US20100252446A1 - Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive - Google Patents

Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive Download PDF

Info

Publication number
US20100252446A1
US20100252446A1 US12/671,830 US67183008A US2010252446A1 US 20100252446 A1 US20100252446 A1 US 20100252446A1 US 67183008 A US67183008 A US 67183008A US 2010252446 A1 US2010252446 A1 US 2010252446A1
Authority
US
United States
Prior art keywords
ammonium chloride
metal
group
anion
ionic liquid
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US12/671,830
Other languages
English (en)
Inventor
Boris Kuzmanovic
Lamberdine Johanna Willemina Maria Nabuurs-Willems
Cornelis Johannes Govardus Van Strien
Franz Winfried Welter
Johanna Christina Speelman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Original Assignee
Akzo Nobel NV
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 Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to US12/671,830 priority Critical patent/US20100252446A1/en
Assigned to AKZO NOBEL N.V. reassignment AKZO NOBEL N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUZMANOVIC, BORIS, NABUURS-WILLEMS, LAMBERDINE JOHANNA WILLEMINA MARIA, VAN STRIEN, CORNELIS JOHANNES GOVARDUS, WELTER, FRANZ WINFRIED, SPEELMAN, JOHANNA CHRISTINA
Publication of US20100252446A1 publication Critical patent/US20100252446A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • 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 present invention relates to a method to electrodeposit a metal on a substrate using an ionic liquid as the electrolyte in the presence of an additive, and to the use of said additive to increase the layer thickness of the deposited metal layer.
  • An ionic liquid is a salt in which the ions are poorly coordinated, which results in these solvents being liquid at temperatures below 100° C. Many are liquid even at room temperature. At least one ion in an ionic liquid has a delocalized charge and one component is organic, which prevents the formation of a stable crystal lattice. Ionic liquids generally have very low vapour pressure and thus, in contrast to many conventional solvents, produce virtually no hazardous vapours. It is known that, in general, ionic liquids may be used in many applications, e.g. as reaction solvents, extraction solvents, electrolytes in batteries and electrodeposition, catalysts, heat exchange fluids, as additives in coatings.
  • Well-known systems include those formed from alkylpyridinium halides or dialkylimidazolium halides with an aluminium halide, and those based on choline chloride and a (hydrated) metal salt such as chromium (III) chloride. These systems have been utilized as electrolytes in electroplating, as described for example in EP 0 404 188 and EP 1 322 591.
  • WO 2002/026381 discloses ionic liquids (eutectic mixtures) of choline chloride and a (hydrated) metal salt such as chromium (III) chloride and the use thereof in electrodeposition and electropolishing.
  • the mixtures consist of choline chloride and the (hydrated) metal salt in a ratio of ammonium to metal ion of between 1:1 and 1:2.5 and are specifically said to be suitable for depositing chromium, cobalt, zinc or silver on a metal substrate.
  • PCT/EP/2007/051329 describes a method to electroplate or electropolish a metal on a substrate wherein an ionic liquid selected from the group of
  • any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , at least one of R 5 to R 8 is a fatty alkyl chain, and one or more of R 5 to R 8 can be a (poly)oxyalkylene group wherein the alkylene is a C 1 to C 4 alkylene and the total number of oxyalkylene units can be from 1 to 50 oxyalkylene units, and at least one of R 1 to R 8 is a C 1 to C 4 alkyl chain, R 9 is an alkyl or cycloalkyl
  • ionic liquids as electrolytes in electrodeposition processes has several advantages.
  • Conventional chromic acid plating processes are extremely hazardous because they mainly rely on hexavalent chromium, which is highly toxic and carcinogenic.
  • Ionic liquids may eliminate the necessity to use hexavalent chromium and allow the use of trivalent chromium, which is considered to be far less dangerous.
  • conventional chromium plating baths require the use of strong acids, which poses significant disposal problems, while the use of ionic liquids generally enables such disposal difficulties to be minimized or even eliminated.
  • ionic liquids are non-volatile, so they do not cause atmospheric pollution.
  • metal layers For some applications, such as decorative plating, having thin metal layers is acceptable. However, for applications where the metal layer needs to provide protection against wear or abrasion, or to improve hardness (functional plating), metal layers much thicker than 200 nm are required. More particularly, layers of several micrometers or even several tens of micrometers are desirable.
  • the present invention relates to the use of amorphous silica, graphite powder, or a mixture thereof as additive in a process to electroplate or electropolish a metal on a substrate wherein an ionic liquid is employed as the electrolyte to increase metal layer thickness.
  • Additives have been added to the ionic liquid comprising electrolyte for several reasons.
  • U.S. Pat. No. 7,196,221 discloses the use of brightening agents to improve the appearance of the coatings obtained in ionic liquid solvents/electrolytes during metal plating and electropolishing processes, and in particular in chromium plating processes.
  • the brightening agents include thiourea, saccharin, vanillin, allyl urea, nicotinic acid, citric acid, gelatin, 2-mercaptobenzothiazole, tetraethylammonium fluoride dihydrate or tetramethyl-ammonium hydroxide pentahydrate.
  • these additives have an adverse effect on the homogeneity of the deposited layer, or no effect at all.
  • WO 2006/074523 relates to a process for the recovery of platinum group metal, which comprises electrodeposition of the platinum group metal from an ionic liquid wherein redox reagents, complexing agents, conductivity enhancers may be present.
  • U.S. Pat. No. 6,552,843 which is concerned with devices, such as adjustable mirrors, smart windows, optical attenuators, and displays, for controlling the reflectance and/or transmission of electromagnetic radiation, discloses a reversible electrodeposition optical modulation device employing an ionic liquid electrolyte.
  • the ionic liquid electrolyte is comprised of a mixture of an ionic organic compound and the salt of an electrodepositable metal.
  • the ionic organic compound comprises a heterocyclic cation such as N-alkylpyrrolidinium, pyrrolidinium, 1-alkyl-3-methylimidazolium, N-alkylpyridinium, 2-alkyl-1-pyrrolinium, 1-alkylimidazolium.
  • the electrodepositable metal is silver, copper, tin, zinc, palladium, bismuth, cadmium, mercury, indium, lead, antimony, thallium, and alloys thereof. It is mentioned that said ionic liquid electrolyte may be rendered more viscous, semi-solid or solid by addition of organic or inorganic gelling agents. Inorganic or organic materials, including suspended carbon and dissolved dyes, may be added to the electrolyte to impart a desired colour or to reduce background reflection.
  • electrodeposition in this application should be understood to include both electroplating and electropolishing.
  • electroplating is meant the process of using electrical current to coat an electrically conductive object with a layer of metal. The preferred result is a thin, smooth, even coat of metal on the object.
  • the primary application of electroplating is to deposit a layer of a metal having some desired property (e.g., abrasion and wear resistance, corrosion protection, lubricity, improvement of aesthetic qualities, etc.) onto a surface lacking that property.
  • Another application uses electroplating to build up thickness on undersized parts.
  • electropolishing is meant smoothing and enhancing the appearance of an originally rough or uneven metal surface by coating it with a relatively thin metal layer.
  • the additive used according to the present invention to increase the thickness of the deposited metal layer is amorphous silica, graphite powder, or a mixture thereof.
  • amorphous silica is meant to include colloidal silica particles in any form, where the colloidal silica particles, which are also referred to as silica sols, may be derived from e.g. precipitated silica, silica gels, pyrogenic silica (fumed silica), micro silica (silica fume) or mixtures thereof.
  • Colloidal silica according to the present invention may be modified and can contain other elements such as amines, aluminium and/or boron, which can be present in the particles and/or the continuous phase.
  • the colloidal silica particles can be dispersed in a substantially aqueous solvent, suitably in the presence of stabilizing cations such as K + , Na + , Li + , NH 4 + , organic cations, primary, secondary, tertiary, and quaternary amines, and mixtures thereof, so as to form an aqueous silica sol.
  • stabilizing cations such as K + , Na + , Li + , NH 4 + , organic cations, primary, secondary, tertiary, and quaternary amines, and mixtures thereof.
  • organic solvents e.g. lower alcohols, acetone or mixtures thereof, also denoted as organo-silica sols
  • the silica content in the sol is from about 5 to about 80% by weight.
  • Aqueous silica sols suitable for use according to the present invention are e.g. commercially available from Akzo Nobel.
  • Suitable organo-silica sols are e.g. commercially available from Nissan Chemical Industries.
  • graphite powder finely divided carbon powder or carbon black, e.g. commercially available from Degussa.
  • the additive is preferably used in a quantity of at least 0.01 wt %, more preferably of at least 0.05 wt %, and most preferably of at least 0.1 wt %, based on the total weight of the electrolyte.
  • no more than 5 wt %, more preferably no more than 3 wt %, and most preferably no more than 1 wt % of additive is used, based on the total weight of the electrolyte.
  • electrolyte stands for the total electrolyte mixture, i.e. including dissolved metal salts and additives.
  • the layer thickness can be increased at least 10 times, more preferably at least 20 times, and most preferably at least 40 times, when compared to electrodeposition without said additive(s).
  • the ionic liquid employed as electrolyte is preferably selected from the group consisting of N + R 1 R 2 R 3 R 4 X ⁇ , N + R 5 R 6 R 7 R 8 Y ⁇ , and mixtures thereof, wherein any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , wherein at least one of R 1 to R 4 is an, optionally branched, fatty alkyl chain, wherein R 2 can be a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group with R 16 , R 17 , R 18 being similar to R 1 , R 3 , R 4 , respectively, or a C 1 to C 4 alkyl chain, and wherein one
  • X ⁇ is selected from the group of F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ ; the group of R 10 COO ⁇ anions wherein R 10 may be hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 11 SO 4 ⁇ anions wherein R 11 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 12 SO 3 anions wherein R 12 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; the group of R 13 CO 3 ⁇ anions wherein R 13 may be absent, in which case the cation is divalent, hydrogen, a C 1 -C 22 alkyl, alkenyl or aromatic group; and the group of R 14 —N ⁇ —SO 2 —R 15 anions wherein R 14 and/or R
  • a fatty alkyl chain is meant to include saturated and/or unsaturated chains and contains 8 to 22 carbon atoms; preferably, it contains 10 to 22 carbon atoms, most preferably 12 to 20 carbon atoms.
  • an ionic liquid of the formula N + R 1 R 2 R 3 R 4 X ⁇ is used with R 1 , R 3 , and R 4 being as mentioned above and with R 2 being a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group.
  • R 16 , R 17 , and R 18 are identical to R 1 , R 2 and R 4 , respectively, with at least one of them being an, optionally branched, fatty alkyl chain, resulting in a gemini-type structure (i.e. a symmetrical diquatemary ammonium compound).
  • Y ⁇ is based on a compound known as a sweetener.
  • N + R 5 R 6 R 7 R 8 is an amine wherein the groups R 5 to R 8 are hydrogen or an alkyl or cycloalkyl, optionally substituted with OH or Cl; more preferably, at least three thereof are an alkyl, more preferably a C 1 to C 4 alkyl.
  • the ionic liquid is selected from any one of choline saccharinate, choline acesulphamate, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cocotrimethyl ammonium chloride, tallowtrimethyl ammonium chloride, hydrogenated tallowtrimethyl ammonium chloride, hydrogenated palmtrimethyl ammonium chloride, oleyltrimethyl ammonium chloride, soyatrimethyl ammonium chloride, cocobenzyldimethyl ammonium chloride, C12-16-alkylbenzyldimethyl ammonium chloride, hydrogenated tallowbenzyldimethyl ammonium chloride, dioctyldimethyl ammonium chloride, didecyldimethyl ammonium chloride, dicocodimethyl ammonium nitrite, dicocodimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride
  • ionic liquids suitable for use according to the present invention can be prepared by a simple reaction of salts, for example by a metathesis reaction of choline chloride and sodium saccharinate (acesulphamate) to form a choline saccharinate (acesulphamate) ionic liquid, or by quaternization of the corresponding amines.
  • the molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt is preferably between 1,000:1 and 3:1. More preferred is a molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt of between 500:1 and 5:1, most preferred is a molar ratio between 100:1 and 7:1, this providing a good-quality metal layer, excellent dissolution of the metal in the ionic liquid, and a good balance between the cost of the process and the appearance of the plated substrate product.
  • one of the metals chromium, aluminium, titanium, zinc or copper, or an alloy thereof is deposited. More preferably, chromium or aluminium is deposited, most preferably chromium.
  • This metal deposition can be done from a metal salt dissolved in the electrolyte, for example a metal halide, preferably, but not limited to, a metal chloride. It can also be performed using a pure metal which is applied as anode (i.e. a chromium, aluminium, titanium, zinc, or copper anode). In the embodiment where a metal anode is used, the anode may be in the form of metal pieces, chunks, chips or any other suitable form known to the skilled person.
  • the substrate which can be electroplated or electropolished according to the present invention can be any conductive object.
  • it is an object which is solid metal, such as a carbon steel object, or it comprises conductive elements such as a composite material object.
  • the present invention furthermore relates to a method to electroplate or electropolish a metal on a metal substrate wherein an ionic liquid ionic liquid is selected from the group consisting of N + R 1 R 2 R 3 R 4 X ⁇ , N + R 5 R 6 R 7 R 8 Y ⁇ , and mixtures thereof, wherein any one of R 1 to R 8 independently represents a hydrogen, alkyl, cycloalkyl, aryl, or aralkyl group that may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 , or OR 9 , wherein at least one of R 1 to R 4 is an, optionally branched, fatty alkyl chain, wherein R 2 can be a (C 2 -C 6 alkyl)-N + R 16 R 17 R 18 group with R 16 , R 17 , R 18 being similar to R 1 , R 3
  • a metal salt added to said ionic liquid or a metal anode is employed as metal source, and wherein said ionic liquid comprises at least 0.01 wt%, based on the total weight of electrolyte, of an additive selected from the group consisting of amorphous silica, graphite powder, and of a mixture thereof.
  • the additive is preferably used in the quantities as described above.
  • the electrodeposition is preferably performed at temperatures below 90° C. and more preferably at room temperature, in open electrodeposition vessels, but electrodeposition is not limited to these conditions.
  • Chromium (III) chloride hexahydrate salt was added to cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid containing 0.2 wt % of water and the mixture was agitated at a temperature of about 50° C. until the solid salt dissolved. In the prepared solution the concentration of chromium (III) chloride hexahydrate was 75 g/kg.
  • Platinized titanium plate was applied as the anode and connected to the positive terminal of a DC power source, whereas carbon steel plate was used as the cathode (substrate) and connected to the negative terminal.
  • the substrate plate Prior to introduction into the bath, the substrate plate was cleaned with a commercial scouring powder, washed in demineralized water, in acetone and after that in ethanol, and finally in a 4 M-HCl aqueous solution. When both plates were connected and introduced into the cell, the voltage difference was set to 30 V. The current flow was monitored on a meter connected in series.
  • the cathode was disconnected from the power source and taken out of the cell.
  • the plate was washed in water and acetone and then dried.
  • Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate was performed. It confirmed deposition of chromium onto the carbon steel.
  • the deposited layer thickness was measured using a thickness measurement device obtained from Fischer, Germany. The thickness was found to be lower than 0.5 ⁇ m.
  • Example 2 To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt % of active compound.
  • Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
  • the cathode was disconnected from the power source and taken out of the cell.
  • the plate was washed in water and acetone and then dried.
  • Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
  • the deposited layer thickness measured using a thickness measurement device (Fischer, Germany), was found to be as high as 8 ⁇ m in certain regions of the substrate, which was significantly thicker than when no additive was used. As is typical for the Hull cell experiments, the layer thickness varied with the position on the substrate—in this case from 1 ⁇ m to 8 ⁇ m. To confirm these measurements a cross-cut metallographic analysis was also done. The sample of the substrate was embedded in epoxy resin and the deposit was evaluated under the microscope. The layer thickness determined in this way was in agreement with the thickness measurement device results.
  • Example 2 To the prepared solution of chromium (III) chloride hexahydrate salt in cocoalkylmethyl [polyoxyethylene(15)] ammonium chloride ionic liquid as described in Example 1 was added an amorphous silica aqueous colloidal solution which contained 8 wt % of active compound. The concentration of the amorphous silica in the prepared solution, expressed as the quantity of the active compound, was 4 g/kg.
  • Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
  • the cathode was disconnected from the power source and taken out of the cell.
  • the plate was washed in water and acetone and then dried.
  • Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
  • the deposited layer thickness measured using a thickness measurement device (Fischer, Germany) and by cross-cut metallographic analysis, was found to be ranging from 1 to 9 ⁇ m.
  • Example 2 The same pretreatment of the carbon steel substrate (cathode) as in Example 1 was performed, and again platinized titanium plate was applied as the anode. The potential difference was set to 30 V. The liquid was agitated using a centrally positioned top-entering impeller. The current flow between the electrodes was monitored on a meter connected in series.
  • the cathode was disconnected from the power source and taken out of the cell.
  • the plate was washed in water and acetone and then dried.
  • Chemical analysis by scanning electron microscopy combined with X-ray dispersion (SEM/EDX) of the substrate confirmed deposition of chromium onto the carbon steel plate.
  • the deposited layer thickness measured using a thickness measurement device (Fischer, Germany), was found to be ranging from 1 to 7 ⁇ m. The same thickness values were found by cross-cut metallographic analysis of the substrate samples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Electrolytic Production Of Metals (AREA)
US12/671,830 2007-08-02 2008-07-30 Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive Abandoned US20100252446A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/671,830 US20100252446A1 (en) 2007-08-02 2008-07-30 Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP07113717 2007-08-02
EP07113717.8 2007-08-02
US95443407P 2007-08-07 2007-08-07
PCT/EP2008/059962 WO2009016189A1 (en) 2007-08-02 2008-07-30 Method to electrodeposit metals using ionic liquids in the presence of an additive
US12/671,830 US20100252446A1 (en) 2007-08-02 2008-07-30 Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive

Publications (1)

Publication Number Publication Date
US20100252446A1 true US20100252446A1 (en) 2010-10-07

Family

ID=38870310

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/671,830 Abandoned US20100252446A1 (en) 2007-08-02 2008-07-30 Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive

Country Status (12)

Country Link
US (1) US20100252446A1 (de)
EP (1) EP2171131B1 (de)
JP (1) JP2010535283A (de)
CN (1) CN101765681B (de)
AT (1) ATE493523T1 (de)
CA (1) CA2695488A1 (de)
DE (1) DE602008004255D1 (de)
ES (1) ES2358967T3 (de)
HK (1) HK1143194A1 (de)
PL (1) PL2171131T3 (de)
TW (1) TWI359880B (de)
WO (1) WO2009016189A1 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120000790A1 (en) * 2009-03-17 2012-01-05 Commonwealth Scientific And Industrial Research Organisation Electrorecovery of metals
EP2481836A1 (de) * 2011-01-26 2012-08-01 United Technologies Corporation Beschichtungsverfahren mit Verwendung einer ionischen Flüssigkeit
CN102839403A (zh) * 2012-09-10 2012-12-26 太原理工大学 一种离子液体中电镀铝的方法
WO2013122774A1 (en) * 2012-02-16 2013-08-22 Macdermid Acumen, Inc. Color control of trivalent chromium deposits
US20130319647A1 (en) * 2012-05-31 2013-12-05 Benteler Automobiltechnik Gmbh Method for producing an exhaust-gas heat exchanger
WO2015088861A1 (en) * 2013-12-11 2015-06-18 Lei Chen Electroformed nickel-chromium alloy
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
US10669851B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Nickel-chromium-aluminum composite by electrodeposition
EP3825444A1 (de) * 2019-11-22 2021-05-26 Hamilton Sundstrand Corporation Metallische beschichtung und anwendungsverfahren
US12050389B2 (en) 2020-10-23 2024-07-30 The Regents Of The University Of Colorado, A Body Corporate Electrolyte additive for controlling morphology and optics of reversible metal films

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009035660A1 (de) 2009-07-30 2011-02-03 Ewald Dörken Ag Verfahren zur elektrochemischen Beschichtung eines Werkstücks
CN102888630B (zh) * 2011-07-20 2015-11-18 中国科学院过程工程研究所 一种离子液体/添加剂体系低温电沉积制备纳米铝或纳米铝镀层的方法
KR102135750B1 (ko) 2012-06-08 2020-07-22 온데르조액센트럼 부어 앤웬딩 판 스타알 엔.브이. 금속 코팅을 생성하는 방법
CN103484900A (zh) * 2013-09-18 2014-01-01 湖南工业大学 一种离子液体中直接电沉积晶态纳米晶无微裂纹铬镀层的方法
CN104294327B (zh) * 2014-10-20 2016-07-13 中国科学院过程工程研究所 一种离子液体电解液及用该电解液制备光亮铝镀层的方法
CN105220216B (zh) * 2015-09-28 2017-08-25 中国科学院兰州化学物理研究所 一种铝或铝合金电化学抛光方法
TWI662162B (zh) * 2016-11-15 2019-06-11 財團法人工業技術研究院 一種電鍍方法及其系統
JP7072796B2 (ja) * 2018-02-19 2022-05-23 国立大学法人 名古屋工業大学 調光部材
CN118028962A (zh) * 2024-02-23 2024-05-14 广东倍亮科技有限公司 离子液体在金属固体电解抛光中的应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849438A (en) * 1987-11-18 1989-07-18 Agro-Kanesho Co., Ltd. 1,2-benzoisothiazol-3(2H)-one 1,1-dioxide, ion(1-),2-hydroxy-N,N,N-trimethyl-ethanaminium which is plant protection agent for control of fungi and bacteria
US6552843B1 (en) * 2002-01-31 2003-04-22 Innovative Technology Licensing Llc Reversible electrodeposition device with ionic liquid electrolyte
US20040054231A1 (en) * 2000-09-27 2004-03-18 Andrew Abbott Ionic liquids and their use
US20040061919A1 (en) * 2002-09-27 2004-04-01 Innovative Technology Licensing, Llc Optimum switching of a reversible electrochemical mirror device
US20040097755A1 (en) * 2000-09-27 2004-05-20 Abbott Andrew P. Ionic liquids and their use as solvents
US20040150866A1 (en) * 2003-01-31 2004-08-05 Innovative Technology Licensing, Llc Locally-switched reversible electrodeposition optical modulator
US20050205425A1 (en) * 2002-06-25 2005-09-22 Integran Technologies Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
US20070281176A1 (en) * 2004-12-17 2007-12-06 Integtan Technologies, Inc. Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate
US20090101514A1 (en) * 2005-09-07 2009-04-23 Kyoto University Electrodeposition Method for Metals

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5265120A (en) * 1975-11-26 1977-05-30 Sony Corp Electro plating method of aluminium or aluminium alloy
DE102004059520A1 (de) * 2004-12-10 2006-06-14 Merck Patent Gmbh Elektrochemische Abscheidung von Tantal und/oder Kupfer in ionischen Flüssigkeiten
US8361300B2 (en) * 2006-02-15 2013-01-29 Akzo Nobel N.V. Method to electrodeposit metals using ionic liquids

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849438A (en) * 1987-11-18 1989-07-18 Agro-Kanesho Co., Ltd. 1,2-benzoisothiazol-3(2H)-one 1,1-dioxide, ion(1-),2-hydroxy-N,N,N-trimethyl-ethanaminium which is plant protection agent for control of fungi and bacteria
US20040054231A1 (en) * 2000-09-27 2004-03-18 Andrew Abbott Ionic liquids and their use
US20040097755A1 (en) * 2000-09-27 2004-05-20 Abbott Andrew P. Ionic liquids and their use as solvents
US7196221B2 (en) * 2000-09-27 2007-03-27 Scionix Limited Ionic liquids and their use
US6552843B1 (en) * 2002-01-31 2003-04-22 Innovative Technology Licensing Llc Reversible electrodeposition device with ionic liquid electrolyte
US20050205425A1 (en) * 2002-06-25 2005-09-22 Integran Technologies Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
US20040061919A1 (en) * 2002-09-27 2004-04-01 Innovative Technology Licensing, Llc Optimum switching of a reversible electrochemical mirror device
US20040150866A1 (en) * 2003-01-31 2004-08-05 Innovative Technology Licensing, Llc Locally-switched reversible electrodeposition optical modulator
US20070281176A1 (en) * 2004-12-17 2007-12-06 Integtan Technologies, Inc. Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate
US20090101514A1 (en) * 2005-09-07 2009-04-23 Kyoto University Electrodeposition Method for Metals

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Sweet Success: Ionic Liquids Derived from Non-Nutritive Sweeteners" by Carter et al., Chem. Commun. 6, pages 630-631 (2004) *
F. Endres "Ionic Liquids: Solvents for the Electrodeposition of Metals and Semiconductors" CHEMPHYSCHEM 3, pages 144-154 (2002) *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120000790A1 (en) * 2009-03-17 2012-01-05 Commonwealth Scientific And Industrial Research Organisation Electrorecovery of metals
US9580772B2 (en) * 2009-03-17 2017-02-28 Commonwealth Scientific And Industrial Research Organisation Electrorecovery of metals
EP2481836A1 (de) * 2011-01-26 2012-08-01 United Technologies Corporation Beschichtungsverfahren mit Verwendung einer ionischen Flüssigkeit
WO2013122774A1 (en) * 2012-02-16 2013-08-22 Macdermid Acumen, Inc. Color control of trivalent chromium deposits
TWI468553B (zh) * 2012-02-16 2015-01-11 Macdermid Acumen Inc 三價鉻沉澱物之顏色控制
US9758884B2 (en) 2012-02-16 2017-09-12 Stacey Hingley Color control of trivalent chromium deposits
US20130319647A1 (en) * 2012-05-31 2013-12-05 Benteler Automobiltechnik Gmbh Method for producing an exhaust-gas heat exchanger
CN102839403A (zh) * 2012-09-10 2012-12-26 太原理工大学 一种离子液体中电镀铝的方法
US10669867B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Electrodeposited nickel-chromium alloy
US10669851B2 (en) 2013-12-10 2020-06-02 Raytheon Technologies Corporation Nickel-chromium-aluminum composite by electrodeposition
WO2015088861A1 (en) * 2013-12-11 2015-06-18 Lei Chen Electroformed nickel-chromium alloy
US10378118B2 (en) * 2013-12-11 2019-08-13 United Technologies Corporation Electroformed nickel-chromium alloy
US11732372B2 (en) 2013-12-11 2023-08-22 Raytheon Technologies Corporation Electroformed nickel-chromium alloy
EP3825444A1 (de) * 2019-11-22 2021-05-26 Hamilton Sundstrand Corporation Metallische beschichtung und anwendungsverfahren
US12050389B2 (en) 2020-10-23 2024-07-30 The Regents Of The University Of Colorado, A Body Corporate Electrolyte additive for controlling morphology and optics of reversible metal films

Also Published As

Publication number Publication date
DE602008004255D1 (de) 2011-02-10
CN101765681B (zh) 2013-03-20
CN101765681A (zh) 2010-06-30
JP2010535283A (ja) 2010-11-18
TW200925334A (en) 2009-06-16
EP2171131A1 (de) 2010-04-07
WO2009016189A1 (en) 2009-02-05
HK1143194A1 (en) 2010-12-24
ES2358967T3 (es) 2011-05-17
TWI359880B (en) 2012-03-11
ATE493523T1 (de) 2011-01-15
PL2171131T3 (pl) 2011-05-31
EP2171131B1 (de) 2010-12-29
CA2695488A1 (en) 2009-02-05

Similar Documents

Publication Publication Date Title
EP2171131B1 (de) Verfahren zur elektrodeponierung von metallen mithilfe ionischer flüssigkeiten unter verwendung eines zusatzstoffs
Zhao et al. Electrodeposition of aluminium from nonaqueous organic electrolytic systems and room temperature molten salts
Abbott et al. Electrofinishing of metals using eutectic based ionic liquids
AU2001290119B2 (en) Ionic liquids and their use
US8361300B2 (en) Method to electrodeposit metals using ionic liquids
US8518298B2 (en) Eutectic mixtures based upon multivalent metal ions
EP0181229B1 (de) Kathode
Fellner et al. Electrolytic aluminium plating in molten salt mixtures based on AlCl3 I: Influence of the addition of tetramethylammonium chloride
Ali et al. Electroless and electrolytic deposition of nickel from deep eutectic solvents based on choline chloride a
Hsiu et al. Electrodeposition behaviour of cadmium telluride from 1-ethyl-3-methylimidazolium chloride tetrafluoroborate ionic liquid
TWI402381B (zh) 使用離子液體電沈積金屬之方法
Su et al. Galvanostatic Deposition of Palladium-Gold Alloys in a Lewis Basic EMI Cl BF 4 Ionic Liquid
Omar et al. Electrodeposition of Ni-Co film: a review
Bi et al. Physicochemical characterization of electrosynthesized PbO2 coatings: the effect of Pb2+ concentration and current density
US20210388520A1 (en) Methods and systems for electrochemical deposition of metal from ionic liquids including imidazolium tetrahalo-metallates
Anicai et al. Studies regarding the nickel electrodeposition from choline chloride based ionic liquids
Zhu et al. Electrochemistry of Fe (II)/Fe in a hydrophobic amide-type ionic liquid
EP3417097B1 (de) Elektrochemische abscheidung von elementen in wässrigen medien
Esfahani et al. Electrodeposition of nanocrystalline zinc from sulfate and sulfate-gluconate electrolytes in the presence of additives
WO2012141136A1 (ja) 電気アルミニウムめっき液
Florea et al. Preliminary studies of silver coatings formation from choline chloride based ionic liquids
Li et al. An electrolyte for electrodeposition of hard gold based on choline chloride–urea ionic liquid
KR20160113546A (ko) 알루미늄 도금액, 알루미늄막, 수지 구조체, 알루미늄 다공체 및 알루미늄 다공체의 제조 방법
Ghosh Electrodeposition of Cu, Sn and Cu-Sn alloy from choline chloride ionic liquid
dela Peña Nickel Electrodeposition Using Deep Eutectic Solvent-based Electrolyte

Legal Events

Date Code Title Description
AS Assignment

Owner name: AKZO NOBEL N.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUZMANOVIC, BORIS;NABUURS-WILLEMS, LAMBERDINE JOHANNA WILLEMINA MARIA;VAN STRIEN, CORNELIS JOHANNES GOVARDUS;AND OTHERS;SIGNING DATES FROM 20100112 TO 20100215;REEL/FRAME:023991/0136

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE