EP3067444B1 - Deposition de revetements decoratifs en alliage palladium-fer sur des substances metalliques - Google Patents

Deposition de revetements decoratifs en alliage palladium-fer sur des substances metalliques Download PDF

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Publication number
EP3067444B1
EP3067444B1 EP16156476.0A EP16156476A EP3067444B1 EP 3067444 B1 EP3067444 B1 EP 3067444B1 EP 16156476 A EP16156476 A EP 16156476A EP 3067444 B1 EP3067444 B1 EP 3067444B1
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EP
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Prior art keywords
palladium
iron
electrolyte bath
alloy
electrolyte
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EP16156476.0A
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German (de)
English (en)
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EP3067444A2 (fr
EP3067444A3 (fr
Inventor
Claudia GARHÖFER-ONDREICSKA
Christian GARHÖFER
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Ing W Garhofer GmbH
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Ing W Garhofer GmbH
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Publication of EP3067444A3 publication Critical patent/EP3067444A3/fr
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
    • 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
    • C25D5/10—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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

  • the present invention is directed to an electrolytic bath composition for depositing white, high-gloss, crack-free, abrasion and corrosion-resistant palladium-iron alloys from alkaline aqueous baths, objects and articles coated with these alloys, and a process for producing the coated objects Items.
  • the electrolytes are out JP, 2001-192885, A are also based on ammonium salts and contain additional brighteners and possibly different alloying metals such as iron or tellurium.
  • JP, 2001-181887, A describes palladium-iron alloy baths which are also based on ammonium salts, and additionally contain EDTA.
  • strong chelating agents are generally undesirable in electrolytes since they introduce difficulties in wastewater treatment.
  • JP, 10-046384, A describes palladium alloy baths for the electronics industry. Iron as alloying metal is mentioned, the electrolytes are based on ammonium salts. The examples, however, relate only to palladium-cobalt alloys. Alloys of palladium-iron, palladium-nickel, palladium-rhodium and palladium-ruthenium should be produced in the same way.
  • DE2657925 describes ammonia-free, semi-glossy to bright palladium and palladium alloy baths for electrical engineering, but iron is not mentioned as alloying metal.
  • EP 1396559A1 is an electrolytic bath for the cathodic deposition of binary alloys to form white, corrosion-resistant, crack-free and (high) glossy coatings on at least on their surface metallic or electrically conductive or conductive coated objects known which bath as alloying metals at least one palladium compound as the primary metal and contains at least one iron compound as secondary metal, and for the deposition of a Pd / Fe alloy having a content in the range of 5 to 15 wt% Fe - as an aqueous alkaline solution having a pH of 7.5 to 9 and as essential other components at least one wetting agent from the group of amphoteric surfactants and additionally contains at least one of the usual in palladium baths contained gloss additives and conductive salts, pH stabilizers and voltage reducer, wherein the electrolyte bath has a content of palladium of 0.5 to 15 g / l and of iron from 0.2 to 2 g / l au f réelle.
  • the object of the present invention to develop baths from which high gloss, binary palladium-iron alloys can be deposited without any addition of other metals and.
  • the alloy baths during operation should not present an odor nuisance or health hazard through the release of irritating gases or vapors, and moreover contain no strong complexing agents such as EDTA or NTA, which would cause problems in wastewater treatment.
  • the production is to be cheapened by the use of such alloy baths, and resources of the expensive palladium are spared.
  • Such alloys are therefore particularly well suited for any metallic white decorative coating, e.g. of costume jewelery, but also for industrial applications, especially in the electronics industry.
  • the baths contain 0.5-15 g / l of palladium, 0.2-2 g / l of iron, conductive salts, brighteners and wetting agents. It is possible to deposit layer thicknesses> 5 ⁇ high gloss, crack-free.
  • the corrosion resistance is comparable to pure palladium, the abrasion resistance is better than pure palladium.
  • the invention relates to a novel electrolyte bath for the cathodic deposition of binary alloys with the formation of white, corrosion-resistant, crack-free and (high) glossy coatings on at least metallic or electrically conductive or conductively coated objects on its surface, which bath contains at least one palladium compound as alloying metals.
  • a palladium salt as a primary metal and at least one iron compound, in particular an iron salt, as a secondary metal, which for the deposition of a Pd / Fe alloy with a content in the range of 5 to 15 wt% Fe - as an aqueous, alkaline solution with a pH value of 7.5 to 9, and in addition to the metal compounds mentioned as essential further components at least one wetting agent from the group of amphoteric surfactants, and at least one brightener and conductive salts, pH stabilizers and voltage reducer, wherein the electrolyte bath a Content of P alladium of 0.5 to 15 g / l and iron of 0.2 to 2 g / l and is free of ammonia and ammonium compounds.
  • the new electrolyte bath is characterized in that it contains betaines and sulfobetaines in quantities of 0.5-2 g / l as wetting agents from the group of the amphoteric surfactants, and aromatic N-heterocycles substituted as brightening agents, and as stress relievers saccharin or organic sulfonates, and as conductive salts and / or pH stabilizers, sodium or potassium sulfate, chloride, nitrate, citrate, tartrate, or malonate.
  • the pH of the new alloy bath should be maintained in the range of 7.5 - 9, since at lower pH values (approximately between 7 and 7.5) the incorporation rates of iron decrease. At higher pH values (approximately between 9 and 10), burns occur in the high current density range.
  • the pH is advantageously adjusted by means of sodium or potassium hydroxide.
  • the iron content of the deposited alloy at 5-15 wt .-% Fe since at incorporation rates> 15 wt .- Fe Fe the layers are cracked, and at incorporation rates ⁇ 5% by weight, the deposition receives a milky appearance.
  • palladium in divalent form for example as palladium chloride, sulfate or nitrate, and iron as iron sulfate, chloride, nitrate or citrate are present in the electrolyte bath.
  • an electrolyte bath which is characterized in that it has a content of palladium of 2 to 8 g / l, and more preferably of 4 to 6 g / l and of iron preferably 0.5 to 1 Contains 5 g / l.
  • conductive salts and pH stabilizers such as sodium or potassium sulfate, - nitrate, chloride, citrate, tartrate, or malonate, and further as wetting agents alkyl ether sulfonates, alkyl ether phosphates or fatty alcohol alkoxylates. All conductive salts or pH stabilizers used in the invention are sodium or potassium salts.
  • the total thickness of the binary palladium-iron coating to be achieved in the context of the invention is in each case 0.1 to 5 ⁇ m, in particular approximately 0.5 to 3 ⁇ m, depending on the field of use.
  • a further, electrodeposited final layer of gold and / or another noble metal such as, in particular, rhodium, platinum, ruthenium or an alloy of the same, can be arranged, by means of which the already high usability and the gloss of the coating is still increased.
  • an adherent gold adherent intermediate layer adhered thereto may be disposed on the palladium-iron overlay and an electrolytically deposited, adherent final layer of gold and / or another thereon Noble metal, in particular rhodium, platinum, ruthenium or an alloy of the same.
  • the intermediate layer of adhesive gold may have a thickness of 0.05 to 0.3 microns.
  • the coated new objects or articles can be coated with a final layer of an alloy formed with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) to (30 to 10), in particular of about 80 to 20 his. It is the object of the present invention to adjust the concentration of the metal salts, wetting agents, brighteners and the additional ingredients in the mold and to vary within the weight ratios according to the invention so that the electrolyte solution is clear and remains, so that no metal salts precipitate, and that just according to the invention desired, shiny, adherent, crack-free, abrasion and corrosion resistant layers or coatings are deposited.
  • the working temperature of the electrolyte baths according to the invention is between 35 and 75 ° C.
  • the current density can be set to between 0.01 and 10 amps / dm 2 , depending on the type of coating system.
  • current densities between 0.05 and 0.50 A / dm 2 are particularly preferred.
  • insoluble anodes When using the electrolyte baths according to the invention, various insoluble anodes can be used.
  • insoluble anodes those of a material selected from the group consisting of platinum-plated titanium and iridium-transition metal mixed oxide or combinations of these materials may be used, with platinized titanium anodes being preferred.
  • the production of the objects or articles coated according to the invention is usually carried out as follows: On a respective base material, for example consisting of brass, zinc, iron, steel or their alloys or other materials made conductive at least on its surface is either directly or on a previously applied copper undercoat, deposited from cyanide or non-cyanidic alkaline and / or from acidic copper baths, the new binary palladium-iron alloy is deposited either directly or on Cu / Sn / Zn alloy of cyanide bronze baths applied there.
  • This palladium-iron alloy is in itself a final layer. However, it can be further coated by methods known per se. Other coatings may, as mentioned above, be gold-containing or other noble metal-containing layers, such as those of rhodium, platinum, ruthenium or their alloys.
  • the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
  • a thickness of the palladium layer of about 0.5-5 microns is recommended. Usually a layer thickness of about 1 ⁇ m is considered sufficient.
  • rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
  • the invention further relates to a per se conventional method for cathodic deposition of the binary alloys according to the invention with an Fe content of 5-15% by weight on at least on their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention ,
  • the corrosion resistance of the palladium-iron alloy in comparison with a coating of a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH), produced on the same base material in the SO 2 test is equally good.
  • a brass disc in the palladium-iron electrolyte of example 1 and a brass disc in a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH) were coated with 2 .mu.m. Ansch manend both discs were abraded. The pure palladium was rubbed much earlier than the palladium-iron alloy.
  • a jewelery blank made of die-cast zinc is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
  • a weakly alkaline cyanide-free cleaner degreasing 1018, product of the company Ing. W. Garhöfer GesmbH
  • the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) were 5 microns of copper at 1 A / dm 2 and 50 ° C deposited.
  • the pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 ⁇ m copper leveling and high gloss deposited at 4 A / dm 2 and 25 ° C.
  • the thus coppered part is rinsed and pre-immersed in a 10% KCN solution.
  • the galvanized part of the jewelry performed just as well in the corrosion tests as a jewelery part coated with pure palladium using the same process.

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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)

Claims (5)

  1. Bain électrolytique pour le dépôt cathodique d'alliages binaires avec formation de revêtements blancs, résistants à la corrosion, sans fissure et (hautement) brillants sur des objets qui, au moins au niveau de leur surface, sont métalliques ou électriquement conducteurs ou recouverts d'une couche électriquement conductrice, lequel bain contient comme métaux d'alliage au moins un composé du palladium, en particulier un sel de palladium, comme métal primaire et au moins un composé du fer, en particulier un sel de fer, comme métal secondaire, lequel bain est présent, pour le dépôt d'un alliage Pd/Fe avec une teneur comprise entre 5 et 15 % en poids de fer, sous forme de solution aqueuse alcaline avec une valeur pH de 7,5 à 9 et contient hormis les composés métalliques mentionnés, comme autre composants essentiels, au moins un agent mouillant du groupe des tensioactifs amphotères et au moins un produit brillanteur ainsi que des sels conducteurs, des stabilisateurs de pH et des réducteurs de tension, lequel bain électrolytique présente une teneur en palladium de 0,5 à 15 g/l et en fer de 0,2 à 2 g/l et est exempt d'ammoniac et de composés de l'ammonium,
    caractérisé en ce qu'il contient comme agent mouillant du groupe des tensioactifs amphotères 0,5 à 2 g/l de bétaïne et de sulfobétaïne et comme produit brillanteur des hétérocyles N aromatiques substitués et comme réducteurs de tension de la saccharine ou des sulfonates organiques et comme sels conducteurs et/ou stabilisateurs de pH du sulfate de sodium ou de potassium, du chlorure de sodium ou de potassium, du nitrate de sodium ou de potassium, du citrate de sodium ou de potassium, du tartrate de sodium ou de potassium ou du malonate de sodium ou de potassium.
  2. Bain électrolytique selon la revendication 1, caractérisé en ce que le bain électrolytique présente une teneur en palladium de 2 à 8 g/l, de préférence de 4 à 6 g/l, et en fer de 0,5 à 1,5 g/l.
  3. Bain électrolytique selon la revendication 1 ou 2, caractérisé en ce que les métaux d'alliage contenus dans celui-ci sont présents sous forme bivalente le palladium comme chlorure, sulfate ou nitrate de palladium et le fer comme sulfate, chlorure, nitrate ou citrate de fer III.
  4. Bain électrolytique selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient comme autre agent mouillant du sulfonate d'alkyléther, du phosphate d'alkyléther ou de l'alkoxylate d'alcool gras.
  5. Procédé de fabrication d'objets ou articles, munis d'un revêtement blanc ou d'un revêtement de ce type résistant à la corrosion, sans fissure, fortement résistant à l'abrasion et à l'adhérence, brillant, du groupe des articles de bijouterie ou de décoration, du groupe des composants et éléments électrotechniques ou électroniques en laiton, zinc, étain, fer ou acier ou alliages de ceux-ci ou en un plastique rendu conducteur, dans lequel on dépose un alliage Pd/Fe de préférence sur une couche de substrat métallique, en particulier en cuivre, située sur la surface de l'ébauche d'objet ou article, caractérisé en ce que les objets ou articles à revêtir, le cas échéant après un revêtement de base avec du cuivre, sont soumis à une électrolyse dans un bain électrolytique selon l'une quelconque des revendications 1 à 4 à des températures comprises entre 35 et 75 °C et avec des densités de courant comprises entre 0,1 et 10 A/dm2, en particulier entre 0,2 et 5 A/dm2, en utilisant au moins une anode insoluble.
EP16156476.0A 2015-03-09 2016-02-19 Deposition de revetements decoratifs en alliage palladium-fer sur des substances metalliques Active EP3067444B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ATA50188/2015A AT516876B1 (de) 2015-03-09 2015-03-09 Abscheidung von dekorativen Palladium-Eisen-Legierungsbeschichtungen auf metallischen Substanzen

Publications (3)

Publication Number Publication Date
EP3067444A2 EP3067444A2 (fr) 2016-09-14
EP3067444A3 EP3067444A3 (fr) 2016-12-07
EP3067444B1 true EP3067444B1 (fr) 2019-03-27

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AT (1) AT516876B1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT522158B1 (de) * 2019-05-03 2020-09-15 Iwg Ing W Garhoefer Ges M B H Beschichtungssystem zum Aufbringen durch galvanische Abscheidung auf einen Rohling
US10612149B1 (en) 2019-09-05 2020-04-07 Chow Sang Sang Jewellery Company Limited Platinum electrodeposition bath and uses thereof
AT523922B1 (de) * 2020-09-08 2022-01-15 Iwg Ing W Garhoefer Ges M B H Elektrolytbad für Palladium-Ruthenium-Beschichtungen

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Publication number Priority date Publication date Assignee Title
FR2364980A1 (fr) * 1976-09-17 1978-04-14 Parker Ste Continentale Bain et procede pour le depot electrolytique d'alliages a base de palladium
DE2657925A1 (de) 1976-12-21 1978-06-22 Siemens Ag Ammoniakfreies, waessriges bad zur galvanischen abscheidung von palladium bzw. palladiumlegierungen
DE2906783A1 (de) * 1979-02-22 1980-10-16 Degussa Verfahren zur vorbehandlung von leichtmetallen vor dem galvanisieren
DE19512888A1 (de) * 1995-04-06 1996-10-10 Vacuumschmelze Gmbh Verfahren zur elektrolytischen Beschichtung von Seltene Erden enthaltenden Dauermagneten mit minimaler Oberflächenschädigung
JPH1046384A (ja) 1996-05-10 1998-02-17 Lucent Technol Inc パラジウム合金メッキ浴
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process
GB2382353B (en) * 1999-10-27 2004-10-27 Kojima Chemicals Co Ltd Palladium Plating Solution
JP3601005B2 (ja) 1999-10-27 2004-12-15 小島化学薬品株式会社 パラジウムめっき液
JP3208131B2 (ja) 1999-12-24 2001-09-10 株式会社ビクトリア パラジウム／鉄合金メッキ液及びパラジウム合金メッキ基材
JP4811880B2 (ja) * 2006-01-06 2011-11-09 エントン インコーポレイテッド 艶消し金属層を堆積するための電解液および工程
EP2283170B1 (fr) * 2008-05-07 2012-04-25 Umicore Galvanotechnik GmbH Bains d'électrolyte au pd et au pd-ni
DE502008001789D1 (de) * 2008-11-21 2010-12-23 Umicore Galvanotechnik Gmbh Edelmetallhaltige Schichtfolge für dekorative Artikel
DE102009055828A1 (de) * 2008-12-19 2010-07-01 Merck Patent Gmbh Verfahren zur Herstellung metallbeschichteter Partikel

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Publication number Publication date
EP3067444A2 (fr) 2016-09-14
EP3067444A3 (fr) 2016-12-07
AT516876B1 (de) 2016-11-15
AT516876A1 (de) 2016-09-15

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