EP1135538B1 - Thermal spraying method and device used for coating surfaces - Google Patents

Thermal spraying method and device used for coating surfaces Download PDF

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Publication number
EP1135538B1
EP1135538B1 EP99953958A EP99953958A EP1135538B1 EP 1135538 B1 EP1135538 B1 EP 1135538B1 EP 99953958 A EP99953958 A EP 99953958A EP 99953958 A EP99953958 A EP 99953958A EP 1135538 B1 EP1135538 B1 EP 1135538B1
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EP
European Patent Office
Prior art keywords
wire
atomizing gas
supply
plasma
melting
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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.)
Expired - Lifetime
Application number
EP99953958A
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German (de)
French (fr)
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EP1135538A1 (en
Inventor
Dietmar Kley
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Grillo Werke AG
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Grillo Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying

Definitions

  • the invention is directed to a method according to claim 1 and a device according to claim 6 for thermal Spraying, in particular of metals, for the coating of surfaces, wherein the supplied for coating material in the form of a wire, is melted and sprayed.
  • Such devices are known in different designs. So are for example, manually operated spray guns are known in which two Wires on Vorschab driving an angle to each other in front of a Nebulizer gas nozzle are merged, with a between the wire tips the wires melting arc is generated.
  • EP-0 is for arc technology 239 585-B with further references.
  • the object of the invention is to provide a method and a device for Spraying of metallic wire without destroying at least one of Electrodes.
  • Burning heads with a plasma arc are known per se as the Cutting cutting heads to be used with metal sheets that work with compressed air.
  • this arc plasma cutting the heat energy and the kinetic Energy of an ionized gas column (plasma) used to melt the metal and from the kerf to displace.
  • This property makes the invention exploited by the plasma arc is a compressed air plasma arc and a Such a plasma cutting head, a wire is supplied to the atomization.
  • the arc burns between a non-melting, fixed Electrode and a Melting Wire
  • the molten material is poured into Wound wire spraying.
  • the plasma arc is initially between the ignited two electrodes.
  • An electrically conductive wire takes over Function of an electrode. After ignition, the consuming wire becomes tracked.
  • the combustion head is designed as a compressed air plasma arc burner.
  • the feeding nozzle of the wire with the Zerstäubergas is useful at an angle to the central axis of Plasma torch arranged, for example, the angle in more Design between wire feed and plasma torch central axis about 75 ° is.
  • the atomizing gas nozzle expediently surrounds the central wire feed ring-shaped.
  • an inert gas plasma burner of the atomizing gas nozzle is assigned and / or that a non-metallic wire for melting and the Splashing the atomizer gas nozzle can be assigned.
  • the particular advantage of the invention is, inter alia, that a higher Abmelz intricate can be provided, the order efficiency can be increase at least 10%, with dust formation and material evaporation be reduced.
  • At least two combustion heads with associated Drahtzuschreibund Nebulizer gas nozzles are provided, It is possible to different Supply materials to the different combustion heads and the material mixture then apply to the surface to be coated.
  • the generally designated 1 device consists of a spray gun housing 2 with a handle 3 as an actuation switch 4, wherein the housing 2 a Is assigned to the spray wire feed head 5 and a compressed air plasma burner head 6, whose Central axes to each other in the example shown occupy an angle of 75 °.
  • the plasma burner head 6 is associated with a merely indicated hose package 7 with power supply and compressed air supply, while the wire feed head Supply hose 8 is associated with the designated 9 wire
  • the Compressed air is supplied via the housing 2, as is apparent in particular from FIG.
  • the wire 9 exits the front of the nebulizer gas nozzle designated 10 and is in melted with a designated plasma arc 11 and by means of the Zerstäubergases thrown as spray jet 12 on a surface, not shown.
  • Fig. 2 the wire to be melted itself is not shown, only one Wire guide channel 13, which passes through the Zerstäubergasdüse 10 centrally.
  • the Zerstäubergas is about the housing 2 via respective channels 14 a Ring chamber 15 is supplied, which in turn is substantially centrally the feed channel 13 for the wire surrounds.
  • control devices that ensure, for example, that the compressed air supply for the plasma torch 6 and the compressed air supply for the Formation of Zerstäubergasstrahles can be set differently.
  • the described embodiment of the invention is even more numerous Change their views without leaving the basic idea.
  • the arc not only between the burner as a cathode and
  • the spray wire can be formed as an anode, it can also be Arc inside the burner between a cathode and an anode are then formed, then electrically non-conductive wires, e.g. plastic-coated oxide powder filling wires can be processed.
  • electrically non-conductive wires e.g. plastic-coated oxide powder filling wires can be processed.
  • This Embodiment makes the device more flexible in processing different materials.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Nozzles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Plasma Technology (AREA)

Abstract

The invention relates to a method for thermally spraying, in particular, metals in order to coat surfaces, whereby the material used for coating is fed in the form of a wire, is melted, and is sprayed. The inventive method utilizes a plasma arc.

Description

Die Erfindung richtet sich auf ein Verfahren gemäß Anspruch 1 und eine Vorrichtung gemäß Anspruch 6 zum thermischen Spritzen insbesondere von Metallen, zur Beschichtung von Oberflächen, wobei das zur Beschichtung herangezogene Material in Form eines Drahtes zugeführt, aufgeschmolzen und verspritzt wird.The invention is directed to a method according to claim 1 and a device according to claim 6 for thermal Spraying, in particular of metals, for the coating of surfaces, wherein the supplied for coating material in the form of a wire, is melted and sprayed.

Derartige Vorrichtungen sind in unterschiedlichen Ausführungen bekannt. So sind beispielsweise von Hand zu betätigende Spritzpistolen bekannt, bei denen zwei Drähte über Vorschabeinrichtungen im Winkel zueinander vor einer Zerstäubergasdüse zusammengeführt werden, wobei zwischen den Drahtspitzen ein die Drähte aufschmelzender Lichtbogen erzeugt wird.Such devices are known in different designs. So are For example, manually operated spray guns are known in which two Wires on Vorschabeinrichtungen at an angle to each other in front of a Nebulizer gas nozzle are merged, with a between the wire tips the wires melting arc is generated.

Es ist auch bekannt, im Spritzkopf eine Schmelzflamme zu erzeugen, mit deren Hilfe das aufzusprühende Gut aufgeschmolzen wird, wobei dann über Druckluft oder dergleichen die aufgeschmolzenen Partikel auf die zu beschichtende Oberfläche gefördert werden. Lediglich als Beispiel sei für eine Lichtbogentechnologie die EP-0 239 585-B genannt mit weiteren Literaturhinweisen.It is also known to produce a molten flame in the spray head, with the help of which the aufzusprühende Good is melted, then using compressed air or Like the melted particles on the surface to be coated be encouraged. By way of example only, EP-0 is for arc technology 239 585-B with further references.

Aufgabe der Erfindung ist die Schaffung eines Verfahrens und einer Vorrichtung zum Verspritzen von metallischem Draht ohne Zerstörung wenigstens einer der Elektroden. Dabei sollen ein hoher Wirkungsgrad, ein geringer Geräuschpegel und eine leichte Handhabung gewährleistet sein. The object of the invention is to provide a method and a device for Spraying of metallic wire without destroying at least one of Electrodes. Here are a high efficiency, a low noise level and be ensured easy handling.

Mit dem Verfahren und der Vorrichtung der eingangs bezeichneten Art wird diese Aufgabe gemäß der Erfindung dadurch gelöst, dass die Aufschmelzenergie durch einen Plasmalichtbogen erzeugt wird, wobei der Lichtbogen zwischen einer nicht abschmelzenden, feststehenden Elektrode und einer abschmelzenden Elektrode in Form des Drahtes brennt, und das aufgeschmolzene Material in Drahtlaufrichtung verspritzt wird.With the method and the device of the type described is this Problem solved according to the invention characterized in that the melting energy a plasma arc is generated, wherein the arc between a not melting, fixed electrode and a consumable electrode in Form of the wire burns, and the molten material in the wire running direction is sprayed.

Brennköpfe mit einem Plasmalichtbogen sind für sich gesehen bekannt als zum Schneiden von Metallblechen einzusetzende Schneidköpfe, die mit Druckluft arbeiten. Bei diesem Lichtbogen-Plasmaschneiden wird die Wäremenergie und die kinetische Energie einer ioinisierten Gassäule (Plasma) genutzt, um das Metall zu schmelzen und aus der Schnittfuge zu verdrängen. Diese Eigenschaft macht sich die Erfindung zunutze, indem der Plasmalichtbogen ein Druckluft-Plasmalichtbogen ist und einem solchen Plasmaschneidkopf ein Draht zur Zerstäubung zugeführt wird. Vorzugsweise brennt dabei der Lichtbogen zwischen einer nicht abschmelzenden, feststehenden Elektrode und einem abschmelzenden Draht Das aufgeschmolzene Material wird in Drahtlsufrichtung verspritzt. Der Plasmalichtbogen wird zunächst zwischen den beiden Elektroden gezündet. Dabei übernimmt ein elektrisch leitender Draht die Funktion einer Elektrode. Nach der Zündung wird der sich verbrauchende Draht nachgeführt.Burning heads with a plasma arc are known per se as the Cutting cutting heads to be used with metal sheets that work with compressed air. In this arc plasma cutting, the heat energy and the kinetic Energy of an ionized gas column (plasma) used to melt the metal and from the kerf to displace. This property makes the invention exploited by the plasma arc is a compressed air plasma arc and a Such a plasma cutting head, a wire is supplied to the atomization. Preferably while the arc burns between a non-melting, fixed Electrode and a Melting Wire The molten material is poured into Wound wire spraying. The plasma arc is initially between the ignited two electrodes. An electrically conductive wire takes over Function of an electrode. After ignition, the consuming wire becomes tracked.

Ausgestaltungen der Erfindung ergeben sich aus den Unteransprüchen, wobei insbesondere, wie oben schon angedeutet, vorgesehen sein kann, dass der Brennkopf als Druckluft-Plasmalichtbogen-Brenner ausgebildet ist. Die Zuführdüse des Drahtes mit dem Zerstäubergas ist dabei zweckmäßig im Winkel zur Mittelachse des Plasmabrenners angeordnet, wobei beispielsweise der Winkel in weiterer Ausgestaltung zwischen Drahtzufuhr und Plasmabrenner-Mittelachse etwa 75° beträgt. Embodiments of the invention will become apparent from the dependent claims, wherein in particular, as already indicated above, it can be provided that the combustion head is designed as a compressed air plasma arc burner. The feeding nozzle of the wire with the Zerstäubergas is useful at an angle to the central axis of Plasma torch arranged, for example, the angle in more Design between wire feed and plasma torch central axis about 75 ° is.

Zweckmäßig umgibt die Zerstäubergasduse die zentrische Drahtzufuhr ringförmig.The atomizing gas nozzle expediently surrounds the central wire feed ring-shaped.

Vorteilhaft kann es sein, wenn ein Inertgas-Plasmabrenner der Zerstäubergasdüse zugeordnet ist und/oder dass ein nicht metallischer Draht zur Aufschmelzung und zum Verspritzen der Zerstäubergasdüse zugeordnet werden kann.It may be advantageous if an inert gas plasma burner of the atomizing gas nozzle is assigned and / or that a non-metallic wire for melting and the Splashing the atomizer gas nozzle can be assigned.

Der besondere Vorteil der Erfindung besteht unter anderem darin, dass eine höhere Abschmelzleistung erbracht werden kann, die Auftragseffizienz lässt sich um wenigstens 10% erhöhen, wobei die Staubbildung sowie die Materialverdampfung reduziert werden.The particular advantage of the invention is, inter alia, that a higher Abmelzleistung can be provided, the order efficiency can be increase at least 10%, with dust formation and material evaporation be reduced.

Je nach Einsatz der erfindungsgemäßen Vorrichtung kann in weiterer Ausgestaltung vorgesehen sein, dass wenigstens zwei Brennköpfe mit zugeordneten Drahtzufuhrund Zerstäubergasdüsen vorgesehen sind, Dabei ist es möglich, unterschiedliche Materialien den unterschiedlichen Brennköpfen zuzuführen und das Materialgemisch dann auf die zu beschichtende Oberfläche aufzubringen.Depending on the use of the device according to the invention can in a further embodiment be provided that at least two combustion heads with associated Drahtzufuhrund Nebulizer gas nozzles are provided, It is possible to different Supply materials to the different combustion heads and the material mixture then apply to the surface to be coated.

Weitere Einzelheiten, Vorteile und Merkmale der Erfindung ergeben sich aufgrund der nachfolgenden Beschreibung sowie anhand der Zeichnung. Diese zeigt in

Fig. 1.
eine vereinfachte Wiedergabe einer Vorrichtung nach der Erfindung sowie in
Fig.2
eine vergrößerte Schnittdarstellung der Kopfausbildung der erfindungsgemäßen Vorrichtung.
Further details, advantages and features of the invention will become apparent from the following description and from the drawing. This shows in
Fig. 1.
a simplified representation of a device according to the invention and in
Fig.2
an enlarged sectional view of the head training of the device according to the invention.

Die allgemein mit 1 bezeichnete Vorrichtung besteht aus einem Spritzpistolengehäuse 2 mit einem Handgriff 3 als Betätigungsschalter 4, wobei dem Gehäuse 2 ein Spritzdrahtzuführkopf 5 und ein Druckluft-Plasmabrennkopf 6 zugeordnet ist, deren Mittelachsen zueinander im dargestellten Beispiel einen Winkel von 75° einnehmen. Dem Plasmabrennkopf 6 ist ein lediglich angedeutetes Schlauchpaket 7 zugeordnet mit Stromzuführung und Druckluftzuführung, während dem Drahtzuführkopf ein Zuführschlauch 8 für den mit 9 bezeichneten Draht zugeordnet ist Die Druckluftzufuhr erfolgt über das Gehäuse 2, wie sich insbesondere aus Fig. 2 ergibt.The generally designated 1 device consists of a spray gun housing 2 with a handle 3 as an actuation switch 4, wherein the housing 2 a Is assigned to the spray wire feed head 5 and a compressed air plasma burner head 6, whose Central axes to each other in the example shown occupy an angle of 75 °. The plasma burner head 6 is associated with a merely indicated hose package 7 with power supply and compressed air supply, while the wire feed head Supply hose 8 is associated with the designated 9 wire The Compressed air is supplied via the housing 2, as is apparent in particular from FIG.

Der Draht 9 tritt vorne aus der mit 10 bezeichneten Zerstäubergasdüse aus und wird in einem mit 11 bezeichneten Plasmalichtbogen aufgeschmolzen und mittels des Zerstäubergases als Spritzstrahl 12 auf eine nicht dargestellte Oberfläche geworfen.The wire 9 exits the front of the nebulizer gas nozzle designated 10 and is in melted with a designated plasma arc 11 and by means of the Zerstäubergases thrown as spray jet 12 on a surface, not shown.

In Fig. 2 ist der aufzuschmelzende Draht selbst nicht dargestellt, lediglich ein Drahtführungskanal 13, der die Zerstäubergasdüse 10 zentrisch durchsetzt. Das Zerstäubergas wird über das Gehäuse 2 über entsprechende Kanäle 14 einer Ringkammer 15 zugeführt, die ihrerseits im wesentlichen zentrisch den Zuführkanal 13 für den Draht umgibt. Im Plasmabrennkopf 6 befindet sich eine Elektrode 16 mit einem Zr/Hf-Einsatz 17, wobei auch hier eine zentrische Druckluftzuführung 18 vorgesehen ist, die von Isolierelementen 19 umgeben ist.In Fig. 2, the wire to be melted itself is not shown, only one Wire guide channel 13, which passes through the Zerstäubergasdüse 10 centrally. The Zerstäubergas is about the housing 2 via respective channels 14 a Ring chamber 15 is supplied, which in turn is substantially centrally the feed channel 13 for the wire surrounds. In the plasma burner head 6 is an electrode 16 with a Zr / Hf insert 17, wherein here too a centric compressed air supply 18th is provided, which is surrounded by insulating elements 19.

Nicht näher dargestellt sind Regeleinrichtungen, die beispielsweise dafür sorgen, dass die Druckluftzufuhr für den Plasmabrenner 6 und die Druckluftzufuhr für die Ausbildung des Zerstäubergasstrahles unterschiedlich eingestellt werden kann.Not shown in detail are control devices that ensure, for example, that the compressed air supply for the plasma torch 6 and the compressed air supply for the Formation of Zerstäubergasstrahles can be set differently.

Natürlich ist das beschriebene Ausführungsbeispiel der Erfindung noch in vielfacher Hinsicht abzuändern, ohne den Grundgedanken zu verlassen. So kann, statt wie dargestellt, der Lichtbogen nicht nur zwischen dem Brenner als Kathode und beispielsweise dem Spritzdraht als Anode ausgebildet werden, es kann auch der Lichtbogen innerhalb des Brenners zwischen einer Kathode und einer Anode ausgebildet werden, wobei dann auch elektrisch nicht leitende Drähte, z.B. kunststoffummantelte Oxidpulverfülldrähte verarbeitet werden können. Diese Ausführungsform macht die Vorrichtung flexibler in der Verarbeitung von verschiedenen Werkstoffen.Of course, the described embodiment of the invention is even more numerous Change their views without leaving the basic idea. So, instead of how shown, the arc not only between the burner as a cathode and For example, the spray wire can be formed as an anode, it can also be Arc inside the burner between a cathode and an anode are then formed, then electrically non-conductive wires, e.g. plastic-coated oxide powder filling wires can be processed. This Embodiment makes the device more flexible in processing different materials.

Claims (11)

  1. A method for thermal spraying, especially of metals, for the coating of surfaces, wherein the material employed for coating is supplied in the form of a wire, molten and sprayed using an atomizing gas, characterized in that the melting energy is produced by a compressed-air or inert-gas plasma arc, wherein the arc is formed between a non-melting stationary electrode and a melting electrode in the form of the wire, and the molten material is sprayed by the atomizing gas in the direction of wire feeding, wherein the gas stream for the plasma arc and that for the atomizing gas can be adjusted independently of each other.
  2. The method according to claim 1, characterized in that said wire is surrounded by the atomizing gas in an annular arrangement.
  3. The method according to any of the preceding claims, characterized in that said atomizing gas is an inert gas or compressed air.
  4. The method according to any of the preceding claims, characterized in that said wire is advanced at a settable angle with the center line of the plasma arc.
  5. The method according to any of the preceding claims, characterized in that the angle between the wire and plasma arc is about 75°.
  6. A device for thermal spraying, especially of metals, for the coating of surfaces, consisting of a spray gun housing (2), a spray wire supply head (5), a compressed-air plasma torch head (6), a bundle of flexible tubes for electric power supply and compressed air supply, a supply tube (8) for the wire supply head (5), an atomizing gas nozzle (10), an electrode (16), insulating members (19) surrounding said electrode, as well as controlling means for differently settable supply rates of compressed air for the plasma torch (6) and the atomizing gas (12).
  7. The device according to claim 6, characterized in that the supply nozzle (5) for the wire with the atomizing gas nozzle (10) is arranged at a settable angle with the medium line of the plasma torch (6).
  8. The device according to any of the preceding claims, characterized in that the angle between the wire supply (8) and the plasma torch (6) is about 75°.
  9. The device according to any of the preceding claims, characterized in that said atomizing gas nozzle (10) surrounds the centric wire supply (13) in an annular arrangement.
  10. The device according to any of the preceding claims, characterized in that a non-metallic wire is associated with the atomizing gas nozzle for melting and spraying.
  11. The device according to any of the preceding claims, characterized in that at least two torch heads with associated wire supply and atomizing gas nozzles are provided.
EP99953958A 1998-10-31 1999-10-29 Thermal spraying method and device used for coating surfaces Expired - Lifetime EP1135538B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE29819453U 1998-10-31
DE29819453U DE29819453U1 (en) 1998-10-31 1998-10-31 Thermal spraying device for coating surfaces
PCT/EP1999/008247 WO2000026429A1 (en) 1998-10-31 1999-10-29 Thermal spraying method and device used for coating surfaces

Publications (2)

Publication Number Publication Date
EP1135538A1 EP1135538A1 (en) 2001-09-26
EP1135538B1 true EP1135538B1 (en) 2003-10-08

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EP99953958A Expired - Lifetime EP1135538B1 (en) 1998-10-31 1999-10-29 Thermal spraying method and device used for coating surfaces

Country Status (10)

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EP (1) EP1135538B1 (en)
AT (1) ATE251678T1 (en)
AU (1) AU1044600A (en)
DE (2) DE29819453U1 (en)
DK (1) DK1135538T3 (en)
ES (1) ES2204168T3 (en)
NO (1) NO331815B1 (en)
PL (1) PL190514B1 (en)
PT (1) PT1135538E (en)
WO (1) WO2000026429A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10329673B2 (en) 2014-06-27 2019-06-25 Sika Technology Ag Galvanic anode system for the corrosion protection of steel in concrete

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10043295C1 (en) * 2000-09-02 2002-04-25 Rheinzink Gmbh Heliothermal flat collector module

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB959027A (en) * 1959-09-14 1964-05-27 British Oxygen Co Ltd Apparatus and process for spraying molten metal
DE2002472A1 (en) * 1970-01-21 1971-07-29 Afam Arbeitsgruppe Fuer Angewa Tubular wire plasma arc spraying device
CS150108B1 (en) * 1970-09-04 1973-09-04
FR2148811A5 (en) * 1971-08-04 1973-03-23 Commissariat Energie Atomique
US5109150A (en) * 1987-03-24 1992-04-28 The United States Of America As Represented By The Secretary Of The Navy Open-arc plasma wire spray method and apparatus
US4970091A (en) * 1989-10-18 1990-11-13 The United States Of America As Represented By The United States Department Of Energy Method for gas-metal arc deposition
DE4409002A1 (en) * 1994-03-16 1994-09-01 Arnim Wirth Method for applying materials in the form of powders or wires by means of a plasma arc which is not transmitted to the workpiece
US5796064A (en) * 1996-10-29 1998-08-18 Ingersoll-Rand Company Method and apparatus for dual coat thermal spraying cylindrical bores

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10329673B2 (en) 2014-06-27 2019-06-25 Sika Technology Ag Galvanic anode system for the corrosion protection of steel in concrete

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Publication number Publication date
DE29819453U1 (en) 1999-01-14
PT1135538E (en) 2004-02-27
WO2000026429A1 (en) 2000-05-11
AU1044600A (en) 2000-05-22
DK1135538T3 (en) 2004-02-16
PL190514B1 (en) 2005-12-30
ATE251678T1 (en) 2003-10-15
PL347364A1 (en) 2002-04-08
NO20012025L (en) 2001-04-25
NO331815B1 (en) 2012-04-10
EP1135538A1 (en) 2001-09-26
DE59907320D1 (en) 2003-11-13
ES2204168T3 (en) 2004-04-16
NO20012025D0 (en) 2001-04-25

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