CN100540765C - 气相生长碳纤维和无机细粒的复合材料及其用途 - Google Patents

气相生长碳纤维和无机细粒的复合材料及其用途 Download PDF

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CN100540765C
CN100540765C CNB2004800267430A CN200480026743A CN100540765C CN 100540765 C CN100540765 C CN 100540765C CN B2004800267430 A CNB2004800267430 A CN B2004800267430A CN 200480026743 A CN200480026743 A CN 200480026743A CN 100540765 C CN100540765 C CN 100540765C
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gas
phase growth
carbon fibre
inorganic particle
fine inorganic
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CN1853012A (zh
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森田利夫
外轮千明
山本龙之
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

本发明涉及气相生长碳纤维和无机细粒的复合材料，其含有：气相生长碳纤维，碳纤维的各纤维丝在结构中带有沿其轴延伸的空腔，并具有0.001至1微米的直径和5至15，000的纵横比；和无机细粒，其粒度为0.0001至5微米，这些粒子沉积在碳纤维表面上，其中气相生长碳纤维的平均直径与无机细粒的平均粒度的比率为1∶0.01至1∶5，气相生长碳纤维与无机细粒的质量比为1∶0.005至1∶50；且保持了碳纤维的碳晶体结构并改变了表面特性。

Description

气相生长碳纤维和无机细粒的复合材料及其用途
相关申请的交叉参考
本申请是依据35 U.S.C.Section 111(a)提交的，其依据35 U.S.C.Section 119(e)(1)要求于2003年9月25日依据35 U.S.C.Section 111(b)的规定提交的美国临时申请60/505,621的权利。
技术领域
本发明涉及由气相生长碳纤维和无机细粒形成的复合材料及其用途。特别地，本发明涉及通过在气相生长碳纤维表面上沉积无机细粒来形成的复合材料，其中使碳纤维表面的特性改变；还涉及其中气相生长碳纤维起到承载无机细粒的载体作用的气相生长碳纤维和无机细粒的复合材料(下文中，该复合材料可缩写成“气相生长碳纤维/无机细粒复合材料”)。
背景技术
在将具有长成的碳晶体的气相生长碳纤维与树脂或其它材料混合形成复合材料的情况下，碳纤维对树脂之类的基质润湿的能力是关键因素。如果气相生长碳纤维不易被基质润湿，碳纤维就难以在基质中均匀分散，且碳纤维或气相生长碳纤维会在基质中形成互相分离的聚集体。同时，碳晶体已经长成的气相生长碳纤维的表面是非活性的，因此该碳纤维表面不易受到偶联剂或添加剂的作用。
在将碳纤维或气相生长碳纤维的表面改性的尝试中，已经提出了多种表面氧化法。这些方法的典型例子是(1)利用硝酸或硫酸的酸处理法，(2)空气氧化法，和(3)臭氧氧化法(参看日本公开专利出版物(kokai)61-12967号、日本公开专利出版物(kokai)2000-96429号、和日本公开专利出版物(kokai)61-119767号)。近年来，还提出了用氟在等离子体气氛中处理碳纤维表面的方法(参看日本公开专利出版物(kokai)3-227325号)。
在氧化处理之后，在碳纤维的表面碳层中引入官能团，例如羧基、羰基、羟基或类似基团，由此碳纤维表面变成活性。因此，可以使偶联剂等作用于表面上的这类官能团，由此进一步使碳纤维表面改性(“Tanso Sen-i”(“碳纤维”)作者Otani，Kindai Henshu Ltd.(1972))。
发明公开
在传统的通过氧化处理在气相生长碳纤维表面引入官能团的方法中，碳纤维表面的特性得到了提高。然而，碳纤维表面的氧化会破坏碳晶体结构；碳晶体结构有助于引出气相生长碳纤维的原始物理性质，包括强度、导电性和导热性。
因此，本发明的一个目的是提供气相生长碳纤维和无机细粒的复合材料，其表面特性改变了但碳纤维的碳晶体结构未被破坏。
本发明人发现，当在气相生长碳纤维表面上沉积表现出各种特性的无机细粒以形成复合材料时，可以将碳纤维表面改性，从而表现出所需特性，并且，当通过物理(机械)技术(即通过机械化学法)形成这种复合材料时，与使用传统的溶剂分散法的情况相比，容易形成复合材料，而且抑制了碳纤维表面晶体结构的破坏，由此使所得复合材料表现出优异的特性。本发明人还发现，当通过机械化学法由气相生长碳纤维和能够用作催化剂等的无机细粒形成复合材料时，碳纤维可用作无机细粒催化剂的载体。已经基于这些发现完成了本发明。
因此，如下所述，本发明提供了气相生长碳纤维/无机细粒复合材料及其用途。
1.气相生长碳纤维和无机细粒的复合材料，其含有：气相生长碳纤维，碳纤维的各纤维丝在结构中带有沿其轴延伸的空腔，并具有0.001至1微米的直径和5至15,000的纵横比；和无机细粒，其粒度为0.0001至5微米，这些粒子沉积在碳纤维表面上，其中气相生长碳纤维的平均直径与无机细粒的平均粒度的比率为1∶0.01至1∶5。
2.按照上文1的气相生长碳纤维和无机细粒的复合材料，其中气相生长碳纤维与无机细粒的质量比为1∶0.005至1∶50。
3.按照上文1或2的气相生长碳纤维和无机细粒的复合材料，其中无机细粒是由属于元素周期表第2至15族的元素或含有该元素的化合物形成的。
4.按照上文3的气相生长碳纤维和无机细粒的复合材料，其中属于元素周期表第2至15族的元素是镁、钙、钛、锆、钒、铬、钼、钨、锰、铁、钌、锇、钴、铑、镍、钯、铂、铜、银、金、锌、镉、铝、镓、铟、硅、锗、锡、磷或铋。
5.按照上文3的气相生长碳纤维和无机细粒的复合材料，其中含有属于元素周期表第2至15族的元素的化合物是氧化物、碳酸盐、硫酸盐、硝酸盐、络合物或卤化物的形式。
6.按照上文3的气相生长碳纤维和无机细粒的复合材料，其中含有属于元素周期表第2至15族的元素的化合物是氧化物的形式。
7.按照上文1或2的气相生长碳纤维和无机细粒的复合材料，其中无机细粒是由至少一种选自由二氧化硅、碳酸钙、氧化铝、二氧化钛和氧化铁的物质形成的。
8.按照上文1的气相生长碳纤维和无机细粒的复合材料，其中气相生长碳纤维含有0.01至5质量％的硼。
9.一种树脂复合材料，其含有如上文1至8任一项所述的气相生长碳纤维和无机细粒的复合材料。
10.一种糊状物，其含有如上文1至8任一项所述的气相生长碳纤维和无机细粒的复合材料。
11.一种催化剂，其含有如上文1至8任一项所述的气相生长碳纤维和无机细粒的复合材料。
下面将详细描述本发明的气相生长碳纤维和无机细粒的复合材料。
本发明中使用的气相生长碳纤维(下文可缩写成“VGCF”(注册商标))的各纤维丝具有沿其轴延伸的空腔、0.001至1微米的直径和5至15,000的纵横比。优选地，纤维丝具有0.002至0.5微米的直径和10至10,000的纵横比。
可以通过烃之类的气体在金属催化剂存在下的气相热分解来制造气相生长碳纤维。
例如，公开了下列制造VGCF的方法：将例如苯之类的用作原材料的有机化合物和例如二茂铁之类的用作催化剂的有机-过渡金属化合物与载气一起加入高温反应炉，由此在基材上制造VGCF的方法(日本公开专利出版物(kokai)60-27700号)；以分散状态制造VGCF的方法(注册商标)(日本公开专利出版物(kokai)60-54998号)；和VGCF在反应炉壁上生长的方法(日本专利2778434)。将通过上述任何方法制得的VGCF在惰性气氛(例如氩气)中于600至1,500℃进行热处理，并在2,000至3,300℃下进一步热处理，由此使VGCF石墨化。
通过上述方法，可以制造直径相对较小且纵横比相对较高的碳纤维，其表现出优异的导电性和导热性，并适合用作填充材料。
VGCF的特点在于其形状和晶体结构。VGCF的丝具有如下结构：包括在中部的非常薄的空腔，以及许多在空腔周围生长的碳六边形网络层以形成年轮形态的同心圆柱体。
在本发明中使用的VGCF可以是，例如，日本公开专利出版物(kokai)2002-266170号中公开的支化气相生长碳纤维，其中具有带有这种空腔的结构的部分互相连接。
本发明中使用的VGCF可以具有80至500纳米、优选80至140纳米、更优选80至110纳米的平均纤维丝直径；纤维丝直径的变动很小，即总纤维中65％或更多、优选70％或更多、更优选75％或更多(基于纤维的数)落在平均直径的±20％的范围内。此外，本发明中使用的VGCF可以具有0.015克/立方厘米或更低的堆积密度和0.015Ωcm或更低的电阻率。
上述VGCF或支化VGCF可以按照国际公开WO00/58536小册子中公开的方法(硼处理法)在存在硼或硼化合物(例如硼酸、硼酸盐、氧化硼或碳化硼)的情况下在惰性气氛(例如氩气)中于2,000至3,300℃进行热处理；或按照日本公开专利出版物(kokai)2003-20527号中公开的方法(气体接触法)进行热处理而制造；而且在本发明中可以使用含有硼、或者硼和硼化合物的气相生长碳纤维。
本发明中使用的无机细粒是由属于元素周期表第2至15族的元素的单质或含有该元素的化合物形成的。优选地，无机细粒是由镁、钙、钛、锆、钒、铬、钼、钨、锰、铁、钌、锇、钴、铑、镍、钯、铂、铜、银、金、锌、镉、铝、镓、铟、硅、锗、锡、磷或铋的单质或含有这种元素的化合物形成的。更优选地，无机细粒是由镁、钙、钛、锆、钒、铬、钼、钨、锰、铁、钌、锇、铑、钯、铂、铜、银、金、锌、镉、铝、镓、铟、硅、锗、锡、磷或铋的单质或含有这种元素的化合物形成的。
这种化合物的例子包括氧化物、碳酸盐、硫酸盐、硝酸盐、络合物和卤化物。其中，氧化物、碳酸盐和卤化物是优选的，氧化物特别优选的。此处所用的术语“氧化物”(也就是由氧与氧之外的元素形成的化合物)包括过氧化物、超氧化物、酸性氧化物、碱性氧化物、两性氧化物、双氧化物和含氧酸盐。
氧化物的具体例子包括二氧化硅、碳酸钙、氧化铝、二氧化钛、氧化铁和钛酸钡。
使用这种无机化合物，可以使气相生长碳纤维的表面改性，使其表现出例如亲水性或疏水性的特性。
在本发明中，无机细粒的平均粒度与气相生长碳纤维的平均直径的比率优选为0.01∶1至5∶1，更优选0.01∶1至3∶1，再优选0.1∶1至1∶1。当无机细粒的平均粒度与气相生长碳纤维的平均直径的比率低于0.01∶1时，会变得难以调节无机细粒的粒度，而当无机细粒的平均粒度与气相生长碳纤维的平均直径的比率高于5∶1时，就会变得难以将无机细粒结合到气相生长碳纤维表面上，并降低将碳纤维表面改性的效果。
在本发明中，当气相生长碳纤维与无机细粒形成复合材料时，无机细粒与气相生长碳纤维的质量比优选为0.005∶1至50∶1，更优选0.01∶1至40∶1，再优选0.05∶1至30∶1。当无机细粒与气相生长碳纤维的质量比低于0.005∶1时，就难以获得将碳纤维表面改性的效果，而当无机细粒与气相生长碳纤维的质量比高于50∶1时，会变得难以将细粒结合到碳纤维表面上，并降低将碳纤维表面改性的效果。
可以通过机械化学法制造本发明的气相生长碳纤维和无机细粒的复合材料，其中无机细粒物理(机械)沉积到气相生长碳纤维表面上。
在机械化学法中，原则上，不使用溶剂而在施加压力和剪切力的同时将无机细粒与气相生长碳纤维干混在一起，由此使碳纤维和粒子互相结合。机械化学法几乎不使用溶剂，因此有利之处在于不必在溶剂中分散气相生长碳纤维和无机细粒并且不必去除溶剂。通过使用机械化学法，可以使无机细粒沉积到气相生长碳纤维上，而不会破坏构成碳纤维和气相生长碳纤维的碳晶体，由此改进碳纤维的表面特性。
工业适用性
在本发明的气相生长碳纤维和无机细粒的复合材料中，用无机细粒将气相生长碳纤维的表面改性，而不会破坏碳纤维的碳晶体结构。因此，该复合材料具有由气相生长碳纤维产生的强度、导电性和导热性，其可用作填充材料，例如在导电树脂中使用的填料，或在铅蓄电池中使用的添加剂。此外，当气相生长碳纤维用作无机细粒的载体时，该载体可以没有损害地利用原始碳纤维的特性(即强度、导电性和导热性)。此外，通过调节树脂复合材料中所含的气相生长碳纤维和无机细粒的复合材料中无机细粒的沉积度(量)，可以调节该材料的导电性。
本发明的最佳实施方式
下面将参照实施例描述本发明。实施例中使用的气相生长碳纤维和无机细粒描述如下。
气相生长碳纤维：
使用苯和二茂铁(催化剂)通过日本专利2778434号中描述的方法制造气相生长碳纤维(平均直径：150纳米；平均长度：20微米)。将由此制得的碳纤维在氩气氛中于1,000℃进行热处理，然后在2,800℃进行石墨化处理。发现所得气相生长碳纤维具有0.678纳米的层间距离C0和0.2个点/微米(通过SEM图像分析计算而得的每微米纤维丝中支化点的数量)的支化度，即表示纤维丝之间结合程度的指数。
无机细粒：
(1)碳酸钙：平均初级粒度：700纳米(Shiraishi Calcium Kaisha，Ltd.，SECTACARB HG的产品)
(2)氧化铝：平均初级粒度：30纳米(Showa Denko K.K.，UFA-40的产品)
(3)二氧化钛：平均初级粒度：30纳米(Showa Denko K.K.的产品，SUPERTITANIA(注册商标)F-4)
实施例1-6：由气相生长碳纤维和无机细粒形成复合材料
将气相生长碳纤维与碳酸钙以98∶2(按质量计)的比率混合，并在下述条件下对所得混合物进行机械化学处理，由此形成气相生长碳纤维/碳酸钙复合材料(2)(实施例1)。
将实施例1中使用的碳酸钙分别替换成氧化铝和二氧化钛，由此形成气相生长碳纤维/氧化铝复合材料(2)(实施例2)和气相生长碳纤维/二氧化钛复合材料(2)(实施例3)。
将气相生长碳纤维与二氧化钛以95∶5(按质量计)的比率混合，并对所得混合物进行相同的机械化学处理，由此形成气相生长碳纤维/二氧化钛复合材料(5)(实施例4)。
将气相生长碳纤维与二氧化钛以90∶10(按质量计)的比率混合，并对所得混合物进行相同的机械化学处理，由此形成气相生长碳纤维/二氧化钛复合材料(10)(实施例5)。
使用下述气相生长碳纤维：具有0.012克/立方厘米的堆积密度，压缩到0.8克/立方厘米的堆积密度时具有0.007Ωcm的电阻率，具有97纳米的纤维丝直径，纤维丝直径标准偏差为23.4纳米，平均纤维丝长度为13微米(平均纵横比＝130)，其中总纤维中75％(基于纤维的数)落在平均直径±20％的范围内，由此形成与实施例3的复合材料类似的气相生长碳纤维/二氧化钛复合材料(2)(实施例6)
机械化学处理条件：
所用装置：MICROS-O型，Nara Machinery Co.，Ltd.的产品。
容积：0.75升
有效容积：0.45升
处理量：20克
主轴旋转速度：1,800rpm
处理时间：90分钟
实施例7-13和对比例1-6：含有气相生长碳纤维/无机细粒复合材料的树脂复合材料
使用下述方法，将实施例1至6中形成的各种气相生长碳纤维和无机细粒的复合材料与树脂(尼龙66，下文缩写成“PA”)混合，由此评测所得复合材料在树脂复合材料中的分散性。通过测量树脂复合材料的导电性评测复合材料的分散性。使用CM3001(Toray Industries，Inc.的产品)作为PA。
PA复合材料的形成：
使用Labo Plastomill(Toyo Seiki)在270℃和40rpm下将PA(在实施例7-11和13中为74克，在实施例12中为70克)与气相生长碳纤维/无机细粒复合材料(在实施例7-11和13中为4克，在实施例12中为8克)熔融混合10分钟。通过施加热压力(280℃，20MPa(200千克力/平方厘米)，30秒)将所得PA复合材料制成尺寸为100毫米×100毫米×2毫米的板材。使用由此制成的板材作为样品。为了比较，制备下列样品：由PA和其上没有沉积无机细粒的气相生长碳纤维的复合材料制成的样品；由PA(74克)和气相生长碳纤维(3.9克)/碳酸钙(0.08克)的混合物制成的样品；和仅由PA制成的样品。
使用四探针测量装置和绝缘电阻表测量各样品的导电性。表1显示了电阻和强度的测量结果(JIS K7194)。
表1
Figure C20048002674300111
从表1中看出，气相生长碳纤维和无机细粒的复合材料(其中无机细粒沉积在气相生长碳纤维表面上)表现出提高的对于树脂的可湿性。由该复合材料形成的树脂复合材料与由其上没有沉积无机细粒的气相生长碳纤维形成的树脂复合材料(这些复合材料是在相同条件下形成的)之间的对比表明，前一复合材料表现出更高的导电性。
实施例14和对比例7：含有气相生长碳纤维和无机细粒的复合材料的糊状物
使用三辊磨将气相生长碳纤维/氧化铝复合材料(2)(实施例14)(10质量％：基于干燥糊状物)与二甲苯改性的苯氧基树脂和用作溶剂的二醇醚捏合，由此制备导电糊。为了比较，将复合材料(2)替换成其上没有沉积无机细粒的气相生长碳纤维(对比例7)，并按照与上述相同的方式制备导电糊。
使用由此制备的糊状物，通过丝网印刷在环氧基材上印刷图案(n＝5)，然后在200℃干燥固化。完成干燥固化后，发现图案具有10微米的厚度。
发现由上述糊状物形成的图案的表面电阻分别为200Ω/□(实施例14)和400Ω/□(对比例7)。这些结果表明，当在相同条件下用于糊状物(涂膜)时，与其上没有沉积无机细粒的气相生长碳纤维相比，本发明的复合材料(其中在气相生长碳纤维表面上沉积了无机细粒)表现出改进的对树脂的可湿性和更高的导电性。
实施例15：含有气相生长碳纤维和无机细粒的复合材料的催化剂
按照与实施例1类似的方式，将气相生长碳纤维与氧化铁(WakoPureChemical Industries，Ltd.的产品，平均初级粒度：300纳米)以95∶5(按质量计)的比率混合，由此形成复合材料。将由此形成的气相生长碳纤维/氧化铁(5)复合材料(1克)置于氧化铝板上，然后将氧化铝板置于具有水平摆放的石英管(内径：20毫米，长度：600毫米)的反应炉中部，然后在氢气氛中于900℃进行还原处理60分钟。使用X-射线衍射装置分析气相生长碳纤维/氧化铁(5)复合材料，没有表现出与氧化铁对应的峰，但是表现出与铁对应的峰。将所得气相生长碳纤维/铁复合材料(0.1克)置于氧化铝板上，并将氧化铝板置于前述反应炉中。将反应炉的温度升至1,150℃，并在炉中加入氢(100毫升/分钟)和苯(1毫升/分钟)，由此使反应继续进行20分钟。在将反应炉冷却之后，发现在气相生长碳纤维/铁复合材料周围产生了大量的网状气相生长碳纤维产品(纤维直径：200纳米，纵横比：50，平均层间距离C0：0.69纳米)。
结果表明，气相生长碳纤维/铁复合材料对于由苯制造气相生长碳纤维的过程起到催化剂的作用。

Claims (8)

1.制造气相生长碳纤维和无机细粒的复合材料的方法，包括通过机械化学法不使用溶剂而在施加压力和剪切力的同时将无机细粒与气相生长碳纤维干混在一起，由此使无机细粒沉积到气相生长碳纤维的表面上，所述气相生长碳纤维的各纤维丝在结构中具有沿其轴延伸的空腔，并具有0.001至1微米的直径和5至15,000的纵横比，所述无机细粒的粒度为0.0001至5微米，其中气相生长碳纤维的平均直径与无机细粒的平均粒度的比率为1∶0.01至1∶5。
2.按照权利要求1的方法，其中气相生长碳纤维与无机细粒的质量比为1∶0.005至1∶50。
3.按照权利要求1或2的方法，其中无机细粒是由属于元素周期表第2至15族的元素或含有该元素的化合物形成的。
4.按照权利要求3的方法，其中属于元素周期表第2至15族的元素是镁、钙、钛、锆、钒、铬、钼、钨、锰、铁、钌、锇、钴、铑、镍、钯、铂、铜、银、金、锌、镉、铝、镓、铟、硅、锗、锡、磷或铋。
5.按照权利要求3的方法，其中含有属于元素周期表第2至15族的元素的化合物是氧化物、碳酸盐、硫酸盐、硝酸盐、络合物或卤化物的形式。
6.按照权利要求3的方法，其中含有属于元素周期表第2至15族的元素的化合物是氧化物的形式。
7.按照权利要求1或2的方法，其中无机细粒是由至少一种选自由二氧化硅、碳酸钙、氧化铝、二氧化钛和氧化铁组成的组的物质形成的。
8.按照权利要求1的方法，其中气相生长碳纤维含有0.01至5质量％的硼。
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