CN111902464B - 用于制造耐热湿条件的复合部件的预浸料 - Google Patents
用于制造耐热湿条件的复合部件的预浸料 Download PDFInfo
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- CN111902464B CN111902464B CN201980019790.9A CN201980019790A CN111902464B CN 111902464 B CN111902464 B CN 111902464B CN 201980019790 A CN201980019790 A CN 201980019790A CN 111902464 B CN111902464 B CN 111902464B
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Abstract
本申请提供可以固化/模塑以形成航空航天复合部件的预浸渍的复合材料(预浸料),所述航空航天复合部件被设计为耐热湿条件。预浸料包括纤维和未固化的树脂。未固化的树脂包括环氧树脂组分,该环氧树脂组分是三官能的环氧树脂、四官能的环氧树脂和固体环氧树脂的组合。树脂包括聚醚砜并且可以包括热塑性颗粒组分。未固化的树脂也包括固化剂。
Description
技术领域
本发明总地涉及用于制造尤其适宜用作航空航天组件的高性能复合部件的预浸渍的复合材料(预浸料)。本发明更特别地涉及用于制造下述航空航天组件或结构的预浸料,所述航空航天组件或结构必须对于同时暴露于热温度和湿条件耐受。
背景技术
复合材料通常由作为两个主要构成组分的树脂基质和增强纤维组成。通常需要复合材料在苛刻环境中进行,例如在航空航天领域中进行,在这样的环境中复合部件或结构的物理极限和特征是至关重要的。
预浸渍的复合材料(预浸料)广泛用于制造复合部件。预浸料是通常包括未固化树脂和纤维的组合,其为随时可进行模塑和固化成最终复合部件的形式。通过用树脂预浸渍纤维增强材料,制造商可以小心控制树脂浸渍到纤维网络中的量和位置,并确保树脂按需要将树脂分布到网络中。公知的是,复合部件中纤维和树脂的相对量和树脂在纤维网络中的分布会影响部件的结构性质。
预浸料是用于制造承重或主要结构部件、以及特别是航空航天主要结构部件例如机翼,机身,舱壁和控制面的优选材料。重要的是,这些部件具有足够的强度、损伤容限以及对于这些部件和结构常规确定的其它要求。包围喷气发动机的机舱是飞机的独特结构组件,这是由于机舱紧邻重要的热源且机舱暴露于外部环境元件。存在于机舱中的很多复合部件和结构必须能够耐受热条件和湿条件两者。
通常用于航空航天预浸料的纤维是包含彼此平行延伸的纤维的多向机织物或单向带材。纤维的形式通常是大量单个纤维或单丝的捆束,其称为“丝束”。纤维或丝束也可以在树脂中是短切的和无规取向的,以形成无纺毡。将这些各种纤维配置与小心控制量的未固化树脂结合。所得预浸料通常置于保护层之间并且卷起以便储存或运输到生产设备。
固化复合部件的压缩强度主要由以下控制:增强纤维和基质树脂的各自性质,以及这两种组分之间的相互作用。而且,纤维-树脂体积比、以及预浸料在部件中的取向是影响压缩强度的因素。在很多航天航空应用中,期望的是,复合部件表现出高压缩强度。开孔压缩(OHC)试验是固化的复合材料的压缩强度的标准量度。
在很多航天航空应用中,期望的是,复合部件或结构在室温/干燥条件和热/湿条件下都表现出高压缩强度。对于位于喷气发动机附近且需要考虑暴露于高温和湿气两者的复合部件和结构而言,这是特别重要的。但是,在热湿条件下保持压缩强度较高的尝试可能对其它所需性质例如用于形成预浸料的未固化树脂的玻璃化转变温度(亚Tg)产生不利影响。
未固化的树脂的亚Tg与树脂的粘度相关。如果亚Tg过高,未固化的树脂可能变得过粘,且不适用于形成预浸料。同样,如果亚Tg过低,未固化的树脂可能具有的粘度不适当地低因而无法用作预浸料树脂。因此,必须权衡改变树脂配方以最大化所得固化的复合材料在室温/干燥条件和热/湿条件两者下的压缩强度的任何尝试与对未固化的树脂的亚Tg的潜在负面影响。
包括环氧树脂的树脂通常用于很多航空航天预浸料。已知不同类型环氧树脂的各种组合可以导致未固化的树脂和最终复合部件的性质产生广泛的变化。用于固化环氧树脂基质的固化剂也可以显著影响未固化的树脂和最终复合部件两者的性质。
当配制环氧树脂以用作航空航天预浸料中的树脂基质时,难以预期环氧树脂类型和固化剂的新组合或更换组合是否将会不利地改变还是有利地改变未固化的树脂和/或固化的复合部件的现有性质。这会使得改变树脂配方以实现所需性质组合的方法变得特别麻烦。所需性质组合的一个实例是其中未固化的树脂具有适于制备预浸料的粘度的情形以及所得预浸料适于制造必须能够耐热湿条件的喷气发动机机舱部件和结构的情形。
也已知将热塑性增韧剂添加到环氧树脂预浸料中。增韧剂例如聚醚砜(PES)或聚醚酰亚胺(PEI)溶解在环氧树脂中,然后将其与纤维组合以形成预浸料。热塑性增韧的环氧树脂已经广泛与碳纤维组合使用以制备航空航天预浸料。改变增韧剂的量会影响未固化的树脂的亚Tg和粘度以及所得固化的复合材料的性质。
也难以预期改变现有环氧树脂预浸料树脂配制物中的增韧剂的量或类型是否将会有利地改变还是不利地改变未固化的树脂和/或固化的复合材料的一种或多种性质。当改变其它树脂配制物变量例如环氧树脂和固化剂的量和类型时,这个问题会变得更加复杂和不可预期。提供一种所需性能的树脂配方更改会导致对另一种性能的不期望的不利影响。例如,将固化的复合材料的热/湿OHC增加至所需水平的配方更改可导致未固化的树脂的亚Tg变化,从而使树脂不适用于制备预浸料。
现有航空航天预浸料非常适合其预期用途。但是,仍然继续需要开发具有适合于制造航空航天预浸料的性能的树脂,其中该预浸料然后被用于制造发动机机舱部件或结构,其中该部件或结构的压缩强度不会受机舱环境中存在的热湿条件的不利影响。
发明内容
根据本发明,提供预浸渍的复合材料(预浸料),其可经模塑以形成在室温/干燥条件和热/湿条件两者下均具有高水平的压缩强度的复合部件或结构。
本发明的预浸料由纤维和未固化的树脂构成。未固化的树脂包括由三缩水甘油基氨基苯酚环氧树脂、四官能的环氧树脂和固体环氧树脂组成的树脂组分。未固化的树脂还包括热塑性增韧剂和固化剂。
本发明也包括制备预浸料的方法以及用于将预浸料模塑成当暴露于热湿条件时保持压缩强度的复合部件或结构的方法。本发明也包括使用改善的预浸料制备的复合部件和结构。本发明特别可适用于飞机发动机机舱的部件和结构。
已经发现,具有如上所述配方的树脂具有适用于制备预浸料的亚Tg和粘度,且该预浸料可以经模塑以形成能够耐受喷气发动机机舱的环境中存在的热湿条件的复合部件和结构。
通过参照以下详述连同附图,可更好理解本发明的上述和很多其它特征以及随之而来的益处。
附图说明
图1是喷气发动机的简化截面图,该喷气发动机包括机舱,该机舱由使用根据本发明的预浸料制备的部件和结构构成。
具体实施方式
根据本发明的未固化的环氧树脂组合物可以用于其中需要热塑性增韧的环氧树脂基质的众多情况。虽然未固化的环氧树脂组合物可以单独使用,但是该组合物在本发明中作为与纤维组合以形成复合材料的基质树脂使用,所述复合材料由纤维和树脂基质构成。复合材料的形式可以是预浸料、部分固化的预浸料、或由一个或多个预浸料层制备的完全固化的最终部件。术语“未固化的”当与以下表述一起使用时意在涵盖可能已经经受一定固化、但是还未完全固化以形成最终复合部件或结构的物品:预浸料;浸渍到纤维中之前的树脂;当纤维用树脂浸渍时形成的树脂基质;或复合材料。
虽然未固化的复合材料可以用于任何预期目的,但是它们优选用于制造航空航天飞行器、例如商用飞机和军用飞机的部件。例如,未固化的复合材料可以用于制备非一级(二级)飞机结构。但是,未固化的复合材料的优选用途是用于结构应用,例如一级飞机结构。一级飞机结构或部件是固定翼或旋转翼飞机的那些元件,其在飞行过程中经历显著应力并且对于飞机维持受控飞行是必要的。
认为包围飞机喷气发动机的内部组件的机舱是主要飞机结构。本发明的预浸料特别适用于制造存在于机舱中的复合部件和结构。
一种示例性喷气发动机显示在图1中的10。喷气发动机10包括燃烧芯部或热区12,其产生由箭头14表示的主要热空气流。热区或高温区域12内的热空气流可以处于500°F(260℃)至750°F(399℃)范围内的温度以及更高的温度,这取决于喷气发动机类型和设计。机舱结构16位于热区12周围以提供环形管道18,其中冷二次空气如箭头20所示流动通过该环形通道18。冷空气流在等于外部空气温度的温度进入喷气发动机,且随着其穿过环形通道18被加热至等于或稍低于热区12温度的温度。
本发明的预浸料可以用作目前用于形成机舱16中存在的复合部件和结构的现有预浸料的替代物。本发明的一个方面包括用本发明的树脂配制物代替用于制备经模塑以形成机舱部件或结构的预浸料的现有树脂。因此,本发明的树脂配制物适宜在涉及用于制造与喷气发动机机舱相关的部件和结构的预浸料的常规制造和固化方法中用作基质树脂。
本发明的预浸料由纤维和未固化的树脂基质构成。纤维可以是用于预浸料和复合片材模塑工业中的任何常规纤维构造。目前用于制造喷气发动机机舱部件和结构的纤维类型和构造是优选的。碳纤维是优选的纤维类型。
用于形成树脂基质的未固化的树脂包括由三官能的环氧树脂、四官能的环氧树脂和固体环氧树脂组成的环氧树脂组分。树脂进一步包括热塑性增韧剂和固化剂。
优选的示例性三官能的环氧树脂是三缩水甘油基间-氨基苯酚。三缩水甘油基间-氨基苯酚以商业名称Araldite MY0610购自Huntsman Advanced Materials(TheWoodlands,TX)。三缩水甘油基间-氨基苯酚也以商业名称KDS-8808购自Kukdo Chemicals(Seoul,South Korea)和以商业名称ELM-120购自Sumitomo Chemical Co.(Osaka,Japan)。另一种适宜的三官能的环氧树脂是三缩水甘油基对-氨基苯酚。三缩水甘油基对-氨基苯酚以商业名称Araldite MY0510购自Huntsman Advanced Materials(The Woodlands,TX)。可以使用其它三官能的环氧树脂,条件是它们具有的性质与三缩水甘油基间-氨基苯酚或三缩水甘油基对-氨基苯酚的性质相同或相似。
示例性的四官能的环氧树脂是N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷(TGDDM),其作为Araldite MY720和MY721商购自Huntsman Advanced Materials(TheWoodlands,TX),或作为ELM 434购自Sumitomo Chemical Industries,Ltd.(Chuo,Tokyo)。优选MY721。可用使用其它四官能的环氧树脂,条件是它们具有的性质与N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷的性质相同或相似。例如,基于N,N,N',N'-四缩水甘油基-4,4'-亚甲基双-苯胺的四官能的环氧树脂也是适宜的。此类树脂以商业名称AralditeMY9663购自Huntsman Advanced Materials(The Woodlands,TX)。
优选的是,三官能的树脂和四官能的树脂之间的重量比为1.0:1.4至1.4:1.0。特别优选的是,三官能的树脂和四官能的树脂之间的重量比为1.2:1.0至1.2:1.0。最优选的是其中三官能的树脂和四官能的树脂之间的重量比为1.0:1.0的配制物。
环氧树脂组分也包含固体环氧树脂。认为固体环氧树脂是下述环氧树脂,其在室温(20-25℃)为固体或半固体,且其软化点为40-90℃。第一示例性固体环氧树脂具有下式:
第一示例性固体环氧树脂以商业名称Tactix 742购自Huntsman(The Woodlands,TX)。Tactix 742在室温为半固体,且软化点为48.9℃。Tactix 742的环氧当量为150-170g/eq。树脂在25℃的密度为1.23g/cm3,其中树脂的闪点(闭杯)为204℃。
第二示例性固体环氧树脂具有下式:
第二示例性树脂也称为9,9-双[4-(缩水甘油氧基)苯基]芴。第二示例性固体环氧树脂以商业名称SE 250购自Shin A T&C(Overland Park,Kansas)。
第三示例性固体环氧树脂具有下式:
其中G是缩水甘油基或环氧基团,且n=1.5至2。
第三示例性固体环氧树脂以商业名称NC7000H购自Nippon Kayaku(Tokyo,Japan)。
第四示例性固体环氧树脂具有下式:
第四示例性固体环氧树脂以商业名称HP4770购自DIC(Singapore)。HP4770是萘型环氧树脂,其环氧当量为200-210g/eq且软化点为67-77℃。HP4700为购自DIC(Singapore)的萘型环氧树脂,其也是适宜的。
未固化的树脂包括至少一种固化剂。适宜的固化剂是下述那些,其促进环氧官能化合物的固化,特别是促进这样的环氧化合物的开环聚合。这样的固化剂包括在其开环聚合中与一种或多种环氧官能的化合物聚合的那些化合物。已经用于使用于制造主要结构和部件的航空航天预浸料中的环氧树脂固化的任何固化剂可以是适宜的。两种或更多种这样的固化剂也可以组合使用。
示例性优选的固化剂包括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),两者都购自Huntsman(The Woodlands,TX)。3,3'-DDS是优选的固化剂。
也可以包括促进剂以增强或促进固化。适宜的促进剂是通常用于使环氧树脂固化的任何urone化合物。可以单独或组合使用的促进剂的具体实例包括N,N-二甲基,N’-3,4-二氯苯基脲(Diuron),N’-3-氯苯基脲(Monuron),和优选为N,N-(4-甲基-间-亚苯基二[N’,N’-二甲基脲](例如购自Degussa的Dyhard UR500)。
本发明的未固化的树脂基质也包括热塑性增韧剂。通常,将热塑性增韧剂作为颗粒添加到树脂混合物中,所述颗粒通过在添加固化剂之前加热而溶解于树脂混合物中。一旦热塑性试剂充分溶解于热树脂前体(即,环氧树脂的共混物)中,则将前体冷却,添加固化剂,并与冷却的树脂共混物混合。
适宜的增韧剂,例如为,颗粒聚醚砜(PES),其以商业名称Sumikaexcel 5003P出售,其商购自Sumitomo Chemicals(New York,NY)。5003P的替代物是Solvay聚醚砜105RP,或非羟基封端的等级例如Solvay 1054P,其商购自Solvay Chemicals(Houston,TX)。致密PES颗粒可以用作增韧剂。PES的形式不是特别重要,因为PES在树脂的形成过程中是溶解的。致密PES颗粒可以根据美国专利4,945,154的教导制备,其内容通过参考并入本申请。致密PES颗粒也可作为商业名称HRI-1商购自Hexcel Corporation(Dublin,CA)。增韧剂的平均粒度应该小于100微米,以促使和确保PES完全溶解于树脂前体中。
未固化的树脂也可以包括另外的成分,例如性能增强或改性剂,条件是它们不会不利地影响当在室温/干燥条件和热/湿条件两者下测量时未固化的树脂的粘度或固化的复合材料的压缩强度。性能增强或改性剂例如可以选自核壳橡胶,阻燃剂,润湿剂,颜料/染料,UV吸收剂,抗菌化合物,填料,导电粒子,和粘度改性剂。
示例性的核壳橡胶(CSR)颗粒由以下构成:交联的橡胶核,通常为丁二烯的共聚物;和壳,其由苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和/或丙烯腈构成。核壳颗粒通常作为分散在环氧树脂中的颗粒提供。颗粒的粒度范围通常为50至150nm。适宜的CSR颗粒详细描述于美国专利公开US2007/0027233A1,其内容并入本申请以作参考。优选的核壳颗粒是MX核壳粒子,其购自Kane Ace(Pasadena,Texas)。用于包含在未固化的树脂中的优选的核壳颗粒是Kane Ace MX-418。MX-418作为核壳颗粒在四官能的环氧树脂中的25wt%悬浮液提供。MX-418中的核壳颗粒是平均粒度为100纳米的聚丁二烯(PBd)核壳颗粒。
适宜的填料包括,例如,单独或组合的任何以下物质:二氧化硅,氧化铝,二氧化钛,玻璃,碳酸钙和氧化钙。
适宜的导电粒子包括,例如,单独或组合使用的以下导电粒子中的任一种:银,金,铜,铝,镍,导电级碳,巴克敏斯特富勒烯,碳纳米管和碳纳米纤维。也可以使用金属包覆填料,例如,镍包覆的碳粒子和银包覆的铜粒子。
土豆形石墨(PSG)颗粒是适宜的导电粒子。在碳纤维/环氧树脂复合物中使用PSG颗粒详细描述于美国专利公开US 2015/0179298 A1,其内容并入本申请以作参考。PSG颗粒作为SG25/99.95 SC颗粒商购自NGS Naturgraphit(Germany)或作为GHDR-15-4颗粒商购自Nippon Power Graphite Company(Japan)。这些商购的PSG颗粒的平均粒度为10-30微米,其中GHDR-15-4颗粒具有在PSG颗粒的外表面上的碳的蒸气沉积涂层。
未固化的树脂根据标准预浸料基质树脂加工制备。通常,将三官能的环氧树脂、四官能的环氧树脂和固体环氧树脂在室温混合在一起以形成向其中添加热塑性增韧剂的树脂混合物。然后将该混合物加热至约120℃并保持约1至2小时以溶解热塑性增韧剂。然后将混合物冷却至约80℃。然后,若存在,则将固化剂、热塑性颗粒和另外的成分混合进树脂中以形成进一步冷却至室温或以下的最终的未固化的树脂。
将未固化的树脂施用于纤维增强材料以根据任何已知的预浸料制造技术形成围绕该纤维的未固化的树脂基质。纤维增强材料可以完全或部分浸渍有未固化的树脂。在可替换的实施方式中,未固化的树脂可以作为单独的层施用于纤维增强材料,该层最邻近、且接触纤维增强材料,但是不会充分浸渍纤维增强材料。预浸料也称为半浸料,通常用保护膜覆盖在两个面上并且卷起以用于在下述温度储存和运输,所述温度通常保持充分低于室温以避免过早固化。不形成实际的树脂基质,直到进一步加工半浸料才形成。如果期望,可以使用任何其它预浸料制造方法和储存/运输系统。
预浸料的纤维部分也称为纤维增强物或纤维支撑物,其可以选自任何玻璃纤维、碳纤维或芳纶(芳族聚酰胺)纤维。纤维增强物优选为碳纤维。优选的碳纤维是包含3,000至50,000根碳单丝(3K至50K)的丝束的形式。优选包含6,000、12,000或24,000根碳单丝(6K、12K或24K)的商购碳纤维丝束。
预浸料的纤维部分可以包含断裂(即拉断)、选择性不连续或连续的纤维。使用断裂或选择性不连续的纤维可以有助于复合材料在完全固化前的铺叠,并改善其成型能力。纤维增强材料可以为机织、非卷曲、非机织、单向、或多轴的纺织品结构形式,例如用于形成片材模塑混配物的准各向同性的短切预浸料。机织形式可以选自平纹、缎纹、或斜纹编织样式。非卷曲和多轴形式可以具有多个铺层和纤维取向。这些样式和形式是复合增强材料领域公知的,且可商购自多个公司,包括Hexcel Reinforcements(Les Avenieres,France)。
预浸料的形式可以为连续带,丝束预浸料,网幅,或短切长度(短切和纵切操作可以在浸渍后的任何点进行)。预浸料可以是粘合剂或铺膜,并且可以另外具有各种形式(机织编织和非机织两者)的植入载体。预浸料可以完全或仅部分浸渍,例如以有助于在固化过程中移除空气。
将以下示例性树脂配制物浸渍到纤维支撑物中以形成根据本发明的预浸料(所有重量百分比均基于总树脂重量):
22wt%至26wt%的三缩水甘油基间-氨基苯酚;22wt%至26wt%的四官能的环氧树脂;4wt%至8wt%的固体环氧树脂;15wt%至19wt%的聚醚砜;和27wt%至32wt%的作为固化剂的3,3'-DDS。
以下是优选的示例性树脂配制物,其中给定量的各成分可以相差±1wt%(所有重量百分比均基于总树脂重量):
23.8wt%的三缩水甘油基间-氨基苯酚;23.8wt%的四官能的环氧树脂;6wt%的固体环氧树脂;16.9wt%的聚醚砜;和29wt%的作为固化剂的3,3'-DDS。
预浸料可以使用用于形成复合部件的任何标准技术模塑。通常,将一个或多个层的预浸料放进适宜的模具中并固化以形成最终的复合部件。本发明的预浸料可以使用本领域已知的任何适宜的温度、压力和时间条件完全或部分固化。通常,预浸料将在高压釜中在160℃至190℃的温度固化。复合材料可以使用选自以下的方法固化:微波辐射,电子束,γ辐射,或其它适宜的热辐射或非热辐射。
由本发明的改进预浸料制造的复合部件特别适合用于制造喷气发动机机舱中存在的复合部件和结构。未固化的树脂的亚Tg适宜用于制备预浸料,且由该预浸料模塑的复合部件和结构能够耐受存在于喷气发动机机舱环境中的热湿条件。
针对本说明书的目的,如果部件或结构的固化复合材料当在132℃在ASTM D6484的现有版本中记载的湿条件(热/湿OHC)下测量时的开孔压缩(OHC)为37或更大,则认为复合部件或结构能够耐受热湿条件。优选地,固化的复合材料的132℃/湿OHC将为至少38。
针对本说明书的目的,为了适宜用作制备经模塑以形成发动机机舱部件和结构的预浸料的未固化树脂,树脂的亚Tg应该在-10℃至5℃的范围内,其通过以10℃/分钟的加热速率进行的差示扫描量热法(DSC)测定。优选地,亚Tg将为-5℃至5℃,最优选为0℃至5℃。
实施例
实践的实施例如下:
实施例1
根据本发明的第一优选的示例性未固化树脂配方列于表1。未固化的树脂如下制备:将环氧成分在室温与聚醚砜混合以形成树脂共混物,将树脂共混物加热至120℃并保持60分钟以完全溶解聚醚砜。将混合物冷却至80℃,添加固化剂并彻底混合。
表1
树脂的亚Tg通过DSC以10℃/分钟的加热速率测量,发现其为2.2℃。
示例性的预浸料如下制备:用表1的树脂配制物浸渍一个或多个单向碳纤维层。单向碳纤维((12K AS4),购自Hexcel Corporation)用于制备下述预浸料,其中基质树脂总计达总未固化预浸料重量的35wt%,且纤维单位面积重量为192克每平方米(gsm)。使用标准预浸料制造过程制备26-层层合体。使层合体在高压釜中在177℃固化约2小时。测试固化的层合体以根据ASTM D6484在以下条件下确定OHC:室温/干燥条件;82℃/湿条件;和132℃/湿条件。结果分别为55.7、45.4和38.6。
实施例2
按照与实施例1相同的方式制备具有表2所列配方的第二优选的示例性未固化的树脂。
表2
树脂的亚Tg按照与实施例1相同的方式测量,发现其为2.4℃。
按照与实施例1相同的方式制备26-层层合体,使其固化并测量OHC。层合体在以下条件下的OHC分别为54.3、42.3和38.3:室温/干燥条件;82℃/湿条件;和132℃/湿条件。
实施例3
按照与实施例1相同的方式制备具有表3所列配方的第三优选的示例性未固化的树脂。
表3
树脂的亚Tg按照与实施例1相同的方式测量,发现其为2.6℃。
按照与实施例1相同的方式制备26-层层合体,使其固化并测量OHC。层合体在以下条件下的OHC分别为53.4、45.0和37.8:室温/干燥条件;82℃/湿条件;和132℃/湿条件。
实施例4
按照与实施例1相同的方式制备具有表4所列配方的第四优选的示例性未固化的树脂。
表4
树脂的亚Tg按照与实施例1相同的方式测量,发现其为2.4℃。
按照与实施例1相同的方式制备26-层层合体,使其固化并测量OHC。层合体在以下条件下的OHC分别为54.7、44.9和37.1:室温/干燥条件;82℃/湿条件;和132℃/湿条件。
所有优选的示例性未固化树脂均特别适宜于制备预浸料,所述预浸料用于制造喷气发动机机舱中存在的复合部件和结构,因为未固化的树脂全部具有的亚Tg在2℃至3℃之间,且所有由所述树脂制备的层合体在132℃/湿条件下均具有37至39之间的OHC。
对比实施例如下:
对比实施例1-7
具有表5所列配方的未固化树脂的对比实施例按照与实施例1相同的方式制备。按照与实施例1相同的方式制备26-层层合体,使其固化并测量OHC。也按照与实施例1相同的方式测试未固化的对比树脂的亚Tg。OHC和亚Tg测试的结果列于表5。
表5
对比实施例1-4证明,树脂配制物中缺少固体环氧树脂阻碍在132℃/湿条件下根据本发明达到优选的亚Tg(0℃至5℃)和/或适宜的OHC(至少37)。对比实施例5-6证明,添加显著量的固体环氧树脂(超过10wt%)提供在132℃/湿条件下适宜的OHC,但是亚Tg(几乎17℃)显著高于根据本发明的适于制备机舱预浸料的优选的亚Tg范围。
也在160℃/湿条件下根据ASTM D6484测试根据实施例4制备的层合体的OHC。在160℃/湿条件下的OHC为34.0,这是特别高且预料不到的,因为发现对比实施例7在160℃/湿条件下的OHC仅为22.0。用于对比实施例7的Tactix 556是具有二环戊二烯主链的烃线型酚醛环氧树脂,其购自Huntsman(The Woodlands,TX)。Tactix 556是半固体树脂,其软化点为53℃。
多层预浸料通常用于形成具有层状结构的复合部件。这种复合部件的分层是重要的失效模式。当两个层彼此脱粘时,发生分层。重要的设计限制因素包括启动分层所需的能量和使分层扩散所需的能量两者。分层的启动和发展通常通过检验模式I和模式II断裂韧度来确定。断裂韧度通常使用具有单向纤维取向的复合材料测量。复合材料的层间断裂韧性使用G1c(双悬臂梁(Double Cantilever Beam))和G2c(最终缺口弯曲(End NotchFlex))试验定量。在模式I中,预开裂层合体失效以剥离力为准,在模式II中,开裂通过剪切力扩散。
根据本发明,少量的热塑性颗粒(1至5wt%,基于未固化的树脂的总重量)作为热塑性颗粒组分包括在未固化的树脂中以提供增加的层间断裂韧性。优选地,热塑性颗粒组分中的热塑性颗粒的量将为3wt%±1wt%,基于未固化的树脂的总重量。
一种或多种类型的热塑性颗粒可以包括在未固化的树脂中以形成热塑性颗粒组分。示例性的热塑性颗粒是聚酰胺颗粒,其由双(4-氨基环己基)甲烷的甲基衍生物和选自癸烷二甲酸和十二烷二甲酸的脂族二羧酸的聚合缩合产物形成。双(4-氨基环己基)甲烷的甲基衍生物在本申请称为“胺组分”,其也称为4,4’-二氨基环己基甲烷的甲基衍生物。该类型的聚酰胺颗粒及其制备方法详细描述于美国专利3,936,426和5,696,202,其内容并入本申请以作参考。
聚合缩合产物的胺组分的化学式为
其中R2是氢,R1为甲基或氢。
聚合缩合产物的单体单元的化学式如下展示:
聚合缩合产物的分子数将为14,000至20,000,优选的分子数为约17,000。
聚酰胺颗粒的粒度应该低于100微米。优选的是,颗粒的尺寸为5至60微米,更优选为10至30微米。优选的是,平均粒度为15至25微米。聚酰胺颗粒的形状可以为规则的或不规则的。例如,颗粒可以是基本上球形的,或者它们可以是具有锯齿形状的颗粒。
一种示例性的聚酰胺颗粒由下述聚酰胺制备,其中聚合缩合产物的胺组分具有以上化学式,其中R1都是甲基,R2都是氢。这样的聚酰胺颗粒可以由3,3’-二甲基-双(4-氨基环己基)-甲烷和1,10-癸烷二甲酸的聚合缩合产物制备。聚酰胺颗粒如下制备:在加热的接收容器中将13,800克1,10-癸烷二甲酸和12,870克3,3’-二甲基-双(4-氨基环己基)-甲烷与30克50%含水磷酸、150克苯甲酸和101克水组合。将混合物在高压釜中搅拌,直到均匀。在压缩、减压和排气阶段之后,将聚酰胺缩合产物作为线料压出、在冷水下通过、并制粒以形成聚酰胺颗粒。其中R1都是甲基且R2都是氢的聚酰胺颗粒也可以由GRILAMID TR90制备,其商购自EMS-Chime(Sumter,SC)。GRILAMID TR90是3,3’-二甲基-双(4-氨基环己基)-甲烷和1,10-癸烷二甲酸的聚合缩合产物。
另一种示例性的聚酰胺颗粒由下述聚酰胺制备,其中聚合缩合产物的胺组分具有以上化学式,其中R1都是氢且R2都是氢。这样的聚酰胺颗粒可以按与上述相同的方式制备,所不同的是聚酰胺是3,3’-二甲基-双(4-氨基环己基)-丙烷和1,10-癸烷二甲酸的聚合缩合产物。其中R1都是氢且R2都是氢的聚酰胺颗粒也可以由TROGAMIDE CX7323或CX9705制备,其商购自Evonik(Mobile,AL)。CX7323和CX9705是3,3’-二甲基-双(4-氨基环己基)-丙烷和1,10-癸烷二甲酸的聚合缩合产物。
热塑性颗粒组分可以包括一种或多种类型的通常用于热塑性增韧的环氧树脂的聚酰胺颗粒,其包括例如,聚酰胺(PA)11,PA6,PA12,PA6/PA12共聚物,PA4,PA8,PA6.6,PA4.6,PA10.10,PA6.10和PA10.12。
示例性热塑性颗粒组分包含:不包含交联的聚酰胺的第一组聚酰胺颗粒,和包含交联的聚酰胺的第二组聚酰胺颗粒。
第一组聚酰胺颗粒可以是任何下述聚酰胺颗粒:其包含交联的聚酰胺且通常用于热塑性增韧的基于环氧树脂的预浸料。这样的颗粒由以下组成:聚酰胺(PA)11,PA6,PA12,PA6/PA12共聚物,PA4,PA8,PA6.6,PA4.6,PA10.10,PA6.10和PA10.12。非交联的聚酰胺颗粒商购自多个来源。适宜的非交联的聚酰胺12颗粒以商业名称SP10L购自Kobo Products。SP10L可以包含超过98wt%的PA 12。粒度分布为7微米至13微米,其中平均粒度为10微米。颗粒的密度为1g/cm3。优选的是,PA12颗粒是至少95wt%的PA12,除水分含量之外。
其它适宜的非交联的颗粒以商业名称Orgasol 1002粉末和Orgasol 3803粉末购自Arkema(Colombes,France)。Orgasol 1002粉末由100%的平均粒度为20微米的PA6颗粒构成。Orgasol 3803由平均粒度为17至24微米的颗粒构成,所述颗粒是80%PA12和20%PA6的共聚物。Orgasol 2002是由也可以用于第一组颗粒的非交联的PA12颗粒构成的粉末。
第一组热塑性颗粒的示例性非交联的聚酰胺颗粒是聚酰胺11颗粒,其也可商购自多个来源。优选的聚酰胺11颗粒以商业名称Rislan PA11购自Arkema(Colombes,France)。这些颗粒包含超过98wt%的PA 11且粒度分布为15微米至25微米。平均粒度为20微米。Rislan PA11颗粒的密度为1g/cm3。优选的是,PA 11颗粒是至少95wt%PA11,除水分含量之外。
第二组热塑性聚酰胺颗粒是下述颗粒,其在颗粒的表面上包含交联的聚酰胺、在颗粒的内部包含交联的聚酰胺,或两者皆有。交联的聚酰胺颗粒可以由在颗粒形成之前已经交联的聚酰胺制备,或者非交联的聚酰胺颗粒可以用适宜的交联剂处理以制备交联的聚酰胺颗粒。
适宜的交联的颗粒包含交联的PA11,PA6,PA12,PA6/PA12共聚物,PA4,PA8,PA6.6,PA4.6,PA10.10,PA6.10和PA10.12。通常用于使聚酰胺交联的任何交联剂是适宜的。适宜的交联剂是基于环氧树脂的交联剂,基于异氰酸酯的交联剂,基于碳二亚胺的交联剂,基于酰基内酰胺的交联剂和基于唑啉的交联剂。优选的交联的颗粒是PA12颗粒,其包含已经用环氧交联剂交联的PA12。用于使热塑性聚合物(包括聚酰胺)交联的过程是已知的。例如,参见美国专利6399714,美国专利8846818和美国公布的专利申请US 2016/0152782 A1。这三篇参考文献的内容并入本申请以作参考。
交联的PA12颗粒以商业名称ORGASOL 2009聚酰胺粉末商购自Arkema(Colombes,France),其也称为CG352。存在于ORGASOL 2009聚酰胺粉末中的PA12颗粒由至少40%的PA12构成,其已经用基于环氧树脂的交联剂交联。ORGASOL 2009交联的聚酰胺颗粒的平均粒度为14.2微米,其中仅0.2%的颗粒的直径大于30微米。ORGASOL 2009交联的颗粒的熔点为180℃。ORGASOL 2009颗粒的比表面积为1.9,颗粒的水分含量为0.34%。
交联的聚酰胺颗粒应该包含40至70%的交联的聚酰胺。优选地,交联的聚酰胺颗粒应该各自包含40至60%的交联的聚酰胺。
优选地,非交联的聚酰胺颗粒和交联的聚酰胺颗粒的粒度应该都低于100微米。优选的是,颗粒的尺寸为5至60微米,更优选为5至30微米。优选的是,平均粒度为5至20微米。颗粒的形状可以是规则的或不规则的。例如,颗粒可以是基本上球形的,或者它们可以是具有锯齿形状的颗粒。优选的是,非交联的颗粒的平均粒度大于交联的颗粒。优选地,平均非交联粒度将为15至25微米,平均交联粒度将为10至20微米。
当使用交联的颗粒和非交联的颗粒的组合时,非交联的颗粒和交联的颗粒的相对量可以变化。非交联的颗粒与交联的颗粒的重量比可以为4:1至1.5:1。优选地,非交联的颗粒与交联的颗粒的重量比将为3.5:1至2.5:1。
另一种示例性热塑性颗粒组分可以包括聚酰亚胺颗粒和聚酰胺颗粒的组合,其中聚酰胺颗粒由双(4-氨基环己基)甲烷的甲基衍生物和脂族二羧酸的聚合缩合产物构成。
优选的聚酰亚胺颗粒作为P84聚酰亚胺模塑粉末商购自HP Polymer GmbH(Lenzig,Austria)。适宜的聚酰胺颗粒也以商业名称P84NT商购自Evonik Industries(Austria)。用于制备颗粒的聚酰亚胺公开于美国专利3,708,458,其内容并入本申请以作参考。聚酰亚胺通过将苯甲酮-3,3’,4,4’-四甲酸二酐与4,4’-亚甲基双(苯基异氰酸酯)和甲苯二异氰酸酯的混合物(2,4-异构体或2,6-异构体)组合制备。胺类似物可以用于替代芳族异氰酸酯和二异氰酸酯。聚酰亚胺的CAS登记号为58698-66-1。
聚酰亚胺颗粒由具有下式的重复单体的芳族聚酰亚胺组成:
其中总聚合物中10至90%的R基团是具有下式的芳族基团:
聚合物中剩余的R是
聚酰亚胺颗粒在粉末中的尺寸通常为2微米至35微米。优选的聚酰亚胺粉末将包含下述颗粒,其尺寸为2至30微米,且平均粒度为5微米至15微米。优选地,粉末中至少90wt%的聚酰亚胺颗粒的尺寸将为2微米至20微米。聚酰亚胺颗粒的形状可以是规则的或不规则的。例如,颗粒可以是基本上球形的,或者它们可以是具有锯齿形状的颗粒。
聚酰亚胺颗粒包含至少95wt%的聚酰亚胺。少量(至多5wt%)其它材料可以包括在颗粒中,条件是它们不会不利地影响颗粒的整体特征。
聚酰亚胺颗粒的玻璃化转变温度(Tg)应该为约330℃,其中单个颗粒的密度为1.34克每立方厘米。颗粒的线性热膨胀系数为50。
聚酰胺颗粒与聚酰亚胺颗粒之间的重量比可以为3.5:1.0至1.0:1.0。优选地,聚酰胺颗粒和聚酰亚胺颗粒之间的重量比为3.2:1.0至2.8:1.0。
关于在未固化的树脂中包含热塑性颗粒组分的实践的实例如下:
实施例5
具有表5A中所列配方的优选的示例性未固化树脂按照与实施例1相同的方式制备,所不同的是将热塑性颗粒组分(CX9705的颗粒,其粒度小于20微米,平均粒度为5微米)在与固化剂混合的同时与未固化的树脂混合。
表5A
示例性预浸料如下制备:用表5A的树脂配制物浸渍一个或多个碳纤维织物层。碳纤维织物(AS4D碳纤维织物,购自Hexcel Corporation,Dublin,CA)用于制备预浸料,其中基质树脂的量达到总未固化预浸料重量的35wt%,且碳纤维单位面积重量为193克每平方米(gsm)。20-层层合体使用标准预浸料制造过程制备。将层合体在高压釜中在177℃固化约2小时。固化的层合体为0.16±0.01英寸厚,对其进行测试以根据BSS 7273的当前版本确定G1c。
发现G1c为4.0in-lb/in2。未固化的树脂的亚Tg为-5.8℃。实施例4中所列的树脂缺少热塑性颗粒,所述树脂用于制备等同于实施例5的预浸料且经受相同的G1c测试过程。实施例4预浸料的G1c为2.8in-lb/in2。
实施例6
按照与实施例5相同的方式制备具有表6所列配方的示例性未固化的树脂。
表6
预浸料和层合体按照与实施例5相同的方式制备和固化,并测试其G1c。发现G1c为3.2in-lb/in2。未固化的树脂的亚Tg为2.0℃。
实施例7
按照与实施例5相同的方式制备具有表7所列配方的示例性未固化的树脂。
表7
预浸料和层合体按照与实施例5相同的方式制备和固化,并测试其G1c。发现G1c为3.5in-lb/in2。亚Tg为-5.3℃。
实施例8
除了使用Rislan PA11颗粒代替CX9705颗粒之外,按照与实施例5相同的方式制备具有表8所列配方的示例性未固化的树脂。
表8
预浸料和层合体按照与实施例5相同的方式制备和固化,并测试其G1c。发现G1c为3.02in-lb/in2。未固化的树脂的亚Tg为-3.2℃。
实施例9
按照与实施例8相同的方式制备具有表9所列配方的示例性未固化的树脂。
表9
预浸料和层合体按照与实施例5相同的方式制备和固化,并测试其G1c。发现G1c为3.03in-lb/in2。未固化的树脂的亚Tg为-3.4℃。
得益于如此描述的本发明的示例性实施方式,本领域技术人员应注意范围内的公开内容仅是示例性的,可以在本发明的范围内进行各种其它替换、改编和修改。因此,本发明不限于上述实施方式,而仅由所附权利要求限定。
Claims (16)
1.一种预浸料,其可固化以形成复合材料,所述复合材料在132℃的温度在湿条件下具有至少37的开孔压缩,所述预浸料包含:
A)纤维;和
B)未固化的树脂,其具有0℃至5℃的亚玻璃化转变温度,所述未固化的树脂包含:
a)环氧树脂组分,其包含:
1)22至26wt%的三缩水甘油基氨基苯酚环氧树脂,基于所述未固化的树脂的总重量;
2)22至26wt%的四官能的环氧树脂,基于所述未固化的树脂的总重量;
3)4至8wt%的固体环氧树脂,基于所述未固化的树脂的总重量,其中所述固体环氧树脂选自具有下式的固体环氧树脂:
其中G是缩水甘油基或环氧基团,且n=1.5至2;和
b)15至19wt%的聚醚砜,基于所述未固化的树脂的总重量;和
c)固化剂,其量足以提供所述未固化的树脂的固化以形成所述复合材料。
2.根据权利要求1所述的预浸料,其中所述三缩水甘油基氨基苯酚环氧树脂与所述四官能的环氧树脂的重量比为1:1。
3.复合部件或结构,其已经通过固化根据权利要求1所述的预浸料形成。
4.根据权利要求3所述的复合部件或结构,其中所述复合部件或结构形成飞机发动机机舱的至少一部分。
5.制备预浸料的方法,所述预浸料可固化以形成复合材料,所述复合材料在132℃的温度在湿条件下具有至少37的开孔压缩,所述方法包括以下步骤:
A)提供纤维;和
B)用未固化的树脂浸渍所述纤维,所述未固化的树脂具有0℃至5℃的亚玻璃化转变温度,所述未固化的树脂包含:
a)环氧树脂组分,其包含:
1)22至26wt%的三缩水甘油基氨基苯酚环氧树脂,基于所述未固化的树脂的总重量;
2)22至26wt%的四官能的环氧树脂,基于所述未固化的树脂的总重量;
3)4至8wt%的固体环氧树脂,基于所述未固化的树脂的总重量,其中所述固体环氧树脂选自具有下式的固体环氧树脂:
其中G是缩水甘油基或环氧基团,且n=1.5至2;和
b)15至19wt%的聚醚砜,基于所述未固化的树脂的总重量;和
c)固化剂,其量足以提供所述未固化的树脂的固化以形成所述复合材料。
6.根据权利要求5所述的制备预浸料的方法,其中所述三缩水甘油基氨基苯酚环氧树脂与所述四官能的环氧树脂的重量比为1:1。
7.制造复合部件或结构的方法,其包括以下步骤:提供根据权利要求1所述的预浸料,和固化所述预浸料以形成所述复合部件或结构。
8.预浸料,其可固化以形成复合材料,所述预浸料包含:
A)纤维;和
B)未固化的树脂,其包含:
a)环氧树脂组分,其包含:
1)23至27wt%的三缩水甘油基氨基苯酚环氧树脂,基于所述未固化的树脂的总重量;
2)23至27wt%的四官能的环氧树脂,基于所述未固化的树脂的总重量;
3)4至8wt%的固体环氧树脂,基于所述未固化的树脂的总重量,其中所述固体环氧树脂选自具有下式的固体环氧树脂:
其中G是缩水甘油基或环氧基团,且n=1.5至2;和
b)12至16wt%的聚醚砜,基于所述未固化的树脂的总重量;
c)1至5wt%的热塑性颗粒组分,基于所述未固化的树脂的总重量;和
d)固化剂,其量足以提供所述未固化的树脂的固化以形成所述复合材料。
9.根据权利要求8所述的预浸料,其中所述三缩水甘油基氨基苯酚环氧树脂是三缩水甘油基对-氨基苯酚环氧树脂。
10.根据权利要求8所述的预浸料,其中所述四官能的环氧树脂是N,N,N’,N’-四缩水甘油基-4,4'-二氨基二苯基甲烷。
11.根据权利要求10所述的预浸料,其中所述三缩水甘油基氨基苯酚环氧树脂是三缩水甘油基对-氨基苯酚环氧树脂。
12.根据权利要求8所述的预浸料,其中所述三缩水甘油基氨基苯酚环氧树脂与所述四官能的环氧树脂的重量比为1:1。
13.复合部件或结构,其已经通过固化根据权利要求8所述的预浸料形成。
14.根据权利要求13所述的复合部件或结构,其中所述复合部件或结构形成飞机发动机机舱的至少一部分。
15.制备可固化以形成复合材料的预浸料的方法,所述方法包括以下步骤:
A)提供纤维;和
B)用未固化的树脂浸渍所述纤维,所述未固化的树脂包含:
a)环氧树脂组分,其包含:
1)23至27wt%的三缩水甘油基氨基苯酚环氧树脂,基于所述未固化的树脂的总重量;
2)23至27wt%的四官能的环氧树脂,基于所述未固化的树脂的总重量;
3)4至8wt%的固体环氧树脂,基于所述未固化的树脂的总重量,其中所述固体环氧树脂选自具有下式的固体环氧树脂:
其中G是缩水甘油基或环氧基团,且n=1.5至2;和
b)12至16wt%的聚醚砜,基于所述未固化的树脂的总重量;
c)1至5wt%的热塑性颗粒组分,基于所述未固化的树脂的总重量;和
d)固化剂,其量足以提供所述未固化的树脂的固化以形成所述复合材料。
16.制造复合部件或结构的方法,其包括以下步骤:提供根据权利要求8所述的预浸料,和固化所述预浸料以形成所述复合部件或结构。
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