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An Insight into the Critical Role of Microstructure and Surface Preparation on Localized Conversion Coating Deposition on Cast Al Alloys
Jönköping University, School of Engineering, JTH, Materials and Manufacturing.ORCID iD: 0000-0002-6245-7693
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The spontaneous cerium conversion coating formation over aluminium alloys is affected by the chemical process conditions, the surface preparation prior to conversion treatment and the microstructure of the underlying alloy. Most research performed until now focus only on the former whereas the influence of the latter two is poorly understood. The microstructure of aluminium alloys contains cathodic intermetallic particles that have a crucial role in conversion coating formation as they are responsible for the increase in pH to a critical level where chemical precipitation reaction of conversion coating compounds becomes possible. There are many different types of intermetallics in the aluminium alloys’ microstructure whose cathodic potential depends on their chemical composition, but no systematic study exists on the influence of their geometric properties on the reactivity of intermetallics. The surface preparation also critically affects reactivity of intermetallics, and a consensus exists regarding which preparation procedure makes an alloy surface most conducive for conversion coating deposition, but little is known about the topographical and volta potential changes occurring around the intermetallics from the surface preparations. An insight into both the role of microstructure and surface preparation is thus crucial as they can help design better treatments.

To address this knowledge gap, model microstructures of hypoeutectic cast Al-7Si alloys have been created in the study with the desired intermetallic composition and geometry. By addition of Cu and Fe to the hypoeutectic cast alloy, two types of intermetallics, namely θ-Al2Cu and β-Al5FeSi form and are the main objects of investigation in the study. The geometrical dimensions of the intermetallics were modified by directionally solidifying the cast alloys at different rates. Different surface preparation procedures, namely mechanical polishing, NaOH, NaOH-HNO3 and NaOH-H2SO4 have been tried in the study. Furthermore, parameters such as etching time have been varied to understand their influence. The microstructural features, particularly intermetallic geometry and cathodic potential have been systematically compared with localized deposition on them through conversion coating treatment. Experimentally derived data-based analyses have been conducted to come to conclusions in the study.

Firstly, the study found differences in the initiation of localized deposits on θ-Al2Cu and β-Al5FeSi attributed this to the conductivity variation due to compositional difference. Among the three differently sized θ-IM investigated in the study, namely fine, coarse and bulky θ, increasing the size from fine to coarse led to increase in reactivity of the IM for localized deposition. But increasing the size even further from coarse to bulky θ decreased the reactivity. Such a decrease in reactivity was found to be due to a combination of factors such as volta potential difference relative to the matrix and geometry.

Surface preparation affected localized deposition and the choice of procedure applied critically depends on the intermetallics present in the microstructure. The β-Al5FeSi is most reactive for conversion coating deposition when prepared with NaOH etching solution but becomes passive when further pickled with HNO3 solution. The θ-Al2Cu, on the other hand, becomes most active when subjected to multi-step NaOH- HNO3 procedure. Such observations make the choice of a surface preparation procedure difficult when the alloy microstructure contains both θ-Al2Cu and β-Al5FeSi intermetallics. The localized deposition of cerium conversion compounds after surface preparation are triggered due to a combination of surface factors like including volta potential and presence of Al(OH)3 smut, with varying degrees of dominance depending on the type of IM. Al(OH)3 smut content was found sensitive to the NaOH etching time. A further HNO3 pickling step cleans the surface. A “cleaner” surface was found to be associated with more consistent coverage numbers, while the presence of Al(OH)3 smut, on the one hand provides additional source of alkalinity, does not consistently result in good coverage.

Abstract [sv]

Den spontana formationen av Ce-omvandlingsbeläggningar på aluminiumlegeringar påverkar förhållandet i den kemiska processen, behandlingen av ytan före beläggning samt legeringens mikrostruktur. Den största delen av den forskning som bedrivits inom detta område har, fram tills nu, framför allt fokuserat på förståelsen kring den kemiska processen, medan inverkan av de två sistnämnda nästintill saknas. Mikrostrukturen i aluminiumlegeringar innehåller katodiska, intermetalliska partiklar vilka har en avgörande roll för omvandlingsbeläggningar, då de är orsaken till ökandet av pH till den kritiska nivå där den kemiska utfällningsreaktionen för omvandlingsbeläggningssammansättningar blir möjlig. Det finns ett flertal olika typer av intermetalliska föreningar i en aluminiumlegerings mikrostruktur, där dess katodiska potential beror på legeringens kemiska sammansättning, men inga tidigare studier av systematisk karaktär finns gällande hur reaktiviteten påverkas av intermetallernas geometriska egenskaper. Även förbehandlingen av ytan påverkar reaktiviteten hos intermetalliska föreningar, och det råder en allmän konsensus gällande vilken typ av behandling som gör en legeringsyta mest gynnsam för omvandlingsbeläggning, men kunskapen om de topografiska och voltapotentialförändringar som sker kring intermetallerna från ett ytbehanlingsperspektiv är inte allmänt känd. Insikt om hur mikrostruktur och ytbehandlingsmetod påverkar är därför avgörande då de kan hjälpa till att designa förbättrade behandlingar.

För att belysa denna kunskapslucka har modellmikrostrukturer av hypoeutektiska gjutna Al-7Si-legeringar, med den önskade intermetalliska sammansättningen och geometrin skapats till studien. Genom tillsats av Cu och Fe till den hypoeutektiska legeringen bildas två typer av intermetallföreningar, nämligen θ-Al2Cu och β-Al5FeSi, och är de huvudsakliga undersökningsobjekten i studien. De geometriska dimensionerna hos de intermetalliska materialen modifierades genom riktningsstelning, med olika hastigheter, av de gjutna legeringarna. Olika ytbehandlingsmetoder, nämligen mekanisk polering, NaOH, NaOH-HNO3 och NaOH-H2SO4 provades i studien. Dessutom har parametrar, så som etsningstid, varierats för att förstå dess inverkan. De mikrostrukturella egenskaperna, särskilt intermetallisk geometri och katodpotential, har systematiskt jämförts med lokal deposition på dem genom omvandlingsbeläggningsbehandling. Experimentellt härledda databaserade analyser har genomförts för slutsatserna i studien.

Primärt fann studien skillnader i initieringen av lokala depositioner på θ-Al2Cu och β-Al5FeSi och tillskrev detta till konduktivitetsvariationen orsakad av skillnad i sammansättningen. Bland de tre olika stora θ-IM som undersöktes i studien, nämligen fina, grova samt skrymmande θ, ledde ökning av storleken från fin till grov till ökad reaktivitet hos IM för lokal deposition. Men genom att öka storleken ytterligare från grov till skrymmande θ minskade reaktiviteten. En sådan minskning i reaktivitet visade sig bero på en kombination av faktorer så som voltapotentialskillnad i förhållande till matrisen och geometrin.

Förbehandling av ytan påverkade lokal deposition och valet av tillvägagångssätt som tillämpas beror på de intermetalliska föreningar i mikrostrukturen. Mest reaktiv för omvandlingsbeläggningsavsättning är β-Al5FeSi när den framställs med NaOH-etsningslösning men blir passiv när den betas ytterligare med HNO3-lösning. När det gäller θ-Al2Cu, blir ytan som mest aktiv när den utsätts för en flerstegs NaOH-HNO3-behandling. Dessa observationer gjorde valet av en ytbehandlingsprocedur svår när legeringens mikrostruktur innehåller både θ-Al2Cu och β-Al5FeSi intermetalliska föreningar. Den lokala depositionen av Ce-omvandlingssammansättningar efter ytbehandling utlöses på grund av en kombination av faktorer som, inklusive voltapotential och närvaro av Al(OH)3 ”smut”, med varierande grader av dominans beroende på typen av IM. Al(OH)3- ”smut”- innehåll befanns vara känsligt för etsningstiden med NaOH. Ytterligare ett HNO3-betningssteg rengör ytan. En "renare" yta visade sig vara associerad med mer konsekventa täckningstal, medan närvaron av Al(OH)3- smut ger ytterligare en källa till alkalinitet, inte konsekvent resulterar i god täckning.

Place, publisher, year, edition, pages
Jönköping: Jönköping University, School of Engineering , 2022. , p. 58
Series
JTH Dissertation Series ; 073
Keywords [en]
aluminium alloys, cast Al-Si alloys, conversion coating treatment, cerium, localized deposition, surface preparation, microstructure, SEM, FIB-SEM, AFM-SKPFM
Keywords [sv]
Aluminiumlegeringar, gjutna Al-Si legeringar, Cerium, lokal deposition, omvandlingsbeläggningsbehandling, förbehandling av yta, mikrostruktur, SEM, FIB-SEM, AFM-SKPFM
National Category
Metallurgy and Metallic Materials
Identifiers
URN: urn:nbn:se:hj:diva-58601ISBN: 978-91-87289-79-8 (print)OAI: oai:DiVA.org:hj-58601DiVA, id: diva2:1701908
Public defence
2022-11-09, E3231, School of Engineering, Jönköping, 10:00 (English)
Opponent
Supervisors
Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2025-10-13Bibliographically approved
List of papers
1. The role of microstructure and cathodic intermetallics in localised deposition mechanism of conversion compounds on Al (Si, Fe, Cu) alloy
Open this publication in new window or tab >>The role of microstructure and cathodic intermetallics in localised deposition mechanism of conversion compounds on Al (Si, Fe, Cu) alloy
2020 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 402, article id 126502Article in journal (Refereed) Published
Abstract [en]

Cerium-based conversion coating formation is triggered by a local rise in pH at cathodic sites produced by the oxygen reduction reaction. Therefore, size, morphology distribution and electrochemical potential of those sites play a crucial role. While the deposition reaction is sensitive to both immersion bath concentrations and underlying substrate microstructure, only the former has been widely investigated. This research attempts to fill the gap by studying the effect of controlled microstructure variables like the cathodic intermetallics' geometry and spatial distribution on the conversion compound deposit initiation. A controlled cast Al alloy was synthesised for this study and consisted of distinct cathodic phases: Cu-rich intermetallics, Fe-rich intermetallics and Si particles. The localised deposition preferentially formed only on strong cathodic Cu-rich intermetallics. Size (surface area) of the Cu-rich intermetallic correlated linearly with the deposited area over it in terms of lateral and z-direction spread. The pH gradient occurring from the oxygen reduction near an IM is very local and does not affect pH gradients of a neighbouring IM. When immersion time is increased from 0.5 h to 1 h, the percentage of Cu-rich IM covered with conversion coating increases. Big Cu-rich IM activate faster for deposition reaction than small Cu-rich IM.

Place, publisher, year, edition, pages
Elsevier, 2020
Keywords
AFM, Al-Si cast, Cerium, Conversion coatings, Microstructure-induced localised deposition, SEM, SKPFM, Aluminum alloys, Coatings, Deposition, Electrolytic reduction, Intermetallics, Iron alloys, Microstructure, Morphology, Oxygen, Oxygen reduction reaction, Silicon, Bath concentrations, Cerium-based conversion coatings, Deposition mechanism, Deposition reactions, Electrochemical potential, Fe-Rich intermetallics, Morphology distributions, Substrate microstructure, Copper alloys
National Category
Materials Engineering
Identifiers
urn:nbn:se:hj:diva-50953 (URN)10.1016/j.surfcoat.2020.126502 (DOI)000590183000064 ()2-s2.0-85094840175 (Scopus ID)HOA JTH 2020;JTHMaterialIS (Local ID)HOA JTH 2020;JTHMaterialIS (Archive number)HOA JTH 2020;JTHMaterialIS (OAI)
Funder
EU, Horizon 2020, 764977
Available from: 2020-11-09 Created: 2020-11-09 Last updated: 2025-10-13Bibliographically approved
2. A study of the localized ceria coating deposition on Fe-rich intermetallics in an AlSiFe cast alloy
Open this publication in new window or tab >>A study of the localized ceria coating deposition on Fe-rich intermetallics in an AlSiFe cast alloy
2021 (English)In: Materials, E-ISSN 1996-1944, Vol. 14, no 11, article id 3058Article in journal (Refereed) Published
Abstract [en]

Corrosion inhibiting conversion coating formation is triggered by the activity of micro-galvanic couples in the microstructure and subsequent local increase in pH at cathodic sites, which in the case of aluminium alloys are usually intermetallics. Ceria coatings are formed spontaneously upon immersion of aluminium alloys in a cerium conversion coating solution, the high pH gradient in the vicinity of intermetallics drives the local precipitation of ceria conversion compounds. Cu-rich intermetallics demonstrate a highly cathodic nature and have shown the local precipitation reaction to occur readily. Fe-rich intermetallics are, however, weaker cathodes and have shown varied extents of localized deposits and are in focus in the current work. Model cast Al-7wt.%Si alloys have been designed with 1 wt.% Fe, solidified at different cooling rates to achieve two different microstructures, with big and small intermetallics, respectively. Upon subjecting the two microstructures to the same conversion coating treatment (immersion in a 0.1 M CeCl3 solution) for a short period of 2 h, preferential heavy deposition on the boundaries of the big intermetallics and light deposition on the small intermetallics was observed. Based on these observations, a mechanism of localized coating initiation at these Fe-rich intermetallic particles (IM) is proposed.

Place, publisher, year, edition, pages
MDPI, 2021
Keywords
conversion coating; cerium; localized deposition; Fe; intermetallic; SEM; EDS; AFM; SKPFM; microstructure-induced localized deposition
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:hj:diva-51563 (URN)10.3390/ma14113058 (DOI)000660272500001 ()2-s2.0-85107757358 (Scopus ID)GOA;;1519165 (Local ID)GOA;;1519165 (Archive number)GOA;;1519165 (OAI)
Funder
EU, Horizon 2020, 764977
Note

Included in licentiate thesis in manuscript form with the title: "A study on the localized cerium coating deposition on Fe-rich intermetallics in an Al-Si-Fe cast alloy".

Available from: 2021-01-18 Created: 2021-01-18 Last updated: 2025-10-13Bibliographically approved
3. A localized study on the influence of surface preparation on the reactivity of cast Al-7Si-1Fe and Al-7Si-2Cu-1Fe alloys and their effect on cerium conversion coating deposition
Open this publication in new window or tab >>A localized study on the influence of surface preparation on the reactivity of cast Al-7Si-1Fe and Al-7Si-2Cu-1Fe alloys and their effect on cerium conversion coating deposition
2022 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 585, article id 152730Article in journal (Refereed) Published
Abstract [en]

The spontaneous triggering of cerium-based conversion coating deposition occurs due to active micro-galvanic couple induced local rise in pH at cathodic sites. Since surface preparations prior to conversion coating treatment modify the surface reactivity or the extent of micro-galvanic coupling between the anodic and cathodic phases, they are of crucial importance. While many past works have studied the effect of various preparations including alkaline etching and/or acid pickling and their parameters on the resulting conversion coating, very few studies focus on the local surface reactivity changes from the surface preparation. Moreover, most of the studies use high Cu containing AA2024, and related work on other alloys are scarce. In this study, two model cast alloys Al-7Si-1Fe and Al-7Si-2Cu-1Fe have been created to obtain a relatively homogeneous microstructure containing two different cathodic activity intermetallics Fe-rich IM β-Al5FeSi and Cu-rich IM θ-Al2Cu. Changes in the surface state of each alloy are monitored with AFM-SKPFM after subjecting them to four specific surface preparations: (1) Mechanical polishing (2) NaOH etching (3) NaOH etching + HNO3 Pickling (4) NaOH etching + H2SO4 pickling and correlations have been made with localized conversion coating deposit observations.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
AFM-SKPFM, Cerium, Conversion coating, Localized deposition, SEM, Volta potential, Alkalinity, Aluminum coatings, Copper alloys, Etching, Iron alloys, Silicon alloys, Sodium hydroxide, AFM, Cerium conversion coatings, Coatings deposition, Conversion coatings, Localised, Surface preparation, Surface reactivity, Deposition
National Category
Manufacturing, Surface and Joining Technology
Identifiers
urn:nbn:se:hj:diva-55961 (URN)10.1016/j.apsusc.2022.152730 (DOI)000776625500004 ()2-s2.0-85124178334 (Scopus ID)HOA;;798115 (Local ID)HOA;;798115 (Archive number)HOA;;798115 (OAI)
Funder
EU, Horizon 2020, 764977
Available from: 2022-03-02 Created: 2022-03-02 Last updated: 2025-10-13Bibliographically approved
4. Reviewing the role of underlying aluminium alloy microstructure on localized deposition mechanism of conversion coatings
Open this publication in new window or tab >>Reviewing the role of underlying aluminium alloy microstructure on localized deposition mechanism of conversion coatings
(English)Manuscript (preprint) (Other academic)
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:hj:diva-58598 (URN)
Note

Included in thesis in manuscript form.

Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2025-10-13
5. The influence of cathodic θ‐Al2Cu intermetallic geometry on the localized‐corrosion‐triggered conversion coating deposition
Open this publication in new window or tab >>The influence of cathodic θ‐Al2Cu intermetallic geometry on the localized‐corrosion‐triggered conversion coating deposition
(English)Manuscript (preprint) (Other academic)
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:hj:diva-58599 (URN)
Note

Included in thesis in manuscript form.

Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2025-10-13
6. The effect of etching and pickling on the reactivity of intermetallics in cast aluminium alloys towards conversion coating deposition
Open this publication in new window or tab >>The effect of etching and pickling on the reactivity of intermetallics in cast aluminium alloys towards conversion coating deposition
2025 (English)In: Discover Electrochemistry, E-ISSN 3005-1215, Vol. 2, article id 8Article in journal (Refereed) Published
Abstract [en]

In Al–Si–Cu–Fe alloys, localized cerium conversion coating (CeCC) deposition on intermetallic (IM) particles is strongly influenced by surface preparation. Here, we investigate how single-step etching (NaOH only) and multi-step etching and pickling (NaOH + HNO3​) preparation times affect CeCC nucleation and growth on Cu-rich θ-Al2Cu and Fe-rich β-Al5FeSi IMs in directionally solidified Al-7Si-2Cu-1Fe and Al-7Si-1Fe alloys. The reactivity of surface was characterized with AFM–SKPFM and surface coverage of CeCC deposits characterized with SEM. A quantitative analysis was performed to discern the effects of different surface preparation procedures on CeCC deposition. Single-step NaOH activates both IMs but leaves substantial Al(OH)3​ smut on θ-containing alloys, which elevates local pH yet introduces variability in coating coverage. In contrast, multi-step etching removes smut, ensuring more consistent CeCC on θ-Al2Cu driven primarily by cathodic activity of the IMs. Fe-rich β-Al5FeSi IMs exhibit nearly 100% coverage even after a short 30 s NaOH etch and 0.5 h CeCC treatment, whereas Cu-rich θ-Al2Cu requires 120 s NaOH etching plus HNO3​ pickling for reliable coverage. Prolonged CeCC times promote lateral deposit growth on both IM types when using single-step NaOH, but such growth is absent for θ-Al2Cu in multi-step samples. These findings reveal that Al(OH)3​ smut, coupled with local Volta potential and alkaline microenvironments, governs IM reactivity during conversion coating formation. Accordingly, single-step NaOH is sufficient for Fe-rich alloys, while multi-step etching is recommended for Cu-rich alloys. This work provides insights into optimizing surface preparation for improved and predictable CeCC deposition on distinct intermetallic phases.

Place, publisher, year, edition, pages
Springer, 2025
Keywords
Aluminium, Intermetallics, Oxygen reduction, Surface preparation, Conversion coating, Cerium, Localized deposition, Volta potential, AFM, SKPFM, SEM
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:hj:diva-58600 (URN)10.1007/s44373-025-00022-0 (DOI)GOA;;1701889 (Local ID)GOA;;1701889 (Archive number)GOA;;1701889 (OAI)
Funder
EU, Horizon 2020, 764977
Note

Included in doctoral thesis in manuscript form.

Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2026-01-03Bibliographically approved

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