CN106192407A - 碳纤维表面改性处理方法 - Google Patents
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Abstract
本发明提出了一种碳纤维表面改性处理方法,包括以下步骤:首先将碳纤维浸渍在相容剂溶液中,然后在真空条件下用高锰酸钾的硫酸溶液对CF‑1进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为6~8,烘干,得到CF‑2,然后在乙醚中用硼氢化锂进行还原,将还原后的CF‑3用硅烷偶联剂的醇水溶液进行处理获得CF‑4。该方法在提高纤维表面活性的同时,对纤维本体无损伤。
Description
技术领域
本发明属于碳纤维技术领域,具体涉及一种碳纤维表面改性处理方法。
背景技术
碳纤维是一种具备碳材料的高抗拉强度和纤维的柔软可加工性两大特性的新一代增强纤维,它兼具金属材料的导电性和导热性、陶瓷材料的耐热性和耐化学腐蚀性以及纺织纤维的柔软性和可编性等众多优点。它的比重仅为钢的1/4,抗拉强度却可达到钢的7~9倍,因此在航空航天、汽车制造、体育休闲等众多领域得到了广泛应用,高性能碳纤维已成为国内外新材料领域研究的重点和热点。
碳纤维是由缩合多环芳烃构成的石墨片层所组成,属于二维乱层石墨结构。石墨微晶在整体中分布不均匀,呈现出“皮-芯”结构分布:内部“芯”层的微晶尺寸较小,结构疏松且含有裂纹和孔洞;表面“皮”层是沿纤维轴择优取向的同质多晶结构,微晶尺寸较大且排列整齐,有序度较高。因此,未经处理的碳纤维表面较光滑,惰性大,表面能低,活性官能团的种类和数目都很少,与树脂间的界面粘结性能较差,所制备复合材料存在较多界面缺陷。表面改性既可以通过化学反应在纤维表面引入活性基团,增加纤维与树脂间的润湿性和化学键合,也可以通过改变纤维的表面形貌和粗糙度,增加纤维与树脂间的机械啮合,从而化学和物理两方面同时改善复合材料的界面粘结性能,有效增强复合材料性能。
目前,常用的表面改性方法主要分以下几类:
(1)表面氧化法,又可分为气相氧化法、液相氧化法、等离子体氧化法和电化学氧化法等。
(2)表面涂层法,又可分为偶联剂涂层和聚合物涂层等。
(3)表面沉积法,又可分为电泳沉积法、化学气相沉积法和表面生长晶须法等。
(4)表面接枝法,包括化学接枝法、等离子体接枝聚合和辐射接枝聚合等。
然而,单一方法改性均有其局限性,在提高纤维表面活性的同时,也会对纤维本体造成不同程度的损伤,而且单一方法改性效果有限,仍未在工业生产中得到广泛应用。
发明内容
为解决现有单一方法改性对碳纤维表面造成损伤等问题,本发明提出一种碳纤维表面改性处理方法,该方法在提高纤维表面活性的同时,对纤维本体无损伤。
本发明的技术方案是这样实现的:
一种碳纤维表面改性处理方法,包括如下步骤:
1)将碳纤维浸渍在相容剂溶液中加热到50~60℃处理2~5h,烘干,得到CF-1;
2)在100℃~150℃的真空条件下,将CF-1添加进高锰酸钾的硫酸溶液中,进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为6~8,烘干,得到CF-2;
3)将CF-2分散于乙醚中,加入硼氢化锂,在10~30℃搅拌3~4h,然后加入1.5~2.5mol/L的盐酸,搅拌滤出碳纤维,再经四氢呋喃浸泡洗涤12~24h,烘干,得到CF-3;
4)将硅烷偶联剂加入醇水溶液中,充分搅拌混合均匀,获得硅烷偶联剂水解液,将CF-3分散于其中,搅拌或超声,滤出纤维,干燥,得到CF-4。
进一步,所述相容剂溶液是将相容剂溶于有机溶剂中形成质量浓度为10~15wt%的溶液。
进一步,所述相容剂选自马来酸酐接枝或者苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯的三元无规共聚物。
进一步,所述高锰酸钾的硫酸溶液是指将50~60ml摩尔浓度为0.5~0.9mol/L的硫酸中加入0.4~0.8g高锰酸钾配制而成的溶液。
进一步,所述硼氢化锂的使用量为0.05~0.1g/gCF-2;盐酸的使用量为20~40mL/gCF-2。
进一步,所述步骤4)中的醇为甲醇、乙醇、异丙醇中的一种,硅烷偶联剂为KH550,KH5501,KH560,KH570,KH580,KH602或KH792中的一种。
进一步,所述硅烷偶联剂的加入量为醇水溶液质量的0.5~2%,醇和水的质量比5~10:1。
进一步,所述碳纤维是高性能沥青基碳纤维或丙烯腈碳纤维。
本发明的有益效果:
本发明对碳纤维进行氧化之前用相容剂的溶液进行浸泡处理对碳纤维表面的活性基团进行活化后,同时对碳纤维表面的其他基团进行保护,然后在真空条件下,用高锰酸钾的硫酸溶液对碳纤维表面进行了改性处理,使碳纤维表面的含氧量在18%~26%,而且可以保持对碳纤维本体强度的损失控制在4%以内,解决了现有碳纤维表面改性方法中存在的在提高碳纤维的表面性能的同时也损失了碳纤维的本体强度的问题。然后再用硅烷偶联剂处理,获得的具有硅烷偶联剂涂层的碳纤维,其单丝拉伸强度较无涂层碳纤维明显提高,并且保持了无涂层碳纤维所具有的柔顺性和可编织性,同时解决了碳纤维与某些复合材料基体间的界面浸润性和相容性问题。
具体实施方式
实施例1
一种碳纤维表面改性处理方法,包括如下步骤:
1)将6g丙烯腈碳纤维浸渍在10wt%马来酸酐接枝的有机溶剂溶液中加热到50℃处理5h,烘干,得到CF-1。
2)在100℃的真空条件下,将CF-1添加进150ml高锰酸钾的硫酸溶液中,进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为6,烘干,得到CF-2;高锰酸钾的硫酸溶液为50ml摩尔浓度为0.5mol/L的硫酸中加入0.4g高锰酸钾配制而成的溶液。
3)将CF-2分散于乙醚中,加入硼氢化锂(使用量为0.05g硼氢化锂/gCF-2),在10℃搅拌4h,然后加入120ml的1.5mol/L的盐酸,搅拌滤出碳纤维,再经四氢呋喃浸泡洗涤24h,烘干,得到CF-3;
4)将硅烷偶联剂KH5501加入乙醇水溶液中(硅烷偶联剂的加入量为醇水溶液质量的0.5%,醇和水的质量比5:1),充分搅拌混合均匀,获得硅烷偶联剂水解液,将CF-3分散于其中,搅拌或超声,滤出纤维,干燥,得到CF-4。复合改性后的碳纤维单丝拉伸强度可达4.56GPa,与聚氨酯间的界面剪切强度可达32.33MPa。
实施例2
一种碳纤维表面改性处理方法,包括如下步骤:
1)将5g高性能沥青基碳纤维浸渍在12wt%苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯的丙酮溶液中加热到60℃处理2h,烘干,得到CF-1。
2)在120℃的真空条件下,将CF-1添加进高锰酸钾的硫酸溶液中,进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为8,烘干,得到CF-2;高锰酸钾的硫酸溶液是指将55ml摩尔浓度为0.6mol/L的硫酸中加入0.6g高锰酸钾配制而成的溶液。
3)将CF-2分散于乙醚中,加入硼氢化锂(使用量为0.07g硼氢化锂/gCF-2),在20℃搅拌3.5h,然后加入2mol/L的盐酸150ml,搅拌滤出碳纤维,再经四氢呋喃浸泡洗涤12~24h,烘干,得到CF-3;
4)将硅烷偶联剂KH570加入90wt%甲醇水溶液中(硅烷偶联剂的加入量为醇水溶液质量的1%),充分搅拌混合均匀,获得硅烷偶联剂水解液,将CF-3分散于其中,搅拌或超声,滤出纤维,干燥,得到CF-4。复合改性后的碳纤维单丝拉伸强度可达4.87GPa,与聚氨酯间的界面剪切强度可达34.56MPa。
实施例3
一种碳纤维表面改性处理方法,包括如下步骤:
1)将8g丙烯腈碳纤维浸渍在15wt%马来酸酐接枝的乙醇溶液中加热到60℃处理2h,烘干,得到CF-1。
2)在150℃的真空条件下,将CF-1添加进高锰酸钾的硫酸溶液中,进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为7,烘干,得到CF-2。高锰酸钾的硫酸溶液是指将60ml摩尔浓度为0.9mol/L的硫酸中加入0.8g高锰酸钾配制而成的溶液。
3)将CF-2分散于乙醚中,加入硼氢化锂(使用量为0.1g硼氢化锂/gCF-2),在30℃搅拌3h,然后加入2.5mol/L的盐酸320ml,搅拌滤出碳纤维,再经四氢呋喃浸泡洗涤12h,烘干,得到CF-3;
4)将硅烷偶联剂KH580加入85%异丙醇水溶液中(硅烷偶联剂的加入量为醇水溶液质量的2%),充分搅拌混合均匀,获得硅烷偶联剂水解液,将CF-3分散于其中,搅拌或超声,滤出纤维,干燥,得到CF-4。复合改性后的碳纤维单丝拉伸强度可达4.65GPa,与聚氨酯间的界面剪切强度可达33.84MPa。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种碳纤维表面改性处理方法,其特征在于,包括如下步骤:
1)将碳纤维浸渍在相容剂溶液中加热到50~60℃处理2~5h,烘干,得到CF-1;
2)在100℃~150℃的真空条件下,将CF-1添加进高锰酸钾的硫酸溶液中,进行氧化刻蚀处理,处理完毕后自然降温到室温并水洗至pH为6~8,烘干,得到CF-2;
3)将CF-2分散于乙醚中,加入硼氢化锂,在10~30℃搅拌3~4h,然后加入1.5~2.5mol/L的盐酸,搅拌滤出碳纤维,再经四氢呋喃浸泡洗涤12~24h,烘干,得到CF-3;
4)将硅烷偶联剂加入醇水溶液中,充分搅拌混合均匀,获得硅烷偶联剂水解液,将CF-3分散于其中,搅拌或超声,滤出纤维,干燥,得到CF-4。
2.根据权利要求1所述的碳纤维表面改性处理方法,其特征在于,所述相容剂溶液是将相容剂溶于有机溶剂中形成质量浓度为10~15wt%的溶液。
3.根据权利要求2所述的碳纤维表面改性处理方法,其特征在于,所述相容剂选自马来酸酐接枝或者苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯。
4.根据权利要求1所述的碳纤维表面改性处理方法,其特征在于,所述高锰酸钾的硫酸溶液是指将50~60ml摩尔浓度为0.5~0.9mol/L的硫酸中加入0.4~0.8g高锰酸钾配制而成的溶液。
5.根据权利要求1所述的碳纤维表面改性处理方法,其特征在于,所述硼氢化锂的使用量为0.05~0.1g/gCF-2;盐酸的使用量为20~40mL/gCF-2。
6.根据权利要求1所述的碳纤维表面改性处理方法,其特征在于,所述步骤4)中的醇为甲醇、乙醇、异丙醇中的一种,硅烷偶联剂为KH550,KH5501,KH560,KH570,KH580,KH602或KH792中的一种。
7.根据权利要求6所述的碳纤维表面改性处理方法,其特征在于,所述硅烷偶联剂的加入量为醇水溶液质量的0.5~2%,醇和水的质量比5~10:1。
8.根据权利要求1所述的碳纤维表面改性处理方法,其特征在于,所述碳纤维是高性能沥青基碳纤维或丙烯腈碳纤维。
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