CN1929990A - 复合材料中的或涉及复合材料的改善 - Google Patents
复合材料中的或涉及复合材料的改善 Download PDFInfo
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- CN1929990A CN1929990A CNA2005800078611A CN200580007861A CN1929990A CN 1929990 A CN1929990 A CN 1929990A CN A2005800078611 A CNA2005800078611 A CN A2005800078611A CN 200580007861 A CN200580007861 A CN 200580007861A CN 1929990 A CN1929990 A CN 1929990A
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- composite
- layer
- epoxy
- epoxy material
- foams
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Abstract
具有高弯曲强度的轻质复合材料包括夹在两层表面材料之间的环氧泡沫体,该复合材料具有高强度和低重量,并可用来代替钢结构。所述表面层可以是纤维材料,特别是玻璃纤维或碳纤维,所述表面材料优选嵌入环氧基体。或者,它们可以是匹配盒结构或同心金属管。所述夹心结构可以通过如下方法制备:敷设纤维,用环氧树脂涂布和/或浸渍该层,敷设一层可热活化的可发泡环氧材料,在该可发泡材料上提供另一层任选用环氧树脂涂布和/或浸渍的纤维材料,并加热以使环氧材料发泡和固化。或者,它们可以通过在表面层之间挤出可发泡材料而形成。
Description
本发明涉及改善的层状复合结构和它们的生产方法。特别地,本发明涉及高强度的轻质、刚性复合材料和它们的生产。本发明进一步涉及从这样的复合材料生产高强度的轻质制品。钢通常用于需要高强度的结构中。然而,钢往往是重的,并因此给制品增加了额外的重量。虽然有一些强度高于钢的轻质材料,但它们极为昂贵。
我们已发现,本发明的轻质、刚性复合材料特别适合用作运输工业中的材料,例如在汽车、飞机和船运工业中,在这些工业中,它们可以被用来代替金属和玻璃增强的塑料制品,例如板材和加强件。近年来,存在用相当强度的更轻的材料,例如铝、纤维增强的聚合物材料、泡沫材料和复合材料(特别是含有发泡层的复合材料)代替传统钢构件的倾向。但是,仍需要具有增大的强度和减轻的重量的材料。
本发明的复合材料在其中要求高强度与轻重量相结合的另外的应用中具有广泛的用途,特别地,它能提供具有与钢材相比相当的或改善的强度的廉价轻质材料。所述复合材料特别可用在使用钢材的应用中,例如金属管,建筑中使用的金属结构和所有运输形式。另外,所述结构可以被用来改善其中使用较轻的材料例如铝的制品的强度。其它用途包括作为体育用品例如雪橇和溜冰鞋的生产以及家具的生产中的原料。
材料的所要求的强度将取决于其目标用途。例如,重要的特性可能是通过ASTM D790/ISO 178标准测量的高拉伸强度和高弯曲模量,或者它可能是耐冲击性、抗压强度或抗扭强度,而且在某些用途中,可能需要这些性能的组合。
我们已发现,从由包封一层刚性环氧泡沫体的至少两个表面层构成的夹心结构复合材料可以得到特别需要的性能,特别是低重量和高强度和劲度的组合。
具有泡沫体芯的复合夹心结构是已知的,并且已被提议作为具有很大强度和劲度以及从重量方面考虑的优点的材料。例如,日本专利公布JP 58049223 A2的摘要公开了包括夹在两个金属板之间的环氧泡沫体的夹心结构。S.Venkatraman和Kishore的两篇文章,Journal ofReinforced Plastics and Composites Vol 16 No.7/1997中的第一篇和Journal of Reinforced Plastics and Composites Vol 17No.8/1998中的第二篇公开了包含夹在两个玻璃-环氧树脂材料厚层之间的柔性泡沫体薄层的复合材料。这些文章中的第一篇涉及对玻璃/环氧层压材料的冲击研究,而第二篇涉及对泡沫体层在经历重复冲击的玻璃-环氧复合材料的破坏中的作用的研究。在两篇文章中,柔性环氧泡沫体层以预先发泡的柔性层的形式被提供,并且被通过粘合剂粘附在玻璃/环氧层上。后一篇文章得出结论,柔性泡沫体的片层相对于冲击方向的安排方式影响重复冲击时裂纹的扩散。
美国专利3598671公开了制备泡沫塑料层压结构的方法,其中将泡沫体形成材料的至少一种组分作为涂料涂覆在基础材料的一个片的表面上。将泡沫体形成材料的另一组分作为涂料涂覆在基础材料的第二个片的表面上。然后将所述的片放在一起,以使所述泡沫体形成材料的组分接触,使得它们发泡和生产出芯发泡的塑料层压结构。US3598671的实施例2生产了这样一种层压材料,其包含夹在两个各自约1/8英寸厚的玻璃纤维层之间的1/4英寸厚的环氧泡沫体层。因此,两层玻璃纤维的总厚度基本上与泡沫体的厚度相同。所述泡沫体还特别重,具有7.5磅/平方英尺的密度。所以,美国专利3598671没有设想本发明的高强度的轻质材料。
可热活化的可发泡环氧材料是已知的,并且被用于汽车的结构性加强件的生产中。例如,该可发泡材料可以被涂布到金属或塑料载体的表面以生产一种部件,该部件被插入到需要增强的车辆结构的部分中。可以复配所述可热活化的可发泡环氧材料,使得它将在用于给车辆结构的金属表面提供防腐涂层的电涂(e-coat)方法或任何其它涂漆操作中普遍存在的条件下发泡。这样的可发泡环氧材料及其应用被描述于美国专利4922596、4978562、5124186和5884960中。我们现已发现,改善的轻质高强度复合材料可以从这种类型的可发泡环氧材料获得。美国专利申请09/939152公开了结构增强的板材,它包含金属板和纺织粗纱并粘接在基材一侧,所述基材可以是环氧泡沫体。
所以,本发明提供了一种包括夹心结构的复合材料,所述夹心结构包括附着在刚性环氧泡沫体中间层上的至少两个表面层,其中所述环氧泡沫体层是所述两个表面层的总厚度的至少1.5倍,而且所述泡沫体具有0.2~1.5g/cc、优选0.4~1.5g/cc的密度。特别地,我们优选所述泡沫体具有0.3~0.6g/cc的密度。
在又一个实施方案中,本发明提供了一种复合材料,它包括至少两个厚度各为0.2~10毫米的表面层和厚度为2~200毫米的刚性环氧泡沫体芯层。
在本发明的又一个实施方案中,本发明的复合材料具有0.1~2.0g/cc、优选0.1~1.0g/cc的密度,该密度取决于用作所述表面层的材料的性质。在又一个实施方案中,通过ASTM D790/ISO 178标准测定,5~8毫米厚的本发明的复合材料具有100mPa~700mPa、优选200mPa、更优选200mPa~700mPa的弯曲模量。
本发明复合材料的优选的表面层可以是任何合适的材料。合适的材料的实例包括:金属,包括金属箔如铝箔或钢箔;塑料膜或片,例如聚丙烯或聚乙烯膜或聚对苯二甲酸乙二醇酯膜。但是,优选所述材料是纤维性材料。特别优选所述表面层是多孔性的以至于所述环氧材料能渗透进表面层中的孔中,使得所述表面层变成嵌入环氧泡沫体中。本发明特别适用于生产中空截面的轻质复合材料,例如管或盒结构,并且在这里,所述表面例如可以是塑料或金属(优选铝)的同心管或匹配盒部分。所述表面层可以相同或不同,并且在一些实施方案中,可以选择所述层以提供所需的性能,例如在中空截面的复合材料如管中,外层可以是金属例如铝,以提供耐冲击性,并且内层可以是一种管状物例如碳纤维,以提供强度。
在使用纤维材料的情况下,它可以是任何合适材料的,而且它的选择将取决于所述复合材料的目标用途。可以使用的纤维材料的实例包括纺织的或无纺的织物,例如得自聚酯、聚酰胺、聚烯烃、纸、碳和芳纶纤维的织物。这些织物可以被纺织,或者通过无纺织物生产技术例如针穿孔或点粘接来得到。还可以使用金属纤维网,尽管我们优选使用玻璃纤维,它也可以是纺织的或无纺的。特别地,我们优选使用重量为40克/平方米~400克/平方米的玻璃纤维织物。其它优选的纤维材料包括碳纤维和芳纶。所述表面层本身可以通过将两层或更多层可以相同或不同的材料层叠来生产。
术语“嵌入”被用来描述一种复合材料,其中表面层虽然在复合材料的表面,但大致上由环氧材料包裹。这可以从材料的截面的电子显微照片例如图4来确定,图4显示了延伸入表面层而且有时穿过表面层的环氧材料的基本上连续的层。应该明白,为了嵌入,不必要全部表面材料被环氧材料包住。延伸入表面层而且有时穿过表面层的环氧材料可以与所述环氧泡沫体相同,尽管在本发明的一个优选实施方案中,它是与所述可发泡环氧材料相容的、单独的不发泡的环氧材料,并且与所述可发泡材料形成基本上连续的基体,考虑到由于环氧材料的发泡而形成的空隙。所以,所述表面层材料嵌入该环氧基体。
所述泡沫体层是刚性的环氧泡沫体。“刚性”是指它触摸起来是硬的,并且抗手工施加的压力。优选所述泡沫体层具有5~15毫米、优选7~13毫米、最优选8~13毫米的厚度。在本发明的复合材料的生产中,优选由其生产所述泡沫体的所述可发泡材料在未发泡状态时具有1~5毫米、优选2~4毫米、更优选2~3.5毫米的厚度。
本发明还提供了生产复合材料的方法,该方法包括:提供第一层;将可热活化的可发泡环氧材料层敷设在其上;并在可热活化的可发泡环氧材料层的背离所述第一层的表面上提供第二表面层;和加热以活化所述环氧材料,导致其发泡和固化,并由此形成粘在表面层上的刚性的发泡的环氧材料。
在又一个实施方案中,本发明提供了另一种生产复合材料的方法,它包括在两个表面层之间喷雾可发泡环氧材料,并且允许所述可发泡材料膨胀和固化并粘在所述表面层上。
在本发明方法的一个优选实施方案中,所述表面层是多孔性的,优选是纤维材料。在又一个优选的实施方案中,在加热前用一种环氧材料涂布和/或浸渍所述表面层。优选地,当使用这样一种环氧材料时,它与所述可热活化的可发泡环氧材料相容,从而与其形成基本上连续的基体,如上文所述。这样,当表面层是多孔性的时,它们可变成嵌入在所述环氧材料中。优选地,该环氧材料也在与所述可热活化的可发泡环氧材料固化的相同条件下固化。在该实施方案中,本发明方法的加热步骤将固化两种环氧树脂。方便地,用于涂布和/或浸渍所述多孔性层的环氧材料与用作可热活化的可发泡材料的基料的环氧材料是相同的环氧材料,尽管它不必是可发泡的。
在另一个优选的实施方案中,所述层是匹配的中空轮廓,而且在所述轮廓之间产生泡沫体。例如,所述层可以是同心管或匹配盒部分。在该实施方案中,可以通过在所述两个匹配的轮廓之间提供可发泡材料来产生所述结构,所述两个匹配的轮廓优选保持分离以允许形成所需厚度的泡沫体层。例如,可以在两根移动的、间隔开的同心管之间挤出所述可发泡材料,随后使所述可发泡材料发泡,以生产本发明的复合材料。
本发明的各实施方案另外设想了包含四层或更多层的夹心复合材料,它们的生产和从它们制成的材料。例如,除了三层夹心结构之外,复合材料可以包含由两个外层,例如纤维、金属或塑料层,和一个纤维、金属或塑料材料的内层,以及插在所述层间的两层环氧泡沫体或可热活化的环氧泡沫体形成材料组成的5层。含有更多层的复合材料也被设想,但是前提是所述复合材料的两个表面层是按照本发明的。
可发泡环氧材料通常含有环氧树脂、发泡剂和固化剂,并且经常还含有填料。可以选择发泡剂和固化剂,使得发泡和固化(硬化)在所需的温度范围内发生。因此应当选择所述材料,使得发泡和固化所需的温度不损坏表面层。可以根据产品中所要求的劲度来选择环氧树脂。经常使用胺固化剂,在这种情况下,一般要求至少100℃的固化温度。优选的是,选择发泡剂和固化剂,使得发泡在稍微低于固化温度的温度下开始。所述可发泡环氧树脂可以以液体形式施用,通常通过利用溶剂例如醇。在该实施方案中,可以将环氧树脂喷到或涂到表面层的一面或两面。然后可以通过蒸发除去溶剂,以提供可发泡环氧材料的连续或不连续的层。或者,所述可发泡环氧材料可以被挤出和切割成片以用于本发明,或者被挤出在表面层之一上,方便地被挤出在两个表面层之间。
可热活化的环氧泡沫体形成材料应当根据所述复合材料的目标应用来选择。然而,所述可热活化的环氧基树脂应当在通过使用热来活化时具有可发泡的特性,由此它膨胀、交联而产生硬的、刚性的泡沫体,并且固化以粘附在表面层上。优选的复配物的一个实例是可以包括聚合物改性剂如乙烯共聚物或三元共聚物的环氧基材料,它们可从L&L Products,Inc of Romeo,Michigan以名称L-5204、L-5206、L-5207、L-5208、L-5209、L-5214和L-5222商购,以及从Core Products以Core 5207、5214、5234和5231的名称商购。这些产品还可以包括填料,例如玻璃微球、碳酸钙和滑石,它们可减小泡沫体的密度。这些优选的可热活化的可发泡材料的一个优点是,它们可以被以数种方法加工以产生本发明的可热活化的可发泡层。所述可发泡的可活化环氧材料层可以是连续或不连续的。提供可发泡的可活化材料层的可能技术包括:提供片状材料、注射成型、吹塑、热成形、堆放的(palletized)材料的直接沉积、挤出或用微型涂布挤出机的挤出。优选的环氧材料在活化前是柔性的,并且这种柔性使得可以产生这样的设计,其允许生产复杂的形状而且超过大多数现有技术的高强度材料的设计灵活性。
无论所述可热活化的可发泡环氧树脂呈条或点的形式,它都是可热膨胀的。即,在施加热时,它们将膨胀,一般通过发泡反应,并且优选膨胀到未膨胀状态的体积的至少130%,更优选膨胀到未膨胀状态的体积的至少150%,但更优选膨胀到未膨胀状态的体积的至少两倍。所述材料还固化,以提供粘接在表面层上的刚性环氧泡沫体。所述可发泡材料优选在室温下触摸时是不粘的,而且它是这样的,即它将由于发泡剂的激活而软化并然后膨胀,环氧树脂然后将开始固化和显出粘合性能,以至于它将粘合在所述表面层上,并且最后固化将被完成以使发泡的环氧树脂硬化。得到的产品是夹心结构,包括粘附在硬的、刚性环氧泡沫体上的表面层。
环氧树脂优选占所述可活化的可发泡环氧材料组合物的约5%~约75%重量,更优选占约15%~约65%重量。填料优选占所述组合物的约0%~约70%重量,更优选占约20%~约50%重量。发泡剂优选占所述组合物的约0.5%~约10%重量,更优选占约0.2%~约5%重量。固化剂优选占所述组合物的约0%~约10%重量,更优选占约0.5%~约5%重量。促进剂优选占所述组合物的约0%~约10%重量,更优选占约0.3%~约5%重量。优选的配方示于下表。
成分 | 重量% |
环氧树脂乙烯共聚物发泡剂固化剂促进剂填料 | 15%~65%0%~20%0.2%~5%0.5%~5%0.3%~5%20%~50% |
在本发明方法的所述优选实施方案中,在加热以使所述可热活化的环氧材料发泡和固化之前,用环氧材料涂布和/或浸渍一个或多个表面层。在该实施方案中,优选的是,用于涂布和/或浸渍所述表面层的环氧材料在与所述可热活化的可发泡材料固化的相同条件下固化。在一个特别优选的实施方案中,所述环氧材料与所述可热活化的可发泡材料所基于的环氧材料相同。当表面层是多孔性的以至于它们可以用环氧材料浸渍时,该实施方案是特别优选的。或者,所述浸渍可以通过涂布呈液体形式的所述可发泡环氧材料来完成。
优选用于所述可发泡材料的环氧树脂具有约200~5000、更优选300~3000的环氧当量值,因为这些树脂具有合适的固化活性和熔点。因此,可以制备具有令人满意的刚性的泡沫体。更优选地,环氧树脂含有约500~2500的环氧当量,最优选含有约500~1500的环氧当量。
具有合适的环氧当量的环氧树脂不限于一种类型的环氧树脂,而是可以使用环氧树脂的组合。代表性的环氧树脂包括但不限于双酚A、双酚F、溴化双酚A、氢化双酚A、双酚S、双酚AF、联苯、萘、氟、线型酚醛树脂、邻甲酚(ortho-cresone)线型酚醛树脂、DPP线型酚醛树脂、三官能的、三羟基苯基甲烷、四苯酚乙烷和其它缩水甘油醚型是优选的。
固化剂是能固化环氧树脂的材料。优选地,固化剂能与呈未膨胀形式的环氧树脂在室温或通常的贮存温度下共存而不与环氧树脂反应,同时保持它的固化反应性。固化剂优选在高于环氧树脂的熔点的温度下固化环氧树脂,所以当调合和/或挤出所述可发泡环氧树脂复配物时,固化剂的固化反应性不应当减小。
优选地,固化剂在可发泡材料的生产和贮存过程中保持足够的反应性,以便在需要时固化环氧树脂。所以,虽然在泡沫母体材料的生产和贮存过程中可以发生环氧树脂的有限程度的固化,但这样的固化不应当实质性地影响固化剂的固化反应性。因此,当在室温或通常的贮存温度下贮存时,固化剂还优选具有与环氧树脂的低反应性,以便允许可发泡材料长期贮存。优选地,使用在约100℃~200℃的温度范围内开始固化的固化剂。更优选地,固化温度是约130℃~180℃。
优选的固化剂包括加聚型、催化型和缩合型固化剂。加聚型固化剂包括但不限于基于多元胺的双氰胺和基于酸酐的甲基降冰片烯二酸酐。催化型固化剂包括但不限于基于咪唑的2-甲基咪唑、2-乙基-4-甲基咪唑和2-十七烷基咪唑,基于路易斯酸的一乙胺三氟化硼、哌嗪三氟化硼和其它相关的化合物。
用于泡沫母体材料中的固化剂的量将不同,取决于环氧树脂的环氧当量,并且将足以提供刚性的泡沫体结构。通常,使用将有效地固化环氧树脂的固化剂量。优选的量是1~25重量份,更优选1~10重量份,相对于100重量份环氧树脂。
发泡剂在高于使用的环氧树脂的熔点的温度下分解和膨胀,而在可发泡材料的调合和生产过程中,例如在调合和/或挤出过程中不分解。
选择在取决于使用的固化剂的预定加热温度范围内分解并因此使环氧树脂膨胀的发泡剂。固化剂能固化环氧树脂的温度范围应当优选与发泡剂分解和膨胀的温度范围重叠。具体地说,发泡(分解)温度优选是约100℃或更高,更优选是120℃或更高。
优选地,使用有机分解类型的发泡剂。例如,可以使用偶氮二酰胺、偶氮二甲酰胺、偶氮二异丁腈、偶氮二羧酸钡、N,N1-二亚硝基五亚甲基四胺、N,N1-二亚硝基-N,N1-二甲基对苯二甲酰胺、对甲苯磺酰肼、苯磺酰肼、4,41-氧苯磺酰阱和其它相关的化合物。可使用这些发泡剂的任何一种或者两种或更多种的组合。偶氮二酰胺是特别优选的。
发泡剂优选以提供约30%~100%、优选50%~400%、更优选约100%~300%的发泡率的量添加。也就是说,使用的发泡剂的量将产生具有泡沫母体材料体积的1.3~10倍、优选1.5~5倍、更优选约2~4倍的体积的泡沫体材料。虽然具体的量将取决于所选择的特定环氧树脂,但发泡剂可以以约0.5~15重量份/100重量份环氧树脂、更优选0.5~10重量份/100重量份环氧树脂添加。
可以将各种其它添加剂加到所述可发泡组合物中,例如其它树脂组分,包括例如热固性树脂和/或热塑性树脂,无机添加剂,包括例如碳酸钙、滑石或云母,反应性稀释组合物,固化促进剂,发泡助剂,阻燃剂,着色剂,和增强材料(呈粉末形式、碎片形式、纤维形式、珠形式等),包括例如玻璃、金属、陶瓷或类似的材料。
可以添加除环氧树脂之外的热固性树脂,包括例如聚酯树脂、三聚氰胺树脂、脲树脂和酚树脂。如果使用这样的热固性树脂,可以根据固化剂适当地确定热固性树脂的量。如果添加热塑性树脂,得到的泡沫体通常比仅使用热固性树脂时具有更大的弹性。所以,通过改变泡沫母体材料中包括的热塑性树脂和热固性树脂的量,可以生产具有不同质量的泡沫材料。例如,添加这样的添加剂可以增大泡沫材料的韧性。
如果添加热塑性树脂作为添加剂,该树脂组分优选是聚乙烯、聚醋酸乙烯酯或者乙烯和丙烯酸烷基酯的共聚物。乙烯和丙烯酸烷基酯的共聚物可以包括乙烯-丙烯酸甲酯聚合物、乙烯-丙烯酸乙酯聚合物、乙烯-丙烯酸丁酯聚合物等,而且优选的共聚物是乙烯和烷基中具有约1~4个碳原子的丙烯酸烷基酯的共聚物。热塑性树脂可以是一种化合物或物质的组合物,或者两种或多种化合物或者物质的组合物的组合。
如果添加热塑性树脂,还可以添加可聚合的单体。合适的可聚合的单体包括氰脲酸三烯丙酯、异氰脲酸三烯丙酯、三羟甲基丙烷三甲基丙烯酸酯和类似的化合物。
通过添加增强材料(呈粉末形式、碎片形式、纤维形式、珠形式等)例如玻璃、金属或陶瓷,可以增大所得的泡沫材料的刚性。具体地说,如果添加纤维形成的材料,可以增大得到的泡沫材料的弹性。添加的这类增强材料的量优选是1~300重量份/100重量份树脂组分,更优选是1~100重量份/100重量份树脂组分。
在本发明的其中所述表面层是纤维层的实施方案中,所述纤维层优选如前所述是碳纤维或玻璃纤维层,并且用环氧材料涂布和/或浸渍过,所述环氧材料包含的环氧树脂优选占组合物的约5%~约75%重量,更优选约15%~65%重量。填料优选占组合物的约0%~约70%重量,更优选约20%~约50%重量。固化剂优选占组合物的约0%~约10%重量,更优选约0.5%~约5%重量。促进剂优选占组合物的约0%~约10%重量,更优选约0.3%~约5%重量。优选的涂层配方示于下表。
成分 | %重量 |
环氧树脂乙烯共聚物固化剂促进剂填料 | 15%~65%0%~20%0.5%~5%0.3%~5%20%~50% |
本发明的组合物可以呈任何要求的形状,并且可方便地在设计用来提供所要求的形状的模具中形成。在某些实施方案中,所述表面层和所述可热活化的可发泡材料(在发泡之前)通常是柔性材料。因此,所述复合材料可以通过如下方法生产:在模具中敷设第一表面层,任选用环氧材料涂布和/或浸渍所述第一层,然后在第一表面层上提供一层可热活化的可发泡环氧材料,在所述可热活化的材料层上提供第二表面层。该第二表面层可任选用环氧材料预涂布和/或浸渍,或者任选地,在它被提供到所述可热活化的材料层上之后用环氧材料涂布和/或浸渍。然后可以关闭模具,并将其加热到导致可热活化的可发泡环氧材料发泡和固化和导致用来涂布和/或浸渍所述表面层的任何环氧材料固化所要求的温度。在生产具有三个以上层的复合材料的情况下,可以在关闭模具和加热以引起发泡和固化以前提供另外的层。所述另外的层可以是任何合适的材料,例如连续的片或纤维层。
或者,所述表面层可以是刚性的,例如匹配盒结构或同心管,而且在该实施方案中,可以在所述匹配的结构或管子之间提供所述可发泡环氧材料,所述匹配的结构或管子通过合适的手段保持分离以允许所述可发泡材料进行希望的膨胀。在一个优选的实施方案中,所述盒结构或管子是金属的。
被用于使环氧材料发泡和固化的加热步骤的温度将取决于发泡剂和固化剂的选择,然而,我们已发现,在100℃~240℃范围内的温度是特别适用的,尽管在更低温度下混合组分时发泡的环氧树脂体系是已知的。或者,可以使用在较低温度下发泡的体系,例如其中提供两种或更多种组分并且在室温下混合的那些。本发明方法的一个益处是,在模制过程中可以不需要外压来实现希望的表面整理,因为所述可热活化的可发泡环氧树脂的发泡本身能够产生足够的内压。
在模制操作之后,可以开启模具,并且获得所需的复合材料。如果必要的话,可以给模具的表面提供脱模内衬材料,以保证复合材料不粘附到模具上。
我们已发现,本发明的复合材料具有高的弯曲强度和低的重量。通常,厚度为5毫米~8毫米的复合材料在0.1~1.0g/cc的密度下具有100mPa~700mPa、通常300mPa~700mPa的弯曲强度,该强度有利地与每单位面积相似重量的现有轻质铝基材料相当,而所述轻质铝基材料的弯曲模量是每单位面积相当重量的本发明产品复合材料的弯曲模量的约10%。我们还发现,本发明的复合材料比目前的钢盒结构或管形结构能保明显更大的最大负荷;该复合材料也是轻质的,特别是如果它们是铝基材料时。所以,它们提供了重量大为减轻的牢固体系。
此外,我们还发现,本发明的复合材料具有比相当的钢和铝基材料大得多的负荷下弹性范围。由标准三点弯曲试验中增大的负荷下弹性区的延伸证实了改善的弹性。
本发明的复合材料可广泛用于要求高强度和轻重量的应用中。例如,它们可被用于建筑工业,运输工业,包括汽车、飞机、航天和船运工业。所述复合材料可被用于其中盒部分或管被用来提供强度和/或增强的应用中。例如,它们可用于飞机,特别是轻质无人驾驶侦察飞机,在这里它们可提供轻质管形结构,而且还可以提供用于支承设备的结实的轻质板。其它应用包括汽车中的增强,例如抗汽车前方和侧面撞击的门增强,在此处,所述复合材料可被用在目前使用钢结构的应用中以在减轻的重量下提供增大的强度。显然,在其中要求强度和轻质的组合的很多应用中可以实现相似的益处。此外,它们可以被用于生产体育用品,例如雪橇、滚轴溜冰鞋、滚轴冰刀等。
所述复合材料还可以用作建筑物、车辆、体育用品和家具中的构件。
如果所述复合材料在完成的制品内将与其它构件连接,则在复合材料内可以提供连接件以使得能够进行装配。在本发明的该实施方案中,可以在加热以进行发泡和固化前在所述可活化的可发泡材料内设置连接件。这样,可发泡材料能够在连接件周围膨胀,以随着环氧材料的固化而将它牢固地保持在本来的位置。典型的连接件包括夹子、双头螺栓、螺钉等,它们可以是任何材料的,只要它们在用于活化和发泡的条件下能保持它们的强度即可。
通过附图1~5图解本发明,其中:
图1显示了本发明的一个片状复合材料。
图2显示了本发明的一个管。
图3显示了一个实施方案,其中一个金属插入物已经在发泡前被放在可发泡材料中。
图4是根据如下实施例生产的复合材料的一个外表面的横截面的显微照片。
图5是比较本发明材料的性能和现有高强度铝合金的性能的图。
参考如下实施例进一步阐述本发明。
实施例1
将可得自Core Products的、名为CORE-5234的挤出的可发泡环氧材料置于两层重量为245g/m2的纺织碳纤维垫之间,所述垫已用与用于所述可发泡材料的环氧树脂相同的环氧树脂浸渍。然后将所述三层结构置于模具中,并在175℃和常压下固化45分钟,以形成5.4毫米厚的复合材料。
实施例2
重复实施例1的方法,不同的是,不用单独的环氧树脂而是用采用甲醇溶剂改性成液体的可发泡材料本身来浸渍纤维粗纱。
差异在于,这种复合材料夹心结构(嵌入的纤维粗纱+可发泡材料+嵌入的纤维)现在触摸起来是干的并且容易处理。
图5比较了实施例1中生产的复合材料的样品和厚度为1.25mm、具有相似单位面积重量的传统高强度铝的样品的弯曲模量,所述弯曲模量根据ASTM D790/ISO 178测定。本发明的复合材料具有0.5g/cc的密度,而所述铝层的密度是2.7g/cc。本发明复合材料的重量是6.955克/平方米,而所述铝样品的重量是7.13克/平方米。图5显示,本发明的复合材料具有360mPa的弯曲模量,而铝样品的模量是31.5mPa。图5还显示,通过本发明的复合材料能维持的最大负荷是590牛顿,而铝样品能维持的最大负荷是100牛顿。
通过显示了三根管的附图6进一步阐释本发明。
a)外径为35毫米、钢材厚度为1.5毫米、每米重量为1133克和密度为7.2g/cc的钢管。
b)外径为35毫米、铝材厚度为1.5毫米、每米重量为425克和密度为2.7g/cc的铝管。
c)每米重量为837克和密度为1.6g/cc的本发明的复合材料管,它包括一个外径为35毫米、铝材厚度为1.5毫米的外铝管,一个外径为25毫米、铝材厚度为1毫米的内铝管。一层厚度为4.25毫米的刚性环氧泡沫体被包含在所述同心铝管之间,泡沫体密度是0.66g/cc。
本发明的产品是通过如下方法制备的:从可得自Core Products的、名为Core 5207的复配物挤出可发泡的环氧树脂组合物,以提供3毫米厚的可发泡材料的条。然后切割该条,并手工缠绕在内铝管上。随后环绕所述泡沫体条提供外管,在两端提供塞子以限定和保持可发泡材料与外管的内表面之间的间隙。然后将该结构在170℃下加热30分钟,以引起可发泡材料膨胀并且粘附在两个金属管上,从而产生图6的(c)中所示的结构。
如图7中所示,使用三点弯曲试验机对上述管进行弯曲试验,试验结果如图8中所示。弯曲试验中使用的速率是20mm/min。
图8显示,与钢管(达约3250N)和铝管(达约1250N)相比,本发明的复合材料具有更大的弹性范围(达5000N)。此外,所述复合材料的强度比钢管和铝管二者都大得多,所述复合材料的抗力达到约7250N,而钢管达到约4750N,铝管达到约3250N。这些结果清楚显示了由本发明的复合材料获得的强度的改善和重量的显著降低。
Claims (31)
1.一种包括夹心结构的复合材料,所述夹心结构包括附着在刚性环氧泡沫体中间层上的至少两个表面层,其中所述环氧泡沫体层是所述两个表面层的总厚度的至少1.5倍,而且所述泡沫体具有0.2~1.5g/cc的密度。
2.权利要求1所述的复合材料,其中所述泡沫体具有0.4~1.5g/cc的密度。
3.权利要求1或权利要求2所述的复合材料,其中所述泡沫体具有0.3~0.6g/cc的密度。
4.一种复合材料,它包括至少两个厚度各为0.2~10毫米的表面层和厚度为2~200毫米的刚性环氧泡沫体芯层。
5.前述权利要求任一项所述的复合材料,它具有通过ASTM D790/ISO178测定的200mPa~700mPa的弯曲模量。
6.前述权利要求任一项所述的复合材料,其中所述表面层是金属箔,例如铝箔或钢箔,塑料膜或片,例如聚丙烯或聚乙烯膜或聚对苯二甲酸乙二醇酯膜。
7.前述权利要求任一项所述的复合材料,其中所述表面层是多孔性的。
8.权利要求1~5和7任一项所述的复合材料,其中所述表面层是纤维性的。
9.权利要求8所述的复合材料,其中所述纤维是碳纤维、玻璃纤维或芳纶。
10.前述权利要求任一项所述的复合材料,它具有0.1~1.0g/cc的密度。
11.前述权利要求任一项所述的复合材料,其中所述表面层是匹配的内结构件和外结构件。
12.权利要求11所述的复合材料,其中所述结构件是中空盒部分。
13.权利要求11所述的复合材料,其中所述结构件是管。
14.权利要求13所述的复合材料,其中所述管是同心的。
15.权利要求11~14任一项所述的复合材料,其中所述表面层是金属。
16.权利要求15所述的复合材料,其中所述金属是铝。
17.前述权利要求任一项所述的复合材料,其中所述表面层是不同的材料。
18.前述权利要求任一项所述的复合材料在建筑或运输工业中提供结构件的应用。
19.权利要求18所述的应用,用于在车辆中提供抗撞击的加强件。
20.权利要求19所述的应用,用于提供汽车门加强件。
21.权利要求1~17任一项所述的复合材料在体育用品中提供强度的应用。
22.一种生产复合材料的方法,该方法包括:提供第一表面层,在其上敷设一层可热活化的可发泡环氧材料,并在所述可热活化的可发泡环氧材料层的背离所述第一纤维材料层的表面上提供第二表面层,和热活化所述环氧材料使得它发泡并且粘在所述表面层上。
23.一种生产复合材料的方法,该方法包括在两个表面层之间喷雾可发泡环氧材料,并且允许所述可发泡材料膨胀和固化并粘在所述表面层上。
24.权利要求22或权利要求23所述的方法,其中所述表面层是多孔性的,并且用环氧材料涂布和/或浸渍。
25.权利要求24所述的方法,其中所述环氧材料与所述可热活化的可发泡环氧材料是相容的。
26.权利要求25所述的方法,其中所述环氧材料与所述可热活化的材料在相同的条件下固化。
27.权利要求24~26任一项所述的方法,其中用与构成所述热活化可发泡材料的基体的环氧材料相同的环氧材料涂布和/或浸渍所述多孔层。
28.权利要求22~27任一项所述的方法,其中所述第一表面层是匹配结构件的内组件的外表面。
29.权利要求28所述的方法,其中所述第一表面层是两个同心管的内管的外表面,而第二表面是外管的内表面。
30.权利要求28所述的方法,其中所述第一表面是内盒部分的外表面,而第二表面是外盒部分的内表面。
31.权利要求28~30任一项所述的方法,其中将所述匹配结构件保持分离,以允许所述环氧材料发泡。
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2005
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- 2005-02-01 EP EP20050707155 patent/EP1718458A2/en not_active Withdrawn
- 2005-02-01 JP JP2006550148A patent/JP5082030B2/ja not_active Expired - Fee Related
- 2005-02-01 US US10/597,610 patent/US8334055B2/en not_active Expired - Fee Related
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2012
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2015
- 2015-11-17 US US14/943,981 patent/US10035326B2/en active Active
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2018
- 2018-07-27 US US16/047,779 patent/US10688752B2/en active Active
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2020
- 2020-06-19 US US16/906,650 patent/US11046042B2/en active Active
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2021
- 2021-05-27 US US17/332,297 patent/US11618239B2/en active Active
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2023
- 2023-04-03 US US18/130,114 patent/US20230241863A1/en active Pending
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US20160151998A1 (en) | 2016-06-02 |
US20230241863A1 (en) | 2023-08-03 |
US20080241576A1 (en) | 2008-10-02 |
WO2005075189A8 (en) | 2006-10-12 |
JP5082030B2 (ja) | 2012-11-28 |
US11618239B2 (en) | 2023-04-04 |
US8334055B2 (en) | 2012-12-18 |
US20140065390A1 (en) | 2014-03-06 |
US10035326B2 (en) | 2018-07-31 |
US10688752B2 (en) | 2020-06-23 |
JP2007519540A (ja) | 2007-07-19 |
US20210283880A1 (en) | 2021-09-16 |
GB0402221D0 (en) | 2004-03-03 |
US9186864B2 (en) | 2015-11-17 |
US20200376799A1 (en) | 2020-12-03 |
US11046042B2 (en) | 2021-06-29 |
WO2005075189A3 (en) | 2005-12-01 |
US20180339488A1 (en) | 2018-11-29 |
EP1718458A2 (en) | 2006-11-08 |
WO2005075189A2 (en) | 2005-08-18 |
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