EP1903132A2 - Electropolishing method for cobalt and cobalt alloys - Google Patents

Electropolishing method for cobalt and cobalt alloys Download PDF

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Publication number
EP1903132A2
EP1903132A2 EP07018326A EP07018326A EP1903132A2 EP 1903132 A2 EP1903132 A2 EP 1903132A2 EP 07018326 A EP07018326 A EP 07018326A EP 07018326 A EP07018326 A EP 07018326A EP 1903132 A2 EP1903132 A2 EP 1903132A2
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Prior art keywords
cobalt
electrolyte
acid
alloys
electropolishing
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German (de)
French (fr)
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EP1903132A3 (en
EP1903132B1 (en
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Siegfried Piesslinger-Schweiger
Olaf BÖHME
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Poligrat GmbH
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Poligrat GmbH
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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

Definitions

  • the present invention relates to a method of electrochemically polishing cobalt or cobalt alloy surfaces, and to an electrolyte for electrochemically polishing such surfaces.
  • the electrolyte comprises glycolic acid and at least one alkanesulfonic acid.
  • cobalt alloys consisting of cobalt or cobalt alloys, or having surfaces of cobalt or cobalt alloys, are becoming increasingly important.
  • cobalt alloys are used in various fields because of their high resistance to corrosion and wear.
  • Applications include areas as diverse as mechanical engineering, where cobalt alloys are used to protect against wear, and medical technology, where cobalt alloys are used for implants because of their high corrosion resistance, strength, and absence of nickel.
  • US 6,679,980 B1 describes an electropolishing process that can be used to electropolish stents that may be cobalt-chromium-tungsten.
  • the electrolyte used contains concentrated hydrochloric acid and concentrated sulfuric acid.
  • An electrolyte containing sulfuric acid and hydrochloric acid, which also contains glycol, is also available in Automated Design of Fuzzy Systems ", H. Surmann, VDI Verlag, Erasmus 8, Nr. 452 described.
  • the methods described in these documents focus primarily on special equipment and controls of the electropolishing process. This is not surprising since with the electrolytes described therein under conventional electropolishing conditions smoothing or deburring of the desired quality surfaces is frequently not possible is. This too can be attributed to the carbides contained in the structure of the workpieces, since these are not removed to the same extent as the metal or the metallic alloy and can thus in some cases even lead to an increase in the roughness of the surfaces.
  • cobalt alloys are becoming increasingly important in the field of medical technology.
  • One of the reasons for this is that an increasing proportion of the population suffers from allergies to nickel. For this reason, efforts are increasingly being made to restrict the use of nickel-containing stainless steels for medical implants.
  • cobalt-chromium alloys are considered as a substitute for this.
  • implant alloys cobalt-chromium alloys
  • the surfaces of these workpieces must be polished to a high quality.
  • chromium-nickel steels this is done mainly by electrochemical polishing, since this method gives the best results.
  • cobalt-chromium alloys so far no comparable suitable electropolishing available.
  • Cobalt-based hard metals are also frequently used in mechanical and plant engineering, as their hardness and high wear resistance significantly exceed those of other materials.
  • the surfaces of pumps, valves, bearings, and other components, which are particularly at risk from wear are often armored with the cobalt alloy Stellite.
  • the mechanical polish of stellite often creates stresses that are at the expense of the corrosion resistance of the workpieces.
  • Subsequent heat treatment of the surfaces to relieve these stresses is cumbersome and often not possible to the extent that would be required due to the nature of the machine parts. Because of these drawbacks, there has long been a need for electropolishing methods that enable smoothing and deburring of surfaces of cobalt or cobalt alloy workpieces of comparable quality as can be achieved in electropolishing stainless steel surfaces.
  • the subject of the present invention is a novel electrolyte which enables the production of shiny, smooth and deburred surfaces of cobalt or cobalt alloys.
  • This electrolyte comprises at least one alkanesulfonic acid having an alkyl radical having 1, 2 or 3 carbon atoms and glycolic acid.
  • the at least one alkanesulfonic acid comprises methanesulfonic acid.
  • Elek trolyte may for example consist of glycolic acid, methanesulfonic acid and water.
  • an electrolyte consisting of a mixture of alkanesulfonic acid (or more alkanesulfonic acids) having an alkyl group of 1 to 3 carbon atoms and glycolic acid is capable of smoothing cobalt-based surfaces to an unprecedented extent was completely surprising and unexpected .
  • this mixture as electrolyte, cobalt and cobalt alloys, including alloys such as stellite, can be electropolished without any appreciable grain boundary attack.
  • Such an electropolishing process makes it possible to routinely obtain surfaces of cobalt-containing workpieces in a previously unattained gloss and smoothness grade.
  • the electrolyte according to the invention has a ratio of alkanesulfonic acid to glycolic acid in the range from 30:70 to 80:20, based on the pure substances. Further preferred is a mixture having a ratio of alkanesulfonic acid to glycolic acid in the range of 60:40 to 70:30, based on the pure substances.
  • the active substances alkanesulfonic acid and glycolic acid are present in the electrolyte in high concentration. So contains the Electrolyte in one embodiment, a maximum of 35 wt .-% water. Preferably, the electrolyte contains a maximum of 25 wt .-% water.
  • the active substances either as pure substance or as concentrated solutions.
  • the glycolic acid is suitably used as a concentrated aqueous solution containing 60-80% by weight of glycolic acid, preferably ⁇ 70% by weight.
  • Such solutions are commercially available.
  • alkanesulfonic acid or alkanesulfonic acids are preferably used in highly concentrated form.
  • methanesulfonic acid can be used as about 85% or as ⁇ 99% solution as it is commercially available.
  • the electrolyte according to the invention contains no explosive substances, in particular no perchloric acid or salts of perchloric acid.
  • Another aspect of the invention are methods for electrochemically polishing cobalt-containing surfaces using the electrolytes described above. These electropolishing methods of the present invention are useful for producing high-quality, micro-smooth surfaces of cobalt or cobalt alloy workpieces.
  • Such a process may be carried out under any conditions known in the art and known to those skilled in the art.
  • Process temperatures in the range between 40 ° C and 70 ° C have proven particularly suitable.
  • the regulation and monitoring of the temperature may be carried out in any manner known to those skilled in the art.
  • the process is performed at an anodic current density that is between 5 and 25 A / dm 2 .
  • the anodic current density is about 10 A / dm 2 .
  • the duration of the electropolishing process depends on the roughness of the workpiece to be polished and the desired smoothing.
  • the optimum exposure time the expert in the context of routine experiments depending on determine the current density used, the temperature, the composition of the electrolyte and the electropolishing apparatus in routine experiments.
  • the treated workpiece is removed from the polishing bath and typically rinsed with demineralized water and optionally dried.
  • inventive methods are particularly suitable for the electrochemical polishing of workpieces with a surface consisting of a cobalt-chromium alloy.
  • cobalt-chromium alloys may contain other constituents in addition to the elements cobalt and chromium.
  • Such cobalt-chrome alloy surfaces smoothed and deburred by methods of the present invention may be used as medical implants because of their high compatibility with human or general biological tissue.
  • the cobalt-chromium alloy stellite which consists of about 50-60% cobalt, 30-40% chromium and 8-20% tungsten, but may also contain smaller amounts of other elements, can be with the methods described herein in a hitherto Smooth and deburr unrecognized quality.
  • the electropolishing methods described here for workpieces made of cobalt alloys, such as stellite can be used in particular in nuclear technology both in the manufacture of new components prior to their use, as well as for cleaning and decontamination of cobalt-containing components that are already in use or in use to allow a safer repair or disposal of these components.
  • the electropolishing method according to the invention is also suitable for producing high-quality smooth wear protection layers based on cobalt or cobalt alloy, which are applied to workpieces made of other materials.
  • the treatment was carried out at a current density of 10 A / dm 2 and temperatures between 40 ° C and 70 ° C in an electrolyte consisting of a mixture of ⁇ 99% methanesulfonic acid and ⁇ 70% glycolic acid (in water) in a mixing ratio from 55:45. This corresponds to a ratio of the pure substances of about 65:35 and a water content of less than 15%.

Abstract

For electro-chemical polishing of cobalt and cobalt alloy surfaces, an electrolyte is used containing glycolic acid and at least one alkane sulfonic acid with an alkyl residue containing 1-3 carbon atoms. The alkane sulfonic acid includes methane sulfonic acid. The electro-chemical polishing is at a temperature of 40-70[deg] C with an anode current density of 5-25 A/dm 2>.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum elektrochemischen Polieren von Oberflächen aus Kobalt oder Kobaltlegierungen, sowie einen Elektrolyten zum elektrochemischen Polieren solcher Oberflächen. Der Elektrolyt umfasst dabei Glykolsäure und mindestens eine Alkansulfonsäure.The present invention relates to a method of electrochemically polishing cobalt or cobalt alloy surfaces, and to an electrolyte for electrochemically polishing such surfaces. The electrolyte comprises glycolic acid and at least one alkanesulfonic acid.

Werkstücke, die aus Kobalt oder Kobaltlegierungen bestehen, bzw. die Oberflächen aus Kobalt oder Kobaltlegierungen aufweisen, gewinnen zunehmend an Bedeutung. So werden Kobaltlegierungen aufgrund ihrer hohen Widerstandsfähigkeit gegen Korrosion und Verschleiß auf verschiedenen Gebieten eingesetzt. Die Anwendungsgebiete erstrecken sich dabei über so unterschiedliche Bereiche wie den Maschinen-und Anlagebau, wo Kobaltlegierungen zum Schutz vor Verschleiß eingesetzt werden, und die Medizintechnik, wo Kobaltlegierungen aufgrund ihrer hohen Korrosionsbeständigkeit, ihrer Festigkeit und der Abwesenheit von Nickel für Implantate verwendet werden.Workpieces consisting of cobalt or cobalt alloys, or having surfaces of cobalt or cobalt alloys, are becoming increasingly important. Thus, cobalt alloys are used in various fields because of their high resistance to corrosion and wear. Applications include areas as diverse as mechanical engineering, where cobalt alloys are used to protect against wear, and medical technology, where cobalt alloys are used for implants because of their high corrosion resistance, strength, and absence of nickel.

Ein wesentliches Hemmnis bei der Verwendung von kobalthaltigen Werkstücken besteht jedoch in der schwierigen Glättung und Entgratung ihrer Oberflächen. Ursache hierfür sind die in Kobalt und Kobaltlegierungen enthaltenen harten und sehr widerstandsfähigen Carbide. Eine mechanische Politur solcher Oberflächen ist aufwendig und verursacht häufig Spannungen im oberflächennahen Gefüge des Werkstücks, welche sich nachteilig auf die Korrosionsbeständigkeit der Werkstücke auswirken können.However, a major obstacle to the use of cobalt-containing workpieces is the difficulty of smoothing and deburring their surfaces. This is due to the hard and highly resistant carbides contained in cobalt and cobalt alloys. A mechanical polishing of such surfaces is expensive and often causes tensions in the near-surface structure of the workpiece, which can adversely affect the corrosion resistance of the workpieces.

Eine Alternative besteht im elektrochemischen Polieren solcher Oberflächen. US 6,679,980 B1 beschreibt ein Elektropolierverfahren, das zum Elektropolieren von Stents verwendet werden kann, die aus Kobalt-Chrom-Wolfram bestehen können. Der dabei eingesetzte Elektrolyt enthält konzentrierte Salzsäure und konzentrierte Schwefelsäure. Ein Schwefelsäure- und Salzsäure-haltiger Elektrolyt, der darüber hinaus Glykol enthält, ist auch in " Automatisierter Entwurf von Fuzzy Systemen", H. Surmann, VDI Verlag, Reihe 8, Nr. 452 beschrieben. Die in diesen Dokumenten beschriebenen Verfahren konzentrieren sich in erster Linie auf spezielle Apparaturen und Steuerungen des Elektropolierprozesses. Dies ist nicht verwunderlich, da mit den darin beschriebenen Elektrolyten unter herkömmlichen Elektropolierbedingungen ein Glätten bzw. Entgraten der Oberflächen in erwünschter Qualität häufig nicht möglich ist. Auch dies ist auf die im Gefüge der Werkstücke enthaltenen Carbide zurückzuführen, da diese nicht in gleichem Maße wie das Metall bzw. die metallische Legierung abgetragen werden und somit teilweise sogar zu einer Erhöhung der Rauheit der Oberflächen führen können.An alternative is the electrochemical polishing of such surfaces. US 6,679,980 B1 describes an electropolishing process that can be used to electropolish stents that may be cobalt-chromium-tungsten. The electrolyte used contains concentrated hydrochloric acid and concentrated sulfuric acid. An electrolyte containing sulfuric acid and hydrochloric acid, which also contains glycol, is also available in Automated Design of Fuzzy Systems ", H. Surmann, VDI Verlag, Reihe 8, Nr. 452 described. The methods described in these documents focus primarily on special equipment and controls of the electropolishing process. This is not surprising since with the electrolytes described therein under conventional electropolishing conditions smoothing or deburring of the desired quality surfaces is frequently not possible is. This too can be attributed to the carbides contained in the structure of the workpieces, since these are not removed to the same extent as the metal or the metallic alloy and can thus in some cases even lead to an increase in the roughness of the surfaces.

Auch in der Literatur beschriebene Elektrolyte aus Perchlorsäure und Essigsäure liefern oftmals keine zufriedenstellenden Ergebnisse. Darüber hinaus ist die in diesen Verfahren verwendete Perchlorsäure explosiv und brandfördernd, weshalb erhebliche Gefahren und mit deren Vermeidung verbundene Kosten mit der Verwendung solcher Perchlorsäure-haltigen Elektrolyte einhergehen.Also described in the literature electrolytes from perchloric acid and acetic acid often do not provide satisfactory results. In addition, the perchloric acid used in these processes is explosive and fire-promoting, which is why considerable risks and costs associated with their avoidance are associated with the use of such perchloric acid-containing electrolytes.

Wie erwähnt, gewinnen Kobaltlegierungen gerade auf dem Gebiet der Medizintechnik zunehmend an Bedeutung. Eine Ursache hierfür liegt unter anderem darin, dass ein zunehmender Anteil der Bevölkerung unter Allergien gegen Nickel leidet. Aus diesem Grunde ist man in verstärktem Maße bestrebt, die Anwendung von nickelhaltigen Edelstählen für medizinische Implantate einzuschränken. Als Ersatz hierfür kommen neben Titan vor allem Kobalt-Chrom-Legierungen (sogenannte Implantat-Legierungen) in Betracht. Damit die Implantate eine ausreichende Korrosionsbeständigkeit und Biokompatibilität aufweisen, müssen die Oberflächen dieser Werkstücke jedoch hochwertig poliert sein. Bei den herkömmlich verwendeten Chrom-Nickel-Stählen geschieht dies überwiegend durch elektrochemisches Polieren, da dieses Verfahren die besten Ergebnisse liefert. Für Kobalt-Chrom-Legierungen stehen jedoch bisher keine vergleichbar geeigneten Elektropolierverfahren zur Verfügung.As mentioned, cobalt alloys are becoming increasingly important in the field of medical technology. One of the reasons for this is that an increasing proportion of the population suffers from allergies to nickel. For this reason, efforts are increasingly being made to restrict the use of nickel-containing stainless steels for medical implants. In addition to titanium, especially cobalt-chromium alloys (so-called implant alloys) are considered as a substitute for this. In order for the implants to have sufficient corrosion resistance and biocompatibility, however, the surfaces of these workpieces must be polished to a high quality. In the conventionally used chromium-nickel steels this is done mainly by electrochemical polishing, since this method gives the best results. For cobalt-chromium alloys, however, so far no comparable suitable electropolishing available.

Hartmetalle auf Kobaltbasis werden auch häufig im Maschinen- und Anlagebau eingesetzt, da ihre Härte und hohe Verschleißfestigkeit die anderer Materialien merklich übertreffen. So werden beispielsweise in Kernkraftwerken die Oberflächen von Pumpen, Ventilen, Lagern und anderen Bauteilen, die besonders durch Verschleiß gefährdet sind, häufig mit der Kobaltlegierung Stellit gepanzert. Die mechanische Politur von Stellit erzeugt aber häufig Spannungen, die zu Lasten der Korrosionsbeständigkeit der Werkstücke gehen. Eine anschließende Wärmebehandlung der Oberflächen zum Abbau dieser Spannungen ist jedoch aufwändig und aufgrund der Art der Maschinenteile häufig nicht in dem Umfang möglich, wie es erforderlich wäre. Aufgrund dieser Nachteile besteht seit längerer Zeit ein Bedarf an Elektropolierverfahren, mit denen ein Glätten und Entgraten von Oberflächen von Werkstücken aus Kobalt oder Kobaltlegierungen in vergleichbarer Qualität ermöglicht wird, wie sie beim Elektropolieren von Edelstahl-Oberflächen erzielt werden kann.Cobalt-based hard metals are also frequently used in mechanical and plant engineering, as their hardness and high wear resistance significantly exceed those of other materials. For example, in nuclear power plants, the surfaces of pumps, valves, bearings, and other components, which are particularly at risk from wear, are often armored with the cobalt alloy Stellite. However, the mechanical polish of stellite often creates stresses that are at the expense of the corrosion resistance of the workpieces. Subsequent heat treatment of the surfaces to relieve these stresses, however, is cumbersome and often not possible to the extent that would be required due to the nature of the machine parts. Because of these drawbacks, there has long been a need for electropolishing methods that enable smoothing and deburring of surfaces of cobalt or cobalt alloy workpieces of comparable quality as can be achieved in electropolishing stainless steel surfaces.

Detaillierte Beschreibung der ErfindungDetailed description of the invention

Gegenstand der vorliegenden Erfindung ist ein neuartiger Elektrolyt, der die Erzeugung von glänzenden, glatten und entgrateten Oberflächen aus Kobalt oder Kobaltlegierungen ermöglicht. Dieser Elektrolyt umfasst mindestens eine Alkansulfonsäure mit einem Alkylrest, der 1, 2 oder 3 Kohlenstoffatome aufweist, sowie Glykolsäure. In einer Ausführungsform umfasst die mindestens eine Alkansulfonsäure Methansulfonsäure. Ein solcher Elek-trolyt kann etwa aus Glykolsäure, Methansulfonsäure und Wasser bestehen.The subject of the present invention is a novel electrolyte which enables the production of shiny, smooth and deburred surfaces of cobalt or cobalt alloys. This electrolyte comprises at least one alkanesulfonic acid having an alkyl radical having 1, 2 or 3 carbon atoms and glycolic acid. In one embodiment, the at least one alkanesulfonic acid comprises methanesulfonic acid. Such Elek trolyte may for example consist of glycolic acid, methanesulfonic acid and water.

Dass ein Elektrolyt, bestehend aus einem Gemisch von Alkansulfonsäure (oder mehreren Alkansulfonsäuren), die einen Alkylrest aus 1 bis 3 Kohlenstoffatomen aufweisen, und Glykolsäure in der Lage ist, Oberflächen auf Kobaltbasis in einem bisher nicht erreichten Ausmaß zu glätten, war völlig überraschend und unerwartet. Mit diesem Gemisch als Elektrolyten können Kobalt und Kobaltlegierungen, darunter auch Legierungen wie Stellit, elektropoliert werden, ohne dass dabei ein nennenswerter Korngrenzenangriff erfolgt. Ein solches Elektropolierverfahren ermöglicht es, Oberflächen kobalthaltiger Werkstücke in einer bisher nicht erreichten Güte bezüglich Glanz und Glätte routinemäßig zu erhalten. Mit diesem Verfahren können Unebenheiten ebenso abgetragen werden wie spannungsbelastete und geschädigte Werkstoffschichten, und kobalthaltige Werkstücke mit einer hochwertig polierten, spannungsfreien Oberfläche können auf diese Weise erhalten werden. Diese Oberflächen weisen im Vergleich zu Oberflächen, die mechanisch poliert wurden, bzw. die mit einem Elektrolyten gemäß dem bisherigen Stand der Technik elektropoliert wurden, außerdem eine wesentlich höhere Korrosionsbeständigkeit auf.That an electrolyte consisting of a mixture of alkanesulfonic acid (or more alkanesulfonic acids) having an alkyl group of 1 to 3 carbon atoms and glycolic acid is capable of smoothing cobalt-based surfaces to an unprecedented extent was completely surprising and unexpected , With this mixture as electrolyte, cobalt and cobalt alloys, including alloys such as stellite, can be electropolished without any appreciable grain boundary attack. Such an electropolishing process makes it possible to routinely obtain surfaces of cobalt-containing workpieces in a previously unattained gloss and smoothness grade. With this method, unevenness can be removed as well as stress-loaded and damaged material layers, and cobalt-containing workpieces with a high-quality, stress-free surface can be obtained in this way. These surfaces also have a much higher corrosion resistance compared to surfaces which have been mechanically polished or which have been electropolished with a prior art electrolyte.

In einer bevorzugten Ausführungsform weist der Elektrolyt gemäß der Erfindung ein Verhältnis von Alkansulfonsäure zu Glykolsäure im Bereich von 30:70 bis 80:20, bezogen auf die Reinsubstanzen, auf. Weiter bevorzugt wird ein Gemisch, das ein Verhältnis von Alkansulfonsäure zu Glykolsäure im Bereich von 60:40 bis 70:30, bezogen auf die Reinsubstanzen, aufweist. Diese Mengenangaben beziehen sich wie alle anderen in der vorliegenden Anmeldung angegeben Mengenangaben, relativen Verhältnisse und Prozentangaben auf das Gewicht der jeweiligen Substanzen, Komponenten und Lösungen soweit nichts Gegenteiliges angegeben ist.In a preferred embodiment, the electrolyte according to the invention has a ratio of alkanesulfonic acid to glycolic acid in the range from 30:70 to 80:20, based on the pure substances. Further preferred is a mixture having a ratio of alkanesulfonic acid to glycolic acid in the range of 60:40 to 70:30, based on the pure substances. These quantities are like all other quantities given in the present application, relative ratios and percentages based on the weight of the respective substances, components and solutions unless otherwise specified.

In einer weiteren bevorzugten Ausführungsform liegen die Wirksubstanzen Alkansulfonsäure und Glykolsäure im Elektrolyten in hoher Konzentration vor. So enthält der Elektrolyt in einer Ausführungsform maximal 35 Gew.-% Wasser. Vorzugsweise enthält der Elektrolyt maximal 25 Gew.-% Wasser.In a further preferred embodiment, the active substances alkanesulfonic acid and glycolic acid are present in the electrolyte in high concentration. So contains the Electrolyte in one embodiment, a maximum of 35 wt .-% water. Preferably, the electrolyte contains a maximum of 25 wt .-% water.

Bei der Herstellung des Elektrolyten gemäß der vorliegenden Erfindung wird daher bevorzugt, die Wirksubstanzen entweder als Reinsubstanz oder als konzentrierte Lösungen einzusetzen. So wird die Glykolsäure in geeigneter Weise als konzentrierte wässrige Lösung, die 60-80 Gew.-% Glykolsäure, vorzugsweise ≥ 70 Gew.-% aufweist, eingesetzt. Solche Lösungen sind kommerziell erhältlich. Es können aber ebenfalls die Reinsubstanz, bzw. selbst erzeugte Lösungen von Glykolsäure in Wasser verwendet werden.In the preparation of the electrolyte according to the present invention, it is therefore preferred to use the active substances either as pure substance or as concentrated solutions. Thus, the glycolic acid is suitably used as a concentrated aqueous solution containing 60-80% by weight of glycolic acid, preferably ≥70% by weight. Such solutions are commercially available. However, it is also possible to use the pure substance or self-produced solutions of glycolic acid in water.

Auch die Alkansulfonsäure oder Alkansulfonsäuren werden vorzugsweise in hochkonzentrierter Form eingesetzt. So kann beispielsweise Methansulfonsäure als etwa 85%ige oder als ≥ 99%ige Lösung, wie sie kommerziell erhältlich ist, eingesetzt werden.The alkanesulfonic acid or alkanesulfonic acids are preferably used in highly concentrated form. For example, methanesulfonic acid can be used as about 85% or as ≥99% solution as it is commercially available.

In einer bevorzugten Ausführungsform enthält der Elektrolyt gemäß der Erfindung keine explosiven Substanzen, insbesondere keine Perchlorsäure oder Salze der Perchlorsäure.In a preferred embodiment, the electrolyte according to the invention contains no explosive substances, in particular no perchloric acid or salts of perchloric acid.

Einen weiteren Aspekt der Erfindung stellen Verfahren zum elektrochemischen Polieren von kobalthaltigen Oberflächen unter Verwendung der zuvor beschriebenen Elektrolyten dar. Diese erfindungsgemäßen Elektropolierverfahren eignen sich zur Herstellung hochwertiger, mikroglatter Oberflächen von Werkstücken aus Kobalt oder Kobaltlegierungen.Another aspect of the invention are methods for electrochemically polishing cobalt-containing surfaces using the electrolytes described above. These electropolishing methods of the present invention are useful for producing high-quality, micro-smooth surfaces of cobalt or cobalt alloy workpieces.

Ein solches Verfahren kann unter sämtlichen auf dem Gebiet üblichen und dem Fachmann bekannten Bedingungen durchgeführt werden. Als besonders geeignet haben sich Verfahrenstemperaturen im Bereich zwischen 40°C und 70°C herausgestellt. Die Regulierung und Überwachung der Temperatur kann auf jede, dem Fachmann bekannte Art und Weise erfolgen. In einer bevorzugten Ausführungsform wird das Verfahren bei einer anodischen Stromdichte durchgeführt, die zwischen 5 und 25 A/dm2 liegt. In einer weiteren Ausführungsform der Erfindung liegt die anodische Stromdichte bei etwa 10 A/dm2.Such a process may be carried out under any conditions known in the art and known to those skilled in the art. Process temperatures in the range between 40 ° C and 70 ° C have proven particularly suitable. The regulation and monitoring of the temperature may be carried out in any manner known to those skilled in the art. In a preferred embodiment, the process is performed at an anodic current density that is between 5 and 25 A / dm 2 . In a further embodiment of the invention, the anodic current density is about 10 A / dm 2 .

Die Dauer des Elektropoliervorgangs richtet sich natürlich jeweils nach der Rauheit des zu polierenden Werkstücks und der gewünschten Glättung. Die optimale Einwirkzeit kann der Fachmann im Rahmen von Routineexperimenten in Abhängigkeit von der verwendeten Stromdichte, der Temperatur, der Zusammensetzung des Elektrolyten und der Elektropolierapparatur in Routineexperimenten ermitteln.Of course, the duration of the electropolishing process depends on the roughness of the workpiece to be polished and the desired smoothing. The optimum exposure time, the expert in the context of routine experiments depending on determine the current density used, the temperature, the composition of the electrolyte and the electropolishing apparatus in routine experiments.

Im Anschluss an das Elektropolieren wird das behandelte Werkstück aus dem Polierbad entfernt und üblicherweise mit entmineralisiertem Wasser gespült und gegebenenfalls getrocknet.Following electropolishing, the treated workpiece is removed from the polishing bath and typically rinsed with demineralized water and optionally dried.

Die erfindungsgemäßen Verfahren eignen sich besonders auch zur elektrochemischen Politur von Werkstücken mit einer Oberfläche, die aus einer Kobalt-Chrom-Legierung besteht. Diese Kobalt-Chrom-Legierungen können neben den Elementen Kobalt und Chrom auch weitere Bestandteile enthalten. Solche durch Verfahren gemäß der vorliegenden Erfindung geglätteten und entgrateten Werkstücke mit Oberflächen aus Kobalt-Chrom-Legierungen können aufgrund ihrer hohen Verträglichkeit mit menschlichem bzw. allgemein biologischem Gewebe als medizinische Implantate verwendet werden.The inventive methods are particularly suitable for the electrochemical polishing of workpieces with a surface consisting of a cobalt-chromium alloy. These cobalt-chromium alloys may contain other constituents in addition to the elements cobalt and chromium. Such cobalt-chrome alloy surfaces smoothed and deburred by methods of the present invention may be used as medical implants because of their high compatibility with human or general biological tissue.

Auch die Kobalt-Chrom-Legierung Stellit, die aus etwa 50-60% Kobalt, 30-40% Chrom und 8-20% Wolfram besteht, aber auch geringere Mengen anderer Elemente enthalten kann, lässt sich mit den hier beschriebenen Verfahren in einer bisher nicht gekannten Güte glätten und entgraten. Die hier beschriebenen Elektropolierverfahren für Werkstücke aus Kobaltlegierungen, etwa aus Stellit, können insbesondere auch in der Kerntechnik sowohl bei der Herstellung neuer Bauteile vor deren Einsatz verwendet werden, als auch zur Reinigung und Dekontamination von kobalthaltigen Bauteilen, die sich bereits im Einsatz befinden oder im Einsatz befunden haben, um eine gefahrlosere Reparatur bzw. Entsorgung dieser Bauteile zu ermöglichen. Darüber hinaus eignet sich das erfindungsgemäße Elektropolierverfahren auch zur Erzeugung hochwertiger glatter Verschleißschutzschichten auf Kobalt- bzw. Kobaltlegierungsbasis, welche auf Werkstücken aus anderen Materialien aufgebracht werden.The cobalt-chromium alloy stellite, which consists of about 50-60% cobalt, 30-40% chromium and 8-20% tungsten, but may also contain smaller amounts of other elements, can be with the methods described herein in a hitherto Smooth and deburr unrecognized quality. The electropolishing methods described here for workpieces made of cobalt alloys, such as stellite, can be used in particular in nuclear technology both in the manufacture of new components prior to their use, as well as for cleaning and decontamination of cobalt-containing components that are already in use or in use to allow a safer repair or disposal of these components. In addition, the electropolishing method according to the invention is also suitable for producing high-quality smooth wear protection layers based on cobalt or cobalt alloy, which are applied to workpieces made of other materials.

Die Erfindung wird in den folgenden Beispielen näher erläutert. Diese Beispiele stellen nur mögliche Ausführungsformen des hier beschriebenen Elektropolierverfahrens dar und sollen in keiner Weise eine Beschränkung auf die hier verwendeten Bedingungen implizieren.The invention is explained in more detail in the following examples. These examples are only possible embodiments of the electropolishing process described herein and are not intended to imply any limitation to the conditions used herein.

BeispieleExamples

Elektropoliert wurden

  • Implantate aus einer Kobalt-Chrom-Molybdän-Legierung,
  • Werkzeuge aus einer Kobalt-Chrom-Wolfram-Legierung,
  • Werkzeuge aus massivem Stellit, sowie
  • Werkzeuge aus nichtrostendem Stahl mit einer aufgeschweißten Panzerung.
Were electropolished
  • Implants of a cobalt-chromium-molybdenum alloy,
  • Tools made of a cobalt-chromium-tungsten alloy,
  • Tools made of solid stellite, as well
  • Tools made of stainless steel with a welded-on armor.

Die Bearbeitung erfolgte bei einer Stromdichte von 10 A/dm2 und Temperaturen zwischen 40°C und 70°C.in einem Elektrolyten, bestehend aus einem Gemisch von ≥ 99%iger Methansulfonsäure und ≥ 70%iger Glykolsäure (in Wasser) in einem Mischungsverhältnis von 55:45. Dies entspricht einem Verhältnis der Reinsubstanzen von etwa 65:35 und einem Wassergehalt von weniger als 15 %.The treatment was carried out at a current density of 10 A / dm 2 and temperatures between 40 ° C and 70 ° C in an electrolyte consisting of a mixture of ≥ 99% methanesulfonic acid and ≥ 70% glycolic acid (in water) in a mixing ratio from 55:45. This corresponds to a ratio of the pure substances of about 65:35 and a water content of less than 15%.

Die Ergebnisse zeigten für alle Werkstücke hochglänzende, glatte Oberflächen ohne dass ein selektiver Angriff auf Korngrenzen beobachtet werden konnte.The results showed high-gloss, smooth surfaces for all workpieces without a selective attack on grain boundaries could be observed.

Claims (14)

Elektrolyt, umfassend mindestens eine Alkansulfonsäure mit einem Alkylrest, der 1, 2 oder 3 Kohlenstoffatome aufweist, und Glykolsäure, zum Elektropolieren von Oberflächen aus Kobalt oder Kobaltlegierungen.An electrolyte comprising at least one alkanesulfonic acid having an alkyl radical having 1, 2 or 3 carbon atoms and glycolic acid for electropolishing surfaces of cobalt or cobalt alloys. Elektrolyt gemäß Anspruch 1, dadurch gekennzeichnet, dass die mindestens eine Alkansulfonsäure Methansulfonsäure umfasst.Electrolyte according to claim 1, characterized in that the at least one alkanesulfonic acid comprises methanesulfonic acid. Elektrolyt gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Verhältnis von Alkansulfonsäure zu Glykolsäure im Bereich von 30:70 bis 80:20 liegt, bezogen auf das Gewicht der Reinsubstanzen.An electrolyte according to claim 1 or 2, characterized in that the ratio of alkanesulfonic acid to glycolic acid is in the range from 30:70 to 80:20, based on the weight of the pure substances. Elektrolyt gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Verhältnis von Alkansulfonsäure zu Glykolsäure im Bereich von 60:40 bis 70:30 liegt, bezogen auf das Gewicht der Reinsubstanzen.An electrolyte according to claim 1 or 2, characterized in that the ratio of alkanesulfonic acid to glycolic acid is in the range of 60:40 to 70:30, based on the weight of the pure substances. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt maximal 35 Gew.-% Wasser enthält.Electrolyte according to one of the preceding claims, characterized in that the electrolyte contains a maximum of 35 wt .-% water. Elektrolyt gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Elektrolyt maximal 25 Gew.-% Wasser enthält.Electrolyte according to one of claims 1 to 4, characterized in that the electrolyte contains a maximum of 25 wt .-% water. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt keine Perchlorsäure oder Perchlorate enthält.Electrolyte according to one of the preceding claims, characterized in that the electrolyte contains no perchloric acid or perchlorates. Verfahren zum Elektropolieren von Oberflächen aus Kobalt oder Kobaltlegierungen mit einem Elektrolyten gemäß einem der Ansprüche 1 bis 7.Process for electropolishing surfaces of cobalt or cobalt alloys with an electrolyte according to one of claims 1 to 7. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass das Verfahren bei einer Temperatur zwischen 40°C und 70°C durchgeführt wird.A method according to claim 8, characterized in that the method is carried out at a temperature between 40 ° C and 70 ° C. Verfahren gemäß Anspruch 8 oder 9, dadurch gekennzeichnet, dass das Verfahren bei einer anodischen Stromdichte von 5 bis 25 A/dm2 durchgeführt wird.A method according to claim 8 or 9, characterized in that the method is carried out at an anodic current density of 5 to 25 A / dm 2 . Verfahren gemäß Anspruch 8 oder 9, dadurch gekennzeichnet, dass das Verfahren bei einer anodischen Stromdichte von etwa 10 A/dm2 durchgeführt wird.A method according to claim 8 or 9, characterized in that the method is carried out at an anodic current density of about 10 A / dm 2 . Verfahren gemäß einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, dass die Oberfläche aus einer Kobalt-Chrom-Legierung besteht.A method according to any one of claims 8 to 11, characterized in that the surface consists of a cobalt-chromium alloy. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass die Oberfläche eine Oberfläche eines medizinischen Implantats ist.A method according to claim 12, characterized in that the surface is a surface of a medical implant. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass die Kobalt-Chrom-Legierung Stellit ist.A method according to claim 12, characterized in that the cobalt-chromium alloy is stellite.
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AT520365B1 (en) * 2017-08-29 2019-10-15 Hirtenberger Eng Surfaces Gmbh ELECTROLYTE FOR ELECTROPOLISHING METAL SURFACES
CN109778297B (en) * 2019-03-25 2020-12-15 山东吉威医疗制品有限公司 Electrochemical polishing solution for Co-Cr alloy bracket and polishing method thereof
CN110724999B (en) * 2019-10-23 2021-09-28 沈阳航空航天大学 Electrolyte for CoCrNi multi-principal-element alloy with high Cr content and corrosion process
CN112710529B (en) * 2020-12-18 2022-09-20 国电浙江北仑第三发电有限公司 Preparation method of sample simultaneously used for observation of HR3C precipitate after service and EBSD characterization
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