Pretreated aluminum alloy pull ring material

Abstract

A 5xxx series aluminum alloy substrate and a method of making a 5xxx series aluminum alloy substrate having a pre-treated film on a surface of the substrate are described herein. The beverage tab may include a pretreated 5xxx series aluminum alloy substrate. A method of making a 5xxx series aluminum alloy substrate as described herein includes creating a pre-treated film on a surface of a 5xxx series aluminum alloy substrate to provide a pre-treated 5xxx series aluminum alloy substrate, and controlling a coating weight of the pre-treated film to not greater than 10 mg / ft2.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 371,560, filed on August 16, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates generally to the processing of metal substrates, such as aluminum alloys. More specifically, the present disclosure relates to the pretreatment of metal substrates, and in particular aluminum alloy tab stock. Background Art

[0004] High productivity is an important consideration for facilities that produce aluminum beverage cans. Conventional aluminum alloy products have been found to cause excessive wear on equipment used in some metal substrate forming systems. Excessive wear on equipment such as converting presses can change the profile of the tool edge and subsequently cause changes in product quality. Excessive wear can lead to increased maintenance and tooling costs and production losses because the operating line may have to be shut down for repair or replacement of worn or damaged equipment. Summary of the invention

[0005] The term embodiment and similar terms are intended to refer broadly to all subject matter of the present disclosure and the following claims. Statements containing these terms should not be understood to limit the subject matter described herein, or to limit the meaning or scope of the following claims. The various embodiments of the present disclosure covered herein are defined by the following claims rather than by this disclosure. This disclosure is a high-level overview of various aspects of the present disclosure, and introduces some concepts that are further described in the following detailed description section. This disclosure is not intended to confirm the key features or essential features of the claimed subject matter, nor is it intended to be used alone to determine the scope of the claimed subject matter. The subject matter should be understood by reference to the appropriate parts of the entire specification of the present disclosure, any or all drawings, and each claim.

[0006] A method of making a 5xxx series aluminum alloy substrate is described herein, the method comprising producing a pretreatment film on a surface of the 5xxx series aluminum alloy substrate to provide a pretreated 5xxx series aluminum alloy substrate, and controlling the coating weight of the pretreatment film to be no greater than 10 mg / ft 2 (For example, 3 mg / ft 2 Up to 9mg / 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 a combination thereof. In some cases, the pretreatment solution comprises trivalent chromium (Cr(III)), a phosphate, or a combination thereof, and in some cases, the pretreatment solution comprises a compound of titanium and zirconium (Ti / Zr). Contacting may optionally comprise spraying, rolling, or immersing at least a portion of the aluminum alloy substrate.

[0007] The pretreatment film may 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 methods described herein may also include degreasing at least a portion of the surface of the aluminum alloy substrate prior to producing the pretreatment film. Degreasing may include contacting at least a portion of the substrate with an acidic solution, an alkaline solution, an alkaline organic compound, or a combination thereof.

[0008] Optionally, the methods described herein further comprise preheating the aluminum alloy substrate to a temperature below 300° C. prior to producing the pretreatment film. Optionally, the 5xxx series aluminum alloy substrate is AA5182.

[0009] The present invention also describes an aluminum alloy substrate prepared according to the above method. The pretreatment film has a carbon content of not more than 10 mg / ft 2 (For example, 3 mg / ft 2 Up to 9mg / ft 2 ) coating weight. Optionally, the pretreatment film has a thickness of at most 300 nm (e.g., at most 250 nm). The 5xxx series aluminum alloy substrate may have a friction coefficient 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 may optionally be AA5182.

[0010] Further described herein is a beverage container comprising an aluminum alloy substrate as described herein. Optionally, the beverage container further comprises a 1xxx series aluminum alloy or a 3xxx series aluminum alloy.

[0011] Also described herein is a beverage pull ring comprising an aluminum alloy substrate as described herein.

[0012] Other objects and advantages will become apparent from the following detailed description given by way of non-limiting example. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] This description refers to the following drawings, in which the use of the same reference numerals in different drawings is intended to illustrate the same or similar components.

[0014] Figure 1is a diagram of the wear profile of the forming tool.

[0015] Figure 2 is a graph of the life of tools for forming aluminum alloy substrates according to embodiments of the present disclosure.

[0016] Figure 3 is a graph of tool wear for tools forming aluminum alloy substrates according to embodiments of the present disclosure.

[0017] Figure 4 is a graph of coefficients of friction of aluminum alloy substrates according to embodiments of the present disclosure.

[0018] Figure 5-Figure 7 is a graph of nanoindentation hardness values ​​of aluminum alloy substrates according to embodiments of the present disclosure.

[0019] Figure 8 is a graph comparing nanoindentation hardness values ​​of aluminum alloy substrates according to embodiments of the present disclosure.

[0020] Fig. 9 is a scanning transmission electron microscope (STEM) micrograph of an aluminum alloy substrate according to an embodiment of the present disclosure.

[0021] Fig.10 is a STEM micrograph of an aluminum alloy substrate according to an embodiment of the present disclosure.

[0022] Fig.11 is a graph of oxide thickness ranges for aluminum alloy substrates according to embodiments of the present disclosure. DETAILED DESCRIPTION

[0023] Metal products and methods of making metal products are described herein that reduce wear on die equipment used in metal substrate forming systems. Reduction in die wear can reduce maintenance and die costs and maintain productivity of metal substrate forming systems. The metal products herein include aluminum alloy sheet substrates. The metal products can exhibit improved properties compared to conventional metal products. For example, the metal product can have a reduced pretreatment layer thickness, a softer outer layer, a lower coefficient of friction, or a combination thereof, compared to the properties of conventional metal products. The metal products can reduce wear on die equipment and extend service life, which can reduce operating costs and increase production.

[0024] Definition and Description

[0025] As used herein, the terms "invention," "the invention," "this invention," and "the present invention" are intended to refer broadly to the subject matter of this patent application and the claims that follow in their entirety. Statements containing these terms should not be construed to limit the subject matter described herein or to limit the meaning or scope of the patent claims that follow.

[0026] In this specification, reference is made to alloys identified by AA numbers and other related names, such as "Series" or "5xxx". For information on the numbering system most commonly used to name and identify aluminum and its alloys, see "International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys" or "Registration Record of Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot" published by The Aluminum Association.

[0027] As used herein, a plate generally has a thickness greater than about 15 mm. For example, a plate may refer to an aluminum product having a thickness greater than 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.

[0028] As used herein, a shat board (also referred to as a sheet board) typically has a thickness of about 4 mm to about 15 mm. For example, a shat board can 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.

[0029] As used herein, sheet generally refers to an aluminum product having a thickness of less than about 4 mm. For example, the 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).

[0030] Reference may be made to alloy tempers or states in this application. For descriptions of the most commonly used alloy tempers, see "American National Standards (ANSI) H35 on Alloy and Temper Designation Systems". The F state or temper refers to a manufactured aluminum alloy. The O state or temper refers to an aluminum alloy after annealing. The Hxx state or temper, also referred to herein as the H temper, refers to a non-heat-treatable aluminum alloy that has been subjected to or not subjected to a heat treatment (e.g., annealing) after cold rolling. Suitable H tempers include HX1, HX2, HX3, HX4, HX5, HX6, HX7, HX8, or HX9 tempers. For example, an aluminum alloy may be cold rolled to produce a possible H19 temper. In another example, an aluminum alloy may be cold rolled and annealed to produce a possible H23 temper.

[0031] As used herein, terms such as "cast metal product", "cast product", "cast aluminum alloy product" and the like are interchangeable and refer to products produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by using a twin-belt caster, a twin-roll caster, a block caster or any other continuous casting machine), electromagnetic casting, hot top casting or any other casting method.

[0032] As used herein, "room temperature" may include a temperature of about 15° C. to about 30° C., such as about 15° C., about 16° C., about 17° C., about 18° C., about 19° C., about 20° C., about 21° C., about 22° C., about 23° C., about 24° C., about 25° C., about 26° C., about 27° C., about 28° C., about 29° C., or about 30° C. As used herein, "ambient conditions" may include a temperature of approximately room temperature, a relative humidity of about 20% to about 100%, and an atmospheric pressure of about 975 millibars (mbar) to about 1050 mbar. For example, the relative humidity can be about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about %, 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 any value therebetween. For example, the gas pressure may be about 975 mbar, about 980 mbar, about 985 mbar, about 990 mbar, about 995 mbar, about 1000 mbar, about 1005 mbar, about 1010 mbar, about 1015 mbar, about 1020 mbar, about 1025 mbar, about 1030 mbar, about 1035 mbar, about 1040 mbar, about 1045 mbar, about 1050 mbar, or any value therebetween.

[0033] All ranges disclosed herein will be understood to encompass any and all subranges contained therein. For example, the specified range "1 to 10" should be considered to include any and all subranges between (and including) a minimum of 1 and a maximum of 10; that is, all subranges start with a minimum of 1 or a greater number, such as 1 to 6.1, and end with a maximum of 10 or a lesser number, such as 5.5 to 10. Unless otherwise stated, when referring to the composition amount of an element, the expression "up to" means that the element is optional and includes zero percent composition of the particular element. Unless otherwise stated, all composition percentages are weight percent (wt%).

[0034] As used herein, the meanings of "a", "an" and "the" include both singular and plural references unless the context clearly indicates otherwise.

[0035] In various examples, aluminum alloy products and parts thereof may be described in terms of their elemental composition expressed in weight percent (wt %). In each alloy, the remainder is aluminum, with a maximum wt % of 0.15% for the sum of all impurities.

[0036] Incidental elements, such as grain refiners and deoxidizers, or other additives may be present in the present invention and may themselves add other properties without departing from or significantly altering the alloys described herein or the properties of the alloys described herein.

[0037] Small amounts of unavoidable impurities, including materials or elements, may be present in the alloy due to the inherent properties of aluminum or leaching from contact with processing equipment. As described, some alloys may contain no more than about 0.25% by weight of any element other than alloying elements, incidental elements, and unavoidable impurities.

[0038] Containers, container closures and container bodies

[0039] In this specification, reference is made to a metal container, including a body (e.g., a metal container body) having a sealable opening, a body side facing a product (e.g., an inner side), and a body side facing a consumer (e.g., an outer side). The metal container also includes an end closure having a closure side facing the product and a closure side facing the consumer. The sealable opening is configured to receive the end closure, and likewise, the end closure is configured to engage the sealable opening.

[0040] The metal container may be made of any suitable metal product. In some examples, the metal container includes aluminum, aluminum alloys, magnesium, magnesium-based materials, titanium, titanium-based materials, copper, copper-based materials, steel, steel-based materials, bronze, bronze-based materials, brass, brass-based materials, composite materials, sheets used in composite materials, or any other suitable metal or material combination. The metal product may include integral materials, as well as non-integral materials, such as roll-bonded materials, clad materials, composite materials (such as but not limited to materials containing carbon fibers), or various other materials. In some examples, the metal product used to make the metal container may be a metal coil, a metal strip, a metal plate, a metal sheet, a metal billet, a metal ingot, etc.

[0041] In some cases, the metal article used to prepare the metal container is an aluminum alloy, such as the 1xxx series aluminum alloy, 3xxx series aluminum alloy, or 5xxx series aluminum alloy described herein. As a non-limiting example, an exemplary 1xxx series aluminum alloy may include AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, or AA1199. Non-limiting exemplary 3xxx series aluminum alloys may include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3008, AA3009, AA3110, AA3111A, AA3111B, AA3112, AA3113, AA3114, AA3115A, AA3116, AA3117, AA3118, AA3119, AA3120 AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.Non-limiting exemplary 5xxx series aluminum alloys may include AA5182, AA5183, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5019B, AA5020C, AA5021C, AA5022A, AA5023, AA5024, AA5025A, AA5026, AA5027, AA5028, AA5029A, AA5030 21. AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA5251A ,AA5351,AA5451,AA5052,AA5252,AA5352,AA5154,AA5154A,AA5154B,AA5154C,AA5254,AA5354,AA5454,AA5554 ,AA5654,AA5654A,AA5754,AA5854,AA5954,AA5056,AA5356,AA5356A,AA5456,AA5456A,AA5456B,AA5556,AA5556 A. 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.

[0042] In some non-limiting examples, the metal product described herein is an aluminum can end stock (CES) product or an aluminum bare pull ring stock. As used herein, CES refers to an aluminum alloy formed into a shape used as a closure for an aluminum can. In some cases, the closure may include a scored orifice that a consumer may break to form an opening in the can lid to retrieve any product stored in the can. In some non-limiting examples, the end closure may be an easy-open closure (e.g., a pull ring closure (ring pull closure)), a peel closure (e.g., a thin foil closure), a beverage closure or seam (e.g., a double seam), a stay-on tab closure (stay-on tab closure), any suitable container end closure or any combination thereof.

[0043] 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. Thus, the CES product can be formed into any shape suitable for forming a closure of the container body. For example, the closure of the container body can be a disc (e.g., a sealed cylinder), a square (e.g., a sealed cube), a rectangle (e.g., a sealed cuboid), a hemispherical (e.g., a sealed sphere), a conical top (e.g., a sealed cone), a tetrahedral top (e.g., a sealed tetrahedron), a pyramidal top (e.g., a sealed pyramid), any suitable closure complementary to the body (e.g., a closure that completes the shape of the body when connected together), or any combination thereof.

[0044] 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 canned sardine can, a pet food can, or an emergency food can), any suitable metal container, or any combination thereof.

[0045] Methods of producing alloys and aluminum alloy products

[0046] Methods for making and treating metals and metal alloys (especially including aluminum, aluminum alloys, magnesium, magnesium alloys, magnesium composites and steel), and the resulting treated metals and metal alloys are described herein. In some instances, the metal used in the methods described herein includes an aluminum alloy, such as a 5xxx series aluminum alloy. In some instances, the material used in the methods described herein includes a non-ferrous material, 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.

[0047] The aluminum alloy products described herein (such as aluminum alloy sheet metal substrates) can be prepared using suitable methods. For example, the aluminum alloy can be cast, homogenized, hot rolled, cold rolled, heat treated, formed or similarly processed to produce an aluminum alloy product.

[0048] The 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 slat, 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.

[0049] Non-limiting examples of casting processes include direct chill (DC) casting processes or continuous casting (CC) processes. A continuous casting system may include a pair of moving opposing casting surfaces (e.g., moving opposing belts, rollers, or blocks), a casting cavity between the pair of moving opposing casting surfaces, and a molten metal ejector. The molten metal ejector may have an end opening from which the molten metal may exit the molten metal ejector and be ejected into the casting cavity.

[0050] The cast aluminum alloy product, such as an ingot, a billet or other cast product, can be processed by any desired technique. Optionally, the processing step can be used to produce a rolled aluminum alloy product, such as an aluminum alloy sheet. Exemplary optional processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, annealing, solution heat treatment, and pre-aging.

[0051] In the homogenization step, the cast product may be heated to a temperature in the range of about 400°C to about 600°C. For example, the cast product may be heated to a temperature of about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, 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 soaked (i.e., maintained at a specified temperature) for a period of time to form a homogenized product. In some examples, the total time of the homogenization step (including the heating and soaking stages) may be up to 24 hours. For example, for the homogenization step, the product may be heated to a total time of up to 500°C to 600°C and soaked for up to 18 hours. Optionally, for the homogenization step, the product can be heated to less than 490°C and homogenized for a total time of greater than 18 hours. In some cases, the homogenization step includes multiple processes. In some non-limiting examples, the homogenization step includes heating the cast product to a first temperature for a first time period, and then heating to a second temperature for a second time period. For example, the 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.

[0052] After the homogenization step, a hot rolling step may optionally be performed. Before starting the hot rolling, the homogenized product may be cooled to a temperature of 300 to 450° C. For example, the homogenized product may be cooled to a temperature of 325 to 425° C. or 350 to 400° C. The homogenized product may then be hot rolled at a temperature between 300°C and 450°C to form a hot rolled plate, hot rolled Saudi plate or hot rolled sheet having a specification of 3 mm to 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm or any value therebetween).

[0053] Optionally, the cast product may be a continuously cast product, and the continuously cast product may be cooled to a temperature of 300° C. to 450° C. For example, the continuously cast product may be cooled to a temperature of 325° C. to 425° C. or 350° C. to 400° C. The continuously cast product may then be hot rolled at a temperature of 300° C. to 450° C. to form a hot rolled plate, hot rolled Saudi plate or hot rolled sheet having a specification of 3 mm to 200 mm (e.g., 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm or any value therebetween). During hot rolling, temperature and other operating parameters may be controlled so that the temperature of the hot rolled intermediate product does not exceed 470°C, does not exceed 450°C, does not exceed 440°C, or does not exceed 430°C when leaving the hot rolling mill.

[0054] The product of casting, homogenization or hot rolling can be optionally cold rolled into a thinner product, such as a cold rolled sheet, using a cold rolling mill. The cold rolled product can have a specification of about 0.5mm to 10mm, for example about 0.7mm to 6.5mm. Optionally, the cold rolled product can have a specification of 0.5mm, 1.0mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm, 4.5mm, 5.0mm, 5.5mm, 6.0mm, 6.5mm, 7.0mm, 7.5mm, 8.0mm, 8.5mm, 9.0mm, 9.5mm or 10.0mm. Cold rolling may be performed to obtain a final gauge thickness that represents a gauge reduction of up to 85% (e.g., a reduction of 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%) compared to the gauge before cold rolling began. Optionally, an intermediate annealing step may be performed during the cold rolling step, such as applying a first cold rolling process, followed by an annealing process (intermediate annealing), and then a second cold rolling process. The intermediate annealing step may be performed at a temperature of about 300°C to about 450°C (e.g., about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 430°C, about 440°C, or about 450°C). In some cases, the intermediate annealing step includes multiple processes. In some non-limiting examples, the intermediate annealing step includes heating the partially cold rolled product to a first temperature for a first period of time, and then heating to a second temperature for a second period of time. For example, the partially cold rolled product may be heated to about 410°C for about 1 hour, and then heated to about 330°C for about 2 hours.

[0055] The methods described herein include pretreating a metal substrate to form a conversion layer or pretreatment film on the surface of the metal substrate, thereby providing a pretreated metal substrate. The conversion layer can provide corrosion resistance, especially in high humidity climate conditions, wear resistance, and improved behavior during manufacturing with less wear on molds used in the manufacturing process.

[0056] The method of producing a conversion layer or pretreatment film on the surface of a metal substrate is not particularly limited, and any suitable method known in the art can be used. In some embodiments, producing a pretreatment film may include contacting the metal substrate with a pretreatment composition. In some cases, producing a pretreatment film may include applying the pretreatment composition to the surface of the metal substrate. For example, in some cases, the pretreatment composition (e.g., an inorganic pretreatment composition) can be sprayed or rolled on the surface of the metal substrate. In some cases, the metal substrate can be immersed in the pretreatment composition (e.g., an inorganic pretreatment composition). The pretreatment composition (e.g., an inorganic pretreatment composition) can 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 a combination thereof. In some examples, the conversion layer or pretreatment film may include a compound of trivalent chromium (Cr (III)) and phosphate. In some cases, the conversion layer or pretreatment film may include a compound of titanium and zirconium (Ti / Zr).

[0057] In addition to chemical surface treatment, the generation of pretreatment film may also include electrochemical methods, such as anodic oxidation and other deposition methods known in the art. In some embodiments, the step of generating pretreatment film may include anodizing the surface of the metal substrate. Anodization 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 supply and / or direct current (DC)) to the metal substrate. In some cases, anodizing the metal substrate produces a pretreated metal substrate with a thin pretreatment film, which may include an oxide layer. Suitable methods for anodization are described in U.S. Publication No. 2020 / 0082972, which is incorporated herein by reference.

[0058] The composition or structure of the pretreatment film on the pretreated metal substrate is not particularly limited. Pretreatment films known in the art can be classified into organic pretreatment films, inorganic pretreatment films, and combined pretreatment films. Organic pretreatment films may include organic compounds (i.e., carbon-containing compounds), such as organic polymers. Inorganic pretreatment films may include inorganic compounds (i.e., compounds that do not contain carbon), such as metal ion analogs and metal coordination complexes. Combined pretreatment films may include both organic compounds and inorganic compounds, or organic-inorganic compounds including both organic and inorganic parts.

[0059] In general, the pretreatment film includes a thin layer on a portion (e.g., at least a portion) of the surface of the metal substrate. In some cases, the pretreatment film can be produced on one surface of the metal substrate. In some cases, the pretreatment film can be produced on one or more surfaces (e.g., two surfaces) of the metal substrate. In some cases, the pretreatment film is produced on all surfaces of the metal substrate.

[0060] The pretreatment film is applied so that the coating weight of the pretreatment film is controlled to be no greater than about 10 mg / ft on average. 2 (e.g., about 0.5 mg / ft 2 About 9 mg / ft 2 , about 1mg / ft 2 About 9 mg / ft 2 , about 2mg / ft 2 About 9 mg / ft 2 , about 3mg / ft 2 About 9 mg / ft 2 , about 4mg / ft 2 About 9 mg / ft 2 , about 5mg / ft 2 About 9 mg / ft 2 , about 6mg / ft 2 About 9 mg / ft 2 or about 7 mg / ft 2 About 9 mg / ft 2 or any value therebetween). In some cases, the coating weight of the pretreatment film on the surface of the metal substrate may be about 0.5 mg / ft 2 , about 1mg / ft 2 , about 1.5mg / ft 2 , about 2mg / ft 2 , about 2.5mg / ft 2 , about 3mg / ft 2 , about 3.5mg / ft 2 , about 4mg / ft 2 , about 4.5mg / ft 2 , about 5mg / ft 2 , about 5.5mg / ft 2 , about 6mg / ft 2 , about 6.5mg / ft 2 , about 7mg / ft 2 , about 7.5mg / ft 2 , about 8mg / ft 2 , about 8.5mg / ft 2 , about 9mg / ft 2 , about 9.5mg / ft 2 or about 10 mg / ft 2 .

[0061] The thickness of the pre-treatment film can vary. As mentioned above, the pre-treatment film is generally a thin layer. The thickness of the pre-treatment film can be in the range of about 1 nm to about 1000 nm. In some cases, the thickness of the pre-treatment film is less than about 1000 nm, for example, 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 less than about 400 nm, less than about 300 nm, less than about 200 nm or less than about 100 nm. For example, the thickness of the pre-treatment film can be about 5 nm to about 1000 nm, about 10 nm to about 900 nm, about 20 nm to about 800 nm or about 30 nm to about 700 nm. In some examples, the thickness of 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 or any value in between.

[0062] 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 different 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 non-porous aluminum oxide) and a filament layer (e.g., composed of aluminum oxide, such as porous aluminum oxide). The properties of either layer may be controlled by the method of producing the pretreatment film (e.g., anodizing parameters or conditions).

[0063] 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 acidic solution) to clean the surface. In some aspects, the process may include cleaning the metal substrate prior to coating. In some cases, the metal substrate is cleaned with an acid treatment. For example, the cleaning process may include an acid treatment, including sulfuric acid (H 2 SO 4 ), hydrofluoric acid (HF), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), hydrochloric acid (HCl), hydrobromic acid (HBr), perchloric acid (HClO 4 ), hydroiodic acid (HI), boric acid (H 3BO 3 ) and / or any combination thereof. In some cases, the metal substrate is cleaned with an alkaline (i.e., base) treatment. For example, the cleaning process may include an alkaline treatment including sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) 2 ) or any combination thereof. In some cases, the metal substrate is treated with a basic organic compound (i.e., an organic base) for cleaning. For example, the cleaning process may include an organic base treatment including barium tert-butoxide (C 8 H 18 BaO 2 ), choline hydroxide (C 5 H 15 NO 2 ), diethylamine (C 4 H 11 N), dimethylamine (C 2 H 7 N), ethylamine (C 2 H 7 N), methylamine (CH 5 N), piperidine (C 5 H 11 N) and / or any combination thereof. Such a cleaning process can reduce and / or remove any aluminum oxide or aluminum hydroxide layer on the surface of the metal substrate (eg, aluminum alloy strip).

[0064] In some embodiments, the metal substrate may be optionally preheated before entering the pretreatment coating application system. The metal substrate may enter a preheating furnace that heats the sheet metal substrate to a preheating temperature (T 1 ). In some embodiments, the preheating temperature T 1 is 175°C to 300°C, such as 175°C to 290°C, 175°C to 280°C, 175°C to 270°C, 175°C to 260°C, 175°C to 250°C, 185°C to 300°C, 185°C to 290°C, 185°C to 280°C, 185°C to 270°C, 185°C to 260°C, 185°C to 250°C, 195°C to 300°C, 195°C to 290°C, 195°C to 280°C, 195°C to 270°C, 195°C to 260°C, 195°C to 250°C ℃, 205℃ to 300℃, 205℃ to 290℃, 205℃ to 280℃, 205℃ to 270℃, 205℃ to 260℃, 205℃ to 250℃, 215℃ to 300℃, 215℃ to 290℃, 215℃ to 280℃, 215℃ to 270℃, 215℃ to 260℃, 215℃ to 250℃, 225℃ to 300℃, 225℃ to 290℃, 225℃ to 280℃, 225℃ to 270℃, 225℃ to 260℃ or 225℃ to 250℃. In terms of the lower limit, T1 It 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, T 1 It 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.

[0065] The metal substrate may be further processed or may be coiled as is, such as for transport or subsequent processing. Optionally, the metal substrate may be processed in a blanking or cutting system to produce metal blanks or metal strips or metal segments. The blanking or cutting system may include any suitable system for cutting or blanking the annealed metal substrate to create smaller metal products that may undergo further processing.

[0066] The metal substrate or the smaller metal product cut or punched out from the metal substrate can be subjected to forming in the forming system. The forming system can be any suitable forming system, for example including roll forming equipment, stamping equipment, punching equipment, etc. In some instances, a variety of different types of forming equipment can be used, such as to prepare metal products of different shapes. The equipment used in the forming system can suffer excessive wear due to the increase in the oxide layer of the metal product and / or the increase in the hardness of the outer layer. In some instances, the pretreated 5xxx series aluminum alloy substrate can be highly formable and reduce the wear on cutting or other forming equipment compared to the unpretreated 5xxx series aluminum alloy substrate.

[0067] Characteristics of the disclosed aluminum alloy products

[0068] The aluminum alloy substrates described herein may have an average of no greater than about 10 mg / ft 2 (e.g., about 0.5 mg / ft 2 About 9 mg / ft 2 , about 1mg / ft 2 About 9 mg / ft 2 , about 2mg / ft 2 About 9 mg / ft 2 , about 3mg / ft 2 About 9 mg / ft 2 , about 4mg / ft 2 About 9 mg / ft 2 , about 5mg / ft 2 About 9 mg / ft 2 , about 6mg / ft 2 About 9 mg / ft 2 or about 7 mg / ft 2 About 9 mg / ft 2or any value therebetween) is applied to the surface of the substrate. In some cases, the coating weight of the pretreatment film on the surface of the metal substrate may be about 0.5 mg / ft 2 , about 1mg / ft 2 , about 1.5mg / ft 2 , about 2mg / ft 2 , about 2.5mg / ft 2 , about 3mg / ft 2 , about 3.5mg / ft 2 , about 4mg / ft 2 , about 4.5mg / ft 2 , about 5mg / ft 2 , about 5.5mg / ft 2 , about 6mg / ft 2 , about 6.5mg / ft 2 , about 7mg / ft 2 , about 7.5mg / ft 2 , about 8mg / ft 2 , about 8.5mg / ft 2 , about 9mg / ft 2 , about 9.5mg / ft 2 or about 10 mg / ft 2 .

[0069] The aluminum alloy substrate described herein may have a pretreatment film thickness of up to 300 nm. For example, the thickness of the pretreatment film may 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 some examples, the thickness of 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 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, or any value therebetween. The aluminum alloy substrate described herein may have a coefficient of friction of less than 0.5 after 2 cycles according to ASTM G99 (2017) and DIN-50324 testing. For example, the coefficient of friction may 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 may 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 any value therebetween.

[0070] Methods of using the disclosed aluminum alloy products

[0071] 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 can be used to produce pull rings used on beverage or food containers.

[0072] The examples disclosed herein will be used to further illustrate various aspects of the present invention, but will not constitute any limitation of the present invention at the same time. On the contrary, it should be clearly understood that after reading the specification of this article, those skilled in the art can think of making various other embodiments, modifications and equivalent schemes without departing from the spirit of the present invention. Unless otherwise stated, the embodiments and embodiments described herein can also utilize conventional procedures. Some programs are described herein for illustrative purposes.

[0073] Example

[0074] Samples of the metal substrates used for testing were prepared in a production facility using standard die equipment. Repeated control tests were run on approximately 20 million conversion ends per roll, with new dies installed for each test. Examples 1-4 are different rolled standard bare 5182AA products. Examples 1 and 2 are bare materials that were subjected to standard industry cleaning methods known to those skilled in the art. Example 3 is bare material that was not cleaned, and Example 4 is bare material at 3 to 9 mg / ft 2 The only sample to which a pretreatment (trivalent chromium solution) was applied had an average coating weight of 1.5 Å (see Table 1).

[0075] Table 1

[0076]

[0077] The wear profile of the die equipment was measured and the length of the production run before the die equipment needed to be replaced due to wear was recorded. Figure 1 A typical wear profile on one corner of an exemplary mold device is shown. Figure 2 As shown, the mold equipment operated with the substrate without pretreatment exhibited the shortest operating time before replacement was required. Even for new mold equipment, the substrate without pretreatment resulted in a shorter operating time before replacement was required. Figure 3 A tool wear comparison of Example 1 and Example 4 is shown. As mentioned above, Example 1 and Example 4 are different rolled standard bare 5182AA products. Example 1 is the bare material after standard industry cleaning methods, while Example 4 was tested with a pre-treatment applied. Figure 3 In the , each data bar represents measurements on 4 to 10 tools from a run of approximately 20 million cycles.

[0078] Examples 3 and 4 were friction tested according to ASTM #G99 with a 0.5 inch 52100 steel ball using a Falex ball-to-flat configuration at 44 N, 10 rpm, and 5 cycles. Figure 4 The difference in the measured coefficient of friction for each test (2 runs each) is shown.

[0079] The accelerated property mapping (XPM) nanoindentation hardness of Example 1, Example 2 and Example 4 was measured. XPM uses shallow surface penetration to measure the hardness of the outer layer of the metal substrate. The test analysis area is 100μm x 20μm. Approximately 500 tests were run for each sample, with an indentation depth of less than 80nm. Figure 5-7 The hardness distribution of each sample is provided, and Figure 8 The average measured hardness values ​​of the tested materials were compared. The pre-treated substrate was softer than the standard rolled substrate and had a smaller variance.

[0080] Cross sections of the test materials were analyzed using scanning transmission electron microscopy (STEM) and the oxide and coating layer thicknesses were measured. Fig. 9 and Fig.10 is an example of a STEM micrograph. The thickness of the oxide layer of the test sample is shown in Fig.11 middle.

[0081] Illustrative aspects

[0082] As used below, any reference to a series of aspects (e.g., “Aspects 1-4”) or an unlisted group of aspects (e.g., “any previous or subsequent aspect”) should be understood as a separate reference to each of those aspects (e.g., “Aspects 1-4” should be understood as “Aspect 1, Aspect 2, Aspect 3, or Aspect 4”).

[0083] Aspect 1 is a method for manufacturing a 5xxx series aluminum alloy substrate, the method comprising generating a pretreatment film on a surface of the 5xxx series aluminum alloy substrate to provide a pretreated 5xxx series aluminum alloy substrate, and controlling the coating weight of the pretreatment film to be no greater than 10 mg / ft 2 .

[0084] Aspect 2 is the method of any preceding or subsequent aspect, wherein producing the pretreatment film comprises contacting the 5xxx series aluminum alloy substrate with a pretreatment solution.

[0085] Aspect 3 is the method of any preceding or subsequent aspect, wherein the pretreatment solution comprises chromium, molybdenum, titanium, zirconium, manganese, or a combination thereof.

[0086] Aspect 4 is the method of any preceding or subsequent aspect, wherein the pretreatment solution comprises trivalent chromium (Cr(III)), phosphate, or a combination thereof.

[0087] Aspect 5 is the method of any preceding or subsequent aspect, wherein the pretreatment solution comprises a compound of titanium and zirconium (Ti / Zr).

[0088] Aspect 6 is the method of any preceding or subsequent aspect, wherein contacting comprises spraying, rolling, or immersing at least a portion of the aluminum alloy substrate.

[0089] Aspect 7 is the method of any preceding or subsequent aspect, wherein the coating weight of the pretreatment film is 3 mg / ft 2 Up to 9mg / ft 2 .

[0090] Aspect 8 is the method of any preceding or subsequent aspect, wherein the pretreatment film has a thickness of at most 300 nm or at most 250 nm.

[0091] Aspect 9 is the method of any preceding 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.

[0092] Aspect 10 is the method of any preceding or subsequent aspect, further comprising degreasing at least a portion of the surface of the aluminum alloy substrate prior to producing the pretreatment film.

[0093] Aspect 11 is the method of any preceding 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 a combination thereof.

[0094] Aspect 12 is the method of any preceding or subsequent aspect, further comprising preheating the aluminum alloy substrate to a temperature below 300° C. prior to producing the pretreatment film.

[0095] Aspect 13 is the method of any preceding or subsequent aspect, wherein the 5xxx series aluminum alloy substrate is AA5182.

[0096] Aspect 14 is an aluminum alloy substrate prepared according to the method of any preceding or subsequent aspect.

[0097] Aspect 15 is the aluminum alloy substrate of any preceding or subsequent aspect, wherein the pretreatment film has a thickness of at most 300 nm.

[0098] Aspect 16 is the aluminum alloy substrate of any preceding or subsequent aspect, wherein the pretreatment film has a thickness of at most 250 nm.

[0099] Aspect 17 is the aluminum alloy substrate of any preceding 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.

[0100] Aspect 18 is the aluminum alloy substrate of any preceding or subsequent aspect, wherein the pretreatment film comprises trivalent chromium.

[0101] Aspect 19 is the aluminum alloy substrate of any preceding or subsequent aspect, wherein the 5xxx series aluminum alloy substrate is AA5182.

[0102] Aspect 20 is a beverage container comprising the aluminum alloy substrate described in any preceding or subsequent aspect.

[0103] Aspect 21 is the beverage container of any preceding or subsequent aspect, further comprising a 1xxx series aluminum alloy or a 3xxx series aluminum alloy.

[0104] Aspect 22 is a beverage pull ring, which includes the aluminum alloy substrate described in any of the preceding aspects.

[0105] All patents and publications cited herein are incorporated by reference in their entirety. The foregoing description of the embodiments, including the illustrated embodiments, is presented for purposes of illustration and description only and is not intended to be exhaustive or limited to the precise forms disclosed. Numerous modifications, adaptations, and uses of the present invention will be apparent to those skilled in the art.

Claims

1. A method for manufacturing a 5xxx series aluminum alloy substrate, the method include: producing a pretreatment film on a surface of a 5xxx series aluminum alloy substrate to provide a pretreated 5xxx series aluminum alloy substrate; as well as The coating weight of the pre-treated film is controlled to be no greater than 10 mg / ft 2 .

2. The method of claim 1, wherein producing the pretreatment film comprises contacting the 5xxx series aluminum alloy substrate with a pretreatment solution.

3. The method of claim 2, wherein the pretreatment solution comprises chromium, molybdenum, titanium, zirconium, manganese, or a combination thereof.

4. The method of claim 2, wherein the pretreatment solution comprises trivalent chromium (Cr(III)), phosphate, or a combination thereof.

5. The method of claim 2, wherein the pretreatment solution comprises a compound of titanium and zirconium (Ti / Zr).

6. The method of any one of claims 2-5, wherein contacting comprises spraying, rolling, or immersing at least a portion of the 5xxx series aluminum alloy substrate.

7. The method of any one of claims 1-6, wherein the coating weight of the pretreatment film is 3 mg / ft 2 Up to 9mg / ft 2 .

8. The method of any one of claims 1 to 7, wherein the pretreatment film has a thickness of at most 300 nm.

9. The method of any one of claims 1-8, 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.

10. The method of any one of claims 1-9, further comprising degreasing at least a portion of a surface of the 5xxx series aluminum alloy substrate prior to producing the pretreatment film.

11. The method of claim 10, wherein degreasing comprises contacting at least a portion of the 5xxx series aluminum alloy substrate with an acidic solution, an alkaline solution, an alkaline organic compound, or a combination thereof.

12. The method of any one of claims 1-11, further comprising preheating the 5xxx series aluminum alloy substrate to a temperature below 300°C prior to producing the pretreatment film.

13. The method of any one of claims 1-12, wherein the 5xxx series aluminum alloy substrate is AA5182.

14. An aluminum alloy substrate, wherein the aluminum alloy substrate is prepared according to the method according to any one of claims 1 to 13.

15. The aluminum alloy substrate of claim 14, wherein the coating weight of the pretreatment film is 3 mg / ft 2 Up to 9mg / ft 2 .

16. The aluminum alloy substrate of claim 15, wherein the pretreatment film has a thickness of at most 300 nm.

17. The aluminum alloy substrate of any one of claims 14-16, wherein the 5xxx series aluminum alloy substrate has a coefficient of friction of less than 0.5 after 2 cycles according to ASTM #G99.

18. The aluminum alloy substrate of any one of claims 14-17, wherein the pretreatment film comprises trivalent chromium.

19. The aluminum alloy substrate of any one of claims 14-18, wherein the 5xxx series aluminum alloy substrate is AA5182.

20. A beverage container comprising the aluminum alloy substrate according to any one of claims 14 to 19.

21. The beverage container of claim 20, further comprising a 1xxx series aluminum alloy or a 3xxx series aluminum alloy.

22. A beverage pull ring comprising the aluminum alloy substrate according to any one of claims 14 to 21.

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