Extractive Metallurgy Division - High-Temperature Stability of Tungsten Oxide Structures (TN)

ThE tendency toward further oxidation of the intermediate oxides and the high volatilization rates of the higher oxides have prevented direct attainment of equilibrium data for the system tungsten-oxygen. As a result, St. Pierre et al.1 have proposed a phase diagram (to 800°C) based on thermody-namic data to 1200°C for the known tungsten oxides (WO2z, W18O49, W20O58, and WO3) and a report on a tungsten suboxide W3O.2 Recent modification of a technique previously described3 5 now permits adequate preservation of compositions of mixtures of metallic tungsten and metal oxides (e.g., of tungsten, cobalt, calcium, samarium, titanium) in order that condensed phase relations may be established to 1700 This method has been applied to study the high-temperature stability of tungsten oxides. In the method used, the desired compositions were sealed in nonreactive containers such that only a small gas volume remained. Each sample then established its own equilibrium atmosphere at temperature. This method has advantages in the study of systems of the W-0 type where knowledge of the condensed phases is desirable but for which composition and pressure of the gas phase are not readily attainable because of oxide volatility. Mixtures of 99.99 pct tungsten metal powder and purified tungsten anhydride (WO3) or in some cases W18O49* were equilibrated in pellet form in sealed