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CN1176014C - 一种直接合成超长连续单壁碳纳米管的工艺方法 - Google Patents

一种直接合成超长连续单壁碳纳米管的工艺方法 Download PDF

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CN1176014C
CN1176014C CNB021006849A CN02100684A CN1176014C CN 1176014 C CN1176014 C CN 1176014C CN B021006849 A CNB021006849 A CN B021006849A CN 02100684 A CN02100684 A CN 02100684A CN 1176014 C CN1176014 C CN 1176014C
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朱宏伟
徐才录
吴德海
魏秉庆
P·M·阿加亚
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Abstract

一种直接合成超长连续单壁碳纳米管的工艺方法，涉及一种碳纳米材料的制备工艺。本发明采用立式浮动催化裂解法，以正己烷为碳源，二茂铁为催化剂，噻吩为添加剂制成反应溶液，以蒸汽的形式随氢气一同引入反应器进行催化裂解。在特定的工艺参数下，制得的超长绳状单壁碳纳米管产物，管束定向性良好，纯度最高可达85%；管束中的单壁碳纳米管生长连续、平直，长度可达20cm(单根单壁碳纳米管长径比＞108)。本发明由于采用立式浮动催化裂解法，仅需一个立式电炉，且不需要石墨基底，二茂铁直接溶解在正己烷溶液中，无需预先在氢气气氛下还原，因此操作简单、方便，可实现超长连续单壁碳纳米管束的低成本批量制备。

Description

一种直接合成超长连续单壁碳纳米管的工艺方法
技术领域
本发明涉及一种碳纳米材料的制备工艺，尤其涉及一种单壁碳纳米管的合成工艺方法。
背景技术
单壁碳纳米管的发现极大地推动了纳米科技研究及其应用领域的发展。1996年，Smalley研究小组在《科学》杂志(Science，1996，273(5274)：483～487)上报道了采用激光蒸发工艺合成高纯度单壁碳纳米管的方法。1997年，Journet等人在《自然》杂志(Nature，1997，388：756～758)报道了采用直流电弧法批量制备单壁碳纳米管的工艺。另外，采用催化裂解工艺制备单壁碳纳米管也成为该研究领域的焦点之一，因为该方法是最可能实现碳纳米管大批量工业化的制备方法。Dai等人在文献(Chemical Physics Letters，1996，260：471～475)中首先采用CO气体为碳源制备了单壁碳纳米管，但其产量及产率很低。该方法制备单壁碳纳米管的工艺条件比较苛刻，参数控制比较严格。后来，乙烯、甲烷、苯等都被作为碳源制备单壁碳纳米管，通过对工艺参数的改进，产量和产率有所提高。目前单壁碳纳米管的批量制备仍是该领域的难点和热点。Cheng等人在文献(Applied Physics Letters，1998，72(25)：3282～3284)中介绍了卧式浮动催化裂解工艺制备单壁碳纳米管。虽然以上方法实现了单壁碳纳米管的制备，但所得单壁碳纳米管的长度均为微米量级，且管束间定向性差，单壁碳纳米管纯度低，从而限制了理论及实验上对超长连续单壁碳纳米管的研究。制备超长连续的单壁碳纳米管是一个重点、难点，在理论及应用方面具有重要意义。这里所指的“超长”是指单壁碳纳米管的长度达到十厘米量级；“连续”是指管束中的单壁碳纳米管连续生长，无间断，并且有良好的定向性。
在催化裂解法中，立式浮动催化裂解法(Carbon，2000，38(14)：1933～1937)是大批量制备多壁碳纳米管和碳纳米纤维的一种有效方法。现有的立式浮动催化裂解法以苯为碳源，二茂铁(Fe(C5H5)2)为催化剂，噻吩(C4H4S)为添加剂。设备简单，成本低，适于大批量生产。同卧式浮动催化裂解法实验设备相比，立式浮动催化裂解法仅需一个立式电炉，并且不需要石墨基底。二茂铁直接溶解在碳源中，无需预先在氢气气氛下还原，二茂铁随溶液注入蒸发器，操作简单方便。但由于苯含碳量高，仅适用于制备多壁碳纳米管和碳纳米纤维。且苯有毒性，对环境造成污染。要使用立式浮动催化裂解法实现单壁碳纳米管的制备，就需要寻找一种含碳量低且无毒性的碳源。
发明内容
本发明的目的是提供一种直接合成超长连续单壁碳纳米管的工艺方法，实现超长连续单壁碳纳米管束的低成本批量制备，使所制得的单壁碳纳米管束定向性良好，纯度高且长度长。
本发明的目的是通过如下技术方案实现的：一种直接合成超长连续单壁碳纳米管的工艺方法，采用立式浮动催化裂解法，以二茂铁(Fe(C5H5)2)为催化剂，噻吩(C4H4S)为添加剂溶入碳源中制成反应溶液，以蒸汽的形式随氢气一同引入反应器进行催化裂解，其特征在于该方法是以正己烷(C6H14)为碳源。
所述反应溶液是由正己烷、(0.010～0.020g/ml)的二茂铁和(0.2～0.6wt.％)噻吩组成的混合液。反应溶液引入流量为0.2～0.8ml/min，氢气的流量为150～300ml/min。
本发明由于采用立式浮动催化裂解法，该方法仅需一个立式电炉，并且不需要石墨基底，二茂铁直接溶解在正己烷溶液中，无需预先在氢气气氛下还原，且二茂铁随溶液注入蒸发器，因此操作简单、方便，可实现超长连续单壁碳纳米管束的低成本批量制备。制得的超长绳状单壁碳纳米管产物，管束定向性良好，纯度最高可达85％；管束中的单壁碳纳米管生长连续、平直，长度可达20cm(单根单壁碳纳米管长径比＞108)。
附图说明
图1：为本发明(立式浮动催化裂解法)所用设备的结构原理示意图。
图2：为利用扫描电子显微镜检测的产物的微观形貌图。
图3：为利用透射电子显微镜检测的产物的微观形貌图。
具体实施方式
下面结合附图1具体说明本发明的工艺过程及实施方式：
立式浮动催化裂解法的设备主体为立式陶瓷反应管1(外径68mm，内径58mm，长度1600mm)，该管垂直放置在电阻炉2(额定温度为1200℃，额定功率6KW)中。反应容器的上部是蒸发器3，包括进气口4及反应溶液(正己烷、二茂铁、噻吩的混合溶液)入口5。反应溶液6通过液体微流量泵7引入蒸发器3(蒸发温度150～200℃)随载气(氢气)以蒸汽的形式一同引入反应容器1。反应容器1下面安装产物收集瓶8、过滤器9及尾气出口10。其具体操作步骤如下：
(1)首先通氩气100ml/min并开始升高炉温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1100～1200℃)，引入反应溶液开始制备产物。反应溶液6为正己烷(C6H14)、二茂铁(Fe(C5H5)2)和噻吩(C4H4S)的混合溶液。其中正已烷为碳源，二茂铁(0.010～0.020g/ml)为催化剂，噻吩(0.2～0.6wt.％)作为添加剂。
(3)反应溶液6引入流量为0.2～0.8ml/min，氢气的流量为150～300ml/min。
(4)保温一段时间后停止升温，通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
使用扫描电子显微镜(如图2所示)和透射电子显微镜(如图3所示)检测产物的微观形貌。
使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。
检测结果表明，立式浮动催化技术可以实现超长连续的单壁碳纳米管的批量制备。产物由大量密集排列的定向单壁碳纳米管束组成；管束中的单壁碳纳米管长度可达20cm，直径分布在1～2nm之间。单壁碳纳米管的纯度最高可达85％。
实施例1：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1100℃)，引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.010g/ml)为催化剂，噻吩(C4H4S，0.6wt.％)作为添加剂。
(3)反应溶液引入流量为0.5ml/min，氢气的流量为200ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和部分碳纳米管纤维组成，单壁碳纳米管含量为60％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20～60nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。
实施例2：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1150℃)，引入反应溶液开始制备产物。反应溶液采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.020g/ml)为催化剂，噻吩(C4H4S，0.4wt.％)作为添加剂。
(3)反应溶液引入流量为0.5ml/min，氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和少量双壁碳纳米管组成，单壁碳纳米管含量为85％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10～50nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。
实施例3：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃)，引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.018g/ml)为催化剂，噻吩(C4H4S，0.4wt.％)作为添加剂。
(3)反应溶液引入流量为0.2ml/min，氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和少量多壁碳纳米管、碳纳米纤维组成，单壁碳纳米管含量为80％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10～60nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。
实施例4：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃)，引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.018g/ml)为催化剂，噻吩(C4H4S，0.2wt.％)作为添加剂。
(3)反应溶液引入流量为0.8ml/min，氢气的流量为250ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和碳纳米纤维组成，单壁碳纳米管含量为70％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20～60nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。
实施例5：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃)，引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.018g/ml)为催化剂，噻吩(C4H4S，0.5wt.％)作为添加剂。
(3)反应溶液引入流量为0.5ml/min，氢气的流量为150ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和多壁碳纳米管、碳纳米纤维组成，单壁碳纳米管含量为70％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径20～60nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。
实施例6：
(1)首先通氩气100ml/min并开始升温，至1000℃左右时开始通氢气并停止氩气。
(2)升温到预定反应温度(1200℃)，引入反应溶液开始制备产物。反应溶液中采用正己烷(C6H14)为碳源，二茂铁(Fe(C5H5)2，0.018g/ml)为催化剂，噻吩(C4H4S，0.5wt.％)作为添加剂。
(3)反应溶液引入流量为0.5ml/min，氢气的流量为300ml/min。
(4)保温约60min后停止升温。通氩气(100ml/min)冷却并停止氢气，温度降至室温后收集产物。
(5)使用扫描电子显微镜和透射电子显微镜检测产物的微观形貌。产物为20cm长细丝，由单壁碳纳米管和少量多壁碳纳米管组成，单壁碳纳米管含量为80％。
(6)使用显微共焦拉曼光谱仪检测产物的直径分布及晶化程度。单壁碳纳米管产物由大量密集排列的定向单壁碳纳米管束(直径10～50nm)组成。管束由直径在1～2nm间的单壁碳纳米管组成。

Claims (3)

1.一种直接合成超长连续单壁碳纳米管的工艺方法，采用立式浮动催化裂解法，以二茂铁为催化剂，噻吩为添加剂溶入碳源中制成反应溶液，以蒸汽的形式随氢气一同引入反应器进行催化裂解，其特征在于该方法是以正己烷为碳源。
2.按照权利要求1所述的一种直接合成超长连续单壁碳纳米管的工艺方法，其特征在于所述反应溶液是由正己烷、0.010～0.020g/ml的二茂铁和0.2～0.6wt.％的噻吩组成的混合液。
3.按照权利要求1所述的一种直接合成超长连续单壁碳纳米管的工艺方法，其特征在于反应溶液引入流量为0.2～0.8ml/min，氢气的流量为150～300ml/min。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7824649B2 (en) 2005-08-19 2010-11-02 Tsinghua University Apparatus and method for synthesizing a single-wall carbon nanotube array

Families Citing this family (93)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5978833A (en) * 1996-12-31 1999-11-02 Intel Corporation Method and apparatus for accessing and downloading information from the internet
CN100411979C (zh) * 2002-09-16 2008-08-20 清华大学 一种碳纳米管绳及其制造方法
WO2004065294A2 (en) * 2003-01-17 2004-08-05 Duke University Systems and methods for producing single-walled carbon nanotubes (swnts) on a substrate
CN101230145B (zh) * 2003-02-13 2012-05-30 斯蒂茨丁荷兰聚合物学会 增强聚合物
WO2005053828A2 (en) * 2003-11-07 2005-06-16 Ahwahnee Technology, Inc. Systems and methods for manufacture of carbon nanotubes
WO2006073455A2 (en) * 2004-05-07 2006-07-13 The Regents Of The University Of California Los Alamos National Laboratory Preparation of single-walled carbon nanotubes
DE102004059814A1 (de) * 2004-12-06 2006-06-08 C. & E. Fein Gmbh Kupplung, insbesondere für ein Elektrowerkzeug
CN100500555C (zh) * 2005-04-15 2009-06-17 清华大学 碳纳米管阵列结构及其制备方法
US7754183B2 (en) 2005-05-20 2010-07-13 Clemson University Research Foundation Process for preparing carbon nanostructures with tailored properties and products utilizing same
CA2897320A1 (en) 2005-07-28 2007-01-28 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
CN100387516C (zh) * 2005-11-10 2008-05-14 上海交通大学 直接连续制备超短碳纳米管的方法
CN100391834C (zh) * 2006-09-22 2008-06-04 北京交通大学 高纯度多壁碳纳米管的制备方法
CN100443403C (zh) * 2006-11-09 2008-12-17 上海交通大学 连续合成大直径单壁碳纳米管的方法
CN100450922C (zh) * 2006-11-10 2009-01-14 清华大学 一种超长定向的碳纳米管丝/薄膜及其制备方法
US8951631B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused metal fiber materials and process therefor
US9005755B2 (en) 2007-01-03 2015-04-14 Applied Nanostructured Solutions, Llc CNS-infused carbon nanomaterials and process therefor
US8951632B2 (en) 2007-01-03 2015-02-10 Applied Nanostructured Solutions, Llc CNT-infused carbon fiber materials and process therefor
US8158217B2 (en) 2007-01-03 2012-04-17 Applied Nanostructured Solutions, Llc CNT-infused fiber and method therefor
AU2008219693B2 (en) * 2007-02-27 2012-04-12 Nanocomp Technologies, Inc. Materials for thermal protection and methods of manufacturing same
EP2125212A2 (en) 2007-03-23 2009-12-02 Lydall, Inc. Substrate for carrying catalytic particles
TW200840888A (en) * 2007-04-04 2008-10-16 Univ Nat Cheng Kung Carbon fiber of high thermal conduction and continuous gaseous growth and its manufacturing method and application
US9061913B2 (en) 2007-06-15 2015-06-23 Nanocomp Technologies, Inc. Injector apparatus and methods for production of nanostructures
JP2011508364A (ja) 2007-08-07 2011-03-10 ナノコンプ テクノロジーズ インコーポレイテッド 非金属電気伝導性および熱伝導性ナノ構造体ベースアダプター
US8308930B2 (en) * 2008-03-04 2012-11-13 Snu R&Db Foundation Manufacturing carbon nanotube ropes
EP2274464A4 (en) 2008-05-07 2011-10-12 Nanocomp Technologies Inc COMPOSITE SHEETS WITH NANOSTRUCTURES AND METHODS OF USE
JP5968621B2 (ja) 2008-05-07 2016-08-10 ナノコンプ テクノロジーズ インコーポレイテッド ナノ構造体ベースの加熱装置およびその使用方法
US8673258B2 (en) * 2008-08-14 2014-03-18 Snu R&Db Foundation Enhanced carbon nanotube
US8357346B2 (en) * 2008-08-20 2013-01-22 Snu R&Db Foundation Enhanced carbon nanotube wire
US8021640B2 (en) 2008-08-26 2011-09-20 Snu R&Db Foundation Manufacturing carbon nanotube paper
BRPI0806065B1 (pt) * 2008-10-16 2021-05-18 Petroleo Brasileiro S. A. - Petrobras método para a produção de nanoesferas de carbono
CA2750484A1 (en) 2009-02-17 2010-12-16 Applied Nanostructured Solutions, Llc Composites comprising carbon nanotubes on fiber
BRPI1008131A2 (pt) 2009-02-27 2016-03-08 Applied Nanostructured Sols "crescimento de nanotubo de carbono de baixa temperatura usando método de preaquecimento de gás".
US20100227134A1 (en) 2009-03-03 2010-09-09 Lockheed Martin Corporation Method for the prevention of nanoparticle agglomeration at high temperatures
CA2758694C (en) 2009-04-17 2017-05-23 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
EP2422595A1 (en) 2009-04-24 2012-02-29 Applied NanoStructured Solutions, LLC Cnt-infused emi shielding composite and coating
US9111658B2 (en) 2009-04-24 2015-08-18 Applied Nanostructured Solutions, Llc CNS-shielded wires
KR101696207B1 (ko) 2009-04-27 2017-01-13 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. 복합 구조물 제빙을 위한 ｃｎｔ계 저항 가열
CN101927995A (zh) * 2009-04-30 2010-12-29 中国科学院成都有机化学有限公司 一种制备大内径长度可控碳纳米管的方法
US8354593B2 (en) * 2009-07-10 2013-01-15 Nanocomp Technologies, Inc. Hybrid conductors and method of making same
BR112012002216A2 (pt) 2009-08-03 2016-05-31 Applied Nanostructured Sols método de incorporação de nanopartículas em fibras compósitas, fibra de vidro e tapete de fibra picada ou compósito
CN101996706B (zh) * 2009-08-25 2015-08-26 清华大学 一种耳机线及具有该耳机线的耳机
CN101998200A (zh) * 2009-08-25 2011-03-30 鸿富锦精密工业（深圳）有限公司 一种耳机线及具有该耳机线的耳机
WO2011035157A2 (en) * 2009-09-18 2011-03-24 Applied Materials, Inc. Apparatus and methods for forming energy storage and photovoltaic devices in a linear system
CN101696491B (zh) * 2009-10-22 2011-05-04 清华大学 石墨烯/碳纳米管复合薄膜的原位制备方法
KR20120120172A (ko) 2009-11-23 2012-11-01 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. Ｃｎｔ 맞춤형 복합재 해상 기반의 구조체
CN102596564B (zh) 2009-11-23 2014-11-12 应用纳米结构方案公司 含有碳纳米管并入的纤维材料的陶瓷复合材料及其制备方法
AU2010353294B2 (en) 2009-12-14 2015-01-29 Applied Nanostructured Solutions, Llc Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials
US9167736B2 (en) 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
CN102741465A (zh) 2010-02-02 2012-10-17 应用纳米结构方案公司 包含平行排列的碳纳米管的碳纳米管并入的纤维材料、其制造方法及从其衍生的复合材料
AU2011223743A1 (en) 2010-03-02 2012-08-30 Applied Nanostructured Solutions,Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
BR112012021968A2 (pt) 2010-03-02 2016-06-07 Applied Nanostructured Sols dispositivos elétricos enrolados em espiral que contêm materiais de eletrodo infundidos por nanotubo de carbono e métodos e aparelhos para a produção dos mesmos
US8780526B2 (en) 2010-06-15 2014-07-15 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
BR112013005802A2 (pt) 2010-09-14 2016-05-10 Applied Nanostructured Sols substratos de vidro com nanotubos de carbono crescidos sobre os mesmos e métodos para sua produção
KR101877475B1 (ko) 2010-09-22 2018-07-11 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. 탄소 나노튜브가 성장된 탄소 섬유 기판 및 그의 제조 방법
EP2619767A2 (en) 2010-09-23 2013-07-31 Applied NanoStructured Solutions, LLC Cnt-infused fiber as a self shielding wire for enhanced power transmission line
EP2661369B1 (en) 2011-01-04 2019-04-10 Nanocomp Technologies, Inc. Thermal insulators based on nanotubes, their use and method for thermal insulation.
KR20140014224A (ko) * 2011-03-08 2014-02-05 고쿠리츠 다이가쿠 호우징 나고야 다이가쿠 카본 나노 튜브의 제조 방법
RU2497752C2 (ru) * 2011-11-29 2013-11-10 Инфра Текнолоджис Лтд. Способ получения длинных углеродных нанотрубок и устройство для осуществления этого способа
US9085464B2 (en) 2012-03-07 2015-07-21 Applied Nanostructured Solutions, Llc Resistance measurement system and method of using the same
EP2838839B1 (en) 2012-04-16 2020-08-12 Seerstone LLC Method for producing solid carbon by reducing carbon dioxide
NO2749379T3 (zh) 2012-04-16 2018-07-28
JP6379085B2 (ja) 2012-04-16 2018-08-22 シーアストーン リミテッド ライアビリティ カンパニー 炭素酸化物を含有するオフガスを処理するための方法
MX2014012548A (es) 2012-04-16 2015-04-10 Seerstone Llc Metodos y estructuras para reducir oxidos de carbono con catalizadores no ferrosos.
WO2013158161A1 (en) 2012-04-16 2013-10-24 Seerstone Llc Methods and systems for capturing and sequestering carbon and for reducing the mass of carbon oxides in a waste gas stream
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
CN104619637B (zh) 2012-07-12 2017-10-03 赛尔斯通股份有限公司 包含碳纳米管的固体碳产物以及其形成方法
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
WO2014085378A1 (en) 2012-11-29 2014-06-05 Seerstone Llc Reactors and methods for producing solid carbon materials
CN102994980B (zh) * 2012-12-13 2015-01-14 苏州汉纳材料科技有限公司 高导电碳纳米管薄膜的制备方法及装置
CN104995134B (zh) * 2013-01-22 2018-06-05 Mcd技术有限公司 生产碳纳米结构的方法及装置
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
EP3129135A4 (en) 2013-03-15 2017-10-25 Seerstone LLC Reactors, systems, and methods for forming solid products
EP3114077A4 (en) 2013-03-15 2017-12-27 Seerstone LLC Methods of producing hydrogen and solid carbon
EP3129321B1 (en) 2013-03-15 2021-09-29 Seerstone LLC Electrodes comprising nanostructured carbon
US9783421B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Carbon oxide reduction with intermetallic and carbide catalysts
CN103204492A (zh) * 2013-05-03 2013-07-17 苏州汉纳材料科技有限公司 一种提高单壁碳纳米管产率的新方法
EP3010853B1 (en) 2013-06-17 2023-02-22 Nanocomp Technologies, Inc. Exfoliating-dispersing agents for nanotubes, bundles and fibers
SG11201601113SA (en) * 2013-09-04 2016-03-30 Ngee Ann Polytechnic A method for producing carbon nanotubes
EP3253709A4 (en) 2015-02-03 2018-10-31 Nanocomp Technologies, Inc. Carbon nanotube structures and methods for production thereof
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US10581082B2 (en) 2016-11-15 2020-03-03 Nanocomp Technologies, Inc. Systems and methods for making structures defined by CNT pulp networks
US11279836B2 (en) 2017-01-09 2022-03-22 Nanocomp Technologies, Inc. Intumescent nanostructured materials and methods of manufacturing same
US10870089B2 (en) * 2017-03-14 2020-12-22 4th Phase Water Technologies, Inc. Hydrophilic graphitic material
CN107601458B (zh) * 2017-09-12 2020-07-28 刘云芳 一种单壁碳纳米管的制备方法
JP7441799B2 (ja) * 2018-12-27 2024-03-01 住友電気工業株式会社 カーボンナノチューブの製造方法、カーボンナノチューブ集合線の製造方法、カーボンナノチューブ集合線バンドルの製造方法、カーボンナノチューブ製造装置、カーボンナノチューブ集合線製造装置及びカーボンナノチューブ集合線バンドル製造装置
CN113490638B (zh) 2019-02-22 2024-03-29 住友电气工业株式会社 碳纳米管及其集合线、集合线集束的制法、它们的制造装置
US11508498B2 (en) 2019-11-26 2022-11-22 Trimtabs Ltd Cables and methods thereof
CN114477141B (zh) * 2020-10-24 2023-11-24 江苏天奈科技股份有限公司 一种寡壁碳纳米管纤维束及其制备工艺
CN113562724B (zh) * 2021-07-06 2024-03-19 上海大学 一种单壁碳纳米管封装超长线性碳链及其制备方法
WO2023239500A1 (en) * 2022-06-07 2023-12-14 ExxonMobil Technology and Engineering Company Integrated production of thiophene and carbon nanotubes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5458784A (en) * 1990-10-23 1995-10-17 Catalytic Materials Limited Removal of contaminants from aqueous and gaseous streams using graphic filaments
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
US6333016B1 (en) * 1999-06-02 2001-12-25 The Board Of Regents Of The University Of Oklahoma Method of producing carbon nanotubes

Cited By (1)

* Cited by examiner, † Cited by third party
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US7824649B2 (en) 2005-08-19 2010-11-02 Tsinghua University Apparatus and method for synthesizing a single-wall carbon nanotube array

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