EP4019670A1 - Dispositif d'oxydation pour surfaces métalliques planes, telles qu'une tôle, un tissu ou un treillis métallique et procédé d'application du traitement - Google Patents

Dispositif d'oxydation pour surfaces métalliques planes, telles qu'une tôle, un tissu ou un treillis métallique et procédé d'application du traitement Download PDF

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Publication number
EP4019670A1
EP4019670A1 EP21020636.3A EP21020636A EP4019670A1 EP 4019670 A1 EP4019670 A1 EP 4019670A1 EP 21020636 A EP21020636 A EP 21020636A EP 4019670 A1 EP4019670 A1 EP 4019670A1
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EP
European Patent Office
Prior art keywords
metal surface
treated
planar
electrode
planar metal
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.)
Pending
Application number
EP21020636.3A
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German (de)
English (en)
Inventor
Stefano Muratori
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.)
METALY Srl
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METALY Srl
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Filing date
Publication date
Application filed by METALY Srl filed Critical METALY Srl
Publication of EP4019670A1 publication Critical patent/EP4019670A1/fr
Pending legal-status Critical Current

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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
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/005—Apparatus specially adapted for electrolytic conversion coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/022—Anodisation on selected surface areas
    • 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
    • C25D17/005—Contacting devices
    • 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
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/14—Electrodes, e.g. composition, counter electrode for pad-plating

Definitions

  • the present invention relates to an apparatus for the oxidation of planar metal surfaces, i.e. an apparatus for applying the desired oxidation onto metal surfaces in order to obtain a desired uniform colouring or decoration in limited areas of the surface being treated, so as to obtain graphic shapes and drawings or even lettering on the surface concerned.
  • the method for applying the treatment of the planar, sheet metal, cloth or wire mesh surface is also described.
  • the state of the art comprises generally continuous metal surface oxidation apparatuses wherein the apparatus applies the chemical action, possibly enhanced and accelerated by electrolytic action, of a product acting on the metal of the surface to force the formation of an oxide on the surface itself.
  • the metals involved in the aforementioned treatment are those that, in oxidation, generate a stable oxide at the end of the treatment and do not further damage the metal itself over time, hence iron and carbon steel, which are subject to the formation of the unstable oxide constituting the ferrous or ferric oxide, are conveniently excluded, although nothing prevents the treatment of these metals with oxidation, though they can still subsequently rust.
  • Known in the art from prior document JP 2003211324 A is a method of surface action engraving on a metal surface in which an electrode conformed to the shape to be engraved on the workpiece is facing, though not in contact with the surface being worked upon.
  • the electrode has a layer of high electrical conductivity in the electrolytic action parts and an insulating mask applied to define the contours of the electrolytic action surface that is to be reproduced on the surface being treated.
  • the electrolytic solution here a sodium hydroxide solution obtained by dissolving sodium nitrate in water, is forcibly circulated in the space between the electrode and the surface being treated, without any part of the electrode being in contact, but placed at a short distance of less than 1 millimetre from the surface being treated.
  • the treatment takes place in a closed cell into/from which the electrolyte enters and exits and where the advantage for the electrode is that there is little or no wear of the electrode that is covered by the high electrical conductivity layer; hence the limitation of the surface extension of the treatment is given by the limitation of the cell, meaning that this method is not suitable for carrying out oxidations on large surfaces.
  • a method for decorating metal surfaces is also known by arranging a thin spacer screen between an electrode and the metal surface to be decorated in which figures, shapes or lettering are provided and highlighted for electrode attachment mediated by the electrolyte solution.
  • the electrode is equipped with a buffer soaked in an electrolytic solution and is moved in a variable motion over the surface to be treated.
  • a similar embodiment is described in US 2014/03600881 A1 .
  • the presence of surface discontinuities prevents the long life of the buffer in oxidation by the means known in the art that operates by friction, such as the use of the buffer in insulating fabric or electrode in contact with the insulating fabric, or even if carried out with a bath in an electrolytic tank.
  • the treatment is carried out on the entire surface of the grid or metallic cloth, with a limitation on the operation times, the treated surface being much greater than that in the external view of the cloth or grid/metallic mesh which, conversely, is to be decorated and/or coloured with a special uniform oxide on the visible parts from only one side of the grid/mesh or metallic cloth surface.
  • the technical problem, therefore, underlying the present invention is that of making an apparatus that allows application of the electrolytic oxidation of large planar metal surfaces by carrying out the treatment quickly and limiting the wear or damage of the active surfaces of the electrode that applies the treatment to the metal surface, also limiting or reducing to zero the wear of the device interposed between the electrode and the surface being treated.
  • An aim inherent in the above technical problem is to produce an apparatus that applies the aforementioned electrolytic action which in turn allows the rapid treatment of large metal surfaces such as metal sheets, cloths or wire meshes in the application of the treatment.
  • a corollary to the technical problem described above is the possibility of making the apparatus for applying the electrolytic oxidation treatment with zero electrode wear and that is indifferent to the size of the treated surface.
  • an apparatus for oxidising planar metal surfaces comprising a tank within which the planar metal surface being treated is laid; a circuit electric power supply; the two electric power supply heads of the circuit are in contact with electrodes, with high electrical conductivity; a first planar electrode is placed below the metal surface being treated on the bottom of the aforementioned tank; an electrolyte is placed in the tank to close the electrolytic oxidation circuit; a second electrode is placed sliding and spaced on the planar metal surface being treated in an immersed position at the level of the electrolyte in the tank; characterised in that it has the second electrode consisting of a conductive roller placed so as to roll on the planar metal surface being treated, avoiding contact between the cylindrical surface of the roller electrode towards the planar metal surface being treated by the interposition of a permeable spacer element; the spacer is made of a material resistant to the electrolytic action of oxidation and is placed on at least one of the two surfaces, either the cylindrical surface of the roller electrode or the
  • a specific form of the spacer element is applied to the cylindrical surface of the roller of the roller electrode and consists of absorbent and insulating material to form a coating sheath covering the cylindrical surface.
  • a further improved form of the spacer element is created by a passage printing screen placed, before treatment, on the planar metal surface to be treated, in contact with it, and creating a distance with the thickness of the screen itself between the cylindrical surface of the roller electrode and the planar metal surface being treated.
  • planar metal surface under treatment are masks, resistant to electrolytic action, to make decorations, images or lettering on the planar metal surface with the oxidation treatment.
  • the passage printing screen features electrolytically resistant masks for creating decorations, images or lettering on the planar metal surface with the oxidation treatment.
  • the passage printing screen with masking in order to create decorations, images or lettering on its planar metal surface with oxidation treatment, is laid against the planar metal surface under treatment with the masking facing above and in contact with said planar metal surface, while the electrolytic oxidation action of the roller electrode with its cylindrical surface is applied on the upper side of the passage printing screen.
  • the first planar electrode is constituted by a graphite planar plate or graphite mesh placed on the bottom of the tank on which the planar metal surface being treated is laid.
  • the roller electrode is made from a cylindrical graphite tube in which an axial metal pin is connected at the ends with the second head of the electrical circuit: the rotational support between the central pin and the graphite tube roller is achieved by a conical turning pair, made of metallic material, close to each end of the roller.
  • the Figures show the oxidation apparatus 1 of a metal surface 2 of a planar plate 3, visible in Figure 1 ; the planar plate being treated is placed on the bottom 4 of a planar tank 5 with a planar electrode 6 interposed, here in the form of a mesh 7; the electrode is connected with a first head 8 of the electrical circuit for activating the electrolytic action.
  • the end 9 and side 10 walls of the planar tank 5 contain an electrolyte with level 11 such as to submerge completely the planar electrode 6, the metal surface 2 being treated and, partly, a roller electrode 12 with a roller 13 which brings the second head 14 of the electrical activation circuit inside the electrolytic solution; the roller is made of metallic or graphite electrical conductive material.
  • the roller electrode 12 is supported in rotation by a frame 15 on which the manual action of the operator acts, with the handle 16; or, more advantageously, the frame 15 is connected to a drive mechanism, not shown, of the frame to bring the roller electrode to roll on the metal surface 2 being treated.
  • a coating 18 with insulating and permeable material, also resistant to electrolytic action, is placed on the cylindrical surface 17 of the roller, visible in Figure 3 , with the aim of isolating the cylindrical surface 17 of the roller 13 from the metal surface 2 being treated.
  • Figure 2 also shows a mask 19 for making a decoration, lettering or other graphic form on the metal surface 2 being treated that the user wishes to transfer onto the metal surface.
  • the planar electrode 6 depicted, in addition to being made of wire mesh 7, can be made of graphite mesh, which is known to be a good electrical conductor and is also resistant to the action of the electrolyte.
  • Figure 3 shows the electrolytic oxidation apparatus 1 with a planar electrode 6, consisting of a metal plate 20, placed on the bottom 4 of the tank 5 and in contact with the lower face of the metal surface 2 to allow the electrical contact of the first electrical head 8 of the circuit.
  • the metal surface 2 has masking 19 to create, on the metal surface being treated, the graphic shapes that the user intends to transfer onto the metal surface.
  • the planar electrode 6 depicted can be made with a graphite plate as a good electrical conductor which is also resistant to the action of the electrolyte.
  • Figure 5 shows the axial section of the roller electrode and the rotating support frame with trace V-V.
  • Dimension B i.e. the active face of the roller electrode 12 is made with a value suitable for the size of the planar tank 5 used, and, in the most convenient size, also reaches 1,550 mm.
  • the oxidation apparatus performs the processing of planar surfaces with dimensions of 3,000x1,500 millimetres, or even smaller, mainly for samples of 700x400 millimetres using a roller with a size B of 450 mm.
  • the roller 13 is rotatably supported on the frame 15 by means of a pin 21 to the ends 22 of which the connection and union cables are connected to the second electrical head 14 of the circuit.
  • the pin 21 crosses the entire roller within a hole 23 with diameter DI and, near the ends 24 of the roller 13, has conical turning pairs 25, each formed by an outer ring 26, keyed to the end housing 24 of the roller 13, and an inner ring 27 keyed and tightened against the taper of the outer ring, on said pin 21, with the thrust of a ring nut 28.
  • sealing rings 29 are keyed to said end housing of the roller and in contact with the pin 21 for sealing.
  • roller 13 has an outer diameter DE which in operation is maintained below the level 11 of the electrolyte.
  • Figure 5 also shows a coating in insulating and permeable material 18 used for the treatment of metal surfaces with uniform oxidation with or without the use of masking 19.
  • the roller 13 is advantageously made of graphite as a conductive material, while the pin is made of metallic material; finally, the frame 15 is made of insulating material.
  • the electrolytic oxidation apparatus 1 is made in a modified form with the interposition, between the roller 13 of the roller electrode 12 with the metal surface 2 to be treated, of a passage printing screen 30, which is known to be resistant to the action of the electrolyte while insulating the surface 17 of the roller 13 with respect to said metal surface 2 of the plate 3 depicted.
  • a passage printing screen 30 which is known to be resistant to the action of the electrolyte while insulating the surface 17 of the roller 13 with respect to said metal surface 2 of the plate 3 depicted.
  • the oxidation action takes place through the screen, stretched on the metal surface 2 being treated by means of a frame 31 larger than the metal surface itself, also to accommodate the roller 13 of the roller electrode 12 during the treatment.
  • a mask 32 can be applied to the screen so as to create, on the metal surface being treated, the graphic shapes that the user intends to transfer to the metal surface 2.
  • the masking is carried out on the underside of the passage printing screen 37; this means that the lower masking 38 comes into contact
  • Figures 8 and 9 show the oxidation apparatus 1 of metal surfaces wherein the metal surface 2 undergoing treatment is represented by a metal cloth 33 during the treatment with uniform colouration;
  • Figure 9 shows the oxidation apparatus 1 on which a metal surface undergoing treatment is placed, consisting of metal mesh 34 placed on a planar electrode 6 also of metal mesh 35, while masking 36 is done on the metal surface 2 undergoing treatment to highlight the graphic forms, lettering or decorations desired by the user.
  • the metal surface being treated is placed in an electrolyte containment tank so as to keep the entire metal surface 2 being treated wetted by the electrolyte: the level of the electrolyte 11 in the tank 5 must be higher than the lower cylindrical surface 17 of the roller electrode 12, so as to maintain at all times an electrolyte head on the metal surface 2 being treated.
  • the planar metal surface 2 is in contact with the lower planar electrode 6 and, therefore, is connected with the first head 8 of the electrical circuit for activating the oxidation electrolytic action.
  • the roller 13 of the roller electrode 12 is in electrical contact with the second head 14 of the electrical circuit for activating the aforementioned electrolytic oxidation action.
  • the applied current can be either direct or alternating, depending on the type of metallic surface 2 being treated and the metallic material that, to achieve the required oxidation, requires one or other type of electric current.
  • the interposition of a passage printing screen 30 or of the coating layer in insulating and permeable material 18 allows the surface to avoid direct contact and the formation of high intensity short circuits that would prevent activation of the electrolytic oxidation action.
  • the motion of the treatment takes place by rotating the roller electrode 12 on the surface either in an alternating motion or in a one-way motion normal to the axis of rotation of the roller 13.
  • the electrical current applied can be in direct or alternating current with a voltage of between 5 and 25 Volts and a current intensity on the affected surface of the electrode and the underlying metal surface with density commensurate with the size of the surface being treated.
  • the electrolytic action takes place from the contact line of the cylindrical surface 17 near the metal surface 2 being treated; with a coated roller 18 it can therefore operate from 1.0 to 10.0 A/cm2, whereas with only the rigid surface 17 of the roller 13 it operates at a current density ranging from at least 4.0 to 20.0 A/cm2.
  • the material constituting the roller electrode 12 is graphite, which in the most convenient dimension has the roller with an outer diameter DE of 64 mm and an inner diameter of 42 mm, while the electric current passes through the pin 21; only in the turning conical pair 25 does it pass from the pin to the roller which is substantially a graphite tube with the inner and outer diameters in the more advantageous size already mentioned.
  • the material constituting the pin and the turning pair is metallic and corrosion resistant. Furthermore, the turning pair can be made more advantageously of graphite.
  • the planar electrode, whether in a single plate or in a mesh, can be made either of metallic material, advantageously nickel, titanium and similar corrosion-resistant materials, or of graphite in the form of a continuous plate or even of a perforated plate, similar to a mesh, to allow the electrolyte to pass through the holes inside it.
  • the graphite design is preferred as it is cheaper and equally functional.
  • the planar electrode whether it is made of a metal that is obviously different from the metal of the surface being treated, or even of graphite, is not at all subject to wear by the electrolytic action developed.
  • the oxidation action was concentrated on the metal surface undergoing treatment so as to achieve high oxidation rates even for large surfaces to be treated.
  • Another very advantageous result over the known art lies in the uniformity of the treatment on the metal surface, be it sheet metal, wire cloth or wire mesh.
  • the metal surfaces on which the treatment takes place without masking the effect of the uniformity of the current density on the electrode and the constant distance, determined either by the thickness of the coating 18 or by the thickness of the passage printing screen, between the electrode and the metal surface allows, as mentioned, quick achievement of a desired and uniform colouration with the oxidation of the metal surface.
  • the advantage of placing the mask 38 on the passage printing screen 37 in the lower face of the screen itself, in contact with the surface being treated, has been verified: in this arrangement, even a simple digital ink printing, possibly carried out with UV printing, allows the mask to perform its function even for dozens of subsequent treatments.
  • the advantage obtained results from the practicality of the masking (very weak but effective), as it is not applied directly to a plate or surface being worked upon, thus avoiding the known operations of removing the masking applied to the surface being worked upon.
  • the advantage of using a band-coated roller electrode in absorbent and heat-resistant material makes it possible to carry out the treatment even with mechanised handling or robotic means, i.e. already present in devices and therefore not requiring direct human intervention.
  • the simplest form, and of manual application has allowed the functional and production tests described above, both with the various current densities indicated and with the treatment of the most varied metal surfaces as described.
  • the method of applying the oxidation described with the tank apparatus in forming an electrolytic cell makes it possible to automate fully the execution of the oxidation process.

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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)
  • Printing Plates And Materials Therefor (AREA)
  • Printing Methods (AREA)
EP21020636.3A 2020-12-11 2021-12-13 Dispositif d'oxydation pour surfaces métalliques planes, telles qu'une tôle, un tissu ou un treillis métallique et procédé d'application du traitement Pending EP4019670A1 (fr)

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Application Number Priority Date Filing Date Title
IT202000030569 2020-12-11

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EP4019670A1 true EP4019670A1 (fr) 2022-06-29

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2540602A (en) * 1946-07-03 1951-02-06 Lockheed Aircraft Corp Method and apparatus for the surface treatment of metals
JPS53124134A (en) * 1977-04-06 1978-10-30 Ichirou Sasaki Alumite treatment method of aluminium and its alloy
US4569730A (en) * 1984-01-26 1986-02-11 Bbc Brown, Boveri & Co., Ltd. Method for continuous coating of a solid electrolyte with a catalytically active material
JP2003211324A (ja) 2002-01-21 2003-07-29 Koyo Seiko Co Ltd 電解加工用電極およびそれを用いた電解加工方法
DE10344424A1 (de) * 2003-09-25 2005-05-12 Daimler Chrysler Ag Vorrichtung zur elektrochemischen Abscheidung eines Beschichtungsmaterials auf einem Substrat sowie Verfahren zur elektrochemischen Abscheidung
US20140360881A1 (en) 2013-04-05 2014-12-11 Metaly S.R.L. Electro-mark process and decoration of metallic surface and relative device
US20150014173A1 (en) 2012-01-30 2015-01-15 Metaly S.R.L. Machine for the electro-marking of large metallic surfaces and relative process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3554881A (en) * 1966-04-23 1971-01-12 Roberto Piontelli Electrochemical process for the surface treatment of titanium,alloys thereof and other analogous metals
FR1585605A (fr) * 1968-04-29 1970-01-30
JP2014525517A (ja) * 2011-09-08 2014-09-29 クリア メタルズ インコーポレイテッド 平らな導電性表面への酸化物層の形成

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2540602A (en) * 1946-07-03 1951-02-06 Lockheed Aircraft Corp Method and apparatus for the surface treatment of metals
JPS53124134A (en) * 1977-04-06 1978-10-30 Ichirou Sasaki Alumite treatment method of aluminium and its alloy
US4569730A (en) * 1984-01-26 1986-02-11 Bbc Brown, Boveri & Co., Ltd. Method for continuous coating of a solid electrolyte with a catalytically active material
JP2003211324A (ja) 2002-01-21 2003-07-29 Koyo Seiko Co Ltd 電解加工用電極およびそれを用いた電解加工方法
DE10344424A1 (de) * 2003-09-25 2005-05-12 Daimler Chrysler Ag Vorrichtung zur elektrochemischen Abscheidung eines Beschichtungsmaterials auf einem Substrat sowie Verfahren zur elektrochemischen Abscheidung
US20150014173A1 (en) 2012-01-30 2015-01-15 Metaly S.R.L. Machine for the electro-marking of large metallic surfaces and relative process
US20140360881A1 (en) 2013-04-05 2014-12-11 Metaly S.R.L. Electro-mark process and decoration of metallic surface and relative device

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