EP0139958A1 - Process for electrolytically polishing a work piece made of a nickel, cobalt or iron based alloy - Google Patents

Process for electrolytically polishing a work piece made of a nickel, cobalt or iron based alloy Download PDF

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EP0139958A1
EP0139958A1 EP84109758A EP84109758A EP0139958A1 EP 0139958 A1 EP0139958 A1 EP 0139958A1 EP 84109758 A EP84109758 A EP 84109758A EP 84109758 A EP84109758 A EP 84109758A EP 0139958 A1 EP0139958 A1 EP 0139958A1
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electrolyte
concentrated
volume
fluorosurfactant
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EP0139958B1 (en
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Vladimir Sova
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BBC Brown Boveri AG Switzerland
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/16Polishing
    • C25F3/22Polishing of heavy metals

Definitions

  • the invention is based on a method for the electrolytic polishing of a workpiece made of an alloy based on nickel, cobalt or iron, according to the preamble of claim 1.
  • Electrolytes based on concentrated acids such as sulfuric acid, phosphoric acid and nitric acid are mostly used in the electrolytic polishing of metals and alloys of groups IVB, VB, VIB and VIII of the periodic system of the elements. Due to the action of the acids mentioned, a preferred removal of surface roughness should occur during the anodic treatment of the metal objects. If the working conditions are set appropriately, this removal can lead to the surface shining.
  • Various theories were elaborated to clarify the electropolishing processes. Usually there are considerations about the physical properties of the electrolyte. The viscosity of the electrolyte plays an important role here with regard to the diffusion processes at the anode. Another factor is the influence of conductivity on the current-voltage ratio.
  • the electrolytic polishing of stainless steels is known, inter alia, from DE-PS 938 402, DE-PS 754 703, DE-AS 1 913 570, US-PS 3 751 352.
  • the corresponding method for superalloys is described, for example, in DE-OS 26 54 484.
  • the reason for this is the uneven dissolution of all metals involved or even the concentration of the poorly soluble components on the treated surface.
  • the perchloric acid-based electrolyte has brought about very good electropolishing effects, but from a practical point of view such an electrolyte cannot be used in production.
  • the required operating temperature is too low for this and there is a risk of later corrosive attack due to degraded chloride ions.
  • the invention has for its object to provide a method for the electrolytic polishing of a workpiece made of a nickel, cobalt or iron alloy, in particular superalloy, which provides clean, shiny workpiece surfaces and can be carried out under normal workshop conditions and in indoor and outdoor temperatures without risk of explosion .
  • the corresponding electrolyte should have a long usability.
  • the finished electrolysis bath had approximately the following composition:
  • a gas turbine blade made of a nickel superalloy with the trade name Nimonic was electrolytically polished as the workpiece.
  • the workpiece was first degreased in organic solvents and then placed in a suitable hooking device (frame).
  • the frame was with the workpiece as an anode in the electrolysis bath and a cell voltage of 50 V set.
  • Electrolytically polishing was then carried out for 3 minutes at a current density of 80 A / dm 2 and a temperature of 0 ° C. After the polishing process was completed, the power was switched off, the workpiece with the frame was removed from the bath and rinsed several times in cold and warm water. Then the workpiece was in the hot air flow at a temperature of
  • the workpiece consisted of a nickel-based superalloy with the trade name Hastelloy. Before electrolytic polishing, it was degreased in organic solvents (trichlorethylene, perchlorethylene) and then hung in a device similar to that described in Example I. The whole was immersed in the above-mentioned electrolysis bath, where it served as an anode. The cell voltage was set at 20 V and polished electrolytically for 5 min. Further processing of the workpiece, the rinsing, drying, etc. was carried out in the manner given under Example I.
  • the finished electrolysis bath therefore had approximately the following composition:
  • a component made of an austenitic iron alloy of the type XlOCrNiW 17/13 was used as the workpiece. It was first degreased in organic solvents and then installed in a suitable rack. The procedure of Example I was also followed. The cell voltage was kept at 70 V during the electrolytic polishing. The polishing time was 7 min. The workpiece was then treated in the manner specified in Example I.
  • the invention is not restricted to the exemplary embodiment.
  • the method is basically applicable to Ni, Co or Fe-based alloys - mainly austenitic materials. That is usually concentrated on one non-oxidizing acid such as H 2 SO 4 or H 3 PO 4 , furthermore an electrolyte containing a fluorosurfactant and a weak polar organic compound, a fluorine compound in the form of a simple or complex fluoride is added in an amount of at least 2% by volume.
  • the content of concentrated H 2 SO 4 or N 3 PO 4 can be between 20 and 80% by volume. If both of the aforementioned acids were used at the same time, their content would advantageously be 10 to 40% by volume.
  • the electrolyte may also contain 10 to 30% by volume of C 2 H 5 OH and 2-propanol. Approximately 0.2% by volume of a fluorosurfactant is added to the electrolyte throughout.
  • the electrolytic polishing is advantageously carried out at temperatures between -20 and +30 ° C at anodic current densities of 20 to 250 A / dm 2 under cell voltages of 20 to 70 V for 20 sec to 20 min.

Abstract

Elektrochemisches Polierverfahren für Fe-, Co- und Ni- Le-gierungen, insbesondere Nickelsuperlegierungen bei welchem dem auf der Basis einer starken Säure, mindestens einer schwach polaren organischen Verbindung und einem Fluorotensid aufgebauten Elektrolyten zusätzlich eine Fluorverbindung beigemengt wird. Bevorzugt wird HBF4 in einer Menge von 5 bis 40 Vol.-% zugegeben. Weitere günstig wirkende Fluorverbindungen sind Ammoniumdifluorid, HF und Natriumfluosilikat.Electrochemical polishing process for Fe, Co and Ni alloys, in particular nickel superalloys, in which a fluorine compound is additionally added to the electrolyte, which is based on a strong acid, at least one weakly polar organic compound and a fluorosurfactant. HBF4 is preferably added in an amount of 5 to 40% by volume. Other beneficial fluorine compounds are ammonium difluoride, HF and sodium fluorosilicate.

Description

Die Erfindung geht aus von einem Verfahren zum elektrolytischen Polieren eines Werkstücks aus einer Legierung auf Nickel-, Kobalt- oder Eisenbasis nach der Gattung des Oberbegriffs des Anspruchs 1.The invention is based on a method for the electrolytic polishing of a workpiece made of an alloy based on nickel, cobalt or iron, according to the preamble of claim 1.

Beim elektrolytischen Polieren von Metallen und Legierungen der Gruppen IVB, VB, VIB und VIII des periodischen Systems der Elemente werden meistens Elektrolyte auf der Basis konzentrierter Säuren wie Schwefelsäure, Phosphorsäure und Salpetersäure eingesetzt. Durch die Wirkung der erwähnten Säuren sollte bei der anodischen Behandlung der Metallgegenstände eine bevorzugte Abtragung von Oberflächenrauheiten zustandekommen. Diese Abtragung kann bei geeigneter Einstellung der Arbeitsbedingungen bis zum Glänzen der Oberfläche führen. Zur Abklärung der Elektropoliervorgänge wurden verschiedene Theorien ausgearbeitet. Meistens sind es Ueberlegungen über physikalische Eigenschaften des Elektrolyten. Hier spielt eine wichtige Rolle die Viskosität des Elektrolyten hinsichtlich der Diffusionsvorgänge an der Anode. Ein anderer Faktor ist der Einfluss der Leitfähigkeit bezüglich des Strom-Spannungsverhält-Das elektrolytische Polieren rostfreier Stähle ist unter anderem bekannt aus der DE-PS 938 402, DE-PS 754 703, DE-AS 1 913 570, US-PS 3 751 352. Das entsprechende Verfahren für Superlegierungen ist z.B. in der DE-OS 26 54 484 beschrieben.Electrolytes based on concentrated acids such as sulfuric acid, phosphoric acid and nitric acid are mostly used in the electrolytic polishing of metals and alloys of groups IVB, VB, VIB and VIII of the periodic system of the elements. Due to the action of the acids mentioned, a preferred removal of surface roughness should occur during the anodic treatment of the metal objects. If the working conditions are set appropriately, this removal can lead to the surface shining. Various theories were elaborated to clarify the electropolishing processes. Mostly there are considerations about the physical properties of the electrolyte. The viscosity of the electrolyte plays an important role here with regard to the diffusion processes at the anode. Another factor is the influence of conductivity on the current-voltage ratio. The electrolytic polishing of stainless steels is known, inter alia, from DE-PS 938 402, DE-PS 754 703, DE-AS 1 913 570, US-PS 3 751 352. The corresponding method for superalloys is described, for example, in DE-OS 26 54 484.

Beim elektrolytischen Polieren sind hauptsächlich zwei gleichzeitig zu bewerkstellende Prozesse zu beachten: Die Einebnung der Oberfläche, d.h. die bevorzugte Auflösung der makro- bis mikroskopisch vorliegenden Rauheiten der Oberfläche, ohne dass dabei ein Kornangriff in die Tiefe erfolgt, sowie die Auflösung der gebildeten Metalloxydschicht an der Oberfläche. Bei der Behandlung von Legierungen kommt noch ein dritter, wichtiger Faktor zum Zuge, die gleichmässige Auflösung von allen beteiligten Metallkomponenten. Diese gleichmässige Auflösung von allen in der Legierung vorhandenen Metallen ist umso schwieriger, je mehr die Metalle aus verschiedenen Gruppen des periodischen Systems der Elemente stammen. Bei sehr komplex zusammengesetzten Legierungen des Nickelbasis-Typs (beispielsweise Superlegierungen wie die "Nimonics") konnte zwar mit herkömmlichen Mitteln ein elektrolytischer Poliereffekt erreicht werden, doch blieb die Oberfläche stumpf und matt. Der Grund dafür ist die ungleichmässige Auflösung aller beteiligten Metalle oder sogar die Aufkonzentrierung der schwerlöslichen Komponenten an der behandelten Oberfläche. Der Elektrolyt auf Perchlorsäurebasis hat zwar sehr gute Elektropolierwirkung gebracht, aber aus der praktischen Sicht ist ein solcher Elektrolyt in der Produktion nicht verwendbar. Dazu ist die erforderliche Betriebstemperatur zu tief und es besteht die Gefahr des späteren korrosiven Angriffs durch abgebaute Chloridionen. Ausserdem besteht bei diesem Verfahren Explosionsgefahr und die Verwendungszeit (Lebensdauer) der Elektrolyten ist zu kurz.With electrolytic polishing, there are two main processes to be considered at the same time: the preferred resolution of the macro- to microscopic roughness of the surface without any grain attack in depth, and the resolution of the metal oxide layer formed on the surface. When treating alloys, a third, important factor comes into play: the uniform dissolution of all metal components involved. This uniform dissolution of all metals present in the alloy is more difficult the more the metals come from different groups in the periodic system of the elements. In the case of very complex alloys of the nickel-based type (for example superalloys such as "Nimonics"), an electrolytic polishing effect could be achieved using conventional means, but the surface remained dull and matt. The reason for this is the uneven dissolution of all metals involved or even the concentration of the poorly soluble components on the treated surface. The perchloric acid-based electrolyte has brought about very good electropolishing effects, but from a practical point of view such an electrolyte cannot be used in production. The required operating temperature is too low for this and there is a risk of later corrosive attack due to degraded chloride ions. In addition, there is a risk of explosion with this method and the usage time (service life) of the electrolytes is too short.

Es besteht daher ein Bedürfnis nach der Verbesserung der konventionellen Verfahren des elektrolytischen Polierens. Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum elektrolytischen Polieren eines Werkstücks aus einer Nickel-, Kobalt- oder Eisenlegierung, insbesondere Superlegierung anzugeben, das saubere, glänzende Werkstückoberflächen liefert und ohne Explosionsgefahr unter normalen Werkstattbedingungen sowie im Raum und im Freien vorkommenden Temperaturen durchführbar ist. Der entsprechende Elektrolyt soll dabei eine möglichst lange Verwendbarkeit aufweisen.There is therefore a need to improve conventional electrolytic polishing processes. The invention has for its object to provide a method for the electrolytic polishing of a workpiece made of a nickel, cobalt or iron alloy, in particular superalloy, which provides clean, shiny workpiece surfaces and can be carried out under normal workshop conditions and in indoor and outdoor temperatures without risk of explosion . The corresponding electrolyte should have a long usability.

Diese Aufgabe wird durch die im kennzeichnenden Teil des Anspruchs 1 angegebenen Merkmale gelöst.This object is achieved by the features specified in the characterizing part of claim 1.

Die Erfindung wird anhand der nachfolgenden Ausführungsbeispiele näher beschrieben.The invention is described in more detail using the following exemplary embodiments.

Ausführungsbeispiel I:Embodiment I:

Zur Herabsetzung des Elektrolysebades wurden zunächst 6 Volumenteile konzentrierte H2SO4 mit 2 Volumenteilen c2H5OH gemischt. Dann wurde 1 Volumenteil HBF4 beigemischt. Zuletzt wurden noch 1 Volumenteil Glyzerin und 0,1 Vol.-% eines Fluorotensids zugegeben. Danach wurde das Bad auf die Arbeitstemperatur von 0 °C abgekühlt.To reduce the electrolysis bath, 6 volumes of concentrated H 2 SO 4 were initially mixed with 2 volumes of c 2 H 5 OH. Then 1 volume part of HBF 4 was added. Finally, 1 volume part of glycerin and 0.1 volume% of a fluorosurfactant were added. The bath was then cooled to the working temperature of 0 ° C.

Das fertige Elektrolysebad hatte ungefähr folgende Zusammensetzung:

Figure imgb0001
The finished electrolysis bath had approximately the following composition:
Figure imgb0001

Als Werkstück wurde eine Gasturbinenschaufel aus einer Nickel-Superlegierung mit dem Handelsnamen Nimonic elektrolytisch poliert. Das Werkstück wurde zunächst in organischen Lösungsmitteln entfettet und dann in eine geeignete Einhängevorrichtung (Gestell) gebracht. Das Gestell wurde mit dem Werkstück als Anode in das Elektrolysebad eingehängt und eine Zellenspannung von 50 V eingestellt. Nun wurde während 3 min bei einer Stromdichte von 80 A/dm2 etwa einer Temperatur von 0 °C elektrolytisch poliert. Nach Abschluss des Poliervorganges wurde der Strom abgeschaltet, das Werkstück mit Gestell aus dem Bad herausgenommen und mehrmals in kaltem und warmem Wasser gespült. Dann wurde das Werkstück im Warmluftstrom bei einer Temperatur vonA gas turbine blade made of a nickel superalloy with the trade name Nimonic was electrolytically polished as the workpiece. The workpiece was first degreased in organic solvents and then placed in a suitable hooking device (frame). The frame was with the workpiece as an anode in the electrolysis bath and a cell voltage of 50 V set. Electrolytically polishing was then carried out for 3 minutes at a current density of 80 A / dm 2 and a temperature of 0 ° C. After the polishing process was completed, the power was switched off, the workpiece with the frame was removed from the bath and rinsed several times in cold and warm water. Then the workpiece was in the hot air flow at a temperature of

80 bis 90 °C getrocknet. Nach der Entfernung aus dem Gestell und der Abkühlung auf Raumtemperatur zeigte das Werkstück eine glänzende spiegelnde Oberfläche.Dried 80 to 90 ° C. After removal from the frame and cooling to room temperature, the workpiece showed a shiny, reflective surface.

Ausführungsbeispiel II:Working example II:

Zunächst wurden zur Zubereitung des Elektrolysebades 3 Volumenteile konzentrierte H3PO4 mit 5 Volumenteilen C2H5OH und 1 Volumenteil Glyzerin sowie 1 Volumenteil Ammoniumdifluorid inkl. 0,1 Vol.-% Fluorotensid gemischt. Das Bad wurde auf eine Arbeitstemperatur von -10 °C abgekühlt. Das fertige Elektrolysebad hatte ungefähr folgende Zusammensetzung:

Figure imgb0002
First, to prepare the electrolysis bath, 3 volumes of concentrated H 3 PO 4 were mixed with 5 volumes of C 2 H 5 OH and 1 volume of glycerol and 1 volume of ammonium difluoride incl. 0.1 volume percent of fluorosurfactant. The bath was cooled to a working temperature of -10 ° C. The finished electrolysis bath had approximately the following composition:
Figure imgb0002

Das Werkstück bestand aus einer Nickelbasis-Superlegierung mit dem Handelsnamen Hastelloy. Vor dem elektrolytischen Polieren wurde es in organischen Lösungsmitteln (Trichloräthylen, Perchloräthylen) entfettet und dann in eine Vorrichtung ähnlich wie unter Beispiel I beschrieben, eingehängt. Das Ganze wurde in das oben angegebene Elektrolysebad eingetaucht, wo es als Anode diente. Die Zellenspannung wurde auf den Wert 20 V eingestellt und während 5 min elektrolytisch poliert. Die Weiterbehandlung des Werkstücks, das Spülen, Trocknen etc. erfolgte in der unter Beispiel I angegebenen Weise.The workpiece consisted of a nickel-based superalloy with the trade name Hastelloy. Before electrolytic polishing, it was degreased in organic solvents (trichlorethylene, perchlorethylene) and then hung in a device similar to that described in Example I. The whole was immersed in the above-mentioned electrolysis bath, where it served as an anode. The cell voltage was set at 20 V and polished electrolytically for 5 min. Further processing of the workpiece, the rinsing, drying, etc. was carried out in the manner given under Example I.

Ausführungsbeispiel III:Working example III:

Zur Herstellung des Elektrolysebades wurden 2 Volumenteile konzentrierte H3P04 und 2 Volumenteile konzentrierte H2SO4 mit 2 Volumenteilen C2H5OH und 2 Teilen 2-Propanol gemischt. Ausserdem wurde eine Lösung von 1 Volumenteil Natriumfluosilikat und 1 Volumenteil HF inkl. 0,1 Vol.-% eines Fluorotensids hergestellt und der ersten Mischung beigegeben. Das auf diese Weise hergestellte Bad wurde auf eine Arbeitstemperatur von 12 °C gebracht.To produce the electrolysis bath , 2 parts by volume of concentrated H3P04 and 2 parts by volume of concentrated H 2 SO 4 were mixed with 2 parts by volume of C 2 H 5 OH and 2 parts of 2-propanol. In addition, a solution of 1 volume of sodium fluorosilicate and 1 volume of HF including 0.1% by volume of a fluorosurfactant was prepared and added to the first mixture. The bath prepared in this way was brought to a working temperature of 12 ° C.

Das fertige Elektrolysebad hatte demgemäss ungefähr folgende Zusammensetzung:

Figure imgb0003
The finished electrolysis bath therefore had approximately the following composition:
Figure imgb0003

Als Werkstück wurde ein Bauteil aus einer austenitischen Eisenlegierung des Typs XlOCrNiW 17/13 verwendet. Es wurde zunächst in organischen Lösungsmitteln entfettet und dann in ein geeignetes Gestell eingebaut. Des weiteren wurde gemäss Beispiel I verfahren. Die Zellenspannung während des elektrolytischen Polierens wurde auf 70 V gehalten. Die Dauer des Polierens betrug 7 min. Die Behandlung des Werkstücks erfolgte dann in der unter Beispiel I angegebenen Weise.A component made of an austenitic iron alloy of the type XlOCrNiW 17/13 was used as the workpiece. It was first degreased in organic solvents and then installed in a suitable rack. The procedure of Example I was also followed. The cell voltage was kept at 70 V during the electrolytic polishing. The polishing time was 7 min. The workpiece was then treated in the manner specified in Example I.

Die Erfindung ist nicht auf die Ausführungsbeispiel beschränkt. Das Verfahren ist grundsätzlich auf Ni-, Co-oder Fe-Basislegierungen - vorwiegend austenitische Werkstoffe anwendbar. Dem in der Regel auf einer konzentrierten nichtoxydierenden Säure wie H2SO4 oder H3PO4 aufgebauten, ferner ein Fluorotensid und eine schwache polare organische Verbindung enthaltenden Elektrolyten wird eine Fluorverbindung in Form eines einfachen oder komplexen Fluorids in einer Menge von mindestens 2 Vol.-% beigemengt.The invention is not restricted to the exemplary embodiment. The method is basically applicable to Ni, Co or Fe-based alloys - mainly austenitic materials. That is usually concentrated on one non-oxidizing acid such as H 2 SO 4 or H 3 PO 4 , furthermore an electrolyte containing a fluorosurfactant and a weak polar organic compound, a fluorine compound in the form of a simple or complex fluoride is added in an amount of at least 2% by volume.

Der Gehalt an konzentrierter H2SO4 oder N3PO4 kann zwischen 20 und 80 Vol.-% betragen. Würden beide vorgenannten Säuren gleichzeitig verwendet, so betrüge deren Gehalt vorteilhafterweise je 10 bis 40 Vol.-%.The content of concentrated H 2 SO 4 or N 3 PO 4 can be between 20 and 80% by volume. If both of the aforementioned acids were used at the same time, their content would advantageously be 10 to 40% by volume.

Als schwach polare organische Verbindungen werden vorzugsweise 10 bis 50 Vol.-% C2H50H und 5 bis 40 Vol.-% Glyzerin verwendet. Statt dessen können im Elektrolyten auch je 10 bis 30 Vol.-% C2H5OH und 2-Propanol enthalten sein. Durchwegs werden dem Elektrolyten ca. 0,2 Vol.-% eines Fluorotensids beigegeben.10 to 50% by volume of C 2 H 5 0H and 5 to 40% by volume of glycerol are preferably used as weakly polar organic compounds. Instead, the electrolyte may also contain 10 to 30% by volume of C 2 H 5 OH and 2-propanol. Approximately 0.2% by volume of a fluorosurfactant is added to the electrolyte throughout.

Als Fluorverbindungen, welche für das Verfahren geeignet und typisch sind, können HBF4 (5 bis 40 Vol.-%); Ammoniumdifluorid (5 bis 40 Vol.-%) oder eine Mischung von HF und Natriumfluorsilikat (je 5 bis 20 Vol.-%) Verwendung finden. Selbstverständlich sind auch andere Kombinationen von geeigneten Fluorverbindungen für die Durchführung des Verfahrens verwendbar.As fluorine compounds which are suitable and typical for the process, HBF 4 (5 to 40% by volume); Ammonium difluoride (5 to 40 vol .-%) or a mixture of HF and sodium fluorosilicate (each 5 to 20 vol .-%) are used. Of course, other combinations of suitable fluorine compounds can also be used to carry out the process.

Das elektrolytische Polieren wird vorteilhafterweise bei Temperaturen zwischen -20 und +30 °C bei anodischen Stromdichten von 20 bis 250 A/dm2 unter Zellenspannungen von 20 bis 70 V während 20 sec bis 20 min durchgeführt.The electrolytic polishing is advantageously carried out at temperatures between -20 and +30 ° C at anodic current densities of 20 to 250 A / dm 2 under cell voltages of 20 to 70 V for 20 sec to 20 min.

Claims (6)

1. Verfahren zum elektrolytischen Polieren eines Werkstücks aus einer Legierung auf Nickel-, Kobalt- oder Eisenbasis mittels eines eine konzentrierte nichtoxydierende Säure sowie ein Fluorotensid und eine schwach polare organische Verbindung enthaltenden Elektrolyten, wobei das Werkstück zunächst entfettet und nach dem Polieren gespült und getrocknet wird, dadurch gekennzeichnet, dass dem Elektrolyten mindestens eine Fluorverbindung in Form eines einfachen oder komplexen Fluorids in einer Menge von mindestens 2 Vol.-% beigemengt wird und dass das Polieren in einem Temperaturbereich von -20 bis +30 °C bei einer Stromdichte von 20 bis 250 A/dm2 unter einer Spannung von 20 bis 70 V während einer Zeit von 20 sec bis 20 min durchgeführt wird.1. A method for electrolytically polishing a workpiece made of a nickel, cobalt or iron-based alloy by means of an electrolyte containing a concentrated non-oxidizing acid and a fluorosurfactant and a weakly polar organic compound, the workpiece first being degreased and, after polishing, rinsed and dried , characterized in that at least one fluorine compound in the form of a simple or complex fluoride is added to the electrolyte in an amount of at least 2% by volume and that the polishing in a temperature range from -20 to +30 ° C at a current density of 20 to 250 A / dm 2 is carried out under a voltage of 20 to 70 V for a period of 20 sec to 20 min. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Elektrolyt 20 bis 80 Vol.-% konzentrierte H2SO4 enhält.2. The method according to claim 1, characterized in that the electrolyte contains 20 to 80 vol .-% concentrated H 2 SO 4 . 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass der Elektrolyt 20 bis 60 Vol.-% konzentrierte H2SO4, 10 bis 50 Vol.-% C2H5OH, 5 bis 40 Vol.-% Glyzerin, 5 bis 40 Vol.-% HBF4 und 0,1 Vol.-% eines Fluorotensids enthält.3. The method according to claim 2, characterized in that the electrolyte 20 to 60 vol .-% concentrated H 2 SO 4 , 10 to 50 vol .-% C 2 H 5 OH, 5 to 40 vol .-% glycerol, 5 to Contains 40 vol .-% HBF 4 and 0.1 vol .-% of a fluorosurfactant. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Elektrolyt 20 bis 60 Vol.-% konzentrierte H3PO4 enthält.4. The method according to claim 1, characterized in that the electrolyte contains 20 to 60 vol .-% concentrated H 3 PO 4 . 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Elektrolyt 20 bis 60 Vol.-% konzentrierte H3PO4, 10 bis 50 Vol.-% C2H5OH, 5 bis 40 Vol.-% Glyzerin, 5 bis 40 Vol.-% Ammoniumdifluorid und 0,1 Vol.-% eines Fluorotensids enthält.5. The method according to claim 4, characterized in that the electrolyte 20 to 60 vol .-% concentrated H 3 PO 4 , 10 to 50 vol .-% C 2 H 5 OH, 5 to 40 vol .-% glycerol, 5 to Contains 40 vol .-% ammonium difluoride and 0.1 vol .-% of a fluorosurfactant. 6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Elektrolyt je 10 bis 40 Vol.-% konzentrierte H2SO4 und H3PO4; ferner je 10 bis 30 Vol.-% C2H5OH und 2-Propanol; je 5 bis 20 Vol.-% HF und Natriumfluosilikat und 0,1 Vol.-% eines Fluorotensids enthält.6. The method according to claim 1, characterized in that the electrolyte each 10 to 40 vol .-% concentrated H 2 SO 4 and H 3 PO 4 ; further 10 to 30% by volume of C 2 H 5 OH and 2-propanol; contains 5 to 20 vol .-% HF and sodium fluorosilicate and 0.1 vol .-% of a fluorosurfactant.
EP84109758A 1983-08-23 1984-08-16 Process for electrolytically polishing a work piece made of a nickel, cobalt or iron based alloy Expired EP0139958B1 (en)

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Publication number Priority date Publication date Assignee Title
US5574486A (en) * 1993-01-13 1996-11-12 Tektronix, Inc. Ink jet print heads and methos for preparing them
US6409936B1 (en) 1999-02-16 2002-06-25 Micron Technology, Inc. Composition and method of formation and use therefor in chemical-mechanical polishing
US6426295B1 (en) 1999-02-16 2002-07-30 Micron Technology, Inc. Reduction of surface roughness during chemical mechanical planarization(CMP)
DE10320909A1 (en) * 2003-05-09 2004-11-18 Poligrat Holding Gmbh Electrolyte for the electrochemical polishing of metal surfaces
WO2005005693A1 (en) * 2003-07-01 2005-01-20 Superpower, Inc. Process control methods of electropolishing for metal substrate preparation in producing ybco coated conductors
EA201500017A1 (en) * 2009-11-23 2015-07-30 МЕТКОН, ЭлЭлСи ELECTROLYTE SOLUTION AND METHOD OF ELECTROLYTIC POLISHING
US8580103B2 (en) 2010-11-22 2013-11-12 Metcon, Llc Electrolyte solution and electrochemical surface modification methods
GB201200360D0 (en) * 2012-01-11 2012-02-22 Rolls Royce Plc Component production method
US9162301B2 (en) * 2012-08-06 2015-10-20 General Electric Company Electrochemical machining tools and methods
US9163322B2 (en) * 2013-07-01 2015-10-20 General Electric Company Method and apparatus for refurbishing turbine components

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542779A (en) * 1948-01-07 1951-02-20 Columbus Metal Products Inc Electropolishing composition and process
DE1127170B (en) * 1955-08-04 1962-04-05 Minnesota Mining & Mfg Use of perhalocarboxylic acids as an additive to aqueous solutions for the surface treatment of metal objects
DE1220697B (en) * 1962-08-07 1966-07-07 Manfred Ohle Self-regulating bath for anodic polishing of metals
GB2017150A (en) * 1978-03-22 1979-10-03 Latszereszeti Eszkoezoek Gyara Optimum Regulation of an Electrolytic Polishing Process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342711A (en) * 1963-11-14 1967-09-19 Kyowa Hakko Kogyo Kk Electrolytic polishing of stainless steel
US3239440A (en) * 1964-11-23 1966-03-08 Titanium Metals Corp Electrolytic pickling of titanium and titanium base alloy articles
US3389065A (en) * 1964-12-28 1968-06-18 Kyowa Hakko Kogyo Kk Method for electrolytically polishing stainless steel
US3627654A (en) * 1969-11-19 1971-12-14 Atomic Energy Commission Electrolytic process for cleaning high-carbon steels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542779A (en) * 1948-01-07 1951-02-20 Columbus Metal Products Inc Electropolishing composition and process
DE1127170B (en) * 1955-08-04 1962-04-05 Minnesota Mining & Mfg Use of perhalocarboxylic acids as an additive to aqueous solutions for the surface treatment of metal objects
DE1220697B (en) * 1962-08-07 1966-07-07 Manfred Ohle Self-regulating bath for anodic polishing of metals
GB2017150A (en) * 1978-03-22 1979-10-03 Latszereszeti Eszkoezoek Gyara Optimum Regulation of an Electrolytic Polishing Process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115353808A (en) * 2022-07-13 2022-11-18 锦矽半导体(上海)有限公司 Polishing solution for nickel coating
CN115353808B (en) * 2022-07-13 2024-01-23 锦矽半导体(上海)有限公司 Polishing solution for nickel plating

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US4563257A (en) 1986-01-07
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DE3461202D1 (en) 1986-12-11

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