CN103998683A - 结构用芯材 - Google Patents
结构用芯材 Download PDFInfo
- Publication number
- CN103998683A CN103998683A CN201280063055.6A CN201280063055A CN103998683A CN 103998683 A CN103998683 A CN 103998683A CN 201280063055 A CN201280063055 A CN 201280063055A CN 103998683 A CN103998683 A CN 103998683A
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- CN
- China
- Prior art keywords
- resin
- modulus
- core
- fiber
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
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Classifications
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
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- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
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- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
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- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
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Abstract
本发明涉及包含非织造纤维加强碳纳米管纤维网的结构用芯材,所述纤维网涂覆有热固性或热塑性树脂,其中碳纳米管在加强纤维网内取向成使得在树脂涂覆之后,纤维网在平面内沿第一方向的模量与沿正交于第一方向的第二方向的模量的比率不大于2.0;树脂涂覆的纤维网的平面内杨氏模量为至少14GPa,并且涂层树脂占纤维网加上树脂的重量的15至75重量%。
Description
背景技术
1.技术领域
本发明涉及由包含碳纳米管的纤维网制成的高强度芯结构。芯结构可以为蜂窝结构或折叠芯材的形式。
2.相关领域的描述
授予Furuzuki的日本专利申请号JP2010037660A公开了可通过在造纸工艺中添加相对于固体材料的总量1至50wt%的量的单分散状态碳纳米管来制备含纸的碳纳米管(CNT)。含纸的CNT的组成纤维组分为天然纤维、合成纤维、无机纤维、金属纤维等。
授予Wang的中国专利申请号CN101284661A提出,通过向包含金属颗粒的溶液中添加碳纳米管材料,进行絮凝处理,添加还原剂,然后从溶液分离出纳米管絮凝结构来制备碳纳米管片。
授予Shah的PCT公开WO2011054008A描述了包含注入到芳族聚酰胺纤维材料的碳纳米管(CNT)的组合物,所述组合物包含可螺旋化维度的芳族聚酰胺纤维材料、共形地设置在芳族聚酰胺纤维材料周围的阻隔涂层和注入到芳族聚酰胺纤维材料的碳纳米管(CNT)。所注入的CNT长度一致,并且密度均匀。
得自高模量高强度纤维非织造片材的用于复合夹心板的芯结构(大多呈蜂窝形式)用于不同的应用中,但主要用于其中强重比或刚重比具有非常高的值的航空和航天工业。例如,授予Lin的美国专利5,137,768描述了一种由高密度湿法成网的非织造材料制成的蜂窝结构芯材,所述非织造材料包含50wt.%或更多的对位芳族聚酰胺纤维,其中该组合物的其余部分为基料和其它添加剂。
公布WO2011/062980描述了由包含20-85重量%的碳纤维絮凝物的纸材制成的蜂窝芯材。碳纤维具有至少1.5∶1的非圆形横截面长宽比。纸材具有至少35%的纤维体积分数。碳纤维的算术平均长度为至少0.5mm,并且长度加权平均长度为至少0.9mm。公布WO2011/062980描述了由相同纸材制成的折叠芯材。
持续需要提供包含具有改善的机械性能(如刚度、强度和韧性)的芯材的芯结构和复合板。对用于航空器、火车和轮船的结构尤其如此。
发明内容
本发明涉及包含非织造纤维加强碳纳米管纤维网的结构用芯材,所述纤维网涂覆有热固性或热塑性树脂,其中:
(i)碳纳米管在加强纤维网内取向,为使得在树脂涂覆之后,纤维网在平面内沿第一方向的模量与沿正交于第一方向的第二方向的模量的比率不大于2.0,
(ii)树脂涂覆纤维网的平面内杨氏模量为至少14GPa,并且
(iii)涂层树脂占纤维网加上树脂的重量的15至75重量%。
本发明还涉及包含芯结构的复合板。
附图说明
图1A和1B分别为六边形蜂窝结构的平面图和端视图。
图2为六边形蜂窝结构的透视图。
图3为具有面板的蜂窝结构的透视图。
图4为折叠芯结构的透视图。
图5A至5D示出多层加强纤维网的实施例的端视图。
具体实施方式
芯结构
本发明涉及由纤维加强纤维网和基质树脂制成的高强度芯结构。芯结构可以为蜂窝结构或折叠芯材形式。
图1A为本发明的一个蜂窝结构1的平面图示意图,并且示出由孔室壁3形成的孔室2。图1B为图1A所示蜂窝结构的端视图,并且示出在孔室壁的两端形成的两个外表面或面4。芯材也具有边缘5。图2为蜂窝结构的透视图。所示为具有六边形孔室2和孔室壁3的蜂窝结构1。图2中在“10”处示出蜂窝结构的“T”维度或厚度。所示为六边形孔室,然而,其它几何排列也是可能的,其中正方形孔室、过度扩展孔室和弯曲芯材孔室是最常见的可能排列。此类孔室类型为本领域的人们所熟知,并且可以参考T.Bitzer的Honeycomb Technology第14至20页(Chapman&Hall,publishers,1997)中关于可能的几何孔室类型的其它信息。
图3示出由蜂窝结构芯材6与面板7和8装配成的结构用复合材料夹心板5,其中所述两个面板附接到所述芯材的两个外表面。优选的面板材料为预浸料坯、浸渍有热固性或热塑性树脂的纤维片,但是也可利用其它塑性或金属面板。如果使用金属面板,以及在一些情况下使用塑性或预浸料坯面板,那么也使用粘合剂膜9。通常在芯材的两个侧面上均有至少两个预浸料坯面板。
图4示出折叠芯结构,它是由比较薄的平面片材料折叠而成的折叠几何图案的三维结构。此类折叠或棋盘格状片结构在美国专利6,935,997B2和6,800,351B1中有所论述。山形是用于三维折叠的棋盘格状芯结构的常见图案。此类结构不同于蜂窝结构。优选的棋盘格状折叠结构为美国专利申请号6,913,570B2和美国专利申请公布2010/0048078中所描述的类型。
加强纤维网
芯结构包含由碳纳米管制成的纤维加强纤维网。在一些实施例中,纤维加强纤维网为可以呈纸材或无规取向短纤维垫形式的非织造片材。
适宜作为碳纳米管的纤维网以制备高强度芯材的片结构购自NanocompTechnologies,Inc.(Concord,NH)并在美国专利申请公布2009/0215344中有所描述。优选CNT具有至少100的长宽比,以便提供能够承受进一步连续处理的足够强度的非织造结构。
在一些实施例中,纤维网厚度为12至100微米(0.5至4密耳),并且基重为10至50克/平方米(0.3至1.5盎司/平方码)。
在纤维网内取向CNT,使得在树脂涂覆之后,纤维网的沿第一方向的模量与沿正交于第一方向的第二方向的模量的比率不大于2.0。在一些实施例中,纤维网的沿第一方向的模量与沿正交于第一方向的第二方向的模量的比率不大于1.5。纤维网将具有约1的模量比,在所述纤维网中CNT是贯穿纤维网无规分布的。具有显著程度纤维取向的纤维网将具有大于2的模量比。在一些实施例中,第一方向为轴向。轴向是纤维网在平面内的长方向,即,其中通过机器制备纤维网的方向。该方向也被称为纵向。在一些实施例中,第二方向为横向。横向在正交于轴向的方向上横跨纤维网。
CNT的成形非织造片材可以任选被压延,从而增大其密度。在本发明的一些实施例中,压延使得在用树脂涂覆之前加强纤维网的密度为至少0.7g/cm3。在压延过程中,纤维网被压缩但是没有被拉伸,因此最小化CNT的取向程度。
由碳纤维制成的非织造片和织造片材通常不能承受压延工艺,因为超高压连同剪切力会压碎该片,尤其是在纤维彼此交叠处。令人惊讶的是,已发现,来自如上所述碳纳米管的非织造片材可在金属一金属压料辊之间以非常高的线压力(如以几千N/cm)被压延并致密。没有观察到拉伸强度的损耗,仅注意到断裂伸长率略微下降。较低的伸长值仍足够用于片结构的进一步加工。该令人惊讶的发现的详细数据示于下面的例子。
在一些实施例中,纤维加强纤维网包含至少两层,其中第一层由碳纳米管的非织造片材形成。第二层可以为由以下材料形成的另一层:碳纳米管的非织造片材、包含不同于碳纳米管的一类高模量高强度纤维的非织造片材、或包含碳纳米管和另一类高模量高强度纤维的组合的非织造片材。纤维网可包含多个第一层、第二层或两者。
当纤维加强纤维网包含几层碳纳米管的非织造片材时,每层可包含无规取向的碳纳米管,或者每层可包含显著地在一个特定方向上取向的纤维。这种取向可用于增大树脂浸渍纤维网的模量和强度。然而,树脂浸渍纤维网沿第一方向的模量与纤维网沿第二方向的模量的比率不应当超过2。所谓显著地取向,意思是指在一个特定方向上比另一个特定方向有更多纤维取向,也就是说,纤维取向不是无规的。在一些实施例中,可将包含取向纤维的各层布置为使得一层中纤维的取向正交于另一层中纤维的取向。在一些情况下,各层的取向纤维可以彼此相邻。一层中的纤维取向可不正交于另一层中的纤维取向,例如一层中的纤维可以在零度方向上取向,而另一层中的纤维取向成与零方向成45度角。纤维网也可以包含具有无规和非无规纤维取向的各层的共混物。
涂层树脂
加强纤维网的表面涂覆有基质树脂。在一些实施例中,树脂完全或部分浸渍纤维网。涂层树脂占纤维网加上树脂的重量的15至75重量%。基质树脂可以为热固性或热塑性树脂。合适的树脂包括酚树脂、环氧树脂、阻燃环氧树脂、聚酯、聚酰胺、聚酰亚胺、聚苯硫醚(PPS)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚砜(PES),以及它们的共混物。基质树脂可包含另外的性能加强或改性成分,从而改善本发明的结构用芯材的特性。此类成分包括粘土纳米颗粒、碳纳米管、云母粉末等。
合适的酚醛树脂通常符合美国军用规格(United States MilitarySpecification)MIL-R-9299C。优选地,树脂为苯酚甲醛树脂,并且可以为甲阶酚醛树脂或酚醛环氧树脂。可以使用其它醛,例如糠醛,也可以使用其它酚,例如对苯二酚和对甲酚。对甲酚的制备和此类树脂的特性描述于“Phenolic Resins,”作者A.Knop和L.A.Pilato,Springer-Verlag,Berlin,1985年。只施加热就可以固化甲阶酚醛树脂,而热塑性酚醛树脂的固化需要另外存在甲醛生成物质,例如六亚甲基四胺(也称为六胺)。甲阶酚醛类型树脂是优选的。合适的酚树脂购自诸如Hexion Specialty Chemicals,Columbus,OH、Georgia Pacific Resins Inc.(Atlanta,AL)或Durez Corporation(Detroit,MI)的公司。
当在芯材形成之前进行纤维网的完全或部分树脂浸渍时,优选树脂是部分固化的。这种部分固化方法(称为B-分段)在复合材料工业中是熟知的。我们用B-分段表示聚合反应中的中间体阶段,其中树脂遇热软化并且是塑性的和可溶的,但是没有完全溶解或者熔合。B-分段的加强纤维网仍能够进一步加工成期望的芯材形状。在其中第一涂覆步骤中的树脂含量很低,例如5至15重量%,或纤维网非常薄,例如0.5至0.7密耳厚的实施例中,在形成芯材之前树脂可以完全固化。
当在芯材已经形成之后进行树脂浸渍时,通常顺序地进行以下重复的步骤:浸渍、然后除去溶剂并使树脂固化。优选的最终芯材密度(非织造片材加上树脂)在20至150kg/m3的范围内。在树脂浸渍过程中,将树脂涂覆到加强纤维网上并吸收到加强纤维网中。
树脂可用作溶剂或分散介质(例如水、丙酮、异丙醇、丁酮、乙酸乙酯、乙醇和甲苯)中的溶液或分散体。可以使用这些溶剂的混合物,以实现可接受的溶剂从芯材的蒸发速率。所用溶剂的量将根据多个因素而广泛改变,这些因素包括所用芯材材料的类型。一般来讲,应当添加溶剂的量可提供根据已知工艺容易地应用的树脂溶液。
热塑性树脂可以熔融相使用,或可在加热和压力的作用下作为膜施用。呈纤维、沉析纤维、纸浆或粉末形式的热塑性树脂也可以作为另外纤维网的组分引入,然后施加热和压力,从而提供更好的树脂渗透和连续基质的形成。一些树脂,如苯并恶嗪树脂,可作为热熔融粘合剂施用,然后在适当温度下固化。
所施用树脂涂层的量将根据多个因素而变化。例如,相对多孔并且具有高空隙率的非织造材料将需要更多树脂,以便实现蜂窝结构壁的足够润湿和填充。对于相对无孔的芯材材料或具有低空隙率的材料,基质树脂的量可以相对低。根据已知的块浸渍或纤维网涂覆工序将涂层树脂施用到芯材上。涂覆之后,本发明的芯结构的树脂涂覆纤维网具有至少14GPa的平面内杨氏模量。在一些实施例中,杨氏模量为至少20GPa或甚至30GPa。
在将加强纤维网制成蜂窝结构芯结构时,有两种基本制造方法:伸展或起皱。两种方法均为本领域的人们所熟知,并且在Engineered MaterialsHandbook,Volume1-Composites,ASM International,1988(工程材料手册,第一卷一复合物,美国材料信息学会,1988年)第721页进一步详细说明。
在一些实施例中,在伸展或起皱工艺之前,可用第一量的涂层树脂涂覆纤维网,在蜂窝结构形成之后以第二量施用残留的树脂。
在将加强纤维网制成折叠芯结构时,需要不同的生产技术。美国专利6,913,570B2和7,115,089B2以及美国专利申请2007/0141376中描述了用于将纤维网坯转换加工为折叠芯结构的方法。在一些实施例中所有的涂层树脂均在折叠芯材形成之后施用,而在其它实施例中在芯材形成之前用第一量的涂层树脂涂覆纤维网基底,芯材形成之后以第二量涂覆残留的涂层树脂。
用于在芯材形成之前和之后涂覆纤维网的方法为本领域的人们所熟知。
施用基质树脂之前加强纤维网的厚度取决于蜂窝结构芯材的最终用途或期望特性,并且在一些实施例中通常为25至100毫米(1至4密耳)厚。在一些实施例中,纤维网的基重为10至50克/平方米(0.3至1.5盎司/平方码)。
多层纤维网
本发明还涉及包含涂覆有热固性或热塑性树脂的非织造纤维的多层加强纤维网的结构用芯材,其中
(i)加强纤维网包含至少一个碳纳米管的第一层和至少一个包含长丝的第二层,所述长丝具有大于1微米的直径、10至65克/分特的韧度以及100至3500克/分特的模量,并且
(ii)所述涂层树脂占纤维网加上树脂的重量的15至75重量%。
图5A大致在“50”处示出包含第一层51和第二层52的多层加强纤维网。图5B大致在“53”处示出包含位于第二层52两侧的两个第一层51的多层加强纤维网。图5C大致在“54”处示出包含第一层51,第一层的两侧各有一个第二层52的多层加强纤维网。图5D大致在“55”处示出包含交替的分别显示于51和52的第一层和第二层的多层加强纤维网。图5E大致在“56”处示出包含多个第一层51毗连多个第二层52的多层加强纤维网。对于多层加强纤维网,可以设想纤维网内各层的数目和位置的其它组合。可以通过机械或化学手段将相邻层结合在一起。机械手段的例子包括缝编或针刺。化学手段的一个例子为粘合剂粘结。
第一层
包含碳纳米管的多层加强纤维网的第一层如上所述。
第二层
在本发明的一些实施例中,多层加强纤维网的至少一个第二层为纸材形式的非织造片材。优选的第二层的纸材包含高强度纤维和基料。在一个实施例中,纸材包含10至100重量%的纤维和相应的0至90重量%的基料。在另一个实施例中,纸材包含10至85重量%的纤维和15至90重量%的基料。在另一个实施例中,纸材包含50至100重量%的纤维和0至50重量%的基料。
高强度纤维具有10至65克/分特的韧度。在一些实施例中,纤维韧度为15至40克/分特;并且在其它实施例中,韧度为20至35克/分特。纤维优选具有100至3500克/分特的模量。在一些实施例中,模量为150至2700克/分特。纤维优选具有50至4,500分特的线密度。在一些实施例中,线密度为100至3500分特;并且在其它实施例中,线密度为300至1800分特。纤维优选具有3.6至5.0百分比的断裂伸长率。在一些其它实施例中,断裂伸长率为3.6%至4.5%。
在一个实施例中,高强度纤维的长度为0.5至26mm。在另一个实施例中,纤维的长度为1至8mm,并且在另一个实施例中,纤维的长度为1.5至6mm。在一个实施例中,此类纤维的直径为5至14微米。
加强纤维网也可以包含与较高强度纤维共混的较低强度和模量的纤维。共混物中较低强度纤维的量将根据折叠芯结构所期望的强度而变化。低强度纤维的量越高,芯结构的强度将会越低。在一个优选的实施例中,较低强度纤维的量不应当超过30%。此类较低强度纤维的例子为间位芳族聚酰胺纤维和聚(乙烯对苯二甲酰胺)纤维。
加强纤维网可包含小量的无机颗粒,并且代表性的颗粒包括云母、蛭石等等;这些性能增强添加剂的加入旨在向非织造片材和最终的折叠芯结构赋予诸如改善的耐火性、热导率、尺寸稳定性等特性。
在一些实施例中,纤维网厚度为25至100微米(1至4密耳),并且纤维网基重为10至50克/平方米(0.3至1.5盎司/平方码)。
纤维网的高强度纤维可以呈单独使用或组合使用的短纤维(毛束)或纸浆的形式。
一般通过将连续的卷绕丝切割成特定长度的段来制备絮凝物。如果絮凝物的长度小于0.5毫米,那么一般来讲太短,不能形成具有足够强度的纸材;如果絮凝物的长度大于26毫米,那么非常难以形成均匀的湿铺纤维网。难以制备具有足够横截面均匀度和可重复生产性的直径小于5微米的絮凝物,尤其是直径小于3微米的絮凝物。如果絮凝物的直径大于20微米,那么非常难以形成轻至中等基重的均匀纸材。
如本文所用,术语“纸浆”是指具有杆和一般从其中延伸的纤丝的纤维材料的颗粒,其中杆一般为柱形并且直径为约10至50微米,并且纤丝为一般附接到杆上的细小的、毛发样的构件,所述构件测量的直径仅为一微米的若干分之几或者几微米并且长度为约10至100微米。在美国专利5,084,136中一般性地描述了一种用于制备芳族聚酰胺纸浆的可能的例证性方法。
纸材中一种优选的基料为沉析纤维。如本文所用,术语“沉析纤维”是指小的薄膜状的基本上为二维颗粒的非常细分的聚合物产品,其具有大约100至1000微米的长度和宽度以及大约0.1至1微米的厚度。通常通过使聚合物溶液流动至与该溶液的溶剂不混溶的液体的凝固浴中来制备沉析纤维。聚合物溶液物流在聚合物凝固时经历剧烈剪切力和紊流。沉析纤维的制备在美国专利3,756,908中提出,工艺的综述性讨论存在于美国专利2,999,788。应当根据美国专利3,756,908的教导内容来精修沉析纤维,只精修到用于允许最终纸的持久压实和饱和度的程度。
用于本发明的沉析纤维的优选聚合物包括芳族聚酰胺(聚间苯二甲酰间苯二胺和聚对苯二甲酰对苯二胺)。其它基料包括聚磺酰氨(PSA)、聚苯硫醚(PPS)和聚酰亚胺。其它基料材料为一般形式的树脂,并且可以为环氧树脂、酚醛树脂、聚脲、聚氨酯、三聚氰胺甲醛树脂、聚酯、聚醋酸乙烯酯、聚丙烯腈、醇酸树脂等等。优选的树脂为水分散性和热固性的。最优选的树脂基料包括水分散性环氧树脂。
高强度纤维和沉析纤维的组成可以是变化的。优选的高强度纤维种类包括芳族聚酰胺、液晶聚酯、聚吲哚、聚吡啶并唑、聚磺酰胺、聚苯硫醚、聚烯烃、碳、玻璃和其它无机纤维或者它们的混合物。
使用沉析纤维和短纤维制成的纸材纤维网曾描述于授予Gross的美国专利3,756,908和授予Lin的美国专利5,137,768。
合适的高强度纤维是对位芳族聚酰胺。用于制备芯结构的可商购获得的对位芳族聚酰胺高模量高强度纤维加固纸材为N636纸材,由E.I.DuPont de Nemours and Company(Wilmington,DE)出售。芯结构也可以由间位芳族聚酰胺纤维非织造纤维网制成,也以商品名购自杜邦。
纸纤维网也可以包含纤维素,如由牛皮纸举例说明。纤维素也可以存在于包含芳族聚酰胺和纤维素纤维的共混物的纸材中。
合适的玻璃纤维包括S-玻璃和E-玻璃。E-玻璃是可商购获得的低碱玻璃。一种典型的组合物由54重量%的SiO2、14重量%的Al2O3、22重量%的CaO/MgO、10重量%的B2O3和少于2重量%的Na2O/K2O组成。一些其它材料也可以杂质含量存在。S-玻璃是可商购获得的氧化镁-氧化铝-二氧化硅玻璃。该组合物比E-玻璃更硬、更坚固、也更贵,其通常用于聚合物基质复合材料。
基于聚丙烯腈的碳纤维可以标准、中间或高模量等级商购获得,如购自Toray Carbon fibers America(Decatur,AL)的购自HexcelCorporation,Stamford,CT的碳纤维也可以为沥青基的,如购自Cytec Carbon fibers LLC(Piedmont,SC)的
在一些实施例中,第二层可以为包含碳纳米管的非织造片材。
本发明的蜂窝结构的孔室壁或折叠芯材的外表面除了包含树脂浸渍或涂覆的非织造加强纤维网之外,还可以包含一层或多层树脂浸渍或涂覆的织造材料或针织物或膜。织造材料和针织物的例子包括合并了芳族聚酰胺、碳纤维或玻璃纤维的那些。
合适膜的例子包括聚酰亚胺、聚磺酰氨(PSA)、聚苯硫醚(PPS)、液晶聚酯、PEEK和PEKK膜。
多层加强纤维网结构可在芯材形成之前形成,或在芯材形成期间直接形成。在第一种情况下,可在涂覆/浸渍过程中将各层合并在一起。在第二种情况下,可以应用美国专利号6,592,963中描述的方法。
涂层树脂
多层加强纤维网涂覆有树脂。涂层树脂、涂覆到纤维网上或里面的树脂量以及涂覆方法如先前所描述。
复合板
基于CNT纤维网或包含至少一层CNT的多层加强纤维网的芯结构,可用于制造具有粘结到芯结构的至少一个外表面上的面板的结构化复合板。所述面板材料可以为塑料片材或板材、纤维加强的塑料(预浸料坯)或金属。在压力并且通常在加热的条件下,用粘性薄膜或者来自预浸料坯中的树脂将面板附接到芯结构上。在压机、烤箱或者高压釜中进行固化。此类技术为本领域的技术人员所熟知。
测试方法
根据ASTM D374-99(2004年审核)来测定浸渍基质树脂之前和之后的片结构的厚度。
根据ASTM D646-96(2001年审核)来测定浸渍基质树脂之前和之后的片结构的基重和密度。
通过比较涂覆树脂之前和之后样本的干燥重量,并且计算树脂在原料纸材和固化树脂的总重量中的重量%,来测定树脂浸渍量。
根据ASTM D828来测定树脂浸渍之前和之后片结构的拉伸特性(杨氏模量、抗拉刚度、拉伸强度、抗张指数和断裂伸长率)。
比刚度计算为涂布纸或浸渍纸的第一(纵)方向和第二(横)方向的算术平均抗拉刚度值除以涂布纸的基重。
通过用第一(纵)方向的杨氏模量除以第二(横)方向的杨氏模量来获得杨氏模量比。
实例
在以下实例中,除非另外指明,否则所有份数和百分比均按重量计,并且所有度数均按摄氏度计。根据本发明制备的实例用数值来指示。对照例或比较例用字母来指示。与比较例和本发明的实例相关的数据和测试结果示于表1。
在以下实例中,所用的酚醛树脂为酚醛树脂溶剂化树脂类型GP445D05,由Geogia-Pacific Resins,Inc供应。碳纳米管片由NanocompTechnologies Inc.供应。除非独立指出,否则树脂固化循环为85度15分钟、121度15分钟和180度120分钟的三阶段循环。
比较例A
将两片1.4N636纸材层压在一起,同时用酚醛树脂浸渍,然后固化树脂。固化的层合结构的机械性能如表1所示。
实例1
用酚醛树脂浸渍具有基重10.4gsm、厚度0.019mm、密度0.58g/cu.cm、第一和第二方向的拉伸强度分别为7.0N/cm和9.3N/cm、第一和第二方向的断裂伸长率分别为16.0%和14.1%的碳纳米管片结构。浸渍之后,固化树脂。固化片结构的机械性能如表1所示。
实例2
在环境温度和3000N/cm的线压力下,将具有基重27.6gs/m、厚度0.047mm、密度0.58g/cm3、第一和第二方向的拉伸强度分别为37N/cm和20N/cm、第一和第二方向的断裂伸长率分别为15.7%和14.1%的碳纳米管片结构在金属辊之间压延。压延片材具有基重27.6g/m2、厚度0.036mm、密度0.78g/cm3、第一和第二方向的拉伸强度分别为33N/cm和24N/cm、第一和第二方向的断裂伸长率分别为7.4%和9.7%。用酚醛树脂浸渍该片材,然后固化。固化片结构的机械性能如表1所示。
实例3
将实例2的压延片材在两片1.4N636对位芳族聚酰胺纸材之间层压,同时用酚醛树脂浸渍。芳族聚酰胺纸可购自E.I.duPont de Nemoursand Company,Wilmington,DE。浸渍之后,固化层合结构。固化的层合结构的机械性能如表1所示。
实例4
在环境温度和3000N/cm的线压力下,将两层实例2的纳米管片在金属辊之间压延。压延的层合片具有基重55.9gsm、厚度0.064mm和密度0.88g/cm3。用酚醛树脂浸渍两层片层合体并固化。固化的层合结构的机械性能如表1所示。
实施5
由实例2的CNT片形成蜂窝结构。用酚醛树脂浸渍该片。树脂固化循环的第三步是于180度三分钟而不是与前面的实例一样于180度20分钟。
以2mm的宽度和5mm的间距将粘合剂节线施用到片材表面。粘合剂包含50%固体溶液,固体溶液包含70重量份的环氧树脂,识别为Epon826并由Shell Chemical Co.出售;30重量份的弹性体改性的环氧树脂,识别为Heloxy WC8006并由Wilmington Chemical Corp(Wilmington,DE,USA)出售;54重量份的双酚A-甲醛树脂固化剂,识别为UCAR BRWE5400并由Union Carbide Corp.出售;0.6重量份的乙二醇醚溶剂中的2-甲基咪唑,识别为Dowanol PM并由The Dow Chemical Company出售,并且由Miller-Stephenson Chemical Co.出售;和1.5重量份的热解法二氧化硅,识别为Cab-O-Sil并由Cabot Corp出售。在烘箱中于130℃进行6.5分钟将粘合剂部分固化在片上。
将具有粘合剂节线的片材切割成500mm的长度。将四十个片一个叠一个地堆起来,使得每个片中的节线相对于相邻片偏置半节,即相邻节线之间间距的一半。偏置可交替地发生在一侧或另一侧上,使得最终堆叠件均匀地竖直。然后将多个堆叠的片于粘合剂的软化点在板之间热压,导致粘合剂节线熔化和固化,冷却后将相邻片粘结在节线的区域中。对于以上节线粘合剂,压制循环为于140度进行30分钟,然后于177度进行40分钟。所施加的压力为3.5kg每平方cm。
然后,将粘合的CNT片的叠堆沿与堆叠方向相反的方向展开,从而形成具有等边横截面的孔室。每个片材在彼此间延伸,使得沿粘合的节线的边缘折叠片材,并且未粘合的部分沿张力方向延伸,从而使片材彼此分离。使用机架来展开蜂窝结构并将其保持为展开的形状。
然后将展开的蜂窝结构放置在包含酚醛树脂的浴槽中。在用树脂浸渍之后,将蜂窝结构从浴槽中取出,并在干燥炉中用热空气首先于82度干燥15分钟,然后于121度干燥15分钟,最后于182度干燥60分钟。该干燥循环将除去溶剂并固化树脂。随后移除固定蜂窝结构的机架。
实例6
在两层片成形纸材之间压延实例2的CNT片。该纸材包含70重量%的对位芳族聚酰胺絮凝物和30重量%的间位芳族聚酰胺沉析纤维。对位芳族聚酰胺絮凝物为49,其具有1.5旦尼尔/长丝(1.7分特/长丝)的标称长丝线密度、6.4mm的切割长度、24克/旦尼尔的韧度和960克/旦尼尔的模量。这种絮凝物购自E.I.DuPont de Nemours and Company(Wilmington,DE)。间位芳族聚酰胺沉析纤维如授予Gross的美国专利3,756,908中所述制备。在环境温度和2000N/cm的线压力下进行压延。
由压延的3层片形成折叠芯材。用酚醛树脂浸渍该片。蒸发溶剂并将树脂部分固化至B分段,由此制备树脂浸渍的非织造片材(预浸料坯)。然后根据授予Kehrle的美国专利6,913,570,由该预浸渍的B-分段材料形成折叠芯材。制备出了如图4所示的之字形折叠图案。所述芯材的几何参数为:V=14.26mm,T=5.00mm,S=4.63mm,L=10.62mm,H=30.00mm。通过将最终的芯材在180C加热处理1.5小时来完全固化树脂。最终的折叠芯结构具有25.0kg/m3的密度和总芯材重量41%的树脂含量。
表1
*FD=第一(纵)方向 *SD=第二(横)方向
结果显示,在用树脂浸渍之后,包含碳纳米管的增强非织造纤维网提供具有高杨氏模量(14GPa或更高,如依照实例11)的蜂窝结构或折叠的芯材壁。
在转变成蜂窝结构或折叠芯材之前CNT非织造片材的另外压实,向芯结构的壁提供甚至更高的杨氏模量和比刚度,如由实例2和4所示,同时仍保持合格水平的张力性能。
包含碳纳米管的非织造层和对位芳族聚酰胺纸材层的加强纤维网(实例3)在用基质树脂浸渍之后,与由两层对位芳族聚酰胺纸材制成的类似结构(比较例A)相比较,具有显著更高的杨氏模量、比刚度和抗张指数。
所有实例显示,可能保持沿第一方向的杨氏模量与沿第二方向的杨氏模量的比率低于2。该特征是重要的,因为其允许蜂窝结构和折叠芯结构保持最终结构的压缩和剪切特性之间的最佳平衡。
来自实例2的数据也示出,碳纳米管的非织造片材在压延后未损失拉伸强度。压延后断裂伸长率的降低不会显著地影响性能,因此被认为是合格的。因此,为了最终复合材料中特性更好,片结构的密度被增大。尽管密度增大,但是片材仍具有不同的芯材制备方法所需的良好的可加工性特性。
Claims (15)
1.包含非织造纤维加强碳纳米管纤维网的结构用芯材,所述纤维网涂覆有热固性或热塑性树脂,其中:
(i)所述碳纳米管在所述加强纤维网内取向为使得在树脂涂覆之后,所述纤维网在平面内沿第一方向的模量与沿正交于所述第一方向的第二方向的模量的比率不大于2.0,
(ii)所述树脂涂覆的纤维网的平面内杨氏模量为至少14GPa,并且
(iii)涂层树脂占纤维网加上树脂的重量的15至75重量%。
2.根据权利要求1所述的芯材,其中所述树脂涂覆的纤维网的平面内杨氏模量为至少20GPa。
3.根据权利要求1所述的芯材,其中所述树脂涂覆的纤维网的平面内杨氏模量为至少30GPa。
4.根据权利要求1所述的芯材,其中沿第一方向的模量与沿正交于第一方向的第二方向的模量的比率不大于1.5。
5.根据权利要求1所述的芯材,其中在用树脂涂覆之前所述加强纤维网的密度为至少0.7g/cm3。
6.根据权利要求1所述的芯材,其中所述芯材为蜂窝结构的形式。
7.根据权利要求6所述的芯材,其中所述蜂窝结构的孔室形状为六边形。
8.根据权利要求1所述的芯材,其中所述芯材为折叠结构的形式。
9.包含涂覆有热固性或热塑性树脂的非织造纤维多层加强纤维网的结构用芯材,其中:
(i)所述加强纤维网包含至少一个碳纳米管的第一层和至少一个包含纤维的第二层,所述纤维具有大于1微米的直径、10至65克/分特的韧度以及100至3500克/分特的模量,并且
(ii)涂层树脂占纤维网加上树脂的重量的15至75重量%。
10.根据权利要求9所述的芯材,其中:
(i)所述纤维网在平面内沿第一方向的模量与沿正交于所述第一方向的第二方向的模量的比率不大于2.0,并且
(ii)所述树脂涂覆的多层纤维网的平面内杨氏模量为至少14GPa。
11.根据权利要求9所述的芯材,其中所述芯材为蜂窝结构或折叠芯结构的形式。
12.根据权利要求9所述的芯材,其中沿第一方向的模量与沿正交于所述第一方向的第二方向的模量的比率不大于1.5。
13.根据权利要求8所述的芯材,其中所述至少一个第二层的纤维为对位芳族聚酰胺纤维、玻璃纤维、碳纤维或它们的共混物。
14.复合板,其包含根据前述权利要求中任一项所述的芯结构和附接到所述芯结构的至少一个外表面的至少一个面板。
15.根据权利要求14所述的复合板,其中所述面板由树脂浸渍的纤维、塑料或金属制成。
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