EP0123631B2 - Procédé et dispositif de traitement électrochimique de la surface de produits métalliques de forme allongée - Google Patents

Procédé et dispositif de traitement électrochimique de la surface de produits métalliques de forme allongée Download PDF

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Publication number
EP0123631B2
EP0123631B2 EP84420045A EP84420045A EP0123631B2 EP 0123631 B2 EP0123631 B2 EP 0123631B2 EP 84420045 A EP84420045 A EP 84420045A EP 84420045 A EP84420045 A EP 84420045A EP 0123631 B2 EP0123631 B2 EP 0123631B2
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EP
European Patent Office
Prior art keywords
cell
product
zones
electrodes
groups
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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EP84420045A
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German (de)
English (en)
French (fr)
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EP0123631A1 (fr
EP0123631B1 (fr
Inventor
Robert Guillermet
Michel Ladet
Gérard Laslaz
Claude Le Villard Le Bars
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Softal Te Clichy Frankrijk
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SOFTAL
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Publication date
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Application filed by SOFTAL filed Critical SOFTAL
Priority to AT84420045T priority Critical patent/ATE24209T1/de
Publication of EP0123631A1 publication Critical patent/EP0123631A1/fr
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Publication of EP0123631B1 publication Critical patent/EP0123631B1/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
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • 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
    • C25D1/02—Tubes; Rings; Hollow bodies
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating

Definitions

  • the present invention relates to a method and a device for electrochemical treatment in static or defiled the surface of metal products of elongated shape such as bars, circles, sections, strips, wires, etc.
  • It relates more particularly to the anodization of metals and alloys based on aluminum, magnesium and titanium.
  • This treatment can be carried out in particular by the electrochemical route which consists in immersing the product in an electrolyte solution and in simultaneously subjecting it to the action of an electric current so as to develop on its surface differently charged areas such as anodic zones of positive charge and cathodic zones of negative charge.
  • the electrochemical route which consists in immersing the product in an electrolyte solution and in simultaneously subjecting it to the action of an electric current so as to develop on its surface differently charged areas such as anodic zones of positive charge and cathodic zones of negative charge.
  • anodizing treatment which consists of immersing the product in an oxacid such as sulfuric acid and in a development of an anode zone so that an artificial oxide layer having better corrosion resistance than the natural oxide layer is formed on the surface of the product, under the combined action of these two means.
  • the investment costs are notably linked to the dimensions of the devices and those of operation depend mainly on the consumption of electric current per unit of surface treated, the expenditure of labor and the speed of treatment.
  • the electrochemical treatment processes are conventionally carried out in devices comprising one or more tanks of elongated shape along the vertical or horizontal, filled with electrolyte, in which the product is immersed in the fixing, if it is a static process or, on the contrary, allowing it to move along the tanks and guiding it, in the case of a process at the parade.
  • This or these tanks are grouped under the name of cell and this cell is generally equipped on its side walls with one or more electrodes which immerse in the electrolyte without having mechanical contact with the product to be treated and are connected to the one of the poles of the generator. As for the other pole, two main modes of connection are currently used.
  • connection is carried out directly by mechanical contact on the product by means of means which differ according to whether it is a static or parade process.
  • the means is constituted by a clamping device either by screw, by jaws or by stirrups, connected to the generator by flexible cables and which is applied to one of the ends of the product to be treated.
  • the contact area between the product and the device must be sufficiently large, all the more so as the intensity of the current to be admitted is high.
  • the surface trapped by the device will not be able to undergo the combined action of the electrolyte and the electric current, so that this surface will not be treated and that it will therefore be necessary to reject get a homogeneously treated product.
  • the material yield of the process is reduced, all the more so when the current intensities used are high.
  • each treatment operation is accompanied by assembly and disassembly operations of the clamping device on the product, which increases the labor costs and decreases the speed of treatment, and therefore contributes to an increase in the cost price.
  • This drawback can be mitigated by the automation of such devices, but with an expensive investment which, ultimately, will also increase the cost price of the products treated.
  • This first mode of connection by mechanical contact with the product is very suitable for the use of a single electrolyte tank. It is different in the second connection mode where the electrical connection of each of the generator poles is carried out in the same way via electrodes and an electrolyte volume and where two separate tanks are used: an actual treatment tank and a so-called liquid current intake tank inside which the product to be treated is placed.
  • these two tanks are generally contiguous and elongate in the same direction, the second being often shorter than the first.
  • these two tanks can be produced from a cell which is divided into two compartments by means of a transverse partition.
  • the electrical circuit used can be illustrated by taking the example of a DC anodizing method.
  • the electrodes of the liquid current plug connected to the positive pole of the generator, the electrolyte layer separating these electrodes from the surface of the product placed in the plug which contributes to developing a cathode zone in the vicinity of the product, the length of the product between this zone and the anode zone located in the treatment tank, the electrolyte layer which separates this last zone from the electrodes connected to the negative pole of the generator.
  • connection method constitutes a significant improvement compared to the direct connection by mechanical contact because it avoids in static all the operations of assembly and disassembly of the clamping devices and, in the process, the arcing or sparking problems.
  • it does not solve the problem of heterogeneity of treatment because the part of the product located in the liquid outlet is always in a zone of polarity opposite to that necessary for treatment and therefore cannot undergo this treatment. This part must therefore be discarded and recycled just as in the contact connection.
  • Such a mode of connection can also be applied in a process of treatment at the parade, as the Japanese patent application published under the number 52 59037 teaches.
  • a metal strip is anodized continuously in a cell having a partition no longer transverse but longitudinal, so as to have an anode chamber and a cathode chamber which elongate in the direction of translation of the product.
  • the electric current preferably borrows the circuits of least resistance. If the seal is not perfect between the socket outlet and the treatment compartment, it will tend during treatment to flow through the electrolyte rather than passing through the product. Therefore, it will simply be used to heat the electrolyte by the Joule effect and will not participate in the treatment itself, hence a reduction in the electrical efficiency of the installation.
  • This invention relates firstly to a method of electrochemical treatment in static or in the process of the surface of metal products of elongated shape in a cell comprising a single compartment which contains an electrolyte and on the walls of which are arranged at least a set of four groups of electrodes.
  • This process is characterized in that an electric current is passed through the electrodes so as to develop constantly over time along the cell in each set and successively an anode zone, a non-polarized zone, a cathode zone and a non-polarized zone, separated from each other, that the polarities of said groups are changed simultaneously along the cell while keeping the same order of succession, and that, when the treatment is carried out at the parade, the speed of movement of the zones is greater than the translation speed of the product.
  • this process also has the particularity of presenting essentially anodic and cathodic zones established in the same volume of electrolyte.
  • the structure of the cell is greatly simplified since it becomes a single compartment.
  • a characteristic of the process consists in having zones which extend parallel to the axis of the product to be treated over a certain length, but are separate, that is to say that they are not adjacent and that there has a portion of product located between the two zones, which is neither essentially cathodic nor essentially anodic. This reduces the current losses from the electrolyte.
  • the space between two zones cannot be fixed a priori because it depends on the operating parameters of the treatment operation. But it is determined so as to have a reduced current loss compared to the processing current.
  • the length of the zones themselves, they must meet the imperative that one cannot exceed a certain amount of current per unit area of the product to be treated, in particular in cathodic zones, if one wishes to avoid breakdowns of the oxide layer in the case of an anodization for example.
  • we are also linked to the desired productivity of the cell which, in the case of anodization, depends on the amount of current admitted into the anodic zone, and consequently on its length.
  • Another originality of the process according to the invention consists in the fact that the zones are displaced simultaneously all along the product. This displacement, or sweeping, is done simultaneously so that, during an operation, the zones keep their initial length and remain spaced at the same interval.
  • the displacement is carried out all along the product, that is to say that each portion of the latter, even in a static process, whether located at the end or in the middle of the length contained in the cell, is found placed at least once in time in an essentially anodic area and then in an essentially cathodic area or vice versa.
  • the entire surface of the product is treated anodically for example in an anodizing or etching operation or cathodically for example in a colorization operation, there is therefore no heterogeneity of treatment from point to the other of the product and, as a result, the operation will not subsequently cause a loss of material.
  • this scanning can be done with a suitable speed to allow the passage of an area a quantity of current per unit area determined which does not exceed, for example for anodization, the critical amount of breakdown current.
  • this scanning is also carried out cyclically, that is to say that, during an operation, an anodic zone for example which has traversed the entire length of product contained in the cell again traverses one or more times all this same length and, similarly, for the other zones and spacings. Each sweep from one end to the other constitutes a cycle and this cycle is therefore repeated n times in time.
  • the scanning speed during the n cycles can be constant or variable depending on the problem to be solved. We can therefore establish a regular periodicity or not.
  • each cycle or group of cycles is different from the following cycle and from the group of following cycles either by the length of the zones or the spacings between zones, or by the reciprocal arrangement of the zones.
  • anodic and cathodic zones of the same length can be had, then, during another cycle or another group of cycles, zones or spacings between zones of different lengths.
  • a large number of possibilities based on scanning and varying the configuration of the electrical states can thus be realized without departing from the scope of the invention.
  • the speed of movement of the zones is greater than the speed of translation of the product through the cell and by an amount sufficient to be able to benefit from the advantages of scanning.
  • a speed greater than twice the translation speed is preferably chosen.
  • the invention also relates to a particular device for implementing the method.
  • This device conventionally comprises a cell in elongated form having a single compartment which contains an electrolyte solution within which the product to be treated is immersed, which is provided on its longitudinal walls with electrodes immersed in said solution, arranged at the neighborhood of at least part of the periphery of the part and capable of being aligned by one of the poles of an electric generator so as to create by passing a current through a fraction of the volume of the solution and over a portion of the product length of essentially anodic and cathodic areas.
  • the electrodes at all times form at least one set of four successive groups of at least one electrode per group, each set comprising in the same direction two groups supplied by each. generator poles, two non-powered groups, one of which is located between the two preceding ones, and the other following, that, according to a certain program, at least one of the electrodes placed at the end of each of the groups changes electrical state so that the same electrical configuration is found over the entire length of the cell, but offset by at least one electrode along the cell, the offset at one of the ends of the cell being transferred to the other side.
  • the elements of the usual devices are reproduced in the device according to the invention, namely a cell with a liquid current outlet, which makes it possible to contain the product to be treated over at least part of its length as well as the electrolyte solution. and whose walls are equipped with a series of electrodes separated from each other, which can completely surround the product or simply lie parallel to one or both large faces of the product depending on which one wishes to perform a treatment on one or two sides of the product. But, instead of having several compartments, the cell has only one.
  • each group can include one or more electrodes but, in each set, there are two groups which are supplied by the opposite poles of the generator. These two groups each produce an electrical circuit formed, on the one hand, by the electrolyte volumes located between the electrode (s) of each of the groups supplied and the product, and which constitute the anode and cathode zones and, on the other hand , the length of the product that separates the two areas.
  • two groups of electrodes which are not supplied and make it possible to separate the polarized zones from one another.
  • groups 1 and 3 are supplied each by one of the poles of the generator, while groups 2 and 4 are not.
  • groups 1 and 3 are no longer supplied and the generator poles supply groups 2 and 4 in the same order.
  • the electrodes supplied are the same as at the instant t, but under opposite polarities; similarly, at time t + 3, the electrodes 2 and 4 are supplied as at time t + 1, but by reversing the polarities.
  • An electrical scan is carried out along all of the four groups of electrodes, which leads to a displacement of the zones.
  • the scanning can be done electrode by electrode so as to carry out an electrical sliding and a displacement of the zones either by sector, but step by step.
  • this scanning is carried out so as to establish a certain synchronism between the sets and to have identical electrical states in each group at a given instant.
  • this device accommodates for its electrical supply one or more independent sources controlled in current and in voltage, synchronized or not with the frequency of the network and connected to the electrodes.
  • the cyclical scanning of the connections implies, during the displacement of the configurations, the cutting and the re-supply of a certain number of electrodes according to the time division and in number of electrodes predetermined in advance.
  • an electric power switch which is chosen from different systems and combinations thereof, such as automatic disconnectors, pneumatic or electromagnetic contactors, power relays, bipolar power transistors, power transistors field effect, thyristors (SCR), TRIAC, controlled thyristors (GTO) or any system capable of providing this power supply function or not.
  • control of these supply systems is carried out according to the speed and complexity of the cycles envisaged by various electrical means leading to sequential logic.
  • various electrical means leading to sequential logic mention may be made of rotary electrical current supply switches, sets of electromagnetic relays, wired static switching circuits, programmable logic controllers, computer systems based on microprocessors or minicomputers.
  • This product which can flow in a direction perpendicular to the plane of the figure, has two portions delimited by the sealed opening (9) formed in the partition (2).
  • the cell (10) filled with an electrolyte (11) comprises a series of partitions (12) forming cathode (13) and anode (14) compartments, equipped with anodes (15) and cathodes ( 16) in which cathode and anode zones are developed respectively.
  • the product (17) circulates in the cell in the direction (18) and in an anodization process, the oxide layer is formed when the product passes through each anodic zone.
  • Such a device does not require rejecting part of the product but, given the relatively limited speed at which the product can circulate and the need to work at current densities in the cathode compartment below a critical value, we are forced to '' have a large number of compartments to carry out the desired treatment.
  • FIG. 3 represents a cell according to the invention in longitudinal section.
  • the cell body (19) filled with electrolyte (20) in which the product to be treated (21) is immersed.
  • a set of 4 groups (22), (23), (24), (25) is distributed along the cell.
  • the electrodes (22) and (24) are connected to the positive and negative poles of an electric generator not shown so as to develop in their vicinity respectively cathodic and anodic zones, and the electrodes (23) and ( 25) are not supplied in such a way as to separate these zones.
  • the zones are moved along the product so that the entire surface is successively scanned by zones of opposite polarity and therefore undergoes treatment.
  • FIG. 4 gives the state of the connections of the electrodes in the cell at times t, t + 1 and t + 2.
  • This movement takes place here by sliding step by step, the electrical configuration with two successive istants t and t + 1, or t + 1 and t + 2, corresponding to an offset of an electrode.
  • FIG. 5 is a diagram of the twenty electrical configurations which arise during a cycle in a cell equipped with twenty electrodes identified by the letters A, B, C ... T and where each displacement identified from 0 to 20 s' performs electrode by electrode.
  • the electrodes A B C D E are supplied positively and the electrodes K L M N O negatively while the electrodes F G H 1 J and P Q R S T are not supplied.
  • the invention can be illustrated using the following application example: an aluminum alloy profile of the type 6000 according to the standards of the American Aluminum Association, 6 meters long with a section perimeter of 0 , 30 m was subjected to an anodization treatment by means of a sulfuric acid solution at 200 g / liter in a cell of neighboring length, of 0.03 m 2 of section provided with 100 electrodes distributed regularly all along of the cell and spaced 0.06 meters apart, center to center. These electrodes were supplied so as to constitute four zones, 1.5 m in length each: an anode zone and a cathode zone separated by a non-polarized zone and the cathode zone being extended by a zone which is also non-polarized. These areas moved electrode by electrode at the speed of 0.4 m / second. The current density in each of the polarized areas was 12 A / dm2.
  • the duration of the operation was 20 minutes and the loss of current by leakage in the electrolyte was less than 5%, which constitutes a good compromise between productivity and electrical efficiency.
  • the present invention finds its application in any electrochemical treatment of metals of elongated shape, in static or in parade, whether it is intended for anodizing, etching, coloring, galvanizing or any other surface modification and for which we want regular treatment of the entire surface of the product under optimum operating cost conditions and with a reduced investment.

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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)
  • Chemical Treatment Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Lead Frames For Integrated Circuits (AREA)
  • Elimination Of Static Electricity (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Pyrrole Compounds (AREA)
EP84420045A 1983-03-16 1984-03-14 Procédé et dispositif de traitement électrochimique de la surface de produits métalliques de forme allongée Expired - Lifetime EP0123631B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84420045T ATE24209T1 (de) 1983-03-16 1984-03-14 Verfahren und vorrichtung zur elektrochemischen behandlung der oberflaechen von langgestreckten, metallischen gegenstaenden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8304612 1983-03-16
FR8304612A FR2542766B1 (fr) 1983-03-16 1983-03-16 Procede et dispositif de traitement electrochimique de la surface de produits metalliques de forme allongee

Publications (3)

Publication Number Publication Date
EP0123631A1 EP0123631A1 (fr) 1984-10-31
EP0123631B1 EP0123631B1 (fr) 1986-12-10
EP0123631B2 true EP0123631B2 (fr) 1992-09-02

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EP84420045A Expired - Lifetime EP0123631B2 (fr) 1983-03-16 1984-03-14 Procédé et dispositif de traitement électrochimique de la surface de produits métalliques de forme allongée

Country Status (15)

Country Link
US (1) US4681665A (fi)
EP (1) EP0123631B2 (fi)
JP (1) JPS59173293A (fi)
KR (1) KR840007909A (fi)
AT (1) ATE24209T1 (fi)
CA (1) CA1205779A (fi)
DE (1) DE3461654D1 (fi)
DK (1) DK159730C (fi)
ES (1) ES530627A0 (fi)
FI (1) FI75608C (fi)
FR (1) FR2542766B1 (fi)
GR (1) GR73548B (fi)
IS (1) IS1324B6 (fi)
NO (1) NO164850C (fi)
PT (1) PT78256B (fi)

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Publication number Priority date Publication date Assignee Title
US5681441A (en) * 1992-12-22 1997-10-28 Elf Technologies, Inc. Method for electroplating a substrate containing an electroplateable pattern
US5968203A (en) * 1997-02-28 1999-10-19 Sybron Chemicals Inc. Clay-containing textile material treating composition and method
AU7126798A (en) * 1997-04-16 1998-11-11 Drexel University Bipolar electrochemical connection of materials
US6350363B1 (en) 1997-04-16 2002-02-26 Drexel University Electric field directed construction of diodes using free-standing three-dimensional components
US5853561A (en) * 1997-06-23 1998-12-29 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for surface texturing titanium products
AU3201699A (en) 1998-03-24 1999-10-18 Drexel University Process of making bipolar electrodeposited catalysts and catalysts so made
US6120518A (en) * 1998-04-01 2000-09-19 Promex, Inc. Non-reflective surfaces for surgical procedures
EP0999295A3 (de) * 1998-10-23 2006-05-17 SMS Demag AG Anordnung zur elektrogalvanischen Metallbeschichtung von Bändern
JP5323677B2 (ja) * 2007-03-02 2013-10-23 古河電気工業株式会社 表面粗化銅板の製造方法及び装置、並びに表面粗化銅板
TW200840120A (en) * 2007-03-20 2008-10-01 Industrie De Nora Spa Electrochemical cell and method for operating the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267146A (en) * 1934-07-30 1941-12-23 Sharon Steel Corp Apparatus for electrically pickling and cleaning stainless steel and other metals
NL131875C (fi) * 1964-02-04 1900-01-01 Aluminium Lab Ltd
US3420760A (en) * 1965-04-30 1969-01-07 Gen Dynamics Corp Process for descaling steel strip in an aqueous organic chelating bath using alternating current
US3453201A (en) * 1965-10-05 1969-07-01 Asahi Chemical Ind Polarity reversing electrode units and electrical switching means therefor
US3718547A (en) * 1970-11-16 1973-02-27 Alcan Res & Dev Continuous electrolytic treatment for cleaning and conditioning aluminum surfaces
JPS517081B1 (fi) * 1971-04-17 1976-03-04
CH562334A5 (fi) * 1972-02-04 1975-05-30 Alusuisse
GB1434701A (en) * 1974-02-20 1976-05-05 Alcan Res & Dev Process and apparatus for electrolytic colouration of anodised aluminium
US4214961A (en) * 1979-03-01 1980-07-29 Swiss Aluminium Ltd. Method and apparatus for continuous electrochemical treatment of a metal web

Also Published As

Publication number Publication date
GR73548B (fi) 1984-03-13
EP0123631A1 (fr) 1984-10-31
DK98084D0 (da) 1984-02-24
US4681665A (en) 1987-07-21
DK98084A (da) 1984-09-17
JPS59173293A (ja) 1984-10-01
DK159730C (da) 1991-04-22
ATE24209T1 (de) 1986-12-15
IS1324B6 (is) 1988-08-03
FR2542766B1 (fr) 1987-07-03
ES8504975A1 (es) 1985-04-16
NO841012L (no) 1984-09-17
DE3461654D1 (en) 1987-01-22
JPH0124237B2 (fi) 1989-05-10
FI841057A0 (fi) 1984-03-15
PT78256B (fr) 1986-04-22
FI75608B (fi) 1988-03-31
FI841057A (fi) 1984-09-17
DK159730B (da) 1990-11-26
NO164850C (no) 1990-11-21
NO164850B (no) 1990-08-13
ES530627A0 (es) 1985-04-16
FR2542766A1 (fr) 1984-09-21
KR840007909A (ko) 1984-12-11
CA1205779A (fr) 1986-06-10
FI75608C (fi) 1988-07-11
IS2898A7 (is) 1984-09-17
EP0123631B1 (fr) 1986-12-10
PT78256A (fr) 1984-04-01

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