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EP1975282B1 - Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir. - Google Patents

Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir. Download PDF

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Publication number
EP1975282B1
EP1975282B1 EP07006380A EP07006380A EP1975282B1 EP 1975282 B1 EP1975282 B1 EP 1975282B1 EP 07006380 A EP07006380 A EP 07006380A EP 07006380 A EP07006380 A EP 07006380A EP 1975282 B1 EP1975282 B1 EP 1975282B1
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EP
European Patent Office
Prior art keywords
acid
electrolyte
ruthenium
phosphonic acid
layers
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.)
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Application number
EP07006380A
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German (de)
English (en)
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EP1975282A1 (fr
Inventor
Philip Dipl.-Ing. Schramek
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Umicore Galvanotechnik GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Priority to EP07006380A priority Critical patent/EP1975282B1/fr
Application filed by Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Priority to AT07006380T priority patent/ATE449201T1/de
Priority to DE502007002036T priority patent/DE502007002036D1/de
Priority to JP2010500099A priority patent/JP5449130B2/ja
Priority to BRPI0809382-2A priority patent/BRPI0809382A2/pt
Priority to CN2008800147422A priority patent/CN101675185B/zh
Priority to US12/532,296 priority patent/US8211286B2/en
Priority to KR1020097020293A priority patent/KR101416253B1/ko
Priority to PCT/EP2008/001751 priority patent/WO2008116545A1/fr
Priority to TW097108314A priority patent/TWI427195B/zh
Publication of EP1975282A1 publication Critical patent/EP1975282A1/fr
Application granted granted Critical
Publication of EP1975282B1 publication Critical patent/EP1975282B1/fr
Priority to HK10103898.5A priority patent/HK1138044A1/xx
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • 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

Definitions

  • the invention relates to a ruthenium electrolyte, which is suitable for the deposition of decorative and technical layers with particular blackness. Furthermore, the invention relates to a method for the deposition of decorative and technical layers of ruthenium with special blackness ("black-ruthenium”) on jewelry, decorative items, durable goods and technical items.
  • black-ruthenium ruthenium with special blackness
  • Durable consumer goods and technical articles, jewelery and decorative goods are finished with thin oxidation-stable metal layers to protect against corrosion and / or for visual enhancement. These layers must be mechanically stable and should not show tarnish or signs of wear even after prolonged use.
  • a proven means for producing such layers are electroplating processes, which can be used to obtain a variety of metal and alloy layers in high quality form. Examples well-known from everyday life are galvanic bronze and brass layers on doorknobs or buttons, chrome plating of vehicle parts, galvanized tools or gold plating on watch straps.
  • a particular challenge in the field of galvanic finishing is the production of oxidation-stable and mechanically strong metal coatings in black color, which can be interesting not only in the decorative and decorative sector but also for technical applications, for example in the field of solar technology. Only a few metals are available for producing oxidation-stable, black layers.
  • ruthenium, rhodium and nickel are suitable.
  • the use of the precious metal rhodium is limited to the jewelry sector because of the high raw material costs.
  • the use of cost-effective nickel and nickel-containing alloys is especially in the jewelry and durable goods sector only in exceptional cases and in compliance with strict conditions possible, since it is nickel and nickel-containing Metal layers around contact allergens is.
  • the use of ruthenium is a useful alternative for all described applications.
  • Electrolytes for producing black ruthenium layers in electroplating processes are known in the art.
  • the most common baths contain ruthenium in complexed form with sulfamic acid or ruthenium as nitridochloro or nitridobromo complex.
  • JP 63259095 a process for ruthenium electroplating using a bath containing 5 g / l ruthenium and 100 to 150 g / l amidosulfonic acid.
  • the WO 2001/011113 discloses a ruthenium electrolyte containing ruthenium sulfate and sulfamic acid (amidosulfonic acid).
  • a blackening additive a thio compound is used. To protect the thio compound from decomposition by anodic oxidation, a sacrificial substance must also be added.
  • An electrolyte for the electrodeposition of low-stress, crack-resistant ruthenium layers contains ruthenium in complexed with amidosulfuric acid and pyridine or N-alkylated pyridinium salts.
  • US 4,375,392 claims an acidic electrolyte for depositing ruthenium on various substrates containing a complex of ruthenium and amidosulfonic acid present in a molar ratio of 4 to 10 moles of amidosulfonic acid per mole of ruthenium and in appropriate concentration, and containing a second compound of a metal selected from the group containing nickel, cobalt, iron, tin, lead and magnesium. The concentration of the second metal is chosen so that crack-free ruthenium layers can be deposited.
  • the pH of the bath is between 0.1 and 2.2.
  • DE 1 959 907 describes the use of the dinuclear ruthenium complex [Ru 2 NCl x Br 8-x (H 2 O) 2 ] 3- in an electroplating plating bath.
  • the nitrido-chloro complex [Ru 2 NCl 8 (H 2 O) 2 ] 3- is used.
  • This nitridochloro complex of ruthenium is also used in the aqueous, non-acidic bath for electrodeposition of ruthenium, which is used in the US 4,297,178 is described. It also contains oxalic acid or an oxalate.
  • the invention relates to a ruthenium electrolyte which contains, in addition to 1 to 20 g / l of ruthenium, one or more compounds selected from the group consisting of dicarboxylic and tricarboxylic acids, benzenesulfonic acid, N-containing aromatics, and amino acids or derivatives of said compounds, and in which moreover 0.01 to 10 g / l of a thio compound is used as a blackening additive.
  • JP 2054792 contains, in addition to an inorganic ruthenium salt, preferably ruthenium sulfate, and an inorganic acid, preferably sulfuric acid, a "metal of group III", preferably Sc, Y, In or Ga.
  • black layers For the finishing of jewelery and decorative objects, black layers must have a perfect optical adhesive quality in addition to an excellent mechanical adhesion. If necessary, they must be able to be produced in a glossy or matt form and with a very deep blackness. The same applies to applications in the technical field, in particular in solar technology. Blackcoats for processing consumer goods must also meet high mechanical stability requirements. In particular, they must not show any black abrasion even with frequent use for a long time.
  • ruthenium baths described in the prior art which meet these requirements are either dependent on the use of toxicologically harmful compounds such as thio compounds as blackening additive or contain another transition metal to ensure the required mechanical adhesion, making it difficult to guide the bath during the deposition process.
  • the present invention was therefore based on the object of providing a non-toxic electrolyte for depositing layers of ruthenium with particular blackness ("black ruthenium”), with which black layers can be produced in a galvanic standard process, which are characterized by high mechanical properties Stability, in particular by abrasion resistance even with frequent use, distinguished and which can be generated in various degrees of gloss preserving gloss.
  • black ruthenium ruthenium with particular blackness
  • an electrolyte containing one or more phosphonic acid derivatives as a blackening additive wherein the volume concentration of the ruthenium after complete dissolution of the compound is between 0.2 and 20 grams per liter of electrolyte, calculated as ruthenium metal.
  • a method is provided, with the use of the electrolyte according to the invention decorative and technical layers of ruthenium with special blackness (“black-ruthenium”) can be applied to jewelry, Dekorgüter, consumer goods and technical items, wherein the substrates to be coated in be immersed in the electrolyte of the invention.
  • Non-toxic in the sense of this document is understood to mean that in the so-called electrolyte according to the invention no substances are contained, which according to the regulations in force in Europe for handling dangerous goods and hazardous substances as “toxic” (T) or “very toxic "(T + ) are to be classified.
  • Ruthenium is used in the form of a water-soluble compound, preferably as a binuclear anionic nitrido-halo-complex compound of the formula [Ru 2 N (H 2 O) 2 X 8 ] 3- wherein X is a halide ion. Particularly preferred is the chloro complex [Ru 2 N (H 2 O) 2 Cl 8 ] 3- .
  • the amount of the complex compound in the electrolyte of the invention is preferably selected so that the final electrolyte contains 1 to 15 grams of ruthenium per liter of electrolyte, most preferably 3 to 10 grams of ruthenium per liter of electrolyte.
  • the blackening of the electrodeposited ruthenium layers is achieved by selectively inhibiting the rate of deposition from the plating bath.
  • an inhibitor and thus as a blackening additive one or more phosphonic acid derivatives are contained in the bath according to the invention.
  • the compounds used are preferably the compounds aminophosphonic acid AP, 1-aminomethylphosphonic acid AMP, amino-tris (methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2-trichloroethyl) -phosphonic acid, Amino-1-phosphona-actyl) -phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl) -phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl) -phosphonic acid, (4-chlorophenyl-hydroxymethyl) -phosphonic acid Diethylenetriamine penta (methylenephosphonic acid) DTPMP, ethylenediamine tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP, hydroxyethyl-amino-d
  • Particular preference is given to using one or more compounds selected from the group consisting of amino-tris (methylenephosphonic acid) ATMP, diethylenetriamine-penta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP, hydroxyethylamino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine tetra (methylphosphonic acid) HDTMP, salts derived therefrom or condensates derived therefrom, or combinations thereof.
  • amino-tris methylenephosphonic acid
  • DTPMP diethylenetriamine-penta
  • EDTMP ethylenediamine-tetra (methylenephosphonic acid)
  • 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP hydroxyethylamino-di (methylenephosphonic acid) HEMPA
  • HEMPA
  • Amino-tris (methylenephosphonic acid) ATMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP and 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP and salts derived therefrom or condensates derived therefrom are outstandingly suitable in particular for the coating of decorative and consumer goods , or combinations thereof.
  • the concentration of the blackening additive determines the degree of blackening of the layer to be produced. It must be chosen so that the desired depth of blackening is achieved, but must not be too high. If the concentration of the blackening additive is chosen too high, current densities must be selected in order to ensure economical deposition rates, in which the adhesive strength of the resulting ruthenium layer is no longer guaranteed.
  • the electrolyte according to the invention preferably contains between 0.1 and 20 grams of phosphonic acid derivatives per liter of electrolyte, more preferably 1 to 10 grams of phosphonic acid derivatives per liter of electrolyte. If dark gray, not deep black dyeings are to be achieved, 0.1 to 4 grams of phosphonic acid derivatives in liters of electrolyte are preferred.
  • the phosphonic acid derivatives used are gloss-preserving.
  • the color of the resulting Layer can be adjusted in all variants from light black to deep black, without changing their characteristic gloss.
  • the pH of the bath according to the invention is preferably between 0 and 3, particularly preferably between 0.5 and 2.
  • the electrolyte according to the invention may contain inorganic mineral acids, preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, amidosulfonic acid , Sulfuric acid, sulfuric acid, disulfuric acid, dithionic acid, disulfurous acid and dithionic acid, or combinations thereof.
  • hydrochloric acid hydrobromic acid, sulfamic acid and sulfuric acid or combinations thereof are suitable.
  • the preferred volume concentration of inorganic mineral acid is between 0 and 50 grams per liter of electrolyte, more preferably between 0 and 40 grams per liter of electrolyte.
  • Particularly suitable electrolytes for the deposition of uniform, decorative black ruthenium layers contain between 1 and 10 grams of sulfuric acid per liter of electrolyte.
  • the electrolyte may contain, in addition to ruthenium and the phosphonic acid derivatives, organic additives which take over the function of the wetting agent.
  • the addition of one or more compounds is preferably selected from the group of the alkanesulfonic acids or the ionic and nonionic surfactants or combinations thereof. Alkanesulfonic acids are particularly suitable.
  • the erfuidungswele bath is suitable for the deposition of layers of pure ruthenium, but not for the deposition of ruthenium alloys. Except ruthenium, the electrolyte contains no transition metal ions.
  • the described ruthenium electrolyte which is the subject of the present invention, is particularly suitable for the deposition of decorative deep black-glossy layers, for example, on jewelery and decorative objects. It can preferably be used in drum and frame coating processes.
  • the pieces of jewelery, decorative goods, consumer goods or technical articles (collectively referred to as substrates) to be coated dip into the electrolyte according to the invention and form the cathode.
  • the electrolyte is preferably tempered in a range of 20 to 80 ° C.
  • Particularly decorative layers are obtained at electrolyte temperatures of 60 to 70 ° C.
  • a current density of 0.01 to 10 A / dm 2 is preferably set, particularly preferably 0.05 to 5 A / dm 2 .
  • the chosen value is also determined by the type of coating process. In a drum coating process, the preferred current density is between 0.05 to 1 A / dm 2 . In frame coating processes, a current density of 0.5 to 5 A / dm 2 leads to optically flawless black ruthenium layers.
  • Insoluble anodes are suitable for carrying out the galvanic deposition process from the acidic ruthenium bath according to the invention.
  • Anodes are preferably used from a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon” DLC) or combinations thereof.
  • an inventive electrolyte was used, which in addition to 2.5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- 15 g / L 1-hydroxyethane (1,1-di phosphonic acid) HEDP dissolved in water as a blackening additive and containing 20 g / L sulfuric acid.
  • the electrolyte had a pH of 0.8.
  • the substrates were provided with mechanically stable, abrasion-resistant black layers, which are considered optically flawless in the consumer goods sector.
  • a slight irregularity in the layer thickness of the layers obtained limits the use of this bath according to the invention to applications outside the jewelry area.
  • an electrolyte according to the invention was used, the 5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 1.5 g / L ethylenediaminetetra (methylenephosphonic) EDTMP as Blackening additive contained in water.
  • 4 g / L sulfuric acid was added to the electrolyte so that the pH at the beginning of the deposition was 1.3.
  • suitable substrates were finished at a set current density of 0.5 to 3 A / dm 2 with black ruthenium layers.
  • the electrolyte was heated at 60 to 70 ° C.
  • the layers obtained had a very good mechanical stability, showed a deep black color and high gloss.
  • the optical quality of the layers thus produced was so high that the suitability of this bath according to the invention is also given for the jewelry and decor area.
  • Another bath according to the invention was investigated, which contained 5 g / l of ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 5 g / l of amino-tris (methylenephosphonic acid) ATMP in water.
  • the pH of the bath was adjusted to 1.4 with 4 g / L sulfuric acid.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Secondary Cells (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (12)

  1. Électrolyte non toxique pour le dépôt de couches techniques et décoratives à base de ruthénium avec des noirs particuliers ("ruthénium-noir"), caractérisé en ce que l'électrolyte contient un ou plusieurs dérivés d'acide phosphonique en tant qu'additif de noircissement et la concentration volumique du ruthénium est comprise entre 0,2 et 20 g par litre d'électrolyte, calculée en tant que ruthénium métallique.
  2. Électrolyte selon la revendication 1, caractérisé en ce que le ruthénium se trouve sous forme de composé complexe nitrurohalogénoruthénium anionique binucléaire de formule [Ru2N(H2O)2X8]3-.
  3. Électrolyte selon la revendication 2, caractérisé en ce que l'électrolyte est exempt d'autres ions de métaux de transition.
  4. Électrolyte selon la revendication 2, caractérisé en ce qu'il contient comme acide phosphonique un ou plusieurs composés choisis dans le groupe constitué par l'acide aminophosphonique AP, l'acide 1-aminométhylphosphonique AMP, l'acide amino-tris(méthylènephosphonique) ATMP, l'acide 1-aminoéthyl-phosphonique AEP, l'acide 1-aminopropylphosphonique APP, l'acide (1-acétylamino-2,2,2-trichloréthyl)-phosphonique, l'acide (1-amino-1-phosphono-octyl)-phosphonique, l'acide (1-benzoylamino-2,2,2-trichloréthyl)-phosphonique, l'acide (1-benzoylamino-2,2-dichlorovinyl)-phosphonique, l'acide (4-chloro-phényl-hydroxyméthyl)-phosphonique, l'acide diethylène-triaminepenta(méthylènephosphonique) DTPMP, l'acide éthylènediamine-tétra(méthylènephosphonique) EDTMP, l'acide 1-hydroxyéthane-(1,1-diphosphonique) HEDP, l'acide hydroxyéthylamino-di(méthylènephosphonique) HEMPA, l'acide hexaméthylènediamine-tétra(méthyl-phosphonique) HDTMP, l'acide ((hydroxyméthyl-phosphonométhylamino)-méthyl)-phosphonique, l'acide nitrilo-tris(méthylènephosphonique) NTMP, l'acide 2,2,2-trichloro-1-(furanne-2-carbonyl)-amino-éthyl-phosphonique, des sels dérivés de ceux-ci ou des produits de condensation dérivés de ceux-ci, ou des associations de ceux-ci.
  5. Électrolyte selon la revendication 4, caractérisé en ce qu'il contient entre 0,1 et 20 grammes de dérivés d'acide phosphonique par litre d'électrolyte.
  6. Électrolyte selon la revendication 4, caractérisé en ce que le pH de l'électrolyte est compris entre 0 et 3.
  7. Électrolyte selon la revendication 6, caractérisé en ce que l'électrolyte contient des acides inorganiques minéraux choisis dans le groupe constitué par l'acide chlorhydrique, l'acide bromhydrique, l'acide iodhydrique, l'acide nitrique, l'acide nitreux, l'acide amidosulfonique, l'acide sulfurique, l'acide sulfureux, l'acide disulfurique, l'acide dithionique, l'acide disulfureux et l'acide dithioneux ou des associations de ceux-ci.
  8. Électrolyte selon l'une quelconque des revendications 4 à 7, caractérisé en ce que l'électrolyte contient comme agent mouillant un ou plusieurs composés choisis dans le groupe des acides alcanesulfoniques ou des tensioactifs ioniques et tensioactifs non ioniques ou des associations de ceux-ci.
  9. Procédé pour l'application par galvanoplastie de couches décoratives et techniques à base de ruthénium avec des noirs particuliers ("ruthénium-noir") sur des bijoux, des articles de décoration, des articles d'usage courant et des objets industriels, dans lequel on trempe les supports à revêtir dans un électrolyte qui contient du ruthénium sous forme dissoute, caractérisé en ce qu'on utilise un électrolyte qui contient un ou plusieurs dérivés d'acide phosphonique en tant qu'additif de noircissement.
  10. Procédé selon la revendication 9, caractérisé en ce que l'électrolyte est soumis à un traitement thermique dans la plage de 20 à 80 °C.
  11. Procédé selon la revendication 10, caractérisé en ce qu'on ajuste une densité de courant qui se situe dans la plage allant de 0,01 à 10 ampères par dm2.
  12. Procédé selon la revendication 11, caractérisé en ce qu'on utilise des anodes insolubles à base d'un matériau choisi dans le groupe constitué par le titane platiné, le graphite, un oxyde mixte d'iridium-métal de transition et un matériau carboné spécial ("Diamond Like Carbon" DLC) ou des associations de ces anodes.
EP07006380A 2007-03-28 2007-03-28 Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir. Active EP1975282B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
AT07006380T ATE449201T1 (de) 2007-03-28 2007-03-28 Elektolyt und verfahren zur abscheidung von dekorativen und technischen schichten aus schwarz-ruthenium
DE502007002036T DE502007002036D1 (de) 2007-03-28 2007-03-28 Elektolyt und Verfahren zur Abscheidung von dekoraium
EP07006380A EP1975282B1 (fr) 2007-03-28 2007-03-28 Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir.
BRPI0809382-2A BRPI0809382A2 (pt) 2007-03-28 2008-03-05 Eletrólito e método para depositar camadas decorativas e técnicas de rutênio negro
CN2008800147422A CN101675185B (zh) 2007-03-28 2008-03-05 电解质和沉积黑钌的装饰技术层的方法
US12/532,296 US8211286B2 (en) 2007-03-28 2008-03-05 Electrolyte and method for depositing decorative and technical layers of black ruthenium
JP2010500099A JP5449130B2 (ja) 2007-03-28 2008-03-05 電解質、並びに黒ルテニウムの装飾用の及び技術的な層を堆積するための方法
KR1020097020293A KR101416253B1 (ko) 2007-03-28 2008-03-05 블랙 루테늄의 장식층 및 기술층을 전착시키기 위한 전해액 및 방법
PCT/EP2008/001751 WO2008116545A1 (fr) 2007-03-28 2008-03-05 Électrolyte et procédé de dépôt de couches décoratives et techniques de ruthénium noir
TW097108314A TWI427195B (zh) 2007-03-28 2008-03-10 用於沈積出黑色釕裝飾層與技術層的電解液與方法
HK10103898.5A HK1138044A1 (en) 2007-03-28 2010-04-21 Electrolyte and method for depositing decorative and technical layers of black ruthenium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07006380A EP1975282B1 (fr) 2007-03-28 2007-03-28 Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir.

Publications (2)

Publication Number Publication Date
EP1975282A1 EP1975282A1 (fr) 2008-10-01
EP1975282B1 true EP1975282B1 (fr) 2009-11-18

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EP07006380A Active EP1975282B1 (fr) 2007-03-28 2007-03-28 Electrolyte et procédé de dépôt électrolytique de couches décoratives et techniques de ruthénium noir.

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Country Link
US (1) US8211286B2 (fr)
EP (1) EP1975282B1 (fr)
JP (1) JP5449130B2 (fr)
KR (1) KR101416253B1 (fr)
CN (1) CN101675185B (fr)
AT (1) ATE449201T1 (fr)
BR (1) BRPI0809382A2 (fr)
DE (1) DE502007002036D1 (fr)
HK (1) HK1138044A1 (fr)
TW (1) TWI427195B (fr)
WO (1) WO2008116545A1 (fr)

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DE102011105207B4 (de) * 2011-06-17 2015-09-10 Umicore Galvanotechnik Gmbh Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge und Artikel
CN107722361B (zh) * 2017-09-26 2020-01-10 同济大学 一种纳米氨基三亚甲基膦酸镁负载还原氧化石墨烯阻燃剂的制备方法
DE102019109188B4 (de) * 2019-04-08 2022-08-11 Umicore Galvanotechnik Gmbh Verwendung eines Elektrolyten zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten
CN110965088A (zh) * 2019-08-27 2020-04-07 周大福珠宝金行（深圳）有限公司 一种黄金的复古工艺以及复古黄金
CN115261937B (zh) * 2022-03-22 2024-12-13 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
CN115787010B (zh) * 2022-12-02 2024-11-12 周大福珠宝文化产业园(武汉)有限公司 黑钌镀液及其在复古黄金或铂金等饰品制备中的应用

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EP1975282A1 (fr) 2008-10-01
HK1138044A1 (en) 2010-08-13
WO2008116545A1 (fr) 2008-10-02
CN101675185A (zh) 2010-03-17
BRPI0809382A2 (pt) 2014-09-09
DE502007002036D1 (de) 2009-12-31
KR20090123928A (ko) 2009-12-02
ATE449201T1 (de) 2009-12-15
US20100051468A1 (en) 2010-03-04
JP5449130B2 (ja) 2014-03-19
KR101416253B1 (ko) 2014-07-09
TW200914650A (en) 2009-04-01
JP2010522277A (ja) 2010-07-01
TWI427195B (zh) 2014-02-21
CN101675185B (zh) 2011-04-13
US8211286B2 (en) 2012-07-03

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