CN113329866A - 制备夹层形式的复合材料的方法 - Google Patents

制备夹层形式的复合材料的方法 Download PDF

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Publication number
CN113329866A
CN113329866A CN201980084765.9A CN201980084765A CN113329866A CN 113329866 A CN113329866 A CN 113329866A CN 201980084765 A CN201980084765 A CN 201980084765A CN 113329866 A CN113329866 A CN 113329866A
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CN
China
Prior art keywords
core
insert
polymeric material
outer layer
sandwich
Prior art date
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Pending
Application number
CN201980084765.9A
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English (en)
Inventor
盖坦·马奥
尼古拉斯·迪蒙
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Saint Gobain Performance Plastics France
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Saint Gobain Performance Plastics France
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Filing date
Publication date
Application filed by Saint Gobain Performance Plastics France filed Critical Saint Gobain Performance Plastics France
Publication of CN113329866A publication Critical patent/CN113329866A/zh
Pending legal-status Critical Current

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    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
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    • B29D24/002—Producing articles with hollow walls formed with structures, e.g. cores placed between two plates or sheets, e.g. partially filled
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/16—Cooling
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    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明的目的可以是一种制造夹层形式的产品的方法，所述夹层包括芯和外层。所述外层可以由包含纤维增强聚合物基体的复合材料构成。所述方法使用耐热材料***物，所述耐热材料例如是硅树脂。本发明的目的可以是提供一种制造夹层的方法，所述方法将所述夹层的所述芯的材料选择与所述外层的材料选择分开。

Description

制备夹层形式的复合材料的方法
技术领域
本发明涉及由复合材料制成的产品领域。由复合材料制成的产品是指可包括由聚合材料特别是热塑性或热固性材料组成的树脂基体的产品。该基体可由这样的材料增强：即，该材料的熔点可高于聚合材料熔点。FRP通常是指“纤维增强塑料”。
背景技术
FRP类型的复合材料相对于材料的重量具有良好的机械阻力。该类型的复合材料还具有非常好的耐腐蚀性。它们具有比单独使用的部件更优越的特性。特别是在汽车或航空领域，它们可以减轻传统上由钢制成的零件的重量。它们还具有良好的抗疲劳性。
复合物的增强可以通过不同的方式获得：在基体中添加分散的矿物纤维，使用由钢或合成材料制成的支撑结构，使用增强纤维织物，使用通过纺织方法获得的无纺布或垫或其他产品。
织物增强件可以具有扁平结构并且可以由垂直交叉和交织的纬纱和经纱构成。制造织物增强件可能需要使用单独的经线织轴。
最近，已有使用针织增强件。针织增强件可以指通常由连续纱线获得的产品，其中纱线形成连续成行排列的交织网孔。生产传统针织物只需要一个纱线织轴形成纱网。
纱线可以是单丝或复丝类型。复丝可以是粗纱(即一组没有加捻组装的平行连续细丝)、短纤纱(即一组有加捻组装的短纤维)。纱线也可以是多种不同材料的纱线或细丝的组件。该组件可以通过扭曲、缠绕来完成。因此可以生产包含聚合材料和增强材料的纱线。例如，可以组装芳纶纱线、碳纱线、玻璃类型纱线和热塑性纱线(即聚丙烯、聚碳酸酯、聚醚酰亚胺(PEI))构成的增强纱线。这种类型的纱线可以称为混合纱线。
针织这种类型的混合纱线可以获得包含增强体和基体两者的预制件。这种预制件可以说是“干的”，与通常称为“预浸料坯”的胶粘和粘性树脂预浸渍织物相反。
还可以生产夹层形式的产品，该夹层可以包括FRP型复合材料制成的两个外层或表层以及泡沫类型的轻型材料或多孔蜂窝状材料制成的中心体或芯。由于其夹层形式的结构，这些产品可以在同等重量的情况下实现更好的性能。
表层的浸渍以及它们与芯的粘结可能影响夹层复合物的最终特性。表层的良好浸渍通常需要一种分多个阶段进行的固结方法，这会耗费时间和资源。当成品具有复杂的3D形状时尤其如此。
用于制作夹层的传统方法一般可以包括以下步骤：
使用以聚合材料预浸渍的表层生产外层；
外层在芯(例如蜂窝状或泡沫状)的两侧并置；
固结外层以确保聚合材料的熔化，同时确保所有层与芯的连接。
根据表层的厚度，可能需要堆叠多个折层。然后可能需要几个固化循环以确保每个表层的织物折层的良好固结并确保表层与芯之间的良好粘附。使用这种制造方法，可以具体地选择夹层的芯来抵抗外层的固化。在某些情况下，已经发现芯会因温度和压力而受损。例如，已经观察到泡沫状芯在该处理过程中可能凹陷或收缩。
此外，还发现在固化过程中，聚合材料可能会流入蜂窝状结构的孔中。
文档EP 0 770 472 A1概述了一种用于制造复合材料夹层板的方法，该复合材料夹层板具有由开孔结构形成的芯以及纤维和树脂形成的表层。为了避免芯的开孔中的树脂熔化，该文档提供了在表层和芯之间***防水膜和胶膜。闭合模具后，单个热循环可以使胶水聚合，然后在压力下将树脂注入纤维中，最后使树脂聚合。
然而，该方法的缺点是需要使用多个层，特别是防水膜。这增加了成品的成本。
文档EP 1 086 801 A1概述了一种利用树脂注射技术RTM制造夹层板的方法。为了避免填充蜂窝状结构，该方法需要在模具中形成膨胀材料薄膜以及在芯的每个面上形成阻隔织物。
根据本发明的方法使用耐热材料***物来形成外层，而不是芯，并且当外层被固结时，***物由芯代替。剩下的就是进行热处理以将外层粘结至芯。
具体实施方式
根据第一实施例，根据本发明的方法可以包括以下步骤：
外层或预浸渍表层的实施例，例如通过针织或编织可包括聚合材料和增强材料的纱线；
在模具中并置外层、耐热材料***物和第二外层；
通过在可允许聚合材料在未达到增强材料熔点的情况下固结和融合的温度和压力进行固化而将表层成形；
移除***物并在两个预成型表层之间引入夹层的芯(例如泡沫状或蜂窝状)；
在允许外层与夹层的芯之间粘附的温度固化组件。
根据另一个实施例，表层可以由增强材料的织物制成并且聚合材料可以通过注射提供。
该方法然后可以包括以下步骤：
在模具中并置增强织物、耐热材料***物，然后是另一种增强织物；
树脂注射；
移除***物并在两个预制表层之间引入夹层的芯(例如泡沫状或蜂窝状)；
在允许外层与夹层的芯之间粘附的温度固化整体。
***物可以是刚性或非刚性的。特别地，它可以是硅树脂。
在一些实施例中，它可以在该温度膨胀。这可以允许在固结过程中增加压缩。
***物可为成品提供特定形状，例如斜面形状。
在一些实施例中，可以在夹层体与外层之间***粘合剂层。该粘合剂可以是液体胶、粘合膜或包含热塑性纤维的针织预制件。
外层可以相同或不同。
有利地，为了获得良好的夹层效果，芯的厚度一般可以为至少约2mm且不大于约50mm，优选地至少约3mm且不大于约40mm，且更优选地至少约5mm且不大于约25mm，并且表层的厚度可以为至少约0.2mm且不大于约5mm，优选地至少约0.4mm且不大于约2mm，且更优选地至少约0.5mm且不大于约1mm。
本发明的目的可以是提供一种制造夹层的替代方法，特别是提供一种将夹层的主体的材料选择和外层的材料选择分开的制造方法。
聚合材料可包括热塑性材料，例如聚碳酸酯(PC)、聚醚酰亚胺(PEI)、聚丙烯(PP)、聚(对苯二甲酸乙二酯)(PET)、聚醚醚酮(PEEK)或热固性材料，诸如环氧树脂、氰酸酯、酚醛树脂、聚酯。
增强材料可包括合成材料，诸如对位芳纶、聚丙烯；天然材料，诸如亚麻布；无机材料，例如玻璃、石英、碳、玄武岩、金属。
根据本发明的方法已被证明是特别有利的，因为它可以将夹层的芯类型的选择与转换方法的选择分开。根据本发明的方法可以实现外表层的良好浸渍。
许多不同的方面和实施例都是可能的。本文描述了这些方面和实施例中的一些。在阅读本说明书之后，本领域的技术人员会理解，那些方面和实施例仅是说明性的，并不限制本发明的范围。实施例可以根据下面列出的任何一个或多个实施例。
实施例1.一种制造夹层形复合材料产品的方法，其中所述夹层形复合材料产品包括两个外层和一个芯，所述外层具有纤维增强聚合材料的基体，所述聚合材料的熔点低于构成所述纤维的材料的所述熔点；其中所述方法的特征在于其使用由熔点高于所述聚合材料的所述熔点的材料组成的***物，所述外层固结在所述***物上；并且其中所述***物随后被所述夹层的所述芯替换，然后组件经历固结处理以将所述外层粘结至所述芯。
实施例2.根据实施例1所述的方法，其特征在于包括以下步骤：生产由纤维增强聚合材料组成的预制件，所述预制件旨在成为所述夹层的所述外层；在模具中并置第一预制件、***物和第二预制件；通过加热和加压以达到所述聚合材料的所述熔点的温度，在未达到所述增强材料或所述***物的材料的所述熔点的温度的情况下，固结所述预制件以获得所述外层；移除所述***物、分离所述外层并***所述夹层的所述芯；热处理以将所述外层粘合至所述芯；冷却由此获得的所述产品。
实施例3.根据实施例2所述的方法，其特征在于，所述预制件使用预浸渍的聚合物树脂织物制成。
实施例4.根据实施例2所述的方法，其特征在于，通过针织包含所述增强材料和所述聚合材料的纱线来制成所述预制件。
实施例5.根据实施例2所述的方法，其特征在于，在旨在形成没有芯的区域的位置处增加所述预制件之间的剥离成本。
实施例6.根据实施例1的方法，其特征在于包括以下步骤：在模具中并置增强材料制成的织物或针织物、所述***物、和增强材料制成的第二织物或针织物；在压力和温度下注入聚合材料树脂；移除所述***物并***所述夹层的所述芯；固结固化以将所述外层粘附至所述夹层的所述芯；冷却由此获得的所述产品。
实施例7.根据实施例1所述的方法，其特征在于，所述***物由硅树脂制成。
实施例8.根据实施例1所述的方法，其特征在于，所述增强材料选自玻璃纤维、碳纤维和芳纶纤维。
实施例9.根据实施例1所述的方法，其特征在于，所述聚合材料为热塑性类型，特别地选自聚碳酸酯(PC)、聚醚酰亚胺(PEI)、聚丙烯(PP)、聚(对苯二甲酸乙二酯)(PET)、聚醚醚酮(PEEK)。
实施例10.根据实施例1所述的方法，其特征在于，所述聚合材料为热固性类型，特别地选自环氧树脂、氰酸酯、酚醛树脂和聚酯。
实施例11.根据实施例1所述的方法，其特征在于，所述夹层的所述芯由多孔蜂窝状材料组成。
实施例12.根据实施例1所述的方法，其特征在于，所述芯的厚度为至少约2mm且不大于约50mm。
实施例13.根据实施例1所述的方法，其特征在于，所述外层中的每个的厚度为至少约0.2mm且不大于约5mm。
以下实例以非限制性方式说明本发明。
实例
实例1
将数个“预浸料坯”氰酸酯浸渍碳纤维织物铺覆在钢模具中以形成夹层的第一表层。
刚性***物(例如几毫米的
Figure BDA0003122382960000061
块)沉积在织物上。
夹层的第二表层是通过在刚性***物上铺覆数个“预浸料坯”织物制成的。
特氟龙涂覆的剥离层(PTFE涂覆的玻璃纤维)放置在两个表层之间的结合处。结合处是表层结合以覆盖芯区域的区域。
模具由柔性的反模闭合。
通过在约180-220℃的真空下热处理几个小时使表层固结。
使组件冷却并移除***物。
将耐高温胶水涂在每个要与芯接触的面上。
引入聚酰亚胺泡沫状芯(密度约为50kg/m3)代替***物。
然后将整个夹层在约90-120℃的真空下进行最终固结处理，以确保表层和芯的良好粘附。
实例2
第一表层由多个未浸渍的碳纤维增强织物堆叠形成，其沉积在钢模具中。
柔软的***物(几毫米厚的硅树脂板)沉积在织物上。
第二表层由沉积在***物上的相同类型的织物形成。
模具由钢制反模闭合。
在10至15巴的压力下，在80至120℃的温度通过已知的RTM类型方法注入氰酸酯树脂。
热处理持续4小时。
使模具冷却，然后移除***物并通过移除剥离层使表层分离。
一层非常薄的氰酸酯树脂被添加到表层上(在与蜂窝状结构接触的面上)。
在两个表层之间引入蜂窝状芯，代替***物，以形成夹层。
整个夹层在真空下接受4小时热处理(180-200℃)，以粘结表层和芯。
实例3
针织物是使用包含玻璃纤维和热塑性纤维的混合纱线制成的。
该针织物沉积在钢模具中以形成第一表层。
将可在温度作用下膨胀的材料***物沉积在针织物上。
相同类型的第二针织物沉积在***物上以形成第二表层。
特氟龙涂覆的剥离层(PTFE涂覆的玻璃纤维)放置在两个表层之间的结合处。结合处是两个表层结合以覆盖芯区域的区域。
特氟龙涂覆的剥离层放置在两个表层之间的结合处。
模具由钢制反模闭合。
在3至10巴的压力下，在200-250℃的温度热处理几十分钟使表层固结。
使模具冷却，然后移除***物并通过移除剥离层使表层分离。
热塑性纱线的针织预制件沉积在蜂窝状芯的两侧，以便在夹层的芯与表层之间形成连接层。
蜂窝状芯和针织预制件被引入两个表层之间，代替***物，以形成夹层。
整个夹层在真空下接受几个小时的热处理(200-250℃)，以粘结表层和芯。
实例4
针织物是使用包含玻璃纤维和热塑性纤维的混合纱线制成的。
该针织物沉积在钢模具中以形成第一表层。
将可在温度作用下膨胀的刚性材料***物沉积在针织物上。
相同类型的第二针织物沉积在***物上以形成第二表层。
特氟龙涂覆的剥离层放置在两个表层之间的结合处。
模具由钢制反模闭合。
在3至10巴的压力下，在200-250℃的温度热处理几十分钟使表层固结。
使模具冷却，然后移除***物并通过移除剥离层使表层分离。
膨胀的环氧树脂泡沫状芯被注入到两个表层之间，代替***物，以形成夹层。
整个夹层在真空下接受几个小时的热处理(65-120℃)，以粘结表层和芯。
实例5
针织物是使用包含玻璃纤维和热塑性纤维的混合纱线制成的。
第一针织物铺覆在硅树脂囊袋上方，并且该组件被沉积在第一钢模具中以用于外表层固结。闭合模具并抽真空。将模具加压(3至10巴)并通过感应加热快速加热至200至250℃。温度保持几分钟。冷却后，移除囊袋并由此产生第一表层。
第二表层(内表层)在第二模具中的制造方法与第一表层相同。
在用于固结外表层的工具中，依次沉积以下材料：先前固结的外表层、环氧树脂或液态胶膜、蜂窝状结构、最终复合产品的先前固结的内表层。
将用于固结内表层的硅树脂囊袋放置到位并闭合模具。将真空抽到最大，并将组件加热到65-120℃维持数小时(烤箱加热法)，以粘结表层和芯。

Claims (13)

1.一种制造夹层形复合材料产品的方法，其中所述夹层形复合材料产品包括两个外层和一个芯，所述外层具有纤维增强聚合材料的基体，所述聚合材料的熔点低于构成所述纤维的材料的所述熔点；
其中所述方法的特征在于其使用由熔点高于所述聚合材料的所述熔点的材料组成的***物，所述外层固结在所述***物上；并且
其中所述***物随后被所述夹层的所述芯替换，然后组件经历固结处理以将所述外层粘结至所述芯。
2.根据权利要求1所述的方法，其特征在于包括以下步骤：
生产由纤维增强聚合材料组成的预制件，所述预制件旨在成为所述夹层的所述外层；
在模具中并置第一预制件、所述***物和第二预制件；
通过加热和加压以达到所述聚合材料的所述熔点的温度，在未达到所述增强材料或所述***物的材料的所述熔点的温度的情况下，固结所述预制件以获得所述外层；
移除所述***物、分离所述外层并***所述夹层的所述芯；
热处理以将所述外层粘合至所述芯；
冷却由此获得的所述产品。
3.根据权利要求2所述的方法，其特征在于，所述预制件使用预浸渍的聚合物树脂织物制成。
4.根据权利要求2所述的方法，其特征在于，通过针织包含所述增强材料和所述聚合材料的纱线来制成所述预制件。
5.根据权利要求2至4中任一项所述的方法，其特征在于，在旨在形成没有芯的区域的位置处增加所述预制件之间的剥离成本。
6.根据权利要求1或3或5所述的方法，其特征在于包括以下步骤：
在模具中并置增强材料制成的织物或针织物、所述***物、和增强材料制成的第二织物或针织物；
在压力和温度下注入聚合材料树脂；
移除所述***物并***所述夹层的所述芯；
固结固化以将所述外层粘附至所述夹层的所述芯；
冷却由此获得的所述产品。
7.根据权利要求1至6中任一项所述的方法，其特征在于，所述***物由硅树脂制成。
8.根据权利要求1至7中任一项所述的方法，其特征在于，所述增强材料选自玻璃纤维、碳纤维和芳纶纤维。
9.根据权利要求1至8中任一项所述的方法，其特征在于，所述聚合材料为热塑性类型，特别地选自聚碳酸酯(PC)、聚醚酰亚胺(PEI)、聚丙烯(PP)、聚(对苯二甲酸乙二酯)(PET)、聚醚醚酮(PEEK)。
10.根据权利要求1至8中任一项所述的方法，其特征在于，所述聚合材料为热固性类型，特别地选自环氧树脂、氰酸酯、酚醛树脂和聚酯。
11.根据权利要求1至10中任一项所述的方法，其特征在于，所述夹层的所述芯由多孔蜂窝状材料组成。
12.根据权利要求1至11中任一项所述的方法，其特征在于，所述芯的厚度为至少约2mm且不大于约50mm。
13.根据权利要求1至12中任一项所述的方法，其特征在于，所述外层中的每个的厚度为至少约0.2mm且不大于约5mm。
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