EP3101155B1 - Metallisation method and tool for the production of complex shadings - Google Patents

Metallisation method and tool for the production of complex shadings Download PDF

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Publication number
EP3101155B1
EP3101155B1 EP16172954.6A EP16172954A EP3101155B1 EP 3101155 B1 EP3101155 B1 EP 3101155B1 EP 16172954 A EP16172954 A EP 16172954A EP 3101155 B1 EP3101155 B1 EP 3101155B1
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EP
European Patent Office
Prior art keywords
connector
support arm
support
metallization
tool
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EP16172954.6A
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German (de)
French (fr)
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EP3101155A1 (en
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Olivier CARTON
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Individual
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating

Definitions

  • the invention relates to a metallization method of a surface of a part such as a bottle or a bottle, and a workpiece support tool for carrying out this method.
  • the invention is particularly applicable to the metallization of glass or plastic parts.
  • This process involves several steps of preparation and treatment of the part to improve the efficiency of the metallization.
  • the method comprises firstly a step of projecting a base varnish on the surface of the part, then allowing the deposited metal to adhere to the surface of the part.
  • a surface treatment is then used to oxidize the base varnish and change the surface tension of the varnish to improve its wettability.
  • This surface treatment is for example a flame, that is to say the exposure for a reduced duration of the room to a flame.
  • the treatment may then comprise an activation step, or sensitization of the surface to be covered, by spraying a solution based on stannous chloride SnCl 2, and then rinsing.
  • the metallization itself is carried out by projecting on the surface of the piece one or more redox solutions containing metal ions, causing a precipitation of metal directly on the surface of the piece.
  • the metallization is advantageously carried out by simultaneous spraying of a solution containing Ag + silver ions, and a reducing solution.
  • the piece to be metallized is fixed on a support.
  • a support For example, in the case where the piece is a bottle or a bottle, it is mounted on a support by its mouth, the support being arranged vertically of the piece, below or above it.
  • the carrier generally drives the rotating part to provide uniform metallization over the entire circumference of the part.
  • Such a metallization process makes it possible to produce an opaque or translucent metal coating, as a function of the quantity of metal precipitated on the surface, and therefore of the duration of the spray of redox solution and / or the speed of rotation of the part. on its support.
  • the method of metallization by spraying redox solutions involves spraying these solutions in excess relative to the amount of metal to be deposited on the surface of the workpiece.
  • the result of the spraying is a runoff of water and silver on the surface of the room, which flows along the room to the ground due to gravity, and some of the money can be deposited. on the piece.
  • the most opaque portion of a metallization gradient is necessarily on the side of the room closest to the ground when spraying is performed.
  • the bottle is held by its mouth by a support disposed above the bottle, a metallic gradient is obtained from the mouth, which is translucent or transparent, towards the base, completely opaque.
  • the aim of the invention is to overcome the drawbacks of the prior art by proposing a metallization process which makes it possible to produce a double gradient one piece, comprising, at the ends of a piece, two relatively little metallized areas, and between the ends, at least one relatively more metallized area.
  • the invention also aims to provide a tool for implementing this method.
  • the method according to the invention provides for tilting the workpiece from a substantially vertical position for the implementation of the redox solution projection step. In this way, the piece can be brought on a substantially horizontal axis, which has the effect of eliminating the flow of metal to other sections than the section that is to be metallized.
  • the proposed tool can be mounted directly on existing industrial installations. It makes it possible to impart to the part a rotational movement around its support arm regardless of the angle formed between the support arm and the drive shaft on which the tool is mounted, which makes it possible to conserve homogeneity of metallization on a circumferential section of the part, whatever the angle in which the support arm is located.
  • the tool makes it possible to block the piece and its support arm at several possible angles in an angular range, which makes it possible to bring parts of complex geometries into a horizontal position.
  • the part 1 to be metallized is advantageously a rigid part, made of a material such as a glass, a plastic, a composite material, or a metal, an alloy, etc.
  • the part 1 is preferably a bottle having a neck 10, such as for example a bottle for storing a cosmetic product or perfume, a bottle, etc.
  • the piece 1 is not limited in its form to a bottle. It may for example be any other type of container, for example a glass, or any other three-dimensional object.
  • the metallization process comprises a succession of steps for treating the surface of the part to be metallized.
  • the part 1 is positioned on a support arm 20, extending along a longitudinal axis.
  • the support arm 20 is mounted on a conveyor and driven in translation by it, to bring the part 1 to the different stages of the process.
  • the support arm 20 is advantageously shaped to be able to be fixed to the workpiece 1 without degrading it.
  • the support arm 20, visible on the figure 3 may for example comprise a tube 21 adapted to be mounted inside or outside a neck 10 of a bottle, and two elastic rods 22 can be folded against each other for their insertion to the inside of the bottle by the neck.
  • the elastic nature of the rods 22 tends to remove them once they are inside the bottle to bear against the inner walls of the bottle.
  • This support makes it possible to maintain the bottle in position relative to the support arm 20, and also to make the bottle integral with rotation of the arm 20 when it itself pivots.
  • the support arm may comprise at least one clamp (not shown) for fixing the workpiece by clamping the clamp on the workpiece.
  • the first step 100 of the method comprises the projection on the part 1 of a base coating.
  • This coating makes it possible to smooth the surface of the part to prepare it for the projection of a metallic precipitate.
  • a water-soluble or organic varnish preferably water-soluble selected, depending on the constituent material of the part to be coated, among the following compounds: alkyds, polyurethanes, epoxys, vinyls, acrylics and mixtures thereof.
  • it is an epoxy varnish, or a water-soluble vinyl or polyurethane varnish.
  • the part 1 is fixed to the support arm 20, which is in a vertical position, that is to say that the axis of the arm 20 is vertical.
  • the axis of the support arm 20 is generally coincident with the axis of the neck 10, so that the axis of the neck is also vertical.
  • the part 1 has a generally cylindrical shape, coaxial with the axis of the neck. This is particularly the case for most bottles.
  • the workpiece extends substantially vertically above or below the conveyor.
  • the support arm 20 is rotatable about its longitudinal axis to rotate the workpiece 1. In this way, the base coat projection is uniform over the entire surface of the workpiece.
  • the part is thus conveyed by the conveyor to a module 3 in which nozzles 30 project the base coating onto the part.
  • the part 1 is advantageously subjected to firing or exposure to UV radiation to crosslink the base coating.
  • the method then comprises a step 200 of decreasing the surface tension of the base coating, to facilitate the adhesion of the metal precipitate on the part.
  • This step 200 is advantageously a flaming step, that is to say a step of subjecting the surface of the piece 1 to a flame.
  • this step can be implemented by rotating the workpiece, and subjecting it to a flame at between 1200 and 1700 ° C, for example 1400 ° C, for a duration of a few seconds, advantageously between 4 and 50 seconds.
  • a temperature of flame of 1400 ° C the part being rotated at a speed of 120 revolutions / minutes, the flame lasts 20 seconds.
  • the support arm 20 holding the workpiece is advantageously always in a vertical position, and rotates the workpiece, so as to allow a homogeneous flame of the entire surface of the workpiece.
  • the support arm 20 of the workpiece can be inclined with respect to the vertical position in accordance with the description which follows in step 330.
  • the part 1 is always driven by the conveyor, from the output of the module 3 to a flaming module 4 comprising nozzles 40 flaming.
  • the step 200 of decreasing the surface tension of the base coating can also be implemented by treatments of the corona treatment, plasma treatment or chemical treatment type, as described in more detail in the document FR 2 934 609 .
  • the method then comprises a metallization step 300 comprising the projection 330 of at least one oxido-reducing solution comprising metal ions on the surface of the part 1.
  • this step 330 is implemented using pairs of nozzles 50 positioned in a projection module 5.
  • a first nozzle projects onto the part a solution of metal ions, for example silver ions Ag +, for example a solution of silver nitrate.
  • the silver concentration of the Ag + ion solution is preferably chosen to be between 0.1 g / l and 100 g / l, and preferably between 1 and 60 g / l.
  • a second nozzle simultaneously projects on the part a reducing solution, for example an aqueous solution based on glucose at 15 g / L.
  • the reducing agent of the solution may be chosen from the group of compounds comprising borohydrides, dimethlaminoborane, hydrazine, sodium hupophosphite, formaldehyde, lithium aluminum hydride, reducing sugars, and mixtures thereof.
  • the reducing concentration of the solution is preferably between 0.1 g / l and 100 g / l and preferably between 1 and 60 g / l.
  • the support arm 20 of the part 1 is inclined, automatically or manually, with respect to the vertical position in which it was during steps 100 and 200.
  • the support arm 20 is inclined up to its longitudinal axis is in a position between the vertical position and a horizontal position.
  • the support arm is inclined in a horizontal position.
  • the support arm 20 is inclined at an angle such that a surface S of the part to be metallized homogeneously extends substantially vertically. In this way, the gravity causing a vertical run off of the surplus chemical reaction, they remain on the surface S of the piece to be metallized.
  • a preferred embodiment is that in which the piece is a symmetrical bottle of revolution about an axis coincident with the axis of the neck 10 of the bottle.
  • the surface is a circumferential surface extending perpendicularly to the axis of revolution of the bottle.
  • the support arm 20 is advantageously inclined until it reaches a horizontal position, so that the bottle also extends horizontally and that the strip S to be metallized extends vertically.
  • the support arm 20 is inclined at an angle equal to the angle ⁇ with respect to the vertical, so as to bring the surface S in a substantially vertical direction during the projection step.
  • ⁇ is less than or equal to 90 ° so that the bottle does not bother the conveyor.
  • the piece 1 the piece is preferably always rotated around the arm 20 during the 330 projection step.
  • the surface to be metallized extends along a vertical direction during the projection step 330 while pivoting around the arm 20 makes it possible to eliminate the effects of the gravity tending to make the surpluses of the reaction reaction run off. Oxidation reduction along the piece towards one of its ends. Instead, the surpluses remain on the projection surface, being distributed homogeneous way around the entire circumference of the room through the rotation of the room.
  • the modulation of the gradient on the surface of the part can also be obtained by modulating the speed of the conveyor and by varying the concentrations of the reagents of the redox solution (s).
  • the method further comprises preliminary steps 310, 320 to the projection of redox solutions, to prepare the surface to be metallized.
  • a preliminary preliminary step 310 the part 1 is brought, at the output of the flaming module 4, into a module 6 in which an activation solution is projected onto the part.
  • This solution is advantageously a stannous chloride solution.
  • the activation step 310 can be implemented according to the sensitization step described in the document FR 2 763 962 .
  • a step 320 rinsing the stannous chloride residues, by spraying a rinsing liquid, for example water.
  • a rinsing liquid for example water.
  • the part can then be dried by air circulation (not shown).
  • the inclination of the support arm 20 in perspective of step 330 is implemented at the end of this step 320 rinsing. Alternatively, it can be implemented before or after the flaming step. The inclination can be implemented manually or automatically.
  • step 330 of redox solution projection to metallize the workpiece the workpiece 1 is then brought into a finishing module 7 to obtain a finishing layer during a finishing step 400.
  • the support arm 20 of the part is repositioned vertically for the implementation of this step, the repositioning can be performed manually or automatically.
  • the finishing step is carried out for example by projection on the piece of a finishing varnish.
  • finishing step described in the document FR 2 934 609 for more information on possible implementations of the finishing step.
  • This tool 9 comprises a first connector 90, adapted to be mounted integral with a support arm 20 of the part, shown in dotted lines on the figure 4b .
  • the connector 90 is advantageously a shaft comprising means for rotating the support arm.
  • these means may take the form of splines (not shown) arranged on the circumference of the connector 90, and adapted to cooperate with complementary splines of the support arm 20.
  • one of the connector 90 and the support arm 20 can receive the other by snapping, tightening, or screwing, etc.
  • the support tool 9 also comprises a second connector 91.
  • This second connector is adapted to be mounted integral with a drive shaft 23.
  • This drive shaft 23 is itself mounted on the conveyor 2 and is driven by rotation and translation by the conveyor 2.
  • the connector 91 is advantageously a shaft comprising means for driving in rotation from or through the drive shaft 23.
  • the connector 91 comprises splines 910 adapted to drive in rotation complementary splines of the drive shaft 23 (not shown).
  • one of the connector 91 and the drive shaft 23 can receive the other by snapping, tightening, screwing, etc.
  • the connectors 90, 91 of the tool therefore extend along respective longitudinal axes, which are advantageously coplanar.
  • the connector pins 90, 91 form between them an angle that can vary over an angular range.
  • This angular range is advantageously between 10 and 100 °, preferably of the order of 90 °, to allow, in use, the support arm 20 to move from a vertical position to a horizontal position while the rotary shaft 23 remains upright.
  • the support tool comprises a housing formed of two shells 92, 93, the shells being able to be assembled one on the other by allowing a relative pivoting movement between the two shells on said angular range.
  • each connector 90, 91 is attached to a respective shell 92, 93.
  • Each connector 90, 91 comprises an end 902, 912 penetrating inside the housing 94 through an orifice arranged in the wall of one or both shells.
  • each connector is integral in rotation with the shell on which it is mounted.
  • the first shell 92 comprises a bottom wall 920 comprising a circular edge and a cylindrical or cylinder sector wall 921 extending around a portion of the edge of the bottom wall 920, perpendicular to the plane of the wall 920.
  • the cylindrical wall 921 extends over an angular aperture corresponding to the complementary of the angular range of relative rotation of the connectors over 360 °.
  • the second shell 93 also comprises a bottom wall 930, comprising a circular edge of slightly smaller diameter than that of the wall 920.
  • the second shell 93 also comprises a cylindrical wall 931 extending circumferentially around the edge of the wall 930, perpendicularly in the plane of the wall 930.
  • the difference in diameter between the bottom walls 920 and 930 corresponds to the thickness of the cylindrical wall 930.
  • the first shell 92 can be mounted around the second 93 and pivot on it with respect to an axis passing through the centers of the bottom walls 920, 930, perpendicular to the axes of the connectors 90 and 91.
  • the cylindrical walls 931 extending in opposite directions with respect to the respective bottom walls 920, 930, the shells cooperate to form the housing 94.
  • first shell 92 comprises an orifice 922 adapted to receive a section of the connector 90.
  • the connector 90 is rotatably mounted in the orifice 922 but is held fixed in translation by stop means 80 shown schematically on the figure 4b .
  • the first shell 93 also comprises an orifice 932 adapted to receive a section of the connector 91.
  • the connector 91 is rotatably mounted in the orifice 932 but is also held fixed in translation by stop means 81.
  • the second shell also comprises a second orifice 933 extending over an angular sector corresponding to the relative rotation range of the connectors.
  • the orifice 922 opens into the orifice 933 so as to allow the pivot of the connector 90 relative to the shell 93 on the angular range of displacement.
  • the orifice 932 of the first shell opens on the portion of the shell 92 without cylindrical wall, so as to allow the pivot of the connector 91 relative to the shell 92 on the angular range of displacement.
  • the tool 9 also comprises stop means 95 rotating a connector relative to the other connector on a plurality of relative positions among those covered by the angular range of pivot.
  • the stop means may advantageously be a plurality of shims in an arc of a diameter equal to the diameter of the shell 92. These shims may be inserted between the connector 91 and the cylindrical wall 921 to prevent relative rotation of these two elements. . Depending on the angular sector covered by the wedges, several angles can thus be blocked.
  • the shells 92 and 93 may comprise latching means which hold the shells in a constant relative position, until pressure is exerted to disengage the latching means.
  • snap-fastening means 95 consisting of a pin 950 projecting on the cylindrical wall 931 and several orifices 951 arranged on a surface facing the housing 94 of the cylindrical wall 921. In which hole is engaged the pin, several relative angular positions of the shells (and connectors) can be blocked.
  • the support tool also comprises a member 96 for transmitting a rotational movement from one to the other connector over the entire angular range of relative displacement of the connectors.
  • the member 96 comprises for this purpose a conical pinion which is arranged inside the housing, the conical pinion having an axis orthogonal to the plane in which the connectors 90, 91 extend. This axis corresponds to the pivot axis relative of the two hulls 92, 93 and connectors.
  • each connector located inside the housing 94 also comprises a respective conical pinion 903, 913 adapted to mesh with the pinion 96.
  • means 82 preventing this drive can be provided.
  • it may be a bearing interposed between the connector 91 and the hull 93.
  • the shell 93 may comprise a protrusion 82 extending around the connector 91 and having a square section end.
  • the conveyor 2 is advantageously lined with slides 83 in the metallization module 5, whose width corresponds to one side of the section of the protuberance 82.
  • the support tool is held fixed in one direction only by the slides at the approach of the module 5.
  • An operator can to check that this direction is correct, and reposition if necessary the tool in the right direction, for example a direction parallel to the direction of travel of the conveyor as in Fig 2c.
  • a system comprising a tool 9, a support arm 20 and a drive shaft 23 mounted on a conveyor 2 can thus allow the assembly of a part for the realization of complex metallizations, and in particular metallizations comprising several gradients on the same room.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Description

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

L'invention concerne un procédé de métallisation d'une surface d'une pièce telle qu'un flacon ou une bouteille, et un outil de support de la pièce permettant la mise en oeuvre de ce procédé.The invention relates to a metallization method of a surface of a part such as a bottle or a bottle, and a workpiece support tool for carrying out this method.

L'invention s'applique notamment à la métallisation de pièces en verre ou en plastique.The invention is particularly applicable to the metallization of glass or plastic parts.

ETAT DE LA TECHNIQUESTATE OF THE ART

On connaît déjà du document FR 2 934 609 un procédé de métallisation d'une pièce telle qu'un flacon, pouvant être en verre, en plastique, en matériau composite, ou encore en métal, etc.We already know document FR 2 934 609 a method of metallizing a part such as a bottle, which may be glass, plastic, composite material, or metal, etc.

Ce procédé comporte plusieurs étapes de préparation et de traitement de la pièce pour améliorer l'efficacité de la métallisation.This process involves several steps of preparation and treatment of the part to improve the efficiency of the metallization.

En particulier, le procédé comporte d'abord une étape de projection d'un vernis de base sur la surface de la pièce, permettant ensuite au métal déposé d'adhérer à la surface de la pièce.In particular, the method comprises firstly a step of projecting a base varnish on the surface of the part, then allowing the deposited metal to adhere to the surface of the part.

Un traitement de surface est ensuite mis en oeuvre pour oxyder le vernis de base et modifier la tension de surface du vernis pour améliorer sa mouillabilité. Ce traitement de surface est par exemple un flammage, c'est-à-dire l'exposition pendant une durée réduite de la pièce à une flamme.A surface treatment is then used to oxidize the base varnish and change the surface tension of the varnish to improve its wettability. This surface treatment is for example a flame, that is to say the exposure for a reduced duration of the room to a flame.

Le traitement peut ensuite comprendre une étape d'activation, ou de sensibilisation de la surface à recouvrir, par projection d'une solution à base de chlorure stanneux SnCl2, puis un rinçage.The treatment may then comprise an activation step, or sensitization of the surface to be covered, by spraying a solution based on stannous chloride SnCl 2, and then rinsing.

Enfin, la métallisation en tant que telle est effectuée en projetant sur la surface de la pièce une ou plusieurs solutions oxydo-réductrices contenant des ions métalliques, causant une précipitation de métal directement sur la surface de la pièce.Finally, the metallization itself is carried out by projecting on the surface of the piece one or more redox solutions containing metal ions, causing a precipitation of metal directly on the surface of the piece.

Par exemple, la métallisation est avantageusement effectuée par pulvérisation simultanée d'une solution contenant des ions argent Ag+, et d'une solution réductrice.For example, the metallization is advantageously carried out by simultaneous spraying of a solution containing Ag + silver ions, and a reducing solution.

Pour la mise en oeuvre industrielle de cette étape, la pièce à métalliser est fixée sur un support. Par exemple, dans le cas où la pièce est un flacon ou une bouteille, elle est montée sur un support par son embouchure, le support étant disposé à la verticale de la pièce, en-dessous ou au-dessus de celle-ci.For the industrial implementation of this step, the piece to be metallized is fixed on a support. For example, in the case where the piece is a bottle or a bottle, it is mounted on a support by its mouth, the support being arranged vertically of the piece, below or above it.

En outre, le support entraine en général la pièce en rotation pour assurer une métallisation uniforme sur toute la circonférence de la pièce.In addition, the carrier generally drives the rotating part to provide uniform metallization over the entire circumference of the part.

Un tel procédé de métallisation permet de réaliser un revêtement métallique opaque ou translucide, en fonction de la quantité de métal précipitée sur la surface, et donc de la durée de pulvérisation de solution oxydo-réductrice et/ou de la vitesse de rotation de la pièce sur son support.Such a metallization process makes it possible to produce an opaque or translucent metal coating, as a function of the quantity of metal precipitated on the surface, and therefore of the duration of the spray of redox solution and / or the speed of rotation of the part. on its support.

Il est également possible de réaliser des dégradés de métallisation, depuis une zone translucide jusqu'à une zone complètement opaque, en faisant varier la quantité de métal déposée le long de la surface de la pièce.It is also possible to perform metallization gradients, from a translucent zone to a completely opaque zone, by varying the amount of metal deposited along the surface of the part.

Cependant, compte-tenu des contraintes industrielles de production des pièces, toutes les possibilités de dégradés ne sont pas permises. En effet, le procédé de métallisation par pulvérisation de solutions oxydo-réductrices implique de pulvériser ces solutions en excès par rapport à la quantité de métal à déposer sur la surface de la pièce.However, given the industrial constraints of production of the parts, all the possibilities of gradients are not allowed. Indeed, the method of metallization by spraying redox solutions involves spraying these solutions in excess relative to the amount of metal to be deposited on the surface of the workpiece.

Il résulte de la pulvérisation un ruissellement d'eau et d'argent sur la surface de la pièce, qui s'écoule le long de la pièce vers le sol du fait de la gravité, et dont une partie de l'argent peut se déposer sur la pièce.The result of the spraying is a runoff of water and silver on the surface of the room, which flows along the room to the ground due to gravity, and some of the money can be deposited. on the piece.

Ainsi la partie la plus opaque d'un dégradé de métallisation se trouve nécessairement du côté de la pièce le plus proche du sol lorsque la pulvérisation est réalisée.Thus the most opaque portion of a metallization gradient is necessarily on the side of the room closest to the ground when spraying is performed.

On comprend que pour un flacon, si le flacon est tenu par son embouchure, par un support disposé sous le flacon, il est possible de faire un dégradé métallique depuis la base, translucide ou transparente, vers l'embouchure du flacon complètement opaque.It is understood that for a bottle, if the bottle is held by its mouth, by a support disposed under the bottle, it is possible to make a metal gradient from the base, translucent or transparent, towards the mouth of the bottle completely opaque.

Si en revanche le flacon est tenu par son embouchure par un support disposé au-dessus du flacon, on obtient un dégradé métallique depuis l'embouchure, translucide ou transparente, vers la base, complètement opaque.If, on the other hand, the bottle is held by its mouth by a support disposed above the bottle, a metallic gradient is obtained from the mouth, which is translucent or transparent, towards the base, completely opaque.

Il n'est donc pas possible de réaliser un dégradé double, comprenant une partie complètement métallisée et opaque au milieu d'une pièce, et deux parties moins métallisées aux extrémités de la pièce.It is therefore not possible to achieve a double gradient, including a completely metallized and opaque part in the middle of a room, and two less metallized parts at the ends of the room.

DESCRIPTION DE L'INVENTIONDESCRIPTION OF THE INVENTION

L'invention a pour but de pallier les inconvénients de l'art antérieur, en proposant un procédé de métallisation permettant de réaliser un dégradé double d'une pièce, comprenant, aux extrémités d'une pièce, deux zones relativement peu métallisées, et entre les extrémités, au moins une zone relativement plus métallisée.The aim of the invention is to overcome the drawbacks of the prior art by proposing a metallization process which makes it possible to produce a double gradient one piece, comprising, at the ends of a piece, two relatively little metallized areas, and between the ends, at least one relatively more metallized area.

L'invention a également pour but de proposer un outil permettant la mise en oeuvre de ce procédé.The invention also aims to provide a tool for implementing this method.

A cet égard, l'invention a pour objet un procédé de métallisation de la surface d'une pièce, la pièce étant maintenue sur un bras de support, le procédé comprenant les étapes consistant à :

  1. a) projeter sur la pièce un revêtement de base,
  2. b) appliquer un traitement de diminution de la tension de surface du revêtement de base, et
  3. c) projection d'au moins une solution oxydo-réductrice comprenant des ions métalliques sur la pièce pour métalliser une surface de la pièce,
dans lequel, lors de l'étape a), le bras de support de la pièce s'étend verticalement, le procédé étant caractérisé en qu'il comprend en outre une étape consistant à incliner le bras de support de la pièce à partir de la position verticale entre l'étape a) et l'étape c).In this regard, the subject of the invention is a method of metallizing the surface of a workpiece, the workpiece being held on a support arm, the method comprising the steps of:
  1. a) project on the part a base coating,
  2. b) apply a treatment for decreasing the surface tension of the base coating, and
  3. c) projecting at least one redox solution comprising metal ions on the part to metallize a surface of the part,
wherein, in step a), the work support arm of the workpiece extends vertically, the method being characterized by further comprising a step of tilting the work support arm from the workpiece. vertical position between step a) and step c).

Avantageusement, mais facultativement, le procédé selon l'invention peut en outre comprendre au moins l'une des caractéristiques suivantes : à l'issue de l'inclinaison du bras de support (20), celui-ci peut s'étendre dans une position comprise entre la position verticale et une position horizontale.

  • l'étape b) peut comprendre un traitement de flammage.
  • Le procédé peut en outre comprendre des étapes préliminaires à l'étape c) de projection, lesdites étapes comprenant une activation de la surface du flacon par projection de chlorure stanneux et un rinçage.
  • l'inclinaison du bras de support de la pièce peut être mise en oeuvre entre l'étape a) et l'étape b), entre l'étape b) et l'étape c), ou entre l'étape de rinçage et l'étape c).
  • le bras de support de la pièce peut être rotatif lors de la mise en oeuvre des étapes a) à c).
Advantageously, but optionally, the method according to the invention may further comprise at least one of the following features: after the inclination of the support arm (20), the latter can extend into a position between the vertical position and a horizontal position.
  • step b) may comprise a flame treatment.
  • The method may further comprise steps preliminary to the spraying step c), said steps comprising activation of the surface of the flask by sputtering stannous chloride and rinsing.
  • the inclination of the support arm of the workpiece can be implemented between step a) and step b), between step b) and step c), or between the rinsing step and the step c).
  • the support arm of the workpiece can be rotatable during the implementation of steps a) to c).

L'invention a également pour objet un outil de support d'une pièce pour la mise en oeuvre du procédé selon la description qui précède, comprenant :

  • un premier connecteur, adapté pour être monté solidaire en rotation d'un bras de support de la pièce, et
  • un deuxième connecteur, adapté pour être monté solidaire en rotation d'un arbre d'entrainement, et
l'outil de support étant caractérisé en ce que les connecteurs sont montés pivotants l'un par rapport à l'autre, de manière à former entre eux un angle variable sur une plage angulaire,
et en ce qu'il comprend en outre un organe de transmission d'un mouvement de rotation d'un connecteur à l'autre sur toute ladite plage angulaire.The invention also relates to a tool for supporting a part for implementing the method according to the preceding description, comprising:
  • a first connector, adapted to be mounted integral in rotation with a support arm of the part, and
  • a second connector, adapted to be mounted integral in rotation with a drive shaft, and
the support tool being characterized in that the connectors are pivotally mounted relative to one another, so as to form between them a variable angle over an angular range,
and in that it further comprises a member for transmitting a rotational movement from one connector to the other over all said angular range.

Avantageusement, mais facultativement, l'outil de support selon l'invention peut en outre comprendre au moins l'une des caractéristiques suivantes :

  • la plage angulaire peut être égale à 90°.
  • chaque connecteur peut comprendre, à une extrémité, un pignon conique, et l'organe de transmission de mouvement peut comprendre un pignon conique adapté pour engrener avec les pignons des deux connecteurs.
  • L'outil de support peut en outre comprendre un boitier formé de deux coques, chaque connecteur étant fixé à une coque respective, et les coques étant montées pivotantes l'une à l'autre sur ladite plage angulaire.
  • L'outil peut en outre comprend des moyens de blocage d'un connecteur selon une pluralité de positions angulaires dans la plage angulaire.
Advantageously, but optionally, the support tool according to the invention may further comprise at least one of the following features:
  • the angular range can be equal to 90 °.
  • each connector may comprise, at one end, a bevel gear, and the motion transmission member may comprise a bevel gear adapted to mesh with the gears of the two connectors.
  • The support tool may further comprise a housing formed of two shells, each connector being attached to a respective shell, and the shells being pivotally mounted to one another on said angular range.
  • The tool may further comprise locking means of a connector at a plurality of angular positions in the angular range.

L'invention porte également sur un système de support d'un flacon comprenant :

  • un outil de support selon la description qui précède,
  • un bras de support d'une pièce, fixé au premier connecteur de l'outil de support, et
  • un arbre d'entrainement, fixé au deuxième connecteur de l'outil de support.
The invention also relates to a vial support system comprising:
  • a support tool according to the foregoing description,
  • a one-piece support arm, attached to the first connector of the support tool, and
  • a drive shaft, attached to the second connector of the support tool.

Le procédé selon l'invention prévoit d'incliner la pièce à partir d'une position sensiblement verticale pour la mise en oeuvre de l'étape de projection de solution oxydo-réductrice. De cette manière, la pièce peut être amenée sur un axe sensiblement horizontal, ce qui a pour effet de supprimer le ruissellement de métal vers d'autres sections que la section que l'on souhaite métalliser.The method according to the invention provides for tilting the workpiece from a substantially vertical position for the implementation of the redox solution projection step. In this way, the piece can be brought on a substantially horizontal axis, which has the effect of eliminating the flow of metal to other sections than the section that is to be metallized.

Ainsi il est en particulier possible de réaliser un dégradé dans lequel les extrémités de la pièce sont faiblement métallisées et une portion entre les extrémités est plus fortement métallisée.Thus it is possible in particular to produce a gradient in which the ends of the part are weakly metallized and a portion between the ends is more strongly metallized.

L'outil proposé peut être monté directement sur les installations industrielles existantes. Il permet d'impartir à la pièce un mouvement de rotation autour de son bras de support quel que soit l'angle formé entre le bras de support et l'arbre d'entrainement sur lequel est monté l'outil, ce qui permet de conserver une homogénéité de métallisation sur une section circonférentielle de la pièce, quel que soit l'angle dans lequel le bras de support se trouve.The proposed tool can be mounted directly on existing industrial installations. It makes it possible to impart to the part a rotational movement around its support arm regardless of the angle formed between the support arm and the drive shaft on which the tool is mounted, which makes it possible to conserve homogeneity of metallization on a circumferential section of the part, whatever the angle in which the support arm is located.

En outre, l'outil permet de bloquer la pièce et son bras de support selon plusieurs angles possibles dans une plage angulaire, ce qui permet d'amener dans une position horizontale des parties de pièces de géométries complexes.In addition, the tool makes it possible to block the piece and its support arm at several possible angles in an angular range, which makes it possible to bring parts of complex geometries into a horizontal position.

DESCRIPTION DES FIGURESDESCRIPTION OF THE FIGURES

D'autres caractéristiques, buts et avantages de l'invention ressortiront de la description qui suit, qui est purement illustrative et non limitative, et qui doit être lue en regard des dessins annexés, sur lesquels :

  • Les figures 1a et 1b représentent schématiquement la mise en oeuvre des principales étapes du procédé selon un mode de réalisation de l'invention,
  • Les figures 2a et 2b représentent une pièce montée sur un outil de support lors de la mise en oeuvre du procédé,
  • La figure 2c représente une vue de dessus d'un convoyeur lors de la mise en oeuvre d'une étape de pulvérisation de solution oxydo-réductrice,
  • La figure 3 représente schématiquement une vue d'ensemble d'un outil de support selon un mode de réalisation de l'invention,
  • Les figures 4a et 4b représentent, en coupe longitudinale, un système de support comprenant un outil de support,
  • Les figures 5a et 5b sont des vues en perspective d'éléments d'un outil de support selon un mode de réalisation de l'invention.
Other characteristics, objects and advantages of the invention will emerge from the description which follows, which is purely illustrative and nonlimiting, and which should be read with reference to the appended drawings, in which:
  • The figures 1a and 1b schematically represent the implementation of the main steps of the method according to one embodiment of the invention,
  • The Figures 2a and 2b represent a part mounted on a support tool during the implementation of the method,
  • The Figure 2c represents a top view of a conveyor during the implementation of an oxidation-reduction solution spraying step,
  • The figure 3 schematically represents an overview of a support tool according to one embodiment of the invention,
  • The Figures 4a and 4b represent, in longitudinal section, a support system comprising a support tool,
  • The Figures 5a and 5b are perspective views of elements of a support tool according to an embodiment of the invention.

DESCRIPTION DETAILLEE D'AU MOINS UN MODE DE REALISATION DE L'INVENTIONDETAILED DESCRIPTION OF AT LEAST ONE EMBODIMENT OF THE INVENTION Procédé de métallisation d'une pièceMethod of metallization of a part

En référence aux figures 1a et 1b, on a représenté les principales étapes d'un procédé de métallisation d'une pièce 1.With reference to figures 1a and 1b the main steps of a metallization process of a part 1 are shown.

La pièce 1 à métalliser est avantageusement une pièce rigide, réalisée en un matériau tel qu'un verre, un plastique, un matériau composite, ou encore un métal, un alliage, etc.The part 1 to be metallized is advantageously a rigid part, made of a material such as a glass, a plastic, a composite material, or a metal, an alloy, etc.

La pièce 1 est de préférence un flacon comportant un goulot 10, comme par exemple un flacon destiné au stockage de produit cosmétique ou de parfum, une bouteille, etc. Cependant la pièce 1 n'est pas limitée dans sa forme à un flacon. Il peut par exemple s'agir de tout autre type de conteneur, par exemple un verre, ou tout autre objet tridimensionnel.The part 1 is preferably a bottle having a neck 10, such as for example a bottle for storing a cosmetic product or perfume, a bottle, etc. However, the piece 1 is not limited in its form to a bottle. It may for example be any other type of container, for example a glass, or any other three-dimensional object.

Le procédé de métallisation comprend une succession d'étapes de traitement de la surface de la pièce à métalliser. Pour réaliser avantageusement cette succession d'étapes, la pièce 1 est positionnée sur un bras de support 20, s'étendant selon un axe longitudinal.The metallization process comprises a succession of steps for treating the surface of the part to be metallized. To advantageously perform this succession of steps, the part 1 is positioned on a support arm 20, extending along a longitudinal axis.

Le bras de support 20 est monté sur un convoyeur et entrainé en translation par celui-ci, pour amener la pièce 1 aux différentes étapes du procédé.The support arm 20 is mounted on a conveyor and driven in translation by it, to bring the part 1 to the different stages of the process.

Le bras de support 20 est avantageusement conformé pour pourvoir être fixé à la pièce 1 sans la dégrader. Ainsi, dans l'exemple dans lequel la pièce 1 est un flacon pourvu d'un goulot 10, le bras de support 20, visible sur la figure 3, peut par exemple comprendre un tube 21 adapté pour être monté à l'intérieur ou à l'extérieur d'un goulot 10 d'un flacon, et deux tiges élastiques 22 pouvant être repliées l'une contre l'autre pour leur insertion à l'intérieur du flacon par le goulot. Le caractère élastique 22 des tiges tend à les écarter une fois que celles-ci sont à l'intérieur du flacon pour venir en appui contre les parois intérieures du flacon. Cet appui permet de maintenir le flacon en position par rapport au bras de support 20, et en outre à rendre le flacon solidaire en rotation du bras 20 lorsque lui-même pivote.The support arm 20 is advantageously shaped to be able to be fixed to the workpiece 1 without degrading it. Thus, in the example in which the piece 1 is a bottle provided with a neck 10, the support arm 20, visible on the figure 3 , may for example comprise a tube 21 adapted to be mounted inside or outside a neck 10 of a bottle, and two elastic rods 22 can be folded against each other for their insertion to the inside of the bottle by the neck. The elastic nature of the rods 22 tends to remove them once they are inside the bottle to bear against the inner walls of the bottle. This support makes it possible to maintain the bottle in position relative to the support arm 20, and also to make the bottle integral with rotation of the arm 20 when it itself pivots.

Alternativement le bras de support peut comprendre au moins une pince (non représentée) permettant la fixation de la pièce par serrage de la pince sur la pièce.Alternatively the support arm may comprise at least one clamp (not shown) for fixing the workpiece by clamping the clamp on the workpiece.

On pourra avantageusement se référer au document FR 2 934 609 pour obtenir d'avantage de détails concernant la mise en oeuvre des étapes 100, 200 et 300 du procédé décrit ci-après.We can advantageously refer to the document FR 2 934 609 for more details regarding the implementation of steps 100, 200 and 300 of the method described hereinafter.

De retour aux figures 2a et 2b, la première étape 100 du procédé comprend la projection sur la pièce 1 d'un revêtement de base. Ce revêtement permet de lisser la surface de la pièce pour la préparer à la projection d'un précipité métallique.Back to Figures 2a and 2b , the first step 100 of the method comprises the projection on the part 1 of a base coating. This coating makes it possible to smooth the surface of the part to prepare it for the projection of a metallic precipitate.

Il s'agit avantageusement d'un vernis hydrosoluble ou organique, de préférence hydrosoluble choisi, selon le matériau constitutif de la pièce à revêtir, parmi les composés suivants : alkydes, polyuréthanes, époxys, vinyles, acryliques et leurs mélanges. De préférence, il s'agit d'un vernis époxy, ou un vernis hydrosoluble vinylique ou polyuréthane.It is advantageously a water-soluble or organic varnish, preferably water-soluble selected, depending on the constituent material of the part to be coated, among the following compounds: alkyds, polyurethanes, epoxys, vinyls, acrylics and mixtures thereof. Preferably, it is an epoxy varnish, or a water-soluble vinyl or polyurethane varnish.

Lors de cette étape, la pièce 1 est fixée au bras 20 de support, qui se trouve dans une position verticale, c'est-à-dire que l'axe du bras 20 est vertical. Lorsque la pièce 1 est un flacon comportant un goulot cylindrique 10, l'axe du bras 20 de support est en général confondu avec l'axe du goulot 10, de sorte que l'axe du goulot est également vertical. Dans certains cas la pièce 1 présente une forme généralement cylindrique, coaxiale avec l'axe du goulot. C'est notamment le cas de la plupart des bouteilles. Dans ces cas, la pièce s'étend sensiblement verticalement au-dessus ou en-dessous du convoyeur. De plus, le bras de support 20 est rotatif autour de son axe longitudinal pour entrainer en rotation la pièce 1. De cette façon, la projection de revêtement de base est uniforme sur toute la surface de la pièce.During this step, the part 1 is fixed to the support arm 20, which is in a vertical position, that is to say that the axis of the arm 20 is vertical. When the part 1 is a bottle having a cylindrical neck 10, the axis of the support arm 20 is generally coincident with the axis of the neck 10, so that the axis of the neck is also vertical. In some cases the part 1 has a generally cylindrical shape, coaxial with the axis of the neck. This is particularly the case for most bottles. In these cases, the workpiece extends substantially vertically above or below the conveyor. In addition, the support arm 20 is rotatable about its longitudinal axis to rotate the workpiece 1. In this way, the base coat projection is uniform over the entire surface of the workpiece.

La pièce est ainsi amenée par le convoyeur jusqu'à un module 3 dans lequel des buses 30 projettent le revêtement de base sur la pièce. Une fois le revêtement projeté sur la pièce 1, la pièce 1 est avantageusement soumise à une cuisson ou une exposition à un rayonnement UV pour réticuler le revêtement de base.The part is thus conveyed by the conveyor to a module 3 in which nozzles 30 project the base coating onto the part. Once the coating is projected on the part 1, the part 1 is advantageously subjected to firing or exposure to UV radiation to crosslink the base coating.

Le procédé comprend ensuite une étape 200 de diminution de la tension de surface du revêtement de base, pour faciliter l'adhésion du précipité métallique sur la pièce. Cette étape 200 est avantageusement une étape de flammage, c'est-à-dire une étape consistant à soumettre la surface de la pièce 1 à une flamme.The method then comprises a step 200 of decreasing the surface tension of the base coating, to facilitate the adhesion of the metal precipitate on the part. This step 200 is advantageously a flaming step, that is to say a step of subjecting the surface of the piece 1 to a flame.

Par exemple cette étape peut être mise en oeuvre en entrainant en rotation la pièce, et en la soumettant à une flamme à comprise entre 1200 et 1700°C, par exemple 1400°C, pendant une durée quelques secondes, avantageusement comprise entre 4 et 50 secondes. Selon un exemple, avec une température de flamme de 1400°C, la pièce étant mise en rotation à une vitesse de 120 tours/minutes, le flammage dure 20 secondes.For example this step can be implemented by rotating the workpiece, and subjecting it to a flame at between 1200 and 1700 ° C, for example 1400 ° C, for a duration of a few seconds, advantageously between 4 and 50 seconds. In one example, with a temperature of flame of 1400 ° C, the part being rotated at a speed of 120 revolutions / minutes, the flame lasts 20 seconds.

Dans cette étape, le bras de support 20 maintenant la pièce est avantageusement toujours en position verticale, et entraine en rotation la pièce, de manière à permettre un flammage homogène de toute la surface de la pièce. Alternativement, en fonction du résultat à obtenir, le bras de support 20 de la pièce peut être incliné par rapport à la position verticale conformément à la description qui suit lors de l'étape 330.In this step, the support arm 20 holding the workpiece is advantageously always in a vertical position, and rotates the workpiece, so as to allow a homogeneous flame of the entire surface of the workpiece. Alternatively, depending on the result to be obtained, the support arm 20 of the workpiece can be inclined with respect to the vertical position in accordance with the description which follows in step 330.

La pièce 1 est toujours entrainée par le convoyeur, depuis la sortie du module 3 vers un module 4 de flammage comprenant des buses 40 de flammage.The part 1 is always driven by the conveyor, from the output of the module 3 to a flaming module 4 comprising nozzles 40 flaming.

Alternativement, l'étape 200 de diminution de la tension de surface du revêtement de base peut également être mise en oeuvre par des traitements de type traitement corona, traitement plasma, ou un traitement chimique, comme décrit plus en détails dans le document FR 2 934 609 .Alternatively, the step 200 of decreasing the surface tension of the base coating can also be implemented by treatments of the corona treatment, plasma treatment or chemical treatment type, as described in more detail in the document FR 2 934 609 .

Le procédé comprend ensuite une étape de métallisation 300 comprenant la projection 330 d'au moins une solution oxydo-réductrice comprenant des ions métalliques sur la surface de la pièce 1.The method then comprises a metallization step 300 comprising the projection 330 of at least one oxido-reducing solution comprising metal ions on the surface of the part 1.

Avantageusement, cette étape 330 est mise en oeuvre à l'aide de couples de buses 50 positionnées dans un module 5 de projection. Dans un couple de buse, une première buse projette sur la pièce une solution d'ions métalliques, par exemple d'ions argent Ag+, par exemple une solution de nitrate d'argent. La concentration en argent de la solution d'ions Ag+ est de préférence choisie comprise entre 0,1 g/L et 100 g/L, et de préférence entre 1 et 60 g/L.Advantageously, this step 330 is implemented using pairs of nozzles 50 positioned in a projection module 5. In a pair of nozzles, a first nozzle projects onto the part a solution of metal ions, for example silver ions Ag +, for example a solution of silver nitrate. The silver concentration of the Ag + ion solution is preferably chosen to be between 0.1 g / l and 100 g / l, and preferably between 1 and 60 g / l.

Une deuxième buse projette simultanément sur la pièce une solution réductrice, par exemple une solution aqueuse à base de glucose à 15 g/L. Alternativement, le réducteur de la solution peut être choisi parmi le groupe de composés comprenant les borohydrures, le diméthlaminoborane, l'hydrazine, l'hupophosphite de sodium, le formol, l'aluminohydrure de lithium, les sucres réducteurs, et leurs mélanges. La concentration en réducteur de la solution est de préférence comprise entre 0,1 g/L et 100 g/L et de préférence entre 1 et 60 g/L....A second nozzle simultaneously projects on the part a reducing solution, for example an aqueous solution based on glucose at 15 g / L. Alternatively, the reducing agent of the solution may be chosen from the group of compounds comprising borohydrides, dimethlaminoborane, hydrazine, sodium hupophosphite, formaldehyde, lithium aluminum hydride, reducing sugars, and mixtures thereof. The reducing concentration of the solution is preferably between 0.1 g / l and 100 g / l and preferably between 1 and 60 g / l.

On se réfèrera avantageusement au document FR 2 934 609 pour obtenir davantage de détails sur les choix possibles solution(s) oxydo-réductrices et l'implémentation de l'étape 330 de projection.We will refer to the document FR 2 934 609 for further details on the possible choices of redox solution (s) and the implementation of step 330 projection.

Lors de cette étape, le bras de support 20 de la pièce 1 est incliné, de manière automatique ou manuelle, par rapport à la position verticale dans laquelle il était lors des étapes 100 et 200. Avantageusement, le bras de support 20 est incliné jusqu'à ce que son axe longitudinal se trouve dans une position comprise entre la position verticale et une position horizontale. Par exemple le bras de support est incliné en position horizontale.During this step, the support arm 20 of the part 1 is inclined, automatically or manually, with respect to the vertical position in which it was during steps 100 and 200. Advantageously, the support arm 20 is inclined up to its longitudinal axis is in a position between the vertical position and a horizontal position. For example, the support arm is inclined in a horizontal position.

De préférence, comme visible sur la figure 2a, le bras de support 20 est incliné d'un angle tel qu'une surface S de la pièce à métalliser de manière homogène s'étende sensiblement verticalement. De cette manière, la gravité entrainant un ruissellement vertical des excédents de la réaction chimique, ceux-ci restent sur la surface S de la pièce à métalliser.Preferably, as visible on the figure 2a , the support arm 20 is inclined at an angle such that a surface S of the part to be metallized homogeneously extends substantially vertically. In this way, the gravity causing a vertical run off of the surplus chemical reaction, they remain on the surface S of the piece to be metallized.

Un exemple de réalisation préféré est celui dans lequel la pièce est une bouteille symétrique de révolution autour d'un axe confondu avec l'axe du goulot 10 du flacon.A preferred embodiment is that in which the piece is a symmetrical bottle of revolution about an axis coincident with the axis of the neck 10 of the bottle.

Sur le mode de réalisation de la figure 2a, on souhaite métalliser un bandeau horizontal de la surface de la bouteille. La surface est donc une surface circonférentielle s'étendant perpendiculairement à l'axe de révolution du flacon.On the embodiment of the figure 2a it is desired to metallize a horizontal strip of the surface of the bottle. The surface is a circumferential surface extending perpendicularly to the axis of revolution of the bottle.

Selon cet exemple, le bras de support 20 est avantageusement incliné jusqu'à atteindre une position horizontale, de sorte que la bouteille s'étende aussi horizontalement et que le bandeau S à métalliser s'étende verticalement.According to this example, the support arm 20 is advantageously inclined until it reaches a horizontal position, so that the bottle also extends horizontally and that the strip S to be metallized extends vertically.

Alternativement, comme représenté sur la figure 2b, lorsque la surface S à métalliser est un bandeau s'étendant selon une direction formant un angle α non nul avec l'axe du goulot 10, le bras de support 20 est incliné d'un angle égal à l'angle α par rapport à la verticale, de manière à ramener la surface S selon une direction sensiblement verticale lors de l'étape de projection. De préférence, α est inférieur ou égal à 90° pour que la bouteille de gêne pas le convoyeur.Alternatively, as shown on the figure 2b when the surface S to be metallized is a strip extending in a direction forming a non-zero angle α with the axis of the neck 10, the support arm 20 is inclined at an angle equal to the angle α with respect to the vertical, so as to bring the surface S in a substantially vertical direction during the projection step. Preferably, α is less than or equal to 90 ° so that the bottle does not bother the conveyor.

De plus, la pièce 1 la pièce est préférablement toujours entrainée en rotation autour du bras 20 lors de l'étape 330 de projection.In addition, the piece 1 the piece is preferably always rotated around the arm 20 during the 330 projection step.

Le fait que la surface à métalliser s'étende le long d'une direction verticale lors de l'étape 330 de projection tout en pivotant autour du bras 20 permet de supprimer les effets de la gravité tendant à faire ruisseler les excédents de la réaction d'oxydo-réduction le long de la pièce vers l'une de ses extrémités. A la place, les excédents restent sur la surface de projection, en étant répartis de manière homogène sur toute la circonférence de la pièce grâce à la rotation de la pièce.The fact that the surface to be metallized extends along a vertical direction during the projection step 330 while pivoting around the arm 20 makes it possible to eliminate the effects of the gravity tending to make the surpluses of the reaction reaction run off. Oxidation reduction along the piece towards one of its ends. Instead, the surpluses remain on the projection surface, being distributed homogeneous way around the entire circumference of the room through the rotation of the room.

Le fait de contrecarrer les effets de la gravité permet de réaliser des dégradés variés sur la surface de la pièce, en modulant la vitesse de rotation de la pièce autour du bras de support 20 et/ou la durée de projection de la solution oxydo-réductrice. Par exemple, il est possible de laisser les extrémités de la pièce dépourvues de revêtement de métal, et faire un dégradé depuis chaque extrémité vers un bandeau se trouvant entre les extrémités, ce bandeau étant opaque car entièrement revêtu de métal.Counteracting the effects of gravity makes it possible to perform various gradations on the surface of the part, by modulating the speed of rotation of the part around the support arm 20 and / or the projection time of the redox solution. . For example, it is possible to leave the ends of the piece devoid of metal coating, and make a gradient from each end to a strip between the ends, this strip being opaque because fully coated with metal.

Alternativement ou en complément, la modulation du dégradé sur la surface de la pièce peut aussi être obtenue en modulant la vitesse du convoyeur et en faisant varier les concentrations des réactifs de la ou des solution(s) oxydo-réductrice(s).Alternatively or in addition, the modulation of the gradient on the surface of the part can also be obtained by modulating the speed of the conveyor and by varying the concentrations of the reagents of the redox solution (s).

Il est également possible de réaliser plusieurs bandeaux disjoints séparés par une zone non revêtue de métal. Le cas échéant, un dégradé peut être réalisé entre la zone et chaque bandeau.It is also possible to make several disjoint strips separated by an uncoated area of metal. If necessary, a gradient can be made between the zone and each banner.

Avantageusement, mais facultativement, le procédé comprend en outre des étapes préliminaires 310, 320 à la projection de solutions oxydo-réductrices, pour préparer la surface à métalliser.Advantageously, but optionally, the method further comprises preliminary steps 310, 320 to the projection of redox solutions, to prepare the surface to be metallized.

Au cours d'une première étape préliminaire 310, la pièce 1 est amenée, en sortie du module 4 de flammage, dans un module 6 dans lequel une solution d'activation est projetée sur la pièce. Cette solution est avantageusement une solution de chlorure stanneux. L'étape 310 d'activation peut être mise en oeuvre conformément à l'étape de sensibilisation décrite dans le document FR 2 763 962 .During a preliminary preliminary step 310, the part 1 is brought, at the output of the flaming module 4, into a module 6 in which an activation solution is projected onto the part. This solution is advantageously a stannous chloride solution. The activation step 310 can be implemented according to the sensitization step described in the document FR 2 763 962 .

Elle est alors immédiatement suivie, dans le même module, d'une étape 320 de rinçage des résidus de chlorure stanneux, par projection d'un liquide de rinçage, par exemple de l'eau. La pièce peut ensuite être séchée par circulation d'air (non représenté).It is then immediately followed, in the same module, a step 320 rinsing the stannous chloride residues, by spraying a rinsing liquid, for example water. The part can then be dried by air circulation (not shown).

Avantageusement, l'inclinaison du bras de support 20 en perspective de l'étape 330 est mise en oeuvre à l'issue de cette étape 320 de rinçage. Alternativement, elle peut être mise en oeuvre avant ou à l'issue de l'étape de flammage. L'inclinaison peut être mise en oeuvre manuellement ou automatiquement.Advantageously, the inclination of the support arm 20 in perspective of step 330 is implemented at the end of this step 320 rinsing. Alternatively, it can be implemented before or after the flaming step. The inclination can be implemented manually or automatically.

De retour à l'étape 330 de projection de solution oxydo-réductrice pour métalliser la pièce, la pièce 1 est ensuite amenée dans un module 7 de finition pour obtenir une couche de finition lors d'une étape 400 de finition. Avantageusement, le bras de support 20 de la pièce est repositionné à la verticale pour la mise en oeuvre de cette étape, le repositionnement pouvant être réalisé manuellement ou automatiquement.Returning to step 330 of redox solution projection to metallize the workpiece, the workpiece 1 is then brought into a finishing module 7 to obtain a finishing layer during a finishing step 400. Advantageously, the support arm 20 of the part is repositioned vertically for the implementation of this step, the repositioning can be performed manually or automatically.

L'étape de finition est réalisée par exemple par projection sur la pièce d'un vernis de finition.The finishing step is carried out for example by projection on the piece of a finishing varnish.

On se réfèrera avantageusement à l'étape de finition décrite dans le document FR 2 934 609 pour obtenir davantage d'informations sur les mises en oeuvre possibles de l'étape de finition.Advantageously refer to the finishing step described in the document FR 2 934 609 for more information on possible implementations of the finishing step.

Outil et Système de support d'une pièceTool and Support System of a Part

En référence aux figures 3 à 5b, on va maintenant décrire un outil de support permettant la mise en oeuvre du procédé décrit ci-avant.With reference to Figures 3 to 5b , we will now describe a support tool for carrying out the method described above.

Cet outil 9 comprend un premier connecteur 90, adapté pour être monté solidaire d'un bras de support 20 de la pièce, représenté en pointillés sur la figure 4b.This tool 9 comprises a first connector 90, adapted to be mounted integral with a support arm 20 of the part, shown in dotted lines on the figure 4b .

Le connecteur 90 est avantageusement un arbre comprenant des moyens d'entrainement en rotation du bras de support. Par exemple, ces moyens peuvent prendre la forme de cannelures (non représentées) agencées sur la circonférence du connecteur 90, et adaptées pour coopérer avec des cannelures complémentaires du bras de support 20.The connector 90 is advantageously a shaft comprising means for rotating the support arm. For example, these means may take the form of splines (not shown) arranged on the circumference of the connector 90, and adapted to cooperate with complementary splines of the support arm 20.

Alternativement, l'un du connecteur 90 et du bras de support 20 peut recevoir l'autre par encliquetage, serrage, ou encore vissage, etc.Alternatively, one of the connector 90 and the support arm 20 can receive the other by snapping, tightening, or screwing, etc.

L'outil 9 de support comprend également un deuxième connecteur 91. Ce deuxième connecteur est adapté pour être monté solidaire d'un arbre d'entraînement 23. Cet arbre d'entraînement 23 est lui-même monté sur le convoyeur 2 et est entrainé en rotation et en translation par le convoyeur 2.The support tool 9 also comprises a second connector 91. This second connector is adapted to be mounted integral with a drive shaft 23. This drive shaft 23 is itself mounted on the conveyor 2 and is driven by rotation and translation by the conveyor 2.

De manière analogue, le connecteur 91 est avantageusement un arbre comprenant des moyens d'entrainement en rotation de ou par l'arbre d'entrainement 23. Sur la figure 3, le connecteur 91 comprend des cannelures 910 adaptées pour entrainer en rotation des cannelures complémentaires de l'arbre d'entrainement 23 (non représenté).Similarly, the connector 91 is advantageously a shaft comprising means for driving in rotation from or through the drive shaft 23. figure 3 , the connector 91 comprises splines 910 adapted to drive in rotation complementary splines of the drive shaft 23 (not shown).

Alternativement, l'un du connecteur 91 et de l'arbre d'entrainement 23 peut recevoir l'autre par encliquetage, serrage, vissage, etc.Alternatively, one of the connector 91 and the drive shaft 23 can receive the other by snapping, tightening, screwing, etc.

Les connecteurs 90, 91 de l'outil s'étendent donc selon des axes longitudinaux respectifs, qui sont avantageusement coplanaires. De plus, les axes connecteurs 90, 91 forment entre eux un angle pouvant varier sur une plage angulaire. Cette plage angulaire est avantageusement comprise entre 10 et 100°, de préférence de l'ordre de 90°, pour permettre, en utilisation, au bras de support 20 de passer d'une position verticale à une position horizontale tandis que l'arbre rotatif 23 reste en position verticale.The connectors 90, 91 of the tool therefore extend along respective longitudinal axes, which are advantageously coplanar. In addition, the connector pins 90, 91 form between them an angle that can vary over an angular range. This angular range is advantageously between 10 and 100 °, preferably of the order of 90 °, to allow, in use, the support arm 20 to move from a vertical position to a horizontal position while the rotary shaft 23 remains upright.

Pour ce faire, l'outil de support comprend un boitier formé de deux coques 92, 93, les coques étant pouvant être assemblées l'une sur l'autre en autorisant un mouvement de pivot relatif entre les deux coques sur ladite plage angulaire. De plus, chaque connecteur 90, 91 est fixé à une coque respective 92, 93.To do this, the support tool comprises a housing formed of two shells 92, 93, the shells being able to be assembled one on the other by allowing a relative pivoting movement between the two shells on said angular range. In addition, each connector 90, 91 is attached to a respective shell 92, 93.

Les coques délimitent entre elles, lorsqu'elles sont assemblées, un logement 94 interne. Chaque connecteur 90, 91 comprend une extrémité 902, 912 pénétrant à l'intérieur du logement 94 au travers d'un orifice agencé dans la paroi de l'une ou des deux coques. Ainsi, chaque connecteur est solidaire en rotation de la coque sur laquelle il est monté.The shells delimit between them, when assembled, an internal housing 94. Each connector 90, 91 comprises an end 902, 912 penetrating inside the housing 94 through an orifice arranged in the wall of one or both shells. Thus, each connector is integral in rotation with the shell on which it is mounted.

Selon un exemple de réalisation particulier représenté sur les figures 4a et 4b, la première coque 92 comprend une paroi de fond 920 comprenant un bord circulaire et une paroi cylindrique ou en secteur de cylindre 921 s'étendant autour d'une partie du bord de la paroi de fond 920, perpendiculairement au plan de la paroi 920. Avantageusement, la paroi cylindrique 921 s'étend sur une ouverture angulaire correspondant au complémentaire de la plage angulaire de rotation relative des connecteurs sur 360°.According to a particular embodiment shown on the Figures 4a and 4b the first shell 92 comprises a bottom wall 920 comprising a circular edge and a cylindrical or cylinder sector wall 921 extending around a portion of the edge of the bottom wall 920, perpendicular to the plane of the wall 920. Advantageously, the cylindrical wall 921 extends over an angular aperture corresponding to the complementary of the angular range of relative rotation of the connectors over 360 °.

La deuxième coque 93 comprend également une paroi de fond 930, comprenant un bord circulaire de diamètre légèrement inférieur à celui de la paroi 920. La deuxième coque 93 comprend également une paroi cylindrique 931 s'étendant circonférentiellement autour du bord de la paroi 930, perpendiculairement au plan de la paroi 930. La différence de diamètre entre les parois de fond 920 et 930 correspond à l'épaisseur de la paroi cylindrique 930. Ainsi, la première coque 92 peut être montée autour de la seconde 93 et pivoter sur celle-ci par rapport à un axe passant par les centres des parois de fond 920, 930, perpendiculaire aux axes des connecteurs 90 et 91.The second shell 93 also comprises a bottom wall 930, comprising a circular edge of slightly smaller diameter than that of the wall 920. The second shell 93 also comprises a cylindrical wall 931 extending circumferentially around the edge of the wall 930, perpendicularly in the plane of the wall 930. The difference in diameter between the bottom walls 920 and 930 corresponds to the thickness of the cylindrical wall 930. Thus, the first shell 92 can be mounted around the second 93 and pivot on it with respect to an axis passing through the centers of the bottom walls 920, 930, perpendicular to the axes of the connectors 90 and 91.

Lorsque les deux coques 92, 93 sont montées l'une sur l'autre, les parois cylindriques 931 s'étendant dans des directions opposées par rapport aux parois de fond respectives 920, 930, les coques coopèrent pour former le logement 94.When the two shells 92, 93 are mounted on each other, the cylindrical walls 931 extending in opposite directions with respect to the respective bottom walls 920, 930, the shells cooperate to form the housing 94.

De plus la première coque 92 comprend un orifice 922 adapté pour recevoir une section du connecteur 90. Le connecteur 90 est monté rotatif dans l'orifice 922 mais est maintenu fixe en translation par des moyens d'arrêt 80 représentés schématiquement sur la figure 4b.In addition the first shell 92 comprises an orifice 922 adapted to receive a section of the connector 90. The connector 90 is rotatably mounted in the orifice 922 but is held fixed in translation by stop means 80 shown schematically on the figure 4b .

La première coque 93 comprend également un orifice 932 adapté pour recevoir une section du connecteur 91. Le connecteur 91 est monté rotatif dans l'orifice 932 mais est également maintenu fixe en translation par des moyens d'arrêt 81.The first shell 93 also comprises an orifice 932 adapted to receive a section of the connector 91. The connector 91 is rotatably mounted in the orifice 932 but is also held fixed in translation by stop means 81.

La deuxième coque comprend également un deuxième orifice 933 s'étendant sur un secteur angulaire correspondant à la plage de rotation relative des connecteurs.The second shell also comprises a second orifice 933 extending over an angular sector corresponding to the relative rotation range of the connectors.

Lorsque les coques sont assemblées, l'orifice 922 débouche dans l'orifice 933 de manière à autoriser le pivot du connecteur 90 par rapport à la coque 93 sur la plage angulaire de déplacement.When the shells are assembled, the orifice 922 opens into the orifice 933 so as to allow the pivot of the connector 90 relative to the shell 93 on the angular range of displacement.

De même, l'orifice 932 de la première coque débouche sur la portion de la coque 92 dépourvue paroi cylindrique, de manière à permettre le pivot du connecteur 91 par rapport à la coque 92 sur la plage angulaire de déplacement.Similarly, the orifice 932 of the first shell opens on the portion of the shell 92 without cylindrical wall, so as to allow the pivot of the connector 91 relative to the shell 92 on the angular range of displacement.

Ainsi, lorsque les deux coques 92 et 93 sont montées ensemble, elles forment une articulation entre le bras de support 20 et l'arbre d'entrainement rotatif 23 via les connecteurs respectifs 90, 91, autorisant un pivotement du bras de support 20 par rapport à l'arbre d'entrainement rotatif 23.Thus, when the two shells 92 and 93 are mounted together, they form an articulation between the support arm 20 and the rotary drive shaft 23 via the respective connectors 90, 91, allowing pivoting of the support arm 20 relative to to the rotary drive shaft 23.

Avantageusement, l'outil 9 comprend également des moyens d'arrêt 95 en rotation d'un connecteur par rapport à l'autre connecteur sur une pluralité de positions relatives parmi celles couvertes par la plage angulaire de pivot.Advantageously, the tool 9 also comprises stop means 95 rotating a connector relative to the other connector on a plurality of relative positions among those covered by the angular range of pivot.

Les moyens d'arrêt peuvent avantageusement être une pluralité de cales en arc de cercle, de diamètre égal au diamètre de la coque 92. Ces cales peuvent être intercalées entre le connecteur 91 et la paroi cylindrique 921 pour interdire une rotation relative de ces deux éléments. En fonction du secteur angulaire couvert par les cales, plusieurs angles peuvent ainsi être bloqués.The stop means may advantageously be a plurality of shims in an arc of a diameter equal to the diameter of the shell 92. These shims may be inserted between the connector 91 and the cylindrical wall 921 to prevent relative rotation of these two elements. . Depending on the angular sector covered by the wedges, several angles can thus be blocked.

Alternativement, les coques 92 et 93 peuvent comprendre des moyens d'encliquetage qui maintiennent les coques en une position relative constante, jusqu'à ce qu'une pression soit exercée pour dégager les moyens d'encliquetage.Alternatively, the shells 92 and 93 may comprise latching means which hold the shells in a constant relative position, until pressure is exerted to disengage the latching means.

On a représenté à titre d'exemple des moyens d'encliquetage 95 composé d'un picot 950 en saillie sur la paroi cylindrique 931 et de plusieurs orifices 951 agencés sur une surface face au logement 94 de la paroi cylindrique 921. En fonction de l'orifice dans lequel est engagé le picot, plusieurs positions angulaires relatives des coques (et des connecteurs) peuvent être bloquées.There is shown by way of example snap-fastening means 95 consisting of a pin 950 projecting on the cylindrical wall 931 and several orifices 951 arranged on a surface facing the housing 94 of the cylindrical wall 921. In which hole is engaged the pin, several relative angular positions of the shells (and connectors) can be blocked.

Enfin, l'outil de support comprend également un organe 96 de transmission d'un mouvement de rotation de l'un à l'autre connecteur, et ce sur toute la plage angulaire de déplacement relatif des connecteurs.Finally, the support tool also comprises a member 96 for transmitting a rotational movement from one to the other connector over the entire angular range of relative displacement of the connectors.

L'organe 96 comprend à cet effet un pignon conique qui est agencé à l'intérieur du logement, le pignon conique présentant un axe orthogonal au plan dans lequel s'étendent les connecteurs 90, 91. Cet axe correspond à l'axe de pivot relatif des deux coques 92, 93 et des connecteurs.The member 96 comprises for this purpose a conical pinion which is arranged inside the housing, the conical pinion having an axis orthogonal to the plane in which the connectors 90, 91 extend. This axis corresponds to the pivot axis relative of the two hulls 92, 93 and connectors.

De plus, l'extrémité de chaque connecteur se trouvant à l'intérieur du logement 94 comprend également un pignon conique respectif 903, 913, adapté pour engrener avec le pignon 96.In addition, the end of each connector located inside the housing 94 also comprises a respective conical pinion 903, 913 adapted to mesh with the pinion 96.

De la sorte, un mouvement de rotation du connecteur 91 prélevé à partir de l'arbre d'entrainement rotatif 23 est transmis par le pignon conique 96 au connecteur 90 qui le transmet ensuite au bras de support 20 de la pièce.In this way, a rotational movement of the connector 91 taken from the rotary drive shaft 23 is transmitted by the bevel gear 96 to the connector 90 which then transmits it to the support arm 20 of the workpiece.

Ce faisant, quelle que soit l'inclinaison du connecteur 90 par rapport au connecteur 91, un mouvement de rotation est quand même transmis.In doing so, regardless of the inclination of the connector 90 relative to the connector 91, a rotational movement is still transmitted.

De plus, pour éviter que le connecteur 91 n'entraine en rotation tout le boitier composé des deux coques 92, 93, des moyens 82 empêchant cet entraînement peuvent être prévus. Par exemple, il peut s'agir d'un roulement interposé entre le connecteur 91 et la coque 93.In addition, to prevent the connector 91 from rotating all the housing consisting of two shells 92, 93, means 82 preventing this drive can be provided. For example, it may be a bearing interposed between the connector 91 and the hull 93.

Alternativement, et comme représenté sur les figures 4a, 4b, et 5a, la coque 93 peut comprendre une protubérance 82 s'étendant autour du connecteur 91 et présentant une extrémité de section carrée. Comme visible sur la figure 2c, le convoyeur 2 est avantageusement bordé de glissières 83 dans le module 5 de métallisation, dont la largeur correspond à un côté de la section de la protubérance 82.Alternatively, and as shown on the Figures 4a , 4b , and 5a , the shell 93 may comprise a protrusion 82 extending around the connector 91 and having a square section end. As visible on the Figure 2c , the conveyor 2 is advantageously lined with slides 83 in the metallization module 5, whose width corresponds to one side of the section of the protuberance 82.

De cette manière, même si des frottements entre le connecteur 91 et la coque 93 entrainent celle-ci en rotation, l'outil de support est maintenu fixe dans une direction uniquement par les glissières à l'approche du module 5. Un opérateur peut se charger de vérifier que cette direction est la bonne, et repositionner le cas échéant l'outil dans la bonne direction, par exemple une direction parallèle à la direction de déplacement du convoyeur comme sur la figue 2c.In this way, even if friction between the connector 91 and the shell 93 causes the latter to rotate, the support tool is held fixed in one direction only by the slides at the approach of the module 5. An operator can to check that this direction is correct, and reposition if necessary the tool in the right direction, for example a direction parallel to the direction of travel of the conveyor as in Fig 2c.

Un système comprenant un outil 9, un bras de support 20 et un arbre d'entrainement 23 monté sur un convoyeur 2 peut ainsi permettre le montage d'une pièce pour la réalisation de métallisations complexes, et notamment des métallisations comprenant plusieurs dégradés sur une même pièce.A system comprising a tool 9, a support arm 20 and a drive shaft 23 mounted on a conveyor 2 can thus allow the assembly of a part for the realization of complex metallizations, and in particular metallizations comprising several gradients on the same room.

Claims (12)

  1. A method for metallization of the surface of a part (1), the part being held on a support arm (20), the method comprising the steps consisting of:
    a) projecting (100) a base coating onto the part,
    b) applying (200) a treatment for reducing the surface tension of the base coating, and
    c) projecting (330) at least one redox solution comprising metal ions onto the part to metallize a surface of the part,
    wherein, during step a), the support arm of the part extends vertically,
    the method being characterized in that it further comprises a step of tilting the support arm of the part from the vertical position between step a) and step c).
  2. The method for metallization of a flask according to claim 1, wherein at the end of the tilting of the support arm (20), the latter extends in a position between the vertical position and a horizontal position.
  3. The method for metallization of a flask according to one of claims 1 or 2, wherein step b) comprises a flame treatment.
  4. The method for metallization of a flask according to one of the preceding claims, further comprising steps prior to projection step c), said steps comprising activation (310) of the surface of the flask by projection of stannous chloride and rinsing (320).
  5. The method for metallization of a flask according to claim 4, wherein the tilting of the support arm (20) of the part is implemented between step a) and step b), between step b) and step c), or between the rinsing step and step c).
  6. The method for metallization of a flask according to one of the preceding claims, wherein the support arm (20) of the part (1) is rotatable during implementation of steps a) to c).
  7. A tool (9) for supporting a part (1) for implementing the method according to one of the preceding claims, comprising:
    - a first connector (90), adapted to be mounted in a rotationally fixed manner on a support arm (20) of the part, and
    - a second connector (91), adapted to be mounted in a rotationally fixed manner on a drive shaft (23), and
    the support tool being characterized in that the connectors are mounted pivotably relative to each other, so as to form therebetween a variable angle over an angular range,
    and in that it further comprises a member (96) for transmitting rotary motion from one connector to another throughout said angular range.
  8. The support tool (9) according to claim 7, wherein the angular range is equal to 90°.
  9. The support tool (9) according to one of claims 7 or 8, wherein each connector (90, 91) comprises, at one end, a bevel pinion (903, 913), and the motion-transmitting member (96) comprises a bevel pinion adapted to engage the pinions of the two connectors.
  10. The support tool (9) according to one of claims 7 to 9, further comprising a housing formed from two shells (92, 93), each connector being attached to a respective shell, and the shells being mounted pivotably to each other over said angular range.
  11. The support tool (9) according to one of claims 7 to 10, further comprising means for locking (95) a connector in a plurality of angular positions in the angular range.
  12. A system for supporting a flask comprising:
    - a support tool (9) according to one of claims 7 to 11,
    - a support arm (20) of a part (1), attached to the first connector (90) of the support tool, and
    - a drive shaft (23), attached to the second connector (91) of the support tool.
EP16172954.6A 2015-06-05 2016-06-03 Metallisation method and tool for the production of complex shadings Not-in-force EP3101155B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16172954T PL3101155T3 (en) 2015-06-05 2016-06-03 Metallisation method and tool for the production of complex shadings

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1555141A FR3037081B1 (en) 2015-06-05 2015-06-05 METALLIZATION METHOD AND TOOL FOR PERFORMING COMPLEX DEGRADES

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EP3101155A1 EP3101155A1 (en) 2016-12-07
EP3101155B1 true EP3101155B1 (en) 2017-11-22

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FR (1) FR3037081B1 (en)
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Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
FR2763962B1 (en) 1997-05-29 1999-10-15 Guy Stremsdoerfer NON-ELECTROLYTIC PROCESS FOR METALLIZING A SUBSTRATE BY MEANS OF REDUCING METAL SALT (S) AND BY SPRAYING AEROSOL (S)
FR2934609B1 (en) * 2008-07-30 2011-07-22 Jet Metal Technologies NON-ELETROLYTIC METHOD FOR ONLINE METALLIZATION OF PROJECTION SUBSTRATES WITH PRECONDITIONAL SURFACE TREATMENT AND DEVICE FOR IMPLEMENTING THE METHOD
FR3011558A1 (en) * 2013-10-09 2015-04-10 Vetver PROCESS FOR DECORATION BY METALLIZATION OF GLASS BOTTLES PREFALLABLY FILLED WITH A CHAMPAGNE WINE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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EP3101155A1 (en) 2016-12-07
PL3101155T3 (en) 2018-07-31
FR3037081B1 (en) 2017-08-04

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