WO2020060763A1 - Alliage d'aluminium résistant à la corrosion - Google Patents

Alliage d'aluminium résistant à la corrosion Download PDF

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WO2020060763A1
WO2020060763A1 PCT/US2019/049661 US2019049661W WO2020060763A1 WO 2020060763 A1 WO2020060763 A1 WO 2020060763A1 US 2019049661 W US2019049661 W US 2019049661W WO 2020060763 A1 WO2020060763 A1 WO 2020060763A1
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aluminum alloy
another embodiment
corrosion resistant
resistant additive
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Carolyn G. NORWOOD
Elizabeth L. RALPH
Hasso Weiland
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Howmet Aerospace Inc
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Arconic Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023—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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/046—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present disclosure is directed towards corrosion resistant aluminum alloys.
  • Utilizing aluminum alloy compositions as an electrode (anode) in an electrochemical cell can be evaluated by quantifying and/or qualifying two phenomena: (1) the anodic reaction and (2) the corrosion reaction of the aluminum alloy composition.
  • the anodic reaction aluminum reacts with hydroxyl ions which results in the release of electrons, the primary and desirable product of an electrochemical cell.
  • the corrosion reaction the aluminum in the anode material is oxidized in the presence of water and, as the oxygen in the water reacts with the aluminum, aluminum oxide is formed, generating hydrogen gas as a byproduct of the corrosion reaction of the aluminum alloy composition.
  • aluminum is consumed without contributing to the production of (creating) electrical energy in the electrochemical cell.
  • the extent of the corrosion reaction i.e. the amount of hydrogen generated for an aluminum alloy used as an anode, is a function of electrolyte temperatures and current densities in the electrochemical cell. As operating temperatures and applied current vary for the operation of the cell, so too does the aluminum alloy composition experience varying instances of high anodic reaction and high corrosion reaction windows within the operating parameters/ranges of the electrolytic cell
  • the new aluminum alloys used to produce the new aluminum electrode alloys described herein may be any suitable aluminum alloy having low amounts of iron (e.g. from O.001 wt. % Fe to 0.06 wt. % Fe) and an effective amount of a corrosion resistant additive plus phosphorous such that the aluminum electrode alloy has improved corrosion resistance as compared to an aluminum electrode alloy without such corrosion resistant additives and phosphorous.
  • a reference to an aluminum alloy composition is also a reference to an aluminum electrode alloy composition.
  • “aluminum alloy” means an alloy having aluminum as the predominant alloying element.
  • the phrase“aluminum electrode alloy” means an aluminum electrode alloy configured for use as an anode or cathode in an electrochemical cell.
  • an aluminum alloy is one of a lxxx, 2xxx, 3xxx, 4xxx, 5xxx, 6xxx, 7xxx, or 8xxx series aluminum alloys, as defined by the Aluminum Association document “International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys” (2015).
  • the aluminum alloy is a lxxx series aluminum alloy.
  • the aluminum alloy is a 2xxx series aluminum alloy.
  • the aluminum alloy is a 3xxx series aluminum alloy. In yet another embodiment, the aluminum alloy is a 4xxx series aluminum alloy. In another embodiment, the aluminum alloy is a 5xxx series aluminum alloy. In yet another embodiment, the aluminum alloy is 6xxx series aluminum alloy. In another embodiment, the aluminum alloy is a 7xxx series aluminum alloy. In yet another embodiment, the aluminum alloy is an 8xxx series aluminum alloy. In another embodiment, the aluminum alloy is selected from the group consisting of a lxxx series aluminum alloy and a 5xxx series aluminum alloy. In one embodiment, the aluminum electrode alloy may comprise a 5252 aluminum alloy. In another embodiment, the aluminum electrode alloy may comprise a 5005 aluminum alloy.
  • the aluminum alloys may include phosphorous.
  • the addition of phosphorous to the aluminum alloy may facilitate, for instance, lower corrosion, i.e. hydrogen generation.
  • the aluminum alloy includes at least 0.0001 wt. % (1 ppm) P.
  • the aluminum alloy includes at least 0.0002 wt. % (2 ppm) P.
  • the aluminum alloy includes at least 0.0003 wt. % (3 ppm) P.
  • the aluminum alloy includes at least 0.0004 wt. % (4 ppm)
  • the aluminum alloy includes at least 0.0005 wt. % (5 ppm) P. In another embodiment, the aluminum alloy includes at least 0.001 wt. % (10 ppm) P. In one embodiment, the aluminum alloy includes less than 0.10 wt. % (1000 ppm) P. In another embodiment, the aluminum alloy includes not greater than 0.0975 wt. % (975 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.095 wt. % (950 ppm) P. In another embodiment, the aluminum alloy includes not greater than 0.0925 wt. % (925 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.09 wt.
  • the aluminum alloy includes not greater than 0.0875 wt. % (875 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.085 wt. % (850 ppm) P. In another embodiment, the aluminum alloy includes not greater than 0.0825 wt. % (825 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.08 wt. % (800 ppm) P. In another embodiment, the aluminum alloy includes not greater than 0.06 wt. % (600 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.04 wt. % (400 ppm) P.
  • the aluminum alloy includes not greater than 0.02 wt. % (200 ppm) P. In yet another embodiment, the aluminum alloy includes not greater than 0.01 wt. % (100 ppm) P. In another embodiment, the aluminum alloy includes not greater than 0.005 wt. % (50 ppm) P. In one embodiment, the aluminum alloy includes 0.0001 to 0.10 wt. % (1 to 1000 ppm) P. In one embodiment, the aluminum alloy includes 0.0005 to 0.08 wt. % (5 to 800 ppm) P. In another embodiment, the aluminum alloy includes 0.0005 to 0.06 wt. % (5 to 600 ppm) P. In yet another embodiment, the aluminum alloy includes 0.0005 to 0.04 wt.
  • the aluminum alloy includes 0.0005 to 0.02 wt. % (5 to 200 ppm) P. In yet another embodiment, the aluminum alloy includes 0.0005 to 0.01 wt. % (5 to 100 ppm) P. In another embodiment, the aluminum alloy includes 0.0005 to 0.005 wt. % (5 to 50 ppm) P. In yet another embodiment, the aluminum alloy includes 0.001 to 0.08 wt. % (10 to 800 ppm) P.
  • the aluminum alloys generally comprise an effective amount of a corrosion resistant additive.
  • corrosion resistant additives are defined and described in commonly-owned International Patent Application No. PCT/US2017/066053, entitled,“Corrosion Resistant Aluminum Alloy,” filed December 13, 2017, published as WO2018/112018.
  • Various embodiments relating to corrosion resistant additives are described in section i.a., below.
  • the aluminum alloys may include from 0.001 to 0.06 wt. %
  • the aluminum alloy includes at least 0.001 wt. % Fe (10 ppm). In another embodiment, the aluminum alloy includes at least 0.0015 wt. % (15 ppm) Fe. In one embodiment, the aluminum alloy includes not greater than 0.06 wt. % (600 ppm) Fe. In another embodiment, the aluminum alloy includes not greater than 0.04 wt. % (400 ppm) Fe. In yet another embodiment, the aluminum alloy includes not greater than 0.03 wt. % (300 ppm) Fe. In another embodiment, the aluminum alloy includes not greater than 0.025 wt. % (250 ppm) Fe.
  • the aluminum alloy includes not greater than 0.02 wt. % (200 ppm) Fe. In another embodiment, the aluminum alloy includes not greater than 0.01 wt. % (100 ppm) Fe. In yet another embodiment, the aluminum alloy includes not greater than 0.0075 wt. % (75 ppm). In another embodiment, the aluminum alloy includes not greater than 0.005 wt. % (50 ppm) Fe. Fe. In one embodiment, the aluminum alloy includes 0.001 to 0.04 wt. % (10 to 400 ppm) Fe. In another embodiment, the aluminum alloy includes 0.001 to 0.03 wt. % (10 to 300 ppm) Fe. In yet another embodiment, the aluminum alloy includes 0.001 to 0.025 wt.
  • the aluminum alloy includes 0.001 to 0.01 wt. % (10 to 100 ppm) Fe. In yet another embodiment, the aluminum alloy includes 0.001 to 0.0075 wt. % (10 to 75 ppm) Fe. In another embodiment, the aluminum alloy includes 0.001 to 0.005 wt. % (10 to 50 ppm) Fe. In yet another embodiment, the aluminum alloy includes 0.015 to 0.025 wt. % (150 to 250 ppm) Fe. Appropriate aluminum alloy base materials may be used to facilitate casting of the new aluminum alloy; such base materials generally will have similar iron and silicon contents. Thus, the aluminum alloys described herein generally contain silicon levels similar to the above-described levels of iron.
  • the new aluminum alloys may be a 5xxx series alloy.
  • the aluminum alloy may include at least 0.01 wt. % Mg.
  • the aluminum alloy may include at least 0.1 wt. % Mg.
  • the aluminum alloy may include at least 0.5 wt. % Mg.
  • the aluminum alloy may include at least 1.0 wt. % Mg.
  • the aluminum alloy may include at least 1.5 wt. % Mg.
  • the aluminum alloy may include at least 2.0 wt. % Mg.
  • the aluminum alloy may include not greater than 5.0 wt. % Mg.
  • the aluminum alloy may include not greater than 4.0 wt. % Mg. In another embodiment, the aluminum alloy may include not greater than 3.0 wt. % Mg. In yet another embodiment, the aluminum alloy may include not greater than 2.0 wt. % Mg. In another embodiment, the aluminum alloy may include not greater than 1.5 wt. % Mg. In yet another embodiment, the aluminum alloy may include not greater than 1.0 wt. % Mg. In another embodiment, the aluminum alloy may include not greater than 0.5 wt. % Mg. In one embodiment, the aluminum alloy may include 0.01 to 5.0 wt. % Mg. In another embodiment, the aluminum alloy may include 0.1 to 5.0 wt. % Mg.
  • the aluminum alloy may include 0.5 to 5.0 wt. % Mg. In another embodiment, the aluminum alloy may include 1.0 to 5.0 wt. % Mg. In yet another embodiment, the aluminum alloy may include 1.5 to 5.0 wt. % Mg. In another embodiment, the aluminum alloy may include 2.0 to 5.0 wt. % Mg. In yet another embodiment, the aluminum alloy may include 3.0 to 5.0 wt. % Mg. In another embodiment, the aluminum alloy may include 4.0 to 5.0 wt. % Mg. In another embodiment, the aluminum alloy may include 0.01 to 4.0 wt. % Mg. In yet another embodiment, the aluminum alloy may include 0.01 to 3.0 wt. % Mg.
  • the aluminum alloy may include 0.01 to 2.0 wt. % Mg. In another embodiment, the aluminum alloy may include 0.01 to 1.5 wt. % Mg. In another embodiment, the aluminum alloy may include 0.01 to 1.0 wt. % Mg. In one embodiment, the aluminum alloy has no Mg (i.e. includes Mg as an impurity only).
  • the new aluminum alloy may be substantially free of impurities, meaning that the alloy contains no more than 0.10 wt. % of any one impurity, and that the total combined amount of the impurities in the aluminum alloy does not exceed 0.35 wt. %.
  • each one of the impurities, individually, does not exceed 0.05 wt. % in the aluminum alloy, and the total combined amount of the impurities does not exceed about 0.15 wt. %.
  • each one of the impurities, individually, does not exceed 0.03 wt. % in the aluminum alloy, and the total combined amount of the impurities does not exceed about 0.12 wt. %.
  • each one of the impurities, individually, does not exceed 0.01 wt. % in the aluminum alloy, and the total combined amount of the impurities does not exceed about 0.03 wt. %.
  • the aluminum alloys generally comprise an effective amount of a corrosion resistant additive.
  • an“effective amount” in this embodiment is a large enough quantity to provide an improved corrosion resistance in the aluminum alloy composition (e.g. measurable, observable, and/or quantifiable).
  • “corrosion resistant additive” refers to an addition of a component to the aluminum alloy in order to impart corrosion resistance (e.g. reduce corrosion when evaluated as an electrode in an electrochemical cell) as compared to the alloy’s corrosion without such additions.
  • the corrosion resistant additive is Zn. In another embodiment, the corrosion resistant additive is Ga. In yet another embodiment, the corrosion resistant additive is Zn and Ga. In another embodiment, the corrosion resistant additive is selected from the group consisting of: Zn, Ga, and combinations thereof. [0015] In some embodiments, the effective amount of corrosion resistant additive is at least 0.0005 wt. % (5 ppm); at least 0.001 wt. % (10 ppm); at least 0.0015 wt. % (15 ppm); at least 0.002 wt. % (20 ppm); at least 0.005 wt. % (50 ppm); at least 0.01 wt. % (100 ppm); at least 0.015 wt.
  • the effective amount of corrosion resistant additive is at least 0.0005 wt. % (5 ppm); at least 0.001 wt. % (10 ppm); at least 0.0015 wt. % (15 ppm); at least 0.002 wt. % (20
  • % 150 ppm; at least 0.02 wt. % (200 ppm); at least 0.025 wt. % (250 ppm); at least 0.03 wt. % (300 ppm); at least 0.035 wt. % (350 ppm); at least 0.04 wt. % (400 ppm); at least 0.045 wt. % (450 ppm); at least 0.05 wt. % (500 ppm); at least 0.055 wt. % (550 ppm); at least 0.06 wt. % (600 ppm); at least 0.065 wt. % (650 ppm); at least 0.07 wt.
  • % 700 ppm; at least 0.075 wt. % (750 ppm); at least 0.08 wt. % (800 ppm); at least 0.085 wt. % (850 ppm); at least 0.09 wt. % (900 ppm); at least 0.095 wt. % (950 ppm); or at least 0.10 wt. % (1000 ppm), where at least some (an effective amount of) Zn and Ga are present, when both Zn and Ga are utilized as the corrosion resistant additives.
  • the effective amount of corrosion resistant additive is not greater than 0.0005 wt. % (5 ppm); not greater than 0.001 wt. % (10 ppm); not greater than 0.0015 wt. % (15 ppm); not greater than 0.002 wt. % (20 ppm); not greater than 0.005 wt. % (50 ppm); not greater than 0.01 wt. % (100 ppm); not greater than 0.015 wt. % (150 ppm); not greater than 0.02 wt. % (200 ppm); not greater than 0.025 wt. % (250 ppm); not greater than 0.03 wt.
  • % (300 ppm); not greater than 0.035 wt. % (350 ppm); not greater than 0.04 wt. % (400 ppm); not greater than 0.045 wt. % (450 ppm); not greater than 0.05 wt. % (500 ppm); not greater than 0.055 wt. % (550 ppm); not greater than 0.06 wt. % (600 ppm); not greater than 0.065 wt. % (650 ppm); not greater than 0.07 wt. % (700 ppm); not greater than 0.075 wt. % (750 ppm); not greater than 0.08 wt.
  • % (800 ppm); not greater than 0.085 wt. % (850 ppm); not greater than 0.09 wt. % (900 ppm); not greater than 0.095 wt. % (950 ppm); or not greater than 0.10 wt. % (1000 ppm), where not greater than some (an effective amount of) Zn and Ga are present, when both Zn and Ga are utilized as the corrosion resistant additives.
  • the amount of Zn as a corrosion resistant additive as an individual addition is not greater than 0.05 wt. % of the corrosion resistant alloy.
  • the effective amount of corrosion resistant additive of Zn is at least 0.002 wt. % (20 ppm); at least 0.005 wt. % (50 ppm); at least 0.01 wt. % (100 ppm); at least 0.015 wt. % (150 ppm); at least 0.02 wt. % (200 ppm); at least 0.025 wt. % (250 ppm); at least 0.03 wt. % (300 ppm); at least 0.035 wt.
  • the effective amount of corrosion resistant additive of Zn is not greater than 0.002 wt. % (20 ppm); not greater than 0.005 wt. % (50 ppm); not greater than 0.01 wt. % (100 ppm); not greater than 0.015 wt. % (150 ppm); not greater than 0.02 wt. % (200 ppm); not greater than 0.025 wt. % (250 ppm); not greater than 0.03 wt.
  • an effective amount of the corrosion resistant additive of Zn is at least 0.002 wt. % (20 ppm) to not greater than 0.05 wt. % (500 ppm).
  • the amount of Ga as a corrosion resistant additive as an individual addition is not greater than 0.06 wt. % of the corrosion resistant alloy. In one or more of the aforementioned embodiments, the amount of Ga as a corrosion resistant additive as an individual addition is not greater than 0.0 wt. % of the corrosion resistant alloy. In some embodiments, the effective amount of corrosion resistant additive of Ga is at least 0.0005 wt. % (5 ppm); at least 0.001 wt. % (10 ppm); at least 0.0015 wt. % (15 ppm); at least 0.002 wt. % (20 ppm); at least 0.005 wt.
  • % (50 ppm); at least 0.01 wt. % (100 ppm); at least 0.015 wt. % (150 ppm); at least 0.02 wt. % (200 ppm); at least 0.025 wt. % (250 ppm); at least 0.03 wt. % (300 ppm); at least 0.035 wt. % (350 ppm); at least 0.04 wt. % (400 ppm); at least 0.045 wt. % (450 ppm); at least 0.05 wt. % (500 ppm); at least 0.055 wt. % (550 ppm); or at least 0.06 wt. % (600 ppm).
  • the effective amount of corrosion resistant additive of Ga is not greater than 0.0005 wt. % (5 ppm); not greater than 0.001 wt. % (10 ppm); not greater than 0.0015 wt. % (15 ppm); not greater than 0.002 wt. % (20 ppm); not greater than 0.005 wt. % (50 ppm); not greater than 0.01 wt. % (100 ppm); not greater than 0.015 wt. % (150 ppm); not greater than 0.02 wt. % (200 ppm); not greater than 0.025 wt. % (250 ppm); not greater than 0.03 wt.
  • an effective amount of the corrosion resistant additive of Ga is at least 0.002 wt. % (20 ppm) to not greater than 0.05 wt. % (500 ppm).
  • an effective amount of the corrosion resistant additive is at least 0.0005 wt. % (5 ppm) to not greater than 0.06 wt. % (600 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.001 wt. % (10 ppm) to not greater than 0.03 wt. % (300 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.0005 wt. % (5 ppm) to not greater than 0.01 wt. % (100 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.0005 wt. % (5 ppm) to not greater than 0.005 wt.
  • an effective amount of the corrosion resistant additive is at least 0.002 wt. % (20 ppm) to not greater than 0.01 wt. % (100 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.002 wt. % (20 ppm) to not greater than 0.005 wt. % (50 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.002 wt. % (20 ppm) to not greater than 0.10 wt. % (1000 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.005 wt.
  • an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.10 wt. % (1000 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.07 wt. % (700 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.05 wt. % (500 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.03 wt. % (300 ppm).
  • an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.02 wt. % (200 ppm). In some embodiments, an effective amount of the corrosion resistant additive is at least 0.005 wt. % (50 ppm) to not greater than 0.01 wt. % (100 ppm). In some embodiments, an effective amount of corrosion resistant additive is at least 0.002 wt. % (20 ppm) to not greater than 0.05 wt. % (500 ppm) of each additive, where the total amount of corrosion resistant additive is not greater than 0.10 wt. % (1000 ppm).
  • an effective amount of corrosion resistant additive is not greater than 0.10 wt. % (1000 ppm), where at least some corrosion resistant additive is present. In some embodiments, an effective amount of corrosion resistant additive is not greater than 0.05 wt. % (500 ppm), where at least some corrosion resistant additive is present. In some embodiments, an effective amount of corrosion resistant additive is not greater than 0.025 wt. % (250 ppm), where at least some corrosion resistant additive is present. In some embodiments, an effective amount of corrosion resistant additive is not greater than 0.01 wt. % (100 ppm), where at least some corrosion resistant additive is present. In some embodiments, an effective amount of corrosion resistant additive is not greater than 0.005 wt.
  • an effective amount of corrosion resistant additive is not greater than 0.002 wt. % (20 ppm), where at least some corrosion resistant additive is present.
  • the corrosion resistant additive is Zn and Ga in equal amounts. In any of the foregoing embodiments, the corrosion resistant additive is Zn and Ga, with a greater amount of Zn than Ga. In any of the foregoing embodiments, the corrosion resistant additive is Zn and Ga, with a lesser amount of Zn than Ga.
  • the new aluminum alloys described herein may be formed/processed by any suitable processing method.
  • a method comprises casting the aluminum alloy (100) and then forming an aluminum electrode alloy (200) from the cast aluminum alloy.
  • the composition of the aluminum alloy may be any composition described in Section i, above.
  • the casting may be any suitable casting method.
  • the casting (100) may be continuous casting.
  • the continuous casting comprises continuous casting as described in U.S. Patent Nos. 7,823,623, 7,380,583, and 6,672,368.
  • the continuous casting comprises roll casting.
  • the continuous casting comprises belt casting.
  • the continuous casting comprises block casting.
  • the continuous casting may result in an as-cast product in the form of a strip.
  • the casting may be shape casting.
  • the shape casting comprises die casting.
  • the casting (100) may be semi-continuous casting.
  • the semi-continuous casting may be direct chill casting.
  • the direct chill casting may result in an as-cast product in the form of an ingot or billet.
  • the casting comprises additive manufacturing processes.
  • the casting step (100) comprises solidifying a melt (150) of the aluminum alloy.
  • the solidification rate of the solidifying step (150) may be any appropriate rate that facilitates achievement of a suitable amount of iron particles in the aluminum alloy.
  • “solidification rate” means the rate of cooling of a molten material (e.g. molten alloy, molten aluminum alloy), which is defined as the rate of temperature loss (in Kelvin/second) in the liquid metal immediately ahead of the solidification front.
  • molten material e.g. molten alloy, molten aluminum alloy
  • the solidification rate is sometimes deduced and/or quantified from the spacing of the secondary dendrite arms in the as-cast product.
  • the solidification rate is selected based, at least in part, on the amount of iron in solid solution, e.g. as shown in FIG. 1.
  • the amount of iron in the aluminum alloy may be related to the amount of hydrogen generated when a current is applied to an aluminum electrode alloy in an electrochemical cell.
  • the total amount of iron in the as-cast alloy is the sum of iron in solid solution and the iron contained in iron-bearing particles (“iron particles”). Iron in solid solution may contribute less to the hydrogen generation than iron particles. Thus, the presence of iron particles may be detrimental vis-a-vis hydrogen generation.
  • the cast aluminum alloy may contain iron in solid solution and/or iron particles.
  • the total amount of iron in the as-cast alloys may be determined by chemical analysis such as a Quantometer (spark source optical emission spectrometry).
  • the volume fraction of iron particles (vol. % of iron) in the as-cast alloys may be quantified by SEM analysis. The quantification process is described in detail in Example 3.
  • an as-cast aluminum alloy includes not greater than 0.03 vol. % of iron particles. In another embodiment, an as-cast aluminum alloy includes not greater than 0.02 vol. % of iron particles. In yet another embodiment, an as-cast aluminum alloy includes not greater than 0.01 vol. % of iron particles. In another embodiment, an as- cast aluminum alloy includes not greater than 0.005 vol. % of iron particles. In one embodiment, the iron particles are iron-bearing intermetallic particles. In another embodiment, the iron particles consist essentially of iron.
  • the solidification rate is at or above a threshold solidification rate, and the threshold solidification rate is sufficiently high to achieve a volume fraction of iron particles in the as-cast product of not greater than 0.03 vol. %.
  • the solidification rate is at or above a threshold solidification rate, and the threshold solidification rate is sufficiently high to achieve a volume fraction of iron particles in the as-cast product of not greater than 0.02 vol. %.
  • the solidification rate is at or above a threshold solidification rate, and the threshold solidification rate is sufficiently high to achieve a volume fraction of iron particles in the as-cast product of not greater than 0.01 vol. %.
  • the solidification rate is at or above a threshold solidification rate, and the threshold solidification rate is sufficiently high to achieve a volume fraction of iron particles in the as-cast product of not greater than 0.005 vol. %.
  • the casting process is conducted to achieve a solidification rate of at least 10 Kelvin/second (K/s). In another embodiment, the casting process is conducted to achieve a solidification rate of at least 50 K/s. In yet another embodiment, the casting process is conducted to achieve a solidification rate of at least 70 K/s. In another embodiment, the casting process is conducted to achieve a solidification rate of at least 100 K/s. In yet another embodiment, the casting process is conducted to achieve a solidification rate of at least 150 K/s. In one embodiment, the casting process is conducted to achieve a solidification rate of not greater than 200 K/s. In another embodiment, the casting process is conducted to achieve a solidification rate of not greater than 500 K/s.
  • the casting process is conducted to achieve a solidification rate of not greater than 3000 K/s. In one embodiment, the casting process is conducted to achieve a solidification rate of lOK/s to 200 K/s. In yet another embodiment, the casting process is conducted to achieve a solidification rate of 70 K/s to 200 K/s. In another embodiment, the casting process is conducted to achieve a solidification rate of 100 K/s to 200 K/s. In yet another embodiment, the casting process is conducted to achieve a solidification rate of 150 K/s to 200 K/s. In another embodiment, the casting process is conducted to achieve a solidification rate of 10 K/s to 150 K/s.
  • the casting process is conducted to achieve a solidification rate of 50 K/s to 150 K/s. In another embodiment, the casting process is conducted to achieve a solidification rate of 50 K/s to 100 K/s. In yet another embodiment, the casting process is conducted to achieve a solidification rate of 50 K/s to 75 K/s. In one embodiment, the casting process is conducted to achieve a solidification rate of 10 K/s to 3000 K/s. In one embodiment, the casting process is conducted to achieve a solidification rate is 50 K/s to 3000 K/s. In one embodiment, the casting process is conducted to achieve a solidification rate of 50 K/s to 500 K/s.
  • the as-cast product may have any suitable as-cast thickness (e.g. to achieve appropriate solidification rates (150)). Faster solidification rates may be achieved in thinner as-cast alloys.
  • the as-cast aluminum alloy comprises a thickness of at least 1 millimeter (mm).
  • the as-cast aluminum alloy comprises a thickness of at least 2 mm.
  • the as-cast aluminum alloy comprises a thickness of at least 3 mm.
  • the as-cast aluminum alloy comprises a thickness of at least 5 mm.
  • the as-cast aluminum alloy comprises a thickness of at least 10 mm.
  • the as-cast aluminum alloy comprises a thickness of at least 12 mm. In yet another embodiment, the as- cast aluminum alloy comprises a thickness of at least 15 mm. In another embodiment, the as- cast aluminum alloy comprises a thickness of at least 20 mm. In one embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 25 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 20 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 15 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 12 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 10 mm.
  • the as-cast aluminum alloy comprises a thickness of not greater than 8 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 5 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 3 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of not greater than 2 mm. In one embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 25 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 20 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 15 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 12 mm.
  • the as-cast aluminum alloy comprises a thickness of 1 to 10 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 8 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 5 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 3 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of 1 to 2 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 2 to 25 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of 3 to 25 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 5 to 25 mm.
  • the as-cast aluminum alloy comprises a thickness of 10 to 25 mm. In another embodiment, the as-cast aluminum alloy comprises a thickness of 12 to 25 mm. In yet another embodiment, the as-cast aluminum alloy comprises a thickness of 15 to 25 mm. In another embodiment, the as-cast aluminum electrode alloy comprises a thickness of 20 to 25 mm .
  • the cast aluminum alloy may be formed into an aluminum electrode alloy (200). In one embodiment, the forming may comprise working of the as-cast alloy. In one embodiment, due to the working, the formed aluminum electrode alloy may comprise a wrought microstructure. In one embodiment, the working may include rolling. In one embodiment, the rolling may include hot and/or cold rolling.
  • the rolled product is a sheet. In another embodiment, the rolled product is a foil. In yet another embodiment, the rolled product is a plate.
  • the working may include extruding. In another embodiment, the working may include forging. In one embodiment, the working may comprise free form forging, also known as open die forging. In one embodiment, the forming may include solution heat treatment.
  • the method may comprise producing the final product form (300).
  • the producing (300) may comprise machining.
  • the producing (300) may comprise cutting.
  • the producing (300) may comprise stamping.
  • the producing (300) comprises producing disc.
  • the producing (300) comprises producing a block.
  • an aluminum alloy may be selected (50) from one of the previously described aluminum alloy compositions.
  • An appropriate aluminum alloy may be selected, e.g. to achieve a low volume fraction of iron particles.
  • a user may predetermine an aluminum alloy composition prior to the selecting step (50).
  • phosphorous in combination with effective amounts of corrosion resistant additives (e.g. Zn and/or Ga) in aluminum alloys will provide improved corrosion resistance (e.g. reduced corrosion), as compared to aluminum alloys that do not have phosphorous and effective amounts of corrosion resistant additives (e.g. Zn and/or Ga).
  • improved corrosion resistance of an electrode in an electrochemical cell may be realized during a wide range of electrochemical cell operating conditions (e.g. temperature and current efficiency).
  • using phosphorous in combination with effective amounts of corrosion resistant additives (e.g. Zn and/or Ga) will provide significant improvement to corrosion resistance at electrochemical cell operating conditions of high corrosion (e.g. low current densities and/or low temperatures) over aluminum alloys without phosphorous and effective amounts of corrosion resistant additives (e.g. Zn and/or Ga).
  • FIG. 1 is a schematic view of an example of an electrochemical cell that is configured for use in evaluating the corrosion of electrodes in an electrolyte in accordance with the present disclosure.
  • FIG. 2 is a graph showing the hydrogen generation for various Example 1 low iron alloys.
  • FIG. 3 is a graph showing the hydrogen generation for various Example 1 medium iron alloys.
  • FIG. 4 is a flow chart illustrating one embodiment of the processing steps for producing an aluminum electrode alloy.
  • FIG. 5 is a flow chart illustrating another embodiment of the processing steps for producing an aluminum electrode alloy.
  • Aluminum electrode alloys having the compositions shown in Table 1, were cast as ingots, rolled to the desired thickness, and machined into disks (samples) having the desired thickness and a diameter, with a sufficient cross-sectional surface area to provide a viable testing surface for immersion into an electrochemical cell, schematically depicted in FIG. 1.
  • Two general categories of samples were tested: low-iron samples (e.g. ⁇ 0.002 wt. % or ⁇ 20 ppm iron, Control 1 and Alloys 1-3) and medium-iron samples (about 0.02 wt. % or 200 ppm iron, Control 2 and Alloys 4-5). All samples included about 2.5 wt. % Mg.
  • Controls 1-2 and Alloys 1-5 were tested for hydrogen generation via an electrochemical cell system (schematically depicted in FIG. 1).
  • the electrochemical cell consisted of a counter electrode and an aluminum electrode (anode) alloy (the control or sample) submerged in an aqueous electrolyte.
  • the electrochemical cell was equipped with a mass-flow meter for measuring hydrogen gas evolved from the aluminum electrode alloy product. Current was applied to the electrochemical cell and hydrogen was measured to quantify corrosion.
  • Control 1 generated 1153 cm 3 of hydrogen. Alloy 1 generated 1628 cm 3 of hydrogen. Both Alloys 2 and 3 generated significantly less hydrogen at 370 cm 3 and 313 cm 3 . There was a significant improvement in hydrogen generation over the control when Zn and Ga are added to the low- iron alloy (Alloy 2). There was even further improvement, and the lowest hydrogen generated of all samples, with the addition of Zn, Ga and P to the low-iron alloy (Alloy 3). There was no improvement, and in fact, hydrogen generation increased with the addition of only phosphorous to the low-iron alloy (Alloy 1).
  • Control 2 generated 2728 cm 3 .
  • Alloys 4 and 5 both generated less hydrogen than the control at 2673 cm 3 and 2621 cm 3 , respectively.
  • Adding phosphorous (Alloy 4) to the medium -iron alloy resulted in some improvement over the control, while the addition of Zn, Ga and P (Alloy 5) resulted in the largest improvement over the control.

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Abstract

L'invention concerne une composition d'alliage d'aluminium. La composition d'alliage d'aluminium comprend une quantité efficace d'un additif résistant à la corrosion, et une quantité efficace de phosphore ; l'additif résistant à la corrosion et le phosphore étant présents dans des quantités suffisantes destinés à fournir un alliage d'électrode en aluminium doté d'une résistance à la corrosion améliorée par rapport à un alliage d'électrode en aluminium sans additif résistant à la corrosion de ce type ni phosphore, lorsqu'il est mesuré conformément à un test de cellule électrochimique.
PCT/US2019/049661 2018-09-17 2019-09-05 Alliage d'aluminium résistant à la corrosion Ceased WO2020060763A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04213810A (ja) * 1990-12-11 1992-08-04 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH11117077A (ja) * 1997-10-15 1999-04-27 Nippon Steel Corp 耐糸錆性に優れたＭｇ含有アルミニウム合金処理板
JP2007302982A (ja) * 2006-05-15 2007-11-22 Nippon Steel Corp 昇温特性、加工性、塗装後耐食性に優れたホットプレス用Ａｌめっき鋼材
JP2007308805A (ja) * 2002-05-07 2007-11-29 Nippon Foil Mfg Co Ltd アルミニウム合金箔及びその製造方法
US20170327930A1 (en) * 2014-10-31 2017-11-16 Uacj Corporation Aluminum alloy substrate for magnetic disk

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04213810A (ja) * 1990-12-11 1992-08-04 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH11117077A (ja) * 1997-10-15 1999-04-27 Nippon Steel Corp 耐糸錆性に優れたＭｇ含有アルミニウム合金処理板
JP2007308805A (ja) * 2002-05-07 2007-11-29 Nippon Foil Mfg Co Ltd アルミニウム合金箔及びその製造方法
JP2007302982A (ja) * 2006-05-15 2007-11-22 Nippon Steel Corp 昇温特性、加工性、塗装後耐食性に優れたホットプレス用Ａｌめっき鋼材
US20170327930A1 (en) * 2014-10-31 2017-11-16 Uacj Corporation Aluminum alloy substrate for magnetic disk

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