EP3332044B1 - Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée - Google Patents
Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- cyanide
- alloy
- palladium
- grain
- potassium
- 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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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 64
- 229910052763 palladium Inorganic materials 0.000 title claims description 37
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims 2
- 229910000881 Cu alloy Inorganic materials 0.000 title description 4
- 229910001128 Sn alloy Inorganic materials 0.000 title description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 239000000956 alloy Substances 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 20
- 239000011135 tin Substances 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910000906 Bronze Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 241000054822 Lycaena cupreus Species 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkyl ether phosphonates Chemical class 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940079864 sodium stannate Drugs 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002677 Pd–Sn Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 235000021310 complex sugar Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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.
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- 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)
Claims (9)
- Alliage de bronze ayant la composition suivante, dans lequel les pourcentages sont exprimés en poids par rapport au poids total de l'alliage :
Sn 25 à 45 % Zn 0 à 15 % Pd 0,25 à 10 % Cu autant nécessaire 100 % que jusqu'à - Alliage selon la revendication 1 comprenant :
Sn 34 à 40 % Zn 5 à 10 % Pd 0,7 à 3 % - Alliage selon la revendication 2 ayant la composition suivante :
Cu 52 % Sn 38 % Zn 8 % Pd 2 % - Alliage selon les revendications 1 à 3, contenant également des brillanteurs ou des agents de finition de grain à l'état de traces.
- Procédé pour la préparation des alliages selon les revendications 1 à 4 par dépôt électrolytique galvanique, dans lequel des bains galvaniques sont utilisés, constitués de solutions aqueuses contenant du cyanure, Cu, Sn, Pd et facultativement Zn et comprenant également facultativement un ou plusieurs agents complexants, un ou plusieurs tensioactifs, un ou plusieurs brillanteurs et des éléments de finition de grain de dépôt à l'état de traces.
- Procédé selon la revendication 5, dans lequel les métaux ci-dessus sont présents en solution sous forme d'oxydes, de sulfates, de cyanures, de sels d'ammoniac solubles et le cyanure est sous forme de cyanure de sodium ou de potassium, ou est dérivé des sels des métaux constituant l'alliage sous la forme de complexes de cyanure.
- Procédé selon les revendications 5 et 6, dans lequel lesdites solutions contiennent :
cyanure 1 à 100 g/L. cuivre 2 à 30 g/L avec un rapport cuivre sur cyanure compris entre 1:1 et 1:10 calculé sur la base du cyanure de potassium ou de sodium. étain 2 à 30 g/L avec une quantité d'hydroxyde libre dans la plage d'entre 0 et 20 g/L calculée sur la base d'hydroxyde de potassium ou de sodium. zinc 0 à 5 g/L sur la base de la concentration relative des autres métaux. palladium 0,001 g/L à 5 g/L, de préférence entre 0,005 et 0,5 g/L. - Procédé selon les revendications 5 et 6, dans lequel les solutions contiennent également : un ou plusieurs agents complexants, des agents mouillants et des agents de finition de grain.
- Utilisation des alliages selon les revendications 1 à 4 pour le placage d'accessoires vestimentaires, de bijoux de fantaisie, de chaussures ou d'articles en cuir, par exemple des boucles, des dispositifs autobloquants, des chaînes, des bracelets, des coulisseaux, des fermetures à glissière, des crochets, des pinces de chaussures pour la haute couture.
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 (fr) | 2015-08-05 | 2016-08-04 | Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3332044A2 EP3332044A2 (fr) | 2018-06-13 |
| EP3332044B1 true EP3332044B1 (fr) | 2020-01-01 |
Family
ID=54364603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP16767356.5A Active EP3332044B1 (fr) | 2015-08-05 | 2016-08-04 | Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3332044B1 (fr) |
| CN (1) | CN108138263A (fr) |
| HK (1) | HK1253577A1 (fr) |
| IT (1) | ITUB20152876A1 (fr) |
| WO (1) | WO2017021916A2 (fr) |
Families Citing this family (4)
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293990A (ja) | 1993-04-07 | 1994-10-21 | Nippon Shinkinzoku Kako Kk | Ｓｎ−Ｃｕ−Ｐｄ合金めっき部材、その製造に用いるめっき浴 |
| 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 (fr) | 2013-05-03 | 2014-11-05 | Delphi Technologies, Inc. | Elément de contact électrique |
| WO2015039152A1 (fr) | 2013-09-18 | 2015-03-26 | Ing.W.Garhöfer Gesellschaft M.B.H. | Dépôt de couches de cu, sn, zn sur des substrats métalliques |
| WO2017021916A2 (fr) | 2015-08-05 | 2017-02-09 | Bluclad S.R.L. | Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097644C (zh) * | 1995-12-07 | 2003-01-01 | 西铁城钟表有限公司 | 装饰件 |
| EP1930478B1 (fr) * | 2006-12-06 | 2013-06-19 | Enthone, Inc. | Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre |
-
2015
- 2015-08-05 IT ITUB2015A002876A patent/ITUB20152876A1/it unknown
-
2016
- 2016-08-04 WO PCT/IB2016/054703 patent/WO2017021916A2/fr active Application Filing
- 2016-08-04 EP EP16767356.5A patent/EP3332044B1/fr active Active
- 2016-08-04 CN CN201680045399.2A patent/CN108138263A/zh active Pending
-
2018
- 2018-10-08 HK HK18112782.7A patent/HK1253577A1/zh unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293990A (ja) | 1993-04-07 | 1994-10-21 | Nippon Shinkinzoku Kako Kk | Ｓｎ−Ｃｕ−Ｐｄ合金めっき部材、その製造に用いるめっき浴 |
| 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 (fr) | 2013-05-03 | 2014-11-05 | Delphi Technologies, Inc. | Elément de contact électrique |
| WO2015039152A1 (fr) | 2013-09-18 | 2015-03-26 | Ing.W.Garhöfer Gesellschaft M.B.H. | Dépôt de couches de cu, sn, zn sur des substrats métalliques |
| WO2017021916A2 (fr) | 2015-08-05 | 2017-02-09 | Bluclad S.R.L. | Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée |
Non-Patent Citations (1)
| Title |
|---|
| 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> |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108138263A (zh) | 2018-06-08 |
| WO2017021916A3 (fr) | 2017-03-16 |
| EP3332044A2 (fr) | 2018-06-13 |
| WO2017021916A2 (fr) | 2017-02-09 |
| HK1253577A1 (zh) | 2019-06-21 |
| ITUB20152876A1 (it) | 2017-02-05 |
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