Facile preparation of Fe/N-based biomass porous carbon composite towards enhancing the thermal decomposition of DAP-4

Fe/N-based biomass porous carbon composite(Fe/N-p Carbon) was prepared by a facile high-temperature carbonization method from biomass,and the effect of Fe/N-p Carbon on the thermal decomposition of energetic molecular perovskite-based material DAP-4 was studied.Biomass porous carbonaceous materials was considered as the micro/nano support layers for in situ deposition of Fe/N precursors.Fe/Np Carbon was prepared simply by the high-temperature carbonization method.It was found that it showed the inherent catalysis properties for thermal decomposition of DAP-4.The heat release of DAP-4/Fe/N-p Carbon by DSC curves tested had increased slightly,compared from DAP-4/Fe/N-p Carbon-0.The decomposition temperature peak of DAP-4 at the presence of Fe/N-p Carbon had reduced by 79°C from384.4°C(pure DAP-4) to 305.4°C(DAP-4/Fe/N-p Carbon-3).The apparent activation energy of DAP-4thermal decomposition also had decreased by 29.1 J/mol.The possible catalytic decomposition mechanism of DAP-4 with Fe/N-p Carbon was proposed.

Non-isothermal thermal decomposition kinetics of high iron gibbsite ore based on Popescu method

The thermal decomposition kinetics of high iron gibbsite ore was investigated under non-isothermal conditions.Popescu method was applied to analyzing the thermal decomposition mechanism.The results show that the most probable thermal decomposition mechanism is the three-dimensional diffusion model of Jander equation,and the mechanism code is D3.The activation energy and pre-exponential factor for thermal decomposition of high iron gibbsite ore calculated by the Popescu method are 75.36 kJ/mol and 1.51×10-5 s-（-1）,respectively.The correctness of the obtained mechanism function is validated by the activation energy acquired by the iso-conversional method.Popescu method is a rational and reliable method for the analysis of the thermal decomposition mechanism of high iron gibbsite ore.

Thermal decomposition effect of MgCo_(2)O_(4)nanosheets on ammonium perchlorate-based energetic molecular perovskites

Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH_4ClO_4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate （AP） decomposition was investigated by differential scanning calorimetry （DSC）. The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 - 350 ℃ and 400 - 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g^- 1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7℃ by reduction of 114.6℃ and increases the apparent decomposition heat from 515 to 1240 J·g^-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Effect of preparation methods on Pt/alumina catalysts for the hydrogen iodide catalytic decomposition

Three kinds of Pt/alumina catalysts were prepared by impregnation-hydrogen reduction, impregnation-hydrazine reduction and electroless plating methods. Their differences in the structures, specific areas and particle sizes were characterized by XRD, BET and TEM, respectively. Furthermore, their catalytic activities for the hydrogen iodide （HI） decomposition were evaluated in a fixed bed reactor. The results show that the catalyst 5%Pt/Al2O3 prepared by the electroless plating has the optimum catalytic properties for HI decomposition owing to the high dispersion of the platinum nano-particles （〈5 nm） on the alumina supports.

Salt-Assisted Combustion Synthesis of NdCoO_3 Nanoparticles and Their Catalytic Properties in Thermal Decomposition of Ammonium Perchlorate

Highly dispersed perovskite NdCoO3 nanoparticles were prepared by a novel salt-assisted combustion process. The effects of NaCl content and calcination temperature on the characteristics of the products were characterized by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and BET surface area measurement. The facile introduction of NaCl in the conventional combustion synthesis process was found to result in the formation of well-dispersed perovskite nanoparticles and increase specific surface areas of the resultants from 1.7 to 43.2 m2·g-1. The catalytic properties of the typical NdCoO3 samples for thermal decomposition of ammonia perchlorate (AP) and their correlation with the NdCoO3 microstructure were investigated by Differential Scanning Calorimetry (DSC). The DSC results indicate that the addition of the amorphous NdCoO3 nanoparticles to AP incorporates two small exothermic peaks of AP into a strong exothermic peak, decreases the temperature of the AP exothermic peak to 314.0 ℃ by reduction of 138.3 ℃ and increases the apparent decomposition heat from 515 J·g-1 to over 1441 J·g-1, showing the intense catalytic activity for thermal decomposition of AP. It is also clear that the catalytic activity of the resultant NdCoO3 is related to their microstructure. According to Kissinger′s method, the kinetics parameters of the thermal decomposition of AP catalyzed by the as-prepared NdCoO3 samples were calculated to account for the order of their catalytic activity.

Reaction pathway and kinetics of CdO nanoparticles prepared from CdCO_3 precursor using thermal decomposition method

The non-isothermal kinetics of CdO nanoparticles prepared from CdCO3 precursor using thermal decomposition method was investigated. A model-fitting Malek approach and a model-free advanced isoconversional method of Vyazovkin were applied to the analysis of the DSC and TGA data. The results showed that CdO nanoparticles prepared from CdCO3 followed an autocatalytic reaction. Sestak–Berggren model could favorably describe the studied reaction process. Moreover, the apparent activation energy of CdCO3 decomposition was calculated to be (119.19±9.97) kJ/mol and the explicit rate equation form of CdCO3 decomposition was established.

Progress on the application of graphene-based composites toward energetic materials:A review

Carbon material is an important additive in energetic materials.Graphene is a monolayer carbon material in which carbon atoms are arranged in two-dimensional honeycomb structure,who has special optical,electrical,and mechanical properties.Recently,the application of graphene-based composites in energetic materials has received extensive attention.This review mainly summarizes the applications of graphene and graphene-based nanomaterials in energetic materials.The effects of these materials on the thermal stability,sensitivity,mechanical property,ignition and combustion of energetic materials were discussed.Furthermore,the progress of functionalized modification of graphene has been summarized,including covalent bonding modification and doping modification.These studies show that graphenebased materials exhibit excellent performances and might emerge as promising candidate for energetic materials.

Effect of inorganic salt on the thermal degradation of nitrocellulose and reaction mechanism of its mixture

In this study,to better understand the reaction mechanism between inorganic salts and nitrocellulose,CaCO_(3) and Li_(2)CO_(3) were evaluated with respect to their effects on the thermal degradation of NC in nitrogen atmosphere using TG/DSC at three different heating rates(2,5,10 K/min).The numerical relationship between activation energy(E)and conversion rate was obtained by FWO and KAS method,and it was discovered that CaCO_(3) could improve the thermal stability of NC.Activation energy values were calculated by Kissinger method,and it was found that NC that contain Li2CO3had the highest activation energy while NC containing CaCO3had the lowest E value.By combining the thermal analysis data with Malek method,the most probable mechanism model of thermal degradation is obtained as Sesták-Berggren model,which expression is f(α)=α^(m)(1-α)^(n).As a result of this study,there are certain guiding principles that can be applied to the pyrolysis reaction model and to the actual production process of nitrocellulose.

Synthesis of Co Nanoparticles and Their Catalytic Effect on the Decomposition of Ammonium Perchlorate

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.

Thermal Stability and Thermal Decomposition Kinetics of 1-Butyl-3-methylimidazolium Dicyanamide

Thermal stability and thermal decomposition kinetics of 1-butyl-3-methylimidazolium dicyanamide ([bmin+][N(CN) ]2-) were investigated using both isothermal and non-isothermal thermogravimetric analyses (TGA) under high pure nitrogen as carrier gas. The long-term thermogravimetric studies revealed that the highest temperature used should be 110 °C, at which [bmin+][N(CN)2-] lost less than 10% by mass in 10 hours. The non-isothermal activation energy values determined using Friedman and ASTM methods were (150±13) and (147±2) kJ·mol –1 , respectively. Multivariate non-linear-regression methods showed that expanded Fn and CnB models were the best fit models with highest correlation coefficient of 0.9994, and the apparent activation energies were consistent with iso-conversional methods.

Study on Non-Isothermal Decomposition Kinetics of Ephedrini Hydrochloridum

The thermal decomposition processes of ephedrini hydrochloridum and its kinetics are studied by TG-DTG techniques. A combined method, which includes Achar method, Coats-Redfera method, and Ozawa method, is put forward for determining kinetic model under non-isothermal conditions. By applying the combined method, it is determined that the thermal decomposition of ephedrini hydrochloridum is subjected to cylindrical symmetric diffusion. And the reaction function isƒ(α)=2(1-α)?, apparent activation energy (115.26±3.55) kJ·mol−1, pre-exponential factor 4.62×108 s−1. Results show that the combined method is feasible and simple.

Efficient destruction of sodium cyanide by thermal decomposition with addition of ferric oxide

Efficient destruction of cyanide by thermal decomposition with ferric oxide addition was proposed. The mechanism of destruction of sodium cyanide with or without ferric oxide addition under various conditions was examined by XRD, DSC-TG, and chemical analysis technologies. In the absence of ferric oxide, sodium cyanide decomposes at 587.4 ℃ in air and 879.2 ℃ in argon atmosphere. In the presence of ferric oxide, about 60% of sodium cyanide decomposes at 350 ℃ for 30 min in argon, while almost all sodium cyanide decomposes within 30 min in air or O2 with mass ratio of ferric oxide to sodium cyanide of 1:1. The increase of ferric oxide addition, temperature, and heating time facilitates the destruction of sodium cyanide. It is believed that with ferric oxide addition, NaCN reacts with Fe2O3 to form Na4Fe(CN)6, Na2CO3, NaNO2 and Fe3O4 in argon. NaCN decomposes into NaCNO, Na4Fe(CN)6, minor NaNO2, and the formed NaCNO and Na4Fe(CN)6 further decompose into Na2CO3, CO2, N2, FeOx, and minor NOx in air or O2.

Thermal Decomposition Kinetics of Abietic Acid in Static Air

The thermal decomposition of abietic acid in air was investigated under non-isothermal condition using thermogravimetric analysis-differential thermal analysis （TGA-DTA） technique with heating rates of 5, 10, 15 and 25 K.min-~. The non-isothermal kinetic parameters were obtained via the analysis of the thermogravimetric and differential thermogravimetric （TG-DTG） curves by using Flynn-Wall-Ozawa method and Kissinger method. The thermal decomposition mechanism of abietic acid was studied with four integral methods （Satava-Sestak, MacCallum-Tanner, ordinary integral and Agrawal）. The results show that the thermal decomposition mechanism is nu- cleation and growth, and the mechanism function is Avrami-Erofeev equation with n equates 1/2. The activation energy and the pre-exponential factor are 64.04 kJ.mol^-1 and 5.89×10^5 s^-1, respectively.

The Thermal Decomposition of Ammonium Perchlorate-Aluminum Propellants in Presence of Metallic Zinc Particles

The thermal decomposition of ammonium perchlorate (AP) with Al and Zn metallic particles was studied at different heating rates in dry air atmosphere and the combustion behavior of AP/Al/Zn propellant was evaluated. The exothermic reaction kinetics was studied by differential thermal analysis (DTA) in non-isothermal conditions and compare with the thermal decomposition of pure AP and AP/aluminum particles analyzed in the same experimental conditions. The Arrhenius parameters were estimated according to the Ozawa and Kissinger methods. The calculated activation energies for the low and high temperature exothermic reactions were 91 and 229 kJ/mol for pure AP, 90 and 112 kJ/mol for 80 wt% AP/20 wt% Al particles. When zinc was incorporated, activation energy of 56 kJ/mol was determined for the only exothermic peak observed for 90 wt% AP/10 wt% Zn and 44 kJ/mol for 78.4 wt% AP/19.6 wt% Al/2 wt% Zn propellant composition.

Response Surface Modeling of Fuel Rich and Fuel Lean Catalytic Combustion of the Stabilized Confined Turbulent Gaseous Diffusion Flames

The Response Surface Methodology (RSM) has been applied to explore the thermal structure of the experimentally studied catalytic combustion of stabilized confined turbulent gaseous diffusion flames. The Pt/γAl2O3 and Pd/γAl2O3 disc burners were situated in the combustion domain and the experiments were performed under both fuel-rich and fuel-lean conditions at a modified equivalence (fuel/air) ratio (ø) of 0.75 and 0.25 respectively. The thermal structure of these catalytic flames developed over the Pt and Pd disc burners were inspected via measuring the mean temperature profiles in the radial direction at different discrete axial locations along the flames. The RSM considers the effect of the two operating parameters explicitly (r), the radial distance from the center line of the flame, and (x), axial distance along the flame over the disc, on the measured temperature of the flames and finds the predicted maximum temperature and the corresponding process variables. Also the RSM has been employed to elucidate such effects in the three and two dimensions and displays the location of the predicted maximum temperature.

Fabrication of a monoclinic/hexagonal junction in WO_3 and its enhanced photocatalytic degradation of rhodamine B

A series of WO3 samples with different crystalline phases were prepared by the thermal decomposition method from ammonium tungstate hydrate.X-ray diffraction（XRD）,scanning electron microscopy（SEM）,high-resolution transmission electron microscopy（HRTEM）,X-ray photoelectron spectroscopy,and N2 adsorption-desorption were used to characterize the crystalline phase,morphology,particle size,chemical composition,and surface area of the WO3 samples.The formation of hexagonal（h-WO3） and monoclinic（m-WO3） crystal structures of WO3 at different temperatures or different times was confirmed by XRD.m-WO3 is formed at 600 ℃,while m-WO3 starts to transform into h-WO3 at 800℃.However,h-WO3,which forms at 800℃,may transform into m-WO3 by increasing the calcination temperature to 1000℃.SEM results indicate that m-WO3 particles exhibit a bulky shape with heavy aggregates,while h-WO3 particles exhibit a rod-like shape.Moreover,m-WO3 crystals are sporadically patched on the surface of the h-WO3 rod-like particles,resulting in the exposure of both m-WO3 and h-WO3 on the surface.It is observed that the monoclinic phase（m-WO3）/hexagonal phase（h-WO3） junction was fabricated by tuning the calcination temperature and calcination time.The relative ratios between m-WO3 and h-WO3 in the phase junction can readily be tailored by control of the calcination time.The photocatalytic activities of WO3 with different crystalline phases were evaluated by the photocatalytic degradation of rhodamine B as a model pollutant.A higher photocatalytic activity was observed in the WO3 sample with the m-WO3/h-WO3junction as compared with the sample with only m-WO3.The improvement of photocatalytic activity can be attributed to the reduction of the electron-hole recombination rate owing to the formation of the phase junction,whose presence has been confirmed by HRTEM and photoluminescence spectra.

Catalytic thermal decomposition of ammonium perchlorate by a series of lanthanide EMOFs

Given their unique and excellent properties,metal-organic frameworks(MOFs)materials have been used in many scientific fields.EMOFs use energetic materials as ligands,which can provide part of the energy for the system while catalyzing ammonium perchlorate.The energetic material 1.1'-dihydroxyazotetrazole(H_(2)AzTO),as a high-energy nitrogen-rich material,was selected as a ligand.Five kinds of La^(3+),Ce^(3+),Pr^(3+),Nd^(3+),and Sm^(3+)lanthanide EMOFs were synthesized and obtained.Single crystal X-ray diffraction tests were conducted to obtain the crystal structures of EMOFs 1-5,which indicate that they have similar crystal structures.The thermal stabilities of EMOFs 1-5,which are obtained by differential scanning calorimetry(DSC)tests,are improved compa red with that of the ligand.The results of thermicdecomposition of ammonium perchlorate(AP)and AP mixtures with 10 wt%EMOFs 1-5 show that except for AP mixed with 10 wt%co mpound 2,the high-temperature decomposition peak tempe rature of AP mixed with other compounds is significantly advanced(up to 59.3-88.3 K),and the decomposition of AP is continuous and violent.EMOFs 3-5 have good application prospects for the catalytic thermicdecomposition of AP.

Recent advances in catalytic combustion of AP-based composite solid propellants

Composite solid propellants(CSPs) have widely been used as main energy source for propelling the rockets in both space and military applications. Internal ballistic parameters of rockets like characteristic exhaust velocity, specific impulse, thrust, burning rate etc., are measured to assess and control the performance of rocket motors. The burn rate of solid propellants has been considered as most vital parameter for design of solid rocket motors to meet specific mission requirements. The burning rate of solid propellants can be tailored by using different constituents, extent of oxidizer loading and its particle size and more commonly by incorporating suitable combustion catalysts. Various metal oxides(MOs),complexes, metal powders and metal alloys have shown positive catalytic behaviour during the combustion of CSPs. These are usually solid-state catalysts that play multiple roles in combustion of CSPs such as reduction in activation energy, enhancement of rate of reaction, modification of sequences in reaction-phase, influence on condensed-phase combustion and participation in combustion process in gas-phase reactions. The application of nanoscale catalysts in CSPs has increased considerably in recent past due to their superior catalytic properties as compared to their bulk-sized counterparts. A large surface-to-volume ratio and quantum size effect of nanocatalysts are considered to be plausible reasons for improving the combustion characteristics of propellants. Several efforts have been made to produce nanoscale combustion catalysts for advanced propellant formulations to improve their energetics. The work done so far is largely scattered. In this review, an effort has been made to introduce various combustion catalysts having at least a metallic entity. Recent developments of nanoscale combustion catalysts with their specific merits are discussed. The combustion chemistry of a typical CSP is briefly discussed for providing a better understanding on role of combustion catalysts in burning rate enhancement. Available information on different types of combustion nanocatalysts is also presented with critical comments.