ea): EKAS was 419 kJ/mol for pEGM45 and 470 kJ/mol for pEGM60, with the highest values observed for pEGM60 systems with fillers (496 kJ/mol for SiO2 and 514 kJ/mol for CaCO3). Rheological studies employing three-interval thixotropy tests revealed the onset of thixotropic behavior upon filler addition and an increase in structure recovery after deformation of up to 56%. These findings underscore the potential of pEGM-based systems for low-temperature curing and for the design of composite materials with improved thermal resistance.
30 December 2022 in Bulletin of the Karaganda University. "Chemistry" Series
In order to evaluate the possibility of using different catalysts prepared for the hydrogenation process of primary coal tar, the method of differential thermal analysis was used, which allows to determine the kinetic parameters of thermal destruction, such as the rate constant, activation energy, and pre-exponential multiplier. The effect of catalysts on characteristics of mass loss during heating of "Shubarkol Komir" JSC primary coal tar at a constant speed (20 K/min) in a nitrogen medium has been considered. Microsphere, NiO/microsphere, CoO/microsphere, chrysotile and NiCo/chrysotile have been taken as catalytic additives. In the presence of the catalysts, the rate of thermal destruction of primary coal tar increases in the following order: CoO/microsphere < NiO/microsphere < NiCo/chrysotile. While microsphere catalysts extend the range of thermal destruction, chrysotile catalysts lead to the rapid completion of the destruction process. This fact is characterized by the formation of bonds between catalytic additives and primary coal tar. It is important to determine such parameters that affect on the activation energy and macrokinetics of the thermal decomposition process for prediction of catalyst activity during hydrogenation of heavy hydrocarbon raw materials.
Thermal decomposition of the copolymer based on polyethylene glycol fumarate with acrylic acid (p-EGF:AA) at four different heating rates in a nitrogen atmosphere has been investigated by the dynamic thermogravimetry (TGA) method. The TGA curves show that the decomposition process occurs in several stages. The experimental data processed by the Kissinger–Akahira–Sunose and Friedman isoconversion methods made it possible to calculate the activation energy of the main decomposition stage. According to the calculations results, one can see that the values found by these methods do not strongly depend on the conversion. The Achar–Brindley–Sharp method has been applied to determine the compensation parameters. Then, using the compensation effect, the invariant kinetic parameters of the decomposition processes have been found. An experimental curve has been plotted to find the reaction model in comparison with theoretical ones.