CN1469803A - 耐冲击硬质复合材料和制造方法 - Google Patents
耐冲击硬质复合材料和制造方法 Download PDFInfo
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- CN1469803A CN1469803A CNA018174590A CN01817459A CN1469803A CN 1469803 A CN1469803 A CN 1469803A CN A018174590 A CNA018174590 A CN A018174590A CN 01817459 A CN01817459 A CN 01817459A CN 1469803 A CN1469803 A CN 1469803A
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Images
Classifications
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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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Abstract
一种耐冲击硬质复合材料有多个纤维层,其中每一层都包含一个单丝网络。这些纤维层配置于一种基体中,在它们之间有弹性体层。在该基体固化之前,相继纤维层彼此之间显示出至少约3g/cm的耐剥离性能。该复合材料有高刚性兼备优异的防弹性能。当在一个或两个表面上粘结一种选自金属和陶瓷组成的一组的硬板时,该复合材料提供了对铠装贯穿弹丸的更大防护。
Description
技术领域
本发明涉及一种有改善冲击和防弹性能的刚性、纤维增强复合材料、其前体物组件、及其制造方法。
背景技术
对于耐冲击和防弹的物品例如盔兜、面板、和背心中使用的复合材料来说,已知各种构造。这些复合材料显示出对来自弹丸例如BB、子弹、炮弹、榴霰弹、玻璃碎片等的高速冲击贯穿的不同程度耐受能力。美国专利Nos.5,587,230;5,552,208;5,330,820;5,196,252;5,190,802;5,187,023;5,185,195;5,175,040;5,167,876;5,165,989;5,124,195;5,112,667;5,061,545;5,006,390;4,953,234;4,916,000;4,883,700;4,820,568;4,748,064;4,737,402;4,737,401;4,681,792;4,650,710;4,623,574;4,613,535;4,584,347;4,563,392;4,543,286;4,501,856;4,457,985;和4,403,012,PCT公报No.WO91/12136,以及题为“用T-963 3300 dtex杜邦凯弗拉29纤维制作的轻质复合材料硬铠装非服装系统”的E.I.DuPont De NemousInternational S.A.的1984年出版物,描述了包括从伸直链超高分子量聚乙烯和芳香族聚酰胺等材料制成的高强度纤维的防弹复合材料。据说这样的复合材料既可以是柔软的也可以是刚性,因其构造的性质和所采用的材料而异。
防弹复合材料是从叠加在一起的多个织物层或单方向取向的纤维片材层形成的。在各层都是单方向取向纤维的情况下,相继各层是彼此相对而言以诸如0°/90°或0°/45°/90°/45°/0°的角度或以其它角度旋转的。在以前的工艺中,各个织物层或纤维层一直是未涂布的,或镶入一种填满纤维之间空隙的聚合物基体材料中。如果没有基体存在,则该复合材料固有地是可挠曲的。为了刚性,需要与一种硬板粘结。一种对比构造类型是一种由纤维和一种单—主要基体材料组成的复合材料。为了构造这种类型的硬质复合材料,用热量和压力使各层粘结在一起以使每层中的基体粘合,在它们之间形成一种键,并使整体融合成单一物品。
刚性复合材料中采用的基体树脂是诸如乙烯酯树脂或苯乙烯-丁二烯嵌段共聚物这样的材料,而且也是诸如乙烯酯和邻苯二甲酸二烯丙酯或苯酚甲醛和聚乙烯醇缩丁醛这样的树脂混合物。所得到复合材料的刚性、冲击和冲击撕裂品质在很高程度上取决于该基体树脂的拉伸模量(例外的是,如专门说明的,本文中使用的拉伸模量和模量这些术语系指对基体或夹层材料用ASTM D638-94测定、而对纤维材料用ASTM D2256测定的弹性模量)。例如,美国专利No.4,623,574公开用拉伸模量低于约6000psi(41,300kPa)的弹性体基体构建的纤维增强复合材料,与用更高模量树脂构建的复合材料比较以及与无基体的相同纤维结构比较,都有优异的防弹性能。不幸的是,低拉伸模量基体树脂虽然产生更大的防弹性能,但也产生较低刚性复合材料。在某些应用上,尤其那些复合材料在防弹方式和结构方式上都必须发挥作用的应用上,需要防弹性能和刚性的优异组合。
先有技术工作者采取的替代思路倾向于以牺牲另一种性能为代价来使一种性能最大化,或在一种单一基体中混合低模量材料和高模量材料以达到两种性能的折衷。因此,另一方面,以上引用的1984年杜邦出版物公开了已知具有800,000psi(0.55GPa)的高拉伸模量的邻苯二甲酸聚酯树脂的使用。美国专利No.4,403,012用实例说明了另一种思路,该专利公开了一种混合的高模量苯酚树脂和低模量聚乙烯醇缩丁醛树脂基体。目前需要一种兼备高刚性和高防弹和耐冲击性能的刚性复合材料物品。
寻求以经济方式制造刚性防弹复合材料的熟练技术人员面临的另一个问题是,当该基体树脂有高模量时,难以使预浸渍片材粘结。美国专利No.5,149,391和美国专利No.5,587,230中公开并举例说明了预浸渍(预浸)连续纤维网的有用形成方法,其公开文书专门列为本文参考文献。这些方法能很好地产生预浸单轴取向纤维片材(unitape)的连续绕卷。当unitape的连续绕卷向基础双层复合材料构建用斜交帘布层机转移时,困难产生了。此类机器的描述见美国专利No.5,173,138和美国专利No.5,766,725,其公开文书专门列为本文参考文献。
该斜交帘布层机的功能是使单轴取向纤维片材的第一卷和第二卷按顺序合股,使第二层的纵轴相对于第一层的纵轴而言发生旋转,用热量和压力使这两层固结,并将斜交帘布层基础复合材料的连续卷材卷绕起来。
有高模量基体树脂的斜交帘布层unitape的技术熟练人员面临着若干问题,当树脂含量仅约25wt%或以下时尤其如此。首先,在低于约120°F的相对低温时,各unitape彼此的粘合与对载体纤维网或脱模纸的粘合大致相同。这使得难以将unitape从脱模纸转移到第二unitape片材上。第二,这样的树脂要求在该斜交帘布层机上高温、高压和时间的组合才能充分固结,而卷绕成一种连续的产品卷材。时间越长,意味着生产能力越低。温度越高,越会引起基体树脂的过早交联。进而,在这些高温、高压和时间条件下,这些unitape片材不仅相互粘合,而且也粘合到该斜交帘布层机本身上,引起生产上的频繁故障和中断。目前需要一种使用高模量基体树脂生产有高刚性和高耐冲击与防弹性能的复合材料物品的改进方法。
发明内容
本发明提供一种包含多个纤维层的耐冲击刚性复合材料。各层中每一层都包含一种韧性等于或大于7g/旦、拉伸模量为至少约150g/旦、和断裂能量用ASTM D2256测定时为至少约8J/g的单丝网络。每一个纤维层都在一种拉伸模量用ASTM D638测定时超过约1×106psi(0.69GPa)的基体中,在相邻纤维层之间配置一个弹性体层。该弹性体的拉伸模量用ASTM D638测定时小于约6000psi(41,300kPa)。在该基体于66℃以332psi(2290kPa)加压5秒钟进行固化之前相继纤维层之间的耐剥离性能是至少约3g/cm、较好至少约5g/cm。相邻纤维层之间的耐剥离性能在适用的情况下用ASTM D1876-95方法测定,或者当各该纤维层是单轴取向的时用本文中描述的D1876-95改进方法测定。
本发明的复合材料有高刚性兼备优异的防弹性能。虽然有这些杰出性能,但预期可能需要针对旨在铠甲贯穿的弹丸的额外防护。为了达到这个目标,在本发明的另一种实施方案中,以上公开的刚性复合材料在一个或两个表面粘结到一种选自金属和陶瓷组成的一组的硬板上。
本发明的又另一种实施方案向一种耐冲击刚性复合材料提供一种组件前体物。一般来说,该组件前体物包含多个纤维层。各纤维层中每一层都包含一种韧性等于或大于约7g/旦、拉伸模量为至少约150g/旦、断裂能量为至少约8J/g的单丝网络。每一个纤维层都在一种热固性基体中,后者充分固化时的拉伸模量用ASTM D638测定时为至少约1×106psi(6895MPa)。在这些纤维层之间配置一个弹性体层。该弹性体的拉伸模量用ASTM D638测定时小于约6000psi(41,300kPa)。两个纤维层之间的耐剥离性能在该基体于66℃以332psi(2290kPa)加压5秒种进行固化之前是至少约3g/cm、较好是至少约5g/cm。
本发明也提供一种耐冲击刚性复合材料生产方法,包含下列步骤:(a)形成韧性等于或大于约7g/旦、拉伸模量为至少约150g/旦、断裂能量为至少约8J/g的高强度单丝的第一和第二纤维网络片材;(b)用一种固化时拉伸模量用ASTM D638测定时为至少约1×106psi(6895MPa)的基体树脂浸渍这些纤维网络片材中每一种;(c)在这些纤维网络片材之一的至少一个表面上施用一种其拉伸模量用ASTM D638测定时小于约6000psi(41,300kPa)的弹性体材料;(d)把第一纤维网络片材铺到第二纤维网络片材的表面上,使该弹性体材料介于这两者之间;(e)使该第一和第二纤维网络片材固结成双层复合材料;(f)把多个双层复合材料彼此铺叠在一起;和(g)借助于热量和压力使多个双层复合材料固结并使基体树脂完全固化。
已经发现,一个低模量弹性体层在这些刚性纤维层之间的加入显著改善了该复合材料的冲击和抗冲击撕裂性能。令人惊讶的是,得到了改善的性能而不影响该基体的玻璃化温度或该复合材料的刚性。按照本发明制造的物品显示出改善了对需要耐冲击和防弹性能兼备高刚性的应用的效用。此类物品的代表是盔兜、盾牌、胸铠、直升飞机和飞机的翼段与结构部件。
低模量弹性体层的加入进一步改善了本发明复合材料生产时实现的制造效率和经济性。在斜交帘布层机上可以利用较低的温度和压力,而且避免了连续作业中经历的粘性问题。
附图说明
当参照本发明的较好实施方案的以下详细说明和附图时,会更充分地理解本发明,进一步的优点也会变得显而易见,其中:
图1(a)是本发明的纤维网络层和弹性体层的制作和使这些层成形为一种固结unitape的工艺的图示表述;和
图1(b)是图1(a)所示固结unitape的顶视平面图。
具体实施方式
本发明提供一种尤其可用于防弹“硬”铠装物品中的改进复合材料。所谓“硬”铠装系指一种物品例如军用运输器的盔兜或翼段,该物品有充分的机械强度,以致它当遭遇到显著数量的应力时能维持结构刚性而且能自由站立而不坍塌。
本文中使用的“纤维”系指一种细长物体,其长度尺度比宽度和厚度等横向尺度大得多。因此,“纤维”包括单丝、多丝、带、条、束、以及有规则或无规则横截面的切段、切割或不连续纤维的其它形式。“纤维”包括以上任何一种或以上的组合等多种。
本发明中使用的单丝的横截面可以有很大差异。它们的横截面可以是圆的、扁平的或扁长的。它们也可以有无规则或规则的多叶横截面,后者有一个或多个从单丝的线性轴或纵轴投射出来的规则或无规则叶片。特别好的是,这些单丝有实质上圆的、扁平的或扁长的横截面、最好的是前者。
本文中使用的“纤维网络”系指多根纤维排布成一种预定构型,或者多根纤维组合在一起形成一种加捻或无加捻纱,这些纱排布成一种预定构型。该纤维网络可以有各种不同构型。例如,该纤维或纱可以成形为一种毡或其它无纺布、针织或机织成一种网络、或用任何一种惯常技术成形为一种网络。按照一种特别好的网络构型,这些纤维是对准一个方向的,因此,它们实质上是沿一个共同纤维方向彼此平行的。
本发明中使用的高强度纤维是其韧性等于或大于约7g/旦、拉伸模量等于或大于约150g/旦、断裂能量等于或大于约8J/g的纤维。较好的纤维是其韧性等于或大于约10g/旦、拉伸模量等于或大于约200g/旦、断裂能量等于或大于约20J/g的纤维。特别好的纤维是其韧性等于或大于约16g/旦、拉伸模量等于或大于约400g/旦、断裂能量等于或大于约27J/g的纤维。在这些特别好的实施方案中,最好的是那些其中纤维的韧性等于或大于约22g/旦、拉伸模量等于或大于约900g/旦、断裂能量等于或大于约27J/g的实施方案。在本发明的实施中,选用的纤维的韧性等于或大于约28g/旦、拉伸模量等于或大于约1200g/旦、断裂能量等于或大于约40J/g。
可用的高强度纤维包括伸直链聚烯烃纤维、尤其伸直链聚乙烯(ECPE)纤维,芳香族聚酰胺纤维,聚吲哚纤维例如聚苯并噁唑和聚苯并噻唑,聚乙烯醇纤维,聚酰胺例如尼龙-6、尼龙-66、和尼龙-46,聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯,聚丙烯腈,液晶共聚酯、玻璃纤维和碳纤维。
美国专利No.4,457,985一般性地讨论了这样的伸直链聚乙烯和聚丙烯纤维,此专利的公开文书在其并非与本文不一致的程度上专门列为本文参考文献。在聚乙烯的情况下,适用的纤维是重均分子量为至少150,000、较好至少一百万、更好在200万~500万之间的那些。这样的伸直链聚乙烯纤维可以在溶液中生长,如美国专利No.4,137,394(Meihuzen等人)或1982年10月26日公布的Kavesh等人的美国专利No.4,356,138中所述的,或者是一种从溶液纺成的丝以形成凝胶结构,如German Off.No.3,004,699和GB No.2051667中所述、尤其如美国专利No.4,413,110中所述。这样的纤维也可以通过熔体丝或固态挤塑来形成。本文中使用的聚乙烯这一术语系指占主导的线型聚乙烯材料,该材料可以含有少量链支化或每100个主链碳原子不超过5个改性单元的共聚单体,而且也可以含有与其混合的、不超过约50wt%的一种或多种聚合物添加剂例如链烯-1-聚合物,尤其低密度聚乙烯、聚丙烯或聚丁烯、含单烯烃作为主单体的共聚物、氧化聚烯烃、接枝聚烯烃共聚物、和聚甲醛,或低分子量添加剂例如抗氧剂、润滑剂、紫外线屏蔽剂、着色剂等,这些通常仅供参考。因形成技术、拉伸比、温度、及其它条件而异,可以赋予这些单丝以各种各样性能。这些单丝的韧性应当是至少15g/旦、较好至少20g/旦、更好至少25g/旦、最好至少30g/旦。类似地,该单丝的拉伸模量用Instron拉伸试验机测定时是至少300g/旦、较好至少500g/旦、更好至少1,000g/旦、最好至少1,200g/旦。拉伸模量和韧性的这些最高值一般只有通过采用溶液纺丝工艺才能得到。这些单丝中很多具有比用来形成它们的聚合物的熔点更高的熔点。因此,例如,150,000、一百万和二百万的高分子量聚乙烯一般具有138℃的本体熔点。由这些材料制成的高度聚向聚乙烯单丝具有高出约7℃~约13℃的熔点。因此,熔点的稍微提高反映出与本体聚合物比较而言这些单丝的结晶完整性和更高的结晶取向。
类似地,可以使用平均分子量至少200,000、较好至少一百万、更好至少二百万的高取向伸直链聚丙烯纤维。这样的伸直链聚丙烯可以采用以上提到的各种参考文献中所述的技术、尤其采用美国专利No.4,413,110的技术成形为合理良好取向的单丝。由于聚丙烯是结晶度比聚乙烯低得多的材料而且含有侧链甲基基团,因而用聚丙烯可达到的韧性值一般来说实质上低于聚乙烯的对应值。因此,适用的韧性是至少8g/旦、较好的韧性是至少11g/旦。聚丙烯的拉伸模量是至少160g/旦、较好至少200g/旦。该聚丙烯的熔点一般会因取向过程而提高若干度,因此,聚丙烯单丝较好有至少168℃、更好至少170℃的主熔点。以上提到的参数的特别好的范围会有利地提供最终物品的改善性能。采用重均分子量为至少约200,000兼备以上所述参数(模量和韧性)的较好范围的纤维会有利地提供最终物品的改善性能。
有高拉伸模量的高分子量聚乙烯醇(PV-OH)纤维的描述见美国专利No.4,440,711(Y.Kwon等人),该专利在并非与本文不一致的程度上专门列为本文参考文献。高分子量PV-OH纤维应当具有至少约200,000的重均分子量。特别有用的PV-OH纤维应当具有至少约300g/旦的模量,至少约7g/旦、较好至少约10g/旦、更好至少约14g/旦、最好至少约17g/旦的韧性,和至少约8J/g的断裂能量。重均分子量为至少约200,000、韧性为至少约10g/旦、模量为至少约300g/旦、断裂能量为约8J/g的PV-OH纤维是更可用于生产防弹物品的。有这样一些性能的PV-OH纤维可以例如用美国专利No.4,599,267中公开的工艺生产。
在聚丙烯腈(PAN)的情况下,PAN纤维应当具有至少约400,000的重均分子量。特别有用的PAN纤维应当具有至少约10g/旦的韧性和至少约8J/g的断裂能量。分子量为至少约400,000、韧性为至少约15~20g/旦、断裂能量为至少约8J/g的PAN纤维是最有用的;这样的纤维公开于例如美国专利No.4,535,027中。
在芳香族聚酰胺纤维的情况下,主要从芳香族聚酰胺形成的适用芳香族聚酰胺纤维在美国专利No.3,671,542中有描述,该专利专门列为本文参考文献。较好的芳香族聚酰胺纤维将有至少约20g/旦的韧性、至少约400g/旦的拉伸模量、和至少约8J/g的断裂能量,特别好的芳香族聚酰胺纤维将有至少约20g/旦的韧性、和至少约20J/g的断裂能量。最好的芳香族聚酰胺纤维将有至少约20g/旦的韧性、至少约900g/旦的模量、和至少约30J/g的断裂能量。例如,杜邦公司以商品名Kevlar29和49商业性生产而且有中等高模量和韧性值的聚对苯二甲酰对苯二胺单丝尤其可用于形成防弹复合材料(Kevlar29的模量值和韧性值分别为500g/旦和22g/旦,Kevlar49的模量值和韧性值分别为1000g/旦和22g/旦)。也可用于本发明实施的是杜邦公司以商品名Nomex商业性生产的聚间苯二甲酰间苯二胺。
适合于本发明实施的液晶共聚酯纤维公开于例如美国专利3,975,487、4,118,372、和4,161,470中。
适合于本发明实施的聚吲哚类纤维公开于例如美国专利5,286,833、5,296,185、5,356,584、5,534,205和6,040,050中。
高强度纤维网是通过将一种基体组合物施用到该高强度纤维上然后使该基体组合物/纤维组合固结而浸渍或包埋于该基体组合物中的。所谓“固结”系指该基体材料和该纤维网层组合成一个单一单元层。固结可以经由干燥、冷却、加热、压力或其组合发生。
本发明中使用的基体材料是一种热固性树脂,较好可溶于碳-碳饱和溶剂例如甲乙酮中,而且具有固化时用ASTM D638测定时至少约1×106psi(6895MPa)的高拉伸模量。较好的基体组合物包括至少一种热固性乙烯酯、邻苯二甲酸二烯丙酯、和任选地一种该乙烯酯树脂固化用催化剂。
较好的是,该乙烯酯是通过一种多官能环氧树脂用一种不饱和单羧酸、通常为甲基丙烯酸或丙烯酸进行酯化而产生的乙烯酯。乙烯酯实例包括己二酸二缩水甘油酯、间苯二甲酸二缩水甘油酯、己二酸二(2,3-环氧丁酯)、草酸二(2,3-环氧丁酯)、琥珀酸二(2,3-环氧己酯)、马来酸二(3,4-环氧丁酯)、庚二酸二(2,3-环氧辛酯)、邻苯二甲酸二(2,3-环氧丁酯)、四氢邻苯二甲酸二(2,3-环氧辛酯)、马来酸二(4,5-环氧十二烷酯)、对苯二甲酸二(2,3-环氧丁酯)、硫二丙酸二(2,3-环氧戊酯)、联苯二羧酸二(5,6-环氧十四烷酯)、磺酰二丁酸二(3,4-环氧庚酯)、1,2,4-丁烷三羧酸三(2,3-环氧丁酯)、马来酸二(5,6-环氧十五烷酯)、壬二酸二(2,3-环氧丁酯)、柠檬酸二(3,4-环氧十五烷酯)、环己烷-1,3-二羧酸二(4,5-环氧辛酯)、丙二酸二(4,5-环氧十八烷酯)、双酚A-富马酸聚酯和类似材料。特别好的是可从Dow化学公司以商品名Derakane购买的乙烯酯。
适用的催化剂,例如,包括过苯甲酸叔丁酯、2,5-二甲基-2,5-二-2-乙基己酰过氧基己烷、过氧化苯甲酰、及其组合。
该基体组合物的较好溶剂是碳-碳饱和的低沸点溶剂、包括甲乙酮、丙酮、乙醇、甲醇、异丙醇、环己烷、乙基丙酮、及其组合。这里使用的“碳-碳饱和”系指一种其中碳原子之间的键全部是单键的化合物。换言之,碳-碳饱和化合物不包括任何不饱和碳-碳双键。固结之后,只存在痕量—若有的话—溶剂和催化剂。
施用于该纤维网络的基体组合物,以该组合物的总重量为基准,应当包括约35~65、较好55~65wt%乙烯酯树脂,约2~8、较好约3~6wt%邻苯二甲酸二烯丙酯,其余由低沸点溶剂组成。如果有固化催化剂存在,则它应当占约0.05~1.0wt%、较好约0.2~0.8wt%。固结之后,以基体组合物的总重量为基准,该基体组合物应当包括约5~15、较好约8~12wt%邻苯二甲酸二烯丙酯,其余基本上由乙烯酯组成。该基体组合物可以配混填料例如碳黑、硅石、玻璃微珠等,可多达不超过该基体树脂的约300wt%、较好不超过100wt%的数量。
该复合材料中基体组合物与纤维的比例可以有很大差异,这取决于终端用途。如果该基体组合物的密度类似于该纤维的密度,则以各单层或最终复合材料的重量为基准,该基体组合物一般可以占约10~约40wt%、较好约14~30wt%、更好约16~28wt%、最好约18~24wt%。对于防弹复合材料物品来说,较好的范围是可高达28wt%。如果该基体组合物和该纤维的密度不类似,则以各单层或最终复合材料的体积为基准,该基体组合物可以占约5~约40vol%、较好约6~30vol%、更好约7~24vol%、最好约8~22vol%。
本发明实施中采用的弹性体可以是任何一种具有用ASTM D638测定时小于约6000psi(41,300kPa)的拉伸模量的弹性体,该弹性体在该基体于66℃以332psi(2290kPa)加压5秒钟进行固化之前提供用ASTM 1876-72耐剥离性能试验测定时至少约5g/cm的相邻纤维层之间耐剥离性能。本发明中可以利用种类繁多的弹性体材料和配方。适用弹性体的代表性实例有其在Encyclopedia of Polymer Science,Volume 5,Elastomers-Synthetic节(John Wiley & Sons Ine.,1964)中总结的结构、性能和配方。基本要求是它们有适当低的模量并产生所需要的耐剥离性能。例如,可以采用下列材料:聚丁二烯、聚异戊二烯、天然橡胶、乙烯-丙烯共聚物、乙烯-丙烯-双烯三元共聚物、热塑性弹性体等。较好的是,该弹性体具有低于约2000psi(13,800kPa)的拉伸模量。更好的是,该弹性体具有低于约1000psi(6895kPa)的拉伸模量。
特别有用的是共轭双烯和乙烯基芳香族单体的嵌段共聚物。这些聚合物中很多是壳牌化学公司商业性生产的,详见简报“KratonThermoplastic Rubber”,se:68:82。最好的是苯乙烯/丁二烯共聚物-聚萜烯-聚双戊烯组合物。这种材料是3M公司商业性生产的,并以环己烷/丙酮溶液在商品名Scotch-Grip下销售。
该弹性体层只占该复合材料的一个微小部分,即该复合材料的约2~10wt%。较好,该弹性体占该复合材料的约2~7wt%。该弹性体层不一定是连续的,可以由该纤维层上的各分立区域组成。较好,这些弹性体覆盖分立区域均匀分布于该纤维层表面上。
用纤维的几何形状来表征本发明复合材料的几何形状是方便的。一种这样的适用排布是一种其中各纤维沿一个共同纤维方向彼此平行地排列的纤维网络层(以下简称为“单方向排列纤维网”)。这样的单方向排列纤维的相继各层可以相对于上一层而言进行旋转。较好,该复合材料的各纤维网层是斜交铺叠的,即每个网络层的单方向纤维的纤维方向相对于毗邻层的单方向纤维的纤维方向而言是旋转的。一个实例是一种五层物品,其第二层、第三层、第四层和第五层相对于第一层而言旋转+45°、-45°、90°和0°。一个较好的实例包括两层以0°/90°敷层。这样的旋转单方向排列在例如美国专利4,457,985、4,748,064、4,916,000、4,403,012、4,623,573、和4,737,402中有描述。
一般来说,本发明的纤维层是通过把基体组合物施用到高强度纤维上然后使该基体材料/纤维组合固结来形成的。例如,可以将该纤维或纱经由该基体组合物的一种溶液输送以实质上涂布该纤维或纱,然后干燥而形成一种涂布纤维或纱。然后,所得到的涂布纤维或纱可以排列成所希望的构型。替而代之,可以先构建该纤维网络,然后涂布该基体组合物。
该纤维网络可以经由各种众所周知的方法构建。在单方向排列纤维网络的较好情况下,较好有约30~约2000根小于约12旦的单丝、更好有约100根小于约7旦/单丝的高强度单丝纱束从一个粗纱架供给,经由导纱器以及一个或多个伸幅杆引导到一台准直梳中,然后涂布或浸渍该基体材料。该准直梳使各单丝以共平面和实质上单方向的方式排列。这些纤维网络层典型地含有约6~12根纱/英寸(2.4~4.7根/cm)、较好8~11根纱/英寸(3.2~4.3根/cm)。每个纤维网络层(包括基体材料)典型地是约0.01~0.2、较好约0.04~0.12、最好约0.06~0.10mm厚。
本发明的纤维层和弹性体层的较好形成方法包括先形成纤维网络层、较好一种如上所述单方向网络,把该基体组合物的一种溶液施用到该纤维网络层上,然后使该基体浸渍纤维网络层干燥,详见例如专门列为本文参考文献的美国专利No.5,552,208。如图1中所示,纱102从一个粗纱架供给,并通过精梳站104形成单方向纤维网。使该纤维网进入槽108中,在此使其浸渍该基体树脂的一种溶液。然后,让该涂布纤维网通过一双辊110。这对辊将过量基体溶液挤出,并使该基体组合物实质上均匀地铺展于各单丝之间。然后将涂布纤维网置于一种载体纤维网上,后者可以是一种纸或薄膜基材106。用夹辊114控制层厚度。然后,让浸渍纤维网络层通过第一加热炉112进行干燥。在该炉中,该浸渍纤维网络层(unitape)遭遇到足以使该基体组合物中的溶剂挥发的热量。通过在116喷洒一种溶液,把一个弹性体层施用到该纤维网络的上表面。该弹性体层不一定是连续的。它可以在该纤维网的表面上形成较好均匀分布的分立喷雾滴。借助于喷雾施用的弹性体层的替代,可以通过让该纤维网在一个与含有弹性体溶液的液池接触的辊(未画出)下运行来施用该弹性体层。让有弹性体层的纤维网络通过第二个加热炉118以使该弹性体组合物中的溶剂挥发。夹辊120用来拉动该载体纤维网和unitape通过该系统。然后,该基材和固结的unitape可以在辊122上卷绕成一种连续卷材。
该固结的unitape可以切割成分立的片材并敷成一叠以成形为终端用途复合材料,也可以把它们成形为一种组件前体物,随后用来形成该终端用途复合材料。所谓“终端用途复合材料”系指整体多层复合材料,即本发明的物品例如盔兜或运输器铠装板。如前面提到过的,最好的复合材料是其每一层的纤维网都单方向地排列和取向从而相继各层中的纤维方向呈0°/90°构型者。
在最好的实施方案中,两个纤维网络层斜交成0°/90°构型,然后模塑形成一种组件前体物。这两个纤维网络层可以是连续斜交的,较好通过将这些网络之一切割成可以横跨另一个网络层宽度相继放置成0°/90°取向的长度来进行。美国专利5,173,138和5,766,725描述了连续斜交用装置。如PCT公报WO91/12136中所述,然后,所得到的连续双层组件可以卷绕成一种每层之间都有一个隔离材料层的卷材。当准备形成该终端用途复合材料时,使该卷材解绕并将该隔离材料剥离掉。然后将该双层组件切割成分立片材、叠成多层、然后遭遇到热量和压力,以期形成成品形状和使该基体树脂固化。
该纤维网络为模塑而暴露的温度和/或压力因所使用的高强度纤维的类型而异。铠装板板中使用的终端用途复合材料可以通过在约150~400psi(1,030~2,760kPa)、较好约180~250psi(1,240~1,720kPa)的压力和约104~127℃的温度下模塑一叠双层组件来制造。盔兜中使用的终端用途复合材料可以通过在约1500~3000psi(10.3~20.6MPa)的压力和约104~127℃的温度下模塑一叠双层组件来制造。
本发明的复合材料,与缺乏过渡性弹性体层的先有复合材料相比,兼备高刚性和改进的耐冲击和防弹性能。不拘泥于本发明何以管用的一种特定理论,相信该过渡性弹性体层在冲击负荷下起到了使龟裂钝化和使该复合材料中传播的应力分散的作用。少量过渡层材料在能有效地改善冲击性能的同时不足以使刚性降低。差示扫描量热法(DSC)已经显示该过渡层材料对该基体的玻璃化温度没有显著影响。
以下实施例是为提供本发明的更完整理解而列举的。为说明本发明的原理而提出的特定技术、条件、材料、比例和报告数据是例示性的,不应当理解为对本发明范围的限定。
纤维层之间的耐剥离性能,在适用的情况下用ASTM D1876-95测定,而当这些纤维层是unitape且相邻层中的纤维呈0°/90°时用ASTMD1876-95的如下改进方法测定。
耐剥离性能试样是6英寸×2英寸(15.2cm×5.08cm),包含第一纤维层、过渡层、第二纤维层和北、南、东和西边缘。第一纤维层中的单丝是与北南方向上试样的长尺度平行排列的。第二纤维层中的单丝是与东西方向上试样的短尺度平行排列的。在北南方向上试样的南边切割2个1/4英寸(0.63cm)狭缝,一个在离东边1/2英寸(1.27cm)的距离上,另一个在离西边1/2英寸(1.27cm)的距离上。这两个狭缝在试样的南边形成三个小垂片,即一个1英寸(2.54cm)宽中心垂片和该中心垂片任意一侧的两个半英寸(1.27cm)宽垂片。
这两个半英寸垂片(1.27cm)在Instron公司制造的试验机的一个夹具中夹紧。中心1英寸垂片(2.54cm)在该试验机的对面夹具中夹紧。这些夹具以10英寸/分钟(25.4cm/分钟)的速度分开,使第一纤维层与第二纤维层剥离。测定和记录使这两个夹具分离所需要的力。在ASTM D1876-95中所述的初始峰之后测定分离的平均力,并记录为耐剥离性能。
总面密度(ADT)指出该复合材料每单位面积的重量。它是用kg/m2单位表达的。
实施例的碎片弹道试验是按照军事规格MIL STD 662E用17格令、22口径、FSP硬化碎片模拟器执行的。样品复合材料的防护本领的一种量度是通过提到能使弹丸的50%停止的冲击速度来表达。用m/秒单位表达的这种速度指定为V50值。面密度越高的复合材料,预期有越高的V50。复合材料的防护本领的第二种量度是对该复合材料的总面密度(ADT)归一化。与复合材料的总面密度成比例的、V50速度的复合材料所吸收的弹丸的能量称为复合材料的比能量吸收(SEAC)。SEAC用J/kg/m2单位或等效地用J-m2/kg单位表达。
实施例的复合材料的挠曲模量用ASTM D790测定。
实施例的复合材料冲击性能是由Delsen试验实验室(公司)用先进复合材料供应商协会(SACMA)试验方法SRM2R-94测定的。
实施例
实施例1
Honeywell国际公司以商品名SPECTRA 1000制造的225根1100旦伸直链聚乙烯纱从一个粗纱架供给图1中所示的浸渍工艺。这些纱铺展开、梳直、放置在一种硅酮涂布脱模纸上。把一种由5000份树脂溶液和35份催化剂组成的基体溶液施用到该单轴纤维网上。这种从Dow化学公司得到的树脂溶液由64wt%乙烯酯树脂、3wt%邻苯二甲酸二烯丙酯和33wt%甲乙酮组成。从Elf Atochem得到的催化剂是2,5-二甲基-2,5-二(2-乙基己酰过氧基)己烷。让该纤维网从一个夹辊下通过以使该基体溶液铺展开并迫使该溶液从这些纱的单丝中和它们之间通过。让该纤维网从82℃温度的第一加热炉中通过,让该基体中的溶剂干燥,将一种由约10wt%苯乙烯/丁二烯共聚物、约10wt%聚萜烯、约10wt%聚双戊烯、约10wt%丙酮和约60wt%环己烷组成的弹性体溶液(商品名Scotch-Grip,购自3M公司)以分立小滴均匀喷洒在该纤维网上。当通过82℃温度的第二加热炉时,该弹性体溶液中的溶剂干燥。该纤维网通过一对最终夹辊,卷绕成连续的unitape卷材。该unitape的组成为81wt%纤维、16wt%基体、和3wt%弹性体。
以上所述弹性体溶液的一个样品在室温下于开放空气中蒸发。干弹性体的拉伸模量用ASTM D638测定。其拉伸模量是406psi(2,800kPa)。
把该unitape的第一卷和第二卷装到一台如美国专利No.5,173,138中所述的斜交帘布层机上。以这些层中的纤维呈0°/90°取向形成一种双层组件。让这些层在66℃的温度、在约332psi(2,290kPa)的压力下从一个辊下通过,进行斜交层固结。一给定区域在该辊的压力下的停留时间是约5秒钟。该斜交组件各层之间的耐剥离性能实测为21g/cm。该组件中基体的玻璃化温度用DSC以5℃/分钟的加热速度进行三次测定的实测值是91.3℃、87.4℃、和85.1℃。
将51层该斜交帘布层组件从脱模纸上剥离下来、叠在一起并在121℃和1800psi(12,400kPa)下模塑,形成一种面密度(ADT)为4.84kg/m2(0.99磅/平方英尺)的复合材料。
实施例2(比较)
像在实施例1中那样生产连续unitape卷材,所不同的是不使用任何弹性体,但其它材料和条件全都相同。该unitape的组成为81wt%纤维和19wt%基体。将该unitape的第一卷和第二卷装到与实施例1中相同的斜交帘布层机上。
在从室温到可高达116℃范围内的固结温度,进行了该unitape斜交的尝试。在较低温度下,该unitape仍然粘到该脱模纸上,且纬层和经层互不粘合。增大各层之间的压力并没有改善粘合力。在116℃时,该unitape中的基体变得非常软而粘。然而,各层之间的粘合力并不大于该unitape对该脱模纸的粘合力。在38℃至116℃之间尝试了很多温度,以确认该材料会粘到足以形成斜交帘布层并具有比对该脱模纸更大的层对层亲合力的温度。并尝试了不同的脱模纸,看哪些脱模纸在该unitape在斜交帘布层作业之前接近于脱离该纸的那一点上有更好的脱模性能。在低温下该unitape各层又互相粘,而当加热时,该纬层对该纸的粘性与对经层的粘性一样大。在该机器上,任何斜交帘布层作业都是不可能的。
为了制备与实施例1中那种可比的复合材料,切割单层片材,让它们留在脱模纸上。将这些片材料进行unitape对unitape斜交并使该脱模纸在外侧,在66℃和200psi(1380kPa)下加压20分钟。对于连续工艺来说,这会是一个不实用的停留时间。将这些片材从该压机上取下,并使之冷却到室温。此时,可以将脱模纸从该双层组件上剥离下来。
该组件中基体的玻璃化温度用DSC以5℃/分钟的加热速度进行三次测定的实测值是83.2℃、84.7℃、和86.2℃。与实施例1中的玻璃化温度比较,可以看出,实施例1的基体树脂不因弹性体层的存在而受影响。
同实施例1中一样,将51层该组件叠在一起并在121℃和1800psi(12,400kPa)模塑,形成一种面密度(ADT)为5.09kg/m2(1.04磅/平方英尺)的复合材料。
实施例3
对实施例1和(比较)实施例2的复合材料,像前面所述那样测试了防弹性能。结果如下:
实施例1 | 实施例2(比较) | |
ADT,Kg/m2 | 4.84 | 5.09 |
V50,m/sec | 540 | 514 |
SEAC,J/Kg/m2 | 33 | 29 |
可以看出,本发明的复合材料比能量吸收(SEAC)比先有技术材料的超出13.8%。
实施例4
像实施例1中那样制备本发明的一种复合材料,所不同的是,该unitape中纤维、基体和弹性体的比例是83wt%纤维、14wt%基体、和3wt%弹性体。
实施例5(比较)
像比较实施例2中那样制备一种复合材料,所不同的是,该unitape中纤维和基体的比例是80wt%纤维和20wt%基体。
实施例6
对实施例4和(比较)实施例5的复合材料,像前面所述那样测试了挠曲模量和冲击性能。结果如下:
复合材料挠曲模量,GPa | 冲击性能 | ||
吸收的能量,焦耳 | 持续时间,毫秒 | ||
实施例4 | 16.9 | 13.1 | 10.1 |
实施例5(比较) | 16.9 | 7.1 | 16.2 |
可以看出,本发明复合材料的刚性(挠曲模量)是与先有技术复合材料相同的。进而,本发明复合材料的能量吸收能力比先有技术材料超出84%,且冲击事件的持续时间短得多。这意味着该冲击事件期间较少凹陷和较少脱层,这是盔兜等应用的一种重要品质。
实施例7
像实施例1中那样制备本发明的一种复合材料,所不同的是,施用Kraton D1107的一种溶液作为弹性体,且该unitape中各组分的比例是75wt%纤维、18wt%基体和7wt% Kraton D1107。Kraton D1107的拉伸模量实测值为196psi(1,350kPa)。该复合材料由51层该组件组成,其面密度为5.19kg/m2(1.06磅/平方英尺)。
本复合材料的弹道试验显示V50为549m/秒,且SEAC为32J/kg/m2。将会看到的是,这些弹道性能优于(比较)实施例2的先有材料。
实施例和比较例8~13
使用相同的纱和基体树脂,像实施例1中那样制备一种unitape片材。从这种unitape制备一系列样品,其中,在其表面上喷洒有不同拉伸模量的过渡层材料的溶液并在82℃的温度干燥。在实施例8~11和比较例12中,该unitape含有16wt%基体。在比较例13中,该unitape含有19wt%基体。在实施例8~11中,该过渡层占该unitape的3wt%。切割这些unitape的片材,使其留在该脱模纸上。该脱模纸是SILOX3.2D2D/D6B,购自International Paper公司Akrosil分部。这些unitape片材以脱模纸在外侧形成unitape对unitape斜交帘布层,并在66℃以332psi(2,290kPa)压制5秒钟。将这些片材从压机中取出,并使之冷却到室温。然后测定A)该unitape的层间耐剥离性能,和B)该斜交帘布层unitape与该脱模纸之间的耐剥离性能,两者都用ASTMD1876-72测定。结果如下:
实施例或比较例 | 过渡层材料 | 过渡层拉伸模量Psi(KPa) | 耐剥离性能g/cm | ||
Unitape与Unitape之间A | Unitape与脱模纸之间B | 比值,A/B | |||
实施例8 | Kraton D1107 | 196(1,350) | 17.5 | 1.25 | 14.0 |
实施例9 | Scotch-Grip | 406(2,800) | 21.8 | 2.7 | 8.1 |
实施例10 | Dynaflex D3204 | 509(3,510) | 15.6 | 1.1 | 14.5 |
实施例11 | Kraton G1650 | 3,279(22,610) | 11.8 | 1.1 | 11.0 |
对照比较例12 | 无 | <0.2 | 1.8 | <1 | |
对照比较例13 | 无 | <0.2 | 2.0 | <1 |
Scotch-Grip是一种3M公司产品,包含苯乙烯-丁二烯聚合物、聚萜烯树脂、和双戊烯聚合物的环己烷/丙酮溶液。
Kraton D1107和Kraton G1650是壳牌化学公司的产品。KratonD1107是一种苯乙烯-异戊二烯-苯乙烯嵌段共聚物。Kraton G1650是一种苯乙烯-乙烯-丁二烯-苯乙烯共聚物。
Dynaflex D3204是GLS公司的热塑性弹性体产品。
为了使斜交帘布层作业能连续运行,有必要的是,在该机器的压力、温度和停留时间条件下,单层片材之间的粘合力大于该单层片材与脱模纸之间的粘合力。将会看到的是,在实施例8~13中没有一个实例的unitape与脱模纸之间的耐剥离性能上升到2.7g/cm以上。因此,当在66℃以332psi(2,290kPa)加压5秒钟的毗邻纤维层有至少约3g/cm的耐剥离性能时,A栏与B栏的耐剥离性能比大于1.0的要求得到了满足。较好的是,毗邻纤维层之间的耐剥离性能是至少约5g/cm。最好的是,该耐剥离性能是至少10g/cm。
虽然已经如此全面、详细地描述了本发明,但要理解的是,不一定严格拘泥于这样的细节,而是业内人士可以做进一步改变和改进,这些全都落入如随后权利要求书所定义的本发明的范围内。
Claims (13)
1.一种耐冲击刚性复合材料,包含
(a)多个纤维层,所述层中每一个都包含一种韧性等于或大于约7g/旦、拉伸模量为至少约150g/旦、和断裂能量用ASTM D2256测定时为至少约8J/g的单丝网络,所述纤维层就在一种其拉伸模量用ASTMD638测定时为至少约1×106psi(6895MPa)的基体中;和
(b)一个弹性体层,配置于毗邻纤维层之间,其拉伸模量用ASTMD638测定时小于约6,000psi(41,300kPa);
其中,在所述基体固化之前,相继纤维层当在66℃以332psi(2,290kPa)加压5秒钟时显示出它们之间至少约3g/cm的耐剥离性能。
2.权利要求1记载的耐冲击复合材料,其中,该网络中的单丝选自伸直链聚乙烯、芳香族聚酰胺和聚吲哚组成的一组。
3.权利要求1记载的耐冲击复合材料,其中,该弹性体层中的弹性体的拉伸模量用ASTM D638测定时小于约4,000psi(13,800kPa)。
4.权利要求1记载的耐冲击复合材料,其中,该弹性体层中的弹性体的拉伸模量用ASTM D638测定时小于约1000psi(6895kPa)。
5.权利要求1记载的耐冲击复合材料,其中,该网络中的单丝有等于或大于约16g/旦的韧性、等于或大于约400g/旦的拉伸模量、和等于或大于约27J/g的断裂能量。
6.权利要求1记载的耐冲击复合材料,其中,在该基体固化之前,相继纤维层之间的耐剥离性能当在66℃以332psi(2,290kPa)加压5秒钟时是至少约10g/cm。
7.权利要求1记载的耐冲击复合材料,其中,该基体占该复合材料的约14~30wt%,且该弹性体层占该复合材料的约2~约10wt%之间。
8.权利要求1记载的耐冲击复合材料,其中,所述纤维网络包含一种片材状单丝排布,其中所述单丝是沿一个共同单丝方向实质上彼此平行排列的,且其中,相继纤维层有彼此相对旋转的单丝方向。
9.权利要求8记载的耐冲击复合材料,其中,相继纤维层中单丝的方向彼此旋转90度。
10.权利要求8记载的耐冲击复合材料,其中,该复合材料的一个表面上粘结一种板材,且其中,该板材包含一种或多种选自金属和陶瓷组成的一组的材料。
11.权利要求8记载的耐冲击复合材料,其中,该复合材料的一个表面上粘结一种板材,且该板材包含一种或多种选自钢、钛、氧化铝和碳化硼组成的一组的材料。
12.耐冲击刚性复合材料的未固化子组件前体物,包含
(a)多个纤维层,所述层中每一个都包含一种韧性等于或大于约7g/旦、拉伸模量为至少约150g/旦、和断裂能量为至少约8J/g的单丝网络,所述纤维层配置于一种热固性基体中,该基体当充分固化时的拉伸模量用ASTM D638测定时为至少约1×106psi(6895MPa);和
(b)在这些纤维层之间的一个弹性体层,所述弹性体用ASTMD638测定时有低于约6000psi(41,300kPa)的拉伸模量;其中,所述基体固化之前所述两个纤维层在66℃以332psi(2,290kPa)加压5秒钟时显示出其间的耐剥离性能为至少约3g/cm。
13.耐冲击刚性复合材料的生产方法,包含下列步骤:
(a)形成高强度单丝的第一和第二纤维网络片材,该单丝有等于或大于约7g/旦的韧性、至少约150g/旦的拉伸模量、和至少约8J/g的断裂能量;
(b)用一种基体树脂浸渍这些纤维网络片材中每一种,该树脂固化后的拉伸模量用ASTM D638测定时为至少约1×106psi(6895MPa);
(c)向所述纤维网络片材之一的至少一个表面上施用一种弹性体材料,后者用ASTM D638测定时有低于约6,000psi(41,370kPa)的拉伸模量;
(d)把第一纤维网络片材铺到第二纤维网络片材的表面上,使所述弹性体材料介于两者之间;
(e)使第一和第二纤维网络片材固结成一种双层复合材料;
(f)把多个双层复合材料彼此叠合在一起;和
(g)使这多个双层复合材料固结,并通过加热和加压使该基体树脂固化。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/639,903 US6642159B1 (en) | 2000-08-16 | 2000-08-16 | Impact resistant rigid composite and method for manufacture |
US09/639,903 | 2000-08-16 |
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CN100413679C CN100413679C (zh) | 2008-08-27 |
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US (1) | US6642159B1 (zh) |
EP (1) | EP1315612B1 (zh) |
JP (1) | JP2004506539A (zh) |
KR (1) | KR100776382B1 (zh) |
CN (1) | CN100413679C (zh) |
AT (1) | ATE375249T1 (zh) |
AU (2) | AU2001284815B2 (zh) |
BR (1) | BR0113279B1 (zh) |
CA (1) | CA2419755C (zh) |
DE (1) | DE60130903T2 (zh) |
ES (1) | ES2292613T3 (zh) |
IL (2) | IL154474A0 (zh) |
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Cited By (12)
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CN101517352B (zh) * | 2006-09-26 | 2013-12-04 | 霍尼韦尔国际公司 | 仅改变树脂含量得到的高性能相同纤维复合材料杂混体 |
CN103917713A (zh) * | 2011-09-06 | 2014-07-09 | 霍尼韦尔国际公司 | 刚性结构uhmwpe ud和复合材料和制造方法 |
CN103917713B (zh) * | 2011-09-06 | 2016-06-29 | 霍尼韦尔国际公司 | 刚性结构uhmwpe ud和复合材料和制造方法 |
CN102632665A (zh) * | 2012-04-13 | 2012-08-15 | 中国兵器工业集团第五三研究所 | 一种芳纶纤维增强树脂基防刺复合材料 |
CN102632665B (zh) * | 2012-04-13 | 2016-03-23 | 中国兵器工业集团第五三研究所 | 一种芳纶纤维增强树脂基防刺复合材料 |
CN105143812A (zh) * | 2013-02-14 | 2015-12-09 | 帝人芳纶有限公司 | 硬耐冲击制品和制造所述制品的方法 |
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CN103866576A (zh) * | 2014-02-25 | 2014-06-18 | 西安工程大学 | 树脂基纳米高强高模防护复合材料及其制备方法 |
CN103866576B (zh) * | 2014-02-25 | 2016-08-24 | 西安工程大学 | 树脂基纳米高强高模防护复合材料及其制备方法 |
CN108351191A (zh) * | 2015-11-13 | 2018-07-31 | 帝斯曼知识产权资产管理有限公司 | 耐冲击复合材料 |
CN112074562A (zh) * | 2018-06-07 | 2020-12-11 | 霍尼韦尔国际公司 | 混合纤维多轴预浸料坯 |
CN112074562B (zh) * | 2018-06-07 | 2023-06-02 | 霍尼韦尔国际公司 | 混合纤维多轴预浸料坯 |
Also Published As
Publication number | Publication date |
---|---|
DE60130903D1 (de) | 2007-11-22 |
ATE375249T1 (de) | 2007-10-15 |
EP1315612A2 (en) | 2003-06-04 |
TW581728B (en) | 2004-04-01 |
DE60130903T2 (de) | 2008-07-17 |
WO2002014408A3 (en) | 2002-05-02 |
ES2292613T3 (es) | 2008-03-16 |
AU2001284815B2 (en) | 2005-02-17 |
WO2002014408A2 (en) | 2002-02-21 |
JP2004506539A (ja) | 2004-03-04 |
IL154474A0 (en) | 2003-09-17 |
MXPA03001380A (es) | 2004-12-13 |
CA2419755C (en) | 2010-02-09 |
KR20030024885A (ko) | 2003-03-26 |
EP1315612B1 (en) | 2007-10-10 |
US6642159B1 (en) | 2003-11-04 |
KR100776382B1 (ko) | 2007-11-16 |
AU8481501A (en) | 2002-02-25 |
BR0113279A (pt) | 2005-02-15 |
IL154474A (en) | 2009-07-20 |
BR0113279B1 (pt) | 2011-07-12 |
CA2419755A1 (en) | 2002-02-21 |
CN100413679C (zh) | 2008-08-27 |
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