Electroplating device and method for depositing a electroplating layer and workpiece having a electroplating layer

Abstract

The invention relates to an electroplating device 1 for producing an electroplated layer on a workpiece 2, wherein the electroplating device comprises at least one cathode and one catholyte 11, wherein the workpiece 2 is configured as the cathode or is electrically connected to the cathode, and wherein the catholyte 11 contacts the workpiece 2. Furthermore, the electroplating device 1 comprises an anode 4, an anolyte 6, and preferably a membrane 7, wherein the anode 4 contacts the anolyte 6 and the optional membrane 7 is arranged between the catholyte 11 and the anolyte 6. In addition, the electroplating device 1 comprises a catholyte carrier 8, wherein the catholyte carrier 8 is impregnated with the catholyte 11 and is in contact with the workpiece 2 in a contact area, such that the catholyte 11 from the catholyte carrier 8 contacts the workpiece 2.Furthermore, the electroplating device 1 is designed such that the contact area between workpiece 2 and catholyte carrier 8 is shifted by a relative movement of both. The invention further relates to a method for depositing an electroplated layer on the workpiece 2 using the electroplating device 1, as well as to a workpiece 2 with an electroplated layer.

Description

[0001] The invention relates to an electroplating device for producing an electroplating layer on a workpiece and a method for depositing an electroplating layer on a workpiece, as well as a workpiece with an electroplating layer.

[0002] Electroplating, also known as galvanic coating, is a widely used method for improving the surface properties of materials. The underlying process utilizes electrochemical processes to deposit a thin layer of metal onto a base material, significantly enhancing its functionality and aesthetics. In modern industry, electroplating has diverse applications and is an essential part of the manufacturing and finishing of products in numerous sectors.

[0003] The publication DE 10 2006 035 871 B3 describes a process for the deposition of chromium(III) layers, as well as chromium(III) layers produced therefrom, wherein a body is connected as a cathode and is immersed in a catholyte.

[0004] The invention is based on the objective of creating an electroplated layer on a workpiece.

[0005] The invention relates to an electroplating device for producing an electroplated layer on a workpiece with the features of claim 1 and a method for depositing an electroplated layer on a workpiece with the features of claim 13 as well as a workpiece with an electroplated layer according to the features of claim 15.

[0006] Preferred or advantageous embodiments of the invention will become apparent from the dependent claims, the following description and / or the accompanying figures.

[0007] The invention relates to an electroplating device for producing an electroplated layer on a workpiece, comprising at least one cathode, wherein the workpiece is designed as the cathode or is electrically connected to the cathode, a catholyte, wherein the catholyte contacts the workpiece, an anolyte and an anode, wherein the anode contacts the anolyte, the electroplating device having a catholyte carrier, wherein the catholyte carrier is impregnated with the catholyte and is in contact with the workpiece in a contact area, such that the catholyte from the catholyte carrier contacts the workpiece, and wherein the electroplating device is designed to generate a relative movement between the catholyte carrier and the workpiece, such that the contact area on the workpiece shifts in order to produce the electroplated layer on the workpiece.

[0008] The electroplating device comprises at least the cathode, wherein the cathode is connected to the negative terminal of a voltage and / or current source to charge it negatively. Furthermore, the workpiece is configured as the cathode or electrically connected to the cathode, the workpiece being the object to be coated. In particular, the workpiece is configured such that it has the ability to become electrically charged, at least on the surface to be coated. Specifically, the workpiece is made of an electrically conductive material, particularly a metal. Alternatively, the workpiece can also be made of a non-conductive material coated with a metal, such as a metal-coated polymer, in which case the metal-coated surface is connected to the voltage and / or current source.

[0009] Furthermore, the electroplating device includes the catholyte, wherein the catholyte is the electrolyte that is in contact with the cathode, in particular the workpiece. Specifically, the catholyte comprises the metal or metals and, in particular, also non-metals that are deposited on the surface of the workpiece and form an electroplated layer. The catholyte is in contact with the workpiece. Specifically, the catholyte contacts the workpiece in an area on the surface of the workpiece, wherein the entire surface or only a part of the surface of the workpiece is in contact with the catholyte. Specifically, the part of the surface of the workpiece in contact with the catholyte is the area in which the deposition of an electroplated layer is possible. The electroplated layer can be a metallic electroplated layer made of a single metal, an alloy of several metals, or an alloy of one or more metals and a non-metal.In particular, the catholyte contains finely dispersed particles, for example made of solids such as diamond or boron nitride or of plastics such as PTFE, which are incorporated into the electroplating layer by dispersion deposition.

[0010] The electroplating device includes an anode, the anode being the electrode connected to the electrically positive terminal of the voltage and / or current source. The anode is in contact with the anolyte, with the surface of the anode being wholly or partially in contact with the anolyte. The anode is configured to become electrically positively charged, at least on its surface. In particular, the anode is partially or entirely made of an electrically conductive material. Preferably, the anode is made of an electrically conductive material, at least on its surface, and especially on the portion of the surface that is in contact with the anolyte. For example, the anode can be made entirely of one or more metals or be coated with a metal.

[0011] The anolyte contains an acid or a salt of the acid. Specifically, the anolyte is a second-class conductor and thus an ionic conductor, conducting electric current and, in particular, completing the circuit. This conduction of electric current involves a combined process of ion and charge transport. The electrode surface forms the interface between electron and ion conduction. However, since the oxidation potential for water is significantly lower, oxygen evolution (water oxidation) can occur at the anode.

[0012] The electroplating device preferably includes an optional membrane, which is arranged between the catholyte and the anolyte. In particular, the optional membrane serves to separate the catholyte and the anolyte from each other. Preferably, the optional membrane prevents the anolyte and the catholyte from mixing, while simultaneously allowing an electric current, particularly by ionic conduction. The optional membrane is specifically designed to prevent or limit the oxidation of the metal cations of the catholyte at the anode. Preferably, the optional membrane is configured as a microporous partition. In particular, the optional membrane can be configured as a diaphragm.

[0013] Furthermore, the electroplating device includes a catholyte carrier, which is impregnated with the catholyte. In particular, the catholyte carrier is designed to receive and retain the catholyte. The ability of the catholyte carrier to receive and retain the catholyte is specifically attributable to its material and / or structure. The catholyte carrier is arranged in the electroplating device such that it is in contact with the workpiece. Specifically, the catholyte carrier is designed to touch or enclose the area of ​​the workpiece surface where the electroplating layer is to be deposited. In particular, the catholyte carrier can also be designed to completely enclose a portion of the workpiece along its longitudinal axis.The catholyte carrier serves to make the catholyte contact the workpiece in the area where the catholyte carrier and the workpiece are in contact. In other words, this means that the catholyte carrier provides or releases the catholyte onto the area of ​​the workpiece where the electroplating layer is to be deposited.

[0014] Preferably, the electroplating device is designed such that the catholyte is dispensed onto or supplied to the catholyte carrier. In particular, the catholyte can be dispensed onto the catholyte carrier via a piping system and an outlet, e.g., a hose, whereby the catholyte carrier becomes saturated with the catholyte, or in particular, is saturated with it. Furthermore, the piping system can also be connected directly to the catholyte carrier, whereby the catholyte flows through the catholyte carrier. In particular, the catholyte is supplied to the catholyte carrier in such a way that the catholyte is renewed, or in particular continuously renewed, whereby the consumed catholyte is displaced by the newly flowing catholyte, or in particular replaced by the newly flowing catholyte, wherein the exchange takes place in particular in the area where the electroplating layer is deposited.In particular, the surface of the workpiece to be coated is exposed to the catholyte flowing through the catholyte carrier, whereby the catholyte that contacts the surface of the workpiece is preferably continuously renewed by the incoming catholyte.

[0015] In particular, the electroplating device is designed such that the workpiece rests in or against the catholyte carrier, the catholyte carrier preferably being arranged next to the optional membrane, the optional membrane being in direct contact with the catholyte carrier or separated from it by a catholyte layer. Preferably, the optional membrane is connected to the catholyte carrier. In particular, the anolyte and the anode are contained in a vessel, the vessel preferably being rigidly connected to the catholyte carrier and / or the optional membrane. In particular, the catholyte carrier, the optional membrane, the anode, and the anolyte and its vessel form a unit, the unit being capable of being supplemented by further elements.

[0016] Furthermore, the electroplating device is designed to generate relative movement between the catholyte carrier and the workpiece. This movement shifts the contact area on the workpiece, resulting in the deposition of the electroplated layer on different areas of the workpiece surface. In particular, the relative movement is designed such that different areas of the workpiece surface are coated with the electroplated layer multiple times in succession. Preferably, the relative movement is designed such that the time between coating processes of the same partial area of ​​the workpiece surface can be set and preferably remains constant.

[0017] This offers the advantage that a smaller quantity of catholyte can be used, since only the contact area between the catholyte carrier and the workpiece is supplied with the catholyte. Further advantages arise from the relative movement between the catholyte-impregnated catholyte carrier and the surface of the workpiece to be coated.

[0018] During the deposition of the electroplating layer on the workpiece, particularly the workpiece acting as the cathode, hydrogen is released / evolved from the catholyte. The relative movement of the catholyte-impregnated catholyte carrier and its contact with the workpiece surface, especially the displacement of the contact area on the workpiece surface, facilitates the removal of hydrogen from the surface of the workpiece to be coated and / or already coated, particularly the hydrogen already bound in the electroplating layer. This results in an electroplating layer with improved optical and / or technical properties. Furthermore, the grain growth and microstructure of the electroplating layer are positively influenced. A finer and / or more uniform microstructure is formed because grain growth, and thus the microstructure formation, occurs more uniformly.This suppresses, and in particular prevents, uncontrolled grain growth. The result is a fine structure with uniform and smaller grains. This leads to an electroplated layer with improved optical and / or technical properties.

[0019] An additional advantage arises from the supply, and in particular the contact, between the surface to be coated and the catholyte. Because the workpiece is not immersed in a stationary, static catholyte, but rather the catholyte is supplied dynamically via the catholyte carrier, the ions present in the catholyte, which form the electroplating layer, or at least a portion thereof, are transported closer to the surface of the workpiece to be coated. This increases the electrical potential between the workpiece surface and the ions to be deposited, thereby promoting the deposition process of the electroplating layer on the workpiece surface.

[0020] In one embodiment, the catholyte carrier has cavities, particularly open and permeable cavities, wherein the cavities are specifically designed as pores, channels, or open capillaries. Furthermore, the cavities are specifically designed to be small enough to absorb and preferably retain the liquid catholyte due to surface tension and / or capillary action. In particular, the catholyte carrier is made of a textile fabric, wherein the textile can be made of a natural or synthetic material, and the material is particularly chemically inert. Specifically, the catholyte carrier is made of a fiber or thread material. This offers the advantage of enhancing the absorption and retention capacity of liquids.

[0021] In a further embodiment, the catholyte carrier is made, for example, of a nonwoven fabric, woven fabric, braid, knitted fabric, knitted fabric, laid fabric, felt, or wadding. For instance, the catholyte carrier can be a micro-perforated polypropylene nonwoven fabric. The material "PermaWrap" from Sifco asc serves as an example. This offers the advantage that the catholyte carrier is particularly well-suited to absorbing and retaining liquids while simultaneously causing no damage to the surface to be coated or to the already coated surface of the workpiece.

[0022] Another embodiment provides that the relative motion is designed as a rotational motion. In particular, the electroplating device is designed such that the contact area between the workpiece and the catholyte carrier changes, especially shifts, through a rotational motion on the surface of the workpiece to be coated. Specifically, the rotational motion is generated by an actuator, which is, for example, one or more electric motors.

[0023] A first embodiment provides that the workpiece is the fixed component, or one that is immobile with respect to rotation about the axis of rotation, while the rest of the electroplating device, in particular the unit comprising the catholyte carrier, the optional membrane, the anode, the anolyte, and its container, is mounted to rotate about a horizontal and / or vertical axis. Specifically, the unit comprising the catholyte carrier, the optional membrane, the anode, the anolyte, and its container is functionally connected to the actuator, with the actuator generating the rotational movement.

[0024] A preferred embodiment provides that the rotational movement is achieved by the rotation of the workpiece, with the remainder of the electroplating device preferably mounted immobile for rotation about an axis of rotation. In particular, the workpiece is functionally connected to the actuator, which generates the rotational movement. Preferably, the actuator is designed such that the workpiece is connected to it by force-fit, form-fit, and / or material-fit, and in particular also serves as a clamping device for the workpiece. This offers the advantage that a rotational movement about an axis can be performed, and simple and cost-effective actuators can be used to realize the rotational movement.Furthermore, the rotary motion allows the time between two coating processes of the same sub-area of ​​the workpiece surface to be set, with the coating pauses depending on the rotational speed. This enables, for example, pulse deposition, in particular mechanical pulse deposition.

[0025] One embodiment provides that the electroplating device has at least one height actuator for generating a linear movement of the workpiece. For example, the linear movement can be achieved by hydraulic pistons, pneumatic pistons, or electromechanical actuators such as electric motors or electromechanical cylinders. In particular, the linear movement is performed along a vertical or horizontal axis, parallel to the surface to be coated, especially parallel to the surface of the optional membrane. The actuator is also specifically designed as a clamping device for the workpiece, wherein the workpiece is connected to the actuator by a material, form, and / or force-fit connection and / or is clamped within it.

[0026] Another embodiment provides that the linear movement is performed by the unit comprising the catholyte carrier, the optional membrane, the anode, the anolyte, and its container. This offers the advantage that the area in which the electroplated layer is to be deposited on the surface of the workpiece can be precisely controlled. Furthermore, this also allows the time during which the coating process for a given area is interrupted to allow hydrogen bound in the electroplated layer to escape.

[0027] A preferred embodiment of the invention provides that the linear movement takes place simultaneously and / or as a superposition with the rotational movement.

[0028] A first embodiment provides that the workpiece, by means of one or more actuators, performs both rotational and linear motion, wherein the workpiece rotates about its longitudinal axis while being moved up or down along its longitudinal axis parallel to the surface to be coated. In particular, a height actuator can be used to generate the linear motion and an actuator to generate the rotational motion. Preferably, an actuator is used which is configured to perform both the rotational and linear motions as relative motions.

[0029] A second embodiment provides that the workpiece, in particular the actuator connected to the workpiece, performs the rotational movement along its longitudinal axis, wherein the unit comprising the catholyte carrier, the optional membrane, the anode, as well as the anolyte and its container performs the linear movement parallel to the longitudinal axis of the workpiece, wherein the linear movement is generated in particular by an actuator.

[0030] A third embodiment provides that the workpiece, and in particular the actuator connected to the workpiece, performs the linear movement along its longitudinal axis, wherein the unit comprising the catholyte carrier, the optional membrane, the anode, the anolyte, and its container rotates about the longitudinal axis of the workpiece, the rotational movement being generated in particular by an actuator. A fourth embodiment provides that the unit comprising the catholyte carrier, the optional membrane, the anode, the anolyte, and its container performs both the rotational movement about the longitudinal axis of the workpiece and the linear movement parallel to the longitudinal axis of the workpiece. In particular, a height actuator can be used to generate the linear movement and an actuator can be used to generate the rotational movement. Preferably, an actuator is used which is configured to perform both the rotational and linear movements as relative movements.

[0031] In particular, the unit may comprise the catholyte carrier, the optional membrane, the anode, as well as the anolyte and its container, only the catholyte carrier, or be formed from it.

[0032] This allows for a uniform deposition of the electroplating layer on the surface of the workpiece, especially in the case of cylindrical workpieces.

[0033] In one possible embodiment, the height actuator for generating a linear movement of the workpiece and / or the actuator for generating a rotational movement of the workpiece and / or the actuator for generating both linear and rotational movement of the workpiece is connected to a voltage or current source, with the workpiece being electrically conductively connected to at least one of said actuators. This allows the workpiece to act as the cathode, thus enabling the deposition of the electroplated layer.

[0034] A preferred embodiment provides that the workpiece is designed as a rotationally symmetric body. In particular, the workpiece is designed such that the surface to be coated is concentric with the axis of rotation and / or the surface to be coated extends from the lower end of the workpiece along the axis of rotation to the upper end of the workpiece. Specifically, the workpiece is designed as a rotationally symmetric solid or hollow cylinder, wherein the solid or hollow cylinder preferably has a uniform inner and / or outer diameter. This offers the advantage that rotationally symmetric bodies, especially cylindrical bodies, are well suited for performing a rotational movement and can be coated uniformly with minimal effort.

[0035] In a further embodiment, the electroplating device includes a voltage and / or current source for supplying the cathode and / or anode with a voltage and / or current, thereby generating a potential difference between the cathode and anode. In particular, the voltage and / or current source is configured to generate one or more current and / or voltage pulses. This allows the technical and / or optical properties of the deposited electroplated layer to be influenced and improved.

[0036] In particular, the relative movement between the workpiece and the catholyte carrier serves to effect pulsed deposition of the electroplated layer on the workpiece surface. This relative movement is generated or utilized in such a way that the area where the electroplated layer is deposited is shifted on the workpiece surface in such a way that each area is coated multiple times. Specifically, each area is coated several times with a coating pause defined by the relative movement. This allows the optical and technical properties of the electroplated layer to be influenced and improved. For example, the grain growth and grain size of the deposited metal layer can be regulated.

[0037] In a preferred embodiment of the invention, the optional membrane is configured as a semipermeable membrane, in particular as an anion-selective membrane, wherein it is permeable to anions and impermeable to cations. In particular, the membrane is permeable to the anions present on the cathode side. The optional membrane is configured such that the metals contained in the catholyte, in particular the metal cations present on the cathode side, cannot reach the anode, thereby preventing or limiting oxidation of the metal cations at the anode. In particular, the optional membrane can also be configured to limit or prevent the salting of the catholyte or its enrichment with salt(s). Preferably, the optional membrane is made of or comprises a polymer. For example, the optional membrane can be an anion exchange membrane, such as...The product "FM-FAS-PET-75" from Quintech can be used. Alternatively, a PTFE membrane, such as that distributed by Rescom (DuPont), can also be used. This offers the advantage that the deposition reaction is not slowed down or halted by the oxidation of the metal cations at the anode.

[0038] The electroplating device serves to deposit the electroplated layer onto the surface of the workpiece, wherein the electroplated layer is formed as a metal layer. In particular, the electroplated layer is deposited from the catholyte, which contains one or more metal salts. The catholyte also includes other components, such as wetting agents and / or complexing agents and / or buffer substances and / or surfactants. The metal salts and / or the other components are present in a liquid medium, particularly water, and are dissolved in this liquid medium. The components are preferably dissolved in distilled, or even demineralized, water. It is also possible to dissolve the components in an organic solvent, which allows even sparingly soluble components to be dissolved.The electroplating layer is formed in particular by the deposition of metal cations on the workpiece surface, whereby the metal cations are present in particular dissolved in the catholyte.

[0039] One possible embodiment of the invention provides for the electroplating layer to be formed as a chromium layer and / or deposited from a catholyte containing a chromium(III) salt. In particular, a hard chromium layer consisting of trivalent chromium cations is deposited as a chromium layer on the workpiece surface.

[0040] Chromium(III) cations: To introduce the chromium(III) cations required for deposition into the catholyte, the following substances, for example, can be dissolved in the catholyte, preferably being present in a concentration of 0.2 to 2 mol / l of the respective chromium compound in the catholyte, selected from the group comprising: • Chromium(III) hydroxide sulfate: Cr OH (SO 2 ) • Chromium(III) sulfate: Cr 2 (SO 4 ) 3 x 18 H 2 O • Chromium(III) formate: Cr (COO) 3 • Chromium(III) potassium sulfate: CrK (SO4) 2 x 12 H 2 O • basic chromium(III) acetate: Cr3(CH3COO)7(OH)2x3H2O

[0041] To improve the deposition process, in particular to stabilize it and / or to improve the technical or optical properties of the deposited electroplating layer, the catholyte preferably comprises further components. Buffer components:

[0042] For pH regulation, particularly for buffering, the catholyte comprises in particular one or more buffer components, preferably with a concentration of 0.5 - 3 mol / l each, selected from the group comprising: • Aluminum sulfate: Al 2 (SO 4 ) 3 x 16 H 2 O • Magnesium acetate: Mg(CH3COO)2

[0043] In particular, for buffering the pH value in the cathode film, the catholyte comprises a buffer component, preferably with a concentration of 3-6 mol / l or 25 wt. %, selected from the group comprising: • Ammonia: NH4OH Complexing agents:

[0044] Further components that the catholyte may comprise for complexation of the chromium(III) ion, preferably with a concentration of 3-6 mol / l each, are selected from the group comprising: • Potassium formate: KCOO • Ammonium formate: NH4 COO • Potassium acetate: KCH 3 COO • Ammonium acetate: NH4CH3COO • Potassium oxalate: K 2 (COO) 2 • Formic acid HCOOH

[0045] Further components for improving the wetting of the workpiece and / or the gas, in particular hydrogen, removal from the deposited electroplating layer, preferably with a concentration of 0.5-5 g / l each, are selected from the group comprising: Anionic surfactants:

[0046] • Diisohexyl sulfosuccinate: C 16 H 29 NaO 7 S • Diisobutyl sulfosuccinate: C 12 H 21 NaO 7 S • Sodium lauryl sulfate: C 12 H 25 SO 4 Na Non-ionic surfactants:

[0047] Polyethylene glycol (PEG 200) Polyvinylpyrrolidone (PVP 50) Sulfur-containing compounds:

[0048] • Sodium saccharinate: C 7 H 4 SO 3 NNa • Potassium thiocyanate: KSCN

[0049] The catholyte is used, in particular, within a temperature range of 30 to 60°C, or is heated or cooled such that it has a temperature between 30 and 60°C in the area to be coated. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the catholyte is used with a pH value between 2 and 6, and the electroplating device specifically includes a pH probe and / or a pH controller. Finally, the workpiece is connected to the voltage and / or current source in such a way that a current density in the range of 20 to 100 A / dm² is generated at the workpiece surface, particularly in the area to be coated.

[0050] The anolyte comprises, in particular, one or more acids, which are preferably dissolved in a solvent. In particular, the same solvents used for the catholyte may be used. For example, the anolyte may comprise the following acids and / or their salts, which are preferably present in a concentration of 10 to 20 wt.% in the anolyte. The acids and / or their salts are selected from the group comprising: • Formic acid: COOH • Acetic acid: CH3COOH • Sulfuric acid: H₂SO₄

[0051] The anode is made of an electrically conductive material. For example, the anode can be made of graphite or metal, or of a metal coated with a metal. The following list provides an overview of possible anode designs, particularly regarding the anode material: Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, especially highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, especially the product "Ridurid V 1017" from Ringsdorf; stainless steel with gold coating

[0052] The anolyte is used, in particular, within a temperature range of 20 to 60°C, or is heated or cooled such that it has a temperature between 20 and 60°C. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the anode is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 50 A / dm² is present at the surface of the anode, particularly at the surface of the anode that is in contact with the anolyte.

[0053] The deposition of a chromium layer from a catholyte containing chromium(III) ions offers the advantage, in contrast to the deposition of a chromium layer from a catholyte containing chromium(VI) ions, that the cathode film, which forms as an electroplating layer on the cathode during the deposition process, does not need to be permanently maintained. Unlike the deposition of a chromium layer from a catholyte containing chromium(VI) ions, where a complex cathode film must be formed on the surface of the workpiece to be coated and, above all, maintained throughout the entire deposition process, it is not necessary to permanently maintain the cathode film present when deposition from a catholyte containing chromium(III) ions.When depositing a chromium layer from a chromium(VI)-containing catholyte, the catholyte carrier would destroy the cathode film through the relative movement between the workpiece and the catholyte carrier, thus preventing or hindering the deposition of the chromium layer. When depositing a chromium layer from a chromium(III)-containing catholyte, a cathode film also forms on the area of ​​the workpiece surface in contact with the catholyte, but this film has a less complex structure and forms more quickly. Therefore, after being destroyed by the catholyte carrier through the relative movement between the workpiece and the catholyte carrier, this cathode film is immediately renewed, or rather, regenerated, thus maintaining the deposition capacity.Another advantage of depositing a chromium layer from a catholyte containing chromium(III) ions is that the optional membrane prevents or inhibits the oxidation of chromium(III) to chromium(VI).

[0054] The catholyte support reduces the diffusion layer thickness. This results in a continuous supply of catholyte to the electrolyte / chromium interface, particularly the cathode film between the catholyte and the workpiece surface, especially the deposited chromium layer. Consequently, no chromium depletion or pH increase occurs. This suppresses or prevents the precipitation of chromium hydroxide. Furthermore, the hydrogen produced is removed. This hydrogen would otherwise lead to the formation of chromium hydride, which would then cause the chromium layer to become brittle. The catholyte support also suppresses bud formation.

[0055] Furthermore, it is provided that the chromium layer deposited on the workpiece surface has a layer thickness, in particular a layer thickness averaged at different points of the chromium layer of at least 20 µm, in particular 200 µm and / or a Vickers hardness according to EN ISO 6507, in particular a Vickers hardness averaged at different points of the chromium layer according to EN ISO 6507 of at least 800 HV, in particular at least 900 HV, preferably 1000 HV and particularly preferably 1100 HV.

[0056] Further development of the electroplating layer as a chromium layer and / or the chromium layer produced from a catholyte containing a chromium(III) salt involves forming the electroplating layer as a chromium alloy layer. In this case, the electroplating layer can be or be formed as a chromium-indium, chromium-bismuth, or chromium-antimony layer. Specifically, the electroplating layer is produced from a catholyte containing a chromium(III) salt, which also contains indium, bismuth, or antimony cations and / or anions. The indium, bismuth, or antimony anions can be introduced as sulfate or formate compounds. The addition of indium, antimony, or bismuth cations can form alloy phases that reduce cracking of the chromium layer or result in an improved surface with fewer cracks.

[0057] One possible embodiment of the invention provides for the electroplating layer to be formed as a nickel-phosphorus layer and / or to be deposited from a catholyte containing nickel(II) salt and phosphorus. Nickel(II) cations:

[0058] To introduce the nickel(II) cations required for deposition into the catholyte, the following substances, for example, may be dissolved in the catholyte, preferably being present in a concentration of 0.5-2 mol / l in the catholyte, selected from the group comprising: • Nickel chloride: NiCl 2 x 6 H 2 O • Nickel sulfate: NiSO 4 x7 H 2 O • Nickel methanesulfonate: Ni(H 3 CSO 3 ) 2 Phosphorus:

[0059] In particular, negatively charged phosphorus compounds are reduced to elemental phosphorus at the cathode using hydrogen and incorporated into the layer. To introduce the phosphorus required for deposition into the catholyte, the following substances, for example, can be dissolved in the catholyte, preferably in a concentration of 0.5–3 mol / L, and are selected from the group comprising: • Phosphorous acid: H3PO3 • Phosphoric acid: H3PO4 • Na-hypophosphite: NaH₂PO₂

[0060] To improve the deposition process, in particular to stabilize it and / or to improve the technical or optical properties of the deposited electroplating layer, the catholyte preferably comprises further components. Buffer components:

[0061] For pH regulation, particularly for buffering, the catholyte comprises in particular a buffer component, preferably with a concentration of 0.5-1 mol / l, selected from the group comprising: • Boric acid: B(OH) 3 Complexing agents:

[0062] Further components that the catholyte may comprise for complexing the nickel, preferably with a concentration of 0.5-3 mol / l, are selected from the group of organic acids, comprising: • Citric acid: C6H8O7 • Malonic acid: C3H4O4

[0063] Further components for improving the wetting of the workpiece and / or the gas, in particular hydrogen, removal from the deposited electroplating layer, preferably with a concentration of 0.5-5 g / l each, are selected from the group comprising: Anionic surfactants:

[0064] • Diisohexyl sulfosuccinate: C 16 H 29 NaO 7 S • Diisobutyl sulfosuccinate: C 12 H 21 NaO 7 S • Sodium lauryl sulfate: C12H25SO4Na

[0065] The catholyte is used, in particular, within a temperature range of 50 to 75°C, or is heated or cooled such that it has a temperature between 50 and 75°C in the area to be coated. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the catholyte is used with a pH value between 2 and 5, and the electroplating device specifically includes a pH probe and / or a pH controller. Finally, the workpiece is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 5 A / dm² is generated at the workpiece surface, particularly in the area to be coated.

[0066] The anolyte comprises, in particular, one or more acids, which are preferably dissolved in a solvent. In particular, the same solvents used for the catholyte may be used. For example, the anolyte may comprise the following acids and / or their salts, which are preferably present in a concentration of 5-20 wt.% in the anolyte. The acids and / or their salts are selected from the group comprising: • Phosphorous acid: H3PO3 • Phosphoric acid: H3PO4

[0067] The anode is made of an electrically conductive material. For example, the anode can be made of graphite or metal, or of a metal coated with a metal. The following list provides an overview of possible anode designs, particularly regarding the anode material: Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0068] The anolyte is used, in particular, within a temperature range of 20 to 60°C, or is heated or cooled to maintain a temperature between 20 and 60°C. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the anode is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 10 A / dm² is present at the surface of the anode, particularly at the surface of the anode in contact with the anolyte.

[0069] One possible embodiment of the invention provides for the electroplating layer to be formed as a nickel layer and / or to be deposited from a catholyte containing nickel(II) salt. Nickel(II) cations:

[0070] To introduce the nickel(II) cations required for deposition into the catholyte, the following substances, for example, may be dissolved in the catholyte, preferably being present in a concentration of 0.5-2 mol / l in the catholyte and being selected from the group comprising: • Nickel chloride: NiCl 2 x 6 H 2 O • Nickel sulfate: NiSO 4 x 7 H 2 O • Nickel methanesulfonate: Ni(H3CSO3)2 • Ni-bis-sulfamidate: Ni(H2NSO3)2

[0071] To improve the deposition process, in particular to stabilize it and / or to improve the technical or optical properties of the deposited electroplating layer, the catholyte preferably comprises further components. Buffer components:

[0072] For pH regulation, particularly for buffering, the catholyte comprises in particular a buffer component, preferably with a concentration of 0.5-2 mol / l, selected from the group comprising: • Boric acid: B(OH) 3 Other components:

[0073] Further components for improving the wetting of the workpiece and / or the gas, in particular hydrogen, removal from the deposited electroplating layer, preferably in a concentration of 0.5-5 g / l each, are selected from the group comprising: Anionic surfactants:

[0074] • Diisohexyl sulfosuccinate: C 16 H 29 NaO 7 S • Diisobutyl sulfosuccinate: C 12 H 21 NaO 7 S • Sodium lauryl sulfate: C12H25SO4Na

[0075] The catholyte is used, in particular, within a temperature range of 30 to 60°C, or is heated or cooled such that it has a temperature between 30 and 60°C in the area to be coated. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the catholyte is used with a pH value between 3 and 5, and the electroplating device specifically includes a pH probe and / or a pH controller. Finally, the workpiece is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 10 A / dm² is generated at the workpiece surface, particularly in the area to be coated.

[0076] The anolyte comprises, in particular, one or more acids, which are preferably dissolved in a solvent. In particular, the same solvents used for the catholyte may be used. For example, the anolyte may comprise the following acids and / or their salts, which are preferably present in a concentration of 10-30 wt.% in the anolyte. The acids and / or their salts are selected from the group comprising: • Amidosulfonic acid: H 2 NSO 3 H

[0077] The anode is made of an electrically conductive material. For example, the anode can be made of graphite or metal, or of a metal coated with a metal. The following list provides an overview of possible anode designs, particularly regarding the anode material: Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0078] The anolyte is used, in particular, within a temperature range of 20 to 60°C, or is heated or cooled to maintain a temperature between 20 and 60°C. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the anode is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 10 A / dm² is present at the surface of the anode, particularly at the surface of the anode in contact with the anolyte.

[0079] One possible embodiment of the invention provides for the electroplating layer to be formed as a bronze layer and / or to be deposited from a catholyte containing a tin(II) salt and a copper(II) salt. Tin(II) cations:

[0080] To introduce the tin(II) cations required for deposition into the catholyte, the following substances, for example, can be dissolved in the catholyte, preferably being present in a concentration of 0.1-1 mol / l in the catholyte, selected from the group comprising: • Tin methanesulfonate: Sn(CH3SO3)2

[0081] To introduce the copper(II) cations required for deposition into the catholyte, the following substances, for example, can be dissolved in the catholyte, preferably being present in a concentration of 0.1-1 mol / l in the catholyte, selected from the group comprising: • Copper methanesulfonate: Cu(CH3SO3)2

[0082] To improve the deposition process, in particular to stabilize it and / or to improve the technical or optical properties of the deposited electroplating layer, the catholyte preferably comprises further components. Oxidation inhibitor:

[0083] To regulate the pH value, in particular to prevent the oxidation of Sn(II) to Sn(IV) and preferably with a concentration of 0.1-10 g / l, the catholyte comprises in particular a buffer component selected from the group comprising: • Pyrocatechin: C 6 H 6 O 2 Complexing agents:

[0084] Other components that the catholyte may include for pH regulation, preferably at a concentration of 100-400 g / l, are selected from the group comprising: • Methanesulfonic acid: CH3SO3H Gloss-forming agents:

[0085] Furthermore, the catholyte may comprise additional components, preferably with a concentration of 1-5 g / l each, particularly for gloss formation, wherein these are selected from the group comprising: • 3,3-Thiodipropanol: C 6 H 14 O 2 S • 3,6 Dithiooctanol-1,8: C 6 H 14 O 2 S 2

[0086] Further components for improving the wetting of the workpiece and / or the gas, in particular hydrogen, removal from the deposited electroplating layer, preferably in a concentration of 0.5-40 g / l each, are selected from the group comprising: Non-ionic surfactants:

[0087] • β-Naphthol ethoxylate: (C 2 H 2 O) n C 10 H 8 O • Nonylphenol ethoxylate (eg Lutensol AP-14): C 43 H 79 O 14

[0088] The catholyte is used, in particular, within a temperature range of 20 to 30°C, or is heated or cooled such that it has a temperature between 20 and 30°C in the area to be coated. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the catholyte is used with a pH value of <1, and in particular, this pH value is set. The electroplating device specifically includes a pH probe and / or a pH controller. Finally, the workpiece is connected to the voltage and / or current source in such a way that a current density in the range of 0.2 to 2 A / dm² is generated at the workpiece surface, particularly in the area to be coated.

[0089] The anolyte comprises, in particular, one or more acids, which are preferably dissolved in a solvent. In particular, the same solvents used for the catholyte may be used. For example, the anolyte may comprise the following acids and / or their salts, which are preferably present in a concentration of 10–30 wt.% in the anolyte. The acids and / or their salts are selected from the group comprising: Methanesulfonic acid (70 wt. %):CH3SO3H

[0090] The anode is made of an electrically conductive material. For example, the anode can be made of graphite or metal, or of a metal coated with a metal. The following list provides an overview of possible anode designs, particularly regarding the anode material: Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0091] The anolyte is used, in particular, within a temperature range of 20 to 40°C, or is heated or cooled to maintain a temperature between 20 and 40°C. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the anode is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 10 A / dm² is present at the surface of the anode, particularly at the surface of the anode in contact with the anolyte.

[0092] One possible embodiment of the invention provides for the electroplating layer to be formed as a tin-nickel layer and / or to be deposited from a catholyte containing a tin(II) salt and a nickel(II) salt. Tin(II) cations:

[0093] To introduce the tin(II) cations required for deposition into the catholyte, the following substances, for example, may be dissolved in the catholyte, preferably being present in a concentration of 0.05-0.5 mol / l in the catholyte, selected from the group comprising: • Tin(II) chloride: SnCl 2 2 H 2 O • Tin methanesulfonate: Sn(CH3SO3)2

[0094] To introduce the nickel(II) cations required for deposition into the catholyte, the following substances, for example, may be dissolved in the catholyte, preferably being present in a concentration of 0.5-2 mol / l in the catholyte, selected from the group comprising: • Nickel methanesulfonate: Ni(CH3SO3)2 • Nickel chloride: NiCl 2 x 6 H 2 O

[0095] To improve the deposition process, in particular to stabilize it and / or to improve the technical or optical properties of the deposited electroplating layer, the catholyte preferably comprises further components. Conductivity improver:

[0096] To increase conductivity, the catholyte comprises in particular a component, preferably with a concentration of 3-5 mol / l, selected from the group comprising: • Potassium chloride: KCl • Ammonium chloride: NH4Cl Complex formation:

[0097] Further components that the catholyte may comprise for stabilizing the electrolyte, preferably with a concentration of 0.5-2 mol / l, are selected from the group comprising: • Ammonium bifluoride: HF NH 4 F • Sodium fluoride: NaF Gloss-forming agents:

[0098] Furthermore, the catholyte may comprise additional components, particularly for gloss formation, preferably at a concentration of 0.001-1 g / l, wherein these are selected from the group comprising: • Phenylpropionamide: C 9 H 11 N

[0099] Further components for improving the wetting of the workpiece and / or the gas, in particular hydrogen, removal from the deposited electroplating layer, preferably in a concentration of 0.001-1 g / l each, are selected from the group comprising: Anionic surfactants:

[0100] • Sodium lauryl sulfate: C 12 H 25 SO 4 Na Sulfur-containing compounds:

[0101] • 3,6 Dithiooctanol-1,8: C6H14O2S2

[0102] The catholyte is used, in particular, within a temperature range of 60 to 90°C, or is heated or cooled such that it has a temperature between 60 and 90°C in the area to be coated. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the catholyte is used with a pH value <1, and in particular, this pH value is set. The electroplating device specifically includes a pH probe and / or a pH controller. Finally, the workpiece is connected to the voltage and / or current source in such a way that a current density in the range of 0.5 to 5 A / dm² is generated at the workpiece surface, particularly in the area to be coated.

[0103] The anolyte comprises, in particular, one or more acids, which are preferably dissolved in a solvent. In particular, the same solvents used for the catholyte may be used. For example, the anolyte may comprise the following acids and / or their salts, which are preferably present in a concentration of 10-20 wt% hydrochloric acid in the anolyte. The acids and / or their salts are selected from the group comprising: • Potassium chloride (300g / L): KCl • Hydrochloric acid: HCl

[0104] The anode is made of an electrically conductive material. For example, the anode can be made of graphite or metal, or of a metal coated with a metal. The following list provides an overview of possible anode designs, particularly regarding the anode material: Niobium with platinum coating; graphite, especially highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, especially the product "Ridurid V 1017" from Ringsdorf

[0105] The anolyte is used, in particular, within a temperature range of 20 to 40°C, or is heated or cooled to maintain a temperature between 20 and 40°C. The electroplating device specifically includes a heat source and a temperature controller for regulating the heat source. Furthermore, the anode is connected to the voltage and / or current source in such a way that a current density in the range of 1 to 10 A / dm² is present at the surface of the anode, particularly at the surface of the anode in contact with the anolyte.

[0106] In one possible embodiment, the electroplated layer can also be formed as a layer of iron, aluminum, copper, gold, cobalt, tin, or zinc, or as an alloy thereof. The electroplated layer consists of a catholyte containing a corresponding metal salt, the metal salt being present in a dissolved form within the catholyte.

[0107] In a preferred embodiment, the workpiece is made of a metallic material and / or already has a galvanic coating on its surface. In particular, the workpiece can also consist of a polymer with a metallic galvanic coating, with a further galvanic coating being deposited on top of the existing coating. This results in a wide variety of workpieces that can be coated, and the galvanic coatings can be tailored to the material and / or the workpiece surface.

[0108] A further object of the invention is a method for depositing an electroplated layer using an electroplating device as previously described, wherein the electroplated layer is deposited on a workpiece, the electroplating device comprising at least one cathode, the workpiece being configured as the cathode or being electrically connected to the cathode. The electroplating device further comprises a catholyte, an anolyte, and an anode, wherein the electroplated layer is deposited from the catholyte onto the workpiece, the catholyte contacting the workpiece, and the anode contacting the anolyte. Preferably, the electroplating device includes an optional membrane, the optional membrane being arranged between the catholyte and the anolyte, thereby preventing or limiting, in particular, the transfer of cations from the catholyte to the anolyte.The electroplating device comprises a catholyte carrier, the catholyte carrier being impregnated with the catholyte and in contact with the workpiece in a contact area, such that the catholyte from the catholyte carrier contacts the workpiece. The electroplating device is designed to generate a relative movement between the catholyte carrier and the workpiece, causing the contact area on the workpiece to shift in order to create the electroplated layer on the workpiece.

[0109] In one possible implementation, the electroplated layer is thermally treated after deposition on the workpiece. Specifically, the thermal post-treatment process is designed as heat aging, particularly as annealing. Here, the electroplated layer, or more precisely the entire workpiece, is heated and held at this temperature for a specific period. Depending on the electroplated layer and the desired effect, the workpiece and / or the electroplated layer is heated to a temperature between 100 and 400 °C and held at this temperature for a period of 0.5 to 5 hours. This can, for example, drive off hydrogen bound in the electroplated layer and / or the workpiece. Furthermore, depending on the metal or metal alloys deposited, any cracks in the electroplated layer can be closed or reduced in size.This allows the optical and technical properties of the electroplated layer to be improved.

[0110] Another object of the invention is a workpiece with a galvanic layer, wherein the galvanic layer is deposited on the workpiece according to the method described above.

[0111] Further features, advantages, and effects of the invention will become apparent from the following description of preferred embodiments of the invention. These will show: Figure 1 shows an embodiment of an electroplating device with a vertically arranged workpiece;

[0112] Corresponding or identical parts are each provided with the same reference symbols in the figures.

[0113] The Figure 1Figure 1 shows an embodiment of an electroplating device 1 for depositing an electroplated layer on a workpiece 2. The workpiece 2 is connected via an electrical connection 9a to a negative pole of a voltage and / or current source and is supplied with a DC voltage and / or a DC current, wherein the workpiece 2 is designed as the cathode.

[0114] Furthermore, the workpiece 2, which serves as the cathode, is mechanically connected to an actuator 3. In particular, the actuator 3 can be configured such that the workpiece 2 is connected to the actuator 3 by a material, force, and / or form-fit connection or is fixed by the actuator 3. In particular, the actuator 3 can also be configured as a clamping device to fix, and especially to clamp, the workpiece 2. For example, the workpiece 2 can be fixed by a chuck or collet integrated into the actuator 3.

[0115] Actuator 3 is shown in the diagram. Figure 1 The actuator 3 is designed to generate a rotational movement about the longitudinal axis and / or a linear movement along the longitudinal axis of the workpiece 2. The longitudinal axis is represented by a dashed line. The actuator 3 can be configured as one or more electric motors or comprise one or more electric motors, with the rotational movement and / or the linear movement being generated by the one or more electric motors.

[0116] In particular, the actuator 3 can also be configured to generate the rotational movement of the workpiece 2, but is moved along the longitudinal axis of the workpiece 2 by another actuator 3, for example along a guide. In particular, the other actuator 3 can be configured as a purely vertical actuator, for example as a pneumatic, hydraulic or electromechanical piston.

[0117] In another embodiment, the linear relative movement between workpiece 2 and catholyte carrier 8 along the longitudinal axis of the workpiece 2 can also be generated by the linear movement of the unit consisting of catholyte carrier 8, optional membrane 7, anolyte container 5, anolyte 6, anode 4 and catholyte line 12, wherein the linear movement is generated by a height actuator.

[0118] In particular, the workpiece 2 is designed as a rotationally symmetric body, especially as a cylindrical body. The workpiece 2 is positioned such that its longitudinal axis is parallel to the catholyte carrier 8, with the workpiece 2 and the catholyte carrier 8 being in contact within a contact area.

[0119] The electroplating device 1 comprises the catholyte carrier 8, the optional membrane 7, the anolyte container 5, the anolyte 6 and the anode 4, wherein these are arranged according to the exemplary embodiment in Figure 1The anode 4 is connected to each other and is fixedly arranged in the electroplating device 1. The anode 4 is arranged such that it is completely or partially surrounded by the anolyte 6. The anode 4 is connected via the electrical connection 9b to a voltage and / or current source, in particular to the positive terminal of a voltage and / or current source, and is preferably supplied with a direct voltage and / or direct current. The anolyte 6 is in direct contact with the anode 4, the anolyte container 5, and in particular the optional membrane 7.

[0120] Furthermore, it shows Figure 1The exemplary electroplating device 1 comprises a catholyte container 10, which is arranged below the workpiece 2 and serves to supply the catholyte 11 for the deposition of the electroplating layer. Furthermore, the catholyte container 10 serves to collect the excess catholyte 11, in particular the catholyte 11 that seeps through the catholyte carrier 8 or escapes from the contact area between the workpiece 2 and the catholyte carrier 8. The exemplary electroplating device 1 also includes a heating element 13, which is attached in or to the catholyte container 10 and regulates the temperature of the catholyte 11. In particular, the heating element 13 is designed to detect the temperature and regulate it based on a temperature setting.

[0121] A catholyte line 12 is used to impregnate the catholyte carrier 8 with the catholyte 11 and to supply the contact area between workpiece 2 and catholyte carrier 8 with the catholyte 11. This line delivers the catholyte 11 to the catholyte carrier 8 or to the contact area between workpiece 2 and catholyte carrier 8. Furthermore, the catholyte line 12 can also be connected to the catholyte carrier 8 in such a way that the catholyte 11 is delivered directly into the catholyte carrier 8. The catholyte line 12 includes, in particular, a filter 14 for filtering the catholyte 11 of impurities and a pump 15, wherein the pump 15 conveys the catholyte 11 through the filter 14 and the catholyte line 12, in particular from the catholyte container 10 to the catholyte carrier 8 and / or the contact area between workpiece 2 and catholyte carrier 8. This creates a catholyte cycle whereby the catholyte 11 in the contact area between workpiece 2 and catholyte carrier 8 is continuously renewed.

[0122] The deposition of the electroplated layer takes place in the contact area between workpiece 2 and catholyte carrier 8, with the electroplated layer being deposited on the surface of workpiece 2. Specifically, the contact area between workpiece 2 and catholyte carrier 8 is shifted on the workpiece surface by the rotational and / or linear movement of workpiece 2, thereby depositing a uniform electroplated layer. In particular, the electroplated layer is a metal layer and is deposited from the metal cations of the catholyte 11 on the workpiece surface.

[0123] In a first embodiment, the electroplated layer is formed as a chromium layer. The following are embodiments of the catholytes 11, anolytes 6, and anode materials used together in the electroplating device 1, as well as the set anode, cathode, anolyte, and catholyte parameters for the deposition of the electroplated layer, in particular a chromium layer, on the surface of the workpiece 2, with the main components of the catholytes 11 and anolytes 6 being listed. Example 1: Catholic:

[0124] • Chromium(III) sulfate solution: Cr 2 (SO 4 ) 3 x 18 H 2 O 0.25 mol / l • Ammonium formate: NH4 COO 2.5 mol / l • Aluminum sulfate: Al 2 (SO 4 ) 3 x 16 H 2 O 0.2 mol / l • Potassium thiocyanate: KSCN 0.05 mol / l • Temperature: 45 °C + / - 2 • pH value: 4.5 + / - 0.1 • Current density: 20 A / dm²< Anolyte:

[0125] • 20 wt. % sulfuric acid H₂SO₄ • Temperature: 20 - 40 °C • pH value <1 • Anode current density: 5 A / dm²< Anode:

[0126] Titanium with platinum coating Example 2: Catholic:

[0127] • Chromium(III) sulfate solution: Cr 2 (SO 4 ) 3 x 18 H 2 O 0.3 mol / l • Potassium formate: KCOO 2.5 mol / l • Aluminum sulfate: Al 2 (SO 4 ) 3 x 16 H 2 O 0.2 mol / l • Sodium lauryl sulfate: C 12 H 25 SO 4 Na 0.05 mol / l • Temperature 50 °C + / - 2 • pH value: 4.5 + / - 0.3 • Current density: 30 A / dm²< Anolyte:

[0128] • 20 wt. % sulfuric acid: H₂SO₄ • Temperature: 20 - 40°C • pH value <1 • Anode current density: 5 A / dm²< Anode:

[0129] Titanium with platinum coating Example 3: Catholic:

[0130] • Chromium(III) hydroxide sulfate: Cr OH (SO 4 ) 0.35 mol / l • Ammonium formate: NH4 COO 2.5 mol / l • Aluminum sulfate: Al 2 (SO 4 ) 3 x 16 H 2 O 0.2 mol / l • Sodium lauryl sulfate: C 12 H 25 SO 4 Na 0.05 mol / l • Temperature 50 °C + / - 2 • pH value: 4.5 + / - 0.5 • Current density: 50 A / dm²< Anolyte:

[0131] • 20 wt. % formic acid: COOH • 50g / l sodium sulfate: Na₂SO₄ • Temperature: 20 - 40 °C • pH value <2 • Anode current density: 5 A / dm²< Anode:

[0132] Titanium with platinum coating

[0133] In a further embodiment, the electroplating layer is designed as a chromium alloy layer, in particular a chromium-indium layer. The following are exemplary embodiments of the catholytes 11, anolytes 6, and anode materials used in the electroplating device 1, as well as the set anode, cathode, anolyte, and catholyte parameters for the deposition of the electroplating layer, in particular a chromium-indium layer, on the surface of the workpiece 2, with the main components of the catholytes 11 and anolytes 6 being listed. Example 1: Catholic:

[0134] • Chromium(III) hydroxide sulfate: Cr OH (SO 4 ) 0.35 mol / l • Ammonium formate: NH4 COO 2.5 mol / l • Indium sulfate: In 2 (SO 4 ) 3 x 9 H 2 O 0.01 mol / l • Sodium lauryl sulfate: C 12 H 25 SO 4 Na 0.05 mol / l • Temperature 50 °C + / - 5 • PH value: 5,2 + / - 0,5 • Current density: 35 A / dm²< Anolyte:

[0135] • 10 wt. % sulfuric acid: H₂SO₄ • Temperature: 20 - 40 °C • PH value <1 • Anode current density: 5 A / dm²< Anode:

[0136] Titanium with platinum coating Example 2: Catholic:

[0137] • Chromium(III) hydroxide sulfate: Cr OH (SO 4 ) 0.3 mol / l • Ammonium formate: NH4 COO 2.0 mol / l • Bismuth sulfate: Bi 2 (SO 4 )3 0.01 mol / l • Sodium lauryl sulfate: C 12 H 25 SO 4 Na 0.05 mol / l • Temperature 50 °C + / - 2 • PH value: 5,2 + / - 0,5 • Current density: 30 A / dm²< Anolyte:

[0138] • 10 wt. % sulfuric acid: H₂SO₄ • Temperature: 20 - 50 °C • PH value <1 • Anode current density: 5 A / dm²< Anode: Titanium with platinum coating:

[0139] As an alternative to forming the electroplating layer as a chromium-indium layer, the electroplating layer can also be formed as a chromium-bismuth layer or a chromium-antimony layer. It is possible that the electroplating layer is or will be formed as described in EP 4 151 779 A1, the disclosure of which is preferably incorporated into the present disclosure by reference.

[0140] In another embodiment, the electroplated layer is formed as a nickel-phosphorus layer. An exemplary embodiment of the catholyte 11, anolyte 6, and anode material used together in the electroplating device 1 is described below, along with the set anode, cathode, anolyte, and catholyte parameters for the deposition of the nickel-phosphorus layer on the surface of the workpiece 2, and the main components of the catholyte 11 and anolyte 6 are named. Example implementation: Catholic:

[0141] • Nickel chloride: NiCl 2 x 6 H 2 O: 166 g / l, especially 41 g / l Ni • Phosphorous acid: H3PO3 148 g / l • Phosphoric acid: H3PO4 20 g / l • Glyoxal: (40%) C₂H₂O₂ 20 ml / l • Citric acid: C6H8O7 10 g / l • Temperature: 65 °C • PH value <1 • Current density: 1 A / dm²< Anolyte:

[0142] • 10 wt. % phosphoric acid H3PO4 • Temperature: 20 - 40 °C • PH value <1 • Current density: 5 - 10 A / dm²< Anode:

[0143] Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0144] Another embodiment provides that the electroplating layer is formed as a nickel layer. An exemplary embodiment of the catholyte 11, anolyte 6, and anode material used together in the electroplating device 1 is listed below, along with the set anode, cathode, anolyte, and catholyte parameters for the deposition of the nickel layer on the surface of the workpiece 2, and the main components of the catholyte 11 and anolyte 6 are named. Example implementation: Catholic:

[0145] • Nickel sulfamate: Ni(NH₂SO₃) 2 x 4 H₂O 80 g / l (Ni) • Nickel chloride: NiCl 2 x 6 H 2 O: 5 g / l • Boric acid: B(OH) 3 30 g / l • Current density: 1 A / dm²< • Temperature: 30 °C • PH value: 4,5 Anolyte:

[0146] • 20 wt. % amidosulfonic acid: NH₂SO₃H • Temperature: 20 - 40 °C • PH value <2 • Current density: 5 - 10 A / dm²< Anode:

[0147] Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0148] Another embodiment provides that the electroplated layer is formed as a bronze layer. An exemplary embodiment of the catholyte 11, anolyte 6, and anode material used together in the electroplating device 1 is listed below, along with the set anode, cathode, anolyte, and catholyte parameters for the deposition of the bronze layer on the surface of the workpiece 2, and the main components of the catholyte 11 and anolyte 6 are named. Example implementation: Catholic:

[0149] • Tin methanesulfonic acid: Sn(CH 3 SO 3 ) 2 10 g / l • Copper methanesulfonic acid: Cu(CH3SO3)2 50 g / l • Methanesulfonic acid: CH 3 SO 3 H 230 g / l • Nonylphenol ethoxylate: 10 g / l • Bismuth sulfonate: Bi(CH3SO3)2 5 g / l • Brenzchatechin: C6H6O2 5 g / l • 3,6 Dithiooctanol- 1,8: C6H14O2S2 1g / L • β-Naphtholethoxylate: (C 2 H 2 O) n C 10 H 8 O 40g / L Anolyte:

[0150] • 20 wt. % methanesulfonic acid: CH 3 SO 3 H • Temperature: 20 - 40 °C • PH value: >1 • Current density: 5 - 10 A / dm²< Anode:

[0151] Titanium with platinum coating; titanium with mixed oxide coating, for example, an iridium-titanium mixed oxide coated titanium electrode from Umicore; niobium with platinum coating; graphite, in particular highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, in particular the product "Ridurid V 1017" from Ringsdorf

[0152] In a further embodiment, the electroplating layer is designed as a tin-nickel layer. An embodiment of the catholyte 11, anolyte 6, and anode material used together in the electroplating device 1 is described below, along with the set anode, cathode, anolyte, and catholyte parameters for deposition of the tin-nickel layer on the surface of the workpiece 2, and the main components of the catholyte 11 and anolyte 6 are named. Example implementation: Catholic:

[0153] • Nickel chloride: NiCl 2 x 6 H 2 O: 250 g / l • Tin chloride: Sn Cl 2 x 2 H 2 O 15 g / l • Ammonium bifluoride: NH 4 F x HF 2 g / l • Potassium chloride: KCI 200 g / L • 3,6 Dithiooctanol- 1,8: C6H14O2S2 0.01 g / L • Temperature: 75 °C • PH value: <1 • Current density: 1 A / dm²< Anolyte:

[0154] • 10% by volume hydrochloric acid (32% by weight) HCl • Temperature: 65 °C • PH value: >1 • Current density: 1 - 5 A / dm²< Anode:

[0155] Niobium with platinum coating; graphite, especially highly oriented pyrolytic graphite with high electrical conductivity, such as "HOPG-ZYH" from the original brand "Advanced Ceramik"; graphite, especially the product "Ridurid V 1017" from Ringsdorf Reference symbol list

[0156] 1 Electroplating device 2 Workpiece 3 Actuator 4 Anode 5 Anolyte container 6 Anolyte 7 Membrane 8 Catholyte carrier 9a, b Electrical connection 10 Catholyte container 11 Catholyte 12 Catholyte line 13 Heating element 14 Filter 15 Pump

Claims

1. Electroplating device (1) for producing an electroplated layer on a workpiece (2), comprising the workpiece (2), comprising at least one cathode, wherein the workpiece (2) is designed as the cathode or is electrically connected to the cathode, comprising a catholyte (11), comprising an anode (4) and an anolyte (6), wherein the anode (4) contacts the anolyte (6), characterized by the fact that the electroplating device (1) has a catholyte carrier (8), wherein the catholyte carrier (8) is impregnated with the catholyte (11) and is in contact with the workpiece (2) in a contact area, such that the catholyte (11) from the catholyte carrier (8) contacts the workpiece (2), and that the electroplating device (1) is configured to generate a relative movement between the catholyte carrier (8) and the workpiece (2), such that the contact area on the workpiece (2) shifts in order to produce the electroplating layer on the workpiece (2).

2. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the catholyte carrier (8) has open capillaries and / or open pores.

3. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the catholyte carrier (8) is formed as a fleece, woven fabric, braid, knitted fabric, crochet, laid fabric, felt or as cotton wool.

4. Electroplating device (1) according to one of the preceding claims, characterized by the fact that The relative motion is formed as a rotational motion and / or as a linear motion.

5. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the workpiece (2) is designed as a rotationally symmetric body.

6. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the electroplating device (1) has a membrane (7) wherein the membrane (7) is arranged between the catholyte (11) and the anolyte (6).

7. Electroplating device (1) according to one of the preceding claims, characterized by the fact that which has a voltage and / or current source for generating an electrical potential at the cathode and / or anode.

8. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the electroplating layer is formed as a chromium layer or chromium alloy layer and / or is deposited from a catholyte (11) containing a chromium(III) salt, wherein the anolyte (6) contains an acid and / or a salt of the acid.

9. Electroplating device (1) according to any one of the preceding claims 1 to 7, characterized by the fact that the electroplating layer is formed as a nickel layer and / or is deposited from a nickel(II) salt containing catholyte (11), wherein the anolyte (6) contains an acid and / or the salt of the acid.

10. Electroplating device (1) according to any one of the preceding claims 1 to 7, characterized by the fact thatthe electroplating layer is formed as a bronze layer and / or is deposited from a catholyte (11) containing a copper(II) salt and a tin(II) salt, wherein the anolyte (6) contains an acid and / or the salt of the acid.

11. Electroplating device (1) according to any one of the preceding claims 1 to 7, characterized by the fact that the electroplating layer is formed as a tin-nickel layer and / or is deposited from a catholyte (11) containing a nickel(II) salt and a tin(II) salt, wherein the anolyte (6) contains an acid and / or the salt of the acid.

12. Electroplating device (1) according to one of the preceding claims, characterized by the fact that the workpiece (2) is made of a metal and / or already has a metallic electroplating layer on its surface.

13. Method for depositing a galvanic layer on a workpiece (2) using the electroplating device (1) according to any one of claims 1 to 12, wherein the electroplating device (1) is provided, wherein a relative movement is generated between the catholyte carrier (8) and the workpiece (2), wherein the contact area between the catholyte carrier (8) and the workpiece (2) shifts on the workpiece (2), and wherein a galvanic layer (8) is generated in the contact area between the catholyte carrier (8) and the workpiece (2) on the surface of the workpiece (2).

14. Method for depositing a galvanic layer on a workpiece (2) according to claim 13, wherein the galvanic layer is thermally treated after deposition on the workpiece (2).

15. Workpiece (2) with a galvanic layer, wherein the galvanic layer was produced by the method according to claim 13 or 14.

Images