WO1994014303A1 - Procede et appareil pour traitement au plasma a decharge luminescente a la pression atmospherique - Google Patents

Procede et appareil pour traitement au plasma a decharge luminescente a la pression atmospherique Download PDF

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Publication number
WO1994014303A1
WO1994014303A1 PCT/JP1992/001607 JP9201607W WO9414303A1 WO 1994014303 A1 WO1994014303 A1 WO 1994014303A1 JP 9201607 W JP9201607 W JP 9201607W WO 9414303 A1 WO9414303 A1 WO 9414303A1
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WO
WIPO (PCT)
Prior art keywords
gas
tube
plasma processing
atmospheric pressure
processing apparatus
Prior art date
Application number
PCT/JP1992/001607
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English (en)
Japanese (ja)
Inventor
Satiko Okazaki
Masuhiro Ogoma
Original Assignee
Satiko Okazaki
Masuhiro Ogoma
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 Satiko Okazaki, Masuhiro Ogoma filed Critical Satiko Okazaki
Priority to PCT/JP1992/001607 priority Critical patent/WO1994014303A1/fr
Publication of WO1994014303A1 publication Critical patent/WO1994014303A1/fr

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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
    • C23C16/44—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
    • C23C16/513—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 plasma jets
    • 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
    • H05H1/26—Plasma torches
    • H05H1/30—Plasma torches using applied electromagnetic fields, e.g. high frequency or microwave energy

Definitions

  • the present invention relates to an atmospheric pressure glow discharge plasma processing apparatus.
  • the present invention provides an atmospheric pressure glow discharge plasma capable of performing a surface treatment of various substances or materials under atmospheric pressure, or a reaction such as synthesis or decomposition. It is related to processing equipment.
  • plasma CVD a method using a glow discharge plasma generated under so-called high vacuum conditions
  • ion plating or the like. It is important for plasma, plasma etching, and plasma surface treatment.
  • the inventor of the present invention has established a glow discharge plasma technique under atmospheric pressure as an alternative to the conventional glow discharge plasma technique as a low-pressure method, and has discussed its application. Has also been diligently examining. As a result, this atmospheric pressure glow discharge plasma does not require a complicated vacuum system as in the past, and enables high-efficiency, high-quality surface treatment and thin film formation. And find that Practical application in various fields has been attempted. Since then, this atmospheric pressure glow discharge plasma has been further developed as being useful for so-called waste gas treatment and gas phase synthesis reaction.
  • the inventors of the present invention use a rare gas as a diluent gas mainly with He ', dilute the reactive gas to a large extent, maintain the total pressure under atmospheric pressure, and perform a glow discharge.
  • the atmospheric pressure glow discharge plasma treatment method to be generated has already been proposed.This method can generate a stable glow discharge under the atmospheric pressure, so the vacuum evacuation system is omitted. This makes it possible to significantly reduce the cost of the processing equipment.
  • the inner surface of the insulator tube such as a cylindrical tube is It is not suitable for the treatment and for obtaining a gaseous reaction product flowing through the inside of the tube, and various improvements were also required in this regard.
  • An object of the present invention is to provide a new atmospheric pressure glow discharge plasma processing apparatus capable of realizing a large amount of discharge processing by a simple apparatus.
  • the present invention solves the above-mentioned problems by using a metal cylinder having a tip at the end of the outlet port as an electrode, and supplying rare gas and gas through the outlet port of the electrode metal pipe.
  • Atmospheric pressure plasma processing characterized by blowing out an inert gas or air or a mixed gas of these and a reactive gas and applying a voltage to generate discharge plasma under atmospheric pressure.
  • the present invention provides a plurality of ring-shaped electrode pairs in the length direction of the outer peripheral portion, and a reactive gas and a rare gas are supplied from one end of an insulator tube in which each of the pair of multi-electrodes is connected in parallel or in series.
  • a gas mixture with a gas is introduced, and a glow discharge plasma is generated inside the tube under atmospheric pressure, and the inner surface of the tube or the inside of the tube becomes static.
  • an in-pipe atmospheric pressure glow discharge plasma processing apparatus characterized by stopping, moving, or processing a flowing material.
  • FIGS. 1 to 9 of the attached drawings are configuration diagrams each showing a blow-off type plasma processing apparatus of the present invention.
  • FIG. 10 is a configuration diagram illustrating an in-tube plasma processing apparatus. The symbols in the figure indicate the following: 1 Insulation tube
  • FIG. 11 is a spectrum diagram of wavelength and absorption.
  • FIG. 12 is a correlation diagram between the discharge power and the concentration in the waste gas.
  • the blow-off type plasma processing apparatus may be configured such that metal electrodes having variously shaped protruding portions are used as electrodes, and the metal pipes may be cylindrical, rectangular, or cylindrical. Alternatively, it may have any of a variety of shapes, such as a flat cylindrical body, and a structure of a single cylinder or multiple cylinders.
  • the tip may be formed by a notched inclined surface at the edge, or the peripheral edge may be a tooth-like or needle-like body, or a plurality of loop-like wires. It may also be formed by disposing of the components.
  • the plasma reaction is also possible, such as formation of a thin film on the surface of the substrate facing the outlet, processing such as surface modification, synthesis of gas compounds, gas decomposition, etc.
  • the device of the present invention is applied to an object. This device realizes highly efficient plasma reaction at extremely low cost. For this reason, for example, there is no need for an expensive device for keeping the gap mm uniform with a long cylinder in a conventional ozonizer. It is advantageously applied to various synthesis and decomposition reactions.
  • a metal tube is used as an electrode for glow discharge.
  • the metal pipe () can be formed with a slope with the edge (3) of the outlet (2) cut out to form a tip.
  • a voltage is applied to the electrode of the metal tube (1) by a power supply (4), and a voltage is applied to the conduit of the metal tube (1).
  • the surface of (7) is treated, and film formation or surface modification is performed.
  • the metal tube (1) may be carbon as long as it is conductive, but the type is not particularly limited, but it is heat-resistant such as stainless steel, tungsten, and molybdenum. However, when the outside of the pipe is cooled by a water cooling jacket or the like, a copper pipe or the like can be used.
  • the inner and outer diameters are not limited, and may be a large-diameter metal tube having an inner diameter exceeding 10 cm or a thin tube having a diameter of 0.1 mm or less.
  • the distance (I) between the metal tube (1) as the electrode and the substrate (7) can be appropriately determined depending on the type of gas, the blowing speed thereof, the state of the green plasma, and the like. For example, it can be set to about 0.1 mm to 100 mm or more. Further, in order to prevent external creeping discharge of the metal tube '(1), as shown in FIG. 2, the peripheral surface thereof may be covered with an insulator (8).
  • the power supply (4) connected to such a metal tube (1), and a low frequency of several KHz to a high frequency of several 10 KHz or 13.56 MHz. It can be done.
  • the discharge occurs with respect to the arc pole, that is, the stray capacitance between the counter electrode and the high-voltage pole.
  • it is effective to place the substrate (7) on a dielectric.
  • arcing can be prevented by adding a small capacitor in series between the high-voltage electrode and the power supply.
  • inorganic gas such as oxygen and ammonia is used.
  • Compounds and fluorine chemicals such as C 2 F 4 and C 3 F 6,
  • Fluorinated paraffinic hydrocarbons such as CF4 ⁇ and C2F6, or chain hydrocarbons with side chains containing fluorine atoms, or fluorinated aromatic hydrocarbons any organic compound such as hydrocarbon having functional groups, does not have also rather like, the are al N 0 x, S 0, ⁇ you can in this transgression using waste gas, etc. containing.
  • Such reactive gases are rare gases such as He and Ar.
  • an inert gas such as N 2 or air
  • the total pressure of the gas (5) should be around 1 atm.
  • ketones and meta- It is also advantageous to mix hydrocarbon compounds such as ethane and ethane.
  • the mixing ratio is from the order of ppm to several percent.
  • Glow plasma can be generated stably and, depending on the selection of conditions, can be used effectively as other types of discharge.
  • the substrate (7) when used, it can be made of rubber plastic, glass, ceramics, or any other appropriate type and in various shapes, such as bulk, plate, It can be a fibrous body, powder, film or the like. It is not necessary to use such a substrate (7) for waste gas treatment or gas phase synthesis.
  • a further example of a metal cylinder as an electrode is:
  • the metal pipe (1) may have an inclined surface on the inner periphery of the edge (3), or may have an inclined surface as shown in FIG. 4 and FIG.
  • a tooth-like body (9) or a needle-like body (10) may be provided on the peripheral edge.
  • the electric field is concentrated on these protruding parts, that is, the parts having a small radius of curvature.
  • the preferred range of the radius of curvature is determined by the type of gas.
  • a plurality of loop-shaped wires may be provided at the edge (3).
  • a suitable thickness is determined depending on the gas to be used. Therefore, the discharge can be controlled by the thickness of the wire (11). For example, in the case of argon (Ar), about 0.3 mm and N 2 are considered, and in the case of air, about 0.025 mm is considered.
  • a wire of the same thickness can be filled into the pipe leading to the outlet at a constant bulk density.
  • a metal wire coated with an insulating material may be filled in a dielectric solid cylinder such as a glass. These coating wires constitute the tip of the present invention.
  • the coating wire (110) is placed inside a tube made of a metal tube (111) with an insulating coat (112) such as glass. It may be arranged at a location.
  • the coating wire (110) is coated, even if it comes into contact with the metal tube (111), the entire length thereof effectively functions as an electrode.
  • Such a variety of protruding portions can be employed in a case where a single metal cylinder is used or in a multi-layer structure as illustrated in FIG.
  • a gas (A) that is difficult to discharge is blown out to the center, and a gas (B) that is easy to discharge is blown out, so that the gas that is difficult to discharge is discharged. Therefore, the discharge efficiency can be further improved.
  • FIG. 8 For fine processing such as surface etching of the base (7), an apparatus as shown in FIG. 8 may be used.
  • waste gas treatment and gas phase synthesis as shown in Fig. 9,
  • the electrode metal tube (14) may be made to face the lower tube (13) covered or uncoated by (12).
  • the outer peripheral portion of an insulator tube (1) such as a cylindrical tube is provided.
  • a pair of rig-shaped electrodes (2) and (3) are provided. So A plurality of combinations of lever electrodes (2) and (3) are provided in the pipe length direction.
  • the material of the insulating tube (1) For example, general-purpose plastics such as glass and vinyl tubes, as well as PTFT, FEP, PET, PPS.PEEK, ABS, silicone tubes, etc. Any general-purpose plastic material for industrial use, ceramics, etc. can be used.
  • the thickness of the insulating tube (1) is not particularly limited, and the diameter is 10 mm. Large-diameter pipe exceeding cm ⁇ Can be made of any material such as ultra-fine pipe of 0.1 mm ⁇ or less.
  • the cross-sectional shape can be circular or polygonal.
  • a foil-shaped electrode is used as a pair of the ring-shaped electrodes (2) and (3), and this can be attached to the outer peripheral surface of the insulator tube (1).
  • the insulator tube can be moved in the axial direction of the electrodes (2) and (3), so that a long object can be continuously connected. Processing becomes possible.
  • various conductive materials such as copper, silver, nigel, anolymium, stainless steel, and carbon can be arbitrarily used. .
  • the distance (L) between the electrodes of such ring-shaped electrodes (2) and (3) can be up to about 25 mm. Preferably from 5 mm 20 mm.
  • the width (m) is preferably from 0.1 mm to about 20 mm. In addition, it can correspond to the diameter of the insulating tube (1). Further, in order to prevent external creeping discharge, the entire outer peripheral surface can be covered with an insulating adhesive such as epoxy or silicone adhesive.
  • a pair of electrodes can be connected in parallel or in series, for example, as illustrated in FIG.
  • connection direction between the above-mentioned electrodes it is preferable to make them parallel in order to reduce the applied voltage.
  • the frequency can be as low as K Hz and several ⁇ ⁇ ⁇ or as high as 13.56 MHz.
  • the reactive gas of the mixed gas (5) introduced from one end of the insulator tube (1) may be an inorganic monomer such as oxygen or ammonia, or C 2 F 4 or C 3 F 6.
  • a reactive gas is greatly diluted with a diluent gas mainly composed of He to obtain a mixed gas (5).
  • the mixing ratio of He is large, but an inert gas such as Ar or N2 can be mixed if necessary.
  • the mixing ratio of Ar to He can be about 90%. This makes it possible to reduce the amount of expensive He used and reduce the cost.
  • the total pressure of the mixed gas (5) should be around 1 atm.
  • the generated glow discharge plasma can cause various chemical treatments such as various surface treatments, thin film formation, synthesis, decomposition, etc., and the efficiency can be significantly improved.
  • Targets include the inner surface of the insulator tube (1), as well as objects placed inside the insulator tube (1) or moving body surfaces such as powders that are suspended or vibrated and carried inside the tube. Arbitrarily, such as a circulated material, a liquid surface partially leaving a gas phase. There are no particular restrictions on the surfaces that can be treated, including untreated surfaces. As such, any surface formed or treated with cellulose, biomaterial, or the like can be used.
  • the tip of a stainless steel cylinder with an outer diameter of 3 mm and an inner diameter of 2 mm is sharply polished as shown in Fig. 1 to form a discharge tube.
  • a stainless steel plate with a thickness of 5 mm was used as the lower electrode, on which a soft film and a polyethylene film with a thickness of 40 mm were attached as a sample.
  • the gap between the tip of the discharge tube and the lower electrode was 20 mm.
  • the area around the discharge tube is open to the atmosphere.
  • the surface of the sample polyethylene placed at the tip of the jet stream is exposed to the stream of excited argon atoms generated in the plasma, causing a chemical change.
  • the gas in the jet stream Since the temperature remains low, even low-melting soft polyethylene does not melt.
  • Table 1 shows the contact angles of water droplets on the polyethylene surface treated by the above method.
  • Example 1 The lower electrode in Example 1 is removed, and only the polyethylene film is supported by an insulator support rod and stretched perpendicular to the blowout electrode. A plasma jet was sprayed on the surface of the sample film at a distance of 20 from the discharge tube tip.
  • Table 2 shows the contact angles of water droplets on the treated sample surface.
  • Example 2 In both Example 1 and Example 2, the contact angle on the surface was extremely reduced within a very short time of several seconds to 10 seconds.
  • Polyethylene surface which originally has high water-based and water-based properties and thus lacks the ability to bond with various adhesives, has been easily converted to hydrophilic, that is, an active surface that can be bonded by the above method. become.
  • the discharge tube can be moved left, right, up and down, or the discharge tube having a different diameter can be used. This shows that surface treatment can be performed with any shape and size regardless of the size and shape of the object to be processed or the presence or absence of the lower electrode, which is an extremely useful method.
  • the opposite electrode is the earth potential located at infinity, and it goes without saying that the discharge is caused through the stray capacitance of the discharge tube.
  • the surface to be treated is discolored to a whitish color over a long period of time of 20 seconds or more, indicating a chemical change such as oxidation.
  • a r Metastable excited atoms that are in a high electron energy state are generated in the plasma and sprayed on the surface, cutting high molecular chains on the surface, resulting in cross-link bonds inside and peroxide on the surface It is considered that a hydrophilic reactive group such as a product was generated.
  • Example 3 ′ Since the metastable atom is in a highly excited state only in the electronic state and the gas temperature is around room temperature, it does not cause phenomena such as melting of the surface to be processed, which is likely to occur in high-temperature plasma jet processing.
  • Example 3 ′ Since the metastable atom is in a highly excited state only in the electronic state and the gas temperature is around room temperature, it does not cause phenomena such as melting of the surface to be processed, which is likely to occur in high-temperature plasma jet processing.
  • the gas to be polymerized was mixed with a carrier gas such as Ar and blown out, dissociated in the carrier gas plasma jet, and placed on the partner electrode. It was formed as a polymer thin film on a substrate.
  • a mirror-polished 0.5 mm thick silicon wafer was used as a sample substrate mounted on a stainless steel electrode.
  • Fig. 11 shows the transmitted infrared spectrum of this powder.
  • the mixed gas containing PP m is mixed into N 2 carrier gas, blown out together with N 2 plasma, decomposed, and sampled with a glass tube with a diameter of 10 mm downstream of the plasma. Analysis was performed by the chromatographic method. The experimental conditions are described below.
  • one electrode width (m) is set to the outside of a Pyrex glass tube with an outer diameter of 15 mm, a thickness of 2 mm, and a length of 500 mm. mm, the distance between the poles (L) was 20 mm, a plurality of electrode pairs were arranged, and the total length of the electrode group was 310 mm.
  • PET polyethylene terephthalate
  • the electrode material was a copper plate.
  • the discharge conditions were as follows.
  • Example 5 In the same manner as in Example 5, a mixed gas of He and C 2 F 4 (tetrafluoroethylene, TFE) was introduced at 1 atm to generate a discharge. A polyimid film was inserted into the glass tube, but a transparent film was formed on the inner surface.
  • C 2 F 4 tetrafluoroethylene
  • PT'FE polytetrafluoroethylene
  • the present invention is not limited by the above examples. It goes without saying that various modes are possible for details such as the form and material of the electrode, the type of reactive gas and rare gas to be introduced, and the applied voltage and its frequency.
  • a highly efficient and stable plasma reaction is realized with a simple structure. Stationary or moving inside or inside an insulator tube such as a cylindrical tube made of glass, plastic, ceramics, etc. Alternatively, it becomes possible to perform plasma treatment on the flowable material under atmospheric pressure.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Plasma Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention se rapporte à un appareil de traitement au plasma à décharge luminescente de pression atmosphérique, qui utilise comme électrode un cylindre métallique (1) ayant une partie pointue au bord (3) d'un orifice de soufflage (2). Cet appareil projette un gaz rare, un gaz inerte ou de l'air ou encore un mélange (5) de ces gaz avec un gaz réactif depuis l'orifice de soufflage (2) du cylindre métallique servant d'électrode (1), afin d'appliquer une tension, et il génère un plasma par décharge (6) à une pression atmosphérique. Plusieurs paires d'électrodes de forme annulaire sont disposées dans le sens longitudinal de la partie périphérique externe d'un tube isolant, et ces paires d'électrodes sont connectées en parallèle ou en série. Le mélange gazeux constitué par le gaz réactif et par le gaz rare est introduit depuis la partie terminale de ce tube isolant et un plasma par décharge luminescente est généré à l'intérieur du tube à une pression atmosphérique. Ainsi, on obtient grâce à la présente invention un appareil à plasma pour traiter des objets résidant à l'intérieur du tube ou passant à travers le tube.
PCT/JP1992/001607 1992-12-09 1992-12-09 Procede et appareil pour traitement au plasma a decharge luminescente a la pression atmospherique WO1994014303A1 (fr)

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PCT/JP1992/001607 WO1994014303A1 (fr) 1992-12-09 1992-12-09 Procede et appareil pour traitement au plasma a decharge luminescente a la pression atmospherique

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Application Number Priority Date Filing Date Title
PCT/JP1992/001607 WO1994014303A1 (fr) 1992-12-09 1992-12-09 Procede et appareil pour traitement au plasma a decharge luminescente a la pression atmospherique

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999059385A1 (fr) * 1998-05-12 1999-11-18 Masarykova Univerzita Procede d'obtention d'un environnement physiquement et chimiquement actif au moyen d'un jet de plasma et jet de plasma associe
US6528947B1 (en) 1999-12-06 2003-03-04 E. I. Du Pont De Nemours And Company Hollow cathode array for plasma generation
WO2012010299A1 (fr) 2010-07-21 2012-01-26 Dow Corning France Traitement au plasma de substrats
WO2012146348A1 (fr) 2011-04-27 2012-11-01 Dow Corning France Traitement par plasma de substrats
WO2013068085A1 (fr) 2011-11-09 2013-05-16 Dow Corning France Traitement au plasma de substrats
EP3988686A1 (fr) * 2020-10-26 2022-04-27 Nadir S.r.l. Procede de fabrication d'un revêtement catalytique et dispositif de catalyse heterogene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62247076A (ja) * 1986-04-18 1987-10-28 Hitachi Ltd プラスチツク管のコ−テイング方法
JPS6350478A (ja) * 1986-08-21 1988-03-03 Tokyo Gas Co Ltd 薄膜形成法
JPH0353482A (ja) * 1989-07-20 1991-03-07 Toray Ind Inc 放電処理装置の放電電極
JPH03219082A (ja) * 1989-11-30 1991-09-26 Sumitomo Precision Prod Co Ltd 吹出型表面処理装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62247076A (ja) * 1986-04-18 1987-10-28 Hitachi Ltd プラスチツク管のコ−テイング方法
JPS6350478A (ja) * 1986-08-21 1988-03-03 Tokyo Gas Co Ltd 薄膜形成法
JPH0353482A (ja) * 1989-07-20 1991-03-07 Toray Ind Inc 放電処理装置の放電電極
JPH03219082A (ja) * 1989-11-30 1991-09-26 Sumitomo Precision Prod Co Ltd 吹出型表面処理装置

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999059385A1 (fr) * 1998-05-12 1999-11-18 Masarykova Univerzita Procede d'obtention d'un environnement physiquement et chimiquement actif au moyen d'un jet de plasma et jet de plasma associe
US6525481B1 (en) 1998-05-12 2003-02-25 Masarykova Univerzita Method of making a physically and chemically active environment by means of a plasma jet and the related plasma jet
US6528947B1 (en) 1999-12-06 2003-03-04 E. I. Du Pont De Nemours And Company Hollow cathode array for plasma generation
WO2012010299A1 (fr) 2010-07-21 2012-01-26 Dow Corning France Traitement au plasma de substrats
WO2012146348A1 (fr) 2011-04-27 2012-11-01 Dow Corning France Traitement par plasma de substrats
WO2013068085A1 (fr) 2011-11-09 2013-05-16 Dow Corning France Traitement au plasma de substrats
EP3988686A1 (fr) * 2020-10-26 2022-04-27 Nadir S.r.l. Procede de fabrication d'un revêtement catalytique et dispositif de catalyse heterogene

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