Laser-induced modification of composite Cu-C nanosized particles synthesized using a pulsed electrical discharge in a liquid

Composite copper-containing carbon nanosized structures were synthesized in the plasma of a pulsed electrical discharge, initiated between two graphite electrodes in an aqueous copper chloride solution. We studied the effect of laser radiation on the morphology of the nanoparticles formed, whose properties we studied by optical absorption spectroscopy and transmission electron microscopy. We discuss the mechanisms for nanoparticle formation in a discharge submerged in a liquid, and the possibilities for laser-induced modification of the nanoparticles. We estimated the temperature of the nanoparticles when exposed to laser radiation pulses. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 372–378, May–June, 2008.     

Growth of small diameter multi-walled carbon nanotubes by arc discharge process

Multi-walled carbon nanotubes （MWCNTs） are grown by arc discharge method in a controlled methane environment. The arc discharge is produced between two graphite electrodes at the ambient pressures of 100 tort, 300 torr, and 500 torr. Arc plasma parameters such as temperature and density are estimated to investigate the influences of the ambient pressure and the contributions of the ambient pressure to the growth and the structure of the nanotubes. The plasma temperature and density are observed to increase with the increase in the methane ambient pressure. The samples of MWCNT synthesized at different ambient pressures are analyzed using transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. An increase in the growth of MWCNT and a decrease in the inner tube diameter are observed with the increase in the methane ambient pressure.     

Effect of carbon nanotubes on the anode performance of natural graphite for lithium ion batteries

A comparative investigation was carried out on carbon black and multiwalled carbon nanotubes as conductive additives in spherical natural graphite for lithium ion batteries. Scanning electron microscopy images showed that carbon nanotubes interlaced graphite particles in series to form a three-dimensional network. The constant current charge-discharge experiments showed that carbon nanotubes were more effective in improving reversible capacity and cycle stability. The reversible capacity was improved to 366 mAh/g and the cycle stability was improved effectively when carbon nanotubes were used. The research is of potential interest to the application of carbon nanotubes as conductive additives in anode materials for high-power lithium ion batteries.     

Structure comparison of nanotubes produced by different processes

Several methods used for the synthesis of carbon nanotubes have been developed in the last decade. The preparation techniques used, and their associated parameters, have an ultimate effect on the structure of the resulting nanotubes. Consequently, it is of great interest to compare the structure of carbon nanotubes synthesized by different techniques. We investigated a range of nanotubes of different origin by scanning probe microscopy (TM-AFM), and by scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). Three different types of nanotubes have been investigated: commercial SWNT and MWNT, MWNT (synthesized using a CCVD process) and its SiO₂ coated variant, and nanostructures produced using an electrochemical method. A preparative technique is described and different tube parameters are measured. The quality of coated MWNT-s is investigated and nano-structured rings are revealed in samples obtained by electrolysis of molten salts on graphite electrodes.     

Formation of sub-micron size carbon structures by plasma jets emitted from a pulsed capillary discharge

We have performed an experimental investigation of the potential use of intense plasma jets produced in a repetitive pulsed capillary discharge (PCD) operating in methane gas, to irradiate Si (1 0 0) substrates. The surface modifications induced by the plasma jet using two different material inserts at the capillary end, graphite and titanium, are characterized using standard surface science diagnostic tools, such as scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analysis and Raman spectroscopy (RS). It has been found that the application of methane plasma jet results in the formation of sub-micron size carbon structures. It is observed that the resulting plasma irradiated surface morphologies are different, depending on the different material inserts used at the capillary end, at otherwise identical operational conditions. To investigate the species responsible for the observed surface changes in different material inserts to the capillary, optical-emission spectroscopy (OES) was recorded using a 300-1000 nm spectrometer. The OES results show the presence of H, CH and C₂ Swan band in the discharge plasma, which play a significant role in the formation of the carbon structures.     

Electron beam induced formation of carbon nanorods

Electron beam induced formation of carbon nanorods was realized in situ under high resolution scanning electron microscopy (HRSEM). When a CVD deposited carbon nanotube sample was irradiated with an electron beam in an HRSEM, progressive etching of the sample, expanding of the nanotubes, and formation of additional nanorods have been observed. Transmission electron microscopy study revealed typical nanorods of 20 nm in diameter and with amorphous structure. The direct observation of the synthesis of nanorods under electron microscopy manifests the possibility of nano-machining of such nanomaterials using electron beams. This may lead to future integration and networking of nanostructures of different functionalities, which is crucial for nanotechnology.     

Preparation of graphene/polyaniline-modified carbon nanotubes and their electrochemical properties in microbial fuel cell

Using chemical vapor deposition methods to prepare carbon nanotubes growing in situ on a carbon felt, graphene and polyaniline were applied to the carbon felt for modifying carbon nanotubes. Microbial fuel cell was constructed with graphene/polyaniline-modified carbon nanotubes as anode, graphite as cathode, and glucose solution as substrate. The effects of electrodes, substrate concentration, and temperature on the properties of microbial fuel cell have been studied. At 38 °C using glucose solution of 1450 mg L^?1 and external resistance of 2500 Ω, the optimum output voltage of 687 mV and removal rate of 83% for chemical oxygen demand were obtained in the microbial fuel cell. The prepared nanomaterials are stable and reusable.     

Structure and optical properties of tungsten oxide nanomaterials prepared by a modified plasma arc gas condensation technique

With the use of a modified plasma arc gas condensation technique and control of the processing parameters, namely, plasma current and chamber pressure, we synthesized tungsten oxide nanomaterials with aspect ratios ranging from 1.1 (for equiaxed particles with the length and width of 48 nm and 44 nm, respectively) to 12.7 (for rods with the length and width of 266 nm and 21 nm, respectively). The plasma current and chamber pressure, respectively, ranged from 70 to 90 A and from 200 to 600 Torr. We then characterized the tungsten oxide nanomaterials by means of X-ray diffraction, high-resolution transmission electron microscope, UV–visible spectroscope, and photoluminescence (PL) spectroscope. Experimental results show that equiaxed tungsten oxide nanoparticles were produced at a relatively low plasma current of 70 A, whereas nanorods were produced when plasma currents or chamber pressures were increased. All of the as-prepared tungsten oxide nanomaterials exhibited a WO_2.8 phase. Compared to the nanoparticles, the nanorods exhibited unique properties, such as a redshift in the UV–visible spectrum, a blue emission in PL spectrum, and a good performance in field emission. With respect to the field emission, the turn-on voltage for WO_2.8 nanorods was found to be as low as 1.7 V/μm.     

A novel method for synthesis of colloidal silver nanoparticles by arc discharge in liquid

This paper presents a novel, inexpensive and one-step approach for synthesis of silver nanoparticles (Ag NPs) using arc discharge between titanium electrodes in AgNO₃ solution. The resulting nanoparticles were characterized using UV–Vis spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Silver nanoparticles of 18 nm diameter were formed during reduction of AgNO₃ in plasma discharge zone. Optical absorption spectroscopy of as prepared samples at 15 A arc current in AgNO₃ solution shows a surface plasmon resonance around 410 nm. It was found that sodium citrate acts as a stabilizer and surface capping agent of the colloidal nanoparticles. SEM images exhibit the increase of reduced nanoparticles in 6 min arc duration compared with 1 min arc duration. TEM image of the sample prepared at 6 min arc duration shows narrow size distribution with 18 nm mean particle size. Antibacterial activities of silver nanoparticles were investigated at the presence of Escherichia coli (E-coli) bacteria.     

Effects of graphite additives in electrolytes on the microstructure and corrosion resistance of Alumina PEO coatings

In the present work, graphite grains of different sizes were added into the electrolyte to prepare ceramic coatings on aluminum by plasma electrolytic oxidation (PEO). Scanning electron microscopy (SEM) coupled with an energy dispersive X-ray analysis system (EDX), Raman spectroscopy and X-ray diffractometer (XRD) were used to characterize the coatings. A three-electrode system was used to evaluate the corrosion performances of the coatings in a 3.5 wt.% NaCl solution. It was found that the morphology and corrosion performance of the coatings were significantly influenced by the size of the graphite grains. Compared with bigger graphite grains, finer ones were involved in the oxidation process and embedded within the ceramic coatings, which made the coatings less porous and more compact. Thus, the corrosion resistance of the coatings with embedded graphite grains was greatly improved.     

Transparent ultrathin conducting carbon films

Ultrathin conductive carbon layers (UCCLs) were created by spin coating resists and subsequently converting them to conductive films by pyrolysis. Homogeneous layers as thin as 3 nm with nearly atomically smooth surfaces could be obtained. Layer characterization was carried out with the help of atomic force microscopy, profilometry, four-point probe measurements, Raman spectroscopy and ultraviolet-visible spectroscopy. The Raman spectra and high-resolution transmission electron microscopy image indicated that a glassy carbon like material was obtained after pyrolysis. The electrical properties of the UCCL could be controlled over a wide range by varying the pyrolysis temperature. Variation in transmittance with conductivity was investigated for applications as transparent conducting films. It was observed that the layers are continuous down to a thickness below 10 nm, with conductivities of 1.6 × 10⁴ S/m, matching the best values observed for pyrolyzed carbon films. Further, the chemical stability of the films and their utilization as transparent electrochemical electrodes has been investigated using cyclic voltammetry and electrochemical impedance spectroscopy.     

Synthesis of carbon nanotubes by ECR plasma-assisted chemical vapor deposition

Carbon nanotubes have been grown using an electron cyclotron resonance (ECR) plasma source at a substrate temperature of 500 °C. Methane has been used as the source gas. A network of carbon nanotubes has been observed in scanning electron microscopy. Transmission electron microscopy revealed that the structure consists of straight, Y-junction and ring-like nanotubes. Further, electron diffraction of the nanotubes confirms a graphite crystal structure. PACS 81.16.He; 68.37.Lp; 68.37.Hk; 85.35.Kt; 75.75.+a     

Carbon nanostructures synthesized by arc discharge between carbon and iron electrodes in liquid nitrogen

An idea of using pure iron and graphite electrodes was employed for synthesizing carbon nanoparticles by arc discharge in liquid nitrogen. The synthesized products consist of multiwalled carbon nanotubes (MW–CNT), carbon nanohorns (CNH), and carbon nanocapsules (CNC) with core–shell structure. Effect of metallic cathode and discharge current on product structure and yield had been experimentally investigated. Typical evidence of transmission electron microscopic images revealed that under some certain conditions of discharge in liquid nitrogen the synthesized products mainly consisted of CNCs with mean diameter of 50–400 nm. When conventional graphitic electrodes were employed, CNHs with some MW–CNTs were mainly synthesized. Meanwhile, MW–CNTs with diameter of 8–25 nm and length 150–250 nm became less selectively synthesized as cathode deposit under the condition of discharge in liquid nitrogen with higher arc current. The production yield of carbon nanoparticles synthesized by either carbon–carbon or carbon–iron electrodes became also lower with an increase in the arc current.     

A novel combinative Raman and SEM mapping method for the detection of exfoliation of graphite in electrodes at very positive potentials

The random exfoliation at very positive potentials (>5 V vs Li/Li⁺) of graphite (used as a conductive component in positive electrodes of lithium‐ion batteries) was investigated with in situ Raman microscopy and post mortem scanning electron microscopy (SEM). A novel semiautomated computational method for the data analysis of both characterization methods was developed to correlate Raman and SEM information with good lateral resolution, in order to locate exfoliated graphite particles. Proof is given that the exfoliating particles detected via the semiautomatic in situ Raman microscopy mappings correctly describes exfoliated areas, as confirmed via post mortem SEM pictures. Copyright © 2011 John Wiley & Sons, Ltd.     

Crystallization of Carbon Nanotube and Nanofiber Polypropylene Composites

A variety of semicrystalline isotactic polypropylene composites containing carbon nanotubes and nanofibers were produced by melt and solution techniques. The effect of the nanofillers on the crystallization process was investigated by transmission electron microscopy, scanning electron microscopy, and differential scanning calorimetry. Under the processing conditions applied in this study, the surfaces of the carbon nanomaterials act as nucleation sites in bulk samples and highly oriented composite films. This conclusion is confirmed by the calculation of Avrami exponents and, in particular, by direct microscopy evidence.     

Effect of adding W to Fe catalyst on the synthesis of SWCNTs by arc discharge

Combining iron (Fe) and tungsten (W) as a bimetallic catalyst, we synthesized high-yield single-wall carbon nanotubes (SWCNTs) of narrow diameter distribution by a hydrogen–argon arc discharge method. Raman spectra indicate that the diameters of SWCNTs prepared using the Fe–W catalysts are about 0.5 nm smaller than those using Fe catalyst alone. The transmission electron microscopy and X-ray diffraction studies show that the SWCNTs prepared by the bimetallic catalyst coexist with few graphite flakes and other amorphous carbon. At the W content of 2–4 at%, tungsten cannot be found in the SWCNT samples. Thus by using a simple two-step purification process, high-purity SWCNT samples can be obtained. We have demonstrated the growth mechanism for the high melting metal (such as W, Mo)–Fe catalyst synthesis of SWCNTs by the arc discharge method.     

Electrical properties of boron-doped MWNTs synthesized by hot-filament chemical vapor deposition

We have synthesized a large amount of boron-doped multiwalled carbon nanotubes (MWNTs) by hot-filament chemical vapor deposition. The synthesis was carried out in a flask using a methanol solution of boric acid as a source material. The scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were performed to evaluate the structural properties of the obtained MWNTs. In order to evaluate the electrical properties, temperature dependence of resistivity was measured in an individual MWNTs with four metal electrodes. The Raman shifts suggest carrier injection into the boron-doped MWNTs, but the resistivity of the MWNTs was high and increased strongly with decreasing temperature. Defects induced by the plasma may cause this enhanced resistivity.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

IR laser-induced metal ablation and dielectric breakdown in benzene

IR laser-induced irradiation of Co and Ni sheets leads to metal ablation and when carried out in gaseous benzene (1–10 Torr) to dielectric breakdown which is accompanied by metal plasma and deposition of nanostructured carbon. The metal plasma (metal atoms and ions) as well as transients of benzene decomposition (neutral and ionic carbon and C₂ species) were detected by optical emission spectra. Different features of carbon deposited at benzene pressure 5–10 Torr on a distant glass and on the irradiated metal sheets were revealed by FTIR, Auger and Raman spectroscopy and electron microscopy and explained by surface assisted carbonization. The reported process suggests a novel approach to gas-phase carbonization of organic molecules.