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EP4570965A1 - Dispositif et procédé de dépôt galvanique de chrome - Google Patents

Dispositif et procédé de dépôt galvanique de chrome Download PDF

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Publication number
EP4570965A1
EP4570965A1 EP23217110.8A EP23217110A EP4570965A1 EP 4570965 A1 EP4570965 A1 EP 4570965A1 EP 23217110 A EP23217110 A EP 23217110A EP 4570965 A1 EP4570965 A1 EP 4570965A1
Authority
EP
European Patent Office
Prior art keywords
anode
chromium
iii
substrate
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23217110.8A
Other languages
German (de)
English (en)
Inventor
Falko Krambeer
Daniel Bossart
Johannes Klos
Klaus-Peter Klos
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.)
Topocrom Systems AG
Original Assignee
Topocrom Systems AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Topocrom Systems AG filed Critical Topocrom Systems AG
Priority to EP23217110.8A priority Critical patent/EP4570965A1/fr
Priority to PCT/EP2024/085387 priority patent/WO2025125189A1/fr
Publication of EP4570965A1 publication Critical patent/EP4570965A1/fr
Pending legal-status Critical Current

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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
    • C25D3/04—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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms

Definitions

  • the present invention relates to an apparatus and a method for the electroplating of a hard chromium layer made of a chromium(III) compound on a surface of a substrate.
  • Coating objects with a layer of chrome has been a practice for many years. A distinction is made between so-called bright chrome coatings of up to 2 ⁇ m thickness, which primarily serve decorative purposes, and so-called hard chrome coatings with greater layer thicknesses. Hard chrome coatings impart technical functionality to an object and are used, for example, in the manufacture of skin-pass rolls or straightening rolls in the steel industry or conveyor rolls for fiber-like products.
  • Hard chrome coatings are commercially deposited from chromium electrolytes containing chromium in the hexavalent In recent years, however, the use of Cr(VI) electrolytes has been increasingly restricted by regulations, as Cr(VI) compounds are considered to pose a significant health and environmental risk.
  • Cr(III) electrolytes are already used in decorative chrome plating processes.
  • Cr(III) electrolytes are already used in decorative chrome plating processes.
  • WO 2021/214389 A1 A method for depositing a chromium layer on an article made of a Cr(III) electrolyte is disclosed, in which heat treatment with the formation of chromium carbides is not required to achieve the desired hardness. Details of the coating process are not disclosed. However, the presence of iron and/or nickel cations is necessary for the deposition of a chromium-containing Layer is described as necessary. In the examples, the substrate to be coated was pretreated, in particular, a prior application of a nickel layer prior to chrome plating.
  • the present invention relates to a device for the electroplating of a hard chromium layer from a chromium(III) compound on a surface of a substrate, comprising an anode and an electroplating bath into which the substrate acting as a cathode can be introduced, wherein the electroplating bath contains a Cr(III) compound and a carboxyl compound of the formula R-COOH or a salt thereof, wherein R is a C1-10 alkyl radical, characterized in that the anode is separated from the electroplating bath by a cation-ion selective membrane.
  • the present invention enables stable process control over an extended period of time, as there is no rapid and significant increase in pH. This allows the high layer thicknesses required for hard chrome plating to be deposited stably.
  • the anode is therefore made of a material which does not oxidize Cr(III) ions to Cr(VI) ions.
  • the present invention can, in principle, be carried out with any anode material that can be used for electrodeposition from a chromium-containing electroplating bath.
  • an anode is used that is a mixed metal oxide (MMO) electrode.
  • MMO mixed metal oxide
  • MMO electrodes are well known and commercially available.
  • a substrate e.g., a titanium plate or a titanium grid
  • a thin layer of other metals e.g., selected from the group consisting of ruthenium, iridium, and tantalum
  • other metals e.g., selected from the group consisting of ruthenium, iridium, and tantalum
  • compounds thereof such as their oxides, to impart specific properties to the anodes.
  • MMO mixed metal oxide
  • the anode is separated from the electroplating bath by a cation-selective membrane.
  • Cation-selective membranes are well known and commercially available. Examples include perfluorinated cation exchange membranes. Cation-selective membranes can be penetrated by cations, but not by anions.
  • the anode can be separated from the electroplating bath in any way using a cation-selective membrane.
  • the electroplating bath can be divided into two sections, preferably two halves, by a cation-selective membrane by providing a cation-selective membrane at a desired position within the electroplating bath.
  • the anode and the cation-selective membrane are arranged in a container, preferably a plastic container, wherein the container comprises an inlet and an interior space, wherein the anode is located in the interior space, and a medium passing through the inlet can only reach the interior space by passing through the cation-selective membrane.
  • the shape of the container is freely selectable and can, for example, be in the form of a cube, cuboid, or cylinder.
  • it can be a cuboid or cube-shaped container with an open side surface.
  • This open side surface can be closed with a plate that has openings for the passage of the electrolyte solution into the container.
  • the openings must be dimensioned such that the molecules and ions contained in the electrolyte solution can pass through.
  • a cation-selective membrane is arranged in such a way that the molecules and ions passing through the plate must pass through the cation-selective membrane in order to reach the interior of the container and thus to the anode arranged in this interior.
  • the container is preferably dimensioned in such a way that it has sufficient space to accommodate a conventional anode, but takes up as little volume of the electroplating bath as possible.
  • the anode located in the container is connected to a power source, such as a battery, by an electrical connection such as a power cable.
  • the electrical connection is routed through a surface, preferably the top surface, of the container in such a way that no molecules or ions of the electrolyte solution can enter the container at the point of penetration.
  • the device according to the invention comprises a galvanic bath.
  • the galvanic bath is provided in a container as is commonly used in electroplating.
  • the container also contains the above-described anode, the cation-selective membrane, and a substrate to be coated.
  • the substrate acts as the cathode.
  • the substrate is preferably made of a metal such as iron or steel.
  • the substrate for electrodeposition it is not necessary to subject the substrate for electrodeposition to a conventional pretreatment, such as applying a nickel layer, in order to make it accessible for electrodeposition.
  • a conventional pretreatment such as applying a nickel layer
  • a chromium layer made from a Cr(III) electrolyte can be applied directly to the substrate.
  • a layer of a polyhydroxy compound such as glycerol may be applied to the substrate prior to electrodeposition, as described in EP-3 000 918 A1 described.
  • the anode and the substrate acting as the cathode are connected to a power source via electrical wires, such as power cables.
  • the power source together with the anode and the substrate acting as the cathode, forms an electrical circuit through which direct current flows during operation.
  • Conventional direct current sources can be used.
  • the device may preferably comprise a temperature control unit in order to be able to carry out a galvanic deposition at a temperature preferred according to the invention in the range of 35 to 75°C, preferably 40 to 60°C, particularly preferably 50 to 60°C.
  • a temperature control unit for example external heating elements, are well known.
  • EP-3 000 918 A1 a device and a method are preferred as described in EP-3 000 918 A1 is described, in which the process steps are not realized by heating or cooling a single electrolyte contained in the reactor, but rather an electrolyte solution with a temperature T1 is replaced for the next process step by an electrolyte solution with a temperature T2 ⁇ T1.
  • the electroplating bath ie, the electrolyte solution
  • the electrolyte solution contains at least one Cr(III) compound in an aqueous solution for the electrodeposition of chromium on the substrate acting as the cathode.
  • Cr(III) compound used in the prior art for electroplating processes can be used.
  • Cr(III) sulfate (Cr 2 (SO 4 ) 3 ) is preferred according to the invention.
  • the electroplating bath i.e., the electrolyte solution
  • R is a C1-10 alkyl radical, preferably a C1-4 alkyl radical.
  • the alkyl radical can be linear or branched, but does not contain any further functional groups. Examples include formic acid or acetic acid.
  • a salt of the above carboxylate compound can also be used.
  • alkali metal salts, alkaline earth metal salts, or ammonium salts of the corresponding carboxylate compound can preferably be used.
  • a preferred salt is ammonium formate as the formic acid salt.
  • the electroplating bath contains no added foreign ions such as lead, copper, iron, or nickel ions. Such foreign ions can interfere with or influence the electroplating deposition of chromium from a Cr(III) electrolyte.
  • the electroplating bath consists of the above-described Cr(III) compound and the above-described carboxylate compound.
  • the galvanic bath preferably has a concentration of Cr(III) ions in the range from 0.5 mol/l to 2.0 mol/l, preferably 0.6 mol/l to 1.5 mol/l.
  • the electroplating bath preferably has a concentration of carboxylate ions such that the molar ratio of Cr(III) ions to carboxylate ions is in the range of 0.1-0.9, preferably 0.12 to 0.7 and particularly preferably 0.13 to 0.5.
  • the galvanic bath preferably has a pH value in the range of 4.5 to 6.0, preferably 5.0 to 5.5.
  • the separation of the anode or the anode chamber from the electroplating bath by means of a cation-selective membrane essentially prevents undesired oxidation of the carboxyl compound contained in the electroplating bath at the anode.
  • the carboxyl compound contained in the galvanic bath is thus protected from decomposition.
  • the process in step b) is preferably carried out at a temperature in the range of 35 to 75°C, preferably 40 to 60°C, particularly preferably 50 to 60°C, if a single chromium layer is to be deposited.
  • the deposition preferably takes place in several process stages at different or optionally the same temperatures.
  • a base layer of chromium can be deposited using an electrolyte which has a temperature in the range of 40 to 60°C, preferably 45 to 55°C.
  • a structural chromium layer can be deposited using an electrolyte which has a temperature in the range of 25 to 39°C, preferably 30 to 38°C, or alternatively in the range of 40 to 60°C, preferably 45 to 55°C.
  • a top chromium layer can be deposited using an electrolyte which again has a higher temperature in the range of 40 to 60°C, preferably 45 to 55°C.
  • the process in step b) is preferably carried out at a pH in the range from 4.5 to 6.0, preferably 5.0 to 5.5.
  • the deposition of a base layer as described above can be dispensed with, so that only one or two chromium layers (structural and, if applicable, top layer) must be deposited as described above.
  • the layer stability or passivity of the deposited chromium layer can be further increased if the process additionally comprises a step c) in which a direct current is applied to the anode of the device and the substrate acting as cathode at a pH value in the range of 6.0 to 7.0.
  • step c) can preferably be carried out by adding a pH-increasing substance.
  • Step c), if carried out, is preferably carried out at the end of the electrodeposition for a short period of time of 1 second to 60 minutes, preferably 1 minute to 30 minutes.
  • step b) and optionally step c) is carried out with a current density in the range from 10 to 300 A/dm 2 , preferably 25 to 200 A/dm 2 and particularly preferably 30 to 120 A/dm 2 .
  • hard chromium layers can be deposited from an electrolyte containing Cr(III) ions, which layers have the layer thickness required for hard chromium layers. This is achieved by the fact that, according to the invention, it is possible to carry out the deposition of chromium consistently over a long period of time.
  • the chromium layers obtained according to the invention can be applied to untreated substrates as described above.
  • the chromium layers obtained according to the invention have comparable properties, for example gloss properties, to chromium layers which are electrodeposited from electrolytes containing Cr(VI) ions.
  • a multi-layer chrome coating system can be created using the TOPOCROM® process.
  • a direct current base layer can be applied to a substrate first, before a structural layer is applied to this base layer.
  • an additional chrome layer can be applied to the structural layer.
  • a structural layer with dome-shaped (hemispherical) elevations is formed, via which the desired roughness and closedness of the surface (topography) can be adjusted as required. This surface is absolutely free of sharp edges.
  • the base layer preferably has a thickness of 1 to 500 ⁇ m, preferably 10 to 250 ⁇ m.
  • the layer thickness of the structural layer is roughness-dependent.
  • An exemplary roughness value (average roughness Ra according to DIN EN ISO 4287:2010, ie the calculated mean of all deviations of the roughness profile from the mean line along the reference distance) of a structural layer according to the invention is 0.1-15 ⁇ m, preferably 0.4-12 ⁇ m.
  • the finished chrome layer for protecting the structural layer preferably has a thickness of 2 to 20 ⁇ m, particularly preferably 3 to 15 ⁇ m, and in particular 4 to 10 ⁇ m.
  • current densities in the range of 30 to 50 A/dm 2 , preferably 35 to 45 A/dm 2 are preferably applied for a period of 5 to 3600 min, preferably 5 to 60 min, preferably 30 to 50 min.
  • the structural layer is then applied to this base layer.
  • the structural chrome layer formed there comprises hemispherical domes.
  • the structural layer is preferably produced by means of a direct current application process, wherein nucleation of the deposition material is achieved by means of at least one initial pulse of electrical voltage and/or electrical current on the surface to be coated and then growth of the deposition material nuclei is brought about by the deposition of further deposition material by means of at least one follow-up pulse, wherein during the nucleation phase the electrical voltage and/or electrical current is increased or decreased in several stages, the time between the increases is between 0.1 and 120 seconds, preferably 0.1 and 30 seconds, wherein current density changes occur in stages of 0.5 to 50 A/dm2, preferably 1 to 6 A/ dm2 .
  • a surface coating comprising a base layer and a structural layer applied thereon, wherein the base layer comprises at least two sub-layers in which the deposited chromium is contained in different amounts.
  • the deposition of a base layer as described above can be dispensed with, so that only one or two chromium layers (structural and optionally cover layer) have to be deposited as described above.
  • Fig. 1 A schematic representation of an embodiment of the device 1 according to the invention is shown.
  • the device 1 can have any shape.
  • a cylindrical shape is preferred.
  • the dimensions of the device 1 can be varied depending on the body to be coated.
  • the device (1) contains a substrate 2 acting as a cathode and an anode 3, for example, an MMO electrode.
  • Substrate 2 and anode 3 are located in a galvanic bath 4, which represents the electrolyte solution required for the galvanic deposition.
  • the galvanic bath contains Cr(III) ions, preferably in the form of chromium(III) sulfate, and a carboxyl compound, preferably ammonium formate.
  • the anode 3 is separated from the galvanic bath 4 by a cation-selective membrane 5.
  • Substrate 2 and anode 3 are connected to a direct current source 6.
  • Fig. 2 1 shows a schematic representation of an embodiment of the device 1 according to the invention with an embodiment of a container 7 for an anode 3.
  • the container 7 has dimensions adapted to the size of the anode 3 and is preferably cuboid-shaped.
  • the container 7 has an inlet 7a and an interior space 7b.
  • the interior space 7b contains the anode 3 and the anolyte 7c (i.e. the part of the electroplating bath 4 influenced by the anode).
  • the inlet is preferably a plate 7a, with which a side surface of the container 7 can be closed in the usual way (for example by clamp closures).
  • the plate 7a has openings through which the molecules and/or ions contained in the electroplating bath 4 can reach the interior space 7b.
  • the molecules and/or ions contained in the electroplating bath 4 after passing through the plate 7a, must pass through the cation-selective membrane 5, which is arranged between the inlet 7a and the interior 7b in a conventional manner (e.g., by clamp closures).
  • the anode 3 in the interior 7b of the container 7 is thus separated from the electroplating bath 4 by the cation-selective membrane 5.

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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)
EP23217110.8A 2023-12-15 2023-12-15 Dispositif et procédé de dépôt galvanique de chrome Pending EP4570965A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP23217110.8A EP4570965A1 (fr) 2023-12-15 2023-12-15 Dispositif et procédé de dépôt galvanique de chrome
PCT/EP2024/085387 WO2025125189A1 (fr) 2023-12-15 2024-12-10 Dispositif et procédé de dépôt galvanique de chrome

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP23217110.8A EP4570965A1 (fr) 2023-12-15 2023-12-15 Dispositif et procédé de dépôt galvanique de chrome

Publications (1)

Publication Number Publication Date
EP4570965A1 true EP4570965A1 (fr) 2025-06-18

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Application Number Title Priority Date Filing Date
EP23217110.8A Pending EP4570965A1 (fr) 2023-12-15 2023-12-15 Dispositif et procédé de dépôt galvanique de chrome

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EP (1) EP4570965A1 (fr)
WO (1) WO2025125189A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1602404A (en) 1978-04-06 1981-11-11 Ibm Electroplating of chromium
EP0565070B1 (fr) 1992-04-09 1997-07-30 Heidelberger Druckmaschinen Aktiengesellschaft Procédé d'électrodéposition
EP0722515B1 (fr) 1993-10-07 1998-01-28 Heidelberger Druckmaschinen Aktiengesellschaft Procede d'application d'un revetement superficiel par galvanisation
JP2015212406A (ja) * 2014-05-01 2015-11-26 奥野製薬工業株式会社 ３価クロムめっき方法
EP3000918A1 (fr) 2014-09-24 2016-03-30 topocrom systems AG Procédé et dispositif d'application galvanique d'un revêtement de surface
JP2016060918A (ja) * 2014-09-16 2016-04-25 株式会社Ｊｃｕ 装飾用３価クロムめっき液およびこれを利用した装飾クロムめっき方法
EP3607115A1 (fr) * 2017-04-04 2020-02-12 ATOTECH Deutschland GmbH Procédé commandé de dépôt d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
EP3733932A1 (fr) * 2019-04-09 2020-11-04 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'une bande métallique revêtue d'un revêtement de chrome et d'oxyde de chrome à base d'une solution électrolytique avec un composé à base de chrome trivalent et système d'électrolyse permettant la mise en oeuvre dudit procédé
WO2021214389A1 (fr) 2020-04-23 2021-10-28 Savroc Ltd Objet comprenant un revêtement à base de chrome ayant une dureté vickers élevée, procédé de production et bain aqueux de galvanoplastie pour celui-ci
EP4012074A1 (fr) 2020-12-14 2022-06-15 topocrom systems AG Revêtement de surface et son procédé de fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006035871B3 (de) 2006-08-01 2008-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Abscheidung von Chromschichten als Hartverchromung, Galvanisierungsbad sowie hartverchromte Oberflächen und deren Verwendung
EP2899299A1 (fr) * 2014-01-24 2015-07-29 COVENTYA S.p.A. Électrolyte au chrome trivalent et méthode de déposition du chrome métallique
CN110062819B (zh) * 2016-11-14 2021-07-23 塔塔钢铁艾默伊登有限责任公司 用于使用镀覆层电镀未涂覆的钢带材的方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1602404A (en) 1978-04-06 1981-11-11 Ibm Electroplating of chromium
EP0565070B1 (fr) 1992-04-09 1997-07-30 Heidelberger Druckmaschinen Aktiengesellschaft Procédé d'électrodéposition
EP0722515B1 (fr) 1993-10-07 1998-01-28 Heidelberger Druckmaschinen Aktiengesellschaft Procede d'application d'un revetement superficiel par galvanisation
JP2015212406A (ja) * 2014-05-01 2015-11-26 奥野製薬工業株式会社 ３価クロムめっき方法
JP2016060918A (ja) * 2014-09-16 2016-04-25 株式会社Ｊｃｕ 装飾用３価クロムめっき液およびこれを利用した装飾クロムめっき方法
EP3000918A1 (fr) 2014-09-24 2016-03-30 topocrom systems AG Procédé et dispositif d'application galvanique d'un revêtement de surface
EP3607115A1 (fr) * 2017-04-04 2020-02-12 ATOTECH Deutschland GmbH Procédé commandé de dépôt d'une couche de chrome ou d'alliage de chrome sur au moins un substrat
EP3733932A1 (fr) * 2019-04-09 2020-11-04 ThyssenKrupp Rasselstein GmbH Procédé de fabrication d'une bande métallique revêtue d'un revêtement de chrome et d'oxyde de chrome à base d'une solution électrolytique avec un composé à base de chrome trivalent et système d'électrolyse permettant la mise en oeuvre dudit procédé
WO2021214389A1 (fr) 2020-04-23 2021-10-28 Savroc Ltd Objet comprenant un revêtement à base de chrome ayant une dureté vickers élevée, procédé de production et bain aqueux de galvanoplastie pour celui-ci
EP4012074A1 (fr) 2020-12-14 2022-06-15 topocrom systems AG Revêtement de surface et son procédé de fabrication

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