CN116217316B - 一种复合含能材料及其制备工艺 - Google Patents
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Abstract
本发明属于火炸药技术领域，具体涉及一种复合含能材料及其制备工艺。所涉及的复合含能材料由核芯颗粒、金属粉和钝感剂制备而成；所述核芯颗粒的制备方法包括：将硝铵类含能材料和硼粉的混合溶液经喷雾干燥后制得炸药颗粒，接着将炸药颗粒与硝铵类含能材料的饱和溶液混合后干燥制备核芯颗粒；所述金属粉选自硼粉，或硼粉与铝粉的混合物。所涉及的制备工艺是将步核芯颗粒与金属粉混合研磨制备混合包覆颗粒；之后将混合包覆颗粒于钝感剂的溶液混合后干燥制得复合含能材料。本发明的复合含能材料具有较高的安全性，可实现含硼炸药压制成型；同时本发明的复合含能材料具有较强的爆轰输出能力。
Description
技术领域
本发明属于火炸药技术领域，涉及一种复合含能材料及其制备工艺，具体涉及一种基于无定型金属硼和黑索今为基的含能复合物及其制备工艺，目的是提高硼的爆轰输出性能。
背景技术
以含铝炸药为代表的金属化炸药因其高爆热、高爆温和爆轰反应时间长等特点，显著提升炸药的能量和做功能力，广泛应用于先进常规武器装药，如温压战斗部、侵彻战斗部和空中兵器、水中兵器等。在含铝炸药的研究基础上，从热力学角度分析不同金属燃烧的内在潜力，铝并非金属可燃剂中最具优势的材料，由于硼具有显著高于铝粉的体积单位热值，作为在炸药中有应用潜质的可燃剂，在金属化炸药应用中具有显著能量优势和广泛的应用前景。
硼粉在氧化过程中生成氧化硼释放很高的热量(140GJ/m3)，远高于铝粉的氧化放热(85GJ/m3)。但因金属硼的能量无法有效释放，导致其在炸药中的应用较少。金属硼在炸药中的能量释放困难主要由于三个原因。一是硼的燃烧是多相燃烧，燃烧时表面会形成液态的B2O3膜包裹在硼的表面，抑制了硼的反应，二是常规的无定型硼工艺成型性困难，三是无定型硼的复杂结构导致其在炸药中的感度高、安全性差。
发明内容
针对现有技术的缺陷或不足，本发明提供了一种复合含能材料。
为此，本发明所提供的复合含能材料由核芯颗粒、金属粉和钝感剂制备而成；
所述核芯颗粒的制备方法包括：将硝铵类含能材料和硼粉的混合溶液经喷雾干燥后制得炸药颗粒，接着将炸药颗粒与硝铵类含能材料的饱和溶液混合后干燥制备核芯颗粒；
所述金属粉选自硼粉，或硼粉与铝粉的混合物；
以质量百分比为100％计，核芯颗粒含量为58％～82％，金属粉含量为10％～38％，钝感剂含量为4％～8％；
所述核芯颗粒中硼粉质量占核芯颗粒质量的2％～3％；所述金属粉中硼粉质量占金属粉质量的30％～100％。
可选的方案中，所述核心颗粒中的硼粉为纳米级硼粉。
可选的方案中，所述金属粉中的硼粉为微米级、无定形硼粉。
本发明同时提供了上述复合含能材料的制备方法。所提供的制备方法包括：
步骤1，制备核芯颗粒：将硝铵类含能材料和硼粉的混合溶液经喷雾干燥后制得炸药颗粒，接着将炸药颗粒与硝铵类含能材料的饱和溶液混合后干燥制备核芯颗粒；
步骤2，将核芯颗粒与金属粉混合研磨制备混合包覆颗粒；
步骤3，将混合包覆颗粒于钝感剂的溶液混合后干燥制得复合含能材料。
进一步，本发明制备方法所制备的复合含能材料中所述核芯颗粒中硼粉嵌入在硝铵类含能材料颗粒内部和/或表面；所述金属粉粘结在核芯颗粒表面形成球壳结构；所述的钝感剂包覆在球壳结构外。
根据本征爆轰理论，混合炸药在爆轰反应初期，爆轰反应区除了氧化剂分解外还有少量的金属粉参与爆轰反应并将能量贡献给冲击波峰值压力；根据该理论，本发明的构思是：设计一种结构，在硝铵类含能材料无氧爆轰时有少量的金属硼粉参与反应，一方面提高反应释能效率，另一方面爆轰反应区内的高温高压使硼能够快速熔化，利用同性材料互熔的特征，降低未反应B的反应阈值，提升体系的能量。
基于上述构思，参见图1所示，本发明的设计思路是在硝铵类含能材料如黑所今(RDX)中嵌入少量的纳米金属硼粉形成核芯结构，参与无氧爆轰反应；在核芯外层包覆一层含有微米硼的金属粉形成球壳，在爆轰反应区内的高温高压使纳米硼能够熔化后粘接金属粉，纳米硼反应释放能量支持微米硼活化，使金属粉持续燃烧放热；在球壳外面包覆一层钝感剂制备成造型粉。进一步利用造型粉压装工艺制备成炸药，造型粉压装工艺是当前最主要的火炸药制备工艺，该工艺是将炸药组分制备成可以压制的造型粉，再将造型粉压制成一定密度和性状的炸药药柱。
本发明与现有技术相比，本发明的复合含能材料具有较高的安全性，相对于同比例常规混合结构，撞击感度和摩擦感度降低到40％以下，可实现含硼炸药压制成型；同时本发明的复合含能材料具有较强的爆轰输出能力，相对于同比例炸药常规混合，爆炸场温度提高100℃以上，内爆环境爆热提升5％以上。
附图说明
图1是本发明复合含能材料的结构涉及示意图；图中各个标号的含义为：1-核芯颗粒，2-金属粉，3-钝感剂，4-RDX，5-纳米硼粉；
图2是本发明实施例核芯结构扫面电镜图。
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。
本发明所述喷雾干燥工艺采用炸药或含能材料领域的常用喷雾干燥设备及相应工艺。常见的喷雾干燥工艺如，将原料与氮气混合(可在静态混合器中进行混合)后送入喷雾干燥设备进行喷雾干燥。本发明所述研磨采用采用炸药或含能材料领域的常用研磨工艺，确保操作安全和混合研磨充分。
本发明所述钝感剂可选用炸药领域的钝感剂，如但不限于EVA、石蜡等。
下面结合附图和实施例对本发明的使用过程作进一步的详细说明，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。以下实施例所用钝感剂为EVA和石蜡。
实施例1：
该实施例的复合含能材料制备原料为：核芯颗粒含量77％，金属粉含量18％，钝感剂含量5％(其中EVA含量3％，石蜡含量2％)；核芯颗粒由RDX和纳米硼粉(粒度20纳米～500纳米)制成，且核芯颗粒中纳米硼粉的质量百分比含量3％；金属粉为微米级、无定形硼粉，粒度50微米～100微米；
制备过程如下：
步骤1，核芯颗粒制备，将RDX溶解于环己酮中配制成溶液，然后加入硼粉搅拌形成悬浮液；在静态混合器中和氮气混合，注入到喷雾干燥装置中进行喷雾干燥，进料速率5ml/min，抽气速率35m3/h，制备炸药微粒；接着在无桨混合器中加入炸药微粒和RDX饱和溶液进行炸药表面修复，搅拌速率5r/min，搅拌时间30分钟，抽滤干燥获得该实施例的核芯颗粒；
步骤2，将粒径为12mm的聚四氟乙烯研磨球倒入研磨腔中，在步骤1制备的核芯颗粒中加入无水乙醇浸润，将浸润后的核芯颗粒和金属粉倒入研磨腔中；研磨15分钟，搅拌速度5r/min，研磨后的浆料经研磨腔的出料口排出，抽滤、烘干，得到该实施例的混合包覆颗粒；
步骤3，将EVA、石蜡溶解到石油醚中，配置钝感剂的溶液，加入步骤2制备的混合包覆颗粒，脱挥干燥制得该实施例的复合含能材料。
该实施例制备的核芯颗粒进行扫描电镜分析，结果如图2所示，其中纳米硼粉嵌入在RDX颗粒内部和(或)表面。
实施例2：
该实施例与实施例1不同的是，所用制备原料为：核芯颗粒含量58％，金属粉含量38％，钝感剂含量4％(其中EVA含量2％，石蜡含量2％)；所述的核芯颗粒中纳米硼粉含量3％；金属粉由微米级无定形硼粉(粒度5微米～50微米)和微米级铝粉(粒度5微米～50微米)制成，且金属粉中硼粉的质量百分比含量为30％，微米铝粉的质量百分比含量为70％。
实施例3：
该实施例与实施例1不同的是，所用制备原料为：核芯颗粒含量82％，金属粉含量10％，钝感剂含量8％(其中EVA含量5％，石蜡含量3％)；所述的核芯颗粒中纳米硼粉含量2％。
对比例：
本实施例为对比例，组成与实施例1相同，参考文献《CL-20炸药基含铝炸药组分微结构对其爆炸释能特性的影响》(火炸药学报，2009年，第12期)，以常规制备工艺，在粘结剂的溶液中加入其余各种族分，脱挥干燥制备复合含能材料。
进一步对上述实施例和对比例的复合含能材料进行如下性能测试：
(1)爆炸场温度：采用模压方式，在100MPa压力下将复合材料颗粒压制成炸药药柱，参考文献《CL-20炸药基含铝炸药组分微结构对其爆炸释能特性的影响》(火炸药学报，2009年，第12期)进行爆炸场温度测试；
(2)能量：在爆炸罐中注入空气，采用模压方式，在100MPa压力下将复合材料颗粒压制成炸药药柱，质量50g，参考GJB 772A-97方法701.1在量热弹中心起爆；量热弹容积20L，通过内爆试验前后蒸馏水温度变化计算炸药爆热；
(3)药粉撞击感度：采用GJB772A-97方法601.1爆炸概率法进行撞击感度测试；
(4)药粉摩擦感度：采用GJB772A-97方法602.1爆炸概率法进行摩擦感度测试。
测试结果如表1所示。
表1本发明与对比例实施效果对比
从表1可以看出，本发明具有较强的爆轰输出能力，相对于同比例共混炸药常规混合，爆炸场温度提高100℃以上；爆热提高7％以上；具有较高的安全性，相对于同比例普通混合结构，撞击感度和摩擦感度显著下降。
Claims (1)
1.一种复合含能材料，其特征在于，所述复合含能材料由核芯颗粒、金属粉和钝感剂制备而成；所述复合含能材料的制备方法包括：
步骤1，制备核芯颗粒：将硝铵类含能材料和硼粉的混合溶液经喷雾干燥后制得炸药颗粒，接着将炸药颗粒与硝铵类含能材料的饱和溶液混合后干燥制备核芯颗粒；所述的核芯颗粒中硼粉嵌入在硝铵类含能材料颗粒内部和/或表面；所述核芯颗粒中的硼粉为纳米级硼粉；
步骤2，将核芯颗粒与金属粉混合研磨制备混合包覆颗粒；所述金属粉粘结在核芯颗粒表面形成球壳结构；所述金属粉选自硼粉，或硼粉与铝粉的混合物；所述金属粉中的硼粉为微米级、无定形硼粉；
步骤3，将混合包覆颗粒于钝感剂的溶液混合后干燥制得复合含能材料；所述的钝感剂包覆在球壳结构外；
以质量百分比为100％计，核芯颗粒含量为58％～82％，金属粉含量为10％～38％，钝感剂含量为4％～8％；
所述核芯颗粒中硼粉质量占核芯颗粒质量的2％～3％；所述金属粉中硼粉质量占金属粉质量的30％～100％。
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| CN112939711A (zh) * | 2021-02-01 | 2021-06-11 | 西安近代化学研究所 | 一种混合炸药结构及制备工艺 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4331080A (en) * | 1980-06-09 | 1982-05-25 | General Electric Co. | Composite high explosives for high energy blast applications |
| CN112479795A (zh) * | 2020-12-11 | 2021-03-12 | 西安近代化学研究所 | 一种含硼炸药及其制备方法 |
| CN112939711A (zh) * | 2021-02-01 | 2021-06-11 | 西安近代化学研究所 | 一种混合炸药结构及制备工艺 |
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