CN101568795A - 防弹片和防弹制品 - Google Patents
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/2913—Rod, strand, filament or fiber
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Laminated Bodies (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
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Abstract
本发明涉及一种防弹片,其包含至少4个单层的叠层,每一单层包含拉伸强度介于3.5GPa和4.5GPa之间的单向取向增强纤维和至多20质量%的基体材料,单层的面密度为至少25g/m2,且每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。本发明还涉及一种防弹模制制品,即成型部件,包含至少两个根据本发明的防弹片,其可以被用作例如用于车辆中的板(尤其是弯曲板);例如用于保护服和防弹背心等中的硬插件。防弹模制制品可选具有陶瓷或金属冲击面。根据本发明的防弹模制制品提供抵抗弹道冲击(例如子弹和弹片)的保护。
Description
本发明涉及防弹片和防弹制品。
防弹片包含至少4个单层的叠层,每一单层包含单向取向的增强纤维以及至多20质量%的基体材料,并且每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。这样的防弹片非常适用于压制或模制防弹制品,诸如板尤其是弯曲板。
从US 4,623,574可知这样的防弹片。此出版物公开了通过如下制造防弹片:交叉层叠多层单层,每一单层包含单向排列拉伸链聚乙烯纤维以及基体材料;然后将其压制成片。此公开的实施例1提到了通过如下来制备单层:将多根聚乙烯纤维并排螺旋卷绕在鼓卷筒上,从而利用KratonD1107溶液涂敷单向排列的纤维。多层这样获得的单层被叠置,使得单层中的纤维方向垂直于相邻单层中的纤维方向。所获得的叠层被置于Apollo压机中的平行板之间,并且用0.6MPa的压力在130℃下压制5分钟,然后冷却。
对于改善的防弹模制制品存在持续的追求,并且本发明人已经惊讶地发现一种防弹片,其能够以改善的可模制性制造压制板或防弹模制制品。改善的可模制性意指,在模制包含本发明的数个防弹片的防弹制品尤其是弯曲防弹制品时,获得了均质产品;这可以由人眼例如通过在模制之后在所述制品中不存在防弹片的不均匀褶皱的现象来判断。
根据本发明,提供了一种改善的防弹片,其包含至少4个单层的叠层,每一单层包含拉伸强度介于3.5和4.5GPa之间的单向取向的增强纤维以及至多20质量%的基体材料,单层的面密度为至少25g/m2,并且每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。
根据本发明的防弹片提供了良好的可模制性。
这可以在模制包含数个层叠起来的本发明的防弹片的弯曲防弹制品时观察到,其中,获得均质的模制制品而不存在防弹片的不规则褶皱。额外的优点在于,根据本发明的防弹片表现出进一步改善的防弹性能。
在本发明中,术语“单层”是指一层单向取向的增强纤维和将纤维基本保持在一起的基体材料。
防弹片包含至少4个单层的叠层,优选地,所述至少4个单层彼此连接或贴附。单层以如下的方式叠置:每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。表示由相邻的单层的纤维所夹的最小角度的旋转角优选介于0°和90°之间,更优选介于10°和80°之间。最优选地,该角度介于45°和90°之间。
本发明的防弹片中的纤维具有介于3.5GPa和4.5GPa之间的拉伸强度。纤维优选具有介于3.6GPa和4.3GPa之间的拉伸强度,更优选具有介于3.7GPa和4.1GPa之间的拉伸强度,最优选地具有介于3.75GPa和4.0GPa之间的拉伸强度。
纤维可以是无机纤维或有机纤维。合适的无机纤维例如为玻璃纤维、碳纤维和陶瓷纤维。
具有这样的高拉伸强度的合适有机纤维例如为:芳族聚酰胺纤维(也常常被称为芳族尼龙纤维),特别是聚对苯二甲酰对苯二胺;液晶聚合物及梯状聚合物纤维,诸如聚苯并咪唑或聚苯并噁唑,特别是聚(1,4-苯撑-2,6-苯并二噁唑)(PBO)或聚(1,4-(2,5-二羟基)苯撑-2,6-吡啶并[4,5-b-4’,5’-e]二咪唑)(PIPD;也被称为M5);以及高度取向的例如聚烯烃、聚乙烯醇和聚丙烯腈的纤维,诸如例如通过凝胶纺丝工艺获得的那些。优选使用高度取向的聚烯烃纤维、芳族聚酰胺纤维、PBO纤维和PIPD纤维或其中至少两种纤维的组合。
甚至更优选使用由通过凝胶纺丝工艺(例如在GB 2042414A或WO01/73173中所述的)制备出的聚乙烯丝构成的高性能聚乙烯纤维或高度拉伸聚乙烯纤维。这些纤维的优点在于,其具有非常高的拉伸强度,同时具有轻的重量,使得其尤其适用于重量轻的防弹制品。
更优选地,使用超高摩尔质量的线性聚乙烯的多丝纱线,所述超高摩尔质量的线性聚乙烯具有至少5dl/g的特性粘度。
这些纤维或纱线的单丝的纤度优选为至多2但尼尔,更优选地,这些纤维的单丝的纤度为至多1.9但尼尔。这使得包含所述防弹片的防弹模制制品具有更好的可模制性。最优选地,这些纤维的单丝的纤度为至多1.8但尼尔。
术语“基体材料”是指如下的材料,其将纤维粘结或保持在一起,并且可以将纤维完全或部分包裹,使得单层的结构在预制片的制造和处理过程被保持。基体材料可以各种形式和方式施加,例如作为纤维单层之间的膜、作为单向排列的纤维之间的横向粘结带或者作为横向纤维(相对于单向纤维为横向的)、或者通过用基体材料浸渍和/或包埋纤维。
在优选实施例中,基体材料是聚合物基体材料,并且可以是热固性材料或热塑性材料,或者这两者的混合物。基体材料的断裂伸长率优选大于纤维的伸长率。基体材料优选具有3%-500%的伸长率。在另一个优选实施例中,基体材料是优选具有至少200%、更优选从300%-1500%、更优选从400%-1200%的伸长率的聚合物基体材料。对于热固性材料组,优选选择乙烯基酯、不饱和聚酯、环氧树脂或苯酚树脂作为基体材料。对于热塑性材料组,优选选择聚氨酯、聚乙烯基类树脂、聚丙烯酸类树脂、聚烯烃或热塑性弹性体嵌段共聚物(诸如聚异戊二烯-聚乙烯-丁烯-聚苯乙烯或聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物)作为基体材料。
更优选地,根据本发明的工艺中的基体材料具有至少3MPa的100%模量。这被理解为在100%的应变处根据ISO 527测量的正割模量。
可以作为水分散体施加的那些基体材料是特别合适的。合适的热塑性材料的实例包括:丙烯酸酯类、聚氨酯、改性聚烯烃和乙烯乙酸乙烯酯(ethylene vinyl acetate)。优选地,基体材料包含聚氨酯。更优选地,聚氨酯是基于聚醚二醇的聚醚聚氨酯。其在宽的温度范围内提供了良好的性能。在具体实施例中,聚氨酯或聚醚聚氨酯是基于脂族二异氰酸酯的,因为这进一步改善的产品性能,尤其是其颜色稳定性。
优选地,100%模量为至少5MPa。100%模量通常低于500MPa。
单层中的基体材料的含量为至多20质量%。这得到防弹性能和可模制性的良好组合。优选地,单层中的基体材料的含量为至多18.5质量%、更优选至多17.5质量%。这得到防弹性能和可模制性的甚至更好的组合。最优选地,单层中的基体材料的含量为至多16质量%。这得到防弹性能和可模制性的最好组合。
业已发现,为了获得所需的可模制性,单层的重量或面密度需要为至少25g/m2。优选地,单层的重量介于30g/m2与200g/m2之间。更优选地,单层的重量介于30g/m2与180g/m2之间。最优选地,单层的重量介于40g/m2与150g/m2之间。
为了制造根据本发明的防弹片,例如通过如下用基体材料浸渍单向增强纤维:将一层或者多层塑料膜施加到纤维平面的顶面、底面或者两侧,然后将这些与纤维一起通过热压辊。然而优选地,纤维在以平行的方式在一个平面中被取向之后,用一定量的含基体材料的液体物质对纤维进行涂层。其优点是可获得对纤维的更快速和更好的浸渍。液体物质可以是例如塑料的溶液、分散液或者熔体。如果塑料的溶液或者分散液被用于制造单层,则该方法还包括蒸发溶剂或者分散剂。以此方式获得单层。随后,至少4个这样的单层以如下方式被叠置:每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。最后,对叠置的单层进行处理,使得其彼此连接或贴附。合适的处理可以是在足够高到获得粘附的温度下压制或层叠叠层。一般来说,更高的温度将提供更好的粘附。通过施加一定的压力可以进一步提高粘附。通过常规实验可以找出合适的压力和温度。在高性能聚乙烯纤维的情况下,这样的温度不能超过150℃。
根据本发明的防弹片可以被合适地堆叠起来,并被压制形成防弹模制制品。防弹模制制品意指成型部件,包含至少两个根据本发明的防弹片,其可以被用作例如用于车辆中的板(尤其是弯曲板);例如用于保护服和防弹背心等中的硬插件。所有这些应用提供抵抗弹道冲击(例如子弹和弹片)的保护。
本发明还涉及包含至少两个根据本发明的防弹片的防弹模制制品。为了使得防弹模制制品具有良好的防弹性,制品中的防弹片的数量为至少10、更优选至少15并且最优选至少20。
一般来说,本发明的防弹模制制品将不厚于125mm;优选地不厚于100mm,并更优选地不厚于80mm。
根据本发明的防弹模制制品可以适于与陶瓷层和/或金属层组合。于是,这样的金属和/或陶瓷层被布置在防弹模制制品的面向弹道冲击的一侧,即作为冲击面。
在根据本发明的防弹模制制品被用于其中可能遇到穿甲弹的威胁的弹道应用的情况下,冲击面优选是陶瓷层。这样,获得具有如下多层结构的制品:陶瓷层/压制堆叠防弹片。可选地,金属层可以作为额外的层存在于陶瓷层和压制堆叠防弹片之间。
合适的陶瓷材料包括例如氧化铝、氧化钛、氧化硅、碳化硅、氮化硅和碳化硼。陶瓷层的厚度取决于弹道威胁水平,但是通常在2mm和30mm之间变化。此复合制品将被优选地布置成使得陶瓷层面向弹道威胁。
合适的金属包括铝、镁、钛、铜、镍、铬、钡、铁(包括其合金,例如钢、不锈钢以及铝与镁的合金(所谓的铝5000系列)、铝与锌和镁的合金或者与锌、镁和铜的合金(所谓的铝7000系列))。
本发明还涉及用于制备防弹模制制品的方法。在根据本发明的方法中,根据本发明的堆叠的防弹片可以在大于16.5MPa的压力下在压机或者压制成型机械中被适当地压制。优选地,压力为至少20MPa,或者至少25MPa,因为这进一步提高了模制件的防弹性能。压制过程中的温度优选介于125℃和150℃之间。较高的温度的优点是可以进一步减小压制时间,但是这样的较高温度应该低于纤维的机械性能开始劣化的温度至少10℃。在高性能聚乙烯纤维的情况下,该温度应该不超过150℃,该温度处于纤维的熔融范围以下。在优选的实施例中,优选包含聚氨酯基体材料的叠层在125℃和135℃之间的温度下被压制至少60分钟。在高温下压制之后,叠层在从压机取出之前被冷却到低于100℃、优选低于80℃的温度。在优选实施例中,叠层被冷却同时仍然处在压力之下,优选处在至少5MPa的压力下,更优选处在与前面的处理步骤中的相同的压力下。
最后,本发明涉及保护服,诸如防弹背心,其包含硬板形式的本发明的防弹模制制品。
本申请中所提到的测试方法如下:
·特性粘度IV:根据方法PTC-179(Hercules nc.Rev.Apr.29,1982)在135℃和萘烷中确定特性粘度,溶解时间为16小时,使用DBPC作为抗氧化剂,用量为2g/l溶液,通过在不同浓度下测量的粘度外推到零浓度;
·拉伸性能(在25℃下测量):按照ASTM D885M的规定,利用500mm的名义计量长度的纤维、50%/min的十字头速度,对多丝纱线确定和定义拉伸强度(或强度)、拉伸模量(或模量)以及断裂伸长率。基于所测量的应力-应变曲线,以0.3%和1%应变之间的斜率确定模量。为了计算模量和强度,将所测量的拉伸力除以纤度(通过称重10米的纤维来确定),假定0.97g/cm3的密度,计算得到单位为GPa的值。根据ISO1184(H)测量薄膜的拉伸性能。
·根据ISO 527确定基体材料的模量。对于100mm长(夹具之间的自由长度)和24mm宽的膜条确定100%模量。100%模量是0%和100%的应变之间的正割模量。
现在将利用下面的实例和对比实验进一步阐明本发明,但是本发明不限于此。
实例1
首先,在鼓卷筒上制造单向单层。为此,将硅化纸贴附到鼓卷筒的鼓上。鼓的周长和宽度都为160cm。每根丝的纤度为1.92但尼尔以及抗断强度(tenacity)为3.6GPa的聚乙烯纱线以3.08mm的间距被卷绕在鼓卷筒上。在被卷绕在鼓上之前,将纱线用苯乙烯异戊二烯苯乙烯嵌段共聚物在水中的分散液润湿。通过稀释分散液,由纱线吸收的固体量被调节到18wt%(相对于纱线量)。
通过将鼓加热到~65℃蒸发所有的水。这样,制备出具有48.6g/m2的纱线面密度和10.7g/m2的基体面密度的单层。
在添加第二单层之前,第一单层被从鼓取出,旋转90°,并再次被贴附到鼓上。利用同样的过程,通过将纱线卷绕在鼓上,将第二单层粘附到第一单层上。第二层的纱线基本垂直于第一单层中的纱线取向。此过程被重复,以添加第三和第四单层。
最终的片,即根据本发明的防弹片,由4个以0°/90°/0°/90°方向取向的单层构成。其具有237.4g/m2的面密度(AD)。
总共67个40×40cm的这样的最终片被叠置在一起,并被压制成防弹板。
用于获得防弹板的压制条件如下:
具有67个最终片的叠层被置于标准压机的两个压板之间。压板的温度介于125-130℃之间。组件被保持在压机中,直到组件中心处的温度处于115-125℃之间。随后,将压力增大到30MPa的压制压力,并且将组件在此压力下保持65分钟。随后,在相同的压制压力下将组件冷却到60℃的温度。
压制板的面密度为15.9kg/m2。板中的纱线的面密度为13kg/m2。
根据STANAG 2920中描述的过程,对所获得的板进行射击测试。使用7.62×39mm软钢芯子弹(常常也被称为‘AK47MSC子弹’)。子弹从Messrs Sellier & Belliot,Czech Republic获得。进行这些测试的目的是确定V50和/或能量吸收。V50是50%的射弹将穿透装甲板的速度。测试过程如下。首先,以预计的V50速度射击第一射弹。在撞击之前的即刻测量实际速度。如果射弹被阻挡,则以提高约10%的预期速度射击下一射弹。如果其穿透,则以降低约10%的预期速度射击下一射弹。总是测量撞击的实际速度。V50是两个最高的被阻挡速度和两个最低的穿透速度的平均值。装甲的性能还通过如下来确定:计算在V50下射弹的动能,将其除以板的面密度,即所谓的‘Eabs’。
板的V50被发现为782m/s,Eabs为186J m2/kg。
对比实验A
使用与实例1中所述的相同的过程来制造片,不同之处在于每根丝的纤度为3.3但尼尔,纱抗断强度为3.3GPa,基体含量为22%,并且纱间距为6.08mm。这得到包含4个单层的片,每一单层具有24.3g/m2的纱线面密度和6.9g/m2的基体面密度。
通过压制134个片,获得面密度为16.7kg/m2、纱线面密度为13.0kg/m2的板。此纱线面密度等于实例1中的纱线面密度。
板的V50被发现为666m/s,Eabs为142J m2/kg。
这些结果表明尽管板中的聚乙烯纤维的用量相同,即13kg/m2,但是实例1中的根据本发明的板表现出明显更高的Eabs。
表1
实例1 | 对比实验A | |
拉伸强度 [GPa]每片中的单层数 [-]基体的质量%每一单层的纱线AD [g/m2]每一单层的基体AD [g/m2]单层AD [g/m2]每片AD [g/m2]每一组件的片数组件AD [kg/m2]组件中的纱线AD [kg/m2]V50 [m/s]Eabs纱线 | 3.641848.610.759.4237.46715.913.0782188 | 3.342224.36.931.2124.913416.713.0683143 |
Claims (11)
1.一种防弹片,其包含至少4个单层的叠层,每一单层包含拉伸强度介于3.5GPa和4.5GPa之间的单向取向增强纤维和至多20质量%的基体材料,单层的面密度为至少25g/m2,且每一单层中的纤维方向相对于相邻单层中的纤维方向旋转。
2.如权利要求1所述的防弹片,其中单层的面密度为至少40g/m2。
3.如权利要求1或2所述的防弹片,其中所述单层包含至多18.5质量%的基体材料。
4.如权利要求1-3中任意一项所述的防弹片,其中所述单向取向增强纤维具有介于3.6GPa和4.3GPa之间的拉伸强度。
5.如权利要求1-4中任意一项所述的防弹片,其中所述单向取向增强纤维是高度拉伸聚乙烯纤维。
6.如权利要求1-5中任意一项所述的防弹片,其中所述基体材料具有至少3MPa的100%模量。
7.如权利要求1-6中任意一项所述的防弹片,其中单丝的纤度为至多2但尼尔。
8.防弹模制制品,其包含至少10个如权利要求1-6中任意一项所述的防弹片。
9.如权利要求8所述的防弹模制制品,还包含陶瓷或金属冲击面。
10.保护服,其诸如为防弹背心,包含权利要求8或9所述的防弹模制制品。
11.如权利要求1-7中任意一项所述的防弹片在制造防弹制品中的用途。
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-
2007
- 2007-12-21 JP JP2009541904A patent/JP2010513836A/ja active Pending
- 2007-12-21 WO PCT/EP2007/011324 patent/WO2008077605A1/en active Application Filing
- 2007-12-21 MX MX2009006774A patent/MX2009006774A/es unknown
- 2007-12-21 CA CA002672720A patent/CA2672720A1/en not_active Abandoned
- 2007-12-21 US US12/520,711 patent/US8592023B2/en active Active
- 2007-12-21 EA EA200900863A patent/EA014219B1/ru not_active IP Right Cessation
- 2007-12-21 KR KR1020097015255A patent/KR20090094851A/ko not_active Application Discontinuation
- 2007-12-21 AU AU2007338373A patent/AU2007338373B2/en active Active
- 2007-12-21 CN CNA2007800477983A patent/CN101568795A/zh active Pending
- 2007-12-21 EP EP07857044.7A patent/EP2095057B1/en active Active
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2009
- 2009-06-11 IL IL199320A patent/IL199320A/en active IP Right Grant
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105452797A (zh) * | 2013-08-07 | 2016-03-30 | 帝斯曼知识产权资产管理有限公司 | 防弹片、包含这种片的制品及其制造方法 |
KR20160048768A (ko) * | 2013-08-07 | 2016-05-04 | 디에스엠 아이피 어셋츠 비.브이. | 방탄 시트, 이러한 시트를 포함하는 물품 및 그 제조 방법 |
KR102236608B1 (ko) * | 2013-08-07 | 2021-04-06 | 디에스엠 아이피 어셋츠 비.브이. | 방탄 시트, 이러한 시트를 포함하는 물품 및 그 제조 방법 |
CN111559120A (zh) * | 2020-05-30 | 2020-08-21 | 汕头东风印刷股份有限公司 | 一种平压平压纹方法 |
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AU2007338373A1 (en) | 2008-07-03 |
US20100064404A1 (en) | 2010-03-18 |
JP2010513836A (ja) | 2010-04-30 |
CA2672720A1 (en) | 2008-07-03 |
MX2009006774A (es) | 2009-07-06 |
EP2095057A1 (en) | 2009-09-02 |
US8592023B2 (en) | 2013-11-26 |
AU2007338373B2 (en) | 2014-01-09 |
WO2008077605A1 (en) | 2008-07-03 |
IL199320A (en) | 2013-10-31 |
EA014219B1 (ru) | 2010-10-29 |
EP2095057B1 (en) | 2017-04-12 |
EA200900863A1 (ru) | 2009-10-30 |
KR20090094851A (ko) | 2009-09-08 |
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