Institute of Metals Division - Oxidation of Titanium

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. 'The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew' suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman's' observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with