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EP1675971B1 - Procede de revetement de la surface d'un substrat avec utilisation d'un jet de plasma - Google Patents

Procede de revetement de la surface d'un substrat avec utilisation d'un jet de plasma Download PDF

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Publication number
EP1675971B1
EP1675971B1 EP04786991A EP04786991A EP1675971B1 EP 1675971 B1 EP1675971 B1 EP 1675971B1 EP 04786991 A EP04786991 A EP 04786991A EP 04786991 A EP04786991 A EP 04786991A EP 1675971 B1 EP1675971 B1 EP 1675971B1
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EP
European Patent Office
Prior art keywords
plasma
powder
fine granular
nozzle
substrate surface
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Revoked
Application number
EP04786991A
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German (de)
English (en)
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EP1675971A1 (fr
Inventor
Michael Dvorak
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Individual
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Individual
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Priority to PL04786991T priority Critical patent/PL1675971T3/pl
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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
    • 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

Definitions

  • the invention relates to a method for coating a substrate surface using a plasma jet according to the preamble of claim 1 and to an application of the method according to claim 12.
  • refractory layers to a substrate surface by means of a plasma jet
  • suitable substances e.g. Tungsten or oxide ceramics are supplied in powder form in a plasma free jet.
  • thermal plasmas in which temperatures of up to 20,000 ° C. prevail in the core of the exiting free plasma jet.
  • the plasma stabilization takes place here by high currents (> 200 A) and easy to ionizing gases.
  • Such a plasma causes a high temperature load of the component to be coated. If the coating process takes place under atmosphere, metallic coating materials also partly oxidize. Therefore, the range of use is very narrow.
  • the coating and / or processing of low-melting materials is possible, if at all, only by extremely complex process control and the use of strong cooling.
  • WO 01/32949 describes a method for coating surfaces, in which a precursor material is reacted by means of a plasma and the reaction product is then deposited on the surface to be coated.
  • This precursor material be it liquid and / or solid, is fed separately from the working gas into the plasma jet. As soon as a reaction of the introduced material is to take place, sufficient heating of the recurser material must be achieved.
  • the present invention has for its object to provide a method of the type mentioned, by means of which well adhering layers can be applied to metal, glass, plastic or other substrate surfaces.
  • the powder applied to the substrate surface by the free plasma jet is applied with good adhesion without the substrate temperature rising inadmissibly. Nevertheless, an excellent adhesion of the applied layer is achieved even under air atmosphere by this microscopic plasma process.
  • Metallic layers are also characterized by their extremely low oxygen content.
  • Fig.1 shows a known per se plasma nozzle 1 for generating a free plasma jet 2, which emerges from a lower nozzle opening 3 of the Plasmatrons 1 and is directed to a substrate surface 4.
  • the plasmatron 1 usually has an elongated, tubular housing 5, which tapers conically in the lower region 6 to the already mentioned nozzle opening 3.
  • the metal housing 5 is grounded and forms with the nozzle tip, for example, an outer electrode.
  • a primary imbalance plasma with low electrical power ( ⁇ 5 kW) is indicated within the plasmatron 5 - with box 11 - by high frequency alternating current (> 10 kHz), for example via a magnetron, an RF plasma, a direct high voltage discharge, a Coronabarriereentladung or similar generated.
  • a plasma or working gas is introduced from above through a supply line 7 so fluidly that thereby stabilizes the primary plasma (gas-stabilized plasmatron and, for example, vortex-stabilized plasmatron).
  • plasma or working gas preferably air or steam is used (cost).
  • the air can still be added as needed.
  • Nitrogen, carbon dioxide, methane or noble gases are added.
  • these other gases can also be used in pure form or in mixtures.
  • vapors of other liquids in pure form or in mixtures are to be used as plasma gases.
  • the emerging atmospheric plasma jet 2 is characterized in particular by a low temperature (in the core region ⁇ 500 ° C.) and low geometric expansion (diameter typically ⁇ 5 mm).
  • the free plasma jet 2 is then added as a fluidized, fine-grained powder in exactly metered amount, which is intended to form the intended coating on the substrate surface. There it is due to the interaction with the plasma up or even melted and accelerated in the direction of the surface to be coated, where it ultimately settles.
  • the powder material is delivered from a container 15 by means of a powder conveyor 16 and optionally introduced into the secondary plasma or primary plasma.
  • the low-temperature plasma is characterized in that after formation of an electrically or electromagnetically generated primary imbalance plasma (non-thermal plasma) in a partially closed plasma generator, the directed by suitable measures primary plasma jet by means of an annular nozzle at the transition to the environment (outlet 3) strong is accelerated and consequently after the nozzle forms a secondary plasma at ambient pressure. If the substrate surface is electrically conductive, a further voltage (so-called transferred arc or also direct plasmatron) can also be applied between the nozzle and the substrate.
  • the temperature of the plasma measured with a thermocouple type NiCr / Ni, tip diameter 4 mm, at 10 mm distance from the nozzle outlet is less than 900 ° C in the core of the secondary plasma jet (2) at ambient pressure.
  • a powder conveyor 16 is preferably one of the PCT patent application no. PCT / EP02 / 10709 known device for supplying metered quantities of fine-grained bulk material used, which has at least two alternately fillable and emptying metering chambers, wherein the metering chambers each by connection to a suction or. Vacuum line filled with the powder and emptied by connection to a compressed gas line while the powder is fluidized by the pressurized gas and pneumatically conveyed on.
  • Such a device as a powder conveyor 16 allows a highly precise metering and both a pulsed and a continuous, agglomeration-free supply of the finest powder whose grain size in the nanometer range to micrometer range (1 nm to 100 microns).
  • the possible embodiments of such a powder conveyor for electronically controllable promotion can be found in the aforementioned patent application and are therefore not described here in detail in detail.
  • the fluidized, fine-grained powder is introduced via a line 20 into the plasmatron 1 and there into the secondary plasma and / or introduced via a line 21 directly into the emerging from the nozzle opening 3 plasma jet 2.
  • a further possibility is to supply the powder via a likewise indicated by dashed lines 23 directly through the primary plasma in the flow direction of the plasma jet to the nozzle opening 3.
  • the amount of compressed gas required for the pneumatic delivery of the powder material is preferably 2 to 20% of the plasma gas amount.
  • the plasma gas consumption is about 100 to 5000 nl / h).
  • the powder applied to the substrate surface 4 by the plasma jet 2 is applied with good adhesion without the substrate temperature rising inadmissibly.
  • the temperature of the plasma measured with a thermocouple type NiCr / Ni, tip diameter 3 mm, at a distance of 10 mm from the nozzle outlet is less than 900 ° C in the core of the secondary plasma free jet at ambient pressure.
  • the substrate temperature increase during and after the coating process is well below 100 ° C., preferably below 50 ° C. Nevertheless, excellent adhesion of the coated layer is achieved by this microscopic atmospheric plasma process.
  • An advantage of the method according to the invention is that the substrate surface 4 to be coated requires no special preparation.
  • a surface cleaning can be carried out by the plasma process itself.
  • initially one or more times the plasma jet is directed without powder additive on the surface to be coated before the actual coating takes place.
  • This process is used primarily for tempering the surface and for its micro- or nanostructuring.
  • the inventive method is excellent for example for applying a zinc layer on welding or soldering of galvanized metal parts or sheets, which are used in particular in the auto industry. It is known that the zinc layer of the conventionally galvanized metal parts or sheets is removed during welding or soldering, whereby there is a risk of corrosion at such locations.
  • a plasma jet having a precisely defined width can be directed onto the site to be treated, for example a weld, and a zinc layer having a corresponding width (eg 2 to 3 ⁇ m / s) can be directed through a relative feed substrate / plasma nozzle (eg 0.3 m / s) 8 mm) can be applied exactly.
  • the powder feed is in the range of about 0.5 to 10 g / min.
  • the achievable layer thicknesses are typically 0.1 to 100 microns per overflow.
  • the device can be applied directly after the welding process (in-line process).
  • the method can also be used for medical purposes and serve, for example, for applying biologically active layers to skin substitutes or bone implants, with the aim of faster and improved integration of the implant into the human tissue.
  • the method can also be used for the metered or selective pretreating or metallization of plastics, paper, semiconductors or nonconductors, for example for the production of electrically conductive layers of Zn, Cu or Ag on Si wafers.
  • the method can be used for the decomposition-free application of well-adhering layers of plastics, such as polyamide, or high-performance plastics, such as PEEK with or without addition of inorganic nanometer to some micrometer-sized particles on plastics, wood, paper or metals.
  • plastics such as polyamide
  • high-performance plastics such as PEEK
  • powders with a specifically chemically and / or physically modified surface result. These powders can then serve as an improved or new precursor for other processes (eg, changing the hydrophobic behavior of soot into a hydrophilic behavior).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Plasma Technology (AREA)
  • Percussion Or Vibration Massage (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (17)

  1. Procédé de revêtement d'une surface de substrat (4) réalisé en utilisant un jet de plasma (2), auquel on ajoute en quantité dosée une poudre de fine granulométrie formant le revêtement au moyen d'un convoyeur de poudre pouvant être commandé (16), caractérisé en ce que
    l'on dirige sur la surface de substrat (4) un jet (8, 2) de plasma à faible température, auquel est ajoutée cette poudre en quantité dosée, de sorte que l'augmentation de température du substrat se situe, pendant et après le processus de revêtement, en dessous de 100 °C, de préférence, en dessous de 50 °C.
  2. Procédé selon la revendication 1, caractérisé en ce que la taille particulaire de la poudre de fine granulométrie ou du mélange pulvérulent peut se situer dans la plage nanométrique comprise entre 1 nanomètre et 100 micromètres.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la poudre de fine granulométrie est délivrée à partir d'un récipient (15) au moyen d'un convoyeur de poudre (16) présentant au moins deux chambres de dosage pouvant être remplies ou vidées en alternance, les chambres de dosage étant, respectivement, remplies de poudre par raccordement à une conduite d'aspiration ou à une conduite sous vide, et vidées de la poudre par raccordement à une conduite de gaz comprimé, de sorte que la poudre soit fluidisée par le gaz comprimée, puis acheminée par voie pneumatique, dans lequel la mise en marche et hors marche du raccordement d'aspiration, ainsi que du raccordement à gaz comprimé, sont réalisées par le biais de soupapes à commande pneumatique et/ou hydraulique.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le plasma est formé dans une buse à plasma (1) en acheminant un gaz de travail et/ou un liquide évaporable et en produisant une décharge qui est générée sous haute tension ou par le biais d'une alimentation électrique et/ou électromagnétique à haute fréquence, et en ce que le jet de plasma primaire (8) est projeté, à travers une ouverture (3) du plasmatron(1), conformée en buse, sur la surface de substrat (4), dans lequel la poudre de fine granulométrie est délivrée dans le plasma primaire et, de là, dans le jet de plasma secondaire (2) et/ou est directement délivrée dans le jet de plasma secondaire (2) qui sort de l'ouverture (3) de la buse.
  5. Procédé selon la revendication 4, caractérisé en ce que la poudre de fine granulométrie est acheminée dans une zone (6) de la buse à plasma (1) s'amincissant vers l'ouverture (3) de la buse.
  6. Procédé selon la revendication 4, caractérisé en ce que la poudre de fine granulométrie est délivrée directement (23) dans le plasma primaire.
  7. Procédé selon l'une quelconque des revendications 3 à 6, caractérisé en ce que la quantité de gaz comprimé destinée au transport pneumatique (20) de la poudre de fine granulométrie représente 2 à 20 % de la quantité de gaz de plasma (7).
  8. Procédé selon l'une quelconque des revendications 4 à 7, caractérisée en ce que l'on utilise de l'air comme gaz de travail ou gaz de plasma.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le plasma à faible température obtenu après formation d'un plasma primaire en déséquilibre généré par voie électrique ou électromagnétique dans un générateur de plasma partiellement fermé, accélère fortement le jet de plasma primaire dirigé au moyen d'une buse en forme d'anneau (3) à la jonction avec l'environnement et il se forme, en conséquence, après la buse, un plasma secondaire à pression ambiante.
  10. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la surface de substrat (4) subit un nettoyage ou une microstructuration ou une nanostructuration par le jet de plasma secondaire (2) en l'absence d'une alimentation en poudre.
  11. Procédé selon l'une quelconque des revendications 4 à 10, caractérisé en ce que l'on utilise, pour la production du plasma primaire (8), un courant alternatif ou continu à haute fréquence, dont les fréquences se situent dans la plage de 10 kHz à 10 GHz, et une puissance électrique inférieure à 5 kW.
  12. Procédé selon la revendication 1 ou 2, caractérisé en ce que la poudre de fine granulométrie est transférée dans une suspension aqueuse et est acheminée au plasma à l'aide d'au moins une unité de transport.
  13. Utilisation du procédé selon l'une quelconque des revendications 1 à 12 dans le but d'appliquer une couche de zinc sur des points de brasage ou de soudure de pièces métalliques ou de tôles galvanisées.
  14. Utilisation du procédé selon l'une quelconque des revendications 1 à 12 dans le but d'appliquer des soudures avec et sans fondant sur des composants.
  15. Utilisation du procédé selon l'une quelconque des revendications 1 à 12 dans le but d'appliquer des couches de cuivre.
  16. Utilisation du procédé selon l'une quelconque des revendications 1 à 12 en vue d'effectuer une pré-métallisation ou une métallisation dosée de matériaux synthétiques, de papier, de semi-conducteurs ou de composants non conducteurs, notamment pour la fabrication de couches électroconductrices de Zn, Cu ou Ag, sur des tranches de Si.
  17. Utilisation du procédé selon l'une quelconque des revendications 1 à 12 dans le but d'appliquer, sans provoquer de décompositions, des couches de matériaux synthétiques, tels que du polyamide, ou de matériaux synthétiques de hautes performances, tels que le PEEK, en ajoutant ou non des particules inorganiques d'une taille allant du nanomètre à quelques micromètres, sur des matériaux synthétiques, du bois, du papier ou des métaux.
EP04786991A 2003-09-26 2004-09-23 Procede de revetement de la surface d'un substrat avec utilisation d'un jet de plasma Revoked EP1675971B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04786991T PL1675971T3 (pl) 2003-09-26 2004-09-23 Metoda powlekania powierzchni przedmiotów przy użyciu strumienia plazmy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH01639/03A CH696811A5 (de) 2003-09-26 2003-09-26 Verfahren zur Beschichtung einer Substratoberfläche unter Verwendung eines Plasmastrahles.
PCT/EP2004/010675 WO2005031026A1 (fr) 2003-09-26 2004-09-23 Procede de revetement de la surface d'un substrat avec utilisation d'un jet de plasma

Publications (2)

Publication Number Publication Date
EP1675971A1 EP1675971A1 (fr) 2006-07-05
EP1675971B1 true EP1675971B1 (fr) 2010-05-19

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EP04786991A Revoked EP1675971B1 (fr) 2003-09-26 2004-09-23 Procede de revetement de la surface d'un substrat avec utilisation d'un jet de plasma

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EP (1) EP1675971B1 (fr)
JP (1) JP2007521395A (fr)
AT (1) ATE468418T1 (fr)
CH (1) CH696811A5 (fr)
DE (1) DE502004011185D1 (fr)
ES (1) ES2345986T3 (fr)
PL (1) PL1675971T3 (fr)
WO (1) WO2005031026A1 (fr)

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WO2012065704A1 (fr) 2010-11-15 2012-05-24 Michael Dvorak Procédé de réalisation de revêtements à partir de poudres à grains fins
WO2012123530A1 (fr) 2011-03-16 2012-09-20 Reinhausen Plasma Gmbh Revêtement ainsi que procédé et dispositif de revêtement
DE102011052120A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Verwendung speziell belegter, pulverförmiger Beschichtungsmaterialien und Beschichtungsverfahren unter Einsatz derartiger Beschichtungsmaterialien
WO2013014212A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé d'application d'un revêtement sur un substrat, revêtement, et utilisation de particules
WO2013014213A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé de revêtement de substrat et utilisation de matériaux de revêtement pulvérulents avec additifs dans de tels procédés
WO2013014214A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé de revêtement mettant en oeuvre des matériaux de revêtement pulvérulents spéciaux et utilisation de tels matériaux de revêtement
DE102011052119A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Verfahren zur Substratbeschichtung und Verwendung additivversehener, pulverförmiger Beschichtungsmaterialien in derartigen Verfahren
DE202012011217U1 (de) 2012-11-21 2014-02-27 Leoni Bordnetz-Systeme Gmbh Vorrichtung zur Aufteilung eines Stoffstromes in einer Oberflächenbeschichtungsanlage sowie eine solche Beschichtungsanlage
WO2015055486A1 (fr) 2013-10-14 2015-04-23 Plasma Innovations GmbH Procédé de production d'un article façonné revêtu par plasma et composant
EP2959992A1 (fr) 2014-06-26 2015-12-30 Eckart GmbH Procédé de fabrication d'un aérosol contenant des particules

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EP2419231B1 (fr) * 2009-04-17 2021-05-05 Michael Dvorak Procédé de revêtement par poudre ou de fabrication de matériaux composites, de préférence lors de la fabrication de plastiques ou du formage par pulvérisation de métaux
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Cited By (15)

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Publication number Priority date Publication date Assignee Title
WO2012065704A1 (fr) 2010-11-15 2012-05-24 Michael Dvorak Procédé de réalisation de revêtements à partir de poudres à grains fins
WO2012123530A1 (fr) 2011-03-16 2012-09-20 Reinhausen Plasma Gmbh Revêtement ainsi que procédé et dispositif de revêtement
WO2013014211A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Utilisation de matériaux de revêtement pulvérulents à enrobage spécial et procédés de revêtement mettant en oeuvre de tels matériaux 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
DE102011052118A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Verfahren zum Aufbringen einer Beschichtung auf einem Substrat, Beschichtung und Verwendung von Partikeln
WO2013014213A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé de revêtement de substrat et utilisation de matériaux de revêtement pulvérulents avec additifs dans de tels procédés
DE102011052120A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Verwendung speziell belegter, pulverförmiger Beschichtungsmaterialien und Beschichtungsverfahren unter Einsatz derartiger Beschichtungsmaterialien
WO2013014214A2 (fr) 2011-07-25 2013-01-31 Eckart Gmbh Procédé de revêtement mettant en oeuvre des matériaux de revêtement pulvérulents spéciaux et utilisation de tels matériaux de revêtement
DE102011052121A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Beschichtungsverfahren nutzend spezielle pulverförmige Beschichtungsmaterialien und Verwendung derartiger Beschichtungsmaterialien
DE102011052119A1 (de) 2011-07-25 2013-01-31 Eckart Gmbh Verfahren zur Substratbeschichtung und Verwendung additivversehener, pulverförmiger Beschichtungsmaterialien in derartigen Verfahren
US9580787B2 (en) 2011-07-25 2017-02-28 Eckart Gmbh Coating method using special powdered coating materials and use of such coating materials
DE202012011217U1 (de) 2012-11-21 2014-02-27 Leoni Bordnetz-Systeme Gmbh Vorrichtung zur Aufteilung eines Stoffstromes in einer Oberflächenbeschichtungsanlage sowie eine solche Beschichtungsanlage
WO2015055486A1 (fr) 2013-10-14 2015-04-23 Plasma Innovations GmbH Procédé de production d'un article façonné revêtu par plasma et composant
DE102013111306A1 (de) 2013-10-14 2015-04-30 Ensinger Gmbh Herstellungsverfahren für einen plasmabeschichteten Formkörper und Bauteil
EP2959992A1 (fr) 2014-06-26 2015-12-30 Eckart GmbH Procédé de fabrication d'un aérosol contenant des particules

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DE502004011185D1 (de) 2010-07-01
JP2007521395A (ja) 2007-08-02
CH696811A5 (de) 2007-12-14
PL1675971T3 (pl) 2010-10-29
ATE468418T1 (de) 2010-06-15
EP1675971A1 (fr) 2006-07-05
ES2345986T3 (es) 2010-10-07
WO2005031026A1 (fr) 2005-04-07

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