CN116157254A - 复合材料 - Google Patents

复合材料 Download PDF

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CN116157254A
CN116157254A CN202180060542.6A CN202180060542A CN116157254A CN 116157254 A CN116157254 A CN 116157254A CN 202180060542 A CN202180060542 A CN 202180060542A CN 116157254 A CN116157254 A CN 116157254A
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fibres
use according
graphite foil
composite material
fibers
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法比安·舒伯特
托马斯·科克
维尔纳·朗格尔
尤尔根·乔斯
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SGL Carbon SE
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Abstract

本发明涉及复合材料作为防火面板的用途。

Description

复合材料
技术领域
本发明涉及复合材料作为防火面板和/或散热面板的用途。
背景技术
在本发明的上下文中，防火面板和/或散热面板应理解为被成形为片状或弯曲片状并且可能具有承重功能的包层元件。
迄今为止，膨胀材料已用于防火应用。为此目的，通常使用石墨盐，即膨胀石墨，将被嵌入复合树脂中或并入矿物纤维针织物中。这描述于例如WO2018/094002A1中。
具体来说，对于相应的防火效果，矿物防火方案具有比较高的防火层材料厚度，而且也不是很柔韧。当用于承重组件或结构元件时，相对薄弱的防火层必须与承重材料连接。一方面，防火层与承重材料之间的连接点以及所得复合材料的总厚度都有问题。由此产生的有限的设计自由度导致例如防火门的厚度相当高，因此重量也相对较高。这进而导致门往往难以打开和关闭，从而需要更多的努力。此外，常用复合材料缺乏可塑的柔韧性。此外，在火灾的情况下，由于复合材料基质的化学分解，可能会释放出临界量的烟雾和/或有毒气体。此外，膨胀材料需要阈值温度，所述阈值温度则仅导致所用的防火层膨胀。
发明内容
因此，本发明的目标是提供一种复合材料和复合材料作为防火面板和/或散热面板的用途，由此克服现有技术的上述缺点。
所述目标通过使用包含纤维和石墨箔的复合材料作为防火面板和/或散热面板来实现。
为了生产石墨箔，首先必须生产具有蠕虫状结构的膨胀石墨。为此目的，将石墨如天然石墨通常与嵌入物如硝酸或硫酸混合，并在例如600℃至1200℃的高温下进行热处理。(DE10003927A1)
例如，与天然石墨相比，膨胀石墨在垂直于六角形碳层的平面内膨胀了80倍以上。由于膨胀，膨胀石墨具有优异可塑性和良好联锁性的特征。膨胀石墨可以借助于压力压成箔状。优选地，使用密度为1.3至1.8g/cm3的箔。具有此密度范围的箔在所述平面上的热导率为300W/(mK)至500W/(mK)。热导率通过埃斯特朗方法(
Figure BDA0004113778110000021
method)确定(“/>
Figure BDA0004113778110000022
Method of Measuring Thermal Conductivity”；Amy L.Lytle；Physics Department,TheCollege of Wooster,Theses)。
由于所用的材料系统，可以节约重量和厚度，同时保持与常规防火面板相同的承重能力。在发生火灾时，使用石墨箔不会像使用膨胀石墨时那样导致形状剧烈变化，在膨胀石墨的情况下是因为石墨盐发生膨胀导致形状剧烈变化。此外，所用的复合材料提供了可塑性的优点，因此所述复合材料可以呈现多种几何形状。与常规防火面板和/或散热面板相比，这允许更加多变的用途。此外，所述复合材料在z方向具有良好的隔热效果(热导率为5W/(mK)，即穿过石墨箔)，并且在石墨箔平面内(X和Y方向)具有非常好的热导率(300W/(mK)至500W/(mK))。
根据本发明，所述纤维和所述石墨箔各自被布置为彼此顶部的至少一个层。
所述复合材料通常具有两个外表面。
如果石墨箔层形成了一个外表面，则在使用时应该使其面向潜在的热源，因为这将允许石墨箔特别有效地散热并且不允许可能产生的任何气体和烟雾逸出。
在另一个有利实施方案中，所述纤维嵌入基质中。
根据本发明，所述基质由塑料材料制成。
在另一个有利实施方案中，所述塑料材料选自热塑性材料、弹性体或硬质体或其混合物，优选热固性材料或热塑性材料。
硬质体为例如环氧树脂；热塑性材料为例如聚酰胺；弹性体为例如丙烯腈丁二烯橡胶；或者热塑性材料为在一定的温度范围内可能变形的塑料材料，该过程是可逆的，只要所述热塑性材料没有因热过热而分解即可。
通过使用塑料材料作为基质，它充当粘合材料，其中塑料材料和石墨箔形成了形状配合连接。所述连接不需要粘合剂。这样做的优点是，基质的性质决定了连接强度，并且不会像使用粘合剂时那样削弱连接。当使用环氧树脂时，可以任选地加入阻燃剂。阻燃剂防止环氧树脂着火，减少烟雾产生，并促进自灭。例如，氢氧化铝、磷酸铵、氯化或溴化共聚物如十溴二苯醚(DecaBDE)、四溴双酚A(TBBPA)或六溴环十二烷(HBCD)可以用作阻燃剂。
根据本发明，所述纤维选自碳纤维、玻璃纤维、芳族聚酰胺纤维、金属纤维、陶瓷纤维、天然纤维和玄武岩纤维或其混合物，优选碳纤维。
天然纤维应理解为亚麻、黄麻、剑麻和大麻纤维。
根据本发明，纤维呈短纤维、长纤维、连续纤维、粗纱、织造织物、稀松布、非织造物或其混合物的形式。
粗纱应理解为包含一束或多束单独纤维细丝的纤维束。稀松布是一种多个粗纱在一起的纺织表面结构。织造织物是具有至少两个不平行并因此相交的股线体系的纺织纤维。非织造材料应理解为在表面具有各向同性纤维取向而无优选表面方向的结构。
根据一个有利的实施方案，所述石墨箔的厚度为0.15至2mm，优选0.5至1mm。
当厚度超过2mm时，石墨箔的柔韧性较差，即，石墨箔变脆。如果厚度小于0.15mm，则防火效果不再充分。
在另一个有利的实施方案中，所述石墨箔具有孔。
所述孔可以是任何形状。例如，它们可以是三角形、正方形、五边形、六边形、圆形或卵形。所述孔的长度与宽度之比不受限制。在优选的实施方案中，所述孔是圆形或卵形的。圆形的孔特别容易通过冲孔制造，这有利于特别有效地生产。穿孔工艺也可以用于产生所述孔。每一个单独孔的面积在0.1mm2至400mm2的范围内，优选在1mm2至100mm2的范围内。所述孔在石墨箔上的分布不受限制。
在根据本发明的复合材料中，所述孔中的至少一些至少部分地填充有树脂。这进一步稳定了所述复合材料，因为石墨箔中的孔允许一侧上的层与另一侧上的层粘合。
因此，增加了机械稳定性。同样，在由具有孔的石墨箔和在石墨箔一侧上的层组成的复合材料的情况下，稳定性因树脂穿透到石墨箔的孔中而增加。在本发明的上下文中，“所述孔中的至少一些”意指未必所有孔都填充有树脂。“至少部分地填充有树脂”意指对于小于1mm的箔厚度，至少50％的孔填充有树脂，而对于超过1mm的膜厚度，至少30％的孔填充有树脂就足够了。
根据本发明的复合材料是通过树脂浸渍工艺如湿压法生产的。所述复合材料的强化纤维，例如玻璃和/或碳纤维，优选玻璃纤维，是以从纺织品(优选织造织物、稀松布或非织造物)切割的层的形式干式提供。这些层与一层或多层石墨箔一起按所期望的纤维取向层叠。将未反应的液体合成树脂，优选环氧树脂，在所述层之间或仅在所述叠层顶部涂覆几次。合成树脂应理解为树脂和硬化剂的混合物。树脂还可以与上述阻燃添加剂混合。将用液体树脂润湿的纺织品层和石墨箔叠层插入在压制工具的模具半部分之间并将其封闭，通常在压力机的帮助下进行封闭。封闭压力一方面将所述层压成防火面板和/或散热面板所期望的形状，另一方面以液体合成树脂浸渍所述干纺织品层。由于石墨箔中的孔，它也可以被充分地浸渍并稳固地并入所述复合材料中。树脂然后反应形成固体基质材料，通常通过增加模具的温度进行加速。然后可以从模具中取出成品面板。
根据另一个有利的实施方案，所述石墨箔具有保护膜。所述保护膜保护石墨箔免受刮擦和磨损。此外，所述保护膜增强了可涂饰性。
有利地，所述保护膜选自塑料材料、树脂或陶瓷。
还可以向所述保护膜添加阻燃剂如氢氧化铝、磷酸铵、氯化或溴化共聚物如十溴二苯醚(DecaBDE)、四溴双酚A(TBBPA)或六溴环十二烷(HBCD)。
有利地，所述保护膜的厚度小于1mm，优选0.02-0.3mm。如果保护膜的厚度大于1mm，则它会影响石墨箔的热性质、机械性质以及重量比(weight-specific)性质。
有利地，对所述复合材料的边缘区域应用冷却，因此，在火灾的情况下，热量可以更快地逸散。可以使用所有类型的冷却，包括主动冷却和被动冷却二者。在本发明的上下文中，主动冷却应理解为借助冷却介质通过强制对流或传导进行主动散热。这可以例如通过复合材料的边缘区域含有冷却介质流经的管道或通过流过复合材料表面的气流来进行。被动冷却是通过自然传导或对流进行散热。例如，冷却可以采取金属框形式的散热片的形式，所述金属框可设有冷却翅片例如以增加表面积。
根据本发明，所述防火面板是防火门。所述复合材料的其它可能应用包括用作运输容器(例如冷藏运输用绝缘货运容器)的壁，作为冷藏运输车辆用箱体的壁，或者也用于电动车辆或飞机的电池外壳，这是材料的防火和绝缘性能都很重要的一种应用。
下面纯粹通过示例的方式，通过有利的实施方案并参考附图来描述本发明。
附图说明
图1a和图1b各自是具有石墨箔(2)或穿孔石墨箔(3)的复合材料(1)的透视图。
图1c和图1d各自是具有石墨箔(2)或穿孔石墨箔(3)的复合材料(1)的横截面。
图2a和图2b各自是具有石墨箔(2)或穿孔石墨箔(3)和保护膜(5)的复合材料(1)的透视图。
图2c和图2d各自是具有石墨箔(2)或穿孔石墨箔(3)和保护膜(5)的复合材料(1)的横截面。
图3a是复合材料(1)的透视图，其中穿孔石墨箔(3)位于两个纤维和基质层之间。
图3b是复合材料(1)的横截面，其中穿孔石墨箔(3)位于两个纤维和基质层之间。
图1a是复合材料(1)的透视图。石墨箔(2)应用于由纤维和基质构成的层(4)。由纤维和基质构成的层(4)与石墨箔(2)形成了形状配合连接。
图1b是复合材料(2)的透视图。穿孔石墨箔(3)应用于由纤维和基质构成的层(4)。由纤维和基质构成的层(4)与穿孔石墨箔(3)形成了形状配合连接。
图1c和图1d各自是具有石墨箔(2)或穿孔石墨箔(3)的复合材料(1)的横截面。
图2a是复合材料(1)的透视图。石墨箔(2)应用于由纤维和基质构成的层(4)，保护膜(5)应用于所述石墨箔。由纤维和基质构成的层(4)与石墨箔(2)形成了形状配合连接。
图2b是复合材料(1)的透视图。穿孔石墨箔(3)应用于由纤维和基质构成的层(4)，保护膜(5)应用于所述石墨箔。由纤维和基质构成的层(4)与石墨箔(2)形成了形状配合连接。
图2c和图2d各自是具有石墨箔(2)或穿孔石墨箔(3)和保护膜(5)的复合材料(1)的横截面。
图3是复合材料(1)的透视图，其中穿孔石墨箔(3)位于两个纤维和基质层(4)之间。
图3b是复合材料(1)的横截面，其中穿孔石墨箔(3)位于两个纤维和基质层之间。
具体实施方式
下面使用实施方案说明本发明，然而，所述实施方案不代表对本发明的任何限制。
医疗技术组件的生产可以如下所述来进行。
实施方案1：
在一个实施方案中，制造2.5mm厚的复合材料以用作阻燃面板。为此目的，八层具有单取向碳纤维且纤维表面重量为250g/m2的环氧树脂预浸料在0°、45°、90°、-45°、-45°、90°、45°和0°方向上准各向同性地层叠在彼此顶部，其中“准各向同性”意指由纤维和基质构成的层(4)在平面内的所有方向上产生了大致相同的机械性能。还添加0.5mm厚的石墨箔(2)作为顶层。所述石墨箔不需要单独的粘合剂来粘合，而是由于固化过程中由纤维和基质构成的层(4)的树脂表面与石墨箔(2)之间形成的材料连接而粘合。对于此固化过程，平放的片材在130℃的温度下，在5巴的压力下硬化2小时。此过程将碳纤维半成品转变为稳定的碳纤维强化塑料材料(CFRP)(由纤维和基质构成的层(4))，并将此层与石墨箔(2)组合形成形状配合的复合材料(1)。在本申请中，石墨箔侧面向潜在的火源或热源，以由于xy平面内的热分布和石墨箔(2)的不透气性实现最佳可能防火效果。
实施方案2：
在另一个实施方案2中，程序与实施方案1的类似，但使用了穿孔石墨箔(3)。这种0.5mm厚的石墨箔(3)是由穿孔工艺提供的，其中孔以相等间隔均匀分布在整个箔上。孔图案中孔直径为1.3mm，孔间距为5.3mm。这导致开放孔表面占5.5％。由于树脂系统的可流动性和施加的压力，树脂能够流经这些孔，并因此形成与比较薄弱的穿孔石墨箔(3)的机械稳定性树脂桥。因此增加了石墨箔平面内的内部强度。
实施方案3：
在另一个实施方案中，使用与实施方案2完全相同的结构，但另外向穿孔石墨箔(3)施加0.1mm厚的树脂膜作为保护膜(5)。固化过程与实施方案2相同；额外的树脂膜确保了在石墨箔上形成均匀的保护膜，从而保护石墨箔的柔软表面不受机械磨损或刮擦影响。
实施方案4：
在另一个实施方案4中，不使用环氧树脂预浸料，而是使用用聚酰胺6基质进行了碳纤维强化的热塑性胶带作为由纤维和基质构成的层(4)的前体。这些胶带还具有纤维表面重量为250g/m2的单向纤维强化。CFRP层结构以与之前的实施方案相同的方式放置，并在它上面放置厚度为0.5mm的石墨箔(2)。在后续处理步骤中，在260℃和10巴压力下将层固结20分钟。所产生的层压材料在另一个处理步骤中成型。为此目的，借助于红外辐照器将层压材料加热到玻璃化转变温度以上，使得热塑性基质再次成为可塑的。借助于机器人手臂，将柔软的结构转移到所期望的压模中，并经由模具配对件实现所期望的几何形状。在30巴压力下，将层压材料再次冷却，在层压材料温度为80℃时可以取出。
实施方案5
在另一个实施方案中，将石墨箔夹在两层由碳纤维构成的双轴稀松布之间，每一层稀松布的基重为290g/m2，其中纤维取向为+/-45°。石墨箔的热导率为350W/(mK)，厚度为0.6mm，因此提供了足以用作散热用散热面板的高热导能力。石墨箔设有间隔1.5cm的孔，孔直径为2mm。将由树脂和硬化剂(树脂/硬化剂比为100:21质量份)混合以备在60℃的温度下反应的环氧树脂施加到两层稀松布中的每一层上。将石墨箔插入两层经树脂涂覆的稀松布之间，将整个叠层压入加热到120℃的模具中持续3分钟，使树脂浸渍纺织品，然后固化。通过箔中的孔的树脂提供了两层纤维之间的连接，并确保石墨箔牢固地并入复合材料片中。在完成压制过程后，可以从模具中取出所制造的防火面板。
附图标记列表
(1)复合材料
(2)石墨箔
(3)穿孔石墨箔
(4)纤维和基质层
(5)保护膜

Claims (15)

1.一种包含纤维和石墨箔的复合材料作为防火面板和/或散热面板的用途。
2.根据权利要求1所述的用途，其中所述纤维和所述石墨箔各自被布置为彼此顶部的至少一个层。
3.根据权利要求1或2所述的用途，其中所述纤维嵌入基质中。
4.根据权利要求3所述的用途，其中所述基质由塑料材料制成。
5.根据权利要求4所述的用途，其中所述塑料材料选自热塑性材料、弹性体、硬质体或其混合物。
6.根据权利要求1或2所述的用途，其中所述纤维选自碳纤维、玻璃纤维、芳族聚酰胺纤维、金属纤维、陶瓷纤维、天然纤维和玄武岩纤维或其混合物。
7.根据权利要求1或2所述的用途，其中所述纤维以短纤维、长纤维、连续纤维、粗纱、织造织物、稀松布、非织造织物或其混合物的形式存在。
8.根据权利要求1或2所述的用途，其中所述石墨箔具有0.15mm至2mm的厚度。
9.根据权利要求1或2所述的用途，其中所述石墨箔具有孔。
10.根据权利要求9所述的用途，其中所述孔中的至少一些至少部分地填充有树脂。
11.根据权利要求1或2所述的用途，其中所述石墨箔具有保护膜。
12.根据权利要求11所述的用途，其中所述保护膜选自塑料材料、树脂或陶瓷。
13.根据权利要求11或12所述的用途，其中所述保护膜具有小于1mm的厚度。
14.根据权利要求1或2所述的用途，其中将主动或被动冷却施加至所述复合材料的边缘区域。
15.根据权利要求1或2所述的用途，其中所述防火面板为防火门、绝缘运输容器壁或电池外壳。
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