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Title: In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface

Abstract

Currently, reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we determine in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow “crevice corrosion” processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica–nickel confined interface of total area ~0.03 mm 2. The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6–7 μm and depth ~2–3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reflect a mechanism that suggests initial corrosion results inmore » formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces.« less

Authors:
; ; ; ; ; ; ORCiD logo;
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); European Research Council (ERC)
OSTI Identifier:
1375819
Alternate Identifier(s):
OSTI ID: 1535355
Grant/Contract Number:  
FG02-87ER45331
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; crevice corrosion; surface forces apparatus; pitting dynamics; surface electrochemistry

Citation Formats

Merola, C., Cheng, H. -W., Schwenzfeier, K., Kristiansen, K., Chen, Y. -J., Dobbs, H. A., Israelachvili, J. N., and Valtiner, M. In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface. United States: N. p., 2017. Web. doi:10.1073/pnas.1708205114.
Merola, C., Cheng, H. -W., Schwenzfeier, K., Kristiansen, K., Chen, Y. -J., Dobbs, H. A., Israelachvili, J. N., & Valtiner, M. In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface. United States. doi:10.1073/pnas.1708205114.
Merola, C., Cheng, H. -W., Schwenzfeier, K., Kristiansen, K., Chen, Y. -J., Dobbs, H. A., Israelachvili, J. N., and Valtiner, M. Mon . "In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface". United States. doi:10.1073/pnas.1708205114.
@article{osti_1375819,
title = {In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface},
author = {Merola, C. and Cheng, H. -W. and Schwenzfeier, K. and Kristiansen, K. and Chen, Y. -J. and Dobbs, H. A. and Israelachvili, J. N. and Valtiner, M.},
abstractNote = {Currently, reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we determine in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow “crevice corrosion” processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica–nickel confined interface of total area ~0.03 mm2. The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6–7 μm and depth ~2–3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reflect a mechanism that suggests initial corrosion results in formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces.},
doi = {10.1073/pnas.1708205114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = ,
volume = ,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1708205114

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Cited by: 6 works
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