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1.
Two energetic strontium(II) complexes with nitrogen-rich 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) were synthesized. The metal complexes were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. DSC and TG-DTG were used to study the thermal behavior, non-isothermal decomposition reaction kinetics, self-accelerating decomposition temperature (T SADT), thermal ignition temperature (T TIT), critical temperature of thermal explosion (T b), and the adiabatic time-to-explosion (t TIad). The data indicate competitive energetic materials.  相似文献   

2.
The thermal decomposition behavior of composite modified double-base propellant containing hexanitrohexaazaisowurtzitane (CL-20/CMDB propellant) was studied by microcalorimetry. The kinetic and thermodynamic parameters were obtained from the analysis of the heat flow curves. The effect of different proportion of CL-20 to the thermal decomposition behavior, kinetics, and thermal hazard was investigated at the same time. The critical temperature of thermal explosion (T b), the self acceleration decomposition temperature (T SADT), and the adiabatic decomposition temperature rise (??T ad) were calculated to evaluate the thermal hazard of the CL-20/CMDB propellant. It shows that the CMDB propellant with 38% CL-20 has relative lower values of E and lgA, and with 18% CL-20 has the highest potential hazard.  相似文献   

3.
利用DSC和TG/DTG法研究了1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE)热分解行为及分解动力学,第一热分解过程的动力学方程为: ,其热爆炸临界温度为98.16 ºC。同时,利用微量热法测定了AHDNE的比热容,298.15K时的标准摩尔比热容为211.86 J•mol-1•K-1。计算得到了AHDNE的绝热至爆时间为59.21 s。AHDNE是不稳定的,其热稳定性远低于母体化合物FOX-7。  相似文献   

4.
Nitro compounds have been actively researched as driven by their potential to be high‐performing energetic materials. Herein, three new nitro compounds including semicarbazide 3,5‐dinitrobenzoate, (SCZ)(DNBA), manganese 3,5‐dinitrobenzoate dihydrate, [Mn(DNBA)2(H2O)2]n, and bis(semicarbazide) manganese(II) 3,5‐dinitrobenzoate, Mn(SCZ)2(DNBA)2, were synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. The results indicated that the above mentioned compounds are ionic, polymeric, and molecular in nature, respectively. Moreover, their thermal decomposition properties were assessed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Their non‐isothermal reaction kinetics parameters, critical temperature of thermal explosion (Tbp), entropy of activation (ΔS), enthalpy of activation (ΔH), and free energy of activation (ΔG) of the exothermic decomposition process were also calculated. Results suggest that there was a relationship between the structure and thermal stability.  相似文献   

5.
2,2,2-三硝基乙基-N-硝基甲胺的热安全性   总被引:1,自引:0,他引:1  
为评价2,2,2-三硝基乙基-N-硝基甲胺(TNMA)的热安全性, 得到计算TNMA热安全性参数用的基本数据, 用经验式估算了TNMA的比热容(Cp)和热导率(λ). 用键能贡献于生成热Qf的加和法, 估算了TNMA的标准生成焓ΔcHmθ(TNMA, s, 298.15 K). 用热力学公式计算了TNMA的标准燃烧焓ΔUmθ(TNMA, s, 298.15 K)和标准燃烧能ΔcHmθ(TNMA, s, 298.15 K). 用Kamlet-Jacobs 公式估算了爆速、爆压和爆热. 用经验式估算了分解热(Qd). 通过差示扫描量热(DSC)曲线和高灵敏度布鲁顿玻璃薄膜压力计测得的逸出气体标准体积(VH)-时间(t)曲线, 得到了TNMA放热分解反应的动力学参数. 用上述基本数据得到了评价TNMA的热安全性参数: 自加速分解温度(TSADT), 热爆炸临界温度(Tbe0和Tbp0), 绝热至爆时间(tTIad), 撞击感度50%落高(H50), 热点起爆临界温度(Tcr), 被300 K环境包围的半厚和半径为1 m的无限大平板、无限长圆柱和球形TNMA的热感度概率密度函数S(T), 相应于S(T)-T关系曲线最大值的峰温(TS(T)max), 安全度(SD), 临界热爆炸环境温度(Tacr)和热爆炸概率(PTE). 结果表明: (1) TNMA有较好的热安全性和对热抵抗能力, 与环三亚甲基三硝胺(RDX)相比, TNMA易从热分解过渡到热爆炸; (2) 不同形状大药量TNMA 热安全性降低的次序为: 球>无限长圆柱>无限大平板; (3)TNMA有高的燃烧能、高的爆轰化学能(爆热)和接近环四亚甲基四硝胺(HMX)的爆炸性能, 其对冲击敏感, 冲击感度与季戊四醇四硝酸酯(PETN)和特屈尔接近, 可用作混合炸药主组分.  相似文献   

6.
NaNTO·H2O was prepared by mixing 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) aqueous solution and sodium hydroxide aqueous solution. Its thermal decomposition and kinetics were studied under non‐isothermal conditions by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by the Kissinger method, the Ozawa method, the differential method and the integral method. The most probable mechanism function for the thermal decomposition of the first stage was suggested by comparing the kinetic parameters. The critical temperature of thermal explosion (Tb) was 240.93 °C. The theoretical investigation on the structure unit of the title compound was carried out by DFT‐B3LYP/CEP‐31G methods; atomic net charges and the population analysis were discussed.  相似文献   

7.
The thermal behavior of 4,6‐bis‐(5‐amino‐3‐nitro‐1,2,4‐triazol‐1‐yl)‐5‐nitropyrimidine (BANTNP) was studied under a non‐isothermal condition by DSC, PDSC and TG/DTG methods. The kinetic parameters (Ea and A) of the exothermic decomposition reaction are 304.52 kJ·mol?1 and 1024.47 s?1 at 0.1 MPa, 272.52 kJ·mol?1 and 1021.76 s?1 at 5.0 MPa, respectively. The kinetic equation at 0.1 MPa can be expressed as: dα/dT=1025.3(1?α)3/4exp(?3.8044×104/T)/β The critical temperature of thermal explosion is 588.28 K. The specific heat capacity of BANTNP was determined with a Micro‐DSC method, and the standard molar specific heat capacity is 397.54 J·mol?1·K?1 at 298.15 K. The adiabatic time‐to‐explosion of BANTNP was calculated to be 11.75 s.  相似文献   

8.
The thermal decomposition behavior and kinetic parameters of the exothermic decomposition reactions of the title compound in a temperature‐programmed mode have been investigated by means of DSC, TG‐DTG and lower rate Thermolysis/FTIR. The possible reaction mechanism was proposed. The critical temperature of thermal explosion was calculated. The influence of the title compound on the combustion characteristic of composite modified double base propellant containing RDX has been explored with the strand burner. The results show that the kinetic model function in differential form, apparent activation energy Ea and pre‐exponential factor A of the major exothermic decomposition reaction are 1‐a,207.98 kJ*mol?1 and 1015.64 s?1, respectively. The critical temperature of thermal explosion of the compound is 312.87 C. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as: dα/dT=1016.42 (1–α)e‐2.502×104/T As an auxiliary catalyst, the title compound can help the main catalyst lead salt of 4‐hydroxy‐3,5dinitropyridine oxide to enhance the burning rate and reduce the pressure exponent of RDX‐CMDB propellant.  相似文献   

9.
HU  Rongzu  ZHAO  Fengqi  GAO  Hongxu  ZHANG  Jiaoqiang  ZHANG  Hai  MA  Haixia 《中国化学》2009,27(11):2145-2154
Based on reasonable hypothesis, two general expressions and their six derived formulae for estimating the critical temperature (Tb) of thermal explosion for energetic materials (EM) were derived from the Semenov's thermal explosion theory and eight non‐isothermal kinetic equations. We can easily obtain the values of the initial temperature (T0i) at which DSC curve deviates from the baseline of the non‐isothermal DSC curve of EM, the onset temperature (Tei), the exothermic decomposition reaction kinetic parameters and the values of T00 and Te0 from the equation T0i or ei=T00 or e0+a1βi+a2βi2+···+aL?2βiL?2, i=1, 2, ;···, L and then calculate the values of Tb by the six derived formulae. The Tb values for seven nitrosubstituted azetidines, 3,3‐dinitroazetidinium nitrate ( 1 ), 3,3‐dinitroazetidinium picrate ( 2 ), 3,3‐dinitroazetidinium‐3‐nitro‐1,2,4‐triazol‐5‐onate ( 3 ), 1,3‐bis(3′,3′‐dinitroazetidine group)‐2,2‐dinitropropane ( 4 ), 1‐(2′,2′,2′‐trinitroethyl)‐3,3‐dinitroazetidine ( 5 ), 3,3‐dinitroazetidinium perchlorate ( 6 ) and 1‐(3′,3′‐dinitroazetidineyl)‐2,2‐dinitropropane ( 7 ), obtained with the six derived formulae are agreeable to each other, whose differences are within 1.5%. The results indicate that the heat‐resistance stability of the seven nitrosubstituted azetidines decreases in the order 6 > 7 > 5 > 4 > 3 > 2 > 1 .  相似文献   

10.
2‐(Dinitromethylene)‐1,3‐diazacycloheptane (DNDH) was prepared by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,4‐diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non‐isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process. The kinetic equation of the decomposition reaction is dα/dT=1033.88×3α2/3exp(−3.353×105/RT)/β. The critical temperature of thermal explosion is 215.97°C. Specific heat capacity of DNDH was studied with micro‐DSC method and theoretical calculation method, and the molar heat capacity is 215.40 J·mol−1·K−1 at 298.15 K. Adiabatic time‐to‐explosion was calculated to be 92.07 s. DNDH has same thermal stability to FOX‐7.  相似文献   

11.
A new energetic material, 4,5‐diacetoxyl‐2‐(dinitromethylene)‐imidazolidine (DADNI), was synthesized by the reaction of 4,5‐dihydroxyl‐2‐(dinitromethylene)‐imidazolidine (DDNI) and acetic anhydride, and characterized by single crystal X‐ray diffraction. Crystal data for DADNI are monoclinic, space group C2/c, a=15.9167(3) Å, b=8.6816(4) Å, c=8.5209(3) Å, β=103.294(9)°, V=1145.9(3) Å3, Z=4, µ=0.150 mm−1, F(000)=600, Dc=1.682 g·cm−3, R1=0.0565 and wR2=0.1649. Thermal decomposition behavior of DADNI was studied and an intensely exothermic process was observed. The kinetic equation of the decomposition reaction is: dα/dT=(1016.64/β)×4α3/4exp(−1.582×105/RT). The critical temperature of thermal explosion is 163.76°C. The specific heat capacity of DADNI was studied with micro‐DSC method and theoretical calculation method. The molar heat capacity is 343.30 J·mol−1·K−1 at 298.15 K. The adiabatic time‐to‐explosion of DADNI was calculated to be 87.7 s.  相似文献   

12.
This study investigated the role played by green thermal analysis technology in promoting the use of resources, preventing pollution, reducing energy consumption and protecting the environment. The chemical tert-butyl peroxybenzoate (TBPB) has been widely employed in the petrifaction industries as an initiator of polymerization formation agent. This study established the thermokinetic parameters and thermal explosion hazard for a reactor containing TBPB via differential scanning calorimetry (DSC). To simulate thermokinetic parameters, a 5-ton barrel reactor of liquid thermal explosion model was created in this study. The approach was to develop a precise and effective procedure on thermal decomposition, runaway, and thermal hazard properties, such as activation energy (E a), control temperature (CT), critical temperature (TCR), emergency temperature (ET), heat of decomposition (∆H d), self-accelerating decomposition temperature (SADT), time to conversion limit (TCL), total energy release (TER), time to maximum rate under isothermal condition (TMR iso), etc. for a reactor containing TBPB. Experimental results established the features of thermal decomposition and huge size explosion hazard of TBPB that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.  相似文献   

13.
The high nitrogen compound 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine and the high energy density material hexanitrohexaazaisowurtzitane (HNIW), were used as substitute of hexogen (RDX) in the composite modified double base (CMDB) propellant formulations, the propellant samples were prepared, the thermal behaviors, nonisothermal reaction kinetics, and thermal safety were carried out, and the eight important parameters were calculated and obtained as the self-accelerating decomposition temperature (T SADT), thermal ignition temperature (T TIT), critical temperatures of thermal explosion (T b), critical temperature of hot-spot initiation (T cr,hot-spot), characteristic drop height of impact sensitivity (H 50), critical thermal explosion ambient temperature (T acr), safety degree (S d), and thermal explosion probability (P TE). It shows that the content of HNIW has a large effect on the decomposition reaction mechanism of the CMDB propellant, when the content of HNIW is 10 %, the decomposition reaction are controlled by the random nucleation and subsequent growth (n = l), and the reaction mechanism obeys Mampel law; but when the content of HNIW is 20 %, the decomposition reaction are controlled by the chemical reaction (n = 1/4). The mechanism can not be changed by the catalysts, and they just make the apparent activation energy change slightly. For the sample, from BC01 to BC04, the values of T SADT and T TIT making an upward tendency, show the resistivity to heat: BC04 > BC03 > BC02 > BC01; the values of T acr and S d, BC01 are the maximum and BC02 are the minimum, show the heat sensitivity: BC01 > BC03 > BC04 > BC02. For the same radius, the thermal safety of the sphere sample is greater than that of the infinite cylinder one.  相似文献   

14.
A new unsymmetrical s‐tetrazine derivative, namely 4‐({2‐[6‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1,2,4,5‐tetrazin‐3‐yl]hydrazin‐1‐ylidene}methyl)phenol (DPHM), C14H14N8O, was synthesized based on 3‐(3,5‐dimethylpyrazol‐1‐yl)‐6‐hydrazinyl‐s‐tetrazine (DPHT). The structure was characterized by elemental analysis and single‐crystal X‐ray diffraction. Crystal structure determination shows that DPHM crystallizes in the monoclinic P21/c space group with high coplanarity and a zigzag layered structure. In addition, its thermal behaviour was investigated by DSC and TG–DTG methods. The thermal safety of DPHM was evaluated by self‐accelerating decomposition temperature (TSADT), critical temperature of thermal explosion (Tb), entropy of activation (ΔS), enthalpy of activation (ΔH) and free energy of activation (ΔG). Meanwhile, the kinetic parameters and specific heat capacity of DPHM were also determined. The results show that DPHM has better stability and detonation properties than 3‐(2‐benzylidenehydrazin‐1‐yl)‐6‐(3,5‐dimethylpyrazol‐1‐yl)‐s‐tetrazine (DAHBTz), due to the introduction of a hydroxy group, which increases the number of hydrogen‐bond interactions and improves the stability and density of DPHM. This study demonstrates that the performance of an explosive can be optimized through structural modification.  相似文献   

15.
Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate   总被引:1,自引:0,他引:1  
陈沛  赵凤起  罗阳  胡荣祖  李上文  高茵 《中国化学》2004,22(10):1078-1082
Introduction Triethylene glycol dinitrate (TEGDN) is a novel en-ergetic material containing two groups of NO2, which can be used as an energetic plasticizer ingredient in propellants because of its excellent proformance.1 It exhibits lower impact sensitivity, better thermostability, weaker poisonousness and volatility, and stronger effec-tiveness of plasticizing cellulose nitrate than nitroglyc-erine (NG). As a new plasticizer TEGDN has good ap-plication prospects in the near future. The…  相似文献   

16.
The thermal behavior and kinetic parameters of the exothermic decomposition reaction of N-methyl-N-nitro-2,2,2-trinitroethanamine in a temperature-programmed mode have been investigated by means of differential scanning calorimetry (DSC).The kinetic equation of the exothermic decomposition process of the compound is proposed. The values of the apparent activation energy (Ea), pre-exponential factor (A), entropy of activation (ΔS^≠ ), enthalpy of activation (ΔH^≠ ), and free energy of activation (ΔG^≠ ) of this reaction and the critical temperature of thermal explosion of the compound are reported. Information is obtained on the mechanism of the initial stage of the thermal decomposition of the compound.  相似文献   

17.
Plenty of thermal explosions and runaway reactions of cumene hydroperoxide (CHP) were described from 1981 to 2010 in Taiwan. Therefore, a thermal explosion accident of CHP in oxidation tower in 2010 in Taiwan was investigated because of piping breakage. In general, high concentration of CHP for thermal analysis using the calorimeter is dangerous. Therefore, a simulation method and a kinetic parameter were used to simulate thermal hazard of high concentrations of CHP only by the researcher. This study was applied to evaluate thermal hazard and to analyze storage parameters of 80 and 88 mass% CHP using three calorimeters for the oxidation tower, transportation, and 50-gallon drum. Differential scanning calorimetry (DSC) (a non-isothermal calorimeter), thermal activity monitor III (TAM III) (an isothermal calorimeter), and vent sizing package 2 (VSP2) (an adiabatic calorimeter) were employed to detect the exothermic behavior and runaway reaction model of 80 and 88 mass% CHP. Exothermic onset temperature (T 0), heat of decomposition (ΔH d), maximum temperature (T max), time to maximum rate under isothermal condition (TMRiso) (as an emergency response time), maximum pressure (P max), maximum of self-heating rate ((dT/dt)max), maximum of pressure rise rate ((dP/dt)max), half-life time (t 1/2), reaction order (n), activation energy (E a), frequency factor (A), etc., of 80 and 88 mass% CHP were applied to prevent thermal explosion and runaway reaction accident and to calculate the critical temperature (T c). Experimental results displayed that the n of 80 and 88 mass% CHP was determined to be 0.5 and the E a of 80 and 88 mass% CHP were evaluated to be 132 and 134 kJ mol?1, respectively.  相似文献   

18.
In this study, the thermal hazard features of various lithium-ion batteries, such as LiCoO2 and LiFePO4, were assessed properly by calorimetric techniques. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was used to measure the thermal hazards and runaway characteristics of the 18650 lithium-ion batteries under an adiabatic condition. The thermal behaviors of the lithium-ion batteries were obtained at normal and abnormal conditions in this study. The critical parameters for thermal hazardous behavior of lithium-ion batteries were obtained including the exothermic onset temperature (T 0), heat of decomposition (ΔH), maximum temperature (T max), maximum pressure (P max), self-heating rate (dT/dt), and pressure rise rate (dP/dt). Therefore, the result indicates the thermal runaway situation of the lithium-ion battery with different materials and voltages in view the of TNT-equivalent method by VSP2. The hazard gets greater with higher voltage. Without the consideration of other anti-pressure measurements, different voltages involving 3.3, 3.6, 3.7, and 4.2 V are evaluated to 0.11, 0.23, 0.88, and 1.77 g of TNT. Further estimation of thermal runaway reaction and decomposition reaction of lithium-ion battery can also be confirmed by VSP2. It shows that the battery of a fully charged state is more dangerous than that of a storage state. The technique results showed that VSP2 can be used to strictly evaluate thermal runaway reaction and thermal decomposition behaviors of lithium-ion batteries. The loss prevention and thermal hazard assessment are very important for development of electric vehicles as well as other appliances in the future. Therefore, our results could be applied to define important safety indices of lithium-ion batteries for safety concerns.  相似文献   

19.
In the experimental part of this study, thermal properties of the Al and NiO composites in micro‐ and nano‐sized Al are investigated. Differential scanning calorimetry (DSC) analysis of the onset temperatures of ignition, activation energy (Ea), frequency factor (A), rate constant (k), critical ignition temperature of thermal explosion (Tb), and self‐accelerating decomposition temperature (TSADT), as well as the thermodynamic parameters (ΔS , ΔH , and ΔG ) are used to explore the thermal behavior and analyze the kinetics. Thermal analysis suggests that the mechanism is based on solid–solid diffusion and liquid–gas for the nano‐ and micro‐Al/NiO composite, respectively. Our results indicate that the incorporation of nano‐Al particles can significantly reduce the ignition temperature, Ea, A, k, Tb, and TSADT. In the second part of this work, molecular dynamics (MD) simulation is used to investigate the behavior of Al/NiO thermite reaction using the Reaxff force field to evaluate the experimental results. Theoretically, MD results show 1,154 K as the reaction ignition temperature, which is in reasonably good agreement with experimental temperature of 893°C (1,166 K). The radial distribution function (RDF) shows that no reaction occurs at 500 K but it is complete at 1,200 K.  相似文献   

20.
制备了含3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)铅复合物(LCBTATZ)的双基推进剂和改性双基推进剂. 采用热重-微商热重法(TG-DTG)及差示扫描量热法(DSC)研究了其热分解行为和非等温分解动力学并在此基础上评价了其热安全性. 结果表明, LCBTATz-DB复合物中在350-540 K之间只存在一个放热分解峰, LCBTATz-CMDB复合物中存在两个连续的放热分解峰在390-540 K温度范围内, 其机理方程分别为: f(α)=α-1/2和f(α)=2(1-α)3/2. 计算了热加速分解温度(TSADT)、热爆炸临界温度(Tb)、热点火温度(TTIT)和绝热至爆时间(tTlad),其值分别为: DB001复合物TSADT=444.50 K, TTITT=453.96 K, Tb=471.84 K; tTlad=39.36 s; CMDB100复合物, TSADT=442.38 K, TTITT=452.89 K,Tb=464.13 K,tTlad=21.3 s,并以此来评价化合物的热安全性. 考察了LCBTATz-DB以及LCBTATz-CMDB的燃烧性能, 结果表明LCBTATZ 是一种高效的双基燃烧催化剂, 在较大的压力范围内可以显著的提高燃速并且大幅度的降低压力指数. 对于双基推进剂在2-8 MPa压力范围内出现了明显的超燃速现象, 8-12 MPa出现了“麦撒”效应, 对于改性双基推进剂的压力指数降到0.18.  相似文献   

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