CA2520584A1 - Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur, cathode activee en resultant et son utilisation pour l'electrolyse de solutions aqueuses de chlorures de metaux alcalins - Google Patents

Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur, cathode activee en resultant et son utilisation pour l'electrolyse de solutions aqueuses de chlorures de metaux alcalins Download PDF

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CA2520584A1
CA2520584A1 CA002520584A CA2520584A CA2520584A1 CA 2520584 A1 CA2520584 A1 CA 2520584A1 CA 002520584 A CA002520584 A CA 002520584A CA 2520584 A CA2520584 A CA 2520584A CA 2520584 A1 CA2520584 A1 CA 2520584A1
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metal
acetylacetonate
substrate
solvent
electrolysis
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CA2520584C (fr
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Francoise Andolfatto
Philippe Joubert
Gerard Duboeuf
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Arkema SA
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Arkema
Francoise Andolfatto
Philippe Joubert
Gerard Duboeuf
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Chemically Coating (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

L'invention concerne un procédé de formation d'un revêtement d'oxydes métalliques comprenant au moins un métal précieux du groupe VIII de la classification des éléments éventuellement associé à du titane et/ou du zirconium sur un substrat électroconducteur en acier ou en fer, qui consiste à appliquer une solution d'acétylacétonates dudit (desdits) métal (métaux) dissout(s) dans un (des) solvant(s) solubilisant spécifiquement chaque acétylacétonate métallique, puis à sécher et calciner le substrat revêtu. L'invention concerne également une cathode activée obtenue à partir du substrat électroconducteur revêtu d'oxydes métalliques et son utilisation po ur l'électrolyse de solutions aqueuses de chlorures de métaux alcalins.

Claims (19)

1. Procédé de formation d'un revêtement d'oxydes métalliques comprenant au moins un métal précieux du groupe VIII de la classification périodique des éléments éventuellement associé à du titane et/ou du zirconium, sur un substrat électroconducteur, ledit procédé consistant à appliquer sur ledit substrat une solution comprenant au moins un composé organométallique puis à transformer ledit (ou lesdits) composé(s) organométallique(s) en oxyde(s) métallique(s) au moyen d'un traitement thermique, ledit procédé étant caractérisé en ce que le substrat électroconducteur est en acier ou en fer et en ce que la seule solution appliquée sur ledit substrat est une solution, non aqueuse, d'acétylacétonate métallique ou d'un mélange d'acétylacétonates métalliques dissout(s) dans un (des) solvant(s) solubilisant spécifiquement chaque acétylacétonate métallique, le (les) solvant(s) étant choisi(s) parmi les alcools, les cétones, les chlorométhanes ou un mélange de deux ou plusieurs solvants ci-dessus mentionnés.
2. Procédé selon la revendication 1, caractérisé en ce que le métal précieux du groupe VIII de la classification périodique des éléments est le ruthénium, le rhodium, le palladium, l'osmium, l'iridium ou le platine.
3. Procédé selon la revendication 2, caractérisé en ce que le métal précieux est le ruthénium ou l'iridium.
4. Procédé selon la revendication 3, caractérisé en ce que le métal précieux est le ruthénium.
5. Procédé selon la revendication 1, caractérisé en ce que l'alcool est l'éthanol ou l'isopropanol.
6. Procédé selon la revendication 1, caractérisé en ce que la cétone est l'acétone.
7. Procédé selon la revendication 1, caractérisé en ce que le chlorométhane est le chloroforme.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la solution d'acétylacétonate métallique est obtenue par dissolution dudit acétylacétonate métallique dans son solvant spécifique ou dans un mélange de solvants contenant le solvant spécifique.
9. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la solution contenant plusieurs acétylacétonates métalliques est obtenue :
- soit par dissolution desdits acétylacétonates métalliques dans un mélange de solvants contenant les solvants spécifiques desdits acétylacétonates métalliques ;
- soit par mélange de solutions ne contenant qu'un seul acétylacétonate métallique obtenues par dissolution dudit acétylacétonate métallique dans un solvant spécifique ou dans un mélange de solvants contenant le solvant spécifique dudit acétylacétonate.
10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que, pour obtenir le revêtement d'oxyde(s) métallique(s), on effectue dans une première étape, un prétraitement du substrat en acier ou en fer puis dans une seconde étape, on dépose sur ledit substrat prétraité la solution contenant le (ou les) acétylacétonate(s) métallique(s), on sèche puis on calcine le substrat ainsi revêtu.
11. Procédé selon la revendication 10, caractérisé en ce que le séchage est effectué à une température au plus égale à 150°C.
12. Procédé selon la revendication 10, caractérisé en ce que le substrat revêtu par le (ou les) acétylacétonate(s) métallique(s) est calciné sous air ou bien sous gaz inerte enrichi avec de l'oxygène à une température au moins égale à
300°C et, de préférence, à une température comprise entre 400°C et 600°C
pendant une durée allant de 10 minutes à 2 heures.
13. Procédé selon la revendication 10, caractérisé en ce que la seconde étape est répétée au moins 1 fois et, de préférence, répétée entre 2 et 6 fois.
14. Substrat électroconducteur en acier ou en fer portant un revêtement d'oxydes métalliques formé au moyen d'un procédé selon l'une des revendications 1 à 13.
15. Utilisation du substrat électroconducteur selon la revendication 14 pour l'obtention d'une cathode activée.
16. Utilisation d'une cathode activée selon la revendication 15 pour l'électrolyse de solutions aqueuses de chlorures de métaux alcalins.
17. Utilisation selon la revendication 16, caractérisée en ce que les solutions aqueuses de chlorures de métaux alcalins sont des solutions aqueuses de chlorure de sodium.
18. Procédé de fabrication de chlore et d'hydroxyde de métal alcalin par électrolyse du chlorure correspondant au moyen d'une cathode selon la revendication 15.
19. Procédé de fabrication de chlorate de métaux alcalins par électrolyse du chlorure correspondant au moyen d'une cathode selon la revendication 15.
CA2520584A 2003-03-28 2004-03-25 Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur, cathode activee en resultant et son utilisation pour l'electrolyse de solutions aqueuses de chlorures de metaux alcalins Expired - Fee Related CA2520584C (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0303867A FR2852973B1 (fr) 2003-03-28 2003-03-28 Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur; cathode activee en resultant et son utilisation pour l'electrolyse de solutions acqueuses de chorures de meteaux alcalins.
FR03/03867 2003-03-28
PCT/FR2004/000746 WO2004087992A2 (fr) 2003-03-28 2004-03-25 Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur, cathode activee en resultant et son utilisation pour l'electrolyse de solutions aqueuses de chlorures de metaux alcalins.

Publications (2)

Publication Number Publication Date
CA2520584A1 true CA2520584A1 (fr) 2004-10-14
CA2520584C CA2520584C (fr) 2011-08-23

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CA2520584A Expired - Fee Related CA2520584C (fr) 2003-03-28 2004-03-25 Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur, cathode activee en resultant et son utilisation pour l'electrolyse de solutions aqueuses de chlorures de metaux alcalins

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Country Link
US (1) US7790233B2 (fr)
EP (1) EP1608795B1 (fr)
JP (1) JP4532471B2 (fr)
KR (1) KR101111369B1 (fr)
CN (1) CN1795291B (fr)
AT (1) ATE330043T1 (fr)
BR (1) BRPI0408905A (fr)
CA (1) CA2520584C (fr)
DE (1) DE602004001230T2 (fr)
ES (1) ES2270380T3 (fr)
FR (1) FR2852973B1 (fr)
MX (1) MXPA05010353A (fr)
PL (1) PL1608795T3 (fr)
UA (1) UA80610C2 (fr)
WO (1) WO2004087992A2 (fr)
ZA (1) ZA200507825B (fr)

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ATE330043T1 (de) 2006-07-15
JP4532471B2 (ja) 2010-08-25
CN1795291B (zh) 2011-08-31
CA2520584C (fr) 2011-08-23
EP1608795A2 (fr) 2005-12-28
KR20050114265A (ko) 2005-12-05
PL1608795T3 (pl) 2006-11-30
ES2270380T3 (es) 2007-04-01
BRPI0408905A (pt) 2006-03-28
US20060263614A1 (en) 2006-11-23
FR2852973B1 (fr) 2006-05-26
JP2006521469A (ja) 2006-09-21
CN1795291A (zh) 2006-06-28
DE602004001230D1 (de) 2006-07-27
DE602004001230T2 (de) 2007-04-19
KR101111369B1 (ko) 2012-04-09
WO2004087992A2 (fr) 2004-10-14
UA80610C2 (en) 2007-10-10
MXPA05010353A (es) 2005-12-14
ZA200507825B (en) 2007-01-31
EP1608795B1 (fr) 2006-06-14
US7790233B2 (en) 2010-09-07
FR2852973A1 (fr) 2004-10-01
WO2004087992A3 (fr) 2005-02-17

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