采用动态真空安定性（DVST）方法研究了叠氮化铅（LA）和羧甲基纤维素叠氮化铅（CMC-LA）的热分解过程。利用微分法分析了测试数据。获得了LA和CMC-LA的反应机理函数和表观活化能,剖析了羧甲基纤维素钠晶型控制剂对LA安定性和热分解反...采用动态真空安定性（DVST）方法研究了叠氮化铅（LA）和羧甲基纤维素叠氮化铅（CMC-LA）的热分解过程。利用微分法分析了测试数据。获得了LA和CMC-LA的反应机理函数和表观活化能,剖析了羧甲基纤维素钠晶型控制剂对LA安定性和热分解反应动力学参数的影响。结果表明,在非等温阶段,60~100℃,LA热分解反应的机理函数为Zhuralev-Lesokin-Tempelman方程,表观活化能（Ea）分别是86.53、42.26、39.43、38.09 k J·mol-1和10.84k J＂mol-1。在60~70℃,CMC-LA热分解反应的机理函数为Avrami-Erofeev方程,Ea分别是133.02 k J·mol-1和41.87 k J·mol-1,在80~100℃,CMC-LA热分解反应的机理为减速型α-t曲线,Ea分别是43.07、34.34 k J·mol-1和33.46 k J·mol-1。添加羧甲基纤维素钠改变了LA的反应机理函数,使得CMC-LA在60~70℃产气量更小,热安定性更好。展开更多
Vacuum Stability Test(VST)was used to determine the thermal behavior and kinetic parameters of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)and its mixture with hydroxyl-terminated polybutadiene(HTPB)as a binder coded a...Vacuum Stability Test(VST)was used to determine the thermal behavior and kinetic parameters of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)and its mixture with hydroxyl-terminated polybutadiene(HTPB)as a binder coded as HMX/HTPB.Model fitting and isoconversional method were applied to determine the kinetic parameters based on VST results.For comparison,non-isothermal thermogravimetry analysis data(TGA)was also used to calculate the kinetic parameters by using Kissinger,OFW(Ozawa,Flynn,and Wall)and KAS(Kissinger-Akahira-Sunose)methods.Advanced Kinetics and Technology Solution(AKTS)software was also used to determine the decomposition kinetics of the studied samples.Differential Scanning Calorimetry(DSC)was employed to determine the decomposition heat flow properties of the studied samples.Results show that the activation energies obtained using VST results is 360.1kJ/mol for pure HMX and 186.9kJ/mol for HMX/HTPB.The activation energies obtained by the three different methods using TGA results are in the range of 360-368kJ/mol for pure HMX and 190-206kJ/mol for HMX/HTPB.It is concluded that values of kinetic parameters obtained by VST are close to that obtained by the different techniques using TG/DTG results.The onset decomposition peak of HMX/HTPB is lower than that of HMX where the HTPB binder has negative effect on the thermal stability of HMX.The results of all the applied techniques prove that HMX/HTPB has lower activation energy and heat release than the pure HMX.HTPB polymeric matrix has negative effect on the kinetic parameters of HMX.展开更多
文摘采用动态真空安定性（DVST）方法研究了叠氮化铅（LA）和羧甲基纤维素叠氮化铅（CMC-LA）的热分解过程。利用微分法分析了测试数据。获得了LA和CMC-LA的反应机理函数和表观活化能,剖析了羧甲基纤维素钠晶型控制剂对LA安定性和热分解反应动力学参数的影响。结果表明,在非等温阶段,60~100℃,LA热分解反应的机理函数为Zhuralev-Lesokin-Tempelman方程,表观活化能（Ea）分别是86.53、42.26、39.43、38.09 k J·mol-1和10.84k J＂mol-1。在60~70℃,CMC-LA热分解反应的机理函数为Avrami-Erofeev方程,Ea分别是133.02 k J·mol-1和41.87 k J·mol-1,在80~100℃,CMC-LA热分解反应的机理为减速型α-t曲线,Ea分别是43.07、34.34 k J·mol-1和33.46 k J·mol-1。添加羧甲基纤维素钠改变了LA的反应机理函数,使得CMC-LA在60~70℃产气量更小,热安定性更好。
文摘Vacuum Stability Test(VST)was used to determine the thermal behavior and kinetic parameters of 1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)and its mixture with hydroxyl-terminated polybutadiene(HTPB)as a binder coded as HMX/HTPB.Model fitting and isoconversional method were applied to determine the kinetic parameters based on VST results.For comparison,non-isothermal thermogravimetry analysis data(TGA)was also used to calculate the kinetic parameters by using Kissinger,OFW(Ozawa,Flynn,and Wall)and KAS(Kissinger-Akahira-Sunose)methods.Advanced Kinetics and Technology Solution(AKTS)software was also used to determine the decomposition kinetics of the studied samples.Differential Scanning Calorimetry(DSC)was employed to determine the decomposition heat flow properties of the studied samples.Results show that the activation energies obtained using VST results is 360.1kJ/mol for pure HMX and 186.9kJ/mol for HMX/HTPB.The activation energies obtained by the three different methods using TGA results are in the range of 360-368kJ/mol for pure HMX and 190-206kJ/mol for HMX/HTPB.It is concluded that values of kinetic parameters obtained by VST are close to that obtained by the different techniques using TG/DTG results.The onset decomposition peak of HMX/HTPB is lower than that of HMX where the HTPB binder has negative effect on the thermal stability of HMX.The results of all the applied techniques prove that HMX/HTPB has lower activation energy and heat release than the pure HMX.HTPB polymeric matrix has negative effect on the kinetic parameters of HMX.
