统一动力学三维分区模型预测含能材料的晶体生长  

Prediction of the Crystal Growth of Energetic Materials by a unified Kinetic Three-dimensional Partition Model

作　　者：宋亮 陈博聪 张泳 苏浩龙 侯方超 叶婧 佘冲冲 SONG Liang;CHEN Bo-cong;ZHANG Yong;SU Hao-long;Hou Fang-chao;YE Jing;SHE Chong-chong(Faculty of Chemical Engineering,Huaiyin Institute of Technology,Huaian,223003,China;School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China;State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing,100081,China)

机构地区：[1]淮阴工学院化学工程学院,江苏淮安223003 [2]南京理工大学化学与化工学院,江苏南京210094 [3]北京理工大学爆炸科学与技术国家重点实验室,北京100081

出　　处：《含能材料》2024年第7期702-710,共9页Chinese Journal of Energetic Materials

基　　金：中国博士后科学基金(2023M731685)。

摘　　要：为了研究黑索今(RDX)、奥克托今(HMX)和六硝基茋(HNS)晶体的形貌特征,采用了统一动力学三维分区方法对这3种含能材料晶体的实时生长形貌进行了模拟,研究了结晶生长条件对晶体外形和晶面拓扑结构的影响。研究结果表明,RDX预测的晶形呈现类菱形,主要晶面包括(010)、(100)和(110)面;HMX晶体呈柱状,主要晶面包括(011)、(010)和(11−1)面;而HNS晶体呈薄片状,其中(100)面的显露面积最大,所预测的含能材料晶体外形与实验结果吻合。当RDX、HMX和HNS晶体呈现二维成核和外延生长模式时,较高的驱动力(Δμ=418.59 kJ·mol^(−1))导致晶体的分子层不断堆叠,呈现分层生长;而温度较低时,生长单元首先附着在晶面平台区域,逐渐形成“岛状”集聚,随后进行外延生长;当晶面足够大时,可能出现多个大小不同的“岛状”结构,并随时间增长逐渐合并。在较低驱动力下(Δμ=27.21 kJ·mol^(−1)),HNS晶体呈现螺旋位错生长,其中(100)晶面通过一个螺旋轴引发片层生长,形成“梯田”型晶面。通过附着能力分析发现,螺旋的扭结位和台阶面具有较强的吸附能力,而平台上的位点吸附能力较弱。In order to describe the characteristics of the crystal morphologies of hexogen(RDX),octogen(HMX),and hexanitrostilbene(HNS),the unified kinetic three-dimensional partitioning method was used to simulate the real-time growth morphologies of these three energetic material crystals.The influence of crystal growth conditions on crystal morphology and the topology of crystal face were studied.The research results show that the predicted crystal shape of RDX is rhombus-like,with the main crystal faces being(010),(100),and(110).The crystal morphology of HMX exhibits a columnar shape,with the main crystal faces including(011),(010),and(11-1).The crystal morphology of HNS has a flake-like shape,with the(100)face having the largest exposed area.The predicted crystal morphologies of energetic materials are consistent with experimental results.When RDX,HMX,and HNS crystals exhibit 2D nucleation and growth modes,a higher driving force(Δμ=418.59 kJ·mol^(−1))causes the molecular layers of the crystal to continuously stack,resulting in layered growth.When the temperature is low,growth units first attach to the crystal faces in the platform area,gradually forming"island-like"agglomerations,followed by epitaxial growth.When the crystal face is sufficiently large,multiple"island-like"structures of different sizes may appear,gradually merging over time.At lower driving force(Δμ=27.21 kJ·mol^(−1)),HNS crystals exhibit spiral dislocation growth,where the(100)crystal face triggers lamellar growth through a spiral axis,resulting in"terraced"crystal face.Adsorption ability analysis reveals that the kink sites and step surfaces of the helix have strong adsorption ability,while the sites on the face have weak adsorption ability.

关 键 词：动力学 Voronoi三维分区 黑索今(RDX) 奥克托今(HMX) 六硝基茋(HNS) 晶体生长 形貌预测 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]