水分子对α相CL-20热分解机理影响的分子动力学研究

引用本文: 张力, 陈朗, 王晨, 伍俊英. 水分子对α相CL-20热分解机理影响的分子动力学研究[J]. 物理化学学报, 2013, 29(06): 1145-1153. doi: 10.3866/PKU.WHXB201303221 shu

Citation: ZHANG Li, CHEN Lang, WANG Chen, WU Jun-Ying. Molecular Dynamics Study of the Effect of H₂O on the Thermal Decomposition of α Phase CL-20[J]. Acta Physico-Chimica Sinica, 2013, 29(06): 1145-1153. doi: 10.3866/PKU.WHXB201303221 shu

水分子对α相CL-20热分解机理影响的分子动力学研究

摘要:

研究六硝基六氮杂异伍兹烷(CL-20)晶体不同晶型在不同温度下的反应机理, 对于深入认识含能材料在极端条件下的冲击起爆、冲击点火和爆轰过程等具有重要意义. 基于反应力场, 研究水分子在纯α相CL-20及其水合物的晶体结构中数量随时间的变换, 分析水分子对两种体系的初始分解和第二阶段的分解路径的影响. 计算结果表明: CL-20 分子的初始分解路径与水分子无关, 第二阶段的分解反应与水分子有关. 在低温(T<1500 K)下, 水分子对两种体系没有影响, 二者的初始分解路径均为N-NO₂键生成NO₂自由基; 在1500 K≤T≤2500 K时, 水分子作为反应物或与NO₂、、OH自由基等组成催化体系, 生成O₂、H₂O₂等产物, 加速水合物体系在高温下的第二阶段反应, 使得高温下水合物体系的化学反应速率和反应生成的NO₂自由基的数量比纯CL-20体系的化学反应速率和反应生成的NO₂自由基的数量大; 在T>2500 K时, 水分子的催化反应抑制CL-20初始分解反应, 使得在3000 K时纯CL-20体系的反应速率大于水合物体系中CL-20的反应速率.

关键词:

English

Molecular Dynamics Study of the Effect of H₂O on the Thermal Decomposition of α Phase CL-20

1.
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, P. R. China
Received Date: 31 January 2013
Available Online: 17 May 2013

Abstract:

The response of the mechanisms of the α polymorph of CL-20 (α-CL-20) to high temperature is important for understanding the phenomenon of shock initiation, shock ignition, and detonation. The thermal decomposition of α-CL-20 hydrate and pure α-CL-20 were studied by ReaxFF reactive molecular dynamics simulations to obtain the time evolution of water molecules and the effect of H₂O on the mechanisms of CL-20 at high temperatures. It was determined that the initial decomposition mechanisms of CL-20 are not dependent on the presence of water, but the secondary reaction pathways are. At low temperatures (T<1500 K), there is no relationship between the H₂O, hydrate CL-20, and pure CL-20 systems, as the mechanism is only the dissociation of the N―NO₂ bond to form the NO₂ radical. At high temperatures (1500 K≤T≤2500 K), water molecules act as a reactant or form catalytic systems with NO₂ radical to form OH radical, leading to the formation of O₂, H₂O₂, and other products. Water molecules accelerate the secondary stage reaction of hydrate systems, leading to increased secondary reaction rates and number of NO₂ radicals in the CL-20 hydrate compared with the pure CL-20 system. At very high temperatures (T>2500 K), the dissociation of water molecules competes with the initial thermal decomposition pathway of CL-20, leading to a larger rate constant for the pure CL-20 than for the hydrate CL-20.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

水分子对α相CL-20热分解机理影响的分子动力学研究

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