CN111491792A - 防弹成形制品 - Google Patents
防弹成形制品 Download PDFInfo
- Publication number
- CN111491792A CN111491792A CN201880081347.XA CN201880081347A CN111491792A CN 111491792 A CN111491792 A CN 111491792A CN 201880081347 A CN201880081347 A CN 201880081347A CN 111491792 A CN111491792 A CN 111491792A
- Authority
- CN
- China
- Prior art keywords
- layer
- binder
- layers
- polyolefin fibers
- shaped article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Classifications
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Abstract
本发明提供一种用于制造防弹成形制品的方法,其中所述成形制品包括:i)多个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及ii)多个粘结剂层;并且所述方法包括:a)提供多个前驱片材,其中所述前驱片材的每个包括i)至少一个实质上缺乏结合基质的单向排列的聚烯烃纤维层,以及ii)至少一个粘结剂层;b)堆叠所述前驱片材以形成叠层,其中基于所述叠层的总重量,在所述叠层中的粘结剂总量为5.0重量%至12.0重量%;c)在低于所述聚烯烃纤维的熔点1℃至30℃的温度和至少8MPa的压力下压制在步骤b)中制造的叠层;并且d)在维持压力的同时将在步骤c)中制造的压制的叠层冷却至低于所述聚烯烃纤维的熔点至少50℃。
Description
本发明涉及一种用于制造防弹成形制品的方法,该制品包括多个实质上缺乏结合基质的单向排列的聚烯烃纤维层和多个粘结剂层。本发明进一步涉及一种可通过该方法获得的防弹成形制品以及一种适于在该方法中使用的前驱片材。
通过将嵌入基质中单向排列的纤维叠层进行压制来制造防弹成形制品是在本领域中已知的。在本领域中还教导了为了改进在所提供的面密度下的防弹性能使所存在的结合基质的比例最小化。为此所提出的基本原理为虽然需要某些基质来对成形制品提供机械完整性,但结合基质不会有助于弹头拦截能力,因此应该最小化或甚至避免其存在。
WO 2009/056286描述出一种不存在基质的单向排列聚乙烯纤维的材料片,而是通过对绕着板卷绕的纤维施加热和压力而使纤维熔合在一起。绕着板相继地卷绕多个垂直层;挤压卷绕有纤维层的板;然后,从板上取下所产生的两个固结层的片材。
WO 2010/1222099描述出在缺乏结合基质的情况下将织造纤维层固结成硬面板的实施方式。在WO 2012/080274中进一步描述了在不存在结合基质的情况下,使单向排列的纤维经受热和压力来制造带。在没有加入结合基质的情况下,使用所述带来制造单层的固结叠层。
WO 2013/131996描述出一种由热塑性聚合物带制成的复合面板,所述热塑性聚合物带例如由超高分子量聚乙烯纤维以及塑性体(作为粘结剂)来制造。通过压制由热塑性聚合物带所形成的片材来制造防弹成形制品。
现有技术中还已知,随着压制的叠层的密度增加时,其弹道性能(特定吸收能量)增加。WO 1997/00766描述了压制用结合基质浸透的超高分子量聚乙烯层的叠层来实现使压紧叠层的密度高达理论最大密度的99.5%。但是,随着压制压力的增加,叠层的密度会以减少的速率增大。因此,已建议了有益的压制压力上限。
在现有技术中所描述的材料可具有令人满意的防弹性能;但是,其性能可以进行改进。
因此,本发明的一个目标为提供一种防弹成形制品,该防弹成形制品在所提供的面密度下具有改进的防弹性能。另一个目标是一种用于制造具有改进的弹道性能的防弹成形制品的改进方法。
发明人们已发现通过在特定的压力和温度条件下,压制多个实质上缺乏结合基质的单向排列的聚烯烃纤维层和多个粘结剂层会产生具有改进的弹道性能的成形制品,其中基于该成形制品的总重量,粘结剂的总量为5.0至12.0重量%。
此外,本发明提供一种用于制造防弹成形制品的方法,其中该成形制品包括:
i)多个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)多个粘结剂层;并且该方法包括:
a)提供多个前驱片材,所述前驱片材的每个包括:i)至少一个实质上缺乏结合基质的单向排列的聚烯烃纤维层,以及ii)至少一个粘结剂层;
b)堆叠所述前驱片材以形成叠层;
c)在比该聚烯烃纤维的熔点低1℃至30℃的温度并且至少8Mpa的压力下,压制在步骤b)中制造的叠层;并且
d)在维持压力的同时将在步骤c)中制造的压制的叠层冷却至比所述聚烯烃纤维的熔点低至少50℃。
此外,本发明提供一种可通过上述方法获得的防弹成形制品。
再者,本发明提供一种防弹成形制品,该防弹成型制品包括:
i)多个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)多个粘结剂层,其中基于所述防弹成形制品的总重量,所存在的粘结剂总量为5.0至12.0重量%。
本发明进一步提供一种前驱片材,所述前驱片材包括至少两个实质上缺乏结合基质的单向排列的聚烯烃纤维层以及至少两个粘结剂层,其中单向排列的聚烯烃纤维层的每一个都由一个粘结剂层隔开,其特征在于基于前驱片材的总重量粘结剂以5.0至12.0重量%的量存在。
如本文中所使用的,术语“多个”意味着大于1的整数。
如本文中所使用的,术语“单向排列”意味着层中的纤维在由该层所限定的平面中实质上彼此平行取向。
如本文中所使用的,术语“实质上缺乏结合基质(bonding matrix)”意味着纤维层可包括痕量的结合基质,前提是该痕量在物质上不明显。实质上缺乏结合基质通常意味着该层包括至多1.0重量%的结合基质。换句话说,该层基本上无结合基质。优选地,实质上缺乏意味着缺乏。
如本文中所使用的,术语“缺乏结合基质”意味着基于该层的重量包含0.0重量%的结合基质。因此,包括单向排列的聚烯烃纤维的层优选为不含结合基质;换句话说,完全缺乏结合基质。粘结剂层与单向排列拉伸的聚烯烃纤维层有区别。包括单向排列的聚烯烃纤维的层可包含机械熔合的单向排列聚烯烃纤维。
如本文中所使用的,术语“结合基质”指与纤维自身不同的的物质,其作用为将纤维结合在一起。
如本文中所使用的,术语“前驱片材”指合适于形成防弹成形制品的中间多层材料片。
如本文中所使用的,“熔点”指纤维的差示扫描量热法(DSC)的二次加热曲线(以10℃/分钟的加热速率进行)的主波峰出现时的温度。
在本申请的上下文中,纤维是长度尺寸远大于其宽度和厚度的细长体。因此,术语“纤维”包括单丝、多丝纱、缎带、长条或带及其类似物。包括长条或带的层可以邻接或重叠。纤维可具有任何截面形状。截面可沿着纤维长度变化。通常,纤维是单丝。通常,纤维的截面纵横比小于5:1,优选为至多3:1;更优选为小于2:1,所述截面纵横比被定义为在纤维截面外周的两点之间的最大尺寸与在同一外周上的两点之间的最小尺寸的比率。
当聚烯烃纤维为聚乙烯纤维时可获得好的结果。合适的聚烯烃特别是乙烯与丙烯的共聚物和均聚物,其还可包括小量的一种或多种其它聚合物,特别是其它烯烃-1-聚合物。优选的聚乙烯纤维是高分子量和超高分子量聚乙烯([U]HMWPE)纤维。
聚乙烯纤维可通过在本领域中已知的任何技术制造,优选为通过熔融或凝胶纺丝法。最优选的纤维是凝胶纺丝UHMWPE纤维,例如,由DSM Dyneema(海尔伦,荷兰)以的名称出售的那些。如果使用熔融纺丝法,用于制造纤维的聚乙烯起始材料重均分子量优选在20,000至600,000g/mol之间,更优选为在60,000至200,000g/mol之间。熔融纺丝法的示例公开于EP 1,350,868,其以引用的方式并入本文中。如果使用凝胶纺丝法来制造所述纤维,优选使用特性粘度(IV,如根据ASTM 1601测定并且优选如关于实施例所描述的,在十氢萘的溶液中,在135℃下)优选为至少3dl/g、更优选为至少4dl/g、最优选为至少5dl/g的UHMWPE。优选地,IV为至多40dl/g,更优选为至多25dl/g,更优选为至多15dl/g。优选地,UHMWPE中每100个C原子小于1条侧链,更优选地每300个C原子小于1条侧链。优选地,UHMWPE纤维按照如下许多公开文献中所描述的凝胶纺丝方法制造,包括EP 0205960 A、EP 0213208 A1、US 4413110、GB 2042414 A、GB-A-2051667、EP 0200547 B1、EP 0472114B1、WO 01/73173 A1、EP 1,699,954;以及“Advanced Fiber Spinning Technology”(Ed.T.Nakajima,Woodhead Publ.Ltd(1994),ISBN 185573 182 7)。
优选地,来自这些聚烯烃的纤维通过在合适温度下拉伸来进行高度定向从而获得经拉伸的聚烯烃纤维。拉伸通常在低于纤维熔点的高温下进行。聚烯烃纤维优选为经拉伸的聚烯烃纤维。
聚烯烃纤维的拉伸强度优选为至少1.2GPa,更优选为至少2.5GPa,最优选为至少3.5GPa。聚烯烃纤维的拉伸模量优选为至少5GPa,更优选为至少15GPa,最优选为至少25GPa。当聚烯烃纤维是拉伸强度为至少2GPa,更优选为至少3Gpa并且拉伸模量优选为至少50GPa,更优选为至少90GPa,最优选为至少120Gpa的UHMWPE纤维时,获得最好的结果。
实质上缺乏结合基质的单向排列的聚烯烃纤维层通常是由纤维的熔合形成的。熔合(fusing)优选为在产生实质上不熔融结合(melt bonding)的压力、温度和时间组合下实现。优选地,没有可检测的熔融结合,如通过DSC检测(10℃/分钟)。没有可检测的熔融结合意味着当以一式三份来分析样品时,没有检测到可见的与部分熔融再结晶的纤维一致的吸热效应。优选地,熔合是机械熔合。机械熔合被认为由纤维变形引起,由此导致平行纤维的机械联锁增加以及在纤维之间的范德华相互作用增加。相应地,在层内的纤维通常被熔合。因此,该层可以没有任何结合基质或粘结剂存在而具有好的结构稳定性。此外,它可以没有任何纤维熔融而具有好的结构稳定性。
实质上缺乏结合基质的单向排列的聚烯烃纤维层可通过使细丝的平行阵列经受高温和压力而形成。用于施加压力的工具可以是压延机、平滑化设备、双带式压机或交替式压机。优选的施加压力的方式是将单向定向纤维的阵列引入到压延机的辊隙(nip),实质上如在WO 2012/080274 A1中所描述的。
优选地,包括单向排列的聚烯烃纤维的层的厚度是单个聚烯烃纤维的粗度的至少1.0倍,更优选为至少1.3,最优选为至少1.5倍。如果使用具有不同粗度的聚烯烃纤维,那么单个纤维的粗度在这里理解为所使用的纤维的平均粗度。优选地,所述层的最大厚度不超过单个聚烯烃纤维的粗度的20倍,更优选为不超过10倍,甚至更优选为不超过5倍并且最优选为不超过3倍。
本发明的单向排列的聚烯烃纤维层的机械性质通常类似于用来制造该层的纤维的机械性质。单向排列的聚烯烃纤维层的拉伸强度优选为至少1GPa,更优选为至少2GPa,最优选为至少3GPa。单向排列的聚烯烃纤维层的拉伸模量优选为至少40GPa,更优选为至少80GPa,更优选为至少100GPa。
通常,单向排列的聚烯烃纤维层具有10至200微米的厚度。优选地,厚度为25至120微米,更优选地厚度为35至100微米。层的厚度可例如使用显微镜采用三次测量的平均值来度量。
由多个前驱片材形成叠层。叠层可仅包括相同的前驱片材,或可包括不同前驱片材的混合物。叠层通常在用于制造防弹成形制品的常规压机中进行压制。优选地,步骤c)的压力为至少10MPa。更优选地,步骤c)的压力为至少12MPa,更优选为至少15MPa。虽然理论压力上限可较高,但是实际上步骤c)的压力为至多30MPa。在步骤c)中,温度优选为低于聚烯烃的熔点至少3℃,更优选为低于聚烯烃纤维的熔点至少5℃,最优选为低于聚烯烃纤维的熔点至少10℃。聚烯烃纤维的熔点是按照本文中所描述的通过DSC测定的。
优选地,基于叠层的总重量,存在的粘结剂总量为6.0至11.0重量%。更优选地,基于叠层的总重量,存在的粘结剂总量为7.0至10.5重量%,更优选为7.5至10.0重量%,最优选为8.0至9.5重量%。
在步骤d)中,压制的叠层在压力下冷却。维持压力直到压制的叠层冷却,这确保了单向排列聚烯烃纤维层良好地粘结。特别地,它防止了在压力降低时层松弛。优选地,在压力下冷却至低于80℃。优选地,在步骤d)中维持在步骤c)中所施加的压力。可替代地,可以施加较低的压力。
术语“粘结剂”指将邻接的单向排列纤维层粘结在一起的材料。粘结剂对本发明的前驱片材提供结构刚度。它还用于改进在本发明的成形制品中的邻接的单向排列纤维层间的层间结合。在本发明的成形制品中,粘结剂在邻接的单向排列纤维层之间形成层。粘结剂可完全覆盖邻接的单向排列纤维层的表面或它可仅部分覆盖该表面。粘结剂可以多种形式和方法施加,例如,呈膜、呈横向结合条或横向纤维(相对于单向纤维呈横向);或通过例如以聚合物熔融物或聚合物材料在液体中的溶液或分散液来涂布单向排列的纤维层。优选地,粘结剂均一地分布在纤维层的整体表面上,而结合条或结合纤维可局部施加。
合适的粘结剂包括热固性聚合物或热塑性聚合物或二者的混合物。热固性聚合物包括乙烯基酯、不饱和聚酯、环氧化物或酚树脂。热塑性聚合物包括聚氨酯、聚乙烯基、聚丙烯酸类、聚烯烃、聚对苯二甲酸丁二醇酯(PBT);或热塑性弹性体嵌段共聚物,诸如聚苯乙烯-聚丁烯-聚苯乙烯、或聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物。来热固性聚合物组的乙烯基酯、不饱和聚酯、环氧化物或酚树脂是优选的。
优选的热塑性聚合物包括乙烯的共聚物,其可包括一种或多种具有2至12个C原子的烯烃作为共单体,特别是乙烯、丙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、丙烯酸、甲基丙烯酸及醋酸乙烯酯。在聚合物树脂中缺乏共单体的情况下,可存在各种各样的聚乙烯,例如,线性低密度聚乙烯(LLDPE)、非常低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)或其共混物。然而,高密度聚乙烯(HDPE)是优选的。
一种特别优选的热塑性聚合物包括乙烯与丙烯酸的共聚物(乙烯丙烯酸共聚物);或乙烯与甲基丙烯酸的共聚物(乙烯甲基丙烯酸共聚物)。优选地,所述粘结剂以水性悬浮液施用。
另一种特别优选的热塑性聚合物为塑性体,其中所述塑性体是乙烯或丙烯与一种或多种C2至C12α-烯烃共单体的无规共聚物。更优选地,热塑性聚合物是乙烯和/或丙烯的均聚物或共聚物。
粘结剂的熔点低于聚烯烃纤维的熔点。通常,粘结剂具有低于155℃的熔点。优选地,熔点为115℃至150℃。
优选地,基于防弹成形制品的总重量,所存在的粘结剂总量为6.0至11.0重量%。更优选地,基于防弹成形制品的总重量,所存在的粘结剂总量为7.0至10.5重量%,更优选为7.5至10.0重量%,最优选为8.0至9.5重量%。
粘结剂通常并不实质上渗透到单向排列的聚烯烃纤维层中。优选地,粘结剂根本不渗透到单向排列的聚烯烃纤维层中。此外,粘结剂不用作在单向排列纤维的单层内的各纤维之间的结合剂。优选地,防弹成形制品包括多个实质上缺乏结合基质的单向排列的聚烯烃纤维层与多个粘结剂层。
在本发明的防弹制品中,粘结剂层可包括完整层,例如膜;连续的部分层,例如膜片(web);或分散的部分层,例如,粘结剂的点或岛。
优选地,在步骤b)中,相对于邻接的单向排列聚烯烃纤维层的单向排列聚烯烃纤维的取向,每个单向排列聚烯烃纤维层呈角度45°至135°取向。优选角度为75°至105°,例如约90°。优选地,在步骤b)中,单向排列的聚烯烃纤维的每个层与邻接的单向排列聚烯烃纤维层通过粘结剂层隔开。
本发明的前驱片材包括至少一个聚烯烃纤维层和至少一个粘结剂层。通常,前驱片材包括相等数目的实质上缺乏结合基质的单向排列的聚烯烃纤维层和粘结剂层。通常,前驱片材包括2至8个单向排列的聚烯烃纤维层,优选为2或4层。通常,前驱片材包括2至8个粘结剂层,优选为2或4层。通常,前驱片材仅包括实质上缺乏结合剂的单向排列的聚烯烃纤维层和粘结剂层。优选地,相对于邻接的聚烯烃纤维层的单向排列的聚烯烃纤维的取向,单向排列的聚烯烃纤维的每层呈角度45°至135°取向。优选的角度为75°至105°,例如约90°。优选地,单向排列的聚烯烃纤维的每层与邻接的单向排列聚烯烃纤维层通过粘结剂层隔开。
通常,该方法进一步在步骤a)前包括步骤a’):通过将粘结剂层施加到实质上缺乏结合基质的单向排列的聚烯烃纤维层来制造前驱片材,该前驱片材包括:
i)至少一个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)至少一个粘结剂层。
优选地,在步骤a’)中,将5.0至12.0重量%的粘结剂施加到实质上缺乏结合基质的单向排列的聚烯烃纤维层上,所述用量基于该层和粘结剂的总重量。优选地,基于前驱片材的总重量,存在的粘结剂总量为6.0至11.0重量%。优选地,基于前驱片材的总重量,存在的粘结剂总量为7.0至10.5重量%,更优选为7.5至10.0重量%,最优选为8.0至9.5重量%。
具有多于一个单向排列的聚烯烃纤维层和/或多于一个粘结剂层的前驱片材可通过如下制造:制造多个前驱片材;例如,如在步骤a’)一样,随后堆叠许多所述前驱片材;并且在高温和压力下固结前驱片材,所述前驱片材的每个均包括:i)一个实质上缺乏结合基质的单向排列的聚烯烃纤维层,以及ii)一个粘结剂层。可选择所施加的温度和压力以便在邻接的薄片之间造成粘着力。该温度必需低于聚烯烃纤维的熔点。
优选地,步骤a’)进一步包括固结两个实质上缺乏结合基质的单向排列的聚烯烃纤维层以及粘结剂层,其中单向排列聚烯烃纤维层由粘结剂层隔开。更优选地,在步骤a’)中,两个单向排列的纤维层彼此呈45°至135°取向。优选的角度为75°至105°,例如约90°。
通常,包括一个聚烯烃纤维层和一个粘结剂层的前驱片材具有25至150gm-2,优选为35至100gm-2,更优选为45至75gm-2的面密度。通常,包括两个聚烯烃纤维层和两个粘结剂层的前驱片材具有50至300gm-2,优选为70至200gm-2,更优选为90至150gm-2的面密度。
通常,本发明的成形制品包括20至480个的单向定向聚烯烃纤维层。优选地,其包括60至360层,更优选为100至240层。所需要的层数根据应用和要防御对抗的弹道威胁而定。
防弹成形制品的面密度将取决于层数目和所选择的层的面密度。防弹成形制品的面密度通常为1至100Kgm-2。优选地,本发明的成形制品具有5至50Kgm-2的面密度。更优选地,其具有7至20Kgm-2的面密度,最优选为8至15Kgm-2。
根据本发明的防弹成形制品可以是平坦的。这种成形制品通过在平板之间压制来制造。但是,防弹成形制品可以可替代地是弯曲的成形制品。其可在一个方向上或在二个方向上弯曲。此曲率可通过在常规压机中在弯曲模具中压制来实现,其中该模具定义了要制造的成形制品的形状。圆顶是在两个方向上弯曲的形状的示例。
本发明的或通过本发明的方法所制造的防弹成形制品是硬质弹道材料的形式。它适于以嵌件使用在防弹织物中或作为用于个人防护的头盔壳体或用于车辆保护的盔甲。它还可适于作为防弹头盔的组件,例如,附饰物(appliqué)或下颚(mandible)。通常,在弹道织物中的嵌件在一个或两个方向上弯曲。例如,胸板嵌件可在两个方向上稍微弯曲。车辆盔甲可在一个或两个方向上弯曲或者是平坦的。头盔壳体在两个方向上大程度弯曲。
已经发现,随着压制步骤期间所施加的压力增加,根据本发明的成形制品的特定能量吸收(Eabs或SEA)增加。在WO 1997/00766中对增加弹道性能提出的一种机制是由于驱逐被捕捉的气体以移除在材料中的空穴,从而导致材料密度增加。但是,在本发明中,令人惊人地发现,材料厚度减少的量远低于现有技术的材料。通过驱逐气体来减少空穴的机制无法解释在本发明的防弹制品中所观察到的低厚度减少的效应。
本发明的这种防弹成形制品的增加的尺寸稳定性效应的优点在于不管在成形期间所施加的压力,其厚度实质上相同。换句话说,在用于压制材料的模具组件之间的间隙变化惊人地低。增加的尺寸稳定性能够更准确地设计出成形制品。甚至当在多种不同压制设备上在不同条件下制造时,成形制品被制造成对产品规格的高容限。
增加的尺寸稳定性在压制高弯曲成形制品(例如高弯曲形状的车辆盔甲或头盔)时具有特别的优点。在此应用中,在常规压机中压制会仅在一个轴上施压压力,这意味着对此轴施加的横向压力仅仅是该力的分量。例如,在常规压机中压制头盔壳体将对头盔壳体的顶冠施加比对其外周高的压力。准确预测头盔模具的外周处所必需的模具间隙的能力可保证在横向方向中施加适当压力,从而导致在外周处有较高的性能。
本领域中已知使用两阶段压制方法来减轻此问题的效应。在第一阶段中,在第一模具中以相对低的压力来固结材料层以形成具有成品的大概形状的部分压制的物体。在第二阶段中,在第二模具中以高压压制经部分压制的制品以制造出成品。第一压力可以是2MPa;并且第二压力可以是16.5MPa。因为本发明的材料的高尺寸稳定性,即,其具有低固结参数,140T16.5-2(以%表示出),所以不需要第一部分的压制步骤。因此,制造高弯曲成形制品的方法可以从两步骤压制方法简化成一步骤压制方法。
因此,本发明优选为提供一种防弹成形制品,其中该防弹成形制品具有小于7%的固结参数(140T16.5-2),其中140T16.5-2是当在140℃下经受16.5MPa的压力时多个实质上缺乏结合基质的单向排列的聚烯烃纤维层与多个粘结剂层的厚度基于当在140℃下经受2MPa的压力时的厚度的减少%。
优选地,防弹成形制品具有小于5%的固结参数(140T16.5-2)。更优选地,140T16.5-2小于4%、小于3%或甚至小于2%。
本发明的成形制品可在一面或两面处包括膜。这种膜具有保护表面不被刮伤或磨损的性质。合适的膜包括例如小于20,小于15或甚至小于10微米厚的由热塑性聚合物制成的薄膜,所述热塑性聚合物例如为聚烯烃,例如聚乙烯、聚丙烯或其共聚物;聚四氟乙烯;聚酯、聚酰胺或聚氨酯,包括所述聚合物的热塑性弹性体版本。然而,通常,所述防弹成形制品仅包括实质上缺乏结合剂的单向排列的聚烯烃纤维层和粘结剂层。
本发明的防弹成形制品可具有改进的特定能量吸收(Eabs或SEA)、背衬变形或层离或其组合。特别地,已经发现成形制品对来复枪威胁,例如7.62×39毫米MSC(AK47)或SS109的特定能量吸收(Eabs或SEA)特别好。
优选地,本发明的防弹成形制品具有至多11Kgm-2的面密度,并且所述成形制品对抗7.62×39毫米MSC(AK47)符合NIJ水平III+性能。更选地,本发明的防弹成形制品具有至多10Kgm-2或甚至至多9Kgm-2的面密度,并且所述成形制品对抗7.62×39毫米MSC(AK47)符合NIJ水平III+性能。
根据本发明的防弹成形制品对抗7.62×39毫米MSC(AK47)通常具有至少205JKg- 1m2的Eabs。然而,可制造出对抗7.62×39毫米MSC(AK47)Eabs为至少240JKg-1m2,更优选为至少280JKg-1m2,至少300JKg-1m2或甚至至少330JKg-1m2的防弹成形制品。Eabs通常在9.8Kgm-2下测定。
根据本发明的防弹成形制品的背衬凹陷深度(back face signature)(BFS)通常小于5毫米,所述背衬凹陷深度是针对9毫米FMJ RN(Remmington)测量的,间隔的(spaced),并且基于6.8Kgm-2的面密度。优选地,背衬凹陷深度小于4毫米,更优选为小于3毫米,或甚至小于2毫米。
如于本文中所描述的防弹成形制品可与一种或多种另外的防弹材料层结合。这些另外的防弹材料包括聚合物防弹材料或无机防弹材料。聚合物防弹材料通常包括高强度纤维,例如对-芳族聚酰胺或超高分子量聚乙烯纤维。通常,如果存在聚合物防弹材料,将其放置在远离防弹成形制品的冲击面处。
另外的防弹材料层可供选择地是选自于以下各项组成的组的无机材料片材:陶瓷、金属、金属合金、玻璃、石墨或其组合。特别优选为金属,例如,铝、镁、钛、铜、镍、铬、铍、铁和铜,包括其合金。无机片材的厚度可在广泛范围内变化并且优选为在1毫米至50毫米之间,更优选为在2毫米至30毫米之间。通常,如果存在无机防弹材料,那么将其置于防弹成形制品的冲击面处。
另外的防弹材料可粘结到防弹成形制品上或者可以是单独的。粘结可以在存在或不存在另外的粘结剂的情况下通过压制来实现。这种粘结剂可以包括环氧树脂、聚酯树脂、聚氨酯树脂或乙烯基酯树脂。在另一个优选的实施方案中,结合层可进一步包括无机纤维的织造或非织造层,所述无机纤维例如为玻璃纤维或碳纤维。
本申请中所指的测试方法如下:
·IV:特性粘度如下测定:根据ASTM D1601方法,在135℃下,在十氢萘中,溶解时间为16小时,作为抗氧化剂的DBPC的量为2克/升溶液,通过对如在不同浓度下所测量的粘度外推至零浓度;
·拉伸性能(在25℃下测量):拉伸强度(或强度)和拉伸模量(或模量)如在ASTMD885M中指定的复丝纱线上定义和测定,使用标称计量长度为500毫米的纤维,50%/分钟的十字头速度。以所测量的应力-应变曲线为基础,模量被测定为在0.3至1%应变之间的梯度。为了计算模量和强度,将所测量的拉力除以如通过称重10米纤维所测定的纤度;假设密度为0.97g/cm3来计算以GPa计的值。根据ISO 1184(H)来测量薄膜的拉伸性能。
·成形制品的弹道性能是通过如下测定的:将面板夹在除空气外无背衬材料的框架中,在400毫米×400毫米的样品上,以散开模式(spread pattern)在每个样品上射击六发来计算V50值。V50是从4个样品计算的。所使用的弹药是7.62×39毫米MSC(AK47)。
·V50是通过如下测定的:取最低的两个贯穿速度以及最高的两个非贯穿速度的平均值,如在Lightweight Ballistic Composites(Military and Law EnforcementApplications,Bhatnagar,2006,Woodhead Publishing Limited.Page 29)中所定义。
·背衬凹陷深度(BFS)通过以下方式测定:使用四个Team Wendy Zorbium垫,每个角落一个,将400毫米×400毫米的6.8Kgm-2的样品与罗马黏土(roma clay)背衬间隔大约20毫米。在垫之间以及距离成形制品的边缘至少5cm,以均匀间隔开的模式射击成形制品四次。测试四个成形制品。以卡尺测量在每次射击的黏土中的凹痕;并且以16次射击的平均来计算BFS。所使用的弹药为9毫米FMJ-RN(Remmington)。
实施例
实施例1
从40个SK76 1760dtex纱线(可购自DSM Dyneema,Heerlen,荷兰)制造前驱片材。在张力受控的纱架上,将纱线从线轴退绕并且使其通过钢筘(reed)。随后,通过将纱线进料到展纱单元上,将纱线展开以形成具有320毫米宽度的低间隙细丝床。然后,将展开的纱线进料至压延机中。该压延机的辊具有400毫米的直径并且所施加的线压力是2000N/cm。该线以8米/分钟的线速度并且在154℃的辊表面温度下操作。在压延机中,将纱线熔合成纤维带。通过第一辊架将纤维带带从压延机移除。在压延机与第一辊架间放置粉末散布单元,粉末散布单元将7重量%的可购自Borealis(维也纳,奥地利)的Queo 1007粉末施加到带的上表面上。在高温下压延含有粉末的带并且将其卷绕到辊架上。
获得宽度为320毫米和厚度为46微米的纤维带。该纤维带具有35.4cN/dTex的韧性以及1387cN/dTex的模量。
五条所述带平行并且邻接排列以形成1600毫米宽的片材。在第一片材顶上形成相同的五条带的第二片材,并且两个片材的粘结剂层面向上,但是纤维呈垂直排列。产生了面密度为95gm-2的两层正交层叠的片材。将此片材切割成400毫米×400毫米的方形前驱片材。叠层多片方形前驱片材,以保证维持所述带层呈交替的0°/90°方向。将该前驱片材叠层加工成9.8Kgm-2的成形制品。该成形制品包括206层的单向排列带。在2Mpa和145℃下40分钟将该片材叠层压制为成形制品,随后在2MPa下经过20分钟的冷却时间段。
用7.62×39毫米MSC(AK47)子弹射击成形制品以测定V50。以下表1中列出了结果。
实施例2
根据实施例1制造成形制品,不同之处在于施加8MPa的压力。
实施例3
根据实施例1制造成形制品,不同之处在于施加16MPa的压力。
比较实验A
对400mm×400mm的单向排列的纤维层的片材(可购自DSM Dyneema(海尔伦,荷兰)的HB210)进行堆叠,以形成具有13.0Kgm-2的面密度的组件。所述片材各自都包括4层,每层都包括埋入17%的聚氨酯树脂基质中的单向排列的UHMWPE纤维,并且以纤维方向0°/90°/0°/90°的配置进行层叠。总共使用96片片材,其中整个叠层维持邻接层的交替0°/90°方向。在2MPa和125℃下压制该片材组件40分钟,接着在2MPa下经过20分钟的冷却时期。得到具有13.0Kgm-2的面密度的成形制品。采用7.62×39毫米MSC(AK47)子弹来射击该成形制品以测定V50。以下表1中列出了结果。
比较实验B
根据比较实验A制造成形制品,不同之处在于施加8MPa的压力。
比较实验C
根据比较实验C制造成形制品,不同之处在于施加16.5MPa的压力。
表1
这些结果表明,对由根据本发明的材料构成的防弹成形制品,可通过仅施加8MPa的压力来达到超过200的Eabs;然而,对根据现有技术的成形制品来说,需要16.5MPa的压力来达到超过200的Eabs。此外,将所施加的压力从压力2MPa增加至16.5MPa来达到此性能,导致在本发明的材料中厚度仅从10.4减小到10.1毫米,然而在比较实验中观察到厚度从14.3毫米减小到13.0毫米。
比较实验D
重复实施例1,但是使用4重量%的Queo 1007粉末,反而仅堆叠足够的前驱片材以制造具有6.8Kgm-2的面密度的400毫米×400毫米成形制品。以9毫米(Remington)弹药来射击成形制品以测定背衬凹陷深度(BFS)。下列表2中给出了结果。
实施例4
重复比较实验D,但是使用7重量%的Queo 1007粉末。
实施例5
重复比较实验D,但是使用10重量%的Queo 1007粉末。
表2
实施例编号 | 粘结剂(重量%) | BFS[mm] |
比较实验D | 4 | 6.3 |
实施例4 | 7 | 3.4 |
实施例5 | 10 | 3.4 |
这些结果表明,与具有较高重量%的粘结剂(粘结剂浸透进纤维层中)的成形制品(比较实验D)相比,在根据本发明的实施例4和5中的背衬变形令人惊讶地减少。此外,实施例4与实施例5之间的差异未指示出加入10%基质而非7%基质在BFS上有产生任何改进。
Claims (15)
1.一种用于制造防弹成形制品的方法,其中所述成形制品包括:
i)多个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)多个粘结剂层;并且所述方法包括:
a)提供多个前驱片材,其中所述前驱片材中的每个包括:
i)至少一个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)至少一个粘结剂层;
b)堆叠所述前驱片材以形成叠层,其中基于所述叠层的总重量,在所述叠层中的粘结剂总量为5.0至12.0重量%;
c)在比所述聚烯烃纤维的熔点低1℃至30℃的温度以及至少8MPa的压力下压制在步骤b)中制造的所述叠层;并且
d)在维持压力的同时将在步骤c)中制造的压制的叠层冷却至比所述聚烯烃纤维的熔点低至少50℃。
2.根据权利要求1所述的方法,其中,步骤c)的所述压力为至少10MPa。
3.根据权利要求1或2所述的方法,其中,基于所述叠层的总重量,存在的粘结剂总量为6.0重量%至11.0重量%。
4.根据权利要求1至3中任一项所述的方法,其中,在步骤b)中,相对于邻接的实质上缺乏结合基质的聚烯烃纤维层的单向排列聚烯烃纤维的取向,每个实质上缺乏结合基质的单向排列的聚烯烃纤维层呈角度45°至135°取向。
5.根据权利要求1至4中任一项所述的方法,其中,每个实质上缺乏结合基质的单向排列的聚烯烃纤维层与邻接的实质上缺乏结合基质的单向排列的聚烯烃纤维层通过粘结剂层隔开。
6.根据权利要求1至5中任一项所述的方法,所述方法进一步包括在步骤a)前的步骤a’):通过将粘结剂层施加到实质上缺乏结合基质的单向排列的聚烯烃纤维层上来制造前驱片材,其中所述前驱片材包括:
i)至少一个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)至少一个粘结剂层。
7.根据权利要求6所述的方法,其中,在步骤a’)中将5.0至12.0重量%的粘结剂施加到实质上缺乏结合基质的单向排列的聚烯烃纤维层上,所述用量基于所述层和所述粘结剂的总重量。
8.根据权利要求7所述的方法,其中,步骤a’)进一步包括将两个实质上缺乏结合基质的单向排列的聚烯烃纤维层以及粘结剂层固结,其中,单向排列的聚烯烃纤维的各层通过所述粘结剂层隔开。
9.根据权利要求8所述的方法,其中,在步骤a’)中,所述两个实质上缺乏结合基质的单向排列的聚烯烃纤维层彼此定向成呈45°至135°。
10.一种防弹成形制品,所述防弹成形制品可通过根据权利要求1至9中任一项所述的方法获得。
11.一种防弹成形制品,所述防弹成形制品包括:
i)多个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)多个粘结剂层;其中
基于所述防弹成形制品的总重量,存在的粘结剂总量为5.0重量%至12.0重量%。
12.根据权利要求11所述的防弹成形制品,其中,所述防弹制品包括基于所述防弹成形制品的总重量6.0重量%至11.0重量%的粘结剂。
13.根据权利要求11或12所述的防弹成形制品,其中,所述防弹成形制品具有小于7%的固结参数(140T16.5-2),其中140T16.5-2是在140℃下经受16.5MPa的压力时所述多个实质上缺乏结合基质的单向排列的聚烯烃纤维层和多个粘结剂层的厚度基于在140℃下经受2MPa的压力时的厚度的减少。
14.根据权利要求13所述的防弹成形制品,其中,所述防弹成形制品具有至多11Kgm-2的面密度,并且所述防弹成形制品对抗7.62×39毫米MSC(AK47)符合NIJ水平III+性能。
15.一种前驱片材,所述前驱片材包括:
i)至少两个实质上缺乏结合基质的单向排列的聚烯烃纤维层;以及
ii)至少两个粘结剂层;其中
实质上缺乏结合基质的单向排列的聚烯烃纤维层的每一个由一个粘结剂层隔开,其特征在于基于所述前驱片材的总重量,所述粘结剂以5.0重量%至12.0重量%的量存在。
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