EP3825444A1 - Metallische beschichtung und anwendungsverfahren - Google Patents

Metallische beschichtung und anwendungsverfahren Download PDF

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Publication number
EP3825444A1
EP3825444A1 EP20208879.5A EP20208879A EP3825444A1 EP 3825444 A1 EP3825444 A1 EP 3825444A1 EP 20208879 A EP20208879 A EP 20208879A EP 3825444 A1 EP3825444 A1 EP 3825444A1
Authority
EP
European Patent Office
Prior art keywords
mixture
solvent
electroplating
substrate
eutectic point
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
EP20208879.5A
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English (en)
French (fr)
Inventor
Weilong Zhang
Weina LI
Georgios S. Zafiris
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.)
Hamilton Sundstrand Corp
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Hamilton Sundstrand Corp
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Filing date
Publication date
Application filed by Hamilton Sundstrand Corp filed Critical Hamilton Sundstrand Corp
Publication of EP3825444A1 publication Critical patent/EP3825444A1/de
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

  • Metallic coatings are applied to substrates to protect the substrate.
  • the metallic coatings can provide corrosion resistance, high temperature oxidation resistance, protection from mechanical damage (e.g., scratching) or other protections for the substrate.
  • Metallic coatings, and in particular refractory metal coatings that comprise high entropy alloys (HEAs) are typically applied to substrates in a very limited variety of ways, including ball milling and sintering, arc induction plasma melting, plasma spray, or laser cladding.
  • HSAs high entropy alloys
  • Some metallic coatings can be applied to non-line-of-sight surfaces by electroplating.
  • electroplating requires the preparation of a solution containing metallic cations dissolved in a carrier liquid. An electrical current is applied to the solution to deposit the metallic cations into a substrate. Preparing such an aqueous solution for electrodeposition of HEA is difficult and expensive, and leads to poor coating structure and low current efficiencies due to the high rate of hydrogen reduction and evolution at the substrate cathode, which makes electrodepositon of refractory HEA from such an aqueous solution difficult and impractical.
  • a method of depositing a metallic coating onto a substrate according to an example of this disclosure includes or comprises mixing metallic salts of one or more elements with a solvent to form a mixture (e.g. a mixture comprised in a solution for electroplating as disclosed herein), heating the mixture to form a liquid, such that constituents of the mixture are in a mobile ionic state, and electroplating the metallic salts onto a substrate from the liquid.
  • a mixture e.g. a mixture comprised in a solution for electroplating as disclosed herein
  • the mixture has a eutectic point that is lower than about 100°C.
  • the heating is to a temperature at or near the eutectic point.
  • the heating is to a temperature that is between the eutectic point and a temperature 10°C above the eutectic point.
  • the eutectic point is between about 10°C and 100°C.
  • one or more elements include one or more refractory metals.
  • one or more elements includes at least one of zirconium, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, and hafnium, and combinations thereof.
  • one or more elements includes at least one metal selected from the group of zirconium, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, and hafnium.
  • one or more elements includes at least one of zirconium, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, and hafnium.
  • the substrate is a component of a gas turbine engine.
  • the substrate includes at least one non-line-of-sight surface.
  • the electroplating is on the at least one non-line-of-sight-surfaces.
  • the liquid is free from water.
  • the solvent is selected from the group of ionic liquids and deep eutectic solvents.
  • the solvent is a deep eutectic solvent, and incudes at least one of choline chloride with urea, ethylene glycol, glycerol, and malonic acid.
  • a solution for electroplating according to an example of this disclosure includes or comprises a mixture of metallic salts of one or more refractory metal elements and a solvent, wherein the mixture has a eutectic point below about 100°C.
  • the eutectic point is between about 10°C and 100°C.
  • the refractory metal elements include at least one of zirconium, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, and hafnium, and combinations thereof.
  • the refractory metal elements include at least one metal selected from the group of zirconium, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, and hafnium.
  • the mixture is free from water.
  • the solvent is selected from the group of ionic liquids and deep eutectic solvents.
  • Metallic coatings can be applied to substrates in order to protect the substrates from high temperatures, corrosion, mechanical damage, or other conditions.
  • metallic coatings are applied to substrates, such as gas turbine engine components, to provide high temperature resistance for the substrates.
  • Figure 1 shows an example cross section of a substrate 10 having a coating 12. The coating has a thickness t.
  • Metallic coatings can be alloys of multiple metals.
  • One example type of metallic coating is a high entropy alloy (HEA).
  • HEAs typically include four or more metallic elements in relatively high proportions, e.g., the four or more metallic elements each comprise higher than trace amounts of the HEA.
  • one or more of the elements is a refractory metal.
  • a refractory metal HEA coating example comprises at least one of niobium, molybdenum, tantalum, tungsten, rhenium, and combinations thereof.
  • Another refractory HEA coating example comprises at least one of zirconium, niobium, titanium, tantalum, hafnium, and combinations thereof.
  • Yet another example of a refractory metals HEA coating comprises at least one of niobium, molybdenum, tantalum, tungsten, rhenium, zirconium, hafnium, titanium, and combinations thereof.
  • Electroplating is generally known in the art. Essentially, electroplating includes dissolving metallic cations in a carrier liquid to form a solution. The solution is then applied to the substrate, and an electrical current is applied to the solution and substrate. The electrical current causes the metallic cations to deposit onto the substrate, forming a coating on the substrate. Electroplating can be used to apply coatings to non-line-of-sight surfaces, such as internal cooling passages of a component. For instance, the component can be submerged in the solution, which infiltrates the component to the non-line-of-sight surfaces. The metallic cations can then be electroplated onto the component.
  • non-line-of-sight surfaces such as internal cooling passages of a component. For instance, the component can be submerged in the solution, which infiltrates the component to the non-line-of-sight surfaces.
  • the metallic cations can then be electroplated onto the component.
  • FIG. 2 shows an example method 100 of electroplating a metallic coating 12, such as an HEA metal coating, onto a substrate 10.
  • a refractory metal HEA coating is an exemplary case of the above.
  • salts of one or more metallic elements such as a refractory metals
  • a solvent to form a mixture.
  • the resulting mixture is a low temperature eutectic mixture (i.e., the mixture has a lower melting point than its individual components).
  • Example solvents are deep eutectic solvents (DESs) or ionic liquids.
  • Example ionic liquids are imidazolium, pyridinium, and quaternary ammonium salts.
  • DESs are eutectic mixtures of two or more components, typically consisting of a hydrogen-bond acceptor (HBA), for example a quaternary ammonium halide salt, and a hydrogen-bond donor (HBD).
  • HBA hydrogen-bond acceptor
  • HBD hydrogen-bond donor
  • DESs include eutectic mixtures of choline chloride with urea, ethylene glycol, glycerol, malonic acid, or other hydrogen bond donor species of amides, alcohols or carboxylic acids, respectively.
  • the mixture is heated to a temperature at or near its eutectic point to melt it (e.g., form a liquid).
  • the mixture is heated to a temperature between the eutectic point and about 10°C above the eutectic point.
  • the eutectic point of the salt mixture is below 100°C.
  • the eutectic point is between about 10°C and 100°C. Because the eutectic point is on the order of room temperature, the mixture can be heated easily and inexpensively by any known means.
  • the heating causes the constituent chemical species to exist in the liquid in a mobile ionic state (e.g., a liquid that includes ionic assemblies of the metallic salts (cations) and anions).
  • the liquid mixture is free from water.
  • the metal salts and solvents from step 102 are selected so that the liquid in step 104 is free from water.
  • the metal salts (such as refractory metal cations, in one example) in the liquid mixture are electroplated onto the substrate 10 as generally discussed above and known in the art to form the coating 12 on the substrate 10.
  • the electroplating can be any known type of electroplating, including pulsed electroplating and potentiostatic electroplating. In potentiostatic electroplating, the electrical current remains constant through the process. In pulsed electroplating, the electrical current is periodically raised and lowered between high and low values, and the polarity can also be momentarily reversed, to control the composition and thickness t of the resulting coating 12.
  • Refractory metals in particular were previously difficult to electroplate because the refractory metals have very high melting points.
  • Creating a low eutectic point liquid with constituents including the desired refractory metals as discussed above greatly reduces the heating required to melt the mixture and form the liquid for electroplating the desired metallic composition onto the substrate 10 of choice, as discussed above. Therefore, the above-described method allows for the relatively simple and inexpensive electro-deposition of metallic coatings such as HEAs containing one or more refractory metals onto substrates, including on non-line-of-sign surfaces.
  • the reduction half-reaction for refractory metal cations generally involves very high potential as compared to other metals like nickel, zinc, etc. This means that if the carrier liquid includes water, the reaction system will tend towards the electrolysis of water, which reaction has a much lower potential than the electroplating reaction for other metals. This in turn produces hydrogen, which is detrimental to the properties of the substrate metal (e.g. hydrogen embrittlement).
  • the electroplating efficiency e.g., amount of metallic coating deposited on the substrate over time
  • very high voltages would be required to be applied to create the electrical current to drive the electroplating.
  • the above-described method includes a liquid including refractory metal that is free from water and can be used for electrodeposition. Accordingly, by using the above described method with a water-free liquid, electroplating of refractory metals and metal alloys becomes possible.
  • plasma deposition of refractory metal alloys would create different surface morphologies and potentially compositions compared to electrodeposited coatings via the method described in the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
EP20208879.5A 2019-11-22 2020-11-20 Metallische beschichtung und anwendungsverfahren Pending EP3825444A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US16/691,917 US20210156041A1 (en) 2019-11-22 2019-11-22 Metallic coating and method of application

Publications (1)

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EP3825444A1 true EP3825444A1 (de) 2021-05-26

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411125A (zh) * 2021-12-21 2022-04-29 苏州大学 一种高熵金属氧化物涂层及其制备方法与应用
CN115925423A (zh) * 2022-11-21 2023-04-07 中国科学院兰州化学物理研究所 一种高性能单相自润滑高熵陶瓷材料及其制备方法
WO2024016268A1 (zh) * 2022-07-21 2024-01-25 深圳先进技术研究院 一种高熵合金电极、制备方法、气体传感器及其应用

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* Cited by examiner, † Cited by third party
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CN115305444B (zh) * 2022-07-06 2023-09-05 成都理工大学 锆合金基耐高温水腐蚀的AlCrNbTiZr高熵合金涂层及其制备方法

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US20120052324A1 (en) * 2010-08-30 2012-03-01 Honda Motor Co., Ltd. Electric Al-Zr-Mn Alloy-Plating Bath Using Room Temperature Molten Salt Bath, Plating Method Using the Same and Al-Zr-Mn Alloy-Plated Film
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US20180087175A1 (en) * 2016-08-08 2018-03-29 Seagate Technology Llc Method of forming one or more metal and/or metal alloy layers in processes for making tranducers in sliders, and related sliders

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US20120052324A1 (en) * 2010-08-30 2012-03-01 Honda Motor Co., Ltd. Electric Al-Zr-Mn Alloy-Plating Bath Using Room Temperature Molten Salt Bath, Plating Method Using the Same and Al-Zr-Mn Alloy-Plated Film
EP2465977A1 (de) * 2010-12-16 2012-06-20 Honeywell International, Inc. Verfahren zur Herstellung einer oxidationsbeständigen Hochtemperaturbeschichtung auf Superlegierungssubstraten und auf diese Weise hergestellte beschichtete Superlegierungssubstrate
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411125A (zh) * 2021-12-21 2022-04-29 苏州大学 一种高熵金属氧化物涂层及其制备方法与应用
CN114411125B (zh) * 2021-12-21 2023-02-21 苏州大学 一种高熵金属氧化物涂层及其制备方法与应用
WO2024016268A1 (zh) * 2022-07-21 2024-01-25 深圳先进技术研究院 一种高熵合金电极、制备方法、气体传感器及其应用
CN115925423A (zh) * 2022-11-21 2023-04-07 中国科学院兰州化学物理研究所 一种高性能单相自润滑高熵陶瓷材料及其制备方法
CN115925423B (zh) * 2022-11-21 2023-07-18 中国科学院兰州化学物理研究所 一种高性能单相自润滑高熵陶瓷材料及其制备方法

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