Corrosion protection with Al/Zn-based coatings
11807941 · 2023-11-07
Assignee
Inventors
- Ross McDowall Smith (Cordeaux Heights, AU)
- Qiyang Liu (Mount Keira, AU)
- Bryan Andrew Shedden (Albion Park, AU)
- Aaron Kiffer Neufeld (Figtree, AU)
- Joe Williams (Woonona, AU)
- David James Nolan (Gerringong, AU)
- Wayne Renshaw (Unanderra, AU)
Cpc classification
Y10T428/12021
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C23C2/14
CHEMISTRY; METALLURGY
Y10T428/12028
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
Red rust staining of Al/Zn coated steel strip in “acid rain” or “polluted” environments can be minimised by forming the coating as an Al—Zn—Si—Mg alloy coating with an OT:SDAS ratio greater than a value of 0.5:1, where OT is the overlay thickness on a surface of the strip and SDAS is the measure of the secondary dendrite arm spacing for the Al-rich alpha phase dendrites in the coating. Red rust staining in “acid rain” or “polluted” environments and corrosion at cut edges in marine environments can be minimised in Al—Zn—Si—Mg alloy coatings on steel strip by selection of the composition (principally Mg and Si) and solidification control (principally by cooling rate) and forming Mg.sub.2Si phase particles of a particular morphology in interdendritic channels.
Claims
1. A method for forming a coating of a corrosion resistant Al—Zn—Si—Mg alloy on a metal strip, the method comprising: (a) passing the metal strip through a molten bath of the Al—Zn—Si—Mg alloy and forming a coating of the alloy on one or both surfaces of the metal strip, wherein the alloy contains 40-65 wt. % Al, 35-50 wt. % Zn, 1.0-3 wt. % Si, 1.5-2.5 wt. % Mg, and optionally other elements in amounts of less than 0.5 wt. % for each other element, (b) solidifying the coating on the metal strip and forming a solidified coating having a microstructure that comprises dendrites of Al-rich alpha phase and interdendritic channels of Zn-rich eutectic phase mixture extending from the metal strip, wherein particles of Mg.sub.2Si phase are positioned in the interdendritic channels in the solidified coating, and (c) controlling the cooling rate during coating solidification step (b) such that the particles of Mg.sub.2Si phase in the interdendritic channels in the solidified coating block corrosion along the interdendritic channels, wherein greater than 60% of the interdendritic channels are blocked by particles of Mg.sub.2Si phase, and wherein the solidified coating has an overlay thickness greater than 5 μm and less than 30 μm.
2. The method defined in claim 1, wherein controlling step (a) and the cooling rate in step (b) to form particles of Mg.sub.2Si phase in the interdendritic channels forms Mg.sub.2Si phase particles in the interdendritic channels in the solidified coating having a size range and a spacial distribution that activates the Al-rich alpha phase to provide sacrificial protection.
3. The method defined in claim 1, wherein the cooling rate CR during coating solidification is less than 170-4.5CT, where CR is the cooling rate in ° C./second and CT is the coating thickness on a surface of the strip in micrometres.
4. The method defined in claim 1, wherein greater than 70% of the total volume fraction of Mg.sub.2Si phase in the coating is in the lower two thirds of the overlay thickness of the coating.
5. The method defined in claim 1, wherein greater than 70% of the interdendritic channels are blocked by Mg.sub.2Si phase particles.
6. The method defined in claim 1, wherein the overlay thickness of the coating is less than 20 μm.
7. The method defined in claim 1, wherein the Zn concentration is 39-48 wt. %.
8. The method defined in claim 1, wherein the Mg concentration is 1.7-2.3 wt. %.
9. The method defined in claim 1, wherein the Si concentration is 1.3-2.5 wt. %.
10. The method defined in claim 1, wherein the metal strip is a steel strip.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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1. BLOCKING
(17) According to the present invention there is provided a method for forming a coating of a corrosion resistant Al—Zn—Si—Mg alloy on a metal, typically steel, strip, that is suitable, by way of example, for “acid rain” or “polluted” environments comprises: (a) passing metal strip through a molten bath of the Al—Zn—Si—Mg alloy and forming a coating of the alloy on one or both surfaces of the strip, (b) solidifying the coating on the strip and forming a solidified coating having a microstructure that comprises dendrites of Al-rich alpha phase and interdendritic channels of Zn-rich eutectic phase mixture, extending from the metal strip, and with Mg.sub.2Si phase in the interdendritic channels, and the method comprising selecting the Mg and Si concentrations and controlling the cooling rate in step (b) to form particles of Mg.sub.2Si phase in the interdendritic channels in the solidified coating that block corrosion along the interdendritic channels.
(18) By way of explanation, in Al/Zn-based coatings with a dendritic structure, Si is present as particles with a flake-like morphology and, although it does not corrode, it does not fill and block the interdendritic channels from interdendritic corrosion to the steel strip. The applicant has found that Mg added to Al/Zn-based coatings containing Si can combine with Si to form Mg.sub.2Si phase particles in the interdendritic channels between the arms of the Al-rich alpha phase dendrites that have an appropriate size and morphology which block what would otherwise be direct corrosion pathways to the steel strip and helps to isolate the underlying steel substrate cathode. The appropriate size and morphology particles are formed by controlling solidification, i.e. cooling rate, of the coating.
(19) In particular, the applicant has found that the cooling rate CR during coating solidification should be maintained less than 170-4.5CT, where CR is the cooling rate in ° C./second and CT is the coating thickness on a surface of the strip in micrometres.
(20) The morphology of the appropriately sized Mg.sub.2Si phase particles may be described as being in the form of “Chinese script” when viewed in planar images and as being in the form of flower petals when viewed in 3-dimensional images. The morphology is shown, by way of example, in
(21) The petals of the Mg.sub.2Si particles may have a thickness less than 8 μm.
(22) The petals of the Mg.sub.2Si phase particles may have a thickness less than 5 μm.
(23) The petals of the Mg.sub.2Si phase particles may have a thickness in a range of 0.5-2.5 μm.
(24) The Mg concentration may be selected to be greater than 0.5%. Below this concentration there are insufficient Mg.sub.2Si phase particles to fill and block interdendritic channels.
(25) The Mg concentration may be selected to be less than 3%. Above this concentration large Mg.sub.2Si particles with a cube-type morphology form that are ineffective at blocking interdendritic corrosion.
(26) In particular, the Al—Zn—Si—Mg alloy may contain more than 1% Mg.
(27) For coatings with Si concentrations from 0.5 to 2%, the volume fraction of interdendritic Mg.sub.2Si phase compared to other Si-containing phases may be greater than 50%.
(28) The volume fraction of interdendritic Mg.sub.2Si phase compared to other Si-containing phases may be greater than 80%.
(29) The proportion of interdendritic Mg.sub.2Si phase situated in the lower two thirds of the overlay thickness of the coating may be greater than 70% of the total volume fraction of Mg.sub.2Si phase in the coating in order to provide good blocking of interdendritic channels.
(30) The proportion of interdendritic channels “blocked” by Mg.sub.2Si phase may be greater than 60%, typically greater than 70%, of the total number of channels.
(31) The applicant has also found that the improved protection that is possible with the present invention applies across a range of microstructures, from coarse dendrite structures with OT:SDAS ratios of 0.5:1 to fine dendrite structures with OT:SDAS ratios of 6:1.
(32) Corrosion along these pathways in general, and red rust staining via these pathways in particular, in “acid rain” or “polluted” environments is therefore retarded.
(33) In Al/Zn alloy coatings, corrosion along the interdendritic channels may also be restricted by reducing the size of the channels as a consequence of increasing the cooling rate during solidification and thereby reducing the SDAS of the coating, as disclosed in U.S. Pat. No. 3,782,909. However, while this may slow surface corrosion of the coating (as often determined by mass loss testing), it restricts the availability of the zinc rich phases mixture to provide sacrificial protection for the steel substrate. Consequently, corrosion of the steel substrate occurs more readily.
2. ACTIVATION OF ALPHA PHASE
(34) According to the present invention there is provided a method for forming a coating of a corrosion resistant Al—Zn—Si—Mg alloy on a metal, typically steel, strip, that is suitable, by way of example, for “acid rain” or “polluted” environments comprises: (a) passing metal strip through a molten bath of the Al—Zn—Si—Mg alloy and forming a coating of the alloy on one or both surfaces of the strip, (b) solidifying the coating on the strip and forming a solidified coating having a microstructure that comprises dendrites of Al-rich alpha phase and interdendritic channels of Zn-rich eutectic phase mixture, extending from the metal strip, and with Mg.sub.2Si phase in the interdendritic channels,
and the method comprising selecting the Mg and Si concentrations and controlling the cooling rate in step (b) to form particles of Mg.sub.2Si phase in the interdendritic channels in the solidified coating having a size range, morphology and a spacial distribution that activates the Al-rich alpha phase to provide sacrificial protection.
(35) In particular, the applicant has found that Mg.sub.2Si phase by itself is reactive and can corrode readily. However, the applicant has also found conditions that render the Mg.sub.2Si phase passive, enable channel blocking and promote, and enhance activation of the Al-rich alpha phase in the sacrificial protection of the steel strip.
(36) In particular, the applicant has found that the addition of suitable Mg and Si concentrations to Al/Zn-based alloy coating compositions and the selection of the cooling rate to solidify a coating of the alloy composition on a steel strip can result in the formation of a Mg.sub.2Si phase in a suitable dispersion and location in interdendritic channels to activate Al-rich alpha phase to provide sacrificial protection of the steel in certain marine and “acid rain” and “polluted” environments.
(37) Activation of the Al-rich alpha phase enables the application of finer dendritic structures without the consequent loss of sacrificial protection ability at cut edges or other regions where the steel substrate has been exposed.
(38) The selection of Mg and Si concentrations and the cooling rate is in line with the description of these parameters under the heading “Blocking”.
(39) Specifically, in the case of cooling rate, the applicant has found that the cooling rate CR during coating solidification should be maintained less than 170-4.5CT, where CR is the cooling rate in ° C./second and CT is the coating thickness on a surface of the strip in micrometres.
(40) In the case of composition, by way of example, in “acid rain” or “polluted” environments and “acid” micro-environments, the Mg concentration may be greater than 0.5% for the formation of Mg.sub.2Si.
(41) The Mg concentration may be greater than 1% to ensure effective activation of the alpha phase.
(42) The Mg concentration may be less than 3%. At higher concentrations coarse, widely dispersed primary Mg.sub.2Si phase can form which cannot provide uniform activation of the Al-rich alpha phase.
(43) In particular, the Al—Zn—Si—Mg alloy may contain more than 1% Mg.
(44) The applicant has also found that the improved sacrificial protection that is possible with the present invention applies across a range of microstructures, from coarse dendrite structures with OT:SDAS ratios of 0.5:1 to fine dendrite structures with OT:SDAS ratios of 6:1.
(45) The applicant has also found that Al—Zn—Si—Mg alloy coated strip manufactured in accordance with the present invention, and subsequently painted, shows the development of a more narrow, uniform corrosion front as a result of Al-rich alpha phase activation and a reduced level of edge undercutting in marine environments.
(46) Samples manufactured in accordance with the present invention showed a reduced rate of “edge creep” or “undercutting” from cut-edges, compared to conventional Al/Zn coatings, in experimental work carried out by the applicant.
(47) The improved performance has been shown to apply to a range of coating structures and for a range of paint films.
(48) The present invention is described further with reference to the accompany drawings, of which:
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(68) The improved corrosion performance of examples of Al—Zn—Si—Mg alloy coated steel strip in accordance with the present invention has been demonstrated by the applicant on test samples exposed in a range of actual “acid rain”, “polluted” and marine environment sites.
(69) The test samples include test panels developed by the applicant to provide information on corrosion of coatings.
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(71) Performance in marine environments was assessed by outdoor exposure testing at sites with ISO ratings from C2 to C5 as per AS/NZS 1580.457.1.1996 Appendix B and by laboratory Cyclic Corrosion Testing (CCT).
(72) Table 1 presents data that shows the improved performance in the level of painted edge undercutting of examples of Al—Zn—Si—Mg coated steel test panels in accordance with the present invention for a range of metallic coating mass (unit: mm) for washed exposure in a severe marine environment. The table also includes comparative data for conventional Al/Zn-based alloy coated test panels.
(73) TABLE-US-00001 Edge Undercutting - Edge Undercutting - Coating Conventional Al/Zn Invention Al/Zn Mass Coating Coating 150 g/m.sup.2 12 5 100 g/m.sup.2 20 8 75 g/m.sup.2 21 9 50 g/m.sup.2 66 10
(74) It is evident from Table 1 that there was significantly less edge undercutting with the Al—Zn—Si—Mg coated steel test panels in accordance with the present invention than with the conventional Al/Zn-based alloy coated test panels.
(75) Table 2 presents further data that shows the improved performance in the level of undercutting of examples of painted Al—Zn—Si—Mg coated steel test panels in accordance with the present invention for a range of paint types (unit: mm) for washed exposure in a severe marine environment. The table also includes comparative data for conventional Al/Zn-based alloy coated test panels.
(76) TABLE-US-00002 Edge Undercutting - Edge Undercutting - Coating Conventional Al/Zn Invention Al/Zn Paint Type Mass Coating Coating Polyester 150 g/m.sup.2 9 3.5 Polyester 100 g/m.sup.2 15 5 Water Based 150 g/m.sup.2 8 3.2 Water Based 100 g/m.sup.2 22 4.5 “Cr-Free” 150 g/m.sup.2 22 6
(77) It is evident from Table 2 that there was significantly less edge undercutting with the painted Al—Zn—Si—Mg coated steel test panels in accordance with the present invention that with the painted conventional Al/Zn-based alloy coated test panels.
(78) The photographs of the test panels and the images of the corrosion fronts in
(79) The photographs of the test panels in
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(81) Finally, the applicant found in microstructural analysis of examples of Al—Zn—Si—Mg coatings in accordance with the present invention that the microstructure includes Mg.sub.2Si phase particles of a particular morphology in the interdendritic channels of Zn-rich eutectic phase mixture that are between dendrites of Al-rich alpha phase and this morphology is important in improving the corrosion resistance of the coatings, as discussed above. The applicant found that the size and distribution of the Mg.sub.2Si phase particles are also important factors contributing to the improved corrosion performance of the Al—Zn—Si—Mg coatings in accordance with the present invention. The applicant also found that desirable morphology, size and distribution of Mg.sub.2Si phase particles were possible by selection of coating compositions and control of cooling rates during coating solidification.
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(83) In the planar image of
(84) In the 3-dimensional image of
(85) Many modifications may be made to the present invention described above without departing from the spirit and scope of the invention.