Development of Advanced Electrochemical Emission Spectroscopy for Monitoring Corrosion in Simulated DOE Liquid Waste

The different tasks that have been carried out under the current program are as follows: (1) Theoretical and experimental assessment of general corrosion of iron/steel in borate buffer solutions by using electrochemical impedance spectroscopy (EIS), ellipsometry and XPS techniques; (2) Development of a damage function analysis (DFA), which would help in predicting the accumulation of damage due to pitting corrosion in an environment prototypical of DOE liquid waste systems; (3) Experimental measurement of crack growth rate, acoustic emission signals, and coupling currents for fracture in carbon and low alloy steels as functions of mechanical (stress intensity), chemical (conductivity), electrochemical (corrosion potential, ECP), and microstructural (grain size, precipitate size, etc) variables in a systematic manner, with particular attention being focused on the structure of the noise in the current and its correlation with the acoustic emissions; (4) Development of fracture mechanisms for carbon and low alloy steels that are consistent with the crack growth rate, coupling current data and acoustic emissions; (5) Inserting advanced crack growth rate models for SCC into existing deterministic codes for predicting the evolution of corrosion damage in DOE liquid waste storage tanks; (6) Computer simulation of the anodic and cathodic activity on the surface of the steel samples in order to exactly predict the corrosion mechanisms; (7) Wavelet analysis of EC noise data from steel samples undergoing corrosion in an environment similar to that of the high level waste storage containers, to extract data pertaining to general, pitting and stress corrosion processes, from the overall data. The work has yielded a number of important findings, including an unequivocal demonstration of the role of chloride ion in passivity breakdown on nickel in terms of cation vacancy generation within the passive film, the first detection and characterization of individual micro fracture events in stress corrosion cracking, and the determination of kinetic parameters for the generation and annihilation of point defects in the passive film on iron. The existence of coupling between the internal crack environment and the external cathodic environment, as predicted by the coupled environment fracture model (CEFM), has also been indisputably established for the AISI 4340/NaOH system. It is evident from the studies that analysis of coupling current noise is a very sensitive tool for studying the crack tip processes in relation to the chemical, mechanical, electrochemical, and microstructural properties of the system. Experiments are currently being carried out to explore these crack tip processes by simultaneous measurement of the acoustic activity at the crack tip in an effort to validate the coupling current data. These latter data are now being used to deterministically predict the accumulation of general and localized corrosion damage on carbon in prototypical DOE liquid waste storage tanks. Computer simulation of the cathodic and anodic activity on the steel surfaces is also being carried out in an effort to simulate the actual corrosion process. Wavelet analysis of the coupling current data promises to be a useful tool to differentiate between the different corrosion mechanisms. Hence, wavelet analysis of the coupling current data from the DOE waste containers is also being carried out to extract data pertaining to general, pitting and stress corrosion processes, from the overall data which is bound to contain noise fluctuations due to any or all of the above mentioned processes