Institute of Metals Division - Internal Oxidation in Iron-Chromium-Yttrium Alloys (TN)

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high