Attorney Docket #: 108050-1492445 COMMINUTION AND RECONSTITUTION OF GRAIN REFINER FOR CASTING INCLUSION SENSITIVE ALLOYS FIELD OF THE INVENTION [0001] This application relates to treatment of molten aluminum and aluminum alloys. Particularly, the present technology is related to the comminution and refining of grain refiner products and treatment of molten aluminum and aluminum alloys therewith. BACKGROUND [0002] Nucleating agents, such as titanium-containing grain refiner products are often added to molten aluminum and aluminum alloys during the casting process. Grain refiner products may be incorporated in the melt to improve the as-cast grain structure to be more uniform and contain a high percentage of fine grains. However, grain refiners are carefully tailored to the aluminum alloy present in the melt, as various alloying elements may result in undesired crystal formation during solidification. Namely, conventional grain refiners negatively interact with some alloying elements, such as magnesium and vanadium, particularly at high concentrations of the alloying elements, forming intermetallic particles. Such intermetallic particle do not disburse or dissolve in the melt, causing cracks and other defects in the cast product. [0003] Recycled scrap metal includes metal from used metal products that is collected and used to prepare other metal products. Used beverage can (UBC) scrap is collected metal from used beverage cans and similar products that can be recycled for use in further metal products. Aluminum UBC scrap is often a mixture of various aluminum alloys (e.g., from different alloys used for can bodies and can ends) and can often include foreign substances, such as rainwater, drink remainders, organic matter (e.g., paints and laminated films), and other materials. UBC scrap can be shredded and decoated or delacquered prior to being melted for use as liquid metal stock in casting a new metal product. However, such recycled scrap from beverage containers and other recycled content contains impurities and unbalanced alloying elements, such as increased levels of silicon (Si), magnesium (Mg), vanadium (V), calcium (Ca), strontium (Sr), titanium (Ti),
Attorney Docket #: 108050-1492445 beryllium (Be), chromium (Cr), and/or manganese (Mn), which are difficult to remove from the recycled scrap and resulting alloy melt. [0004] Controlling the alloy to be within the elemental range for traditional grain refiner products has become increasing problematic with the rise in the desire to utilize recycled scrap metals. Namely, the use of traditional grain refiner products has resulted in large intermetallic particles detected in articles containing recycled alloy content, which can lead to cracking, and other issues, such as rivet formation defects. Thus, there is a need in the art for a grain refiner product that is compatible with various alloy impurities. There is also a need in the art for casting an aluminum alloy with alloy impurities having improved grain properties. SUMMARY [0005] Embodiments covered by this patent are defined by the claims below, not this summary. This summary is a high-level overview of various embodiments 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 patent, any or all drawings, and each claim. [0006] The present technology is generally directed to methods of metal casting as well as suitable grain refiner products. Methods include forming an aluminum alloy liquid metal. Methods include mechanically deforming a grain refiner product into grain refiner chips having a particle size of less than 1000 μm, where at least a portion of the mechanically deformed grain refiner chip particles include one or more TiAl3 phase particles having an equivalent spherical diameter of less than or about 50 μm. Methods include, adding the mechanically deformed grain refiner chips to the aluminum alloy liquid metal, casting the liquid metal into a metal product, and rolling the metal product. [0007] In embodiments, substantially all of the grain refiner chips include TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. Furthermore, in embodiments, the mechanically deformed grain refiner chips are added in the form of chips, pellets, tablets, or a combination thereof. In more embodiments, the mechanical deforming includes sawing, grinding,
Attorney Docket #: 108050-1492445 rolling, extruding, machining, impaction, or a combination thereof. Additionally or alternatively, in embodiments, the mechanical deforming is conducted for a period of time to produce greater than or 500 TiAl3 particles/mm2. In yet more embodiments, metal products include one or more intermetallic particles, wherein each of the one or more intermetallic particles exhibits an equivalent spherical diameter of less than or about 10 μm. Furthermore, in embodiments, the aluminum alloy includes one or more of beryllium, magnesium, vanadium, strontium, titanium, and calcium. In more embodiments, the aluminum alloy includes a 5xxx series alloy. In embodiments, the molten metal includes greater than or 10 wt.% recycled aluminum alloy. In more embodiments, the aluminum alloy includes from 0.01 wt.% titanium to 0.1 wt.% titanium. Moreover, in embodiments, the aluminum alloy includes from 1 wt.% to 7 wt.% magnesium. In embodiments, the aluminum alloy includes from 0.01 wt.% vanadium to 0.1 wt.% vanadium. Embodiments include where greater than or 50 wt.% of the grain refiner chips include TiAl3 phase particles having an equivalent diameter of less than or 50 μm. Additionally or alternatively, in embodiments, greater than or 50 wt.% of the grain refiner chips include TiAl3 phase particles having an equivalent diameter of less than or 20 μm. Further, in embodiments, greater than or 50 wt.% of the grain refiner chips include TiAl3 phase particles having an equivalent diameter of less than or 10 μm. The present technology is also generally directed to metal product cast from any one or more of the methods discussed above. [0008] The present technology is also generally directed to 5xxx series aluminum alloy aluminum alloy products. 5xxx series aluminum alloy products include 0.01 – 1.0 wt.% Cu, 0.1 – 0.8 wt.% Fe, 0.5 – 7.0 wt.% Mg, 0.01 – 1.2 wt.% Mn, 0 – 1.5 wt.% Si, 0 – 0.2 wt.% Ti, 0 – 8.0 wt.% Zn, 0 – 0.3 wt.% Cr, 0 – 0.15 wt.% Zr, 0 – 0.1 wt.% V, 0 – 0.15 wt.% Ca, up to 0.15 wt.% impurities, and Al. The aluminum alloy product includes intermetallic particles, where the intermetallic particles include two or more of aluminum, beryllium, magnesium, vanadium, strontium, titanium, and calcium, wherein the intermetallic particles exhibit an equivalent spherical diameter of less than 50 μm. The present technology is also generally directed to a beverage container including the aluminum alloy product as discussed herein.. [0009] The present technology is also generally directed to a TiAl3 containing grain refiner product. The grain refiner product includes grain refiner chips having a particle size of less than 1000 μm, where greater than 50 wt.% of the grain refiner chips include TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. In embodiments, substantially all
Attorney Docket #: 108050-1492445 of the grain refiner chips include TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. [0010] Various implementations described herein may include additional systems, methods, features, and advantages, which cannot necessarily be expressly disclosed herein but will be apparent to one of ordinary skill in the art upon examination of the following detailed description and accompanying drawings. It is intended that all such systems, methods, features, and advantages be included within the present disclosure and protected by the accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGS [0011] 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. [0012] FIG.1 illustrates a metal treatment system according to embodiments. DETAILED DESCRIPTION [0013] The subject matter of embodiments is described herein with specificity to meet statutory requirements, but this description is not necessarily intended to limit the scope of the claims. The claimed subject matter may be embodied in other ways, may include different elements or steps, and may be used in conjunction with other existing or future technologies. This description should not be interpreted as implying any particular order or arrangement among or between various steps or elements except when the order of individual steps or arrangement of elements is explicitly described. Directional references such as “up,” “down,” “top,” “bottom,” “left,” “right,” “front,” and “back,” among others, are intended to refer to the orientation as illustrated and described in the figure (or figures) to which the components and directions are referencing. While the systems and methods described herein can be used with any metal, they may be especially useful with aluminum or aluminum alloys. [0014] Grain refiner products are generally manufactured by reacting molten aluminum with various reactive salts, such as K2TiF4 and KBF4, as examples only, to form a suspension of TiB2 and TiAl3. The suspension is then formed into rods having diameters of about 9.5 millimeters to about 50 millimeters. The grain refiner products are then introduced into the molten aluminum alloy early in the casting process, such as upstream of a degasser and/or metal filter, interacting
Attorney Docket #: 108050-1492445 with the alloy and nucleating the system. Grain refiner products are generally introduced at this stage in order to allow for full dissolution of TiAl3 prior to ingot formation. Namely, existing grain refiner products require significant residence time in the melt in order to fully dissolve and disburse TiAl3 particles. However, with increases in recycled content in alloy precursor materials, extended residence time in the melt is believed to lead to formation of intermetallic particle. For instance, as discussed above, the presence, or increased concentration, of Ti, Mg, V, and/or Ca in the recycled content may lead to the formation of AlxMgyTizVtCau intermetallic particles, where, as an example only, x may range from 0 to 18, y and u may be independently selected to range from 0 to 3, and z and t may be independently selected to range from 0 to 2. Moreover, due to the nucleating effect of the grain refiner products, it is believed that such intermetallic particles may form around, or even fully enclose TiAl3 particles, preventing dissolution and dispersion of the TiAl3 particles, and allowing TiAl3 particles and/or intermetallic particles of greater than 100 μm to form in the final melt and ingot. This is increasingly problematic for products having a thin gauge, such as for beverage containers, as rivet formation in the can body or can end may have a product thickness of less than 150 μm, rendering the article susceptible to cracking and damage due to the large particles formed in and around the grain refiner. [0015] Described herein are grain refiner products having improved performance, even in alloys containing one or more impurities, such as one or more impurities from recycled content. The present technology also includes methods of forming such grain refiner products, and methods of forming an aluminum alloy article utilizing such grain refiner products. The present technology has surprisingly found that by mechanically deforming the grain refiner product to a carefully controlled particle size of the grain refiner, referred to herein as “grain refiner chips”, one or more of the above problems may be addressed. Namely, grain refiner chips according to the present technology may decrease the necessary residence time, decreasing the formation of intermetallic particles having a particle diameter of greater than or about 50 μm. Moreover, grain refiner chips according to the present technology may also exhibit reduced TiAl3 phase particle sizes, thus allowing for further decreased intermetallic or TiAl3 particle sizes in the final melt due to the smaller nucleation particles.
Attorney Docket #: 108050-1492445 Definitions and Descriptions: [0016] The terms “invention,” “the invention,” “this invention,” and “the present invention” used herein are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below. [0017] As used herein, the meaning of “a,” “an,” or “the” includes singular and plural references unless the context clearly dictates otherwise. [0018] 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. [0019] 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. [0020] 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). [0021] As used herein, the term foil indicates an alloy thickness in a range of up to about 0.2 mm (i.e., 200 microns (μm)). For example, a foil may have a thickness of up to 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, or 200 μm. [0022] In this description, reference is made to alloys identified by aluminum industry 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
Attorney Docket #: 108050-1492445 Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot,” both published by The Aluminum Association. [0023] Reference is made in this application to alloy temper or condition. For an understanding of the alloy temper descriptions most commonly used, see “American National Standards (ANSI) H35 on Alloy and Temper Designation Systems.” An F condition or temper refers to an aluminum alloy as fabricated. An O condition or temper refers to an aluminum alloy after annealing. An Hxx condition or temper, also referred to herein as an H temper, refers to a non-heat treatable aluminum alloy after cold rolling with or without thermal treatment (e.g., annealing). Suitable H tempers include HX1, HX2, HX3 HX4, HX5, HX6, HX7, HX8, or HX9 tempers. A T1 condition or temper refers to an aluminum alloy cooled from hot working and naturally aged (e.g., at room temperature). A T2 condition or temper refers to an aluminum alloy cooled from hot working, cold worked and naturally aged. A T3 condition or temper refers to an aluminum alloy solution heat treated, cold worked, and naturally aged. A T4 condition or temper refers to an aluminum alloy solution heat treated and naturally aged. A T5 condition or temper refers to an aluminum alloy cooled from hot working and artificially aged (at elevated temperatures). A T6 condition or temper refers to an aluminum alloy solution heat treated and artificially aged. A T7 condition or temper refers to an aluminum alloy solution heat treated and artificially overaged. A T8x condition or temper refers to an aluminum alloy solution heat treated, cold worked, and artificially aged. A T9 condition or temper refers to an aluminum alloy solution heat treated, artificially aged, and cold worked. A W condition or temper refers to an aluminum alloy after solution heat treatment. [0024] 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. [0025] 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.
Attorney Docket #: 108050-1492445 [0026] As used herein, the term metal product can refer to any suitable shape or size of cast product, as appropriate. [0027] 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. [0028] The following aluminum alloys are described in terms of their elemental composition in weight percentage (wt. %) based on the total weight of the alloy. In certain examples of each alloy, the remainder is aluminum, with a maximum wt. % of 0.15 % for the sum of the impurities. [0029] As used herein, the terms recycled scrap (e.g., recycled stock) can refer to a collection of recycled metal. Recycled scrap can include materials recycled from any suitable source, such as from a metal production facility (e.g., metal casting facility), from a metalworking facility (e.g., production facility that uses metal product to create consumable products), or from post-consumer sources (e.g., regional recycling facilities). Certain aspects of the present disclosure can be well- suited for recycled scrap from sources other than a metal production facility, since such recycled scrap likely contains a mixture of alloys or is mixed with other impurities or elements (e.g., such as paints or coatings). Recycled scrap can refer to recycled aluminum, such as recycled sheet aluminum products (e.g., aluminum pots and pans), recycled cast aluminum products (e.g., aluminum grills and wheel rims), UBC scrap (e.g., beverage cans), aluminum wire, and other aluminum materials. Aluminum Alloys [0030] Described herein are aluminum alloys. As discussed above, aluminum alloys may be prepared from at least a portion of recycled scrap. However, it should be understood that the alloys discussed herein may also including one or more of the following alloying elements (also referred to as “impurities”) from an independent source, and in embodiments, may not include any recycled content. Thus, it should be understood that the following discussion and amounts of various components may be obtained from recycled content or from an alloy mixture.
Attorney Docket #: 108050-1492445 [0031] Nonetheless, in embodiments, the techniques disclosure herein can allow suitable cast products to be produced from a modified liquid metal containing at or more than about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 92%, about 94%, about 96%, or about 98% recycled scrap, or any ranges or values therebetween. In other words, the cast products described herein can include at or less than about 90%, about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, about 20%, about 10%, about 8%, about 6%, about 4%, about 2%, primary aluminum, or any ranges or values therebetween. [0032] In some cases, the recycled scrap includes recycled aluminum scrap, such as UBC scrap. UBC scrap, for example, generally contains a mixture of metal from various alloys, such as metal from can bodies (e.g., 3104, 3004, or other 3xxx aluminum alloy) and can ends (e.g., 5182 or other 5xxx aluminum alloy). Other modified liquid metals includes other mixtures of alloys, as well as mixtures that include primary aluminum. [0033] Optionally, the modified liquid metal can be modified with one or more additional elements to prepare the alloys. In some examples, it can be desirable to add further magnesium (Mg) and/or other alloying elements to the modified liquid metal, which can result in an alloy with improved castability of the liquid metal and improved metallurgical properties of the end product. For example, added Mg can increase the formability and strength of the cast metal product. However, as discussed above, previously high levels of Mg were problematic, as they contributed to increased intermetallic particle size. However, utilizing the methods discussed herein, in some examples, Mg can be added to the modified liquid metal to achieve, in a modified metal alloy, a percentage of Mg of from about 0.50 % to about 7.0 % based on the total weight of the alloy (e.g., from about 1.5 % to about 6.0 %, from about 2.0 % to about 5.0 %, from about 2.5 % to about 4.5 %, or from about 3.0 % to about 4.0 %). The Mg percentage can be at or greater than approximately 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %, 6.0 %, 6.1 %, 6.2 %, 6.3 %, 6.4 %, 6.5 %, 6.6 %, 6.7 %, 6.8 %, 6.9 %, or 7.0 %. In some cases, Mg can be added to the modified liquid metal to achieve, in a metal alloy, a percentage of Mg by weight of at least 1.5% and at or less than approximately 6.0 %, 5.9 %, 5.8 %, 5.7 %, 5.6 %, 5.5 %, 5.4 %, 5.3 %, 5.2 %, 5.1 %, 5.0 %, 4.9
Attorney Docket #: 108050-1492445 %, 4.8 %, 4.7 %, 4.6 %, 4.5 %, 4.4 %, 4.3 %, 4.2 %, 4.1 %, 4.0 %, 3.9 %, 3.8 %, 3.7 %, 3.6 %, 3.5 %, 3.4 %, 3.3 %, 3.2 %, 3.1 %, or 3.0 %. [0034] In some examples, the metal alloys described herein can have the following elemental composition as provided in Table 1. [0035] Table 1
[0036] In some examples, the metal alloys described herein can have the following elemental composition as provided in Table 2. [0037] Table 2
Attorney Docket #: 108050-1492445
[0038] In some examples, the metal alloys described herein can have the following elemental composition as provided in Table 3. [0039] Table 3
Attorney Docket #: 108050-1492445
[0040] In some examples, the alloys described herein include Cu in an amount of from about 0.01 % to about 1.0 % (e.g., from about 0.02 % to about 1.0 %, from about 0.03 % to about 0.9 %, from about 0.04 to about 0.8 %, or from about 0.05 % to about 0.40 %), based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, or 1.0 % Cu. All are expressed in wt. %. [0041] In some examples, the alloys described herein include iron (Fe) in an amount of from about 0.1 % to about 0.8 % (e.g., from about 0.15 % to about 0.7 % or from about 0.2 % to about 0.6 %) based on the total weight of the alloy. For example, the alloy can include 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 % Fe. All are expressed in wt. %. [0042] In some examples, the alloys described herein include Mg in an amount of from about 0.50 % to about 7.0 % (e.g., from about 1.0 % to about 6.0 %, from about 2 % to about 5.5 %, from about 2.5 % to about 5.0 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy. For example, the alloy can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %,
Attorney Docket #: 108050-1492445 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %, 6.0 %, 6.1 %, 6.2 %, 6.3 %, 6.4 %, 6.5 %, 6.6 %, 6.7 %, 6.8 %, 6.9 %, or 7.0 % Mg. All are expressed in wt. %. [0043] In some examples, the alloys described herein include manganese (Mn) in an amount of from about 0.01 % to about 1.2 % (e.g., from about 0.05 % to about 1.0 %, from about 0.1 % to about 0.9 %, or from about 0.2 % to about 0.7 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.01 %, 1.02 %, 1.03 %, 1.04 %, 1.05 %, 1.06 %, 1.07 %, 1.08 %, 1.09 %, 1.10 %, 1.11 %, 1.12 %, 1.13 %, 1.14 %, 1.15 %, 1.16 %, 1.17 %, 1.18 %, 1.19 %, or 1.20 % Mn. All are expressed in wt. %. [0044] In some examples, the alloys described herein include Si in an amount up to about 1.5 wt. % (e.g., from about 0.01 % to about 1.0 %, from about 0.02 % to about 0.5 %, or from about 0.03 % to about 0.1 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %,
Attorney Docket #: 108050-1492445 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.01 %, 1.02 %, 1.03 %, 1.04 %, 1.05 %, 1.06 %, 1.07 %, 1.08 %, 1.09 %, 1.10 %, 1.11 %, 1.12 %, 1.13 %, 1.14 %, 1.15 %, 1.16 %, 1.17 %, 1.18 %, 1.19 %, 1.20 %, 1.21 %, 1.22 %, 1.23 %, 1.24 %, 1.25 %, 1.26 %, 1.27 %, 1.28 %, 1.29 %, 1.30 %, 1.31 %, 1.32 %, 1.33 %, 1.34 %, 1.35 %, 1.36 %, 1.37 %, 1.38 %, 1.39 %, 1.40 %, 1.41 %, 1.42 %, 1.43 %, 1.44 %, 1.45 %, 1.46 %, 1.47 %, 1.48 %, 1.49 %, or 1.50 % Si. In some cases, Si is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0045] In some examples, the alloys described herein include titanium (Ti) in an amount up to about 0.2 % (e.g., from about 0.01 % to about 0.15 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, or 0.20 % Ti. In some cases, Ti is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0046] In some examples, the alloys described herein include zinc (Zn) in an amount of from about 0 % to about 8.0 % (e.g., from about 0.01 % to about 5.0 % or from about 0.02 % to about 1.0 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6%, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %,
Attorney Docket #: 108050-1492445 6.0 %, 6.1 %, 6.2 %, 6.3 %, 6.4 %, 6.5 %, 6.6 %, 6.7 %, 6.8 %, 6.9 %, 7.0 %, 7.1 %, 7.2 %, 7.3 %, 7.4 %, 7.5 %, 7.6 %, 7.7 %, 7.8 %, 7.9 %, or 8.0 %. Zn. In some cases, Zn is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0047] In some examples, the alloys described herein include chromium (Cr) in an amount up to about 0.30 % (e.g., from about 0.01 % to about 0.25 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, or 0.30 % Cr. In some cases, Cr is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0048] In some examples, the alloys described herein include zirconium (Zr) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.01 % to about 0.1 % or from about 0.02 % to about 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Zr. In some cases, Zr is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0049] In some examples, the alloys described herein include vanadium (V) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.01 % to about 0.1 % or from about 0.02 % to about 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % V. In some cases, V is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0050] In some examples, the alloys described herein include calcium (Ca) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Ca. In some cases, Ca is not present in the alloy (i.e., 0 %). All are expressed in wt. %. However, in embodiments, alloys discussed herein may include one or more of calcium, vanadium, and titanium.
Attorney Docket #: 108050-1492445 [0051] In some examples, the alloys described herein include strontium (Sr) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Sr. In some cases, Sr is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0052] In some examples, the alloys described herein include beryllium (Be) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy. For example, the alloy can include 0.0001 %, 0.0002 %, 0.0003 %, 0.0004 %, 0.0005 %, 0.0006 %, 0.0007 %, 0.0008 %, 0.0009 %, 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Be. In some cases, Be is not present in the alloy (i.e., 0 %). All are expressed in wt. %. [0053] Optionally, the alloy compositions described herein can further include other minor elements, sometimes referred to as impurities, in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below for each impurity. These impurities may include, but are not limited to, Sn, Ga, Bi, Na, Pb, Li, W, Mo, Ni, B, C, or combinations thereof. Accordingly, Sn, Ga, Bi, Na, Pb, Li, W, Mo, Ni, B, or C may be present in alloys in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below or 0.01 % or below. In some cases, the sum of all impurities does not exceed 0.15 % (e.g., 0.10 %). All expressed in wt. %. The remaining percentage of the alloy is aluminum. [0054] In some examples, suitable alloys for use in the alloys described herein can be a 1xxx series aluminum alloy, a 2xxx series aluminum alloy, a 3xxx series aluminum alloy, a 4xxx series aluminum alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, an 8xxx series aluminum alloy, or any combination thereof. The 1xxx, 2xxx, 3xxx, 4xxx, 5xxx, 6xxx, 7xxx, or 8xxx series aluminum alloy can be modified to include an amount of Mg, Cu, and/or Si as described above.
Attorney Docket #: 108050-1492445 [0055] Suitable 1xxx series aluminum alloys for use in the alloys described herein include, for example, AA1050, AA1060, AA1070, AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, and AA1199. [0056] Suitable 2xxx series aluminum alloys for use in the alloys described herein include, for example, AA2001, A2002, AA2004, AA2005, AA2006, AA2007, AA2007A, AA2007B, AA2008, AA2009, AA2010, AA2011, AA2011A, AA2111, AA2111A, AA2111B, AA2012, AA2013, AA2014, AA2014A, AA2214, AA2015, AA2016, AA2017, AA2017A, AA2117, AA2018, AA2218, AA2618, AA2618A, AA2219, AA2319, AA2419, AA2519, AA2021, AA2022, AA2023, AA2024, AA2024A, AA2124, AA2224, AA2224A, AA2324, AA2424, AA2524, AA2624, AA2724, AA2824, AA2025, AA2026, AA2027, AA2028, AA2028A, AA2028B, AA2028C, AA2029, AA2030, AA2031, AA2032, AA2034, AA2036, AA2037, AA2038, AA2039, AA2139, AA2040, AA2041, AA2044, AA2045, AA2050, AA2055, AA2056, AA2060, AA2065, AA2070, AA2076, AA2090, AA2091, AA2094, AA2095, AA2195, AA2295, AA2196, AA2296, AA2097, AA2197, AA2297, AA2397, AA2098, AA2198, AA2099, and AA2199. [0057] Suitable 3xxx series aluminum alloys for use in the alloys described herein include, for example, AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, and AA3065. [0058] Suitable 4xxx series aluminum alloys for use in the alloys described herein include, for example, AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, and AA4147. [0059] Suitable 5xxx series aluminum alloys for use in the alloys described herein include, for example, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106,
Attorney Docket #: 108050-1492445 AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA5150, AA5051, AA5051A, AA5151, AA5251, AA5251A, AA5351, AA5451, AA5052, AA5252, AA5352, AA5154, AA5154A, AA5154B, AA5154C, AA5254, AA5354, AA5454, AA5554, AA5654, AA5654A, AA5754, AA5854, AA5954, AA5056, AA5356, AA5356A, AA5456, AA5456A, AA5456B, AA5556, AA5556A, AA5556B, AA5556C, AA5257, AA5457, AA5557, AA5657, AA5058, AA5059, AA5070, AA5180, AA5180A, AA5082, AA5182, AA5083, AA5183, AA5183A, AA5283, AA5283A, AA5283B, AA5383, AA5483, AA5086, AA5186, AA5087, AA5187, and AA5088. [0060] Suitable 6xxx series aluminum alloys for use in the alloys described herein include, for example, AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA6016, AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027, AA6028, AA6031, AA6032, AA6033, AA6040, AA6041, AA6042, AA6043, AA6151, AA6351, AA6351A, AA6451, AA6951, AA6053, AA6055, AA6056, AA6156, AA6060, AA6160, AA6260, AA6360, AA6460, AA6460B, AA6560, AA6660, AA6061, AA6061A, AA6261, AA6361, AA6162, AA6262, AA6262A, AA6063, AA6063A, AA6463, AA6463A, AA6763, A6963, AA6064, AA6064A, AA6065, AA6066, AA6068, AA6069, AA6070, AA6081, AA6181, AA6181A, AA6082, AA6082A, AA6182, AA6091, and AA6092. [0061] Suitable 7xxx series aluminum alloys for use in the alloys described herein include, for example, AA7019, AA7020, AA7021, AA7039, AA7072, AA7075, AA7085, AA7108, AA7108A, AA7015, AA7017, AA7018, AA7019A, AA7024, AA7025, AA7028, AA7030, AA7031, AA7035, AA7035A, AA7046, AA7046A, AA7003, AA7004, AA7005, AA7009, AA7010, AA7011, AA7012, AA7014, AA7016, AA7116, AA7122, AA7023, AA7026, AA7029, AA7129, AA7229, AA7032, AA7033, AA7034, AA7036, AA7136, AA7037, AA7040, AA7140, AA7041, AA7049, AA7049A, AA7149, AA7249, AA7349, AA7449, AA7050, AA7050A,
Attorney Docket #: 108050-1492445 AA7150, AA7250, AA7055, AA7155, AA7255, AA7056, AA7060, AA7064, AA7065, AA7068, AA7168, AA7175, AA7475, AA7076, AA7178, AA7278, AA7278A, AA7081, AA7181, AA7185, AA7090, AA7093, AA7095, and AA7099. [0062] Suitable 8xxx series aluminum alloys for use in the alloys described herein include, for example, AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA8019, AA8021, AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, AA8090, AA8091, and AA8093. [0063] Nonetheless, in embodiments, the aluminum alloy may be a 5xxx aluminum alloy, such as 5182. [0064] Various products including the alloys described herein can be produced. In some examples, the products prepared including the alloys described herein can be a cladded product including a core layer and one or more cladding layers. The core layer has a first side and a second side and one or more cladding layer(s) can be bonded to the first side or the second side of the core layer. In some examples, the core layer is clad on only one side (i.e., one cladding layer is present in the clad aluminum alloy product). In other examples, the core layer is clad on both sides (i.e., two cladding layers are present in the clad aluminum alloy product). [0065] The cladding layer(s) can be attached to a core layer by direct chill co-casting (i.e., fusion casting) as described in, for example, U.S. Patent Nos. 7,748,434 and 8,927,113, both of which are hereby incorporated by reference in their entireties, by hot and cold rolling a composite cast ingot as described in U.S. Patent No. 7,472,740, which is hereby incorporated by reference in its entirety, or by roll bonding to achieve the required metallurgical bonding between the core and the cladding. [0066] The alloys described herein can be used as the core layer or as the one or more cladding layers. Optionally, the one or more cladding layers can include a 1xxx series aluminum alloy, a 2xxx series aluminum alloy, a 3xxx series aluminum alloy, a 4xxx series aluminum alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, or an 8xxx series aluminum alloy. In some examples, the cladded product is prepared from an alloy as
Attorney Docket #: 108050-1492445 described herein as the core and a 5xxx or 6xxx series aluminum alloy as one or both of the cladding layers. [0067] The aluminum alloy product described herein can have any suitable gauge. The alloys can be cast and processed into various sizes and thicknesses, such as foil (e.g., below approximately 0.20 mm), sheet (e.g., from approximately 0.20 mm to 4.0 mm), shate (e.g., from approximately 4.0 mm to 15.0 mm), or plate (e.g., greater than approximately 15.0 mm), although other thicknesses and ranges can be used as well. In some examples, the aluminum alloy products described herein can be provided and delivered to a customer or an end user in an intermediate gauge (e.g., a gauge that will be further reduced by the customer or end user, as desired). In some examples, the aluminum alloy products described herein can be provided and delivered to a customer or an end user in a final gauge (e.g., a gauge that will not be further reduced by the customer or end user). [0068] Products including the alloys described herein can include a hydrogen content of 0.15 mL/100 grams or less (e.g., at or less than 0.10 mL/100 grams, at or less than 0.08 mL/100 grams, or at or less than 0.06 mL/100 grams). For example, the amount of hydrogen included in the aluminum alloy products can be at or less than approximately 0.15 mL/100 grams, 0.14 mL/100 grams, 0.13 mL/100 grams, 0.12 mL/100 grams, 0.11 mL/100 grams, 0.1 mL/100 grams, 0.09 mL/100 grams, 0.08 mL/100 grams, 0.07 mL/100 grams, 0.06 mL/100 grams, 0.05 mL/100 grams, 0.04 mL/100 grams, 0.03 mL/100 grams, 0.02 mL/100 grams, or 0.01 mL/100 grams. Optionally, the hydrogen content in the products can be at least 0.08 mL/100 grams. For example, the hydrogen content can be from 0.08 mL/100 grams to 0.25 mL/100 grams, from 0.1 mL/100 grams to 0.20 mL/100 grams, or from 0.12 mL/100 grams to 0.18 mL/100 grams. The amount of dissolved hydrogen present impacts the properties of the resulting metal product. During casting, the dissolved hydrogen can have an impact on the castability of the metal product (e.g., resistance to hot cracking) as well as the resultant metal product’s mechanical properties (e.g., bending strength, toughness, fatigue strength, maximum elongation, crash worthiness, surface quality, corrosion resistance, and other properties). Dissolved hydrogen can affect solidification and can result in porosity in the cast metal product. Products prepared from the alloys described herein, having the above-described hydrogen content, do not suffer from these detrimental effects.
Attorney Docket #: 108050-1492445 [0069] The aluminum alloy products described herein include intermetallic particles containing one or more of aluminum (Al), silicon (Si), magnesium (Mg), vanadium (V), calcium (Ca), strontium (Sr), titanium (Ti), beryllium (Be), chromium (Cr), and/or manganese (Mn), such as aluminum (Al), magnesium (Mg), titanium (Ti), vanadium (V), and/or calcium (Ca), in embodiments. However, surprisingly, due to the methods and grain refiner chips discussed herein, the intermetallic particles in the aluminum alloy products may have a length, (e.g. equivalent diameter or largest dimension), that is less than or about 50 μm, such as less than or about 45 μm, such as less than or about 40 μm, such as less than or about 35 μm, such as less than or about 30 μm, or ranging from about 1 μm to about 50 μm (e.g., from about 5 μm to about 45 μm or from about 10 μm to about 40 μm). In embodiments, the intermetallic particles may be AlxMgyTixVtCav particles, alone or nucleated from one or more TiAl3 particles. Nonetheless, the present technology has found that the methods and grain refiner chips discussed herein may prevent the formation of intermetallic particles having a length, or largest dimension, of greater than 50 μm. [0070] In embodiments, the intermetallic particles may contain Mg in an amount of from about 1.0 % to about 10.0 % (e.g., from about 2.0 % to about 9.5 %, from about 2.5 % to about 9.0 %, from about 3.0 % to about 8.5 %, or from about 3.5 % to about 8.0 %) based on the total weight of the alloy. For example, the intermetallic particle can include 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %, 6.0 %, 6.1 %, 6.2 %, 6.3 %, 6.4 %, 6.5 %, 6.6 %, 6.7 %, 6.8 %, 6.9 %, 7.0 %, 7.1 %, 7.2 %, 7.3 %, 7.4 %, 7.5 %, 7.6 %, 7.7 %, 7.8 %, 7.9 %, 8.0 %, 8.1 %, 9.2 %, 9.3 %, 9.4 %, 9.5 %, 9.6 %, 9.7 %, 9.8 %, 9.9 %, or 10.0 % Mg. All are expressed in wt. %. [0071] In embodiments, the intermetallic particles may contain Ti in an amount of from about 0.50 % to about 7.0 % (e.g., from about 1.0 % to about 6.0 %, from about 2 % to about 5.5 %, from about 2.5 % to about 5.0 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy. For example, the intermetallic particle can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.1
Attorney Docket #: 108050-1492445 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %, 6.0 %, 6.1 %, 6.2 %, 6.3 %, 6.4 %, 6.5 %, 6.6 %, 6.7 %, 6.8 %, 6.9 %, or 7.0 % Ti. All are expressed in wt. %. [0072] In embodiments, the intermetallic particles may contain V in an amount of from about 0.50 % to about 6.0 % (e.g., from about 1.0 % to about 5.5 %, from about 2 % to about 5.0 %, from about 2.5 % to about 4.5 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy. For example, the intermetallic particle can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9 %, or 6.0 % V. All are expressed in wt. %. [0073] In embodiments, the intermetallic particles may contain Ca in an amount of from about 0.10 % to about 5.0 % (e.g., from about 0.5 % to about 4.5 %, from about 1.0 % to about 4.0 %, from about 1.5 % to about 3.5 %, or from about 2.0 % to about 3.0 %) based on the total weight of the alloy. For example, the intermetallic particle can include 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %,
Attorney Docket #: 108050-1492445 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, or 5.0 % Ca. All are expressed in wt. %. [0074] In embodiments, the intermetallic particles may contain Cr in an amount of from about 0 % to about 1.0 % (e.g., from about 0.01 % to about 0.5 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy. For example, the intermetallic particle can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, or 1.0. Cr. In some cases, Cr is not present in the intermetallic particle (i.e., 0 %). All are expressed in wt. %. [0075] In embodiments, the intermetallic particles may contain Mn in an amount of from about 0 % to about 1.0 % (e.g., from about 0.01 % to about 0.5 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy. For example, the intermetallic particle can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, or 1.0. Mn. In some cases, Mn is not present in the intermetallic particle (i.e., 0 %). All are expressed in wt. %. [0076] In embodiments, the remainder of the intermetallic particle may be aluminum.
Attorney Docket #: 108050-1492445 [0077] In some cases, the metal products described herein can have a yield strength of at least about 100 MPa. For example, the metal products described herein can have a yield strength of from about 100 MPa to about 300 MPa (e.g., from about 150 MPa to about 250 MPa). In some cases, the yield strength can be about 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, or 300 MPa. [0078] In some cases, the metal products described herein can have an ultimate tensile strength of at least about 210 MPa. For example, the metal products described herein can have an ultimate tensile strength of from about 210 MPa to about 350 MPa (e.g., from about 250 MPa to about 325 MPa). In some cases, the ultimate tensile strength can be about 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, 300 MPa, 310 MPa, 320 MPa, 330 MPa, 340 MPa, or 350 MPa. [0079] In some cases, the metal products described herein can have a uniform elongation of at least about 18%. For example, the metal products described herein can have a uniform elongation of from about 18% to about 25% (e.g., from about 19% to about 23%). In some cases, the uniform elongation can be about 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, or 25%. [0080] In some cases, the metal products described herein can have a total elongation of at least about 20.5%. For example, the metal products described herein can have a total elongation of from about 20.5% to about 27.5% (e.g., from about 22% to about 26%). In some cases, the total elongation can be about 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, or 27.5%. Methods of Making [0081] The alloys discussed herein, which main contain one or more impurities, can be used to cast various metallic cast products, such as billets, ingots, or strips. Prior to casting, grain refiner chips, as discussed herein are introduced to the liquid metal. As discussed above, the grain refiner chips are reduced in particle size while being simultaneously or sequentially exposed to mechanical deformation. Namely, the present technology has surprisingly found that the unique combination of particle size and particle deformation provide unique benefits to the melt, even in the presence of sensitizing impurities (e.g. impurities prone to formation of intermetallic particles,
Attorney Docket #: 108050-1492445 particularly in the presence of grain refiner products). After introduction of the grain refiner chips, the liquid metal can optionally be degassed to reduce the amount of hydrogen dissolved in the liquid metal. In some cases, the degassing can include bubbling a gas, such as an inert gas (e.g., argon or nitrogen), through the liquid metal to induce dissolving of the hydrogen bubbles into the gas, and thus out of the liquid metal. Any suitable degassing technique can be used. [0082] While the melt may be optionally filtered utilizing a metal filter after the optional degassing, the alloys described herein can be cast using any suitable casting method known to those of ordinary skill in the art. Surprisingly, residence time of the melt after the introduction of the grain refiner chips is maintained or even decreased as compared to conventional casting processes, as the grain refiner chips interact more completely in a shorter amount of time, even in the presence of a large weight percentage of impurities. This is surprising, as previously, grain refiner products required additional residence time in the presence of a high weight percentage of impurities. [0083] As a few non-limiting examples, the casting process can include a direct chill (DC) casting process or a continuous casting (CC) process. A direct chill casting system can include a mold cavity and a retractable bottom block. As liquid metal solidifies in the mold cavity, the bottom block can be retracted away from the mold cavity to support the solidifying ingot (e.g., embryonic ingot) as the ingot continuous to grow in length due to solidifying metal at the surfaces of the ingot and as the ingot continuous to solidify throughout. The 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. Certain aspects of the present disclosure can involve continuous casting using a twin belt continuous casting device or a twin roll continuous casting device. [0084] After casting, the metal product (e.g., metal sheets, plates, or other cast products) can be rolled to a desired gauge. The metal product cast from the alloys as disclosed herein can have higher-than-usual concentrations of alloying elements and/or impurities. The traditional rolling technique is to pass the metal product through a hot rolling process and then a cold rolling process. Hot rolling occurs at temperatures above the recrystallization temperature of the metal, while cold
Attorney Docket #: 108050-1492445 rolling occurs at temperatures below the recrystallization temperature. Since cold rolling involves deforming the metal at temperatures below the recrystallization temperature, the metal is strain hardened through the formation of dislocations within the metal’s matrix. [0085] Optionally, the metal products described herein can be delivered in any suitable gauge as described herein. For example, the metal product can be delivered in an intermediate gauge or in a final gauge to a customer (e.g., an original equipment manufacturer) or any other suitable end user. In some cases, hot rolling to gauge can include receiving a metal product from a direct casting device and/or a continuous casting device, although that need not always be the case. [0086] These illustrative examples are given to introduce the reader to the general subject matter discussed here and are not intended to limit the scope of the disclosed concepts. The following sections describe various additional features and examples with reference to the drawings in which like numerals indicate like elements, and directional descriptions are used to describe the illustrative embodiments but, like the illustrative embodiments, should not be used to limit the present disclosure. The elements included in the illustrations herein may not be drawn to scale. [0087] FIG. 1 is a flowchart depicting a process 100 for casting and hot rolling a metal product that can include recycled scrap, according to certain aspects of the present disclosure. At block 102, the melt is formed from a melt precursor, which may include primary aluminum and/or recycled scrap as discussed above. The melt precursor can be melted in any suitable vessel, such as a rotary furnace, a crucible furnace, or any other suitable heating device. The liquid metal resulting from the melt precursor can include alloying elements that would render the liquid metal a non-standard alloy, such as an alloy that is not normally used for beverage parts (e.g., can ends or can bodies) or automotive parts (e.g., automotive hood liners), such as when recycled scrap is utilized. [0088] Sequentially or simultaneously, the grain refiner chips may be formed at block 103. In embodiments where blocks 102 and 103 occur sequentially, the grain refiner chips may be formed prior to forming the melt at block 102 or after forming the melt at block 102. Nonetheless, as discussed above the present technology has found that block 103 may produce grain refiner chips that have a maximum particle size and a high degree of deformation, providing grain refiner chips that improve the uniformity of the melt and decrease the likelihood of large intermetallic particle formation. For instance, block 103 may contain one or more operations 103A and 103B. In
Attorney Docket #: 108050-1492445 embodiments, the grain refiner chips may be formed by mechanically comminuting an as received grain refiner product at operation 103A. Operation 103A may include cutting, sawing, grinding, rolling, extruding, machining, impaction, as well as other mechanical refining processes as known in the art, the as received grain refiner product or combinations thereof, as well as any one or more of the mechanical deformations discussed herein. In embodiments, the as received grain refiner product may include rods, bars, ingots, and the like, as well as combinations thereof, having one or more dimensions discussed above prior to deformation. [0089] In embodiments, the mechanical comminuting may be conducted for a time and utilizing a mechanical deformation sufficient to significantly deform the received grain refiner into a plurality of individual grain refiner particles, such as greater than or about 500 particles/mm2, such as greater than or about 750 particles/mm2, such as greater than or about 1000 particles/mm2, such as greater than or about 1250 particles/mm2, such as greater than or about 1500 particles/mm2, such as greater than or about 1750 particles/mm2, such as greater than or about 2000 particles/mm2, such as greater than or about 2250 particles/mm2, such as greater than or about 2500 particles/mm2, such as greater than or about 2750 particles/mm2, such as greater than or about 3000 particles/mm2, or any ranges or values therebetween. [0090] Regardless of the mechanical method(s) selected, the grain refiner product may be comminuted to grain refiner chips having a particle size (e.g. equivalent diameter or largest dimension) of less than or about 1000 μm, such as less than or about 950 μm, such as less than or about 900 μm, such as less than or about 850 μm, such as less than or about 800 μm, such as less than or about 750 μm, such as less than or about 700 μm, such as less than or about 650 μm, such as less than or about 600 μm, such as less than or about 550 μm, such as less than or about 500 μm, such as less than or about 450 μm, such as less than or about 400 μm, such as less than or about 350 μm, such as less than or about 300 μm, such as less than or about 250 μm, such as less than or about 200 μm, such as less than or about 150 μm, such as less than or about 100 μm, such as less than or about 50 μm, or any ranges or values therebetween. [0091] Moreover, due to the mechanical comminution, the grain refiner chips contain aluminide phases, such as TiAl3 phases, boride clusters, carbide clusters, oxide stringers, and refraction impurities, with significantly reduced sizes. For instance, in embodiments operation 103A may be conducted for a period of time and/or at a mechanical force such that some, substantially all, or all
Attorney Docket #: 108050-1492445 of the TiAl3 phases present in the grain refiner chips have an equivalent spherical diameter of less than or about 100 μm, such as less than or about 95 μm, such as less than or about 90 μm, such as less than or about 85 μm, such as less than or about 80 μm, such as less than or about 75 μm, such as less than or about 70 μm, such as less than or about 65 μm, such as less than or about 60 μm, such as less than or about 55 μm, such as less than or about 50 μm, such as less than or about 45 μm, such as less than or about 40 μm, such as less than or about 35 μm, such as less than or about 30 μm, such as less than or about 25 μm, such as less than or about 20 μm, such as less than or about 15 μm, such as less than or about 10 μm, such as less than or about 5 μm, or any ranges or values therebetween. Furthermore, a high proportion of the grain refiner chip particles may have any one or more of the above particle size, such as greater than or about 50% (D50), greater than or about 60%, greater than or about 70%, greater than or about 80%, greater than or about 90%, or any ranges or values therebetween. [0092] In embodiments, the grain refiner chips may be added in particle form at block 103. However, in embodiments, the grain refiner chips may be incorporated into a rod, pellet, or the like prior to addition to the melt, as illustrated in optional operation 103B. For instance, the mechanically deformed grain refiner product particles may be reconstituted into one or more forms for convenient handling, such as taking the particles, which may also be or include chips and/or flakes, and forming a compact, puck, coarse granules, rods, blocks, combinations thereof, or the like. Regardless of the form in which the grain refiner chips are incorporated into the melt, in embodiments, the grain refiner chips may maintain the independent particles and sizes thereof, even when reconstituted into one or more larger forms for convenient handling. [0093] At block 104, the grain refiner chips, as well as any optional additional alloying elements can be added to the liquid metal. However, it should be understood that, in embodiments, the deformed grain refiner product may be incorporated at any point prior to or during casting, such as before or after degassing and/or filtration. In addition, in embodiments, the grain refiner product may be incorporated continuously during processing, before or during casting. Block 104 is shows as being upstream of a degassing operation (block 105, which may contain an optional metal filter operation). However, in embodiments, due to the increased nucleation speed and dispersion, and increased dissolution speed of the grain refiner, the grain refiner chips may be introduced after degassing block 105. Namely, as discussed above, traditional grain refiner products are introduced prior to degassing and/or metal filtering as traditional grain refiner products require lengthy
Attorney Docket #: 108050-1492445 residence times in the melt to fully dissolve and for any impurities to be dispersed prior to ingot formation. However, this is increasingly problematic when various impurities, or high concentrations thereof, of magnesium, vanadium, calcium, and/or titanium are present, as longer residence times allow for greater intermetallic particle formation. Thus, the present technology may provide for a faster melt process due at least in part to the increased surface area and deformed facets, or may include the grain refiner chips at a later stage (e.g. downstream of degassing), allowing further improvements in melt homogeneity and intermetallic particle size. Namely, without wishing to be bound by theory, it is believed that the high degree of deformation allows for decreased dissolution times, which, alone or in combination with the increased surface area, provides for a greatly improved dissolution and dispersion time for the grain refiner chips as compared to traditional grain refiner products. [0094] Nonetheless, adding optional alloying elements can include dissolving raw elements or mixtures of aluminum and the alloying elements into the liquid metal from block 102. After adding the alloying elements, the modified liquid metal can have a desired composition of alloying elements and aluminum. [0095] At block 105, the liquid metal from block 104 can be degassed to decrease the amount of dissolved gasses in the modified liquid metal. Degassing the liquid metal can include lowering the concentration of hydrogen in the modified liquid metal to a desired concentration, such as those identified above (e.g., at or below 0.25 mL/100 grams). For example, the amount of hydrogen included in the liquid metal after degassing can be at or less than approximately 0.25 mL/100 grams, 0.24 mL/100 grams, 0.23 mL/100 grams, 0.22 mL/100 grams, 0.21 mL/100 grams, 0.2 mL/100 grams, 0.19 mL/100 grams, 0.18 mL/100 grams, 0.17 mL/100 grams, 0.16 mL/100 grams, 0.15 mL/100 grams, 0.14 mL/100 grams, 0.13 mL/100 grams, 0.12 mL/100 grams, 0.11 mL/100 grams, 0.1 mL/100 grams, 0.09 mL/100 grams, 0.08 mL/100 grams, 0.07 mL/100 grams, 0.06 mL/100 grams, or 0.05 mL/100 grams. Any suitable technique can be used to degas the modified liquid metal. [0096] At block 106, the degassed liquid metal from block 105 can be cast using a direct chill casting to result in an intermediate metal product 116. In some cases, instead of casting using a direct chill casting device, as described with reference to block 106, the degassed liquid metal from block 105 can be cast using a continuous casting device at block 107. The resulting metal product
Attorney Docket #: 108050-1492445 at the intermediate gauge can be an intermediate metal product 116. Rolling to an intermediate gauge can include reducing the thickness of a direct-chill-cast ingot using any suitable equipment, such as using a reversing mill. [0097] At block 108, the intermediate metal product 116 can be hot rolled to gauge or intermediate gauge. Hot rolling to gauge can include applying pressure to the intermediate metal product 116 through one or more work rolls at elevated temperatures, such as temperatures at or above the recrystallization temperature of the intermediate metal product 116, although lower temperatures can also be used. For example, in some cases the hot rolling can occur at temperatures at or above approximately 400 °C, although other temperatures can be used. As a result of the hot rolling at block 108, the intermediate metal product 116 is reduced in thickness from an as-cast gauge to a desired gauge for delivery to an original equipment manufacturer (OEM) or other user or to an intermediate gauge. In an example, the as-cast gauge of an intermediate metal product 116 can be approximately 10 mm, whereas the final gauge (e.g., a desired gauge for delivery to an OEM) can be approximately 1.5 mm, although other gauges can be used. During hot rolling, the metal product can pass through any number of rollers implemented through any number of roll stands. After hot rolling, the metal product can be considered a hot-rolled metal product 118. The hot-rolled metal product 118 can have a T4 or O temper. [0098] In some cases, the metal product can be preheated prior to hot rolling. For example, the metal product can be preheated to a temperature at or above the recrystallization temperature. In an example, a metal product can be preheated to a temperature at or above approximately 400 °C, 450 °C, 500 °C, 550 °C, 560 °C, 570 °C, or 580 °C. In some cases, the metal product can be preheated in an oven at 400 °C to 580 °C for a period of 5 minutes to 24 hours. In some cases, the oven temperature can be approximately 550 °C to 570 °C and the time can be between 30 minutes and 6 hours. In some cases, the oven temperature can be approximately 560 °C and the time can be between 30 minutes and 6 hours. In some cases, preheating can occur at other temperatures and for other durations. [0099] At block 110, the hot-rolled metal product 118 can be optionally cold rolled from the intermediate gauge to the final gauge, if needed or desired. Cold rolling to gauge can include applying pressure to the hot-rolled metal product 118 through one or more work rolls at temperatures below the recrystallization temperature of the hot-rolled metal product 118. For
Attorney Docket #: 108050-1492445 example, in some cases the cold rolling can occur at temperatures below approximately 400 °C, although other temperatures can be used. As a result of the cold rolling at block 110, the hot-rolled metal product 118 is reduced in thickness from an intermediate gauge to a desired gauge for delivery to an OEM or other user. In an example, the intermediate gauge of a hot-rolled metal product 118 can be approximately 4 mm, whereas the final gauge (e.g., a desired gauge for delivery to an OEM) can be approximately 1.5 mm, although other gauges can be used. During cold rolling, the metal product can pass through any number of rollers implemented through any number of roll stands. After cold rolling, the metal product can be considered a cold-rolled metal product 119. The cold-rolled metal product 119 can have a T3 temper. [0100] At optional block 112, the hot-rolled metal product 118 can undergo heat treatment. In some cases, the heat treatment includes annealing. At block 112, the hot-rolled metal product 118 can be reheated to at or above an annealing temperature for a suitable period of time. For example, heating the hot-rolled metal product 118 to a temperature at or above 350° C for approximately 1 hour can bring the metal product to an O temper. [0101] In some cases, heat treatment can include solutionizing the hot-rolled metal product 118 to put certain alloying elements back into solution, such as silicon and copper. As part of solutionizing, the reheated metal product can be quenched to facilitate keeping the alloying elements in solution. [0102] Heat treatment can improve metallurgical and/or mechanical properties of the metal product. For example, annealing can result in improvements to the formability of the metal product. [0103] At block 114, the metal product can be coiled for delivery to an OEM. In some cases, the metal product can undergo further processing before delivery or can proceed directly into part manufacturing without coiling. [0104] Regardless of the method selected, the metal product may be well suited for part formation, such as for can end or can lid stock, as examples. Namely, the metal products discussed herein may exhibit a combination of strength and other key attributes, such as corrosion resistance, formability, and joining capabilities. Joining methods can include, but are not limited to, resistance spot welding (RSW), friction stir welding, remote laser welding, metal inert gas (MIG) welding, tungsten inert gas (TIG) welding, adhesive bonding, and self-piercing riveting. The alloy products
Attorney Docket #: 108050-1492445 can be used in a variety of applications, including beverage containers, automotive, transportation, electronics, and other applications. As discussed above, the metal products discussed herein may exhibit reduced cracking and breaking, even at very low final gauges, such as those utilized in beverage container applications, and particularly, at rivet locations on such beverage containers. [0105] Furthermore, due at least in part to the mechanical comminution during formation of the metal melt, the metal product may contain little to no aluminide phases or intermetallic particles, such as TiAl3 phases, boride clusters, oxide stringers, and refraction impurities. Moreover, if any aluminide phases remain, some, substantially all, or all of the phases exhibit significantly reduced equivalent spherical diameters to metal products formed utilizing traditional grain refiner products. For instance, in embodiments, some, substantially all, or all of the TiAl3 phases present in the metal product have an equivalent spherical diameter of less than or about 50 μm, such as less than or about 45 μm, such as less than or about 40 μm, such as less than or about 35 μm, such as less than or about 30 μm, such as less than or about 25 μm, such as less than or about 20 μm, such as less than or about 15 μm, such as less than or about 10 μm, such as less than or about 5 μm, or any ranges or values therebetween. Furthermore, a high proportion of the grain refiner chip particles may have any one or more of the above particle size, such as greater than or about 50% (D50), greater than or about 60%, greater than or about 70%, greater than or about 80%, greater than or about 90%, greater than or about 95%, greater than or about 97.5%, greater than or about 99% or any ranges or values therebetween. However, it should be understood that, in embodiments, little to no aluminide phases or intermetallic particles remain in the metal product. [0106] A collection of exemplary embodiments are provided below, including at least some explicitly enumerated as “Illustrations” providing additional description of a variety of example embodiments in accordance with the concepts described herein. These illustrations are not meant to be mutually exclusive, exhaustive, or restrictive; and the disclosure not limited to these example illustrations but rather encompasses all possible modifications and variations within the scope of the issued claims and their equivalents. [0107] As used below, any reference to a series of aspects (e.g., “Aspects 1-4”) or non- enumerated 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”).
Attorney Docket #: 108050-1492445 Aspect 1: A metal casting method comprising: forming an aluminum alloy liquid metal; mechanically deforming a grain refiner product into grain refiner chips having a particle size of less than 1000 μm, wherein at least a portion of the mechanically deformed grain refiner chip particles comprise one or more TiAl3 phase particles having an equivalent spherical diameter of less than or about 50 μm; adding the mechanically deformed grain refiner chips to the aluminum alloy liquid metal casting the liquid metal into a metal product; and rolling the metal product. [0108] Aspect 2: The method of aspect 1, wherein substantially all of the grain refiner chips comprise TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. [0109] Aspect 3: The method of aspect 1 or 2, wherein the mechanically deformed grain refiner chips are added in the form of chips, pellets, tablets, or a combination thereof. [0110] Aspect 4: The method of any one of aspects 1 to 3, wherein the mechanical deforming comprises sawing, grinding, rolling, extruding, machining, impaction, or a combination thereof. [0111] Aspect 5: The method of any one of aspects 1 to 4, wherein the mechanical deforming is conducted for a period of time to produce greater than or 500 TiAl3 particles/mm2. [0112] Aspect 6: The method of any one of aspects 1 to 5, wherein the metal product comprises one or more intermetallic particles, wherein each of the one or more intermetallic particles comprises an equivalent spherical diameter of less than or about 10 μm. [0113] Aspect 7: The method of any one of aspects 1 to 6, wherein the aluminum alloy comprises one or more of beryllium, magnesium, vanadium, strontium, titanium, and calcium. [0114] Aspect 8: The method of any one of aspects 1 to 7, wherein the aluminum alloy comprises a 5xxx series alloy. [0115] Aspect 9: The method of any one of aspects 1 to 8, wherein the molten metal comprises greater than or 10 wt.% recycled aluminum alloy. [0116] Aspect 10: The method of any one of aspects 1 to 9, wherein the aluminum alloy comprises from 0.01 wt.% titanium to 0.1 wt.% titanium. [0117] Aspect 11: The method of any one of aspects 1 to 10, wherein the aluminum alloy comprises from 1 wt.% to 7 wt.% magnesium.
Attorney Docket #: 108050-1492445 [0118] Aspect 12: The method of any one of aspects 1 to 11, wherein the aluminum alloy comprises from 0.01 wt.% vanadium to 0.1 wt.% vanadium. [0119] Aspect 13: The method of any one of aspects 1 to 12, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl3 phase particles having an equivalent diameter of less than or 50 μm. [0120] Aspect 14: The method of any one of aspects 1 to 13, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl3 phase particles having an equivalent diameter of less than or 20 μm. [0121] Aspect 15: The method of any one of aspects 1 to 14, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl3 phase particles having an equivalent diameter of less than or 10 μm. [0122] Aspect 16: A metal product cast from the method of any one of aspects 1 to 15. [0123] Aspect 17: A 5xxx series aluminum alloy product comprising 0.01 – 1.0 wt.% Cu, 0.1 – 0.8 wt.% Fe, 0.5 – 7.0 wt.% Mg, 0.01 – 1.2 wt.% Mn, 0 – 1.5 wt.% Si, 0 – 0.2 wt.% Ti, 0 – 8.0 wt.% Zn, 0 – 0.3 wt.% Cr, 0 – 0.15 wt.% Zr, 0 – 0.1 wt.% V, 0 – 0.15 wt.% Ca, up to 0.15 wt.% impurities, and Al, wherein the aluminum alloy product comprises intermetallic particles, the intermetallic particles comprising two or more of aluminum, beryllium, magnesium, vanadium, strontium, titanium, and calcium comprising an equivalent spherical diameter of less than 50 μm. [0124] Aspect 18: A beverage container comprising the aluminum alloy product of aspect 17, or cast from the method of any one of aspects 1 to 15. [0125] Aspect 19: A TiAl3 containing grain refiner product comprising, grain refiner chips having a particle size of less than 1000 μm, wherein greater than 50 wt.% of the grain refiner chips comprise TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. [0126] Aspect 20: The A TiAl3 containing grain refiner product of aspect 19, wherein substantially all of the grain refiner chips comprise TiAl3 phase particles having an equivalent spherical diameter of less than or 50 μm. [0127] The above-described aspects are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the present disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially
Attorney Docket #: 108050-1492445 from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included herein within the scope of the present disclosure, and all possible claims to individual aspects or combinations of elements or steps are intended to be supported by the present disclosure. Moreover, although specific terms are employed herein, as well as in the claims that follow, they are used only in a generic and descriptive sense, and not for the purposes of limiting the described embodiments, nor the claims that follow.