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EP1194617A1 - Bath composition for electropolishing of titanium and method for using same - Google Patents

Bath composition for electropolishing of titanium and method for using same

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Publication number
EP1194617A1
EP1194617A1 EP00951614A EP00951614A EP1194617A1 EP 1194617 A1 EP1194617 A1 EP 1194617A1 EP 00951614 A EP00951614 A EP 00951614A EP 00951614 A EP00951614 A EP 00951614A EP 1194617 A1 EP1194617 A1 EP 1194617A1
Authority
EP
European Patent Office
Prior art keywords
solution
titanium
vol
polishing
bath
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.)
Granted
Application number
EP00951614A
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German (de)
French (fr)
Other versions
EP1194617B1 (en
Inventor
Jean Guerin
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ORGANISATION EUROPEENNE POUR LA RECHERCHE NUCLEAIRE (CERN)
Original Assignee
ORGANISATION EUROPEENNE POUR LA RECHERCHE NUCLEAIRE (CERN)
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Publication of EP1194617A1 publication Critical patent/EP1194617A1/en
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Publication of EP1194617B1 publication Critical patent/EP1194617B1/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/26—Polishing of heavy metals of refractory metals

Definitions

  • the present invention relates to a bath composition for the electrolytic polishing of a metallic surface of unalloyed titanium, as well as to a method of using this bath.
  • polishing is meant a treatment aimed at reducing the roughness of a metal surface and, consequently, at increasing its gloss with, as a consequence, a lower sensitivity to corrosion.
  • the present invention is situated in the technical context of electrolytic polishing.
  • Electrolytic polishing is based on two simultaneous and antagonistic reactions, whose relative speeds and diffusion phenomena at the metal / solution interface control the operating process.
  • One of these reactions is a dissolution reaction during which the metal goes into solution in ionic form; the other reaction is an oxidation reaction during which an oxide layer is formed more or less protective limiting by its presence the evolution of the first reaction.
  • These two reactions, antagonistic and complex enter into competition with the consequence of a self-limitation of the chemical attack on the metallic surface, the polishing of which is only a particular result.
  • the polishing obtained by electrolytic means is appreciably influenced by the viscosity and / or the resistivity of the electrolyte used. It is known to use various acid compositions, in particular compositions based on hydrofluoric, sulfuric, nitric, phosphoric acids in various concentrations. Some of these acids (for example hydrofluoric acid) allow the dissolution of the oxide layer formed on the metal surface, while others (for example phosphoric acid, sulfuric, etc.) form the viscous medium necessary for the evolution of electrolytic polishing. Correct control of the concentrations of the constituents of the electrolytes is essential to ensure the proper development of the process and determine the life of these electrolytes.
  • the main object of the present invention is therefore to propose a bath composition for the specific electrolytic polishing of unalloyed titanium, so to obtain a metal surface having a high quality and measurable degree of polishing, but also so as to obtain, by an appropriate choice of the electrical parameters for processing the composition, metal surfaces having a predetermined roughness ("adjustable") and measurable (for example for biocompatible titanium body implants).
  • a bath composition for the electrolytic polishing of a metal surface of unalloyed titanium is characterized, being in accordance with the invention, in that it comprises:
  • a so-called addition agent can also be added to the above-mentioned bath composition.
  • cationic wetting agent for example a quaternary ammonium salt such as cetyltrimethylammonium bromide or a substituted derivative such as hexadecylpyridinium bromide in an amount of 0.1 to 0.5 g / l.
  • This agent modifies the polarization of one of two electrodes (alternating phenomena of adsorption and desorption) in the medium and leads to modifications of the phenomena of double layer. This results in an improvement in the quality of polishing with less removal of metal.
  • bath temperature of between 20 and 22 ° C., so that the necessary balance between the speed of oxidation and the speed of dissolution of the oxide layer formed; density of the anode current of about 7 A / dm; electrical polishing voltage (voltage between electrodes) of approximately 11 volts, these electrical characteristics (current density and voltage) being adapted according to the shape of the surfaces to be polished and / or the possible use of anode ( s) auxiliary (s); moderate agitation of the bath, adaptable for each specific application, so as to respect the stability of the viscous layer at the interface of the electrode (surface to be polished) and the liquid solution (excessive agitation or insufficient fisante would destabilize this interfacial layer and lead to poor polishing results), which makes the titanium dissolution rate around 6 microns / min.
  • the means proposed by the invention it is possible to regulate and control with extreme precision the conditions of electrochemical dissolution of the metal surface in titanium and it is also possible to achieve a degree of polishing of the titanium much higher than what allowed the techniques known to date.
  • a surface in rough rolling titanium which has a maximum roughness Rt of the order of 1 to 2 ⁇ m and an average roughness Ra of the order of 0.1 to 0.15 ⁇ m
  • composition mentioned above without addition agent, is the following: - sulfuric acid: 98% solution; density

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

A bath composition for the electropolishing of a metal surface made of nonalloyed titanium is disclosed. The bath composition may comprise sulfuric acid of 2 to 40% by volume, hydrofluoric acid of 10 to 18% by volume and acetic acid of 42 to 62% by volume.

Description

COMPOSITION DE BAIN POUR LE POLISSAGE ELECTROLYTIQUE DU TITANE, ET SON PROCEDE D'UTILISATION BATH COMPOSITION FOR ELECTROLYTIC POLISHING OF TITANIUM AND METHOD OF USING SAME
La présente invention concerne une composition de bain pour le polissage electrolytique d'une surface métallique en titane non allié, ainsi qu'un procédé d'utilisation de ce bain.The present invention relates to a bath composition for the electrolytic polishing of a metallic surface of unalloyed titanium, as well as to a method of using this bath.
Sous le terme "polissage", on entend un traitement visant à diminuer la rugosité d'une surface métallique et, partant, à en augmenter la brillance avec, comme conséquence, une moindre sensibilité à la corrosion.By the term "polishing" is meant a treatment aimed at reducing the roughness of a metal surface and, consequently, at increasing its gloss with, as a consequence, a lower sensitivity to corrosion.
Mis à part les moyens mécaniques utilisés dans ce but (emploi de poudres abrasives de granulométries décroissantes, usinages fins, rodages, etc.), il existe également des techniques reposant sur la mise en œuvre de réactions chimiques et/ou électrolytiques . C'est ainsi que l'on parle de polissage chimique lorsque les réactions engendrées ne font pas appel à une source extérieure de courant et de polissage electrolytique lorsque les réactions sont sous la dépendance d'une source extérieure de courant, une des électrodes ( en principe celle reliée au pôle positif de la source de courant électrique) étant constituée par la pièce à polir.Apart from the mechanical means used for this purpose (use of abrasive powders with decreasing particle sizes, fine machining, lapping, etc.), there are also techniques based on the implementation of chemical and / or electrolytic reactions. This is how we speak of chemical polishing when the reactions generated do not call on an external source of current and electrolytic polishing when the reactions are dependent on an external source of current, one of the electrodes (in principle that connected to the positive pole of the electric current source) being constituted by the part to be polished.
La présente invention se situe dans le contexte technique du polissage electrolytique.The present invention is situated in the technical context of electrolytic polishing.
Le polissage electrolytique repose sur deux réactions simultanées et antagonistes, dont les vitesses relatives et les phénomènes de diffusion à l'interface métal/solution contrôlent le processus opératoire. L'une de ces réactions est une réaction de dissolution au cours de laquelle le métal passe en solution sous forme ionique ; l'autre réaction est une réaction d'oxydation durant laquelle se forme une couche d'oxyde plus ou moins protectrice limitant par sa présence l'évolution de la première réaction. Ces deux réactions, antagonistes et complexes, entrent en compétition avec pour conséquence une auto-limitation de l'attaque chimique de la surface métallique, dont le polissage n'est qu'un résultat particulier .Electrolytic polishing is based on two simultaneous and antagonistic reactions, whose relative speeds and diffusion phenomena at the metal / solution interface control the operating process. One of these reactions is a dissolution reaction during which the metal goes into solution in ionic form; the other reaction is an oxidation reaction during which an oxide layer is formed more or less protective limiting by its presence the evolution of the first reaction. These two reactions, antagonistic and complex, enter into competition with the consequence of a self-limitation of the chemical attack on the metallic surface, the polishing of which is only a particular result.
Le polissage obtenu par voie electrolytique est sensiblement influencé par la viscosité et/ou la résistivité de l' electrolyte mis en œuvre. Il est connu d'avoir recours à diverses compositions d'acides, notamment des compositions à base d'acides fluorhydrique, sulfurique, nitrique, phosphorique dans des concentrations diverses. Les uns de ces acides (par exemple l'acide fluorhydrique) permettent la dissolution de la couche d'oxyde formée sur la surface métallique, tandis que les autres (par exemple acide phosphorique, sulfurique, etc.) forment le milieu visqueux nécessaire à l'évolution du polissage electrolytique. Un contrôle correct des concentrations des constituants des électrolytes est indispensable pour assurer l'évolution convenable du processus et déterminer la durée de vie de ces électrolytes .The polishing obtained by electrolytic means is appreciably influenced by the viscosity and / or the resistivity of the electrolyte used. It is known to use various acid compositions, in particular compositions based on hydrofluoric, sulfuric, nitric, phosphoric acids in various concentrations. Some of these acids (for example hydrofluoric acid) allow the dissolution of the oxide layer formed on the metal surface, while others (for example phosphoric acid, sulfuric, etc.) form the viscous medium necessary for the evolution of electrolytic polishing. Correct control of the concentrations of the constituents of the electrolytes is essential to ensure the proper development of the process and determine the life of these electrolytes.
De nombreuses compositions de bain d' électropolissage sont connues (voir par exemple US 3 766 030, US 3 864 238, US 5 591 320, US 5 565 084, etc.). Certaines de ces compositions connues sont polyvalentes et permettent de traiter aussi bien le titane pur que ses alliages. De ce fait, la qualité d'action de ces bains est le résultat d'un compromis et le polissage des surfaces métalliques traitées n'est pas optimum.Numerous electropolishing bath compositions are known (see, for example, US 3,766,030, US 3,864,238, US 5,591,320, US 5,565,084, etc.). Some of these known compositions are versatile and make it possible to treat both pure titanium and its alloys. Therefore, the quality of action of these baths is the result of a compromise and the polishing of the treated metal surfaces is not optimum.
La présente invention a donc essentiellement pour but de proposer une composition de bain pour le polissage electrolytique spécifique du titane non allié, de manière à obtenir une surface métallique ayant un degré de polissage de haute qualité et mesurable, mais aussi de manière à obtenir, par un choix approprié des paramètres électriques de mise en œuvre de la composition, des surfaces métalliques présentant une rugosité prédéterminable ("réglable") et mesurable (par exemple pour des implants corporels en titane biocompatibles).The main object of the present invention is therefore to propose a bath composition for the specific electrolytic polishing of unalloyed titanium, so to obtain a metal surface having a high quality and measurable degree of polishing, but also so as to obtain, by an appropriate choice of the electrical parameters for processing the composition, metal surfaces having a predetermined roughness ("adjustable") and measurable (for example for biocompatible titanium body implants).
A ces fins, une composition de bain pour le polissage electrolytique d'une surface métallique en titane non allié se caractérise, étant conforme à l'invention, en ce qu'elle comprend :For these purposes, a bath composition for the electrolytic polishing of a metal surface of unalloyed titanium is characterized, being in accordance with the invention, in that it comprises:
- acide sulfurique (solution 95 à 98 %) : 20 à 40 % en volume, cet acide présentant de légères propriétés oxydantes et une forte viscosité ; - acide fluorhydrique (solution 40 à 48 %) : 10 à- sulfuric acid (solution 95 to 98%): 20 to 40% by volume, this acid having slight oxidizing properties and a high viscosity; - hydrofluoric acid (solution 40 to 48%): 10 to
18 % en volume, cet acide donnant naissance à des sels qui sont solubles ; et18% by volume, this acid giving rise to salts which are soluble; and
- acide acétique (solution 90 à 100 %) : 42 à 62 % vol., propre à modifier les équilibres électrochimiques à l' interface solution-métal, l'acide acétique permettant de mieux contrôler l'oxydation et la dissolution de la surface de titane, et de conduire à une auto-limitation de la dissolution chimique de la surface métallique, dont le polissage de la surface métallique est l'un des résultats.- acetic acid (solution 90 to 100%): 42 to 62% vol., capable of modifying the electrochemical equilibria at the solution-metal interface, acetic acid making it possible to better control the oxidation and the dissolution of the surface of titanium, and lead to a self-limitation of the chemical dissolution of the metal surface, of which the polishing of the metal surface is one of the results.
Les caractéristiques de solution et de concentration des acides sulfurique et fluorhydrique sont adaptées au type de métal à polir (titane non allié) . Aucune des formulations connues de l'état de la technique ne met en œuvre l'acide acétique pour polir spécifiquement le titane. L'acide acétique, eu égard à ses propriétés chimiques ( faible dissociation, etc ) , permet une meilleure régulation des processus électrochimiques mis en œuvre lors de la réalisation du polissage electrolytique du titane.The solution and concentration characteristics of sulfuric and hydrofluoric acids are adapted to the type of metal to be polished (unalloyed titanium). None of the formulations known from the prior art uses acetic acid to specifically polish titanium. Acetic acid, having regard to its chemical properties (weak dissociation, etc.), allows better regulation of the electrochemical processes implemented during the electrolytic polishing of titanium.
De façon avantageuse, on peut ajouter en outre à la composition de bain précitée un agent d'addition ditAdvantageously, a so-called addition agent can also be added to the above-mentioned bath composition.
"mouillant cationique", par exemple un sel quaternaire d'ammonium tel que le cétyltriméthylammonium bromure ou un dérivé substitué tel que l' hexadécylpyridinium bromure à raison de 0,1 à 0,5 g/1. Cet agent modifie la polarisation de l'une de deux électrodes (phénomènes alternés d' adsorption et de désorption) dans le milieu et conduit à des modifications des phénomènes de double couche. Il en résulte une amélioration de la qualité du polissage avec un enlèvement moindre de métal . Pour la mise en œuvre de la composition de bain précitée, on réunira les conditions suivantes : température du bain comprise entre 20 et 22 °C, de manière que ne soit pas perturbé l'équilibre nécessaire entre la vitesse d'oxydation et la vitesse de dissolution de la couche d'oxyde formée ; densité du courant anodique d' environ 7 A/dm; tension électrique de polissage (tension entre électrodes) d'environ 11 volts, ces caractéristi- ques électriques (densité de courant et tension) étant adaptées en fonction de la forme des surfaces à polir et/ou de l'utilisation éventuelle d'anode (s) auxiliaire (s) ; agitation modérée du bain, adaptable pour chaque application spécifique, de manière à respecter la stabilité de la couche visqueuse à l'interface de l'électrode (surface à polir) et de la solution liquide (une agitation trop importante ou insuf- fisante déstabiliserait cette couche interfaciale et conduirait à de mauvais résultats de polissage) , ce grâce à quoi la vitesse de dissolution du titane est d'environ 6 microns/mn."cationic wetting agent", for example a quaternary ammonium salt such as cetyltrimethylammonium bromide or a substituted derivative such as hexadecylpyridinium bromide in an amount of 0.1 to 0.5 g / l. This agent modifies the polarization of one of two electrodes (alternating phenomena of adsorption and desorption) in the medium and leads to modifications of the phenomena of double layer. This results in an improvement in the quality of polishing with less removal of metal. For the implementation of the abovementioned bath composition, the following conditions will be met: bath temperature of between 20 and 22 ° C., so that the necessary balance between the speed of oxidation and the speed of dissolution of the oxide layer formed; density of the anode current of about 7 A / dm; electrical polishing voltage (voltage between electrodes) of approximately 11 volts, these electrical characteristics (current density and voltage) being adapted according to the shape of the surfaces to be polished and / or the possible use of anode ( s) auxiliary (s); moderate agitation of the bath, adaptable for each specific application, so as to respect the stability of the viscous layer at the interface of the electrode (surface to be polished) and the liquid solution (excessive agitation or insufficient fisante would destabilize this interfacial layer and lead to poor polishing results), which makes the titanium dissolution rate around 6 microns / min.
Grâce aux moyens proposés par l'invention, il est possible de réguler et de contrôler avec une extrême précision les conditions de dissolution électrochimique de la surface métallique en titane et on est aussi en mesure de parvenir à un degré de polissage du titane bien supérieur à ce que permettaient les techniques connues à ce jour. Ainsi, pour fixer les idées, à partir d'une surface en titane brute de laminage qui présente une rugosité maximale Rt de l'ordre de 1 à 2 μm et une rugosité moyenne Ra de l'ordre de 0,1 à 0,15 μm, il est possible d'obtenir, après polissage electrolytique dans les conditions de l'invention, une rugosité maximale Rt de l'ordre de 0,5 μm et une rugosité moyenne Ra de l'ordre de 0,05 à 0,10 μm avec une épaisseur dissoute de métal de l'ordre de 50 à 100 μm. En outre et surtout, les conditions de conduite du processus de polissage electrolytique sont parfaitement maîtrisables de manière à obtenir une rugosité mesurable et prédéterminable . Enfin le recours à un agent d'addition comme indiqué plus haut permet, par un meilleur contrôle des conditions d'évolution du processus, d'éliminer une épaisseur moindre de métal pour parvenir à une valeur donnée de rugosité.Thanks to the means proposed by the invention, it is possible to regulate and control with extreme precision the conditions of electrochemical dissolution of the metal surface in titanium and it is also possible to achieve a degree of polishing of the titanium much higher than what allowed the techniques known to date. Thus, to fix the ideas, starting from a surface in rough rolling titanium which has a maximum roughness Rt of the order of 1 to 2 μm and an average roughness Ra of the order of 0.1 to 0.15 μm, it is possible to obtain, after electrolytic polishing under the conditions of the invention, a maximum roughness Rt of the order of 0.5 μm and an average roughness Ra of the order of 0.05 to 0.10 μm with a dissolved metal thickness of the order of 50 to 100 μm. In addition and above all, the conditions for conducting the electrolytic polishing process are perfectly controllable so as to obtain a measurable and predetermined roughness. Finally, the use of an addition agent as indicated above makes it possible, by better control of the conditions of evolution of the process, to eliminate a lesser thickness of metal in order to achieve a given value of roughness.
Un exemple spécifique de la composition mentionnée plus haut, sans agent d'addition, est la suivante : - acide sulfurique : solution à 98 % ; densitéA specific example of the composition mentioned above, without addition agent, is the following: - sulfuric acid: 98% solution; density
1,84 ; 25 % vol ; acide fluorhydrique : solution à 40 % ; densité 1, 10 ; 15 % vol ; acide acétique glacial : solution à 100 % ; densité 1,05 ; 60 % vol.1.84; 25% vol; hydrofluoric acid: 40% solution; density 1, 10; 15% vol; glacial acetic acid: 100% solution; density 1.05; 60% vol.
Des mesures de rugosité effectuées sur une surface métallique en titane non allié, avant et après polissage electrolytique, ont donné les résultats suivants (Rt = rugosité maximale ; Ra = rugosité moyenne) :Roughness measurements carried out on a metal surface made of unalloyed titanium, before and after electrolytic polishing, gave the following results (Rt = maximum roughness; Ra = average roughness):
avant polissage (surface brute de laminage) Rt = 1,80 μm Ra = 0,176 μmbefore polishing (gross rolling surface) Rt = 1.80 μm Ra = 0.176 μm
après polissage (épaisseur de métal dissoute = 22 uni) Rt = 0,670 μm Ra = 0,080 μmafter polishing (dissolved metal thickness = 22 uni) Rt = 0.670 μm Ra = 0.080 μm
après polissage (épaisseur de métal dissoute = 59 μm) Rt = 0,396 μm Ra = 0,057 μmafter polishing (dissolved metal thickness = 59 μm) Rt = 0.396 μm Ra = 0.057 μm
après polissage (épaisseur de métal dissoute = 116 μm) Rt = 0,432 μm Ra= 0,080 μm. after polishing (dissolved metal thickness = 116 μm) Rt = 0.432 μm Ra = 0.080 μm.

Claims

REVENDICATIONS
1. Composition de bain pour le polissage electrolytique d'une surface métallique en titane non allié, caractérisée en ce qu'elle comprend : acide sulfurique (solution 95 à 98 %) : 20 à 40 % vol., acide fluorhydrique (solution 40 à 48 %) : 10 à 18 % vol., et - acide acétique (solution 90 à 100 %) : 42 à 62 % vol., propre à modifier les équilibres électrochimiques à l'interface solution-métal, l'acide acétique permettant de mieux contrôler l'oxydation et la dissolution de la surface de titane et de conduire à une auto-limitation de la dissolution chimique de la surface métallique.1. Bath composition for the electrolytic polishing of a metallic surface of unalloyed titanium, characterized in that it comprises: sulfuric acid (solution 95 to 98%): 20 to 40% vol., Hydrofluoric acid (solution 40 to 48%): 10 to 18% vol., And - acetic acid (solution 90 to 100%): 42 to 62% vol., Capable of modifying the electrochemical equilibria at the solution-metal interface, acetic acid making it possible to better control the oxidation and dissolution of the titanium surface and lead to self-limitation of the chemical dissolution of the metal surface.
2. Composition selon la revendication 1, caractérisée en ce qu'elle comprend : - acide sulfurique : solution à 98 % ; densité2. Composition according to claim 1, characterized in that it comprises: - sulfuric acid: 98% solution; density
1,84 ; 25 % vol ;1.84; 25% vol;
- acide fluorhydrique : solution à 40 % ; densité 1,10 ; 15 % vol ;- hydrofluoric acid: 40% solution; density 1.10; 15% vol;
- acide acétique glacial : solution à 100 % ; densité 1,05 ; 60 % vol.- glacial acetic acid: 100% solution; density 1.05; 60% vol.
3. Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle comprend en outre un agent d'addition choisi parmi le cetyltrimethylammonium bromure et l'hexadécylpyridinium bromure, à raison de 0,1 à 0,5 g/1.3. Composition according to claim 1 or 2, characterized in that it further comprises an addition agent chosen from cetyltrimethylammonium bromide and hexadecylpyridinium bromide, in an amount of 0.1 to 0.5 g / 1.
4. Procédé d'utilisation d'une composition de bain pour le polissage electrolytique du titane selon l'une quelconque des revendications 1 à 3, caractérisé en ce que : la température du bain est comprise entre environ 20 et 22°C, la densité de courant est d'environ 7 A/dm2, la tension de polissage est d'environ 11 volts, le bain est agité de façon modérée, ce grâce à quoi la vitesse de dissolution du titane est d'environ 6 microns/mn. 4. Method of using a bath composition for the electrolytic polishing of titanium according to one any one of claims 1 to 3, characterized in that: the bath temperature is between approximately 20 and 22 ° C, the current density is approximately 7 A / dm 2 , the polishing voltage is approximately 11 volts , the bath is stirred moderately, whereby the dissolution rate of the titanium is approximately 6 microns / min.
EP00951614A 1999-06-25 2000-06-20 Bath composition for electropolishing of titanium and method for using same Expired - Lifetime EP1194617B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9908151 1999-06-25
FR9908151A FR2795433B1 (en) 1999-06-25 1999-06-25 BATH COMPOSITION FOR ELECTROLYTIC POLISHING OF TITANIUM, AND METHOD OF USING SAME
PCT/FR2000/001694 WO2001000906A1 (en) 1999-06-25 2000-06-20 Bath composition for electropolishing of titanium and method for using same

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EP (1) EP1194617B1 (en)
JP (1) JP4536975B2 (en)
CN (1) CN1230576C (en)
AT (1) ATE237010T1 (en)
AU (1) AU6449700A (en)
DE (1) DE60002084T2 (en)
DK (1) DK1194617T3 (en)
ES (1) ES2197110T3 (en)
FR (1) FR2795433B1 (en)
HK (1) HK1047774A1 (en)
PT (1) PT1194617E (en)
RU (1) RU2241791C2 (en)
WO (1) WO2001000906A1 (en)

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AU6449700A (en) 2001-01-31
EP1194617B1 (en) 2003-04-09
WO2001000906A1 (en) 2001-01-04
DE60002084T2 (en) 2004-03-04
ATE237010T1 (en) 2003-04-15
ES2197110T3 (en) 2004-01-01
JP2003513166A (en) 2003-04-08
PT1194617E (en) 2003-10-31
US6610194B1 (en) 2003-08-26
HK1047774A1 (en) 2003-03-07
FR2795433A1 (en) 2000-12-29
RU2241791C2 (en) 2004-12-10
DK1194617T3 (en) 2003-07-21
DE60002084D1 (en) 2003-05-15
JP4536975B2 (en) 2010-09-01
FR2795433B1 (en) 2001-08-31
CN1358240A (en) 2002-07-10
CN1230576C (en) 2005-12-07

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