Complex dynamics of carbon nanotube probe tips

Carbon nanotube (CNT) tips in tapping mode atomic force microscopy (AFM) enable very high-resolution imaging, measurements, and manipulation at the nanoscale. We present recent results based on experimental analysis that yield new insights into the dynamics of CNT probe tips in tapping mode AFM. Experimental measurements are presented of the frequency response and dynamic amplitude-distance data of a high-aspect-ratio multi-walled (MW) CNT tip. Higher harmonics of the microcantilever are measured in frequency ranges corresponding to attractive regime and the repulsive regime where the CNT buckles dynamically. Surface scanning is performed using a MWCNT tip on a SiO(2) grating to verify the imaging instabilities associated with MWCNT buckling when used with normal control schemes in the tapping mode. Lastly, the choice of optimal setpoints for tapping mode control using CNT tip are discussed using the experimental results.     

Effect of carbon nanotube structural parameters on field emission properties

Experimental studies were devoted to the effect of structural parameters, i.e., tube diameter and density, on the field electron emission characteristics of carbon nanotubes. Thermal chemical vapor deposition system was employed to synthesize carbon nanotubes. Nanotubes with different diameters and densities were obtained by adjusting the thickness of the iron (Fe) catalyst film. The morphologies of the Fe and carbon nanotube film were characterized by scanning electron microscopy respectively. Further field emission measurement confirmed that the tube diameter and density could significantly affect the electron emission properties of the carbon nanotube. Possible physical reasons for the effect are discussed.     

Tribological behavior and graphitization of carbon nanotubes grown on 440C stainless steel

Vertically aligned carbon nanotube (CNT) arrays were directly grown onto 440C stainless steel substrates by plasma-enhanced chemical vapor deposition. Tribological properties of both short and long CNTs samples were studied under normal loads of 10 g, 25 g and 100 g. The CNTs had a steady-state friction coefficient of about 0.2 in humid air. In dry nitrogen, a friction of 0.2 was measured under a load of 10 g while high friction was measured at 25 g and 100 g loads. No significant variation of tribological behavior was measured between the short and long CNTs samples. SEM observations showed that rubbing caused the CNTs to align or lay down along the wear scar. They formed aggregates and were compressed by rubbing, which resulted in layer-structured graphite formations. SEM observation of the wear scars revealed loss of CNT structures accompanied by the appearance of dark areas. Micro Raman spectroscopic studies demonstrated that the dark areas were graphitized CNTs. Shear stress aligned the basal planes of the small graphene sheets in the CNT layers to the low friction orientation and eventually caused formation of more ordered graphite. The tribological formation of interfacial carbon layers increased with increasing stress from higher loads.     

In situ measurements on individual thin carbon nanotubes using nanomanipulators inside a scanning electron microscope

We demonstrate here a novel method for performing in situ mechanical, electrical and electromechanical measurements on individual thin carbon nanotubes (CNTs) by using nanomanipulators inside a scanning electron microscope. The method includes three key steps: picking up an individual thin CNT from a substrate, connecting the CNT to a second probe or an atomic force microscope cantilever for the measurements and placing the CNT onto a holey carbon film on a transmission electron microscope grid for further structure characterization. With the method, Young’s modulus, the breaking strength and the effects of axial strain on electrical transport properties of individual thin CNTs can be studied. As examples, the mechanical, electrical and electromechanical properties of a double-walled CNT (DWCNT) and a single-walled CNT (SWCNT) were measured. We observed a strain-induced metallic-to-semiconducting transition of the DWCNT and a bandgap increase of the SWCNT. More importantly, the electromechanical properties of the SWCNT were correlated to its chirality determined by electron diffraction. The method enables us to relate mechanical, electrical and electromechanical properties of the measured thin CNTs to their atomic structures.     

Micromechanical scribing and indentation behavior of injection-molded polymeric carbon nanotube (CNT) nanocomposites

Polymeric carbon nanotube (CNT) nanocomposites have unique mechanical, electrical, and thermal properties. Anisotropy can be induced depending on the alignment of the CNT fillers within polymeric composites, which is known to affect material properties. In order to investigate the effects of CNT alignments in micromechanical scribing using a single crystal diamond tool, a microindenter–scriber system was developed. Multiwalled carbon nanotube–polystyrene (MWCNT–PS) samples with varying CNT concentrations were prepared through a microinjection molding process, where the injection enables the partial alignment of CNTs in the flow direction through high shear stress. A mechanistic scribing force model was proposed based on the material properties that could be obtained using the microindentation techniques. Scribing experiments were performed in the parallel and perpendicular directions to the CNT alignment. Forces in three axes were measured and analyzed to identify three unknown parameters—the shearing, plowing, and adhesion friction coefficients. The resulting coefficients for scribing perpendicular to the CNT alignment showed distinguishable trends from scribing parallel to the CNT alignment as the CNT loadings increased. Their linear trends in relation to the material properties identified from indentation techniques can be used to predict microscribing parameters and resulting cutting forces, in combination with the proposed mechanistic model.     

Lubricant Additives Based on Carbon Nanotubes Produced from Carbon-Rich Fly Ash

Carbon-rich fly ash has been reported to be a suitable precursor and catalyst for carbon nanotube (CNT) growth. In this work, CNTs grown from carbon-rich fly ash were evaluated as a lubricant oil additive to reduce the friction coefficient of metallic surfaces using a ball-on-disk tribometer. Different concentrations of the as-grown CNTs in the range 0.005–0.5 wt% were dispersed in a base sunflower oil. The value of the friction coefficient was also investigated as a function of load. Excellent results were obtained for the value of the friction coefficient, where it drastically decreased to around 58% of its original value without additives. This was achieved at a very low concentration of CNTs; that is, 0.1 wt%. The obtained result was compared with that of a commercial multiwalled CNT at the same concentration and found to be superior. This superiority of CNTs produced from fly ash could be attributed to the existence of active radical sites on their side wall. Moreover, the friction coefficient value was observed to decrease with increasing load, which might be due to the formation of protective graphitic carbon layers on antagonist surfaces. The viscosity of pure and 0.1 wt% CNTs-impregnated base oil was also studied in the 25–100°C temperature range. No significant changes are observed in the viscosity of the CNTs-impregnated base oil. These results suggest that the low-cost CNTs produced from fly ash are excellent nanomaterials as additives for lubricant oil.     

Tribological properties of carbon nanotube-doped carbon/carbon composites

Carbon nanotube (CNT)-doped carbon/carbon (C/C) composites were fabricated by the chemical vapor infiltration (CVI) method to investigate the effect of CNTs on tribological properties of C/C composites. CNTs, which had been synthesized by catalytic pyrolysis of hydrocarbons, were added to carbon fiber formed preforms before CVI process. Ring-on-block-type wear tests were performed to evaluate the frictional properties of CNT-doped C/C composites. Results show that CNTs can not only increase wear resistance of C/C composites but also maintain stable friction coefficients under different loads. Polarized light microscopy, X-ray diffraction, scanning electron microscopy and Raman spectroscopy analyses demonstrate that favorable effects of CNTs on tribological properties of C/C composites have been achieved indirectly by altering microstructure of pyrocarbons and directly by serving as high-strength lubricative frictional media at the same time. Electron dispersive spectroscopy (EDS) analyses verify the existence of adhesive wear mechanism in both pure C/C composites and CNT-doped C/C composites albeit the two-body abrasive mechanism dominates in pure C/C composites.     

纳米碳管对MWPCVD过程增强金刚石形核的影响

利用石英钟罩式微波等离子体化学气相沉积（ＭＷＰＣＶＤ）实验装置,研究了硅基体表面沉积金刚石薄膜时纳米碳管对金刚石形核过程的影响。扫描电子显微镜（ＳＥＭ）形貌分析结果显示,纳米碳管处理能够促进金刚石形核。对非研磨基体而言,这是一种有效的增强金刚石形核的表面预处理方式。     

High-yield synthesis of conductive carbon nanotube tips for multiprobe scanning tunneling microscope

We have established a fabrication process for conductive carbon nanotube (CNT) tips for multiprobe scanning tunneling microscope (STM) with high yield. This was achieved, first, by attaching a CNT at the apex of a supporting W tip by a dielectrophoresis method, second, by reinforcing the adhesion between the CNT and the W tip by electron beam deposition of hydrocarbon and subsequent heating, and finally by wholly coating it with a thin metal layer by pulsed laser deposition. More than 90% of the CNT tips survived after long-distance transportation in air, indicating the practical durability of the CNT tips. The shape of the CNT tip did not change even after making contact with another metal tip more than 100 times repeatedly, which evidenced its mechanical robustness. We exploited the CNT tips for the electronic transport measurement by a four-terminal method in a multiprobe STM, in which the PtIr-coated CNT portion of the tip exhibited diffusive transport with a low resistivity of 1.8 kOmega/microm. The contact resistance at the junction between the CNT and the supporting W tip was estimated to be less than 0.7 kOmega. We confirmed that the PtIr thin layer remained at the CNT-W junction portion after excess current passed through, although the PtIr layer was peeled off on the CNT to aggregate into particles, which was likely due to electromigration or a thermally activated diffusion process. These results indicate that the CNT tips fabricated by our recipe possess high reliability and reproducibility sufficient for multiprobe STM measurements.     

Microstructure and wear resistance of nickel–carbon nanotube composite coating from brush plating technique

This paper investigates the microstructure and wear resistance of nickel–carbon nanotube (CNT) composite coating deposited by brush plating technique. The Ni/CNT coating deposited with a pulse current source has less porosity, higher hardness and higher wear resistance than that with a DC source. CNTs greatly improve the coating performance. The wear mechanism is mainly the smearing of the Ni/CNTs coatings, instead of the fracture for the Ni coatings.     

Comparative characterization of chemical vapor deposition diamond films by scanning cathodoluminescence microscopy

Thin diamond films grown by chemical vapor deposition (CVD) process on Si substrates under similar deposition conditions in the microwave-excited (MW) and direct current (DC) plasma discharges were taken for comparative examination. Raman spectra, photoluminescence (PL) spectroscopy, and color cathodoluminescence scanning electron microscopy (CCL-SEM) have been used for characterization of the structure and composition features of poly-crystalline diamond films. No essential difference in Raman spectra for the CVD diamond films was detected. A significant difference was revealed in the PL spectra and in CCL-SEM images.     

CVD金刚石涂层拉丝模的研制与应用

:以市售大孔径 (>2mm)硬质合金拉丝模为衬底 ,经酸腐蚀去钴、研磨和还原处理后 ,以氢气和丙酮为原料 ,用穿孔直拉热丝CVD法制备了金刚石涂层。利用扫描电镜和喇曼谱图对涂层均匀性进行了评估。初步应用试验表明 ,金刚石涂层的附着力能满足实际拉伸要求 ,涂层拉丝模的工作寿命可提高 3～ 5倍。     

Influence of humidity on microtribology of vertically aligned carbon nanotube film

The aim of this study is to probe the influence of water vapor environment on the microtribological properties of a forestlike vertically aligned carbon nanotube (VACNT) film, deposited on a silicon (001) substrate by chemical vapor deposition. Tribological experiments were performed using a gold tip under relative humidity varying from 0 to 100%. Very low adhesion forces and high friction coefficients of 0.6–1.3 resulted. The adhesion and friction forces were independent of humidity, due probably to the high hydrophobicity of VACNT. These tribological characteristics were compared to those of a diamond like carbon (DLC) sample.     

Using carbon nanotube probes for high-resolution three-dimensional imaging of cells

While atomic force microscopy (AFM) has become a promising tool for visualizing membrane morphology of cells, many studies have reported the presence of artifacts such as cliffs on the edges of cells. These artifacts shield important structural features such as lamellopodia, filopodia, microvilli and membrane ridges, which represent characteristic status in signaling processes such as spreading and activation. These cliff-like edges arise from a premature contact of the probe side contact with the cell prior to the probe top apex-cell contact. Carbon nanotube (CNT) modified AFM probes were utilized to address this drawback. Using rat basophilic leukemia (RBL) cells, this work revealed that CNT probes diminish cliff-like artifacts and enabled visualization of entire membrane morphology and structural features in three dimensions. The high aspect ratio of CNT probes provides a very effective remedy to the cliff-like artifacts as well as tip convolution of conventional probes, which shall enhance the validity and application of AFM in cellular biology research.     

Dry friction and wear characteristics of nickel/carbon nanotube electroless composite deposits

Ni/carbon nanotube (Ni/CNTs) composite coatings were deposited on carbon steel plate by electroless deposition. The friction and wear properties were examined under dry sliding conditions using the ball-on-disk configuration. For reference, carbon steel plate was coated with Ni, Ni/SiC and Ni/graphite. The results show that the Ni/CNT coating has a microhardness value of 865 Hv, greater than for SiC reinforced composite deposits. The Ni/CNTs composite coating possesses not only a higher wear resistance but also a lower friction coefficient, resulting from their improved mechanical characteristics and the unique topological structure of the hollow nanotubes.     

Influence of Surface Roughness on the Lubrication Effect of Carbon Nanoparticle-Coated Steel Surfaces

In the present study, a systematic evaluation of the influence of the surface roughness on the lubrication activity of multi-wall carbon nanotubes (MWCNT) and onion-like carbon (OLC) is performed. MWCNT and OLC are chosen as they both present an sp²-hybridization of carbon atoms, show a similar layered atomic structure, and exhibit the potential to roll on top of a surface. However, their morphology (size and aspect ratio) clearly differs, allowing for a methodical study of these differences on the lubrication effect on systematically varied surface roughness. Stainless steel platelets with different surface finishing were produced and coated by electrophoretic deposition with OLC or MWCNT. The frictional behavior is recorded using a ball-on-disk tribometer, and the resulting wear tracks are analyzed by scanning electron microscopy in order to reveal the acting tribological mechanisms. It is found that the lubrication mechanism of both types of particles is traced back to a mixture between a rolling motion on the surfaces and particle degradation, including the formation of nanocrystalline graphitic layers. This investigation further highlights that choosing the suitable surface finish for a tribological application is crucial for achieving beneficial tribological effects of carbon nanoparticle lubricated surfaces.     

微波等离子体CVD法在非平面基体上生长金刚石膜

介绍了在微波等离子体CVD装置中,用甲烷和氢气作为原料,在非平面基体(如钨丝、钻头、铣刀等)上生长金刚石薄膜的研究。在金刚石沉积过程中,由于"尖端效应",在基体的尖端很难沉积出金刚石膜。在采用金属丝屏蔽后,克服了"尖端效应",成功地在非平面基体上沉积出了金刚石膜。用扫描电镜(SEM)和激光拉曼光谱(Raman)分析了金刚石膜的形貌和质量。结果表明:非平面基体不同位置金刚石的晶形不同,晶粒比较细小,膜的质量较高。     

Optically active centers in diamond as-grown at temperatures 1200–1350°C

Diamonds were grown in the vicinity of the “diamond-graphite” equilibrium state by the spontaneous crystallization method to study the creation of defects and crystalline imperfections. Crystals were synthesized in the graphite-Ni-Mn system. Raman and luminescence spectroscopy, electron microscopy, and optical absorption spectroscopy were used for diamond crystal inspection. Diamonds were classified into three groups: (1) black, nontransparent, curved, flat-faced crystals; (2) dark or black semitransparent crystals of cubic habit with faceting of the cube vertices by (111) planes; (3) amber-yellow crystals showing a cubic-octahedral habit. The yellow crystals revealed the infrared (IR) absorption spectra within the range of 800–4000 cm^-1 that are peculiar for diamonds of the 1a group. IR spectra displayed a number of additional absorption peaks for black semitransparent crystals. A marked peak at 2835 cm^-1 and a less pronounced peak at 2919 cm^-1 unambiguously demonstrate the presence of hydrogen. An intensive absorption in the range of 800–1100 cm^-1 with a maximum at 969 cm^-1 may be explained by both the presence of hydrogen and extended defects, taking into account the data arrived at by cathodoluminescence, emission spectra, and Raman spectroscopy. For the first time, the narrow peak at 1332 cm^-1, unknown for mined diamonds and observed in flame-chemical vapor deposition (FL-CVD) diamond films, was revealed in diamonds synthesized under high pressure. The presence of peaks with maximum at 2919, 1252, and 1332 cm^-1 in the IR spectra of the black diamonds and FL-CVD diamond films indicated a certain similarity in diamond formation for high- pressure and vapor deposition techniques and an important role of hydrogen in high-pressure diamond growth. The source of hydrogen is probably graphite used in the synthesis. The increase in diamond synthesis temperature decreases the probability of hydrogen capture and provides a better crystal quality. Cathodoluminescence scanning electron microscopy demonstrated the spatial distribution of luminescence centers on different diamond crystal faces. Some crystal fragments emit A-band (420–460 nm) and have well-faceted faces that confirm their high perfection and quality that are close to natural diamonds.     

Synthesis of single-walled carbon nanotubes using laser-vaporized metal nanoparticle catalyst

SWNTs were synthesized by laser-vaporized CCVD (catalytic chemical vapor deposition). The diameter distributions and the abundance of SWNTs synthesized at different temperatures and using different catalysts were investigated by Raman spectroscopy. Further, this technique was compared with other synthesis techniques (laser-oven and conventional-alcohol CCVD), and C₆₀ was synthesized simultaneously as a byproduct only using the laser-oven technique. With increasing synthesis temperature, the diameter distribution shifted towards larger diameters, and the G/D ratio became larger as the synthesis temperature increased to 1000°C. Ni, Co, and Fe played a catalytic role, though Fe was less effective under our experimental conditions. The diameter distribution of SWNTs synthesized with the Fe catalyst was shifted to smaller values compared to those synthesized with Ni or Co catalysts.     

Growth of compound single- and multi-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) are complement to each other in many of their physical properties. We report the synthesis of carbon nanotube cables-a form of compound single- and multi-walled carbon nanotubes which could have the superior properties of both the SWCNTs and MWCNTs. This compound form of carbon nanotubes consists of a bundle of SWCNTs formed into a MWCNT, and the diameter of the inner most shell of the MWCNT ranges from a few to tens nanometers. The growth of these compound carbon nanotubes cannot be explained readily via existing modes of carbon nanotube growth, but promises a new way for improving and controlling the physical properties of either single- or multi-walled carbon nanotubes.