EP3109348B1 - Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats - Google Patents

Elektrolyt und verfahren zum elektrolytischen polieren eines metallischen substrats Download PDF

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Publication number
EP3109348B1
EP3109348B1 EP15173718.6A EP15173718A EP3109348B1 EP 3109348 B1 EP3109348 B1 EP 3109348B1 EP 15173718 A EP15173718 A EP 15173718A EP 3109348 B1 EP3109348 B1 EP 3109348B1
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European Patent Office
Prior art keywords
range
amount
electrolyte
acid
fluoride
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English (en)
French (fr)
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EP3109348A1 (de
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Sarah BAGEHORN
Tobias Mertens
Freerk Syassen
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Airbus Defence and Space GmbH
Airbus Operations GmbH
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Airbus Defence and Space GmbH
Airbus Operations GmbH
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Priority to EP15173718.6A priority Critical patent/EP3109348B1/de
Priority to US15/189,170 priority patent/US20160376724A1/en
Publication of EP3109348A1 publication Critical patent/EP3109348A1/de
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00

Definitions

  • the shaping and surface finishing of metallic substrates has often proven a challenge.
  • the shaping and surface finishing of metallic substrates obtained from generative processes such as additive layer manufacturing often exhibit rough surfaces.
  • the commonly known shaping and surface finishing methods such as abrasive flow machining are often not applicable to complex surfaces.
  • electrochemical methods are known, such as electrolytic polishing.
  • the electrolytic polishing effect relies on a dissolution reaction occurring on a metallic substrate forming part of an electrolytic cell when a current is applied, wherein the metallic substrate is dissolved into the electrolyte in form of ions.
  • US 4,740,280 A is directed to an electrolyte for electrochemically polishing articles made of steel, stainless steel, nickel alloys, aluminum, and aluminum alloys, containing phosphoric acid and sulfuric acid and comprising an addition of a chelating agent on the basis of phosphonic acids and, if desired, a stabilizer for the latter.
  • US 2007/029209 A1 relates to electrolytes for electrochemically polishing workpieces consisting of titanium, titanium alloys, niobium, niobium alloys, tantalum and tantalum alloys, which electrolytes contain sulfuric acid, ammonium bifluoride and at least one hydroxycarboxylic acid, and a method for electrochemical polishing.
  • JP S63 195300 A is directed to an easily handleable electrolytic solution for electropolishing by which smooth polished surfaces having fine surface luster and free from pits are formed on Zr and Zr alloys, by adding sulfuric acid or sulfate to an electrolytic solution containing fluoride at a proper concentration.
  • CN 1249367 A relates to a non-corrosion pulsively electrochemical polishing solution prepared from phosphoric acid, sulfuric acid, glycol, polyethylene glycol, perfluoro surfactant, EDTA, Lan 826 and water, which can be used in wider operation temperature range and at high current density.
  • US 2012/115759 A1 is directed to treatment fluids for use in subterranean formations which may contain a source of fluoride ions to aid in mineral dissolution.
  • US 2009/107851 A1 relates to an electrolytic polishing method of a substrate having a barrier film and an interconnect metal layer on a surface to be processed under the presence of an electrolytic solution.
  • the finding of the present invention is an electrolyte (EL) for the application in an electrolytic polishing process for metallic substrates, resulting in an excellent reduction of surface roughness.
  • EL electrolyte
  • the invention is directed at an electrolyte (EL) for the electrolytic polishing of a metallic substrate comprising
  • the electrolyte (EL) comprises
  • the electrolyte (EL) consists of
  • the electrolyte (EL) comprises
  • the at least one acid compound (A) is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, or mixtures thereof, preferably is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, or mixtures thereof, more preferably is sulfuric acid.
  • the at least one fluoride compound (F) is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, trifluoracetic acid, or mixtures thereof, preferably is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or mixtures thereof, more preferably is ammonium fluoride.
  • the at least one complexing agent (CA) is selected from the group consisting of metylglycinediacetic acid (MGDA), ethylenediaminetetraacetate (EDTA), aminopolycarboxylic acids (APC), diethylenetriaminepentaacetate (DTPA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) or mixtures thereof, preferably is metylglycinediacetic acid (MGDA).
  • the present invention is directed at a process for the electrolytic polishing of a metallic substrate comprising the steps of
  • the current is applied at a voltage of not more than 100 V, preferably of not more than 80 V, more preferably of not more 50 V, even more preferably of not more than 20 V, like in the range of 1 to 100 V, preferably in the range of 1 to 80 V, more preferably in the range of 1 to 50 V, even more preferably in the range of 1 to 20 V, yet even more preferably in the range of 5 to 20 V.
  • the electrolyte has a temperature in the range of 10 to 95 °C, preferably a temperature in the range of 40 to 95 °C, more preferably a temperature in the range of 60 to 95 °C, even more preferably a temperature in the range of 70 to 90 °C, yet even more preferably a temperature in the range of 75 to 85 °C.
  • the current is applied at a current density in the range of 0.05 to 10 A/cm 2 , preferably at a current density in the range of 0.05 to 5 A/cm 2 , more preferably at a current density in the range of 0.1 to 2.5 A/cm 2 , even more preferably at a current density in the range of 0.1 to 2.0 A/cm 2 , yet even more preferably at a current density in the range of 0.1 to 1.5 A/cm 2 .
  • the current is applied for a time in the range of 1 to 240 min, preferably for a time in the range of 1 to 120 min, more preferably for a time in the range of 1 to 60 min, even preferably for a time in the range of 1 to 30 min, yet even more preferably for a time in the range of 2 to 20 min.
  • the process comprises at least one additional process step of treating the metallic substrate with a cleaning composition.
  • the present invention is directed at the use of at least one complexing agent (CA) selected from the group consisting of metylglycinediacetic acid (MGDA) in an electrolyte to increase the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate.
  • CA complexing agent
  • MGDA metylglycinediacetic acid
  • the present invention is directed at the use of at least one complexing agent (CA) selected from the group consisting of metylglycinediacetic acid (MGDA) in an electrolyte to increase the lifetime of the electrolyte when applied in an electrolytic polishing process of a metallic substrate.
  • CA complexing agent
  • MGDA metylglycinediacetic acid
  • the invention is directed at an electrolyte (EL) for the electrolytic polishing of a metallic substrate with excellent long-term stability and efficiency of surface roughness reduction when applied in an according process.
  • EL electrolyte
  • the invention is directed at an electrolyte (EL).
  • EL electrolyte
  • electrolyte electrolyte
  • electrolyte as used according to the present invention is directed at a fluid that can be applied in an electrolytic cell as conducting medium in which the flow of current is accompanied by the movement of matter in the form of ions.
  • the electrolyte (EL) for the electrolytic polishing of a metallic substrate comprises at least one acid compound (A), at least one fluoride compound (F), and at least one complexing agent (CA).
  • the electrolyte (EL) does not comprise any other acid compounds, fluoride compounds and complexing agents beside the at least one acid compound (A), the at least one fluoride compound (F), and the at least one complexing agent (CA).
  • the electrolyte (EL) is acidic. It is appreciated that the electrolyte has a pH of not more than 6.5, preferably a pH of not more than 6.0, more preferably a pH of not more than 5.5, like a pH in the range of 0.5 to 6.5, preferably a pH in the range of 1.0 to 6.0, more preferably a pH in the range of 2.0 to 5.5, even more preferably a pH in the range of 3.0 to 5.0.
  • acid compound as used according to the present invention is directed at an organic or inorganic compound that can accept a pair of electrons to form a covalent bond.
  • the at least one acid compound (A) is an essential constituent of the electrolyte (EL).
  • the at least one acid compound (A) increases the conductivity of the electrolyte and may benefit an electrolytic polishing process as a catalyst depending on the metallic substrate to be treated.
  • the at least one acid compound (A) is comprised in the electrolyte (EL) in an amount in the range of 0.05 to 20 wt.-%, preferably in an amount of not more than 15 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, like an amount in the range of 0.5 to 15 wt.-%, preferably an amount in the range of 1 to 10 wt.-%, more preferably an amount in the range of 1 to 5 wt.-%, based on the weight of the electrolyte (EL).
  • the at least one acid compound (A) is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, or mixtures thereof, preferably is selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, or mixtures thereof, more preferably is sulfuric acid.
  • the at least one acid compound (A) is aqueous sulfuric acid, wherein sulfuric acid is comprised in an amount in the range of 100 to 20 wt.-%, preferably in an amount in the range of 98 to 50 wt.-%, more preferably in an amount in the range of 98 to 80 wt.-%, even more preferably in an amount in the range of 98 to 90 wt.-%, based on the weight of the at least one acid compound (A).
  • fluoride compound as used according to the present invention is directed at a compound that can serve as a source of fluoride ions.
  • fluoride ions may be required to support the dissolution process, for example by forming stable complexes with dissolved metal ions.
  • the at least one fluoride compound (F) is comprised in the electrolyte (EL) in an amount in the range of 1 to 40 wt.-%, preferably in an amount of not more than 30 wt.-%, more preferably in an amount of not more than 15 wt.-%, even more preferably in an amount of not more than 10 wt.-%, like an amount in the range of 1 to 30 wt.-%, preferably in an amount the range of 2 to 15 wt.-%, more preferably an amount in the range of 4 to 10 wt.-%, based on the weight of the electrolyte (EL).
  • the at least one fluoride compound (F) is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, trifluoracetic acid, or mixtures thereof, preferably is selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or mixtures thereof, more preferably is ammonium fluoride.
  • ammonium fluoride additionally benefits the process of electrolytic polishing of metallic substrates by providing a cationic wetting agent (NH 4 + ) which modifies the polarization of the electrodes.
  • complexing agent as used according to the present invention is directed at compounds that form coordinate bonds with a metal atom or ion.
  • Chelating agents are complexing agents that form a particular type of complex, that involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a multivalent single central atom.
  • these ligands are organic compounds, and are called chelants, chelators, chelating agents, or sequestering agents.
  • complexing agent includes both non-chelating complexing agents and chelating complexing agents, the latter being preferred.
  • the at least one complexing agent (CA) is an essential constituent of the electrolyte (EL).
  • the at least one complexing agent (CA) benefits the long-term stability of the electrolyte (EL) and increases the efficiency of surface roughness reduction achieved by electrolytic polishing of a metallic substrate.
  • the at least one complexing agent (CA) is comprised in the electrolyte (EL) in an amount of not more than 30 wt.-%, preferably in an amount of not more than 20 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, like an amount in the range of 0.5 to 30 wt.-%, preferably an amount in the range of 0.5 to 20 wt.-%, more preferably an amount in the range of 0.5 to 10 wt.-%, even more preferably an amount in the range of 0.5 to 5 wt.-%, yet even more preferably an amount in the range of 1 to 3 wt.-%, based on the weight of the electrolyte (EL) It is appreciated that the at least one complexing agent (CA) is selected from the group consisting of metylglycinediacetic acid (MGDA), ethylenediaminetetraacetate (EDTA
  • the electrolyte (EL) may comprise at least one medium (M).
  • the term "medium” as used according to the present invention is directed at any organic or inorganic compound suitable for providing a medium wherein the electrolytic polishing of metallic substrates can be conducted.
  • the at least one medium (M) benefits the process of electrolytic polishing of metallic substrates, for example by increasing the conductivity of the electrolytic cell, by stabilizing the complexes formed by the at least one complexing agent (CA) and/or by providing a sufficient solubility with respect to the compounds comprised in the electrolyte (EL).
  • the at least one medium (M) is comprised in the electrolyte (EL) in an amount of at least 10 wt.-%, preferably in an amount of at least 30 wt.-%, more preferably in an amount of at least 50 wt.-%, even more preferably in an amount of at least 70 wt.-%, like an amount in the range of 10 to 98.5 wt.-%, preferably an amount in the range of 30 to 95 wt.-%, more preferably an amount in the range of 50 to 90 wt.-%, even more preferably an amount in the range of 70 to 85 wt.-% , based on the weight of the electrolyte (EL).
  • the at least one medium (M) is selected from the group consisting of water, alcohols, ethers, esters, carboxylic acids, and mixtures thereof, like C 1 to C 8 aliphatic alcohols, C 1 to C 8 aliphatic ethers, C 1 to C 8 aliphatic esters, C1 to C8 aliphatic carboxylic acids, and mixtures thereof, preferably from the group consisting of water, alcohols, ethers, and mixtures thereof, like C 1 to C 8 aliphatic alcohols, C 1 to C 8 aliphatic ethers, and mixtures thereof.
  • the at least one medium (M) is water.
  • water is directed at deionized water.
  • the at least one medium (M) is an electrolyte which is compounded with the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA) and optionally additives (AD) to form the electrolyte (EL).
  • the at least one medium (M) is water which is compounded with the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA) and optionally additives (AD) to form the electrolyte (EL).
  • the electrolyte (EL) is an aqueous electrolyte comprising the at least one acid compound (A), the at least one fluoride compound (F) and the at least one complexing agent (CA).
  • the electrolyte (EL) may comprise additional additives (AD) that are applied in the electrolytic polishing of metallic substrates to benefit the process.
  • AD additional additives
  • Typical additives are known to a person skilled in the art of electrolytic polishing of metallic substrates and are applied according to needs.
  • Typical additives for the electrolytic polishing of metallic substrates are for example surfactants, polyvalent alcohols, silicates, thickeners, and the like.
  • the additives (AD) are present in the electrolyte (EL) in an amount of not more than 25 wt.-%, preferably in an amount of not more than 15 wt.-%, more preferably in an amount of not more than 10 wt.-%, even more preferably in an amount of not more than 5 wt.-%, yet even more preferably in an amount of not more than 2 wt.-%, like an amount in the range of 0.01 to 25 wt.-%, preferably an amount in the range of 0.01 to 10 wt.-%, more preferably an amount in the range of 0.01 to 5 wt.-%, even more preferably an amount in the range of 0.01 to 2 wt.-%, based on the weight of the electrolyte (EL).
  • the invention is further directed at a process for the electrolytic polishing of a metallic substrate.
  • a process for the electrolytic polishing of a metallic substrate comprising the steps of
  • electrolytic cell as used according to the present invention is directed at an electrochemical cell that undergoes a redox reaction when electrical energy is applied.
  • the electrolytic cell can be used to decompose a metallic substrate, in a process called electrolysis.
  • the electrolyte (EL) is provided in an electrolytic cell which also contains a suitable cathode.
  • the electrolytic cell comprises a container receiving the electrolyte wherein the container is made the cathode of the electrolytic cell.
  • at least one separate electrode is present in the electrolytic cell which is made the cathode of the electrolytic cell.
  • the electrolytic cell comprises a container receiving the electrolyte and at least one separate electrode, wherein both container and the at least one separate electrode are made the cathode of the electrolytic cell.
  • the cathode material is not critical and suitable materials include copper, nickel, mild steel, stainless steel, graphite, carbon and the like.
  • the surface of the cathode and the surface of the anode have a surface ratio of at least 10:1, preferably a surface ratio of at least 12:1, even more preferably a surface ratio of at least 15:1, like a surface ratio in the range of 10:1 to 100:1, preferably a surface ratio in the range of 12:1 to 100:1, more preferably a surface ratio in the range of 12:1 to 50:1, even more preferably a surface ratio in the range of 12:1 to 20:1.
  • the current from a power source is applied between the at least one electrode and the metallic substrate, i.e. between the cathode and the anode of the electrolytic cell before the metallic substrate is immersed in the electrolyte (EL).
  • process step (iii) is conducted before process step (iv).
  • the current from a power source is applied between the at least one electrode and the metallic substrate, i.e. between the cathode and the anode of the electrolytic cell after the metallic substrate has been immersed in the electrolyte (EL).
  • process step (iii) is conducted after process step (iv).
  • composition of the electrolyte (EL) is critical. It is to be understood that the information provided above and below with respect to the electrolyte (EL) mutually applies to the inventive process for the electrolytic polishing of a metallic substrate in presence of the electrolyte (EL).
  • the electrolyte (EL) for the electrolytic polishing of a metallic substrate comprises at least one acid compound (A) selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, or mixtures thereof in an amount in the range of 0.05 to 20 wt.-%, at least one fluoride compound (F) in an amount in the range of 1 to 40 wt.-%, wherein the fluoride compound is a compound that can serve as a source of fluoride ions, and at least one complexing agent (CA) selected from the group consisting of methylglycinediacetic acid (MGDA), ethylenediaminetetraacetate (EDTA), aminopolycarboxylic acids (APC), diethylenetriaminepentaacetate (DTPA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), or mixtures thereof in an amount of not more than 30 wt.
  • the electrolyte (EL) for the electrolytic polishing of a metallic substrate consists of at least one acid compound (A) selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, or mixtures thereof in an amount in the range of 0.05 to 20 wt.-%, at least one fluoride compound (F) in an amount in the range of 1 to 40 wt.-%, wherein the fluoride compound is a compound that can serve as a source of fluoride ions, at least one complexing agent (CA) selected from the group consisting of methylglycinediacetic acid (MGDA), ethylenediaminetetraacetate (EDTA), aminopolycarboxylic acids (APC), diethylenetriaminepentaacetate (DTPA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), or mixtures thereof in an amount of not more than 30
  • A
  • the information provided above and below with respect to the at least one acid compound (A), the at least one fluoride compound (F), the at least one complexing agent (CA), the at least one medium (M) and optionally additives (AD) mutually applies to the inventive process for the electrolytic polishing of a metallic substrate in presence of at least one acid compound (A), at least one fluoride compound (F), at least one complexing agent (CA), at least one medium (M) and/or optionally additives (AD).
  • the process for the electrolytic polishing of a metallic substrate can inter alia be applied to metallic substrates with complex surfaces.
  • the metallic substrate may be in any form such as, for example, bars, plates, flat sheets, sheets of expanded metal, cuboids, or complex structures.
  • the term "metallic substrate” as used herein is meant to encompass substrates comprising at least one conductive metal or metal alloy.
  • the metallic substrate consists of at least one conductive metal or metal alloy.
  • the metallic substrate comprises, preferably consists of, metals selected from the group consisting of aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, silver, hafnium, tungsten, platinum, gold, steel and combinations thereof, such as alloys, preferably selected from the group consisting of aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, steel and combinations thereof, such as alloys, more preferably selected from the group consisting of aluminium, titanium and vanadium, and combinations thereof, such as alloys.
  • the metal substrate is selected from the group consisting of Ti-6Al-4V, AlSi 10 Mg, Al
  • the current is applied at a voltage of not more than 100 V, preferably of not more than 80 V, more preferably of not more 50 V, even more preferably of not more than 20 V, like in the range of 1 to 100 V, preferably in the range of 1 to 80 V, more preferably in the range of 1 to 50 V, even more preferably in the range of 1 to 20 V, yet even more preferably in the range of 5 to 20 V.
  • the current is applied at a voltage of at least 20 V, preferably of at least 50 V, more preferably of at least 100 V, even more preferably of at least 200 V, yet even more preferably of at least 250 V, like in the range of 20 to 800 V, preferably a voltage in the range of 50 to 600 V, more preferably a voltage in the range of 100 to 500 V, even more preferably a voltage in the range of 200 to 400 V, yet even more preferably a voltage in the range of 250 to 350 V.
  • the current is applied at a current density in the range of 0.05 to 10 A/cm 2 , preferably at a current density in the range of 0.05 to 5 A/ cm 2 , more preferably at a current density in the range of 0.1 to 2.5 A/cm 2 , even more preferably at a current density in the range of 0.1 to 2.0 A/cm 2 , yet even more preferably at a current density in the range of 0.1 to 1.5 A/cm 2 .
  • the temperature of the electrolyte is at least 10 °C, preferably is at least 40 °C, more preferably is at least 60 °C, even more preferably is at least 70 °C, yet even more preferably is at least 75 °C, like a temperature in the range of 10 to 95 °C, preferably a temperature in the range of 40 to 95 °C, more preferably a temperature in the range of 60 to 95 °C, even more preferably a temperature in the range of 70 to 90 °C, yet even more preferably a temperature in the range of 75 to 85 °C.
  • the treatment time is generally within the range of 1 to 240 min.
  • the treatment of some metallic substrates may require a shorter or longer treatment for the desired reduction in surface roughness, depending on factors such as initial surface roughness and desired surface roughness, surface area, surface geometry and the like.
  • the current is applied for a time in the range of 1 to 240 min, preferably for a time in the range of 1 to 120 min, more preferably for a time in the range of 1 to 60 min, even preferably for a time in the range of 1 to 30 min, yet even more preferably for a time in the range of 2 to 20 min.
  • the electrolyte is continuously agitated during the process for the electrolytic polishing of a metallic substrate.
  • the agitation may be achieved by immersing a pressurized gas. Suitable gases for immersion are for example, nitrogen, hydrogen helium, argon, and combinations thereof.
  • a pressurized gas may have a pressure in the range of 0.01 to 1000 kg/cm 2 , preferably a pressure in the range of 1 to 1000 kg/cm 2 .
  • the process for the electrolytic polishing of a metallic substrate comprises a post-treatment step of treating the metallic substrate with a cleaning composition, preferably a post-treatment step of treating the metallic substrate with water, preferably deionized water.
  • the process for the electrolytic polishing of a metallic substrate provides metallic substrate with reduced surface roughness.
  • the average surface roughness (R a ) of a metallic substrate treated according to the process for the electrolytic polishing of a metallic substrate described is reduced by at least 0.1 ⁇ m, preferably is reduced by at least 0.5 ⁇ m, even more preferably is reduced by at least 1.0 ⁇ m, like in the range of 0.1 to 100 ⁇ m, preferably in the range of 0.5 to 10 ⁇ m, even more preferably in the range of 1.0 to 5.0 ⁇ m.
  • a metallic substrate is obtained with an average surface roughness (R a ) of not more than 10 ⁇ m, preferably of not more than 5 ⁇ m, more preferably of not more than 1 ⁇ m, even more preferably of not more than 0.5 ⁇ m, yet even more preferably of not more than 0.1 ⁇ m, like an average surface roughness (R a ) in the range of 10 to 0.01 ⁇ m, preferably an average surface roughness (R a ) in the range of 5 to 0.01 ⁇ m, more preferably an average surface roughness (R a ) in the range of 1 to 0.01 ⁇ m, even more preferably an average surface roughness (R a ) in the range of 0.5 to 0.01 ⁇ m, yet even more preferably an average surface roughness (R a ) in the range of 0.1 to 0.01 ⁇ m.
  • R a average surface roughness
  • the electrolyte (EL) can be applied for electrolytic polishing of metallic substrates comprising metals or metal alloys. It is a finding of the present invention that the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate can be improved when providing at least one complexing agent (CA). In addition hereto it is a finding of the present invention that the lifetime of an electrolyte can be increased when providing at least one complexing agent (CA).
  • CA complexing agent
  • the invention is further directed at the use of at least one complexing agent (CA) selected from the group consisting of methylglycinediacetic acid (MGDA) in an electrolyte to increase the efficiency of surface roughness reduction in an electrolytic polishing process of a metallic substrate.
  • CA complexing agent
  • MGDA methylglycinediacetic acid
  • the invention is further directed at the use of at least one complexing agent (CA) selected from the group consisting of methylglycinediacetic acid (MGDA) in an electrolyte to increase the lifetime of the electrolyte when applied in an electrolytic polishing process of a metallic substrate.
  • CA complexing agent
  • MGDA methylglycinediacetic acid
  • the at least one complexing agent (CA) is described in more detail above and below, in particular in the section “The Complexing Agent (CA) ".
  • the average surface roughness (R a ) is determined according to DIN EN 4287:1998-10 using the tactile incision technique according to DIN EN ISO 3274 (Hommel Tester T1000 Wave of Jenoptik, tipradius 5 ⁇ m, taper angle 90°)
  • the pH is determined according to DIN 19261:2005-6.
  • a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
  • the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F, 4 wt.-% H 2 SO 4 and 1 wt.-% MGDA.
  • the electrolyte has a pH of 3.5.
  • the metallic substrate is treated for 10 min.
  • a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
  • the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F and 1 wt.-% H 2 SO 4 .
  • the electrolyte has a pH of 3.5.
  • the metallic substrate is treated for 10 min.
  • the building of oxide layers can be partially be observed on the surface.
  • a current of 20 V is applied from a direct current power source between the cathode and the metallic substrate.
  • the metallic substrate is immersed in an electrolyte consisting of 6 wt.-% NH 4 F, 4 wt.-% H 2 SO 4 and 1 wt.-% MGDA.
  • the electrolyte has a pH of 3.5.
  • the metallic substrate is treated for 10 min.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • ing And Chemical Polishing (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Claims (14)

  1. Elektrolyt (EL) zum Elektropolieren eines Metallsubstrats, der Folgendes umfasst:
    (i) mindestens eine aus der Gruppe bestehend aus Schwefelsäure, Salpetersäure, Phosphorsäure, Salzsäure, Ameisensäure, Essigsäure, Propionsäure oder Mischungen davon ausgewählte Säureverbindung (A) in einer Menge im Bereich von 0,05 bis 20 Gew.-%,
    (ii) mindestens eine Fluoridverbindung (F) in einer Menge im Bereich von 1 bis 40 Gew.-%, wobei es sich bei der Fluoridverbindung um eine Verbindung handelt, die als Quelle für Fluoridionen dienen kann, und
    (iii) mindestens einen aus der Gruppe bestehend aus Methylglycindiessigsäure (MGDA), Ethylendiamintetraacetat (EDTA), Aminopolycarbonsäuren (APC), Diethylentriaminpentaacetat (DTPA), N-(Hydroxyethyl)ethylendiamintriessigsäure (HEDTA) oder Mischungen davon ausgewählten Komplexbildner (CA) in einer Menge von nicht mehr als 30 Gew.-%.
  2. Elektrolyt (EL) nach Anspruch 1, der
    (i) die mindestens eine Säureverbindung (A) in einer Menge von nicht mehr als 15 Gew.-%, vorzugsweise in einer Menge von nicht mehr als 10 Gew.-%, weiter bevorzugt in einer Menge von nicht mehr als 5 Gew.-%, wie beispielsweise in einer Menge im Bereich von 0,5 bis 15 Gew.-%, vorzugsweise im Bereich von 1 bis 10 Gew.-%, weiter bevorzugt im Bereich von 1 bis 5 Gew.-%, umfasst, und/oder
    (ii) die mindestens eine Fluoridverbindung (F) in einer Menge von nicht mehr als 30 Gew.-%, vorzugsweise in einer Menge von nicht mehr als 15 Gew.-%, weiter bevorzugt in einer Menge von nicht mehr als 10 Gew.-%, wie beispielsweise in einer Menge im Bereich von von 1 bis 30 Gew.-%, vorzugsweise im Bereich von 2 bis 15 Gew.-%, weiter bevorzugt im Bereich von 4 bis 10 Gew.-%, umfasst und/oder
    (iii) den mindestens einen Komplexbildner (CA) in einer Menge von nicht mehr als 20 Gew.-%, vorzugsweise in einer Menge von nicht mehr als 10 Gew.-%, weiter bevorzugt in einer Menge von nicht mehr als 5 Gew.-%, wie beispielsweise in einer Menge im Bereich von 0,5 bis 30 Gew.-%, vorzugsweise im Bereich von 0,5 bis 20 Gew.-%, weiter bevorzugt im Bereich von 0,5 bis 10 Gew.-%, noch weiter bevorzugt im Bereich von 0,5 bis 5 Gew.-%, ganz besonders bevorzugt im Bereich von 1 bis 3 Gew.-%, umfasst,
    jeweils bezogen auf das Gewicht des Elektrolyten (EL).
  3. Elektrolyt (EL) nach einem der vorhergehenden Ansprüche 1 oder 2, der ferner Folgendes umfasst:
    (iv) mindestens ein Medium (M) in einer Menge von mindestens 10 Gew.-% und
    (v) gegebenenfalls Additive (AD) in einer Menge von nicht mehr als 25 Gew.-%.
  4. Elektrolyt (EL) nach einem der vorhergehenden Ansprüche 1 oder 3, der
    (iv) das mindestens eine Medium (M) in einer Menge von mindestens 30 Gew.-%, vorzugsweise in einer Menge von mindestens 50 Gew.-%, weiter bevorzugt in einer Menge von mindestens 70 Gew.-%, wie beispielsweise in einer Menge im Bereich von 10 bis 98,5 Gew.-%, vorzugsweise im Bereich von 30 bis 95 Gew.-%, weiter bevorzugt im Bereich von 50 bis 90 Gew.-%, noch weiter bevorzugt im Bereich von 70 bis 85 Gew.-%, umfasst
    und/oder
    (v) Additive (AD) in einer Menge von nicht mehr als 15 Gew.-%, vorzugsweise in einer Menge von nicht mehr als 10 Gew.-%, weiter bevorzugt in einer Menge von nicht mehr als 5 Gew.-%, noch weiter bevorzugt in einer Menge von nicht mehr als 2 Gew.-%, wie beispielsweise in einer Menge im Bereich von 0,01 bis 25 Gew.-%, vorzugsweise im Bereich von 0,01 bis 10 Gew.-%, weiter bevorzugt im Bereich von 0,01 bis 5 Gew.-%, noch weiter bevorzugt im Bereich von 0,01 bis 2 Gew.-%, umfasst,
    jeweils bezogen auf das Gewicht des Elektrolyten (EL).
  5. Elektrolyt (EL) nach einem der vorhergehenden Ansprüche 1 bis 4, wobei die mindestens eine Säureverbindung (A) aus der Gruppe bestehend aus Schwefelsäure, Salpetersäure, Phosphorsäure oder Mischungen davon ausgewählt ist, vorzugsweise Schwefelsäure ist.
  6. Elektrolyt (EL) nach einem der vorhergehenden Ansprüche 1 bis 5, wobei die mindestens eine Fluoridverbindung (F) aus der Gruppe bestehend aus Ammoniumfluorid, Natriumfluorid, Kaliumfluorid, Magnesiumfluorid, Calciumfluorid, Trifluoressigsäure oder Mischungen davon ausgewählt ist, vorzugsweise aus der Gruppe bestehend aus Ammoniumfluorid, Natriumfluorid, Kaliumfluorid, Magnesiumfluorid, Calciumfluorid oder Mischungen davon ausgewählt ist, weiter bevorzugt Ammoniumfluorid ist.
  7. Elektrolyt nach einem der vorhergehenden Ansprüche 1 bis 6, wobei es sich bei dem mindestens einen Komplexbildner (CA) um Methylglycindiessigsäure (MGDA) handelt.
  8. Verfahren zum Elektropolieren eines Metallsubstrats, das die folgenden Schritte umfasst:
    (i) Bereitstellen eines Elektrolyten (EL) nach einem der vorhergehenden Ansprüche 1 bis 7 in einer mindestens eine Elektrode umfassenden Elektrolysezelle,
    (ii) Anordnen eines Metallsubstrats als Anode in der Elektrolysezelle,
    (iii) Anlegen eines Stroms aus einer Stromquelle zwischen der mindestens einen Elektrode und dem Metallsubstrat und
    (iv) Eintauchen des Metallsubstrats in den Elektrolyten (EL) .
  9. Verfahren nach Anspruch 8, wobei der Strom mit einer Spannung von nicht mehr als 100 V, vorzugsweise von nicht mehr als 80 V, weiter bevorzugt von nicht mehr als 50 V, noch weiter bevorzugt von nicht mehr als 20 V, wie beispielsweise im Bereich von 1 bis 100 V, vorzugsweise im Bereich von 1 bis 80 V, weiter bevorzugt im Bereich von 1 bis 50 V, noch weiter bevorzugt im Bereich von 1 bis 20 V, ganz besonders bevorzugt im Bereich von 5 bis 20 V, angelegt wird.
  10. Verfahren nach einem der vorhergehenden Ansprüche 8 oder 9, wobei der Elektrolyt (EL) eine Temperatur im Bereich von 10 bis 95 °C, vorzugsweise im Bereich von 40 bis 95 °C, weiter bevorzugt im Bereich von 60 bis 95 °C, noch weiter bevorzugt im Bereich von 70 bis 90 °C, ganz besonders bevorzugt im Bereich von 75 bis 85 °C, aufweist.
  11. Verfahren nach einem der vorhergehenden Ansprüche 8 bis 10, wobei der Strom mit einer elektrischen Stromdichte im Bereich von 0,05 bis 10 A/cm2, vorzugsweise mit einer elektrischen Stromdichte im Bereich von 0,05 bis 5 A/cm2, weiter bevorzugt mit einer elektrischen Stromdichte im Bereich von 0,1 bis 2,5 A/cm2, noch weiter bevorzugt mit einer elektrischen Stromdichte im Bereich von 0,1 bis 2,0 A/cm2, ganz besonders bevorzugt mit einer elektrischen Stromdichte im Bereich von 0,1 bis 1,5 A/cm2, angelegt wird.
  12. Verfahren nach einem der vorhergehenden Ansprüche 8 bis 10, wobei der Strom für einen Zeitraum im Bereich von 1 bis 240 min, vorzugsweise im Bereich von 1 bis 120 min, weiter bevorzugt im Bereich von 1 bis 60 min, noch weiter bevorzugt im Bereich von 1 bis 30 min, ganz besonders bevorzugt im Bereich von 2 bis 20 min, angelegt wird.
  13. Verwendung von mindestens einem aus der Gruppe bestehend aus Methylglycindiessigsäure (MGDA) ausgewählten Komplexbildner (CA) in einem Elektrolyten zur Steigerung der Effizienz der Oberflächenrauigkeitsverringerung bei einem Verfahren zum Elektropolieren eines Metallsubstrats.
  14. Verwendung von mindestens einem aus der Gruppe bestehend aus Methylglycindiessigsäure (MGDA) ausgewählten Komplexbildner (CA) in einem Elektrolyten zur Erhöhung der Lebensdauer des Elektrolyten bei der Anwendung in einem Verfahren zum Elektropolieren eines Metallsubstrats.
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EP3269848B1 (de) * 2016-07-13 2019-09-11 Airbus Defence and Space GmbH Verfahren zur oberflächenbehandlung von metallen und legierungen
DE102016125244A1 (de) * 2016-12-21 2018-06-21 Airbus Defence and Space GmbH Verfahren für das Elektropolieren von einem metallischen Substrat
JP7177425B2 (ja) * 2017-12-28 2022-11-24 株式会社日本科学エンジニアリング ステンレス鋼用電解研磨液
DE102019207857A1 (de) * 2019-05-28 2020-12-03 Airbus Operations Gmbh Verfahren zur Herstellung eines komplexen Bauteils und Trennwerkzeug
CN113862769A (zh) * 2021-11-08 2021-12-31 中国工程物理研究院机械制造工艺研究所 一种用于AlSi10Mg合金表面的电解抛光方法及工件

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