EP0279803B1 - Anlage zur kontinuierlichen Herstellung einer sehr dünnen Metallfolie durch elektrolytische Abscheidung - Google Patents

Anlage zur kontinuierlichen Herstellung einer sehr dünnen Metallfolie durch elektrolytische Abscheidung Download PDF

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Publication number
EP0279803B1
EP0279803B1 EP19880870017 EP88870017A EP0279803B1 EP 0279803 B1 EP0279803 B1 EP 0279803B1 EP 19880870017 EP19880870017 EP 19880870017 EP 88870017 A EP88870017 A EP 88870017A EP 0279803 B1 EP0279803 B1 EP 0279803B1
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EP
European Patent Office
Prior art keywords
belt
anodes
installation according
installation
cathode
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
EP19880870017
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English (en)
French (fr)
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EP0279803A1 (de
Inventor
Marios Economopoulos
Nicole Lambert
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Centre de Recherches Metallurgiques CRM ASBL
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Centre de Recherches Metallurgiques CRM ASBL
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Publication date
Priority claimed from LU86773A external-priority patent/LU86773A1/fr
Priority claimed from LU86831A external-priority patent/LU86831A1/fr
Application filed by Centre de Recherches Metallurgiques CRM ASBL filed Critical Centre de Recherches Metallurgiques CRM ASBL
Priority to AT88870017T priority Critical patent/ATE67527T1/de
Publication of EP0279803A1 publication Critical patent/EP0279803A1/de
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Publication of EP0279803B1 publication Critical patent/EP0279803B1/de
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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
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils

Definitions

  • the present invention relates to an installation for the continuous manufacture of an extra-thin metal sheet by electrolytic deposition.
  • the electroplating technique has been known and used for a long time to form thin metal coatings on substrates having the most diverse shapes. Continuous deposition is particularly suited to elongated products of great length, such as strips or wires, which can pass through the deposition device. This technique makes it possible to produce adhesive coatings, which remain permanently on the surface of the substrate, or non-adhesive coatings, which can be detached from the substrate and thus constitute independent products.
  • patent LU-A-86.119 (corresponding to EP-A-0222724 document belonging to the state of the art according to Art. 54 (3) EPC) from the same applicant, a device is known for depositing an electrolytic coating , in particular non-adherent, on a rotary cathode.
  • This device comprises an anode which is designed so as to ensure high turbulence of the electrolyte in the space between the anode and the cathode, by practicing an electrolyte supply perpendicular to the plane of the cathode and without using any excessive motor pressures.
  • this device does not make it possible to reach the high level of production required by industrial exploitation.
  • the average thickness and the width of the extra-thin sheet to be produced are determined according to the needs of the users and therefore vary, for a given installation, within relatively narrow limits.
  • the increase in production implies an increase in the speed of the substrate which in turn leads to an increase in the length, and therefore in the size, of the deposition device, in order to maintain the same deposition time.
  • the size of the deposition device can, to a certain extent, be minimized by resorting to some special precautions, such as the use of an anode making it possible to operate with high current densities and the implementation of a electrolyte flow and current density as high as possible. It nevertheless remains necessary to increase the net deposition length, that is to say the length of the zone where the electrodes are actually opposite one another.
  • This increase is obtained by a simultaneous increase in the length of the anode and the cathode in the direction of travel of the substrate.
  • the length of the anode can be easily increased by juxtaposing several devices such as those described in patent LU-A-86,119 already cited.
  • the desired increase in the net deposition length implies a substantial increase in the diameter of the drum, which is limited, in practice, for reasons of manufacturing, mounting and size.
  • a mobile cathode constituted by a metal belt rotating around two parallel rollers.
  • Such a belt can have a sufficient length for the deposition to be carried out completely on a single belt, regardless of the speed thereof. It overcomes the aforementioned drawbacks of rotary drum cathodes, but it gives rise to other difficulties related in particular to the length and speed of the belt. In particular, one can mention the difficulty of guiding a very long belt and the need to compensate for chain deformation, which are further complicated by the aggressive nature of the environment. Such an installation also faces problems of sealing and braking of the belt linked to the electrical supply of the belt by brushes.
  • the object of the present invention is to provide an installation for the continuous manufacture of an extra-thin metal sheet by electrolytic deposition of a non-adherent coating on a mobile substrate followed by the detachment of this coating, an installation which makes it possible to avoid various aforementioned drawbacks and ensuring high production of extra-thin sheet.
  • the installation which is the subject of the present invention is based on the use of anodes of the type described in the aforementioned patent LU-A-86,119 and of a mobile cathode moving opposite these anodes.
  • the device of the invention comprises means for rinsing the extra-thin sheet, respectively means for drying this extra-thin sheet, which are located before the device for separating said sheet.
  • sheet and movable cathode the device may also include an installation for subjecting the sheet to a treatment causing an increase in its carbon content.
  • said cathode is constituted by a titanium belt, preferably polished.
  • the surface condition of the cathode strongly influences the detachment and the quality of the extra-thin sheet produced, and it is advantageous in this regard that the cathode has an active surface as polished as possible.
  • the active surface of the belt is that which receives the electrolytic deposit.
  • the second of said preferably horizontal rollers is also equipped with a drive motor.
  • the device of the invention comprises a second plurality of anodes arranged opposite a portion of the length of the second strand of said belt, the plate of said anodes being electrically connected to the positive terminal of a source of direct electric current.
  • said first and second pluralities of anodes are arranged opposite portions of substantially equal length of the respective strands of said belt, from a first of said horizontal rollers, the assembly comprising said first roller, said first and second pluralities of anodes and the corresponding portions of the strands of the belt is enveloped by a sealed enclosure, the second of said rollers is located outside of said enclosure and said enclosure comprises liquid-tight means for the entry and exit of said belt.
  • At least one anode is constituted by a parallelepipedic box whose wall located in front of the cathode is made of an electrically conductive material, preferably graphite, the other walls of said box being preferably made of an electrically insulating and chemically inert material vis-à-vis the electrolyte.
  • the means for electrically connecting an anode comprise copper bars connected to the plate of said anode, preferably on both sides of the width of said plate.
  • the electrical connection means of said metal belt include brushes, which are preferably immersed in the electrolyte.
  • the means for rinsing, respectively drying, the extra-thin metal sheet comprise devices for spraying water, respectively air, in the direction of said sheet.
  • Fig. 1 shows a general view of this particular embodiment
  • Fig. 2 illustrates the circuit of the electrolyte in this embodiment
  • Fig. 3 illustrates a particular variant of the installation comprising a carburizing device.
  • FIG. 1 shows a general view, in length, of a particular embodiment of the installation of the invention.
  • This installation comprises a mobile cathode in the form of a metal belt (1) stretched between two parallel horizontal rollers (2,3).
  • the edges of the belt (1) can be masked, on the anode side, by means of a suitable coating so as to give the extra-thin sheet the desired width.
  • the rollers are driven in rotation by motors, not shown, and their direction of rotation is indicated by a curved arrow.
  • the metal belt (1) thus defines an upper strand (4) which, as will be explained below, is the input strand, and a lower strand (5) or output strand.
  • the installation also includes anodes of the type described in the aforementioned patent LU-A-86,119, in which the wall pierced with two series of orifices is a flat graphite plate.
  • These anodes are divided into two groups, namely an upper group (6) in which the anodes are positioned such that their respective graphite plates are opposite and parallel to the outer face of the upper strand (4) of the belt, and a lower group (7) in which the anodes are positioned so that their respective graphite plates are opposite and parallel to the outer face of the lower strand (5) of the belt.
  • the metal belt (1) is only partially immersed in the electrolyte and it can therefore be considered that the installation for manufacturing an extra-thin metal sheet consists of two distinct parts, despite the physical continuity of the belt (1).
  • the submerged part of the installation is surrounded by a sealed enclosure (8), which includes airlocks for entering and leaving the belt.
  • a polarization electrode making it possible to eliminate any chemical attack on the extra-thin sheet by the electrolyte during the passage of the upper group ( 6) to the lower group (7) of the anodes. This arrangement also makes it possible to avoid the manufacture of cylindrical anodes.
  • This submerged roller (3) must have a diameter large enough to transmit to the belt the torque necessary for its rotation and to minimize the risk of rupture of the belt by fatigue.
  • the supply of both an electrolyte and an electric current to the anodes of the two aforementioned groups can be carried out either individually or by cells grouping together any number of anodes.
  • the various power supplies will be described with reference to a cell, it being understood that such a cell could have only one anode.
  • the electrical supply of a cell is ensured by means of a set of copper bars, known per se, connected to the graphite plate, on both sides of the width thereof; this arrangement has the effect of reducing the ohmic losses in the graphite plate and thus minimizing the variations in the current density liable to cause variations in the thickness of the deposit along the width of the belt.
  • the cathode is supplied with electricity by means of brushes immersed in the electrolyte and distributed over the "internal" surface of the belt (1), opposite the groups of anodes.
  • the electrolyte acts as a lubricant and thus reduces the friction force applied to the belt.
  • the electrolyte reduces the contact resistance between the cathode and the brushes and thus contributes to improving the electrical efficiency of the installation.
  • the non-submerged roller (2) has a diameter equal to that of the submerged roller (3). It ensures the transmission of half of the torque necessary for driving the belt, as well as guiding the belt in the transverse direction.
  • the means for rinsing and / or drying the extra-thin metal sheet are located before the device for separating said sheet and the belt (1).
  • This arrangement makes it possible to carry out the important and delicate rinsing and / or drying operations while the extra-thin sheet still adheres to the belt; this reduces the risk of degradation or tearing of this sheet.
  • the installation comprises rinsing means (9) for example by spraying hot water, possibly followed drying means (10) such as air blowing apparatus, hot or cold.
  • Peeling of the extra-thin sheet is carried out by means of a small motorized roller (11), placed approximately at the height of the axis of rotation of the non-submerged roller (2).
  • FIG. 2 illustrates the circuit of the electrolyte in an installation of the type represented in FIG. 1. As indicated above, reference is again made here to an anode cell.
  • FIG. 2 which results from a cross section along the plane II of FIG. 1, the upper (4) and lower (5) strands of the belt have been shown diagrammatically, as well as the graphite plate of an anode of each of the upper (6) and lower (7) groups.
  • the present installation includes an electrolyte circuit in which the pressure drops are low.
  • Each pair of superimposed cells, one belonging to the upper group (4, 6) and the other to the lower group (5, 7) is supplied with electrolyte by a pump (12) taking the liquid from a collection basin (13 ).
  • the pump (12) sends the electrolyte through the conduits (14) and (15) which supply the first series of orifices of the anodes (6) and (7) respectively.
  • the collection basin (13) is located directly below the lower group (7) of anodes and it extends at least over the entire length of the submerged part of the installation.
  • the electrolyte discharged from the rear face of the cells of the lower group (7) falls directly into the collection basin (13).
  • the electrolyte discharged from the rear face of the cells of the upper group (6) is collected by a channel (16) of large section which runs along the immersed part of the installation over its entire length and which brings the electrolyte back into the basin. collection (13) via a cascade (17) bypassing the submerged roller (3).
  • the installation also comprises, at the entrance to its submerged part, pinch rollers (18) which make it possible to prevent the belt (1) from twisting in the deposition section.
  • the device of the invention can advantageously be equipped with means for, after separation of the iron-based sheet and the movable cathode, subjecting said iron-based sheet to a treatment causing an increase in its carbon content; according to the invention, this treatment is advantageously constituted by a gas carburizing operation.
  • Such treatment by gas carburizing has proved to be particularly advantageous for increasing the carbon content of a sheet.
  • iron-based initial produced by electrolytic deposition.
  • the tests carried out by the Applicant have shown, in an absolutely unexpected manner, that the rate of cementation of such a sheet was particularly high, provided that the conditions of the treatment are judiciously chosen.
  • This high cementation speed which could in particular be due to the purity of the initial sheet, makes it possible to achieve the desired degree of cementation in a very short time, perfectly compatible with a continuous manufacturing process.
  • the means for applying the treatment in question comprise a heating oven up to a temperature between 900 ° C. and 1050 ° C., under a fuel atmosphere, a zone for maintaining in this temperature range and under this atmosphere for a period not exceeding 5 min., and a cooling zone with a speed of 5 ° C / s to 20 ° C / s in the temperature range from 800 ° C to 600 ° C, then a cooling zone down to room temperature.
  • the installation may also include at least one device for covering said sheet with a protective metal layer, with a flash heating step to cause the formation of an intermediate layer of intermetallic alloy between said sheet and the protective layer.
  • the device of the invention as just described in the above variant can also be equipped with means for coating the sheet with a protective film consisting of an oxide such as chromium oxide or an organic substance such as a lacquer, a resin or a varnish.
  • a protective film consisting of an oxide such as chromium oxide or an organic substance such as a lacquer, a resin or a varnish.
  • FIG. 3 shows a variant of the installation of FIG. 1, in which a device is provided for cementing the extra-thin metal sheet, after it has been detached from the movable cathode.
  • this device (19) Downstream of the installation (1) described in detail above, is located a device (19) intended to cause an increase in the carbon content of the extra-thin sheet.
  • this device (19) consists of a gas carburizing furnace, where the extra-thin sheet is exposed to a fuel atmosphere, for example CH4, at a high temperature.
  • This device (19) can be followed by other coating installations such as a dip galvanizing installation (20) or a tinning installation (21). Finally, a finishing device (22), such as an installation for depositing a protective coating by chromating, lacquering or the like, can also be installed downstream.
  • a finishing device (22) such as an installation for depositing a protective coating by chromating, lacquering or the like, can also be installed downstream.
  • the installations 20, 21 and 22 are, in themselves, well known in the art and do not require a detailed description. It is nevertheless advisable to limit the tensile force exerted in these installations, in order to take account of the relatively low tensile strength of the extra-thin sheet.

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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. Einrichtung zur Herstellung eines extradünnen Metallbleches durch galvanische Abscheidung auf eine bewegliche Kathode und nachfolgende Trennung des Überzugs von der Kathode, die Anoden umfaßt, von denen jede eine Platte aufweist, die mit einer ersten Reihe von Öffnungen, die mit Elektrolytzufuhrmitteln (14, 15) verbunden sind, und mit einer zweiten Reihe von Öffnungen, die mit Elektrolytabführmitteln (16, 17) verbunden sind, durchlocht ist, dadurch gekennzeichnet, daß
(a) die bewegliche Kathode aus einem zwischen zwei parallelen, vorzugsweise waagrechten Rollen (2, 3) gespannten Metallband besteht;
(b) mindestens eine jener Rollen (2; 3) angetrieben wird, so daß das Band um die beiden Rollen in Umlauf versetzt wird;
(c) eine erste Mehrzahl jener Anoden (6) gegenüber einem ersten Längsabschnitt eines ersten Trums (4) jenes Bandes (1) angeordnet ist;
(d) elektrische Anschlussmittel vorgesehen sind, zum Verbinden jener Platte jedder Anoden jener ersten Anodenmehrzahl (6) mit der positiven Anschlußklemme einer Gleichstromquelle;
(e) elektrische Anschlußmittel vorgesehen sind, zum Verbinden jenes Metallbandes (1) mit der negativen Anschlussklemme jener Gleichstromquelle;
(f) Sie Mittel aufweist zur Regelung der Geschwindigkeit jenes Metallbandes (1), der Zufuhr- und Abführmenge an Elektrolyt (12), sowie der Stromstärke.
2. Einrichtung nach Anspruch 1, dadurch gekennzeichnet, daß sie Spül- (9) und/oder Trockenmittel (10) für das extradünne Blech umfaßt, die sich vor der Trennvorrichtung (11) jenes Blechs und der beweglichen Kathode befinden.
3. Einrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Kathode aus einem vorzugsweise polierten Titanband (1) besteht.
4. Einrichtung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie eine zweite Mehrzahl von gegenüber einem Längsabschnitt des zweiten Trums (5) jenes Bandes (1) angeordneten Anoden (7) umfaßt, wobei die Platte jener Anoden elektrisch an die positive Anschlußklemme einer Gleichstromquelle angeschlossen ist.
5. Einrichtung nach Anspruch 4, dadurch gekennzeichnet, daß jene erste und zweite Mehrzahl von Moden (6, 7) ab einer ersten (2) jener vorzugsweise waagrechten Rollen gegenüber im wesentlichen gleichen Längsabschnitten der jeweiligen Trums (4, 5) jenes Bandes (1) angeordnet sind, daß das Ganze, bestehend aus jener ersten Rolle (2), jener ersten und zweiten Anodenmehrzahl (6, 7) und den entsprechenden Abschnitten der Bandtrums (4, 5), von einem dichten Schutzgehäuse (8) umgeben ist, daß sich die zweite (3) jener Rollen außerhalb jenes Schutzgehäuses (8) befindet und daß jenes Schutzgehäuse (8) flüssigkeitsdichte Mittel für den Ein- und Austritt jenes Bandes (1) umfaßt.
6. Einrichtung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß mindestens eine jener Anoden aus einem parallelepipeden Kasten besteht, dessen der Kathode gegenüberliegende Wand aus einem elektrisch leitenden Material, vorzugsweise Graphit, besteht und dessen andere Wände vorzugsweise aus einem elektrisch nicht leitenden und gegenüber dem Elektrolyten chemisch inerten Material bestehen.
7. Einrichtung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die elektrischen Anschlußmittel einer Anode Rupferstäbe umfassen, die an der Platte jener Anode und zwar vorzugsweise an beiden Breitseiten jener Platte angeschlossen sind.
8. Einrichtung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die elektrischen Anschlußmittel jenes Metallbandes (1) Bürsten umfassen, die vorzugsweise im Elektrolyten eingetaucht sind.
9. Einrichtung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie mit einem Mittel (19) zur Durchfürung einer Behandlung ausgerüstet ist, mit der eine Erhöhung des Kohlenstoffgehaltes in dem extradünnen Blech hervorgerufen werden kann.
10. Einrichtung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß sie mindestens eine Vorrichtung (20, 21) zum Überziehen jenes Blechs mit einer Schutzschicht umfaßt.
EP19880870017 1987-02-13 1988-02-15 Anlage zur kontinuierlichen Herstellung einer sehr dünnen Metallfolie durch elektrolytische Abscheidung Expired - Lifetime EP0279803B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88870017T ATE67527T1 (de) 1987-02-13 1988-02-15 Anlage zur kontinuierlichen herstellung einer sehr duennen metallfolie durch elektrolytische abscheidung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
LU86773 1987-02-13
LU86773A LU86773A1 (fr) 1987-02-13 1987-02-13 Installation pour la fabrication en continu d'une feuille metallique extra-mince par depot electrolytique
LU86831A LU86831A1 (fr) 1987-03-27 1987-03-27 Feuille metallique extra-mince et procede de fabrication d'une telle feuille
LU86831 1987-03-27

Publications (2)

Publication Number Publication Date
EP0279803A1 EP0279803A1 (de) 1988-08-24
EP0279803B1 true EP0279803B1 (de) 1991-09-18

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EP19880870017 Expired - Lifetime EP0279803B1 (de) 1987-02-13 1988-02-15 Anlage zur kontinuierlichen Herstellung einer sehr dünnen Metallfolie durch elektrolytische Abscheidung

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EP (1) EP0279803B1 (de)
JP (1) JPH01502204A (de)
DE (1) DE3864850D1 (de)
WO (1) WO1988006195A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19983254C2 (de) * 1999-05-06 2002-09-12 Union Steel Mfg Co Ltd Vorrichtung und Verfahren zur Herstellung einer dünnen Folie aus einer Ni-Fe-Legierung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19706675A1 (de) * 1997-02-20 1998-08-27 Hoechst Ag Sulfonamid-substituierte Chromane, Verfahren zu ihrer Herstellung, ihre Verwendung als Medikament oder Diagnostikum sowie sie enthaltendes Medikament
KR101343951B1 (ko) * 2011-06-23 2013-12-24 코닉이앤씨 주식회사 금속박의 제조 방법 및 제조 장치

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1696086A1 (de) * 1968-02-16 1971-11-18 Beckmann Werner Dr Ing Vorrichtung zum kontinuierlichen Herstellen von Metallfolien,insbesondere Kupferfolien auf elektrolytischem Weg
JPS515627A (ja) * 1974-07-03 1976-01-17 Katsuji Fujiwara Eatoratsupu
DE2619821A1 (de) * 1976-05-05 1977-11-17 Hoechst Ag Verfahren und vorrichtung zur kontinuierlichen elektrolytischen behandlung eines metallbandes
JPS5841358B2 (ja) * 1980-01-12 1983-09-12 株式会社小糸製作所 メツキ装置
JPS5816093A (ja) * 1981-07-23 1983-01-29 Nippon Steel Corp 金属ストリツプの電気メツキ用セル
US4529486A (en) * 1984-01-06 1985-07-16 Olin Corporation Anode for continuous electroforming of metal foil

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19983254C2 (de) * 1999-05-06 2002-09-12 Union Steel Mfg Co Ltd Vorrichtung und Verfahren zur Herstellung einer dünnen Folie aus einer Ni-Fe-Legierung

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WO1988006195A1 (fr) 1988-08-25
JPH01502204A (ja) 1989-08-03
EP0279803A1 (de) 1988-08-24
DE3864850D1 (de) 1991-10-24

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