CN1948144A - 一种超长定向的碳纳米管丝/薄膜及其制备方法 - Google Patents
一种超长定向的碳纳米管丝/薄膜及其制备方法 Download PDFInfo
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Abstract
一种超长定向的碳纳米管丝/薄膜及其制备方法，涉及一种碳纳米管丝和碳纳米管薄膜及其制备方法。所述的碳纳米管丝/薄膜由多束碳纳米管管束端部相互缠绕连接而成，其取向基本一致，宏观直径在微米级以上，长度在厘米级以上；碳纳米管薄膜其宏观厚度在几十纳米以上，宽度在几十微米以上，长度在厘米级以上。其制备方法包括利用浮游法在基底表面生长出碳纳米管阵列，然后使用拉伸工具从碳纳米管阵列一端抽取碳纳米管丝或薄膜，通过持续拉伸，使碳纳米管管束沿拉伸方向形成定向碳纳米管丝/薄膜。利用该方法可以实现批量制备这种碳纳米管丝/薄膜，拉伸时碳管无需在基板上，且容易控制碳纳米管束初始拉伸形状来进一步控制碳纳米管丝/薄膜的尺寸。
Description
发明领域
本发明是关于一种超长定向的碳纳米管丝/薄膜及其制备方法。
背景技术
现有的制备碳纳米管技术一般得到微米级的碳纳米管，例如“纳米聚团床催化裂解法”(专利申请号：01118349.7；PCT/CN02/00044)可以获得大批量的这类碳纳米管；进一步采用浮游方法可以获得长度在毫米级的碳纳米管(专利公开号：CN 1724343A)。制备更长的碳纳米管宏观体仍然是一个难点，其在理论和实验研究具有重要意义。
朱宏伟等(专利公开号：CN 02100684)采用立式浮动催化裂解制备了单壁碳纳米管，其碳纳米管长度为几厘米，直径和人的头发丝相当的单壁碳纳米管管束。但是该碳纳米管制备方法由于受到反应器尺寸的限制，催化剂在反应器内停留时间不能够过长，且生长温度较高。而姜开利等(专利公开号：CN 1483667A)采用在硅基板上面镀一层催化剂膜，然后进行碳纳米管的生长，再采用拉伸的方法获得依靠范德华力连接的碳纳米管绳。但是该方法受到硅片尺寸的限制，且先镀膜的方法不容易大批量制备碳纳米管。
发明内容
本发明的目的在于提供一种碳纳米管丝、碳纳米管薄膜及其制备方法，使所制备的碳纳米管丝或薄膜具有超长定向的特点，且该方法不受反应器尺寸的限制，以解决碳纳米管大批量生产的问题。
本发明的技术方案如下：
一种超长定向碳纳米管丝，其特征在于：所述的碳纳米管丝由多束碳纳米管管束端部相互缠绕连接而成，其中的碳纳米管取向基本一致，且宏观直径在微米级以上，长度在厘米级以上。
一种超长定向碳纳米管薄膜，其特征在于：所述的碳纳米管薄膜由多束碳纳米管管束相互交错连接而成，碳纳米管取向基本一致，且宏观厚度在几十纳米以上，宽度在几十微米以上，长度在厘米级以上。
本发明提供的制备上述超长定向碳纳米管丝的方法，其特征在于该方法按如下步骤进行：
1)提供曲率半径不小于10μm的基底置于反应器中，所述的基底采用硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底；
2)在保护气体存在的情况下，向反应器内通入碳纳米管催化剂前体和碳源，在生长温度为600～900℃下，在基底上长出碳纳米管阵列；
3)利用拉伸工具，从碳纳米管阵列一端抽取碳纳米管束拉伸成丝，通过持续拉伸，使碳纳米管管束沿拉伸方向形成定向碳纳米管丝。
本发明提供的制备上述超长定向碳纳米管薄膜的方法，其特征在于该方法按如下步骤进行：
1)提供曲率半径不小于10μm的基底置于反应器中，所述的基底采用硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底；
2)在保护气体存在的情况下，向反应器通入碳纳米管催化剂前体和碳源，在生长温度为600～900℃下，在基底上长出碳纳米管阵列；
3)利用拉伸工具，从碳纳米管阵列一端抽取多束碳纳米管管束拉伸成膜，通过持续拉伸，使多束碳纳米管管束沿拉伸方向形成定向碳纳米管膜。
在本发明的上述方法中，所述的碳纳米管催化剂前体为铁基、镍基、钴基的金属有机化合物或无机化合物，或者它们的混合物。所述的铁基、镍基、钴基的金属有机化合物为二茂铁、羰基铁、乙酰丙酮铁、二茂镍或二茂钴；所述的铁基、镍基、钴基的金属无机化合物为三氯化铁、硝酸铁、硝酸钴或硝酸镍。
在本发明的上述方法中，所述的碳源采用低碳烷烃、烯烃、环烷烃、芳烃或它们的混合物；所述的保护气体采用氢气、氩气、氮气、氦气或它们的混合物。所述的反应器为流化床、喷动床、转鼓、移动床或固定床中的一种或其几种反应器的组合形式。
本发明的技术特征还在于：所形成的定向碳纳米管丝还可以进行加捻。
相比现有技术，本发明具有如下优点：该方法中制备碳纳米管阵列不需要预先镀催化剂薄膜，且碳纳米管可以生长在硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底，这样提供了在生长时可以原位移入移出反应器的可能性，从而解决了碳纳米管阵列大批量制备的问题。同时使用拉伸工具牵引碳纳米管阵列，可以得到特征尺寸在厘米级别以上的碳纳米管丝或者薄膜。该过程可以通过拉伸工具控制碳纳米管束初始拉伸形状来进一步控制碳纳米管丝和薄膜的尺寸；且在拉伸获得碳纳米管丝或膜的过程中碳纳米管阵列不需留在基底上。
附图说明
图1是本发明方法制得的碳纳米管阵列的SEM图。
图2是从碳纳米管阵列的一端通过镊子连续拉伸形成碳纳米管丝的示意图。
图3是所制备的碳纳米管丝的SEM图。
图4是所制备的碳纳米管薄膜的SEM图。
具体实施方式
本发明所述的超长定向碳纳米管丝，是由多束碳纳米管管束端部相互缠绕连接而成，其中的碳纳米管取向基本一致，且宏观直径在微米级以上，长度在厘米级以上，通过连续拉伸可以长达数百米或更长的丝(如图3所示)。
本发明所述的超长定向碳纳米管薄膜，是由多束碳纳米管管束相互交错连接而成，碳纳米管取向基本一致，且宏观厚度在几十纳米以上，宽度在几十微米以上，长度在厘米级以上。(如图4所示)
制备过程首先提供曲率半径不小于10μm的基底，基底可采用硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底；然后在保护气体存在的情况下，向反应器通入碳纳米管催化剂前体和碳源，在生长温度为600～900℃下，在基底上长出碳纳米管阵列；之后利用拉伸工具，从碳纳米管阵列一端抽取碳纳米管束拉伸成丝，通过持续拉伸，使碳纳米管管束沿拉伸方向形成定向碳纳米管丝。丝的直径通过初始拉伸碳纳米管管束的尺寸来控制，通过持续拉伸碳纳米管阵列进一步控制丝长度。或利用拉伸工具，从碳纳米管阵列一端抽取多束碳纳米管管束拉伸成膜，通过持续拉伸，使多束碳纳米管管束沿拉伸方向形成定向碳纳米管膜。薄膜的厚度和宽度通过初始拉伸的多束碳纳米管束的轴向尺寸来控制，通过持续拉伸碳纳米管阵列进一步控制膜长度。
在上述制备方法中，所述的碳纳米管催化剂前体为铁基、镍基、钴基的金属有机化合物或无机化合物，或者它们的混合物。所述的铁基、镍基、钴基的金属有机化合物为二茂铁、羰基铁、乙酰丙酮铁、二茂镍或二茂钴；所述的铁基、镍基、钴基的金属无机化合物为三氯化铁、硝酸铁、硝酸钴或硝酸镍。这些催化剂前体在其高于其分解温度下可以获得金属原子，团聚形成金属颗粒，即为碳纳米管催化剂。所述的碳源采用低碳烷烃、烯烃、环烷烃、芳烃或它们的混合物；所述的保护气体采用氢气、氩气、氮气、氦气或它们的混合物。所述的反应器为流化床、喷动床、转鼓、移动床或固定床中的一种或其几种反应器的组合形式。另外，我们可以对其形成的定向碳纳米管丝进行加捻。
下面通过几个具体的实施例对本发明的制备方法做进一步的说明。
实施例1.本实施例考察采用浮游法制备碳纳米管阵列，采用其曲率半径无穷大的厚度为1mm，长宽为25mm×25mm的二氧化硅片作为基底，然后将球颗粒放入固定床反应器中，在氢气和氩气的气氛下升温到反应温度900℃。然后通入二茂铁的环己烷溶液，碳纳米管催化剂前体二茂铁原位分解形成铁催化剂，碳源催化裂解形成碳纳米管阵列。经过2.5hr后可以在二氧化硅片表面获得长度为5.4mm的阵列(图1)。
取出二氧化硅基板，保留阵列在其表面，直接采用拉伸工具镊子将碳纳米管阵列中选定一段包括多个碳纳米管管束的一端牵引抽取直径为1μm碳纳米管束，通过以0.1m/s的速度持续拉伸(图2)，通过1hr的拉伸，使碳纳米管管束沿拉伸方向形成直径约为1μm，长度达到数百米的超长定向碳纳米管丝(图3)。
在拉伸过程中，拉伸所用的力大小取决于开始所选的碳纳米管管束大小，即丝越粗，所用的力越大。且通过控制初始碳纳米管束的直径进而控制碳纳米管丝的直径。用该方法制备的碳纳米管丝由多根碳纳米管管束相互交错进行连接而成，其取向基本一致。
通过对得到的碳纳米管丝进行加捻，进一步提高其强度，改善其力学性能。将该碳纳米管丝通过含量为0.8％的PVA的水溶液，碳纳米管丝表面包覆一层PVA，从而形成了碳纳米管丝/PVA复合物。
实施例2.采用曲率半径为1mm的二氧化硅/二氧化锆复合材质球作为基底，将球颗粒放入移动床反应器中，在氢气和氮气的气氛下升温到反应温度750℃。然后通入含有1∶1的二茂镍、二茂铁的二甲苯溶液，催化剂前体原位分解形成碳纳米管催化剂，碳源催化裂解形成碳纳米管阵列。经过1hr后可以在球表面获得长度为0.5mm的阵列。
将如上得到的长满碳纳米管阵列从二氧化硅球表面剥离，然后采用带固定拉伸模具将碳纳米管阵列中选定一段包括多个碳纳米管管束的一端牵引抽取直径约为100μm碳纳米管束，通过以0.01m/s的速度持续拉伸，通过0.3hr的拉伸，使碳纳米管管束沿拉伸方向形成直径约为100μm，长度达到数米的超长定向碳纳米管丝。
实施例3.采用曲率半径为10μm石英纤维作为基板，然后将纤维放入移动床反应器中，在氢气和氩气的气氛下升温到反应温度800℃。然后通入羰基钴的苯溶液，羰基钴原位分解形成镍催化剂，碳源催化裂解形成碳纳米管阵列。经过0.8hr后可以在石英纤维表面获得长度为0.3mm的阵列。
取出长满阵列的石英纤维，保留阵列在其表面，直接采用拉伸工具镊子将碳纳米管阵列中选定一段包括多个碳纳米管管束的一端牵引抽取直径为0.8μm碳纳米管束，通过以0.1cm/s的速度持续拉伸，通过10min的拉伸，使碳纳米管管束沿拉伸方向形成直径为0.8μm，长度达到半米的超长定向碳纳米管丝。
实施例4.采用曲率半径为100μm的石英砂作为基板，然后将球颗粒放入流化床反应器中，在氢气和氮气的气氛下升温到反应温度600℃。然后通入三氯化铁蒸气作为催化剂前体，三氯化铁原位分解形成铁催化剂，通入丙烯作为碳纳米管生长碳源，碳源催化裂解形成碳纳米管阵列。经过1hr后可以在石英砂表面获得长度为0.1mm的阵列。
取出长满阵列的石英砂，保留阵列在其表面，直接采用拉伸工具镊子将碳纳米管阵列中选定一段包括多个碳纳米管管束的一端牵引抽取直径为10μm碳纳米管束，通过以0.1cm/s的速度持续拉伸，通过2min的拉伸，使碳纳米管管束沿拉伸方向形成直径为10μm，长度达到厘米级别的超长定向碳纳米管丝。
实施例5.采用曲率半径为25mm的石英管管壁作为基板，其本身作为固定床反应器，在氦气的气氛下升温到反应温度700℃。然后在100℃的条件下蒸发羰基铁，羰基铁原位分解形成铁催化剂，通入乙烷作为碳源，其催化裂解形成碳纳米管阵列。经过1hr后可以在石英管表面获得长度为1.1mm的阵列。
将上述阵列从石英管上剥离，然后采用3M纸粘附碳纳米管一段，从碳纳米管阵列中抽取成膜的多束碳纳米管管束，通过以0.1cm/s持续拉伸，通过20min的拉伸，使碳纳米管管束沿拉伸方向形成宏观厚度在100nm，宽度在1cm，长度达到米级别的超长定向碳纳米管薄膜(图4)。
用该方法制备的碳纳米管薄膜包括多根碳纳米管管束，每个碳纳米管管束由多根有较好取向的碳纳米管组成。该薄膜可以独立存在，也可以依附在某种基板上形成具有透明导电的薄膜。
实施例6.采用曲率半径为100mm的石英管管壁作为基板，其本身作为固定床反应器，在氢气和氩气的气氛下升温到反应温度800℃。然后在300℃的条件下进入二茂铁的苯溶液，二茂铁原位分解形成铁催化剂，其催化裂解形成碳纳米管阵列。经过0.5hr后可以在球表面获得长度为0.6mm的阵列。然后待炉冷却至室温后再次升温到800℃，再次通入二茂铁的苯溶液1hr，此时在原有的阵列底部长出长度为1.1mm的阵列。此时阵列累计高度为1.7mm。
将上述阵列从石英管上剥离，然后采用3M纸粘附碳纳米管一段，从碳纳米管阵列中抽取成膜的多束碳纳米管管束，通过以0.3cm/s持续拉伸，通过5min的拉伸，使碳纳米管管束沿拉伸方向形成宏观厚度在0.5μm以上，宽度在3cm，长度达到米级别的超长定向碳纳米管薄膜。
实施例7.采用曲率半径为2mm的石英砂作为基板，然后将石英砂颗粒放入转鼓反应器中，在氢气和氩气的气氛下升温到反应温度730℃。然后通入硝酸钴的乙醇作为催化剂前体，硝酸钴原位分解形成铁催化剂，通入丁二烯作为碳纳米管生长碳源，碳源催化裂解形成碳纳米管阵列。经过0.5hr后可以在石英砂表面获得长度为0.1mm的阵列。
取出长满阵列的石英砂，保留阵列在其表面，直接采用拉伸工具镊子将碳纳米管阵列中选定一段包括多个碳纳米管管束的一端牵引抽取直径为30μm碳纳米管束，通过以0.5cm/s的速度持续拉伸，通过4min的拉伸，使碳纳米管管束沿拉伸方向形成直径约为30μm，长度达到近米级别的超长定向碳纳米管丝。
Claims (9)
1.一种超长定向碳纳米管丝，其特征在于：所述的碳纳米管丝由多束碳纳米管管束端部相互缠绕连接而成，其中的碳纳米管取向基本一致，且宏观直径在微米级以上，长度在厘米级以上。
2.一种超长定向碳纳米管薄膜，其特征在于：所述的碳纳米管薄膜由多束碳纳米管管束相互交错连接而成，碳纳米管取向基本一致，且宏观厚度在几十纳米以上，宽度在几十微米以上，长度在厘米级以上。
3.一种如权利要求1所述的超长定向碳纳米管丝的制备方法，其特征在于该方法按如下步骤进行：
1)提供曲率半径不小于10μm的基底置于反应器中，所述的基底采用硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底；
2)在保护气体存在的情况下，向反应器内通入碳纳米管催化剂前体和碳源，在生长温度为600～900℃下，在基底上长出碳纳米管阵列；
3)利用拉伸工具，从碳纳米管阵列一端抽取碳纳米管束拉伸成丝，通过持续拉伸，使碳纳米管管束沿拉伸方向形成定向碳纳米管丝。
4.按照权利要求3所述的碳纳米管丝的制备方法，其特征在于：所述的碳纳米管催化剂前体为铁基、镍基、钴基的金属有机化合物或无机化合物，或者它们的混合物。
5.按照权利要求4所述的碳纳米管丝的制备方法，其特征在于：所述的铁基、镍基、钴基的金属有机化合物为二茂铁、羰基铁、乙酰丙酮铁、二茂镍或二茂钴；所述的铁基、镍基、钴基的金属无机化合物为三氯化铁、硝酸铁、硝酸钴或硝酸镍。
6.按照权利要求4所述的碳纳米管丝的制备方法，其特征在于：所述的碳源采用低碳烷烃、烯烃、环烷烃、芳烃或它们的混合物；所述的保护气体采用氢气、氩气、氮气、氦气或它们的混合物。
7.按照权利要求3、4、5或6所述的所述的碳纳米管丝的制备方法，其特征在于：所述的反应器为流化床、喷动床、转鼓、移动床或固定床中的一种或其几种反应器的组合形式。
8.按照权利要求3所述的碳纳米管丝的制备方法，其特征在于：对步骤3)中所形成的定向碳纳米管丝进行加捻。
9.一种如权利要求2所述的碳纳米管薄膜的制备方法，其特征在于该方法按如下步骤进行：
1)提供曲率半径不小于10μm的基底置于反应器中，所述的基底采用硅、二氧化硅、氧化铝、氧化锆、氧化镁或含有这些物质的耐高温基底；
2)在保护气体存在的情况下，向反应器通入碳纳米管催化剂前体和碳源，在生长温度为600～900℃下，在基底上长出碳纳米管阵列；
3)利用拉伸工具，从碳纳米管阵列一端抽取多束碳纳米管管束拉伸成膜，通过持续拉伸，使多束碳纳米管管束沿拉伸方向形成定向碳纳米管膜。
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| US20090208708A1 (en) | 2009-08-20 |
| WO2008055421A1 (en) | 2008-05-15 |
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