EP3911779A1 - Treatment method and device for depositing a barrier-effect coating - Google Patents

Treatment method and device for depositing a barrier-effect coating

Info

Publication number
EP3911779A1
EP3911779A1 EP19745683.3A EP19745683A EP3911779A1 EP 3911779 A1 EP3911779 A1 EP 3911779A1 EP 19745683 A EP19745683 A EP 19745683A EP 3911779 A1 EP3911779 A1 EP 3911779A1
Authority
EP
European Patent Office
Prior art keywords
container
enclosure
gas
coupling
excitation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19745683.3A
Other languages
German (de)
French (fr)
Inventor
Nasser Beldi
Fabrice Oge
Patrick Chollet
Mikaël JAOUEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Innovative Systems Et Technologies Isytech
Original Assignee
Innovative Systems Et Technologies Isytech
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Innovative Systems Et Technologies Isytech filed Critical Innovative Systems Et Technologies Isytech
Publication of EP3911779A1 publication Critical patent/EP3911779A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4409—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber characterised by sealing means
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/517—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H01J37/32211—Means for coupling power to the plasma
    • H01J37/32229—Waveguides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32394—Treating interior parts of workpieces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H05H1/461—Microwave discharges
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H05H1/4645—Radiofrequency discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H2245/00—Applications of plasma devices
    • H05H2245/40—Surface treatments

Definitions

  • the invention relates to the field of surface treatment to obtain the deposition of a barrier effect coating from a low pressure plasma.
  • polyethylene, polypropylene and polyethylene terephthalate are widely used in industry.
  • the coating deposition operation is for example carried out with a
  • This technique consists in introducing at low pressure into an enclosure a gas, called a precursor, comprising the atomic elements forming the molecular structure of the coating.
  • the precursor gas is then excited to be transformed into an unstable form and very reactive, called plasma, leading to recombination and deposition of solid material in a thin layer on the wall to be coated.
  • a microwave type energy source is commonly used to excite the precursor gas and transform it into the plasma state because it has the advantage of creating very dense plasmas, which makes it possible to obtain a speed of significant deposition, compatible with industrial rates.
  • An example of a microwave-generated plasma surface treatment device is given in document FR2792854.
  • Such a device consists mainly of a metal chamber
  • a microwave coupling enclosure which communicates with a waveguide allowing the introduction of microwaves into said metal chamber.
  • This device is also provided with an enclosure made of gas-tight dielectric material called a vacuum enclosure. The container to be treated is placed in this vacuum chamber.
  • the metal trays do not constitute a sufficient means of adjustment and the plasma obtained can be very unstable regardless of the position of the trays.
  • the formats used have geometries which disturb the propagation of the microwaves. The portion of microwave energy coupled, that is to say transmitted to the plasma, is then not sufficient to maintain a stable plasma promoting the formation of a
  • the invention proposes a solution aimed at overcoming the drawbacks and the
  • An objective of the invention is to obtain a stable plasma regardless of the geometry and the position of the container to be treated in order to deposit thereon on its internal surface a coating with a high-performance barrier effect.
  • the invention relates to a method of treatment in an enclosure of a
  • barrier effect coating comprising:
  • microwave type electromagnetic and secondary excitation by means of an electric discharge of alternating voltage having a frequency between 1 kHz and 15 MHz.
  • the alternating voltage has a frequency between 10kHz and 200kHz.
  • microwave electromagnetic waves with a frequency between 300 MHz and 3000 MHz.
  • the microwaves have a frequency between 915 MHz and 2450 MHz.
  • carrier effect coating means a coating deposited on a wall having the property of reducing the diffusion of gases and liquids through the wall.
  • the main excitation by means of electromagnetic waves of the microwave type is the excitation which makes it possible to transform the precursor gas into the plasma state and which makes it possible to carry out the deposit to constitute the barrier effect coating.
  • the power of the main excitation is greater than the power of the secondary excitation and it is the main excitation which provides the energy necessary for the transformation of the precursor gas into the plasma state and necessary for the deposition.
  • the secondary excitation by means of an electric discharge of alternating voltage makes it possible to obtain a stable plasma, whatever the geometric shape or the position of the container in the coupling enclosure, that is to say a portion of the gas is transformed into plasma and remains in the plasma state throughout the duration of the excitation. This portion of the gas transformed into plasma and remaining in the plasma state will then allow the main excitation by means of microwaves to be established in a stable manner throughout its duration.
  • the combination of the main excitation and the secondary excitation is beneficial because in certain cases, in particular for certain formats, the excitation by means of electromagnetic waves of the microwave type alone is not sufficient insofar as the transmission of energy from microwaves to plasma can be disturbed by the shape of the container and is then not totally consumed by the gas to be transformed into the plasma state. Consequently, the precursor gas does not transform in a sufficiently durable manner to achieve a performance coating. It should be noted that the excitation by means of an electric discharge of alternating voltage alone does not make it possible to have sufficiently fast deposition rates for rates
  • electromagnetic microwave type and the excitation by means of an electric discharge is to obtain simultaneously, the speed of treatment conferred by a plasma generated by microwaves and the stability of a plasma generated by an excitation by an electric shock.
  • the excitation by means of an electrical discharge of alternating voltage can be carried out simultaneously during a phase of the treatment called the plasma phase.
  • the plasma phase time can be between one
  • the peak value of the voltage of the electric discharge may be between 100 V and 1000 V, preferably between 200 V and 500 V.
  • the precursor gas may be a gas chosen from alkanes, alkenes, alkynes, aromatics, or a combination of some of them.
  • the precursor gas can be a tetrafluoroethane gas- 1, 1, 1, 2, pentafluoroethane, difluoromethane, acetylene, or a combination of some of them or a mixture of some of them. 'between them with a rare gas such as argon.
  • the method may further include a preliminary step of treating the surface with a plasma of oxygen, hydrogen, argon, carbon dioxide, helium, nitrogen or a combination of some of them.
  • the method may include the deposition of a succession of coating layers.
  • the electromagnetic can be between 0.01 W / cm 3 and 1 W / cm 3 .
  • the power of the electromagnetic waves can be between 40 W and 4 kW, for a 20 L can, the power of the waves
  • electromagnetic can be between 200 W and 20 kW.
  • the power of the electric discharge can be between 1 W and 2000 W, preferably between 4 W and 100 W.
  • the power of the main excitation by means of microwave-type electromagnetic waves is greater than the power of the secondary excitation by means of a voltage electric discharge
  • the gas can be introduced into the enclosure with a flow rate
  • the surface may be, for example and without a limiting nature, a polymer material of polyethylene, polypropylene, polyamide, PET or polyvinyl chloride type.
  • the treated surface is for example made up of the internal faces of a hollow container having an opening.
  • the invention also relates to a device for treating a surface
  • the processing device further comprising:
  • - a voltage generator designed and arranged so as to be able to supply the electrode with an alternating voltage of frequency between 1 kHz and 15 MHz.
  • low-pressure gas is understood to mean a gas having a pressure of between 0.002 mbar and 10 mbar.
  • the device of the invention is designed so as to be able to implement the method of the invention.
  • the gas injector and the electrode can be one and
  • the coupling enclosure can be metallic.
  • the coupling enclosure can be cylindrical and have an axis of symmetry.
  • the vacuum chamber may be made of dielectric material and
  • the vacuum chamber can be cylindrical and have an axis of symmetry.
  • the vacuum chamber is concentric with the chamber of
  • the frequency of emission of microwave-type electromagnetic waves may be 2.45 GHz and the diameter of the coupling enclosure may be between 70 and 2000 millimeters (mm).
  • the device may further include at least two annular metal wave distribution plates, having the same axis of symmetry as the coupling enclosure, each plate having an adjustable position in a movement according to the axis of symmetry independently of the other plate.
  • annular metal wave distribution plates having the same axis of symmetry as the coupling enclosure, each plate having an adjustable position in a movement according to the axis of symmetry independently of the other plate.
  • the frequency of emission of microwave-type electromagnetic waves may be 2.45 GHz and the waveguide be of rectangular section and have dimensions of a quarter of the length d wave guided in the direction of the axis A of revolution of the cylinder and half the wavelength guided in the perpendicular direction.
  • the device may include several waveguides
  • each waveguide being coupled to a magnetron supplied by a power supply and designed to emit microwave-type electromagnetic waves in the waveguide .
  • the device may include a control module
  • the device can be adapted to the treatment of a surface consisting of the internal faces of a hollow receptacle comprising an opening and the vacuum chamber be provided with a tight sealing cover comprising a duct surrounded by a gasket designed to sealingly separate the interior from the exterior of the container, the conduit comprising the gas injector and the suction port.
  • a conduit has the advantage of positioning the gas injector and the suction port in the container.
  • the pumping circuit may further include another suction orifice opening into the vacuum chamber outside the space intended to receive the container to be treated in order to generate a vacuum on the outside of the container.
  • the other suction port makes it possible to create a vacuum outside the container in order to compensate for the negative pressure produced inside the container and to prevent the container from being excessively deformed when the vacuum is created. inside the container.
  • the pressure is greater outside the container than inside the container in order to obtain a pressure favorable to the creation of a plasma inside the container and unfavorable to the creation of the plasma. outside the container.
  • the pressure on the outside of the container is low enough to limit the pressure differential between the inside and the outside of the container to prevent deformation of the container.
  • the coupling enclosure can be confused with the vacuum enclosure.
  • the enclosure is microwave tight and gas tight.
  • the presence of a single speaker instead of two saves space and simplifies the device.
  • FIG. 1 schematically shows a top view of a device according to one embodiment of the invention
  • FIG. 2 schematically shows a view of the device of Figure 1 in vertical section along the section plane II-II;
  • FIG.3 schematically shows a vertical sectional view of a device according to a second embodiment of the invention.
  • Figures 1 and 2 show a treatment device 1 of a surface 2 to deposit a barrier effect coating.
  • the surface 2 is made of polymer and consists of the internal faces of a hollow container 20.
  • the container 20 has an opening 21.
  • the container is typically a bottle or canister.
  • Device 1 comprises:
  • the gas source comprises a precursor gas intended to be transformed into the plasma state and then to be deposited at least in part on the internal surface 2 of the container to constitute the coating.
  • the gas source is for example a pressurized gas cylinder or a wall supply.
  • the coupling enclosure 10 is metallic in order to be hermetic to microwaves.
  • the microwaves are intended to propagate in the coupling enclosure 10 while being confined there.
  • the coupling enclosure is cylindrical in shape and has an axis A of symmetry of revolution.
  • the diameter of the coupling enclosure may be between 70 and 2000 millimeters (mm).
  • the vacuum chamber 3 is intended to receive the container 20 to be treated, as illustrated in Figure 2.
  • the vacuum chamber 3 is gas-tight in order to allow the treatment which is carried out under a modified atmosphere.
  • the treatment is carried out at low pressure, between 0.002 mbar and 10 mbar.
  • the vacuum chamber 3 is dielectric and has a low property
  • the vacuum chamber 3 is placed in the coupling chamber 10.
  • the vacuum chamber is cylindrical and has the same axis A of rotational symmetry as the coupling chamber 10.
  • the vacuum chamber 3 and the coupling enclosure 10 are therefore concentric.
  • the coupling enclosure 10 is merged with the vacuum enclosure 3.
  • the enclosure is hermetic to microwaves and gas-tight.
  • the cover 31 allows the sealing of the vacuum chamber 3 of
  • the cover 31 can be removable or attached to the vacuum chamber 3.
  • the cover 31 has a duct 32, provided with a gasket 34, sealingly separating the interior from the exterior of the container.
  • the conduit 32 comprises the gas injector 5 and an orifice d.
  • the suction 41 connected to the pumping circuit 4.
  • the pipe 32 positions the gas injector 5 and the suction port 41 in the container 20.
  • the base 33 is removable. It is arranged to support the container and allows the loading and unloading of the container, the container being placed on the base 33.
  • the pumping circuit comprises two suction ports including the suction port 41 located in the conduit 32 and a second suction port 42 provided with an isolation valve and opening into the vacuum chamber outside the conduit 32 to generate a vacuum outside the container 20.
  • the suction port 41 located in the conduit 32
  • a second suction port 42 provided with an isolation valve and opening into the vacuum chamber outside the conduit 32 to generate a vacuum outside the container 20.
  • the second suction port 42 is placed in the cover 31.
  • the pumping circuit 4 is arranged to generate a depression on the one hand through the suction port 41 and on the other hand, when the valve isolation is open, through the second suction port 42.
  • the suction port 41 makes it possible to produce a vacuum inside the container 20.
  • the second suction port 42 makes it possible to produce a vacuum at the 'exterior of the container in order to compensate for the depression produced inside the container 20 and to prevent the container from deforming.
  • a device 1 'according to a second embodiment is shown in Figure 3.
  • the device 1' of the second embodiment differs from the device 1 of the first embodiment in that the pumping circuit has only one only suction port, namely the suction port 41 located in the duct 32.
  • the cover 31 'of the device 1' does not include a second suction port 42.
  • the relative position of the container 20 relative to the conduit 32 is variable between a first position and a second position. In the first position, the duct 32 provided with the seal 34 is not in contact with the opening of the container and the pumping circuit can then perform suction throughout the enclosure, the pressure inside the container then being equal to the pressure outside the container.
  • the duct 32 provided with the seal 34 is in contact with the opening of the container in a sealed manner and the pumping circuit performs suction only in the container.
  • the container is placed on a support operable between a low position and a high position, the support making it possible to move the container between the first position and the second position.
  • This second embodiment makes it possible to eliminate the problems of pressure drop within the pumping circuit present in the first variant, which induce deformation of the containers. These pressure drop problems are due to a poor pressure balance between the two orifices. Good balancing is difficult to find given the high production rates.
  • the gas injector 5 is supplied by the source of precursor gas and opens into the space intended to receive the container 20 to be treated.
  • the gas is injected in a controlled manner to obtain a pressure between 0.002 mbar and 10 mbar in the container 20.
  • the pressure can be controlled by a pressure sensor and the gas flow rate in the gas injector can be controlled by a flowmeter. .
  • the waveguides 6 open into the coupling enclosure 10 and are
  • Each waveguide has a rectangular section and has dimensions of a quarter of the guided wavelength in the direction of the axis A of revolution of the coupling chamber 10 and of a half of the guided wavelength in the transverse direction of the coupling chamber 10, that is to say a direction tangent to the perimeter of the cylinder formed by the coupling enclosure 10.
  • Each magnetron 7 is designed and arranged to emit microwave-type electromagnetic waves into the adjoining waveguide 6.
  • Each magnetron is powered by an AC power supply 13 and is designed to emit microwave-type electromagnetic waves, with a frequency between 915 MHz and 2450 MHz, in the adjoining waveguide 6.
  • Each magnetron 7 is placed in a housing 70.
  • the device may include a control module 14 programmed to operate the power supplies of the magnetrons in turn or simultaneously.
  • the electrode 8 is placed at least partially in the vacuum chamber 3.
  • the gas injector and the electrode are here one and the same element.
  • the gas injector is tubular, preferably metallic with good properties of electrical conductivity.
  • the voltage generator 9 is designed and arranged so as to be able to supply the electrode 8 with an alternating voltage of frequency between 1 kHz and 15 MHz.
  • the two plates 11 and 12 are annular and metallic. Plates 11 and 12 have the same axis of symmetry as the coupling enclosure. Each plate 11 or 12 has an adjustable position in a movement along the axis of symmetry independently of the other plate 11 or 12.
  • the plates 11 and 12 comprise adjustment means 110 and 120, respectively.
  • the adjustment means comprise for example a screw and a thumbwheel to turn the screw.
  • the treatment process makes it possible to deposit a coating with a barrier effect on a surface made of polymer material.
  • the surface is, for example and without a limiting nature, made of a polymer material of polyethylene, polypropylene, polyamide, PET or polyvinyl chloride type.
  • the treatment method comprises the following steps:
  • the introduction of the container 20 into the vacuum chamber 3 is carried out as follows.
  • the removable base 33 is removed from the vacuum chamber 3.
  • the container 20 to be treated is placed on the base 33 and then the base 33 is repositioned so as to close the vacuum chamber hermetically.
  • the pumping cycle is performed as follows.
  • the container 20 is positioned so that the seal 34 of the conduit 32 contacts the opening 21 of the container to isolate the inner part from the outer part of the container. container 20.
  • the valve In a first phase of the pumping cycle, the valve
  • isolation valve is opened and the pumping is activated so as to drop the pressure simultaneously in the container 20 through the suction port 41 and in the rest of the vacuum chamber 3 through the second orifice of suction 42.
  • the pressure in the container 20 and in the vacuum chamber 3 drops from a value corresponding to atmospheric pressure to a first predetermined value P1.
  • the isolation valve is closed and pumping continues only through port 41 in the container.
  • the pressure in the container 20 continues to drop to a second predetermined value P2, lower than the first predetermined value P1, while the pressure in the rest of the vacuum chamber 3 is maintained at the first predetermined value P1. .
  • the pumping cycle is carried out as follows.
  • the container 20 is positioned so that the seal 34 of the conduit 32 does not contact the opening 21 of the container so that the inner part and the outer part of the container 20 communicate.
  • the pumping is activated so as to drop the pressure
  • the container 20 is positioned so that the seal 34 of the conduit 32 comes into contact with the opening 21 of the container to isolate the inner part from the outer part of the container 20 and pumping continues. only in the container through the opening 41.
  • the pressure in the container 20 continues to drop to a second predetermined value P2 while the pressure in the rest of the vacuum chamber 3 is maintained at the first predetermined value P1.
  • the pressure outside the container is low enough to limit the pressure differential between the inside and the outside of the container in order to avoid deformation of the container.
  • the introduction of the precursor gas into the container 20 is carried out through the gas injector 5.
  • the precursor gas is intended, once transformed into the state of plasma, to be deposited at least in part on the internal surface 2 of the container 20 to constitute the coating.
  • the precursor gas can be a gas selected from alkanes, alkenes, alkynes, aromatics, or a combination of some of them.
  • the precursor gas can be a gas of tetrafluoroethane- 1, 1, 1, 2, of pentafluoroethane, of difluoromethane, of acetylene, or a
  • the method may further comprise a preliminary step of treating the surface with a plasma of oxygen, hydrogen, argon, carbon dioxide, helium, nitrogen or a combination of certain d 'between them.
  • the method may include depositing a succession of coating layers.
  • the gas is introduced into the enclosure at a controlled flow rate so as to
  • the excitation by means of microwave-type electromagnetic waves, and the excitation by means of an electric discharge are carried out simultaneously during a phase of the treatment known as the plasma phase.
  • the plasma phase time is between one second and 30 seconds.
  • the excitation by means of electromagnetic waves of the microwave type is carried out with a frequency between 915 MHz and 2450 MHz.
  • the power density of electromagnetic waves is between 0.01 W / cm 3 and 1 W / cm 3 .
  • the excitation by means of an electric discharge is carried out with an alternating voltage having a frequency between 20kHz and 200kHz.
  • the peak value of the voltage of the electric discharge is for example between 200 V and 500 V.
  • the power of the electric discharge is then between 4 W and 30 W.

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Abstract

The invention concerns a method for treating, in an enclosure, (3) an inner surface (2) of a container (20) made from polymer material, in order to deposit a barrier-effect coating there, comprising: - inserting the container (20) into the enclosure, - introducing a so-called precursor gas into the container (20) intended, once transformed into the plasma state, to be deposited at least partially on the inner surface of the container in order to constitute the coating, the method further comprising: - transforming the precursor gas into the plasma state by a combination of excitations comprising a main excitation by means of electromagnetic waves of the microwave type, and a secondary excitation by means of an electrical discharge of alternating voltage having a frequency of between 1 kHz and 15 MHz. The invention also relates to a device for implementing the method of the invention.

Description

Description Description
Titre de l'invention : Procédé et dispositif de traitement pour le dépôt d’un revêtement à effet barrière Title of the invention: Process and treatment device for depositing a barrier-effect coating
[0001] jL’invention concerne le domaine du traitement de surface pour obtenir le dépôt d’un revêtement à effet barrière à partir d’un plasma à basse pression. The invention relates to the field of surface treatment to obtain the deposition of a barrier effect coating from a low pressure plasma.
L’invention trouve une application particulière dans le domaine du The invention finds particular application in the field of
conditionnement de produits dans des récipients en matériau polymère. packaging of products in containers of polymer material.
[0002] Le dépôt d’un revêtement à effet barrière sur une paroi d’un récipient en matériau polymère permet de diminuer la diffusion des gaz et des liquides à travers la paroi. [0002] The deposition of a barrier effect coating on a wall of a container made of polymer material makes it possible to reduce the diffusion of gases and liquids through the wall.
[0003] En effet, l’utilisation de polymères pour le conditionnement de produits [0003] Indeed, the use of polymers for the packaging of products
présente de nombreux avantages en termes de légèreté, de souplesse, de résistance, de coût de production et de mise en œuvre, notamment en comparaison aux métaux et aux verres. En particulier, le polyéthylène, le polypropylène et le polyéthylène téréphtalate sont largement employés dans l’industrie. has many advantages in terms of lightness, flexibility, resistance, cost of production and implementation, in particular compared to metals and glasses. In particular, polyethylene, polypropylene and polyethylene terephthalate are widely used in industry.
[0004] Cependant, ces polymères présentent une résistance insuffisante à la [0004] However, these polymers exhibit insufficient resistance to
diffusion de certains produits chimiques liquides ou gazeux pour permettre leur conditionnement. Parmi ces produits chimiques se trouvent des solvants, des produits phytosanitaires ou des hydrocarbures. diffusion of certain liquid or gaseous chemicals to allow their conditioning. Among these chemicals are solvents, phytosanitary products or hydrocarbons.
[0005] Il est connu de déposer un revêtement à effet barrière sur une paroi en [0005] It is known to deposit a barrier effect coating on a wall made of
polymère afin de diminuer la diffusion de gaz et de liquides à travers la paroi. Le document FR2880027 donne des exemples de procédés de dépôt de tels revêtements. polymer to reduce the diffusion of gases and liquids through the wall. Document FR2880027 gives examples of processes for depositing such coatings.
[0006] L’opération de dépôt du revêtement est par exemple réalisée avec une [0006] The coating deposition operation is for example carried out with a
technique mettant en œuvre un plasma. Cette technique consiste à introduire à basse pression dans une enceinte un gaz, dit précurseur, comportant les éléments atomiques formant la structure moléculaire du revêtement. Le gaz précurseur est ensuite excité afin d’être transformé sous une forme instable et très réactionnelle, appelée plasma, conduisant à une recombinaison et une déposition de matière solide en couche mince sur la paroi à revêtir. Une source d’énergie de type micro-onde est communément utilisée pour exciter le gaz précurseur et le transformer en l’état de plasma car elle présente l’avantage de créer des plasmas très denses, ce qui permet l’obtention d’une vitesse de déposition importante, compatible avec des cadences industrielles. Un exemple de dispositif de traitement de surface par plasma généré par micro-ondes est donné dans le document FR2792854. technique using a plasma. This technique consists in introducing at low pressure into an enclosure a gas, called a precursor, comprising the atomic elements forming the molecular structure of the coating. The precursor gas is then excited to be transformed into an unstable form and very reactive, called plasma, leading to recombination and deposition of solid material in a thin layer on the wall to be coated. A microwave type energy source is commonly used to excite the precursor gas and transform it into the plasma state because it has the advantage of creating very dense plasmas, which makes it possible to obtain a speed of significant deposition, compatible with industrial rates. An example of a microwave-generated plasma surface treatment device is given in document FR2792854.
[0007] Un tel dispositif est constitué principalement d’une chambre métallique, [0007] Such a device consists mainly of a metal chamber,
appelée généralement enceinte de couplage micro-ondes, laquelle communique avec un guide d’ondes permettant l’introduction des micro-ondes dans la dite chambre métallique. Ce dispositif est muni également d’une enceinte en matériau diélectrique étanche au gaz appelée enceinte à vide. Le récipient à traiter est placé dans cette enceinte à vide. Generally referred to as a microwave coupling enclosure, which communicates with a waveguide allowing the introduction of microwaves into said metal chamber. This device is also provided with an enclosure made of gas-tight dielectric material called a vacuum enclosure. The container to be treated is placed in this vacuum chamber.
[0008] Dans le cadre d’une production industrielle, les dispositifs de traitement de surface par plasma généré par micro-ondes doivent permettre de traiter des parois de récipients de différents formats et de différents volumes. Il est connu d’équiper de tels dispositifs de plateaux métalliques annulaires placés dans l’enceinte de couplage, chaque plateau ayant une position réglable, [0008] In the context of industrial production, the devices for surface treatment by plasma generated by microwave must make it possible to treat the walls of containers of different formats and of different volumes. It is known to equip such devices with annular metal plates placed in the coupling enclosure, each plate having an adjustable position,
indépendamment de l’autre plateau, dans un déplacement selon un axe, pour faire varier la répartition des micro-ondes dans l’enceinte de couplage de manière adaptée au format du récipient à traiter pour obtenir une bonne homogénéité et une bonne stabilité du plasma à l’intérieur du récipient à traiter. Cependant, pour certains formats de récipients et/ou certains positionnements des récipients dans l’enceinte à vide, les plateaux métalliques ne constituent pas un moyen de réglage suffisant et le plasma obtenu peut être très instable quelle que soit la position des plateaux. En effet, dans ce cas, les formats utilisés ont des géométries qui perturbent la propagation des micro-ondes. La part d’énergie des micro-ondes couplée, c’est-à-dire transmise au plasma, n’est alors pas suffisante pour entretenir un plasma stable favorisant la formation d’un independently of the other plate, in a displacement along an axis, to vary the distribution of the microwaves in the coupling chamber in a manner adapted to the format of the container to be treated in order to obtain good homogeneity and good stability of the plasma at inside the container to be treated. However, for certain container formats and / or certain positions of the containers in the vacuum chamber, the metal trays do not constitute a sufficient means of adjustment and the plasma obtained can be very unstable regardless of the position of the trays. In fact, in this case, the formats used have geometries which disturb the propagation of the microwaves. The portion of microwave energy coupled, that is to say transmitted to the plasma, is then not sufficient to maintain a stable plasma promoting the formation of a
revêtement à effet barrière performant. En outre, pendant une production industrielle le positionnement des récipients dans l’enceinte n’est pas toujours reproductible et peut parfois varier, ce qui engendre également des perturbations de l’excitation du plasma. Ces perturbations entraînent des taux de rebus qui peuvent être importants. high-performance barrier effect coating. In addition, during industrial production, the positioning of the containers in the enclosure is not always reproducible and can sometimes vary, which also causes disturbances in plasma excitation. These disruptions lead to reject rates which can be significant.
[0009] L’invention propose une solution visant à pallier les inconvénients et les [0009] The invention proposes a solution aimed at overcoming the drawbacks and the
problèmes précités. Un objectif de l’invention est d’obtenir un plasma stable quelle que soit la géométrie et la position du récipient à traiter pour y déposer sur sa surface interne un revêtement à effet barrière performant. aforementioned problems. An objective of the invention is to obtain a stable plasma regardless of the geometry and the position of the container to be treated in order to deposit thereon on its internal surface a coating with a high-performance barrier effect.
[0010] L’invention concerne un procédé de traitement dans une enceinte d’une [0010] The invention relates to a method of treatment in an enclosure of a
surface interne d’un récipient en matériau polymère pour y déposer un internal surface of a container made of polymer material to deposit a
revêtement à effet barrière, comprenant : barrier effect coating, comprising:
- l’introduction du récipient dans l’enceinte, - the introduction of the container into the enclosure,
- l’introduction dans le récipient d’un gaz dit précurseur destiné, une fois transformé en l’état de plasma, à être déposé au moins en partie sur la surface interne du récipient pour constituer le revêtement, et - the introduction into the container of a so-called precursor gas intended, once transformed into the plasma state, to be deposited at least in part on the internal surface of the container to constitute the coating, and
- la transformation en l’état de plasma du gaz précurseur par une combinaison d’excitations comprenant une excitation principale au moyen d’ondes - the transformation into the plasma state of the precursor gas by a combination of excitations including a main excitation by means of waves
électromagnétiques de type micro-ondes, et une excitation secondaire au moyen d’une décharge électrique de tension alternative ayant une fréquence comprise entre 1 kHz et 15 MHz. microwave type electromagnetic, and secondary excitation by means of an electric discharge of alternating voltage having a frequency between 1 kHz and 15 MHz.
De préférence, la tension alternative a une fréquence comprise entre 10kHz et 200kHz. Preferably, the alternating voltage has a frequency between 10kHz and 200kHz.
On entend par micro-ondes des ondes électromagnétiques de fréquence comprise entre 300 MHz et 3000 MHz. By microwave is meant electromagnetic waves with a frequency between 300 MHz and 3000 MHz.
De préférence, les micro-ondes ont une fréquence comprise entre 915 Mhz et 2450 MHz. Preferably, the microwaves have a frequency between 915 MHz and 2450 MHz.
On entend par revêtement à effet barrière un revêtement déposé sur une paroi ayant la propriété de diminuer la diffusion de gaz et de liquides à travers la paroi. L’excitation principale au moyen d’ondes électromagnétiques de type micro ondes est l’excitation qui permet d’opérer la transformation du gaz précurseur en l’état de plasma et qui permet de réaliser le dépôt pour constituer le revêtement à effet barrière. En effet, la puissance de l’excitation principale est supérieure à la puissance de l’excitation secondaire et c’est l’excitation principale qui fournit l’énergie nécessaire à la transformation du gaz précurseur en l’état de plasma et nécessaire au dépôt. L’excitation secondaire au moyen d’une décharge électrique de tension alternative permet d’obtenir un plasma stable, quel que soit la forme géométrique ou la position du récipient dans l’enceinte de couplage, c’est-à-dire qu’une portion du gaz est transformée en plasma et reste à l’état de plasma pendant toute la durée de l’excitation. Cette portion du gaz transformée en plasma et demeurant à l’état de plasma va ensuite permettre à l’excitation principale au moyen des micro-ondes de s’établir de façon stable durant toute sa durée. La combinaison de l’excitation principale et de l’excitation secondaire est bénéfique car dans certains cas, notamment pour certains formats, l’excitation au moyen d’ondes électromagnétiques de type micro-ondes seule n’est pas suffisante dans la mesure où la transmission de l’énergie des micro-ondes au plasma peut être perturbée par la forme du récipient et n’est alors pas totalement consommée par le gaz pour être transformé en l’état de plasma. Par conséquent, le gaz précurseur ne se transforme pas de manière suffisamment durable pour réaliser un revêtement performant. Il convient de préciser que l’excitation au moyen d’une décharge électrique de tension alternative seule ne permet pas d’avoir des vitesses de dépôt suffisamment rapides pour des cadences The term “barrier effect coating” means a coating deposited on a wall having the property of reducing the diffusion of gases and liquids through the wall. The main excitation by means of electromagnetic waves of the microwave type is the excitation which makes it possible to transform the precursor gas into the plasma state and which makes it possible to carry out the deposit to constitute the barrier effect coating. Indeed, the power of the main excitation is greater than the power of the secondary excitation and it is the main excitation which provides the energy necessary for the transformation of the precursor gas into the plasma state and necessary for the deposition. The secondary excitation by means of an electric discharge of alternating voltage makes it possible to obtain a stable plasma, whatever the geometric shape or the position of the container in the coupling enclosure, that is to say a portion of the gas is transformed into plasma and remains in the plasma state throughout the duration of the excitation. This portion of the gas transformed into plasma and remaining in the plasma state will then allow the main excitation by means of microwaves to be established in a stable manner throughout its duration. The combination of the main excitation and the secondary excitation is beneficial because in certain cases, in particular for certain formats, the excitation by means of electromagnetic waves of the microwave type alone is not sufficient insofar as the transmission of energy from microwaves to plasma can be disturbed by the shape of the container and is then not totally consumed by the gas to be transformed into the plasma state. Consequently, the precursor gas does not transform in a sufficiently durable manner to achieve a performance coating. It should be noted that the excitation by means of an electric discharge of alternating voltage alone does not make it possible to have sufficiently fast deposition rates for rates
industrielles. L’avantage de combiner l’excitation au moyen d’ondes industrial. The advantage of combining excitement by means of waves
électromagnétiques de type micro-ondes et l’excitation au moyen d’une décharge électrique est d’obtenir de manière simultanée, la rapidité de traitement conférée par un plasma généré par micro-ondes et la stabilité d’un plasma généré par une excitation par une décharge électrique. electromagnetic microwave type and the excitation by means of an electric discharge is to obtain simultaneously, the speed of treatment conferred by a plasma generated by microwaves and the stability of a plasma generated by an excitation by an electric shock.
[0011] Selon l’invention : [0011] According to the invention:
- l’excitation au moyen d’ondes électromagnétiques de type micro-ondes, et - the excitation by means of electromagnetic waves of the microwave type, and
- l’excitation au moyen d’une décharge électrique de tension alternative peuvent être réalisées simultanément au cours d’une phase du traitement dite phase plasma. - the excitation by means of an electrical discharge of alternating voltage can be carried out simultaneously during a phase of the treatment called the plasma phase.
[0012] Selon l’invention, le temps de phase plasma peut être compris entre une [0012] According to the invention, the plasma phase time can be between one
seconde et 10 minutes, de préférence entre une seconde et 30 secondes. second and 10 minutes, preferably between one second and 30 seconds.
[0013] Selon l’invention la valeur crête de la tension de la décharge électrique peut être comprise entre 100 V et 1000 V, de préférence entre 200 V et 500 V. [0014] Selon l’invention, le gaz précurseur peut être un gaz choisi parmi les alcanes, les alcènes, les alcynes, les aromatiques, ou une combinaison de certains d’entre eux. [0013] According to the invention, the peak value of the voltage of the electric discharge may be between 100 V and 1000 V, preferably between 200 V and 500 V. [0014] According to the invention, the precursor gas may be a gas chosen from alkanes, alkenes, alkynes, aromatics, or a combination of some of them.
[0015] Selon l’invention le gaz précurseur peut être un gaz de tétrafluoroéthane- 1 ,1 , 1 ,2, de pentafluoroéthane, de difluorométhane, d’acétylène, ou une combinaison de certains d’entre eux ou un mélange de certains d’entre eux avec un gaz rare tel que l’argon. According to the invention the precursor gas can be a tetrafluoroethane gas- 1, 1, 1, 2, pentafluoroethane, difluoromethane, acetylene, or a combination of some of them or a mixture of some of them. 'between them with a rare gas such as argon.
[0016] Selon l’invention, le procédé peut comporter en outre une étape préalable de traitement de la surface par un plasma d’oxygène, d’hydrogène, d’argon, de dioxyde de carbone, d’hélium, d’azote ou une combinaison de certains d’entre eux. [0016] According to the invention, the method may further include a preliminary step of treating the surface with a plasma of oxygen, hydrogen, argon, carbon dioxide, helium, nitrogen or a combination of some of them.
[0017] Selon l’invention, le procédé peut comporter le dépôt d’une succession de couches de revêtement. [0017] According to the invention, the method may include the deposition of a succession of coating layers.
[0018] Selon l’invention, la densité volumique de puissance des ondes [0018] According to the invention, the power volume density of the waves
électromagnétiques peut être comprise entre 0,01 W/cm3 et 1 W/cm3. Ainsi, pour un bidon de 4 L, la puissance des ondes électromagnétiques peut être comprise entre 40 W et 4 kW, pour un bidon de 20 L, la puissance des ondes electromagnetic can be between 0.01 W / cm 3 and 1 W / cm 3 . Thus, for a 4 L can, the power of the electromagnetic waves can be between 40 W and 4 kW, for a 20 L can, the power of the waves
électromagnétiques peut être comprise entre 200 W et 20 kW. electromagnetic can be between 200 W and 20 kW.
[0019] Selon l’invention, la puissance de la décharge électrique peut être comprise entre 1 W et 2000 W, de préférence entre 4 W et 100 W. [0019] According to the invention, the power of the electric discharge can be between 1 W and 2000 W, preferably between 4 W and 100 W.
[0020] Selon l’invention, la puissance de l’excitation principale au moyen d’ondes électromagnétiques de type micro-ondes est supérieure à la puissance de l’excitation secondaire au moyen d’une décharge électrique de tension [0020] According to the invention, the power of the main excitation by means of microwave-type electromagnetic waves is greater than the power of the secondary excitation by means of a voltage electric discharge
alternative. alternative.
[0021] Selon l’invention, le gaz peut être introduit dans l’enceinte avec un débit [0021] According to the invention, the gas can be introduced into the enclosure with a flow rate
contrôlé de manière à maintenir l’enceinte à une pression comprise entre 0,002 mbar et 10 mbar, de préférence entre 0,01 mbar et 1 mbar. controlled so as to maintain the enclosure at a pressure between 0.002 mbar and 10 mbar, preferably between 0.01 mbar and 1 mbar.
[0022] Selon l’invention, la surface peut être par exemple et sans caractère limitatif en matériau polymère de type polyéthylène, polypropylène, polyamide, PET, ou polychlorure de vinyle. [0023] Selon l’invention, la surface traitée est par exemple constituée des faces internes d’un récipient creux comportant une ouverture. [0022] According to the invention, the surface may be, for example and without a limiting nature, a polymer material of polyethylene, polypropylene, polyamide, PET or polyvinyl chloride type. [0023] According to the invention, the treated surface is for example made up of the internal faces of a hollow container having an opening.
[0024] L’invention concerne également un dispositif de traitement d’une surface [0024] The invention also relates to a device for treating a surface
interne d’un récipient en matériau polymère pour y déposer un revêtement à effet barrière comportant : inside of a container made of polymer material to deposit a barrier-effect coating comprising:
- une enceinte de couplage constituant un espace de propagation d’ondes électromagnétiques de type micro-onde, - a coupling enclosure constituting a microwave-type electromagnetic wave propagation space,
- une enceinte à vide étanche aux gaz placée dans l’enceinte de couplage et comportant un espace destiné à recevoir le récipient, - a gas-tight vacuum chamber placed in the coupling chamber and comprising a space intended to receive the container,
- un circuit de pompage agencé pour engendrer une dépression dans l’enceinte à vide au travers d’un orifice d’aspiration, - a pumping circuit designed to generate a vacuum in the vacuum chamber through a suction port,
- une source de gaz dit précurseur destiné, une fois transformé en l’état de plasma, à être déposé au moins en partie sur la surface interne du récipient pour constituer le revêtement, - a source of so-called precursor gas intended, once transformed into the plasma state, to be deposited at least in part on the internal surface of the container to form the coating,
- un injecteur de gaz alimenté par la source de gaz précurseur et débouchant dans l’espace destiné à recevoir le récipient, - a gas injector supplied by the source of precursor gas and opening into the space intended to receive the container,
- au moins un guide d’onde débouchant dans l’enceinte de couplage, - at least one waveguide opening into the coupling enclosure,
- au moins un magnétron conçu et agencé de manière à émettre des ondes électromagnétiques de type micro-onde, dans l’au moins un guide d’onde, le dispositif de traitement comportant en outre : - at least one magnetron designed and arranged so as to emit microwave-type electromagnetic waves in at least one waveguide, the processing device further comprising:
- une électrode placée au moins partiellement dans l’espace destiné à recevoir le récipient, et - an electrode placed at least partially in the space intended to receive the container, and
- un générateur de tension conçu et agencé de manière à pouvoir alimenter l’électrode avec une tension alternative de fréquence comprise entre 1 kHz et 15 MHz . - a voltage generator designed and arranged so as to be able to supply the electrode with an alternating voltage of frequency between 1 kHz and 15 MHz.
On entend par gaz à basse pression un gaz ayant une pression comprise entre 0,002 mbar et 10 mbar. The term “low-pressure gas” is understood to mean a gas having a pressure of between 0.002 mbar and 10 mbar.
Le dispositif de l’invention est conçu de manière à pouvoir mettre en œuvre le procédé de l’invention. The device of the invention is designed so as to be able to implement the method of the invention.
[0025] Selon l’invention, l’injecteur de gaz et l’électrode peuvent être un seul et [0025] According to the invention, the gas injector and the electrode can be one and
même élément. same element.
[0026] Selon l’invention, l’enceinte de couplage peut être métallique. [0027] Selon l’invention, l’enceinte de couplage peut être cylindrique et présenter un axe de symétrie. [0026] According to the invention, the coupling enclosure can be metallic. [0027] According to the invention, the coupling enclosure can be cylindrical and have an axis of symmetry.
[0028] Selon l’invention, l’enceinte à vide peut être en matériau diélectrique et [0028] According to the invention, the vacuum chamber may be made of dielectric material and
présente une faible propriété d’absorption des micro-ondes. exhibits poor microwave absorption property.
[0029] Selon l’invention, l’enceinte à vide peut être cylindrique et présenter un axe de symétrie. [0029] According to the invention, the vacuum chamber can be cylindrical and have an axis of symmetry.
[0030] Selon l’invention, l’enceinte à vide est concentrique avec l’enceinte de [0030] According to the invention, the vacuum chamber is concentric with the chamber of
couplage. coupling.
[0031] Selon l’invention, la fréquence d’émission des ondes électromagnétiques de type micro-onde peut être de 2,45 GHz et le diamètre de l’enceinte de couplage être compris entre 70 et 2000 millimètres (mm). According to the invention, the frequency of emission of microwave-type electromagnetic waves may be 2.45 GHz and the diameter of the coupling enclosure may be between 70 and 2000 millimeters (mm).
[0032] Selon l’invention, le dispositif peut comporter en outre au moins deux plateaux annulaires métalliques de répartition des ondes, ayant le même axe de symétrie que l’enceinte de couplage, chaque plateau ayant une position réglable dans un déplacement selon l’axe de symétrie indépendamment de l’autre plateau. De tels plateaux permettent de faire varier la répartition des micro-ondes dans l’enceinte de couplage pour obtenir une bonne homogénéité et une bonne stabilité du plasma à proximité de la surface du récipient à traiter According to the invention, the device may further include at least two annular metal wave distribution plates, having the same axis of symmetry as the coupling enclosure, each plate having an adjustable position in a movement according to the axis of symmetry independently of the other plate. Such plates make it possible to vary the distribution of the microwaves in the coupling chamber to obtain good homogeneity and good stability of the plasma near the surface of the container to be treated
[0033] Selon l’invention, la fréquence d’émission des ondes électromagnétiques de type micro-onde peut être de 2,45 GHz et le guide d’onde être de section rectangulaire et présenter des dimensions d’un quart de la longueur d’onde guidée selon la direction de l’axe A de révolution du cylindre et d’un demi de la longueur d’onde guidée selon la direction perpendiculaire. According to the invention, the frequency of emission of microwave-type electromagnetic waves may be 2.45 GHz and the waveguide be of rectangular section and have dimensions of a quarter of the length d wave guided in the direction of the axis A of revolution of the cylinder and half the wavelength guided in the perpendicular direction.
[0034] Selon l’invention, le dispositif peut comporter plusieurs guides d’onde [0034] According to the invention, the device may include several waveguides
débouchant dans l’enceinte de couplage et répartis autour de l’enceinte de couplage, chaque guide d’onde étant couplé à un magnétron alimenté par une alimentation électrique et conçu pour émettre des ondes électromagnétiques de type micro-onde dans le guide d’onde. opening into the coupling enclosure and distributed around the coupling enclosure, each waveguide being coupled to a magnetron supplied by a power supply and designed to emit microwave-type electromagnetic waves in the waveguide .
[0035] Selon l’invention, le dispositif peut comporter un module de contrôle [0035] According to the invention, the device may include a control module
programmé pour faire fonctionner les alimentations électriques des magnétrons à tour de rôle ou simultanément. [0036] Selon l’invention, le dispositif peut être adapté au traitement d’une surface constituée des faces internes d’un récipient creux comportant une ouverture et l’enceinte à vide être munie d’un couvercle d’obturation étanche comportant un conduit entouré d’un joint conçu pour séparé de manière étanche l’intérieur de l’extérieur du récipient, le conduit comportant l’injecteur de gaz et l’orifice d’aspiration. Un tel conduit présente l’avantage de positionner l’injecteur de gaz et l’orifice d’aspiration dans le récipient. programmed to operate magnetron power supplies in turn or simultaneously. According to the invention, the device can be adapted to the treatment of a surface consisting of the internal faces of a hollow receptacle comprising an opening and the vacuum chamber be provided with a tight sealing cover comprising a duct surrounded by a gasket designed to sealingly separate the interior from the exterior of the container, the conduit comprising the gas injector and the suction port. Such a conduit has the advantage of positioning the gas injector and the suction port in the container.
[0037] Selon l’invention, le circuit de pompage peut comporter en outre un autre orifice d’aspiration débouchant dans l’enceinte à vide en dehors de l’espace destiné à recevoir le récipient à traiter pour engendrer une dépression à l’extérieur du récipient. L’autre orifice d’aspiration permet de réaliser une dépression à l’extérieur du récipient afin de compenser la dépression réalisée à l’intérieur du récipient et d’éviter que le récipient ne se déforme de manière excessive lorsque le vide est créé à l’intérieur du récipient. Suite au pompage, la pression est plus importante à l’extérieur du récipient qu’à l’intérieur du récipient afin d’obtenir une pression favorable à la création d’un plasma à l’intérieur du récipient et défavorable à la création du plasma à l’extérieur du récipient. De plus, la pression à l’extérieur du récipient est suffisamment faible pour limiter le différentiel de pression entre l’intérieur et l’extérieur du récipient afin d’éviter la déformation du récipient. According to the invention, the pumping circuit may further include another suction orifice opening into the vacuum chamber outside the space intended to receive the container to be treated in order to generate a vacuum on the outside of the container. The other suction port makes it possible to create a vacuum outside the container in order to compensate for the negative pressure produced inside the container and to prevent the container from being excessively deformed when the vacuum is created. inside the container. Following pumping, the pressure is greater outside the container than inside the container in order to obtain a pressure favorable to the creation of a plasma inside the container and unfavorable to the creation of the plasma. outside the container. In addition, the pressure on the outside of the container is low enough to limit the pressure differential between the inside and the outside of the container to prevent deformation of the container.
[0038] Selon l’invention, l’enceinte de couplage peut être confondue avec l’enceinte à vide. Dans ce cas, l’enceinte est hermétique aux micro-ondes et étanche aux gaz. La présence d’une seule enceinte au lieu de deux permet un gain de place et une simplification du dispositif. [0038] According to the invention, the coupling enclosure can be confused with the vacuum enclosure. In this case, the enclosure is microwave tight and gas tight. The presence of a single speaker instead of two saves space and simplifies the device.
[0039] D'autres caractéristiques et avantages de la présente invention apparaîtront plus clairement à la lecture de la description détaillée qui suit d'un mode de réalisation de l'invention donné à titre d'exemple nullement limitatif et illustré par les dessins annexés, dans lesquels : Other characteristics and advantages of the present invention will emerge more clearly on reading the following detailed description of an embodiment of the invention given by way of non-limiting example and illustrated by the accompanying drawings, wherein :
[0040] [Fig. 1] représente schématiquement une vue de dessus d’un dispositif selon un mode de réalisation de l’invention ; et [0041] [Fig. 2] représente schématiquement une vue du dispositif de la figure 1 en coupe verticale selon le plan de coupe ll-ll ; et [Fig. 1] schematically shows a top view of a device according to one embodiment of the invention; and [0041] [Fig. 2] schematically shows a view of the device of Figure 1 in vertical section along the section plane II-II; and
[0042] [Fig.3] représente schématiquement une vue en coupe verticale d’un dispositif selon un deuxième mode de réalisation de l’invention. [0042] [Fig.3] schematically shows a vertical sectional view of a device according to a second embodiment of the invention.
[0043] Les figures 1 et 2 représentent un dispositif de traitement 1 d’une surface 2 pour y déposer un revêtement à effet barrière. La surface 2 est en polymère et est constituée des faces internes d’un récipient 20 creux. Le récipient 20 comporte une ouverture 21. Le récipient est typiquement une bouteille ou un bidon. Figures 1 and 2 show a treatment device 1 of a surface 2 to deposit a barrier effect coating. The surface 2 is made of polymer and consists of the internal faces of a hollow container 20. The container 20 has an opening 21. The container is typically a bottle or canister.
Le dispositif 1 comporte : Device 1 comprises:
- une enceinte de couplage 10, - a coupling enclosure 10,
- une enceinte à vide 3, - a vacuum chamber 3,
- un circuit de pompage 4, - a pumping circuit 4,
- une source de gaz (non représentée), - a gas source (not shown),
- un injecteur de gaz 5, - a gas injector 5,
- deux guides d’onde 6, - two waveguides 6,
- deux magnétrons 7, - two magnetrons 7,
- une électrode 8, - an electrode 8,
- un générateur de tension 9, - a voltage generator 9,
- deux plateaux 11 et 12 - two trays 11 and 12
- un module de contrôle 14, - a control module 14,
- un couvercle 31 , et - a cover 31, and
- un socle 33. - a base 33.
[0044] La source de gaz comprend un gaz précurseur destiné à être transformé en l’état de plasma puis à être déposé au moins en partie sur la surface 2 interne du récipient pour constituer le revêtement. La source de gaz est par exemple une bouteille de gaz sous pression ou une alimentation murale. [0044] The gas source comprises a precursor gas intended to be transformed into the plasma state and then to be deposited at least in part on the internal surface 2 of the container to constitute the coating. The gas source is for example a pressurized gas cylinder or a wall supply.
[0045] L’enceinte de couplage 10 est métallique afin d’être hermétique aux micro ondes. Les micro-ondes sont destinées à se propager dans l’enceinte de couplage 10 tout en y étant confinées. L’enceinte de couplage est de forme cylindrique et présente un axe A de symétrie de révolution. A titre illustratif et nullement limitatif, le diamètre de l’enceinte de couplage peut être compris entre 70 et 2000 millimètres (mm). The coupling enclosure 10 is metallic in order to be hermetic to microwaves. The microwaves are intended to propagate in the coupling enclosure 10 while being confined there. The coupling enclosure is cylindrical in shape and has an axis A of symmetry of revolution. For illustrative purposes and in no way limiting, the diameter of the coupling enclosure may be between 70 and 2000 millimeters (mm).
[0046] L’enceinte à vide 3 est destinée à recevoir le récipient 20 à traiter, comme illustré sur la figure 2. L’enceinte à vide 3 est étanche aux gaz afin de permettre le traitement qui est réalisé sous atmosphère modifiée. En particulier le traitement est réalisé à basse pression, entre 0,002 mbar et 10 mbar. The vacuum chamber 3 is intended to receive the container 20 to be treated, as illustrated in Figure 2. The vacuum chamber 3 is gas-tight in order to allow the treatment which is carried out under a modified atmosphere. In particular, the treatment is carried out at low pressure, between 0.002 mbar and 10 mbar.
[0047] L’enceinte à vide 3 est diélectrique et présente une faible propriété [0047] The vacuum chamber 3 is dielectric and has a low property
d’absorption des micro-ondes afin de permettre la transmission de l’énergie portée par les micro-ondes au gaz qu’elle contient sans que cette énergie ne soit absorbée par l’enceinte à vide 3 elle-même. absorption of the microwaves in order to allow the transmission of the energy carried by the microwaves to the gas it contains without this energy being absorbed by the vacuum chamber 3 itself.
[0048] L’enceinte à vide 3 est placée dans l’enceinte de couplage 10. L’enceinte à vide est cylindrique et présente le même axe A de symétrie de révolution que l’enceinte de couplage 10. L’enceinte à vide 3 et l’enceinte de couplage 10 sont donc concentriques. The vacuum chamber 3 is placed in the coupling chamber 10. The vacuum chamber is cylindrical and has the same axis A of rotational symmetry as the coupling chamber 10. The vacuum chamber 3 and the coupling enclosure 10 are therefore concentric.
[0049] Selon une variante non représentée, l’enceinte de couplage 10 est confondue avec l’enceinte à vide 3. Dans ce cas, l’enceinte est hermétique aux micro-ondes et étanche aux gaz. According to a variant not shown, the coupling enclosure 10 is merged with the vacuum enclosure 3. In this case, the enclosure is hermetic to microwaves and gas-tight.
[0050] Le couvercle 31 permet de réaliser l’obturation de l’enceinte à vide 3 de The cover 31 allows the sealing of the vacuum chamber 3 of
manière étanche. Le couvercle 31 peut être amovible ou fixé sur l’enceinte à vide 3. Le couvercle 31 comporte un conduit 32, muni d’un joint 34, séparant de manière étanche l’intérieur de l’extérieur du récipient. Ainsi, le gaz précurseur peut être confiné à l’intérieur du récipient 20 et la pression dans le récipient 20 peut être différente de la pression à l’extérieur du récipient 20. Le conduit 32 comporte l’injecteur de gaz 5 et un orifice d’aspiration 41 connecté au circuit de pompage 4. Le conduit 32 positionne l’injecteur de gaz 5 et l’orifice d’aspiration 41 dans le récipient 20. waterproof way. The cover 31 can be removable or attached to the vacuum chamber 3. The cover 31 has a duct 32, provided with a gasket 34, sealingly separating the interior from the exterior of the container. Thus, the precursor gas can be confined inside the container 20 and the pressure in the container 20 can be different from the pressure outside the container 20. The conduit 32 comprises the gas injector 5 and an orifice d. The suction 41 connected to the pumping circuit 4. The pipe 32 positions the gas injector 5 and the suction port 41 in the container 20.
[0051] Le socle 33 est amovible. Il est agencé pour supporter le récipient et permet le chargement et le déchargement du récipient, le récipient étant posé sur le socle 33. [0051] The base 33 is removable. It is arranged to support the container and allows the loading and unloading of the container, the container being placed on the base 33.
[0052] Selon un premier mode de réalisation représenté aux figures 1 et 2, le circuit de pompage comporte deux orifices d’aspiration dont l’orifice d’aspiration 41 situé dans le conduit 32 et un deuxième orifice d’aspiration 42 muni d’une vanne d’isolement et débouchant dans l’enceinte à vide en dehors du conduit 32 pour engendrer une dépression à l’extérieur du récipient 20. Dans l’exemple According to a first embodiment shown in Figures 1 and 2, the pumping circuit comprises two suction ports including the suction port 41 located in the conduit 32 and a second suction port 42 provided with an isolation valve and opening into the vacuum chamber outside the conduit 32 to generate a vacuum outside the container 20. In the example
représenté, le deuxième orifice d’aspiration 42 est placé dans le couvercle 31. Le circuit de pompage 4 est agencé pour engendrer une dépression d’une part au travers de l’orifice d’aspiration 41 et d’autre part, lorsque la vanne d’isolement est ouverte, au travers du deuxième orifice d’aspiration 42. L’orifice d’aspiration 41 permet de réaliser une dépression à l’intérieur du récipient 20. Le deuxième orifice d’aspiration 42 permet de réaliser une dépression à l’extérieur du récipient afin de compenser la dépression réalisée à l’intérieur du récipient 20 et d’éviter que le récipient ne se déforme. shown, the second suction port 42 is placed in the cover 31. The pumping circuit 4 is arranged to generate a depression on the one hand through the suction port 41 and on the other hand, when the valve isolation is open, through the second suction port 42. The suction port 41 makes it possible to produce a vacuum inside the container 20. The second suction port 42 makes it possible to produce a vacuum at the 'exterior of the container in order to compensate for the depression produced inside the container 20 and to prevent the container from deforming.
[0053] Un dispositif 1’ selon un deuxième mode de réalisation est représenté à la figure 3. Le dispositif 1’ du deuxième mode de réalisation diffère du dispositif 1 du premier mode de réalisation en ce que le circuit de pompage ne comporte qu’un seul orifice d’aspiration, à savoir l’orifice d’aspiration 41 situé dans le conduit 32. Dans ce deuxième mode de réalisation, le couvercle 31’ du dispositif 1’ ne comporte pas de deuxième orifice d’aspiration 42. La position relative du récipient 20 par rapport au conduit 32 est variable entre une première position et une deuxième position. Dans la première position, le conduit 32 muni du joint 34 n’est pas en contact avec l’ouverture du récipient et le circuit de pompage peut réaliser alors une aspiration dans toute l’enceinte, la pression à l’intérieur du récipient étant alors égale à la pression à l’extérieur du récipient. Dans la deuxième position, le conduit 32 muni du joint 34 est en contact avec l’ouverture du récipient de manière étanche et le circuit de pompage réalise une aspiration uniquement dans le récipient. Ainsi, il est possible d’obtenir un différentiel de pression entre l’intérieur du récipient et l’extérieur du récipient avec une pression plus faible à l’intérieur du récipient. Par exemple, le récipient est placé sur un support actionnable entre une position basse et une position haute, le support permettant de déplacer le récipient entre la première position et la deuxième position. Ce deuxième mode de réalisation permet d’éliminer des problèmes de perte de charge au sein du circuit de pompage présents dans la première variante, lesquels induisent des déformations des récipients. Ces problèmes de perte de charge sont dus à un mauvais équilibrage des pressions entre les deux orifices. Un bon équilibrage est difficile à trouver étant donné les cadences importantes de production. A device 1 'according to a second embodiment is shown in Figure 3. The device 1' of the second embodiment differs from the device 1 of the first embodiment in that the pumping circuit has only one only suction port, namely the suction port 41 located in the duct 32. In this second embodiment, the cover 31 'of the device 1' does not include a second suction port 42. The relative position of the container 20 relative to the conduit 32 is variable between a first position and a second position. In the first position, the duct 32 provided with the seal 34 is not in contact with the opening of the container and the pumping circuit can then perform suction throughout the enclosure, the pressure inside the container then being equal to the pressure outside the container. In the second position, the duct 32 provided with the seal 34 is in contact with the opening of the container in a sealed manner and the pumping circuit performs suction only in the container. Thus, it is possible to obtain a pressure differential between the inside of the container and the outside of the container with a lower pressure inside the container. For example, the container is placed on a support operable between a low position and a high position, the support making it possible to move the container between the first position and the second position. This second embodiment makes it possible to eliminate the problems of pressure drop within the pumping circuit present in the first variant, which induce deformation of the containers. These pressure drop problems are due to a poor pressure balance between the two orifices. Good balancing is difficult to find given the high production rates.
[0054] L’injecteur de gaz 5 est alimenté par la source de gaz précurseur et débouche dans l’espace destiné à recevoir le récipient 20 à traiter. Le gaz est injecté de manière contrôlée pour obtenir une pression comprise entre 0,002 mbar et 10 mbar dans le récipient 20. La pression peut être contrôlée par un capteur de pression et le débit de gaz dans l’injecteur de gaz peut être contrôlé par un débitmètre. [0054] The gas injector 5 is supplied by the source of precursor gas and opens into the space intended to receive the container 20 to be treated. The gas is injected in a controlled manner to obtain a pressure between 0.002 mbar and 10 mbar in the container 20. The pressure can be controlled by a pressure sensor and the gas flow rate in the gas injector can be controlled by a flowmeter. .
[0055] Les guides d’onde 6 débouchent dans l’enceinte de couplage 10 et sont [0055] The waveguides 6 open into the coupling enclosure 10 and are
répartis autour de l’enceinte de couplage 10. Dans l’exemple, ils sont distributed around the coupling enclosure 10. In the example, they are
diamétralement opposés par rapport au diamètre du cylindre formé par l’enceinte de couplage 10. Chaque guide d’onde a une section rectangulaire et présente des dimensions d’un quart de la longueur d’onde guidée selon la direction de l’axe A de révolution de l’enceinte de couplage 10 et d’un demi de la longueur d’onde guidée selon la direction transverse de l’enceinte de couplage 10, c’est-à- dire une direction tangente au périmètre du cylindre formé par l’enceinte de couplage 10. diametrically opposed with respect to the diameter of the cylinder formed by the coupling enclosure 10. Each waveguide has a rectangular section and has dimensions of a quarter of the guided wavelength in the direction of the axis A of revolution of the coupling chamber 10 and of a half of the guided wavelength in the transverse direction of the coupling chamber 10, that is to say a direction tangent to the perimeter of the cylinder formed by the coupling enclosure 10.
[0056] Chaque magnétron 7 est conçu et agencé de manière à émettre des ondes électromagnétiques de type micro-ondes dans le guide d’onde 6 attenant. Each magnetron 7 is designed and arranged to emit microwave-type electromagnetic waves into the adjoining waveguide 6.
Chaque magnétron est alimenté par une alimentation électrique 13 alternative et est conçu pour émettre des ondes électromagnétiques de type micro-onde, de fréquence comprise entre 915 Mhz et 2450 MHz, dans le guide d’onde 6 attenant. Chaque magnétron 7 est placé dans un boîtier 70. Each magnetron is powered by an AC power supply 13 and is designed to emit microwave-type electromagnetic waves, with a frequency between 915 MHz and 2450 MHz, in the adjoining waveguide 6. Each magnetron 7 is placed in a housing 70.
[0057] Le dispositif peut comporter un module de contrôle 14 programmé pour faire fonctionner les alimentations électriques des magnétrons à tour de rôle ou simultanément. The device may include a control module 14 programmed to operate the power supplies of the magnetrons in turn or simultaneously.
[0058] L’électrode 8 est placée au moins partiellement dans l’enceinte à vide 3. [0058] The electrode 8 is placed at least partially in the vacuum chamber 3.
L’injecteur de gaz et l’électrode sont ici un seul et même élément. Ainsi, l’injecteur de gaz est tubulaire, de préférence métallique avec de bonnes propriétés de conductivité électrique. [0059] Le générateur de tension 9 est conçu et agencé de manière à pouvoir alimenter l’électrode 8 avec une tension alternative de fréquence comprise entre 1 kHz et 15 MHz. The gas injector and the electrode are here one and the same element. Thus, the gas injector is tubular, preferably metallic with good properties of electrical conductivity. The voltage generator 9 is designed and arranged so as to be able to supply the electrode 8 with an alternating voltage of frequency between 1 kHz and 15 MHz.
[0060] Les deux plateaux 11 et 12 sont annulaires et métalliques. Les plateaux 11 et 12 ont le même axe de symétrie que l’enceinte de couplage. Chaque plateau 11 ou 12 a une position réglable dans un déplacement selon l’axe de symétrie indépendamment de l’autre plateau 11 ou 12. Les plateaux 11 et 12 comportent des moyens de réglage respectivement 110 et 120. Les moyens de réglage comportent par exemple une vis et une molette permettant de faire tourner la vis. De tels plateaux 11 et 12 permettent de faire varier la répartition des micro-ondes dans l’enceinte de couplage pour obtenir une bonne homogénéité et une bonne stabilité du plasma à proximité de la surface à traiter The two plates 11 and 12 are annular and metallic. Plates 11 and 12 have the same axis of symmetry as the coupling enclosure. Each plate 11 or 12 has an adjustable position in a movement along the axis of symmetry independently of the other plate 11 or 12. The plates 11 and 12 comprise adjustment means 110 and 120, respectively. The adjustment means comprise for example a screw and a thumbwheel to turn the screw. Such plates 11 and 12 make it possible to vary the distribution of the microwaves in the coupling chamber to obtain good homogeneity and good stability of the plasma near the surface to be treated
[0061] Le dispositif décrit plus haut permet de mettre en œuvre le procédé de The device described above makes it possible to implement the method of
traitement de l’invention. Le procédé de traitement permet de déposer un revêtement à effet barrière sur une surface en matériau polymère. treatment of the invention. The treatment process makes it possible to deposit a coating with a barrier effect on a surface made of polymer material.
La surface est par exemple et sans caractère limitatif en matériau polymère de type polyéthylène, polypropylène, polyamide, PET, ou polychlorure de vinyle. The surface is, for example and without a limiting nature, made of a polymer material of polyethylene, polypropylene, polyamide, PET or polyvinyl chloride type.
[0062] Le procédé de traitement comprend les étapes suivantes : The treatment method comprises the following steps:
- introduction du récipient 20 dans l’enceinte à vide 3, - introduction of the container 20 into the vacuum chamber 3,
- réalisation d’un cycle de pompage dans l’enceinte à vide 3 et dans le récipient 20 au moyen du circuit de pompage 4, - carrying out a pumping cycle in the vacuum chamber 3 and in the container 20 by means of the pumping circuit 4,
- introduction dans le récipient 20 d’un gaz précurseur, - introduction into the container 20 of a precursor gas,
- transformation en l’état de plasma du gaz précurseur par une double excitation. - transformation of the precursor gas into the plasma state by double excitation.
[0063] L’introduction du récipient 20 dans l’enceinte à vide 3 est réalisée comme suit. Le socle 33 amovible est retiré de l’enceinte à vide 3. Le récipient 20 à traiter est posé sur le socle 33 puis le socle 33 est repositionné de sorte à refermer l’enceinte à vide hermétiquement. The introduction of the container 20 into the vacuum chamber 3 is carried out as follows. The removable base 33 is removed from the vacuum chamber 3. The container 20 to be treated is placed on the base 33 and then the base 33 is repositioned so as to close the vacuum chamber hermetically.
[0064] Dans le cas d’un dispositif 1 selon le premier mode de réalisation représenté à la figure 2, le cycle de pompage est réalisé comme suit. Le récipient 20 est positionné de sorte que le joint 34 du conduit 32 vienne en contact avec l’ouverture 21 du récipient pour isoler la partie intérieure de la partie extérieure du récipient 20. Dans une première phase du cycle de pompage, la vanne In the case of a device 1 according to the first embodiment shown in Figure 2, the pumping cycle is performed as follows. The container 20 is positioned so that the seal 34 of the conduit 32 contacts the opening 21 of the container to isolate the inner part from the outer part of the container. container 20. In a first phase of the pumping cycle, the valve
d’isolement est ouverte et le pompage est activé de manière à faire chuter la pression simultanément dans le récipient 20 au travers de l’orifice d’aspiration 41 et dans le reste de l’enceinte à vide 3 au travers du deuxième orifice d’aspiration 42. Ainsi, la pression dans le récipient 20 et dans l’enceinte à vide 3 chute depuis une valeur correspondant à la pression atmosphérique jusqu’à une première valeur prédéterminée P1. Dans une deuxième phase du cycle de pompage, la vanne d’isolement est fermée et le pompage se poursuit uniquement au travers de l’orifice 41 dans le récipient. Ainsi, la pression dans le récipient 20 continue de chuter jusqu’à une deuxième valeur prédéterminée P2, inférieure à la première valeur prédéterminée P1 , tandis que la pression dans le reste de l’enceinte à vide 3 est maintenue à la première valeur prédéterminée P1. isolation valve is opened and the pumping is activated so as to drop the pressure simultaneously in the container 20 through the suction port 41 and in the rest of the vacuum chamber 3 through the second orifice of suction 42. Thus, the pressure in the container 20 and in the vacuum chamber 3 drops from a value corresponding to atmospheric pressure to a first predetermined value P1. In a second phase of the pumping cycle, the isolation valve is closed and pumping continues only through port 41 in the container. Thus, the pressure in the container 20 continues to drop to a second predetermined value P2, lower than the first predetermined value P1, while the pressure in the rest of the vacuum chamber 3 is maintained at the first predetermined value P1. .
[0065] Dans le cas d’un dispositif 1’ selon le deuxième mode de réalisation [0065] In the case of a device 1 ’according to the second embodiment
représenté à la figure 3, le cycle de pompage est réalisé comme suit. Le récipient 20 est positionné de sorte que le joint 34 du conduit 32 n’est pas en contact avec l’ouverture 21 du récipient de manière que la partie intérieure et la partie extérieure du récipient 20 communiquent. Dans une première phase du cycle de pompage, le pompage est activé de manière à faire chuter la pression shown in Figure 3, the pumping cycle is carried out as follows. The container 20 is positioned so that the seal 34 of the conduit 32 does not contact the opening 21 of the container so that the inner part and the outer part of the container 20 communicate. In a first phase of the pumping cycle, the pumping is activated so as to drop the pressure
simultanément dans le récipient 20 et dans le reste de l’enceinte à vide 3 au travers de l’orifice d’aspiration 41. Ainsi, la pression dans le récipient 20 et dans l’enceinte à vide 3 chute depuis une valeur correspondant à la pression atmosphérique jusqu’à une première valeur prédéterminée P1. Dans une deuxième phase du cycle de pompage, le récipient 20 est positionné de sorte que le joint 34 du conduit 32 vienne en contact avec l’ouverture 21 du récipient pour isoler la partie intérieure de la partie extérieure du récipient 20 et le pompage se poursuit uniquement dans le récipient au travers de l’orifice 41. simultaneously in the container 20 and in the rest of the vacuum chamber 3 through the suction port 41. Thus, the pressure in the container 20 and in the vacuum chamber 3 drops from a value corresponding to the atmospheric pressure up to a first predetermined value P1. In a second phase of the pumping cycle, the container 20 is positioned so that the seal 34 of the conduit 32 comes into contact with the opening 21 of the container to isolate the inner part from the outer part of the container 20 and pumping continues. only in the container through the opening 41.
Ainsi, la pression dans le récipient 20 continue de chuter jusqu’à une deuxième valeur prédéterminée P2 tandis que la pression dans le reste de l’enceinte à vide 3 est maintenue à la première valeur prédéterminée P1. Thus, the pressure in the container 20 continues to drop to a second predetermined value P2 while the pressure in the rest of the vacuum chamber 3 is maintained at the first predetermined value P1.
[0066] Selon le procédé de l’invention, suite au pompage, la pression est plus [0066] According to the method of the invention, following pumping, the pressure is more
importante à l’extérieur du récipient 20 qu’à l’intérieur du récipient afin d’obtenir une pression favorable à la création d’un plasma à l’intérieur du récipient 20 et défavorable à la création du plasma à l’extérieur du récipient 20. De plus, la pression à l’extérieur du récipient est suffisamment faible pour limiter le différentiel de pression entre l’intérieur et l’extérieur du récipient afin d’éviter la déformation du récipient. important outside the container 20 than inside the container in order to obtain a pressure favorable to the creation of a plasma inside the container 20 and unfavorable to the creation of the plasma outside the container 20. In addition, the pressure outside the container is low enough to limit the pressure differential between the inside and the outside of the container in order to avoid deformation of the container.
[0067] L’introduction du gaz précurseur dans le récipient 20 est réalisée au travers de l’injecteur de gaz 5. The introduction of the precursor gas into the container 20 is carried out through the gas injector 5.
[0068] Le gaz précurseur est destiné, une fois transformé en l’état de plasma, à être déposé au moins en partie sur la surface 2 interne du récipient 20 pour constituer le revêtement. Le gaz précurseur peut être un gaz choisi parmi les alcanes, les alcènes, les alcynes, les aromatiques, ou une combinaison de certains d’entre eux. En particulier, le gaz précurseur peut être un gaz de tétrafluoroéthane- 1 ,1 , 1 ,2, de pentafluoroéthane, de difluorométhane, d’acétylène, ou une The precursor gas is intended, once transformed into the state of plasma, to be deposited at least in part on the internal surface 2 of the container 20 to constitute the coating. The precursor gas can be a gas selected from alkanes, alkenes, alkynes, aromatics, or a combination of some of them. In particular, the precursor gas can be a gas of tetrafluoroethane- 1, 1, 1, 2, of pentafluoroethane, of difluoromethane, of acetylene, or a
combinaison de certains d’entre eux ou un mélange de certains d’entre eux avec un gaz rare tel que l’argon. a combination of some of them or a mixture of some of them with a rare gas such as argon.
[0069] Le procédé peut comporter en outre une étape préalable de traitement de la surface par un plasma d’oxygène, d’hydrogène, d’argon, de dioxyde de carbone, d’hélium, d’azote ou une combinaison de certains d’entre eux. En outre, le procédé peut comporter le dépôt d’une succession de couches de revêtement. The method may further comprise a preliminary step of treating the surface with a plasma of oxygen, hydrogen, argon, carbon dioxide, helium, nitrogen or a combination of certain d 'between them. In addition, the method may include depositing a succession of coating layers.
[0070] Le gaz est introduit dans l’enceinte avec un débit contrôlé de manière à The gas is introduced into the enclosure at a controlled flow rate so as to
maintenir l’enceinte à une pression comprise entre 0,01 mbar et 1 mbar. maintain the enclosure at a pressure between 0.01 mbar and 1 mbar.
[0071] La double excitation comprend : The double excitation comprises:
- une excitation au moyen d’ondes électromagnétiques de type micro-ondes, et - excitation by means of electromagnetic waves of microwave type, and
- une excitation au moyen d’une décharge électrique. - excitation by means of an electric shock.
L’excitation au moyen d’ondes électromagnétiques de type micro-ondes, et l’excitation au moyen d’une décharge électrique sont réalisées simultanément au cours d’une phase du traitement dite phase plasma. Le temps de phase plasma est compris entre une seconde et 30 secondes. The excitation by means of microwave-type electromagnetic waves, and the excitation by means of an electric discharge are carried out simultaneously during a phase of the treatment known as the plasma phase. The plasma phase time is between one second and 30 seconds.
[0072] L’excitation au moyen d’ondes électromagnétiques de type micro-ondes est réalisée avec une fréquence comprise entre 915 Mhz et 2450 MHz. La densité volumique de puissance des ondes électromagnétiques est comprise entre 0,01 W/cm3 et 1 W/cm3. [0073] L’excitation au moyen d’une décharge électrique est réalisée avec une tension alternative ayant une fréquence comprise entre 20kHz et 200kHz. La valeur crête de la tension de la décharge électrique est par exemple comprise entre 200 V et 500 V. La puissance de la décharge électrique est alors comprise entre 4 W et 30 W. The excitation by means of electromagnetic waves of the microwave type is carried out with a frequency between 915 MHz and 2450 MHz. The power density of electromagnetic waves is between 0.01 W / cm 3 and 1 W / cm 3 . The excitation by means of an electric discharge is carried out with an alternating voltage having a frequency between 20kHz and 200kHz. The peak value of the voltage of the electric discharge is for example between 200 V and 500 V. The power of the electric discharge is then between 4 W and 30 W.
[0074] On comprendra que diverses modifications et/ou améliorations évidentes pour l'homme du métier peuvent être apportées aux différents modes de réalisation de l’invention décrits dans la présente description sans sortir du cadre de l'invention défini par les revendications annexées. It will be understood that various modifications and / or improvements obvious to a person skilled in the art can be made to the various embodiments of the invention described in the present description without departing from the scope of the invention defined by the appended claims.

Claims

Revendications Claims
[Revendication 1] ÎProcédé de traitement dans une enceinte (3) d’une [Claim 1] ÎProcess of treatment in an enclosure (3) of a
surface (2) interne d’un récipient (20) en matériau polymère pour y déposer un revêtement à effet barrière, comprenant : internal surface (2) of a container (20) made of polymer material to deposit a barrier effect coating, comprising:
- l’introduction du récipient (20) dans l’enceinte, - the introduction of the container (20) into the enclosure,
- l’introduction dans le récipient (20) d’un gaz dit précurseur destiné, une fois transformé en l’état de plasma, à être déposé au moins en partie sur la surface (2) interne du récipient (20) pour constituer le revêtement, le procédé étant caractérisé en ce qu’il comporte en outre : - the introduction into the container (20) of a said precursor gas intended, once transformed into the plasma state, to be deposited at least in part on the internal surface (2) of the container (20) to constitute the coating, the process being characterized in that it further comprises:
- la transformation en l’état de plasma du gaz précurseur par une - the transformation into the plasma state of the precursor gas by a
combinaison d’excitations comprenant une excitation principale au moyen d’ondes électromagnétiques de type micro-ondes, et une excitation secondaire au moyen d’une décharge électrique de tension alternative ayant une fréquence comprise entre 1 kHz et 15 MHz. combination of excitations comprising a main excitation by means of microwave-type electromagnetic waves, and a secondary excitation by means of an electric discharge of alternating voltage having a frequency between 1 kHz and 15 MHz.
[Revendication 2] Procédé de traitement selon la revendication 1 [Claim 2] A processing method according to claim 1
caractérisé en ce que : characterized in that:
- l’excitation au moyen d’ondes électromagnétiques de type micro-ondes, et - the excitation by means of electromagnetic waves of the microwave type, and
- l’excitation au moyen d’une décharge électrique de tension alternative sont réalisées simultanément au cours d’une phase du traitement dite phase plasma. - the excitation by means of an electric discharge of alternating voltage are carried out simultaneously during a phase of the treatment known as the plasma phase.
[Revendication 3] Procédé de traitement selon la revendication 2 [Claim 3] A treatment method according to claim 2
caractérisé en ce que le temps de phase plasma est compris entre une seconde et 10 minutes, de préférence entre une seconde et 30 secondes. characterized in that the plasma phase time is between one second and 10 minutes, preferably between one second and 30 seconds.
[Revendication 4] Procédé de traitement selon l’une quelconque des [Claim 4] A processing method according to any of
revendications 1 à 3, caractérisé en ce que la valeur efficace de la tension de la décharge électrique est comprise entre 100 V et 1000 V, de préférence entre 200 V et 500 V. claims 1 to 3, characterized in that the effective value of the voltage of the electric discharge is between 100 V and 1000 V, preferably between 200 V and 500 V.
[Revendication 5] Procédé de traitement selon l’une quelconque des [Claim 5] A method of treatment according to any of
revendications 1 à 4, caractérisé en ce que le gaz précurseur est un gaz de tétrafluoroéthane-1 ,1 ,1 ,2, de pentafluoroéthane, de difluorométhane, d’acétylène, ou une combinaison de certains d’entre eux ou un mélange de certains d’entre eux avec un gaz rare tel que l’argon. Claims 1 to 4, characterized in that the precursor gas is a gas of tetrafluoroethane-1, 1, 1, 2, of pentafluoroethane, of difluoromethane, acetylene, or a combination of some of them or a mixture of some of them with a rare gas such as argon.
[Revendication 6] Procédé de traitement selon l’une quelconque des [Claim 6] Treatment method according to any of
revendications 1 à 5, caractérisé en ce que la puissance de la décharge électrique est comprise entre 1 W et 2000 W, de préférence entre 4W et 100W. claims 1 to 5, characterized in that the power of the electric discharge is between 1 W and 2000 W, preferably between 4W and 100W.
[Revendication 7] Procédé de traitement selon l’une quelconque des [Claim 7] Treatment method according to any of
revendications 1 à 6, caractérisé en ce que le gaz est introduit dans l’enceinte (3) avec un débit contrôlé de manière à maintenir l’enceinte (3) à une pression comprise entre 0,002 mbar et 10 mbar, de préférence entre 0,01 mbar et 1 mbar. claims 1 to 6, characterized in that the gas is introduced into the enclosure (3) with a controlled flow rate so as to maintain the enclosure (3) at a pressure of between 0.002 mbar and 10 mbar, preferably between 0, 01 mbar and 1 mbar.
[Revendication 8] Dispositif de traitement (1 , 1’) d’une surface (2) interne d’un récipient (20) en matériau polymère pour y déposer un revêtement à effet barrière comportant : [Claim 8] Device for treating (1, 1 ’) an internal surface (2) of a container (20) made of polymer material in order to deposit thereon a barrier effect coating comprising:
- une enceinte de couplage (10) constituant un espace de propagation d’ondes électromagnétiques de type micro-onde, - a coupling enclosure (10) constituting a microwave-type electromagnetic wave propagation space,
- une enceinte à vide (3) étanche aux gaz placée dans l’enceinte de couplage (10) et comportant un espace destiné à recevoir le récipient (20), - a gas-tight vacuum chamber (3) placed in the coupling chamber (10) and comprising a space intended to receive the container (20),
- un circuit de pompage (4) agencé pour engendrer une dépression dans l’enceinte à vide (3) au travers d’au moins un orifice d’aspiration (41 , 42), - a pumping circuit (4) arranged to generate a vacuum in the vacuum chamber (3) through at least one suction port (41, 42),
- une source de gaz dit précurseur destiné, une fois transformé en l’état de plasma, à être déposé au moins en partie sur la surface interne du récipient pour constituer le revêtement, - a source of so-called precursor gas intended, once transformed into the plasma state, to be deposited at least in part on the internal surface of the container to form the coating,
- un injecteur de gaz (5) alimenté par la source de gaz précurseur et débouchant dans l’espace destiné à recevoir le récipient (20), - a gas injector (5) supplied by the source of precursor gas and opening into the space intended to receive the container (20),
- au moins un guide d’onde (6) débouchant dans l’enceinte de couplage (10), - at least one waveguide (6) opening into the coupling enclosure (10),
- au moins un magnétron (7) conçu et agencé de manière à émettre des ondes électromagnétiques de type micro-onde dans l’au moins un guide d’onde (6), - at least one magnetron (7) designed and arranged so as to emit microwave-type electromagnetic waves in at least one waveguide (6),
caractérisé en ce que le dispositif de traitement comporte en outre : characterized in that the processing device further comprises:
- une électrode (8) placée au moins partiellement dans l’espace destiné à recevoir le récipient (20), et - un générateur de tension (9) conçu et agencé de manière à pouvoir alimenter l’électrode (8) avec une tension alternative de fréquence comprise entre 1 kHz et 15 MHz . - an electrode (8) placed at least partially in the space intended to receive the container (20), and - a voltage generator (9) designed and arranged so as to be able to supply the electrode (8) with an alternating voltage of frequency between 1 kHz and 15 MHz.
[Revendication 9] Dispositif de traitement (1 , 1’) selon la revendication 8, caractérisé en ce que l’injecteur de gaz (5) et l’électrode (8) sont un seul et même élément. [Claim 9] A treatment device (1, 1 ’) according to claim 8, characterized in that the gas injector (5) and the electrode (8) are one and the same element.
[Revendication 10] Dispositif de traitement (1 , 1’) selon l’une quelconque des revendications 8 à 9, caractérisé en ce que l’enceinte de couplage (10) est cylindrique et présente un axe de symétrie (A). [Claim 10] Processing device (1, 1 ’) according to any one of claims 8 to 9, characterized in that the coupling enclosure (10) is cylindrical and has an axis of symmetry (A).
[Revendication 11 ] Dispositif de traitement (1 , 1’) selon l’une quelconque des revendications 8 à 10, caractérisé en ce qu’il comporte plusieurs guides d’onde (6) débouchant dans l’enceinte de couplage (10) et répartis autour de l’enceinte de couplage (10), chaque guide d’onde (6) étant couplé à un magnétron (7) alimenté par une alimentation électrique (13) et conçu pour émettre des ondes électromagnétiques de type micro-onde dans le guide d’onde. [Claim 11] Treatment device (1, 1 ') according to any one of claims 8 to 10, characterized in that it comprises several waveguides (6) opening into the coupling chamber (10) and distributed around the coupling enclosure (10), each waveguide (6) being coupled to a magnetron (7) supplied by a power supply (13) and designed to emit microwave-type electromagnetic waves into the waveguide.
[Revendication 12] Dispositif de traitement (1 , 1’) selon l’une quelconque des revendications 8 à 11 , caractérisé en ce qu’il est adapté au traitement d’une surface (2) constituée des faces internes d’un récipient (20) creux comportant une ouverture (21 ) et en ce que l’enceinte à vide (3) est munie d’un couvercle (31 , 31’) d’obturation étanche comportant un conduit (32) entouré d’un joint (34) conçu pour séparer de manière étanche l’intérieur de l’extérieur du récipient (20), le conduit (32) comportant l’injecteur de gaz (5) et l’orifice d’aspiration (41 ). [Claim 12] A treatment device (1, 1 ') according to any one of claims 8 to 11, characterized in that it is suitable for treating a surface (2) consisting of the internal faces of a container ( 20) hollow comprising an opening (21) and in that the vacuum chamber (3) is provided with a sealed closure cover (31, 31 ') comprising a duct (32) surrounded by a seal (34 ) designed to sealably separate the interior from the exterior of the container (20), the conduit (32) comprising the gas injector (5) and the suction port (41).
[Revendication 13] Dispositif de traitement (1 , 1’) selon l’une quelconque des revendications 8 à 12, caractérisé en ce que l’enceinte de couplage (10) est confondue avec l’enceinte à vide (3). [Claim 13] Processing device (1, 1 ’) according to any one of claims 8 to 12, characterized in that the coupling enclosure (10) is coincident with the vacuum enclosure (3).
EP19745683.3A 2019-01-17 2019-06-17 Treatment method and device for depositing a barrier-effect coating Pending EP3911779A1 (en)

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