EP1800764B1 - Process for coating graphite foils - Google Patents
Process for coating graphite foils Download PDFInfo
- Publication number
- EP1800764B1 EP1800764B1 EP20060125967 EP06125967A EP1800764B1 EP 1800764 B1 EP1800764 B1 EP 1800764B1 EP 20060125967 EP20060125967 EP 20060125967 EP 06125967 A EP06125967 A EP 06125967A EP 1800764 B1 EP1800764 B1 EP 1800764B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- graphite foil
- coated
- coating material
- particles
- 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.)
- Not-in-force
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/06—Applying particulate materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/08—Plant for applying liquids or other fluent materials to objects
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Beschichten von flächigen Gebilden aus Graphitfolie mit einer eine Flachseite und die Kanten bedeckenden Schutz- bzw. Isolierschicht.The present invention relates to a method for coating flat structures made of graphite foil with a flat side and the edges covering protective or insulating layer.
Mit Schutz- bzw. Isolierschichten aus einem Thermoplast beschichtete Artikel aus Graphitfolie und Verfahren zum Aufbringen derartiger Schutzschichten sind aus der Patentanmeldung
Kritisch für alle vorgeschlagenen Verfahren ist, dass eine geringe Dicke (maximal 0,025 mm) der aufzutragenden Schicht gewünscht ist, wobei diese Schicht über die gesamte zu beschichtende Oberfläche gleichmäßig dünn sein soll, und dass neben mindestens einer Flachseite des Artikels aus Graphitfolie auch die Kantenflächen, welche aufgrund der Dicke der Graphitfolie Höhen von 0,25 bis 1,5 mm aufweisen, mitbeschichtet werden sollen.
Häufig wird nur auf einer der Flachseiten des Artikels aus Graphitfolie eine Beschichtung benötigt. Für diese Variante wird im folgenden die zu beschichtende Flachseite als Vorderseite bezeichnet, und im Gegensatz dazu die andere, unbeschichtete Flachseite als Rückseite.With protective or insulating layers of a thermoplastic coated articles of graphite foil and methods for applying such protective layers are disclosed in the patent application
Critical for all proposed methods is that a small thickness (maximum 0.025 mm) of the layer to be applied is desired, this layer should be evenly thin over the entire surface to be coated, and that in addition to at least one flat side of the article made of graphite foil and the edge surfaces, which have due to the thickness of the graphite foil heights of 0.25 to 1.5 mm, to be coated.
Often, only one of the flat sides of the graphite foil article requires a coating. For this variant, the flat side to be coated is referred to as the front side, and in contrast, the other, uncoated flat side as the back.
Eine Beschichtung im Sprühverfahren kann beispielsweise mit einem als Pulver oder als Schmelze vorliegenden Material erfolgen. Sprüht man die Kantenflächen direkt an, so ergibt sich durch den dabei unvermeidbaren Overspray (überschüssigen Materialauftrag) auf die Vorderseite des Werkstücks neben einem erhöhten Materialverbrauch auch eine unerwünschte Erhöhung der Dicke der Sprühschicht an der Vorderseite des Werkstücks.
Soll der die Kantenbeschichtung einschließende Sprühprozess automatisiert werden, so müsste der Sprühapparat zusätzlich zu den Bewegungsachsen in x- und in y-Richtung, d.h. parallel zur Vorderseite des zu beschichtenden Werkstücks, für die Beschichtung der Kanten eine zusätzliche Bewegungsachse in z-Richtung parallel zur Höhenausdehnung (Dicke) des zu beschichtenden Werkstücks aufweisen.A coating in the spraying process can be carried out, for example, with a material present as a powder or as a melt. If the edge surfaces are sprayed directly on, the unavoidable overspray on the front side of the workpiece results in an increased material consumption as well as an undesirable increase in the thickness of the spray layer on the front side of the workpiece.
If the spraying process including the edge coating is to be automated, the spraying apparatus would have to have an additional movement axis in the z-direction parallel to the vertical extent in addition to the axes of movement in the x and y directions, ie parallel to the front of the workpiece to be coated Have (thickness) of the workpiece to be coated.
Die Aufgabe der vorliegenden Erfindung besteht darin, ein Sprühverfahren zur Beschichtung flächiger Gebilde aus Graphitfolie mit einer eine Flachseite und die Kantenflächen bedeckenden Schutz-, Isolier- oder sonstigen Funktionsschicht bereit zu stellen, welches die vorgenannten Nachteile des Standes der Technik überwindet.The object of the present invention is to provide a spray process for coating flat structures made of graphite foil with a flat side and the edge surfaces covering protective, insulating or other functional layer, which overcomes the aforementioned disadvantages of the prior art.
Diese Aufgabe wird erfindungsgemäß gelöst, indem das Beschichtungsmaterial durch elektrostatisches Pulversprühen gefolgt von einem Sinterzyklus bzw. einem Aufschmelz-zyklus auf die zu beschichtende Flachseite (Vorderseite) des flächigen Gebildes aus Graphitfolie aufgetragen wird, wobei während des Sprühens das flächige Gebilde aus Graphitfolie auf einer begrenzten Fläche nahezu in der Mitte seiner der Sprührichtung abgewandten Rückseite elektrisch kontaktiert wird. Begrenzte Fläche bedeutet hier mindestens 5 mm von den Rändern entfernt.
Aufgrund der Schichtebenenstruktur des Graphits ist die elektrische Leitfähigkeit in der Folienebene signifikant höher als senkrecht zur Folienebene. Durch diese Anisotropie der elektrischen Leitfähigkeit der Graphitfolie bildet sich ein Feldlinienverlauf aus, der geeignet ist, eine Mitbeschichtung der Kantenflächen zu bewirken. Daher sind bei der erfindungsgemäßen Verfahrensweise nur zwei Bewegungsachsen (in x- und in y-Richtung) für die Sprühvorrichtung erforderlich.This object is achieved by applying the coating material by electrostatic powder spraying followed by a sintering cycle or a melting cycle on the flat side to be coated (front side) of the sheet-like structure made of graphite foil, wherein during the spraying the sheet-like structure of graphite foil on a limited Surface is contacted almost in the middle of its back facing away from the spraying direction electrically. Limited area here means at least 5 mm away from the edges.
Due to the layer plane structure of the graphite, the electrical conductivity in the film plane is significantly higher than perpendicular to the film plane. As a result of this anisotropy of the electrical conductivity of the graphite foil, a field line pattern is formed which is suitable for co-coating the edge surfaces. Therefore, in the method of the invention, only two axes of movement (in the x and y directions) are required for the spray device.
Die Technik der elektrostatischen Pulverbeschichtung als solche ist in der Fachwelt bekannt.
Sie beruht auf der Tatsache, dass sich Körper mit entgegengesetzter elektrischer Ladung anziehen. Zwischen dem Sprühkopf und dem geerdeten Werkstück bildet sich ein elektrisches Feld. Die Pulverpartikel folgen dessen Feldlinien und bleiben aufgrund der Restladung auf dem Werkstück haften. So setzt sich das Pulver an der Oberfläche des Werkstücks ab und dringt selbst in kleinste mikrofeine Unebenheiten der Oberfläche ein.
In diesem Zustand muss das beschichtete Werkstück für kurze Zeit bei 160 bis 280 °C ca. 15 bis 30 Minuten lang "eingebacken" werden. Temperatur und Dauer dieses sogenannten Backprozesses hängen von der Zusammensetzung der gewählten Beschichtung ab. Während dieses Prozesses kommt es zu einem Zusammensintern aufgesprühten Partikel bzw. zu einem Zusammenschmelzen der aufgesprühten Partikel zu einer hochviskosen Schmelze, so dass eine zusammenhängende, gleichmäßige, in sich geschlossene Oberflächenbeschichtung entsteht.
Danach wird das beschichtete Werkstück erkalten gelassen.As such, the art of electrostatic powder coating is known in the art.
It is based on the fact that bodies attract with opposite electric charge. An electric field forms between the spray head and the grounded workpiece. The powder particles follow its field lines and adhere to the workpiece due to the residual charge. Thus, the powder settles on the surface of the workpiece and penetrates even in the smallest microfine unevenness of the surface.
In this condition, the coated workpiece must be baked for a short time at 160 to 280 ° C for about 15 to 30 minutes. Temperature and duration of this so-called baking process depend on the composition of the selected coating. During this process, particles sprayed together on sintering together or the particles sprayed together melt to form a highly viscous melt, so that a coherent, uniform, self-contained surface coating is formed.
Thereafter, the coated workpiece is allowed to cool.
Der gesamte vorstehend beschriebene Prozess umfassend die Erwärmung auf die Schmelz- bzw. Sintertemperatur, die Haltezeit bei dieser Temperatur und die anschließende Abkühlung unter Verfestigung der Beschichtung wird hier als Sinter- bzw. Aufschmelzzyklus bezeichnet. Üblicherweise dienen so erzeugte Schichten, beispielsweise auf Werkstücken aus Metall, zum Korrosionsschutz oder als Dekorschicht. Die typischen Schichtdicken liegen im Bereich von 0,1 bis 0,2 mm, um die erwähnten Effekte zu erzielen.The entire process described above, including heating to the melting or sintering temperature, the holding time at this temperature and the subsequent cooling to solidify the coating, are referred to herein as the sintering cycle. Usually, layers produced in this way, for example on workpieces made of metal, serve for corrosion protection or as a decorative layer. The typical layer thicknesses are in the range of 0.1 to 0.2 mm in order to achieve the mentioned effects.
Grundsätzlich sind bei der elektrostatischen Pulversprühtechik die gleichen Probleme (Overspray, Notwendigkeit einer weiteren Bewegungsachse für die Kantenbeschichtung etc.) wie bei herkömmlichen Sprühtechniken zu erwarten. Diese Probleme lassen sich jedoch bei der Beschichtung flächiger Gebilde aus Graphitfolie durch die erfindungsgemäße Positionierung und Dimensionierung des elektrischen Kontakts vermeiden.In principle, the same problems (overspray, necessity of a further movement axis for the edge coating, etc.) in electrostatic powder spraying technology are to be expected as with conventional spraying techniques. However, these problems can be avoided in the coating of sheet-like structures made of graphite foil by the positioning and dimensioning of the electrical contact according to the invention.
Die zu beschichtenden flächigen Gebilde aus Graphitfolie können beispielsweise quadratisch oder rechteckig sein, jedoch sind selbstverständlich auch andere geometrische Formen möglich, je nach Einsatzzweck.
Das erfindungsgemäße Verfahren wird beispielsweise benutzt, um flächige Gebilde aus Graphitfolie, die als Wärmeableiter (sog. heat spreader oder thermal interface) in elektronischen Geräten eingesetzt werden, mit einer Schutzschicht zu versehen, welche das Herausbrechen, Abblättern oder Abplatzen von Graphitpartikeln von der Oberfläche bzw. den Kanten der Graphitfolie verhindert ("antiflaking"-Beschichtung) oder/und als elektrische Isolierschicht wirkt.
Für diese Zwecke geeignete Beschichtungsmaterialien sind beispielsweise Thermoplaste wie Polyethylen, Polypropylen und Polyester. Besonders bevorzugt ist als Beschichtungsmaterial ein polymeres Bindemittel, welches thermisch leitfähige Partikel enthält. Die thermisch leitfähigen Partikel sind vorzugsweise nicht elektrisch leitfähig. Das enthält beispielsweise als Partikel Bornitrid in einer Menge von 1 bis 15 Gew.-%, wobei insbesondere hexagonales Bornitrid in einer Menge von 5 bis 10 Gew.-% im polymeren Bindemittel enthalten ist.The planar structures of graphite foil to be coated can be, for example, square or rectangular, but of course other geometric shapes are also possible, depending on the intended use.
The method according to the invention is used, for example, to provide sheet-like structures made of graphite foil, which are used as heat conductors (so-called heat spreaders or thermal interface) in electronic devices, with a protective layer which prevents the break-off, peeling or flaking off of graphite particles from the surface or surface prevents the edges of the graphite foil ("antiflaking" coating) or / and acts as an electrical insulating layer.
Suitable coating materials for these purposes are, for example, thermoplastics such as polyethylene, polypropylene and polyester. Particularly preferred as the coating material is a polymeric binder which contains thermally conductive particles. The thermally conductive particles are preferably not electrically conductive. This contains, for example, as particles boron nitride in an amount of 1 to 15 wt .-%, in particular hexagonal boron nitride in an amount of 5 to 10 wt .-% is contained in the polymeric binder.
Bevorzugt beträgt die Schichtdicke nur 5 bis 10 µm, um den Wärmedurchgang so wenig wie möglich zu beeinträchtigen. Durch geeignete Auswahl der Düsen des Sprühkopfes und der Bewegungsgeschwindigkeit der Sprühkopfes lassen sich diese für das elektrostatische Sprühverfahren untypisch niedrigen Schichtdicken erzielen.Preferably, the layer thickness is only 5 to 10 microns in order to affect the heat transfer as little as possible. By suitable selection of the nozzles of the spray head and the speed of movement of the spray head, these can be achieved for the electrostatic spraying atypically low layer thicknesses.
Während des Aufschmelz- bzw. Sinterzyklusses erfolgt eine Aufheizung auf eine Temperatur zwischen 160 und 280 °C. Diese Temperatur wird ca. 15 bis 30 Minuten lang gehalten.During the melting or sintering cycle, heating takes place at a temperature between 160 and 280.degree. This temperature is maintained for about 15 to 30 minutes.
Die Erfindung wird im folgenden anhand von Figuren und Ausführungsbeispielen näher beschrieben.The invention will be described in more detail below with reference to figures and embodiments.
Die Figuren zeigen:
- Figur 1:
- Feldlinienverlauf bei flächiger Kontaktierung an der Rückseite des zu beschichtenden flächigen Gebildes aus Graphitfolie (Vergleichsbeispiel 1)
- Figur 1A:
- Feldlinienverlauf an der Kante des zu beschichtenden flächigen Gebildes aus Graphitfolie (Ausschnitt IA aus
Figur 1 ) - Figur 2:
- Feldlinienverlauf bei punktförmiger Kontaktierung ungefähr in der Mitte der Rückseite eines flächigen Werkstücks aus Metall (Vergleichsbeispiel 2)
- Figur 2A:
- Feldlinienverlauf an der Kante des zu beschichtenden flächigen Werkstücks aus Metall (Ausschnitt IIA aus
Figur 2 ) - Figur 3:
- Feldlinienverlauf bei erfindungsgemäßer punktförmiger Kontaktierung ungefähr in der Mitte der Rückseite des zu beschichtenden flächigen Gebildes aus Graphitfolie (Beispiel 3)
- Figur 3A
- Feldlinienverlauf an der Kante des zu beschichtenden flächigen Gebildes aus Graphitfolie (Ausschnitt IIIA aus
Figur 3 )
- FIG. 1:
- Field line course in the case of areal contacting at the rear side of the sheet-like structure made of graphite foil to be coated (Comparative Example 1)
- FIG. 1A
- Field line profile at the edge of the planar structure to be coated made of graphite foil (detail IA
FIG. 1 ) - FIG. 2:
- Field line course with punctiform contacting approximately in the middle of the rear side of a flat workpiece made of metal (Comparative Example 2)
- FIG. 2A
- Field line profile at the edge of the sheet metal workpiece to be coated (section IIA aus
FIG. 2 ) - FIG. 3:
- Field line course in point-like contacting according to the invention approximately in the middle of the rear side of the sheet-like structure made of graphite foil to be coated (Example 3)
- FIG. 3A
- Field line profile at the edge of the planar structure to be coated made of graphite foil (detail IIIA aus
FIG. 3 )
Wie bei der bekannten elektrostatischen Pulverbeschichtungstechnik üblich, wird das zu beschichtende flächige Gebilde aus Graphitfolie 1 auf eine leitend verbundene Unterlage 2 gelegt, oder die Gegenelektrode wird mit einer Krokodilklemme am Rand des flächigen Gebildes 1 aus Graphitfolie angeschlossen.
Als Folge der elektrischen Anisotropie der Graphitfolie bildet sich zwischen Graphitfolie 1 und Sprühkopf 3 ein Feldlinienverlauf 5 gemäß
Eine Mitbeschichtung der leitende Unterlage 2kann beispielsweise durch eine nichtleitende Abdeckung (in
As a consequence of the electrical anisotropy of the graphite foil, a
Co-coating of the
Die Schichtdicke der aufgebrachten Beschichtung 6 betrug etwa 10 µm.The layer thickness of the applied
Ein flächiges Werkstück 1' aus Metall wird in der Mitte der nicht zu beschichtenden Rückseite 1c punktförmig kontaktiert (Kontakt 4). Die Unterlage 2 ist nicht leitfähig.
Da in Metallen die elektrische Leitfähigkeit isotrop (unabhängig von der Richtung) ist, resultiert zwischen Werkstück 1 ' und Sprühkopf 3 der Feldlinienverlauf 5 gemäß
Die Schichtdicke der aufgebrachten Beschichtung 6 betrug etwa 10 µm.A sheet-like workpiece 1 'made of metal is punctiform contacted in the middle of the non-coated
Since the electrical conductivity is isotropic in metals (irrespective of the direction), the
The layer thickness of the applied
Erfindungsgemäß wird das flächige Gebilde aus Graphitfolie 1 in der Mitte der nicht zu beschichtenden Rückseite 1c punktförmig kontaktiert (Kontakt 4), so dass als Folge der elektrischen Anisotropie der Graphitfolie ein Feldlinienverlauf 5 gemäß
Die Unterlage 2 ist nicht leitfähig.
Die Schichtdicke der aufgebrachten Beschichtung 6 betrug etwa 10 µm.According to the invention, the planar structure made of
The
The layer thickness of the applied
Durch Einsatz eines etwa 7 Gew.-% hexagonales Bornitrid enthaltendes, polymeren Bindemittels für die Beschichtung wird eine elektrisch Isolation der beschichteten Hauptseite und der Kanten erzielt, die das Herausbrechen, Abblättern oder Abplatzen von Graphitpartikeln von der Oberfläche bzw. den Kanten der Graphitfolie verhindert ("antiflaking"-Beschichtung). Die Wärmeleitfähigkeit des Systems wird nicht nennenswert verschlechtert. Gegenüber einer unbeschichteten Graphitfolie mit einer Wärmeleitfähigkeit senkrecht zur Oberfläche von 4,9 W/(m K) zeigt eine erfindungsgemäß mit einer Schichtdicke von etwa 10 µm beschichtete Vergleichsprobe eine Wärmeleitfähigkeit senkrecht zur Oberfläche von 4,6 W/(m K).By using a polymer binder for the coating containing about 7% by weight of hexagonal boron nitride, an electrical insulation of the coated main side and the edges is achieved, which prevents the break-off, peeling or flaking off of graphite particles from the surface or edges of the graphite foil ( "antiflaking" coating). The thermal conductivity of the system is not appreciably worsened. Compared with an uncoated graphite foil having a thermal conductivity perpendicular to the surface of 4.9 W / (m K), a comparison sample coated according to the invention with a layer thickness of about 10 μm exhibits a thermal conductivity perpendicular to the surface of 4.6 W / (m K).
Claims (10)
- A method for applying a coating to a flat side, in particular the front side, and the edge surfaces of a flat structure consisting of graphite foil, comprising the following steps• applying the coating material by electrostatic powder spraying,• sintering cycle or melting cycle of the sprayed powdercharacterised in that
the flat structure consisting of graphite foil to be coated, during the spraying process, is electrically contacted practically in the centre of its rear side facing away from the spraying direction over a limited area at least 5 mm from the edges. - The method according to claim 1, characterised in that the layer thickness of the applied coating is at most 10 µm.
- The method according to claim 1, characterised in that the coating material is a thermoplastic.
- The method according to claim 3, characterised in that the coating material is polyethylene, polypropylene and polyester.
- The method according to claim 3, characterised in that the coating material is a polymeric binder which contains thermally conductive particles.
- The method according to claim 5, characterised in that the thermally conductive particles are not electrically conductive.
- The method according to claim 5 or 6, characterised in that the polymeric binder, as particles, contains boron nitride in an amount from 1 to 15 % by weight.
- The method according to claim 7, characterised in that the polymeric binder, as particles, contains hexagonal boron nitride in an amount from 5 to 10 % by weight.
- The method according to claim 1, characterised in that heating to a temperature between 160 and 280 °C is performed during the sintering or melting cycle, and this temperature is maintained for approximately 15 to 30 minutes.
- Use of the flat structure consisting of graphite foil coated by the method according to claim 1 to 5 for heat dissipation in electronic devices.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP20060125967 EP1800764B1 (en) | 2005-12-20 | 2006-12-12 | Process for coating graphite foils |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05027845A EP1800763A1 (en) | 2005-12-20 | 2005-12-20 | Process for coating graphite foils |
EP20060125967 EP1800764B1 (en) | 2005-12-20 | 2006-12-12 | Process for coating graphite foils |
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Publication Number | Publication Date |
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EP1800764A1 EP1800764A1 (en) | 2007-06-27 |
EP1800764B1 true EP1800764B1 (en) | 2014-06-11 |
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ID=38068828
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EP20060125967 Not-in-force EP1800764B1 (en) | 2005-12-20 | 2006-12-12 | Process for coating graphite foils |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3444884A1 (en) | 2017-08-17 | 2019-02-20 | FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. | Electrically conductive contact plate for electrochemical cells, electrochemical cell with such a contact plate and method for the production thereof |
Family Cites Families (1)
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US3903328A (en) * | 1974-04-26 | 1975-09-02 | Ibm | Conductive coating |
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- 2006-12-12 EP EP20060125967 patent/EP1800764B1/en not_active Not-in-force
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3444884A1 (en) | 2017-08-17 | 2019-02-20 | FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. | Electrically conductive contact plate for electrochemical cells, electrochemical cell with such a contact plate and method for the production thereof |
DE102017007718A1 (en) | 2017-08-17 | 2019-02-21 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrically conductive contact plate for electrochemical cells, electrochemical cell with such a contact plate and method for their preparation |
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EP1800764A1 (en) | 2007-06-27 |
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