摘要
3,4-二硝基吡唑(DNP)是一种性能优良的熔铸炸药载体,但由于强酸性和高感度的特点限制了其在含能材料领域的广泛应用。而与3,4-二氨基呋咱(DAF)形成共晶后其酸度和感度都显著降低,且具有低熔点的性能。采用MAE模型和分子动力学方法对DNP/DAF/H 2O共晶在不同条件下的晶体生长进行计算和模拟,探讨生长条件对晶体形貌的影响。计算DNP/DAF/H 2O在真空条件下的附着能,求得该共晶有(002)、(011)和(101)3个重要生长晶面。探究温度对晶体形貌的影响,其中在298 K条件下的晶体形貌与实验结果相符;且随着温度的升高,晶体的长径比逐渐减小;当温度升高至358 K时,长径比降至2.233,有利于提高其力学性能并降低感度。最后运用分子动力学模拟研究了DNP/DAF/H 2O在摩尔比为1∶1的乙腈/水、甲醇/水、乙醇/水、丙酮/水、乙酸乙酯/水5种混合溶剂中的晶体形貌。发现相比于单一的水溶剂,在甲醇/水溶剂中,晶体的长径比为2.150,更易生长出接近球形化的晶体,为该三元共晶的实验优化提供新思路。
3,4-Dinitropyrazole(DNP)is a high-performance fused explosive carrier,but its strong acidity and high sensitivity limit its wide application in the field of energetic materials.After cocrystalization with 3,4-diaminofurazan(DAF),its acidity and sensitivity were significantly reduced,and it exhibits low melting point properties.The crystal growth of DNP/DAF/H 2O cocrystal under different conditions is calculated and simulated by using MAE model and molecular dynamics method to explore the influence of different conditions on the cocrystal morphology.Firstly,the attachment energies of DNP/DAF/H 2O crystal under vacuum conditions were calculated,and the cocrystal is found to have three important growth planes(002),(011)and(101).The influence of temperature on crystal morphology was investigated,and the crystal morphology at 298 K was consistent with the experimental results.As the temperature increases,the aspect ratio of the crystal gradually decreases.When the temperature reaches 358 K,the aspect ratio decreases to 2.233,which is beneficial for improving mechanical properties and reducing sensitivity.Finally,molecular dynamics simulations were used to study the crystal morphology of DNP/DAF/H 2O in five mixed solvents with a molar ratio of 1∶1:acetonitrile/water,methanol/water,ethanol/water,acetone/water,and ethyl acetate/water.It was found that compared to a single water solvent,the aspect ratio of the crystals in methanol/water solvent was 2.150,making it easier to grow nearly spherical crystals,providing new ideas for the experimental optimization of this ternary cocrystal.
作者
周璇
曾秀琳
宋亮
居学海
ZHOU Xuan;ZENG Xiulin;SONG Liang;JU Xuehai(School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China;School of Chemistry and Materials Engineering,Huainan Normal University,Huainan 232038,China;School of Chemical Engineering,Huaiyin Institute of Technology,Huai’an 223003,China)
出处
《兵器装备工程学报》
2025年第9期267-273,共7页
Journal of Ordnance Equipment Engineering
基金
国家自然科学基金项目(22408120)
中国博士后基金项目(2023M731685)。
作者简介
周璇(2001-),女,硕士研究生,E-mail:2311608659@qq.com;通信作者:曾秀琳(1972-),女,博士,教授,E-mail:zengxiulin1992@163.com。
