Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This charact...Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This characteristic holds significant implications in the realm of novel satellite propulsion.Introducing a fraction of the electrical energy into energetic ionic liquid fuels,the thermal decomposition process is facilitated by reducing the apparent activation energy required,and electrical energy can trigger the electrochemical decomposition of ionic liquids,presenting a promising approach to enhance combustion efficiency and energy release.This study applied an external voltage during the thermal decomposition of 1-ethyl-3-methylimidazole nitrate([EMIm]NO_(3)),revealing the effective alteration of the activation energy of[EMIm]NO_(3).The pyrolysis,electrochemical decomposition,and electron assisted enhancement products were identified through Thermogravimetry-Differential scanning calorimetry-Fourier transform infrared-Mass spectrometry(TG-DSC-FTIR-MS)and gas chromatography(GC)analyses,elucidating the degradation mechanism of[EMIm]NO_(3).Furthermore,an external voltage was introduced during the combustion of[EMIm]NO_(3),demonstrating the impact of voltage on the combustion process.展开更多
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
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
The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffracti...The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.展开更多
[Mg(H2O)6](NTO)2·2H2O Was prepared by adding magnesium carbonate hydroxide to the aqueous solution of 3-nitro-1，2，4-triazol-5-one(NTO)．Its thermal decomposition mechanism was studied by DSC，TG／DTGand IR．The...[Mg(H2O)6](NTO)2·2H2O Was prepared by adding magnesium carbonate hydroxide to the aqueous solution of 3-nitro-1，2，4-triazol-5-one(NTO)．Its thermal decomposition mechanism was studied by DSC，TG／DTGand IR．The quantum chemical calculation on the title complex as a structure unit with the experimental geometry as atartmg values was carried out at B3LYP level with 6-31G basis set．The results show that the bonds between the coordinate waters and the Mgatom have certain extent covalent character．The net charges on nitrogen atoms of the NTO ring appear to be negative while the nitrogen atom on the nitro group(—NO2)appears to be positive which indicates—NO2 will lost first when the complex is heated to some uniform temperature and this result is in agreement with that of the thermal decomposition experiment．展开更多
Monodispersed MgO microspheres were successfully synthesized by a simple solvothermal method using PEG-400 as solvent. The samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). Th...Monodispersed MgO microspheres were successfully synthesized by a simple solvothermal method using PEG-400 as solvent. The samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The results reveal that the precusor was monoclinic Mg5(CO3)4(OH)2·4H2O and composed of nanosheets with the thickness of about 250 nm. By calcining the precusor at 500 °C for 5 min, cubic MgO with similar morphology was obtained. According to the SEM images, it is found that the volume ratio of PEG-400 to deionized water is considered as a crucial factor in the evolution of the morphology. Based on the SEM images obtained under different experimental conditions, a possible growth mechanism which involves self-assembly process was proposed. The thermal decomposition process of MgO precusor was studied by thermogravimetry-differential thermogravimetry(TG-DTG) at different heating rates in air. Thermal analysis kinetics results show that the most probale mechanism models of MgO precusor are An and D3, respectively. In addition, isothermal prediction was studied to quantitatively characterize the thermal decomposition process.展开更多
The coupling effect of heat absorption and release exists in the thermal decomposition of a few chemical materials.However,the impact of the above coupling on thermal hazard assessment is not considered in the literat...The coupling effect of heat absorption and release exists in the thermal decomposition of a few chemical materials.However,the impact of the above coupling on thermal hazard assessment is not considered in the literature studies.In this work,nitroguanidine(NQ)and 1,3,5-trinitro-1,3,5-triazine(RDX)are selected as representative materials to explore the influence of the coupling effect on the thermal hazard assessment of chemical materials.The linear heating experiments of NQ and RDX are carried out by a microcalorimeter and synchronous thermal analyser.The thermal decomposition curves are decoupled by advanced thermokinetics software.The thermal decomposition and kinetic parameters before and after decoupling are calculated.The results of TG experiment show that both NQ and RDX began to lose mass during the endothermic stage.The endothermic melting and exothermic decomposition of NQ and RDX are coupled within this stage.The coupling effect has different degrees of influence on its initial decomposition temperature and safety parameters.Compared with the parameters in the coupling state,the initial decomposition temperature and adiabatic induction period after decoupling decrease.The self-accelerating decomposition temperature increases,and internal thermal runaway time decreases.In the thermal hazard assessment of chemical materials with coupling effects,the calculated parameters after decoupling should be taken as an important safety index。展开更多
The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS....The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS.The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method.The TG/DTG curves in non-isothermal method are obtained in range of 25℃-400℃at heating rates of 3℃/min,5℃/min,8℃/min,10℃/min and 12℃/min.The data of weighttemperature are used for calculation of activation energy(E_a) of thermal decomposition reactions by methods of Ozawa,Kissinger,Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) as modelfree methods and Strink's equation as model-fitting method.The compensation effect is used for prediction of mechanism and determination of pre-exponential factor(InA) of the decomposition reaction.A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS.This result shows the lower thermal stability of HNBB in comparison to HNS,The Avrami equation(A_(3/2)) with function f(α)=3/2(1-α)[-In(1-α)]^(1/3) indicates the predicted mechanism for thermal decomposition reaction both explosives.展开更多
To study the thermal decomposition of Al/Zr H_(2)/PTFE with different Al particle size as well as mechanical strength and impact sensitivity under medium and low strain rates,molding-vacuum sintering was adopted to pr...To study the thermal decomposition of Al/Zr H_(2)/PTFE with different Al particle size as well as mechanical strength and impact sensitivity under medium and low strain rates,molding-vacuum sintering was adopted to prepare four groups of power materials and cylindrical specimens with different Al particle size.The active decomposition temperature of Zr H_(2) was obtained by TG-DSC,and the quasi-static mechanics/reaction characteristics as well as the impact sensitivity of the specimen were studied respectively by quasi-static compression and drop-hammer test.The results show that the yield strength of the material decreased with the increase of the Al particle size,while the compressive strength,failure strain and toughness increased first and then decreased,which reached the maximum values of 116.61 MPa,191%,and 119.9 MJ/m respectively when the Al particle size is 12-14 mm because of particle size grading.The specimens with the highest strength and toughness formed circumferential open cracks and reacted partly when pressed.Those with developmental cracks formed inside did not react.It is considered that fracture of specimens first triggered initial reaction between Al and PTFE to release an amount of heat.Then ZrH_(2) was activated and decomposed,and participated in subsequent reaction to generate Zr C.The impact sensitivity of the specimens decreased with the increase of Al particle size.展开更多
To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a com...To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a common effective approach.For this purpose,polyurethane(PU),a typical inert binder,was mixed with nitrocellulose(NC)as an energetic polymer.Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared.The prepared formulations were characterized using Fourier transform infrared spectroscopy(FTIR),RAMAN spectroscopy,X-ray diffraction(XRD),electron densimetry,thermogravimetric(TG)analysis,and differential scanning calorimetry(DSC).A kinetic study was then performed using the iterative KissingerAkahira-Sunose(It-KAS),Flynn-Wall-Ozawa(It-FWO),and non-linear Vyazovkin integral with compensation effect(VYA/CE)methods.The theoretical performances,such as theoretical specific impulse,adiabatic flame temperature,and ideal exhaust gaseous species,were also determined using the NASA Lewis Code,Chemical Equilibrium with Application(CEA).Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants.According to density tests,the density of the propellant increases as the nitrocellulose component increases.According to the thermal analysis and kinetics study,the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants.Based on the theoretical study,increasing the amount of NC in the propellant increased the specific impulse and,as a result,the overall performance.展开更多
A differential/integral method to estimate the kinetic parameters(apparent activation energy Eaand pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied...A differential/integral method to estimate the kinetic parameters(apparent activation energy Eaand pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane(HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy(Ea) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion(Tb) and adiabatic time-toexplosion(tTIad) based on Kooij formula are used to calculate the values of Tband tTIadto evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Eaand A of decomposition reaction of HNIW are 3(1 a)[ ln(1 a)]2/3, 152.73 kJ mol 1and 1011.97s 1, respectively, and the values of self-accelerating decomposition temperature(TSADT), Tband tTIadare 486.55 K, 493.11 K and52.01 s, respectively.展开更多
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 ...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.展开更多
The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanis...The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-systems for 2-DMAT. The azotetrazol has aromaic characteristic and its thermal decomposition can proceed in two steps: ring opening and N2 separation. The activation energies of the two steps are 152.3kJ/mol and 44.67kJ/mol respectively. The ring opening is the rate-controlling step.展开更多
To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed ...To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed via mechanical ball milling.The samples were characterized by SEM,XRD,TG-DSC,constant volume and constant pressure combustion experiments.The first exothermic peaks of Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) appear at 579°C and 564.5°C,respectively.The corresponding activation energies are similar.The corresponding mechanism functions are set as G(a) = [-ln(1-a)]^(3/4) and G(a) =[-ln(1-a)]2/3,respectively,which belong to the Avrami-Erofeev equation.Al/Fe_(2)O_(3)/CuO has better thermal safety.For small dose samples,its critical temperature of thermal explosion is 121.05°C higher than that of Al/Fe_(2)O_(3)/Bi_(2)O_(3).During combustion,the flame of Al/Fe_(2)O_(3)/CuO is spherical,and the main products are FeAl_(2)O_(4) and Cu.The flame of Al/Fe_(2)O_(3)/Bi_(2)O_(3)is jet-like,and the main products are Al_(2)O_(3),Bi and Fe.Al/Fe_(2)O_(3)/Bi_(2)O_(3)has better ignition and gas production performance.Its average ignition energy is 4.2 J lower than that of Al/Fe_(2)O_(3)/CuO.Its average step-up rate is 28.29 MPa/s,which is much higher than 6.84 MPa/s of Al/Fe_(2)O_(3)/CuO.This paper provides a reference for studying the thermal safety and combustion performance of ternary thermite.展开更多
The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparat...The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparatus,The kinetic parameters of the thermal decomposition reaction(the apparent activation energy(E,)and pre-exponential factor(A))were calcu-lated by non-isothermal DSC curves.The results show that the differential mlechanism function and values of E,and A of the ther-mal decomposition reaction of HNIW are 3(1-a)[-ln(1-a)]"·,155.04 kJ·mol^(-1)and 10""s^(-1),respectively.The critical tem-perature of thermal explosion of the title compound is 226.60℃.The entropy of activation(AS·),enthalpy of activation(AH·)and free energy of activation(AG·)of this reaction are 11.60J·mol·K^(-1),152.04 kJ·mol^(-1)and 146.29 kJ·mol^(-1),respec-tively.The equation of specific heat capacity of HNIW with temperature is C,=0.2472+0.002705992Tin the temperature range of 283 K to 343K.The values of self-accelerating decomposition temperature,adiabatic time-to-maximum decomposition rate and adiabatic time-to-explosion are 486.5K,54.81s and 54.31s,respectively.Thermal sensitivity probability density distribution curve of HNIW is constructed.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.52206165)。
文摘Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This characteristic holds significant implications in the realm of novel satellite propulsion.Introducing a fraction of the electrical energy into energetic ionic liquid fuels,the thermal decomposition process is facilitated by reducing the apparent activation energy required,and electrical energy can trigger the electrochemical decomposition of ionic liquids,presenting a promising approach to enhance combustion efficiency and energy release.This study applied an external voltage during the thermal decomposition of 1-ethyl-3-methylimidazole nitrate([EMIm]NO_(3)),revealing the effective alteration of the activation energy of[EMIm]NO_(3).The pyrolysis,electrochemical decomposition,and electron assisted enhancement products were identified through Thermogravimetry-Differential scanning calorimetry-Fourier transform infrared-Mass spectrometry(TG-DSC-FTIR-MS)and gas chromatography(GC)analyses,elucidating the degradation mechanism of[EMIm]NO_(3).Furthermore,an external voltage was introduced during the combustion of[EMIm]NO_(3),demonstrating the impact of voltage on the combustion process.
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.
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.
基金Project(20876160) supported by the National Natural Science Foundation of China
文摘The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.
文摘[Mg(H2O)6](NTO)2·2H2O Was prepared by adding magnesium carbonate hydroxide to the aqueous solution of 3-nitro-1，2，4-triazol-5-one(NTO)．Its thermal decomposition mechanism was studied by DSC，TG／DTGand IR．The quantum chemical calculation on the title complex as a structure unit with the experimental geometry as atartmg values was carried out at B3LYP level with 6-31G basis set．The results show that the bonds between the coordinate waters and the Mgatom have certain extent covalent character．The net charges on nitrogen atoms of the NTO ring appear to be negative while the nitrogen atom on the nitro group(—NO2)appears to be positive which indicates—NO2 will lost first when the complex is heated to some uniform temperature and this result is in agreement with that of the thermal decomposition experiment．
基金Project(CL11034)supported by the Training Program of Innovation and Entrepreneurship for Undergraduates of ChinaProject(CSUZC2013033)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,ChinaProject(201210533003)supported by National Training Programs of Innovation and Entrepreneurship for Undergraduates,China
文摘Monodispersed MgO microspheres were successfully synthesized by a simple solvothermal method using PEG-400 as solvent. The samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The results reveal that the precusor was monoclinic Mg5(CO3)4(OH)2·4H2O and composed of nanosheets with the thickness of about 250 nm. By calcining the precusor at 500 °C for 5 min, cubic MgO with similar morphology was obtained. According to the SEM images, it is found that the volume ratio of PEG-400 to deionized water is considered as a crucial factor in the evolution of the morphology. Based on the SEM images obtained under different experimental conditions, a possible growth mechanism which involves self-assembly process was proposed. The thermal decomposition process of MgO precusor was studied by thermogravimetry-differential thermogravimetry(TG-DTG) at different heating rates in air. Thermal analysis kinetics results show that the most probale mechanism models of MgO precusor are An and D3, respectively. In addition, isothermal prediction was studied to quantitatively characterize the thermal decomposition process.
基金the project of the Open Research Fund Program of Science and Technology on Aerospace Chemical Power Laboratory(Grant No.STACPL320221B04)Key Laboratory of Explosion Science and Technology(Beijing Institute of Technology)The project number is ZDKT21-01.
文摘The coupling effect of heat absorption and release exists in the thermal decomposition of a few chemical materials.However,the impact of the above coupling on thermal hazard assessment is not considered in the literature studies.In this work,nitroguanidine(NQ)and 1,3,5-trinitro-1,3,5-triazine(RDX)are selected as representative materials to explore the influence of the coupling effect on the thermal hazard assessment of chemical materials.The linear heating experiments of NQ and RDX are carried out by a microcalorimeter and synchronous thermal analyser.The thermal decomposition curves are decoupled by advanced thermokinetics software.The thermal decomposition and kinetic parameters before and after decoupling are calculated.The results of TG experiment show that both NQ and RDX began to lose mass during the endothermic stage.The endothermic melting and exothermic decomposition of NQ and RDX are coupled within this stage.The coupling effect has different degrees of influence on its initial decomposition temperature and safety parameters.Compared with the parameters in the coupling state,the initial decomposition temperature and adiabatic induction period after decoupling decrease.The self-accelerating decomposition temperature increases,and internal thermal runaway time decreases.In the thermal hazard assessment of chemical materials with coupling effects,the calculated parameters after decoupling should be taken as an important safety index。
基金the research committee of Malek-ashtar University of Technology(MUT)for supporting this work。
文摘The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS.The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method.The TG/DTG curves in non-isothermal method are obtained in range of 25℃-400℃at heating rates of 3℃/min,5℃/min,8℃/min,10℃/min and 12℃/min.The data of weighttemperature are used for calculation of activation energy(E_a) of thermal decomposition reactions by methods of Ozawa,Kissinger,Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) as modelfree methods and Strink's equation as model-fitting method.The compensation effect is used for prediction of mechanism and determination of pre-exponential factor(InA) of the decomposition reaction.A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS.This result shows the lower thermal stability of HNBB in comparison to HNS,The Avrami equation(A_(3/2)) with function f(α)=3/2(1-α)[-In(1-α)]^(1/3) indicates the predicted mechanism for thermal decomposition reaction both explosives.
基金financial support from the National Natural Science Foundation of China(General Program.Grant No.51673213)the National Natural Science Foundation of China(Youth Science Foundation.Grant No.51803235)。
文摘To study the thermal decomposition of Al/Zr H_(2)/PTFE with different Al particle size as well as mechanical strength and impact sensitivity under medium and low strain rates,molding-vacuum sintering was adopted to prepare four groups of power materials and cylindrical specimens with different Al particle size.The active decomposition temperature of Zr H_(2) was obtained by TG-DSC,and the quasi-static mechanics/reaction characteristics as well as the impact sensitivity of the specimen were studied respectively by quasi-static compression and drop-hammer test.The results show that the yield strength of the material decreased with the increase of the Al particle size,while the compressive strength,failure strain and toughness increased first and then decreased,which reached the maximum values of 116.61 MPa,191%,and 119.9 MJ/m respectively when the Al particle size is 12-14 mm because of particle size grading.The specimens with the highest strength and toughness formed circumferential open cracks and reacted partly when pressed.Those with developmental cracks formed inside did not react.It is considered that fracture of specimens first triggered initial reaction between Al and PTFE to release an amount of heat.Then ZrH_(2) was activated and decomposed,and participated in subsequent reaction to generate Zr C.The impact sensitivity of the specimens decreased with the increase of Al particle size.
文摘To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a common effective approach.For this purpose,polyurethane(PU),a typical inert binder,was mixed with nitrocellulose(NC)as an energetic polymer.Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared.The prepared formulations were characterized using Fourier transform infrared spectroscopy(FTIR),RAMAN spectroscopy,X-ray diffraction(XRD),electron densimetry,thermogravimetric(TG)analysis,and differential scanning calorimetry(DSC).A kinetic study was then performed using the iterative KissingerAkahira-Sunose(It-KAS),Flynn-Wall-Ozawa(It-FWO),and non-linear Vyazovkin integral with compensation effect(VYA/CE)methods.The theoretical performances,such as theoretical specific impulse,adiabatic flame temperature,and ideal exhaust gaseous species,were also determined using the NASA Lewis Code,Chemical Equilibrium with Application(CEA).Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants.According to density tests,the density of the propellant increases as the nitrocellulose component increases.According to the thermal analysis and kinetics study,the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants.Based on the theoretical study,increasing the amount of NC in the propellant increased the specific impulse and,as a result,the overall performance.
文摘A differential/integral method to estimate the kinetic parameters(apparent activation energy Eaand pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane(HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy(Ea) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion(Tb) and adiabatic time-toexplosion(tTIad) based on Kooij formula are used to calculate the values of Tband tTIadto evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Eaand A of decomposition reaction of HNIW are 3(1 a)[ ln(1 a)]2/3, 152.73 kJ mol 1and 1011.97s 1, respectively, and the values of self-accelerating decomposition temperature(TSADT), Tband tTIadare 486.55 K, 493.11 K and52.01 s, respectively.
基金the National Natural Science Foundation of China(NSFC,Grants No.52176114 and 52111530091)Jiangsu Funding Program for Excellent Postdoctoral Talent。
文摘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.
基金Sponsored by National Basic Research Programof China Throughthe Grant(2004CB217802) Educational Committee of Beijing(XK114140479)
文摘The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-systems for 2-DMAT. The azotetrazol has aromaic characteristic and its thermal decomposition can proceed in two steps: ring opening and N2 separation. The activation energies of the two steps are 152.3kJ/mol and 44.67kJ/mol respectively. The ring opening is the rate-controlling step.
基金supported by the National Natural Science Foundation of China, project number: 51704302the Natural Science Foundation of Shaanxi Province, China, project number: Grant No.2020JC-50。
文摘To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed via mechanical ball milling.The samples were characterized by SEM,XRD,TG-DSC,constant volume and constant pressure combustion experiments.The first exothermic peaks of Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) appear at 579°C and 564.5°C,respectively.The corresponding activation energies are similar.The corresponding mechanism functions are set as G(a) = [-ln(1-a)]^(3/4) and G(a) =[-ln(1-a)]2/3,respectively,which belong to the Avrami-Erofeev equation.Al/Fe_(2)O_(3)/CuO has better thermal safety.For small dose samples,its critical temperature of thermal explosion is 121.05°C higher than that of Al/Fe_(2)O_(3)/Bi_(2)O_(3).During combustion,the flame of Al/Fe_(2)O_(3)/CuO is spherical,and the main products are FeAl_(2)O_(4) and Cu.The flame of Al/Fe_(2)O_(3)/Bi_(2)O_(3)is jet-like,and the main products are Al_(2)O_(3),Bi and Fe.Al/Fe_(2)O_(3)/Bi_(2)O_(3)has better ignition and gas production performance.Its average ignition energy is 4.2 J lower than that of Al/Fe_(2)O_(3)/CuO.Its average step-up rate is 28.29 MPa/s,which is much higher than 6.84 MPa/s of Al/Fe_(2)O_(3)/CuO.This paper provides a reference for studying the thermal safety and combustion performance of ternary thermite.
基金The National Nature Science Foundation of China(21173163)
文摘The thermal behavior,non-isothermal thermal decomposition reaction kinetics and specific heat capacity of hexanitro-hexaazaisowurtzitane(HNIW)were studied by differential scanning calorimeter(DSC)and Micro-DSCIapparatus,The kinetic parameters of the thermal decomposition reaction(the apparent activation energy(E,)and pre-exponential factor(A))were calcu-lated by non-isothermal DSC curves.The results show that the differential mlechanism function and values of E,and A of the ther-mal decomposition reaction of HNIW are 3(1-a)[-ln(1-a)]"·,155.04 kJ·mol^(-1)and 10""s^(-1),respectively.The critical tem-perature of thermal explosion of the title compound is 226.60℃.The entropy of activation(AS·),enthalpy of activation(AH·)and free energy of activation(AG·)of this reaction are 11.60J·mol·K^(-1),152.04 kJ·mol^(-1)and 146.29 kJ·mol^(-1),respec-tively.The equation of specific heat capacity of HNIW with temperature is C,=0.2472+0.002705992Tin the temperature range of 283 K to 343K.The values of self-accelerating decomposition temperature,adiabatic time-to-maximum decomposition rate and adiabatic time-to-explosion are 486.5K,54.81s and 54.31s,respectively.Thermal sensitivity probability density distribution curve of HNIW is constructed.
