CN106113814A - 一种环氧树脂基防弹复合材料及其制备方法 - Google Patents
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Abstract
本发明提供一种环氧树脂基防弹复合材料及其制备方法,其特点是:受弹层和阻弹层相同,均为氧化石墨烯/芳纶机织布/环氧树脂,能量吸收层(缓冲层)为氧化石墨烯/芳纶三维机织间隔织物/环氧树脂,其主要特点是:受弹层、能量吸收层和阻弹层中的氧化石墨烯片均以布面取向均匀排列在树脂、芳纶机织布和芳纶三维机织间隔织物中。以上三层以环氧树脂固化在一起,成为整体的防弹复合材料。本发明防弹复合材料具有比现有钢化、金属、陶瓷等防弹材料更加优异的防弹性能,可以用于柔性防弹衣的致命部位增强、各种防子弹直弹冲击、工程抗冲击材料等,并且材料轻薄,制作简单。
Description
技术领域
本发明属于新型复合材料技术领域,涉及防弹材料及制备方法的改进,具体说是一种环氧树脂基防弹复合材料及其制备方法。
背景技术
目前防弹材料主要有两种:一种是软质材料,一种是硬质材料。软质材料主要由芳纶或高密度聚乙烯等柔性材料以不同的方式编织制成,主要用于非直弹即流弹或弹片的冲击,抗冲击效果有待进一步提高;硬质材料主要是陶瓷材料、金属材料、复合材料等组成,这些材料虽然可以达到较好的抗冲击效果,但还存在质量重、厚度较厚及佩戴不方便等缺点,应用范围受到很大限制。如何设计一种质量轻薄,抗冲击效果好、制作方便的多用途防弹复合材料,这是本技术领域亟待解决的问题。
发明内容
本发明为解决现有技术存在的上述问题,提供一种环氧树脂基防弹复合材料及其制备方法,防弹复合材料质量轻薄,抗冲击效果好,制备方法合理、方便。
本发明的目的是通过以下技术方案来实现的:
一种环氧树脂基防弹复合材料,包括受弹层、能量吸收层和阻弹层,其特征在于,所述受弹层和阻弹层的组成相同,均为氧化石墨烯/芳纶机织布/环氧树脂制成,所述能量吸收层为氧化石墨烯/芳纶三维机织间隔织物/环氧树脂制成,所述受弹层、能量吸收层及阻弹层中的氧化石墨烯均以布面取向均匀排列在所述环氧树脂、所述芳纶机织布和芳纶三维机织间隔织物中,所述受弹层、能量吸收层及阻弹层用所述环氧树脂固化在一起,形成整体的防弹复合材料。
对上述技术方案的改进:所述受弹层和阻弹层中的芳纶机织布规格为:纱线1000-3000D,单重200-500g/m2,厚度0.20-0.50mm;所述能量吸收层中的芳纶三维机织间隔织物规格为:纱线1000-3000D,单重500-1200g/m2,厚度5-12mm。
一种上述环氧树脂基防弹复合材料的制备方法,其特征在于,制备方法包括如下步骤:
(1)氧化石墨烯水溶液的制备:采用改进的Hummers法制备氧化石墨,得到氧化石墨烯水溶液;
(2)氧化石墨烯水溶液与环氧树脂混合:氧化石墨烯水溶液先与固化剂混合;然后将氧化石墨烯制成水溶液与环氧树脂混合,得到氧化石墨烯片/环氧树脂混合液。
(3)氧化石墨烯/环氧树脂混合液剪流取向:将所述氧化石墨烯片/环氧树脂混合液放入树脂罐,经管道以一定的压力挤出剪流狭缝,氧化石墨烯/环氧树脂混合液流经狭缝高压剪切作用使氧化石墨烯片在氧化石墨烯片/环氧树脂混合液内转向,并沿狭缝取向,浸涂于下方的所述芳纶机织布和芳纶三维机织间隔织物上,结合布面的前进使氧化石墨烯片沿布面取向。
对上述技术方案的改进:所述步骤(1)氧化石墨烯溶液的具体制备方法:采用改进的Hummers法制备氧化石墨,分两步进行制备:一是预氧化阶段,对石墨进行预氧化后晾干备用;二是对预氧化的石墨进一步氧化,最终得到氧化石墨烯水溶液。氧化石墨烯带有大量含氧官能团,使得其带负电荷,片层之间通过静电排斥作用,达到较好地分散效果,并能相互排列取向,最终能够平行排列、均匀地分散在液体中。
所述步骤(2)的具体方法:将氧化石墨烯制成水溶液100-150mg/L,与环氧树脂以氧化石墨烯与环氧树脂质量百分比1%混合,在超声条件下,氧化石墨烯水溶液与环氧树脂通过搅拌进行混合,混合时间30分钟,脱泡1小时,得到氧化石墨烯片/环氧树脂混合液。
所述步骤(3)中,树脂混合液经管道以0.35-0.50MPa压力挤出剪流狭缝,所述受弹层、阻弹层中的芳纶机织布以及能量吸收层中的芳纶三维机织间隔织物各由一套送布机构带动以1-3m/min的速度前进,对应每层芳纶机织布和芳纶三维机织间隔织物的上方各有一个剪流狭缝,所述剪流狭缝尺寸为1.5mm-2mm,将氧化石墨烯片/环氧树脂混合液均匀浸涂于布面,然后依次进行层合、75-95℃干燥1-1.5小时、10-15GPA热压固化24-30小时。
对上述技术方案的进一步改进:所述的环氧树脂基防弹复合材料至少包含2层受弹层、2层能量吸收层和2层阻弹层的复合层压织物,以用于对抗冲击效果要求更高的场合。
对上述技术方案的进一步改进:所述热压固化过程用模具模压,形成固定形状的防弹复合材料产品,例如:护膝、安全帽等特定形状的抗冲击复合材料产品。
本发明与现有技术相比有许多优点和积极效果:
1、本发明在环氧树脂基防弹复合材料中加入氧化石墨烯,可以显著提高复合材料的力学性能(拉伸、弯曲等);本发明的技术关键是:受弹层、能量吸收层及阻弹层中的氧化石墨烯均以布面取向均匀排列在环氧树脂和所述芳纶机织布或芳纶三维机织间隔织物中,可以显著提高复合材料抗冲击性能;
2、本发明采用的芳纶机织布可以提高复合材料的整体性能;采用的三维机织间隔芳纶布用于增强体可以高效吸收冲击能量,使抗冲击效果大幅度提高;
3、本发明防弹复合材料具有比现有钢化、金属、陶瓷等防弹材料更加优异的防弹性能,可以用于柔性防弹衣的致命部位增强、各种防子弹直弹冲击、工程抗冲击材料等,并且材料轻薄,制备方法合理、简单;
4、本发明防弹复合材料的抗冲击效果较单纯的芳纶布/环氧树脂复合材料高3-5倍或以上,且硬度较大。
附图说明
图1为本发明环氧树脂基防弹复合材料制备过程中剪流狭缝的剪流作用示意图;
图2为本发明环氧树脂基防弹复合材料制备过程中氧化石墨烯片转向、沿布面取向的示意图;
图3为本发明环氧树脂基防弹复合材料制备的制备方法中涂浸胶过程示意图;
图4为一种环氧树脂基防弹复合材料中受弹层、能量吸收层和阻弹层的结构示意图。
具体实施方式
下面结合附图和实施例对本发明做进一步详细描述。
参见图3、图4,本发明一种环氧树脂基防弹复合材料的实施例,防弹复合材料包括受弹层6、能量吸收层5和阻弹层7,受弹层6和阻弹层7的组成相同,均为氧化石墨烯/芳纶机织布3/环氧树脂制成,所述能量吸收层5为氧化石墨烯/芳纶三维机织间隔织物4/环氧树脂制成。所述受弹层6、能量吸收层5及阻弹层7中的氧化石墨烯均以布面取向均匀排列在环氧树脂、芳纶机制布3和芳纶三维机织间隔织物4中,所述受弹层6、能量吸收层5及阻弹层7用环氧树脂固化在一起,形成整体的防弹复合材料。
具体而言:所述受弹层6和阻弹层7中的芳纶机织布3规格为:纱线采用1000-3000D的芳纶纱线,芳纶机织布3的单重为200-500g/m2,厚度0.20-0.50mm;所述能量吸收层中的芳纶三维机织间隔织物4规格为:纱线采用1000-3000D的芳纶纱线,芳纶三维机织间隔织物4的单重500-1200g/m2,厚度5-12mm。
参见图1-图4,本发明一种环氧树脂基防弹复合材料的制备方法的具体实施方式,制备方法包括如下步骤:
一种上述环氧树脂基防弹复合材料的制备方法,其特征在于,制备方法包括如下步骤:
(1)氧化石墨烯水溶液的制备:采用改进的Hummers法制备氧化石墨,得到氧化石墨烯水溶液;
(2)氧化石墨烯水溶液与环氧树脂混合:氧化石墨烯水溶液先与固化剂混合;然后将氧化石墨烯制成水溶液与环氧树脂混合,得到氧化石墨烯片/环氧树脂混合液。
(3)氧化石墨烯/环氧树脂混合液剪流取向:将所述氧化石墨烯片/环氧树脂混合液放入树脂罐,经管道以一定的压力挤出剪流狭缝2,氧化石墨烯/环氧树脂混合液流经狭缝高压剪切作用使氧化石墨烯片在混合液内转向,并沿剪流狭缝取向2(如图2所示),浸涂于下方的所述芳纶机织布3和芳纶三维机织间隔织物4上,结合布面的前进使氧化石墨烯片沿布面取向(如图3所示)。
具体而言:上述步骤(1)氧化石墨烯溶液的具体制备方法:采用改进的Hummers法制备氧化石墨,分两步进行制备:一是预氧化阶段,对石墨进行预氧化后晾干备用;二是对预氧化的石墨进一步氧化,最终得到氧化石墨烯水溶液。氧化石墨烯带有大量含氧官能团,使得其带负电荷,片层之间通过静电排斥作用,达到较好地分散效果,并能相互排列取向,最终能够平行排列、均匀地分散在液体中。
上述步骤(2)的具体方法:将氧化石墨烯制成水溶液100-150mg/L,以氧化石墨烯与环氧树脂质量百分比1%混合,在超声条件下,氧化石墨烯水溶液与环氧树脂通过搅拌进行混合,混合时间30分钟,脱泡1小时,得到氧化石墨烯片/环氧树脂混合液。
上述步骤(3)中,树脂混合液经管道以0.35-0.50MPa压力挤出剪流狭缝(如图2所示),所述受弹层6、阻弹层7中的芳纶机织布3以及能量吸收层5中的芳纶三维机织间隔织物4各由一套送布机构带动以1-3m/min的速度前进,对应每层芳纶机织布和芳纶三维机织间隔织物的上方各有一个剪流狭缝2,所述剪流狭缝尺寸为1.5mm-2mm,将氧化石墨烯片/环氧树脂混合液均匀浸涂于布面(如图3所示),然后依次进行层合、75-95℃干燥1-1.5小时、10-15GPA热压固化24-30小时。
以下为本发明制备方法的具体实施例:
实施例1:
1、氧化石墨烯制成水溶液118mg/L,环氧树脂为双酚A型E一51;固化剂QS-1850,按氧化石墨烯溶液与环氧树脂的体积比为1:10混合(氧化石墨烯与环氧树脂的质量百分比约为1%)。
2、受弹层6和阻弹层7的芳纶机织布3规格:纱线1000D,单重220g/m2,厚度0.28mm;能量吸收层5芳纶三维机织间隔织物4规格:纱线1000D,单重650g/m2,厚度5.5mm。
3、环氧树脂管道压力0. 35MPa,送布机构速度3m/min,对应受弹层6、能量吸收层5和阻弹层7的剪流狭缝尺寸分别为1.5mm、2mm、1.5mm。
4、层合热压固化条件:干燥温度75℃,干燥时间1小时,热压压力:10GPa,固化温度140℃,固化时间24小时。得到的复合材料抗冲击性能,落锤冲击能量吸收达到了1.58KJ,为类似结构的芳纶布/环氧树脂复合材料的2.8倍。
实施例2:
1、氧化石墨烯制成水溶液118mg/L,环氧树脂为双酚A型E一51;固化剂QS-1850,按氧化石墨烯溶液与环氧树脂的体积比为1:10混合。
2、受弹层6和阻弹层7的芳纶机织布3规格:平纹,纱线1500D,单重240g/m2,厚度0.3mm;能量吸收层5的芳纶三维机织间隔织物4规格:纱线1500D,单重850g/m2,厚度8.5mm。
3、环氧树脂管道压力0. 42MPa,送布机构速度1.5m/min,对应受弹层6、能量吸收层5和阻弹层7的剪流狭缝尺寸分别为1.5mm、2mm、1.5mm。
4、层合热压固化条件:干燥温度75℃,干燥时间1.5小时,热压压力:10GPa,固化温度140℃,固化时间24小时。得到的复合材料抗冲击性能,落锤冲击能量吸收达到了2.05KJ,为类似结构的芳纶布/环氧树脂复合材料的3.0倍。
实施例3:
1、氧化石墨烯制成水溶液118mg/L,环氧树脂为双酚A型E一51;固化剂QS-1850,按氧化石墨烯溶液与环氧树脂的体积比为1:10混合。
2、受弹层6和阻弹层7的芳纶机织布3规格:平纹,纱线3000D,单重440g/m2,厚度0.42mm;能量吸收层5中芳纶三维机织间隔织物4规格:纱线3000D,单重1050g/m2,厚度11.5mm。
3、树脂管道压力0.5MPa,送布机构速度1m/min),对应受弹层6、能量吸收层5和阻弹层7的剪流狭缝尺寸分别为1.5mm、2mm、1.5mm。
4、层合热压固化条件:干燥温度85℃,干燥时间1.5小时,热压压力:10GPa,固化温度140℃,固化时间24小时。得到的复合材料抗冲击性能,落锤冲击能量吸收达到了2.58KJ,为类似结构的芳纶布/环氧树脂复合材料的3倍。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (6)
1.一种环氧树脂基防弹复合材料,包括受弹层、能量吸收层和阻弹层,其特征在于,所述受弹层和阻弹层的组成相同,均为氧化石墨烯/芳纶机织布/环氧树脂制成,所述能量吸收层为氧化石墨烯/芳纶三维机织间隔织物/环氧树脂制成,所述受弹层、能量吸收层及阻弹层中的氧化石墨烯均以布面取向均匀排列在所述环氧树脂、所述芳纶机织布和芳纶三维机织间隔织物中,所述受弹层、能量吸收层及阻弹层用所述环氧树脂固化在一起,形成整体的防弹复合材料。
2.根据权利要求1所述的环氧树脂基防弹复合材料,其特征在于,所述受弹层和阻弹层中的芳纶机织布规格为:纱线1000-3000D,单重200-500g/m2,厚度0.20-0.50mm;所述能量吸收层中的芳纶三维机织间隔织物规格为:纱线1000-3000D,单重500-1200g/m2,厚度5-12mm。
3.一种如权利要求1或2所述环氧树脂基防弹复合材料的制备方法,其特征在于,制备方法包括如下步骤:
(1)氧化石墨烯水溶液的制备:采用改进的Hummers法制备氧化石墨,得到氧化石墨烯水溶液;
(2)氧化石墨烯水溶液与环氧树脂混合:氧化石墨烯水溶液先与固化剂混合;然后将氧化石墨烯制成水溶液与环氧树脂混合,得到氧化石墨烯片/环氧树脂混合液;
(3)氧化石墨烯/环氧树脂混合液剪流取向:将所述氧化石墨烯片/环氧树脂混合液放入树脂罐,经管道以一定的压力挤出剪流狭缝,氧化石墨烯/环氧树脂混合液流经狭缝高压剪切作用使氧化石墨烯片在氧化石墨烯片/环氧树脂混合液内转向,并沿狭缝取向,浸涂于下方的所述芳纶机织布和芳纶三维机织间隔织物上,结合布面的前进使氧化石墨烯片沿布面取向。
4.根据权利要求3所述环氧树脂基防弹复合材料的制备方法,其特征在于,所述步骤(1)氧化石墨烯溶液的具体制备方法:采用改进的Hummers法制备氧化石墨,分两步进行制备:一是预氧化阶段,对石墨进行预氧化后晾干备用;二是对预氧化的石墨进一步氧化,最终得到氧化石墨烯水溶液;
所述步骤(2)的具体方法:将氧化石墨烯制成水溶液100-150mg/L,以氧化石墨烯与环氧树脂质量百分比1%混合,在超声条件下,氧化石墨烯水溶液与环氧树脂通过搅拌进行混合,混合时间30分钟,脱泡1小时,得到氧化石墨烯片/环氧树脂混合液;
所述步骤(3)中,树脂混合液经管道以0.35-0.50MPa压力挤出剪流狭缝,所述受弹层、阻弹层中的芳纶机织布以及能量吸收层中的芳纶三维机织间隔织物各由一套送布机构带动以1-3m/min的速度前进,对应每层芳纶机织布和芳纶三维机织间隔织物的上方各有一个剪流狭缝,所述剪流狭缝尺寸为1.5mm-2mm,将氧化石墨烯片/环氧树脂混合液均匀浸涂于布面,然后依次进行层合、75-95℃干燥1-1.5小时、10-15GPA热压固化24-30小时。
5.根据权利要求3或4所述环氧树脂基防弹复合材料的制备方法,其特征在于,所述的环氧树脂基防弹复合材料包含至少2层受弹层、2层能量吸收层和2层阻弹层的复合层压织物。
6.根据权利要求3或4所述环氧树脂基防弹复合材料的制备方法,其特征在于,所述热压固化过程用模具模压,形成固定形状的抗冲击复合材料产品。
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