摘要
以二氯乙二肟、叠氮化钠、盐酸羟胺和三氯化钛等为原料,合成了1,1′-二羟基-5,5′-联四唑钛盐(Ti-BHT)燃烧催化剂。利用差示扫描量热法和热重法研究了不同升温速率下Ti-BHT金属盐的热分解过程,获得了热分解动力学参数和热分解机理函数;用Ozawa法和Kissinger法计算了热分解动力学参数,进而计算出自加速分解温度、热爆炸临界温度和热力学参数;用微量热法测定了Ti-BHT的比热容。结果表明,Ti-BHT的活化能Ek为143.49kJ/mol,指前因子Ak为1.23×10^(13)s^(-1),热分解属于n=3的随机成核和随后生长机理;自加速分解温度TSADT为466.21K,临界爆炸温度Tbpo为505.42K,热分解活化自由能ΔG~≠为142.74kJ/mol,活化焓ΔH~≠为139.41kJ/mol,活化熵ΔS~≠为-6.78J/(mol·K);Ti-BHT在298.15K的标准摩尔比热容为800.51J/(mol·K);摩擦爆炸概率为20%,特性落高大于125.9cm,说明其机械感度较低,具有较好的安全性能。
1,1′-Dihydxy-5,5′-bitetrazolate titanium salt （Ti-BHT）combustion catalyst was synthesized using dichloroglyoxime, sodium azide, hydroxylamine hydrochloride and titanium trichloride as raw materials. The thermal decomposition process of Ti-BHT was studied by differential scaning calorimetry （DSC） and thermogravimetry （TG） at different heating rates, and the kinetic parameters and mechanism functions of the thermal decomposition were obtained. Its thermal decomposition kinetic parameters were studied by Ozawa′s and Kissinger′s methods, and then the self-accelerating decomposition temperature, critical temperature of thermal explosion and thermodynamic parameters were calculated. The specific heat capacity of Ti-BHT was determined by microcalorimetry. The results show that the apparent activation energy E k is 143.49 kJ/mol, pre-exponential factor A k is 1.23×10^13 s^-1 , thermal decomposition belongs to the random nucleation and subsequent growth mechanism with n =3. The self-accelerating decomposition temperature T SADT and the critical temperature of thermal explosion T bpo are 466.21 and 505.42 K, respectively; the free energy of activation of thermal decomposition Δ G ≠ is 142.74 kJ/mol, the enthalpy of activation Δ H ≠ is 139.41 kJ/mol, and entropy of activation Δ S ≠ is -6.78 J/（mol·K）. The standard molar specific heat capacity is 800.51 J/（mol·K） at 298.15 K. Its explosion probability of impact sensitivity is 20%, the characteristic drop height is more than 125.9 cm, showing that its mechanical sensitivity is low and it has good safety performance.
作者
崔子祥
冯雅楠
范杰
赵凤起
薛永强
肖立柏
CUI Zi-xiang;FENG Ya-nan;FAN Jie;ZHAO Feng-qi;XUE Yong-qiang;XIAO Li-bai(Science and Technology on Combustion and Explosion Laboratory,Xi′an Modern Chemistry ResearchInstitute,Xi′an 710065,China;Department of Applied Chemistry,Taiyuan University ofTechnology,Taiyuan 030024,China)
出处
《火炸药学报》
EI
CAS
CSCD
北大核心
2018年第3期250-255,共6页
Chinese Journal of Explosives & Propellants
基金
国家自然科学基金(No.21573157
No.21373147)
