Aluminum alloys and coated aluminum alloys with high corrosion resistance and methods of making same

Abstract

The invention relates to an aluminum alloy and a coated aluminum alloy with high corrosion resistance and a manufacturing method thereof. Provided herein are novel aluminum alloys comprising Ca, Mg, and / or Zn and novel coated aluminum alloys comprising a surface layer (e.g., a coating), such as a cladding layer, that can be used in aluminum alloy products, the surface layer comprising Ca, Mn, Zn, and / or Ni. Methods of making these aluminum alloys, coated aluminum alloys and clad layers and clad products are also provided. These alloys, coating alloys, cladding layers, and products have a combination of strength and other critical properties, such as corrosion resistance, formability, and coating line pre-treatment suitability. The materials may be used in a variety of applications, including automotive, transport and electronic applications.

Description

[0001] This application is a divisional application of the parent application No. 202180009981.4. The application date of the parent application is January 15, 2021; the name of the invention is "Aluminum alloy and coated aluminum alloy with high corrosion resistance and method for manufacturing the same".

[0002] priority

[0003] This application claims priority to and the benefit of U.S. Provisional Application Serial No. 62 / 963,904, filed on January 21, 2020, which is incorporated herein by reference in its entirety. Technical Field

[0004] The present disclosure relates to novel aluminum alloys, novel aluminum alloy claddings, novel surface layers (e.g., coatings) for aluminum alloys, and products made from these novel aluminum alloys, novel aluminum alloy claddings, and novel surface layers. The present disclosure also relates to methods for making novel aluminum alloys, novel aluminum alloy claddings, novel surface layers, and products. The aluminum alloy claddings and products, in addition to having good strength and formability, also exhibit high corrosion resistance and excellent paint line pretreatment suitability. Background Art

[0005] In order to be used in various applications, such as in the production of automotive parts, aluminum alloy products must provide a good combination of properties, especially when compared with alternatives. Available aluminum alloy products, such as clad products or coated aluminum alloy products, provide good formability and mechanical properties, as well as other key attributes, such as corrosion resistance and high paint line pretreatment suitability. Current aluminum alloy products can provide some but not all of these properties. For example, previously known alloys can provide good formability and mechanical properties, as well as sufficient paint line pretreatment suitability, but limited corrosion resistance. Some previously known alloys can provide good formability, but may be affected by low strength and / or paint line pretreatment suitability. Summary of the invention

[0006] The term "embodiment" and similar terms are intended to refer broadly to all subject matter of the present disclosure and the appended claims. Statements containing these terms should not be understood to limit the subject matter described herein, or to limit the meaning or scope of the appended claims. The embodiments of the present disclosure covered by this document are defined by the appended claims rather than by this disclosure. This disclosure is a high-level overview of various aspects of the present disclosure and introduces some concepts that are further described in the following detailed description section. This disclosure is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used to determine the scope of the claimed subject matter in isolation. The subject matter should be understood by reference to the entire specification of the present disclosure, any or all drawings, and the appropriate portions of each claim.

[0007] Provided herein are novel aluminum alloys, novel surface layers (e.g., coatings) for aluminum alloys, coated aluminum alloy products made from these novel coatings, and novel clad products made from these novel aluminum alloys and novel coated aluminum alloys, and methods for making clad aluminum alloy layers, clad products, and coated aluminum alloy products. These aluminum alloys, clad aluminum alloy layers, coated aluminum alloys, clad products, and coated aluminum alloy products have unexpected strength and a combination of other key attributes, such as corrosion resistance, formability, and good coating line pretreatment suitability.

[0008] In one embodiment, the novel aluminum alloy comprises calcium (Ca) and zinc (Zn). In another embodiment, the novel aluminum alloy may comprise magnesium (Mg) and Zn. In yet another embodiment, the novel aluminum alloy may comprise Ca, Mg and Zn. In some aspects, the aluminum alloy described herein may be used as a clad aluminum alloy layer and comprise Ca and Zn. In some aspects, the aluminum alloy described herein may be used as a clad aluminum alloy layer and comprise Mg and Zn. In some aspects, the aluminum alloy described herein may be used as a clad aluminum alloy layer and comprise Ca, Mg and Zn. As described herein, the clad aluminum alloy layer achieves excellent surface properties.

[0009] In another embodiment, the novel coated aluminum alloy product includes a surface layer (e.g., a coating) comprising Mg, Ca, Zn, nickel (Ni), or a combination thereof. The surface layer may be positioned on an aluminum alloy substrate. The Mg, Ca, Zn, Ni, or a combination thereof may be in a form wherein the Mg, Ca, Zn, and / or Ni may be used to inhibit corrosion of the aluminum alloy substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a graph of coverage results of filiform corrosion testing of clad aluminum alloy layers.

[0011] Figure 2is a graph showing the average filament length results of a filiform corrosion test of a clad aluminum alloy layer.

[0012] Figure 3 is a graph of coverage results of filiform corrosion testing of clad aluminum alloy layers.

[0013] Figure 4 is a graph of the average corrosion wire length results of the filiform corrosion test of the clad aluminum alloy layer.

[0014] Figure 5 is a micrograph showing the microstructure of the clad aluminum alloy layer after filiform corrosion testing.

[0015] Figure 6 is a micrograph showing the microstructure of the clad aluminum alloy layer after filiform corrosion testing.

[0016] Figure 7 It is a digital image showing the phosphatability results of the coated aluminum alloy layer.

[0017] Figure 8 is a graph of average and maximum corrosion wire length results from filiform corrosion testing of aluminum alloys.

[0018] Fig. 9 is a graph of coverage results of filiform corrosion testing of aluminum alloy. DETAILED DESCRIPTION

[0019] New aluminum alloys, new surface layers (e.g., coatings) for aluminum alloys, coated aluminum alloy products made from these new coatings, and new clad products made from these new aluminum alloys and new coated aluminum alloys, and methods of making clad aluminum alloy layers, clad products, and coated aluminum alloy products are described. These aluminum alloys, clad aluminum alloy layers, coated aluminum alloys, clad products, and coated aluminum alloy products have unexpected combinations of strength and other key properties, such as corrosion resistance, formability, and good paint line pretreatment suitability.

[0020] Definition and Description:

[0021] As used herein, the terms "invention," "the invention," "this invention," and "present invention" are intended to broadly refer to all subject matter of this patent application and the appended claims. Statements containing these terms should not be construed as limiting the subject matter described herein, or limiting the meaning or scope of the appended patent claims.

[0022] In this specification, reference is made to alloys identified by AA numbers and other related names, such as "Series" or "7xxx". For information on the numbering system most commonly used to name and identify aluminum and its alloys, see "International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys" or "Registration Record of Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot" published by The Aluminum Association.

[0023] As used herein, a plate generally has a thickness greater than about 15 mm. For example, a plate may refer to an aluminum product having a thickness greater than 15 mm, greater than 20 mm, greater than 25 mm, greater than 30 mm, greater than 35 mm, greater than 40 mm, greater than 45 mm, greater than 50 mm, or greater than 100 mm.

[0024] As used herein, the thickness of the satt board (also referred to as sheet board) is generally about 4 mm to about 15 mm. For example, the thickness of the satt board can be 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm or 15 mm.

[0025] As used herein, sheet generally refers to an aluminum product having a thickness of less than about 4 mm. For example, the sheet can have a thickness of less than 4 mm, less than 3 mm, less than 2 mm, less than 1 mm, less than 0.5 mm, less than 0.3 mm, or less than 0.1 mm.

[0026] Reference is made to alloy tempers or conditions in this application. For descriptions of the most commonly used alloy tempers, see "American National Standard (ANSI) H35 on Alloy and Temper Nomenclature System". The F condition or temper refers to the aluminum alloy as manufactured. The O condition or temper refers to the aluminum alloy after annealing. The Hxx condition or temper, also referred to herein as the H temper, refers to a non-heat-treatable aluminum alloy that has been subjected to or not subjected to a heat treatment (e.g., annealing) after cold rolling. Suitable H tempers include Hx1, Hx2, Hx3, Hx4, Hx5, Hx6, Hx7, Hx8, or Hx9 tempers. The T1 condition or temper refers to an aluminum alloy that has been cooled from hot working and naturally aged (e.g., at room temperature). The T2 condition or temper refers to an aluminum alloy that has been cooled from hot working, cold worked, and naturally aged. The T3 condition or temper refers to an aluminum alloy that has been solution heat treated, cold worked, and naturally aged. The T4 condition or temper refers to an aluminum alloy that has been solution heat treated and naturally aged. The T5 temper or temper refers to aluminum alloys that have been cooled from hot working and artificially aged (at elevated temperatures). The T6x temper or temper refers to aluminum alloys that have been solution heat treated and artificially aged. The T7 temper or temper refers to aluminum alloys that have been solution heat treated and artificially over-aged. The T8x temper or temper refers to aluminum alloys that have been solution heat treated, cold worked, and artificially aged. The T9 temper or temper refers to aluminum alloys that have been solution heat treated, artificially aged, and cold worked.

[0027] As used herein, terms such as "cast metal product", "cast product", "cast aluminum alloy product" are interchangeable and refer to products produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by using a twin-belt caster, a twin-roll caster, a block caster or any other continuous casting machine), electromagnetic casting, hot top casting or any other casting method.

[0028] As used herein, "room temperature" may include a temperature of about 15° C. to about 30° C., such as 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. As used herein, "ambient conditions" may include a temperature of approximately room temperature, a relative humidity of about 20% to about 100%, and an air pressure of about 975 millibars (mbar) to about 1050 mbar. For example, the relative humidity can be about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, about 101%, about 102%, about 103%, about 104%, about 105%, about 106%, about 107%, about 108%, about 109%, about 110%, about 111%, about 112%, about 113%, about 114%, about 115%, about 116%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, about 100%, about 101%, about 102%, about 103%, about 104%, about 105%, about 106%, about 107%, about 108%, about 109%, about 110%, about 111%, about 112%, about 113%, about 114%, about 115%, about 116%, about 117%, about 118%, about 119%, about 120%, about 121%, about 122%, about 123%, about 124%, about 125%, about 126%, about 127%, about 128%, about 129%, about 130%, about 131%, about 132%, about 133%, about 134%, about 135%, about 136%, about 137%, about 138%, about 139%, about 140%, about 141%, about 142%, about 143%, about 144%, about 145%, about 146%, about 147%, about 148%, about 149%, about 150%, about For example, the gas pressure may be about 975 mbar, about 980 mbar, about 985 mbar, about 990 mbar, about 995 mbar, about 1000 mbar, about 1005 mbar, about 1010 mbar, about 1015 mbar, about 1020 mbar, about 1025 mbar, about 1030 mbar, about 1035 mbar, about 1040 mbar, about 1045 mbar, about 1050 mbar, or any value therebetween.

[0029] All ranges disclosed herein should be understood to encompass any and all subranges contained therein. For example, a range of "1 to 10" should be considered to include any and all subranges between a minimum of 1 and a maximum of 10 (and including 1 and 10); that is, all subranges start with a minimum of 1 or greater (such as 1 to 6.1) and end with a maximum of 10 or less (such as 5.5 to 10).

[0030] As used herein, the meanings of “a,” “an,” and “the” include both singular and plural referents unless the context clearly dictates otherwise.

[0031] As used herein, "cladding layer" or "clad aluminum alloy layer" refers to a material used or to be used as a cladding layer on a core layer. "Core layer" or "aluminum alloy core layer" refers to an internal material that can be a major component (e.g., at least 50% or more of the clad product) in a clad product. "Cladding product" or "clad aluminum alloy product" refers to a combination of at least one cladding layer on a core layer.

[0032] As used herein, "corrosion coverage percentage" refers to the percentage of corrosion coverage area to the total surface area. "Corrosion coverage area" is the area of ​​corrosion coverage after a surface is subjected to corrosion testing.

[0033] As used herein, "bond durability" refers to the ability of an adhesive bonding two articles together to withstand cyclic mechanical stress or non-cyclic stress (e.g., using a neutral salt spray ("NSS") test) after exposure to environmental conditions that cause adhesive failure. In one example using cyclic mechanical stress, bond durability can be characterized based on the number of cycles of mechanical stress applied to the bonded article until the bond fails.

[0034] As used herein, "atomic percent" or "atomic %" is the number of atoms of a given component (e.g., Ca, Mg, Zn and / or Ca) per 100 atoms of a substance (e.g., aluminum alloy, substrate, sheet, surface), expressed as a percentage.

[0035] Throughout this application, aluminum alloys and clad products and parts thereof are described according to their elemental compositions expressed in weight percent (wt%). In some aspects, in each alloy, the remainder is aluminum, wherein the sum of all impurities is a maximum of 0.50 wt% (e.g., a maximum of 0.45 wt%, a maximum of 0.40 wt%, a maximum of 0.35 wt%, a maximum of 0.30 wt%, a maximum of 0.25 wt%, a maximum of 0.20 wt%, a maximum of 0.15 wt%, and / or a maximum of 0.10 wt%).

[0036] Aluminum Alloy

[0037] New aluminum alloys are described herein, comprising Ca and Zn; Mg and Zn; or Ca, Mg, and Zn, and in some aspects, clad aluminum alloy layers (sometimes referred to as cladding layers or cladding). The inventors have discovered that clad aluminum alloy layers containing amounts of Ca and Zn or Mg and Zn (or Ca, Mn, and Zn) as described herein unexpectedly achieve excellent filiform corrosion resistance and excellent paint line pretreatment suitability in addition to good strength and formability. Conventional thinking in the art previously was that having increased Ca and / or Mg content, such as the amounts described herein, would cause corrosion.

[0038] In some aspects, the aluminum alloy includes up to about 1.0 wt % Ca, e.g., up to about 0.95 wt % Ca, up to about 0.90 wt % Ca, up to about 0.85 wt % Ca, up to about 0.80 wt % Ca, up to about 0.75 wt % Ca, up to about 0.70 wt % Ca, up to about 0.65 wt % Ca, up to about 0.60 wt % Ca, up to about 0.55 wt % Ca, up to about 0.50 wt % Ca, up to about 0.45 wt % Ca, up to about 0.40 wt % Ca, up to about 0.35 wt % Ca, up to about 0.30 wt % Ca, up to about 0.25 wt % Ca, up to about 0.20 wt % Ca, up to about 0.15 wt % Ca, up to about 0.10 wt % Ca, up to about 0.05 wt % Ca, or up to about 0.01 wt % Ca. In terms of ranges, the aluminum alloy can include from about 0.01 wt % to about 1.0 wt % Ca, e.g., from about 0.03 wt % to about 0.90 wt % Ca, from about 0.05 wt % to about 0.80 wt % Ca, from about 0.10 wt % to about 0.80 wt % Ca, from about 0.20 wt % to about 0.75 wt % Ca, from about 0.20 wt % to about 0.70 wt % Ca, from about 0.20 wt % to about 0.60 wt % Ca, from about 0.20 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.50 wt % Ca, from about 0.25 wt % to about 0.45 wt % Ca, from about 0.30 wt % to about 0.45 wt % Ca, or from about 0.30 wt % to about 0.40 wt % Ca. In some embodiments, Ca is absent (eg, 0%).

[0039] In some aspects, the aluminum alloy includes up to about 3.0 wt % Zn, e.g., up to about 2.9 wt % Zn, up to about 2.8 wt % Zn, up to about 2.7 wt % Zn, up to about 2.6 wt % Zn, up to about 2.5 wt % Zn, up to about 2.4 wt % Zn, up to about 2.3 wt % Zn, up to about 2.2 wt % Zn, up to about 2.1 wt % Zn, up to about 2.0 wt % Zn, up to about 1.9 wt % Zn, up to about 1.8 wt % Zn, up to about 1.7 wt % Zn, up to about 1.6 wt % Zn, up to about 1.5 wt % Zn, up to about 1.4 wt % Zn, up to about 1.3 wt % Zn, up to about 1.2 wt % Zn, up to about 1.1 wt % Zn, up to about 1.0 wt % Zn, % Zn, up to about 0.95 wt % Zn, up to about 0.90 wt % Zn, up to about 0.85 wt % Zn, up to about 0.80 wt % Zn, up to about 0.75 wt % Zn, up to about 0.70 wt % Zn, up to about 0.65 wt % Zn, up to about 0.60 wt % Zn, up to about 0.55 wt % Zn, up to about 0.50 wt % Zn, up to about 0.45 wt % Zn, up to about 0.40 wt % Zn, up to about 0.35 wt % Zn, up to about 0.30 wt % Zn, up to about 0.25 wt % Zn, up to about 0.20 wt % Zn, up to about 0.15 wt % Zn, up to about 0.10 wt % Zn, up to about 0.05 wt % Zn, or up to about 0.01 wt % Zn. In terms of ranges, the aluminum alloy can include from about 0.01 wt % to about 3.0 wt % Zn, e.g., from about 0.03 wt % to about 1.2 wt % Zn, from about 0.05 wt % to about 1.2 wt % Zn, from about 0.10 wt % to about 1.1 wt % Zn, from about 0.20 wt % to about 1.0 wt % Zn, from about 0.30 wt % to about 1.0 wt % Zn, from about 0.4 % Zn, from about 0.20 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.50 wt % Zn, from about 0.25 wt % to about 0.45 wt % Zn, from about 0.30 wt % to about 0.45 wt % Zn, or from about 0.30 wt % to about 0.40 wt % Zn.

[0040] In some aspects, the aluminum alloy can include up to about 1.0 wt % Mg, e.g., up to about 0.95 wt % Mg, up to about 0.90 wt % Mg, up to about 0.85 wt % Mg, up to about 0.80 wt % Mg, up to about 0.75 wt % Mg, up to about 0.70 wt % Mg, up to about 0.65 wt % Mg, up to about 0.60 wt % Mg, up to about 0.55 wt % Mg, up to about 0.50 wt % Mg, up to about 0.45 wt % Mg, up to about 0.40 wt % Mg, up to about 0.35 wt % Mg, up to about 0.30 wt % Mg, up to about 0.25 wt % Mg, up to about 0.20 wt % Mg, up to about 0.15 wt % Mg, up to about 0.10 wt % Mg, up to about 0.05 wt % Mg, or up to about 0.01 wt % Mg. In terms of ranges, the aluminum alloy may include from about 0.01 wt % to about 1.0 wt % Mg, e.g., from about 0.03 wt % to about 0.95 wt % Mg, from about 0.05 wt % to about 0.90 wt % Mg, from about 0.10 wt % to about 0.90 wt % Mg, from about 0.20 wt % to about 0.85 wt % Mg, from about 0.30 wt % to about 0.85 wt % Mg, from about 0.40 wt % to about 0.85 wt % Mg, or from about 0.50 wt % to about 0.80 wt % Mg. In some embodiments, Mg is absent (e.g., 0%).

[0041] In some aspects, the aluminum alloy comprises from about 0.01 wt % to about 1.0 wt % Ca and from about 0.1 wt % to about 2.0 wt % Zn. In some aspects, the ratio of Ca wt % to Zn wt % in the aluminum alloy can be from about 1:10 to about 2:1 Ca:Zn (e.g., from about 1:9 to about 1:1; from about 1:7 to about 1:1; from about 1:5 to about 1:1; from about 1:4 to about 1:1; or from about 1:3 to about 1:1.5). Optionally, the aluminum alloy may also comprise from about 0.01 wt % to about 5.0 wt % Si. Optionally, the aluminum alloy may comprise from about 0.05 wt % to about 1.0 wt % Fe. Optionally, the aluminum alloy may comprise from 0.01 wt % to 1.0 wt % Cu.

[0042] In addition, in some aspects, the aluminum alloy includes from about 0.01 wt % to about 1.0 wt % Mg and from about 0.01 wt % to about 2.0 wt % Zn. In some aspects, the ratio of Mg wt % to Zn wt % in the aluminum alloy can be from about 100:1 to about 1:1 Mg:Zn (e.g., from about 50:1 to about 1:1; from about 50:1 to about 20:1; or from about 20:1 to about 1:1). Optionally, the aluminum alloy may also include from about 0.01 wt % to about 5.0 wt % Si. Optionally, the aluminum alloy may include from about 0.05 wt % to about 1.0 wt % Fe. Optionally, the aluminum alloy may include from 0.01 wt % to 1.0 wt % Cu.

[0043] Moreover, in some aspects, the aluminum alloy includes from about 0.01 wt % to about 1.0 wt % Ca, from about 0.01 wt % to about 1.0 wt % Mg, and from about 0.01 wt % to about 2.0 wt % Zn.

[0044] Aluminum alloy surface layer

[0045] In addition to novel aluminum alloys containing Ca and Zn, Mg and Zn, or Ca, Zn and Mg, novel surface layers for (e.g., coatings) aluminum alloys are described herein, wherein the surface layer may include Mg, Ca, Zn, Ni, or a combination thereof. One or more surface layers may be positioned on an aluminum alloy substrate, such as an aluminum alloy described above or an aluminum alloy substrate other than those described above. Mg, Ca, Zn, Ni, or a combination thereof may be in a form in which Mg, Ca, Zn, and / or Ni can be used to inhibit or prevent corrosion in the aluminum alloy substrate. Mg, Ca, Zn, Ni, or a combination thereof should also be present in an amount sufficient to inhibit or prevent corrosion in the aluminum alloy substrate. In certain aspects, an amount sufficient to inhibit or prevent corrosion in an aluminum alloy substrate can be at least about 0.3 atomic % of Mg, Ca, Zn, Ni, or a combination thereof (e.g., at least about 0.36 atomic %, at least about 0.38 atomic %, at least about 0.40 atomic %, at least about 0.42 atomic %, at least about 0.44 atomic %, at least about 0.45 atomic %, at least about 0.46 atomic %, at least about 0.48 atomic %, at least about 0.50 atomic %, at least about 0.55 atomic %, at least about 0. %, at least about 4.0 atomic %, at least about 4.5 atomic %, or at least about 5.0 atomic %). As a specific example, in certain aspects, an amount sufficient to inhibit or prevent corrosion in an aluminum alloy substrate can be at least about 0.17 atomic % Ca and at least about 0.19 atomic % Zn (e.g., at least about 0.17 atomic % Ca and at least about 0.20 atomic % Zn, at least about 0.18 atomic % Ca and at least about 0.19 atomic % Zn, or at least about 0.18 atomic % Ca and at least about 0.20 atomic % Zn). In terms of ranges, in some aspects, an amount sufficient to inhibit or prevent corrosion can be from about 0.3 atomic % Mg, Ca, Zn, Ni, or a combination thereof to about 8.0 atomic % Mg, Ca, Zn, Ni, or a combination thereof (e.g., from about 0.35 atomic % to about 6.0 atomic %, from about 0.36 atomic % to about 5.0 atomic %, from about 0.40 atomic % to about 4.0 atomic %, from about 0.45 atomic % to about 3.0 atomic %, from about 0.50 atomic % to about 2.0 atomic %, from about 0.55 atomic % to about 1.5 atomic %, or from about 0.60 atomic % to about 1.25 atomic %). In some aspects, the atomic % can be measured using x-ray photoelectron spectroscopy ("XPS").

[0046] For example, the coating may comprise magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), or a combination thereof. Unexpectedly, the described coated aluminum alloy exhibits significant filiform corrosion resistance. Filiform corrosion typically occurs on the coating surface when moisture or corrosive solutions contact the metal surface. It is caused by active galvanic cells on the metal surface. Without being bound by theory, filiform corrosion in aluminum alloys expands with an acidic head and a relatively higher tail pH. This pH difference, combined with different oxygen concentrations (caused by oxygen diffusion), produces a net anodic reaction at the head and a net cathodic reaction at the tail, leading to corrosion. The inventors unexpectedly discovered that substances in the coating, such as the aforementioned MgO, CaO, and / or ZnO, can poison the acidic nature of the head to interrupt corrosion expansion.

[0047] In another embodiment, corrosion of aluminum alloys can be reduced by inhibiting the reactivity of the cathode tail. The inventors unexpectedly discovered that this can be achieved by using a coating to deliver an inorganic cathode inhibitor on the aluminum alloy. Some examples of inorganic cathode inhibitors are ions of Mg, Ca, Zn, Ni, or combinations thereof from the coating. These ions can react with the hydroxyl groups ( - OH) to form insoluble hydroxides, such as Mg(OH) 2 , Ca(OH) 2 、Zn(OH) 2 or Ni(OH) 2 , these hydroxides are deposited at the cathode position on the metal surface, protecting the metal surface. Other examples of inorganic cathode inhibitors can include phosphonates, tannins and / or lignin. In some embodiments, corrosion can be prevented by poisoning the acidic nature of the corrosion head and inhibiting the cathode tail.

[0048] In some aspects, the coating can be applied to the aluminum alloy surface with a chemical detergent containing Mg, Ca, Zn, Ni, or a combination thereof, for example, in a rinse step, using physical vapor deposition ("PVD") or using chemical vapor deposition ("CVD"). Some examples of methods that can be used to coat the aluminum alloy surface with a chemical detergent are dipping (e.g., by immersing the aluminum alloy surface in a bath or other type of container containing Mg, Ca, Zn, and / or Ni ions), rinsing or spraying, or rolling an ion-containing fluid onto the surface. Suitable methods and conditions are selected and optimized based on various considerations such as the type of ion or ions used and / or the type of surface being treated.

[0049] The coated aluminum alloy can be used for aluminum alloy products, such as clad products. For example, the coated aluminum alloy can be used as a cladding layer or as a core layer in a clad aluminum alloy product.

[0050] Properties of Aluminum Alloys and Coated Aluminum Alloys

[0051] Unexpectedly, the novel aluminum alloys and coated aluminum alloys described herein exhibit excellent corrosion resistance. For example, corrosion resistance can be measured by a filiform corrosion test ("FFC"). Corrosion resistance can be tested according to standard methods used in the art. An example of such a standard method is ID-3678, ISO 4623-2 (2016). ASTM D2803 is another suitable standard that can be used to test filiform corrosion. DIN EN ISO 9227 is also a standard that can be used to test filiform corrosion. Filiform corrosion is a special form of crevice corrosion. This type of corrosion usually occurs on the coating surface when moisture or corrosive solutions penetrate a defective coating. It is caused by active galvanic cells on the metal surface. Unexpectedly, the novel aluminum alloys and novel coated aluminum alloys described herein show significant filiform corrosion resistance when tested by standard test methods.

[0052] For example, when subjected to the filiform corrosion test, the aluminum alloy and the coated aluminum alloy can have a corrosion coverage percentage (i.e., the percentage of corrosion coverage area to total area) of 25% or less (e.g., 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less) in the horizontal direction, the vertical direction, the diagonal direction, or any and all combinations of these directions (measured individually). In addition, the aluminum alloy and coated aluminum alloy may have an average corrosion wire length of 0.50 mm or less (e.g., 0.45 mm or less, 0.40 mm or less, 0.35 mm or less, 0.30 mm or less, 0.25 mm or less, 0.20 mm or less, 0.15 mm or less, 0.10 mm or less, or 0.05 mm or less) in the horizontal direction, the vertical direction, the diagonal direction, or any and all combinations of these directions (measured individually) during the filiform corrosion test.

[0053] In one aspect, the new aluminum alloys and coated aluminum alloys described herein can have a yield strength of up to about 600 MPa (e.g., from about 150 MPa to about 600 MPa, from about 300 MPa to about 600 MPa, or from about 400 MPa to about 600 MPa) at a T6 temper. In one aspect, the new aluminum alloys and coated aluminum alloys described herein can have a yield strength of up to about 200 MPa (e.g., from about 50 MPa to about 200 MPa, from about 100 MPa to about 200 MPa, or from about 120 MPa to about 200 MPa) at a T4 temper. The new aluminum alloys and coated aluminum alloys described herein can have an elongation (overall or uniform) of at least about 25% (measured individually) (e.g., at least about 26%, at least about 27%, at least about 28%, at least about 29%, at least about 30%, at least about 31%, at least about 32%, at least about 33%, at least about 34%, at least about 35%, at least about 36%, at least about 37%, at least about 38%, at least about 39%, at least about 40%, at least about 41%, at least about 42%, at least about 43%, at least about 44%, or at least about 45%) in any direction or in any combination of directions (longitudinal (L), diagonal (D), and / or transverse (T)). In terms of ranges, the new aluminum alloys and coated aluminum alloys described herein can have an elongation of from about 25% to about 50% (e.g., from about 27% to about 48%, from about 28% to about 47%, from about 29% to about 46%, from about 30% to about 45%, from about 30% to about 42%, from about 30% to about 41%, from about 31% to about 40%, from about 32% to about 40%, from about 32% to about 39%, or from about 35% to about 45%).

[0054] Due to the unexpectedly increased corrosion resistance properties of the inventive alloy products, increased amounts of various metals can be used in alloys that were previously abandoned due to corrosion issues.For example, the aluminum alloy can contain significant levels of copper (Cu). For example, in some aspects, the aluminum alloy can include up to about 1.0 wt % Cu, e.g., up to about 0.95 wt % Cu, up to about 0.90 wt % Cu, up to about 0.85 wt % Cu, up to about 0.80 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, up to about 0.65 wt % Cu, up to about 0.60 wt % Cu, up to about 0.55 wt %, up to about 0.50 wt % Cu, up to about 0.45 wt % Cu, up to about 0.40 wt % Cu, up to about 0.35 wt % Cu, up to about 0.30 wt % Cu, up to about 0.25 wt % Cu, up to about 0.20 wt % Cu, up to about 0.15 wt % Cu, or up to about 0.10 wt % Cu. In terms of ranges, the aluminum alloy may optionally include from about 0.1 wt % to about 1.0 wt % Cu, e.g., from about 0.1 wt % to about 0.8 wt % Cu, from about 0.2 wt % to about 0.7 wt % Cu, or from about 0.5 wt % to about 0.6 wt % Cu. Previously, such significant ranges of Cu may not be used due to perceived corrosion.

[0055] Aluminum alloy cladding

[0056] The novel aluminum alloy and coating aluminum alloy described herein can be used as a clad aluminum alloy layer in a clad aluminum alloy product. The clad aluminum alloy product described herein may include a first clad aluminum alloy layer positioned on a first side of the core aluminum alloy layer. In some aspects, the clad aluminum alloy product described herein may further include a second clad aluminum alloy layer positioned on the second side of the core layer. The first clad aluminum alloy layer and the second clad aluminum alloy layer may include the same or different alloys. In some aspects, the first clad aluminum alloy layer may include Ca, Zn, and Al. In some cases, the first clad aluminum alloy layer may include from about 0.01 wt % to about 1.0 wt % Ca and from about 0.1 wt % to about 2.0 wt % Zn. In some aspects, the first clad aluminum alloy layer may include Mg, Zn, and Al. In some cases, the first clad aluminum alloy layer may include from about 0.01 wt % to about 1.0 wt % Mg and from about 0.1 wt % to about 2.0 wt % Zn. In some aspects, the first clad aluminum alloy layer may include Ca, Zn, Mg and Al. In some aspects, the first clad aluminum alloy layer may include Mg, Zn, Ca and Al. In some cases, the first clad aluminum alloy layer may include from about 0.01 wt % to about 1.0 wt % Mg, from about 0.1 wt % to about 2.0 wt % Zn and from about 0.01 wt % to about 1.0 wt % Ca. In some aspects, the first clad aluminum alloy may include a coating, the coating comprising ions of Mg, Ca, Zn, Ni or a combination thereof positioned on the outward surface of the first clad aluminum alloy (i.e., on the surface facing away from the core layer).

[0057] In some aspects, the second clad aluminum alloy layer may include Ca, Zn and Al. In some cases, the second clad aluminum alloy layer may include Ca from about 0.01 wt % to about 1.0 wt % and Zn from about 0.1 wt % to about 2.0 wt %. In some aspects, the second clad aluminum alloy layer may include Mg, Zn and Al. In some cases, the second clad aluminum alloy layer may include Mg from about 0.01 wt % to about 1.0 wt % and Zn from about 0.1 wt % to about 2.0 wt %. In some aspects, the second clad aluminum alloy layer may include Mg, Zn, Ca and Al. In some cases, the second clad aluminum alloy layer may include Mg from about 0.01 wt % to about 1.0 wt %, Zn from about 0.1 wt % to about 2.0 wt % and Ca from about 0.01 wt % to about 1.0 wt %. In some aspects, the second clad aluminum alloy may include a coating comprising ions of Mg, Ca, Zn, Ni, or a combination thereof positioned on an outwardly facing surface of the second clad aluminum alloy (ie, on a surface facing away from the core layer).

[0058] Also provided herein are materials comprising the clad aluminum alloy products described herein. The materials may include automotive products (e.g., automotive structural parts), aerospace products (e.g., aerospace structural parts or aerospace non-structural parts), marine products (e.g., marine structural parts or marine non-structural parts), or electronic products (e.g., electronic device housings), etc. Also provided herein are aluminum alloy sheets, plates, and Saudi plates comprising the clad aluminum alloy products described herein.

[0059] Cladding aluminum alloy products

[0060] The coated aluminum alloy product includes one or more coated aluminum alloy layers in contact with the core layer. In some examples, the core layer has a coating layer only on one side (i.e., there is one coating layer in the coated aluminum alloy product). In other examples, the core layer is coated on more than one side, such as on both sides (i.e., there are two coating layers in the coated aluminum alloy product). In one embodiment, at least one coating layer comprises Al, Ca and Zn. In another embodiment, at least one coating layer comprises Al, Mg and Zn. In another embodiment, at least one coating layer comprises Al, Ca, Mg and Zn. In another embodiment, at least one coating layer comprises a coating comprising ions of Mg, Ca, Zn, Ni or a combination thereof. The coating is positioned outside at least one coating layer, back to the core layer. Typically, the core layer is a larger component of the material, and therefore typically mainly determines the overall mechanical properties of the coated product, such as the strength of the coated product. On the other hand, the coating layer, which typically (but not always) represents a smaller component of the coated product, is in contact with the surrounding environment, and therefore determines chemical activity (e.g., corrosion resistance) and can affect the formability and bonding characteristics of the coated product.

[0061] In some aspects, the first side of the core layer is adjacent to and in contact with the first cladding layer to form a first interface (e.g., no layer (such as a coating) intervenes between the first cladding layer and the first side of the core layer), although this is not necessary. In some aspects, the coated aluminum alloy product includes a second cladding layer. In some cases, the second side of the core layer is adjacent to and in contact with the second cladding layer to form a second interface (i.e., no layer (such as a coating) intervenes between the second cladding layer and the second side of the core layer), although this is not necessary. In some aspects, the first cladding layer and the second cladding layer may have the same chemical composition. In other aspects, the first cladding layer and the second cladding layer may have different chemical compositions.

[0062] In some aspects, the coated product can have a thickness of from about 0.1 mm to about 6 mm (e.g., from about 0.1 mm to about 5.8 mm, from about 0.2 mm to about 5.5 mm, from about 0.3 mm to about 5.3 mm, from about 0.4 mm to about 5.2 mm, from about 0.5 mm to about 5.0 mm, from about 0.6 mm to about 4.8 mm, from about 0.7 mm to about 4.6 mm, from about 0.8 mm to about 4.5 mm, from about 0.8 mm to about 4.3 mm, from about 0.9 mm to about 4.2 mm, from about 1 mm to about 4 mm, from about 1.3 mm to about 3.8 mm, from about 1.5 mm to about 3.5 mm, from about 1.7 mm to about 3.2 mm, or from about 2 mm to about 3 mm).

[0063] Core layer

[0064] The core layer is an aluminum-containing alloy. In some aspects, the core layer can be any aluminum-containing alloy suitable as a core layer when covered by a coating layer comprising Al, Ca, and Zn; a coating layer comprising Al, Mg, and Zn; a coating layer comprising Al, Ca, Mg, and Zn; or a coating layer comprising a coating comprising ions of Mg, Ca, Zn, Ni, or a combination thereof. In some aspects, the core layer can comprise the novel aluminum alloy and / or novel coated aluminum alloy described above.

[0065] The thickness of the core layer can be from about 30% to about 99% of the thickness of the clad aluminum alloy product described herein, for example, from about 40% to 99%, from about 50% to 99%, from about 55% to 99%, from about 60% to 98%, from about 70% to 98%, from about 75% to 95%, or from about 80% to 90%. For example, in a clad aluminum alloy product having a thickness of about 1000 microns, the core layer can have a thickness of about 300 microns to about 990 microns. Optionally, the core layer can have a thickness in the range of about 0.1 mm to about 5 mm (e.g., about 0.5 mm to about 3 mm, from about 0.7 mm to about 2.5 mm, or from about 1 mm to about 2.2 mm). For example, the thickness of the core layer may be about 0.5 mm, about 0.6 mm, about 0.7 mm, about 0.8 mm, about 0.9 mm, about 1.0 mm, about 1.1 mm, about 1.2 mm, about 1.3 mm, about 1.4 mm, about 1.5 mm, about 1.6 mm, about 1.7 mm, about 1.8 mm, about 1.9 mm, about 2.0 mm, about 2.1 mm, about 2.2 mm, about 2.3 mm, about 2.4 mm, about 2.5 mm, about 2.6 mm, about 2.7 mm, about 2.8 mm, about 2.9 mm, or about 3.0 mm.

[0066] In some instances, any alloy designated as a "1xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 1xxx series alloys suitable for use as a core layer may include AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, or AA1199.

[0067] In some examples, any alloy designated as a "2xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 2xxx series alloys suitable for use as a core layer may include AA2001, A2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012, AA2013, AA2014, AA2014B, AA2015, AA2016, AA2017, AA2018, AA2019, AA2020, AA2021 A. AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA23 19. AA2419, AA2519, AA2021, AA2022, AA2023, AA2024, AA2024A, AA2124, AA2224, AA2224A, AA2324, AA24 24. AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA2028, AA2028A, AA2028B, AA2028C, AA 2029, AA2030, AA2031, AA2032, AA2034, AA2036, AA2037, AA2038, AA2039, AA2139, AA2040, AA2041, AA20 44. AA2045, AA2050, AA2055, AA2056, AA2060, AA2065, AA2070, AA2076, AA2090, AA2091, AA2094, AA209 5. AA2195, AA2295, AA2196, AA2296, AA2097, AA2197, AA2297, AA2397, AA2098, AA2198, AA2099 or AA2199.

[0068] In some examples, any alloy designated as a "3xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 3xxx series alloys suitable for use as a core layer may include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA300 7. AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.

[0069] In some instances, any alloy designated as a "4xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 4xxx series alloys suitable for use as a core layer may include AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, or AA4147.

[0070] In some instances, any alloy designated as a "5xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 5xxx series alloys suitable for use as a core layer may include AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5210, AA5211, AA5212, AA5213, AA5214, AA5215, AA5216, AA5217, AA5218, AA5219A, AA5219B, AA5220, AA5221C, AA5222A, AA5222A, AA5223, AA5224, AA5225 A5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA52 49. AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA5251A, AA 5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5154C, AA5254, AA5354, AA5454, AA5554, AA 5654, AA5654A, AA5754, AA5854, AA5954, AA5056, AA5356, AA5356A, AA5456, AA5456A, AA5456B, AA5556, AA5556A, AA5556B, AA5556C, AA5257, AA5457, AA5557, AA5657, AA5058, AA5059, AA5070, AA5180, AA5180A, AA5082, AA5182, AA5083, AA5183, AA5183A, AA5283, AA5283A, AA5283B, AA5383, AA5483, AA5086, AA5186, AA5087, AA5187 or AA5088.

[0071] In some examples, any alloy designated as a "6xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 6xxx series alloys suitable for use as a core layer may include AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA600 8. AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA601 6. AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027, AA6028 ,AA6031,AA6032,AA6033,AA6040,AA6041,AA6042,AA6043,AA6151,AA6351,AA6351A,AA6451,AA6951,AA6053, AA6055, AA6056, AA6156, AA6060, AA6160, AA6260, AA6360, AA6460, AA6460B, AA6560, AA6660, AA6061, AA6061A, AA6261, AA6361, AA6162, AA6262, AA6262A, AA6063, AA6063A, AA6463, AA6463A, AA6763, A6963, AA6064, AA6064A, AA6065, AA6066, AA6068, AA6069, AA6070, AA6081, AA6181, AA6181A, AA6082, AA6082A, AA6182, AA6091, or AA6092.

[0072] In some examples, any alloy designated as a "7xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 7xxx series alloys suitable for use as a core layer may include AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7109, AA7110, AA71111A, AA7112, AA7113, AA7114, AA7115A, AA7116, AA7117, AA7118, AA7119A, AA7117, AA7118, AA7119B, AA7114, AA7115A, AA7116, AA7117, AA7118, AA7119A ... 7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009 ,AA7010,AA7011,AA7012,AA7014,AA7016,AA7116,AA7122,AA7023,AA7026,AA7029,AA712 9. AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA70 49. AA7049A, AA7149, 7204, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7150, AA7250, AA7 7055, AA7055, AA7255, AA7056, AA7060, AA7064, AA7065, AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, or AA7099.

[0073] In some examples, any alloy designated as an "8xxx series" alloy is suitable for use as a core layer. By way of non-limiting example, 8xxx series alloys suitable for use as a core layer may include AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA8019, AA8021, AA8222, AA8223, AA8224, AA8225, AA8226, AA8227, AA8228, AA8229, AA8230, AA8231, AA8232, AA8233, AA8234, AA8235, AA8236, AA8237, AA8238, AA8239, AA8240, AA8241, AA8242, AA8243, AA8244, AA8245, AA8246, AA8247, AA8248, AA8249, AA8250, AA8251, AA8252, AA8253, AA8254, AA8255, AA8256, AA8257, AA8258, AA8259, AA8260 AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, AA8090, AA8091, or AA8093.

[0074] Coating

[0075] The present invention also describes an aluminum alloy for use as a clad aluminum alloy layer in a clad aluminum alloy product. In addition to aluminum, the clad aluminum alloy layer contains Ca and Zn, or Zn and Mg, or Ca, Zn and Mg, and achieves excellent surface properties.

[0076] The thickness of each clad aluminum alloy layer can be about 1% to about 50% (e.g., from about 1% to about 25%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 12%, or about 10%) of the total thickness of the clad aluminum alloy product described herein. For example, in a clad aluminum alloy product having a thickness of 1000 microns, each clad aluminum alloy layer can have a thickness of at most about 250 microns (e.g., at most about 200 microns, at most about 180 microns, at most about 160 microns, at most about 150 microns, at most about 130 microns, at most about 120 microns, at most about 100 microns, at most about 80 microns, at most about 50 microns, at most about 30 microns, at most about 20 microns, at most about 15 microns, from about 10 microns to about 250 microns, from about 20 microns to about 200 microns, from about 25 microns to about 200 microns, from about 40 microns to about 180 microns, from about 50 microns to about 150 microns, or from about 70 microns to about 130 microns). Optionally, each clad aluminum alloy layer can have a thickness in the range of about 0.10 mm to about 1.0 mm (e.g., about 0.20 mm to about 0.80 mm, about 0.25 mm to about 0.70 mm, about 0.30 mm to about 0.75 mm, about 0.35 mm to about 0.70 mm, about 0.40 mm to about 0.65 mm, about 0.40 mm to about 0.60 mm, or about 0.50 mm).

[0077] In some aspects, the clad aluminum alloy layer includes up to about 1.0 wt % Ca, e.g., up to about 0.95 wt % Ca, up to about 0.90 wt % Ca, up to about 0.85 wt % Ca, up to about 0.80 wt % Ca, up to about 0.75 wt % Ca, up to about 0.70 wt % Ca, up to about 0.65 wt % Ca, up to about 0.60 wt % Ca, up to about 0.55 wt % Ca, up to about 0.50 wt % Ca, up to about 0.45 wt % Ca, up to about 0.40 wt % Ca, up to about 0.35 wt % Ca, up to about 0.30 wt % Ca, up to about 0.25 wt % Ca, up to about 0.20 wt % Ca, up to about 0.15 wt % Ca, up to about 0.10 wt % Ca, up to about 0.05 wt % Ca, or up to about 0.01 wt % Ca. In terms of ranges, the cladding aluminum alloy layer can include from about 0.01 wt % to 1.0 wt % Ca, e.g., from about 0.03 wt % to about 0.90 wt % Ca, from about 0.05 wt % to about 0.80 wt % Ca, from about 0.10 wt % to about 0.80 wt % Ca, from about 0.20 wt % to about 0.75 wt % Ca, from about 0.20 wt % to about 0.70 wt % Ca, from about 0.10 wt % to about 0.80 wt % Ca, % Ca, from about 0.20 wt % to about 0.60 wt % Ca, from about 0.20 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.50 wt % Ca, from about 0.25 wt % to about 0.45 wt % Ca, from about 0.30 wt % to about 0.45 wt % Ca, or from about 0.30 wt % to about 0.40 wt % Ca. In addition, the cladding aluminum alloy layer comprises at most about 3.0 wt % Zn, at most about 2.9 wt % Zn, at most about 2.8 wt % Zn, at most about 2.7 wt % Zn, at most about 2.6 wt % Zn, at most about 2.5 wt % Zn, at most about 2.4 wt % Zn, at most about 2.3 wt % Zn, at most about 2.2 wt % Zn, at most about 2.1 wt % Zn, at most about 2.0 wt % Zn, at most about 1.9 wt % Zn, at most about 1.8 wt % Zn, at most about 0.85 wt % Zn, at most about 0.80 wt % Zn, at most about 0.75 % Zn, up to about 0.70 wt % Zn, up to about 0.65 wt % Zn, up to about 0.60 wt % Zn, up to about 0.55 wt % Zn, up to about 0.50 wt % Zn, up to about 0.45 wt % Zn, up to about 0.40 wt % Zn, up to about 0.35 wt % Zn, up to about 0.30 wt % Zn, up to about 0.25 wt % Zn, up to about 0.20 wt % Zn, up to about 0.15 wt % Zn, up to about 0.10 wt % Zn, up to about 0.05 wt % Zn, or up to about 0.01 wt % Zn.In some aspects, the clad aluminum alloy layer can include at least 0.30 wt % Zn, e.g., at least 0.31 wt % Zn, at least 0.32 wt % Zn, at least 0.33 wt % Zn, at least 0.34 wt % Zn, at least 0.35 wt % Zn, at least 0.38 wt % Zn, at least 0.40 wt % Zn, at least 0.43 wt % Zn, at least 0.45 wt % Zn, at least 0.47 wt % Zn, at least 0.48 wt % Zn, at least 0.50 wt % Zn, at least 0.51 wt % Zn, at least 0.55 wt % Zn, at least 0.60 wt % Zn, at least 0.61 wt % Zn, at least 0.62 wt % Zn, at least 0.63 wt % Zn, at least 0.64 wt % Zn, at least 0.65 wt % Zn, at least 0.66 wt % Zn, at least 0.67 wt % Zn, at least 0.68 wt % Zn, at least 0.69 wt % Zn, at least 0.70 wt % Zn, at least 0.71 wt % Zn, at least 0.72 wt % Zn, at least 0.73 wt % Zn, at least 0.74 wt % Zn % Zn, at least 0.60 wt % Zn, at least 0.70 wt % Zn, at least 0.80 wt % Zn, at least 0.90 wt % Zn, at least 1.0 wt % Zn, at least 1.1 wt % Zn, at least 1.2 wt % Zn, at least 1.3 wt % Zn, at least 1.4 wt % Zn, at least 1.5 wt % Zn, at least 1.6 wt % Zn, at least 1.7 wt % Zn, at least 1.8 wt % Zn, at least 1.9 wt % Zn, at least 2.2 wt % Zn, at least 2.5 wt % Zn, or at least 2.7 wt % Zn. In terms of ranges, the coating can include from about 0.01 wt % to about 3.0 wt % Zn, e.g., from about 0.01 wt % to about 2.0 wt % Zn, from about 0.01 wt % to about 1.5 wt % Zn, from about 0.03 wt % to about 0.90 wt % Zn, from about 0.05 wt % to about 0.80 wt % Zn, from about 0.10 wt % to about 0.80 wt % Zn, from about 0.20 wt % to about 0.75 wt % Zn ...1.5 wt % Zn % Zn, from about 0.20 wt % to about 0.60 wt % Zn, from about 0.20 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.50 wt % Zn, from about 0.25 wt % to about 0.45 wt % Zn, from about 0.30 wt % to about 0.45 wt % Zn, or from about 0.30 wt % to about 0.40 wt % Zn.

[0078] Thus, in terms of ratios, in some aspects, Ca and Zn can be present in the clad aluminum alloy layer in a Ca:Zn ratio of about 1:10 to about 2:1 by weight (e.g., about 1:9 to about 1:1; about 1:7 to about 1:1; about 1:5 to about 1:1; about 1:4 to about 1:1; or about 1:3 to about 1:1.5).

[0079] In other aspects, the clad aluminum alloy includes up to about 1.0 wt % Mg, e.g., up to about 0.95 wt % Mg, up to about 0.90 wt % Mg, up to about 0.85 wt % Mg, up to about 0.80 wt % Mg, up to about 0.75 wt % Mg, up to about 0.70 wt % Mg, up to about 0.65 wt % Mg, up to about 0.60 wt % Mg, up to about 0.55 wt % Mg, up to about 0.50 wt % Mg, up to about 0.45 wt % Mg, up to about 0.40 wt % Mg, up to about 0.35 wt % Mg, up to about 0.30 wt % Mg, up to about 0.25 wt % Mg, up to about 0.20 wt % Mg, up to about 0.15 wt % Mg, up to about 0.10 wt % Mg, up to about 0.05 wt % Mg, or up to about 0.01 wt % Mg. In terms of ranges, the clad aluminum alloy may include from about 0.01 wt % to about 1.0 wt % Mg, e.g., from about 0.03 wt % to about 0.95 wt % Mg, from about 0.05 wt % to about 0.90 wt % Mg, from about 0.10 wt % to about 0.90 wt % Mg, from about 0.20 wt % to about 0.85 wt % Mg, from about 0.30 wt % to about 0.85 wt % Mg, from about 0.40 wt % to about 0.85 wt % Mg, or from about 0.50 wt % to about 0.80 wt % Mg. In addition, the cladding aluminum alloy layer comprises at most about 3.0 wt % Zn, at most about 2.9 wt % Zn, at most about 2.8 wt % Zn, at most about 2.7 wt % Zn, at most about 2.6 wt % Zn, at most about 2.5 wt % Zn, at most about 2.4 wt % Zn, at most about 2.3 wt % Zn, at most about 2.2 wt % Zn, at most about 2.1 wt % Zn, at most about 2.0 wt % Zn, at most about 1.9 wt % Zn, at most about 1.8 wt % Zn, at most about 0.85 wt % Zn, at most about 0.80 wt % Zn, at most about 0.75 % Zn, up to about 0.70 wt % Zn, up to about 0.65 wt % Zn, up to about 0.60 wt % Zn, up to about 0.55 wt % Zn, up to about 0.50 wt % Zn, up to about 0.45 wt % Zn, up to about 0.40 wt % Zn, up to about 0.35 wt % Zn, up to about 0.30 wt % Zn, up to about 0.25 wt % Zn, up to about 0.20 wt % Zn, up to about 0.15 wt % Zn, up to about 0.10 wt % Zn, up to about 0.05 wt % Zn, or up to about 0.01 wt % Zn.In some aspects, the clad aluminum alloy layer can include at least 0.30 wt % Zn, e.g., at least 0.31 wt % Zn, at least 0.32 wt % Zn, at least 0.33 wt % Zn, at least 0.34 wt % Zn, at least 0.35 wt % Zn, at least 0.38 wt % Zn, at least 0.40 wt % Zn, at least 0.43 wt % Zn, at least 0.45 wt % Zn, at least 0.47 wt % Zn, at least 0.48 wt % Zn, at least 0.50 wt % Zn, at least 0.51 wt % Zn, at least 0.55 wt % Zn, at least 0.60 wt % Zn, at least 0.61 wt % Zn, at least 0.62 wt % Zn, at least 0.63 wt % Zn, at least 0.64 wt % Zn, at least 0.65 wt % Zn, at least 0.66 wt % Zn, at least 0.67 wt % Zn, at least 0.68 wt % Zn, at least 0.69 wt % Zn, at least 0.70 wt % Zn, at least 0.71 wt % Zn, at least 0.72 wt % Zn, at least 0.73 wt % Zn, at least 0.74 wt % Zn % Zn, at least 0.60 wt % Zn, at least 0.70 wt % Zn, at least 0.80 wt % Zn, at least 0.90 wt % Zn, at least 1.0 wt % Zn, at least 1.1 wt % Zn, at least 1.2 wt % Zn, at least 1.3 wt % Zn, at least 1.4 wt % Zn, at least 1.5 wt % Zn, at least 1.6 wt % Zn, at least 1.7 wt % Zn, at least 1.8 wt % Zn, at least 1.9 wt % Zn, at least 2.2 wt % Zn, at least 2.5 wt % Zn, at least 2.7 wt % Zn. In terms of ranges, the coating can include from about 0.01 wt % to about 3.0 wt % Zn, e.g., from about 0.01 wt % to about 2.0 wt % Zn, from about 0.01 wt % to about 1.5 wt % Zn, from about 0.03 wt % to about 0.90 wt % Zn, from about 0.05 wt % to about 0.80 wt % Zn, from about 0.10 wt % to about 0.80 wt % Zn, from about 0.20 wt % to about 0.75 wt % Zn ...1.5 wt % Zn % Zn, from about 0.20 wt % to about 0.60 wt % Zn, from about 0.20 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.50 wt % Zn, from about 0.25 wt % to about 0.45 wt % Zn, from about 0.30 wt % to about 0.45 wt % Zn, or from about 0.30 wt % to about 0.40 wt % Zn.

[0080] Thus, in terms of ratios, in some aspects, the ratio of Mg and Zn in the clad aluminum alloy can be about 100:1 to about 1:1 Mg:Zn (e.g., about 50:1 to about 1:1; about 50:1 to about 20:1; or about 20:1 to about 1:1).

[0081] In other aspects, the clad aluminum alloy layer contains up to about 1.0 wt % Ca, e.g., up to about 0.95 wt % Ca, up to about 0.90 wt % Ca, up to about 0.85 wt % Ca, up to about 0.80 wt % Ca, up to about 0.75 wt % Ca, up to about 0.70 wt % Ca, up to about 0.65 wt % Ca, up to about 0.60 wt % Ca, up to about 0.55 wt % Ca, up to about 0.50 wt % Ca, up to about 0.45 wt % Ca, up to about 0.40 wt % Ca, up to about 0.35 wt % Ca, up to about 0.30 wt % Ca, up to about 0.25 wt % Ca, up to about 0.20 wt % Ca, up to about 0.15 wt % Ca, up to about 0.10 wt % Ca, up to about 0.05 wt % Ca, or up to about 0.01 wt % Ca. In terms of ranges, the cladding aluminum alloy layer can include from about 0.01 wt % to 1.0 wt % Ca, e.g., from about 0.03 wt % to about 0.90 wt % Ca, from about 0.05 wt % to about 0.80 wt % Ca, from about 0.10 wt % to about 0.80 wt % Ca, from about 0.20 wt % to about 0.75 wt % Ca, from about 0.20 wt % to about 0.70 wt % Ca, from about 0.10 wt % to about 0.80 wt % Ca, % Ca, from about 0.20 wt % to about 0.60 wt % Ca, from about 0.20 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.55 wt % Ca, from about 0.25 wt % to about 0.50 wt % Ca, from about 0.25 wt % to about 0.45 wt % Ca, from about 0.30 wt % to about 0.45 wt % Ca, or from about 0.30 wt % to about 0.40 wt % Ca. In addition, the clad aluminum alloy includes up to about 1.0 wt % Mg, for example, up to about 0.95 wt % Mg, up to about 0.90 wt % Mg, up to about 0.85 wt % Mg, up to about 0.80 wt % Mg, up to about 0.75 wt % Mg, up to about 0.70 wt % Mg, up to about 0.65 wt % Mg, up to about 0.60 wt % Mg, up to about 0.55 wt % Mg, up to about 0.50 wt % Mg, up to about 0.45 wt % Mg, up to about 0.40 wt % Mg, up to about 0.35 wt % Mg, up to about 0.30 wt % Mg, up to about 0.25 wt % Mg, up to about 0.20 wt % Mg, up to about 0.15 wt % Mg, up to about 0.10 wt % Mg, up to about 0.05 wt % Mg, or up to about 0.01 wt % Mg.In terms of ranges, the clad aluminum alloy may include from about 0.01 wt % to about 1.0 wt % Mg, e.g., from about 0.03 wt % to about 0.95 wt % Mg, from about 0.05 wt % to about 0.90 wt % Mg, from about 0.10 wt % to about 0.90 wt % Mg, from about 0.20 wt % to about 0.85 wt % Mg, from about 0.30 wt % to about 0.85 wt % Mg, from about 0.40 wt % to about 0.85 wt % Mg, or from about 0.50 wt % to about 0.80 wt % Mg. In addition, the cladding aluminum alloy layer comprises at most about 3.0 wt % Zn, at most about 2.9 wt % Zn, at most about 2.8 wt % Zn, at most about 2.7 wt % Zn, at most about 2.6 wt % Zn, at most about 2.5 wt % Zn, at most about 2.4 wt % Zn, at most about 2.3 wt % Zn, at most about 2.2 wt % Zn, at most about 2.1 wt % Zn, at most about 2.0 wt % Zn, at most about 1.9 wt % Zn, at most about 1.8 wt % Zn, at most about 0.85 wt % Zn, at most about 0.80 wt % Zn, at most about 0.75 % Zn, up to about 0.70 wt % Zn, up to about 0.65 wt % Zn, up to about 0.60 wt % Zn, up to about 0.55 wt % Zn, up to about 0.50 wt % Zn, up to about 0.45 wt % Zn, up to about 0.40 wt % Zn, up to about 0.35 wt % Zn, up to about 0.30 wt % Zn, up to about 0.25 wt % Zn, up to about 0.20 wt % Zn, up to about 0.15 wt % Zn, up to about 0.10 wt % Zn, up to about 0.05 wt % Zn, or up to about 0.01 wt % Zn. In some aspects, the clad aluminum alloy layer can include at least 0.30 wt % Zn, e.g., at least 0.31 wt % Zn, at least 0.32 wt % Zn, at least 0.33 wt % Zn, at least 0.34 wt % Zn, at least 0.35 wt % Zn, at least 0.38 wt % Zn, at least 0.40 wt % Zn, at least 0.43 wt % Zn, at least 0.45 wt % Zn, at least 0.47 wt % Zn, at least 0.48 wt % Zn, at least 0.50 wt % Zn, at least 0.51 wt % Zn, at least 0.55 wt % Zn, at least 0.60 wt % Zn, at least 0.61 wt % Zn, at least 0.62 wt % Zn, at least 0.63 wt % Zn, at least 0.64 wt % Zn, at least 0.65 wt % Zn, at least 0.66 wt % Zn, at least 0.67 wt % Zn, at least 0.68 wt % Zn, at least 0.69 wt % Zn, at least 0.70 wt % Zn, at least 0.71 wt % Zn, at least 0.72 wt % Zn, at least 0.73 wt % Zn, at least 0.74 wt % Zn % Zn, at least 0.60 wt % Zn, at least 0.70 wt % Zn, at least 0.80 wt % Zn, at least 0.90 wt % Zn, at least 1.0 wt % Zn, at least 1.1 wt % Zn, at least 1.2 wt % Zn, at least 1.3 wt % Zn, at least 1.4 wt % Zn, at least 1.5 wt % Zn, at least 1.6 wt % Zn, at least 1.7 wt % Zn, at least 1.8 wt % Zn, at least 1.9 wt % Zn, at least 2.2 wt % Zn, at least 2.5 wt % Zn, or at least 2.7 wt % Zn.In terms of ranges, the coating can include from about 0.01 wt % to about 3.0 wt % Zn, e.g., from about 0.01 wt % to about 2.0 wt % Zn, from about 0.01 wt % to about 1.5 wt % Zn, from about 0.03 wt % to about 0.90 wt % Zn, from about 0.05 wt % to about 0.80 wt % Zn, from about 0.10 wt % to about 0.80 wt % Zn, from about 0.20 wt % to about 0.75 wt % Zn ...1.5 wt % Zn % Zn, from about 0.20 wt % to about 0.60 wt % Zn, from about 0.20 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.55 wt % Zn, from about 0.25 wt % to about 0.50 wt % Zn, from about 0.25 wt % to about 0.45 wt % Zn, from about 0.30 wt % to about 0.45 wt % Zn, or from about 0.30 wt % to about 0.40 wt % Zn.

[0082] Thus, in terms of ratios, in some aspects, Ca and Zn can be present in the clad aluminum alloy layer at a Ca:Zn ratio of about 1:10 to about 2:1 (e.g., about 1:9 to about 1:1; about 1:7 to about 1:1; about 1:5 to about 1:1; about 1:4 to about 1:1; or about 1:3 to about 1:1.5) by weight. In addition, Ca and Mg can be present in the clad aluminum alloy layer at a Ca:Mg ratio of about 1:100 to about 100:1.

[0083] The coated aluminum alloy layer can optionally include silicon (Si). In some respects, the coated aluminum alloy layer can include up to about 5.0 wt %Si, for example, up to about 4.5 wt %Si, up to about 4.0 wt %Si, up to about 3.0 wt %Si, up to about 2.0 wt %Si, up to about 1.0 wt %Si, up to about 0.50 wt %Si, up to about 0.25 wt %Si, up to about 0.10 wt %Si, up to about 0.05 wt %Si, up to about 0.04 wt %Si, up to about 0.03 wt %Si, up to about 0.02 wt %Si or up to about 0.01 wt %Si. In terms of scope, coating layer can optionally comprise from about 0.01 weight % to about 5.0 weight % Si, for example, from about 0.03 weight % to about 3.0 weight % Si, from about 0.03 weight % to about 1.0 weight % Si, from about 0.03 weight % to about 0.50 weight % Si, from about 0.03 weight % to about 0.10 weight % Si or from about 0.04 weight % to about 0.06 weight % Si. In some embodiments, Si does not exist (for example, 0 weight %).

[0084] The cladding aluminum alloy layer may optionally include up to about 1.0 wt % iron (Fe), for example, up to about 0.95 wt % Fe, up to about 0.90 wt % Fe, up to about 0.85 wt % Fe, up to about 0.80 wt % Fe, up to about 0.75 wt % Fe, up to about 0.70 wt % Fe, up to about 0.65 wt % Fe, up to about 0.60 wt % Fe, up to about 0.55 wt % Fe, up to about 0.50 wt % Fe. Fe, up to about 0.45 wt % Fe, up to about 0.40 wt % Fe, up to about 0.35 wt % Fe, up to about 0.30 wt % Fe, up to about 0.25 wt % Fe, up to about 0.20 wt % Fe, up to about 0.15 wt % Fe, up to about 0.10 wt % Fe, up to about 0.08 wt % Fe, up to about 0.05 wt % Fe, up to about 0.03 wt % Fe, or up to about 0.01 wt % Fe. In terms of ranges, the cladding aluminum alloy layer can optionally include from about 0.01 wt % to about 1.0 wt % Fe, e.g., from about 0.03 wt % to about 0.90 wt % Fe, from about 0.05 wt % to about 0.80 wt % Fe, from about 0.08 wt % to about 0.80 wt % Fe, from about 0.08 wt % to about 0.75 wt % Fe, from about 0.01 wt % to about 0.70 wt % Fe, from about 0.20 wt % to about 0.60 wt % Fe, from about 0.20 wt % to about 0.55 wt % Fe, from about 0.25 wt % to about 0.55 wt % Fe, from about 0.25 wt % to about 0.50 wt % Fe, or from about 0.30 wt % to about 0.50 wt % Fe. In some embodiments, Fe is absent (e.g., 0 wt %).

[0085] The cladding aluminum alloy layer may optionally include copper (Cu). In some aspects, the cladding aluminum alloy layer may include up to about 1.0 wt % Cu, for example, up to about 0.95 wt % Cu, up to about 0.90 wt % Cu, up to about 0.85 wt % Cu, up to about 0.80 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, up to about 0.65 wt % Cu, up to about 0.60 wt % Cu, up to about 0.55 wt %, up to about 0.50 wt % Cu, up to about 0.08 wt % Cu, up to about 0.10 wt % Cu, up to about 0.15 wt % Cu, up to about 0.20 wt % Cu, up to about 0.25 wt % Cu, up to about 0.30 wt % Cu, up to about 0.40 wt % Cu, up to about 0.55 wt %, up to about 0.50 wt % Cu, up to about 0.60 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, up to about 0.65 wt % Cu, up to about 0.60 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, .45 wt % Cu, up to about 0.40 wt % Cu, up to about 0.35 wt % Cu, up to about 0.30 wt % Cu, up to about 0.25 wt % Cu, up to about 0.20 wt % Cu, up to about 0.15 wt % Cu, up to about 0.10 wt % Cu, up to about 0.05 wt % Cu, up to about 0.04 wt % Cu, up to about 0.03 wt % Cu, up to about 0.02 wt % Cu or up to about 0.01 wt % Cu. In terms of scope, coating layer can optionally comprise from about 0.01 wt % to about 1.0 wt % Cu, for example, from about 0.03 wt % to about 0.80 wt % Cu, from about 0.03 wt % to about 0.30 wt % Cu, from about 0.03 wt % to about 0.10 wt % Cu, from about 0.05 wt % to about 0.6 wt % Cu, from about 0.1 wt % to about 0.6 wt % Cu or from about 0.5 wt % to about 0.6 wt % Cu. In some embodiments, Cu does not exist (for example, 0 wt %).

[0086] The coated aluminum alloy layer can optionally include manganese (Mn). In some aspects, the coated aluminum alloy layer can include up to about 0.5 wt %Mn, for example, up to about 0.45 wt %Mn, up to about 0.40 wt %Mn, up to about 0.35 wt %Mn, up to about 0.30 wt %Mn, up to about 0.25 wt %Mn, up to about 0.20 wt %Mn, up to about 0.15 wt %Mn, up to about 0.10 wt %Mn, up to about 0.05 wt %Mn, up to about 0.04 wt %Mn, up to about 0.03 wt %Mn, up to about 0.02 wt %Mn or up to about 0.01 wt %Mn. In terms of scope, coating layer can optionally be from comprising about 0.01 wt % to about 0.5 wt % Mn, for example, from about 0.03 wt % to about 0.40 wt % Mn, from about 0.03 wt % to about 0.30 wt % Mn, from about 0.03 wt % to about 0.25 wt % Mn, from about 0.04 wt % to about 0.20 wt % Mn or from about 0.10 wt % to about 0.20 wt % Mn. In some embodiments, Mn does not exist (for example, 0 wt %).

[0087] The cladding aluminum alloy layer can optionally include titanium (Ti). In some respects, the cladding layer aluminum alloy layer can include about 0.5 wt %Ti at the most, for example, about 0.45 wt %Ti at the most, about 0.40 wt %Ti at the most, about 0.35 wt %Ti at the most, about 0.30 wt %Ti at the most, about 0.25 wt %Ti at the most, about 0.20 wt %Ti at the most, about 0.15 wt %Ti at the most, about 0.12 wt %Ti at the most, about 0.10 wt %Ti at the most, about 0.05 wt %Ti at the most, about 0.03 wt %Ti at the most, about 0.02 wt %Ti at the most or about 0.01 wt %Ti at the most. In terms of scope, the coating layer can optionally include from about 0.01 wt % to about 0.5 wt % Ti, for example, from about 0.03 wt % to about 0.40 wt % Ti, from about 0.05 wt % to about 0.30 wt % Ti, from about 0.05 wt % to about 0.25 wt % Ti, from about 0.07 wt % to about 0.20 wt % Ti or from about 0.08 wt % to about 0.15 wt % Ti. In some embodiments, Ti does not exist (for example, 0 wt %).

[0088] The coated aluminum alloy layer may optionally include vanadium (V). In some aspects, the coated aluminum alloy layer may include up to about 0.3 wt % V, for example, up to about 0.25 wt % V, up to about 0.20 wt % V, up to about 0.15 wt % V, up to about 0.10 wt % V, up to about 0.08 wt % V, up to about 0.05 wt % V, up to about 0.03 wt % V, up to about 0.02 wt % V or up to about 0.01 wt % V. In terms of ranges, the coating can optionally include from about 0.01 wt % to about 0.30 wt % V, e.g., from about 0.01 wt % to about 0.30 wt % V, from about 0.03 wt % to about 0.30 wt % V, from about 0.05 wt % to about 0.25 wt % V, from about 0.06 wt % to about 0.25 wt % V, from about 0.07 wt % to about 0.20 wt % V, or from about 0.08 wt % to about 0.15 wt % V. In some embodiments, V is absent (e.g., 0 wt %).

[0089] Optionally, the clad aluminum alloy layer described herein may also include other minor elements, sometimes referred to as impurities, in an amount of about 0.05 wt % or less, about 0.04 wt % or less, about 0.03 wt % or less, about 0.02 wt % or less, or about 0.01 wt % or less. These impurities may include, but are not limited to, V, Ni, Sc, Hf, Zr, Sn, Ga, Bi, Na, Pb, or a combination thereof. Thus, for example, V, Ni, Sc, Hf, Zr, Sn, Ga, Bi, Na, or Pb may each be present in the alloy in an amount of about 0.05 wt % or less, about 0.04 wt % or less, about 0.03 wt % or less, about 0.02 wt % or less, or about 0.01 wt % or less. The sum of all impurities does not exceed about 0.50 wt % (e.g., does not exceed about 0.40 wt %, about 0.30 wt %, about 0.25 wt %, about 0.20 wt %, about 0.15 wt %, or about 0.10 wt %). All are expressed in wt %. In some aspects, the remainder of the alloy is aluminum.

[0090] In some respects, Ca, Mg and / or Zn can be alloyed with any suitable series alloy to produce coating as described herein. By a non-limiting example, Ca can be combined with other components of 1xxx series alloy (comprising Fe) to form a coating aluminum alloy layer, such as AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198 or AA1199. As another non-limiting example, Ca can be combined with other components of a 7xxx series alloy (including Zn) to form a cladding aluminum alloy layer, such as 7xxx series alloys: AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A ... A7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA 7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7122, AA7023, AA702 6. AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, A A7041, AA7049, AA7049A, AA7149, AA7204, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7150, AA 7250, AA7055, AA7155, AA7255, AA7056, AA7060, AA7064, AA7065, AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, and AA7099.As another non-limiting example, Ca can be combined with other components of 8xxx series alloys (including Fe) to form a clad aluminum alloy layer, such as AA8006, AA8008, AA8010, AA8112, AA8014, AA8015, AA8016, AA8021, AA8023, AA8026, AA8030, AA8130, AA8150, AA8076, AA8076A, and AA8177.

[0091] In another non-limiting example, due to the increased corrosion resistance provided by the aluminum alloys and coated aluminum alloys, increased levels of alloying elements such as Cu that are traditionally associated with increased corrosion can be included and used in products such as clad products. An example is a high Cu6xxx series aluminum alloy. For example, the aluminum alloy can contain up to 1.0 wt % Cu (e.g., up to about 0.95 wt % Cu, up to about 0.90 wt % Cu, up to about 0.85 wt % Cu, up to about 0.80 wt % Cu, up to about 0.75 wt % Cu, up to about 0.70 wt % Cu, up to about 0.65 wt % Cu, up to about 0.60 wt % Cu, up to about 0.55 wt %, up to about 0.50 wt % Cu, up to about 0.45 wt % Cu, up to about 0.6 ... In some embodiments, Cu is not present (e.g., 0 wt %). Manufacturers are generally reluctant to use such materials due to potential filiform corrosion problems. The corrosion resistance of the increase of the aluminum alloy and the coated aluminum alloy makes it possible to use new alloys such as high Cu 6xxx series aluminum alloys.

[0092] In some examples, the alloy used as the cladding layer can have the following elemental composition as provided in Table 1.

[0093] Table 1

[0094] element Weight Percentage (wt%) Zn 0.01 to 3.0 Ca 0.01 to 1.0 Si Up to 5.0 Mn Up to 0.50 Fe At most 1.0 Cu At most 1.0 Ti Up to 0.50 V Up to 0.30 Impurities Up to 0.25 Al the remaining

[0095] As another example, an alloy used as a cladding layer may have the following elemental composition as provided in Table 2.

[0096] Table 2

[0097] element Weight Percentage (wt%) Zn 0.01 to 3.0 Mg 0.01 to 1.0 Si Up to 5.0 Mn Up to 0.50 Fe At most 1.0 Cu At most 1.0 Ti Up to 0.50 V Up to 0.30 Impurities Up to 0.25 Al the remaining

[0098] As another example, an alloy used as a cladding layer may have the following elemental composition as provided in Table 3.

[0099] Table 3

[0100]

[0101]

[0102] As described above, the clad aluminum alloy product may include one cladding layer or more than one cladding layer. In some cases, the clad aluminum alloy product includes only the first cladding layer. In some cases, the clad aluminum alloy product includes a first cladding layer and a second cladding layer. In some cases, the composition of the first cladding layer and the second cladding layer is the same. In other cases, the composition of the first cladding layer and the second cladding layer is different. The resulting clad aluminum alloy product exhibits excellent balance properties, such as strength, formability, corrosion resistance, dent resistance and hemming performance.

[0103] In some cases, the thickness of the first coating layer can be about 1% to 25% of the total coated product thickness (e.g., about 1% to about 12% of the total coated product thickness or about 10% of the total coated product thickness). In some cases, when the second coating layer exists, the thickness of the second coating layer can be about 1% to 25% of the total coated product thickness (e.g., about 1% to about 12% of the total coated product thickness or about 10% of the total coated product thickness).

[0104] The cladding layer as described herein can improve the surface corrosion resistance of the product, improve pretreatment efficiency, assist bending, rivet hole perforation and press riveting, and make some parts of the alloy product available in T4 temper without hot forming. In addition, when a filler wire alloy such as AA7021 is used as a cladding layer, laser welding can be completed without using a filler wire.

[0105] Methods for preparing aluminum alloys, coated aluminum alloys and clad aluminum alloy products

[0106] The alloys described herein for use as core layers and cladding layers may be cast using any suitable casting method. As some non-limiting examples, the casting process may include a direct chill (DC) casting process or a continuous casting (CC) process.

[0107] The cladding layer as described herein may be attached to the core layer as described herein by any means known to those of ordinary skill in the art to form a clad aluminum alloy product. For example, the cladding layer may be attached to the core layer by direct chill co-casting (i.e., melt casting), such as described in, for example, U.S. Patents 7,748,434 and 8,927,113, both of which are hereby incorporated by reference in their entirety; or hot rolling and cold rolling clad ingots, such as described in U.S. Patent 7,472,740, which is hereby incorporated by reference in its entirety; or roll bonding to achieve the desired metallurgical bond between the core layer and the cladding layer; or other methods known to those of ordinary skill in the art. The initial and final dimensions of the clad aluminum alloy product described herein may be determined by the desired properties of the overall final product.

[0108] The roll bonding process can be performed in different ways. For example, the roll bonding process can include hot rolling and cold rolling. In addition, the roll bonding process can be a one-step process or a multi-step process, in which the material is reduced in size during successive rolling steps. The individual rolling steps can optionally be separated by other processing steps, including, for example, annealing steps, cleaning steps, heating steps, cooling steps, etc.

[0109] The co-cast ingot or other cast product can be processed by any means known to those of ordinary skill in the art. Optionally, a processing step can be used to produce sheet. Such processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, solution heat treatment, and optional pre-aging steps, as known to those of ordinary skill in the art.

[0110] In the homogenization step of the DC casting process, the co-cast ingot described herein is heated to a temperature in the range of about 400°C to about 500°C, or any suitable temperature. For example, the ingot may be heated to a temperature of about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, or about 500°C. The ingot is then soaked (i.e., maintained at a specified temperature) for a period of time. In some examples, the total time of the homogenization step (including the heating and soaking stages) may be up to 24 hours. For example, in a homogenization step with a total time of up to 18 hours, the ingot may be heated to up to 500°C and soaked. Optionally, in a homogenization step with a total time of more than 18 hours, the ingot may be heated to less than 490°C and soaked. In some cases, the homogenization step includes multiple processes. In some non-limiting examples, the homogenization step includes heating the ingot to a first temperature and holding it for a first period of time, and then heating it to a second temperature and holding it for a second period of time. For example, the ingot can be heated to about 465°C and held for about 3.5 hours, and then heated to about 480°C and held for about 6 hours.

[0111] After the homogenization step of the co-cast ingot, a hot rolling step may be performed. Before starting hot rolling, the homogenized ingot may be cooled to a temperature such as about 300° C. to about 450° C. For example, the homogenized ingot may be cooled to a temperature of about 325° C. to about 425° C. or about 350° C. to about 400° C. The ingot may then be hot rolled at a temperature between 300° C. and 450° C. to form a hot rolled plate, hot rolled satur plate, or hot rolled sheet having a gauge from about 3 mm to about 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or any value therebetween).

[0112] Optionally, the cast product can be a continuously cast product, which can be cooled after the high temperature continuous casting step to a temperature such as from about 300° C. to about 450° C. For example, the continuously cast product can be cooled to a temperature from about 325° C. to about 425° C. or from about 350° C. to about 400° C. The continuously cast product can then be hot rolled at a temperature from about 300° C. to about 450° C. to form a hot rolled plate, hot rolled Saudi plate, or hot rolled sheet having a gauge from about 3 mm to about 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or any value therebetween). During hot rolling, temperature and other operating parameters may be controlled so that the temperature of the clad alloy hot rolled product when leaving the hot rolling mill does not exceed about 470°C, does not exceed about 450°C, does not exceed about 440°C, or does not exceed about 430°C.

[0113] The clad plate, Saudi plate or sheet can then be cold rolled using conventional cold rolling mills and techniques. Optionally, the cold rolled clad product (e.g., sheet or Saudi plate) can have a specification of about 0.5 mm to about 10 mm (e.g., between about 0.7 mm to about 6.5 mm). Optionally, the cold rolled clad sheet can have a specification of 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, 5.5 mm, 6.0 mm, 6.5 mm, 7.0 mm, 7.5 mm, 8.0 mm, 8.5 mm, 9.0 mm, 9.5 mm or 10.0 mm. Cold rolling can be performed to obtain a final gauge thickness representing a gauge reduction of up to about 85% (e.g., a reduction of up to about 10%, up to about 20%, up to about 30%, up to about 40%, up to about 50%, up to about 60%, up to about 70%, up to about 80%, or up to about 85%). Optionally, an intermediate annealing step can be performed during the cold rolling step. The intermediate annealing step can be performed at a temperature such as from about 300°C to about 450°C (e.g., about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, or about 450°C). In some cases, the intermediate annealing step includes multiple processes. In some non-limiting examples, the intermediate annealing step includes heating the cold rolled clad plate, saturated plate or sheet to a first temperature and maintaining it for a first period of time, and then heating it to a second temperature and maintaining it for a second period of time. For example, the cold rolled clad plate, saturated plate or sheet can be heated to about 410°C and maintained for about 1 hour, and then heated to about 330°C and maintained for about 2 hours.

[0114] Subsequently, the clad plate, the saud plate or the sheet material may undergo a solution heat treatment step. The solution heat treatment step may include any conventional treatment of the clad plate, which results in the solubilization of soluble particles. The clad plate, the saud plate or the sheet material may be heated to a peak metal temperature (PMT) of at most, for example, about 590°C (e.g., about 400°C to about 590°C), and soaked for a period of time at this temperature. For example, the clad plate, the saud plate or the sheet material may be soaked for up to about 30 minutes (e.g., 0 seconds, about 60 seconds, about 75 seconds, about 90 seconds, about 5 minutes, about 10 minutes, about 20 minutes, about 25 minutes or about 30 minutes) at about 480°C. After heating and soaking, the clad plate, the saud plate or the sheet material may be rapidly cooled to a temperature of about 500°C to about 200°C at a rate greater than 50°C / second (°C / s). In one example, the clad plate, satin plate or sheet is cooled from a temperature of about 450° C. to a temperature of about 200° C. at a quenching rate greater than 200° C. / s. Optionally, the cooling rate may be faster in other cases.

[0115] After quenching, the clad plate, saturated plate or sheet can be optionally pre-aged by reheating the plate, saturated plate or sheet and then coil cooling. The pre-aging treatment can be carried out at a temperature of about 50°C to about 150°C for a period of time such as up to about 6 hours. For example, the pre-aging treatment can be carried out at a temperature of about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 110°C, about 115°C, about 120°C, about 125°C, about 130°C, about 135°C, about 140°C, about 145°C or about 150°C. Optionally, a pre-aging treatment of about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours or about 6 hours can be carried out. The pre-aging treatment may be performed by passing the board, satin board or sheet through a heating device, such as a device that emits radiant heat, convection heat, induction heat, infrared heat, or the like.

[0116] Co-cast ingots or other co-cast products as described herein can also be used to prepare products or other suitable products in the form of plates. The products can be prepared using technology known to those of ordinary skill in the art. For example, the plate comprising the coated product as described herein can be prepared by processing the co-cast ingots in a homogenization step or casting the co-cast products in a continuous casting machine and then carrying out a hot rolling step. In the hot rolling step, the cast product can be hot rolled to a specification of 200mm thick or less (for example, about 10mm to about 200mm). For example, the cast product can be hot rolled into a plate having a final specification thickness of about 10mm to about 175mm, about 15mm to about 150mm, about 20mm to about 125mm, about 25mm to about 100mm, about 30mm to about 75mm or about 35mm to about 50mm.

[0117] Properties of clad aluminum alloy products

[0118] The clad aluminum alloy product described herein can be designed to reach any desired strength level determined by those of ordinary skill in the art. For example, the clad aluminum alloy product described herein can have a yield strength of at most about 600MPa (e.g., from about 150MPa to about 600MPa, from about 450MPa to about 600MPa, or from about 500MPa to about 600MPa). In some embodiments, the yield strength of the product can be about 400MPa, about 425MPa, about 450MPa, about 475MPa, about 500MPa, about 525MPa, about 550MPa, about 575MPa, or about 600MPa.

[0119] In addition, the clad aluminum alloy products described herein can have an elongation of up to about 50%. For example, the elongation can be about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, or about 5%.

[0120] In addition, the clad aluminum alloy product described herein can have strong bendable properties. Depending on the desired use of the product, a bending angle of about 45° to about 120° can be achieved, as measured by a three-point bending test according to VDA standard 238-100, and the measurement result is normalized to 2.0 mm. For example, the clad aluminum alloy product described herein can achieve a bending angle of about 45°, about 50°, about 55°, about 60°, about 65°, about 70°, about 75°, about 80°, about 85°, about 90°, about 95°, about 100°, about 105°, about 110°, about 115° or about 120°.

[0121] In some instances, the clad aluminum alloy product (e.g., clad aluminum alloy sheet) manufactured according to the method described herein may have a minimum R / t ratio (i.e., f factor) of about 1.2 without breaking. The R / t ratio can provide an assessment of the bendability of the material. As described below, bendability is assessed based on the R / t ratio, where R is the radius of the tool (die) used and t is the thickness of the material. A lower R / t ratio indicates that the bendability of the material is better. The R / t ratio of the clad aluminum alloy layer described herein can be about 1.1 or lower (e.g., about 1.0 or lower, about 0.9 or lower, about 0.8 or lower, or about 0.7 or lower).

[0122] How to use clad aluminum alloy products

[0123] The coated aluminum alloy products described herein can be used for automotive applications and other transportation applications, including aircraft and railway applications. For example, the coated aluminum alloy products can be used to prepare automotive structural parts, such as bumpers, side beams, top beams, cross beams, pillar reinforcements (e.g., A-pillars, B-pillars and C-pillars), inner panels, outer panels, side panels, inner covers, outer covers or trunk covers. The coated aluminum alloy products and methods described herein can also be used in applications of aircraft or railway vehicles to prepare, for example, outer and inner panels. In some instances, the coated aluminum alloy products can be used for aerospace structural parts and non-structural parts or marine structural parts or non-structural parts.

[0124] The clad aluminum alloy products and methods described herein can also be used in electronic applications. For example, the clad aluminum alloy products and methods described herein can be used to prepare housings for electronic devices, including mobile phones and tablet computers. In some examples, the clad aluminum alloy products can be used to prepare housings for mobile phones (e.g., smart phones) and outer covers for tablet chassis.

[0125] The clad aluminum alloy products and methods described herein can also be used in other applications as needed. The clad aluminum alloy products described herein can be provided as clad aluminum alloy sheets and / or clad aluminum alloy plates suitable for further processing by end users. For example, the clad aluminum alloy sheets can be further surface treated by end users to be used as building cladding panels for aesthetic and structural purposes.

[0126] The clad aluminum alloy products described herein can also be joined to other materials to form useful products. Methods of joining the clad alloy products to other materials can include, but are not limited to, resistance spot welding (RSW), friction stir welding, remote laser welding, metal inert gas (MIG) welding, tungsten inert gas (TIG) welding, bonding, and self-piercing riveting. The alloy products can be used in a variety of applications, including automotive, transportation, electronics, and other applications.

[0127] The following examples will be used to further illustrate the present invention, but do not constitute any limitation of the present invention. On the contrary, it should be clearly understood that after reading the specification of this article, those skilled in the art can think of making various other embodiments, modifications and equivalent schemes without departing from the spirit of the present invention. In the research process described in the following examples, unless otherwise stated, conventional procedures are followed. Some programs are described below for illustrative purposes.

[0128] Example

[0129] Aluminum alloy coating

[0130] The cladding aluminum alloy layer is produced by subjecting the alloy described in Table 4 to casting, hot rolling and cold rolling, annealing at a temperature above 500°C, and quenching.

[0131] As shown in Table 4, Comparative Example Alloys 1, 2, and 3 were prepared as comparisons to Example Alloy 1, which had a similar composition to Comparative Example Alloys 1, 2, and 3, but also had a combination of Ca (0.25 wt%) and higher Zn (0.45 wt%). Comparative Example Alloys 4 and 5 were prepared as comparisons to Example Alloy 2, which had a similar composition to Alloys 4 and 5, but also had a combination of Ca (0.54 wt%) and higher Zn (0.95 wt%).

[0132] Table 4

[0133]

[0134]

[0135] All figures are expressed in wt%. Each composition contains a maximum of 0.25 wt% impurities. The remainder is Al.

[0136] Strength properties of clad aluminum alloy

[0137] ISO 4623-2 (2016) was used to measure the filiform corrosion of comparative alloys 1 to 5 and example alloys 1 and 2. In addition, the phosphatization treatability of comparative alloy 1 and example alloys 1 and 2 was measured using a classic 3-cation zinc-phosphate process. Figures 1 to 4 The filiform corrosion tests of comparative alloys 1 to 5 and example alloys 1 and 2 are shown. Figure 1 and Figure 2 As shown, Example Alloy 1 shows excellent filiform corrosion resistance compared to the comparative example. In terms of the lowest coverage (%) in the horizontal and vertical directions and the lowest average corrosion wire length in the vertical and horizontal directions, Example Alloy 1 gives the best filiform corrosion results compared to the comparative example. Similarly, Figure 3 and Figure 4 As shown, Example Alloy 2 shows excellent filiform corrosion resistance compared to the comparative example. In terms of the lowest coverage (%) in the horizontal and vertical directions and the lowest average corrosion wire length in the vertical and horizontal directions, Example Alloy 2 gives the best filiform corrosion results compared to the comparative example.

[0138] Figure 5 and Figure 6 The same results are shown visually. Figure 5 Micrographs of filiform corrosion test results for Comparative Example Alloys 1 to 3 and Example Alloy 1 are shown. Figure 6 Micrographs showing the filiform corrosion test results for Comparative Example Alloys 4 to 5 and Example Alloy 2. Figure 5 and Figure 6 As shown, for Example Alloys 1 and 2, significantly less filiform corrosion was observed in the microstructure of the samples than for the Comparative Example alloys.

[0139] Figure 7 The phosphating properties of Comparative Example Alloy 1 and Example Alloys 1 and 2 are shown. Figure 7 The results show that the phosphate treatment of the three samples is comparable and all are good. The grade of phosphate crystal homogeneity was determined using scanning electron microscopy and ranged from 1-4. The coating weight is expressed in g / m 2 Comparative Example Alloy 1 has a grade of 2-3 and a coating weight of 5.1 g / m 2 Example Alloy 1 is grade 2-3 and the coating weight is 4.7 g / m 2 , which is comparable to Comparative Example Alloy 1. Example Alloy 2 has a rating of 3, which is also comparable to the other test samples, and the coating weight was not measured.

[0140] Aluminum Alloy

[0141] The aluminum alloy is prepared with the composition in Table 5. The adhesion durability performance of the aluminum alloy is measured using a stress durability test of adhesive bonding. The adhesion durability test evaluates the bond strength produced between the bonded products, and can indicate the ability of the near-surface microstructure of the aluminum alloy product to be firmly bonded to the adhesive under long-term use and corrosion conditions or conditions different from environmental conditions. During the test, a bond is produced between two aluminum alloy products by an adhesive such as an epoxy resin. Then, the bonded aluminum alloy products are subjected to strain and / or other conditions. For example, the bonded aluminum alloy products may be immersed or sprayed (e.g., according to the NSS test) with a salt solution, subjected to wet conditions or dry conditions. After a series of cycles under one or more conditions, the chemical and mechanical failure of the bond between the aluminum alloy products is evaluated in the instance of the use cycle. In other instances, the chemical and mechanical failure of the product is evaluated after a single immersion or spraying. The adhesion durability performance of the aluminum alloy product indicates or depends on the reactivity and corrosion sensitivity of the near-surface microstructure of the product.

[0142] The example standard test for determining the adhesion durability is ASTM D3433-99 (2012) Standard Test Method for Fracture Strength in Cleavage of Adhesives in Bonded Metal Joints, ASTM International, West Conshohocken, PA, 2012, which is hereby incorporated by reference. During the adhesion durability test, each sample is made of two aluminum alloy products, prepared and processed using the same conditions, and bonded together using epoxy resin adhesives through six bonding points. Then, each sample is subjected to various test conditions. For example, the test conditions may include immersion in a salt solution, exposure to wet conditions, exposure to dry conditions, or one or more of the forces that cause stress or strain. Each sample is subjected to multiple cycles of these test conditions. The number of cycles that the sample is subjected to is the number of cycles or 60 cycles that reach mechanical failure, i.e., the maximum number of cycles used in this particular test. Mechanical failure includes adhesion failure, metal product fracture or adhesion fracture. Therefore, the bonding surface may be related to the waiting period before being bonded to another surface, substrate or product.

[0143] The example alloys are arranged in the order of increasing stress durability performance in Table 5, wherein example alloy 7 has the highest stress durability performance.

[0144] Table 5

[0145]

[0146] Aluminum Alloy Filiform Corrosion Test

[0147] The other aluminum alloys were produced by subjecting the alloy compositions described in Table 6 to casting, hot and cold rolling, annealing at a temperature of 500° C. or higher, and quenching.

[0148] Table 6

[0149]

[0150] All figures are expressed in wt%. All compositions contain a maximum of 0.25 wt% impurities. The remainder is Al.

[0151] ISO4623-2 (2016) was used to measure the filiform corrosion of Comparative Example Alloy 6 and Example Alloys 8 to 11. The filiform corrosion test results of Comparative Example Alloy 6 and Example Alloys 8 to 11 are shown in Figure 8 and 9 middle. Figure 8 The average and maximum corrosion filament lengths in the vertical and horizontal directions are shown. Fig. 9 The coverage (%) in the horizontal and vertical directions is shown.

[0152] illustrate

[0153] As used hereinafter, any reference to a series of instructions should be understood as a reference to each of those instructions individually (eg, "Instructions 1 to 4" should be understood as "Instructions 1, 2, 3, or 4").

[0154] Description 1 is an aluminum alloy comprising about 0.01 wt % to about 1.0 wt % Ca; about 0.01 wt % to about 2.0 wt % Zn; up to 5.0 wt % Si; up to 1.0 wt % Fe; up to 0.25 wt % impurities; and Al.

[0155] Description 2 is an aluminum alloy comprising about 0.01 wt % to about 5.0 wt % Mg; about 0.01 wt % to about 8.0 wt % Zn; up to 5.0 wt % Si; up to 1.0 wt % Fe; up to 0.25 wt % impurities; and Al.

[0156] Statement 3 is an aluminum alloy as described in any preceding or subsequent statement, wherein the aluminum alloy is a cladding layer.

[0157] Statement 4 is an aluminum alloy as described in any preceding or subsequent statement, wherein the Ca and Zn are present in a ratio of about 1 :5 to about 1 :1 by weight Ca to Zn.

[0158] Statement 5 is an aluminum alloy as described in any preceding or subsequent statement, wherein the Ca and Zn are present in a ratio of about 1 :3 to about 1 :1.5 by weight Ca to Zn.

[0159] Statement 6 is an aluminum alloy as described in any preceding or subsequent statement, further comprising from about 0.01 wt % to about 0.9 wt % Cu.

[0160] Note 7 is an aluminum alloy as described in any preceding or subsequent note, further comprising from about 0.5 wt % to about 0.6 wt % Cu.

[0161] Note 8 is an aluminum alloy as described in any preceding or subsequent note, further comprising from about 0.01 wt % to about 0.5 wt % Mn.

[0162] Note 9 is an aluminum alloy as described in any preceding or subsequent note, further comprising from about 0.01 wt % to about 0.3 wt % V.

[0163] Note 10 is an aluminum alloy as described in any preceding or subsequent note, comprising from about 0.2 wt % to about 0.6 wt % Ca, optionally from 0.3 wt % to 0.6 wt % Ca.

[0164] Description 11 is an aluminum alloy as described in any preceding or subsequent description, comprising from about 0.4 wt % to about 1.0 wt % Zn, optionally from 0.5 wt % to 1.0 wt %.

[0165] Description 12 is an aluminum alloy as described in any preceding or subsequent description, comprising from about 0.03 wt % to about 0.10 wt % Si.

[0166] Description 13 is an aluminum alloy as described in any preceding or subsequent description, comprising from about 0.08 wt % to about 0.80 wt % Fe.

[0167] Description 14 is an aluminum alloy as described in any preceding or subsequent description, having a coverage percentage of 18% or less in each of the horizontal and vertical directions when tested according to the filiform corrosion test of ISO 4623-2 (2016).

[0168] Description 15 is an aluminum alloy as described in any preceding or subsequent description, having an average corrosion wire length of 0.50 mm or less in each of the horizontal and vertical directions during filiform corrosion testing as measured according to ISO 4623-2 (2016).

[0169] Description 16 is an automotive structural component comprising an aluminum alloy as described in any preceding or subsequent description.

[0170] Description 17 is a coated aluminum alloy product comprising an aluminum alloy substrate, a coating on a surface of the aluminum alloy substrate, the coating comprising Mg, Ca, Zn, Ni, or a combination thereof in an amount sufficient to prevent corrosion in the aluminum alloy substrate.

[0171] Description 18 is a coated aluminum alloy product as described in any preceding or subsequent description, wherein the coating on the surface of the aluminum alloy substrate is applied using chemical washed physical vapor deposition ("PVD") or chemical vapor deposition ("CVD").

[0172] Description 19 is a coated aluminum alloy product as described in any preceding or subsequent description, wherein the coated aluminum alloy product is a cladding layer.

[0173] Description 20 is a clad aluminum alloy product comprising a core layer having a first side and a second side; and a first cladding layer in contact with the first side of the core layer, wherein the first cladding layer comprises from about 0.01 wt % to about 2.0 wt % Zn, from about 0.1 wt % to about 1.0 wt % Ca, and from about 0.1 wt % to about 1.0 wt % Mg.

[0174] Statement 21 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the Ca and Zn are present in the first cladding layer in a ratio of Ca to Zn from about 1 :5 to about 1 :1 by weight.

[0175] Statement 22 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the first cladding layer comprises from about 0.20 wt % to about 0.60 wt % Ca, optionally from 0.30 wt % to 0.60 wt % Ca.

[0176] Statement 23 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the first cladding layer comprises between about 0.40 wt % and about 1.0 wt % Zn, optionally from 0.50 wt % to 1.0 wt % Zn.

[0177] Statement 24 is the clad aluminum alloy product of any preceding or subsequent statement, wherein the first cladding layer has a thickness of about 1% to 25% of the total thickness of the clad aluminum alloy product.

[0178] Note 25 is a clad aluminum alloy product as described in any preceding or subsequent note, wherein the core layer has a thickness of about 0.7 mm to 2.3 mm.

[0179] Statement 26 is a clad aluminum alloy product as described in any preceding or subsequent statement, further comprising a second cladding layer positioned on the second side of the core layer.

[0180] Statement 27 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the first cladding layer and the second cladding layer comprise the same alloy.

[0181] Statement 28 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the first cladding layer and the second cladding layer comprise different alloys.

[0182] Note 29 is a clad aluminum alloy product as described in any preceding or subsequent note, wherein the second cladding layer comprises between about 0.20 wt % and about 0.60 wt % Ca and between about 0.40 wt % and about 1.0 wt % Zn, optionally from 0.30 wt % to 0.60 wt % Ca and from 0.50 wt % to 1.0 wt % Zn.

[0183] Description 30 is a clad aluminum alloy product as described in any preceding or subsequent description, wherein the core layer comprises a 1xxx series aluminum alloy, a 2xxx series alloy, a 3xxx series aluminum alloy, a 4xxx series alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, or an 8xxx series aluminum alloy.

[0184] Note 31 is a clad aluminum alloy product as described in any preceding or subsequent note, wherein the core layer comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0185] Statement 32 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the clad aluminum alloy product has a yield strength of at least 550 MPa.

[0186] Statement 33 is a clad aluminum alloy product as described in any preceding or subsequent statement, wherein the clad aluminum alloy product has a total elongation of at most 20%.

[0187] Description 34 is a clad aluminum alloy product as described in any preceding or subsequent description, wherein the clad aluminum alloy product is a sheet, a plate, an electronic device housing, an automotive structural component, an aerospace structural component, an aerospace non-structural component, a marine structural component, or a marine non-structural component.

[0188] All patents, publications and abstracts cited above are incorporated herein by reference in their entirety. In order to achieve the various objects of the present invention, various embodiments of the present invention have been described. It should be appreciated that these embodiments are merely illustrative of the principles of the present invention. Various modifications and alterations thereof will be apparent to those skilled in the art without departing from the spirit and scope of the present invention as defined in the following claims.

Claims

1. A clad aluminum alloy product, comprising: a core layer having a first side and a second side; as well as A first cladding layer in contact with the first side of the core layer, wherein the first cladding layer comprises from 0.01 wt % to 2.0 wt % Zn, from 0.1 wt % to 1.0 wt % Ca, and from 0.1 wt % to 1.0 wt % Mg, and Al.

2. The clad aluminum alloy product of claim 1, wherein the Ca and Zn are present in the first cladding layer in a ratio of Ca to Zn of from 1:5 to 1:1 by weight.

3. The clad aluminium alloy product of claim 1 or 2, wherein the first cladding layer comprises from 0.20 wt% to 0.60 wt% Ca.

4. The clad aluminium alloy product of any one of claims 1 to 3, wherein the first cladding layer comprises between 0.40 wt. % and 1.0 wt. % Zn.

5. The clad aluminum alloy product according to any one of claims 1 to 4, wherein the first cladding layer has a thickness of 1% to 25% of the total thickness of the clad aluminum alloy product.

6. The clad aluminium alloy product according to any one of claims 1 to 5, wherein the core layer has a thickness of 0.7 mm to 2.3 mm.

7. The clad aluminum alloy product of any one of claims 1 to 6, further comprising a second cladding layer positioned on the second side of the core layer.

8. The clad aluminum alloy product of claim 7, wherein the first cladding layer and the second cladding layer comprise the same alloy.

9. The clad aluminum alloy product of claim 7, wherein the first cladding layer and the second cladding layer comprise different alloys.

10. The clad aluminium alloy product of any one of claims 1 to 9, wherein the second cladding layer comprises between 0.20 wt% and 0.60 wt% Ca and between 0.40 wt% and 1.0 wt% Zn.

11. The clad aluminum alloy product of any one of claims 1-10, wherein the core layer comprises a 1xxx series aluminum alloy, a 2xxx series alloy, a 3xxx series aluminum alloy, a 4xxx series alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, or an 8xxx series aluminum alloy.

12. The clad aluminum alloy product of any one of claims 1-11, wherein the core layer comprises a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, or a 7xxx series aluminum alloy.

13. The clad aluminum alloy product of any one of claims 1-12, wherein the clad aluminum alloy product has a yield strength of at least 550 MPa.

14. The clad aluminium alloy product of any one of claims 1 to 13, wherein the clad aluminium alloy product has a total elongation of at most 20%.

15. The clad aluminum alloy product of any one of claims 1 to 14, wherein the clad aluminum alloy product is a sheet, a plate, an electronic device housing, an automotive structural component, an aerospace structural component, an aerospace non-structural component, a marine structural component, or a marine non-structural component.

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