碳纳米管制备工艺对其产量和形貌的影响

系统考察了反应温度和催化剂前驱体二茂铁用量对碳纳米管产量和形貌的影响,发现在本实验条件下,最佳反应温度为700～800℃,最佳二茂铁用量为0.15～0.20g,且通过反应温度和二茂铁用量的控制,在一定程度上能够控制所得碳纳米管的管径与管长.     

裂解温度对碳纳米管制备的影响

以纳米级复合物NiO/SiO2为催化剂，甲烷为碳源，采用催化分解法制备了碳纳米管，并运用TEM对不同实验条件下得到的纳米碳管进行了形貌分析，结果表明：反应温度对碳纳米管的产率和形貌有着很重要的影响。反应温度过高或过低，碳纳米管的产率都很低。适合碳纳米管生长的温度范围是620℃-720℃，在660℃-680℃之间反应可得到稳定的产率。在640℃-680℃之间可以得到高纯度的产物，温度过高或过低时得到的碳纳米管形貌不均一而且含有很多杂质。     

微波固相法合成纳米氧化镁

以乙酸镁和草酸为原料,用微波固相法制备了立方晶系结构的纳米氧化镁.TGA对前驱体的热分析表明微波处理能降低分解温度.采用XRD、TEM和IR对不同制备条件下MgO的晶型、晶粒尺寸、以及表观形貌等进行了表征,结果表明:焙烧温度、时间、微波加热时间对粒径影响较大;在600℃下焙烧3h制备的MgO平均晶粒尺寸为14.33nm.     

环己烷浮游催化法在碳纤维表面生长碳纳米管

以环己烷为碳源、二茂铁为催化剂前躯,采用浮游催化法成功的在碳纤维表面生长了碳纳米管(CNT),制备了多尺度杂化材料CNTs/CF。实验重点考察了反应温度、二茂铁浓度、载气等参数对CNT在纤维表面生长的影响,通过扫描电镜(SEM)、投射电镜(TEM)研究了CNTs/CF的形貌及产物CNT的微观结构。当固定反应温度为820℃、二茂铁-环己烷浓度为2g/100mL时,随着氢气在载气中含量在0～100%范围内变化,产物CNT直径亦有86nm降低至39nm。通过单丝拉伸测试发现,相比初始碳纤维,不同长度的CNTs/CF单纤维强度下降幅度均在10%以内。     

碳纳米管／PMMA／PVAc复合膜的制备及其导电性能研究

用竖式炉流动法，以二茂铁为催化剂，硫为助催化剂，苯为碳源制备碳纳米管（CNT），反应温度为1100-1200℃，碳纳米管的外径为20-40nm，内径10-30nm，长度5-20μm，并在2800℃对碳纳米管进行石墨化处理。用超声分散和溶液浇铸工艺制备碳纳米管，聚甲基丙烯酸甲酯（PMMA）／聚醋酸乙烯酯（PVAc）复合膜和石墨化碳纳米管／PMMA／PVAc复合膜，石墨化碳纳米管复合膜的导电性能明显优于碳纳米管复合膜，石墨化碳纳米管／PMMA／PVAc复合膜和碳纳米管／PMMA／PVAc复合膜的渗流阈值分别为2．5％和5％（质量分数），碳纳米管／PMMA／PVAc复合膜是很好的气敏候选材料。     

反应温度对碳纳米管的影响

本文利用化学气相沉积( CVD)法,以乙烯为碳源气体,二茂铁为催化剂,在二氧化硅上制备出一系列碳纳米管,并通过拉曼光谱和扫描电子显微镜( SEM)对其形貌、结构和组分进行表征,分析反应温度对碳纳米管的影响.研究发现:当反应温度为860℃时,有均匀的碳纳米管薄膜生成,其管径和长度分别达到104 nm和95 μm,同时结构缺陷少,非碳管杂质较少,纯度较高.     

不同基底上碳纳米管的制备及生长机理

以二茂铁为催化前驱物,C2H2为碳源,N2为载气,采用浮动催化法,在蓝宝石、单晶硅、石英、玻璃以及碳纤维基底上制备了不同形貌和结构的碳纳米管.利用扫描电子显微镜和Raman光谱对碳纳米管的形貌和微结构进行了表征.结果表明在蓝宝石和石英基底上所生长的碳纳米管薄膜具有较好的定向性和较高的石墨化程度;单晶硅基底上碳纳米管薄膜呈"底疏顶密"分布;而玻璃和碳纤维基底上所生长的碳纳米管不具有定向性.最后,对不同基底对碳纳米管生长的影响进行了分析和讨论.     

定向碳纳米管薄膜的制备

以二茂铁为催化剂前驱体,氢气为载气,乙炔为碳源,硅片作衬底,用化学气相沉积法,采用不同的催化剂引入方式,在700℃下分别制备出定向碳纳米管薄膜及非定向碳纳米管薄膜.并基于实验结果对影响生长定向碳纳米管的因素进行分析,表明催化剂颗粒的诱导作用是导致生长定向碳纳米管的重要原因.     

薄壁碳纳米管的制取

采用催化裂解法,以二氯苯为碳源,二茂铁为催化剂,制取了薄壁碳纳米管.引入多壁碳纳米管的薄壁指数?来表征多壁碳纳米管的薄壁程度.研究了氢气流量、反应温度和催化剂浓度对薄壁碳纳米管制取的影响.确定了制取薄壁碳纳米管的优化参数:反应温度为850℃,催化剂浓度为0.06g/ml,氩气流量为500ml/min,氢气流量为200ml/min,反应溶液进给量为0.012ml/min.制备出薄壁指数达5.6的大中空薄壁碳纳米管.     

使用硅油-水体系制备纳米氢氧化镁

以硫酸镁和氢氧化钠为主要原料,用化学沉淀法在硅油-水体系中制备氢氧化镁阻燃剂,用X射线衍射(XRD)、透射电镜(TEM)、傅里叶变换红外光谱(FT-IR)和热重分析仪(TGA)对产物的形貌、粒径、晶型结构和热稳定性进行表征,研究了反应时间、温度、搅拌速度、盐和碱溶液浓度、加料方式等因素对氢氧化镁形貌和分解温度的影响.结果表明:当反应时间为6 h、反应温度为60℃、搅拌速度为1500 r/min时,制得质量和性能较好的纳米氢氧化镁.     

Low Temperature Growth of Vertically Aligned Carbon Nanotubes via Floating Catalyst Chemical Vapor Deposition Method

Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups.However,the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced.In this work,the effects of varying the preheating temperature on the synthesis of CNT were investigated.The reaction temperature was set at 570℃.The preheating set temperature was varied from 150 to 400℃ at 50℃ interval.Three O-ring shape heating mantels were used as heating source for the preheater.In situ monitoring device was used to observe the temperature profile in the reactor.Benzene and ferrocene were used as the carbon source and catalyst precursor,respectively.Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃.When the preheating temperature was increased up to 400℃,both the length and the alignment of CNTs produced were improved.     

Study on the controllable scale-up growth of vertically-aligned carbon nanotube arrays

Vertically aligned carbon nanotubes (VA-CNTs) with high purity have been grown on quartz substrate via the gas phase catalytic chemical vapour deposition (CVD) by using ferrocene as the catalyst source and camphor as the carbon source. The effects of catalyst concentration, flow rate and water assistance on the morphology and structure of VA-CNTs are investigated by SEM, TEM, Raman and XPS characterizations. Under the optimized CVD conditions with modest ferrocene concentration and flow rate, dense and well VA-CNT arrays have been obtained. The water concentration should be controlled to improve CNTs alignment and impurity without damaging the walls of CNTs.     

Influence of catalyst particles on multi-walled carbon nanotubes morphology and structure

Multi-walled carbon nanotubes (MWCNTs) have been successfully grown by Chemical Vapor Deposition (CVD) method. Elucidating the key characteristics of catalyst sources that affect carbon nanotubes growth is of great importance for improving and control MWCNTs morphology and structure. In this work we present a systematically study of CVD parameters, such as catalyst source, substrate morphology and temperature and how it affects carbon nanotubes synthesis. The novelty of this work lies on the catalyst composition. Two specific catalyst sources were analyzed: (i) Fe₂Co and (ii) Fe₂Co with ferrocene. Cyclic Voltammetry results confirmed the presence of Fe²⁺ in the Fe₂Co with ferrocene solution. X-Ray Diffraction analysis confirmed the presence of iron particles on the substrate surface after its submission to growth conditions. Raman results suggested an improvement in carbon nanotubes crystalline quality catalyzed by Fe₂Co with ferrocene. For tridimensional substrates such as fibers, the Fe₂Co with ferrocene provided aligned CNTs with lower defects density noticed in Raman spectra and SEM micrographs. Finally, we corroborated the Fe²⁺ encapsulation relation with the growth mechanism and MWCNTs formation.     

Gaseous detonation fabrication of CNTs and CNTs doping with Fe based composites

The carbon nanotubes (CNTs) and CNTs doping with Fe based composites were rapid fabricated by gaseous detonation decomposition of oxygen, benzene and ferrocene mixed precursors. A series of novel experiments were designed to investigate the condensation and formation of carbon structural nanomaterials. The TEM, EDS, EDX, XRD and Raman characterizations provide fundamental evidence of the high yield and purity of the CNTs, CNTs doping with Fe composites during the gaseous detonation reaction process. The results showed that CNTs, CNTs with Fe based nanocrystals, spherical CCFNPs and their mixed products are with variant morphologies. The obtained CNTs is multi-walled carbon nanotubes and CNTs doping with a body-centered cubic iron or iron carbide cores, which can be obtained respectively through adjusting and controlling the detonation reaction environment and the precursors.     

气相生长纳米碳纤维的形态控制

报道了在浮动催化系统中,催化剂、促进剂以及苯/氢气比例等因素对气相生长纳米碳纤维形态的决定性作用和不同结构形态纳米碳纤维的选择生长.利用控制催化剂前体和促进剂的含量以及苯与氢气的比例等因素,制备了平直碳纳米管、弯曲碳纳米管、碳珠/纳米碳纤维、纳米碳纤维等不同结构的气相生长纳米碳纤维.实验结果表明,在浮动催化系统中,调节催化剂和促进剂的含量以及苯与氢气的摩尔比等关键性因素可以实现对气相生长纳米碳纤维形态结构的控制.     

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。     

Synthesis of carbon and carbon–nitrogen nanotubes using green precursor: jatropha-derived biodiesel

The jatropha-derived biodiesel, a green precursor was found to be a new and promising precursor for the synthesis of carbon nanotubes (CNTs) and carbon–nitrogen (C–N) nanotubes. The CNTs and C–N nanotubes have been synthesised by spray pyrolysis of biodiesel with ferrocene and ferrocene–acetonitrile, respectively, at elevated temperature under an argon atmosphere. The typical length and diameter of as-grown CNTs are 20?µm and 20–50?nm, respectively. The C–N nanotubes are found in bundles with effective length of ～30?µm and diameter ranging between 30 and 60?nm with bamboo-shaped morphology. The as-grown CNTs and C–N nanotubes were characterised through scanning and transmission electron microscopes, X-ray photoelectron, Raman and Fourier transform infrared spectroscopic techniques. These investigations revealed that the nanotubes synthesised by jatropha-derived biodiesel are clean from carbonaceous impurities and the bamboo compartment formations in C–N nanotubes are due to nitrogen incorporation. The nitrogen concentration in C–N nanotubes decreases with the increase in synthesis temperature.     

碳源对碳纳米管形态的影响

以苯和甲苯为碳源,二茂铁为催化剂,含硫化合物为助催化剂,采用浮游催化裂解法制备了碳纳米管,并采用TEM对不同条件下所得碳纳米管进行了形态分析。结果发现,碳源中苯和甲苯的配比对碳纳米管的形态有着重要的影响。以纯苯为碳源时,产物主要为直线型碳纳米管,并存在极少量短的弯曲型碳纳米管。随着碳源中甲苯比例的增加,产物中折线型碳纳米管增加。以纯甲苯为碳源,产物中仍有少量直线型碳纳米管,而不完全是折线型碳纳米管;此外,产物中还发现了极少量分支型碳纳米管。根据所得结果讨论分析了甲苯的加入对碳纳米管形态的影响以及各种碳纳米管的形成机理,认为可能是由于甲苯在催化热解过程中产生的碳种不同于苯催化热解所产生的碳种,造成碳在催化剂颗粒各处浓度不同,从而在碳纳米管的不同部位引入五元环和七元环而形成各种形态的碳纳米管。     

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.