EP3088571B1 - Umweltfreundliche aluminiumüberzüge als opferbeschichtungen für hochfeste stahllegierungen - Google Patents

Umweltfreundliche aluminiumüberzüge als opferbeschichtungen für hochfeste stahllegierungen Download PDF

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EP3088571B1
EP3088571B1 EP15382212.7A EP15382212A EP3088571B1 EP 3088571 B1 EP3088571 B1 EP 3088571B1 EP 15382212 A EP15382212 A EP 15382212A EP 3088571 B1 EP3088571 B1 EP 3088571B1
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aluminum
substrate
coating
coatings
alloy steel
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English (en)
French (fr)
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EP3088571A1 (de
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Usoa Izagirre Etxeberria
Laura Sanchez Cupido
Nieves Lapeña Rey
Ainhoa Unzurrunzaga
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Boeing Co
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Boeing Co
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Priority to US15/137,965 priority patent/US20160319449A1/en
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Priority to US16/721,081 priority patent/US20200123672A1/en
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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
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/003—Electroplating using gases, e.g. pressure influence
    • 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
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/52—After-treatment of electroplated surfaces by brightening or burnishing

Definitions

  • This specification refers to an environmentally friendly electroplating process for coating a ferrous alloy steel substrate, preferably a high strength steel alloy, using a novel aluminum bath formulation comprising more safe-handling, less-harzardous and environmentally friendly components than the formulation used in the AlumiPlateTM process, which was the most promising aluminum coating alternative for Cd replacement known until now. Additionally, the present patent application refers to both the aluminum coating and the coated ferrous alloy steel substrate obtained by such process, as well as the use of both in applications such as aeronautical, automotive, marine, construction, industrial and household applications.
  • this specification provides an electroplating process and aluminum bath formulation suitable for providing an aluminum coating useful as a safe nickel-free alternative to the cadmium coatings used in high strength steel components in aerospace.
  • AlumiPlateTM is a plating technology that uses organic solvents as electrolytes, a toluene-based very flammable and toxic solution which also contains pyrophoric alkylaluminum constituent components. Therefore, it involves handling hazardous and non-environmentally friendly plating solutions.
  • Zinc-nickel electroplating is one of the most promising candidates. Zinc-nickel plating is possible in a wide range of pHs, using both alkaline or acidic electrolyte baths, so several chemistries have been developed in a wide range of pH leading to a range of Zn-Ni alloy compositions. Amongst all of them, only 2 coating specifications are compatible with high strength steel substrates: the AMS 2417G and the ASTM B 841. These specifications allow both alkaline and acid plating baths.
  • Ion Vapour Deposition (IVD) aluminum technology has been developed as a replacement of cadmium electroplating in some aeronautic applications.
  • Some of the disadvantages of this technology include the limited ability to coat internal and deeply recessed surfaces: depending on the orientation of the part's surfaces in the chamber, the coating thickness may not be equivalent in all areas (especially for internal diameters), the coating does not pass the re-embrittlement test as per HSSJTP [ High-Strength Steel Joint Test Protocol, for Validation of Alternatives to Low Hydrogen Embrittlement Cadmium For High-Strength Steel Landing Gear and Component Applications, July 31, 2003; AFRL/MLSC/WPAFB, OH 45433-7718; Approved for public release; distribution unlimited (26 March 2003 )] and large components may be physically restricted from IVD-AI coating by the dimensions of the vacuum vessel.
  • the magnetron sputtered aluminum process was specifically designed to coat internal diameters or recessed areas to overcome the limitations of Ion Vapor Deposited Aluminum (IVD-AI).
  • IVD-AI Ion Vapor Deposited Aluminum
  • electroplating is the one of the most versatile and economic alternatives.
  • aprotic electrolytes such as nonaqueous inorganic or organic electrolyte systems can be used to electroplate this metal.
  • AlumiPlateTM is an aluminum electroplating technology from organic electrolyte systems. This technology is commercially produced by means of the Siemens Sigal® process, which was developed by Siemens AG (Germany), and most recently has also been processed in Europe at Aluminal Corporation. The process was licensed in the United States to AlumiPlate, Inc. in 1995.
  • the plating formulation of AlumiPlateTM comprises a toluene-based solution containing a pyrophoric alkylaluminum constituent and other compounds, such as ethers, aluminoxanes or ammonium salts [ US2007261966A1, 2007-11-15 , Alumiplate Inc. (US), Aluminum Electroplating Formulations].
  • the aluminum coatings obtained with the AlumiPlateTM plating process have demonstrated to have better performance than cadmium in a number of tests, such as hydrogen embrittlement, stress corrosion cracking, acidified (SO 2 ) salt fog, fluid corrosion resistance tests, etc. If compared with to IVD-AI, it provides coatings with better corrosion resistance and density. This process can also lead to a similar throwing power or coverage than cadmium plating by using auxiliary anodes to coat the internal recessed surfaces.
  • a key disadvantage of this process is that is not environmentally friendly, since it employs a toluene-based toxic and very flammable solution which also contains pyrophoric alkylaluminum constituent components. Therefore, it must be operated in an humidity and oxygen controlled atmosphere line.
  • the elimination of the cadmium by this method addresses only one aspect of cadmium substitution on high strength steel components, the elimination of a toxic coating.
  • the process still involves handling toxic and non-environmentally friendly plating solutions [ US2007261966A1, 2007-11-15 , Alumiplate Inc. (US), Aluminum Electroplating Formulations].
  • Global lonix has developed a plating chemistry composed by more environmentally preferred organic solvents for aluminum electrodeposition.
  • the plating formulation comprises non aromatic organic solvents, such as ethanol, isopropanol or butanol, a conductive additive and aluminum salts, such as aluminum alcoxides and aluminum chloride.
  • Global lonix has reported that this formulation provides coatings with throwing power comparable to cadmium electroplating [ WO2004079054A1, 2004-09-16 , Global lonix (CA), Electrodeposition of aluminum and refractory metals from non-aromatic organic solvents].
  • Hitachi Metals LTD has developed an aluminum electroplating bath comprising dimethyl sulfone solvent and ammonium chloride or a tetraalkylammonium chloride which is applied by means of a barrel plating method. According to the inventors of this formulation, this plating solution has improved the coatings electrical conductivity, which in turn provides uniform aluminum coatings. They also state that this bath possesses an extended bath life [ US2011253543A1, 2011-10-20 , Hitachi Metals Ltd. Aluminum Electroplating Solution and Method for forming Aluminum Plating Film].
  • Ionic liquids are novel fluids entirely consisting of ionic species which usually have a melting point of 100 oC or below. If the adequate chemical structure is selected, they can have a wide electrochemical window, negligible-volatility (which provides them with a non-flammable nature), high solubility of metal salts, aprotic nature, or a high conductivity in comparison to organic solvents [ Phys. Chem. Chem. Phys., 2006, 8, 4265-4279, Andrew P. Abbott and Katy J. McKenzie, Application of ionic liquids to the electrodeposition of metals ].
  • Al-Zr coatings electroplated with this formulation have good adhesion (in the tape test, which is less severe than the bend test), smooth cross section and can stand from 700 to 1500 hours in the SST (Salt Spray Test- JISZ2371) without developing red rust
  • US2010285322A1, 2010-11-11 Dipsol Chem (Japan), Hyundai Motor Co Ltd (Japan), Electric Al-Zr Alloy Plating Bath Using Room Temperature Molten Salt Bath and Plating Method Using the Same; US2012205249A1, 2012-08-16 , Hyundai Motor CO LTD (Japan) Dipsol Chem. (Japan), Aluminum or Aluminum Alloy Barrel Electroplating Method].
  • a more recent patent of Dipsol discloses new formulations including the same ionic liquid, a brightening agent, an organic polymer but without any organic solvent. These formulations also contain dimethylamine borane and hydrides, such as aluminum lithium hydride. They have demonstrated that this process has a good throwing power [ US2013292255 A1, 2013-11-07 , Dipsol Chem. (Japan), Electrical Aluminium or Aluminium alloy fused salt plating bath having good throwing power, and electroplating method and pretreatment using the same].
  • this formulation still has serious handling and health risks since the hydrides in this bath liberate extremely flammable gases in contact with water, causing severe burns. Also, in this particular case, no hydrogen embrittlement performance has yet been reported.
  • JP2008195990 (2008-08-08 , Dipsol Chem Co Ltd; Hyundai Motor Co Ltd) discloses an electric aluminum plating bath and plating method.
  • the plating bath comprises AlCl 3 , 1-methyl 3-propyl imidazolium bromide, NaCl, KCI and 1,10 phenanthroline.
  • US 2012/0006688 A1 discloses an electroplating process for coating ferrous alloy steel with aluminum which comprises immersing an aluminum anode in an aluminum bath, pretreating the steel by electrolytic degreasing and pickling, electroplating the steel in the aluminum bath in argon gas and rinsing the aluminum coated steel.
  • the plating bath comprises AlCl 3 , EMIMCL (ionic liquid) and sodium laurylsulfate.
  • JP H04072089 (1992-03-06 , Dipsol Chem) discloses an aluminum plating bath comprising AlCl 3 , 1-methyl-3-porpyl imidazolium bromide, a brightener and ZrCl4 as metal salt.
  • US 2012/031766 A1 discloses an electric aluminum or aluminum alloy plating bath which can be handled industrially with safety and high resistance to corrosion for parts of motorcars.
  • the bath comprises an aliminum halide, a N-alkyl imidazolium halide and a high boiling point aromatic hydrocarbon solvent with specific molar ratios.
  • EP 0339536 A1 (1989-11-02 Nisshin Steel Co Ltd; Mitsubishi Petrochemical Co) discloses a plating bath for electrodeposition of aluminum using a mixed molted salt bath comprising an aluminum halide and 1-alkyl or 1,3-dialkylimidazolium halide without generation of burnt deposits.
  • This specification provides a safer handling, less-hazardous and more environmentally friendly process, compared with other known processes such as AlumiPlateTM, for coating ferrous alloy steel such as high strength steel alloy with an aluminum coating.
  • AlumiPlateTM for coating ferrous alloy steel such as high strength steel alloy with an aluminum coating.
  • this patent application provides a process suitable for complying with environmental and occupational health and safety regulations.
  • This aluminum coating can be useful in applications such as aeronautical, automotive, marine, construction, industrial and household applications, in particular as a Ni-free Cd replacement for high strength steel alloys.
  • this specification provides a process for obtaining aluminum metallic coatings as a Ni-free Cd replacement for ferrous alloy steel such as high strength steel alloys, with the main objective of achieving similar or better performance than the LHE Cd or the AlumiPlateTM methods, but plating using safer handling, less-hazardous and more environmentally friendly electrolytes, i.e., the developed ionic liquid electrolytes for aluminum plating described in this patent application.
  • the Al coating obtained by the electroplating process described herein is suitable for complying with environmental and occupational health and safety regulations, while passing the structural and functional requirements established for Cd replacement process qualification in high strength ferrous alloy steels.
  • the coatings proposed in this patent application show comparable behavior to Low Hydrogen Embrittlement Cd (LHE Cd) and AlumiPlateTM reference coatings with respect to compliance with most or, more preferably, all the preliminarily acceptance criteria established for Cd replacement in ferrous alloy steel such as high strength steel alloys, i.e. coating appearance, morphology, throwing power, adhesion, corrosion resistance and hydrogen embrittlement performance. But, advantageously, they are produced with an environmentally friendly and safe handling plating bath and plating process.
  • both the aluminum coating and the ferrous alloy steel substrate, preferably high strength steel alloy, coated with an aluminum coating by the process described in this patent application are particularly useful in aerospace applications.
  • the aluminum coating obtained by the process described herein may be particularly useful as sacrificial coatings in such applications wherein Cd sacrificial coatings were used, for example, high strength steel landing gear, high strength steel actuators, steel fasteners (bolts, rivets) or electrical connector shells.
  • This specification provides an electroplating process for coating a ferrous alloy steel cathode substrate with an aluminum coating, characterised in that the process comprises:
  • the aluminum coated ferrous steel alloy is rinsed with alcohol and water, followed by drying.
  • the aluminum plating bath formulation is preferably anhydrous and the electroplating is conducted under a dry inert gas stream in order to prevent contact of the electrolyte with the ambient's moisture.
  • a dry inert gas stream in order to prevent contact of the electrolyte with the ambient's moisture.
  • an accurate control of oxygen and moisture in the electrochemical cell is not needed.
  • the process described herein can be applied to different types of ferrous alloy steel substrates [ ASM Handbook Volume 1, Properties and Selection: Irons, Steels, and High Performance Alloys ]. Specifically, the process can be applied to plain carbon steels with low-carbon (lower than 0.2% C), medium-carbon (between 0.2-0.5% C) or high-carbon (more than 0.5% C); to low alloy steels (alloys with not more than 8% of alloying elements) and to high-alloy steels (alloys with more than 8% alloying elements).
  • the ferrous steel alloy substrate is a medium-carbon ultra-high strength structural low-alloy steel, e.g., a ferrous steel alloy substrate containing between 0.2 and 0.5% of C, not more than 8% of alloying elements and with an ultra-high structural strength.
  • This substrate is also referred to as "high strength steel alloy" in this patent application.
  • Low-alloy steels constitute a category of ferrous materials that exhibit mechanical properties superior to plain carbon steels as the result of additions of such alloying elements as nickel, chromium, and molybdenum.
  • Total alloy content in low-alloy steels can range from 2% up to levels just below that of stainless steels, which contain a minimum of 10% Cr.
  • the primary function of the alloying elements is to increase hardenability in order to optimize mechanical properties and toughness after heat treatment.
  • medium-carbon ultra-high strength steels are structural steels with yield strengths that can exceed 1380 MPa (200 ksi).
  • SAE-AISI designations or are proprietary compositions and include AISI/SAE 4130, the higher-strength AISI/SAE 4140, and the deeper hardening, higher-strength AISI/SAE 4340.
  • SAE-AISI designations or are proprietary compositions and include AISI/SAE 4130, the higher-strength AISI/SAE 4140, and the deeper hardening, higher-strength AISI/SAE 4340.
  • the high strength steel alloys may be those which currently are being electroplated with cadmium as sacrificial coating in aerospace applications.
  • medium carbon ultra-high strength low-alloy steels may include, for example:
  • the source of aluminum is an aluminum halide. More preferably, the aluminum halide is aluminum trichloride as it provides good performance for Al electroplating and is cost effective.
  • the aluminum bath formulation described herein comprises a source of aluminum and a further compound, refered to as "ionic liquid” in this specification, which is an ionic compound or salt in the liquid state.
  • ionic liquid is liquid in the electroplating working condition, giving rise to an electrolyte solution capable to electroplate aluminum.
  • the term "ionic liquid” may be understood as ionic compounds or salts whose melting point is below some established temperature, such as 100°C. While ordinary liquids are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions and short-lived ion pairs. The term ionic liquid was coined to distinguish these lower temperature ionic liquids from the high temperature analogues (i.e. high temperature molten salts) which are composed predominantly of inorganic ions.
  • the ionic liquid comprised in the aluminum plating bath formulation is 1-ethyl-3-methylimidazolium chloride.
  • the molar ratio between aluminum trichloride and the nitrogen-containing compound may range from 80:40 to 60:40.
  • imidazolium based ionic liquids generally offer lower viscosity and higher conductivity than the pyrrolidinium based ones. A high conductivity and low viscosity are beneficial to increase the throwing power and decrease the ohmic losses of the electrodeposition process.
  • the molar ratio of the aluminum trichloride and the nitrogen-containing compound, for example, 1-ethyl-3-methylimidazolium chloride is too low, there will be not enough concentration of active aluminum species to electrodeposit aluminum coatings.
  • the aluminum bath formulation described herein comprises a brightening agent, which is an organic compound that may be selected, for example, from a large organic cyclic compound, a bicyclic compound, a monocyclic compound or an acyclic compound..
  • the brightening agent is preferably less-hazardous and more environmentally friendly than the constituents of other aluminum plating baths such as the AlumiPlateTM plating baths.
  • the brightening agent is 1,10-phenantroline, since its use allows the electrodeposition of uniform, highly levelled aluminum coatings.
  • the brightening agent specifically wherein this agent is 1,10-phenanthroline, is present in the aluminum bath formulation in an amount ranging from 0.01 to 1.0 by weight respect to the total weight of the aluminum plating bath formulation.
  • the counter-anion of the metal salt and the counter-anion of the source of aluminum and/or the counter-anion of the ionic liquid may be the same. As a result, the solubility of the components may be improved.
  • the metal salt is the alkali metal halide potassium chloridepresent in an amount ranging from 0.04 to 3.70 % by weight respect to the total weight of the aluminum plating bath formulation, which corresponds to a range from 5 g/L to 50 g/L.
  • the aluminum plating bath formulation used in the electroplating process as described therein consists of:
  • the aluminum plating bath formulation consists of: a range from 95.3 to 99.5 wt% of a mixture of aluminum trichloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio of 60:40; a range from 0.1 to 1.0 wt% of 1,10-phenantroline and a range from 0.4 to 3.7 wt% of KCl.
  • the preferred bath formulations described in the above paragraphs comprise the required amounts of all the components in order to get aluminum coatings with improved performance and particularly suitable to be used as Ni-free Cd replacement coating.
  • a molar ratio of the aluminum trichloride and 1-ethyl-3-methylimidazolium chloride of 60:40 provides enough concentration of active aluminum species and, therefore, to get a suitable Al coating.
  • the reported amounts of 1,10-phenantroline and KCI give rise to an improvement in the delicate balance between the requirements needed to use aluminum coatings as Ni-free Cd replacement coatings.
  • the plating bath formulation Prior to the anodic polarization step, the plating bath formulation may be conditioned by purging the electrolyte with a dry inert gas stream inside the plating bath formulation during at least 30 minutes. Once the electrolyte has been appropriately conditioned, the anodic polarization and electroplating steps may be performed with dry inert gas outside the electrolyte.
  • the electroplating step e) is carried out with a current density ranging from 5 to 25 mA/cm 2 , a temperature ranging from 40 to 75 oC and stirring the electrolyte in a range from 500 to 1000 rpm.
  • the throwing power of the aluminum coatings usually decreases when increasing the temperature with respect to the range stated above.
  • Aluminum coatings composed by multiple consecutive layers, poorly adhered to each other, are usually obtained when plating without stirring the electrolyte.
  • Aluminum coatings with a more brittle appearance may be produced when higher current densities than 25 mA/cm 2 are applied.
  • the aluminum anode substrate is immersed in the etching/plating bath, and then the bath formulation may be conditioned, for example, as previously described.
  • the ferrous alloy steel cathode substrate preferably high strength steel alloy
  • the ferrous alloy steel cathode substrate is immersed in the conditioned bath formulation described in this patent application, which will be used afterwards for aluminum plating, and an anodic polarization step ranging from 0.6 to 1.2 V may be applied during a period ranging from 10 to 30 seconds.
  • This etching step d) may be done, for example, at the same temperature as the plating step e).
  • the aluminum anode substrate used in the electroplating process described in this patent application pre-treated (step a).
  • This pre-treatment comprises mechanical polishing (i), alkaline cleaning (ii), deoxidizing (iii) and driyin (iv) to obtain a polished, clean, deoxidized and dry aluminum anode substrate.
  • the electroplating process is more easily performed if the aluminum substrate is polished, e.g., is free from oxides and compounds formed upon the exposure of the anode to the air or during previous electrodeposition processes.
  • the aluminum substrate should also be cleaned and dried to avoid contamination of the plating formulation bath.
  • the aluminum anode substrate used in the electroplating described herein is subject to a pre-treatment comprising:
  • the step iv) may comprise the drying of the aluminum substrate with hot air at a temperature of at least 60oC during at least 1 minute, until constant weight is achieved.
  • the mechanical polishing may comprise first manual polish with P-120 emery paper and then removing the powder remaining on the surface, for example, with a white cloth.
  • the alkaline cleaning may be done by immersing the aluminum anode substrate in an aqueous alkaline cleaning agent such as, for example, a range from 45 to 60 g/L of Turco-4215 NC LT and a range from 1 to 3 g/L of T-4215 NC LT ADD (additive) during a period ranging from 5 to 30 min.
  • the alkaline cleaning may be carried out, for example, stirring in a range from 200 to 500 rpm, at a temperature ranging from 45 to 55oC.
  • the aluminum anode substrate may be rinsed, for example, first with tap water followed by deionized water.
  • the deoxidizing step may be carried out by immersing the aluminum anode substrate in the deoxidizing bath containing a deoxidizing agent such as, for example, a range from 60 to 120 g/L of Turco Smut Go NC and a range from 15 to 30 g/L of HNO 3 (42oBé) during a period ranging from 1 to 10 min.
  • the deoxidizing step may be carried out, for example, at a temperature in the range from 20 to 50oC.
  • the aluminum anode substrate may be rinsed, for example, first with tap water followed by deionized water.
  • the pretreated aluminum anode substrate is dried, for example, using hot air. Previously to the drying step, it may be rinsed with a more volatile solvent such as acetone in order to remove part of water with this solvent.
  • a more volatile solvent such as acetone
  • the ferrous alloy steel cathode substrate is pre-treated (step b) by degreasing (v) and blasting (vi) the ferrous alloy steel cathode.
  • a degreased and blasted high strength steel alloy Preferably a degreased and blasted high strength steel alloy.
  • the electroplating process is more easily performed if the steel substrate is degreased, i.e. it is free from any grease or oil on its surface that could hinder a uniform aluminum electrodeposition.
  • the steel substrate would be blasted in order to get a mechanical etching of the surface and subsequent good adhesion of the electrodeposited aluminum layer.
  • this mechanical etching helps coating adhesion but does not provoke any risk of hydrogen embrittlement for the substrate, on the contrary to conventional chemical acid or alkaline pre-treatments.
  • the ferrous alloy steel used in the electroplating process is subjected to the pre-treatment in order to get a degreased and blasted ferrous alloy steel.
  • the pre-treatment comprising:
  • the ferrous alloy steel cathode substrate may be degreased using any degreasing agent such as, for example, acetone or an aqueous alkaline degreasing agent.
  • This step may comprise the immersion of the steel in a degreasing agent, manual cleaning with the help of a white cloth and the application of ultrasonic agitation for at least 10 minutes, until neither oil nor grease remains on their surface.
  • the steel may be dried, for example, using hot air.
  • the degreased steel surface may be blasted, for example, with alumina grit, silicon carbide grit, glass beads or steel grit to remove any possible oxide and impurities off the steel substrate.
  • the powder remaining on the surface after blasting may be removed with compressed air.
  • the blasting agent has a particle size from F-36 to F-80 macrogrits (i.e. a mean diameter ranging from 185 to 525 microns), since the use of this blasting agent in the electroplating process described herein results in an improvement in the bend adhesion of the aluminum coating obtained.
  • Examples of those preferred blasting agents are F-80 and F-36 alumina grit.
  • the electroplating process described in this patent application preferably comprises rinsing the aluminum coated ferrous alloy steel with alcohol and water.
  • it may comprise rinsing first with ethyl alcohol followed by water rinsing such as deionized water rinsing, until a clean surface free of any rest of ionic liquid is obtained.
  • the aluminum plated specimens may be stored in a humidity controlled atmosphere.
  • the electroplating coating process described herein further comprises step g), wherein a heat treatment is applied to the aluminum coated ferrous steel alloy obtained in step f).
  • the aluminum coated specimens are baked at 190 ⁇ 14oC for at least 23 hours.
  • the addition of step g) is preferably included in order to the aluminum coated specimens obtained comply with the hydrogen embrittlement requirements.
  • the electroplating coating process described herein further comprises applying a conversion coating to the aluminum coated ferrous steel alloy obtained in step f), or preferably the ones obtained in step g), wherein this conversion coating is selected from hexavalent chromium conversion coating and a Cr-free conversion coating, in particular Cr-free conversion coating with a similar performance to the hexavalent chromium conversion coating.
  • the aluminum plated specimens may be optionally conversion coated using conventional Cr VI based conversion treatments, such as Alodine 1200S or similar.
  • Cr-free conversion treatments such as those described in US 8,298,350 B2 and US 2013/0052352 A1 patent disclosures or similar products and developments may be used.
  • this specification provides a safer handling and more environmentally friendly electroplating process and bath formulation for coating ferrous alloy steel, preferably a high strength steel alloy, with an aluminum coating.
  • the Al coatings obtained by the process described herein are also more environmentally friendly than Cd coatings and other known Cd alternative coatings (e.g. Zn-Ni).
  • this specification provides a process to obtain an aluminum coating useful in the applications such as aeronautical, automotive, marine, construction, industrial and household applications.
  • the coating obtained by the process described in this patent application can be used as Cd replacement in sacrificial coatings for high strength steel alloys.
  • the electroplating process described herein comprises: the pre-treatment of the high strength steel alloy cathode substrate and the aluminum anode substrate as described in this patent application; the electroplating treatment using an aluminum plating bath formulation which comprises: a range from 95.30 to 99.95 wt% of a mixture of aluminum trichloride and 1-ethyl-3-methylimidazolium chloride in a molar ratio ranging from 80:40 to 60:40, a range from 0.01 to 1.0 wt% of 1,10-phenantroline, and a range from 0.04 to 3.7 wt% of KCI; and the post-treatment of the obtained coating as described in this patent application.
  • This specific combination of process steps and bath composition provides an aluminum coating with particularly improved properties that makes the product obtained a particularly preferred candidate for Cd replacement as sacrificial coatings for high strength steel alloys.
  • the electroplating process for coating a high strength steel alloy substrate with an aluminum coating comprises:
  • the ferrous steel alloy is a high strength steel alloy as described therein.
  • this specification refers to the aluminum coated ferrous alloy steel substrate obtained by the process described herein.
  • the aluminum coating obtained by the electroplating process described can be used in the aeronautical industry, preferably as Ni-free Cd replacement in sacrificial coatings for high strength steel alloys.
  • the aluminum coated ferrous alloy steel substrate described herein can achieve a similar or better performance than the one obtained by LHE Cd or the AlumiPlateTM methods, but plating using safer handling, less-hazardous and more environmentally friendly electrolytes.
  • the environmentally friendly optimized aluminum plating bath formulation allows getting an aluminum coating particularly useful as Ni-free Cd replacement in sacrificial coatings for high strength steel alloys.
  • the aluminum coating obtained with this environmentally friendly formulation shows similar or better performance than the LHE Cd or the AlumiPlateTM methods but plating using safer handling, less hazardous and more environmentally friendly electrolytes.
  • the aluminum bath formulation described herein may be synthesized as follows: The ionic liquid, for example the nitrogen-containing compound, may be dried at 70oC under vacuum. Then, the required amount of aluminum halide may be added slowly under inert gas, such as argon, flow. Finally, the ionic liquid may be cooled down and, optionally, stored in a humidity-free atmosphere. Alternatively, commercial ionic liquid comprising the required ratio of ionic liquid (for example, nitrogen-containing compound) and aluminum halide may also be used.
  • the ionic liquid may be heated up to 80oC in a closed vessel under a dry inert gas stream while stirring and the brightening agent may be added to the heated ionic liquid.
  • this mixture may be stirred during 2 h at 80oC in the closed vessel under a dry inert gas stream.
  • the alkali metal halide may be added to the mixture, and the formulation may be stirred during 2 h at 80oC in the closed vessel under a dry inert gas stream.
  • the bath formulation may be cooled down and stored in a humidity-free atmosphere.
  • the ionic liquid electrolytes used in these examples were synthesized as follows: B01: Either the as-received BasionicsTM Al01 ionic liquid electrolyte from BASF or the house-made AlCl 3 -EMIC 60:40 electrolyte (see below) were independently used as baseline electrolytes to be modified with the different additives.
  • the house-made AlCl 3 -EMIC 60:40 electrolyte was prepared by mixing the corresponding amounts of aluminum trichloride and 1-ethyl-3-methyl-imidazolium chloride, as follows: The 1-ethyl-3-methylimidazolium chloride [EMIC] (Fluka Ref. 30764, purity min 93%), was dried at 70oC under vacuum for several hours. Then, it was placed into a glass vessel. The aluminum trichloride [AlCl 3 ] (Across Organics Ref.
  • B01-phen The baseline electrolyte was heated up to 80oC in a closed vessel under a dry inert gas stream while stirring. Then, a range from 0.1 to 1.0 %wt of 1,10-phenantroline was added. The Basionics TMAl01 ionic liquid modified with the 1,10-phenantroline was stirred during 2 h at 80oC in the closed vessel under a dry inert gas stream. Finally, the ionic liquid formulation obtained was cooled down and stored in a humidity-free atmosphere.
  • B01-phen-KCl An ionic liquid formulation comprising 1,10-phenantroline obtained as described above (B01-phen) was heated up to 80oC in a closed vessel under a dry inert atmosphere gas stream while stirring. Then, a range from 5 to 50 g/L of KCI was added and the formulation obtained was stirred during 2 h at 80oC in the closed vessel under a dry inert gas stream. Finally, the aluminum plating formulation bath was cooled down and stored in a humidity-free atmosphere.
  • the cathode was a high strength steel rectangular sheet panel.
  • the cathode was a rectangular flat panel machined from 4130 alloy steel conforming to AMS 6350 steel sheet.
  • the anodes were 2 rectangular 99.999% purity aluminum sheets and were positioned at both sides of the cathode.
  • the cathode was a high strength steel cylindrical specimen.
  • the cathode was a cylindrical 1.a.1 geometry type AISI 4340 / SAE AMS-S-5000 steel specimen with the size and geometry required by the ASTM F-519 standard.
  • the material was certified by the supplier according to the requirements of the ASTM F-519 standard.
  • the anode was an Al1050 aluminum cylindrical sheet, which was positioned around the cathode.
  • the aluminum anode substrates were all pre-treated following a same procedure, independently of the plating bath's formulation and the electroplating conditions. These pre-treatment involved:
  • the steel cathode substrates were all pre-treated following the same procedure, independently of the plating bath formulation and the electroplating conditions. These pre-treatment involved:
  • the aluminum anode substrates were immersed in the plating bath and the electrolyte was conditioned by purging the plating bath formulation with a dry inert gas stream placed inside the plating bath during 30 minutes. Once the electrolyte had been conditioned, the dry inert gas purger was placed outside the electrolyte.
  • the steel cathode substrates were immersed in the conditioned ionic liquid bath, which was to be used afterwards for aluminum plating, and an anodic polarization step of 0.6 V was applied during 30 seconds. Etching was done at the same temperature as plating.
  • the experimental set-up for aluminum plating was the same independently of the plating bath's composition and the plating conditions. This set-up slightly changed depending on the geometry of the specimens (cathode substrates) to be electroplated.
  • the electrochemical cell consisted of a closed vessel containing a predetermined amount of the ionic liquid electrolyte.
  • the electroplating was conducted under a dry inert gas stream in order to prevent contact of the electrolyte with the ambient's moisture.
  • an accurate control of oxygen and moisture in the electrochemical cell was not needed.
  • the cover of the vessel had different slots and holes where the cathode, the anodes, the temperature controller and the inert gas inlet and exhaust were assembled.
  • the electroplating process comprised the immersion of the pre-treated steel specimens in the bath formulation, closing the electric circuit with the adequate fixtures and applying a pre-determined cathodic direct current density to the cathode for a pre-determined amount of time and temperature while the electrolyte is kept at a pre-determined temperature.
  • the electroplating experiments were performed using a current rectifier to provide the power supply under dry inert gas stream.
  • a hot plate with magnetic stirrer coupled to a temperature controller provided the necessary heat and stirred the electrolyte at different rpms.
  • Table I Aluminum electroplating conditions Ref. Current density (mA/cm 2 ) Temperature (oC) Bath agitation Plating time (minutes) B01-1 2.5-7.5 50 No 60-180 B01-2 5 40 No 270 B01-phen 5-25 40-75 Yes 30-120 B01-phen-KCI 5-25 40-75 Yes 30-120
  • the aluminum coatings were all post-treated following the procedure described below, independently of the plating bath's composition and the plating conditions used.
  • the aluminum plated cathode substrates were manually rinsed with deionized water or, alternatively, with ethyl alcohol followed by deionized water until a clean surface free of any rest of ionic liquid were obtained.
  • the aluminum plated cathode substrates were dried using hot air. Finally, some of the aluminum plated cathode substrates were baked at 190 ⁇ 14oC for 23 hours.
  • the aluminum plated cathode substrates were stored in a controlled atmosphere without humidity.
  • Some of the aluminum plated cathode substrates were conversion coated using the conventional Cr VI based conversion treatment Alodine 1200S.
  • the high strength steel specimens Al plated using the electrolyte compositions and process conditions described above were tested in terms of coating's appearance, thickness, composition, cross section morphology, adhesion, corrosion resistance, throwing power and hydrogen embrittlement susceptibility according to the test procedures described in Table II (see below).
  • LHE Cd plated specimens conforming to MIL-STD-870B specification Class 2 Type II were also tested for comparison.
  • the different aluminum plated coatings as well as the LHE Cd controls were rated, at a minimum, providing pass/fail results according to the success criteria agreed in Table II for each test.
  • a "pass" rating typically indicates a performance equivalent or better than that of Cd.
  • the results were also compared to those found for AlumiPlateTM in the literature ([Final report WP-200022] and [ Report number JF130828, Juergen Fischer et al, Electrodeposition of aluminum with different ionic liquid based electrolytes and their comparison with the AlumiPlate® layer, University of North Dakota, January 2014 ]).
  • the types of substrates and test specimens that were used for evaluating coating appearance, thickness, composition, cross section morphology, adhesion and corrosion resistance were rectangular flat panels machined from 4130 alloy steel conforming to AMS 6350 steel sheet.
  • test-specimens for thickness and composition determination, cross section morphology examination and adhesion tests were nominally 1 inch x 4 inch x 0.04 inches (25.4 mm x 101.6 mm x 0.10 mm). Unless otherwise specified, two specimens were used for each test.
  • test-specimens for corrosion resistance tests were nominally 2 inch x 4 inch x 0.04 inches (50.8 mm x 101.6 mm x 0.10 mm). Unless otherwise specified, two specimens were used for each test (2 scribed and 2 unscribed).
  • the types of substrates and test-specimens that were used for hydrogen embrittlement were cylindrical 1.a.1 geometry type AISI 4340 / SAE AMS-S-5000 steel specimens with the size and geometry required by the ASTM F-519 standard.
  • the material and the test-specimens were certified by the supplier according to the requirements of the ASTM F-519 standard. Unless otherwise specified, four specimens were used for hydrogen embrittlement testing.
  • test-specimens for the throwing power assessment were cylindrical 1.a.1 geometry type AISI 4340 / SAE AMS-S-5000 steel specimens conforming to ASTM F-519 standard. Unless otherwise specified, the coverage of the notch by the coating in all specimens to be subjected to hydrogen embrittlement tests was evaluated.
  • Tested samples are:
  • the thickness of B01-phen and B01-phen-KCI coatings was determined to be acceptable (between 12 and 20 ⁇ m) as well as that of the baseline LHE Cd coating. Thus, these coatings were given a "pass" rating for thickness.
  • the thickness of the B01-1 and B01-2 coatings was not fine-tuned to be within 12-20 ⁇ m and, thus, they were given a "fail” rating.
  • the detailed results of the cross section's inspection of the coatings (according to ASTM B-487) are shown in Table IV.
  • Table IV Thickness (cross-section examination ASTM B-487) Coating Reading average ( ⁇ m) Pass/Fail Specimen 1 Specimen 2 AlumiPlateTM ⁇ 13 (targeted 23) Pass LHE Cd (1)(8) 12 12 Pass B01-1 (2)(3)(5)(8) 7.3 6.9 Fail B01-2 (2)(3)(5)(8) 23 25 Fail B01-phen (2)(4)(5)(8) 12 12 Pass B01-phen-KCI (2)(4)(6)(8) 14 14 Pass B01-phen-KCI (1)(4)(6)(8) 17 16 Pass
  • composition of the tested coatings was determined to be acceptable (not less than 99% of Al). Thus, the coatings were given a "pass" rating for composition.
  • the composition of B01-phen-KCI (1)(4)(6)(8) was less than 99% of Al due to the Cr-VI post-treatment on top of the aluminum coating.
  • the detailed results of the surface SEM/EDS examination are shown in Table V.
  • Table V Composition (surface SEM/EDS examination) Coating Reading Average Pass/ Fail Wt% O Wt% Al Wt% S Wt% Cl Wt% Cr Wt% Fe Wt% Cd AlumiPlateTM 100 Pass LHE Cd (1)(8) 53.73 0 0.80 0 7.66 0 37.81 - B01-1 (2)(3)(5)(8) 0 100 0 0 0 0 0 0 Pass B01-2 (2)(3)(5)(8) - - - - - - - - B01-phen (2)(4)(5)(8) 0 100 0 0 0 0 0 0 Pass B01-phen-KCI (2)(4)(6)(8) 0 99.14 0 0.0 0 0.86 0 Pass B01-phen-KCI (1)(4)(6)(8) 19.47 75.66 0.25 0 4.02 0.61 0 -
  • the cross section morphology of the coatings electroplated from the B01-phen and B01-phen-KCI electrolytes was determined to be acceptable (uniform, adherent, dense and levelled coatings) as well as that of the baseline LHE Cd coating. Thus, these coatings were given a "pass" rating for cross section morphology.
  • the coatings electroplated from the B01-1 and B01-2 electrolytes failed since non-uniform, non-dense coatings tending to dendritic morphology were obtained.
  • the cross section morphology of the aluminum coatings was radically improved when the AlCl 3 -EMIC 60:40 (Basionics TMAl01) baseline electrolyte was modified with the 1,10-phenantroline additive.
  • the addition of KCI did not jeopardize the cross section morphology of the coatings while improving other properties.
  • the cross section morphology for B01 -phen-KCI coatings was acceptable even if a bigger alumina particle size of F-80 grit was used during blasting in the pre-treatment.
  • B01-phen-KCI (2)(4)(6)(9) Uniform adherent and levelled coatings that completely covered the substrate; Pass Borders were uniformly and well covered.
  • B01-phen-KCI (2)(4)(6)(10) Uniform adherent and levelled coatings that completely covered the substrate; Pass Borders were uniformly and well covered.
  • the bend adhesion of the coatings electroplated from the B01-1 electrolyte was determined to be acceptable, since no separation of the coating from the basis metal at the rupture edge occurred, as well as that of the baseline LHE Cd coating. These coatings were given a "pass" rating for bend adhesion. The rest of the coatings failed, even if the failure was only marginal for the coatings electroplated from the B01-phen-KCI electrolyte.
  • the coatings electroplated from the B01-2 electrolyte were considerably thicker than those plated from the B01-1 electrolyte, which resulted detrimental for the adhesion.
  • the coatings electroplated from the B01-phen-KCI electrolyte passed the adhesion test.
  • Table VIII The detailed results of the visual examination conducted after subjecting the specimens to the adhesion test are shown in Table VIII.
  • Figure 4 shows representative panels of each candidate coating after the adhesion tests.
  • Table VIII Bend adhesion (ASTM B 571 / s. 3) Coating Bend adhesion results Pass/Fail AlumiPlateTM Cracking of coating up to 1/8 inch.
  • Pass LHE Cd (1)(8) No separation of the coating from the basis metal at the rupture edge.
  • the corrosion resistance of unscribed panels of coatings electroplated from the B01-phen-KCI electrolyte was determined to be acceptable (more than 3,000 hours to red rust) as well as that of the baseline LHE Cd coating, both with CrVI post-treatment on top. These coatings were given a "pass" rating for unscribed salt spray corrosion resistance according to HSSJTP criteria. The B01-2 coatings were also given a "pass” since they were able to withstand more than 3,000 hours to red rust without any kind of conversion coating post-treatment on top.
  • the corrosion resistance of the coatings obtained with B01-1, B01-2 and B01-phen-KCl was determined to be acceptable according to the criteria of the MIL-DTL-83488D standard (Class 3 coatings - minimum of 8 micron thick: more than 168 hours to red rust for unpassivated coatings; Class 2 coatings - minimum of 13 microns thick: more than 336 hours to red rust for unpassivated coatings; Class 3 coatings - minimum of 8 micron thick: more than 336 hours to red rust for coatings with supplementary CrVI treatment; Class 2 coatings - minimum of 13 microns thick: more than 504 hours to red rust for coatings with supplementary CrVI treatment).
  • the coatings electroplated from the B01-2 electrolyte were considerably thicker than those plated from the B01-1 electrolyte, which resulted advantageous for the corrosion resistance.
  • Table IX The detailed results of the visual examination conducted after subjecting the specimens to the corrosion test are shown in Table IX.
  • Figure 5 shows representative panels of each coating after the corrosion test.
  • Table IX NSSF Corrosion resistance - Unscribed panels (ASTM B-117 angle 6ooff) Coating Reading average thickness ( ⁇ m) Hours to red rust ( 2 speciments) Pass/Fail HSSJTP (with CrVI post-treatment) MIL-DTL-83488 AlumiPlateTM ⁇ 13 (targeted 23) >3,000 Pass Pass LHE Cd (1)(8) 12 >3,000 Pass - B01-1 (2)(3)(5)(8) 10 216 - Pass 216 - Pass B01-2 (2)(3)(5)(8) ⁇ 30 3,864 Pass Pass 5,208 Pass Pass B01-phen (2)(4)(5)(8) - - - - B01-phen-KCI (2)(4)(6)(8) ⁇ 17 504 - Pass 504 B01-phen-KCI (1)(4)(6)(8) ⁇ 17 >3,500 Pass Pass >3,500
  • the corrosion resistance of scribed panels of the B01-phen-KCI coatings and that of the baseline LHE Cd coating (both with Cr-VI post-treatment on top) was determined to be acceptable (requirement of more than 1,000 hours to red rust) and were given a "pass" rating for scribed salt spray corrosion resistance according to HSSJTP criteria.
  • Table X The detailed results of the visual examination conducted after subjecting the specimens to the corrosion test are shown in Table X.
  • Figure 6 shows representative panels of each coating after the corrosion tests.
  • Table X NSSF Corrosion resistance - Scribed panels (ASTM B-117 angle 6ooff) Coating Reading average thickness ( ⁇ m) (3) Hours to red rust Pass/Fail (HSSJTP) (with CrVI post-treatment) AlumiPlateTM ⁇ 13 (targeted 23) 1000 Pass LHE Cd (1)(8) 12 >1,000 Pass B01-1 (2)(3)(5)(8) 9.5 192 - 168 B01-2 (2)(3)(5)(8) ⁇ 30 1512 - 336 B01-phen (2)(4)(5)(8) - - B01-phen-KCI (2)(4)(6)(8) ⁇ 19 336 - 336 B01-phen-KCI (1)(4)(6)(8) 21 >3,500 Pass 17 3,168
  • the throwing power of the coatings electroplated from the B01-2 and B01-phen-KCI electrolytes was determined to be acceptable, since achieved full coating coverage in the notch, as well as that of the baseline LHE Cd coating. Thus, these coatings were given a "pass" rating for throwing power. The coatings electroplated from the B01-1 and B01-phen electrolytes failed.
  • Rinsing with ethyl alcohol rather than water during post-treatment helped to remove completely the remaining electrolyte from the notch avoiding stains and preventing possible corrosion due to the presence of electrolyte.
  • FIG. 7a and 7b show representative photographs of the notched areas of 1.a.1 geometry type specimens.
  • Table XI Throwing power (surface / cross section examination) Coating Coverage of 1.a.1 geometry type notch Pass/Fail AlumiPlateTM Full coating coverage in the notch Pass LHE Cd (1)(8) Full coating coverage in the notch Pass B01-1 (2)(3)(5)(8) Uncoated areas in the notch root Fail B01-2 (2)(3)(5)(8) Full coating coverage in the notch Pass B01-phen (2)(4)(5)(8) Uncoated areas in the notch root Fail B01-phen-KCI (2)(4)(6)(8) Full coating coverage in the notch Pass B01-phen-KCI (1)(4)(6)(8) Full coating coverage in the notch Pass B01-phen-KCI (2)(4)(6)(7)(8) Full coating coverage in the notch Pass
  • Table XII Hydrogen embrittlement (ASTM F-519) Coating Load/Loading time required by ASTM F-519 Hours without fracturing Pass/Fail AlumiPlateTM 200 Pass 200 200 200 LHE Cd (1)(8) 75% NFS / 200h 200 Pass 200 200 200 B01-1 (2)(3)(5)(8) 75% NFS / 200h 200 Pass 200 200 200 B01-2 (2)(3)(5)(8) 75% NFS / 200h 200 Pass 200 200 B01-phen (2)(4)(5)(8) - - - B01-phen-KCI (2)(4)(6)(8) - - - B01-phen-KCI (1)(4)(6)(8) 75% NFS / 200h 216 Fail 123,3 215,4 177,6 B01-phen-KCI (2)(4)(6)(7)(8) 75% NFS / 200h 200 Pass 200 200 200 200 200
  • the throwing power of the electrolyte was considerably improved with respect to that of the B01-phen.
  • This electrolyte also allowed an acceptable aluminum plating at higher current density and higher temperature than the B01 (without any additives), which results in higher electrodeposition rates.
  • the B01-phen-KCI electroplating bath achieves an improvement of the electrical conductivity of the bath and facilitates the deposition of aluminum because of the shift of the reduction potential of Al towards a nobler direction, so that an improvement of the throwing power can also be achieved.
  • the B01-phen-KCI electroplating process also achieved good adhesion properties of the resulting aluminum coating when F-80 to F-36 alumina grit blasting from was used during pre-treatment.
  • the B01-phen-KCI electroplating process also achieved good hydrogen embrittlement resistance when a baking step at 190 ⁇ 14oC for at least 23 hours was used during post-treatment.
  • the aluminum coating complying with all of the tests reported may be considered a more environmentally friendly coating than other sacrificial coatings for high strength ferrous steel parts such as Cd and Zn-Ni.
  • the process to achieve such coating would be considered more environmentally friendly, more safe and easier to handle than Cd plating, Zn/Ni plating, Al plating from organic solvents or AlumiPlateTM plating process.
  • the aluminum coating complying with most of the tests reported may still be considered a more environmentally friendly coating than other sacrificial coatings for ferrous steel parts such as Cd and Zn-Ni providing similar or superior corrosion resistance performance than Cd or Zn/Ni.
  • the process to achieve such coating would be still considered more environmentally friendly, more safe and easier to handle than Cd plating, Zn/Ni plating, Al plating from organic solvents or AlumiPlateTM plating process.

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Claims (7)

  1. Elektroplattierungsverfahren zum Beschichten eines Kathodensubstrats aus eisenhaltigem Legierungsstahl mit einem Aluminiumüberzug, dadurch gekennzeichnet, dass das Verfahren Folgendes umfasst:
    a) Vorbehandlung des Aluminium-Anodensubstrats, Folgendes umfassend:
    i) mechanisches Polieren eines Aluminium-Anodensubstrats,
    ii) alkalisches Reinigen des polierten Aluminiumsubstrats, gefolgt von einer Wasserspülung,
    iii) Entzundern des alkalisch gereinigten Aluminiumsubstrats, gefolgt von einer Wasserspülung, und
    iv) Trocknen des entzunderten Aluminiumsubstrats, um ein poliertes, gereinigtes, entzundertes und trockenes Aluminium-Anodensubstrat zu erhalten;
    b) Vorbehandlung des Kathodensubstrats aus eisenhaltigem Legierungsstahl, Folgendes umfassend:
    v) Entfetten des Kathodensubstrats aus eisenhaltigem Legierungsstahl und
    vi) Trockenstrahlen des entfetteten Kathodensubstrats aus eisenhaltigem Legierungsstahl, gefolgt von dem Entfernen von etwaigem Pulver, das auf der Oberfläche des abgebeizten, entfetteten Substrats aus eisenhaltigem Legierungsstahl verblieben ist, um ein entfettetes und gestrahltes Kathodensubstrat aus eisenhaltigem Legierungsstahl zu erhalten;
    c) Eintauchen des polierten, gereinigten, entzunderten und getrockneten Aluminium-Anodensubstrats, welches in Schritt a) vorbehandelt wurde, in eine Aluminiumplattierungsbad-Formulierung, bestehend aus:
    - einem Gemisch aus Aluminiumtrichlorid und 1-Ethyl-3-methylimidazoliumchlorid im Bereich von 95,30 bis 99,95 Gew.-%, wobei beide Bestandteile in dem Gemisch in einem Molverhältnis im Bereich von 80:40 bis 60:40 vorhanden sind,
    - 1,10-Phenantrolin in einem Bereich von 0,01 bis 1,0 Gew.-% und
    - KCl in einem Bereich von 0,04 bis 3,7 Gew.-%;
    d) Ätzen des entfetteten und trockengestrahlten Kathodensubstrats aus eisenhaltigem Legierungsstahl, welches in Schritt b) vorbehandelt wurde, durch Eintauchen in die Aluminiumplattierungsbad-Formulierung von Schritt c) und Durchführen eines anodischen Polarisationsschrittes;
    e) Elektroplattieren des geätzten Kathodensubstrats aus eisenhaltigem Legierungsstahl von Schritt d) mit der Aluminiumplattierungsbad-Formulierung von Schritt c), wobei Schritt e) mit einer Stromdichte im Bereich von 1 bis 100 mA/cm2, bei einer Temperatur im Bereich von 20 bis 100 °C und unter einem trockenen Inertgas durchgeführt wird;
    f) Spülen des in Schritt e) erhaltenen aluminiumüberzogenen Kathodensubstrats aus eisenhaltigem Legierungsstahl; und
    g) Wärmebehandlung des in Schritt f) erhaltenen aluminiumüberzogenen Kathodensubstrats aus eisenhaltigem Legierungsstahl.
  2. Elektroplattierungsverfahren gemäß Anspruch 1, wobei das Substrat aus eisenhaltigem Legierungsstahl zwischen 0,2 und 0,5 Gew.-% C und nicht mehr als 8 Gew.-% an Legierungselementen enthält.
  3. Elektroplattierungsverfahren gemäß einem der Ansprüche 1 bis 2, wobei der Schritt e) der Elektroplattierung mit einer Stromdichte im Bereich von 5 bis 25 mA/cm2, einer Temperatur im Bereich von 40 bis 75 °C und dem Rühren des Elektrolyten in einem Bereich von 500 bis 1000 U/min durchgeführt wird.
  4. Elektroplattierungsverfahren gemäß einem der Ansprüche 1 bis 3, wobei die Wärmebehandlung g) bei 190 ± 14 °C für mindestens 23 Stunden durchgeführt wird.
  5. Elektroplattierungsverfahren gemäß einem der Ansprüche 1 bis 4, welches ferner das Aufbringen einer Konversionsbeschichtung auf das in Schritt f) oder Schritt g) erhaltene aluminiumüberzogene Substrat aus eisenhaltigem Legierungsstahl umfasst, wobei die Konversionsbeschichtung aus einer Konversionsbeschichtung aus sechswertigem Chrom und einer chromfreien Konversionsbeschichtung ausgewählt wird.
  6. Aluminiumüberzogenes Substrat aus eisenhaltigem Legierungsstahl, welches gemäß dem in einem der Ansprüche 1 bis 5 beschriebenen Verfahren erhalten wird.
  7. Verwendung des aluminiumüberzogenen Substrats aus eisenhaltigem Legierungsstahl gemäß Anspruch 6 in Anwendungen in der Luftfahrt, im Automobilbau, im maritimen Bereich, im Bauwesen, in der Industrie und im Haushalt.
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