Low temperature and cost-effective growth of vertically aligned carbon nanofibers using spin-coated polymer-stabilized palladium nanocatalysts

We describe a fast and cost-effective process for the growth of carbon nanofibers (CNFs) at a temperature compatible with complementary metal oxide semiconductor technology, using highly stable polymer–Pd nanohybrid colloidal solutions of palladium catalyst nanoparticles (NPs). Two polymer–Pd nanohybrids, namely poly(lauryl methacrylate)-block-poly((2-acetoacetoxy)ethyl methacrylate)/Pd (LauMA_x-b-AEMA_y/Pd) and polyvinylpyrrolidone/Pd were prepared in organic solvents and spin-coated onto silicon substrates. Subsequently, vertically aligned CNFs were grown on these NPs by plasma enhanced chemical vapor deposition at different temperatures. The electrical properties of the grown CNFs were evaluated using an electrochemical method, commonly used for the characterization of supercapacitors. The results show that the polymer–Pd nanohybrid solutions offer the optimum size range of palladium catalyst NPs enabling the growth of CNFs at temperatures as low as 350 °C. Furthermore, the CNFs grown at such a low temperature are vertically aligned similar to the CNFs grown at 550 °C. Finally the capacitive behavior of these CNFs was similar to that of the CNFs grown at high temperature assuring the same electrical properties thus enabling their usage in different applications such as on-chip capacitors, interconnects, thermal heat sink and energy storage solutions.     

平直碳纳米纤维与螺旋碳纳米纤维的共同生长

研究了采用乙醇催化燃烧法制备的碳纳米纤维的形貌和结构，并且讨论了平直碳纳米纤维与螺旋碳纳米纤维分别对应的生长机制。分析结果表明在特定的实验条件下，可以制备出平直碳纳米纤维与螺旋碳纳米纤维的共生材料。螺旋碳纳米纤维的生长机制是基于催化剂颗粒的各向异性。本实验方法具有制备工艺简单，碳源无毒性，制备过程无环境污染等特点，因而有望实现大量生产。     

Interactions of gold nanoparticles with the interior of hollow graphitized carbon nanofibers

Interactions of free-standing gold nanoparticles and hollow graphitized nanofibers in colloidal suspension are investigated, revealing the first example of the controlled arrangement of nanoparticles inside nano-containers, as directed by their internal structure. The ordering is highly effective for small gold nanoparticles whose sizes are commensurate with the height of graphitic step-edges in the graphitized carbon nanofibers and is less effective for larger gold nanoparticles. Studies aimed at understanding the role of the organic-solvent surface tension, employed for the filling experiments, demonstrate that gold nanoparticles become preferentially anchored into the hollow graphitized carbon nanofibers under a mixture of pentane/CO(2) in supercritical conditions. It is shown that a three-step cleaning procedure enables effective removal of gold nanoparticles adsorbed on the exterior surface of graphitized carbon nanofibers, while ordered arrays of encapsulated nanoparticles are retained.     

Field emission characteristics of carbon nanofibers grown on copper micro-tips at low temperature

Carbon nanofibers (CNFs) were grown on copper micro-tips formed by electroplating. The nickel layer electroplated over the copper micro-tips was used as a catalyst. The CNFs were synthesized by using plasma-enhanced chemical vapor deposition (PECVD) of C₂H₂ and NH₃ at 480 °C. The copper micro-tips were formed by high current pulse electroplating, which played a significant role in characterizing our CNFs. The CNFs grown on the copper micro-tips showed outstanding field emission performance and stability, whose turn-on field, defined as one at the current density of 10 μA/cm², was 1.30 V/μm and the maximum current density reached 5.39 mA/cm² at an electric field of 4.9 V/μm.     

含铁碳纳米纤维的制备与表征

在聚丙烯腈的N,N-二甲基甲酰胺和四氢呋喃的混合溶剂中添加聚二茂铁硅烷,通过溶液的静电纺丝,制备了含聚二茂铁硅烷微相分离的微纳前驱体纤维,经预氧化和炭化,得到负载Fe的碳纳米纤维膜;利用SEM、SEM-EDS和XPS分别对纳米纤维的形貌、尺寸、结构和组成进行了表征。     

低碳钢基体表面氧乙炔碳化焰法沉积纳米炭纤维

低碳钢经浓硝酸浸蚀预处理后,调节氧乙炔火焰成碳化焰,预处理过的低碳钢基体表面火焰沉积获得纳米炭纤维涂层。采用扫描电镜、X射线衍射和显微激光拉曼光谱等先进分析手段对其形态和结构进行了表征。研究发现纳米炭纤维相互缠绕弯曲,石墨化程度高,直径为80nm~100nm、长度为4μm~5μm,形态短而粗。纳米炭纤维相互排列紧密但与基体结合力弱易从低碳钢表面脱落,浓硝酸浸蚀预处理的低碳钢表面在火焰中形成大量氧化铁颗粒,催化纳米炭纤维成核生长。     

Low temperature growth of SWNTs on a nickel catalyst by thermal chemical vapor deposition

Single-walled carbon nanotubes (SWNTs) have been grown on a silica-supported monometallic nickel (Ni) catalyst at temperatures ranging from as low as 450 °C to 800 °C. Different spectroscopic techniques, such as Raman, photoluminescence emission (PLE), and ultra violet-visible-near infrared (UV-vis-NIR) absorption spectroscopy were used to evaluate the diameter and quality of the SWNTs grown over the Ni catalyst at different temperatures. The analysis revealed that high quality SWNTs with a very narrow diameter distribution were obtained at a growth temperature of 500 °C. In the PLE and absorption spectra, differences were observed between the SWNTs grown on Ni and those grown on cobalt (Co). This result expands the potential of growing a specific (n, m) tube species with relatively high abundance by tuning the catalyst composition. Furthermore, the prerequisites for the low temperature growth of SWNTs over a monometallic transition metal catalyst have been elucidated.      

多孔纳米碳纤维的制备及其在超级电容器中的应用研究

利用溶胶凝胶燃烧法制备了碱金属氧化物掺杂的铜催化剂,并使用这种催化剂在不同的温度、掺杂比例下通过热CVD法合成出了具有多孔分叉结构的纳米碳纤维.通过TEM、HRTEM、BET和激光拉曼光谱等手段对产物进行表征,显示这种纳米碳纤维的比表面积可高达1162m2/g,远高于普通的碳电极材料,并且具有非常丰富的中孔结构,克服了常规碳纳米纤维在应用中表现出的相对有效利用面积不大,比电容不高等缺陷,具备做电极材料的潜力.在将其应用于超级电容器电极材料后,利用二次电池测试仪及电化学工作站对其进行了循环伏安曲线及恒流充放电曲线的测试,结果显示这种纳米碳纤维具有良好的电化学电容行为,电极的可逆性良好,并且比电容值高达203F/g.这些发现将有助于碳纳米材料可控制备的研究,并且提供了一种有一定应用潜力的超级电容器电极材料.     

碳纳米管有序排列对碳纤维增强环氧树脂基复合材料低温性能的影响

为了提高碳纤维增强环氧树脂(CF/EP)复合材料在低温(77K)循环条件下的抗微裂纹性能,采用共沉淀法制备了具有良好顺磁性的Fe_3O_4修饰氧化碳纳米管(Fe_3O_4-O—MWCNTs),并研究了Fe_3O_4-O—MWCNTs在环氧树脂(EP)基体中的有序排列对EP及CF/EP复合材料低温性能的影响。结果表明:Fe_3O_4-O—MWCNTs的有序排列可有效提高EP基体的低温力学性能及降低EP基体的热膨胀系数,相对于纯EP,Fe_3O_4-O—MWCNTs改性EP的热膨胀系数降低了41.6%;相对于CF/EP复合材料,Fe_3O_4-O—MWCNTs改性CF/EP复合材料在低温环境下的微裂纹密度降低了56.2%。     

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.     

常温生长类金刚石薄膜的实验研究

利用射频等离子体增强化学气相沉积(RFPECVD)工艺在常温下实现在不锈钢、硅片、玻璃等基底上大面积沉积类金刚石(DLC)膜.薄膜表面光滑致密,与衬底的结合力较高.用Raman,FTIR,SEM,EDX研究了薄膜的形貌、结构与组分.用栓-盘摩擦磨损试验机测试了薄膜的摩擦系数.通过优化沉积参数,所沉积的DLC膜在与100Cr6钢球对磨时摩擦系数低于0.01.在摩擦过程中DLC膜的磨损机制借助SEM进行了研究.     

A method to evaluate the tensile strength and stress-strain relationship of carbon nanofibers, carbon nanotubes, and C-chains

A method is introduced to assess the tensile strength of carbon nanofibers, carbon nanotubes (CNTs), and linear chains of carbon atoms (C-chains) obtained from thin amorphous carbon films by electron irradiation. Transmission electron microscopy images show that the nanofibers undergo a radiation-induced necking process, characterized by CNT formation and often followed by the formation of a C-chain. Simulations of the necking process are carried out to determine the tensile stress supported by the nanofiber and CNT neck.     

纳米碳纤维表面修饰及其在水溶液中的分散

为了研究纳米碳纤维(CNFs)在水溶液中的分散情况,对其进行高温纯化处理,以甲基纤维素(MC)为分散剂,制备分散良好的CNFs悬浮液.采用差热分析(DTA)和热重分析(TGA)研究了高温处理对CNFs的影响,通过测定悬浮液的紫外可见光吸光度、等温吸附曲线、zeta电位及表面张力等方法研究了MC对CNFs分散性能的影响,并讨论分析了MC对CNFs的分散机理.结果表明:MC的加入使CNFs悬浮液的zeta电位由-15.4 mV升至0,表面张力由38.87 mN/m降至36.54 mN/m;等温吸附曲线表明MC在CNFs的表面为"单阶段吸附",当MC的质量浓度达到0.4 g/L时,MC在CNFs表面饱和吸附;当CNFs达到最佳分散状态时,MC与CNFs的质量比为2∶1.     

Fabrication of a room temperature hydrogen sensor based on thin film of single-walled carbon nanotubes doped with palladium nanoparticles

A new sensor for the detection of hydrogen at parts per million (ppm) levels was fabricated by coating a thin film of palladium-doped activated single-walled carbon nanotube on the inner wall of a glass tube. The response of the sensor was based on the changes in the impedance of the sensor upon the adsorption of hydrogen molecules. The linear dynamic range of the sensor was from 1 to 50?ppm. The relative standard deviation of six replicate analyses of 5?ppm of H₂ was 2.1% and the limit of detection was 0.73?ppm for H₂ species. Humidity, methane and hydrogen sulphide did not have any serious effect on hydrogen recognition. Also, no interfering effect was observed when 20-fold excess (mass/mass) of carbon dioxide or carbon monoxide was present with hydrogen.     

直接在金属基片上生长超长宏观定向碳纳米管

在水辅助氧化作用下，直接在金属镍片上生长出宏观上定向生长的螺旋状碳纳米管，其长度达到7mm，直径在100-200nm，测试其场发射特性，开启场强为1．6V／μm，最大发射电流密度可达6mA／cm^2。     

喷雾热解法制备高产率石墨/炭纳米纤维及其特征研究

基于石墨/炭纳米纤维(GNFs)的克量级(>1 g)制备及其特征表征,通过苯的喷雾热解制备了GNFs,并采用XRD,TEM及SEM对GNFs进行了表征.结果表明:高产率GNFs的最佳生长条件是:喷管内径～0.52mm,苯液流量～5 mL/min,反应温度～750℃,载气H2流量～1 500 mL/min.所制GNFs的典型长度和直径分别为～60um和～250 nm,大部分GNFs样品呈现螺圈/螺旋纤维状.喷雾热解生长模式中GNFs的产率为克量级(1.45 g)/产程.     

具有有序宏观结构纳米碳纤维的制备及其性能应用

以CH4为碳源,金属Ni为催化剂,采用化学气相沉积法（CVD）在有序宏观基体材料（SiO2纤维,Al2O3纤维）上制备出纳米碳纤维。利用场发射扫描电镜（FE—SEM）、透射电镜（TEM）、拉曼光谱（Raman）以及热重分析（TG）对产物进行了微观形貌和结构的检测。结果表明,所制备的纳米碳纤维具有取向性,能够在有序宏观基体材料上形成致密有序的纳米碳纤维层;与Al2O3纤维相比,SiO2纤维更易于生成高质量的纳米碳纤维;所制备的纳米碳纤维遵循顶端生长模式。此外,采用纳米碳纤维作模板可以原位合成出具有有序宏观结构的纳米LaMnO3,它能明显降低碳黑颗粒的起燃温度,具有潜在的应用前景。     

Thermometer for between 0.01 and 4 K using a carbon resistor

We present an original mounting for a carbon resistor. This device, when used as a thermometer, has displayed very good cooling ability and excellent reproducibility down to 10 mK.     

Controlled growth of carbon nanofibers using plasma enhanced chemical vapor deposition: Effect of catalyst thickness and gas ratio

The characteristics of carbon nanofibers (CNFs) grown, using direct current plasma enhanced chemical vapor deposition system reactor under various acetylene to ammonia gas ratios and different catalyst thicknesses were studied. Nickel/Chromium-glass (Ni/Cr-glass) thin film catalyst was employed for the growth of CNF. The grown CNFs were then characterized using Raman spectroscopy, field emission scanning electron microscopy and transmission electron microscopy (TEM). Raman spectroscopy showed that the Ni/Cr-glass with thickness of 15 nm and gas ratio acetylene to ammonia of 1:3 produced CNFs with the lowest I_D/I_G value (the relative intensity of D-band to G-band). This indicated that this catalyst thickness and gas ratio value is the optimum combination for the synthesis of CNFs under the conditions studied. TEM observation pointed out that the CNFs produced have 104 concentric walls and the residual catalyst particles were located inside the tubes of CNFs. It was also observed that structural morphology of the grown CNFs was influenced by acetylene to ammonia gas ratio and catalyst thickness.     

Low temperature synthesis of spherical nano-diamond

Thin film nano-diamonds have been synthesised using CH₄/H₂ mixture by micro-wave plasma enhanced CVD (MW-PECVD) at a substrate temperature as low as 250°C. These are found to be spherically shaped, homogeneously distributed on the film surface (size ～100?nm) and are related to ball-like or ballas-like nano-diamonds. With the increment of temperature from 200°C to 250°C, these spherical structures are found to form in increasing number density, but the same could not be grown with the variation of power and pressure. However, the bulk material is found to improve in crystallinity with the increment of pressure and highly polycrystalline nano-diamonds (111), along with Graphitic [(100), (004)] inclusions, have been grown using a gas pressure of 70?Torr and 500?W of MW power. The preliminary results on FE-SEM, Raman and HR-TEM studies are discussed here. Further developments of the material and characterisation are in progress.