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EP0320482B1 - Vorrichtung zur elektrolytischen Metallabscheidung und Verfahren zu deren Anwendung - Google Patents

Vorrichtung zur elektrolytischen Metallabscheidung und Verfahren zu deren Anwendung Download PDF

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Publication number
EP0320482B1
EP0320482B1 EP88870180A EP88870180A EP0320482B1 EP 0320482 B1 EP0320482 B1 EP 0320482B1 EP 88870180 A EP88870180 A EP 88870180A EP 88870180 A EP88870180 A EP 88870180A EP 0320482 B1 EP0320482 B1 EP 0320482B1
Authority
EP
European Patent Office
Prior art keywords
substrate
electrically conductive
electrolyte
conductive elements
slots
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 - Lifetime
Application number
EP88870180A
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English (en)
French (fr)
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EP0320482A1 (de
Inventor
Marios Economopoulos
Robert Pirlet
Roger Franssen
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.)
Centre de Recherches Metallurgiques CRM ASBL
Original Assignee
Centre de Recherches Metallurgiques CRM ASBL
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Publication date
Application filed by Centre de Recherches Metallurgiques CRM ASBL filed Critical Centre de Recherches Metallurgiques CRM ASBL
Priority to AT88870180T priority Critical patent/ATE79655T1/de
Publication of EP0320482A1 publication Critical patent/EP0320482A1/de
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Publication of EP0320482B1 publication Critical patent/EP0320482B1/de
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers

Definitions

  • the present invention relates to a device for the electrolytic deposition of a metal on a mobile substrate.
  • the invention also relates to the method of using such a device, as well as to the product obtained by the implementation of this method.
  • foil preferably in iron
  • the invention is however not limited to this single application, and it extends in an equally advantageous manner to the formation of a permanent electrolytic deposit, in particular to the electrolytic coating of a steel strip.
  • the device of the invention belongs to the type described in patent BE-A-08700561, which reveals an electrode comprising a body, one wall of which is profiled so as to match the shape of the substrate.
  • this walls are provided with narrow and parallel slots, serving alternately to introduce the electrolyte into the electrolysis interval and to take it back from this interval; this arrangement ensures turbulent circulation and a short trajectory of the electrolyte between the electrodes as well as a uniform flow over the entire width of the substrate.
  • an increase in the current density in the electrolysis cells makes it possible, for a given deposit thickness, to reduce the number of electrolysis cells and / or to increase the speed of the substrate.
  • This current density is nevertheless limited by the phenomenon of concentration polarization, corresponding to a local depletion of the electrolyte near the electrodes, which results in the formation of fragile, even powdery deposits, called "burnt deposits".
  • the object of the present invention is to propose a device for the electrolytic deposition of a metal on a mobile substrate, which makes it possible to use the pulsed current technique under advantageous conditions not only from the economic point of view, but also from that of the flexibility of the deposition process and the quality of the products obtained.
  • a device for the electrolytic deposition of a metal on a mobile substrate which comprises an electrode having at least one wall, the outer surface of which is located opposite said substrate with which it delimits an electrolysis interval and a plurality of parallel slots formed in said wall and connected alternately to electrolyte supply means and to electrolyte discharge means, is characterized in that said wall consists of a plurality of electrically elements conductors separated by electrically insulating elements, in that at least part of the electrolyte supply slots are located in said electrically conductive elements, while part of the electrolyte discharge slots are located in said elements electrically insulating, and in that at least a portion of said electrically insulating elements conductors are connected to one terminal of a direct current source, the other terminal of the direct current source being connected to said substrate.
  • This arrangement makes it possible to create, in the electrolysis interval, a maximum electric field under the electrically conductive elements and a minimum electric field under the electrically insulating elements.
  • the substrate circulating in said electrolysis interval is thus alternately subjected to a maximum current density corresponding to the maximum electric field and to a minimum current density corresponding to the minimum electric field.
  • said electrically conductive elements separated by electrically insulating elements are only provided in an initial portion of said wall, considered in the direction of progression of said substrate.
  • This arrangement makes it possible to apply the technique of pulsed currents in the period when they are most useful, that is to say at the start of the electrolytic deposition, which corresponds to the birth of the bites.
  • the height of the electrolysis interval varies periodically and continuously between minima situated in line with the electrolyte supply slots and maxima situated in line with the discharge slots of the electrolyte, at least in the portion of the wall where said electrically conductive elements are separated by electrically insulating elements.
  • the low height of the electrolysis interval makes it possible on the one hand to reduce the ohmic losses in the zones corresponding to the high current densities and on the other hand to reduce the pressure losses and the energy consumption resulting in areas with low current density.
  • At least one of said electrically conductive elements is connected to a terminal of a direct current source, the polarity of which is opposite to that of the terminal to which the other electrically connected elements are connected conductive, the electrical potential of the substrate being intermediate between the respective potentials of said electrically conductive elements.
  • Such an arrangement makes it possible to intensify the effects of pulsed current electrolysis by interposing, preferably periodically, a current pulse of opposite direction in a succession of pulses of electrolysis current of direct direction.
  • the substrate is connected to the negative terminal of a source of direct electric current and that it thus constitutes the cathode of the electrolytic deposition device, while the anode consists in particular by the above electrically conductive elements.
  • said electrically conductive elements having said opposite polarity in fact constitute cathodes with respect to the substrate which is thus locally anodic.
  • said substrate can be either a temporary support such as a metal belt, for example made of titanium, on which a detachable film is deposited, or a product such as a steel strip on which one deposits a permanent coating.
  • a temporary support such as a metal belt, for example made of titanium, on which a detachable film is deposited, or a product such as a steel strip on which one deposits a permanent coating.
  • FIG. 1 the fragmentary views of Figs. 2 to 4 show portions of the wall of the electrode which faces the substrate and the general arrangement of which is visible in FIG. 1.
  • Fig. 1 schematically illustrates in partial section an electrolytic deposition device belonging to the prior art, in which an anode 1 and a mobile substrate 2 are connected respectively to the positive terminal and to the negative terminal of a direct current source.
  • the anode 1 has a flat wall 10 which faces the substrate 2 and which defines therewith an electrolysis interval 11 of constant height.
  • the wall 10 is provided with narrow parallel slots 5, 6 transverse to the substrate, which open into the electrolysis interval; these slots respectively provide the supply (5) of electrolyte and the evacuation (6) of the electrolyte from the electrolysis interval 11.
  • the electrolyte circuit is represented by the arrows a, b, c, d , e, f.
  • the electrolysis interval 11 is the seat of a constant electric field and the current density is normally uniform there.
  • the substrate 2 moves in the direction of the arrow g.
  • the wall fragment, according to the invention, illustrated in FIGS. 2 to 4 corresponds to a portion comprising two supply slots 5 and a discharge slot 6, such as the portion framed by a dashed line in FIG. 1.
  • the substrate 2 is covered with an electrolytic deposit 12; it is connected by means of brushes 13 to the negative terminal of a source of direct electric current 14.
  • Fig. 2 shows that, in accordance with the present invention, the wall 10 consists of electrically conductive elements 15, separated by electrically insulating elements 16.
  • the supply slots 5 are located in the conductive elements 15, while the slots discharge 6 are located in the insulating elements 16.
  • the conducting elements 15 are connected to the positive terminal of the source of direct electric current 14.
  • the conductive elements 15 In the direction of progression of the substrate 2, the conductive elements 15 have a length A and the insulating elements 16 have a length B.
  • each point of the substrate 2 is subjected to the above-mentioned electric field varying in space; the current density prevailing at this point therefore varies between a maximum value corresponding to the passage through a maximum of electric field and a minimum value corresponding to the passage through a minimum of field.
  • This minimum value can moreover be positive, zero or even negative.
  • the maximum value of the electric field, and consequently that of the current density is located under the conductive elements 15, and more precisely at the level of the slots. feed 5; similarly, the minimum value of the electric field, and consequently that of the current density, is located under the insulating elements 16, and more precisely at the level of the evacuation slots 6.
  • the electric field and the current density vary continuously between these extreme values.
  • the electrolytic deposition 12 on the substrate 2 is therefore carried out under pulsed current conditions, although the electric field does not vary over time and the electric supply voltage therefore remains constant.
  • FIG. 2 is only produced in the initial portion of the wall 10, with respect to the direction of progression of the substrate 2.
  • This portion is for example that which is included in the box in phantom in FIG. 1.
  • the rest of the wall 10 is then formed in accordance with the prior art, that is to say by a single conductive wall in which are formed the supply slots 5 and the discharge slots 6.
  • This arrangement allows reduce the energy consumption due to ohmic losses while maintaining the advantageous use of pulsed currents in the most interesting portion of the electrolysis interval. It is indeed in this initial portion that the pits responsible for the porosity of the electrolytic deposit arise.
  • the height of the electrolysis interval 11 varies periodically, and continuously, in the direction of movement of the substrate 2. This height is minimum in line with the feed slots 5, that is to say in areas with a maximum electric field and maximum current density. This low height is justified in these places, because it reduces ohmic losses and therefore the consumption of electrical energy. On the other hand, this height is maximum at the level of the evacuation slots 6, that is to say in areas where a minimum electric field and a current density prevail. minimum. In this zone, the ohmic losses are low and little influenced by the height of the electrolysis interval. On the other hand, a greater height of this electrolysis interval results in an increase in the cross-section of the electrolyte and a reduction in the pressure drops. This results in a reduction in energy consumption to ensure the circulation of the electrolyte.
  • FIG. 4 shows that an electrically conductive element such as 15a can be connected to the negative terminal of a direct current source 14a, while the other electrically conductive elements 15 are connected to the positive terminal of another source of direct electric current 14.
  • the substrate 2 is, via the brushes 13, connected between the two sources 14 and 14a placed in series.
  • the conductive element 15 is therefore anodic with respect to the substrate 2, while the element 15a is cathodic with respect to this substrate 2.
  • cathode elements 15a can be made up of any number of these conductive elements, and in any order relative to the anode elements 15.
  • the substrate 2 traversing the electrolysis interval 11 can be subjected to any desired sequence of anodic and cathodic pulses, caused by electric fields considered here as positive and negative respectively. This results in an accentuation of the effects of electrolysis, in particular an improvement in the regularity of the deposition of the metal.
  • the length of the electroplating device according to the invention depends in particular on the required production capacity and on the average current density.
  • the wall 10 of this device consists of conductive elements 15 of length A and insulating elements 16 of length B, the lengths A and B being considered in the direction of movement of the substrate 2.
  • the device includes a certain number n of identical groups (conductive element 15 - insulating element 16) and its total length is n (A + B).
  • the slots supply 5 and discharge 6 are preferably centered respectively in the conductive 15 and insulating 16 elements.
  • the electrolyte had the following composition: and a temperature of 98 ° C.
  • the device included 1622 identical A-B groups; all the conductive elements 15 were anodic.
  • the active length A was 12.5 mm, the inactive length B was 37.5 mm, and the resulting active ratio was thus 0.25.
  • the active period was 3 ms and the inactive period 9 ms.
  • the electrolysis interval was 1 mm high.
  • the electric generator supplied a current of 810.8 kA at a DC voltage of 10.25 V, which corresponded to an installed power of 8476 kW.
  • the peak current density Dc reached 320 A / dm2 and the average current density Dm was 80 A / dm2.

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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)
  • Electrolytic Production Of Metals (AREA)

Claims (10)

1. Vorrichtung zur elektrolytischen Abscheidung eines Metalls auf einem beweglichen Substrat (2), die eine Elektrode mit mindestens einer Wand (10), deren Außenfläche jenem Substrat, mit dem sie einen Elektrolysenzwischenraum (11) begrenzt, gegenüberliegt, sowie mehrere in jener Wand ausgesparte parallele Schlitze (5,6) umfaßt, die abwechselnd mit Mitteln zur Zufuhr von Elektrolyt und mit Mitteln zum Abfließen von Elektrolyt verbunden sind, dadurch gekennzeichnet, daß jene Wand aus mehreren durch elektrisch isolierende Elementen (16) getrennten elektrisch leitenden Elementen (15) besteht, daß sich mindestens ein Teil der Schlitze (5) zur Zufuhr von Elektrolyt in jenen elektrisch leitenden Elementen befindet, während sich ein Teil der Schlitze (6) zum Abfließen von Elektrolyt in jenen elektrisch isolierenden Elementen befindet, und daß mindestens ein Teil jener elektrisch leitenden Elemente mit einem Anschluß einer elektrischen Gleichstromquelle (14) verbunden ist, während der andere Anschluß der Gleichstromquelle mit jenem Substrat verbunden ist.
2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß jene durch elektrisch isolierende Elementen (16) getrennten elektrisch leitenden Elemente (15) lediglich im Anfangsteil jener Wand (10) bezüglich der Fortbewegungsrichtung jenes Substrats vorgesehen sind.
3. Vorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sich die Höhe des Elektrolysenzwischenraums (11) zwischen den sich genau oberhalb der Schlitze (5) zur Zufuhr von Elektrolyt befindlichen Minima und den sich genau oberhalb der Schlitze (6) zum Abfließen von Elektrolyt befindlichen Maxima periodisch und kontinuierlich ändert, zumindest in dem Teil der Wand (10), in dem jene elektrisch leitenden Elemente durch elektrisch isolierende Elemente getrennt sind.
4. Vorrichtung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß mindestens eines jener elektrisch leitenden Elemente (15a) mit einem Anschluß einer Gleichstromquelle verbunden ist, deren Polarität entgegegesetzt ist zu der jenes Anschlusses, mit dem die übrigen elektrisch leitenden Elemente (15) verbunden sind, wobei das elektrische Potential des Substrats (2) zwischen den jeweiligen Potentialen jener elektrisch leitenden Elemente (15, 15a) liegt.
5. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, daß die jene entgegengesetzte Polarität aufweisenden elektrisch leitenden Elemente (15a) periodisch zwischen den anderen elektrisch leitenden Elementen (15) zwischengeschaltet sind.
6. Verfahren zur elektrolytischen Abscheidung eines Metalls auf einem beweglichen Substrat, bei dem sich jenes Substrat entläng einer Elektrodenwand bewegt, mit der es einen Elektrolysenzwischenraum begrenzt, in dem ein Elektrolyt zirkuliert, dadurch gekennzeichnet, daß man zumindest in einem Teil jenes Elektrolysenzwischenraums ein stationäres elektrisches Feld erzeugt, dessen Intensität in Fortbewegungsrichtung jenes Substrats veränderlich und in zu dieser Fortbewegung senkrechter Richtung im wesentlichen gleichmässig ist, wobei jenes veränderliche elektrische Feld innerhalb des Elektrolyten zu einer in Richtung der Fortbewegung jenes Substrats veränderlichen und in zu jener Fortbewegung senkrechter Richtung im wesentlichen gleichmässigen Stromdichte führt, und daß man jenes Substrat in jenem veränderlichen elektrischen Feld derart entlanglaufen läßt, daß jenes Substrat mehreren aufeinanderfolgenden elektrischen Stromstößen ausgesetzt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die Intensität des elektrischen Feldes, und somit die elektrische Stromdichte in jenem Elektrolysenzwischenraum, periodisch verändert.
8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß die Dauer eines elektrischen Stromstoßes zwischen 1 ms und 10 ms beträgt.
9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß das Verhältnis (w) zwischen der Dauer eines elektrischen Stromstoßes und der Zeitspanne zwischen dem Beginn zweier aufeinanderfolgender Stromstöße zwischen 0,2 und 0,8 liegt.
10. Verfahren nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, daß die mittlere Stromdichte (Dm) während der Zeitspanne zwischen dem Beginn zweier aufeinanderfolgender Stromstöße für.das Herstellen einer Folie jeweils zwischen 50 A/dm² und 100 A/dm², und für die Bildung eines permanenten Überzugs zwischen 200 A/dm² und 300 A/dm² liegt.
EP88870180A 1987-12-11 1988-12-06 Vorrichtung zur elektrolytischen Metallabscheidung und Verfahren zu deren Anwendung Expired - Lifetime EP0320482B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88870180T ATE79655T1 (de) 1987-12-11 1988-12-06 Vorrichtung zur elektrolytischen metallabscheidung und verfahren zu deren anwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE8701421A BE1001295A6 (fr) 1987-12-11 1987-12-11 Dispositif pour le depot electrolytique d'un metal et son procede d'utilisation.
BE8701421 1987-12-11

Publications (2)

Publication Number Publication Date
EP0320482A1 EP0320482A1 (de) 1989-06-14
EP0320482B1 true EP0320482B1 (de) 1992-08-19

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EP88870180A Expired - Lifetime EP0320482B1 (de) 1987-12-11 1988-12-06 Vorrichtung zur elektrolytischen Metallabscheidung und Verfahren zu deren Anwendung

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EP (1) EP0320482B1 (de)
AT (1) ATE79655T1 (de)
BE (1) BE1001295A6 (de)
DE (1) DE3873892D1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4121032A1 (de) * 1991-06-26 1993-01-07 Schmid Gmbh & Co Geb Vorrichtung zum behandeln von plattenfoermigen gegenstaenden, insbesondere leiterplatten

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2619821A1 (de) * 1976-05-05 1977-11-17 Hoechst Ag Verfahren und vorrichtung zur kontinuierlichen elektrolytischen behandlung eines metallbandes
BE905588A (fr) * 1986-10-09 1987-04-09 Centre Rech Metallurgique Dispositif de depot electrolytique et procede pour sa mise en oeuvre.

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Publication number Publication date
DE3873892D1 (de) 1992-09-24
EP0320482A1 (de) 1989-06-14
BE1001295A6 (fr) 1989-09-19
ATE79655T1 (de) 1992-09-15

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