EP1048751A1 - Method for adhering a hard coating to a substrate and coated substrate - Google Patents

Method for adhering a hard coating to a substrate and coated substrate Download PDF

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Publication number
EP1048751A1
EP1048751A1 EP00810336A EP00810336A EP1048751A1 EP 1048751 A1 EP1048751 A1 EP 1048751A1 EP 00810336 A EP00810336 A EP 00810336A EP 00810336 A EP00810336 A EP 00810336A EP 1048751 A1 EP1048751 A1 EP 1048751A1
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EP
European Patent Office
Prior art keywords
layer
titanium dioxide
aluminum oxide
aluminum
coating
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EP00810336A
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German (de)
French (fr)
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EP1048751B1 (en
Inventor
Stefan Horst
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Hort Coating Center SA
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Hort Coating Center SA
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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof

Definitions

  • the invention relates to a method according to the preamble of patent claim 1 and a coated object according to the preamble of claim 6.
  • the object of the invention is to produce an object essentially made of aluminum or to provide or create an aluminum alloy with a coating, wherein the coating is preferably hard and the good thermal conductivity of the article supported, so that this is preferred as a heater (iron, ...), kitchen appliance for roasting, baking, etc., as well as on other occasions where one uniform heating over the largest possible surface area desired or is required.
  • the above object is achieved in that for a coating appropriately pretreated surface one in particular essentially Aluminum or an aluminum alloy existing object a coating is applied, in which diamonds are embedded.
  • the diamonds in particular care due to their extremely good thermal conductivity for a good heat transfer from one Good lying on the coating to the object, which is also a good heat conductor. This ensures uniform heating of the goods.
  • This coating is preferably used to support the mechanical Hardness of the embedded diamonds as a hard layer consisting essentially of an aluminum oxide / titanium dioxide mixed layer apply.
  • Aluminum oxide as well as titanium dioxide in nature Known as sapphire or rutile, they are very hard. This great hardness is in the Aluminum oxide / titanium dioxide mixture then through the embedded diamond crystals enlarged.
  • Diamond not only has the highest known hardness, but also that best (largest) known thermal conductivity.
  • the hard aluminum oxide / titanium dioxide mixed layer as a so-called binder for the even harder diamond crystals a very hard coating, which has a very good thermal conductivity.
  • the object to be coated from a good heat-conducting material namely in essential (negligible impurities are always present) aluminum or an aluminum alloy
  • a coated object can anywhere wherever possible, the most uniform temperature possible over a large area.
  • the layer containing diamonds is reduced compared to known layers, which also have an anti-adhesive effect, the "thermal barrier" resulting from this layer is essential.
  • the invention is therefore preferred as a kitchen appliance (e.g. frying pan, ...) and in the Medical technology and aviation can be used.
  • the hard layer can be provided with non-stick layers, which further improves its use as a non-stick pan.
  • Non-stick coatings usually have a dark color. If a hard layer with 80 to 40 percent by weight of aluminum oxide (Al 2 O 3 ) and 20 to 60 percent by weight of titanium dioxide (TiO 2 ), preferably with about 60% of aluminum oxide and 40% of titanium dioxide, is applied, it is dark. A slight injury to a non-stick layer made of PTFE (polytetrafluoroethylene) applied over the hard layer is therefore no longer visible.
  • PTFE polytetrafluoroethylene
  • the hard layer can be covered by a fluorosilane layer, in which diamond crystals are also preferably incorporated, in their hardness behavior and in their flat thermal conductivity and their non-stick behavior can still be improved.
  • This layer can then additionally be pigmented, in particular darkly pigmented which also causes minor injuries to the non-stick coating which do not disturb their non-stick effect, are hardly visible anymore.
  • the coating 1 shown in the single figure is applied as an object to a pan base 3 made of aluminum.
  • the surface 5 of the pan base 3 is pretreated for the subsequent coating.
  • the surface 5 is degreased and sandblasted with corundum powder.
  • the corundum powder has fine grains to which coarse grains are mixed.
  • the coarse grains produce a roughness of approximately one hundred to two hundred micrometers on the surface 5 to be coated. This roughly roughened surface structure is overlaid with a finer roughness by fine grains of about ten to thirty micrometers.
  • the whole object (pan) is brought to a temperature below 600 ° C in an oven.
  • a temperature of 450 ° C. is preferably selected.
  • a mixture with 80 to 40 percent by weight of aluminum oxide (Al 2 O 3 ) and 20 to 60 percent by weight of titanium dioxide (TiO 2 ) is applied.
  • Al 2 O 3 aluminum oxide
  • TiO 2 titanium dioxide
  • about sixty percent by weight of aluminum oxide and forty percent by weight of titanium dioxide with an admixture of five to ten percent by weight of aluminum fluoride (AlF 3 ) are applied as a homogeneous mixture in a plasma spraying process as a thermal spraying process.
  • AlF 3 aluminum fluoride
  • aluminum fluoride is not mandatory; other non-stick materials can also be used. However, it is important to ensure compatibility with the aluminum oxide-titanium dioxide mixture.
  • the material used must also remain under the thermal conditions of plasma spraying. In plasma spraying, diamond crystals are added, which have a diameter between 0.5 ⁇ m and 10 pm.
  • the aluminum oxide-titanium dioxide-aluminum fluoride mixture with embedded diamond crystals is sprayed onto the surface 5 as a hard layer 7 up to a layer thickness of 50 ⁇ m to 150 ⁇ m. The applied hard layer 7 appears black.
  • the diamond crystals must be mixed in such a way that they have no temperature exposed to temperatures above 900 ° C. At 900 ° C, diamond can transform into graphite or burn when exposed to oxygen. Of these 900 ° C should a sufficient temperature distance should be kept.
  • the aluminum oxide as a relatively inexpensive material, gives the layer 7 the necessary hardness, while titanium dioxide gives this layer 7 the ductility and the dark or black color. Due to the ductility of the titanium dioxide, the coating is resistant to large temperature fluctuations, such as occur in frying pans.
  • a further layer 9 made of fluorosilane, likewise with embedded diamond crystals with a diameter of 0.5 ⁇ m to 10 ⁇ m, can be applied to the hard layer 7 as a suspension.
  • a pigment is preferably added to the suspension, with which the shade of the hard layer 7 is adjusted.
  • the article is then heated in an oven in several stages (100 ° C, 250 ° C, 400 ° C) to 400 ° C to 430 ° C and held at the final temperature for about ten to fifteen minutes. It is not essential to apply this layer 9 .
  • the non-stick effect of the coating is also given without this layer 9 ; however, it is still improved by this.
  • a carbon black pigment is used as the pigment.
  • PTFE polytetrafluoroethylene
  • the coating 1 described here is very well non-stick to food to be heated (roasted) lying on it and also resistant to scratching with good "heat distribution" over the pan bottom. Should the top PTFE layer 11 nevertheless be scratched, this scratching is not visible due to the color adaptation of the layer 9 to the color of the hard layer 7 . The anti-adhesive property is hardly affected by this, since the layer 9 is also “anti-adhesive”.
  • surfaces of irons, pots, surfaces of machine parts such as bearing shells, ... can be coated with the coating 1 described above.
  • the diamonds can also be deposited using a reactive coating process in the presence of methane.
  • this method is currently more expensive than directly inserting the diamond crystals.
  • Group IVb includes titanium (Ti), zircon (Zr) and hafnium (Hf).
  • Group Vb includes vanadium (V), niobium (Nb) and tantalum (Ta).
  • the Vlb group includes chromium (Cr), molybdenum (Mo) and tungsten (W).
  • the mixture described above has proven to be particularly advantageous.
  • the layer 9 can also be applied and, after it has dried, the layer 11 immediately, both of which, as described above, then gradually or gradually increasing be heated.
  • a PFA layer (P he f luor a lcyd) and a FEP-layer (F luor e Thylen p ropylene) as well as allied materials are used instead of a layer of PTFE.
  • a hard layer on the object with embedded diamond crystals it is also possible to use another, for example Teflon-like, layer with embedded diamond crystals, which is not necessarily to be referred to as a hard layer.
  • the item out of aluminum or an aluminum alloy it can also be made of stainless steel or iron.
  • Aluminum or however, its alloys have the advantage of good thermal conductivity. Objects too copper can be coated accordingly; however, it is here make sure that no oxidation of the copper surface occurs.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Cookers (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Frying-Pans Or Fryers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The surface (5) of the object (3) is pretreated, to receive the coating (1) containing distributed diamond crystals. An Independent claim is included for the high thermal conductivity-, especially aluminum, object so coated.

Description

Technisches GebietTechnical field

Die Erfindung betrifft ein Verfahren gemäß dem Oberbegriff des Patentanspruchs 1 sowie einen beschichteten Gegenstand gemäß dem Oberbegriff des Patentanspruchs 6.The invention relates to a method according to the preamble of patent claim 1 and a coated object according to the preamble of claim 6.

Aufgabe der ErfindungObject of the invention

Aufgabe der Erfindung ist es, einen Gegenstand im wesentlichen aus Aluminium oder einer Aluminiumlegierung mit einer Beschichtung zu versehen bzw. zu schaffen, wobei die Beschichtung vorzugsweise hart ist und die gute Wärmeleitfähigkeit des Gegenstands unterstützt, damit dieser bevorzugt als Heizgerät (Bügeleisen,...), Küchengerät zum Braten, Backen etc. sowie bei anderen Gelegenheiten verwendbar ist, bei denen eine gleichmäßige Erwärmung über einen möglichst großen Flächenbereich gewünscht bzw. gefordert ist. The object of the invention is to produce an object essentially made of aluminum or to provide or create an aluminum alloy with a coating, wherein the coating is preferably hard and the good thermal conductivity of the article supported, so that this is preferred as a heater (iron, ...), kitchen appliance for roasting, baking, etc., as well as on other occasions where one uniform heating over the largest possible surface area desired or is required.

Lösung der AufgabeSolution of the task

Die obengenannte Aufgabe wird dadurch gelöst, dass auf die für eine Beschichtung entsprechend vorbehandelte Oberfläche eines insbesondere im wesentlichen aus Aluminium oder einer Aluminiumlegierung bestehenden Gegenstands eine Beschichtung aufgebracht wird, in die Diamanten eingelagert sind. Die Diamanten sorgen insbesondere aufgrund ihrer äußerst guten Wärmeleitfähigkeit für einen guten Wärmeübergang von einem auf der Beschichtung liegenden Gut zum ebenfalls gut wärmeleitenden Gegenstand. Hierdurch wird eine gleichmäßige Erwärmung des Gutes erreicht.The above object is achieved in that for a coating appropriately pretreated surface one in particular essentially Aluminum or an aluminum alloy existing object a coating is applied, in which diamonds are embedded. The diamonds in particular care due to their extremely good thermal conductivity for a good heat transfer from one Good lying on the coating to the object, which is also a good heat conductor. This ensures uniform heating of the goods.

Vorzugsweise wird man diese Beschichtung zur Unterstützung der mechanischen Härte der eingelagerten Diamanten als eine Hartschicht im wesentlichen aus Aluminiumoxid/Titandioxid-Mischschicht aufbringen. Aluminiumoxid sowie Titandioxid, in der Natur als Saphir bzw. Rutil bekannt, haben eine sehr große Härte. Diese große Härte wird in der Aluminiumoxid/Titandioxid-Mischschicht dann noch durch die eingelagerte Diamantkristalle vergrößert. Diamant hat nicht nur die höchste bekannte Härte, sondern auch die beste (größte) bekannte Wärmeleitfähigkeit. Die harte Aluminiumoxid/Titandioxid-Mischschicht als sogenanntes Bindemittel für die noch härteren Diamantkristalle ergibt somit eine sehr harte Beschichtung, welche eine sehr gute Wärmeleitfähigkeit besitzt. Da auch der zu beschichtende Gegenstand aus einem gut wärmeleitenden Material, nämlich im wesentlichen (zu vernachlässigende Verunreinigungen sind immer vorhanden) Aluminium bzw. einer Aluminiumlegierung besteht, kann ein derart beschichteter Gegenstand überall dort eingesetzt werden, wo es darauf ankommt, eine möglichst gleichmäßige Temperatur über einen großen Flächenbereich zu erhalten. Die Diamanten enthaltende Schicht reduziert gegenüber bekannten Schichten, welche ebenfalls eine antihaftende Wirkung zeigen, die durch diese Schicht sich ergebende "Thermobarriere" wesentlich. Der erfindungsgemäße Gegenstand ist somit bevorzugt als Küchengerät (z.B. Bratpfanne, ...) sowie in der Medizintechnik und der Luftfahrt einsetzbar.This coating is preferably used to support the mechanical Hardness of the embedded diamonds as a hard layer consisting essentially of an aluminum oxide / titanium dioxide mixed layer apply. Aluminum oxide as well as titanium dioxide, in nature Known as sapphire or rutile, they are very hard. This great hardness is in the Aluminum oxide / titanium dioxide mixture then through the embedded diamond crystals enlarged. Diamond not only has the highest known hardness, but also that best (largest) known thermal conductivity. The hard aluminum oxide / titanium dioxide mixed layer as a so-called binder for the even harder diamond crystals a very hard coating, which has a very good thermal conductivity. There too the object to be coated from a good heat-conducting material, namely in essential (negligible impurities are always present) aluminum or an aluminum alloy, such a coated object can anywhere wherever possible, the most uniform temperature possible over a large area. The layer containing diamonds is reduced compared to known layers, which also have an anti-adhesive effect, the "thermal barrier" resulting from this layer is essential. The invention The object is therefore preferred as a kitchen appliance (e.g. frying pan, ...) and in the Medical technology and aviation can be used.

Wie nachfolgend ausgeführt, lässt sich die Hartschicht mit Antihaftschichten versehen, was deren Einsatz als nicht "anklebende" Pfanne noch verbessert. Antihaftbeschichtungen haben in der Regel eine dunkle Färbung. Wird nun eine Hartschicht mit 80 bis 40 Gewichtsprozent Aluminiumoxid (Al2O3) und 20 bis 60 Gewichtsprozent Titandioxid (TiO2), bevorzugt mit etwa 60 % Aluminiumoxid und 40 % Titandioxid aufgebracht, so ist diese dunkel. Eine leichte Verletzung einer über der Hartschicht aufgebrachten Antihaftschicht aus PTFE (Polytetrafluorethylen) ist somit nicht mehr sichtbar. As explained below, the hard layer can be provided with non-stick layers, which further improves its use as a non-stick pan. Non-stick coatings usually have a dark color. If a hard layer with 80 to 40 percent by weight of aluminum oxide (Al 2 O 3 ) and 20 to 60 percent by weight of titanium dioxide (TiO 2 ), preferably with about 60% of aluminum oxide and 40% of titanium dioxide, is applied, it is dark. A slight injury to a non-stick layer made of PTFE (polytetrafluoroethylene) applied over the hard layer is therefore no longer visible.

Die Hartschicht kann durch eine über ihr angeordnete Fluorsilanschicht, in welcher bevorzugt ebenfalls Diamantkristalle eingelagert werden, in ihrem Härteverhalten sowie in ihrer flächigen Wärmeleitfähigkeit und ihrem Antihaftverhalten noch verbessert werden. Diese Schicht kann dann zusätzlich noch pigmentiert, insbesondere dunkel pigmentiert werden, wodurch ebenfalls kleine Verletzungen der darüber liegenden Antihaftbeschichtung, welche deren Antihaftwirkung nicht stören, kaum mehr sichtbar sind.The hard layer can be covered by a fluorosilane layer, in which diamond crystals are also preferably incorporated, in their hardness behavior and in their flat thermal conductivity and their non-stick behavior can still be improved. This layer can then additionally be pigmented, in particular darkly pigmented which also causes minor injuries to the non-stick coating which do not disturb their non-stick effect, are hardly visible anymore.

Kurze Beschreibung der ZeichnungenBrief description of the drawings

Anschließend werden Beispiele des erfindungsgemäßen Verfahrens sowie des erfindungsgemäßen Gegenstands an Hand einer einzigen Figur erläutert.Subsequently, examples of the method according to the invention and of the invention Item explained using a single figure.

Wege zur Ausführung der ErfindungWays of Carrying Out the Invention

Die in der einzigen Figur dargestellte beispielsweise Beschichtung 1 ist auf einem Pfannenboden 3 aus Aluminium als Gegenstand aufgebracht. Die Oberfläche 5 des Pfannenbodens 3 ist für die nachfolgende Beschichtung vorbehandelt. Hierzu wird die Oberfläche 5 entfettet und mit Korundpulver sandgestrahlt. Das Korundpulver hat feine Körner, denen grobe Körner beigemischt sind. Die groben Körner erzeugen auf der zu beschichtenden Oberfläche 5 eine Rauhigkeit von etwa einhundert bis zweihundert Mikrometer. Dieser grob aufgerauhten Oberflächenstruktur wird eine feinere Rauhigkeit durch feine Körner von etwa zehn bis dreißig Mikrometern überlagert.The coating 1 shown in the single figure , for example, is applied as an object to a pan base 3 made of aluminum. The surface 5 of the pan base 3 is pretreated for the subsequent coating. For this purpose, the surface 5 is degreased and sandblasted with corundum powder. The corundum powder has fine grains to which coarse grains are mixed. The coarse grains produce a roughness of approximately one hundred to two hundred micrometers on the surface 5 to be coated. This roughly roughened surface structure is overlaid with a finer roughness by fine grains of about ten to thirty micrometers.

Nach dem Aufrauhen wird der ganze Gegenstand (Pfanne) in einem Ofen auf eine Temperatur unter 600°C gebracht. Vorzugsweise wird eine Temperatur von 450°C gewählt. Unmittelbar nach Erreichen dieser Temperatur wird ein Gemisch mit 80 bis 40 Gewichtsprozent Aluminiumoxid (Al2O3) und 20 bis 60 Gewichtsprozent Titandioxid (TiO2) aufgebracht. Es werden hier beispielsweise etwa sechzig Gewichtsprozent Aluminiumoxid und vierzig Gewichtsprozent Titandioxid mit einer Beimischung von fünf bis zehn Gewichtsprozent Aluminium-Fluorid (AlF3) als homogenes Gemisch in einem Plasmasprühverfahren als thermisches Sprühverfahren aufgebracht. Das beigemischte Aluminium-Fluorid erzeugt eine antihaftende Wirkung in der Hartschicht 7. Die Verwendung von Aluminium-Fluorid ist nicht zwingend; es können auch andere Materialien mit antihaftender Wirkung verwendet werden. Es ist jedoch auf eine Verträglichkeit mit dem Aluminiumoxid-Titandioxid-Gemisch zu achten. Auch muss das verwendete Material unter den thermischen Bedingungen des Plasmasprühens bestehen bleiben. Beim Plasmasprühen werden Diamantkristalle beigemischt, welche einen Durchmesser zwischen 0,5 µm und 10 pm haben. Das Aluminiumoxid-Titandioxid-Aluminiumfluorid-Gemisch mit eingelagerten Diamantkristallen wird als Hartschicht 7 bis zu einer Schichtdicke von 50 µm bis 150 µm auf die Oberfläche 5 aufgesprüht. Die aufgebrachte Hartschicht 7 wirkt schwarz.After roughening, the whole object (pan) is brought to a temperature below 600 ° C in an oven. A temperature of 450 ° C. is preferably selected. Immediately after reaching this temperature, a mixture with 80 to 40 percent by weight of aluminum oxide (Al 2 O 3 ) and 20 to 60 percent by weight of titanium dioxide (TiO 2 ) is applied. For example, about sixty percent by weight of aluminum oxide and forty percent by weight of titanium dioxide with an admixture of five to ten percent by weight of aluminum fluoride (AlF 3 ) are applied as a homogeneous mixture in a plasma spraying process as a thermal spraying process. The admixed aluminum fluoride produces an anti-adhesive effect in the hard layer 7 . The use of aluminum fluoride is not mandatory; other non-stick materials can also be used. However, it is important to ensure compatibility with the aluminum oxide-titanium dioxide mixture. The material used must also remain under the thermal conditions of plasma spraying. In plasma spraying, diamond crystals are added, which have a diameter between 0.5 µm and 10 pm. The aluminum oxide-titanium dioxide-aluminum fluoride mixture with embedded diamond crystals is sprayed onto the surface 5 as a hard layer 7 up to a layer thickness of 50 μm to 150 μm. The applied hard layer 7 appears black.

Das Beimischen der Diamantkristalle hat derart zu erfolgen, dass sie keiner Temperatur ausgesetzt werden, welche über 900°C liegt. Bei 900°C kann sich nämlich Diamant in Graphit verwandeln bzw. bei Sauerstoffzutritt verbrennen. Von diesen 900°C sollte ein ausreichender temperaturmäßiger Abstand gehalten werden.The diamond crystals must be mixed in such a way that they have no temperature exposed to temperatures above 900 ° C. At 900 ° C, diamond can transform into graphite or burn when exposed to oxygen. Of these 900 ° C should a sufficient temperature distance should be kept.

Vereinfacht ausgedrückt gibt das Aluminiumoxid als relativ preisgünstiges Material der Schicht 7 die notwendige Härte, während Titandioxid dieser Schicht 7 die Duktilität und die dunkle bzw. schwarze Farbe gibt. Durch die Duktilität des Titandioxids ist eine gute Resistenz der Beschichtung gegenüber großen Temperaturschwankungen gegeben, wie sie nun einmal bei Bratpfannen auftreten.Put simply, the aluminum oxide, as a relatively inexpensive material, gives the layer 7 the necessary hardness, while titanium dioxide gives this layer 7 the ductility and the dark or black color. Due to the ductility of the titanium dioxide, the coating is resistant to large temperature fluctuations, such as occur in frying pans.

Nach dem Aufsprühen des obigen Pulvergemisches lässt man den Gegenstand auf Raumtemperatur abkühlen. Auf die Hartschicht 7 kann dann, wie in der Figur gezeigt, eine weitere Schicht 9 aus Fluorsilan ebenfalls mit eingelagerten Diamantkristallen eines Durchmessers von 0,5 um bis 10 µm als Suspension aufgebracht werden. Der Suspension ist vorzugsweise ein Pigment beigemischt, mit dem an den Farbton der Hartschicht 7 angeglichen wird. Es wird eine Schichtdicke von 1 bis 10 µm, bevorzugt von 2 um bis 5 µm aufgebracht. Diese Suspension dringt in die Rauhigkeit und Poren der Hartschicht 7 ein. Anschließend wird der Gegenstand in einem Ofen in mehreren Stufen (100°C, 250°C, 400°C) auf 400°C bis 430°C erhitzt und auf der Endtemperatur etwa zehn bis fünfzehn Minuten gehalten. Das Aufbringen dieser Schicht 9 ist nicht zwingend. Die antihaftende Wirkung der Beschichtung ist auch ohne diese Schicht 9 gegeben; sie wird jedoch durch diese noch verbessert. Als Pigment wird beispielsweise ein Rußpigment (Carbonbasis) verwendet.After spraying on the above powder mixture, the object is allowed to cool to room temperature. Then, as shown in the figure , a further layer 9 made of fluorosilane, likewise with embedded diamond crystals with a diameter of 0.5 μm to 10 μm, can be applied to the hard layer 7 as a suspension. A pigment is preferably added to the suspension, with which the shade of the hard layer 7 is adjusted. A layer thickness of 1 to 10 μm, preferably 2 μm to 5 μm, is applied. This suspension penetrates into the roughness and pores of the hard layer 7 . The article is then heated in an oven in several stages (100 ° C, 250 ° C, 400 ° C) to 400 ° C to 430 ° C and held at the final temperature for about ten to fifteen minutes. It is not essential to apply this layer 9 . The non-stick effect of the coating is also given without this layer 9 ; however, it is still improved by this. For example, a carbon black pigment is used as the pigment.

Auf die weitere Schicht 9 wird als Antihaftbelag eine Deckschicht 11 mit ein bis drei Lagen eines Fluorpolymers, bevorzugt PTFE (Polytetrafluorethylen), als Suspension nach einem Abkühlen auf Raumtemperatur aufgebracht. Diese Suspension dringt ebenfalls in eine noch verbliebene Rauhigkeit und in die Poren ein. Nach dem Aufbringen wird ein Erhitzungsprogramm analog demjenigen der Schicht 9 gefahren. Dadurch, dass auch hier die Endtemperatur zehn bis fünfzehn Minuten gehalten wird, erfolgt ein Einbrennen des PTFEs. Die Erweichungstemperatur des PTFE liegt bei 360°C. Die Temperatur des Gegenstands ist somit während des Einbrennens eindeutig über dieser Temperatur, so dass die Suspensionspartikel zu einer zähen und elastischen Schicht gesintert werden. Durch das Zusammensintern entsteht eine elastische PTFE-Deckschicht 11, welche mit einer Schichtdicke von zwei bis zehn Mikrometer Dicke sich an die verbleibende Rauhigkeit der darunterliegenden Schicht 9 gut anschmiegt.A cover layer 11 with one to three layers of a fluoropolymer, preferably PTFE (polytetrafluoroethylene), is applied to the further layer 9 as a non-stick coating as a suspension after cooling to room temperature. This suspension also penetrates into a remaining roughness and into the pores. After the application, a heating program analogous to that of layer 9 is carried out. The fact that the final temperature is held here for ten to fifteen minutes means that the PTFE is burned in. The softening temperature of the PTFE is 360 ° C. The temperature of the object is thus clearly above this temperature during the baking, so that the suspension particles are sintered to form a tough and elastic layer. The sintering together creates an elastic PTFE cover layer 11 which, with a layer thickness of two to ten micrometers, conforms well to the remaining roughness of the underlying layer 9 .

Die hier beschriebene Beschichtung 1 ist sehr gut antihaftend gegen auf ihr liegende zu erwärmende (zu bratende) Lebensmittel und zudem resistent gegen Verkratzen bei einer guten "Wärmeverteilung" über dem Pfannenboden. Sollte dennoch die oberste PTFE-Schicht 11 verkratzt werden, so ist diese Verkratzung auf Grund der Farbanpassung der Schicht 9 an die Farbe der Hartschicht 7 nicht sichtbar. Die antihaftende Eigenschaft wird hierdurch so gut wie nicht beeinträchtigt, da die Schicht 9 ebenfalls "antihaftend" ist.The coating 1 described here is very well non-stick to food to be heated (roasted) lying on it and also resistant to scratching with good "heat distribution" over the pan bottom. Should the top PTFE layer 11 nevertheless be scratched, this scratching is not visible due to the color adaptation of the layer 9 to the color of the hard layer 7 . The anti-adhesive property is hardly affected by this, since the layer 9 is also “anti-adhesive”.

Anstelle von Bratpfannen können auch Oberflächen von Bügeleisen, Töpfen, Oberflächen von Maschinenteilen wie Lagerschalen, ... mit der oben beschriebenen Beschichtung 1 beschichtet werden.Instead of frying pans, surfaces of irons, pots, surfaces of machine parts such as bearing shells, ... can be coated with the coating 1 described above.

Anstatt in die Hartschicht 7 Diamantkristalle einzubringen, können die Diamanten auch mit einem reaktiven Beschichtungsverfahren in Gegenwart von Methan abgeschieden werden. Dieses Verfahren ist aber im Augenblick noch teurer als ein direktes Einbringen der Diamantkristalle.Instead of introducing 7 diamond crystals into the hard layer, the diamonds can also be deposited using a reactive coating process in the presence of methane. However, this method is currently more expensive than directly inserting the diamond crystals.

Anstelle von Aluminiumoxid und Titandioxid als Material der Hartschicht 7 können auch andere keramische Oxide, Nitride, Carbide, Oxinitride oder Carbooxinitride eines oder mehrerer Elemente aus den chemischen Gruppen IVb bis Vlb, des Aluminiums, des Nickels oder des Siliziums oder deren Mischungen verwendet werden. Zur Gruppe IVb gehören Titan (Ti), Zirkon (Zr) und Hafnium (Hf). Zur Gruppe Vb gehören Vanadium (V), Niob (Nb) und Tantal (Ta). Zur Gruppe Vlb gehören Chrom (Cr), Molybdän (Mo) und Wolfram (W). Die oben beschriebene Mischung hat sich jedoch als besonders vorteilhaft herausgestellt.Instead of aluminum oxide and titanium dioxide as the material of the hard layer 7 , other ceramic oxides, nitrides, carbides, oxynitrides or carboxynitrides of one or more elements from chemical groups IVb to VIb, aluminum, nickel or silicon or mixtures thereof can be used. Group IVb includes titanium (Ti), zircon (Zr) and hafnium (Hf). Group Vb includes vanadium (V), niobium (Nb) and tantalum (Ta). The Vlb group includes chromium (Cr), molybdenum (Mo) and tungsten (W). However, the mixture described above has proven to be particularly advantageous.

Anstatt die Schicht 9 aufzubringen und stufenweise zu erhitzen und dann die Deckschicht 11 aufzubringen und ebenfalls stufenweise zu erhitzen, kann auch die Schicht 9 aufgebracht werden und nach deren Antrocknen sofort die Schicht 11, welche dann beide, wie oben beschrieben, stufenförmig oder annähernd kontinuierlich ansteigend erhitzt werden.Instead of applying the layer 9 and heating it step by step and then applying the top layer 11 and also heating it step by step, the layer 9 can also be applied and, after it has dried, the layer 11 immediately, both of which, as described above, then gradually or gradually increasing be heated.

Anstelle einer Deckschicht aus PTFE kann auch eine PFA- Schicht (Perfluoralcyd) bzw. eine FEP-Schicht (Fluorethylenpropylen) sowie artverwandte Materialien verwendet werden. Anstelle einer Hartschicht auf den Gegenstand mit eingelagerten Diamantkristallen kann auch eine andere z.B. teflonartige, nicht unbedingt als Hartschicht zu bezeichnende Schicht mit eingelagerten Diamantkristallen verwendet werden.A PFA layer (P he f luor a lcyd) and a FEP-layer (F luor e Thylen p ropylene) as well as allied materials are used instead of a layer of PTFE. Instead of a hard layer on the object with embedded diamond crystals, it is also possible to use another, for example Teflon-like, layer with embedded diamond crystals, which is not necessarily to be referred to as a hard layer.

Anstatt den Gegenstand aus Aluminium oder aus einer Aluminiumlegierung herzustellen, kann er auch aus rostfreiem Stahl oder Eisen hergestellt werden. Aluminium bzw. dessen Legierungen haben jedoch den Vorteil einer guten Wärmeleitfähigkeit. Auch Gegenstände aus Kupfer können entsprechend beschichtet werden; es ist jedoch hierbei darauf zu achten, dass keine Oxidation der Kupferoberfläche eintritt.Instead of making the item out of aluminum or an aluminum alloy, it can also be made of stainless steel or iron. Aluminum or however, its alloys have the advantage of good thermal conductivity. Objects too copper can be coated accordingly; however, it is here make sure that no oxidation of the copper surface occurs.

Claims (10)

Verfahren zum Aufbringen einer, insbesondere antihaftenden Beschichtung (1) auf einem metallischen, eine hohe Wärmeleitfähigkeit ausweisendem Gegenstand (3), insbesondere im wesentlichen aus Aluminium oder einer Aluminiumlegierung, dadurch gekennzeichnet, dass auf eine für die Beschichtung (1) vorbehandelte Oberfläche (5) des Gegenstands (3) eine Schicht (7) mit eingelagerten Diamantkristallen aufgebracht wird.Method for applying a, in particular non-stick coating (1) to a metallic object (3) exhibiting a high thermal conductivity, in particular essentially made of aluminum or an aluminum alloy, characterized in that on a surface (5) pretreated for the coating (1 ) the object (3) a layer (7) with embedded diamond crystals is applied. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Beschichtung mit eingelagerten Diamantkristallen Aluminiumoxid/Titandioxid-Mischschicht als Hartschicht (7) aufgebracht wird, wobei vorzugsweise die Hartschicht (7) mit 97 bis 40 Gewichtsprozent Aluminiumoxid (Al2O3) und 3% bis 60 Gewichtsprozent Titandioxid (TiO2), insbesondere mit 85% bis 40% Aluminiumoxid und 15% bis 60% Titandioxid, bevorzugt mit etwa 60% Aluminiumoxid und 40% Titandioxid aufgebracht wird, welcher vorzugsweise ein antihaftend wirkendes Material, dem insbesondere 5% bis 10% Aluminium-Fluorid (AlF3) unter entsprechender Reduzierung der Aluminiumoxid- bzw. Titandioxid-Anteile beigemischt werden.A method according to claim 1, characterized in that is coated with embedded diamond crystals aluminum oxide / titanium dioxide mixed layer as a hard layer (7), preferably wherein the hard layer (7) with 97 to 40 weight percent aluminum oxide (Al 2 O 3) and 3% to 60% by weight of titanium dioxide (TiO 2 ), in particular with 85% to 40% of aluminum oxide and 15% to 60% of titanium dioxide, preferably with about 60% of aluminum oxide and 40% of titanium dioxide, which is preferably an anti-adhesive material, in particular 5% to 10 % Aluminum fluoride (AlF 3 ) can be added with a corresponding reduction in the aluminum oxide or titanium dioxide content. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Hartschicht (7) mit einem thermischen Sprühverfahren, insbesondere mit einem Plasmasprühverfahren, bevorzugt mit einem Hochgeschwindigkeitsverfahren (HVOF = high velocity oxigen fuel)) aufgebracht wird.The method of claim 2, characterized in that the hard layer (7) with a thermal spraying method, in particular a plasma spraying method, preferably with a high-speed process (HVOF = h igh v eLocity Xigen o f uel)) is applied. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass auf die Hartschicht (7) eine weitere Schicht (9) im wesentlichen aus Fluorsilan aufgebracht wird, in welche bevorzugt ebenfalls Diamantkristalle eingelagert werden. Method according to one of claims 1 to 3, characterized in that a further layer (9) consisting essentially of fluorosilane is applied to the hard layer (7) , in which diamond crystals are preferably also incorporated. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die weitere Schicht (9) pigmentiert wird, um einen Schichtfarbton zu erreichen, welcher der Hartschicht (7) angeglichen ist, und bevorzugt eine Deckschicht (11) aufgebracht wird, wobei diese insbesondere als eine dünne PTFE-Schicht aufgebracht wird und in bevorzugter Weise in die Hartschicht (7) sowie insbesondere auch in die weitere Schicht (9) eingelagerte Diamantkristalle eine Größe zwischen 0.5 µm bis 10 µm haben.A method according to claim 4, characterized in that the further layer (9) is pigmented in order to achieve a layer color which matches the hard layer (7) , and preferably a cover layer (11) is applied, this in particular as a thin PTFE Layer is applied and diamond crystals embedded in the hard layer (7) and in particular also in the further layer (9) preferably have a size between 0.5 μm to 10 μm. Eine hohe Wärmeleitfähigkeit aufweisender Gegenstand (3), insbesondere im wesentlichen aus Aluminium oder einer Aluminiumlegierung, beschichtet mit einem Verfahren nach einem der Patentansprüche 1 bis 5, gekennzeichnet durch eine Beschichtung (1), in die Diamantkristalle eingelagert sind.An object (3) having a high thermal conductivity, in particular essentially made of aluminum or an aluminum alloy, coated with a method according to one of the claims 1 to 5, characterized by a coating (1) in which diamond crystals are embedded. Gegenstand (3) nach Anspruch 6, dadurch gekennzeichnet, dass die Beschichtung eine Antihaftwirkung hat und wenigstens aus einer im wesentlichen aus einer Mischung von Aluminiumoxid (Al2O3) und Titiandioxid (TiO2), bestehenden Hartschicht (7), in die dann die Diamantkristalle eingelagert sind, aufgebaut ist.Article (3) according to claim 6, characterized in that the coating has a non-stick effect and at least consists of a hard layer (7) consisting essentially of a mixture of aluminum oxide (Al 2 O 3 ) and titanium dioxide (TiO 2 ) , into which then the diamond crystals are embedded. Gegenstand (3) nach Anspruch 7, dadurch gekennzeichnet, dass die Hartschicht (7) im wesentlichen 97 bis 40 Gewichtsprozent Aluminiumoxid und 3 bis 60 Gewichtsprozent Titandioxid, insbesondere 80% bis 40% Aluminiumoxid und 20% bis 60% Titandioxid, bevorzugt etwa 60% Aluminiumoxid und 40% Titandioxid enthält und vorzugsweise die Haftschicht (7) 5% bis 10% Aluminium-Fluorid (AlF3) als ein Antihaftwirkung entfaltendes Material unter entsprechender Reduzierung der Aluminiumoxid- bzw. Titandioxid-Anteile beigemischt sind.Article (3) according to claim 7, characterized in that the hard layer (7) essentially 97 to 40 weight percent aluminum oxide and 3 to 60 weight percent titanium dioxide, in particular 80% to 40% aluminum oxide and 20% to 60% titanium dioxide, preferably about 60% Contains aluminum oxide and 40% titanium dioxide and preferably the adhesive layer (7) 5% to 10% aluminum fluoride (AlF 3 ) is added as a non-stick material with a corresponding reduction in the aluminum oxide or titanium dioxide content. Gegenstand nach Anspruch 6, dadurch gekennzeichnet, dass die Beschichtung eine Hartschicht im wesentlichen aus einem keramischen Oxid und/oder einem keramischen Nitrid und/oder einem keramischen Carbid und/oder einem keramischen Oxinitrid und/oder einem keramischen Carbooxinitrid eines oder mehrerer Elemente aus den chemischen Gruppen IVb bis Vlb, des Aluminiums, des Nickels oder des Siliziums oder deren Mischungen ist.Article according to claim 6, characterized in that the coating comprises a hard layer essentially of a ceramic oxide and / or a ceramic nitride and / or a ceramic carbide and / or a ceramic oxynitride and / or a ceramic carbooxynitride of one or more elements from the chemical Groups IVb to Vlb, aluminum, nickel or silicon or mixtures thereof. Gegenstand (3) nach Anspruch 6 bis 9, dadurch gekennzeichnet, dass auf der Diamanten enthaltenden Beschichtung (7) eine weitere Schicht (9) im wesentlichen aus Fluorsilan liegt, in die bevorzugt ebenfalls Diamantkristalle eingelagert sind, wobei vorzugsweise die Diamantkristalle in dieser weiteren Schicht (9) sowie in der Hartschicht (7) einen Durchmesser zwischen 0,5 µm und 10 µm haben und insbesondere eine Deckschicht (11) im wesentlichen aus PTFE als die oberste Schicht der Beschichtung (1) vorhanden ist.Article (3) according to Claims 6 to 9, characterized in that on the diamond-containing coating (7) there is a further layer (9) consisting essentially of fluorosilane, in which diamond crystals are preferably also embedded, the diamond crystals preferably being in this further layer (9) and in the hard layer (7) have a diameter between 0.5 µm and 10 µm and in particular a cover layer (11) consisting essentially of PTFE as the top layer of the coating (1) is present.
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EP2332661A1 (en) 2005-12-14 2011-06-15 Dupont-Mitsui Fluorochemicals Company, Ltd. Non-stick coating composition comprising diamond particles and substrate having the composition applied thereto
EP2586892A2 (en) 2011-10-25 2013-05-01 Stefan Hort Cooking device
EP2586891A1 (en) 2011-10-25 2013-05-01 Stefan Hort Cooking device
EP2586892A3 (en) * 2011-10-25 2014-05-21 Stefan Hort Cooking device
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EP2592174A1 (en) * 2011-11-14 2013-05-15 Siemens Aktiengesellschaft Coating system with structured substrate surface and method for manufacture
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JP2014091833A (en) * 2012-10-31 2014-05-19 Seb Sa Ceramic coating with improved scratch resistance and heat conduction properties
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CN106435564A (en) * 2016-11-14 2017-02-22 北京联合涂层技术有限公司 Electromagnetic coating of high-performance cooker and manufacturing method of electromagnetic coating
CN109930103A (en) * 2017-12-15 2019-06-25 佛山市顺德区美的电热电器制造有限公司 A kind of heating utensil and preparation method thereof
CN109930103B (en) * 2017-12-15 2023-11-14 佛山市顺德区美的电热电器制造有限公司 Heating appliance and preparation method thereof
DE202023102922U1 (en) 2023-05-26 2023-07-17 SurFunction GmbH Cooking device for cooking food

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