EP3399072B1 - Verfahren zur herstellung eines aluminiumbeschichteten metalls - Google Patents

Verfahren zur herstellung eines aluminiumbeschichteten metalls Download PDF

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Publication number
EP3399072B1
EP3399072B1 EP18159986.1A EP18159986A EP3399072B1 EP 3399072 B1 EP3399072 B1 EP 3399072B1 EP 18159986 A EP18159986 A EP 18159986A EP 3399072 B1 EP3399072 B1 EP 3399072B1
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EP
European Patent Office
Prior art keywords
metal substrate
aluminum
anode
substrate
liquid electrolyte
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EP18159986.1A
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English (en)
French (fr)
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EP3399072A1 (de
Inventor
Lei Chen
Dean Nguyen
Xiaomei Yu
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Sikorsky Aircraft Corp
Hamilton Sundstrand Corp
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Sikorsky Aircraft Corp
Hamilton Sundstrand Corp
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Publication of EP3399072A1 publication Critical patent/EP3399072A1/de
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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
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • 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

Definitions

  • Metal plating such as cadmium plating has been widely used on various materials, including but not limited to high-strength steel, aircraft components, fasteners, electrical connectors, and numerous others. Metal plating can be used to promote properties such as corrosion resistance, lubricity, and electrical conductivity. Cadmium has been used as a metal plating material for various reasons such as the cost of plating and its anti-galling performance (no adhesive wear on threaded surfaces). However, continued commercial uses of cadmium have been facing pressure due to health concerns in recent years, including being listed as a substance of very high concern (SVHC) in 2012 by the European Union environment & safety regulatory agency REACH.
  • SVHC very high concern
  • metal plating technologies have been developed and evaluated over the years.
  • aluminum has been proposed as a metal plating material, and has been approved for corrosion protection of high-strength structural steels in aircraft as set forth in specifications such as MIL-DTL-83488.
  • various technical issues continue to present challenges.
  • Commercially available aluminum metal plating processes utilize toxic or environmentally unfriendly organic solvents and pyrophoric alkylaluminum compounds that require extra measures for operation under inert conditions. Therefore, there continues to be a need for further developments regarding aluminum metal coatings.
  • High strength steels are used throughout aerospace industries for components such as aircraft landing gear, bolts, aircraft tail hooks on aircraft carriers etc. High strength steels are protected by sacrificial coatings such as electroplated cadmium, zinc-nickel and non-electrolytic aluminum-based SermeTel (Praxair Surface Technologies) coatings. It has been known that HSS are prone to hydrogen embrittlement representing brittle mechanical failures under stress that is manifested by brittle intergranular fracture and trans-granular cleavage. Incorporation of hydrogen during either the electroplating process or the corrosion during service promotes the increased risk of failure arising from hydrogen embrittlement.
  • Porous electroplated coatings can allow hydrogen to be released from the steel substrates via a post-plating baking process.
  • substrates coated with porous coatings can become susceptible to re-embrittlement due to galvanic cells formed on exposed area.
  • Dense coatings of lower porosity can mitigate the risk of hydrogen re-embrittlement; however, dense coatings can prevent hydrogen from being released.
  • Hydrogen embrittlement can also be caused by pre-treatment processes for of HSS, such as treatment with acids or electrolytic cathodic cleaning which can generate hydrogen.
  • Method plating technologies are taught in CN105200476 , US 2012/031766 , EP 2 492 376 , US 2016/319449 and ABBOTT, A.P.
  • An article, made according to the method comprises a metal substrate and a layer thereon comprising aluminum.
  • the layer comprising aluminum has a volumetric density greater than 99%, and the coated article meets or exceeds hydrogen embrittlement test requirements of ASTM F519-10.
  • FIG. 1 schematically depicts a cross-sectional view of a coated article 10 comprising a substrate 12 having thereon a surface layer 14 comprising aluminum.
  • the substrate 12 can comprise high strength steels that are particularly prone to hydrogen embrittlement due to lack of corrosion resistance and facile hydrogen diffusion in the steel lattice.
  • the substrate 12 comprises a metal or metal alloy having a first oxidation-reduction equilibrium (corrosion) potential more noble than aluminum and aluminum alloys. This difference in potential can allow the layer to provide sacrificial corrosion protection in an electrolyte that is experienced in the service environment where the parts are used.
  • the metal or metal alloy of substrate 12 has an electrode potential of -1.0 V to 0 V with respect to saturated calomel electrode (SCE) in 3.5% wt. sodium chloride solution or sea water solution or synthetic sea water solution, more specifically -0.6 to -0.1, and even more specifically from -0.4 V to -0.2 V.
  • SCE saturated calomel electrode
  • metals or metal alloys for the substrate 12 include but are not limited to high-strength steels (e.g., D6AC, 300M, M-50, AERMET 100, 4330, 4340, 52100).
  • the substrate 12 comprises a high strength low alloy (HSLA) steel as that term is defined by SAE (Society of Automotive Engineers) standards.
  • SAE Society of Automotive Engineers
  • the thickness of layer 14 can be specified to meet target specifications.
  • the layer 14 has a thickness in a range having a low end of 2.5 ⁇ m (0.0001 inches), more specifically 7.5 ⁇ m (0.0003 inches), and even more specifically 12.5 ⁇ m (0.0005 inches), and an upper end of 17.5 ⁇ m (0.0007 inches), more specifically 25 ⁇ m (0.001 inches), and even more specifically 250 ⁇ m (0.010 inches).
  • the above range endpoints can be independently combined to serve as a disclosure of a number of different ranges, which are hereby expressly disclosed.
  • the layer 14 can be utilized to promote resistance to corrosion.
  • the layer 14 can be utilized to promote resistance to galling along contact portions of the article.
  • the layer 14 can be disposed on surface to be subjected to sliding contact with another article or component.
  • articles can include, but are not limited to, threaded fasteners, press-fit connections, propeller barrels, electrical connectors, press-fit high strength steel bolts used in turboprop propellers, and other various fasteners or connectors.
  • articles such as shown in FIG. 1 can be prepared by methods shown in FIGS. 2 (not according to the present invention) and 3.
  • the surface of the substrate 12 can optionally be subjected to physical surface preparation such as degreasing, grit blasting, or both degreasing and grit blasting as shown in FIGS. 2 and 3 .
  • degreasing agents include organic solvents such as acetone or methyl ethyl ketone, alkaline degreasers such as aqueous solutions of sodium hydroxide, potassium hydroxide, or ammonia, or aqueous surfactants with degreasing capability.
  • the substrate can optionally be dried such as by radiant heat or blowing with air.
  • Grit blasting can be performed by directing abrasive particles at the substrate at velocities of 50 to 100 in/min.
  • materials for grit blasting include alumina grit, silicon carbide grit, steel grit, or glass particles.
  • the particles for grit blasting can have particle sizes expressed as mean diameter and distribution as described in ANSI B74.12-2001.
  • the substrate is subjected to anodic alkaline electrolytic treatment.
  • This treatment involves disposing the metal substrate as an anode in an electrolytic circuit comprising an aqueous alkaline liquid electrolyte, and applying an electrical voltage differential between the metal substrate anode and a cathode.
  • Conditions for anodic alkaline electrolytic treatment can be controlled to promote formation of oxygen at the metal substrate surface according to the reaction 40H - ⁇ 2H 2 O + O 2 and to minimize formation of metal oxide at the metal surface substrate.
  • the formation of oxygen at the metal substrate surface can promote cleaning of the metal substrate surface.
  • the alkaline electrolyte can comprise aqueous solutions of alkaline compounds such as sodium hydroxide, potassium hydroxide, and their weak acid salts such as Na 2 CO3, Na 3 PO 4 , Na 2 SiO 4 at concentrations in a range having a lower end of 15 wt.%, 10 wt.%, or 5 wt.%, and an upper end of 50 wt.%, 75 wt.%, or 100 wt.%.
  • Commercial alkaline cleaning products such as Henkel Turco 4181 can be used as well.
  • the above range endpoints can be independently combined to serve as a disclosure of a number of different ranges, each of which is hereby expressly disclosed.
  • the alkaline electrolyte can have a pH in a range having a lower end of 9, 8, or 7.5, and an upper end of 14.
  • the above range endpoints can be independently combined to serve as a disclosure of a number of different ranges, each of which is hereby expressly disclosed.
  • the alkaline electrolyte can be at a temperature in a range having a lower end of 25°C and an upper end of 50°C.
  • the voltage differential applied between the cathode and the metal substrate anode can provide an electrical current density (based on anode surface area) between the cathode and anode in a range having a lower end of 5 mA/cm 2 , 10 mA/cm 2 , or 15 mA/cm 2 , and an upper end of 25 mA/cm 2 , 50 mA/cm 2 , or 75 mA/cm 2 , and can be applied for a duration in a range having a lower end of 15 seconds, 30 seconds, or 60 seconds, and an upper end of 120 seconds, 180 seconds, or 300 seconds.
  • the above range endpoints can be independently combined to serve as a disclosure of a number of different ranges, each of which is hereby expressly disclosed.
  • the current can be pulsed or varied.
  • Other conditions e.g., temperature
  • the metal substrate can be rinsed with deionized water and dried in nitrogen or air.
  • the anodic alkaline electrolytically-treated metal substrate is further subjected to an anodic ionic liquid electrolytic treatment.
  • This treatment involves disposing the metal substrate as an anode in an electrolytic circuit comprising a liquid electrolyte that comprises an ionic liquid, and applying an electrical voltage differential between the metal substrate anode and a cathode to induce current.
  • this treatment can etch the surface of the metal substrate, which can promote release of metal oxide from the surface.
  • the ionic liquid electrolyte can be at a temperature in a range having a lower end of 25°C, 40°C, or 55°C, and an upper end of 60°C, 70°C, or 80°C.
  • the voltage differential applied between the cathode and the metal substrate anode can be set to produce a current density (based on anode surface area) in a range having a lower end of 5 mA/cm 2 , 10 mA/cm 2 , or 15 mA/cm 2 , and an upper end of 20 mA/cm 2 , 30 mA/cm 2 , or 40 mA/cm 2 , and can be applied for a duration in a range having a lower end of 15 seconds, 30 seconds, or 45 seconds, and an upper end of 60 seconds, 120 seconds, or 300 seconds.
  • the voltage can be pulsed or varied.
  • Other conditions e.g., temperature
  • the metal substrate can be rinsed (e.g., with methanol, ethanol, deionized water, or a combination of rinsing agents) and dried (e.g., with heat or blown air), or can remain in the ionic liquid electrolyte for further processing.
  • the anodic ionic liquid electrolytically-treated metal substrate is subjected to sonicating treatment in the same or a different electrolyte bath.
  • anodic etching treatment of steel substrates in ionic liquids can produce smut on the substrate, which can interfere with the subsequent aluminum plating process, leading to poor coating quality.
  • Sonicating the parts can be conducted in ionic liquids or in water-free organic solvents such as ethanol, toluene, acetone, etc.
  • sonic treatment can promote the removal of smut or other substances that may have been formed on the surface by the treatment process or are otherwise disposed on the surface.
  • sonicating treatment can involve exposure of the metal substrate to sonic energy in a frequency range having a lower end of 10 kHz and an upper end of 200 kHz. In some embodiments, the sonic treatment can be applied for a duration in a range having a lower end of 30 seconds and an upper end of 300 seconds. In some embodiments, the sonic energy can be pulsed or varied.
  • a layer comprising aluminum is deposited onto the treated metal substrate by disposing the metal substrate as a cathode in an electrolytic circuit comprising a liquid electrolyte that comprises an ionic liquid and an aluminum salt, and applying an electrical voltage differential between the metal substrate and an anode.
  • ionic liquid means a salt having a melting point below the processing temperature (e.g., below 100°C). In some embodiments, the ionic liquid is non-volatile or of low volatility at the process temperature. Cations for the ionic liquid used as electrolyte for cathodic electrodeposition of aluminum shown in FIGS. 2 and 3 , as well as for the anodic electrolytic treatment shown in FIG.
  • 3 can include, but are not limited to imidazolium (e.g., 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium (“BMI”), 1-hexyl-3-methyl-imidazolium (“HMI”), pyridinium (e.g., N-methylpyridinium), tetraalkylammonium, pyrrolidinium (e.g., 1-butyl-1-methyl-pyrrolidinium (“BMPyr”), trialkylsulfonium (e.g., triethylsulfonium), pyrazolium, triazolium, thiazolium, oxazolium, pyridazinium, pyrimidinium, pyrazinium.
  • imidazolium e.g., 1-ethyl-3-methylimidazolium, 1-ethyl-2,3
  • Exemplary anions for ionic liquids used in the embodiments described herein include, but are not limited to, chloroaluminate (Al 2 Cl 7 - ), tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), trifluoromethanesulfonate (CF 3 SO 3 ), bis(trifluoromethylsulfonyl)imide, trifluoroethanoate, nitrate, SCN, HSO 4 , HCO 3 , CH 3 SO 3 , CH 3 CH 2 SO 4 , (CH 3 (CH 2 ) 3 O) 2 POO, (CF 3 SO 2 ) 2 N, dicyanamide, (CF 3 CF 2 SO 2 ) 2 N, L-(+)-lactate, CH 3 SO 4 , and CH 3 COO, and the like.
  • chloroaluminate Al 2 Cl 7 -
  • BF 4 tetrafluoroborate
  • PF 6 hexafluorophosphate
  • the ionic liquid has a cation that is an imidazolium, and more specifically the ionic liquid has the formula: wherein, R and R 1 are independently selected from H, an unsubstituted or substituted alkyl group having 1 to 30 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 30 carbon atoms.
  • X is an anionic group, as described hereinabove, that associates with imidazolium to form an ionic-liquid cation/anion pair.
  • the liquid electrodeposition composition for depositing the layer comprising aluminum also comprises an aluminum salt.
  • Aluminum salt can be introduced to the composition in the form of aluminum chloride (AlCl 3 ), but will tend to form different aluminum-containing ions in the ionic liquid composition, including but not limited to AlCl 4 - (tetrachloroaluminate) or Al 2 Cl 7 - (heptachlorodialuminate).
  • Aluminum-containing anions can also be introduced electrolytically by electrochemical reaction of metallic aluminum in the anode(s) of an electrochemical cell of which the electrodeposition forms a part.
  • the electrodeposition composition can also include additives to improve the integrity of the aluminum coating such as a nucleation aid like a surfactant.
  • additives are known in the art, see, e.g., US 2012/0006688 A1 , and can be included as well.
  • Organic solvents can also be present in amounts up to 30 wt. %, such as toluene, chlorobenzene, dichlorobenzenes, xylene, cyclohexane, heptane, and others.
  • process conditions for deposition of the layer comprising aluminum can be managed to promote targeted results such as density of the aluminum layer as described in more detail below.
  • an electrical current is provided by a power source that is sufficient to provide an electric current density (current per effective electrode area) of at least 5 mA/cm 2 , more specifically of at least 10 mA/m 2 , even more specifically at least 20mA/cm 2 , and even more specifically at least 30 mA/cm 2 .
  • Current is applied until the desired aluminum coating layer thickness is achieved (e.g., 5 ⁇ m to 50 ⁇ m).
  • the electrodeposition method can be carried out at temperatures ranging from 20°C. to 100° C., more specifically from 20° C. to 80° C., and even more specifically from 60° C. to 70° C.
  • the above range endpoints can be independently combined to serve as a disclosure of a number of different ranges, each of which is hereby expressly disclosed.
  • the above-described methods can avoid conditions that can contribute to hydrogen embrittlement of the substrate 12.
  • the above-described electrolytic treatment of the substrate 12 as an anode in aqueous alkaline electrolyte can evolve oxygen at the surface of the metal substrate that can promote cleaning of the surface before electrolytic deposition of aluminum in an ionic liquid electrolyte.
  • Cathodic electrocleaning in an acidic electrolyte would evolve hydrogen at the surface of the metal substrate that could contribute to the promotion of hydrogen embrittlement of the substrate 12.
  • Hydrogen embrittlement of the substrate 12 can be managed by post-fabrication heat treatment to drive hydrogen out of the substrate, but the effectiveness of such post-fabrication heat treatment can be limited in the case of dense aluminum overlayers, which can inhibit removal of hydrogen from the substrate.
  • the above-described methods can avoid conditions that contribute to hydrogen embrittlement, thereby allowing for deposition of higher density aluminum layers (i.e., volumetric density greater than 99%).
  • the methods described herein don't require baking after the coating is applied to the substrate.
  • the coated article meets or exceeds requirements of the hydrogen embrittlement test as prescribed in ASTM F519-10. As used herein, the coated article meets or exceeds these requirements if the article passes the sustained load test of ASTM F519-10 of greater than 200 hours at 75% of the notch fracture strength.
  • the layer 14 can be treated with a trivalent chromium passivation process.
  • a trivalent chromium passivation process can be carried out by treatment of the layered substrate (e.g., by dipping or application with a brush, sponge, spray, or other coating applicator) with an aqueous solution or non-aqueous solution comprising trivalent chromium and various anions.
  • exemplary anions include nitrate, sulfate, phosphate, and/or acetate.
  • Specific exemplary trivalent chromium salts can include Cr 2 (SO 4 ) 3 , (NH) 4 Cr(SO 4 ) 2 , KCr(SO 4 ) 2 , CrF 3 Cr(NO3) 3 , and mixtures comprising any of the foregoing.
  • compositions and the application thereof to substrates are described in US Patent Nos. 5,304,257 , 5,374,347 , 6,375,726 , 6,511,532 , 6,521,029 , and 6,511,532 .
  • Various additives and other materials can be included in the composition comprising trivalent chromium as disclosed in the patent literature, and the trivalent chromium salt composition can be selected from any of a number of known commercially-available compositions.

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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)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (4)

  1. Verfahren zur Beschichtung eines Metallsubstrat, das Stahl umfasst, wobei das Verfahren Folgendes umfasst
    Anordnen des Metallsubstrats (12) als eine Anode in einem elektrolytischen Kreislauf, der einen wässrigen alkalinen Flüssigelektrolyt umfasst, und Anlegen eines elektrischen Spannungsdifferenzials an das Metallsubstrat und eine Kathode; Anordnen des anodischen alkalinen elektrolytisch behandelten Metallsubstrats als eine Anode in einem elektrolytischen Kreislauf, der einen Flüssigelektrolyt umfasst, der eine ionische Flüssigkeit umfasst, und Anlegen eines elektrischen Spannungsdifferenzials an das Metallsubstrat und eine Kathode; Unterziehen des anodischen ionischen elektrolytisch behandelten Metallsubstrats einer Ultraschallreinigung; und
    Anordnen des ultraschallgereinigten Metallsubstrats als eine Kathode in einem elektrolytischen Kreislauf, der einen Flüssigelektrolyt umfasst, der eine ionische Flüssigkeit und ein Aluminiumsalz umfasst, und Anlegen eines elektrischen Spannungsdifferenzials an das Metallsubstrat und eine Anode, um eine Schicht (14) auszubilden, die Aluminium auf dem Metallsubstrat umfasst.
  2. Verfahren nach Anspruch 1, ferner umfassend Entfetten des Metallsubstrats vor dem Anordnen in dem wässrigen alkalinen Flüssigelektrolyt.
  3. Verfahren nach Anspruch 1 oder 2, ferner umfassend Kiesstrahlen des Metallsubstrats vor dem Anordnen in dem wässrigen alkalinen Flüssigelektrolyt.
  4. Verfahren nach einem der Ansprüche 1-3, wobei der elektrolytische Kreislauf, der einen Flüssigelektrolyt umfasst, der eine ionische Flüssigkeit und ein Aluminiumsalz umfasst, eine Aluminiumanode beinhaltet.
EP18159986.1A 2017-05-05 2018-03-05 Verfahren zur herstellung eines aluminiumbeschichteten metalls Active EP3399072B1 (de)

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US15/587,880 US20180320282A1 (en) 2017-05-05 2017-05-05 Method of making aluminum-coated metal

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105200476A (zh) * 2015-10-29 2015-12-30 中物院成都科学技术发展中心 一种不锈钢螺栓电镀预处理方法

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Publication number Priority date Publication date Assignee Title
US5304257A (en) 1993-09-27 1994-04-19 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium conversion coatings for aluminum
US5374347A (en) 1993-09-27 1994-12-20 The United States Of America As Represented By The Secretary Of The Navy Trivalent chromium solutions for sealing anodized aluminum
US6511532B2 (en) 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6521029B1 (en) 2000-10-31 2003-02-18 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
EP2419551A2 (de) 2009-03-18 2012-02-22 Basf Se Elektrolyt und oberflächenaktive additive für die galvanische abscheidung glatter, dichter aluminium-schichten aus ionischen flüssigkeiten
JP5581523B2 (ja) * 2009-10-19 2014-09-03 ディップソール株式会社 アルミニウムまたはアルミニウム合金バレル電気めっき方法
US8821707B2 (en) * 2010-08-04 2014-09-02 Dipsol Chemicals Co., Ltd. Electric Al or Al alloy plating bath using room temperature molten salt bath and plating method using the same
EP3088571B1 (de) * 2015-04-28 2021-06-02 The Boeing Company Umweltfreundliche aluminiumüberzüge als opferbeschichtungen für hochfeste stahllegierungen

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN105200476A (zh) * 2015-10-29 2015-12-30 中物院成都科学技术发展中心 一种不锈钢螺栓电镀预处理方法

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