Thermal Decomposition Behavior Research Articles

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.

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.

Influences of the Decomposition Atmosphere and Heating Rate on the Pyrolysis Behaviors of Resin Sand

The pouring of sand casting is accompanied by severe heat conduction, and there is an urgent need to investigate the pyrolysis properties of foundry sand. The main purpose of this study was to investigate the pyrolysis behaviors of resin sand, including precoated sand (PCS), hot box sand (HBS), and warm box sand (WBS), at heating rates of 20 °C/min, 30 °C/min, and 40 °C/min in nitrogen and air atmospheres. The mass loss of the resin sand was monitored continuously with a simultaneous thermal analyzer, and the kinetic parameters of the resin sand were calculated based on the Coats–Redfern method and thermal data. The average mass loss of the resin sand during pyrolysis was 3.03%, which was much smaller than that of the other sands. The volatile release characteristic index of resin sand could not be calculated based on this concept. To solve this issue, the term Tstv/mloss was established, and its value was determined. With increasing heating rates from 20 °C/min to 30 °C/min and from 30 °C/min to 40 °C/min, the mass losses of the resin sand increased by 0.79% and 0.64%, respectively, and the volatile release characteristic indices of the resin sand increased by 3.8 × 10−10 and 1.06 × 10−9, respectively. In addition, the mass losses and volatile release characteristic indices of resin sand in an air atmosphere were greater than those in a nitrogen atmosphere. With increasing heating rate, the activation energy of the resin sand decreased in a nitrogen atmosphere. The findings concerning the thermal decomposition behaviors of resin sand provided a theoretical basis for the pouring step of the sand casting process.

Analytical Pyrolysis of Soluble Bio-Tar from Steam Pretreatment of Bamboo by Using TG-FTIR and Py-GC/MS.

Steam pretreatment at high temperatures enables fresh bamboo to possess antifungal and antiseptic properties. The process produces a large amount of wastewater that urgently needs to be recycled. Soluble bio-tars derived from wastewater under low-temperature (LTS-tar) and high-temperature (HTS-tar) steam pretreatments of moso bamboo were studied with a thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS). Thermogravimetric analysis showed that in the three stages of the thermal decomposition process, the final residue of the bamboo and HTS-tar had two main peaks of 0.88 wt% and 6.85 wt%. The LTS-tar had much more complicated thermal decomposition behavior, with six steps and a high residue yield of 23.86 wt%. A large quantity of CH4 was observed at the maximum mass loss rates of the bamboo and bio-tars. Acids, aldehydes, ketones, esters, and phenolic compounds were found in the pyrolysis products of the bamboo and soluble bio-tars. Both bio-tars contained carbohydrates and lignin fragments, but the LTS-tar under mild steam conditions had more saccharides and was much more sensitive to temperature. The lignin in the bamboo degraded under harsh steam conditions, resulting in high aromatic and polymeric features for the HTS-tar. The significant differences between LTS-tar and HTS-tar require different techniques to achieve the resource utilization of wastewater in the bamboo industry.

Cure Kinetics and Thermal Decomposition Behavior of Novel Phenylacetylene-Capped Polyimide Resins.

Based on a novel phenylacetylene capped polyimide (PI) with unique high-temperature resistance, its curing kinetics and thermal decomposition behavior were investigated. The curing mechanism and kinetics were studied by differential scanning calorimetry (DSC), and the activation energy (Ea) and pre-exponential factor (A) of the curing reaction were calculated based on the Kissinger equation, Ozawa equation, and Crane equation. According to the curve of conversion rate changing with temperature, the relationship between the dynamic reaction Ea and conversion rate (α) was calculated by the Friedman equation, Starink equation, and Ozawa-Flynn-Wall (O-F-W) equation, and the reaction Ea in different stages was compared with the results of molecular dynamics. Thermogravimetric analysis (TGA) and a scanning electron microscope (SEM) were used to analyze the thermal decomposition behavior of PI resins before and after curing. Temperatures at 5% and 20% mass loss (T5%, T20%), peak decomposition temperature (Tmax), residual carbon rate (RW), and integral process decomposition temperature (IPDT) were used to compare the thermal stability of PI resins and cured PI resins. The results display that the cured PI has excellent thermal stability. The Ea of the thermal decomposition reaction was calculated by the Coats-Redfern method, and the thermal decomposition behavior was analyzed. The thermal decomposition reaction of PI resins at different temperatures was simulated by molecular dynamics, the initial thermal decomposition reaction was studied, and the pyrolysis mechanism was analyzed more comprehensively and intuitively.

Comparative assessment of failure in single shear lap joints fabricated using various joining techniques

The current research endeavour reports the performance of single shear lap joints of flax/PP composite laminates. The joints were fabricated using mechanical joining, fusion bonding (ultrasonic and hot plate joining), and hybrid joining techniques (mechanical/ultrasonic joining and mechanical/hot plate joining). In case of the mechanical and hybrid joining, the effect of the bolt size, and number of bolts (single and double) on the tensile failure load was investigated. Pertaining to mechanical joining, the large bolt size and double bolts recorded higher tensile failure load compared to smaller bolt size and single bolt, respectively. Whereas with double bolts, no increase in the tensile failure load was observed for the hybrid joints, due to reduction in bonded area. The hybrid joints (mechanical/ultrasonic) recorded the maximum tensile failure load compared to all other type of joints. The load-extension behaviour and failure of joints was also examined. Expect mechanical joints, all other joints exhibited structural type of failure. In contrast, the mechanical joints resulted in a net-tension failure mode with failure line passing through the hole. However, the thermal decomposition and crystalline behaviour (XRD spectra) of developed joints did not vary significantly. The morphology of failed joints was examined using scanning electron microscope.

Plant-Assisted Green Synthesis of MgO Nanoparticles as a Sustainable Material for Bone Regeneration: Spectroscopic Properties.

This work is devoted to magnesium oxide (MgO) nanoparticles (NPs) for their use as additives for bone implants. Extracts from four different widely used plants, including Aloe vera, Echeveria elegans, Sansevieria trifasciata, and Sedum morganianum, were evaluated for their ability to facilitate the "green synthesis" of MgO nanoparticles. The thermal stability and decomposition behavior of the MgONPs were analyzed by thermogravimetric analysis (TGA). Structure characterization was performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-Vis), dynamic light scattering (DLS), and Raman scattering spectroscopy (RS). Morphology was studied by scanning electron microscopy (SEM). The photocatalytic activity of MgO nanoparticles was investigated based on the degradation of methyl orange (MeO) using UV-Vis spectroscopy. Surface-enhanced Raman scattering spectroscopy (SERS) was used to monitor the adsorption of L-phenylalanine (L-Phe) on the surface of MgONPs. The calculated enhancement factor (EF) is up to 102 orders of magnitude for MgO. This is the first work showing the SERS spectra of a chemical compound immobilized on the surface of MgO nanoparticles.

Preparation, characterization, and combustion properties of NGO/GF/B composite system

Boron is a potential fuel for energetic materials due to its high volumetric and gravimetric energy density. However, its application has long been constrained by ignition difficulties and insufficient combustion. In this study, a mixture of NGO and GF was introduced as an additive to boron particles. We prepared NGO/GF-coated B complexes and performed several characterizations, showing that NGO combined with GF had a good coating effect on B. The combustion heat was measured by an oxygen bomb calorimeter, while the combustion mechanism was proposed. Its effect on the thermal decomposition behavior of AP was also analyzed. The results showed that the combustion efficiency of NGO/GF-modified B was significantly improved, which was 14.34% higher than that of pure B. This enhancement was attributed to the synergistic effect of NGO and GF, which promoted ignition and combustion by releasing heat, gases, and fluorocarbon radicals. In addition, both boron and NGO/GF-modified boron accelerated the decomposition of AP, especially, in the presence of NGO/GF, the decomposition temperature of AP was advanced by 73.2 °C compared to that in the presence of boron alone. These findings may provide valuable theoretical guidance for the design and potential application of NGO/GF modified boron in energetic materials.

Thermodynamics and energy properties of the lowest eutectic mixture of TNBA/MTNP

In light of the challenges posed by the low density, diminished energy levels, and shrinkage holes in the loading arise of the current cast-cured explosive liquid vehicle, TNT, the investigation of low-melting eutectic materials as potential substitutes for TNT has emerged as a focal point of research. By employing the solvent-nonsolvent method, the lowest eutectic mixture of TNBA(2,4,6-trinitro-3-bromoanisole)/MTNP(1-methyl-3,4,5-trinitropyrazole) was synthesized, distinguished by a moderate melting point and markedly elevated energy levels as compared to TNT. Comprehensive SEM, EDS, IR, XRD, and XPS analyses were conducted on the lowest eutectic mixture, substantiating the absence of any chemical interaction between TNBA and MTNP and affirming their exceptional compatibility. Moreover, an exploration into the thermal decomposition behavior and mechanism of the lowest eutectic mixture was undertaken, its mechanical sensitivity was tested, and its detonation performance was evaluated by EXPLO-5 software. The thermal decomposition parameters of the lowest eutectic mixture closely paralleled those of the precursor materials, with the thermal decomposition kinetics model function being identified as the Jander function. The impact sensitivity of the lowest eutectic was 48.1 cm and the friction sensitivity was 12%. Furthermore, the density of the lowest eutectic mixture surpassed 1.8 g/cm3, and its detonation velocity approached 8000 m/s, markedly surpassing the explosive performance of TNT.

Thermal decomposition behavior of Mountain Pass rare earth concentrate in air/CO2 atmosphere

The Mountain Pass mine is recognized as one of the world’s primary sources of rare earth minerals. These rare earth minerals mainly consist of bastnaesite and a small amount of monazite phosphate, which cannot be decomposed and recovered through conventional oxidative roasting and hydrochloric acid leaching process. An efficient, clean, and economical process called the "combined method" was proposed for the utilization of the Mountain Pass mine to extract rare earths from Mountain Pass rare earth concentrate (MPREC). The main steps of this process include weak oxidation atmosphere roasting, step leaching of hydrochloric acid, solid-liquid separation, the monazite slag with sulfuric acid roasting water leaching, etc. In this paper, the roasting process of MPREC under a weak oxidation atmosphere was investigated. The study examines the thermal decomposition kinetics, phase transition process, and leaching behavior of MPREC in air/CO2 atmosphere. Results show that, the activation energy (Ea) for MPREC thermal decomposition in air and CO2 atmosphere are 146 and 320 kJ/mol, respectively. At temperature above 500 °C in air or above 700 °C in CO2 atmosphere, REOF are generated from bastnaesite through an in-situ reaction with CaO, which is decomposed from CaCO3, to form CaF2 and rare earth oxide (REO). Thus, F is regulated into solid phase. In an oxidizing atmosphere, the thermal decomposition of bastnaesite is accompanied by the rapid oxidation of Ce(Ⅲ). In contrast, the oxidation of Ce(Ⅲ) in a CO2 atmosphere is significantly inhibited. At 700 °C, the oxidation rate of Ce in air is 74.09%, while in a CO2 atmosphere, it is only 33.83%. The hydrochloric acid leaching experiment shows that, the leaching rate of rare earth after roasting at 600 °C under an air atmosphere reaches to 82.9%, and it reaches 87% after roasting at 800 °C under a CO2 atmosphere. The reduction of Ce oxidation in a weak oxidizing atmosphere significantly improves the leaching rate of Ce.

Thermal Decomposition and Combustion Analysis of Malaysian Peat Soil Samples Using Coats Redfern Model-free Method

This research investigates the thermal decomposition behaviour of Malaysian peat soil through thermogravimetric analysis at varying heating rates. The study aims to analyse the thermal kinetics of decomposition for distinct peat soil types under inert and oxidative atmospheres while considering the role of available oxygen. The investigation encompasses virgin and agricultural peat, employing a non-isothermal thermogravimetric analysis technique to evaluate thermal decomposition characteristics and compute kinetic parameters using the Coats Redfern model-free approach. The pyrolysis profiles reveal three primary stages: moisture evaporation (30–180°C), organic component decomposition (200–500°C), and mineral decomposition (600–800°C). Virgin peat experiences a 43% mass loss during pyrolysis, while agricultural peat shows a 46% mass loss, emphasising insights into thermal behaviour and consistent decomposition patterns across peat types. Combustion profiles exhibit three main stages: dehydration (30–180°C), oxidative pyrolysis transforming organic matter into volatiles and char (200–300°C), and subsequent char oxidation (300–500°C). The study determines average activation energy trends, measuring 14.87 kJ/mol for virgin peat and 5.37 kJ/mol for agricultural peat under an inert atmosphere, and 28.89 kJ/mol for virgin peat and 36.66 kJ/mol for agricultural peat under an oxidative atmosphere. The research introduces an innovative two-step reaction model elucidating peat thermal decomposition kinetics (excluding dehydration), including a discussion on the impact of oxygen availability on kinetic parameters. These findings essential peat fire smouldering modelling, contributing to peat combustion behaviour for effective strategies to reduce peat fire risks.

Insight into the Types of Alkanolamines on the Properties of Copper(II) Formate-Based Conductive Ink.

Conductive inks are one of the most important functional materials for printed flexible electronic devices, and their properties determine the methods of subsequent patterning and metallization. In comparison with copper nanoparticle or nanowire inks, copper particle-free inks employing copper(II) formate (Cuf) as a precursor have attracted the interest of researchers due to their flexibility in preparation, excellent stability, and lower conversion temperature. Alkanolamines can provide Cuf with excellent solubility in alcohols while being less toxic and having a certain reducibility, making them preferable ligands in comparison with aliphatic amines and pyridine. However, there have been few studies on the effects of the alkanolamine types on the performance of Cuf inks. Also, the decomposition mechanism of copper-alkanolamine complex inks is not clear. In this work, different kinds of alkanolamines were chosen as ligands to formulate Cuf inks to address the mentioned issues. The influences of amine types on the stability, wettability, thermal decomposition behavior, and electrical performance of the formulated Cuf particle-free inks were investigated in detail. The results show that the utilization of alkanolamines could provide Cuf with excellent solubility in alcohols, resulting in an ink with good stability and favorable wetting properties. The thermal decomposition temperature and electrical performance of the formulated copper ink are largely dependent on the amine used. When amines with a longer carbon chain and more branches were utilized to prepare the ink, a decreased decomposition temperature was observed on the derived inks because of the steric hindrance effect. Copper films with good morphology and conductivity could be obtained at low temperatures by selecting the appropriate alkanolamine. Copper particle-free conductive ink from 2-amino-2-methyl-1-propanol demonstrated better morphology and electrical performance (16.09 μΩ·cm) and was successfully used for conductive circuits by direct-writing.

An Experimental Analysis of a Nuclear-Grade Cable Based on Fire Combustion Characteristics and Pyrolysis Behavior

Nuclear power fire protection is an important part of nuclear safety, and strengthening fire protection technology research is essential for improving nuclear safety and fire protection. The operating platform inside a containment structure is one important element in fire risk evaluation in nuclear power plants. In this paper, a combustible nuclear-grade cable in a fire scenario was firstly selected as the research object, and then the nuclear-grade cable was separately subjected to a combustion test as well as a thermogravimetric test in order to obtain the relevant thermal parameters, which provide more accurate data support for the establishment of a cable fire development and spread model. The nuclear-grade cable material data obtained from the test were compared with a civil PVC cable in order to conduct a specific analysis of the fire risk of nuclear-grade cables. This study shows that the effects of different heating rates and heating atmospheres on the thermal decomposition behavior of cable materials are meaningful and helpful in understanding whether the materials will undergo combustion processes at high temperatures and whether fire spread will occur.

Investigating Thermal Decomposition Kinetics and Thermodynamic Parameters of Hydroxyl-Terminated Polybutadiene-based Energetic Composite

Background: Hydroxyl-Terminated Polybutadiene (HTPB)-based energetic compositions have been developed for enhanced blast energetic composite, composite rocket propellant formulations, metal cutting, demolition, welding and explosive reactive armour in civil and military applications. The types and choice of curing agents are crucial in enhancing the mechanical and structural integrity of the binder. To understand the stability and safety of energetic composites for potential applications, it is necessary to understand the thermal decomposition kinetics and thermodynamic parameters clearly. Objective: The main objective is to study the decomposition kinetic and thermodynamic parameters of energetic composites cured by different curing agents. Methods: A series of energetic composites based on HMX (1,3,5,7-tetranitro-1,3,5,7- tetrazocane) and HTPB-based binder system cured with various curing agents were prepared by the cast cured method. The curatives, namely MDI (4,4’-methylene diphenyl diisocyanate), IPDI (isophorone diisocyanate), TDI (toluene dissocyanate) and TMDI (2,2,4-trimethylhexamethylene diisocyanate) were used. The thermal analysis method was employed to investigate the thermal decomposition characteristics, which are closely associated with the thermal stability and safety considerations during handling, processing, and storage. The kinetic parameters for thermal decomposition reactions were studied by employing the Flynn-Wall-Ozawa method. The thermodynamic parameters of the activation enthalpy, activation Gibbs energy free and activation entropy of all energetic composites were also determined by the theory of activated complex. Results: The thermogravimetric results show that the thermal stability is almost similar for all composites cured with the different types of curing agents. The average activation energy of the energetic composites cured with IPDI, MDI, TMDI and TDI was 207.5, 237.3, 243.3 and 187.6 kJ/mol, respectively. The thermodynamic parameters for the thermal decomposition process show that they are generally thermodynamically stable and non-spontaneous. Scanning electron microscope (SEM) micrographs of all the samples clearly indicate that HMX crystals are well embedded in the polymer matrices. result: The thermogravimetric results show that the thermal stability and thermal decomposition behaviour do not change significantly by varying the type of the curing agent in the HTPB-based binder. The SEM micrographs of all the samples clearly indicate that HMX crystals are well embedded in the polymer matrices. The averaged activation energy for the HMX/HTPB/MDI, HMX/HTPB/IPDI, HMX/HTPB/TDI and HMX/HTPB/TMDI samples obtained from FO method was 237.3, 207.5, 187.6 and 243.3 kJ/mol, respectively. The thermodynamic parameters including the activation enthalpy, activation Gibbs free energy and activation entropy for the thermal decomposition process show that they are generally thermodynamically stable and non-spathaceous. Conclusion: The thermal stability of all energetic composites is almost constant. The activation energy of the prepared energetic composites is significantly varied with varying the type of curing agents in the HTPB-based binder system. The thermodynamic parameters indicate that composites possess superior stability and thermal safety. The SEM micrographs indicate that HMX crystals of prepared composites are embedded in the polymer matrix.

Tuning combustion and energy in hydroxylammonium nitrate (HAN)-based electrically controlled solid propellant

Solid propellants have been widely applied due to its high energy, rapid reaction, easy storage and convenient equipment. However, the further development of solid propellants has been hindered by the challenges associated with controlling their combustion process. In this research, we presented an electrically controlled solid propellant (ECSP), and its burning rate could be continuously adjusted with voltage. We investigated thermal decomposition behavior and gaseous products of ECSP using thermogravimetry–differential scanning calorimetry-mass spectrometry (TG-DSC-MS). The solid products were analyzed through energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Based on the thermal decomposition behavior, gaseous products, and solid products, it was found that the thermal decomposition process could be divided into two stages: decomposition of ammonium nitrate (AN) and interactions between hydroxylamine nitrate (HAN) and other substances. The electrochemical impedance spectroscopy (EIS) experiments revealed that the electrical conductivity of ECSP increased with the pressure. Significantly, the peak combustion pressure of propellant increased by the rise of voltage from 3.17 MPa (150 V) to 5 MPa (250 V) in closed bomb. In addition, electricity reinforced the burning rate and powder force of propellant. Additionally, the electricity simultaneously affects electric and thermal decomposition processes. Electricity is used to control the burning rate and the total energy produced by propellant combustion. The characteristics of controllable energy has the potential to achieve controllable range of weapons, providing a new direction for development of smart weapons.

Thermal chemistry and decomposition behaviors of energetic materials with trimerizing furoxan skeleton

AbstractTrimerizing furoxans are ideal molecular skeletons for the construction of high energetic substances due to their compact structures and high enthalpy of formations. To explore and compare the thermal behaviors of energetic materials with tandem trimerizing furoxan molecular skeleton, we reported the first systematic research on the thermochemical behaviors and decomposition mechanism of 3,4‐bis(3‐fluorodinitromethylfuroxan‐4‐yl)furoxan (BFTF), 3,4‐bis(3‐cyanofurazan)furazan oxide (BCTFO) and benzotrifuroxan (BTF). According to the research results of the DSC‐TG experiments, both the substituted furoxan based energetic compounds (BCTFO and BFTF) exhibited low melting points and complicated thermal decomposition behaviors around 240 °C, while the melting point of unsubstituted furoxan (BTF) was much higher. Their detailed decomposition mechanisms were proposed based on the experimental results through tandem techniques including in‐situ FTIR spectroscopy method and DSC‐TG‐FTIR‐MS quadruple technology, which indicated that the cleavage of substituent would trigger the decompositions of BFTF and the decomposition of trimerizing furoxan skeletons almost synchronous occurrence with substituents in BCTFO. The self‐oxidation‐reduction of the linear and annular trimerizing furoxans lead to similar decomposition fragmented small molecule products.

Preparation of a series of metal-organic-framework-199 (Cu) and their catalytic effect on the decomposition of hexahydro-1,3,5-trinitro-s-triazine

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

Investigation into the Performance Enhancement of Calcium Phosphate Mineralization-Compacted Chinese Fir

The utilization of wood as a construction material offers inherent advantages, including its renewability, good process property, wide availability, and carbon sequestration. However, its susceptibility to combustion and limited mechanical properties also constrain its applications. In this work, calcium phosphate was in situ deposited in dignified Chinese fir wood, followed by hot-pressed densification. Thermogravimetric analysis (TG) reveals that mineralization and densification alleviate the thermal decomposition and combustion behavior of wood, which greatly promotes the formation of the dense char layer during wood combustion. Therefore, the maximum heat release rate (HRR), total heat release rate (THR), and total smoke production rate (TSP) of the as-prepared mineralized dense wood were significantly reduced by 37%, 32%, and 56% compared with the control one. Further, the mineralized dense wood showed a remarkable enhancement in flexural strength and flexural modulus of elasticity, 203% and 220% higher than the natural wood, respectively. This study demonstrated a straightforward and eco-friendly approach to fabricating structural wood possessing exceptional flame retardancy and mechanical characterization, which holds immense potential for application in energy-efficient green buildings.