Search Results (148)

To address the issues of cities being overwhelmed by the waste and energy crisis, the pyrolysis of municipal solid waste (MSW), oil shale (OS) and their blends was investigated using a thermogravimetric simultaneous thermal analyzer in this study. The experimental research was conducted to investigate the thermal behavior and kinetic parameters of the different blending ratios of MSW and OS, to better utilize these intractable resources, observing whether there is a synergistic effect and trying to find the optimal process conditions. The Ozawa–Flynn–Wall method and the Kissinger–Akahira–Sunose method were used to calculate the activation energy at four different heating rates. The existence of interactions between MSW and OS was confirmed by comparing the experimental thermogravimetric and derivative thermogravimetric curves with the calculated ones. The findings of the thermogravimetric analysis, the calculation of theoretical and experimental curves, and kinetic analysis confirmed the interaction between the components and that the optimal blending ratio is 30% MSW and 70% OS. The optimality results in a relatively smaller activation energy (Eave = 115 kJ/mol), better comprehensive pyrolysis characteristics, and a more beneficial mutual effect. Full article

Hybrid silica xerogels functionalised with chlorinated organosilanes combine tunable porosity and surface chemistry, rendering them attractive for applications in sensing, membrane technology, and photonics. This study quantitatively investigates the thermal decomposition kinetics of organochlorinated xerogels and correlates with volatile compounds previously identified via Thermogravimetric Analysis (TGA) coupled to Fourier-Transform Infrared Spectroscopy (FT–IR) and Gas Chromatography coupled with Mass Spectrometry (GC–MS). The xerogels were synthesised via the sol–gel process using organochlorinated alkoxysilane precursors and yielded highly condensed nanostructures in which the precursor nature strongly influences the morphology and textural properties. In this study, the molar percentage of the organochlorinated compounds was fixed at 10%. Standard N₂ adsorption-desorption isotherm at 77 K revealed that increasing the precursor content systematically decreased the specific surface area and pore volume of the materials while promoting the formation of periodic domains, which are observed even at low organosilane molar percentages. Thermal characterisation via TGA/FT–IR/GC–MS revealed at least two main decomposition stages, with thermal stability following the order of 4–chlorophenyl > chloromethyl > 3–chloropropyl > 2–chloroethyl. This study focuses on kinetic and mechanistic insights in the thermal decomposition process through the Flynn–Wall–Ozawa isoconversional method and Criado master plots, using TGA/Differential Scanning Calorimetry (DSC) measurements under nitrogen at multiple heating rates (5, 10, 20, 30, and 40 K min⁻¹), which revealed activation energies ranging from 53 to 290 kJ mol⁻¹. Demonstrating that the chlorinated organosilane precursor directly controls both the textural properties and thermal behaviour of the resulting silica materials, with aromatic groups providing superior thermal stability compared to aliphatic chains. These quantitative kinetic insights provide a predictive framework for designing thermally stable hybrid materials while ensuring safe processing conditions to prevent hazardous volatile release. Full article

Estrogens are cholesterol-derived hormones, with four endogenous estrogens being presented in the scientific literature, namely, estradiol, estrone, estriol, and estetrol. In this study, we aim to obtain a complete thermoanalytical profile for the three most important endogenous estrogens: estradiol, estriol, and estrone. To achieve this, the TG/DTG were registered in non-isothermal conditions at five different heating rates (β = 2, 4, 6, 8, and 10 °C min⁻¹). To describe the mechanisms of the degradation processes, a complex kinetic analysis was performed by applying a preliminary method (ASTM E698), two isoconversional methods (Flynn–Wall–Ozawa and Friedman), and the non-parametric kinetic method. The results indicate that estradiol undergoes a single-step degradation process, while estriol and estrone present a complex degradation process. The determination of the shelf life of pharmaceutical products represents a critical factor in ensuring their safety and efficacy. This parameter can be estimated from the activation energy derived from non-isothermal experiments through the application of the Arrhenius equation and appropriate kinetic models. Full article

In this study, thermogravimetric analysis (TGA) was coupled with Fourier-transform infrared (FTIR) spectroscopy to systematically investigate the pyrolysis characteristics and mechanisms of cement fiberboard across varying heating rates. Experimental findings demonstrated that the thermal degradation process occurs in four distinct phases. Overlapping decomposition peaks in DTG curves were successfully resolved using a double-Gaussian deconvolution algorithm. A comprehensive kinetic analysis was conducted by integrating model-free iso-conversional methods (Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose analysis) with a model-fitting technique (Coats–Redfern approximation) to determine the activation energies for each degradation stage. A subsequent FTIR spectroscopic analysis revealed that the evolution of gaseous products follows the sequence CO₂ > H₂O > CH₄. The CO₂ release was found to originate from multiple pathways, including the decomposition of organic components and high-temperature inorganic reactions. Notably, while the heating rate had a negligible impact on product speciation, it exhibited a statistically significant influence on CO₂ emission intensities. Finally, mechanistic interpretations integrating Arrhenius parameters with time-resolved infrared spectral features were proposed for each thermal decomposition stage. Full article

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 T_max 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. Full article

This study presents an integrated approach to processing the heavy fraction of coal tar (HFCT) using oil shale (OS) from Shubarkol Komir JSC to simultaneously increase the yield of valuable hydrocarbon fractions and extract rare and dispersed trace elements. The lack of data on the effect of shale on the process and the kinetics of multi-component “tar + shale” systems limits the development of effective technologies. TG/DTG analysis was combined with the Friedman, Ozawa–Flynn–Wall, and Šesták–Berggren methods for the first time to evaluate the role of oil shale (OS). It was shown that the addition of 13% OS provides a sustained reduction in activation energy (~85–86 kJ/mol) and optimal conditions for hydrometallization. At 420 °C, an initial H₂ pressure of 4 MPa, and a reaction time of 60 min, the yield of light fractions reaches 62.6%, and the solid residue concentrates Ti, Mo, Ge, and other rare and dispersed elements reach up to 66,000 g/t in total. The possibility of extracting Ge using the Purolite C100 sorbent has also been confirmed. The novelty of the study lies in demonstrating the donor–catalytic effect of shale and the practical prospects of solid residue as a secondary mineral raw materials. Full article

Chemical recycling via catalytic pyrolysis is constrained by coke deposition and costly catalyst make-up. We investigate polypropylene (PP) and low-density polyethylene (LDPE) conversion over a spent FCC equilibrium catalyst (AXL) and, critically, quantify the re-activation energy landscape of the resulting coke. Using a semi-batch reactor (350 °C) and thermogravimetric analysis to 1100 °C combined with the Ozawa–Flynn–Wall method, we distinguish soft and hard coke under inert, oxidative, and sequential N₂ to air regimes. LDPE yields mainly gas (70.7 wt%) with 5.5 wt% coke, whereas PP favors liquids (47.1 wt%) with 3.4 wt% coke. LDPE-derived coke is softer (71% of total; E_A = 170 kJ mol⁻¹ soft) than PP coke (60% soft; E_A = 166 kJ mol⁻¹), evidencing a more refractory PP residue. Oxygen lowers E_A to ~155 kJ mol⁻¹ for both polymers. We introduce a simple TGA-based “softness ratio” to guide regeneration severity and show that a refinery-waste FCC catalyst delivers selective plastic-to-fuel conversion while enabling energy-aware regeneration protocols. The framework directly supports scale-up by linking polymer structure, coke quality, and atmosphere-dependent re-activation energetics. Full article

Thermogravimetric analysis (TGA) has been extensively applied in polymeric characterization and quality inspection, facilitating in-depth investigations of the microstructural thermal response characteristics of polymers, including thermal stability, composition analysis, and thermal decomposition mechanisms. Here, the impacts of six factors on the TG thermal analysis curves obtained during operation are systematically examined while analyzing their causes and recommending solutions. Furthermore, the thermal degradation kinetics of an ionomer formed by neutralizing an ethylene–methacrylic acid copolymer with metal ions (SGP membrane) used in laminated tempered glass is analyzed using the Arrhenius equation, Ozawa–Flynn–Wall hypothesis and Kissinger method. Kinetic parameters at 5% degradation are fitted and used to predict the service lifetime of the SGP membrane. The results indicate that the SGP membrane sample exhibits activation energy Ea = 136.90 kJ/mol, reaction order n = 1.65 and pre-factor A = e^25.93. It can be seen that the service lifetime of the SGP membrane sample is 16 years at 80 °C and 1.65 years at 100 °C. Full article

Amaranth is important for the agro-industrial complex. However, when extracting flour and oil from seeds, a lot of waste remains. Waste recycling by co-pyrolysis aims at obtaining new products with high added value. This study examined a combination of A. cruentus (AC) residues and low-density polyethylene (LDPE) waste. The addition of polymer was aimed at obtaining hydrocarbon-rich pyrolysis liquid and biochar. Pyrolysis was performed on an experimental setup, along with thermogravimetry–Fourier infrared spectroscopy–gas chromatography mass spectrometry (TG-FTIR-GC MS), to examine the thermochemical conversion. Experiments were carried out using a thermogravimetric analyzer at heating rates of 5, 10, and 20 °C/min. The average activation energy values for the pyrolysis of the AC/LDPE blend by the Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS) techniques were 301.39 kJ/mol and 287.69 kJ/mol, respectively. A visual examination of the correlations of the kinetic parameters of AC/LDPE was carried out using the Kriging method. The pyrolysis liquid from AC contains 38.14% hydrocarbons, with the main part being aliphatic hydrocarbons. During the pyrolysis of the AC/LDPE mixture, hydrocarbons were found in the resinous and waxy organic fractions of the pyrolysis liquid. The composition and properties of AC and AC/LDPE biochar are similar, and they can both be applied to agriculture. Full article

This study examined the impact of storage and operational aging on the thermal stability, structural degradation, and electrical properties of styrene–butadiene rubber (SBR) compound by analyzing three distinct materials: a laboratory-stored sample, an operationally aged one, and an original unaged reference. Thermal degradation was analyzed through thermogravimetric analysis (TGA), which examined weight loss as a function of temperature and time at different heating rates. Results showed that the onset temperature and peak position in the 457 °C to 483 °C range remained stable. The activation energy (Ea) was determined using the Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), and Friedman methods, with the original unaged sample’s (OUS) Ea averaging 203.7 kJ/mol, decreasing to 163.47 kJ/mol in the laboratory-stored sample (LSS), and increasing to 224.18 kJ/mol in the operationally aged sample (OAS). The Toop equation was applied to estimate the thermal degradation lifetime at a 50% conversion rate. Since the material had been exposed to electricity, the evolution of electrical conductivity was studied and found to have remained stable after storage at around 0.070 S/cm. However, after operational aging, it showed a considerable increase in conductivity, to 0.321 S/cm. Scanning Electron Microscopy (SEM) was employed to analyze microstructural degradation and chemical changes, providing insights into the impact of aging on thermal stability and electrical properties. Full article

To study the influence of curing agent structure on the properties of epoxy resin, four types of aromatic diamines with the structure of diphenyl methane (4,4′-methylenedianiline (MDA), 4,4′-methylenebis(2-ethylaniline) (MOEA), 4,4′-methylenebis(2-chloroaniline) (MOCA), and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA)) and a high-performance epoxy resin, 3-(oxiran-2-ylmethoxy)-N,N-bis(oxiran-2-ylmethyl)aniline (AFG-90MH), were used in this study. The resulting resin systems were designated as AFG-90MH-MDA, AFG-90MH-MOEA, AFG-90MH-MOCA, and AFG-90MH-MCDEA. After curing, these systems were named AFG-90MH-MDA-C, AFG-90MH-MOEA-C, AFG-90MH-MOCA-C, and AFG-90MH-MCDEA-C. The influence of the structure of the diamines on the processability, curing reaction activity, and thermal and mechanical properties (including flexural and tensile properties) of the epoxy resins were investigated. These systems demonstrate excellent processability with wide processing windows ranging from 30 °C to 110–160 °C while maintaining low viscosity. Consistent apparent activation energy (E_a) trends via both Kissinger and Flynn-Wall-Ozawa methods were observed. The epoxy systems exhibit the following increasing E_a sequence: AFG-90MH-MDA < AFG-90MH-MOEA < AFG-90MH-MOCA < AFG-90MH-MCDEA. The processability and curing reaction kinetic results indicate that the reactivities of the diamines decrease in the order: MDA > MOEA > MOCA > MCDEA. Polar chlorine substituents in diamines strengthen intermolecular interactions, thereby enhancing mechanical performance. The flexural strength of cured epoxy systems decreases as follows with corresponding values: AFG-90MH-MOCA-C (165 MPa) > AFG-90MH-MDA-C (158 MPa) > AFG-90MH-MCDEA-C (148 MPa) > AFG-90MH-MOEA-C (136 MPa). Diamines with substituents like chlorine or ethyl groups reduce the glass transition temperatures (T_g) of the cured resin systems. However, the cured resin systems with the diamines containing chlorine demonstrate superior thermal performance compared to those with ethyl groups. The cured epoxy systems exhibit the following descending glass transition temperature order with corresponding values: AFG-90MH-MDA-C (213 °C) > AFG-90MH-MOCA-C (190 °C) > AFG-90MH-MCDEA-C (183 °C) > AFG-90MH-MOEA-C (172 °C). Full article

Stainless steel dust (SSD) is a by-product generated during the smelting process of stainless steel, which is rich in valuable metals such as Fe, Cr, Ni, and Mn. To optimize the carbothermic reduction process of SSD, this study first conducted the thermodynamic analysis of the carbothermic reduction of SSD and then employed walnut shell biochar as a reductant with non-isothermal thermogravimetric analysis with linear heating rates of 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min. The activation energies of the carbothermic reduction reactions were calculated using the FWO method, KAS method, and Friedman method, respectively. Subsequently, the corresponding kinetic models were fitted and matched using the Málek method. The results indicate that before 600 °C, the direct reduction of SSD by carbon plays a dominant role. As the temperature increases, the indirect reduction becomes the main reduction reaction for SSD due to the generation of CO. The activation energies calculated by the Flynn–Wall–Ozawa (FWO) method, Kissinger–Akahira–Sunose (KAS) method, and Friedman method are 412.120 kJ/mol, 416.930 kJ/mol, and 411.778 kJ/mol, respectively, showing close values and a general trend of increasing activation energy as the conversion rate increased from 10% to 90%. Moreover, the reduction reaction is staged. In the conversion range of 10% to 50%, the carbothermic reduction reaction conforms to the shrinking core model within phase boundary reactions, coded as R1/4. In the conversion range of 50% to 60%, it conforms to the shrinking core model within phase boundary reactions, coded as R1/2; in the conversion range of 60% to 90%, the carbothermic reduction reaction follows the second-order chemical reaction model, coded as F2. Full article

Mango peel (MP), an abundant agro-industrial residue, was evaluated as a solid biofuel using combined physicochemical characterisation and non-isothermal thermogravimetric kinetics (TGA). Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) revealed hydroxyl-rich surfaces and porous microstructures. Thermogravimetric combustion, conducted at heating rates of 20–80 K min⁻¹, displayed three distinct stages. These stages correspond to dehydration (330–460 K), hemicellulose/cellulose oxidation (420–590 K), and cellulose/lignin oxidation (540–710 K). Kinetic analysis using six model-free methods (Friedman (FR), Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), Starink (STK), Kissinger (K), and Vyazovkin (VY)) yielded activation energies (E_a) of 52–197 kJ mol⁻¹, increasing with conversion (mean E_a ≈ 111 kJ mol⁻¹). Coats–Redfern (CR) fitting confirmed a three-dimensional diffusion mechanism (D3, R² > 0.99). Thermodynamic analysis revealed that the formation of the activated complex is endothermic, with activation enthalpy (ΔH) values of 45–285 kJ mol⁻¹. The process was found to be non-spontaneous under the studied conditions, with Gibbs free energy (ΔG) values ranging from 83 to 182 kJ mol⁻¹. With a high heating value (HHV) of 21.9 MJ kg⁻¹ and favourable combustion kinetics, MP is a promising supplementary fuel for industrial biomass boilers. However, its high potassium oxide (K₂O) content requires dedicated ash management strategies to mitigate slagging risks, a key consideration for its practical, large-scale application. Full article

TGA kinetic analysis can assess the thermal stability and degradation properties of PCMs by calculating activation energies and onset degradation temperatures, which are critical elements when developing optimal PCM composition and assessing long-term performance in thermal energy storage applications. In this study, we utilize a thermogravimetric analyzer to examine the thermal stability of both solar salt phase change material (i.e., commonly used in medium-temperature applications) (NaNO₃ + KNO₃) and a composite eutectic PCM mixture (i.e., PCM with 20% biochar). The activation energies of both the pure solar salt and composite solar salt PCM sample were evaluated using a variety of different kinetic models such as Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO), and Starink. For pure PCM, the mean activation energies calculated using the KAS, FWO, and Starink methods are 581.73 kJ/mol, 570.47 kJ/mol, and 581.31 kJ/mol, respectively. Conversely, for the composite solar salt PCM sample, the calculated experimental average activation energies are 51.67 kJ/mol, 62.124 kJ/mol, and 51.383 kJ/mol. Additionally, various machine learning models, such as linear regression, decision tree regression, gradient boosting regression, random forest regression, polynomial regression, Gaussian process regression, and KNN regression models, are developed to predict the degradation behaviour of pure and composite solar salts under different loading rates. In the machine learning models, the mass loss of the samples is the output variable and the input features are PCM type, heating rate, and temperature. The machine learning models had a great prediction performance based on experimental TGA data, with KNN regression outperforming the other models by achieving the lowest RMSE of 0.0318 and the highest R² score of 0.977. Full article

The pyrolysis of non-recyclable construction, renovation, and demolition (CRD) wood waste is a complex thermochemical process involving devolatilization, diffusion, phase transitions, and char formation. CRD wood, a low-ash biomass containing 24–32% lignin, includes both hardwood and softwood components, making it a viable heterogeneous feedstock for bioenergy production. Thermogravimetric analysis (TGA) of CRD wood residues was conducted at heating rates of 10, 20, 30, and 40 °C/min up to 900 °C, employing model-fitting (Coats–Redfern (CR)) and model-free (Ozawa–Flynn–Wall (OFW), Kissinger–Akahira–Sunose (KAS), and Friedman (FM)) approaches to determine kinetic and thermodynamic parameters. The degradation process exhibited three stages, with peak weight loss occurring at 350–400 °C. The Coats–Redfern method identified diffusion and phase interfacial models as highly correlated (R² > 0.99), with peak activation energy (E_a) at 30 °C/min reaching 114.96 kJ/mol. Model-free methods yielded E_a values between 172 and 196 kJ/mol across conversion rates (α) of 0.2–0.8. Thermodynamic parameters showed enthalpy (ΔH) of 179–192 kJ/mol, Gibbs free energy (ΔG) of 215–275 kJ/mol, and entropy (ΔS) between −60 and −130 J/mol·K, indicating an endothermic, non-spontaneous process. These results support CRD wood’s potential for biochar production through controlled pyrolysis. Full article