CN104160081B - 平面复合材料 - Google Patents

平面复合材料 Download PDF

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Publication number
CN104160081B
CN104160081B CN201380013314.9A CN201380013314A CN104160081B CN 104160081 B CN104160081 B CN 104160081B CN 201380013314 A CN201380013314 A CN 201380013314A CN 104160081 B CN104160081 B CN 104160081B
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CN
China
Prior art keywords
layer
fiber
fibre
thermoplastic
composite according
Prior art date
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Expired - Fee Related
Application number
CN201380013314.9A
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English (en)
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CN104160081A (zh
Inventor
B.巴瑟
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Quadrant Plastic Composites AG
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Quadrant Plastic Composites AG
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Publication of CN104160081A publication Critical patent/CN104160081A/zh
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Expired - Fee Related legal-status Critical Current
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/083—Combinations of continuous fibres or fibrous profiled structures oriented in one direction and reinforcements forming a two dimensional structure, e.g. mats
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
    • B29C70/506—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
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    • B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
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Abstract

本发明涉及一种平面复合材料，其包括由离散的强化纤维粗纱制成的UD纤维层A和由热塑性无纺布制成的纤维无纺布层B，该纤维无纺布层包含强化纤维，其中所述层A和B彼此针织在一起。

Description

平面复合材料
技术领域
本发明涉及一种平面复合材料，其包括至少一个由单向的强化纤维粗纱(unidirectional reinforcing fiber roving)制成的层A和至少一个由热塑性无纺布(nonwoven)或热塑性定向纤维层制成的层B，所述的热塑性无纺布或热塑性定向纤维层可以任选地包含强化纤维，其中所述层A和B彼此针织(needle)在一起。
背景技术
热塑性塑料因其重量轻而越来越多地应用于部件、尤其是汽车部件的制造中。为了赋予热塑性塑料足够的刚度和强度，通常将热塑性材料与强化纤维复合。例如，通过融合连续的玻璃纤维毡片(mat)和热塑性熔融片材并且在双带压力机(double band press)上加以固化的方式，由玻璃毡片强化的热塑性材料(glass mat reinforcedthermoplastics)(GMT半成品)制造平面半成品。然而，这个过程需要消耗高能量，因为相对粘稠的熔化物必须在远高于1bar的压力下才能被挤入所述毡片中。此外，所述纤维强化是无定向的，而在汽车领域中特别希望在一个或多个优选方向上进行强化。
根据WO 2006/111037的复合材料正是这种情形。在WO 2006/111037中，描述了一种可热塑性模制的复合材料，其包括由热塑性纤维、和任选的强化纤维制成的纤维无纺布层和由强化纤维制成的纺织或定向层(woven or oriented layer)，所述纤维无纺布层和所述纺织或定向层优选针织在一起。定向纤维层是预制的纤维结构，其中通过缝合线将多个单向纤维粗纱层紧密且牢固地针织在一起。这种纤维结构的制造是相当复杂的，此外，在这些层的针织过程中，由于粗纱被缝合线紧密地绑住而不能充分展开，使得它们只能不充分地且不规则地浸渍有热塑性材料，因此，不利地影响由此制造的模制品的机械性质。
EP-A 323 571涉及一种纤维强化的、可热塑性模制的半成品，其具有通过针织固定的平面纤维结构，该半成品的组成为：
-至少两个由定向连续纤维制成的层A，该定向连续纤维具有的面积重量
最大为300g/m2，和
-至少一个由非定向的纤维制成的层B。
EP-A 323 571的织物平面部分优选包含玻璃纤维，但是还提到了其它纤维，例如碳纤维和由芳香族聚酰胺制成的纤维或者其它热塑性材料。但是，EP-A 323 571未具体说明这些热塑性纤维是否可以存在于层A中或者层B中或两层中。为了制造该半成品，在第二个独立的加工步骤中使所述织物平面部分经历(处理)以浸渍有热塑性熔化物并压制成固体半成品，从而在随后的第三个步骤中可以将该半成品加工成热塑性组件。为了确保良好的浸渍效果，EP-A 323 571强制性要求层A的面积重量不应该大于300g/m2。
GB 2 237 583描述了制造预浸渍制品(prepreg)的方法，其中将热塑性粘合纤维(thermoplastic binding fibers)连续分散于单向的强化纤维上并与该单向的强化纤维一起固化，并且由此压制成型材部件(profile part)或平面半成品。该文没有提及针织。
发明内容
因此，本发明的目的是提供一种基于单向的纤维粗纱的复合材料，其没有上述缺点并且能直接被加工成模制品(molded part)而不需要例如EP-A 323571所要求的在织物结构的制造之后的单独的第二加工步骤。
现已发现，通过直接使用离散的互不相连的强化纤维粗纱(所谓的“单向纤维”，下文称作“单向纤维”)代替定向纤维层，并将它们与具有无规纤维的纤维毡片针织在一起，实现了这一目的。
因此，本发明的主题是平面复合材料，其包括：
A.至少一个面积重量大于300～2000g/m2的单向纤维层，该单向纤维层是由彼此互不相连的离散的、单向的强化纤维粗纱制成的；以及
B.至少一个单位面积重量为100～2000g/m2的无规纤维层B，该无规纤维层B是由强化纤维含量可高达70重量％的热塑性纤维无纺布或热塑性定向纤维层制成的，
其中，所述层A和所述层B彼此针织在一起。
附图说明
图1以透视图的方式示出了根据第一项实施方式的用于制造复合材料的方法的方案。
图2示出了根据第二项实施方式的复合材料的制造方法的方案的透视图。
具体实施方式
本发明的复合材料优选包括为A–B的层序(lay sequence)，但原理上也包括其它层序，举例来说，A–B–A或A–B–A–B是可行的。
在本发明的第一项优选的实施方式中，无规纤维层B包含面积重量为100～2000g/m2、优选为200～1200g/m2和特别是300～1000g/m2的热塑性纤维无纺布，例如针织无纺布或非针织的梳理或气流成网无纺布(carding or airlay nonwoven)。该热塑性纤维无纺布优选包含100％的热塑性纤维，但是其也可包含高达70重量％、特别是30～70重量％的强化纤维。热塑性纤维和强化纤维均优选具有20～100mm的长度。
作为无规纤维层B的热塑性纤维，可以使用任何可纺的(spinnable)热塑性塑料，但是优选MFI为25～150g/10分钟(230℃,2.16kp)的聚丙烯、特别是未改性的聚丙烯(即不含羧基的聚丙烯)，还有聚酰胺、例如聚酰胺-6和聚酰胺-6,6，但此外还有线性的聚酯、聚砜、聚酮和聚醚酰亚胺。希望所述热塑性纤维作为“粘合纤维”，也就是说，在本发明的复合材料的后续加工过程中，应该使它们可热塑性地压制入基体中。
优选的加强纤维是玻璃纤维和碳纤维，但是此外，天然纤维和玄武岩纤维(basaltfibers)以及更高熔点的热塑性材料(例如聚芳酰胺)的纤维也是合适的。在上下文中，术语“高熔点”应该理解为和被提供作为粘合纤维的热塑性纤维(即用于形成聚合物基体)相关联的。特别地，无规纤维层B中强化纤维的熔点和软化点应明显高于热塑性纤维的熔点和软化点，例如至少高50℃。
此外，复合材料可包含在背离层A的层B侧上的由非定向强化纤维制成的相对薄的纤维层C，该非定向强化纤维具有的面积重量为50～500g/m2、优选为100～300g/m2，由此形成了层序A–B–C。所述层C为复合材料提供了额外的强化作用，这在使用具有面积重量相对较小的纤维无纺布时是重要的。玻璃纤维或碳纤维特别适合用作非定向纤维。
在第二项实施方式中，无规纤维层B包括具有连续的热塑性纤维的热塑性定向纤维层，所述热塑性定向纤维层任选地还可以包含连续的强化纤维。优选的热塑性纤维是纤度为600～2400特克斯的聚丙烯纤维，其可以用熟知的稳定剂和粘合促进剂来精制。
所述复合材料优选排他性地包括层A和层B以及任选的层C，而不包括其它类型的另外层。
本发明的复合材料优选包含30～80重量％、特别是50～70重量％的单向纤维。该复合材料的面积重量优选大于400～4000g/m2、特别是1000～2000g/m2。在非固化状态下，其厚度优选为5～15mm。
强化纤维粗纱为例如纤度优选为100～4800特克斯、特别为200～3000特克斯的玻璃、碳、芳香族聚酰胺或玄武岩纤维。特别优选的是碳纤维。基于此的复合材料在纵向上具有特别高的刚度和非常好的灵活性。层A的面积重量大于300～2000g/m2、优选350～2000g/m2。由含相对更重的单向纤维的复合材料所制造的部件比例如在EP-A 323 571中所述的由轻单向纤维所制造的部件表现出更好的强度。此外，这种更重的复合材料、特别是若它们仅具有两层A-B可以比较轻的复合材料更好地被处理。
特别优选的复合材料包含作为单向纤维的碳纤维，并且纤维无纺布层包含作为热塑性材料的聚酰胺、特别是聚酰胺-6和还有30～70重量％的碳纤维。为此，优选使用再循环碳纤维，例如通过已知的再循环方法从经粉碎、精制的由碳纤维强化的部件中获得的再循环碳纤维。这样的复合材料具有良好的耐温性。
图1以透视图的方式示出了根据第一项实施方式的用于制造复合材料的方法的方案。首先，按照梳理或气流成网法制造纤维无纺布层，并将其针织以形成针织无纺布2。首先在循环连续带(4)上彼此相邻(优选尽可能地彼此接近)地布置单向纤维6，由此形成层A。于是，然后连续布置预制的针织无纺布2以形成层B，并且然后在针织装置8中将这两层A和B彼此针织在一起。
此外，还可以不经针织直接将按照梳理或气流成网法制造的无纺布布置在单向纤维上，并在此之后针织。
如果复合材料应分别包括另外的层A或B，那么可以额外地提供并针织相应的网状物(web)。
如果复合材料应该额外地包括薄层C，那么该层C的无规纤维10作为连续的毡片布置到上层B的纤维无纺布上，或者作为短纤维分散在上层B的纤维无纺布上。然后将这所有的三个层彼此针织在一起。这在图1中示意性地被示出。
图2示出了根据第二项实施方式的复合材料的制造方法的方案的透视图。首先，将层A的单向纤维6布置在循环连续带4上，然后通过形成对应于层B的定向纤维层16，将来自桥式送料器14(traversing feeder)的热塑性纤维12和任选的强化纤维布置在单向纤维6上，并且随后在针织装置8中将层A、B彼此针织在一起。这在图2中示意性地被示出。
可将本发明的复合材料切割成薄板。然后在无规纤维层B的热塑性材料的软化温度以上的温度下，通过将这些预切割部件(pre-cut part)挤压入模具中可将其直接加工成三维组件。然而，在无规纤维层B的热塑性材料的软化温度以上的温度和0.5～5bar的压力下、例如在双带压机上，通过连续固化平面复合材料网状物可以制造半成品。还可以在层压设备上进行挤压。经固化的半成品的厚度优选为0.3～5.0mm、特别为1.0～3.0mm。此外，也可以通过将预切割部件和GMT或NMT半成品(即基于玻璃毡片强化的或天然纤维毡片强化的热塑性塑料的半成品)一并插入模具并将它们彼此针织在一起，所述预切割部件由专门用于强化纤维复合物模制品的复合物材料制成。
由本发明的复合材料制成的成品部件是非常轻型的且高刚性的。它们可以用作汽车部件、用于运动用具、用于有轨货车和飞机的制造。

Claims (21)

1.一种平面复合材料，其包括：
a) 至少一个具有单位面积重量为300~2000 g/m²的单向纤维层A，其是由彼此互不相连的离散的、单向的强化纤维粗纱(6)制成的；以及
b) 至少一个具有面积重量为100~2000 g/m²的、由热塑性纤维无纺布(2)或热塑性定向纤维层(16)制成的无规纤维层B，所述热塑性纤维无纺布(2)或热塑性定向纤维层(16)中任一种包含高达70重量%的强化纤维，
其中，所述层A和所述层B彼此针织在一起。
2.根据权利要求1所述的复合材料，其特征在于包括层序A – B。
3.根据权利要求1所述的复合材料，其特征在于所述无规纤维层B由热塑性纤维无纺布形成，所述热塑性纤维无纺布为针织无纺布、或非针织的梳理或气流成网无纺布，以及所述热塑性纤维无纺布由热塑性纤维形成。
4.根据权利要求3所述的复合材料，其特征在于所述热塑性纤维无纺布由热塑性纤维形成并且包含30~70重量%的强化纤维。
5.根据权利要求3所述的复合材料，其特征在于所述复合材料额外地包含在背离所述层A的所述层B侧上的纤维层C，所述纤维层C是由面积重量为50~500 g/m²的非定向强化纤维制成的。
6.根据权利要求1所述的复合材料，其特征在于所述无规纤维层B由具有连续的热塑性纤维的热塑性定向纤维层形成。
7.根据权利要求1所述的复合材料，其特征在于所述无规纤维层B由具有连续的热塑性纤维的热塑性定向纤维层形成，并且包含连续的强化纤维。
8.根据权利要求1或5所述的复合材料，其特征在于所述复合材料包含30~80重量%的单向纤维。
9.根据权利要求1或5所述的复合材料，其特征在于所述层A的强化纤维粗纱是纤度为200~4800特克斯的玻璃、碳、芳香族聚酰胺或玄武岩纤维。
10.根据权利要求1或5所述的复合材料，其特征在于所述层B的热塑性纤维是未改性的聚丙烯或聚酰胺-6或聚酰胺-6,6。
11.根据权利要求10所述的复合材料，其特征在于所述热塑性纤维为热塑性定向纤维。
12.根据权利要求3所述的复合材料，其特征在于所述层A的单向纤维是碳纤维，以及所述无规纤维层B包含30~70重量%的再循环碳纤维和30~70重量%的聚酰胺。
13.用于连续地制造根据权利要求3所述的复合材料的方法，其特征在于首先在循环连续带(4)上彼此面对地布置所述层A的单向纤维并将所述层B的纤维无纺布布置在其上，以及随后将层A和B彼此针织在一起。
14.用于连续地制造根据权利要求5所述的复合材料的方法，其特征在于首先在循环连续带(4)上彼此面对地布置所述层A的单向纤维并将所述层B的纤维无纺布布置在其上，以及随后将层A和B彼此针织在一起，其中在针织之前，将所述层Ｃ的非定向强化纤维布置在所述层B上，并且随后将层A、层B和层C彼此针织在一起。
15.用于连续地制造根据权利要求6所述的复合材料的方法，其特征在于首先将所述层A的单向纤维布置在循环连续带(4)上，并且从桥式送料器将所述层B的连续纤维布置在所述单向纤维上，以及随后将层A和B彼此针织在一起。
16.根据权利要求1或3所述的复合材料用于通过在所述无规纤维层B的热塑性纤维的软化温度以上的温度下将由所述复合材料制成的预切割部件挤压入模具的方式制造组件的用途。
17.根据权利要求16所述的用途，其特征在于所述热塑性纤维为热塑性定向纤维。
18.根据权利要求1或3所述的复合材料用于通过在所述无规纤维层B的热塑性纤维的软化温度以上的温度下、在双带压机中挤压的方式制造可热塑性模制的平面半成品的用途。
19.根据权利要求18所述的用途，其特征在于所述热塑性纤维为热塑性定向纤维。
20.根据权利要求1或3所述的复合材料用于通过在所述无规纤维层B的热塑性纤维的软化温度以上的温度下将由所述复合材料制成的预切割部件和基于玻璃毡片强化的热塑性塑料或基于天然纤维毡片强化的热塑性塑料的半成品一并挤压入模具的方式制造组件的用途。
21.根据权利要求20所述的用途，其特征在于所述热塑性纤维为热塑性定向纤维。
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