CN113087936A - 一种纤维表面处理方法 - Google Patents
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Abstract
一种纤维表面处理方法,属于纤维表面改性领域。本方法将纤维置于小分子表面活化剂进行表面活化后,浸渍于聚合物稀溶液中,超声处理后干燥表面水分;将上述纤维浸渍在交联剂中进行化学交联,在纤维表面形成一层聚合物交联网状结构;再将上述纤维置于树脂溶液中,通过溶液置换将树脂溶液填充至聚合物交联网状结构中,在纤维表面构筑交联双网络结构。与现有技术相比,本发明提供的方法具有如下优势:在提高纤维与树脂基体结合强度的同时提升纤维本体拉伸强度,方法简单有利于大规模生产使用。
Description
技术领域
本发明属于纤维表面改性技术领域,具体涉及一种纤维表面处理方法。
背景技术
纤维基树脂复合材料是一种先进的具有很大应用价值和应用前景的一种复合材料,是由高性能纤维和高分子树脂两部分复合而成,具有高强度、高模量、抗疲劳、耐腐蚀、可设计性强、易加工成型等特点。高性能复合材料于20世纪60年代被开发并实现产业化生产,推动了国防军工和航天科技的发展。几十年来高性能纤维复合材料不断发展,已从航空航天领域向防护装备、体育器材、交通、建筑、工业设备等多领域迅速推广。此外,高性能纤维例如PBO纤维、芳纶纤维等已被广泛应用于各种武器装备,对于促进武器装备的轻量化、小型化和高性能化起着至关重要的作用。
但是,由于这些具有高强度、高模量的高性能纤维表面比较光滑,表面活性较低,纤维具有较强的化学惰性,因此这些高性能纤维几乎与所有的树脂基体都不能很好的浸润,与树脂基体的粘结性很差,导致高性能纤维增强复合材料的层间剪切强度极低,不能较好地进行应力的传递,极大地影响了复合材料综合性能的发挥,限制了高性能纤维在先进复合材料领域中的应用。
目前,主要通过对纤维进行表面改性,来改善纤维与基体树脂间的界面粘结性。通过改变纤维表面晶态、形态、极性、表面化学组成及表面能,提高纤维表面粗糙度,增强纤维与树脂基体的机械啮合作用以及增加纤维表面极性基团和不饱和碳原子比例,提高纤维与树脂间浸润性。常用的表面改性方式有化学处理、等离子体处理、辐射和电晕处理法等。这些方法虽一定程度上改善了纤维的界面性能,但是大部分都是以牺牲纤维的力学性能和热性能为代价。
专利CN101235590A介绍了一种对高性能纤维的超声化学改性方法。将PBO纤维浸渍于混合均匀的多聚磷酸混合化学溶剂中水浴并超声处理进行PBO纤维的表面改性。该方法虽然一定程度上提升了PBO纤维与基体树脂的界面结合性能,但是也对PBO纤维的力学性能造成了损伤。
发明内容
本发明的目的是为了解决纤维表面惰性从而导致纤维与树脂基体界面结合性能较差的问题,提供一种纤维表面处理方法,该方法能够在不损失纤维力学性能的前提下增加纤维与树脂基体界面结合性能。
为实现上述目的,本发明采取的技术方案如下:
一种纤维表面处理方法,所述方法包括以下步骤:
步骤一:将纤维浸渍在0.1%~15%小分子表面活化剂溶液中1~120min,得活化纤维1;
步骤二:将活化纤维1浸渍在浓度为1%~40%聚合物溶液中1min~60min,超声处理后取出,表面干燥后得活化纤维2;
步骤三:将活化纤维2浸渍在0.1%~60%交联剂溶液中,进行化学交联,使聚合物在纤维表面形成三维交联网络结构,得活化纤维3;
步骤四:将活化纤维3浸渍在0.1%-15%树脂溶液中1min~60min,利用溶剂置换将树脂溶液填充至聚合物交联网络结构中,形成双网络表面,去除溶剂,得到活化纤维4;
步骤五:将活化纤维4与树脂混合并制备高性能纤维复合材料。
本发明相对于现有技术的有益效果是:
1、本发明将纤维用小分子表面活性剂活化后,在纤维表面形成聚合物交联树脂双交联网络,与树脂混合制备得高性能纤维复合材料;
2、本发明利用在聚合物表面形成的交联凝胶结构干燥后坍缩力减少纤维原纤之间缝隙,提高了纤维本体的力学性能;
3、本发明所用的材料价格低廉,有利于节约成本;
4、本发明在提高纤维与树脂基体结合强度的同时提升纤维本体拉伸强度,所用制备方法简单,有利于规模化生产,具有非常好的应用前景。
附图说明
图1为实施例1制备的活化纤维SEM照片;
图2为实施例1处理得到的PBO纤维单丝拉伸强度比较图;
图3为实施例1处理得到的PBO纤维界面剪切强度比较图。
具体实施方式
下面结合附图和实施例对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修改或者等同替换,而不脱离本发明技术方案的范围,均应涵盖在本发明的保护范围中。
具体实施方式一:本实施方式记载的是一种纤维表面处理方法,所述方法包括以下步骤:
步骤一:将纤维浸渍在0.1%~15%小分子表面活化剂溶液中1~120min,小分子表面活化剂可以与纤维惰性表面形成化学联结,改善纤维表面粘结性,得活化纤维1;
步骤二:将活化纤维1浸渍在浓度为1%~40%聚合物溶液中1min~60min,超声处理后取出,表面干燥后得活化纤维2;
步骤三:将活化纤维2浸渍在0.1%~60%交联剂溶液中,进行化学交联,使聚合物在纤维表面形成三维交联网络结构,得活化纤维3;
步骤四:将活化纤维3浸渍在0.1%-15%树脂溶液中1min~60min,利用溶剂置换将树脂溶液填充至聚合物交联网络结构中,形成双网络表面,去除溶剂,得到活化纤维4;
步骤五:将活化纤维4与树脂混合并制备高性能纤维复合材料。
本发明将纤维用小分子表面活性剂活化后,在纤维表面形成聚合物交联树脂双交联网络,与树脂混合制备得高性能纤维复合材料。
具体实施方式二:具体实施方式一所述的一种纤维表面处理方法,步骤一中,所述纤维为PBO纤维、芳纶纤维、碳纤维、聚酯纤维、玻璃纤维、尼龙66、聚苯硫醚纤维、玄武岩纤维或超高分子量聚乙烯纤维中的一种。
具体实施方式三:具体实施方式一所述的一种纤维表面处理方法,步骤一中,所述小分子表面活化剂为硅烷偶联剂、乙二酰氯、己二酰氯、丁烯二酰氯、丙二酰氯、戊二醛或己二醛中的一种或多种混合。这些小分子表面活化剂能够活化纤维表面,增加纤维表面活性基团,有利于纤维与聚合物网络的复合。
具体实施方式四:具体实施方式三所述的一种纤维表面处理方法,所述硅烷偶联剂为KH-550、KH-560、KH-570、KH-151、KH-171或KH-792中的一种或多种复合。这些硅烷偶联剂能够在纤维表面形成胺基基团,增加纤维表面能。
具体实施方式五:具体实施方式一所述的一种纤维表面处理方法,步骤二中,所述聚合物为琼脂糖,甲基纤维素,透明质酸,明胶,壳聚糖,弹性蛋白样多肽,聚丙烯酰胺,聚乙烯醇,聚丙烯酸钠,丙烯酸酯中的一种或多种复合。这些聚合物能够在纤维表面形成交联网络,替代纤维原本惰性表面,增加纤维表面活性,同时可以增加纤维的比表面积。
具体实施方式六:具体实施方式五所述的一种纤维表面处理方法,步骤三中,所述交联剂能够在聚合物分子链之间形成桥键,使得聚合物由二维结构变为三维结构。
具体实施方式七:具体实施方式一所述的一种纤维表面处理方法,步骤四中,所述树脂溶液为热塑性树脂或热固性树脂的溶液。这些树脂溶液能够通过溶剂置换的方式溶胀进聚合物交联网络形成双互穿网络聚合物,同时能够很好的跟树脂结合,从而提高纤维与树脂的粘结力。
具体实施方式八:具体实施方式七所述的一种纤维表面处理方法,所述热塑性树脂为PE-聚乙烯、PP-聚丙烯、PVC-聚氯乙烯、PS-聚苯乙烯、PA-聚酰胺、POM-聚甲醛、PC-聚碳酸酯、聚苯醚、聚砜、橡胶中的一种或多种复合。
具体实施方式九:具体实施方式七所述的一种纤维表面处理方法,所述热固性树脂为环氧树脂、聚酯树脂、乙烯基酯、双马来酰胺、热固性聚酰亚胺、氰酸酯、酚醛树脂、有机硅树脂、聚丁二烯树脂、呋喃树脂中的一种或多种复合。
具体实施方式十:具体实施方式一所述的一种纤维表面处理方法,步骤四中,通过干燥、挥发或萃取中的一种或多种方式去除溶剂。
实施例1:
(1)将PBO纤维浸渍于5%硅烷偶联剂KH-550中处理时间为5h,得到活化PBO纤维1;
(2)将活化PBO纤维1浸渍在1%聚乙烯醇水溶液中,超声15S,浸泡15min后取出,室温放置1h干燥表面水分后得到活化PBO纤维2;
(3)配置10%戊二醛水溶液,并用HCl调节PH=2,将活化PBO纤维2浸泡在上述戊二醛水溶液中,60℃水浴加热10min,用去离子水洗去过量交联剂,在PBO表面形成聚乙烯醇交联网络,得到活化PBO纤维3;
(4)将活化PBO纤维3浸泡在10%E-51环氧树脂/丙酮溶液中1h,用丙酮清洗至恒重,100℃干燥6h得到活化PBO纤维4;图1是制备得到PBO活化纤维4的SEM图片,表面较粗糙。
(5)将活化PBO纤维4与环氧树脂混合,静置5h使纤维与树脂充分浸润,使用热压机热压固化成型,制备高性能PBO纤维复合材料。
如图2、图3所示,对本发明方法改性后的PBO纤维进行单丝拉伸强度测试及界面剪切强度测试,可以看出本发明同时提高了PBO纤维的单丝力学强度和PBO纤维与树脂基体的结合强度。
实施例2:
(1)将芳纶纤维浸渍于5%硅烷偶联剂KH-550中处理时间为5h,得到活化芳纶纤维1;
(2)将活化芳纶纤维1浸渍在2%聚乙烯醇水溶液中,超声15S,浸泡15min后取出,室温放置1h干燥表面水分后得到活化芳纶纤维2;
(3)配置10%戊二醛水溶液,并用HCl调节PH=2,将活化芳纶纤维2浸泡在上述戊二醛水溶液中,60℃水浴加热10min,用去离子水洗去过量交联剂,在芳纶表面形成聚乙烯醇交联网络,得到活化芳纶纤维3;
(4)将活化芳纶纤维3浸泡在10%E-51环氧树脂/丙酮溶液中1h,用丙酮清洗至恒重,100℃干燥6h得到活化芳纶纤维4;
(5)将活化芳纶纤维4与环氧树脂混合,静置5h使纤维与树脂充分浸润,使用压机热压固化成型,制备高性能芳纶纤维复合材料。
实施例3:
(1)将PBO纤维浸渍于5%硅烷偶联剂和己二酰氯的无水氯仿溶液中处理时间为5h,得到活化PBO纤维1;
(2)将活化PBO纤维1浸渍在3%壳聚糖水溶液中,超声15S,浸泡30min后取出,室温放置1h干燥表面水分后得到活化PBO纤维2;
(3)配置10%戊二醛水溶液,将活化PBO纤维2浸泡在上述戊二醛水溶液中,60℃水浴加热30min,用去离子水洗去过量交联剂,在PBO表面形成壳聚糖交联网络,得到活化PBO纤维3;
(4)将活化PBO纤维3浸泡在10%E-51环氧树脂/酚醛树脂/丙酮溶液(环氧树脂:酚醛树脂=1:1)中1h,用丙酮清洗至恒重,100℃干燥6h得到活化PBO纤维4;
(5)将活化PBO纤维4与环氧树脂混合静置5h使纤维与树脂充分浸润,使用压机热压固化成型,制备高性能PBO纤维复合材料。
实施例4:
(1)将PBO纤维浸渍于5%硅烷偶联剂KH-550中处理时间为5h,得到活化PBO纤维1;
(2)将活化PBO纤维1浸渍在3%聚乙烯醇水溶液中,超声15S,浸泡30min后取出,室温放置1h干燥表面水分后得到活化PBO纤维2;
(3)配置10%硼酸水溶液,将活化PBO纤维2浸泡在上述硼酸水溶液中,用去离子水洗去过量硼酸交联剂,在PBO表面形成聚乙烯醇交联网络,得到活化PBO纤维3;
(4)将活化PBO纤维3浸泡在10%聚酰胺/丙酮溶液中1h,用丙酮清洗至恒重,100℃干燥6h得到活化PBO纤维4;
(5)将活化PBO纤维4与聚酰胺混合,加热共混挤压成型制备高性能PBO纤维复合材料。
对上述四个实施例制备的改性纤维进行界面剪切强度测试,结果如下表所示:
样品 | 原始IFSS(Gpa) | 处理后IFSS(Gpa) | IFSS提升率/% |
实施例1 | 30.52 | 44.29 | 45.1 |
实施例2 | 34.36 | 45.13 | 31.3 |
实施例3 | 30.52 | 43.36 | 42.1 |
实施例4 | 30.52 | 40.57 | 32.9 |
Claims (10)
1.一种纤维表面处理方法,其特征在于:所述方法包括以下步骤:
步骤一:将纤维浸渍在0.1%~15%小分子表面活化剂溶液中1~120min,得活化纤维1;
步骤二:将活化纤维1浸渍在浓度为1%~40%聚合物溶液中1min~60min,超声处理后取出,表面干燥后得活化纤维2;
步骤三:将活化纤维2浸渍在0.1%~60%交联剂溶液中,进行化学交联,使聚合物在纤维表面形成三维交联网络结构,得活化纤维3;
步骤四:将活化纤维3浸渍在0.1%-15%树脂溶液中1min~60min,利用溶剂置换将树脂溶液填充至聚合物交联网络结构中,形成双网络表面,去除溶剂,得到活化纤维4;
步骤五:将活化纤维4与树脂混合并制备高性能纤维复合材料。
2.根据权利要求1所述的一种纤维表面处理方法,其特征在于:步骤一中,所述纤维为PBO纤维、芳纶纤维、碳纤维、聚酯纤维、玻璃纤维、尼龙66、聚苯硫醚纤维、玄武岩纤维或超高分子量聚乙烯纤维中的一种。
3.根据权利要求1所述的一种纤维表面处理方法,其特征在于:步骤一中,所述小分子表面活化剂为硅烷偶联剂、乙二酰氯、己二酰氯、丁烯二酰氯、丙二酰氯、戊二醛或己二醛中的一种或多种混合。
4.根据权利要求3所述的一种纤维表面处理方法,其特征在于:所述硅烷偶联剂为KH-550、KH-560、KH-570、KH-151、KH-171或KH-792中的一种或多种复合。
5.根据权利要求1所述的一种纤维表面处理方法,其特征在于:步骤二中,所述聚合物为琼脂糖,甲基纤维素,透明质酸,明胶,壳聚糖,弹性蛋白样多肽,聚丙烯酰胺,聚乙烯醇,聚丙烯酸钠,丙烯酸酯中的一种或多种复合。
6.根据权利要求5所述的一种纤维表面处理方法,其特征在于:步骤三中,所述交联剂能够在聚合物分子链之间形成桥键,使得聚合物由二维结构变为三维结构。
7.根据权利要求1所述的一种纤维表面处理方法,其特征在于:步骤四中,所述树脂溶液为热塑性树脂或热固性树脂的溶液。
8.根据权利要求7所述的一种纤维表面处理方法,其特征在于:所述热塑性树脂为PE-聚乙烯、PP-聚丙烯、PVC-聚氯乙烯、PS-聚苯乙烯、PA-聚酰胺、POM-聚甲醛、PC-聚碳酸酯、聚苯醚、聚砜、橡胶中的一种或多种复合。
9.根据权利要求7所述的一种纤维表面处理方法,其特征在于:所述热固性树脂为环氧树脂、聚酯树脂、乙烯基酯、双马来酰胺、热固性聚酰亚胺、氰酸酯、酚醛树脂、有机硅树脂、聚丁二烯树脂、呋喃树脂中的一种或多种复合。
10.根据权利要求1所述的一种纤维表面处理方法,其特征在于:步骤四中,通过干燥、挥发或萃取中的一种或多种方式去除溶剂。
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