WO2014147180A1 - Appareil et procédé pour dépôt électrolytique de couches métalliques sur des pièces - Google Patents

Appareil et procédé pour dépôt électrolytique de couches métalliques sur des pièces Download PDF

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Publication number
WO2014147180A1
WO2014147180A1 PCT/EP2014/055612 EP2014055612W WO2014147180A1 WO 2014147180 A1 WO2014147180 A1 WO 2014147180A1 EP 2014055612 W EP2014055612 W EP 2014055612W WO 2014147180 A1 WO2014147180 A1 WO 2014147180A1
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WIPO (PCT)
Prior art keywords
zinc
anode
soluble
plating bath
foregoing
Prior art date
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PCT/EP2014/055612
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English (en)
Inventor
Björn Dingwerth
Peter BAUMGÄRTEL
Original Assignee
Atotech Deutschland Gmbh
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 Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Priority to KR1020157030282A priority Critical patent/KR20150132574A/ko
Priority to EP14714193.1A priority patent/EP2976447A1/fr
Priority to CN201480017083.3A priority patent/CN105189831A/zh
Priority to US14/774,716 priority patent/US20160024683A1/en
Publication of WO2014147180A1 publication Critical patent/WO2014147180A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to an apparatus for the electrolytic deposition of a zinc or zinc alloy layer on a workpiece utilising a special anode assembly comprising a soluble and an insoluble anode.
  • the invention also relates to a process for zinc or zinc alloy layer deposition from an electrolytic plating bath using such apparatus.
  • Electrolytic metal deposition requires the use of at least one electrode which is cathodically (the cathode) polarized to another electrode, which is anodically polarized (the anode).
  • such anode could either be a soluble anode, which upon anodic oxidation releases ions of the metal it is made from into the bath solution or it could be designed as an insoluble anode, sometimes referred to as inert anode.
  • an insoluble anode needs to utilize another anodic reaction than the metal's dissolution in order to allow for a current flow.
  • anodic reaction is the solvent's decomposition.
  • the most applied solvent is water. Therefore, the most common anodic reaction in galvanic deposition with insoluble anodes is oxygen evolution due to oxidation of the oxygen in the water molecule, which can be represented by the following formula:
  • insoluble anode is commonly used not to express that absolutely no material of the anode is anodically oxidized and thus dissolved, but the majority of the current is utilized to generate oxygen.
  • insoluble anodes made from e.g. titanium or platinised titanium are virtually not oxidised and do not release platinum or titanium ions into the bath solution, thus remain stable.
  • Soluble anodes in contrast utilize the majority of the applied current to oxidize the anode material forming the ions of the anode material, e.g. Zn 2+ ions from soluble zinc anodes.
  • zinc ions are formed by the anodic oxidation reaction, which can be represented by the following formula: Zn Zn 2+ + 2e "
  • insoluble anodes are more common in alkaline electrolyte compositions whereas soluble anodes are mostly employed in acidic bath compositions.
  • insoluble anodes are dimensionally stable and do not require anode material replenishment.
  • the metal being deposited at the cathode needs to be replenished frequently into the bath by means of the corresponding metal ion source, most often a metal ion salt of the metal to be deposited at the cathode.
  • the advantage of soluble anodes is that the metal being deposited on the cathode can be replenished into the bath from the anode material. This working mode requires new anode material to replenish the dissolved metal.
  • the anodic current efficiency of the metal dissolution reaction is usually almost 100%, e.g. acidic zinc electrolytes when applying common anodic current densities and normal working conditions.
  • the cathodic current efficiency is usually well below 100% due to additional processes like reduction of certain organic bath components and water decomposition, particularly at high current densities.
  • the higher current efficiency at the anode compared to the cathode results in an increase of the metal ions dissolved from the soluble anode material because less metal ions are reduced at the cathode than dissolved from the anode.
  • the anode and cathode current efficiency are the same because under these conditions all metal ions dissolved from the anode are reduced at the cathode and the ion concentration in the plating bath remains constant.
  • a common solution to reduce the increasing metal ion concentration in plating operations is to frequently dilute the bath and thus control the metal content.
  • the apparatus according to the present invention is characterised in that it contains two types of anodes, soluble and insoluble anodes which allow adjustment of the current efficiency at the soluble anodes to correspond to the cathode efficiency at the cathode, i.e. the workpiece.
  • concentration of metal ions dissolved from the soluble anodes corresponds to the amount of ions deposited on the cathode by an electrochemical reaction and the amount of metal ions in the plating bath solution remains constant.
  • the apparatus is used for electrochemical deposition of zinc and zinc alloys from metal plating baths and results in deposits of high uniformity.
  • the apparatus is particularly suited for deposition of zinc alloys exhibiting a homogeneous deposit having a constant ratio of metals in the alloy.
  • Document WO 01 /96631 A1 relates to a plating process utilising a cationic ion exchange membrane and an insoluble anode to prevent formation of anodic breakdown products in the bath.
  • the present invention in contrast is not directed to a method to prevent the formation of breakdown products or the cementation of nobler metals, but to control the metal ion concentrations by a special electrode assembly enabling metal deposition with constant deposition results and homogeneous deposits.
  • Document DE 42 29 917 C1 relates to operation of an electrolytic bath for metal coating a substrate which uses a secondary anode cell containing alkaline or ammonium solutions and is sealed with a membrane to allow the pas- sage of alkali or ammonium ions into the plating solution. Acid needs to be added to the bath to compensate for the pH rise which occurs as hydrogen is evolved at the cathode. This method is disadvantageous because it requires pH control.
  • JP S56 1 12500 A describes a method for the metal plating with the aim to stabilize the composition of a plating bath and thus enable operation for a long period by providing an insoluble auxiliary anode, in addition to a soluble anode, in an aqueous acid solution via a cationic ion exchange membrane in a plating tank, and flowing a part of current thereto for plating.
  • This document fails to teach the specific advantages of the setup according to the present invention for zinc and zinc alloy plating methods.
  • JP 2006 322069 A relates to an electrogalvanizing method which is performed in a plating bath provided with an insoluble anode isolated by a cationic ion exchange membrane and a soluble anode.
  • the substrate to be plated is successively washed by water in washing tanks, and the plating liquid from the plating bath is recovered. Due to the isolation of the insoluble anode, the decomposition of salt and organic matter on the insoluble anode is prevented.
  • the problem to be solved is to avoid decomposition by oxidation at the anode and thus differs from the object of the present invention. This becomes apparent by the substantially different setup of the electrode assembly.
  • Fig. 1 shows an embodiment of an apparatus according to the present invention comprising in a first compartment a soluble anode, the workpiece as a cathode and in a second compartment an insoluble anode.
  • the first and the second compartment are divided by an ion exchange, e.g. cationic exchange membrane.
  • Fig. 2 shows an embodiment of an apparatus according to the present invention, wherein two power supplies (6a) and (6b) are used in order to distribute the current soluble zinc anode (2) and insoluble anode (5).
  • Fig. 3 shows an embodiment of an apparatus according to the present invention which additionally contains a second soluble anode (2') to provide metal ions for alloy deposition.
  • an apparatus comprising in a metal plating bath for zinc and zinc alloy plating at least one soluble zinc anode to provide a source zinc ions to be deposited and the cathode and in an anolyte compartment an insoluble anode, wherein the plating bath and the anolyte are separated from each other by an enclosure bearing on at least a portion of the enclosure an ion exchange membrane, which preferably is a cationic exchange membrane (also denoted cationic membrane).
  • the insoluble anode can be selected from the group consisting of titanium anodes, platinized titanium anodes, ceramic coated anodes and carbon based anodes like graphite anodes.
  • the plating bath contains the at least one soluble zinc anode and the cathode, which corresponds to the workpiece to be metal plated.
  • the first compartment can contain two or more soluble anodes made from to the metals to be plated.
  • the first compartment can contain a first soluble anode made of zinc and the second soluble anode made of nickel.
  • the second soluble anode in addition to the soluble zinc anode can alternatively be selected from at least one of the group consisting of nickel, cobalt, iron, chromium, cadmium, tin, copper , silver, gold, platinum, palladium, manganese, ruthenium, or rhodium, iridium, osmium, rhenium, tungsten, molybdenum, vanadium, indium, bismuth, antimony, selenium, germanium, gallium and tantalum, niobium.
  • Nickel and iron are preferred as the second soluble anode material, nickel being particularly preferred.
  • the second metal can be provided via its salt.
  • a typical setup would be an apparatus comprising in the plating bath a soluble zinc anode, nickel sulphate as the nickel source, and complexing agents, and in the anolyte an acid, preferably sulphuric acid in an aqueous solution.
  • the apparatus according to the present invention can preferably be applied for the deposition of zinc nickel binary or ternary alloys.
  • the deposition of binary zinc nickel alloys is particularly preferred.
  • a typical setup for the deposition of a zinc nickel deposit is shown in Fig.1 .
  • the container (1 ) comprises in the plating bath (1 a) the soluble anode (2) made from zinc which generates zinc ions when electric current is provided by the adjustable power supply (6).
  • the plating bath (1 a) further contains hydrochloric acid or sulfuric acid, nickel chloride as nickel ion source, typically potassium chloride to increase the conductivity and auxiliary components like wetting agents, buffers and brightening agents.
  • the plating bath (1 a) also contains the cathode (3) which is the workpiece to be metal plated.
  • the anolyte compartment is divided from the first compartment by suitable separation means.
  • the means bears on at least a portion thereofan ion exchange membrane (4a).
  • the membrane (4a) preferably is a cationic ion exchange membrane in case the plating bath is acidic in pH.
  • the separation by suitable means can for example be an enclosure made of polymers chemically resistant to the plating bath, e.g. made from polypropylene.
  • the anolyte also holds the insoluble anode (5).
  • the current flow is adjusted by the adjustable power supply (6) in such a way that essentially all zinc ions dissolved from the soluble anode (2) are deposited onto the cathode (3) as zinc nickel alloy deposit.
  • the nickel ions (3) deposited at the cathode as nickel metal are replenished by adding the corresponding nickel salt, i.e. nickel chloride.
  • a typical zinc nickel electroplating bath suitable for use in the apparatus according to the present invention contains zinc ion concentrations ranging from 0.1 to 100 g/l, preferably from 5 to 60 g/l and even more preferred from 20 to 35 g/l.
  • the electroplating bath of the present invention further comprises nickel ions with concentrations ranging from 0.1 to 60 g/l, preferably from 10 or 50 g/l and even more preferred from 25 to 35 g/l.
  • Sources of nickel ions which can be used comprise inorganic salts of nickel and organic salts of nickel.
  • the nickel source includes one or more of nickel hydroxide, nickel sulfate, nickel carbonate, ammonium nickel sulfate, nickel sulfamate, nickel acetate, nickel formiate, nickel bromide, nickel chloride.
  • the zinc ions and the nickel ions are present at concentrations sufficient to deposit a zinc-nickel alloy comprising a nickel content from 3 wt.% to 25 wt.% of the alloy. In another embodiment, the zinc ions and the nickel ions are present at concentrations sufficient to deposit a zinc-nickel ternary or higher alloy comprising a nickel content from 8 wt.% to 22 wt.% of the alloy.
  • the electroplating bath in accordance with the present invention can further include one or more of Te-, Bi- and Sb-ions, and in some embodiments may also include one or more additional ionic species selected from ions of Ag, Cd, Co, Cr, Cu, Fe, In, Mn, Mo, P, Sn and W.
  • the alloying elements are contained in the deposited zinc nickel alloy in smaller weight percentages only and are preferably provided in the plating bath via its salts. Generally, all water soluble salts are suitable.
  • the electroplating baths of the invention contain an acidic component in sufficient quantity to provide the bath with an acidic pH.
  • the acidic electroplating bath has a pH in the range from 0 to 6.5.
  • the acidic electroplating bath has a pH in the range from 0.5 to 6, and in another from 1 to 5, and in yet another, from 1 to 3.
  • the pH of the acidic bath is in the range from 3.5 to 6.
  • the acidic pH includes any pH up to, but less than 7. A pH range of 0.5 to 6 is preferred.
  • the acidic electroplating bath may include any appropriate acid, organic or inorganic or appropriate salt thereof.
  • the acidic electroplating bath comprises one or more of hydrochloric acid, sulfuric acid, sulfu- rous acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, an aromatic sulfonic acid such as substituted or unsubstituted benzene sulfonic acids, toluene sulfonic acid, and similar and related aromatic sulfonic acids, methane sulfonic acids and similar alkyl sulfonic acids, a poly carboxylic acid such as citric acid, sulfamic acid, fluoroboric acid or any other acid capable of providing a suitable acidic pH.
  • the acid itself or an appropriate salt thereof may be used, as needed, e.g., to obtain the desired pH.
  • acidic zinc and zinc alloy plating bath compositions for a method and in an apparatus according to the present invention is preferred over alkaline plating bath compositions.
  • the first advantage is the safety of an apparatus, wherein both compartments are acidic in pH. In case of leakages no strongly exothermic reaction occurs when the solutions of the plating bath as well as the anolyte are within the same pH range, which would happen if the plating bath would be alkaline and the anolyte would be acidic in pH (neutralisation reaction).
  • H 3 0 + ions are the species migrating from the anolyte compartment through the cationic ion exchange membrane into the plating bath during the metal deposition process. This migration also helps to keep the pH value of the plating bath constant.
  • a cathod- ic side reaction during metal plating particularly when working at a higher current densities, is the evolution of hydrogen gas from acidic solutions.
  • H 3 0 + ions are reduced to hydrogen and the pH of the plating bath would increase.
  • Migrating H 3 0 + ions from the anolyte into the plating bath help to maintain the pH, which is beneficial.
  • the electroplating baths of the invention contain an inorganic alkaline component in sufficient quantity to provide the bath with an alkaline pH.
  • the amount of the alkaline component contained in the electroplating bath is an amount sufficient to provide a pH of at least 10, and in one embodiment, an amount sufficient to provide a pH of at least 1 1 or, in one embodiment, a pH of 14.
  • the alkaline pH is in the range from a pH of 7.5 to a pH of 14.
  • the alkaline electroplating bath may contain any appropriate base.
  • the alkaline component is an alkali metal derivative such as sodium or potassium hydroxide, sodium or potassium carbonate, and sodium or potassium bicarbonate, etc., and mixtures thereof.
  • the electroplating bath of the invention further comprises one or more complexing agents.
  • the electroplating bath has an alkaline pH. In this case it is required to include a complexing agent to help dissolve and maintain the nickel ions in solution and prevent their precipitation. In an acidic electroplating bath, nickel does not need a complexing agent to remain in solution. It is noted that some of the complexing agents are also listed above as acids useable in the acidic baths.
  • the deposition of the coatings is carried out at a current density in the range from about 0.01 to about 150 A/dm 2 , in one embodiment, from about 0.5 to about 25 A/dm 2 and in one embodiment, from about 1 to about 10 A/dm 2 .
  • the process conveniently may be carried out at room temperature.
  • the process may be carried out at a temperature in the range from 10°C to 90° C, and in one embodiment, from 15°C to 45 °C, and in one embodiment, 25°C to 40°C.
  • the disclosed higher temperatures may be useful, e.g. for inducing evaporation of water from the electrolyte or to provide beneficial deposition conditions.
  • the apparatus according to the present invention enables the operator to change the dissolution rate of the metal from the at least one soluble anode material to adjust it according to the deposition rate at the cathode and thereby maintain a constant metal ion concentration in the plating bath.
  • the electrode assembly comprises the at least one soluble zinc anode (2), the cathode (workpiece) (3) and the at least one insoluble anode (5).
  • the soluble anode (2) and the insoluble anode (5) are both connected to the cathode (3) by an adjustable power supply (6).
  • the current at the soluble anode (2) can be adjusted by an adjustable resistor element 7a and/or the current at the insoluble anode (5) can be adjusted by an adjustable resistor element 7b.
  • the current distribution between soluble anode (2) and insoluble anode (5) can be adjusted by varying the distance between soluble anode (2) and the cathode (3) and/or the distance between insoluble anode (5) and the cathode (3). In such a case no resistor element is required.
  • the current distribution between soluble anode (2) and insoluble anode (5) can be adjusted by varying the active surface area of the soluble anode (2) and/or the active surface area of the insoluble anode (5). In such a case no resistor element is required.
  • the soluble anode (2) and the cathode (3) are connected by a first adjustable power supply (6a) and the insoluble anode (5) and the cathode (3) are connected by a second adjustable power supply (6b).
  • first adjustable power supply (6a) the insoluble anode (5) and the cathode (3) are connected by a second adjustable power supply (6b).
  • second adjustable power supply (6b) the current between soluble anode (2) and cathode (3) and between insoluble anode (5) and cathode (3) can be adjusted independently.
  • a second soluble anode (2') is provided which is the metal ion source of the second metal to be plated.
  • This setup is particularly useful for alloy deposition on the cathode (3).
  • the first soluble anode (2) and the second soluble anode (2') are both connected to the cathode (3) by a first (6a) and a second (6c) adjustable power supply.
  • the current between the soluble anodes (2) and (2'), respectively and cathode (3) and between insoluble anode (5) and cathode (3) can be adjusted independently.
  • a constant current from one rectifier could be applied to all three anodes via a switching apparatus distributing the current to the different anodes alternating-
  • the current distribution between the at least one soluble anode (2) and the insoluble anode (5) is adjusted in a way that the resulting current effi- ciency at the at least one soluble anode (2) corresponds to the cathode efficiency of the cathode (3).
  • the remainder of the anodic current is directed to the insoluble anode (5) and consumed in a secondary anode reaction.
  • the current of the soluble anode (2) is adjusted by the first adjustable power supply (6a) to dissolve the amount of ions necessary for the plating of the cathode (3).
  • the additional current of the insoluble anode (5) is adjusted by the second adjustable power supply (6b) to compensate the lower efficiency, in comparison to the efficiency of the soluble anode, of the cathode (3) to achieve the desired plating quantity at the cathode.
  • ion exchange membrane materials are suitable for the necessary separation of the plating bath and the anolyte.
  • Such membrane materials are commercially available and are selected by the expert skilled in the art depending on the plating bath composition, e.g. its pH, the metals ions to be deposited, the temperature etc.
  • cationic ion exchange membranes if the plating bath pH is acidic, e.g. made from fluorinated polymers like National.
  • the ion-selective membrane may not only be anionic or cationic, but can also be of bipolar or charge-mosaic type.
  • the anionic membrane may also be referred to as an anion-exchange membrane, and the cationic membrane may also be referred to as a cationic-exchange membrane.
  • a bipolar membrane is an ion-exchange membrane having a structure in which a cationic membrane and an anionic membrane are attached together.
  • a charge-mosaic membrane is composed of a two-dimensional or three-dimensional alternating cation- and anion-exchange channels throughout the membrane.
  • a combination of an anionic and a cationic membrane is used, with the anionic- selective membrane on the anode side and the cationic-selective membrane on the cathode side.
  • a combination of an anionic and a cationic membrane is used, with the cationic-selective membrane on the anode side and the anionic-selective membrane on the cathode side.
  • the membranes are separated at least slightly during use, in distinction to a bipolar membrane, in which the two membranes are attached together.
  • the bipolar ion- selective membrane is disposed with its cationic side towards the cathode and its anionic side towards the anode, and in another embodiment, in the opposite configuration.
  • Any known anionic, cationic, bipolar or charge-mosaic membrane may be used, and appropriate membranes may be selected from those known in the art.
  • Cationic ion selective membranes are particularly preferred.
  • Exemplary cationic ion selective membranes can be made from materials such as NAFION, perfluorosulfonate ionomers and polyperfluorosulfonic acid; eth- ylene-styrene interpolymer (ESI) available from Dow Chemical; sulfonate dpolyarylether ketones, such as VICTREX, PEEK, polybenzimidazole, available as PBI from Celanese GmbH.
  • materials such as NAFION, perfluorosulfonate ionomers and polyperfluorosulfonic acid
  • ESI eth- ylene-styrene interpolymer
  • sulfonate dpolyarylether ketones such as VICTREX, PEEK, polybenzimidazole, available as PBI from Celanese GmbH.
  • the solution in the second compartment can correspond to the plating bath of the first compartment.
  • it is for example an acid like diluted (e.g. 5 wt.%) sulfuric acid or hydrochloric acid.
  • the insoluble (also denoted inert) anode material inside the second compartment is for example a titanium anode, a platinised titanium anode or a ceramic coated anode or a graphite or any other carbon electrode. Particularly preferred is a platinised titanium mesh metal anode.
  • a zinc nickel plating bath is provided containing 20 g/l of zinc ions, 30 g/l of nickel ions (both added as their chloride salts) and potassium chloride to establish a total chloride ion concentration of 160 g/l chloride as well as 20 g/l boric acid, 2 g/l polyalkyleneimine, 2 g/l of an aromatic carboxylic acid, 0,4 mol/l acetate, 20 mg/l benzylidene acetone, 8 g/l of an anionic polyoxyalkylat- ed surfactant and 1 g/l of a polyoxyalkylated nonionic surfactant.
  • the process is run using a soluble zinc anode and a soluble nickel anode, but no ion exchange membrane.
  • the anodic current is being distributed between both anodes in an 5:1 (Zn:Ni) ratio at an anodic current density of 2 A/dm 2 and a ca- thodic current density of 2 A/dm 2 with mild steel workpieces on a cathode rack.
  • the process is run at 35 °C and at pH of 5.3 with mechanical cathode agitation for 30 min.
  • the metal at the cathode is deposited showing a smooth, glossy coating of an average thickness of 13.8 ⁇ having 14 wt.% of nickel homogenously distributed within the deposit.
  • the plating thickness corresponds to a cathodic current efficiency of 90%.
  • the thickness of the deposit on a rectangular shaped workpiece taken from the center of the rack is 20 ⁇ on the corners, 7 ⁇ in the center and 10 ⁇ in between center and corner. The results correspond to a plating bath without ageing.
  • Example 2 The same plating procedure as described in Example 1 using the same bath is conducted several times in the same bath with a drag-out of 150 ml/m 2 bath and a drag-in of 150 ml/m 2 of water achieving an overall throughput of 2.500 kAh. Replenishment is performed to compensate for drag-out losses.
  • the zinc and nickel concentrations are monitored and an increase of both metals can be detected, reaching 28 g/l Zn-ions and 35 g/l Ni-ions after 2500 kAh.
  • the pH is adjusted by addition of hydrochloric acid or potassium hydroxide in order to keep the nickel concentration in the alloy constant.
  • the thickness of the deposited zinc-nickel layer on a rectangular shaped workpiece taken from the center of the rack is 25 ⁇ on the corners, 5 ⁇ in the center and 7 ⁇ in between corner and center.
  • a plating bath without ion exchange membrane system does not provide a homogeneous thickness distribution after prolonged plating (ageing).
  • the same plating procedure as described in Example 2 using the same bath make-up and replenishment is conducted up to 2500 kAh.
  • the plating bath contains an cationic exchange membrane with a National membrane to separate the anolyte from the plating bath (catholyte).
  • the corresponding setup is shown in Figure 3.
  • a carbon anode is used, the anolyte is a 5 wt.% aqueous sulfuric acid solution.
  • a separate rectifier is used for the anolyte.
  • the rectifiers used on the zinc and nickel anode remain in place with their cathodes connected together with the cathode from the now added third rectifier to the workpieces.
  • the anode of the third rectifier is connected to the carbon anode in the membrane compartment.
  • the current is adjusted so that 5 % of the current is run through the new carbon anode in the membrane anode compartment, 79 % on the zinc anode and the remaining 16 % on the nickel anode.
  • the process still yields a smooth and glossy deposit of 13.8 ⁇ average thickness and 14 wt.% Ni content in the deposit.
  • the zinc and nickel ion concentrations in the bath remained constant at 20 g/l zinc ions and 30 g/l of nickel ions.
  • the thickness on a rectangular shaped work- piece taken from the center of the rack is 20 ⁇ on the corners, 7 ⁇ in the center and 10 ⁇ in between corner and centers, thus indicating maintained thickness distribution and deposit quality even after prolonged plating.

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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)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne un appareil et un procédé pour le dépôt électrolytique d'une couche de zinc ou d'alliage de zinc sur une pièce, l'appareil comprenant un contenant pour contenir le bain de revêtement métallique divisé en au moins deux compartiments, un ensemble électrode se trouvant dans le contenant, l'ensemble comprenant, dans un premier compartiment, une anode soluble pour fournir des ions du ou des métaux destinés à être déposés et une cathode qui correspond à la pièce qui doit recevoir un revêtement métallique, et, dans un compartiment anolyte séparé du premier compartiment par une membrane d'échange d'ions, comprenant une anode insoluble, l'ensemble électrode dans les compartiments étant connecté par une alimentation en énergie électrique réglable.
PCT/EP2014/055612 2013-03-21 2014-03-20 Appareil et procédé pour dépôt électrolytique de couches métalliques sur des pièces WO2014147180A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020157030282A KR20150132574A (ko) 2013-03-21 2014-03-20 가공물에 금속층을 전해 전착하기 위한 장치와 방법
EP14714193.1A EP2976447A1 (fr) 2013-03-21 2014-03-20 Appareil et procédé pour dépôt électrolytique de couches métalliques sur des pièces
CN201480017083.3A CN105189831A (zh) 2013-03-21 2014-03-20 用于在工件上电解沉积金属层的装置和方法
US14/774,716 US20160024683A1 (en) 2013-03-21 2014-03-20 Apparatus and method for electrolytic deposition of metal layers on workpieces

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Application Number Priority Date Filing Date Title
EP13160397 2013-03-21
EP13160397.9 2013-03-21

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WO2014147180A1 true WO2014147180A1 (fr) 2014-09-25

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US (1) US20160024683A1 (fr)
EP (1) EP2976447A1 (fr)
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CN104975332A (zh) * 2015-07-30 2015-10-14 江苏金曼科技有限责任公司 一种调整镀液中离子浓度的方法
CN109023496A (zh) * 2018-06-26 2018-12-18 南通汇丰电子科技有限公司 一种用于控制电镀锡铋合金的方法及系统
EP3461933A1 (fr) * 2017-09-28 2019-04-03 ATOTECH Deutschland GmbH Procédé de dépôt électrolytique d'une couche d'alliage zinc-nickel sur au moins un substrat devant être traité
JP2021085068A (ja) * 2019-11-28 2021-06-03 ユケン工業株式会社 めっき液の亜鉛濃度の上昇を抑制する方法および亜鉛系めっき部材の製造方法
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CN107119289A (zh) * 2017-05-08 2017-09-01 安徽长青电子机械（集团）有限公司 一种提高均镀性的电镀方法
KR101998605B1 (ko) * 2017-11-27 2019-07-10 주식회사 지에스켐텍 아연니켈합금 전기도금액 및 이를 이용한 전기도금법
KR20200116163A (ko) * 2018-02-23 2020-10-08 램 리써치 코포레이션 불활성 애노드 및 활성 애노드를 갖는 전기도금 시스템
KR102135212B1 (ko) 2018-10-24 2020-07-17 (주)애니캐스팅 전해생성물 제거가 가능한 전해가공장치
EP3914757B1 (fr) * 2019-01-24 2023-04-05 Atotech Deutschland GmbH & Co. KG Procede de dépôt électrolytique d'un alliage zinc-nickel utilsant un système d'anode à membrane
CN110462107A (zh) * 2019-02-15 2019-11-15 迪普索股份公司 锌或锌合金电镀方法和系统
CN110106524A (zh) * 2019-05-21 2019-08-09 西安汇创贵金属新材料研究院有限公司 一种金电解液制备装置及制备方法
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CN114787425A (zh) * 2019-12-20 2022-07-22 德国艾托特克有限两合公司 用于在衬底上沉积锌-镍合金的方法及系统
KR20200047459A (ko) 2020-03-31 2020-05-07 (주)애니캐스팅 전해생성물 제거가 가능한 전해가공장치
CN114059143A (zh) * 2020-07-31 2022-02-18 苏州市汉宜化学有限公司 一种碱性电沉积锌及锌合金专用的阳极及其制备方法

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CN104313657A (zh) * 2014-11-10 2015-01-28 临安振有电子有限公司 Hdi印制线路板通孔的电沉积装置
CN104975332A (zh) * 2015-07-30 2015-10-14 江苏金曼科技有限责任公司 一种调整镀液中离子浓度的方法
US11339492B2 (en) 2017-02-07 2022-05-24 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Method for electrodepositing zinc and zinc alloy coatings from an alkaline coating bath with reduced depletion of organic bath additives
EP3461933A1 (fr) * 2017-09-28 2019-04-03 ATOTECH Deutschland GmbH Procédé de dépôt électrolytique d'une couche d'alliage zinc-nickel sur au moins un substrat devant être traité
WO2019063197A1 (fr) * 2017-09-28 2019-04-04 Atotech Deutschland Gmbh Procédé de dépôt électrolytique d'une couche d'alliage zinc-nickel sur au moins un substrat à traiter
US10961637B2 (en) 2017-09-28 2021-03-30 Atotech Deutschland Gmbh Method for electrolytically depositing a zinc nickel alloy layer on at least a substrate to be treated
CN109023496A (zh) * 2018-06-26 2018-12-18 南通汇丰电子科技有限公司 一种用于控制电镀锡铋合金的方法及系统
JP2021085068A (ja) * 2019-11-28 2021-06-03 ユケン工業株式会社 めっき液の亜鉛濃度の上昇を抑制する方法および亜鉛系めっき部材の製造方法
WO2021106291A1 (fr) * 2019-11-28 2021-06-03 ユケン工業株式会社 Procédé de suppression d'augmentation de la concentration en zinc dans une solution de placage, et procédé de production d'élément de placage à base de zinc
CN113195798A (zh) * 2019-11-28 2021-07-30 油研工业股份有限公司 抑制镀覆液的锌浓度上升的方法以及锌系镀覆构件的制造方法

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EP2976447A1 (fr) 2016-01-27

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