Topography,structure,and formation kinetic mechanism of carbon deposited onto nickel in the temperature range from 400 to 850°C

The carbon deposition behavior on nickel particles was observed within the temperature range from 400 to 800°C in a pure methane atmosphere.The topography,properties,and molecular structure of the deposited carbon were investigated using field-emission scanning electron microscopy(FESEM),temperature-programmed oxidation(TPO) technology,X-ray diffraction(XRD),and Raman spectroscopy.The deposited carbon is present in the form of a film at 400–450°C,as fibers at 500–600°C,and as particles at 650–800°C.In addition,the structure of the deposited carbon becomes more ordered at higher temperatures because both the TPO peak temperature of deposited carbon and the Raman shift of the G band increase with the increase in experimental temperature,whereas the intensity ratio between the D bands and the G band decreases.An interesting observation is that the carbon deposition rate is suppressed in the medium-temperature range(M-T range) and the corresponding kinetic mechanism changes.Correspondingly,the FWHM of the G and D1 bands in the Raman spectrum reaches a maximum and the intensities of the D2,D3,and D4 bands decrease to low limits in the M-T range.These results indicate that carbon structure parameters exhibit two different tendencies with respect to varying temperature.Both of the two group parameters change dramatically as a peak function with increasing reaction temperature within the M-T range.     

Carbon deposition in porous nickel/yttria-stabilized zirconia anode under methane atmosphere

A commercial solid oxide fuel cell with a Ni/YSZ anode was characterized under a pure methane atmosphere. The amount of deposited carbon increased with an increase in temperature but decreased when the temperature exceeded 700°C. The reactivity of carbon decreased with increasing deposition temperature. Filamentous carbon was deposited from 400 to 600°C, whereas flake carbon was deposited at 700 and 800°C. With increasing temperature, the intensity ratio of the D band over the sum of the G and D bands was constant at the beginning and then decreased with the transformation of the carbon morphology. The crystallite size increased from 2.9 to 13 nm with increasing temperature. The results also indicated that the structure of the deposited carbon was better ordered with increasing deposition temperature. In comparison with pure Ni powders, the interaction between the YSZ substrate and Ni particles could not only modify the carbon deposition kinetics but also reduce the temperature effect on the structure and reactivity variation of carbon.     

Effects of specific surface area of metallic nickel particles on carbon deposition kinetics

Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I(D)/I(G) of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.     

Chemical leaching of an Indian bituminous coal and characterization of the products by vibrational spectroscopic techniques

High volatile bituminous coal was demineralized by a chemical method. The vibrations of the "aromatics" structure of graphite, crystalline or non-crystalline, were observed in the spectra at the 1600 cm-1 region. The band at 1477 cm-1 is assigned as V_R band, the band at 1392 cm-1 as V_L band and the band at 1540 cm-1 as G_R band. Graphite structure remains after chemical leaching liberates oxygenated functional groups and mineral groups. The silicate bands between 1010 and 1100 cm-1 are active in the infrared (IR) spectrum but inactive in the Raman spectrum. Absorption arising from C-H stretching in alkenes occurs in the region of 3000 to 2840 cm-1. Raman bands because of symmetric stretch of water molecules were also observed in the spectrum at 3250 cm-1 and 3450 cm-1. Scanning electron microscopy analysis revealed the presence of a graphite layer on the surface. Leaching of the sample with hydrofluoric acid decreases the mineral phase and increases the carbon content. The ash content is reduced by 84.5wt% with leaching from its initial value by mainly removing aluminum and silicate containing minerals.     

Investigation of nanocrystalline structure in selected carbonaceous materials

The structural parameters of nine Indian coals were determined by X-ray diffraction (XRD) and Raman spectroscopy. The study revealed that the coals contain crystalline carbon of turbostratic structure with amorphous carbon. The stacking height (L_c) and interlayer spacing (d₀₀₂) of the crystallite structure of the coals ranged from 1.986 to 2.373 nm and from 0.334 to 0.340 nm, respectively. The degree of graphitization was calculated to range from 42% to 99%, thereby confirming the ordering of the carbon layers with the increase in coal rank. An exponential correlation was observed among the aromaticity (f_a), the lateral size (L_a), and the rank (I₂₀/I₂₆), suggesting that the coal crystallites are nanocrystalline in nature. A very strong correlation was observed between the structural parameters (f_a, d₀₀₂, L_c, the H/C ratio, and I₂₀/I₂₆), the volatile matter content, and the elemental carbon content, indicating the structures of coals are controlled by the degree of contact metamorphism. The Raman spectra exhibited two prominent bands: the graphitic band (G) and the first-order characteristic defect band (D). The deconvolution resulted in five peaks: G, D1, D2, D3, and D4. The intense D1 band, which appeared at ~1350 cm?1, corresponds to a lattice vibration mode with A_1g symmetry. The D2 mode, which appeared at ~1610 cm?1, arises from the structural disorder as a shoulder on the G band.     

Photoluminescence from Ge-SiO2 thin films and its mechanism

Ge-SiO₂ thin films were deposited on p-type Si substrates using the radio frequency (rf) magnetron sputtering technique with a Ge-SiO₂ composite target. Films were annealed in N₂ ambience for 30 min at 300℃—1000℃ with an interval of 100℃. Through the X-ray diffraction, the average size of Ge nanocrystals (nc-Ge) was determined. They increased from 3.9 to 6.1 nm with increasing annealing temperature in the range of 600℃—1000℃. Under ultraviolet excitation, all samples emit a strong violet band centered at 396 nm. With the formation of nc-Ge, the samples exhibit another emission of orange band with the peak at 580 nm and its intensity increases with the increasing size of nc-Ge. The peak positions of two bands do not shift obviously. Experimental data indicate that the violet band comes from GeO defect and the orange band originates mainly from the luminescence centers at the interface between the nc-Ge and SiO₂ matrix.     

Temperature dependence of surface enhanced Raman scattering on C<Subscript>70</Subscript>

The temperature dependence of surface enhanced Raman scattering of the C70 molecule is reported. The Raman scattering of C70 molecules adsorbed on the surface of a silver mirror was measured at different temperatures. The experimental results indicate that the relative intensities of the Raman features vary with the temperature of the sample. When the temperature decreases from room temperature to 0℃, the relative intensifies of certain Raman bands decrease abruptly. If we like the strongest band 1565cm^-1 as a standard value 100, the greatest decrease approaches to 43%. However, with the further decrease in the temperature these relative intensities increase and resume the value at room temperature. And such a temperature dependence is reversible. Our results show that the adsorption state of the C70 molecules on the silver surface around 0℃ changes greatly with the temperature, resulting in a decrease in relative intensities for some main Raman features of C70 molecule. When the temperature is lower than 0℃, the adsorption state changes continually and more slowly. Synchronously, eight new Raman features, which have not ever been reported in fiterature, are observed in our experiment and this enriches the basic information of the vibrational modes for C70 molecule.     

Raman spectra of nitrogen-doped tetrahedral amorphous carbon from first principles

The non-resonant vibrational Raman spectra of nitrogen-doped tetrahedral amorphous carbon have been calculated from first principles, including the generation of a structural model, and the calculation of vibrational frequencies, vibrational eigenmodes and Raman coupling tensors. The calculated Raman spectra are in good agreement with the experimental results. The broad band at around 500 cm^-1 arises from mixed bonds. The T peak originates from the vibrations of sp^3 carbon and the G peak comes from the stretching vibrations of sp^2-type bonding of C=C and C=N. The simulation results indicate the direct contribution of N vibrations to Raman spectra.     

Evolution of carbides and carbon content in matrix of an ultra-high carbon sintered steel during heat treatment process

DTA, thermal expansion, XRD, and SEM were used to evaluate the effect of quenching temperature on the mechanical properties and microstructure of a novel sintered steel Fe-6Co-1Ni-5Cr-5Mo-1C. Lattice parameters and the mass fraction of carbon dissolved in the matrix of the steel quenched were investigated. It is discovered that the hardness of the steel increases with quenching temperature in the range of 840-900℃ and remains constant in the range of 900 to 1100℃. It decreases rapidly when the temperature is higher than 1100℃. The mass fraction of carbon dissolved in the matrix of the steel quenched at 840℃ is 0.38, but when the quenching temperature is increased to 1150℃, it increases to 0.98. The carbides formed during sintering are still present at grain boundaries and in the matrix of the steel quenched at low quenching temperatures, such as 840℃. When the quenching temperature is increased to 1150℃, most of the carbides at grain boundaries are dissolved with just a small amount of spherical M₂₃C₆ existing in the matrix of the quenched steel.     

Structure and Composition of Crystalline Carbon Nitride Films Synthesized by Microwave Plasma Chemical Vapor Deposition

Crystalline carbon nitride thin films were prepared on Si (100) substrates by a microwave plasma chemical vapor deposition method, using CH₄/N₂ as precursor gases. The surface morphologies of the carbon nitride films deposited on Si substrate at 830℃ are consisted of hexagonal crystalline rods. The effect of substrate temperature on the formation of carbon nitrides was investigated. X-ray photoelectron spectroscopy analysis indicated that the maximum value of N/C in atomic ratio in the films deposited at a substrate temperature of 830℃ is 1.20, which is close to the stoichiometric value of C₃N₄. The X-ray diffraction pattern of the films deposited at 830℃ indicates no amorphous phase in the films, which are composed of β- and α-C₃N₄ phase containing an unidentified C-N phase. Fourier transform infrared spectroscopy supports the existence of C-N covalent bond.     

FTIR-ATR chamber for observation of efflorescence and deliquescence processes of NaClO4 aerosol particles on ZnSe substrate

NaClO4 aerosol particles with diameter of 5-20 microns are deposited on the ZnSe substrate. An FTIR-ATR chamber on the ZnSe substrate is set up to observe the structural changes of NaClO4 aerosol particles at crystallization relative humidity （CRH） and deliquescence relative humidity （DRH）. With the decrease of RH （relative humidity） from 96% to 24% in the efflorescence process, the absorbance of O-H stretching band of the aerosol solutions continuously decreases. A sudden decrease of the water peak is observed at RH20%, where solid particles form. Very small amount of residual interfacial water, with two weak peaks at 3602 and 3533 cm^-1, can still be resolved in the FTIR-ATR spectra of the solid particles. In the deliquescence process of the same sample, little spectral changes are observed when the value of RH varies from 5% to 29%. Before the abrupt increase of the O-H stretching band at the DRH of about RH46%, a pre-deliquescence process is observed, i.e. in the RH range between 33% and 46%, there is really a slow absorbance increase for the peak area of O-H stretching band. The O-H stretching band shows an arciform O-H en- velope, totally different from not only the FTIR-ATR spectra of ClO4^- solutions either under supersaturated state or in diluted state, but also the characteristic of the residually interfacial water discussed in the efflorescence process. Such kind of water is considered as pure water, indicating that small amount of water aggregates in the microspaces of solid aerosol particles due to the capillary cohesion effect. When the RH arrives at RH44%, two weak shoulders at 3384 and 3260 cm^-1 can be resolved, and the solid NaClO4 particles begin to be dissolved by increasing capillary cohesion water. The spectral characteristic of the v3-ClO4^- band also shows the transition from solid particles to mainly solvated ClO4^- ions.     

Piezoresistive effect in carbon nanotube films

The piezoresistive effect of the pristine carbon nanotube(CNT)films has been studied.Carbon nanotubes were synthesized by hot filament chemical vapor deposition.The piezoresistive effect in the pristine CNT films was studied by a three-point bending test.The gauge factor for the pristine CNT films under 500 microstrains was found to be at least 65 at room temperature,and increased with temperature,exceeding that of polycrystalline silicon(30at)30℃.The origin of the piezoresistivity in CNT films may be ascribed to a pressure-induced change in the band gap and the defects.     

Effects of deposition parameters on the properties of VO2 thin films

The vanadium oxide thin films are deposited for microbolometers by radio frequency reactive sputtering method at room temperature. The effects of the oxygen partial pressure on the deposition rate, electrical properties and compositions of the films are discussed. The as-deposited VO_x thin films with x value of nearly 2 are deposited by adjusting the oxygen partial pressure. After oxidation annealing of these films in air, the VO₂ films with high temperature coefficients of resistivity (about -4%/℃) and low resistivity can be obtained. The square resistances of the films are in the range of 100 kΩ/squ?300 kΩ/squ. All films are deposited at room temperature and annealed at 400℃, in which the compatibility between VO_x deposition process and MEMS (micro electromechanical systems) is greatly improved.     

Effects of deposition parameters on the properties of VO2 thin films

The vanadium oxide thin films are deposited for microbolometers by radio frequency reactive sputtering method at room temperature. The effects of the oxygen partial pressure on the deposition rate, electrical properties and compositions of the films are discussed. The as-deposited VO_x thin films with x value of nearly 2 are deposited by adjusting the oxygen partial pressure. After oxidation annealing of these films in air, the VO₂ films with high temperature coefficients of resistivity (about -4%/℃) and low resistivity can be obtained. The square resistances of the films are in the range of 100 kΩ/squ?300 kΩ/squ. All films are deposited at room temperature and annealed at 400℃, in which the compatibility between VO_x deposition process and MEMS (micro electromechanical systems) is greatly improved.     

Synthesis and characterization of Au@Pt nanoparticles

Aucore-Ptshell （Au@Pt） nanoparticles were synthesized at room temperature by reducing K2PtCl6 with hydrogen in the solution containing Au colloids and polyvinylpyrrolidone （PVP）. The particles obtained were characterized with UV-Vis, TEM and XPS techniques. UV-Vis spectra show that the surface plasmon absorption feature of Au colloids is significantly reduced with increasing the amount of reduced Pt. TEM images that the metals are found always appear as spherical nanoparticles and their sizes grow apparently due to the reduction of PtCl6^2- ions, indicating that Pt is deposited from solution onto Au particle surface and forms a Pt-layer with uniform thickness. In the XPS spectra, the signals of Au metal decrease due to the reductive deposition of Pt on the surface of the Au colloids. UV-Vis and XPS data are consistent in showing that when the amount of Pt in the AuPt colloids is increased to reach an overall atomic ratio of Pt/Au=2, the Pt deposits form a shell covering completely the surface of Au particles, demonstrating the core-shell structure of the synthesized AuPt particles.     

Novel sintering behavior of polystyrene nano-latex particles in filming process

Filming process of polystyrene nano-latex (NPS) particles was studied by a combination of various methods. For a constant annealing time of 1 h, the AFM images showed that the deformation and sintering temperatures for NPS particles were ca. 90℃ and 100℃ respectively. In spin-lattice relaxation measurements of solid state NMR, it is found that T_1L, T_1S and I_1L/I₀ increased significantly after annealing at 90℃ and above. DSC results showed that there was an exothermic peak near T_g after annealing for 1 h at the selected temperatures below 95℃; otherwise, the exothermic peak disappeared after annealing at 100℃ or above. The apparent density of NPS increased suddenly in the temperature range. The results implied that the macromolecules in NPS particles are in a confined state with higher conformational energy and less cohensional interactions which are the drive force for the sintering at a lower temperature compared with the multichain PS particles and the bulk polymer.     

Growth behavior of electroless copper on silicon substrate

The growth behavior containing deposit morphology, growth rate, activation energy, and growth mechanism of copper on silicon substrate, especially at the initial stage, in the electroless plating process was studied. Copper was deposited on the surface of the silicon substrate in an electloless plating bath containing formalin (CH₂O 37vol%) as a reducing agent at a pH value of 12.5 and a temperature of 50-75℃. The copper deposit was characterized using a field emission scanning electron microscope and transmission electron microscope. The results showed that after the activation process, nanoscale Pd particles were distributed evenly on the surface of the silicon; in the deposition process, copper first nucleated at locations not only near the Pd particles but also between the Pd particles; the growth rate of electroless Cu ranged from 0.517 nm/s at 50℃ to 1.929 nm/s at 75℃. The activation energy of electroless Cu on Si was 52.97 kJ/mol.     

Correlation between structure and hardness of magnetron sputtering deposited CNx films

Carbon nitride films are deposited on Si (001) substrates by reactive dc magnetron sputtering graphite in a pure N2 discharge. The structure of carbon nitride films has been probed using Fourier transformation infrared, near edge X-ray absorption fine structure (NEXAFS) and high resolution electron microscopy (HREM), and the hardness has been evaluated in nanoin-dentation experiments. FTIR spectra show that N atoms are bound to sp1, sp2, and sp3 hybridized C atoms. C1s NEXAFS spectra show that the intensity of π* resonance is the lowest for the film grown at substrate temperature TS = 350℃, with a turbostratic-like structure and high hardness, while it is the highest for the film grown at TS = 100℃, with an amorphous structure and low hardness. The correlation between the structure and hardness of carbon nitride films has been discussed.     

Texture of the nano-crystalline AlN thin films and the growth conditions in DC magnetron sputtering

DC reactive magnetron sputtering technique has been used for the preparation of Al N thin fi lms. The deposition temperature and the fl ow ratio of N2/Ar were varied and subsequent dependency of the fi lms crystallites orientation/texture has been addressed. In general, deposited fi lms were found hexagonal polycrystalline with a(002) preferred orientation. The X-ray diffraction(XRD) data revealed that the fi lm crystallinity improves,with the increase of substrate temperature from 300 ℃to 500℃. The dropped in full width half maximum(FWHM) of the XRD rocking curve value further con fi rmed it. However, increasing substrate temperature above 500 ℃or reducing the nitrogen condition(from 60 to 30% in the environment) induced the growth of crystallites with(102) and(103) orientations. The rise of rocking curve FWHM for the corresponding conditions depicted that the fi lms texture quality deteriorated. A further con fi rmation of the variation in fi lm texture/orentation with the growth conditions has been obtained from the variation in FWHM values of a dominant E1(TO) mode in the Fourier transform infrared(FTIR) spectra and the E2(high) mode in Raman spectra. We have correlated the columnar structure in AFM surface analyses with the(002) or c-axis orientation as well. Spectroscopic ellipsometry of the samples have shown a higher refractive index at 500 ℃growth temperature.     

Synthesis of few layer single crystal graphene grains on platinum by chemical vapour deposition

The present competition of graphene electronics demands an ef fi cient route which produces high quality and large area graphene. Chemical vapour deposition technique, where hydrocarbons dissociate in to active carbon species and form graphene layer on the desired metal catalyst via nucleation is considered as the most suitable method. In this study, single layer graphene with the presence of few layer single crystal graphene grains were grown on Pt foil via chemical vapour deposition. The higher growth temperature changes the surface morphology of the Pt foil so a delicate process of hydrogen bubbling was used to peel off graphene from Pt foil samples with the mechanical support of photoresist and further transferred to Si O2/Si substrates for analysis. Optical microscopy of the graphene transferred samples showed the regions of single layer along with different oriented graphene domains. Two type of interlayer stacking sequences, Bernal and twisted, were observed in the graphene grains.The presence of different stacking sequences in the graphene layers in fl uence the electronic and optical properties; in Bernal stacking the band gap can be tunable and in twisted stacking the overall sheet resistance can be reduced. Grain boundaries of Pt provides low energy sites to the carbon species, therefore the nucleation of grains are more at the boundaries. The stacking order and the number of layers in grains were seen more clearly with scanning electron microscopy. Raman spectroscopy showed high quality graphene samples due to very small D peak. 2D Raman peak for single layer graphene showed full width half maximum(FWHM) value of 30 cm-1. At points A, B and C, Bernal stacked grain showed FWHM values of 51.22, 58.45 and 64.72 cm-1, while twisted stacked grain showed the FWHM values of 27.26, 28.83 and 20.99 cm-1,respectively. FWHM values of 2D peak of Bernal stacked grain showed an increase of 20–30 cm-1 as compare to single layer graphene which showed its dispersive nature and con fi rmed Bernal sequence. On the other hand, the slightest decrease in FWHM values of 2D peak in twisted grain comparing to single layer con fi rmed the twisted sequence of grains. Atomic force microscopy analysis showed an increasing trend in grain height pro fi le with an increase in the number of layers.