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EP3500689A1 - Aluminium anodisé de couleur gris foncé - Google Patents

Aluminium anodisé de couleur gris foncé

Info

Publication number
EP3500689A1
EP3500689A1 EP17758674.0A EP17758674A EP3500689A1 EP 3500689 A1 EP3500689 A1 EP 3500689A1 EP 17758674 A EP17758674 A EP 17758674A EP 3500689 A1 EP3500689 A1 EP 3500689A1
Authority
EP
European Patent Office
Prior art keywords
aluminum
alloy
dispersoids
sheet
aluminum alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17758674.0A
Other languages
German (de)
English (en)
Other versions
EP3500689B1 (fr
Inventor
DaeHoon KANG
Martin Frank
Simon Barker
Devesh Mathur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novelis Inc Canada
Novelis Inc
Original Assignee
Novelis Inc Canada
Novelis Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novelis Inc Canada, Novelis Inc filed Critical Novelis Inc Canada
Publication of EP3500689A1 publication Critical patent/EP3500689A1/fr
Application granted granted Critical
Publication of EP3500689B1 publication Critical patent/EP3500689B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/14—Producing integrally coloured layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • anodized aluminum alloy sheets and, in particular, dark gray colored anodized aluminum alloy sheets.
  • a dark gray color is a desirable property in certain anodized aluminum products, such as anodized quality (“AQ”) architectural sheets.
  • An anodization process is an electrochemical process that converts the aluminum alloy surface to aluminum oxide. Because the aluminum oxide forms in place on the surface, it is fully integrated with the underlying aluminum substrate.
  • the surface oxide layer produced by an anodization process is a highly ordered structure that, when pure, can be clear and colorless so that the anodized sheet has a shiny, light gray color.
  • the surface oxide layer is also porous and susceptible to additional colorization by treatment subsequent to and/or separate from the anodization process.
  • Conventional colored anodized alloys are colored by additional absorptive or electrolytic coloration processes, which increase production costs for colored alloys relative to alloys that are not colored.
  • the alloys have economic and environmental advantages over conventional anodized aluminum alloys that require a separate coloration process in order to achieve a desired color.
  • aluminum alloys that have a natural dark gray color when anodized are described herein.
  • the aluminum alloys include up to 0.40 wt. % Fe, up to 0.25 wt. % Si, up to 0.2 wt. % Cr, 2.0 wt. % to 3.2 wt. % Mg, 0.8 wt. % to 1.5 wt. % Mn, up to 0.1 wt. % Cu, up to 0.05 wt.% Zn, up to 0.05 wt.% Ti, and up to 0.15 wt.
  • the aluminum alloys include up to 0.05 wt. % to 0.2 wt. % Fe, 0.03 wt. % to 0.1 wt. % Si, up to 0.05 wt. % Cr, 2.5 wt. % to 3.2 wt. % Mg, 0.8 wt. % to 1.3 wt. % Mn, up to 0.05 wt. % Cu, up to 0.05 wt. % Zn, up to 0.05 wt. % Ti, and up to 0.15 wt.
  • the method comprises casting an aluminum alloy to form an ingot; homogenizing the ingot to form a homogenized ingot; hot rolling the homogenized ingot to produce a hot rolled intermediate product; cold rolling the hot rolled intermediate product to produce a cold rolled intermediate product; interannealing the cold rolled intermediate product to produce an interannealed product; cold rolling the interannealed product to produce a cold rolled sheet; and annealing the cold rolled sheet to form an annealed sheet comprising dispersoids, wherein the alloy is a 2xxx, 3xxx, 5xxx, or 7xxx series alloy.
  • FIG. 1A is a scanning transmission electron microscopy (STEM) image of dispersoids in a comparative aluminum alloy.
  • FIG.1B is a STEM image of dispersoids in a comparative aluminum alloy.
  • FIG. 1C is a STEM image of dispersoids in an aluminum alloy with a dark anodized color, as described herein.
  • FIG.2A is a high-resolution scanning electron microscopy (SEM) image of dispersoids in a comparative anodized aluminum alloy.
  • FIG. 2B is a high-resolution SEM image of dispersoids in a comparative anodized aluminum alloy.
  • FIG. 1A is a scanning transmission electron microscopy (STEM) image of dispersoids in a comparative aluminum alloy.
  • FIG.1B is a STEM image of dispersoids in a comparative aluminum alloy.
  • FIG. 1C is a STEM image of dispersoids in an aluminum alloy with a dark anodized color, as described herein.
  • FIG.2A is
  • FIG.3A is a phase diagram of phases in a comparative alloy.
  • FIG.3B is a phase diagram of phases in a comparative alloy.
  • FIG. 3C is a phase diagram of phases in an anodized aluminum alloy with natural dark anodized color.
  • alloys and processes providing colorized anodized substrates designed based on in-depth microstructure and metallurgical analysis.
  • an anodized layer on a conventional aluminum alloy substrate is almost transparent and the anodized substrate shows a deep and shiny light gray metallic color due to light reflectance from both the surface of the anodized layer and the surface of the base metal.
  • fine intermetallic particle dispersoids (alternately called precipitates) inside the normally-transparent anodized oxide layers of the anodized alloys described herein affect the color of the anodized material by interrupting light as it passes through the anodized layer before it can reach the surface of the base metal.
  • anodized aluminum sheet as described herein has a dark gray color.
  • the color of the anodized aluminum sheet can be quantified by colorimetry measurement by CIE lab 1931 standard and/or ASTM E313-15 (2015).
  • the anodized aluminum sheet has an L* value lower than 60, lower than 55, or lower than 50, as measured by CIE lab 1931 standard.
  • the anodized sheet has a white balance of lower than 35, lower than 30, or lower than 25, as measured by ASTM E313-15 (2015).
  • the meaning of “a,”“an,” and“the” includes singular and plural references unless the context clearly dictates otherwise.
  • the meaning of“room temperature” can include a temperature of from about 15 °C to about 30 °C, for example about 15 °C, about 16 °C, about 17 °C, about 18 °C, about 19 °C, about 20 °C, about 21 °C, about 22 °C, about 23 °C, about 24 °C, about 25 °C, about 26 °C, about 27 °C, about 28 °C, about 29 °C, or about 30 °C.
  • the dark anodized aluminum alloy sheets described herein can be prepared from any suitable aluminum alloy.
  • the final anodized quality and color will vary depending on the alloy composition.
  • the aluminum alloy used in the methods described herein is a 2xxx, 3xxx, 5xxx, or 7xxx series alloy.
  • Non-limiting exemplary AA2xxx series alloys include AA2001, A2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012, AA2013, AA2014, AA2014A, AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA2319, AA2419, AA2519, AA2021, AA2022, AA2023, AA2024, AA2024A, AA2124, AA2224, AA2224A, AA2324, AA2424, AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA20
  • Non-limiting exemplary AA3xxx series alloys for use as the aluminum alloy product can include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, and AA3065.
  • Non-limiting exemplary AA5xxx series alloys include AA5182, AA5183, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA
  • Non-limiting exemplary AA7xxx series alloys include AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7122, AA7023, AA7026, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040,
  • the aluminum alloys useful for providing dark anodized aluminum alloy sheets as described herein include those having compositions with up to about 0.40 wt. % Fe, up to about 0.25 wt. % Si, up to about 0.2 wt. % Cr, about 2.0 wt. % to about 3.2 wt. % Mg, about 0.8 wt. % to about 1.5 wt. % Mn, up to about 0.1 wt. % Cu, up to about 0.05 wt. % Zn, up to about 0.05 wt. % Ti, and up to about 0.15 wt. % total impurities, with the remainder as Al.
  • the aluminum alloy for use as anodized aluminum having a dark gray color includes up to about 0.05 wt. % to about 0.20 wt. % Fe, about 0.03 wt. % to about 0.1 wt. % Si, up to about 0.05 wt. % Cr, about 2.5 wt. % to about 3.2 wt. % Mg, about 0.8 wt.% to about 1.3 wt. % Mn, up to about 0.05 wt. % Cu, up to about 0.05 wt.% Zn, up to about 0.05 wt.% Ti, and up to about 0.15 wt. % total impurities, with the remainder as Al.
  • the aluminum alloy includes up to about 0.30 wt. % Fe, up to about 0.13 wt. % Si, up to about 0.07 wt. % Cr, from about 2.0 wt. % to about 2.75 wt. % Mg, from about 0.80 wt. % to about 1.5 wt. % Mn, up to about 0.05 wt. % Cu, up to about 0.05 wt.% Zn, up to about 0.05 wt.% Ti, and up to 0.15 wt. % impurities, with the remainder as Al.
  • the aluminum alloy includes about 0.1 wt. % Fe, about 0.06 wt. % Si, about 0.005 wt.
  • an aluminum sheet includes any one of the aluminum alloys described herein.
  • the aluminum alloy includes iron (Fe) in an amount of from 0 % to 0.4 % (e.g., from about to 0.05 wt. % to about 0.20 wt. %) based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, about 0.05 %, about 0.06 %, about 0.07 %, about 0.08 %, about 0.09 %, about 0.1 %, about 0.11 %, about 0.12 %, about 0.13 %, about 0.14 %, about 0.15 %, about 0.16 %, about 0.17 %, about 0.18 %, about 0.19 %, about 0.2 %, about 0.21 %, about 0.22 %, about 0.23 %, about 0.24 %, about 0.25 %, about 0.26 %, about 0.27 %, about 0.28 %, about 0.29 %, about 0.3 %, about 0.31 %, about
  • the aluminum alloy includes silicon (Si) in an amount of from 0 % to about 0.25% (e.g., from about 0.03 % to about 0.1 %) based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, about 0.05 %, about 0.06 %, about 0.07 %, about 0.08 %, about 0.09 %, about 0.1 %, about 0.11 %, about 0.12 %, about 0.13 %, about 0.14 %, about 0.15 %, about 0.16 %, about 0.17 %, about 0.18 %, about 0.19 %, about 0.2 %, about 0.21 %, about 0.22 %, about 0.23 %, about 0.24 %, or about 0.25 % Si.
  • the aluminum alloy includes chromium (Cr) in an amount of from 0 % to about 0.2% (e.g., from about 0.001 % to about 0.15 %) based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, about 0.05 %, about 0.06 %, about 0.07 %, about 0.08 %, about 0.09 %, about 0.1 %, about 0.11 %, about 0.12 %, about 0.13 %, about 0.14 %, about 0.15 %, about 0.16 %, about 0.17 %, about 0.18 %, about 0.19 %, or about 0.2 % Cr.
  • the aluminum alloy includes magnesium (Mg) in an amount of from about 2.0 % to about 3.2 % (e.g., from about 2.5 % to about 3.2 %) based on the total weight of the alloy.
  • the alloy can include about 2.0 %, about 2.1 %, about 2.2 %, about 2.3 %, about 2.4 %, about 2.5 %, about 2.6 %, about 2.7 %, about 2.75 %, about 2.8 %, about 2.9 %, about 3.0 %, about 3.1 %, or about 3.2 % Mg.
  • the aluminum alloy includes manganese (Mn) in an amount of from about 0.8 % to about 1.5 % (e.g., from about 0.8 % to about 1.3 %) based on the total weight of the alloy.
  • the alloy can include about 0.1 %, about 0.2 %, about 0.3 %, about 0.4 %, about 0.5 %, about 0.6 %, about 0.7 %, about 0.8 %, about 0.9 %, about 1.0 %, about 1.1 %, about 1.2 %, or about 1.3 % Mn. All expressed in wt. %.
  • the aluminum alloy includes copper (Cu) in an amount of from 0 % to about 0.1 % (e.g., from 0 % to about 0.05 %) based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, about 0.05 %, about 0.06 %, about 0.07 %, about 0.08 %, about 0.09 %, or about 0.1 % Cu.
  • the aluminum alloy includes zinc (Zn) in an amount of from 0 % to about 0.05 % based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, or about 0.05 % Zn.
  • the aluminum alloy includes titanium (Ti) in an amount of from 0 % to about 0.05 % based on the total weight of the alloy.
  • the alloy can include about 0.001 %, about 0.002 %, about 0.003 %, about 0.004 %, about 0.005 %, about 0.006 %, about 0.007 %, about 0.008 %, about 0.009 %, about 0.01 %, about 0.02 %, about 0.03 %, about 0.04 %, or about 0.05 % Ti.
  • the alloy compositions described herein can further include other minor elements, sometimes referred to as impurities, in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below each.
  • impurities may include, but are not limited to, V, Zr, Ni, Sn, Ga, Ca, or combinations thereof.
  • V, Zr, Ni, Sn, Ga, or Ca may be present in alloys in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below. In some cases, the sum of all impurities does not exceed 0.15% (e.g., 0.10%). All expressed in wt. %. The remaining percentage of the alloy is aluminum.
  • the alloys described herein can be prepared as sheets and can be anodized.
  • the surface oxide layer produced by an anodization process of a conventional alloy is a highly ordered structure that, when pure, can be clear and colorless.
  • the alloys described herein are designed to form fine intermetallic particles (e.g., dispersoids or precipitates) in the substrate that are maintained inside the oxide layer formed during the anodization process.
  • the intermetallic particles include two or more elements, for example, two or more of Al, Fe, Mn, Si, Cu, Ti, Zr, Cr, and/or Mg.
  • the intermetallic particles include, but are not limited to, Al x (Fe,Mn), Al 3 Fe, Al 12 (Fe,Mn) 3 Si, Al 7 Cu 2 Fe, Al 20 Cu 2 Mn 3 , Al 3 Ti, Al 2 Cu, Al(Fe,Mn) 2 Si 3 , Al 3 Zr, Al 7 Cr, Al x (Mn,Fe), Al 12 (Mn,Fe) 3 Si, Al 3 ,Ni, Mg 2 Si, MgZn 3 , Mg 2 Al 3 , Al 32 Zn 49 , Al 2 CuMg, and Al 6 Mn. While many intermetallic particles contain aluminum, there also exist intermetallic particles that do not contain aluminum, such as Mg 2 Si.
  • the alloys described herein include various weight percent of phases Al x (Fe,Mn), Al 12 (Fe,Mn) 3 Si, and Al 6 Mn, Mg 2 Si.
  • Al x (Fe,Mn) indicates that the element can be Fe or Mn, or a mixture of the two.
  • the notation (Fe,Mn) indicates that the particle contains more of the element Fe than the element Mn, while the notation (Fe,Mn) indicates that the particle contains more of the element Mn than the element Fe.
  • the weight percent of each phase differs at different annealing temperatures used in the methods for preparing the aluminum alloy sheets, as detailed below.
  • An alloy having a higher weight percent of Al x (Fe,Mn) and/or Al 12 (Fe,Mn) 3 Si particles will have a darker natural anodized color.
  • the aluminum alloy includes at least 1.5 weight % Al x (Fe,Mn) and/or Al 12 (Fe,Mn) 3 Si at 400 oC (e.g., at least 1.0 %, at least 1.25 %, at least 1.5 %, or at least 1.75 %, all weight %).
  • the aluminum alloy includes at least 2.0 weight % Al x (Fe,Mn) and/or Al 12 (Fe,Mn) 3 Si at 500 oC (e.g., at least 2.0 %, at least 2.2 %, or at least 2.4 %, all weight %).
  • the aluminum sheet having a dark gray color includes dispersoids at a density of at least 1 dispersoid per 25 square micrometers (e.g., at least 1 dispersoid per 25 square micrometers, at least 2 dispersoids per 25 square micrometers, at least 4 dispersoids per 25 square micrometers, at least 10 dispersoids per 25 square micrometers, or at least 20 dispersoids per 25 square micrometers).
  • the dispersoids have an average dimension of greater than 50 nanometers in any direction.
  • “any direction” means height, width, or depth.
  • the dispersoids can have an average particle dimension of greater than 50 nanometers, greater than 100 nanometers, greater than 200 nanometers, or greater than 300 nanometers.
  • the dispersoids include one or more of Al, Fe, Mn, Si, Cu, Ti, Zr, Cr, Ni, Zn, and/or Mg.
  • the dispersoids include Al-Mn-Fe-Si dispersoids.
  • the dispersoids include one or more of Al 3 Fe, Al 12 (Fe,Mn) 3 Si, Al 20 Cu 2 Mn 3 , Al(Fe,Mn) 2 Si 3, Al 3 Zr, Al 7 Cr, Al 12 (Mn,Fe) 3 Si, Mg 2 Si, Al 2 CuMg, and Al 6 Mn.
  • the dispersoids include one or more of Al 3 Fe, Al x (Fe,Mn), Al 3 Fe, Al 12 (Fe,Mn) 3 Si, Al 7 Cu 2 Fe, Al 20 Cu 2 Mn 3 , Al 3 Ti, Al 2 Cu, Al(Fe,Mn) 2 Si 3 , Al 3 Zr, Al 7 Cr, Al x (Mn,Fe), Al 12 (Mn,Fe) 3 Si, Al 3 ,Ni, Mg 2 Si, MgZn 3 , Mg 2 Al 3 , Al 32 Zn 49 , Al 2 CuMg, and Al 6 Mn.
  • the aluminum sheet has a grain size of from 10 microns to 50 microns.
  • the aluminum sheet can have a grain size of from 15 microns to 45 microns, from 15 microns to 40 microns, or from 20 microns to 40 microns.
  • the method includes casting the aluminum; homogenizing the aluminum; hot rolling the homogenized aluminum to produce a hot rolled intermediate product; cold rolling the hot rolled intermediate product to produce a cold rolled intermediate product; interannealing the cold rolled intermediate product to produce an interannealed product; cold rolling the interannealed product to produce a cold rolled sheet; and annealing the cold rolled sheet to form an annealed sheet.
  • the method further includes etching the annealed aluminum sheets (e.g., in an acid or base bath) and anodizing the annealed aluminum sheets.
  • the alloys described herein can be cast into ingots using a direct chill (DC) process.
  • the resulting ingots can optionally be scalped.
  • the alloys described herein can be cast in a continuous casting (CC) process.
  • the cast product can then be subjected to further processing steps.
  • the processing steps further include a homogenization step, a hot rolling step, a cold rolling step, an optional interannealing step, a cold rolling step, and a final annealing step.
  • the processing steps described below exemplify processing steps used for an ingot as prepared from a DC process.
  • the homogenization step described herein can be a single homogenization step or a two-step homogenization process.
  • the first homogenization step dissolves metastable phases into the matrix and minimizes microstructural inhomogeneity.
  • An ingot is heated to attain a peak metal temperature of 500-550 °C for about 2-24 hours.
  • the ingot is heated to attain a peak metal temperature ranging from about 510 °C to about 540 °C, from about 515 °C to about 535 °C, or from about 520 °C to about 530 °C.
  • the heating rate to reach the peak metal temperature can be from about 30 °C per hour to about 100 °C per hour.
  • the ingot is then allowed to soak (i.e., maintained at the indicated temperature) for a period of time during the first homogenization stage.
  • the ingot is allowed to soak for up to 5 hours (e.g., up to 1 hour, up to 2 hours, up to 3 hours, up to 4 hours, inclusively).
  • the ingot can be soaked at a temperature of about 515 °C, about 525 °C, about 540 °C, or about 550 °C for 1 hour to 5 hours (e.g., 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours).
  • the ingot temperature is decreased to a temperature of from about 480 °C to 550 °C prior to subsequent processing.
  • the ingot temperature is decreased to a temperature of from about 450 °C to 480 °C prior to subsequent processing.
  • the ingot in the second stage the ingot can be cooled to a temperature of about 450 °C, about 460 °C, about 470 °C, or about 480 °C and allowed to soak for a period of time.
  • the ingot is allowed to soak at the indicated temperature for up to eight hours (e.g., from 30 minutes to eight hours, inclusively).
  • the ingot can be soaked at a temperature of about 450 °C, of about 460 °C, of about 470 °C, or of about 480 °C for 30 minutes to 8 hours.
  • a hot rolling step can be performed.
  • the hot rolling step can include a hot reversing mill operation and/or a hot tandem mill operation.
  • the hot rolling step can be performed at a temperature ranging from about 250 °C to about 450 °C (e.g., from about 300 °C to about 400 °C or from about 350 °C to about 400 °C).
  • the ingots can be hot rolled to a thickness of 10 mm gauge or less (e.g., from 3 mm to 8 mm gauge).
  • the ingots can be hot rolled to a 8 mm gauge or less, 7 mm gauge or less, 6 mm gauge or less, 5 mm gauge or less, 4 mm gauge or less, or 3 mm gauge or less.
  • the hot rolling step can be performed for a period of up to one hour.
  • the aluminum sheet is coiled to produce a hot rolled coil.
  • the hot rolled coil can be uncoiled into a hot rolled sheet which can then undergo a cold rolling step.
  • the hot rolled sheet temperature can be reduced to a temperature ranging from about 20 °C to about 200 °C (e.g., from about 120 °C to about 200 °C).
  • the cold rolling step can be performed for a period of time to result in a final gauge thickness of from about 1.0 mm to about 3 mm, or about 2.3 mm.
  • the cold rolling step can be performed for a period of up to about 1 hour (e.g., from about 10 minutes to about 30 minutes) and the sheet can be coiled to produce a cold rolled coil.
  • the cold rolled coil can then undergo an interannealing step.
  • the interannealing step can include heating the coil to a peak metal temperature of from about 300 °C to about 400 °C (e.g., about 300 °C, 305 °C, 310 °C, 315 °C, 320 °C, 325 °C, 330 °C, 335 °C, 340 °C, 345 °C, 350 °C, 355 °C, 360 °C, 365 °C, 370 °C, 375 °C, 380 °C, 385 °C, 390 °C, 395 °C, or 400 °C).
  • a peak metal temperature of from about 300 °C to about 400 °C (e.g., about 300 °C, 305 °C, 310 °C, 315 °C, 320 °C, 325 °C, 330 °C, 335 °C, 340 °C, 345 °C, 350 °C, 355
  • the heating rate for the interannealing step can be from about 20 °C per minute to about 100 °C per minute (e.g., about 40 °C per minute, about 50 °C per minute, about 60 °C per minute, or about 80 °C per minute).
  • the interannealing step can be performed for a period of about 2 hours or less (e.g., about 1 hour or less).
  • the interannealing step can be performed for a period of from about 30 minutes to about 50 minutes.
  • the interannealing step can optionally be followed by another cold rolling step.
  • the cold rolling step can be performed for a period of time to result in a final gauge thickness between about 0.5 mm and about 2 mm, between about 0.75 and about 1.75 mm, between about 1 and about 1.5 mm, or about 1.27 mm.
  • the cold rolling step can be performed for a period of up to about 1 hour (e.g., from about 10 minutes to about 30 minutes).
  • the cold rolled coil can then undergo an annealing step.
  • the annealing step can include heating the cold rolled coil to a peak metal temperature of from about 180 °C to about 350 °C.
  • the heating rate for the annealing step can be from about 10 °C per hour to about 100 °C per hour.
  • the annealing step can be performed for a period of up to 48 hours or less (e.g., 1 hour or less). For example, the annealing step can be performed for a period of from 30 minutes to 50 minutes.
  • the aluminum sheets can be etched. Any known etching process may be used, including alkaline etching or acidic etching. As an example, an alkaline etching process can be performed with sodium hydroxide (e.g., a 10% aqueous sodium hydroxide solution) followed by a desmutting process. As another example, an acidic etching process can be performed with phosphoric acid, sulfuric acid, or a combination of these.
  • the acidic etching process can be performed using 75% phosphoric acid and 25% sulfuric acid at an elevated temperature.
  • an elevated temperature refers to a temperature higher than room temperature (e.g., greater than 40 °C, greater than 50 °C, greater than 60 °C, greater than 70 °C, greater than 80 °C, or greater than 90 °C, such as 99 oC).
  • room temperature e.g., greater than 40 °C, greater than 50 °C, greater than 60 °C, greater than 70 °C, greater than 80 °C, or greater than 90 °C, such as 99 oC.
  • the bulk aluminum matrix and intermetallic particles/dispersoids are dissolved.
  • the degree and uniformity of etched surface can be varied.
  • the aluminum sheets described herein are anodized.
  • the aluminum sheets described herein are anodized by placing the aluminum in an electrolytic solution and passing a direct current through the solution.
  • the electrolytic solution is an acidic solution, such as, but not limited to, a solution including hydrochloric acid, sulfuric acid, chromic acid, phosphoric acid, and/or an organic acid.
  • Anodization creates an oxide surface layer on the aluminum alloy.
  • the aluminum sheet includes an oxide surface layer.
  • An inventive alloy sheet and three comparative alloy sheets having the compositions detailed in Table 1 were prepared.
  • the sheets were prepared by casting an ingot at approximately 650 o C, homogenizing the ingot at 525 o C for less than 1 hour soaking time, hot rolling the homogenized ingot for 10 minutes at 250-450 o C to produce a hot rolled intermediate product, and cold rolling the hot rolled intermediate product for 10 minutes at 150-180 o C to produce a cold rolled intermediate product.
  • Table 1 Alloy elemental compositions, with up to 0.15 weight % total impurities, the balance Aluminum.
  • FIG. 1A and FIG. 1B are STEM images of Comparative Alloy 1 and Comparative Alloy 2, respectively.
  • FIG. 1C is a STEM image of Alloy 4. Alloy 4 showed a much higher density of dispersoids than the comparative alloys. Alloy 3 had a lower density of dispersoids than Alloys 1 and 2, and thus is not pictured.
  • Thermodynamic modelling by Thermo-Calc software was used to calculate the equilibrium phase transformation behavior of Comparative Alloys 1-2 (see FIGs. 3A and 3B, respectively) and Alloy 4 (see FIG. 3C).
  • Equilibrium phases at each temperature of given alloy composition was calculated by CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) technique. Each line represents specific phase.
  • Line 1 liquid; line 2: Al matrix; line 3: Al 6 Mn; line 4: Al(Fe,Mn) 2 Si 3 ; line 5: Mg 2 Si; line 6: AlCuMn; line 7: AlCuMg; line 8: Al 8 Mg 5 ; line 9: Al 12 Mn.
  • Modeling results indicate that the amount of Al 6 Mn dispersoids (line 3) is the most in alloy 4 ( Figure 3C).
  • the inventive alloy’s higher Mn content relative to the comparative alloys results in a greater concentration of Al 6 Mn dispersoids in the inventive alloy oxide layer, which provides scattering of incoming light.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Continuous Casting (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Powder Metallurgy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne des alliages d'aluminium et des feuilles d'aluminium comprenant des alliages qui ont une couleur gris foncé naturelle lorsqu'ils sont anodisés. Les alliages ne nécessitent pas de processus de coloration électrolytique ou par absorption distinct du processus d'anodisation pour obtenir la coloration gris foncé. L'invention concerne également des procédés de fabrication de ces alliages d'aluminium.
EP17758674.0A 2016-08-17 2017-08-11 Aluminium anodisé de couleur gris foncé Active EP3500689B1 (fr)

Applications Claiming Priority (2)

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US201662375932P 2016-08-17 2016-08-17
PCT/US2017/046444 WO2018034960A1 (fr) 2016-08-17 2017-08-11 Aluminium anodisé de couleur gris foncé

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EP3875629A1 (fr) * 2020-03-03 2021-09-08 Elvalhalcor Hellenic Copper and Aluminium Industry S.A. Procédé et installation pour la production d'une tôle de boîte d'aluminium

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JP2640993B2 (ja) * 1990-06-11 1997-08-13 スカイアルミニウム株式会社 超塑性成形用アルミニウム合金圧延板
JP3200523B2 (ja) * 1994-10-11 2001-08-20 ワイケイケイ株式会社 グレー発色用時効硬化型アルミニウム合金押出形材及びその製造方法
RU2221891C1 (ru) * 2002-04-23 2004-01-20 Региональный общественный фонд содействия защите интеллектуальной собственности Сплав на основе алюминия, изделие из этого сплава и способ изготовления изделия
JP3958182B2 (ja) * 2002-10-15 2007-08-15 古河スカイ株式会社 後成形性良好なアルミニウム合金陽極酸化処理板
JP2004332002A (ja) * 2003-04-30 2004-11-25 Furukawa Sky Kk 透明潤滑樹脂被覆陽極酸化処理板
JP2006026938A (ja) * 2004-07-12 2006-02-02 Furukawa Sky Kk 成形加工性に優れる水溶性潤滑樹脂被覆陽極酸化処理板
JP2009209426A (ja) * 2008-03-05 2009-09-17 Sumitomo Light Metal Ind Ltd 筐体用アルミニウム合金材
JP5640399B2 (ja) * 2010-03-03 2014-12-17 日本軽金属株式会社 陽極酸化皮膜を備えたアルミニウム合金板およびその製造方法
ES2569664T3 (es) * 2012-08-28 2016-05-12 Hydro Aluminium Rolled Products Gmbh Aleación de aluminio resistente a la corrosión intercristalina
RU2544331C1 (ru) * 2014-01-23 2015-03-20 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Алюминиевый сплав
CN107406921A (zh) * 2015-03-13 2017-11-28 诺维尔里斯公司 用于高度塑形封装产品的铝合金及其制作方法
JP2019524989A (ja) * 2016-06-28 2019-09-05 ノベリス・インコーポレイテッドＮｏｖｅｌｉｓ Ｉｎｃ． 陽極酸化品質アルミニウム合金およびその関連製品ならびに方法

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BR112019002606B1 (pt) 2022-07-12
PL3500689T3 (pl) 2024-01-15
US20180051387A1 (en) 2018-02-22
BR112019002606A2 (pt) 2019-05-28
CN109642300A (zh) 2019-04-16
SA519401070B1 (ar) 2022-06-19
KR20190040007A (ko) 2019-04-16
AU2017312853B2 (en) 2019-09-19
CA3033962C (fr) 2021-01-26
ES2960834T3 (es) 2024-03-06
JP2019531404A (ja) 2019-10-31
HUE063474T2 (hu) 2024-01-28
AU2017312853A1 (en) 2019-03-07
WO2018034960A1 (fr) 2018-02-22
CN109642300B (zh) 2021-05-25
CA3033962A1 (fr) 2018-02-22
JP7149262B2 (ja) 2022-10-06
EP3500689B1 (fr) 2023-10-04
RU2717622C1 (ru) 2020-03-24
MX2019001837A (es) 2019-05-09

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