EP3500689B1 - Anodized aluminum with dark gray color - Google Patents

Anodized aluminum with dark gray color Download PDF

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Publication number
EP3500689B1
EP3500689B1 EP17758674.0A EP17758674A EP3500689B1 EP 3500689 B1 EP3500689 B1 EP 3500689B1 EP 17758674 A EP17758674 A EP 17758674A EP 3500689 B1 EP3500689 B1 EP 3500689B1
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Prior art keywords
aluminum
sheet
dispersoids
aluminum alloy
alloy
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German (de)
English (en)
French (fr)
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EP3500689A1 (en
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DaeHoon KANG
Martin Frank
Simon Barker
Devesh Mathur
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Novelis Inc Canada
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Novelis Inc Canada
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    • 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
    • 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
    • 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.
  • JP2009209426 A discloses an aluminum alloy for a housing comprising: 5000 type aluminum alloy having less than 0.05 wt% Cu and an anodized film and its production method.
  • aluminum alloys that have a dark gray color when anodized.
  • the alloys do not require any absorptive or electrolytic coloration process separate from the anodization process to achieve the dark gray coloration.
  • 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.
  • this invention provides an aluminum alloy as defined in claim 1 with preferred composition defined in depend claim 2.
  • this invention provides an aluminum sheet as defined in claim 3 with preferred embodiments defined in dependent claims 4-7.
  • this invention provides a method of preparing an aluminum sheet as defined in claim 8 with preferred embodiments defined in dependent claims 9 and 10.
  • Described herein are 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.
  • the number density of certain dispersoids inside the anodized layer is maximized. Those dispersoids give the anodized substrate a dark gray color without an additional coloring process.
  • the alloys and methods disclosed herein provide dark anodized sheets that can be prepared with significantly reduced processing and cost as compared to known dark anodized sheets.
  • the methods described herein eliminate conventional adsorptive or electrolytic coloration steps which are required in current production of dark colored anodized materials.
  • the methods described herein result in fewer byproducts and are more environmentally friendly than conventional methods of producing similarly colored products.
  • an 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).
  • Aluminum alloys are described herein in terms of their elemental composition in weight percentage (wt. %) based on the total weight of the alloy.
  • 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 aluminum alloys useful for providing dark anodized aluminum alloy sheets as described herein comprise 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. % impurities, with the remainder as Al.
  • the aluminum alloy includes 0.05 wt. % to 0.20 wt. % Fe, 0.03 wt. % to 0.1 wt.
  • the aluminum alloy includes up to 0.30 wt. % Fe, up to 0.13 wt. % Si, up to 0.07 wt. % Cr, from 2.0 wt. % to 2.75 wt. % Mg, from 0.80 wt. % to 1.5 wt.
  • the aluminum alloy includes 0.1 wt. % Fe, 0.06 wt. % Si, 0.005 wt. % Cr, 2.74 wt. % Mg, 1.13 wt. % Mn, 0.024 wt. % Cu, aout 0.005 wt.% Zn, 0.005 wt.% Ti, and up to 0.15 wt. % total impurities, with the remainder as Al.
  • the aluminum alloy includes iron (Fe) in an amount of from 0 % to 0.4 % (e.g., from to 0.05 wt. % to 0.20 wt. %) based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.1 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.2 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.
  • the aluminum alloy includes silicon (Si) in an amount of from 0 % to 0.25% (e.g., from 0.03 % to 0.1 %) based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.1 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.2 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, or 0.25 % Si. In some cases, Si is not present in the alloy (i.e., 0
  • the aluminum alloy includes chromium (Cr) in an amount of from 0 % to 0.2% (e.g., from 0.001 % to 0.15 %) based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.1 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, or 0.2 % Cr. In some cases, Cr is not present in the alloy (i.e., 0 %). All expressed in wt. %.
  • the aluminum alloy includes magnesium (Mg) in an amount of from 2.0 % to 3.2 % (e.g., from 2.5 % to 3.2 %) based on the total weight of the alloy.
  • the alloy can include 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.75 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, or 3.2 % Mg. All expressed in wt. %.
  • the aluminum alloy includes manganese (Mn) in an amount of from 0.8 % to 1.5 % (e.g., from 0.8 % to 1.3 %) based on the total weight of the alloy.
  • the alloy can include 0.8 %, 0.9 %, 1.0 %, 1.1 %, 1.2 %, or 1.3 % Mn. All expressed in wt. %.
  • the aluminum alloy includes copper (Cu) in an amount of from 0 % to 0.1 % (e.g., from 0 % to 0.05 %) based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, or 0.1 % Cu.
  • Cu is not present in the alloy (i.e., 0 %). All expressed in wt. %.
  • the aluminum alloy includes zinc (Zn) in an amount of from 0 % to 0.05 % based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, or 0.05 % Zn.
  • Zn is not present in the alloy (i.e., 0 %). All expressed in wt. %.
  • the aluminum alloy includes titanium (Ti) in an amount of 0 % to 0.05 % based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, or 0.05 % Ti. In some cases, Ti is not present in the alloy (i.e., 0 %). All expressed in wt. %.
  • 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.
  • 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 in contrast, 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 alloys comprise at least 1.5 weight percent intermetallic particles Al 12 (Mn,Fe) 3 Si, and/or Al 6 Mn having an average dimension of greater than 50 nm in any direction. While many intermetallic particles contain aluminum, there also exist intermetallic particles that do not contain aluminum, such as Mg 2 Si. The composition and properties of intermetallic particles are described further below.
  • 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.
  • the notation (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 ) (such as Al 6 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 6 Mn and/or Al 12 (Fe,Mn) 3 Si at 400 °C (e.g., at least 1.5 %, or at least 1.75 %, all weight %).
  • the aluminum alloy includes at least 2.0 weight % Al 6 Mn and/or Al 12 (Fe,Mn) 3 Si at 500 °C (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 additionally include one or more of Al 3 Fe, Al 20 Cu 2 Mn 3 , Al(Fe,Mn) 2 Si 3 , Al 3 Zr, Al 7 Cr, Mg 2 Si, and AhCuMg.
  • 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.
  • Methods of producing an aluminum sheet comprise: casting an aluminum alloy to form an ingot; homogenizing the ingot in a two-step homogenization process to form a homogenized ingot, wherein a first homogenization step is heating to attain a peak metal temperature of 500-550°C for 2-24h and soaking for a period of time, and a second homogenization step is decreasing the temperature to a temperature of from 480-550°C; 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 aluminum sheet comprising dispersoids having an average dimension of greater than 50 nanometers in any direction.
  • the method further includes etching the annealed aluminum sheets (e.g., in an acid or base bath) and anodizing
  • 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 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. In some examples, 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. In some examples, the ingot is allowed to soak at the indicated temperature for up to eight hours (e.g., from 30 minutes to eight hours, inclusively). For example, 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.
  • 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 undergoes 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 undergoes 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).
  • 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 is 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 then undergoes 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 4.8 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.
  • an alkaline etching process can be performed with sodium hydroxide (e.g., a 10% aqueous sodium hydroxide solution) followed by a desmutting process.
  • 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 °C).
  • 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 °C.
  • 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 °C.
  • 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.
  • the materials described herein are particularly useful in architectural quality applications as well as other decorative applications, such as decorative panels, street signs, appliances, furniture, jewelry, artwork, boating and automotive components, and even consumer electronics where high quality dark gray color in anodized sheets are required by customers.
  • 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 °C, homogenizing the ingot at 525 °C for less than 1 hour soaking time, hot rolling the homogenized ingot for 10 minutes at 250-450 °C to produce a hot rolled intermediate product, and cold rolling the hot rolled intermediate product for 10 minutes at 150-180 °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 Treatment Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Laminated Bodies (AREA)
EP17758674.0A 2016-08-17 2017-08-11 Anodized aluminum with dark gray color Active EP3500689B1 (en)

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US201662375932P 2016-08-17 2016-08-17
PCT/US2017/046444 WO2018034960A1 (en) 2016-08-17 2017-08-11 Anodized aluminum with dark gray color

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EP3875629A1 (en) * 2020-03-03 2021-09-08 Elvalhalcor Hellenic Copper and Aluminium Industry S.A. Method and installation for producing aluminum can sheet
JP7439632B2 (ja) 2020-04-20 2024-02-28 マツダ株式会社 車両の前部車体構造

Citations (1)

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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

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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
JP4218635B2 (ja) 2004-12-17 2009-02-04 パナソニック株式会社 磁性材の製造方法およびアンテナ装置
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
ES2734736T3 (es) * 2015-03-13 2019-12-11 Novelis Inc Aleaciones de aluminio para productos de envasado altamente conformados y métodos de fabricación de las mismas
WO2018005442A1 (en) * 2016-06-28 2018-01-04 Novelis Inc. Anodized-quality aluminum alloys and related products and methods

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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BR112019002606B1 (pt) 2022-07-12
JP7149262B2 (ja) 2022-10-06
WO2018034960A1 (en) 2018-02-22
JP2019531404A (ja) 2019-10-31
CN109642300A (zh) 2019-04-16
CA3033962C (en) 2021-01-26
MX2019001837A (es) 2019-05-09
SA519401070B1 (ar) 2022-06-19
ES2960834T3 (es) 2024-03-06
CN109642300B (zh) 2021-05-25
AU2017312853B2 (en) 2019-09-19
CA3033962A1 (en) 2018-02-22
EP3500689A1 (en) 2019-06-26
KR20190040007A (ko) 2019-04-16
AU2017312853A1 (en) 2019-03-07
HUE063474T2 (hu) 2024-01-28
RU2717622C1 (ru) 2020-03-24
BR112019002606A2 (pt) 2019-05-28
PL3500689T3 (pl) 2024-01-15
US20180051387A1 (en) 2018-02-22

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