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作 者:王志强 张浩斌[1] 刘渝[1] 胡双启 胡立双 徐金江[1] WANG Zhi-qiang;ZHANG Hao-bin;LIU Yu;HU Shuang-qi;HU Li-shuang;XU Jin-jiang(Institute of Chemical Materials,CAEP,Mianyang 621999,China;School of Environment and Safety Engineering,North University of China,Taiyuan 030051,China)
机构地区:[1]中国工程物理研究院化工材料研究所,四川绵阳621999 [2]中北大学环境与安全工程学院,山西太原030051
出 处:《含能材料》2023年第2期142-151,共10页Chinese Journal of Energetic Materials
基 金:国家自然科学基金资助(21805259,21975234)。
摘 要:六硝基六氮杂异伍兹烷(CL-20)的晶型转变与控制技术是含能材料领域的热点,也是其应用推广时必须解决的关键问题。为了更加深入掌握不同晶体特性ε-CL-20的晶型转变规律与机制,采用原位X射线粉末衍射仪技术,对其热晶变行为及等温晶变动力学进行研究,探讨了晶体表面及内部缺陷对CL-20的ε→γ热晶变行为的影响,计算了不同晶体特性ε-CL-20的等温晶变动力学并获得了相关参数。结果表明,温度是影响ε-CL-20热晶变的主导因素,对于几十到几百微米的ε-CL-20,随着晶体内部及表面缺陷的增多,热晶变起始温度降低、热晶变速率增大。与粒径100μm的ε-CL-20晶体相比,超细ε-CL-20(0.5~1μm)的热晶变起始温度更高,热晶变速率也较快,并从晶体缺陷的两面性解释了超细ε-CL-20的异常热晶变行为。CL-20在热刺激作用下发生ε→γ晶变时,晶体的表面缺陷及内部缺陷作为相变过程的薄弱环节对其有诱导作用,γ晶型在ε-CL-20晶体上成核势垒较低的空位、杂质或位错等缺陷处优先成核,随后在这些位置逐渐长大。The polymorphic transformation(PT) and control technology of hexanitrohexaazaisowurtzitane(CL-20) has been a hot area of research in energetic materials, which is also the key issue must be addressed to promote its application. In order to further understand the PT characteristics and mechanism of ε-CL-20 with different crystallization characteristics, the PT laws and isothermal PT kinetics of ε-CL-20 were studied based on in-situ X-ray powder diffraction(XRD) technology. The effect of surface and internal defects on the ε→γ PT behavior of CL-20 was discussed. The isothermal PT kinetics of ε-CL-20 with different crystallization characteristics was analyzed and the related parameters were calculated. The results show that temperature is the dominant factor affecting the solid-solid PT of ε-CL-20. For the conventional particle ε-CL-20, with the increase of internal and surface defects in the crystal, the initial temperature of PT decreases and the PT rate increases. Compared with 100 μm CL-20, ultrafine(0.5-1 μm) ε-CL-20 has higher starting temperature of PT, but its PT rate is also faster. The abnormal PT behavior of ultrafine ε-CL-20 is explained from the two-sidedness of crystal defects. When CL-20 undergoes ε→γ PT under thermal stimulation, both the surface and internal defects of the crystal have an induction effect on the PT process, and the γ crystal preferentially nucleates at the defects such as vacancies, impurities or dislocations with low nucleation barrier on the ε-CL-20 crystal, and then gradually grows up at these positions.
关 键 词:晶体特性 CL-20 原位XRD 热诱导晶型转变 晶变动力学
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]
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