US3776822A - Gold plating electrolyte - Google Patents
Gold plating electrolyte Download PDFInfo
- Publication number
- US3776822A US3776822A US00238615A US3776822DA US3776822A US 3776822 A US3776822 A US 3776822A US 00238615 A US00238615 A US 00238615A US 3776822D A US3776822D A US 3776822DA US 3776822 A US3776822 A US 3776822A
- Authority
- US
- United States
- Prior art keywords
- gold
- liter
- grams
- sulfite
- metal
- 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 33
- 239000010931 gold Substances 0.000 title abstract description 33
- 229910052737 gold Inorganic materials 0.000 title abstract description 33
- 239000003792 electrolyte Substances 0.000 title abstract description 26
- 238000007747 plating Methods 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 24
- 239000002253 acid Substances 0.000 abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 8
- 150000001340 alkali metals Chemical class 0.000 abstract description 6
- 230000003139 buffering effect Effects 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 14
- 229960003975 potassium Drugs 0.000 description 14
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 235000006408 oxalic acid Nutrition 0.000 description 10
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 7
- -1 alkali metal sulfite Chemical class 0.000 description 7
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical class [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical class [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- NHFMFALCHGVCPP-UHFFFAOYSA-M azanium;gold(1+);sulfite Chemical compound [NH4+].[Au+].[O-]S([O-])=O NHFMFALCHGVCPP-UHFFFAOYSA-M 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 235000019846 buffering salt Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical class [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- KRZKNIQKJHKHPL-UHFFFAOYSA-J tripotassium;gold(1+);disulfite Chemical group [K+].[K+].[K+].[Au+].[O-]S([O-])=O.[O-]S([O-])=O KRZKNIQKJHKHPL-UHFFFAOYSA-J 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000002913 oxalic acids 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
- 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
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 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
- a gold plating electrolyte for providing gold deposits with controlled hardness below 130 Knoop, which contains gold as the sulfite complex, an alkali metal sulfite, a buffering and conducting salt and the combination of a polycarboxylic acid together with a semi-metal brightener.
- the addition of a controlled amount of the polycarboxylic acid and the semi-metal brightener provide for bright, ductile pure gold deposits having a hardness below 130 Knoop, and by altering the quantities of the aforesaid acid and semi-metal, deposits having a hardness below 90 Knoop are obtained.
- the gold electrolyte according to the invention contains:
- the gold sulfite complex is selected from the group consisting of potassium gold sulfite, sodium gold sulfite and ammonium gold sulfite.
- alkali metal or ammonium buffering salts examples include alkali metal or ammonium citrates, borates, phosphates, sulfamates and pyrophosphates.
- the alkali metal sulfites employed are sodium or potassium sulfites.
- polycarboxylic acids which are often used as bulfering or conducting media in gold electrolytes.
- soluble salts of the semi-metal employed are the soluble salts of antimony, arsenic, selenium and tellurium such as potassium antimony tartrate, arsenic trioxide, selenium as selenic acid neutralized with an alkali such as potassium or sodium hydroxide, and tellurium as a soluble salt such as tellurium dioxide dissolvedin potassium or sodium hydroxide.
- the preferred combination of a polycarboxylic acid and semi-metal is oxalic acid and arsenic trioxide.
- the brightening hardness control solution is prepared by warming to dissolve the arsenic trioxide in an aqueous solution of oxalic acid. It has been determined that by increasing or decreasing the concentration of oxalic acid in the brightener or electrolyte, with, for example, the same concentration of arsenic, electrodeposits of varying hardness are obtained. It is preferred that the oxalic acid be added together with the brightening semi-metal.
- EXAMPLE 1 Solution A. Into an amount of water suflicient to form one liter of solution is dissolved: 50 grams oxalic acid crystals and 10 grams arsenic as arsenic trioxide.
- EXAMPLE 2 Solution B. Into an amount of water sufiicient to form one liter of solution is dissolved: grams oxalic acid crystals and 10 grams arsenic as arsenic trioxide.
- the polycarboxylic acid and semi-metal brightener combination is added to the solution in the range of 4:1 to 20:1 ratio of polycarboxylic acid to semi-metal.
- the ratio may be 5:1 which gives the deposit a hardness of 90 to 130 Knoop and, preferably, the ratio may be :1 which gives the deposit a hardness of below 90 Knoop.
- the quantity of such additive in the electrolyte is dependent upon the speed at which the electrolyte is operated.
- the following example illustrates the use of the additive in an electrolyte which is formulated to operate at substantially high current density where the current density is higher than given in Examples 1-4.
- the increase in the concentration of gold and potassium citrate is necessary to operate the electrolyte at such higher current density.
- EXAMPLE 6 Gold as potassium gold cyanide-10 grams/liter Potassium citrate-70 grams/liter Potassium dihydrogen phosphate grams/liter Solution A (from Example 1)3 mls./liter pH adjusted to 6.5 with H PO or KOH The hardness of the deposit plated at 5 ASP was 140 Knoop.
- Example 6 the same hardness of Example 6 is obtained without the use of the combination additive of the invention, i.e. where the polycarboxylic acid (oxalic acid) is eliminated.
- EXAMPLE 7 Gold as potassium gold cyanide10 grams/liter Potassium citrate-70 grams/liter Potassium dihydrogen phosphate-30 grams/liter Arsenic as arsenic trioxide30 mg./liter pH adjusted to 6.5 with H PO or KOH The hardness of the deposit plated at 5 ASP was 140 Knoop.
- Example 6 indicate that the efiect of the hardness control additive is eifective. only in the noncyanide gold electrolytes.
- An aqueous alkaline goldplating electrolyte comprising:
- a bulfering salt selected from the group consisting of alkali metal or ammonium citrates, borates', phosphates, sulfamates and pyrophosphates,
- a semi-metal brightener as metal, selected from the group consisting'of arsenic, antimony, selenium and tellurium, the combination of the non-hydroxy polycarboxylic acid and the semi-metal brightener being in the range of a 4:1 to 20:1 ratio of non-hydroxy polycarboxylic acid to semi-metal brightener, and sufficient alkali metal hydroxide to adjust the pH of the electrolyte to 8-11.
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 |
|---|---|---|---|
| US23861572A | 1972-03-27 | 1972-03-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3776822A true US3776822A (en) | 1973-12-04 |
Family
ID=22898643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00238615A Expired - Lifetime US3776822A (en) | 1972-03-27 | 1972-03-27 | Gold plating electrolyte |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3776822A (it) |
| JP (1) | JPS497129A (it) |
| DE (1) | DE2315309A1 (it) |
| FR (1) | FR2177969B1 (it) |
| GB (1) | GB1430799A (it) |
| IT (1) | IT979980B (it) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981782A (en) * | 1972-07-28 | 1976-09-21 | Johnson Matthey & Co., Limited | Electroplating of gold and gold compounds therefor |
| US3990954A (en) * | 1973-12-17 | 1976-11-09 | Oxy Metal Industries Corporation | Sulfite gold plating bath and process |
| US4435253A (en) | 1983-01-28 | 1984-03-06 | Omi International Corporation | Gold sulphite electroplating solutions and methods |
| US4744871A (en) * | 1986-09-25 | 1988-05-17 | Vanguard Research Associates, Inc. | Electrolyte solution and process for gold electroplating |
| US5277790A (en) * | 1992-07-10 | 1994-01-11 | Technic Incorporated | Non-cyanide electroplating solution for gold or alloys thereof |
| CN105112953A (zh) * | 2015-09-17 | 2015-12-02 | 深圳市瑞世兴科技有限公司 | 无氰镀金液 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH615464A5 (en) * | 1976-06-01 | 1980-01-31 | Systemes Traitements Surfaces | Special compositions and particular additives for gold electrolysis baths and their use |
| US5318687A (en) * | 1992-08-07 | 1994-06-07 | International Business Machines Corporation | Low stress electrodeposition of gold for X-ray mask fabrication |
| CN113046790A (zh) * | 2021-02-04 | 2021-06-29 | 德诚珠宝集团有限公司 | 一种用于黄金无氰电铸工艺的电铸液及其电铸工艺 |
-
1972
- 1972-03-27 US US00238615A patent/US3776822A/en not_active Expired - Lifetime
-
1973
- 1973-03-23 JP JP48033421A patent/JPS497129A/ja active Pending
- 1973-03-23 IT IT48989/73A patent/IT979980B/it active
- 1973-03-26 FR FR7310728A patent/FR2177969B1/fr not_active Expired
- 1973-03-26 GB GB1440073A patent/GB1430799A/en not_active Expired
- 1973-03-27 DE DE2315309A patent/DE2315309A1/de active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981782A (en) * | 1972-07-28 | 1976-09-21 | Johnson Matthey & Co., Limited | Electroplating of gold and gold compounds therefor |
| US3990954A (en) * | 1973-12-17 | 1976-11-09 | Oxy Metal Industries Corporation | Sulfite gold plating bath and process |
| US4435253A (en) | 1983-01-28 | 1984-03-06 | Omi International Corporation | Gold sulphite electroplating solutions and methods |
| DE3400670A1 (de) * | 1983-01-28 | 1984-08-02 | Omi International Corp., Warren, Mich. | Waessriges goldsulfit enthaltendes galvanisches bad und verfahren zur galvanischen abscheidung von gold unter verwendung dieses bades |
| US4744871A (en) * | 1986-09-25 | 1988-05-17 | 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 |
| US5277790A (en) * | 1992-07-10 | 1994-01-11 | Technic Incorporated | Non-cyanide electroplating solution for gold or alloys thereof |
| CN105112953A (zh) * | 2015-09-17 | 2015-12-02 | 深圳市瑞世兴科技有限公司 | 无氰镀金液 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2315309A1 (de) | 1973-10-11 |
| JPS497129A (it) | 1974-01-22 |
| IT979980B (it) | 1974-09-30 |
| FR2177969B1 (it) | 1976-09-10 |
| GB1430799A (en) | 1976-04-07 |
| FR2177969A1 (it) | 1973-11-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ENGELHARD CORPORATION 70 WOOD AVENUE SOUTH, METRO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PHIBRO CORPORATION, A CORP. OF DE;REEL/FRAME:003968/0801 Effective date: 19810518 |