Oxidation of Zr-2.5 Nb nuclear reactor pressure tubes - A new model

The corrosion and associated deuterium (D) uptake of Zr alloy nuclear reactor pressure tubes have been studied for over 40 years. Zircaloy tubes exhibit rapid D ingress after a period of in-reactor exposure, and have been replaced with tubes fabricated from the more resistant Zr-25 wt % Nb alloy. Recently. however, a small percentage of Zr-2.5 Nb tubes have been found to contain high D contents. There is currently no clear understanding of the mechanism for this increased D uptake, and concern exists that an increasing number of high-D tubes will develop with time. A new model for Zr-2.5 Nh corrosion is presented in this paper. The rate of corrosion is shown to be dependent on the rate of transformation of the protective inner oxide layer (closer to the metal) to a porous outer layer. The mechanism of this transformation is not known and should be the subject of future investigations. it is assumed in the model that zirconia chemically dissolves into the solution at the pore bottom. The rate of this dissolution reaction depends on the local pH, which increases if there is a buildup of deuteroxyl ions generated in the cathodic part of the Zr corrosion reaction. A mathematical description of this model, containing several parameters with unknown values, is presented. Assigning certain values to these parameters results in predictions of oxide formation (and thus D buildup) that correspond well with observations. (C) 1999 The Electrochemical Society. S0013-4651(98)11-007-8. All rights reserved.