Thermal Degradation Kinetics Research Articles

Investigating the Impact of Nano‐Metal Oxides (Copper and Iron) on the Thermal Decomposition Behavior of Advanced Propellants with Nitrocellulose/Polyurethane Binders

AbstractThis research delves into the combined effects of green nano metal oxides (copper and iron) and polyurethane (PU) modification on the thermal degradation kinetics of propellant based on solid ammonium nitrate composite modified simple base (CMSB). Surface modification of ammonium nitrate particles was achieved through repeated spray coating, ensuring effective catalyst binding. The formulated compositions of propellants underwent thorough thermal characterization, including thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses. TG analysis revealed a significant decrease in the propellant's thermal degradation temperature, attributed to AN modification with nano metal oxides (nMOs) and the use of PU/NC as a binder. Isoconversional kinetic methods (It‐KAS, It‐FWO, and VYA/CE) were employed for further analysis, allowing prediction of kinetic parameters. Additionally, kinetic analysis results allowed calculation of the critical ignition temperature. The thermokinetic results underscore the substantial impact of nMOs particles and PU modification regarding the reactivity and catalytic performance of propellant containing ammonium nitrate, leading to a noteworthy reduction in activation energy and critical ignition temperature. Furthermore, modifying the binder with nitrocellulose and incorporating nanoparticles significantly reduces ignition delay and combustion duration while increasing flame intensity in CMDB solid propellants, enhancing overall combustion efficiency.

Thermoanalytical and Kinetic Studies for the Thermal Stability of Emerging Pharmaceutical Pollutants Under Different Heating Rates.

Emerging pharmaceutical pollutants like ciprofloxacin (CIP) and ibuprofen (IBU) are frequently detected in aquatic environments, posing risks to ecosystems and human health. Since pollutants rarely exist alone in the environment, understanding the thermal stability and degradation kinetics of these compounds, especially in mixtures, is crucial for developing effective removal strategies. This study therefore investigates the thermal stability and degradation kinetics of CIP and IBU, under different heating rates. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were employed to examine the thermal behavior of these compounds individually and in mixture (CIP + IBU) at heating rates of 10, 20, and 30 °C/min. The kinetics of thermal degradation were analyzed using both model-fitting (Coats-Redfern (CR)) and model-free (Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Friedman (FR)) methods. The results showed distinct degradation patterns, with CIP decomposing between 280 and 550 °C and IBU between 152 and 350 °C, while the mixture exhibited multistep decomposition in the 157-500 °C range. The CR model indicated first-order kinetics as a better fit for the degradation (except for IBU). Furthermore, CIP exhibits higher thermal stability and activation energy compared to IBU, with the KAS model yielding activation energies of 58.09 kJ/mol for CIP, 11.37 kJ/mol for IBU, and 41.09 kJ/mol for CIP + IBU mixture. The CIP + IBU mixture generally showed intermediate thermal properties, suggesting synergistic and antagonistic interactions between the compounds. Thermodynamic parameters (ΔH°, ΔG°, ΔS°) were calculated, revealing non-spontaneous, endothermic processes for all samples (except in the FWO method) with a decrease in molecular disorder and positive ΔG° values across all models and heating rates. The study found that higher heating rates led to less thermodynamically favorable conditions for degradation. These findings provide important information concerning the thermal behavior of these pharmaceutical pollutants, which can inform strategies for their removal from the environment and the development of more effective waste-treatment processes.

Thermal degradation of polytetrafluoroethylene, modified polytetrafluoroethylene, and their nanocomposites with boron nitride nanobarbs: Lifetime predictions and kinetic analysis

AbstractFlexible polymeric materials including dielectric thermal interface materials (TIMs) used in integrated circuits and other high frequency applications are exposed to extreme thermal and electrical conditions during their service life. Insight into the in‐use thermal stability and material lifetime is valuable to maintaining performance durability and preventing premature failure in actual end use. Herein, the thermal stability of polytetrafluoroethylene (PTFE), modified PTFE and their nanocomposites with recent generation boron nitride nanobarbs (BNNBs) was investigated based on lifetime prediction from thermogravimetric analysis and tensile strength deterioration of heat‐aged samples. Additionally, thermal degradation kinetics and mechanism was investigated using the model‐free advanced isoconversional method based on changing activation energy. The result shows that BNNB extends the lifetime of the PTFE by an order of magnitude. The degradation mechanism proposed from TGA‐MS result is supported by the multistep degradation mechanism identified in the kinetic computation. These results are valuable for predicting materials' in‐use lifetime to avoid premature failure.

Effect of the heat treatment on the physicochemical characteristics of rubberwood: Results of thermal analysis and FTIR spectroscopy

Heat treatment is an environmentally friendly method used to improve properties of rubberwood. In this work, the changes in the chemical composition, thermal behavior and thermal degradation kinetics of heat-treated Hevea brasiliensis (rubber tree) were evaluated using thermogravimetry, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The rubberwood samples were exposed to temperatures of 180 °C and 220 °C in air under atmospheric pressure for durations of 15 25 and 35 h. Thermal analysis revealed degradation of hemicelluloses, an increase in the relative proportions of cellulose and lignin in heat-treated rubberwood. The thermal decomposition of rubberwood heat-treated at 220 °C started at a higher temperature compared to untreated wood. A shift in the position of peaks on differential thermogravimetry and differential scanning calorimetry curves of heat-treated samples was observed, indicating changes in the structure of wood polymers. The temperature of heat treatment had a stronger effect on the chemical composition of rubberwood than duration. Significant changes in the chemical composition of rubberwood occurred after the treatment duration of 15 h at both 180 °C and 220 °C. The duration of 25 h and 35 h had no further substantial effect. The isoconversional method of Flynn-Wall-Ozawa was used to determine the kinetics of thermal degradation of untreated and heat-treated rubberwood. It is found that the average values of activation energy in the conversion degree range of 0,05 - 0,65 (the thermal degradation of polysaccharides) increased with increasing treatment temperature and duration. Fourier transform infrared spectra demonstrated alterations in wood polymers.

Study of the Acidic, Basic, and Thermal Degradation Kinetics of Three Antihypertensive Drugs-Individually and in Combination.

The importance of fixed-dose combinations (FDCs) for the treatment of hypertension is well established. However, from a stability perspective, FDCs present a challenge since the degradation of one active pharmaceutical ingredient (API) can be affected by the presence of another API. The aim of this study was to compare the degradation behaviors and evaluate the degradation kinetics of three antihypertensive drugs, perindopril tert-butylamine (PER), amlodipine besylate (AML), and indapamide (IND). The degradation processes were studied using the previously developed reverse phase high-performance liquid chromatographic (RP-HPLC) method after exposing each drug individually, as well as the combinations of two/three drugs, to different stress factors, such as light, oxidation, acidic, basic, or neutral pH values at different temperatures. The results show that PER is most unstable under basic conditions and that AML displays a negative, while IND displays a positive effect, on PER stability when combined. AML is most affected by basic conditions and oxidation, and its stability is affected by both drugs positively; IND undergoes extreme photolysis, which is positively affected by AML but negatively by PER. Great care must be taken when formulating FDCs with these three drugs, as well as solutions or oral suspensions adjusted for geriatric or pediatric populations, since the stability of all three drugs is greatly affected by pH conditions, as well as light or oxidation factors and their interactions.

Biocompounds recovery from purple corn cob by-product: extraction kinetics, thermal and physicochemical stability of liquid and powdered anthocyanin-rich extract

This study evaluated the thermal degradation kinetics of total monomeric anthocyanins (TMA) from in-natura purple corn cob and the recovery of bioactive compounds from their by-products. The TMA and antioxidant capacity (AC) extraction kinetics were evaluated by conventional (CE) and ultrasound-assisted extraction (UAE, 25°C, 40kHz, 32W/L) methods. The stability of liquid and powdered extract by using maltodextrin (M) [M(2%)] and corn starch (C) [M(1.5%) + C(0.5%)], was evaluated. Thermal degradation kinetics (65-90°C) showed that TMA are relatively stable at high temperatures, with a half-life of 5.3h at 90°C and an activation energy of 949.2J·mol-1. The TMA and AC extraction kinetics from corn cob by-product, described by the Peleg model, showed that the UAE had the highest extraction rate (<k1) and equilibrium yield (<k2), reducing CE times by up to 58% and 67%, for TMA and AC respectively. Furthermore, the stability of this extract was greater at pH ≤ 3, decreasing at neutral and alkaline pH. On the other hand, the water adsorption isotherms modeled by GAB model showed that the powder [M(1.5%) + C(0.5%)] had greater stability (Xm = 5.97g/100g d.m.) compared to the powder [M(2%)] (Xm = 3.71g/100g d.m.). Additionally, significant differences were observed between treatments in terms of color density, polymeric color, and % tannin contribution, where the powder [M(1.5%) + C(0.5%)] demonstrated greater stability. These results highlight the effectiveness of the UAE method for recovering TMA and AC from purple corn cob by-products and the importance of storage conditions and pH in the stability of anthocyanin-rich extracts and powders with potential applications in food and non-food industries.

Microblog‐Assisted Synthesis of Schiff Base Network Polymers for SO2/Epoxide Copolymerization and Thermal Degradation Kinetics of the Products

AbstractThis study successfully prepared three environmentally friendly Schiff base network (SNW) polymers, SNW‐1, SNW‐2, and SNW‐3, using melamine and aldehyde compounds as raw materials through a microwave‐assisted synthesis method. The SNW materials were applied to catalyze the copolymerization reaction of SO2 and epoxides. Through detailed analysis of the chemical structure and properties of SNW‐1, SNW‐2, and SNW‐3, their catalytic efficiency was thoroughly investigated. Three thermal degradation kinetic models, Flynn–Wall–Ozawa (FWO), Kissinger, and Coats–Redfern, were employed to calculate the kinetic parameters of the thermal degradation of poly(cyclohexene sulfite) (PCS). Potential thermal degradation mechanisms were speculated. Additionally, the Kissinger model accurately described the thermal degradation kinetics features of PCS. Based on experimental results and kinetic analysis, this paper elucidates the potential mechanism of the copolymerization reaction of SO2 and epoxides. The study indicates that microwave‐assisted synthesis exhibits convenience and high efficiency in preparing efficient catalysts, demonstrating significant potential across various application domains.

Mesoporous, high surface area and microrod-shaped cobalt (II) coordination polymer for assessment of molecular structure, thermolysis and non-isothermal kinetics parameters

This study is significant as it presents the assessment of molecular identification, thermal degradation, and non-isothermal kinetics of a cobalt (II) coordination polymer [Co (II) CPs] synthesized from suberoyl bis (2-ethoxybenzamide) (sbebz) and cobalt acetate through the condensation process. The condensation product sbebz was obtained from suberoyl chloride and 2-ethoxybenzamide. The XRD, FT-IR, Raman, and XPS investigated as aspects to identify its structure, purity, and chemical state. The morphological facet was confirmed by SEM and TEM. The morphology data revealed a microrod-shaped morphology of Co (II) CPs with an average particle size 0.7 µm to 1 µm. The pore size, and surface properties were examined by Brunauer-Emmett-Teller (BET) and atomic force microscopy (AFM), revealing a highly large surface area (1076 m2/g), mesoporous and monodisperse nature. The molecular interaction of ligand was estimated using protein molecule. The thermal-decomposition behavior and non-isothermal kinetics of Co (II) CPs were estimated at different heating rates (5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min) under nitrogen atmosphere by thermogravimetry/Derivative thermogravimetry (TG/DTG). As-synthesized Co (II) CPs show enhanced thermal stability compared to the ligand (sbebz). The multiple heating TG/DTG curve exhibits a more or less identical degradation profile/pattern. The kinetic parameters like order of reaction (n), pre-exponential Arrhenius factor (A), activation entropy (∆s), activation energy (Ea), activation free-energy (∆G), and activation enthalpy (∆H) were calculated using Coats-Redfern (CR) method.

Unveiling the impact of nitrocellulose-enveloped nCuO on the thermal characteristics of ammonium nitrate-based solid composite propellants utilizing polyurethane/nitrocellulose blend binders

ABSTRACT This study investigates the combined effects of coated nano copper oxide (NC@nCuO) and polyurethane (PU) modification on the thermal degradation kinetics and combustion properties of ammonium nitrate-based solid composite propellant. Nitrocellulose (NC) is used as a coating for nCuO, forming a core-shell structure, and as a binder in a PU/NC blend. Surface modification of ammonium nitrate was achieved through repeated spray coating. The formulations underwent thorough thermal characterization using thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses. TG analysis showed a significant decrease in thermal degradation temperature due to AN modification with NC@nCuO and the use of PU/NC as a binder. Isoconversional kinetic methods (it-KAS, it-FWO, and VYA/CE) based on DSC tests were used to predict kinetic parameters, revealing a substantial impact of NC-coated nCuO and PU modification on the reactivity of the propellant, reducing the activation energy from 125 kJ/mol (reference) to 99 kJ/mol (nCuO) and 94 kJ/mol (NC@nCuO). Additionally, combustion tests were conducted. The results showed that the introduction of nCuO reduces the ignition delay by 5.25 ms and the combustion duration by 0.06 ms, while NC@nCuO further reduces these by 8.17 ms and 0.12 ms, respectively. Additionally, there is a 23% and 65% increase in flame intensity relative to the reference formulation after the incorporation of nCuO and NC@nCuO, repectively.

Isothermal co‐pyrolytic kinetics investigation of polystyrene/polymethyl methacrylate blended Bakelite

AbstractThe widespread use of Bakelite, polystyrene (PS), and polymethylmethacralate (PMMA) has caused significant pollution, requiring advanced recycling methods. Pyrolysis, co‐pyrolysis, and catalytic co‐pyrolysis are key for recycling these wastes, necessitating kinetic studies and specific reactor designs of their thermal degradation. Isothermal thermogravimetric analysis at 300, 350, 400, 450, and 500°C was used to study thermal degradation kinetics, based on the non‐isothermal degradation zone of Bakelite. The batch pyrolysis of discarded Bakelite and PS/PMMA–Bakelite blends was conducted at 450°C. The thermal decomposition of Bakelite and its blends increases with higher isothermal pyrolytic temperatures. The addition of PS or PMMA to Bakelite substantially accelerates its thermal decomposition. The maximum weight loss of Bakelite, PS–Bakelite, and PMMA–Bakelite are 55%, 96.75%, and 89.51% at 500°C, respectively. The kinetic analysis is crucial for designing specific reactors, utilizing the D1‐diffusion‐based method for Bakelite, with an activation energy (Ea) of 17.178 kJ/mol and Arrhenius constant (A) of 0.095 min−1. The A2‐ and A3‐Avrami–Erofeyev methods explain the isothermal degradation of PS–Bakelite and PMMA–Bakelite blends, with activation energies of 9.031 and 12.59 kJ/mol, and Arrhenius constants of 0.056 and 0.075 min−1, respectively. The co‐pyrolysis of PS–Bakelite yields the highest condensable products (66.76%) and needs the longest reaction time (320 min). The Fourier transform Infrared (FTIR) and gas chromatography–mass spectrometry (GC–MS) analyses confirm the presence of alkanes, cycloalkanes, alkenes, cycloalkenes, aromatic hydrocarbons, and oxygenated compounds in the pyrolytic oils. This study provides unique kinetic parameters and product analyses, showing effects of blending on the decomposition rates and yields valuable compounds, advancing recycling technologies.

Thermal stability and thermal degradation kinetics of urea-formaldehyde resin modified by sodium lignosulfonate

ABSTRACT In this paper, an environmentally friendly urea-formaldehyde resin (UF) was prepared by using sodium lignosulfonate (SL) as a modifier. According to the basic properties of the resin, the strength of the plywood and the formaldehyde emission, the optimum addition amount of SL was determined. At the same time, the thermal curing and thermal degradation behavior of the resin were studied. The results show that the addition of SL can significantly reduce the formaldehyde emission of plywood. When the addition amount of SL was 1%, the wet bonding strength and formaldehyde emission of SL-modified UF (SL-UF) resin were 1.28 MPa and 0.35 mg·L−1, respectively, which were 23% higher and 71% lower than those of UF resin. Moreover, the initial curing temperature of SL-UF resin is lower, but the thermal curing activation energy is higher. SL also has a significant effect on the thermal degradation performance of UF resin. SL is a modifier that can effectively improve the performance of UF.

Study on Thermal Oxygen Aging Characteristics and Degradation Kinetics of PMR350 Resin.

The thermal stability and aging kinetics of polyimides have garnered significant research attention. As a newly developed class of high thermal stability polyimide, the thermal aging characteristics and degradation kinetics of phenylene-capped polyimide prepolymer (PMR350) have not yet been reported. In this article, the thermo-oxidative stability of PMR350 was investigated systematically. The thermal degradation kinetics of PMR350 resin under different atmospheres were also analyzed using the Flynn-Wall-Ozawa method, the Kissinger-Akahira-Sunose method, and the Friedman method. Thermogravimetric analysis (TGA) results revealed that the 5% thermal decomposition temperature (Td5%) of PMR350 in a nitrogen atmosphere was 29 °C higher than that in air, and the maximum thermal degradation rate was 0.0025%/°C, which is only one-seventh of that observed in air. Isothermal oxidative aging results indicated that the weight loss rate of PMR350 and the time-dependence relationship follow a first-order exponential growth function. PMR350 resin thermal decomposition reaction under air atmosphere includes one stage, with a degradation activation energy of approximately 57 kJ/mol. The reaction model g(α) fits the F2 model, and the integral form is given by g(α) = 1/(1 - α). In contrast, the thermal decomposition reaction under a nitrogen atmosphere consists of two stages, with degradation activation energies of 240 kJ/mol and 200 kJ/mol, respectively. The reaction models g(α) correspond to the A2 and D3 models, with the integral forms represented as g(α) = [-ln(1 - α)]2 and g(α) = [1 - (1 - α)1/3]2 due to the oxygen accelerating thermal degradation from multiple perspectives. Moreover, PMR350 resin maintained high hardness and modulus even after thermal aging at 350 °C for 300 h. The results indicate that the resin exhibits excellent resistance to thermal and oxygen aging. This study represents the first systematic analysis of the thermal stability characteristics of PMR350 resin, offering essential theoretical insights and data support for understanding the mechanisms of thermal stability modification in PMR350 and its engineering applications.

Investigation of kinetics, reaction mechanisms, thermodynamics, and synergetic effects in co-pyrolysis of wood sawdust and linear low-density polyethylene using the thermogravimetric approach.

This study focused on investigating thermal degradation behaviors, kinetics, reaction mechanisms, synergistic effects, and thermodynamic parameters of wood sawdust (WSD), linear low-density polyethylene (LLDPE), and their blends (LW1:3, LW1:1, and LW3:1) during co-pyrolysis in a thermogravimetric analyzer (TGA). Thermal behavior exhibited a LW1:3 blend (25 wt.% LLDPE) showing significant mass loss at lower temperatures (150 to 300°C) compared to the individual feedstocks, such as 150 to 400°C and 300 to 520°C for WSD and LLDPE, respectively. The iso-conversional methods (KAS, FWO, and FM) were used to determine the kinetic parameters (Ea and A), and the activation energy drop was highest for the LW1:3 blend. According to the master plots, the third-order reaction (O3), nucleation (P2/3), and diffusional model (D4) were the predominant reaction mechanisms for the co-pyrolysis of the LW1:3, LW1:1, and LW3:1 blend, respectively. The thermodynamic parameters demonstrate that a small amount of plastic addition into WSD can improve the reactivity of the blend, shorten the reaction time, and cause less energy-intensive reactions. The values of ΔH, ΔG, and ΔS also confirmed the co-pyrolysis process's spontaneity and endothermic nature. The Fourier transforms infrared spectrometer (FTIR) spectra of raw feedstock, blends, and their biochar revealed some of the peaks were shifted, the intensity was reduced, and disappearance can happen when the temperature was increased. Using the experimental and theoretical/predicted activation energies, the parity chart illustrates the synergistic effects of co-pyrolysis of different blends, and the LW1:3 blend has a favorable synergistic impact. These results could be helpful in process optimization and designing an effective reactor system for co-pyrolysis.

Influence of polypropylene and high-density polyethylene on isothermal pyrolytic degradation of discarded bakelite: Kinetic analysis and batch pyrolysis studies

The recycling of thermosetting plastics such as discarded bakelite poses greater challenges than thermoplastic polymers like polypropylene (PP) and high-density polyethylene (HDPE), particularly through pyrolysis requiring specialized reactors. This study examines the isothermal thermal degradation kinetics and batch pyrolysis behaviors of bakelite, along with its blends with PP and HDPE, emphasizing the characterization of pyrolytic oils for designing optimized reactors. For the study on isothermal thermal degradation kinetics, isothermal thermogravimetric analysis was performed at specified temperatures (300, 350, 400, 450, and 500°C), chosen based on the predominant non-isothermal degradation behavior of bakelite. The batch pyrolysis of discarded bakelite and blended bakelite with PP/HDPE is carried out at 450°C. The chemical composition analysis of pyrolytic oils is performed using Fourier transform infrared (FTIR) spectroscopy, with comprehensive compound analysis conducted using Gas Chromatography-Mass Spectrometry (GCMS). Isothermal thermogravimetry at temperatures ranging from 300°C to 500°C reveals increased thermal degradation with rising pyrolytic temperatures, reaching maximum weight losses of 55 % for bakelite, 82.74 % for PP-bakelite blends, and 90.8 % for HDPE-bakelite blends at 500°C. The isothermal kinetics study reveals that bakelite degrades via D1-diffusion, polypropylene-blended bakelite via A2-Avrami-Erofeyev, and high-density polyethylene-blended bakelite via A3-Avrami-Erofeyev, with activation energies of 17.178, 7.193, and 3.550 kJ/mol, and Arrhenius constants of 0.095, 0.042, and 0.017 min.−1, respectively. The highest condensable yield of 58.76 % during PP-blended bakelite co-pyrolysis underscores its potential for resource recovery. FTIR and GC-MS confirm the presence of alkanes, cycloalkanes, alkenes, cycloalkenes, aromatic hydrocarbons, and oxygenated compounds in the pyrolytic oils, providing detailed insights into their chemical composition. These findings offer critical insights into the thermal degradation behavior and kinetics of bakelite and polypropylene/high-density polyethylene-blended bakelite, highlighting opportunities for efficient waste plastic utilization through pyrolysis for resource recovery and energy generation, and providing essential knowledge for designing isothermal pyrolysis reactors.

The effects of the interaction between cyanidin-3-O-glucoside (C3G) and walnut protein isolate (WPI) on the thermal and oxidative stability of C3G.

This study explores the interaction between cyanidin-3-O-glucoside (C3G), a water-soluble pigment known for its diverse functional activities, and walnut protein isolate (WPI) as a potential stabilizing agent. Given the inherent instability of C3G, particularly its limited application in the food industry due to sensitivity to thermal and oxidative conditions, this research study aims to enhance its stability. According to the results of the fluorescence quenching experiment, C3G can efficiently quench WPI's intrinsic fluorescence through static quenching. Structural exploration revealed that C3G bound WPI via hydrophobic interaction force, with the number of bound C3G molecules (n) almost equivalent to 1. The ΔG value denoting change in Gibbs free energy for C3G binding with WPI was -8.05 kJ/mol, which indicated that the interaction between C3G and WPI is spontaneous. Moreover, the conformational structures of WPI were altered by C3G binding with a decrease in α-helix contents and an increase in β-turn, β-sheet, and random coil contents. The thermal degradation kinetics indicate that after interacting with WPI, the half-life of C3G increased by 1.62 times and 1.05 times at 80 and 95°C, respectively. The results of the oxidation stability test showed that the presence of WPI effectively reduced the discoloration and degradation of C3G caused by oxidation, and improved the oxidation stability of C3G. This study's findings will help to clarify the interaction mechanism between C3G and WPI, and broaden C3G's application scope in the food processing field.

Effects of novel halogen-free flame-retardant binary additives on thermal stability, degradation kinetics and flame retardancy of cotton cellulose biomacromolecule

The principal component of cotton fibers is the cellulose biological macromolecule. However, its highly flammable nature has significantly constrained its utilization in fields where flame retardancy is essential. Herein, in this work, a highly effective binary composite flame retardant coating (APP/MEL-SWCNHs) with ammonium polyphosphate and modified single-walled carbon nanohorns (MEL-SWCNHs) was chemically attached to cotton fabric. With the add-on of 11.3 %, the treated cotton fabric (APP/MEL-SWCNHs)4 exhibited remarkable flame-retardant and self-extinguishing properties. Its LOI value increased to 23.7 ± 0.1 %, and the damage length was significantly reduced from 30.0 ± 0.1 % cm to 7.9 ± 0.1 % cm compared to the pristine cotton fabric. Despite partial carbonization, (APP/MEL-SWCNHs)4 preserved its original structure. Importantly, in the cone calorimeter test, both the pHRR and THR of (APP/MEL-SWCNHs)4 were drastically decreased by 71.8 % and 35.8 %, respectively. The APP/MEL-SWCNHs coating functioned as a flame retardant by inhibiting the emission of flammable volatiles, releasing non-flammable gases, and encouraging the formation of char layer during combustion. Significantly, thermal degradation kinetic analysis revealed that the third-order kinetic equation (O3) was found to have the strongest correlation with (APP/MEL-SWCNHs)4 in both air and N2 atmospheres. The higher activation energy (E) for (APP/MEL-SWCNHs)4 confirmed that incorporating MEL-SWCNHs improved the thermal stability of the char layer.

Investigation of thermal, optical properties, AC conductivity and broadband dielectric spectroscopy of poly(ethyl methacrylate)/poly(vinyl chloride) polymer blend

This work reports the structural, thermal, optical and electrical properties of PEMA, PVC and their polyblends. These properties are investigated by FTIR, TGA, UV/Vis and broadband dielectric spectroscopy. FTIR spectra showed that the characteristic bands of PEMA and PVC are affected by blending and displayed red and blue shifts confirming that an intermolecular interaction between PEMA and PVC is occurred. Thermal degradation kinetics of PEMA, PVC and its polyblend samples is investigated in details and the thermal properties of each decomposition stage are estimated. UV measurements analysis revealed that Urbach energy (EU) is increased while optical bandgap decreased upon increasing the PVC content. The indirect and direct band gap (Eig/Edg) values are decreased from (3.95/4.21) to (3.10/3.92) eV. Also, upon increasing the content of PVC, the lattice dielectric constant (εL) is increased from 2.71 to 7.83. Wemple-DiDomenico model is applied for investigating the refractive index dispersion and to calculate the oscillator and dispersion energies. It is observed that the linear/nonlinear parameters are increased nonlinearly with increasing the PVC content. χ(1), χ(3) and n2 values are found to increase from 0.104, 0.213 × 10−13 and 4.01 × 10−12 to 0.363, 31.26 × 10−13 and 5.33 × 10−12. These results make PEMA/PVC polyblend strong candidates for use in the development and design of advanced optoelectronic devices. AC conductivity (σac) and dielectric measurements are carried out at various temperatures in wide frequency range. Jonscher power law is applied and showed that the predominant conduction mechanism in our samples is overlapping large-polaron tunneling (OLPT). The dielectric constant and electrical impedance are found to be frequency and temperature dependent. The investigation of the electric modulus (M*) revealed that M′ is increased non-linearly with increasing the frequency, while M″ spectra displayed two different modes of relaxation. The interfacial polarization (IP) is observed in low frequency region, while, dipolar relaxation is detected in high frequency region.

Conversion of palm kernel shell to sustainable energy and the effect of wet synthesized nanoparticles of iron on its thermal degradation kinetics

Pisifera Palm kernel shells (PPKS) were torrefied at 260, 280, and 300 °C, and ASTM methods were used to determine variations in their ultimate and proximate parameters. Iron nanoparticles were synthesized via coprecipitation of FeCl3.6H2O and NaBH4, characterized, and used as catalysts in the thermal degradation of torrefied PPKS. Torrefied PPKS samples showed moderate MC (9.26–10.73 %), high carbon content (46.74 %), AC (2.77–3.39 %), VM (49.48–54.12 %), and FC (31.76 %–38.49 %). At 300 °C, the calorific value of the untreated PPKS increased by 13.3 % to 18.02 kJ/mol, making it suitable as a solid fuel. An increase in heating rate enhances faster decomposition and higher devolatization of torrefied PPKS at lower temperatures. Hemicellulosic components degrade at a reduced temperature as compared to cellulosic and lignin components. The 47.58 % Fe in the nanoparticle made it a good catalyst for the thermal degradation of PPKS. The Ea expended on catalyzed torrefied PPKS was lower as compared to torrefied PPKS calculated via the Coats-Redfern kinetic model. Torrefaction improved untreated PPKS by achieving higher fuel quality and calorific value, suitable physical properties, and a suitable chemical composition. The nano-Fe was suitable to reduce Ea needed for the thermal degradation of torrefied PPKS.

Combustion characteristics and thermal degradation kinetics of microporous triazine-based organic polymers: the role of organic linkers

Combustion characteristics and thermal degradation kinetics of microporous triazine-based organic polymers: the role of organic linkers

Insights into the oxidative thermal stability of mesoporous triazine‐based organic polymers: Kinetics and thermodynamic parameters

AbstractThis study investigates the thermal degradation kinetics of mesoporous triazine‐based polymers, namely triazine‐amine and triazine‐ether polymers. The synthesis, physicochemical characterization, and catalytic applications of these polymers were discussed in our previous report. Herein, the thermal stability parameters, including kinetic triplets and thermodynamic parameters, were determined using thermogravimetric analysis (TGA) and non‐isothermal mathematical approximations such as Coats‐Redfern, Broido, and Horowitz–Metzger methods. Triazine‐ether polymers exhibit thermal stability within the range of 200°C–300°C, while triazine‐amine polymer demonstrates superior thermal stability, reaching up to 450°C. According to the Coats‐Redfern method, the degradation follows reaction orders of 0.5 ≤ n ≤ 1. The activation energy of triazine‐amine polymer is notably high, particularly at the third degradation stage (e.g., 89.0 kJ/mol by the Broido method), attributed to its high nitrogen content. Conversely, the higher carbon content of triazine‐ether polymers reduces their activation energy to approximately 30 kJ/mol at all stages and thus, facilitates the degradation process. Thermodynamically, the degradation process is favorable yet non‐spontaneous, with intermediate states of the polymers exhibiting higher entropy, indicative of their enhanced degradation capability.