Transfer processes in low-temperature plasma on the formation of carbon nanostructures on the steel surface of a reactor as a result of the decomposition of hydrocarbons in the low-temperature plasma. 2. Modernization of the experimental setup,search for optimum operating conditions,determination of additional controlling factors of the process

Results of experimental investigations on the formation of carbon nanostructures in a reactor as a result of the decomposition of hydrocarbons in a low-temperature plasma are presented. Data on the production rate of the process and the content of structured carbon in the material obtained before and after the modernization of the setup were compared. Different schemes of supply of the working mixture to the plasma flow are proposed.     

Obtaining carbon nanomaterials in a plant with a plasma generator and a working zone of rectangular cross section

Results of experimental investigations of the conditions of formation of carbon nanostructures in a plasmachemical reactor of rectangular cross-section from the products of decomposition of hydrocarbons in a low-temperature plasma are presented. The influence of the additional flow region on the process was determined. Data on the content of structurized carbon in the material obtained and on the yield of the process are presented.     

Carbon Xerogel-supported Iron as a Catalyst in Combustion Synthesis of Carbon Fibrous Nanostructures

The catalytically assisted self-propagating high-temperature synthesis of carbon fibrous nanostructures, where the iron-doped colloidal carbon xerogel is proposed as a catalyst system, was examined. The carbon xerogel was prepared through carbonization of an iron doped organic xerogel at temperatures ranging from 600 to 1050 C. The reaction between calcium carbide and hexachloroethane in the presence of sodium azide is exothermic enough to proceed at a high temperature, self-sustaining regime. The combustion reactions of those mixtures enriched with iron-doped carbon xerogels were conducted in a stainless steel reactor-calorimetric bomb under an initial pressure of 1 MPa of argon. Scanning electron microscopy analysis of the combustion products revealed low yield of various type of carbon fibers (presumably nanotubes), which grew via the tip-growth mechanism. The fibrous nanostructures were found in the vicinity of the spot of ignition, while in the outer and cooler area of the reactor, dusty products with soot-like morphology dominated. No significant correlation between the pyrolysis temperature of the carbon xerogel and the morphology of the obtained carbon fibrous nanostructures was observed.     

Preparation temperature effect on the synthesis of various carbon nanostructures

Various carbon nanostructures (CNs) have been prepared by a simple deposition technique based on the pyrolysis of a new carbon source material tetrahydrofuran (THF) mixed with ferrocene using quartz tube reactor in the temperature range 700–1100 °C. A detailed study of how the synthesis parameter such as growth temperature affects the morphology of the carbon nanostructures is presented. The obtained CNs are investigated by scanning electron microscope (SEM), X-ray diffraction (XRD), electron dispersive scattering (EDS), thermogravimetry analysis (TGA), Raman and transmission electron microscope (TEM). It is observed that at 700 °C, normal CNTs are formed. Iron filled multi-walled carbon nanotubes (MWCNTs) and carbon nanoribbons (CNRs) are formed at 950 °C. Magnetic characterization of iron filled MWCNTs and CNRs studied at 300 K by superconducting quantum interference device (SQUID) reveals that these nanostructures have an enhanced coercivity (Hc = 1049 Oe) higher than that of bulk Fe. The large shape anisotropy of MWCNTs, which act on the encapsulated material (Fe), is attributed for the contribution of the higher coercivity. Coiled carbon nanotubes (CCNTs) were obtained as main products in large quantities at temperature 1100 °C.     

Formation of carbon nanostructures in the decomposition of methane in the plasma of a high-voltage atmospheric-pressure discharge

Results of experimental investigations of the conditions of formation of carbon nanomaterials in the decomposition of methane in the plasma of a high-voltage atmospheric-pressure discharge have been presented. The influence of the temperature gradient, the cathode material, and the deposition-surface material on the process of formation of carbon nanostructures has been investigated. It has been established that the processes of catalytic decomposition of methane occur, with a large degree of probability, on the metallic deposition surface in the presence of the temperature gradient between the gas flow and the surface. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 81, No. 4, pp. 617–620, July–August, 2008.     

Formation of multi-walled carbon nanotubes with a metal-free chemical vapor deposition and their stepwise evolution

Multi-walled carbon nanotubes and one-dimensional wire-like nanostructures have been synthesized using acetylene as carbon sources with a metal-free mild chemical vapor deposition process. It shows that anisotropic carbon nanostructures can interact to form nanotubes by self-function. Furthermore, the detailed microscopic observation of the obtained nanostructures indicates that the development of fully hollow carbon nanotubes should undergo a quite complex physical and chemical transformation process, and their formation abides by the “particle-wire-tube” stepwise evolution mechanism. In this process, the one-dimensional wire-like nanostructures can be viewed as the intermediate stages of carbon nanotube formation, which record traces about nanotube evolution.     

On the properties of a steel modified with carbon nanomaterials

Results of investigation of the surface of a steel modified with carbon nanomaterials having different contents of carbon nanostructures by the method of atomic-force microscopy are presented. Experiments on the microhardness of this steel have been carried out and the thickness of its modified layer was determined.     

Comparative process analysis of fullerene production by the arc and the radio-frequency discharge methods

In this work, comparative analysis of processes in carbon arc and radio frequency (RF) plasma during fullerene synthesis has been presented. The kinetic model of fullerene formation developed earlier has been verified in both types of plasma reactors. The fullerene yield depended on carbon concentration, velocity of plasma flame and rotational temperature of C2 radicals predominantly. When mean rotational temperature of C2 radicals was 3000 K, the fullerene yield was the highest regardless of the type of used reactor. The zone of fullerene formation is larger significantly in RF plasma reactor compared to arc reactor.     

Modeling of the HiPco process for carbon nanotube production. II. Reactor-scale analysis

The high-pressure carbon monoxide (HiPco) process, developed at Rice University, has been reported to produce single-walled carbon nanotubes from gas-phase reactions of iron carbonyl in carbon monoxide at high pressures (10-100 atm). Computational modeling is used here to develop an understanding of the HiPco process. A detailed kinetic model of the HiPco process that includes of the precursor, decomposition metal cluster formation and growth, and carbon nanotube growth was developed in the previous article (Part I). Decomposition of precursor molecules is necessary to initiate metal cluster formation. The metal clusters serve as catalysts for carbon nanotube growth. The diameter of metal clusters and number of atoms in these clusters are some of the essential information for predicting carbon nanotube formation and growth, which is then modeled by the Boudouard reaction with metal catalysts. Based on the detailed model simulations, a reduced kinetic model was also developed in Part I for use in reactor-scale flowfield calculations. Here this reduced kinetic model is integrated with a two-dimensional axisymmetric reactor flow model to predict reactor performance. Carbon nanotube growth is examined with respect to several process variables (peripheral jet temperature, reactor pressure, and Fe(CO)5 concentration) with the use of the axisymmetric model, and the computed results are compared with existing experimental data. The model yields most of the qualitative trends observed in the experiments and helps to understanding the fundamental processes in HiPco carbon nanotube production.     

Growth of carbon nanostructures on carbonized electrospun nanofibers with palladium nanoparticles

This paper studies the mechanism of the formation of carbon nanostructures on carbon nanofibers with Pd nanoparticles by using different carbon sources. The carbon nanofibers with Pd nanoparticles were produced by carbonizing electrospun polyacrylonitrile (PAN) nanofibers including Pd(Ac)(2). Such PAN-based carbon nanofibers were then used as substrates to grow hierarchical carbon nanostructures. Toluene, pyridine and chlorobenzine were employed as carbon sources for the carbon nanostructures. With the Pd nanoparticles embedded in the carbonized PAN nanofibers acting as catalysts, molecules of toluene, pyridine or chlorobenzine were decomposed into carbon species which were dissolved into the Pd nanoparticles and consequently grew into straight carbon nanotubes, Y-shaped carbon nanotubes or carbon nano-ribbons on the carbon nanofiber substrates. X-ray diffraction analysis and transmission electron microscopy (TEM) were utilized to capture the mechanism of formation of Pd nanoparticles, regular carbon nanotubes, Y-shaped carbon nanotubes and carbon nano-ribbons. It was observed that the Y-shaped carbon nanotubes and carbon nano-ribbons were formed on carbonized PAN nanofibers containing Pd-nanoparticle catalyst, and the carbon sources played a crucial role in the formation of different hierarchical carbon nanostructures.     

Effective load transfer by a chromium carbide nanostructure in a multi-walled carbon nanotube/copper matrix composite

Multi-walled carbon nanotube (MWCNT) reinforced copper (Cu) matrix composites, which exhibit chromium (Cr) carbide nanostructures at the MWCNT/Cu interface, were prepared through a carbide formation using CuCr alloy powder. The fully densified and oriented MWCNTs dispersed throughout the composites were prepared using spark plasma sintering (SPS) followed by hot extrusion. The tensile strengths of the MWCNT/CuCr composites increased with increasing MWCNTs content, while the tensile strength of MWCNT/Cu composite decreased from that of monolithic Cu. The enhanced tensile strength of the MWCNT/CuCr composites is a result of possible load-transfer mechanisms of the interfacial Cr carbide nanostructures. The multi-wall failure of MWCNTs observed in the fracture surface of the MWCNT/CuCr composites indicates an improvement in the load-bearing capacity of the MWCNTs. This result shows that the Cr carbide nanostructures effectively transferred the tensile load to the MWCNTs during fracture through carbide nanostructure formation in the MWCNT/Cu composite.     

A planar diamond-like carbon nanostructure for a low-voltage field emission cathode with a developed surface

Issues pertaining to the effective solution of problems related to the creation of durable low-voltage field emission cathodes with developed working surface and high density of emission current are considered. Results of practical implementation of the concept of multielectrode field emission planar nanostructures based on diamond-like carbon are presented. High average current density (0.1–0.3 A cm^–2) is ensured by the formation of a controlled zone of electrostatic field localization at the planar-edge structure. The working life of cathode samples reaches 700–3000 h due to several positive factors, such as the stabilizing properties of a diamond-like carbon film, protection of the emitter from ion bombardment, use of a system of ballast resistors, and low-voltage operation of submicron interelectrode gaps.     

ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.     

Carbon additive effects on the nanostructure and magnetic property of the Co-Fe-Zr-B-C films

In this study, the carbon additive Co-Fe-Zr-B alloy films were prepared by dual-gun co-sputtering. The effects of the carbon addition and heat treatment on the nanostructure and magnetic properties of the Co-Fe-Zr-B-C alloy films are reported. The experimental results show that a crystalline (Co, Fe) phase formed after heat treatment at 400 in the Co-Fe-Zr-B-C films with low carbon additive level. Carbon atoms inhibited the crystallization of the as-deposited Co-Fe-Zr-B-C films. From the TEM observation, the nanostructures, such as the atomic structure and grain sizes, showed a strong carbon content dependence. The coercivities of the Co-Fe-Zr-B-C films annealed at 400 varied from 18 to 0.3 Oe with the increasing carbon addition. However, the films annealed at higher temperature exhibited a dramatic increase in the coercivities, which correlated to the formation of the crystalline (Co, Fe) phase. The resistivities of the Co-Fe-Zr-B-C films relied on the carbon contents rather than on annealing temperatures.     

ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

ABSTRACT

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.     

Studies on mechanism of single-walled carbon nanotube formation

We presented detailed studies of the formation of single-walled carbon nanotubes by an aerosol method based on the introduction of pre-formed catalyst particles into conditions leading to carbon nanotube synthesis. Carbon monoxide and iron nanoparticles were used as a carbon source and a catalyst, respectively. The vital role of etching agents such as CO2 and H2O in CNT formation was demonstrated on the basis of on-line Fourier-transform infrared spectroscopy measurements. Hydrogen was shown to participate in the reaction of carbon release and to prevent the oxidation of the catalyst particles and the hot wire. The addition of H2 and small amounts of CO2 and H2O led to an increase in the carbon nanotube lengths. The catalyst particle evaporation process inside the reactor was found to become significant at temperatures higher than 1100 degrees C. The carbon nanotube growth was found to occur at a temperature of around 900 degrees C in the heating section of the reactor by in situ sampling and the growth rate was calculated to exceed 1.1 microm/s. A detailed analysis of possible processes during carbon nanotube formation revealed heptagon transformation as a limiting stage. A mechanism for carbon nanotube formation was proposed.     

Preparation of carbon nanostructures from medium and high ash Indian coals via microwave-assisted pyrolysis

This study is focused on valorizing low value and low quality Indian coals via microwave pyrolysis to produce good quality carbon nanostructures in the heat-treated coal char. The effects of operating conditions such as coal type, coal:susceptor (Fe) mass ratio, and microwave power on product yield and quality are evaluated. The quality of the heat-treated coal char was assessed using different characterization techniques such as electron microscopy, porosimetry, X-ray diffraction, and Raman spectroscopy. The addition of Fe enhanced the heating rates, and led to the formation of carbon nanotubes and nanoparticles. Increasing the proportion of Fe resulted in increase in size of nanotubes and nanoparticles, which is attributed to the fusion of small tubes and particles caused by enhanced localized heating. The yield of carbon nanostructures was more from medium ash (~45%) than from high ash coal (~37%) due to the high fixed carbon and low ash content in the former. In addition to char, coal tar and non-condensable gases were characterized. The major compounds in the coal tar were aromatic hydrocarbons, simple phenols and aliphatic hydrocarbons. Hydrogen and methane were the major gases from medium ash coal, while hydrogen, methane and CO were produced in significant quantities from high ash coal. Microwave-assisted pyrolysis is shown to be a promising process to produce carbon nanostructures in a short time period as compared to conventional thermal processes.     

Synthesis of multicomponent nanocomposites containing filamentary carbon nanostructures

Abstract

In this work, the multicomponent nanocomposites containing filamentary carbon nanostructures were synthesized using materials based on iron oxides with a predominant content of the epsilon phase (ε-Fe₂O₃). These iron oxide-based materials were obtained by a direct plasma-dynamic synthesis with supersonic outflow of an iron-containing electric discharge plasma into an oxygen atmosphere. Subsequently, they were used as an initial precursor and placed in the plasma-chemical reactor, where the multicomponent C/Si_xO_y/Fe₂O₃ nanostructures were synthesized under the influence of the pulsed electron beam. This method was based on the volume excitation of the reaction gas by a pulsed electron beam in such a way as to control the uniform process implementation in the entire excitation region. The morphology and phase composition of the synthesized C/Si_xO_y/Fe₂O₃ nanocomposites were studied. A typical morphological feature of the C/Si_xO_y/Fe₂O₃ samples was found to be the formation of filamentary nanostructures. Their diameter does not exceed 10–20?nm, while their length varies up to 1?μm.     

Preparation of polymer composites using nanostructured carbon produced at large scale by catalytic decomposition of methane

Polymer-based composites were prepared using different concentrations of nanostructured carbons (NCs), produced by catalytic decomposition of methane (CDM). Four carbonaceous nanostructures were produced using different catalysts (with Ni and Fe as active phases) in a rotary bed reactor capable of producing up to 20 g of carbon per hour. The effect of nanostructured carbon on the thermal and electrical behaviour of epoxy-based composites is studied. An increase in the thermal stability and the decrease of electrical resistivity were observed for the composites at carbon contents as low as 1 wt%. The highest reduction of the electrical resistivity was obtained using multi-walled carbon nanotubes obtained with the Fe based catalysts. This effect could be related to the high degree of structural order of these materials. The results were compared with those obtained using a commercial carbon nanofibre, showing that the use of carbon nanostructures from CDM can be a valid alternative to the commercial nanofibres.     

Novel silicon-carbon fullerene-like nanostructures: an Ab initio study on the stability of Si54C6 and Si60C6 clusters

Silicon fullerene like nanostructures with six carbon atoms on the surface of Si60 cages by substitution, as well as inside the cage at various symmetry orientations have been studied within the generalized gradient approximation to density functional theory. Full geometry optimizations have been performed without any symmetry constraints using the Gaussian 03 suite of programs and the LANL2DZ basis set. Thus, for the silicon atom, the Hay-Wadt pseudopotential with the associated basis set are used for the core electrons and the valence electrons, respectively. For the carbon atom, the Dunning/Huzinaga double zeta basis set is employed. Electronic and geometric properties of the nanostructures are presented and discussed in detail. It was found that optimized silicon-carbon fullerene like nanostructures have increased stability compared to bare Si60 cage and the stability depends on the orientation of carbon atoms, as well as on the nature of bonding between silicon and carbon atoms and also on the carbon-carbon bonding.