CN111433398A - 缝合纱线及包含此种纱线的ncf织物 - Google Patents

缝合纱线及包含此种纱线的ncf织物 Download PDF

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Publication number
CN111433398A
CN111433398A CN201880078491.8A CN201880078491A CN111433398A CN 111433398 A CN111433398 A CN 111433398A CN 201880078491 A CN201880078491 A CN 201880078491A CN 111433398 A CN111433398 A CN 111433398A
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China
Prior art keywords
yarns
stitching
yarn
multifilament
less
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Pending
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CN201880078491.8A
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English (en)
Inventor
D·旁索勒
C·L·雷斯图恰
A·纳赫尔
P-Y·拉阿里
J·毕卡德
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Cytec Industries Inc
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Cytec Industries Inc
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Publication of CN111433398A publication Critical patent/CN111433398A/zh
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    • D04H3/115—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by applying or inserting filamentary binding elements
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Abstract

本披露涉及一种缝合纱线以及含有此种纱线的无屈曲织物。本文所述的缝合纱线是复丝缝合纱线，该缝合纱线的特征在于以下特性中的两种或更多种：(a)包含多个聚合物纤维，(b)具有小于或等于80分特的线密度，(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或(d)具有小于200转/米(r/m)的捻度。本披露还涉及含有该无屈曲织物的纤维预成型件、复合材料、以及复合制品。

Description

缝合纱线及包含此种纱线的NCF织物
相关申请的交叉引用
本申请要求于2017年12月4日提交的美国临时申请号62/594129的优先权，将该申请的全部内容通过援引并入本申请。
技术领域
本发明涉及缝合纱线以及含有此类纱线的NCF织物。本发明进一步涉及含有本文所述的NCF织物的预成型件、复合材料、及复合制品。根据本披露的预成型件、复合材料、及复合制品特别适合于生产用于许多应用如航空领域以及汽车和海军工业中的复合零件。
背景技术
无屈曲织物(NCF)通常包含一层或多层结构纤维、长丝、或纱线，每层具有的纤维、长丝、或纱线是在离散方向上取向的。纤维、长丝、或纱线也被称为增强纤维、长丝、或纱线。这些层典型地通过缝合纱线固结。
然而，此种缝合在缝合穿透这些层的点处限制了纱线在层内的膨胀。效果是在增强纱线之间创建了分隔区，也被称为“鱼眼”。在缝合点处，分隔区留下一个空间，然后当在复合制品和/或零件的生产期间将NCF织物随后与树脂基质组合时，该空间被树脂填充，并且促进形成不期望的富树脂区。
当在复合零件的生产期间将NCF织物与树脂基质组合时形成富树脂区在成品零件内导致具有不均匀结构的区域，在这些区域处湿热应力变得集中。当经受热循环和潮湿周期时，复合零件经历收缩和膨胀应力，并且在富树脂区可能形成微裂纹。因此，持续需要减轻或防止在随后生产的、经受湿热应力的复合零件中出现微裂纹。
Beraud等人的美国专利9,695,533和Wockatz的美国专利8,613,257分别描述了通过减少缝合纱线的纤度来最小化复合零件中富树脂区的尺寸的策略，以改善复合材料的微开裂行为和复合材料的平面内方向上的机械特性。
在本文中，描述了一种新策略，该策略通过减小NCF织物中鱼眼的尺寸来限制复合制品的微开裂行为，该NCF织物用于通过对缝合纱线进行设计来制造。
发明内容
在第一方面，本披露涉及一种无屈曲织物，其包含至少一层单向取向的复丝碳纱线和将这些复丝碳纱线互连的复丝缝合纱线，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
在第二方面，本披露涉及一种纤维预成型件，该预成型件包含本文所述的无屈曲织物。
在第三方面，本披露涉及一种复合材料，该复合材料包含：
-基质树脂，以及
-本文所述的无屈曲织物。
在第四方面，本披露涉及一种复合制品，其通过使本文所述的复合材料固化来获得。
在第五方面，本披露涉及一种用于制造NCF织物的方法，该方法包括使用复丝缝合纱线将多个复丝碳纱线互连成单向取向的层，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
附图说明
图1示出了NCF织物中的分隔区以及当使用根据本发明的复丝缝合纱线时该分隔区的尺寸减小的示意图。
图2示出了(a)具有高捻度量的缝合纱线的效果和(b)具有低捻度量的缝合纱线的效果的示意图。
具体实施方式
本披露涉及一种无屈曲织物，其包含至少一层单向取向的复丝碳纱线和将这些复丝碳纱线互连的复丝缝合纱线，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
如本文使用的，术语“一个/一种(a/an)”、或“该(the)”意指“一个(种)或多个(种)”或“至少一个(种)”，除非另外说明。
如本文使用的，术语“包含”包括“主要由……组成”和“由……组成”。术语“包含”包括“主要由……组成”和“由……组成”。
术语“无屈曲织物(non-crimp fabric或non-crimped fabric)”，有时称为“NCF”，是指包含一层或多层纤维、长丝、或纱线的构造物。单层中的纤维、长丝、或纱线被布置从彼此平行并且在单一方向上取向(即，单向的)。可以堆叠多个层，使得一层的纤维、长丝、或纱线与相邻层的纤维、长丝、或纱线平行取向，或者与相邻层的纤维、长丝、或纱线交叉取向。当一层的纤维、长丝、或纱线与相邻层的纤维、长丝、或纱线交叉取向时，一层的轴线(该轴线是由该层中的纤维、长丝、或纱线的方向确定的)与相邻层的轴线之间的角度实质上是无限可调的。例如，相邻纤维层之间的角度可以是0°或90°，或此角度加或减25°、加或减30°、加或减45°、或者加或减60°，零度方向是通过本领域普通技术人员已知的方法确定的。例如，机器方向可以被指定为0°方向。因此，术语“多轴”是指NCF织物具有多于一个层，每个层沿不同方向取向。多轴织物包括其中的层在两个方向上取向的双轴织物和其中的层在三个方向上取向的三轴织物等等。可以例如通过经向针织织布机或缝编机来生产多轴无屈曲织物。
在实施例中，无屈曲织物包含一层单向取向的复丝碳纱线。在另一个实施例中，该无屈曲织物包含多于一层的单向取向的复丝碳纱线。在实施例中，该无屈曲织物包含多于一层的单向取向的复丝碳纱线，这些层沿相同方向取向。在另一个实施例中，该无屈曲织物包含多于一层的单向取向的复丝碳纱线，这些层沿不同方向取向。
如本文使用的，纱线是一个或多个纤维、一根或多根长丝的连续股，或是呈适合用于生产纺织品、缝纫、钩编、针织、编织、缝合等形式的材料。纱线包括，例如，(1)在没有施加或有意捻度的情况下铺设或捆扎在一起的多根长丝，有时被称为零捻纱线或无捻纱线；(2)铺设或捆扎在一起的并且交织(有假捻)或以某种方式使其变形的多根长丝；(3)铺设或捆扎在一起的具有一定程度的捻度的多根长丝，有时被称为加捻纱线；(4)在有或没有捻度的情况下的单根长丝，有时被称为单丝或单丝纱线。变形纱线可以是通过物理、化学、或热处理或这些的组合而具有明显更大体积的长丝或纺成纱线。在一些情况下，纱线被称为长丝纱线或复丝纱线，二者通常都是由多根长丝制成的纱线。
如本文使用的，“纤维”是指具有高的长度与厚度之比的材料。纤维可以是连续的，在这种情况下，此类纤维被称为长丝，或者是短纤维长度(即离散长度)。
本披露的NCF的单层内的单向取向的复丝碳纱线通过具有某些特性的复丝缝合纱线互连，这些特性有助于减小NCF织物中鱼眼的尺寸，并且从而在由NCF织物制成的复合制品中减小不期望的富树脂区的尺寸。
复丝缝合纱线的聚合物纤维可以是以下各项的纤维：聚酰胺如脂族聚酰胺(PA)、脂环族聚酰胺、芳族聚酰胺、聚邻苯二甲酰胺(PPA)、醚或酯嵌段聚酰胺(PEBAX、PEBA)；聚酯如聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)和聚对苯二甲酸丙二醇酯(PTT)；聚烯烃如聚丙烯(PP)、聚乙烯(PE)、热塑性聚烯烃(TPO)(如乙烯丙烯二烯(EPDM)和乙烯丙烯(EPR)橡胶)；聚苯硫醚(PPS)；聚醚酰亚胺(PEI)；聚酰亚胺(PI)；具有苯基三甲基茚满结构的聚酰亚胺；聚酰胺基酰胺(PAI)；聚砜；聚芳砜如聚醚砜(PES)、聚醚砜-醚醚砜(PES:PEES)、聚醚醚砜(PEES)；聚酮；聚芳醚酮(PAEK)如聚醚酮(PEK)、聚醚醚酮(PEEK)和聚醚酮酮(PEKK)；聚氨酯；聚醚或聚酯-b-氨基甲酸酯；热塑性聚氨酯；聚碳酸酯；聚缩醛；聚苯醚(PPO)；聚醚；聚醚腈；聚苯并咪唑；热塑性弹性体如苯乙烯乙烯丁烯苯乙烯(SEBS)、苯乙烯乙烯丙烯苯乙烯(SEPS)和苯乙烯丁烯苯乙烯(SBS)嵌段共聚物及其氢化型式；硫化热塑性弹性体(TPV)如硫化乙烯丙烯二烯嵌段共聚物；液晶聚合物(LCP)及其组合和共聚物。
在实施例中，复丝缝合纱线的聚合物纤维是聚酰胺、聚酯、聚羟基醚、或其共聚物。在另一个实施例中，复丝缝合纱线的聚合物纤维包括PA 6、PA 6/6、PA 6T、PA 12、PA 6/10、PA 9T、PA 10/10、PA 10T、PA11、PA 6/12、PA 10/12、或者其共混物或共聚物。
复丝缝合纱线的聚合物纤维的特征可以在于密度。如本文使用的，密度是指用于制造纤维的聚合物材料的密度。复丝缝合纱线的聚合物纤维具有从0.5至2.0g/cm3、典型地从0.8至1.8g/cm3、更典型地从0.9至1.5g/cm3的密度。在实施例中，复丝缝合纱线的聚合物纤维具有从0.9至1.4g/cm3的密度。
复丝缝合纱线的特征可以在于某些特性，如线性质量密度和/或长丝支数(当纱线包括多于一根长丝时)。
纱线的线性质量密度以特(tex)、或更常见地以分特(dtex)为单位给出。一特定义为每1000米纱线按克计的质量。因此，一分特是每10,000米纱线按克计的质量。根据本发明，复丝缝合纱线的线密度小于或等于80分特。典型地，线密度是在1至60分特、更典型地1至40分特的范围内。
复丝缝合纱线的特征可以在于长丝支数，这是组成纱线的长丝数。复丝缝合纱线的长丝支数小于或等于缝合纱线的分特值的1.0倍、典型地小于或等于该分特值的0.9倍、更典型地小于或等于该分特值的0.8倍。
在一些实施例中，长丝支数是在该纱线的分特值的0.1至0.8倍、典型地该纱线的分特值的0.1至0.6倍、更典型地该纱线的分特值的0.1至0.5倍的范围内。
根据本领域普通技术人员已知的方法，可以将复丝缝合纱线的纤维或长丝交织，也被称为缠结或交缠(intermingled)。例如，可以通过将多根长丝暴露于局部流体射流(如空气流)来交织纱线长丝。交织产生缠结点，被称为结点，这些结点由未缠结的长丝空间隔开。因此，交织的程度典型地以每米纱线的结点数表示。复丝缝合纱线的交织程度小于25个结点/米。
在实施例中，无屈曲织物是多轴的并且包含多于一层的单向取向的复丝碳纱线。多轴NCF织物的层可以根据本领域普通技术人员已知的方法彼此连接和固定，例如，通过彼此平行布置并且彼此平行递送并形成针迹的多个缝合或针织线。用于将多轴NCF织物的层彼此连接和固定的缝合或针织线可以与本文所述的复丝缝合纱线相同或不同。在实施例中，用于将多轴NCF织物的层彼此连接和固定的缝合或针织线与本文所述的复丝缝合纱线相同。
复丝缝合纱线将NCF的单层内的单向取向的复丝纱线保持在一起和/或将NCF织物中的两层或更多层彼此固定，并且不提供任何结构增强。因此，根据本披露的用于将NCF的单层内的单向取向的复丝碳纱线互连和/或将NCF织物中的两层或更多层固结的复丝缝合纱线是非结构性的。相反，单向取向的复丝碳纱线是结构性的，因为它们在由其制成的复合材料或制品中提供结构增强。
无屈曲织物可以进一步包含一层或多层非织造面纱。例如，无屈曲织物可以包含单向取向的复丝碳纱线层连同非织造面纱层。可以使用本领域普通技术人员已知的任何非织造面纱。构成NCF织物(包括一层或多层非织造面纱)的层可以根据本领域普通技术人员已知的方法来彼此连接和固定，例如通过多个缝合或针织线。当使用非织造面纱层时，有利地提供改进的工艺性能如渗透性，以及机械性能如抗冲击性和抗分层性。可以使用的示例性非织造面纱在PCT公开WO 2017/083631和WO 2016/003763中描述，将这些公开通过援引并入。
NCF单层内的单向取向的复丝碳纱线的互连和/或NCF织物中的两层或更多层的固结可以使用本领域普通技术人员已知的多种针迹类型、针迹宽度(即，在纬向上的点之间的距离)、和针迹长度(即，在经向上的点之间的距离)来实现。合适的针迹式样包括直形针迹、链式针迹、锁型针步锁缝针迹、之字形针迹、经编针迹、或其组合。在实施例中，针迹式样是经编针迹。可以使用的针迹宽度和针迹长度没有特别限制。例如，针迹宽度可以在1至20mm、典型地1至10mm的范围内。针迹长度可以在例如1至20mm、典型地1至10mm的范围内。
本披露还涉及一种包含本文所述的无屈曲织物的纤维预成型件。该纤维预成型件包含至少一层无屈曲织物。
如本文使用的，术语“预成型件”是指其中将一层或多层增强材料(如本文所述的NCF织物)在没有用于进行进一步加工(如基质树脂的灌注或注入)以形成复合材料或制品的基质树脂的情况下放在模具中的构造物。
纤维预成型件可以进一步包含普通技术人员已知的用于制造复合材料的任何类型的纺织品的层。适合的织物类型或构造的实例包括但不限于：所有织造织物，其实例是平纹编织、斜纹编织、缎纹编织、螺旋编织、和单编织(uni-weave)织物；经向针织织物；针织物；编织织物；所有非织造织物，其实例包括但不限于，非织造面纱、由短切和/或连续纤维长丝构成的垫织物、毡、及上述织物类型的组合。
在实施例中，纤维预成型件可以进一步包含非织造面纱。可以使用本领域普通技术人员已知的任何非织造面纱。例如，可以使用在PCT国际公开WO2017/083631中描述的面纱。粘合剂组分可以分布在非织造面纱层的至少一侧上或穿透非织造面纱的部分，或者分布在整个无屈曲织物(包括在单向取向纤维之间的空间中和在面纱的部分上)中。例如，可以使用在PCT国际公开WO2016/003763(将该公开通过援引并入本申请)中描述的粘合剂。粘合剂可以以小于或等于最终织物的按重量计15％或更少的量存在。典型地，粘合剂组分在纤维材料的表面不形成连续的膜。
本披露涉及一种用于制造NCF织物的方法，该方法包括使用复丝缝合纱线将多个复丝碳纱线互连成单向取向的层，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
使用本文所述的复丝缝合纱线来实现将多个复丝碳纱线互连成单向取向的层。
当NCF织物包含多于一个层时，可以根据已知方法使用缝合纱线(如本文所述的复丝缝合纱线)通过缝合或针织将多层彼此连接并固定。当NCF织物是多轴时，此种多轴NCF的生产是已知的并且利用常规技术，例如，在Ts Wei Chou和Franck K.Ko的书“TextileStructural Composites,Composite Materials Series Volume 3[纺织结构复合材料，复合材料系列第3册]”，ISBN-0-44442992-1,爱思唯尔科学出版社有限责任公司(ElsevierScience Publishers B.V.),1989,第5章,第3.3段中描述的。
可以通过模制预成型件并在许多液体模制方法中用热固性树脂灌注预成型件来制造复合材料。可以使用的液体模制方法包括但不限于真空辅助树脂传递模制(VARTM)，其中使用真空产生的压差将树脂灌注到预成型件中。另一种方法是树脂传递模制(RTM)，其中在压力下将树脂灌注到密闭模具中的预成型件中。第三种方法是树脂膜灌注(RFI)，其中将半固态树脂放置在预成型件的底下或顶上，在零件上放置适当的工具，将零件装袋，并且然后放入高压釜中融化并将树脂灌注到预成型件中。
因此，本披露还涉及一种复合材料，该复合材料包含：
-基质树脂，以及
-本文所述的无屈曲织物。
用于浸渍或灌注本文所述的预成型件的基质树脂是可固化树脂。本披露中的“固化(curing或cure)”是指通过聚合物链的化学交联使聚合物材料硬化。关于组合物的术语“可固化的”意指该组合物能够经受将致使该组合物达到硬化或热固性状态的条件。基质树脂典型地是含有一种或多种未固化的热固性树脂的可硬化或热固性树脂。合适的基质树脂包括但不限于环氧树脂、氧杂环丁烷、酰亚胺(如聚酰亚胺或双马来酰亚胺)、乙烯基酯树脂、氰酸酯树脂、异氰酸酯改性的环氧树脂、酚醛树脂、呋喃树脂、苯并噁嗪、甲醛缩合树脂(如与脲、三聚氰胺或苯酚)、聚酯、丙烯酸树脂、其混合物、共混物及组合。
合适的环氧树脂包括芳族二胺、芳族单伯胺、氨基苯酚、多元酚、多元醇、多元羧酸的缩水甘油基衍生物和通过烯烃双键的过氧化而产生的非缩水甘油基树脂。合适的环氧树脂的实例包括双酚如双酚A、双酚F、双酚S、双酚K和双酚Z的聚缩水甘油醚；甲酚和苯酚基酚醛清漆的聚缩水甘油醚，酚醛加合物的缩水甘油醚，脂族二醇的缩水甘油醚，二缩水甘油醚，二乙二醇二缩水甘油醚，芳族环氧树脂，脂族聚缩水甘油醚，环氧化烯烃，溴化树脂，芳族缩水甘油胺，杂环缩水甘油酰亚胺(imidine)和酰胺，缩水甘油醚，氟化环氧树脂，或其组合。
具体实例是4,4'-二氨基二苯基甲烷(TGDDM)的四缩水甘油基衍生物、间苯二酚二缩水甘油醚、三缩水甘油基-对-氨基苯酚、三缩水甘油基-间-氨基苯酚、溴双酚F二缩水甘油醚、二氨基二苯基甲烷的四缩水甘油基衍生物、三羟基苯基甲烷三缩水甘油醚、苯酚-甲醛酚醛清漆的聚缩水甘油醚、邻甲酚酚醛清漆的聚缩水甘油醚或四苯基乙烷的四缩水甘油醚。
合适的氧杂环丁烷化合物是每分子包含至少一个氧杂环丁烷基团的化合物，包括以下化合物，例如像3-乙基-3[[(3-乙基氧杂环丁烷-3-基)甲氧基]甲基]氧杂环丁烷、氧杂环丁烷-3-甲醇、3,3-双-(羟甲基)氧杂环丁烷、3-丁基-3-甲基氧杂环丁烷、3-甲基-3-氧杂环丁烷甲醇、3,3-二丙基氧杂环丁烷、和3-乙基-3-(羟甲基)氧杂环丁烷。
可固化基质树脂可以任选地包含一种或多种添加剂，如固化剂、固化催化剂、共聚单体、流变控制剂、增粘剂、无机或有机填充剂、作为增韧剂的热塑性和/或弹性体聚合物、稳定剂、抑制剂、颜料、染料、阻燃剂、活性稀释剂、UV吸收剂以及本领域普通技术人员熟知的用于改性固化之前和/或之后的基质树脂的特性的其他添加剂。
合适的固化剂的实例包括但不限于芳族、脂族和脂环族胺，或胍衍生物。合适的芳族胺包括4,4'-二氨基二苯砜(4,4'-DDS)、和3,3'-二氨基二苯砜(3,3'-DDS)、1,3-二氨基苯、1,4-二氨基苯、4,4'-二氨基二苯基甲烷、苯二胺(BDA)；合适的脂族胺包括乙二胺(EDA)、4,4'-亚甲基双(2,6-二乙基苯胺)(M-DEA)、间二甲苯二胺(mXDA)、二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、三氧杂十三烷二胺(TTDA)、聚氧丙烯二胺、以及另外的同系物；脂环族胺，如二氨基环己烷(DACH)、异佛尔酮二胺(IPDA)、4,4'二氨基二环己基甲烷(PACM)、双氨基丙基哌嗪(BAPP)、N-氨基乙基哌嗪(N-AEP)；其他合适的固化剂还包括酸酐，典型地是多元羧酸酐，如纳迪克酸酐、甲基纳迪克酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、内亚乙基-四氢邻苯二甲酸酐、均苯四酸二酐、氯桥酸酐(chloroendic anliydride)以及偏苯三酸酐。
还其他固化剂是路易斯酸:路易斯碱络合物。合适的路易斯酸:路易斯碱络合物包括例如以下各项的络合物：BCl3:胺络合物；BF3:胺络合物，如BF3:单乙胺、BF3:丙胺、BF3:异丙胺、BF3:苄胺、BF3:氯苄胺、BF3:三甲胺、BF3:吡啶、BF3:THF；AlCl3:THF；AlCl3:乙腈；和ZnCl2:THF。
附加的固化剂是聚酰胺、聚胺、酰胺基胺、聚酰胺基胺、聚脂环族、聚醚酰胺、咪唑、双氰胺、取代的脲和脲酮(urone)、肼和硅酮。
基于脲的固化剂是以商品名DYHARD(由阿兹肯公司(Alzchem)销售)可获得的一系列材料，以及脲衍生物，如作为UR200、UR300、UR400、UR600和UR700可商购的那些。脲酮促进剂包括例如4,4-亚甲基二亚苯基双(N,N-二甲基脲)(从Onmicure公司作为U52 M可获得)。
当存在固化剂时，固化剂的总量在树脂组合物的1wt％至60wt％的范围内。典型地，固化剂以15wt％至50wt％的范围、更典型地20wt％至30wt％的范围存在。
合适的增韧剂可以包括但不限于单独或与以下各项组合的均聚物或共聚物：聚酰胺、共聚酰胺、聚酰亚胺、芳族聚酰胺、聚酮、聚醚酰亚胺(PEI)、聚醚酮(PEK)、聚醚酮酮(PEKK)、聚醚醚酮(PEEK)、聚醚砜(PES)、聚醚醚砜(PEES)、聚酯、聚氨酯、聚砜、多硫化物、聚苯醚(PPO)和改性的PPO、聚(环氧乙烷)(PEO)和聚环氧丙烷、聚苯乙烯、聚丁二烯、聚丙烯酸酯、聚苯乙烯、聚甲基丙烯酸酯、聚丙烯酸化物、聚苯砜、高性能烃聚合物、液晶聚合物、弹性体、链段弹性体和核-壳颗粒。
当存在增韧颗粒或增韧剂时，增韧颗粒或增韧剂可以以树脂组合物的0.1wt％至30wt％的范围存在。在实施例中，增韧颗粒或增韧剂可以以10wt％至25wt％的范围存在。在另一个实施例中，增韧颗粒或增韧剂可以以0.1至10wt％的范围存在。合适的增韧颗粒或增韧剂包括，例如，来自苏威公司(Solvay)的Virantage VW10200 FRP、VW10300 FP和VW10700FRP，来自住友化学公司(Sumitomo Chemicals)的BASF Ultrason E2020和Sumikaexcel5003P。
增韧颗粒或增韧剂可以是呈直径小于或等于5微米、典型地小于或等于1微米的颗粒形式。可以选择增韧颗粒或增韧剂的尺寸，使得它们不被纤维增强材料过滤。任选地，该组合物还可以包含硅胶、硅酸钙、氧化硅、磷酸盐、钼酸盐、气相二氧化硅、无定形二氧化硅、无定形熔融石英、粘土(如膨润土、有机粘土)、三水合铝、中空玻璃微球、中空聚合物微球、微空心球(microballoon)和碳酸钙。
该组合物还可以含有导电颗粒，如在PCT国际公开WO 2013/141916、WO 2015/130368和WO 2016/048885中描述的导电颗粒。
复丝碳纱线的碳可以是呈石墨的形式。碳可以用不连续或连续的金属层进行金属化。已经发现在本发明中尤其有用的石墨纤维是由苏威公司以商品名称T650-35、T650-42和T300供应的那些；由东丽公司(Toray)以商品名称T700、T800和T1000供应的那些；以及由赫氏公司(Hexcel)以商品名称AS4、AS7、IM7、IM8和IM10供应的那些。碳纤维(典型地长丝)可以不上浆或用与树脂组合物相容的材料上浆。
用于树脂灌注的模具可以是双组分封闭模具或真空袋密封的单面模具。将基质树脂灌注到模具中之后，将模具加热以使树脂固化，以生产复合制品，该复合制品是最终零件。
因此，本披露涉及一种复合制品，其通过使上文所述复合材料固化来获得。
在加热期间，树脂与自身反应，以在复合材料的基质中形成交联。在加热的初始时间段之后，树脂胶凝。在胶凝后，树脂不再流动，而是表现为固体。在胶凝之后，可以将温度或固化斜升至最终温度以完成固化。最终固化温度取决于所选热固性树脂的性质和特性。因此，在实施例中，将复合材料加热至适合于使基质树脂胶凝的第一温度，此后将温度斜升至第二温度并在该第二温度下保持一定时间以完成固化。
通过缝合将NCF织物的单层内的纱线固结和/或将多个层的纱线连接和固定的效果是形成空间或分隔区，该空间或分隔区是由于缝合线穿透而导致的纱线移位所留下的。分隔区具有细长的晶状体形状，因此称为“鱼眼”。类似于椭圆形，分隔区的形状可以由长轴和短轴表征。在本文中，分隔区的宽度(有时也被称为鱼眼宽度)是在沿短轴的最宽部分处测量的。
分隔区在缝合点处产生空的空间。随后在复合制品和/或零件的生产期间，这些空间被树脂填充，并且促进形成不期望的富树脂区。复合零件内的富树脂区表示其中湿热应力变得集中的不均匀结构区域。当经受热循环和潮湿周期时，复合零件经历收缩和膨胀。由于富树脂区和复合材料其他区域的结构差异，湿热应力集中在富树脂区，这可能导致微开裂。
因此，据信分隔区的尺寸至少是导致复合制品中微开裂存在的一个影响因素，并且据信减小分隔区的尺寸将有助于减少微开裂或消除微开裂。
当用于将NCF的单层内的单向取向的复丝碳纱线互连和/或用于将多个层的单向取向的复丝碳纱线连接和固定时，具有本文所述的特性的复丝缝合纱线有助于减小NCF织物和/或预成型件中的鱼眼的尺寸，并且因此减小了由其制成的复合制品中的富树脂区的尺寸。
图1示出了当使用根据本发明的复丝缝合纱线时，NCF织物中的分隔区(10)和该分隔区的尺寸减小的示意图。大圆(11)表示非本发明的缝合纱线的截面，而小圆(12)表示本发明的复丝缝合纱线的截面。
如图1所示，当复丝缝合纱线的长丝排列(line up)时获得较小的分隔区或鱼眼，从而有利于使分隔区的尺寸最小化的变窄效果。
分隔区的尺寸也可能受到用于将NCF织物的单层内的纱线固结和/或将多个层的纱线连接和固定的复丝缝合纱线的捻度的影响。如本文使用的，捻度是指纤维或长丝围绕纱线轴线的螺旋排列。本披露的复丝缝合纱线可以含有或可以不含有捻度。当存在捻度时，捻度以每单位长度的转数(典型地转/米)提供。如图2a所示，具有高捻度量的纱线(20)引起具有较大距离(22)的鱼眼(21)，因为纱线更多被排列并且有利于变窄效果所限制。然而，如图2b所示，具有低捻度量的纱线(23)引起具有更窄的距离(25)的鱼眼(24)，因为纱线较少被排列并且有利于变窄效果所限制。
因此，本文所述的复丝缝合纱线具有低的捻度量。该复丝缝合纱线具有小于200转/米的捻度。在实施例中，该缝合纱线具有小于150r/m、典型地小于100r/m、更典型地小于50r/m的捻度。在实施例中，该缝合纱线不具有捻度。
可能影响分隔区的尺寸的其他参数是在缝合纱线插入NCF期间对缝合纱线的张力及其控制、对碳纤维的张力及其控制、碳单位面积重量的影响、碳层的取向以及缝合式样连同缝合长度等等。
施加到缝合纱线的张力及其控制是可调节的，并且基于几个参数的组合来选择张力水平，这些参数包括例如缝合纱线属性、缝合式样和期望的悬垂性等等。尽管在缝合纱线插入NCF期间施加于缝合纱线的张力没有特别限制，但是典型地施加到缝合纱线的张力低，结果是分隔区较窄。
对碳纤维的张力及其控制取决于铺放前碳丝束的制备品质以及将它们铺放并夹紧到机器输送机后的制备品质。尽管对碳纤维的张力没有特别限制，但是较高的张力典型地导致较窄的分隔区。
可以使用本领域普通技术人员已知的任何方法来测量NCF织物、预成型件、复合材料、和/或复合制品内的分隔区宽度。例如，光学显微镜可以用于可视化分隔区和使用数字成像软件进行的测量。
典型地，NCF织物、预成型件、复合材料、和/或复合制品内的分隔区宽度小于或等于300微米、典型地小于或等于100微米。
通过以下非限制性实例进一步说明了根据本披露的NCF织物、缝合纱线以及由其制成的预成型件、复合材料、和复合制品。
实例
除非另有说明，否则所有NCF织物都是使用2层碳纤维制造的，其中方向为±45°并且每层的单位面积重量为268gsm(克/平方米)。机器规格是E5，并且针迹式样是经编针迹。针迹密度是12针/英寸。使用了多种缝合纱线。
鱼眼的测量是使用光学显微镜以50X放大率在织物的两个面上进行的。在暗场模式下进行观察，并聚焦在碳纤维床的在鱼眼两侧的边缘上。然后测量鱼眼的短轴长度或鱼眼宽度。沿与织物方向成90度的虚拟线对每个织物样品进行十次测量。在织物的顶面和底面都分别进行测量、绘图、以及分析。
实例1
使用仅具有8根长丝且捻度小于200r/m的55分特缝合纱线(EMS Grillon K140)来制造NCF织物。所得NCF织物的鱼眼宽度是约100微米。
由NCF织物形成复合制品，并且使该复合制品经受最高达1600次湿热循环。在明场光或荧光灯下在100X放大率下在复合制品中未观察到微开裂。
实例2
使用36分特的PET复丝缝合纱线来制造NCF织物，该复丝缝合纱线具有24根长丝(无捻度但是低交缠的)以及1.38g/cm3的密度。所得NCF织物具有约80微米的鱼眼宽度。
实例3
使用39分特的PA 10/10缝合纱线来制造NCF织物，该缝合纱线具有34根长丝和1.04g/cm3的密度(无捻度且无交缠)(苏威公司)。所得NCF织物具有约90微米的鱼眼宽度。

Claims (16)

1.一种无屈曲织物，其包含至少一层单向取向的复丝碳纱线和将这些复丝碳纱线互连的复丝缝合纱线，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
2.如权利要求1所述的无屈曲织物，其中，这些聚合物纤维是聚酰胺纤维、共聚酰胺纤维、聚酯纤维、或共聚酯纤维。
3.如权利要求1或2所述的无屈曲织物，其中，该复丝缝合纱线的线密度是在1至60分特、更典型地1至40分特的范围内。
4.如权利要求1-3中任一项所述的无屈曲织物，其中，该复丝缝合纱线的长丝支数是在该纱线的分特值的0.1至0.8倍、典型地该纱线的分特值的0.1至0.6倍、更典型地该纱线的分特值的0.1至0.5倍的范围内。
5.如权利要求1-4中任一项所述的无屈曲织物，其中，该缝合纱线具有小于150r/m、典型地小于100r/m、更典型地小于50r/m的捻度。
6.如权利要求1-5中任一项所述的无屈曲织物，其中，该缝合纱线不具有捻度。
7.如权利要求1-6中任一项所述的无屈曲织物，其中，这些聚合物纤维具有从0.5至2.0g/cm3、典型地从0.8至1.8g/cm3、更典型地从0.9至1.5g/cm3的密度。
8.如权利要求1-6中任一项所述的无屈曲织物，其中，这些聚合物纤维具有从0.9至1.4g/cm3的密度。
9.如权利要求1-8中任一项所述的无屈曲织物，其中，该缝合纱线具有小于25个结点/米的交织。
10.如权利要求1-9中任一项所述的无屈曲织物，其中，该无屈曲织物是多轴的并且包含多于一层的单向取向的复丝碳纱线。
11.如权利要求1-10中任一项所述的无屈曲织物，其进一步包含非织造面纱。
12.一种纤维预成型件，其包含如权利要求1-11中任一项所述的无屈曲织物。
13.如权利要求12所述的纤维预成型件，其进一步包含非织造面纱。
14.一种复合材料，其包含：
-基质树脂，以及
-如权利要求1-11中任一项所述的无屈曲织物。
15.一种复合制品，其通过使如权利要求14所述的复合材料固化来获得。
16.一种用于制造如权利要求1-11中任一项所述的无屈曲织物的方法，该方法包括：使用复丝缝合纱线将多个复丝碳纱线互连成单向取向的层，其中该缝合纱线的特征在于以下中的两项或更多项：
(a)包含多个聚合物纤维，
(b)具有小于或等于80分特的线密度，
(c)具有小于或等于该缝合纱线的分特值的0.8倍的长丝支数，或
(d)具有小于200转/米(r/m)的捻度。
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