CN106794653B - 具有高压缩强度的蜂窝结构芯 - Google Patents

具有高压缩强度的蜂窝结构芯 Download PDF

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CN106794653B
CN106794653B CN201580054103.9A CN201580054103A CN106794653B CN 106794653 B CN106794653 B CN 106794653B CN 201580054103 A CN201580054103 A CN 201580054103A CN 106794653 B CN106794653 B CN 106794653B
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M.R.勒维特
D.W.卡卡
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DuPont Safety and Construction Inc
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Abstract

本发明涉及制备纤维强化复合结构的方法,所述方法包括以下步骤:(i)形成具有至少200秒/100毫升的Gurley空气阻力的纸片,所述纸片包含30至70重量%的对位芳纶纤维,(ii)在所述纸片的两个表面上沉积基于所述纸张重量计至多5重量%的量的压缩增强层,(iii)由步骤(ii)的纸片形成蜂窝结构,以及(iv)向步骤(iii)的蜂窝结构施加基体树脂涂层。

Description

具有高压缩强度的蜂窝结构芯
技术领域
本发明涉及高压缩强度蜂窝结构芯以及由包含对位芳纶纤维和沉析纤维的纸张制备所述芯的方法。
背景技术
由对位芳纶纤维纸张或湿法成网非织造材料制成的用于夹心板的芯结构(大多数呈蜂窝结构形式)用于不同的应用中,但主要用于航空和航天工业中,其中强度对重量或硬度对重量的比率具有极高的值。传统上,此类芯结构已最优化化,使得芯具有最大剪切模量(硬度)。例如,授予Lin的美国专利5,137,768描述了由高密度纸张制成的蜂窝结构芯,所述纸张包括50重量%或更多的呈絮凝物(切割纤维)形式的对位芳纶纤维,其中所述组合物的其余部分为粘合剂和其它添加剂。
在许多情况下,已经实现了改善的芯剪切性能,而没有显著改善芯压缩强度。在一些情况下,蜂窝结构芯重量减小,同时保持相同或更好的剪切性能,导致部分牺牲了芯的压缩强度。因此,持续需要改善基于对位芳纶纤维纸张的蜂窝结构芯的压缩强度。
发明内容
本发明涉及制备纤维强化复合结构的方法,所述方法包括以下步骤:
(i)形成具有至少200秒/100毫升的Gurley空气阻力的纸片,所述纸片包含30至70重量%的对位芳纶纤维,
(ii)在纸片的两个表面上沉积基于所述纸张重量计至多5重量%的量的压缩增强层,
(iii)由步骤(ii)的纸片形成蜂窝结构,以及
(iv)向步骤(iii)的蜂窝结构施加基体树脂涂层。
本发明还涉及蜂窝结构芯,所述蜂窝结构芯依次包括
(i)纸片,所述纸片包含间位芳纶沉析纤维、对位芳纶沉析纤维、或它们的组合,
(ii)以基于所述纸张重量计至多5重量%的量沉积到所述纸片的两个外表面上的压缩增强层,以及
(iii)涂覆到所述压缩增强层表面上的基体树脂涂层树脂,其中所述基体涂层树脂为酚醛树脂、聚酰亚胺、聚醚酰亚胺、环氧树脂、或它们的组合。
附图说明
图1a和图1b为六边形形状的蜂窝结构的图示。
图2为六边形巢室形状的蜂窝结构的另一图示。
图3为具有面板的蜂窝结构的例证。
图4示出通过本发明蜂窝巢室壁的截面。
具体实施方式
本发明涉及蜂窝结构芯,所述蜂窝结构芯包括具有限定多个蜂窝巢室的表面的多个互连的壁,其中所述巢室壁由纸张形成,在用树脂浸渍之前,所述纸张包含30-70重量份的对位芳纶纤维和30-70重量份的芳纶沉析纤维,并且具有至少200秒/100毫升的Gurley空气阻力。另外,纸张表面通过涂层(压缩增强层)改性,其随后有助于在蜂窝结构中提供改善的压缩粘结强度。
更优选地,所述巢室壁由纸张形成,在用树脂浸渍之前,所述纸张包含50-70重量份的对位芳纶纤维和30-50重量份的芳纶沉析纤维,具有至少500秒/100毫升的Gurley空气阻力。
已发现在压缩增强层材料和优化以具有至少200秒/100毫升的Gurley空气阻力的纸张之间的令人惊奇的协同增强效应。这些特征当单独使用时均不增强压缩强度,但是当组合时,观察到增强的性能。Gurley空气阻力是纸张密度(孔隙率)的便利量度。还令人惊奇的是,发现蜂窝结构芯压缩强度的进一步改善与使纸张密度高于0.8g/cm3相关。
蜂窝结构
图1a为本发明一个蜂窝结构1的平面图,并且示出了由巢室壁3形成的巢室2。图1b为图1a中所示蜂窝结构的正视图,并且示出了在巢室壁的两端形成的所述两个外表面或面4。所述芯也具有边缘5。图2为蜂窝结构的三维视图。示出了具有六边形巢室2和巢室壁3的蜂窝结构1。图2在10处示出了蜂窝结构的“T”尺度或厚度。示出了六方形巢室;然而,其它几何排列也是可能的,其中正方形巢室、过度扩展巢室和弯曲芯巢室是最常见的可能排列。此类巢室类型在本领域中是熟知的,并且关于可能几何巢室类型的其它信息可参考T.Bitzer的Honeycomb Technology(Chapman&Hall出版社,1997年)。
图3示出了由蜂窝结构芯6装配成的结构夹心板5,所述芯具有连结至所述芯的所述两个外表面上的面板7和8。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材料;然而也可使用金属面板。对于金属面板,并且在某些情况下对于预浸料坯,也使用粘合剂膜9。通常在芯的任一侧上存在至少两个预浸料坯表层。
将幅材基底如纸张转变成蜂窝结构芯的方法是本领域技术人员熟知的,并且包括膨胀和波纹。膨胀方法尤其适用于由纸张制备芯。此类方法在工程材料手册第1卷-复合材料(ASM International,1988)第721页中进一步详述。纸幅可在形成蜂窝结构之前或之后用基体树脂涂覆。可使用在施加到纸张上之后交联的树脂,以优化最终性能如刚度和强度。树脂的示例包括环氧树脂、酚醛树脂、丙烯酸类树脂、聚酰亚胺以及它们的混合物,其中酚醛树脂为优选的。United States Military Specification MIL-R-9299C规定了适当的树脂特性。芯的最终机械强度是若干因素组合的结果。主要的已知促成因素是纸张组成和厚度、巢室尺寸和最终芯密度,如用树脂涂覆后。巢室尺寸是蜂窝内芯巢室内的内切圆的直径。就对位芳纶芯而言,典型的巢室尺寸在1/8″-1/4″(3.2mm-6.2mm)范围内,但其它尺寸也是可能的。典型的最终芯密度在38-96kg/m3范围内。
对于相同的巢室尺寸、相同的最终芯密度和相同的树脂含量,与来自本领域已知的对位芳纶纤维纸张的其它芯相比,本发明的芯具有改善的压缩强度。
图4一般在40处示出通过本发明蜂窝巢室壁的截面。所述纸张在41处示出,压缩增强层在42处示出,基体树脂涂层在43处示出。
该概念也适用于其它芯结构如折叠芯。折叠芯的示例描述于美国专利6,935,997B2;6,800,351 B1和6,913,570 B2中。
纸张
用于制备芯的纸张的厚度取决于芯结构的最终用途或期望性质,并且在一些实施方案中为0.6至20密耳(15至500微米)厚。更优选地,厚度为1.0至3.0密耳(25至75微米)。在一些实施方案中,纸张的基重为0.5至6盎司/平方码(15至200克/平方米)。
除了对位芳纶纤维之外,本发明芯纸张还可包含其它纤维,如间位芳纶、碳、聚吲哚、聚吡啶并唑、聚醚酰亚胺、聚苯砜、液晶聚酯。另外,所述纸张可包含无机颗粒如云母、蛭石等;这些性能增强添加剂的加入向所述纸张和最终芯结构赋予性能如改善的耐火性、导热性、尺寸稳定性等。
用于制备本发明蜂窝结构芯的纸张可在实验室用筛分仪至商业规模造纸机器范围内的任何规模的设备上形成,包括如长网造纸机或斜网造纸机的常用机器。典型方法涉及:制造纤维材料的分散体诸如絮凝物和/或纸浆,并且制备含水液体中的沉析纤维,从分散体中排出液体以获得湿组合物并干燥湿纸组合物。可通过如下方式来制备分散体:分散纤维,然后加入沉析纤维;或分散沉析纤维,然后加入纤维。也可通过组合纤维的分散体与沉析纤维的分散体来制备最终分散体。所述分散体可任选地包含其它添加剂诸如无机材料。来自分散体中絮凝物和纸浆的纤维的浓度以所述分散体的总重量计可在0.01至1.0重量%范围内。沉析纤维浓度的合适范围的一个示例为:按固体的总重量计,其应当等于或小于30重量%。在典型方法中,分散体的含水液体通常为水,但是可包括各种其它物质,例如pH值调节材料、成型助剂、表面活性剂、消泡剂等。含水液体通常以如下方式从分散体中排出:将分散体引导至筛网或其它有孔支撑件上,保留分散的固体,然后使液体流过,从而得到湿纸组合物。湿组合物在支撑件上形成之后,通常通过真空或其它压力进一步脱水,并且通过蒸发剩余液体进一步干燥。
在一个优选实施方案中,可将纤维和沉析纤维一起制浆以形成混合物,该混合物在网筛或网带上转化成纸张。参考授予Tokarsky的美国专利4,698,267和4,729,921;授予Hesler等人的5,026,456;授予Kirayoglu等人的5,223,094和5,314,742中的用于由芳纶纤维和芳纶沉析纤维形成纸张的例证性方法。
纸张形成后,将它压延以达到最终所需的密度和厚度。纸张制造过程中的任选最终步骤可包括在电晕或等离子气氛中对纸张进行表面处理以进一步改善芯结构的机械特性。
一般通过将连续的卷绕丝切割成具体长度的段来制备絮凝物。絮凝物长度优选为2至25毫米。如果絮凝物的长度小于2毫米,其一般太短而无法向纸张提供足够的强度;如果絮凝物的长度大于25毫米,其将非常难以形成均匀的湿法成网纤维网。制备的具有小于5微米,尤其是小于3微米的直径的絮凝物难以具有足够的剖视均匀性和再现性;如果絮凝物的直径大于20微米,其将非常难以形成均匀的纸张重量由轻至中等的纸张。
通常通过使聚合物溶液流动至与所述溶液的溶剂不混溶的液体凝固浴中,来制备沉析纤维。聚合物溶液流在聚合物凝聚时受到剧烈剪切力和紊流的影响。本发明的沉析纤维材料可选自间位或对位芳纶或它们的共混物。
芳纶纤维
本发明蜂窝巢室壁纸张中的对位芳纶纤维可为切割纤维(絮凝物)形式、纸浆形式、或它们的共混物。絮凝物包括通过将连续长丝纤维切割成短长度而没有显著原纤化而制得的短纤维。适用于本发明的增强短纤维是授予Hoiness的美国专利5,474,842中公开的那些。
如本文所用,术语“纸浆”是指具有纤柄和通常从纤柄延伸的原纤维的纤维材料颗粒,其中纤柄通常为柱形并且直径为10至50微米,并且原纤维为通常与纤柄连接的细毛发状构件,经测量其直径仅为一微米的若干分之一或几微米,并且长度为约10至100微米。
如本文所用,术语“沉析纤维”是指基本上为二维薄膜状小颗粒的极细分的聚合物产品,已知其具有100至1000微米的长度和宽度以及0.1至1微米的厚度。
如本文所用,术语芳纶是指聚酰胺,其中至少85%的酰胺(-CONH-)键直接连接至两个芳族环。添加剂可与芳纶一起使用。实际上已发现,可将多达10重量%的其它聚合材料与芳纶共混,或者可使用共聚物,所述共聚物具有多达10%的替代芳纶的二胺的其它二胺,或多达10%的替代芳纶的二酰氯的其它二酰氯。对位芳纶纤维和这些纤维的各种形式可从E.I.du Pont de Nemours and Company(Wilmington,Delaware)以商标以及从Teijin,Ltd.以商标购得。
压缩增强层
如本文所用,术语“压缩增强层”是指可以任何适宜的量施加在纸张表面上的任何物质,所述量可为所述纸张重量的至多5重量%,并且包括5重量%。在施加基体树脂涂层之前,压缩增强层的材料可在蜂窝结构制备过程中的任何方便阶段施加到纸张上。例如,在用于制备蜂窝结构的膨胀工艺情况下,可在印刷节点线之前将压缩增强层施加到纸张上。在用于制备蜂窝结构的波纹工艺情况下,可在波纹之前将压缩增强层施加到纸张上。在另一个替代形式中,在形成蜂窝结构形状之后,可将压缩增强层施加到纸张上,而不管蜂窝结构制备过程如何。
根据纸张组合物、基体树脂的类型等,可将任何适宜的材料用于压缩增强层。适宜材料的一个示例是基于甘油三缩水甘油醚的环氧树脂涂层。另一个示例是多肽蛋白质-碳纳米管复合物,例如授予Wolf等人的PCT专利申请公开WO2011/027342中所述。偶联剂和引物也可用作本发明中的压缩增强层材料。
压缩增强层可以纸张重量的约0.1%至约5%的任何适宜量施加,这取决于在该层中使用的特定类型材料。
测试方法
纸张密度使用基于ASTM D374-99(2004年再认证)的采用0.9kPa足压测量的纸张厚度计算,而基重通过ASTM D646-96(2001年再认证)测量。使用ASTM D1907-07来测定纤维的纤度。
根据TAPPI T460om-96,通过使用1.22kPa压差测量6.4平方厘米圆形面积纸张的每100毫升气缸位移的空气阻力(秒),确定纸张Gurley孔隙率。
根据ASTM C271/C271M-05测量芯的密度,并且根据ASTM C365/C365M-05测量稳定的压缩强度。
实施例
实施例1
在常规造纸设备上形成由49絮凝物和沉析纤维构成的对位芳纶纤维纸张。纸张的组成为60重量%的絮凝物和40重量%的沉析纤维。絮凝物具有1.5丹尼尔/长丝(1.7分特/长丝)的标称长丝线密度和6.4mm的切割长度。如授予Gross的美国专利3,756,908中所述制备沉析纤维。
然后在2600N/cm的线性压力下,在330℃温度下压延所述纸张。这产生厚度为38微米,密度为0.75g/cm3,基重为0.9oz/yd2(33.9g/m2),并且Gurley空气阻力为700秒/100毫升的最终纸张。
将所述纸张用包含含量分别为17.8、0.11、0.15和72重量%的EX-313树脂(甘油多缩水甘油醚)、Aerosol OT、碳酸钠和软水的水基乳液在线处理,以形成压缩增强层。EX-313由Nagase ChemteX Corporation提供,Aerosol OT由Fitz ChemCorp.提供,并且碳酸钠由Fisher Scientific(Chemicals Division)提供。压缩增强层的总量以所述纸张重量计为1.2重量%。
然后由处理过的纸张形成蜂窝结构。将溶剂化粘合剂的节线以2mm的宽度和5mm的节距施加到纸张表面上,并且除去溶剂。
将具有粘合剂节线的片材切割成500mm的长度。将多个片材以一个位于另一个的上面的方式堆叠起来,使得这些片材中的每一个均按所施加粘合剂节线的一半节距或一半间隔移位到另一个上。移位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。然后在粘合剂的软化点下,在板之间热压多个叠堆片材,致使粘合剂节线流动。移除热量后,粘合剂硬化以将相邻的片材彼此粘合。然后将粘合的芳纶纸片沿与叠堆方向相反的方向膨胀,以形成具有等边截面的巢室。每个片材彼此之间延伸,使得片材沿着结合节点线的边缘折叠,并且未结合的部分在拉伸力的方向上延伸以将片材彼此分离。使用机架来展开蜂窝结构并将其保持为展开的形状。展开的巢室尺寸为3.2mm。
然后将展开的蜂窝结构放置在包含溶剂基MIL-R-9299C标准酚醛树脂的浴中。以液体形式使用酚醛树脂,其中树脂溶解在乙醇中。树脂粘附到并涂覆巢室壁的内表面并且透入到纸张的孔中。在用树脂浸渍之后,将蜂窝结构从浴中取出并且在干燥炉中用热空气干燥以除去溶剂并固化酚醛树脂。将树脂浴中的浸渍步骤和干燥炉中的干燥步骤再重复两次。所述蜂窝结构芯具有如表1中所示的性质。
比较例1
在常规造纸设备上形成由49絮凝物和沉析纤维构成的对位芳纶纤维纸张。纸张的组成为73重量%的絮凝物和27重量%的沉析纤维。絮凝物具有1.5丹尼尔/长丝(1.7分特/长丝)的标称长丝线密度和6.4mm的切割长度。如授予Gross的美国专利3,756,908中所述制备沉析纤维。然后在2600N/cm的线性压力下,在330℃温度下压延所述纸张。这产生厚度为38微米,密度为0.75g/cm3,基重为0.9oz/yd2(33.9g/m2),并且Gurley空气阻力为15秒/100毫升的最终纸张。如实施例1中,在线处理纸张以形成压缩增强层。
然后以与实施例1中所述相同的方式,由处理过的纸张形成蜂窝结构。所述芯具有如表1中所示的性质。
比较例2
除了没有压缩增强层之外,按照实施例1制备纸张和蜂窝结构。所述芯具有如表1中所示的性质。
从表1和图4的数据可看出,对于相同的芯密度,与来自两个比较例的芯相比,本发明的蜂窝结构芯具有令人惊奇的更高压缩强度。
实施例2
如实施例1制备纸张,不同的是将其压延至0.85g/cm3的较高密度。如实施例1,将压缩增强层涂覆到纸张上,并且如前所述制备蜂窝结构芯。该芯的性质也示于表1中。
表1
实施例1 比较例1 比较例2 实施例2
纸张基重(g/m<sup>2</sup>) 3.9 33.9 33.9 33.9
纸张密度,g/cm3 0.75 0.75 0.75 0.85
纸张Gurley空气阻力(秒/100mL) 700 15 700 1500
存在压缩增强层
蜂窝巢室尺寸,(mm) 3.2 3.2 3.2 3.2
芯密度(kg/m<sup>3</sup>) 40 40 40 40
蜂窝结构芯的稳定压缩强度(MPa) 2.14 1.65 1.70 2.30
从表1中的数据可看出,使用具有恰当Gurley空气阻力水平的纸张(比较例2)或使用具有压缩增强层的纸张(比较例1),不足以从对位芳纶纸张获得蜂窝结构芯压缩强度的显著改善。只有恰当Gurley空气阻力水平的特征和如实施例1和2中压缩增强层的特征的组合提供了压缩强度的显著改善,在该情况下分别为约20%和35%。

Claims (5)

1.一种制备纤维强化复合结构的方法,所述方法包括以下步骤:
(i) 形成具有至少200秒/100毫升的Gurley空气阻力的纸片,所述纸片包含30至70重量%的对位芳纶纤维,
(ii) 在所述纸片的两个表面上沉积基于所述纸张重量计至多5重量%的量的压缩增强层,其中所述压缩增强层包含甘油多缩水甘油醚、多肽-碳纳米管复合物、多肽-石墨复合物、或它们的组合,
(iii) 由步骤(ii)的纸片形成蜂窝结构,以及
(iv) 向步骤(iii)的蜂窝结构施加基体树脂涂层。
2.根据权利要求1所述的方法,其中所述纸张包含间位芳纶沉析纤维、对位芳纶沉析纤维、或它们的组合。
3.根据权利要求1所述的方法,其中所述基体涂层树脂为酚醛树脂、聚酰亚胺、聚醚酰亚胺、环氧树脂、或它们的组合。
4.根据权利要求1所述的方法,其中所述纸张密度大于0.8g/cm3
5.一种蜂窝结构,所述蜂窝结构依次包括
(i) 纸片,所述纸片包含间位芳纶沉析纤维、对位芳纶沉析纤维、或它们的组合,
(ii) 以基于所述纸张重量计至多5重量%的量沉积到所述纸片的两个外表面上的压缩增强层,其中所述压缩增强层包含甘油多缩水甘油醚、多肽-碳纳米管复合物、多肽-石墨复合物、或它们的组合,以及
(iii) 涂覆到所述压缩增强层表面上的基体树脂涂层树脂,其中所述基体涂层树脂为酚醛树脂、聚酰亚胺、聚醚酰亚胺、环氧树脂、或它们的组合。
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