Below 1000°C the oxidation of nickel cannot be controlled by the diffusion of ions through the bulk crystal lattice of the pure oxide, because the measured oxidation rates are several orders of magnitude faster than would be predicted on this basis. Short-circuit diffusion through oxide grain boundaries or dislocations has usually been held responsible, but there has hitherto been no proper quantitative confirmation of this mechanism. We report measurements of the oxide scale thickness and oxide grain size as a function of time during the oxidation of high-purity nickel in the temperature range 500–800°C. All the oxidation experiments were carried out in pure oxygen at a pressure of one atmosphere. The measured parabolic oxidation rate constants have been compared with those calculated from grain boundary diffusion data obtained in our previous work, using a grain boundary diffusion model for the oxidation process. The quantitative agreement between measured and calculated oxidation rates shows c...

A quantitative demonstration of the grain boundary diffusion mechanism for the oxidation of metals

Mechanisms controlling the durability of thermal barrier coatings

A phenomenological description of crystallographic slip and pencil glide in single crystals is outlined, with emphasis on the behavior under prescribed strains Theoretical relations are established between these single-crystal properties and the behavior of quasi-homogeneous, quasi-isotropic polycrystals deforming uniformly on a macroscopic scale, at subdiffusive temperatures Experimental comparisons between single crystals and polycrystals are reviewed, considering flow stress, work hardening, temperature and strain rate effects, and various effects of grain size

The relation between polycrystal deformation and single-crystal deformation

Some of the important principles that determine the establishment, growth and long-term maintenance of protective Cr2O3, Al2O3 and SiO2 scales on hightemperature iron-, nickel- and cobalt-base alloys are reviewed and discussed. Emphasis is placed on the effects of alloying elements and other additions, such as third elements and reactive elements or oxide dispersions, on each of these processes. Particular attention is paid to transport processes in the scales and the importance of short-circuit paths. Some of the important parameters that influence the long-term mechanical stability of such scales are considered and evaluated.

The influence of alloying elements on the development and maintenance of protective scales

Currentunderstanding of the complex interrelationships among growth kinetics, microstructure, and adhesion of protective Cr2O3 and Al2O3 scales is critically reviewed. Similarities and differences in the behavior of these two systems are highlighted. The morphology of the alloy-scale interface appears to be a critical factor. Recent ideas are advanced to interpret the effect of oxygen-active elements on the development of a tortuous interface conducive to improved scale tenacity.

/pdf/microstructure-adhesion-and-growth-kinetics-of-protective-2v2aeq1h8a.pdf

Microstructure, adhesion and growth kinetics of protective scales on metals and alloys

The oxidation of nickel near 1000°C is accompanied by the generation of stresses parallel with the metal-oxide interface and of magnitude (~1500 psi) sufficient to elongate nickel rod, increase sheet area, and sharpen the angle of bend of ells and helices. A primary cause of this stress is identified with the formation of layers of new nickel oxide upon boundaries of columnar grains where nickel, diffusing through the oxide crystals, meets oxygen, diffusing along grain boundaries. Classical parabolic growth of the scale gives way to a slower quasilinear rate when the major site of new oxide formation is abruptly shifted to a system of grain boundaries lying close to the metal surface and created by recrystallization of the oxide under the influence of stress and high temperature. Another source of stress in the scale arises from the constantly changing area of the metal-oxide interface when oxidation is occurring upon curved metal surfaces. This stress reinforces that generated by deposition of material at oxide grain boundaries when the surface is convex and opposes it when the surface is concave.

F. N. Rhines

Papers

The role of oxide microstructure and growth stresses in the high-temperature scaling of nickel