EP2457412B1 - Heater, in particular high-temperature heater, and method for the production thereof - Google Patents

Heater, in particular high-temperature heater, and method for the production thereof Download PDF

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Publication number
EP2457412B1
EP2457412B1 EP10736624.7A EP10736624A EP2457412B1 EP 2457412 B1 EP2457412 B1 EP 2457412B1 EP 10736624 A EP10736624 A EP 10736624A EP 2457412 B1 EP2457412 B1 EP 2457412B1
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EP
European Patent Office
Prior art keywords
layer
electrically conductive
substrate
protective layer
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP10736624.7A
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German (de)
French (fr)
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EP2457412A1 (en
Inventor
Harun Erismis
Michael Geiss
Dominik Nemec
Frank JÖRDENS
Gerhard Schmidmayer
Philipp Schaller
Jürgen Salomon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
BSH Hausgeraete GmbH
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
BSH Bosch und Siemens Hausgeraete GmbH
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Priority to SI201030272T priority Critical patent/SI2457412T1/en
Priority to PL10736624T priority patent/PL2457412T3/en
Publication of EP2457412A1 publication Critical patent/EP2457412A1/en
Application granted granted Critical
Publication of EP2457412B1 publication Critical patent/EP2457412B1/en
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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/68—Heating arrangements specially adapted for cooking plates or analogous hot-plates
    • H05B3/74—Non-metallic plates, e.g. vitroceramic, ceramic or glassceramic hobs, also including power or control circuits
    • H05B3/748—Resistive heating elements, i.e. heating elements exposed to the air, e.g. coil wire heater
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/0014—Devices wherein the heating current flows through particular resistances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/26—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/26—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base
    • H05B3/265—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base the insulating base being an inorganic material, e.g. ceramic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/68—Heating arrangements specially adapted for cooking plates or analogous hot-plates
    • H05B3/74—Non-metallic plates, e.g. vitroceramic, ceramic or glassceramic hobs, also including power or control circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/002—Heaters using a particular layout for the resistive material or resistive elements
    • H05B2203/005—Heaters using a particular layout for the resistive material or resistive elements using multiple resistive elements or resistive zones isolated from each other
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/011—Heaters using laterally extending conductive material as connecting means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013—Heaters using resistive films or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/028—Heaters specially adapted for trays or plates to keep food or liquids hot
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/04—Heating means manufactured by using nanotechnology
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49082—Resistor making
    • Y10T29/49083—Heater type

Definitions

  • the invention relates to a method for producing a heater, in particular high-temperature heating, as well as such a heater, in particular a high-temperature heating, in which on a carrier material at a current flow heat generating layer is provided.
  • Such heaters are used for products of white goods, for example as a heater for an oven, toaster or hobs or glass ceramic hobs.
  • a heater for an oven toaster or hobs or glass ceramic hobs.
  • the use of such heating elements leads to an inhomogeneous warm-up process. A targeted focus on the food or to be heated Good is not given.
  • there is an air cushion between the heating wires and the carrier material which has a negative effect on the heat transfer.
  • induction hobs are known in which the heat is generated directly in the cooking pot by eddy currents.
  • the initial cost is complex, and it requires special pots for heating the food.
  • this high-temperature heating can not be easily transferred to any white goods.
  • a plate-shaped heating element has become known, which is used for the air conditioning of homes and buildings.
  • a heating layer of a carbon-fiber mixture with non-conductive materials has become known, which is applied to a gypsum board or composite panel provided on the backside with a composite building material.
  • strip-shaped contact elements are provided, so that a surface heating of the layer is made possible on carbon-fiber mixture.
  • Such sheet-like heaters allow due to their design of the heating layer only temperatures in a range of ⁇ 50 ° C and are not suitable for the use of white goods.
  • the application of such fiber blends or fiber fabrics is very costly.
  • an electric hotplate with at least one cooking zone has become known which uses glass ceramic, glass or ceramic as the carrier material.
  • an electrical insulation layer is provided for heating the cooking zones and a thermally insulating cover layer, wherein a Schuwiderstandsmaterial is provided therebetween lying.
  • the heating resistor material consists of electrically conductive carbon, graphite particles or carbon fibers which are contacted with electrodes.
  • the heating resistor element may be mixed with a binder of heat-resistant organic or inorganic substances.
  • the second thermally insulating covering layer applied thereon terminates airtight with respect to the atmosphere of the heating resistance element, wherein the covering layer consists of heat-resistant glass or an enamel layer.
  • the assembly of the hot plate body is carried out by electrochemical bonding of the superimposed layers, wherein it is provided that the heating resistance element is brought by heating to a temperature above 400 ° C and in addition an electrical voltage of more than 400 V to the hotplate body and the Schuwiderstandselement is applied.
  • This layer structure of the cooking zone has the disadvantage that a complex representation of the adhesion properties is given by high voltages and no free choice of the contacting method is possible because the contact must be directly on the conductive layer.
  • an electric roasting oven plate for heating which is based on a structure of the electric hotplate according to of the DE 100 01 330 A1 Reference, this structure for electric baking, cooking or electric roasting ovens should be used.
  • An infrared CNT heating device which comprises a thermally loadable molded body with an electrically conductive structural layer, which generates infrared heat rays when current flows through.
  • the electrically conductive structural layer consists of CNT materials, which are obtained by extraction or manual application of CNT suspensions and applied to the molding with suitable support materials such as gel or pasty emulsions.
  • a functional coating of thermally treated ceramic, metal, enamel, blocking, adhesive or insulating layer may be present between the shaped body and the conductive structural layer.
  • the invention has the object of providing a method for producing a heater, in particular a high-temperature heating and a heater, in particular a high-temperature heating to propose, in which a heating element in a simple manner can be applied over the entire surface as a thin layer and allows homogeneous heat transfer.
  • a method for producing a heater in particular for thermal household appliances, in which on the carrier material, a first electrically conductive layer is applied, which is formed from a flowable base material and carbon nanotubes dispersed therein that on the first Layer, a protective layer is applied, which penetrates by applying to the first layer in this, by compressing the layers by a temperature treatment and to prepare the protective layer, a silicate is used to form an inorganic layer.
  • This method makes it possible to produce a very thin heating element which can be heated up very quickly and allows a uniform heat transfer to the carrier material.
  • the heat treatment process after applying the first layer and the protective layer has surprisingly revealed that the carbon nanotube selected as the conductive material is temperature resistant in the first layer and the protective layer can be introduced and burning is avoided.
  • a silicate as a protective layer, the carbon nanotubes dispersed in the base material can be completely incorporated or protected from the environment, so that especially at elevated temperatures oxidation protection of the carbon nanotubes is given, since they begin to degrade at these high temperatures , By penetrating the protective layer and the subsequent compression of this degradation is counteracted.
  • a heating element which enables a corresponding thermal shock stability and a mechanical adhesion to the carrier material.
  • the at least one layer is contacted with contact elements and the layers applied to the carrier material are heated.
  • an increased mechanical adhesion between the contact element and the carrier material can be achieved.
  • a further preferred embodiment of the method provides that the contact elements are strip-shaped. As a result, a sheet-like heating can be achieved.
  • the applied first layer and protective layer is heated in particular to a temperature between 300 ° C to 700 ° C.
  • a sintering process of the layers takes place. This can be done in particular a compression of the layers.
  • This has the advantage that such high-temperature heaters are compressed by the sintering oxygen-tight and thus suitable for operation at temperatures of> 400 ° C and are resistant.
  • a preferred embodiment of the method provides that the first layer is dried after application and then the protective layer is applied.
  • This drying process has the advantage that the first layer is at least slightly compressed, in particular water-soluble constituents can evaporate before the further protective layer is applied. As a result, a thin structure of the heating element can be favored.
  • the first layer and separately the protective layer or the functional layer are applied by a spray method by knife coating or a printing process.
  • a screen printing method can be provided, by which the in particular pasty first layer is applied in a simple manner to the carrier material.
  • the likewise preferred pasty trained second protective layer can be applied in the same way.
  • known technologies can be used for the production of high-temperature heating elements.
  • a spraying method or a spraying method may be provided in order to apply the first and second layer to the carrier material.
  • a so-called spray coating, a dip coating, so a dip coating or a spin coating can be realized.
  • a further preferred embodiment of the method provides that the first layer is applied over the entire surface or in adjacent strips, the protective layer is applied over the entire surface of the first layer and this completely envelopes the substrate, in particular before or after the application of the first layer strip-shaped contact elements be applied.
  • the first layer is connected as an electrically conductive layer with the strip-shaped contact elements and then allows electrical insulation through the protective layer with the exception of connection points on the strip-shaped contact elements.
  • the complete encapsulation of the first electrically conductive layer by the protective layer further makes it possible to use water-soluble materials as the basis for a dispersion for the production of the first electrically conductive layer. These in turn have the advantage that processing without the use of solvents is possible and thus harmless to health.
  • a further preferred embodiment of the method provides that before applying the first layer to the carrier material in the heating region, an electrically insulating layer is applied to the carrier material. This is done in particular when the carrier material is not made of a dielectric material, but of an electrically conductive or weakly electrically conductive material.
  • a preferred embodiment of the method provides that an aqueous solution, in particular water or distilled water, is used for producing the first layer as electrically non-conductive base material, which preferably comprises a dispersant, such as gum arabic.
  • a dispersant such as gum arabic.
  • a further preferred embodiment of the method provides that incorporated into the electrically non-conductive base material fillers of carbon nanotubes and / or graphite and this paste can then be printed.
  • the last step describes the application of the protective layer (TopCoat), which preferably consists of ethyl silicate with graphite.
  • single, double or multiwalled nanotubes can preferably be used.
  • the combination of graphite and carbon nanotubes has the advantage that a flowable dispersion for the first layer for full-surface application to a carrier material is achieved.
  • an adhesive in particular gum arabic
  • an adhesive is dispersed into the first layer.
  • an adhesion mediation between the first layer and a carrier material can be improved.
  • the gum arabic is used before the application of the protective layer (TopCoat) as a primer. This guarantees that when printing the protective layer (TopCoat) this does not destroy the first layer (PreCoat).
  • gum arabic During the penetration of the layers, the gum arabic is burned out. Before the protective layer forms gas-tight, the volatile constituents of gum arabic diffuse out.
  • other surfactants such as SDS or Triton are also conceivable.
  • a heating element in particular a high-temperature heating element, for example for thermal household appliances, in which a first electrically conductive layer consisting of a base material and a carbon nanotube dispersed therein and a protective layer are provided on the carrier material the first layer is penetrated and that the protective layer consists of silicate.
  • a heating element allows high temperature resistance and thermal shock stability to be achieved.
  • any desired geometries for the heating elements on a carrier material, in particular for forming a high-temperature heating can thereby be selected.
  • a preferred embodiment of the heating element provides that the layers are contacted with contact elements. As a result, a simple connection can be created.
  • the contact elements are strip-shaped.
  • Eint further preferred embodiment of the heating provides that the layers are compressed by a temperature treatment. As a result, the temperature resistance and / or thermal shock stability can be further increased.
  • the first layer and the protective layer form a heating element with a layer thickness of less than 500 ⁇ m, in particular less than 100 ⁇ m. Due to the choice of materials, an ultra-thin application may be possible. At the same time, a homogeneous heat generation within the first electrically conductive layer and thus of the carrier material can take place.
  • the heater preferably has a first layer, which has a concentration of 0.1 to 100 wt% CNT in the flowable base material, in particular in water or distilled water. This can be given a high electrical conductivity, so that you can work with low voltages.
  • a concentration of 1 to 3 wt% CNT and 5 to 50 wt% graphite is provided as a filler in the base material. By adding graphite, the flowability of the first layer or the mixture can be increased.
  • the heating element preferably has a heating element with a first layer and a protective layer which has an electrical resistance of less than 100 ohms / sq. having. This allows a temperature generation of> 400 ° C on large substrates by means of a conventional power supply in the home. In addition, the layers could be made even thinner to ensure even better mechanical stabilities.
  • a carrier material is preferably provided which consists of ceramic, glass ceramic, ceran ceramic, aluminum oxide ceramic, MgO, KER 520.
  • FIG. 1 is a schematic side view of a heater 11, in particular a high-temperature heating shown.
  • FIG. 2 shows a schematic view from below.
  • the high-temperature heating 11 comprises a carrier material 12, which may be formed, for example, when used in the field of white goods as ceramics, glass ceramic, Cerankeramik, alumina ceramics or the like.
  • On the underside of a heating element 14 is provided within a heating area.
  • This heating element 14 comprises a first electrically conductive layer 16, on which a protective layer 17 is applied.
  • the protective layer 17 completely surrounds the first electrical layer 16, so that it is electrically insulated and mechanically protected against the environment on the substrate 12 is provided.
  • the first electrically conductive layer 16 extends between two strip-shaped contact elements 18, which are guided for contacting the electrical layer 16, for example, to an edge region of the carrier material 12. Between the two preferably parallel to each other extending contact elements 18, the first layer 16 extends and forms the heating area.
  • the protective layer 17 covers the first layer 16 and preferably the strip-shaped contact elements 18, so that only for example in the edge region a free contact point can be recessed. Alternatively, it can also be provided that initially the first layer 16 and the protective layer 17 are applied and then the strip-shaped contact elements 18 are brought to the heating zone formed by the first layer 16 and protective layer 17.
  • the first electrically conductive layer 16 consists of a flowable, electrically non-conductive base material.
  • an aqueous-based dispersion is provided. Carbon nanotubes are dispersed in this dispersion as an electrically conductive material.
  • the dispersion comprises a filler, in particular graphite, in order to support the electrical conductivity and to adjust the flowability.
  • an adhesive is preferably provided in the dispersion. This may be, for example, gum arabic. Other surfactants such as SDS or Triton can be used. As a result, a flowable or pasty mass can be produced, which can be applied to the carrier material 12 by a printing process or spraying process.
  • the protective layer 17 is preferably made of a silicate, which may preferably be enriched with adhesive, filler or other particles in order to increase the adhesion properties. As a result, the thermal shock stability and the mechanical adhesion to the substrate can be improved. By penetrating the protective layer 17 into the first layer 16, these CNTs are also suitable for use at temperatures above 350 ° C., since the protective layer 17 encloses the CNTs airtight.
  • the electrically conductive material preferably consists of a composite of CNTs and graphite or further electrically conductive particles or constituents which make it possible to form a pasty mass or a sprayable mass.
  • heating element 14 is prepared by first mixing the components of an electrically non-conductive base material and carbon nanotubes dispersed therein or a composite of carbon nanotubes with other electrically conductive materials to form a flowable or pasty mass, which by means of a Screen printing process is applied over the entire surface of the substrate 12. Subsequently, the strip-shaped contact elements 18 can preferably be printed by applying a conductive paste, in particular silver conductive paste, by screen printing. These contact elements 18 can also be provided on the carrier material 12 before the application of the first layer 16. Following this For example, according to a variant of the first embodiment of the production method, this first layer 16 can be subjected to temperature treatment.
  • the protective layer 17 is preferably applied by a screen printing method. Alternatively, this can also be applied without an intervening drying process of the first layer 16.
  • the carrier material 12 is treated with the layers 17 applied thereto as well as the contact elements 18, so that at least the protective layer 17 is preferably sintered.
  • the compression takes place and requires a further "compression" of the conductive particles, which due to the increased number of contacts and the compactness to a lower spec. Resistance leads. This in turn can be used to create a conductivity improvement in the first layer 16.
  • Such high-temperature heaters 11 have heating elements 14, the thickness of which may be formed, for example, ⁇ 100 ⁇ m.
  • heating elements 14 the thickness of which may be formed, for example, ⁇ 100 ⁇ m.
  • the full-surface arrangement of the electrically conductive layer 16 on the carrier material 12 a homogeneous heating and thermal radiation of the carrier material 12 is made possible.
  • the protective layer 17 may be associated with a reflector to reflect the heat radiation from the heating element 14 in the opposite direction to the carrier material 12 and to accelerate the heating of the carrier material 12.
  • FIG. 3 is an alternative embodiment to FIG. 1 shown.
  • This embodiment differs from that in FIG. 1 from that prior to the application of the first electrically conductive layer 16, an electrical insulating layer 19 is applied over the entire surface of the carrier material 12 in order to arrange the electrically conductive layer 16 relative to the carrier material 12 in isolation.
  • This arrangement of the insulating layer 19 may also be provided when applying a mixture consisting of the first electrically conductive layer 16 and the protective layer 17.
  • an electrically insulating layer 19 are applied over the entire surface.
  • FIG. 4 is an alternative embodiment to FIG. 1 shown.
  • This embodiment differs only in that instead of a full-surface first electrically conductive layer 16, a strip-shaped layer 16 is formed.
  • Such webs or ribs can be adapted in geometry and contour to the corresponding applications.
  • the strip geometry can heat targeted areas. In addition, it further favors the adhesion properties of the respective substrate.
  • the strips can be arranged as desired, so that different heating zones can be implemented on a substrate in a targeted manner.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer Heizung, insbesondere Hochtemperaturheizung, sowie eine solche Heizung, insbesondere eine Hochtemperaturheizung, bei der auf einem Trägermaterial eine bei Stromdurchfluss Wärme erzeugende Schicht vorgesehen ist.The invention relates to a method for producing a heater, in particular high-temperature heating, as well as such a heater, in particular a high-temperature heating, in which on a carrier material at a current flow heat generating layer is provided.

Solche Heizungen, insbesondere Hochtemperaturheizungen, werden für Produkte der Weißen Ware, beispielsweise als Heizung für einen Backofen, Toaster oder auch Herdplatten bzw. Glaskeramikkochfelder, eingesetzt. Zur Aufheizung dieser Gegenstände bis zu Temperaturen von > 400 °C werden bislang Heizstäbe eingesetzt, von denen aus eine Wärmestrahlung erfolgte, um das angrenzende Trägermaterial aufzuheizen. Durch den Einsatz solcher Heizstäbe kommt es zu einem inhomogenen Aufwärmvorgang. Eine gezielte Fokussierung auf das Kochgut oder das zu erwärmende Gut ist dadurch nicht gegeben. Des Weiteren besteht zwischen den Heizdrähten und dem Trägermaterial ein Luftpolster, welches sich negativ auf die Wärmeübertragung auswirkt.Such heaters, especially high-temperature heaters, are used for products of white goods, for example as a heater for an oven, toaster or hobs or glass ceramic hobs. To heat these objects up to temperatures of> 400 ° C so far heating rods are used, from which a heat radiation took place in order to heat the adjacent carrier material. The use of such heating elements leads to an inhomogeneous warm-up process. A targeted focus on the food or to be heated Good is not given. Furthermore, there is an air cushion between the heating wires and the carrier material, which has a negative effect on the heat transfer.

Zur Vermeidung eines inhomogenen Aufheizvorganges sind beispielsweise Induktionskochfelder bekannt, bei denen die Wärme im Kochtopf durch Wirbelströme direkt erzeugt wird. Dadurch wird zwar eine homogene Aufheizung des Kochgutes erzielt, jedoch sind die Anschaffungskosten aufwändig, und es werden spezielle Töpfe zum Erwärmen des Kochgutes benötigt. Diese Hochtemperaturheizung lässt sich jedoch nicht ohne Weiteres auf beliebige Produkte der Weißen Ware übertragen.To avoid an inhomogeneous heating process, for example induction hobs are known in which the heat is generated directly in the cooking pot by eddy currents. As a result, although a homogeneous heating of the cooking material is achieved, however, the initial cost is complex, and it requires special pots for heating the food. However, this high-temperature heating can not be easily transferred to any white goods.

Aus der DE 10 2005 049 428 A1 ist ein plattenförmiges Heizelement bekannt geworden, welches zur Raumklimatisierung von Wohnungen und Gebäuden eingesetzt wird. Auf einer Verbundplatte ist eine Heizschicht aus einem Kohlenstoff-Fasergemisch mit nicht leitenden Materialien bekannt geworden, welche auf einer Gipskartonplatte oder eine rückseitig mit einem Verbundbaustoff versehene Verbundplatte aufgebracht ist. Zur Kontaktierung der Heizschicht sind streifenförmige Kontaktelemente vorgesehen, so dass eine flächige Erwärmung der Schicht auf Kohlenstoffiaser-Gemisch ermöglicht wird. Solche flächenförmige Heizungen ermöglichen aufgrund deren Ausgestaltung der Heizschicht lediglich Temperaturen in einem Bereich von < 50 °C und eignen sich nicht für den Einsatz der Weißen Ware. Darüber hinaus ist das Aufbringen von solchen Fasergemischen oder Fasergeweben sehr kostenintensiv.From the DE 10 2005 049 428 A1 is a plate-shaped heating element has become known, which is used for the air conditioning of homes and buildings. On a composite panel, a heating layer of a carbon-fiber mixture with non-conductive materials has become known, which is applied to a gypsum board or composite panel provided on the backside with a composite building material. For contacting the heating layer strip-shaped contact elements are provided, so that a surface heating of the layer is made possible on carbon-fiber mixture. Such sheet-like heaters allow due to their design of the heating layer only temperatures in a range of <50 ° C and are not suitable for the use of white goods. In addition, the application of such fiber blends or fiber fabrics is very costly.

Analoges gilt beispielsweise für die aus der DE 20 2005 013 822 bekannt gewordenen flächenförmigen Heizelemente, welche analog zum Heizungselement zur Raumklimatisierung aufgebaut sind. Solche Verbundsysteme mit einer papierähnlichen Faserstruktur sind in der Herstellung aufwändig und kostenintensiv. Darüber hinaus ist die Anpassung an beliebige Geometrien und ein leichtes Aufbringen erschwert.The same applies, for example, for those from the DE 20 2005 013 822 have become known sheet-like heating elements, which are constructed analogously to the heating element for room air conditioning. Such composite systems with a paper-like fiber structure are complex to manufacture and costly. In addition, the adaptation to any geometry and easy application is difficult.

Aus der DE 100 01 330 A1 ist eine Elektrokochplatte mit mindestens einer Kochzone bekannt geworden, welche als Trägermaterial Glaskeramik, Glas oder Keramik einsetzt. An deren Unterseite ist zum Beheizen der Kochzonen eine elektrische Isolierschicht vorgesehen sowie eine thermisch isolierende Abdeckschicht, wobei dazwischen liegend ein Heizwiderstandsmaterial vorgesehen ist. Das Heizwiderstandsmaterial besteht aus elektrisch leitfähigem Kohlenstoff, Graphitteilchen oder Kohlenstofffasem, die mit Elektroden kontaktiert sind. Das Heizwiderstandselement kann mit einem Bindemittel aus hitzebeständigen organischen oder anorganischen Stoffen vermischt sein. Die darauf aufgebrachte zweite thermisch isolierende Abdeckschicht schließt luftdicht gegenüber der Atmosphäre des Heizwiderstandselementes ab, wobei die Abdeckschicht aus hitzebeständigem Glas oder einer Emailschicht besteht. Der Zusammenbau des Kochplattenkörpers erfolgt durch elektrochemisches Verbinden der aufeinander liegenden Schichten, wobei vorgesehen ist, dass das Heizwiderstandselement durch Aufheizen auf eine Temperatur über 400 °C gebracht wird und zusätzlich eine elektrische Spannung von mehr als 400 V an den Kochplattenkörper und das Heizwiderstandselement angelegt wird.From the DE 100 01 330 A1 is an electric hotplate with at least one cooking zone has become known which uses glass ceramic, glass or ceramic as the carrier material. On the underside, an electrical insulation layer is provided for heating the cooking zones and a thermally insulating cover layer, wherein a Heizwiderstandsmaterial is provided therebetween lying. The heating resistor material consists of electrically conductive carbon, graphite particles or carbon fibers which are contacted with electrodes. The heating resistor element may be mixed with a binder of heat-resistant organic or inorganic substances. The second thermally insulating covering layer applied thereon terminates airtight with respect to the atmosphere of the heating resistance element, wherein the covering layer consists of heat-resistant glass or an enamel layer. The assembly of the hot plate body is carried out by electrochemical bonding of the superimposed layers, wherein it is provided that the heating resistance element is brought by heating to a temperature above 400 ° C and in addition an electrical voltage of more than 400 V to the hotplate body and the Heizwiderstandselement is applied.

Dieser Schichtaufbau der Kochzone weist den Nachteil auf, dass eine aufwendige Darstellung der Haftungseigenschaften durch hohe Spannungen gegeben ist und keine freie Wahl der Kontaktierungsmethode ermöglicht ist, da die Kontaktierung direkt an der leitfähigen Schicht sein muss.This layer structure of the cooking zone has the disadvantage that a complex representation of the adhesion properties is given by high voltages and no free choice of the contacting method is possible because the contact must be directly on the conductive layer.

Aus der DE 103 36 920 A1 geht des Weiteren eine Elektrobratofenplatte zum Heizen vor, welche auf einen Aufbau der Elektrokochplatte gemäß der DE 100 01 330 A1 Bezug nimmt, wobei dieser Aufbau für Elektroback-, Gar- oder Elektrobratöfen eingesetzt werden sollen.From the DE 103 36 920 A1 Furthermore, an electric roasting oven plate for heating, which is based on a structure of the electric hotplate according to of the DE 100 01 330 A1 Reference, this structure for electric baking, cooking or electric roasting ovens should be used.

Aus der DE 20 2009 000 136 U1 ist eine Infrarot-CNT-Heizeinrichtung bekannt, welche einen thermisch belastbaren Formkörper mit einer elektrisch leitfähigen Strukturschicht umfasst, die bei Stromdurchfluss infrarote Wärmestrahlen erzeugt. Die elektrisch leitfähige Strukturschicht besteht aus CNT-Werkstoffen, die durch Extrahieren oder manuellen Auftrag aus CNT-Suspensionen gewonnen und mit geeigneten Trägermaterialien wie Gel oder pastösen Emulsionen auf den Formkörper aufgebracht werden. Zwischen dem Formkörper und der leitfähigen Strukturschicht kann eine funktionelle Beschichtung aus thermisch behandelter Keramik-, Metall, Email-, Blocker-, Haft- oder Isolierschicht vorhanden sein.From the DE 20 2009 000 136 U1 An infrared CNT heating device is known, which comprises a thermally loadable molded body with an electrically conductive structural layer, which generates infrared heat rays when current flows through. The electrically conductive structural layer consists of CNT materials, which are obtained by extraction or manual application of CNT suspensions and applied to the molding with suitable support materials such as gel or pasty emulsions. A functional coating of thermally treated ceramic, metal, enamel, blocking, adhesive or insulating layer may be present between the shaped body and the conductive structural layer.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung einer Heizung, insbesondere eine Hochtemperaturheizung sowie eine Heizung, insbesondere eine Hochtemperaturheizung, vorzuschlagen, bei welchem ein Heizelement in einfacher Weise als dünne Schicht ganzflächig aufgebracht werden kann und eine homogene Wärmeübertragung ermöglicht.The invention has the object of providing a method for producing a heater, in particular a high-temperature heating and a heater, in particular a high-temperature heating to propose, in which a heating element in a simple manner can be applied over the entire surface as a thin layer and allows homogeneous heat transfer.

Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Herstellung einer Heizung, insbesondere für thermische Hausgeräte, gelöst, bei dem auf dem Trägermaterial eine erste elektrisch leitfähige Schicht aufgebracht wird, welche aus einem fließfähigen Grundmaterial und darin dispergierten Carbon-Nanotubes gebildet wird, dass auf diese erste Schicht eine Schutzschicht aufgebracht wird, welche durch das Aufbringen auf die erste Schicht in diese penetriert, indem die Schichten durch eine Temperaturbehandlung komprimiert werden und zur Herstellung der Schutzschicht ein Silikat zur Bildung einer anorganischen Schicht eingesetzt wird.This object is achieved by a method for producing a heater, in particular for thermal household appliances, in which on the carrier material, a first electrically conductive layer is applied, which is formed from a flowable base material and carbon nanotubes dispersed therein that on the first Layer, a protective layer is applied, which penetrates by applying to the first layer in this, by compressing the layers by a temperature treatment and to prepare the protective layer, a silicate is used to form an inorganic layer.

Dieses Verfahren ermöglicht, dass ein sehr dünnes Heizelement hergestellt wird, welches sehr schnell aufgeheizt werden kann und eine gleichmäßige Wärmeübertragung auf das Trägermaterial ermöglicht. Durch den Wärmebehandlungsprozess nach dem Auftragen der ersten Schicht und der Schutzschicht hat sich erstaunlicherweise herausgestellt, dass die als leitfähiges Material ausgewählten Carbon-Nanotubes temperaturbeständig in der ersten Schicht und der Schutzschicht eingebracht werden können und ein Verbrennen vermieden wird. Durch die Verwendung eines Silikats als Schutzschicht können die in dem Grundmaterial dispergierten Carbon-Nanotubes vollständig eingebunden beziehungsweise gegenüber der Umgebung geschützt werden, so dass gerade bei erhöhten Temperaturen ein Oxidationsschutz der Carbon-Nanotubes gegeben ist, da diese bei diesen hohen Temperaturen mit einer Degradation beginnen. Durch das Einpenetrieren der Schutzschicht und der anschließenden Komprimierung wird dieser Degradation entgegengewirkt. Dadurch wird ein Heizelement bereitgestellt, welches eine entsprechende Thermoschockstabilität und eine mechanische Haftung auf dem Trägermaterial ermöglicht. Durch die Wärmebehandlung beziehungsweise durch das Erhitzen wird ergänzend bei der ersten Schicht und der Schutzschicht eine Komprimierung der Schichten erzielt. Dies weist den Vorteil auf, dass solche Hochtemperaturheizelemente luft- beziehungsweise sauerstoffdicht komprimiert werden. Dadurch kann auch die Temperaturstabilität der eindispergierten Carbon-Nanotubes erzielt werden.This method makes it possible to produce a very thin heating element which can be heated up very quickly and allows a uniform heat transfer to the carrier material. The heat treatment process after applying the first layer and the protective layer has surprisingly revealed that the carbon nanotube selected as the conductive material is temperature resistant in the first layer and the protective layer can be introduced and burning is avoided. By using a silicate as a protective layer, the carbon nanotubes dispersed in the base material can be completely incorporated or protected from the environment, so that especially at elevated temperatures oxidation protection of the carbon nanotubes is given, since they begin to degrade at these high temperatures , By penetrating the protective layer and the subsequent compression of this degradation is counteracted. As a result, a heating element is provided which enables a corresponding thermal shock stability and a mechanical adhesion to the carrier material. By the heat treatment or by heating, in addition to the first layer and the protective layer, a compression of the layers is achieved. This has the advantage that such Hochtemperaturheizelemente be compressed air or oxygen tight. As a result, the temperature stability of the dispersed carbon nanotubes can be achieved.

Nach einer bevorzugten Ausgestaltung des Verfahrens ist vorgesehen, dass die zumindest eine Schicht mit Kontaktelementen kontaktiert und die auf dem Trägermaterial aufgebrachten Schichten erhitzt werden. Dadurch kann eine erhöhte mechanische Haftung zwischen dem Kontaktelement und dem Trägermaterial erzielt werden.According to a preferred embodiment of the method, it is provided that the at least one layer is contacted with contact elements and the layers applied to the carrier material are heated. As a result, an increased mechanical adhesion between the contact element and the carrier material can be achieved.

Eine weitere bevorzugte Ausgestaltung des Verfahrens sieht vor, dass die Kontaktelemente streifenförmig sind. Dadurch kann eine flächenförmige Aufheizung erzielt werden.A further preferred embodiment of the method provides that the contact elements are strip-shaped. As a result, a sheet-like heating can be achieved.

Nach einer bevorzugten Ausgestaltung des Verfahrens ist vorgesehen, dass die aufgebrachte erste Schicht und Schutzschicht insbesondere auf eine Temperatur zwischen 300 °C bis 700 °C erhitzt wird. Durch diese Temperaturbehandlung erfolgt ein Sinterprozess der Schichten. Dadurch kann insbesondere eine Komprimierung der Schichten erfolgen. Dies weist den Vorteil auf, dass solche Hochtemperaturheizungen durch den Sinterprozess luftsauerstoffdicht komprimiert werden und somit für einen Betrieb bei Temperaturen von > 400 °C geeignet und beständig sind.According to a preferred embodiment of the method is provided that the applied first layer and protective layer is heated in particular to a temperature between 300 ° C to 700 ° C. By this temperature treatment, a sintering process of the layers takes place. This can be done in particular a compression of the layers. This has the advantage that such high-temperature heaters are compressed by the sintering oxygen-tight and thus suitable for operation at temperatures of> 400 ° C and are resistant.

Eine bevorzugte Ausgestaltung des Verfahrens sieht vor, dass die erste Schicht nach dem Aufbringen getrocknet und anschließend die Schutzschicht aufgebracht wird. Dieser Trocknungsvorgang weist den Vorteil auf, dass die erste Schicht zumindest geringfügig komprimiert wird, insbesondere wasserlösliche Bestandteile ausdampfen können, bevor die weitere Schutzschicht aufgetragen wird. Dadurch kann ein dünner Aufbau des Heizungselementes begünstigt werden.A preferred embodiment of the method provides that the first layer is dried after application and then the protective layer is applied. This drying process has the advantage that the first layer is at least slightly compressed, in particular water-soluble constituents can evaporate before the further protective layer is applied. As a result, a thin structure of the heating element can be favored.

Nach einer weiteren bevorzugten Ausgestaltung des Verfahrens ist vorgesehen, dass die erste Schicht und getrennt davon die Schutzschicht oder die Funktionsschicht durch ein Sprühverfahren durch Aufrakeln oder ein Druckverfahren aufgebracht werden. Beispielsweise kann ein Siebdruckverfahren vorgesehen sein, durch welches die insbesondere pastöse erste Schicht in einfacher Weise auf das Trägermaterial aufgebracht wird. Anschließend kann in gleicher Weise die ebenfalls bevorzugt pastös ausgebildete zweite Schutzschicht aufgetragen werden. Somit können bekannte Technologien für die Herstellung von Hochtemperaturheizelementen eingesetzt werden. Alternativ kann ein Spritzverfahren bzw. ein Sprühverfahren vorgesehen sein, um die erste und zweite Schicht das Trägermaterial aufzubringen. Hier kann ein sogenanntes Spraycoating, ein Dipcoating, also eine Tauchbeschichtung oder ein Spincoating realisiert werden.According to a further preferred embodiment of the method, it is provided that the first layer and separately the protective layer or the functional layer are applied by a spray method by knife coating or a printing process. For example, a screen printing method can be provided, by which the in particular pasty first layer is applied in a simple manner to the carrier material. Subsequently, the likewise preferred pasty trained second protective layer can be applied in the same way. Thus, known technologies can be used for the production of high-temperature heating elements. Alternatively, a spraying method or a spraying method may be provided in order to apply the first and second layer to the carrier material. Here, a so-called spray coating, a dip coating, so a dip coating or a spin coating can be realized.

Eine weitere bevorzugte Ausgestaltung des Verfahrens sieht vor, dass die erste Schicht vollflächig oder in nebeneinander liegenden Streifen aufgebracht wird, die Schutzschicht vollflächig auf die erste Schicht aufgebracht wird und diese vollständig zum Trägermaterial umhüllt, wobei insbesondere vor oder nach dem Aufbringen der ersten Schicht streifenförmige Kontaktelemente aufgebracht werden. Dadurch wird die erste Schicht als elektrisch leitfähige Schicht mit den streifenförmigen Kontaktelementen verbunden und anschließend eine elektrische Isolierung durch die Schutzschicht mit Ausnahme von Anschlussstellen an den streifenförmigen Kontaktelementen ermöglicht. Durch die vollständige Umhüllung der ersten elektrisch leitfähigen Schicht durch die Schutzschicht wird des Weiteren ermöglicht, dass für die Herstellung der ersten elektrisch leitfähigen Schicht wasserlösliche Materialien als Basis für eine Dispersion eingesetzt werden können. Diese weisen wiederum den Vorteil auf, dass eine Verarbeitung ohne den Einsatz von Lösungsmitteln möglich und somit gesundheitlich unbedenklich ist.A further preferred embodiment of the method provides that the first layer is applied over the entire surface or in adjacent strips, the protective layer is applied over the entire surface of the first layer and this completely envelopes the substrate, in particular before or after the application of the first layer strip-shaped contact elements be applied. Thereby, the first layer is connected as an electrically conductive layer with the strip-shaped contact elements and then allows electrical insulation through the protective layer with the exception of connection points on the strip-shaped contact elements. The complete encapsulation of the first electrically conductive layer by the protective layer further makes it possible to use water-soluble materials as the basis for a dispersion for the production of the first electrically conductive layer. These in turn have the advantage that processing without the use of solvents is possible and thus harmless to health.

Eine weitere bevorzugte Ausgestaltung des Verfahrens sieht vor, dass vor dem Aufbringen der ersten Schicht auf das Trägermaterial im Erwärmungsbereich eine elektrisch isolierende Schicht auf das Trägermaterial aufgebracht wird. Dies erfolgt insbesondere dann, wenn das Trägermaterial nicht aus einem dielektrischen Material, sondern aus einem elektrisch leitfähigen oder schwach elektrisch leitfähigem Material, hergestellt ist.A further preferred embodiment of the method provides that before applying the first layer to the carrier material in the heating region, an electrically insulating layer is applied to the carrier material. This is done in particular when the carrier material is not made of a dielectric material, but of an electrically conductive or weakly electrically conductive material.

Eine bevorzugte Ausführung des Verfahrens sieht vor, dass zur Herstellung der ersten Schicht als elektrisch nicht leitfähiges Grundmaterial eine wässrige Lösung, insbesondere Wasser oder destilliertes Wasser, eingesetzt wird, welches vorzugsweise einen Dispergenten, wie beispielsweise Gummi Arabicum umfasst. Dieser ermöglicht ein einfaches Aufbringen, insbesondere als vollflächige Schicht, ohne Lösungsmittel für die Herstellung der Dispersion als auch für die Reinigung von Maschinen einzusetzen.A preferred embodiment of the method provides that an aqueous solution, in particular water or distilled water, is used for producing the first layer as electrically non-conductive base material, which preferably comprises a dispersant, such as gum arabic. This allows easy application, in particular as a full-surface layer, without using solvents for the preparation of the dispersion as well as for the cleaning of machines.

Eine weitere bevorzugte Ausgestaltung des Verfahrens sieht vor, dass in das elektrisch nicht leitende Grundmaterial Füllstoffe aus Carbon-Nanotubes und/oder Graphit eingearbeitet und diese Paste dann verdruckt werden kann. Der letzte Schritt beschreibt das Aufbringen der Schutzschicht (TopCoat), welche vorzugsweise aus Ethylsilikat mit Graphit besteht.A further preferred embodiment of the method provides that incorporated into the electrically non-conductive base material fillers of carbon nanotubes and / or graphite and this paste can then be printed. The last step describes the application of the protective layer (TopCoat), which preferably consists of ethyl silicate with graphite.

Dabei können bevorzugt Single-, Double- oder Multiwalled-Nanotubes eingesetzt werden. Insbesondere die Kombination von Graphit und Carbon-Nanotubes weist den Vorteil auf, dass eine fließfähige Dispersion für die erste Schicht zum vollflächigen Aufbringen auf ein Trägermaterial erzielt wird.In this case, single, double or multiwalled nanotubes can preferably be used. In particular, the combination of graphite and carbon nanotubes has the advantage that a flowable dispersion for the first layer for full-surface application to a carrier material is achieved.

Nach einer weiteren bevorzugten Ausgestaltung des Verfahrens ist vorgesehen, dass in die Schutzschicht ein Füllmittel, insbesondere Graphit, eindispergiert wird. Dies weist den Vorteil auf, dass insbesondere bei der ersten alternativen Ausführungsform des Verfahrens beim Einpenetrieren der Schutzschicht in die erste elektrisch leitfähige Schicht das Füllstoffverhältnis erhöht wird, wodurch sich auch die Leitfähigkeit in der zweiten Schicht erhöht. Dadurch kann die Kontaktierung zu beliebigen Zeitpunkten aufgebracht und an unterschiedlichen Orten flexibel angebracht werden. Die Schutzschicht dient nicht nur zur Isolierung gegen Luftsauerstoff, durch die Zugabe von Graphit, welches temperaturstabiler an Luft als die CNTs ist, wird ebenso nach der Penetration und der daraus resultierenden Verschiebung der Gewichtsprozentanteile der Füllstoffe eine Funktionsschicht zur effektiven Durchkontaktierung gegeben. Insgesamt hat diese Schicht also drei Merkmale:

  • 1) Haftung durch Penetration; 2) Isolierung gegen Luftsauerstoff; 3) leitfähige, CNT freie Schicht zur Durchkontaktierung.
According to a further preferred embodiment of the method, it is provided that a filler, in particular graphite, is dispersed in the protective layer. This has the advantage that, in particular in the first alternative embodiment of the method when penetrating the protective layer into the first electrically conductive layer, the filler ratio is increased, as a result of which the conductivity in the second layer also increases. As a result, the contacting can be applied at any desired time and flexibly attached to different locations. The protective layer is not only used for insulation against atmospheric oxygen, By the addition of graphite, which is more stable in air temperature than the CNTs, a functional layer for effective via contact is also given after the penetration and the resulting shift of the weight percentages of the fillers. Overall, this layer has three characteristics:
  • 1) liability by penetration; 2) insulation against atmospheric oxygen; 3) conductive, CNT-free layer for via.

Des Weiteren ist bevorzugt vorgesehen, dass in die erste Schicht ein Haftmittel, insbesondere Gummi Arabicum eindispergiert wird. Dadurch kann eine Haftvermittlung zwischen der ersten Schicht und einem Trägermaterial verbessert werden. Das Gummi Arabicum dient vor dem Aufbringen der Schutzschicht (TopCoat) als Haftvermittler. Dadurch ist garantiert, dass beim Aufdrucken der Schutzschicht (TopCoat) dieses nicht die erste Schicht (PreCoat) zerstört.Furthermore, it is preferably provided that an adhesive, in particular gum arabic, is dispersed into the first layer. As a result, an adhesion mediation between the first layer and a carrier material can be improved. The gum arabic is used before the application of the protective layer (TopCoat) as a primer. This guarantees that when printing the protective layer (TopCoat) this does not destroy the first layer (PreCoat).

Während dem Einbrand der Schichten wird das Gummi Arabicum ausgebrannt. Bevor sich die Schutzschicht gasdicht ausbildet, diffundieren die flüchtigen Bestandteile des Gummi Arabicum aus. Alternativ zum Gummi Arabicum sind auch ebenso andere Tenside wie SDS oder Triton denkbar.During the penetration of the layers, the gum arabic is burned out. Before the protective layer forms gas-tight, the volatile constituents of gum arabic diffuse out. As an alternative to gum arabic, other surfactants such as SDS or Triton are also conceivable.

Die Aufgabe wird des Weiteren erfindungsgemäß durch ein Heizelement, insbesondere ein Hochtemperaturheizelement, beispielsweise für thermische Hausgeräte, gelöst, bei dem auf dem Trägermaterial eine erste elektrisch leitfähige Schicht bestehend aus einem Grundmaterial und einem darin eindispergierten Carbon-Nanotube und eine Schutzschicht vorgesehen sind, welche in die erste Schicht penetriert ist und dass die Schutzschicht aus Silikat besteht. Dieser besondere Aufbau des Heizelementes ermöglicht, dass eine hohe Temperaturbeständigkeit sowie die Thermoschockstabilität geschaffen werden kann. Gleichzeitig können dadurch beliebige Geometrien für die Heizelemente auf einem Trägermaterial, insbesondere zur Bildung einer Hochtemperaturheizung, ausgewählt werden.The object is further achieved according to the invention by a heating element, in particular a high-temperature heating element, for example for thermal household appliances, in which a first electrically conductive layer consisting of a base material and a carbon nanotube dispersed therein and a protective layer are provided on the carrier material the first layer is penetrated and that the protective layer consists of silicate. This special design of the heating element allows high temperature resistance and thermal shock stability to be achieved. At the same time, any desired geometries for the heating elements on a carrier material, in particular for forming a high-temperature heating, can thereby be selected.

Eine bevorzugte Ausgestaltung des Heizelementes sieht vor, dass die Schichten mit Kontaktelementen kontaktiert sind. Dadurch kann ein einfacher Anschluss geschaffen sein.A preferred embodiment of the heating element provides that the layers are contacted with contact elements. As a result, a simple connection can be created.

Bevorzugt sind die Kontaktelemente streifenförmig ausgebildet.Preferably, the contact elements are strip-shaped.

Eint weitere bevorzugte Ausgestaltung der Heizung sieht vor, dass die Schichten durch eine Temperaturbehandlung komprimiert sind. Dadurch kann die Temperaturbeständigkeit und/oder Thermoschockstabilität weiter erhöht werden.Eint further preferred embodiment of the heating provides that the layers are compressed by a temperature treatment. As a result, the temperature resistance and / or thermal shock stability can be further increased.

Des Weiteren ist bevorzugt vorgesehen, dass die erste Schicht und die Schutzschicht ein Heizelement mit einer Schichtdicke von weniger als 500 µm, insbesondere weniger als 100 µm, bilden. Aufgrund der Auswahl der Materialien kann ein ultradünnes Auftragen ermöglicht sein. Gleichzeitig kann eine homogene Wärmeerzeugung innerhalb der ersten elektrisch leitfähigen Schicht und somit des Trägermaterials erfolgen.Furthermore, it is preferably provided that the first layer and the protective layer form a heating element with a layer thickness of less than 500 μm, in particular less than 100 μm. Due to the choice of materials, an ultra-thin application may be possible. At the same time, a homogeneous heat generation within the first electrically conductive layer and thus of the carrier material can take place.

Die Heizung weist bevorzugt eine erste Schicht auf, welche eine Konzentration von 0,1 bis 100 wt% CNT im fließfähigen Grundmaterial, insbesondere im Wasser oder destilliertem Wasser, aufweist. Dadurch kann eine hohe elektrische Leitfähigkeit gegeben sein, so dass mit niederen Spannungen gearbeitet werden kann. Bevorzugt ist eine Konzentration von 1 bis 3 wt% CNT und 5 bis 50 wt% Graphit als Füllmittel in dem Grundmaterial vorgesehen. Durch die Hinzugabe von Graphit kann die Fließfähigkeit der ersten Schicht oder des Gemisches erhöht werden.The heater preferably has a first layer, which has a concentration of 0.1 to 100 wt% CNT in the flowable base material, in particular in water or distilled water. This can be given a high electrical conductivity, so that you can work with low voltages. Preferably, a concentration of 1 to 3 wt% CNT and 5 to 50 wt% graphite is provided as a filler in the base material. By adding graphite, the flowability of the first layer or the mixture can be increased.

Das Heizelement weist bevorzugt ein Heizelement mit einer ersten Schicht und einer Schutzschicht auf, welches einen elektrischen Widerstand von weniger als 100 Ohm/Sq. aufweist. Dies ermöglicht eine Temperaturgenerierung von > 400 °C auf großen Substraten mittels einer üblichen Spannungsversorgung im Haushalt. Darüber hinaus könnten die Schichten noch dünner ausgelegt werden, um noch bessere mechanische Stabilitäten zu gewährleisten.The heating element preferably has a heating element with a first layer and a protective layer which has an electrical resistance of less than 100 ohms / sq. having. This allows a temperature generation of> 400 ° C on large substrates by means of a conventional power supply in the home. In addition, the layers could be made even thinner to ensure even better mechanical stabilities.

Zur Herstellung der Heizung ist bevorzugt ein Trägermaterial vorgesehen, welches aus Keramik, Glaskeramik, Cerankeramik, Aluminiumoxidkeramik, MgO, KER 520 besteht. Dadurch werden vielfältige Einsatzbereiche, insbesondere in der Weißen Ware, ermöglicht. Gleichzeitig kann dadurch eine kostengünstige Herstellung erzielt werden.To produce the heating, a carrier material is preferably provided which consists of ceramic, glass ceramic, ceran ceramic, aluminum oxide ceramic, MgO, KER 520. As a result, a variety of applications, especially in the white goods, allows. At the same time, a cost-effective production can be achieved.

Die Erfindung sowie weitere vorteilhafte Ausführungsformen und Weiterbildungen derselben werden im Folgenden anhand der in den Zeichnungen dargestellten Beispiele näher beschrieben und erläutert. Die der Beschreibung und den Zeichnungen zu entnehmenden Merkmale können einzeln für sich oder zu mehreren in beliebiger Kombination erfindungsgemäß angewandt werden. Es zeigen:

Figur 1
eine schematische Schnittdarstellung einer ersten Ausführungsform einer Heizung,
Figur 2
eine schematische Seitenansicht von unten auf die Heizung gemäß Figur 1,
Figur 3
eine schematische Seitenansicht einer alternativen Heizung zu Figur 1 und
Figur 4
eine schematische Seitenansicht einer weiteren alternativen Ausführungsform zu Figur 1.
The invention as well as further advantageous embodiments and developments thereof are described below with reference to the drawings illustrated examples described and explained. The features to be taken from the description and the drawings can be applied individually according to the invention individually or in combination in any combination. Show it:
FIG. 1
a schematic sectional view of a first embodiment of a heater,
FIG. 2
a schematic side view of the bottom of the heater according to FIG. 1 .
FIG. 3
a schematic side view of an alternative heating to FIG. 1 and
FIG. 4
a schematic side view of another alternative embodiment to FIG. 1 ,

In Figur 1 ist eine schematische Seitenansicht einer Heizung 11, insbesondere einer Hochtemperaturheizung dargestellt. Figur 2 zeigt eine schematische Ansicht von unten. Die Hochtemperaturheizung 11 umfasst ein Trägermaterial 12, welches beispielsweise beim Einsatz im Bereich der Weißen Ware als Keramik, Glaskeramik, Cerankeramik, Aluminiumoxidkeramik oder dergleichen ausgebildet sein kann. Auf deren Unterseite ist innerhalb eines Erwärmungsbereiches ein Heizelement 14 vorgesehen. Dieses Heizelement 14 umfasst eine erste elektrisch leitfähige Schicht 16, auf der eine Schutzschicht 17 aufgebracht ist. Bevorzugt umgibt die Schutzschicht 17 vollständig die erste elektrische Schicht 16, so dass diese elektrisch isoliert und mechanisch geschützt gegenüber der Umgebung an dem Trägermaterial 12 vorgesehen ist. Die erste elektrisch leitfähige Schicht 16 erstreckt sich zwischen zwei streifenförmigen Kontaktelementen 18, welche zur Kontaktierung der elektrischen Schicht 16, beispielsweise bis an einen Randbereich des Trägermaterials 12, geführt sind. Zwischen den beiden bevorzugt parallel zueinander verlaufenden Kontaktelementen 18 erstreckt sich die erste Schicht 16 und bildet den Erwärmungsbereich. Die Schutzschicht 17 überdeckt die erste Schicht 16 und bevorzugt die streifenförmigen Kontaktelemente 18, so dass lediglich beispielsweise im Randbereich eine freie Kontaktierungsstelle ausgespart sein kann. Alternativ kann auch vorgesehen sein, dass zunächst die erste Schicht 16 und die Schutzschicht 17 aufgebracht wird und anschließend die streifenförmigen Kontaktelemente 18 zu dem durch die erste Schicht 16 und Schutzschicht 17 gebildeten Erwärmungsbereich gebracht werden.In FIG. 1 is a schematic side view of a heater 11, in particular a high-temperature heating shown. FIG. 2 shows a schematic view from below. The high-temperature heating 11 comprises a carrier material 12, which may be formed, for example, when used in the field of white goods as ceramics, glass ceramic, Cerankeramik, alumina ceramics or the like. On the underside of a heating element 14 is provided within a heating area. This heating element 14 comprises a first electrically conductive layer 16, on which a protective layer 17 is applied. Preferably, the protective layer 17 completely surrounds the first electrical layer 16, so that it is electrically insulated and mechanically protected against the environment on the substrate 12 is provided. The first electrically conductive layer 16 extends between two strip-shaped contact elements 18, which are guided for contacting the electrical layer 16, for example, to an edge region of the carrier material 12. Between the two preferably parallel to each other extending contact elements 18, the first layer 16 extends and forms the heating area. The protective layer 17 covers the first layer 16 and preferably the strip-shaped contact elements 18, so that only for example in the edge region a free contact point can be recessed. Alternatively, it can also be provided that initially the first layer 16 and the protective layer 17 are applied and then the strip-shaped contact elements 18 are brought to the heating zone formed by the first layer 16 and protective layer 17.

Die erste elektrisch leitfähige Schicht 16 besteht aus einem fließfähigen, elektrisch nicht leitfähigen Grundmaterial. Bevorzugt ist eine Dispersion auf wässriger Basis vorgesehen. In dieser Dispersion sind als elektrisch leitfähiges Material Carbon-Nanotubes dispergiert. Ergänzend umfasst die Dispersion ein Füllmittel, insbesondere Graphit, um die elektrische Leitfähigkeit zu unterstützen und die Fließfähigkeit einzustellen. Ergänzend ist bevorzugt in der Dispersion ein Haftmittel vorgesehen. Dieses kann beispielsweise Gummi Arabicum sein. Auch andere Tenside wie SDS oder Triton sind einsetzbar. Dadurch kann eine fließfähige oder pastöse Masse hergestellt werden, welche durch ein Druckverfahren oder Sprühverfahren auf das Trägermaterial 12 applizierbar ist. Diese Dispersion ist hochtemperatur-, thermoschockstabil und hydrophob. Die Schutzschicht 17 besteht bevorzugt aus einem Silikat, das bevorzugt mit Haftmittel, Füllmittel oder weiteren Partikeln angereichert sein kann, um die Haftungseigenschaften zu erhöhen. Dadurch kann die Thermoschockstabilität sowie die mechanische Haftung auf dem Trägermaterial verbessert werden. Durch das Penetrieren der Schutzschicht 17 in die erste Schicht 16 sind diese CNT's auch für einen Temperatureinsatz oberhalb von 350 °C geeignet, da die Schutzschicht 17 die CNT's luftdicht einschließt. Bevorzugt besteht das elektrisch leitfähige Material aus einem Verbund aus CNT's und Graphit oder weiteren elektrisch leitfähigen Partikeln oder Bestandteilen, die das Ausbilden einer pastösen Masse oder einer sprühfähigen Masse ermöglichen.The first electrically conductive layer 16 consists of a flowable, electrically non-conductive base material. Preferably, an aqueous-based dispersion is provided. Carbon nanotubes are dispersed in this dispersion as an electrically conductive material. In addition, the dispersion comprises a filler, in particular graphite, in order to support the electrical conductivity and to adjust the flowability. In addition, an adhesive is preferably provided in the dispersion. This may be, for example, gum arabic. Other surfactants such as SDS or Triton can be used. As a result, a flowable or pasty mass can be produced, which can be applied to the carrier material 12 by a printing process or spraying process. This dispersion is high-temperature, thermoshock-stable and hydrophobic. The protective layer 17 is preferably made of a silicate, which may preferably be enriched with adhesive, filler or other particles in order to increase the adhesion properties. As a result, the thermal shock stability and the mechanical adhesion to the substrate can be improved. By penetrating the protective layer 17 into the first layer 16, these CNTs are also suitable for use at temperatures above 350 ° C., since the protective layer 17 encloses the CNTs airtight. The electrically conductive material preferably consists of a composite of CNTs and graphite or further electrically conductive particles or constituents which make it possible to form a pasty mass or a sprayable mass.

Das in Figur 1 dargestellte Heizelement 14 wird dadurch hergestellt, dass zunächst die Bestandteile aus einem elektrisch nicht leitfähigen Grundmaterial und darin dispergiertem Carbon-Nanotubes oder ein Verbund aus Carbon-Nanotubes mit weiteren elektrisch leitfähigen Materialien gemischt werden, um eine fließfähige oder pastöse Masse zu bilden, die mittels eines Siebdruckverfahrens vollflächig auf das Trägermaterial 12 aufgebracht wird. Anschließend können die streifenförmigen Kontaktelemente 18 vorzugsweise durch Auftragen einer leitfähigen Paste, insbesondere Silberleitpaste, im Siebdruckverfahren aufgedruckt werden. Diese Kontaktelemente 18 können auch vor dem Aufbringen der ersten Schicht 16 auf dem Trägermaterial 12 vorgesehen sein. Darauf folgend kann gemäß einer Variante der ersten Ausführungsform des Herstellungsverfahrens diese erste Schicht 16 temperaturbehandelt werden. Dies weist den Vorteil auf, dass eine Aushärtung und Austrocknung des Grundmaterials beziehungsweise der wässrigen Basis für die als Dispersion ausgebildete erste Schicht 16 erfolgt, wodurch eine anschließende Penetration der Schutzschicht 17 verbessert wird. Anschließend wird die Schutzschicht 17 bevorzugt durch ein Siebdruckverfahren aufgebracht. Alternativ kann diese auch ohne einen dazwischengeschalteten Trocknungsvorgang der ersten Schicht 16 aufgebracht werden. Anschließend wird das Trägermaterial 12 mit den darauf aufgebrachten Schichten 17 als auch den Kontaktelementen 18 temperaturbehandelt, so dass zumindest die Schutzschicht 17 vorzugsweise gesintert wird. Hier findet die Komprimierung statt und bedingt ein weiteres "Zusammenpressen" der leitfähigen Partikel, was wegen der erhöhten Berührungsanzahl und der Kompaktheit zu einem geringeren spez. Widerstand führt. Dadurch kann wiederum eine Leitfähigkeitsverbesserung in der ersten Schicht 16 geschaffen werden.This in FIG. 1 shown heating element 14 is prepared by first mixing the components of an electrically non-conductive base material and carbon nanotubes dispersed therein or a composite of carbon nanotubes with other electrically conductive materials to form a flowable or pasty mass, which by means of a Screen printing process is applied over the entire surface of the substrate 12. Subsequently, the strip-shaped contact elements 18 can preferably be printed by applying a conductive paste, in particular silver conductive paste, by screen printing. These contact elements 18 can also be provided on the carrier material 12 before the application of the first layer 16. Following this For example, according to a variant of the first embodiment of the production method, this first layer 16 can be subjected to temperature treatment. This has the advantage that hardening and drying of the base material or the aqueous base takes place for the first layer 16 formed as a dispersion, whereby a subsequent penetration of the protective layer 17 is improved. Subsequently, the protective layer 17 is preferably applied by a screen printing method. Alternatively, this can also be applied without an intervening drying process of the first layer 16. Subsequently, the carrier material 12 is treated with the layers 17 applied thereto as well as the contact elements 18, so that at least the protective layer 17 is preferably sintered. Here the compression takes place and requires a further "compression" of the conductive particles, which due to the increased number of contacts and the compactness to a lower spec. Resistance leads. This in turn can be used to create a conductivity improvement in the first layer 16.

Solche Hochtemperaturheizungen 11 weisen Heizelemente 14 auf, deren Dicke beispielsweise < 100 µm ausgebildet sein können. Darüber hinaus wird aufgrund der vollflächigen Anordnung der elektrisch leitfähigen Schicht 16 an dem Trägermaterial 12 eine homogene Erwärmung und Wärmestrahlung des Trägermaterials 12 ermöglicht.Such high-temperature heaters 11 have heating elements 14, the thickness of which may be formed, for example, <100 μm. In addition, due to the full-surface arrangement of the electrically conductive layer 16 on the carrier material 12, a homogeneous heating and thermal radiation of the carrier material 12 is made possible.

Bevorzugt kann der Schutzschicht 17 ein Reflektor zugeordnet sein, um die vom Heizelement 14 in entgegengesetzter Richtung zum Trägermaterial 12 erfolgende Wärmestrahlung zu reflektieren und das Aufheizen des Trägermaterials 12 zu beschleunigen.Preferably, the protective layer 17 may be associated with a reflector to reflect the heat radiation from the heating element 14 in the opposite direction to the carrier material 12 and to accelerate the heating of the carrier material 12.

In Figur 3 ist eine alternative Ausführungsform zu Figur 1 dargestellt. Diese Ausführungsform weicht dahingehend von der in Figur 1 ab, dass vor dem Aufbringen der ersten elektrisch leitfähigen Schicht 16 eine elektrische Isolierschicht 19 vollflächig auf dem Trägermaterial 12 aufgebracht wird, um die elektrisch leitfähige Schicht 16 gegenüber dem Trägermaterial 12 isoliert anzuordnen. Diese Anordnung der Isolierschicht 19 kann ebenfalls beim Aufbringen eines Gemisches bestehend aus der ersten elektrisch leitfähigen Schicht 16 und der Schutzschicht 17 vorgesehen sein. Ebenso kann vor dem Aufbringen der Funktionsschicht 21 auf das Trägermaterial eine elektrisch isolierende Schicht 19 vollflächig aufgebracht werden.In FIG. 3 is an alternative embodiment to FIG. 1 shown. This embodiment differs from that in FIG FIG. 1 from that prior to the application of the first electrically conductive layer 16, an electrical insulating layer 19 is applied over the entire surface of the carrier material 12 in order to arrange the electrically conductive layer 16 relative to the carrier material 12 in isolation. This arrangement of the insulating layer 19 may also be provided when applying a mixture consisting of the first electrically conductive layer 16 and the protective layer 17. Likewise, before applying the functional layer 21 on the substrate an electrically insulating layer 19 are applied over the entire surface.

In Figur 4 ist eine alternative Ausführungsform zu Figur 1 dargestellt. Diese Ausführungsform unterscheidet sich lediglich dadurch, dass anstelle einer vollflächigen ersten elektrisch leitfähigen Schicht 16 eine streifenförmige Schicht 16 gebildet ist. Solche Stege oder Rippen können in der Geometrie und der Kontur an die entsprechenden Anwendungsfälle angepasst werden. Die Streifengeometrie kann gezielte Bereiche aufheizen. Darüber hinaus begünstigt sie weiterhin die Haftungseigenschaften an dem jeweiligen Substrat. Die Streifen können beliebig angeordnet werden, so dass auf einem Substrat gezielt verschiedene Heizzonen implementiert werden können.In FIG. 4 is an alternative embodiment to FIG. 1 shown. This embodiment differs only in that instead of a full-surface first electrically conductive layer 16, a strip-shaped layer 16 is formed. Such webs or ribs can be adapted in geometry and contour to the corresponding applications. The strip geometry can heat targeted areas. In addition, it further favors the adhesion properties of the respective substrate. The strips can be arranged as desired, so that different heating zones can be implemented on a substrate in a targeted manner.

Claims (17)

  1. Method for producing a heating installation, particularly for thermal household appliances, in which a layer generating heat by electricity flow is provided on a substrate (12) as a heating element (14), and on the substrate (12), a first electrically conductive layer (16) is applied, which is formed from a flowable base material, and carbon nanotubes dispersed therein, characterised in
    - that on this first layer (16), a protective layer (17) is applied, which by means of the application onto the first layer (16) penetrates into this,
    - that the layers (16, 17) are compressed by temperature-treatment and
    - that for producing the protective layer (17), a silicate is used to form an inorganic layer.
  2. Method according to claim 1, characterised in that the at least one layer (16, 17) contacts with preferably strip-shaped contact elements (18), and the layers (16, 17), applied to the substrate, are heated, in particular are only heated by applying a voltage to the contact elements (18).
  3. Method according to any one of the preceding claims, characterised in that the layers (16, 17), applied on the substrate (12), are heated to a temperature of 300 °C to 700 °C.
  4. Method according to claim 1, characterised in that the first electrically conductive layer (16) is dried after application on the substrate (12), and the protective layer (17) is subsequently applied.
  5. Method according to any one of the preceding claims, characterised in that the first electrically conductive layer (16), and, separately, the protective layer (17) are applied by a spraying process, by squeegee or a printing process.
  6. Method according to any one of the preceding claims, characterised in that the first electrically conductive layer (16) is applied onto the substrate (12) over the whole area or in strips, whereby the protective layer (17) is subsequently applied onto the first layer (16) over the whole area, and covering the substrate (12), whereby before or after the application of the first electrically conductive layer (16) or protective layer (17), strip-shaped contact elements (18) are applied on the substrate (12).
  7. Method according to any one of the preceding claims, characterised in that before the application of the first electrically conductive layer (16) in the heating region, an electrically insulating layer (19) is applied onto the substrate (12).
  8. Method according to any one of the preceding claims, characterised in that for producing a first electrically conductive layer (16), as a non- electrically conductive, flowable base material, an aqueous solution, particularly water or distilled water is used, which preferably includes a dispergent, such as gum arabic, for example.
  9. Method according to any one of the preceding claims, characterised in that carbon nanotubes and/or graphite are dispersed as an electrically conductive, flowable material into the base material, of the first electrically conductive layer (16).
  10. Method according to claim 1, characterised in that a filler, particularly graphite, is dispersed into the protective layer (17).
  11. Method according to claim 1, characterised in that an adhesive agent, particularly gum arabic, is dispersed into the first layer (16).
  12. Heating installation, particularly high-temperature heating installation, in particular for household appliances, which comprise a layer generating heat by electricity flow on a substrate (12) as a heating element (11), characterised in that on the substrate (12), a first electrically conductive layer (16) consisting of a base material and carbon nanotubes dispersed therein and a protective layer (17) is provided, which is penetrated into the first layer (16), and that the protective layer (17) consists of silicate.
  13. Heating installation according to claim 12, characterised in that the layers (16, 17) are contacted with particularly strip-shaped contact elements (18).
  14. Heating installation according to claim 12 or 13, characterised in that the first and second layer (16, 17) comprise a layer thickness of less than 500 µm, particularly less than 100 µm.
  15. Heating installation according to claim 12 to 14, characterised in that the first electrically conductive layer (16) has a concentration of 0.1 to 100 wt% carbon nanotubes in the flowable base material, or that a matrix of a concentration of 1 to 3 wt% carbon nanotubes and 5 to 50 wt% graphite is provided in the base material.
  16. Heating installation according to claim 12 to 15, characterised in that the heating element (14) produced by the first and second layer (16, 17) has an electrical resistance of less than 100 Ω/Sq.
  17. Heating installation according to claim 12 to 16, characterised in that the substrate (12) consists of ceramic, glass ceramic, Ceran ceramic, aluminium oxide ceramic, MgO, KER500.
EP10736624.7A 2009-07-21 2010-07-19 Heater, in particular high-temperature heater, and method for the production thereof Active EP2457412B1 (en)

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DE102009034307A DE102009034307A1 (en) 2009-07-21 2009-07-21 High temperature heating and process for its production
PCT/EP2010/004389 WO2011009577A1 (en) 2009-07-21 2010-07-19 Heater, in particular high-temperature heater, and method for the production thereof

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US20120118873A1 (en) 2012-05-17
EP2457412A1 (en) 2012-05-30
US10149350B2 (en) 2018-12-04
SI2457412T1 (en) 2013-08-30
US9578691B2 (en) 2017-02-21
DE102009034307A1 (en) 2011-01-27
ES2422704T3 (en) 2013-09-13
PL2457412T3 (en) 2013-09-30
WO2011009577A1 (en) 2011-01-27
US20170150552A1 (en) 2017-05-25
KR20120038998A (en) 2012-04-24

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