K. Natesan

Oxidation of Copper and Electronic Transport in Copper Oxides

AbstractOxidation of copper and electronic transport in thermally-grown large-grain polycrystals of nonstoichiometric copper oxides were studied at elevated temperatures. Thermogravimetric copper oxidation was studied in air and oxygen at temperatures between 350 and 1000°C. From the temperature dependence of the oxidation rates, three different processes can be identified for the oxidation of copper: bulk diffusion, grain-boundary diffusion, and surface control with whisker growth; these occur at high, intermediate, and low temperatures, respectively. Electrical-conductivity measurements as a function of temperature (350–1134°C) and oxygen partial pressure (10−8–1.0 atm) indicate intrinsic electronic conduction in CuO over the entire range of conditions. Electronic behavior of nonstoichiometric Cu2O indicates that the charge defects are doubly-ionized oxygen interstitials and holes. The calculated enthalpy of formation of oxygen (

Electronic transport in thermally grown Cr2O3

\Delta H_{{\text{O}}_{\text{2}} }

Oxidation-sulfidation behavior of iron-chromium-nickel alloys

) and hole-conduction energy (EH) at constant composition for nonstoichiometric Cu2O are 2.0±0.2 eV and 0.82±0.02 eV, respectively.

Sulfidation-oxidation of advanced metallic materials in simulated low-Btu coal-gasifier environments

The metal-dusting phenomenon, which is a metal loss process that occurs in hot reactive gases, was investigated in iron and certain iron-base alloys by Raman scattering, X-ray diffraction (XRD), and scanning-electron microscopy (SEM). Coke from metal dusting exhibits six Raman bands at 1330(D band), 1580(G band), 1617, 2685, 3920, and 3235 cm-1. The bandwidths and the relative intensities of the 1330 and 1580 cm-1 bands are related to the crystallinity and defect structure of the coke. Both Raman and XRD analyses suggest that the metal-dusting process influences the catalytic crystallization of carbon. A new mechanism of metal dusting is, therefore, proposed, based on the premise that coke cannot crystallize well by deposition from carburizing gases at low temperature without catalytic activation because of its strong C–C bonds and high melting temperature. Cementite or iron participates in the coke-crystallizing process in a manner that tends to improve the crystallinity of the coke. At the same time, fine iron or cementite particles are liberated from the pure metal or alloys.

Transient oxidation in Fe-Cr-Ni alloys: A Raman-scattering study

Electrical conductivity of thermally grown Cr2O3 has been measured as a function of temperature and over a range of oxygen partial pressures from that of air to that of the Cr/Cr2O3 equilibrium. The conductivity showed p-type behavior over the range of the present investigation. At temperatures above 1000°C, the conductivity values were independent of oxygen partial pressure and indicated intrinsic semiconductor behavior. The mobility of holes, determined by measuring conductivity at fixed compositions (i.e., fixed δ in Cr2-δO3), increased with temperature. This behavior can be attributed to hopping-type conduction. For δ ∼ 10−5, the activation energy for hole hopping was 0.248 eV, and the calculated hole mobilities were 5.4x10−2 and 2.4x10−1 V/cm2 · s at 500 and 1000°C, respectively. The oxidation kinetics of Cr were determined by measuring the electrical conductivity and electromotive force across the oxide layer at 875°C. The result agreed well with the oxidation data obtained in thermogravimetric tests.

Oxidation-sulfidation behavior of Ni aluminide in oxygen-sulfur mixed-gas atmospheres

Structural Fe-Cr-Ni alloys may be rapidly degraded in oxygen-sulfur mixed-gas environments at elevated temperatures unless protective oxide scales can be formed and maintained. The breakaway corrosion process was examined in model alloys of Fe-25wt.% Cr-20wt.% Ni with and without Nb and Zr additions. Oxide scales were preformed in S-free environments and subsequently exposed to oxygen-sulfur mixed-gas atmospheres. Preformed scales were found to delay the onset of breakaway corrosion. The beneficial effects of refractory metal additions were achieved via formation of a barrier layer at the Cr2O3 alloy interface.

A study of the initial stages of oxidation of Fe-Cr-Ni-Zr alloysin situ using a high-voltage electron microscope

Oxidation-sulfidation studies of Fe-Cr-8Ni alloys with 4, 12, and 22 wt. % Cr were conducted at 750 and 875°C in multicomponent gas mixtures that contained CO, CO2, CH4, H2, and H2S. The reaction processes resulted in parabolic kinetics. A chromium concentration in the range 0–12 wt. % in the alloy had a negligible effect on the parabolic rate constant; however, the rate constant for the alloy with 22 wt. % Cr was significantly lower. For a given sulfur partial pressure, the oxygen partial pressures required for the formation of a continuous oxide layer in an Fe-22Cr-8Ni alloy were ∼102 to 103 times those calculated for Cr-Cr2O3 equilibrium at temperatures of 875 and 750° C, respectively.

Oxidation and sulfidation behavior of Fe-20Cr-16Ni-4Al-1Y2O3 oxide-dispersion-strengthened alloy

The corrosion behavior of structural alloys in complex multicomponent gas environments is of considerable interest for their effective utilization in coal conversion schemes. Little understanding of the degradation mechanisms of advanced high-temperature alloys in conditions typical of low-Btu coal gasifiers presently exists. Analysis of scale and subscale characteristics of several alloy types after exposure to the aggressive simulated low-Btu gasifier environments yielded a reaction model for these sulfidation-oxidation conditions. Initial competition between reactive metal oxide and base metal sulfide nuclei is followed by base metal sulfide overgrowth, chromium sulfide formation at the scale-metal interface, dissociation near voids in the subscale, and internal chromium sulfide precipitation. Additions of aluminum, titanium, and an oxide dispersion improve the sulfidation resistance by increasing the number of oxide nucleation sites and their growth kinetics on the surface in the crucial competition stage. Thermogravimetric tests carried out in three mechanistic regimes agreed with these hypotheses.