EP1194617B1 - Bath composition for electropolishing of titanium and method for using same - Google Patents

Bath composition for electropolishing of titanium and method for using same Download PDF

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Publication number
EP1194617B1
EP1194617B1 EP00951614A EP00951614A EP1194617B1 EP 1194617 B1 EP1194617 B1 EP 1194617B1 EP 00951614 A EP00951614 A EP 00951614A EP 00951614 A EP00951614 A EP 00951614A EP 1194617 B1 EP1194617 B1 EP 1194617B1
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solution
titanium
vol
polishing
bath
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German (de)
French (fr)
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EP1194617A1 (en
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Jean Guerin
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ORGANISATION EUROPEENNE POUR LA RECHERCHE NUCLEAIRE (CERN)
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    • 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 composition of bath for the electrolytic polishing of a surface unalloyed titanium metal and a process of use of this bath.
  • polishing is meant a treatment to reduce the roughness of a metal surface and, hence, to increase the brightness with, as consequently, less sensitivity to corrosion.
  • the present invention is in the context electrolytic polishing technique.
  • Electropolishing is based on two simultaneous and antagonistic reactions, including relative and diffusion phenomena at the interface metal / solution control the operating process.
  • Moon of these reactions is a dissolution reaction during from which the metal goes into solution in form ionic; the other reaction is an oxidation reaction during which an oxide layer is formed more or less protection limiting the evolution of the first reaction.
  • These two reactions, antagonistic and complex compete with the consequence a self-limitation of the chemical attack of the surface metal, whose polishing is only a result particular.
  • the polishing obtained electrolytically is significantly influenced by viscosity and / or resistivity of the electrolyte used.
  • He is known to use various acid compositions, especially compositions based on hydrofluoric acids, sulfuric, nitric, phosphoric in concentrations variety. Some of these acids (eg acid hydrofluoric) allow the dissolution of the formed on the metal surface, while the others (eg phosphoric acid, sulfuric acid, etc.) form the viscous medium necessary for the evolution of the electrolytic polishing. Proper control of concentrations of the constituents of the electrolytes is necessary to ensure the proper evolution of the process and determine the lifespan of these electrolytes.
  • the present invention therefore essentially for purpose of proposing a bath composition for polishing electrolytic specificity of unalloyed titanium, so to obtain a metal surface having a degree of polishing of high quality and measurable, but also of way to obtain, by an appropriate choice of parameters implementation of the composition, metal surfaces with roughness predeterminable (“adjustable”) and measurable (eg for biocompatible titanium implants).
  • a so-called additive "cationic wetting agent" for example a quaternary salt ammonium such as cetyltrimethylammonium bromide or a substituted derivative such as hexadecylpyridinium bromide 0.1 to 0.5 g / l.
  • a quaternary salt ammonium such as cetyltrimethylammonium bromide or a substituted derivative such as hexadecylpyridinium bromide 0.1 to 0.5 g / l.
  • This agent modifies the polarization of one of two electrodes (alternating phenomena adsorption and desorption) in the medium and leads to modifications of double layer phenomena. It results in an improvement in the quality of polishing with less metal removal.
  • the means proposed by the invention it is possible to regulate and control with extreme precision the conditions of electrochemical dissolution of the titanium metal surface and we are also able to achieve a polishing degree of titanium well better than the techniques known to this day. So, to fix ideas, from a raw titanium rolling surface which has a maximum roughness Rt of the order of 1 to 2 ⁇ m and a average roughness Ra of the order of 0.1 to 0.15 ⁇ m, it is possible to obtain, after electrolytic polishing in the conditions of the invention, a maximum roughness Rt of the order of 0.5 ⁇ m and an average roughness Ra of the order of 0.05 to 0.10 ⁇ m with a dissolved thickness of metal of in the order of 50 to 100 ⁇ m.

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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)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (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

La présente invention concerne une composition de bain pour le polissage électrolytique d'une surface métallique en titane non allié, ainsi qu'un procédé d'utilisation de ce bain.The present invention relates to a composition of bath for the electrolytic polishing of a surface unalloyed titanium metal and a process of use of 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.Under the term "polishing" is meant a treatment to reduce the roughness of a metal surface and, hence, to increase the brightness with, as consequently, less 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 oeuvre 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 électrolytique 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 in this purpose (use of abrasive powders of granulometry decreasing, fine machining, honing, etc.), there are also techniques based on the implementation of chemical and / or electrolytic reactions. Therefore we talk about chemical polishing when the reactions generated do not use an external source of current and electrolytic polishing when the reactions are dependent on an outside source of current, one of the electrodes (in principle the connected one at the positive pole of the electric power source) being formed by the piece to polish.

La présente invention se situe dans le contexte technique du polissage électrolytique.The present invention is in the context electrolytic polishing technique.

Le polissage électrolytique 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.Electropolishing is based on two simultaneous and antagonistic reactions, including relative and diffusion phenomena at the interface metal / solution control the operating process. Moon of these reactions is a dissolution reaction during from which the metal goes into solution in form ionic; the other reaction is an oxidation reaction during which an oxide layer is formed more or less protection limiting the evolution of the first reaction. These two reactions, antagonistic and complex, compete with the consequence a self-limitation of the chemical attack of the surface metal, whose polishing is only a result particular.

Le polissage obtenu par voie électrolytique est sensiblement influencé par la viscosité et/ou la résistivité de l'électrolyte mis en oeuvre. 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 électrolytique. 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 electrolytically is significantly influenced by viscosity and / or resistivity of the electrolyte used. He is known to use various acid compositions, especially compositions based on hydrofluoric acids, sulfuric, nitric, phosphoric in concentrations variety. Some of these acids (eg acid hydrofluoric) allow the dissolution of the formed on the metal surface, while the others (eg phosphoric acid, sulfuric acid, etc.) form the viscous medium necessary for the evolution of the electrolytic polishing. Proper control of concentrations of the constituents of the electrolytes is necessary to ensure the proper evolution of the process and determine the lifespan 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.Many bath compositions electropolishing 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 treat both pure titanium and its alloys. As a result, the quality of action of these baths is the result of a compromise and the polishing of surfaces treated metal is not optimum.

La présente invention a donc essentiellement pour but de proposer une composition de bain pour le polissage électrolytique 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 oeuvre de la composition, des surfaces métalliques présentant une rugosité prédéterminable ("réglable") et mesurable (par exemple pour des implants corporels en titane biocompatibles).The present invention therefore essentially for purpose of proposing a bath composition for polishing electrolytic specificity of unalloyed titanium, so to obtain a metal surface having a degree of polishing of high quality and measurable, but also of way to obtain, by an appropriate choice of parameters implementation of the composition, metal surfaces with roughness predeterminable ("adjustable") and measurable (eg for biocompatible titanium implants).

A ces fins, une composition de bain pour le polissage électrolytique d'une surface métallique en titane non allié se caractérise, étant conforme à l'invention, en ce qu'elle comprend :

  • 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 18 % en volume, cet acide donnant naissance à des sels qui sont solubles ; 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, dont le polissage de la surface métallique est l'un des résultats.
For these purposes, a bath composition for the electrolytic polishing of a nonalloyed titanium metal surface is characterized, according to the invention, in that it comprises:
  • sulfuric acid (95 to 98% solution): 20 to 40% by volume, this acid having slight oxidizing properties and a high viscosity;
  • hydrofluoric acid (40 to 48% solution): 10 to 18% by volume, this acid giving rise to salts which are soluble; and
  • acetic acid (90 to 100% solution): 42 to 62% vol., suitable for modifying the electrochemical equilibrium at the solution-metal interface, acetic acid making it possible to better control the oxidation and dissolution of the titanium surface , 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).The features of solution and concentration of sulfuric and hydrofluoric acids are adapted to the type of metal to be polished (unalloyed titanium).

Aucune des formulations connues de l'état de la technique dans le context du polissage électrolytique ne met en oeuvre 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 oeuvre lors de la réalisation du polissage électrolytique du titane.None of the known formulations of the state of the technique in the context of electrolytic polishing only uses acetic acid to polish specifically titanium. Acetic acid, having regard to its chemical properties (low dissociation, etc.), allows better regulation of electrochemical processes implemented during the polishing process electrolytic titanium.

De façon avantageuse, on peut ajouter en outre à la composition de bain précitée un agent d'addition dit "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/l. 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.Advantageously, it can additionally be added to the aforementioned bath composition a so-called additive "cationic wetting agent", for example a quaternary salt ammonium such as cetyltrimethylammonium bromide or a substituted derivative such as hexadecylpyridinium bromide 0.1 to 0.5 g / l. This agent modifies the polarization of one of two electrodes (alternating phenomena adsorption and desorption) in the medium and leads to modifications of double layer phenomena. It results in an improvement in the quality of polishing with less metal removal.

Pour la mise en oeuvre 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 caractéristiques 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 insuffisante 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.For the implementation of the abovementioned bath composition, the following conditions will be met:
  • bath temperature between 20 and 22 ° C, so that the necessary balance between the oxidation rate and the dissolution rate of the formed oxide layer is not disturbed;
  • anodic current density of about 7 A / dm;
  • electrical polishing voltage (voltage between electrodes) of about 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 or insufficient agitation would destabilize this interfacial layer and would lead to poor polishing results),
this is why the dissolution rate of titanium is about 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 électrolytique 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 électrolytique sont parfaitement maítrisables 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 titanium metal surface and we are also able to achieve a polishing degree of titanium well better than the techniques known to this day. So, to fix ideas, from a raw titanium rolling surface which has a maximum roughness Rt of the order of 1 to 2 μm and a average roughness Ra of the order of 0.1 to 0.15 μm, it is possible to obtain, after electrolytic polishing in 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 thickness of metal of in the order of 50 to 100 μm. In addition and above all, driving conditions of the polishing process electrolytic are perfectly controllable so as to obtain a measurable and predictable roughness. Finally the use of an addition agent as indicated above allows, by a better control of the conditions process evolution, eliminate a lower thickness of metal 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 % ; densité 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.
A specific example of the composition mentioned above, without addition agent, is as follows:
  • sulfuric acid: 98% solution; density 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 électrolytique, ont donné les résultats suivants (Rt = rugosité maximale ; Ra = rugosité moyenne) : avant polissage (surface brute de laminage) Rt = 1,80 µm Ra = 0,176 µm après polissage (épaisseur de métal dissoute = 22 µm) Rt = 0,670 µm Ra = 0,080 µm après polissage (épaisseur de métal dissoute = 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. Roughness measurements made on a nonalloyed titanium metal surface, before and after electrolytic polishing, gave the following results (Rt = maximum roughness, Ra = average roughness): before polishing (gross surface of rolling) Rt = 1.80 μm Ra = 0.176 μm after polishing (thickness of dissolved metal = 22 μm) Rt = 0.670 μm Ra = 0.080 μm after polishing (thickness of dissolved metal = 59 μm) Rt = 0.396 μm Ra = 0.057 μm after polishing (dissolved metal thickness = 116 μm) Rt = 0.432 μm Ra = 0.080 μm.

Claims (4)

  1. A bath composition for the electropolishing of a metal surface made of nonalloyed titanium, characterized in that it comprises:
    sulfuric acid (95 to 98% solution): 20 to 40 vol%,
    hydrofluoric acid (40 to 48% solution) : 10 to 18 vol%, and
    acetic acid (90 to 100% solution): 42 to 62 vol%, suitable for modifying the electrochemical equilibria at the solution/metal interface, acetic acid allowing better control of the oxidation and the dissolution of the titanium surface and resulting in self-limitation of the chemical dissolution of the metal surface.
  2. The composition as claimed in claim 1, characterized in that it comprises:
    sulfuric acid: 98% solution; density 1.84; 25 vol%;
    hydrofluoric acid: 40% solution; density 1.10; 15 vol%;
    glacial acetic acid: 100% solution; density 1.05; 60 vol%.
  3. The composition as claimed in claim 1 or 2, characterized in that it furthermore includes an addition agent chosen from cetyltrimethylammonium bromide and hexadecylpyridinium bromide, in an amount ranging from 0.1 to 0.5 g/l.
  4. A method of using a bath composition for the electropolishing of titanium as claimed in any one of claims 1 to 3, characterized in that:
    the bath temperature is between about 20 and 22°C;
    the current density is about 7 A/dm2;
    the polishing voltage is about 11 volts;
    the bath is stirred moderately,
    whereby the rate of dissolution of the titanium is about 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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EP1194617B1 true EP1194617B1 (en) 2003-04-09

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FR (1) FR2795433B1 (en)
HK (1) HK1047774A1 (en)
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AU6449700A (en) 2001-01-31
FR2795433A1 (en) 2000-12-29
DE60002084T2 (en) 2004-03-04
WO2001000906A1 (en) 2001-01-04
DE60002084D1 (en) 2003-05-15
JP4536975B2 (en) 2010-09-01
EP1194617A1 (en) 2002-04-10
ES2197110T3 (en) 2004-01-01
HK1047774A1 (en) 2003-03-07
PT1194617E (en) 2003-10-31
FR2795433B1 (en) 2001-08-31
US6610194B1 (en) 2003-08-26
ATE237010T1 (en) 2003-04-15
RU2241791C2 (en) 2004-12-10
CN1230576C (en) 2005-12-07
JP2003513166A (en) 2003-04-08
CN1358240A (en) 2002-07-10
DK1194617T3 (en) 2003-07-21

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