EP2669407A1 - Galvanische Bäder zur Herstellung einer niederkarätigen Goldlegierung und galvanischer Prozess diese Bäder verwendend - Google Patents
Galvanische Bäder zur Herstellung einer niederkarätigen Goldlegierung und galvanischer Prozess diese Bäder verwendend Download PDFInfo
- Publication number
- EP2669407A1 EP2669407A1 EP13170067.6A EP13170067A EP2669407A1 EP 2669407 A1 EP2669407 A1 EP 2669407A1 EP 13170067 A EP13170067 A EP 13170067A EP 2669407 A1 EP2669407 A1 EP 2669407A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- galvanic
- salts
- gold
- baths
- bath
- 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
Links
- 238000000034 method Methods 0.000 title claims description 9
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 6
- 239000003353 gold alloy Substances 0.000 title claims description 6
- 239000010931 gold Substances 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 17
- 150000002343 gold Chemical class 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 150000002471 indium Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid 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
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 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
- 239000004094 surface-active agent Substances 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
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 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
- 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- 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 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
- 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
- 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
- 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
- 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
- 125000004149 thio group Chemical group *S* 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
- 238000007747 plating Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 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
- 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
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 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
- 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 description 1
- 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
- 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 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 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
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KFGJUQRJVQDJHL-UHFFFAOYSA-N ethanethiol Chemical compound CCS.CCS KFGJUQRJVQDJHL-UHFFFAOYSA-N 0.000 description 1
- 229940093495 ethanethiol Drugs 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- -1 ethylenediamine tetramethyl phosphonic acid Chemical compound 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
- 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 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
- 150000003573 thiols Chemical class 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).
- 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.
- the present invention makes it possible to satisfy the above-mentioned needs due to alkaline galvanic baths containing: gold salts, copper salts and indium salts, organic polycarboxylic acid salts, organic amines, and possibly complexing agents, surfactants and other metals in minor amounts, such as gloss additives and deposit refiners.
- 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 and diethylenetetramine, but other organic amines, such as ethylenediamine, tetraethylenepentamine and other amines of similar structure, may also perform the same role.
- 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 general effect of these substances is that of regulating the deposition of the gold, improving the uniformity of the deposit and reducing the tendency thereof towards chemical deposition and stain formation.
- the amounts to be used expediently range from 0.01 to 0.500 g/L, and more in particular from 0.05 to 0.200 g/L.
- 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:
- the bath was brought to pH 8.5 with potassium hydroxide and heated to 60°C.
- 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 Au: 74% In: 5% Cu: 22% Corresponding to an alloy definable as 18 carats.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Paints Or Removers (AREA)
- Prevention Of Electric Corrosion (AREA)
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 |
|---|---|
| EP2669407A1 true EP2669407A1 (de) | 2013-12-04 |
| EP2669407B1 EP2669407B1 (de) | 2022-03-30 |
Family
ID=46582807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP13170067.6A Active EP2669407B1 (de) | 2012-06-01 | 2013-05-31 | Galvanische Bäder zur Herstellung einer niederkarätigen Goldlegierung und galvanischer Process verwendent diese Bäder |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2669407B1 (de) |
| ES (1) | ES2918576T3 (de) |
| IT (1) | ITFI20120103A1 (de) |
| PT (1) | PT2669407T (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
| EP2990507A1 (de) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Zusammensetzung, ihre Verwendung und Verfahren zur galvanischen Abscheidung von Gold enthaltenden Schichten |
| EP3023520A1 (de) * | 2014-11-21 | 2016-05-25 | Rohm and Haas Electronic Materials LLC | Umweltfreundliche goldelektroplattierungszusammensetzungen und verfahren |
| CN109504991A (zh) * | 2019-01-21 | 2019-03-22 | 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 |
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| US3174918A (en) * | 1961-01-24 | 1965-03-23 | Sel Rex Corp | Bright gold electroplating |
| US3878066A (en) * | 1972-09-06 | 1975-04-15 | Manfred Dettke | Bath for galvanic deposition of gold and gold alloys |
| US3883409A (en) * | 1972-07-10 | 1975-05-13 | Degussa | Gold alloy electroplating bath |
| US4088549A (en) * | 1976-04-13 | 1978-05-09 | Oxy Metal Industries Corporation | Bright low karat silver gold electroplating |
| GB2028873A (en) * | 1978-08-31 | 1980-03-12 | Lea Ronal Uk Ltd | Gold Alloy Electroplating Bath and Method |
| US4358351A (en) | 1980-05-31 | 1982-11-09 | Degussa Aktiengesellschaft | Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers |
| US4487664A (en) | 1983-03-16 | 1984-12-11 | Degussa Aktiengesellschaft | Method and electrolytic bath for the deposition of low carat bright gold-silver alloy coatings |
| EP0188386A2 (de) * | 1985-01-18 | 1986-07-23 | Engelhard Corporation | Gold-Elektroplattierungsbad |
| US4687557A (en) | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| JP2000319794A (ja) * | 1999-04-28 | 2000-11-21 | Seiko Corp | 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 |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| US20060283714A1 (en) * | 2005-06-02 | 2006-12-21 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
| WO2009037180A1 (fr) * | 2007-09-21 | 2009-03-26 | G. Aliprandini | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques |
| EP2135972A1 (de) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Goldlegierungsbeschichtung, mit goldlegierungsbeschichtung umhülltes laminat und mit goldlegierungsbeschichtung umhülltes element |
-
2012
- 2012-06-01 IT IT000103A patent/ITFI20120103A1/it unknown
-
2013
- 2013-05-31 ES ES13170067T patent/ES2918576T3/es active Active
- 2013-05-31 EP EP13170067.6A patent/EP2669407B1/de active Active
- 2013-05-31 PT PT131700676T patent/PT2669407T/pt unknown
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3174918A (en) * | 1961-01-24 | 1965-03-23 | Sel Rex Corp | Bright gold electroplating |
| US3883409A (en) * | 1972-07-10 | 1975-05-13 | Degussa | Gold alloy electroplating bath |
| US3878066A (en) * | 1972-09-06 | 1975-04-15 | Manfred Dettke | Bath for galvanic deposition of gold and gold alloys |
| US4088549A (en) * | 1976-04-13 | 1978-05-09 | Oxy Metal Industries Corporation | Bright low karat silver gold electroplating |
| GB2028873A (en) * | 1978-08-31 | 1980-03-12 | Lea Ronal Uk Ltd | Gold Alloy Electroplating Bath and Method |
| US4358351A (en) | 1980-05-31 | 1982-11-09 | Degussa Aktiengesellschaft | Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers |
| US4487664A (en) | 1983-03-16 | 1984-12-11 | Degussa Aktiengesellschaft | Method and electrolytic bath for the deposition of low carat bright gold-silver alloy coatings |
| EP0188386A2 (de) * | 1985-01-18 | 1986-07-23 | Engelhard Corporation | Gold-Elektroplattierungsbad |
| US4687557A (en) | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| JP2000319794A (ja) * | 1999-04-28 | 2000-11-21 | Seiko Corp | 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 |
| US20060283714A1 (en) * | 2005-06-02 | 2006-12-21 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
| EP2135972A1 (de) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Goldlegierungsbeschichtung, mit goldlegierungsbeschichtung umhülltes laminat und mit goldlegierungsbeschichtung umhülltes element |
| WO2009037180A1 (fr) * | 2007-09-21 | 2009-03-26 | G. Aliprandini | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
| EP2990507A1 (de) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Zusammensetzung, ihre Verwendung und Verfahren zur galvanischen Abscheidung von Gold enthaltenden Schichten |
| WO2016030290A1 (en) * | 2014-08-25 | 2016-03-03 | Atotech Deutschland Gmbh | Composition, use thereof and method for electrodepositing gold containing layers |
| CN106661751A (zh) * | 2014-08-25 | 2017-05-10 | 德国艾托特克公司 | 用于电沉积含金的层的组合物、其用途以及方法 |
| CN106661751B (zh) * | 2014-08-25 | 2019-11-12 | 德国艾托特克公司 | 用于电沉积含金的层的组合物、其用途以及方法 |
| EP3023520A1 (de) * | 2014-11-21 | 2016-05-25 | Rohm and Haas Electronic Materials LLC | Umweltfreundliche goldelektroplattierungszusammensetzungen und verfahren |
| CN109504991A (zh) * | 2019-01-21 | 2019-03-22 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| ITFI20120103A1 (it) | 2013-12-02 |
| ES2918576T3 (es) | 2022-07-19 |
| EP2669407B1 (de) | 2022-03-30 |
| PT2669407T (pt) | 2022-06-28 |
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