EP0222724B1 - Verfahren und Vorrichtung zur Herstellung einer hauchdünnen Metallfolie durch galvanische Beschichtung - Google Patents

Verfahren und Vorrichtung zur Herstellung einer hauchdünnen Metallfolie durch galvanische Beschichtung Download PDF

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Publication number
EP0222724B1
EP0222724B1 EP86870147A EP86870147A EP0222724B1 EP 0222724 B1 EP0222724 B1 EP 0222724B1 EP 86870147 A EP86870147 A EP 86870147A EP 86870147 A EP86870147 A EP 86870147A EP 0222724 B1 EP0222724 B1 EP 0222724B1
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EP
European Patent Office
Prior art keywords
orifices
extra
series
thin metal
metal sheet
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
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EP86870147A
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English (en)
French (fr)
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EP0222724A1 (de
Inventor
Marios Economopoulos
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Centre de Recherches Metallurgiques CRM ASBL
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Centre de Recherches Metallurgiques CRM ASBL
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Priority to AT86870147T priority Critical patent/ATE58921T1/de
Publication of EP0222724A1 publication Critical patent/EP0222724A1/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
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0685—Spraying of electrolyte

Definitions

  • the present invention relates to the manufacture of an extra-thin metal sheet by electrolytic deposition of a metallic material on a substrate.
  • Document FR-A 2 350 142 discloses a device for the continuous electrolytic treatment of a metal strip. This device is however limited to the electrolytic treatment of the surface of the strip and to the deposition of an adherent coating on this surface. It does not relate to the manufacture of an extra-thin metal sheet.
  • the object of the present invention is to propose a device and a method which not only make it possible to manufacture an extra-thin metal sheet by electrolytic deposition but also to fix the processing properties of this sheet. .
  • said tubes connected to the orifices of the second series are, at their other end, connected to suction means, for example to a pump via a collector .
  • the operating principle of this device is as follows: the box, connected to the positive pole of a direct current source, is arranged in such a way that its wall provided with the two series of orifices is located near the surface of the substrate, which is connected to the negative pole of the same DC source.
  • the electrolyte is introduced, under moderate pressure, into the interior volume of the box through the supply orifice. Under the effect of the supply pressure, the electrolyte leaves the box through the orifices of the first series, and it circulates in the narrow space existing between the wall of the box and the substrate, therefore between the anode and the cathode.
  • the electrolyte is taken up by the orifices of the second series, for example by suction, and led, by the tubes connected to these orifices, to a sufficient distance from the substrate. It can then be introduced again into the box, possibly after regeneration, and again run through the circuit which has just been described.
  • the device of the invention comprises a box 1, one of the walls of which is arranged in parallel and at a very short distance from the surface of a metal strip 2 in movement.
  • the box 1 is provided with an orifice 3 to which is connected a pipe 4 for supplying electrolyte from a source not shown.
  • a first series of orifices 5 making the interior volume of the box 1 communicate with the narrow space existing between the box 1 and the strip 2.
  • a second series of orifices 6 to which tubes 7 are connected which pass through the interior volume of the box 1 and which exit therefrom passing in leaktight manner through another wall of the box 1.
  • these tubes open into a manifold 8 which can be connected to a pump 9.
  • the latter is connected to the negative pole of a direct current source, or possibly to the ground, while the box 1 is connected to the positive pole of this same direct current source.
  • the box therefore constitutes the anode and the strip constitutes the cathode of an electrolysis circuit.
  • the electrolyte enters the interior volume of the box 1 through the supply orifice 3 connected to the pipe 4. Under the effect of the supply pressure, the electrolyte fills the interior volume of the box, then it flows through the orifices 5 to occupy the narrow space existing between the box 1 and the strip 2. An electric current can thus flow between the anode and the cathode and ensure the desired electrolytic deposition on the strip 2. Thanks to the short distance separating the orifices 5 from the orifices 6, the electrolyte is very quickly taken up, by suction, through the orifices 6 and the tubes 7, to the collector 8 and to the pump 9. After having possibly been regenerated and having received a quantity backup by known means not shown, the electrolyte is then returned, by the action of the pump 9, in the supply line 4 and starts the circuit again.
  • the suction devices namely the manifold 8 and the pump 9, are eliminated completely.
  • the box 1 is completely submerged in the tank containing the electrolyte and the tubes 7 open directly into this tank.
  • the electrolyte then flows through the tubes 7 under the effect of the pressure established between the anode and the cathode.
  • FIG. 2 represents a box 1, one wall of which comprises a semi-cylindrical cavity where the orifices 5 and 6 defined above are formed.
  • the orifices 6 are connected to a manifold 8 by tubes 7.
  • a cylinder 10 coaxial with said cavity in which it can rotate.
  • the outside diameter of the cylinder is slightly smaller than that of the cavity, so as to leave a narrow annular gap between them.
  • the box 1 and the cylinder 10 are respectively connected to the positive pole and to the negative pole of a direct current source.
  • the electrolyte is introduced through the supply line 4, arrives through the orifices 5 in the annular slot where it undergoes electrolysis, then is taken up through the orifices 6 and the tubes 7 towards the collector 8.
  • the metal sheet 11 formed on the cylinder is then detached in a manner known per se.
  • the device according to the invention made it possible to achieve a specific electrolyte flow rate of 20 l / m 2 .s under a pressure of 1 kg / cm 2 with an anode-cathode distance equal to 0.1 mm. Such a specified flow which ensures high turbulence, which in turn promotes the electrical behavior of the installation.
  • FIG. 3 illustrates the variation of the specific flow rate of the electrolyte as a function of the pressure, for different values of the anode-cathode distance. It clearly shows that the device of the invention makes it possible to very greatly reduce this distance while ensuring appreciable specific flow rates and without requiring excessive pressures.
  • FIG. 4 shows the influence of the anode-cathode distance on the pressure of the electrolyte ensuring a predetermined specific flow rate.
  • the device of the invention has made it possible to reduce the anode-cathode distance to 0.2 mm, while the pressure has only gone from 0.4 to 0 , 6 kg / c m2 .
  • the device of the invention also proves to be advantageous in this respect, because an increase in the current density leads to the possibility of increasing the speed and therefore the productivity of the deposition lines, for a given thickness of extra-thin sheet at produce.
  • An additional advantage of the installation according to the invention is that it makes it possible to achieve high levels of turbulence and current density while using only low pressures. As a result, the anode and the substrate are not subjected to significant forces and therefore do not deform significantly. In addition, the energy consumption of the pump remains low.
  • the device of the present invention also makes it possible to vary the width of the area coated with the substrate or the width of the extra-thin sheet, by adapting the length - in the transverse direction of the product - of the box 1 or of the cylinder 10, respectively .
  • This adaptation can be carried out for example by modifying the number of boxes juxtaposed according to the width of the product or by partitioning a long box into several compartments with clean supply and evacuation, or by closing off part of the electrolyte passage orifices.
  • the process for manufacturing an extra-thin metal sheet by electrolytic deposition on a substrate by means of a device of the type described above, in which said substrate constituting the cathode is placed at very short distance from an anode constituted by a plate pierced with a first series of orifices distributed over the surface of the plate and connected to electrolyte supply means as well as a second series of orifices, also distributed over the surface of the plate and neighbors of the orifices of said first series, the orifices of said second series being connected to means for discharging the electrolyte, is characterized in that after the electrolytic deposition of a coating on said substrate, the substrate and an extra-thin metal sheet formed by the electrolytic coating deposited on said substrate, in that said extra-thin metal sheet is heated to a temperature higher than its recrystallization temperature and in that the said extra-thin metal sheet is then rapidly cooled to a temperature close to ambient temperature.
  • the reheating temperature is higher than approximately 650 ° C., in order to cause the recrystallization of the metal, and thus to improve its ductility by reducing its yield strength and its breaking load compared to the levels observed immediately after l '' electroforming.
  • the reheating step is preferably carried out by direct resistance heating.
  • Rapid cooling can be carried out, for example, by immersing the extra-thin sheet in an aqueous quenching bath which may be at a temperature above ambient temperature. Such rapid cooling exerts on the extra-thin sheet a softening effect which promotes the appearance of the ability to fold.
  • the degree of softening thus reached depends of course on the purity of the metal constituting said sheet, and in particular on its contents of carbon and free nitrogen.
  • an extra-thin sheet (10 ! Lm) of iron containing less than 0.002% carbon and less than 0.0007% nitrogen was recrystallized by heating and maintaining between 650 ° C and 850 ° C, then cooled to around 5600 ° C / s by immersion in boiling water. It thus acquired an excellent folding ability without spring effect without losing anything of its flatness or its surface appearance.
  • An extra-thin sheet of iron, produced and heat treated according to the process of the invention has a folding ability at least equivalent to that of the aluminum sheets currently used.
  • the device and the method in accordance with the present invention make it possible to manufacture high-quality extra-thin sheets, with high productivity of the installation and with limited energy consumption.
  • the arrangement which is the subject of the present invention makes it possible to achieve high turbulence without requiring significant electrolyte flow rates; moreover, the required pressure being low, the pumping power and consequently the energy consumption are limited.
  • the hydraulic path is very short due to the short distance separating the supply ports from the discharge ports.
  • the arrangement of the invention makes it possible to discharge practically all of the electrolyte through the discharge orifices; there is therefore no significant lateral flow and the device of the present invention has the advantage, important in practice, of not requiring side seals.
  • the recrystallization and softening heat treatment then provides the sheet with the ductility properties which provide it with the ability to fold without the spring effect required for its use in the packaging industry.

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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)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Executing Machine-Instructions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Secondary Cells (AREA)
  • Physical Vapour Deposition (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Claims (10)

1. Vorrichtung zur Herstellung einer besonders dünnen Metallfolie durch elektrolytische Abscheidung auf einem Träger, bestehend aus einer Kathode, die sich im allgemeinen aus dem Substrat zusammensetzt, und einer Anode, die in sehr kurzer Entfernung von der Kathode angebracht ist, sich aus einer Platte zusammensetzt, die von einer ersten Reihe von auf der Oberfläche der Platte verteilten und mit Mitteln zur Zufuhr des Elektrolyten verbundenen Löchern sowie von einer zweiten Reihe von Öffnungen, die ebenfalls auf der Oberfläche der Platte verteilt und den Öffnungen jener ersten Reihe benachbart sind, durchbohrt ist, wobei die Öffnungen jener zweiten Reihe mit Mitteln zum Abziehen des Elektrolyten verbunden sind, dadurch gekennzeichnet, daß sie außerdem Mittel zur Trennung des Trägers und der besonders dünnen Metallfolie, die aus der auf jenem Träger abgeschiedenen elektrolytischen Beschichtung besteht, Heizvorrichtungen zum Erhitzen jener besonders dünnen Metallfolie auf eine Temperatur oberhalb ihrer Rekristallisationstemperatur, sowie Kühlvorrichtungen zum schnellen Abkühlen der besonders dünnen Metallfolie auf eine Temperatur im Bereich der Umgebungstemperatur umfaßt.
2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß jene durch jene erste und zweite Serie von Öffnungen durchbohrte Platte eine Wand eines Kastens darstellt, der von einer Mehrzahl von Wänden gebildet wird und ein geschlossenes inneres Volumen begrenzt, wobei besagter Kasten
(a) mindestens eine Öffnung, genannt Zufuhröffnung, die eine Wand jenes Kastens durchsetzt und Zutritt zu jenem inneren Volumen verschafft; und
(b) mit den Öffnungen jener zweiten Reihe verbundene Rohre umfaßt, die jenes innere Volumen des Kastens durchsetzen, ohne damit verbunden zu sein, und an der Außenseite jenes Kastens münden.
3. Vorrichtung nach Anspruch 2, dadurch gekennzeichnet, daß mindestens ein Teil jener mit den Öffnungen der zweiten Reihe verbundenen Rohre an ihrem anderen Ende mit Saugmitteln verbunden sind.
4. Vorrichtung nach Anspruch 3, dadurch gekennzeichnet, daß jene Saugmittel einen Sammelbehälter und eine Pumpe umfassen.
5. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß die Öffnungen einer beliebigen der zwei Reihen von Öffnungen mit einzelnen Zufuhrleitungen verbunden sind, daß diese einzelnen Zufuhrleitungen einzeln oder in beliebigen Gruppen mit einer Elektrolytquelle verbunden sind, und daß die Öffnungen der anderen Reihe mit Rückführungsleitungen für den Elektrolyten verbunden sind.
6. Verfahren zur Herstellung einer besonders dünnen Metallfolie durch elektrolytische Abscheidung auf einem Träger mittels einer Vorrichtung nach einem der Ansprüche 1 bis 5, wobei das Verfahren darin besteht, daß man jenen die Kathode darstellenden Träger in einem sehr geringen Abstand von einer Anode anbringt, die sich zusammensetzt aus einer Platte, die von einer ersten Reihe von Löchern, die auf der Oberfläche der Platte verteilt und mit Mitteln zur Zufuhr eines Elektrolyten verbunden sind, sowie von einer zweiten Reihe von Öffnungen, die ebenfalls auf der Oberfläche der Platte verteilt und den Öffnungen jener ersten Serie benachbart sind, durchbohrt ist, wobei die Öffnung der zeiten Reihe mit Mitteln zum Abziehen des Elektrolyten verbunden sind, dadurch gekennzeichnet, daß nach der elektrolytischen Abscheidung einer Beschichtung auf jenem Träger dieser und eine besonders dünne Metallfolie, bestehend aus der darauf abgeschiedenen elektrolytischen Beschichtung, getrennt werden, daß jene besonders dünne Metallfolie bis auf eine Temperatur oberhalb ihrer Rekristallisationstemperatur erhitzt wird und daß anschließend jene besonders dünne Metallfolie schnell bis auf eine Temperatur im Bereich der Umgebungstemperatur abgekühlt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man jene besonders dünne Metallfolie auf eine Temperatur oberhalb 650°C erhitzt.
8. Verfahren nach einem der Ansprüche 6 oder 7, dadurch gekennzeichnet, daß man jene besonders dünne Metallfolie mittels direkter elektrischer Widerstandsheizung erhitzt.
9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, daß man jene besonders dünne Metallfolie durch Eintauchen in ein wäßriges Bad abkühlt.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man eine wäßriges Bad verwendet, das sich auf einer Temperatur oberhalb der Umgebungstemperatur befindet.
EP86870147A 1985-10-15 1986-10-13 Verfahren und Vorrichtung zur Herstellung einer hauchdünnen Metallfolie durch galvanische Beschichtung Expired - Lifetime EP0222724B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86870147T ATE58921T1 (de) 1985-10-15 1986-10-13 Verfahren und vorrichtung zur herstellung einer hauchduennen metallfolie durch galvanische beschichtung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
LU86119A LU86119A1 (fr) 1985-10-15 1985-10-15 Dispositif de depot electrolytique et procede pour sa mise en oeuvre
LU86119 1985-10-15

Publications (2)

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EP0222724A1 EP0222724A1 (de) 1987-05-20
EP0222724B1 true EP0222724B1 (de) 1990-12-05

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EP86870147A Expired - Lifetime EP0222724B1 (de) 1985-10-15 1986-10-13 Verfahren und Vorrichtung zur Herstellung einer hauchdünnen Metallfolie durch galvanische Beschichtung

Country Status (14)

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US (1) US4702812A (de)
EP (1) EP0222724B1 (de)
JP (1) JPH0788597B2 (de)
KR (1) KR940002262B1 (de)
AT (1) ATE58921T1 (de)
AU (1) AU592378B2 (de)
BR (1) BR8605023A (de)
CA (1) CA1313508C (de)
DE (1) DE3676053D1 (de)
ES (1) ES2020199B3 (de)
FI (1) FI85290C (de)
LU (1) LU86119A1 (de)
NO (1) NO864100L (de)
ZA (1) ZA867788B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU86773A1 (fr) * 1987-02-13 1988-11-17 Centre Rech Metallurgique Installation pour la fabrication en continu d'une feuille metallique extra-mince par depot electrolytique
US5228965A (en) * 1990-10-30 1993-07-20 Gould Inc. Method and apparatus for applying surface treatment to metal foil
US5393396A (en) * 1990-10-30 1995-02-28 Gould Inc. Apparatus for electrodepositing metal
JP4586423B2 (ja) * 2004-02-27 2010-11-24 Ｊｆｅスチール株式会社 電気めっき鋼板の製造方法
KR101403891B1 (ko) * 2007-10-10 2014-06-11 한국생산기술연구원 니켈-철 합금층과, 그의 전주 장치 및 전주 방법과, 그의제조 장치 및 방법

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* 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
US4174261A (en) * 1976-07-16 1979-11-13 Pellegrino Peter P Apparatus for electroplating, deplating or etching
JPS5827993A (ja) * 1981-08-10 1983-02-18 Sonitsukusu:Kk 微小部分メツキ方法及びその装置
US4529486A (en) * 1984-01-06 1985-07-16 Olin Corporation Anode for continuous electroforming of metal foil

Also Published As

Publication number Publication date
FI85290C (fi) 1992-03-25
CA1313508C (en) 1993-02-09
BR8605023A (pt) 1987-07-14
NO864100L (no) 1987-04-21
KR870004170A (ko) 1987-05-07
FI864136A0 (fi) 1986-10-14
LU86119A1 (fr) 1987-06-02
ZA867788B (en) 1987-05-27
FI85290B (fi) 1991-12-13
DE3676053D1 (de) 1991-01-17
ATE58921T1 (de) 1990-12-15
EP0222724A1 (de) 1987-05-20
AU6396986A (en) 1987-04-16
JPH0788597B2 (ja) 1995-09-27
NO864100D0 (no) 1986-10-14
AU592378B2 (en) 1990-01-11
JPS6296694A (ja) 1987-05-06
ES2020199B3 (es) 1991-08-01
KR940002262B1 (ko) 1994-03-19
FI864136A (fi) 1987-04-16
US4702812A (en) 1987-10-27

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