WO2018142430A1 - Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages - Google Patents

Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages Download PDF

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Publication number
WO2018142430A1
WO2018142430A1 PCT/IT2017/000016 IT2017000016W WO2018142430A1 WO 2018142430 A1 WO2018142430 A1 WO 2018142430A1 IT 2017000016 W IT2017000016 W IT 2017000016W WO 2018142430 A1 WO2018142430 A1 WO 2018142430A1
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WIPO (PCT)
Prior art keywords
ruthenium
metal
per
electrolytic bath
previous
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.)
Ceased
Application number
PCT/IT2017/000016
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English (en)
Inventor
Ester Falletta
Andrea TORRACCHI
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.)
Valmet Plating SRL
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Valmet Plating SRL
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 Valmet Plating SRL filed Critical Valmet Plating SRL
Priority to PCT/IT2017/000016 priority Critical patent/WO2018142430A1/fr
Publication of WO2018142430A1 publication Critical patent/WO2018142430A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention refers to a galvanic deposition process for obtaining the deposit of ruthenium and/or of its alloys, on an object in order to obtain final ruthenium layers with particular colorations, otherwise not obtainable with traditional electro-deposited deposits .
  • the deposits obtained in this way can be used as a decorative finishing layer, or they can be undergone to a further "re-uncoating” treatment, such as with abrasive ceramic materials, in order to obtain "un-coated” finishing "of vintage type".
  • metal objects or of metal-non- metal compounds can be realized with the use of various well-known technigues which depend on the type of object to be realized.
  • said objects can be realized through the well-known process of galvanic deposition; thanks to it, one or more metallic layers (also of precious metals) can be electro-deposited on a support (for example, an object) made of either a specific composite metal (for example a suitable polymer) or of a specific composite metal non-metal or non-metal metal.
  • a support for example, an object
  • a specific composite metal for example a suitable polymer
  • a specific composite metal non-metal or non-metal metal for example a suitable polymer
  • bronze or brass objects are treated through galvanic deposition of suitable metals, in such a manner so as to improve their features of resistance to corrosion, mechanical features, as well aesthetic ones (for example, shininess, smooth or rough appearance, colour), especially if those objects are intended for the industry of fashion or of jewelry in general.
  • one or more layers of metallic material/s (even precious) can be deposited on the substrate, so as to obtain the desired final result/object.
  • the process of the invention comprises substantially a treatment phase of the object mentioned above, by means of a suitable galvanic deposition on it with a suitable metallic element for making the desired final product coloured with colorations, differently not achievable with conventional electro-deposited deposits.
  • the applicant has surprisingly found that the formation through suitable galvanic deposition of ruthenium deposits or of its alloys on an object as described beforehand and further, allows to lend the finished product colorations and shades of colour differently not achievable with conventional electro- deposited deposits.
  • said ruthenium- based deposits and/or of its alloys, obtained by the process of the invention can be used as a decorative layer of finishing.
  • said deposits mentioned above can also be further undergone to a treatment of un-coating to give uncoated finishes of "vintage" type.
  • the process of galvanic deposition allows to coat an object made of generally not precious metallic material (for example, copper, brass, bronze), as well as a suitable non-metallic material, or a suitable metallic non-metallic compound, with one or more layers of generally more precious metal/s, by taking advantage of electrolytic deposition.
  • precious metallic material for example, copper, brass, bronze
  • suitable non-metallic material for example, copper, brass, bronze
  • suitable metallic non-metallic compound for example, copper, brass, bronze
  • the cathode is constituted by the object to be coated, while the anode can be constituted by the metal which has to be deposited (sacrificial anode) , by another inert metal or by graphite.
  • a difference of potential is imposed to such electrodes by means of a power generator. In such conditions, the cations of the metal to be deposited will move towards the cathode (negatively charged) while anions will move towards the anode (positively charged) .
  • “re-uncoating” means the mechanic process through which part of the superficial layer coating the selected item/object is removed by using suitable abrasive material for this purpose, based on the desired superficial finishing effect.
  • tumble finishing means a superficial finishing process which takes place by means of impacts of pieces inserted in a specific circular vibrator (tumbling barrel), led to vibrate, filled with abrasive material, of size, dimensions and hardness depending on the desired superficial finishing.
  • abrasive material of size, dimensions and hardness depending on the desired superficial finishing.
  • pieces are wet with a specific liquid, commonly known in this field, to make the superficial finishing more homogeneous.
  • the rotation speed of the tumbling barrel influences the final effect of the processing.
  • "of vintage type” means a particular type of re-uncoating and/or tumble finishing which simulates an oxidation/natural ageing of the item.
  • the object of the present invention is a process for obtaining the deposit of ruthenium and/or of its alloys, on an object, said process comprising or consisting at least of the following phases:
  • an electrolytic bath comprising or consisting of: an aqueous solution of salts of ruthenium and/or ruthenium and metals that can co-deposit with the ruthenium, possibly complexed with suitable complexing agents; conductor salts; any suitable organic and/or inorganic additives;
  • a cathode constituted by the object which is to be coated by said coloured deposit of ruthenium and/or ruthenium and metals that can co- deposit with ruthenium; and an anode consisting of metallic ruthenium (sacrificial anode) , titanium, platinized titanium, mixed oxides, graphite;
  • ruthenium is used in the form of pure metal (for example, as a sacrificial anode) , or as a salt thereof, optionally complexed, or together with co-be deposited elements selected from the group consisting of Cr, Mn, Fe , Co, Ni, Cu, Zn, Rh, Pd, Ag, Cd, In, Sn, Pt, Au, Pb, Bi, P, V, Ga, Y, Zr, W; preferably, Fe, Cu, Zn, Rh, Pd, Ag, Sn, Pt, Au, Bi, W; more preferably Fe, Rh, Pd, Ag, Pt, Au, W.
  • the ions of ruthenium salts in the electrolytic bath are selected from the group consisting of: chloride, nitrosilchloride, bromide, iodide, sulfamate, nitrosilnitrate and/or complexing ions, sulfates, sulfamates, phosphates, pyrophosphates, phosphonates , mono-, di- and tri-carboxylates , acetates, citrates, oxalates, gluconates, succinates, glutarates, adipates, tartrates, eptonates, malates, maleates, malonates and/or tetracarboxylic acids such as EDTA (ethylenediaminetetra-acetic acid) ; NTA (nitrilo triacetic acid) and/or their analogous substituted ones.
  • EDTA ethylenediaminetetra-acetic acid
  • NTA nitrilo triacetic acid
  • Said complexing salts are usually used in stoichiometric quantity in respect to the ruthenium or also in an excess in respect to the same quantity.
  • said conductor salts in the electrolytic bath are selected from the group consisting of: sulfates, sulfamates, phosphates, pyrophosphates, phosphonates , mono-, di- and tri-carboxylates , acetates, citrates, oxalates, gluconates, succinates, glutarates, adipates, tartrates, eptonates, malates, maleates, malonates, and/or tetracarboxylic acids such as EDTA (ethylenediaminetetra- acetic acid); NTA (nitrilo triacetic acid) and/or their analogous substituted ones.
  • EDTA ethylenediaminetetra- acetic acid
  • NTA nitrilo triacetic acid
  • the concentration of the salts in the electrolytic bath solution of the invention is usually comprised from 1 to 500 g/L; preferably, from 10 to 400 g/L; more preferably, from 20 to 300 g/L.
  • organic additives in the electrolytic bath are selected from the group consisting of: surfactants, non-ionic, cationic or anionic, anti-pitting agents, brighteners, amphoteric compounds, betaines and solfobetaine, sulfur compounds, aromatics and non, and similar ones, in a variable quantity (based on the experience of the specialist of the field) to be determined case by case, depending on the desired final colour .
  • inorganic additives in the electrolytic bath are selected from the group consisting of: Au, Pd, Rh, Pt, Ag, Ir, Cr, Fe, Co, Ni, Cu, Zn, Cd, In, Sn, Pb, Bi, V, Ga, Y, Zr, Mo, .
  • concentrations of said metals in the electrolytic bath solution of the invention are usually comprised from 0.001 g/L to 500 g/L; preferably, from 0.001 to 300 g/L; more preferably, from 0.01 to 200 g/L.
  • the concentration of ruthenium, as an element or in form of a salt in the electrolytic bath solution of the invention is comprised from 0.1 g/L to 10 g/L; preferably, from 0.2 g/L to 5 g/L; more preferably, from 0.5 g/L to 3 g/L.
  • the object (or, as also called further, substrate) that constitutes the cathode is in turn formed from a metal, or a metal alloy, or by more metal layers (precious or non-precious), or by a non-metal (for example a suitable organic polymer) , or a composite metal-non-metal or non-metal-metal suitable to undergo a galvanic deposition process as that of the present invention.
  • said non- metallic substrate can be an organic object, organic- polymer, or an organic-metal composite/organic-polymer- metal (such as an object of a suitable plastic material, coated by one or more layers of metals or metal alloys) able to be undergone to the galvanic process of the present invention.
  • the metallic substrate is usually selected from the group consisting of Fe, Ni, In, Co, Sn, Cu, Zn, Cr, Bi, Al, V, Mn, Mo, Bi, Au, Ru, Pt, Ag and Pd and/or their alloys; preferably consisting of Fe, Ni, In, Co, Sn, Cu, Zn, Cr, Bi, Al, Au, Ru, Pt, Ag and Pd and/or their alloys; more preferably consisting of Fe, Ni, In, Sn, Cu, Zn, Al, Au, Ru, Pt, Ag, Pd and/or their alloys.
  • said metallic substrate is selected from copper and/or nickel and/or brass and/or bronze and/or zamak (alloy of Zn, Al, Mg, Cu) , as such or conveniently galvanized with additional layers of more noble metals as known over the prior art.
  • the anodes used in the above phase 2) of the process of the present invention normally the same ones are appropriately selected from those commonly used in the prior art, depending on needs.
  • the anodes can be selected from: soluble electrodes, inert electrodes such as graphite electrodes, mixed oxides, platinized titanium.
  • the electrodes are selected from those previously described in phase 2) of the process of the present invention.
  • the intensity of the used processing currents is usually comprised from 0.001 A/dm 2 to 100 A/dm 2 ; preferably, from 0.01 to 50 A/dm 2 ; more preferably, from 0.05 to 25 A/dm 2 ; even more preferably, from 0.1 to 10 A/dm 2 ; even more preferably, from 0.05 to 5 A/dm 2 .
  • the processing temperature of the electrolytic bath of the present invention is comprised from room temperature (about 25°C) to about 80°C depending on the substrate to be treated; preferably, ranging from about 35°C to about 75°C; more preferably, from about 40 °C to about 70 °C; even more preferably, from about 45°C to about 65°C; even more preferably, from about 50°C to about 60°C; in one form of realization, to 55°C.
  • this can vary, depending on the temperature of the electrolytic bath, from 0.5 to 15-30 minutes depending on the desired final color.
  • the deposition period of ruthenium to obtain an orange colour is 2 minutes; to obtain a purple colour is 4 minutes; to obtain a blue colour is of 6 minutes; to obtain a green colour is of 8 minutes .
  • the thickness of the metal layer (ruthenium and/or its alloy) to be deposited is between 0.001 ⁇ and 10 ym; preferably, between 0.001 ⁇ and 5 ym; more preferably, between 0.05 and 0.5 m.
  • the colours obtained with the galvanic deposition process of the present invention described previously can be, for example regulated from blue to fuchsia, orange, petroleum blue, violet, green by varying conveniently the process parameters of the invention (composition of the electrolytic bath, its temperature, electrodes, applied current intensity, deposition period, and so on) described previously .
  • the electrolytic bath contained:
  • Cathode a plate of 20 mm x 10 mm x 2 mm brass, subjected to a galvanic cycle thus described: copper plating, deposition of white bronze, deposition of gold .
  • Anode platinized titanium
  • the coloured ruthenium deposits and/or of its alloys obtained as described previously can be advantageously used as a decorative finishing layer of the object on which it was applied (for example, as such or after polishing) , thus improving the aesthetic appearance and the duration.
  • the so coloured objects are finally washed in water and undergone to drying in a ventilated oven, with temperatures between 35°C and 90°C, preferably between 60°C and 80°C, for periods ranging between 30 minutes and 90 minutes.
  • said deposits can be undergone to a further treatment, so-called “re-uncoating”, for example with the use of abrasive ceramic materials or of known similar substances, in order to obtain a "re-uncoated” finishing "of vintage type".
  • the objects coated by a colored layer of ruthenium and/or an alloy thereof obtained through the process of the present invention are undergone to a known treatment in tumble finishing with one or more abrasive ceramic materials for a variable duration depending on the desired degree of un- coating.
  • Some of the preferred abrasive ceramic materials are selectable, for example, among the following commercial products: RS 06/06, RS 10/10, RS 10/10/05, RS 02/05 (supplier: Rosier Italiana S.R.L., Concorezzo, IT).
  • Said products are abrasive ceramic materials of RS quality, namely of high abrasive power, with a specific weight equal to 2.52 g/cm .
  • Rosier, ceramics of 06/06 type have "triangular" shape, that is pentahedral with triangular base, with characteristic dimensions of 6 mm x 6 mm (h x w) ; ceramics of type 10/10 have "triangular" shape, that is pentahedral with triangular base, with characteristic dimensions of 10 mm x 10 mm (h x w) ; the ceramic 10/10/05 have "elliptical" form or of a cylinder with an elliptical base with characteristic dimensions of 10 mm x 10 mm x 5 mm (height x major axes of ellipse x minor axis of ellipse); ceramic 02/05 are "cylindrical angular cut"- shape with characteristic dimensions of 2 mm x 5
  • Circular Vibrator model MB 25 (of Rosier Italiana S.R.L., Concorezzo, IT); specifications of the machinery; 400 V, 50 Hz, 1,500 rpm; Un-coating period: 10-40 minutes, depending on the desired finisihing.
  • the present invention has allowed to obtain (metallic and non-metallic) objects coated with final ruthenium layers with particular colorations, not obtainable with traditional electro-deposited deposits, by means of a particular galvanic deposition process of ruthenium and/or of a metallic alloy of it, in such conditions as to provide the desired final coloration.
  • the deposits obtained in this way can be used as a decorative finishing layer, or they can be undergone to a further "re-uncoating” treatment, such as with abrasive ceramic materials, in order to obtain "un-coated finishing "of vintage type” .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un procédé de dépôt galvanique permettant de former un dépôt de ruthénium et/ou de ses alliages sur un objet afin d'obtenir des couches finales de ruthénium ayant des colorations particulières, qui sinon ne pourraient pas être obtenues avec des dépôts réalisés par électrodéposition classique. Les dépôts ainsi obtenus peuvent être utilisés comme couche de finition décorative, ou ils peuvent être soumis à un traitement ultérieur de "ré-élimination de revêtement", par exemple à l'aide de matériaux céramiques abrasifs, pour obtenir une finition "à nu" "de type vintage".
PCT/IT2017/000016 2017-01-31 2017-01-31 Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages Ceased WO2018142430A1 (fr)

Priority Applications (1)

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PCT/IT2017/000016 WO2018142430A1 (fr) 2017-01-31 2017-01-31 Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages

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PCT/IT2017/000016 WO2018142430A1 (fr) 2017-01-31 2017-01-31 Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019109188A1 (de) * 2019-04-08 2020-10-08 Umicore Galvanotechnik Gmbh Elektrolyt zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten
CN111850631A (zh) * 2020-07-30 2020-10-30 金川集团股份有限公司 高光泽装饰性镀铑层电镀液
CN112095129A (zh) * 2020-09-23 2020-12-18 深圳市森泰金属技术有限公司 一种铜合金表面复古工艺方法
CN113774435A (zh) * 2021-09-08 2021-12-10 周大福珠宝金行（深圳）有限公司 一种黄金的复古工艺
WO2022112379A1 (fr) 2020-11-26 2022-06-02 Umicore Galvanotechnik Gmbh Couche d'alliage de ruthénium et ses combinaisons de couches
CN115261937A (zh) * 2022-03-22 2022-11-01 东莞市弘裕表面处理技术有限公司 钌镀液及其制备方法、镀钌方法、钌镀层及含有其的器件

Citations (2)

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DE1959907A1 (de) * 1968-11-28 1970-06-18 Johnson Matthey Co Ltd Rutheniumkomplex und seine Verwendung bei der Elektroplattierung
US4082625A (en) * 1976-06-08 1978-04-04 The International Nickel Company, Inc. Electrodeposition of ruthenium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1959907A1 (de) * 1968-11-28 1970-06-18 Johnson Matthey Co Ltd Rutheniumkomplex und seine Verwendung bei der Elektroplattierung
US4082625A (en) * 1976-06-08 1978-04-04 The International Nickel Company, Inc. Electrodeposition of ruthenium

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019109188B4 (de) 2019-04-08 2022-08-11 Umicore Galvanotechnik Gmbh Verwendung eines Elektrolyten zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten
WO2020208004A1 (fr) * 2019-04-08 2020-10-15 Umicore Galvanotechnik Gmbh Électrolyte pour déposer des couches d'alliage d'anthracite/rhodium noir/ruthénium
CN113508195A (zh) * 2019-04-08 2021-10-15 优美科电镀技术有限公司 用于沉积深灰色/黑色铑/钌合金层的电解质
TWI825262B (zh) * 2019-04-08 2023-12-11 德商烏明克葛凡諾科技有限公司 用於沉積無煙煤／黑銠／釕合金層之電解質
US11421335B2 (en) 2019-04-08 2022-08-23 Umicore Galvanotechnik Gmbh Electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers
DE102019109188A1 (de) * 2019-04-08 2020-10-08 Umicore Galvanotechnik Gmbh Elektrolyt zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten
CN111850631A (zh) * 2020-07-30 2020-10-30 金川集团股份有限公司 高光泽装饰性镀铑层电镀液
CN111850631B (zh) * 2020-07-30 2021-10-08 金川集团股份有限公司 高光泽装饰性镀铑层电镀液
CN112095129A (zh) * 2020-09-23 2020-12-18 深圳市森泰金属技术有限公司 一种铜合金表面复古工艺方法
DE102020131371A1 (de) 2020-11-26 2022-06-02 Umicore Galvanotechnik Gmbh Rutheniumlegierungsschicht und deren Schichtkombinationen
WO2022112379A1 (fr) 2020-11-26 2022-06-02 Umicore Galvanotechnik Gmbh Couche d'alliage de ruthénium et ses combinaisons de couches
CN116157557A (zh) * 2020-11-26 2023-05-23 优美科电镀技术有限公司 钌合金层及其层组合
JP2023550807A (ja) * 2020-11-26 2023-12-05 ウミコレ・ガルファノテフニック・ゲーエムベーハー ルテニウム合金層及び該層の組み合わせ
US20240018679A1 (en) * 2020-11-26 2024-01-18 Umicore Galvanotechnik Gmbh Ruthenium Alloy Layer and Its Layer Combinations
DE102020131371B4 (de) 2020-11-26 2024-08-08 Umicore Galvanotechnik Gmbh Verwendung eines Elektrolyten zur Erzeugung einer Rutheniumlegierungsschicht
CN113774435A (zh) * 2021-09-08 2021-12-10 周大福珠宝金行（深圳）有限公司 一种黄金的复古工艺
CN115261937A (zh) * 2022-03-22 2022-11-01 东莞市弘裕表面处理技术有限公司 钌镀液及其制备方法、镀钌方法、钌镀层及含有其的器件

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