EP2646603B1 - Method for the electrochemical polishing of metallic objects and electrolyte solution suitable therefor - Google Patents

Method for the electrochemical polishing of metallic objects and electrolyte solution suitable therefor Download PDF

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Publication number
EP2646603B1
EP2646603B1 EP11801589.0A EP11801589A EP2646603B1 EP 2646603 B1 EP2646603 B1 EP 2646603B1 EP 11801589 A EP11801589 A EP 11801589A EP 2646603 B1 EP2646603 B1 EP 2646603B1
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electrolyte solution
mass
solution according
group
carbon atoms
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German (de)
French (fr)
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EP2646603A1 (en
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Marco Renoffio
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Otec Praezisionsfinish GmbH
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Otec Praezisionsfinish 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

Definitions

  • the invention relates to a method for the electrochemical polishing of metal objects from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and at least one of these metals containing alloys wherein the metal article is electrically conductively connected to an anode and immersed in an electrolyte solution having a cathode, wherein the electrodes are supplied with an electric voltage. It also refers to a suitable electrolyte solution for the electrochemical polishing of metals from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and at least one of these Metals containing alloys.
  • Electropolishing is a known method of abrasive surface treatment in which the electropolishing articles are immersed in an electrolyte solution and connected to the positive electrode (anode) of a voltage source.
  • the electrolyte solution In the electrolyte solution is arranged the negative electrode (cathode) of the voltage source, so that it comes as a result of the electrical conductivity of the solution to a current flow, which provides for the surface, anodic removal of the metal article.
  • the electrodes can be fed either with DC voltage or with pulsed voltages.
  • the objects are moved in the electrolyte solution in order to minimize concentration gradients formed there.
  • electrochemical polishing in the context of the present invention includes an electrochemical smoothing and an electrochemical glazing.
  • a suitable electrolyte solution here represents an important parameter, it has been shown that some solutions that lead to the one metal to a perfect electropolishing, in another metal achieve virtually no effect or in a rough, fissured or dull surface result.
  • strong inorganic acids in particular phosphoric acid and sulfuric acid, are used for electropolishing aluminum and steel, which may be mixed with alcohols.
  • copper and brass e.g. a mixture of phosphoric acid and alcohols.
  • the DE 10 2005 055 768 A1 describes an electrolyte composition for the electrolytic cleaning and descaling of metallic workpieces, in particular of steel, wherein the electrolyte composition mainly contains hydrochloric acid and sulfuric acid from main constituents.
  • the electrolyte composition may include a Alcohol polyethylene glycol ethers, an n-alkylbenzenesulfonate sodium salt, a secondary alkanesulfonate sodium salt and small amounts of a mineral oil-based defoamer.
  • 5% by mass of the aforementioned electrolyte composition is mixed with 75% by mass of water and 20% by mass of hydrochloric acid to form the final electrolyte, which has a pH of well below zero ,
  • cyanide (CN -) electrolyte solutions are used which are capable of providing satisfactory results in addition to their high toxicity and consequent handling problematic particularly in the case of silver.
  • the WO 2007/121999 A2 describes an intended for electropolishing electrolyte solution containing alkylbenzenesulfonic acid or alkylbenzenesulfonates, ie their salts or derivatives.
  • the electrolyte solution consists of between 2.4 mass% and 3.2 mass% of decylbenzenesulfonates in the form of sodium salts, between 12 mass% and 15 mass% of sodium salts of dialkylbenzenesulfonic acid with alkyl radials between 10 and 14 carbon atoms, between 13 mass% and 16.5 mass% of a petroleum fraction having 17 to 35 carbon atoms, between 0.2 mass% and 0.7 mass% ethanolamine, 1.4 mass .-% copper sulfate and water.
  • this electrolyte solution has also become particular For the electropolishing of silver proved to be only very suitable.
  • the invention is therefore based on the object of proposing a suitable for electropolishing silver and preferably other precious and / or semiprecious metals, simple and inexpensive electrolyte solution of the type mentioned, which has at most a very low health risk potential and consequently is easy to handle , It is further directed to a process for the electrochemical polishing of metal articles including those of silver or its alloys of the type mentioned above.
  • the invention also provides for solving this problem in an electropolishing method of the type mentioned above, that an electrolyte solution is used with the aforementioned composition.
  • an electrolyte solution which contains or also entirely consists of the abovementioned components (a) to (e) in the abovementioned proportions has outstanding suitability for the electropolishing of silver and silver-containing alloys, which also applies in the case of articles With a very complex surface structure, such as jewelry, a smooth, shiny surface can be awarded.
  • electrolyte solution according to the invention does not necessarily have to be used at elevated temperatures for electropolishing, but in particular also enables electropolishing at room temperature.
  • the health risk potential of the solution according to the invention is very low and consequently allows easy and uncomplicated handling by the operating personnel of a corresponding electropolishing device.
  • the solution is very low odor to practically odorless, and in particular may also have a certain viscosity, and mostly largely transparent, although in spite of a certain brown color, which may have the solution, any objects that undergo an electropolishing in the solution, visually detected can be.
  • the ethoxylated alcohol of the electrolytic solution of the present invention may preferably have between 5 and 30 carbon atoms, more preferably between 7 and 25 carbon atoms, preferably between 9 and 20 carbon atoms, with a chain length of such ethoxylated alcohol having between about 10 and about 16 carbon atoms being particularly preferred has proved advantageous. It should be noted that said chain length relates in each case to the ethoxylated alcohol and not to the ethoxylate obtained by addition of ethylene oxide during the ethoxylation.
  • the ethoxylated alcohol may be an alkanol, in particular an isoalkanol, and it may furthermore be advantageous if the ethoxylated alcohol is a primary alcohol, i. the hydroxyl group (OH group) binds to a terminal carbon atom.
  • the ethoxylated alcohol has a relatively low degree of ethoxylation (EO) of in particular between 1 and 50, preferably between 1 and 40, most preferably between 1 and 30.
  • EO ethoxylation
  • Particularly preferred degrees of ethoxylation are between about 1 and about 20, and more preferably between about 2 and about 20.
  • the ethoxylated alcohol may, in a further preferred embodiment, be a monoalcohol having only one hydroxyl group.
  • the at least one substance from the group of sulfonic acids and sulfonates of the electrolytic solution according to the invention may preferably from the group of arenesulfonic and arenesulfonates (ie the sulfur atom of the sulfonic or sulfonate group binds to an aromatic group), in particular from the group of benzenesulfonic acids, alkylbenzenesulfonic acids, benzenesulfonates and Alkylbenzenesulfonates be selected.
  • the at least one substance from the group of sulfonic acids and sulfonates may further preferably from the group benzenesulfonic acid, their alkyl derivatives, in particular their C10-C16-alkyl derivatives, preferably their C10-C13-alkyl derivatives, and salts of benzenesulfonic acid and their alkyl derivatives, in particular with alkali metal - (For example, sodium and potassium salts), alkaline earth metal (eg magnesium and calcium salts), ammonium ions (NH 4 + ) and / or organic amines, in particular triethanolamine and / or triethylamine, be selected.
  • alkyl derivatives of benzenesulfonic acids and their sulfonates have proved to be particularly advantageous for the electrochemical polishing.
  • the at least one inorganic acid from the group of mineral acids such as nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), hydrochloric acid (HCl) and the like, in particular from the group of oxidizing mineral acids, such as preferably nitric acid and / or nitrous acid (HNO 2 ) is selected.
  • nitric acid has proven to be particularly advantageous for electrochemical polishing.
  • Component (d) Liquid hydrocarbon or hydrocarbon mixture:
  • the at least one liquid hydrocarbon of the electrolytic solution of the invention may preferably have a chain length between 5 and 30 carbon atoms, more preferably between 5 and 25 carbon atoms, preferably between 5 and 20 carbon atoms, with chain lengths between about 5 and about 18 carbon atoms being particularly advantageous.
  • the at least one liquid hydrocarbon is a hydrocarbon mixture, in particular from the group of petroleum or a petroleum fraction (eg one having a boiling point or boiling range between about 80 ° C and about 350 ° C, preferably between about 90 ° C and about 330 ° C, in particular between about 100 ° C and about 310 ° C), preferably in the form of light petroleum (kerosene), gasoline or a gasoline fraction, such as light gasoline (eg with a boiling point or boiling range between about 25 ° C and about 100 ° C), white spirit or the like.
  • a hydrocarbon mixture in particular from the group of petroleum or a petroleum fraction (eg one having a boiling point or boiling range between about 80 ° C and about 350 ° C, preferably between about 90 ° C and about 330 ° C, in particular between about 100 ° C and about 310 ° C), preferably in the form of light petroleum (kerosene), gasoline or a gasoline fraction, such as light gasoline (eg with a boiling point or boiling range between about 25
  • hydrocarbon mixtures come into consideration, as obtained in the fractional distillation of petroleum, wherein - as already mentioned - in particular the resulting petroleum fraction or sub-fractions thereof and preferably the light petroleum fraction, ie the kerosene fraction, as well as the gasoline fraction including the light benzene fraction have been found to be suitable.
  • the at least one liquid hydrocarbon or the hydrocarbon mixture may in a preferred embodiment have a boiling point or a boiling range between 25 ° C and 350 ° C, in particular between 50 ° C and 330 ° C, preferably between 75 ° C and 310 ° C, wherein a particularly preferred boiling range may be between about 80 ° C and 300 ° C.
  • the water is present in the form of demineralized or distilled water or in the form of pure water.
  • a pH of the electrolytic solution according to the invention which is advantageous for electropolishing is expediently between 1 and 5, in particular between 1.5 and 4.5, preferably between 2 and 3.5, in particular a pH in the range from about 2 to about 3 has proved to be particularly advantageous.
  • redox potentials of the electrolyte solution of between 350 mV and 700 mV, in particular between 400 mV and 650 mV, preferably between 450 mV and 600 mV, have proved to be advantageous in this connection.
  • the electrolyte solution also contains a proportion of granule particles, in particular in the form of plastic particles.
  • granule particles which are expedient with respect to the constituents
  • the solution should be chemically substantially inert, can serve to be whirled up on the occasion of the electrochemical polishing of metal objects and to come into contact with the objects in order to minimize the formation of a concentration gradient on the surface of the objects.
  • An inventive method for electrochemical polishing of metal objects in particular from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt), wherein the metal article with a Anode is electrically conductively connected and immersed in an electrolyte solution with a cathode and the electrodes are supplied with an electrical voltage, characterized in that an electrolyte solution of the aforementioned type is used, wherein the method otherwise carried out in a conventional manner known in the art can be.
  • the object to be treated can be connected in a customary manner to the positive electrode (anode), while the negative electrode (cathode) is immersed in the electrolyte solution or, in particular, substantially completely inside a container accommodating the solution, around the objects to be treated, to ensure as homogeneous a current density as possible.
  • the electrode voltage can also be changed during an electropolishing process, wherein, for example, depending on the state and type of metal surface of the workpiece different voltages can be set over different periods of time.
  • the voltage may be, for example, a DC voltage or a pulsed voltage.
  • this may preferably be between 0.1 and 5 A / dm 2 , in particular between 0.2 and 4 A / dm 2 , preferably between 0.3 and 3 A / dm 2 .
  • a voltage density of between about 0.5 A / dm 2 and about 2.5 A / dm 2 has proved particularly suitable for silver and its alloys.
  • these should preferably be moved in the electrolyte solution, wherein in the case of an electrolyte solution containing granules the objects can be moved at least at periodic intervals in the fluidized granules, as already indicated above.
  • MARLOPON AT 50 TM Sasol Germany GmbH (DE) (with a proportion of benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine between 50 and 60%) (15 to 30% by mass, for example about 25% by mass) ;
  • MARLOPON AT 50 TM Sasol Germany GmbH (DE) (with a proportion of benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine between 50 and 60%) (15 to 30% by mass, for example about 23% by mass) ;
  • Component (c) Nitric acid (HNO 3 ), concentrated CAS no. [7697-37-2] (1 to 5 mass%, eg 1.6 mass%);

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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)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • ing And Chemical Polishing (AREA)

Description

Die Erfindung betrifft ein Verfahren zum elektrochemischen Polieren von metallenen Gegenständen aus der Gruppe Kupfer (Cu), Zink (Zn), Silber (Ag), Zinn (Sn), Gold (Au), Platin (Pt) sowie wenigstens eines dieser Metalle enthaltenden Legierungen, wobei der metallene Gegenstand mit einer Anode elektrisch leitfähig verbunden und in eine Elektrolytlösung mit einer Kathode eingetaucht wird, wobei die Elektroden mit einer elektrischen Spannung beaufschlagt werden. Sie bezieht sich ferner auf eine hierfür geeignete Elektrolytlösung zum elektrochemischen Polieren von Metallen aus der Gruppe Kupfer (Cu), Zink (Zn), Silber (Ag), Zinn (Sn), Gold (Au), Platin(Pt) sowie wenigstens eines dieser Metalle enthaltenden Legierungen.The invention relates to a method for the electrochemical polishing of metal objects from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and at least one of these metals containing alloys wherein the metal article is electrically conductively connected to an anode and immersed in an electrolyte solution having a cathode, wherein the electrodes are supplied with an electric voltage. It also refers to a suitable electrolyte solution for the electrochemical polishing of metals from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and at least one of these Metals containing alloys.

Das Elektropolieren stellt ein bekanntes Verfahren der abtragenden Oberflächenbearbeitung dar, wobei die zu elektropolierenden Gegenstände in eine Elektrolytlösung eingetaucht und mit der positiven Elektrode (Anode) einer Spannungsquelle verbunden werden. In der Elektrolytlösung ist die negative Elektrode (Kathode) der Spannungsquelle angeordnet, so dass es infolge der elektrischen Leitfähigkeit der Lösung zu einem Stromfluss kommt, welcher für den oberflächigen, anodischen Abtrag des metallenen Gegenstandes sorgt. Die Elektroden können hierbei entweder mit Gleichspannung oder auch mit gepulsten Spannungen gespeist werden. Üblicherweise werden die Gegenstände in der Elektrolytlösung bewegt, um sich dort ausbildende Konzentrationsgradienten möglichst gering zu halten.Electropolishing is a known method of abrasive surface treatment in which the electropolishing articles are immersed in an electrolyte solution and connected to the positive electrode (anode) of a voltage source. In the electrolyte solution is arranged the negative electrode (cathode) of the voltage source, so that it comes as a result of the electrical conductivity of the solution to a current flow, which provides for the surface, anodic removal of the metal article. The electrodes can be fed either with DC voltage or with pulsed voltages. Usually, the objects are moved in the electrolyte solution in order to minimize concentration gradients formed there.

An dieser Stelle sei im Übrigen angemerkt, dass der Begriff "elektrochemisches Polieren" im Sinne der vorliegenden Erfindung ein elektrochemischen Glätten sowie ein elektrochemisches Glänzen mit einschließt.It should also be noted at this point that the term "electrochemical polishing" in the context of the present invention includes an electrochemical smoothing and an electrochemical glazing.

Die Auswahl einer geeigneten Elektrolytlösung stellt hierbei einen wichtigen Parameter dar, wobei sich gezeigt hat, dass einige Lösungen, welche bei dem einen Metall zu einer einwandfreien Elektropolitur führen, bei einem anderen Metall praktisch keine Wirkung erzielen oder in einer rauen, zerklüfteten bzw. matten Oberfläche resultieren. So werden zum Elektropolieren von Aluminium und Stahl gegenwärtig beispielsweise starke anorganische Säuren, insbesondere Phosphorsäure und Schwefelsäure, eingesetzt, welche mit Alkoholen versetzt sein können. Für Kupfer und Messing eignet sich z.B. eine Mischung aus Phosphorsäure und Alkoholen.The choice of a suitable electrolyte solution here represents an important parameter, it has been shown that some solutions that lead to the one metal to a perfect electropolishing, in another metal achieve virtually no effect or in a rough, fissured or dull surface result. Thus, for example, strong inorganic acids, in particular phosphoric acid and sulfuric acid, are used for electropolishing aluminum and steel, which may be mixed with alcohols. For copper and brass, e.g. a mixture of phosphoric acid and alcohols.

Die DE 10 2005 055 768 A1 beschreibt eine Elektrolytzusammensetzung zur elektrolytischen Reinigung und Entzunderung von metallischen Werkstücken, insbesondere aus Stahl, wobei die Elektrolytzusammensetzung vornehmlich Salzsäure und Schwefelsäure aus Hauptbestandteile enthält. Gemäß einem Ausführungsbeispiel kann die Elektrolytzusammensetzung einen Alkoholpolyethylenglykolether, ein n-Alkylbenzolsulfonat Natriumsalz, ein sekundäres Alkansulfonat Natriumsalz sowie geringen Mengen eines Entschäumers auf Mineralölbasis. Zum Einsatz in der elektrolytischen Reinigung und Entzunderung eines metallischen Werkstückes werden 5 Mass.% der vorgenannten Elektrolytzusammensetzung mit 75 Mass.-% Wasser und 20 Mass.-% Salzsäure unter Bildung des fertigen Elektrolyten gemischt, welcher einen pH-Wert von weit unter 0 aufweist.The DE 10 2005 055 768 A1 describes an electrolyte composition for the electrolytic cleaning and descaling of metallic workpieces, in particular of steel, wherein the electrolyte composition mainly contains hydrochloric acid and sulfuric acid from main constituents. According to one embodiment, the electrolyte composition may include a Alcohol polyethylene glycol ethers, an n-alkylbenzenesulfonate sodium salt, a secondary alkanesulfonate sodium salt and small amounts of a mineral oil-based defoamer. For use in the electrolytic cleaning and descaling of a metallic workpiece, 5% by mass of the aforementioned electrolyte composition is mixed with 75% by mass of water and 20% by mass of hydrochloric acid to form the final electrolyte, which has a pH of well below zero ,

Soweit Edelmetalle bzw. Halbedelmetalle, wie beispielsweise Schmuckstücke, mittels Elektropolieren behandelt werden sollen, so stellt insbesondere Silber insoweit ein Problem dar, als eine einwandfrei glänzende, optisch ansprechende und glatte Oberfläche unter Einsatz von bekannten Elektrolytlösungen praktisch nicht erhalten werden kann. Hierfür werden gegenwärtig einerseits cyanidhaltige (CN-) Elektrolytlösungen eingesetzt, welche neben ihrer hohen Toxizität und dadurch bedingten problematischen Handhabung insbesondere bei Silber keine zufriedenstellenden Ergebnisse zu liefern vermögen. Die WO 2007/121999 A2 beschreibt eine für die Elektropolitur vorgesehene Elektrolytlösung, welche Alkylbenzolsulfonsäure oder Alkylbenzolsulfonate, d.h. deren Salze oder Derivate, enthält. Gemäß dem in der Druckschrift angegebenen Ausführungsbeispiel besteht die Elektrolytlösung aus zwischen 2,4 Mass.-% und 3,2 Mass.-% Decylbenzolsulfonate in Form von Natriumsalzen, zwischen 12 Mass.-% und 15 Mass.-% Natriumsalzen von Dialkylbenzolsulfonsäure mit Alkylradialen zwischen 10 und 14 Kohlenstoffatomen, zwischen 13 Mass.-% und 16,5 Mass.-% einer Petroleumfraktion mit 17 bis 35 Kohlenstoffatomen, zwischen 0,2 Mass.-% und 0,7 Mass.-% Ethanolamin, 1,4 Mass.-% Kupfersulfat und Wasser. Indes hat sich auch diese Elektrolytlösung insbesondere zum Elektropolieren von Silber als nur sehr bedingt geeignet erwiesen.As far as precious metals or semi-precious metals, such as jewelry, are to be treated by electropolishing, so silver in particular is a problem insofar as a perfectly shiny, visually appealing and smooth surface using known electrolyte solutions can not be practically obtained. For this purpose, currently one hand, cyanide (CN -) electrolyte solutions are used which are capable of providing satisfactory results in addition to their high toxicity and consequent handling problematic particularly in the case of silver. The WO 2007/121999 A2 describes an intended for electropolishing electrolyte solution containing alkylbenzenesulfonic acid or alkylbenzenesulfonates, ie their salts or derivatives. According to the embodiment given in the document, the electrolyte solution consists of between 2.4 mass% and 3.2 mass% of decylbenzenesulfonates in the form of sodium salts, between 12 mass% and 15 mass% of sodium salts of dialkylbenzenesulfonic acid with alkyl radials between 10 and 14 carbon atoms, between 13 mass% and 16.5 mass% of a petroleum fraction having 17 to 35 carbon atoms, between 0.2 mass% and 0.7 mass% ethanolamine, 1.4 mass .-% copper sulfate and water. However, this electrolyte solution has also become particular For the electropolishing of silver proved to be only very suitable.

Der Erfindung liegt daher die Aufgabe zugrunde, eine zum Elektropolieren von Silber sowie vorzugsweise auch anderen Edel- und/oder Halbedelmetalle geeignete, einfache und kostengünstige Elektrolytlösung der eingangs genannten Art vorzuschlagen, welche ein allenfalls sehr geringes gesundheitliches Gefährdungspotenzial besitzt und folglich in einfacher Weise handhabbar ist. Sie ist ferner auf ein Verfahren zum elektrochemischen Polieren von metallenen Gegenständen einschließlich solcher aus Silber oder dessen Legierungen der eingangs genannten Art gerichtet.The invention is therefore based on the object of proposing a suitable for electropolishing silver and preferably other precious and / or semiprecious metals, simple and inexpensive electrolyte solution of the type mentioned, which has at most a very low health risk potential and consequently is easy to handle , It is further directed to a process for the electrochemical polishing of metal articles including those of silver or its alloys of the type mentioned above.

Erfindungsgemäß wird diese Aufgabe mit einer Elektrolytlösung der eingangs genannten Art dadurch gelöst, welche die folgenden Inhaltsstoffe enthält:

  1. (a) zwischen 2 und 50 Mass.-% wenigstens eines ethoxylierten Alkohols;
  2. (b) zwischen 2 und 50 Mass.-% wenigstens einer Substanz aus der Gruppe der Sulfonsäuren und Sulfonate;
  3. (c) zwischen 0,2 und 10 Mass.-% wenigstens einer anorganischen Säure;
  4. (d) zwischen 6 und 50 Mass.-% wenigstens eines flüssigen Kohlenwasserstoffes; und
  5. (e) zwischen 5 und 90 Mass.-% Wasser;
wobei der pH-Wert der Elektrolytlösung wenigstens 1 beträgt.According to the invention, this object is achieved with an electrolyte solution of the type mentioned in the introduction which contains the following ingredients:
  1. (a) between 2 and 50% by weight of at least one ethoxylated alcohol;
  2. (b) between 2 and 50% by weight of at least one substance selected from the group consisting of sulfonic acids and sulfonates;
  3. (c) between 0.2 and 10 mass% of at least one inorganic acid;
  4. (d) between 6 and 50 mass% of at least one liquid hydrocarbon; and
  5. (e) between 5 and 90% by weight of water;
wherein the pH of the electrolyte solution is at least 1.

In verfahrenstechnischer Hinsicht sieht die Erfindung zur Lösung dieser Aufgabe bei einem Elektropolierverfahren der eingangs genannten Art ferner vor, dass eine Elektrolytlösung mit der vorgenannten Zusammensetzung verwendet wird.In procedural terms, the invention also provides for solving this problem in an electropolishing method of the type mentioned above, that an electrolyte solution is used with the aforementioned composition.

Überraschenderweise wurde gefunden, dass sich eine Elektrolytlösung, welche die vorgenannten Komponenten (a) bis (e) in den genannten Anteilen enthält oder auch gänzlich hieraus besteht, eine hervorragende Eignung für die Elektropolitur von Silber und silberhaltigen Legierungen besitzt, welchen auch im Falle von Gegenständen mit sehr komplexer Oberflächenstruktur, wie beispielsweise Schmuckstücken, eine glatte, glänzende Oberfläche verliehen werden kann. Entsprechendes gilt für andere Edel- und Halbedelmetalle sowie deren Legierungen, beispielsweise für Kupfer, Zinn, Zink, Messing, Bronze, Gold oder Platin bzw. hieraus gebildete legierungen aus den vorgenannten und/oder mit weiteren Legierungsbestandteilen. Ein weiterer Vorteil der erfindungsgemäßen Elektrolytlösung besteht darin, dass sie nicht notwendigerweise bei erhöhten Temperaturen für die Elektropolitur eingesetzt werden muss, sondern insbesondere auch ein Elektropolieren bei Raumtemperatur ermöglicht. Das gesundheitliche Gefährdungspotenzial der erfindungsgemäßen Lösung ist sehr gering und erlaubt folglich eine einfache und unkomplizierte Handhabung durch das Bedienpersonal einer entsprechenden Elektropoliervorrichtung. Dabei ist die Lösung sehr geruchsarm bis praktisch geruchsfrei, wobei sie insbesondere auch eine gewisse Viskosität aufweisen kann, sowie zumeist weitestgehend transparent, wobei trotz einer gewissen Braunfärbung, welche die Lösung aufweisen kann, etwaige Gegenstände, welche eine Elektropolitur in der Lösung erfahren, visuell erfasst werden können.Surprisingly, it has been found that an electrolyte solution which contains or also entirely consists of the abovementioned components (a) to (e) in the abovementioned proportions has outstanding suitability for the electropolishing of silver and silver-containing alloys, which also applies in the case of articles With a very complex surface structure, such as jewelry, a smooth, shiny surface can be awarded. The same applies to other precious and semi-precious metals and their alloys, for example, copper, tin, zinc, brass, bronze, gold or platinum or alloys thereof formed from the aforementioned and / or other alloying ingredients. Another advantage of the electrolyte solution according to the invention is that it does not necessarily have to be used at elevated temperatures for electropolishing, but in particular also enables electropolishing at room temperature. The health risk potential of the solution according to the invention is very low and consequently allows easy and uncomplicated handling by the operating personnel of a corresponding electropolishing device. In this case, the solution is very low odor to practically odorless, and in particular may also have a certain viscosity, and mostly largely transparent, although in spite of a certain brown color, which may have the solution, any objects that undergo an electropolishing in the solution, visually detected can be.

Komponente (a): Ethoxylierter Alkohol:Component (a): Ethoxylated alcohol:

Der ethoxylierte Alkohol der erfindungsgemäßen Elektrolytlösung kann in bevorzugter Ausführung zwischen 5 und 30 Kohlenstoffatome, insbesondere zwischen 7 und 25 Kohlenstoffatome, vorzugsweise zwischen 9 und 20 Kohlenstoffatome, aufweisen, wobei sich eine Kettenlänge eines solchen ethoxylierten Alkohols mit zwischen etwa 10 und etwa 16 Kohlenstoffatomen als besonders vorteilhaft erwiesen hat. Es sei darauf hingewiesen, dass sich die genannte Kettenlänge jeweils auf den ethoxylierten Alkohol und nicht auf das durch Anlagerung von Ethylenoxid anlässlich der Ethoxylierung erhaltene Ethoxylat bezieht.The ethoxylated alcohol of the electrolytic solution of the present invention may preferably have between 5 and 30 carbon atoms, more preferably between 7 and 25 carbon atoms, preferably between 9 and 20 carbon atoms, with a chain length of such ethoxylated alcohol having between about 10 and about 16 carbon atoms being particularly preferred has proved advantageous. It should be noted that said chain length relates in each case to the ethoxylated alcohol and not to the ethoxylate obtained by addition of ethylene oxide during the ethoxylation.

In weiterhin bevorzugter Ausgestaltung kann der ethoxylierte Alkohol ein Alkanol, insbesondere ein Isoalkanol, sein, wobei es darüber hinaus vorteilhaft sein kann, wenn der ethoxylierte Alkohol ein primärer Alkohol ist, d.h. die Hydroxylgruppe (OH-Gruppe) bindet an ein endständiges Kohlenstoffatom.In a further preferred embodiment, the ethoxylated alcohol may be an alkanol, in particular an isoalkanol, and it may furthermore be advantageous if the ethoxylated alcohol is a primary alcohol, i. the hydroxyl group (OH group) binds to a terminal carbon atom.

Überdies kann es von Vorteil sein, wenn der ethoxylierte Alkohol einen relativ geringen Ethoxylierungsgrad (EO) von insbesondere zwischen 1 und 50, vorzugsweise zwischen 1 und 40, höchst vorzugsweise zwischen 1 und 30, aufweist. Besonders bevorzugte Ethoxylierungsgrade liegen zwischen etwa 1 und etwa 20 und insbesondere zwischen etwa 2 und etwa 20.Moreover, it may be advantageous if the ethoxylated alcohol has a relatively low degree of ethoxylation (EO) of in particular between 1 and 50, preferably between 1 and 40, most preferably between 1 and 30. Particularly preferred degrees of ethoxylation are between about 1 and about 20, and more preferably between about 2 and about 20.

Der ethoxylierte Alkohol kann in weiterhin bevorzugter Ausgestaltung ein Monoalkohol mit nur einer Hydroxylgruppe sein.The ethoxylated alcohol may, in a further preferred embodiment, be a monoalcohol having only one hydroxyl group.

Komponente (b): Sulfonsäure bzw. Sulfonat:Component (b): sulfonic acid or sulfonate:

Die wenigstens eine Substanz aus der Gruppe der Sulfonsäuren und Sulfonate der erfindungsgemäßen Elektrolytlösung kann vorzugsweise aus der Gruppe der Arensulfonsäuren und Arensulfonate (d.h. das Schwefelatom der Sulfonsäure- oder Sulfonatgruppe bindet an eine aromatische Gruppe), insbesondere aus der Gruppe der Benzolsulfonsäuren, Alkylbenzolsulfonsäuren, Benzolsulfonate und Alkylbenzolsulfonate, gewählt sein.The at least one substance from the group of sulfonic acids and sulfonates of the electrolytic solution according to the invention may preferably from the group of arenesulfonic and arenesulfonates (ie the sulfur atom of the sulfonic or sulfonate group binds to an aromatic group), in particular from the group of benzenesulfonic acids, alkylbenzenesulfonic acids, benzenesulfonates and Alkylbenzenesulfonates be selected.

Die wenigstens eine Substanz aus der Gruppe der Sulfonsäuren und Sulfonate kann hierbei ferner vorzugsweise aus der Gruppe Benzolsulfonsäure, deren Alkylderivate, insbesondere deren C10-C16-Alkylderivate, vorzugsweise deren C10-C13-Alkylderivate, sowie Salzen von Benzolsulfonsäure und deren Alkylderivaten, insbesondere mit Alkalimetall- (z.B. Natrium- und Kaliumsalze), Erdalkalimetall- (z.B. Magnesium- und Calciumsalze), Ammoniumionen (NH4 +) und/oder organischen Aminen, insbesondere Triethanolamin und/oder Triethylamin, gewählt sein. Als besonders vorteilhaft für die elektrochemische Politur haben sich insbesondere Alkylderivate von Benzolsulfonsäuren und deren Sulfonate erwiesen.The at least one substance from the group of sulfonic acids and sulfonates may further preferably from the group benzenesulfonic acid, their alkyl derivatives, in particular their C10-C16-alkyl derivatives, preferably their C10-C13-alkyl derivatives, and salts of benzenesulfonic acid and their alkyl derivatives, in particular with alkali metal - (For example, sodium and potassium salts), alkaline earth metal (eg magnesium and calcium salts), ammonium ions (NH 4 + ) and / or organic amines, in particular triethanolamine and / or triethylamine, be selected. In particular, alkyl derivatives of benzenesulfonic acids and their sulfonates have proved to be particularly advantageous for the electrochemical polishing.

Komponente (c): Anorganische Säure:Component (c): Inorganic acid:

Während sich als anorganische Säure für die erfindungsgemäße Elektrolytlösung vornehmlich starke Säuren mit einem relativ hohen pKs-Wert anbieten, kann gemäß einer vorteilhaften Ausgestaltung vorgesehen sein, dass die wenigstens eine anorganische Säure aus der Gruppe der Mineralsäuren, wie z.B. Salpetersäure (HNO3), Schwefelsäure (H2SO4), Phosphorsäure (H3PO4), Salzsäure (HCl) und dergleichen, insbesondere aus der Gruppe der oxidierenden Mineralsäuren, wie vorzugsweise Salpetersäure und/oder salpetrige Säure (HNO2), gewählt ist. Als besonders vorteilhaft für die elektrochemische Politur hat sich dabei insbesondere Salpetersäure erwiesen.While offer as inorganic acid for the electrolytic solution according to the invention primarily strong acids with a relatively high pKs, can be provided according to an advantageous embodiment that the at least one inorganic acid from the group of mineral acids, such as nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), hydrochloric acid (HCl) and the like, in particular from the group of oxidizing mineral acids, such as preferably nitric acid and / or nitrous acid (HNO 2 ) is selected. In particular, nitric acid has proven to be particularly advantageous for electrochemical polishing.

Komponente (d): Flüssiger Kohlenwasserstoff oder Kohlenwasserstoffgemisch:Component (d): Liquid hydrocarbon or hydrocarbon mixture:

Der wenigstens eine flüssige Kohlenwasserstoff der erfindungsgemäßen Elektrolytlösung kann vorzugsweise eine Kettenlänge zwischen 5 und 30 Kohlenstoffatomen, insbesondere zwischen 5 und 25 Kohlenstoffatomen, vorzugsweise zwischen 5 und 20 Kohlenstoffatomen, aufweisen, wobei sich Kettenlängen zwischen etwa 5 und etwa 18 Kohlenstoffatomen als besonders vorteilhaft erwiesen haben.The at least one liquid hydrocarbon of the electrolytic solution of the invention may preferably have a chain length between 5 and 30 carbon atoms, more preferably between 5 and 25 carbon atoms, preferably between 5 and 20 carbon atoms, with chain lengths between about 5 and about 18 carbon atoms being particularly advantageous.

Gemäß einer bevorzugten Ausgestaltung kann insbesondere vorgesehen sein, dass der wenigstens eine flüssige Kohlenwasserstoff ein Kohlenwasserstoffgemisch ist, insbesondere aus der Gruppe Petroleum oder einer Petroleumfraktion (z.B. einer solchen mit einem Siedepunkt bzw. Siedebereich zwischen etwa 80°C und etwa 350°C, vorzugsweise zwischen etwa 90°C und etwa 330°C, insbesondere zwischen etwa 100°C und etwa 310°C), vorzugsweise in Form von leichtem Petroleum (Kerosin), Benzin oder einer Benzinfraktion, wie beispielsweise Leichtbenzin (z.B. mit einem Siedepunkt bzw. Siedebereich zwischen etwa 25°C und etwa 100°C), Testbenzin oder dergleichen. Hierbei kommen insbesondere solche Kohlenwasserstoffgemische in Betracht, wie sie bei der fraktionierten Destillation von Erdöl anfallen, wobei sich - wie bereits erwähnt - insbesondere die hierbei anfallende Petroleumfraktion bzw. Unterfraktionen derselben und vorzugsweise die leichte Petroleumfraktion, d.h. die Kerosinfraktion, sowie die Benzinfraktion einschließlich der Leichtbenzinfraktion als geeignet erwiesen haben.According to a preferred embodiment, it may in particular be provided that the at least one liquid hydrocarbon is a hydrocarbon mixture, in particular from the group of petroleum or a petroleum fraction (eg one having a boiling point or boiling range between about 80 ° C and about 350 ° C, preferably between about 90 ° C and about 330 ° C, in particular between about 100 ° C and about 310 ° C), preferably in the form of light petroleum (kerosene), gasoline or a gasoline fraction, such as light gasoline (eg with a boiling point or boiling range between about 25 ° C and about 100 ° C), white spirit or the like. In particular, those hydrocarbon mixtures come into consideration, as obtained in the fractional distillation of petroleum, wherein - as already mentioned - in particular the resulting petroleum fraction or sub-fractions thereof and preferably the light petroleum fraction, ie the kerosene fraction, as well as the gasoline fraction including the light benzene fraction have been found to be suitable.

Der wenigstens eine flüssige Kohlenwasserstoff bzw. das Kohlenwasserstoffgemisch kann in bevorzugter Ausführung einen Siedepunkt bzw. einen Siedebereich zwischen 25°C und 350°C, insbesondere zwischen 50°C und 330°C, vorzugsweise zwischen 75°C und 310°C, aufweist, wobei ein besonders bevorzugter Siedebereich zwischen etwa 80°C und 300°C betragen kann.The at least one liquid hydrocarbon or the hydrocarbon mixture may in a preferred embodiment have a boiling point or a boiling range between 25 ° C and 350 ° C, in particular between 50 ° C and 330 ° C, preferably between 75 ° C and 310 ° C, wherein a particularly preferred boiling range may be between about 80 ° C and 300 ° C.

Komponente (e): Wasser:Component (s): Water:

Um einen unkontrollierten Eintrag von Salzen und gegebenenfalls weiteren Inhaltsstoffen in die erfindungsgemäße Elektrolytlösung zu verhindern und lokal unterschiedlichen Leitungswasserqualitäten Rechnung zu tragen, kann es zweckmäßig sein, wenn das Wasser in Form von demineralisierten oder destillierte Wasser bzw. in Form von Reinwasser vorliegt.In order to prevent an uncontrolled entry of salts and optionally further ingredients into the electrolyte solution according to the invention and to take into account locally different tap water qualities, it may be expedient if the water is present in the form of demineralized or distilled water or in the form of pure water.

Weitere Parameter:Other parameters:

In Bezug auf die Massenanteile der obigen Komponenten (a) bis (e), welche die erfindungsgemäße Elektrolytlösung enthält oder auch gänzlich hieraus besteht, können in bevorzugter Ausgestaltung die folgenden Anteile vorgesehen sein:

  1. (a) zwischen 3,5 und 40 Mass.-%, insbesondere zwischen 5 und 30 Mass.-%, vorzugsweise zwischen etwa 10 und etwa 20 Mass.-%, des wenigstens einen ethoxylierten Alkohols;
  2. (b) zwischen 3,5 und 40 Mass.-%, insbesondere zwischen 5 und 30 Mass.-%, vorzugsweise zwischen etwa 7,5 und etwa 25 Mass.-%, der wenigstens einen Substanz aus der Gruppe der Sulfonsäuren und Sulfonate;
  3. (c) zwischen 0,2 und 7,5 Mass.-%, insbesondere zwischen 0,2 und 5 Mass.-%, vorzugsweise zwischen etwa 0,2 und etwa 4 Mass.%, der wenigstens einen anorganischen Säure;
  4. (d) zwischen 8 und 40 Mass.-%, insbesondere zwischen 10 und 30 Mass.-%, vorzugsweise zwischen etwa 10 und etwa 20 Mass.-%, des wenigstens einen flüssigen Kohlenwasserstoffes; und
  5. (e) zwischen 10 und 80 Mass.-%, insbesondere zwischen 15 und 70 Mass.-%, vorzugsweise zwischen etwa 25 und etwa 65 Mass.-%, Wasser.
With regard to the proportions by mass of the above components (a) to (e), which contains or also consists entirely of the electrolyte solution according to the invention, the following proportions can be provided in a preferred embodiment:
  1. (a) between 3.5 and 40 mass%, in particular between 5 and 30 mass%, preferably between about 10 and about 20 mass%, of the at least one ethoxylated alcohol;
  2. (b) between 3.5 and 40 mass%, in particular between 5 and 30 mass%, preferably between about 7.5 and about 25 mass%, of the at least one substance from the group of sulfonic acids and sulfonates;
  3. (c) between 0.2 and 7.5 mass%, in particular between 0.2 and 5 mass%, preferably between about 0.2 and about 4 mass%, of the at least one inorganic acid;
  4. (d) between 8 and 40 mass%, in particular between 10 and 30 mass%, preferably between about 10 and about 20 mass%, of the at least one liquid hydrocarbon; and
  5. (e) between 10 and 80 mass%, in particular between 15 and 70 mass%, preferably between about 25 and about 65 mass%, of water.

Ein für die Elektropolitur vorteilhafter pH-Wert der erfindungsgemäßen Elektrolytlösung beträgt zweckmäßig zwischen 1 und 5, insbesondere zwischen 1,5 und 4,5, vorzugsweise zwischen 2 und 3,5, wobei sich insbesondere ein pH-Wert im Bereich von etwa 2 bis etwa 3 als besonders vorteilhaft erwiesen hat.A pH of the electrolytic solution according to the invention which is advantageous for electropolishing is expediently between 1 and 5, in particular between 1.5 and 4.5, preferably between 2 and 3.5, in particular a pH in the range from about 2 to about 3 has proved to be particularly advantageous.

In Bezug auf ein bevorzugtes Redoxpotenzial haben sich in diesem Zusammenhang Redoxpotenziale der Elektrolytlösung von zwischen 350 mV und 700 mV, insbesondere zwischen 400 mV und 650 mV, vorzugsweise zwischen 450 mV und 600 mV, als vorteilhaft erwiesen.With respect to a preferred redox potential, redox potentials of the electrolyte solution of between 350 mV and 700 mV, in particular between 400 mV and 650 mV, preferably between 450 mV and 600 mV, have proved to be advantageous in this connection.

Darüber hinaus kann vorgesehen sein, dass die Elektrolytlösung ferner einen Anteil an Granulatpartikeln enthält, insbesondere in Form von Kunststoffpartikeln. Derartige Granulatpartikel, welche zweckmäßig gegenüber den Bestandteilen der Lösung chemisch weitestgehend inert sein sollten, können dazu dienen, anlässlich dem elektrochemischen Polieren von metallenen Gegenständen aufgewirbelt zu werden und mit den Gegenständen in Berührung zu kommen, um die Ausbildung eines Konzentrationsgradienten an der Oberfläche der Gegenständen möglichst gering zu halten.In addition, it can be provided that the electrolyte solution also contains a proportion of granule particles, in particular in the form of plastic particles. Such granule particles which are expedient with respect to the constituents The solution should be chemically substantially inert, can serve to be whirled up on the occasion of the electrochemical polishing of metal objects and to come into contact with the objects in order to minimize the formation of a concentration gradient on the surface of the objects.

Ein erfindungsgemäßes Verfahren zum elektrochemischen Polieren von metallenen Gegenständen, insbesondere aus der Gruppe Kupfer (Cu), Zink (Zn), Silber (Ag), Zinn (Sn), Gold (Au), Platin (Pt), wobei der metallene Gegenstand mit einer Anode elektrisch leitfähig verbunden und in eine Elektrolytlösung mit einer Kathode eingetaucht wird und die Elektroden mit einer elektrischen Spannung beaufschlagt werden, ist dadurch gekennzeichnet, dass eine Elektrolytlösung der vorgenannten Art zum Einsatz kommt, wobei das Verfahren ansonsten in einer üblichen, dem Fachmann bekannten Weise durchgeführt werden kann.An inventive method for electrochemical polishing of metal objects, in particular from the group copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt), wherein the metal article with a Anode is electrically conductively connected and immersed in an electrolyte solution with a cathode and the electrodes are supplied with an electrical voltage, characterized in that an electrolyte solution of the aforementioned type is used, wherein the method otherwise carried out in a conventional manner known in the art can be.

Als Elektrodenspannung hat sich im Zusammenhang mit der erfindungsgemäßen Elektrolytlösung insbesondere eine solche zwischen 0,5 V und 20 V, insbesondere zwischen 0,75 V und 15 V, vorzugsweise zwischen etwa 1 V und etwa 10 V, als günstig erwiesen. Dabei kann der zu behandelnde Gegenstand in üblicher Weise mit der positiven Elektrode (Anode) verbunden werden, während die negative Elektrode (Kathode) in die Elektrolytlösung eintaucht oder insbesondere im Wesentlichen vollumfänglich im Innern eines die Lösung aufnehmenden Behälters um die behandelnden Gegenstände herum angeordnet ist, um für eine möglichst homogene Stromdichte zu sorgen. Die Elektrodenspannung kann ferner während eines Elektropoliervorganges verändert werden, wobei z.B. je nach Zustand und Art der metallenen Oberfläche des Werkstückes verschiedene Spannungen über verschiedene Zeiträume hinweg eingestellt werden können. Die Spannung kann darüber hinaus beispielsweise eine Gleichspannung oder eine gepulste Spannung sein.In particular, between 0.5 V and 20 V, in particular between 0.75 V and 15 V, preferably between about 1 V and about 10 V, has proved favorable as electrode voltage in connection with the electrolyte solution according to the invention. In this case, the object to be treated can be connected in a customary manner to the positive electrode (anode), while the negative electrode (cathode) is immersed in the electrolyte solution or, in particular, substantially completely inside a container accommodating the solution, around the objects to be treated, to ensure as homogeneous a current density as possible. The electrode voltage can also be changed during an electropolishing process, wherein, for example, depending on the state and type of metal surface of the workpiece different voltages can be set over different periods of time. In addition, the voltage may be, for example, a DC voltage or a pulsed voltage.

Was die anlässlich der Elektropolitur eingestellte, vorteilhafte Stromdichte betrifft, so kann diese vorzugsweise zwischen 0,1 und 5 A/dm2, insbesondere zwischen 0,2 und 4 A/dm2, vorzugsweise zwischen 0,3 und 3 A/dm2. Als besonders geeignet für Silber und dessen Legierungen hat sich beispielsweise eine Spannungsdichte zwischen etwa 0,5 A/dm2 etwa 2,5 A/dm2 erwiesen.With regard to the advantageous current density set on the occasion of the electropolishing, this may preferably be between 0.1 and 5 A / dm 2 , in particular between 0.2 and 4 A / dm 2 , preferably between 0.3 and 3 A / dm 2 . For example, a voltage density of between about 0.5 A / dm 2 and about 2.5 A / dm 2 has proved particularly suitable for silver and its alloys.

Hinsichtlich eines bereits oben angesprochenen Entgegenwirkens auf die Ausbildung eines Konzentrationsgradienten an der Oberfläche der zu behandelnden, metallenen Gegenstände sollten diese vorzugsweise in der Elektrolytlösung bewegt werden, wobei im Falle einer Granulatpartikel enthaltenden Elektrolytlösung die Gegenstände zumindest in periodischen Zeitabständen in dem aufgewirbelten Granulat bewegt werden können, wie es ebenfalls weiter oben bereits angedeutet ist.With regard to an above-mentioned opposition to the formation of a concentration gradient on the surface of the metal objects to be treated, these should preferably be moved in the electrolyte solution, wherein in the case of an electrolyte solution containing granules the objects can be moved at least at periodic intervals in the fluidized granules, as already indicated above.

Nachstehend sind exemplarische Ausführungsbeispiele für je eine aus denselben Bestandteilen zusammengesetzte Elektrolytlösung angegeben, welche sich für das elektrochemische Polieren einschließlich des elektrochemischen Glättens und Glänzens von metallenen Gegenständen auch und insbesondere aus Silber und dessen Legierungen als hervorragend geeignet erwiesen haben: Ausführungsbeispiel 1: Komponente (a): Isotridecanol (C13H27OH), ethoxyliert mit einem Ethoxylierungsgrad (EO) von 2-5 CAS-Nr. [69011-36-5] MARLIPAL O 13/50™, Sasol Germany GmbH (DE) (10 bis 20 Mass.-%, z.B. etwa 15 Mass.-%); Komponente (b): Benzolsulfonsäure, C10-13-Alkylderivate, Verbindungen mit Triethanolamin CAS-Nr. [68411-31-4] MARLOPON AT 50™, Sasol Germany GmbH (DE) (mit einem Anteil an Benzolsulfonsäure, C10-13-Alkylderivate, Verbindungen mit Triethanolamin zwischen 50 und 60%) (15 bis 30 Mass.-%, z.B. etwa 25 Mass.-%); Komponente (c): Salpetersäure (HNO3), konzentriert CAS-Nr. [7697-37-2] (1 bis 5 Mass.-%, z.B. 2,5 Mass.-%); Komponente (d): Mischung aus Kerosinkomponenten, Kohlenwasserstoffgemisch, Bereich C9 bis C16, Siedebereich 130°C bis 290°C CAS-Nrn. [8008-20-6], [64742-81-0], [64742-47-8] Nr. 139 - Leuchtpetroleum, Nr. 140 - Petroleum, Agip Deutschland GmbH (DE) (10 bis 20 Mass.-%, z.B. etwa 15 Mass.-%); Komponente (e): Destilliertes Wasser (25 bis 65 Mass.-%, z.B. etwa 42,5 Mass.-%) Weitere Parameter: r: pH-Wert: etwa 2; Redoxpotenzial: etwa 520 mV. Ausführungsbeispiel 2: Komponente (a): Isotridecanol (C13H27OH), ethoxyliert mit einem Ethoxylierungsgrad (EO) von 2-5 CAS-Nr. [69011-36-5] MARLIPAL O 13/50™, Sasol Germany GmbH (DE) (10 bis 20 Mass.-%, z.B. etwa 10 Mass.-%); Komponente (b): Benzolsulfonsäure, C10-13-Alkylderivate, Verbindungen mit Triethanolamin CAS-Nr. [68411-31-4] MARLOPON AT 50™, Sasol Germany GmbH (DE) (mit einem Anteil an Benzolsulfonsäure, C10-13-Alkylderivate, Verbindungen mit Triethanolamin zwischen 50 und 60%) (15 bis 30 Mass.-%, z.B. etwa 23 Mass.-%); Komponente (c): Salpetersäure (HNO3), konzentriert CAS-Nr. [7697-37-2] (1 bis 5 Mass.-%, z.B. 1,6 Mass.-%); Komponente (d): Mischung aus Kerosinkomponenten, Kohlenwasserstoffgemisch, Bereich C9 bis C16, Siedebereich 130°C bis 290°C CAS-Nrn. [8008-20-6], [64742-81-0], [64742-47-8] Nr. 139 - Leuchtpetroleum, Nr. 140 - Petroleum, Agip Deutschland GmbH (DE) (10 bis 20 Mass.-%, z.B. etwa 13 Mass.-%); Komponente (e): Destilliertes Wasser (25 bis 65 Mass.-%, z.B. etwa 52,4 Mass.-%) Weitere Parameter: pH-Wert: etwa 2,3; Redoxpotenzial: etwa 510 mV. In the following, exemplary embodiments are given for each of an electrolyte solution composed of the same constituents, which have proven to be outstandingly suitable for electrochemical polishing, including the electrochemical smoothing and shining of metal objects and in particular of silver and its alloys: <b> Embodiment 1: </ b> Component (a): Isotridecanol (C 13 H 27 OH), ethoxylated with a degree of ethoxylation (EO) of 2-5 CAS-No. [69011-36-5] MARLIPAL O 13/50 ™, Sasol Germany GmbH (DE) (10 to 20 Mass .-%, for example about 15 Mass .-%); Component (b): Benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine CAS-No. [68411-31-4] MARLOPON AT 50 ™ , Sasol Germany GmbH (DE) (with a proportion of benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine between 50 and 60%) (15 to 30% by mass, for example about 25% by mass) ; Component (c): Nitric acid (HNO 3 ), concentrated CAS-No. [7697-37-2] (1 to 5 mass%, eg 2.5 mass%); Component (d): Mixture of kerosene components, hydrocarbon mixture, range C9 to C16, boiling range 130 ° C to 290 ° C CAS Nos. [8008-20-6], [64742-81-0], [64742-47-8] No. 139 - Petroleum kerosene, No. 140 - Petroleum, Agip Deutschland GmbH (DE) (10 to 20% by mass, eg about 15% by mass); Component (s): Distilled water (25 to 65 mass%, eg about 42.5 mass%) Other parameters: r: pH: about 2; Redox potential: about 520 mV. Component (a): Isotridecanol (C 13 H 27 OH), ethoxylated with a degree of ethoxylation (EO) of 2-5 CAS-No. [69011-36-5] MARLIPAL O 13/50 ™, Sasol Germany GmbH (DE) (10 to 20 Mass .-%, for example about 10 Mass .-%); Component (b): Benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine CAS-No. [68411-31-4] MARLOPON AT 50 ™ , Sasol Germany GmbH (DE) (with a proportion of benzenesulfonic acid, C10-13-alkyl derivatives, compounds with triethanolamine between 50 and 60%) (15 to 30% by mass, for example about 23% by mass) ; Component (c): Nitric acid (HNO 3 ), concentrated CAS no. [7697-37-2] (1 to 5 mass%, eg 1.6 mass%); Component (d): Mixture of kerosene components, hydrocarbon mixture, range C9 to C16, boiling range 130 ° C to 290 ° C CAS Nos. [8008-20-6], [64742-81-0], [64742-47-8] No. 139 - kerosene, No. 140 - Petroleum, Agip Deutschland GmbH (DE) (10 to 20% by mass, eg about 13% by mass); Component (s): Distilled water (25 to 65 mass%, eg about 52.4 mass%) Other parameters: pH: about 2.3; Redox potential: about 510 mV.

Claims (18)

  1. Electrolyte solution for electrochemical polishing of metals from the group of copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and alloys containing at least one of these metals, comprising:
    (a) between 2% and 50% by mass of at least one ethoxylated alcohol;
    (b) between 2% and 50% by mass of at least one substance from the group of the sulphonic acids and sulphonates;
    (c) between 0.2% and 10% by mass of at least one inorganic acid;
    (d) between 6% and 50% by mass of at least one liquid hydrocarbon; and
    (e) between 5% and 90% by mass of water;
    wherein the pH of the electrolyte solution is at least 1.
  2. Electrolyte solution according to Claim 1, characterized in that the ethoxylated alcohol of (a) has between 5 and 30 carbon atoms, especially between 7 and 25 carbon atoms, preferably between 9 and 20 carbon atoms.
  3. Electrolyte solution according to Claim 1 or 2, characterized in that the ethoxylated alcohol of (a) is an alkanol, especially an isoalkanol.
  4. Electrolyte solution according to any of Claims 1 to 3, characterized in that the ethoxylated alcohol of (a) is a primary alcohol.
  5. Electrolyte solution according to any of Claims 1 to 4, characterized in that the ethoxylated alcohol of (a) has an ethoxylation level (EO) between 1 and 50, especially between 1 and 40, preferably between 1 and 30.
  6. Electrolyte solution according to any of Claims 1 to 5, characterized in that the at least one substance from the group of the sulphonic acids and sulphonates of (b) is selected from the group of the arenesulphonic acids and arenesulphonates, especially from the group of the benzenesulphonic acids, alkylbenzenesulphonic acids, benzene-sulphonates and alkylbenzenesulphonates.
  7. Electrolyte solution according to any of Claims 1 to 6, characterized in that the at least one substance from the group of the sulphonic acids and sulphonates of (b) is selected from the group of benzenesulphonic acid, the alkyl derivatives thereof, especially the C10-C16-alkyl derivatives thereof, preferably the C10-C13-alkyl derivatives thereof, and salts of benzenesulphonic acid and the alkyl derivatives thereof, especially with alkali metal, alkaline earth metal or ammonium ions and/or organic amines, especially triethanolamine and/or triethylamine.
  8. Electrolyte solution according to any of Claims 1 to 7, characterized in that the at least one inorganic acid is selected from the group of the mineral acids, especially from the group of the oxidizing mineral acids.
  9. Electrolyte solution according to any of Claims 1 to 8, characterized in that the at least one inorganic acid is selected from the group of nitric acid (HNO3), nitrous acid (HNO2) and mixtures thereof.
  10. Electrolyte solution according to any of Claims 1 to 9, characterized in that the at least one liquid hydrocarbon of (d) has a chain length between 5 and 30 carbon atoms, especially between 5 and 25 carbon atoms, preferably between 5 and 20 carbon atoms.
  11. Electrolyte solution according to any of Claims 1 to 10, characterized in that the at least one liquid hydrocarbon of (d) is a hydrocarbon mixture, especially from the group of petroleum or a petroleum fraction, preferably in the form of light petroleum (kerosene), benzine or a benzine fraction.
  12. Electrolyte solution according to any of Claims 1 to 11, characterized in that the at least one liquid hydrocarbon of (d) or the hydrocarbon mixture has a boiling point or boiling range between 25°C and 350°C, especially between 50°C and 330°C, preferably between 75°C and 310°C.
  13. Electrolyte solution according to any of Claims 1 to 12, characterized in that the water of (e) is demineralized or distilled water.
  14. Electrolyte solution according to any of Claims 1 to 13, characterized in that it has
    - a pH between 1 and 5, especially between 1.5 and 4.5, preferably between 2 and 3.5, and/or
    - a redox potential between 350 mV and 700 mV, especially between 400 mV and 650 mV, preferably between 450 mV and 600 mV.
  15. Electrolyte solution according to any of Claims 1 to 14, characterized in that it further comprises a content of granule particles, especially in the form of polymer particles.
  16. Method for electrochemical polishing of metallic articles from the group of copper (Cu), zinc (Zn), silver (Ag), tin (Sn), gold (Au), platinum (Pt) and alloys containing at least one of these metals, wherein the metallic article is connected in an electrically conductive manner to an anode and is dipped into an electrolyte solution having a cathode, and the electrodes are supplied with an electrical voltage, characterized in that an electrolyte solution according to any of Claims 1 to 15 is used.
  17. Method according to Claim 16, characterized in that
    - an electrode voltage between 0.5 V and 20 V, especially between 0.75 V and 15 V, and/or
    - a current density between 0.1 and 5 A/dm2, especially between 0.2 and 4 A/dm2, preferably between 0.3 and 3 A/dm2,
    is established.
  18. Method according to Claim 16 or 17, characterized in that the articles are agitated in the electrolyte solution, and in the case of an electrolyte solution containing granule particles there is agitation of the articles at least at periodic time intervals in the fluidized granular material.
EP11801589.0A 2010-11-30 2011-11-25 Method for the electrochemical polishing of metallic objects and electrolyte solution suitable therefor Not-in-force EP2646603B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010052778 DE102010052778B4 (en) 2010-11-30 2010-11-30 Process for the electrochemical polishing of metal objects and suitable electrolyte solution for this purpose
PCT/EP2011/005937 WO2012072219A1 (en) 2010-11-30 2011-11-25 Method for the electrochemical polishing of metallic objects and electrolyte solution suitable therefor

Publications (2)

Publication Number Publication Date
EP2646603A1 EP2646603A1 (en) 2013-10-09
EP2646603B1 true EP2646603B1 (en) 2016-03-02

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EP11801589.0A Not-in-force EP2646603B1 (en) 2010-11-30 2011-11-25 Method for the electrochemical polishing of metallic objects and electrolyte solution suitable therefor

Country Status (4)

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EP (1) EP2646603B1 (en)
CN (1) CN103228822B (en)
DE (1) DE102010052778B4 (en)
WO (1) WO2012072219A1 (en)

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Publication number Priority date Publication date Assignee Title
DE102022123211A1 (en) 2022-09-12 2024-03-14 Otec Präzisionsfinish GmbH Electrolyte medium and method for electrochemical polishing of metallic workpieces using such an electrolyte medium

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CN103528873B (en) * 2013-10-24 2016-06-01 国家电网公司 The finishing method of self-forced type high-voltage electric contact material afterbody chromium bronze metallographic specimen
CN103834986B (en) 2014-02-28 2016-01-06 京东方科技集团股份有限公司 The method of electrochemical etching solution and electrochemical etching graphite grid, graphite grid
CN105058213A (en) * 2015-08-10 2015-11-18 常州二维碳素科技股份有限公司 Continuous polishing device

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US3234137A (en) * 1962-10-03 1966-02-08 Lemaire Emile Etching bath and process for photoengraved plates
US3935118A (en) * 1973-03-05 1976-01-27 Philip A. Hunt Chemical Corporation Nitric acid system for etching magnesium plates
GB1443537A (en) * 1973-10-08 1976-07-21 Kenseido Kagaku Kogyo Kk Etching composition for nickel or nickel alloy screen rolls or plates
JPS5477239A (en) * 1977-12-01 1979-06-20 Kouei Kasei Kk Electropolishing solution for gold* silver or alloys thereof
DD153897A1 (en) * 1978-12-21 1982-02-10 Vogel Heinz Ruediger METHOD FOR INTENSIVING SURFACE TREATMENT METHOD
JPH01177392A (en) * 1988-01-08 1989-07-13 Kansai Paint Co Ltd Pretreatment of body to be coated by electrodeposition
JPH05214600A (en) * 1992-02-04 1993-08-24 Tsutsumi Seisakusho:Kk Electrolytic grinding method and device therefor
DE102005055768A1 (en) * 2005-11-21 2007-05-24 Ralf Waldmann Method and means for the electrolytic cleaning and descaling of a metallic workpiece
ES2286938B1 (en) * 2006-04-26 2008-11-01 Supramol.Lecular Systems S.L. ELECTROLYTIC SOLUTION FOR ELECTROCHEMICAL POLISHING OF METAL ITEMS.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022123211A1 (en) 2022-09-12 2024-03-14 Otec Präzisionsfinish GmbH Electrolyte medium and method for electrochemical polishing of metallic workpieces using such an electrolyte medium
WO2024056315A1 (en) 2022-09-12 2024-03-21 Otec Präzisionsfinish GmbH Electrolyte medium and method for electrochemical polishing of metal workpieces using such an electrolyte medium

Also Published As

Publication number Publication date
DE102010052778A1 (en) 2012-05-31
DE102010052778B4 (en) 2013-01-17
WO2012072219A1 (en) 2012-06-07
EP2646603A1 (en) 2013-10-09
CN103228822B (en) 2016-03-16
CN103228822A (en) 2013-07-31

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