共查询到20条相似文献,搜索用时 15 毫秒
1.
Pyrocarbon layers were deposited from methane on planar substrates (pyrolytic boron nitride) at a temperature of 1100 °C and residence times of 0.1, 0.5 and 2.5 s. The depositions were performed in a hot-wall reactor with the substrates oriented parallel to the gas flow. Transmission electron microscopy was applied to study the texture and the structure of the carbon layers on a micrometer and nanometer scale. The texture is influenced by the residence time. An alteration from medium- to high-textured carbon is observed from short to long residence times. The nanostructure of high- and medium-textured pyrocarbon is characterized by domains whose sizes do not generally differ. 相似文献
2.
Pyrolytic carbon layers were deposited from methane/oxygen/argon mixtures on planar substrates (silicon wafers) at a total pressure of 100 kPa, a maximum gas residence time of 2 s and a temperature of 1100 °C. The depositions were performed in a hot-wall reactor with the substrate oriented parallel to the gas flow. Particular attention was paid to factors that influence the reproducibility of the deposited layers. Scanning and transmission electron microscopy were applied to study the thickness profiles and the texture of the carbon layers. The surface topography was investigated by atomic force microscopy. For pyrolytic carbon deposited without oxygen, an alteration from medium- to high-textured carbon is observed with increasing residence time. Islands are observed on the surface of the layer whose size increases with the texture. For pyrolytic carbon deposited with 3% oxygen, lower deposition rates were obtained and a strong modification of the texture is found compared to gas mixtures without oxygen. 相似文献
3.
V. De Pauw 《Carbon》2008,46(2):236-244
Electron microscopic and electron spectroscopic techniques were applied to study interface properties, microstructure and texture of pyrolytic carbon obtained after short-time chemical vapor deposition (CVD) on planar Si substrates. The pyrolytic carbon was obtained in a hot-wall reactor from methane at a total pressure of 20 kPa and temperature of 1100 °C. Only short depositions between 2.5 and 240 min were performed. The carbon deposition starts with the nucleation of isolated islands. The increase of residence and deposition time leads to the formation of a continuous layer by larger island sizes and higher island densities, a transition from rough to smooth surfaces and formation of pores on smooth surfaces. An increased deposition rate during the first 15 min is observed which is correlated with a granular morphology of the carbon layer. Using BN-covered Si wafers with a surface roughness on a 100 nm scale reduces the texture degree in the vicinity of the interface and strengthens adhesion of the pyrolytic carbon compared to the smooth Si substrate. The texture of high-textured pyrolytic carbon is improved significantly by annealing at 1100 °C. 相似文献
4.
Chemistry and kinetics of chemical vapor deposition of pyrocarbon: VI. influence of temperature using methane as a carbon source 总被引:1,自引:0,他引:1
The chemical vapor deposition of carbon from methane was investigated at an ambient pressure of about 100 kPa, a methane partial pressure of 10 kPa and temperatures ranging from 1050–1125°C. Carbon deposition rates and compositions of the gas phase as a function of residence time have been determined using a substrate with a surface area/reactor volume ratio of 40 cm−1. Increasing temperatures lead to strongly increasing deposition rates, decreasing partial pressures of ethane and increasing partial pressures of ethene, ethine and benzene. The overall activation energy of carbon deposition, determined from the initial deposition rates at a residence time versus zero amounts to 446 kJ/mol as compared to 431.5, 448 and 452.5 kJ/mol reported in earlier papers. Two possible rate-limiting steps are discussed, namely dissociation of methane, which is favored in the earlier papers, and dissociation of carbon–hydrogen surface complexes. 相似文献
5.
The kinetics of carbon deposition from methane were studied over broad ranges of pressures, temperatures and reciprocal surface area/volume ratios. Based on these results, it was possible to distinguish between a growth and a nucleation mechanism of carbon deposition and to select conditions for the preparation of well-defined samples for texture analysis by transmission electron microscopy and selected area electron diffraction. Maximal texture degrees were obtained at medium or high values of the above parameters, but never at low values, at which carbon formation is based on the growth mechanism and dominated by small linear hydrocarbons. High-textured carbon resulting from the growth mechanism is concluded to be formed from a gas phase with an optimum ratio of aromatic to small linear hydrocarbons, which supports the earlier proposed particle-filler model of carbon formation. High-textured carbon may also be formed from a gas phase dominated by polycyclic aromatic hydrocarbons (nucleation mechanism) provided that the residence time is sufficiently long that fully condensed, planar polycyclic aromatic hydrocarbons can be formed in the gas phase. 相似文献
6.
Capillaries, 1.1 mm in diameter and 17.0 or 32.5 mm in length, were infiltrated at a temperature of 1100 °C and methane pressures from 5 to 30 kPa. Layer thickness and carbon texture were determined at cross-sections of 2, 16 and 32 mm from the open end of the capillaries using polarized light microscopy. Average deposition rates, determined from layer thickness and infiltration time, as a function of methane pressure indicate a rate increase up to a saturation adsorption at pressures between 10 and 15 kPa (range 1) and a strong rate increase above these pressures (range 2). This result implies carbon formations based on the growth mechanism in range 1 and the nucleation mechanism in range 2. The carbon texture shows a maximum in range 1 and a minimum in the transition from range 1 to range 2 followed by a clear increase in range 2. The maximum in range 1 corresponds to the particle-filler model describing formation of various textures of carbon by the ratio of aromatic species to C2 species. Increasing texture degrees in range 2 suggest that the nucleation mechanism may lead to high textured carbon provided that the residence time for intramolecular rearrangments of polycyclic aromatic hydrocarbons is sufficient. 相似文献
7.
P.J. Meadows 《Carbon》2009,47(1):251-262
Pyrolytic carbon coatings were deposited on top of alumina particles at deposition temperatures from 1250 °C to 1450 °C and with acetylene and acetylene/propylene mixtures at concentrations between 25% and 70%, v/v. The anisotropy of pyrolytic carbon coatings was quantified using electron diffraction and Raman peak intensities, and related to the deposition conditions and microstructure. In correlation with the TEM images, it was found that the value of orientation angle (OA) measured from selected area electron diffraction patterns, increased with increasing deposition temperature and precursor concentration corresponding to a reduction in texture. The effect of temperature was more pronounced for the acetylene/propylene mixture and at low temperatures highly anisotropic material was obtained on a local scale. However, the use of larger TEM selecting apertures showed that the majority of coatings were isotropic overall. A correlation was found between OA and Raman D band intensity which allows quick classification of pyrolytic carbon texture. 相似文献
8.
A new method for forming isotropic, laminar, and columnar pyrolytic carbons is proposed. For this, a low RPM (below 2.4 rpm) tumbling bed has been used to deposit pyrolytic carbons from hydrocarbon gases. All deposits were made on graphite substrates from propane and methane at a constant temperature of 1200°C. The microstructures of the pyrolytic carbons deposited were dependent on the flow pattern of the reactant gas, the rpm of the reactor, the hydrocarbon concentration, the nature of the hydrocarbon, and the geometry of the bed. Isotropic pyrolytic carbon is formed under deposition conditions where homogeneous nucleation occurs in the gas phase and at the gas flow conditions where the gas-borne droplets can collide on the substrate. Laminar carbon is formed under deposition conditions where homogeneous nucleation does not occur in the gas phase and at gas flow conditions where the carbon species existing in the bulk of the gas phase can collide on the substrate. Columnar carbon is formed when any carbon products existing in the bulk of the gas phase cannot collide on the substrate. The suggested deposition mechanism can also be applied to pyrolytic carbons deposited in a fluidized bed or in a stationary bed. In particular, isotropic carbon can be obtained even in a stationary bed if the requirements for the deposition of the isotropic carbon described above are satisfied. 相似文献
9.
The processing and microstructure of carbon coatings deposited using liquid reagent CVD were studied. High density pyrolytic carbon coatings were successfully deposited on graphite and molybdenum substrates from benzene and cyclohexane precursors. Very high deposition rates were obtained. Examination via transmission electron microscopy showed that the deposits were of the desired turbostratic nodular structure with low texture. 相似文献
10.
A FaißtH v. Löhneysen 《Carbon》2002,40(3):321-327
Electrical resistivity measurements in an applied magnetic field B up to 14 T were performed at low temperatures T on several samples of pyrolytic carbon deposited on a substrate of pyrolytic boron nitride. The films were produced in a CVD reactor at 1100°C from a methane/argon gas flow. For B, a maximum is observed in the electrical resistance at low temperatures T≈10 K which has been previously found for carbon fibers. The magnetoresistance in this T region can be separated into an isotropic positive part and an anisotropic negative contribution. 相似文献
11.
Steven Wang Woo Jin Lee Chao'en Li Benny Kuan Nick Burke Jim Patel 《American Institute of Chemical Engineers》2019,65(3):1035-1046
This study of methane pyrolysis was designed to look at carbon deposition on the internal reactor and wafer surface during CH4 pyrolysis. The rate of carbon deposition on the internal reactor surfaces could be reduced with: lower methane/oxygen ratios, shorter residence times, and lower temperatures. The type of carbon formed appeared to have a significant effect on the pyrolysis process. Pyrolytic carbon with a lower order structure produces a higher selectivity for carbon formation compared to carbon with a higher order structure. Form a process perspective, there are two obvious means of addressing this: deposited carbon could be regularly removed; and/or pyrolysis conditions are selected that produce carbon with a higher order structure. From the results, it is very clear that any development of a commercial process for natural gas pyrolysis in ceramic reactor systems would have to carefully address the selection of reactor material. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1035–1046, 2019 相似文献
12.
The textures, growth features, microstructures and binding of carbon atoms of pyrolytic carbons prepared by chemical vapor deposition (CVD) at a temperature between 800–1200 °C on graphite substrate and carbon fibers were studied. The intermediate product phase of pyrolytic carbons was also investigated. Based on the present study a deposition model of viscous droplet was proposed in this paper. The viscous droplet here refers to all kinds of fine spheroids that are more or less viscous. The mechanism of the formation of three typical textures namely, smooth laminar, rough laminar and isotropic carbons can be satisfactorily explained by this model. 相似文献
13.
Koyo Norinaga 《Carbon》2003,41(8):1509-1514
Carbon deposition from ethene, ethine and propene as a function of pressure was studied at various temperatures and two different surface area/volume ratios. Deposition rates as a function of pressure of all hydrocarbons indicate Langmuir-Hinshelwood kinetics which suggests that the deposition process is controlled by the heterogeneous surface reactions (growth mechanism). These kinetics are favored at decreasing reactivity (C3H6>C2H2>C2H4), decreasing temperature and residence time as well as increasing surface area/volume ratio. A linear rate increase at high pressures suggests that carbon is additionally or preferentially deposited by aromatic condensation reactions between polycyclic aromatic hydrocarbons large enough to be physisorbed or condensed on the substrate surface (nucleation mechanism). The results completely agree with earlier results obtained with methane. 相似文献
14.
A carbon fiber felt with a fiber volume fraction of 7.1% was infiltrated at temperatures of 1070 and 1095 °C and methane pressures from 5 to 30 kPa to confirm the inside-outside densification derived from model studies with capillaries 1 mm in diameter. Bulk densities and residual open porosities were determined as a function of infiltration depth at various heights of the felt. The texture of the infiltrated carbon was studied by polarized-light microscopy and characterized with the aid of the extinction angle. Inside-outside densification was demonstrated up to the maximum pressure of 30 kPa at 1070 °C and up to 13.5 kPa at 1095 °C, leading to bulk densities above 1.9 g/cm3. A pure, high-textured carbon matrix is formed in the pressure range from 9.5 to 11 kPa at 1095 °C. At lower and higher methane pressures and lower temperature, a less textured carbon is formed. The results are based on the growth mechanism of carbon deposition. They strongly support recent conclusions that high-textured carbon is formed from a gas phase exhibiting an optimum ratio of aromatic hydrocarbons to small linear hydrocarbons, preferentially ethine. This model is called the particle-filler model. Aromatic hydrocarbons are the molecular particles and small linear hydrocarbons are the molecular filler, necessary to generate fully condensed planar structures. 相似文献
15.
Understanding the chemical reaction mechanism and deposition kinetics is of great importance to guide the production of pyrolytic carbon (PC). A practical approach to mimic the commercial chemical vapor deposition (CVD) process and eventually predict the PC deposition rate is highly desired. In this work, a simplified two-step reaction mechanism was proposed for the CVD of PC, with the first step in the gas phase and the second step on the substrate surface. The kinetic parameters were determined by trial and error using a computational fluid dynamics simulation. The velocity, temperature, and concentration profiles in a cold-wall, forced-flow reactor were modeled based on the geometry and experimentally determined boundary conditions. The computed PC deposition rates for substrate temperatures between 700 and 3000 °C were in good accordance with experimental results. Rate limiting steps were observed for both the deposition experiments and simulations. Mass-transport-limited and reaction-limited regimes were identified in wide temperature and flow rate ranges. A higher deposition rate was found in a cold-wall reactor compared with those in an insulated reactor or a hot-wall reactor. Finally, the PC microstructure was characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy, and X-ray diffraction, demonstrating progressive development of graphitization with increasing deposition temperature. 相似文献
16.
King Hong Kwok 《Carbon》2003,41(12):2295-2305
The feasibility of using pyrolytic laser-induced chemical vapor deposition (LCVD) to deposit carbon coatings on moving fused quartz substrates is investigated. This LCVD system uses a CO2 laser to locally heat a substrate in open air to create a hot spot. Pyrolysis of hydrocarbon species occurs and subsequently deposits a layer of carbon film onto the substrate surface. The results of this study indicate that growth kinetics and the geometry of uniform carbon stripes deposited by pyrolytic LCVD strongly related to the laser power, the traverse velocity of the substrate, the type of hydrocarbon species used in deposition, and the diameter of the substrate. The deposition rate of carbon film increases exponentially with the laser power, while an increase in traverse velocity of the substrate will also increase the deposition rate until a maximum deposition rate is reached; further increases in the traverse velocity will decrease the deposition rate. We suspect that this optimal deposition rate is caused by substrate motion, which affects the substrate surface temperature, and consequently the effective surface area available for film deposition. The substrate temperature is observed to behave linearly with the deposition parameters considered in this study. 相似文献
17.
The early stages of chemical vapor deposition of pyrolytic carbon on planar silicon substrates were studied by the atomic force microscopy-based technique of chemical contrast imaging. Short deposition times were chosen to focus on the early stages of the deposition process, and three different types of nucleation were found: random nucleation of single islands, nucleation of carbon islands along lines and secondary nucleation which corresponds to the nucleation of carbon islands at the edges of already existing carbon islands. The transition from individual carbon islands to a complete carbon film was observed with increasing residence time. 相似文献
18.
D. King M.K. Yaran T. Schuelke T.A. Grotjohn D.K. Reinhard J. Asmussen 《Diamond and Related Materials》2008,17(4-5):520-524
The scale up of two microwave plasma assisted chemical vapor deposition processes from 75 mm to 200 mm substrates is investigated. A thermally floating 2.45 GHz reactor is scaled up by increasing its physical size by a factor of 2.7 and exciting the reactor with 915 MHz microwave energy. Two processes are investigated, 1) the deposition of ultananocrystalline diamond films (UNCD) and 2) the deposition of polycrystalline diamond films (PCD). Gas chemistries of argon/methane/hydrogen were used for UNCD deposition and hydrogen/methane was used for PCD deposition. Experimental pressures range from 40–110 Torr while microwave power input ranged from 1.9–7 kW resulting in steady state substrate temperatures from 630–950 °C. Uniform deposition was demonstrated over 150–200 mm substrates, i.e. thickness variations of 4% over 150 mm and 6% over 200 mm were achieved with deposition rates ranging from 30–460 nm/h. Low temperature deposition at 633 °C was achieved and thereby demonstrated the potential of integrating the process with temperature sensitive materials. A comparison of the power densities between the two reactors indicates that the large reactor operates at five to nine times lower discharge power densities than smaller reactors suggesting improved deposition efficiencies. 相似文献
19.
20.
Chemical vapour infiltration is simulated by deposition of pyrolytic carbon on planar boron nitride substrates and carbon fibers in a hot-wall tubular reactor at about 1100 °C for varied pressure and flow-velocity of methane. The degree of orientation of the deposited graphite-like domains can be monitored via orientation and temperature dependence of the electron spin resonance parameters (g-tensor, linewidth). The electronic structure of the localized defects and conduction electrons is accessible by a quantitative modelling of these parameters. The interaction of the built-in hydrogen atoms with the unpaired electron spins is analysed by electron-proton spin double resonance technique (Overhauser shift) 相似文献