Chemistry and kinetics of chemical vapour deposition of pyrocarbon: VII. Confirmation of the influence of the substrate surface area/reactor volume ratio

Carbon deposition from a methane–hydrogen mixture (p_CH4=17.5 kPa, p_H2=2.5 kPa) was studied at an ambient pressure of about 100 kPa and a temperature of 1100°C, using deposition arrangements with surface area/reactor volume ratios, [A_S/V_R], of 10, 20, 40 and 80 cm⁻¹. Steady-state deposition rates and corresponding compositions of the gas phase as a function of residence were determined. The deposition rates in mol/h increase with increasing [A_S/V_R] ratio at all investigated residence times up to 1 s. However, surface-related deposition rates in mol/m²h decreased. As the same results have been obtained in a preceding study using pure methane at a partial pressure of 10 kPa, it has been confirmed that all the kinetics can be determined by changing the [A_S/V_R] ratio.     

Carbon fiber growth kinetics and thermodynamics using temperature controlled LCVD

The chemical kinetics of carbon fiber deposition using Laser Chemical Vapor Deposition (LCVD) was studied. Using methane as the precursor at a total pressure of 78.4 kPa, the activation energy was 176 kJ/mol and the order of the reaction was 3.47. Using propylene as the primary reagent at a total pressure of 21.3 kPa, the activation energy was 286 kJ/mol and the order of the reaction was 1.90. The values are based on measured temperatures ranging from 1720 to 2170 °C. The cause of volcano shaped deposits was also explored through experimentation and thermodynamic modeling, and found to be an etching reaction induced by the elevated temperatures at the center of the laser spot.     

Kinetic Studies on Karlıova Coal

In this study, reaction kinetics of the liquefaction of Karlova coal in a process development unit having three reactors in series have been studied at temperatures of 530–570°C and pressures of 15–25 MPa. It is shown that the rate of hydrogen consumption can be expressed as a function of the concentrations of coal and catalyst, hydrogen partial pressure, reaction temperature, and residence time, and is controlled by the rates of hydrogenation of polynuclear aromatic components and the rates of formation and stabilization of radicals. The relative contribution of these reactions, at any temperature, determines the influence of the hydrogen partial pressure on the rate of the hydrogen consumption. The kinetics of the decomposition reactions of coal to preasphaltene, asphaltene, and oil also have been studied. The apparent activation energies determined are 20 kJ/mol for coal to preasphaltene, 40 kJ/mol for preasphaltene, 66 kJ/mol for asphaltene to oil, and 174 kJ/mol for oil to gases.     

Influence of the deposition parameters on the texture of pyrolytic carbon layers deposited on planar substrates

Pyrolytic carbon layers were deposited from methane on planar substrates (pyrolytic boron nitride) at various residence times, methane pressures and deposition temperatures. The depositions were performed in a cavity oriented perpendicular to the gas flow. The small surface area/reactor volume ratio of the reactor geometry allows depositions in the growth and nucleation mechanism. Transmission electron microscopy was applied to study the texture and microstructure of the carbon layers. A texture transition from medium- to high-textured pyrolytic carbon occurs as a result of increasing residence times, methane pressures and temperatures. Improved textures are generally correlated with increasing deposition rates, which are not necessarily constant during long-term depositions. Lower textures are observed in the vicinity of the substrate interface that are attributed to the influence of the substrate morphology and microstructure.     

Kinetics of surface reactions in carbon deposition from light hydrocarbons

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.     

C,CO and CO2 hydrogenation on cobalt foil model catalysts: evidence for the need of CoO reduction

The hydrogenation of C, CO, and CO₂ has been studied on polycrystalline cobalt foils using a combination of UHV studies and atmospheric pressure reactions in temperature range from 475 to 575 K at 101 kPa total pressure. The reactions produce mainly methane but with selectivities of 98, 80, and 99 wt% at 525 K for C, CO, and CO₂, respectively. In the C and CO₂ hydrogenation the rest is ethane, whereas in CO hydrogenation hydrocarbons up to C₄ were detected. The activation energies of methane formation are 57, 86, and 158 kJ/mol from C, CO, and CO₂, respectively. The partial pressure dependencies of the CO and CO₂ hydrogenation indicate roughly first order dependence on hydrogen pressure (1.5 and 0.9), negative first order on CO (–0.75) and zero order on CO₂ (–0.05). Post reaction spectroscopy revealed carbon deposition from CO and oxygen deposition from CO₂ on the surface above 540 K. The reduction of cobalt oxide formed after dissociation of C-O bonds on the surface is proposed to be the rate limiting step in CO and CO₂ hydrogenation.     

Chemical vapor infiltration of carbon fiber felt: optimization of densification and carbon microstructure

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.     

Hydrogen production from catalytic decomposition of methane over ordered mesoporous carbons (CMK-3) and carbide-derived carbon (DUT-19)

This paper presents a thermogravimetric analysis of catalytic methane decomposition using ordered mesoporous carbon nanorods (CMK-3) and ordered mesoporous carbide-derived carbon (DUT-19) as catalysts. X-ray diffraction and N₂ physisorption analyses were performed for both fresh catalysts. Threshold temperatures for methane decomposition with DUT-19 and CMK-3 were estimated by three different methods found in literature. Carbon formation rate and carbon weight gain as a function of time at various temperatures and methane partial pressures were studied, and the kinetics of CMK-3 and DUT-19 as catalysts for methane decomposition were investigated. Arrhenius energy values of 187 kJ/mol for CMK-3 and 196 kJ/mol for DUT-19 with a reaction order of 0.5 were obtained for both catalysts. Results show that carbon deposition on the catalyst during the reaction lead to catalyst deactivation with significant surface modification. Scanning electron microscope studies of fresh and deactivated catalyst samples show the blocking of catalyst pores and the formation of agglomerates on the outer surface of the catalyst during the course of reaction. DUT-19 catalytically outperforms CMK-3 because of a lower threshold temperature, higher surface area, and higher pore volume. These results show that ordered mesoporous carbons are promising catalysts for methane decomposition.     

Multiple steady-states for the oxidation of aqueous ethanol with oxygen on a carbon supported platinum catalyst

The selective oxidation of aqueous ethanol by dioxygen over a platinum on carbon catalyst was investigated in a three-phase continuously stirred tank reactor at a total pressure of 600 kPa, a temperature of 323 K, a pH of 8.4, and a catalyst concentration of 2.3 kg m^–3. Multiple steady-states were obtained by systematic changes in the start-up procedure and variation of the feed concentration of ethanol and partial oxygen pressure in the reactor. The ethanol feed concentration was varied from 100 to 2500 mol m^–3 and the partial oxygen pressure from 8 to 120 kPa. On the time scale of the experiments, i.e. 21 ks, two steady-states of the net disappearance rate of ethanol are observed in the ethanol feed concentration range from 500 to 2500 mol m^–3 at a partial oxygen pressure of 58 kPa and in the range of partial pressure of oxygen from 8 to 120 kPa at an ethanol feed concentration of 500 mol m^–3. Three steady-states are observed in the feed ethanol concentration range from 200 to 400 mol m^–3 and a partial oxygen pressure of 58 kPa.     

Influence of the surface area/volume ratio on the chemistry of carbon deposition from methane

The chemistry of carbon deposition from methane as a function of methane pressure was studied at a temperature of 1100 °C and surface area/volume ratios of 0.8 and 3.2 mm⁻¹ by analysis of both gaseous and condensing, i.e. aromatic reaction products. Conversion of methane as well as the yields of the hydrocarbons formed increase with increasing pressure. The surface area/volume ratio has a significant influence on the formation of aromatic hydrocarbons showing much higher yields at the lower ratio. This result, expected from preceding studies of deposition rates, confirms that a change of this ratio leads to a change of the deposition chemistry of carbon.     

Investigation of the effect of the total pressure and methane concentration on the growth rate and quality of diamond thin films grown by MPCVD

The influence of total gas pressure (50–125 Torr) and methane concentration (0.75%–10%) on diamond growth by microwave plasma chemical vapor deposition (MPCVD) was investigated. Within the regimes studied, the growth rate was proportional to the methane concentration in the source gas while it exhibited a super-linear dependence on total pressure. For a fixed methane concentration, characterization by Raman spectroscopy, scanning electron microscopy and X-ray diffraction indicated there was a minimum pressure required for the growth of large grain diamond, and conversely, for a fixed pressure, there was a maximum methane concentration that yielded diamond deposition. Higher pressures and higher carbon concentrations yielded diamond growth rates more than 10 times higher than achieved by the conventional low pressure MPCVD process.     

Textures of pyrolytic carbon formed in the chemical vapor infiltration of capillaries

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.     

Low-temperature oxidation of soot

The oxidation rate of propane soot over the temperature range (770–1250 K) has been measured using two methods. These were direct measurements of the burn-out of soot produced by a laminar diffusion flame, and a thermal gravimetric technique using collected soot. The reaction order with respect to oxygen (over the range 1–20 kPa) was determined at a variety of particle temperatures and found to lie between 0 and 0.65. The intrinsic reaction rate at an oxygen partial pressure of 101 kPa was found to be given by ρ_i = 1.05 exp(− 143.5/RT) units where the activation energy is given in kJ/mol. Some values for the oxidation rate of methane soot are also given.     

Neopentane cracking catalyzed by iron- and manganese-promoted sulfated zirconia

Cracking of neopentane was catalyzed by a sulfated oxide of zirconium promoted with iron and manganese. Reaction at 300–450°C, atmospheric pressure, and neopentane partial pressures of 0.00025–0.005 bar gave methane as the principal product, along with C₂ and C₃ hydrocarbons, butenes, and coke. The order of reaction in neopentane was determined to be 1, consistent with a monomolecular reaction mechanism and with the formation of methane andt-butyl cations; the latter was presumably converted into several products, including only little isobutylene. At 450°C and a neopentane partial pressure of 0.005 bar, the rate of cracking at 5 min onstream was 5×10^–8 mol/(g of catalyst s). Under the same conditions, the rates observed for unpromoted sulfated zirconia and USY zeolite were 3×10^–8 and 6×10^–9 mol/ (g of catalyst s), respectively. The observation that the promoted sulfated zirconia is not much more active than the other catalysts is contrasted to published results showing that the former catalyst is more than two orders of magnitude more active than the others forn-butane isomerization at temperatures <100°C. The results raise a question about whether the superacidity attributed to sulfated zirconia as a low-temperature butane isomerization catalyst pertains at the high temperatures of cracking.     

Methylamine hydrogenolysis on a rhodium catalyst: kinetics at high hydrogen partial pressures

The kinetics of hydrogenolysis of methylamine to methane and ammonia on a rhodium catalyst were investigated at hydrogen partial pressures in the range of 2–10 atm at temperatures of 368, 383, and 408 K. At a fixed methylamine partial pressure, the rate decreased with increasing hydrogen partial pressure. When the hydrogen pressure was held constant, the rate increased with increasing methylamine pressure. Results of a previous investigation by our group at lower hydrogen partial pressures (0.01–1 atm) indicated that the hydrogenolysis rate passed through a maximum with increasing hydrogen pressure. Moreover, at the lower hydrogen pressures, there was an inverse rather than positive dependence of the rate on methylamine partial pressure. With the aid of the present results, there is a much clearer definition of the maximum in the experimental data relating the reaction rate to hydrogen partial pressure. The inversion of the effect of methylamine pressure on the rate as the hydrogen pressure is varied over a sufficiently wide range is also firmly established. With regard to the interpretation of the many interesting features of the kinetics, we retain the suggestion from our earlier work that the rate limiting step at the highest hydrogen pressures is the scission of the carbon-nitrogen bond in a partially dehydrogenated methylamine intermediate chemisorbed on the rhodium, with no direct participation of hydrogen as a reactant in this step. At the lowest hydrogen pressures, however, there is a different rate limiting step in which hydrogen does participate directly as a reactant.     

Densification of a 2D carbon fiber preform by isothermal, isobaric CVI: Kinetics and carbon microstructure

Chemical vapor infiltration of a 2D carbon fiber preform with a 0/0/90/90° fiber architecture and a fiber volume fraction of 22.5% was investigated as a function of methane pressure at various temperatures as well as a function of infiltration time at constant pressure. Inside-outside densification was obtained at the most attractive temperature of 1095 °C up to 29 kPa resulting in a maximum bulk density of 1.84 g cm⁻³ and a matrix density of 2.17 g cm⁻³, which corresponds to high-textured carbon. Texture formation can be perfectly explained with the earlier proposed particle-filler model. Studies at increasing infiltration times suggest a recrystallization of carbon deposited in the early stages of the infiltration.     

Deposition rates during the early stages of pyrolytic carbon deposition in a hot-wall reactor and the development of texture

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.     

Effects of Processing Parameters on Alumina Coatings Deposited on Nickel Substrates by Reacting Aluminum Chloride and Hydrogen/Carbon Dioxide Gas Mixtures

Pure nickel coupons were used as substrates in the deposition of alumina (Al₂O₃) from the reaction of aluminum chloride (AlCl₃) with hydrogen/carbon dioxide gas mixtures in the temperature range of 954°–1100°C and system pressures of 2.7–13.3 kPa. The apparent activation energy estimated from the coating growth rate averaged 320 kJ/mol at 13.3 kPa. At temperatures <1000°C, transition theta, kappa, and delta modifications were codeposited with alpha-Al₂O₃, whereas single-phase alpha-Al₂O₃ was deposited at higher temperatures. At high AlCl₃ partial pressures, nickel aluminide phases were sometimes codeposited with Al₂O₃, which was attributed to the reaction of AlCl₃ with the nickel substrate in the presence of hydrogen gas.     

Partial oxidation of methane to syngas over Co/MgO catalysts. Is it low temperature?

Co/MgO catalysts with high Co-loading (>28 wt%) are able to initiate the reaction of methane with oxygen at temperatures around 500 °C. High conversions of methane ( 70%) and very high selectivities for hydrogen and carbon monoxide ( 90%) are obtained at very high reactant gas space velocities (10⁵–10⁶ h^–1). The temperature of the catalyst at the conditions of partial oxidation of methane to form syngas was found to be extremely high (1200–1300 °C); it is about 600–850 °C higher than that previously reported by others. At these temperatures, high temperature homogeneous reactions may prevail. It is suggested that combustion of methane to carbon dioxide occurs on the catalyst with major heat release and that methane and water, respectively methane and carbon dioxide are reformed thermally in an endothermic reaction leading to syngas.     

Kinetics of the reaction of hydrogen with thin films of carbon

The kinetics of the reaction of hydrogen with thin films of carbon has been studied over the temperature range 870–1150K and at pressures of hydrogen from 50–300 Torr (6.7–40 KPa). Thin films of carbon of average thickness about 30 nm were deposited on the surface of a quartz reactor by the pyrolysis of methane at 1100 K and the kinetics were studied in a static system. The products of the reaction were methane, ethane and ethylene, formed in successive hydrogenation steps, which in the low temperature region occurred largely on the surface of the carbon. In this region the activation energy of the rate of formation of methane was 6.5 kcal/mole. At temperatures above about 1050 K the thermal dissociation of hydrogen provided a source of radicals which caused a rapid increase in the rate of hydrogenation, both heterogeneous and homogeneous, giving an activation energy for the rate of formation of methane of 51 kcal/mole. A self-inhibition was observed, probably caused by a heterogeneous polymerization reaction leading to the formation of higher molecular weight products which remained adsorbed on the surface.