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含NHnn=0~4)的化合物对DNAN凝固过程及凝固温度的影响机理
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作者单位:

1.西安近代化学研究所, 陕西 西安 710065;2.甘肃银光化学工业集团有限公司, 甘肃 白银 730900

作者简介:

张蒙蒙(1986-),男,副研究员,主要从事含能材料制备及表征研究。e-mail:XSKY2000@163.com

通讯作者:

罗一鸣(1980-),男,研究员,从事混合炸药制备与表征研究。e-mail:iamrlym@126.com

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Solidification Process and Solidification Temperature of DNAN Containing NHnn=0-4) Compounds and Its Mechanism
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Affiliation:

1.Xi′an Modern Chemistry Research Institute, Xi′an 710065, China;2.Gansu Yinguang Chemical Industry Group Co. Ltd., Baiyin 730900, China

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    摘要:

    为了研究高氯酸铵(AP)、硝酸胍(GN)、硝基胍(NQ)、N-甲基-4-硝基苯胺(MNA)、奥克托今(HMX)等含NHnn=0~4)的化合物影响2,4-二硝基苯甲醚(DNAN)凝固过程及凝固温度的机制,采用差示扫描量热(DSC)法和光学显微镜法研究了AP含量及不同添加物对DNAN凝固温度的影响;采用显微镜观测了含添加物DNAN试样在薄层中的凝固过程,计算了凝固线速度,获得了试样动态结晶过程特征;采用扫描电镜测试了Φ20 mm药柱断面微观形貌,研究添加物对样品成型性的影响规律;根据结晶热力学理论研究了DNAN凝固焓与凝固温度的关系;分析了含NHnn=0~4)的化合物对DNAN凝固温度的影响机理并开展了试验验证。结果表明,AP可显著提高DNAN凝固温度,但AP含量及GN、NQ、MNA、HMX等化合物的加入对凝固温度无显著影响;由于凝固温度提高,含AP试样在薄层中凝固线速率最低、结晶为粗大树枝晶。而在体生长时,受结晶潜热影响的纯DNAN微观形貌为柱块状,而含添加物的DNAN试样则显示出结晶细小的特征。分析了DNAN的凝固热力学特征,凝固温度与凝固焓体现出正相关性,且受异质添加物颗粒对非均匀形核的影响。而DNAN凝固温度影响机理及试验验证表明,含NH4+离子的化合物可显著提高DNAN凝固温度。

    Abstract:

    This study probed the influence of compounds containing NHn n=0-4) groups such as ammonium perchlorate (AP), guanidine nitrate (GN), nitroguanidine (NQ), N-methyl-4-nitroaniline (MNA) and cyclotetramethylene-tetranitramine (HMX) on the solidification process and solidification temperature of 2,4-dinitroanisole (DNAN). The effects of the type of additives and AP content on the solidification temperature of DNAN were disclosed by a DSC and an optical microscope technique. Furthermore, as-calculated solidification linear velocity and the characteristics of dynamic crystallization process were analyzed based on the solidification process of addictive-containing DNAN in thin layer observed by microscope. The influence of the additives on the formability of the DNAN was studied by cross-section images of a Φ20 mm test pieces. In addition, relationships between solidification enthalpy and corresponding temperature of DNAN was studied based on crystallization thermodynamics. Besides, the mechanisms towards the influences of NHn compounds on DNAN solidification was analyzed and verified. The results showed that an remarkable-increased solidification temperature of DNAN was achieved by the AP, while being slightly influenced by the AP content and other compounds like GN, NQ, MNA and HMX. The lowest solidification line rate of AP containing object with dendrite-like crystallization could be attributed to the elevated solidification temperature. Influenced by crystallization latent heat during the bulk-growth of DNAN, the microstructure of pure DNAN could be demonstrated as columnar blocks while additive-containing counterparts were disclosed as tiny crystallization. Solidified thermodynamic analysis showed that the DNAN solidification enthalpy was positively correlated with the solidification temperature, which is also affected by heterogeneous additive particles on heterogeneous nucleation. The mechanism and verification of the solidification temperature of DNAN in the present paper demonstrated that the additives with NH4+ can significantly improve the solidification temperature of DNAN.

    表 1 含 NHn(n=0~4)的化合物及试样组成Table 1 The type of NHn(n=0-4) compounds and composition of different samples
    表 2 试样的凝固温度Table 2 The solidification temperature of samples
    图1 凝固温度测试程序曲线Fig.1 The solidification temperature measurement procedure curve
    图2 不同AP含量的DNAN的凝固过程DSC曲线Fig.2 DSC curves of solidification process of DNAN with different AP contents
    图5 含NHn(n=0~4)的化合物DNAN凝固相变焓与凝固温度Fig.5 The ΔHm and TDSC of DNAN containing NHn(n=0-4) compounds
    图6 含AP、AN、NH4Cl的DNAN试样凝固温度Fig.6 The solidification temperature of DNAN with AP, AN and NH4Cl
    表 3 试样凝固线速率Table 3 Solidification rate of samples
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引用本文

张蒙蒙,王红星,李秉擘,等.含NHnn=0~4)的化合物对DNAN凝固过程及凝固温度的影响机理[J].含能材料, 2022, 30(2):130-137. DOI:10.11943/CJEM2021073.
ZHANG Meng-meng, WANG Hong-xing, LI Bing-bo, et al. Solidification Process and Solidification Temperature of DNAN Containing NHnn=0-4) Compounds and Its Mechanism[J]. Chinese Journal of Energetic Materials, 2022, 30(2):130-137. DOI:10.11943/CJEM2021073.

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  • 收稿日期: 2021-04-06
  • 最后修改日期: 2021-05-04
  • 录用日期: 2021-05-06
  • 在线发布日期: 2022-03-17
  • 出版日期: 2022-02-25