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Title: Anodic Polarization Behavior of Titanium Grade 7 in Dust Deliquescence Salt Environments

Abstract

It is planned to use the highly corrosion resistant titanium grade 7 (Ti Gr 7) and a high strength titanium alloy (Ti Gr 29) to fabricate the drip shield for the Yucca Mountain repository. Ti Gr 7 contains 0.15% Palladium (Pd) to increase its corrosion performance, mainly under reducing conditions. It was important to determine the corrosion behavior of Ti Gr 7 in concentrated brines at temperatures higher than 100 C, which may represent the behavior of dust deliquescence solutions. Tests were performed in concentrated NaCl + KCl solutions containing also nitrates and fluorides. Results show that Ti Gr 7 was highly resistant to general and localized corrosion. Some specimens were polarized to potentials higher than 4 volts. None of the tightly creviced specimens suffered crevice corrosion. The presence of fluoride promoted localized corrosion around the edges of the crevice former.

Authors:
;
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
914604
Report Number(s):
UCRL-PROC-228934
TRN: US0803349
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Conference
Resource Relation:
Conference: Presented at: 2007 ASME Pressure Vessels and Piping Division Conference, San Antonio, TX, United States, Jul 22 - Jul 27, 2007
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; BRINES; CORROSION; CREVICE CORROSION; FLUORIDES; NITRATES; PALLADIUM; PERFORMANCE; POLARIZATION; PRESSURE VESSELS; SHIELDS; TITANIUM; TITANIUM ALLOYS; YUCCA MOUNTAIN

Citation Formats

Evans, K J, and Rebak, R B. Anodic Polarization Behavior of Titanium Grade 7 in Dust Deliquescence Salt Environments. United States: N. p., 2007. Web.
Evans, K J, & Rebak, R B. Anodic Polarization Behavior of Titanium Grade 7 in Dust Deliquescence Salt Environments. United States.
Evans, K J, and Rebak, R B. Fri . "Anodic Polarization Behavior of Titanium Grade 7 in Dust Deliquescence Salt Environments". United States. doi:. https://www.osti.gov/servlets/purl/914604.
@article{osti_914604,
title = {Anodic Polarization Behavior of Titanium Grade 7 in Dust Deliquescence Salt Environments},
author = {Evans, K J and Rebak, R B},
abstractNote = {It is planned to use the highly corrosion resistant titanium grade 7 (Ti Gr 7) and a high strength titanium alloy (Ti Gr 29) to fabricate the drip shield for the Yucca Mountain repository. Ti Gr 7 contains 0.15% Palladium (Pd) to increase its corrosion performance, mainly under reducing conditions. It was important to determine the corrosion behavior of Ti Gr 7 in concentrated brines at temperatures higher than 100 C, which may represent the behavior of dust deliquescence solutions. Tests were performed in concentrated NaCl + KCl solutions containing also nitrates and fluorides. Results show that Ti Gr 7 was highly resistant to general and localized corrosion. Some specimens were polarized to potentials higher than 4 volts. None of the tightly creviced specimens suffered crevice corrosion. The presence of fluoride promoted localized corrosion around the edges of the crevice former.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Mar 09 00:00:00 EST 2007},
month = {Fri Mar 09 00:00:00 EST 2007}
}

Conference:
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  • Stress corrosion crack growth studies have been performed on annealed and cold worked Titanium Grade 7 and Alloy 22 in 110 C, aerated, concentrated, high pH salt environments characteristic of concentrated ground water. Following a very careful transition from fatigue precracking conditions to SCC conditions, the long term behavior under very stable conditions was monitored using reversing dc potential drop. Titanium Grade 7 exhibited continuous crack growth under both near-static and complete static loading conditions. Alloy 22 exhibited similar growth rates, but was less prone to maintain stable crack growth as conditions approached fully static loading.
  • The nitrate ion (NO{sub 3}{sup -}) is an inhibitor for crevice corrosion of Alloy 22 (N06022) in chloride (Cl{sup -}) aqueous solutions. Naturally formed electrolytes may contain both chloride and nitrate ions. The higher the ratio R = [NO{sub 3}{sup -}]/[Cl{sup -}] in the solution the stronger the inhibition of crevice corrosion. Atmospheric desert dust contains both chloride and nitrate salts, generally based on sodium (Na{sup +}) and potassium (K{sup +}). Some of these salts may deliquescence at relatively low humidity at temperatures on the order of 150 C and higher. The resulting deliquescent brines are highly concentrated and especiallymore » rich in nitrate. Electrochemical tests have been performed to explore the anodic behavior of Alloy 22 in high chloride high nitrate electrolytes at temperatures as high as 150 C at ambient atmospheres. Naturally formed brines at temperatures higher than 120 C do not induce crevice corrosion in Alloy 22 because they contain high levels of nitrate. The inhibitive effect of nitrate on crevice corrosion is still active for temperatures higher than 100 C.« less
  • Titanium Grade 7 (UNS R52400) is a titanium-based alloy with 0.12-0.25% Pd. The addition of the small amount of palladium is to ennoble the corrosion potential of Ti, thus improving the corrosion resistance of titanium in reducing environments. In most aqueous environments, Ti and Ti alloys demonstrate excellent corrosion resistance due to the protective oxide film that forms spontaneously and remains stable on the surface. However, Ti and Ti alloys are susceptible to corrosion in fluoride-containing environments due to the formation of complexes such as TiF{sub 6}{sup 2-} and TiF{sub 6}{sup 3-}, which are stable and soluble in electrolyte solutions.more » Without the presence of fluoride, only slight effects from [Cl{sup -}], pH and temperature have been reported [1]. It has been reported that the kinetics of passive corrosion of titanium in neutral solutions and controlled by the migration of the defects in the oxide across the surface film [2]. Thus, the increase in thickness and improvement in film properties, by thermal oxidation, would lead to a significant decrease in the susceptibility to film breakdown and in the passive corrosion rate. This report summarizes recent experiment results in studies of the environmental influence on the corrosion behavior of Titanium Grade 7 (Ti-7) in NaCl brines containing fluoride. The environmental factors to be studied include temperature, pH, chloride and fluoride concentration. This report also includes the effects of oxide film, formed during an anneal treatment, on the corrosion behavior of Ti-7. Polarization measurement techniques including potentiodynamic and potentiostatic scans were use3d to characterize corrosion kinetics and susceptibility. Due to the unique alloying in Titanium Grade 7, the long-term corrosion behavior is heavily influenced by the surface enrichment of Pd. Use of electrochemical impedance spectroscopy in conjunction with a potentiostatic scan will reveal the transformation in the corrosion behavior as a function of Pd enrichment on the metal surface. Surface characterization was done using various analytical techniques including X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and scanning electron microscopy (SEM). The effect of fluoride ion on the corrosion behavior of Ti-7 is strongly dependent on the solution pH. In neutral (pH 8) and alkaline (pH 11) solutions, fluoride did not affect the corrosion rate significantly even though it altered the anodic polarization curve drastically. With pH decreased to 4, the corrosion rate of Ti-7 was increased significantly by the presence of fluoride.« less
  • The effects of fluoride on the corrosion behavior of Titanium Grade 7 (0.12-0.25% Pd) have been investigated. Up to 0.1 mol/L fluoride was added to the NaCl brines at 95 C, and three pH values of 4, 8, and 11 were selected for studying pH dependence of fluoride effects. It was observed that fluoride significantly altered the anodic polarization behavior, at all three pH values of 4, 8, and 11. Under acidic condition fluoride caused active corrosion. The corrosion of Titanium grade 7 was increased by three orders of magnitude when a 0.1 mol/L fluoride was added to the NaClmore » brines at pH 4, and the Pd ennoblement effect was not observed in acidic fluoride-containing environments. The effects of fluoride were reduced significantly when pH was increased to 8 and above.« less