Role of alloying elements and carbides in the chlorine-induced corrosion of steels and alloys

The high temperature corrosion of steels and Ni-base alloys in oxidizing and chloridizing environments is of practical interest in relation to problems in waste incineration plants and power plants using Cl containing fuels. The behaviour of the most important alloying elements Fe, Cr, Ni, Mo, Mn, Si, Al upon corrosion in an oxidizing and chloridizing atmosphere was elucidated: the reactions and kinetics can be largely understood on the base of thermodynamic data, i.e. free energy of chloride formation, vapor pressure of the chlorides and oxygen pressure pO2 needed for the conversion chlorides -> oxides. The mechanism is described by 'active oxidation', comprising inward penetration of chlorine into the scale, formation of chlorides at the oxide/metal interface, evaporation of the chlorides and conversion of the evaporating chlorides into oxides, which occurs in more or less distance from the surface (depending on pO2). This process leads to loose, fragile, multilayered oxides which are unprotective (therefore: active oxidation). Fe and Cr are rapidly transferred into such scale, Ni and Mo are relatively resistant. In many cases, the grain boundaries of the materials are strongly attacked, this is due to a susceptibility of chromium carbides to chloridation. In contrast the carbides Mo2C, TiC and NbC are less attacked than the matrix. Alloys on the basis Fe-Cr-Si proved to be rather resistant, and the alloying elements Ni and Mo clearly retard the attack in an oxidizing and chloridizing environment