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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/48—Ion implantation
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
  • C03C23/0055—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ion implantation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
  • A61L2/02—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using physical processes
  • A61L2/14—Plasma, i.e. ionised gases
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M15/00—Inhalators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
  • A61M2205/00—General characteristics of the apparatus
  • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
  • A61M2205/0233—Conductive materials, e.g. antistatic coatings for spark prevention
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

• the present invention relates to a surface treatment method for fluid dispensing devices.
• Dispensing devices for fluid products are well known. They generally comprise a reservoir, a dispensing member, such as a pump or a valve, and a dispensing head provided with a dispensing orifice.
• the fluid dispensing devices may also be inhalers comprising a plurality of reservoirs each containing an individual dose of powder or liquid, and means for opening and expelling said doses during successive actuations.
• these devices have many parts that come into contact with the fluid during actuation. There is therefore a risk that the product remains glued or hooked to one or more parts of the device before being distributed to the user. This results in a decrease in the dose distributed over the theoretical dose, which can create serious problems, for example for crisis treatments, such as asthma.
• These gluing problems can arise in particular at the level of the tank or tanks, but also at the level of the piston and the pump chamber or the valve and the valve chamber. It is the same in the pushers or dispensing heads.
• the present invention aims to provide a surface treatment method that does not reproduce the aforementioned drawbacks.
• the present invention aims to provide a surface treatment method that is effective, durable, non-polluting and simple to achieve.
• the subject of the invention is in particular a method for treating a polymer part with multicharged and multi-energy ions belonging to the list consisting of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), this polymer part forming part of a fluid dispensing device, in particular pharmaceutical.
• multicharged and multi-energy ions belonging to the list consisting of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), this polymer part forming part of a fluid dispensing device, in particular pharmaceutical.
• the dissipation of electrostatic charges it is obtained with dissipative materials and conductors which prevent electrical discharges and dissipate the charges resulting from the movements at high speed.
• the conductivity can be obtained by different ways:
• non-permanent additives such as fatty amine esters or quaternary amines. These substances, incorporated into a polymer matrix, migrate to the surface and react with the humidity of the air. By forming a wet film on the surface, they decrease the surface resistivity to about 10 14 ⁇ / ⁇ .
• Adhesion is an important phenomenon in the case of polymers which results for example in the bonding of active product on a surface. This adhesion results from the contribution of the Van Der Walls forces produced by the polarity of the molecules located on the surface of the polymer and by the electrostatic forces induced by the very high surface resistivity.
• Some polymers are loaded with chemical agents that protect against UV rays and oxidation.
• the rejection of these chemical agents to the outside has the effect of accelerating the surface oxidation which in turn reinforces the insulating nature of the polymer.
• the aim of the invention is to reduce the aforementioned drawbacks and in particular to allow a sharp reduction in the surface resistivity of a solid polymer part while retaining in the mass its elastic properties and avoiding the use of chemical agents which are detrimental to health.
• the subject of the invention is therefore a method for treating at least one surface of a massive piece of polymer with helium ions, characterized in that X + and X 2+ multi-energy ions are simultaneously implanted.
• the inventors have for example found that the simultaneous presence of He + and He 2+ ions makes it possible to very significantly improve the surface antistatic properties of the polymers compared with known treatments where only He + or He 2 ions are used. + are implanted. They were able to show that a significant improvement was obtained for RHe less than or equal to 100, for example less than or equal to 20.
• the invention makes it possible to reduce the surface resistivity of a piece of solid polymer, and / or to eliminate the bonding of the dust or even to reduce the polarization of the surface by eliminating strongly polarized chemical groups such as OH, COOH. These functional groups can induce Van der Walls forces which have the effect of sticking ambient chemical molecules to the surface of the polymer.
• the invention also makes it possible to increase the chemical stability of the polymer by creating, for example, a permeation barrier. This last can slow the propagation of ambient oxygen in the polymer, and / or delay the diffusion of chemical protective agents contained in the polymer to the outside, and / or inhibit the release of toxic agents contained in the polymer to the polymer. 'outside.
• solid means a polymer part produced by mechanical or physical transformation of a block of material, for example by extrusion, molding or any other technique adapted to transform a polymer block.
• PET Polyethylene terephthalate
• the process is low energy, inexpensive and allows its use in an industrial setting without any environmental impact.
• the treatment of a polymer part is performed by simultaneous implantation of multicharged multi-energy ions. These are especially obtained by extracting with the same single extraction voltage ions mono- and multi-charged created in the plasma chamber of an electron cyclotron resonance ion source (ECR source). Each ion produced by said source has an energy that is proportional to its state of charge. As a result, the ions with the highest charge state, therefore the highest energy, are implanted in the polymer part at greater depths.
• ECR source electron cyclotron resonance ion source
• An implementation with an ECR source is fast and inexpensive since it does not require a high extraction voltage of the ion source. Indeed, to increase the implantation energy of an ion, it is economically preferable to increase its state of charge rather than increase its extraction voltage.
• RX is less than or equal to 100. With such sources, on the contrary, it is generally greater than or equal to 1000.
• the source is an electron cyclotron resonance source producing multi-energy ions which are implanted in the room at a temperature below 50 ° C and the implantation of ions of the implantation beam. is performed simultaneously at a depth controlled by the extraction voltage of the source.
• the ions excite during their passage the electrons of the polymer causing splits of covalent bonds which recombine immediately to generate, by a mechanism said crosslinking, a high density of covalent chemical bonds mainly consisting of carbons.
• Lighter elements like hydrogen and oxygen are removed from the polymer during degassing.
• This densification in carbon-rich covalent bonds has the effect of superficially increasing the conductivity and reducing or even eliminating the superficial polar groups at the origin of the Van der Walls forces at the origin of the bonding.
• the crosslinking process is all the more effective as the ion is light.
• N nitrogen
• O oxygen
• Ne neon
• Ne argon
• Kr krypton
• Xe xenon
• a preferred mode consists, for example, in combining:
• the extraction voltage of the source enabling implantation of the multi-energy ions He + and He 2+ is between 10 and 400 kV, for example greater than or equal to 20 kV and / or less than or equal to 100 kV;
• the dose of multi-energy ion He + and He 2+ is between 5.10 14 and 10 18 ions / cm 2 , for example greater than or equal to 10 15 ions / cm 2 and / or less than or equal to 5.10 17 ions / cm 2 , or even greater than or equal to 5.10 15 ions / cm 2 and / or less than or equal to 10 17 ions / cm 2 ;
• the variation of a characteristic property of the evolution of the surface of a solid piece of polymer is determined, for example, the surface resistivity of the polymer of a polymeric material representative of that of the part to be treated as a function of doses of multi-energy ions He + and He 2+ so as to determine an ion dose range where the variation of the selected characteristic property is advantageous and evolves in a differentiated manner in three consecutive zones of doses of ions forming said ion dose domain, with a change in the first substantially linear zone and reversible over a period of less than one month, an evolution in the second zone that is substantially linear and stable over a period of time greater than one month; finally, an evolution in the third zone that is constant and stable over a period of time greater than one month and where the dose of multi-energy ions He + is chosen and He 2+ in the third zone of ion doses to treat the massive piece of polymer; reversible evolution (first zone) means that the resistivity decreases and then rises to recover its original
• Parameters of the source and displacement of the surface of the polymer part to be treated are adjusted so that the surface speed of treatment of the surface of the polymer part to be treated is between 0.5 cm 2 / s and 1000 cm 2 / s, for example greater than or equal to 1 cm 2 / s and / or less than or equal to 100 cm 2 / s;
• parameters of the source and displacement of the surface of the polymer part to be treated are adjusted so that the dose of implanted helium is between 5.10 14 and 10 18 ions / cm 2 , for example greater than or equal to at 5.10 15 ions / cm 2 and / or less than or equal to 10 17 ions / cm 2 ;
• parameters of the source and displacement of the surface of the polymer part to be treated are adjusted so that the depth of penetration of the helium on the surface of the treated polymer part is between 0.05 and 3 ⁇ , for example greater than or equal to 0.1 ⁇ and / or less than or equal to 2 ⁇ ; the parameters of the source and the displacement of the surface of the polymer part to be treated are adjusted so that the temperature of the surface of the polymer part being treated is less than or equal to 100.degree. example less than or equal to 50 ° C;
• the polymer part is for example a profiled strip, and said piece scrolls in a processing device, for example at a speed between 5 m / min and 100 m / min; for example, the polymer part is a profiled strip which scrolls longitudinally;
• the helium implantation of the surface of the workpiece is carried out by means of a plurality of He + and He 2+ multi-energy ion beams produced by a plurality of ion sources; for example, the ion sources are arranged along a direction of movement of the workpiece; preferably the sources are spaced so that the distance between two ion beams is sufficient to allow the part to cool between successive ion implantation; said sources produce ion beams whose diameter is adapted to the width of the tracks to be treated.
• the polymer of the part is chosen from polycarbonates, polyethylenes, polyethylene terephthalates, polyamides, polymethylacrylates and polypropylenes.
• the list is not exhaustive. Other types of polymer are conceivable given the generic nature of the crosslinking process.
• the invention also relates to a part where the thickness where the helium is implanted is greater than or equal to 50 nm, for example greater than or equal to 200 nm and whose surface resistivity p, is less than or equal to 10 14 ⁇ / ⁇ , for example less than or equal to 10 9 ⁇ / ⁇ , or even less than or equal to 10 5 ⁇ / ⁇ .
• surface resistivity refer to the IEC 60093 standard.
• the subject of the present invention is therefore a method for surface treatment of a fluid product dispensing device, said method comprising the step of modifying by ion implantation, by means of multicharged and multi-energy ion beams, at least a surface to be treated with at least a portion of said device in contact with said fluid product, said modified surface to be treated having anti-stick properties for said fluid product, said multicharged ions being selected from helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), the ion implantation being carried out at a depth of 0 to 3 ⁇ .
• FIG. 1 represents an example of helium implantation distribution according to the invention in a polycarbonate
• FIG. 2 shows the scales according to different standards describing the electrostatic properties of a material
• FIG. 3 represents the variation of the surface resistivity of the surface of a treated polycarbonate sample according to the invention, as a function of time, for a plurality of helium doses; the surface resistivity was measured according to the IEC 60093 standard, by implementing an electrode consisting of a disc of diameter d, surrounded by a ring of internal diameter D where D is greater than d;
• FIG. 4 represents the variation of the surface resistivity of the surface of a polycarbonate sample treated according to the invention, as a function of time, for three types of He, N, Ar ions in a plurality of doses; surface resistivity was measured according to IEC 60093; and
• FIG. 5 represents the variation of the surface resistivity of the surface of a polycarbonate sample treated according to the invention, as a function of time, for a plurality of nitrogen doses but according to two beam displacement speeds; the surface resistivity was measured according to the IEC 60093 standard.
• the present invention provides for the use of a method similar to that described in document WO 2005/085491, which concerns an ion implantation process, and more particularly the use of a multicharged multi-energy ion beam in order to to structurally modify the surface of metallic materials on depths around the ⁇ to give them particular physical properties.
• This implantation method has in particular been used to treat parts made of aluminum alloy which are used as molds for series production of plastic parts.
• the surfaces to be treated may comprise a synthetic material, such as polyethylene (PE) and / or polypropylene (PP) and / or polyvinyl chloride (PVC) and / or polytetrafluoroethylene (PTFE). They can also be metal, glass, or elastomer.
• PE polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PTFE polytetrafluoroethylene
• the method of the invention has the effect of inhibiting the effects of electrostatic charges and modifying the tribology surfaces in contact with the powder, thereby mitigating the risk of sticking everywhere or the powder passes, particularly with regard to the first dose expelled.
• the method consists in using one or more ion sources, such as an electron cyclotron resonance source, referred to as ECR source.
• ECR source can deliver an initial beam of multi-energy ions, for example having a total current of about 10 mA (all loads combined), under an extraction voltage that can vary from 20 kV to 200 kV.
• the RCE source emits the ion beam towards adjustment means which focus and adjust the initial beam emitted by the ECR source into an ion implantation beam that strikes a workpiece.
• the ions can be selected from helium, boron, carbon, nitrogen, oxygen, neon, argon, krypton and xenon.
• the maximum temperature of the workpiece varies depending on its nature.
• the typical implantation depth is between 0 and 3 ⁇ , and depends not only on the surface to be treated, but also on the properties that one wishes to improve.
• RCE ions The specificity of a source of RCE ions lies notably in the fact that it delivers mono- and multicharged ions, which makes it possible to simultaneously implant multi-energy ions with the same extraction voltage. It is thus possible to obtain simultaneously, over the entire thickness treated, a better distributed implantation profile. This improves the quality of the surface treatment.
• the process is carried out in a vacuum chamber using a vacuum pump.
• This vacuum is intended in particular to prevent the interception of the beam by residual gases and to avoid the contamination of the surface of the room by these same gases during implantation.
• the adjustment means mentioned above can comprise, from the ECR source to the part to be treated, the following elements:
• a mass spectrometer able to filter the ions according to their charge and their mass.
• a spectrometer is however optional if a pure gas is injected, for example a pure nitrogen gas (N2). It is then possible to recover all the mono- and multicharged ions produced by the source to obtain a multi-energy ion beam.
• N2 pure nitrogen gas
• one or more lenses for giving the ion beam a predetermined shape, for example a cylindrical shape, with a predetermined radius.
• a profiler for analyzing, during the first implantation, the intensity of the beam in a perpendicular section plane.
• an intensity transformer for continuously measuring the intensity of the ion beam without intercepting it.
• One of the functions of this instrument is to detect any interruption of the ion beam and to allow the recording of beam intensity variations during the treatment.
• a shutter which may for example be a Faraday cage, for interrupting the trajectory of the ions at certain times, for example during a displacement without treatment of the part.
• the workpiece is movable relative to the ECR source.
• the piece can for example be mounted on a movable support whose movement can be controlled by a numerically controlled machine.
• the displacement of the workpiece is calculated according to the radius of the beam, the external and internal contours of the zones to be treated, the constant or variable speed of movement as a function of the angle of the beam relative to the surface and the number previously completed.
• One possible implementation of the treatment method is as follows.
• the workpiece is fixed on a suitable support in an enclosure, then the enclosure is closed and a high vacuum is installed by means of a pump. empty.
• the production and adjustment of the ion beam is carried out.
• the shutter is raised and the numerically controlled machine is actuated, which then performs the displacement in position and speed of the workpiece in front of the beam in one or more passes.
• the shutter is lowered to cut the beam, the production of the beam is stopped, the vacuum is broken by opening the chamber to the ambient air, the cooling circuit is eventually stopped and take the treated part out of the enclosure.
• the ratio RHe is less than or equal to 100, for example less than 20, and preferably greater than 1.
• the He + and He2 + ions are advantageously produced simultaneously by an ECR source.
• the extraction voltage of the source allowing implantation of the multi-energy ions He + and He + 2 can be between 10 and 400 kV, for example greater than or equal to 20 kV and / or less than or equal to 100 kV.
• the multi-energy ion He + and He2 + dose is between 1014 and 1018 ions / cm 2 , for example greater than or equal to 1015 ions / cm 2 and / or less than or equal to 1017 ions / cm 2 , or even greater or equal to 1015 ions / cm 2 and / or less than or equal to 1016 ions / cm 2 .
• the depth of implantation is advantageously between 0.05 and 3 ⁇ , for example between 0.1 and 2 ⁇ .
• the temperature of the elastomeric surface being treated is advantageously less than 100 ° C., preferably less than 50 ° C.
• different ion implantations are performed on the same surface to be treated, to give several properties to this surface to be treated.
• the surfaces of elastomers, and in particular the seals of dispensing devices for fluid products such as medicaments, metal or glass surfaces, or synthetic surfaces, for example made of polyethylene or polypropylene, are susceptible to interact with the fluid product, for example by releasing extractables in said fluid, which can have a detrimental effect on it.
• the invention advantageously provides for modifying the surface to be treated in order to prevent or limit the interactions between the fluid product and the surface to be treated.
• These additional surface treatments can be applied during successive ion implantation steps. It should be noted that the order of these successive steps of ion implantation may be arbitrary. Alternatively, the different properties could also be granted to the same surface to be treated in a single ion implantation step.
• the method of the invention is non-polluting, especially since it does not require chemicals. It is carried out dry, which avoids the relatively long drying periods of the liquid treatment processes. It does not require a sterile atmosphere outside the vacuum chamber, and so it can be done at any desired location.
• a particular advantage of this method is that it can be integrated into the assembly line of the fluid dispenser device, and operate continuously in this chain. This integration of the treatment process with the production tool simplifies and accelerates the manufacturing and assembly process as a whole, and therefore positively impacts its cost.
• the present invention is applicable to multi-dose devices, such as pump or valve devices mounted on a reservoir and operated for successive distribution of doses. It also applies to multi-dose devices comprising a plurality of individual reservoirs each containing a dose of fluid, such as pre-dosed powder inhalers. It also applies to single-dose or bidose devices, in which a piston moves directly into a reservoir each time it is actuated.
• the invention is particularly applicable to nasal or oral spray devices, ophthalmic dispensing devices and syringe-type needle devices.
• FIGS 1 to 5 illustrate advantageous embodiments of the invention.
• FIG. 1 represents a schematic example of helium implantation distribution as a function of the depth according to the invention, in a polycarbonate.
• Curve 101 corresponds to the distribution of He + and curve 102 corresponds to that of He 2+ . It can be estimated that for energies of 100 keV, He 2+ travels an average distance of about 800 nm for an average ionization energy of 10 eV / Angstrom. For energies of 50 keV, He + travels an average distance of about 500 nm for an average ionization energy of 4 eV / Angstrom. The ionization energy of an ion is related to its crosslinking power.
• FIG. 2 represents, according to the DOD HDBK 263 standard, the resistivity values qualifying the electrostatic properties of a material.
• a polymer has insulating properties for surface resistivity values greater than 10 14 ⁇ / ⁇ (ZONE I), antistatic properties for surface resistivity values of between 10 14 ⁇ / ⁇ and 10 9 ⁇ / ⁇ (zone A) .
• the electrostatic charge dissipating properties appear for values of surface resistivity between 10 5 ⁇ / ⁇ and 10 9 ⁇ / ⁇ (zone D) and conductive properties for values less than 10 5 ⁇ / ⁇ (zone C)
• the resistivity measurement was carried out according to IEC 60093.
• the resistivity measurement technique used does not make it possible to measure resistivities greater than 10 15 ⁇ / ⁇ corresponding to the zone N, it saturates at 10 15 ⁇ / ⁇ .
• the abscissa axis corresponds to the time separating the treatment of the sample to the measurement of its surface resistivity.
• the ordinate axis corresponds to the measurement of the surface resistivity expressed in ⁇ / ⁇ .
• a first zone is distinguished for doses less than or equal to 10 15 ions / cm 2 , the surface resistivity decreases for less than a month by about 3 orders of magnitude (passing 1, 5.10 16 ⁇ / ⁇ to 5.10 12 ⁇ / ⁇ ) before returning to its original value around 1, 5.10 16 ⁇ / ⁇ (curve 1).
• the antistatic properties are ephemeral, the free radicals still present recombine with the oxygen and the ambient air.
• the antistatic properties (curve 2 and 3) strengthen to become dissipative of electrostatic charges (curve 4). For these doses, the resistivities remain constant over more than 140 days.
• the beam has a diameter of 15 mm and an intensity of 0.225 mA, the extraction voltage is about 35 kV.
• the abscissa represents dose in ions per unit area expressed in October 15 ions / cm 2.
• the ordinate axis represents the surface resistivity expressed in ⁇ / ⁇ .
• the resistivity measurement was carried out according to the standard IEC 60093.
• the heavier ions are the most effective for reducing the surface resistivity, the PC treated with nitrogen at a surface resistivity at least 10 times lower than that of the PC treated with helium, the PC treated with argon at a surface resistivity at least 10 times lower than that of the PC treated with nitrogen and 100 times lower than that of the PC treated with 'helium.
• the inventors advocate the use of even heavier ions such as xenon to further reduce the resistivity of polycarbonate.
• the beam has a diameter of 15 mm and an intensity of 0.150 mA, the extraction voltage is about 35 kV.
• the abscissa represents dose in ions per unit area expressed in October 15 ions / cm 2.
• the ordinate axis represents the surface resistivity expressed in ⁇ / ⁇ .
• the resistivity measurement was carried out according to IEC 60093. From these curves, it appears that the reduction in speed by a factor of 2 has the effect of reducing by a factor of 10 the surface resistivity of the PC. Without wishing to be bound by any scientific theory, it may be thought that reducing the speed of the beam increases the surface temperature of the PC. This temperature strongly favors the recombination of the free radicals with each other, thereby promoting the formation of a dense and conductive layer of amorphous carbon. The heating also has the effect of expelling the residual gases produced by ion-bombardment-induced splitting / crosslinking mechanisms.
• the inventors have deduced from this experiment that for any polymer treated with a beam of known diameter and power, there is a minimum speed of displacement of the beam causing a maximum reduction of the surface resistivity of the polymer without risk of degradation of the polymer under the effect of heat produced.
• the thermal degradation of the polymer has for signature a significant degassing followed by a rise in pressure at the extraction system of the source RCE. This rise in pressure results in electrical breakdowns.
• the extraction system is used to extract ions from the plasma from the ECR source to form the beam.
• the inventors recommend a test step which consists in progressively reducing the speed of the beam while retaining the other characteristics:
• the polymer thermally degrades under the effect of heat, when the rise in pressure measured by a gauge located both in the extraction system and in the treatment chamber, makes a jump of 10 "5 mbar in a few seconds
• the test should be stopped immediately to keep only the beam displacement speed of the previous test, which is 10 "5 mbar in a few seconds. second or less, is the signature of a thermal degradation of the polymer.
• the treatment of at least one surface of a solid polymer part by implantation of helium ions He + and He 2+ has been carried out with He + and He 2+ multi-energy ions. , produced simultaneously by an ECR source.
• the treated polymers include the following: polypropylene (PP), polymethylacrilate (PMMA).
• the surface antistatic properties of a polymer are significantly improved from a dose greater than 5 ⁇ 10 15 ions / cm 2 , which represents a treatment speed of about 15 cm 2 / s for a Helium beam consisting of 9 mA of He + ion and 1 mA of He 2+ ions.
• the simultaneous implantation of helium ions can be done at varying depths, depending on the needs and the shape of the piece to be treated. These depths depend in particular on the implantation energies of the ions of the implantation beam; they may for example vary from 0.1 to about 3 ⁇ for a polymer. For applications where one looks for properties such as anti-gluing, for example, one could be content with a thickness less than one micron, reducing the processing times accordingly.
• the implantation conditions of the He + and He 2+ ions are chosen so that the polymer part retains its elastic mass properties by maintaining the workpiece at treatment temperatures of less than 50 ° C.
• This result can be achieved in particular for a beam with a diameter of 4 mm delivering a total intensity of 60 microamperes with an extraction voltage of 40 kV, moving at 40 mm / s on displacement amplitudes of 100 mm.
• This beam has a power per unit area of 20 W / cm 2 .
• beams of greater intensity and maintain the elastic properties of mass it is possible to suggest a rule of scale which consists in increasing the diameter of the beam, to increase the speed of displacement and to increase the amplitudes of displacements, in a ratio corresponding to the square root (desired intensity / 60 microamperes).
• the beam can have a diameter of 40 mm to maintain a pfd of 20 W / cm 2 .
• the number of micro accelerators placed for example on the path of a strip can be multiplied according to the same ratio.
• the invention is not limited to these embodiments and should be interpreted in a nonlimiting manner, and encompassing the treatment of any type of polymer.
• the method according to the invention is not limited to the use of an ECR source, and even if it may be thought that other sources would be less advantageous, it is possible to implement the method according to the invention with mono-ion sources or other multi-ion sources, as long as these sources are configured so as to allow simultaneous implantation of multi-energy ions belonging to the list consisting of helium (He), nitrogen, (N) oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe).

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