Thermal Decomposition Behavior Research Articles

Thermal decomposition behaviors, kinetics and thermodynamics of colemanite

Thermal decomposition behaviors, kinetics and thermodynamics of colemanite

Characterization and Comparative Investigation of Hydroxyapatite/Carboxymethyl Cellulose (CaHA/CMC) Matrix for Soft Tissue Augmentation in a Rat Model.

This study endeavors to develop an injectable subdermal implant material tailored for soft tissue repair and enhancement. The material consists of a ceramic phase of calcium hydroxyapatite (CaHA), which is biocompatible, 20-60 μm in size, known for its biocompatibility and minimal likelihood of causing foreign body reactions, antigenicity, and minimal inflammatory response, dispersed in a carrier phase composed of carboxymethyl cellulose (CMC), glycerol, and water for injection. The gel formulation underwent comprehensive characterization via various analytical techniques. X-ray diffraction (XRD) was employed to identify crystalline phases and investigate the structural properties of ceramic particles, while thermogravimetric analysis (TGA) was conducted to evaluate the thermal stability and decomposition behavior of the final formulation. Scanning electron microscopy (SEM) was utilized to examine the surface morphology and particle size distribution, confirming the homogeneous dispersion of spherical CaHA particles within the matrix. SEM analysis revealed particle sizes ranging from approximately 20-60 μm. Elemental analysis confirmed a stoichiometric Ca/P ratio of 1.65 in the hydroxyapatite (HA) structure. Heavy metal content exhibited suitability for surgical implant use without posing toxicity risks. Rheological analysis revealed a storage modulus of 58.6 and 68.9 kPa and a loss modulus of 21.7 and 24.8 kPa at the frequencies of 2 and 5 Hz, respectively. 150 μL of sterilized CaHA/CMC was injected subcutaneously into rats and compared with a similar product, Crystalys, to assess its effects on soft tissues. Skin tissue samples of rats were collected at specific intervals throughout the study (30, 45, 60, 90 and 120 days), and examined histologically. Results demonstrated that CaHA/CMC gel led to a significant increase in dermal thickness, elastic fibers, and collagen density. Based on the findings, the formulated CaHA/CMC gel was found to be biocompatible, biodegradable, nonimmunogenic, nontoxic, safe, and effective, and represents a promising option for soft tissue repair and augmentation.

Thermal decomposition kinetics and spectral analysis of mixed ester propellants

Mixed ester propellants are extensively used in artillery weapons due to their superior mechanical properties. This study investigates the decomposition kinetics and mechanism of mixed ester propellants using Differential Scanning Calorimetry (DSC) and Thermogravimetry-Fourier Transform Infrared Spectroscopy-Mass Spectrometry (TG-FTIR-MS). Kinetic parameters were determined via a model-free approach, while laser diagnostic technology captured radicals and molecular fragments during the decomposition-combustion process. Results indicate a single exothermic peak during decomposition, with apparent activation energy (Ea) increasing initially (0.01 ≤ α ≤ 0.4) and stabilizing around 278.43 kJ/mol later. The thermal decomposition behavior of mixed ester propellants follows the Sestak-Berggren equation, consistent with an autocatalytic reaction. NO2 generated during decomposition acts as a catalyst, accelerating the decomposition process. CN* radicals were detected throughout the combustion stages, indicating the resilience of the CN bond against breaking. This study can provide a theoretical basis for predicting fire development and for the selection or design of fire sensors.

Thermal Decomposition of Bio-Based Plastic Materials.

This research delves into a detailed exploration of the thermal decomposition behavior of bio-based polymers, specifically thermoplastic starch (TPS) and polylactic acid (PLA), under varying heating rates in a nitrogen atmosphere. This study employs thermogravimetry (TG) to investigate, providing comprehensive insights into the thermal stability of these eco-friendly polymers. In particular, the TPS kinetic model is examined, encompassing the decomposition of three distinct fractions. In contrast, PLA exhibits a simplified kinetic behavior requiring only a fraction described by a zero-order model. The kinetic study involves a systematic investigation into the individual contributions of key components within TPS, including starch, glycerin, and polyvinyl alcohol (PVA). This detailed analysis contributes to a comprehensive understanding of the thermal degradation process of TPS and PLA, enabling the optimization of processing conditions and the prediction of material behavior across varying thermal environments. Furthermore, the incorporation of different starch sources and calcium carbonate additives in TPS enhances our understanding of the polymer's thermal stability, offering insights into potential applications in diverse industries.

Characterization of Carbamide Peroxide: Stability Studies, and Degradation Kinetics under Isothermal Conditions for Industrial Application

Background: Carbamide peroxide (CP) is a hydrogen peroxide derivative bonded with urea. It is a solid substitute for liquid hydrogen peroxide in the chemical, cosmetics, and pharmaceutical industries, mainly as a disinfectant and bleaching application. However, it has an unstable nature, and there are scant studies on CP thermal analysis. Objective: This study focuses on CP thermal analysis and degradation behavior. Methods: CP was characterized by differential scanning calorimetry, thermogravimetric analysis, Fourier-transformed infrared, diffraction by X-ray, as well as, thermal and photodegradation was determined by ultraviolet spectrophotometer. Results: CP was characterized with a sharp endothermic event (88.50 oC; ΔH= -643.20 J.g-1), and a thermal decomposition behavior in a four-steps process. The pattern diffraction presented sharp peaks at 2θ: 15.2, 25.1 and 26.0o. The Arrhenius plot obtained by isothermal thermogravimetric analysis showed a linear relation with temperature in two steps. The first step the activation energy values was Ea = 45.73 J.mol-1.K-1. The thermal degradation recovery was 3.29% after 5 days, and 11.31% against 97.4% under the dark control to photostability. Conclusion: The study contributed to characterizing the CP and the results suggest that degradation depends on the surface transition state and the ternary formed system (CP-urea-water) and that the temperature influenced this system. The data were obtained through quick and easy techniques, which use wispy raw material and presented a significant result that can be used by the entire industry in the development of new formulations.

Co-pyrolysis behavior of municipal solid waste and food waste residue: A thermogravimetric study to discern synergistic effect

Effective solid waste disposal necessitates suitable combination and clean conversion technologies to maximize resource utilization. Thus, this study investigates the behavior of co-pyrolysis in municipal solid waste (MSW) and food waste (FW) via thermogravimetric analysis, aiming to discern synergistic effects and optimize waste to energy conversion. The impacts of heating rate and blending ratios were evaluated under an inert N2 atmosphere, within a temperature range of 30–900℃, during single and combined pyrolysis processes respectively. Results revealed slight variations in weight loss patterns and thermal decomposition behavior. When heating rate increased from 10 to 30℃.min−1, decomposition process delayed, resulting in higher initial (Ti), peak (TP), and final (Tf) temperatures due to inadequate heat transfer. As food waste increased, mass loss rose and favorable synergistic effect was observed at 20 % FW during medium temperatures, while other blends showed inhibitory effects. The pyrolytic index (D) rose nonlinearly from 6.29 × 10−7 to 7.72 × 10−7 with a higher FW proportion, peaking at 20 % FW, suggesting an optimal MSW and FW mixing ratio. This blend also exhibited the lowest activation energy, indicating a more efficient thermal decomposition process. Those outcomes offer crucial insights for optimizing co-pyrolysis systems and provide essential information for co-disposal of MSW and FW, potentially reducing pollutant emissions and enhancing waste to energy conversion.

The synthesis and properties of low sensitivity and heat resistant guanidine salts

This paper uses a simple method to synthesis four guanidine salts of nitrophenols and tetrazoles with low sensitivity (friction sensitivity and impact sensitivity) and high decomposition temperature. The crystal structures were tested by an X-ray single crystal diffractometer. Thermal decomposition behaviors were examined via differential scanning calorimetry (DSC), revealing decomposition temperatures of 295.04 °C, 332.57 °C, 252.51 °C, and 301.17 °C, all exceeding 250.00 °C. The detonation velocities and pressures were calculated using Explo5 based on the experimentally measured combustion heat. The detonation velocities for the four guanidine salts followed the order 4 (7667 m s−1)＞ 2 (6909 m s−1)＞ 3 (6722 m s−1)＞ 1 (6560 m s−1), and the explosion pressures were ranked as 4 (19.13 GPa)＞ 2 (17.72 GPa)＞ 1 (14.96 GPa)＞ 3 (12.43 GPa). The combustion heats were measured using oxygen bomb calorimetry and were found to be 2 (11.85 kJ g⁻1) > 3 (11.66 kJ g⁻1) > 4 (11.31 kJ g⁻1) > 1 (10.57 kJ g⁻1). The impact sensitivity was greater than 100 J, and the friction sensitivity was greater than 360 N. Given these advantages, it is anticipated that these compounds could have applications in propellants and gas generators.

Tripiperidinium pentaformato copper(II) – A unique homoleptic Cu(II) formate

The synthesis, structure and thermal decomposition behaviour of unique mononuclear, homoleptic [pipH]3[Cu(O2CH)5] (2) (pipH+ = piperidinium) is discussed in which the copper(II) ion is exclusively coordinated by five formate anions forming a distorted square-pyramidal coordination sphere. Thermogravimetric studies confirmed a comparatively low decomposition temperature (Tonset = 107 °C) affording solely elemental Cu. Based on TG-MS experiments a decomposition mechanism is presented.______________________________________________________________________________

Decomposition and migration behavior of Pt salt on Al2O3 and SiO2 upon calcination studied by XAFS and UV–visible spectroscopy using a laboratory-type spectrometer

Thermal decomposition behavior of two kinds of Pt salts, namely, H2PtCl6 and Pt(NH3)4Cl2, on amorphous SiO2 and γ-Al2O3 under air to prepare supported platinum catalysts up to 773 K was investigated by in-situ laboratory X-ray absorption fine structure (XANES/EXAFS) and UV–Vis spectroscopy. Changing the oxidation state of platinum species and the coordination environment, the migration to vacant sites or aggregation process on the surface were discussed. The supported H2PtCl6 was reduced to Pt2+ species under air flow around 573 K by eliminating Cl/O ligand atoms until 573 K. High-temperature treatment caused the re-oxidation of the supported Pt species on Al2O3, but it did not affect the oxidation state of SiO2-supported species. The formed platinum oxychloride on Al2O3 was stable under air, but it partly decomposed to atomic-like species above 673 K, followed by migration on the surface, trapping at the cation vacant site because of its defect spinel structure. The lattice oxygen atoms of Al2O3 adjacent to Pt atom captured might cause the re-oxidation, and molecular oxygen was not the oxidant. The partly formed atomic-like species migrates on the SiO2 surface, followed by aggregation to form metallic Pt particles above 573 K.

Hydrated carboxylate ionic liquids as chemical CO2 sorbents of high capacity and moderate enthalpy of absorption

Tetralkylphosphonium carboxylate ionic liquids are herein presented as efficient carbon dioxide chemisorbents in the presence of water. The ionic liquids tetrabutylphosphonium formate and acetate, tributylmethylphosphonium formate and a series of triethylalkylphosphonium formates and acetates, have been prepared by various synthetic procedures either from hydroxide or methylcarbonate precursors, or via multiple steps starting from the parent triethylphosphine. Their physicochemical properties, namely melting or glass transition temperatures, thermal decomposition behaviour, densities and viscosities have been determined. As dry substances, they are viscous liquids or low-melting solids, whereas they show little tendency to solidify in their hydrated forms. They were used mostly as monohydrates in CO2 solubility measurements, exhibiting highest capacities (3 mol L−1, i.e. ≈ 0.9 molCO2 molIL−1, at 5 bar, 25 °C) at equimolar H2O/ionic liquid ratios, approaching those of commercial aqueous amine sorbents. Carbon dioxide chemisorption into hydrogencarbonate takes place, as demonstrated by infrared spectroscopy with isotopic labelling. CO2 absorption isotherms were recorded at various temperatures and the data used to estimate the heat of absorption according to three different thermodynamic models. Enthalpies of CO2 absorption depended heavily on the model used. Rationalisation of this was done on the grounds of the expected relevance of physical and chemical sorption processes. Average heats of CO2 absorption lie between −40 and −45 kJ mol−1, in accordance with mild chemical absorption albeit significantly lower than those for typical chemical sorbents such as amines. This reinforces the feasibility of hydrated carboxylate ionic liquids for CO2 capture technologies of low regeneration energies.

Investigation of bio-based rigid polyurethane foams synthesized with lignin and castor oil

In this study, polyurethane (PU) foams were manufactured using kraft lignin and castor oil as bio-based polyols by replacing 5–20 wt% and 10–100 wt% of conventional polyol, respectively. To investigate the effects of unmodified bio-based polyols on PU foam production, reactivity and morphology within PU composites was analyzed as well as mechanical and thermal properties of the resulting foams. Bio-based PU foam production was carried out after characterizing the reagents used in the foaming process (including hydroxyl group content, molecular weight distribution, and viscosity). To compare the resulting bio-based PU foams, control foam were produced without any bio-based polyol under the same experimental conditions. For lignin-incorporated PU foams, two types, LPU and lpu, were manufactured with index ratio of 1.01 and 1.3, respectively. The compressive strength of LPU foams increased with lignin content from 5 wt% (LPU5: 147 kPa) to 20 wt% (LPU20: 207 kPa), although it remained lower than that of the control foam (PU0: 326 kPa). Similarly, the compressive strength of lpu foams was lower than that of the control foam (pu0: 441 kPa), with values of 164 kPa (lpu5), 163 kPa (lpu10), 167 kPa (lpu15), and 147 kPa (lpu20). At 10 wt% lignin content, both foams (LPU10 and lpu10) exhibited the smallest and most homogenous pore sizes and structures. For castor oil-incorporated PU foams with an index of 1.01, denoted as CPU, increasing castor oil content resulted in larger cell sizes and void fractions, transitioning to an open-cell structure and decreasing the compressive strength of the foams from 284 kPa (CPU10) to 23 kPa (CPU100). Fourier transform infrared (FT-IR) results indicated the formation of characteristic urethane linkages in PU foams and confirmed that bio-based polyols were less reactive with isocyanate compared to traditional polyol. Thermogravimetric analysis (TGA) showed that incorporating lignin and castor oil affected the thermal decomposition behavior. The thermal stability of lignin-incorporated PU foams improved as the lignin content increased with char yields increasing from 11.5 wt% (LPU5) to 15.8 wt% (LPU20) and from 12.4 wt% (lpu5) to 17.5 wt% (lpu20). Conversely, the addition of castor oil resulted in decreased thermal stability, with char yields decreasing from 10.6 wt% (CPU10) to 4.2 wt% (CPU100). This research provides a comprehensive understanding of PU foams incorporating unmodified biomass-derived polyols (lignin and castor oil), suggesting their potential for value-added utilization as bio-based products.

Effect of the silanization process on the fire resistance and thermal properties of closed-cell foams with sunflower husk ash

The topics covered in this paper are relevant to the further development of polyurethane materials and propose a new method for producing sustainable and innovative foams. In this study, the effect of filler silanization on the flammability and thermal stability of rigid polyurethane foam (RPUF) was investigated. The RPUF composites study was preceded by an analysis of sunflower husk ash (SHA). Thermal decomposition behaviour and particle size distribution were carried out for the SHA samples. More, the elemental composition and structure of the fillers were investigated. The use of silanization of the filler results in homogenization of its structure. Sunflower husk ash has higher characteristic melting points than most biomass ashes and good thermal stability. The foam flammability results were preceded by an analysis of density and cell morphology. The use of silanized filler in RPUFs results in a homogenized structure and a 14 % reduction in apparent density. A wide range of tests were carried out as part of the flammability tests, which included: limiting oxygen index (LOI), gross calorific value, cone calorimeter, and optical density test. Additionally, thermal analysis methods were used to investigate the thermal stability of the foams. Flammability tests carried out confirm the positive effect of filler salinization on flammability. Heat release during combustion is reduced by 10 % and the release of toxic gases is also reduced. On the other hand, the thermal stability results are similar for foam with unmodified filler and those with silanized ash. Based on the comprehensive flammability and smoke results, a trend towards improved flame-retardant properties of RPUFs was observed.

Preparation of metal–organic framework-199 (Cu) and their effects on catalytic decomposition of hexahydro-1,3,5-trinitro-s-triazine

In this study, a series of metal–organic framework-199 (MOF-199) products were prepared with copper (Cu) as the metal center and trimesic acid as the organic ligand. The morphological changes of MOF-199 under different preparation conditions and its application in the catalytic thermal decomposition of hexahydro-1,3,5-trinitro-s-triazine (RDX) were studied. The morphological changes of MOF-199 were compared by scanning electron microscopy (SEM), the crystal structures of MOF-199 were analyzed by X-ray diffraction and the effects of MOF-199 with different morphological characteristics on the thermal decomposition behavior of RDX were studied by differential scanning calorimetry. The results showed that MOF-199 with different morphologies could effectively adjust the thermal decomposition process of RDX and reduce the decomposition peak temperature of RDX, and the catalytic effect of MOF-199 was different due to different crystal surfaces exposed. Among them, (110) was a highly active crystal plane with a high catalytic activity. In addition to the crystal plane structure, the defects on the surface of MOF-199 would also affect its catalytic performance. This study provides some theoretical support for the catalytic mechanism of MOFs in the thermal decomposition of nitro compounds.

Study on Pyrolysis Behavior of Avermectin Mycelial Residues and Characterization of Obtained Gas, Liquid, and Biochar

The proper disposal of antibiotic mycelial residue (AMR) is a critical concern due to the spread of antibiotics and environmental pollution. Pyrolysis emerges as a promising technology for AMR treatment. In this study, we investigated the effect of pyrolysis temperature on the thermal decomposition behavior and product characteristics of avermectin (AV) mycelial residues. Various characterization techniques were employed to analyze thoroughly the compositions and yields of the obtained gas, liquid, and biochar products. The results indicated that most of the organic matter such as protein, carbohydrate, and aliphatic compounds in AV mycelial residues decomposed intensely at 322 °C and tended to end at 700 °C, with a total weight loss of up to 72.6 wt%. As the pyrolysis temperature increased, the biochar yield decreased from 32.81 wt% to 26.39 wt% because of the enhanced degradation of volatiles and secondary reactions of the formed aromatic rings. Accordingly, more gas components were formed with the gas yield increased from 9.76 wt% to 15.42 wt%. For bio-oil, the contents were maintained in the range of 57.43–60.13 wt%. CO and CO2 dominated the gas components with a high total content of almost 62.37–97.54 vol%. At the same time, abundant acids, esters (42.99–48.85%), and nitrogen-containing compounds (32.14–38.70%) such as nitriles, amides, and nitrogenous heterocyclic compounds were detected for the obtained bio-oil. As for the obtained biochars, particle accumulation and irregular pores were presented on their bulk surface, which was primarily composed of calcium oxalate (CaC2O4) and calcium carbonate (CaCO3). This work can provide theoretical insights for the harmless disposal and resource recovery for AMR, contributing significantly to the field of solid waste reuse and management.

Thermal decomposition study of 4-methyloxybenzyl-glycoside by TG/DTA and on-line pyrolysis-photoionization mass spectrometry

A flavor precursor of 4-methyloxybenzyl-2, 3, 4, 6-tetra-O-acetyl-β-d-glucopyranoside (MBGL) was synthesized via a modified Koenigs–Knorr reaction. The thermal decomposition behaviour and pyrolysis intermediate products of the glycoside were studied by simultaneous thermogravimetric/differential thermal analysis (TG/DTA) and synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). TG/DTA results showed that the largest mass loss rate appeared at a Tp of 246.7 °C. PIMS was used to identify the pyrolysis products of MBGL at 300 °C, 500 °C and 700 °C, respectively. The experimental apparatus had some advantages in real-time analysis and fewer secondary reactions. Some important pyrolysis intermediates, such as the ions of the 4-methyloxybenzyl group at m/z 121 and the glycone moiety at m/z 347, were detected by PIMS. The results indicate that the MBGL was probably showed a different pyrolysis way compared with the other glycosides. This work reports a useful application of synchrotron VUV PIMS in a thermal decomposition study of glycoside flavor precursors.

Study of using cork powder as an adjuvant bio-flame retardant in acrylonitrile-butadiene-styrene flame retardant formulations

By having a challenging prospect of developing more environmentally friendly flame-retardant (FR) acrylonitrile-butadiene-styrene (ABS) formulations, an initial study related to the effect of combining ammonium polyphosphate (APP) with cork powder (C), a bio-waste of the cork industry on ABS-FR thermal stability and fire performance is proposed and discussed in the present work. ABS composites with a global filler weight content of 30 wt.% were prepared by using a melt-compounding process. Two different types of thermal decomposition behavior, assessed by means of thermogravimetric analysis (TGA), were observed for ABS/C/APP composites. For formulations with C/APP weight ratio < 1, the thermal decomposition of APP polyphosphate network was shifted to lower temperature. On the other hand, when C/APP ratio was ≥ 1, a new thermal decomposition (TD) step related to an earlier thermal decomposition of cork components was registered between 320 °C and 370 °C. Moreover, by means of Fourier-transform infrared spectroscopy (FTIR) analysis of the pyrolysis gasses, a broader temperature range of ammonia and water release was noticed when APP and C were simultaneously incorporated in ABS. In addition, a micro-scale combustion calorimeter (MCC) analysis revealed that replacing APP by cork led to a decrease of the heat release capacity (HRC) and an increase of the residue formation compared to when only APP was present in ABS composite. Furthermore, forced flaming fire characterization of ABS formulations, studied by means of cone calorimetry (CC), revealed that replacing 20 wt.% of APP by cork (ABS/20C/10APP) led to a similar fire performance to the ABS formulation with 30 wt.% of APP (ABS/30APP). A similar trend under horizontal UL-94 was observed, nevertheless, for the composite with cork in its composition no dripping was noticed. Additionally, by only replacing a 3 wt.% of APP (ABS/3C/27APP) by cork an optimum improvement in fire retardancy was achieved, with the highest efficiency in reducing the peak heat release rate (pHRR) of 21 % regarding ABS/30APP. These results have been related to the chemical interaction between APP and cork components in the condensed phase confirmed by the observance of a more intense P-O-C absorbance peak of the CC residue of ABS/3C/27APP, analyzed by means of FTIR. This composite also showed a more cohesive and expanded char layer, observed by scanning electron microscopy (SEM), which acted as a more efficient protective barrier, reducing heat and mass transfer phenomena during combustion which also led to the highest reduction in linear burning rate (LBR) under horizontal UL-94.

Withdrawn: Co-hydropyrolysis of sewage sludge and algae biomass: A systematic study on thermal decomposition behaviors and kinetic characteristics

In the present study, a thermogravimetric analyzer was used to assess the co-hydropyrolysis kinetics of sewage sludge and algae biomass. Three isoconversional methods (Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Friedman) and one model-fitting method (DAEM) accurately fitted the experimental data at three heating rates (10, 30 and 50 °C/min) between 10 % and 90 % conversion. These methods agree with the trends shown by the activation energy (Ea) distribution calculated, with fluctuations between 120 and 330 kJ/mol. Compared with the pyrolysis of a single sample, the reaction activation energy of sludge and algae was significantly reduced in the case of co-pyrolysis. When 20 % algae are added, the activation energy is only 50 % of the original, below 100KJ/mol. Physiochemical characterization confirmed that they have the potential for fuel and energy production. Kinetic parameters fitted by DAEM were successfully verified at the highest heating rate studied and the linear fitting curve of DAEM is better. The kinetic results confirm that the activation energy is related to the conversion rate, and the change of activation energy and conversion rate indicates that the biomass undergoes a very complex pyrolysis process. In this study, the mixing of sewage sludge and algal biomass in hydrogen atmosphere can significantly change the energy required for pyrolysis reaction, which provides data support for the development, design and optimization of pyrolysis reactors. According to the change of weight loss and activation energy, it provides support for the feed amount, reaction temperature and gas flow of the pyrolysis furnace in the process of pyrolysis reaction.

Thermal decomposition characteristics of BHT and its peroxide (BHTOOH).

2,6-Di-tert-butyl-4-methylphenol (BHT) is an excellent antioxidant that is easily oxidized to 2,6-di-tert-butyl-4-hydroperoxyl-4-methyl-2,5-cyclohexadienone (BHTOOH). For the safety of BHT production and usage, it is meaningful to study the thermal stability and decomposition properties of BHT and BHTOOH. In this paper, the thermal decomposition properties of BHT and BHTOOH were compared by the mini closed pressure vessel test (MCPVT) and differential scanning calorimetry (DSC). Their kinetics of thermal decomposition were studied using thermogravimetric analysis (TGA). The thermal decomposition products of BHT and BHTOOH were analyzed by gas chromatography-mass spectrometry (GC-MS). The results show that there was no significant change in temperature pressure when BHT was warmed up under a nitrogen atmosphere, indicating that BHT was stable within 400K. The thermal decomposition reaction of BHTOOH was rapid with an initial reaction temperature of 375.2K. The initial exothermic temperature (Ti) and heat release (QDSC) of DSC were 384.9K and 865.0Jg-1, respectively. The apparent activation energies (Ea) for the thermal decomposition reactions of BHT and BHTOOH calculated by the Kissinger method were 151.8kJmol-1 and 66.07kJmol-1, respectively. The main decomposition products of BHT were isobutene and 2-tert-butyl-4-methylphenol. The thermal decomposition products of BHTOOH included BHT, 2,6-di-tert-butyl-4-ethylphenol, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 4,4'-(1,2-ethanediyl) bis [2,6-bis (1,1-dimethylethyl) phenol, etc. Based on the thermal decomposition behavior and products, the reaction pathway has been described. These results indicate that BHT is a potential thermal hazard during production, storage and application. For the safety of the chemical industry, the oxidation of BHT should be avoided.

Pyrolysis characteristics and kinetic investigation of waste groundnut shells using thermogravimetric analyzer, Py-FTIR, and Py-GC-MS

The objective of the present study was to investigate the bioenergy and resource recovery potential of groundnut shells (GNS) through pyrolysis. The release of vapours at short time scales and their composition were investigated using analytical pyrolysis coupled with Fourier transform infrared (FTIR) spectroscopy and gas chromatography/mass spectrometry (GC/MS). The thermal decomposition behaviour and kinetic evaluation were carried out using a thermogravimetric analyzer (TGA). Five iso-conversional models and master plots method were utilized to explore the kinetic parameters and reaction mechanism at dynamic heating rates (10, 20, and 30 °C min−1). X-ray fluorescence spectroscopy (XRF) was employed to detect the ash composition, which is essential to evaluate the slagging and fouling potential of the biomass when used for bioenergy. TG data revealed three distinct stages of decomposition, while an immense amount of biomass disruption was observed at a higher heating rate (30 °C min−1). Further, the average apparent activation energy of pyrolysis determined using KAS, ST, DAEM, and VZ were 223.26, 214.57, 207.97, and 117.24 kJ mol−1, respectively. The extreme emission of carbon dioxide and carbonyl compounds was discovered through Py-FTIR. The increased formation of hydrocarbons (14.22–34.26%), alcohols (1.41–9.43%), and reduction in phenols (19.13–18.67%) at different temperatures (450, 550, and 650 °C) were validated by Py-GC-MS. Overall, the findings demonstrate that GNS is a promising feedstock for pyrolysis to produce valuable fuel molecules and chemicals.

Kinetic models of HMX decomposition via chemical reaction neural network

1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX) is commonly used in solid propellants and explosives as energetic materials. The study of its kinetics and decomposition mechanism is of great significance to its application in the aerospace industries. This work investigates the thermal decomposition of HMX based on the combined thermogravimetric (TG) measurements and chemical reaction neural network (CRNN). Two compact kinetic models for HMX are introduced, with one consisting of four substances and a single global reaction (4–1 model) and the other consisting of four substances and four reactions (4–4 model). In the 4–1 model, the calculated activation energy is 328.44 kJ·mol−1, which agrees with the experimental value. As for the 4–4 model, the substances and reactions are assigned based on a skeleton mechanism involving reactions of N-N and C-N bond cleavage and HONO elimination. Moreover, the catalytic effects of TiO2 and Al2O3 on HMX are well simulated using the aforementioned kinetic models. The CRNN models can reproduce the peak temperature with a reduced activation energy, but the initial decomposition temperature is overestimated owing to the complex nature of catalytic impact. This work presents the application of the CRNN model to obtain a decomposition mechanism of HMX, highlighting its efficacy in accurately capturing the thermal decomposition behavior. The potential extension of CRNN to kinetic modeling of other energetic materials is anticipated in future studies.