CN102137754A - 碳纳米管加强的纳米复合物 - Google Patents

碳纳米管加强的纳米复合物 Download PDF

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CN102137754A
CN102137754A CN2008801309960A CN200880130996A CN102137754A CN 102137754 A CN102137754 A CN 102137754A CN 2008801309960 A CN2008801309960 A CN 2008801309960A CN 200880130996 A CN200880130996 A CN 200880130996A CN 102137754 A CN102137754 A CN 102137754A
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茅东升
Z·彦尼夫
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Abstract

碳纳米管(CNT)很长，所以在预浸渍体制备过程中它们不能在碳纤维之间贯穿，将它们缩短，避免它们被碳纤维滤出。这导致与纯环氧树脂相比，机械性质明显提高(挠曲强度和挠曲模量)。

Description

碳纳米管加强的纳米复合物
本申请是美国专利申请序列号11/757,272的部分继续，后者要求美国临时专利申请序列号60/819,319和60/810,394的优先权，所有这些申请都通过参考结合于此。本申请是美国专利申请序列号11/693,454的部分继续，后者要求美国临时申请序列号60/788,234和60/810,394的优先权，所有这些申请都通过参考结合于此。本申请是美国专利申请序列号11/695,877的部分继续，后者要求美国临时申请序列号60/789,300和60/810,394的优先权，所有这些申请都通过参考结合于此。
背景技术
自从在1991年首次观察到碳纳米管(CNT)以来，碳纳米管已经成为大量研究的重点(S.Iijima，“石墨碳的螺旋状微管(Helical microtubules of graphitic carbon)”，Nature 354，56(1991))。许多研究者已经报导了这种新形式碳的不寻常的物理和机械性质。单壁CNT(SWNT)的直径通常为0.5-1.5纳米，而双壁CNT(DWNT)的直径为1-3纳米，多壁CNT(MWNT)的直径为5-100纳米。碳纳米管独特的电子性质、优于金刚石的热传导性，以及劲度、强度和回弹性优于目前任何材料的机械性质，使得CNT给基础新材料体系的开发提供了极大的机会。特别是CNT杰出的机械性质(E＞1.0TPa，拉伸强度为50GPa)以及低密度(1-2.0克/厘米3)使得人们对于CNT加强复合材料的开发非常感兴趣(Eric W.Wong，Paul E.Sheehan，Charles M.Lieber，″纳米棒和纳米管的纳米束机械性质：弹性，强度和韧性(Nanobeam Mechanics：Elasticity，Strength，and Toughness of Nanorods and Nanotubes)″，Science 277，1971(1997))。CNT是目前地球上已知最强的材料。与MWNT相比，SWNT和DWNT是更有前景的用于复合物的加强材料，这是因为它们具有更高的表面积和纵横比。表1列出了SWNT、DWNT和MWNT的表面积和纵横比。
表1
问题是CNT在生长时通常相当长(从数微米到超过100μm)，而且最接近纤维之间的距离非常小，所以它们难以穿透到纤维加强塑料(FRP)的基质中。例如，对于单向碳纤维或织物加强的环氧复合物，碳纤维的含量约为60体积％，因此最接近的碳纤维之间的间距约为1微米(假设碳纤维的直径为7-8μm，密度约为1.75-1.80克/厘米3，环氧基质的密度为1.2克/厘米3)。用于制备复合物的玻璃纤维和其它类型纤维也是如此。CNT可加强聚合物树脂，以改进强度和模量之类的机械性质，但是CNT不能加强FRP，因为在FRP制备过程中它们被纤维滤出。
附图简要说明
图1说明依据本发明实施方式的纳米复合物的制备方法；
图2显示MWNT的SEM数字图像；
图3A-3C分别显示MWNT加强的环氧树脂、DWNT加强的环氧树脂和SWNT加强的环氧树脂的断裂表面的SEM数字图像；
图4A显示DWNT加强的CFRP的断裂表面的SEM数字图像，显示在碳纤维之间无DWNT贯穿；
图4B显示DWNT加强的CFRP的断裂表面的SEM数字图像，显示DWNT被滤出到预浸渍体的端层；
图5A-5C分别显示缩短的MWNT、DWNT和SWNT的SEM数字图像；和
图6A-6C分别显示MWNT加强的CFRP、DWNT加强的CFRP和SWNT加强的CFRP的断裂表面的SEM数字图像。
发明详述
短到2微米或比2微米更短的CNT能在纤维之间贯穿，因此明显提高FRP的机械性质。
在本发明的一个实施方式中，给出该实施方式的详细例子，从而更好地说明本发明。
环氧树脂，SWNT，DWNT，MWNT和硬化剂
从日本阿瑞斯洼公司(Arisawa Inc.，Japan)获得环氧树脂(双酚A)。还从该公司获得硬化剂(双氰胺)，用于使环氧纳米复合物固化。从比利时的纳农塞公司(Nanocyl，Inc.，Belgium)获得SWNT、DWNT和MWNT。CNT可以纯化到＞90％的碳含量。但是，原始CNT或用羧酸或胺之类的官能团官能化的CNT同样也可以。CNT的长度约为5-20μm。图2显示MWNT的SEM数字图像。除了环氧树脂外，也可以采用其它热固性材料，例如聚酰亚胺、酚醛塑料、氰酸酯和双马来酰亚胺，或热塑性材料，例如尼龙。
图1显示了制备依据本发明实施方式的环氧/CNT纳米复合物的工艺流程示意图。所有组分在70℃的真空烘箱中干燥16小时，以除去水分。对于各树脂，CNT的装载量可以为1.0重量％。将CNT放入丙酮中(101)，在步骤102中用微流仪(可从微流公司(Microfluidics Co.)购得，型号为Y110)分散。微流仪使用高压物流，这些物流以超高的速率在精确限定的微米尺寸通道中碰撞。对产品的剪切力和冲击力的共同作用产生均匀的分散体。随后CNT/丙酮作为凝胶形成(103)，结果使CNT良好地分散在丙酮溶剂中。但是，也可以采用其它方法，例如超声法或高剪切混合法。还可以使用表面活性剂将CNT分散在溶液中。然后在步骤104中，将环氧树脂加入CNT/丙酮凝胶，产生环氧/CNT/丙酮溶液105，然后在70℃的浴中超声处理1小时(步骤106)，产生环氧/CNT/丙酮悬浮液107。在步骤108中，在70℃以1400转/分钟的速率搅拌混合处理半小时，将CNT进一步分散在环氧树脂中，产生环氧/CNT/丙酮凝胶109。然后在步骤110中，以4.5重量％的比率将硬化剂加入环氧/CNT/丙酮凝胶109中，在70℃搅拌1小时。在步骤112中，将所得凝胶111在70℃的真空烘箱中脱气48小时。然后将材料113在160℃固化2小时。为了测试材料113，随后将材料倒入特氟隆模中，在抛光处理115后表征样品的机械性质(挠曲强度和挠曲模量)。
上述树脂(环氧/CNT/硬化剂)在70℃脱气48小时后，也可以用于通过热熔法制备FRP。碳纤维(从托里工业公司(Toray Industries，Inc.)购得，型号T700-12k)可用于制备预浸渍体。“预浸渍体”(或“预浸渍材料”)是本领域已知的用于表示″预浸渍的″复合纤维的术语。这些纤维的形式可以是编织状的，或者是单向的。它们含有一定量的基质材料，用于在制造过程中将它们粘结在一起，并且将它们与其它组分粘结在一起。预浸渍体可存储在冷却区域中，因为活化大多在加热条件下才发生。因此，预浸渍体复合结构的形成通常需要烘箱或高压釜使其固化。
首先，将CNT加强的环氧树脂涂布在隔离纸上。然后，通过用CNT加强的环氧树脂薄膜浸渍单向碳纤维来得到预浸渍体。将碳纤维的体积控制在60％。预浸渍体的面积重量为180克/米2。
纳米复合物的机械性质
表2显示了CNT加强的环氧树脂以及再用单向碳纤维加强的样品的机械性质(挠曲强度和挠曲模量)。可以看出，在树脂形式时，与纯(neat)环氧树脂相比，机械性质明显提高(挠曲强度的提高都在30％以上，挠曲模量的提高至少达到10％)。但是，在碳纤维加强的聚合物(CFRP)形式中，与纯环氧CFRP相比，CNT加强的CFRP的两种机械性质都没有提高。
表2
Figure BPA00001328494900041
然后，可使用扫描电子显微镜(SEM)来检测树脂和CFRP样品中CNT的分散性。在树脂形式中，所有CNT加强的环氧样品表现出极佳的CNT分散(参见图3A-3C)。但是，CNT被单向碳纤维滤出到预浸渍体的端层(参见DWNT加强的环氧CFRP的图4A-4B)。这是因为CNT很长，而最接近的碳纤维之间的间距只有约1微米，所以CNT不能在碳纤维之间贯穿。这也是树脂中CNT加强并不能转移到CFRP中的原因。
CNT的缩短以及环氧树脂和CFRP的加强
因为CNT很长，所以在预浸渍体制备过程中它们不能在碳纤维之间贯穿，必需将它们缩短，避免被碳纤维滤出。可将MWNT、DWNT和SWNT与浓酸混合物(HNO3∶H2SO4＝3∶1)混合，在120℃搅拌4小时。使用滤纸(聚碳酸酯滤纸，具有2微米孔，以滤出酸)过滤CNT。然后，可用离子化水洗涤CNT 4-5次，在50℃的真空烘箱中干燥12小时。图5A-5C分别显示缩短到小于2微米长度的MWNT、DWNT和SWNT的SEM图像。
表3显示缩短的CNT加强的环氧树脂以及再用单向碳纤维加强的样品的机械性质(挠曲强度和挠曲模量)。可以看出，在树脂形式时，与纯环氧树脂相比，机械性质明显提高(挠曲强度的提高都在30％以上，挠曲模量的提高至少达到10％)，与上述较长的CNT加强的环氧树脂类似。在CFRP形式中，与纯环氧CFRP相比，两种性质都提高。例如，与纯环氧CFRP相比，SWNT加强的CFRP的挠曲强度提高17％。
表3
Figure BPA00001328494900051
然后，可使用扫描电子显微镜(SEM)来检测CFRP样品中CNT的分散性。如图6A-6C所示，缩短的MWNT、DWNT和SWNT在碳纤维之间贯穿并良好分散。

Claims (7)

1.一种复合材料，其包含碳纳米管、聚合物和碳纤维，其中所述碳纳米管的平均长度小于2微米。
2.如权利要求1所述的复合材料，其特征在于，所述聚合物是热固性塑料或热塑料。
3.如权利要求2所述的复合材料，其特征在于，所述热固性塑料选自下组：聚酰亚胺、酚醛塑料、氰酸酯和双马来酰亚胺。
4.如权利要求1所述的复合材料，其特征在于，所述碳纳米管未官能化。
5.如权利要求1所述的复合材料，其特征在于，所述碳纳米管用羧酸官能团或胺官能团官能化。
6.如权利要求1所述的复合材料，其特征在于，所述碳纳米管用胺官能团官能化。
7.如权利要求1所述的复合材料，其特征在于，所述碳纤维是单向碳纤维。
CN2008801309960A 2008-07-25 2008-09-30 碳纳米管加强的纳米复合物 Pending CN102137754A (zh)

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