Reactive molecular dynamics insight into the thermal decomposition mechanism of 2,6-Bis(picrylamino)-3,5-dinitropyridine

2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)has excellent thermostability,which makes its thermal decomposition mechanism receive much attention.In this paper,the mechanism of PYX thermal decomposition was investigated thoroughly by the ReaxFF-lg force field combined with DFT-B3LYP(6-311++G)method.The detailed decomposition mechanism,small-molecule product evolution,and cluster evolution of PYX were mainly analyzed.In the initial stage of decomposition,the intramolecular hydrogen transfer reaction and the formation of dimerized clusters are earlier than the denitration reaction.With the progress of the reaction,one side of the bitter amino group is removed from the pyridine ring,and then the pyridine ring is cleaved.The final products produced in the thermal decomposition process are CO_(2),H_(2)O,N_(2),and H_(2).Among them,H_(2)O has the earliest generation time,and the reaction rate constant(k_(3))is the largest.Many clusters are formed during the decomposition of PYX,and the formation,aggregation,and decomposition of these clusters are strongly affected by temperature.At low temperatures(2500 K-2750 K),many clusters are formed.At high temperatures(2750 K-3250 K),the clusters aggregate to form larger clusters.At 3500 K,the large clusters decompose and become small.In the late stage of the reaction,H and N in the clusters escaped almost entirely,but more O was trapped in the clusters,which affected the auto-oxidation process of PYX.PYX's initial decomposition activation energy(E_(a))was calculated to be 126.58 kJ/mol.This work contributes to a theoretical understanding of PYX's entire thermal decomposition process.

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.

Study on thermal decomposition kinetics of azobenzene-4,4′-dicarboxylic acid by using compensation parameter method and nonlinear fitting evaluation

Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.

Thermal decomposition of magnesium ammonium phosphate and adsorption properties of its pyrolysis products toward ammonia nitrogen

High-purity magnesium ammonium phosphate （MAP） was precipitated by controlling pH value of the reaction system of 9.0-9.5. The thermal decomposition behavior of MAP and the adsorption properties of its pyrolysis products toward ammonia-nitrogen were also studied by XRD, SEM, TGA-DTA and FT-IR methods. The results indicated that high-purity MAP was obtained at pH value of 9.0-9.5. Upon heating to 100-120℃ for 120 min, MAP was thermally decomposed, losing water and ammonia concomitantly with a reduction in grain size and crystallinity. The capacity of pyrolysis products for ammonia nitrogen adsorption reached 72.5 mg/g, with a removal rate of up to 95% from an 800 mg/L solution. The characteristic diffraction peaks corresponding to MAP mainly appeared in their XRD patterns after adsorption of ammonia nitrogen. The pyrolysis products of MAP at 100-120 ℃ could be recycling-used as the chemical treatment regents of ammonia nitrogen in the practical application.

Kinetics of thermal decomposition of lanthanum oxalate hydrate

Lanthanum oxalate hydrate La2（C2O4）3·10H2O,the precursor of La2O3 ultrafine powders,was prepared by impinging stream reactor method with PEG 20000 as surfactant.Thermal decomposition of La2（C2O4）3·10H2O from room temperature to 900 °C was investigated and intermediates and final solid products were characterized by FTIR and DSC-TG.Results show that the thermal decomposition process consists of five consecutive stage reactions.Flynn-Wall-Ozawa（FWO） and Kissinger-Akahira-Sunose（KAS） methods were implemented for the calculation of energy of activation（E）,and the results show that E depends on α,demonstrating that the decomposition reaction process of the lanthanum oxalate is of a complex kinetic mechanism.The most probable mechanistic function,G（α）=[1-（1＋α）1/3]2,and the kinetic parameters were obtained by multivariate non-linear regression analysis method.The average E-value that is compatible with the kinetic model is close to value which was obtained by FWO and KAS methods.The fitting curve matches the original TG curve very well.

Separation of W and Mo from their peroxoacids solutions by thermal decomposition

A separation method for W and Mo from peroxoacids solution by thermal decomposition wasstudied. Thermal decomposition of peroxotungstic acid and peroxomolybdic acid was investigated respectively. The results confirmed that peroxomolybdic acid showed a preferable stability compared with peroxotungstic acid. This thermal stability difference was the basic principle of theseparationof W and Mo. Experiments were performed to study the effects of temperature, stirring speed, free acid concentration and Mo concentration on the separation efficiency. The results indicated that peroxotungstic acid decomposed into tungstic acid（H2WO4） and precipitated selectively,while Mo was rejected in aqueous solution,realizing good separation of W and Mo. The separation factorof W and Moreached 112 under the studied conditions, which indicated that this method has potential for use in separating W and Mo.

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.

Preparation of fibrous nickel powder by precipitation transformation coupled with thermal decomposition

Fibrous particulate precursor was obtained by precipitation transformation in the ternary solution system of ammonium oxalate, nickel chloride and ammonia. The composition and morphology of precursor were characterized by XRD, SEM, IR and DTA/TGA analyses. The results show that the chemical composition and morphology of precursor precipitates at pH=8.4？8.8 are different from those of precursor precipitates at pH=6.0, and the mechanisms of the thermal decomposition of the precursors are different. The effects of various conditions in the process of thermal decomposition, including precursor morphology, atmosphere, temperature and time on the morphology and dispersion degree of obtained nickel powders were studied in detail. The final product inherits the morphology of precursor when the thermal decomposition is conducted under a weakly reducing atmosphere at temperature range of 400？440 °C for 30 min. Fibrous nickel powder can be produced with good dispersion, and its shape changes from smooth, straight and compact fiber into loose and curved fiber with rough surface.

Reactive Molecular Dynamics Simulation on Thermal Decomposition of n-Heptane

The thermal decomposition of n-heptane is an important process in petroleum industry. The theoretical investigations show that the main products are C2H4, H2, CH4, and C3H6, which agree well with the experimental results. The products populations depend strongly on the temperature. The quantity of ethylene increases quickly as the temperature goes up. The conversion of n-heptane and the mole fraction of primary products from reactive molecular dynamic and chemical kinetic modeling are compared with each other. We also investigated the pre-exponential factor and activation energy for thermal decomposition of n-heptane by kinetic analysis from the reactive force field simulations, which were extracted to be 1.78×10^14 s^-1 and 47.32 kcal/mol respectively.

Thermal decomposition of ammonium hexafluoroaluminate and preparation of aluminum fluoride

The thermal decomposition process of （NH4）3AlF6 was studied by DTA-TGA method and the related thermodynamic data were obtained. The results show that AlF3 is obtained after three-step decomposition reaction of （NH4）3AlF6, and the solid products of the first two decomposition reactions are NH4AlF4 and AlF3（NH4F）0.69, respectively. The three reactions occur at 194.9, 222.5 and 258.4 ℃, respectively. Gibbs free energy changes of pertinent materials at the reaction temperatures were calculated. Enthalpy and entropy changes of the three reactions were analyzed by DSC method. Anhydrous aluminum fluoride was prepared. The XRD analysis and mass loss calculation show that AlF3 with high purity can be obtained by heating （NH4）3AlF6 at 400 ℃ for 3 h.

Synthesis and photoluminescence properties of single-crystal ZnO hexagonal pyramids by PEG400-assisted thermal decomposition route

Large-scale synthesis of ZnO hexagonal pyramids was achieved by a simple thermal decomposition route of precursor at 240 oC in the presence of PEG400. The precursor was obtained by room-temperature solid-state grinding reaction between Zn（CH3COO）2-2H2O and Na2CO3. Crystal structure and morphology of the products were analyzed and characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and high-resolution transmission electron microscopy （HRTEM）. The results of further experiments show that PEG400 has an important role in the formation of ZnO hexagonal pyramids. Difference between the single and double hexagonal pyramid structure may come from the special thermal decomposition reaction. The photoluminescence （PL） spectra of ZnO hexagonal pyramids exhibit strong near-band-edge emission at about 386 nm and weak green emission at about 550 nm. The Raman-active vibration at about 435 cm-1 suggests that the ZnO hexagonal pyramids have high crystallinity.

Effects of Metal and Composite Metal Nanopowders on the Thermal Decomposition of Ammonium Perchlorate (AP) and the Ammonium Perchlorate/Hydroxyterminated Polybutadiene (AP/HTPB) Composite Solid Propellant

Effects of metal (Ni, Cu, Al) and composite metal (NiB, NiCu, NiCuB) nanopowders on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellant ammonium perchlorate/hydroxyterminated polybutadiene (AP/HTPB) were studied by thermal analysis (DTA). The results show that metal and composite metal nanopowders all have good catalytic effects on the thermal decomposition of AP and AP/HTPB composite solid propellant. The effects of metal nanopowders on the thermal decomposition of AP are less than those of the composite metal nanopowders. The effects of metal and composite metal nanopowders on the thermal decomposition of AP are different from those on the thermal decomposition of the AP/HTPB composite solid propellant.

Influence of Ammonium Polyphosphate on Thermal Decomposition of Reconstituted Tobacco and CO Evolution

The thermal behaviors and burning characteristics of reconstituted tobacco （RT） are strongly related with evolved gaseous products. The effect of ammonium polyphosphate （APP） as an additive of RT on the pyrolysis behavior and CO evolution was studied, emphasizing the role of heating velocity in reducing CO delivery of the mainstream smoke by APP. Thermogravimetric analysis （TGA） was employed to investigate the influence of APP on RT thermal behavior. Slow and flash pyrolysis of RT were compared to discuss the role of heating rate in decreasing CO by APP. TGA results demonstrated that, in dependence on APP concentration, APP influenced exothermal amount and weight loss rate during RT thermal decomposition, promoted the formation of char and retarded the thermal decomposition of RT. In addition, APP had a considerable influence on the evolution of gaseous products during thermal decomposition of RT. Both CO delivery per cigarette and that per puff in the smoking process were significantly reduced in dependence on APP content in RT. Comparative analysis of CO evolution patterns in the flash and slow pyrolysis elucidated that heating rate played a key role in decreasing CO evolution by APP. The results suggest that APP is a potential burning additive for controlling CO delivery in mainstream smoke of RT.

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.

Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

Syntheses,Crystal Structures and Kinetic Mechanisms of Thermal Decomposition of Rare Earth Complexes with Schiff Base Derived from o-Vanillin and p-Toluidine

Three complexes, [Pr（NO3）3（HL）2] （1）, [Nd（NO3）3（HL）2] （2） and [Er（NO3）3（HL）2] ·0.5H2O （3）, were synthesized from the reaction of a Schiff base ligand 2-[ （4-methylphenylimino）methyl ]-6-methoxyphenol （C15 H15 NO2, HL） with Ln（NO3）3·6H2O （Ln = Pr, Nd, Er）. Characterization by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, ^1H NMR and thermal analysis shows the title complexes are neutral molecules where the central Ln（ Ⅲ） ion is ten-coordinated in biapical anti-hexahedron prism geometry, with four oxygen atoms of the phenolic hydroxy and methoxy groups in the two bidentate Schiff base ligands and six oxygen atoms provided by the three bidentate NO3 - anions. Additionally, the kinetic mechanism of thermal decomposition of complex 3 was determined with a TG-DTG curves by both integral and differential methods. The functions of thermal decomposition reaction mechanism and the equation of kinetic compensation effect were obtained.

Thermal decomposition and mechanical properties of hydroxyapatite ceramic

Pure hydroxyapatite（HAP）ceramic and HAP composite ceramic with B2O3 were prepared by isostatic press forming and pressureless sintering.The relationships between thermal decomposition ratio and mechanical properties for pure HAP ceramic and the composite ceramic were investigated by means of FTIR,X-ray diffraction and three-point bending method.The results indicate that the decomposition ratio of pure HAP ceramic increases with ascending the sintering temperature and nearly reaches 80%at 1 350？殆or the HAP composite ceramic,the thermal decomposition is inhibited obviously due to the addition of B2O3.The added B atoms incorporate into the crystal lattice of HAP to form solid solution,resulting in an enlargement in the crystal spacing and an improvement in the binding strength of HAP crystal cell.Thermal decomposition ratio of HAP decreases but bending strength and fracture toughness are enhanced for HAP composite ceramics.However,when the added B2O3 is more than 5%（mass fraction）,HAP decomposition is promoted and a steady？-TCP is formed due to the fact that when B atoms with higher negative electricity are combined with O,sp2 and a full-air p are formed,and those voids have a strong trend to intake of the outer electrons.So,it is very possible to occupy the place where HAP loses OH - or PO4 3- .

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

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.

Thermal Decomposition of Ammonium 3-Nitro-1,2,4-triazol-5-onate Monohydrate

The thermal decomposition of ammonium 3-nitro-1,2,4-triazol-5-onate monohydrate[NH4（NTO）·H2O] was studied by means of thermal analysis-MS coupling and the combination technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy. The results show that there are two endothermic steps and one exothermic step in the decomposition process of NH4（NTO）·H2O. The detected gas products consist of NH3, H2O, N2, CO2, CO, and NO2.