NTO晶体空穴缺陷对热分解机理的影响  

Effect of Vacancy Defects on Thermal Decomposition Mechanism of NTO Crystals

作　　者：宁丽媛 李丽洁[1] 陈锟 金韶华[1] 鲁志艳 NING Liyuan;LI Lijie;CHEN Kun;JIN Shaohua;LU Zhiyan(School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China;Gansu Yinguang Chemical Industry Group Corporation,Baiyin 730900,China)

机构地区：[1]北京理工大学材料学院,北京100081 [2]甘肃银光化学工业集团有限公司,白银730900

出　　处：《高等学校化学学报》2023年第8期97-106,共10页Chemical Journal of Chinese Universities

基　　金：基础产品创新科研项目(批准号:202120929076)资助.

摘　　要：为了研究晶体缺陷对3-硝基-1,2,4-三唑-5-酮(NTO)热分解过程的影响,构建了内含256个NTO分子的完美晶体模型及分别含有0.78%,1.17%,2.34%,3.13%和5.10%空穴缺陷的晶体模型,分别计算了1500 K下6种模型的势能、产物变化等,分析了反应初始路径并计算了热分解反应速率.结果表明,在1500 K条件下,NTO初始分解反应包含NTO聚集产生团簇、C—NO_(2)键断裂脱硝基、分子间质子转移导致的开环反应和环断裂反应(包括C3—N4,N1—C5键的断裂和C3—N4,N1—N2键的断裂)4种类型.在0.78%~2.34%空穴浓度范围内,随着缺陷浓度增加,4种初始反应发生频次增加,质子化反应提前,环断裂反应延后.当缺陷浓度超过2.34%时,空穴的存在导致晶体塌陷,4种初始反应频次降低,复杂反应频次增加.空穴缺陷的存在使整体热分解进程加快.A perfect crystal model containing 2563-nitro-1,2,4-triazol-5-one(NTO)molecules and defects crystal models containing 0.78%,1.17%,2.34%,3.13%and 5.10%vacancy content,respectively,were constructed to study the effect of vacancy defects on the thermal decomposition of NTO.The potential energy and products of the six models at 1500 K were calculated,respectively.The initial reaction paths and decomposition rates were analyzed.The results show that at 1500 K,there are four paths for the initial decomposition of NTO:NTO aggregates to produce clusters,C—NO_(2)bond breaks to remove nitro,intermolecular proton transfer to cause ring opening and breaking(including C3—N4,N1—C5 bond fracture and C3—N4,N1—N2 bond fracture).In the range of 0.78%—2.34%vacancy content,with the increase of defect content,the frequency of the four initial reactions increases,the protonation reaction advances,and the ring fracture reaction delays.When the defect content exceeds 2.34%,the existence of vacancy leads to crystal collapse,the frequency of four initial reactions decreases,and the frequency of complex reactions increases.The existence of vacancy defects accelerates the overall thermal decomposition process.The above research results can be used to guide the regulation of NTO thermal safety.

关 键 词：3-硝基-1 2 4-三唑-5-酮 分子反应动力学 热分解 晶体缺陷 热安全性 

分 类 号：O641[理学—物理化学]