EP1675971A1 - Method for coating a substrate surface using a plasma beam - Google Patents

Method for coating a substrate surface using a plasma beam

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Publication number
EP1675971A1
EP1675971A1 EP04786991A EP04786991A EP1675971A1 EP 1675971 A1 EP1675971 A1 EP 1675971A1 EP 04786991 A EP04786991 A EP 04786991A EP 04786991 A EP04786991 A EP 04786991A EP 1675971 A1 EP1675971 A1 EP 1675971A1
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EP
European Patent Office
Prior art keywords
plasma
powder
fine
nozzle
substrate surface
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EP04786991A
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German (de)
French (fr)
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EP1675971B1 (en
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Michael Dvorak
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Individual
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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.
  • 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 inventive method for applying a zinc layer on welding or soldering of galvanized metal parts or sheets ideally directly after the welding or soldering process in which the Plasmatron is tracked behind the welding process and utilizes the process heat of the previous joining process in order to achieve improved bonding of the zinc layer to the component.
  • 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 schematically a principle of the inventive method.
  • FIG. 1 shows a known plasma nozzle 1 for producing a free plasma jet 2, which emerges from a lower nozzle opening 3 of the plasmatron 1 and is directed onto 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 follows 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 a device known from PCT patent application no. PCT / EP02 / 10709 for supplying metered quantities of a fine-grained bulk material, which has at least two metering chambers which can be filled and emptied alternately, the metering chambers each being connected to a suction chamber. 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.
  • the switching on and off of the suction connection as well as the switching on and off of the compressed gas connection takes place via pneumatically and / or hydraulically controlled valves.
  • 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 powder feed in the area 6 of the plasma rim 1 tapering towards the nozzle opening 3 (or into the nozzle opening 3 itself) via a line 22 indicated by dashed lines in FIG. 1 is also advantageous. Another possibility is to dash the powder over a likewise dashed line indicated line 23 directly through the primary plasma in the flow direction of the plasma jet to the nozzle opening 3 supply.
  • 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 ⁇ l /).
  • 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 with a corresponding width (for example 2 to 3) can be directed through a relative feed substrate / plasma nozzle (eg 0.3 m / s) 8 mm) can be applied exactly.
  • a relative feed substrate / plasma nozzle eg 0.3 m / s 8 mm
  • 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)
  • Plasma Technology (AREA)
  • Other Surface Treatments For Metallic Materials (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)

Abstract

The invention relates to a method for coating a substrate surface (4) using a plasma beam (2), by directing a beam (2) of a low temperature plasma at the substrate surface (4). A fine granular powder, forming the coating is added to the beam (2) in precisely metered amounts. The particle size of the fine powder or the powder mixture is preferably in the nanometre range, in particular, 1 to 10,000 nanometres. The powder can thus be applied with good bonding and with high service life.

Description

Verfahren zur Beschichtung einer Substratoberfläche unter Verwendung eines Plasmastrahles Process for coating a substrate surface using a plasma jet
Die Erfindung betrifft ein Verfahren zur Beschichtung einer Substratoberfläche unter Verwendung eines Plasmastrahles gemäss dem Oberbegriff des Anspruches 1 sowie eine Anwendung des Verfahrens nach Anspruch 12.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.
Es ist bekannt, mittels eines Plasmastrahles hochschmelzende Schichten auf eine Substratoberfläche aufzutragen, indem geeignete Stoffe wie z.B. Wolfram oder Oxidkeramik in Pulverform in einen Plasmafreistrahl zugeführt werden. Es handelt sich dabei um sogenannte thermische Plasmen, bei denen im Kern des austretenden freien Plasmastrahles Temperaturen bis zu 20'000°C herrschen. Die Plasmastabilisierung findet hierbei durch hohe Stromstärken (> 200 A) und einfach zu ionisierende Gase statt. Ein derartiges Plasma bedingt eine hohe Temperaturbelastung des zu beschichtenden Bauteiles. Findet der Beschichtungsvorgang unter Atmosphäre statt, oxidieren ausserdem metallische Beschichtungswerkstoffe teilweise. Daher ist der Verwendungsbereich sehr eingeengt. Die Beschichtung und oder Verarbeitung niedrigschmelzender Werkstoffe ist, wenn überhaupt, nur durch eine äusserst aufwendige Prozessführung und dem Einsatz starker Kühlung möglich.It is known to apply by means of a plasma jet high-melting layers on a substrate surface by suitable substances such as tungsten or oxide ceramics in powder form are fed into a plasma free jet. These are so-called thermal plasmas, in which temperatures 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.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art vorzuschlagen, mittels welchen gut haftende Schichten auf Metall, Glas, Kunststoff oder andere Substratoberflächen aufgetragen werden können.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.
Diese Aufgabe wird er findungs gemäss durch ein Verfahren mit den Merkmalen des Anspruches 1 gelöst.This object is achieved according to the invention by a method having the features of claim 1.
Bevorzugte Weitergestaltungen des erfindungsgemässen Verfahrens bilden den Gegenstand der abhängigen Ansprüche.Preferred refinements of the inventive method form the subject of the dependent claims.
Besonders vorteilhaft ist die Anwendung des erfindungsgemässen Verfahrens zum Aufbringen einer Zinkschicht auf Schweiss- oder Lötstellen von verzinkten Metallteilen oder Blechen, idealerweise direkt nach dem Schweiss- bzw. Lötvorgang in dem das Plasmatron hinter dem Schweiss- verfahren nachgeführt wird und die Prozesswärme des vorherigen Fügevorganges ausnutzt, um eine verbesserte Anbindung der Zinkschicht an das Bauteil zu erreichen. Das vom freien Plasmastrahl auf die Substratoberfläche aufgebrachte Pulver wird auf diese gut haftend aufgetragen, ohne dass die Substrattemperatur unzulässig ansteigt. Dennoch wird durch diesen mikroskopischen Plasmaprozess auch unter Luftatmosphäre eine ausgezeichnete Haftung der aufgetragenen Schicht erreicht. Metallische Schichten zeichnen sich ferner durch Ihren äusserst geringen Sauerstoffgehalt aus.Particularly advantageous is the application of the inventive method for applying a zinc layer on welding or soldering of galvanized metal parts or sheets, ideally directly after the welding or soldering process in which the Plasmatron is tracked behind the welding process and utilizes the process heat of the previous joining process in order to achieve improved bonding of the zinc layer to the component. 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.
Die Erfindung wird nachfolgend anhand der Zeichnung näher erläutert. Es zeigt:The invention will be explained in more detail with reference to the drawing. It shows:
Fig. 1 schematisch ein Prinzip des erfindungsgemässen Verfahrens.Fig. 1 shows schematically a principle of the inventive method.
Fig.1 zeigt eine an sich bekannte Plasmadüse 1 zur Erzeugung eines freien Plasmastrahles 2, der aus einer unteren Düsenöffnung 3 des Plasmatrons 1 austritt und auf eine Substratoberfläche 4 gerichtet ist.1 shows a known plasma nozzle 1 for producing a free plasma jet 2, which emerges from a lower nozzle opening 3 of the plasmatron 1 and is directed onto a substrate surface 4.
Das Plasmatron 1 weist üblicherweise ein langgestrecktes, rohrförmiges Gehäuse 5 auf, das sich im unteren Bereich 6 zu der bereits erwähnten Düsenöffnung 3 konisch verjüngt. Das metallene Gehäuse 5 ist geerdet und bildet mit der Düsenspitze zum Beispiel eine Aussenelektrode. Ein primäres Ungleichgewichts-Plasma mit niedriger elektrischer Leistung (< 5 kW) wird innerhalb des Plasmatrons 5 - mit Box 11 angedeutet - durch hochfrequenten Wechselstrom (> 10 KHz) beispielsweise über ein Magnetron, ein RF-Plasma, eine direkte Hochspannungsentladung, einer Coronabarriereentladung oder ähnlichem erzeugt. In das Plasmatron 1 wird von oben durch eine Zuleitung 7 ein Plasma- bzw. Arbeitsgas so strömungstechnisch eingeleitet, dass dadurch das primäre Plasma stabilisiert wird (gasstabilisiertes Plasmatron und bspw. auch vortexstabilsiertes Plasmatron).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. In the Plasmatron 1, 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).
Als Plasma- bzw. Arbeitsgas wird vorzugsweise Luft oder auch Wasserdampf eingesetzt (kostengünstig). Der Luft können bei Bedarf noch z.B. Stickstoff, Kohlendioxid, Methan oder Edelgase beigemischt werden. Diese anderen Gase können jedoch auch in reiner Form oder in Mischungen verwendet werden. Auch sind Dämpfe anderer Flüssigkeiten in reiner Form oder in Mischungen als Plasmagase zu verwenden.As 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. However, these other gases can also be used in pure form or in mixtures. Also, vapors of other liquids in pure form or in mixtures are to be used as plasma gases.
Der austretende atmosphärische Plasmafreistrahl 2 zeichnet sich insbesondere durch eine niedrige Temperatur (im Kernbereich < 500 °C) und geringer geometrischer Ausdehnung aus (Durchmesser typischerweise < 5 mm). Erfindungsgemäss wird nun dem freien Plasmastrahl 2 als ein fluidi- siertes, feinkörniges Pulver dasjenige Material in genau dosierter Menge zugefügt, das die vorgesehene Beschichtung der Substratoberfläche bilden soll. Dort wird es infolge der Wechselwirkung mit dem Plasma auf- oder auch nur angeschmolzen und in Richtung der zu beschichtenden Oberfläche beschleunigt, wo es sich letztlich niederschlägt. Das Pulvermaterial wird dabei aus einem Behälter 15 mittels eines Pulverförderers 16 geliefert und wahlweise in das sekundäre Plasma oder auch primäre Plasma eingeleitet.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). According to the invention, 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.
Das Niedertemperaturplasma zeichnet sich dadurch aus, dass das nach Ausbildung eines elektrisch oder elektromagnetisch erzeugten primären Ungleichgewichts-Plasmas (Nichtthermisches Plasma) in einem partiell geschlossen Plasmaerzeuger, der durch geeignete Massnahmen gerichtete primäre Plasmastrahl mittels einer ringförmigen Düse am Übergang zur Umgebung (Austrittsöffnung 3) stark beschleunigt wird und sich folgedes- sen nach der Düse ein sekundäres Plasma bei Umgebungsdruck ausbildet. Ist die Substratoberfläche elektrisch leitend, kann zudem eine weitere Spannung (sogenannter übertragener Lichbogen oder auch direktes Plasmatron) zwischen Düse und dem Substrat angelegt werden. Die Temperatur des Plasmas gemessen mit einem Thermoelement Typ NiCr/Ni, Spitzendurchmesser 4 mm, in 10 mm Abstand vom Düsenaustritt beträgt weniger als 900°C im Kern des sekundären Plasmastrahles (2) bei Umgebungsdruck.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 follows 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.
Als Pulverförderer 16 wird vorzugsweise eine aus der PCT- Patentanmeldung Nr. PCT/EP02/10709 bekannte Vorrichtung zur Zuführung dosierter Mengen eines feinkörnigen Schüttgutes verwendet, die mindestens zwei wechselweise füll- und entleerbare Dosierkammern aufweist, wobei die Dosierkammern jeweils durch Anschluss an eine Saug- bzw. Vakuumleitung mit dem Pulver gefüllt und durch Anschluss an eine Druckgasleitung entleert und dabei das Pulver vom Druckgas fluidisiert und pneumatisch weitergefördert wird.A powder conveyor 16 is preferably a device known from PCT patent application no. PCT / EP02 / 10709 for supplying metered quantities of a fine-grained bulk material, which has at least two metering chambers which can be filled and emptied alternately, the metering chambers each being connected to a suction chamber. 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.
Das Einschalten und Ausschalten des Sauganschlusses sowie das Einschalten und Ausschalten des Druckgasanschlusses erfolgt über pneumatisch und/oder hydraulisch gesteuerte Ventile. Eine solche Vorrichtung als Pulverförderer 16 erlaubt eine höchst präzise Dosierung und sowohl eine gepulste als auch eine kontinuierliche, agglomerationsfreie Zuführung des feinsten Pulvers, dessen Korngrösse im Nanometerbereich bis Mikrometerbereich (1 nm bis 100 μm) liegt. Die möglichen Ausgestaltungen eines derartigen Pulverförderers zur elektronisch steuerbaren Förderung sind der vorstehend genannten Patentanmeldung zu entnehmen und werden daher hier im Detail nicht näher beschrieben. Das fluidisierte, feinkörnige Pulver wird über eine Leitung 20 in das Plasmatron 1 und dort in das sekundäre Plasma eingeführt und/oder über eine Leitung 21 direkt in den aus der Düsenöffnung 3 austretenden Plasmastrahl 2 eingeleitet. Von Vorteil ist auch eine Pulverzuführung in den sich zur Düsenöffnung 3 hin verjüngenden Bereich 6 des Plasmatrons 1 (oder in die Düsenöffnung 3 selber) über eine in Fig. 1 gestrichelt angedeutete Leitung 22. Eine weitere Möglichkeit besteht darin, das Pulver über eine ebenfalls gestrichelt angedeutete Leitung 23 direkt durch das primäre Plasma hindurch in Strömungsrichtung des Plasmastrahles bis zu der Düsenöffnung 3 zuzuführen.The switching on and off of the suction connection as well as the switching on and off of the compressed gas connection takes place via pneumatically and / or hydraulically controlled valves. 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 powder feed in the area 6 of the plasma rim 1 tapering towards the nozzle opening 3 (or into the nozzle opening 3 itself) via a line 22 indicated by dashed lines in FIG. 1 is also advantageous. Another possibility is to dash the powder over a likewise dashed line indicated line 23 directly through the primary plasma in the flow direction of the plasma jet to the nozzle opening 3 supply.
Die Menge des für die pneumatische Förderung des Pulvermaterials benötigten Druckgases beträgt vorzugsweise 2 bis 20% der Plasmagasmenge. Der Plasmagasverbrauch liegt etwa bei 100 bis 5000 ήl/ ).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 ήl /).
Das vom Plasmafreistrahl 2 auf die Substratoberfläche 4 aufgebrachte Pulver wird auf diese gut haftend aufgetragen, ohne dass die Substrattemperatur unzulässig ansteigt. Die Temperatur des Plasmas gemessen mit einem Thermoelement Typ NiCr/Ni, Spitzendurchmesser 3 mm, in 10 mm Abstand vom Düsenaustritt beträgt weniger als 900° C im Kern des sekundären Plasmafreistrahles bei Umgebungsdruck. Die Substrattemperaturerhöhung liegt während und nach dem Beschichtungsprozess deutlich unterhalb 100°C, vorzugsweise unter 50°C. Dennoch wird durch diesen mikroskopischen atmosphärischen Plasmaprozess eine ausgezeichnete Haftung der aufgetragenen Schicht erreicht.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.
Ein Vorteil des erfindungsgemässen Verfahrens besteht darin, dass die zu beschichtende Substratoberfläche 4 keiner speziellen Vorbereitung bedarf. Eine Oberflächenreinigung kann durch den Plasmaprozess selber durchgeführt werden. Mit Vorteil wird zu diesem Zweck anfänglich ein- oder mehrmals der Plasmastrahl ohne Pulverzusatz auf die zu beschichtende Fläche gerichtet, bevor die eigentliche Beschichtung erfolgt. Dieser Vorgang dient vor allem zur Temperierung der Oberfläche und zu deren Mik- ro- bzw. Nanostrukturierung.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. Advantageously, for this purpose 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.
Das erfindungsgemässe Verfahren eignet sich ausgezeichnet beispielsweise zum Aufbringen einer Zinkschicht auf Schweiss- oder Lötstellen von verzinkten Metallteilen oder Blechen, die insbesondere in der Autoindustrie verwendet werden. Bekanntlich wird die Zinkschicht der konventionell verzinkten Metallteile oder Bleche beim Schweissen oder Löten entfernt, wodurch eine Korrosionsgefahr an solchen Stellen besteht. Mit dem erfindungsgemässen Verfahren kann ein Plasmastrahl mit genau definierter Breite auf die zu behandelnde Stelle, beispielsweise eine Schweissnaht, gerichtet werden und durch einen relativen Vorschub Substrat/Plasmadüse (z.B. 0,3 m/s) eine Zinkschicht mit einer entsprechenden Breite (z.B. 2 bis 8 mm) exakt aufgetragen werden. Als das feinkörnige, dem Plasmastrahl zugefügte Pulvermaterial wird kommerziell erhältlicher Zinkstaub verwendet. Die Pulverzufuhr liegt im Bereich von ca. 0,5 bis 10 g/min. Die erzielbaren Schichtdicken betragen typischerweise 0,1 bis 100 Mikrometer pro Überlauf. Die Vorrichtung kann direkt dem Schweissprozess nachlaufend angewendet werden (In-Line Prozess).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. With the method according to the invention, 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 with a corresponding width (for example 2 to 3) can be directed through a relative feed substrate / plasma nozzle (eg 0.3 m / s) 8 mm) can be applied exactly. As the fine-grained powder material added to the plasma jet, commercially available zinc dust is used. 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).
Selbstverständlich können auch andere Materialien (Metalle, Keramiken, Thermoplaste oder auch deren Mischungen etc.) auf andere Substratflächen (Metall, Glas, Kunststoff etc.) mit dem erfindungsgemässen Verfahren aufgetragen werden und Funktionsschichten wie beispielsweise Schutz-, Verschleiss-, Isolierschichten oder auch Schichten mit antibakte- riellen, selbstreinigenden oder auch katalytischen Eigenschaften bilden. Das Verfahren kann aber auch zu medizinischen Zwecken genutzt werden und beispielsweise zum Aufbringen von biologisch aktiven Schichten auf Hautersatz oder Knochenimplantaten dienen, mit Ziel einer schnelleren und verbesserten Integration des Implantates in das menschliche Gewebe.Of course, other materials (metals, ceramics, thermoplastics or their mixtures, etc.) can be applied to other substrate surfaces (metal, glass, plastic, etc.) with the inventive method and functional layers such as protective, wear, insulating layers or layers with antibacterial rial, self-cleaning or catalytic properties. However, 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.
Das Verfahren kann auch zum dosierten bzw. schonenden und gezielten Vormetallisieren oder Metallisieren von Kunststoffen, Papier, Halbleitern oder Nichtleitern, beispielsweise zur Herstellung elektrisch leitfähiger Schichten aus Zn, Cu oder Ag auf Si-Wafern, angewendet werden.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.
Des Weiteren kann das Verfahren angewendet werden zur zersetzungsfreien Aufbringung von gut haftenden Schichten aus Kunststoffen, wie Polyamid, oder Hochleistungs-Kunststoffen, wie PEEK ohne oder mit Zusätzen von anorganischen nanometer- bis einige mikrometergrosse Partikel auf Kunststoffe, Holz, Papier oder Metalle.Furthermore, 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.
Wird das in den Plasmastrahl eingegebene Pulver oder Pulvergemisch nachfolgend nicht auf eine Oberfläche als Schicht aufgetragen, sondern über eine geeignete Vorrichtung gefangen, ergeben sich Pulver mit gezielt chemisch und oder physikalisch veränderter Oberfläche. Diese Pulver können dann als verbessertes oder neues Vorprodukt für andere Prozesse dienen (bspw. Änderung des hydrophoben Verhaltens von Russ in ein hydrophiles Verhalten). If the powder or powder mixture introduced into the plasma jet is subsequently not applied to a surface as a layer but trapped by means of a suitable device, 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).

Claims

PATENTANSPRÜCHE
1. Verfahren zur Beschichtung einer Substratoberfläche (4) unter Verwendung eines Plasmastrahles (2), dadurch gekennzeichnet, dass auf die Substratoberfläche (4) ein Strahl (2) eines Niedertemperaturplasmas gerichtet wird, dem ein feinkörniges, die Beschichtung bildendes Pulver in genau dosierter Menge zugefügt wird.1. A method for coating a substrate surface (4) using a plasma jet (2), characterized in that on the substrate surface (4) a jet (2) of a low-temperature plasma is directed to a fine-grained, the coating forming powder in exactly metered amount is added.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Korngrösse des feinkörnigen Pulvers oder der Pulvergemische im Nanometerbereich, insbesondere zwischen 1 Nanometer bis 100 Mikrometer liegen kann. 2. The method according to claim 1, characterized in that the grain size of the fine-grained powder or powder mixtures in the nanometer range, in particular between 1 nanometer to 100 micrometers can be.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das feinkörnige Pulver aus einem Behälter (15) mittels eines mindestens zwei wechselweise füll- und entleerbare Dosierkammern aufweisenden Pulverförderers (16) geliefert wird, wobei die Dosierkammern jeweils durch Anschluss an eine Saug- bzw. Vakuumleitung mit dem Pulver gefüllt und durch Anschluss an eine Druckgasleitung entleert und dabei das Pulver vom Druckgas fluidisiert und pneumatisch weitergefördert wird, wobei das Einschalten und Ausschalten des Sauganschlusses sowie des Druckgasanschlusses über pneumatisch und/oder hydraulisch gesteuerte Ventile erfolgt.3. The method according to claim 1 or 2, characterized in that the fine-grained powder from a container (15) by means of at least two alternately fillable and emptying metering chambers having powder conveyor (16) is supplied, wherein the metering chambers in each case 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 compressed gas and pneumatically conveyed on, the switching on and off of the suction port and the compressed gas connection via pneumatically and / or hydraulically controlled valves.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Plasma in einer Plasmadüse (1) unter Zuführung eines Arbeitsgases und/oder einer verdampfbaren Flüssigkeit und Erzeugung einer Entladung die durch Hochspannung oder hochfrequenter elektrischer und/oder elektromagnetischer Einkopplung entsteht und der primäre Plasmastrahl (2) durch eine als Düse ausgeformte Öffnung (3) des Plasmatrons (1) zu der Substratoberfläche (4) ausgeblasen wird, wobei das feinkörnige Pulver in das primäre Plasma beispielsweise über das Arbeitsgas eingeleitet und von dort in den sekundären Plasmastrahl (2) gelangt und/oder direkt in den aus der Düsenöffnung (3) austretenden sekundären Plasmastrahl (2) eingeleitet wird.4. The method according to any one of claims 1 to 3, characterized in that the plasma in a plasma nozzle (1) under supply of a working gas and / or an evaporable liquid and generating a discharge caused by high voltage or high frequency electrical and / or electromagnetic coupling and the primary plasma jet (2) is blown out to the substrate surface (4) through an opening (3) of the plasmatron (1) formed as a nozzle, the fine-grained powder being introduced into the primary plasma, for example via the working gas, and from there into the secondary plasma jet ( 2) and / or is introduced directly into the secondary plasma jet (2) emerging from the nozzle opening (3).
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass das feinkörnige Pulver in einen sich zur Düsenöffnung (3) hin verjüngenden Bereich (6) der Plasmadüse (1) eingeleitet wird. 5. The method according to claim 4, characterized in that the fine-grained powder in a to the nozzle opening (3) towards tapered region (6) of the plasma nozzle (1) is introduced.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass das feinkörnige Pulver direkt (23) in das primäre Plasma eingegeben wird.6. The method according to claim 4, characterized in that the fine-grained powder is input directly (23) into the primary plasma.
7. Verfahren nach einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, dass die Druckgasmenge zur pneumatischen Förderung (20) des feinkörnigen Pulvers 2 bis 20% der Plasmagasmenge (7) beträgt.7. The method according to any one of claims 3 to 6, characterized in that the amount of compressed gas for pneumatic conveying (20) of the fine-grained powder is 2 to 20% of the plasma gas quantity (7).
8. Verfahren nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass als Arbeits- bzw. Plasmagas Luft verwendet wird.8. The method according to any one of claims 4 to 7, characterized in that air is used as working or plasma gas.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Niedertemperaturplasma nach Ausbildung eines elektrisch oder elektromagnetisch erzeugten primären Ungleichgewichts-Plasmas in einem partiell geschlossen Plasmaerzeuger, der durch geeignete Massnah- men gerichtete primäre Plasmastrahl mittels einer ringförmigen Düse (3) am Übergang zur Umgebung stark beschleunigt wird und sich folgedessen nach der Düse ein sekundäres Plasma bei Umgebungsdruck ausbildet.9. The method according to any one of claims 1 to 8, characterized in that the low-temperature plasma after formation of an electrically or electromagnetically generated primary imbalance plasma in a partially closed plasma generator, the measures directed by suitable measures primary plasma jet by means of an annular nozzle (3) is greatly accelerated at the transition to the environment and consequently forms after the nozzle, a secondary plasma at ambient pressure.
10. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Substratoberfläche (4) durch den sekundären Plasmastrahl (2) ohne Pulverzufuhr gereinigt und/oder Mikro- bzw. Nanostrukturiert wird.10. The method according to any one of claims 1 to 8, characterized in that the substrate surface (4) by the secondary plasma jet (2) cleaned without powder feed and / or micro- or nanostructured.
11. Verfahren nach einem der Ansprüche 4 bis 10, dadurch gekennzeichnet, dass zur Erzeugung des primären Plasmas (8) ein hochfrequenter Wechsel- oder Gleichstrom mit Frequenzen von 10 kHz bis 10GHz und einer elektrischen Leistung von weniger als 5 kW verwendet werden. 11. The method according to any one of claims 4 to 10, characterized in that for the production of the primary plasma (8) a high-frequency AC or DC with frequencies of 10 kHz to 10 GHz and an electrical power of less than 5 kW are used.
12. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das feinkörnige Pulver in eine wässrige Suspension überführt und mit Hilfe wenigstens einer Fördereinheit dem Plasma zugefügt wird.12. The method according to claim 1 or 2, characterized in that the fine-grained powder is transferred into an aqueous suspension and added by means of at least one delivery unit to the plasma.
13. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 12 zum Aufbringen einer Zinkschicht auf Schweiss- oder Lötstellen von verzinkten Metallteilen oder Blechen.13. Application of the method according to any one of claims 1 to 12 for applying a zinc layer on welding or soldering of galvanized metal parts or sheets.
14. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 12 zum Aufbringen von Loten mit und ohne Flussmittel auf Bauteile.14. Application of the method according to one of claims 1 to 12 for applying solders with and without flux to components.
15. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 12 zum Aufbringen von hochwertigen, sauerstoffarmen Kupferschichten.15. Application of the method according to one of claims 1 to 12 for the application of high-quality, oxygen-poor copper layers.
16. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 12 zum dosierten Vormetallisieren oder Metallisieren von Kunststoffen, Papier, Halbleitern oder Nichtleitern, beispielsweise zur Herstellung elektrisch leitfähiger Schichten aus Zn, Cu oder Ag auf Si-Wafern.16. Application of the method according to one of claims 1 to 12 for the metered pre-metallizing or metallizing of plastics, paper, semiconductors or non-conductors, for example for the production of electrically conductive layers of Zn, Cu or Ag on Si wafers.
17. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 12 zur zersetzungsfreien Aufbringung von gut haftenden Schichten aus Kunststoffen, wie Polyamid, oder Hochleistungs-Kunststoffen, wie PEEK ohne oder mit Zusätzen von anorganischen nanometer- bis einige mikrometergrosse Partikel auf Kunststoffe, Holz, Papier oder Metalle. 17. Application of the method according to one of claims 1 to 12 for the decomposition-free application of well-adherent layers of plastics, such as polyamide, or high performance plastics, such as PEEK without or with additions of inorganic nanometer to some micrometer-sized particles on plastics, wood, paper or metals.
EP04786991A 2003-09-26 2004-09-23 Method for coating a substrate surface using a plasma beam Revoked EP1675971B1 (en)

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ATE468418T1 (en) 2010-06-15
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CH696811A5 (en) 2007-12-14
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DE502004011185D1 (en) 2010-07-01

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