SRNL SHELF LIFE STUDIES - SCC STUDIES AT ROOM TEMPERTURE [stress corrosion cracking ]
Phase II, Series 2 corrosion testing performed by the Savannah River National Laboratory (SRNL) for the Department of Energy 3013 container has been completed. The corrosion tests are part of an integrated plan conducted jointly by Los Alamos National Laboratory and the Savannah River Site. SRNL was responsible for conducting corrosion studies in small-scale vessels to address the influence of salt composition, water loading, and type of oxide/salt contact on the relative humidity inside a 3013 container and on the resulting corrosion of Type 304L and 316L stainless steel (304L and 316L). This testing was conducted in two phases: Phase I evaluated a broad spectrum of salt compositions and initial water loadings on the salt mixtures exposed to 304L and 316L and the resulting corrosion; Phase II evaluated the corrosion of 304L at specific water loadings and a single salt composition. During Phase I testing at high initial moisture levels (0.35 to 1.24 wt%)a, the roomtemperature corrosion of 304L exposed to a series of plutonium oxide/chloride salt mixtures ranged from superficial staining to pitting and stress corrosion cracking (SCC). 304L teardrop coupons that exhibited SCC were directly exposed to a mixture composed of 98 wt % PuO2, 0.9 wt % NaCl, 0.9 wt % KCl, and 0.2 wt % CaCl2. Cracking was not observed in a 316L teardrop coupon. Pitting was also observed in this environment for both 304L and 316L with depths ranging from 20 to 100 μm. Neither pitting nor SCC was observed in mixtures with a greater chloride salt concentration (5 and 28 wt%). These results demonstrated that for a corrosive solution to form a balance existed between the water loading and the salt chloride concentration. This chloride solution results from the interaction of loaded water with the hydrating CaCl2 salt. In Phase II, Series 1 tests, the SCC results were shown to be reproducible with cracking occurring in as little as 85 days. The approximate 0.5 wt% moisture level was found to result in an initial relative humidity of ~55% within the small-scale vessels. Pits were found to be associated with cracks and appeared to act as initiators for the cracking. In a vapor-space only exposure, the weld oxide, which results from the TIG closure weld used to fabricate the teardrop coupon, was also shown to be more susceptible to pitting corrosion than a surface free from weld oxide. This result has important implications for the closure weld of the 3013 inner can since the weld oxide on the can internal surface cannot be removed. The results from the Phase II, Series 2 tests further demonstrated the significance of forming a solution with a critical chloride concentration for corrosion to proceed. 304L teardrop coupons were found to corrode only by pitting with a similar oxide/salt mixture as used in Series 1 testing but with a lower water loading of 0.2 wt%, which resulted in an initial relative humidity of 35-38%. These tests ran twice as long as those for Series 1 testing. The exposure condition was also found to impact the corrosion with salt-exposed surfaces showing lower corrosion resistance. Additional analyses of the Series 2 coupons are recommended especially for determining if cracks emanate from the bottom of pits. Data generated under the 2009 3013 corrosion test plan, as was presented here, increased the understanding of the corrosion process within a sealed 3013 container. Along with the corrosion data from destructive evaluations of 3013 containers, the inner can closure weld region (ICCWR) has been identified as the most vulnerable area of the inner can where corrosion may lead to corrosive species leaking to the interior surface of the outer container, thereby jeopardizing the integrity of the 3013 container. A new corrosion plan has been designed that will characterize the corrosion at the ICCWR of 3013 DEs as well as parameters affecting this corrosion.