Aluminum alloy products produced from recycled aluminum alloy materials for controlled atmosphere brazing

Abstract

Disclosed herein are aluminum alloy products including one or more cladding layers. The core aluminum alloy may include a 3xxx series aluminum alloy including a Mg content greater than 0.05 wt. % and up to 1.5 wt. %. The core layer may comprise high amounts of recycled aluminum alloy material and maintain corrosion resistance and suitability for controlled atmosphere brazing (CAB) processes. The cladding layer prevents Mg migration and / or diffusion from within the core aluminum alloy to the surface of the core aluminum alloy, thereby preventing formation of a MgO film via oxidation, which can disrupt the CAB processes. Such clad aluminum alloy products may be formed into a structural shape that may be welded and / or brazed to a metal substrate.

Description

ALUMINUM ALLOY PRODUCTS PRODUCED FROM RECYCLED ALUMINUM ALLOY MATERIALS FOR CONTROLLED ATMOSPHERE BRAZINGCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 611,959, filed on December 19, 2023, and U.S. Provisional Patent Application No. 63 / 708,942, filed on October 18, 2024, the contents of which are hereby incorporated by reference in their entireties.FIELD

[0002] This disclosure relates to the fields of material science, material chemistry, metallurgy, aluminum alloys, aluminum alloy products, aluminum fabrication, and related fields. More specifically, the disclosure provides aluminum alloy products with high sag resistance and corrosion resistance that can be used in a variety of applications, including, for example, as a protective layer for an aluminum alloy product (e.g., a clad aluminum alloy product) for controlled atmosphere brazing.BACKGROUND

[0003] There has long been an interest in using recycled aluminum alloy materials for producing aluminum alloys. Incorporating recycled aluminum alloy materials to produce new aluminum alloys leads to decreased carbon emissions (e.g., decreased global impact and specific carbon footprints) due to a reduced use of primary aluminum in the melting furnace charge. Recycled aluminum alloy materials, however, may be unsuitable for use in preparing high performance aluminum alloys as the recycled aluminum alloy materials may contain higher levels of certain undesirable elements, such as magnesium. For example, aluminum alloy parts used in a heat exchanger require high corrosion resistance and good brazing among other properties. Therefore, aluminum alloy parts used in a heat exchanger have strict compositional limits to provide the desired properties. Magnesium can negatively influence the brazing process. Aluminum alloys having a high prime content, at less than 0.05 wt. % magnesium, may be used for such applications to account for deleterious influence of magnesium on controlled atmosphere brazing (CAB). The strict bounds on composition and processing for many high performance aluminum alloy products severely limit the amounts and types of recycled aluminum alloy materials and process-related scraps that can be used.For example, recycled scrap may include certain elements in amounts that adversely affect the mechanical properties of an aluminum alloy and its corrosion resistance. Most scrap aluminum alloy compositions include levels of magnesium that prevent their use in applications that involve CAB brazing. For these reasons, it is impractical to use high amounts of recycled scrap in producing certain aluminum alloys, especially for heat exchangers that require strictly controlled aluminum alloy compositions and material properties.SUMMARY

[0004] Covered embodiments of the invention are defined by the claims, not this summary. This summary is a high-level overview of various aspects of the invention and introduces some of the concepts that are further described in the Detailed Description section below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used in isolation to determine the scope of the claimed subject matter. The subject matter should be understood by reference to appropriate portions of the entire specification, any or all drawings and each claim.

[0005] Provided herein are aluminum alloy products including cladding layers for controlled atmosphere brazing. The clad aluminum alloy products may comprise a core layer having a first surface and a second surface on opposing sides of the core layer and a cladding layer adjacent to and in contact with at least one of the first surface or the second surface of the core layer. In some embodiments, an aluminum alloy product comprises: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy. Optionally, the cladding layer may comprise a 7xxx series aluminum alloy comprising up to 3 wt. % Zn. In some embodiments, the core layer comprises at least 0.05 wt. % Mg. In some embodiments, the core layer comprises up to 0.25 wt. % Cr and up to 0.25 wt. % Zr. In some embodiments, the cladding layer has a thickness of from 5 % to 15 % of the total thickness of the aluminum alloy product. In some embodiments, the cladding layer comprises a Ixxx series or a 7xxx series aluminum alloy including up to 0.25 wt. % Mn, up to 0.25 wt. % Cr, up to 0.25 wt. % Zr, or combinations thereof. In some embodiments, the cladding layer is roll bonded as a continuous layer on a portion of at least one of the first side or the second side of the corelayer. In some embodiments, the cladding layer is spray coated as a continuous layer on at least one of the first side or the second side of the core layer. In some embodiments, the cladding layer covers up to 75 % of the core layer. In some embodiments, the cladding layer enables flux free brazing in a controlled atmosphere brazing process. In some embodiments, the core layer comprises recycled aluminum alloy materials. In some embodiments, the recycled aluminum alloy materials comprise used clad aluminum alloy products comprising a mixture of 3xxx series aluminum alloys and 4xxx series aluminum alloys. In some embodiments, the aluminum alloy product is used as fin stock. In some embodiments, the cladding layer is deposited in discrete regions on at least one of the first side or the second side of the core layer. In some embodiments, a heat exchanger comprises the aluminum alloy product described herein. In some embodiments, the clad aluminum alloy product may be formed into a structural shape that is welded and / or brazed to a metal substrate.

[0006] In some embodiments, a method of forming an aluminum alloy product is provided, the method comprising: casting an aluminum alloy to form a cast product, wherein the aluminum alloy comprises a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; homogenizing the cast product; hot rolling the cast product to produce a hot rolled product; cold rolling the hot rolled product to produce an aluminum alloy product; and applying cladding layer on at least one a first side or a second side of the aluminum alloy product to produce a clad aluminum alloy product, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0007] In some embodiments, a process for producing a clad aluminum alloy product comprising a core layer and a cladding layer, may comprise joining the core layer and the cladding layer where the cladding layer is adjacent with and bonded to at least one surface of the core layer.

[0008] In some embodiments, the method may comprise co-casting an ingot having a core and a cladding on at least one outer surface of the core and processing the ingot to form the clad aluminum alloy product.

[0009] In some embodiments, the method for producing a clad aluminum alloy product comprising a core layer and a cladding layer may comprise depositing an aluminum alloy composition on at least one surface of the core layer by thermal spray or cold spray to form the cladding layer. In some embodiments, the cladding layer is spray coated by depositing a spray mixture comprising metal particles on the aluminum alloy product. In some embodiments, the spray mixture further comprises flux particles combined with the metalparticles. In some embodiments, applying the cladding layer includes roll bonding the cladding layer on at least one the first side or the second side of the aluminum alloy product. In some embodiments, the aluminum alloy product is heated during the hot rolling step to a hot roll temperature of between 350 °C and 580 °C prior to roll bonding. In some embodiments, the aluminum alloy product is reduced to a thickness of 0.05 mm to 2.50 mm prior to spray coating the cladding layer on the aluminum alloy product. In some embodiments, the cladding layer is a sacrificial layer configured to corrode prior to the aluminum alloy product. In some embodiments, the cladding layer prevents Mg migration and / or diffusion from within the aluminum alloy product to a surface of the aluminum alloy product.

[0010] In some embodiments, a method of forming a brazing product is provided. The method may comprise assembling and securing via welding and / or brazing the clad aluminum alloy product described herein to a metal substrate. In some embodiments, the method comprising the steps of providing one or more metal parts; providing a clad aluminum alloy product on or between the one or more metal parts to form an assembly, wherein the clad aluminum alloy product comprises: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy; and brazing the assembly in a controlled atmosphere to join the clad aluminum alloy product and the one or more metal parts to produce a brazed assembly; optionally applying a flux load before brazing; and cooling the brazed assembly. In some embodiments, the assembly is brazed at a brazing temperature from 550° C to 620° C for 5 to 10 minutes.

[0011] Further aspects, objects, and advantages will become apparent upon consideration of the detailed description of non-limiting examples that follow.BRIEF DESCRIPTION OF THE FIGURES

[0012] The specification makes reference to the following appended figures, in which use of like reference numerals in different figures is intended to illustrate like or analogous components.

[0013] FIG. 1 provides a schematic illustration of a spray deposition system for depositing one or more cladding layers on high-recycled content aluminum alloy substrates.

[0014] FIG. 2 provides a schematic illustration of an example clad aluminum alloy product including a core layer with a Mg content of greater than 0.05 wt. % and a cladding layer deposited on a first side and a second side of the core layer.

[0015] FIG. 3 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 1.

[0016] FIG. 4 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 1.

[0017] FIG. 5 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 2.

[0018] FIG. 6 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 2.

[0019] FIG. 7 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 3.

[0020] FIG. 8 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 3.

[0021] FIG. 9 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 4.

[0022] FIG. 10 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 4.

[0023] FIG. 11 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 5.

[0024] FIG. 12 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 5.

[0025] FIG. 13 provides a photograph of cladded aluminum alloy fins brazed to a metal substrate for Example 6.

[0026] FIG. 14 provides a micrograph of a cross-section of a cladded aluminum alloy fin brazed to a metal substrate for Example 6.DETAILED DESCRIPTION

[0027] Described herein are aluminum alloy products including high recycled content aluminum alloys. The aluminum alloy products described herein comprise “recycle-friendly” aluminum alloys that can be used in a variety of applications, including, for example, as a core alloy in a clad aluminum product (e.g., a brazing sheet or fin stock), that can replacecore aluminum alloys produced from a high content of primary aluminum. For example, the aluminum alloy product can be a core layer in a clad aluminum alloy product. In some embodiments, the disclosure is directed to clad aluminum alloy products that include a core layer comprising a 3xxx series aluminum alloy and cladding layer comprising a Ixxx series or a 7xxx series aluminum alloy. Optionally, the 7xxx series aluminum alloy in the cladding layer may comprise up to 3 wt. % Zn.

[0028] Conventional aluminum alloys used in controlled atmosphere brazing (CAB) brazing include less than 0.05 wt. % magnesium (Mg) to ensure good brazability. The aluminum alloys for use as core alloys (e.g., 3xxx series aluminum alloys) used in heat exchanger products cannot be produced with a high content of recycled aluminum alloy materials (e.g., having high amounts of Mg) without sacrificing properties of the aluminum alloy products. For example, recycled aluminum materials that include greater than 0.05 wt. % Mg cannot be used to produce core aluminum alloys because the Mg in the core aluminum alloy may migrate or diffuse to the surface of the clad product and oxidize, forming MgO or other magnesium-containing compounds. This may lead to corrosion and poor adhesion to a cladding layer.

[0029] Advantageously, the clad aluminum alloys described herein are tailored to utilize increased amounts of Mg as compared to traditional monolithic aluminum alloys used in CAB brazing while maintaining good brazability. In some examples, the aluminum alloys described herein may include up to 1.5 wt. % Mg. Most scrap aluminum alloy compositions include levels of Mg that prevent their use in products used in CAB brazing. The use of alloys having higher Mg content in CAB brazing is desirable to increase sustainability and enable the use of recycled materials.

[0030] Beneficially, the cladding layers described herein can prevent or reduce Mg or Mg-containing compounds from migrating and / or diffusing to a surface of a core aluminum alloy during brazing applications (e.g., controlled atmosphere brazing). Therefore, the core aluminum alloy can include higher amounts of Mg than conventional aluminum alloys used in core aluminum alloys (e.g., used for brazing sheets), enabling the use of recycled aluminum alloy materials. Specifically, recycled aluminum alloy scrap including high amounts of Mg (e.g., greater than 0.05 wt. %) can be used to produce the core layers of the aluminum alloy products described herein.

[0031] Additionally, there is a significant market need for aluminum alloys produced from recycled aluminum alloy materials to reduce carbon footprint. Besides factors like price and material properties, the recycled content of specific aluminum alloys is increasinglyimportant for the automotive and non-automotive industries. Although there are aluminum alloys available on the market that can incorporate high amounts of recycled aluminum alloy materials that have wide chemistry windows for alloying elements (e.g., Mg, Si, Cu, and Mn), these aluminum alloys cannot be considered for critical components (e.g., corrosion critical parts in heat exchangers). In particular, the Mg content in aluminum alloys for use as core alloys is limited because Mg can migrate or diffuse to a surface of the aluminum alloy. The Mg that migrates to the surface of the aluminum can oxidize to form a MgO film. MgO interacts with traditional salt flux and disrupts the flow of melting clad layer such that adequate fillets are not formed during the brazing cycle.

[0032] The aluminum alloy products described herein include core aluminum alloys produced from higher amounts of recycled aluminum alloy materials (e.g., high-Mg containing aluminum alloy scrap), as compared to conventional core aluminum alloys, and still maintain good mechanical properties, for example, for brazing applications. Specifically, the aluminum alloy products described herein include a cladding layer that surprisingly provides an aluminum alloy product having little to no Mg migration to a surface of the core aluminum alloys. In some embodiments, the core aluminum alloys described herein are 3xxx series aluminum alloys, 6xxx series aluminum alloys, or 7xxx series aluminum alloys having a Mg content of greater than 0.05 wt. %. Without being bound by theory, it was found that providing the cladding layer on at least one side of the core aluminum alloy prevents or significantly reduces Mg in the core aluminum alloy from migrating or diffusing to the surface of the alloy. Beneficially, suppressing Mg migration to the surface prevents or limits formation of MgO from disrupting the brazing process, thereby allowing higher amounts of Mg from recycled aluminum alloy materials to be used in the core layer. Additionally, the cladding layer can enable flux free brazing during CAB. The combination of properties of the cladding layer described herein enables incorporating high recycled content in the core aluminum alloy of clad aluminum alloy products.

[0033] In some embodiments, the aluminum alloy products including the high recycled content aluminum alloys described herein can be a cladded product including a core layer and one or more cladding layers. The core layer has a first side and a second side and one or more cladding layer(s) can be bonded to the first side or the second side of the core layer. In some examples, the core layer is clad on only one side (i.e., one cladding layer is present in the clad aluminum alloy product). In other examples, the core layer is clad on both sides (i.e., two cladding layers are present in the clad aluminum alloy product). The cladding layer(s) can be attached to a core layer in a variety of ways. For example, the cladding layer(s) can beattached to a core layer by direct chill co-casting (i.e., fusion casting) as described in, for example, U.S. Pat. Nos. 7,748,434 and 8,927,113, both of which are hereby incorporated by reference in their entireties, by hot and cold rolling a composite cast ingot as described in U.S. Pat. No. 7,472,740, which is hereby incorporated by reference in its entirety, or by roll bonding to achieve the required metallurgical bonding between the core and the cladding. In some embodiments, the cladding layer(s) can be spray deposited to a core layer.

[0034] In some embodiments, the cladding layer can be a Ixxx series aluminum alloy or a 7xxx series aluminum alloy. The cladding layer comprising the Ixxx series aluminum alloy or 7xxx series aluminum alloy may include 0.05 wt. % to 0.25 wt. % of one or more of Mn, Cr, and Zr. In some embodiments, the cladding layer may be deposited on at least one side of the of core layer. The cladding layer may comprise from 5 % to 15 % of the total thickness of a clad aluminum alloy product. For example, for a clad aluminum alloy product including a cladding layer on each side of the core alloy, each cladding layer may comprise from 5 % to 10 % of the total thickness of the clad aluminum alloy product. In some embodiments, the cladding layer may comprise 5 %, 6 %, 7 %, 8 %, 9 %, 10 %, 11 %, 12 %, 13 %, 14 % or 15 % of the total thickness of the clad aluminum alloy product.

[0035] The clad aluminum alloy product may include a core layer. In some embodiments, the core layer comprises a 3xxx series aluminum alloy. In some embodiments, the 3xxx series aluminum alloy may include up to 3.00 wt. % Zn and up to 1.50 wt. % Mg. In some embodiments, the 3xxx series aluminum alloy may include up to 0.25 wt. % Cr and / or up to 0.25 wt. % Zr.

[0036] The aluminum alloy products described herein possess a combination of properties that are suitable for the heat exchanger market (e.g., including the electrification of vehicles). In summary, the aluminum alloys described herein possess a combination of higher relative recycled content (e.g., 50 wt. % to 70 wt. %) that can be sourced from high-Mg containing materials to lower the carbon footprint of the aluminum alloy. The cladding layer of the aluminum alloy products enable using aluminum alloys having a high-Mg content (e.g., greater than 0.05 wt. %) as core layers in the aluminum alloy products. By incorporating the cladding layer in the aluminum alloy products, the aluminum alloys used in the core layer can be produced with high recycle rates while having added corrosion protection from the cladding layer.Definitions and Descriptions:

[0037] The terms “invention,” “the invention,” “this invention,” and “the present invention” used herein are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below.

[0038] In this description, reference is made to alloys identified by aluminum industry designations, such as “series” or “3xxx.” For an understanding of the number designation system most commonly used in naming and identifying 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,” both published by The Aluminum Association.

[0039] As used herein, the meaning of “a,” “an,” or “the” includes singular and plural references unless the context clearly dictates otherwise.

[0040] As used herein, the meaning of “metals” includes pure metals, alloys and metal solid solutions unless the context clearly dictates otherwise.

[0041] In this description, reference is made to alloys identified by aluminum industry designations, such as “series” or “3xxx” or “3xxx.” For an understanding of the number designation system most commonly used in naming and identifying 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,” both published by The Aluminum Association.

[0042] As used herein, a plate generally has a thickness of greater than about 15 mm. For example, a plate may refer to an aluminum product having a thickness of greater than about 15 mm, greater than about 20 mm, greater than about 25 mm, greater than about 30 mm, greater than about 35 mm, greater than about 40 mm, greater than about 45 mm, greater than about 50 mm, or greater than about 100 mm.

[0043] As used herein, a shate (also referred to as a sheet plate) generally has a thickness of from about 4 mm to about 15 mm. For example, a shate may have a thickness of about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm, about 12 mm, about 13 mm, about 14 mm, or about 15 mm.

[0044] As used herein, a sheet generally refers to an aluminum product having a thickness of less than about 4 mm. For example, a sheet may have a thickness of less than about 4 mm, less than about 3 mm, less than about 2 mm, less than about 1 mm, less than about 0.5 mm, less than about 0.3 mm, or less than about 0.1 mm.

[0045] Reference is made in this application to alloy temper or condition. For an understanding of the alloy temper descriptions most commonly used, see “American National Standards (ANSI) H35 on Alloy and Temper Designation Systems.” 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 an aluminum alloy after cold rolling with or without thermal treatment (e.g., annealing). Suitable H tempers include HIX, H2X, H3X, H4X, H5X, H6X, H7X, H8X, or H9X tempers. For example, the aluminum alloy can be strain hardened to various tempers, for example, H16, H18, or other HIX tempers.

[0046] Reference is made in this application to recycled content. The term “recycled content” incorporates, but is not limited to, what is typically called internal process waste or scrap but also different types of external scrap, for instance, post-consumer scrap, remelt scrap ingot (RSI), among others. Since primary aluminum (aside from the alloying elements and hardeners) is responsible for the majority of the Scope 3 emissions (described below), all types of recycled content inputs (whether they are internal or external scrap) contribute to more sustainable aluminum alloy products and support possible closed-loop material circularity (production) processes.

[0047] The following aluminum alloys are described in terms of their elemental composition in weight percentage (wt. %) based on the total weight of the alloy. In certain examples of each alloy, the remainder is aluminum, with a maximum wt. % of 0.15 % for the sum of the impurities.

[0048] Incidental elements, such as grain refiners and deoxidizers, or other additives may be present in the invention and may add other characteristics on their own without departing from or significantly altering the alloy described herein or the characteristics of the alloy described herein.

[0049] As used herein, “controlled atmosphere brazing” or “CAB” refers to a brazing process which utilizes an inert gas atmosphere, for example, nitrogen or argon, in the brazing of the various alloy articles.

[0050] 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 bydirect 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.

[0051] As used herein, the meaning of “room temperature” can include a temperature of from about 15° C to about 30° C, for example about 15° C, about 16° C, about 17° C, about 18° C, about 19° C, about 20° C, about 21° C, about 22° C, about 23° C, about 24° C, about 25° C, about 26° C, about 27° C, about 28° C, about 29° C, or about 30° C. As used herein, the meaning of “ambient conditions” can include temperatures of about room temperature, relative humidity of from about 20% to about 100%, and barometric pressure of from about 975 millibar (mbar) to about 1050 mbar.

[0052] All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, e.g., 1 to 6.1, and ending with a maximum value of 10 or less, e.g., 5.5 to 10. Unless stated otherwise, the expression “up to” when referring to the compositional amount of an element means that element is optional and includes a zero percent composition of that particular element. Unless stated otherwise, all compositional percentages are in weight percent (wt. %).

[0053] Aluminum alloys for use in the products and methods described herein include 3xxx series aluminum alloys. By way of non-limiting example, 3xxx series aluminum alloys 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.

[0054] Aluminum alloys for use in the products and methods described herein include Ixxx series aluminum alloy or a 7xxx series aluminum alloy. Exemplary Ixxx series aluminum alloys 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. Suitable 7xxx series aluminum alloys can include AA7004, AA7204, AA7009, AA7010, AA7012, AA7014, AA7015, AA7017,AA7019, AA7019A, AA7022, AA7122, AA7023, AA7028, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7035, AA7035A, AA7036, AA7136, AA7037, AA7039, AA7040, AA7140, AA7041, AA7042, AA7049, AA7049A, AA7349, AA7449, AA7050, AA7050A, AA7150, AA7055, AA7155, AA7255, AA7056, AA7060, AA7160, AA7064, AA7068, AA7168, AA7072, AA7075, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7090, AA7093, AA7095, AA7097, AA7099, and AA7199.Clad Aluminum Alloy Products

[0055] The terms “cladding,” “clad,” “cladding layer,” “clad layer,” and the related terms are used generally to refer to a relatively thin surface layer of clad aluminum alloy products. The terms “core,” “core layer,” and the related terms are used to refer to a relatively thicker layer of clad aluminum alloy products. In some examples, a clad aluminum alloy product (e.g., a clad sheet aluminum alloy) can have cladding layers on both sides of the core layer, in which case a core layer is an internal layer of the aluminum material. However, a clad aluminum alloy product (e.g., a clad sheet aluminum alloy) can alternatively have a cladding layer on only one side of the core layer, in which case the core layer can also be a surface. The core layer and cladding layer(s) typically have different chemical compositions. In some cases, a clad aluminum alloy product can have two different cladding layers with different compositions and properties.

[0056] It is to be understood that clad aluminum alloy products suitable for brazing applications do not necessarily contain only a core layer and one or two cladding layers. Clad aluminum alloy products can contain other layers (e.g., to form multilayer aluminum materials), some of which may be referred to as “interlayers,” “outer layers,” “liners,” and by other related terms. For example, clad aluminum alloy products can have 2, 3, 4, 5, 6 or more distinct layers, each having a certain function. More generally, clad aluminum alloy products can have as many layers as can be stacked and bonded together in one or more operations. In the commercial context, one possible limiting factor is the cost of production and / or scrap generated during production of clad aluminum alloy products, which can become too high with the increased number of layers for the clad aluminum alloy products to be commercially viable. In the context of clad aluminum alloy products suitable for brazing applications, one or more of the cladding layers can be the portion of the product that melts during a braze cycle. A liner can be a layer that is not expected to melt during a braze cycle and may confer some other benefits, such as corrosion resistance or increased strength, to the clad aluminumalloy products. A core can also include multiple layers, such as one or more interlayers on one or both sides of the main core layer.

[0057] In some embodiments, the clad aluminum alloy products include a core layer and at least one cladding layer attached to at least one of a first side or a second side of the core layer. FIG. 1 provides a schematic of a spray deposition system 100 for spray coating one or more cladding layers on high-recycled content aluminum alloy substrates (e.g., a core layer). While spray deposition is discussed with respect to FIG. 1, the cladding layer can be attached to the core layer by any suitable means. For example, one or more cladding layers can be attached to a core layer by direct chill co-casting (i.e., fusion casting), by hot and / or cold rolling a composite cast ingot, or by roll bonding.

[0058] In certain aspects, the spray deposition system 100 may implement thermal spray techniques to spray coat one or more cladding layers onto a core layer. An example of thermal spraying can include cold spraying that involves supersonic particle deposition. In some implementations, the deposition system 100 can include a nozzle 102 for depositing a spray mixture 104 including metal particles that form a cladding layer 106 on at least one side of a core layer 108 formed from high-recycled content aluminum alloys including greater than 0.05 wt. % Mg. In certain aspects, the spray mixture 104 may include flux particles combined with the spray mixture 104 to avoid an additional step when brazing the clad aluminum alloy product. In certain embodiments, more than one nozzle 102 may be positioned in the spray deposition system 100 to deposit the spray mixture 104 on the core layer 108 to form the cladding layer 106. The core layer 108 and the cladding layer 106 are further described below with respect to FIG. 2. In certain aspects, the spray deposition system 100 can deposit the cladding layer 106 having a thickness from 5 pm to 300 pm (e.g., from 5 pm to 20 pm, from 10 pm to 50 pm, from 25 pm to 75 pm, from 50 pm to 100 pm, from 80 pm to 160 pm, from 150 pm to 250 pm, or from 200 pm to 300 pm). The one or more cladding layers may comprise from 5 % to 15 % of the total thickness of the clad aluminum alloy product. For example, the one or more cladding layers may comprise 5 %, 6 %, 7 %, 8 %, 9 %, 10 %, 11 %, 12 %, 13 %, 14 % or 15 % of the total thickness of the clad aluminum alloy product. As depicted in FIG. 1, the spray deposition system 100 may deposit the spray mixture 104 on a first side 110a of the core layer 108. In other embodiments, the spray deposition system 100 can deposit the spray mixture 104 on a second side 110b of the core layer 108 or on both the first side 110a and the second side 110b of the core layer 108. In certain aspects, the spray deposition system 100 may additionally include a particle feeder 112 for receiving a supply of the spray mixture 104. The particle feeder 112 may receive thesupply of the spray mixture 104 and can provide the spray mixture 104 to the nozzle 102. In certain embodiments, the particle feeder 112 can control a rate at which the spray mixture 104 are supplied to the nozzle 102, thereby controlling a rate at which the spray mixture 104 are deposited onto the core layer 108. The rate of deposition for the spray mixture 104 can be used to control the thickness of the cladding layer 106. In additional or alternative aspects, the spray deposition system 100 can include a heater. In some examples in which the spray deposition system 100 implements cold spraying techniques, the heater can be used for heating a gas that is used to accelerate the particles of the spray mixture 104 onto the core layer 108.

[0059] The spray mixture 104 may include various types of powdered materials that are suitable for cold spraying. In certain embodiments, the spray mixture 104 is at least in part aluminum metal or aluminum alloys. As some non-limiting examples, the spray mixture 104 can include a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy. In some non-limiting examples, the spray mixture 104 may include combinations of various types of metals as desired. In some embodiments, at least one characteristic or property of the aluminum alloy(s) used as the spray mixture 104 may be different from the aluminum alloy of the core layer 108. The particles of the spray mixture 104 may have various diameters as desired. In some implementations, the diameters of the particles may be up to about 100 pm (e.g., up to 25 pm, up to 50 pm, or up to 75 pm). In some embodiments, the aluminum alloy used as the spray mixture 104, the diameter of the particles, or a combination thereof may be selected to control the thickness of the cladding layer 106.

[0060] During the spray coating process, the nozzle 102 may traverse over at least a portion of the core layer 108 to spray coat the spray mixture 104 on the core layer 108, thereby forming the cladding layer 106. In some embodiments, the spray coating process can involve providing the spray mixture 104 and heated gas to the nozzle 102 such that the particles of the spray mixture 104 are accelerated to high velocities and then sprayed onto the core layer 108. Upon impact with the core layer 108, the particles can undergo adiabatic heating and plastically deform, causing the spray mixture 104 to mechanically adhere to the core layer 108 to form the cladding layer 106.

[0061] In certain aspects, the spray deposition system 100 can deposit the cladding layer 106 in a single pass. As another example, the spray deposition system 100 may deposit the cladding layer 106 in a plurality of passes (e.g., two or more passes, three or more passes, four or more passes, etc.). In some embodiments, the cladding layer 106 can be spray coatedas a continuous layer on at least one of the first side 110a or the second side 110b of the core layer 108. In alternative embodiments, the cladding layer 106 can be spray coated as a non- continuous layer on the core layer 108. For example, the nozzle 102 may deposit the spray mixture 104 to form a non-continuous pattern layer on the core layer 108. If the cladding layer 106 is non-continuous, the cladding layer 106 may cover up to 75 % of the core layer 108 (e.g., up to 25 %, up to 50 %, or up to 70 %).

[0062] In some embodiments, the cladding layer is deposited in discrete regions on at least one of the first side or the second side of the core layer. For example, the cladding layer can be a non-continuous layer on the core layer that is separated by a gap. In some embodiments, the cladding layer can be deposited on a plurality of regions of the first side or the second side of the core layer. Each of the plurality of regions of the cladding layer can be an individual discrete region that is separated from another one of the plurality of regions. In this way, the cladding layer can be a patterned layer on at least one of the first side or the second side of the core layer.

[0063] FIG. 2 provides a schematic of a clad aluminum alloy product 200 having a core layer 202 adjacent to a first cladding layer 204a and a second cladding layer 204b. The core layer 202 can be an aluminum alloy product that has been reduced to a thickness of 0.05 mm to 2.50 mm prior to the cladding layers 204a-b being deposited. For example, the thickness of the core layer 202 can be from 0.05 mm to 0.10 mm, from 0.15 mm to 0.25 mm, from 1.00 mm to 2.00 mm, or from 1.50 mm to 2.50 mm. The cladding layers 204a-b can be deposited onto the core layer 202 using a spray deposition system (e.g., the spray deposition system 100 of FIG. 1). In some cases, the first cladding layer 204a can be adjacent to and contact a first side of the core layer 202 to form a first interface (i.e., no layers intervene between the first cladding layer 204a and the first side of the core layer 202). The second cladding layer 204b can be adjacent to and contact a second side of the core layer 202 to form a second interface (i.e., no layers intervene between the second cladding layer 204b and the second side of the core layer 202). The cladding layers 204a-b can function as sacrificial layers that can corrode prior to or in place of the core layer 202. The first cladding layer 204a and the second cladding layer 204b may each comprise the alloy compositions described herein. In some embodiments, the core layer 202 is clad on only one side. In other embodiments, the core layer 202 is clad on both sides. In some aspects, the first cladding layer 204a and the second cladding layer 204b may include multiple layers.

[0064] The aluminum alloy products described herein can include 3xxx series aluminum alloys, 6xxx series aluminum alloys, or 7xxx series aluminum alloys having a Mg contentgreater than 0.05 wt. % as a core layer of a clad aluminum alloy product. By including a cladding layer deposited on at least one side of the core layer, the aluminum alloy products can tolerate higher amounts of Mg than conventional clad aluminum alloy products affected by Mg migration and diffusion to a surface of the core layer. As such, the aluminum alloys for the core layer can be produced from higher amounts of recycled aluminum alloys. For example, the aluminum alloy products may include a core layer comprising a 3xxx series aluminum alloy, 6xxx series aluminum alloys, or a 7xxx series aluminum alloy having a Mg content of greater than 0.05 wt. %. The aluminum alloy products described herein can tolerate higher amounts of Mg and therefore can utilize clad aluminum alloy products as recycled material. In particular, the aluminum alloys described herein can be produced from more than 50 % of recycled aluminum alloy materials (e.g., mixed 3xxx / 4xxx series aluminum alloy process scrap).

[0065] The aluminum alloy products described herein can be used in industrial applications including sacrificial parts, filler parts, heat dissipation, packaging, and building materials. In some embodiments, the aluminum alloy products described herein can be employed in aluminum alloy parts for heat exchangers, including use with dissimilar metals and as / or with extruded components. Specifically, the aluminum alloy products described herein can form brazed products. Suitable cladding layers and core layers for use in such aluminum alloy products are described below.

[0066] In some embodiments, the cladding layer can be a Ixxx series aluminum alloy or a 7xxx series aluminum alloy. The Ixxx series aluminum alloy or 7xxx series aluminum alloy for the cladding layer may include 0.05 wt. % to 0.25 wt. % of one or more of Mn, Cr, and Zr. Optionally, the cladding layer may include up to 3 wt. % Zn. In some embodiments, the cladding layer may be deposited on at least one side of the of core layer. The cladding layer may comprise from 5 % to 15 % of the total thickness of the clad aluminum alloy product. For example, for a clad aluminum alloy product including a cladding layer on each side of the core alloy, each cladding layer may comprise from 5 % to 10 % of the total thickness of the clad aluminum alloy product.Core Layer

[0067] Described below are aluminum alloy compositions that can be produced with a relatively high content of recycled aluminum alloy materials. In some embodiments, the aluminum alloy described herein can be used as a core layer, in combination with at least one cladding layer, to produce aluminum alloy products described herein. The aluminum alloyproducts described herein can include a cladding layer coupled to at least one side of the core layer to form a clad aluminum alloy product. The resulting aluminum alloy products are suitable for use in a variety of applications, including for instance, as use as a corrosion resistant brazing sheet package in manufacturing cold plates (e.g., cooling plates or battery cooling plates) for electric vehicle batteries.

[0068] In some embodiments, the core layer is produced from recycled aluminum alloy scrap. The recycled aluminum alloy scrap may comprise a 3xxx series aluminum alloy, 6xxx series aluminum alloys, a 7xxx series aluminum alloy, or combinations thereof. The recycled aluminum alloy scrap may include at least 0.05 wt. % Mg. For example, if the aluminum alloy is a 3xxx series aluminum alloy, the aluminum alloy can be an AA3104 aluminum alloy or an AA3105 aluminum alloy. As another example, if the aluminum alloy is a 7xxx series aluminum alloy, the aluminum alloy can be an AA7075 aluminum alloy. The aluminum alloys described herein exhibit good brazing performance and corrosion resistance despite being produced from relatively high amounts of recycled aluminum alloys (e.g., Mg- containing aluminum materials) due to a cladding layer deposited on at least one side of the aluminum alloy.

[0069] In some examples, suitable alloys for use in the recycled content alloys described herein can be a 3xxx series aluminum alloy or a 7xxx series aluminum alloy. The 3xxx or 7xxx series aluminum alloy can be modified to include an amount of Mg as described above.

[0070] Suitable 3xxx series aluminum alloys for use as the core alloys described herein include, for example, AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, and AA3065.

[0071] Suitable 6xxx series aluminum alloys for use as the core alloys described herein include, for example, 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.

[0072] Suitable 7xxx series aluminum alloys for use as the core alloys described herein include, for example, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, 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, 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.

[0073] The core layer of the aluminum alloy product can utilize high amounts of recycled aluminum alloy scrap since the aluminum alloy can tolerate higher amounts of Mg than conventional aluminum alloys for core layers. For example, the aluminum alloy described herein can be produced from Mg containing aluminum alloy process scraps such as used clad aluminum alloy products containing a mixture of 3xxx series aluminum alloys and 4xxx series aluminum alloys.

[0074] For conventional core alloys, the Mg content in aluminum alloys can affect the type or amount of flux needed during the CAB process. However, conventional fluxes (e.g., fluxes containing fluoride) can only tolerate small amounts of Mg (e.g., up to 0.05 wt. %) at a surface of the core layer. In some embodiments, the cladding layer(s) of the aluminum alloy product can prevent or reduce Mg or Mg-containing compounds of the core layer from migrating to the surface of the core layer. Therefore, the aluminum alloys described herein can tolerate higher amounts of Mg and can be produced using recycled aluminum alloy materials. In additional or alternative embodiments, the cladding layer(s) can enable flux -free CAB to avoid problems caused by flux residues when applying flux.

[0075] In some embodiments, the core layer comprises a modified 3xxx series aluminum alloy. For example, the core layer may include a 3xxx series aluminum alloy modified with intentionally added alloying elements, or alloying elements present in recycled scrap sources. In some embodiments, the aluminum alloy for the core layer includes up to 3.00 wt. % Znand up to 1.50 wt. % Mg. In some embodiments, the aluminum alloy for the core layer includes up to 0.25 wt. % Cr and up to 0.25 wt. % Zr.

[0076] In some examples, the aluminum alloy for the core layer can be a 3xxx series aluminum alloy including the following additional alloy elements as provided in Table 1.Table 1

[0077] In some examples, the aluminum alloy for the core layer can be a 3xxx series aluminum alloy including the following additional alloy elements as provided in Table 2.Table 2

[0078] In some examples, the aluminum alloy for the core layer can be a 3xxx series aluminum alloy including the following additional alloy elements as provided in Table 3.Table 3

[0079] Aluminum alloys suitable for use in the core layer of the compositions, products, and methods described herein can, for example, have the following elemental composition as provided in Table 4.Table 4

[0080] It is to be understood that, in various embodiments of the alloys described herein, including those in Tables 1-4, the predominant element is aluminum (Al), sometimes called “remainder Al.” In other words, the term “remainder” can be used to describe predominant aluminum (Al) content in the aluminum alloys described herein. inc (Zn)

[0081] In some examples, the aluminum alloy described herein includes Zn in an amount of up to 3.00 % (e.g., up to 2.50 %, up to 2.00 %, up to 1.50 %, up to 1.00 %, from 0.50 % to 3.00 %, from 1.00 % to 2.50 %, 1.00 % to 2.00 % or from 2.00 % to 3.00 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %,0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %,0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %,0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %,0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %,0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %,0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %,0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %,0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.00 %, 1.01 %, 1.02 %, 1.03 %,1.04 %, 1.05 %, 1.06 %, 1.07 %, 1.08 %, 1.09 %, 1.10 %, 1.11 %, 1.12 %, 1.13 %, 1.14 %,1.15 %, 1.16 %, 1.17 %, 1.18 %, 1.19 %, 1.20 %, 1.21 %, 1.22 %, 1.23 %, 1.24 %, 1.25 %,1.26 %, 1.27 %, 1.28 %, 1.29 %, 1.30 %, 1.31 %, 1.32 %, 1.33 %, 1.34 %, 1.35 %, 1.36 %,1.37 %, 1.38 %, 1.39 %, 1.40 %, 1.41 %, 1.42 %, 1.43 %, 1.44 %, 1.45 %, 1.46 %, 1.47 %,1.48 %, 1.49 %, 1.50 %, 1.51 %, 1.52 %, 1.53 %, 1.54 %, 1.55 %, 1.56 %, 1.57 %, 1.58 %,1.59 %, 1.60 %, 1.61 %, 1.62 %, 1.63 %, 1.64 %, 1.65 %, 1.66 %, 1.67 %, 1.68 %, 1.69 %,1.70 %, 1.71 %, 1.72 %, 1.73 %, 1.74 %, 1.75 %, 1.76 %, 1.77 %, 1.78 %, 1.79 %, 1.80 %,1.81 %, 1.82 %, 1.83 %, 1.84 %, 1.85 %, 1.86 %, 1.87 %, 1.88 %, 1.89 %, 1.90 %, 1.91 %,1.92 %, 1.93 %, 1.94 %, 1.95 %, 1.96 %, 1.97 %, 1.98 %, 1.99 %, 2.00 %, 2.01 %, 2.02 %,2.03 %, 2.04 %, 2.05 %, 2.06 %, 2.07 %, 2.08 %, 2.09 %, 2.10 %, 2.11 %, 2.12 %, 2.13 %,2.14 %, 2.15 %, 2.16 %, 2.17 %, 2.18 %, 2.19 %, 2.20 %, 2.21 %, 2.22 %, 2.23 %, 2.24 %,2.25 %, 2.26 %, 2.27 %, 2.28 %, 2.29 %, 2.30 %, 2.31 %, 2.32 %, 2.33 %, 2.34 %, 2.35 %,2.36 %, 2.37 %, 2.38 %, 2.39 %, 2.40 %, 2.41 %, 2.42 %, 2.43 %, 2.44 %, 2.45 %, 2.46 %,2.47 %, 2.48 %, 2.49 %, 2.50 %, 2.51 %, 2.52 %, 2.53 %, 2.54 %, 2.55 %, 2.56 %, 2.57 %,2.58 %, 2.59 %, 2.60 %, 2.61 %, 2.62 %, 2.63 %, 2.64 %, 2.65 %, 2.66 %, 2.67 %, 2.68 %,2.69 %, 2.70 %, 2.71 %, 2.72 %, 2.73 %, 2.74 %, 2.75 %, 2.76 %, 2.78 %, 2.79 %, 2.80 %,2.81 %, 2.82 %, 2.83 %, 2.84 %, 2.85 %, 2.86 %, 2.87 %, 2.88 %, 2.89 %, 2.90 %, 2.91 %,2.92 %, 2.93 %, 2.94 %, 2.95 %, 2.96 %, 2.97 %, 2.98 %, 2.99 %, or 3.00 % Zn. In some cases, Zn is not present in the alloy (i.e., 0 %). All expressed in wt. %.Magnesium (Mg)

[0082] In some examples, the aluminum alloy described herein can include Mg in an amount up to 1.50 % (e.g., up to 1.40 %, up to 1.30 %, up to 1.25 %, up to 1.20 %, up to 1.10 %, up to 1.00 %, up to 0.90 %, up to 0.75 %, up to 0.50 %, up to 0.25 %, 0.10 % to 1.00 %, from 0.20 % to 1.00 %, from 0.25 % to 0.80 %, from 0.30 % to 0.75 %, or from 0.40 to 0.60 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %,0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %,0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %,0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %,0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %,0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %,0.69 %, 0.70 %, 0.71%, 0.72%, 0.73 %, 0.74%, 0.75, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80%, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91%,0.92%, 0.93 %, 0.94%, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.00 %, 1.01 %, 1.02 %, 1.03 %, 1.04 %, 1.05 %, 1.06 %, 1.07 %, 1.08 %, 1.09 %, 1.10 %, 1.11 %, 1.12 %, 1.13 %,1.14 %, 1.15 %, 1.16 %, 1.17 %, 1.18 %, 1.19 %, 1.20 %, 1.21 %, 1.22 %, 1.23 %, 1.24 %,1.25 %, 1.26 %, 1.27 %, 1.28 %, 1.29 %, 1.30 %, 1.31 %, 1.32 %, 1.33 %, 1.34 %, 1.35 %,1.36 %, 1.37 %, 1.38 %, 1.39 %, 1.40 %, 1.41 %, 1.42 %, 1.43 %, 1.44 %, 1.45 %, 1.46 %,1.47 %, 1.48 %, 1.49 %, or 1.50 % Mg. All expressed in wt. % Chromium (Cr)

[0083] In some examples, the aluminum alloy described herein includes Cr in an amount of up to 0.3 % (e.g., up to 0.25 %, up to 0.15 %, up to 0.10 %, up to 0.05 %, up to 0.03 %, from 0.01 % to 0.20 %, from 0.01 % to 0.15 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16%, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27%, 0.28 %, 0.29 %, or 0.30 % Cr. In some cases, Cr is not present in the alloy (i.e., 0 %). All expressed in wt. %.Zirconium (Zr)

[0084] In some examples, the aluminum alloy described herein includes Zr in an amount of up to 0.25 % (e.g., up to 0.20 %, up to 0.15 %, up to 0.10 %, up to 0.05 %, up to 0.03 %, from 0.01 % to 0.20 %, from 0.01 % to 0.15 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, or 0.25 % Zr. In some cases, Zr is not present in the alloy (i.e., 0 %). All expressed in wt. %.Silicon (Si)

[0085] In certain examples, the disclosed aluminum alloy used in the core layer includes silicon (Si) in an amount up to about 1.00 % (e.g., from 0 % to 1.00 %, from 0.05 % to 1.00 %, from 0 % to 0.70 %, from 0.05 % to 0.70 %, from 0 % to 0.40 %, or from 0.05 % to 0.40 %) based on the total weight of the alloy. For example, the alloy can include 0.03 %, 0.04 %, 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, or 1.00 % Si. In some cases, thedisclosed alloy does not include Si (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Iron (Fe)

[0086] In certain examples, the disclosed aluminum alloy used in the core layer includes iron (Fe) in an amount up to about 1.00 % (e.g., from 0 % to 1.00 %, from 0.05 % to 1.00 %, from 0 % to 0.50 %, from 0.05 % to 0.50 %, from 0 % to 0.30 %, or from 0.05 % to 0.30 %) based on the total weight of the alloy. For example, the alloy can include 0.03 %, 0.04 %, 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, or 1.00 % Fe. In some cases, the disclosed alloy does not include Fe (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Copper (Cu)

[0087] In certain examples, the disclosed aluminum alloy used in the core layer includes copper (Cu) in an amount up to about 0.90 % (e.g., from 0 % to 0.90 %, from 0.05 % to 0.90 %, from 0 % to 0.70 %, from 0.05 % to 0.70 %, from 0 % to 0.40 %, or from 0.05 % to 0.40 %) based on the total weight of the alloy. For example, the alloy can include 0.03 %, 0.04 %, 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, or 0.90 % Cu. All expressed in wt. % based on the total weight of the aluminum alloy.Manganese (Mn)

[0088] In certain examples, the disclosed aluminum alloy used in the core layer includes manganese (Mn) in an amount up to about 1.80 % (e.g., from 0 % to 1.80 %, from 0.05 % to 1.80 %, from 0.10 % to 1.80 %, from 0 % to 1.00 %, from 0.05 % to 1.00 %, from 0.30 % to 1.80 %, from 0.30 % to 1.00 %, from 0.05 % to 0.75 %, or from 0.10 % to 0.75 %) based on the total weight of the alloy. For example, the alloy can include 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, 1.00 %, 1.05 %, 1.10 %, 1.15 %, 1.20 %, 1.25 %, 1.30 %, 1.35 %, 1.40 %, 1.45 %, 1.50 %, 1.55 %, 1.60 %, 1.65 %, 1.70 %, 1.75 %, or 1.80 % Mn. In some cases, the disclosed alloy does not include Mn (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Nickel (Ni)

[0089] In certain examples, the disclosed aluminum alloy used in the core layer includes nickel (Ni) in an amount up to about 0.10 % (e.g., from 0 % to 0.10 %, from 0.01 % to 0.10 %, from 0 % to 0.05 %, or from 0.01 % to 0.05 %) based on the total weight of the alloy. Forexample, the alloy can include 0.010 %, 0.015 %, 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085 %, 0.090 %, 0.095 %, or 0.100 % Ni. In some cases, the disclosed alloy does not include Ni (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Titanium (Ti)

[0090] In certain aspects, the disclosed aluminum alloy used in the core layer includes titanium (Ti) in an amount up to about 0.20 % (e.g., from 0 % to 0.20 %, from 0.05 % to 0.20 %, from 0 % to 0.10 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.010 %, 0.015 %, 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085%, 0.090 %, 0.095 %, 0.100 %, 0.110 %, 0.120 %, 0.115 %, 0.120 %, 0.125 %, 0.130 %,0.135 %, 0.140 %, 0.145 %, 0.150 %, 0.155 %, 0.160 %, 0.165 %, 0.170 %, 0.175 %, 0.180%, 0.185 %, 0.190 %, 0. 195 %, or 0.200 % Ti. In some cases, the disclosed alloy does not include Ti (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.

[0091] Optionally, the alloy can further include other minor elements, sometimes referred to as impurities, in amounts of about 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below or each of said impurities. These impurities may include, but are not limited to, vandium (V), scandium (Sc), yttrium (Y), hafnium (Hf), thallium (Th), gallium (Ga), tin (Sn), lead (Pb), silver (Ag), bismuth (Bi), strontium (Sr), calcium (Ca), lithium (Li), or combinations thereof. Accordingly, Sc, Y, Hf, Th, Ga, Sn, Pb, Ag, Bi, Sr, Ca, or Li, if present, may each independently be present in an alloy in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below. In certain aspects, the sum of all impurities does not exceed 0.15 % (e.g., does not exceed 0.10 %, or does not exceed 0.05 %). In certain aspect, the apply compositions may be devoid of (not comprise or comprise at 0.00 %) one or more of: Sc, Y, Hf, Th, Ga, Sn, Pb, Ag, Bi, Sr, Ca, and Li. All expressed in wt. % based on the total weight of the aluminum alloy.

[0092] The remaining percentage of the aluminum alloy may be aluminum, e.g., remainder Al.

[0093] Regarding the composition of the core layer, any alloy designated as a 3xxx series aluminum alloy including modified versions thereof to achieve the desired composition of Mg is suitable for use as the core layer. In some examples, the core layer may be an AA3105 series aluminum alloy or modification thereof.

[0094] In some embodiments, the aluminum alloy includes up to 1.00 wt. % Si, up to 1.00 wt. % Fe, up to 0.90 wt. % Cu, up to 1.50 wt. % Mg, up to 1.80 wt. % Mn, up to 0.10wt. % Ni, up to 0.25 wt. % Cr, up to 3.00 wt. % Zn, up to 0.25 wt. % Zr, up to 0.20 wt. % Ti, up to 0.15 wt. % impurities, and aluminum.

[0095] In some embodiments, the aluminum alloy includes up to 1.00 wt. % Si, up to 1.00 wt. % Fe, up to 0.90 wt. % Cu, from 0.05 to 1.50 wt. % Mg, up to 1.80 wt. % Mn, up to 0.10 wt. % Ni, up to 0.20 wt. % Cr, from 0.10 to 3.00 wt. % Zn, up to 0.20 wt. % Zr, up to 0.20 wt. % Ti, up to 0.15 wt. % impurities, and aluminum.

[0096] In some embodiments, the aluminum alloy includes up to 1.00 wt. % Si, up to 1.00 wt. % Fe, up to 0.90 wt. % Cu, from 0.05 to 1.00 wt. % Mg, up to 1.80 wt. % Mn, up to 0.10 wt. % Ni, up to 0.15 wt. % Cr, from 0.25 to 2.00 wt. % Zn, up to 0.15 wt. % Zr, up to 0.20 wt. % Ti, up to 0.15 wt. % impurities, and aluminum.Cladding Layer

[0097] Described below are aluminum alloy compositions for cladding layers. The cladding layer can be attached to high recycled content aluminum alloy substrates (e.g., a core layer) to prevent or reduce Mg migration and / or diffusion to a surface of the aluminum alloy substrates. The cladding layer can function as a barrier to prevent or reduce Mg content of the core layer from migrating to the surface of the aluminum alloy substrates. Additionally, the cladding layer can improve corrosion resistance of the core layer. In some implementations, the cladding layer can act as a sacrificial layer by corroding in place of the core layer, thereby minimizing corrosion of the core layer. In certain aspects, the cladding layer can be deposited as a continuous layer. In additional or alternative aspects, the cladding layer may be deposited as a non-continuous layer, for example in a predefined pattern. The predefined pattern of the cladding layer can correspond to areas of the core layer to be bonded by CAB.

[0098] In some embodiments, the cladding layer is a Ixxx series aluminum alloy, 4xxx series aluminum alloy, or 7xxx series aluminum alloy. Suitable Ixxx series aluminum alloys for use in the cladding layer described herein include, for example, AA1050, AA1060, AA1070, 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, AA1199, and modifications thereof. Suitable 4xxx series aluminum alloys for use in the cladding layer described herein include, for example, 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, AA4147, and modifications thereof. Suitable 7xxx series aluminum alloys for use in the cladding layer described herein include, for example, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, 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, 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, AA7099, and modifications thereof.

[0099] In some embodiments, the cladding layer is produced from a Ixxx series aluminum alloy, 4xxx series aluminum alloy, or 7xxx series aluminum alloy including the intentional addition of alloying components. For example, the cladding layer may include a Ixxx series or a 7xxx series aluminum alloy modified with intentionally added alloying elements, or alloying elements present in recycled scrap sources that are used to produce the cladding layer. In some embodiments, the aluminum alloy for the cladding layer includes up to 0.25 wt. % (e.g., from 0.05 wt. % to 0.25 wt. %) of Mn, Cr, Zr, or combinations thereof. The intentionally added Mn, Cr, and / or Zr promotes larger grain sizes of the cladding layer. The addition of Mn, Cr, and / or Zr can potentially increase the grain size of the aluminum such that during brazing the number of potential sites for liquid penetration and dissolution is reduced.

[0100] In some examples, the aluminum alloy for the cladding layer can be Ixxx series or a 7xxx series aluminum alloy including the following additional alloy elements as provided in Table 5.Table 5

[0101] In some examples, the aluminum alloy for the cladding layer can be Ixxx series or a 7xxx series aluminum alloy including the following additional alloy elements as provided in Table 6.Table 6

[0102] In some examples, the aluminum alloy for the cladding layer can be Ixxx series or a 7xxx series aluminum alloy including the following additional alloy elements as provided in Table 7.Table 7

[0103] Aluminum alloys suitable for use in the cladding layer of the compositions, products, and methods described herein can, for example, have the following elemental composition as provided in Table 8.Table 8

[0104] It is to be understood that, in various embodiments of the alloys described herein, including those in Tables 4-6, the predominant element is Al, sometimes called “remainder Al.” In other words, the term “remainder” can be used to describe predominant aluminum (Al) content in the aluminum alloys described herein.Manganese (Mn)

[0105] In some examples, the aluminum alloy described herein includes Mn in an amount of up to 0.25 % (e.g., up to 0.20 %, up to 0.15 %, up to 0.10 %, up to 0.05 %, up to 0.07 %, from 0.01 % to 0.20 %, from 0.01 % to 0.15 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, or 0.25 % Mn. In some cases, Mn is not present in the alloy (i.e., 0 %). All expressed in wt. %.Chromium (Cr)

[0106] In some examples, the aluminum alloy described herein includes Cr in an amount of up to 0.25 % (e.g., up to 0.20 %, up to 0.15 %, up to 0.10 %, up to 0.05 %, up to 0.07 %, from 0.01 % to 0.20 %, from 0.01 % to 0.15 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16%, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, or 0.25 % Cr. In some cases, Cr is not present in the alloy (i.e., 0 %). All expressed in wt. %.Zirconium (Zr)

[0107] In some examples, the aluminum alloy described herein includes Zr in an amount of up to 0.25 % (e.g., up to 0.20 %, up to 0.15 %, up to 0.10 %, up to 0.05 %, up to 0.07 %, from 0.01 % to 0.20 %, from 0.01 % to 0.15 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, or 0.25 % Zr. In some cases, Zr is not present in the alloy (i.e., 0 %). All expressed in wt. %.Silicon (Si)

[0108] In certain examples, the disclosed aluminum alloy used in the cladding layer includes Si in an amount up to about 1.00 % (e.g., from 0 % to 1.00 %, from 0.05 % to 1.00 %, from 0 % to 0.70 %, from 0.05 % to 0.70 %, from 0 % to 0.40 %, or from 0.05 % to 0.40 %) based on the total weight of the alloy. For example, the alloy can include 0.03 %, 0.04 %, 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, or 1.00 % Si. In some cases, the disclosed alloy does not include Si (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Iron (Fe)

[0109] In certain examples, the disclosed aluminum alloy used in the cladding layer includes Fe in an amount up to about 1.40 % (e.g., from 0 % to 1.40 %, from 0.05 % to 1.40 %, from 0 % to 1.00 %, or from 0.05 % to 1.00 %) based on the total weight of the alloy. For example, the alloy can include 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %, 0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, 1.00 %, 1.05 %, 1.10 %, 1.15 %, 1.20 %, 1.25 %, 1.30 %, 1.35 %, or 1.40 % Fe. In some cases, the disclosed alloy does not include Fe (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Copper (Cu)

[0110] In certain examples, the disclosed aluminum alloy used in the cladding layer includes Cu in an amount up to about 0.25 % (e.g., from 0 % to 0.25 %, from 0.05 % to 0.25 %, from 0 % to 0.10 %, or from 0.05 % to 0.10 %) based on the total weight of the alloy. For example, the alloy can include 0.010 %, 0.015 %. 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085%, 0.090 %, 0.095 %, 0.100 %, 0.105 %, 0.110 %, 0.115 %, 0.120 %, 0.125 %, 0.130 %, 0.135 %, 0.140 %, 0.145 %, 0.150 %, 0.155 %, 0.160 %, 0.165 %, 0.170 %, 0.175 %, 0.180 %, 0.185 %, 0.190 %, 0.195 %, 0.200 %, 0.205 %, 0.210 %, 0.215 %, 0.220 %, 0.225 %, 0.230 %, 0.235 %, 0.240 %, 0.245 %, or 0.250 % Cu. All expressed in wt. % based on the total weight of the aluminum alloy.Magnesium (Mg)[OHl] In certain aspects, the disclosed aluminum alloy used in the cladding layer includes Mg in an amount up to about 0.20 % (e.g., from 0 % to 0.20 %, from 0.01 % to 0.20 %, from 0 % to 0.10 %, or from 0.01 % to 0.10 %, from 0 % to 0.05 %, or from 0.01 % to 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.010 %, 0.015 %, 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085 %, 0.090 %, 0.095 %, 0.100 %, 0.105 %, 0.110 %, 0.115 %, 0.120 %, 0.125 %, 0.130 %, 0.135 %, 0.140 %, 0.145 %, 0.150 %, 0.155 %, 0.160 %, 0.165 %, 0.170 %, 0.175 %, 0.180 %, 0.185 %, 0.190 %, 0.195 %, or 0.200 % Mg. In some cases, the disclosed alloy does not include Mg (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Nickel (Ni)

[0112] In certain aspects, the disclosed aluminum alloy used in the cladding layer Ni in an amount up to about 0.10 % (e.g., from 0 % to 0.10 %, from 0.01 % to 0.10 %, from 0 % to 0.05 %, or from 0.01 % to 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.010 %, 0.015 %, 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085 %, 0.090 %, 0.095 %, or 0.100 % Ni. In some cases, the disclosed alloy does not include Ni (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Zinc (Zn)

[0113] In certain examples, the disclosed aluminum alloy used in the cladding layer includes Zn in an amount up to about 3.00 % (e.g., from 0 % to 3.00 %, from 0.05 % to 3.00 %, from 0 % to 2.00 %, from 0.05 % to 1.00 %, from 0 % to 1.00 %, or from 0.05 % to 1.00 %) based on the total weight of the alloy. For example, the alloy can include 0.05 %, 0.10 %, 0.15 %, 0.20 %, 0.25 %, 0.30 %, 0.35 %, 0.40 %, 0.45 %, 0.50 %, 0.55 %, 0.60 %, 0.65 %,0.70 %, 0.75 %, 0.80 %, 0.85 %, 0.90 %, 1.00 %, 1.05 %, 1.10 %, 1.15 %, 1.20 %, 1.25 %,1.30 %, 1.35 %, 1.40 %, 1.45 %, 1.50 %, 1.55 %, 1.60 %, 1.65 %, 1.70 %, 1.75 %, 1.80 %,1.85 %, 1.90 %, 2.00 %, 2.05 %, 2.10 %, 2.15 %, 2.20 %, 2.25 %, 2.30 %, 2.35 %, 2.40 %,2.45 %, 2.50 %, 2.55 %, 2.60 %, 2.65 %, 2.70 %, 2.75 %, 2.80 %, 2.85 %, 2.90 %, or 3.00 %Zn. In some cases, the disclosed alloy does not include Zn (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.Titanium (Ti)

[0114] In certain aspects, the disclosed aluminum alloy used in the cladding layer includes Ti in an amount up to about 0.15 % (e.g., from 0 % to 0.15 %, from 0.01 % to 0.15 %, from 0.01 % to 0.05 %, or from 0.05 % to 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.010 %, 0.015 %, 0.020 %, 0.025 %, 0.030 %, 0.035 %, 0.040 %, 0.045 %, 0.050 %, 0.055 %, 0.060 %, 0.065 %, 0.070 %, 0.075 %, 0.080 %, 0.085 %, 0.090 %, 0.095 %, 0.100 %, 0.110 %, 0.120 %, 0.115 %, 0.120 %, 0.125 %, 0.130 %, 0.135 %, 0.140 %, 0.145 %, or 0.150 % Ti. In some cases, the disclosed alloy does not include Ti (i.e., 0 %). All expressed in wt. % based on the total weight of the aluminum alloy.

[0115] Optionally, the disclosed aluminum alloy used in the cladding layer can further include other minor elements, sometimes referred to as impurities, in amounts of about 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below or each of said impurities. These impurities may include, but are not limited to, V, Sc, Y, Hf, Th, Ga, Sn, Pb, Ag, Bi, Sr, Ca, Li, or combinations thereof. Accordingly, Sc, Y, Hf, Th, Ga, Sn, Pb, Ag, Bi, Sr, Ca, or Li, if present, may each independently be present in an alloy in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below. In certain aspects, the sum of all impurities does not exceed 0.15 % (e.g., does not exceed 0.10 %, or does not exceed 0.05 %). In certain aspect, the apply compositions may be devoid of (not comprise or comprise at 0.00 %) one or more of: Sc, Y, Hf, Th, Ga, Sn, Pb, Ag, Bi, Sr, Ca, and Li. All expressed in wt. % based on the total weight of the aluminum alloy.

[0116] The remaining percentage of the aluminum alloy may be aluminum, e.g., remainder Al.

[0117] Regarding the composition of the cladding layer, any alloy designated as a Ixxx series aluminum alloy or a 7xxx series aluminum alloy including modified versions thereof to achieve the desired chemical composition is suitable for use as the cladding layer. In some examples, the cladding layer may be a 7xxx series aluminum alloy such as F772 or modification thereof.Recycled Aluminum Alloy Materials for Core Alloy

[0118] The aluminum alloy products described herein can tolerate high amounts of recycled aluminum alloy materials, thereby reducing greenhouse gas emissions associated with producing the aluminum alloy products. The impact of the impurities and / or alloyingelements on the mechanical properties of the aluminum alloy products from incorporating the recycled aluminum alloy materials is reduced by providing a cladding layer on at least one side of the core layer of the aluminum alloy products. The cladding layer enables the aluminum alloy products to include recycled aluminum alloy materials with high Mg content (e.g., used clad aluminum alloy products including 3xxx / 4xxx series aluminum alloy) for producing aluminum alloy products that can still exhibit desirable properties.

[0119] The core layer of the aluminum alloy products described herein includes less primary aluminum than conventional 3xxx series aluminum alloys or 7xxx series aluminum alloys, thereby lowering carbon emissions during production to reduce an overall carbon footprint. The aluminum alloy compositions described herein can include higher amounts of recycled aluminum alloy materials to reduce the overall carbon footprint of the aluminum alloy compared to conventional 3xxx series aluminum alloys. Aluminum alloys produced from recycled aluminum alloys with little to no primary aluminum minimize potential environmental impacts.

[0120] In some embodiments, the aluminum alloys described herein provide a composition that is well-suited for utilizing used clad aluminum alloy products as recycled material. Specifically, the aluminum alloys described herein can be produced from a substantial portion of used clad aluminum alloy products including a mixture of 3xxx and 4xxx series aluminum alloy. In some embodiments, used clad aluminum alloy products comprising a mixture of the 3xxx and 4xxx series aluminum alloy can be used as recycled material. As discussed herein, the aluminum alloy composition can utilize recycled aluminum alloy materials (e.g., used clad aluminum alloy products) to produce the aluminum alloy due to the cladding layer that prevents or reduce Mg content of the aluminum alloy from migrating and affecting CAB for the aluminum alloy product. The aluminum alloy can be produced with higher volumes of recycled aluminum alloy materials and reduced amounts of primary aluminum. In some embodiments, the aluminum alloy composition described herein can be produced from a mixture of 3xxx series and 4xxx series aluminum alloys. In some aspects, the aluminum alloys described herein include an amount of recycled aluminum alloy materials at or greater than 50 % (e.g., at or greater than 52 %, at or greater than 54 %, at or greater than 56 %, at or greater than 58 %, at or greater than 60 %, at or greater than 62 %, at or greater than 64 %, or at or greater than 65 %). As discussed above, in some aspects, the aluminum alloys described herein for use as the core layer of the aluminum alloy product are particularly well-suited to incorporate a mixture of 3xxx series aluminum alloy scrap and 4xxx series aluminum alloy scrap.

[0121] In some aspects, the aluminum alloys described herein include less than 50 % primary aluminum, e.g., less than 45 %, less than 40 %, less than 35 %, less than 30 %, less than 29 %, less than 28 %, less than 27 %, less than 26 %, less than 25 %, less than 24 %, less than 23 %, less than 22 %, less than 21 %, or less than 20 %. All percentages are expressed in wt. %.Methods of Preparing and Processing

[0122] In certain aspects, the disclosed aluminum alloy product is a product of a disclosed method. Without intending to limit the disclosure, aluminum alloy product properties are partially determined by the cladding layer deposited during the preparation of the aluminum alloy product. In certain aspects, the method of preparation for the cladding layer of the aluminum alloy product may influence or even determine whether the aluminum alloy product will have properties adequate for a desired application.Casting

[0123] A cladding layer as described herein can be attached to a core layer as described herein to form a clad product by any means known to persons of ordinary skill in the art. For example, a cladding layer can be attached to a core layer by direct chill co-casting (i.e., fusion casting) as described in, for example, U.S. Pat. Nos. 7,748,434 and 8,927,113, both of which are hereby incorporated by reference in their entireties; by hot and cold rolling a composite cast ingot as described in U.S. Pat. No. 7,472,740, which is hereby incorporated by reference in its entirety; or by roll bonding to achieve the required metallurgical bonding between the core layer and the cladding 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.

[0124] In some embodiments, the casting process can include a direct chill (DC) casting process. The DC casting process is performed according to standards commonly used in the aluminum industry as known to one of skill in the art. The DC process can provide an ingot. Optionally, the ingot can be scalped before downstream processing. Optionally, the casting process can include a continuous casting (CC) process. In some embodiments, the ingot can be scalped after casting.

[0125] The roll bonding process can be carried out in different manners, as known to those of ordinary skill in the art. 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 amulti-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.

[0126] 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. The cast aluminum alloy product can then be subjected to further processing steps. For example, the processing methods as described herein can include, but are not limited to, homogenization, preheating, hot rolling, cold rolling, solution heat treatment, annealing and an optional pre-aging step, as known to those of ordinary skill in the art.Preheating

[0127] The preheating step can include heating a cast aluminum alloy product as described herein to attain a preheating temperature of at least 350° C (e.g., 360° C, 370° C, 380° C, 390° C, 400° C, 410° C, 420° C, 430° C, 440° C, 450° C, 460° C, 470° C, 480° C,490° C, 500° C, 510° C, 520° C, 530° C, 540° C, 550° C, 560° C, 570° C, 580° C, 580° C,590° C, 600° C, 610° C, 620° C, 630° C, or anywhere in between). For example, the cast aluminum alloy product can be heated to a temperature of from 350° C to 630° C, 360° C to620° C, 375° C to 610° C, 400° C to 600° C, 410° C to 575° C, from 420° C to 550° C, from 440° C to 540° C, from 450° C to 530° C, or from 450° C to 480° C. In some cases, the heating rate to the preheating temperature can be 10° C / hour or greater, 20° C / hour or greater, 30° C / hour or greater, 40° C / hour or greater, 50° C / hour or greater, 60° C / hour or greater, or 70° C / hour or greater. In other cases, the heating rate to the preheating temperature can be from 10° C / min to 100° C / min (e.g., 10° C / min to 90° C / min, 20° C / min to 80° C / min, 30° C / min to 70° C / min, from 40° C / min to 65° C / min, from 45° C / min to 60° C / min, or from 50° C / min to 60° C / min).

[0128] Optionally, the cast aluminum alloy product is then allowed to soak (i.e., held at the indicated temperature) for a period of time at the preheating temperature range.According to one non-limiting example, the cast aluminum alloy product is allowed to soak for up to 30 hours (e.g., from 10 minutes to 30 hours, inclusively). For example, the cast aluminum alloy product can be soaked at a temperature from 450° C to 560° C (e.g., up to 480° C) for 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, or anywhere in between. In someembodiments, the cast aluminum alloy product is soaked at a preheating temperature from 480° C to 560° C for 5 hours to 7 hours.Homogenization

[0129] In some embodiments, the method may include an optional homogenization step. In some embodiments, the homogenization step can be used in lieu of the preheating step. In some embodiments, the homogenization step can be used in combination with the preheating step. For example, the cast aluminum alloy product can be homogenized and then subjected to preheating.

[0130] The homogenization step can include heating a cast aluminum alloy product as described herein to attain a homogenization temperature of at least 500° C (e.g., 500° C, 510° C, 520° C, 530° C, 540° C, 550° C, 560° C, 570° C, 580° C, 580° C, 590° C, 600° C, 610° C, 620° C, 630° C, or anywhere in between). For example, the cast aluminum alloy product can be heated to a temperature of from 500° C to 630° C, 510° C to 615° C, 500° C to 575° C, 510° C to 600° C, or from 525° C to 625° C. In some cases, the heating rate to the homogenization temperature can be 10° C / hour or greater, 20° C / hour or greater, 30° C / hour or greater, 40° C / hour or greater, 50° C / hour or greater, 60° C / hour or greater, or 70° C / hour or greater. In other cases, the heating rate to the homogenization temperature can be from 10° C / min to 100° C / min (e.g., 10° C / min to 90° C / min, 20° C / min to 80° C / min, 30° C / min to 70° C / min, from 40° C / min to 65° C / min, from 45° C / min to 60° C / min, or from 50° C / min to 60° C / min).

[0131] The cast aluminum alloy product is then allowed to soak (i.e., held at the indicated temperature) for a period of time at the homogenization temperature range. According to one non-limiting example, the cast aluminum alloy product is allowed to soak for up to 30 hours (e.g., from 10 minutes to 30 hours, inclusively). For example, the cast aluminum alloy product can be soaked at a temperature from 500° C to 630° C for 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, or anywhere in between.

[0132] In some embodiments, the cast aluminum alloy product is hot rolled directly after the cast aluminum alloy product reaches the preheating or homogenization temperature. For example, for an aluminum alloy product including a cladding layer comprising a 4xxx seriesaluminum alloy, the product may be hot rolled as soon as the product reaches the preheating or homogenization temperature to prevent Si migration to the core layer.Hot Rolling

[0133] Following the homogenization step and / or preheating step, a hot rolling step can be performed to form a hot rolled product from the cast aluminum alloy product. In certain aspects, the spray coating step can be performed during or after the hot rolling step. The cast aluminum alloy product can be hot rolled at a temperature from 350° C to 580° C (e.g., from 375° C to 560° C, from 400° C to 570° C, from 425° C to 530° C, from 460° C to 520° C, or from 475° C to 520° C). For example, the hot rolling step can be performed at a temperature of 350° C, 360° C, 370° C, 380° C, 390° C, 400° C, 410° C, 420° C, 430° C, 440° C, 450° C, 460° C, 470° C, 480° C, 490° C, 500° C, 510° C, 520° C, 530° C, 540° C, 550° C, 560° C, 570° C, 580° C or anywhere in between. In some embodiments, the hot rolling temperature ranges from 460° C to 520° C.

[0134] In certain cases, the cast aluminum alloy product can be hot rolled to a thickness of from 2 mm to 15 mm (e.g., from 2.5 mm to 12 mm). In certain cases, the cast aluminum alloy product can be hot rolled to a thickness of from 0.5 mm to 10 mm (e.g., from 1.5 mm to 8 mm). For example, the cast aluminum alloy product can be hot rolled to a thickness of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, or anywhere in between. In certain cases, the cast aluminum alloy product can be hot rolled to a gauge greater than 15 mm (i.e., a plate). In other cases, the cast aluminum alloy product can be hot rolled to a gauge less than 4 mm (i.e., a sheet).

[0135] The spray coating step can be performed after the cast aluminum alloy product is heated during the hot rolling step. In certain aspects, the spray coating step may be performed after the hot rolled product has been heated to the hot roll temperature and reduced to a thickness of up to 2.50 mm. As an example, a cladding layer having a thickness of 250 pm can be deposited on the hot rolled product after the hot rolled product has been reduced to a thickness of 2.50 mm. Spray coating the cladding layer while the hot rolled product is hot (e.g., at or above 350 °C) can improve the cladding layer due to porosity and surface adhesion with respect to the aluminum alloy of the hot rolled product.Cold Rolling

[0136] Following the hot rolling step, an optional cold rolling step can be performed. The cold rolling step can include one or more cold rolling passes. In certain embodiments, the hot rolled product from the hot rolling step can be cold rolled to produce a cold rolled product (e.g., a thin-gauge shate or a sheet). In some embodiments, the cold rolled product is further processed during the cold rolling step to have a final gauge thickness ranging from 0.02 mm to 10.0 mm (e.g., from 0.04 mm to 1.0 mm or from 0.2 mm to 3.0 mm). The cold rolling can be performed to result in a final gauge thickness that represents a gauge reduction of up to about 85% (e.g., 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% reduction). The thickness of a single cladding layer may be between about 2% and about 10% (e.g., about 2% to about 4%, about 3% to about 5%, about 4% to about 6%, about 5% to about 7%, about 6% to about 8%, about 7% to about 9%, or about 8% to about 10%) of the total thickness of the cold rolled clad sheet.

[0137] The cladding layer can be deposited on the cold rolled product having the intermediate gauge thickness or the final gauge thickness. As an example, a cladding layer with a thickness of 25 pm can be deposited on a cold rolled product having a thickness of 0.25 mm. As another example, a cladding layer with a thickness of 8 pm can be spray coated onto a cold rolled product having a thickness of 0.08 mm.

[0138] In some embodiments, the cold rolling step can include two more cold rolling steps. The two or more cold rolling steps can reduce the thickness successively to the final gauge thickness. Optionally, the method can further comprise intermittent and / or final annealing steps in between or after the cold rolling steps.Method of Producing Clad Aluminum Alloy Product

[0139] 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 10 mm thick gauge or less (e.g., from about 0.5 mm to about 10 mm). For example, the cast product can be hot rolled to a plate having a final gauge thickness of about 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.

[0140] In some embodiments, the aluminum alloy products including the high recycled content aluminum alloys described herein can be a cladded product including a core layer and one or more cladding layers. In some examples, the core layer is clad on only one side (i.e., one cladding layer is present in the clad aluminum alloy product). In other examples, the core layer is clad on both sides (i.e., two cladding layers are present in the clad aluminum alloy product). The cladding layer(s) can be attached to a core layer in a variety of ways. For example, the cladding layer(s) can be attached to a core layer by direct chill co-casting (i.e., fusion casting), by hot and / or cold rolling a composite cast ingot, or by roll bonding the core layer and cladding layer,

[0141] In some embodiments, the cladding layer can be spray coated on the core layer. In certain embodiments, the spray coating step may be performed during or after the cold rolling step. For example, once the hot rolled product has been cold rolled to produce the cold rolled product, a cladding layer can be spray deposited on at least one of a first side or a second side of the cold rolled product.

[0142] In some examples, a thermal spray process or cold spray process may be used to deposit a dispersed aluminum alloy to form a cladding layer on an aluminum alloy sheet having the composition of the core layer described herein. The powdered aluminum alloys may comprise an 4xxx and / or a Ixxx aluminum alloy. For example, a combination of AA4343 and AA1350 may be used. Exemplary thermal spray techniques include Twin Wire Arc Spray (TWAS) and Wire Flame Spray (WFS).

[0143] In some examples, the thermal spray process or cold spray process may be performed prior to rolling the 3xxx aluminum alloy sheet to final gauge thickness.

[0144] In some examples, the surface of the 3xxx aluminum alloy sheet may be treated prior to a thermal spray or cold spray process to improve the consistency and uniformity of the cladding layer on the substrate (3xxx sheet). Non-limiting examples surface treatments include grit blasting and chemical etching.

[0145] Prior to depositing the cladding layer, the cold rolled product can be cleaned (e.g., in a cleaning process chamber) to remove residual oils and excessive metal oxide species from the surface(s) of the final gauge product. In some embodiments, cleaning the final gauge product can involve etching one or more surfaces of the final gauge product. Optionally, residual oils can be removed from a first surface and a second surface of the final gauge product (e.g., a top surface and a bottom surface can be cleaned). In some aspects, all surfaces of the final gauge product are cleaned (e.g., the top surface, the bottom surface, afirst side, and a second side are cleaned). At least a first surface of the final gauge product is then engineered according to methods described herein.Methods of Making Clad Aluminum Products

[0146] The clad aluminum alloy products described herein may be formed into a desired structural shape where welding and / or brazing is used to create joints. For example, the process may include assembling and securing the clad aluminum alloy product of the present disclosure to a metal product (e.g., via welding and / or brazing to form a joint therebetween). The joint may be a seam where the clad aluminum alloy product is joined to itself. The joint may be between clad aluminum alloy product and another aluminum alloy product, which may or may not be a clad aluminum alloy product. The joint may be between clad aluminum alloy product and product having a composition other than aluminum alloy, for example, steel.

[0147] One skilled in the art will recognize the joining method appropriate based on the compositions to be joined. Examples of joining methods may include, but are not limited to, vacuum brazing, controlled atmosphere brazing (CAB), Ni plating processes, flame brazing, induction brazing, laser brazing, open atmosphere brazing, molten salt brazing, laser beam welding, friction stir welding, and the like.Methods of Brazing

[0148] The clad aluminum alloy products described herein are suitable for brazing applications. Accordingly, various brazing processes and technological steps can be suitably employed in the embodiments of the present disclosure. The clad aluminum alloy products can be brazed in an inert gas atmosphere. Any suitable inert gas may be employed including, for example, argon, helium, nitrogen, etc. The clad aluminum alloy products described herein are suitable for CAB. For the brazing cycle, the clad aluminum alloy products can be heated in a CAB furnace. In some embodiments, the aluminum alloys can be used in other joining processes (e.g., flame brazing, fluxed braze rings / shims, inductive heating, laser brazing, welding, adhesive bonding, etc.).

[0149] In some embodiments, the brazing process is carried out in a dry atmosphere with little or no oxygen in the atmosphere. In some embodiments, the brazing process is carried out in an inert atmosphere of nitrogen, argon, or helium. The brazing process can include heating the clad aluminum alloy products as described herein to attain a brazing temperature of at least 485° C (e.g., at least 490° C, at least 500° C, at least 510° C, at least 520° C, oranywhere in between). For example, the clad aluminum alloy product can be heated to a temperature of from 485° C to 560° C, from 500° C to 615° C, or from 570° C to 620° C. In some cases, the heating rate to the brazing temperature can be 200° C / hour or less, 180° C / hour or less, 160° C / hour or less, 140° C / hour or less, 120° C / hour or less, 100° C / hour or less, 75° C / hour or less, 50° C / hour or less, 40° C / hour or less, 30° C / hour or less, 25° C / hour or less, 20° C / hour or less, 15° C / hour or less, or 10° C / hour or less. In other cases, the heating rate to the brazing temperature can be from 10° C / min to 200° C / min (e.g., 10° C / min to 175° C / min, 10° C / min to 150° C / min, 10° C / min to 100° C / min, from 20° C / min to 90° C / min, from 30° C / min to 80° C / min, from 40° C / min to 70° C / min, or from 50° C / min to 60° C / min). In some embodiments, the heating rate to peak temperature in the CAB furnace is less than 3 minutes.

[0150] In some embodiments, a method of manufacturing a brazing product, such as a heat exchanger, joined by brazing or an assembly of brazed components is provided. The method may include providing the components of which at least one is made from a clad aluminum alloy product described herein. The method may include assembling the components, such as corrugated fin stock material and other components such as tubes, into an assembly. The method may further include brazing the assembly without applying a brazing flux on the assembly of components. The whole assembly is brazed in a controlled inert gas atmosphere at a brazing temperature, typically at a temperature in a range of 485° C to 620° C for a period long enough for melting and spreading of a filler joining the various components (e.g., a dwell time of 1 to 10 minutes). In some embodiments, the dwell time may be up to 10 minutes (e.g., from 5 to 10 minutes, up to 9 minutes, up to 8 minutes, up to 7 minutes, up to 6 minutes, up to 5 minutes, up to 4 minutes, up to 3 minutes, up to 2 minutes, up to 1 minutes, any time in between). The oxygen content in the brazing atmosphere should be as low as reasonably possible, and is preferably below 100 ppm, and more preferably below 50 ppm, for example at 25 ppm or less. The method further includes cooling of the brazed assembly, typically to below 100° C, e.g., to room temperature using, for example, blown air or any other suitable cooling medium.

[0151] While metal parts such as aluminum alloy articles are described throughout the text, the methods and articles apply to any metal. In some examples, the metal part is aluminum, an aluminum alloy, magnesium, a magnesium-based material, titanium, a titanium-based material, copper, a copper-based material, steel, a steel-based material, bronze, a bronze-based material, brass, a brass-based material, a composite, a sheet used in composites, or any other suitable metal or combination of materials.Uses and Applications of Clad Aluminum Products

[0152] Uses and applications of the clad aluminum alloy products described herein are included within the scope of the present invention, as are products, forms, apparatuses, and similar things fabricated with or comprising the aluminum alloys described herein. The processes for fabricating, producing, or manufacturing such products, forms, apparatuses, and similar things are also included within the scope of the present invention.

[0153] The aluminum alloy products and methods described herein can be used in industrial applications including sacrificial parts, heat dissipation, heating, ventilation, air conditioning and refrigeration, or packaging and building materials. The aluminum alloy products described herein can be used in various applications, for example, as fin stock for heat exchangers. In one example, the aluminum alloy products described herein are useful for high performance, light weight automotive heat exchangers. More generally, the aluminum alloys described herein can be used in motor vehicle heat exchangers such as radiators, condensers, heaters, intercoolers, charge air coolers, oil coolers, exhaust coolers, fuel coolers, turbulators, cold plates (e.g., cooling plates or battery cooling plates) and evaporators. Cold plates are typically produced by brazing a bare aluminum flat sheet to a formed sheet with a clad liner on one side and possible a Ixxx or a 7xxx sacrificial liner on the other side (e.g., coolant channel side). As discussed above, the compositions and the processes for producing the aluminum alloy products described herein lead to aluminum alloy products possessing a combination of beneficial characteristics and properties that make it suitable for manufacturing cold plates, base plates, tubes, pipes, headers, manifolds, side supports or other parts of automotive or industrial heat exchangers. However, the uses and applications of the aluminum alloy products described herein are not limited to automotive or industrial heat exchangers and other uses are envisioned. The aluminum alloy products described herein can be used for manufacture of various devices employing heat exchangers and produced by brazing, such as devices employed in heating, ventilation, and air conditioning (HVAC).

[0154] The aluminum alloy products disclosed herein are suitable substitutes for metals conventionally used in indoor and outdoor HVAC units. As used herein, the meaning of “indoor” refers to a placement contained within any structure produced by humans with controlled environmental conditions. As used herein, the meaning of “outdoor” refers to a placement not fully contained within any structure produced by humans and exposed to geological and meteorological environmental conditions comprising air, solar radiation, wind, rain, sleet, snow, freezing rain, ice, hail, dust storms, humidity, aridity, smoke (e.g., tobaccosmoke, house fire smoke, industrial incinerator smoke, wildfire smoke, etc.), smog, fossil fuel exhaust, bio-fuel exhaust, salts (e.g., high salt content air in regions near a body of salt water), radioactivity, electromagnetic waves, corrosive gases, corrosive liquids, galvanic metals, galvanic alloys, corrosive solids, plasma, fire, electrostatic discharge (e.g., lightning), biological materials (e.g., animal waste, saliva, excreted oils, vegetation), wind-blown particulates, barometric pressure change, and diurnal temperature change. Due to the cladding layer(s), the aluminum alloy products described herein provide better corrosion performance compared to conventional aluminum alloy products currently employed in heat exchanger applications.EXAMPLES

[0155] The following examples serve to further illustrate the present invention without, however, constituting any limitation thereof. On the contrary, it is to be clearly understood that resort may be had to various embodiments, modifications and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the invention. During the studies described in the following examples, conventional procedures were followed, unless otherwise stated. Some of the procedures are described below for illustrative purposes.

[0156] Clad aluminum alloy products having the core layer compositions and cladding layer compositions shown in Table 9 were prepared to evaluate brazing performance. Example 1 was used as a baseline sample to evaluate inventive Examples 2 and 3. Example 4 was used as a baseline control to evaluate inventive Examples 5 and 6.Table 9Table 9, cont.

[0157] To prepare each sample, a liner of cladding material was hot roll bonded on both sides of a core sheet, and cold rolled to 100 pm. The cores were homogenized following a 50 °C / hr heat up to 590 °C and soaked for 6 to 7 hours. This was followed by hot rolling to a specified roll gap (18.5 mm or 0.73”). Cores and liners were sectioned, caustic cleaned, desmutted in 50% HNO3, rinsed and forced air dried. The liners were welded on both sides of the cores, about 10 mm from the leading edge to allow the rolls to grab onto the sample during the first hot rolling reduction to bond the liners to the core. The bonded samples were inserted in a furnace, holding at 450 °C, at 5 min interval. The total soak duration was between 45 and 60 minutes. A portion of each hot band was cold rolled from 3 mm to about 100 pm and cut into strips for evaluation.

[0158] Coupons of a Novelis AB987 brazing sheet was used as the substrate for all samples. The control core material was an AA3003 aluminum alloy. The control samples had a gauge thickness of 65 pm. The samples were formed into angled fins and brazed to the AB987 clad sheet for evaluation.

[0159] Brazing was conducted using a quartz tube set within a clam-shell furnace to expose bent strips (8 mm x 55 mm) on coupons to a simulated braze cycle. The graphite plate was heated to approximately 605 °C to 608 °C and the clam-shell would be opened to rapidly cool for each cycle. The flux solution was 32g Nocolok Flux ONS in 200 mL isopropyl alcohol. The final cycle was 40 °C / min from approximately 300 °C up to a furnace temperature of 630 °C. Argon was flowing through the quartz tube during the full duration of the braze cycle. Multiple runs were carried out using a Cl / F-based flux (HARRIS Al-Braze E.C. Model ECDF 1 / 2) to define the brazing cycle.

[0160] Photographs of each brazed sample and micrographs showing a cross-section of the clad aluminum alloy fins brazed to a metal substrate are shown in FIGS. 3-14. The cladproduct in FIGS. 3 and 4 includes 0.003 wt. % Mg in its core layer. The clad product in FIGS. 5 and 6 includes 0.25 wt. % Mg in its core layer. The clad product in FIGS. 7 and 8 includes 0.48 wt. % Mg in its core layer. The clad product in FIGS. 9 and 10 includes 0.002 wt. % Mg in its core layer. The clad product in FIGS. 11 and 12 includes 0.259 wt. % Mg in its core layer. The clad product in FIGS. 13 and 14 includes 0.503 wt. % Mg in its core layer. Samples with higher amounts of Mg in the core (Ex. 2 and 3) had comparable dissolution and brazing performance as baseline Example 1. Samples with higher amounts of Mg in the core (Ex. 5 and 6) had comparable dissolution and brazing performance as baseline Example 4.ILLUSTRATIONS

[0161] A collection of exemplary illustrations of embodiments is provided below, including at least some explicitly enumerated as an “illustration” providing additional description of a variety of example embodiments in accordance with the concepts described herein.

[0162] Illustration 1 : An aluminum alloy product comprising: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0163] Illustration 2: The illustration of any preceding or subsequent illustration, wherein the core layer comprises at least 0.05 wt. % Mg.

[0164] Illustration 3: The illustration of any preceding or subsequent illustration, wherein the core layer comprises up to 0.25 wt. % Cr and up to 0.25 wt. % Zr.

[0165] Illustration 4: The illustration of any preceding or subsequent illustration, wherein the cladding layer has a thickness of from 5 % to 15 % of the total thickness of the aluminum alloy product.

[0166] Illustration 5: The illustration of any preceding or subsequent illustration, wherein the cladding layer comprises a Ixxx series or a 7xxx series aluminum alloy including up to 0.25 wt. % Mn, up to 0.25 wt. % Cr, up to 0.25 wt. % Zr, or combinations thereof.

[0167] Illustration 6: The illustration of any preceding or subsequent illustration, wherein the cladding layer is roll bonded as a continuous layer on a portion of at least one of the first side or the second side of the core layer.

[0168] Illustration 7: The illustration of any preceding or subsequent illustration, wherein the cladding layer is spray coated as a continuous layer on at least one of the first side or the second side of the core layer.

[0169] Illustration 8: The illustration of any preceding or subsequent illustration, wherein the cladding layer covers up to 75 % of the core layer.

[0170] Illustration 9: The illustration of any preceding or subsequent illustration, wherein the cladding layer enables flux free brazing in a controlled atmosphere brazing process.

[0171] Illustration 10: The illustration of any preceding or subsequent illustration, wherein the core layer comprises recycled aluminum alloy materials.

[0172] Illustration 11 : The illustration of any preceding or subsequent illustration, wherein the recycled aluminum alloy materials comprise used clad aluminum alloy products comprising a mixture of 3xxx series aluminum alloys and 4xxx series aluminum alloys.

[0173] Illustration 12: The illustration of any preceding or subsequent illustration, wherein the aluminum alloy product is used as fin stock.

[0174] Illustration 13: The illustration of any preceding or subsequent illustration, wherein the cladding layer is deposited in discrete regions on at least one of the first side or the second side of the core layer.

[0175] Illustration 14: A heat exchanger comprising the aluminum alloy product of any preceding or subsequent illustration.

[0176] Illustration 15: A method of forming an aluminum alloy product, the method comprising: casting an aluminum alloy to form a cast product, wherein the aluminum alloy comprises a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; homogenizing the cast product; hot rolling the cast product to produce a hot rolled product; cold rolling the hot rolled product to produce an aluminum alloy product; and applying cladding layer on at least one a first side or a second side of the aluminum alloy product to produce a clad aluminum alloy product, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy.

[0177] Illustration 16: The illustration of any preceding or subsequent illustration, wherein the cladding layer is spray coated by depositing a spray mixture comprising metal particles on the aluminum alloy product.

[0178] Illustration 17: The illustration of any preceding or subsequent illustration, wherein the spray mixture further comprises flux particles combined with the metal particles.

[0179] Illustration 18: The illustration of any preceding or subsequent illustration, wherein applying the cladding layer includes roll bonding the cladding layer on at least one the first side or the second side of the aluminum alloy product.

[0180] Illustration 19: The illustration of any preceding or subsequent illustration, wherein the aluminum alloy product is heated during the hot rolling step to a hot roll temperature of between 350 °C and 580 °C prior to roll bonding.

[0181] Illustration 20: The illustration of any preceding or subsequent illustration, wherein the aluminum alloy product is reduced to a thickness of 0.05 mm to 2.50 mm prior to spray coating the cladding layer on the aluminum alloy product.

[0182] Illustration 21 : The illustration of any preceding or subsequent illustration, wherein the cladding layer is a sacrificial layer configured to corrode prior to the aluminum alloy product.

[0183] Illustration 22: The illustration of any preceding or subsequent illustration, wherein the cladding layer prevents Mg migration and / or diffusion from within the aluminum alloy product to a surface of the aluminum alloy product.

[0184] Illustration 23: A method of forming a brazing product, the method comprising the steps of: providing one or more metal parts; providing a clad aluminum alloy product on or between the one or more metal parts to form an assembly, wherein the clad aluminum alloy product comprises: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy; and brazing the assembly in a controlled atmosphere to join the clad aluminum alloy product and the one or more metal parts to produce a brazed assembly; optionally applying a flux load before brazing; and cooling the brazed assembly.

[0185] Illustration 24: The illustration of any preceding or subsequent illustration, wherein the assembly is brazed at a brazing temperature from 550° C to 620° C for 5 to 10 minutes.

[0186] Illustration 25: A clad aluminum alloy product comprising a core layer having a first surface and a second surface on opposing sides of the core layer, wherein the core layer comprises a first aluminum alloy comprising a 3xxx series aluminum alloy comprising up to 1.5 wt. % Mg; and a cladding layer adjacent to and in contact with at least one of the first surface or the second surface of the core layer, wherein the cladding layer comprises a secondaluminum alloy comprising a Ixxx series or a 7xxx series aluminum alloy comprising up to 3 wt. % Zn.

[0187] Illustration 26: The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein the core layer further comprises up to 1 wt. % Si, up to 1 wt. % Fe, up to 0.9 wt. % Cu, up to 1.8 wt. % Mn, up to 0.1 wt. % Ni, up to 0.3 wt. % Cr, up to 3 wt. % Zn, up to 0.2 wt. % Ti, up to 0.15 wt. % impurities, and aluminum.

[0188] Illustration 27: The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein the cladding layer further comprises up to 1 wt. % Si, up to 1.4 wt. % Fe, up to 0.25 wt. % Cu, up to 0.2 wt. % Mn, up to 0.2 wt. % Mg, up to 0.1 wt. % Ni, up to 0.25 wt. % Cr, up to 0.15 wt. % Ti, up to 0.15 wt. % impurities, and aluminum.

[0189] Illustration 28: The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein a Mg content in the core layer is greater than a Mg content in the cladding layer.

[0190] Illustration 29: The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein the core layer comprises up to 0.5 wt. % Mg.

[0191] Illustration 30: The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein the core layer comprises up to 0.25 wt. % Mg.

[0192] Illustration 31 : The clad aluminum alloy product of any preceding or subsequent aspect or combination of aspects, wherein the core layer comprises a recycled aluminum alloy.

[0193] Illustration 32: The clad aluminum alloy product of any preceding aspect or combination of aspects, wherein the cladding layer is adjacent to and in contact with both the first surface and the second surface of the core layer.

[0194] Illustration 33: A product fabricated with the clad aluminum alloy product of any preceding aspect or combination of aspects, wherein the product is formed into a structural shape that is welded and / or brazed to a metal substrate.

[0195] Illustration 34: The product of any preceding aspect, wherein the product is a heater, an evaporator plate, an evaporator, a radiator, a heater core, a condenser, a turbulator, a tube, a pipe, or a manifold.

[0196] Illustration 35: A process comprising assembling and securing via welding and / or brazing the clad aluminum alloy product of any preceding aspect or combination of aspects to a metal substrate.

[0197] Illustration 36: A process for producing a clad aluminum alloy product comprising a core layer and a cladding layer, the process comprising co-casting an ingot having a core and a cladding on at least one outer surface of the core, and processing the ingot to form the clad aluminum alloy product, wherein the core layer comprises a 3xxx series aluminum alloy comprising up to 1.5 wt. % Mg and wherein the cladding layer comprises a Ixxx series or a 7xxx series aluminum alloy comprising up to 3 wt. % Zn.

[0198] Illustration 37: A process for producing a clad aluminum alloy product comprising a core layer and a cladding layer, the process comprising joining the core layer and the cladding layer where the cladding layer is adjacent with and bonded to at least one surface of the core layer, wherein the core layer comprises a 3xxx series aluminum alloy comprising up to 1.5 wt. % Mg and wherein the cladding layer comprises a Ixxx series, 4xxx series, or a 7xxx series aluminum alloy comprising up to 3 wt. % Zn.

[0199] Illustration 38: A process for producing a clad aluminum alloy product comprising a core layer and a cladding layer, the process comprising depositing an aluminum alloy composition on at least one surface of the core layer by thermal spray or cold spray to form the cladding layer, wherein the core layer comprises a 3xxx series aluminum alloy comprising up to 1.5 wt. % Mg and wherein the cladding layer comprises a Ixxx series aluminum alloy comprising up to 3 wt. % Zn.

[0200] Illustration 39: The process of any preceding aspect or combination of aspects, wherein the cladding layer further comprises an 4xxx series aluminum alloy.

[0201] All patents, publications and abstracts cited above are incorporated herein by reference in their entireties. Various embodiments of the invention have been described in fulfillment of the various objectives of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptions thereof will be readily 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

WHAT IS CLAIMED IS:

1. An aluminum alloy product comprising: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy. The aluminum alloy product of claim 1, wherein the core layer comprises at least 0.05 wt. % Mg.

2. The aluminum alloy product of claim 1, wherein the core layer comprises up to 0.25 wt. % Cr and up to 0.25 wt. % Zr.

3. The aluminum alloy product of claim 1, wherein the cladding layer has a thickness of from 5 % to 15 % of the total thickness of the aluminum alloy product.

4. The aluminum alloy product of claim 1, wherein the cladding layer comprises a Ixxx series or a 7xxx series aluminum alloy including up to 0.25 wt. % Mn, up to 0.25 wt. % Cr, up to 0.25 wt. % Zr, or combinations thereof.

5. The aluminum alloy product of claim 1, wherein the cladding layer is roll bonded as a continuous layer on a portion of at least one of the first side or the second side of the core layer.

6. The aluminum alloy product of claim 1, wherein the cladding layer is spray coated as a continuous layer on at least one of the first side or the second side of the core layer.

7. The aluminum alloy product of claim 7, wherein the cladding layer covers up to 75 % of the core layer.

8. The aluminum alloy product of claim 1, wherein the cladding layer enables flux free brazing in a controlled atmosphere brazing process.

9. The aluminum alloy product of claim 1, wherein the core layer comprises recycled aluminum alloy materials.

10. The aluminum alloy product of claim 10, wherein the recycled aluminum alloy materials comprise used clad aluminum alloy products comprising a mixture of 3xxx series aluminum alloys and 4xxx series aluminum alloys.

11. The aluminum alloy product of claim 1, wherein the aluminum alloy product is used as fin stock.

12. The aluminum alloy product of claim 1, wherein the cladding layer is deposited in discrete regions on at least one of the first side or the second side of the core layer.

13. A heat exchanger comprising the aluminum alloy product of any of claims 1-13.

14. A method of forming an aluminum alloy product, the method comprising: casting an aluminum alloy to form a cast product, wherein the aluminum alloy comprises a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; homogenizing the cast product; hot rolling the cast product to produce a hot rolled product; cold rolling the hot rolled product to produce an aluminum alloy product; and applying cladding layer on at least one a first side or a second side of the aluminum alloy product to produce a clad aluminum alloy product, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy.

15. The method of claim 15, wherein the cladding layer is spray coated by depositing a spray mixture comprising metal particles on the aluminum alloy product.

16. The method of claim 16, wherein the spray mixture further comprises flux particles combined with the metal particles.

17. The method of claim 15, wherein applying the cladding layer includes roll bonding the cladding layer on at least one the first side or the second side of the aluminum alloy product.

18. The method of claim 18, wherein the aluminum alloy product is heated during the hot rolling step to a hot roll temperature of between 350 °C and 580 °C prior to roll bonding.

19. The method of claim 15, wherein the aluminum alloy product is reduced to a-so-thickness of 0.05 mm to 2.50 mm prior to spray coating the cladding layer on the aluminum alloy product.

20. The method of claim 15, wherein the cladding layer is a sacrificial layer configured to corrode prior to the aluminum alloy product.

21. The method of claim 15, wherein the cladding layer prevents Mg migration and / or diffusion from within the aluminum alloy product to a surface of the aluminum alloy product.

22. A method of forming a brazing product, the method comprising the steps of: providing one or more metal parts; providing a clad aluminum alloy product on or between the one or more metal parts to form an assembly, wherein the clad aluminum alloy product comprises: a core layer comprising a 3xxx series aluminum alloy comprising up to 3.00 wt. % Zn and up to 1.50 wt. % Mg; and a cladding layer disposed on at least one of a first side or a second side of the core layer, wherein the cladding layer comprises a Ixxx series aluminum alloy, a 4xxx series aluminum alloy, or a 7xxx series aluminum alloy; and brazing the assembly in a controlled atmosphere to join the clad aluminum alloy product and the one or more metal parts to produce a brazed assembly; optionally applying a flux load before brazing; and cooling the brazed assembly.

23. The method of claim 23, wherein the assembly is brazed at a brazing temperature from 550° C to 620° C for 5 to 10 minutes.

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