WO2012072219A1 - Procédé de polissage électrochimique d'objets métalliques et solution électrolytique appropriée - Google Patents

Procédé de polissage électrochimique d'objets métalliques et solution électrolytique appropriée Download PDF

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Publication number
WO2012072219A1
WO2012072219A1 PCT/EP2011/005937 EP2011005937W WO2012072219A1 WO 2012072219 A1 WO2012072219 A1 WO 2012072219A1 EP 2011005937 W EP2011005937 W EP 2011005937W WO 2012072219 A1 WO2012072219 A1 WO 2012072219A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte solution
mass
group
solution according
carbon atoms
Prior art date
Application number
PCT/EP2011/005937
Other languages
German (de)
English (en)
Inventor
Marco Renoffio
Original Assignee
Otec Präzisionsfinish GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Otec Präzisionsfinish GmbH filed Critical Otec Präzisionsfinish GmbH
Priority to EP11801589.0A priority Critical patent/EP2646603B1/fr
Priority to CN201180056582.XA priority patent/CN103228822B/zh
Publication of WO2012072219A1 publication Critical patent/WO2012072219A1/fr

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Classifications

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

Definitions

  • the invention relates to a method for the electrochemical polishing of metal objects, in particular 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 object is electrically conductively connected to an anode and immersed in an electrolyte solution having a cathode, wherein the electrodes are subjected to an electrical voltage. It also relates to a suitable electrolyte solution for the electrochemical polishing of metals, in particular 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 articles to be electro-polished are immersed in an electrolyte solution and connected to the positive electrode (anode) of a voltage source.
  • the negative electrode (cathode) of the voltage source is arranged, 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.
  • electrolyte solution here represents an important parameter, it has been shown that some solutions that lead in one metal to a perfect electropolishing, in another metal achieve virtually no effect or in a rough, jagged or matt 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 electrolyte composition may include an alcohol polyethylene glycol ether, an n-alkylbenzenesulfonate sodium salt, a secondary alkanesulfonate sodium salt, and minor 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 far below 0 having.
  • 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.
  • cyanide (CN ⁇ ) are used electrolyte solutions, which are able to provide satisfactory results in addition to their high toxicity and consequent handling problematic in particular in silver.
  • WO 2007/121999 A2 describes an electrolytic solution intended for electropolishing which contains alkylbenzenesulfonic acid or alkylbenzenesulfonates, ie their salts or derivatives.
  • the electrolyte solution consists of between 2.4% by mass and 3.2% by mass of decylbenzenesulfonates in the form of sodium salts, between 12% by mass and 15% by mass of dialkylbenzenesulfonic acid Alkyl Radials between 10 and 14 carbon atoms, between 13 Mass .-% and 16.5 Mass .- a petroleum fraction having 17 to 35 carbon atoms, between 0.2 Mass.-I and 0.7 Mass .-% ethanolamine, 1.4 Mass .-% copper sulfate and water.
  • this electrolyte solution in particular for the electropolishing of silver, has proved to be of only very limited suitability.
  • the invention is therefore based on the object to propose a suitable for the electropolishing of silver and preferably other precious and / or semiprecious metals, simple and cost-effective electrolyte solution of the type mentioned, which has a very low potential health hazard and therefore in a simple manner is manageable. It is also interested in a drive for the electrochemical polishing of metal objects including those made of silver or its alloys of the type mentioned.
  • pH of the electrolyte solution is at least 1.
  • 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 electropolitre of silver and silver-containing alloys, which is also the case of objects with a very complex Surface structure, such as jewelry, a smooth, shiny surface can be awarded.
  • a further advantage of the electrolytic solution according to the invention is that it does not necessarily have to be used at elevated temperatures for electropolitical use, 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 permits simple 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 according to the invention may in a preferred embodiment have between 5 and 30 carbon atoms, especially between 7 and 25 carbon atoms, preferably between 9 and 20 carbon atoms, with a chain length of such ethoxylated alcohol with between about 10 and about 16 carbon atoms has been found to be particularly advantageous. It should be noted that the said chain length in each case on the ethoxylated alcohol and not on refers to the ethoxylation obtained by addition of ethylene oxide during the ethoxylation.
  • the ethoxylated alcohol can be an alkanol, in particular an isoalkanol, and it can 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 the sulfonic acids and sulfonates of the electrolytic solution according to the invention can preferably be selected from the group of arenesulfonic acids and arenesulfonates (ie the sulfur atom of the sulfonic acid or sulfonate group binds to an aromatic group), in particular from the group of benzenesulfonic acids, alkylbenzenesulfonates. sulfonic acids, benzenesulfonates and alkylbenzenesulfonates.
  • the at least one substance from the group of sulfonic acids and sulfonates may furthermore preferably be selected from the group of benzenesulfonic acid, their alkyl derivatives, in particular their C 10 -C 16 -alkyl derivatives, preferably their C 10 -C 13 -alkyl derivatives, and salts of benzenesulfonic acid and their alkyl derivatives, especially with alkali metal (eg 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.
  • alkyl derivatives of benzenesulfonic acids and their sulfonates have proved to be particularly advantageous for the electrochemical polishing.
  • the inorganic acid used for the electrolytic solution according to the invention are primarily strong acids having a relatively high pKa value
  • the at least one inorganic acid from the group of mineral acids such as nitric acid (HNO3), sulfuric acid ( H 2 S0 4 ), phosphoric acid (H3PO4), hydrochloric acid (HCl) and the like, in particular from the group of oxidizing mineral acids, such as preferably nitric acid and / or nitrous acid (HN0 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 according to the invention may preferably comprise a ketone ten length between 5 and 30 carbon atoms, in particular between 5 and 25 carbon atoms, preferably between 5 and 20 carbon atoms, wherein chain lengths between about 5 and about 18 carbon atoms have proven to be 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, especially between about 100 ° C and about 310 ° C), preferably in the form of light petroleum (kerosene), gasoline or a gasoline fraction, such as example mineral spirits (eg with a boiling point or Siedebe rich between about 25 ° C and about 100 ° C), white spirit or the like.
  • the at least one liquid hydrocarbon or the hydrocarbon mixture may in a preferred embodiment ei nen 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
  • the electrolyte solution also contains a proportion of granule particles, in particular in the form of plastic particles.
  • granule particles which should be suitably chemically inert to the components of the solution, may 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 to keep low.
  • 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 electrically conductively connected and in an electric lytange is immersed with a cathode and the electrodes are subjected to an electrical voltage is characterized in that an electrolyte solution of the aforementioned type is used, wherein the method otherwise in a conventional manner known to the expert can be performed.
  • 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 may also be changed during an electropolishing process, e.g. depending on the state and type of metal surface of the workpiece different voltages over different periods of time can be adjusted.
  • 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 particles can be moved at least at periodic intervals in the fluidized granules, as already indicated above.
  • Component (d) Mixture of kerosene components, hydrocarbon mixture, range C9 to C16, boiling range 130 ° C to 290 ° C
  • Component (e) Distilled water
  • pH about 2;
  • Redox potential about 520 mV.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Component (d) mixture of kerosene components, hydrocarbon mixture, range C9 to C16, boiling range 130 ° C to 290 ° C
  • Component (e) Distilled water
  • pH about 2.3;
  • Redox potential about 510 mV.

Abstract

L'invention concerne un procédé de polissage électrochimique d'objets métalliques, en particulier du groupe constitué par le cuivre (Cu), le zinc (Zn), l'argent (Ag), l'étain (Sn), l'or (Au), le platine (Pt) ainsi que des alliages contenant au moins l'un de ces métaux, l'objet métallique étant relié de manière électroconductrice à une anode et étant immergé dans une solution électrolytique avec une cathode, les électrodes étant soumises à une tension électrique. L'invention concerne en outre une solution électrolytique appropriée, laquelle contient les composants suivants ou est constituée entièrement de ceux-ci : (a) entre 2 et 50 % en masse d'au moins un alcool éthoxylé ; (b) entre 2 et 50 % en masse d'au moins une substance choisie dans le groupe constitué par les acides sulfoniques et les sulfonates ; (c) entre 0,2 et 10 % en masse d'au moins un acide inorganique ; (d) entre 6 et 50 % en masse d'au moins un hydrocarbure liquide ; et (e) entre 5 et 90 % en masse d'eau ; la valeur du pH de la solution électrolytique s'élevant au moins à 1.
PCT/EP2011/005937 2010-11-30 2011-11-25 Procédé de polissage électrochimique d'objets métalliques et solution électrolytique appropriée WO2012072219A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11801589.0A EP2646603B1 (fr) 2010-11-30 2011-11-25 Procédé de polissage électrochimique d'objets métalliques et solution électrolytique appropriée
CN201180056582.XA CN103228822B (zh) 2010-11-30 2011-11-25 电化学抛光金属物体的方法及其适用的电解质溶液

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010052778 DE102010052778B4 (de) 2010-11-30 2010-11-30 Verfahren zum elektrochemischen Polieren von metallenen Gegenständen und hierfür geeignete Elektrolytlösung
DE102010052778.5 2010-11-30

Publications (1)

Publication Number Publication Date
WO2012072219A1 true WO2012072219A1 (fr) 2012-06-07

Family

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PCT/EP2011/005937 WO2012072219A1 (fr) 2010-11-30 2011-11-25 Procédé de polissage électrochimique d'objets métalliques et solution électrolytique appropriée

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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103528873B (zh) * 2013-10-24 2016-06-01 国家电网公司 自力式高压电触头材料尾部铬青铜金相试样的抛光方法
CN103834986B (zh) 2014-02-28 2016-01-06 京东方科技集团股份有限公司 电化学抛光溶液及电化学抛光石墨栅极的方法、石墨栅极
CN105058213A (zh) * 2015-08-10 2015-11-18 常州二维碳素科技股份有限公司 一种连续抛光设备
DE102022123211A1 (de) 2022-09-12 2024-03-14 Otec Präzisionsfinish GmbH Elektrolytmedium und Verfahren zum elektrochemischen Polieren von metallischen Werkstücken unter Verwendung eines solchen Elektrolytmediums

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE102005055768A1 (de) 2005-11-21 2007-05-24 Ralf Waldmann Verfahren und Mittel zur elektrolytischen Reinigung und Entzunderung eines metallischen Werkstücks
WO2007121999A2 (fr) 2006-04-26 2007-11-01 Supramol.Lecular Systems, S.L. Solution électrolytique pour polissage électrochimique d'articles métalliques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5477239A (en) * 1977-12-01 1979-06-20 Kouei Kasei Kk Electropolishing solution for gold* silver or alloys thereof
DD153897A1 (de) * 1978-12-21 1982-02-10 Vogel Heinz Ruediger Verfahren zum intensivieren von oberflaechenbehandlungsverfahren
JPH01177392A (ja) * 1988-01-08 1989-07-13 Kansai Paint Co Ltd 電着塗装のための被塗物の前処理方法
JPH05214600A (ja) * 1992-02-04 1993-08-24 Tsutsumi Seisakusho:Kk 電解研磨方法及びその装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE102005055768A1 (de) 2005-11-21 2007-05-24 Ralf Waldmann Verfahren und Mittel zur elektrolytischen Reinigung und Entzunderung eines metallischen Werkstücks
WO2007121999A2 (fr) 2006-04-26 2007-11-01 Supramol.Lecular Systems, S.L. Solution électrolytique pour polissage électrochimique d'articles métalliques

Also Published As

Publication number Publication date
DE102010052778A1 (de) 2012-05-31
CN103228822B (zh) 2016-03-16
EP2646603A1 (fr) 2013-10-09
CN103228822A (zh) 2013-07-31
DE102010052778B4 (de) 2013-01-17
EP2646603B1 (fr) 2016-03-02

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