CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63/371,560, filed August 16, 2022, which is incorporated herein by reference in its entirety.

FIELD

[0002] The present disclosure generally relates to processing of metal substrates, such as aluminum alloys. More specifically, the present disclosure relates to pretreatment of metal substrates, and in particular, aluminum alloy tab stock.

BACKGROUND

[0003] High throughput rates are an important consideration for facilities producing aluminum beverage cans. Conventional aluminum alloy products have been found to cause excessive wear to equipment used in some metal substrate forming systems. Excessive wear to equipment such as conversion presses can change the profile of a tool edge and subsequently cause changes in product quality. The excessive wear can lead to increased maintenance and tooling costs and production loss because the operating lines may have to be shutdown to conduct repairs or replacement of the worn or damaged equipment.

SUMMARY

[0004] The term embodiment and like terms are intended to refer broadly to all of the subject matter of this disclosure 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 claims below. Embodiments of the present disclosure covered herein are defined by the claims below, not this summary. This summary is a high-level overview of various aspects of the disclosure 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 of this disclosure, any or all drawings and each claim.

[0005] Described herein is a method of making a 5xxx series aluminum alloy substrate, the method comprising producing a pretreatment film on a surface of a 5xxx series aluminum alloy substrate to provide a pretreated 5xxx series aluminum alloy substrate and controlling a coat weight of the pretreatment film to no greater than 10 mg/ft ² (e.g., from 3 mg/ft ² to 9 mg/ft ² ). In some cases, producing the pretreatment film comprises contacting the 5xxx series aluminum alloy substrate with a pretreatment solution. Optionally, the pretreatment solution comprises chromium, molybdenum, titanium, zirconium, manganese, or combinations thereof. In some cases, the pretreatment solution comprises trivalent chromium (Cr(III)), phosphates, or combinations thereof, and in some instances, the pretreatment solution comprises compounds of titanium and zirconium (Ti/Zr). The contacting can optionally comprise spraying, roll coating, or submerging at least a portion of the aluminum alloy substrate.

[0006] The pretreatment film can have a thickness of up to 300 nm (e.g., up to 250 nm). Optionally, the pretreated 5xxx series aluminum alloy substrate has a coefficient of friction of less than 0.5 after 2 cycles according to ASTM #G99. The method described herein can further comprise degreasing at least a portion of the surface of the aluminum alloy substrate prior to producing the pretreatment film. The degreasing can comprise contacting at least a portion of the substrate with an acidic solution, an alkaline solution, an alkaline organic compound, or combinations thereof.

[0007] Optionally, the methods described herein further comprise preheating the aluminum alloy substrate to a temperature of less than 300 °C prior to producing the pretreatment film. Optionally, the 5xxx series aluminum alloy substrate is AA5182.

[0008] Also described herein is an aluminum alloy substrate prepared according to the method described above. The pretreatment film has a coat weight of no greater than 10 mg/ft ² (e.g., from 3 mg/ft ² to 9 mg/ft ² ). Optionally, the pretreatment film has a thickness of up to 300 nm (e.g., up to 250 nm). The 5xxx series aluminum alloy substrate can have a coefficient of friction of less than 0.5 after 2 cycles according to ASTM #G99. Optionally, the pretreatment film comprises trivalent chromium. The 5xxx series aluminum alloy substrate can optionally be AA5182. [0009] Further described herein is a beverage container comprising the aluminum alloy substrate as described herein. Optionally, the beverage container further comprises a Ixxx series aluminum alloy or a 3xxx series aluminum alloy.

[0010] Also described herein is a beverage tab comprising the aluminum alloy substrate as described herein.

[0011] Other objects and advantages will be apparent from the following detailed description of non-limiting examples.

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. l is a chart of the wear profile for a forming tool.

[0014] FIG. 2 is a chart of the lifespan of tools forming aluminum alloy substrates according to examples of the disclosure.

[0015] FIG. 3 is a chart of tool wear for tools forming aluminum alloy substrates according to examples of the disclosure.

[0016] FIG. 4 is a chart of the coefficient of friction of aluminum alloy substrates according to examples of the disclosure.

[0017] FIGS. 5-7 are charts of nano-indentation hardness values of aluminum alloy substrates according to examples of the disclosure.

[0018] FIG. 8 is a chart comparing nano-indentation hardness values of aluminum alloy substrates according to examples of the disclosure.

[0019] FIG. 9 is a scanning transmission electron microscope (STEM) micrograph of an aluminum alloy substrate according to examples of the disclosure.

[0020] FIG. 10 is a STEM micrograph of an aluminum alloy substrate according to examples of the disclosure.

[0021] FIG. 11 is a chart of oxide thickness range of aluminum alloy substrates according to examples of the disclosure. DETAILED DESCRIPTION

[0022] Described herein are metal products and methods of making metal products that reduce wear on tooling equipment used in metal substrate forming systems. The reduction in tooling wear can decrease maintenance and tooling costs and maintain production rates in metal substrate forming systems. The metal products herein include aluminum alloy sheet substrates. The metal products can exhibit improved properties over conventional metal products. For example, the metal products may have reduced pretreatment layer thicknesses, a softer outer layer, a lower coefficient of friction, or combinations thereof as compared to the properties of conventional metal products. The metal products can reduce wear to tooling equipment and expand in-service time, which can reduce operating costs and increase throughput.

[0023] Definitions and Descriptions

[0024] As used herein, the terms “invention,” “the invention,” “this invention” and “the present invention” 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.

[0025] In this description, reference is made to alloys identified by AA numbers and other related designations, such as “series” or “5xxx ” 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.

[0026] 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.

[0027] 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.

[0028] 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, or less than about 0.3 mm (e.g., about 0.2 mm).

[0029] Reference may be 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 a non-heat treatable aluminum alloy after cold rolling with or without thermal treatment (e.g., annealing). Suitable H tempers include HX1, HX2, HX3 HX4, HX5, HX6, HX7, HX8, or HX9 tempers. For example, the aluminum alloy can be cold rolled to result in a possible Hl 9 temper. In a further example, the aluminum alloy can be cold rolled and annealed to result in a possible H23 temper.

[0030] As used herein, terms such as “cast metal product,” “cast product,” “cast aluminum alloy product,” and the like are interchangeable and refer to a product produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by use of a twin belt caster, a twin roll caster, a block caster, or any other continuous caster), electromagnetic casting, hot top casting, or any other casting method. [0031] 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. For example, relative humidity can be about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or anywhere in between. For example, barometric pressure can be about 975 mbar, about 980 mbar, about 985 mbar, about 990 mbar, about 995 mbar, about 1000 mbar, about 1005 mbar, about 1010 mbar, about 1015 mbar, about 1020 mbar, about 1025 mbar, about 1030 mbar, about 1035 mbar, about 1040 mbar, about 1045 mbar, about 1050 mbar, or anywhere in between.

[0032] 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.%).

[0033] As used herein, the meaning of “a,” “an,” and “the” includes singular and plural references unless the context clearly dictates otherwise.

[0034] In examples, aluminum alloy products and their components may be described in terms of their elemental composition in weight percent (wt.%). In each alloy, the remainder is aluminum, with a maximum wt.% of 0.15% for the sum of all impurities.

[0035] 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.

[0036] Unavoidable impurities, including materials or elements may be present in an alloy in minor amounts due to inherent properties of aluminum or leaching from contact with processing equipment. Some alloys, as described, may contain no more than about 0 25 wt.% of any element besides the alloying elements, incidental elements, and unavoidable impurities.

Containers, Container Closures, and Container Bodies

[0037] In this description, reference is made to metal containers, including a body (e.g., a metal container body) having a sealable opening, a product facing body side (e.g., an inside), and a consumer facing body side (e.g., an outside). The metal container further includes an end closure having a product facing closure side and a consumer facing closure side. The sealable opening is configured to receive the end closure, and likewise, the end closure is configured to engage the sealable opening.

[0038] The metal container can be prepared from any suitable metal article. In some examples, the metal container includes 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. The metal article may include monolithic materials, as well as non-monolithic materials such as roll-bonded materials, clad materials, composite materials (such as, but not limited to, carbon fiber-containing materials), or various other materials. In some examples, the metal article used to prepare the metal container can be a metal coil, a metal strip, a metal plate, a metal sheet, a metal billet, a metal ingot, or the like.

[0039] In some cases, the metal article for use in preparing the metal container is an aluminum alloy, such as a Ixxx series aluminum alloy, a 3xxx series aluminum alloy, or a 5xxx series aluminum alloy described herein. By way of non-limiting example, exemplary Ixxx series aluminum alloys can include AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA135OA, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, or AA1199. Non-limiting exemplary 3xxx series aluminum alloys can include AA3002, AA3102, AA3OO3, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3OO5, AA3005A, AA31O5, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3O15, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065. Nonlimiting exemplary 5xxx series aluminum alloys can include AA5182, AA5183, AA5005, AA5OO5A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5O5O, AA5050A, AA5050C, AA5150, AA5051, AA5O51A, AA5151, AA5251, AA5251A, AA5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5154C, AA5254, AA5354, AA5454, AA5554, AA5654, AA5654A, AA5754, AA5854, AA5954, AA5056, AA5356, AA5356A, AA5456, AA5456A, AA5456B, AA5556, AA5556A, AA5556B, AA5556C, AA5257, AA5457, AA5557, AA5657, AA5058, AA5059, AA5070, AA5180, AA5180A, AA5082, AA5182, AA5083, AA5183, AA5183A, AA5283, AA5283A, AA5283B, AA5383, AA5483, AA5086, AA5186, AA5087, AA5187, or AA5088. [0040] In some non-limiting examples, the metal article described herein is an aluminum can end stock (CES) product or an aluminum bare tab stock. CES as used herein refers to an aluminum alloy formed to a shape to serve as a closure for an aluminum can. In some cases, the closure may include a scored orifice that can be broken by a consumer to form an opening in the can end to retrieve any product stored within the can. In some non-limiting examples, the end closure can be an easy open closure (e.g., a ring pull closure), a peel off closure (e.g., a thin foil closure), a beverage closure or seam (e.g., a double seam), a stay-on tab closure, any suitable container end closure, or any combination thereof.

[0041] In some non-limiting examples, the metal container can have any suitable body shape, including a cylinder, a cube, a cuboid, a sphere, a cone, a tetrahedron, a pyramid, any other suitable three-dimensional (3-D) shape, or any combination thereof. Accordingly, the CES product can be formed into any shape suitable to form a closure for the container body. For example, the closure for the container body can be a disc (e.g., to seal a cylinder), a square (e.g., to seal a cube), a rectangle (e.g., to seal a cuboid), a hemisphere (e.g., to seal a sphere), a cone top (e.g., to seal a cone), a tetrahedron top (e.g., to seal a tetrahedron), a pyramid top (e.g., to seal a pyramid), any suitable closure that is complementary to a body (e.g., a closure that completes the shape of the body when joined together), or any combination thereof. [0042] The container can be a beverage can (e.g., a soda can, a water can, an alcoholic beverage can, any pressurized beverage can, or any non-pressurized beverage can), a food storage can (e.g., a canned vegetable can, a canned meat can, a sardine can, a pet food can, or an emergency provisions can), any suitable metal container, or any combination thereof.

Methods of Producing the Alloys and Aluminum Alloy Products

[0043] Described herein are methods of making and treating metals and metal alloys, including aluminum, aluminum alloys, magnesium, magnesium alloys, magnesium composites, and steel, among others, and the resultant treated metals and metal alloys. In some examples, the metals for use in the methods described herein include aluminum alloys, for example, 5xxx series aluminum alloys. In some examples, the materials for use in the methods described herein include non-ferrous materials, including aluminum, aluminum alloys, magnesium, magnesium- based materials, magnesium alloys, magnesium composites, titanium, titanium-based materials, titanium alloys, copper, copper-based materials, composites, sheets used in composites, or any other suitable metal, non-metal or combination of materials.

[0044] The aluminum alloy products described herein, such as aluminum alloy sheet metal substrates, can be prepared using suitable methods. For example, aluminum alloys may be cast, homogenized, hot-rolled, cold-rolled, pretreated, formed, or the like to generate aluminum alloy products.

[0045] An aluminum alloy is cast to form a cast aluminum alloy product, such as an ingot or other cast product. The cast aluminum alloy product is homogenized to form a homogenized aluminum alloy product. The homogenized aluminum alloy product is subjected to one or more hot rolling passes and/or one or more cold rolling passes to form a rolled aluminum alloy product, which may correspond to an aluminum alloy article, such as an aluminum alloy plate, an aluminum alloy shate, or an aluminum alloy sheet. Optionally, the rolled aluminum alloy product is subjected to additional processing steps, as described below, to form an aluminum alloy article.

[0046] Non-limiting examples of casting processes include a direct chill (DC) casting process or a continuous casting (CC) process. A continuous casting system can include a pair of moving opposed casting surfaces (e.g., moving opposed belts, rolls or blocks), a casting cavity between the pair of moving opposed casting surfaces, and a molten metal injector. The molten metal injector can have an end opening from which molten metal can exit the molten metal injector and be injected into the casting cavity.

[0047] A cast aluminum alloy product, such as a cast ingot, cast slab, or other cast product, can be processed by any desirable techniques. Optionally, the processing steps can be used to prepare rolled aluminum alloy products, such as aluminum alloy sheets. Example optional processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, annealing, solution heat treatment, and pre-aging.

[0048] In a homogenization step, a cast product may be heated to a temperature ranging from about 400 °C to about 600 °C. For example, the cast product can be heated to a temperature of about 400 °C, about 410 °C, about 420 °C, about 430 °C, about 440 °C, about 450 °C, about 460 °C, about 470 °C, about 480 °C, about 490 °C, about 500 °C, about 510 °C, about 520 °C, about 530 °C, about 540 °C, about 550 °C, about 560 °C, about 570 °C, about 580 °C, about 590 °C, or about 600 °C. The product may then be allowed to soak (i.e., held at the indicated temperature) for a period of time to form a homogenized product. In some examples, the total time for the homogenization step, including the heating and soaking phases, can be up to 24 hours. For example, the product can be heated up to 500 °C to 600 °C, and soaked, for a total time of up to 18 hours for the homogenization step. Optionally, the product can be heated to below 490 °C and soaked, for a total time of greater than 18 hours for the homogenization step. In some cases, the homogenization step includes multiple processes. In some non-limiting examples, the homogenization step includes heating a cast product to a first temperature for a first period of time followed by heating to a second temperature for a second period of time. For example, a cast product can be heated to about 465 °C for about 3.5 hours and then heated to about 480 °C for about 6 hours.

[0049] Following a homogenization step, a hot rolling step optionally can be performed. Prior to the start of hot rolling, the homogenized product can be allowed to cool to a temperature from 300 °C to 450 °C. For example, the homogenized product can be allowed to cool to a temperature of from 325 °C to 425 °C or from 350 °C to 400 °C. The homogenized product can then be hot rolled at a temperature between 300 °C to 450 °C to form a hot rolled plate, a hot rolled shate or a hot rolled sheet having a gauge from 3 mm and 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 1 10 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or anywhere in between).

[0050] Optionally, the cast product can be a continuously cast product that can be allowed to cool to a temperature from 300 °C to 450 °C. For example, the continuously cast product can be allowed to cool to a temperature of from 325 °C to 425 °C or from 350 °C to 400 °C. The continuously cast products can then be hot rolled at a temperature from 300 °C to 450 °C to form a hot rolled plate, a hot rolled shate or a hot rolled sheet having a gauge from 3 mm and 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or anywhere in between). During hot rolling, temperatures and other operating parameters can be controlled so that the temperature of the hot rolled intermediate product upon exit from the hot rolling mill is no more than 470 °C, no more than 450 °C, no more than 440 °C, or no more than 430 °C.

[0051] Cast, homogenized, or hot-rolled products can be optionally cold rolled using cold rolling mills into thinner products, such as a cold rolled sheet. The cold rolled product can have a gauge from about 0.5 to 10 mm, e.g., from about 0.7 to 6.5 mm. Optionally, the cold rolled product can have a gauge of 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, 5.5 mm, 6.0 mm, 6.5 mm, 7.0 mm, 7.5 mm, 8.0 mm, 8.5 mm, 9.0 mm, 9.5 mm, or 10.0 mm. The cold rolling can be performed to result in a final gauge thickness that represents a gauge reduction of up to 85% (e.g., up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, or up to 85% reduction) as compared to a gauge prior to the start of cold rolling. Optionally, an interannealing step can be performed during the cold rolling step, such as where a first cold rolling process is applied, followed by an annealing process (interannealing), followed by a second cold rolling process. The interannealing step can be performed at a temperature of from about 300 °C to about 450 °C (e.g., about 310 °C, about 320 °C, about 330 °C, about 340 °C, about 350 °C, about 360 °C, about 370 °C, about 380 °C, about 390 °C, about 400 °C, about 410 °C, about 420 °C, about 430 °C, about 440 °C, or about 450 °C). In some cases, the interannealing step comprises multiple processes. In some nonlimiting examples, the interannealing step includes heating the partially cold rolled product to a first temperature for a first period of time followed by heating to a second temperature for a second period of time. For example, the partially cold rolled product can be heated to about 410 °C for about 1 hour and then heated to about 330 °C for about 2 hours.

[0052] The methods described herein include pretreating the metal substrate to produce a conversion layer or a pretreatment film on a surface of the metal substrate to provide a pretreated metal substrate. This conversion layer can provide resistance to corrosion, especially in high humidity climate conditions, provide resistance to abrasion, and improved behavior during manufacturing with less wear to tooling used in the manufacturing process.

[0053] The method of producing the conversion layer or pretreatment film on a surface of the metal substrate is not particularly limited, and any suitable method known in the art may be used. In some embodiments, producing the pretreatment film may comprise contacting the metal substrate with a pretreatment composition. In some cases, producing the pretreatment film may comprise applying a pretreatment composition to the surface of the metal substrate. For example, in some cases the pretreatment composition (e.g., an inorganic pretreatment composition) may be sprayed or roll coated on a surface of the metal substrate. In some cases, the metal substrate may be submerged in a pretreatment composition (e.g., an inorganic pretreatment composition). The pretreatment composition (e.g., an inorganic pretreatment composition) may be specially formulated to produce a pretreatment film on the surface of the metal substrate. For example, the pretreatment composition may include chromium, molybdenum, titanium, zirconium, manganese, or combinations thereof. In some examples, the conversion layer or pretreatment film can include compounds of trivalent chromium (Cr(III)) and phosphates. In some cases, this conversion layer or pretreatment film can include compounds of titanium and zirconium (Ti/Zr). [0054] In addition to chemical surface treatment, producing the pretreatment film may include electrochemical methods, such as anodizing and other deposition methods as known in the art. In some embodiments, the step of producing the pretreatment film can include anodizing a surface of the metal substrate. Anodizing may include, for example, contacting the surface of the metal substrate with an electrolyte solution and applying an electric current (e.g., alternating current (AC) power and/or direct current (DC)) to the metal substrate. In some cases, anodizing the metal substrates produces a pretreated metal substrate having a thin pretreatment film, which may comprise an oxide layer. Suitable methods for anodizing are described in U.S. Pub. No. 2020/0082972, which is incorporated herein by reference. [0055] The composition or structure of the pretreatment film on the pretreated metal substrate is not particularly limited. Pretreatment films known in the art may be classified as organic pretreatment films, inorganic pretreatment films, and combination pretreatment films. Organic pretreatment films can include an organic compound (i.e., a carbon-containing compound), such as organic polymers. Inorganic pretreatment films can include an inorganic compound (i.e., a non-carbon containing compound), such as metal ion analogues and metallic coordination complexes. Combination pretreatment films can include both an organic compound and an inorganic compound or an organic-inorganic compound that includes both organic and inorganic moieties.

[0056] Generally, the pretreatment film comprises a thin layer on a portion (e.g., at least a portion) of a surface of the metal substrate. In some cases, the pretreatment film may be produced on one surface of the metal substrate. In some cases, the pretreatment film may be produced on one or more surfaces of the metal substrate, e.g., two surfaces. In some cases, the pretreatment film is produced on all surfaces of the metal substrate.

[0057] The pretreatment film is applied such that the coat weight of the pretreatment film is controlled to no greater than about 10 mg/ft ² (e.g., from about 0.5 mg/ft ² to about 9 mg/ft ² , from about 1 mg/ft ² to about 9 mg/ft ² , from about 2 mg/ft ² to about 9 mg/ft ² , from about 3 mg/ft ² to about 9 mg/ft ² , from about 4 mg/ft ² to about 9 mg/ft ² , from about 5 mg/ft ² to about 9 mg/ft ² , from about 6 mg/ft ² to about 9 mg/ft ² , or from about 7 mg/ft ² to about 9 mg/ft ² , or anywhere between), on average. In some cases, the coat weight of the pretreatment film on the surface of the metal substrate can be about 0.5 mg/ft ² , about 1 mg/ft ² , about 1.5 mg/ft ² , about 2 mg/ft ² , about 2.5 mg/ft ² , about 3 mg/ft ² , about 3.5 mg/ft ² , about 4 mg/ft ² , about 4.5 mg/ft ² , about 5 mg/ft ² , about 5.5 mg/ft ² , about 6 mg/ft ² , about 6.5 mg/ft ² , about 7 mg/ft ² , about 7.5 mg/ft ² , about 8 mg/ft ² , about 8.5 mg/ft ² , about 9 mg/ft ² , about 9.5 mg/ft ² , or about 10 mg/ft ² .

[0058] The thickness of the pretreatment film may vary. As noted, the pretreatment film is generally a thin layer. The thickness of the pretreatment film can range from about 1 nm to about 1000 nm. In some cases, the pretreatment film is less than about 1000 nm in thickness, e.g., less than about 900 nm, less than about 800 nm, less than about 700 nm, less than about 600 nm, less than about 500 nm, less than about 400 nm, less than about 300 nm, less than about 200 nm, or less than about 100 nm. For example, the pretreatment film can be from about 5 nm to about 1000 nm, from about 10 nm to about 900 nm, from about 20 nm to about 800 nm, or from about 30 nm to about 700 nm in thickness. Tn some examples, the pretreatment film can be about 1 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, about 750 nm, about 800 nm, about 850 nm, about 900 nm, about 950 nm, or about 1000 nm in thickness, or anywhere in between.

[0059] In some cases, the pretreatment film on the pretreated metal substrate may be composed of multiple layers. Certain methods of producing the pretreatment film may produce distinct layers within the pretreatment film. For example, anodizing the metal substrate may produce a pretreatment film including a barrier layer (e.g., composed of aluminum oxide, such as nonporous aluminum oxide) and a filament layer (e.g., composed of aluminum oxide, such porous aluminum oxide). The characteristics of either layer may be controlled by the method of producing the pretreatment film (e.g., the anodizing parameters or conditions).

[0060] In some cases, the metal substrate may be processed before entering the pretreatment application system. In some embodiments, the surface of the metal substrate may be degreased (e.g., using an acid solution) to clean the surface. In some aspects, the process can include cleaning the metal substrate before coating. In some cases, the metal substrate is cleaned with an acid treatment. For example, the cleaning process can include an acid treatment comprising sulfuric acid (H2SO4), hydrofluoric acid (HF), phosphoric acid (H3PO4), nitric acid (HNO3), hydrochloric acid (HC1), hydrobromic acid (HBr), perchloric acid (HCIO4), hydroiodic acid (HI), boric acid (H3BO3), and/or any combination thereof. In some cases, the metal substrate is cleaned with an alkaline (i.e., a base) treatment. For example, the cleaning process can include an alkaline treatment comprising sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), or any combination thereof. In some cases, the metal substrate is cleaned with an alkaline organic compound (i.e., an organic base) treatment. For example, the cleaning process can include an organic base treatment comprising barium tert-butoxide (C8HisBaO2), choline hydroxide (C5H15NO2), di ethylamine (C4H11N), dimethylamine (C2H7N), ethylamine (C2H7N), methylamine (CH5N), piperidine (C5H11N), and/or any combination thereof. This cleaning treatment can reduce and/or remove any aluminum oxide or hydroxide layers on the surface of the metal substrate (e.g., an aluminum alloy strip).

[0061] In some embodiments, the metal substrate may be optionally preheated before entering the pretreatment coating application system. The metal substrate may pass into a preheating oven that heats the sheet metal substrate to a pre-heating temperature (Ti). In some embodiments, the pre-heating temperature Ti is 175 °C to 300 °C, such as from 175 °C to 290 °C, from 175 °C to 280 °C, from 175 °C to 270 °C, from 175 °C to 260 °C, from 175 °C to 250

°C, from 185 °C to 300 °C, from 185 °C to 290 °C, from 185 °C to 280 °C, from 185 °C to 270

°C, from 185 °C to 260 °C, from 185 °C to 250 °C, from 195 °C to 300 °C, from 195 °C to 290

°C, from 195 °C to 280 °C, from 195 °C to 270 °C, from 195 °C to 260 °C, from 195 °C to 250

°C, from 205 °C to 300 °C, from 205 °C to 290 °C, from 205 °C to 280 °C, from 205 °C to 270

°C, from 205 °C to 260 °C, from 205 °C to 250 °C, from 215 °C to 300 °C, from 215 °C to 290

°C, from 215 °C to 280 °C, from 215 °C to 270 °C, from 215 °C to 260 °C, from 215 °C to 250

°C, from 225 °C to 300 °C, from 225 °C to 290 °C, from 225 °C to 280 °C, from 225 °C to 270

°C, from 225 °C to 260 °C, or from 225 °C to 250 °C. In terms of lower limits, Ti may be greater than 175 °C, such as greater than 185 °C, greater than 195 °C, greater than 205 °C, or greater than 215 °C. In terms of upper limits, Ti may be less than 300 °C, such as less than 290 °C, less than 280 °C, less than 270 °C, less than 260 °C, or less than 250 °C.

[0062] The metal substrate can be subjected to further processing or can be coiled as is, such as for shipment or subsequent processing. Optionally, the metal substrate can be processed at a blanking or cutting system, to prepare metal blanks or metal strips or segments. Blanking or cutting system can comprise any suitable system for cutting or blanking and annealed metal substrate to create smaller metal products, which can be subjected to further processing.

[0063] The metal substrate or smaller metal products cut or blanked from a metal substrate can be subjected to forming at a forming system. The forming system can be any suitable forming system, such as including roll-forming equipment, stamping equipment, punching equipment, or the like. In some examples, multiple different types of forming equipment can be used, such as to prepare differently shaped metal products. The equipment used in forming systems can experience excessive wear from metal products having increased oxide layers and/or having increased outer layer hardness. In some examples, a pretreated 5xxx series aluminum alloy substrate may be highly formable and reduce wear to cutting or other shaping equipment as compared to a 5xxx series aluminum alloy substrate that is not pretreated.

Properties of the Disclosed Aluminum Alloy Products

[0064] The aluminum alloy substrate described herein can have a pretreatment fdm applied to the surface of the substrate at a coat weight of no greater than about 10 mg/ft ² (e.g., from about 0.5 mg/ft ² to about 9 mg/ft ² , from about 1 mg/ft ² to about 9 mg/ft ² , from about 2 mg/ft ² to about 9 mg/ft ² , from about 3 mg/ft ² to about 9 mg/ft ² , from about 4 mg/ft ² to about 9 mg/ft ² , from about 5 mg/ft ² to about 9 mg/ft ² , from about 6 mg/ft ² to about 9 mg/ft ² , or from about 7 mg/ft ² to about 9 mg/ft ² , or anywhere between), on average. In some cases, the coat weight of the pretreatment film on the surface of the metal substrate can be about 0.5 mg/ft ² , about 1 mg/ft ² , about 1.5 mg/ft ² , about 2 mg/ft ² , about 2.5 mg/ft ² , about 3 mg/ft ² , about 3.5 mg/ft ² , about 4 mg/ft ² , about 4.5 mg/ft ² , about 5 mg/ft ² , about 5.5 mg/ft ² , about 6 mg/ft ² , about 6.5 mg/ft ² , about 7 mg/ft ² , about 7.5 mg/ft ² , about 8 mg/ft ² , about 8.5 mg/ft ² , about 9 mg/ft ² , about 9.5 mg/ft ² , or about 10 mg/ft ² .

[0065] The aluminum alloy substrate described herein can have a pretreatment film thickness of up to 300 nm. For example, the pretreatment film thickness can be from about 20 nm to about 100 nm, from about 50 nm to about 250 nm, or from about 100 nm to about 200 nm in thickness. In some examples, the pretreatment film thickness can be about 1 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 110 nm, about 120 nm, about 130 nm, about 140 nm, about 150 nm, about 160 nm, about 170, about 180 nm, about 190 nm, about 200 nm, about 210 nm, about 220 nm, about 230 nm, about 240 nm, about 250 nm, about 260 nm, about 270, about 280 nm, about 290 nm, or about 300 nm in thickness, or anywhere in between. The aluminum alloy substrate described herein can have a coefficient of friction of less than 0.5 after 2 cycles according to ASTM G99 (2017) and DIN-50324. For example, the coefficient of friction can be from about 0.2 to about 0.5, from about 0.2 to about 0.3, or from about 0.3 to about 0.5. In some examples, the coefficient of friction can be less than about 0.5, less than about 0.45, less than about 0.4, less than about 0.35, less than about 0.3, less than about 0.25, less than about 0.2, less than about 0.15, less than about 0.1, or anywhere in between. Methods of Using the Disclosed A luminum A Hoy Products

[0066] The aluminum alloy products described herein can be used in beverage can applications and other container applications. For example, the disclosed aluminum alloy products can be used to produce beverage or food containers. In some examples, the disclosed aluminum alloy products may be used to produce tabs used on beverage or food containers.

[0067] The examples disclosed herein will serve to further illustrate aspects of the invention without, at the same time, 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. The examples and embodiments described herein may also make use of conventional procedures, unless otherwise stated. Some of the procedures are described herein for illustrative purposes.

EXAMPLES

[0068] Samples of metal substrates were prepared for trial in a production facility using standard tooling equipment. Repeated controlled tests of approximately 20 million converted ends per coil were run, each with new tooling installed. Ex. 1-4 were different as-rolled standard bare 5182 AA products. Ex. 1 and Ex. 2 were bare materials after being subjected to standard industry cleaning methods, as known to those of skill in the art. Ex. 3 was bare material without cleaning, and Ex. 4 was the only sample to which a pre-treatment (trivalent chromium solution) was applied at an average coating weight of 3 to 9 mg/ft ² (see Table 1).

Table 1

[0069] The wear profile of the tooling equipment was measured and the length of production run recorded before change-out of the tooling equipment was required due to wear. FIG. 1 shows a typical wear profile over one corner for an example tooling equipment. As shown in FIG. 2, the tooling equipment run with substrates that were not pretreated exhibited the shortest run time before change-out was required. Even for new tooling equipment, substrates that were not pretreated led to shorter run times before change-out was required. A comparison of tool wear for Ex. 1 and Ex. 4 is shown in FIG 3. As described above, Ex. 1 and Ex. 4 were different as- rolled standard bare 5182 AA products. Ex. 1 was a bare material after standard industry cleaning methods, while Ex. 4 was tested with a pre-treatment applied. In FIG. 3, each data bar represents measurements on 4 to 10 tools from a run of approximately 20 million cycles.

[0070] Friction testing was conducted on Ex. 3 and Ex. 4 with a 0.5 inch 52100 steel ball using a Falex ball-on-flat configuration at 44 N, 10 rpm, and 5 cycles according to ASTM #G99. FIG. 4 shows the difference in the measured coefficients of friction for each test (2 runs each). [0071] Accelerated Property Mapping (XPM) Nano-Indention Hardness was determined for Ex. 1, Ex. 2, and Ex. 4. The XPM utilized shallow surface penetration to measure the hardness of the outer layer of the metal substrates. The test analysis area was 100 pm x 20 pm.

Approximately 500 tests were run per sample with an indentation depth of less than 80 nm. FIGS. 5-7 provide the distribution of Hardness for each sample and FIG. 8 compares the average measured hardness values across the test materials. The pretreated substrate was softer than standard rolled substrates and had a smaller variance.

[0072] Cross sections of the trial materials were analyzed using a scanning transmission electron microscope (STEM) and the oxide and coating layer thicknesses were measured. FIGS.

9 and 10 are exemplary of the STEM micrographs. The thicknesses of the oxide layer for the trial samples are shown in FIG. 11.

ILLUSTRATIVE ASPECTS

[0073] As used below, any reference to a series of aspects (e.g., “Aspects 1-4”) or nonenumerated group of aspects (e.g., “any previous or subsequent aspect”) is to be understood as a reference to each of those aspects disjunctively (e.g., “Aspects 1-4” is to be understood as “Aspects 1, 2, 3, or 4”).

[0074] Aspect l is a method of making a 5xxx series aluminum alloy substrate, the method comprising producing a pretreatment fdm on a surface of a 5xxx series aluminum alloy substrate to provide a pretreated 5xxx series aluminum alloy substrate and controlling a coat weight of the pretreatment film to no greater than 10 mg/ft ² . [0075] Aspect 2 is the method of any previous or subsequent aspect, wherein producing the pretreatment fdm comprises contacting the 5xxx series aluminum alloy substrate with a pretreatment solution.

[0076] Aspect 3 is the method of any previous or subsequent aspect, wherein the pretreatment solution comprises chromium, molybdenum, titanium, zirconium, manganese, or combinations thereof.

[0077] Aspect 4 is the method of any previous or subsequent aspect, wherein the pretreatment solution comprises trivalent chromium (Cr(III)), phosphates, or combinations thereof.

[0078] Aspect 5 is the method of any previous or subsequent aspect, wherein the pretreatment solution comprises compounds of titanium and zirconium (Ti/Zr).

[0079] Aspect 6 is the method of any previous or subsequent aspect, wherein contacting comprises spraying, roll coating, or submerging at least a portion of the aluminum alloy substrate.

[0080] Aspect 7 is a method of any previous or subsequent aspect, wherein the coat weight of the pretreatment fdm is from 3 mg/ft ² to 9 mg/ft ² .

[0081] Aspect 8 is the method of any previous or subsequent aspect, wherein the pretreatment fdm has a thickness of up to 300 nm or up to 250 nm.

[0082] Aspect 9 is the method of any previous or subsequent aspect, wherein the pretreated 5xxx series aluminum alloy substrate has a coefficient of friction of less than 0.5 after 2 cycles according to ASTM #G99.

[0083] Aspect 10 is the method of any previous or subsequent aspect, further comprising degreasing at least a portion of the surface of the aluminum alloy substrate prior to producing the pretreatment film.

[0084] Aspect 11 is the method of any previous or subsequent aspect, wherein degreasing comprises contacting at least a portion of the substrate with an acidic solution, an alkaline solution, an alkaline organic compound, or combinations thereof.

[0085] Aspect 12 is the method of any previous or subsequent aspect, further comprising preheating the aluminum alloy substrate to a temperature of less than 300 °C prior to producing the pretreatment fdm. [0086] Aspect 13 is the method of any previous or subsequent aspect, wherein the 5xxx series aluminum alloy substrate is AA5182.

[0087] Aspect 14 is an aluminum alloy substrate prepared according to the method of any previous or subsequent aspect.

[0088] Aspect 15 is the aluminum alloy substrate of any previous or subsequent aspect, wherein the pretreatment film has a thickness of up to 300 nm.

[0089] Aspect 16 is the aluminum alloy substrate of any previous or subsequent aspect, wherein the pretreatment film has a thickness of up to 250 nm.

[0090] Aspect 17 is the aluminum alloy substrate of any previous or subsequent aspect, wherein the 5xxx series aluminum alloy substrate has a coefficient of friction of less than 0.5 after 2 cycles according to ASTM #G99.

[0091] Aspect 18 is the aluminum alloy substrate of any previous or subsequent aspect, wherein the pretreatment film comprises trivalent chromium.

[0092] Aspect 19 is the aluminum alloy substrate of any previous or subsequent aspect, wherein the 5xxx series aluminum alloy substrate is AA5182.

[0093] Aspect 20 is a beverage container comprising the aluminum alloy substrate of any previous or subsequent aspect.

[0094] Aspect 21 is the beverage container of any previous or subsequent aspect, further comprising a Ixxx series aluminum alloy or a 3xxx series aluminum alloy.

[0095] Aspect 22 is a beverage tab comprising the aluminum alloy substrate of any previous aspect.

[0096] All patents and publications cited herein are incorporated by reference in their entirety. The foregoing description of the embodiments, including illustrated embodiments, has been presented only for the purpose of illustration and description and is not intended to be exhaustive or limiting to the precise forms disclosed. Numerous modifications, adaptations, and uses thereof will be apparent to those skilled in the art.