CN110435239A - 一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法 - Google Patents

一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法 Download PDF

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CN110435239A
CN110435239A CN201910573967.1A CN201910573967A CN110435239A CN 110435239 A CN110435239 A CN 110435239A CN 201910573967 A CN201910573967 A CN 201910573967A CN 110435239 A CN110435239 A CN 110435239A
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epoxy resin
carbon
carbon fiber
polyetherimide
preparation
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CN110435239B (zh
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张辉
陈正国
徐磊
周帅
程超
黄壮
王恒星
施燕华
余木火
刘勇
孙泽玉
滕翠青
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Donghua University
National Dong Hwa University
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Abstract

本发明涉及一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法，聚醚酰亚胺PEI纳米纤维膜铺放在上浆后碳纳米纤维层间，灌注环氧树脂，即得。本发明利用热塑性树脂聚醚酰亚胺增强增韧环氧树脂的同时，利用石墨烯，碳纳米管对增韧后树脂基体进行界面改性，改善碳纤维与树脂基体的界面结合，实现对于复合材料纳米‑亚微米两个尺度的增韧。

Description

一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法
技术领域
本发明属于聚合物基复合材料及其制备领域，特别涉及一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法。
背景技术
碳纤维增强环氧基复合材料具有比强度和比刚度高，可设计性强，抗疲劳断裂性能好，耐腐蚀，结构尺寸稳定性好以及便于大面积整体成形的独特优点，因而在航空航天，建筑，机械，交通，能源，化工，电子，体育。E51型环氧树脂是一类具有良好性能的热固性聚合物材料，耐化学腐蚀、绝缘、强度高。产品环氧值高(平均环氧值为0.51eq/100g，环氧值范围为±0.03eq/100g)、粘度低(40℃下不大于2500MPa·S)、色泽浅(色泽号≤2)，挥发物含量低于2％。E51型环氧树脂应用广泛，作为浇注体原料时，E51型环氧树脂工艺性好、流动性好，制备的浇注体机械强度和绝缘性能优异。储存时，应存放于阴凉干燥处，避免被阳光直射、雨淋。同时，应隔绝火源、远离热源，确保实验安全。聚醚酰亚胺(PEI)属于热塑性树脂之一，是一种非结晶性的热塑性树脂，它的尺寸稳定性良好、加工性优异，而且PEI耐高温、强度高。因而，在复合材料领域中，多用于制备高性能纤维增强树脂基复合材料。此外，PEI除了可以作为热塑性树脂基复合材料的基体材料，也可用于热固性树脂基复合材料，作为增韧材料，对热固性树脂产生增韧作用。
Polyetherimide(PEI):
由于EP经过固化交联反应后脆性较大，力学性能不佳，可以向其中加入可溶性工程热塑性聚醚酰亚胺，从而达到改善EP韧性的目的。经实验研究证明：热塑性树脂PEI改性EP的确是一种良好的选择，可以改善基体材料的韧性，提高复合材料的力学性能。使用PEI及其改性物对EP进行共混增韧改性作为材料改性的新方法，对复合材料韧性、刚性、热稳定性有着良好的作用。
碳纳米管具有优异的导电性能，导热性能，因而有大量报道关于碳纳米管提高聚合物导电性能的研究。石墨烯也具有优异的导电性能，导热性能，也有不少关于石墨烯提高聚合物导电性能的研究报道。
发明内容
本发明所要解决的技术问题是提供一种多尺度增韧环氧树脂基碳纤维复合材料及其制备方法，可以用于汽车，航空，海洋等领域中的大型结构件。本发明通过高压静电纺丝方法制的可溶性聚醚酰亚胺(PEI)纳米纤维膜，同时利用溶剂法制备含有聚醚酰亚胺和碳纳米管的上浆剂，通过静置吸附制得含有上浆剂的碳纤维，之后将纳米纤维膜铺放在上浆后碳纤维层间，利用真空辅助树脂灌注成型方法灌注环氧树脂制备碳纳米管/PEI纳米纤维增韧环碳纤维增强氧树脂复合材料。
本发明的一种环氧树脂基碳纤维复合材料，其特征在于，包括：碳纤维，环氧树脂基体材料，聚醚酰亚胺(PEI)和均匀分散于碳纤维中的纳米填料；纳米填料种类有：碳纳米管，石墨烯，其中聚醚酰亚胺PEI为亚微米增韧材料、纳米填料为纳米界面改性填料。
所述复合材料结构依次为碳纤维基底层、聚醚酰亚胺/纳米填料复合层、聚醚酰亚胺/环氧树脂复合层、聚醚酰亚胺/纳米填料复合层、碳纤维基底层。
其中灌注树脂环氧树脂E51和固化剂E100的配方(E51/E100＝4:1，质量比)。
本发明的一种环氧树脂基碳纤维复合材料的制备方法，包括：
(1)将聚醚酰亚胺PEI溶于溶剂中，加入纳米填料，超声，得到聚醚酰亚胺/纳米填料上浆剂；
(2)将聚醚酰亚胺/纳米填料上浆剂对碳纤维布进行上浆处理，得到上浆后碳纳米纤维；
(3)聚醚酰亚胺PEI纳米纤维膜铺放在上浆后碳纳米纤维层间，灌注环氧树脂，即得环氧树脂基碳纤维复合材料。
所述步骤(1)中溶剂为二氯甲烷；纳米填料为碳纳米管和/或石墨烯。
所述步骤(1)中聚醚酰亚胺/纳米填料上浆剂中，聚醚酰亚胺、纳米填料的质量百分数分别为二氯甲烷质量的1％，0.03％-0.15％。
所述步骤(1)中超声功率为300-1000W，时间为2-24h。
所述步骤(2)中碳纤维布为前处理后碳纤维布，具体为：丙酮处理碳纤维布后干燥，然后再用浓硝酸进行酸化处理。
所述丙酮处理碳纤维布为：60-70℃水浴加热下冷凝回流12-36h，干燥为100-110℃干燥12-360h；酸化处理为：避光条件下，70℃水浴加热下冷凝回流8-12h。
进一步，所述碳纤维布为T300、T700、T800平纹碳纤维布。
碳纤维布进行前处理，由于使用的T300、T700、T800平纹碳纤维布在采购回来时已涂覆工厂原始上浆剂，为了使本发明的研究变量多壁碳纳米管能够均匀分散在CFs(碳纤维布)和EP(环氧树脂)之间，需要对CFs原始上浆剂进行去除上浆剂处理。使用丙酮试剂对碳纤维布进行处理，去除其原始上浆剂。操作步骤为：在桶型反应器中放入需要处理的碳纤维布，加入适量丙酮试剂。本发明选择在60-70℃水浴加热下冷凝回流12-36小时。使用丙酮试剂处理之后需要对碳纤维布进行干燥，以脱去丙酮试剂，为后续实验做准备。选择的干燥时间为12-360小时，设定的干燥温度为100-110℃。碳纤维布的酸化处理:对碳纤维布的酸化处理实际上是一种化学刻蚀，表面经过化学刻蚀处理的碳纤维会形成凹凸不平的坑洼，增大了碳纤维的比表面积。与平整光滑的碳纤维表面相比，不平整的碳纤维表面更易和上浆剂结合。所以，碳纤维布的酸化处理是为新上浆剂的顺利涂覆而进行的预先处理。酸化处理是在桶型反应器中放入已去除原始上浆剂的碳纤维布，使用37％质量浓度浓硝酸试剂对其进行酸化处理。本课题实验选择在70℃水浴加热下冷凝回流12小时。此反应过程需要在避光条件下进行，以免光线对浓硝酸的影响。
所述步骤(2)中上浆处理具体为：碳纤维布完全浸没在上浆剂中，使得上浆剂均匀涂覆在碳纤维表面；或采用电泳以及浸胶方式处理碳纤维布在宽幅方向浸胶。
所述步骤(3)中聚醚酰亚胺PEI纳米纤维膜具体为：通过高压静电纺丝方法制的可溶性聚醚酰亚胺PEI纳米纤维膜，PEI粉末和溶剂1-甲基-2-吡咯烷酮NMP混合，搅拌溶解，得到20wt％-30wt％的PEI溶液，进行高压静电纺丝，具体工艺参数为：喷丝头距离接收器距离15-20cm，纺丝温度20-40℃，纺丝电压15-20kV。
步骤(3)中利用真空辅助树脂灌注成型方法灌注环氧树脂，具体工艺见附图4，具体为：准备模具、粘贴胶带、材料铺放、封装(密封胶带，真空袋)、抽真空、配树脂、灌注树脂、脱模修整。
本发明的一种所述方法制备的环氧树脂基碳纤维复合材料。
本发明的一种所述环氧树脂基碳纤维复合材料的应用，用于汽车，航空，海洋等领域中的大型结构件。
有益效果
本发明可以单独用于工程结构件，可以有效的提高工程结构件对于韧性(尤其是航空领域有较高要求的领域)，同时液体成型制备工艺简单，易成型加工，成型周期短，设备投资成本小，配合自动铺放技术可以大伙规模应用；
本发明利用热塑性树脂聚醚酰亚胺增强增韧环氧树脂的同时，利用石墨烯，碳纳米管对增韧后树脂基体进行界面改性，改善碳纤维与树脂基体的界面结合，实现对于复合材料纳米-亚微米两个尺度的增韧。
附图说明
图1两层碳纤维间物料情况示意图；
图2碳纳米管/聚醚酰亚胺上浆后碳纤维电镜图(A)碳纳米管分布情况(B)聚醚酰亚胺及碳纳米管分布情况；
图3中(a)真空袋封装结构以及(b)(c)铺层方式；
图4复合材料真空辅助灌注成型具体工艺流程；
图5多尺度增韧环氧树脂基碳纤维复合材料Ⅰ层间断裂韧性结果。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
复合材料Ⅰ型层间韧性测试按照美国材料与试验协会ASTM D5528-13单向纤维增强聚合物基复合材料I型层间断裂韧性的标准试验方法进行测试。
实施例中灌注树脂环氧树脂和固化剂的配方(E51/E100＝4:1，质量比)。
实施例1
(1)通过高压静电纺丝方法制的可溶性聚醚酰亚胺(PEI)纳米纤维膜：
使用1-甲基-2-吡咯烷酮(NMP)为溶剂，根据质量百分比计算出需要的PEI质量，使用分析天平和量筒准确称量溶质PEI粉末和溶剂NMP试剂，并将两者加入容器，
通过磁力搅拌机对其进行搅拌，使PEI逐步溶解在NMP中，直至完全溶解、均匀混合。配制质量浓度为26wt％的PEI溶液，进行高压静电纺丝，具体工艺参数为：喷丝头距离接收器距离15cm，纺丝温度30℃，纺丝电压15kV。
(2)利用溶剂法制备含有聚醚酰亚胺和碳纳米管的上浆剂:
在桶型反应器中放入需要处理的T300平纹碳纤维布，加入丙酮试剂。在60℃水浴加热下冷凝回流12小时，然后100℃条件下干燥时间10小时，得到已去除原始上浆剂的碳纤维布。
酸化处理:在桶型反应器中放入已去除原始上浆剂的碳纤维布，使用浓硝酸试剂避光条件下，在70℃水浴加热下冷凝回流12小时，进行酸化处理，得到酸化处理后的碳纤维布。
PEI/多壁碳纳米管上浆剂的制备:
选择二氯甲烷作为PEI和碳纳米管的有机溶剂，用于溶解和分散PEI和碳纳米管制备碳纤维上浆剂。根据质量百分比计算出需要的PEI和碳纳米管质量，然后使用分析天平称量需要质量的溶质、使用量筒准确量取需要体积的溶剂，并将溶剂和溶质加入容器。即将溶质PEI粉末溶解在二氯甲烷溶液中，加热搅拌至溶解完全后，向PEI/二氯甲烷溶液体系加入碳纳米管，再用功率为300W的超声设备对碳纳米管-二氯甲烷分散体系溶液进行超声处理超声24h，得到PEI/多壁碳纳米管上浆剂。选择固定PEI的(二氯甲烷)质量浓度1％，分别配制成碳纳米管质量浓度0.03-0.15wt％的PEI/多壁碳纳米管溶液，得到PEI/多壁碳纳米管上浆剂；
(3)PEI/多壁碳纳米管上浆剂对碳纤维布的上浆处理:
将酸化处理后的碳纤维布放入PEI/多壁碳纳米管上浆剂中，使碳布完全浸没在上浆剂溶液中，保证反应充分进行上浆剂均匀吸附在碳纤维表面。
(4)之后将纳米纤维膜铺放在上浆后碳纤维层间，利用真空辅助树脂灌注成型方法灌注环氧树脂(具体的制备工艺(见图4)如下：准备模具—粘贴胶带—材料铺放—封装(密封胶带，真空袋)—抽真空—配树脂—灌注树脂—脱模修整)制备碳纳米管/PEI纳米纤维增韧环碳纤维增强氧树脂复合材料。
实施例2
(1)通过高压静电纺丝方法制的可溶性聚醚酰亚胺(PEI)纳米纤维膜：
使用1-甲基-2-吡咯烷酮(NMP)为溶剂，根据质量百分比计算出需要的PEI质量，使用分析天平和量筒准确称量溶质PEI粉末和溶剂NMP试剂，并将两者加入容器，通过磁力搅拌机对其进行搅拌，使PEI逐步溶解在NMP中，直至完全溶解、均匀混合。配制质量浓度为26wt％的PEI溶液，进行高压静电纺丝，具体工艺为：喷丝头距离接收器距离15cm，纺丝温度30℃，纺丝电压15kV。
(2)利用溶剂法制备含有聚醚酰亚胺和石墨烯的上浆剂:
在5升桶型反应器中放入需要处理的T300平纹碳纤维布，加入5L丙酮试剂，在6℃水浴加热下冷凝回流12小时。使用丙酮试剂处理之后需要对碳纤维布进行干燥，以脱去丙酮试剂，为后续实验做准备。干燥时间为12小时，设定的干燥温度为100℃。
碳纤维布的酸化处理:在桶型反应器中放入已去除原始上浆剂的碳纤维布，使用浓硝酸试剂，在70℃水浴加热下冷凝回流12小时，在避光条件下进行酸化处理，得到酸化处理后的碳纤维布。
PEI/多壁石墨烯上浆剂的制备:选择二氯甲烷作为PEI和石墨烯的有机溶剂，用于溶解和分散PEI和石墨烯制备碳纤维上浆剂。根据质量百分比计算出需要的PEI和石墨烯质量，然后使用分析天平称量需要质量的溶质、使用量筒准确量取需要体积的溶剂，并将溶剂和溶质加入容器。即将溶质PEI粉末溶解在二氯甲烷溶液中，加热搅拌至溶解完全后，向PEI/二氯甲烷溶液体系加入石墨烯，再用功率为300W的超声设备对石墨烯-二氯甲烷分散体系溶液进行超声处理超声2h，得到PEI/石墨烯上浆剂。本实施例选择固定PEI的(二氯甲烷)质量浓度1％，分别配制成石墨烯质量浓度相比PEI分别为0.03-0.15wt％的PEI/多壁石墨烯溶液，得石墨烯-聚醚酰亚胺-二氯甲烷分散体系溶液；
(3)PEI/多壁石墨烯上浆剂对碳纤维布的上浆处理:
将酸化处理后的碳纤维布放入的PEI/多壁石墨烯上浆剂中，使碳布完全浸没在上浆剂溶液中，保证反应充分进行上浆剂均匀吸附在碳纤维表面。
(4)之后将纳米纤维膜铺放在上浆后碳纤维层间，利用真空辅助树脂灌注成型方法灌注环氧树脂(具体的制备工艺(见图4)如下：准备模具—粘贴胶带—材料铺放—封装(密封胶带，真空袋)—抽真空—配树脂—灌注树脂—脱模修整))制备石墨烯/PEI纳米纤维增韧环碳纤维增强氧树脂复合材料。
如图5所示，图中从左至右，不同增韧体系下，GIC分别为336.0J/m2、504.7J/m2、652.6J/m2、414.1J/m2、222.8J/m2和198.3J/m2。结果表明：将碳纳米管加入到15g/m2PEI体系中后，复合材料断裂韧性会进一步得到改善，随着碳纳米管含量的增加改善效果先增加后减小。加入0.03wt％时，对GI的提高有促进作用最佳，相对于未改性复合材料GI增长94.2％；相对于只含PEI不含MWCNTs体系复合材料GI增长29.3％。在MWCNTs含量为0.07wt％、0.11wt％和0.15wt％时，相对于未改性复合材料GI增长比率分别为23.2％、-33.7％和-40.9％。即加入含量不当的MWCNTs，会使复合材料性能无法得到提升且性能会大幅下降。这可能是由于此时体系中的MWCNTs过多导致裂纹导致EP/PEI界面性能下降，较容易从EP/PEI界面引发裂纹导致增韧效果下降。

Claims (10)

1.一种环氧树脂基碳纤维复合材料，其特征在于，所述复合材料依次包括碳纤维基底层、聚醚酰亚胺/纳米填料复合层、聚醚酰亚胺/环氧树脂复合层、聚醚酰亚胺/纳米填料复合层、碳纤维基底层。
2.一种环氧树脂基碳纤维复合材料的制备方法，包括：
(1)将聚醚酰亚胺PEI溶于溶剂中，加入纳米填料，超声，得到聚醚酰亚胺/纳米填料上浆剂；
(2)将聚醚酰亚胺/纳米填料上浆剂对碳纤维布进行上浆处理，得到上浆后碳纳米纤维；
(3)聚醚酰亚胺PEI纳米纤维膜铺放在上浆后碳纳米纤维层间，灌注环氧树脂，即得环氧树脂基碳纤维复合材料。
3.根据权利要求2所述制备方法，其特征在于，所述步骤(1)中溶剂为二氯甲烷；纳米填料为碳纳米管和/或石墨烯。
4.根据权利要求2所述制备方法，其特征在于，所述步骤(1)中聚醚酰亚胺/纳米填料上浆剂中，聚醚酰亚胺、纳米填料的质量百分数分别为溶剂质量的1％，0.03％-0.15％。
5.根据权利要求2所述制备方法，其特征在于，所述步骤(2)中碳纤维布为前处理后碳纤维布，具体为：丙酮处理碳纤维布后干燥，然后再用浓硝酸进行酸化处理。
6.根据权利要求5所述制备方法，其特征在于，所述丙酮处理碳纤维布为：60-70℃水浴加热下冷凝回流12-36h，干燥温度为100-110℃干燥12-360h；酸化处理为：避光条件下，70℃水浴加热下冷凝回流8-12h。
7.根据权利要求2所述制备方法，其特征在于，所述步骤(2)中上浆处理具体为：碳纤维布完全浸没在上浆剂中，使得上浆剂均匀涂覆在碳纤维表面；或采用电泳以及浸胶方式处理碳纤维布在宽幅方向浸胶。
8.根据权利要求2所述制备方法，其特征在于，步骤(3)中利用真空辅助树脂灌注成型方法灌注环氧树脂。
9.一种权利要求2所述方法制备的环氧树脂基碳纤维复合材料。
10.一种权利要求1所述环氧树脂基碳纤维复合材料的应用。
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