EP3744874A1 - Produit plaqué doté d'un revêtement résistant à la corrosion - Google Patents

Produit plaqué doté d'un revêtement résistant à la corrosion Download PDF

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Publication number
EP3744874A1
EP3744874A1 EP19177415.7A EP19177415A EP3744874A1 EP 3744874 A1 EP3744874 A1 EP 3744874A1 EP 19177415 A EP19177415 A EP 19177415A EP 3744874 A1 EP3744874 A1 EP 3744874A1
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EP
European Patent Office
Prior art keywords
layer
zinc
nickel
electroplating
chromium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP19177415.7A
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German (de)
English (en)
Inventor
designation of the inventor has not yet been filed The
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coventya SAS
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Coventya SAS
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Filing date
Publication date
Application filed by Coventya SAS filed Critical Coventya SAS
Priority to EP19177415.7A priority Critical patent/EP3744874A1/fr
Priority to PCT/EP2020/064882 priority patent/WO2020239932A1/fr
Publication of EP3744874A1 publication Critical patent/EP3744874A1/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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

Definitions

  • the present invention refers to an electroplated product comprising a substrate which is coated with a first layer consisting of zinc or a zinc alloy and a second layer composed mainly of chrome with a certain percentage of alloying elements like C, O, N but it is produced from an electrolyte containing trivalent chrome as well as a process for obtaining such an electroplated product.
  • Chrome deposits from trivalent chrome electrolytes are widely used in the industry due to their unique properties they allow substrates to work longer and under tougher conditions that they would normally survive in.
  • Cr(VI) substances are under regulatory pressure due to their toxic nature. They were classified as CMR and the European Union decided to submit its use to specific authorization under REACH regulations.
  • WO2015110627 a trivalent chromium deposition bath is described which contains an organic acid complexing agent with a specific ratio range between this complexing agent and the trivalent chromium.
  • the drawback of such a deposit obtained from this bath is the limited corrosion resistance of the deposit which is not sufficient for the requirements defined by major original equipment manufacturers.
  • WO2018185144 describes the use of a nickel or nickel alloy layer under the chromium or chromium alloy layer.
  • the target is to use a barrier coating (semi-bright nickel) and not a cathodic protection.
  • the drawback of such a composition is that there will be a nickel release which render such composition unsuitable for certain applications.
  • US 3691027 describes the use of an acidic ZnNi process in order to replace a part of the expensive nickel underlayer while maintaining corrosion resistance and brightness of the thin chrome deposit obtained by the use of an hexavalent chromium deposition bath.
  • the drawback of such a process is that the top layer is a chromium deposition obtained from a hexavalent chromium based electrolyte and so with different properties than the one coming from trivalent chromium electrolyte.
  • the hexavalent chrome bath contains toxic and harmful substances that can be avoided with a trivalent chrome bath.
  • there is the need in this process to have a nickel layer above the ZnNi layer which makes the system more complicated to operate.
  • an electroplated product comprising a substrate which is coated with a first layer comprising or consisting of zinc or a zinc alloy and a second layer plated directly above the first layer (i.e. on top of the first layer or adjacent to the first layer) comprising or consisting of chromium or chromium alloy plated from a trivalent chromium based electrolyte, wherein the first layer improves the corrosion resistance of the second layer.
  • the purpose of the present invention is therefore to improve the corrosion resistance of the chrome second layer by using such a first layer.
  • the presence of the first layer comprising zinc or a zinc alloy has the effect to avoid the use of harmful compounds during the fabrication process.
  • the plating is realised at a lower temperature than the one used for nickel first layer plating (around 50°C) having the benefit to decrease the energy consumption and to be less hazardous (decrease in evaporation).
  • the second layer comprises at least 80 wt.-% of chromium and less than 4 wt.-% of car-bon and 3 wt.-% of oxygen.
  • the second layer comprises at least 85 wt.-% of chromium and less than 3 wt.-% of carbon and 1 wt.-% of oxygen.
  • the first layer comprises a zinc nickel alloy.
  • the first layer comprises percentage nickel in that the zinc nickel alloy comprises from 10 wt.-% to 20 wt.-%, preferably from 11 wt.-% to 18 wt.-%, more preferably from 12 wt.-% to 15 wt.-%.
  • the first layer has a thickness comprised between 1 and 25 ⁇ m, preferably between 4 and 16 ⁇ m, more preferably between 5 and 12 ⁇ m.
  • the first layer comprises a zinc iron alloy.
  • the first layer comprises a percentage iron in the zinc iron alloy comprises from 5 wt.-% and to 13 wt.-%, preferably 7 wt.-% and to 10wt.- %, more preferably 7wt.- % and to 8 wt.- %.
  • the first layer comprises a zinc tin alloy.
  • the first layer comprises percentage tin in that the zinc nickel alloy comprises from 65 wt.-% to 80 wt.-%, preferably from 70 wt.-% to 75 wt.-%.
  • the first layer comprises a zinc copper alloy.
  • the first layer comprises percentage tin in that the zinc nickel alloy comprises from 25 wt.-% to 40 wt.-%, preferably from 30 wt.-% to 35 wt.-%.
  • the first layer comprises percentage copper in that the zinc nickel alloy comprises from 45 wt.-% to 55 wt.-%.
  • the second layer is a finish layer and no other layer is added on the second layer.
  • a nickel spectrum will increase at the same moment than the zinc spectrum representing the composition of the zinc nickel first layer.
  • an iron spectrum will increase at the same moment than the zinc spectrum representing the composition of the zinc iron first layer.
  • the iron spectrum will reach a plateau as the zinc spectrum start to decrease.
  • a method for preparing an electroplated product by electroplating a substrate comprising the following steps:
  • both electroplating baths are free of divalent sulphur compounds, boric acids and hexavalent chromium ions.
  • the concentration of the source of zinc ions is from 4 g/L to 80 g/L, preferably from 5 g/L to 50 g/L, more preferably from 6 g/L to 20 g/L.
  • the electroplating step a) also comprises at least one source of nickel ions.
  • the concentration of the source of nickel ions is from 0,1 g/L to 10 g/L.
  • the electroplating step a) also comprises at least one source of ferrous or ferric ions.
  • the concentration of the source of ferrous or of ferric ions is comprised between 0,1 g/L and 10 g/L, preferably between 0,5 g/L and 5 g/L, more preferably between 0,7 g/L and 3 g/L.
  • the electroplating step a) also comprises at least one source of tin ions.
  • the temperature of the bath during step a) is comprised between 10 to 40 °C, preferably between 15 to 35 °C.
  • the electroplating step a) is realized in an alkaline bath defined by a pH above 13.
  • the electroplating step a) is obtained in a current density range from 0,01 to 10 A/dm 2 , preferably from 0,02 to 5 A/dm 2 , more preferably from 0,02 to 3 A/dm 2 .
  • the electroplating step a) is realized in an acidic bath defined by a pH below 6, preferably below 5.3, more preferably below 5.
  • the electroplating step a) is realized in a barrel.
  • the electroplating step a) is realized by rack.
  • the electroplating step b) is realized in a bath at pH comprised between 3 to 9, preferably between 4 to 7, more preferably between 5 to 6.
  • the concentration of trivalent chromium salt is comprised between 100 to 400 g/L, preferably between 110 to 300 g/L.
  • the complexing agent is at concentration comprised between 100 to 300 g/L, more preferably between 150 to 250 g/L.
  • the complexing agent is preferably selected from the group consisting of carboxylic acids and carboxylate salts, preferably formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, oxalic acid, malic acid, citric acid, tartaric acid, succinic acid, gluconic acid, glycine, aspartic acid, glutamic acid, and mixtures thereof, or their salts and mixtures thereof.
  • the temperature of the bath during step b) is comprised between 30 to 70 °C, preferably between 35 to 65 °C, more preferably between 40 to 60 °C.
  • the product of the step a) is pre-activated before the step b).
  • This pre-activation comprises the application of a hydrochloric acid solution on the product of the step a).
  • the product of the step b) is then submitted to a thermal treatment (TTH) comprising of 4 hours at 190°C in an oven.
  • TTH thermal treatment
  • a metal is acid or alkaline
  • a alkaline zinc nickel first layer we mean that this first layer was obtained from an alkaline plating bath.
  • the electroplating bath used for the deposition of zinc and zinc alloy first layer are described below.
  • the plating were realized on a steel substrate.
  • Alkaline zinc-nickel bath containing 120 g/L of sodium hydroxide, 10 g/L of zinc, 1.5 g/L of nickel, 20 g/L de tetraethylenpentamine (TEPA) and 2 g/L of Quadrol (THEED). Parts are plated during 40 minutes at 2A/dm 2 and at room temperature.
  • TEPA de tetraethylenpentamine
  • TEDED Quadrol
  • Acid zinc-nickel bath containing 60-70 g/L of zinc chloride, 100-130 g/L of nickel chloride ⁇ 6H 2 0, 190-220 g/L of potassium chloride, 25 g/L of sodium acetate ⁇ 3H 2 0, 30 g/L of aminoacetic acid, 2-4 g/L of sodium saccharine, 0,025-0,20 g/L of benzal acetone, 0,006-0,01 g/L of orthochlorobenzaldehyde, 0,8-1,2 g/L of octanolethoxylate, 2,5-3,2 g/L of potassium salt of the sulfopropy-lated polyalkoxylated napthol. pH is adjusted at 5-6 and bath is heated up to 33-36°C. Parts are plated at 2 A/dm 2 during 25 minutes.
  • Alkaline zinc bath containing 130 g/L of sodium hydroxide, 10 g/L of zinc and crosslinked polymers mentioned in EP 2111484 from TASKEM. Parts are plated during 40 minutes at 2A/dm 2 and at room temperature.
  • the electroplating bath used for the deposition of trivalent chromium second layer were similar to the one described in Table 1 of the examples of the patent application WO 2015/110627 from Coventya S.P.A.
  • the corrosion resistance was evaluated by the resistance to the NSS Test. Those experiments were conducted with a Braive 2000L corrosion chamber following the norm ISO 9227.
  • the thermal treatment (TTH) of the samples comprises of 4 hours at 190°C in an oven.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
EP19177415.7A 2019-05-29 2019-05-29 Produit plaqué doté d'un revêtement résistant à la corrosion Ceased EP3744874A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19177415.7A EP3744874A1 (fr) 2019-05-29 2019-05-29 Produit plaqué doté d'un revêtement résistant à la corrosion
PCT/EP2020/064882 WO2020239932A1 (fr) 2019-05-29 2020-05-28 Produit électrodéposé avec revêtement résistant à la corrosion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19177415.7A EP3744874A1 (fr) 2019-05-29 2019-05-29 Produit plaqué doté d'un revêtement résistant à la corrosion

Publications (1)

Publication Number Publication Date
EP3744874A1 true EP3744874A1 (fr) 2020-12-02

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EP19177415.7A Ceased EP3744874A1 (fr) 2019-05-29 2019-05-29 Produit plaqué doté d'un revêtement résistant à la corrosion

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EP (1) EP3744874A1 (fr)
WO (1) WO2020239932A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691027A (en) 1970-06-16 1972-09-12 Allied Chem Method of producing corrosion resistant chromium plated articles
US3917517A (en) * 1973-10-10 1975-11-04 Int Lead Zinc Res Chromium plating electrolyte and method
US4048024A (en) * 1975-03-27 1977-09-13 International Lead Zinc Research Organization, Inc. Bright levelling zinc plating
US4159230A (en) * 1977-04-03 1979-06-26 International Lead Zinc Research Organization, Inc. Treatment of chromium electrodeposit
US4407900A (en) * 1980-10-17 1983-10-04 Kabushiki Kaisha Kobe Seiko Sho Electroplated corrosion resistant steels and method for manufacturing same
US20060099439A1 (en) * 2004-11-10 2006-05-11 Kochilla John R Metal pieces and articles having improved corrosion resistance
EP2111484A1 (fr) 2004-03-04 2009-10-28 Taskem Inc. Agent de brillance polyamine
WO2014154884A2 (fr) 2013-03-28 2014-10-02 Coventya Sas Bain d'electroplacage pour des alliages zinc-fer, procede de depot d'alliage zinc-fer sur un dispositif et un tel dispositif
WO2015110627A1 (fr) 2014-01-24 2015-07-30 Coventya S.P.A. Bain galvanoplastique contenant du chrome trivalent et procédé permettant de déposer du chrome
US20150314569A1 (en) * 2014-05-05 2015-11-05 National Taiwan University Steel sheet and fabrication method thereof
WO2018185144A1 (fr) 2017-04-04 2018-10-11 Atotech Deutschland Gmbh Procédé commandé de dépôt d'une couche de chrome ou d'alliage de chrome sur au moins un substrat

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691027A (en) 1970-06-16 1972-09-12 Allied Chem Method of producing corrosion resistant chromium plated articles
US3917517A (en) * 1973-10-10 1975-11-04 Int Lead Zinc Res Chromium plating electrolyte and method
US4048024A (en) * 1975-03-27 1977-09-13 International Lead Zinc Research Organization, Inc. Bright levelling zinc plating
US4159230A (en) * 1977-04-03 1979-06-26 International Lead Zinc Research Organization, Inc. Treatment of chromium electrodeposit
US4407900A (en) * 1980-10-17 1983-10-04 Kabushiki Kaisha Kobe Seiko Sho Electroplated corrosion resistant steels and method for manufacturing same
EP2111484A1 (fr) 2004-03-04 2009-10-28 Taskem Inc. Agent de brillance polyamine
US20060099439A1 (en) * 2004-11-10 2006-05-11 Kochilla John R Metal pieces and articles having improved corrosion resistance
WO2014154884A2 (fr) 2013-03-28 2014-10-02 Coventya Sas Bain d'electroplacage pour des alliages zinc-fer, procede de depot d'alliage zinc-fer sur un dispositif et un tel dispositif
WO2015110627A1 (fr) 2014-01-24 2015-07-30 Coventya S.P.A. Bain galvanoplastique contenant du chrome trivalent et procédé permettant de déposer du chrome
US20150314569A1 (en) * 2014-05-05 2015-11-05 National Taiwan University Steel sheet and fabrication method thereof
WO2018185144A1 (fr) 2017-04-04 2018-10-11 Atotech Deutschland Gmbh Procédé commandé de dépôt d'une couche de chrome ou d'alliage de chrome sur au moins un substrat

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