Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion

Abstract To understand the chloride (Cl)-induced initiation mechanism of localized corrosion of Aluminum (Al) alloys, we apply density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations to investigate the interactions between Cl and hydroxylated α–Al2O3 surfaces...

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Autores principales:	Aditya Sundar, Ganlin Chen, Liang Qi
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Materials of engineering and construction. Mechanics of materials TA401-492
Acceso en línea:	https://doaj.org/article/9706ef9043a64294835ef38f0cc9ce31
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spelling	oai:doaj.org-article:9706ef9043a64294835ef38f0cc9ce312021-12-02T14:26:11ZSubstitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion10.1038/s41529-021-00161-w2397-2106https://doaj.org/article/9706ef9043a64294835ef38f0cc9ce312021-04-01T00:00:00Zhttps://doi.org/10.1038/s41529-021-00161-whttps://doaj.org/toc/2397-2106Abstract To understand the chloride (Cl)-induced initiation mechanism of localized corrosion of Aluminum (Al) alloys, we apply density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations to investigate the interactions between Cl and hydroxylated α–Al2O3 surfaces, mainly (0001) orientation, under aqueous electrochemical conditions. Hydroxylated alumina surfaces thermodynamically stable in aqueous environments are constructed based on DFT calculations for both the single-crystal and bicrystal configurations. AIMD simulations suggest a Cl anion can only be stabilized on these surfaces by substituting a surface hydroxyl (OH) group. This substitution is thermodynamically favorable at sites on surface terminations of grain boundaries (GBs) in bicrystal configurations but not favorable at sites on single-crystal surfaces. Electronic structure analyses show that the different adsorption behaviors originate from the higher sensitivity of the Al–OH bond strength to the local coordination than its counterpart of the Al–Cl bond. The adsorbed Cl significantly increases the thermodynamic driving force for Al cation dissolution from alumina surfaces into the aqueous electrolyte, which can initiate localized corrosion.Aditya SundarGanlin ChenLiang QiNature PortfolioarticleMaterials of engineering and construction. Mechanics of materialsTA401-492ENnpj Materials Degradation, Vol 5, Iss 1, Pp 1-15 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Materials of engineering and construction. Mechanics of materials TA401-492
spellingShingle	Materials of engineering and construction. Mechanics of materials TA401-492 Aditya Sundar Ganlin Chen Liang Qi Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
description	Abstract To understand the chloride (Cl)-induced initiation mechanism of localized corrosion of Aluminum (Al) alloys, we apply density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations to investigate the interactions between Cl and hydroxylated α–Al2O3 surfaces, mainly (0001) orientation, under aqueous electrochemical conditions. Hydroxylated alumina surfaces thermodynamically stable in aqueous environments are constructed based on DFT calculations for both the single-crystal and bicrystal configurations. AIMD simulations suggest a Cl anion can only be stabilized on these surfaces by substituting a surface hydroxyl (OH) group. This substitution is thermodynamically favorable at sites on surface terminations of grain boundaries (GBs) in bicrystal configurations but not favorable at sites on single-crystal surfaces. Electronic structure analyses show that the different adsorption behaviors originate from the higher sensitivity of the Al–OH bond strength to the local coordination than its counterpart of the Al–Cl bond. The adsorbed Cl significantly increases the thermodynamic driving force for Al cation dissolution from alumina surfaces into the aqueous electrolyte, which can initiate localized corrosion.
format	article
author	Aditya Sundar Ganlin Chen Liang Qi
author_facet	Aditya Sundar Ganlin Chen Liang Qi
author_sort	Aditya Sundar
title	Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
title_short	Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
title_full	Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
title_fullStr	Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
title_full_unstemmed	Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
title_sort	substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/9706ef9043a64294835ef38f0cc9ce31
work_keys_str_mv	AT adityasundar substitutionaladsorptionsofchlorideatgrainboundarysitesonhydroxylatedaluminasurfacesinitializelocalizedcorrosion AT ganlinchen substitutionaladsorptionsofchlorideatgrainboundarysitesonhydroxylatedaluminasurfacesinitializelocalizedcorrosion AT liangqi substitutionaladsorptionsofchlorideatgrainboundarysitesonhydroxylatedaluminasurfacesinitializelocalizedcorrosion
_version_	1718391383092363264

Substitutional adsorptions of chloride at grain boundary sites on hydroxylated alumina surfaces initialize localized corrosion

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