The aim of present paper is to present the latest results on investigations of the carbon thin film deposited by
Thermionic Vacuum Arc (TVA) method and laser pyrolysis. X-ray photoelectron spectroscopy (XPS) and X-ray generated Auger electron spectroscopy (XAES) were used to determine composition and sp2 to sp3 ratios in the outer
layers of the film surfaces. The analyses were conducted in a Thermoelectron ESCALAB 250 electron spectrometer
equipped with a hemispherical sector energy analyser. Monochromated Al K X-radiation was employed for the XPS
examination, at source excitation energy of 15 KeV and emission current of 20 mA. Analyzer pass energy of 20 eV with
step size of 0.1 eV and dwell time of 100 ms was used throughout.
Fluids with magnetic characteristics have important values for today applications. This fluids, so called
ferrofluids or magnetic fluids are in general formed by small nanoparticles with mean diameters about 10 nm
and a carrier liquid. In our work we present nanopowders obtained by laser pyrolysis, which have
characteristics for magnetic fluids applications. The important feature of powder was determined by means of
XRD and electron microscopy techniques. The nanopowders have sizes distributed in interval from 2 nm to
10 nm. The high resolution images exhibits single particles with magnetic monodomain. Also, we investigate
nanoparticles for defects. The nanoparticles forms nanoclusters, and high resolution image show adjacent
particles without interface, the coupling mode is only magnetic not chemical. The powders are composed by
magnetite and maghemite phase determined from XRD data, and confirmed by SAED and HRTEM work. The cell parameter calculated from the (220), (311), (511) (440) peaks of sample SF32 is 0.835 nm equal to
the maghemite cell parameter.
Carbon-made materials have been the field of major discoveries with the identification of new phases, which have
stimulated a huge effort to understand their properties. Laser pyrolysis of hydrocarbons is based on a high temperature
C/H/O/... system of well-established composition and allows obtaining carbon nanostructures from the almost
amorphous carbon and particles with a turbostratic structure up to those characterized by a high degree of curvature. The
variation of the gas composition and experimental parameters controls the final particle morphology providing useful
functional properties. Gas-phase hydrocarbons were used either in resonant or non-resonant laser pyrolysis processes.
The formation of different nanostructures is related to the presence of heteroatom in the reactants. Focusing, in the
context of necessary presence of this heteroatom in the gas composition, on the present questions concerning the rational
synthesis of nanostructures with controlled dimensionality, size and potentially properties, the work presents some
significant changes in soot morphology produced by the variation of the experimental parameters and these, sometimes
unavoidable, heterogeneous atoms.
Because of their quantum-scale dimensions, nanoparticles exhibit properties different from those of the bulk. As a result
of their unique properties, numerous efforts have been made to disperse nanoparticles in polymers to enhance or modify
their structural and magnetic properties. A new in situ synthesis method was used to incorporate small iron nanoparticles
into a polyoxocarbosilane polymer matrix. Nano-magnetic iron-based composites were obtained by a one-step procedure
consisting of the IR laser co-pyrolysis of a sensitized (with ethylene) gaseous mixture containing gaseous iron
pentacarbonyl and hexamethyldisiloxane in argon. The simultaneously occurring formation of iron from iron
pentacarbonyl and that of organosilicon polymer from hexamethyldisiloxane yield iron nanoparticles surrounded by an
organosilicon polymer shell. The particles become superficially oxidized in the atmosphere. They were characterized by
Raman analysis, electron microscopy and magnetic measurements. The properties of the nanocomposite particles depend
on the experimental synthesis parameters such as flow rates of precursors, total pressure and laser power. Magnetization
curves, exchange bias Hex at T = 5 K and AC susceptibility were studied in the temperature range 5-400 K. It was found
that the nanocomposite should be in a ferromagnetic blocked state with a minor superparamagnetic contribution of the
smallest nanoparticles.
Multiphase composite nanoparticles presenting core-shell structures have been investigated by performing a detailed correlation between their synthesis parameters and the structural and magnetic properties. Basically in all the experiments iron pentacarbonyl as iron precursor and ethylene as laser energy transfer agent and as a secondary carbon source have been used. The capability of the synthesis technique to form nanocomposite particles by varying laser power density, inlet geometry, pressure in reactor chamber and gas precursors' ratio was tested. The results proved that the laser
pyrolysis can produce particles between 4 and 10 nm diameters. Their sizes may vary according to the reactor pressure and gas flows but their size distributions remain sharp as long as an optimized geometry of the reactor is used. As a second step, the structure and magnetic properties were studied by different techniques such as TEM, HREM, SAED, XRD, FT-IR and Raman spectroscopy. The investigations reveal that, depending on the input parameters, some samples exhibit a nanocomposite structure consisting of iron / iron carbides (Fe3C or Fe2C5) core wrapped in a shell of amorphous or turbostratic carbon. The different magnetic phase identification was performed using Mossbauer spectroscopy and thermo-magnetic analysis.
Soots obtained by laser pyrolysis of different gaseous/vapor hydrocarbons were investigated. The morphology variation of carbon soot versus process parameters and nature of reactants was analyzed and discussed. The role of oxygen is essential in obtaining soot particles having considerable curved-layer content.
A study of the effect of polyaniline doping (with HCl) on the DC and AC conductivity of polyaniline is reported. Additional ESR studies are reported. It is concluded that the charge tansfer in pristine and doped polyaniline occurs through one-dimensional variable large hopping, that the charge transport is dominated by polarons. The presence of high spin bipolarons is ruled out by ESR data.
Laser pyrolysis of a hydrocarbon-based mixture is a continuous method for the synthesis of soot-containing fullerene. In this synthesis process, the mechanism of fullerene formation and soot is the radical mechanism of the PAH formation. In the flames producing both fullerenes and soot, exactly forming carbon cages require particular types of reaction sequences. The fullerene concentrations are strongly correlated with those of PAHs in the flame. The equilibrium soot-PAHs-fullerene is dependent on experimental parameters. FTIR spectra of soot extracts and exhaust gases are discussed in the frame of this dependence.
TiO2 nano powder was prepared by laser pyrolysis of gas phase reactants. TiCl4 (vapor) was used as titanium precursor. The crystalline structures and morphologies of the powder have been analyzed by transmission electron microscopy (TEM), selected area electron diffraction (SAD) and Raman spectrometry. The different characterization techniques suggest that a nano-crystalline mixture of anatase and rutile is obtained.
The embedding of Fe-based nanoparticles in carbon layers allows novel physical and catalyzing properties due to inertness and resistance to external detrimental conditions. We have prepared almost spherical carbon encapsulated iron nanoparticles with narrow size distribution, via laser co-pyrolysis method in which the CW CO2 laser beam irradiates a gas mixture containing iron pentacarbonyl (vapors) and ethylene/acetylene hydrocarbons. Specific flow geometries were used in order to synthesize iron particle first followed by stimulate hydrocarbon decomposition at iron surfaces. High-resolution transmission electron microscopy images reveal the core-shell feature of synthesized nanostructures with around 2 nm thick carbon layers and 3-7 nm diameters iron-based core dimensions. The mean diameter could be experimentally controlled. It was found a decreasing trend of particle size with the decreasing of pressure and total reactant gas flow. EELS, EDAX and Raman spectroscopy analysis confirm the simultaneous presence of carbon and iron. The nanoparticles were seeded onto Si wafer and further used as substrates for laser induced CVD carbon nanotubes growth. Depending on laser power density, nanotubes or nanofibres are formed, in strong dependence with the location of iron based nanoparticles on Si substrates as revealed by SEM analysis.
Iron-carbon composite nanopowders have been synthesized by the CO2 laser pyrolysis of gas-phase reactants. The experimental device allows for a very low reaction time and a rapid freezing that creates nanoscale-condensed particles. Iron pentacarbonyl and ethylene-acetylene mixtures were used as iron and carbon precursors. In a two-steps experiment, the reaction products may present themselves as iron-based nanoparticles dispersed in a carbon matrix. By a careful control of experimental parameters and radiation geometries we demonstrate the feasibility of an efficient and well-controlled, single-step technique for the production of iron-based nano-cores embedded in carbon layers. Highly dispersed nanoparticles, narrow size distributions and particles with about 4.5 - 6 nm mean diameters were obtained. Electron microscopy and Raman spectroscopy were used in order to analyze the structure and composition of the obtained nanopowders as well as their Soxhlet residue.
The preliminary results on the laser synthesis of carbonaceous nanoparticles, which exhibit some characteristic features of fullerene/iron complexes, are reported. The nanopowders were obtained by the laser pyrolysis of a gas phase mixture containing hydrocarbon and alternatively iron pentacarbonyl vapors or ferrocene aerosols. The vapors of iron pentacarbonyl were carried out in the reactor through the intermediate of a bubblier; in the runs using ferrocene, this one was solved in benzene and brought into the reaction zone as aerosol. The reactant mixture contained also nitrous oxide, as oxidizer, and sulphur hexafluoride as energy transfer agent. The as- synthesized powders were toluene extracted and characterized by different analytical methods, such as High Performance Liquid Chromatography (HPLC), IR transmission spectroscopy and Moessbauer spectroscopy. The identification of fullerene-metal complexes was performed by Moessbauer spectroscopy. The Moessbauer transmission spectrum has evidenced the formation of both fullerene phases with iron inside and outside the cage.
Iron clusters were produced by CO2-laser-induced decomposition of iron pentacarbonyl in a flow reactor using SF6 as a sensitizer. By adding hydrocarbon molecules (e.g. C2H4), which were also dissociated in the laser field, the iron clusters were allowed to react with several radicals. The as-synthesized species were extracted from the reaction zone by a conical nozzle and expanded into the source chamber of a cluster beam apparatus where they were analyzed with a time-of-flight mass spectrometer. At sufficiently high C2H4 concentration, we observed the appearance of a magic peak in the mass spectrum at mass m equals 884 amu. Using C2D4 instead of C2H4, the magic peak shifted by 12 amu to larger masses, indicating that the magic cluster must contain 12 hydrogen atoms. With the given restrictions, we readily derive the sum formula Fe13C12H12. Chemical stability and symmetry considerations suggest that the detailed chemical formula of the magic cluster is Fe13(C2H26 or Fe13(CequalsCH2)6 and that its structure corresponds to a Fe13 icosahedron with six HCequalsCH or CequalsCH2 groups bound to six pairs of the 12 iron surface atoms.
The study of producing metal based oxides has become increasingly interesting because of several specific features which make them extremely attractive for various uses, e.g.: catalysts, pigments, magnetic records, sensors, etc. In the present paper we report the synthesis of various iron, copper and nickel oxides by the IR laser processing of different salts. X ray diffraction technique was used in order to characterize the reaction problems. An analysis of the differences between these oxides and those obtained from the same salt by thermal means is presented. It was found that the oxides obtained by laser processing show specific characters concerning the crystallinity and chemical composition.
Since the theoretical studies of Liu and Cohen who predicted the existence of a superhard phase of carbon nitride, a great deal of effort was underdone in order to synthesize this hypothetical material with a nitrogen content as high as the 57% present in a (beta) -C3N4 structure. This study presents an attempt to produce CNx thin films using the laser-induced CVD technique. CW CO2 laser was used for irradiating various carbon-nitrogen containing mixtures such as C2H4/N2O/NH3. The CNx films were grown alternatively on bare alumina ((alpha) - Al2O3) substrates and on pre-deposited Ti films. A comparative analysis of nitrogen incorporation in the films obtained in different experimental conditions was performed by means of the X-ray photoelectron spectroscopy. The same method was used to identify the chemical states of the CN system.
Hydroxyapatite (HA), Ca10(PO4)6(OH)2, is the primary constituent of the human bone and one of the best biocompatible materials. In this work we developed a simple method for the deposition of polycrystalline HA thin films onto various collectors including substrates of medical interest (e.g. Ti). We proceeded by the pulsed laser deposition of HA targets onto parallel collectors placed at (2-5) cm in vacuum. After deposition the films were heated in air at 500 degree(s)C for 30 minutes. The heated film has a structure which appears in electron diffraction as identical to the structure of the base material. The obtained films are uniform and very adherent to the substrate. The P/Ca atomic ratio, determined by energy dispersive X-ray analysis, was found to be close to that characteristic to HA, for the post-depositing heated films.
Carbides and nitrides of metal have a large number of applications in modern technology owing to their interesting, and in some ways unique, physical and chemical properties. Thin film coatings of titanium carbide and aluminum nitride were deposited on Si (100) substrates using pulsed laser deposition method. The structural and microstructural properties of these films have been characterized using x-ray diffraction, and Fourier transform infrared spectroscopic techniques. The mechanical properties of the films were evaluated to measure the hardness and modulus values. It has been shown that the films deposited at higher temperature have the best crystalline quality structure and also have higher hardness values compared to the film deposited at lower temperatures.
Thin amorphous C-N films were deposited on <100> Si and KBr substrates at room temperature by XeCl laser ablation of graphite in low pressure (0.01 - 2.5 mbar) nitrogen atmosphere. Laser fluences were 3, 6, and 12 J/cm2. Scanning electron microscopy, energy dispersion spectroscopy, x-ray diffraction spectroscopy, Rutherford backscattering spectrometry, Fourier transform infrared spectroscopy were used to characterize the deposited films, which result homogeneous, hard, amorphous and present a high electrical resistivity. The deposition rate decreases with increasing ambient pressure. The N/C atomic ratio into the deposited films generally increases with increasing ambient pressure and laser fluence. N/C values up to 0.5 were measured. Heating of the substrates during film deposition causes a reduction of the N/C ratio.
We report a study of the characteristics of thin films deposited at room temperature on Si and KBr substrates by XeCl laser ablation of graphite in low pressure (0.25-2.5 mbar) nitrogen and ammonia atmospheres. Very hard films, with a very high electrical resistivity were obtained. The deposition rates decrease with increasing ambient pressure. N/C atomic ratios up to 0.6 were calculated from backscattering measurements. Different diagnostic techniques (XPS, IR absorption spectroscopy, etc.) demonstrate the formation of carbon nitride with a prevalent graphite-like structure. Films deposited in NH3 are thinner and present a lower quantity of N atoms bound to C atoms than films deposited in N2 at the same ambient pressure.
Laser photo induced reactions from gaseous precursors have been applied to the synthesis of nanosized silicon carbonitrides and (gamma) -alumina based powders. Silicon carbonitrides with different structures and chemical compositions have been produced by changing the reactant gases or their relative concentrations. The structural and chemical evolution have been studied by thermal treatments in Ar and N2 atmosphere. The results confirm the applicability of this powder for industrial applications. Concerning the (gamma) -alumina powder, changes in the reactants concentration ratio have shown to influence both the process yield and the composition of the outcoming powders. Nitrogen or carbon rich (gamma) - alumina powders (Al3O3N, Al2OC) have been synthesized. Some recent and encouraging results on the thermal properties of laser produced silicon carbide are also presented.
Laser-assisted processes for metal-based thin films deposition are currently using vapor-phase precursors. Either photolytic or thermal, the mechanisms developed during laser-induced interaction between adsorbed precursor and substrate are imposing different trends to the composition and morphology of the growing metallic layer. Various aspects of the dynamics of film growth are discussed, in connection with the deposition of titanium from titanium tetrachloride.
The interaction of CO2 laser radiation with mixtures of silane and molybdenum hexacarbonyl (vapor) results in solid Si/C/O/Mo material and various gaseous compounds (mainly CO). The XPS, SEM and IR spectral analysis of the deposit pointed out an organosilicon polymer structure, with a composition that is strongly affected by SiH4 partial concentration. Possible routes involved in the SiH4-photosensitized decomposition of Mo(CO)6 are discussed. The laser technique can serve as an efficient method for creating metal-modified organosilicon polymers for membrane modification.
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