US20230074427A1 - Techniques for producing aluminum alloy products having improved formability and recyclability - Google Patents
Techniques for producing aluminum alloy products having improved formability and recyclability Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
Definitions
- the present disclosure relates to metallurgy generally and more specifically to aluminum alloy products and techniques for improving formability of aluminum alloy products, particularly those containing high amounts of recycled source content.
- the present disclosure also relates to aluminum alloy products useful for beverage containers and other aluminum alloy products, and methods of preparing aluminum alloy products.
- Formability is an important mechanical property of aluminum alloy products.
- a reduction of constituent particle size within the aluminum alloy microstructure aims to improve formability.
- environmental concerns call for increased recycled source content within aluminum alloy products.
- increasing the recycled source content of aluminum alloy products may reduce formability of the aluminum alloy products.
- AA3104 alloys which contain manganese are commonly used for beverage can body stock, while aluminum alloys containing magnesium (e.g., AA5182) have been used for beverage can end stock.
- AA5182 aluminum alloys containing magnesium
- Different aluminum alloys may be useful for meeting the needs of different beverage container technologies.
- Described herein are aluminum alloy products and methods of making aluminum alloy products in which the aluminum alloy products have been processed to have a favorable distribution of intermetallic particles, particle density, and/or spacing between the particles (inter-particle spacing), which may be beneficial for aluminum beverage container making processes and/or for minimizing and reducing galling and tear-offs during drawing, ironing, and/or necking during forming of an aluminum alloy product, (e.g., in the process of making aluminum beverage containers).
- the ability to control particle density and inter-particle spacing to favorable values may allow for increased recycled source content, benefiting the environmental and economic cost of aluminum alloy product production.
- the aluminum alloy includes a plurality of particles including ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese.
- the aluminum alloy includes a plurality of particles including ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese.
- the aluminum alloy is from a recycled source or is at least partially from a recycled source.
- the aluminum alloys of some embodiments may exhibit ratios of iron to silicon (e.g., ratios of wt. %) that may be greater than iron to silicon ratios in some alloys conventionally used in the beverage container making process. For example, ratios of iron wt. % to silicon wt.
- % in aluminum alloys described herein may range from about 0.5 to about 5.0, or may be about 0.5, 0.6, 0.7, 0.8, 0.9, 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, and/or 5.0, for example.
- the disclosed aluminum alloys of some embodiments may alternatively exhibit ratios of silicon to iron (e.g., ratios of wt. %) that are greater than silicon to iron ratios in alloys conventionally used in the beverage container making process.
- % in aluminum alloys described herein may range from about 0.5 to about 1.0, such as from 0.5 to 1.0, such as from 0.5 to 0.6, from 0.5 to 0.7, from 0.5 to 0.8, from 0.5 to 0.9, from 0.6 to 07, from 0.6 to 0.8, from 0.6 to 0.9, from 0.6 to 1.0, from 0.7 to 0.8, from 0.7 to 0.9, from 0.7 to 1.0, from 0.8 to 0.9, from 0.8 to 1.0, or from 0.9 to 1.0, or about 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9,
- Increasing the amount of iron relative to the amount of silicon or the amount of silicon relative to the amount of iron in an aluminum alloy may be useful for controlling particle sizes, concentrations, distributions, particle density, inter-particle spacing, and/or compositions of intermetallic particles in the aluminum alloy. Additionally, using increased amounts of iron in an aluminum alloy may allow larger amounts of recycled source content to be used.
- Sizes, concentrations, density, inter-particle spacing, compositions of particles, and/or distribution of intermetallic particles in the aluminum alloy may alternatively or additionally be controlled by subjecting the aluminum alloy to suitable homogenization conditions after casting. For example, by homogenizing (soaking) the aluminum alloy at relatively long durations (e.g., more than about 12 hours or more than about 24 hours), less favorable intermetallic particles may be transformed into more favorable particles. Such transformations may not occur or not occur to a significant enough extent during short duration (e.g., less than about 24 hours or less than about 12 hours) homogenization to suitably impact the size, concentration, inter-particle spacing, distribution of intermetallic particles, and/or composition of enough numbers of particles. For example, by subjecting an aluminum alloy to long, high temperature homogenization, less desirable intermetallic particles can have their chemical and crystal structures altered by diffusion of silicon into the particles and/or diffusion of iron out of the particles.
- an aluminum alloy product comprises an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon.
- a ratio of an iron wt. % in the aluminum alloy to a silicon wt. % in the aluminum alloy is from 0.5 to 5.0, such as from 0.5 to 1.0, from 0.5 to 1.1, from 0.5 to 1.5, from 0.5 to 1.8, from 0.5 to 2.0, from 0.5 to 2.5, from 0.5 to 3.0, from 0.5 to 3.5, from 0.5 to 4.0, from 0.5 to 4.5, from 1.0 to 1.1, from 1.0 to 1.5, from 1.0 to 1.8, from 1.0 to 2.0, from 1.0 to 2.5, from 1.0 to 3.0, from 1.0 to 3.5, from 1.0 to 4.0, from 1.0 to 4.5, from 1.0 to 5.0, from 1.1 to 1.5, from 1.1 to 1.8, from 1.1 to 2.0, from 1.1 to 2.5, from 1.1 to 3.0, from 1.1 to 3.5, from 1.1 to 4.0, from 1.0 to 4.5, from
- a ratio of a silicon wt. % to an iron wt. % in an aluminum alloy products may be from 0.5 to 1.0, such as from 0.5 to 0.55, from 0.5 to 0.6, from 0.5 to 0.65, from 0.5 to 0.7, from 0.5 to 0.75, from 0.5 to 0.8, from 0.5 to 0.85, from 0.5 to 0.9, from 0.5 to 0.95, from 0.55 to 0.6, from 0.55 to 0.65, from 0.55 to 0.7, from 0.55 to 0.75, from 0.55 to 0.8, from 0.55 to 0.85, from 0.55 to 0.9, from 0.55 to 0.95, from 0.55 to 1.0, from 0.6 to 0.65, from 0.6 to 0.7, from 0.6 to 0.75, from 0.6 to 0.8, from 0.6 to 0.85, from 0.6 to 0.9, from 0.6 to 0.95, from 0.6 to 1, from 0.65 to 0.65, from 0.65 to 0.7, from 0.65 to 0.75
- An example 3xxx series aluminum alloy may comprise from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.4-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- the cast aluminum alloy product includes ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese and/or ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese.
- a particle density such as of ⁇ -phase intermetallic particles and/or ⁇ -phase intermetallic particles, may be from 5 to 30,000 particles per ⁇ m 2 , such as from 10 to 5,000, from 10 to 20,000, from 10 to 15,000, from 10 to 10,000, from 10 to 9,500, from 10 to 9,000, from 10 to 8,500, from 10 to 8,000, from 10 to 7,500, from 10 to 7,000, from 10 to 6,500, from 10 to 6,000, from 10 to 5,500, from 10 to 5,000, from 10 to 4,500, from 10 to 4,000, from 10 to 3,500, from 10 to 3,000, from 10 to 2,500, from 10 to 2,000, from 10 to 1,500, from 10 to 1,000, from 10 to 950, from 10 to 900, from 10 to 850,
- an inter-particle spacing for the plurality of particles may be from 1 ⁇ m to 25 ⁇ m, such as from 1 ⁇ m to 2 ⁇ m, from 1 ⁇ m to 3 ⁇ m, from 1 ⁇ m to 4 ⁇ m, from 1 ⁇ m to 5 ⁇ m, from 1 ⁇ m to 6 ⁇ m, from 1 ⁇ m to 7 ⁇ m, from 1 ⁇ m to 8 ⁇ m, from 1 ⁇ m to 9 ⁇ m, from 1 ⁇ m to 10 ⁇ m, from 1 ⁇ m to 11 ⁇ m, from 1 ⁇ m to 12 ⁇ m, from 1 ⁇ m to 13 ⁇ m, from 1 ⁇ m to 14 ⁇ m, from 1 ⁇ m to 15 ⁇ m, from 1 ⁇ m to 16 ⁇ m, from 1 ⁇ m to 17 ⁇ m, from 1 ⁇ m to 18 ⁇ m, from 1 ⁇ m to 19 ⁇ m, from 1 ⁇ m to 20 ⁇ m, from 1 ⁇ m to 21 ⁇ m, from 1 ⁇ m to 20
- the plurality of particles may have diameters of from 100 nm to 50 ⁇ m or 500 nm to 10 ⁇ m or 100 nm to 1 ⁇ m, such as from 100 nm to 200 nm, from 100 nm to 300 nm, from 100 nm to 400 nm, from 100 nm to 500 nm, from 100 nm to 600 nm, from 100 nm to 700 nm, from 100 nm to 800 nm, from 100 nm to 900 nm, from 200 nm to 300 nm, from 200 nm to 400 nm, from 200 nm to 500 nm, from 200 nm to 600 nm, from 200 nm to 700 nm, from 200 nm to 800 nm, from 200 nm to 900 nm, from 200 nm to 1 ⁇ m, from 300 nm to 400 nm, from 300 nm to 500 nm, from 300 nm to 600 nm,
- the composition of the aluminum alloy for the aluminum alloy products described above may optionally comprise from 0.1 wt. % to 1.0 wt. % iron (Fe), from 0.05 wt. % to 0.8 wt. % silicon (Si), from 0.2 wt. % to 2.0 wt. % manganese (Mn), from 0.2 wt. % to 2.0 wt. % magnesium (Mg), up to 0.5 wt. % copper (Cu), up to 0.05 wt. % zinc (Zn), and aluminum (Al).
- the composition of the aluminum alloy for the aluminum alloy products described above may comprise up to 0.15 wt. % impurities. Optionally, a remainder may be aluminum.
- the composition of the aluminum alloy for the aluminum alloy products described above may comprise from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium (Ti), up to 0.10 wt. % chromium (Cr), up to 0.10 wt. % zirconium (Zr), up to 0.10 wt.
- Ti titanium
- Cr chromium
- Zr zirconium
- the composition of the aluminum alloy for the aluminum alloy products described above may comprise from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum.
- the aluminum alloy may include a 3xxx series aluminum alloy.
- the aluminum alloy may optionally comprise from 0.8 wt. % to 1.4 wt. % magnesium, from 0.8 wt. % to 1.3 wt. % manganese, up to 0.25 wt. % copper, from 0.25 wt. % to 0.7 wt. % iron, up to 0.7 wt.%, and up to 0.25 wt. % zinc.
- the remainder may be aluminum.
- the aluminum alloys for the aluminum alloy products described above may optionally include ⁇ -phase intermetallic particles comprising from 0.5% to 4.0% by volume of the aluminum alloy, such as from 0.5 to 1.0, from 0.5 to 1.5, from 0.5 to 2.0, from 0.5 to 2.5, from 0.5 to 3.0, from 0.5 to 3.5, from 1.0 to 1.5, from 1.0 to 2.0, from 1.0 to 2.5, from 1.0 to 3.0, from 1.0 to 3.5, from 1.0 to 4.0, from 1.5 to 2.0, from 1.5 to 2.5, from 1.5 to 3.0, from 1.5 to 3.5, from 1.5 to 4.0, from 2.0 to 2.5, from 2.0 to 3.0, from 2.0 to 3.5, from 2.0 to 4.0, from 2.5 to 3.0, from 2.5 to 3.5, from 2.5 to 4.0, from 3.0 to 3.5, from 3.0 to 4.0, or from 3.5 to 4.0.
- ⁇ -phase intermetallic particles comprising from 0.5% to 4.0% by volume of the aluminum alloy, such as from 0.5 to 1.0, from 0.5 to 1.5, from 0.5 to 2.0
- the aluminum alloys for the aluminum alloy products described above may include ⁇ -phase intermetallic particles comprising from 0% to 2.0% by volume of the aluminum alloy, such as from 0 to 0.5, from 0 to 1.0, from 0 to 1.5, from 0.5 to 1.0, from 0.5 to 1.5, from 0.5 to 2.0, from 1.0 to 1.5, from 1.0 to 2.0, or from 1.5 to 2.0.
- the aluminum alloys for the aluminum alloy products described above may include ⁇ -phase intermetallic particles comprising Al 15 (Fe,Mn) 3 Si 2 .
- the aluminum alloys for the aluminum alloy products described above may include ⁇ -phase intermetallic particles comprising Al 6 (Fe,Mn).
- the aluminum alloys for the aluminum alloy products described above may include a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density is from 0.2 to 1,000 or a ratio of a volume % of the ⁇ -phase intermetallic particles to a volume % of the ⁇ -phase intermetallic particles is from 0.6 to 1,000.
- the aluminum alloys for the aluminum alloy products described above may include a ratio of the ⁇ -phase intermetallic particle number density to the ⁇ -phase intermetallic particle number density from 0.3 to 3, such as from 0.3 to 0.4, from 0.3 to 0.5, from 0.3 to 0.6, from 0.3 to 0.7, from 0.3 to 0.8, from 0.3 to 0.9, from 0.3 to 1.0, from 0.3 to 1.1, from 0.3 to 1.2, from 0.3 to 1.3, from 0.3 to 1.4, from 0.3 to 1.5, from 0.3 to 1.6, from 0.3 to 1.7, from 0.3 to 1.8, from 0.3 to 1.9, from 0.3 to 2.0, from 0.3 to 2.1, from 0.3 to 2.2, from 0.3 to 2.3, from 0.3 to 2.4, from 0.3 to 2.5, from 0.3 to 2.6, from 0.3 to 2.7, from 0.3 to 2.8, from 0.3 to 2.9, from 0.4 to 0.5, from 0.4 to 0.6, from 0.4 to 0.7, from 0.4 to
- the aluminum alloy products described above may include a plurality of particles, where 80 percent or more of the inter-particle spacings between particles are from 5 ⁇ m to 15 ⁇ m.
- the plurality of particles may include iron-containing particles, such as iron-containing particles where a majority have a diameter from 1 ⁇ m to 40 ⁇ m.
- the iron-containing particles may comprise from 1% to 4% of a total volume of the aluminum alloy.
- the aluminum alloys for the aluminum alloy products described above may comprise or further comprise manganese-containing dispersoids, such as where a majority of the manganese-containing dispersoids have a diameter of from 10 nm to 1.5 ⁇ m.
- the manganese-containing dispersoids may comprise up to 1% of a total volume of the aluminum alloy.
- dispersoids are not included in counts of particles of other types, such as ⁇ -phase particles and/or ⁇ -phase particles, and/or may optionally be counted separately from other types of particles.
- a metal product may be prepared by any of the methods described herein.
- a metal product comprises a homogenized 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, such as with a ratio of a silicon wt. % in the homogenized 3xxx series aluminum alloy to an iron wt.
- % in the homogenized 3xxx series aluminum alloy of from 0.5 to 1.0, and including ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and optionally ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese, with at least a portion of the ⁇ -phase intermetallic particles corresponding to ⁇ -phase intermetallic particles transformed during homogenization of the homogenized 3xxx series aluminum alloy.
- a ratio of a volume % and/or a number density of the ⁇ -phase intermetallic particles to a volume % or a number density of the ⁇ -phase intermetallic particles is from 0.6 to 1000, or more.
- An example method of this aspect comprises preparing a cast aluminum alloy product comprising an aluminum alloy, such as an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product.
- homogenizing may include heating the cast aluminum alloy product to a homogenization temperature, such as a homogenization temperature that is between 500° C. to 650° C., such as from 500° C. to 510° C., from 500° C. to 520° C., from 500° C. to 530° C., from 500° C. to 540° C., from 500° C.
- the homogenization temperature may optionally be within 75° C. of a solidus temperature of the aluminum alloy, such as within 70° C. of a solidus temperature of the aluminum alloy, within 65° C. of a solidus temperature of the aluminum alloy, within 60° C.
- the cast aluminum alloy product may optionally be at the homogenization temperature (i.e., soaking) for a time duration from 0.1 hours to 36 hours or from 12 hours to 36 hours, such as from 0.1 hours to 0.5 hours, from 0.1 hours to 1 hour, from 0.1 hours to 1.5 hours, from 0.1 hours to 2 hours, from 0.1 hours to 2.5 hours, from 0.1 hours to 3 hours, from 0.1 hours to 3.5 hours, from 0.1 hours to 4 hours, from 0.1 hours to 4.5 hours, from 0.1 hours to 5 hours, from 0.1 hours to 5.5 hours, from 0.1 hours to 6 hours, from 0.1 hours to 6.5 hours, from 0.1 hours to 7 hours, from 0.1 hours to 7.5 hours, from 0.1 hours to 8 hours, from 0.1 hours to 8.5 hours, from 0.1 hours to 9 hours, from 0.1 hours to 9.5 hours, from 0.1 hours to 10 hours, from 0.1 hours to 10.5 hours, from 0.1 hours to 11 hours, from 0.1 hours to 11.5 hours, from 0.1 hours to 12 hours, from a time duration from
- a size of the ⁇ -phase intermetallic particles decreases as compared to a size of the ⁇ -phase intermetallic particles prior to the soaking. In some embodiments, during the soaking, a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product prior to the soaking.
- Methods of this aspect may optionally further comprise subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- the one or more rolling processes comprise at least one of a hot rolling process or a cold rolling process.
- the hot rolling process may comprise an exit temperature of from 100° C. to 500° C., such as from from 100° C. to 150° C., from 100° C. to 200° C., from 100° C. to 250° C., from 100° C. to 300° C., from 100° C. to 350° C., from 100° C. to 400° C., from 100° C. to 450° C., from 150° C. to 200° C., from 150° C.
- the rolled aluminum alloy product produced by the hot rolling process has a thickness from 1 mm to 8 mm, such as from 1 mm to 2 mm, from 1 mm to 3 mm, from 1 mm to 4 mm, from 1 mm to 5 mm, from 1 mm to 6 mm, from 1 mm to 7 mm, from 2 mm to 3 mm, from 2 mm to 4 mm, from 2 mm to 5 mm, from 2 mm to 6 mm, from 2 mm to 7 mm, from 2 mm to 8 mm, from 3 mm to 4 mm, from 3 mm to 5 mm, from 3 mm to 6 mm, from 3 mm to 7 mm, from 3 mm to 8 mm, from 4 mm to 5 mm, from 4 mm to 6 mm, from 4 mm to 7 mm, from 4 mm to 8 mm, from 5 mm to 6 mm, from 5 mm to 7 mm, from 5 mm to 8 mm, from 6 mm to 7 mm, from 6
- the cold rolling process may comprise an exit temperature of from 50° C. to 250° C., such as from 50° C. to 100° C., from 50° C. to 150° C., from 50° C. to 200° C., from 100° C. to 150° C., from 100° C. to 200° C., from 100° C. to 250° C., from 150° C. to 200° C., from 150° C. to 250° C., or from 200° C. to 250° C.
- an exit temperature of from 50° C. to 250° C. such as from 50° C. to 100° C., from 50° C. to 150° C., from 50° C. to 200° C., from 100° C. to 150° C., from 100° C. to 200° C., from 100° C. to 250° C., from 150° C. to 200° C., from 150° C. to 250° C., or from 200° C. to 250° C.
- the rolled aluminum alloy product produced by the cold rolling process has a thickness from 0.15 mm to 0.50 mm, such as from 0.15 mm to 0.20 mm, from 0.15 mm to 0.25 mm, , from 0.15 mm to 0.30 mm, from 0.15 mm to 0.35 mm, from 0.15 mm to 0.40 mm, from 0.15 mm to 0.45 mm, from 0.15 mm to 0.50 mm, from 0.20 mm to 0.25 mm, from 0.20 mm to 0.30 mm, from 0.20 mm to 0.35 mm, from 0.20 mm to 0.40 mm, from 0.20 mm to 0.45 mm, from 0.20 mm to 0.50 mm, from 0.25 mm to 0.30 mm, from 0.25 mm to 0.35 mm, from 0.25 mm to 0.40 mm, from 0.25 mm to 0.45 mm, from 0.25 mm to 0.50 mm, from 0.30 mm to 0.35 mm, from 0.30 mm to 0.40 mm, from 0.25
- An example method of this aspect comprises providing a cast metal product comprising a metal composite, wherein the metal composite comprises iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the metal composite to an iron wt. % in the metal composite is from 0.5 to 1.0, and homogenizing the cast metal product to control an inter-particle spacing of the plurality of particles and to control a particle density of the plurality of particles such to achieve a ratio of a peak inter-particle spacing to a particle number density from 0.0003/ ⁇ m to 0.0006/ ⁇ m.
- the metal composite includes a plurality of particles including ⁇ -phase intermetallic particles comprising silicon and one or more of iron or manganese and ⁇ -phase intermetallic particles comprising one or more of iron or manganese.
- the metal composite of the method described includes an inter-particle spacing is from 1 ⁇ m to 25 ⁇ m. In some embodiments, the metal composite of the method described includes the particle density is from 5 to 30,000 particles per ⁇ m 2 .
- the metal composite of the method described includes the particle density is from 50 to 1,000 particles per ⁇ m 2 . In some embodiments, the metal composite of the method described includes the plurality of particles comprising a particle diameter from 1 ⁇ m to 50 ⁇ m. Optionally, the plurality of particles may have diameters of from 500 nm to 50 ⁇ m.
- the homogenization temperature may be from 400° C. to less than the melting point of aluminum (e.g., 660° C.) or to less than the solidus point of the particular alloy.
- an example time duration for the soaking may be from 0.1 hours to 48 hours.
- the homogenization temperature is within 25° C. of a solidus temperature of the cast metal product.
- the source aluminum alloy(s) for the aluminum alloy products prepared according to the above described methods may correspond to the same series aluminum alloy or a mixture of different series aluminum alloys.
- preparing the cast aluminum alloy product comprises preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy.
- preparing the molten 3xxx series aluminum alloy comprises melting both a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy are from a recycled source.
- aluminum alloys including a higher percentage of silicon may be useful for achieving a target silicon to iron ratio.
- preparing the molten aluminum alloy optionally further comprises melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy along with a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- multiple homogenization steps may be useful.
- a secondary lower temperature homogenization after a first, higher temperature and/or long duration, homogenization may be useful for preparing an aluminum alloy product, such as for rolling or other processing.
- a multiple-step homogenization process may include reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature; and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration, such as a second time duration that is shorter than the time duration of the initial long-duration soak.
- the second time duration may be from 1 hour to 24 hours, such as from 1 hour to 2 hours, from 1 hour to 3 hours, from 1 hour to 4 hours, from 1 hour to 5 hours, from 1 hour to 6 hours, from 1 hour to 7 hours, from 1 hour to 8 hours, from 1 hour to 9 hours, from 1 hour to 10 hours, from 1 hour to 11 hours, from 1 hour to 12 hours, from 1 hour to 13 hours, from 1 hour to 14 hours, from 1 hour to 15 hours, from 1 hour to 16 hours, from 1 hour to 17 hours, from 1 hour to 18 hours, from 1 hour to 19 hours, from 1 hour to 20 hours, from 1 hour to 21 hours, from 1 hour to 22 hours, from 1 hour to 23 hours, from 2 hours to 3 hours, from 2 hours to 4 hours, from 2 hours to 5 hours, from 2 hours to 6 hours, from 2 hours to 7 hours, from 2 hours to 8 hours, from 2 hours to 9 hours, from 2 hours to 10 hours, from 2 hours to 11 hours, from 2 hours to 12 hours, from 2 hours to 13 hours, from 2 hours to 14 hours, from
- the secondary lower temperature for homogenization is from 500° C. to 580° C., such as from 500° C. to 505° C., from 500° C. to 510° C., from 500° C. to 515° C., from 500° C. to 520° C., from 500° C. to 525° C., from 500° C. to 530° C., from 500° C. to 535° C., from 500° C. to 540° C., from 500° C. to 545° C., from 500° C. to 550° C., from 500° C. to 555° C., from 500° C. to 560° C., from 500° C. to 580° C., such as from 500° C. to 505° C., from 500° C. to 510° C., from 500° C. to 515° C., from 500° C. to 520° C., from 500° C. to 525° C., from 500° C. to 530° C., from
- soaking the homogenized aluminum alloy product at the second homogenization temperature controls a surface quality or characteristic of the homogenized aluminum alloy product.
- soaking the homogenized aluminum alloy product at the second homogenization temperature brings a temperature of the homogenized aluminum alloy product to a temperature sufficient for a rolling process.
- Disclosed methods may optionally include subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- FIG. 1 provides an illustrative graph showing a relationship between formability of an aluminum alloy and average particle size according to some embodiments.
- FIG. 2 A provides a schematic illustration of an aluminum alloy sample having particles according to some embodiments.
- FIG. 2 B provides a schematic illustration of forces being exerted on an aluminum alloy sample having particles according to some embodiments.
- FIG. 2 C provides a schematic illustration of crack propagation in an aluminum alloy sample having particles according to some embodiments.
- FIG. 2 D provides a schematic illustration of cracking of an aluminum alloy sample having particles according to some embodiments.
- FIG. 3 provides an optical micrograph image of a crack propagating through an aluminum alloy having particles according some embodiments.
- FIG. 4 provides a schematic overview of an example method for making an aluminum alloy product.
- FIG. 5 provides a plot showing example homogenization conditions used for making aluminum alloy products.
- FIG. 6 provides a method of making an aluminum alloy having favorable particle density and inter-particle spacing according to some embodiments.
- FIG. 7 A and FIG. 7 B provide plots showing predicted equilibrium phase diagrams for two example 3xxx series aluminum alloys.
- FIG. 8 provides electron micrograph images for samples of two example 3xxx series aluminum alloys as cast and after processing according to two different processing regimes.
- FIG. 9 provides electrical conductivity data for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 10 provides electron micrograph images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 11 provides electron micrograph images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 12 provides particle size distributions for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 13 provides images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 14 provides images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 15 A and FIG. 15 B provide charts showing tensile properties for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- FIG. 16 A and FIG. 16 B provide plots showing bendability test results for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes.
- the present disclosure provides aluminum alloy products and methods of making and treating aluminum alloys and aluminum alloy products.
- the aluminum alloys used in the methods and products described herein include, for example, 3xxx series aluminum alloys, 4xxx series aluminum alloys, 5xxx series aluminum alloys, or 6xxx series aluminum alloys.
- the aluminum alloys may include an alloy matrix comprising aluminum, magnesium, manganese, silicon, iron, and optionally copper.
- 3xxx series aluminum alloys may be particularly useful with the disclosed methods and products.
- Exemplary 3xxx series (also referred to herein as AA3xxx series) aluminum alloys for use in the methods and products described herein can include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3405, AA3405A, AA3405B, AA3007, AA3407, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3410, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.
- the present disclosure relates to aluminum alloy products having improved formability.
- Large particles formed within aluminum alloy products may reduce the formability of the aluminum alloy products because large particles can increase cracking susceptibility and can reduce the overall strength of aluminum alloy products.
- Voids may form around particles, especially large particles, within the aluminum alloy material. Large particles often have increased porosity, reduced ductility, and can be more brittle than the aluminum alloy material surrounding the particle.
- the difference in material properties between the particles and aluminum alloy matrix may concentrate stress or strain applied to the aluminum alloy product around the particles. The larger the particle, the greater the propensity for stress or strain to concentrate around the particle. For example, excess or overly large particles may cause tear off to occur during manufacturing processes, such as during drawing or necking of the aluminum alloy, because of the weak points formed around the particles. In other scenarios, large particles may cause an aluminum alloy product to split or fracture during use.
- a general approach to increasing formability is to reduce particle size.
- the density of particles within a set volume of aluminum alloy increases, since the particles may simply decrease in size by breaking into multiple smaller particles. Increased particle density may also be detrimental to the formability of aluminum alloy products.
- the particles become closer together, on average, reducing the spacing between proximate particles (inter-particle spacing).
- Inter-particle spacing Reduced or low inter-particle spacing may be problematic because crack propagation may take less energy when particles are spaced close together, as cracks may preferentially extend between particles.
- cracks may form from voids present around particles or weak points within the aluminum alloy.
- a reduction in inter-particle spacing may increase crack propagation from the weak points around particles because less energy may be required for the crack to reach the next nearest particle.
- reducing particle size can actually be detrimental to the formability of aluminum alloy products.
- controlling particle size and inter-particle spacing may be useful for making aluminum alloy products having improved or optimal formability.
- the presently described aluminum alloy products may exhibit particle sizes and inter-particle spacing that limit or reduce tear off and/or stress induced cracking (i.e., improve formability).
- the aluminum alloys disclosed herein may include an elemental composition which allows for formation of favorable particle size and favorable inter-particle spacing.
- the aluminum alloys disclosed herein may also allow for an increase in recycled source content.
- Increasing the recycled source content of an aluminum alloy can reduce the formability of the aluminum alloy product because of certain higher alloying components present within the recycled source content.
- Recycled source content is generally a mixture of multiple different types of materials.
- the composition of the recycled source content can sometimes include undesirable components in undesirable amounts.
- the mixed composition may create undesirable particles upon casting and/or processing.
- the particles may exhibit undesirable composition, sizing, and/or spacing. Accordingly, by use of the disclosed techniques, particle size and particle density can be controlled to a level that may be able to compensate for the mixed composition and therefore be compatible with high amounts of recycled source content without impacting the formability character of the resultant aluminum alloy product.
- Aluminum alloy products can be prepared by casting an aluminum alloy to form a cast aluminum alloy product and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product.
- aluminum alloy products containing iron and manganese may generate intermetallic particles comprising Al and one or more of Fe or Mn, which may be referred to herein as Al-(Fe, Mn) intermetallic particles or ⁇ -phase intermetallic particles, within the cast aluminum alloy product.
- intermetallic particles comprising Al, Si, and one or more of Fe or Mn also referred to herein as Al-(Fe, Mn)-Si intermetallic particles or ⁇ -phase intermetallic particles, may also be generated.
- many aluminum alloys may include such intermetallic particles upon casting.
- ⁇ -phase particles tend to be larger and more blocky or geometric than ⁇ -phase particles, while ⁇ -phase particles are harder and tend to be smaller than ⁇ -phase particles, in general.
- intermetallic particles may be broken, impacting their size, distribution, and number density, for example.
- intermetallic particles in a cast aluminum alloy product may be beneficial.
- aluminum alloys including intermetallic particles can be beneficial for forming aluminum beverage containers since the intermetallic particles may be significantly harder than other portions of the aluminum alloy product.
- the hard intermetallic particles can reduce galling by cleaning die surfaces.
- the intermetallic particles may abrade drawing, ironing, and necking dies and reduce or remove metal built up on the die surfaces.
- wall thicknesses are reduced.
- the presence of ⁇ -phase intermetallic particles may be detrimental, however, when wall thicknesses are reduced during these processes if the ⁇ -phase particles are too large or present at too high of an amount. Excess or overly large ⁇ -phase particles may cause tear off to occur during drawing or necking, where the beverage container wall splits or fractures, damaging the beverage container wall. Tear off, in some cases, may interrupt the manufacturing processes, as wall portions may completely separate from a damaged beverage container and may need to be removed from within the die or other manufacturing equipment.
- the presently described aluminum alloy products exhibit intermetallic particle sizes, distributions, concentrations, and compositions that limit or reduce tear off.
- the disclosed aluminum alloy products may preferentially generate ⁇ -phase intermetallic particles, such as by converting ⁇ -phase intermetallic particles to ⁇ -phase intermetallic particles during a homogenization process.
- alloying elements may diffuse and migrate throughout a crystal structure of a cast aluminum alloy product and change the size, distribution, concentration, and composition of intermetallic particles.
- silicon atoms present in the aluminum crystal structure may diffuse into ⁇ -phase intermetallic particles and transform the particles into ⁇ -phase intermetallic particles.
- silicon may be present in low amounts, such as less than about 1 wt. %, it may take significant time for silicon to diffuse and accumulate in the ⁇ -phase intermetallic particles in the cast product, so long duration homogenization may be useful for effecting significant transformation of ⁇ -phase intermetallic particles.
- silicon from the aluminum alloy may diffuse and transform at least a fraction of the ⁇ -phase intermetallic particles into ⁇ -phase intermetallic particles.
- Example homogenization conditions may include soaking a cast aluminum alloy product at a high temperature for 12 hours or 24 hours or more. For example, soaking may occur at a homogenization temperature of from about 575° C. to about 615° C., from about 580° C. to about 610° C., or from about 585° C. to about 605° C.
- a secondary homogenization process may also be useful for some embodiments. For example, a temperature of the homogenized aluminum alloy product may be reduced to a lower temperature and the aluminum alloy product may be held (soaked) at the lower temperature for a particular time duration.
- Example secondary homogenization temperatures include from about 500° C. to about 600° C., and may be dependent upon the particular alloy.
- Example secondary homogenization soak time durations include from about 1 hour to about 24 hours.
- a secondary homogenization at reduced temperature of this type may be useful for controlling and/or improving a surface quality or characteristic of the homogenized aluminum alloy product.
- ⁇ -phase intermetallic particles may take up silicon atoms and be transformed into ⁇ -phase particles, at least in part, which may reduce the sizes of any residual ⁇ -phase intermetallic particles.
- an average size of ⁇ -phase intermetallic particles may decrease during homogenization or soaking.
- a number density of ⁇ -phase intermetallic particles may decrease during homogenization or soaking.
- an amount of ⁇ -phase intermetallic particles are transformed into ⁇ -phase intermetallic particles during homogenization or soaking, such as from about 30% to about 100%.
- a number density of ⁇ -phase intermetallic particles may increase during homogenization or soaking.
- Number density ratios of ⁇ -phase intermetallic particles to ⁇ -phase intermetallic particles of from about 2 to about 1000 may be achieved by the long duration homogenization processes described herein. As cast, however, number density ratios of ⁇ -phase intermetallic particles to ⁇ -phase intermetallic particles may be from about 0.3 to about 3 for example.
- Aluminum alloys used for the methods and products described herein may correspond to recycled materials, such as recycled beverage containers.
- source materials such as recycled beverage containers may be melted to prepare a molten aluminum alloy.
- beverage containers tend to include 3xxx series manganese containing aluminum alloys (e.g., AA3104) and 5xxx series magnesium containing aluminum alloys (e.g., AA5182), this source material may be useful for preparing new aluminum alloy products for making new beverage containers.
- a silicon to iron ratio e.g., wt. % ratio
- an additional source of silicon may be used.
- other silicon containing alloys may be added to the molten aluminum, such as a 4xxx series aluminum alloy or a 6xxx series aluminum alloy.
- these sources of supplemental silicon may correspond to recycled aluminum alloy materials.
- Non-limiting exemplary AA4xxx series alloys for use in the methods described herein can include AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, or AA4147.
- Non-limiting exemplary AA6xxx series alloys for use in the methods described herein can include AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA6016, AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027, AA60
- invention As used herein, the terms “invention,” “the invention,” “this invention,” and “the present invention” are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below.
- alloys identified by AA numbers and other related designations such as “series” or “3xxx.”
- series International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys” or “Registration Record of Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot,” both published by The Aluminum Association.
- a plate generally has a thickness of greater than about 15 mm.
- a plate may refer to an aluminum alloy 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.
- a shate (also referred to as a sheet plate) generally has a thickness of from about 4 mm to about 15 mm.
- a shate may have a thickness of about 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, or 15 mm.
- a sheet generally refers to an aluminum alloy product having a thickness of less than about 4 mm.
- 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).
- cast metal product 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.
- room temperature can include a temperature of from about 15° C. to about 30° C., for example about 15° C., 16° C., 17° C., 18° C., 19° C., 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., or 30° C.
- ambient conditions can include temperatures of about room temperature, relative humidity of from about 20% to about 100%, and barometric pressure of from about 975 millibar (mbar) to about 4050 mbar.
- relative humidity can be about 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, or anywhere in between.
- barometric pressure can be about 975 mbar, 980 mbar, 985 mbar, 990 mbar, 995 mbar, 1000 mbar, 1005 mbar, 1010 mbar, 1015 mbar, 1020 mbar, 1025 mbar, 1030 mbar, 1035 mbar, 1040 mbar, 1045 mbar, 4050 mbar, or anywhere in between.
- aspects of the present disclosure relate to aluminum alloy products and methods of making aluminum alloy products that have favorable particle size and inter-particle spacing for improved formability.
- the disclosed aluminum alloy products may have an elemental composition that allows for generation of favorable particle sizes while maintaining inter-particle spacing at a level sufficient to reduce crack formation and propagation.
- the size of included particles such as intermetallic particles, may be reduced.
- the particle density may increase and the inter-particle spacing may decrease.
- the disclosed methods, techniques and products overcome this characteristic by controlling the inter-particle spacing and particle size to a level which minimizes or reduces crack susceptibility and crack propagation, resulting in a product with improved formability characteristics.
- FIG. 1 provides a graph 100 that illustrates the relationship between average particle size and formability.
- Line 110 corresponds to a theoretical approach to improving formability.
- the theoretical approach depicted by line 110 may illustrate the conventional approach to improving formability by reducing particle size.
- As shown by line 110 as particle size increases the formability of the aluminum alloy product should decrease. Conversely, as particle size decreases, theoretically, formability should increase.
- Such a relationship does not hold true in practice when the overall composition of the aluminum alloy product is held constant. For example, when the average particle size decreases at fixed composition, the quantity and number density must increase, as large particles are broken down into more particles of smaller size.
- Line 120 shows that, in practice, the relationship between particle size and product formability may not be linear.
- the relationship between particle size and product formability may be non-linear, and reflect an optimal formability character at a midrange particle size. Following line 120 starting from the origin, as particle size increases, formability may increase as well within an initial range of particle size. However, once the particle size reaches a certain point, the formability of the product may begin to decrease again.
- the relationship of formability and particle size illustrated by line 120 may be representative of how both particle size and inter-particle spacing impact the formability of an aluminum alloy product.
- a reduction in particle size may result in an increase of particle density within a set volume of aluminum alloy when the composition remains fixed.
- An increased density may mean that the particles are positioned closer to each other, or, stated another way, the inter-particle spacing between particles may be reduced.
- Small inter-particle spacing may be detrimental to formability because the shorter the inter-particle spacing, the more susceptible the aluminum alloy may be to crack propagation, as it may be easier (i.e., require less force) for a crack to propagate from one particle to the next particle to the next particle, and so on.
- inter-particle spacing may necessitate larger particle sizes when the composition is fixed (i.e., when the total volume or mass of the particles is held constant), resulting in formation of larger particles and a reduction in the number density of the particles. While an increase in inter-particle spacing may require more energy or force for a crack to propagate from particle to particle, reducing cracking susceptibility to some extent, the resulting larger particles may still act as crack initiation or weak points. As previously noted, larger particles tend to form voids within the aluminum alloy material which can concentrate deformation forces when the aluminum alloy product is under stress or strain.
- FIGS. 2 A- 2 D provide schematic illustrations of an aluminum alloy sample, depicting how smaller particle sizes may detrimentally affect the formability of an aluminum alloy.
- FIG. 2 A an aluminum alloy 210 is illustrated.
- Aluminum alloy 210 includes a plurality of particles 220 .
- Particles 220 may include various types of particles.
- the plurality of particles 220 may include one or more of constituent particles, intermetallic particles, oxides, precipitate or hardening particles.
- particles 220 may include iron-containing particles and/or manganese dispersoids.
- Particles 220 may include one or more intermetallic particles.
- particles 220 may include ⁇ -phase intermetallic particles and ⁇ -phase intermetallic particles.
- Aluminum alloy 210 may have a higher proportion of ⁇ -phase intermetallic particles than ⁇ -phase intermetallic particles, which may correspond to a low average particle size, since ⁇ -phase intermetallic particles may tend to be smaller and less blocky than ⁇ -phase intermetallic particles.
- the iron-containing particles may account for from 1% to 4% of the total volume of the aluminum alloy.
- the iron-containing particles may account for 1% to 2%, from 1% to 3%, from 2% to 3%, from 2% to 4%, or from 3% to 4% of the total volume of the aluminum alloy.
- the iron-containing particles may have a diameter from 1 ⁇ m to 40 ⁇ m, such as from 2 ⁇ m to 40 ⁇ m, 5 ⁇ m to 40 ⁇ m, 7 ⁇ m to 40 ⁇ m, 10 ⁇ m to 40 ⁇ m, 15 ⁇ m to 40 ⁇ m, 20 ⁇ m to 40 ⁇ m, 25 ⁇ m to 40 ⁇ m, 30 ⁇ m to 40 ⁇ m, or 35 ⁇ m to 40 ⁇ m.
- the reference to particle diameters for the iron-containing particles may be for the majority of the iron-containing particles.
- a description that the iron-containing particles have a diameter of from 1 ⁇ m to 40 ⁇ m may mean that the majority (i.e., greater than 50%) of the iron-containing particles have a diameter of 1 ⁇ m to 40 ⁇ m or that 80% of the of the iron-containing particles have a diameter of 1 ⁇ m to 40 ⁇ m.
- force 230 is shown applied to aluminum alloy 210 .
- Force 230 may exemplify forces commonly applied during a manufacturing process or during use of a product produced from aluminum alloy 210 .
- the aluminum alloy 210 may be placed under stress during a drawing process, a rolling process, a stamping process, or the like.
- force 230 may represent forces applied after manufacturing, such as directly to an aluminum alloy product or article prepared from aluminum alloy 210 .
- Force 230 may cause cracks 240 to initiate around particles 220 and propagate through aluminum alloy 210 , as illustrated in FIG. 2 C .
- particles 220 may act as weak points or force concentration points within aluminum alloy 210 . While larger particles tend to form larger weak points, smaller particles may also act as weak points by forming voids or concentrating deformation forces when force 230 is applied.
- the interface between the particles and the surrounding alloy may act as weak points, for example. Differences in hardness, porosity, ductility, and brittleness may all affect the formation of a weak point around particles 220 .
- Inter-particle spacing 225 may correspond to the average or shortest distance between two particles. As noted above, in some embodiments, inter-particle spacing 225 may directly correlate to particle density if the volume fraction of particles 220 remains the same. For example, as the density of particles increases, inter-particle spacing 225 may decrease. Conversely, as the density of particles decreases, inter-particle spacing 225 may increase.
- FIGS. 2 C and 2 D may illustrate how a decrease in inter-particle spacing 225 may be detrimental to formability.
- inter-particle spacing 225 becomes too small, cracks 240 may easily propagate between particles 220 .
- propagation of cracks 240 may follow a lowest energy path.
- cracks 240 may propagate to the next closest weak point, such as particle 220 , within aluminum alloy 210 .
- inter-particle spacing 225 is lowered, then it may take less energy for crack 240 to propagate from one particle to the next. Less energy may correspond to less material for crack 240 to move through.
- inter-particle spacing 225 is higher, more energy may be required for crack 240 to propagate to the next weak point because there is more material between the crack initiation point and the imperfection.
- cracks 240 may easily propagate to nearby particles 220 . This may result in a domino-effect of crack propagation and eventually lead to complete fracturing or shearing 250 of aluminum alloy 210 , as depicted at FIG. 2 D . Fracturing or shearing 250 may result in breakage or where large pieces of aluminum alloy 210 separate from the bulk of aluminum alloy 210 . Fracturing 250 may impact the integrity and strength of aluminum alloy 210 .
- FIG. 3 provides an optical micrograph image 300 of a crack 340 propagating between a large imperfection 350 and particle 320 within an aluminum alloy.
- the aluminum alloy depicted in FIG. 3 may correspond to an aluminum alloy having smaller particle sizes and an overall small average inter-particle spacing 325 .
- imperfection 350 may be a void, crack or crack initiation point, weak point, or another particle within the aluminum alloy.
- crack 340 may propagate between imperfection 350 and the next closest particle 320 .
- An additional imperfection 352 may be present or form around particle 320 .
- imperfection 352 may act as a weak point.
- Crack 340 may propagate to particle 320 along a low energy path between imperfection 350 and imperfection 352 . When further stress or force is applied, cracks may become larger and spur further propagation.
- the aluminum alloys and related products discussed herein may achieve favorable inter-particle spacing while maintaining favorable particle size.
- the aluminum alloys as provided herein may have an inter-particle spacing from about 1 ⁇ m to about 25 ⁇ m.
- the inter-particle spacing may be from about 1 ⁇ m to about 25 ⁇ m, from 1 ⁇ m to 2 ⁇ m, from 1 ⁇ m to 5 ⁇ m, from 1 ⁇ m to 7 ⁇ m, from 1 ⁇ m to 10 ⁇ m, from 1 ⁇ m to 12 ⁇ m, from 1 ⁇ m to 15 ⁇ m, from 1 ⁇ m to 17 ⁇ m, from 1 ⁇ m to 20 ⁇ m, from 1 ⁇ m to 22 ⁇ m, from 1 ⁇ m to 25 ⁇ m, from 2 ⁇ m to 5 ⁇ m, from 2 ⁇ m to 7 ⁇ m, from 2 ⁇ m to 10 ⁇ m, from 2 ⁇ m to 12 ⁇ m, from 2 ⁇ m to 15 ⁇ m, from 2 ⁇ m to 17
- inter-particle spacing may be described with relation to the majority (greater than 50%) of the plurality of particles. For example, 80 percent or more of the plurality of particles within an aluminum alloy may have inter-particle spacing from 1 ⁇ m to 25 ⁇ m.
- a particle density may be represented as a number of particles per unit volume (e.g., particles per ⁇ m 3 ) or as a number of particles per unit area (e.g., particles per ⁇ m 2 ).
- Use of particle density as a number of particles per unit area may be useful for quickly characterizing the number of particles in an aluminum alloy or product by obtaining a scanning electron micrograph image or an optical micrograph image of a region of the aluminum alloy or product and counting the number of particles in the image, which may represent a 2-dimensional slice of the aluminum alloy or product.
- multiple images can be obtained to provide a representative sample of the aluminum alloy or product, such as for counting particles or establishing a particle density.
- the aluminum alloys may have or be controlled to have a particle density of 5 to 30,000 particles per ⁇ m 2 (e.g., 8 to 1,400 particles per ⁇ m 2 ) while maintaining particle diameters from 100 nm to 50 ⁇ m.
- particle diameters may be used to quantify particle size.
- the particle density and/or diameters are characterized by obtaining scanning electron micrograph image(s) or optical micrograph image(s) of a region or regions of the aluminum alloy or product and counting or evaluating the particles in the image(s).
- particle density may be from 5 to 30,000 particles per ⁇ m 2 , such as from 10 to 25,000, from 10 to 20,000, from 10 to 15,000, from 10 to 10,000, from 10 to 9,500, from 10 to 9,000, from 10 to 8,500, from 10 to 8,000, from 10 to 7,500, from 10 to 7,000, from 10 to 6,500, from 10 to 6,000, from 10 to 5,500, from 10 to 5,000, from 10 to 4,500, from 10 to 4,000, from 10 to 3,500, from 10 to 3,000, from 10 to 2,500, from 10 to 2,000, from 10 to 1,500, from 10 to 1,000, from 10 to 950, from 10 to 900, from 10 to 850, from 10 to 800, from 10 to 750, from 10 to 700, from 10 to 650, from 10 to 600, from 10 to 550, from 10 to 500, from 10 to 450, from 10 to 400, from 10 to 350, from 10 to 300, from 10 to 250, from 10 to 200, from 10 to 150, from 10 to 100, from 10 to 75,
- example particle diameters may range from 100 nm to 100 ⁇ m.
- the particle diameters may range from 150 nm to 100 ⁇ m, from 200 nm to 100 ⁇ m, from 300 nm to 100 ⁇ m, from 400 nm to 100 ⁇ m, from 500 nm to 100 ⁇ m, from 600 nm to 100 ⁇ m, from 700 nm to 100 ⁇ m, from 800 nm to 100 ⁇ m, from 1 ⁇ m to 100 ⁇ m, from 5 ⁇ m to 100 ⁇ m, from 10 ⁇ m to 100 ⁇ m , from 15 ⁇ m to 100 ⁇ m, from 25 ⁇ m to 100 ⁇ m, from 50 ⁇ m to 100 ⁇ m, from 75 ⁇ m to 100 ⁇ m, from 150 nm to 75 ⁇ m, from 200 nm to 75 ⁇ m, from 300 nm to 75 ⁇ m, from 400 nm to 75 ⁇ m, from 500 nm.
- diameter ranges may optionally represent the diameters of 80 percent (or more) of the particles, meaning that although some particles may have diameters outside the stated range, at least 80 percent of the particles will have diameters within the stated range.
- the diameter ranges may represent the diameter of 25 percent (or more) of the particles, 30 percent (or more) of the particles, 35 percent (or more) of the particles, 40 percent (or more) of the particles, 45 percent (or more) of the particles, 50 percent (or more) of the particles, 55 percent (or more) of the particles, 60 percent (or more) of the particles, 65 percent (or more) of the particles, 70 percent (or more) of the particles, 75 percent (or more) of the particles, 80 percent (or more) of the particles, 85 percent (or more) of the particles, 90 percent (or more) of the particles, 95 percent (or more) of the particles, 98 percent (or more) of the particles, or 100 percent (or more) of the particles.
- conditions during casting and homogenization may be adjusted to control the size and density of particle generation.
- the composition of the aluminum alloy may control particle generation.
- adjustment of the composition prior to casting may be useful to generate a favorable amount of intermetallic particles and/or to control particle diameters and inter-particle spacing.
- aluminum alloys containing iron and manganese may generate intermetallic particles comprising aluminum and one or more of iron or manganese, which may be referred to herein as Al-(Fe, Mn) intermetallic particles or ⁇ -phase intermetallic particles, within the cast aluminum alloy product.
- intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese also referred to herein as Al-(Fe, Mn)-Si intermetallic particles or ⁇ -phase intermetallic particles
- Exemplary ⁇ -phase and ⁇ -phase intermetallic particles may include Al 15 (Fe,Mn) 3 Si 2 and Al 6 (Fe,Mn), respectively.
- many aluminum alloys may include such intermetallic particles upon casting.
- intermetallic particle types exhibits different properties and contributes in different ways to the structure of the aluminum alloy.
- ⁇ -phase particles tend to be larger and more blocky or geometric than ⁇ -phase particles, while ⁇ -phase particles are harder and tend to be smaller than ⁇ -phase particles, in general.
- intermetallic particles may be broken, impacting their size, inter-particle spacing, and density, for example.
- components may diffuse in and out of intermetallic particles, changing their composition, structure, and/or size.
- Specific aluminum alloys useful with the disclosed methods and aluminum alloy products may include those containing aluminum, iron, magnesium, manganese, and silicon. By using an increased ratio of iron to silicon, the disclosed aluminum alloy products may preferentially generate ⁇ -phase intermetallic particles during processing or may convert ⁇ -phase intermetallic particles to ⁇ -phase intermetallic particles during a homogenization process.
- aluminum alloys useful with the methods and products described herein may have a ratio of a wt. % of iron to a wt. % of silicon of from 0.5 to 5.0.
- an aluminum alloy may have a ratio of a wt. % of iron to a wt.
- % of silicon from 0 such as from 0.5 to 5, from 0.5 to 4.7, from 0.5 to 4.6, from 0.5 to 4.5, from 0.5 to 4.25, from 0.5 to 4.0, from 0.5 to 3.75, from 0.5 to 3.5, from 0.5 to 3.25, from 0.5 to 3.0, from 0.5 to 2.75, from 0.5 to 2.5, from 0.5 to 2.0, from 0.5 to 1.8, from 0.5 to 1.5, from 0.5 to 1.1, from 0.5 to 1.0, from 1.0 to 5.0, from 1.0 to 4.7, from 1.0 to 4.6, from 1.0 to 4.5, from 1.0 to 4.25, from 1.0 to 4.0, from 1.0 to 3.75, from 1.0 to 3.5, from 1.0 to 3.25, from 1.0 to 3.0, from 1.0 to 2.75, from 1.0 to 2.5, from 1.0 to 2.0, from 1.0 to 1.8, from 1.0 to 1.5, from 1.0 to 1.1, from 1.1 to 5.0, from 1.1 to 4.7, from 1.0 to 4.6, from
- the ratio of ⁇ -phase intermetallic particles to a ⁇ -phase intermetallic particles may be based on the density of intermetallic particles instead of the volume fraction.
- a favorable ratio of ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density may be from 0.2 to 1,000.
- the ratio of ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density may be from 0.2 to 1,000, 0.2 to 750, 0.25 to 500, 0.25 to 100, 0.25 to 50, 0.3 to 25, 0.3 to 10, or 0.3 to 3.
- Tables 1-3 provide alloy compositions (wt. %) for aluminum alloys according to some embodiments.
- the provided compositions may be useful in generating aluminum alloy products having favorable inter-particle spacing while maintaining favorable particle size.
- there may be a balance between inter-particle spacing and particle size that provides for improved product formability.
- the following compositions may provide for aluminum alloys and aluminum alloy products having improved formability and permit use of high amounts of recycled source content.
- an aluminum alloy as described herein may have the following elemental composition as provided in Table 1.
- the aluminum alloy may have the following elemental composition as provided in Table 2.
- the alloy may have the following elemental composition as provided in Table 3.
- the alloy may have the following elemental composition as provided in Table 4.
- the alloys described herein may also include iron (Fe) in an amount of from 0.1% to 1.0% (e.g., from 0.20% to 0.8% or from 0.3% to 0.7%) based on the total weight of the alloy.
- the alloy may 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%, 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%, 0.57%
- the alloys described herein may include silicon (Si) in an amount of from 0.05% to 0.80% (e.g., from 0.1% to 0.7% or from 0.15% to 0.5%) based on the total weight of the alloy.
- the alloy may include 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%
- the alloys described herein may include manganese (Mn) in an amount of from 0.2% to 2.0% (e.g., from 0.6% to 1.0% or from 0.8% to 1.4%) based on the total weight of the alloy.
- the alloy may include 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%
- the alloys described herein may include magnesium (Mg) in an amount of from 0.2% to 2.0% (e.g., from 0.7% to 1.0% or from 0.9% to 1.1%) based on the total weight of the alloy.
- the alloy may include 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%,
- the alloys described may include copper (Cu) in an amount of up to 0.5% (e.g., from 0% to 0.25% or from 0.1% to 0.2%) based on the total weight of the alloy.
- the alloy may include 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 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%, or 0.50% copper.
- copper is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- the alloys described herein may include zinc (Zn) in an amount of up to 0.50% (e.g., from 0% to 0.2% or from 0% to 1.5%) based on the total weight of the alloy.
- the alloy may include 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 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%, or 0.50% zinc.
- zinc is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- the alloys described herein may include titanium (Ti) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy.
- Ti titanium
- the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011% 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041% 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.1% titanium. In some cases, titanium may not be present, 0.
- the alloys described herein may include chromium (Cr) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy.
- Cr chromium
- the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011% 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021% 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%,0.03%, 0.031% 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041% 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% chromium. In some cases, chromium. In
- the alloys described herein may include zirconium (Zr) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy.
- Zr zirconium
- the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041%, 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% Zr.
- the alloys may include zirconium in an amount less than 0.05% (e.g., 0.04%, 0.03%, 0.02%, or 0.01%) based on the total weight of the alloy. In some cases, zirconium may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- the alloys described herein may include vanadium (V) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy.
- V vanadium
- the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041%, 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% vanadium.
- the alloys described herein may include one or more rare earth elements (i.e., one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu)) in an amount of up to 0.10% (e.g., from 0.01% to 0.10%, from 0.01% to 0.05%, or from 0.03% to 0.05%) based on the total weight of the alloy.
- rare earth elements i.e., one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce
- the alloy may include 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.10% of one or more of the rare earth elements. All are expressed in wt. %.
- the alloys described herein may include one or more of molybdenum (Mo), niobium (Nb), beryllium (Be), boron (B), cobalt (Co), Tin (Sn), strontium (Sr), vanadium (V), indium (In), hafnium (Hf), silver (Ag), and nickel (Ni) in an amount of up to 0.20% (e.g., from 0.01% to 0.20% or from 0.05% to 0.15%) based on the total weight of the alloy.
- the alloy may include 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% of one or more of molybdenum (Mo), niobium (Nb), beryllium (Be), boron (B), cobalt (Co), tin (Sn), strontium (Sr), vanadium (V), indium (In), hafnium (Hf), silver (Ag), and nickel (Ni). All are expressed in wt. %.
- the alloy compositions described herein may 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.
- impurities may include, but are not limited to gallium (Ga), calcium (Ca), bismuth (Bi), sodium (Na), lead (Pb), or combinations thereof.
- gallium, calcium, bismuth, sodium, or lead 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.
- the sum of all impurities may not exceed 0.15% (e.g., 0.10%). All expressed in wt. %.
- the remaining percentage of the alloy may be aluminum.
- Incidental elements such as grain refiners and deoxidizers, or other additives may be present in the aluminum alloys and aluminum alloy products and may add other characteristics on their own without departing from or significantly altering the aluminum alloys and products described herein or the characteristics of the aluminum alloys or products described herein.
- Unavoidable impurities, including materials or elements may be present in the alloy in minor amounts due to inherent properties of aluminum or leaching from contact with processing equipment.
- Some impurities typically found in aluminum include iron and silicon.
- iron and silicon may not be indicated as impurities.
- the amounts of iron and silicon may be actively controlled to effect certain properties in the alloy.
- FIG. 4 provides an overview of an example method of making an aluminum alloy product.
- the method of FIG. 4 begins at step 405 , where an aluminum alloy 406 may be cast to create a cast aluminum alloy product 407 , such as an ingot or other cast product.
- the cast aluminum alloy product 407 may be homogenized to generate a homogenized aluminum alloy product 411 .
- the homogenized aluminum alloy product 411 may be subjected to one or more hot rolling passes and/or one or more cold rolling passes to form a rolled aluminum alloy product 412 , which may correspond to an aluminum alloy article, such as an aluminum alloy plate, an aluminum alloy shate, or an aluminum alloy sheet.
- the rolled aluminum alloy product 412 may be subjected to one or more forming or stamping processes to form an aluminum alloy article.
- the aluminum alloys described herein may be cast using any suitable casting method.
- the casting process may include a direct chill (DC) casting process or a continuous casting (CC) process.
- FIG. 4 may depict a schematic illustration of a DC casting process at 405 .
- a continuous casting system may be used instead, which may 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 may have an end opening from which molten metal can exit the molten metal injector and be injected into the casting cavity.
- a cast aluminum alloy product such as a cast ingot or other cast product, may be processed by any suitable means.
- the processing steps may be used to prepare sheets.
- Example processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, annealing, solution heat treatment, and pre-aging.
- FIG. 5 provides a plot showing temperature of a cast aluminum alloy product according to the present disclosure as a function of time during a homogenization process according to some examples.
- the cast aluminum alloy product may be heated to a homogenization temperature (HTi). Heating for the homogenization step may take place from ambient conditions, room temperature (RT as shown in FIG. 5 ), or a higher temperature, and may occur at any suitable heating rate. In some embodiments, a heating rate of from about 10° C./hour to about 100° C./hour may be used.
- HTi homogenization temperature
- Example heating rates may be from 20° C./hour to 90° C./hour, from 30° C./hour to 80° C./hour, from 40° C./hour to 70° C./hour, from 50° C./hour to 60° C./hour, about 10° C./hour, 20° C./hour, 30° C./hour, 40° C./hour, 50° C./hour, 60° C./hour, 70° C./hour, 80° C./hour, 90° C./hour, or 100° C./hour.
- the time duration for the heating process is illustrated in FIG. 5 as t R , running from time -t R to time 0.
- the aluminum alloy product may be heated to a homogenization temperature (HTi) ranging from about 500° C. to about 650° C.
- Example homogenization temperatures (HTi) include from about 550° C. to about 615° C., from about 570° C. to about 610° C., from about 580° C. to about 605° C., from about 590° C.
- higher homogenization temperatures may be useful for controlling a size, inter-particle spacing, distribution, concentration, and/or composition of intermetallic particles present in the aluminum alloy, so homogenization temperatures of from about 570° C. to about 620° C. may be desirable. In some embodiments, a homogenization temperature from about 585° C. to about 615° C. may be desirable. Optionally, the homogenization temperature may be within 25° C. of a solidus temperature of the aluminum alloy.
- the heated cast aluminum alloy product may then be allowed to soak (i.e., held at the indicated homogenization temperature) for a period of time.
- the time duration for soaking shown in FIG. 5 is t 1 , which runs from time 0 to time t 1 .
- homogenization may take place in an inert atmosphere, a reduced oxygen atmosphere, an oxygen-free atmosphere, or in air.
- the total time for the homogenization step, including the heating and soaking phases may be up to or greater than 12 hours or 32 hours.
- the soaking phase can be longer, even up to 36 hours. Long duration soaking of over 12 hours or over 24 hours may be useful, in embodiments, for controlling a size, inter-particle spacing, distribution, concentration, density, and/or composition of intermetallic particles present in the aluminum alloy.
- the homogenized aluminum alloy product may have its temperature reduced, such as by an active or passive cooling process.
- the homogenized aluminum alloy may have its temperature reduced to room temperature. Cooling may take place at any suitable cooling rate.
- Example cooling rates include heating rates of from about 10° C./hour to about 50° C./hour, such as about 10° C./hour, 20° C./hour, 30° C./hour, 40° C./hour, or 50° C./hour.
- the homogenized aluminum alloy product may proceed directly to hot rolling without being cooled to room temperature.
- the homogenization step includes multiple processes. As illustrated in FIG. 5 , the homogenization step optionally includes heating the product to a first homogenization temperature (HTi), soaking at or about the first homogenization temperature for a first time duration (ti), followed by cooling to a second homogenization temperature (HT 2 ), and soaking at or about the second homogenization temperature for a second time duration, shown in FIG. 5 as t 2 -t 1 .
- the aluminum alloy product may be cooled after the first soak to a second homogenization temperature of from 500° C.
- the aluminum alloy product may be held at the second homogenization temperature for a second time duration of from about 1 hours to about 24 hours.
- a hot rolling step may be performed.
- hot rolling may occur immediately after homogenization (i.e., without cooling to room temperature).
- the homogenized product may be allowed to cool to a temperature of from 100° C. to 500° C.
- the homogenized product may be allowed to cool to a temperature of from 100° C. to 500° C., from 250° C. to 450° C., from 300° C. to 450° C., from 325° C. to 425° C. or from 350° C. to 400° C.
- the product may then be hot rolled at a temperature between 200° C. to 600° C.
- a hot rolled plate, a hot rolled shate, or a hot rolled sheet having a gauge from 0.5 mm to 200 mm e.g., 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or anywhere in between).
- 0.5 mm to 200 mm e.g., 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm,
- the homogenized product may be hot rolled at a temperature to a thickness from 1 mm to 8 mm.
- temperatures and other operating parameters may be controlled so that the exit temperature of the hot rolled product upon exit from the hot rolling mill is no more than about 500° C., no more than about 450° C., no more than about 300° C., or no more than about 200° C.
- the exit temperature of the hot rolled product may be from 100° C. to 500° C., or from 200° C. to 400° C.
- cast, homogenized, or hot rolled products may be cold rolled using cold rolling mills and technology into a sheet.
- the cold rolled sheet may have a gauge from about 0.10 mm to about 0.50 mm, from about 0.15 mm to about 0.3 mm, from about 0.5 mm to about 10 mm or from about 0.7 mm to about 6.5 mm.
- the cold rolled sheet may have a gauge of about 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, 5.5 mm, 6.0 mm, 6.5 mm, 7.0 mm, 7.5 mm, 8.0 mm, 8.5 mm, 9.0 mm, 9.5 mm, or 10.0 mm .
- the cold rolling may be performed to result in a final gauge thickness that represents a gauge reduction of up to about 95% (e.g., up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 85%, up to 90%, or up to 95% reduction).
- temperatures and other operating parameters may be controlled so that the exit temperature of the cold rolled product upon exit from the cold rolling mill is no more than about 300° C., no more than about 250° C., no more than about 200° C., or no more than about 100° C.
- the exit temperature of the cold rolled product may be from 50° C. to 250° C. or from 100° C. to 200° C.
- an interannealing step may be performed after the cold rolling step or in between multiple cold rolling steps.
- the interannealing step may be performed at a temperature of from about 300° C. to about 450° C. (e.g., about 310° C., 320° C., 330° C., 340° C., 350° C., 360° C., 370° C., 380° C., 390° C., 400° C., 410° C., 420° C., 430° C., 440° C., or 450° C.).
- the interannealing step comprises multiple processes.
- the interannealing step may include heating the plate, shate, or sheet to a first temperature for a first period of time followed by heating to a second temperature for a second period of time.
- the plate, shate or sheet may be heated to about 410° C. for about 1 hour and then heated to about 330° C. for about 2 hours.
- the cast, homogenized, or hot rolled alloy products described herein may also be used to make products in the form of plates or other suitable products.
- plates including the products as described herein can be prepared by processing an ingot in a homogenization step or casting a product in a continuous caster followed by homogenization and subsequently hot rolling the homogenized product.
- the homogenized product can be hot rolled to a 200 mm thick gauge or less (e.g., from about 10 mm to about 200 mm).
- a homogenized aluminum alloy product can be hot rolled to a plate having a final gauge thickness of about 10 mm to about 175 mm, about 15 mm to about 150 mm, about 20 mm to about 125 mm, about 25 mm to about 100 mm, about 30 mm to about 75 mm, or about 35 mm to about 50 mm.
- Monolithic as well as non-monolithic, such as roll-bonded materials, cladded alloys, clad layers, composite materials, such as but not limited to carbon fiber-containing materials, or various other materials are also useful with the methods and aluminum alloys and aluminum alloy products described herein.
- FIG. 6 provides a method 600 of making an aluminum alloy having favorable particle density and inter-particle spacing between the particles according to an embodiment as disclosed herein.
- a cast aluminum alloy product may be prepared.
- a cast aluminum alloy product may comprise an aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, for example.
- the cast aluminum alloy product may include an aluminum alloy having an elemental composition as provided herein, specifically those provided at Tables 1-3.
- Preparing the cast aluminum alloy product may include preparing a molten aluminum alloy and casting the molten aluminum alloy.
- the source aluminum alloy(s) for the aluminum alloy products prepared according to the methods and techniques described herein may correspond to the same series aluminum alloy or a mixture of different series aluminum alloys.
- preparing the cast aluminum alloy product may comprise preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy.
- preparing the molten 3xxx series aluminum alloy may comprise melting both a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- one or more of the source aluminum alloys may be from a recycled source content.
- aluminum alloys including a higher percentage of iron may be useful for achieving a target iron to silicon ratio.
- preparing the molten aluminum alloy optionally may further comprise melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy along with a 3xxx series source aluminum alloy and/or a 5xxx series source aluminum alloy.
- the cast aluminum alloy product may be homogenized.
- homogenizing may include heating the cast aluminum alloy product to a homogenization temperature, such as a homogenization temperature that is between 500° C. and 650° C., and soaking the cast aluminum alloy product at the homogenization temperature for a time duration between 0.1 hours and 36 hours, for example.
- a structure of the aluminum alloy may change.
- silicon from the aluminum alloy may diffuse into and transform at least a fraction of the ⁇ -phase intermetallic particles into ⁇ -phase intermetallic particles.
- iron from the aluminum alloy may diffuse into and transform at least a fraction of the ⁇ -phase intermetallic particles into ⁇ -phase intermetallic particles.
- iron may diffuse out of the ⁇ -phase intermetallic particles and be optionally replaced by manganese.
- iron may diffuse out of the ⁇ -phase intermetallic particles and into dispersoids present within the cast aluminum alloy product.
- the aluminum alloy includes a 3xxx series aluminum alloy
- silicon from the 3xxx series aluminum alloy may diffuse into and transform at least a fraction of the ⁇ -phase intermetallic particles into ⁇ -phase intermetallic particles.
- iron diffuses out of the ⁇ -phase intermetallic particles and is replaced by manganese.
- the iron when the iron diffuses out of the ⁇ -phase intermetallic particles, the iron may combine with dispersoids present within the cast aluminum alloy product to form ⁇ -phase intermetallic particles.
- the dispersoids may include manganese.
- an average size of the ⁇ phase intermetallic particles may increase or decrease.
- an average size of the ⁇ phase intermetallic particles may decrease as compared to an average size of the ⁇ -phase intermetallic particles prior to soaking.
- a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product may increase or decrease.
- a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density in the cast aluminum alloy product is between 0.3 and 3.
- a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density in the homogenized aluminum alloy product may be from 0.2 to 1000 or more (e.g., from 2 to 1000).
- an amount of the ⁇ -phase intermetallic particles may be transformed into ⁇ -phase intermetallic particles during homogenizing, such as 30% or more, 40% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 80% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, 99.5% or more or up to 100%.
- a majority of the ⁇ -phase intermetallic particles are transformed into ⁇ -phase intermetallic particles during homogenizing.
- an amount of the ⁇ -phase intermetallic particles may be transformed into ⁇ -phase intermetallic particles during homogenizing, in particular, during soaking. For example, during soaking, approximately 30% to 100% of the ⁇ -phase intermetallic particles may be transformed into ⁇ -phase intermetallic particles.
- multiple homogenization steps may be useful.
- a secondary lower temperature homogenization after an initial higher temperature, long duration homogenization may be useful for preparing an aluminum alloy product, such as for rolling or other processing.
- a multiple-step homogenization process may include reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature, and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration, such as a second time duration that is shorter than the time duration of the initial long-duration soak.
- soaking the homogenized aluminum alloy product at the second homogenization temperature may control a surface quality or characteristic of the homogenized aluminum alloy product.
- soaking the homogenized aluminum alloy product at the second homogenization temperature may bring a temperature of the homogenized aluminum alloy product to a temperature sufficient for a rolling process.
- the method 600 may optionally include subjecting the homogenized rolled aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- the homogenized rolled aluminum alloy product may be subjected to one or more hot rolling processes at block 642 .
- the homogenized rolled aluminum alloy product may also be subjected to one or more cold rolling processes at block 644 .
- intermetallic particles may be broken, impacting their size, distribution, and number density, for example.
- Hot rolling the rolled aluminum alloy product at relatively high temperatures may encounter difficulties due to roll sticking and bite refusal. This may also result in grain boundary separation and surface tearing, which can enhance oxidation at the surface. Since the affinity of oxide formation is higher at higher temperatures, at least in part due to faster diffusion of solute elements (e.g., magnesium (Mg), silicon (Si), etc.,) on the surface, the new fresh surface that forms from tearing may oxidize promptly and often results in a non-uniform surface with an undesirable oxide layer.
- solute elements e.g., magnesium (Mg), silicon (Si), etc.
- lowering the hot rolling exit temperature such as to a temperature below about 550° C., for example from about 100° C. to 500° C., may give more control on roll bite with higher friction and reduce the tendency of the surface to stick, tear, and oxidize.
- the reduced diffusivity of solute elements at lower temperatures can result in a more uniform surface layer than at higher temperatures.
- controlling the cold rolling exit temperature may also allow for an improved aluminum alloy product.
- Exit temperature from a cold rolling process from about 100° C. to 200° C. may allow for the rolled aluminum alloy product to be rolled to a thickness of 0.15 to 0.30 mm without sticking, tearing, or breakage.
- the aluminum alloy products described herein can be used in a variety of applications.
- the aluminum alloy products described herein are useful for beverage container body stock, such as aluminum can body stock or aluminum bottle body stock.
- Aluminum alloy sheets may be subjected to a blanking process in which discs of the aluminum alloy are cut from an aluminum alloy sheet. The discs may be subjected to one or more drawing, ironing, necking or other forming processes to form a suitable beverage container body or preform.
- the disclosed aluminum alloy products can be used to prepare automotive parts, aircraft or railway vehicle panels, architectural panels, building products, and the like.
- cookware, foils, formed containers, bottle caps, and packaging e.g., food packaging
- packaging e.g., food packaging
- the aluminum alloy products and methods described herein can also be used in electronics applications.
- the aluminum alloy products and methods described herein can be used to prepare housings for electronic devices, including mobile phones and tablet computers.
- the aluminum alloy products can be used to prepare housings for the outer casing of mobile phones (e.g., smart phones), tablet bottom chassis, and other portable electronics.
- Table 1 provides alloying solute compositions (wt. %) of two example 3104 aluminum alloys, Alloy A and Alloy B.
- Alloy A is slightly enriched in solute as compared to Alloy B.
- a ratio of silicon to iron in Alloy A is about 0.60, while in Alloy B the ratio is about 0.56.
- the solidus temperatures of the alloys were calculated to be within 2° C. of one another, indicating that the samples are expected to have similar melting and physical properties.
- the solvus temperature for Mg 2 Si for Alloy A was calculated to be slightly higher than for Alloy B.
- Four sample ingots of each of Alloy A and Alloy B were prepared and used to evaluate the effect of different homogenization regimes on intermetallic particles present in the alloys.
- the as-cast samples had a gauge of about 40 mm.
- Samples of Alloy A and two samples of Alloy B were subjected to a heat-to-roll (HTR) processing scheme, where the samples were heated at a slow rate of about 50° C./h to a temperature of about 500° C.
- Other samples of Alloy A and other samples of Alloy B were subjected to a 2-stage (2STG) processing scheme, where the samples were heated at a slow rate of about 50° C./h to a temperature of about 600° C., held at this temperature for about 24 hours, and then cooled to about 560° C., where they were held for about 4 additional hours.
- HTR heat-to-roll
- Scanning electron micrograph (SEM) images under back-scattered electron (BSE) contrast were obtained of cross-sections of samples of the as-cast Alloy A and Alloy B, as well as samples of Alloy A and Alloy B after the HTR or 2STG processing, in order to evaluate the particle distribution and microstructure of the samples. These images are shown in FIG. 8 .
- the images show that, overall, the sizes of the particles in Alloy A are smaller than the particles in Alloy B.
- no changes in the constituent particles were observed for either Alloy A or Alloy B.
- the as-cast and HTR processed samples showed a mix of ⁇ -phase particles and ⁇ -phase particles.
- the 2STG processing only ⁇ -phase particles were observed in the microstructures, with a more fine particle size distribution. In some cases, the 2STG processing transformed the structure to a more porous character.
- samples of Alloy A and Alloy B were subjected to rolling processes.
- samples of the alloys subjected to HTR processing immediately after the HTR processing, samples of Alloy A and Alloy B were subjected to a hot rolling operation to a gauge of about 7.0 mm, recrystallized, and then subjected to a cold rolling operation to a gauge of about 1.0 mm to form hard H19 temper products. Recrystallizing may optionally be achieved by coiling the hot-rolled product and cooling the coil or may be achieved by annealing the hot-rolled product.
- Some of the cold rolled H19 temper product samples of Alloy A and the cold rolled H19 temper product samples of Alloy B were then annealed at 350° C. for 1 hour to generate soft O temper products.
- the hard H19 temper product samples are referred to as A HTR , H19 and B HTR
- H19 and the soft O temper product samples are referred to as A HTR , O and B HTR , O .
- High resolution cross-sectional images of the A HTR , H19 , B HTR , H19 , A 2STG , H19 , and B 2STG , H19 samples were obtained using a field emission gun scanning electron microscope (FEGSEM) to investigate the spatial distribution of dispersoids (e.g., manganese containing dispersoids) in the final gauge samples.
- FEGSEM field emission gun scanning electron microscope
- the obtained images are shown in FIG. 11 , with the dispersoids identified as white spots in the images.
- the dispersoids in the samples subjected to the HTR processing were numerous and very fine.
- the dispersoids in the samples subjected to the 2STG processing were fewer in number density, but also more coarse, again due to the longer and higher temperatures of the 2STG processing, allowing for more mobility and time for iron atoms to be taken up and convert the dispersoids to ⁇ -phase particles and/or for constituent atoms to be taken up into and grow the dispersoids. Slightly larger size dispersoids can be seen in the Alloy A samples as compared to the Alloy B samples, which may be attributable to a slightly higher amount of solute in Alloy A as compared to Alloy B.
- the samples subjected to 2STG processing showed little or none of these particles, and much higher populations of ⁇ -phase particles, indicating that the ⁇ -phase particles may be generated by transforming ⁇ -phase particles during the prolonged homogenization of the 2STG processing.
- the constituent morphology may be more influential than the number density of particles, as there is less energy present at the interface between the particles and the matrix.
- the 2STG processed samples exhibited spheroidical particles than HTR processed samples, which may allow the strains to be more evenly distributed around the particles than in the more needle-shaped particles of the HTR processed samples, which may result in concentration of strain and earlier crack initiation.
- any reference to a series of illustrations is to be understood as a reference to each of those examples disjunctively (e.g., “Illustrations 1-4” is to be understood as “Illustrations 1, 2, 3, or 4”).
- Illustration 1 is an aluminum alloy product comprising: an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of an iron wt. % in the aluminum alloy to a silicon wt. % in the aluminum alloy is from 0.5 to 5.0, and wherein the aluminum alloy includes a plurality of particles including ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese; and wherein the aluminum alloy has a particle density for the plurality of particles of from 5 to 30,000 particles per ⁇ m 2 and wherein the aluminum alloy has an inter-particle spacing for the plurality of particles of from 1 ⁇ m to 25 ⁇ m.
- Illustration 2 is the aluminum alloy product of any previous or subsequent illustration, wherein the plurality of particles has diameters of from 500 nm to 50 ⁇ m.
- Illustration 3 is the aluminum alloy product of any previous or subsequent illustration, wherein the particle density is from 50 to 1,000 particles per ⁇ m 2 .
- Illustration 4 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy is from a recycled source.
- Illustration 5 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.1 wt. % to 1.0 wt. % iron, from 0.05 wt. % to 0.8 wt. % silicon, from 0.2 wt. % to 2.0 wt. % manganese, from 0.2 wt. % to 2.0 wt. % magnesium, up to 0.5 wt. % copper, up to 0.05 wt. % zinc, and aluminum.
- Illustration 6 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises up to 0.15 wt. % impurities.
- Illustration 7 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium, up to 0.10 wt. % chromium, up to 0.10 wt. % zirconium, up to 0.10 wt. % vanadium, and aluminum.
- Illustration 8 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum.
- Illustration 9 is the aluminum alloy product of any previous or subsequent illustration, wherein the ⁇ -phase intermetallic particles comprise from 0.5% to 4.0% by volume of the aluminum alloy, and wherein the ⁇ -phase intermetallic particles comprise from 0% to 2.0% by volume of the aluminum alloy.
- Illustration 10 is the aluminum alloy product of any previous or subsequent illustration, wherein the ⁇ -phase intermetallic particles comprise Al15(Fe,Mn)3Si2, and wherein the ⁇ -phase intermetallic particles comprise Al6(Fe,Mn).
- Illustration 11 is the aluminum alloy product of any previous or subsequent illustration, wherein a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density is from 0.2 to 1,000 or wherein a ratio of a volume % of the ⁇ -phase intermetallic particles to a volume % of the ⁇ -phase intermetallic particles is from 0.6 to 1,000.
- Illustration 12 is the aluminum alloy product of any previous or subsequent illustration, wherein the ratio of the ⁇ -phase intermetallic particle number density to the ⁇ -phase intermetallic particle number density is from 0.3 to 3.
- Illustration 13 is the aluminum alloy product of any previous or subsequent illustration, wherein 80 percent or more of the plurality of particles have an inter-particle spacing from 5 ⁇ m to 15 ⁇ m.
- Illustration 14 is the aluminum alloy product of any previous or subsequent illustration, wherein the plurality of particles comprise iron-containing particles, wherein a majority of the iron-containing particles have a diameter from 1 ⁇ m to 40 ⁇ m.
- Illustration 15 is the aluminum alloy product of any previous or subsequent illustration, wherein the iron-containing particles comprise from 1% to 4% of a total volume of the aluminum alloy.
- Illustration 16 is the aluminum alloy product of any previous or subsequent illustration, further comprising manganese-containing dispersoids, wherein a majority of the manganese-containing dispersoids have a diameter of from 10 nm to 1.5 ⁇ m.
- Illustration 17 is the aluminum alloy product of any previous or subsequent illustration, wherein the manganese-containing dispersoids comprise up to 1% of a total volume of the aluminum alloy.
- Illustration 18 is a method of making an aluminum alloy product, the method comprising: preparing a cast aluminum alloy product comprising an aluminum alloy, wherein the aluminum alloy comprises aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the aluminum alloy to an iron wt. % in the aluminum alloy is from 0.5 to 1.0, and wherein the aluminum alloy includes a plurality of particles including ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product by: heating the cast aluminum alloy product to a homogenization temperature from 500° C.
- the aluminum alloy product has a particle density for the plurality of particles of from 5 to 30,000 particles per ⁇ m 2 and wherein the aluminum alloy product has an inter-particle spacing for the plurality of particles of from 1 ⁇ m to 25 ⁇ m.
- Illustration 19 is the method of any previous or subsequent illustration, wherein the time duration is from 0.5 to 10 hours.
- Illustration 20 is the method of any previous or subsequent illustration, wherein the homogenization temperature is from 570° C. to 620° C.
- Illustration 21 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the aluminum alloy.
- Illustration 22 is the method of any previous or subsequent illustration, wherein, during the soaking, a size of the ⁇ -phase intermetallic particles decreases as compared to a size of the ⁇ -phase intermetallic particles prior to the soaking.
- Illustration 23 is the method of any previous or subsequent illustration, wherein, during the soaking, a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product prior to the soaking.
- Illustration 24 is the method of any previous or subsequent illustration, further comprising subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- Illustration 25 is the method of any previous or subsequent illustration, wherein the one or more rolling processes comprise at least one of a hot rolling process or a cold rolling process.
- Illustration 26 is the method of any previous or subsequent illustration, wherein the hot rolling process comprises an exit temperature of from 100° C. to 500° C.
- Illustration 27 is the method of any previous or subsequent illustration, wherein the exit temperature is from 200° C. to 400° C.
- Illustration 28 is the method of any previous or subsequent illustration, wherein the rolled aluminum alloy product produced by the hot rolling process has a thickness from 1 mm to 8 mm.
- Illustration 29 is the method of any previous or subsequent illustration, wherein the cold rolling process comprises an exit temperature of from 50° C. to 250° C.
- Illustration 30 is the method of any previous or subsequent illustration, wherein the exit temperature is from 100° C. to 200° C.
- Illustration 31 is the method of any previous or subsequent illustration, wherein the rolled aluminum alloy product produced by the cold rolling process has a thickness from 0.15 mm to 0.30 mm.
- Illustration 32 is the method of any previous or subsequent illustration, wherein the plurality of particles comprises a particle diameter from 500 nm to 50 ⁇ m.
- Illustration 33 is the method of any previous or subsequent illustration, wherein the particle density is from 50 to 1,000 particles per ⁇ m 2 .
- Illustration 34 is the method of any previous or subsequent illustration, wherein the aluminum alloy is from a recycled source.
- Illustration 35 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.1 wt. % to 1.0 wt. % iron, from 0.05 wt. % to 0.8 wt. % silicon, from 0.2 wt. % to 2.0 wt. % manganese, from 0.2 wt. % to 2.0 wt. % magnesium, up to 0.5 wt. % copper, up to 0.05 wt. % zinc, and aluminum.
- Illustration 36 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium, up to 0.10 wt. % chromium, up to 0.10 wt. % zirconium, up to 0.10 wt. % vanadium, and aluminum.
- Illustration 37 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum.
- Illustration 38 is the method of any previous or subsequent illustration, wherein the ⁇ phase intermetallic particles comprise from 0.5% to 4.0% by volume of the aluminum alloy and the ⁇ -phase intermetallic particles comprise from 0 to 2.0% by volume of the aluminum alloy.
- Illustration 39 is the method of any previous or subsequent illustration, wherein the ⁇ phase intermetallic particles comprise Al15(Fe,Mn)3Si2, and wherein the ⁇ -phase intermetallic particles comprise Al6(Fe,Mn).
- Illustration 40 is the method of any previous or subsequent illustration, wherein a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density is from 0.2 to 1,000 or wherein a ratio of a volume % of the ⁇ -phase intermetallic particles to a volume % of the ⁇ -phase intermetallic particles is from 0.6 to 1,000.
- Illustration 41 is the method of any previous or subsequent illustration, wherein the ratio of an ⁇ -phase intermetallic particle number density to the ⁇ -phase intermetallic particle number density is from 0.3 to 3.
- Illustration 42 is the method of any previous or subsequent illustration, wherein 80 percent or more of the plurality of particles have an inter-particle spacing from 5 ⁇ m to 15 ⁇ m.
- Illustration 43 is the method of any previous or subsequent illustration, wherein the plurality of particles comprise iron-containing particles, wherein a majority of the iron-containing particles have an diameter from 1 ⁇ m to 40 ⁇ m.
- Illustration 44 is the method of any previous or subsequent illustration, wherein iron-containing particles comprise from 1% to 4% of a total volume of the aluminum alloy.
- Illustration 45 is the method of any previous or subsequent illustration, wherein the aluminum alloy further comprises manganese-containing dispersoids, wherein the manganese-containing dispersoids have a diameter from 10 nm and 1.5 ⁇ m.
- Illustration 46 is the method of any previous or subsequent illustration, wherein the manganese-containing dispersoids comprise up to 1% of a total volume of the aluminum alloy.
- Illustration 47 is a method for improving formability of a metal product, the method comprising: providing a cast metal product comprising a metal composite, wherein the metal composite comprises iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the metal composite to an iron wt.
- % in the metal composite is from 0.5 to 1.0, and wherein the metal composite includes a plurality of particles including ⁇ -phase intermetallic particles comprising silicon and one or more of iron or manganese and ⁇ -phase intermetallic particles comprising one or more of iron or manganese; and homogenizing the cast metal product to control an inter-particle spacing of the plurality of particles and to control a particle density of the plurality of particles such to achieve a ratio of an inter-particle spacing to particle density from 0.0003/ ⁇ m to 0.0006/ ⁇ m.
- Illustration 48 is the method of any previous or subsequent illustration, wherein the inter-particle spacing is from 1 ⁇ m to 25 ⁇ m.
- Illustration 49 is the method of any previous or subsequent illustration, wherein the particle density is from 5 to 30,000 particles per ⁇ m 2 .
- Illustration 50 is the method of any previous or subsequent illustration, wherein the particle density is from 5 to 1,000 particles per ⁇ m 2 .
- Illustration 51 is the method of any previous or subsequent illustration, wherein the plurality of particles comprise a particle diameter from 1 ⁇ m to 50 ⁇ m.
- Illustration 52 is the method of any previous or subsequent illustration, wherein homogenizing the cast metal product comprises heating the cast metal product to a homogenization temperature from 400° C. to 800° C. and soaking the cast metal product at the homogenization temperature for a time duration from 0.1 hours to 48 hours.
- Illustration 53 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the cast metal product.
- Illustration 54 is the method of any previous or subsequent illustration, wherein homogenizing the cast metal product further comprises subjecting the cast metal product to one or more of a hot rolling process or a cold rolling process.
- Illustration 55 is a method of making an aluminum alloy product, the method comprising: preparing a cast aluminum alloy product, wherein the cast aluminum alloy product comprises a 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the 3xxx series aluminum alloy to an iron wt.
- % in the 3xxx series aluminum alloy is from 0.5 to 1.0
- the cast aluminum alloy product includes ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese and ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product by: heating the cast aluminum alloy product to a homogenization temperature from 575° C. to 615° C.; and soaking the cast aluminum alloy product at the homogenization temperature for a time duration between 12 hours and 36 hours; wherein silicon from the 3xxx series aluminum alloy diffuses into and transforms at least a fraction of the ⁇ phase intermetallic particles into ⁇ -phase intermetallic particles.
- Illustration 56 is the method of any previous or subsequent illustration, wherein the time duration is between 24 hours and 36 hours.
- Illustration 57 is the method of any previous or subsequent illustration, wherein the time duration is between 24 hours and 30 hours.
- Illustration 58 is the method of any previous or subsequent illustration, wherein the homogenization temperature is from 580° C. to 610° C.
- Illustration 59 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the 3xxx series aluminum alloy.
- Illustration 60 is the method of any previous or subsequent illustration, wherein, during the soaking, iron diffuses out of the ⁇ -phase intermetallic particles and is replaced by manganese.
- Illustration 61 is the method of any previous or subsequent illustration, wherein, during the soaking, iron diffuses out of the ⁇ -phase intermetallic particles and combines with dispersoids present within the cast aluminum alloy product to form ⁇ -phase intermetallic particles.
- Illustration 62 is the method of any previous or subsequent illustration, wherein the dispersoids comprise manganese.
- Illustration 63 is the method of any previous or subsequent illustration, wherein, during the soaking, an average size of the ⁇ -phase intermetallic particles decreases as compared to an average size of the ⁇ -phase intermetallic particles prior to soaking.
- Illustration 64 is the method of any previous or subsequent illustration, wherein, during the soaking, a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the ⁇ -phase intermetallic particles in the cast aluminum alloy product prior to soaking.
- Illustration 65 is the method of any previous or subsequent illustration, wherein, during the soaking, 30% to 100% of the ⁇ -phase intermetallic particles are transformed into ⁇ phase intermetallic particles.
- Illustration 66 is the method of any previous or subsequent illustration, wherein a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density in the homogenized aluminum alloy product is from 2 to 1000.
- Illustration 67 is the method of any previous or subsequent illustration, wherein a ratio of an ⁇ -phase intermetallic particle number density to a ⁇ -phase intermetallic particle number density in the cast aluminum alloy product is from 0.3 to 3.
- Illustration 68 is the method of any previous or subsequent illustration, wherein the ratio of the silicon wt. % to the iron wt. % in the 3xxx series aluminum alloy is from 0.55 to 0.9.
- Illustration 69 is the method of any previous or subsequent illustration, wherein the 3xxx series aluminum alloy comprises: from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.25-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- Illustration 70 is the method of any previous or subsequent illustration, wherein preparing the cast aluminum alloy product comprises preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy.
- Illustration 71 is the method of any previous or subsequent illustration, wherein preparing the molten 3xxx series aluminum alloy comprises melting a combination of a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- Illustration 72 is the method of any previous or subsequent illustration, wherein the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy are from a recycled source.
- Illustration 73 is the method of any previous or subsequent illustration, wherein preparing the molten 3xxx series aluminum alloy further comprises melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy with the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy.
- Illustration 74 is the method of any previous or subsequent illustration, wherein the homogenization temperature is a first homogenization temperature, and wherein the method further comprises: reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature; and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration.
- Illustration 75 is the method of any previous or subsequent illustration, wherein the second time duration is from 1 hour to 24 hours.
- Illustration 76 is the method of any previous or subsequent illustration, wherein the second homogenization temperature is from 500° C. to 600° C.
- Illustration 77 is the method of any previous or subsequent illustration, wherein soaking the homogenized aluminum alloy product at the second homogenization temperature controls a surface quality of the homogenized aluminum alloy product.
- Illustration 78 is the method of any previous or subsequent illustration, further comprising subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- Illustration 79 is an aluminum alloy product, comprising: a homogenized 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the homogenized 3xxx series aluminum alloy to an iron wt. % in the homogenized 3xxx series aluminum alloy is from 0.5 to 1.0, and wherein the homogenized 3xxx series aluminum alloy includes ⁇ -phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese, wherein at least a portion of the ⁇ -phase intermetallic particles are transformed from ⁇ -phase intermetallic particles comprising aluminum and one or more of iron or manganese during homogenization of the homogenized 3xxx series aluminum alloy.
- Illustration 80 is the aluminum alloy product of any previous or subsequent illustration, wherein a ratio of an ⁇ -phase intermetallic particle number density in the homogenized 3xxx series aluminum alloy to a ⁇ -phase intermetallic particle number density in the homogenized 3xxx series aluminum alloy is from 2 to 1000 or wherein a ratio of a volume % of the ⁇ -phase intermetallic particles to a volume % of the ⁇ -phase intermetallic particle is from 0.6 to 1000.
- Illustration 81 is the aluminum alloy product of any previous or subsequent illustration, wherein the homogenized 3xxx series aluminum alloy is subjected to one or more rolling processes.
- Illustration 82 is the aluminum alloy product of any previous or subsequent illustration, wherein the homogenized 3xxx series aluminum alloy comprises: from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.25-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- Illustration 83 is the aluminum alloy product of any previous illustration, prepared by the method of any previous illustration.
- Illustration 84 is the method of any previous illustration, comprising a method of making the aluminum alloy product of any previous illustration.
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Abstract
Described are aluminum alloy products and methods of making aluminum alloy products in which the aluminum alloy products have carefully controlled intermetallic particle density and particle size. Such aluminum alloy products may exhibit favorable formability. Control over intermetallic particle size and density may allow for use of high amounts of recycled source content in aluminum alloy products.
Description
- This application claims the benefit of and priority to U.S. Provisional Application No. 62/963,816, filed on Jan. 21, 2020, which is hereby incorporated by reference in its entirety.
- The present disclosure relates to metallurgy generally and more specifically to aluminum alloy products and techniques for improving formability of aluminum alloy products, particularly those containing high amounts of recycled source content. The present disclosure also relates to aluminum alloy products useful for beverage containers and other aluminum alloy products, and methods of preparing aluminum alloy products.
- Formability is an important mechanical property of aluminum alloy products. In some instances, a reduction of constituent particle size within the aluminum alloy microstructure aims to improve formability. At the same time, environmental concerns call for increased recycled source content within aluminum alloy products. However, increasing the recycled source content of aluminum alloy products may reduce formability of the aluminum alloy products.
- One industry that may benefit from increased formability and increased recycled source content is the beverage container industry. However, the composition of aluminum alloys used within the beverage containing industry may impact the formability and recycled source content of the beverage products. For example, AA3104 alloys which contain manganese are commonly used for beverage can body stock, while aluminum alloys containing magnesium (e.g., AA5182) have been used for beverage can end stock. Different aluminum alloys may be useful for meeting the needs of different beverage container technologies.
- The term embodiment and like terms are intended to refer broadly to all of the subject matter of this disclosure and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the claims below. Embodiments of the present disclosure covered herein are defined by the claims below, not this summary. This summary is a high-level overview of various aspects of the disclosure and introduces some of the concepts that are further described in the Detailed Description section below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used in isolation to determine the scope of the claimed subject matter. The subject matter should be understood by reference to appropriate portions of the entire specification of this disclosure, any or all drawings and each claim.
- Described herein are aluminum alloy products and methods of making aluminum alloy products in which the aluminum alloy products have been processed to have a favorable distribution of intermetallic particles, particle density, and/or spacing between the particles (inter-particle spacing), which may be beneficial for aluminum beverage container making processes and/or for minimizing and reducing galling and tear-offs during drawing, ironing, and/or necking during forming of an aluminum alloy product, (e.g., in the process of making aluminum beverage containers). Moreover, the ability to control particle density and inter-particle spacing to favorable values may allow for increased recycled source content, benefiting the environmental and economic cost of aluminum alloy product production. Optionally, the aluminum alloy includes a plurality of particles including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese. Optionally, the aluminum alloy includes a plurality of particles including β-phase intermetallic particles comprising aluminum and one or more of iron or manganese. Optionally, the aluminum alloy is from a recycled source or is at least partially from a recycled source.
- The aluminum alloys of some embodiments may exhibit ratios of iron to silicon (e.g., ratios of wt. %) that may be greater than iron to silicon ratios in some alloys conventionally used in the beverage container making process. For example, ratios of iron wt. % to silicon wt. % in aluminum alloys described herein may range from about 0.5 to about 5.0, or may be about 0.5, 0.6, 0.7, 0.8, 0.9, 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, and/or 5.0, for example. The disclosed aluminum alloys of some embodiments may alternatively exhibit ratios of silicon to iron (e.g., ratios of wt. %) that are greater than silicon to iron ratios in alloys conventionally used in the beverage container making process. For example, ratios of silicon wt. % to iron wt. % in aluminum alloys described herein may range from about 0.5 to about 1.0, such as from 0.5 to 1.0, such as from 0.5 to 0.6, from 0.5 to 0.7, from 0.5 to 0.8, from 0.5 to 0.9, from 0.6 to 07, from 0.6 to 0.8, from 0.6 to 0.9, from 0.6 to 1.0, from 0.7 to 0.8, from 0.7 to 0.9, from 0.7 to 1.0, from 0.8 to 0.9, from 0.8 to 1.0, or from 0.9 to 1.0, or about 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, or 1, for example. Increasing the amount of iron relative to the amount of silicon or the amount of silicon relative to the amount of iron in an aluminum alloy may be useful for controlling particle sizes, concentrations, distributions, particle density, inter-particle spacing, and/or compositions of intermetallic particles in the aluminum alloy. Additionally, using increased amounts of iron in an aluminum alloy may allow larger amounts of recycled source content to be used.
- Sizes, concentrations, density, inter-particle spacing, compositions of particles, and/or distribution of intermetallic particles in the aluminum alloy may alternatively or additionally be controlled by subjecting the aluminum alloy to suitable homogenization conditions after casting. For example, by homogenizing (soaking) the aluminum alloy at relatively long durations (e.g., more than about 12 hours or more than about 24 hours), less favorable intermetallic particles may be transformed into more favorable particles. Such transformations may not occur or not occur to a significant enough extent during short duration (e.g., less than about 24 hours or less than about 12 hours) homogenization to suitably impact the size, concentration, inter-particle spacing, distribution of intermetallic particles, and/or composition of enough numbers of particles. For example, by subjecting an aluminum alloy to long, high temperature homogenization, less desirable intermetallic particles can have their chemical and crystal structures altered by diffusion of silicon into the particles and/or diffusion of iron out of the particles.
- Optionally, an aluminum alloy product comprises an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon. Optionally, a ratio of an iron wt. % in the aluminum alloy to a silicon wt. % in the aluminum alloy is from 0.5 to 5.0, such as from 0.5 to 1.0, from 0.5 to 1.1, from 0.5 to 1.5, from 0.5 to 1.8, from 0.5 to 2.0, from 0.5 to 2.5, from 0.5 to 3.0, from 0.5 to 3.5, from 0.5 to 4.0, from 0.5 to 4.5, from 1.0 to 1.1, from 1.0 to 1.5, from 1.0 to 1.8, from 1.0 to 2.0, from 1.0 to 2.5, from 1.0 to 3.0, from 1.0 to 3.5, from 1.0 to 4.0, from 1.0 to 4.5, from 1.0 to 5.0, from 1.1 to 1.5, from 1.1 to 1.8, from 1.1 to 2.0, from 1.1 to 2.5, from 1.1 to 3.0, from 1.1 to 3.5, from 1.1 to 4.0, from 1.1 to 4.5, from 1.1 to 5.0, from 1.5 to 1.8, from 1.5 to 2.0, from 1.5 to 2.5, from 1.5 to 3.0, from 1.5 to 3.5, from 1.5 to 4.0, from 1.5 to 4.5, from 1.5 to 5.0, from 1.8 to 2.0, from 1.8 to 2.5, from 1.8 to 3.0, from 1.8 to 3.5, from 1.8 to 4.0, from 1.8 to 4.5, from 1.8 to 5.0, from 2.0 to 2.5, from 2.0 to 3.0, from 2.0 to 3.5, from 2.0 to 4.0, from 2.0 to 4.5, from 2.0 to 5.0, from 2.5 to 3.0, from 2.5 to 3.5, from 2.5 to 4.0, from 2.5 to 4.5, from 2.5 to 5.0, from 3.0 to 3.5, from 3.0 to 4.0, from 3.0 to 4.5, from 3.0 to 5.0, from 3.5 to 4.0, from 3.5 to 4.5, from 3.5 to 5.0, from 4.0 to 4.5, from 4.0 to 5.0, or from 4.5 to 5.0. Optionally, a ratio of a silicon wt. % to an iron wt. % in an aluminum alloy products, such as comprising a 3xxx series aluminum alloy, may be from 0.5 to 1.0, such as from 0.5 to 0.55, from 0.5 to 0.6, from 0.5 to 0.65, from 0.5 to 0.7, from 0.5 to 0.75, from 0.5 to 0.8, from 0.5 to 0.85, from 0.5 to 0.9, from 0.5 to 0.95, from 0.55 to 0.6, from 0.55 to 0.65, from 0.55 to 0.7, from 0.55 to 0.75, from 0.55 to 0.8, from 0.55 to 0.85, from 0.55 to 0.9, from 0.55 to 0.95, from 0.55 to 1.0, from 0.6 to 0.65, from 0.6 to 0.7, from 0.6 to 0.75, from 0.6 to 0.8, from 0.6 to 0.85, from 0.6 to 0.9, from 0.6 to 0.95, from 0.6 to 1, from 0.65 to 0.65, from 0.65 to 0.7, from 0.65 to 0.75, from 0.65 to 0.8, from 0.65 to 0.85, from 0.65 to 0.9, from 0.65 to 0.95, from 0.65 to 1.0, from 0.7 to 0.75, from 0.7 to 0.8, from 0.7 to 0.85, from 0.7 to 0.95, from 0.7 to 1, from 0.75 to 0.8, from 0.75 to 0.85, from 0.75 to 0.9, from 0.75 to 0.95, from 0.75 to 1.0, from 0.8 to 0.85, from 0.8 to 0.9, from 0.8 to 0.95, from 0.8 to 1, from 0.85 to 0.9, from 0.85 to 0.95, from 0.85 to 1.0, from 0.9 to 0.95, from 0.9 to 1, or from 0.95 to 1.0. An example 3xxx series aluminum alloy may comprise from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.4-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- In embodiments, the cast aluminum alloy product includes β-phase intermetallic particles comprising aluminum and one or more of iron or manganese and/or α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese. Optionally, a particle density, such as of β-phase intermetallic particles and/or α-phase intermetallic particles, may be from 5 to 30,000 particles per µm2, such as from 10 to 5,000, from 10 to 20,000, from 10 to 15,000, from 10 to 10,000, from 10 to 9,500, from 10 to 9,000, from 10 to 8,500, from 10 to 8,000, from 10 to 7,500, from 10 to 7,000, from 10 to 6,500, from 10 to 6,000, from 10 to 5,500, from 10 to 5,000, from 10 to 4,500, from 10 to 4,000, from 10 to 3,500, from 10 to 3,000, from 10 to 2,500, from 10 to 2,000, from 10 to 1,500, from 10 to 1,000, from 10 to 950, from 10 to 900, from 10 to 850, from 10 to 800, from 10 to 750, from 10 to 700, from 10 to 650, from 10 to 600, from 10 to 550, from 10 to 500, from 10 to 450, from 10 to 400, from 10 to 350, from 10 to 300, from 10 to 250, from 10 to 200, from 10 to 150, from 10 to 100, from 10 to 75, from 10 to 50, from 10 to 25, from 25 to 30,000, from 25 to 25,000, from 25 to 20,000, from 25 to 15,000, from 25 to 10,000, from 25 to 9,500, from 25 to 9,000, from 25 to 8,500, from 25 to 8,000, from 25 to 7,500, from 25 to 7,000, from 25 to 6,500, from 25 to 6,000, from 25 to 5,500, from 25 to 5,000, from 25 to 4,500, from 25 to 4,000, from 25 to 3,500, from 25 to 3,000, from 25 to 2,500, from 25 to 2,000, from 25 to 1,500, from 25 to 1,000, from 25 to 950, from 25 to 900, from 25 to 850, from 25 to 800, from 25 to 750, from 25 to 700, from 25 to 650, from 25 to 600, from 25 to 550, from 25 to 500, from 25 to 450, from 25 to 400, from 25 to 350, from 25 to 300, from 25 to 250, from 25 to 200, from 25 to 150, from 25 to 100, from 25 to 75, from 25 to 50, from 50 to 30,000, from 50 to 25,000, from 50 to 20,000, from 50 to 15,000, from 50 to 10,000, from 50 to 9,500, from 50 to 9,000, from 50 to 8,500, from 50 to 8,000, from 50 to 7,500, from 50 to 7,000, from 50 to 6,500, from 50 to 6,000, from 50 to 5,500, from 50 to 5,000, from 50 to 4,500, from 50 to 4,000, from 50 to 3,500, from 50 to 3,000, from 50 to 2,500, from 50 to 2,000, from 50 to 1,500, from 50 to 1,000, from 50 to 950, from 50 to 900, from 50 to 850, from 50 to 800, from 50 to 750, from 50 to 700, from 50 to 650, from 50 to 600, from 50 to 550, from 50 to 500, from 50 to 450, from 50 to 400, from 50 to 350, from 50 to 300, from 50 to 250, from 50 to 200, from 50 to 150, from 50 to 100, from 50 to 75, from 75 to 30,000, from 75 to 25,000, from 75 to 20,000, from 75 to 15,000, from 75 to 10,000, from 75 to 9,500, from 75 to 9,000, from 75 to 8,500, from 75 to 8,000, from 75 to 7,500, from 75 to 7,000, from 75 to 6,500, from 75 to 6,000, from 75 to 5,500, from 75 to 5,000, from 75 to 4,500, from 75 to 4,000, from 75 to 3,500, from 75 to 3,000, from 75 to 2,500, from 75 to 2,000, from 75 to 1,500, from 75 to 1,000, from 75 to 950, from 75 to 900, from 75 to 850, from 75 to 800, from 75 to 750, from 75 to 700, from 75 to 650, from 75 to 600, from 75 to 550, from 75 to 500, from 75 to 450, from 75 to 400, from 75 to 350, from 75 to 300, from 75 to 250, from 75 to 200, from 75 to 150, from 75 to 100, from 100 to 30,000, from 100 to 25,000, from 100 to 20,000, from 100 to 15,000, from 100 to 10,000, from 100 to 9,500, from 100 to 9,000, from 100 to 8,500, from 100 to 8,000, from 100 to 7,500, from 100 to 7,000, from 100 to 6,500, from 100 to 6,000, from 100 to 5,500, from 100 to 5,000, from 100 to 4,500, from 100 to 4,000, from 100 to 3,500, from 100 to 3,000, from 100 to 2,500, from 100 to 2,000, from 100 to 1,500, from 100 to 1,000, from 100 to 950, from 100 to 900, from 100 to 850, from 100 to 800, from 100 to 750, from 100 to 700, from 100 to 650, from 100 to 600, from 100 to 550, from 100 to 500, from 100 to 450, from 100 to 400, from 100 to 350, from 100 to 300, from 100 to 250, from 100 to 200, from 100 to 150, from 150 to 30,000, from 150 to 25,000, from 150 to 20,000, from 150 to 15,000, from 150 to 10,000, from 150 to 9,500, from 150 to 9,000, from 150 to 8,500, from 150 to 8,000, from 150 to 7,500, from 150 to 7,000, from 150 to 6,500, from 150 to 6,000, from 150 to 5,500, from 150 to 5,000, from 150 to 4,500, from 150 to 4,000, from 150 to 3,500, from 150 to 3,000, from 150 to 2,500, from 150 to 2,000, from 150 to 1,500, from 150 to 1,000, from 150 to 950, from 150 to 900, from 150 to 850, from 150 to 800, from 150 to 750, from 150 to 700, from 150 to 650, from 150 to 600, from 150 to 550, from 150 to 500, from 150 to 450, from 150 to 400, from 150 to 350, from 150 to 300, from 150 to 250, from 150 to 200, from 200 to 30,000, from 200 to 25,000, from 200 to 20,000, from 200 to 15,000, from 200 to 10,000, from 200 to 9,500, from 200 to 9,000, from 200 to 8,500, from 200 to 8,000, from 200 to 7,500, from 200 to 7,000, from 200 to 6,500, from 200 to 6,000, from 200 to 5,500, from 200 to 5,000, from 200 to 4,500, from 200 to 4,000, from 200 to 3,500, from 200 to 3,000, from 200 to 2,500, from 200 to 2,000, from 200 to 1,500, from 200 to 1,000, from 200 to 950, from 200 to 900, from 200 to 850, from 200 to 800, from 200 to 750, from 200 to 700, from 200 to 650, from 200 to 600, from 200 to 550, from 200 to 500, from 200 to 450, from 200 to 400, from 200 to 350, from 200 to 300, from 200 to 250, from 250 to 30,000, from 250 to 25,000, from 250 to 20,000, from 250 to 15,000, from 250 to 10,000, from 250 to 9,500, from 250 to 9,000, from 250 to 8,500, from 250 to 8,000, from 250 to 7,500, from 250 to 7,000, from 250 to 6,500, from 250 to 6,000, from 250 to 5,500, from 250 to 5,000, from 250 to 4,500, from 250 to 4,000, from 250 to 3,500, from 250 to 3,000, from 250 to 2,500, from 250 to 2,000, from 250 to 1,500, from 250 to 1,000, from 250 to 950, from 250 to 900, from 250 to 850, from 250 to 800, from 250 to 750, from 250 to 700, from 250 to 650, from 250 to 600, from 250 to 550, from 250 to 500, from 250 to 450, from 250 to 400, from 250 to 350, from 250 to 300, from 300 to 30,000, from 300 to 25,000, from 300 to 20,000, from 300 to 15,000, from 300 to 10,000, from 300 to 9,500, from 300 to 9,000, from 300 to 8,500, from 300 to 8,000, from 300 to 7,500, from 300 to 7,000, from 300 to 6,500, from 300 to 6,000, from 300 to 5,500, from 300 to 5,000, from 300 to 4,500, from 300 to 4,000, from 300 to 3,500, from 300 to 3,000, from 300 to 2,500, from 300 to 2,000, from 300 to 1,500, from 300 to 1,000, from 300 to 950, from 300 to 900, from 300 to 850, from 300 to 800, from 300 to 750, from 300 to 700, from 300 to 650, from 300 to 600, from 300 to 550, from 300 to 500, from 300 to 450, from 300 to 400, from 300 to 350, from 350 to 30,000, from 350 to 25,000, from 350 to 20,000, from 350 to 15,000, from 350 to 10,000, from 350 to 9,500, from 350 to 9,000, from 350 to 8,500, from 350 to 8,000, from 350 to 7,500, from 350 to 7,000, from 350 to 6,500, from 350 to 6,000, from 350 to 5,500, from 350 to 5,000, from 350 to 4,500, from 350 to 4,000, from 350 to 3,500, from 350 to 3,000, from 350 to 2,500, from 350 to 2,000, from 350 to 1,500, from 350 to 1,000, from 350 to 950, from 350 to 900, from 350 to 850, from 350 to 800, from 350 to 750, from 350 to 700, from 350 to 650, from 350 to 600, from 350 to 550, from 350 to 500, from 350 to 450, from 350 to 400, from 400 to 30,000, from 400 to 25,000, from 400 to 20,000, from 400 to 15,000, from 400 to 10,000, from 400 to 9,500, from 400 to 9,000, from 400 to 8,500, from 400 to 8,000, from 400 to 7,500, from 400 to 7,000, from 400 to 6,500, from 400 to 6,000, from 400 to 5,500, from 400 to 5,000, from 400 to 4,500, from 400 to 4,000, from 400 to 3,500, from 400 to 3,000, from 400 to 2,500, from 400 to 2,000, from 400 to 1,500, from 400 to 1,000, from 400 to 950, from 400 to 900, from 400 to 850, from 400 to 800, from 400 to 750, from 400 to 700, from 400 to 650, from 400 to 600, from 400 to 550, from 400 to 500, from 400 to 450, from 450 to 30,000, from 450 to 25,000, from 450 to 20,000, from 450 to 15,000, from 450 to 10,000, from 450 to 9,500, from 450 to 9,000, from 450 to 8,500, from 450 to 8,000, from 450 to 7,500, from 450 to 7,000, from 450 to 6,500, from 450 to 6,000, from 450 to 5,500, from 450 to 5,000, from 450 to 4,500, from 450 to 4,000, from 450 to 3,500, from 450 to 3,000, from 450 to 2,500, from 450 to 2,000, from 450 to 1,500, from 450 to 1,000, from 450 to 950, from 450 to 900, from 450 to 850, from 450 to 800, from 450 to 750, from 450 to 700, from 450 to 650, from 450 to 600, from 450 to 550, from 450 to 500, from 500 to 30,000, from 500 to 25,000, from 500 to 20,000, from 500 to 15,000, from 500 to 10,000, from 500 to 9,500, from 500 to 9,000, from 500 to 8,500, from 500 to 8,000, from 500 to 7,500, from 500 to 7,000, from 500 to 6,500, from 500 to 6,000, from 500 to 5,500, from 500 to 5,000, from 500 to 4,500, from 500 to 4,000, from 500 to 3,500, from 500 to 3,000, from 500 to 2,500, from 500 to 2,000, from 500 to 1,500, from 500 to 1,000, from 500 to 950, from 500 to 900, from 500 to 850, from 500 to 800, from 500 to 750, from 500 to 700, from 500 to 650, from 500 to 600, from 500 to 550, from 600 to 30,000, from 600 to 25,000, from 600 to 20,000, from 600 to 15,000, from 600 to 10,000, from 600 to 9,500, from 600 to 9,000, from 600 to 8,500, from 600 to 8,000, from 600 to 7,500, from 600 to 7,000, from 600 to 6,500, from 600 to 6,000, from 600 to 5,500, from 600 to 5,000, from 600 to 4,500, from 600 to 4,000, from 600 to 3,500, from 600 to 3,000, from 600 to 2,500, from 600 to 2,000, from 600 to 1,500, from 600 to 1,000, from 600 to 950, from 600 to 900, from 600 to 850, from 600 to 800, from 600 to 750, from 600 to 700, from 600 to 650, from 700 to 30,000, from 700 to 25,000, from 700 to 20,000, from 700 to 15,000, from 700 to 10,000, from 700 to 9,500, from 700 to 9,000, from 700 to 8,500, from 700 to 8,000, from 700 to 7,500, from 700 to 7,000, from 700 to 6,500, from 700 to 6,000, from 700 to 5,500, from 700 to 5,000, from 700 to 4,500, from 700 to 4,000, from 700 to 3,500, from 700 to 3,000, from 700 to 2,500, from 700 to 2,000, from 700 to 1,500, from 700 to 1,000, from 700 to 950, from 700 to 900, from 700 to 850, from 700 to 800, from 700 to 750, from 800 to 30,000, from 800 to 25,000, from 800 to 20,000, from 800 to 15,000, from 800 to 10,000, from 800 to 9,500, from 800 to 9,000, from 800 to 8,500, from 800 to 8,000, from 800 to 7,500, from 800 to 7,000, from 800 to 6,500, from 800 to 6,000, from 800 to 5,500, from 800 to 5,000, from 800 to 4,500, from 800 to 4,000, from 800 to 3,500, from 800 to 3,000, from 800 to 2,500, from 800 to 2,000, from 800 to 1,500, from 800 to 1,000, from 800 to 950, from 800 to 900, from 800 to 850, from 900 to 30,000, from 900 to 25,000, from 900 to 20,000, from 900 to 15,000, from 900 to 10,000, from 900 to 9,500, from 900 to 9,000, from 900 to 8,500, from 900 to 8,000, from 900 to 7,500, from 900 to 7,000, from 900 to 6,500, from 900 to 6,000, from 900 to 5,500, from 900 to 5,000, from 900 to 4,500, from 900 to 4,000, from 900 to 3,500, from 900 to 3,000, from 900 to 2,500, from 900 to 2,000, from 900 to 1,500, from 900 to 1,000, from 900 to 950, from 1,000 to 30,000, from 1,000 to 25,000, from 1,000 to 20,000, from 1,000 to 15,000, from 1,000 to 10,000, from 1,000 to 9,500, from 1,000 to 9,000, from 1,000 to 8,500, from 1,000 to 8,000, from 1,000 to 7,500, from 1,000 to 7,000, from 1,000 to 6,500, from 1,000 to 6,000, from 1,000 to 5,500, from 1,000 to 5,000, from 1,000 to 4,500, from 1,000 to 4,000, from 1,000 to 3,500, from 1,000 to 3,000, from 1,000 to 2,500, from 1,000 to 2,000, from 1,000 to 1,500, from 2,000 to 30,000, from 2,000 to 25,000, from 2,000 to 20,000, from 2,000 to 15,000, from 2,000 to 10,000, from 2,000 to 9,500, from 2,000 to 9,000, from 2,000 to 8,500, from 2,000 to 8,000, from 2,000 to 7,500, from 2,000 to 7,000, from 2,000 to 6,500, from 2,000 to 6,000, from 2,000 to 5,500, from 2,000 to 5,000, from 2,000 to 4,500, from 2,000 to 4,000, from 2,000 to 3,500, from 2,000 to 3,000, from 2,000 to 2,500, from 3,000 to 30,000, from 3,000 to 25,000, from 3,000 to 20,000, from 3,000 to 15,000, from 3,000 to 10,000, from 3,000 to 9,500, from 3,000 to 9,000, from 3,000 to 8,500, from 3,000 to 8,000, from 3,000 to 7,500, from 3,000 to 7,000, from 3,000 to 6,500, from 3,000 to 6,000, from 3,000 to 5,500, from 3,000 to 5,000, from 3,000 to 4,500, from 3,000 to 4,000, from 3,000 to 3,500, from 4,000 to 30,000, from 4,000 to 25,000, from 4,000 to 20,000, from 4,000 to 15,000, from 4,000 to 10,000, from 4,000 to 9,500, from 4,000 to 9,000, from 4,000 to 8,500, from 4,000 to 8,000, from 4,000 to 7,500, from 4,000 to 7,000, from 4,000 to 6,500, from 4,000 to 6,000, from 4,000 to 5,500, from 4,000 to 5,000, from 4,000 to 4,500, from 5,000 to 30,000, from 5,000 to 25,000, from 5,000 to 20,000, from 5,000 to 15,000, from 5,000 to 10,000, from 5,000 to 9,500, from 5,000 to 9,000, from 5,000 to 8,500, from 5,000 to 8,000, from 5,000 to 7,500, from 5,000 to 7,000, from 5,000 to 6,500, from 5,000 to 6,000, from 5,000 to 5,500, from 6,000 to 30,000, from 6,000 to 25,000, from 6,000 to 20,000, from 6,000 to 15,000, from 6,000 to 10,000, from 6,000 to 9,500, from 6,000 to 9,000, from 6,000 to 8,500, from 6,000 to 8,000, from 6,000 to 7,500, from 6,000 to 7,000, from 6,000 to 6,500, from 7,000 to 30,000, from 7,000 to 25,000, from 7,000 to 20,000, from 7,000 to 15,000, from 7,000 to 10,000, from 7,000 to 9,500, from 7,000 to 9,000, from 7,000 to 8,500, from 7,000 to 8,000, from 7,000 to 7,500, from 8,000 to 30,000, from 8,000 to 25,000, from 8,000 to 20,000, from 8,000 to 15,000, from 8,000 to 10,000, from 8,000 to 9,500, from 8,000 to 9,000, from 8,000 to 8,500, from 9,000 to 30,000, from 9,000 to 25,000, from 9,000 to 20,000, from 9,000 to 15,000, from 9,000 to 10,000, from 9,000 to 9,500, from 10,000 to 30,000, from 10,000 to 25,000, from 10,000 to 20,000, from 10,000 to 15,000, from 15,000 to 30,000, from 15,000 to 25,000, from 15,000 to 20,000, from 20,000 to 30,000, from 20,000 to 25,000, or from 25,000 to 30,000.
- Optionally, an inter-particle spacing for the plurality of particles may be from 1 µm to 25 µm, such as from 1 µm to 2 µm, from 1 µm to 3 µm, from 1 µm to 4 µm, from 1 µm to 5 µm, from 1 µm to 6 µm, from 1 µm to 7 µm, from 1 µm to 8 µm, from 1 µm to 9 µm, from 1 µm to 10 µm, from 1 µm to 11 µm, from 1 µm to 12 µm, from 1 µm to 13 µm, from 1 µm to 14 µm, from 1 µm to 15 µm, from 1 µm to 16 µm, from 1 µm to 17 µm, from 1 µm to 18 µm, from 1 µm to 19 µm, from 1 µm to 20 µm, from 1 µm to 21 µm, from 1 µm to 22 µm, from 1 µm to 23 µm, from 1 µm to 24 µm, from 2 µm to 3 µm, from 2 µm to 4 µm, from 2 µm to 5 µm, from 2 µm to 6 µm, from 2 µm to 7 µm, from 2 µm to 8 µm, from 2 µm to 9 µm, from 2 µm to 10 µm, from 2 µm to 11 µm, from 2 µm to 12 µm, from 2 µm to 13 µm, from 2 µm to 14 µm, from 2 µm to 15 µm, from 2 µm to 16 µm, from 2 µm to 17 µm, from 2 µm to 18 µm, from 2 µm to 19 µm, from 2 µm to 20 µm, from 2 µm to 21 µm, from 2 µm to 22 µm, from 2 µm to 23 µm, from 2 µm to 24 µm, from 2 µm to 25 µm, from 3 µm to 4 µm, from 3 µm to 5 µm, from 3 µm to 6 µm, from 3 µm to 7 µm, from 3 µm to 8 µm, from 3 µm to 9 µm, from 3 µm to 10 µm, from 3 µm to 11 µm, from 3 µm to 12 µm, from 3 µm to 13 µm, from 3 µm to 14 µm, from 3 µm to 15 µm, from 3 µm to 16 µm, from 3 µm to 17 µm, from 3 µm to 18 µm, from 3 µm to 19 µm, from 3 µm to 20 µm, from 3 µm to 21 µm, from 3 µm to 22 µm, from 3 µm to 23 µm, from 3 µm to 24 µm, from 3 µm to 25 µm, from 4 µm to 5 µm, from 4 µm to 6 µm, from 4 µm to 7 µm, from 4 µm to 8 µm, from 4 µm to 9 µm, from 4 µm to 10 µm, from 4 µm to 11 µm, from 4 µm to 12 µm, from 4 µm to 13 µm, from 4 µm to 14 µm, from 4 µm to 15 µm, from 4 µm to 16 µm, from 4 µm to 17 µm, from 4 µm to 18 µm, from 4 µm to 19 µm, from 4 µm to 20 µm, from 4 µm to 21 µm, from 4 µm to 22 µm, from 4 µm to 23 µm, from 4 µm to 24 µm, from 4 µm to 25 µm, from 5 µm to 6 µm, from 5 µm to 7 µm, from 5 µm to 8 µm, from 5 µm to 9 µm, from 5 µm to 10 µm, from 5 µm to 11 µm, from 5 µm to 12 µm, from 5 µm to 13 µm, from 5 µm to 14 µm, from 5 µm to 15 µm, from 5 µm to 16 µm, from 5 µm to 17 µm, from 5 µm to 18 µm, from 5 µm to 19 µm, from 5 µm to 20 µm, from 5 µm to 21 µm, from 5 µm to 22 µm, from 5 µm to 23 µm, from 5 µm to 24 µm, from 5 µm to 25 µm, from 6 µm to 7 µm, from 6 µm to 8 µm, from 6 µm to 9 µm, from 6 µm to 10 µm, from 6 µm to 11 µm, from 6 µm to 12 µm, from 6 µm to 13 µm, from 6 µm to 14 µm, from 6 µm to 15 µm, from 6 µm to 16 µm, from 6 µm to 17 µm, from 6 µm to 18 µm, from 6 µm to 19 µm, from 6 µm to 20 µm, from 6 µm to 21 µm, from 6 µm to 22 µm, from 6 µm to 23 µm, from 6 µm to 24 µm, from 6 µm to 25 µm, from 7 µm to 8 µm, from 7 µm to 9 µm, from 7 µm to 10 µm, from 7 µm to 11 µm, from 7 µm to 12 µm, from 7 µm to 13 µm, from 7 µm to 14 µm, from 7 µm to 15 µm, from 7 µm to 16 µm, from 7 µm to 17 µm, from 7 µm to 18 µm, from 7 µm to 19 µm, from 7 µm to 20 µm, from 7 µm to 21 µm, from 7 µm to 22 µm, from 7 µm to 23 µm, from 7 µm to 24 µm, from 7 µm to 25 µm, from 8 µm to 9 µm, from 8 µm to 10 µm, from 8 µm to 11 µm, from 8 µm to 12 µm, from 8 µm to 13 µm, from 8 µm to 14 µm, from 8 µm to 15 µm, from 8 µm to 16 µm, from 8 µm to 17 µm, from 8 µm to 18 µm, from 8 µm to 19 µm, from 8 µm to 20 µm, from 8 µm to 21 µm, from 8 µm to 22 µm, from 8 µm to 23 µm, from 8 µm to 24 µm, from 8 µm to 25 µm, from 9 µm to 10 µm, from 9 µm to 11 µm, from 9 µm to 12 µm, from 9 µm to 13 µm, from 9 µm to 14 µm, from 9 µm to 15 µm , from 9 µm to 16 µm, from 9 µm to 17 µm, from 9 µm to 18 µm, from 9 µm to 19 µm, from 9 µm to 20 µm, from 9 µm to 21 µm, from 9 µm to 22 µm, from 9 µm to 23 µm, from 9 µm to 24 µm, from 9 µm to 25 µm, from 10 µm to 11 µm, from 10 µm to 12 µm, from 10 µm to 13 µm, from 10 µm to 14 µm, from 10 µm to 15 µm, from 10 µm to 16 µm, from 10 µm to 17 µm, from 10 µm to 18 µm, from 10 µm to 19 µm, from 10 µm to 20 µm, from 10 µm to 21 µm, from 10 µm to 22 µm, from 10 µm to 23 µm, from 10 µm to 24 µm, from 10 µm to 25 µm, from 11 µm to 12 µm, from 11 µm to 13 µm, from 11 µm to 14 µm, from 11 µm to 15 µm, from 11 µm to 16 µm, from 11 µm to 17 µm, from 11 µm to 18 µm, from 11 µm to 19 µm, from 11 µm to 20 µm, from 11 µm to 21 µm, from 11 µm to 22 µm, from 11 µm to 23 µm, from 11 µm to 24 µm, from 11 µm to 25 µm, from 12 µm to 13 µm, from 12 µm to 14 µm, from 12 µm to 15 µm, from 12 µm to 16 µm, from 12 µm to 17 µm, from 12 µm to 18 µm, from 12 µm to 19 µm, from 12 µm to 20 µm, from 12 µm to 21 µm, from 12 µm to 22 µm, from 12 µm to 23 µm, from 12 µm to 24 µm, from 12 µm to 25 µm, from 13 µm to 14 µm, from 13 µm to 15 µm, from 13 µm to 16 µm, from 13 µm to 17 µm, from 13 µm to 18 µm, from 13 µm to 19 µm, from 13 µm to 20 µm, from 13 µm to 21 µm, from 13 µm to 22 µm, from 13 µm to 23 µm, from 13 µm to 24 µm, from 13 µm to 25 µm, from 14 µm to 15 µm, from 14 µm to 16 µm, from 14 µm to 17 µm, from 14 µm to 18 µm, from 14 µm to 19 µm, from 14 µm to 20 µm, from 14 µm to 21 µm, from 14 µm to 22 µm, from 14 µm to 23 µm, from 14 µm to 24 µm, from 14 µm to 25 µm, from 15 µm to 16 µm, from 15 µm to 17 µm, from 15 µm to 18 µm, from 15 µm to 19 µm, from 15 µm to 20 µm, from 15 µm to 21 µm, from 15 µm to 22 µm, from 15 µm to 23 µm, from 15 µm to 24 µm, from 15 µm to 25 µm, from 16 µm to 17 µm, from 16 µm to 18 µm, from 16 µm to 19 µm, from 16 µm to 20 µm, from 16 µm to 21 µm, from 16 µm to 22 µm, from 16 µm to 23 µm, from 16 µm to 24 µm, from 16 µm to 25 µm, from 17 µm to 18 µm, from 17 µm to 19 µm, from 17 µm to 20 µm, from 17 µm to 21 µm, from 17 µm to 22 µm, from 17 µm to 23 µm, from 17 µm to 24 µm, from 17 µm to 25 µm, from 18 µm to 19 µm, from 18 µm to 20 µm, from 18 µm to 21 µm, from 18 µm to 22 µm, from 18 µm to 23 µm, from 18 µm to 24 µm, from 18 µm to 25 µm, from 19 µm to 20 µm, from 19 µm to 21 µm, from 19 µm to 22 µm, from 19 µm to 23 µm, from 19 µm to 24 µm, from 19 µm to 25 µm, from 20 µm to 21 µm, from 20 µm to 22 µm, from 20 µm to 23 µm, from 20 µm to 24 µm, from 20 µm to 25 µm, from 21 µm to 22 µm, from 21 µm to 23 µm, from 21 µm to 24 µm, from 21 µm to 25 µm, from 22 µm to 23 µm, from 22 µm to 24 µm, from 22 µm to 25 µm, from 23 µm to 24 µm, from 23 µm to 25 µm, or from 24 µm to 25 µm.
- Optionally, the plurality of particles may have diameters of from 100 nm to 50 µm or 500 nm to 10 µm or 100 nm to 1 µm, such as from 100 nm to 200 nm, from 100 nm to 300 nm, from 100 nm to 400 nm, from 100 nm to 500 nm, from 100 nm to 600 nm, from 100 nm to 700 nm, from 100 nm to 800 nm, from 100 nm to 900 nm, from 200 nm to 300 nm, from 200 nm to 400 nm, from 200 nm to 500 nm, from 200 nm to 600 nm, from 200 nm to 700 nm, from 200 nm to 800 nm, from 200 nm to 900 nm, from 200 nm to 1 µm, from 300 nm to 400 nm, from 300 nm to 500 nm, from 300 nm to 600 nm, from 300 nm to 700 nm, from 300 nm to 800 nm, from 300 nm to 900 nm, from 300 nm to 1 µm, from 400 nm to 500 nm, from 400 nm to 600 nm, from 400 nm to 700 nm, from 400 nm to 800 nm, from 400 nm to 900 nm, from 400 nm to 1 µm, from 500 nm to 600 nm, from 500 nm to 700 nm, from 500 nm to 800 nm, from 500 nm to 900 nm, from 500 nm to 1 µm, from 600 nm to 700 nm, from 600 nm to 800 nm, from 600 nm to 900 nm, from 600 nm to 1 µm, from 700 nm to 800 nm, from 700 nm to 900 nm, from 700 nm to 1 µm, from 800 nm to 900 nm, from 800 nm to 1 µm, or from 900 nm to 1 µm. Optionally, the plurality of particles may have diameters of from 500 nm to 50 µm.
- The composition of the aluminum alloy for the aluminum alloy products described above may optionally comprise from 0.1 wt. % to 1.0 wt. % iron (Fe), from 0.05 wt. % to 0.8 wt. % silicon (Si), from 0.2 wt. % to 2.0 wt. % manganese (Mn), from 0.2 wt. % to 2.0 wt. % magnesium (Mg), up to 0.5 wt. % copper (Cu), up to 0.05 wt. % zinc (Zn), and aluminum (Al). The composition of the aluminum alloy for the aluminum alloy products described above may comprise up to 0.15 wt. % impurities. Optionally, a remainder may be aluminum. Optionally, the composition of the aluminum alloy for the aluminum alloy products described above may comprise from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium (Ti), up to 0.10 wt. % chromium (Cr), up to 0.10 wt. % zirconium (Zr), up to 0.10 wt. % vanadium (V), and aluminum. Optionally, the composition of the aluminum alloy for the aluminum alloy products described above may comprise from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum.
- In some embodiments, the aluminum alloy may include a 3xxx series aluminum alloy. In such embodiments, the aluminum alloy may optionally comprise from 0.8 wt. % to 1.4 wt. % magnesium, from 0.8 wt. % to 1.3 wt. % manganese, up to 0.25 wt. % copper, from 0.25 wt. % to 0.7 wt. % iron, up to 0.7 wt.%, and up to 0.25 wt. % zinc. The remainder may be aluminum.
- The aluminum alloys for the aluminum alloy products described above may optionally include α-phase intermetallic particles comprising from 0.5% to 4.0% by volume of the aluminum alloy, such as from 0.5 to 1.0, from 0.5 to 1.5, from 0.5 to 2.0, from 0.5 to 2.5, from 0.5 to 3.0, from 0.5 to 3.5, from 1.0 to 1.5, from 1.0 to 2.0, from 1.0 to 2.5, from 1.0 to 3.0, from 1.0 to 3.5, from 1.0 to 4.0, from 1.5 to 2.0, from 1.5 to 2.5, from 1.5 to 3.0, from 1.5 to 3.5, from 1.5 to 4.0, from 2.0 to 2.5, from 2.0 to 3.0, from 2.0 to 3.5, from 2.0 to 4.0, from 2.5 to 3.0, from 2.5 to 3.5, from 2.5 to 4.0, from 3.0 to 3.5, from 3.0 to 4.0, or from 3.5 to 4.0. The aluminum alloys for the aluminum alloy products described above may include β-phase intermetallic particles comprising from 0% to 2.0% by volume of the aluminum alloy, such as from 0 to 0.5, from 0 to 1.0, from 0 to 1.5, from 0.5 to 1.0, from 0.5 to 1.5, from 0.5 to 2.0, from 1.0 to 1.5, from 1.0 to 2.0, or from 1.5 to 2.0. Optionally, the aluminum alloys for the aluminum alloy products described above may include α-phase intermetallic particles comprising Al15(Fe,Mn)3Si2. Optionally, the aluminum alloys for the aluminum alloy products described above may include β-phase intermetallic particles comprising Al6(Fe,Mn).
- Optionally, the aluminum alloys for the aluminum alloy products described above may include a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density is from 0.2 to 1,000 or a ratio of a volume % of the α-phase intermetallic particles to a volume % of the β-phase intermetallic particles is from 0.6 to 1,000.
- Optionally, the aluminum alloys for the aluminum alloy products described above may include a ratio of the α-phase intermetallic particle number density to the β-phase intermetallic particle number density from 0.3 to 3, such as from 0.3 to 0.4, from 0.3 to 0.5, from 0.3 to 0.6, from 0.3 to 0.7, from 0.3 to 0.8, from 0.3 to 0.9, from 0.3 to 1.0, from 0.3 to 1.1, from 0.3 to 1.2, from 0.3 to 1.3, from 0.3 to 1.4, from 0.3 to 1.5, from 0.3 to 1.6, from 0.3 to 1.7, from 0.3 to 1.8, from 0.3 to 1.9, from 0.3 to 2.0, from 0.3 to 2.1, from 0.3 to 2.2, from 0.3 to 2.3, from 0.3 to 2.4, from 0.3 to 2.5, from 0.3 to 2.6, from 0.3 to 2.7, from 0.3 to 2.8, from 0.3 to 2.9, from 0.4 to 0.5, from 0.4 to 0.6, from 0.4 to 0.7, from 0.4 to 0.8, from 0.4 to 0.9, from 0.4 to 1.0, from 0.4 to 1.1, from 0.4 to 1.2, from 0.4 to 1.3, from 0.4 to 1.4, from 0.4 to 1.5, from 0.4 to 1.6, from 0.4 to 1.7, from 0.4 to 1.8, from 0.4 to 1.9, from 0.4 to 2.0, from 0.4 to 2.1, from 0.4 to 2.2, from 0.4 to 2.3, from 0.4 to 2.4, from 0.4 to 2.5, from 0.4 to 2.6, from 0.4 to 2.7, from 0.4 to 2.8, from 0.4 to 2.9, from 0.4 to 3, from 0.5 to 0.6, from 0.5 to 0.7, from 0.5 to 0.8, from 0.5 to 0.9, from 0.5 to 1.0, from 0.5 to 1.1, from 0.5 to 1.2, from 0.5 to 1.3, from 0.5 to 1.4, from 0.5 to 1.5, from 0.5 to 1.6, from 0.5 to 1.7, from 0.5 to 1.8, from 0.5 to 1.9, from 0.5 to 2.0, from 0.5 to 2.1, from 0.5 to 2.2, from 0.5 to 2.3, from 0.5 to 2.4, from 0.5 to 2.5, from 0.5 to 2.6, from 0.5 to 2.7, from 0.5 to 2.8, from 0.5 to 2.9, from 0.5 to 3, from 0.6 to 0.7, from 0.6 to 0.8, from 0.6 to 0.9, from 0.6 to 1.0, from 0.6 to 1.1, from 0.6 to 1.2, from 0.6 to 1.3, from 0.6 to 1.4, from 0.6 to 1.5, from 0.6 to 1.6, from 0.6 to 1.7, from 0.6 to 1.8, from 0.6 to 1.9, from 0.6 to 2.0, from 0.6 to 2.1, from 0.6 to 2.2, from 0.6 to 2.3, from 0.6 to 2.4, from 0.6 to 2.5, from 0.6 to 2.6, from 0.6 to 2.7, from 0.6 to 2.8, from 0.6 to 2.9, from 0.6 to 3, from 0.7 to 0.8, from 0.7 to 0.9, from 0.7 to 1.0, from 0.7 to 1.1, from 0.7 to 1.2, from 0.7 to 1.3, from 0.7 to 1.4, from 0.7 to 1.5, from 0.7 to 1.6, from 0.7 to 1.7, from 0.7 to 1.8, from 0.7 to 1.9, from 0.7 to 2.0, from 0.7 to 2.1, from 0.7 to 2.2, from 0.7 to 2.3, from 0.7 to 2.4, from 0.7 to 2.5, from 0.7 to 2.6, from 0.7 to 2.7, from 0.7 to 2.8, from 0.7 to 2.9, from 0.7 to 3, from 0.8 to 0.9, from 0.8 to 1.0, from 0.8 to 1.1, from 0.8 to 1.2, from 0.8 to 1.3, from 0.8 to 1.4, from 0.8 to 1.5, from 0.8 to 1.6, from 0.8 to 1.7, from 0.8 to 1.8, from 0.8 to 1.9, from 0.8 to 2.0, from 0.8 to 2.1, from 0.8 to 2.2, from 0.8 to 2.3, from 0.8 to 2.4, from 0.8 to 2.5, from 0.8 to 2.6, from 0.8 to 2.7, from 0.8 to 2.8, from 0.8 to 2.9, from 0.8 to 3, from 0.9 to 1.0, from 0.9 to 1.1, from 0.9 to 1.2, from 0.9 to 1.3, from 0.9 to 1.4, from 0.9 to 1.5, from 0.9 to 1.6, from 0.9 to 1.7, from 0.9 to 1.8, from 0.9 to 1.9, from 0.9 to 2.0, from 0.9 to 2.1, from 0.9 to 2.2, from 0.9 to 2.3, from 0.9 to 2.4, from 0.9 to 2.5, from 0.9 to 2.6, from 0.9 to 2.7, from 0.9 to 2.8, from 0.9 to 2.9, from 0.9 to 3, from 1.0 to 1.1, from 1.0 to 1.2, from 1.0 to 1.3, from 1.0 to 1.4, from 1.0 to 1.5, from 1.0 to 1.6, from 1.0 to 1.7, from 1.0 to 1.8, from 1.0 to 1.9, from 1.0 to 2.0, from 1.0 to 2.1, from 1.0 to 2.2, from 1.0 to 2.3, from 1.0 to 2.4, from 1.0 to 2.5, from 1.0 to 2.6, from 1.0 to 2.7, from 1.0 to 2.8, from 1.0 to 2.9, from 1.0 to 3, from 1.1 to 1.2, from 1.1 to 1.3, from 1.1 to 1.4, from 1.1 to 1.5, from 1.1 to 1.6, from 1.1 to 1.7, from 1.1 to 1.8, from 1.1 to 1.9, from 1.1 to 2.0, from 1.1 to 2.1, from 1.1 to 2.2, from 1.1 to 2.3, from 1.1 to 2.4, from 1.1 to 2.5, from 1.1 to 2.6, from 1.1 to 2.7, from 1.1 to 2.8, from 1.1 to 2.9, from 1.1 to 3, from 1.2 to 1.3, from 1.2 to 1.4, from 1.2 to 1.5, from 1.2 to 1.6, from 1.2 to 1.7, from 1.2 to 1.8, from 1.2 to 1.9, from 1.2 to 2.0, from 1.2 to 2.1, from 1.2 to 2.2, from 1.2 to 2.3, from 1.2 to 2.4, from 1.2 to 2.5, from 1.2 to 2.6, from 1.2 to 2.7, from 1.2 to 2.8, from 1.2 to 2.9, from 1.2 to 3, from 1.3 to 1.4, from 1.3 to 1.5, from 1.3 to 1.6, from 1.3 to 1.7, from 1.3 to 1.8, from 1.3 to 1.9, from 1.3 to 2.0, from 1.3 to 2.1, from 1.3 to 2.2, from 1.3 to 2.3, from 1.3 to 2.4, from 1.3 to 2.5, from 1.3 to 2.6, from 1.3 to 2.7, from 1.3 to 2.8, from 1.3 to 2.9, from 1.3 to 3, from 1.4 to 1.5, from 1.4 to 1.6, from 1.4 to 1.7, from 1.4 to 1.8, from 1.4 to 1.9, from 1.4 to 2.0, from 1.4 to 2.1, from 1.4 to 2.2, from 1.4 to 2.3, from 1.4 to 2.4, from 1.4 to 2.5, from 1.4 to 2.6, from 1.4 to 2.7, from 1.4 to 2.8, from 1.4 to 2.9, from 1.4 to 3, from 1.5 to 1.6, from 1.5 to 1.7, from 1.5 to 1.8, from 1.5 to 1.9, from 1.5 to 2.0, from 1.5 to 2.1, from 1.5 to 2.2, from 1.5 to 2.3, from 1.5 to 2.4, from 1.5 to 2.5, from 1.5 to 2.6, from 1.5 to 2.7, from 1.5 to 2.8, from 1.5 to 2.9, from 1.5 to 3, from 1.6 to 1.7, from 1.6 to 1.8, from 1.6 to 1.9, from 1.6 to 2.0, from 1.6 to 2.1, from 1.6 to 2.2, from 1.6 to 2.3, from 1.6 to 2.4, from 1.6 to 2.5, from 1.6 to 2.6, from 1.6 to 2.7, from 1.6 to 2.8, from 1.6 to 2.9, from 1.6 to 3, from 1.7 to 1.8, from 1.7 to 1.9, from 1.7 to 2.0, from 1.7 to 2.1, from 1.7 to 2.2, from 1.7 to 2.3, from 1.7 to 2.4, from 1.7 to 2.5, from 1.7 to 2.6, from 1.7 to 2.7, from 1.7 to 2.8, from 1.7 to 2.9, from 1.7 to 3, from 1.8 to 1.9, from 1.8 to 2.0, from 1.8 to 2.1, from 1.8 to 2.2, from 1.8 to 2.3, from 1.8 to 2.4, from 1.8 to 2.5, from 1.8 to 2.6, from 1.8 to 2.7, from 1.8 to 2.8, from 1.8 to 2.9, from 1.8 to 3, from 1.9 to 2.0, from 1.9 to 2.1, from 1.9 to 2.2, from 1.9 to 2.3, from 1.9 to 2.4, from 1.9 to 2.5, from 1.9 to 2.6, from 1.9 to 2.7, from 1.9 to 2.8, from 1.9 to 2.9, from 1.9 to 3, from 2.0 to 2.1, from 2.0 to 2.2, from 2.0 to 2.3, from 2.0 to 2.4, from 2.0 to 2.5, from 2.0 to 2.6, from 2.0 to 2.7, from 2.0 to 2.8, from 2.0 to 2.9, from 2.0 to 3, from 2.1 to 2.2, from 2.1 to 2.3, from 2.1 to 2.4, from 2.1 to 2.5, from 2.1 to 2.6, from 2.1 to 2.7, from 2.1 to 2.8, from 2.1 to 2.9, from 2.1 to 3, from 2.2 to 2.3, from 2.2 to 2.4, from 2.2 to 2.5, from 2.2 to 2.6, from 2.2 to 2.7, from 2.2 to 2.8, from 2.2 to 2.9, from 2.2 to 3, from 2.3 to 2.4, from 2.3 to 2.5, from 2.3 to 2.6, from 2.3 to 2.7, from 2.3 to 2.8, from 2.3 to 2.9, from 2.3 to 3, from 2.4 to 2.5, from 2.4 to 2.6, from 2.4 to 2.7, from 2.4 to 2.8, from 2.4 to 2.9, from 2.4 to 3, from 2.5 to 2.6, from 2.5 to 2.6, from 2.5 to 2.7, from 2.5 to 2.8, from 2.5 to 2.9, from 2.5 to 3, from 2.6 to 2.7, from 2.6 to 2.8, from 2.6 to 2.9, from 2.6 to 3, from 2.7 to 2.8, from 2.7 to 2.9, from 2.7 to 3, from 2.8 to 2.9, from 2.8 to 3, or from 2.9 to 3.
- Optionally, the aluminum alloy products described above may include a plurality of particles, where 80 percent or more of the inter-particle spacings between particles are from 5 µm to 15 µm. Optionally, the plurality of particles may include iron-containing particles, such as iron-containing particles where a majority have a diameter from 1 µm to 40 µm. Optionally, the iron-containing particles may comprise from 1% to 4% of a total volume of the aluminum alloy.
- Optionally, the aluminum alloys for the aluminum alloy products described above may comprise or further comprise manganese-containing dispersoids, such as where a majority of the manganese-containing dispersoids have a diameter of from 10 nm to 1.5 µm. Optionally, the manganese-containing dispersoids may comprise up to 1% of a total volume of the aluminum alloy. In some cases, dispersoids are not included in counts of particles of other types, such as α-phase particles and/or β-phase particles, and/or may optionally be counted separately from other types of particles.
- Metal products, such as aluminum alloy products, are also described herein. In some embodiments, a metal product may be prepared by any of the methods described herein. In some specific embodiments, a metal product comprises a homogenized 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, such as with a ratio of a silicon wt. % in the homogenized 3xxx series aluminum alloy to an iron wt. % in the homogenized 3xxx series aluminum alloy of from 0.5 to 1.0, and including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and optionally β-phase intermetallic particles comprising aluminum and one or more of iron or manganese, with at least a portion of the α-phase intermetallic particles corresponding to β-phase intermetallic particles transformed during homogenization of the homogenized 3xxx series aluminum alloy. Optionally a ratio of a volume % and/or a number density of the α-phase intermetallic particles to a volume % or a number density of the β-phase intermetallic particles is from 0.6 to 1000, or more.
- In another aspect, methods of making aluminum alloy products are described. An example method of this aspect comprises preparing a cast aluminum alloy product comprising an aluminum alloy, such as an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product. Various homogenization conditions are useful with the methods described herein. Optionally, homogenizing may include heating the cast aluminum alloy product to a homogenization temperature, such as a homogenization temperature that is between 500° C. to 650° C., such as from 500° C. to 510° C., from 500° C. to 520° C., from 500° C. to 530° C., from 500° C. to 540° C., from 500° C. to 550° C., from 500° C. to 560° C., from 500° C. to 570° C., from 500° C. to 575° C., from 500° C. to 580° C., from 500° C. to 585° C., from 500° C. to 590° C., from 500° C. to 600° C., from 500° C. to 610° C., from 500° C. to 615° C., from 500° C. to 620° C., from 500° C. to 630° C., from 500° C. to 640° C., from 510° C. to 520° C., from 510° C. to 530° C., from 510° C. to 540° C., from 510° C. to 550° C., from 510° C. to 560° C., from 510° C. to 570° C., from 510° C. to 575° C., from 510° C. to 580° C., from 510° C. to 585° C., from 510° C. to 590° C., from 510° C. to 600° C., from 510° C. to 610° C., from 510° C. to 615° C., from 510° C. to 620° C., from 510° C. to 630° C., from 510° C. to 640° C., from 510° C. to 650° C., from 520° C. to 530° C., from 520° C. to 540° C., from 520° C. to 550° C., from 520° C. to 560° C., from 520° C. to 570° C., from 520° C. to 575° C., from 520° C. to 580° C., from 520° C. to 585° C., from 520° C. to 590° C., from 520° C. to 600° C., from 520° C. to 610° C., from 520° C. to 615° C., from 520° C. to 620° C., from 520° C. to 630° C., from 520° C. to 640° C., from 520° C. to 650° C., from 530° C. to 540° C., from 530° C. to 550° C., from 530° C. to 560° C., from 530° C. to 570° C., from 530° C. to 575° C., from 530° C. to 580° C., from 530° C. to 585° C., from 530° C. to 590° C., from 530° C. to 600° C., from 530° C. to 610° C., from 530° C. to 615° C., from 530° C. to 620° C., from 530° C. to 630° C., from 530° C. to 640° C., from 530° C. to 650° C., from 540° C. to 550° C., from 540° C. to 560° C., from 540° C. to 570° C., from 540° C. to 575° C., from 540° C. to 580° C., from 540° C. to 585° C., from 540° C. to 590° C., from 540° C. to 600° C., from 540° C. to 610° C., from 540° C. to 615° C., from 540° C. to 620° C., from 540° C. to 630° C., from 540° C. to 640° C., from 540° C. to 650° C., from 550° C. to 560° C., from 550° C. to 570° C., from 550° C. to 575° C., from 550° C. to 580° C., from 550° C. to 585° C., from 550° C. to 590° C., from 550° C. to 600° C., from 550° C. to 610° C., from 550° C. to 615° C., from 550° C. to 620° C., from 550° C. to 630° C., from 550° C. to 640° C., from 550° C. to 650° C., from 560° C. to 570° C., from 560° C. to 575° C., from 560° C. to 580° C., from 560° C. to 585° C., from 560° C. to 590° C., from 560° C. to 600° C., from 560° C. to 610° C., from 560° C. to 615° C., from 560° C. to 620° C., from 560° C. to 630° C., from 560° C. to 640° C., from 560° C. to 650° C., from 570° C. to 575° C., from 570° C. to 580° C., from 570° C. to 585° C., from 570° C. to 590° C., from 570° C. to 600° C., from 570° C. to 610° C., from 570° C. to 615° C., from 570° C. to 620° C., from 570° C. to 630° C., from 570° C. to 640° C., from 570° C. to 650° C., from 575° C. to 580° C., from 575° C. to 585° C., from 575° C. to 590° C., from 575° C. to 600° C., from 575° C. to 610° C., from 575° C. to 615° C., from 575° C. to 620° C., from 575° C. to 630° C., from 575° C. to 640° C., from 575° C. to 650° C., from 580° C. to 585° C., from 580° C. to 590° C., from 580° C. to 600° C., from 580° C. to 610° C., from 580° C. to 615° C., from 580° C. to 620° C., from 580° C. to 630° C., from 580° C. to 640° C., from 580° C. to 650° C., from 585° C. to 590° C., from 585° C. to 600° C., from 585° C. to 610° C., from 585° C. to 615° C., from 585° C. to 620° C., from 585° C. to 630° C., from 585° C. to 640° C., from 585° C. to 650° C., from 590° C. to 600° C., from 590° C. to 610° C., from 590° C. to 615° C., from 590° C. to 620° C., from 590° C. to 630° C., from 590° C. to 640° C., from 590° C. to 650° C., from 600° C. to 610° C., from 600° C. to 615° C., from 600° C. to 620° C., from 600° C. to 630° C., from 600° C. to 640° C., from 600° C. to 650° C., from 610° C. to 615° C., from 610° C. to 620° C., from 610° C. to 630° C., from 610° C. to 640° C., from 610° C. to 650° C., from 615° C. to 620° C., from 615° C. to 630° C., from 615° C. to 640° C., from 615° C. to 650° C., from 620° C. to 630° C., from 620° C. to 640° C., from 620° C. to 650° C., from 630° C. to 640° C., from 630° C. to 650° C., or from 640° C. to 650° C. The homogenization temperature may optionally be within 75° C. of a solidus temperature of the aluminum alloy, such as within 70° C. of a solidus temperature of the aluminum alloy, within 65° C. of a solidus temperature of the aluminum alloy, within 60° C. of a solidus temperature of the aluminum alloy, within 55° C. of a solidus temperature of the aluminum alloy, within 50° C. of a solidus temperature of the aluminum alloy, within 45° C. of a solidus temperature of the aluminum alloy, within 40° C. of a solidus temperature of the aluminum alloy, within 35° C. of a solidus temperature of the aluminum alloy, within 30° C. of a solidus temperature of the aluminum alloy, within 25° C. of a solidus temperature of the aluminum alloy, within 20° C. of a solidus temperature of the aluminum alloy, within 15° C. of a solidus temperature of the aluminum alloy, within 10° C. of a solidus temperature of the aluminum alloy, or within 5° C. of a solidus temperature of the aluminum alloy.
- During soaking, the cast aluminum alloy product may optionally be at the homogenization temperature (i.e., soaking) for a time duration from 0.1 hours to 36 hours or from 12 hours to 36 hours, such as from 0.1 hours to 0.5 hours, from 0.1 hours to 1 hour, from 0.1 hours to 1.5 hours, from 0.1 hours to 2 hours, from 0.1 hours to 2.5 hours, from 0.1 hours to 3 hours, from 0.1 hours to 3.5 hours, from 0.1 hours to 4 hours, from 0.1 hours to 4.5 hours, from 0.1 hours to 5 hours, from 0.1 hours to 5.5 hours, from 0.1 hours to 6 hours, from 0.1 hours to 6.5 hours, from 0.1 hours to 7 hours, from 0.1 hours to 7.5 hours, from 0.1 hours to 8 hours, from 0.1 hours to 8.5 hours, from 0.1 hours to 9 hours, from 0.1 hours to 9.5 hours, from 0.1 hours to 10 hours, from 0.1 hours to 10.5 hours, from 0.1 hours to 11 hours, from 0.1 hours to 11.5 hours, from 0.1 hours to 12 hours, from 0.1 hours to 12.5 hours, from 0.1 hours to 13 hours, from 0.1 hours to 13.5 hours, from 0.1 hours to 14 hours, from 0.1 hours to 14.5 hours, from 0.1 hours to 15 hours, from 0.1 hours to 15.5 hours, from 0.1 hours to 16 hours, from 0.1 hours to 16.5 hours, from 0.1 hours to 17 hours, from 0.1 hours to 17.5 hours, from 0.1 hours to 18 hours, from 0.1 hours to 18.5 hours, from 0.1 hours to 19 hours, from 0.1 hours to 19.5 hours, from 0.1 hours to 20 hours, from 0.1 hours to 20.5 hours, from 0.1 hours to 21 hours, from 0.1 hours to 21.5 hours, from 0.1 hours to 22 hours, from 0.1 hours to 22.5 hours, from 0.1 hours to 23 hours, from 0.1 hours to 23.5 hours, from 0.1 hours to 24 hours, from 0.1 hours to 25 hours, from 0.1 hours to 26 hours, from 0.1 hours to 27 hours, from 0.1 hours to 28 hours, from 0.1 hours to 29 hours, from 0.1 hours to 30 hours, from 0.1 hours to 31 hours, from 0.1 hours to 32 hours, from 0.1 hours to 33 hours, from 0.1 hours to 34 hours, from 0.1 hours to 35 hours, from 0.1 hours to 36 hours, from 0.5 hours to 1 hour, from 0.5 hours to 1.5 hours, from 0.5 hours to 2 hours, from 0.5 hours to 2.5 hours, from 0.5 hours to 3 hours, from 0.5 hours to 3.5 hours, from 0.5 hours to 4 hours, from 0.5 hours to 4.5 hours, from 0.5 hours to 5 hours, from 0.5 hours to 5.5 hours, from 0.5 hours to 6 hours, from 0.5 hours to 6.5 hours, from 0.5 hours to 7 hours, from 0.5 hours to 7.5 hours, from 0.5 hours to 8 hours, from 0.5 hours to 8.5 hours, from 0.5 hours to 9 hours, from 0.5 hours to 9.5 hours, from 0.5 hours to 10 hours, from 0.5 hours to 10.5 hours, from 0.5 hours to 11 hours, from 0.5 hours to 11.5 hours, from 0.5 hours to 12 hours, from 0.5 hours to 12.5 hours, from 0.5 hours to 13 hours, from 0.5 hours to 13.5 hours, from 0.5 hours to 14 hours, from 0.5 hours to 14.5 hours, from 0.5 hours to 15 hours, from 0.5 hours to 15.5 hours, from 0.5 hours to 16 hours, from 0.5 hours to 16.5 hours, from 0.5 hours to 17 hours, from 0.5 hours to 17.5 hours, from 0.5 hours to 18 hours, from 0.5 hours to 18.5 hours, from 0.5 hours to 19 hours, from 0.5 hours to 19.5 hours, from 0.5 hours to 20 hours, from 0.5 hours to 20.5 hours, from 0.5 hours to 21 hours, from 0.5 hours to 21.5 hours, from 0.5 hours to 22 hours, from 0.5 hours to 22.5 hours, from 0.5 hours to 23 hours, from 0.5 hours to 23.5 hours, from 0.5 hours to 24 hours, from 0.5 hours to 25 hours, from 0.5 hours to 26 hours, from 0.5 hours to 27 hours, from 0.5 hours to 28 hours, from 0.5 hours to 29 hours, from 0.5 hours to 30 hours, from 0.5 hours to 31 hours, from 0.5 hours to 32 hours, from 0.5 hours to 33 hours, from 0.5 hours to 34 hours, from 0.5 hours to 35 hours, from 0.5 hours to 36 hours, from 1 hour to 1.5 hours, from 1 hour to 2 hours, from 1 hour to 2.5 hours, from 1 hour to 3 hours, from 1 hour to 3.5 hours, from 1 hour to 4 hours, from 1 hour to 4.5 hours, from 1 hour to 5 hours, from 1 hour to 5.5 hours, from 1 hour to 6 hours, from 1 hour to 6.5 hours, from 1 hour to 7 hours, from 1 hour to 7.5 hours, from 1 hour to 8 hours, from 1 hour to 8.5 hours, from 1 hour to 9 hours, from 1 hour to 9.5 hours, from 1 hour to 10 hours, from 1 hour to 10.5 hours, from 1 hour to 11 hours, from 1 hour to 11.5 hours, from 1 hour to 12 hours, from 1 hour to 12.5 hours, from 1 hour to 13 hours, from 1 hour to 13.5 hours, from 1 hour to 14 hours, from 1 hour to 14.5 hours, from 1 hour to 15 hours, from 1 hour to 15.5 hours, from 1 hour to 16 hours, from 1 hour to 16.5 hours, from 1 hour to 17 hours, from 1 hour to 17.5 hours, from 1 hour to 18 hours, from 1 hour to 18.5 hours, from 1 hour to 19 hours, from 1 hour to 19.5 hours, from 1 hour to 20 hours, from 1 hour to 20.5 hours, from 1 hour to 21 hours, from 1 hour to 21.5 hours, from 1 hour to 22 hours, from 1 hour to 22.5 hours, from 1 hour to 23 hours, from 1 hour to 23.5 hours, from 1 hour to 24 hours, from 1 hours to 25 hours, from 1 hours to 26 hours, from 1 hours to 27 hours, from 1 hours to 28 hours, from 1 hours to 29 hours, from 1 hours to 30 hours, from 1 hours to 31 hours, from 1 hours to 32 hours, from 1 hours to 33 hours, from 1 hours to 34 hours, from 1 hours to 35 hours, from 1 hours to 36 hours, from 1.5 hours to 2 hours, from 1.5 hours to 2.5 hours, from 1.5 hours to 3 hours, from 1.5 hours to 3.5 hours, from 1.5 hours to 4 hours, from 1.5 hours to 4.5 hours, from 1.5 hours to 5 hours, from 1.5 hours to 5.5 hours, from 1.5 hours to 6 hours, from 1.5 hours to 6.5 hours, from 1.5 hours to 7 hours, from 1.5 hours to 7.5 hours, from 1.5 hours to 8 hours, from 1.5 hours to 8.5 hours, from 1.5 hours to 9 hours, from 1.5 hours to 9.5 hours, from 1.5 hours to 10 hours, from 1.5 hours to 10.5 hours, from 1.5 hours to 11 hours, from 1.5 hours to 11.5 hours, from 1.5 hours to 12 hours, from 1.5 hours to 12.5 hours, from 1.5 hours to 13 hours, from 1.5 hours to 13.5 hours, from 1.5 hours to 14 hours, from 1.5 hours to 14.5 hours, from 1.5 hours to 15 hours, from 1.5 hours to 15.5 hours, from 1.5 hours to 16 hours, from 1.5 hours to 16.5 hours, from 1.5 hours to 17 hours, from 1.5 hours to 17.5 hours, from 1.5 hours to 18 hours, from 1.5 hours to 18.5 hours, from 1.5 hours to 19 hours, from 1.5 hours to 19.5 hours, from 1.5 hours to 20 hours, from 1.5 hours to 20.5 hours, from 1.5 hours to 21 hours, from 1.5 hours to 21.5 hours, from 1.5 hours to 22 hours, from 1.5 hours to 22.5 hours, from 1.5 hours to 23 hours, from 1.5 hours to 23.5 hours, from 1.5 hours to 24 hours, from 1.5 hours to 25 hours, from 1.5 hours to 26 hours, from 1.5 hours to 27 hours, from 1.5 hours to 28 hours, from 1.5 hours to 29 hours, from 1.5 hours to 30 hours, from 1.5 hours to 31 hours, from 1.5 hours to 32 hours, from 1.5 hours to 33 hours, from 1.5 hours to 34 hours, from 1.5 hours to 35 hours, from 1.5 hours to 36 hours, from 2 hours to 2.5 hours, from 2 hours to 3 hours, from 2 hours to 3.5 hours, from 2 hours to 4 hours, from 2 hours to 4.5 hours, from 2 hours to 5 hours, from 2 hours to 5.5 hours, from 2 hours to 6 hours, from 2 hours to 6.5 hours, from 2 hours to 7 hours, from 2 hours to 7.5 hours, from 2 hours to 8 hours , from 2 hours to 8.5 hours, from 2 hours to 9 hours, from 2 hours to 9.5 hours, from 2 hours to 10 hours, from 2 hours to 10.5 hours, from 2 hours to 11 hours, from 2 hours to 11.5 hours, from 2 hours to 12 hours, from 2 hours to 12.5 hours, from 2 hours to 13 hours, from 2 hours to 13.5 hours, from 2 hours to 14 hours, from 2 hours to 14.5 hours, from 2 hours to 15 hours, from 2 hours to 15.5 hours, from 2 hours to 16 hours, from 2 hours to 16.5 hours, from 2 hours to 17 hours, from 2 hours to 17.5 hours, from 2 hours to 18 hours, from 2 hours to 18.5 hours, from 2 hours to 19 hours, from 2 hours to 19.5 hours, from 2 hours to 20 hours, from 2 hours to 20.5 hours, from 2 hours to 21 hours, from 2 hours to 21.5 hours, from 2 hours to 22 hours, from 2 hours to 22.5 hours, from 2 hours to 23 hours, from 2 hours to 23.5 hours, from 2 hours to 24 hours, from 2 hours to 25 hours, from 2 hours to 26 hours, from 2 hours to 27 hours, from 2 hours to 28 hours, from 2 hours to 29 hours, from 2 hours to 30 hours, from 2 hours to 31 hours, from 2 hours to 32 hours, from 2 hours to 33 hours, from 2 hours to 34 hours, from 2 hours to 35 hours, from 2 hours to 36 hours, from 2.5 hours to 3 hours, from 2.5 hours to 3.5 hours, from 2.5 hours to 4 hours, from 2.5 hours to 4.5 hours, from 2.5 hours to 5 hours, from 2.5 hours to 5.5 hours, from 2.5 hours to 6 hours, from 2.5 hours to 6.5 hours, from 2.5 hours to 7 hours, from 2.5 hours to 7.5 hours, from 2.5 hours to 8 hours, from 2.5 hours to 8.5 hours, from 2.5 hours to 9 hours, from 2.5 hours to 9.5 hours, from 2.5 hours to 10 hours, from 2.5 hours to 10.5 hours, from 2.5 hours to 11 hours, from 2.5 hours to 11.5 hours, from 2.5 hours to 12 hours, from 2.5 hours to 12.5 hours, from 2.5 hours to 13 hours, from 2.5 hours to 13.5 hours, from 2.5 hours to 14 hours, from 2.5 hours to 14.5 hours, from 2.5 hours to 15 hours, from 2.5 hours to 15.5 hours, from 2.5 hours to 16 hours, from 2.5 hours to 16.5 hours, from 2.5 hours to 17 hours, from 2.5 hours to 17.5 hours, from 2.5 hours to 18 hours, from 2.5 hours to 18.5 hours, from 2.5 hours to 19 hours, from 2.5 hours to 19.5 hours, from 2.5 hours to 20 hours, from 2.5 hours to 20.5 hours, from 2.5 hours to 21 hours, from 2.5 hours to 21.5 hours, from 2.5 hours to 22 hours, from 2.5 hours to 22.5 hours, from 2.5 hours to 23 hours, from 2.5 hours to 23.5 hours, from 2.5 hours to 24 hours, from 2.5 hours to 25 hours, from 2.5 hours to 26 hours, from 2.5 hours to 27 hours, from 2.5 hours to 28 hours, from 2.5 hours to 29 hours, from 2.5 hours to 30 hours, from 2 .5 hours to 31 hours, from 2.5 hours to 32 hours, from 2.5 hours to 33 hours, from 2.5 hours to 34 hours, from 2.5 hours to 35 hours, from 2.5 hours to 36 hours, from 3 hours to 3.5 hours, from 3 hours to 4 hours, from 3 hours to 4.5 hours, from 3 hours to 5 hours, from 3 hours to 5.5 hours, from 3 hours to 6 hours, from 3 hours to 6.5 hours, from 3 hours to 7 hours, from 3 hours to 7.5 hours , from 3 hours to 8 hours, from 3 hours to 8.5 hours, from 3 hours to 9 hours, from 3 hours to 9.5 hours, from 3 hours to 10 hours, from 3 hours to 10.5 hours, from 3 hours to 11 hours, from 3 hours to 11.5 hours, from 3 hours to 12 hours, from 3 hours to 12.5 hours, from 3 hours to 13 hours, from 3 hours to 13.5 hours, from 3 hours to 14 hours, from 3 hours to 14.5 hours, from 3 hours to 15 hours, from 3 hours to 15.5 hours, from 3 hours to 16 hours, from 3 hours to 16.5 hours, from 3 hours to 17 hours, from 3 hours to 17.5 hours, from 3 hours to 18 hours, from 3 hours to 18.5 hours, from 3 hours to 19 hours, from 3 hours to 19.5 hours, from 3 hours to 20 hours, from 3 hours to 20.5 hours, from 3 hours to 21 hours, from 3 hours to 21.5 hours, from 3 hours to 22 hours, from 3 hours to 22.5 hours, from 3 hours to 23 hours, from 3 hours to 23.5 hours, from 3 hours to 24 hours, from 3 hours to 25 hours, from 3 hours to 26 hours, from 3 hours to 27 hours, from 3 hours to 28 hours, from 3 hours to 29 hours, from 3 hours to 30 hours, from 3 hours to 31 hours, from 3 hours to 32 hours, from 3 hours to 33 hours, from 3 hours to 34 hours, from 3 hours to 35 hours, from 3 hours to 36 hours, from 3.5 hours to 4 hours, from 3.5 hours to 4.5 hours, from 3.5 hours to 5 hours, from 3.5 hours to 5.5 hours, from 3.5 hours to 6 hours, from 3.5 hours to 6.5 hours, from 3.5 hours to 7 hours, from 3.5 hours to 7.5 hours, from 3.5 hours to 8 hours, from 3.5 hours to 8.5 hours, from 3.5 hours to 9 hours, from 3.5 hours to 9.5 hours, from 3.5 hours to 10 hours, from 3.5 hours to 10.5 hours, from 3.5 hours to 11 hours, from 3.5 hours to 11.5 hours, from 3.5 hours to 12 hours, from 3.5 hours to 12.5 hours, from 3.5 hours to 13 hours, from 3.5 hours to 13.5 hours, from 3.5 hours to 14 hours, from 3.5 hours to 14.5 hours, from 3.5 hours to 15 hours, from 3.5 hours to 15.5 hours, from 3.5 hours to 16 hours, from 3.5 hours to 16.5 hours, from 3.5 hours to 17 hours, from 3.5 hours to 17.5 hours, from 3.5 hours to 18 hours, from 3.5 hours to 18.5 hours, from 3.5 hours to 19 hours, from 3.5 hours to 19.5 hours, from 3.5 hours to 20 hours, from 3.5 hours to 20.5 hours, from 3.5 hours to 21 hours, from 3.5 hours to 21.5 hours, from 3.5 hours to 22 hours, from 3.5 hours to 22.5 hours, from 3.5 hours to 23 hours, from 3.5 hours to 23.5 hours, from 3.5 hours to 24 hours, from 3.5 hours to 25 hours, from 3.5 hours to 26 hours, from 3.5 hours to 27 hours, from 3.5 hours to 28 hours, from 3.5 hours to 29 hours, from 3.5 hours to 30 hours, from 3.5 hours to 31 hours, from 3.5 hours to 32 hours, from 3.5 hours to 33 hours, from 3.5 hours to 34 hours, from 3.5 hours to 35 hours, from 3.5 hours to 36 hours, from 4 hours to 4.5 hours, from 4 hours to 5 hours, from 4 hours to 5.5 hours, from 4 hours to 6 hours, from 4 hours to 6.5 hours, from 4 hours to 7 hours, from 4 hours to 7.5 hours, from 4 hours to 8 hours, from 4 hours to 8.5 hours, from 4 hours to 9 hours, from 4 hours to 9.5 hours, from 4 hours to 10 hours, from 4 hours to 10.5 hours, from 4 hours to 11 hours, from 4 hours to 11.5 hours, from 4 hours to 12 hours, from 4 hours to 12.5 hours, from 4 hours to 13 hours, from 4 hours to 13.5 hours, from 4 hours to 14 hours, from 4 hours to 14.5 hours, from 4 hours to 15 hours, from 4 hours to 15.5 hours, from 4 hours to 16 hours, from 4 hours to 16.5 hours, from 4 hours to 17 hours, from 4 hours to 17.5 hours, from 4 hours to 18 hours, from 4 hours to 18.5 hours, from 4 hours to 19 hours, from 4 hours to 19.5 hours, from 4 hours to 20 hours, from 4 hours to 20.5 hours, from 4 hours to 21 hours, from 4 hours to 21.5 hours, from 4 hours to 22 hours, from 4 hours to 22.5 hours, from 4 hours to 23 hours, from 4 hours to 23.5 hours, from 4 hours to 24 hours, from 4 hours to 25 hours, from 4 hours to 26 hours, from 4 hours to 27 hours, from 4 hours to 28 hours, from 4 hours to 29 hours, from 4 hours to 30 hours, from 4 hours to 31 hours, from 4 hours to 32 hours, from 4 hours to 33 hours, from 4 hours to 34 hours, from 4 hours to 35 hours, from 4 hours to 36 hours, from 4.5 hours to 5 hours, from 4.5 hours to 5.5 hours, from 4.5 hours to 6 hours, from 4.5 hours to 6.5 hours, from 4.5 hours to 7 hours, from 4.5 hours to 7.5 hours, from 4.5 hours to 8 hours, from 4.5 hours to 8.5 hours, from 4.5 hours to 9 hours, from 4.5 hours to 9.5 hours, from 4.5 hours to 10 hours, from 4.5 hours to 10.5 hours, from 4.5 hours to 11 hours, from 4.5 hours to 11.5 hours, from 4.5 hours to 12 hours, from 4.5 hours to 12.5 hours, from 4.5 hours to 13 hours, from 4.5 hours to 13.5 hours, from 4.5 hours to 14 hours, from 4.5 hours to 14.5 hours, from 4.5 hours to 15 hours, from 4.5 hours to 15.5 hours, from 4.5 hours to 16 hours, from 4.5 hours to 16.5 hours, from 4.5 hours to 17 hours, from 4.5 hours to 17.5 hours, from 4.5 hours to 18 hours, from 4.5 hours to 18.5 hours, from 4.5 hours to 19 hours, from 4.5 hours to 19.5 hours, from 4.5 hours to 20 hours, from 4.5 hours to 20.5 hours, from 4.5 hours to 21 hours, from 4.5 hours to 21.5 hours, from 4.5 hours to 22 hours, from 4.5 hours to 22.5 hours, from 4.5 hours to 23 hours, from 4.5 hours to 23.5 hours, from 4.5 hours to 24 hours, from 4.5 hours to 25 hours, from 4.5 hours to 26 hours, from 4.5 hours to 27 hours, from 4.5 hours to 28 hours, from 4.5 hours to 29 hours, from 4.5 hours to 30 hours, from 4.5 hours to 31 hours, from 4.5 hours to 32 hours, from 4.5 hours to 33 hours, from 4.5 hours to 34 hours, from 4.5 hours to 35 hours, from 4.5 hours to 36 hours, from 5 hours to 5.5 hours, from 5 hours to 6 hours, from 5 hours to 6.5 hours, from 5 hours to 7 hours, from 5 hours to 7.5 hours, from 5 hours to 8 hours, from 5 hours to 8.5 hours, from 5 hours to 9 hours, from 5 hours to 9.5 hours, from 5 hours to 10 hours, from 5 hours to 10.5 hours, from 5 hours to 11 hours, from 5 hours to 11.5 hours, from 5 hours to 12 hours, from 5 hours to 12.5 hours, from 5 hours to 13 hours, from 5 hours to 13.5 hours, from 5 hours to 14 hours, from 5 hours to 14.5 hours, from 5 hours to 15 hours, from 5 hours to 15.5 hours, from 5 hours to 16 hours, from 5 hours to 16.5 hours, from 5 hours to 17 hours, from 5 hours to 17.5 hours, from 5 hours to 18 hours, from 5 hours to 18.5 hours, from 5 hours to 19 hours, from 5 hours to 19.5 hours, from 5 hours to 20 hours, from 5 hours to 20.5 hours, from 5 hours to 21 hours, from 5 hours to 21.5 hours, from 5 hours to 22 hours, from 5 hours to 22.5 hours, from 5 hours to 23 hours, from 5 hours to 23.5 hours, from 5 hours to 24 hours, from 5 hours to 25 hours, from 5 hours to 26 hours, from 5 hours to 27 hours, from 5 hours to 28 hours, from 5 hours to 29 hours, from 5 hours to 30 hours, from 5 hours to 31 hours, from 5 hours to 32 hours, from 5 hours to 33 hours, from 5 hours to 34 hours, from 5 hours to 35 hours, from 5 hours to 36 hours, from 5.5 hours to 6 hours, from 5.5 hours to 6.5 hours, from 5.5 hours to 7 hours, from 5.5 hours to 7.5 hours, from 5.5 hours to 8 hours, from 5.5 hours to 8.5 hours, from 5.5 hours to 9 hours, from 5.5 hours to 9.5 hours, from 5.5 hours to 10 hours, from 5.5 hours to 10.5 hours, from 5.5 hours to 11 hours, from 5.5 hours to 11.5 hours, from 5.5 hours to 12 hours, from 5.5 hours to 12.5 hours, from 5.5 hours to 13 hours, from 5.5 hours to 13.5 hours, from 5.5 hours to 14 hours, from 5.5 hours to 14.5 hours, from 5.5 hours to 15 hours, from 5.5 hours to 15.5 hours, from 5.5 hours to 16 hours, from 5.5 hours to 16.5 hours, from 5.5 hours to 17 hours, from 5.5 hours to 17.5 hours, from 5.5 hours to 18 hours, from 5.5 hours to 18.5 hours, from 5.5 hours to 19 hours, from 5.5 hours to 19.5 hours, from 5.5 hours to 20 hours, from 5.5 hours to 20.5 hours, from 5.5 hours to 21 hours, from 5.5 hours to 21.5 hours, from 5.5 hours to 22 hours, from 5.5 hours to 22.5 hours, from 5.5 hours to 23 hours, from 5.5 hours to 23.5 hours, from 5.5 hours to 24 hours, from 5.5 hours to 25 hours, from 5.5 hours to 26 hours, from 5.5 hours to 27 hours, from 5.5 hours to 28 hours, from 5.5 hours to 29 hours, from 5.5 hours to 30 hours, from 5.5 hours to 31 hours, from 5.5 hours to 32 hours, from 5.5 hours to 33 hours, from 5.5 hours to 34 hours, from 5.5 hours to 35 hours, from 5.5 hours to 36 hours, from 6 hours to 6.5 hours, from 6 hours to 7 hours, from 6 hours to 7.5 hours, from 6 hours to 8 hours, from 6 hours to 8.5 hours, from 6 hours to 9 hours, from 6 hours to 9.5 hours, from 6 hours to 10 hours, from 6 hours to 10.5 hours, from 6 hours to 11 hours, from 6 hours to 11.5 hours, from 6 hours to 12 hours, from 6 hours to 12.5 hours, from 6 hours to 13 hours, from 6 hours to 13.5 hours, from 6 hours to 14 hours, from 6 hours to 14.5 hours, from 6 hours to 15 hours, from 6 hours to 15.5 hours, from 6 hours to 16 hours, from 6 hours to 16.5 hours, from 6 hours to 17 hours, from 6 hours to 17.5 hours, from 6 hours to 18 hours, from 6 hours to 18.5 hours, from 6 hours to 19 hours, from 6 hours to 19.5 hours, from 6 hours, from 6 hours to 20.5 hours, from 6 hours to 21 hours, from 6 hours to 21.5 hours, from 6 hours to 22 hours, from 6 hours to 22.5 hours, from 6 hours to 23 hours, from 6 hours, from 6 hours to 24 hours, from 6 hours to 25 hours, from 6 hours to 26 hours, f to 27 hours, from 6 hours to 28 hours, from 6 hours to 29 hours, from 6 hours to 30 hours, from 6 hours to 31 hours, from 6 hours to 32 hours, from 6 hours to 33 hours, from 6 hours to 34 hours, from 6 hours to 35 hours, from 6 hours to 36 hours, from 6.5 hours to 7 hours, from 6.5 hours to 7.5 hours, from 6.5 hours to 8 hours, from 6.5 hours to 8.5 hours, from 6.5 hours to 9 hours, from 6.5 hours to 9.5 hours, from 6.5 hours to 10 hours, from 6.5 hours to 10.5 hours, from 6.5 hours to 11 hours, from 6.5 hours to 11.5 hours, from 6.5 hours to 12 hours, from 6.5 hours to 12.5 hours, from 6.5 hours to 13 hours, from 6.5 hours to 13.5 hours, from 6.5 hours to 14 hours, from 6.5 hours to 14.5 hours, from 6.5 hours to 15 hours, from 6.5 hours to 15.5 hours, from 6.5 hours to 16 hours, from 6.5 hours to 16.5 hours, from 6.5 hours to 17 hours, from 6.5 hours to 17.5 hours, from 6.5 hours to 18 hours, from 6.5 hours to 18.5 hours, from 6.5 hours to 19 hours, from 6.5 hours to 19.5 hours, from 6.5 hours to 20 hours, from 6.5 hours to 20.5 hours, from 6.5 hours to 21 hours, from 6.5 hours to 21.5 hours, from 6.5 hours to 22 hours, from 6.5 hours to 22.5 hours, from 6.5 hours to 23 hours, from 6.5 hours to 23.5 hours, from 6.5 hours to 24 hours, from 6.5 hours to 25 hours, from 6.5 hours to 26 hours, from 6.5 hours to 27 hours, from 6.5 hours to 28 hours, from 6.5 hours to 29 hours, from 6.5 hours to 30 hours, from 6.5 hours to 31 hours, from 6.5 hours to 32 hours, from 6.5 hours to 33 hours, from 6.5 hours to 34 hours, from 6.5 hours to 35 hours, from 6.5 hours to 36 hours, from 7 hours to 7.5 hours, from 7 hours to 8 hours, from 7 hours to 8.5 hours, from 7 hours to 9 hours, from 7 hours to 9.5 hours, from 7 hours to 10 hours, from 7 hours to 10.5 hours, from 7 hours to 11 hours, from 7 hours to 11.5 hours, from 7 hours to 12 hours, from 7 hours to 12.5 hours, from 7 hours to 13 hours, from 7 hours to 13.5 hours, from 7 hours to 14 hours, from 7 hours to 14.5 hours, from 7 hours to 15 hours, from 7 hours to 15.5 hours, from 7 hours to 16 hours, from 7 hours to 16.5 hours, from 7 hours to 17 hours, from 7 hours to 17.5 hours, from 7 hours to 18 hours, from 7 hours to 18.5 hours, from 7 hours to 19 hours, from 7 hours to 19.5 hours, from 7 hours to 20 hours, from 7 hours to 20.5 hours, from 7 hours to 21 hours, from 7 hours to 21.5 hours, from 7 hours to 22 hours, from 7 hours to 22.5 hours, from 7 hours to 23 hours, from 7 hours to 23.5 hours, from 7 hours to 24 hours, from 7 hours to 25 hours, from 7 hours to 26 hours, from 7 hours to 27 hours, from 7 hours to 28 hours, from 7 hours to 29 hours, from 7 hours to 30 hours, from 7 hours to 31 hours, from 7 hours to 32 hours, from 7 hours to 33 hours, from 7 hours to 34 hours, from 7 hours to 35 hours, from 7 hours to 36 hours, from 7.5 hours to 8 hours, from 7.5 hours to 8.5 hours, from 7.5 hours to 9 hours, from 7.5 hours to 9.5 hours, from 7.5 hours to 10 hours, from 7.5 hours to 10.5 hours, from 7.5 hours to 11 hours, from 7.5 hours to 11.5 hours, from 7.5 hours to 12 hours, from 7.5 hours to 12.5 hours, from 7.5 hours to 13 hours, from 7.5 hours to 13.5 hours, from 7.5 hours to 14 hours, from 7.5 hours to 14.5 hours, from 7.5 hours to 15 hours, from 7.5 hours to 15.5 hours, from 7.5 hours to 16 hours, from 7.5 hours to 16.5 hours, from 7.5 hours to 17 hours, from 7.5 hours to 17.5 hours, from 7.5 hours to 18 hours, from 7.5 hours to 18.5 hours, from 7.5 hours to 19 hours, from 7.5 hours to 19.5 hours, from 7.5 hours to 20 hours, from 7.5 hours to 20.5 hours, from 7.5 hours to 21 hours, from 7.5 hours to 21.5 hours, from 7.5 hours to 22 hours, from 7.5 hours to 22.5 hours, from 7.5 hours to 23 hours, from 7.5 hours to 23.5 hours, from 7.5 hours to 24 hours, from 7.5 hours to 25 hours, from 7.5 hours to 26 hours, from 7.5 hours to 27 hours, from 7.5 hours to 28 hours, from 7.5 hours to 29 hours, from 7.5 hours to 30 hours, from 7.5 hours to 31 hours, from 7.5 hours to 32 hours, from 7.5 hours to 33 hours, from 7.5 hours to 34 hours, from 7.5 hours to 35 hours, from 7.5 hours to 36 hours, from 8 hours to 8.5 hours, from 8 hours to 9 hours, from 8 hours to 9.5 hours, from 8 hours to 10 hours, from 8 hours to 10.5 hours, from 8 hours to 11 hours, from 8 hours to 11.5 hours, from 8 hours to 12 hours, from 8 hours to 12.5 hours, from 8 hours to 13 hours, from 8 hours to 13.5 hours, from 8 hours to 14 hours, from 8 hours to 14.5 hours, from 8 hours to 15 hours, from 8 hours to 15.5 hours, from 8 hours to 16 hours, from 8 hours to 16.5 hours, from 8 hours to 17 hours, from 8 hours to 17.5 hours, from 8 hours to 18 hours, from 8 hours to 18.5 hours, from 8 hours to 19 hours, from 8 hours to 19.5 hours, from 8 hours to 20 hours, from 8 hours to 20.5 hours, from 8 hours to 21 hours, from 8 hours to 21.5 hours, from 8 hours to 22 hours, from 8 hours to 22.5 hours, from 8 hours to 23 hours, from 8 hours to 23.5 hours, from 8 hours to 24 hours, from 8 hours to 25 hours, from 8 hours to 26 hours, from 8 hours to 27 hours, from 8 hours to 28 hours, from 8 hours to 29 hours, from 8 hours to 30 hours, from 8 hours to 31 hours, from 8 hours to 32 hours, from 8 hours to 33 hours, from 8 hours to 34 hours, from 8 hours to 35 hours, from 8 hours to 36 hours, from 8.5 hours to 9 hours, from 8.5 hours to 9.5 hours, from 8.5 hours to 10 hours, from 8.5 hours to 10.5 hours, from 8.5 hours to 11 hours, from 8.5 hours to 11.5 hours, from 8.5 hours to 12 hours, from 8.5 hours to 12.5 hours, from 8.5 hours to 13 hours, from hours to 13.5 hours, from 8.5 hours to 14 hours, from 8.5 hours to 14.5 hours, from 8.5 hours to 15 hours, from 8.5 hours to 15.5 hours, from 8.5 hours to 16 hours, from 8.5 hours to 16.5 hours, from 8.5 hours to 17 hours, from 8.5 hours to 17.5 hours, from 8.5 hours to 18 hours,to 18.5 hours, from 8.5 hours to 19 hours, from 8.5 hours to 19.5 hours, from 8.5 hours to 20 hours, from 8.5 hours to 20.5 hours, from 8.5 hours to 21 hours, from 8.5 hours to 21.5 hours, from 8.5 hours to 22 hours, from 8.5 hours to 22.5 hours, from 8.5 hours to 23 hoursto 23.5 hours, from 8.5 hours to 24 hours, from 8.5 hours to 25 hours, from 8.5 hours, from 8.5 hours to 27 hours, from 8.5 hours to 28 hours, from 8.5 hours to 29 hours, from 8.5 hours to 30 hours, from 8.5 hours to 31 hours, from 8.5 hours to 32 hours, from 8.5 hours to 33 hours, from 8.5 hours to 34 hours, from 8.5 hours to 35 hours, from 8.5 hours to 36 hours, from 9 hours to 9.5 hours, from 9 hours to 10 hours, from 9 hours to 10.5 hours, from 9 hours to 11 hours, from 9 hours to 11.5 hours, from 9 hours to 12 hours, from 9 hours to 12.5 hours, from 9 hours to 13 hours, from 9 hours to 13.5 hours, from 9 hours to 14 hours, from 9 hours , from 9 hours to 15 hours, from 9 hours to 15.5 hours, from 9 hours to 16 hours, from 9 hours to 16.5 hours, from 9 hours to 17 hours, from 9 hours to 17.5 hours, from 9 hours to 18 hours, from 9 hours to 18.5 hours, from 9 hours to 19 hours, from 9 hours to 19.5 hours, from 9 hours to 20 hours, from 9 hours to 20.5 hours, from 9 hours to 21 hours, from 9 hours to 21.5 hours, from 9 hours to 22 hours, from 9 hours to 22.5 hours, from 9 hours to 23 hours, from 9 hours to 23.5 hours, from 9 hours to 24 hours, from 9 hours to 25 hours, from 9 hours to 26 hours, from 9 hours to 27 hours, from 9 hours to 28 hours, from 9 hours to 29 hours, from 9 hours to 30 hours, from 9 hours to 31 hours, from 9 hours to 32 hours, from 9 hours to 33 hours, from 9 hours to 34 hours, from 9 hours to 35 hours, from 9 hours to 36 hours, from 9.5 hours to 10 hours, from 9.5 hours to 10.5 hours, from 9.5 hours to 11 hours, from 9.5 hours to 11.5 hours, from 9.5 hours to 12 hours, from 9.5 hours to 12.5 hours, from 9.5 hours to 13 hours, from 9.5 hours to 13.5 hours, from 9.5 hours to 14 hours, from 9.5 hours to 14.5 hours, from 9.5 hours to 15 hours, from 9.5 hours to 15.5 hours, from 9.5 hours to 16 hours, from 9.5 hours to 16.5 hours, from 9.5 hours to 17 hours, from 9.5 hours to 17.5 hours, from 9.5 hours to 18 hours, from 9.5 hours to 18.5 hours, from 9.5 hours to 19 hours, from 9.5 hours to 19.5 hours, from 9.5 hours to 20 hours, from 9.5 hours to 20.5 hours, from 9.5 hours to 21 hours, from 9.5 hours to 21.5 hours, from 9.5 hours to 22 hours, from 9.5 hours to 22.5 hours, from 9.5 hours to 23 hours, from 9.5 hours to 23.5 hours, from 9.5 hours to 24 hours, from 9.5 hours to 25 hours, from 9.5 hours to 26 hours , from 9.5 hours to 27 hours, from 9.5 hours to 28 hours, from 9.5 hours to 29 hours, from 9.5 hours to 30 hours, from 9.5 hours to 31 hours, from 9.5 hours to 32 hours, from 9.5 hours to 33 hours, from 9.5 hours to 34 hours, from 9.5 hours to 35 hours, from 9.5 hours to 36 hours, from 10 hours to 10.5 hours, from 10 hours to 11 hours, from 10 hours to 11.5 hours, from to 12 hours, from 10 hours to 12.5 hours, from 10 hours to 13 hours, from 10 hours to 13.5 hours, from 10 hours to 14 hours, from 10 hours to 14.5 hours, from 10 hours to 15 hours, from 10 hours to 15.5 hours, from 10 hours to 16 hours, from 10 hours to 16.5 hours, from 10 hours to 17 hours, from 10 hours to 17.5 hours, from 10 hours to 18 hours, from 10 hours to 18.5 hours, from 10 hours to 19 hours, from 10 hours to 19.5 hours, from 10 hours to 20 hours, from 10 hours to 20.5 hours, from 10 hours to 21 hours, from 10 hours to 21.5 hours, from 10 hours to 22 hours, from 10 hours to 22.5 hours, from 10 hours to 23 hours, from 10 hours to 23.5 hours, from 10 hours to 24 hours, from 10 hours to 25 hours, from 10 hours to 26 hours, from 10 hours to 27 hours, from 10 hours to 28 hours, from 10 hours to 29 hours, from 10 hours to 30 hours, from 10 hours to 31 hours, from 10 hours to 32 hours, from 10 hours to 33 hours, from 10 hours to 34 hours, from 10 hours to 35 hours, from 10 hours to 36 hours, from 10.5 hours to 11 hours, from 10.5 hours to 11.5 hours, from 10.5 hours to 12 hours, from 10.5 hours to 12.5 hours, from 10.5 hours to 13 hours, from 10.5 hours to 13.5 hours, from 10.5 hours to 14 hours, from 10.5 hours to 14.5 hours, from 10.5 hours to 15 hours, from 10.5 hours to 15.5 hours, from 10.5 hours to 16 hours, from 10.5 hours to 16.5 hours, from 10.5 hours to 17 hours, from 10.5 hours to 17.5 hours, from 10.5 hours to 18 hours, from 10.5 hours to 18.5 hours, from 10.5 hours to 19 hours, from 10.5 hours to 19.5 hours, from 10.5 hours to 20 hours, from 10.5 hours to 20.5 hours, from 10.5 hours to 21 hours, from 10.5 hours to 21.5 hours, from 10.5 hours to 22 hours, from 10.5 hours to 22.5 hours, from 10.5 hours to 23 hours, from 10.5 hours to 23.5 hours, from 10.5 hours to 24 hours, from 10.5 hours to 25 hours, from 10.5 hours to 26 hours, from 10.5 hours to 27 hours, from 10.5 hours to 28 hours, from 10.5 hours to 29 hours, from 10.5 hours to 30 hours, from 10.5 hours to 31 hours, from 10.5 hours to 32 hours, from 10.5 hours to 33 hours, from 10.5 hours to 34 hours, from 10.5 hours to 35 hours, from 10.5 hours to 36 hours, from 11 hours to 11.5 hours, from 11 hours to 12 hours, from 11 hours to 12.5 hours, from 11 hours to 13 hours, from 11 hours to 13.5 hours, from 11 hours to 14 hours, from 11 hours to 14.5 hours, from 11 hours to 15 hours, from 11 hours to 15.5 hours, from 11 hours to 16 hours, from 11 hours to 16.5 hours, from 11 hours to 17 hours, from 11 hours to 17.5 hours, from 11 hours to 18 hours, from 11 hours to 18.5 hours, from 11 hours to 19 hours, from 11 hours to 19.5 hours, from 11 hours to 20 hours, from 11 hours to 20.5 hours, from 11 hours to 21 hours, from 11 hours to 21.5 hours, from 11 hours to 22 hours, from 11 hours to 22.5 hours, from 11 hours to 23 hours, from 11 hours to 23.5 hours, from 11 hours to 24 hours, from 11 hours to 25 hours, from 11 hours to 26 hours, from 11 hours to 27 hours, from 11 hours to 28 hours, from 11 hours to 29 hours, from 11 hours to 30 hours, from 11 hours to 31 hours, from 11 hours to 32 hours, from 11 hours to 33 hours, from 11 hours to 34 hours, from 11 hours to 35 hours, from 11 hours to 36 hours, from 11.5 hours to 12 hours, from 11.5 hours to 12.5 hours, from 11.5 hours to 13 hours, from 11.5 hours to 13.5 hours, from 11.5 hours to 14 hours, from 11.5 hours to 14.5 hours, from 11.5 hours to 15 hours, from 11.5 hours to 15.5 hours, from 11.5 hours to 16 hours, from 11.5 hours to 16.5 hours, from 11.5 hours to 17 hours, from 11.5 hours to 17.5 hours, from 11.5 hours to 18 hours, from 11.5 hours to 18.5 hours, from 11.5 hours to 19 hours, from 11.5 hours to 19.5 hours, from 11.5 hours to 20 hours, from 11.5 hours to 20.5 hours, from 11.5 hours to 21 hours, from 11.5 hours to 21.5 hours, from 11.5 hours to 22 hours, from 11.5 hours to 22.5 hours, from 11.5 hours to 23 hours, from 11.5 hours to 23.5 hours, from 11.5 hours to 24 hours, from 11.5 hours to 25 hours, from 11.5 hours to 26 hours, from 11.5 hours to 27 hours, from 11.5 hours to 28 hours, from 11.5 hours to 29 hours, from 11.5 hours to 30 hours, from 11.5 hours to 31 hours, from 11.5 hours to 32 hours, from 11.5 hours to 33 hours, from 11.5 hours to 34 hours, from 11.5 hours to 35 hours, from 11.5 hours to 36 hours, from 12 hours to 12.5 hours, from 12 hours to 13 hours, from 12 hours to 13.5 hours, from 12 hours to 14 hours, from 12 hours to 14.5 hours, from 12 hours to 15 hours, from 12 hours to 15.5 hours, from 12 hours to 16 hours, from 12 hours to 16.5 hours, from 12 hours to 17 hours, from 12 hours to 17.5 hours, from 12 hours to 18 hours, from 12 hours to 18.5 hours, from 12 hours to 19 hours, from 12 hours to 19.5 hours, from 12 hours to 20 hours, from 12 hours to 20.5 hours, from 12 hours to 21 hours, from 12 hours to 21.5 hours, from 12 hours to 22 hours, from 12 hours to 22.5 hours, from 12 hours to 23 hours, from 12 hours to 23.5 hours, from 12 hours to 24 hours, from 12 hours to 25 hours, from 12 hours to 26 hours, from 12 hours to 27 hours, from 12 hours to 28 hours, from 12 hours to 29 hours, from 12 hours to 30 hours, from 12 hours to 31 hours, from 12 hours to 32 hours, from 12 hours to 33 hours, from 12 hours to 34 hours, from 12 hours to 35 hours, from 12 hours to 36 hours, from 12.5 hours to 13 hours, from 12.5 hours to 13.5 hours, from 12.5 hours to 14 hours, from 12.5 hours to 14.5 hours, from 12.5 hours to 15 hours, from 12.5 hours to 15.5 hours, from 12.5 hours to 16 hours, from 12.5 hours to 16.5 hours, from 12.5 hours to 17 hours, from 12.5 hours to 17.5 hours, from 12.5 hours to 18 hours, from 12.5 hours to 18.5 hours, from 12.5 hours to 19 hours, from 12.5 hours to 19.5 hours, from 12.5 hours to 20 hours, from 12.5 hours to 20.5 hours, from 12.5 hours to 21 hours, from 12.5 hours to 21.5 hours, from 12.5 hours to 22 hours, from 12.5 hours to 22.5 hours, from 12.5 hours to 23 hours, from 12.5 hours to 23.5 hours, from 12.5 hours to 24 hours, from 12.5 hours to 25 hours, from 12.5 hours to 26 hours, from 12.5 hours to 27 hours, from 12.5 hours to 28 hours, from 12.5 hours to 29 hours, from 12.5 hours to 30 hours, from 12.5 hours to 31 hours, from 12.5 hours to 32 hours, from 12.5 hours to 33 hours, from 12.5 hours to 34 hours, from 12.5 hours to 35 hours, from 12.5 hours to 36 hours, from 13 hours to 13.5 hours, from 13 hours to 14 hours, from 13 hours to 14.5 hours, from 13 hours to 15 hours, from 13 hours to 15.5 hours, from 13 hours to 16 hours, from 13 hours to 16.5 hours, from 13 hours to 17 hours, from 13 hours to 17.5 hours, from 13 hours to 18 hours, from 13 hours to 18.5 hours, from 13 hours to 19 hours, from 13 hours to 19.5 hours, from 13 hours to 20 hours, from 13 hours to 20.5 hours, from 13 hours to 21 hours, from 13 hours to 21.5 hours, from 13 hours to 22 hours, from 13 hours to 22.5 hours, from 13 hours to 23 hours, from 13 hours to 23.5 hours, from 13 hours to 24 hours, from 13 hours to 25 hours, from 13 hours to 26 hours, from 13 hours to 27 hours, from 13 hours to 28 hours, from 13 hours to 29 hours, from 13 hours to 30 hours, from 13 hours to 31 hours, from 13 hours to 32 hours, from 13 hours to 33 hours, from 13 hours to 34 hours, from 13 hours to 35 hours, from 13 hours to 36 hours, from 13.5 hours to 14 hours, from 13.5 hours to 14.5 hours, from 13.5 hours to 15 hours, from 13.5 hours to 15.5 hours, from 13.5 hours to 16 hours, from 13.5 hours to 16.5 hours, from 13.5 hours to 17 hours, from 13.5 hours to 17.5 hours, from 13.5 hours to 18 hours, from 13.5 hours to 18.5 hours, from 13.5 hours to 19 hours, from 13.5 hours to 19.5 hours, from 13.5 hours to 20 hours, from 13.5 hours to 20.5 hours, from 13.5 hours to 21 hours, from 13.5 hours to 21.5 hours, from 13.5 hours to 22 hours, from 13.5 hours to 22.5 hours, from 13.5 hours to 23 hours, from 13.5 hours to 23.5 hours, from 13.5 hours to 24 hours, from 13.5 hours to 25 hours, from 13.5 hours to 26 hours, from 13.5 hours to 27 hours, from 13.5 hours to 28 hours, from 13.5 hours to 29 hours, from 13.5 hours to 30 hours, from 13.5 hours to 31 hours, from 13.5 hours to 32 hours, from 13.5 hours to 33 hours, from 13.5 hours to 34 hours, from 13.5 hours to 35 hours, from 13.5 hours to 36 hours, from 14 hours to 14.5 hours, from 14 hours to 15 hours, from 14 hours to 15.5 hours, from 14 hours to 16 hours, from 14 hours to 16.5 hours, from 14 hours to 17 hours, from 14 hours to 17.5 hours, from 14 hours to 18 hours, from 14 hours to 18.5 hours, from 14 hours to 19 hours, from 14 hours to 19.5 hours, from 14 hours to 20 hours, from 14 hours to 20.5 hours, from 14 hours to 21 hours, from 14 hours to 21.5 hours, from 14 hours to 22 hours, from 14 hours to 22.5 hours, from 14 hours to 23 hours, from 14 hours to 23.5 hours, from 14 hours to 24 hours, from 14 hours to 25 hours, from 14 hours to 26 hours, from 14 hours to 27 hours, from 14 hours to 28 hours, from 14 hours to 29 hours, from 14 hours to 30 hours, from 14 hours to 31 hours, from 14 hours to 32 hours, from 14 hours to 33 hours, from 14 hours to 34 hours, from 14 hours to 35 hours, from 14 hours to 36 hours, from 14.5 hours to 15 hours, from 14.5 hours to 15.5 hours, from 14.5 hours to 16 hours, from 14.5 hours to 16.5 hours, from 14.5 hours to 17 hours, from 14.5 hours to 17.5 hours, from 14.5 hours to 18 hours, from 14.5 hours to 18.5 hours, from 14.5 hours to 19 hours, from 14.5 hours to 19.5 hours, from 14.5 hours to 20 hours, from 14.5 hours to 20.5 hours, from 14.5 hours to 21 hours, from 14.5 hours to 21.5 hours, from 14.5 hours to 22 hours, from 14.5 hours to 22.5 hours, from 14.5 hours to 23 hours, from 14.5 hours to 23.5 hours, from 14.5 hours to 24 hours, from 14.5 hours to 25 hours, from 14.5 hours to 26 hours, from 14.5 hours to 27 hours, from 14.5 hours to 28 hours, from 14.5 hours to 29 hours, from 14.5 hours to 30 hours, from 14.5 hours to 31 hours, from 14.5 hours to 32 hours, from 14.5 hours to 33 hours, from 14.5 hours to 34 hours, from 14.5 hours to 35 hours, from 14.5 hours to 36 hours, from 15 hours to 15.5 hours, from 15 hours to 16 hours, from 15 hours to 16.5 hours, from 15 hours to 17 hours, from 15 hours to 17.5 hours, from 15 hours to 18 hours, from 15 hours to 18.5 hours, from 15 hours to 19 hours, from 15 hours to 19.5 hours, from 15 hours to 20 hours, from 15 hours to 20.5 hours, from 15 hours to 21 hours, from 15 hours to 21.5 hours, from 15 hours to 22 hours, from 15 hours to 22.5 hours, from 15 hours to 23 hours, from 15 hours to 23.5 hours, from 15 hours to 24 hours, from 15 hours to 25 hours, from 15 hours to 26 hours, from 15 hours to 27 hours, from 15 hours to 28 hours, from 15 hours to 29 hours, from 15 hours to 30 hours, from 15 hours to 31 hours, from 15 hours to 32 hours, from 15 hours to 33 hours, from 15 hours to 34 hours, from 15 hours to 35 hours, from 15 hours to 36 hours, from 15.5 hours to 16 hours, from 15.5 hours to 16.5 hours, from 15.5 hours to 17 hours, from 15.5 hours to 17.5 hours, from 15.5 hours to 18 hours, from 15.5 hours to 18.5 hours, from 15.5 hours to 19 hours, from 15.5 hours to 19.5 hours, from 15.5 hours to 20 hours, from 15.5 hours to 20.5 hours, from 15.5 hours to 21 hours, from 15.5 hours to 21.5 hours, from 15.5 hours to 22 hours, from 15.5 hours to 22.5 hours, from 15.5 hours to 23 hours, from 15.5 hours to 23.5 hours, from 15.5 hours to 24 hours, from 15.5 hours to 25 hours, from 15.5 hours to 26 hours, from 15.5 hours to 27 hours, from 15.5 hours to 28 hours, from 15.5 hours to 29 hours, from 15.5 hours to 30 hours, from 15.5 hours to 31 hours, from 15.5 hours to 32 hours, from 15.5 hours to 33 hours, from 15.5 hours to 34 hours, from 15.5 hours to 35 hours, from 15.5 hours to 36 hours, from 16 hours to 16.5 hours, from 16 hours to 17 hours, from 16 hours to 17.5 hours, from 16 hours to 18 hours, from 16 hours to 18.5 hours, from 16 hours to 19 hours, from 16 hours to 19.5 hours, from 16 hours to 20 hours, from 16 hours to 20.5 hours, from 16 hours to 21 hours, from 16 hours to 21.5 hours, from 16 hours to 22 hours, from 16 hours to 22.5 hours, from 16 hours to 23 hours, from 16 hours to 23.5 hours, from 16 hours to 24 hours, from 16 hours to 25 hours, from 16 hours to 26 hours, from 16 hours to 27 hours, from 16 hours to 28 hours, from 16 hours to 29 hours, from 16 hours to 30 hours, from 16 hours to 31 hours, from 16 hours to 32 hours, from 16 hours to 33 hours, from 16 hours to 34 hours, from 16 hours to 35 hours, from 16 hours to 36 hours, from 16.5 hours to 17 hours, from 16.5 hours to 17.5 hours, from 16.5 hours to 18 hours, from 16.5 hours to 18.5 hours, from 16.5 hours to 19 hours, from 16.5 hours to 19.5 hours, from 16.5 hours to 20 hours, from 16.5 hours to 20.5 hours, from 16.5 hours to 21 hours, from 16.5 hours to 21.5 hours, from 16.5 hours to 22 hours, from 16.5 hours to 22.5 hours, from 16.5 hours to 23 hours, from 16.5 hours to 23.5 hours, from 16.5 hours to 24 hours, from 16.5 hours to 25 hours, from 16.5 hours to 26 hours, from 16.5 hours to 27 hours, from 16.5 hours to 28 hours, from 16.5 hours to 29 hours, from 16.5 hours to 30 hours, from 16.5 hours to 31 hours, from 16.5 hours to 32 hours, from 16.5 hours to 33 hours, from 16.5 hours to 34 hours, from 16.5 hours to 35 hours, from 16.5 hours to 36 hours, from 17 hours to 17.5 hours, from 17 hours to 18 hours, from 17 hours to 18.5 hours, from 17 hours to 19 hours, from 17 hours to 19.5 hours, from 17 hours to 20 hours, from 17 hours to 20.5 hours, from 17 hours to 21 hours, from 17 hours to 21.5 hours, from 17 hours to 22 hours, from 17 hours to 22.5 hours, from 17 hours to 23 hours, from 17 hours to 23.5 hours, from 17 hours to 24 hours, from 17 hours to 25 hours, from 17 hours to 26 hours, from 17 hours to 27 hours, from 17 hours to 28 hours, from 17 hours to 29 hours, from 17 hours to 30 hours, from 17 hours to 31 hours, from 17 hours to 32 hours, from 17 hours to 33 hours, from 17 hours to 34 hours, from 17 hours to 35 hours, from 17 hours to 36 hours, from 17.5 hours to 18 hours, from 17.5 hours to 18.5 hours, from 17.5 hours to 19 hours, from 17.5 hours to 19.5 hours, from 17.5 hours to 20 hours, from 17.5 hours to 20.5 hours, from 17.5 hours to 21 hours, from 17.5 hours to 21.5 hours, from 17.5 hours to 22 hours, from 17.5 hours to 22.5 hours, from 17.5 hours to 23 hours, from 17.5 hours to 23.5 hours, from 17.5 hours to 24 hours, from 17.5 hours to 25 hours, from 17.5 hours to 26 hours, from 17.5 hours to 27 hours, from 17.5 hours to 28 hours, from 17.5 hours to 29 hours, from 17.5 hours to 30 hours, from 17.5 hours to 31 hours, from 17.5 hours to 32 hours, from 17.5 hours to 33 hours, from 17.5 hours to 34 hours, from 17.5 hours to 35 hours, from 17.5 hours to 36 hours, from 18 hours to 18.5 hours, from 18 hours to 19 hours, from 18 hours to 19.5 hours, from 18 hours to 20 hours, from 18 hours to 20.5 hours, from 18 hours to 21 hours, from 18 hours to 21.5 hours, from 18 hours to 22 hours, from 18 hours to 22.5 hours, from 18 hours to 23 hours, from 18 hours to 23.5 hours, from 18 hours to 24 hours, from 18 hours to 25 hours, from 18 hours to 26 hours, from 18 hours to 27 hours, from 18 hours to 28 hours, from 18 hours to 29 hours, from 18 hours to 30 hours, from 18 hours to 31 hours, from 18 hours to 32 hours, from 18 hours to 33 hours, from 18 hours to 34 hours, from 18 hours to 35 hours, from 18 hours to 36 hours, from 18.5 hours to 19 hours, from 18.5 hours to 19.5 hours, from 18.5 hours to 20 hours, from 18.5 hours to 20.5 hours, from 18.5 hours to 21 hours, from 18.5 hours to 21.5 hours, from 18.5 hours to 22 hours, from 18.5 hours to 22.5 hours, from 18.5 hours to 23 hours, from 18.5 hours to 23.5 hours, from 18.5 hours to 24 hours, from 18.5 hours to 25 hours, from 18.5 hours to 26 hours, from 18.5 hours to 27 hours, from 18.5 hours to 28 hours, from 18.5 hours to 29 hours, from 18.5 hours to 30 hours, from 18.5 hours to 31 hours, from 18.5 hours to 32 hours, from 18.5 hours to 33 hours, from 18.5 hours to 34 hours, from 18.5 hours to 35 hours, from 18.5 hours to 36 hours, from 19 hours to 19.5 hours, from 19 hours to 20 hours, from 19 hours to 20.5 hours, from 19 hours to 21 hours, from 19 hours to 21.5 hours, from 19 hours to 22 hours, from 19 hours to 22.5 hours, from 19 hours to 23 hours, from 19 hours to 23.5 hours, from 19 hours to 24 hours, from 19 hours to 25 hours, from 19 hours to 26 hours, from 19 hours to 27 hours, from 19 hours to 28 hours, from 19 hours to 29 hours, from 19 hours to 30 hours, from 19 hours to 31 hours, from 19 hours to 32 hours, from 19 hours to 33 hours, from 19 hours to 34 hours, from 19 hours to 35 hours, from 19 hours to 36 hours, from 19.5 hours to 20 hours, from 19.5 hours to 20.5 hours, from 19.5 hours to 21 hours, from 19.5 hours to 21.5 hours, from 19.5 hours to 22 hours, from 19.5 hours to 22.5 hours, from 19.5 hours to 23 hours, from 19.5 hours to 23.5 hours, from 19.5 hours to 24 hours, from 19.5 hours to 25 hours, from 19.5 hours to 26 hours, from 19.5 hours to 27 hours, from 19.5 hours to 28 hours, from 19.5 hours to 29 hours, from 19.5 hours to 30 hours, from 19.5 hours to 31 hours, from 19.5 hours to 32 hours, from 19.5 hours to 33 hours, from 19.5 hours to 34 hours, from 19.5 hours to 35 hours, from 19.5 hours to 36 hours, from 20 hours to 20.5 hours, from 20 hours to 21 hours, from 20 hours to 21.5 hours, from 20 hours to 22 hours, from 20 hours to 22.5 hours, from 20 hours to 23 hours, from 20 hours to 23.5 hours, from 20 hours to 24 hours, from 20 hours to 25 hours, from 20 hours to 26 hours, from 20 hours to 27 hours, from 20 hours to 28 hours, from 20 hours to 29 hours, from 20 hours to 30 hours, from 20 hours to 31 hours, from 20 hours to 32 hours, from 20 hours to 33 hours, from 20 hours to 34 hours, from 20 hours to 35 hours, from 20 hours to 36 hours, from 20.5 hours to 21 hours, from 20.5 hours to 21.5 hours, from 20.5 hours to 22 hours, from 20.5 hours to 22.5 hours, from 20.5 hours to 23 hours, from 20.5 hours to 23.5 hours, from 20.5 hours to 24 hours, from 20.5 hours to 25 hours, from 20.5 hours to 26 hours, from 20.5 hours to 27 hours, from 20.5 hours to 28 hours, from 20.5 hours to 29 hours, from 20.5 hours to 30 hours, from 20.5 hours to 31 hours, from 20.5 hours to 32 hours, from 20.5 hours to 33 hours, from 20.5 hours to 34 hours, from 20.5 hours to 35 hours, from 20.5 hours to 36 hours, from 21 hours to 21.5 hours, from 21 hours to 22 hours, from 21 hours to 22.5 hours, from 21 hours to 23 hours, from 21 hours to 23.5 hours, from 21 hours to 24 hours, from 21 hours to 25 hours, from 21 hours to 26 hours, from 21 hours to 27 hours, from 21 hours to 28 hours, from 21 hours to 29 hours, from 21 hours to 30 hours, from 21 hours to 31 hours, from 21 hours to 32 hours, from 21 hours to 33 hours, from 21 hours to 34 hours, from 21 hours to 35 hours, from 21 hours to 36 hours, from 21.5 hours to 22 hours, from 21.5 hours to 22.5 hours, from 21.5 hours to 23 hours, from 21.5 hours to 23.5 hours, from 21.5 hours to 24 hours, from 21.5 hours to 25 hours, from 21.5 hours to 26 hours, from 21.5 hours to 27 hours, from 21.5 hours to 28 hours, from 21.5 hours to 29 hours, from 21.5 hours to 30 hours, from 21.5 hours to 31 hours, from 21.5 hours to 32 hours, from 21.5 hours to 33 hours, from 21.5 hours to 34 hours, from 21.5 hours to 35 hours, from 21.5 hours to 36 hours, from 22 hours to 22.5 hours, from 22 hours to 23 hours, from 22 hours to 23.5 hours, from 22 hours to 24 hours, from 22 hours to 25 hours, from 22 hours to 26 hours, from 22 hours to 27 hours, from 22 hours to 28 hours, from 22 hours to 29 hours, from 22 hours to 30 hours, from 22 hours to 31 hours, from 22 hours to 32 hours, from 22 hours to 33 hours, from 22 hours to 34 hours, from 22 hours to 35 hours, from 22 hours to 36 hours, from 22.5 hours to 23 hours, from 22.5 hours to 23.5 hours, from 22.5 hours to 24 hours, from 22.5 hours to 25 hours, from 22.5 hours to 26 hours, from 22.5 hours to 27 hours, from 22.5 hours to 28 hours, from 22.5 hours to 29 hours, from 22.5 hours to 30 hours, from 22.5 hours to 31 hours, from 22.5 hours to 32 hours, from 22.5 hours to 33 hours, from 22.5 hours to 34 hours, from 22.5 hours to 35 hours, from 22.5 hours to 36 hours, from 23 hours to 23.5 hours, from 23 hours to 24 hours, from 23 hours to 25 hours, from 23 hours to 26 hours, from 23 hours to 27 hours, from 23 hours to 28 hours, from 23 hours to 29 hours, from 23 hours to 30 hours, from 23 hours to 31 hours, from 23 hours to 32 hours, from 23 hours to 33 hours, from 23 hours to 34 hours, from 23 hours to 35 hours, from 23 hours to 36 hours, from 23.5 hours to 24 hours, from 23.5 hours to 25 hours, from 23.5 hours to 26 hours, from 23.5 hours to 27 hours, from 23.5 hours to 28 hours, from 23.5 hours to 29 hours, from 23.5 hours to 30 hours, from 23.5 hours to 31 hours, from 23.5 hours to 32 hours, from 23.5 hours to 33 hours, from 23.5 hours to 34 hours, from 23.5 hours to 35 hours, from 23.5 hours to 36 hours, from 24 hours to 25 hours, from 24 hours to 26 hours, from 24 hours to 27 hours, from 24 hours to 28 hours, from 24 hours to 29 hours, from 24 hours to 30 hours, from 24 hours to 31 hours, from 24 hours to 32 hours, from 24 hours to 33 hours, from 24 hours to 34 hours, from 24 hours to 35 hours, from 24 hours to 36 hours, from 25 hours to 26 hours, from 25 hours to 27 hours, from 25 hours to 28 hours, from 25 hours to 29 hours, from 25 hours to 30 hours, from 25 hours to 31 hours, from 25 hours to 32 hours, from 25 hours to 33 hours, from 25 hours to 34 hours, from 25 hours to 35 hours, from 25 hours to 36 hours, from 26 hours to 27 hours, from 26 hours to 28 hours, from 26 hours to 29 hours, from 26 hours to 30 hours, from 26 hours to 31 hours, from 26 hours to 32 hours, from 26 hours to 33 hours, from 26 hours to 34 hours, from 26 hours to 35 hours, from 26 hours to 36 hours, from 27 hours to 28 hours, from 27 hours to 29 hours, from 27 hours to 30 hours, from 27 hours to 31 hours, from 27 hours to 32 hours, from 27 hours to 33 hours, from 27 hours to 34 hours, from 27 hours to 35 hours, from 27 hours to 36 hours, from 28 hours to 29 hours, from 28 hours to 30 hours, from 28 hours to 31 hours, from 28 hours to 32 hours, from 28 hours to 33 hours, from 28 hours to 34 hours, from 28 hours to 35 hours, from 28 hours to 36 hours, from 29 hours to 30 hours, from 29 hours to 31 hours, from 29 hours to 32 hours, from 29 hours to 33 hours, from 29 hours to 34 hours, from 29 hours to 35 hours, from 29 hours to 36 hours, from 30 hours to 31 hours, from 30 hours to 32 hours, from 30 hours to 33 hours, from 30 hours to 34 hours, from 30 hours to 35 hours, from 30 hours to 36 hours, from 31 hours to 32 hours, from 31 hours to 33 hours, from 31 hours to 34 hours, from 31 hours to 35 hours, from 31 hours to 36 hours, from 32 hours to 33 hours, from 32 hours to 34 hours, from 32 hours to 35 hours, from 32 hours to 36 hours, from 33 hours to 34 hours, from 33 hours to 35 hours, from 33 hours to 36 hours, from 34 hours to 35 hours, from 34 hours to 36 hours, or from 35 hours to 36 hours.
- In some embodiments, during the soaking, a size of the β-phase intermetallic particles decreases as compared to a size of the β-phase intermetallic particles prior to the soaking. In some embodiments, during the soaking, a number density of the β-phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the β-phase intermetallic particles in the cast aluminum alloy product prior to the soaking.
- Methods of this aspect may optionally further comprise subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product. Optionally, the one or more rolling processes comprise at least one of a hot rolling process or a cold rolling process. Optionally, the hot rolling process may comprise an exit temperature of from 100° C. to 500° C., such as from from 100° C. to 150° C., from 100° C. to 200° C., from 100° C. to 250° C., from 100° C. to 300° C., from 100° C. to 350° C., from 100° C. to 400° C., from 100° C. to 450° C., from 150° C. to 200° C., from 150° C. to 250° C., from 150° C. to 300° C., from 150° C. to 350° C., from 150° C. to 400° C., from 150° C. to 450° C., from 150° C. to 500° C., from 200° C. to 250° C., from 200° C. to 300° C., from 200° C. to 350° C., from 200° C. to 400° C., from 200° C. to 450° C., from 200° C. to 500° C., from 250° C. to 300° C., from 250° C. to 350° C., from 250° C. to 400° C., from 250° C. to 450° C., from 250° C. to 500° C., from 300° C. to 350° C., from 300° C. to 400° C., from 300° C. to 450° C., from 300° C. to 500° C., from 350° C. to 400° C., from 350° C. to 450° C., from 350° C. to 500° C., from 400° C. to 450° C., from 400° C. to 500° C., or from 450° C. to 500° C. Optionally, the rolled aluminum alloy product produced by the hot rolling process has a thickness from 1 mm to 8 mm, such as from 1 mm to 2 mm, from 1 mm to 3 mm, from 1 mm to 4 mm, from 1 mm to 5 mm, from 1 mm to 6 mm, from 1 mm to 7 mm, from 2 mm to 3 mm, from 2 mm to 4 mm, from 2 mm to 5 mm, from 2 mm to 6 mm, from 2 mm to 7 mm, from 2 mm to 8 mm, from 3 mm to 4 mm, from 3 mm to 5 mm, from 3 mm to 6 mm, from 3 mm to 7 mm, from 3 mm to 8 mm, from 4 mm to 5 mm, from 4 mm to 6 mm, from 4 mm to 7 mm, from 4 mm to 8 mm, from 5 mm to 6 mm, from 5 mm to 7 mm, from 5 mm to 8 mm, from 6 mm to 7 mm, from 6 mm to 8 mm, or from 7 mm to 8 mm.
- Optionally, the cold rolling process may comprise an exit temperature of from 50° C. to 250° C., such as from 50° C. to 100° C., from 50° C. to 150° C., from 50° C. to 200° C., from 100° C. to 150° C., from 100° C. to 200° C., from 100° C. to 250° C., from 150° C. to 200° C., from 150° C. to 250° C., or from 200° C. to 250° C. Optionally, the rolled aluminum alloy product produced by the cold rolling process has a thickness from 0.15 mm to 0.50 mm, such as from 0.15 mm to 0.20 mm, from 0.15 mm to 0.25 mm, , from 0.15 mm to 0.30 mm, from 0.15 mm to 0.35 mm, from 0.15 mm to 0.40 mm, from 0.15 mm to 0.45 mm, from 0.15 mm to 0.50 mm, from 0.20 mm to 0.25 mm, from 0.20 mm to 0.30 mm, from 0.20 mm to 0.35 mm, from 0.20 mm to 0.40 mm, from 0.20 mm to 0.45 mm, from 0.20 mm to 0.50 mm, from 0.25 mm to 0.30 mm, from 0.25 mm to 0.35 mm, from 0.25 mm to 0.40 mm, from 0.25 mm to 0.45 mm, from 0.25 mm to 0.50 mm, from 0.30 mm to 0.35 mm, from 0.30 mm to 0.40 mm, from 0.30 mm to 0.50 mm, from 0.35 mm to 0.40 mm, from 0.35 mm to 0.45 mm, from 0.35 mm to 0.50 mm, from 0.40 mm to 0.45 mm, from 0.40 mm to 0.50 mm, or from 0.45 mm to 0.50 mm.
- In another aspect, methods for improving formability of a metal product are provided. An example method of this aspect comprises providing a cast metal product comprising a metal composite, wherein the metal composite comprises iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the metal composite to an iron wt. % in the metal composite is from 0.5 to 1.0, and homogenizing the cast metal product to control an inter-particle spacing of the plurality of particles and to control a particle density of the plurality of particles such to achieve a ratio of a peak inter-particle spacing to a particle number density from 0.0003/µm to 0.0006/µm. Optionally, the metal composite includes a plurality of particles including α-phase intermetallic particles comprising silicon and one or more of iron or manganese and β-phase intermetallic particles comprising one or more of iron or manganese.
- In some embodiments, the metal composite of the method described includes an inter-particle spacing is from 1 µm to 25 µm. In some embodiments, the metal composite of the method described includes the particle density is from 5 to 30,000 particles per µm2.
- In some embodiments, the metal composite of the method described includes the particle density is from 50 to 1,000 particles per µm2. In some embodiments, the metal composite of the method described includes the plurality of particles comprising a particle diameter from 1 µm to 50 µm. Optionally, the plurality of particles may have diameters of from 500 nm to 50 µm.
- Various homogenizing conditions are useful with the methods described herein. For example, the homogenization temperature may be from 400° C. to less than the melting point of aluminum (e.g., 660° C.) or to less than the solidus point of the particular alloy. For example, an example time duration for the soaking may be from 0.1 hours to 48 hours. Optionally, the homogenization temperature is within 25° C. of a solidus temperature of the cast metal product.
- The source aluminum alloy(s) for the aluminum alloy products prepared according to the above described methods may correspond to the same series aluminum alloy or a mixture of different series aluminum alloys. Optionally, preparing the cast aluminum alloy product comprises preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy. Optionally, preparing the molten 3xxx series aluminum alloy comprises melting both a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy. Optionally, the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy are from a recycled source. In some embodiments, aluminum alloys including a higher percentage of silicon may be useful for achieving a target silicon to iron ratio. For example, preparing the molten aluminum alloy optionally further comprises melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy along with a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- In some embodiments, multiple homogenization steps may be useful. For example, a secondary lower temperature homogenization after a first, higher temperature and/or long duration, homogenization may be useful for preparing an aluminum alloy product, such as for rolling or other processing. A multiple-step homogenization process may include reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature; and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration, such as a second time duration that is shorter than the time duration of the initial long-duration soak. For example, the second time duration may be from 1 hour to 24 hours, such as from 1 hour to 2 hours, from 1 hour to 3 hours, from 1 hour to 4 hours, from 1 hour to 5 hours, from 1 hour to 6 hours, from 1 hour to 7 hours, from 1 hour to 8 hours, from 1 hour to 9 hours, from 1 hour to 10 hours, from 1 hour to 11 hours, from 1 hour to 12 hours, from 1 hour to 13 hours, from 1 hour to 14 hours, from 1 hour to 15 hours, from 1 hour to 16 hours, from 1 hour to 17 hours, from 1 hour to 18 hours, from 1 hour to 19 hours, from 1 hour to 20 hours, from 1 hour to 21 hours, from 1 hour to 22 hours, from 1 hour to 23 hours, from 2 hours to 3 hours, from 2 hours to 4 hours, from 2 hours to 5 hours, from 2 hours to 6 hours, from 2 hours to 7 hours, from 2 hours to 8 hours, from 2 hours to 9 hours, from 2 hours to 10 hours, from 2 hours to 11 hours, from 2 hours to 12 hours, from 2 hours to 13 hours, from 2 hours to 14 hours, from 2 hours to 15 hours, from 2 hours to 16 hours, from 2 hours to 17 hours, from 2 hours to 18 hours, from 2 hours to 19 hours, from 2 hours to 20 hours, from 2 hours to 21 hours, from 2 hours to 22 hours, from 2 hours to 23 hours, from 2 hours to 24 hours, from 3 hours to 4 hours, from 3 hours to 5 hours, from 3 hours to 6 hours, from 3 hours to 7 hours, from 3 hours to 8 hours, from 3 hours to 9 hours, from 3 hours to 10 hours, from 3 hours to 11 hours, from 3 hours to 12 hours, from 3 hours to 13 hours, from 3 hours to 14 hours, from 3 hours to 15 hours, from 3 hours to 16 hours, from 3 hours to 17 hours, from 3 hours to 18 hours, from 3 hours to 19 hours, from 3 hours to 20 hours, from 3 hours to 21 hours, from 3 hours to 22 hours, from 3 hours to 23 hours, from 3 hours to 24 hours, from 4 hours to 5 hours, from 4 hours to 6 hours, from 4 hours to 7 hours, from 4 hours to 8 hours, from 4 hours to 9 hours, from 4 hours to 10 hours, from 4 hours to 11 hours, from 4 hours to 12 hours, from 4 hours to 13 hours, from 4 hours to 14 hours, from 4 hours to 15 hours, from 4 hours to 16 hours, from 4 hours to 17 hours, from 4 hours to 18 hours, from 4 hours to 19 hours, from 4 hours to 20 hours, from 4 hours to 21 hours, from 4 hours to 22 hours, from 4 hours to 23 hours, from 4 hours to 24 hours, from 5 hours to 6 hours, from 5 hours to 7 hours, from 5 hours to 8 hours, from 5 hours to 9 hours, from 5 hours to 10 hours, from 5 hours to 11 hours, from 5 hours to 12 hours, from 5 hours to 13 hours, from 5 hours to 14 hours, from 5 hours to 15 hours, from 5 hours to 16 hours, from 5 hours to 17 hours, from 5 hours to 18 hours, from 5 hours to 19 hours, from 5 hours to 20 hours, from 5 hours to 21 hours, from 5 hours to 22 hours, from 5 hours to 23 hours, from 5 hours to 24 hours, from 6 hours to 7 hours, from 6 hours to 8 hours, from 6 hours to 9 hours, from 6 hours to 10 hours, from 6 hours to 11 hours, from 6 hours to 12 hours, from 6 hours to 13 hours, from 6 hours to 14 hours, from 6 hours to 15 hours, from 6 hours to 16 hours, from 6 hours to 17 hours, from 6 hours to 18 hours, from 6 hours to 19 hours, from 6 hours to 20 hours, from 6 hours to 21 hours, from 6 hours to 22 hours, from 6 hours to 23 hours, from 6 hours to 24 hours, from 7 hours to 8 hours, from 7 hours to 9 hours, from 7 hours to 10 hours, from 7 hours to 11 hours, from 7 hours to 12 hours, from 7 hours to 13 hours, from 7 hours to 14 hours, from 7 hours to 15 hours, from 7 hours to 16 hours, from 7 hours to 17 hours, from 7 hours to 18 hours, from 7 hours to 19 hours, from 7 hours to 20 hours, from 7 hours to 21 hours, from 7 hours to 22 hours, from 7 hours to 23 hours, from 7 hours to 24 hours, from 8 hours to 9 hours, from 8 hours to 10 hours, from 8 hours to 11 hours, from 8 hours to 12 hours, from 8 hours to 13 hours, from 8 hours to 14 hours, from 8 hours to 15 hours, from 8 hours to 16 hours, from 8 hours to 17 hours, from 8 hours to 18 hours, from 8 hours to 19 hours, from 8 hours to 20 hours, from 8 hours to 21 hours, from 8 hours to 22 hours, from 8 hours to 23 hours, from 8 hours to 24 hours, from 9 hours to 10 hours, from 9 hours to 11 hours, from 9 hours to 12 hours, from 9 hours to 13 hours, from 9 hours to 14 hours, from 9 hours to 15 hours, from 9 hours to 16 hours, from 9 hours to 17 hours, from 9 hours to 18 hours, from 9 hours to 19 hours, from 9 hours to 20 hours, from 9 hours to 21 hours, from 9 hours to 22 hours, from 9 hours to 23 hours, from 9 hours to 24 hours, from 10 hours to 11 hours, from 10 hours to 12 hours, from 10 hours to 13 hours, from 10 hours to 14 hours, from 10 hours to 15 hours, from 10 hours to 16 hours, from 10 hours to 17 hours, from 10 hours to 18 hours, from 10 hours to 19 hours, from 10 hours to 20 hours, from 10 hours to 21 hours, from 10 hours to 22 hours, from 10 hours to 23 hours, from 10 hours to 24 hours, from 11 hours to 12 hours, from 11 hours to 13 hours, from 11 hours to 14 hours, from 11 hours to 15 hours, from 11 hours to 16 hours, from 11 hours to 17 hours, from 11 hours to 18 hours, from 11 hours to 19 hours, from 11 hours to 20 hours, from 11 hours to 21 hours, from 11 hours to 22 hours, from 11 hours to 23 hours, from 11 hours to 24 hours, from 12 hours to 13 hours, from 12 hours to 14 hours, from 12 hours to 15 hours, from 12 hours to 16 hours, from 12 hours to 17 hours, from 12 hours to 18 hours, from 12 hours to 19 hours, from 12 hours to 20 hours, from 12 hours to 21 hours, from 12 hours to 22 hours, from 12 hours to 23 hours, from 12 hours to 24 hours, from 13 hours to 14 hours, from 13 hours to 15 hours, from 13 hours to 16 hours, from 13 hours to 17 hours, from 13 hours to 18 hours, from 13 hours to 19 hours, from 13 hours to 20 hours, from 13 hours to 21 hours, from 13 hours to 22 hours, from 13 hours to 23 hours, from 13 hours to 24 hours, from 14 hours to 16 hours, from 14 hours to 17 hours, from 14 hours to 18 hours, from 14 hours to 19 hours, from 14 hours to 20 hours, from 14 hours to 21 hours, from 14 hours to 22 hours, from 14 hours to 23 hours, from 14 hours to 24 hours, from 15 hours to 16 hours, from 15 hours to 17 hours, from 15 hours to 18 hours, from 15 hours to 19 hours, from 15 hours to 20 hours, from 15 hours to 21 hours, from 15 hours to 22 hours, from 15 hours to 23 hours, from 15 hours to 24 hours, from 16 hours to 17 hours, from 16 hours to 18 hours, from 16 hours to 19 hours, from 16 hours to 20 hours, from 16 hours to 21 hours, from 16 hours to 22 hours, from 16 hours to 23 hours, from 16 hours to 24 hours, from 17 hours to 18 hours, from 17 hours to 19 hours, from 17 hours to 20 hours, from 17 hours to 21 hours, from 17 hours to 22 hours, from 17 hours to 23 hours, from 17 hours to 24 hours, from 18 hours to 19 hours, from 18 hours to 20 hours, from 18 hours to 21 hours, from 18 hours to 22 hours, from 18 hours to 23 hours, from 18 hours to 24 hours, from 19 hours to 20 hours, from 19 hours to 21 hours, from 19 hours to 22 hours, from 19 hours to 23 hours, from 19 hours to 24 hours, from 20 hours to 21 hours, from 20 hours to 22 hours, from 20 hours to 23 hours, from 20 hours to 24 hours, from 21 hours to 22 hours, from 21 hours to 23 hours, from 21 hours to 24 hours, from 22 hours to 23 hours, from 22 hours to 24 hours, or from 23 hours to 24 hours.
- Optionally, the secondary lower temperature for homogenization, after an initial homogenization at higher temperature, is from 500° C. to 580° C., such as from 500° C. to 505° C., from 500° C. to 510° C., from 500° C. to 515° C., from 500° C. to 520° C., from 500° C. to 525° C., from 500° C. to 530° C., from 500° C. to 535° C., from 500° C. to 540° C., from 500° C. to 545° C., from 500° C. to 550° C., from 500° C. to 555° C., from 500° C. to 560° C., from 500° C. to 565° C., from 500° C. to 570° C., from 500° C. to 575° C., from 505° C. to 510° C., from 505° C. to 515° C., from 505° C. to 520° C., from 505° C. to 525° C., from 505° C. to 530° C., from 505° C. to 535° C., from 505° C. to 540° C., from 505° C. to 545° C., from 505° C. to 550° C., from 505° C. to 555° C., from 505° C. to 560° C., from 505° C. to 565° C., from 505° C. to 570° C., from 505° C. to 575° C., from 510° C. to 515° C., from 510° C. to 520° C., from 510° C. to 525° C., from 510° C. to 530° C., from 510° C. to 535° C., from 510° C. to 540° C., from 510° C. to 545° C., from 510° C. to 550° C., from 510° C. to 555° C., from 510° C. to 560° C., from 510° C. to 565° C., from 510° C. to 570° C., from 510° C. to 575° C., from 510° C. to 580° C., from 515° C. to 520° C., from 515° C. to 525° C., from 515° C. to 530° C., from 515° C. to 535° C., from 515° C. to 540° C., from 515° C. to 545° C., from 515° C. to 550° C., from 515° C. to 555° C., from 515° C. to 560° C., from 515° C. to 565° C., from 515° C. to 570° C., from 515° C. to 575° C., from 515° C. to 580° C., from 520° C. to 525° C., from 520° C. to 530° C., from 520° C. to 535° C., from 520° C. to 540° C., from 520° C. to 545° C., from 520° C. to 550° C., from 520° C. to 555° C., from 520° C. to 560° C., from 520° C. to 565° C., from 520° C. to 570° C., from 520° C. to 575° C., from 520° C. to 580° C., from 525° C. to 530° C., from 525° C. to 535° C., from 525° C. to 540° C., from 525° C. to 545° C., from 525° C. to 550° C., from 525° C. to 555° C., from 525° C. to 560° C., from 525° C. to 565° C., from 525° C. to 570° C., from 525° C. to 575° C., from 525° C. to 580° C., from 530° C. to 535° C., from 530° C. to 540° C., from 530° C. to 545° C., from 530° C. to 550° C., from 530° C. to 555° C., from 530° C. to 560° C., from 530° C. to 565° C., from 530° C. to 570° C., from 530° C. to 575° C., from 530° C. to 580° C., from 535° C. to 540° C., from 535° C. to 545° C., from 535° C. to 550° C., from 535° C. to 555° C., from 535° C. to 560° C., from 535° C. to 565° C., from 535° C. to 570° C., from 535° C. to 575° C., from 535° C. to 580° C., from 540° C. to 545° C., from 540° C. to 550° C., from 540° C. to 555° C., from 540° C. to 560° C., from 540° C. to 565° C., from 540° C. to 570° C., from 540° C. to 575° C., from 540° C. to 580° C., from 545° C. to 550° C., from 545° C. to 555° C., from 545° C. to 560° C., from 545° C. to 565° C., from 545° C. to 570° C., from 545° C. to 575° C., from 545° C. to 580° C., from 550° C. to 555° C., from 550° C. to 560° C., from 550° C. to 565° C., from 550° C. to 570° C., from 550° C. to 575° C., from 550° C. to 580° C., from 555° C. to 560° C., from 555° C. to 565° C., from 555° C. to 570° C., from 555° C. to 575° C., from 555° C. to 580° C., from 560° C. to 565° C., from 560° C. to 570° C., from 560° C. to 575° C., from 560° C. to 580° C., from 565° C. to 570° C., from 565° C. to 575° C., from 565° C. to 580° C., from 570° C. to 575° C., from 570° C. to 580° C., or from 575° C. to 580° C. In some embodiments, soaking the homogenized aluminum alloy product at the second homogenization temperature controls a surface quality or characteristic of the homogenized aluminum alloy product. Optionally, soaking the homogenized aluminum alloy product at the second homogenization temperature brings a temperature of the homogenized aluminum alloy product to a temperature sufficient for a rolling process. Disclosed methods may optionally include subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- Other objects and advantages will be apparent from the following detailed description of non-limiting examples.
- 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.
-
FIG. 1 provides an illustrative graph showing a relationship between formability of an aluminum alloy and average particle size according to some embodiments. -
FIG. 2A provides a schematic illustration of an aluminum alloy sample having particles according to some embodiments. -
FIG. 2B provides a schematic illustration of forces being exerted on an aluminum alloy sample having particles according to some embodiments. -
FIG. 2C provides a schematic illustration of crack propagation in an aluminum alloy sample having particles according to some embodiments. -
FIG. 2D provides a schematic illustration of cracking of an aluminum alloy sample having particles according to some embodiments. -
FIG. 3 provides an optical micrograph image of a crack propagating through an aluminum alloy having particles according some embodiments. -
FIG. 4 provides a schematic overview of an example method for making an aluminum alloy product. -
FIG. 5 provides a plot showing example homogenization conditions used for making aluminum alloy products. -
FIG. 6 provides a method of making an aluminum alloy having favorable particle density and inter-particle spacing according to some embodiments. -
FIG. 7A andFIG. 7B provide plots showing predicted equilibrium phase diagrams for two example 3xxx series aluminum alloys. -
FIG. 8 provides electron micrograph images for samples of two example 3xxx series aluminum alloys as cast and after processing according to two different processing regimes. -
FIG. 9 provides electrical conductivity data for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 10 provides electron micrograph images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 11 provides electron micrograph images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 12 provides particle size distributions for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 13 provides images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 14 provides images for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 15A andFIG. 15B provide charts showing tensile properties for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. -
FIG. 16A andFIG. 16B provide plots showing bendability test results for samples of two example 3xxx series aluminum alloys processed according to two different processing regimes. - The present disclosure provides aluminum alloy products and methods of making and treating aluminum alloys and aluminum alloy products. In some examples, the aluminum alloys used in the methods and products described herein include, for example, 3xxx series aluminum alloys, 4xxx series aluminum alloys, 5xxx series aluminum alloys, or 6xxx series aluminum alloys. In some examples, the aluminum alloys may include an alloy matrix comprising aluminum, magnesium, manganese, silicon, iron, and optionally copper. By way of non-limiting example, 3xxx series aluminum alloys may be particularly useful with the disclosed methods and products. Exemplary 3xxx series (also referred to herein as AA3xxx series) aluminum alloys for use in the methods and products described herein can include AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3405, AA3405A, AA3405B, AA3007, AA3407, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3410, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, or AA3065.
- Specifically, the present disclosure relates to aluminum alloy products having improved formability. Large particles formed within aluminum alloy products may reduce the formability of the aluminum alloy products because large particles can increase cracking susceptibility and can reduce the overall strength of aluminum alloy products. Voids may form around particles, especially large particles, within the aluminum alloy material. Large particles often have increased porosity, reduced ductility, and can be more brittle than the aluminum alloy material surrounding the particle. The difference in material properties between the particles and aluminum alloy matrix may concentrate stress or strain applied to the aluminum alloy product around the particles. The larger the particle, the greater the propensity for stress or strain to concentrate around the particle. For example, excess or overly large particles may cause tear off to occur during manufacturing processes, such as during drawing or necking of the aluminum alloy, because of the weak points formed around the particles. In other scenarios, large particles may cause an aluminum alloy product to split or fracture during use.
- A general approach to increasing formability is to reduce particle size. However, when the alloy composition is fixed as particle size is reduced, the density of particles within a set volume of aluminum alloy increases, since the particles may simply decrease in size by breaking into multiple smaller particles. Increased particle density may also be detrimental to the formability of aluminum alloy products. As particle density increases, the particles become closer together, on average, reducing the spacing between proximate particles (inter-particle spacing). Reduced or low inter-particle spacing may be problematic because crack propagation may take less energy when particles are spaced close together, as cracks may preferentially extend between particles. For example, when an aluminum alloy is under stress or strain from use or during the manufacturing process (i.e., being stretched or pulled), cracks may form from voids present around particles or weak points within the aluminum alloy. A reduction in inter-particle spacing may increase crack propagation from the weak points around particles because less energy may be required for the crack to reach the next nearest particle. Thus, in some cases, reducing particle size can actually be detrimental to the formability of aluminum alloy products.
- Accordingly, controlling particle size and inter-particle spacing may be useful for making aluminum alloy products having improved or optimal formability. Advantageously, the presently described aluminum alloy products may exhibit particle sizes and inter-particle spacing that limit or reduce tear off and/or stress induced cracking (i.e., improve formability). Specifically, the aluminum alloys disclosed herein may include an elemental composition which allows for formation of favorable particle size and favorable inter-particle spacing.
- The aluminum alloys disclosed herein may also allow for an increase in recycled source content. Increasing the recycled source content of an aluminum alloy can reduce the formability of the aluminum alloy product because of certain higher alloying components present within the recycled source content. Recycled source content is generally a mixture of multiple different types of materials. Thus, the composition of the recycled source content can sometimes include undesirable components in undesirable amounts. Generally, the mixed composition may create undesirable particles upon casting and/or processing. For example, the particles may exhibit undesirable composition, sizing, and/or spacing. Accordingly, by use of the disclosed techniques, particle size and particle density can be controlled to a level that may be able to compensate for the mixed composition and therefore be compatible with high amounts of recycled source content without impacting the formability character of the resultant aluminum alloy product.
- Aluminum alloy products can be prepared by casting an aluminum alloy to form a cast aluminum alloy product and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product. During a casting process, aluminum alloy products containing iron and manganese may generate intermetallic particles comprising Al and one or more of Fe or Mn, which may be referred to herein as Al-(Fe, Mn) intermetallic particles or β-phase intermetallic particles, within the cast aluminum alloy product. When silicon is present, intermetallic particles comprising Al, Si, and one or more of Fe or Mn, also referred to herein as Al-(Fe, Mn)-Si intermetallic particles or α-phase intermetallic particles, may also be generated. As some amounts of iron and silicon are generally present in almost all aluminum alloys, many aluminum alloys may include such intermetallic particles upon casting.
- Each of these particle types exhibits different properties and contributes in different ways to the structure of the aluminum alloy. For example, β-phase particles tend to be larger and more blocky or geometric than α-phase particles, while α-phase particles are harder and tend to be smaller than β-phase particles, in general. During hot and cold rolling, intermetallic particles may be broken, impacting their size, distribution, and number density, for example.
- The presence of intermetallic particles in a cast aluminum alloy product may be beneficial. For example, aluminum alloys including intermetallic particles can be beneficial for forming aluminum beverage containers since the intermetallic particles may be significantly harder than other portions of the aluminum alloy product. During drawing, ironing, and necking, the hard intermetallic particles can reduce galling by cleaning die surfaces. For example, the intermetallic particles may abrade drawing, ironing, and necking dies and reduce or remove metal built up on the die surfaces.
- As the beverage container making process progresses through various drawing, ironing, and necking processes, wall thicknesses are reduced. The presence of β-phase intermetallic particles may be detrimental, however, when wall thicknesses are reduced during these processes if the β-phase particles are too large or present at too high of an amount. Excess or overly large β-phase particles may cause tear off to occur during drawing or necking, where the beverage container wall splits or fractures, damaging the beverage container wall. Tear off, in some cases, may interrupt the manufacturing processes, as wall portions may completely separate from a damaged beverage container and may need to be removed from within the die or other manufacturing equipment.
- Advantageously, however, the presently described aluminum alloy products exhibit intermetallic particle sizes, distributions, concentrations, and compositions that limit or reduce tear off. By using an increased ratio of silicon to iron, the disclosed aluminum alloy products may preferentially generate α-phase intermetallic particles, such as by converting β-phase intermetallic particles to α-phase intermetallic particles during a homogenization process.
- Further, during homogenization at high temperatures, alloying elements may diffuse and migrate throughout a crystal structure of a cast aluminum alloy product and change the size, distribution, concentration, and composition of intermetallic particles. For example, silicon atoms present in the aluminum crystal structure may diffuse into β-phase intermetallic particles and transform the particles into α-phase intermetallic particles. Since silicon may be present in low amounts, such as less than about 1 wt. %, it may take significant time for silicon to diffuse and accumulate in the β-phase intermetallic particles in the cast product, so long duration homogenization may be useful for effecting significant transformation of β-phase intermetallic particles. By homogenizing at high temperatures for a time duration greater than 12 hours or 24 hours, for example, silicon from the aluminum alloy may diffuse and transform at least a fraction of the β-phase intermetallic particles into α-phase intermetallic particles.
- Example homogenization conditions may include soaking a cast aluminum alloy product at a high temperature for 12 hours or 24 hours or more. For example, soaking may occur at a homogenization temperature of from about 575° C. to about 615° C., from about 580° C. to about 610° C., or from about 585° C. to about 605° C. A secondary homogenization process may also be useful for some embodiments. For example, a temperature of the homogenized aluminum alloy product may be reduced to a lower temperature and the aluminum alloy product may be held (soaked) at the lower temperature for a particular time duration. Example secondary homogenization temperatures include from about 500° C. to about 600° C., and may be dependent upon the particular alloy. Example secondary homogenization soak time durations include from about 1 hour to about 24 hours. A secondary homogenization at reduced temperature of this type may be useful for controlling and/or improving a surface quality or characteristic of the homogenized aluminum alloy product.
- During homogenization, the size, composition, concentration, and distribution of intermetallic particles may change. For example, β-phase intermetallic particles may take up silicon atoms and be transformed into α-phase particles, at least in part, which may reduce the sizes of any residual β-phase intermetallic particles. Thus, an average size of β-phase intermetallic particles may decrease during homogenization or soaking. Similarly, a number density of β-phase intermetallic particles may decrease during homogenization or soaking. In some embodiments, an amount of β-phase intermetallic particles are transformed into α-phase intermetallic particles during homogenization or soaking, such as from about 30% to about 100%. A number density of α-phase intermetallic particles may increase during homogenization or soaking. Number density ratios of α-phase intermetallic particles to β-phase intermetallic particles of from about 2 to about 1000 may be achieved by the long duration homogenization processes described herein. As cast, however, number density ratios of α-phase intermetallic particles to β-phase intermetallic particles may be from about 0.3 to about 3 for example.
- Aluminum alloys used for the methods and products described herein may correspond to recycled materials, such as recycled beverage containers. In the process of casting the aluminum alloys, source materials, such as recycled beverage containers may be melted to prepare a molten aluminum alloy. As beverage containers tend to include 3xxx series manganese containing aluminum alloys (e.g., AA3104) and 5xxx series magnesium containing aluminum alloys (e.g., AA5182), this source material may be useful for preparing new aluminum alloy products for making new beverage containers. For cases where a silicon to iron ratio (e.g., wt. % ratio) is to be increased to obtain the benefits described above with respect to intermetallic particles, an additional source of silicon may be used. For example, other silicon containing alloys may be added to the molten aluminum, such as a 4xxx series aluminum alloy or a 6xxx series aluminum alloy. In some cases, these sources of supplemental silicon may correspond to recycled aluminum alloy materials.
- Non-limiting exemplary AA4xxx series alloys for use in the methods described herein can include AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, or AA4147.
- Non-limiting exemplary AA6xxx series alloys for use in the methods described herein can include AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA6016, AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027, AA6028, AA6031, AA6032, AA6033, AA6040, AA6041, AA6042, AA6043, AA6151, AA6351, AA6351A, AA6451, AA6951, AA6053, AA6055, AA6056, AA6156, AA6060, AA6160, AA6260, AA6360, AA6460, AA6460B, AA6560, AA6660, AA6061, AA6061A, AA6261, AA6361, AA6162, AA6262, AA6262A, AA6063, AA6063A, AA6463, AA6463A, AA6763, A6963, AA6064, AA6064A, AA6065, AA6066, AA6068, AA6069, AA6070, AA6081, AA6181, AA6181A, AA6082, AA6082A, AA6182, AA6091, or AA6092.
- As used herein, the terms “invention,” “the invention,” “this invention,” and “the present invention” are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below.
- In this description, reference is made to alloys identified by AA numbers and other related designations, such as “series” or “3xxx.” For an understanding of the number designation system most commonly used in naming and identifying aluminum and its alloys, see “International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys” or “Registration Record of Aluminum Association Alloy Designations and Chemical Compositions Limits for Aluminum Alloys in the Form of Castings and Ingot,” both published by The Aluminum Association.
- As used herein, a plate generally has a thickness of greater than about 15 mm. For example, a plate may refer to an aluminum alloy 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.
- 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, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, or 15 mm.
- As used herein, a sheet generally refers to an aluminum alloy 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).
- As used herein, terms such as “cast metal product,” “cast product,” “cast aluminum alloy product,” and the like are interchangeable and refer to a product produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by use of a twin belt caster, a twin roll caster, a block caster, or any other continuous caster), electromagnetic casting, hot top casting, or any other casting method.
- As used herein, the meaning of “room temperature” can include a temperature of from about 15° C. to about 30° C., for example about 15° C., 16° C., 17° C., 18° C., 19° C., 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., or 30° C. As used herein, the meaning of “ambient conditions” can include temperatures of about room temperature, relative humidity of from about 20% to about 100%, and barometric pressure of from about 975 millibar (mbar) to about 4050 mbar. For example, relative humidity can be about 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, or anywhere in between. For example, barometric pressure can be about 975 mbar, 980 mbar, 985 mbar, 990 mbar, 995 mbar, 1000 mbar, 1005 mbar, 1010 mbar, 1015 mbar, 1020 mbar, 1025 mbar, 1030 mbar, 1035 mbar, 1040 mbar, 1045 mbar, 4050 mbar, or anywhere in between.
- All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, e.g., 1 to 6.1, and ending with a maximum value of 10 or less, e.g., 5.5 to 10. Unless stated otherwise, the expression “up to” when referring to the compositional amount of an element means that element is optional and includes a zero percent composition of that particular element. Unless stated otherwise, all compositional percentages are in weight percent (wt. %).
- As used herein, the meaning of “a,” “an,” and “the” includes singular and plural references unless the context clearly dictates otherwise.
- Aspects of the present disclosure relate to aluminum alloy products and methods of making aluminum alloy products that have favorable particle size and inter-particle spacing for improved formability. For example, the disclosed aluminum alloy products may have an elemental composition that allows for generation of favorable particle sizes while maintaining inter-particle spacing at a level sufficient to reduce crack formation and propagation. Generally, to increase formability of an aluminum alloy product, the size of included particles, such as intermetallic particles, may be reduced. However, as particle size within an aluminum alloy product is reduced, the particle density may increase and the inter-particle spacing may decrease. Undesirably, when the inter-particle spacing becomes low, this may increase cracking susceptibility and be detrimental to formability. The disclosed methods, techniques and products, however, overcome this characteristic by controlling the inter-particle spacing and particle size to a level which minimizes or reduces crack susceptibility and crack propagation, resulting in a product with improved formability characteristics.
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FIG. 1 provides agraph 100 that illustrates the relationship between average particle size and formability.Line 110 corresponds to a theoretical approach to improving formability. The theoretical approach depicted byline 110 may illustrate the conventional approach to improving formability by reducing particle size. As shown byline 110, as particle size increases the formability of the aluminum alloy product should decrease. Conversely, as particle size decreases, theoretically, formability should increase. Such a relationship, however, does not hold true in practice when the overall composition of the aluminum alloy product is held constant. For example, when the average particle size decreases at fixed composition, the quantity and number density must increase, as large particles are broken down into more particles of smaller size.Line 120 shows that, in practice, the relationship between particle size and product formability may not be linear. Instead, the relationship between particle size and product formability may be non-linear, and reflect an optimal formability character at a midrange particle size. Followingline 120 starting from the origin, as particle size increases, formability may increase as well within an initial range of particle size. However, once the particle size reaches a certain point, the formability of the product may begin to decrease again. The relationship of formability and particle size illustrated byline 120 may be representative of how both particle size and inter-particle spacing impact the formability of an aluminum alloy product. - A reduction in particle size may result in an increase of particle density within a set volume of aluminum alloy when the composition remains fixed. An increased density may mean that the particles are positioned closer to each other, or, stated another way, the inter-particle spacing between particles may be reduced. Small inter-particle spacing may be detrimental to formability because the shorter the inter-particle spacing, the more susceptible the aluminum alloy may be to crack propagation, as it may be easier (i.e., require less force) for a crack to propagate from one particle to the next particle to the next particle, and so on. However, increasing inter-particle spacing may necessitate larger particle sizes when the composition is fixed (i.e., when the total volume or mass of the particles is held constant), resulting in formation of larger particles and a reduction in the number density of the particles. While an increase in inter-particle spacing may require more energy or force for a crack to propagate from particle to particle, reducing cracking susceptibility to some extent, the resulting larger particles may still act as crack initiation or weak points. As previously noted, larger particles tend to form voids within the aluminum alloy material which can concentrate deformation forces when the aluminum alloy product is under stress or strain. Thus, while larger particles may correspond to larger inter-particle spacing, making crack propagation more energy intensive, larger particles may also act as crack initiation points, leading to more overall weak points within the aluminum alloy. Thus, to achieve optimal formability, particle size and inter-particle spacing must be balanced.
FIGS. 2A-2D provide schematic illustrations of an aluminum alloy sample, depicting how smaller particle sizes may detrimentally affect the formability of an aluminum alloy. InFIG. 2A , analuminum alloy 210 is illustrated.Aluminum alloy 210 includes a plurality ofparticles 220.Particles 220 may include various types of particles. For example, the plurality ofparticles 220 may include one or more of constituent particles, intermetallic particles, oxides, precipitate or hardening particles. In some embodiments,particles 220 may include iron-containing particles and/or manganese dispersoids.Particles 220 may include one or more intermetallic particles. For example,particles 220 may include α-phase intermetallic particles and β-phase intermetallic particles.Aluminum alloy 210 may have a higher proportion of α-phase intermetallic particles than β-phase intermetallic particles, which may correspond to a low average particle size, since α-phase intermetallic particles may tend to be smaller and less blocky than β-phase intermetallic particles. In some embodiments, the iron-containing particles may account for from 1% to 4% of the total volume of the aluminum alloy. For example, the iron-containing particles may account for 1% to 2%, from 1% to 3%, from 2% to 3%, from 2% to 4%, or from 3% to 4% of the total volume of the aluminum alloy. In some embodiments, the iron-containing particles may have a diameter from 1 µm to 40 µm, such as from 2 µm to 40 µm, 5 µm to 40 µm, 7 µm to 40 µm, 10 µm to 40 µm, 15 µm to 40 µm, 20 µm to 40 µm, 25 µm to 40 µm, 30 µm to 40 µm, or 35 µm to 40 µm. In some embodiments, the reference to particle diameters for the iron-containing particles may be for the majority of the iron-containing particles. For example, a description that the iron-containing particles have a diameter of from 1 µm to 40 µm may mean that the majority (i.e., greater than 50%) of the iron-containing particles have a diameter of 1 µm to 40 µm or that 80% of the of the iron-containing particles have a diameter of 1 µm to 40 µm. - In
FIG. 2B ,force 230 is shown applied toaluminum alloy 210.Force 230 may exemplify forces commonly applied during a manufacturing process or during use of a product produced fromaluminum alloy 210. For example, thealuminum alloy 210 may be placed under stress during a drawing process, a rolling process, a stamping process, or the like. In some cases,force 230 may represent forces applied after manufacturing, such as directly to an aluminum alloy product or article prepared fromaluminum alloy 210. -
Force 230 may causecracks 240 to initiate aroundparticles 220 and propagate throughaluminum alloy 210, as illustrated inFIG. 2C . As noted above,particles 220 may act as weak points or force concentration points withinaluminum alloy 210. While larger particles tend to form larger weak points, smaller particles may also act as weak points by forming voids or concentrating deformation forces whenforce 230 is applied. In part, becauseparticles 220 have a different material composition than the bulk ofaluminum alloy 210, the interface between the particles and the surrounding alloy may act as weak points, for example. Differences in hardness, porosity, ductility, and brittleness may all affect the formation of a weak point aroundparticles 220. - As illustrated in
FIG. 2B ,particles 220 may be separated as depicted byinter-particle spacing 225.Inter-particle spacing 225 may correspond to the average or shortest distance between two particles. As noted above, in some embodiments,inter-particle spacing 225 may directly correlate to particle density if the volume fraction ofparticles 220 remains the same. For example, as the density of particles increases,inter-particle spacing 225 may decrease. Conversely, as the density of particles decreases,inter-particle spacing 225 may increase. -
FIGS. 2C and 2D may illustrate how a decrease ininter-particle spacing 225 may be detrimental to formability. Wheninter-particle spacing 225 becomes too small,cracks 240 may easily propagate betweenparticles 220. As shown inFIG. 2C , propagation ofcracks 240 may follow a lowest energy path. For example, cracks 240 may propagate to the next closest weak point, such asparticle 220, withinaluminum alloy 210. Ifinter-particle spacing 225 is lowered, then it may take less energy forcrack 240 to propagate from one particle to the next. Less energy may correspond to less material forcrack 240 to move through. In contrast, ifinter-particle spacing 225 is higher, more energy may be required forcrack 240 to propagate to the next weak point because there is more material between the crack initiation point and the imperfection. - When particle density is increased and
inter-particle spacing 225 is decreased,cracks 240 may easily propagate tonearby particles 220. This may result in a domino-effect of crack propagation and eventually lead to complete fracturing or shearing 250 ofaluminum alloy 210, as depicted atFIG. 2D . Fracturing orshearing 250 may result in breakage or where large pieces ofaluminum alloy 210 separate from the bulk ofaluminum alloy 210. Fracturing 250 may impact the integrity and strength ofaluminum alloy 210. -
FIG. 3 provides anoptical micrograph image 300 of acrack 340 propagating between alarge imperfection 350 andparticle 320 within an aluminum alloy. The aluminum alloy depicted inFIG. 3 may correspond to an aluminum alloy having smaller particle sizes and an overall small averageinter-particle spacing 325. In some cases,imperfection 350 may be a void, crack or crack initiation point, weak point, or another particle within the aluminum alloy. As shown inimage 300, crack 340 may propagate betweenimperfection 350 and the nextclosest particle 320. Anadditional imperfection 352 may be present or form aroundparticle 320. In some cases,imperfection 352 may act as a weak point. Crack 340 may propagate toparticle 320 along a low energy path betweenimperfection 350 andimperfection 352. When further stress or force is applied, cracks may become larger and spur further propagation. - The aluminum alloys and related products discussed herein may achieve favorable inter-particle spacing while maintaining favorable particle size. In some embodiments, the aluminum alloys as provided herein may have an inter-particle spacing from about 1 µm to about 25 µm. For example, the inter-particle spacing may be from about 1 µm to about 25 µm, from 1 µm to 2 µm, from 1 µm to 5 µm, from 1 µm to 7 µm, from 1 µm to 10 µm, from 1 µm to 12 µm, from 1 µm to 15 µm, from 1 µm to 17 µm, from 1 µm to 20 µm, from 1 µm to 22 µm, from 1 µm to 25 µm, from 2 µm to 5 µm, from 2 µm to 7 µm, from 2 µm to 10 µm, from 2 µm to 12 µm, from 2 µm to 15 µm, from 2 µm to 17 µm, from 2 µm to 20 µm, from 2 µm to 22 µm, from 2 µm to 25 µm, from 5 µm to 7 µm, from 5 µm to 10 µm, from 5 µm to 12 µm, from 5 µm to 15 µm, from 5 µm to 17 µm, from 5 µm to 20 µm, from 5 µm to 22 µm, from 5 µm to 25 µm, from 7 µm to 10 µm, from 7 µm to 12 µm, from 7 µm to 15 µm, from 7 µm to 17 µm, from 7 µm to 20 µm, from 7 µm to 22 µm, from 7 µm to 25 µm, from 10 µm to 12 µm, from 10 µm to 15 µm, from 10 µm to 17 µm, from 10 µm to 20 µm, from 10 µm to 22 µm, from 10 µm to 25 µm, from 12 µm to 15 µm, from 12 µm to 17 µm, from 12 µm to 20 µm, from 12 µm to 22 µm, from 12 µm to 25 µm, from 15 µm to 17 µm, from 15 µm to 20 µm, from 15 µm to 22 µm, from 15 µm to 25 µm, from 17 µm to 20 µm, from 17 µm to 22 µm, from 17 µm to 25 µm, from 20 µm to 22 µm, from 20 µm to 25 µm, or from 22 µm to 25 µm. In some embodiments, inter-particle spacing may be described with relation to the majority (greater than 50%) of the plurality of particles. For example, 80 percent or more of the plurality of particles within an aluminum alloy may have inter-particle spacing from 1 µm to 25 µm.
- To achieve favorable inter-particle spacing, the size and density of particles within the aluminum alloys may be controlled or limited. A particle density may be represented as a number of particles per unit volume (e.g., particles per µm3) or as a number of particles per unit area (e.g., particles per µm2). Use of particle density as a number of particles per unit area may be useful for quickly characterizing the number of particles in an aluminum alloy or product by obtaining a scanning electron micrograph image or an optical micrograph image of a region of the aluminum alloy or product and counting the number of particles in the image, which may represent a 2-dimensional slice of the aluminum alloy or product. In some examples, multiple images can be obtained to provide a representative sample of the aluminum alloy or product, such as for counting particles or establishing a particle density. In some examples, the aluminum alloys may have or be controlled to have a particle density of 5 to 30,000 particles per µm2 (e.g., 8 to 1,400 particles per µm2) while maintaining particle diameters from 100 nm to 50 µm. As used herein, particle diameters may be used to quantify particle size. In some cases, the particle density and/or diameters are characterized by obtaining scanning electron micrograph image(s) or optical micrograph image(s) of a region or regions of the aluminum alloy or product and counting or evaluating the particles in the image(s).
- In some cases, particle density may be from 5 to 30,000 particles per µm2, such as from 10 to 25,000, from 10 to 20,000, from 10 to 15,000, from 10 to 10,000, from 10 to 9,500, from 10 to 9,000, from 10 to 8,500, from 10 to 8,000, from 10 to 7,500, from 10 to 7,000, from 10 to 6,500, from 10 to 6,000, from 10 to 5,500, from 10 to 5,000, from 10 to 4,500, from 10 to 4,000, from 10 to 3,500, from 10 to 3,000, from 10 to 2,500, from 10 to 2,000, from 10 to 1,500, from 10 to 1,000, from 10 to 950, from 10 to 900, from 10 to 850, from 10 to 800, from 10 to 750, from 10 to 700, from 10 to 650, from 10 to 600, from 10 to 550, from 10 to 500, from 10 to 450, from 10 to 400, from 10 to 350, from 10 to 300, from 10 to 250, from 10 to 200, from 10 to 150, from 10 to 100, from 10 to 75, from 10 to 50, from 10 to 25, from 25 to 30,000, from 25 to 25,000, from 25 to 20,000, from 25 to 15,000, from 25 to 10,000, from 25 to 9,500, from 25 to 9,000, from 25 to 8,500, from 25 to 8,000, from 25 to 7,500, from 25 to 7,000, from 25 to 6,500, from 25 to 6,000, from 25 to 5,500, from 25 to 5,000, from 25 to 4,500, from 25 to 4,000, from 25 to 3,500, from 25 to 3,000, from 25 to 2,500, from 25 to 2,000, from 25 to 1,500, from 25 to 1,000, from 25 to 950, from 25 to 900, from 25 to 850, from 25 to 800, from 25 to 750, from 25 to 700, from 25 to 650, from 25 to 600, from 25 to 550, from 25 to 500, from 25 to 450, from 25 to 400, from 25 to 350, from 25 to 300, from 25 to 250, from 25 to 200, from 25 to 150, from 25 to 100, from 25 to 75, from 25 to 50, from 50 to 30,000, from 50 to 25,000, from 50 to 20,000, from 50 to 15,000, from 50 to 10,000, from 50 to 9,500, from 50 to 9,000, from 50 to 8,500, from 50 to 8,000, from 50 to 7,500, from 50 to 7,000, from 50 to 6,500, from 50 to 6,000, from 50 to 5,500, from 50 to 5,000, from 50 to 4,500, from 50 to 4,000, from 50 to 3,500, from 50 to 3,000, from 50 to 2,500, from 50 to 2,000, from 50 to 1,500, from 50 to 1,000, from 50 to 950, from 50 to 900, from 50 to 850, from 50 to 800, from 50 to 750, from 50 to 700, from 50 to 650, from 50 to 600, from 50 to 550, from 50 to 500, from 50 to 450, from 50 to 400, from 50 to 350, from 50 to 300, from 50 to 250, from 50 to 200, from 50 to 150, from 50 to 100, from 50 to 75, from 75 to 30,000, from 75 to 25,000, from 75 to 20,000, from 75 to 15,000, from 75 to 10,000, from 75 to 9,500, from 75 to 9,000, from 75 to 8,500, from 75 to 8,000, from 75 to 7,500, from 75 to 7,000, from 75 to 6,500, from 75 to 6,000, from 75 to 5,500, from 75 to 5,000, from 75 to 4,500, from 75 to 4,000, from 75 to 3,500, from 75 to 3,000, from 75 to 2,500, from 75 to 2,000, from 75 to 1,500, from 75 to 1,000, from 75 to 950, from 75 to 900, from 75 to 850, from 75 to 800, from 75 to 750, from 75 to 700, from 75 to 650, from 75 to 600, from 75 to 550, from 75 to 500, from 75 to 450, from 75 to 400, from 75 to 350, from 75 to 300, from 75 to 250, from 75 to 200, from 75 to 150, from 75 to 100, from 100 to 30,000, from 100 to 25,000, from 100 to 20,000, from 100 to 15,000, from 100 to 10,000, from 100 to 9,500, from 100 to 9,000, from 100 to 8,500, from 100 to 8,000, from 100 to 7,500, from 100 to 7,000, from 100 to 6,500, from 100 to 6,000, from 100 to 5,500, from 100 to 5,000, from 100 to 4,500, from 100 to 4,000, from 100 to 3,500, from 100 to 3,000, from 100 to 2,500, from 100 to 2,000, from 100 to 1,500, from 100 to 1,000, from 100 to 950, from 100 to 900, from 100 to 850, from 100 to 800, from 100 to 750, from 100 to 700, from 100 to 650, from 100 to 600, from 100 to 550, from 100 to 500, from 100 to 450, from 100 to 400, from 100 to 350, from 100 to 300, from 100 to 250, from 100 to 200, from 100 to 150, from 150 to 30,000, from 150 to 25,000, from 150 to 20,000, from 150 to 15,000, from 150 to 10,000, from 150 to 9,500, from 150 to 9,000, from 150 to 8,500, from 150 to 8,000, from 150 to 7,500, from 150 to 7,000, from 150 to 6,500, from 150 to 6,000, from 150 to 5,500, from 150 to 5,000, from 150 to 4,500, from 150 to 4,000, from 150 to 3,500, from 150 to 3,000, from 150 to 2,500, from 150 to 2,000, from 150 to 1,500, from 150 to 1,000, from 150 to 950, from 150 to 900, from 150 to 850, from 150 to 800, from 150 to 750, from 150 to 700, from 150 to 650, from 150 to 600, from 150 to 550, from 150 to 500, from 150 to 450, from 150 to 400, from 150 to 350, from 150 to 300, from 150 to 250, from 150 to 200, from 200 to 30,000, from 200 to 25,000, from 200 to 20,000, from 200 to 15,000, from 200 to 10,000, from 200 to 9,500, from 200 to 9,000, from 200 to 8,500, from 200 to 8,000, from 200 to 7,500, from 200 to 7,000, from 200 to 6,500, from 200 to 6,000, from 200 to 5,500, from 200 to 5,000, from 200 to 4,500, from 200 to 4,000, from 200 to 3,500, from 200 to 3,000, from 200 to 2,500, from 200 to 2,000, from 200 to 1,500, from 200 to 1,000, from 200 to 950, from 200 to 900, from 200 to 850, from 200 to 800, from 200 to 750, from 200 to 700, from 200 to 650, from 200 to 600, from 200 to 550, from 200 to 500, from 200 to 450, from 200 to 400, from 200 to 350, from 200 to 300, from 200 to 250, from 250 to 30,000, from 250 to 25,000, from 250 to 20,000, from 250 to 15,000, from 250 to 10,000, from 250 to 9,500, from 250 to 9,000, from 250 to 8,500, from 250 to 8,000, from 250 to 7,500, from 250 to 7,000, from 250 to 6,500, from 250 to 6,000, from 250 to 5,500, from 250 to 5,000, from 250 to 4,500, from 250 to 4,000, from 250 to 3,500, from 250 to 3,000, from 250 to 2,500, from 250 to 2,000, from 250 to 1,500, from 250 to 1,000, from 250 to 950, from 250 to 900, from 250 to 850, from 250 to 800, from 250 to 750, from 250 to 700, from 250 to 650, from 250 to 600, from 250 to 550, from 250 to 500, from 250 to 450, from 250 to 400, from 250 to 350, from 250 to 300, from 300 to 30,000, from 300 to 25,000, from 300 to 20,000, from 300 to 15,000, from 300 to 10,000, from 300 to 9,500, from 300 to 9,000, from 300 to 8,500, from 300 to 8,000, from 300 to 7,500, from 300 to 7,000, from 300 to 6,500, from 300 to 6,000, from 300 to 5,500, from 300 to 5,000, from 300 to 4,500, from 300 to 4,000, from 300 to 3,500, from 300 to 3,000, from 300 to 2,500, from 300 to 2,000, from 300 to 1,500, from 300 to 1,000, from 300 to 950, from 300 to 900, from 300 to 850, from 300 to 800, from 300 to 750, from 300 to 700, from 300 to 650, from 300 to 600, from 300 to 550, from 300 to 500, from 300 to 450, from 300 to 400, from 300 to 350, from 350 to 30,000, from 350 to 25,000, from 350 to 20,000, from 350 to 15,000, from 350 to 10,000, from 350 to 9,500, from 350 to 9,000, from 350 to 8,500, from 350 to 8,000, from 350 to 7,500, from 350 to 7,000, from 350 to 6,500, from 350 to 6,000, from 350 to 5,500, from 350 to 5,000, from 350 to 4,500, from 350 to 4,000, from 350 to 3,500, from 350 to 3,000, from 350 to 2,500, from 350 to 2,000, from 350 to 1,500, from 350 to 1,000, from 350 to 950, from 350 to 900, from 350 to 850, from 350 to 800, from 350 to 750, from 350 to 700, from 350 to 650, from 350 to 600, from 350 to 550, from 350 to 500, from 350 to 450, from 350 to 400, from 400 to 30,000, from 400 to 25,000, from 400 to 20,000, from 400 to 15,000, from 400 to 10,000, from 400 to 9,500, from 400 to 9,000, from 400 to 8,500, from 400 to 8,000, from 400 to 7,500, from 400 to 7,000, from 400 to 6,500, from 400 to 6,000, from 400 to 5,500, from 400 to 5,000, from 400 to 4,500, from 400 to 4,000, from 400 to 3,500, from 400 to 3,000, from 400 to 2,500, from 400 to 2,000, from 400 to 1,500, from 400 to 1,000, from 400 to 950, from 400 to 900, from 400 to 850, from 400 to 800, from 400 to 750, from 400 to 700, from 400 to 650, from 400 to 600, from 400 to 550, from 400 to 500, from 400 to 450, from 450 to 30,000, from 450 to 25,000, from 450 to 20,000, from 450 to 15,000, from 450 to 10,000, from 450 to 9,500, from 450 to 9,000, from 450 to 8,500, from 450 to 8,000, from 450 to 7,500, from 450 to 7,000, from 450 to 6,500, from 450 to 6,000, from 450 to 5,500, from 450 to 5,000, from 450 to 4,500, from 450 to 4,000, from 450 to 3,500, from 450 to 3,000, from 450 to 2,500, from 450 to 2,000, from 450 to 1,500, from 450 to 1,000, from 450 to 950, from 450 to 900, from 450 to 850, from 450 to 800, from 450 to 750, from 450 to 700, from 450 to 650, from 450 to 600, from 450 to 550, from 450 to 500, from 500 to 30,000, from 500 to 25,000, from 500 to 20,000, from 500 to 15,000, from 500 to 10,000, from 500 to 9,500, from 500 to 9,000, from 500 to 8,500, from 500 to 8,000, from 500 to 7,500, from 500 to 7,000, from 500 to 6,500, from 500 to 6,000, from 500 to 5,500, from 500 to 5,000, from 500 to 4,500, from 500 to 4,000, from 500 to 3,500, from 500 to 3,000, from 500 to 2,500, from 500 to 2,000, from 500 to 1,500, from 500 to 1,000, from 500 to 950, from 500 to 900, from 500 to 850, from 500 to 800, from 500 to 750, from 500 to 700, from 500 to 650, from 500 to 600, from 500 to 550, from 600 to 30,000, from 600 to 25,000, from 600 to 20,000, from 600 to 15,000, from 600 to 10,000, from 600 to 9,500, from 600 to 9,000, from 600 to 8,500, from 600 to 8,000, from 600 to 7,500, from 600 to 7,000, from 600 to 6,500, from 600 to 6,000, from 600 to 5,500, from 600 to 5,000, from 600 to 4,500, from 600 to 4,000, from 600 to 3,500, from 600 to 3,000, from 600 to 2,500, from 600 to 2,000, from 600 to 1,500, from 600 to 1,000, from 600 to 950, from 600 to 900, from 600 to 850, from 600 to 800, from 600 to 750, from 600 to 700, from 600 to 650, from 700 to 30,000, from 700 to 25,000, from 700 to 20,000, from 700 to 15,000, from 700 to 10,000, from 700 to 9,500, from 700 to 9,000, from 700 to 8,500, from 700 to 8,000, from 700 to 7,500, from 700 to 7,000, from 700 to 6,500, from 700 to 6,000, from 700 to 5,500, from 700 to 5,000, from 700 to 4,500, from 700 to 4,000, from 700 to 3,500, from 700 to 3,000, from 700 to 2,500, from 700 to 2,000, from 700 to 1,500, from 700 to 1,000, from 700 to 950, from 700 to 900, from 700 to 850, from 700 to 800, from 700 to 750, from 800 to 30,000, from 800 to 25,000, from 800 to 20,000, from 800 to 15,000, from 800 to 10,000, from 800 to 9,500, from 800 to 9,000, from 800 to 8,500, from 800 to 8,000, from 800 to 7,500, from 800 to 7,000, from 800 to 6,500, from 800 to 6,000, from 800 to 5,500, from 800 to 5,000, from 800 to 4,500, from 800 to 4,000, from 800 to 3,500, from 800 to 3,000, from 800 to 2,500, from 800 to 2,000, from 800 to 1,500, from 800 to 1,000, from 800 to 950, from 800 to 900, from 800 to 850, from 900 to 30,000, from 900 to 25,000, from 900 to 20,000, from 900 to 15,000, from 900 to 10,000, from 900 to 9,500, from 900 to 9,000, from 900 to 8,500, from 900 to 8,000, from 900 to 7,500, from 900 to 7,000, from 900 to 6,500, from 900 to 6,000, from 900 to 5,500, from 900 to 5,000, from 900 to 4,500, from 900 to 4,000, from 900 to 3,500, from 900 to 3,000, from 900 to 2,500, from 900 to 2,000, from 900 to 1,500, from 900 to 1,000, from 900 to 950, from 1,000 to 30,000, from 1,000 to 25,000, from 1,000 to 20,000, from 1,000 to 15,000, from 1,000 to 10,000, from 1,000 to 9,500, from 1,000 to 9,000, from 1,000 to 8,500, from 1,000 to 8,000, from 1,000 to 7,500, from 1,000 to 7,000, from 1,000 to 6,500, from 1,000 to 6,000, from 1,000 to 5,500, from 1,000 to 5,000, from 1,000 to 4,500, from 1,000 to 4,000, from 1,000 to 3,500, from 1,000 to 3,000, from 1,000 to 2,500, from 1,000 to 2,000, from 1,000 to 1,500, from 2,000 to 30,000, from 2,000 to 25,000, from 2,000 to 20,000, from 2,000 to 15,000, from 2,000 to 10,000, from 2,000 to 9,500, from 2,000 to 9,000, from 2,000 to 8,500, from 2,000 to 8,000, from 2,000 to 7,500, from 2,000 to 7,000, from 2,000 to 6,500, from 2,000 to 6,000, from 2,000 to 5,500, from 2,000 to 5,000, from 2,000 to 4,500, from 2,000 to 4,000, from 2,000 to 3,500, from 2,000 to 3,000, from 2,000 to 2,500, from 3,000 to 30,000, from 3,000 to 25,000, from 3,000 to 20,000, from 3,000 to 15,000, from 3,000 to 10,000, from 3,000 to 9,500, from 3,000 to 9,000, from 3,000 to 8,500, from 3,000 to 8,000, from 3,000 to 7,500, from 3,000 to 7,000, from 3,000 to 6,500, from 3,000 to 6,000, from 3,000 to 5,500, from 3,000 to 5,000, from 3,000 to 4,500, from 3,000 to 4,000, from 3,000 to 3,500, from 4,000 to 30,000, from 4,000 to 25,000, from 4,000 to 20,000, from 4,000 to 15,000, from 4,000 to 10,000, from 4,000 to 9,500, from 4,000 to 9,000, from 4,000 to 8,500, from 4,000 to 8,000, from 4,000 to 7,500, from 4,000 to 7,000, from 4,000 to 6,500, from 4,000 to 6,000, from 4,000 to 5,500, from 4,000 to 5,000, from 4,000 to 4,500, from 5,000 to 30,000, from 5,000 to 25,000, from 5,000 to 20,000, from 5,000 to 15,000, from 5,000 to 10,000, from 5,000 to 9,500, from 5,000 to 9,000, from 5,000 to 8,500, from 5,000 to 8,000, from 5,000 to 7,500, from 5,000 to 7,000, from 5,000 to 6,500, from 5,000 to 6,000, from 5,000 to 5,500, from 6,000 to 30,000, from 6,000 to 25,000, from 6,000 to 20,000, from 6,000 to 15,000, from 6,000 to 10,000, from 6,000 to 9,500, from 6,000 to 9,000, from 6,000 to 8,500, from 6,000 to 8,000, from 6,000 to 7,500, from 6,000 to 7,000, from 6,000 to 6,500, from 7,000 to 30,000, from 7,000 to 25,000, from 7,000 to 20,000, from 7,000 to 15,000, from 7,000 to 10,000, from 7,000 to 9,500, from 7,000 to 9,000, from 7,000 to 8,500, from 7,000 to 8,000, from 7,000 to 7,500, from 8,000 to 30,000, from 8,000 to 25,000, from 8,000 to 20,000, from 8,000 to 15,000, from 8,000 to 10,000, from 8,000 to 9,500, from 8,000 to 9,000, from 8,000 to 8,500, from 9,000 to 30,000, from 9,000 to 25,000, from 9,000 to 20,000, from 9,000 to 15,000, from 9,000 to 10,000, from 9,000 to 9,500, from 10,000 to 30,000, from 10,000 to 25,000, from 10,000 to 20,000, from 10,000 to 15,000, from 15,000 to 30,000, from 15,000 to 25,000, from 15,000 to 20,000, from 20,000 to 30,000, from 20,000 to 25,000, or from 25,000 to 30,000 particles per µm2.
- Depending on composition and/or final application for the aluminum alloy products, example particle diameters may range from 100 nm to 100 µm. For example the particle diameters may range from 150 nm to 100 µm, from 200 nm to 100 µm, from 300 nm to 100 µm, from 400 nm to 100 µm, from 500 nm to 100 µm, from 600 nm to 100 µm, from 700 nm to 100 µm, from 800 nm to 100 µm, from 1 µm to 100 µm, from 5 µm to 100 µm, from 10 µm to 100 µm , from 15 µm to 100 µm, from 25 µm to 100 µm, from 50 µm to 100 µm, from 75 µm to 100 µm, from 150 nm to 75 µm, from 200 nm to 75 µm, from 300 nm to 75 µm, from 400 nm to 75 µm, from 500 nm to 75 µm, from 600 nm to 75 µm, from 700 nm to 75 µm, from 800 nm to 75 µm, from 1 µm to 75 µm, from 5 µm to 75 µm, from 10 µm to 75 µm, from 15 µm to 75 µm, from 25 µm to 75 µm, from 50 µm to 75 µm, from 150 nm to 50 µm, from 200 nm to 50 µm, from 300 nm to 50 µm, from 400 nm to 50 µm, from 500 nm to 50 µm, from 600 nm to 50 µm, from 700 nm to 50 µm, from 800 nm to 50 µm, from 1 µm to 50 µm, from 5 µm to 50 µm, from 10 µm to 50 µm, from 15 µm to 50 µm, from 25 µm to 50 µm, from 150 nm to 25 µm, from 200 nm to 25 µm, from 300 nm to 25 µm, from 400 nm to 25 µm, from 500 nm to 25 µm, from 600 nm to 25 µm, from 700 nm to 25 µm, from 800 nm to 25 µm, from 1 µm to 25 µm, from 5 µm to 25 µm, from 10 µm to 25 µm, from 15 µm to 25 µm, from 150 nm to 15 µm, from 200 nm to 15 µm, from 300 nm to 15 µm, from 400 nm to 15 µm, from 500 nm to 15 µm, from 600 nm to 15 µm, from 700 nm to 15 µm, from 800 nm to 15 µm, from 1 µm to 15 µm, from 5 µm to 15 µm, from 10 µm to 15 µm, from 150 nm to 10 µm, from 200 nm to 10 µm, from 300 nm to 10 µm, from 400 nm to 10 µm, from 500 nm to 10 µm, from 600 nm to 10 µm, from 700 nm to 10 µm, from 800 nm to 10 µm, from 1 µm to 10 µm, from 5 µm to 10 µm, from 150 nm to 5 µm, from 200 nm to 5 µm, from 300 nm to 5 µm, from 400 nm to 5 µm, from 500 nm to 5 µm, from 600 nm to 5 µm, from 700 nm to 5 µm, from 800 nm to 5 µm, from 800 nm to 5 µm, from 1 µm to 5 µm, from 150 nm to 1 µm, from 200 nm to 1 µm, from 300 nm to 1 µm, from 400 nm to 1 µm, from 500 nm to 1 µm, from 600 nm to 1 µm, from 700 nm to 1 µm, from 800 nm to 1 µm, from 150 nm to 800 nm, from 200 nm to 800 nm, from 300 nm to 800 nm, from 400 nm to 800 nm, from 500 nm to 800 nm, from 600 nm to 800 nm, from 700 nm to 800 nm, from 150 nm to 700 nm, from 200 nm to 700 nm, from 300 nm to 700 nm, from 400 nm to 700 nm, from 500 nm to 700 nm, from 600 nm to 700 nm, from 150 nm to 600 nm, from 200 nm to 600 nm, from 300 nm to 600 nm, from 400 nm to 600 nm, from 500 nm to 600 nm, from 150 nm to 500 nm, from 200 nm to 500 nm, from 300 nm to 500 nm, from 400 nm to 500 nm, from 150 nm to 400 nm, from 200 nm to 400 nm, from 300 nm to 400 nm, from 150 nm to 300 nm, from 200 nm to 300 nm, or from 150 nm to 200 nm.
- These diameter ranges may optionally represent the diameters of 80 percent (or more) of the particles, meaning that although some particles may have diameters outside the stated range, at least 80 percent of the particles will have diameters within the stated range. In some cases, the diameter ranges may represent the diameter of 25 percent (or more) of the particles, 30 percent (or more) of the particles, 35 percent (or more) of the particles, 40 percent (or more) of the particles, 45 percent (or more) of the particles, 50 percent (or more) of the particles, 55 percent (or more) of the particles, 60 percent (or more) of the particles, 65 percent (or more) of the particles, 70 percent (or more) of the particles, 75 percent (or more) of the particles, 80 percent (or more) of the particles, 85 percent (or more) of the particles, 90 percent (or more) of the particles, 95 percent (or more) of the particles, 98 percent (or more) of the particles, or 100 percent (or more) of the particles.
- To control the particle sizing and inter-particle spacing, conditions during casting and homogenization may be adjusted to control the size and density of particle generation. In some cases, the composition of the aluminum alloy may control particle generation. Specifically, adjustment of the composition prior to casting, for example, may be useful to generate a favorable amount of intermetallic particles and/or to control particle diameters and inter-particle spacing.
- During casting processes, aluminum alloys containing iron and manganese may generate intermetallic particles comprising aluminum and one or more of iron or manganese, which may be referred to herein as Al-(Fe, Mn) intermetallic particles or β-phase intermetallic particles, within the cast aluminum alloy product. When silicon is present, intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese, also referred to herein as Al-(Fe, Mn)-Si intermetallic particles or α-phase intermetallic particles, may also be generated. Exemplary α-phase and β-phase intermetallic particles may include Al15(Fe,Mn)3Si2 and Al6(Fe,Mn), respectively. As some amounts of iron and silicon are generally present in almost all aluminum alloys, many aluminum alloys may include such intermetallic particles upon casting.
- Each of these intermetallic particle types exhibits different properties and contributes in different ways to the structure of the aluminum alloy. For example, β-phase particles tend to be larger and more blocky or geometric than α-phase particles, while α-phase particles are harder and tend to be smaller than β-phase particles, in general. During hot and cold rolling, intermetallic particles may be broken, impacting their size, inter-particle spacing, and density, for example. During homogenization, heat treatment, and/or aging, components may diffuse in and out of intermetallic particles, changing their composition, structure, and/or size.
- By adjusting the composition of the aluminum alloy, specifically the iron and silicon content, the type of intermetallic particles generated may be controlled and in turn the particle sizes may be controlled. For example, if the intermetallic particle distribution in an aluminum alloy is such that the aluminum alloy contains 99% α-phase intermetallic particles and only 1% β-phase intermetallic particles, then the aluminum alloy may generate overall finer/smaller particles. However, if the amount of α-phase intermetallic particles generated is reduced and the amount of β-phase intermetallic particles generated is increased, then the overall particle size for the aluminum alloy may be larger. Moreover, when the particle volume fraction is constant while adjusting the particle size, inter-particle spacing, and relatedly particle density, may be controlled.
- Specific aluminum alloys useful with the disclosed methods and aluminum alloy products may include those containing aluminum, iron, magnesium, manganese, and silicon. By using an increased ratio of iron to silicon, the disclosed aluminum alloy products may preferentially generate β-phase intermetallic particles during processing or may convert α-phase intermetallic particles to β-phase intermetallic particles during a homogenization process. For example, in some embodiments, aluminum alloys useful with the methods and products described herein may have a ratio of a wt. % of iron to a wt. % of silicon of from 0.5 to 5.0. Optionally, an aluminum alloy may have a ratio of a wt. % of iron to a wt. % of silicon from 0 such as from 0.5 to 5, from 0.5 to 4.7, from 0.5 to 4.6, from 0.5 to 4.5, from 0.5 to 4.25, from 0.5 to 4.0, from 0.5 to 3.75, from 0.5 to 3.5, from 0.5 to 3.25, from 0.5 to 3.0, from 0.5 to 2.75, from 0.5 to 2.5, from 0.5 to 2.0, from 0.5 to 1.8, from 0.5 to 1.5, from 0.5 to 1.1, from 0.5 to 1.0, from 1.0 to 5.0, from 1.0 to 4.7, from 1.0 to 4.6, from 1.0 to 4.5, from 1.0 to 4.25, from 1.0 to 4.0, from 1.0 to 3.75, from 1.0 to 3.5, from 1.0 to 3.25, from 1.0 to 3.0, from 1.0 to 2.75, from 1.0 to 2.5, from 1.0 to 2.0, from 1.0 to 1.8, from 1.0 to 1.5, from 1.0 to 1.1, from 1.1 to 5.0, from 1.1 to 4.7, from 1.1 to 4.6, from 1.1 to 4.5, from 1.1 to 4.25, from 1.1 to 4.0, from 1.1 to 3.75, from 1.1 to 3.5, from 1.1 to 3.25, from 1.1 to 3.0, from 1.1 to 1.75, from 1.1 to 2.5, from 1.1 to 2.0, from 1.1 to 1.8, from 1.1 to 1.5, from 1.5 to 5.0, from 1.5 to 4.7, from 1.5 to 4.6, from 1.5 to 4.5, from 1.5 to 4.25, from 1.5 to 4.0, from 1.5 to 3.75, from 1.5 to 3.5, from 1.5 to 3.25, from 1.5 to 3.0, from 1.5 to 1.75, from 1.5 to 2.5, from 1.5 to 2.0, from 1.5 to 1.8, from 1.8 to 5.0, from 1.8 to 4.7, from 1.8 to 4.6, from 1.8 to 4.5, from 1.8 to 4.25, from 1.8 to 4.0, from 1.8 to 3.75, from 1.8 to 3.5, from 1.8 to 3.25, from 1.8 to 3.0, from 1.8 to 1.75, from 1.8 to 2.5, from 1.8 to 2.0, from 2.0 to 5.0, from 2.0 to 4.7, from 2.0 to 4.6, from 2.0 to 4.5, from 2.0 to 4.25, from 2.0 to 4.0, from 2.0 to 3.75, from 2.0 to 3.5, from 2.0 to 3.25, from 2.0 to 3.0, from 2.0 to 2.75, from 2.0 to 2.5, from 3.0 to 5.0, from 3.0 to 4.5, from 3.0 to 4.0, from 3.0 to 3.75, from 3.0 to 3.5, from 4.0 to 5.0, from 4.0 to 4.7, from 4.0 to 4.6, from 4.0 to 4.5, or from 4.0 to 4.25. Such ratios may allow a cast alloy product to preferentially form desirable amounts of α-phase and β-phase intermetallic particles during or after casting, resulting in controlled inter-particle spacing, and particle sizing.
- These iron to silicon ratios may preferentially form β-phase intermetallic particles and α-phase intermetallic particles in desired ratios such to achieve a desirable volume fraction of each type of intermetallic particle within the aluminum alloy. For example, the aluminum alloy may have from 0.5% to 4.0% by volume of α-phase intermetallic particles and from 0% to 2.0% by volume of β-phase intermetallic particles. In some cases, the ratio of the volume percent of the α-phase intermetallic particles to a volume percent of the β-phase intermetallic particles may be from 0.6 to 1,000; 1 to 800; 10 to 750; 50 to 500; or 100 to 250. In embodiments, the ratio of α-phase intermetallic particles to a β-phase intermetallic particles may be based on the density of intermetallic particles instead of the volume fraction. In such embodiments, a favorable ratio of α-phase intermetallic particle number density to a β-phase intermetallic particle number density may be from 0.2 to 1,000. For example, the ratio of α-phase intermetallic particle number density to a β-phase intermetallic particle number density may be from 0.2 to 1,000, 0.2 to 750, 0.25 to 500, 0.25 to 100, 0.25 to 50, 0.3 to 25, 0.3 to 10, or 0.3 to 3.
- The following Tables 1-3 provide alloy compositions (wt. %) for aluminum alloys according to some embodiments. Specifically, the provided compositions may be useful in generating aluminum alloy products having favorable inter-particle spacing while maintaining favorable particle size. As discussed above with reference to
FIG. 1 , there may be a balance between inter-particle spacing and particle size that provides for improved product formability. The following compositions may provide for aluminum alloys and aluminum alloy products having improved formability and permit use of high amounts of recycled source content. - In some examples, an aluminum alloy as described herein may have the following elemental composition as provided in Table 1.
-
Table 1 Element Weight Percentage (wt. %) Fe 0.1 - 1.0 Si 0.05 - 0.8 Mn 0.2 - 2.0 Mg 0.2 - 2.0 Cu 0 - 0.5 Zn 0 - 0.5 Al Remainder - In some examples, the aluminum alloy may have the following elemental composition as provided in Table 2.
-
Table 2 Element Weight Percentage (wt. %) Fe 0.2 - 0.8 Si 0.1 - 0.7 Mn 0.6 - 1.0 Mg 0.7 - 1.0 Cu 0 - 0.25 Zn 0 - 0.2 Ti 0 - 0.1 Cr 0 - 0.1 Zr 0 - 0.1 V 0 - 0.1 Al Remainder - In some examples, the alloy may have the following elemental composition as provided in Table 3.
-
Table 3 Element Weight Percentage (wt. %) Fe 0.3 - 0.7 Si 0.15 - 0.5 Mn 0.8 - 1.4 Mg 0.9 - 1.1 Cu 0.1 - 0.2 Zn 0 - 0.15 Ti 0 - 0.08 Cr 0 - 0.05 Zr 0 - 0.05 V 0 - 0.05 Al Remainder - In some examples, the alloy may have the following elemental composition as provided in Table 4.
-
Table 4 Element Weight Percentage (wt. %) Fe 0 - 0.7 Si 0.25 - 0.7 Mn 0.8 - 1.3 Mg 0.8 - 1.4 Cu 0 - 0.25 Zn 0 - 0.25 Ti 0 - 0.08 Cr 0 - 0.05 Zr 0 - 0.05 V 0 - 0.05 Al Remainder - In some examples, the alloys described herein may also include iron (Fe) in an amount of from 0.1% to 1.0% (e.g., from 0.20% to 0.8% or from 0.3% to 0.7%) based on the total weight of the alloy. For example, the alloy may 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%, 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% iron. All are expressed in wt. %.
- In some examples, the alloys described herein may include silicon (Si) in an amount of from 0.05% to 0.80% (e.g., from 0.1% to 0.7% or from 0.15% to 0.5%) based on the total weight of the alloy. For example, the alloy may include 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%, or 0.80% silicon. All are expressed in wt. %.
- In some examples, the alloys described herein may include manganese (Mn) in an amount of from 0.2% to 2.0% (e.g., from 0.6% to 1.0% or from 0.8% to 1.4%) based on the total weight of the alloy. For example, the alloy may include 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%, 1.10%, 1.11%, 1.12%, 1.13%, 1.14%, 1.15%, 1.16%, 1.17%, 1.18%, 1.19%, 1.20%, 1.21%, 1.22%, 1.23%, 1.24%, 1.25%, 1.26%, 1.27%, 1.28%, 1.29%, 1.30%, 1.31%, 1.32%, 1.33%, 1.34%, 1.35%, 1.36%, 1.37%, 1.38%, 1.39%, 1.40%, 1.41%, 1.42%, 1.43%, 1.44%, 1.45%, 1.46%, 1.47%, 1.48%, 1.49%, 1.50%, 1.51%, 1.52%, 1.53%, 1.54%, 1.55%, 1.56%, 1.57%, 1.58%, 1.59%, 1.60%, 1.61%, 1.62%, 1.63%, 1.64%, 1.65%, 1.66%, 1.67%, 1.68%, 1.69%, 1.70%, 1.71%, 1.72%, 1.73%, 1.74%, 1.75%, 1.76%, 1.77%, 1.78%, 1.79%, 1.80%, 1.81%, 1.82%, 1.83%, 1.84%, 1.85%, 1.86%, 1.87%, 1.88%, 1.89%, 1.90%, 1.91%, 1.92%, 1.93%, 1.94%, 1.95%, 1.96%, 1.97%, 1.98%, 1.99%, or 2.0% manganese. In some cases, manganese may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include magnesium (Mg) in an amount of from 0.2% to 2.0% (e.g., from 0.7% to 1.0% or from 0.9% to 1.1%) based on the total weight of the alloy. For example, the alloy may include 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%, 1.10%, 1.11%, 1.12%, 1.13%, 1.14%, 1.15%, 1.16%, 1.17%, 1.18%, 1.19%, 1.20%, 1.21%, 1.22%, 1.23%, 1.24%, 1.25%, 1.26%, 1.27%, 1.28%, 1.29%, 1.30%, 1.31%, 1.32%, 1.33%, 1.34%, 1.35%, 1.36%, 1.37%, 1.38%, 1.39%, 1.40%, 1.41%, 1.42%, 1.43%, 1.44%, 1.45%, 1.46%, 1.47%, 1.48%, 1.49%, 1.50%, 1.51%, 1.52%, 1.53%, 1.54%, 1.55%, 1.56%, 1.57%, 1.58%, 1.59%, 1.60%, 1.61%, 1.62%, 1.63%, 1.64%, 1.65%, 1.66%, 1.67%, 1.68%, 1.69%, 1.70%, 1.71%, 1.72%, 1.73%, 1.74%, 1.75%, 1.76%, 1.77%, 1.78%, 1.79%, 1.80%, 1.81%, 1.82%, 1.83%, 1.84%, 1.85%, 1.86%, 1.87%, 1.88%, 1.89%, 1.90%, 1.91%, 1.92%, 1.93%, 1.94%, 1.95%, 1.96%, 1.97%, 1.98%, 1.99%, or 2.0% magnesium. All are expressed in wt. %.
- In some examples, the alloys described may include copper (Cu) in an amount of up to 0.5% (e.g., from 0% to 0.25% or from 0.1% to 0.2%) based on the total weight of the alloy. For example, the alloy may include 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 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%, or 0.50% copper. In some cases, copper is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include zinc (Zn) in an amount of up to 0.50% (e.g., from 0% to 0.2% or from 0% to 1.5%) based on the total weight of the alloy. For example, the alloy may include 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 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%, or 0.50% zinc. In some cases, zinc is not present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include titanium (Ti) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy. For example, the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011% 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041% 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.1% titanium. In some cases, titanium may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include chromium (Cr) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy. For example, the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011% 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021% 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%,0.03%, 0.031% 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041% 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% chromium. In some cases, chromium may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include zirconium (Zr) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy. For example, the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041%, 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% Zr. In other examples, the alloys may include zirconium in an amount less than 0.05% (e.g., 0.04%, 0.03%, 0.02%, or 0.01%) based on the total weight of the alloy. In some cases, zirconium may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include vanadium (V) in an amount of up to 0.10% (e.g., from 0.001% to 0.10%, from 0% to 0.05%, from 0.001% to 0.05%, or from 0.003% to 0.08%) based on the total weight of the alloy. For example, the alloy may include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.010%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.020%, 0.021%, 0.022%, 0.023%, 0.024%, 0.025%, 0.026%, 0.027%, 0.028%, 0.029%, 0.03%, 0.031%, 0.032%, 0.033%, 0.034%, 0.035%, 0.036%, 0.037%, 0.038%, 0.039%, 0.04%, 0.041%, 0.042%, 0.043%, 0.044%, 0.045%, 0.046%, 0.047%, 0.048%, 0.049%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, or 0.10% vanadium. In other examples, the alloys may include vanadium in an amount less than 0.05% (e.g., 0.04%, 0.03%, 0.02%, or 0.01%) based on the total weight of the alloy. In some cases, vanadium may not be present in the alloy (i.e., 0%). All are expressed in wt. %.
- In some examples, the alloys described herein may include one or more rare earth elements (i.e., one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu)) in an amount of up to 0.10% (e.g., from 0.01% to 0.10%, from 0.01% to 0.05%, or from 0.03% to 0.05%) based on the total weight of the alloy. For example, the alloy may include 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.10% of one or more of the rare earth elements. All are expressed in wt. %.
- In some examples, the alloys described herein may include one or more of molybdenum (Mo), niobium (Nb), beryllium (Be), boron (B), cobalt (Co), Tin (Sn), strontium (Sr), vanadium (V), indium (In), hafnium (Hf), silver (Ag), and nickel (Ni) in an amount of up to 0.20% (e.g., from 0.01% to 0.20% or from 0.05% to 0.15%) based on the total weight of the alloy. For example, the alloy may include 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% of one or more of molybdenum (Mo), niobium (Nb), beryllium (Be), boron (B), cobalt (Co), tin (Sn), strontium (Sr), vanadium (V), indium (In), hafnium (Hf), silver (Ag), and nickel (Ni). All are expressed in wt. %.
- Optionally, the alloy compositions described herein may 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. These impurities may include, but are not limited to gallium (Ga), calcium (Ca), bismuth (Bi), sodium (Na), lead (Pb), or combinations thereof. Accordingly, gallium, calcium, bismuth, sodium, or lead 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. The sum of all impurities may not exceed 0.15% (e.g., 0.10%). All expressed in wt. %. The remaining percentage of the alloy may be aluminum.
- Incidental elements, such as grain refiners and deoxidizers, or other additives may be present in the aluminum alloys and aluminum alloy products and may add other characteristics on their own without departing from or significantly altering the aluminum alloys and products described herein or the characteristics of the aluminum alloys or products described herein.
- Unavoidable impurities, including materials or elements may be present in the alloy in minor amounts due to inherent properties of aluminum or leaching from contact with processing equipment. Some impurities typically found in aluminum include iron and silicon. In some cases, iron and silicon may not be indicated as impurities. For example, the amounts of iron and silicon may be actively controlled to effect certain properties in the alloy.
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FIG. 4 provides an overview of an example method of making an aluminum alloy product. The method ofFIG. 4 begins atstep 405, where analuminum alloy 406 may be cast to create a castaluminum alloy product 407, such as an ingot or other cast product. Atstep 410, the castaluminum alloy product 407 may be homogenized to generate a homogenizedaluminum alloy product 411. Atstep 415, the homogenizedaluminum alloy product 411 may be subjected to one or more hot rolling passes and/or one or more cold rolling passes to form a rolledaluminum alloy product 412, which may correspond to an aluminum alloy article, such as an aluminum alloy plate, an aluminum alloy shate, or an aluminum alloy sheet. Optionally, the rolledaluminum alloy product 412 may be subjected to one or more forming or stamping processes to form an aluminum alloy article. - The aluminum alloys described herein may be cast using any suitable casting method. As a few non-limiting examples, the casting process may include a direct chill (DC) casting process or a continuous casting (CC) process. For example,
FIG. 4 may depict a schematic illustration of a DC casting process at 405. A continuous casting system may be used instead, which may 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 may have an end opening from which molten metal can exit the molten metal injector and be injected into the casting cavity. - A cast aluminum alloy product, such as a cast ingot or other cast product, may be processed by any suitable means. Optionally, the processing steps may be used to prepare sheets. Example processing steps include, but are not limited to, homogenization, hot rolling, cold rolling, annealing, solution heat treatment, and pre-aging.
-
FIG. 5 provides a plot showing temperature of a cast aluminum alloy product according to the present disclosure as a function of time during a homogenization process according to some examples. During homogenization, the cast aluminum alloy product may be heated to a homogenization temperature (HTi). Heating for the homogenization step may take place from ambient conditions, room temperature (RT as shown inFIG. 5 ), or a higher temperature, and may occur at any suitable heating rate. In some embodiments, a heating rate of from about 10° C./hour to about 100° C./hour may be used. Example heating rates may be from 20° C./hour to 90° C./hour, from 30° C./hour to 80° C./hour, from 40° C./hour to 70° C./hour, from 50° C./hour to 60° C./hour, about 10° C./hour, 20° C./hour, 30° C./hour, 40° C./hour, 50° C./hour, 60° C./hour, 70° C./hour, 80° C./hour, 90° C./hour, or 100° C./hour. The time duration for the heating process is illustrated inFIG. 5 as tR, running from time -tR totime 0. - The aluminum alloy product may be heated to a homogenization temperature (HTi) ranging from about 500° C. to about 650° C. Example homogenization temperatures (HTi) include from about 550° C. to about 615° C., from about 570° C. to about 610° C., from about 580° C. to about 605° C., from about 590° C. to about 600° C., about 500° C., 510° C., 520° C., 530° C., 540° C., 550° C., 560° C., 570° C., 580° C., 585° C., 590° C., 595° C., 600° C., 605° C., 610° C., 615° C., or 620° C. As described in more detail herein, higher homogenization temperatures may be useful for controlling a size, distribution, concentration, and/or composition of intermetallic particles present in the aluminum alloy, so homogenization temperatures of from about 585° C. to about 615° C. may be desirable.
- In some embodiments, higher homogenization temperatures may be useful for controlling a size, inter-particle spacing, distribution, concentration, and/or composition of intermetallic particles present in the aluminum alloy, so homogenization temperatures of from about 570° C. to about 620° C. may be desirable. In some embodiments, a homogenization temperature from about 585° C. to about 615° C. may be desirable. Optionally, the homogenization temperature may be within 25° C. of a solidus temperature of the aluminum alloy.
- The heated cast aluminum alloy product may then be allowed to soak (i.e., held at the indicated homogenization temperature) for a period of time. The time duration for soaking shown in
FIG. 5 is t1, which runs fromtime 0 to time t1. In some embodiments, homogenization may take place in an inert atmosphere, a reduced oxygen atmosphere, an oxygen-free atmosphere, or in air. In some examples, the total time for the homogenization step, including the heating and soaking phases, may be up to or greater than 12 hours or 32 hours. Optionally, the soaking phase can be longer, even up to 36 hours. Long duration soaking of over 12 hours or over 24 hours may be useful, in embodiments, for controlling a size, inter-particle spacing, distribution, concentration, density, and/or composition of intermetallic particles present in the aluminum alloy. - Following the soaking phase, the homogenized aluminum alloy product may have its temperature reduced, such as by an active or passive cooling process. Optionally, the homogenized aluminum alloy may have its temperature reduced to room temperature. Cooling may take place at any suitable cooling rate. Example cooling rates include heating rates of from about 10° C./hour to about 50° C./hour, such as about 10° C./hour, 20° C./hour, 30° C./hour, 40° C./hour, or 50° C./hour. Optionally, the homogenized aluminum alloy product may proceed directly to hot rolling without being cooled to room temperature.
- In some cases, the homogenization step includes multiple processes. As illustrated in
FIG. 5 , the homogenization step optionally includes heating the product to a first homogenization temperature (HTi), soaking at or about the first homogenization temperature for a first time duration (ti), followed by cooling to a second homogenization temperature (HT2), and soaking at or about the second homogenization temperature for a second time duration, shown inFIG. 5 as t2-t1. For example, the aluminum alloy product may be cooled after the first soak to a second homogenization temperature of from 500° C. to 600° C., such as about 500° C., 505° C., 510° C., 515° C., 520° C., 525° C., 530° C., 535° C., 540° C., 545° C., 550° C., 555° C., 560° C., 565° C., 570° C., 575° C., 580° C., 585° C., 590° C., or 595° C. The aluminum alloy product may be held at the second homogenization temperature for a second time duration of from about 1 hours to about 24 hours. - Following the homogenization step, a hot rolling step may be performed. Optionally, hot rolling may occur immediately after homogenization (i.e., without cooling to room temperature). In other embodiments, prior to the start of hot rolling, the homogenized product may be allowed to cool to a temperature of from 100° C. to 500° C. For example, the homogenized product may be allowed to cool to a temperature of from 100° C. to 500° C., from 250° C. to 450° C., from 300° C. to 450° C., from 325° C. to 425° C. or from 350° C. to 400° C. The product may then be hot rolled at a temperature between 200° C. to 600° C. to form a hot rolled plate, a hot rolled shate, or a hot rolled sheet having a gauge from 0.5 mm to 200 mm (e.g., 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, or anywhere in between). For example, the homogenized product may be hot rolled at a temperature to a thickness from 1 mm to 8 mm. During hot rolling, temperatures and other operating parameters may be controlled so that the exit temperature of the hot rolled product upon exit from the hot rolling mill is no more than about 500° C., no more than about 450° C., no more than about 300° C., or no more than about 200° C. In some cases, the exit temperature of the hot rolled product may be from 100° C. to 500° C., or from 200° C. to 400° C.
- In some cases, cast, homogenized, or hot rolled products may be cold rolled using cold rolling mills and technology into a sheet. The cold rolled sheet may have a gauge from about 0.10 mm to about 0.50 mm, from about 0.15 mm to about 0.3 mm, from about 0.5 mm to about 10 mm or from about 0.7 mm to about 6.5 mm. Optionally, the cold rolled sheet may have a gauge of about 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, 5.5 mm, 6.0 mm, 6.5 mm, 7.0 mm, 7.5 mm, 8.0 mm, 8.5 mm, 9.0 mm, 9.5 mm, or 10.0 mm . The cold rolling may be performed to result in a final gauge thickness that represents a gauge reduction of up to about 95% (e.g., up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 85%, up to 90%, or up to 95% reduction). During cold rolling, temperatures and other operating parameters may be controlled so that the exit temperature of the cold rolled product upon exit from the cold rolling mill is no more than about 300° C., no more than about 250° C., no more than about 200° C., or no more than about 100° C. In some cases, the exit temperature of the cold rolled product may be from 50° C. to 250° C. or from 100° C. to 200° C.
- Optionally, an interannealing step may be performed after the cold rolling step or in between multiple cold rolling steps. The interannealing step may be performed at a temperature of from about 300° C. to about 450° C. (e.g., about 310° C., 320° C., 330° C., 340° C., 350° C., 360° C., 370° C., 380° C., 390° C., 400° C., 410° C., 420° C., 430° C., 440° C., or 450° C.). In some cases, the interannealing step comprises multiple processes. In some non-limiting examples, the interannealing step may include heating the plate, shate, or sheet to a first temperature for a first period of time followed by heating to a second temperature for a second period of time. For example, the plate, shate or sheet may be heated to about 410° C. for about 1 hour and then heated to about 330° C. for about 2 hours.
- The cast, homogenized, or hot rolled alloy products described herein may also be used to make products in the form of plates or other suitable products. For example, plates including the products as described herein can be prepared by processing an ingot in a homogenization step or casting a product in a continuous caster followed by homogenization and subsequently hot rolling the homogenized product. In the hot rolling step, the homogenized product can be hot rolled to a 200 mm thick gauge or less (e.g., from about 10 mm to about 200 mm). For example, a homogenized aluminum alloy product can be hot rolled to a plate having a final gauge thickness of about 10 mm to about 175 mm, about 15 mm to about 150 mm, about 20 mm to about 125 mm, about 25 mm to about 100 mm, about 30 mm to about 75 mm, or about 35 mm to about 50 mm.
- Monolithic as well as non-monolithic, such as roll-bonded materials, cladded alloys, clad layers, composite materials, such as but not limited to carbon fiber-containing materials, or various other materials are also useful with the methods and aluminum alloys and aluminum alloy products described herein.
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FIG. 6 provides amethod 600 of making an aluminum alloy having favorable particle density and inter-particle spacing between the particles according to an embodiment as disclosed herein. Atblock 610, a cast aluminum alloy product may be prepared. A cast aluminum alloy product may comprise an aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, for example. The cast aluminum alloy product may include an aluminum alloy having an elemental composition as provided herein, specifically those provided at Tables 1-3. Preparing the cast aluminum alloy product may include preparing a molten aluminum alloy and casting the molten aluminum alloy. - The source aluminum alloy(s) for the aluminum alloy products prepared according to the methods and techniques described herein may correspond to the same series aluminum alloy or a mixture of different series aluminum alloys. Optionally, preparing the cast aluminum alloy product may comprise preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy. Optionally, preparing the molten 3xxx series aluminum alloy may comprise melting both a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy. In some cases, one or more of the source aluminum alloys may be from a recycled source content. In some embodiments, aluminum alloys including a higher percentage of iron may be useful for achieving a target iron to silicon ratio. For example, preparing the molten aluminum alloy optionally may further comprise melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy along with a 3xxx series source aluminum alloy and/or a 5xxx series source aluminum alloy.
- At
block 620, the cast aluminum alloy product may be homogenized. Optionally, homogenizing may include heating the cast aluminum alloy product to a homogenization temperature, such as a homogenization temperature that is between 500° C. and 650° C., and soaking the cast aluminum alloy product at the homogenization temperature for a time duration between 0.1 hours and 36 hours, for example. During soaking, a structure of the aluminum alloy may change. As an example, during soaking, silicon from the aluminum alloy may diffuse into and transform at least a fraction of the β-phase intermetallic particles into α-phase intermetallic particles. As an example, during soaking, iron from the aluminum alloy may diffuse into and transform at least a fraction of the α-phase intermetallic particles into β-phase intermetallic particles. As another example, during the soaking, iron may diffuse out of the β-phase intermetallic particles and be optionally replaced by manganese. As another example, during the soaking, iron may diffuse out of the β-phase intermetallic particles and into dispersoids present within the cast aluminum alloy product. - In embodiments where the aluminum alloy includes a 3xxx series aluminum alloy, during the soaking, silicon from the 3xxx series aluminum alloy may diffuse into and transform at least a fraction of the β-phase intermetallic particles into α-phase intermetallic particles. Optionally, during these embodiments, during the soaking, iron diffuses out of the β-phase intermetallic particles and is replaced by manganese. In some embodiments, when the iron diffuses out of the β-phase intermetallic particles, the iron may combine with dispersoids present within the cast aluminum alloy product to form α-phase intermetallic particles. The dispersoids may include manganese.
- By controlling the homogenization temperatures and duration, the nature of the intermetallic particles may change. For example, during the soaking, an average size of the βphase intermetallic particles may increase or decrease. For example, an average size of the βphase intermetallic particles may decrease as compared to an average size of the β-phase intermetallic particles prior to soaking. Optionally, a number density of the β-phase intermetallic particles in the cast aluminum alloy product may increase or decrease. Optionally, prior to homogenizing, a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density in the cast aluminum alloy product is between 0.3 and 3. Optionally, after homogenizing, a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density in the homogenized aluminum alloy product may be from 0.2 to 1000 or more (e.g., from 2 to 1000). In some cases, an amount of the α-phase intermetallic particles may be transformed into β-phase intermetallic particles during homogenizing, such as 30% or more, 40% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 80% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, 99.5% or more or up to 100%. In some cases, a majority of the α-phase intermetallic particles are transformed into β-phase intermetallic particles during homogenizing.
- In some embodiments, such as those in which the aluminum alloy includes a 3xxx series aluminum alloy, an amount of the β-phase intermetallic particles may be transformed into α-phase intermetallic particles during homogenizing, in particular, during soaking. For example, during soaking, approximately 30% to 100% of the β-phase intermetallic particles may be transformed into α-phase intermetallic particles.
- In some embodiments, multiple homogenization steps may be useful. For example, a secondary lower temperature homogenization after an initial higher temperature, long duration homogenization may be useful for preparing an aluminum alloy product, such as for rolling or other processing. A multiple-step homogenization process may include reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature, and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration, such as a second time duration that is shorter than the time duration of the initial long-duration soak. In some embodiments, soaking the homogenized aluminum alloy product at the second homogenization temperature may control a surface quality or characteristic of the homogenized aluminum alloy product. Optionally, soaking the homogenized aluminum alloy product at the second homogenization temperature may bring a temperature of the homogenized aluminum alloy product to a temperature sufficient for a rolling process.
- At
block 640, themethod 600 may optionally include subjecting the homogenized rolled aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product. For example, the homogenized rolled aluminum alloy product may be subjected to one or more hot rolling processes atblock 642. In some cases, the homogenized rolled aluminum alloy product may also be subjected to one or more cold rolling processes atblock 644. During the hot and cold rolling processes, intermetallic particles may be broken, impacting their size, distribution, and number density, for example. - Hot rolling the rolled aluminum alloy product at relatively high temperatures, such as above about 550° C., depending on the alloy, may encounter difficulties due to roll sticking and bite refusal. This may also result in grain boundary separation and surface tearing, which can enhance oxidation at the surface. Since the affinity of oxide formation is higher at higher temperatures, at least in part due to faster diffusion of solute elements (e.g., magnesium (Mg), silicon (Si), etc.,) on the surface, the new fresh surface that forms from tearing may oxidize promptly and often results in a non-uniform surface with an undesirable oxide layer. Advantageously, however, lowering the hot rolling exit temperature, such as to a temperature below about 550° C., for example from about 100° C. to 500° C., may give more control on roll bite with higher friction and reduce the tendency of the surface to stick, tear, and oxidize. In addition, the reduced diffusivity of solute elements at lower temperatures can result in a more uniform surface layer than at higher temperatures.
- Similarly, controlling the cold rolling exit temperature may also allow for an improved aluminum alloy product. Exit temperature from a cold rolling process from about 100° C. to 200° C. may allow for the rolled aluminum alloy product to be rolled to a thickness of 0.15 to 0.30 mm without sticking, tearing, or breakage.
- The aluminum alloy products described herein can be used in a variety of applications. In specific embodiments, the aluminum alloy products described herein are useful for beverage container body stock, such as aluminum can body stock or aluminum bottle body stock. Aluminum alloy sheets may be subjected to a blanking process in which discs of the aluminum alloy are cut from an aluminum alloy sheet. The discs may be subjected to one or more drawing, ironing, necking or other forming processes to form a suitable beverage container body or preform.
- Other applications may be suitable for some of the aluminum alloy products described herein. For example, the disclosed aluminum alloy products can be used to prepare automotive parts, aircraft or railway vehicle panels, architectural panels, building products, and the like. In some examples, cookware, foils, formed containers, bottle caps, and packaging (e.g., food packaging) may be made using the disclosed aluminum alloy products.
- The aluminum alloy products and methods described herein can also be used in electronics applications. For example, the aluminum alloy products and methods described herein can be used to prepare housings for electronic devices, including mobile phones and tablet computers. In some examples, the aluminum alloy products can be used to prepare housings for the outer casing of mobile phones (e.g., smart phones), tablet bottom chassis, and other portable electronics.
- The examples disclosed herein will serve to further illustrate aspects of the invention without, at the same time, however, constituting any limitation thereof. On the contrary, it is to be clearly understood that resort may be had to various embodiments, modifications and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the invention. The examples and embodiments described herein may also make use of conventional procedures, unless otherwise stated. Some of the procedures are described herein for illustrative purposes.
- The following Table 1 provides alloying solute compositions (wt. %) of two example 3104 aluminum alloys, Alloy A and Alloy B. Alloy A is slightly enriched in solute as compared to Alloy B. A ratio of silicon to iron in Alloy A is about 0.60, while in Alloy B the ratio is about 0.56. The solidus temperatures of the alloys were calculated to be within 2° C. of one another, indicating that the samples are expected to have similar melting and physical properties. The solvus temperature for Mg2Si for Alloy A was calculated to be slightly higher than for Alloy B. Four sample ingots of each of Alloy A and Alloy B were prepared and used to evaluate the effect of different homogenization regimes on intermetallic particles present in the alloys. The as-cast samples had a gauge of about 40 mm.
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Table 1 Si Fe Cu Mn Mg Cr Solvus (°C) Mg2Si Solidus (°C) Alloy A 0.32 0.53 0.19 0.86 1.25 0.03 409 623 Alloy B 0.27 0.48 0.18 0.85 1.15 0.03 393 625 - Predicted equilibrium phase diagrams for Alloy A and Alloy B were determined and are shown in
FIG. 7A andFIG. 7B , respectively. Both alloys show similar constituent phase types at just below melting, which primarily includes α-phase particles (ALPHA) and β-phase particles (e.g., Al6Mn or Al3Fe), though the Alloy A has a higher α to β ratio than Alloy B, which may be due to higher silicon and iron content in Alloy A. - Samples of Alloy A and two samples of Alloy B were subjected to a heat-to-roll (HTR) processing scheme, where the samples were heated at a slow rate of about 50° C./h to a temperature of about 500° C. Other samples of Alloy A and other samples of Alloy B were subjected to a 2-stage (2STG) processing scheme, where the samples were heated at a slow rate of about 50° C./h to a temperature of about 600° C., held at this temperature for about 24 hours, and then cooled to about 560° C., where they were held for about 4 additional hours.
- Scanning electron micrograph (SEM) images under back-scattered electron (BSE) contrast were obtained of cross-sections of samples of the as-cast Alloy A and Alloy B, as well as samples of Alloy A and Alloy B after the HTR or 2STG processing, in order to evaluate the particle distribution and microstructure of the samples. These images are shown in
FIG. 8 . The images show that, overall, the sizes of the particles in Alloy A are smaller than the particles in Alloy B. After the HTR processing, no changes in the constituent particles were observed for either Alloy A or Alloy B. The as-cast and HTR processed samples showed a mix of α-phase particles and β-phase particles. After the 2STG processing, however, only α-phase particles were observed in the microstructures, with a more fine particle size distribution. In some cases, the 2STG processing transformed the structure to a more porous character. - Samples of the as-cast Alloy A and Alloy B, as well as samples of Alloy A and Alloy B after the HTR or 2STG processing, were subjected to electrical conductivity measurements. A bar chart showing the results of the measurements in terms of a percent of the International Annealed Copper Standard (IACS) is depicted in
FIG. 9 . Overall, Alloy A shows higher resistivity than Alloy B, which may be due to a higher solute level in Alloy A. The conductivity of all processed samples was observed to be higher than the respective as-cast samples, which may be due to precipitation of manganese out of the solid solution and formation of dispersoids. A noticeably smaller conductivity was observed for the 2STG processed samples as compared to the HTR samples, which may be due to a higher solubility of manganese in the 2STG processed samples because of higher processing temperatures can allow manganese present in the dispersoids to dissolve back into the metal solid solution. - To further characterize the properties of the different alloys, samples of Alloy A and Alloy B were subjected to rolling processes. For samples of the alloys subjected to HTR processing, immediately after the HTR processing, samples of Alloy A and Alloy B were subjected to a hot rolling operation to a gauge of about 7.0 mm, recrystallized, and then subjected to a cold rolling operation to a gauge of about 1.0 mm to form hard H19 temper products. Recrystallizing may optionally be achieved by coiling the hot-rolled product and cooling the coil or may be achieved by annealing the hot-rolled product. Some of the cold rolled H19 temper product samples of Alloy A and the cold rolled H19 temper product samples of Alloy B were then annealed at 350° C. for 1 hour to generate soft O temper products. The hard H19 temper product samples are referred to as AHTR,H19 and BHTR,H19 and the soft O temper product samples are referred to as AHTR,O and BHTR,O.
- Similarly, for samples of the alloys subjected to 2STG processing, immediately after the 2STG processing, heated and homogenized samples of Alloy A and Alloy B were subjected to a hot rolling operation to a gauge of about 7.0 mm, recrystallized, and then subjected to a cold rolling operation to a gauge of about 1.0 mm to form hard H19 temper products. One of the cold rolled H19 temper product samples of Alloy A and one of the cold rolled H19 temper product samples of Alloy B were then annealed at 350° C. for 1 hour to generate soft O temper products. The hard H19 temper product samples are referred to as A2STG,H19 and B2STG,H19 and the soft O temper product samples are referred to as A2STG,O and B2STG,O.
- SEM images under BSE contrast were obtained in a plan view configuration for the AHTR,H19, BHTR,H19, A2STG,H19, and B2STG,H19 samples in order to evaluate the particle distribution and microstructure of the samples in the final gauge condition. These images are shown in
FIG. 10 . Less dense and coarser particles were generally observed in Alloy B as compared to Alloy A. A decrease in the overall particle size is observed for the samples subjected to the 2STG processing as compared to the HTR processing. Additionally, in the samples subjected to the 2STG processing, fine particles were noticed surrounding the coarser particles, which may be due to more breakup and/or spheroidization of the particles because of the higher temperatures encountered in the 2STG processing. - High resolution cross-sectional images of the AHTR,H19, BHTR,H19, A2STG,H19, and B2STG,H19 samples were obtained using a field emission gun scanning electron microscope (FEGSEM) to investigate the spatial distribution of dispersoids (e.g., manganese containing dispersoids) in the final gauge samples. The obtained images are shown in
FIG. 11 , with the dispersoids identified as white spots in the images. The dispersoids in the samples subjected to the HTR processing were numerous and very fine. In contrast, the dispersoids in the samples subjected to the 2STG processing were fewer in number density, but also more coarse, again due to the longer and higher temperatures of the 2STG processing, allowing for more mobility and time for iron atoms to be taken up and convert the dispersoids to α-phase particles and/or for constituent atoms to be taken up into and grow the dispersoids. Slightly larger size dispersoids can be seen in the Alloy A samples as compared to the Alloy B samples, which may be attributable to a slightly higher amount of solute in Alloy A as compared to Alloy B. - SEM images obtained in a plan view configuration for the AHTR,H19, BHTR,H19, A2STG,H19, and B2STG,H19 samples were analyzed to identify particle size distributions for various particulate components in the samples (by estimating particle area and size) and plots showing the results are shown in
FIG. 12 . In general, the Alloy A samples showed a finer size distribution for all particles as compared to the Alloy B samples. The samples subjected to HTR processing showed a significant fraction of particles identified in the figures as Al(Fe,Mn), which may correspond to β-phase particles. In contrast, the samples subjected to 2STG processing showed little or none of these particles, and much higher populations of α-phase particles, indicating that the α-phase particles may be generated by transforming β-phase particles during the prolonged homogenization of the 2STG processing. - Cross-sectional images of the AHTR,H19, BHTR,H19, A2STG,H19, and B2STG,H19 samples were obtained to observe the grain structure prior to recrystallization. The images are shown in
FIG. 13 . The grains show an elongated structure for all the samples, and black spots on the grain structures correspond to constituent particles, with the 2STG processed samples showing finer particle distributions, in correspondence with the plots ofFIG. 12 , with overall greater numbers of particles observed in the Alloy A samples as compared to the corresponding Alloy B samples. - Cross-sectional images of the AHTR,O, BHTR,O, A2STG,O, and B2STG,O samples were obtained to observe the grain structure after recrystallization associated with annealing, shown in
FIG. 14 . The Alloy A samples show more equiaxed grains while the Alloy B samples show some elongated grains. Since the Alloy A samples had more particles overall than the corresponding Alloy B samples, particle stimulated nucleation may contribute to the less elongated grain structure in Alloy A samples. Comparing the HTR processed and 2STG processed samples, more equiaxed grains were observed for the 2STG processed samples, which may be due to a larger number density of dispersoids present in the HTR processed samples, which may inhibit recrystallization by pinning at the grain boundaries. - Tensile properties in longitudinal cross-sections of the H19 and O temper samples were measured, and the results are shown in
FIG. 15A andFIG. 15B . In the H19 temper, the yield strength (YS) ultimate tensile strength (UTS), and ultimate elongation (UE) of the Alloy A samples was slightly greater than the Alloy B samples, while the total elongation (TE) did not show an overall alloy trend. A loss in strength and gain in elongation was observed for the 2STG processed samples as compared to the HTR processed samples. Bendability properties of the H19 and O temper samples were also measured by performing wrap bend tests, with the results shown inFIG. 16A andFIG. 16B . Some bendability improvements were observed for the 2STG processed samples as compared to the HTR processed samples, meaning that the 2STG processed samples were able to withstand bending to a smaller radius to thickness (r/t) than the HTR processed samples. - Hole expansion tests were performed on both the H19 and O temper samples, and the results are shown in
FIG. 13 . The 2STG processed samples for both alloys exhibited higher hole expansion ratios than the HTR processed samples. The Alloy B samples also exhibited higher hole expansion ratios than the Alloy A samples. The H19 temper Alloy A sample showed poor hole expansion, which may be due to the presence of a large number density of constituent particles in the sample. The energy stored at the interface between the particles and the matrix may be very high for hard tempers and this energy may trigger initiation of cracks followed by coalescence and propagation to failure. In contrast, Alloy B contains less constituent particles, meaning less stored energy, and less susceptibility to cracking at the same strains at which the Alloy A samples would crack. For the softer temper material, the constituent morphology may be more influential than the number density of particles, as there is less energy present at the interface between the particles and the matrix. The 2STG processed samples exhibited spheroidical particles than HTR processed samples, which may allow the strains to be more evenly distributed around the particles than in the more needle-shaped particles of the HTR processed samples, which may result in concentration of strain and earlier crack initiation. - As used below, any reference to a series of illustrations is to be understood as a reference to each of those examples disjunctively (e.g., “Illustrations 1-4” is to be understood as “
Illustrations -
Illustration 1 is an aluminum alloy product comprising: an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of an iron wt. % in the aluminum alloy to a silicon wt. % in the aluminum alloy is from 0.5 to 5.0, and wherein the aluminum alloy includes a plurality of particles including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and β-phase intermetallic particles comprising aluminum and one or more of iron or manganese; and wherein the aluminum alloy has a particle density for the plurality of particles of from 5 to 30,000 particles per µm2 and wherein the aluminum alloy has an inter-particle spacing for the plurality of particles of from 1 µm to 25 µm. -
Illustration 2 is the aluminum alloy product of any previous or subsequent illustration, wherein the plurality of particles has diameters of from 500 nm to 50 µm. -
Illustration 3 is the aluminum alloy product of any previous or subsequent illustration, wherein the particle density is from 50 to 1,000 particles per µm2. -
Illustration 4 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy is from a recycled source. -
Illustration 5 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.1 wt. % to 1.0 wt. % iron, from 0.05 wt. % to 0.8 wt. % silicon, from 0.2 wt. % to 2.0 wt. % manganese, from 0.2 wt. % to 2.0 wt. % magnesium, up to 0.5 wt. % copper, up to 0.05 wt. % zinc, and aluminum. -
Illustration 6 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises up to 0.15 wt. % impurities. - Illustration 7 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium, up to 0.10 wt. % chromium, up to 0.10 wt. % zirconium, up to 0.10 wt. % vanadium, and aluminum.
- Illustration 8 is the aluminum alloy product of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum.
- Illustration 9 is the aluminum alloy product of any previous or subsequent illustration, wherein the α-phase intermetallic particles comprise from 0.5% to 4.0% by volume of the aluminum alloy, and wherein the β-phase intermetallic particles comprise from 0% to 2.0% by volume of the aluminum alloy.
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Illustration 10 is the aluminum alloy product of any previous or subsequent illustration, wherein the α-phase intermetallic particles comprise Al15(Fe,Mn)3Si2, and wherein the β-phase intermetallic particles comprise Al6(Fe,Mn). - Illustration 11 is the aluminum alloy product of any previous or subsequent illustration, wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density is from 0.2 to 1,000 or wherein a ratio of a volume % of the α-phase intermetallic particles to a volume % of the β-phase intermetallic particles is from 0.6 to 1,000.
- Illustration 12 is the aluminum alloy product of any previous or subsequent illustration, wherein the ratio of the α-phase intermetallic particle number density to the β-phase intermetallic particle number density is from 0.3 to 3.
- Illustration 13 is the aluminum alloy product of any previous or subsequent illustration, wherein 80 percent or more of the plurality of particles have an inter-particle spacing from 5 µm to 15 µm.
- Illustration 14 is the aluminum alloy product of any previous or subsequent illustration, wherein the plurality of particles comprise iron-containing particles, wherein a majority of the iron-containing particles have a diameter from 1 µm to 40 µm.
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Illustration 15 is the aluminum alloy product of any previous or subsequent illustration, wherein the iron-containing particles comprise from 1% to 4% of a total volume of the aluminum alloy. - Illustration 16 is the aluminum alloy product of any previous or subsequent illustration, further comprising manganese-containing dispersoids, wherein a majority of the manganese-containing dispersoids have a diameter of from 10 nm to 1.5 µm.
- Illustration 17 is the aluminum alloy product of any previous or subsequent illustration, wherein the manganese-containing dispersoids comprise up to 1% of a total volume of the aluminum alloy.
- Illustration 18 is a method of making an aluminum alloy product, the method comprising: preparing a cast aluminum alloy product comprising an aluminum alloy, wherein the aluminum alloy comprises aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the aluminum alloy to an iron wt. % in the aluminum alloy is from 0.5 to 1.0, and wherein the aluminum alloy includes a plurality of particles including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and β-phase intermetallic particles comprising aluminum and one or more of iron or manganese; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product by: heating the cast aluminum alloy product to a homogenization temperature from 500° C. to 650° C.; and soaking the cast aluminum alloy product at the homogenization temperature for a time duration from 0.1 hours to 36 hours, and wherein the aluminum alloy product has a particle density for the plurality of particles of from 5 to 30,000 particles per µm2 and wherein the aluminum alloy product has an inter-particle spacing for the plurality of particles of from 1 µm to 25 µm.
- Illustration 19 is the method of any previous or subsequent illustration, wherein the time duration is from 0.5 to 10 hours.
-
Illustration 20 is the method of any previous or subsequent illustration, wherein the homogenization temperature is from 570° C. to 620° C. - Illustration 21 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the aluminum alloy.
- Illustration 22 is the method of any previous or subsequent illustration, wherein, during the soaking, a size of the β-phase intermetallic particles decreases as compared to a size of the β-phase intermetallic particles prior to the soaking.
- Illustration 23 is the method of any previous or subsequent illustration, wherein, during the soaking, a number density of the β-phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the β-phase intermetallic particles in the cast aluminum alloy product prior to the soaking.
- Illustration 24 is the method of any previous or subsequent illustration, further comprising subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
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Illustration 25 is the method of any previous or subsequent illustration, wherein the one or more rolling processes comprise at least one of a hot rolling process or a cold rolling process. - Illustration 26 is the method of any previous or subsequent illustration, wherein the hot rolling process comprises an exit temperature of from 100° C. to 500° C.
- Illustration 27 is the method of any previous or subsequent illustration, wherein the exit temperature is from 200° C. to 400° C.
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Illustration 28 is the method of any previous or subsequent illustration, wherein the rolled aluminum alloy product produced by the hot rolling process has a thickness from 1 mm to 8 mm. - Illustration 29 is the method of any previous or subsequent illustration, wherein the cold rolling process comprises an exit temperature of from 50° C. to 250° C.
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Illustration 30 is the method of any previous or subsequent illustration, wherein the exit temperature is from 100° C. to 200° C. -
Illustration 31 is the method of any previous or subsequent illustration, wherein the rolled aluminum alloy product produced by the cold rolling process has a thickness from 0.15 mm to 0.30 mm. - Illustration 32 is the method of any previous or subsequent illustration, wherein the plurality of particles comprises a particle diameter from 500 nm to 50 µm.
- Illustration 33 is the method of any previous or subsequent illustration, wherein the particle density is from 50 to 1,000 particles per µm2.
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Illustration 34 is the method of any previous or subsequent illustration, wherein the aluminum alloy is from a recycled source. - Illustration 35 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.1 wt. % to 1.0 wt. % iron, from 0.05 wt. % to 0.8 wt. % silicon, from 0.2 wt. % to 2.0 wt. % manganese, from 0.2 wt. % to 2.0 wt. % magnesium, up to 0.5 wt. % copper, up to 0.05 wt. % zinc, and aluminum.
- Illustration 36 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.2 wt. % to 0.8 wt. % iron, from 0.10 wt. % to 0.7 wt. % silicon, from 0.6 wt. % to 1.0 wt. % manganese, from 0.7 wt. % to 1.0 wt. % magnesium, up to 0.25 wt. % copper, up to 0.2 wt. % zinc, up to 0.10 wt. % titanium, up to 0.10 wt. % chromium, up to 0.10 wt. % zirconium, up to 0.10 wt. % vanadium, and aluminum.
-
Illustration 37 is the method of any previous or subsequent illustration, wherein the aluminum alloy comprises: from 0.3 wt. % to 0.7 wt. % iron, from 0.15 wt. % to 0.5 wt. % silicon, from 0.8 wt. % to 1.2 wt. % manganese, from 0.9 wt. % to 1.2 wt. % magnesium, from 0.1 wt. % to 0.2 wt. % copper, up to 0.15 wt. % zinc, up to 0.08 wt. % titanium, up to 0.05 wt. % chromium, up to 0.05 wt. % zirconium, up to 0.05 wt. % vanadium, and aluminum. - Illustration 38 is the method of any previous or subsequent illustration, wherein the αphase intermetallic particles comprise from 0.5% to 4.0% by volume of the aluminum alloy and the β-phase intermetallic particles comprise from 0 to 2.0% by volume of the aluminum alloy.
- Illustration 39 is the method of any previous or subsequent illustration, wherein the αphase intermetallic particles comprise Al15(Fe,Mn)3Si2, and wherein the β-phase intermetallic particles comprise Al6(Fe,Mn).
- Illustration 40 is the method of any previous or subsequent illustration, wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density is from 0.2 to 1,000 or wherein a ratio of a volume % of the α-phase intermetallic particles to a volume % of the β-phase intermetallic particles is from 0.6 to 1,000.
- Illustration 41 is the method of any previous or subsequent illustration, wherein the ratio of an α-phase intermetallic particle number density to the β-phase intermetallic particle number density is from 0.3 to 3.
- Illustration 42 is the method of any previous or subsequent illustration, wherein 80 percent or more of the plurality of particles have an inter-particle spacing from 5 µm to 15 µm.
- Illustration 43 is the method of any previous or subsequent illustration, wherein the plurality of particles comprise iron-containing particles, wherein a majority of the iron-containing particles have an diameter from 1 µm to 40 µm.
- Illustration 44 is the method of any previous or subsequent illustration, wherein iron-containing particles comprise from 1% to 4% of a total volume of the aluminum alloy.
- Illustration 45 is the method of any previous or subsequent illustration, wherein the aluminum alloy further comprises manganese-containing dispersoids, wherein the manganese-containing dispersoids have a diameter from 10 nm and 1.5 µm.
- Illustration 46 is the method of any previous or subsequent illustration, wherein the manganese-containing dispersoids comprise up to 1% of a total volume of the aluminum alloy.
- Illustration 47 is a method for improving formability of a metal product, the method comprising: providing a cast metal product comprising a metal composite, wherein the metal composite comprises iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the metal composite to an iron wt. % in the metal composite is from 0.5 to 1.0, and wherein the metal composite includes a plurality of particles including α-phase intermetallic particles comprising silicon and one or more of iron or manganese and β-phase intermetallic particles comprising one or more of iron or manganese; and homogenizing the cast metal product to control an inter-particle spacing of the plurality of particles and to control a particle density of the plurality of particles such to achieve a ratio of an inter-particle spacing to particle density from 0.0003/µm to 0.0006/µm.
- Illustration 48 is the method of any previous or subsequent illustration, wherein the inter-particle spacing is from 1 µm to 25 µm.
- Illustration 49 is the method of any previous or subsequent illustration, wherein the particle density is from 5 to 30,000 particles per µm2.
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Illustration 50 is the method of any previous or subsequent illustration, wherein the particle density is from 5 to 1,000 particles per µm2. - Illustration 51 is the method of any previous or subsequent illustration, wherein the plurality of particles comprise a particle diameter from 1 µm to 50 µm.
- Illustration 52 is the method of any previous or subsequent illustration, wherein homogenizing the cast metal product comprises heating the cast metal product to a homogenization temperature from 400° C. to 800° C. and soaking the cast metal product at the homogenization temperature for a time duration from 0.1 hours to 48 hours.
- Illustration 53 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the cast metal product.
- Illustration 54 is the method of any previous or subsequent illustration, wherein homogenizing the cast metal product further comprises subjecting the cast metal product to one or more of a hot rolling process or a cold rolling process.
- Illustration 55 is a method of making an aluminum alloy product, the method comprising: preparing a cast aluminum alloy product, wherein the cast aluminum alloy product comprises a 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the 3xxx series aluminum alloy to an iron wt. % in the 3xxx series aluminum alloy is from 0.5 to 1.0, and wherein the cast aluminum alloy product includes β-phase intermetallic particles comprising aluminum and one or more of iron or manganese and α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese; and homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product by: heating the cast aluminum alloy product to a homogenization temperature from 575° C. to 615° C.; and soaking the cast aluminum alloy product at the homogenization temperature for a time duration between 12 hours and 36 hours; wherein silicon from the 3xxx series aluminum alloy diffuses into and transforms at least a fraction of the βphase intermetallic particles into α-phase intermetallic particles.
- Illustration 56 is the method of any previous or subsequent illustration, wherein the time duration is between 24 hours and 36 hours.
- Illustration 57 is the method of any previous or subsequent illustration, wherein the time duration is between 24 hours and 30 hours.
- Illustration 58 is the method of any previous or subsequent illustration, wherein the homogenization temperature is from 580° C. to 610° C.
- Illustration 59 is the method of any previous or subsequent illustration, wherein the homogenization temperature is within 25° C. of a solidus temperature of the 3xxx series aluminum alloy.
- Illustration 60 is the method of any previous or subsequent illustration, wherein, during the soaking, iron diffuses out of the β-phase intermetallic particles and is replaced by manganese.
- Illustration 61 is the method of any previous or subsequent illustration, wherein, during the soaking, iron diffuses out of the β-phase intermetallic particles and combines with dispersoids present within the cast aluminum alloy product to form α-phase intermetallic particles.
- Illustration 62 is the method of any previous or subsequent illustration, wherein the dispersoids comprise manganese.
- Illustration 63 is the method of any previous or subsequent illustration, wherein, during the soaking, an average size of the β-phase intermetallic particles decreases as compared to an average size of the β-phase intermetallic particles prior to soaking.
- Illustration 64 is the method of any previous or subsequent illustration, wherein, during the soaking, a number density of the β-phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the β-phase intermetallic particles in the cast aluminum alloy product prior to soaking.
- Illustration 65 is the method of any previous or subsequent illustration, wherein, during the soaking, 30% to 100% of the β-phase intermetallic particles are transformed into αphase intermetallic particles.
- Illustration 66 is the method of any previous or subsequent illustration, wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density in the homogenized aluminum alloy product is from 2 to 1000.
- Illustration 67 is the method of any previous or subsequent illustration, wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density in the cast aluminum alloy product is from 0.3 to 3.
- Illustration 68 is the method of any previous or subsequent illustration, wherein the ratio of the silicon wt. % to the iron wt. % in the 3xxx series aluminum alloy is from 0.55 to 0.9.
- Illustration 69 is the method of any previous or subsequent illustration, wherein the 3xxx series aluminum alloy comprises: from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.25-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- Illustration 70 is the method of any previous or subsequent illustration, wherein preparing the cast aluminum alloy product comprises preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy.
- Illustration 71 is the method of any previous or subsequent illustration, wherein preparing the molten 3xxx series aluminum alloy comprises melting a combination of a 3xxx series source aluminum alloy and a 5xxx series source aluminum alloy.
- Illustration 72 is the method of any previous or subsequent illustration, wherein the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy are from a recycled source.
- Illustration 73 is the method of any previous or subsequent illustration, wherein preparing the molten 3xxx series aluminum alloy further comprises melting a 4xxx series aluminum alloy or a 6xxx series aluminum alloy with the 3xxx series source aluminum alloy and the 5xxx series source aluminum alloy.
- Illustration 74 is the method of any previous or subsequent illustration, wherein the homogenization temperature is a first homogenization temperature, and wherein the method further comprises: reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature; and soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration.
- Illustration 75 is the method of any previous or subsequent illustration, wherein the second time duration is from 1 hour to 24 hours.
- Illustration 76 is the method of any previous or subsequent illustration, wherein the second homogenization temperature is from 500° C. to 600° C.
- Illustration 77 is the method of any previous or subsequent illustration, wherein soaking the homogenized aluminum alloy product at the second homogenization temperature controls a surface quality of the homogenized aluminum alloy product.
- Illustration 78 is the method of any previous or subsequent illustration, further comprising subjecting the homogenized aluminum alloy product to one or more rolling processes to produce a rolled aluminum alloy product.
- Illustration 79 is an aluminum alloy product, comprising: a homogenized 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the homogenized 3xxx series aluminum alloy to an iron wt. % in the homogenized 3xxx series aluminum alloy is from 0.5 to 1.0, and wherein the homogenized 3xxx series aluminum alloy includes α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese, wherein at least a portion of the α-phase intermetallic particles are transformed from β-phase intermetallic particles comprising aluminum and one or more of iron or manganese during homogenization of the homogenized 3xxx series aluminum alloy.
- Illustration 80 is the aluminum alloy product of any previous or subsequent illustration, wherein a ratio of an α-phase intermetallic particle number density in the homogenized 3xxx series aluminum alloy to a β-phase intermetallic particle number density in the homogenized 3xxx series aluminum alloy is from 2 to 1000 or wherein a ratio of a volume % of the α-phase intermetallic particles to a volume % of the β-phase intermetallic particle is from 0.6 to 1000.
- Illustration 81 is the aluminum alloy product of any previous or subsequent illustration, wherein the homogenized 3xxx series aluminum alloy is subjected to one or more rolling processes.
- Illustration 82 is the aluminum alloy product of any previous or subsequent illustration, wherein the homogenized 3xxx series aluminum alloy comprises: from 0.8-1.4 wt. % magnesium; from 0.8-1.3 wt. % manganese; up to 0.25 wt. % copper; from 0.25-0.7 wt. % silicon; up to 0.7 wt. % iron; up to 0.25 wt. % zinc; and aluminum.
- Illustration 83 is the aluminum alloy product of any previous illustration, prepared by the method of any previous illustration.
- Illustration 84 is the method of any previous illustration, comprising a method of making the aluminum alloy product of any previous illustration.
- All patents, publications and abstracts cited above are incorporated herein by reference in their entirety. The foregoing description of the embodiments, including illustrated embodiments, has been presented only for the purpose of illustration and description and is not intended to be exhaustive or limiting to the precise forms disclosed. Numerous modifications, adaptations, and uses thereof will be apparent to those skilled in the art.
Claims (37)
1. An aluminum alloy product comprising:
an aluminum alloy comprising aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of an iron wt. % in the aluminum alloy to a silicon wt. % in the aluminum alloy is from 0.5 to 5.0, and wherein the aluminum alloy includes a plurality of particles including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and β-phase intermetallic particles comprising aluminum and one or more of iron or manganese; and
wherein the aluminum alloy has a particle density for the plurality of particles of from 5 particles per µm2 to 30,000 particles per µm2 and wherein the aluminum alloy has an inter-particle spacing for the plurality of particles of from 1 µm to 25 µm.
2. The aluminum alloy product of claim 1 , wherein the plurality of particles have diameters of from 500 nm to 50 µm.
3. The aluminum alloy product of claim 1 , wherein the particle density is from 50 to 1,000 particles per µm2.
4. The aluminum alloy product of claim 1 , wherein the aluminum alloy comprises:
from 0.1 wt. % to 1.0 wt. % iron,
from 0.05 wt. % to 0.8 wt. % silicon,
from 0.2 wt. % to 2.0 wt. % manganese,
from 0.2 wt. % to 2.0 wt. % magnesium,
up to 0.5 wt. % copper,
up to 0.05 wt. % zinc, and
aluminum.
5-8. (canceled)
9. The aluminum alloy product of claim 1 , wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density is from 0.2 to 1,000 or wherein a ratio of a volume % of the α-phase intermetallic particles to a volume % of the β-phase intermetallic particles is from 0.6 to 1,000.
10. (canceled)
11. (canceled)
12. The aluminum alloy product of claim 1 , wherein the plurality of particles comprise iron-containing particles, wherein a majority of the iron-containing particles have a diameter from 1 µm to 40 µm.
13. (canceled)
14. The aluminum alloy product of claim 1 , further comprising manganese-containing dispersoids, wherein a majority of the manganese-containing dispersoids have a diameter of from 10 nm to 1.5 µm.
15. (canceled)
16. The aluminum alloy product of claim 1 , wherein the aluminum alloy comprises a homogenized 3xxx series aluminum alloy, wherein the ratio of the iron wt. % in the homogenized 3xxx series aluminum alloy to the silicon wt. % in the homogenized 3xxx series aluminum alloy is from 0.5 to 1.0, and wherein the homogenized 3xxx series aluminum alloy includes α-phase intermetallic particles, and wherein at least a portion of the α-phase intermetallic particles are transformed from β-phase intermetallic particles during homogenization of the homogenized 3xxx series aluminum alloy.
17-19. (canceled)
20. A method of making an aluminum alloy product, the method comprising:
preparing a cast aluminum alloy product comprising an aluminum alloy, wherein the aluminum alloy comprises aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the aluminum alloy to an iron wt. % in the aluminum alloy is from 0.5 to 1.0, and wherein the aluminum alloy includes a plurality of particles including α-phase intermetallic particles comprising aluminum, silicon, and one or more of iron or manganese and β-phase intermetallic particles comprising aluminum and one or more of iron or manganese; and
homogenizing the cast aluminum alloy product to form a homogenized aluminum alloy product by:
heating the cast aluminum alloy product to a homogenization temperature from 500° C. to 650° C.; and
soaking the cast aluminum alloy product at the homogenization temperature for a time duration from 0.1 hours to 36 hours, and
wherein the aluminum alloy product has a particle density for the plurality of particles of from 5 to 30,000 particles per µm2 and wherein the aluminum alloy product has an inter-particle spacing for the plurality of particles of from 1 µm to 25 µm.
21-24. (canceled)
25. The method of claim 20 , wherein, during the soaking, a number density of the β-phase intermetallic particles in the cast aluminum alloy product decreases as compared to a number density of the β-phase intermetallic particles in the cast aluminum alloy product prior to the soaking.
26-38. (canceled)
39. The method of claim 20 , wherein:
the cast aluminum alloy product comprises a 3xxx series aluminum alloy including aluminum, iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the 3xxx series aluminum alloy to an iron wt. % in the 3xxx series aluminum alloy is from 0.5 to 1.0, and wherein the cast aluminum alloy product includes β-phase intermetallic particles and α-phase intermetallic particles;
the homogenization temperature is from 575° C. to 615° C.;
the time duration is from 12 hours to 36 hours; and
silicon from the 3xxx series aluminum alloy diffuses into and transforms at least a fraction of the β-phase intermetallic particles into α-phase intermetallic particles.
40-49. (canceled)
50. The method of claim 39 , wherein a ratio of an α-phase intermetallic particle number density to a β-phase intermetallic particle number density in the homogenized aluminum alloy product is from 2 to 1000.
51-53. (canceled)
54. The method of claim 39 , wherein preparing the cast aluminum alloy product comprises preparing a molten 3xxx series aluminum alloy and casting the molten 3xxx series aluminum alloy.
55-57. (canceled)
58. The method of claim 39 , wherein the homogenization temperature is a first homogenization temperature, and wherein the method further comprises:
reducing a temperature of the homogenized aluminum alloy product to a second homogenization temperature less than the first homogenization temperature; and
soaking the homogenized aluminum alloy product at the second homogenization temperature for a second time duration.
59. (canceled)
60. The method of claim 58 , wherein the second homogenization temperature is from 500° C. to 600° C.
61. (canceled)
62. (canceled)
63. A method for improving formability of a metal product, the method comprising:
providing a cast metal product comprising a metal composite, wherein the metal composite comprises iron, magnesium, manganese, and silicon, wherein a ratio of a silicon wt. % in the metal composite to an iron wt. % in the metal composite is from 0.5 to 1.0, and wherein the metal composite includes a plurality of particles including α-phase intermetallic particles comprising silicon and one or more of iron or manganese and β-phase intermetallic particles comprising one or more of iron or manganese; and
homogenizing the cast metal product to control an inter-particle spacing of the plurality of particles and to control a particle density of the plurality of particles such to achieve a ratio of an inter-particle spacing to particle density from 0.0003/µm to 0.0006/µm.
64. The method of claim 63 , wherein the inter-particle spacing is from 1 µm to 25 µm.
65. The method of claim 63 , wherein the particle density is from 5 to 30,000 particles per µm2.
66. (canceled)
67. (canceled)
68. The method of claim 63 , wherein homogenizing the cast metal product comprises heating the cast metal product to a homogenization temperature from 400° C. to 800° C. and soaking the cast metal product at the homogenization temperature for a time duration from 0.1 hours to 48 hours.
69. (canceled)
70. The method of claim 68 , wherein homogenizing the cast metal product further comprises subjecting the cast metal product to one or more of a hot rolling process or a cold rolling process.
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US17/759,178 US20230074427A1 (en) | 2020-01-21 | 2021-01-20 | Techniques for producing aluminum alloy products having improved formability and recyclability |
PCT/US2021/014183 WO2021150610A1 (en) | 2020-01-21 | 2021-01-20 | Techniques for producing aluminum alloy products having improved formability and recyclability |
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US20060042727A1 (en) * | 2004-08-27 | 2006-03-02 | Zhong Li | Aluminum automotive structural members |
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