US3929595A - Electrolytic burnished gold bath with higher rate of deposition - Google Patents
Electrolytic burnished gold bath with higher rate of deposition Download PDFInfo
- Publication number
- US3929595A US3929595A US520844A US52084474A US3929595A US 3929595 A US3929595 A US 3929595A US 520844 A US520844 A US 520844A US 52084474 A US52084474 A US 52084474A US 3929595 A US3929595 A US 3929595A
- Authority
- US
- United States
- Prior art keywords
- bath
- sulfonic acid
- acid
- article
- gold
- 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.)
- Expired - Lifetime
Links
- 239000010931 gold Substances 0.000 title claims abstract description 46
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 42
- 230000008021 deposition Effects 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 25
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 claims abstract description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 238000000151 deposition Methods 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- ZKIHLVYBGPFUAD-UHFFFAOYSA-N quinoline-2-sulfonic acid Chemical compound C1=CC=CC2=NC(S(=O)(=O)O)=CC=C21 ZKIHLVYBGPFUAD-UHFFFAOYSA-N 0.000 claims description 6
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- RGOPGRSAYPXWIG-UHFFFAOYSA-N pyridin-2-ylmethanesulfonic acid Chemical compound [O-]S(=O)(=O)CC1=CC=CC=[NH+]1 RGOPGRSAYPXWIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000007792 addition Methods 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- -1 heterocyclic nitrogen containing hydrocarbons Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OBITVHZFHDIQGH-UHFFFAOYSA-N [Au].[K]C#N Chemical compound [Au].[K]C#N OBITVHZFHDIQGH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229960002413 ferric citrate Drugs 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PHRNISIZSLWXBY-UHFFFAOYSA-N 2-methylpyridine-3-sulfonic acid Chemical compound CC1=NC=CC=C1S(O)(=O)=O PHRNISIZSLWXBY-UHFFFAOYSA-N 0.000 description 1
- FCKNSNOLDXDAHG-UHFFFAOYSA-N 2-methylpyridine-4-sulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=CC=N1 FCKNSNOLDXDAHG-UHFFFAOYSA-N 0.000 description 1
- PQDKQNSTGLBIAT-UHFFFAOYSA-N 3-methylpyridin-1-ium-2-sulfonate Chemical compound CC1=CC=CN=C1S(O)(=O)=O PQDKQNSTGLBIAT-UHFFFAOYSA-N 0.000 description 1
- YLZRQBQLRFXQPL-UHFFFAOYSA-N 3-methylpyridine-4-sulfonic acid Chemical compound CC1=CN=CC=C1S(O)(=O)=O YLZRQBQLRFXQPL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YQNKGAZLNOIECR-UHFFFAOYSA-N 4-methylpyridine-3-sulfonic acid Chemical compound CC1=CC=NC=C1S(O)(=O)=O YQNKGAZLNOIECR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-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
- 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 1
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 description 1
- RJQXEKDIFMGQLT-UHFFFAOYSA-N N.[Au]C#N Chemical compound N.[Au]C#N RJQXEKDIFMGQLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- RPZMLZLQSXLAMV-UHFFFAOYSA-N [Au]C#N.[Na] Chemical compound [Au]C#N.[Na] RPZMLZLQSXLAMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 210000003056 antler Anatomy 0.000 description 1
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- AZMMUMQYPBKXHS-UHFFFAOYSA-N gold sodium Chemical compound [Na].[Au] AZMMUMQYPBKXHS-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical compound OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 description 1
- 229960004705 kojic acid Drugs 0.000 description 1
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- PTWLOSARXIJRRJ-UHFFFAOYSA-N pyridin-1-ium-4-sulfonate Chemical compound OS(=O)(=O)C1=CC=NC=C1 PTWLOSARXIJRRJ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- KVGSJGNWRDPVKA-UHFFFAOYSA-N quinoline-5-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=N1 KVGSJGNWRDPVKA-UHFFFAOYSA-N 0.000 description 1
- SXVRECLPTCOMIA-UHFFFAOYSA-N quinoline-8-sulfonic acid Chemical compound C1=CN=C2C(S(=O)(=O)O)=CC=CC2=C1 SXVRECLPTCOMIA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- ABSTRACT There is provided an electrolytic gold bath for the deposition of thicker, bright gold coatings at high rates of deposition.
- the bath contains a heterocyclic azohydrocarbon sulfonic acid or salt thereof, e.g. pyridine sulfonic acid.
- the invention is directed to an electrolytic gold bath for the deposition of thick, bright gold coatings at higher rates of deposition which contain sulfonic acids of heterocyclic nitrogen containing hydrocarbons, i.e. heterocyclic azohydrocarbons.
- N-heterocyclic hydrocarbon sulfonic acids i.e., the compounds consist of carbon, hydrogen, the hetero-N-atom and the sulfonic acid group
- salts of such N-heterocyclic sulfonic acids i.e., the compounds consist of carbon, hydrogen, the hetero-N-atom and the sulfonic acid group
- pyridine sulfonic acid e.g. pyridine-3-sulfonic acid, pyridine-4-sulfonic acid and pyridine-2-sulfonic acid and/or their salts, e.g. water solubles such as salts with alkali metals or ammonium, e.g. the sodium or potassium salts, e.g. the sodium salt of pyridine-3-sulfonic acid and the potassium salt of pyridine-3-sulfonic'acid and/or their simple ring alkyl derivatives, as for example the picoline sulfonic acids, e.g. 2-methylpyridine-3-sulfonic acid, 2-methylpyridine-4-sulfonic acid, 3-methylpyridine-2-sulfonic acid, 3-methylpyridine-4-sulfonic acid and 4-methylpyridine-3-sulfonic acid.
- picoline sulfonic acids e.g. 2-methylpyridine-3-sulfonic acid, 2-methylpyridine-4-sulf
- the sulfonic acid derivatives of nitrogen containing heterocyclic also considerably increases the rate of deposition of the gold layer since the baths can be operated at higher current yields at higher current densities.
- the current density can range from 0.5 to 12 A/dm preferably from 2 to 6 Aldm
- pyridine sulfonic acids and picoline sulfonic acid there can also be added the sulfonic acids of other substituted nitrogen containing heterocyclics, as for example quinoline sulfonic acid, e.g. quinoline sulfonic acids such as quinoline-5 -sulfonic acid and quinoline-8- sulfonic acid.
- quinoline sulfonic acid e.g. quinoline sulfonic acids such as quinoline-5 -sulfonic acid and quinoline-8- sulfonic acid.
- pyridine sulfonic acids, especially pyridine-3-sulfonic acid has proven best.
- the pyridine sulfonic acid or salt and/or derivative is employed in weakly acid gold baths, e.g., pH 3 to 5.5.
- weakly acid gold baths e.g., pH 3 to 5.5.
- gold baths according to the invention for example, have the following composition.
- alkali gold cyanide e.g. sodium gold cyanide or potassium gold cyanide or ammonium gold cyanide.
- a weak organic acid preferably citric acid or tartaric acid
- hydroxide e.g. sodium hydroxide or potassium hydroxide or ammonium hydroxide to adjust the pH to between 3.5 and 5.0 or 5.5.
- Additional suitable weak organic acids include formic acid, lactic acid, kojic acid, itaconic acid, citraconic acid, gluconic acid, glutaric acid, glycolic acid, acetic acid and propionic acid.
- pyridine sulfonic acid 1-20 g/l of pyridine sulfonic acid, preferably 1-10 g/l.
- the buffering action of the weak organic acids added can also be produced by addition of or the use of only other buffers known to be usable in the named pH range as for example phosphates and borates, e.g. dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium metaborate and potassium metaborate.
- buffers known to be usable in the named pH range as for example phosphates and borates, e.g. dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium metaborate and potassium metaborate.
- the bright range of the burnished gold baths of the invention in regard to working parameters such as concentration, temperature, pH-value or current density can be widened considerably by small additions of non-noble metals such as iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium and/or antimony in an amount of 3 to mg/l, preferably 10 to 50 mg/l.
- non-noble metals such as iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium and/or antimony in an amount of 3 to mg/l, preferably 10 to 50 mg/l.
- non-noble metals are normally added in the form of soluble salts, e.g. as salts of the acids set forth above such as citric acid and tartaric acid for example.
- the amounts of foreign metals used in the baths of the invention are considerably below the amounts necessary to produce brightness in the known baths.
- compositions can comprise, consist of'or consist essentially of the materials set forth.
- potassium gold cyanide employed was potassium gold (I) cyanide (potassium cyanoaurite).
- potassium gold (I) cyanide potassium gold (I) cyanide
- sodium cyanoaurite potassium gold (I) cyanide
- alkali gold cyanides such as sodium gold (I) cyanide
- bathtemperatures of 45C were used in the working examples, this can be varied as is conventional in the art, e.g. 30 to 50C.
- EXAMPLE 3 acid resulted only in dirty brown coatings. An improvement also was not produced by variation of the current density, pH-value and temperature which showed the decisive influence of the pyridine sulfonic acid in the baths of the invention.
- EXAMPLE 5 The bath composition and temperature were the same as in Example 4 but at an article motion of 25 cm/sec.
- EXAMPLE 6 The bath composition and temperature were the same as in Example 4 but at an article motion of 25 cm/sec. and simultaneous vibration movement of the bath.
- an aqueous, acidic alkali gold cyanide bath suitable for the electrolytic deposition of gold comprising including in the bath a heterocyclic sulfonic acid selected from the group consisting of pyridine sulfonic acid, picoline sulfonic acid and quinoline sulfonic acid or a water soluble salt of such heterocyclic sulfonic acid in an amount sufficient to provide improved bright gold deposition from the bath.
- a heterocyclic sulfonic acid selected from the group consisting of pyridine sulfonic acid, picoline sulfonic acid and quinoline sulfonic acid or a water soluble salt of such heterocyclic sulfonic acid in an amount sufficient to provide improved bright gold deposition from the bath.
- heterocyclic sulfonic acid is pyridine sulfonic acid or quinoline sulfonic acid.
- a bath according to claim 2 wherein the heterocyclic sulfonic acid is pyridine sulfonic acid.
- a bath according to claim 4 containing 2-15 g/l gold as alkali gold cyanide, 30-200 g/l of a weak organic acid and 1-20 g/l of a pyridine sulfonic acid, said bath having a pH of 3.5 to 5.5.
- a bath according to claim 5 including a buffer capable of maintaining the pH within the range 3.5 to 5.5.
- a bath according to claim 5 also including 5-100 mg/l of iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium or antimony in the form ofa water soluble salt thereof.
- a bath according to claim 7 containing 10-50 mg/l of iron.
- a bath according to claim 5 wherein the weak organic acid is an alka'noic acid or a hydroxyalkanoic acid.
- a bath according to claim 10 wherein the acid is a hydroxyalkanoic acid.
- a bath according to claim 11 wherein the acid is citric acid or tartaric acid.
- a bath according to claim 1 containing 1 to 20 g/l of the heterocyclic sulfonic acid.
- a process of electrolytically depositing a glossy gold coating on an article comprising placing the article in the bath of claim 1 and passing a current therethrough at a current density of 0.5 to 12 A/dm 15.
- a process of electrolytically depositing a glossy gold coating on an article comprising placing the article in the bath of claim 1 and passing a current therethrough at a current density of 2 to 6 A/dm 16.
- a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 5 and passing a current therethrough at a current density of 0.5 to 12 A/dm 17.
- a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 5 and passing a current therethrough at a current density of 2 to 6 Aldm 18.
- a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 7 and passing a current therethrough at a current density of 0.5 to 12 A/dm.
- a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 7 and passing a current therethrough at a current density of 2 to 6 A/dm
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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2355581A DE2355581C3 (de) | 1973-11-07 | 1973-11-07 | Galvanisches Glanzgoldbad mit hoher Abscheidungsgeschwindigkeit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3929595A true US3929595A (en) | 1975-12-30 |
Family
ID=5897412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US520844A Expired - Lifetime US3929595A (en) | 1973-11-07 | 1974-11-04 | Electrolytic burnished gold bath with higher rate of deposition |
Country Status (12)
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150439A1 (en) * | 1983-12-22 | 1985-08-07 | LeaRonal (UK) plc | An acid bath for electrodeposition of gold or gold alloys, an electroplating method and the use of said bath |
| US4670107A (en) * | 1986-03-05 | 1987-06-02 | Vanguard Research Associates, Inc. | Electrolyte solution and process for high speed gold plating |
| US4744871A (en) * | 1986-09-25 | 1988-05-17 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| US4755264A (en) * | 1987-05-29 | 1988-07-05 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| US4767507A (en) * | 1986-05-21 | 1988-08-30 | Engelhard Corporation | Gold electroplating bath |
| DE4040526A1 (de) * | 1989-12-19 | 1991-06-20 | H E Finishing Sa | Bad zur galvanischen abscheidung von goldlegierungen |
| DE4105272A1 (de) * | 1990-02-20 | 1991-08-22 | Enthone Omi Inc | Zusammensetzung und verfahren zur herstellung eines galvanischen ueberzuges |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| US6336962B1 (en) * | 1997-10-08 | 2002-01-08 | Atotech Deutschland Gmbh | Method and solution for producing gold coating |
| US6576114B1 (en) | 1995-11-03 | 2003-06-10 | Enthone Inc. | Electroplating composition bath |
| US6814850B1 (en) | 1999-06-17 | 2004-11-09 | Umicore Galvanotechnik Gmbh | Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same |
| US20050205425A1 (en) * | 2002-06-25 | 2005-09-22 | Integran Technologies | Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents |
| EP1403401A3 (en) * | 2002-09-24 | 2005-09-28 | Northrop Grumman Corporation | Precious alloyed metal solder plating process |
| CN103397356A (zh) * | 2013-07-15 | 2013-11-20 | 苏州苏凯路化学科技有限公司 | 一种无毒镀金用金盐及其合成方法 |
| US10570525B2 (en) * | 2015-01-16 | 2020-02-25 | Hutchinson Technology Incorporated | Gold electroplating solution and method |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8501245D0 (en) * | 1985-01-18 | 1985-02-20 | Engelhard Corp | Gold electroplating bath |
| JPS61276992A (ja) * | 1985-05-30 | 1986-12-06 | Shinko Electric Ind Co Ltd | 電解金めつき液 |
| JPS61276990A (ja) * | 1985-05-30 | 1986-12-06 | Shinko Electric Ind Co Ltd | 電解金めつき液 |
| JPS637390A (ja) * | 1986-06-26 | 1988-01-13 | Nippon Engeruharudo Kk | 金−コバルト合金めつき液 |
| GB9522591D0 (en) * | 1995-11-03 | 1996-01-03 | Enthone Omi Suisse S A | Electroplating processes compositions and deposits |
| JP2011122192A (ja) * | 2009-12-09 | 2011-06-23 | Ne Chemcat Corp | 電解硬質金めっき液及びこれを用いるめっき方法 |
| DE102011114931B4 (de) | 2011-10-06 | 2013-09-05 | Umicore Galvanotechnik Gmbh | Verfahren zur selektiveren, elektrolytischen Abscheidung von Gold oder einer Goldlegierung |
| DE102012004348B4 (de) | 2012-03-07 | 2014-01-09 | Umicore Galvanotechnik Gmbh | Verwendung von organischen Thioharnstoffverbindungen zur Erhöhung der galvanischen Abscheiderate von Gold und Goldlegierungen |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2905601A (en) * | 1957-08-13 | 1959-09-22 | Sel Rex Corp | Electroplating bright gold |
| US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
| US2986498A (en) * | 1954-03-13 | 1961-05-30 | Dehydag Gmbh | Process for the production of metal electrodeposits |
| US3023150A (en) * | 1954-03-22 | 1962-02-27 | Dehydag Gmbh | Bath for the production of metal electroplates |
| US3149058A (en) * | 1959-12-31 | 1964-09-15 | Technic | Bright gold plating process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL273924A (enrdf_load_stackoverflow) * | 1961-01-24 | |||
| USB373094I5 (enrdf_load_stackoverflow) * | 1964-08-26 |
-
1973
- 1973-11-07 DE DE2355581A patent/DE2355581C3/de not_active Expired
-
1974
- 1974-09-14 ES ES430054A patent/ES430054A1/es not_active Expired
- 1974-10-02 NL NLAANVRAGE7413010,A patent/NL186825C/xx not_active IP Right Cessation
- 1974-10-04 IT IT69975/74A patent/IT1020940B/it active
- 1974-10-18 JP JP12022574A patent/JPS5615472B2/ja not_active Expired
- 1974-10-21 GB GB4543774A patent/GB1426849A/en not_active Expired
- 1974-10-30 CH CH1453074A patent/CH603825A5/xx not_active IP Right Cessation
- 1974-11-04 US US520844A patent/US3929595A/en not_active Expired - Lifetime
- 1974-11-05 BR BR9243/74A patent/BR7409243A/pt unknown
- 1974-11-06 BE BE6044809A patent/BE821923A/xx not_active IP Right Cessation
- 1974-11-06 FR FR7436860A patent/FR2249979B1/fr not_active Expired
- 1974-11-06 SE SE7413961A patent/SE7413961L/xx unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2986498A (en) * | 1954-03-13 | 1961-05-30 | Dehydag Gmbh | Process for the production of metal electrodeposits |
| US3023150A (en) * | 1954-03-22 | 1962-02-27 | Dehydag Gmbh | Bath for the production of metal electroplates |
| US2905601A (en) * | 1957-08-13 | 1959-09-22 | Sel Rex Corp | Electroplating bright gold |
| US3149058A (en) * | 1959-12-31 | 1964-09-15 | Technic | Bright gold plating process |
| US2967135A (en) * | 1960-06-08 | 1961-01-03 | Barnet D Ostrow | Electroplating baths for hard bright gold deposits |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150439A1 (en) * | 1983-12-22 | 1985-08-07 | LeaRonal (UK) plc | An acid bath for electrodeposition of gold or gold alloys, an electroplating method and the use of said bath |
| US4591415A (en) * | 1983-12-22 | 1986-05-27 | Learonal, Inc. | Plating baths and methods for electro-deposition of gold or gold alloys |
| US4670107A (en) * | 1986-03-05 | 1987-06-02 | Vanguard Research Associates, Inc. | Electrolyte solution and process for high speed gold plating |
| US4767507A (en) * | 1986-05-21 | 1988-08-30 | Engelhard Corporation | Gold electroplating bath |
| US4744871A (en) * | 1986-09-25 | 1988-05-17 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| US4755264A (en) * | 1987-05-29 | 1988-07-05 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| WO1988009401A1 (en) * | 1987-05-29 | 1988-12-01 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| WO1988009834A1 (en) * | 1987-06-01 | 1988-12-15 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| DE4040526A1 (de) * | 1989-12-19 | 1991-06-20 | H E Finishing Sa | Bad zur galvanischen abscheidung von goldlegierungen |
| DE4040526C3 (de) * | 1989-12-19 | 1998-05-20 | H E Finishing Sa | Bad zur galvanischen Abscheidung von Goldlegierungen |
| US5169514A (en) * | 1990-02-20 | 1992-12-08 | Enthone-Omi, Inc. | Plating compositions and processes |
| DE4105272A1 (de) * | 1990-02-20 | 1991-08-22 | Enthone Omi Inc | Zusammensetzung und verfahren zur herstellung eines galvanischen ueberzuges |
| US6576114B1 (en) | 1995-11-03 | 2003-06-10 | Enthone Inc. | Electroplating composition bath |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| US6336962B1 (en) * | 1997-10-08 | 2002-01-08 | Atotech Deutschland Gmbh | Method and solution for producing gold coating |
| US6814850B1 (en) | 1999-06-17 | 2004-11-09 | Umicore Galvanotechnik Gmbh | Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same |
| US20050205425A1 (en) * | 2002-06-25 | 2005-09-22 | Integran Technologies | Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents |
| EP1403401A3 (en) * | 2002-09-24 | 2005-09-28 | Northrop Grumman Corporation | Precious alloyed metal solder plating process |
| CN103397356A (zh) * | 2013-07-15 | 2013-11-20 | 苏州苏凯路化学科技有限公司 | 一种无毒镀金用金盐及其合成方法 |
| CN103397356B (zh) * | 2013-07-15 | 2017-04-19 | 苏州苏凯路化学科技有限公司 | 一种无毒镀金用金盐及其合成方法 |
| US10570525B2 (en) * | 2015-01-16 | 2020-02-25 | Hutchinson Technology Incorporated | Gold electroplating solution and method |
| US12173423B2 (en) | 2015-01-16 | 2024-12-24 | Hutchinson Technology Incorporated | Gold electroplating solution and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5075531A (enrdf_load_stackoverflow) | 1975-06-20 |
| DE2355581B2 (enrdf_load_stackoverflow) | 1978-11-16 |
| IT1020940B (it) | 1977-12-30 |
| FR2249979B1 (enrdf_load_stackoverflow) | 1976-10-22 |
| FR2249979A1 (enrdf_load_stackoverflow) | 1975-05-30 |
| BE821923A (fr) | 1975-05-06 |
| BR7409243A (pt) | 1976-05-18 |
| NL7413010A (nl) | 1975-05-12 |
| NL186825C (nl) | 1991-03-01 |
| JPS5615472B2 (enrdf_load_stackoverflow) | 1981-04-10 |
| DE2355581C3 (de) | 1979-07-12 |
| CH603825A5 (enrdf_load_stackoverflow) | 1978-08-31 |
| GB1426849A (en) | 1976-03-03 |
| ES430054A1 (es) | 1976-10-16 |
| SE7413961L (enrdf_load_stackoverflow) | 1975-05-09 |
| DE2355581A1 (de) | 1975-05-28 |
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