In order to analyze the influences of storage aging on the safety of typical elemental explosives,the aged cyclotrimethylene trinitramine(RDX)and cyclotetramethylene tetranitramine(HMX)were prepared by isothermal agin...In order to analyze the influences of storage aging on the safety of typical elemental explosives,the aged cyclotrimethylene trinitramine(RDX)and cyclotetramethylene tetranitramine(HMX)were prepared by isothermal aging tests.The reaction thresholds of aged RDX and HMX under any ignition probability were studied by Langlie-Optimal D method.The thermal decomposition characteristics of RDX and HMX after aging were analyzed by DSC and ARC.Experimental results showed that compared with unaged RDX and HMX,on the one hand,the critical impact energy and critical friction of RDX and HMX aged for 14,28,and 56 days are significantly reduced at an explosion probability of 50%,0.01%,and 0.0001%,respectively.With the increase of aging time,the mechanical sensitivity of RDX and HMX increases obviously.On the other hand,the initial decomposition temperature of RDX and HMX after 56 days of aging decreases,the decomposition heat decreases,the activation energy increases,and the reaction difficulty increases.展开更多
High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S...High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S under abundant biomass has been reported in these presumed steam sterilized reservoirs ever before.In this study,we propose a new mechanism,biomass thermal decomposition for sulfur compounds(BTDS),to interpret the increasing of sH_(2)S.Sulfur of cells' dry weight took 0.20%-1.92% of the active strains isolated from the in-situ thermal recovery reservoirs of Liaohe Oilfield.When microbial organic sulfur compounds(MOSC) in biomass were exposed to injected steam,it resulted in the BTDS process.The isolated Bacillus subtilis D3(G+) and Pseudomonas aeruginosa XJ14(G-) were chosen to simulate this process.About 36% of sulfur in MOSC emitted as H_(2)S in steam chamber by BTDS.The δ^(34)S of H_(2)S from produced gas ranged from 8.7‰ to 17.0‰,close to the δ^(34)S of H_(2)S 11.2‰ from BTDS simulation experiment.It provides new insight into the contribution and sulfur cycle made by subterranean microorganisms on H_(2)S formation.展开更多
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 de...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/CO_(2)atmosphere.Results show that,the activation energy(Ea)for MPREC thermal decomposition in air and CO_(2)atmosphere are 146 and 320 kJ/mol,respectively.At temperature above 500℃in air or above 700℃in CO_(2)atmosphere,REOF are generated from bastnaesite through an in-situ reaction with CaO,which is decomposed from CaCO_(3),to form CaF_(2)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 co ntrast,the oxidation of Ce(Ⅲ)in a CO_(2)atmosphere is significantly inhibited.At 700℃,the oxidation rate of Ce in air is 74.09%,while in a CO_(2)atmosphere,it is only 33.83%.The hydrochloric acid leaching experiment shows that,the leaching rate of rare earth after roasting at 600℃under an air atmosphere reaches to 82.9%,and it reaches 87%after roasting at 800℃under a CO_(2)atmosphere.The reduction of Ce oxidation in a weak oxidizing atmosphere significantly improves the leaching rate of Ce.展开更多
To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analy...To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analyzer,X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Subsequently,the kinetic parameters of bastnaesite in the suspension roasting process were derived and calculated using the isothermal method.The results show that the decomposition product of bastnaesite in N_(2) is CeOF.However,once the roasting temperature exceeds 600℃,CO is generated in addition to CO_(2),and all the XRD diffraction peaks of CeOF are shifted to the right,indicating that CO_(2) can oxidize CeOF and lead to the transformation of Ce(Ⅲ) into Ce(Ⅳ).When roasted in air,the decomposition product CeOF can be completely converted to CeF3 and Ce_(7)O_(12) as it easily oxidizes.Additionally,the reaction rate of bastnaesite in air is higher than that of N_(2),and the starting reaction temperature is lower than that of N_(2).A large number of irregular cracks and holes appear on the surface of solid-phase products following suspension roasting,which are due to the thermal decomposition of bastnaesite that produces CO_(2) as well as the reconstruction of the lattice of the solid-phase products.The reaction kinetic model of bastnaesite roasted in N_(2)(temperature range 600-750℃) and air(temperatu re range 500-575℃) confo rms to the A_(3/2) model with the mechanism function G(α)=-ln(1-α)^(2/3),and the reaction activation energy is 59.78 kj/mol and lnA is 1.65 s^(-1) in N_(2) atmosphere.In air,the reaction activation energy is 100.30 kj/mol and lnA is 9.63 s^(-1).展开更多
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...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.展开更多
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 investigat...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.展开更多
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 ...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.展开更多
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 pro...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 ...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.展开更多
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 characterize...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.展开更多
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 resu...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.展开更多
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...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.展开更多
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 grindin...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.展开更多
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 polybuta...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.展开更多
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 ...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.展开更多
To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Expe...To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Experimental data indicated that the initial decomposition temperature of the concentrate under N2 atmosphere is 150 ℃ higher than that under O2 atmosphere,most likely because the oxidation of the cerium induces the decomposition of the concentrate. For the roasted samples under N2 atmosphere at500 ℃ and above,the oxidation efficiency of the cerium is 19.8%-26.8% because of the fact that rareearth fluorocarbonate is first decomposed to form rare-earth oxyfluoride and CO2, and the cerium oxyfluoride is then partially oxidized by the CO2 gas. The rest cerium in these samples can be further oxidized in air at room temperature, with the oxidation efficiency of the cerium gradually increasing to above 80% in 7 d. This can be attributed to the obvious changes in the inner morphology of the roasted samples under N2 atmosphere at high temperatures, which largely induce the diffusion of the air and improves the oxidation activity of CeOF, and further induces the oxidation of CeOF by the air. XRD and XPS techniques were used to further verify the significant differences in the thermal decomposition behaviors of the bastnaesite concentrate under N2 and O2 atmosphere. Moreover, no oxidation of Pr^（3＋） to Pr^（4＋） in the roasted samples under both N2 and O2 atmosphere is observed. This gives an overall understanding of the oxidative roasting of the bastnaesite concentrate without additives.展开更多
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 te...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.展开更多
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 poly...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.展开更多
基金supported by the National Key Laboratory of Energetic Materials, China (Grant No. 2023-LB-036-09).
文摘In order to analyze the influences of storage aging on the safety of typical elemental explosives,the aged cyclotrimethylene trinitramine(RDX)and cyclotetramethylene tetranitramine(HMX)were prepared by isothermal aging tests.The reaction thresholds of aged RDX and HMX under any ignition probability were studied by Langlie-Optimal D method.The thermal decomposition characteristics of RDX and HMX after aging were analyzed by DSC and ARC.Experimental results showed that compared with unaged RDX and HMX,on the one hand,the critical impact energy and critical friction of RDX and HMX aged for 14,28,and 56 days are significantly reduced at an explosion probability of 50%,0.01%,and 0.0001%,respectively.With the increase of aging time,the mechanical sensitivity of RDX and HMX increases obviously.On the other hand,the initial decomposition temperature of RDX and HMX after 56 days of aging decreases,the decomposition heat decreases,the activation energy increases,and the reaction difficulty increases.
文摘High concentration of secondary hydrogen sulfide(sH_(2)S) in thermal recovery reservoirs of Liaohe Oilfield,NE China was concluded to originate from thermochemical sulfate reduction(TSR),and no biotic source of H_(2)S under abundant biomass has been reported in these presumed steam sterilized reservoirs ever before.In this study,we propose a new mechanism,biomass thermal decomposition for sulfur compounds(BTDS),to interpret the increasing of sH_(2)S.Sulfur of cells' dry weight took 0.20%-1.92% of the active strains isolated from the in-situ thermal recovery reservoirs of Liaohe Oilfield.When microbial organic sulfur compounds(MOSC) in biomass were exposed to injected steam,it resulted in the BTDS process.The isolated Bacillus subtilis D3(G+) and Pseudomonas aeruginosa XJ14(G-) were chosen to simulate this process.About 36% of sulfur in MOSC emitted as H_(2)S in steam chamber by BTDS.The δ^(34)S of H_(2)S from produced gas ranged from 8.7‰ to 17.0‰,close to the δ^(34)S of H_(2)S 11.2‰ from BTDS simulation experiment.It provides new insight into the contribution and sulfur cycle made by subterranean microorganisms on H_(2)S formation.
基金supported by the National Key Research and Development Program of China(2020YFC1909104)National Natural Science Foundation of China(52274355)Major Science and Technology Project of Inner Mongolia Autonomous Region(2021ZD0016)。
文摘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/CO_(2)atmosphere.Results show that,the activation energy(Ea)for MPREC thermal decomposition in air and CO_(2)atmosphere are 146 and 320 kJ/mol,respectively.At temperature above 500℃in air or above 700℃in CO_(2)atmosphere,REOF are generated from bastnaesite through an in-situ reaction with CaO,which is decomposed from CaCO_(3),to form CaF_(2)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 co ntrast,the oxidation of Ce(Ⅲ)in a CO_(2)atmosphere is significantly inhibited.At 700℃,the oxidation rate of Ce in air is 74.09%,while in a CO_(2)atmosphere,it is only 33.83%.The hydrochloric acid leaching experiment shows that,the leaching rate of rare earth after roasting at 600℃under an air atmosphere reaches to 82.9%,and it reaches 87%after roasting at 800℃under a CO_(2)atmosphere.The reduction of Ce oxidation in a weak oxidizing atmosphere significantly improves the leaching rate of Ce.
基金Project supported by the National Key R&D Program of China (2022YFC2905800)National Natural Science Foundation of China(52174242)。
文摘To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analyzer,X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Subsequently,the kinetic parameters of bastnaesite in the suspension roasting process were derived and calculated using the isothermal method.The results show that the decomposition product of bastnaesite in N_(2) is CeOF.However,once the roasting temperature exceeds 600℃,CO is generated in addition to CO_(2),and all the XRD diffraction peaks of CeOF are shifted to the right,indicating that CO_(2) can oxidize CeOF and lead to the transformation of Ce(Ⅲ) into Ce(Ⅳ).When roasted in air,the decomposition product CeOF can be completely converted to CeF3 and Ce_(7)O_(12) as it easily oxidizes.Additionally,the reaction rate of bastnaesite in air is higher than that of N_(2),and the starting reaction temperature is lower than that of N_(2).A large number of irregular cracks and holes appear on the surface of solid-phase products following suspension roasting,which are due to the thermal decomposition of bastnaesite that produces CO_(2) as well as the reconstruction of the lattice of the solid-phase products.The reaction kinetic model of bastnaesite roasted in N_(2)(temperature range 600-750℃) and air(temperatu re range 500-575℃) confo rms to the A_(3/2) model with the mechanism function G(α)=-ln(1-α)^(2/3),and the reaction activation energy is 59.78 kj/mol and lnA is 1.65 s^(-1) in N_(2) atmosphere.In air,the reaction activation energy is 100.30 kj/mol and lnA is 9.63 s^(-1).
基金National Natural Science Foundation of China(Grant No.21975227)the Found of National defence Science and Technology Key Laboratory (Grant No.6142602210306)。
文摘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.
基金funded by the National Natural Science Foundation of China(Grant No.21975024)。
文摘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.
基金supported by National Natural Science Foundation of China(51974166).
文摘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.
基金Project(ZDSY20120619093952884)supported by Shenzhen Strategic New Industry Development,China
文摘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.
基金Project (IRT0974) supported by Program for Changjiang Scholars and Innovative Research Team in University,ChinaProject (50974098) supported by the National Natural Science Foundation of China
文摘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.
基金Project(51334008)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Key Program of Science and Technology of Hunan Province,China
文摘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.
基金Project(51374058)supported by the National Natural Science Foundation of China
文摘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.
基金Project(2010FJ3012)supported by the Science and Technology Plan Foundation of Hunan Province,China
文摘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.
基金This work was supported by the National Natural Science Foundation of China （No.21103117）.
文摘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.
基金Project(51004034)supported by the National Natural Science Foundation of ChinaProject(N090302009)supported by the Fundamental Research Funds for the Central Universities,China
文摘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.
基金Project (BK2009379) supported by the Natural Science Foundation of Jiangsu Province, ChinaProject (1006-56XNA12069) supported by the Nanjing University of Aeronautics and Astronautics Research Funding, China+3 种基金Projects (51172108, 91023020) supported by the National Natural Science Foundation of ChinaProject (IRT0968) supported by the Program for Changjiang Scholars and Innovative Research Team in University, ChinaProject (NCET-10-0070) supported by the Program for New Century Excellent Talents in University, ChinaProject supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions, China
文摘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.
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(51404035)Beijing Nova program(Z161100004916108)
文摘To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Experimental data indicated that the initial decomposition temperature of the concentrate under N2 atmosphere is 150 ℃ higher than that under O2 atmosphere,most likely because the oxidation of the cerium induces the decomposition of the concentrate. For the roasted samples under N2 atmosphere at500 ℃ and above,the oxidation efficiency of the cerium is 19.8%-26.8% because of the fact that rareearth fluorocarbonate is first decomposed to form rare-earth oxyfluoride and CO2, and the cerium oxyfluoride is then partially oxidized by the CO2 gas. The rest cerium in these samples can be further oxidized in air at room temperature, with the oxidation efficiency of the cerium gradually increasing to above 80% in 7 d. This can be attributed to the obvious changes in the inner morphology of the roasted samples under N2 atmosphere at high temperatures, which largely induce the diffusion of the air and improves the oxidation activity of CeOF, and further induces the oxidation of CeOF by the air. XRD and XPS techniques were used to further verify the significant differences in the thermal decomposition behaviors of the bastnaesite concentrate under N2 and O2 atmosphere. Moreover, no oxidation of Pr^（3＋） to Pr^（4＋） in the roasted samples under both N2 and O2 atmosphere is observed. This gives an overall understanding of the oxidative roasting of the bastnaesite concentrate without additives.
基金Project supported by the National Natural Science Foundation of China (50306008)Advance Research Foundation forGeneral Equipment Department (41328030507)
文摘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.
基金DRDO(TBR-1251)for funding and awarding the Project
文摘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.
