EP2669407B1 - Bains galvaniques pour obtenir un alliage d'or de bas carat, et procédé galvanique qui utilise ces bains - Google Patents
Bains galvaniques pour obtenir un alliage d'or de bas carat, et procédé galvanique qui utilise ces bains Download PDFInfo
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- EP2669407B1 EP2669407B1 EP13170067.6A EP13170067A EP2669407B1 EP 2669407 B1 EP2669407 B1 EP 2669407B1 EP 13170067 A EP13170067 A EP 13170067A EP 2669407 B1 EP2669407 B1 EP 2669407B1
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- EP
- European Patent Office
- Prior art keywords
- salts
- galvanic
- amounts
- gold
- baths
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 8
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 7
- 239000003353 gold alloy Substances 0.000 title claims description 7
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002343 gold Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002471 indium Chemical class 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- GQLPWHMYJOSZCR-UHFFFAOYSA-N (diphosphonoamino)phosphonic acid Chemical compound OP(O)(=O)N(P(O)(O)=O)P(O)(O)=O GQLPWHMYJOSZCR-UHFFFAOYSA-N 0.000 claims description 2
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical class SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 2
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical class SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 claims description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 claims description 2
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229940001468 citrate Drugs 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- KFGJUQRJVQDJHL-UHFFFAOYSA-N ethanethiol Chemical compound CCS.CCS KFGJUQRJVQDJHL-UHFFFAOYSA-N 0.000 claims description 2
- 229940093495 ethanethiol Drugs 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- -1 ethylenediamine tetramethyl phosphonic acid Chemical compound 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004149 thio group Chemical group *S* 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 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 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 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
- MFIHOCAEOJNSOL-UHFFFAOYSA-N [Ag]C#N Chemical class [Ag]C#N MFIHOCAEOJNSOL-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate 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
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- 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 invention relates to the field of compounds used in galvanic processes, in particular galvanic baths for obtaining a low-carat gold alloy, and to the galvanic process for obtaining said alloy.
- Galvanic baths containing considerable amounts of toxic substances, such as cyanides, and heavy metals, which are also toxic and difficult to remove, for example cadmium, in the matrix have been used for decades to obtain a gold alloy containing less than 75% by weight of gold as metal (corresponding to a gold alloy of 18 carats or less).
- baths of this type also include baths that utilise cyanide in the matrix or that, although they do not contain cyanide in the matrix, contain other doped elements of a certain toxicity.
- US4358351 describes a bath containing gold, copper, zinc, free cyanide and arsenic as gloss additive
- US4487664 describes a bath containing gold-silver and free cyanide
- US5085744 describes a bath containing gold, copper, zinc, free cyanide and antimony as gloss additive
- US4687557 describes a bath containing gold, copper, and cadmium devoid of free cyanide in solution.
- WO 2009/037180 describes a gold alloy plating bath comprising gold, copper and indium ions and free cyanide.
- the present invention makes it possible to satisfy the above-mentioned needs due to alkaline galvanic baths according to claim 1.
- galvanic bath means the aqueous solutions in which the surfaces to be treated by means of the galvanic process are immersed.
- the gold salts are preferably selected from: potassium dicyanoaurate, potassium tetracyanoaurate, ammonium cyanoaurate, or a combination thereof.
- the amount of gold calculated on the basis of the respective salts, is between 0.7 and 4 g/L, preferably between 1.5 and 3 g/L, in order to achieve the desired efficiency and thicknesses.
- copper salts means, for example: sulfate, phosphate, pyrophosphate, chloride, or other salts that are stable under the working conditions of the bath.
- Copper calculated on the basis of the respective salts, is present in an amount between 0.3 and 2.5 g/L, preferably between 0.5 and 2 g/L, in relation to the desired carat value in the 12 - 18 carat range.
- Indium salts useful in accordance with the invention are, for example: chloride, sulfate, citrate, tartrate, gluconate, or any other organic or amine complex compatible with the working conditions of the bath.
- the concentration of indium ranges from 0.1 to 2 g/L, preferably from 0.5 to 1,5 g/L, in relation to the desired carat value in the 12 - 18 carat range.
- the matrix of the bath is formed by polycarboxylic acid salts having both buffer characteristics and complexing power, such as citrates, tartrates, gluconates, maleates, malonates, possibly in combination with the corresponding acids for creation of the expedient buffer, and possibly mixed together in order to achieve the expedient complexing power.
- buffer characteristics and complexing power such as citrates, tartrates, gluconates, maleates, malonates, possibly in combination with the corresponding acids for creation of the expedient buffer, and possibly mixed together in order to achieve the expedient complexing power.
- These acids and the respective salts are each used in an amount ranging from 30 to 150 g/L, more commonly from 50 to 100 g/L.
- Complexing agents that can be expediently used in order to improve the stability of the metals in solution and to regulate the properties thereof in alloy include, for example, ethylenediaminetetraacetic acid and salts thereof, etidronic acid and salts thereof, ethylenediamine tetramethyl phosphonic acid and salts thereof, iminodiacetic acid and salts thereof, nitrilotriphosphonic acid and salts thereof, and nitrilotriacetic acid and salts thereof; these complexing agents normally being used in amounts ranging from 1 to 50 g/L according to the complexing power of each one thereof, a person skilled in the art knowing which complexing agent will be the most suitable for use and in what amounts and combinations, according to the desired carat value in the 12 - 18 carat range.
- a complexing and regulatory action of the alloy metals is due to the amine component of the bath.
- the amines used for this purpose are triethylenetetramine, diethylenetetramine, ethylenediamine and tetraethylenepentamine.
- the amine in question is used in amounts ranging from 0.05 to 1 g/L, more expediently from 0.1 to 0.7 g/L, depending on the desired percentage of indium in alloy, within the carat range from 12 to 18 carats.
- the bath may also obviously contain other components normally used in galvanic processes for their glossing and surfactant action.
- elements such as silver, tellurium, bismuth, iron, zinc, iridium, rhenium, vanadium, molybdenum, tungsten, in such a form so as to be soluble and stable under the working conditions; the amounts to be used range from 0.005 to 0.2 g/L of element as such, and more in particular from 0.010 to 0.1 g/L.
- the formulations according to the invention may also comprise sulfurated compounds, such as organic thiols belonging to the classes of mercaptotetrazoles, mercaptopyrimidines, mercaptopyrrols, mercaptoimidazoles and mercaptotriazoles, possibly containing a sulfur atom in the aromatic ring, possibly having a nitrogen ring condensed with a benzene ring, having one or more thio groups.
- sulfurated compounds such as organic thiols belonging to the classes of mercaptotetrazoles, mercaptopyrimidines, mercaptopyrrols, mercaptoimidazoles and mercaptotriazoles, possibly containing a sulfur atom in the aromatic ring, possibly having a nitrogen ring condensed with a benzene ring, having one or more thio groups.
- the surfactants have both glossing and surfactant action, and those used normally within galvanic scope in baths having matrices of this type are used in this invention: a person skilled in the art will be able to identify the most suitable type to use; however, the amounts used are never greater than 0.005 L/L of an aqueous solution thereof (10% w/v): higher doses lower the efficiency of the bath and create interference with the regular properties of the metals in alloy.
- the bath preferably functions in a pH range between 7 and 12, and more expediently between 8 and 10; the pH is regulated with organic acids belonging to the selected buffer pair, or with mineral acids such as sulfuric acid, phosphoric acid, sulfamic acid, methanesulfonic acid, pyridinesulfonic acid, or with alkali metal hydroxides, such as potassium and sodium.
- organic acids belonging to the selected buffer pair, or with mineral acids such as sulfuric acid, phosphoric acid, sulfamic acid, methanesulfonic acid, pyridinesulfonic acid, or with alkali metal hydroxides, such as potassium and sodium.
- the pH is not a critical parameter in this formulation for obtaining a precise carat value, but it is fundamental that the pH is alkaline for the stability of the components in solution.
- the working temperature of the galvanic bath in question is preferably between 50°C and 70°C; however, this is not a critical parameter for obtaining a precise carat value.
- the current to be applied to the galvanic bath according to the invention is normally between 0.5 - 3 A/cm 2 , preferably 0.7 - 2 A/cm 2 .
- the application times vary according to the amperage imposed and the desired thickness: with the bath according to the invention, it is possible to obtain deposits having thicknesses up to 500 microns.
- gold alloys in which the gold varies from 50% to 75% (percentages expressed in weight) are obtained by deposit at the cathode of the galvanic cell.
- a bath having the following composition was prepared:
- a current of 0.7 A/cm 2 was applied for 3 minutes to a sheet of nickel-plated brass having a surface area of 0.5 cm 2 , suitably de-greased and re-rinsed with deionised water.
- the sheet was rinsed with deionised water and dried by compressed air.
- a bath having the following composition was prepared:
- the bath was brought to pH 9.5 with potassium hydroxide and heated to 60°C.
- a current of 1.5 A/cm 2 was applied for 5 minutes to a sheet of nickel-plated brass having a surface area of 0.5 cm 2 , suitably de-greased and re-rinsed with deionised water.
- the sheet was rinsed with deionised water and dried by compressed air.
- the surface of the alloy was analysed by electronic scan microscope; the following percentages were found
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Claims (9)
- Bain galvanique comprenant des solutions aqueuses ayant un pH alcalin et comprenant des sels d'or, des sels de cuivre et des sels d'indium, des sels d'acide polycarboxylique organiques, des amines organiques, et éventuellement des agents de complexation, des composés sulfurés, des tensioactifs et d'autres métaux, dans lequel la concentration en indium, calculée sur la base des sels respectifs, va de 0,1 à 2 g/L ;dans lequel lesdites amines organiques sont sélectionnées parmi le groupe constitué de la triéthylènetétramine, de la diéthylènetétramine, de l'éthylènediamine et de la tétraéthylènepentamine ; lesdites amines étant utilisées dans des quantités allant de 0,05 à 1 g/L ;lesdits agents de complexation sont sélectionnés parmi le groupe constitué de l'acide éthylènediaminetétraacétique et de ses sels, de l'acide étidronique et de ses sels, de l'acide éthylènediaminetétraméthylphosphonique et de ses sels, de l'acide iminodiacétique et de ses sels, de l'acide nitrilotriphosphonique et de ses sels, et de l'acide nitrilotriacétique et de ses sels ;lesdits composés sulfurés sont sélectionnés parmi le groupe constitué des thiols organiques appartenant aux classes du 2-(2-pyrazine)éthanethiol, des mercaptotétrazoles, des mercaptopyrimidines, des mercaptopyrrols, des mercaptoimidazoles et des mercaptotriazoles, contenant éventuellement un atome de soufre dans le cycle aromatique, ayant éventuellement un cycle azoté condensé avec un cycle benzénique, ayant un ou plusieurs groupes thio ;lesdits tensioactifs ayant à la fois une action lustrante et tensioactive et étant ceux normalement utilisés au sein de bains galvaniques ayant des matrices formées par lesdits sels d'acide polycarboxylique organiques ; lesdits tensioactifs étant utilisés dans une quantité jamais supérieure à 0,005 L/L d'une solution aqueuse à 10 % p/v de ceux-ci ;lesdits autres métaux ayant une action lustrante sont sélectionnés parmi le groupe constitué de l'argent, du tellure, du bismuth, du fer, du zinc, de l'iridium, du rhénium, du vanadium, du molybdène, du tungstène, sous une forme leur permettant d'être solubles et stables dans les conditions de travail, en quantités entre 0,005 et 0,2 g/L d'élément en tant que tel ;lesdits sels d'acide polycarboxylique ayant à la fois des caractéristiques de tampon et un pouvoir de complexation, éventuellement en combinaison avec les acides correspondants pour la création du tampon opportun, ces acides et les sels respectifs sont chacun utilisés dans une quantité allant de 30 à 150 g/L ;caractérisé en ce que du cyanure n'est pas présent dans la matrice du bain et sa teneur dans la solution galvanique s'explique par sa fonction de contre-ion dans les sels d'or seuls.
- Bain galvanique selon la revendication 1, dans lequel lesdits sels d'or sont sélectionnés parmi : le dicyanoaurate de potassium, le tétracyanoaurate de potassium, le cyanoaurate d'ammonium, ou une combinaison de ceux-ci ; lesdits sels de cuivre sont sélectionnés parmi : le sulfate, le phosphate, le pyrophosphate, le chlorure, ou d'autres sels qui sont stables dans les conditions de travail du bain lui-même, et lesdits sels d'indium sont sélectionnés parmi le chlorure, le sulfate, le citrate, le tartrate, le gluconate, ou un complexe organique ou aminé.
- Bain galvanique selon la revendication 2, dans lequel la quantité d'or va de 0,7 à 4 g/L, de préférence de 1,5 à 3 g/L, la quantité de cuivre est entre 0,3 et 2,5 g/L, de préférence entre 0,5 et 2 g/L.
- Bain galvanique selon l'une quelconque des revendications 1 à 3, dans lequel lesdits sels d'acide polycarboxylique sont sélectionnés parmi : les citrates, les tartrates, les maléates, les malonates, éventuellement en combinaison avec les acides correspondants pour la création du tampon approprié, et éventuellement dans un mélange de leurs mélanges, et de préférence dans des quantités entre 50 et 100 g/L.
- Bain galvanique selon l'une quelconque des revendications 1 à 4, dans lequel lesdites amines sont la triéthylènetétramine et la diéthylènetétramine, de préférence dans des quantités qui varient de 0,1 à 0,7 g/L.
- Bain galvanique selon l'une quelconque des revendications 1 à 5, dans lequel lesdits autres métaux sont utilisés dans des quantités entre 0,010 et 0,1 g/L.
- Bains galvaniques selon les revendications 1 à 6, dans lesquels lesdits composés sulfurés sont présents dans des quantités entre 0,01 et 0,500 g/L, et plus particulièrement dans des quantités entre 0,05 et 0,200 g/L.
- Procédé galvanique pour le placage d'objets avec des alliages d'or de 12 à 18 carats, dans lequel les bains selon les revendications 1 à 7 sont utilisés.
- Procédé galvanique selon la revendication 8, dans lequel ledit procédé est effectué dans une plage de pH entre 7 et 12, à une température entre 50 °C et 70 °C, et avec un courant appliqué entre 0,5 et 3 A/cm2.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT000103A ITFI20120103A1 (it) | 2012-06-01 | 2012-06-01 | Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. |
Publications (2)
Publication Number | Publication Date |
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EP2669407A1 EP2669407A1 (fr) | 2013-12-04 |
EP2669407B1 true EP2669407B1 (fr) | 2022-03-30 |
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Application Number | Title | Priority Date | Filing Date |
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EP13170067.6A Active EP2669407B1 (fr) | 2012-06-01 | 2013-05-31 | Bains galvaniques pour obtenir un alliage d'or de bas carat, et procédé galvanique qui utilise ces bains |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2669407B1 (fr) |
ES (1) | ES2918576T3 (fr) |
IT (1) | ITFI20120103A1 (fr) |
PT (1) | PT2669407T (fr) |
Families Citing this family (4)
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WO2016020812A1 (fr) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Bain électrolytique, procédé de dépôt électrolytique et article obtenu par ledit procédé |
EP2990507A1 (fr) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Composition, utilisation de la composition et procédé pour le dépôt galvanique de couches contenant de l'or |
US20160145756A1 (en) * | 2014-11-21 | 2016-05-26 | Rohm And Haas Electronic Materials Llc | Environmentally friendly gold electroplating compositions and methods |
CN109504991B (zh) * | 2019-01-21 | 2020-08-07 | 南京市产品质量监督检验院 | 一种无氰18k金电铸液、其制备方法及其应用 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL273924A (fr) * | 1961-01-24 | |||
ZA734253B (en) * | 1972-07-10 | 1975-02-26 | Degussa | Electrolytic bath |
DE2244434C3 (de) * | 1972-09-06 | 1982-02-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
US4088549A (en) * | 1976-04-13 | 1978-05-09 | Oxy Metal Industries Corporation | Bright low karat silver gold electroplating |
GB2028873B (en) * | 1978-08-31 | 1982-11-10 | Lea Ronal Uk Ltd | Gold alloy electroplating bath and method |
DE3020765A1 (de) | 1980-05-31 | 1981-12-10 | Degussa Ag, 6000 Frankfurt | Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten |
DE3309397A1 (de) | 1983-03-16 | 1984-09-20 | Degussa Ag, 6000 Frankfurt | Elektrolytisches bad zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen |
GB8501245D0 (en) * | 1985-01-18 | 1985-02-20 | Engelhard Corp | Gold electroplating bath |
CH662583A5 (fr) | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
DE19629658C2 (de) * | 1996-07-23 | 1999-01-14 | Degussa | Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen |
JP4308969B2 (ja) * | 1999-04-28 | 2009-08-05 | セイコーホールディングス株式会社 | めっき皮膜、それを備えた装飾品及びめっき皮膜の製造方法 |
SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
EP2135972A4 (fr) * | 2007-03-02 | 2011-08-24 | Citizen Tohoku Co Ltd | Revêtement d'alliage d'or, stratifié de gaine de revêtement d'alliage d'or et élément de gaine de revêtement d'alliage d'or. |
CH710184B1 (fr) * | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
-
2012
- 2012-06-01 IT IT000103A patent/ITFI20120103A1/it unknown
-
2013
- 2013-05-31 EP EP13170067.6A patent/EP2669407B1/fr active Active
- 2013-05-31 ES ES13170067T patent/ES2918576T3/es active Active
- 2013-05-31 PT PT131700676T patent/PT2669407T/pt unknown
Also Published As
Publication number | Publication date |
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EP2669407A1 (fr) | 2013-12-04 |
ITFI20120103A1 (it) | 2013-12-02 |
ES2918576T3 (es) | 2022-07-19 |
PT2669407T (pt) | 2022-06-28 |
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