Thermodynamics of Interstitial Impurities Removal from Refractory Metals

Abstract

The applied thermodynamic aspects of removing hydrogen, nitrogen, oxygen, carbon, and silicon from vanadium, niobium and tantalum metals by pyrovacuum treatments are considered in this paper. Two major processes operate in refining by pyrovacuum treatment. One is distillation and the other is degassing. Distillation is mainly used to remove substitutional impurities that arc either already present in the metal or have been added for removing any interstitial impurity. The success is determined by the partial pressure of the impurity element as well as by the difference in partial pressures of the impurity and the metal. The maximum rate of vaporization of impurity can then be estimated using the free evaporation equation. Interstitial impurities, particularly the gases hydrogen, nitrogen and oxygen, are removed by degassing. Thermodynamics of classical degassing, which is essentially the reverse of absorption, is described usefully by the pressure-composition isotherms. This is applicable mainly for the removal of hydrogen and nitrogen. The removal of oxygen, known as deoxidation, occurs by a more complex mechanism that involves the formation and evaporation of metal suboxides. Depending on the suboxide species responsible for deoxidation, the process is known as sacrificial deoxidation, carbon deoxidation, silicon deoxidation, or aluminium deoxidation. The applicability of these different processes to a particular metal, M is determined by the thermodynamic properties of the relevant Af-O, Af-C-O, M-Si-O, and MAl-O system. It is shown in this paper that all the four processes are applicable to niobium and tantalum where as only aluminium deoxidation is useful for vanadium. For the removal of carbon and silicon also, the relevant deoxidation process can be used.