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WO2025207427A1 - Désintégration et reconstitution d'un produit d'affinage de grain pour couler des alliages sensibles aux inclusions - Google Patents

Désintégration et reconstitution d'un produit d'affinage de grain pour couler des alliages sensibles aux inclusions

Info

Publication number
WO2025207427A1
WO2025207427A1 PCT/US2025/020849 US2025020849W WO2025207427A1 WO 2025207427 A1 WO2025207427 A1 WO 2025207427A1 US 2025020849 W US2025020849 W US 2025020849W WO 2025207427 A1 WO2025207427 A1 WO 2025207427A1
Authority
WO
WIPO (PCT)
Prior art keywords
grain refiner
less
aluminum alloy
product
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/020849
Other languages
English (en)
Inventor
Kumar SUNDARAM
Don Allen Doutre
Sailaja BODROTHU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novelis Inc Canada
Original Assignee
Novelis Inc Canada
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Filing date
Publication date
Application filed by Novelis Inc Canada filed Critical Novelis Inc Canada
Publication of WO2025207427A1 publication Critical patent/WO2025207427A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • 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

Definitions

  • Recycled scrap metal includes metal from used metal products that is collected and used to prepare other metal products.
  • Used beverage can (UBC) scrap is collected metal from used beverage cans and similar products that can be recycled for use in further metal products.
  • Aluminum UBC scrap is often a mixture of various aluminum alloys (e.g., from different alloys used for can bodies and can ends) and can often include foreign substances, such as rainwater, drink remainders, organic matter (e.g., paints and laminated films), and other materials. UBC scrap can be shredded and decoated or delacquered prior to being melted for use as liquid metal stock in casting a new metal product.
  • such recycled scrap from beverage containers and other recycled content contains impurities and unbalanced alloying elements, such as increased levels of silicon (Si), magnesium (Mg), vanadium (V), calcium (Ca), strontium (Sr), titanium (Ti), Attorney Docket #: 108050-1492445 beryllium (Be), chromium (Cr), and/or manganese (Mn), which are difficult to remove from the recycled scrap and resulting alloy melt.
  • Si silicon
  • Mg magnesium
  • V vanadium
  • Ca calcium
  • Ti titanium
  • Attorney Docket #: 108050-1492445 beryllium (Be), chromium (Cr), and/or manganese (Mn) which are difficult to remove from the recycled scrap and resulting alloy melt.
  • the present technology is generally directed to methods of metal casting as well as suitable grain refiner products.
  • Methods include forming an aluminum alloy liquid metal.
  • Methods include mechanically deforming a grain refiner product into grain refiner chips having a particle size of less than 1000 ⁇ m, where at least a portion of the mechanically deformed grain refiner chip particles include one or more TiAl 3 phase particles having an equivalent spherical diameter of less than or about 50 ⁇ m.
  • Methods include, adding the mechanically deformed grain refiner chips to the aluminum alloy liquid metal, casting the liquid metal into a metal product, and rolling the metal product.
  • substantially all of the grain refiner chips include TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.
  • the mechanically deformed grain refiner chips are added in the form of chips, pellets, tablets, or a combination thereof.
  • the mechanical deforming includes sawing, grinding, Attorney Docket #: 108050-1492445 rolling, extruding, machining, impaction, or a combination thereof.
  • the mechanical deforming is conducted for a period of time to produce greater than or 500 TiAl 3 particles/mm 2 .
  • metal products include one or more intermetallic particles, wherein each of the one or more intermetallic particles exhibits an equivalent spherical diameter of less than or about 10 ⁇ m.
  • the aluminum alloy includes one or more of beryllium, magnesium, vanadium, strontium, titanium, and calcium.
  • the aluminum alloy includes a 5xxx series alloy.
  • the molten metal includes greater than or 10 wt.% recycled aluminum alloy.
  • the aluminum alloy includes from 0.01 wt.% titanium to 0.1 wt.% titanium.
  • the aluminum alloy includes from 1 wt.% to 7 wt.% magnesium. In embodiments, the aluminum alloy includes from 0.01 wt.% vanadium to 0.1 wt.% vanadium.
  • Embodiments include where greater than or 50 wt.% of the grain refiner chips include TiAl 3 phase particles having an equivalent diameter of less than or 50 ⁇ m. Additionally or alternatively, in embodiments, greater than or 50 wt.% of the grain refiner chips include TiAl 3 phase particles having an equivalent diameter of less than or 20 ⁇ m. Further, in embodiments, greater than or 50 wt.% of the grain refiner chips include TiAl 3 phase particles having an equivalent diameter of less than or 10 ⁇ m.
  • the present technology is also generally directed to metal product cast from any one or more of the methods discussed above. [0008]
  • the present technology is also generally directed to 5xxx series aluminum alloy aluminum alloy products.
  • 5xxx series aluminum alloy products include 0.01 – 1.0 wt.% Cu, 0.1 – 0.8 wt.% Fe, 0.5 – 7.0 wt.% Mg, 0.01 – 1.2 wt.% Mn, 0 – 1.5 wt.% Si, 0 – 0.2 wt.% Ti, 0 – 8.0 wt.% Zn, 0 – 0.3 wt.% Cr, 0 – 0.15 wt.% Zr, 0 – 0.1 wt.% V, 0 – 0.15 wt.% Ca, up to 0.15 wt.% impurities, and Al.
  • the aluminum alloy product includes intermetallic particles, where the intermetallic particles include two or more of aluminum, beryllium, magnesium, vanadium, strontium, titanium, and calcium, wherein the intermetallic particles exhibit an equivalent spherical diameter of less than 50 ⁇ m.
  • the present technology is also generally directed to a beverage container including the aluminum alloy product as discussed herein.. [0009]
  • the present technology is also generally directed to a TiAl 3 containing grain refiner product.
  • the grain refiner product includes grain refiner chips having a particle size of less than 1000 ⁇ m, where greater than 50 wt.% of the grain refiner chips include TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.
  • substantially all Attorney Docket #: 108050-1492445 of the grain refiner chips include TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.
  • Various implementations described herein may include additional systems, methods, features, and advantages, which cannot necessarily be expressly disclosed herein but will be apparent to one of ordinary skill in the art upon examination of the following detailed description and accompanying drawings. It is intended that all such systems, methods, features, and advantages be included within the present disclosure and protected by the accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGS [0011] The specification makes reference to the following appended figures, in which use of like reference numerals in different figures is intended to illustrate like or analogous components.
  • FIG.1 illustrates a metal treatment system according to embodiments.
  • DETAILED DESCRIPTION [0013] The subject matter of embodiments is described herein with specificity to meet statutory requirements, but this description is not necessarily intended to limit the scope of the claims. The claimed subject matter may be embodied in other ways, may include different elements or steps, and may be used in conjunction with other existing or future technologies. This description should not be interpreted as implying any particular order or arrangement among or between various steps or elements except when the order of individual steps or arrangement of elements is explicitly described.
  • Grain refiner products are generally manufactured by reacting molten aluminum with various reactive salts, such as K 2 TiF 4 and KBF 4 , as examples only, to form a suspension of TiB 2 and TiAl 3 . The suspension is then formed into rods having diameters of about 9.5 millimeters to about 50 millimeters.
  • the grain refiner products are then introduced into the molten aluminum alloy early in the casting process, such as upstream of a degasser and/or metal filter, interacting Attorney Docket #: 108050-1492445 with the alloy and nucleating the system.
  • Grain refiner products are generally introduced at this stage in order to allow for full dissolution of TiAl 3 prior to ingot formation.
  • existing grain refiner products require significant residence time in the melt in order to fully dissolve and disburse TiAl 3 particles.
  • extended residence time in the melt is believed to lead to formation of intermetallic particle.
  • the presence, or increased concentration, of Ti, Mg, V, and/or Ca in the recycled content may lead to the formation of Al x Mg y Ti z V t Ca u intermetallic particles, where, as an example only, x may range from 0 to 18, y and u may be independently selected to range from 0 to 3, and z and t may be independently selected to range from 0 to 2.
  • intermetallic particles may form around, or even fully enclose TiAl 3 particles, preventing dissolution and dispersion of the TiAl 3 particles, and allowing TiAl 3 particles and/or intermetallic particles of greater than 100 ⁇ m to form in the final melt and ingot.
  • This is increasingly problematic for products having a thin gauge, such as for beverage containers, as rivet formation in the can body or can end may have a product thickness of less than 150 ⁇ m, rendering the article susceptible to cracking and damage due to the large particles formed in and around the grain refiner.
  • grain refiner products having improved performance, even in alloys containing one or more impurities, such as one or more impurities from recycled content.
  • the present technology also includes methods of forming such grain refiner products, and methods of forming an aluminum alloy article utilizing such grain refiner products.
  • the present technology has surprisingly found that by mechanically deforming the grain refiner product to a carefully controlled particle size of the grain refiner, referred to herein as “grain refiner chips”, one or more of the above problems may be addressed. Namely, grain refiner chips according to the present technology may decrease the necessary residence time, decreasing the formation of intermetallic particles having a particle diameter of greater than or about 50 ⁇ m.
  • grain refiner chips according to the present technology may also exhibit reduced TiAl 3 phase particle sizes, thus allowing for further decreased intermetallic or TiAl 3 particle sizes in the final melt due to the smaller nucleation particles.
  • the terms “invention,” “the invention,” “this invention,” and “the present invention” used herein are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below. [0017]
  • the meaning of “a,” “an,” or “the” includes singular and plural references unless the context clearly dictates otherwise.
  • a plate generally has a thickness of greater than about 15 mm.
  • a plate may refer to an aluminum product having a thickness of greater than about 15 mm, greater than about 20 mm, greater than about 25 mm, greater than about 30 mm, greater than about 35 mm, greater than about 40 mm, greater than about 45 mm, greater than about 50 mm, or greater than about 100 mm.
  • a shate also referred to as a sheet plate
  • a shate may have a thickness of about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, about 10 mm, about 11 mm, about 12 mm, about 13 mm, about 14 mm, or about 15 mm.
  • a sheet generally refers to an aluminum 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).
  • the term foil indicates an alloy thickness in a range of up to about 0.2 mm (i.e., 200 microns ( ⁇ m)).
  • a foil may have a thickness of up to 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m, 110 ⁇ m, 120 ⁇ m, 130 ⁇ m, 140 ⁇ m, 150 ⁇ m, 160 ⁇ m, 170 ⁇ m, 180 ⁇ m, 190 ⁇ m, or 200 ⁇ m.
  • a T2 condition or temper refers to an aluminum alloy cooled from hot working, cold worked and naturally aged.
  • a T3 condition or temper refers to an aluminum alloy solution heat treated, cold worked, and naturally aged.
  • a T4 condition or temper refers to an aluminum alloy solution heat treated and naturally aged.
  • a T5 condition or temper refers to an aluminum alloy cooled from hot working and artificially aged (at elevated temperatures).
  • a T6 condition or temper refers to an aluminum alloy solution heat treated and artificially aged.
  • a T7 condition or temper refers to an aluminum alloy solution heat treated and artificially overaged.
  • a T8x condition or temper refers to an aluminum alloy solution heat treated, cold worked, and artificially aged.
  • a T9 condition or temper refers to an aluminum alloy solution heat treated, artificially aged, and cold worked.
  • the techniques disclosure herein can allow suitable cast products to be produced from a modified liquid metal containing at or more than about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 92%, about 94%, about 96%, or about 98% recycled scrap, or any ranges or values therebetween.
  • the cast products described herein can include at or less than about 90%, about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, about 20%, about 10%, about 8%, about 6%, about 4%, about 2%, primary aluminum, or any ranges or values therebetween.
  • the metal alloys described herein can have the following elemental composition as provided in Table 1. [0035] Table 1 [0036] In some examples, the metal alloys described herein can have the following elemental composition as provided in Table 2. [0037] Table 2 Attorney Docket #: 108050-1492445 [0038] In some examples, the metal alloys described herein can have the following elemental composition as provided in Table 3.
  • the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50
  • the alloys described herein include iron (Fe) in an amount of from about 0.1 % to about 0.8 % (e.g., from about 0.15 % to about 0.7 % or from about 0.2 % to about 0.6 %) based on the total weight of the alloy.
  • the alloy can include 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.50 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59
  • the alloys described herein include Mg in an amount of from about 0.50 % to about 7.0 % (e.g., from about 1.0 % to about 6.0 %, from about 2 % to about 5.5 %, from about 2.5 % to about 5.0 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy.
  • the alloy can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, Attorney Docket #: 108050-1492445 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %,
  • the alloys described herein include manganese (Mn) in an amount of from about 0.01 % to about 1.2 % (e.g., from about 0.05 % to about 1.0 %, from about 0.1 % to about 0.9 %, or from about 0.2 % to about 0.7 %) based on the total weight of the alloy.
  • Mn manganese
  • the alloys described herein include Si in an amount up to about 1.5 wt. % (e.g., from about 0.01 % to about 1.0 %, from about 0.02 % to about 0.5 %, or from about 0.03 % to about 0.1 %) based on the total weight of the alloy.
  • the alloys described herein include titanium (Ti) in an amount up to about 0.2 % (e.g., from about 0.01 % to about 0.15 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy.
  • the alloys described herein include zinc (Zn) in an amount of from about 0 % to about 8.0 % (e.g., from about 0.01 % to about 5.0 % or from about 0.02 % to about 1.0 %) based on the total weight of the alloy.
  • the alloys described herein include zirconium (Zr) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.01 % to about 0.1 % or from about 0.02 % to about 0.05 %) based on the total weight of the alloy.
  • the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Zr.
  • Zr is not present in the alloy (i.e., 0 %).
  • the alloys described herein include vanadium (V) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.01 % to about 0.1 % or from about 0.02 % to about 0.05 %) based on the total weight of the alloy.
  • the alloy can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % V.
  • V is not present in the alloy (i.e., 0 %). All are expressed in wt. %.
  • the alloys described herein include calcium (Ca) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy.
  • alloys discussed herein may include one or more of calcium, vanadium, and titanium.
  • the alloys described herein include strontium (Sr) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy.
  • the alloy can include 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Sr. In some cases, Sr is not present in the alloy (i.e., 0 %). All are expressed in wt. %.
  • the alloys described herein include beryllium (Be) in an amount of from about 0 % to about 0.15 % (e.g., from about 0.003 % to about 0.1 %, from about 0.01 % to about 0.1 %, or from about 0.02 % to about 0.05 %) based on the total weight of the alloy.
  • Be beryllium
  • the alloy can include 0.0001 %, 0.0002 %, 0.0003 %, 0.0004 %, 0.0005 %, 0.0006 %, 0.0007 %, 0.0008 %, 0.0009 %, 0.001 %, 0.002 %, 0.003 %, 0.004 %, 0.005 %, 0.006 %, 0.007 %, 0.008 %, 0.009 %, 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, or 0.15 % Be.
  • the alloy compositions described herein can further include other minor elements, sometimes referred to as impurities, in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below, or 0.01 % or below for each impurity.
  • impurities may include, but are not limited to, Sn, Ga, Bi, Na, Pb, Li, W, Mo, Ni, B, C, or combinations thereof.
  • Sn, Ga, Bi, Na, Pb, Li, W, Mo, Ni, B, or C may be present in alloys in amounts of 0.05 % or below, 0.04 % or below, 0.03 % or below, 0.02 % or below or 0.01 % or below. In some cases, the sum of all impurities does not exceed 0.15 % (e.g., 0.10 %). All expressed in wt. %. The remaining percentage of the alloy is aluminum.
  • suitable alloys for use in the alloys described herein can be a 1xxx series aluminum alloy, a 2xxx series aluminum alloy, a 3xxx series aluminum alloy, a 4xxx series aluminum alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, an 8xxx series aluminum alloy, or any combination thereof.
  • the 1xxx, 2xxx, 3xxx, 4xxx, 5xxx, 6xxx, 7xxx, or 8xxx series aluminum alloy can be modified to include an amount of Mg, Cu, and/or Si as described above.
  • Suitable 1xxx series aluminum alloys for use in the alloys described herein include, for example, AA1050, AA1060, AA1070, AA1100, AA1100A, AA1200, AA1200A, AA1300, AA1110, AA1120, AA1230, AA1230A, AA1235, AA1435, AA1145, AA1345, AA1445, AA1150, AA1350, AA1350A, AA1450, AA1370, AA1275, AA1185, AA1285, AA1385, AA1188, AA1190, AA1290, AA1193, AA1198, and AA1199.
  • Suitable 3xxx series aluminum alloys for use in the alloys described herein include, for example, AA3002, AA3102, AA3003, AA3103, AA3103A, AA3103B, AA3203, AA3403, AA3004, AA3004A, AA3104, AA3204, AA3304, AA3005, AA3005A, AA3105, AA3105A, AA3105B, AA3007, AA3107, AA3207, AA3207A, AA3307, AA3009, AA3010, AA3110, AA3011, AA3012, AA3012A, AA3013, AA3014, AA3015, AA3016, AA3017, AA3019, AA3020, AA3021, AA3025, AA3026, AA3030, AA3130, and AA3065.
  • Suitable 4xxx series aluminum alloys for use in the alloys described herein include, for example, AA4004, AA4104, AA4006, AA4007, AA4008, AA4009, AA4010, AA4013, AA4014, AA4015, AA4015A, AA4115, AA4016, AA4017, AA4018, AA4019, AA4020, AA4021, AA4026, AA4032, AA4043, AA4043A, AA4143, AA4343, AA4643, AA4943, AA4044, AA4045, AA4145, AA4145A, AA4046, AA4047, AA4047A, and AA4147.
  • Suitable 5xxx series aluminum alloys for use in the alloys described herein include, for example, AA5005, AA5005A, AA5205, AA5305, AA5505, AA5605, AA5006, AA5106, Attorney Docket #: 108050-1492445 AA5010, AA5110, AA5110A, AA5210, AA5310, AA5016, AA5017, AA5018, AA5018A, AA5019, AA5019A, AA5119, AA5119A, AA5021, AA5022, AA5023, AA5024, AA5026, AA5027, AA5028, AA5040, AA5140, AA5041, AA5042, AA5043, AA5049, AA5149, AA5249, AA5349, AA5449, AA5449A, AA5050, AA5050A, AA5050C, AA51
  • Suitable 6xxx series aluminum alloys for use in the alloys described herein include, for example, AA6101, AA6101A, AA6101B, AA6201, AA6201A, AA6401, AA6501, AA6002, AA6003, AA6103, AA6005, AA6005A, AA6005B, AA6005C, AA6105, AA6205, AA6305, AA6006, AA6106, AA6206, AA6306, AA6008, AA6009, AA6010, AA6110, AA6110A, AA6011, AA6111, AA6012, AA6012A, AA6013, AA6113, AA6014, AA6015, AA6016, AA6016A, AA6116, AA6018, AA6019, AA6020, AA6021, AA6022, AA6023, AA6024, AA6025, AA6026, AA6027,
  • Suitable 8xxx series aluminum alloys for use in the alloys described herein include, for example, AA8005, AA8006, AA8007, AA8008, AA8010, AA8011, AA8011A, AA8111, AA8211, AA8112, AA8014, AA8015, AA8016, AA8017, AA8018, AA8019, AA8021, AA8021A, AA8021B, AA8022, AA8023, AA8024, AA8025, AA8026, AA8030, AA8130, AA8040, AA8050, AA8150, AA8076, AA8076A, AA8176, AA8077, AA8177, AA8079, AA8090, AA8091, and AA8093.
  • the aluminum alloy may be a 5xxx aluminum alloy, such as 5182.
  • the products prepared including the alloys described herein can be a cladded product including a core layer and one or more cladding layers.
  • the core layer has a first side and a second side and one or more cladding layer(s) can be bonded to the first side or the second side of the core layer.
  • the core layer is clad on only one side (i.e., one cladding layer is present in the clad aluminum alloy product).
  • the core layer is clad on both sides (i.e., two cladding layers are present in the clad aluminum alloy product).
  • the cladding layer(s) can be attached to a core layer by direct chill co-casting (i.e., fusion casting) as described in, for example, U.S. Patent Nos. 7,748,434 and 8,927,113, both of which are hereby incorporated by reference in their entireties, by hot and cold rolling a composite cast ingot as described in U.S. Patent No. 7,472,740, which is hereby incorporated by reference in its entirety, or by roll bonding to achieve the required metallurgical bonding between the core and the cladding.
  • the alloys described herein can be used as the core layer or as the one or more cladding layers.
  • the one or more cladding layers can include a 1xxx series aluminum alloy, a 2xxx series aluminum alloy, a 3xxx series aluminum alloy, a 4xxx series aluminum alloy, a 5xxx series aluminum alloy, a 6xxx series aluminum alloy, a 7xxx series aluminum alloy, or an 8xxx series aluminum alloy.
  • the cladded product is prepared from an alloy as Attorney Docket #: 108050-1492445 described herein as the core and a 5xxx or 6xxx series aluminum alloy as one or both of the cladding layers.
  • the aluminum alloy product described herein can have any suitable gauge.
  • the amount of hydrogen included in the aluminum alloy products can be at or less than approximately 0.15 mL/100 grams, 0.14 mL/100 grams, 0.13 mL/100 grams, 0.12 mL/100 grams, 0.11 mL/100 grams, 0.1 mL/100 grams, 0.09 mL/100 grams, 0.08 mL/100 grams, 0.07 mL/100 grams, 0.06 mL/100 grams, 0.05 mL/100 grams, 0.04 mL/100 grams, 0.03 mL/100 grams, 0.02 mL/100 grams, or 0.01 mL/100 grams.
  • the hydrogen content in the products can be at least 0.08 mL/100 grams.
  • the hydrogen content can be from 0.08 mL/100 grams to 0.25 mL/100 grams, from 0.1 mL/100 grams to 0.20 mL/100 grams, or from 0.12 mL/100 grams to 0.18 mL/100 grams.
  • the amount of dissolved hydrogen present impacts the properties of the resulting metal product.
  • the dissolved hydrogen can have an impact on the castability of the metal product (e.g., resistance to hot cracking) as well as the resultant metal product’s mechanical properties (e.g., bending strength, toughness, fatigue strength, maximum elongation, crash worthiness, surface quality, corrosion resistance, and other properties).
  • Dissolved hydrogen can affect solidification and can result in porosity in the cast metal product.
  • the aluminum alloy products described herein include intermetallic particles containing one or more of aluminum (Al), silicon (Si), magnesium (Mg), vanadium (V), calcium (Ca), strontium (Sr), titanium (Ti), beryllium (Be), chromium (Cr), and/or manganese (Mn), such as aluminum (Al), magnesium (Mg), titanium (Ti), vanadium (V), and/or calcium (Ca), in embodiments.
  • the intermetallic particles in the aluminum alloy products may have a length, (e.g. equivalent diameter or largest dimension), that is less than or about 50 ⁇ m, such as less than or about 45 ⁇ m, such as less than or about 40 ⁇ m, such as less than or about 35 ⁇ m, such as less than or about 30 ⁇ m, or ranging from about 1 ⁇ m to about 50 ⁇ m (e.g., from about 5 ⁇ m to about 45 ⁇ m or from about 10 ⁇ m to about 40 ⁇ m).
  • the intermetallic particles may be Al x Mg y Ti x V t Ca v particles, alone or nucleated from one or more TiAl 3 particles.
  • the intermetallic particle can include 1.0 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2.0 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, 3.0 %, 3.1 %, 3.2 %, 3.3 %, 3.4 %, 3.5 %, 3.6 %, 3.7 %, 3.8 %, 3.9 %, 4.0 %, 4.1 %, 4.2 %, 4.3 %, 4.4 %, 4.5 %, 4.6 %, 4.7 %, 4.8 %, 4.9 %, 5.0 %, 5.1 %, 5.2 %, 5.3 %, 5.4 %, 5.5 %, 5.6 %, 5.7 %, 5.8 %, 5.9
  • the intermetallic particles may contain Ti in an amount of from about 0.50 % to about 7.0 % (e.g., from about 1.0 % to about 6.0 %, from about 2 % to about 5.5 %, from about 2.5 % to about 5.0 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy.
  • the intermetallic particle can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 0.60
  • the intermetallic particles may contain V in an amount of from about 0.50 % to about 6.0 % (e.g., from about 1.0 % to about 5.5 %, from about 2 % to about 5.0 %, from about 2.5 % to about 4.5 %, or from about 3.0 % to about 4.75 %) based on the total weight of the alloy.
  • the intermetallic particle can include 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %, 0.60 %, 0.61 %, 0.62 %, 0.63 %, 0.64 %, 0.65 %, 0.66 %, 0.67 %, 0.68 %, 0.69 %, 0.70 %, 0.71 %, 0.72 %, 0.73 %, 0.74 %, 0.75 %, 0.76 %, 0.77 %, 0.78 %, 0.79 %, 0.80 %, 0.81 %, 0.82 %, 0.83 %, 0.84 %, 0.85 %, 0.86 %, 0.87 %, 0.88 %, 0.89 %, 0.90 %, 0.91 %, 0.92 %, 0.93 %, 0.94 %, 0.95 %, 0.96 %, 0.97 %, 0.98 %, 0.99 %, 0.60
  • the intermetallic particles may contain Ca in an amount of from about 0.10 % to about 5.0 % (e.g., from about 0.5 % to about 4.5 %, from about 1.0 % to about 4.0 %, from about 1.5 % to about 3.5 %, or from about 2.0 % to about 3.0 %) based on the total weight of the alloy.
  • the intermetallic particle can include 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 033 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %, 0.51 %, 0.52 %, 0.53 %, 0.54 %, 0.55 %, 0.56 %, 0.57 %, 0.58 %, 0.59 %,
  • the intermetallic particles may contain Cr in an amount of from about 0 % to about 1.0 % (e.g., from about 0.01 % to about 0.5 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy.
  • the intermetallic particle can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %,
  • the intermetallic particles may contain Mn in an amount of from about 0 % to about 1.0 % (e.g., from about 0.01 % to about 0.5 % or from about 0.02 % to about 0.1 %) based on the total weight of the alloy.
  • the intermetallic particle can include 0.01 %, 0.02 %, 0.03 %, 0.04 %, 0.05 %, 0.06 %, 0.07 %, 0.08 %, 0.09 %, 0.10 %, 0.11 %, 0.12 %, 0.13 %, 0.14 %, 0.15 %, 0.16 %, 0.17 %, 0.18 %, 0.19 %, 0.20 %, 0.21 %, 0.22 %, 0.23 %, 0.24 %, 0.25 %, 0.26 %, 0.27 %, 0.28 %, 0.29 %, 0.30 %, 0.31 %, 0.32 %, 0.33 %, 0.34 %, 0.35 %, 0.36 %, 0.37 %, 0.38 %, 0.39 %, 0.40 %, 0.41 %, 0.42 %, 0.43 %, 0.44 %, 0.45 %, 0.46 %, 0.47 %, 0.48 %, 0.49 %,
  • the metal products described herein can have a yield strength of at least about 100 MPa.
  • the metal products described herein can have a yield strength of from about 100 MPa to about 300 MPa (e.g., from about 150 MPa to about 250 MPa).
  • the yield strength can be about 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, or 300 MPa.
  • the metal products described herein can have an ultimate tensile strength of at least about 210 MPa.
  • the metal products described herein can have an ultimate tensile strength of from about 210 MPa to about 350 MPa (e.g., from about 250 MPa to about 325 MPa).
  • the ultimate tensile strength can be about 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, 300 MPa, 310 MPa, 320 MPa, 330 MPa, 340 MPa, or 350 MPa.
  • the metal products described herein can have a uniform elongation of at least about 18%.
  • the metal products described herein can have a uniform elongation of from about 18% to about 25% (e.g., from about 19% to about 23%).
  • the uniform elongation can be about 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, or 25%.
  • the metal products described herein can have a total elongation of at least about 20.5%.
  • the metal products described herein can have a total elongation of from about 20.5% to about 27.5% (e.g., from about 22% to about 26%).
  • the total elongation can be about 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, or 27.5%.
  • Methods of Making [0081]
  • the alloys discussed herein, which main contain one or more impurities, can be used to cast various metallic cast products, such as billets, ingots, or strips.
  • grain refiner chips Prior to casting, grain refiner chips, as discussed herein are introduced to the liquid metal. As discussed above, the grain refiner chips are reduced in particle size while being simultaneously or sequentially exposed to mechanical deformation.
  • a direct chill casting system can include a mold cavity and a retractable bottom block. As liquid metal solidifies in the mold cavity, the bottom block can be retracted away from the mold cavity to support the solidifying ingot (e.g., embryonic ingot) as the ingot continuous to grow in length due to solidifying metal at the surfaces of the ingot and as the ingot continuous to solidify throughout.
  • the continuous casting system can include a pair of moving opposed casting surfaces (e.g., moving opposed belts, rolls or blocks), a casting cavity between the pair of moving opposed casting surfaces, and a molten metal injector.
  • the molten metal injector can have an end opening from which molten metal can exit the molten metal injector and be injected into the casting cavity.
  • the liquid metal resulting from the melt precursor can include alloying elements that would render the liquid metal a non-standard alloy, such as an alloy that is not normally used for beverage parts (e.g., can ends or can bodies) or automotive parts (e.g., automotive hood liners), such as when recycled scrap is utilized.
  • the grain refiner chips may be formed at block 103. In embodiments where blocks 102 and 103 occur sequentially, the grain refiner chips may be formed prior to forming the melt at block 102 or after forming the melt at block 102.
  • a high proportion of the grain refiner chip particles may have any one or more of the above particle size, such as greater than or about 50% (D50), greater than or about 60%, greater than or about 70%, greater than or about 80%, greater than or about 90%, or any ranges or values therebetween.
  • the grain refiner chips may be added in particle form at block 103.
  • the grain refiner chips may be incorporated into a rod, pellet, or the like prior to addition to the melt, as illustrated in optional operation 103B.
  • the present technology may provide for a faster melt process due at least in part to the increased surface area and deformed facets, or may include the grain refiner chips at a later stage (e.g. downstream of degassing), allowing further improvements in melt homogeneity and intermetallic particle size.
  • adding optional alloying elements can include dissolving raw elements or mixtures of aluminum and the alloying elements into the liquid metal from block 102.
  • the modified liquid metal can have a desired composition of alloying elements and aluminum.
  • the liquid metal from block 104 can be degassed to decrease the amount of dissolved gasses in the modified liquid metal.
  • the intermediate metal product 116 can be hot rolled to gauge or intermediate gauge.
  • Hot rolling to gauge can include applying pressure to the intermediate metal product 116 through one or more work rolls at elevated temperatures, such as temperatures at or above the recrystallization temperature of the intermediate metal product 116, although lower temperatures can also be used. For example, in some cases the hot rolling can occur at temperatures at or above approximately 400 °C, although other temperatures can be used.
  • the intermediate metal product 116 is reduced in thickness from an as-cast gauge to a desired gauge for delivery to an original equipment manufacturer (OEM) or other user or to an intermediate gauge.
  • OEM original equipment manufacturer
  • the hot-rolled metal product 118 can be optionally cold rolled from the intermediate gauge to the final gauge, if needed or desired.
  • Cold rolling to gauge can include applying pressure to the hot-rolled metal product 118 through one or more work rolls at temperatures below the recrystallization temperature of the hot-rolled metal product 118.
  • the cold rolling can occur at temperatures below approximately 400 °C, although other temperatures can be used.
  • the hot-rolled metal product 118 is reduced in thickness from an intermediate gauge to a desired gauge for delivery to an OEM or other user.
  • the intermediate gauge of a hot-rolled metal product 118 can be approximately 4 mm, whereas the final gauge (e.g., a desired gauge for delivery to an OEM) can be approximately 1.5 mm, although other gauges can be used.
  • the metal product can pass through any number of rollers implemented through any number of roll stands. After cold rolling, the metal product can be considered a cold-rolled metal product 119.
  • the cold-rolled metal product 119 can have a T3 temper.
  • the hot-rolled metal product 118 can undergo heat treatment. In some cases, the heat treatment includes annealing. At block 112, the hot-rolled metal product 118 can be reheated to at or above an annealing temperature for a suitable period of time.
  • heat treatment can include solutionizing the hot-rolled metal product 118 to put certain alloying elements back into solution, such as silicon and copper. As part of solutionizing, the reheated metal product can be quenched to facilitate keeping the alloying elements in solution.
  • Heat treatment can improve metallurgical and/or mechanical properties of the metal product. For example, annealing can result in improvements to the formability of the metal product.
  • the metal product can be coiled for delivery to an OEM. In some cases, the metal product can undergo further processing before delivery or can proceed directly into part manufacturing without coiling.
  • the metal products discussed herein may exhibit reduced cracking and breaking, even at very low final gauges, such as those utilized in beverage container applications, and particularly, at rivet locations on such beverage containers.
  • the metal product may contain little to no aluminide phases or intermetallic particles, such as TiAl 3 phases, boride clusters, oxide stringers, and refraction impurities.
  • some, substantially all, or all of the TiAl 3 phases present in the metal product have an equivalent spherical diameter of less than or about 50 ⁇ m, such as less than or about 45 ⁇ m, such as less than or about 40 ⁇ m, such as less than or about 35 ⁇ m, such as less than or about 30 ⁇ m, such as less than or about 25 ⁇ m, such as less than or about 20 ⁇ m, such as less than or about 15 ⁇ m, such as less than or about 10 ⁇ m, such as less than or about 5 ⁇ m, or any ranges or values therebetween.
  • a high proportion of the grain refiner chip particles may have any one or more of the above particle size, such as greater than or about 50% (D50), greater than or about 60%, greater than or about 70%, greater than or about 80%, greater than or about 90%, greater than or about 95%, greater than or about 97.5%, greater than or about 99% or any ranges or values therebetween.
  • D50 50%
  • aluminide phases or intermetallic particles remain in the metal product.
  • a metal casting method comprising: forming an aluminum alloy liquid metal; mechanically deforming a grain refiner product into grain refiner chips having a particle size of less than 1000 ⁇ m, wherein at least a portion of the mechanically deformed grain refiner chip particles comprise one or more TiAl 3 phase particles having an equivalent spherical diameter of less than or about 50 ⁇ m; adding the mechanically deformed grain refiner chips to the aluminum alloy liquid metal casting the liquid metal into a metal product; and rolling the metal product.
  • Aspect 2 The method of aspect 1, wherein substantially all of the grain refiner chips comprise TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.
  • Aspect 3 The method of aspect 1 or 2, wherein the mechanically deformed grain refiner chips are added in the form of chips, pellets, tablets, or a combination thereof.
  • Aspect 4 The method of any one of aspects 1 to 3, wherein the mechanical deforming comprises sawing, grinding, rolling, extruding, machining, impaction, or a combination thereof.
  • Aspect 5 The method of any one of aspects 1 to 4, wherein the mechanical deforming is conducted for a period of time to produce greater than or 500 TiAl 3 particles/mm 2 .
  • Aspect 6 The method of any one of aspects 1 to 5, wherein the metal product comprises one or more intermetallic particles, wherein each of the one or more intermetallic particles comprises an equivalent spherical diameter of less than or about 10 ⁇ m.
  • Aspect 7 The method of any one of aspects 1 to 6, wherein the aluminum alloy comprises one or more of beryllium, magnesium, vanadium, strontium, titanium, and calcium.
  • Aspect 8 The method of any one of aspects 1 to 7, wherein the aluminum alloy comprises a 5xxx series alloy.
  • Aspect 9 The method of any one of aspects 1 to 8, wherein the molten metal comprises greater than or 10 wt.% recycled aluminum alloy.
  • Aspect 10 The method of any one of aspects 1 to 9, wherein the aluminum alloy comprises from 0.01 wt.% titanium to 0.1 wt.% titanium.
  • Aspect 11 The method of any one of aspects 1 to 10, wherein the aluminum alloy comprises from 1 wt.% to 7 wt.% magnesium.
  • Attorney Docket #: 108050-1492445 [0118]
  • Aspect 12 The method of any one of aspects 1 to 11, wherein the aluminum alloy comprises from 0.01 wt.% vanadium to 0.1 wt.% vanadium.
  • Aspect 13 The method of any one of aspects 1 to 12, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl3 phase particles having an equivalent diameter of less than or 50 ⁇ m.
  • Aspect 14 The method of any one of aspects 1 to 13, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl 3 phase particles having an equivalent diameter of less than or 20 ⁇ m.
  • Aspect 15 The method of any one of aspects 1 to 14, wherein greater than or 50 wt.% of the grain refiner chips comprise TiAl 3 phase particles having an equivalent diameter of less than or 10 ⁇ m.
  • Aspect 16 A metal product cast from the method of any one of aspects 1 to 15.
  • a beverage container comprising the aluminum alloy product of aspect 17, or cast from the method of any one of aspects 1 to 15.
  • Aspect 19 A TiAl 3 containing grain refiner product comprising, grain refiner chips having a particle size of less than 1000 ⁇ m, wherein greater than 50 wt.% of the grain refiner chips comprise TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.
  • Aspect 20 The A TiAl 3 containing grain refiner product of aspect 19, wherein substantially all of the grain refiner chips comprise TiAl 3 phase particles having an equivalent spherical diameter of less than or 50 ⁇ m.

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)

Abstract

L'invention divulgue des techniques de coulée de produits métalliques à haute résistance et haute aptitude au formage qui peuvent comprendre des déchets métalliques sans formation de grosses particules intermétalliques dans le produit coulé. Les techniques comprennent la déformation mécanique d'un produit d'affinage de grain et l'utilisation du produit d'affinage de grain déformé mécaniquement pour former un produit coulé d'alliage d'aluminium. Le produit coulé d'alliage d'aluminium comprend des particules intermétalliques ayant un diamètre équivalent sphérique inférieur ou égal à environ 50 µm.
PCT/US2025/020849 2024-03-26 2025-03-21 Désintégration et reconstitution d'un produit d'affinage de grain pour couler des alliages sensibles aux inclusions Pending WO2025207427A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1145413A (zh) * 1995-09-13 1997-03-19 中国科学院金属研究所 一种铝及铝合金用铝钛硼晶粒细化剂
JPH10317083A (ja) * 1997-05-13 1998-12-02 Kobe Steel Ltd アルミニウム合金用結晶粒微細化剤
US20160273075A1 (en) * 2015-03-19 2016-09-22 Citic Dicastal Co., Ltd Aluminium alloy refiner and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1145413A (zh) * 1995-09-13 1997-03-19 中国科学院金属研究所 一种铝及铝合金用铝钛硼晶粒细化剂
JPH10317083A (ja) * 1997-05-13 1998-12-02 Kobe Steel Ltd アルミニウム合金用結晶粒微細化剤
US20160273075A1 (en) * 2015-03-19 2016-09-22 Citic Dicastal Co., Ltd Aluminium alloy refiner and preparation method and application thereof

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