EP3101155B1 - Metallisierungsverfahren und werkzeug, das die erstellung von komplexen abstufungen ermöglicht - Google Patents

Metallisierungsverfahren und werkzeug, das die erstellung von komplexen abstufungen ermöglicht 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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Not-in-force
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EP16172954.6A
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English (en)
French (fr)
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EP3101155A1 (de
Inventor
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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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Claims (12)

  1. Metallisierungsverfahren der Oberfläche eines Teils (1), wobei das Teil auf einem Stützarm (20) gehalten wird, wobei das Verfahren die folgenden Schritte umfasst:
    a) Projizieren (100) einer Basisbeschichtung auf das Teil,
    b) Auftragen (200) einer Behandlung zur Verringerung der Oberflächenspannung der Basisbeschichtung, und
    c) Projizieren (330) mindestens einer oxidationsreduzierenden Lösung, die Metallionen umfasst, auf das Teil, um eine Oberfläche des Teils zu metallisieren,
    wobei sich der Stützarm des Teils beim Schritt a) vertikal erstreckt, wobei das Verfahren dadurch gekennzeichnet ist, dass es ferner einen Schritt umfasst, der darin besteht, den Stützarm des Teils zwischen dem Schritt a) und dem Schritt c) aus der vertikalen Position zu neigen.
  2. Metallisierungsverfahren eines Flakons nach Anspruch 1, wobei sich der Stützarm (20) nach dem Neigen in einer Position zwischen der vertikalen Position und einer horizontalen Position erstreckt.
  3. Metallisierungsverfahren eines Flakons nach einem der Ansprüche 1 oder 2, wobei der Schritt b) eine Beflammungsbehandlung umfasst.
  4. Metallisierungsverfahren eines Flakons nach einem der vorangehenden Ansprüche, umfassend ferner Schritte vor dem Projektionsschritt c), wobei die Schritte eine Aktivierung (310) der Oberfläche des Flakons durch Projektion von Zinndichlorid und eine Reinigung (320) umfassen.
  5. Metallisierungsverfahren eines Flakons nach Anspruch 4, wobei das Neigen des Stützarms (20) des Teils zwischen dem Schritt a) und dem Schritt b), zwischen dem Schritt b) und dem Schritt c) oder zwischen dem Reinigungsschritt und dem Schritt c) durchgeführt wird.
  6. Metallisierungsverfahr en eines Flakons nach einem der vorangehenden Ansprüche, wobei der Stützarm (20) des Teils (1) bei der Durchführung der Schritte a) bis c) rotierend ist.
  7. Stützwerkzeug (9) eines Teils (1) für die Durchführung des Verfahrens nach einem der vorangehendne Ansprüche, umfassend:
    - einen ersten Verbinder (90), der ausgebildet ist, um mit einem Stützarm (20) des Teils rotierend fest verbunden montiert zu sein, und
    - einen zweiten Verbinder (91), der ausgebildet ist, um mit einer Antriebswelle (23) rotierend fest verbunden montiert zu sein, und
    wobei das Stützwerkzeug dadurch gekennzeichnet ist, dass die Verbinder in Bezug zueinander schwenkend montiert sind, so dass sie zwischen sich einen in einem Winkelbereich variablen Winkel bilden,
    und dass es ferner ein Übertragungsorgan (96) einer Rotationsbewegung eines Verbinders auf den anderen im gesamten Winkelbereich umfasst.
  8. Stützwerkzeug (9) nach Anspruch 7, wobei der Winkelbereich 90° entspricht.
  9. Stützwerkzeug (9) nach einem der Ansprüche 7 oder 8, wobei jeder Verbinder (90, 91) an einem Ende ein Kegelrad (903, 913) umfasst und das Bewegungsübertragungsorgan (96) ein Kegelrad umfasst, das ausgebildet ist, um in die Kegelräder der zwei Verbinder einzugreifen.
  10. Stützwerkzeug (9) nach einem der Ansprüche 7 bis 9, umfassend ferner ein von zwei Schalen (92, 93) gebildetes Gehäuse, wobei jeder Verbinder an einer jeweiligen Schale befestigt ist und die Schalen im Winkelbereich zueinander schwenkbar montiert sind.
  11. Stützwerkzeug (9) nach einem der Ansprüche 7 bis 10, umfassend ferner Blockiermittel (95) eines Verbinders in einer Vielzahl von Winkelpositionen im Winkelbereich.
  12. Stützsystem eines Flakons, umfassend:
    - ein Stützwerkzeug (9) nach einem der Ansprüche 7 bis 11,
    - einen Stützarm (20) eines Teils (1), der am ersten Verbinder (90) des Stützwerkzeugs befestigt ist, und
    - eine Antriebswelle (23), die am zweiten Verbinder (91) des Stützwerkzeugs befestigt ist.
EP16172954.6A 2015-06-05 2016-06-03 Metallisierungsverfahren und werkzeug, das die erstellung von komplexen abstufungen ermöglicht Not-in-force EP3101155B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16172954T PL3101155T3 (pl) 2015-06-05 2016-06-03 Sposób metalizowania i narzędzie umożliwiające wykonanie złożonych cieniowań

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1555141A FR3037081B1 (fr) 2015-06-05 2015-06-05 Procede de metallisation et outil permettant la realisation de degrades complexes

Publications (2)

Publication Number Publication Date
EP3101155A1 EP3101155A1 (de) 2016-12-07
EP3101155B1 true EP3101155B1 (de) 2017-11-22

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EP16172954.6A Not-in-force EP3101155B1 (de) 2015-06-05 2016-06-03 Metallisierungsverfahren und werkzeug, das die erstellung von komplexen abstufungen ermöglicht

Country Status (3)

Country Link
EP (1) EP3101155B1 (de)
FR (1) FR3037081B1 (de)
PL (1) PL3101155T3 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2763962B1 (fr) 1997-05-29 1999-10-15 Guy Stremsdoerfer Procede non electrolytique de metallisation d'un substrat par voie de reduction de sel(s) metallique(s) et par projection d'aerosol(s)
FR2934609B1 (fr) * 2008-07-30 2011-07-22 Jet Metal Technologies Procede non eletrolytique de metallisation en ligne de substrats par projection avec traitement de surface prealable et dispositif pour la mise en oeuvre du procede.
FR3011558A1 (fr) * 2013-10-09 2015-04-10 Vetver Procede de decor par metallisation de bouteilles en verre prealablement remplies d'un vin de champagne

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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FR3037081B1 (fr) 2017-08-04
EP3101155A1 (de) 2016-12-07
FR3037081A1 (fr) 2016-12-09
PL3101155T3 (pl) 2018-07-31

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