EP0079032B1 - Appareil pour le dépôt électrolytique d'une pièce métallique - Google Patents

Appareil pour le dépôt électrolytique d'une pièce métallique Download PDF

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Publication number
EP0079032B1
EP0079032B1 EP82110104A EP82110104A EP0079032B1 EP 0079032 B1 EP0079032 B1 EP 0079032B1 EP 82110104 A EP82110104 A EP 82110104A EP 82110104 A EP82110104 A EP 82110104A EP 0079032 B1 EP0079032 B1 EP 0079032B1
Authority
EP
European Patent Office
Prior art keywords
container
cathode
anode
nickel
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82110104A
Other languages
German (de)
English (en)
Other versions
EP0079032A1 (fr
Inventor
Götz Ing. grad. Mielsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayerische Motoren Werke AG
Original Assignee
Bayerische Motoren Werke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayerische Motoren Werke AG filed Critical Bayerische Motoren Werke AG
Publication of EP0079032A1 publication Critical patent/EP0079032A1/fr
Application granted granted Critical
Publication of EP0079032B1 publication Critical patent/EP0079032B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • 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
    • 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
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • 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
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

Definitions

  • the invention relates to a method for the electrodeposition of a metal on a metallic workpiece according to the preamble of claim 1.
  • Coating baths are also known in which the workpiece serving as the cathode is an insoluble anode, e.g. B. a lead anode is assigned (DE-A-1 926 462).
  • the nickel is added directly to the bath in the form of a solution. In the case of discontinuous dosing of the nickel, a considerable amount of work is then required, and in the case of automatic dosing, a correspondingly large amount of equipment is required.
  • nickel carbonate (NiC0 3 ) is preferably added to the bath during the subsequent dosing.
  • nickel carbonate is carcinogenic.
  • the fresh preparation of nickel carbonate via the precipitation of calcium sulfate (CaS0 4 ) from nickel sulfate (NiS0 4 ) and calcium hydroxide (Ca (OH) 2) is expensive.
  • the commercially available technical grade nickel carbonate contains insoluble compounds, e.g. B. insoluble iron, zinc and nickel hydroxy carbonates.
  • a nickel dispersion bath is used in the nickel coating of the cylinder surfaces of piston internal combustion engines.
  • the bathroom is a part, for. B. 100 liters, to which the nickel carbonate is added.
  • the coating bath must also be selectively cleaned of soluble contaminants.
  • the acid pH of the coating bath gradually causes the zinc to dissolve.
  • a device which corresponds to the preamble of claim 1.
  • hydrogen is formed on the cathode of the second container, i. H. exposed the cathode to a very high current density.
  • the cathode of the second container is designed as an oxygen electrode.
  • DE-A-1 926 974 discloses a device for the selective cleaning of galvanic baths, in which a cathode is arranged concentrically around an anode.
  • the anode is preferably insoluble.
  • a nickel anode is not recommended because it will work out.
  • the invention is based on the object, in a galvanizing process in which the workpiece cathode is assigned an insoluble anode, to make replenishment of the electrolyte of the coating bath superfluous with simple equipment and at the same time carry out a selective cleaning of the coating bath.
  • the device essentially consists of a first container 1 and a second container 2, in each of which a cathode 3 or 4 and an anode 5 or 6 are arranged.
  • the container 1 is filled with the coating bath 7, the coating bath 7 depleted of electrolyte in the container 1 by the metal deposition on the cathode 3 being fed to the container 2 via a line 8 and after the accumulation of the electrolyte in the container 2 via a circulation line 9 with a Pump is transported back to the container 1 again.
  • the cathode 3 of the container 1 and the anode 6 of the container 2 are each connected to a direct current source 10 via a line 11 or 12.
  • the cathode 4 of the container 2 is connected to the anode 5 of the container 1 via an electrical line 13.
  • this circuit can also be made that the current in the bath of the container 2 is switched on independently of the current in the bath of the container 1 or the current in the bath of the container 2 is set independently of the current in the bath of the container 1 can be.
  • the cathode 3 of the container 1 is formed by the workpiece to be coated, that is to say for example by the cylinders of a reciprocating piston internal combustion engine, the running surfaces of which are to be coated.
  • the anode 5 consists of lead and is insoluble.
  • the coating bath 7 is formed by a nickel sulfate bath, for example with a nickel salt concentration of 700 grams / liter of water. Silicon carbide can be slurried in the bath 7, for example 30 grams / liter. For an optimal; uniform nickel deposition on the workpiece cathode 3, a pH of the coating bath 7 of 3 to 4 is aimed for.
  • the cathode 4 of the container 2 is porous, for example lattice-shaped and consists of a conductive metal, for. B. a steel mesh, while the anode 6 of the container 2 is formed of nickel.
  • the cathode 4 is cylindrical and is arranged concentrically around the anode 6, so that the surface of the cathode 4 of the container 2 is many times, for example 50 to 200 times larger than the surface of the anode 6 of the container 2.
  • the dissolution rate of the nickel at the anode 6 of the container 2 and the deposition rate of the nickel at the cathode 4 of the container 2 are determined by the current density A / dm 2 at the anode 6 and the cathode 4 of the Container 2 determined. That is, since the surface of the anode 6 of the container 2 is many times smaller than the surface of the cathode 4 of the container 2, the current density on the surface of the anode 6 is many times larger than on the surface of the cathode 4 of the second container 1.
  • the cathode 4 of the second container 2 prevails at the cathode 4 of the second container 2 is a relatively low current density of, for example, 1 A / dm 2 so that nickel is deposited slightly at the cathode 4 of the container 2, while at the anode 6 of the container 2 is a relatively large current density of e.g. 50 A / dm 2 and thus a correspondingly high dissolution rate of the nickel.
  • the size ratio between the surfaces of the anode 6 and the cathode 4 of the container 2 is limited by the fact that the size of the cathode 4 cannot be chosen arbitrarily large for practical reasons, furthermore in the following secondary reaction.
  • the device according to the invention also serves for the selective cleaning of the coating bath from such metallic impurities which, at a given current density, have a higher deposition rate at the cathode 4 of the container 2 than nickel, e.g. B. of zinc ions.
  • the deposition rate of zinc is many times greater than that of nickel, so that zinc and others contained in the coating bath are preferred to nickel Contaminants are deposited on the cathode 4 of the container 2, ie the coating bath is selectively cleaned without nickel being deposited.
  • the soluble nickel anode 6 in the container 2 is expediently surrounded by a porous magnetic filter 14 in order to prevent nickel flakes, which can arise when the anode 6 is dissolved, from entering the coating bath 7.
  • Magnetic filters of this type are known per se (cf. DE-OS 3 007 161

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (8)

1. Procédé pour déposer par électrolyse un métal sur une pièce d'oeuvre métallique, procédé dans lequel la pièce d'oeuvre jouant le rôle de cathode (3) est plongée, avec une anode insoluble (5), dans un premier récipient (1), tandis qu'un second récipient (2) est utilisé avec une cathode (4) et une anode soluble (6) constituée du métal à déposer, le bain de revêtement (7) étant mis en circulation à travers les deux récipients (1 et 2) et la cathode (3) et l'anode (5) du premier récipient (1 ainsi que la cathode (4) et l'anode (6) du second récipient (2) étant susceptible d'être raccordées à une source (10) de courant continu, procédé caractérisé en ce que dans le deuxième récipient (2) est disposée une cathode (4) dont la surface mouillée est 10 fois supérieure à la surface mouillée de l'anode (6) du deuxième récipient (2).
2. Procédé selon la revendication 1, caractérisé en ce que le métal à déposer est du nickel.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise une pompe de circulation (9) pour amener le bain de revêtement du premier récipient (1) au second récipient (2) et pour le ramener du second au premier.
4. Procédé selon une des revendications 1 à 3, caractérisé en ce que la surface mouillée de la cathode (4) du deuxième récipient (2) est 50 à 200 fois plus grande que la surface mouillée de l'anode (6) de ce deuxième récipient.
5. Procédé selon une des précédentes revendications, caractérisé en ce que la cathode (4) du deuxième récipient (2) est disposée concentriquement autour de l'anode (6).
6. Procédé selon une des précédentes revendications, caractérisé en ce qu'on utilise comme cathode (4) du deuxième récipient (2) une cathode poreuse.
7. Procédé selon une des précédentes revendications, caractérisé en ce qu'on utilise uniquement une source de courant (10) et que la cathode (3) du premier récipient (1) et l'anode (6) du deuxième récipient (2) sont reliées à la source (10) de courant continu, tandis que l'anode (5) du premier récipient (1) et la cathode (4) du deuxième récipient (2) sont reliées ensemble, ou bien l'anode (5) du premier récipient (1) et la cathode (4) du deuxième récipient (2) sont reliées ensemble par l'intermédiaire d'une liaison (11. 12, 13), tandis que la cathode (3) du premier récipient (1) et l'anode (6) du deuxième récipient (2) sont reliées ensemble par une liaison.
8. Procédé selon une des précédentes revendications, caractérisé en ce qu'un filtre magnétique (14) est disposé autour de l'anode (6) dans le second récipient (2).
EP82110104A 1981-11-06 1982-11-03 Appareil pour le dépôt électrolytique d'une pièce métallique Expired EP0079032B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3144128 1981-11-06
DE3144128A DE3144128C1 (de) 1981-11-06 1981-11-06 Vorrichtung zum galvanischen Abscheiden eines Metalls auf einem metallischen Werkstueck

Publications (2)

Publication Number Publication Date
EP0079032A1 EP0079032A1 (fr) 1983-05-18
EP0079032B1 true EP0079032B1 (fr) 1987-03-04

Family

ID=6145791

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82110104A Expired EP0079032B1 (fr) 1981-11-06 1982-11-03 Appareil pour le dépôt électrolytique d'une pièce métallique

Country Status (2)

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EP (1) EP0079032B1 (fr)
DE (2) DE3144128C1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4933051A (en) * 1989-07-24 1990-06-12 Omi International Corporation Cyanide-free copper plating process
US6413390B1 (en) * 2000-10-02 2002-07-02 Advanced Micro Devices, Inc. Plating system with remote secondary anode for semiconductor manufacturing

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1273978A (en) * 1968-07-08 1972-05-10 Nat Res Dev Improvements in or relating to electrolytic deposition of metals

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL71231C (fr) * 1948-04-22
DE1496966A1 (de) * 1966-12-29 1969-08-14 Peach Arthur Leslie Plattierungsverfahren
FR1582093A (fr) * 1968-05-31 1969-09-26
DE1926974A1 (de) * 1969-05-23 1970-11-26 Siemens Ag Einrichtung zur selektiven Reinigung galvanischer Baeder

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1273978A (en) * 1968-07-08 1972-05-10 Nat Res Dev Improvements in or relating to electrolytic deposition of metals

Also Published As

Publication number Publication date
DE3275563D1 (en) 1987-04-09
DE3144128C1 (de) 1983-06-09
EP0079032A1 (fr) 1983-05-18

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