A Critique of Internal Oxidation in Alloys During the Post-Wagner Era

Wagner's classical treatment of internal oxidation (generic name allowing for reaction with oxygen, nitrogen, carbon or sulfur) assumed ideal conditions such as uninhibited dissolution of the gas, formation of spherical particles, diffusion of the oxidant in the solvent as the rate-controlling step, equilibrium conditions, etc. However, during the 45 years since his treatment, many observations have been made to complicate the idealized situation suggested by Wagner. This paper examines the most important modifications with respect to Wagner's original analysis. The following items are discussed. (a) The role of solute concentration: The parabolic kinetics are much higher than expected for Ni−Al alloys due to rapid interfacial diffusion of oxygen along the interfaces between cylindrical rods of Al2O3 (perpendicular to the surface) and the matrix. (b) Precipitate morphology: Spherical precipitates seem almost to be the exception. A wide variety of forms have been observed, including Widmanstatten platelets, cylindrical rods, hexagonal plates, dendritic or “fishbone” products, etc. The competition between nucleation and growth is useful to explain the observed structures. (c) Intergranular internal oxidation: Rapid oxygen diffusion in grain boundaries may lead to a wide variety of intergranular-precipitate structures. (d) Internal-oxide bands: Wavy, approximately parallel bands form at a finite distance beneath the surface in certain alloys having very reactive solutes, e.g., Ag−Mg. It is postulated that high stresses generated by precipitation play a major role. (e) Surface nodules of pure solvent metal: High stresses generated during precipitation cause extrusion of solute through dislocation pipes, leading to extensive nodule formation on either grain boundaries or on the grains (or both), depending on the alloy and oxidizing conditions. (f) Nonstoichiometric precipitates: Either hypo- or hyperstoichiometric particles can form as very small clusters in certain alloys (Ag−Al). The nature of precursors and changes in stoichiometry during reaction are discussed. (g) Trapping of oxidant: Diffusion of the oxidant may be slowed appreciably by trapping with the solute, although no precipitates need to form. Lower-than-expected kinetics (based on normal diffusivities of the oxidant) result. (h) High-solubility-product precipitates: Concentration profiles of solute, oxidant and precipitate are quite different than those expected for low-solubility-product precipitates as considered by Wagner. In particular, a variable mole fraction of precipitate exists, and further precipitation occurs in the reaction zone after the front has passed by. Linear kinetics have been observed for some Nb-base alloys at very high temperatures and low oxygen pressures. The rate-controlling step is the arrival of oxygen at the surface and not oxygen diffusion in the metal. (i) Dual oxidants: Two gases may diffuse·simultaneously and each forms its own product with the solute. The thermodynamically most-stable compound forms near the surface, and the less-stable compound deeper in the alloy. The less-stable compound is subsequently converted to the more-stable compound with a concomitant release of the second oxidant. Although numerous examples have been reported of systems which do not behave as predicted by Wagner, his theory still remains as the cornerstone of our understanding and is still the starting point for virtually every study in internal oxidation.