The mechanism of CO oxidation over Cu(110): Effect of CO gas energy

The effect of the temperature of gas phase CO upon the kinetics of the oxygen titration reaction: CO_g +O_a CO_2,g, has been studied. It is found that the reaction's rate is independant of CO gas temperature between 300 and 623 K. The activation energy (6.5 kcal/mole), dependence upon CO pressure (first-order), and independence upon oxygen coverage for 0.1 _o 0.4 are all independant of the CO gas phase temperature. This result rules out any Eley-Rideal type mechanism whereby CO reacts directly from the gas phase with an oxygen adatom without first being accommodated to the surface temperature in an absorbed state. The result is instead interpretable in terms of a Langmuir-Hinshelwood mechanism.Camille and Henry Dreyfus Foundation Teacher-Scholar Fellowship.     

Intergranular oxidation of silicon in 20Cr-25Ni niobium-stabilized stainless steel at 1140–1230 K

The kinetics of intergranular oxidation of silicon in a 20Cr-25Ni Nb-stabilized stainless steel are reported, at temperatures in the range 1140–1230 K, in CO₂ at 40 bar pressure. The depth of attack increased parabolically with respect to time, with an activation energy of 335±30 kJ/mol. The mechanism of growth is discussed in terms of classical internal-oxidation theories, and an alternative explanation based on an available-space theory is developed. The internal oxidation rates in a number of different alloys are compared with diffusivities of metals in the base alloy. It is proposed that intergranular oxidation in the 20–25 Nb steel is controlled by the rate of outward diffusion of iron or chromium in the alloy.     

Evolution of insoluble eutectic Si particles in anodic oxidation films during adipic-sulfuric acid anodizing processes of ZL114A aluminum alloys

The effects of insoluble eutectic Si particles on the growth of anodic oxide films on ZL114A aluminum alloy substrates were in-vestigated by optical microscopy (OM) and scanning electron microscopy (SE...     

Oxidation behavior and mechanism of aluminum oxynitride (AlON) at elevated temperatures

The oxidation behavior and mechanism of aluminum oxynitride (AlON) powder exposed to air at elevated temperatures between 800°C and 1300°C was investigated by X-ray diffractometry (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), nuclear magnetic resonance (NMR), and simultaneous thermogravimetry, differential thermal analysis, and mass spectrometry techniques (TG-DTA-MS). The weight of AlON gradually increases to a maximum value at 1150°C and then decreases with further heating. Meanwhile, AlON powder undergoes chemical changes, as evidenced by lattice expansion, and turns eventually into alumina. ESR spectra reveal the occurrence of lone pair electrons in the oxidized products and the intensity of corresponding resonance signal increases before disappearing with the increase in temperature. Combined with the results of NMR and TG-DTA-MS, the measured data suggest that Al-N in [AlO₃N] tetrahedron and [AlO₅N] octahedron are gradually oxidized into Al-O-N group with lone pair electrons, which causes continuous weight gain and lattice expansion. Further oxidation at higher temperatures results in alumina and N₂.     

Localized swelling of Fe-Cr-Ni alloy rollers in high-temperature applications

Localized swelling has been observed in 24Cr-24Ni-Nb steel transportation rollers used in the normalizing furnace of a plate mill after prolonged service at high temperature. Due to high localized thermal and mechanical stresses, the chromia layer formed on the roller surface ruptures, exposing the roller substrate to furnace oxygen. Oxidation of second-phase carbides results in the formation of carbon monoxide at very high partial pressure. This leads to formation of voids, leading in turn to localized swelling of the roller material.     

Numerical Simulation of Internal Oxidation of Steels during Annealing Treatments

This paper presents a new model for simultaneous diffusion and precipitation of chemical elements in metallic matrices, a scheme for its numerical solution, and several applications to problems of internal oxidation. The model basically stands as an extension of the classical Wagner model for internal oxidation of steels, but is more much general in that it allows for an arbitrary number of diffusing chemical elements, an arbitrary number of precipitate phases with arbitrary compositions, dependence of diffusion coefficients and solubility products upon (time-dependent) temperature, etc., thus allowing for a much broader range of applications. As a counterpart, it is generally impossible to solve the complex, non-linear equations of the model analytically, but this can be done numerically. The simple but efficient numerical scheme proposed is based on explicit 1D finite differences. Experience has shown that this scheme, in spite of its rusticity and the restrictions it imposes on the time-step, is more efficient than more elaborate strategies based on the finite-element method. The applications presented are concerned with internal oxidation of steels during annealing processes. The model and associated numerical scheme allow for evaluation of the amounts of the various oxide precipitates in the external layer of the sheet. This opens the way, through numerical parametric studies of the influence of the process parameters and the chemical composition, to the improvement of existing treatments and the development of new steel grades.     

Oxidation Performance of Fe-Al/WC Composite Coatings Produced by High Velocity Arc Sprayed at 650 ℃

Fe-Al intermetallics with remarkable high-temperatureintensity and excellent erosion,high-temperatureoxidation and sulfuration resistance are potential lowcost high-temperature structural material.ProducingFe-Al/WC composite coating by high velocity arcspraying(HVAS)on structural materials would notonly obviate the problems faced in fabrication of thesealloys into useful shapes,but also allow the effectiveuse of their outstanding high-temperature performance,which might thus promisingly mak…     

Influence of Atomizing Gases on the Oxide-Film Morphology and Thickness of Aluminum Powders

Fine powders of aluminum were produced in a pilot-plant, inert-gas atomizerwith a confined-design nozzle, which operated vertically upward. Argonand helium at 1.85 MPa and nitrogen at 1.56 MPa were used as the atomizingagent. The morphology of the powder particles was examined by SEM. Powderswere sieved dry and wet. The Sauter mean diameter of the powders varied from20.70 to 10.25 m depending on the atomizing gas. The distribution ofsizes was bimodal. The mean thickness of oxide on the surface of the powderwas calculated from the total oxygen contents of powder samples (determinedby a Leco analyzer). In addition, ESCA measurements and BET tests werecarried out for surface-oxide thickness and area measurements,respectively. The finest powder produced under helium incorporated thinnersurface-oxide layers than the coarser ones produced under argon andnitrogen. This was due to differences in physical properties (such asdensity, thermal conductivity) and flow properties (such as gasvelocity and relative velocity) of the atomizing gases used, i.e., helium,argon, and nitrogen. The oxide was very irregular in thickness in thecoarse-size range of the Al powders produced under argon and nitrogen. Thiswas presumably because of the high- and low-temperature oxidation ofaluminum droplets during the atomization and subsequent solidification andcooling periods leading to the rough surfaces observed with SEMinvestigation in the present work.     

High Temperature Oxidation of Steels in Air and CO2–O2 Atmosphere

Three kinds of hot rolled steel slabs, viz. high strength steel, bake hardened steel and low carbon steel, were oxidized isothermally between 1100 and 1250 °C for up to 2 hr in 1 atm of air and an 85%N₂–10%CO₂–5%O₂ gas mixture. The steels were oxidized in a similar fashion in both the atmospheres. The oxidation process followed an initial linear rate law, which then gradually transformed to a nearly parabolic rate law. Thick, porous and nonadherent scales formed rapidly, due to the high oxidation temperature. The scales formed consisted of Fe₂O₃,(Fe₂O₃+Fe₃O₄), (Fe₃O₄+Fe₂O₃ +FeO) and (FeO+Fe₃O₄) from the outer surface. The presence of supersaturated oxygen beneath the scale resulted in grain boundary oxidation and the formation of internal oxide precipitates.     

High-temperature oxidation of pure titanium in CO2 and Ar-10%CO2 atmospheres

The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO₂ or Ar-10%CO₂. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO₂) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.