DSC法与流变学法在测定HTPB基PBX代料固化动力学参数中的应用对比  

Comparison of the Applications of DSC and Rheology Methods in Determining the Curing Kinetics Parameters of HTPB-Based PBX Simulants

作　　者：王泓 王天翔 尹艳华 WANG Hong;WANG Tianxiang;YIN Yanhua(School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 102488,China)

机构地区：[1]北京理工大学化学与化工学院,北京102488

出　　处：《兵工学报》2024年第10期3596-3607,共12页Acta Armamentarii

摘　　要：为优化高聚物黏结炸药(Polymer Bonded Explosive,PBX)制备工艺并深入理解其性能,探寻适用于研究PBX炸药固化动力学的最佳方法,分别采用非等温差示扫描量热(Differential Scanning Calorimetry,DSC)法、流变学等温法及流变学非等温法对HTPB/TDI/Na_(2)SO_(4)/Al体系的固化反应动力学进行深入研究,得到在这3种测试条件下的固化反应动力学方程。同时,针对目前广泛使用的流变学非等温法进行合理优化。实验结果表明:HTPB与TDI间的固化反应遵循自催化模型;使用Kissinger法和Ozawa法获得的固化反应活化能相近,二者相差不超过3%;PBX代料体系的恒温固化表现为起始温度423.29 K,峰值温度440.23 K,终止温度444.49 K;流变学研究固化动力学过程中,需考虑温度对储能模量的影响,不能仅用测量值表征固化度,需要对数据进行修正;DSC法与流变学法各有优劣,若仅需获得固化动力学参数,DSC法是一个更好的选择,但欲了解固化过程中药浆内部结构变化,必须借助流变学法。In order to optimize the preparation process of polymer bonded explosive(PBX)and deeply understand its performance,and explore the best method suitable for studying the curing kinetics of PBX,the curing reaction kinetics of HTPB/TDI/Na 2 SO 4/Al system are thoroughly investigated using non-isothermal differential scanning calorimetry(DSC)method,rheological isothermal method,and rheological non-isothermal method.The curing reaction kinetic equations are obtained under these three test conditions,and the widely used non-isothermal rheological method is optimized.The results show that The curing reaction between HTPB and TDI follows an autocatalytic model,and the activation energies of curing reaction obtained using Kissinger and Ozawa methods are similar,with a difference of no more than 3%between the two.The thermostatic curing of PBX surrogate system exhibits an onset temperature of 423.29 K,a peak temperature of 440.23 K,and a final temperature of 444.49 K.The effect of temperature on the energy storage modulus needs to be considered in the rheological study of curing kinetics.The measured values cannot be used solely to characterize the degree of curing,and the data need to be corrected.DSC method and rheological method have their own advantages and disadvantages:if the objective is to obtain only the parameters of curing kinetics,the DSC method is a better choice.However,the rheological method must be used to understand the internal structure of slurry in the curing process.

关 键 词：高聚物黏结炸药 非等温差示扫描量热法 流变学法 固化反应动力学 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ560.1[化学工程—炸药化工]