沉积条件对碳纤维表面碳纳米管生长的影响

采用化学气相沉积(CVD)法在碳纤维(CF)表面原位生长碳纳米管(CNTs)。考察了不同催化剂、沉积温度、氢气流量以及样品距进气口距离等工艺参数对CNTs-CF生长的影响。利用SEM和高分辨透射电子显微镜(HRTEM)对CNTs-CF形貌和微结构进行了表征和分析。结果表明:在CF表面原位生长的CNTs为多壁结构,其中以Ni为催化剂得到的CNTs直径小、分布均匀;在600~750℃温度范围内,随着温度的升高,CNTs直径和长度减小,产量降低;随着氢气流量的增加,CNTs直径和长度均增加;距进气口30cm,在CF表面得到的CNTs覆盖率高、直径小且分布窄,有利于制备高质量CNTs。     

乙酰丙酮铁为催化剂源在碳纤维表面生长碳纳米管的工艺研究

以乙酰丙酮铁为催化剂源,三甘醇为溶剂,通过溶剂热法在碳纤维表面负载催化剂前驱体,在H2与N2中一定温度下进行还原,采用化学气相沉积法在碳纤维表面生长碳纳米管。研究了催化剂的负载条件和碳纳米管的生长条件,采用XRD、FTIR、RAMAN对乙酰丙酮铁在三甘醇中反应在碳纤维表面负载催化剂前驱体产物进行分析,用SEM、TEM对催化剂前驱体粒子及碳纳米管的形貌进行表征。结果表明:催化剂前驱体为粒径30nm左右的Fe3O4颗粒,当催化剂的还原温度为415℃、还原时间为60min时,Fe3O4颗粒还原成纳米Fe颗粒;当碳纳米管的生长温度为750℃、生长时间为30min、气流体积比为V(N2)∶V(H2)∶V(C2H2)=50∶10∶10时能在碳纤维表面生长出形貌均一、管径为30~60nm的碳纳米管。     

On the role of activation mode in the plasma- and hot filaments-enhanced catalytic chemical vapour deposition of vertically aligned carbon nanotubes

Catalytic chemical vapor deposition (CCVD) with different activation modes (thermal; hot filaments-enhanced; direct current plasma-enhanced and both hot filament and direct current plasma-enhanced) are achieved in order to grow vertically aligned carbon nanotubes (VA CNTs). By widely varying the power of the different activation sources of the gas (plasma, hot filaments, substrate heating) while keeping identical the substrate temperature (973 K) and the catalyst preparation, the results point out the important role of ions in the nucleation of carbon nanotubes (CNTs), as well as the etching behaviour of highly activated radicals such as H˙ in the selective growth of vertically aligned films of CNTs. Moreover, it is demonstrated that, within the deposition conditions (temperature, pressure, flow rate) used in this study, oriented carbon nanotubes can be grown only when both ions, mainly generated by the gas discharge plasma, and highly reactive radicals, mainly formed by the hot filaments, are produced in the gas phase. We propose that highly energetic ions are needed to nucleate the carbon nanotubes by increasing the carbon concentration gradient whereas the highly reactive radicals allow the selective growth of vertically aligned CNTs by preventing carbon deposition on the whole surface through chemical etching of edge carbons in graphene sheets.     

用ECR-CVD方法制备定向碳纳米管

以FeaO4纳米粒子为催化剂,CH4和H2为气源,采用电子回旋共振微波等离子体化学气相沉积技术(ECR-CVD)在多孔硅基底上制备出定向生长的碳纳米管.研究了气氛组成、气压、温度和反应时间对碳纳米管生长特性的影响.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱(Raman spectrum)表征了样品的形貌和结构.结果表明:气氛组成和气压影响了反应腔内离解碳的浓度,从而影响碳纳米管的成核、生长速度及定向生长;温度的变化改变催化剂的尺寸从而改变碳纳米管的直径,在过低的温度下碳纳米管不能实现定向生长;碳纳米管随着反应时间的延长而不断增长,但超过一定时间后催化剂颗粒被碳包覆而失去催化作用,生长停止.     

采用局部加热法选择性制备碳纳米管和纳米金刚石晶体

通过局部加热系统中的化学气相沉积法（chemical vapor deposition,CVD）实现了碳纳米管（carbon nanotube,CNT）和金刚石晶体的选择性生长加热系统只加热硅衬底而对反应过程及担载气体没有加热作用．在衬底温度为700℃时,没有生成CNT或明显的金刚石颗粒当温度升到740℃时,仍没有CNT生成,但是在模样化的铁膜上生成许多尺寸为几十纳米的金刚石颗粒温度为770℃时,在铁膜的中央部位生成许多尺寸为几十到几百纳米的金刚石颗粒,而在铁膜的边缘部位可同时观测到一些CNT的生成．当温度达到850℃时,CNT的生长区域扩大而纳米金刚石的平均尺寸和生成密度减小.在910℃的高温下,生成了大量的CNT,其平均直径为20nm,和通常的热CVD法生成的cNT相同在较低的衬底温度下,表面催化反应占主导地位而可能诱导具有sp^3结构的纳米金刚石的生成随着衬底温度的增加,围绕在衬底周围的气体被加热,在达到其气相自聚合温度后形成不饱和碳氢链,这些生成的碳氢链在sp^2结构CNT的生成中起到了重要的作用．     

Continuous synthesis of carbon nanotubes using a metal-free catalyst by CVD

This study demonstrates the first example of the use of a metal-free catalyst for the continuous synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD). In this paper silica nanoparticles produced from the thermal decomposition of PSS-(2-(trans-3,4-Cyclohexanediol)ethyl)-Heptaisobutyl substituted (POSS) were used as catalyst and ethanol was served as both the solvent and the carbon source for nanotube growth. The POSS/ethanol solution was nebulized by an ultrasonic beam. The tiny mists were continuously introduced into the CVD reactor for the growth of CNTs. The morphology and structure of the CNTs have been investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The obtained CNTs have a multi-walled structure with diameters mainly in the size range from 13 to 16 nm. Detailed investigations on the growth conditions indicate that the growth temperature and POSS concentration are important for achieving high-quality nanotubes, and that the existing of small amount of water in ethanol is effective to remove amorphous carbon species during the formation of CNTs. The mass production of CNTs without any metal contaminant will provide a chance for investing and understanding the intrinsic properties of CNTs and applications particularly in nanoelectronics and biomedicines.     

Growth of metal-free carbon nanotubes on glass substrate with an amorphous carbon catalyst layer

We have investigated the direct growth of metal-free carbon nanotubes (CNTs) on glass substrates with microwave-plasma enhanced chemical vapor deposition (MPECVD). Amorphous carbon (a-C) films were used as a catalyst layer to grow metal-free CNTs. The a-C films were deposited on Corning glass substrates using RF magnetron sputtering with the use of a carbon target (99.99%) at room temperature. They were pretreated with hydrogen plasma using a microwave PECVD at 600 degrees C. Then, CNTs were prepared using microwave PECVD with a mixture of methane (CH4) and hydrogen (H2) gases. The CNTs were grown at different substrate temperatures (400 degrees C, 500 degrees C, and 600 degrees C) for 30 minutes. Other conditions were fixed. The growth trends of CNTs against substrate temperature were observed by field emission scanning electron microscopy (FE-SEM). The structure of a-C catalyst layer and grown CNTs were measured by Raman spectroscopy. High-resolution transmission electron microscopy (HR-TEM) images showed that the CNTs had bamboo-like multi-walled structures. Energy dispersive spectroscopy (EDS) measurements confirmed that the CNTs consisted of only carbon.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.     

Optimization of synthesis condition for carbon nanotubes by chemical vapor deposition on Fe-Ni-Mo/MgO catalyst

Catalyst and reaction conditions are the main affecting factors for the yield and quality of carbon nanotubes (CNTs) produced by the chemical vapor deposition (CVD) method. In this paper a ternary component catalyst based on Fe-Ni-Mo/MgO was explored using methane as precursor. The influences of temperature and methane concentration were investigated, and the as-produced CNTs were characterized by SEM, HRTEM, XRD and TGA. The diameter of the CNTs is in the range of 20-30 nm and the maximum carbon yield can reach up to 80 times of the catalyst under the selected condition. The purity of the as-prepared CNTs is over 93%. Our results indicated that this novel tercomponent catalyst presented a good catalytic activity for manufacturing high quality and quantity of CNTs.     

工业级原料制备碳纳米管的研究

为降低碳纳米管批量制备的原料成本,以焦化苯和二茂铁为主要原料(工业级),采用浮游催化热解法制备碳纳米管,用TEM、SEM、Raman、XRD等对产物的形貌和结构进行观察和表征,着重讨论了二茂铁的分解温度和苯的挥发温度对碳纳米管的制备及其形貌的影响,并对其影响机理进行了分析.研究表明:在噻吩体积分数为0.55 mL/100 mL苯、炉膛反应温度为1170℃的前提下,当二茂铁的分解温度为150℃、苯的挥发温度为50℃时,用工业级原料完全可以制备出碳纳米管,此时,碳纳米管的内径分布在0.88~1.15 nm.     

Carbon dioxide as a carbon source for synthesis of carbon nanotubes by chemical vapor deposition

Carbon dioxide was successfully used as carbon source in the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) over Fe/CaO catalyst. The product was evaluated using both transmission electron microscopy (TEM) and Raman spectroscopy. Crooked and branching structures of multi-walled carbon nanotubes (MCNTs) with diameters of around 50 nm were observed on the TEM micrographs. Raman spectrum results show that the nanotubes have small defects, which is in agreement with the results of TEM. The influence of reaction variable such as furnace temperature and types of support media was also studied and the reaction mechanism was then discussed in this paper.     

定向碳纳米管的化学气相沉积制备法

报道了一种简便有效的合成定向碳纳米管 (CNTs)的化学气相沉积 (CVD)制备方法。以铁为催化剂 ,乙炔为碳源 ,采用单一反应炉 ,直接在石英基底上沉积催化剂颗粒薄膜 ,成功合成了定向性好、管径均匀的高质量大密度的碳纳米管     

Synthesis of multiwalled carbon nanotubes from polyethylene waste to enhance the rheological behavior of lubricating grease

Abstract

Carbon nanotubes (CNTs) are attracting great interest in enhancing rheological behavior and thermal performance of lubricating grease. In this study, CNTs were synthesized by catalytic chemical vapor deposition (CCVD) method using low-density polyethylene (LDPE) waste as a cheap carbon source and Co/MgO as an effective catalyst. The effect of temperature on the catalytic pyrolysis of LDPE to produce CNTs has been studied. Catalytic pyrolysis of LDPE waste was conducted in a temperature range of 350–600?°C using the H-ZSM-5 catalyst. The structure and quality of CNTs were fully characterized using HR-TEM, XRD, and Raman spectroscopy. On the other hand, various concentrations of CNTs (0.2, 0.4, 0.6, 0.8, and 1.0?wt%) were mixed with pure lithium grease to determine the optimum percentage that improves the properties of nano-grease. The results showed that a high yield of multiwalled carbon nanotubes (MWCNTs) was obtained with high quality at temperatures ranging from 400 to 550?°C. Also, the addition of CNTs enhanced the rheological behavior of lithium grease, and the optimum percentage of CNTs was 0.8?wt%. Furthermore, the apparent viscosity and shear stress of lithium nano-grease increased by increasing the concentration of CNTs up to 0.8%. At this concentration, the penetration value of lithium nano-grease was greater than pure grease, and the dropping point increased by 12.5%. These results suggested that CNTs prepared from LDPE waste were an excellent additive to enhance the physicochemical properties of lithium grease.     

Self-assembled interconnection by bamboo-like carbon nanotubes

Carbon nanotubes (CNTs) could be formed on Si substrate using nickel catalyst under microwave plasma-enhanced chemical vapor deposition system. Under the high, negative-bias voltage (−400 V) condition, we found the formation of the carbon nanotube islands and the bamboo-like carbon nanotube interconnection lines. Most of the bamboo-like carbon nanotubes connected with the carbon nanotubes themselves, which indicates the self-assembled characteristics of the carbon nanotube interconnection lines. The self-assembled characteristics of the bamboo-like carbon nanotube interconnection lines were evaluated using computer-aided image analysis.     

聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究

采用聚合物热解化学气相沉积(PP-CVD)法, 通过聚乙二醇(PEG)的原位热解提供碳源、柠檬酸(CA)和硝酸钴反应产生催化剂纳米粒子, 在微纳米级的片状铝粉基底上原位生长碳纳米管(CNTs)。通过实验和反应动力学建模研究了PP-CVD反应机理, 揭示了PEG热解气相成分和催化剂纳米粒子表面气-固反应对CNTs生长速率的影响规律。CO初始分压和反应温度提高, CNTs生长速率提高; H₂初始分压和催化剂密度提高, CNTs生长速率降低。模型预测的CNTs平均长度随反应温度和反应时间的变化趋势符合实验结果。因此, 本研究为进一步优化CNTs/铝复合粉末制备工艺提供了新的理论依据。     

Fe/Fe_3C填充的碳纳米管复合材料的制备与微波吸收性质

利用化学气相沉积法,以乙醇为碳源,二茂铁为催化剂前驱物,对二氯苯为添加剂,制备了Fe/Fe3C纳米线填充的碳纳米管复合材料,并通过SEM、XRD、HRTEM等分析方法对产物的形貌和微结构进行了研究。实验结果表明对二氯苯对碳纳米管的填充起决定作用,产物中Fe/Fe3C纳米线填充率可达33%;使用该复合材料制备的吸波涂层在厚度为2mm、频率为4.5GHz时有强吸收峰,厚度增加时吸收峰往低频方向移动,表明此材料有望在低频段实现对电磁波的有效吸收。     

Fe-Mo/Al_2O_3催化剂催化分解甲烷制备碳纳米管:温度对碳管结构的影响

利用化学气相沉积法,以Fe-Mo/Al_2O_3为催化剂,催化分解甲烷气体制备碳纳米管(CNTs).研究了温度,反应时间和气体流速对碳纳米管结构的影响.结果显示:温度是影响碳纳米管壁厚的关键参数.低温导致壁厚为2 nm～7 nm的多壁碳纳米管(MWCNTs)的生成.相对地,高温有利于双壁碳纳米管(DWCNTs)的生长,而更高的温度促使单壁碳纳米管(SWCNTs)的产生.进一步升高温度,得到了壁厚为3 nm～15 nm的MWCNTs和大的炭颗粒.     

Functionalization of gold-coated carbon nanotubes with self-assembled monolayers of thiolates

Multi-walled carbon nanotubes (CNT) were synthesized by chemical vapor deposition using Co–Fe as a catalyst and ethylene as a carbon source. Afterward, a simple method combining wet-chemistry and chemical reduction was used to prepare carbon nanotube/gold material (CNT/Au). Pristine nanotubes and CNT/Au were characterized by transmission electron microscopy micrographs. It appeared that gold formed nanoparticles on CNTs endings and their sidewalls. Further functionalization was carried out by using thiols of different chemical properties and molecule sizes. Thiols formed self-assembled monolayer on gold surface that led to formation of CNT/gold/thiol-functionalized material. The amounts of chemisorbed thiols were measured by elemental analysis and thermogravimetry.     

Carbon nanotube growth on cobalt-sprayed substrates by thermal CVD

We present a very simple spray-coating method for depositing cobalt catalyst over quartz substrates that can be efficiently utilized in the production of carbon nanotubes (CNTs) by thermal chemical vapor deposition (CVD). Very uniform multi-walled carbon nanotubes (MWNTs) have been grown from cobalt catalyst over large surfaces by thermal CVD using mixtures of acetylene and ammonia. The effect of catalyst pretreatments and CNT growth temperature on the CNT diameter has been studied and discussed.     

In situ synthesis of ceria decorated carbon nanotubes by chemical vapor deposition

Ceria decorated carbon nanotubes (CNTs) were in-situ synthesized by chemical vapor deposition using a Ni/Ce/Cu catalyst. Ceria nanoparticles, with a diameter of about 3-8 nm, were highly dispersed on the CNTs, and it is believed that they are formed at the same time as the CNTs.