EP3332044A2 - Palladiumhaltige zinn-/kupferlegierungen, verfahren zu deren herstellung und verwendung davon - Google Patents

Palladiumhaltige zinn-/kupferlegierungen, verfahren zu deren herstellung und verwendung davon

Info

Publication number
EP3332044A2
EP3332044A2 EP16767356.5A EP16767356A EP3332044A2 EP 3332044 A2 EP3332044 A2 EP 3332044A2 EP 16767356 A EP16767356 A EP 16767356A EP 3332044 A2 EP3332044 A2 EP 3332044A2
Authority
EP
European Patent Office
Prior art keywords
palladium
cyanide
alloy
alloys
copper
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.)
Granted
Application number
EP16767356.5A
Other languages
English (en)
French (fr)
Other versions
EP3332044B1 (de
Inventor
Lorenzo Cavaciocchi
Leandro Luconi
Gabriele Gori
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.)
Bluclad SpA
Original Assignee
BLUCLAD Srl
BLUCLAD 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=54364603&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3332044(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BLUCLAD Srl, BLUCLAD Srl filed Critical BLUCLAD Srl
Publication of EP3332044A2 publication Critical patent/EP3332044A2/de
Application granted granted Critical
Publication of EP3332044B1 publication Critical patent/EP3332044B1/de
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Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/02Alloys based on copper with tin as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/58Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/005Jewels; Clockworks; Coins

Definitions

  • Tin/copper alloys containing palladium method for their preparation and use thereof
  • the present invention relates to the field of alloys, in particular bronzes containing palladium in small amounts, and to the galvanic baths used for their electrodeposition in galvanic processes.
  • Tin and copper alloys containing palladium are already known due to their resistance as possible low cost substitutes of pure palladium deposits and as substitutes of nickel for objects which must comply with non-allergenic characteristics.
  • Patent JP 06293990 describes an alloy of 10-20% tin, 10-80% copper and 10-50% palladium plus other elements in small amounts, which has color and strength comparable to pure palladium.
  • Patent JP 0978286 describes a galvanic bath for the deposition of copper, tin, zinc and palladium alloys with high concentrations of palladium in non-cyanurate environment.
  • Patent JP 10204677 describes generic tin-palladium alloys where tin is present at a variable concentration in the alloy from 21 to 35%, while palladium is present at a variable concentration in the alloy from 35 to 60%.
  • the above alloys require relatively high concentrations of palladium and thus, the plating bath has a considerable initial cost, moreover while there is a net saving of palladium during plating, since a palladium alloy replaces a pure palladium deposit, there is still a fairly high palladium consumption.
  • Tin/copper alloys containing palladium and optionally zinc are described, where the palladium content is from 0.25 to 10% by weight calculated on the total weight of the alloy.
  • the present invention allows to overcome the above drawbacks by means of shiny and bright bronze alloys consisting of copper, tin, palladium and optionally zinc, which exhibit high oxidation resistance and a greater hardness (therefore, greater wear resistance) and where the palladium is present in small amounts.
  • the low presence of palladium allows to reduce production costs considerably compared to the use of pure palladium and alloys thereof, such as those mentioned above.
  • the alloys according to the present invention have the following composition (the percentages are expressed by weight with respect to the total weight of the alloy):
  • the alloys according to the invention may optionally contain brighteners or grain finishing elements in traces, where traces mean amounts of less than 0.25% by weight of the alloy and brighteners or grain finishers are those normally used for this purpose in this field of activity.
  • the alloys according to the invention have the following composition:
  • the present invention also relates to galvanic baths used for making the alloys according to the invention, where "galvanic baths” means the aqueous solutions used in electrogalvanic processes for the electrodeposition of alloys.
  • the galvanic baths as defined above are therefore aqueous solutions consisting of Cu, Sn, Zn, Pd and cyanide and optionally comprising also one or more complexing agents which, in addition to modulating the performance of alloy metals, ensure stability in solution thereof, one or more surfactants, one or more brighteners and trace elements such as deposit grain finishers, as normally used in the solutions of this type.
  • the cyanide content in the solutions is equal to 1 - 100 g/L.
  • the metals listed above are present in solution as soluble oxides, sulfates, cyanides, ammonia salts and other suitable soluble compounds and the cyanide is in the form of sodium or potassium cyanurate, or is derived from metal salts constituting the alloy in the form of cyanurate complexes, such as for example copper cyanide and zinc cyanide.
  • the copper content in solution is normally from 2 to 30 g/L, more suitably from 5 to 15 g/L, with a ratio of copper to cyanide in the electrolyte preferably from 1 :1 to 1 :10, calculated based on the potassium or sodium cyanide.
  • the tin concentration in the electrolyte can range between 2 and 30 g/L with an amount of free hydroxide in the range from 0 to 20 g/L calculated on the basis of potassium or sodium hydroxide.
  • the Zn content in the solution may be from 0.1 to 5 g/L, based on the relative concentration of the other metals to obtain the alloy of the invention.
  • the content of the fourth component of the alloy, Palladium may range between 0.001 g/L and 5 g/L, preferably to obtain the desired alloy it may range between 0.005 and 0.5 g/L.
  • the solution may further contain one or more complexing agents capable of regulating the deposition of the metal components and ensuring stability in solution, as is known for compositions of this type.
  • complexing agents are for example complexing agents suitable for the purpose, they may be nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), of diethylenetriaminepentaacetic acid (DTPA), phosphonate salts of alkali metals such as ethylenediamine tetra(methylene phosphonic acid) (EDTMPA), 1 -hydroxyethane 1 ,1 -diphosphonic acid (HEDP), derivatives or salts of polyhydroxylated organic substances such as gluconates and more or less complex sugars.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • phosphonate salts of alkali metals such as ethylenediamine t
  • surfactants and mixtures of surfactants well known to those skilled in the art may also be present in the solutions, such as wetting agents of the family of alkyl ether phosphonates, alkyl ether sulfonates, alkyl aryl polyethoxylates and sulfonated derivatives thereof, quaternary ammonium salts of alkanes or aromatic compounds.
  • the brighteners and grain finishers commonly used for this purpose may also be included the solutions, including trace metals such as bismuth, tellurium, gallium, indium, silver, molybdenum, thallium, antimony.
  • the thickness of white bronze deposited is equal to 2 microns. Placing a drop of concentrated nitric acid on the deposit only forms a light brown ring at the interphase between acid, deposit and air. The acid takes about 5 minutes to reach the copper layer which can be attacked.
  • the deposit has a concentration by weight of palladium in the alloy of 1 .2%.
  • the deposited alloy has the following composition:
  • the thickness of white bronze deposited is equal to 3 microns.
  • the deposit has a concentration by weight of palladium in the alloy of 5.5%.
  • the deposited alloy has the following composition:
  • the bronze alloys as described above can be used as a intermediate protective deposit having high resistance between the base material and thr deposits of precious material forming the finish, or if with a higher percentage of palladium, they may be used as a finish itself.
  • the alloy is ideal for plating clothing accessories, costume jewelry, footwear and leather goods (e.g. buckles, self-locking devices, chains, bracelets, sliders, zippers, hooks, shoe clamps, etc.) for high fashion.
  • leather goods e.g. buckles, self-locking devices, chains, bracelets, sliders, zippers, hooks, shoe clamps, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP16767356.5A 2015-08-05 2016-08-04 Palladiumhaltige zinn-/kupferlegierungen, verfahren zu deren herstellung und verwendung davon Active EP3332044B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITUB2015A002876A ITUB20152876A1 (it) 2015-08-05 2015-08-05 Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.
PCT/IB2016/054703 WO2017021916A2 (en) 2015-08-05 2016-08-04 Tin/copper alloys containing palladium, method for their preparation and use thereof

Publications (2)

Publication Number Publication Date
EP3332044A2 true EP3332044A2 (de) 2018-06-13
EP3332044B1 EP3332044B1 (de) 2020-01-01

Family

ID=54364603

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16767356.5A Active EP3332044B1 (de) 2015-08-05 2016-08-04 Palladiumhaltige zinn-/kupferlegierungen, verfahren zu deren herstellung und verwendung davon

Country Status (5)

Country Link
EP (1) EP3332044B1 (de)
CN (1) CN108138263A (de)
HK (1) HK1253577A1 (de)
IT (1) ITUB20152876A1 (de)
WO (1) WO2017021916A2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUB20152876A1 (it) 2015-08-05 2017-02-05 Bluclad S R L Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.
ES2790583T3 (es) * 2015-09-30 2020-10-28 Coventya S P A Baño de galvanoplastia para el depósito electroquímica de una aleación de Cu-Sn-Zn-Pd, procedimiento para el depósito electroquímica de dicha aleación, sustrato que comprende dicha aleación y usos del sustrato
IT201800004235A1 (it) * 2018-04-05 2019-10-05 Lega di bronzo bianco, bagno galvanico e procedimento al fine di produrre la lega di bronzo bianco tramite deposizione elettrogalvanica
IT202000011203A1 (it) * 2020-05-15 2021-11-15 Bluclad S P A Lega di bronzo inossidabile e suo impiego in prodotti galvanizzati

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3029948B2 (ja) * 1993-04-07 2000-04-10 シチズン時計株式会社 Sn−Cu−Pd合金めっき部材、その製造に用いるめっき浴
CN1097644C (zh) * 1995-12-07 2003-01-01 西铁城钟表有限公司 装饰件
US5972526A (en) * 1995-12-07 1999-10-26 Citizen Watch Co., Ltd. Decorative member
EP1930478B1 (de) * 2006-12-06 2013-06-19 Enthone, Inc. Zusammensetzung eines Elektrolyten und Verfahren zur Beschichtung von quaternären Kupferlegierungen
EP2975143B1 (de) 2011-03-09 2018-12-19 SAXONIA Technical Materials GmbH Verfahren zur herstellung von amalgamkugeln
EP2799595A1 (de) * 2013-05-03 2014-11-05 Delphi Technologies, Inc. Elektrisches Kontaktelement
AT514818B1 (de) 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
ITUB20152876A1 (it) 2015-08-05 2017-02-05 Bluclad S R L Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.

Also Published As

Publication number Publication date
HK1253577A1 (zh) 2019-06-21
CN108138263A (zh) 2018-06-08
EP3332044B1 (de) 2020-01-01
ITUB20152876A1 (it) 2017-02-05
WO2017021916A3 (en) 2017-03-16
WO2017021916A2 (en) 2017-02-09

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