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An assessment of the potential degradation mechanisms of Types I and II High-Level Waste (HLW) Tanks determined that pitting corrosion and stress corrosion cracking were the two most significant degradation mechanisms. Specifically, nitrate induced stress corrosion cracking was determined to be the principal degradation mechanism for the primary tank steel of non-stress relieved tanks. Controls on the solution chemistry have been in place to preclude the initiation and propagation of degradation in the tanks. However, recent experience has shown that steel not in contact with the bulk waste solution or slurry, but exposed to the ''vapor space'' above the bulk waste, may be vulnerable to the initiation and propagation of degradation, including pitting and stress corrosion cracking. A program to resolve the issues associated with potential vapor space corrosion is in place. The objective of the program is to develop understanding of vapor space (VSC) and liquid/air interface (LAIC) corrosion to ensure a defensible technical basis to provide accurate corrosion evaluations with regard to vapor space and liquid/air interface corrosion (similar to current evaluations). There are several needs for a technically defensible basis with sufficient understanding to perform these evaluations. These include understanding of the (1) surface chemistry evolution, (2) corrosion response through coupon testing, and (3) mechanistic understanding through electrochemical studies. Experimentation performed in FY02 determined the potential for vapor space and liquid/air interface corrosion of ASTM A285-70 and ASTM A537-Cl.1 steels. The material surface characteristics, i.e. mill-scale, polished, were found to play a key role in the pitting response. The experimentation indicated that the potential for limited vapor space and liquid/air interface pitting exists at 1.5M nitrate solution when using chemistry controls designed to prevent stress corrosion cracking. Experimentation performed in FY03 quantified pitting rates as a function of material surface characteristics, including mill-scale and defects within the mill-scale. Testing was performed on ASTM A537-Cl.1 (normalized) steel, the material of construction of the Type III HLW tanks. The pitting rates were approximately 3 mpy for exposure above inhibited solutions, as calculated from the limited exposure times. This translates to a penetration time of 166 years for a 0.5-in tank wall provided that the pitting rate remains constant and the bulk solution chemistry is maintained within the L3 limit. The FY04 testing consisted of electrochemical testing to potentially lend insight into the surface chemistry and further understand the corrosion mechanism in the vapor space. Electrochemical testing lends insight into the corrosion processes through the determination of current potential relationships. The results of the electrochemical testing performed during FY04 are presented here

Cyclic Polarization Behavior of ASTM A537-Cl.1 Steel in the Vapor Space Above Simulated Waste