EP2516698B1 - Procédé de revêtement par pulvérisation thermique et placage électrochimique - Google Patents

Procédé de revêtement par pulvérisation thermique et placage électrochimique Download PDF

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Publication number
EP2516698B1
EP2516698B1 EP10784289.0A EP10784289A EP2516698B1 EP 2516698 B1 EP2516698 B1 EP 2516698B1 EP 10784289 A EP10784289 A EP 10784289A EP 2516698 B1 EP2516698 B1 EP 2516698B1
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EP
European Patent Office
Prior art keywords
layer
workpiece
process according
zones
coating
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EP10784289.0A
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German (de)
English (en)
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EP2516698A1 (fr
Inventor
Jens Dahl Jensen
Oliver Stier
Gabriele Winkler
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Siemens AG
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Siemens AG
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/615Microstructure of the layers, e.g. mixed structure
    • C25D5/617Crystalline layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/67Electroplating to repair workpiece
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/66Electroplating: Baths therefor from melts
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04Electroplating with moving electrodes
    • C25D5/06Brush or pad plating
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/04Tubes; Rings; Hollow bodies

Definitions

  • the invention relates to a method for coating a workpiece, on which a layer is produced electrochemically.
  • a method of the type mentioned is, for example, according to the DE 602 25 352 T2 described. It is possible according to this method to coat the surface of a workpiece electrochemically, for example by means of brush plating.
  • a flow, open-pore sponge or a brush is used as a carrier to transfer an electrolyte to the surface to be coated.
  • a metallic material is deposited on the surface by applying a voltage between the substrate and an electrode arranged in the region of the transmitter for the electrolyte from the electrolyte.
  • metal ions deposited from the molten salt on the surface to be coated must be replaced by new metal ions introduced into the molten salt, so that the separation process does not come to a standstill.
  • a method for keeping the concentration of metal ions constant is, for example, in US Pat DE 43 44 387 A1 described.
  • a method for coating a workpiece involves the coating of the workpiece with a metal layer, this being done by plasma spraying or flame spraying. Then another layer is applied, which can be done, for example, galvanically. The two layers have a different thermal expansion coefficient.
  • a workpiece can be provided by means of plasma spraying or flame spraying with a first layer. Then, a second coating is galvanically produced, for example, these layers having a different coefficient of expansion.
  • WO 02/12595 A1 discloses a method in which a workpiece can be coated with a metal layer by plasma spraying or flame spraying. In addition to this layer, a further coating can be produced, for example, galvanically. Furthermore, it is known that several layers can be produced, in which differences in the coefficient of thermal expansion can be compensated by design features. For this purpose, for example, voids in the layers are proposed. Such technical solutions can be, for example, the US 2005/029109 A1 and the EP 1 029 951 A2 remove.
  • the object of the invention is to improve an electrochemical coating method in such a way that the electrochemically deposited layers exhibit an inhomogeneous expansion behavior.
  • a part of the first material is applied by electrochemical coating on the workpiece, zones of a second material having a thermal expansion coefficient ⁇ , which differs from that of the first material, using a thermal spraying method be applied to the first material and these zones are then embedded by the electrochemical coating in the layer.
  • This embedding can take place in such a way that the zones still form part of the resulting surface of the coated component, so that the embedding takes place only on the lateral flanks of the zones.
  • Zones within the meaning of the invention are to be understood as meaning partial volumes of the layer whose lateral extent (ie extent seen in the direction parallel to the surface to be coated) is greater than its thickness extent (ie extent, measured perpendicular to the surface to be coated).
  • the thermal expansion behavior of the zones in the lateral direction of the layer is more noticeable than perpendicular to this direction.
  • the inhomogeneous expansion behavior of the layer produced is caused.
  • the second material has a larger thermal expansion coefficient ⁇ than the first material.
  • the expansion of the zones causes additional compressive stresses to form in the layer regions adjacent to the zones. These can be used to stabilize the layer structure, if this would react to tensile stresses, for example by formation of cracks.
  • an inhomogeneous expansion behavior of the layer can be produced by a suitable combination of the first and the second material and by suitable geometric design of the zones, which can be adapted to different design requirements for the component to be coated.
  • the zones can also be made of a material which has a lower thermal expansion coefficient ⁇ than the first material.
  • additional compressive stresses would be generated in the first material of the layer when the component is cooled with the layer. This could for example be advantageous if the first material of the layer tends to cold embrittlement and therefore must be protected at low temperatures before the occurrence of tensile stresses.
  • a cold gas spraying is applied as a thermal spraying method.
  • This is a process in which the coating particles adhere primarily due to their high kinetic energy on the surface. It is therefore also referred to as kinetic spraying.
  • the kinetic energy is generated by means of a cold gas spray nozzle, a convergent-divergent nozzle, in a gas jet, wherein heating of the particles not or only in small dimensions. In any case, heating is not enough to melt the particles, as with other thermal spraying methods.
  • the advantage in the application of cold gas spraying is therefore that the integrity of the structure of the particles used by the cold gas spraying is not affected.
  • this method has the advantage that, in particular in the case of a soft, electrochemically produced layer matrix of the preceding layer, the particles penetrate into the layer, as a result of which a better distribution of the particles in the formed layer is achieved.
  • the layer is produced in several layers by the thermal spraying process and the electrochemical coating are carried out alternately several times.
  • a layer structure can be produced in which the zones are completely embedded in the layer, ie. H. do not form a part of the surface. This is particularly advantageous when the material of the zones, for example, must be protected from corrosion attack.
  • the complete embedding of the zones allows a particularly effective introduction of tensile or compressive stresses into the surrounding microstructure matrix of the first material.
  • the thermal spraying and the electrochemical coating are carried out simultaneously, but in each case at different points of the workpiece.
  • This can advantageously achieve a particularly high efficiency in the coating of the workpiece.
  • the prerequisite is that the workpiece is only partially and simultaneously coated (at different locations) with both coating methods.
  • thermal spraying is this is required anyway, because always just the point of impact of the coating jet is coated.
  • electrochemical coating a coating method must be selected in which a partial coating of the component is possible, ie in which the entire component is not immersed in the electrolyte. This is preferably possible when applying the so-called brushing, wherein only the portion of the workpiece is currently electrochemically coated, which is in contact with the transmitter of the electrolyte.
  • the simultaneous coating of the workpiece with both coating methods can be used when a cylindrical body, in particular a work roll for rolling mills, is coated as a workpiece, wherein this is set in rotation about its center axis and at one point of its circumference the electrochemical coating and on another place of its extent the thermal spraying is made.
  • This can be accomplished, for example, by immersing the cylindrical workpiece in the electrolyte with only part of its peripheral surface.
  • For a uniform coating then ensures the uniform rotation of the cylindrical workpiece through which gradually the entire surface can be coated.
  • the thermal coating can be performed.
  • Even when using the Brush Platings the rotation of the roller is very advantageous.
  • the carrier for the brush plating then only has to be brought to the workpiece, wherein a relative movement between the workpiece and the transmitter by the constant rotation of the cylindrical workpiece comes about.
  • an ionic liquid is used as the electrolyte for the electrochemical coating.
  • Ionic liquids are organic liquids consisting of a cation such as an alkylated imidazolium, pyridinium, ammonium or phosphonium ion and an anion such.
  • a cation such as an alkylated imidazolium, pyridinium, ammonium or phosphonium ion and an anion such.
  • simple halides, tetrafluoroborates or Hexafluorophospaten, bi (trifluoromethylsulfonyl) imides or tri (pentafluoroethyl) -Trifluorophospaten exist.
  • ionic liquids also have a high electrochemical stability, inter alia Ti, Ta, Al and Si can be deposited, which can not be deposited from aqueous electrolytes due to the strong evolution of hydrogen.
  • Suitable metal salts which are also mentioned in the introduction WO 2006/061081 A2
  • halides, imides, amides, alcoholates and salts of mono-, di- or polyvalent organic acids such as acetates, oxalates or tartrates are mentioned.
  • the metals to be electrochemically deposited are brought into the appropriate ionic liquid by anodic dissolution.
  • a counter electrode to be coated component a soluble electrode is used. This consists of the metal that is to be coated.
  • the metal to be deposited may also be added as a salt of the ionic liquid.
  • a counterelectrode to the substrate for example, a platinum electrode can be used.
  • concentration of the metal ions to be deposited in the ionic liquid is maintained, which, for example, in the already mentioned DE 43 44 387 A1 will be described in more detail.
  • the metals are also deposited as nanocrystalline layers when using ionic liquids.
  • the ionic liquid suitable cations such as.
  • pyrrolinium ions which are surface active and therefore act as a grain refiner during electrochemical deposition. It is advantageous that it is often possible to dispense with the addition of wetting agents or brighteners under these conditions.
  • the zones can be distributed as island-like depots in a regular pattern on the workpiece.
  • These island-type depots are limited in size down only in that the gas jet of the applied cold gas spraying method creates a point of impact on the component to be coated, which has certain dimensions. This results in the smallest possible extent of the depot. If the depot to be larger, the cold gas jet in the production of the same must be performed in a suitable manner. It is advantageous to produce depots with a round base, but other geometries can be realized. By producing comparatively small depots, it is advantageously achieved that a tight exchange between the first material and the second material in the layer can be realized. As a result, voltage peaks in the structures of the first material and the second material can be kept low as soon as they arise due to the inhomogeneous expansion behavior of the layer.
  • Another possibility is to arrange the zones as strips on the workpiece. This can be an inhomogeneous Create expansion behavior, which is different not only in terms of the expansion behavior of the layer perpendicular to the surface of the workpiece, but also with respect to the lateral expansion behavior in different directions of the layer.
  • the zones are arranged as rectangles in a two-dimensional array on the workpiece.
  • the layer in the region of at least one zone on a sacrificial material for.
  • wax which is removed after the completion of the layer to form a cavity, for example by melting.
  • cantilever structures made of the first material with the zones of the second material and of the layer composite surrounding these zones, which structures can be used as mechanical actuating elements due to their inhomogeneous expansion behavior.
  • the driving force for the actuation of the actuators are therefore temperature differences during operation of the coated component.
  • the zone of the second material is formed together with the first material of the remaining layer to form a multilayer, cantilevered bending beam. At one end of the bending beam is then connected to the rest of the composite layer. Below the bending beam, the already mentioned cavity is formed, wherein the other end of the bending beam is freely movable. Due to the different expansion behavior of the two materials, which are preferably arranged in two adjoining layers, the beam bends according to the mechanism, which is known for example from bimetallic strip. In this way, the actuator is realized.
  • a bending beam formed in this way can be produced with its free-carrying end, for example, above an opening in the surface of the workpiece.
  • This opening can serve, for example, the supply of a cooling medium.
  • the bending beam can be designed so that the opening is only released when a certain temperature is exceeded, so that the coolant is conveyed only in the event of an imminent overheating of the component. This is advantageous realized a temperature-controlled valve. A throttling of the coolant flow can be ensured.
  • the zone is produced as a cantilever beam of the second material.
  • This has a larger thermal expansion coefficient ⁇ than the first material.
  • the bending beam is connected at its one end to the remaining layer composite and executed at its other end with a defined distance to the rest of the layer composite.
  • the beam thus formed on no component of the first material.
  • This structure can be used, for example, as a thermal switch. Upon heating of the component, the beam expands due to the larger thermal expansion coefficient ⁇ of the beam and bridged at a certain temperature the defined distance to the rest of the composite layer. This creates a contact that assumes an electrical conductivity of at least the second material and leads to a change in the electrical behavior of the layer. This can be measured and used as a switching signal. If the first material is an electrical insulator, this can be achieved by a suitable design of supply lines for example, realize an electrical switch with the beam from the first material.
  • the method can be used particularly advantageously for work rolls of a rolling mill. These serve, inter alia, the transport of goods to be rolled, z. As a sheet, which is reduced by the leadership between the work rolls, for example, in its wall thickness. Therefore, the work rolls of a rolling mill are subject to enormous wear. This can be reduced by the coatings applied according to the invention if particles of a hard material are preferably embedded in the zones. These may be, for example, oxides of Al, Co, Mg, Ti, Si or Zr, nitrides of Al, B or Si or carbides of B, Cr, Ti, Si or W or else carbonitrides.
  • the mentioned hard materials can be deposited together with particles of a matrix material as a second material in the zones.
  • the first material can be selected with a smaller thermal expansion coefficient than the second material in order to generate compressive stresses in the zones when heating the roll surface, which must be preserved because of the proportion of hard materials before the occurrence of tensile stresses in the structure. In the zones then comparatively high concentrations of hard material particles can be realized.
  • the hard materials used in the zones of the layer produced on the one hand advantageously reduce their abrasion, so that their wear resistance increases. Furthermore, however, the hard materials also serve the purpose of increasing the surface roughness of the layer, which is required so that the torque of the work rolls can be transferred to the sheet to be rolled. If the hard materials are provided by the multi-layer structure of the roller over the entire layer thickness, it is furthermore advantageously ensured that the surface roughness of the roller is maintained even if the layer undergoes continuous wear by exposing ever new hard material particles. This means that advantageously a component is created which meets the requirements of the surface roughness over its entire intended life in full measure.
  • electrochemically base metals such as Ti, Ta, Si, Al or Mg
  • An inexpensive deposition is especially by selecting the brush Plating process possible, since in this case a comparatively fast layer growth can be achieved. Particulate entry into the forming zones of the second material is possible and high particle concentrations in the layer can be achieved.
  • the process can also be carried out partially on large workpieces since they do not have to be immersed in an electrolyte during brush plating.
  • the method can also be used for repair purposes, wherein the coating system (consisting of a cold gas spray gun and a carrier for brush plating) is transportable and therefore also z. B. can be used at the site of the workpiece to be repaired.
  • a surface cleaning and activation is performed on the workpiece to be coated. This can be done for example by a so-called brush cleaning by means of an alkaline and / or cyanide electrolyte and brush etching by means of an acidic electrolyte such. For example, hydrochloric or sulfuric acid, take place.
  • the first coating step in which a ductile base material, such as. B. nickel or nickel-cobalt, is deposited as a first material. This process is done by means of brush plating.
  • a ductile base material such as. B. nickel or nickel-cobalt
  • the electrolyte for example, a Watts electrolyte can be used.
  • the transfer of the Brush Platings which may be a soaked with the electrolyte felt or sponge, is thereby moved over the surface to be coated.
  • an anode in the form of a rod, wire mesh or balls may be included.
  • the material of the anode is either the base material of the deposited layer, which then dissolves and regularly must be replaced, or an inert anode, such as platinum.
  • the coating is carried out in a non-aqueous electrolyte.
  • the surface cleaning and activation of the workpiece to be coated is carried out in the manner already described by brush cleaning and brush etching.
  • the first coating step takes place, wherein a metal layer is deposited, for example, from titanium. This process is done by means of brush plating.
  • the electrolyte used to deposit titanium as the first material is 1-butyl-3-methylimidazolium tetrafluoroborate, in which titanium tetrafluoroborate is dissolved as ion carrier.
  • a felt or sponge is soaked with this electrolyte and moved over the surface of the component to be coated.
  • the one formed by the felt or sponge Transmitter is equipped in the manner already described with an electrode. This may consist of titanium or an inert material, such as platinum.
  • the second coating step can be carried out in alternation with the electrochemical coating or at the same time at a point at which the electrochemical coating is not currently carried out.
  • zones are made of aluminum, for example, as the second material with said cold gas spraying.
  • the zones are then incorporated in the manner already described in the metal matrix by again titanium is deposited electrochemically.
  • FIG. 1 In the embodiment of the inventive method according to FIG. 1 is a roller-shaped workpiece 11 with a Provided wear protection layer.
  • the workpiece 11 is rotatably mounted with its central axis 12, wherein the axis of rotation 13 is identical to the central axis 12.
  • a bearing 14 is shown schematically, wherein during the coating, the workpiece 11 is rotated by means of a drive, not shown, at a constant speed.
  • FIG. 1 is a plan view of the workpiece 11 from top to bottom vertically shown.
  • a transfer device 15 is brought from one side to the workpiece, which consists of a sponge 16 with open pores.
  • an electrolyte is applied to the surface 18 of the workpiece in a manner not shown via a feed system 17, which moves away under the transmitter.
  • an electrochemical coating takes place, for which purpose the workpiece 11 and the transmitter is connected to a voltage source 19.
  • a cold gas spraying nozzle 20 is directed onto the surface 18 of the workpiece and guided stepwise approximately in the direction of the axis of rotation 13 over the surface.
  • small depots 27 are formed at the dwellers 26 (shown in FIG. 3 ) of the cold gas jet.
  • individual particles from the cold gas jet 21 adhere to the surface and are subsequently incorporated into the layer matrix on the transfer substrate 15 due to the rotation of the workpiece.
  • a range of movement 22 of the cold spray nozzle 20 is slightly less than the length of the workpiece, since for example in work rolls of rolling mills as workpieces to be coated, the respective frontal region is not involved in the rolling process and therefore is not exposed to heavy wear. If the movement region 22 of the cold gas spraying nozzle 20 is selected such that it does not extend to the edge of the workpiece to be coated, this has advantages for the process control.
  • the movement pattern of the cold spray nozzle is in FIG. 2 shown. This takes a course that corresponds to an eight, taking into account the constant movement 24 of the workpiece due to the rotation. By virtue of the eight-shaped course, a line 25 is formed on the surface 18 of the workpiece 11 FIG. 3 described so that it comes to a uniform loading of the surface with particles. In FIG. 3 are also the dwellers 26 of the cold gas jet shown, the construction of depots 27 in the coating material 28 according to FIG. 4 with a checkerboard-like layer structure leads.
  • FIG. 4 is a plan view of the layer surface represents. It can be seen that the depots 27 are embedded in the first material 28 of the layer so that they form part of the layer surface. In FIG. 5 however, the depots 27 are completely surrounded by the material 28 of the layer. This can be achieved by carrying out an electrochemical coating step with the first material 28 of the layer after application of the depots 27 without once again applying the second material. A thus formed layer 29 thus has three layers 30, of which only the middle is equipped with the depots 27.
  • the layer surface is shown with exposed strips 31 of the second material, which are embedded in the first material 28 on the side edges.
  • Another embodiment results when instead of the strips 31 rectangles 32 are produced, as shown in Figure 7. These too are exposed at the top, so that they can be seen in the layer surface, while they are embedded with their sides by the first material.
  • a bending beam 33 can be integrated.
  • wax 34 is applied in a predetermined shape to the component 11 as a sacrificial material, wherein the sacrificial material also closes an opening 35 in the component 11 and thus prevents it from being closed by the coating process.
  • the first material 28 is first deposited electrochemically, wherein the sacrificial material must be provided with an electrically conductive starting layer for this purpose.
  • a zone 36 is produced by cold gas spraying onto the first material and then embedded in the first material 28 at its flanks 36a.
  • FIGS. 9 and 10 Another embodiment is in the FIGS. 9 and 10 to see, with the sectional planes of the other figures are drawn accordingly (section XX corresponds to the sectional plane in FIG. 10 and section IX-IX of the section plane in FIG. 9 ).
  • a bar 37 is shown, which is integrated in the layer 29.
  • the beam 37 which consists entirely of the second material, embedded in the first material 28 (see. FIG. 10 ) and thus fixed in the region of the layer 29.
  • the sacrificial material 34 By the sacrificial material 34, a cavity is defined, which results in that the beam 37 is arranged freely supported in the layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (14)

  1. Procédé de revêtement d'une pièce ( 11 ), sur laquelle est produite électrochimiquement une couche ( 26 ), en un premier matériau,
    caractérisé
    en ce que
    - une partie du premier matériau est déposée sur la pièce ( 11 ) par revêtement électrochimique,
    - des zones d'un deuxième matériau ayant un coefficient α de dilatation thermique, qui s'écarte de celui du premier matériau, sont déposées sur le premier matériau, en appliquant un procédé de pulvérisation thermique et
    - ensuite les zones en le deuxième matériau sont incorporées dans la couche ( 26 ) par le revêtement électrochimique.
  2. Procédé suivant la revendication 1,
    caractérisé
    en ce que le deuxième matériau a un coefficient α de dilatation thermique plus grand que le premier matériau.
  3. Procédé suivant l'une des revendications précédentes,
    caractérisé
    en ce que l'on applique une pulvérisation par gaz froid comme procédé de pulvérisation thermique.
  4. Procédé suivant l'une des revendications précédentes,
    caractérisé
    en ce que l'on produit la couche ( 26 ) en plusieurs strates ( 28 ), en effectuant le procédé de pulvérisation thermique et le revêtement électrochimique plusieurs fois.
  5. Procédé suivant la revendication 4,
    caractérisé
    en ce que l'on effectue la pulvérisation thermique et le revêtement électrochimique en même temps, mais en des endroits différents respectivement de la pièce ( 11 ).
  6. Procédé suivant la revendication 5,
    caractérisé
    en ce que l'on utilise un liquide ionique comme électrolyte pour le revêtement électrochimique.
  7. Procédé suivant l'une des revendications précédentes,
    caractérisé
    en ce que l'on répartit les zones sous la forme de dépôts ( 27 ) de type en îlot suivant un modèle régulier sur la pièce.
  8. Procédé suivant l'une des revendications 1 à 6,
    caractérisé
    en ce que les zones sont disposées sous la forme de bandes ( 31 ) sur la pièce ( 11 ) .
  9. Procédé suivant l'une des revendications 1 à 6,
    caractérisé
    en ce que les zones sont disposées sous la forme de rectangles ( 32 ) suivant un réseau en deux dimensions sur la pièce.
  10. Procédé suivant l'une des revendications 1 à 6,
    caractérisé
    en ce que l'on produit la couche ( 26 ) dans la région d'au moins une zone, sur un matériau ( 34 ) sacrificiel, qui est éliminé avec formation d'une cavité, après que la production de la couche ( 26 ) est finie.
  11. Procédé suivant la revendication 10,
    caractérisé
    en ce que l'on forme la zone, ensemble avec le premier matériau, en une poutre ( 33 ) de flexion en porte à faux à plusieurs strates, qui est reliée à l'une de ses extrémités aux composites de couches restants.
  12. Procédé suivant la revendication 11,
    caractérisé
    en ce que l'on produit la couche ( 33 ) de flexion avec son extrémité en porte à faux au dessus d'une ouverture ( 35 ) de la surface de la pièce ( 11 ).
  13. Procédé suivant la revendication 10,
    caractérisé
    en ce que l'on produit la zone, sous la forme d'une poutre ( 37 ) en porte à faux, en le deuxième matériau,
    • qui a un coefficient α de dilatation thermique plus grand que le premier matériau,
    • qui est reliée, par l'une de ses extrémités, aux composites de couches restants et
    • qui est produite, à son autre extrémité, à une distance définie du composite de couches restant.
  14. Procédé suivant l'une des revendications précédentes,
    caractérisé
    en ce que le composant ( 11 ) a un axe ( 13 ) de rotation et les parties de la couche, pourvues de zones, alternent, dans la direction périphérique considérée par rapport à l'axe ( 13 ) de rotation, avec des parties de la couche sans ces zones.
EP10784289.0A 2009-12-22 2010-11-19 Procédé de revêtement par pulvérisation thermique et placage électrochimique Not-in-force EP2516698B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009060937A DE102009060937A1 (de) 2009-12-22 2009-12-22 Verfahren zum elektrochemischen Beschichten
PCT/EP2010/067830 WO2011076499A1 (fr) 2009-12-22 2010-11-19 Procédé de revêtement électrochimique

Publications (2)

Publication Number Publication Date
EP2516698A1 EP2516698A1 (fr) 2012-10-31
EP2516698B1 true EP2516698B1 (fr) 2014-04-02

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US (1) US20120269982A1 (fr)
EP (1) EP2516698B1 (fr)
DE (1) DE102009060937A1 (fr)
WO (1) WO2011076499A1 (fr)

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CN114505210B (zh) * 2020-11-17 2023-06-23 武汉苏泊尔炊具有限公司 刀具加工方法与刀具

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4753849A (en) * 1986-07-02 1988-06-28 Carrier Corporation Porous coating for enhanced tubes
FI83439C (fi) * 1989-08-24 1991-07-10 Valmet Paper Machinery Inc Vals i pappersmaskin och foerfarande foer framstaellning av denna.
US5268045A (en) * 1992-05-29 1993-12-07 John F. Wolpert Method for providing metallurgically bonded thermally sprayed coatings
DE4344387C2 (de) 1993-12-24 1996-09-05 Atotech Deutschland Gmbh Verfahren zur elektrolytischen Abscheidung von Kupfer und Anordnung zur Durchführung des Verfahrens
CN1122121C (zh) * 1994-05-24 2003-09-24 东洋钢板株式会社 带材处理装置
JP3269827B2 (ja) * 1997-04-04 2002-04-02 ユニバーシティ・オブ・サザン・カリフォルニア 電気化学製造のための物品、方法、および装置
WO2002012595A1 (fr) * 2000-07-24 2002-02-14 Pohang Iron & Steel Co., Ltd Procede destine a la reduction d'une marque de bande sur une feuille d'acier d'electrodeposition
DE10052405A1 (de) * 2000-10-20 2002-05-02 Rwth Aachen Inst Fuer Werkstof Verfahren zum Herstellen einer Verbundstruktur mit einem zellularen Werkstück sowie mit diesem hergestellte Verbundstruktur
US20040146650A1 (en) * 2002-10-29 2004-07-29 Microfabrica Inc. EFAB methods and apparatus including spray metal or powder coating processes
US7259640B2 (en) * 2001-12-03 2007-08-21 Microfabrica Miniature RF and microwave components and methods for fabricating such components
JP4554357B2 (ja) * 2002-05-07 2010-09-29 マイクロファブリカ インク 電気化学的に成型加工され、気密的に封止された微細構造および上記微細構造を製造するための方法および装置
US20050029109A1 (en) * 2002-05-07 2005-02-10 Gang Zhang Method of electrochemically fabricating multilayer structures having improved interlayer adhesion
ATE387522T1 (de) 2002-06-25 2008-03-15 Integran Technologies Inc Verfahren zur elektroplattierung von metallischen und metall-matrix-composite folien, beschichtungen und mikrokomponenten
DE102004059520A1 (de) * 2004-12-10 2006-06-14 Merck Patent Gmbh Elektrochemische Abscheidung von Tantal und/oder Kupfer in ionischen Flüssigkeiten
DE102005008487C5 (de) * 2005-02-24 2011-08-18 Praxair S.T. Technology, Inc., Conn. Beschichteter Körper aus Kohlefaser verstärktem Kunststoff für Papier- und Druckmaschinen, insbesondere Walze, und Verfahren zum Herstellen eines solchen Körpers
JP4469385B2 (ja) * 2007-05-31 2010-05-26 株式会社日立産機システム 微細モールド及びその製造方法
US8609206B2 (en) * 2008-05-01 2013-12-17 Maxim Seleznev Continuous or discrete metallization layer on a ceramic substrate

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US20120269982A1 (en) 2012-10-25
EP2516698A1 (fr) 2012-10-31
DE102009060937A1 (de) 2011-06-30
WO2011076499A1 (fr) 2011-06-30

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