IP Library Granted Patent US 12,305,267
Granted Patent B2
US 12,305,267 · App. 15/901,759 · Granted May 20, 2025

Rapidly solidified aluminum-rare earth element alloy and method of making the same

Inventors: Orlando Rios (Knoxville, TN); Scott McCall (Livermore, CA); Ryan Ott (Ames, IA); Zachary Cole Sims (Knoxville, TN); Michael Kesler (Knoxville, TN); Hunter B. Henderson (Knoxville, TN); Michael McGuire (Knoxville, TN); David Weiss (Manitowoc, WI)
Assignees: UT-Battelle, LLC; University of Tennessee Research Foundation; Iowa State University Research Foundation, Inc.; ECK Industries Incorporated; Lawrence Livermore National Security, LLC
C22F1/002B22D17/2218B22D21/007C22C1/026C22C1/11C22C21/00C22C21/06C22C45/08C22F1/04C22F1/047C22C2200/02
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Quick Facts
Patent No.
US 12,305,267
App. No.
15/901,759
Granted
May 20, 2025
Kind
B2
Abstract

Disclosed herein are embodiments of rapidly solidified alloys that comprise aluminum, a rare earth element, one or more additional alloying elements, such as aluminum, and an optional additive component. The alloy embodiments exhibit a unique microstructure as compared to microstructures obtained from other alloys that are not rapidly cooled. The disclosed aluminum-rare earth element alloys also exhibit improved mechanical properties without the need for post-processing heat treatments and further do not exhibit substantial coarsening.

Claims (13)

1. A method, comprising:

combining aluminum with (i) 0.1 wt % to 8 wt % of an additional alloying element selected from magnesium, zinc, titanium, manganese, zirconium, vanadium, scandium, copper, or nickel, or one or more of magnesium, zinc, titanium, manganese, zirconium, vanadium, and scandium in combination with copper or in combination with nickel; (ii) at least one rare earth component selected from lanthanum, cerium, mischmetal, or a combination thereof; and (iii) 0.1 wt % to 2 wt % of an additive component selected from iron, strontium, boron, manganese, titanium, chromium, cobalt, carbon, or a combination thereof to form an aluminum-based alloy composition; wherein the aluminum-based alloy composition does not comprise both copper and nickel in combination; and

performing a cooling step, wherein the mixed aluminum-based alloy composition is cooled at an average cooling rate range from greater than 100 K/s to 10 8 K/s to provide an aluminum-based alloy comprising an aluminum matrix phase, an Al 11 X 3 intermetallic phase where X is one of lanthanum, cerium, or mischmetal, or a combination thereof, and (i) a semi- to fully-eutectic phase with a maximum spacing between morphologic features of the semi- to fully-eutectic phase being no greater than 8 μm; or (ii) a phase comprising laths and/or rods, wherein the aluminum matrix phase, the Al 11 X 3 intermetallic phase, and the semi- to fully-eutectic phase, or the phase comprising laths and/or rods are obtained without a heat treatment; provided that the cooling step does not comprise continuous cast rolling to cool the mixed aluminum-based alloy composition.

2. The method of claim 1 , wherein the average cooling rate ranges from 1000 K/s to 10 5 K/s.

3. The method of claim 1 , wherein the average cooling rate ranges from greater than 10 5 K/s to 10 8 K/s.

4. The method of claim 1 , wherein the aluminum-based alloy comprises 8 wt % to 12 wt % of the at least one rare earth component and wherein the at least one rare earth component is cerium.

5. The method of claim 1 , wherein the aluminum-based alloy comprises an Al 13 (Mg,Ce) 2 phase, an Al 12 CeMg 6 phase, an FCC matrix phase comprising aluminum and cerium, or any combination of such phases.

6. The method of claim 1 , wherein the aluminum-based alloy consists essentially of 12 wt % cerium, 0.4 wt % magnesium, 1 wt % iron, and a balance of aluminum.

7. The method of claim 1 , wherein the semi- to fully-eutectic phase has a maximum spacing between morphologic features ranging from greater than 0 μm to less than or equal to 5 μm.

8. The method of claim 1 , wherein the method does not comprise a post-processing heat treatment.

9. The method of claim 1 , wherein the aluminum-based alloy does not exhibit substantial coarsening of the semi- to fully-eutectic microstructure such that an increase in average spacing of lamellae and/or particles within the semi- to fully-eutectic microstructure does not occur after being exposed to processing temperatures of 150° C. to 500° C. for 1500 hours.

10. The method of claim 1 , wherein the aluminum-based alloy composition consists of aluminum, the additional alloying element, the at least one rare earth component, the additive component, and trace impurities.

11. The method of claim 1 , wherein the average cooling rate ranges from greater than 100 K/s to less than 1000 K/s.

Assignments (8)
CONFIRMATORY LICENSE Recorded Jan 10, 2020
From: IOWA STATE UNIVERSITY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 051564/0284 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 17, 2018
From: SIMS, ZACHARY C.
To: UNIVERSITY OF TENNESSEE RESEARCH FOUNDATION
Reel/Frame 046893/0012 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 29, 2018
From: WEISS, DAVID
To: ECK INDUSTRIES INCORPORATED
Reel/Frame 046237/0777 →
CONFIRMATORY LICENSE Recorded May 9, 2018
From: UT-BATTELLE, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 045750/0402 →
CONFIRMATORY LICENSE Recorded May 9, 2018
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 045750/0718 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 23, 2018
From: OTT, RYAN
To: IOWA STATE UNIVERSITY RESEARCH FOUNDATION, INC.
Reel/Frame 045326/0706 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 20, 2018
From: RIOS, ORLANDO; KESLER, MICHAEL; HENDERSON, HUNTER B.; MCGUIRE, MICHAEL
To: UT-BATTELLE, LLC
Reel/Frame 045284/0310 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 28, 2018
From: MCCALL, SCOTT
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Reel/Frame 045069/0346 →
Continuity (3)
Provisional Application 62616658 · Jan 12, 2018
Provisional Application 62461899 · Feb 22, 2017
Related Publication 20180237893A1 · Aug 23, 2018
References Cited (121)
US 1960916A · Murphey et al. · 1934 [cited by applicant]
US 2656270A · Russell · 1953 [cited by examiner]
US 4379719A · Hildeman · 1983 [cited by examiner]
US 4464199A · Hildeman · 1984 [cited by examiner]
US 4787943A · Mahajan · 1988 [cited by examiner]
US 4915869A · Aubert et al. · 1990 [cited by applicant]
US 4950452A · Masumoto · 1990 [cited by examiner]
US 5037608A · Tarcy et al. · 1991 [cited by applicant]
US 5074935A · Masumoto · 1991 [cited by examiner]
US 5154780A · Premkumar · 1992 [cited by examiner]
US 5264021A · Kita · 1993 [cited by examiner]
US 5318642A · Kita · 1994 [cited by examiner]
US 5320688A · Masumoto · 1994 [cited by examiner]
US 5431751A · Okochi et al. · 1995 [cited by applicant]
US 3252841A · Foerster · 1996 [cited by applicant]
US 5578144A · Satou · 1996 [cited by examiner]
US 5647919A · Kita · 1997 [cited by examiner]
US 5900210A · Buchler · 1999 [cited by examiner]
US 6231808B1 · Hashikura · 2001 [cited by examiner]
US 6248453B1 · Watson · 2001 [cited by examiner]
US 7811395B2 · Pandey · 2010 [cited by applicant]
US 7875131B2 · Pandey · 2011 [cited by examiner]
US 9079211B1 · Deshpande et al. · 2015 [cited by applicant]
US 9394596B2 · Kramer et al. · 2016 [cited by applicant]
US 9963770B2 · Rios · 2018 [cited by examiner]
US 11383296B2 · Wagstaff · 2022 [cited by examiner]
US 20030183306A1 · Hehmann et al. · 2003 [cited by applicant]
US 20040156739A1 · Song · 2004 [cited by examiner]
US 20040238150A1 · Adachi et al. · 2004 [cited by applicant]
US 20050199318A1 · Doty · 2005 [cited by examiner]
US 20050271543A1 · Pfannen-Mueller et al. · 2005 [cited by applicant]
US 20080219882A1 · Woydt · 2008 [cited by examiner]
US 20090263266A1 · Pandey · 2009 [cited by examiner]
US 20090288796A1 · Song et al. · 2009 [cited by applicant]
US 20100226817A1 · Pandey · 2010 [cited by applicant]
US 20100282428A1 · Pandey · 2010 [cited by applicant]
US 20120058353A1 · Komiyama et al. · 2012 [cited by applicant]
US 20120152414A1 · Che et al. · 2012 [cited by applicant]
US 20130312876A1 · Palm · 2013 [cited by examiner]
US 20140326368A1 · Okamoto · 2014 [cited by applicant]
US 20150135897A1 · Sutkliffe et al. · 2015 [cited by applicant]
US 20160053346A1 · Szuromi et al. · 2016 [cited by applicant]
US 20170096730A1 · Rios et al. · 2017 [cited by applicant]
US 20180237893A1 · Rios et al. · 2018 [cited by applicant]
US 20180291489A1 · Mann et al. · 2018 [cited by applicant]
US 20190085431A1 · Rios et al. · 2019 [cited by applicant]
US 20210032727A1 · Chehab · 2021 [cited by applicant]
US 20210276099A1 · Chehab · 2021 [cited by applicant]
CN 103509977A · 2014 [cited by applicant]
CN 104004947A · 2014 [cited by applicant]
CN 104711464A · 2015 [cited by examiner]
CN 109797326A · 2019 [cited by applicant]
CN 114438383A · 2022 [cited by applicant]
DE 102011111365 · 2013 [cited by applicant]
JP 06184712A · 1994 [cited by applicant]
JP H07268597 · 1995 [cited by applicant]
JP 3392509B2 · 2003 [cited by applicant]
WO WO02086175A1 · 2002 [cited by applicant]
WO WO2011035653A1 · 2011 [cited by examiner]
WO WO2017007908 · 2017 [cited by applicant]
WO WO2018119283A1 · 2018 [cited by applicant]
WO WO2018156651A1 · 2018 [cited by applicant]
WO WO2019155180 · 2019 [cited by applicant]
Gallo, et al; “Aluminum fluxes and fluxing practices”, ASM Handbook, 2008, vol. 15, pp. 230-239 (Year: 2008). [cited by examiner]
Raghavan V.; “Al—Ce—Mg (Aluminum-Cerium-Magnesium)”, ASM International, 2007, p. 453-455 (Year: 2007). [cited by examiner]
Prakash U., et al.; The effect of Mg Addition on Microstructure and Tensile and Stress Rupture Properties of a P/M Al—Fe—Ce alloy; Scripta Materialia, vol. 39., No. 7, pp. 867-872, 1998 (Year: 1998). [cited by examiner]
Fodran E.; “Microstructural Evolution and Thermal Stability of Al—Ce—Ni Ternary Eutectic”; Dissertation from University of Florida, 2002 (Year: 2002). [cited by examiner]
Czerwinski F., et al.; “On the Al—Al11Ce3 Eutectic Transformation in Aluminum-Cerium Binary Alloys”; J. Materials, 13, 2020 (Year: 2020). [cited by examiner]
Park H., et al.; Effect of Fe additions on microstructure and mechanical properties in near-eutectic Al-Ce Alloys; j. of Materials Science & Engineering A; 88, 2023 (Year: 2023). [cited by examiner]
Bakke et al., “Improving the Strength and Ductility of Magnesium Die-Casting Alloys via Rare-Earth Addition,” [cited by applicant]
Cecchinato et al., “Influence of Magnesium Alloy Degradation on Undifferentiated Human Cells,” [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2016/41293 dated Nov. 17, 2016. [cited by applicant]
Plotkowski et al., “Evaluation of an Al—Ce alloy for laser additive manufacturing,” [cited by applicant]
Sims et al., “Cerium-Based, Intermetallic-Strengthened Aluminum Casting Alloy: High-Volume Co-product Development,” [cited by applicant]
Sims et al., “High performance aluminum-cerium alloys for high-temperature applications,” [cited by applicant]
Zhang, “Effect of substituting cerium-rich mischmetal with lanthanum on microstructure and mechanical properties of die-cast Mg—Al—Re alloys,” [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2017/042208 dated Oct. 20, 2017. [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2018/019046 dated Jul. 17, 2018. [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2018/051218 dated Dec. 21, 2018. [cited by applicant]
Yao et al., “Effects of La on the age hardening behavior and precipitation kinetics in the cast Al—Cu alloy,” [cited by applicant]
Fan et al., “Dual characteristic of trace rare earth elements in a commercial casting Al—Cu-X alloy,” [cited by applicant]
Yao et al., “Phase relations in the Cu-poor part of the Ce—Al—Cu system at 503 K,” [cited by applicant]
Jin et al., “Thermodynamic evaluation and optimization of Al—La, Al—Ce, Al—Pr, Al—Nd and Al—Sm systems using the Modified Quasichemical Model for liquids,” [cited by applicant]
Kang et al., “Critical evaluation and thermodynamic optimization of the Al—Ce, Al—Y, Al—Sc and Mg—Sc binary systems,” [cited by applicant]
Meng et al., “Thermodynamic optimization of the Al—Yb binary system,” [cited by applicant]
Riani et al., “Ternary rare-earth aluminum systems with copper: a review and a contribution to their assessment,” [cited by applicant]
Van Dalen et al., “Erbium and ytterbium solubilities and diffusivities in aluminum as determined by nanoscale characterization of precipitates,” [cited by applicant]
Abbas, “Effect of high-power diode laser surface melting on wear resistance of magnesium alloys,” [cited by applicant]
Audebert et al., “Production of glassy metallic layers by laser surface treatment,” [cited by applicant]
Chen et al., “Mechanical Properties of Nanometric Al2O3 Particulate-Reinforced Al-Al11Ce3 Composites Produced by Friction Stir Processing,” [cited by applicant]
Davis, “Aluminum and Aluminum Alloys,” [cited by applicant]
Debroy et al., “Additive Manufacturing of Metallic Components—Process, Structure and Properties,” [cited by applicant]
Dudas et al., “Preventing Weld Cracks in High-Strength Aluminum Alloys,” Weld. Res., vol. 45, pp. 241-249 (Jun. 1966). [cited by applicant]
Eskin et al., “A Quest for a New Hot Tearing Criterion,” Metall. Mater. Trans. A Phys. Metall. Mater. Sci., vol. 38A, pp. 1511-1519 (Jul. 2007). [cited by applicant]
Final Office Action issued for U.S. Appl. No. 16/132,231 on Dec. 27, 2021 (13 pages). [cited by applicant]
Final Office Action issued for U.S. Appl. No. 16/132,231 on Jan. 25, 2023 (12 pages). [cited by applicant]
Frazier, “Metal Additive Manufacturing: A Review,” J. Mater. Eng. Perform., vol. 23(6), pp. 1917-1928 (Jun. 2014). [cited by applicant]
Graham et al., “Coarsening of Eutectic Microstructures at Elevated Temperatures,” Transactions of the Metallurgical Society of AIME, vol. 236, pp. 94-102, Jan. 1966. [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2017/042203 on Oct. 20, 2017. [cited by applicant]
International Search Report and Written Opinion issued for International Application No. PCT/US2018/019046 on May 9, 2018, 21 pages. [cited by applicant]
Jun et al., “Characterization and wear resistance of laser surface melting AZ91D alloy,” [cited by applicant]
Kou, “A Criterion for Cracking During Solidification,” Acta Mater., vol. 88, pp. 366-374 (2015). [cited by applicant]
Kou, “A Simple Index for Predicting the Susceptibility to Solidification Cracking,” Weld. J., vol. 94, pp. 374-388 (Dec. 2015). [cited by applicant]
Kou, “Welding Metallurgy, Second Edition,” John Wiley & Sons, Inc., Hoboken, NJ, 466 pages (2003). [cited by applicant]
Knipling et al., “Criteria for developing castable, creep-resistant aluminum-based alloys—A review,” [cited by applicant]
Lewandowski et al., “Metal Additive Manufacturing: A Review of Mechanical Properties,” Annu. Rev. Mater. Res., vol. 46, pp. 151-186 (2016). [cited by applicant]
Li et al., “Corrosion mechanism associated with T1 and T2 precipitates of Al—Cu—Li alloys in NaCl solution”, Journal of Alloys and Compounds, 460, pp. 688-693 (2008). [cited by applicant]
Lin et al., “Hot-Tear Susceptibility of Aluminum Wrought Alloys and the Effect of Grain Refining,” Metall. Mater. Trans. A Phys. Metall. Mater. Sci., vol. 38, pp. 1056-1068 (2007). [cited by applicant]
Manca et al., “Microstructure and Properties of Novel Heat Resistant Al—Ce—Cu Alloy for Additive Manufacturing,” [cited by applicant]
Miller et al., “Recent Development in Aluminum Alloys for the Automotive Industry,” Mater. Sci. Eng. A., vol. 280, pp. 37-49 (2000). [cited by applicant]
Non-Final Office Action issued for U.S. Appl. No. 16/132,231 on Jun. 15, 2021, 15 pages. [cited by applicant]
Non-Final Office Action issued for U.S. Appl. No. 16/132,231 on Jun. 16, 2022 (14 pages). [cited by applicant]
Phillion et al., “A New Methodology for Measurement of Semi-Solid Constitutive Behavior and its Application to Examination of As-Cast Porosity and Hot Tearing in Aluminum Alloys,” pp. 1-24 (also published as PHILLION et… [cited by applicant]
Plotkowski et al., “Corrigendum to 'Evaluation of an Al-Ce alloy for additive manufacturing,” [Acta Mater. 126 (2017) 507-519] [cited by applicant]
Raghavan, “Al-Cu-Li (Aluminum-Copper-Lithium)”, Journal of Phase Equilibria and Diffusion, vol. 31, No. 3, pp. 288-290 (2010). [cited by applicant]
Rappaz et al., “A New Hot-Tearing Criterion,” Metall. Mater. Trans. A., vol. 30A, pp. 449-455 (Feb. 1999). [cited by applicant]
Sames et al., “The Metallurgy and Processing Science of Metal Additive Manufacturing,” pp. 1-76 (also published as SAMES et al., “The Metallurgy and Processing Science of Metal Additive Manufacturing,” Int. Mater. Rev.,… [cited by applicant]
Sims et al., “Characterization of Near Net-Shape Castable Rare Earth Modified Aluminum Alloys for High Temperature Application,” [cited by applicant]
Tomida et al., “Improvement in wear resistance of hyper-eutectic Al-Si cast alloy by laser surface remelting,” [cited by applicant]
Trevisan, “On the Selective Laser Melting (SLM) of the AISi10Mg Alloy: Process, Microstructure, and Mechanical Properties,” [cited by applicant]
Yilmaz et al., “The microstructure and mechanical properties of unidirectionally solidified Al-Si alloys,” [cited by applicant]