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Long-term corrosion testing plan

Wall, Frederick D.

This document describes the testing and facility requirements to support the Yucca Mountain Project long-term corrosion testing program. The purpose of this document is to describe a corrosion testing program that will (a) reduce model uncertainty and variability, (b) reduce the reliance upon overly conservative assumptions, and (c) improve model defensibility. Test matrices were developed for 17 topical areas (tasks): each matrix corresponds to a specific test activity that is a subset of the total work performed in a task. A future document will identify which of these activities are considered to be performance confirmation activities. Detailed matrices are provided for FY08, FY09 and FY10 and rough order estimates are provided for FY11-17. Criteria for the selection of appropriate test facilities were developed through a meeting of Lead Lab and DOE personnel on October 16-17, 2007. These criteria were applied to the testing activities and recommendations were made for the facility types appropriate to carry out each activity. The facility requirements for each activity were assessed and activities were identified that can not be performed with currently available facilities. Based on this assessment, a total of approximately 10,000 square feet of facility space is recommended to accommodate all future testing, given that all testing is consolidated to a single location. This report is a revision to SAND2008-4922 to address DOE comments.

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Long-term corrosion testing pan

Wall, Frederick D.

This document describes the testing and facility requirements to support the Yucca Mountain Project long-term corrosion testing needs. The purpose of this document is to describe a corrosion testing program that will (a) reduce model uncertainty and variability, (b) reduce the reliance upon overly conservative assumptions, and (c) improve model defensibility. Test matrices were developed for 17 topical areas (tasks): each matrix corresponds to a specific test activity that is a subset of the total work performed in a task. A future document will identify which of these activities are considered to be performance confirmation activities. Detailed matrices are provided for FY08, FY09 and FY10 and rough order estimates are provided for FY11-17. Criteria for the selection of appropriate test facilities were developed through a meeting of Lead Lab and DOE personnel on October 16-17, 2007. These criteria were applied to the testing activities and recommendations were made for the facility types appropriate to carry out each activity. The facility requirements for each activity were assessed and activities were identified that can not be performed with currently available facilities. Based on this assessment, a total of approximately 10,000 square feet of facility space is recommended to meet all future testing needs, given that all testing is consolidated to a single location. This report is a revision to SAND2007-7027 to address DOE comments and add a series of tests to address NWTRB recommendations.

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A critical implanted Cl concentration for pit initiation on aluminum thin films

Journal of the Electrochemical Society

Serna, L.M.; Zavadil, Kevin R.; Johnson, C.M.; Wall, Frederick D.; Barbour, J.C.

The pitting potential of pure aluminum thin films in 50 mM K2 S O4 was measured as a function of implanted Cl fluence. Samples were implanted with 35 keV Cl+ at room temperature using fluences from 2.25× 1016 to 3.25× 1016 ions cm-2 in increments of 0.25× 1016. An empirical relationship between pitting potential and fluence was found which suggests a critical Cl concentration in the oxide is necessary for pit initiation. No correlation between pitting potential and the measured Cl concentration or distribution in the metal was found. © 2006 The Electrochemical Society. All rights reserved.

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Relationship between induction time for pitting and pitting potential for high-purity aluminum

Journal of the Electrochemical Society

Wall, Frederick D.; Martinez, M.A.; Vandenavyle, J.J.

The objective of this study was to determine if a distribution of pit induction times (from potentiostatic experiments) could be used to predict a distribution of pitting potentials (from potentiodynamic experiments) for high-purity aluminum. Pit induction times were measured for 99.99 Al in 50 mM NaCl at potentials of -0.35, -0.3, -0.25, and -0.2 V vs. saturated calomel electrode. Analysis of the data showed that the pit germination rate generally was an exponential function of the applied potential; however, a subset of the germination rate data appeared to be mostly potential insensitive. The germination rate behavior was used as an input into a mathematical relationship that provided a prediction of pitting potential distribution. Good general agreement was found between the predicted distribution and an experimentally determined pitting potential distribution, suggesting that the relationships presented here provide a suitable means for quantitatively describing pit germination rate. © 2004 The Electrochemical Society. All rights reserved.

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Determination of critical length scales for corrosion processes using microelectroanalytical techniques

Zavadil, Kevin R.; Wall, Frederick D.

A key factor in our ability to produce and predict the stability of metal-based macro- to nano-scale structures and devices is a fundamental understanding of the localized nature of corrosion. Corrosion processes where physical dimensions become critical in the degradation process include localized corrosion initiation in passivated metals, microgalvanic interactions in metal alloys, and localized corrosion in structurally complex materials like nanocrystalline metal films under atmospheric and inundated conditions. This project focuses on two areas of corrosion science where a fundamental understanding of processes occurring at critical dimensions is not currently available. Sandia will study the critical length scales necessary for passive film breakdown in the inundated aluminum (Al) system and the chemical processes and transport in ultra-thin water films relevant to the atmospheric corrosion of nanocrystalline tungsten (W) films. Techniques are required that provide spatial information without significantly perturbing or masking the underlying relationships. Al passive film breakdown is governed by the relationship between area of the film sampled and its defect structure. We will combine low current measurements with microelectrodes to study the size scale required to observe a single initiation event and record electrochemical breakdown events. The resulting quantitative measure of stability will be correlated with metal grain size, secondary phase size and distribution to understand which metal properties control stability at the macro- and nano-scale. Mechanisms of atmospheric corrosion on W are dependent on the physical dimensions and continuity of adsorbed water layers as well as the chemical reactions that take place in this layer. We will combine electrochemical and scanning probe microscopic techniques to monitor the chemistry and resulting material transport in these thin surface layers. A description of the length scales responsible for driving the corrosion of the nanocrystalline metal films will be developed. The techniques developed and information derived from this work will be used to understand and predict degradation processes in microelectronic and microsystem devices critical to Sandia's mission.

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The effects of chloride implantation on pit initiation in aluminum

Proposed for publication in the Journal of the Electrochemical Society.

Wall, Frederick D.; Wall, Frederick D.; Barbour, J.C.

High-purity aluminum samples were implanted with 35 keV Cl{sup +} then polarized in both Cl{sup -}-containing and Cl{sup -}-free electrolytes in order to ascertain corrosion behavior as a function of Cl{sup -} content in the oxide. Implant fluence between 5 x 10{sup 15} and 2 x 10{sup 16} Cl{sup +} cm{sup -2} resulted in little or no localized attack. Implant fluences of 3 x 10{sup 16} and 5 x 10{sup 16} Cl{sup +} cm{sup -2} resulted in significant pitting in a Cl{sup -}-free electrolyte with the severity scaling as a function of implant fluence. The low variability in the pitting behavior of the 5 x 10{sup 16} Cl{sup +} cm{sup -2} sample suggests that this implant dosage results in a critical Cl{sup -} concentration in the oxide for pit nucleation. The passive current density (i{sub pass}) decreased with increasing implant fluence. A space-charge effect is proposed to account for this phenomenon, although effects from defect interactions and possible oxide thickening are still under consideration.

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Electronic defects and interface potentials for Al oxide films on Al and their relationship to electrochemical properties

Sullivan, John P.; Dunn, Roberto G.; Barbour, J.C.; Wall, Frederick D.; Missert, Nancy A.

The relative electronic defect densities and oxide interface potentials were determined for naturally-occurring and synthetic Al oxides on Al. In addition, the effect of electrochemical treatment on the oxide electrical properties was assessed. The measurements revealed (1) that the open circuit potential of Al in aqueous solution is inversely correlated with the oxide electronic defect density (viz., lower oxide conductivities are correlated with higher open circuit potentials), and (2) the electronic defect density within the Al oxide is increased upon exposure to an aqueous electrolyte at open circuit or applied cathodic potentials, while the electronic defect density is reduced upon exposure to slight anodic potentials in solution. This last result, combined with recent theoretical predictions, suggests that hydrogen may be associated with electronic defects within the Al oxide, and that this H may be a mobile species, diffusing as H{sup +}. The potential drop across the oxide layer when immersed in solution at open circuit conditions was also estimated and found to be 0.3 V, with the field direction attracting positive charge towards the Al/oxide interface.

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19 Results
19 Results