CN102482438B - 复合材料的改进 - Google Patents

复合材料的改进 Download PDF

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CN102482438B
CN102482438B CN201080039287.9A CN201080039287A CN102482438B CN 102482438 B CN102482438 B CN 102482438B CN 201080039287 A CN201080039287 A CN 201080039287A CN 102482438 B CN102482438 B CN 102482438B
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prepreg
resin
skin
thermoplastic particles
particle
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CN102482438A (zh
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J.考斯
M.西蒙斯
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Hexcel Composites Ltd
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Abstract

一种可固化预浸料，其提供改善的导电性和优异的机械性能，该可固化预浸料包括导电纤维结构层和热固性树脂第一外层，所述树脂层包含热塑性粒子和玻璃碳粒子。

Description

复合材料的改进
技术领域
本发明涉及复合材料在电磁响应方面的改进，具体而言，本发明涉及提高抗雷击(lightning strike)引起的破坏能力。
背景技术
复合材料具有优于传统结构材料的显著优势，特别是能够在材料密度极低的状况下提供优异的机械性能。因而，复合材料的使用日益广泛，其应用领域覆盖“工业”、“运动休闲”以及高性能航空部件。
预浸料(prepreg)广泛用于制造所述复合材料，所述预浸料包括浸渍了树脂(诸如环氧树脂)的纤维排列。通常，根据需要层叠多个所述预浸料层，一般通过经受高温使所得层压体固化，从而制成固化复合层压体。
常见的复合材料由夹有树脂层的多个预浸料纤维层例如碳纤维层的层压体构成。尽管碳纤维具有一定的导电性，但夹层的存在意味着仅在所述复合材料的层压面方向上显现出导电性。在垂直于层压体表面的方向上，即所谓的z方向上导电性较低。
通常认为z方向上导电性的缺失导致复合层压体易受到电磁危害例如雷击的损害。雷击会对复合材料造成破坏，这种破坏的影响可能十分深远，如果发生在飞行中的飞机结构件上这种破坏可能是灾难性的。因而，对于由这种复合材料制成的航空结构件而言，此问题尤为突出。
另外，用于航空应用的复合材料必须符合严格的机械性能标准。因此，导电性能的任何改善必须不会对机械性能造成不良影响。
现有技术已提出了多种为所述复合材料提供雷击保护的技术和方法，典型地，包括以增加复合材料重量为代价来添加导电成分。
在WO2008/056123中，通过使树脂夹层中包含金属导电粒子，以使所述金属导电粒子接触相邻纤维层并在z方向上建立导电通路，而在没有明显增加重量或影响机械性能的情况下，在抗雷击方面作出了明显改善。
EP2053078 A1教导了一种包含导电粒子和热塑性粒子的预浸料。其中，特别优选金属或包覆金属的导电粒子。
然而，已发现将金属引入预浸料具有不利影响，因为可能存在腐蚀效应、爆炸危险以及材料热膨胀系数的不同。
发明内容
本发明涉及可固化预浸料，该可固化预浸料包含导电纤维结构层和热固性树脂第一外层，所述树脂层包含热塑性粒子和玻璃碳粒子(glassy carbonparticle)。
本申请的发明人发现，第一外层中的玻璃碳粒子具有下述作用：在多个所述预浸料层叠在一起，形成预浸料层叠体，该预浸料层叠体包括由树脂夹层隔开的多个导电纤维层的情况下，在z方向上获得了高的导电性，同时还保持了夹层结构所赋予的优异机械性能。此外，由于导电粒子非金属，因而克服了现有技术使用金属所带来的问题。
据信夹层结构能够赋予优异的机械性能是因为该结构的层状布置。所述玻璃碳粒子位于夹层之中并发挥作用来提供相邻导电纤维层之间的电连接。因而，如果形成所述预浸料的层叠体，则优选至少90wt％的所述玻璃碳粒子位于树脂外层或树脂夹层之中。
因而，另一方面，本发明还涉及预浸料层叠体，该预浸料层叠体包括多个如本申请所述的预浸料，并从而包括多个导电纤维结构层和多个由所述第一外层形成的树脂夹层。
例如，所述层叠体可包括4至200个结构层并具有相应数量的树脂层。在EP0274899中披露了适宜的夹层结构。
在优选实施方式中，所述预浸料包括树脂第二外层，所述预浸料的表面由该树脂第二外层形成而不是由所述第一外层形成。该第二外层通常与所述第一外层组成相同并优选与所述第一外层厚度相同。在该实施方式中，当多个所述预浸料层叠在一起时，第一外层和第二外层合并构成所述夹层。
所述夹层优选具有15至50微米的平均厚度。如果所述预浸料仅包括树脂第一外层，该树脂第一外层构成所述预浸料层叠体中的全部夹层，则所述树脂第一外层也优选具有15至50微米的平均厚度。如果所述预浸料具有树脂第一外层和第二外层两者，所述两者合并构成所述夹层，则因此所述树脂第一外层和第二外层的总厚度为15至50微米。
一旦形成预浸料层叠体之后，随即通过经受高温及任选的高压使该预浸料层叠体固化，从而形成固化层压体。可采用已知的固化方法，例如真空袋、高压釜或压力固化法。
热塑性粒子赋予所得层压体韧性并可由多种材料形成，例如聚酰胺、共聚酰胺、聚酰亚胺、芳族聚酰胺、聚酮、聚醚醚酮、聚亚芳基醚(polyaryleneether)、聚酯、聚氨酯和聚砜。优选的是，所述热塑性粒子包含聚酰胺。优选材料包括聚酰胺6、聚酰胺6/12和聚酰胺12。
所述热塑性粒子可以各种水平存在，然而已发现优选水平为所述预浸料中全部树脂的5％至20％，优选10％至20％。如果形成所述预浸料的层叠体，则优选至少90wt％的热塑性粒子位于树脂外层或树脂夹层之中。
所述热塑性粒子可以是球形或非球形的、多孔或非多孔的。然而，多孔非球形甚或形状不规则的增韧剂粒子显示出具有良好的结果，特别是在冲击强度方面。例如，优选球形度为0.5至0.9的粒子。
球形度是衡量粒子球形程度的尺度。球形度等于与粒子具有相同体积的球的表面积除以该粒子的表面积。因而，对于球形粒子，球形度为1。球形度可由下式给定：ψ＝(6Vp)2/3π1/3/Ap，其中Vp为粒子体积，Ap为粒子表面积。
粒子形状的另一常用量度为长径比。本申请将长径比定义为最大截面直径与最小截面直径之比。因而，球形粒子的长径比为1∶1。所述热塑性粒子优选具有3∶1至1.2∶1的长径比。
优选的是，所述热塑性粒子具有5至50微米，优选10至30微米的d50平均粒径。
碳可以多种形式存在，例如石墨薄片、石墨粉、石墨粒子、石墨烯片、富勒烯、炭黑和碳纳米纤维。然而，仅玻璃(或类玻璃)碳粒子适用于本发明。玻璃碳通常是不可石墨化的，且至少70％为sp2键合，优选至少80％、更优选至少90％、最优选实质上100％为sp2键合。
玻璃碳粒子极硬，在与树脂进行共混的操作过程中不发生粉碎。玻璃碳粒子具有极低甚或为零的孔隙率，完全为实心而不是中空的。中空粒子虽然较轻但由于引入了空隙而会牺牲复合材料的机械性能。
所述玻璃碳粒子的用意是在纤维层的相邻层之间搭桥。然而，过多的所述粒子可能对所得层压体的机械性能造成不良影响。因而，所述玻璃碳粒子的存在水平基于预浸料中的全部树脂优选为0.3至2.0wt％，优选为0.5至1.5wt％，更优选为0.5至1.0wt％。
优选的是，所述玻璃碳粒子具有10至50微米，更优选20至40微米的d50平均粒径。
已发现非常窄的粒径分布尤为有利，因而优选的是至少50wt％的所述玻璃碳粒子为平均粒径±5微米以内。
所述玻璃碳粒子可以是球形或非球形的。然而，已发现球形玻璃碳粒子具有优异的导电性和良好的粒子强度。例如，优选球形度为至少0.95的粒子。换言之，所述玻璃碳粒子优选具有小于1.1∶1的长径比。
为使所述玻璃碳粒子具有搭桥功能(bridging function)，所述碳粒子的平均粒径与平均层间厚度之比为0.9∶1至1.5∶1，更优选1∶1至1.3∶1。
已发现热塑性粒子和玻璃碳粒子的含量比对于同时获得良好的导电性和良好的韧性具有重要意义。因而，优选的是，热塑性粒子与玻璃碳粒子的重量比优选为3∶1至50∶1，更优选为3∶1至40∶1，最优选为5∶1至30∶1，进一步优选为8∶1至20∶1。
所述纤维结构层中的纤维可以是单向、织构形式或多轴的。优选的是，所述纤维为单向的，并且例如在所谓的0/90排列(标识相邻纤维层之间夹角)中通过将相邻各层中的纤维布置成相互垂直，使所述纤维的取向在整个所述预浸料层叠体和/或层压体中变化。在诸多其他排列之中，例如0/+45/-45/90等其他排列当然也是可行的。
所述纤维可包括开裂的(即拉伸破裂)、有选择地不连续或连续的纤维。
所述导电纤维可由各种材料例如金属化玻璃、碳、石墨、金属化聚合物及其混合物制成。优选碳纤维。
所述热固性树脂可选自本领域公知的热固性树脂，例如酚醛树脂、脲醛树脂、1，3，5-三嗪-2，4，6-三胺(蜜胺)、双马来酰亚胺、环氧树脂、乙烯基酯树脂、苯并嗪树脂、聚酯、不饱和聚酯、氰酸酯树脂或它们的混合物。
特别优选的是环氧树脂，例如单官能化、双官能化、三官能化或四官能化环氧树脂。优选的双官能化环氧树脂包括双酚F的二缩水甘油醚(例如Araldite GY 281)、双酚A的二缩水甘油醚、二缩水甘油二羟基萘及其混合物。较为优选的环氧树脂为主链上具有至少一个间位取代苯环的三官能化环氧树脂，例如Araldite MY 0600。优选的四官能化环氧树脂为四缩水甘油基二氨基二苯基甲烷(例如Araldite MY721)。双官能化和三官能化环氧树脂的共混物也是较为优选的。
所述热固性树脂还可包括一种或多种固化剂。适宜的固化剂包括：酐类，特别是聚羧酸酐；胺类，特别是芳族胺，例如1，3-二氨基苯、4，4’-二氨基二苯基甲烷，以及特别是砜类，例如4，4’-二氨基二苯基砜(4，4’DDS)和3，3’-二氨基二苯基砜(3，3’DDS)；酚醛树脂。优选的固化剂为氨基砜，特别是4，4’DDS和3，3’DDS。
树脂和纤维的类型及设计的其他实例可见WO 2008/056123。
本发明的预浸料通常如下制成：通常在高温下使纤维结构层与一个或多个树脂层接触，使得树脂流入纤维之间的空隙，浸渍所述纤维。
在一种实施方式中，制备了树脂与热塑性粒子和玻璃碳粒子的混合物。然后将该混合物制成片状并与使其所述结构纤维的一个或两个面接触。所述粒子由于其尺寸的原因而不会同树脂一起浸渍所述纤维，而是滤出保留在树脂外层中。由于仅包括一个树脂施用步骤，因而将该工艺称为单步工艺。
在另一实施方式中，将不包含粒子的树脂制成片状并使其与所述结构纤维的一个或两个面接触。所述树脂浸渍纤维并在外表面上遗留少许或没有遗留。随后，使包含所述热塑性粒子和玻璃碳粒子的树脂接触该经浸渍的结构纤维的一个或两个面。该混合物保留在外表面，没有进一步浸渍所述纤维。由于包括两个树脂施用步骤，因而该工艺称为两步工艺。
优选所述两步工艺，这是因为，鉴于粒子未扰乱纤维之故该工艺易于提供更加有序的层压体。这可导致优异的机械性能。
进一步优选的是将所述两步工艺应用于具有树脂第一外层和树脂第二外层两者的预浸料。在该实施方式中，使两个树脂层接触结构纤维的两个表面。树脂浸渍纤维并在外表面上遗留少许或没有遗留。随后，使包含所述热塑性粒子和玻璃碳粒子的树脂接触该经浸渍的结构纤维的两个表面。由于施用了四个树脂膜，该工艺称为四膜工艺。
本发明特别适于航空工业领域中的应用，特别是飞机主体板面的形成。
与提高抗雷击性一样，还期望减少或避免雷击之后称为“边缘辉光(edgeglow)”的现象。该现象是复合结构端部电荷累积所引起的并可能成为着火的起源。
已发现用于飞机主体的复合材料可能因这种边缘辉光问题而遭受损害。如果意图将复合材料制成燃料箱构件的一部分，这将是尤为危险的问题。
因而，本发明理想地适于提供飞机燃料箱构件的固化层压复合部件。
附图说明
现通过实施例，参考以下附图对本发明进行示例，其中：
图1为本发明的固化复合层压体的截面图。
图2为本发明的另一固化复合层压体的截面图。
图3为本发明的又一固化复合层压体的截面图。
实施例
制造了碳粒子含量和类型不同的预浸料卷材(10m×0.3m)。包括一种不含玻璃碳的预浸料用于对比。
采用0/90叠放方式制造了7块12层层压体形式的电阻板，并在压力为3巴的高压釜中于180℃固化2小时。以下表1示出了包含碳微球的预浸料和不含微球用于对比的预浸料的电阻结果。从所述电阻板上切下方形样品(35mm×35mm)并在各方形面上涂覆金，对电阻进行了测量。将电极置于所述经涂覆的样品之上，然后使用电源提供电流(A)对电压进行了测定。应用欧米定律(R＝V/I)，对电阻进行了计算。
表1
Araldite MY 0600和GY281获自Huntsman(英国)。PES 5003P获自Sumitomo。Orgasol DNat1 1002D获自Arkema。4，4’DDS获自Huntsman(英国)。
第一种碳粒子为获自Alfa Aesar(美国)的20μm至50μm I型碳粒子，该种碳粒子球形度高，具有大于0.99的球形度和30.1μm的d50平均粒径。第二种碳粒子为获自HTW Hochtemperatur-Workstoffe GmbH的20μm至50μm Sigradur G碳粒子，该种碳粒子形状不规则，具有约0.65的球形度和29.3μm的d50平均粒径。第三种碳粒子同为获自HTW的20μm至50μm碳粒子，该种碳粒子球形度高，具有大于0.99的球形度和30.5μm的d50平均粒径。所述粒径使用Malvern Instruments Mastersizer测量，其中采用300mm的变程透镜(range lens)和2.40mm的束长。
可见包含所述玻璃碳粒子的层压体电阻明显降低。此外，可注意到，与包含形状不规则粒子的层压体相比，包含球形粒子的层压体电阻降低更多。据信这是由于使用形状不规则粒子在相邻结构层之间建立的接触较少。
图1、2和3分别示出了实施例4、3和6的固化层压体的截面。
所述截面图示出了伸入页面排列的单向碳纤维构成的层10和沿页面排列的单向碳纤维构成的层12。分离碳纤维层和树脂夹层14。分散在树脂夹层14中的是不规则的增韧剂粒子。分散在所述夹层中的还有球形度高的玻璃碳粒子16。
对根据实施例3，7和对比例8制造的批料进行了各种机械测试。结果如以下表2所示。
表2
*采用不同的测试仪测量。
可见添加本发明的玻璃碳粒子对机械性能没有显著影响。

Claims (18)

1.一种可固化预浸料，该预浸料包括导电纤维的结构层和热固性树脂的第一外层，所述热固性树脂的第一外层包含热塑性粒子和玻璃碳粒子，其中所述热固性树脂的第一外层的厚度为15至50微米，所述玻璃碳粒子具有10至50微米的d50平均粒径和至少0.95的球形度。
2.权利要求1的预浸料，该预浸料包括树脂第二外层，该预浸料的表面由所述树脂第二外层构成，而不是由所述第一外层构成。
3.权利要求1的预浸料，其中所述热塑性粒子包括聚酰胺。
4.权利要求3的预浸料，其中所述热塑性粒子包括聚酰胺6、聚酰胺6/12、聚酰胺12或它们的混合物。
5.权利要求1-4中任一项的预浸料，其中所述热塑性粒子的存在水平基于所述预浸料中的全部树脂为5wt％至20wt％。
6.权利要求5的预浸料，其中所述热塑性粒子具有0.5至0.9的球形度。
7.权利要求5的预浸料，其中所述热塑性粒子具有5至50微米的d50平均粒径。
8.权利要求1的预浸料，其中所述玻璃碳粒子的存在水平基于所述预浸料中的全部树脂为0.3wt％至2.0wt％。
9.权利要求1的预浸料，其中至少50wt％的所述玻璃碳粒子为d50平均粒径±5微米以内。
10.权利要求1的预浸料，其中所述热塑性粒子与所述玻璃碳粒子的重量比为3:1至50:1。
11.权利要求1的预浸料，其中所述热固性树脂的第一外层包括双官能化环氧树脂。
12.权利要求1的预浸料，其中所述热固性树脂的第一外层包括在其主链上具有至少一个间位取代苯环的三官能化环氧树脂。
13.权利要求1的预浸料，其中所述热固性树脂的第一外层包括氨基砜固化剂。
14.一种预浸料层叠体，该预浸料层叠体包括多个权利要求1或2的预浸料。
15.一种固化复合层压体，该固化复合层压体由下述方法获得：
使权利要求14的预浸料层叠体经受高温，从而制成固化复合层压体。
16.一种飞机主体结构，该飞机主体结构包括权利要求15的固化复合层压体。
17.权利要求16的飞机主体结构，所述飞机主体结构为飞机燃料箱构件的部件。
18.制造权利要求1的预浸料的方法，该方法包括以下步骤：使不含粒子的树脂与所述结构纤维的一个面接触，使得该不含粒子的树脂浸渍所述纤维，随后使包含热塑性粒子和玻璃碳粒子的热固性树脂与该经浸渍的结构纤维的一个面接触形成热固性树脂的第一外层。
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