EP3767012B1 - Funktionale chromlegierungsplattierung aus dreiwertigen chromelektrolyten - Google Patents

Funktionale chromlegierungsplattierung aus dreiwertigen chromelektrolyten

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Publication number
EP3767012B1
EP3767012B1 EP20185818.0A EP20185818A EP3767012B1 EP 3767012 B1 EP3767012 B1 EP 3767012B1 EP 20185818 A EP20185818 A EP 20185818A EP 3767012 B1 EP3767012 B1 EP 3767012B1
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EP
European Patent Office
Prior art keywords
electrolyte solution
chromium
iron
per liter
moles per
Prior art date
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Active
Application number
EP20185818.0A
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English (en)
French (fr)
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EP3767012A1 (de
Inventor
Vijaykumar IJERI
Stephen P. Gaydos
Subramanian Mohan
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Boeing Co
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Boeing Co
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Publication of EP3767012A1 publication Critical patent/EP3767012A1/de
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Classifications

    • 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
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • 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

Definitions

  • the present disclosure provides electrolyte solutions for electrodeposition of chromium alloys and methods of electrodepositing chromium alloys. Also disclosed but not presently claimed are methods of forming electrolyte solutions.
  • Chrome plating is an electroplating process that provides a chrome coating on a substrate.
  • Hard chrome plating provides a chrome coating having a thickness typically about 10 microns or greater, thereby providing hardness and wear resistance to the coated substrate.
  • the other type of chrome plating is decorative chrome plating, which provides a chrome coating having a thickness typically ranging from about 0.1 to about 0.5 microns.
  • Chrome plating is often performed using baths containing chromic acid and catalysts based on fluorides, sulfates or organic acids.
  • Chromic acid has chromium in its hexavalent form, chromium (VI), which is not environmentally preferred and expensive to dispose of.
  • Trivalent chromium which has benign properties and lower waste treatment costs, is one alternative to hexavalent chromium. There has been some success implementing trivalent chromium for thin, decorative plating, however, there is still difficulty in achieving thicker or functional coatings. In addition, trivalent chromium-based baths used in decorative plating typically contain boric acid as a buffering agent.
  • KR20170141834 describes a metal plating method for automobile or decorative PC-ABS resin parts.
  • the plating method is executed in the following order: a step of pretreating a resin surface; a copper plating step; a Cu-Sn-Zn ternary alloy electroplating step; and a trivalent chromium plating step.
  • a nickel plating process is replaced by Cu-Sn-Zn ternary alloy plating, and the use of a cyanide is excluded from the ternary alloy plating process.
  • JP2006022358 describes a thermal spraying powder material which is used to form a corrosion-resistant film by thermal spraying on an internal peripheral surface of a container body of an anode container for a sodium-sulfur battery, wherein the cylindrical container body consists of a metallic material.
  • the molten pulverized powder consists of an alloy with chromium (Cr)-iron (Fe) as a base, which contains, by mass, 55-70% chromium (Cr) and 3-20% carbon (C).
  • US2019040540 describes a chromium-based coating including chromium (Cr), carbon (C) and iron (Fe), Cr being electroplated from a trivalent Cr bath.
  • the coating further includes nickel (Ni) electroplated from the Cr bath having at least 20 mg 1 -1 Ni cations, wherein C is at least partially in the form of at least one chromium carbide compound, wherein the coating has been heat-treated at a temperature of 400-1,200° C., and wherein the hardness of the coating is at least 1,500 HV on a Vickers microhardness scale as measured according to standard SFS-EN ISO 4516.
  • a method for producing a coating and to a coated object is also disclosed.
  • EP3241928 describes an electrolyte solution for chrome plating from trivalent chromium, prepared by dissolving in an aqueous medium a trivalent chromium salt (e.g., chromium (III) chloride or chromium (III) sulfate), dissolving an oxalate compound (e.g., sodium oxalate, potassium oxalate, or oxalic acid), dissolving a metal salt (e.g., aluminum sulfate or aluminum chloride), dissolving an alkali metal sulfate (e.g., sodium sulfate or potassium sulfate), and dissolving an alkali metal halide (e.g., sodium fluoride or potassium fluoride).
  • a substrate is chrome plated from trivalent chromium using the electrolyte solution by passing a current between a cathode and an anode through the electrolyte solution to deposit chromium on the substrate.
  • an electrolyte solution for electroplating as defined in claim 1.
  • the present disclosure provides electrolyte solutions for electrodeposition of chromium alloys, methods of forming electrolyte solutions, and methods of electrodepositing chromium alloys.
  • At least one electrolyte solution for electroplating includes a trivalent chromium salt, an oxalate compound, an iron salt, an aluminum sulfate, an alkali metal sulfate, and an alkali metal halide.
  • At least one electrolyte solution for electroplating includes a trivalent chromium salt in an amount ranging from about 0.3 moles per liter to about 0.9 moles per liter of the electrolyte solution.
  • the electrolyte solution further includes an oxalate compound in an amount ranging from about 0.2 moles per liter to about 1.2 moles per liter of the electrolyte solution.
  • the electrolyte solution further includes an iron salt in an amount ranging from about 0.005 moles per liter to about 0.2 moles per liter of the electrolyte solution.
  • the electrolyte solution further includes an aluminum sulfate in an amount ranging from about 0.05 moles per liter to about 0.5 moles per liter.
  • the electrolyte solution further includes an alkali metal sulfate in an amount ranging from about 0.1 moles per liter to about 2.0 moles per liter of the electrolyte solution.
  • the electrolyte solution further includes an alkali metal halide in an amount ranging from about 0.1 moles per liter to about 0.5 moles per liter of the electrolyte solution.
  • At least one method of chrome plating on a substrate using an electrolyte solution includes dissolving in an aqueous medium a trivalent chromium salt in an amount ranging from about 0.3 moles per liter to about 0.9 moles per liter of the electrolyte solution.
  • the method further includes dissolving an oxalate compound in an amount ranging from about 0.2 moles per liter to about 1.2 moles per liter of the electrolyte solution.
  • the method further includes dissolving iron salt in an amount ranging from about 0.005 moles per liter to about 0.2 moles per liter of the electrolyte solution.
  • the method further includes dissolving aluminum sulfate in an amount ranging from about 0.05 moles per liter to about 0.5 moles per liter.
  • the method further includes dissolving an alkali metal sulfate in an amount ranging from about 0.1 moles per liter to about 2.0 moles per liter of the electrolyte solution.
  • the method further includes dissolving an alkali metal halide in an amount ranging from about 0.1 moles per liter to about 0.5 moles per liter of the electrolyte solution.
  • the method further comprises passing a current between a cathode and an anode through the electrolyte solution to deposit a chromium-iron alloy on a substrate.
  • At least one method of chrome plating on a substrate using an electrolyte solution includes introducing a cathode and an anode into an electrolyte solution comprising a trivalent chromium salt, an oxalate compound, an iron salt, an aluminum sulfate, an alkali metal sulfate, and an alkali metal halide.
  • the trivalent chromium salt is present in an amount ranging from about 0.3 moles per liter to about 0.9 moles per liter of the electrolyte solution; the oxalate compound is present in an amount ranging from about 0.2 moles per liter to about 1.2 moles per liter of the electrolyte solution; the iron salt is present in an amount ranging from about 0.005 moles per liter to about 0.2 moles per liter of the electrolyte solution; the aluminum sulfate is present in an amount ranging from about 0.05 moles per liter to about 0.5 moles per liter; the alkali metal sulfate is present in an amount ranging from about 0.1 moles per liter to about 2.0 moles per liter of the electrolyte solution; the alkali metal halide is present in an amount ranging from about 0.1 moles per liter to about 0.5 moles per liter of the electrolyte solution; and the electrolyte solution does not include boric acid.
  • the method further includes
  • At least one substrate including a chromium-iron alloy coating is provided but not presently claimed.
  • the chromium-iron alloy coating has a chromium content in a range of about 40 wt. % to about 90 wt. %, an iron content in a range of about 8 wt. % to about 18 wt. %, and a carbon content in the range of about 5 wt. % to about 50 wt. %.
  • the chromium-iron alloy coating may consist essentially of chromium, iron and carbon.
  • various methods and formulations are provided for chrome plating a substrate using direct current and a trivalent chromium solution that does not include boric acid, while still resulting in a chromium layer (e.g., a chromium coating) formed on the substrate that can be structurally robust and reliable, yet cost-effective.
  • a chromium layer e.g., a chromium coating
  • the methods and formulations described herein can advantageously be used for hard chrome plating to form hard chromium layers (e.g., a robust, functional chromium layer of greater than 10 microns).
  • the present disclosure is not limited to hard chrome plating and the methods and formulations described herein can also be advantageously used to effectively and efficiently perform decorative chrome plating, which forms decorative chromium layers (e.g., a chromium layer ranging from 0.25 micron to 1.0 micron).
  • decorative chrome plating which forms decorative chromium layers (e.g., a chromium layer ranging from 0.25 micron to 1.0 micron).
  • electrolyte solutions of the present disclosure are aqueous.
  • the electrolyte solution comprises an iron salt, such as, for example, ferrous sulfate or ferric chloride. It has been discovered that one or more of these iron salts present in an electrolyte solution provides deposition of thick chromium-iron alloy layers on a substrate, such as a steel substrate without the use of hexavalent chromium and pulsed plating.
  • Electrolyte solutions of the present disclosure further comprise at least one complexing agent such as an oxalate compound, for example, sodium oxalate, which forms complexes with trivalent chromium ions as well as ferrous ions.
  • Electrolyte solutions of the present disclosure provide controllable chromium-iron alloy deposition on a substrate.
  • a substrate is a steel substrate, copper substrate, brass substrate, copper-coated substrate, nickel-coated substrate, or other metal or metal alloy-containing substrate.
  • the electrolyte solutions of the present disclosure when used at temperatures in a range of about 30° C to about 60° C in at a pH in a range of about 2 to about 4 provide satisfactorily hard chromium-iron alloy deposits that are considered comparable to conventional hexavalent chromium based coatings.
  • iron content of a chromium-iron alloy of the present disclosure is from about 1 wt. % iron to about 20 wt. % iron based on the total weight of chromium and iron in the alloy.
  • Chromium-iron alloy coatings of the present disclosure provide similar hardness and wear resistance for substrates, such as steel substrates, to that of conventional hexavalent hard chrome plated substrates.
  • the chromium-iron alloys of the present disclosure can be disposed on components of aircraft, spacecraft, watercraft, engine and blown-flap, exhaust-washed structures, warm-structure components for high-performance supersonic, hypersonic, and space re-entry vehicle structures, automobile parts, architectural structures such as steel bridges and propulsion structures such as power-generation turbines, vehicle engines, alternative-energy applications, and related technologies.
  • alloys of the present disclosure can be disposed on steel-based landing gears and/or a bottom surface of an aircraft.
  • chromium-iron coatings of the present disclosure are formed using a single bath technique.
  • the deposition vessel is a glass beaker at a lab scale or large polypropylene tanks for plating on a commercial scale.
  • the deposition vessel contains an electrolyte solution that is prepared by mixing all ingredients of the electrolyte solution concurrently or in a stepwise manner starting with chromium salts and complexing agents followed by iron salts.
  • the anode e.g., graphite
  • the deposition process is modulated by applying direct current, which creates the chromium-iron alloy coating.
  • the thickness of the chromium-iron alloy coating can be controlled by the duration of the direct current applied to the electrolyte solution electrodes.
  • the total thickness of a chromium-iron alloy coating is from about 1 micron to about 100 microns, such as from about 10 microns to about 50 microns, such as from about 20 microns to about 40 microns, for example about 30 microns.
  • Varying the thickness and composition of a chromium-iron alloy coating can be controlled by current density and time scale of a deposition process of the present disclosure.
  • Electrolyte solutions of the present disclosure comprise a metal salt.
  • metal salt can include anhydrous and /or hydrate forms of a metal salt.
  • metal salts include one or more of a trivalent chromium salt and an iron salt.
  • Electrolyte solutions of the present disclosure further comprise at least one complexing agent such as an alkali metal oxalate compound, for example, sodium oxalate or potassium oxalate.
  • Complexing agents such as alkali metal oxalate compounds, coordinate to iron ions in an electrolyte solution and promote controllable iron deposition on a substrate upon application of a current density to the electrolyte solution.
  • Electrolyte solutions of the present disclosure further comprise at least one buffering agent such as an aluminum salt.
  • the at least one buffering agent is aluminum sulfate.
  • the buffering agent is an aluminum halide. Buffering agents of the present disclosure maintain a desirable pH of the electrolyte solution and do not substantially interfere with chromium and iron deposition on a substrate, as described in more detail below.
  • Electrolyte solutions of the present disclosure further comprise at least one ionic conductivity control agent such as an alkali metal salt.
  • the at least one ionic conductivity control agent is an alkali metal sulfate.
  • the alkali metal sulfate may be, for example, sodium sulfate or potassium sulfate.
  • Ionic conductivity control agents of the present disclosure maintain a desirable conductivity of the electrolyte solution and do not substantially interfere with chromium and iron deposition on a substrate.
  • Electrolyte solutions of the present disclosure further comprise at least one alkali metal halide, for example, sodium fluoride or potassium fluoride.
  • Alkali metal halides of the present disclosure provide the electrolyte solution with wetting and etching properties, and can help chromium adhesion during chrome plating.
  • electrolyte solutions of the present disclosure further comprise at least one surfactant, for example, sodium lauryl sulfate, sodium lauryl ether sulfate, or potassium lauryl sulfate.
  • surfactants of the present disclosure reduce pitting and gas generation during chrome plating.
  • the pH of electrolyte solutions of the present disclosure is between about 1 and about 6, such as between about 1.5 and about 4, for example the pH is 2 or 4.
  • the pH of electrolyte solutions of the present disclosure are controlled by addition of one or more bases, such as a sodium hydroxide (NaOH) solution, to increase the pH of the solution or addition of one or more acids, such as a sulfuric acid (H 2 SO 4 ) solution, to decrease the pH of the solution.
  • bases such as a sodium hydroxide (NaOH) solution
  • acids such as a sulfuric acid (H 2 SO 4 ) solution
  • Chromium salts, iron salts, complexing agents, buffering agents, acids, and bases can be obtained from any suitable commercial source, such as MERCK-India or Sigma-Aldrich Co. LLC of St. Louis, Mo.
  • FIG. 1 is a flow diagram illustrating a method 100 for forming an electrolyte solution according to one or more aspects of the present disclosure.
  • method 100 includes dissolving a trivalent chromium salt in a medium such as water or an aqueous solution to form a first electrolyte solution.
  • the trivalent chromium salt is a trivalent chromium source.
  • the trivalent chromium salt includes a chromium (III) halide, chromium (III) sulfate (e.g., Cr 2 (SO 4 ) 3 , Cr 2 (SO 4 ) 3 ⁇ 12H 2 O, and/or other chromium (III) sulfates), and/or other chromium (III) salts.
  • the chromium (III) halide can include, for example, chromium (III) chloride (e.g., CrCl 3 , CrCl 3 ⁇ 5H 2 O, CrCl 3 ⁇ 6H 2 O, and/or other chromium (III) chlorides).
  • the concentration of the trivalent chromium salt in the electrolyte ranges from about 0.3 moles per liter to about 0.9 moles per liter of the electrolyte solution.
  • the concentration of the trivalent chromium salt in the electrolyte of the present disclosure ranges from about 0.1 moles per liter (mol/L) to about 1 mol/L, such as in a range from about 0.3 mol/L to about 0.9 mol/L, such as in a range from about 0.2 mol/L to about 0.7 mol/L, such as in a range from about 0.4 mol/L to about 0.7 mol/L of the electrolyte solution, for example, in a range from about 0.5 mol/L to about 0.6 mol/L.
  • the amount of the trivalent chromium salt that is dissolved is about 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.7 mol/L, 0.8 mol/L, 0.9 mol/L, or 1 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • concentrations above 1 mol/L it can become difficult to dissolve the trivalent chromium salt in the electrolyte leading to solubility issues.
  • the trivalent chromium salt is dissolved by stirring at ambient temperature, at room temperature, at about 25° C, or at a temperature ranging from about 10° C to about 40° C, for example, from about 20° C to about 30° C.
  • the temperature at which operation 110 is performed can be about 10° C, 15° C, 20° C, 25° C, 30° C, 35° C, or 40° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the stirring can be performed for about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, where any value can form an upper end point or a lower end point, as appropriate, or until all the trivalent chromium salt has been dissolved.
  • the method 100 further includes dissolving an oxalate compound for example, in water or an aqueous solution (such as the first solution) to form an electrolyte solution, such as a second electrolyte solution.
  • the oxalate compound includes oxalate, which can function as a complexing agent.
  • the oxalate compound includes an alkali metal oxalate (e.g., sodium oxalate (Na 2 C 2 O 4 ), a potassium oxalate (K 2 C 2 O 4 ), and/or other alkali metal oxalates) and/or an acid of oxalate (e.g., oxalic acid (H 2 C 2 O 4 ) and/or other acids of oxalate).
  • an alkali metal oxalate e.g., sodium oxalate (Na 2 C 2 O 4 ), a potassium oxalate (K 2 C 2 O 4 ), and/or other alkali metal oxalates
  • an acid of oxalate e.g., oxalic acid (H 2 C 2 O 4 ) and/or other acids of oxalate.
  • the concentration of the oxalate compound in the electrolyte ranges from about 0.2 moles per liter to about 1.2 moles per liter of the electrolyte solution.
  • the concentration of the oxalate compound in the electrolyte of the present disclosure is in a range from about 0.1 mol/L to about 2.0 mol/L, such as in a range from about 0.2 mol/L to about 1.2 mol/L such as in a range from about 0.1 mol/L to about 0.9 mol/L, such as in a range from about 0.2 mol/L to about 0.7 mol/L, such as in a range from about 0.4 mol/L to about 0.7 mol/L of the electrolyte solution, for example, in a range from about 0.5 mol/L to about 0.6 mol/L.
  • the amount of the oxalate compound that is dissolved is about 0.1 mol/L, 0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L, 1.0 mol/L, 1.2 mol/L, 1.4 mol/L, 1.6 mol/L, 1.8 mol/L, or 2.0 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • the oxalate compound is put in solution (e.g., the solution resulting from operation 110 or another operation performed prior to operation 120), the solution can be heated to a higher temperature ranging from about 70° C to about 80° C, and the solution can be stirred for about 1 hour to about 3 hours.
  • the solution is cooled (e.g., to ambient temperature, to room temperature, to about 25° C, or to a temperature ranging from about 20° C to about 30° C).
  • the oxalate compound can be dissolved without heating, in which case a complex of oxalate and trivalent chromium is formed in 3 to 4 days.
  • heating the solution to a temperature ranging from about 70° C to about 80° C at operation 120 allows the electrolyte solution to be prepared more quickly.
  • the stirring is performed for about 1 hour, 1 hour and 15 minutes, 1 hour and 30 minutes, 1 hour and 45 minutes, 2 hours, 2 hours and 15 minutes, 2 hours and 30 minutes, 2 hours and 45 minutes, or 3 hours, where any value can form an upper end point or a lower end point, as appropriate.
  • the temperature at which operation 120 is performed is about 50° C, 55° C, 60° C, 65° C, 70° C, 75° C, or 80° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the method 100 further includes dissolving an iron salt, for example, in water or an aqueous solution (such as the second electrolyte solution) to form an electrolyte solution (e.g., a third electrolyte solution).
  • an iron salt for example, in water or an aqueous solution (such as the second electrolyte solution) to form an electrolyte solution (e.g., a third electrolyte solution).
  • the iron salt is a divalent iron salt, a trivalent iron salt, or a combination thereof.
  • the iron salt is ferrous sulfate heptahydrate, ferric chloride, or a combination thereof.
  • the iron salt is a divalent iron salt.
  • the divalent iron salt includes iron (II) sulfate, iron (II) chloride, iron (II) acetate, and/or other divalent iron salts.
  • Each of these divalent iron salts can include its respective hydrated forms.
  • iron (II) sulfate has the formula FeSO 4 ⁇ xH 2 O, where x is a whole number (e.g., 0, 1, 2, 4, 5, 6, or 7).
  • iron (II) sulfate is anhydrous iron (II) sulfate, iron (II) sulfate monohydrate, iron (II) sulfate dihydrate, iron (II) sulfate tetrahydrate, iron (II) sulfate pentahydrate, iron (II) sulfate hexahydrate, iron (II) sulfate heptahydrate, or iron (II) sulfate with another hydration state.
  • the iron salt is a trivalent iron salt.
  • the trivalent iron salt includes iron (III) sulfate, iron (III) chloride, iron (III) acetate, and/or other trivalent iron salts.
  • Each of these trivalent iron salts can include its respective hydrated forms.
  • iron (III) sulfate has the formula Fe 2 (SO 4 ) 3 ⁇ xH 2 O, where x is a whole number (e.g., 0, 1, 2, 4, 5, 6, or 7).
  • iron (III) sulfate is anhydrous iron (III) sulfate, iron (III) sulfate monohydrate, iron (III) sulfate dihydrate, iron (III) sulfate tetrahydrate, iron (III) sulfate pentahydrate, iron (III) sulfate hexahydrate, iron (III) sulfate heptahydrate, or iron (III) sulfate with another hydration state.
  • iron (III) chloride has the formula FeCl 3 ⁇ xH 2 O, where x is a whole number (e.g., 0, 1, 2, 4, 5, 6, or 7).
  • iron (III) chloride is anhydrous iron (III) chloride, iron (III) chloride monohydrate, iron (III) chloride dihydrate, iron (III) chloride tetrahydrate, iron (III) chloride pentahydrate, iron (III) chloride hexahydrate, iron (III) chloride heptahydrate, or iron (III) chloride with another hydration state.
  • the concentration of the iron salt in the electrolyte of the present disclosure ranges from about 0.005 mol/L to about 0.2 mol/L, such as in a range from about 0.01 mol/L to about 0.2 mol/L, such as in a range from about 0.02 mol/L to about 0.2 mol/L of the electrolyte solution, for example, in a range from about 0.1 mol/L to about 0.2 mol/L.
  • the amount of the iron salt that is dissolved is about 0.005 mol/L, 0.01 mol/L, 0.02 mol/L, 0.03 mol/L, 0.04 mol/L, 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.08 mol/L, 0.09 mol/L, 0.1 mol/L, or 0.2 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate. It has been found by the inventors that at concentrations above 0.2 mol/L, the deposited chromium-iron alloy coating becomes soft and can also be more susceptible to corrosion.
  • the iron salt is dissolved by stirring at ambient temperature, at room temperature, at about 25° C, or at a temperature ranging from about 20° C to about 30° C. In at least one aspect, the stirring is performed for about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, where any value can form an upper end point or a lower end point, as appropriate, or until all the iron salt has been dissolved. In at least one aspect, the temperature at which operation 130 is performed is about 10° C, 15° C, 20° C, 25° C, 30° C, 35° C, or 40° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the method 100 further includes dissolving a metal salt, for example, in water or an aqueous solution (such as the third electrolyte solution) to form an electrolyte solution (e.g., a fourth electrolyte solution).
  • the metal salt is a metal ion source that dissolves to provide metal ions such as aluminum ions, which can function as a buffer and can provide ionic strength due to the high valence of the metal ion in solution (e.g., Al 3+ ).
  • the metal salt includes a group 13 metal salt such as an aluminum salt.
  • the metal salt is aluminum sulfate (Al 2 (SO 4 ) 3 .
  • the metal salt is an aluminum halide such as aluminum chloride (AlCl 3 ), and/or other aluminum salts, and/or other metal salts.
  • the concentration of the metal salt in the electrolyte ranges from about 0.05 moles per liter to about 0.5 moles per liter. In some examples of the present disclosure, the concentration of the metal salt in the electrolyte of the present disclosure ranges from about 0.01 mol/L to about 1.0 mol/L, such as in a range from about 0.05 mol/L to about 0.8 mol/L, such as in a range from about 0.1 mol/L to about 0.7 mol/L, such as in a range from about 0.2 mol/L to about 0.5 mol/L of the electrolyte solution, for example, in a range from about 0.2 mol/L to about 0.3 mol/L.
  • the amount of the metal salt that is dissolved is about 0.01 mol/L, 0.05 mol/L, 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.8 mol/L, or 1.0 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • concentrations above 1.0 mol/L it can become difficult to dissolve the metal salt in the electrolyte leading to solubility issues.
  • the metal salt is dissolved by stirring at ambient temperature, at room temperature, at about 25° C, or at a temperature ranging from about 20° C to about 30° C. In at least one aspect, the stirring is performed for about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, where any value can form an upper end point or a lower end point, as appropriate, or until all the metal salt has been dissolved. In at least one aspect, the temperature at which operation 140 is performed is about 10° C, 15° C, 20° C, 25° C, 30° C, 35° C, or 40° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the method 100 further includes dissolving an alkali metal salt, for example, in water or an aqueous solution (such as the fourth electrolyte solution) to form an electrolyte solution (e.g., a fifth electrolyte solution).
  • the alkali metal salt can increase the conductivity of the electrolyte solution.
  • the alkali metal salt is an alkali metal sulfate (e.g., sodium sulfate (Na 2 SO 4 ), potassium sulfate (K 2 SO 4 ), and/or other alkali metal sulfates).
  • the concentration of the alkali metal salt in the electrolyte of the present disclosure is in a range from about 0.1 mol/L to about 2.0 mol/L, such as in a range from about 0.5 mol/L to about 2.0 mol/L such as in a range from about 1.0 mol/L to about 1.5 mol/L, for example, in a range from about 1.3 mol/L to about 1.4 mol/L.
  • the amount of the oxalate compound that is dissolved is about 0.1 mol/L, 0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L, 1.0 mol/L, 1.2 mol/L, 1.4 mol/L, 1.6 mol/L, 1.8 mol/L, or 2.0 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • concentrations above 2.0 mol/L it can become difficult to dissolve the alkali metal salt in the electrolyte leading to solubility issues.
  • the alkali metal salt is dissolved by stirring at ambient temperature, at room temperature, at about 25° C, or at a temperature ranging from about 10° C to about 40° C, for example, from about 20° C to about 30° C.
  • the temperature at which operation 150 is performed can be about 10° C, 15° C, 20° C, 25° C, 30° C, 35° C, or 40° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the stirring can be performed for about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, where any value can form an upper end point or a lower end point, as appropriate, or until all the alkali metal salt has been dissolved.
  • the alkali metal salt is dissolved by stirring for 15 minutes at ambient temperature, at room temperature, at about 25° C.
  • the method 100 further includes dissolving an alkali metal halide, for example, in water or an aqueous solution (such as the fifth electrolyte solution) to form an electrolyte solution (e.g., a sixth electrolyte solution).
  • the alkali metal halide can provide the electrolyte solution with wetting and etching properties, and can help chromium adhesion during chrome plating.
  • the alkali metal halide includes an alkali metal fluoride (e.g., sodium fluoride (NaF), potassium fluoride (KF), and/or other alkali metal fluorides) and/or other alkali metal halides.
  • the concentration of the alkali metal halide in the electrolyte is in a range from about 0.1 moles per liter to about 0.5 moles per liter of the electrolyte solution.
  • the concentration of the alkali metal halide in the electrolyte of the present disclosure is in a range from about 0.1 mol/L to about 1.0 mol/L, such as in a range from about 0.1 mol/L to about 0.5 mol/L such as in a range from about 0.2 mol/L to about 0.5 mol/L, for example, in a range from about 0.3 mol/L to about 0.4 mol/L.
  • the amount of the oxalate compound that is dissolved is about 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.8 mol/L, or 1.0 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • concentrations above 1.0 mol/L it can become difficult to dissolve the alkali metal halide in the electrolyte leading to solubility issues.
  • the alkali metal halide is dissolved by stirring at ambient temperature, at room temperature, at about 25° C, or at a temperature ranging from about 10° C to about 40° C, for example, from about 20° C to about 30° C.
  • the temperature at which operation 160 is performed is about 10° C, 15° C, 20° C, 25° C, 30° C, 35° C, or 40° C, where any value can form an upper end point or a lower end point, as appropriate.
  • the stirring is performed for about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, where any value can form an upper end point or a lower end point, as appropriate, or until all the alkali metal halide has been dissolved.
  • the alkali metal halide is dissolved by stirring for 15 minutes at ambient temperature, at room temperature, at about 25° C.
  • the method 100 further includes dissolving a surfactant, for example, in water or an aqueous solution (such as the sixth electrolyte solution) to form an electrolyte solution (e.g., a seventh electrolyte solution).
  • a surfactant for example, in water or an aqueous solution (such as the sixth electrolyte solution) to form an electrolyte solution (e.g., a seventh electrolyte solution).
  • the surfactant can prevent or reduce pitting and reduce gas generation (e.g., chlorine gas, hydrogen gas, etc.) during chrome plating.
  • the surfactant includes sodium lauryl sulfate (NaC 12 H 25 SO 4 ), sodium lauryl ether sulfate (CH 3 (CH 2 ) 11 (OCH 2 CH 2 ) n OSO 3 Na), potassium lauryl sulfate (KC 12 H 25 SO 4 ), and/or other surfactants.
  • the concentration of the surfactant in the electrolyte of the present disclosure is in a range from about 0.0001 mol/L to about 0.01 mol/L.
  • the amount of the surfactant that is dissolved can be about 0.0001 mol/L, 0.0002 mol/L, 0.0004 mol/L, 0.0006 mol/L, 0.0008 mol/L, 0.0010 mol/L, 0.0020 mol/L, 0.0040 mol/L, 0.0060 mol/L, 0.0080 mol/L, or 0.0100 mol/L of the electrolyte solution, where any value can form an upper end point or a lower end point, as appropriate.
  • the amount of sodium lauryl sulfate, sodium lauryl ether sulfate, or potassium lauryl sulfate is in a range from about 0.1 g to about 1 g per liter of the electrolyte solution.
  • the surfactant can cause excessive foaming of the bath and nonuniform deposition.
  • the method 100 further includes adjusting the pH of the electrolyte solution using one or more aqueous acid solutions or aqueous base solutions, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), and/or sulfuric acid (H 2 SO 4 ).
  • aqueous acid solutions or aqueous base solutions such as potassium hydroxide (KOH), sodium hydroxide (NaOH), and/or sulfuric acid (H 2 SO 4 ).
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • SO 4 sulfuric acid
  • the volume of aqueous acid solution or aqueous base solution added to the electrolyte solution is sufficiently small such that the concentration of other components (complexing agents, buffering agents, etc.) of the electrolyte solution is not substantially affected.
  • solid potassium hydroxide and/or solid sodium hydroxide is added directly to the electrolyte solution and/or concentrated sulfuric acid is added directly to the electrolyte solution.
  • the pH of the electrolyte solution is adjusted to a target pH from about 1 to about 7, such as from about 1 to about 5, such as from about 1.5 to about 4, for example 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5.
  • the pH of an electrolyte solution of the present disclosure is adjusted before passing a current through the electrolyte solution (as described in more detail below).
  • the pH of an electrolyte solution of the present disclosure is maintained at a target pH or a target pH range during the passing of a current through the electrolyte solution.
  • time is provided to reach equilibrium state.
  • the solution is left to stand for a time ranging from 1 hour to 2 days to reach the equilibrium state.
  • the time provided to reach the equilibrium state can be about 1 hour, 3 hours, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours, 24 hours, 27 hours, 30 hours, 33 hours, 36 hours, 39 hours, 42 hours, 45 hours, or 48 hours, where any value can form an upper end point or a lower end point, as appropriate.
  • the method 100 is performed in the order presented. Alternatively, the method 100 is performed in a different order. In at least one aspect, some operations are performed in order while other operations are performed in a different order. For example, operations 110 and 120 are performed in order, while operations 130, 140, 150, 160, 170, 180, and 190 are performed in a different order after operations 110 and 120. In another example, operations 110 and operations 120 are performed in a different order while operations 130, 140, 150, 160, 170, 180, and 190 are performed in order. In another example, operations 110, 120, 130, 140, 150, and 160 are performed in order, while operations 170, 180, and 190 are performed in a different order. A group of operations can be performed before another group of operations.
  • operations 110 and 120 can be performed in any order, and after operations 110 and 120 are performed, operations 130, 140, 150, and 160 are performed in any order. Other orders are contemplated as one skilled in the art will appreciate. Further, one or more of operations 170, 180, and 190 are omitted in some aspects.
  • FIG. 2 is a flow diagram illustrating a method 200 for forming a chromium alloy coating on a substrate by electrodeposition according to one or more aspects of the present disclosure.
  • an electrolyte solution is prepared, such as by the method 100 of FIG. 1 .
  • the method 200 further includes adjusting and/or maintaining a pH of the electrolyte solution at a target pH or a target pH range.
  • the target pH is a pH ranging from about 1 to about 4.
  • the pH can be maintained at about 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, or 4.0, where any value can form an upper end point or a lower end point, as appropriate.
  • the method 200 further includes adjusting and/or maintaining a temperature of an electrolyte solution, such as the electrolyte solution formed by operation 210.
  • the temperature is adjusted to/maintained at a target temperature of from about 20° C to about 70° C, such as from about 20° C to about 40° C, such as from about 20° C to about 35° C, for example 20° C, 25° C, or 30° C, using any suitable heating or cooling apparatus.
  • the temperature of the electrolyte solution is adjusted before passing a current through the electrolyte solution.
  • the temperature of the electrolyte solution is maintained during the passing of a current through the electrolyte solution to maintain the appearance of a deposited layer. Maintaining the temperature within a desirable range promotes obtaining reproducible results in terms of appearance and alloy composition.
  • the method further includes introducing a cathode and an anode into the electrolyte solution, the cathode including the substrate and at operation 250, passing a current between the cathode and the anode through the electrolyte solution to deposit a chromium alloy onto the cathodic substrate.
  • the cathodic substrate is, for example, a steel substrate, a ferrous alloy substrate, a copper substrate, a brass substrate, a nickel substrate, a copper-coated substrate (e.g., copper-coated steels or copper-coated ferrous alloys), or a nickel-coated substrate (e.g., nickel-coated steels or nickel-coated ferrous alloys).
  • the anode includes a carbonaceous electrode material.
  • the carbonaceous anode can be a graphite anode or other anode that includes carbon.
  • the graphite anode is used for chloride-based electrolyte solutions (e.g., electrolyte solutions that include one or more compounds with chloride such as chromium (III) chloride), sulfate-based electrolyte solutions (e.g., electrolyte solutions that include one or more compounds with sulfate such as chromium (III) sulfate), or chloride and sulfate-based electrolyte solutions (e.g., electrolyte solutions that include one or more compounds with chloride and one or more other compounds with sulfate).
  • chloride-based electrolyte solutions e.g., electrolyte solutions that include one or more compounds with chloride such as chromium (III) chloride
  • sulfate-based electrolyte solutions e.g.
  • the graphite anode or other carbonaceous anode minimizes gas evolution and formation of undesirable byproducts, as well as facilitating a desirable deposition rate (e.g., ranging from about 1 micron to about 2 microns per minute).
  • a platinum anode or a platinized titanium anode can be used for sulfate-based electrolyte solutions (e.g., electrolyte solutions that include one or more compounds with sulfate such as chromium (III) sulfate).
  • the platinum anode or platinized titanium anode can be used when the electrolyte solution does not include compounds with chloride such that chlorine gas is not produced, or when the electrolyte solution has less chloride such that less chlorine gas is generated (e.g., there is no need to reduce the generation of chlorine gas using a carbonaceous anode).
  • passing a current between the cathode and the anode is performed using direct current.
  • direct current having a current density of from about 50 mA/cm 2 to about 600 mA/cm 2 , such as from about 100 mA/cm 2 to about 500 mA/cm 2 , such as from about 100 mA/cm 2 to about 400 mA/cm 2 , such as from about 200 mA/cm 2 to about 400 mA/cm 2 , for example 200 mA/cm 2 , 250 mA/cm 2 , or 300 mA/cm 2 is used.
  • the value of the current density can be adjusted depending on the separation between the cathode and anode.
  • the current density is about 50 mA/cm 2 , 100 mA/cm 2 , 150 mA/cm 2 , 200 mA/cm 2 , 250 mA/cm 2 , 300 mA/cm 2 , 350 mA/cm 2 , 400 mA/cm 2 , 450 mA/cm 2 , or 500 mA/cm 2 , where any value can form an upper end point or a lower end point, as appropriate, depending on the separation between the cathode and anode.
  • a current density ranging from about 200 mA/cm 2 to about 400 mA/cm 2 can be applied when the cathode and the anode is separated by about 3 cm. It has been found by the inventors that a current density in the aforementioned range minimizes the formation of undesirable hexavalent chromium byproducts while achieving a reasonable rate of deposition, for example, 0.5 to 1 micron/minute.
  • the chromium alloy coating layer is a chromium-iron alloy having from about 1 wt. % iron to about 60 wt. % iron, such as from about 1 wt. % iron to about 20 wt. % iron, such as from about 1 wt. % iron to about 5 wt. % iron or from about 10 wt. % iron to about 20 wt. % iron based on the total weight of the alloy.
  • the chromium-iron alloy can have a wt. % iron of about 1 wt. %, 2 wt. %, 10 wt. %, 11 wt. %, or 12 wt. %.
  • the chromium-iron alloy has from about 80 wt. % chromium to about 99 wt. % chromium, such as from about 85 wt. % chromium to about 95 wt. % chromium, for example about 99 wt. % chromium, 98 wt. % chromium, 90 wt. % chromium, 89 wt. % chromium, or 88 wt. % chromium, based on the total weight of the alloy.
  • the chromium-iron alloy may consist essentially of chromium and iron.
  • chromium is deposited on the substrate.
  • chromium and carbon are co-deposited on the substrate.
  • operation 250 is performed until a chromium layer (e.g., a chromium coating) or a chromium-carbon layer (e.g., a chromium carbide coating) having a desired thickness (e.g., a thickness greater than about 5 microns) is formed on the substrate.
  • the chromium layer having a thickness greater than about 5 microns can have hardness greater than about 800 HV.
  • impurities which do not substantially affect the physical properties of a chromium-iron alloy, or a chromium-iron alloy coating, may also be present in a chromium-iron alloy, or a chromium-iron alloy coating, as disclosed herein.
  • the presence of such impurities will not result in a departure from the scope of the present disclosure.
  • the maximum total content of impurities i.e. elements other than chromium and iron, or chromium, iron and carbon
  • Example 1 Chromium chloride hexahydrate (CrCl 3 ⁇ 6H 2 O) 159 g/L 0.6 M Sodium oxalate (Na 2 C 2 O 4 ) 80.4 g/L 0.6 M Ferrous sulfate hetpahydrate (FeSO 4 ⁇ 7H 2 O) 2.78 g/L 0.01 M Aluminum sulfate (Al 2 (SO 4 ) 3 ) 126.1 g/L 0.2 M Sodium sulfate (Na 2 SO 4 ) 184.6 g/L 1.3 M Sodium fluoride (NaF) 16.8 g/L 0.4 M
  • Example 2 The components of Example 2 were mixed in a stepwise manner with the chromium chloride hexahydrate and the sodium oxalate mixed first followed by the metal salts.
  • the components of Example 2 are similar to the components of Example 1, except that the amount of ferrous sulfate heptahydrate was increased 10 times compared to the components of Example 1.
  • the pH of Example 1 was ⁇ 2.2.
  • Example 2 Chromium chloride hexahydrate (CrCl 3 ⁇ 6H 2 O) 159 g/L 0.6 M Sodium oxalate (Na 2 C 2 O 4 ) 80.4 g/L 0.6 M Ferrous sulfate hetpahydrate (FeSO 4 ⁇ 7H 2 O) 27.8 g/L 0.1 M Aluminum sulfate (Al 2 (SO 4 ) 3 ) 126.1 g/L 0.2 M Sodium sulfate (Na 2 SO 4 ) 184.6 g/L 1.3 M Sodium fluoride (NaF) 16.8 g/L 0.4 M
  • Example 3 The components of Example 3 were mixed in a stepwise manner with the chromium chloride hexahydrate and the sodium oxalate mixed first followed by the metal salts.
  • the components of Example 3 are similar to the components of Example 1, except that ferrous sulfate heptahydrate is replaced with ferric chloride in Example 3.
  • the pH of Example 1 was approximately 2.2.
  • Example 3 Chromium chloride hexahydrate (CrCl 3 ⁇ 6H 2 O) 159 g/L 0.6 M Sodium oxalate (Na 2 C 2 O 4 ) 80.4 g/L 0.6 M Ferric chloride (FeCl 3 ) 1.62 g/L 0.01 M Aluminum sulfate (Al 2 (SO 4 ) 3 ) 126.1 g/L 0.2 M Sodium sulfate (Na 2 SO 4 ) 184.6 g/L 1.3 M Sodium fluoride (NaF) 16.8 g/L 0.4 M
  • FIG. 3 is an image 300 of chromium-iron alloy plated substrates 310, 320, 330, and 340, formed by the process of FIG. 2 , each plated at a different current density using the electrolyte solution of Example 1.
  • the plating parameters were a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of 30° C and a pH of approximately 2.2.
  • Chromium-iron alloy plated substrate 310 was plated at a current density of 100 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 12 ⁇ m.
  • Chromium-iron alloy plated substrate 320 was plated at a current density of 200 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 15 ⁇ m.
  • Chromium-iron alloy plated substrate 330 was plated at a current density of 250 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 28 ⁇ m.
  • Chromium-iron alloy plated substrate 340 was plated at a current density of 300 mA/cm 2 resulting in a chromium-iron layer having a thickness of 32 ⁇ m.
  • X-ray fluorescence was performed on a portion of each coating to determine the chromium content and the iron content by wt. %.
  • any current density ranging from 100 mA/cm 2 to about 300 mA/cm 2 provides deposition of a chromium-iron alloy layer.
  • a current density ranging from about 200 mA/cm 2 to about 280 mA/cm 2 provides a thick chromium-iron alloy layer with a low iron content.
  • a current density of 100 mA/cm 2 provides the thinnest chromium-iron alloy with a high iron content relative to a current density ranging from about 200 mA/cm 2 to about 300 mA/cm 2 .
  • FIG. 4 is an image 400 of chromium-iron alloy plated substrates 410, 420, 430, 440, and 450 formed by the process of FIG. 2 , each plated at a different pH using the electrolyte solution of Example 1.
  • the plating parameters were a direct current at a current density of 250 mA/cm 2 at a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of 30° C.
  • Chromium-iron alloy plated substrate 410 was plated at a pH of 1.0 resulting in patchy chromium-iron alloy deposits, which were not measured but were believed to be less than 10 ⁇ m.
  • Chromium-iron alloy plated substrate 420 was plated at a pH of 2.0 resulting in patchy chromium-iron alloy deposits, which were not measured, but were believed to be less than 10 ⁇ m.
  • Chromium-iron alloy plated substrate 430 was plated at a pH of 2.5 resulting in a chromium-iron alloy layer having a thickness of 20 ⁇ m.
  • Chromium-iron alloy plated substrate 440 was plated at a pH of 3.0 resulting in a chromium-iron alloy layer having a thickness of 28 ⁇ m.
  • Chromium-iron alloy plated substrate 450 was plated at a pH of 3.5 resulting in a chromium-iron alloy layer having a thickness of 45 ⁇ m.
  • X-ray fluorescence was performed on a portion of each coating to determine the chromium content and the iron content by wt. %. The results are depicted in Table II.
  • any pH ranging from 2.5 to 3.5 provides deposition of a chromium-iron alloy layer.
  • a pH range of 2.5 to 3.0 advantageously provides a thick chromium-iron alloy layer having a desired iron content.
  • a pH of 3.5 provides a thicker chromium-iron alloy layer with a lower iron content relative to a pH range of 2.5 to 3.0.
  • Table II pH Chromium (wt. %) Iron (wt. %) Thickness ( ⁇ m) 1.5 2.7 97.3 ⁇ 10 2.0 27.6 72.4 ⁇ 10 2.5 74.1 25.9 20 3.0 85.9 14.1 28 3.5 90.3 9.7 45
  • FIG. 5 is an image 500 of chromium-iron alloy plated substrates 510, 520, 530, and 540 formed by the process of FIG. 2 , each plated at a different current density using the electrolyte solution of Example 2.
  • the plating parameters were a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of 30° C and a pH of approximately 2.2.
  • Chromium-iron alloy plated substrate 510 was plated at a current density of 100 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 30 ⁇ m.
  • Chromium-iron alloy plated substrate 520 was plated at a current density of 200 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 40 ⁇ m.
  • Chromium-iron alloy plated substrate 530 was plated at a current density of 250 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 70 ⁇ m.
  • Chromium-iron alloy plated substrate 540 was plated at a current density of 300 mA/cm 2 resulting in a chromium-iron layer having a thickness of 50 ⁇ m.
  • X-ray fluorescence was performed on a portion of each coating to determine the chromium content and the iron content by wt. %. The results are depicted in Table III.
  • any current density ranging from 100 mA/cm 2 to about 300 mA/cm 2 provides deposition of a chromium-iron alloy.
  • a current density ranging from about 100 mA/cm 2 to about 250 mA/cm 2 provides a thick chromium-iron alloy layer.
  • the thickness of the chromium-iron alloy decreases relative to the thickness of the chromium-iron alloy deposited at a current density of 250 mA/cm 2 .
  • FIG. 6 is an image 600 of chromium-iron alloy plated substrates 610, 620, 630, 640, 650, and 660 formed by the process of FIG. 2 , each plated at a different pH using the electrolyte solution of Example 2.
  • the plating parameters were a direct current at a current density of 250 mA/cm 2 at a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of 30° C.
  • Chromium-iron alloy plated substrate 610 was plated at a pH of 1.5 resulting in patchy chromium-iron alloy deposit.
  • Chromium-iron alloy plated substrate 620 was plated at a pH of 2.0 resulting in patchy chromium-iron alloy deposits.
  • Chromium-iron alloy plated substrate 630 was plated at a pH of 2.5 resulting in a chromium-iron alloy layer having a thickness of 50 ⁇ m.
  • Chromium-iron alloy plated substrate 640 was plated at a pH of 3.0 resulting in a chromium-iron alloy layer having a thickness of 70 ⁇ m.
  • Chromium-iron alloy plated substrate 650 was plated at a pH of 3.5 resulting in a chromium-iron alloy layer having a thickness of 50 ⁇ m.
  • Chromium-iron alloy plated substrate 660 was plated at a pH of 4.0. X-ray fluorescence was performed on a portion of each coating to determine the chromium content and the iron content by wt. %. The results are depicted in Table IV.
  • any pH ranging from 1.5 to 4.0 provides deposition of a chromium-iron alloy layer.
  • a pH range of 2.0 to 4.0 advantageously provides a thick chromium-iron alloy layer having a desired high chromium content.
  • a pH of 3.0 provides a thicker chromium-iron alloy layer with good quality deposits.
  • the deposits exhibited burning at the edges, while at a pH of 2 or lower, the deposits were patchy.
  • Table IV pH Chromium (wt. %) Iron (wt. %) Thickness ( ⁇ m) 1.5 20.9 79.1 Patchy deposit 2.0 34.8 65.2 Patchy deposit 2.5 38.4 61.6 50 3.0 43.8 56.8 70 3.5 49.0 51.0 50 4.0 50.6 49.4 Burning at edges
  • FIG. 7 is an image 700 of chromium-iron alloy plated substrates 710, 720, 730, 740, 750, and 760 formed by the process of FIG. 2 , each plated at a different current density using the electrolyte solution of Example 3.
  • the plating parameters were a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of 30° C and a pH of approximately 2.2.
  • Chromium-iron alloy plated substrate 710 was plated at a current density of 100 mA/cm 2 resulting in patchy chromium-iron alloy deposits believed to be less than 10 ⁇ m thick.
  • Chromium-iron alloy plated substrate 720 was plated at a current density of 150 mA/cm 2 resulting in patchy chromium-iron alloy deposits believed to be less than 10 ⁇ m thick.
  • Chromium-iron alloy plated substrate 730 was plated at a current density of 200 mA/cm 2 resulting in a chromium-iron alloy layer having a thickness of 10 ⁇ m.
  • Chromium-iron alloy plated substrate 740 was plated at a current density of 300 mA/cm 2 resulting in a chromium-iron layer having a thickness of 30 ⁇ m.
  • Chromium-iron alloy plated substrate 750 was plated at a current density of 400 mA/cm 2 resulting in a chromium-iron layer having a thickness of 50 ⁇ m.
  • Chromium-iron alloy plated substrate 760 was plated at a current density of 500 mA/cm 2 resulting in deposits, which exhibited burning at the edges.
  • any current density ranging from 200 mA/cm 2 to about 400 mA/cm 2 provides deposition of a chromium-iron alloy.
  • a current density ranging from about 300 mA/cm 2 to about 400 mA/cm 2 provides a thick chromium-iron alloy layer.
  • the thickness of the chromium-iron alloy increased relative to the thickness of the chromium-iron alloy deposited at a current density of 400 mA/cm 2 , but the deposits at the edges were burned (black powder).
  • FIG. 8 is an image 800 of chromium-iron alloy plated substrates 810, 820, 830, 840, 850, 860, and 870 formed by the process of FIG. 2 , each plated at a different pH using the electrolyte solution of Example 3.
  • the plating parameters were a direct current at a current density of 250 mA/cm 2 at a plating time of approximately 1 hour while maintaining the electrolyte solution at a temperature of approximately 30° C.
  • Chromium-iron alloy plated substrate 810 was plated at a pH of 1.0 resulting in a chromium-iron alloy layer having a thickness of 20 ⁇ m.
  • Chromium-iron alloy plated substrate 820 was plated at a pH of 1.5 resulting in a chromium-iron alloy layer having a thickness of 24 ⁇ m.
  • Chromium-iron alloy plated substrate 830 was plated at a pH of 2.0 resulting in a chromium-iron alloy layer having a thickness of 20 ⁇ m.
  • Chromium-iron alloy plated substrate 840 was plated at a pH of 3.0 resulting in a chromium-iron alloy layer having a thickness of 16 ⁇ m.
  • Chromium-iron alloy plated substrate 860 was plated at a pH of 3.5 resulting in a chromium-iron alloy layer having a thickness of 16 ⁇ m.
  • Chromium-iron alloy plated substrate 870 was plated at a pH of 4.0 resulting in patchy chromium-iron alloy deposits of low thickness.
  • X-ray fluorescence was performed on a portion of coatings deposited at a pH of 2 and a pH of 2.5 to determine the chromium content and the iron content by wt. %. The results are depicted in Table VI.
  • any pH ranging from 1.0 to 4.0 provides deposition of a chromium-iron alloy.
  • a pH ranging from 1.0 to 2.5 advantageously provides a thicker chromium-iron alloy layer than a pH that is higher. Further, a pH ranging from 1.5 to 2.0 provides the thickest chromium-iron alloy layer.
  • Table VI pH Chromium (wt. %) Iron (wt. %) Thickness ( ⁇ m) 1.0 20 1.5 24 2.0 45 55 24 2.5 46 54 20 3.0 16 3.5 16 4.0 patchy deposits
  • FIG. 9 is an image 900 of chromium-iron alloy plated substrates 910, 920, 930, and 940 formed by the process of FIG. 2 , each plated at a different temperature using the electrolyte solution of Example 3.
  • the plating parameters were a direct current at a current density of 250 mA/cm 2 at a plating time of approximately 1 hour while maintaining the electrolyte solution at a pH of approximately 2.1.
  • Chromium-iron alloy plated substrate 910 was plated at a temperature of 30 ° C resulting in a chromium-iron alloy layer having a thickness of 40 ⁇ m.
  • Chromium-iron alloy plated substrate 920 was plated at a temperature of 40° C resulting in a chromium-iron alloy layer having a thickness of 30 ⁇ m.
  • Chromium-iron alloy plated substrate 930 was plated at a temperature of 50° C resulting in a chromium-iron alloy layer having a thickness of 30 ⁇ m.
  • Chromium-iron alloy plated substrate 940 was plated at a temperature of 60° C resulting in a chromium-iron alloy layer having a low thickness. The results are depicted in Table VII.
  • any temperature ranging from about 30° C to about 50° C provides deposition of a chromium-iron alloy layer.
  • the operating temperature of 30° C provides the thickest chromium-iron alloy layer, but the deposits at 40° C were aesthetically better.
  • chromium-iron-alloy coatings were deposited on a Taber Wear panels by a direct current at a current density of 300 mA/cm 2 for a plating time of approximately 2 hours while maintaining the electrolyte solution at a temperature of approximately 40° C and a pH of approximately 2.5.
  • the alloy composition of the coating as measured by SEM-EDS was chromium at ⁇ 41 wt. %, iron at ⁇ 10 wt. %, and carbon at ⁇ 49 wt. %. Hardness values were measured on 'as plated' coupons as well as after baking the coupons at approximately 190° C for 23 hours.
  • the obtained chromium-iron-alloy coatings were evaluated as to wear resistance. Measurement of wear resistance was performed using a Taber wear test specified according to ASTM D 4060. The abrasive wheels used were CS10, with a load of 500 g per wheel, abrasion was performed for 10,000 cycles, at a rotary speed of 60 rpm. The Taber wear index was less than 10. The average of 5 hardness measurements for the "as plated" chromium-iron alloy layer was 1056 HV. The average of 5 hardness measurements for the 'baked' chromium-iron alloy layer was 1187 HV.
  • chromium-iron-alloy coatings were deposited on steel substrates by a direct current at a current density of 250 mA/cm 2 for a plating time of approximately 2 hours while maintaining the electrolyte solution at a temperature of approximately 35° C and a pH of approximately 2.5.
  • the alloy composition of the coating as measure by SEM-EDS was chromium at ⁇ 80 wt. %, iron at ⁇ 12 wt. %, and carbon at ⁇ 8 wt. %.
  • Hardness values were measured on 'as plated' coupons as well as after baking the coupons at approximately 190° C for 23 hours.
  • the average of 5 hardness measurements for the "as plated" chromium-iron alloy layer was 1147 HV.
  • the average of 5 hardness measurements for the 'baked' chromium-iron alloy layer was 1249 HV.
  • the present disclosure provides improved electrolyte solutions for electrodeposition of chromium-iron alloys, methods of forming chromium-iron alloys, and methods of electrodepositing chromium-iron alloys.

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  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (15)

  1. Elektrolytlösung zur Elektroplattierung, umfassend:
    ein dreiwertiges Chromsalz;
    eine Oxalatverbindung;
    ein Eisensalz;
    ein Aluminiumsulfat;
    ein Alkalimetallsulfat; und
    ein Alkalimetallhalogenid, wobei:
    das dreiwertige Chromsalz in einer Menge in dem Bereich von etwa 0,3 Mol pro Liter bis etwa 0,9 Mol pro Liter der Elektrolytlösung vorhanden ist;
    die Oxalatverbindung in einer Menge in dem Bereich von etwa 0,2 Mol pro Liter bis etwa 1,2 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Eisensalz in einer Menge in dem Bereich von etwa 0,005 Mol pro Liter bis etwa 0,2 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Aluminiumsulfat in einer Menge in dem Bereich von etwa 0,05 Mol pro Liter bis etwa 0,5 Mol pro Liter vorhanden ist;
    das Alkalimetallsulfat in einer Menge in dem Bereich von etwa 0,1 Mol pro Liter bis etwa 2,0 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Alkalimetallhalogenid in einer Menge in dem Bereich von etwa 0,1 Mol pro Liter bis etwa 0,5 Mol pro Liter der Elektrolytlösung vorhanden ist; und
    die Elektrolytlösung keine Borsäure enthält.
  2. Elektrolytlösung nach Anspruch 1, wobei das Eisensalz ein zweiwertiges Eisensalz umfassend eines oder mehrere von Eisen(II)-sulfat, Eisen(II)-chlorid, Eisen(II)-acetat und Hydraten davon ist und/oder wobei das Eisensalz ein dreiwertiges Eisensalz umfassend eines oder mehrere von Eisen(III)-sulfat, Eisen(III)-chlorid, Eisen(III)-acetat und Hydraten davon ist.
  3. Elektrolytlösung nach Anspruch 1 oder 2, wobei das dreiwertige Chromsalz ausgewählt ist aus einem Chrom(III)-halogenid, einem Chrom(III)-sulfat oder einer Kombination davon.
  4. Elektrolytlösung nach einem der Ansprüche 1-3, wobei die Oxalatverbindung ausgewählt ist aus Natriumoxalat, Kaliumoxalat, einer Säure von Oxalat oder einer Kombination davon.
  5. Elektrolytlösung nach einem der Ansprüche 1-4, wobei das Alkalimetallsulfat ausgewählt ist aus Natriumsulfat, Kaliumsulfat oder einer Kombination davon.
  6. Elektrolytlösung nach einem der Ansprüche 1-5, wobei das Alkalimetallhalogenid ausgewählt ist aus Natriumfluorid, Kaliumfluorid oder einer Kombination davon.
  7. Elektrolytlösung nach einem der Ansprüche 1-6, wobei ein pH-Wert der Elektrolytlösung in einem Bereich von etwa 1 bis etwa 4 liegt.
  8. Elektrolytlösung nach einem der Ansprüche 1-7, ferner umfassend Natriumlaurylsulfat, Natriumlaurylethersulfat oder eine Kombination davon.
  9. Verfahren (200) zur Chromplattierung auf ein Substrat unter Verwendung einer Elektrolytlösung, umfassend:
    Einführen einer Kathode und einer Anode in eine Elektrolytlösung (240) umfassend ein dreiwertiges Chromsalz, eine Oxalatverbindung, ein Eisensalz, ein Aluminiumsulfat, ein Alkalimetallsulfat und ein Alkalimetallhalogenid; und
    Leiten eines Gleichstroms zwischen der Anode und der Kathode (250) durch die Elektrolytlösung, um eine Chromschicht auf dem Substrat abzuscheiden, wobei:
    das dreiwertige Chromsalz in einer Menge in dem Bereich von etwa 0,3 Mol pro Liter bis etwa 0,9 Mol pro Liter der Elektrolytlösung vorhanden ist;
    die Oxalatverbindung in einer Menge in dem Bereich von etwa 0,2 Mol pro Liter bis etwa 1,2 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Eisensalz in einer Menge in dem Bereich von etwa 0,005 Mol pro Liter bis etwa 0,2 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Aluminiumsulfat in einer Menge in dem Bereich von etwa 0,05 Mol pro Liter bis etwa 0,5 Mol pro Liter vorhanden ist;
    das Alkalimetallsulfat in einer Menge in dem Bereich von etwa 0,1 Mol pro Liter bis etwa 2,0 Mol pro Liter der Elektrolytlösung vorhanden ist;
    das Alkalimetallhalogenid in einer Menge in dem Bereich von etwa 0,1 Mol pro Liter bis etwa 0,5 Mol pro Liter der Elektrolytlösung vorhanden ist;
    und die Elektrolytlösung keine Borsäure enthält.
  10. Verfahren (200) nach Anspruch 9, wobei die Kathode ein Stahlsubstrat, ein Kupfersubstrat, ein Messingsubstrat, ein Nickelsubstrat, ein kupferbeschichtetes Substrat oder ein nickelbeschichtetes Substrat ist.
  11. Verfahren (200) nach Anspruch 9 oder 10, wobei die Anode ein Platinmaterial, platiniertes Titanmaterial oder ein kohlenstoffhaltiges Elektrodenmaterial ist.
  12. Verfahren (200) nach einem der Ansprüche 9-11, wobei der Strom eine Stromdichte in einem Bereich von etwa 100 bis etwa 600 mA/cm2 aufweist, durch Leiten von Gleichstrom zwischen der Anode und der Kathode.
  13. Verfahren (200) nach Anspruch 12, wobei die Stromdichte eine Stromdichte in einem Bereich von etwa 200 bis etwa 400 mA/cm2 aufweist.
  14. Verfahren (200) nach einem der Ansprüche 9-13, wobei die Elektrolytlösung bei einer Temperatur in einem Bereich von etwa 20 Grad Celsius und etwa 60 Grad Celsius gehalten wird.
  15. Verfahren (200) nach einem der Ansprüche 9-14, ferner umfassend Einstellen eines pH-Werts der Elektrolytlösung auf einen pH-Wert in einem Bereich von etwa 1,5 bis etwa 4.
EP20185818.0A 2019-07-18 2020-07-14 Funktionale chromlegierungsplattierung aus dreiwertigen chromelektrolyten Active EP3767012B1 (de)

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WO2017042420A1 (en) * 2015-09-09 2017-03-16 Savroc Ltd Chromium-based coating, a method for producing a chromium-based coating and a coated object
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