CN115286474A - 分子钙钛矿型化合物(c6h14n2)k(no3)3作为双基发射药添加组分的应用 - Google Patents
分子钙钛矿型化合物(c6h14n2)k(no3)3作为双基发射药添加组分的应用 Download PDFInfo
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Abstract
本发明公开了分子钙钛矿型化合物(C6H14N2)K(NO3)3作为双基发射药添加组分的应用，所述添加组分可以使双基发射药的火药力提高的同时，降低双基发射药的燃温。
Description
技术领域
本发明涉及分子钙钛矿型化合物的新应用，具体涉及分子钙钛矿型化合物(C6H14N2)K(NO3)3作为双基发射药添加组分的应用。
背景技术
分子钙钛矿型含能晶体是一种致密堆积的三元化合物，具有ABX3钙钛矿拓扑的高对称性。中山大学陈小明、张伟雄、陈劭力等人，首先发明了分子钙钛矿型含能材料(Sci.China Mater.，2018年,61期,1123–1128)，并研制了一系列以高氯酸根为桥联配体的具有高耐热性能、高爆速的含能化合物，并在专利(ZL201610665880.3)中从理论上提出了硝酸根也能用于构筑分子钙钛矿型含能材料，但未指出相关化合物的特征性质和特征用途。
发明内容
发明人深入研究发现，高氯酸为桥联的分子钙钛矿型化合物虽然具有高能量、高爆速的特点，但其感度高、分解过于剧烈以及产物富含HCl酸雾的特点，使得将其用于发射药配方中时压力指数过高且有剧烈烧蚀作用，因此不适合用于发射药领域；发明人进一步研究发现对于硝酸根作为桥联配体构筑的分子钙钛矿型化合物(C6H14N2)K(NO3)3(本文也称DAN-2)，能量计算表明其爆轰性能高于常用炸药，并显示DAN-2加入双基发射药中能提高火药力并降低燃温；此外，钾离子本身具有消焰作用，还可以有效降低身管武器发射时的火焰。因此，DAN-2在发射药中添加，可以在不降低能量水平的同时，降低发射药对身管武器的烧蚀作用，对提高身管武器使用寿命方面有较大的应用价值。
基于发明人的研究发现，本发明提供了分子钙钛矿型化合物(C6H14N2)K(NO3)3作为双基发射药添加组分的应用，所述添加组分用于降低双基发射药火焰温度和提高火药力。
本发明还提供了一种双基发射药，包括基础火药和分子钙钛矿型化合物(C6H14N2)K(NO3)3。
可选的，所述分子钙钛矿型化合物(C6H14N2)K(NO3)3在双基发射药中的添加量为(0％，100％)。
可选的，所述基础火药包括硝化甘油和硝化纤维素。
附图说明
图1为化合物DAN-2的单晶结构图。
具体实施方式
除非有特殊说明，本文中的科学与技术术语根据相关领域普通技术人员的认识理解。
本发明所述分子钙钛矿型化合物(C6H14N2)K(NO3)3(本文也称DAN-2)的制备方法为：常温常压下，将硝酸钾加入水中溶解完全后加入发烟硝酸混匀得混合溶液；之后将三乙烯二胺水溶液滴加至所述混合溶液中反应制得。具体示例如下：
常温常压下，将5.1g(0.05mol)硝酸钾加入到10.2mL水中，溶解后加入7.1g(0.1mol)发烟硝酸混匀后的混合溶液；
搅拌状态下加入5.5g(0.05mol)三乙烯二胺固体和15.0mL水，溶解后制得三乙烯二胺水溶液；
在搅拌状态下，将所述三乙烯二胺水溶液滴加到混合溶液中反应10min，过滤收集反应物，反应物经水洗和乙醇淋洗后常温干燥，得DAN-2白色固体，收率48.0％。
进一步，对所制得的DAN-2的进行结构鉴定，具体采用X射线衍射仪Rigaku XtaLABP300DS diffractometer，采用铜靶
使用SHELXS程序直接法精修结构；结果如图1和表1所示。
表1DAN-2单晶数据表
表1中R1＝Σ||Fo|-|Fc||/Σ|Fo|，wR2＝{Σw[(Fo)2–(Fc)2]2/Σw[(Fo)2]2}1/2。
双基发射药是枪炮弹丸发射的主要能源之一，主要成分为硝化甘油和硝化纤维素等。双基发射药组分的品种和用量不同，赋予发射药的性能有很大的差异。一般来说，双基发射药燃烧时的火焰温度较高，对枪炮武器身管的烧蚀作用较强。为了减小发射药的烧蚀作用，提高武器身管寿命，提高枪炮的射速上限，需要尽可能的降低发射药做功时的火焰温度(燃温)，而通过添加附加物(添加剂)可以起到这类特殊的作用，例如添加碳酸钙、滑石粉等等。但是这类添加剂不具备含能特性，不能大量添加，否则会降低双基发射药的火药力，严重影响火药的能量性能。发明人通过对分子钙钛矿型含能化合物(C6H14N2)K(NO3)3的爆轰性能和能量水平进行分析，证实了分子钙钛矿型含能化合物(C6H14N2)K(NO3)3可用作双基发射药的降低火焰温度和提高火药力作用的添加组分。
其中，爆轰性能分析采用氧弹量热仪，采用EXPLO5热化学计算程序。能量水平分析是通过在双基发射药硝化纤维素—硝化甘油(NC-NG)配方中添加不同比例DAN-2进行内能法分析。
爆轰性能分析结果：
氧弹燃烧热实验表征显示DAN-2的恒容燃烧热为-4212.38kJ·mol-1，根据燃烧方程：
(C6H14N2)[K(NO3)3](s)+5.25O2(g)＝6CO2(g)+7H2O(l)+0.5K2O(s)+2.5N2(g)
换算DAN-2的恒压燃烧热(燃烧焓)：
△cH＝△cU+△nRT,(△n＝n(gaseous products)-n(gaseous reactants),
其中，△cH为恒压燃烧热，△cU为恒容燃烧热，R为理想气体常数，R＝8.314J·mol-1·K-1，T为绝对温度，T＝298.15K，n(gaseous products)为产物气体摩尔数，n(gaseousreactants)为反应物气体摩尔数。
可以得出DAN-2的燃烧焓为-4204.32kJ·mol-1，再根据方程：
△fH(DAN-2)＝6△fH(CO2)+7△fH(H2O)+0.5△fH(K2O)-△cH(DAN-2)
其中，△fH(DAN-2)为DAN-2生成焓，△fH(CO2)为CO2(g)生成焓，△fH(H2O)为H2O(l)生成焓，△fH(K2O)为K2O(s)生成焓(CO2、H2O、K2O的生成焓来自美国国家标准与技术研究院NIST公开标准数据库)，△cH(DAN-2)为DAN-2燃烧焓。
可以得出DAN-2的生成焓为-339.13kJ·mol-1，代入EXPLO5热化学计算程序可得DAN-2的爆轰参数，如表2所示，DAN-2具有比常用军用含能材料TNT更高的密度、爆热、爆速和爆压。
表2DAN-2爆轰性能
表2中：ρ为晶体学密度；△Hf为生成焓，其中DAN-2的生成焓根据氧弹燃烧热实验结果得出；Q为爆热，vD为爆速，p为爆压；TNT的生成焓及爆轰参数来自EXPLO5内置数据库。
能量水平分析及相关结果：
从DAN-2的爆轰性能无法推断其在发射药中表现的能量水平及特征作用，需要根据DAN-2的特征参数(包括元素组成、生成焓、密度等)通过内能法在发射药的特定配方中计算判断。发现将DAN-2添加入经典双基发射药配方硝化纤维素(NC)—硝化甘油(NG)配方中时，能量水平如表3所示：当加入2％DAN-2时，配方火药力上升(1153→1156kJ·kg-1)，火焰温度下降(3603→3568K)；当加入25％DAN-2时，配方火药力大幅增加2.5％(1153→1182kJ·kg-1)，火焰温度大幅降低6.4％(3603→3372K)。可见DAN-2在双基发射药中起到提升火药力，降低火焰温度的作用。
表3DAN-2能量水平
表3中，f为火药力，Qv为定容爆热，Tv为定容爆温。
Claims (4)
1.分子钙钛矿型化合物(C6H14N2)K(NO3)3作为双基发射药添加组分的应用，所述添加组分用于降低双基发射药火焰温度和提高火药力。
2.一种双基发射药，包括基础火药，其特征在于，还包括，分子钙钛矿型化合物(C6H14N2)K(NO3)3。
3.如权利要求2所述的双基发射药，其特征在于，所述分子钙钛矿型化合物(C6H14N2)K(NO3)3在双基发射药中的添加量为(0％，100％)。
4.如权利要求2所述的双基发射药，其特征在于，所述基础火药包括硝化甘油和硝化纤维素。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8828161B1 (en) * | 2006-01-30 | 2014-09-09 | The United States Of America As Represented By The Secretary Of The Navy | Ballistic modification and solventless double base propellant, and process thereof |
| CN106278771A (zh) * | 2016-08-12 | 2017-01-04 | 中山大学 | 一类化合物在作为含能材料方面的用途 |
| CN113149933A (zh) * | 2020-01-22 | 2021-07-23 | 中山大学 | 化合物及其制备方法以及作为含能材料的用途 |
| WO2021147960A1 (zh) * | 2020-01-22 | 2021-07-29 | 中山大学 | 化合物及其制备方法以及作为含能材料的用途 |
| US20210269375A1 (en) * | 2016-08-12 | 2021-09-02 | Xi'an Crysten Materials Technology Corporation Limited | Perovskite type compound abx3 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8828161B1 (en) * | 2006-01-30 | 2014-09-09 | The United States Of America As Represented By The Secretary Of The Navy | Ballistic modification and solventless double base propellant, and process thereof |
| CN106278771A (zh) * | 2016-08-12 | 2017-01-04 | 中山大学 | 一类化合物在作为含能材料方面的用途 |
| CN107721781A (zh) * | 2016-08-12 | 2018-02-23 | 中山大学 | 一类化合物在作为含能材料方面的用途 |
| US20210269375A1 (en) * | 2016-08-12 | 2021-09-02 | Xi'an Crysten Materials Technology Corporation Limited | Perovskite type compound abx3 |
| CN113149933A (zh) * | 2020-01-22 | 2021-07-23 | 中山大学 | 化合物及其制备方法以及作为含能材料的用途 |
| WO2021147960A1 (zh) * | 2020-01-22 | 2021-07-29 | 中山大学 | 化合物及其制备方法以及作为含能材料的用途 |
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