Patent Description:
The invention relates to an automotive structural part.

To be useful in various applications, for example in the production of automobile components, an aluminum alloy product must offer a good combination of properties, especially when compared with the alternatives. A useful aluminum alloy product, for example a clad product or a coated aluminum alloy product, offers good formability and mechanical properties, along with other key attributes, such as corrosion resistance and high applicability of paint line pretreatments. Current aluminum alloy products may offer some of these properties, but not all. For example, previously known alloys may offer good formability and mechanical properties, along with sufficient applicability of paint line pretreatments, but limited corrosion resistance. Some previously known alloys may offer good formability, but may suffer from low strength and/or applicability of paint line pretreatments.

<CIT> discloses a method for adding Ca to aluminum alloy. JPH1180871A discloses aluminum alloy clad material for heat exchanger. <CIT> discloses fin material for heat exchanger made of aluminum. <CIT> discloses a composite material for vacuum brazing. <CIT> discloses a composite aluminum alloy for cables and preparation method of composite aluminum alloy. <CIT> discloses Al-Mg-Si aluminium alloy and preparation method thereof. <NPL>, reports results on the surface treatment of commercial aluminum by nitrogen ion implantation. <CIT> discloses an aluminum alloy brazing sheet. <NPL> is a study on the variations of the microstructure and mechanical properties with Ca and Mn elements for Al-Si-Fe-Cu-Zn alloys. <CIT> discloses a multi-layer metal sheet comprising a core layer and a first cladding layer comprising an aluminium alloy comprising about <NUM>-<NUM>. % Fe, <NUM>-<NUM>. % Mn, up to <NUM>. % Si, up to <NUM>. % Cu, up to <NUM> wt. % Mg, up to <NUM>. % Zn, one or more additional elements selected from the group consisting of Ni, Ti, Co, Nb, Cr, V, Zr, Hf and Ta and up to <NUM> wt. % impurities, with the remainder as Al.

An automotive structural part according to the invention is defined in claim <NUM>.

Described herein are aluminum alloys, surface layers (e.g., coatings) for aluminum alloys, coated aluminum alloy products made from these coatings, and new clad products made from these aluminum alloys and coated aluminum alloys, and methods of 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 possess a surprising combination of strength and other key attributes, such as corrosion resistance, formability, and good applicability of paint line pretreatments. Only the automotive structural part according to the claims belongs to the invention. The rest is outside of the claimed invention.

The aluminium alloys used in the clad aluminium layer of the automotive part according to the invention comprises calcium (Ca) and zinc (Zn). In another embodiment which is not according to the invention, the aluminum alloys can comprise magnesium (Mg) and Zn. In yet another embodiment which is not according to the invention, the aluminum alloys can comprise Ca, Mg, and Zn. The aluminum alloys comprise Ca and Zn according to the claimed composition and are used as the clad aluminum alloy layer in the claimed automotive structural part. In some aspects which are not according to the invention, the aluminum alloys described herein can be used as clad aluminum alloy layers and comprise Mg and Zn. In some aspects which are not according to the invention, the aluminum alloys described herein can be used as clad aluminum alloy layers and comprise Ca, Mg, and Zn. The clad aluminum alloy layers achieve excellent surface properties as described herein.

In another embodiment which is not according to the invention, the coated aluminum alloy products comprise a surface layer (e.g., a coating) comprising Mg, Ca, Zn, nickel (Ni), or combinations thereof. The surface layer can be positioned on an aluminum alloy substrate. The Mg, Ca, Zn, Ni, or combination thereof can be in a form where the Mg, Ca, Zn, and/or Ni is available to inhibit corrosion in the aluminum alloy substrate.

Described are new clad products made from aluminum alloys, and methods of making clad aluminum alloy layers and clad products. These clad aluminum alloy layers and clad products possess a surprising combination of strength and other key attributes, such as corrosion resistance, formability, and good applicability of paint line pretreatments. Only the automotive structural part according to the claims belongs to the invention. The rest is outside of the claimed invention.

In this description, reference is made to alloys identified by AA numbers and other related designations, such as "series" or "7xxx. " For an understanding of the number designation system most commonly used in naming and identifying aluminum and its alloys, see "<NPL>" or "<NPL>.

As used herein, a plate generally has a thickness of greater than about <NUM>. For example, a plate may refer to an aluminum product having a thickness of greater than <NUM>, greater than <NUM>, greater than <NUM>, greater than <NUM>, greater than <NUM>, greater than <NUM>, greater than <NUM>, greater than <NUM>, or greater than <NUM>.

As used herein, a shate (also referred to as a sheet plate) generally has a thickness of from about <NUM> to about <NUM>. For example, a shate may have a thickness of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>.

As used herein, a sheet generally refers to an aluminum product having a thickness of less than about <NUM>. For example, a sheet may have a thickness of less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, less than <NUM>, or less than <NUM>.

Reference is made in this application to alloy temper or condition. For an understanding of the alloy temper descriptions most commonly used, see "<NPL>. " An F condition or temper refers to an aluminum alloy as fabricated. An O condition or temper refers to an aluminum alloy after annealing. An Hxx condition or temper, also referred to herein as an H temper, refers to a non-heat treatable aluminum alloy after cold rolling with or without thermal treatment (e.g., annealing). Suitable H tempers include Hx1, Hx2, Hx3 Hx4, Hx5, Hx6, Hx7, Hx8, or Hx9 tempers. A T1 condition or temper refers to an aluminum alloy cooled from hot working and naturally aged (e.g., at room temperature). A T2 condition or temper refers to an aluminum alloy cooled from hot working, cold worked and naturally aged. A T3 condition or temper refers to an aluminum alloy solution heat treated, cold worked, and naturally aged. A T4 condition or temper refers to an aluminum alloy solution heat treated and naturally aged. A T5 condition or temper refers to an aluminum alloy cooled from hot working and artificially aged (at elevated temperatures). A T6x condition or temper refers to an aluminum alloy solution heat treated and artificially aged. A T7 condition or temper refers to an aluminum alloy solution heat treated and artificially overaged. A T8x condition or temper refers to an aluminum alloy solution heat treated, cold worked, and artificially aged. A T9 condition or temper refers to an aluminum alloy solution heat treated, artificially aged, and cold worked.

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

As used herein, the meaning of "room temperature" can include a temperature of from about <NUM> to about <NUM>, for example about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>. As used herein, the meaning of "ambient conditions" can include temperatures of about room temperature, relative humidity of from about <NUM> % to about <NUM> %, and barometric pressure of from about <NUM> millibar (mbar) to about <NUM> mbar. For example, relative humidity can be about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM>%, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, or anywhere in between. For example, barometric pressure can be about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, about <NUM> mbar, or anywhere in between.

All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of "<NUM> to <NUM>" should be considered to include any and all subranges between (and inclusive of) the minimum value of <NUM> and the maximum value of <NUM>; that is, all subranges beginning with a minimum value of <NUM> or more, e.g. <NUM> to <NUM>, and ending with a maximum value of <NUM> or less, e.g., <NUM> to <NUM>.

As used herein, the meaning of "a," "an," and "the" includes singular and plural references unless the context clearly dictates otherwise.

As used herein, "clad layer," "cladding layer," or "clad aluminum alloy layer" refers to a material that is or will be used as a cladding on a core layer. A "core layer" or "core aluminum alloy layer" refers to the inner material that can be the major component in a clad product (e.g., at least <NUM> % or more of the clad product). A "clad product" or "clad aluminum alloy product" refers to the combination of at least one clad layer on a core layer.

As used herein, "corrosion coverage percent" means the corrosion coverage area as a percentage of the total area of the surface. "Corrosion coverage area" is the area that is covered by corrosion after the surface undergoes corrosion testing.

As used herein, "bond durability" refers to an ability of a bonding agent bonding two articles together to withstand cycled mechanical stress or non-cycled stress (e.g., using the Neutral Salt Spray ("NSS") test) after exposure to environmental conditions that initiate failure of the bonding agent. Bond durability can be characterized in terms of number of mechanical stress cycles applied to the bound articles until the bond fails in one example using cycled mechanical stress.

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 <NUM> atoms of the material (e.g., aluminum alloy, substrate, sheet, surface), expressed as a percent.

Throughout the application, the aluminum alloy and clad products and their components are described in terms of their elemental composition in weight percent (wt. In some aspects, in each alloy the remainder is aluminum, with a maximum of <NUM> wt. % for the sum of all impurities (e.g., a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, a maximum of <NUM> wt. %, and/or a maximum of <NUM> wt. According to the invention, the remainder is Al and the total impurity amount can be up to <NUM> wt.

Described herein are aluminum alloys that comprise Ca and Zn; Mg and Zn, which is not according to the invention; or Ca, Mg, Zn, which is not according to the invention, and can be, in some aspects, clad aluminum alloy layers (sometimes referred to as clad layers, or cladding). The inventors discovered that clad aluminum alloy layers containing amounts of Ca and Zn as described herein surprisingly achieve exceptional resistance to filiform corrosion and excellent applicability of paint line pretreatments, in addition to good strength and formability. The prior conventional thinking in the art was that having increased Ca and/or Mg content, such as in the amounts described herein, would induce corrosion.

In terms of ranges, the aluminum alloy comprises from <NUM> wt. % to <NUM> wt. % Ca, e.g., from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, or from about <NUM> wt. % to about <NUM> wt.

In terms of ranges, the aluminum alloy comprises from <NUM> wt. % to <NUM> wt. % Zn, e.g., from <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn or from about <NUM> wt. % to about <NUM> wt.

In some aspects not according to the invention, the aluminum alloy can comprise up to about <NUM> wt. % Mg, e.g., up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, or up to about <NUM> wt. In terms of ranges, the aluminum alloy can comprise from about <NUM> wt. % to about <NUM> wt. % Mg, e.g., from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Mg is not present (e.g. <NUM>%).

The aluminum alloy comprises from <NUM> wt. % to <NUM> wt. % Ca, and from <NUM> wt. % to <NUM> wt. In some aspects, the ratio of Ca wt. % to Zn wt. % in the aluminum alloy can be from about <NUM>:<NUM> to about <NUM>:<NUM> Ca to Zn (e.g., about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; or about <NUM>:<NUM> to about <NUM>:<NUM>). Optionally, the aluminum alloy can also comprise from about <NUM> wt. % to <NUM> wt. Optionally, the aluminum alloy can comprise from about <NUM> wt. % to <NUM> wt. Optionally, the aluminum alloy can comprise from <NUM> wt. % to <NUM> wt.

Further, in some aspects not according to the invention, the aluminum alloy comprises from about <NUM> wt. % to about <NUM> wt. % Mg, and from about <NUM> wt. % to about <NUM> wt. In some aspects, the ratio of Mg wt. % to Zn wt. % in the aluminum alloy can be from about <NUM>:<NUM> to about <NUM>:<NUM> to Zn (e.g., about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; or about <NUM>:<NUM> to about <NUM>:<NUM>). Optionally, the aluminum alloy can also comprise from about <NUM> wt. % to <NUM> wt. Optionally, the aluminum alloy can comprise from about <NUM> wt. % to <NUM> wt. Optionally, the aluminum alloy can comprise from <NUM> wt. % to <NUM> wt.

Further, in some aspects which are not according to the invention, the aluminum alloy comprises from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Mg, and from about <NUM> wt. % to about <NUM> wt.

In addition to the aluminum alloys containing Ca and Zn, Mg and Zn which are not according to the invention, or Ca, Zn and Mg which are not according to the invention, also described herein are surface layers which are not according to the invention, for (e.g., coatings) aluminum alloys, where the surface layers may comprise Mg, Ca, Zn, Ni, or combinations thereof. The surface layer(s) can be positioned on an aluminum alloy substrate, such as the aluminum alloys described above, or an aluminum alloy substrate other than those described above. The Mg, Ca, Zn, Ni, or combination thereof can be in a form where the Mg, Ca, Zn, and/or Ni is available to inhibit or prevent corrosion in the aluminum alloy substrate. The Mg, Ca, Zn, Ni, or 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 the aluminum alloy substrate can be at least about <NUM> atomic % of Mg, Ca, Zn, Ni, or a combination thereof (e.g., at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, at least about <NUM> atomic %, or at least about <NUM> atomic %). As one specific example, in certain aspects the amount sufficient to inhibit or prevent corrosion in the aluminum alloy substrate can be at least about <NUM> atomic % Ca and at least about <NUM> atomic % Zn (e.g., at least about <NUM> atomic % Ca and at least about <NUM> atomic % Zn, at least about <NUM> atomic % Ca and at least about <NUM> atomic % Zn, or at least about <NUM> atomic % Ca and at least about <NUM> atomic % Zn). In terms of ranges, in some aspects the amount sufficient to inhibit or prevent corrosion can be from about <NUM> atomic % of Mg, Ca, Zn, Ni, or a combination thereof to about <NUM> atomic % of Mg, Ca, Zn, Ni, or a combination thereof (e.g., from about <NUM> atomic % to about <NUM> atomic %, from about <NUM> atomic % to about <NUM> atomic %, from about <NUM> atomic % to about <NUM> atomic %, from about <NUM> atomic % to about <NUM> atomic %, from about <NUM> atomic % to about <NUM> atomic %, from about <NUM> atomic % to about <NUM> atomic %, or from about <NUM> atomic % to about <NUM> atomic %). In some aspects, the atomic % can be measured using x-ray photoelectron spectroscopy ("XPS").

For example, the coatings can comprise magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), or combinations thereof. Surprisingly, the coated aluminum alloys described show significant filiform corrosion resistance. Filiform corrosion typically occurs on coated surfaces when moisture or a corrosive solution contacts a metal surface. It is caused by active galvanic cells across the metal surface. Without being bound by theory, filiform corrosion in an aluminum alloy propagates with an acidic head and a relatively higher pH at the tail. This pH difference, combined with different oxygen concentrations (caused by oxygen diffusion), creates a net anodic reaction at the head and a net cathodic reaction at the tail, resulting in corrosion. The inventors surprisingly found that species such as the aforementioned MgO, CaO, and/or ZnO in the coating can poison the acidic nature of the head to interrupt corrosion propagation.

In another embodiment which is not according to the invention, corrosion of an aluminum alloy can be reduced by inhibiting the reactivity of the cathodic tail. The inventors surprisingly discovered that this could be accomplished by using a coating on an aluminum alloy to deliver an inorganic cathodic inhibitor. Some examples of inorganic cathodic inhibitors are the ions of Mg, Ca, Zn, Ni, or combinations thereof from the coating. These ions can react with the hydroxyl (-OH) of water to form insoluble hydroxides as Mg(OH)<NUM>, Ca(OH)<NUM>, Zn(OH)<NUM>, or Ni(OH)<NUM> which are deposited on the cathodic site of the metal surface, protecting it. Other examples of inorganic cathodic inhibitors can include phosphonates, tannins, and/or lignins. In some embodiments, corrosion can be prevented both by the poisoning of the acidic nature of the corrosion head and inhibiting the cathodic tail.

In some aspects, the coatings described can be applied to the aluminum alloy surface with a chemical wash containing the Mg, Ca, Zn, Ni, or combinations thereof, for example in a rinse step, using physical vapor deposition ("PVD"), or using chemical vapor deposition ("CVD"). Some examples of methods that may be used to coat the aluminum alloy surface with a chemical wash are immersing (for example, by immersion of the aluminum alloy surface into a bath or other type of vessel 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(s) of ion used and/or the type of the surface being treated.

The coated aluminum alloys described can be used in aluminum alloy products such as clad products. For example, the coated aluminum alloys can serve as a clad layer or as a core layer in a clad aluminum alloy product.

Unexpectedly, the aluminum alloys and coated aluminum alloys described herein exhibit exceptional corrosion resistance. The corrosion resistance can be measured by filiform corrosion tests ("FFC"), for example. The corrosion resistance can be tested according to standard methods used in the field. One example of such a standard method is ID-<NUM>, ISO <NUM>-<NUM> (<NUM>). ASTM D2803 is another appropriate standard that can be used for testing the filiform corrosion. DIN EN ISO <NUM> is also a standard that can be used for testing the filiform corrosion. Filiform corrosion is a particular form of crevice corrosion. This type of corrosion typically occurs on coated surfaces when moisture or a corrosive solution penetrates through the defective coatings. It is caused by active galvanic cells across the metal surface. Surprisingly, the aluminum alloys and coated aluminum alloys described herein show significant filiform corrosion resistance when tested by standard test methods.

For example, the aluminum alloys and coated aluminum alloys described can have a corrosion coverage percent (i.e., the corrosion coverage area as a percentage of the total area) of <NUM>% or less in the horizontal direction, the vertical direction, the diagonal direction, or in any and all combinations of these directions (measured separately) (e.g., <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, <NUM>% or less, or <NUM>% or less) when undergoing filiform corrosion testing. In addition, the aluminum alloys and coated aluminum alloys can have an average filament length during filiform corrosion testing of <NUM> or less in the horizontal direction, the vertical direction, the diagonal direction, or in any and all combinations of these directions (measured separately) (e.g., <NUM> or less, <NUM> or less, <NUM> or less, <NUM> or less, <NUM> or less, <NUM> or less, <NUM> or less, <NUM> or less, or <NUM> or less).

In one aspect, the new aluminum alloys and coated aluminum alloys described herein can have a yield strength up to about <NUM> MPa in a T6 temper (e.g., from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, or from about <NUM> MPa to about <NUM> MPa). In one aspect, the new aluminum alloys and coated aluminum alloys described herein can have a yield strength up to about <NUM> MPa in a T4 temper (e.g., from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, or from about <NUM> MPa to about <NUM> MPa). The new aluminum alloys and coated aluminum alloys described herein can have an elongation (either total or uniform) in any direction or in any combination of directions (longitudinal (L), diagonal (D), and/or transverse (T)) of at least about <NUM> % (measured separately) (e.g., at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, at least about <NUM> %, or at least about <NUM> %). In terms of ranges, the new aluminum alloys and coated aluminum alloys described herein can have an elongation of from about <NUM> % to about <NUM> % (e.g., from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, or from about <NUM> % to about <NUM> %).

Due to the unexpected increased anti-corrosion properties of the inventive alloy products described, increased amounts of various metals can be used in the alloys that were previously avoided because of corrosion issues. For example, the aluminum alloys described can comprise significant levels of copper (Cu). In terms of ranges, the aluminum alloys can optionally comprise from <NUM> wt. % to <NUM> wt. %Cu, e.g., from about <NUM> wt. % to about <NUM> wt. % Cu, from about <NUM> wt. % to about <NUM> wt. % Cu or from about <NUM> wt. % to about <NUM> wt. Previously, such significant ranges of Cu may not have been used due to perceived corrosion.

The aluminum alloys and coated aluminum alloys described herein can be used as clad aluminum alloy layers in a clad aluminum alloy product. The automotive structural part according to the invention uses a clad aluminium alloy layer, wherein the clad aluminium layer has the claimed composition. The clad aluminum alloy product described herein can comprise a first clad aluminum alloy layer located on a first side of a core aluminum alloy layer. In some aspects, the clad aluminum alloy product described herein can further comprise a second clad aluminum alloy layer located on a second side of the core layer. The first clad aluminum alloy layer and the second clad aluminum alloy layer can comprise the same or different alloys. According to the invention the first clad aluminum alloy comprises Ca, Zn, and Al. The first clad aluminum alloy layer comprises from <NUM> wt. % to <NUM> wt. % Ca, and from <NUM> wt. % to <NUM> wt. In some aspects which are not according to the invention, the first clad aluminum alloy layer can comprise Mg, Zn, and Al. In some cases which are not according to the invention, the first clad aluminum alloy layer can comprise from about <NUM> wt. % to about <NUM> wt. % Mg, and from about <NUM> wt. % to about <NUM> wt. In some aspects which are not according to the invention, the first clad aluminum alloy layer can comprise Ca, Zn, Mg and Al. In some aspects which are not according to the invention, the first clad aluminum alloy layer can comprise Mg, Zn, Ca, and Al. In some cases which are not according to the invention, the first clad aluminum alloy layer can comprise from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Zn and from about <NUM> wt. % to about <NUM> wt. In some aspects which are not according to the invention, the first clad aluminum alloy can comprise a coating layer comprising ions of Mg, Ca, Zn, Ni, or combinations thereof positioned on an outward facing surface of the first clad aluminum alloy (i.e., on a surface facing away from the core layer).

In some aspects, the second clad aluminum alloy layer can comprise Ca, Zn, and Al. In some cases, the second clad aluminum alloy layer can comprise from about <NUM> wt. % to about <NUM> wt. % Ca, and from about <NUM> wt. % to about <NUM> wt. In some aspects, the second clad aluminum alloy layer can comprise Mg, Zn, and Al. In some cases, the second clad aluminum alloy layer can comprise from about <NUM> wt. % to about <NUM> wt. % Mg, and from about <NUM> wt. % to about <NUM> wt. In some aspects, the second clad aluminum alloy layer can comprise Mg, Zn, Ca, and Al. In some cases, the second clad aluminum alloy layer can comprise from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Zn and from about <NUM> wt. % to about <NUM> wt. In some aspects, the second clad aluminum alloy can comprise a coating layer comprising ions of Mg, Ca, Zn, Ni, or combinations thereof positioned on an outward facing surface of the second clad aluminum alloy (i.e., on a surface facing away from the core layer).

Also provided are materials comprising the clad aluminum alloy products described herein. The materials can include automotive products (e.g., automotive structural parts), aerospace products (e.g., an aerospace structural part or an aerospace non-structural part), marine products (e.g., a marine structural part or a marine non-structural part), or electronic products (e.g., electronic device housings), among others. Further provided are aluminum alloy sheets, plates, and shates comprising a clad aluminum alloy product as described herein. Only the claimed automotive structural part belongs to the invention. The rest of the products are outside of the claimed invention.

The clad aluminum alloy products described include one or more clad aluminum alloy layers in contact with a core layer. In some examples, the core layer has a clad layer on only one side (i.e., one clad layer is present in the clad aluminum alloy product). In other examples, the core layer is cladded on more than one side, for example two sides (i.e., two clad layers are present in the clad aluminum alloy product). According to the invention at least one of the clad layers comprises Al, Ca, and Zn. In another embodiment which are not according to the invention, at least one of the clad layers comprises Al, Mg, and Zn. In another embodiment which are not according to the invention, at least one of the clad layers comprises Al, Ca, Mg, and Zn. In another embodiment, at least one of the clad layers comprises a coating comprising ions of Mg, Ca, Zn, Ni, or combinations thereof. This coating is positioned on the outside of the at least one clad layer, facing away from the core layer. Typically, the core layer is the larger component of the material, and therefore usually predominately determines the bulk mechanical properties of the clad product, for example the strength of the clad product. On the other hand, the clad layer(s), which typically (but not always) represent a smaller component of the clad product, are in contact with the surrounding environment and thus determine the chemical activity (e.g., corrosion resistance) and can affect the formability and joining properties of the clad product.

In some aspects, a first side of the core layer is adjacent to and contacts a first clad layer to form a first interface (e.g., no layers (such as a coating) intervene between the first clad layer and the first side of the core layer), although that need not be the case. In some aspects, the clad aluminum alloy product includes a second clad layer. In some instances, a second side of the core layer is adjacent to and contacts the second clad layer to form a second interface (i.e., no layers (such as a coating) intervene between the second clad layer and the second side of the core layer), although that need not be the case. In some aspects, the first clad layer and the second clad layer can be the same chemical composition. In other aspects, the first clad layer and the second clad layer can be different chemical compositions.

In some aspects, the thickness of the clad products can be from about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>).

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 clad layer comprising Al, Ca, and Zn; a clad layer comprising Al, Mg, and Zn; a clad layer comprising Al, Ca, Mg, and Zn; or a clad layer comprising a coating comprising ions of Mg, Ca, Zn, Ni, or combinations thereof. In aspects, the core layer can comprise the new aluminum alloys and/or new coated aluminum alloys described above.

The thickness of the core layer can be from about <NUM> % to about <NUM> % of the thickness of the clad aluminum alloy products described herein, e.g., from about <NUM> % to <NUM> %, from about <NUM> % to <NUM> %, from about <NUM> % to <NUM> %, from about <NUM> % to <NUM> %, from about <NUM> % to <NUM> %, from about <NUM> % to <NUM> %, or from about <NUM> % to <NUM> %. For example, in a clad aluminum alloy product having a thickness of about <NUM> microns, the core layer can have a thickness of about <NUM> microns to about <NUM> microns. Optionally, the core layer can have a thickness in the range of about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>). For example, the thickness of the core layer can be about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>.

In some examples, any alloy designated as a "1xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 1xxx series alloys suitable for use as the core layer can 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.

In some examples, any alloy designated as a "2xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 2xxx series alloys suitable for use as the core layer can include AA2001, A2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012, AA2013, AA2014, AA2014A, AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA2319, AA2419, AA2519, AA2021, AA2022, AA2023, AA2024, AA2024A, AA2124, AA2224, AA2224A, AA2324, AA2424, AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA2028, AA2028A, AA2028B, AA2028C, AA2029, AA2030, AA2031, AA2032, AA2034, AA2036, AA2037, AA2038, AA2039, AA2139, AA2040, AA2041, AA2044, AA2045, AA2050, AA2055, AA2056, AA2060, AA2065, AA2070, AA2076, AA2090, AA2091, AA2094, AA2095, AA2195, AA2295, AA2196, AA2296, AA2097, AA2197, AA2297, AA2397, AA2098, AA2198, AA2099, or AA2199.

In some examples, any alloy designated as a "3xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 3xxx series alloys suitable for use as the core layer can include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.

In some examples, any alloy designated as a "4xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 4xxx series alloys suitable for use as the core layer can 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.

In some examples, any alloy designated as a "5xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 5xxx series alloys suitable for use as the core layer can include AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA5251A, AA5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5154C, AA5254, AA5354, AA5454, AA5554, AA5654, 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.

In some examples, any alloy designated as a "6xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 6xxx series alloys suitable for use as the core layer can include AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA6016, 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.

In some examples, any alloy designated as a "7xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 7xxx series alloys suitable for use as the core layer can include AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7122, AA7023, AA7026, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA7049, AA7049A, AA7149,<NUM>, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7150, AA7250, AA7055, AA7155, AA7255, AA7056, AA7060, AA7064, AA7065, AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, or AA7099.

In some examples, any alloy designated as an "8xxx series" alloy is suitable for use as the core layer. By way of non-limiting example, the 8xxx series alloys suitable for use as the core layer can include AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA8019, AA8021, AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, AA8090, AA8091, or AA8093.

Also described herein is an aluminum alloy for use as a clad aluminum alloy layer in clad aluminum alloy products. In addition to aluminum, the clad aluminum alloy layer comprises Ca and Zn, or Zn and Mg, which are not according to the invention, or Ca, Zn and Mg, which are not according to the invention, and achieves excellent surface properties.

The thickness of each clad aluminum alloy layer can be from about <NUM> % to about <NUM> % of the total thickness the clad aluminum alloy products described herein (e.g., from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, from about <NUM> % to about <NUM> %, or about <NUM> %). For example, in a clad aluminum alloy product having a thickness of <NUM> microns, each clad aluminum alloy layer can have a thickness up to about <NUM> microns (e.g., up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, up to about <NUM> microns, from about <NUM> microns to about <NUM> microns, from about <NUM> microns to about <NUM> microns, from about <NUM> microns to about <NUM> microns, from about <NUM> microns to about <NUM> microns, from about <NUM> microns to about <NUM> microns, or from about <NUM> microns to about <NUM> microns). Optionally, each clad aluminum alloy layer can have a thickness in the range of about <NUM> to about <NUM> (e.g., about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, or about <NUM>). In terms of ranges, the clad aluminum alloy layer comprises from <NUM> wt. % to <NUM> wt. % Ca, e.g., from <NUM> wt. % to about <NUM> wt. % Ca, from <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, or from about <NUM> wt. % to about <NUM> wt. In terms of ranges, the clad layer comprises from <NUM> wt. % to <NUM> wt. % Zn, from <NUM> wt. % to about <NUM> wt. % Zn, from <NUM> wt. % to about <NUM> wt. % Zn, from <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn or from about <NUM> wt. % to about <NUM> wt.

Thus, in terms of ratios, in some aspects the Ca and Zn can be present in the clad aluminum alloy layer in a ratio of about <NUM>:<NUM> to about <NUM>:<NUM> Ca to Zn (e.g., about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; or about <NUM>:<NUM> to about <NUM>:<NUM>), as determined by weight.

In other aspects which are not according to the invention, the clad aluminum alloy comprises up to about <NUM> wt. % Mg, e.g., up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, or up to about <NUM> wt. In terms of ranges, the clad aluminum alloy may comprise from about <NUM> wt. % to about <NUM> wt. % Mg, e.g., from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, or from about <NUM> wt. % to about <NUM> wt. Additionally, the clad aluminum alloy layer comprises up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, or up to about <NUM> wt. In some aspects, the clad aluminum alloy layer may comprise at least <NUM> wt. % Zn, e.g., at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. In terms of ranges, the clad layer may comprise from about <NUM> wt. % to about <NUM> wt. % Zn, e.g., from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, or from about <NUM> wt. % to about <NUM> wt.

Thus, in terms of ratios, in some aspects the Mg and Zn in the clad aluminum alloy can be in ratios from about <NUM>:<NUM> to about <NUM>:<NUM> to Zn (e.g., about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; or about <NUM>:<NUM> to about <NUM>:<NUM>).

In other aspects which are not according to the invention, the clad aluminum alloy layer comprises up to about <NUM> wt. % Ca, e.g., up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, up to about <NUM> wt. % Ca, or up to about <NUM> wt. In terms of ranges, the clad aluminum alloy layer may comprise from about <NUM> wt. % to <NUM> wt. % Ca, e.g., from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, from about <NUM> wt. % to about <NUM> wt. % Ca, or from about <NUM> wt. % to about <NUM> wt. Additionally, the clad aluminum alloy comprises up to about <NUM> wt. % Mg, e.g., up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, up to about <NUM> wt. % Mg, or up to about <NUM> wt. In terms of ranges, the clad aluminum alloy may comprise from about <NUM> wt. % to about <NUM> wt. % Mg, e.g., from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, from about <NUM> wt. % to about <NUM> wt. % Mg, or from about <NUM> wt. % to about <NUM> wt. Additionally, the clad aluminum alloy layer comprises up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, up to about <NUM> wt. % Zn, or up to about <NUM> wt. In some aspects, the clad aluminum alloy layer may comprise at least <NUM> wt. % Zn, e.g., at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, at least <NUM> wt. % Zn, or at least <NUM> wt. In terms of ranges, the clad layer may comprise from about <NUM> wt. % to about <NUM> wt. % Zn, e.g., from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, from about <NUM> wt. % to about <NUM> wt. % Zn, or from about <NUM> wt. % to about <NUM> wt.

Thus, in terms of ratios, in some aspects which are not according to the invention, the Ca and Zn can be present in the clad aluminum alloy layer in a ratio of about <NUM>:<NUM> to about <NUM>:<NUM> Ca to Zn (e.g., about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; about <NUM>:<NUM> to about <NUM>:<NUM>; or about <NUM>:<NUM> to about <NUM>:<NUM>), as determined by weight. Also, the Ca and Mg can be present in the clad aluminum alloy layer in a ratio of about <NUM>:<NUM> to about <NUM>:<NUM> Ca to Mg.

The clad aluminum alloy layer can optionally comprise silicon (Si). In some aspects, the clad aluminum alloy layer can comprise up to <NUM> wt. % Si, e.g., up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, up to about <NUM> wt. % Si, or up to about <NUM> wt. In terms of ranges, the clad layer can optionally comprise from about <NUM> wt. % to about <NUM> wt. % Si, e.g., from about <NUM> wt. % to about <NUM> wt. % Si, from about <NUM> wt. % to about <NUM> wt. % Si, from about <NUM> wt. % to about <NUM> wt. % Si, from about <NUM> wt. % to about <NUM> wt. % Si, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Si is not present (e.g., <NUM> wt.

The clad aluminum alloy layer can optionally comprise up to <NUM> wt. % iron (Fe), e.g., up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, up to about <NUM> wt. % Fe, or up to about <NUM> wt. In terms of ranges, the clad aluminum alloy layer can optionally comprise from about <NUM> wt. % to about <NUM> wt. % Fe, e.g., from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, from about <NUM> wt. % to about <NUM> wt. % Fe, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Fe is not present (e.g., <NUM> wt.

The clad aluminum alloy layer can optionally comprise copper (Cu) In terms of ranges, the clad layer can optionally comprise from <NUM> wt. % to <NUM> wt. % Cu, e.g., from about <NUM> wt. % to about <NUM> wt. % Cu, from about <NUM> wt. % to about <NUM> wt. % Cu, from about <NUM> wt. % to about <NUM> wt. % Cu, from about <NUM> wt. % to about <NUM> wt. % Cu, from about <NUM> wt. % to about <NUM> wt. % Cu, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Cu is not present (e.g., <NUM> wt.

The clad aluminum alloy layer can optionally comprise manganese (Mn). In terms of ranges, the clad layer can optionally comprise from <NUM> wt. % to <NUM> wt. % Mn, e.g., from about <NUM> wt. % to about <NUM> wt. % Mn, from about <NUM> wt. % to about <NUM> wt. % Mn, from about <NUM> wt. % to about <NUM> wt. % Mn, from about <NUM> wt. % to about <NUM> wt. % Mn, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Mn is not present (e.g., <NUM> wt.

The clad aluminum alloy layer can optionally comprise titanium (Ti). In terms of ranges, the clad layer can optionally comprise from <NUM> wt. % to <NUM> wt. % Ti, e.g., from about <NUM> wt. % to about <NUM> wt. % Ti, from about <NUM> wt. % to about <NUM> wt. % Ti, from about <NUM> wt. % to about <NUM> wt. % Ti, from about <NUM> wt. % to about <NUM> wt. % Ti, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, Ti is not present (e.g., <NUM> wt.

The clad aluminum alloy layer can optionally comprise vanadium (V). In terms of ranges, the clad layer can optionally comprise from <NUM> wt. % to <NUM> wt. % V, e.g., from about <NUM> wt. % to about <NUM> wt. % V, from about <NUM> wt % to about <NUM> wt. % V, from about <NUM> wt. % to about <NUM> wt. % V, from about <NUM> wt. % to about <NUM> wt. % V, from about <NUM> wt. % to about <NUM> wt. % V, or from about <NUM> wt. % to about <NUM> wt. In some embodiments, V is not present (e.g., <NUM> wt.

Optionally, the clad aluminum alloy layer described herein can further include other minor elements, sometimes referred to as impurities, in amounts of about <NUM> wt. % or below, about <NUM> wt. % or below, about <NUM> wt. % or below, about <NUM> wt. % or below, or about <NUM> wt. % or below. These impurities may include, but are not limited to, V, Ni, Sc, Hf, Zr, Sn, Ga, Bi, Na, Pb, or combinations thereof. Accordingly, V, Ni, Sc, Hf, Zr, Sn, Ga, Bi, Na, or Pb, may each be present in alloys in amounts of about <NUM> wt. % or less, about <NUM> wt. % or less, about <NUM> wt. % or less, about <NUM> wt. % or less, or about <NUM> wt. % or less, for example. The sum of all impurities does not exceed about <NUM> wt. % (e.g., does not exceed about <NUM> wt. %, about <NUM> wt. %, about <NUM> wt. %, about <NUM> wt. % about <NUM> wt. %, or about <NUM> wt. All expressed in wt. In some aspects, the remaining percentage of the alloy is aluminum.

In some aspects which are not according to the invention, Ca, Mg, and/or Zn can be alloyed with any appropriate series alloy to produce the clad layers described herein. By way of a non-limiting example which is not according to the invention, Ca can be combined with the other components of a 1xxx series alloy (including Fe) to form the clad 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 which is not according to the invention, Ca can be combined with the other components of a 7xxx series alloy (including Zn) to form the clad aluminum alloy layer, such as 7xxx series alloys: AA7011, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7033, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7122, AA7023, AA7026, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA7049, AA7049A, AA7149, AA7204, AA7249, AA7349, AA7449, AA7050, AA7050A, AA7150, AA7250, 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 which is not according to the invention, Ca can be combined with the other components of an 8xxx series alloy (including Fe) to form the clad aluminum alloy layer, such as AA8006, AA8008, AA8010, AA8112, AA8014, AA8015, AA8016, AA8021, AA8023, AA8026, AA8030, AA8130, AA8150, AA8076, AA8076A, and AA8177.

In another non-limiting example, due to the increased corrosion resistance provided by the aluminum alloys and coated aluminum alloys described, increased levels of alloying elements that are traditionally associated with increased corrosion, e.g., Cu, can be included and used in products, such as clad products. One example, which is not according to the invention, is a high Cu 6xxx series aluminum alloy. For example, the aluminum alloys described can contain up to <NUM> wt. % Cu (e.g., up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. %, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, up to about <NUM> wt. % Cu, from <NUM> wt. % to <NUM> wt. % Cu, from <NUM> wt. % to <NUM> wt. % Cu, from <NUM> wt. % to <NUM> wt. % Cu, from <NUM> wt. % to <NUM> wt. % Cu, or from <NUM> wt. % to <NUM> wt. In some embodiments, Cu is not present (e.g., <NUM> wt. According to the invention the aluminium alloy of the clad aluminium alloy layer of the claimed automotive structural part comprises optionally <NUM> wt. % to <NUM> wt.

Typically manufacturers have been reluctant to use such materials due to potential filiform corrosion issues. The increased corrosion resistance of the aluminum alloys and coated aluminum alloys described make possible the use of new alloys like a high Cu 6xxx series aluminum alloy.

In some examples, an alloy for use as a clad layer can have the following elemental composition as provided in Table <NUM>.

As another example, an alloy for use as a clad layer can have the following elemental composition as provided in Table <NUM>.

As described above, the clad aluminum alloy products can contain one clad layer or more than one clad layer. According to the invention the automotive structural part comprises a clad aluminium alloy layer. In some cases, the clad aluminum alloy products contain only a first clad layer In some cases, the clad aluminum alloy products contain a first clad layer and a second clad layer. In some cases, the first clad layer and the second clad layer are identical in composition. In other cases, the first clad layer and the second clad layer differ in composition. The resulting clad aluminum alloy products exhibit excellent balanced properties, such as strength, formability, corrosion resistance, dent resistance, and hemming performance.

In some cases, the first clad layer can have a thickness of about <NUM> % to <NUM> % of the total clad product thickness (e.g., from about <NUM> % to about <NUM> % of the total clad product thickness or about <NUM>% of the total clad product thickness). In some cases, where a second clad layer is present, the second clad layer can have a thickness of about <NUM> % to <NUM> % of the total clad product thickness (e.g., from about <NUM> % to about <NUM> % of the total clad product thickness or about <NUM> % of the total clad product thickness).

Clad layers as described herein can improve surface corrosion resistance properties of the products, improve pretreatment efficiency, aid bending, riveting hole piercing and clinching, and can make the alloy product usable in T4 temper for some parts without hot forming. Moreover, when a filler wire alloy, such as AA7021, is used as the clad layer, laser welding can be accomplished without using filler wire.

The methods are not part of the claimed invention.

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

A clad layer as described herein can be attached to a core layer as described herein to form a clad aluminum alloy product by any means known to persons of ordinary skill in the art. For example, a clad layer can be attached to a core layer by direct chill co-casting (i.e., fusion casting) as described in, for example, <CIT> and <CIT>, by hot and cold rolling a composite cast ingot as described in <CIT>; or by roll bonding to achieve the required metallurgical bonding between the core and the clad layer; or by other methods as known to persons of ordinary skill in the art. The initial dimensions and final dimensions of the clad aluminum alloy products described herein can be determined by the desired properties of the overall final product.

The roll bonding process can be carried out in different manners. For example, the roll-bonding process can include both hot rolling and cold rolling. Further, the roll bonding process can be a one-step process or a multi-step process in which the material is gauged down during successive rolling steps. Separate rolling steps can optionally be separated by other processing steps, including, for example, annealing steps, cleaning steps, heating steps, cooling steps, and the like.

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

In the homogenization step of a DC casting process, the co-cast ingot described herein is heated to a temperature ranging from about <NUM> to about <NUM>, or any suitable temperature. For example, the ingot can be heated to a temperature of about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>. The ingot is then allowed to soak (i.e., held at the indicated temperature) for a period of time. In some examples, the total time for the homogenization step, including the heating and soaking phases, can be up to <NUM> hours. For example, the ingot can be heated up to <NUM> and soaked, for a total time of up to <NUM> hours for the homogenization step. Optionally, the ingot can be heated to below <NUM> and soaked, for a total time of greater than <NUM> hours for the homogenization step. In some cases, the homogenization step comprises multiple processes. In some non-limiting examples, the homogenization step includes heating the ingot to a first temperature for a first period of time followed by heating to a second temperature for a second period of time. For example, the ingot can be heated to about <NUM> for about <NUM> hours and then heated to about <NUM> for about <NUM> hours.

Following the homogenization step of the co-cast ingot, a hot rolling step can be performed. Prior to the start of hot rolling, the homogenized ingot can be allowed to cool to a temperature, such as from about <NUM> to about <NUM>. For example, the homogenized ingot can be allowed to cool to a temperature of from about <NUM> to about <NUM> or from about <NUM> to about <NUM>. The ingots can then be hot rolled at a temperature between <NUM> to <NUM> to form a hot rolled plate, a hot rolled shate or a hot rolled sheet having a gauge of from about <NUM> to about <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or anywhere in between).

Optionally, the cast product can be a continuously cast product that can be allowed to cool after a high temperature continuous casting step to a temperature such as from about <NUM> to about <NUM>. For example, the continuously cast product can be allowed to cool to a temperature of from about <NUM> to about <NUM> or from about <NUM> to about <NUM>. The continuously cast product can then be hot rolled at a temperature of from about <NUM> to about <NUM> to form a hot rolled plate, a hot rolled shate or a hot rolled sheet having a gauge of from about <NUM> to about <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or anywhere in between). During hot rolling, temperatures and other operating parameters can be controlled so that the temperature of the clad alloy hot rolled product upon exit from the hot rolling mill is no more than about <NUM>, no more than about <NUM>, no more than about <NUM>, or no more than about <NUM>.

The clad plate, shate, or sheet can then be cold rolled using conventional cold rolling mills and technology. Optionally, the cold rolled clad product (e.g., sheet or shate) can have a gauge of from about <NUM> to about <NUM>, e.g., between about <NUM> to about <NUM>. Optionally, the cold rolled clad sheet can have a gauge of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>. The cold rolling can be performed to result in a final gauge thickness that represents a gauge reduction of up to about <NUM> % (e.g., up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, up to about <NUM> %, or up to about <NUM> % reduction). Optionally, an interannealing step can be performed during the cold rolling step. The interannealing step can be performed at a temperature such as from about <NUM> to about <NUM> (e.g., about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>). In some cases, the interannealing step comprises multiple processes. In some non-limiting examples, the interannealing step includes heating the cold rolled clad plate, shate, or sheet to a first temperature for a first period of time followed by heating to a second temperature for a second period of time. For example, the cold rolled clad plate, shate, or sheet can be heated to about <NUM> for about <NUM> hour and then heated to about <NUM> for about <NUM> hours.

Subsequently, the clad plate, shate, or sheet can undergo a solution heat treatment step. The solution heat treatment step can include any conventional treatment for the clad sheet which results in solutionizing of the soluble particles. The clad plate, shate, or sheet can be heated to a peak metal temperature (PMT) of up to, for example, about <NUM> (e.g., from about <NUM> to about <NUM>) and soaked for a period of time at the temperature. For example, the clad plate, shate, or sheet can be soaked at about <NUM> for a soak time of up to about <NUM> minutes (e.g., <NUM> seconds, about <NUM> seconds, about <NUM> seconds, about <NUM> seconds, about <NUM> minutes, about <NUM> minutes, about <NUM> minutes, about <NUM> minutes, or about <NUM> minutes). After heating and soaking, the clad plate, shate, or sheet is rapidly cooled at rates greater than <NUM>/second (°C/s) to a temperature from about <NUM> to about <NUM>. In one example, the clad plate, shate, or sheet is cooled at a quench rate of above <NUM>/s from a temperature of about <NUM> to a temperature of about <NUM>. Optionally, the cooling rates can be faster in other cases.

After quenching, the clad plate, shate or sheet can optionally undergo a pre-aging treatment by reheating the plate, shate, or sheet before coiling. The pre-aging treatment can be performed at a temperature such as from about <NUM> to about <NUM> for a period of time such as up to about <NUM> hours. For example, the pre-aging treatment can be performed at a temperature of about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, about <NUM>, or about <NUM>. Optionally, the pre-aging treatment can be performed for about <NUM> minutes, about <NUM> hour, about <NUM> hours, about <NUM> hours, about <NUM> hours, about <NUM> hours, or about <NUM> hours. The pre-aging treatment can be carried out by passing the plate, shate, or sheet through a heating device, such as a device that emits radiant heat, convective heat, induction heat, infrared heat, or the like.

The co-cast ingots or other co-cast products described herein can also be used to make products in the form of plates or other suitable products. The products can be made using techniques as known to those of ordinary skill in the art. For example, plates including the clad products as described herein can be prepared by processing a co-cast ingot in a homogenization step or casting a co-cast product in a continuous caster followed by a hot rolling step. In the hot rolling step, the cast product can be hot rolled to a <NUM> thick gauge or less (e.g., from about <NUM> to about <NUM>). For example, the cast product can be hot rolled to a plate having a final gauge thickness of about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, about <NUM> to about <NUM>, or about <NUM> to about <NUM>.

The clad aluminum alloy products described herein can be designed to achieve any desired strength level as determined by persons of ordinary skill in the art. For example, the clad aluminum alloy products described herein can have yield strengths of up to about <NUM> MPa (e.g., from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, or from about <NUM> MPa to about <NUM> MPa). In some examples, the yield strengths of the products can be about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, or about <NUM> MPa.

In addition, the clad aluminum alloy products described herein can have elongations of up to about <NUM> %. For example, the elongations can be about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> %, about <NUM> % or about <NUM> %.

Further, the clad aluminum alloy products described herein can have strong bendability properties. A bend angle of from about <NUM>° to about <NUM>° can be achieved, based on the desired use of the product, as measured by a three-point bend test according to VDA Standard <NUM>-<NUM>, normalized to <NUM>. For example, the clad aluminum alloy products described herein can achieve a bend angle of about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, about <NUM>°, or about <NUM>°.

In some examples, a clad aluminum alloy product (e.g., a clad aluminum alloy sheet) made according to a method described herein can have a minimum R/t ratio (i.e., f-factor) of about <NUM> without cracking. The R/t ratio can provide an assessment of the bendability of a material. As described below, the 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 better bendability of the material. The R/t ratio of the clad aluminum alloy layers described herein can be about <NUM> or lower (e.g., about <NUM> or lower, about <NUM> or lower, about <NUM> or lower, or about <NUM> or lower).

The clad aluminum alloy products described herein can be used in automotive applications. The invention relates to the automotive structural part according to claim <NUM>. The clad aluminum alloy products can be used to prepare automotive structural parts, such as bumpers, side beams, roof beams, cross beams, pillar reinforcements (e.g., A-pillars, B-pillars, and C-pillars), inner panels, outer panels, side panels, inner hoods, outer hoods, or trunk lid panels.

The clad aluminum alloy products described herein can also be joined to other materials to form useful products. Methods for 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, adhesive bonding, and self-piercing riveting. The alloy products can be used in a variety of applications, including automotive applications.

The following examples will serve to further illustrate the present invention.

Clad aluminum alloy layers were produced by casting, hot and cold rolling, annealing above a temperature of <NUM>, and quenching the alloys described in Table <NUM>.

As shown in Table <NUM>, Comparative Alloys <NUM>, <NUM>, and <NUM> were prepared as comparatives to Example Alloy <NUM> which has a similar composition as Comparative Alloys <NUM>, <NUM>, and <NUM>, but also a combination of Ca (<NUM> wt. %) and higher Zn (<NUM> wt. Comparative Alloys <NUM> and <NUM> were prepared as comparatives to Example Alloy <NUM>, which has a similar composition as Alloys <NUM> and <NUM>, but also has a combination of Ca (<NUM> wt. %) and higher Zn (<NUM> wt.

All numbers are expressed in wt. Each composition contains up to <NUM> wt. % impurities. The remainder is Al. The invention relates to the claimed automotive structural part. The example alloys <NUM> and <NUM> are not part of the invention themselves but are suitable to be used as the clad aluminum alloy layer for the automotive part of the invention.

The filiform corrosions of Comparative Alloys <NUM>-<NUM> and Example Alloys <NUM> and <NUM> were measured using ISO <NUM>-<NUM> (<NUM>). In addition, the phosphatability was measured for Comparative Alloy <NUM> and Example Alloys <NUM> and <NUM> using a classical <NUM> cation Zn-phosphate process. <FIG> shows the filiform corrosion testing for the Comparative Alloys <NUM>-<NUM> and Example Alloys <NUM> and <NUM>. As shown in <FIG> and <FIG>, Example Alloy <NUM> shows exceptional filiform corrosion resistance against the comparatives. Example Alloy <NUM> gives the best filiform corrosion results in terms of the lowest coverage (%) in both the horizontal and vertical directions and the lowest average filament length in both the vertical and horizontal directions against the comparatives. Similarly, as can be seen in <FIG> and <FIG>, Example Alloy <NUM> shows exceptional filiform corrosion resistance against its comparatives. Example Alloy <NUM> gives the best filiform corrosion results in terms of the lowest coverage (%) in both the horizontal and vertical directions and the lowest average filament length in both the vertical and horizontal directions against the comparatives.

<FIG> and <FIG> show the same results visually. <FIG> shows micrographs of the results of the filiform corrosion tests for Comparative Alloys <NUM>-<NUM> and Example Alloy <NUM>. <FIG> shows micrographs of the results of the filiform corrosion tests for Comparative Alloys <NUM>-<NUM> and Example Alloy <NUM>. As seen from <FIG> and <FIG>, the filiform corrosion observed in the microstructures of the samples was significantly less for Example Alloys <NUM> and <NUM> than the Comparative Alloys.

<FIG> shows the phosphatability of Comparative Alloy <NUM> and Example Alloys <NUM> and <NUM>. As can be seen from the results in <FIG>, the phosphatabilities of the <NUM> samples are comparable and are good. Ratings of the homogeneity of the phosphate crystals were determined using a scanning electronic microscope and ranged from <NUM>-<NUM>. Coating weights were measured in g/m<NUM>. Comparative Alloy <NUM> has a rating of <NUM>-<NUM> and a coating weight of <NUM>/m<NUM>. Example Alloy <NUM> had a rating of <NUM>-<NUM> and a coating weight of <NUM>/m<NUM>, comparable to Comparative Alloy <NUM>. Example Alloy <NUM> had a rating of <NUM>, again comparable to the other samples tested and coating weight was not measured.

Aluminum alloys were prepared with the compositions in Table <NUM>. The bond durability performance of the aluminum alloys was measured using stress durability testing for adhesive joints. Bond durability testing assesses the strength of bonds created between the bonded products and may indicate the ability of the near-surface microstructures of an aluminum alloy product to strongly bind with the adhesive over long periods of use and under corrosive conditions or conditions that otherwise differ from ambient conditions. During testing, bonds are created between two aluminum alloy products, such as by an epoxy adhesive. Then, the bonded aluminum alloy products are subjected to strain and/or other conditions. For example, the bonded aluminum alloy products may be immersed in or sprayed with (e.g., according to the NSS test) a salt solution, subject to humid conditions, or drying conditions. After a series of cycles in one or more conditions, the bonds between the aluminum alloy products are evaluated for chemical and mechanical failure in an example using cycles. In other examples, the products are evaluated for chemical and mechanical failure after a single immersion or spray. The bond durability performance of an aluminum alloy product may indicate or be a function of the reactivity and corrosion sensitivity of the product's near-surface microstructures.

An example standard test for determining bond durability is <NPL>, which is hereby incorporated by reference. During bond durability testing, each sample is made of two pieces of aluminum alloy product, prepared and treated using the same conditions, that are bonded together via six bonding sites using an epoxy adhesive. Next, each sample is subjected to various test conditions. For example, the test conditions may include one or more of immersion in a salt solution, exposure to humid conditions, exposure to dry conditions, or application of force inducing stress or strain. Each sample is subjected to numerous cycles of these test conditions. The number of cycles a sample is subjected to is either the number of cycles to reach mechanical failure or <NUM> cycles, the maximum number of cycles used in this particular test. Mechanical failure includes bond failure, a break in the metal product or a break in the adhesive. As such, the bonding surface may be associated with a wait period before being bonded to another surface, substrate, or product.

The example alloys were arranged in Table <NUM> in order of increasing stress durability performance with Example Alloy <NUM> having the highest stress durability performance.

Additional aluminum alloys were produced by casting, hot and cold rolling, annealing above a temperature of <NUM>, and quenching the alloy compositions described in Table <NUM>.

All numbers are expressed in wt. All compositions contain up to <NUM> wt. % impurities. The remainder is Al.

Claim 1:
An automotive structural part comprising a clad aluminum alloy layer in contact with a core layer, wherein the core layer is an aluminum-containing alloy, and wherein the clad aluminum alloy layer comprises an aluminum alloy, comprising:
from <NUM> wt. % to <NUM> wt. % Ca;
from <NUM> wt. % to <NUM> wt. % Zn;
up to <NUM> wt. % Si;
up to <NUM> wt. % Fe;
up to <NUM> wt. % Ti,
optionally <NUM> wt. % to <NUM> wt. % Cu;
optionally <NUM> wt. % to <NUM> wt. % Mn;
optionally <NUM> wt. % to <NUM> wt. % V;
up to <NUM> wt. % impurities; and
the remainder Al,
wherein the aluminum alloy is the clad aluminum alloy layer.