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EP1230414B1 - Procede et dispositif servant au revetement par plasma de surfaces - Google Patents

Procede et dispositif servant au revetement par plasma de surfaces Download PDF

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Publication number
EP1230414B1
EP1230414B1 EP00926739A EP00926739A EP1230414B1 EP 1230414 B1 EP1230414 B1 EP 1230414B1 EP 00926739 A EP00926739 A EP 00926739A EP 00926739 A EP00926739 A EP 00926739A EP 1230414 B1 EP1230414 B1 EP 1230414B1
Authority
EP
European Patent Office
Prior art keywords
plasma jet
nozzle
precursor material
plasma
precursor
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.)
Expired - Lifetime
Application number
EP00926739A
Other languages
German (de)
English (en)
Other versions
EP1230414A1 (fr
Inventor
Peter FÖRNSEL
Christian Buske
Uwe Hartmann
Alfred Baalmann
Guido Ellinghorst
Klaus-D. Vissing
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.)
Plasmatreat GmbH
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Plasmatreat GmbH
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Plasmatreat GmbH, Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Plasmatreat GmbH
Publication of EP1230414A1 publication Critical patent/EP1230414A1/fr
Application granted granted Critical
Publication of EP1230414B1 publication Critical patent/EP1230414B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • H05H1/32—Plasma torches using an arc
    • H05H1/42—Plasma torches using an arc with provisions for introducing materials into the plasma, e.g. powder or liquid
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • 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
    • H05H1/32—Plasma torches using an arc
    • H05H1/34—Details, e.g. electrodes, nozzles

Definitions

  • the invention relates to a method for coating Surfaces with the characteristics of the generic term of Claim 1.
  • the invention also relates to a device for coating surfaces with the characteristics of Claim 7.
  • DE 198 07 086 A discloses one method and one Device for plasma coating of surfaces, wherein in the excitation zone between two electrodes, one of which at least one is provided with a dielectric, one Corona discharge is ignited. This type of discharge is also known as a tuft of sparks. The corona discharge avoids unwanted hot discharge or arc discharge between the electrodes to destroy the electrodes or the substrate to be coated or the to prevent deposited layer.
  • W099 / 20809 also discloses a method and a Device for coating surfaces in which Help of a radio frequency discharge that deliberately a Discharge arc avoids the working gas being excited in which feeds the precursor material downstream becomes.
  • the present invention has the technical problem based on a procedure of the type mentioned at the beginning create that with simple process control an efficient and easily controllable coating, and a expedient device for performing this method specify.
  • the atmospheric plasma in the shape of a beam is generated, which is essential has a greater range than the discharge zone of one Corona discharge, the coating process simply run by the surface to be coated the substrate is covered with the plasma jet. There no counter electrode on the back of the substrate is required, the substrates can also be act thicker and / or complex shaped workpieces. Since that Precursor material supplied separately from the working gas and in the plasma jet is fed, which only in the Excitation zone arises, needs the precursor material not to cross the entire excitation zone itself. This has the important advantage that it mostly consists of monomers Connections existing precursor material is not already in decomposes in the excitation zone or chemically in some other way is changed.
  • the necessary excitation energies for the desired one Reaction of the monomers is primarily through free electrons, Ions or radicals are still provided in large numbers in the cool plasma jet are included.
  • the precursor material does not necessarily need to be in the gaseous state to be fed in, but can also, for example, in liquid or solid, powdery state can be fed so that it is only in the reaction zone evaporates or sublimates. It is also possible to use the precursor material add solid particles such as color pigments or the like, which then in the embedded polymer-like layer on the substrate surface become. In this way, the color, the roughness or the electrical Adjust the conductivity of the coating as required.
  • the Venturi effect can be exploited to get the precursor material into the plasma jet to suck.
  • the precursor material is actively supplied, can by choosing the angle at which the precursor material is relative to The beam direction of the plasma jet is fed in, the extent of the mixing of the precursor material in the plasma.
  • the feed of the precursor material can take place in the same direction or opposite to the direction of swirl.
  • this temperature can be achieved, for example, by heating the working gas and / or precisely by heating the mouth of the plasma nozzle.
  • a plasma nozzle can be used to generate the plasma jet are, as described - for other purposes - in DE 195 32 412 C2 becomes.
  • a plasma nozzle can be used to generate the plasma jet are, as described - for other purposes - in DE 195 32 412 C2 becomes.
  • a plasma nozzle can be used to generate the plasma jet are, as described - for other purposes - in DE 195 32 412 C2 becomes.
  • a plasma nozzle can be used to generate the plasma jet are, as described - for other purposes - in DE 195 32 412 C2 becomes.
  • EP-A 986 993 eccentrically on a rotary head
  • the plasma nozzle shown in FIG. 1 has a tubular housing 10, the one elongated nozzle channel 12, which tapers conically at the lower end forms.
  • An electrically insulating ceramic tube 14 is inserted in the nozzle channel 12.
  • a working gas, such as air, is from the top in the drawing End her fed into the nozzle channel 12 and with the help of one in the ceramic tube 14 used swirl device 16 so that it is vortex-shaped flows through the nozzle channel 12, as in the drawing by a helical Arrow is symbolized.
  • a vortex core is thus created in the nozzle channel 12, which runs along the axis of the housing.
  • a pin-shaped electrode 18 is mounted on the swirl device 16 protrudes coaxially into the nozzle channel 12 and to the with the help of a high voltage generator 20 a high-frequency AC voltage is applied.
  • the voltage generated by the high-frequency generator 20 is of the order of magnitude of a few kilovolts and has a frequency of the order of magnitude, for example from 20 kilo heart.
  • the metal housing 10 is grounded and serves as a counter electrode, so that an electrical discharge between the electrode 18 and the housing 10 can be caused.
  • This corona discharge an arc discharge from the electrode 18 to the housing 10 is ignited.
  • the Arc 22 of this discharge is swirled by the working gas flowing in taken and channeled in the core of the vortex-shaped gas flow, see above that the arc is then almost rectilinear from the tip of the electrode 18th runs along the housing axis and is only in the area of the mouth of the housing 10 branches radially onto the housing wall.
  • the housing 10 at the tapered end of the nozzle channel 12 a radially inward projecting shoulder 24, which forms the actual counter electrode and the radially branching branches of the arc 22.
  • the branches rotate thereby in the swirl direction of the gas flow, so that a non-uniform erosion on the shoulder 24 is avoided.
  • a cylindrical mouthpiece 26 made of ceramic used In the mouth of the housing 10 is a cylindrical mouthpiece 26 made of ceramic used, the axially inner end of which is flush with the shoulder 24 and is directly surrounded by this shoulder and its length is significantly greater is than the inside diameter.
  • the plasma generated by the arc 22 flows in a swirling manner through the mouthpiece 26 and becomes thermal due to Expansion when flowing through the mouthpiece 26 accelerated and radial expanded so that you get a very strongly fan-shaped expanded plasma jet 28 receives, which is still a few centimeters above the open end 30 of the Mouthpiece 26 extends and rotates in the direction of swirl.
  • This plasma nozzle is used for plasma coating or plasma polymerization of a Substrate 34 used. To do this, the precursor material is removed using a Lance 32 is fed into the concentrated plasma jet inside the mouthpiece 26.
  • a mouthpiece 26 ' is inserted here, which is a Venturi nozzle 36 forms for the self-priming feed of the precursor material.
  • the precursor material is first of all in a ring chamber via a nozzle 38 40 fed to the outer circumference of the mouthpiece 26 'and arrives from there radially through one or more holes in Venturi 36.
  • the feed location is therefore located at the downstream end of the excitation zone, in which is generated by the plasma beam 28 'and by the arc 22 penetrated nozzle channel 12 is formed.
  • the Venturi nozzle 36 opens into a transverse channel 42, which at both ends in another, on the circumference of the mouthpiece 26 'formed ring channel 44 and opens over a narrow, in the direction of a Diameter of the mouthpiece extending groove 46 to the end face of the mouthpiece is open. That emerging from the venturi 36 with the precursor gas mixed plasma is distributed in the transverse channel 42 and then passes far fanned out through the groove 46. In this way, a uniform coating can be achieved on a strip-shaped surface of the substrate, not shown here achieve.
  • FIG. 4 shows the mouth region of a plasma nozzle, with which a rotationally symmetrical, relatively sharply focused plasma beam 28 "generated becomes.
  • the mouthpiece 26 "forms a proportionate small circular nozzle opening 48.
  • the feed of the precursor material takes place again via a lance 32, but here only downstream of the nozzle opening 48 opens into the plasma jet 28 ".
  • This type of feed is below other advantageous in cases where the precursor material is carbon or contains other substances that lead to the formation of electrically conductive precipitates tend.
  • FIG. 4 also illustrates a method variant in which the plasma jet 28 "with the aid of a gassing nozzle concentrically surrounding the nozzle opening 48 50 is gassed with a protective gas 52.
  • FIG. 5 illustrates a method variant in which the feed of the precursor material with the help of an insulating tube 54 coaxially through the interior of the housing 10 and the electrode 18.
  • This arrangement has due to their perfect symmetry the advantage that a uniform Distribution of the precursor material in the plasma jet 28 "is achieved.
  • the feed location of the precursor material depending on the material and process conditions vary by advancing or retracting tube 54 becomes.
  • the tube 54 can also be withdrawn as far as that the feed is within the downstream third of the nozzle channel 12 takes place.
  • the plasma jet 28 "by touching the working gas with the Arc 22 is generated, which here is helical around the tube 54 winds, can also in the downstream region of the nozzle channel 12 of a plasma jet can be spoken, so that in this case the feed still done in the plasma jet.
  • the process the precursor material due to the constriction of the Plasma in the mouth area of the nozzle generally somewhat higher temperatures get abandoned. Under certain circumstances, a - small - proportion of the precursor material can also be destroyed by direct contact with the arc 22. However, this can also have a positive effect, as it does for certain Components of the precursor material high excitation energies are available.
  • a comparable effect can thereby be achieved with the plasma nozzle shown in FIG achieve that the throughput and / or swirl of the working gas is increased.
  • the branches of the arc 22 that are on the walls of the housing 10 and the mouthpiece 26 'branch deeper into the Venturi 36 penetrate and optionally loop-shaped from the nozzle opening "blown out" so that a more or less large part of the supplied precursor gas comes into contact with the arc.
  • the precursor material is fed together with the substrate into the plasma jet, for example by the precursor material z.
  • the precursor material is fed together with the substrate into the plasma jet, for example by the precursor material z.
  • B. by means of aerosol or ultrasound, by vapor deposition, by spraying, rolling or knife coating or electrostatically on the surface of the substrate is applied before this surface with the plasma jet is treated.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Plasma Technology (AREA)
  • Chemical Vapour Deposition (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Coating Apparatus (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Nozzles (AREA)

Claims (13)

  1. Procédé de revêtement de surface, dans lequel
    on génère un faisceau de plasma (28 ; 28', 28") en faisant passer un gaz de travail à travers une zone d'excitation (12),
    on introduit dans le faisceau de plasma un matériau précurseur séparément du gaz de travail,
    on provoque la réaction du matériau précurseur à l'aide du faisceau de plasma et
    on dépose le produit de réaction sur la surface (34),
       la réaction et le dépôt étant effectués à la pression atmosphérique,
       caractérisé en ce que l'on génère une décharge en arc en appliquant une tension alternative de fréquence élevée sur des électrodes (10, 18) placées à l'intérieur de la zone d'excitation.
  2. Procédé selon la revendication 1, caractérisé en ce que le matériau précurseur contient, dans l'état dans lequel il est introduit dans le faisceau de plasma, des composés liquides et/ou solides.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau précurseur est injecté dans une ouverture de sortie (36 ; 48) par laquelle le faisceau de plasma quitte la zone d'excitation (12).
  4. Procédé selon la revendication 3, caractérisé en ce que le gaz précurseur est amené dans l'ouverture de sortie conformée en buse de Venturi (36) en utilisant l'effet de Venturi.
  5. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau précurseur est injecté dans le faisceau de plasma en aval d'une ouverture de sortie (48) par laquelle le faisceau de plasma (28') quitte la zone d'excitation (12).
  6. Procédé selon la revendication 1 ou 2, caractérisé en ce que le matériau précurseur est injecté dans la région aval de la zone d'excitation (12) où est généré le faisceau de plasma.
  7. Dispositif de revêtement de surfaces (34), comportant
    un boítier (10) électriquement conducteur de forme tubulaire qui forme un canal de buse (12),
    une électrode (18) placée coaxialement dans le canal de buse (12), et
    un dispositif d'amenée (32 ; 36, 38, 40) destiné à amener un matériau précurseur dans le faisceau de plasma,
       caractérisé en ce qu'un générateur de fréquences élevées est prévu pour appliquer une tension alternative entre l'électrode (18) et le boítier (10) afin de générer une décharge en arc.
  8. Dispositif selon la revendication 7, caractérisé en ce que le boítier (10) contient un dispositif de vrillage (16) destiné à vriller le gaz de travail dans le canal de buse (12).
  9. Dispositif selon la revendication 7 ou 8, caractérisé en ce que le dispositif d'amenée de gaz précurseur est une lance (32) qui débouche dans le faisceau de plasma en aval de la sortie du canal de buse (12).
  10. Dispositif selon la revendication 9, caractérisé en ce qu'une pièce d'embouchure (26) de forme tubulaire et en matériau électriquement isolant est insérée dans la sortie du canal de buse (12) et en ce que la lance (32) débouche dans la pièce d'embouchure (26).
  11. Dispositif selon la revendication 7 ou 8, caractérisé en ce que le dispositif d'amenée de matériau précurseur est une buse de Venturi (36) conformée dans la sortie du canal de buse (12).
  12. Dispositif selon la revendication 7 ou 8, caractérisé en ce que le dispositif d'amenée de gaz précurseur est un petit tube (54) électriquement isolant qui s'étend coaxialement à travers la buse de plasma et dont l'embouchure peut se trouver au choix à l'intérieur ou à l'extérieur du canal de buse (12).
  13. Dispositif selon l'une des revendications 7 à 12, caractérisé en ce qu'une buse de gaz de protection (50) enveloppant la sortie de la buse de plasma (10) est prévue pour gazéifier le faisceau de plasma sortant avec un gaz de protection (52).
EP00926739A 1999-10-30 2000-03-17 Procede et dispositif servant au revetement par plasma de surfaces Expired - Lifetime EP1230414B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE29919142U DE29919142U1 (de) 1999-10-30 1999-10-30 Plasmadüse
DE29919142U 1999-10-30
PCT/EP2000/002401 WO2001032949A1 (fr) 1999-10-30 2000-03-17 Procede et dispositif servant au revetement par plasma de surfaces

Publications (2)

Publication Number Publication Date
EP1230414A1 EP1230414A1 (fr) 2002-08-14
EP1230414B1 true EP1230414B1 (fr) 2004-10-06

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EP00926739A Expired - Lifetime EP1230414B1 (fr) 1999-10-30 2000-03-17 Procede et dispositif servant au revetement par plasma de surfaces

Country Status (7)

Country Link
US (1) US6800336B1 (fr)
EP (1) EP1230414B1 (fr)
JP (1) JP4082905B2 (fr)
AT (1) ATE278817T1 (fr)
DE (2) DE29919142U1 (fr)
ES (1) ES2230098T3 (fr)
WO (1) WO2001032949A1 (fr)

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DE102008058783A1 (de) 2008-11-24 2010-05-27 Plasmatreat Gmbh Verfahren zur atmosphärischen Beschichtung von Nanooberflächen
DE102009048397A1 (de) * 2009-10-06 2011-04-07 Plasmatreat Gmbh Atmosphärendruckplasmaverfahren zur Herstellung oberflächenmodifizierter Partikel und von Beschichtungen
WO2012123530A1 (fr) 2011-03-16 2012-09-20 Reinhausen Plasma Gmbh Revêtement ainsi que procédé et dispositif de revêtement
WO2013014212A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé d'application d'un revêtement sur un substrat, revêtement, et utilisation de particules
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DE102012102721A1 (de) 2012-03-29 2013-10-02 BSH Bosch und Siemens Hausgeräte GmbH Verfahren zum Passivieren einer Metalloberfläche
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WO2021023605A1 (fr) 2019-08-08 2021-02-11 Plasmatreat Gmbh Procédé pour équiper un dispositif d'affichage électronique avec un dispositif de protection d'écran d'affichage
WO2024068623A1 (fr) 2022-09-29 2024-04-04 Plasmatreat Gmbh Traitement au plasma avec refroidissement par liquide
DE102023106618A1 (de) 2022-09-29 2024-04-04 Plasmatreat Gmbh Plasmabehandlung mit Flüssigkeitskühlung
DE102024117476A1 (de) * 2024-06-20 2025-12-24 Sms Group Gmbh Kathodenteil, Anodenteil, Zuführeinrichtung, Vorrichtung zum thermischen Spritzen, Verfahren zum Herstellen eines derartigen Kathodenteils und/oder Anodenteils, Verfahren zum Betreiben einer Vorrichtung zum thermischen Spritzen, Verwendung eines Kathodenteils, Verwendung eines Anodenteils und Verwendung einer Zuführvorrichtung von Pulverpartikeln

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JP2003514114A (ja) 2003-04-15
JP4082905B2 (ja) 2008-04-30
EP1230414A1 (fr) 2002-08-14
DE29919142U1 (de) 2001-03-08
US6800336B1 (en) 2004-10-05

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