Chromium-Free Coating for Al Alloy Corrosion Protection Based on a Novel Ti/Mg Oxyfluoride

Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2− fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2− hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led...

Full description

Saved in:
Bibliographic Details
Published inJournal of the Electrochemical Society Vol. 171; no. 7; pp. 71501 - 71511
Main Authors Vajo, John J., Adjorlolo, Alain A., Badaeva, Ekaterina A., Locsin, Maribel G., Badger, Jana, Meyer, Christopher A., Ma, Lu, Graetz, Jason
Format Journal Article
LanguageEnglish
Published United States IOP Publishing 04.07.2024
Subjects
active protection
conversion coatings
MATERIALS SCIENCE
non-chromate
Online AccessGet full text

Cover

Abstract Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2− fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2− hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti 5 MgO 7 F 8 . Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO 2 . This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.
AbstractList Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2− fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF 6 2− hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti 5 MgO 7 F 8 . Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO 2 . This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.
Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF62– fluoro-anion-based coating recipe containing boric acid and a Mg salt. Boric acid drove TiF62– hydrolysis enabling up to micrometer-scale thick coatings. The Mg salt led to deposition of a novel crystalline phase Ti/Mg oxyfluoride coating with an approximate composition of Ti5MgO7F8. Corrosion protection performance was characterized by polarization resistance measurements during immersion in 5% aqueous NaCl solution and neutral salt fog exposure following ASTM B.117. The performance is discussed in terms of the presence of fluoride in the coating enabling active behavior during its gradual depletion (in corrosion environments) toward a final composition approaching TiO2. This active corrosion protection mechanism may be more generally applicable for transition metal-based coatings that do not have high oxidation state oxo-anions, but do have stable fluoro-anions.
Author Ma, Lu
Graetz, Jason
Badaeva, Ekaterina A.
Meyer, Christopher A.
Adjorlolo, Alain A.
Badger, Jana
Vajo, John J.
Locsin, Maribel G.
Author_xml – sequence: 1
  givenname: John J.
  orcidid: 0000-0002-6271-4899
  surname: Vajo
  fullname: Vajo, John J.
  organization: HRL Laboratories, LLC, Malibu, California 90265, United States of America
– sequence: 2
  givenname: Alain A.
  surname: Adjorlolo
  fullname: Adjorlolo, Alain A.
  organization: The Boeing Company, Seattle, Washington 98124, United States of America
– sequence: 3
  givenname: Ekaterina A.
  surname: Badaeva
  fullname: Badaeva, Ekaterina A.
  organization: The Boeing Company, Seattle, Washington 98124, United States of America
– sequence: 4
  givenname: Maribel G.
  surname: Locsin
  fullname: Locsin, Maribel G.
  organization: The Boeing Company, Seattle, Washington 98124, United States of America
– sequence: 5
  givenname: Jana
  surname: Badger
  fullname: Badger, Jana
  organization: The Boeing Company, Seattle, Washington 98124, United States of America
– sequence: 6
  givenname: Christopher A.
  surname: Meyer
  fullname: Meyer, Christopher A.
  organization: The Boeing Company, Seattle, Washington 98124, United States of America
– sequence: 7
  givenname: Lu
  surname: Ma
  fullname: Ma, Lu
  organization: National Synchrotron Light Source II (NSLS-II), Brookhaven National Laboratory, Upton, New York 11973, United States of America
– sequence: 8
  givenname: Jason
  orcidid: 0000-0002-2584-2357
  surname: Graetz
  fullname: Graetz, Jason
  organization: HRL Laboratories, LLC, Malibu, California 90265, United States of America
BackLink https://www.osti.gov/servlets/purl/2432553$$D View this record in Osti.gov
BookMark eNp1kD1PwzAQhi1UJNrCzmgxMRDqS-y4GUtFAQkoQ1lYLMd2WldpXNkpov8eR0FMIJ3uS8-d7t4RGjSuMQhdArkFoMUECsoSDgATqZmk2Qka_rYGaEgIZAnNGZyhUQjbWMKU8iH6mG-829nDLll4Y_DcydY2a1w5j2d1tNodY9N7F6xr8Jt3rVFtl97JYDSOicSv7tPUeGUnL2u8_DpW9cF5q805Oq1kHczFTxyj98X9av6YPC8fnuaz50SlOWuTEnLFFU214jLlZU5KlpG0yFRZKV1Fl1cFTXOeaq6Bl8U0S2lGiC5lrg1QyMboqt_rQmtFUDaeuFGuaeKlIrIpY1mESA-p-ErwphJ7b3fSHwUQ0QkoOrVEp5boBYwj1_2IdXuxdQffxC_E1gQBHAQXhAMjIPa6iujNH-i_m78B_5-AIQ
CODEN JESOAN
Cites_doi 10.1016/j.jallcom.2012.07.078
10.1149/1945-7111/aba875
10.1007/s11998-019-00210-9
10.1016/j.apsusc.2011.03.122
10.3103/S1067821212020071
10.1149/2.0371803jes
10.1515/corrrev-2019-0032
10.1149/1945-7111/ab6b0d
10.5006/1.3277570
10.1021/jp501162a
10.1017/S0885715619000812
10.1038/s41529-018-0034-5
10.1246/cl.1996.433
10.1039/a801499j
10.1107/S160057671900997X
10.1107/S0909049505012719
ContentType Journal Article
Copyright 2024 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited
Copyright_xml – notice: 2024 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited
CorporateAuthor Brookhaven National Laboratory (BNL), Upton, NY (United States)
CorporateAuthor_xml – name: Brookhaven National Laboratory (BNL), Upton, NY (United States)
DBID O3W
TSCCA
AAYXX
CITATION
OIOZB
OTOTI
DOI 10.1149/1945-7111/ad5a43
DatabaseName IOP Publishing
IOPscience (Open Access)
CrossRef
OSTI.GOV - Hybrid
OSTI.GOV
DatabaseTitle CrossRef
DatabaseTitleList CrossRef
Database_xml – sequence: 1
  dbid: O3W
  name: IOP Publishing Free Content_
  url: http://iopscience.iop.org/
  sourceTypes:
    Enrichment Source
    Publisher
DeliveryMethod fulltext_linktorsrc
Discipline Engineering
Chemistry
EISSN 1945-7111
ExternalDocumentID 2432553
10_1149_1945_7111_ad5a43
jesad5a43
GroupedDBID -~X
.DC
0R~
29L
5GY
AATNI
ABDNZ
ABJNI
ACBEA
ACHIP
ADNWM
AENEX
AKPSB
ALMA_UNASSIGNED_HOLDINGS
AOAED
CJUJL
CS3
DU5
EBS
F5P
IOP
JGOPE
KOT
MV1
N5L
NFQFE
NHB
O3W
REC
RHI
RNS
ROL
RPA
TAE
TN5
TSCCA
UPT
WH7
YQT
~02
AAYXX
CITATION
IZVLO
OIOZB
OTOTI
ID FETCH-LOGICAL-c265t-b16c7c42dc7a27b60b530293cbfcdfbfc6f942672d7d17b98324300dba6de1413
IEDL.DBID IOP
ISSN 0013-4651
IngestDate Mon Oct 14 04:25:02 EDT 2024
Fri Aug 23 04:45:52 EDT 2024
Sun Aug 18 17:40:26 EDT 2024
Tue Aug 20 22:17:05 EDT 2024
IsDoiOpenAccess true
IsOpenAccess true
IsPeerReviewed true
IsScholarly true
Issue 7
Language English
License This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited.
LinkModel DirectLink
MergedId FETCHMERGED-LOGICAL-c265t-b16c7c42dc7a27b60b530293cbfcdfbfc6f942672d7d17b98324300dba6de1413
Notes JES-112063.R2
BNL-225929-2024-JAAM
USDOE Office of Science (SC), Basic Energy Sciences (BES)
SC0012704
ORCID 0000-0002-2584-2357
0000-0002-6271-4899
0000000225842357
0000000262714899
OpenAccessLink https://proxy.k.utb.cz/login?url=https://iopscience.iop.org/article/10.1149/1945-7111/ad5a43
PageCount 11
ParticipantIDs crossref_primary_10_1149_1945_7111_ad5a43
osti_scitechconnect_2432553
iop_journals_10_1149_1945_7111_ad5a43
PublicationCentury 2000
PublicationDate 2024-07-04
PublicationDateYYYYMMDD 2024-07-04
PublicationDate_xml – month: 07
  year: 2024
  text: 2024-07-04
  day: 04
PublicationDecade 2020
PublicationPlace United States
PublicationPlace_xml – name: United States
PublicationTitle Journal of the Electrochemical Society
PublicationTitleAbbrev JES
PublicationTitleAlternate J. Electrochem. Soc
PublicationYear 2024
Publisher IOP Publishing
Publisher_xml – name: IOP Publishing
References Kendig (jesad5a43bib1) 2003; 59
Šekularac (jesad5a43bib7) 2020; 167
Gates-Rector (jesad5a43bib14) 2019; 34
Lei (jesad5a43bib11) 2011; 257
Becker (jesad5a43bib3) 2019; 3
Gharbi (jesad5a43bib2) 2018; 2
Maki (jesad5a43bib10) 2014; 118
Milošev (jesad5a43bib5) 2018; 165
Kulinich (jesad5a43bib4) 2012; 53
Šekularac (jesad5a43bib6) 2020; 167
jesad5a43bib17
Kishimoto (jesad5a43bib9) 1998; 8
Ravel (jesad5a43bib13) 2005; 12
Zagorac (jesad5a43bib15) 2019; 52
Lei (jesad5a43bib12) 2012; 542
Deki (jesad5a43bib8) 1996; 25
Hesamedini (jesad5a43bib16) 2019; 16
References_xml – volume: 542
  start-page: 164
  year: 2012
  ident: jesad5a43bib12
  article-title: Effect of liquid-phase-deposited parameters on the photogenerated cathodic protection properties of TiO2 films
  publication-title: J. Alloy Comp.
  doi: 10.1016/j.jallcom.2012.07.078
  contributor:
    fullname: Lei
– volume: 167
  year: 2020
  ident: jesad5a43bib6
  article-title: Comparison of the electrochemical behavior and self-sealing of zirconium conversion coatings applied on aluminum alloys of series 1xxx to 7xxx
  publication-title: J. Electrochem. Soc.
  doi: 10.1149/1945-7111/aba875
  contributor:
    fullname: Šekularac
– volume: 16
  start-page: 623
  year: 2019
  ident: jesad5a43bib16
  article-title: Trivalent chromium conversion coatings
  publication-title: J. Coat. Technol. Res.
  doi: 10.1007/s11998-019-00210-9
  contributor:
    fullname: Hesamedini
– volume: 257
  start-page: 7330
  year: 2011
  ident: jesad5a43bib11
  article-title: Low-temperature liquid phase deposited TiO2 films on stainless steel for photogenerated cathodic protection applications
  publication-title: Appl. Surf. Sci.
  doi: 10.1016/j.apsusc.2011.03.122
  contributor:
    fullname: Lei
– volume: 53
  start-page: 176
  year: 2012
  ident: jesad5a43bib4
  article-title: On conversion coating treatments to replace chromating for Al alloys: recent developments and possible future directions’ Russ
  publication-title: J. Non-Ferr. Met.
  doi: 10.3103/S1067821212020071
  contributor:
    fullname: Kulinich
– volume: 165
  start-page: C127
  year: 2018
  ident: jesad5a43bib5
  article-title: Review—Conversion coatings based on zirconium and/or titanium
  publication-title: J. Electrochem. Soc.
  doi: 10.1149/2.0371803jes
  contributor:
    fullname: Milošev
– volume: 3
  start-page: 321
  year: 2019
  ident: jesad5a43bib3
  article-title: Chromate-free chemical conversion coatings for aluminum alloys
  publication-title: Corros. Rev.
  doi: 10.1515/corrrev-2019-0032
  contributor:
    fullname: Becker
– ident: jesad5a43bib17
– volume: 167
  year: 2020
  ident: jesad5a43bib7
  article-title: Electrochemical behavior and self-sealing ability of zirconium conversion coating applied on aluminum alloy 3005 in 0.5 M NaCl solution
  publication-title: J. Electrochem. Soc.
  doi: 10.1149/1945-7111/ab6b0d
  contributor:
    fullname: Šekularac
– volume: 59
  start-page: 379
  year: 2003
  ident: jesad5a43bib1
  article-title: Corrosion inhibition of aluminum and aluminum alloys by soluble chromates, chromate coatings, and chromate-free coatings
  publication-title: Crit. Rev. Corr. Sci. Eng.
  doi: 10.5006/1.3277570
  contributor:
    fullname: Kendig
– volume: 118
  start-page: 11964
  year: 2014
  ident: jesad5a43bib10
  article-title: Ionic equilibria for synthesis of TiO2 thin films by the liquid-phase deposition
  publication-title: J. Phys. Chem. C
  doi: 10.1021/jp501162a
  contributor:
    fullname: Maki
– volume: 34
  start-page: 352
  year: 2019
  ident: jesad5a43bib14
  article-title: The powder diffraction file: a quality materials characterization database
  publication-title: Powder Diffr.
  doi: 10.1017/S0885715619000812
  contributor:
    fullname: Gates-Rector
– volume: 2
  start-page: 12
  year: 2018
  ident: jesad5a43bib2
  article-title: Chromate replacement: what does the future hold?
  publication-title: npj Material Degradation
  doi: 10.1038/s41529-018-0034-5
  contributor:
    fullname: Gharbi
– volume: 25
  start-page: 433
  year: 1996
  ident: jesad5a43bib8
  article-title: Titanium (IV) oxide thin films prepared from aqueous solution
  publication-title: Chem. Lett.
  doi: 10.1246/cl.1996.433
  contributor:
    fullname: Deki
– volume: 8
  start-page: 2019
  year: 1998
  ident: jesad5a43bib9
  article-title: Photocatalytic activity of titanium oxide prepared by liquid phase deposition (LPD)
  publication-title: J. Mater. Chem.
  doi: 10.1039/a801499j
  contributor:
    fullname: Kishimoto
– volume: 52
  start-page: 918
  year: 2019
  ident: jesad5a43bib15
  article-title: Recent developments in the inorganic crystal structure database: theoretical crystal structure data and related features
  publication-title: J. Appl. Cryst.
  doi: 10.1107/S160057671900997X
  contributor:
    fullname: Zagorac
– volume: 12
  start-page: 537
  year: 2005
  ident: jesad5a43bib13
  article-title: ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT
  publication-title: J. Synchrotron Rad.
  doi: 10.1107/S0909049505012719
  contributor:
    fullname: Ravel
SSID ssj0011847
Score 2.5008214
Snippet Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF 6 2− fluoro-anion-based coating...
Chromium-free corrosion protection of aluminum alloys comparable to that of chromates (Cr(VI)) is demonstrated using a TiF62– fluoro-anion-based coating recipe...
SourceID osti
crossref
iop
SourceType Open Access Repository
Aggregation Database
Enrichment Source
Publisher
StartPage 71501
SubjectTerms active protection
conversion coatings
MATERIALS SCIENCE
non-chromate
Title Chromium-Free Coating for Al Alloy Corrosion Protection Based on a Novel Ti/Mg Oxyfluoride
URI https://iopscience.iop.org/article/10.1149/1945-7111/ad5a43
https://www.osti.gov/servlets/purl/2432553
Volume 171
hasFullText 1
inHoldings 1
isFullTextHit
isPrint
link http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV3dSxwxEB_8eLB9qB-t9GorEfTBhz13N9nE0Cc9eqig54OiFCHka-XseXtc90r1r3fi7oqKiPgSwjIkm5kkM5NMfgOwHuvMoSWRR1qwPAqAXZFkEl0Vy802C_jq92e6h0d875QdnGfnU_Dz4S1MMaq3_jZWK6DgioU1sK3cQrc7i0QIx9Eu04xOwyzFpRKm9H7v-OEKAV0X0aQvCAm_mzvKF1p4opOmsV_cnwtcYY80TXceLpp_rAJM_rQnpWnb22fwje8cxAJ8qi1QslORLsKUHy7BXKdJ_LYEHx9hFH6G3wE-97o_uY66Y-9Jp9AhUJqgrUt2sJXBoLjBj2McGEqYHFewD6G6i_rREaxoclT88wNy0t86vCS9_zf5YFKM-85_gdPur5POXlQnZIhsyrMyMgm3wrLUWaFTYXhsQs4hSa3Jrcux4LlEjS9SJ1wijMTdgtE4dkZz5xNUl8swMyyG_isQZoVjjNptQQ0TOSpFbqRkiXCp1ZTFLdhsRKJGFe6Gqt5QSxV4pwLvVMW7Fmwgm1W9-P6-Qrf2hO7KI61IlFBoZ2VxokYub8FKkLxC-QUQXRuijWypcBzoe9Fvb-xpBT6kIfYlPH3n32GmHE_8DzReSrN6P0mx7NGzO9Ym5KI
link.rule.ids 230,315,783,787,888,27938,27939,38879,38904,53856,53882
linkProvider IOP Publishing
linkToPdf http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwpV3dT9swED_xITF4GB8bojDAk-BhD2nz4cT1I-uoYBulDyChvRh_ZSqUpiopovvrd24SBAghJF4iKzrZuTvbdxeffwew58vYoCeRepLR1HOAXR6nHEMVnagmdfjq03-6J53k6Jz-vIgvyjqn07sw2bDc-uvYLICCCxGWwLa8gWF37DGXjiNNLGnUGJp0FuZx5cZuih-fdh-OETB8YVUJA1f0uzqnfKGXJ3ZpFsfGPTrDVfbI2rSX4bL6ziLJ5Lo-zlVd_3sG4fgORlbgY-mJkoOCfBVm7GANPrSqAnBrsPQIq_AT_HEwuje98Y3XHllLWpl0CdMEfV5ygL30-9kEX46QOdQ06RbwD675He2kIdiQpJPd2T456zVO_pLT-0naH2ejnrGf4bx9eNY68srCDJ4Okzj3VJBopmloNJMhU4mvXO0hHmmVapPiI0k5Wn4WGmYCpjjuGjTyfaNkYmyAZnMd5gbZwG4AoZoZSiPdZJGiLEXjmCjOacBMqGVE_Rp8q9QihgX-hijuUnPh5Cec_EQhvxrso6hFuQhvX6H7-oTuyiItCwQT6G_FfiBQDzXYctoXqEMHpqtd1pHOBfKBMVi0-caRdmGh-6Mtfh93fm3BYoj-0DTTl36BuXw0ttvoz-RqZzpn_wPMnOkM
openUrl ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Chromium-Free+Coating+for+Al+Alloy+Corrosion+Protection+Based+on+a+Novel+Ti%2FMg+Oxyfluoride&rft.jtitle=Journal+of+the+Electrochemical+Society&rft.au=Vajo%2C+John+J.&rft.au=Adjorlolo%2C+Alain+A.&rft.au=Badaeva%2C+Ekaterina+A.&rft.au=Locsin%2C+Maribel+G.&rft.date=2024-07-04&rft.issn=0013-4651&rft.eissn=1945-7111&rft.volume=171&rft.issue=7&rft.spage=71501&rft_id=info:doi/10.1149%2F1945-7111%2Fad5a43&rft.externalDBID=n%2Fa&rft.externalDocID=10_1149_1945_7111_ad5a43
thumbnail_l http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=0013-4651&client=summon
thumbnail_m http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=0013-4651&client=summon
thumbnail_s http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=0013-4651&client=summon