A study of chromic oxide decomposition in an RF argon plasma

Vapor-phase thermal decomposition of chromic oxide in an rf argon plasma was studied using a new experimental system. Homogeneous and heterogeneous modes of reaction were compared, the overall process efficiency being substantially higher for the process carried out entirely in the vapor phase. Reaction products were collected along the reactor wall and studied by chemical methods as well as SEM, X-ray, and IR absorption. The collected powder was highly reactive, fine-grained, and of semiamorphous nature, the average particle size being well below 100 nm. Temperature profiles recorded below the coupling coil by spectroscopic methods were typical of an rf plasma, showing maxima slightly exceeding 5000 K, with the presence of off-axis peaks. Local Cr contents and concentration ratio (Cr)/(Cr₂O₃) in the plasma were determined from the deposition data obtained. A diffusion process was assumed for the wall-deposit buildup. The results obtained confirmed the advantages of using plasma vapor-phase systems, these being higher-efficiency processes and more reliable models than those obtained in the case of gas-solid plasma reactors, where solid particles are injected into the plasma. The thermal decomposition conversion of Cr₂O₃ into Cr was about 8 times higher in the homogeneous gas phase than in the plasma solid phase, all other conditions being equal.Nomenclature c velocity of light, cm × s^–1 - C_Cr^m metallic Cr content, % by wt. - C_Cr^t total Cr content, % by wt. - D species diffusivity, cm² · s^–1 - E energy of excited level, eV - f oscillator strength - F rate of species deposition, mol · cm^–2 · s^–1 - g statistical weight - h Planck's constant, J · s^–1 - I radial emission intensity for a given spectral line at a given radius in the plasma, W · sr^–1 · cm^–3 - k Boltzmann's constant, J · K^–1 - l length of collected deposit, cm - m mass of collected deposit, g - M molar weight of Cr - M_Ar^a molar flow of axial argon, mmol · s^–1 - M_Ar^p molar flow of peripheral argon, mmol · s^–1 - M_Cr2O₃ molar flow of evaporated Cr₂O₃, mmol · s^–1 - Cr(I) concentration, cm^–3 - Q_T partition function at temperatureT - r reaction radius, cm - R radius of quartz tube, cm - t duration of deposition, s - T temperature, K - total extent of Cr₂O₃ decomposition into Cr, % - Z position of a plane normal to the plasma axis downward the lower turn of rf coil, cmGreek Letters molar ratio of Cr and Cr₂O₃ in deposit - wavelength, nm - species concentration, mol · cm^–3