CN102514284A - 薄层层压材料 - Google Patents

薄层层压材料 Download PDF

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CN102514284A
CN102514284A CN2011104284032A CN201110428403A CN102514284A CN 102514284 A CN102514284 A CN 102514284A CN 2011104284032 A CN2011104284032 A CN 2011104284032A CN 201110428403 A CN201110428403 A CN 201110428403A CN 102514284 A CN102514284 A CN 102514284A
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layer
thin layer
composite
thickness
sublaminate
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CN102514284B (zh
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史蒂芬·W·柴
川边和正
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Mitsuya-Kisako Inc
Itochu Corp
Fukui Prefecture
Mitsuya Co Ltd
ILT Corp
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Mitsuya-Kisako Inc
Itochu Corp
Fukui Prefecture
ILT Corp
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Abstract

使用厚度小于0.08mm的薄层的纤维复合材料提供了改进的抗分层性和层压材料的更薄最小规格。薄层可以与普通层混合，进行交织以便提高强度，并用粘接剂作为连接的增强物。

Description

薄层层压材料
本申请是名称为“薄层层压材料”、国际申请日为2005年9月23日、国际申请号为PCT/US2005/034961、国家申请号为200580032157.1的发明专利申请的分案申请。
相关申请的交叉引用
本申请要求美国临时申请No.60/612740(申请日为2004年9月24日)和美国临时申请No.60/668341(申请日为2005年4月4日)的优先权。
技术领域
本发明通常涉及纤维复合材料，特别是涉及使用薄层(ply)以便获得改进的物理特性的复合材料以及制造该材料的方法。
背景技术
普通的复合材料层(由树脂浸渍或并不由树脂浸渍)为至少0.12mm厚。复合材料层的层压材料通过将单向层堆垛在一起且随后进行某些凝固和固化处理而形成。需要有不同方向的层，以便提供沿多个方向的机械特性。这样，当需要最少两个层方向时，例如一个层定向为参考0°角，另一个为90°。在下文中，将使用标记[0/90]或[+45/-45]来描述层的层方向，例如，一层在0°且另一层以90°层压在第一层上，或者一层处于45°且层压在-45°的另一层上，表示相对于轴线的方向(单位为度)。另外，层压材料必须对称地堆垛，以避免翘曲。因此，在现有技术中，最少三层(类似[0/90/0])或四层(类似[0/90/90/0])的最小(规格)总厚度为0.36或0.48mm，不管该厚度是否需要，因为各层为至少0.12mm。通常采用方向为[0/90/45/-45]的4层。当形成得对称时，需要8层，且最小总层压材料厚度为大约8×0.12mm，或者为大约1mm(使用至少0.12mm的普通层)。
分层通常产生于层压材料的自由边缘处，或者在施加集中的支承负载的点处，或者在受到横向冲击或在层压材料固化过程中形成应力的点处。不管它的来源如何，分层都是故障模式，它通常限制了对多方向层压材料的关键的平面内承载能力的充分潜力的利用。当复合材料用于越来越多的重要结构(例如波音787以及空中客车350和380飞机)时，复合材料部件可以有数百个层厚。对于接收复合材料的很多用途，分层是严重威胁。
一种常用方案是使层压材料形成为3维织物。这种纺织技术有多种。它们有至少两个缺点：成本可能更高，且平面内特性降低，从而形成用于平面外纤维的空间。作为该方案的一种可选代替方式是使用横向缝合。该方法并不昂贵，但是还不可靠。缝合引起对复合层压材料的附加损坏。
发明内容
简要地说，本发明实施例包括一种层压材料，该层压材料利用0.08mm厚度或更小厚度的薄层来构成。可选实施例包括厚度小于0.08mm的薄层和至少0.12mm厚度的更厚普通层的组合。这些组合提供了改进的抗微破裂和分层的性能，使层压材料的最小规格更薄，提供了较厚和较薄层混合的机会，增强了粘接连接，使交织产品具有比普通织物更高的性能，提高了管和容器的直接强化，并提供了切碎的纤维以便形成更强的板模制混合物。多方向层的子层压材料(下文中称为“子层压材料模块”)能够形成为用于复合层压材料的基本构造块，从而降低了装配成本，同时保持很高的抗分层性。不管是否进行自动化，由薄层子层压材料和层压材料形成的产品相对于由普通厚度层的层压材料构成的产品将在成本上有竞争力。
利用已知的纤维束伸展处理，普通的12k碳、玻璃或Kevlar纤维的纤维束(大约0.12mm厚)可以伸展而形成0.02mm厚的纤维条。通过这样的薄层，例如本发明的3层方向对称子层压材料可以有0.12mm厚度，与普通0.12mm层相同。最小规格减小至普通层的厚度的六分之一(1/6)。在对称4层层压材料中，最小规格将为0.16mm。该小规格模块提供了通过普通厚层无法达到的设计选择，并有更高的抗分层性。实际上，普通复合材料结构的许多设计受到该分层标准的支配。因此，利用薄层层压材料可以有效设计更高性能或更轻重量的结构。
附图说明
图1表示了本发明的薄层层压材料；
图2表示了现有技术的更厚层；
图3是作为层厚的函数的法向应力的曲线图；
图4是作为层厚的函数的剪切应力的曲线图；
图5是作为层厚的函数的分层开始应力的曲线图；
图6A表示了厚层和薄层的使用；
图6B表示了子层压材料；
图7A是使用子层压材料的复合材料的透视图；
图7B是使用子层压材料的复合材料的侧视图，以便表示接头；
图8A是作为层厚的函数的硬度的曲线图；
图8B是作为层厚的函数的最大应力的曲线图；
图9表示了干的薄层；
图10表示了树脂浸渍的薄层板；
图11表示了三层层压材料；
图12表示了层编织和在卷曲交换区域中的角度；
图13A是对于脆性粘接剂的各个温度，负载变形相对于层厚的曲线图；
图13B是对于韧性粘接剂的各个温度，负载变形相对于层厚的曲线图；
图14表示了使用薄层来连接两层；
图15是表示图14的接头的效果的表；
图16表示了金属箔用于层压材料的一个侧面上；
图17表示了金属箔用于层压材料的两侧面上；
图18A表示了金属箔用于层压材料的两侧面上和中心处；
图18B是图18A中的一部分的放大剖视图；以及
图19表示了在层压材料的中心没有箔时的层结构。
具体实施方式
图1中表示了本发明的复合材料10的截面。复合材料10有多层，包括第一层12，该第一层12以点表示，并沿第一方向定向。第一层12由第二层14分开，该第二层14定向成沿与第一方向不同的第二方向。第二层14没有用任何标记来表示，以便在图1中使它们与第一层12区分开。根据本发明，层12、14的厚度“t”小于0.08mm，优选是从0.02mm至0.06mm。图2只是用于表示普通/现有技术的层压材料由交替的层(例如16、18)构成，这些层的厚度大于本发明的层的厚度，各层的厚度“T”为大致0.12mm或更大。
根据本发明，薄层层压材料具有改进的抗分层性。它们不需要平面外的纤维，因此保持优良的平面内特性。例如，在层压材料的自由边缘处的计算的法向应力和剪切应力如图3和4中所示，作为层厚的函数。层厚为至少0.12mm的普通/现有技术如各图右侧所示，其中，层厚向左侧减小至0.02mm。这些测量值显示：当层厚减小至0.12mm的现有技术厚层层压材料的1/3和1/6时，法向应力和剪切应力明显降低。这是现有技术无法预料的结果。因此，薄层层压材料提供了改进的抗分层性的方案。
图5表示了薄层在分层开始时的效果的另一实例，该图5表示了作为有效层厚的函数的、分层所需的应力。当层厚减小时，分层应力再次明显增加。
作为可选实施例，厚层和薄层的混合组合能够提供在性能和成本之间的平衡，且该组合包含于本发明中。薄层不仅增加了刚性，而且还增加了在层下落时的柔性。这通过使用子层压材料模块来实现，其中，具有不同方向的薄层或者不同方向的薄层和厚层组合的模块预先形成为用于层压材料的构造块。子层压材料模块的下落代替了各层的下落。
实例1：本发明的实例包括厚度为0.12mm的厚层和厚度为0.02mm的薄层的组合。这在图6A中表示为具有薄层21和厚层23。而且，图6B中的子层压材料25可以是厚薄混合体，有一个厚层[0]27和一个薄层[90]29。该子层压材料模块的总厚度可以为0.12mm+0.02mm＝0.14mm，这时，[0]的百分数应当为0.12/0.14＝86％。使用这样的子层压材料建造桅杆或吊杆将提供较高的各向异性结构，它具有只使用厚层的普通层压材料所不能达到的刚性。对于普通层压材料，厚层的重复模块必须有9层[0]和1层[90]。总的子层压材料模块的厚度将为1.20mm，其中[0]的百分数等于90％。该设计将9层[0]堆垛在一起，这从刚性的观点来看是很差的设计。这实际上使得桅杆不稳定，并容易由于折断而失效。
实例2：当希望有更高的[0]百分数时，可以有两个厚层[0]，随后有一个薄层[90]。这时，[0]的百分数应当是0.24/0.26＝92％。在具有两个[0]和一个[+/-45]的三方向子层压材料模块中，[0]百分数为0.24/0.28＝86％。这两个实例将使得桅杆或吊杆有更刚性的层压材料。这种混合结构也用于驱动轴、簧片和体育用品(例如撑杆跳高杆、曲棍球棒、高尔夫球棒等)。
实例3：厚薄层层压材料的另一实例是三方向子层压材料，其具有一个0.12mm厚层[0]和两个0.02mm角度薄层[+/-30]或[+/-45]，例如[+30/0/-30]或[+45/0/-45]模块。总的子层压材料的厚度为0.16mm，它可以在层的下降中作为一个步骤来完成。可以制造任何厚层和薄层组合的三方向模块。该设计灵活性使得产品具有明显改进的层压材料性能，且在制造时明显节约成本。
实例4：相同思想的多方向子层压材料可以设计成用于梁和肋，作为复合材料结构的子结构。这时，在网络中的剪切模块最重要。厚薄混合体可以有厚[+/-45]与薄[0]的组合。在所有这些用途中，子层压材料的层合处理可以沿一个方向，例如沿梁的轴向。在用于机翼的蒙皮时，层合可以沿机翼轴线。当用于机身时，层合可以沿两个方向，一个沿箍环方向，另一个沿轴向方向，或者沿两个螺旋角。这能够非常明显地节省层合机器能力以及层合时间和劳动。
本发明的复合材料能够由多个子层压材料模块构成。图7A表示了包括子层压材料模块33的复合材料31。图7B是具有子层压材料37的复合材料35的平面侧视图，它与图7A类似，用于表示子层压材料接头39。子层压材料板沿宽度方向连接，且对板进行堆垛，且接头部分不会沿厚度方向重复。图7A、7B的子层压材料可以都相同，或者它们可以不同。子层压材料可以全部为薄层，或者有薄层和厚层的组合，和/或子层压材料可有交织织物层，如图12所示。使用薄层使得子层压材料厚度与普通层厚近似相同。使用该方法，可以获得具有优良机械特性的大尺寸复合材料模制产品。
形成薄层纤维束的一种方法是通过使普通纤维束伸展。伸展的纤维束的截面为矩形，厚度为0.04mm或更小，宽度为大约20mm。这些伸展的纤维束能够很容易交织，以便形成织物。交织纤维束的截面如图12中所示。交织织物提供了高性能的层压材料，它很容易加工成复杂几何形状。该交织织物的总厚度将为薄层厚度的两倍，即当使用0.02mm的薄层时为0.04mm。具有厚层和薄层的交织织物的结构性能如图8A和8B中所示，其中，增加的机械特性表示为层厚从右至左减小。当使用0.02mm的层代替0.12mm的层时，硬度增加35％，而最大应力减小20％。
薄层24可以为(a)干纤维26(即没有树脂浸渍)，如图9所示，厚度小于0.08mm，优选是小于0.06mm，或者(b)在树脂浸渍(预浸渍)的板28中的纤维26小于0.08mm，优选是小于0.06mm(图10)。
作为实例，层压材料28如图11中所示，具有由多个层36形成的三层30、32、34。层可以在靠近端部38处并沿侧部(例如在40处)以及层相遇处42进行定位。在它们之间可以有间隙。这些间隙对层压材料的机械性能影响很小，因为层厚非常小。
图12是交织层41的剖视图。薄层层压材料具有改进的性能，因为当层厚减小时，图12中所示的卷曲交换区域42的尺寸和形成的角度A变得更小。当伸展的纤维束因为遇到垂直方向的纤维束而进行上下编织时，卷曲的影响区域由于更细纤维束而更小。交换纤维束必须容纳相互的厚度。纤维束越细，在纤维束交换处所需的容纳越小。因此，交织纤维束的宏观硬度和在交换处所形成的应力都受到该厚度的影响。纤维束越细，硬度越高，且局部应力越低。
粘接的接头提供了连接两个复合材料部件的最佳方法。粘接的接头更容易制造，且在接头处引起的应力集中最小。广义地说，有两种粘接接头粘接剂：脆性粘接剂和韧性粘接剂。图13A和13B示出了分别在各种温度下的脆性粘接剂和韧性粘接剂的负载-变形曲线。最硬的粘接剂的负载-变形曲线是室温性能。当温度增高时，粘接剂的性能将越来越象韧性材料。图13A中所示的脆性粘接剂是玻璃粉增强的环氧树脂，韧性粘接剂是PMMA。
新的粘接接头43可以利用薄层作为增强材料来制造，如图14中所示。该接头的效果在图15的表中表示，它表示了由有限元分析得到的预测。应当知道，相对于未增强的粘接剂的应力，应力降低56％和30％。另外，该接头设计获得了在剥离和剪切应力之间的平衡，并不是象未增强的粘接剂那样一个支配另一个。对于薄层增强粘接剂，[0]方向与施加在粘接接头上的轴向力对齐。
板模制复合物和垫可以利用切碎的薄层纤维来制造。这些产品具有很高性能，因为硬度和强度由于减小卷曲交换而损失。另外，薄层通过立方关系而降低了弯曲硬度：即厚层厚度的1/6将为原始硬度的1/216。因此，由切碎的薄层纤维束制成的板模制复合物将更容易适应在模制部件中的曲率和形状的突然变化。该处理的优点是附加提供了硬度和强度。
薄层还有利于碳增强的热塑性带的在线凝固的质量和处理速度。当带的厚度更小时，厚层带通常的僵硬性(高硬度)能够明显降低成更柔软或柔顺的带。与上述相同的立方关系也用于带的弯曲刚性。在使用薄带的在线处理中，并不需要只是为了使带更柔软的预热。该处理能够通过纤维缠绕成形和随后固化而制成压力容器。
图16-18表示了包括金属和薄层层压材料的本发明层压材料的另一实施例。图16表示了金属44施加在薄层层压材料46的一侧面上。图17表示了金属48、50施加在薄层层压材料52的两侧面上。图16和17表示了金属基体复合物粘在薄层层压材料的一侧面或两侧面上时的产品。金属层可以以本领域已知的多种方式产生，包括金属箔、蒸气沉积(CVD)、金属嵌入聚合物中、电镀等。金属保护该层压材料。在未涂覆的薄层层压材料中，表面层非常薄。当层压材料中的外侧纤维受损时(例如由于冲击或刮擦)，在表面层中的纤维破坏能够很容易发生，这能够导致层压材料失效。图16和17中所示的产品有助于防止该纤维破坏和失效。图18A表示了在薄层层压材料60、62的两侧面54、56和中心58处有金属。图18B是图18A的剖视图，用于表示在图18A中的层压材料层中的纤维的方向(90°，-45°)。当金属基体组分插入薄层层压材料中心时，如图18A和18B所示，将防止在层压材料中的双倍厚度。这有助于对称层压，其中，在层压材料中心的双倍厚度可能导致基体破裂和分层。图19表示了当没有金属时中心层的双倍厚度，它使得层压材料易于产生裂纹和分层。
使用金属和薄层复合材料的新类型金属基体复合材料能够以相当低的成本制造。例如，可以形成使用薄碳纤维增强的塑料(CFRP)并结合钛(Tigr：钛-石墨)或铜(Cugr：铜-石墨)的高温复合材料。该金属基体复合材料具有耐高温性和独特的抗腐蚀性，可用于多种用途，包括化学试剂管路和容器。
对于垫和交织织物，包括树脂传递模制(RTM)和真空辅助树脂传递模制(VARTM)处理，使用薄层材料使得材料更容易流动，并提供了对繁杂表面的适应性，同时保持优良的物理特性。
上述实施例是作为本发明的实例。本领域技术人员应当知道这些实例的变化形式。这些变化形式包含在本发明的精神中。

Claims (13)

1.一种复合材料，包括至少一个第一层碳纤维薄层和一第二层相邻的碳纤维薄层，该碳纤维薄层的厚度从0.02mm到0.06mm，其中，第一层中的碳纤维薄层沿第一方向定向，第二层中的碳纤维薄层沿第二方向定向，第二方向与第一方向成一角度；其中：该复合材料包括厚度为至少0.12mm的普通的层和厚度为0.02mm到0.06mm的薄层的组合。
2.根据权利要求1所述的材料，其中：该复合材料包括碳薄层的子层压材料模块的组合。
3.根据权利要求2所述的材料，其中：该复合材料包括碳薄层的子层压材料模块和普通层的子层压材料模块的组合。
4.根据权利要求2所述的材料，其中：该复合材料包括具有碳薄层和普通层的子层压材料模块。
5.根据权利要求1、2、3或4所述的材料，其中：碳薄层进行交织或编织。
6.根据权利要求1、2、3或4所述的材料，其中：该复合材料使用树脂传递模制而形成。
7.根据权利要求1、2、3或4所述的材料，其中：碳薄层与粘接剂组合，以便提供增强的粘接材料，用于使复合材料和/或金属组分通过粘接的接头而连接。
8.根据权利要求1、2、3或4所述的材料，其中：碳薄层与粘接剂组合，以便提供增强的粘接材料，用于具有蜂窝或夹层结构的复合材料组分。
9.一种产品，包括如权利要求1、2、3或4所述的材料，其中：碳薄层包含在热固性或热塑性带中，产品通过带布置方法或带缠绕方法而形成，且对带进行固化。
10.一种纤维金属复合材料，包括如权利要求1、2、3或4所述的材料以及金属板。
11.根据权利要求10所述的复合材料，其中：金属板只布置为表面层。
12.根据权利要求10所述的复合材料，其中：金属板布置在具有相同纤维方向的薄层之间。
13.根据权利要求10所述的基体复合材料，其中：金属板是从钛和铜的组中选择的金属。
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EP1793989A2 (en) 2007-06-13
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CA2581042A1 (en) 2006-04-06
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CA2581042C (en) 2013-11-19
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BRPI0516061A (pt) 2008-08-19
ATE553917T1 (de) 2012-05-15
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EP1793989B1 (en) 2012-04-18
US20060093802A1 (en) 2006-05-04

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