EP3332044B1 - Tin/copper alloys containing palladium, method for their preparation and use thereof - Google Patents

Tin/copper alloys containing palladium, method for their preparation and use thereof Download PDF

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Publication number
EP3332044B1
EP3332044B1 EP16767356.5A EP16767356A EP3332044B1 EP 3332044 B1 EP3332044 B1 EP 3332044B1 EP 16767356 A EP16767356 A EP 16767356A EP 3332044 B1 EP3332044 B1 EP 3332044B1
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Prior art keywords
cyanide
alloy
palladium
grain
potassium
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German (de)
French (fr)
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EP3332044A2 (en
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Lorenzo Cavaciocchi
Leandro Luconi
Gabriele Gori
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Bluclad SpA
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Bluclad SpA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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

Definitions

  • 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-cyanide 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, optionally zinc and optionally brighteners or grain finishers in traces, meaning in an amount of less than 0,25%, 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, optionally zinc, and optionally brighteners or grain finishers in traces, meaning in an amount of less than 0,25%, 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): Sn 25-45% Zn 0-15% Pd 0.25-10% Cu as needed to 100%
  • the alloys according to the invention may optionally contain brighteners or grain finishers 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: Sn 34-40% Zn 5-10% Pd 0.7- 3% Cu as needed to 100%
  • alloy having the following composition: Cu 52% Sn 38% Zn 8% Pd 2%
  • 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 grain finishers in traces, 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 cyanide, or is derived from metal salts constituting the alloy in the form of cyanide 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 tetra(methylene phosphonic acid) (EDTMPA), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), derivatives or salts of polyhydroxylated organic substances such as
  • 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 in the solutions, including metals such as bismuth, tellurium, gallium, indium, silver, molybdenum, thallium, antimony in traces.
  • the thickness of white bronze deposited is equal to 2 microns.
  • the deposit has a concentration by weight of palladium in the alloy of 1.2%.
  • the deposited alloy has the following composition: Cu 52.4% Sn 38.1% Zn 8.3% Pd 1.2%
  • 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: Cu 54.4% Sn 36.3% Zn 3.8% Pd 5.5%
  • the bronze alloys as described above can be used as a intermediate protective deposit having high resistance between the base material and the 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.

Description

    Field of the invention
  • 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.
    • Background art
  • 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 , for example, 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-cyanide 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%.
  • MD. ARIFUR RAHMAN ET AL: "Experimental Studies and Thermodynamic Assessment of Ternary Cu-Pd-Sn Phase Relations Focusing on the Sn-Rich Alloys", JOURNAL OF ELECTRONIC MATERIALS, vol. 43, no. 1, 4 October 2013 (2013-10-04) pages 176 - 186, XP055269831, ISSN: 0361-5235, DOI: 10.1007/s11664-013-2735-4 discloses a ternary alloy used i.a. for microelectronic packaging.
  • US 5,972,526 describes a Sn-Cu-Pd plate layer used for decorative members.
  • 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.
  • Moreover, the use of the processes described in the above prior art, despite the savings allowed compared to the pure palladium deposition, still remains economically unfavorable for nickel-free metal accessories, especially considering the increase in the deposited palladium thickness in order to overcome the wear tests and the oxidation tests after wear.
  • As seen above, the need to develop new alloys and new processes capable of efficiently meeting industrial demands and being similar to the processes using nickel, both in terms of oxidation resistance and wear resistance (nickel thickness of about 10 microns with a hardness of about 400 Vickers) is therefore clear.
    • Summary of the invention
  • Tin/copper alloys containing palladium, optionally zinc and optionally brighteners or grain finishers in traces, meaning in an amount of less than 0,25%, are described, where the palladium content is from 0.25 to 10% by weight calculated on the total weight of the alloy.
    • Detailed description of the invention
  • The present invention allows to overcome the above drawbacks by means of shiny and bright bronze alloys consisting of copper, tin, palladium, optionally zinc, and optionally brighteners or grain finishers in traces, meaning in an amount of less than 0,25%, 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):
    Sn 25-45%
    Zn 0-15%
    Pd 0.25-10%
    Cu as needed to 100%
  • The alloys according to the invention may optionally contain brighteners or grain finishers 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.
  • Preferably, the alloys according to the invention have the following composition:
    Sn 34-40%
    Zn 5-10%
    Pd 0.7- 3%
    Cu as needed to 100%
  • Particularly preferred is an alloy having the following composition:
    Cu 52%
    Sn 38%
    Zn 8%
    Pd 2%
  • According to a further embodiment thereof, 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 grain finishers in traces, 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 cyanide, or is derived from metal salts constituting the alloy in the form of cyanide 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, if present, 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.
  • Some examples of 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.
  • 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. Moreover, the brighteners and grain finishers commonly used for this purpose may also be included in the solutions, including metals such as bismuth, tellurium, gallium, indium, silver, molybdenum, thallium, antimony in traces.
  • The present invention will be better understood in the light of the following examples.
    • Example 1
  • The following electrolytic solution was prepared:
    • 14 g/L of copper as copper cyanide
    • 10 g/L of tin as potassium or sodium stannate
    • 2 g/L of zinc as zinc oxide or zinc cyanide
    • 0.050 g/L of palladium as a complex of tetramine dichloro-palladium
    • 30 g/L of EDTA
    • 20 g/L sodium or potassium carbonate
    • 50 g/L of potassium cyanide
    • 8 g/L of potassium hydroxide
    • 100 ppm of sodium laurylphosphate
  • A sheet of brass of sized 5 x 3.5 cm, on which a copper layer had been previously deposited, was plated with the solution described above at 60 °C, for 10 minutes at a current of 1 A/dmq.
  • 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.
  • At the scanning electron microscope SEM, the deposit has a concentration by weight of palladium in the alloy of 1.2%.
  • The deposited alloy has the following composition:
    Cu 52.4%
    Sn 38.1%
    Zn 8.3%
    Pd 1.2%
    • Example 2
  • The following electrolytic solution was prepared:
    • 10 g/L of copper as copper cyanide
    • 20 g/L of tin as potassium or sodium stannate
    • 3 g/L of zinc as zinc oxide or zinc cyanide
    • 0.5 g/L of palladium as a complex of tetramine dichloro-palladium
    • 30 g/L of EDTA
    • 20 g/L sodium or potassium carbonate
    • 45 g/L of potassium cyanide
    • 15 g/L of potassium hydroxide
    • 150 ppm of sodium laurylphosphate
  • A sheet of brass of sized 5 x 3.5 cm, on which a copper layer had been previously deposited, was plated with the solution described above at 60 °C, for 10 minutes at a current of 1 A/dmq.
  • The thickness of white bronze deposited is equal to 3 microns.
  • Placing a drop of concentrated nitric acid on the deposit does not lead to the deposit attack in the first 5 minutes of waiting.
  • At the scanning electron microscope SEM, the deposit has a concentration by weight of palladium in the alloy of 5.5%.
  • The deposited alloy has the following composition:
    Cu 54.4%
    Sn 36.3%
    Zn 3.8%
    Pd 5.5%
  • The bronze alloys as described above can be used as a intermediate protective deposit having high resistance between the base material and the 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.

Claims (9)

  1. A bronze alloy having the following composition, wherein the percentages are expressed by weight with respect to the total weight of the alloy: Sn 25-45% Zn 0-15% Pd 0.25-10%
    optionally brighteners or grain finishers in traces, meaning in an amount of less than 0.25%, Cu as needed to 100%
  2. The alloy according to claim 1 comprising: Sn 34-40% Zn 5-10% Pd 0.7- 3%
  3. The alloy according to claim 2 having the following composition: Cu 52% Sn 38% Zn 8% Pd 2%
  4. The alloy according to claims 1 - 3, also containing brighteners or grain finishers in traces.
  5. A process for the preparation of the alloys according to claims 1 - 4 by galvanic electrodeposition, wherein galvanic baths are used consisting of aqueous solutions containing cyanide, Cu, Sn, Pd and optionally Zn and optionally comprising also one or more complexing agents, one or more surfactants, one or more brighteners and deposition grain finishing elements in traces.
  6. The process according to claim 5, wherein the above metals are present in solution as soluble oxides, sulfates, cyanides, ammonia salts and cyanide is in the form of sodium or potassium cyanide, or is derived from the salts of the metals constituting the alloy in the form of cyanide complexes.
  7. The process according to claims 5 and 6, wherein said solutions contain: cyanide 1 - 100 g/L. copper 2-30 g/L with a copper to cyanide ratio comprised between 1:1 and 1:10 calculated based on the potassium or sodium cyanide. tin 2-30 g/L with an amount of free hydroxide in the range of between 0 and 20 g/L calculated on the basis of potassium or sodium hydroxide. zinc 0-5 g/L based on the relative concentration of the other metals. palladium 0.001 g/L - 5 g/L, preferably between 0.005 and 0.5 g/L.
  8. The process according to claims 5 and 6, wherein the solutions also contain: one or more complexing agents, wetting agents and grain finishers.
  9. Use of the alloys according to claims 1 - 4 for plating clothing accessories, costume jewelry, footwear or leather goods, for example buckles, self-locking devices, chains, bracelets, sliders, zippers, hooks, shoe clamps for high fashion.
EP16767356.5A 2015-08-05 2016-08-04 Tin/copper alloys containing palladium, method for their preparation and use thereof Active EP3332044B1 (en)

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ITUB2015A002876A ITUB20152876A1 (en) 2015-08-05 2015-08-05 Tin / copper alloys containing palladium, method for their preparation and use.
PCT/IB2016/054703 WO2017021916A2 (en) 2015-08-05 2016-08-04 Tin/copper alloys containing palladium, method for their preparation and use thereof

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EP3332044A2 EP3332044A2 (en) 2018-06-13
EP3332044B1 true EP3332044B1 (en) 2020-01-01

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CN (1) CN108138263A (en)
HK (1) HK1253577A1 (en)
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Publication number Priority date Publication date Assignee Title
ITUB20152876A1 (en) 2015-08-05 2017-02-05 Bluclad S R L Tin / copper alloys containing palladium, method for their preparation and use.
EP3150744B1 (en) * 2015-09-30 2020-02-12 COVENTYA S.p.A. Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy layer, method for electrochemical deposition of said alloy layer, substrate comprising said alloy layer and uses of the coated substrate
IT201800004235A1 (en) * 2018-04-05 2019-10-05 White bronze alloy, galvanic bath and process to produce the white bronze alloy by electro-galvanic deposition
IT202000011203A1 (en) * 2020-05-15 2021-11-15 Bluclad S P A STAINLESS BRONZE ALLOY AND ITS USE IN GALVANIZED PRODUCTS

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JPH06293990A (en) 1993-04-07 1994-10-21 Nippon Shinkinzoku Kako Kk Sn-cu-pd alloy plated member and plating bath for producing the same
US5972526A (en) 1995-12-07 1999-10-26 Citizen Watch Co., Ltd. Decorative member
US20140055026A1 (en) 2011-03-09 2014-02-27 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
EP2799595A1 (en) 2013-05-03 2014-11-05 Delphi Technologies, Inc. Electric contact element
WO2015039152A1 (en) 2013-09-18 2015-03-26 Ing.W.Garhöfer Gesellschaft M.B.H. Deposition of cu, sn, zn-layers on metallic substrates
WO2017021916A2 (en) 2015-08-05 2017-02-09 Bluclad S.R.L. Tin/copper alloys containing palladium, method for their preparation and use thereof

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JPH06293990A (en) 1993-04-07 1994-10-21 Nippon Shinkinzoku Kako Kk Sn-cu-pd alloy plated member and plating bath for producing the same
US5972526A (en) 1995-12-07 1999-10-26 Citizen Watch Co., Ltd. Decorative member
US20140055026A1 (en) 2011-03-09 2014-02-27 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
EP2799595A1 (en) 2013-05-03 2014-11-05 Delphi Technologies, Inc. Electric contact element
WO2015039152A1 (en) 2013-09-18 2015-03-26 Ing.W.Garhöfer Gesellschaft M.B.H. Deposition of cu, sn, zn-layers on metallic substrates
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RICHARD E DEPOTO AND AL GRUENWALD C., UYEMURA & CO. LTD., & JOERG WEBER AND KLAUS LEYENDECKER, UMICORE GALVANOTECHNIK GMBH: "White Bronze, Copper-Tin-Zinc Tri-metal: Expand- ing Applications and New Developments in a Changing Landscape", ELECTROPLATING, 20 May 2013 (2013-05-20), pages 1 - 16, XP055739739, Retrieved from the Internet <URL:www.pfonline.com/articles/white-bronze-copper-tin-zi nc-tri-metal- ex panding-applications-and-new-developments-in-a-changing-landscape>

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WO2017021916A2 (en) 2017-02-09
EP3332044A2 (en) 2018-06-13
HK1253577A1 (en) 2019-06-21
ITUB20152876A1 (en) 2017-02-05
CN108138263A (en) 2018-06-08

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