CN105555519A - 防弹材料、其制备方法和用途 - Google Patents

防弹材料、其制备方法和用途 Download PDF

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CN105555519A
CN105555519A CN201480051344.3A CN201480051344A CN105555519A CN 105555519 A CN105555519 A CN 105555519A CN 201480051344 A CN201480051344 A CN 201480051344A CN 105555519 A CN105555519 A CN 105555519A
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layer
carrier
layers
ballistic fibers
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CN105555519B (zh
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约瑟夫·亚恩卡尔
吉里·托查塞克
彼得·波拉塞克
弗兰蒂泽克·库塞拉
露西·沃伊托瓦
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VUT V BRNE
Vysoke Uceni Technicke V Brne
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
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    • F41H5/007—Reactive armour; Dynamic armour
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
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    • B32B2266/00—Composition of foam
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    • B32B2266/0214—Materials belonging to B32B27/00
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2571/02—Protective equipment defensive, e.g. armour plates, anti-ballistic clothing

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  • Professional, Industrial, Or Sporting Protective Garments (AREA)
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Abstract

本发明提供一种防弹材料，其特征在于所述材料包括：-多个致密的弹道纤维层，和-在所述弹道纤维层之间插入的至少一个呈现由于剪切应力增大引起的粘度增大的非牛顿流体的中间层，其可选地含有具有从1nm至700nm的尺寸的颗粒或者反增塑剂，所述中间层被直接放置于弹道纤维层之间、或者放置在位于所述弹道纤维层之间的填料或穿孔填料上或者被施加在织物上。本发明还提供制备所述材料的方法。该材料是柔性的、具有低重量且可以特别用于防弹背心、战斗头盔、个人防弹衣和/或用于保护轻步兵车辆和乘用车。

Description

防弹材料、其制备方法和用途
技术领域
本发明涉及新型的防弹和防刺穿材料、其制备方法和用途。所述材料特别适用于防弹背心、战斗头盔、个人防弹衣和/或用于保护轻步兵车辆和乘用车、卡车和移动控制司令部免受弹道威胁。
背景技术
在柔韧的防弹材料和材料组合的领域中的新改进正在持续地尝试实施以与弹道技术的发展保持联系。美国专利No.3,841,954公开了由多层织物缝合在一起且在热和压力下压缩而形成的层压面板或层压板，由此产生了刚性面板用作个人防弹衣中的部件。美国专利No.3,509,833公开了安装在以交叉帘布方式倾斜布置的柔性层压纤维的衬垫物上的陶瓷板的柔韧防护衣。美国专利No.4,522,871和美国专利No.4,781,351提出了含有多层编织的芳香聚酰胺(polyaramid)纤维的柔韧防护衣，例如，以商标KEVLAR出售的材料。美国专利No.4,608,717提出了一种柔韧防护衣，其包括与塞满羽毛、泡沫或毡材料的中间层组合的芳香聚酰胺纤维的多个层。这些层被缝制到一起以形成一体的柔韧面板。美国专利No.3,924,038公开了适于用于飞行员的长颈套装的多层面板或者作为在战争地带中飞机或设备的临时覆盖。面板被设计成提供保护免受通过爆炸弹药抛出的弹片。多层面板包括尼龙布和毡的内垫、中间的蜂窝状垫片和陶瓷板的外保护层。蜂窝状垫片用来将面板固定成不可弯曲的结构。美国专利No.5,060,314公开了由柔韧的弹道织物制成的防护外套，其含有用于硬防护衣弹道衬垫的内袋。另外的垫肩具有浮式衬垫以提供水中的飘浮。美国专利No.3,867,239、No.4,198,707和No.4,633,756公开了防护衣面板，其包括已经经历多次硬化的工艺的板，该板布置在织物衬垫物上的多个层中。美国专利No.7,825,045公开了由浸渍有在呈现剪切增稠性能的流体(由于剪切应力增大导致的粘度增大，非牛顿流体的类型)中的粒子悬浮物的聚合纤维制成的个人防弹衣。然而，浸渍带来一定的限制，例如，限制了颗粒尺寸且与增加粘度的纳米颗粒不相容，由此阻止了浸渍。并且，先前的溶液利用通过高速率冲击引起的剪切应力导致的有序结构的创建。膨胀性流体是低粘度溶液，最通常在聚乙二醇中且含有大量的固体颗粒。所述系统的另一变型利用两类分子的组合，该结构在低剪切速度的条件下维持柔性，从而能够实现由于低分子摩擦带来的自由运动。然而，在高的速度下，存在所述分子摩擦上的急剧增大，导致膨胀性流变响应。
迄今已知的防弹材料是高重量和高体积且缺乏柔韧性，由此极大地限制它们的用途。
发明内容
本发明提供了一种用于防弹的柔韧材料，例如用在个人防弹衣中，所述材料包括：
-多个致密的弹道纤维(ballisticfiber)层(例如，层压品、垫子)，和
-在所述弹道纤维层之间插入的至少一个呈现由于剪切应力增大引起的粘度增大的非牛顿(膨胀性)流体(即剪切增稠材料)的中间层，优选地该中间层对弹道纤维层具有良好的粘合性，且可选地含有1nm至700nm尺寸的颗粒或反增塑剂，所述中间层直接地位于弹道纤维层之间、或者插入位于弹道纤维层之间的载体(例如，致密的或穿孔的塑料载体或纤维载体)上。
载体可以为塑料膜，例如聚对苯二甲酸乙二醇酯，或载体织物，例如由聚酯(PET)、聚酰胺(PA)、液晶(市售的Zylon)或聚乙烯(UHMWPE)制成。然而，所述载体织物不同于致密的弹道纤维层。优选地，载体织物是纳米纤维织物，即，具有尺寸为大约单位至数百纳米的纤维。
致密的弹道纤维层可以由任何类型的弹道织物制成。弹道织物对于本领域人员是熟知的。该材料的示例是以诸如Dyneema或Spectra商标市售的超高分子量聚乙烯(UHMWPE)。还可以利用由聚芳酰胺化合物(市售示例为Kevlar)或液晶纤维(例如，Zylon)制成的弹道纤维层。
因此，本发明不涉及浸渍的弹道纤维。本发明涉及通过采用非牛顿流体的中间层来连接它们，该非牛顿流体的中间层可以是直接施加在纤维层表面上的热塑性橡胶材料(由此使层胶合或粘合)的形式，或者其可以放置在载体或穿孔载体上，例如，在填料或穿孔的填料内。因此由于它们通过中间层接合，故将层缝合到一起不是必要的。这使得在正常条件下的弯曲期间能够进行层的相互运动，由此产生了具有更大柔韧性的防弹材料用于诸如个人防弹衣的配件中。然而，当利用弹道射弹击打时，材料变得僵硬，其明显增大了参与导弹的拦截的致密的弹道纤维层的厚度。中间层优选地具有达0.5mm的厚度。
具有呈现由于剪切应力增大引起的粘度增大的非牛顿流体特征的材料是熟知的。特别合适的非牛顿流体例如为含有变化长度侧链的基于丙烯酸单体的低聚物混合物、基于二苯甲撑二异氰酸酯(MDI)和己二异氰酸酯(HDI)与酯或聚醚醇的聚氨酯、或基于来源于苯乙烯-丁二烯/多萜/二戊烯大分子单体的氧化纤维素的聚醇。优选地，出于该目的，也可以利用具有小于-40℃的玻璃化转变温度的热塑性聚氨酯、丁苯橡胶和其他直链的和轻微交联的(0至20％)的非晶态聚合物。所述流体还可以含有纳米颗粒，优选地硅酸盐纳米颗粒、纤维素纳米颗粒、氧化铝纳米颗粒，其可以采取任何形状，例如球形、针形、薄片。合适的填料纳米颗粒包括热解的和胶态的二氧化硅、POSS颗粒的变型(多面体倍半硅氧烷)、硅酸镁锂、Al2O3颗粒或晶须、纤维素晶须和纳米晶体、ZrO2的颗粒、石墨烯、C60、碳纳米管或所述颗粒的混合式组合。优选地，还可以使用纳米颗粒的分级的亚微簇。此外，反增塑剂可以用来实现液体中的膨胀行为。反增塑剂是在高剪切应力期间降低聚合物链段的运动性的分子。反增塑剂的选择取决于待使用的流体。合适的反增塑剂包括氯化联苯和三联苯、聚苯乙烯乙二醇、松脂酸(abietlicacid)衍生物、氨基和/或羧基终止的低聚酰胺、二甲基膦酸甲酯、4-羟基乙酰苯胺和1，2-环氧基-3-苯氧丙烷。为了实现最小的表面密度，颗粒和反增塑剂可以组合。
在优选的实施方式中，泡沫层被放置于材料的朝内的表面上(拦截侧，即，面向所保护的对象的一侧，例如，防弹衣的穿戴者的身体)。泡沫层因此将防护材料与穿戴者的身体隔开使得由弹体冲击所引起的任何变形被防护所保护对象(例如，人的身体)的泡沫层垫料吸收。出于该目的，可以利用诸如聚乙烯泡沫或聚氨酯泡沫的材料。
本发明还提供了制备防弹材料的方法，其中至少两个致密的弹道纤维层通过至少一个呈现由于剪切应力增大引起粘度增大的非牛顿流体的中间层被接合，得到的材料能够可选地与另外的致密的弹道纤维层连接，以及在优选的实施方式中，得到的材料在一侧被提供有泡沫层。
根据本发明所设计的防护装置能够防护如通过国家司法研究院标准(NationalInstituteofJusticeStandard)0101.03所定义的类型IIIA弹道威胁。类型IIIA威胁对应于44Magnum射弹，其具有15.5克的质量且以450m/s的速度冲击，或者9毫米、全金属外壳包围的具有8克质量和在450m/s的速度下冲击的子弹。对威胁的防护要求在射弹运动方向上目标变形不超过44毫米。在V50弹道测试中，本发明能够抵挡大于500m/s、通常大于600m/s的速度，其中美国标准要求最小速度为430m/s。迄今已有的产品通常能够击败以达600m/s的速度行进的导弹。另外，新的纺织物具有比当前产品小20％至25％的表面密度。
本发明特别适用于制造用于军人、维和部队或必须防止免受弹道射弹导致的死亡或受伤的其他个人的防弹衣。
附图说明
图1是用于防弹的柔性材料的层的布置的一个实施方式的示意图。
N-弹道侧，Z-拦截侧(向内面向所保护的对象)，BV-来自超高分子量聚乙烯的致密的弹道纤维层，NNK-剪切增稠材料(非牛顿流体)的层，P-与穿戴者接触的泡沫层。
具体实施方式
实现本发明的实施例
实施例1：防弹材料的制备。
材料X3M
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)，通过具有球形SiO2纳米颗粒和它们的簇的基于苯乙烯-丁二烯/多萜/二戊烯的非牛顿剪切增稠粘合剂被连接(粘合、胶合)到一起。主要纳米颗粒的尺寸范围为1nm至20nm，簇具有的尺寸达500nm。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。三个垫子由此被粘合成型三层。
总共五个三层被用来制作弹道面板(在弹道侧上)，其通过十个另外的独立的垫子被进一步加固。面板的拦截侧的最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
得到的称为X3M的材料非常适合于柔韧的个人防弹衣。
材料X2
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。该三个垫子通过聚对苯二甲酸乙二醇酯(PET)载体膜接合到彼此，该聚对苯二甲酸乙二醇酯(PET)载体膜承载一薄层的基于丙烯酸单体的剪切增稠粘合剂，其具有球形SiO2纳米颗粒和其簇。主要纳米颗粒的尺寸在1nm至20nm的范围中，簇具有达500nm的尺寸。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
总共十个单独的垫子增强该样品的弹道面板的五个三层。面板的拦截侧的最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
得到的称为X2的材料非常适合于柔韧的个人防弹衣。
材料X2-TOP
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。该三个垫子通过聚对苯二甲酸乙二醇酯(PET)载体膜被接合到彼此，该聚对苯二甲酸乙二醇酯(PET)载体膜承载一薄层的基于丙烯酸单体的剪切增稠粘合剂，其具有球形SiO2纳米颗粒和其簇。主要纳米颗粒的尺寸在1nm至20nm的范围中，簇具有达500nm的尺寸。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
总共五个三层被用来制作弹道面板(在弹道侧上)，其通过十个另外的独立的垫子被进一步加固。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
得到的称为X2-TOP的材料非常适合于柔韧的个人防弹衣。
材料X2-M
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。该三个垫子通过聚对苯二甲酸乙二醇酯(PET)载体膜被接合到彼此，该聚对苯二甲酸乙二醇酯(PET)载体膜承载一薄层的基于丙烯酸单体的剪切增稠粘合剂，其具有球形SiO2纳米颗粒和其簇。主要纳米颗粒的尺寸在1nm至20nm的范围中，簇具有达500nm的尺寸。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
该样品包括在弹道侧上的总共五个独立的垫子和通过另外的五个垫子增强的五个三层以形成弹道面板。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
得到的称为X2-M的材料非常适合于柔韧的个人防弹衣。
材料APU
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。三个垫子通过基于聚氨酯的剪切增稠粘合剂被接合到彼此，该粘合剂含有针形和薄片形状的具有最小尺寸0.1nm至20nm和最大尺寸10nm至1mm的颗粒。纤维素晶须为针形纳米颗粒的填料的示例，然而硅酸镁锂是片形纳米颗粒的填料的示例。该粘合剂形成薄的平坦膜，其最大厚度为0.5mm。
总共十个单独的在弹道侧上的垫子进一步通过五个三层加固以形成在该样品中的弹道面板。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
材料APUNS
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。三个垫子通过基于聚氨酯的剪切增稠粘合剂被接合到彼此，该粘合剂含有0.1％至12％w/w(重量/重量)的二氧化硅纳米颗粒。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
总共十个单独的在弹道侧上的垫子进一步由五个三层加固以形成在该样品中的弹道面板。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
材料APUA
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。三个垫子通过基于聚氨酯的剪切增稠粘合剂被接合到彼此，该粘合剂含有12％至20％w/w的氧化铝纳米颗粒。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
总共十个单独的在弹道侧上的垫子进一步由五个三层增强以形成在该样品中的弹道面板。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
材料X2-TOP-MOD2
三个以例如商标Dyneema或Spectra市售的基于超高分子量聚乙烯(UHMWPE)的致密弹道纤维的层(此后称为垫子或层压品)被连接到一起，由此形成三层。该三个垫子通过聚对苯二甲酸乙二醇酯(PET)载体膜被接合到彼此，该聚对苯二甲酸乙二醇酯(PET)载体膜承载一薄层的基于丙烯酸单体的剪切增稠粘合剂，其具有球形SiO2纳米颗粒和其簇。主要纳米颗粒的尺寸在1nm至20nm的范围中，簇具有达500nm的尺寸。该粘合剂形成薄的平坦膜，该膜的最大厚度为0.5mm。
总共六个在弹道侧上的三层用来制造弹道面板，该弹道面板通过十个另外的独立的垫子被进一步加固。最终层是由聚乙烯(PE)泡沫制成的充当冲击吸收内衬的垫料。
实施例2：弹道极限速度
根据NIJ标准-0101.04，测定用于所制备的单个材料的弹道极限速度。利用重8克的9x19FMJRN圆形物(通过S&B制造)进行测试。速度(由此在测试条件下发生的完全或部分的穿透)被评价。结果是5×(次)完全穿透和5×(次)部分穿透的速度的算术平均值。

Claims (8)

1.一种防弹材料，其特征在于，所述材料包括：
-多个致密的弹道纤维层，和
-在所述弹道纤维层之间插入的至少一个呈现由于剪切应力增大引起的粘度增大的非牛顿流体的中间层，所述中间层被直接放置于弹道纤维层之间、或者被放置在位于所述弹道纤维层之间的载体或穿孔的载体上。
2.根据权利要求1所述的材料，其中所述非牛顿流体的中间层含有从1nm至700nm的尺寸的颗粒或者反增塑剂。
3.根据权利要求1或2所述的材料，其中所述载体或所述穿孔的载体是塑料膜。
4.根据权利要求1或2所述的材料，其中所述载体或所述穿孔的载体是纳米纤维织物。
5.如前述权利要求中任一项所述的材料，其中泡沫层被放置在所述材料的一个表面上。
6.一种用于制备根据权利要求1的方法，其特征在于，至少两个致密的弹道纤维层通过至少一个呈现由于剪切应力增大引起的粘度增大的非牛顿流体的中间层被接合，且所得到的材料能够可选地与另外的致密的弹道纤维层连接。
7.根据权利要求6所述的方法，其中所述得到的材料在一侧被提供有泡沫层。
8.根据权利要求1至5中任一项所述的材料用于防弹背心、战斗头盔、个人防弹衣和/或用于保护轻步兵车辆和乘用车的用途。
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CN108546324A (zh) * 2018-05-17 2018-09-18 厦门安踏体育用品有限公司 一种非牛顿流体材料及智能防冲撞纺织品
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