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EP1616041B1 - Flammenbeschichtungsverfahren und entsprechende vorrichtung - Google Patents

Flammenbeschichtungsverfahren und entsprechende vorrichtung Download PDF

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Publication number
EP1616041B1
EP1616041B1 EP04742532A EP04742532A EP1616041B1 EP 1616041 B1 EP1616041 B1 EP 1616041B1 EP 04742532 A EP04742532 A EP 04742532A EP 04742532 A EP04742532 A EP 04742532A EP 1616041 B1 EP1616041 B1 EP 1616041B1
Authority
EP
European Patent Office
Prior art keywords
flame
coating
powder
process according
coating process
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.)
Expired - Lifetime
Application number
EP04742532A
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English (en)
French (fr)
Other versions
EP1616041A1 (de
Inventor
Alain Tournier
Denis Girardin
Michel Chezeau
Alain Secondy
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.)
Saint Gobain PAM SA
Original Assignee
Saint Gobain PAM SA
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Filing date
Publication date
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Publication of EP1616041A1 publication Critical patent/EP1616041A1/de
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Publication of EP1616041B1 publication Critical patent/EP1616041B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/20—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion
    • B05B7/201—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle
    • B05B7/205—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle the material to be sprayed being originally a particulate material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying

Definitions

  • the object of the present invention is to propose a method of flame coating which is economical.
  • the method according to the invention may comprise one or more of the features of the method claims dependent on claim 1.
  • the invention further relates to a coating device by means of a flame adapted for carrying out the method according to any one of the preceding claims, of the type comprising the characteristics of the independent device claim.
  • the device according to the invention may comprise one or more of the features of the device-dependent claims.
  • the installation comprises a raw powder recovery device 4, a main reservoir 6, three feed tanks 8A, 8B, 8C, and three flame coating devices 10A, 10B, 10C.
  • Such powders generally comprise low melting point metal alloy particles, located between 400 ° C and 450 °, and preferably between 425 ° C and 475 ° C.
  • the residual portion of the alloy comprises aluminum and is preferably made of aluminum.
  • the installation 2 further comprises first feed means 12 in powder coating material, adapted to feed the main tank 6.
  • These first feed means 12 comprise a first conveyor 14A whose inlet is connected to an outlet of the raw powder recovery device 4 and whose outlet opens into the main tank 6.
  • the installation 2 further comprises second powder coating material feed means 14B, adapted to supply each of the coating material powder feed tanks, from the main tank 6.
  • these second supply means 14B consist of three conveyors 16A, 16B, 16C, each of which is connected to an outlet of the main tank and to an inlet of the supply tanks 8A, 8B, 8C.
  • Third powder supply means 18 are adapted to convey powder from each of the supply tanks 8A, 8B, 8C to each of the coating devices 10A, 10B, 10C. As it happens, these third feed means 18 consist of three screw conveyors 20A, 20B, 20C.
  • the largest dimension of each of the particles is less than 1000 ⁇ m, preferably less than 800 ⁇ m, and in particular less than 500 ⁇ m.
  • the powder consists of particles whose smallest dimension is greater than 20 ⁇ m, preferably greater than 40 ⁇ m and in particular greater than 60 ⁇ m.
  • FIG. 2 is schematically represented the coating device 10A according to the invention and an object to be coated.
  • the object to be coated is a pipe 40 of generally cylindrical hollow shape having a longitudinal and horizontal axis X-X.
  • the pipe is for example metal and in particular cast iron.
  • the pipe 40 is fixed on a support (not shown) and can be rotated about its longitudinal axis X-X and in translation relative to the coating device 10 along this axis.
  • the coating device 10 comprises a burner 42 which is shown in partial section on the Figure 2 , as well as a device 46 for introducing the coating material powder into a flame 44.
  • the burner 42 is formed by a burner head 48 and means 50 for cooling and guiding the flame 44.
  • the burner head 48 is provided with an oxidizing gas inlet 52 connected to a source of oxidizing gas 54, such as oxygen, via a combustion gas pipe 56 and a first gas valve. flow and pressure setting 58.
  • the burner head 48 is provided with a fuel gas inlet 60, connected to a fuel gas source 62, such as natural gas, acetylene or propane, via a fuel gas pipe. 64 and a second control valve 66 for pressure and flow.
  • a fuel gas source 62 such as natural gas, acetylene or propane
  • the burner head 48 and a part of the device 46 for introducing the powder are represented on a larger scale on the Figure 3 , the burner head 48 being shown in longitudinal section.
  • the burner head 48 is generally of revolution about the Y-axis. It comprises, arranged successively one behind the other, and in the direction of flame F, a mixer 68, a fuel gas nozzle 70, and an oxidizing gas nozzle 72.
  • the combustion gas nozzle 72 is maintained by a nozzle holder 74.
  • the mixer 68 forms the fuel gas inlet 60 and the combustion gas inlet 52 of the burner 42.
  • the mixer 68 and the fuel gas nozzle 70 comprise a fuel gas passage 76, coaxial with the YY axis and a plurality of combustion gas passages 78 distributed regularly around the fuel gas passage 76. These components are known per se.
  • the ratio of the diameters of the passages 76 and 78 is adapted to establish a mixture of stoichiometric gas at a high rate.
  • the oxidizing gas nozzle holder 74 is a Y-Y axis revolution member, which has a stepped through bore 80 whose cross-section decreases from the rear end to the front.
  • the oxidizing gas nozzle holder 74 comprises a threaded cylindrical base 82, to which a frustoconical outer portion 84 is connected.
  • the means 50 for cooling and guiding the flame 44 comprise a cooling sleeve 86, in which the burner head 48 is arranged.
  • the sleeve 86 includes a gas inlet end 88 and a flame outlet end 90.
  • the sleeve 86 comprises, on the side of the inlet end 88, a stepped threaded bore 92, in a part of which is screwed the base 82 of the oxidizing gas nozzle holder 74, so that the frustoconical portion 84 and the remainder of the stepped bore 92 form an annular cooling chamber 94 surrounding an axial portion of the nozzle holder 74.
  • a radial bore 96 of cooling gas inlet is formed in the sleeve 86, bore 96 which opens into the cooling chamber 94, and which is connected to means 98 for supplying cooling air.
  • these cooling air supply means 98 comprise a first air compressor 100 connected to a compressed air pipe 102 which opens into the cooling chamber 94 and into which is inserted a third control valve 104.
  • the sleeve 86 further comprises bores 106 which extend axially from the cooling chamber 94 and open onto a front surface of the sleeve 86, disposed on the outlet end side 90 and formed by an annular groove 108 open in the direction of the flame F to allow a confinement of the flame without disturbance of the initial flow.
  • the sleeve 86 comprises eight bores 106.
  • Each injector 120A, 120B, 120C, 120D essentially consists of a tube having a powder outlet 124, adapted to introduce the coating material powder into the flame 44 in an insertion direction IA to ID.
  • Each of the introduction directions IA to ID is directed substantially radially to the flame axis Y-Y.
  • the two directions of introduction IA and IB of the two injectors 120A, 120B are inclined at 45 ° downwards, while the introduction directions IC and ID of the two injectors 120C, 120D extend substantially horizontally, parallel to the XX axis and are directed towards each other.
  • the directions of introduction IA to ID therefore each have a component extending along the longitudinal axis X-X of the pipe 40.
  • the particles of the powder projected towards the pipe 40 are distributed on an imaginary spot whose preferential direction extends along the axis X-X. As a result, few particles are projected over or under the pipe 40.
  • the supply device 122 of a powder / air mixture comprises a powder / air mixing chamber 126 having an inlet hopper 128 for the coating material powder and a compressed air inlet 130 which is connected to means compressed air supply, formed by a second compressor 132 and a fourth control valve 134.
  • a metering device 140 in this case a vibration conveyor, is disposed above the inlet of the inlet hopper 128.
  • the metering device 140 is adapted to be supplied with powder coating material by the screw conveyor 20A.
  • the installation according to the invention operates as follows.
  • the cast iron pipe 40 is installed on the support (not shown) and is rotated about the X-X axis.
  • the fuel gas flow rate is set to achieve a power of up to 70 kW.
  • As for the flow of the oxidizing gas it is set to generate a stoichiometric flame.
  • the power of 70kW corresponds to a flow of about 7 ⁇ nm 3 h in natural gas.
  • the first compressor 100 is started and the cooling chamber 94 is supplied with pressurized air, for example at a pressure of about 2 bar.
  • the flame 44 is initiated by the priming device 110.
  • the flame 44 which is established has a power between 30 kW and 70 kW.
  • the maximum temperature of the flame 44 is between 2000 ° C. and 3000 ° C., preferably between 2250 ° C. and 2750 ° C., and in particular between 2400 ° C. and 2600 ° C.
  • the maximum speed of the gases of the flame 44 is between 500 m / s and 2000 m / s, and preferably between 700 m / s and 900 m / s.
  • the supply device of the mixture 122 is started and conveys an air / powder mixture to the injectors 120A, 120B, 120C, 120D.
  • the powder flow rate of a single injector 120A, 120B, 120C, 120D is between 15 kg / h and 50 kg / h, and is preferably about 35 kg / h per injector.
  • the powder flow of all the injectors is between 60 kg / h and 250 kg / h.
  • the powder particles are then driven by the flame 44 in the direction F thereof. They are melted completely by the flame 44 and form droplets of molten coating material. Because the particle sizes are within the above range, the particles are melted completely without evaporating. The droplets exit the flame 44 in a sufficiently rapid manner to prevent their evaporation.
  • the droplets are projected onto the pipe 40.
  • the distance between the flame 44 and the pipe 40 is chosen so that the droplets are still in the liquid state when they meet the pipe.
  • the droplets adhere to the pipe 40 and solidify to form a coating.
  • the latter In order to coat the outer surface along the length of the pipe 40, the latter is driven in translation along the axis X-X.
  • the method according to the invention makes it possible to coat an object with a coating layer at a high flow rate in mass of powder while using powder recovered from previous coating processes.
  • the process according to the invention achieves a yield similar to that of flame coating processes using a wire-like coating material, namely of the order of 60%.
  • the device according to the invention as well as the process parameters make it possible to use a powder consisting of a low melting point alloy (about 450 ° C.), such as Zn 85 Al 15 , as a coating material.
  • a low melting point alloy about 450 ° C.
  • the powder consists of at least 50% of a metal or alloy whose melting point is between 400 ° C. and 500 ° C., preferably between 425 ° C. and 475 ° C. ° C.
  • the mixing chamber 126 may be connected to a source of gas other than air, for example a source of an inert gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Nozzles (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Vending Machines For Individual Products (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Insulated Conductors (AREA)
  • Materials For Medical Uses (AREA)

Claims (19)

  1. Verfahren zur Beschichtung eines Objekts (40), das durch ein schmelzbares Material zu beschichten ist, mit folgenden Schritten:
    - Bilden einer Flamme (44) mit einer maximalen Flammengeschwindigkeit und einer Flammenrichtung (F), die mit einer Flammenachse (Y-Y) übereinstimmt und die in Richtung des zu beschichtenden Objekts (40) ausgerichtet ist;
    - Zuführen einer Menge des schmelzbaren Beschichtungsmaterials in die Flamme (44);
    - wobei die maximale Flammengeschwindigkeit und der Abstand zwischen dem zu beschichtenden Objekt (40) und der Flamme (44) derart gewählt sind, dass das schmelzbare Beschichtungsmaterial auf das zu beschichtende Objekt (40) gespritzt wird, und derart, dass sich zumindest ein Teil der Menge an schmelzbarem Beschichtungsmaterials beim Auftreffen auf dem zu beschichtenden Objekt (40) in geschmolzenem Zustand befindet,
    - die Menge an schmelzbarem Beschichtungsmaterial Pulver enthält, das von Partikeln gebildet ist,
    - wobei die Flamme (44) eine Temperatur aufweist, die ausreichend niedrig ist, damit die Partikel des Pulvers nicht zur Gänze verdampfen, und die ausreichend hoch ist, damit die Partikel des Pulvers zumindest teilweise geschmolzen werden,
    dadurch gekennzeichnet, dass zumindest ein Teil des Pulvers ein Pulverrückstand ist, der aus dem Spritzbeschichtungsverfahren hervorgegangen ist, dass das Pulver von einer Legierung gebildet ist, die mindestens 50% Gewichtsanteil an Zn, insbesondere mindestens 85% Gewichtsanteil an Zn und vorzugsweise mindestens 95% Gewichtsanteil an Zn enthält, und dass der Restanteil der Legierung Aluminium enthält und insbesondere aus Aluminium besteht.
  2. Beschichtungsverfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Menge an Material aus Pulver besteht.
  3. Beschichtungsverfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Partikel eine größtmögliche Größe haben, die kleiner als 1.000 µm, vorzugsweise kleiner als 800 µm und insbesondere kleiner als 500 µm ist.
  4. Beschichtungsverfahren entsprechend einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Partikel eine kleinstmögliche Größe haben, die größer als 20 µm, vorzugsweise größer als 40 µm und insbesondere größer als 60 µm ist.
  5. Beschichtungsverfahren entsprechend einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Material in zumindest einer Zuführungsrichtung (IA bis ID) in die Flamme (44) zugeführt wird und dass die Zuführungsrichtung (IA bis ID) eine relativ zu der Flammenachse (Y-Y) radiale Komponente aufweist.
  6. Beschichtungsverfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Zuführungsrichtung (IA bis ID) relativ zu der Flammenachse (Y-Y) im Wesentlichen in radialer Richtung ausgerichtet wird.
  7. Beschichtungsverfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass sich das zu beschichtende Objekt (40) entlang einer Längsachse (X-X) erstreckt und dass die Zuführungsrichtung (IA bis ID) eine Komponente aufweist, die sich parallel zu der Längsachse (X-X) erstreckt.
  8. Beschichtungsverfahren nach Anspruch 7, dadurch gekennzeichnet, dass sich die Zuführungsrichtung (IC, ID) im Wesentlichen parallel zu der Längsachse (X-X) des zu beschichtenden Objekts (40) erstreckt.
  9. Beschichtungsverfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Material in zumindest zwei Zuführungsrichtungen (IA, IS; IC, ID) in die Flamme (44) zugeführt wird und dass sich diese beiden Richtungen symmetrisch beiderseits einer Ebene (P-P) erstrecken, welche die Flammenachse (Y-Y) enthält und sich senkrecht zu der Längsachse (X-X) des zu beschichtenden Objekts erstreckt.
  10. Beschichtungsverfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass das Pulver über zumindest ein Einspritzelement (120A, 1208, 120C, 120D) in die Flamme zugeführt wird und dass die Menge des in die Flamme zugeführten Pulvers zwischen 60 kg/h und 250 kg/h beträgt.
  11. Beschichtungsverfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die maximale Flammengeschwindigkeit zwischen 500 m/s und 2.000 m/s beträgt und vorzugsweise zwischen 700 m/s und 900 m/s liegt.
  12. Beschichtungsverfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Pulverrückstand aus einem Drahtlichtbogenbeschichtungsverfahren hervorgegangen ist, bei dem als Ausgangsmaterial ein Draht oder eine Litze aus schmelzbarem Beschichtungsmaterial verwendet wird.
  13. Beschichtungsverfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Teil des Pulvers durch Sieben einer Menge unverbrannten Pulverrückstands erhalten ist.
  14. Beschichtungsverfahren nach Anspruch 13, dadurch gekennzeichnet, dass zumindest der Teil des Pulvers vor der Zuführung in die Flamme (44) einer Trocknung oder einer Desoxidation unterzogen wird.
  15. Beschichtungsverfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die maximale Temperatur der Flamme zwischen 2.000 °C und 3.000 °C, vorzugsweise zwischen 2.250 °C und 2.750 °C und insbesondere zwischen 2.400 °C und 2.600 °C beträgt.
  16. Vorrichtung zur Beschichtung mittels einer Flamme, angepasst für die Durchführung des Verfahrens nach einem der vorangegangenen Ansprüche, umfassend:
    - einen Brenner (42), der für den Anschluss an eine Verbrennungsgasquelle (62) vorgesehen ist und für die Bildung einer Flamme (44) in einer Flammenrichtung (Y-Y) vorgesehen ist,
    - Mittel (46) für die Zuführung eines schmelzbaren Beschichtungsmaterials in die Flamme,
    dadurch gekennzeichnet, dass die Vorrichtung einen Beschickungsbehälter (8A, 8B, 8C), der zumindest zum Teil einen Pulverrückstand enthält, der aus einem Spritzbeschichtungsverfahren hervorgegangen ist, und Mittel für die Beschickung (18) der Zuführungsmittel (46) aus dem Beschickungsbehälter (8A, 8B, 8C) aufweist, und dass die Mittel (46) für die Zuführung des schmelzbaren Beschichtungsmaterials dafür vorgesehen sind, das schmelzbare Beschichtungsmaterial in Form von Pulver in die Flamme (44) einzuführen, und dass das Pulver von einer Legierung gebildet ist, die mindestens 50% Gewichtsanteil an Zn, insbesondere mindestens 85% Gewichtsanteil an Zn und vorzugsweise mindestens 95% Gewichtsanteil an Zn enthält, und dass der Restanteil der Legierung Aluminium enthält und insbesondere aus Aluminium besteht.
  17. Vorrichtung nach Anspruch 16, dadurch gekennzeichnet, dass die Zuführungsmittel (46) ein Einspritzelement (120A, 120B, 120C, 120D) aufweisen, das dafür vorgesehen ist, ein Gemisch aus Pulver aus Beschichtungsmaterial/Fördergas in einer Zuführungsrichtung (IA, IB, IC, ID) in die Flamme (44) einzuführen.
  18. Vorrichtung nach Anspruch 17, dadurch gekennzeichnet, dass die Zuführungsrichtung (IA bis ID) relativ zu der Flammenachse (Y-Y) im Wesentlichen in radialer Richtung ausgerichtet ist.
  19. Vorrichtung entsprechend einem der Ansprüche 17 bis 18, dadurch gekennzeichnet, dass sie ferner ein Element zum Vermischen (120) von Pulver aus Beschichtungsmaterial/Fördergas enthält, das einen Einlass für das Pulver (128), einen Einlass für das Fördergas (130), der für den Anschluss an eine Fördergasquelle (132) vorgesehen ist, und einen Auslass für das Gemisch aus Pulver aus Beschichtungsmaterial/Fördergas aufweist, dass das Mischelement (120) dafür vorgesehen ist, das Pulver mit einem Fördergasstrom zu vermischen, und dass der Auslass für das Gemisch aus Pulver aus Beschichtungsmaterial/Fördergas an zumindest ein Einspritzelement (120A, 120B, 120C, 120D) angeschlossen ist.
EP04742532A 2003-04-23 2004-04-16 Flammenbeschichtungsverfahren und entsprechende vorrichtung Expired - Lifetime EP1616041B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0304986A FR2854086B1 (fr) 2003-04-23 2003-04-23 Procede de revetement par flamme et dispositif correspondant
PCT/FR2004/000952 WO2004097060A1 (fr) 2003-04-23 2004-04-16 Procede de revetement par flamme et dispositif correspondant

Publications (2)

Publication Number Publication Date
EP1616041A1 EP1616041A1 (de) 2006-01-18
EP1616041B1 true EP1616041B1 (de) 2008-03-26

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Country Link
US (1) US20070026157A1 (de)
EP (1) EP1616041B1 (de)
CN (1) CN1798859B (de)
AT (1) ATE390498T1 (de)
BR (1) BRPI0410501B1 (de)
CA (1) CA2522932C (de)
DE (1) DE602004012728T2 (de)
ES (1) ES2304611T3 (de)
FR (1) FR2854086B1 (de)
RU (1) RU2353704C2 (de)
WO (1) WO2004097060A1 (de)

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Publication number Publication date
RU2353704C2 (ru) 2009-04-27
CN1798859A (zh) 2006-07-05
FR2854086A1 (fr) 2004-10-29
CA2522932A1 (fr) 2004-11-11
CA2522932C (fr) 2012-04-03
US20070026157A1 (en) 2007-02-01
BRPI0410501B1 (pt) 2016-04-05
CN1798859B (zh) 2010-11-03
EP1616041A1 (de) 2006-01-18
DE602004012728D1 (de) 2008-05-08
ES2304611T3 (es) 2008-10-16
ATE390498T1 (de) 2008-04-15
DE602004012728T2 (de) 2009-04-16
BRPI0410501A (pt) 2006-06-20
RU2005136352A (ru) 2007-06-27
FR2854086B1 (fr) 2007-03-30
WO2004097060A1 (fr) 2004-11-11

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