US3238112A - Electroplating of metals using mercapto-metal complex salts - Google Patents
Electroplating of metals using mercapto-metal complex salts Download PDFInfo
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- US3238112A US3238112A US207401A US20740162A US3238112A US 3238112 A US3238112 A US 3238112A US 207401 A US207401 A US 207401A US 20740162 A US20740162 A US 20740162A US 3238112 A US3238112 A US 3238112A
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- metals
- electroplating
- mercapto
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- 238000009713 electroplating Methods 0.000 title claims description 10
- 229910052751 metal Inorganic materials 0.000 title description 16
- 239000002184 metal Substances 0.000 title description 16
- 150000002739 metals Chemical class 0.000 title description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 31
- 239000000243 solution Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- -1 mercapto compounds Chemical class 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- 229960003151 mercaptamine Drugs 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 229940035024 thioglycerol Drugs 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- NBUVVXNTRSKQSQ-UHFFFAOYSA-N 2-sulfanylpropane-1,3-diol Chemical compound OCC(S)CO NBUVVXNTRSKQSQ-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical class [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VILMUCRZVVVJCA-UHFFFAOYSA-M sodium glycolate Chemical compound [Na+].OCC([O-])=O VILMUCRZVVVJCA-UHFFFAOYSA-M 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000003440 toxic substance Substances 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
Definitions
- plating baths containing mercapto compounds have a number of advantages not possessed by conventional plating baths. For example, the need for using such highly toxic substances as cyanide in the baths is eliminated.
- the baths give high efiiciency, both at the anode and at the cathode. They can be used at high pH levels, with their attendant advantages.
- These baths have excellent throwing power, give a high quality plate, and have good conductivity. They also permit the use of copper and tin in their lower valence states, thereby saving plating current.
- the mercapto compounds which can be used according to this invention are those of the formula where R is hydrogen, COOH, an alkyl radical containing from 1 to 4 carbon atoms, or a hydroyalkyl radical containing from 1 to 5 carbon atoms;
- R is hydrogen, COOH, a hydroxyalkyl radical containing from 1 to 4 carbon atoms, or an alkyl radical containing from 1 to 4 carbon atoms;
- n 1 or 2.
- Z-mercaptoethanol Z-mercaptopropanol l-mercaptopropanol-Z Z-mercaptobutanol 2-mercaptobutanol-3 l-thioglycerol 2 thioglycerol a-Thiosorbitol Mercaptoacetic acid Z-mercaptosuccinic acid Mercaptoethylamine
- the metals which can be electrically deposited according to this invention are copper, tin, silver, gold, cadmium and zinc. Alloys of these metals, such as brass, can also be deposited. These metals can be deposited on such other metals as steel, copper and brass.
- the electroplating bath is prepared by dissolving a conventional amount of a salt of the metal to be deposited in an aqueous solution of a mercapto compound which has been previously brought to pH l011 with a stoichiometric amount of sodium or potassium hydroxide.
- the mercapto compound should ordinarily be present at a concentration of from 2 to moles per mole of the metal to be deposited.
- the metals to be deposited are naturally present as salts with the mercapto compound.
- Excess sodium or potassium hydroxide in the bath generally improves plate quality and increases the conductivity of the bath.
- Conventional brightening 3,238,112 Patented Mar. 1, 1966 agents, such as Rochelle salts or sodium hydroxyacetate and other additives, can also be added if desired.
- the plating is then carried out with conventional electr oplating equipment, using ordinary electroplating techmques.
- Example 1 A solution of 45 grams of SnC1 -2H O, milliliters of water and 10 milliliters of concentrated hydrochloric acid was prepared and then diluted to 500 milliliters and adjusted to pH 7 with sodium hydroxide. The resulting precipitate of stannous hydroxide which formed was filtered under vacuum and washed several times with distilled water to remove sodium chloride.
- This precipitate was dissolved in a solution of 75 grams of 2-mercaptoethanol and 150 milliliters of water, previously adjusted to pH 10 with sodium hydroxide.
- This solution was then diluted to 267 milliliters with water and placed in a Hull cell. Five grams of sodium hydroxide were added to the bath.
- This method can also be used to plate silver and gold on brass or copper by substituting 30 grams of Ag(NO or 20 grams of HAuCl -3H O for the SnCl' -2H O. The tallow treatment is omitted.
- Example 2 An electroplating bath was prepared by dissolving 15 grams of cupr-ous oxide in a solution of 75 grams of mercaptoacetic acid in milliliters of water, previously adjusted to pH 10 with sodium hydroxide.
- the resulting copper was bright and attractive over the whole current density range.
- Mercaptoethylamine can be substituted for mercaptoacetic acid in this process, in equivalent amounts, with similar results.
- Example 3 A solution of 20 grams of l-thioglycerol and 20 milliliters of water was adjusted to pH 10 with sodium hydroxide. Ten grams of cadmium oxide were then added to this solution in small quantities and the whole was made up to 267 milliliters with water.
- Example 4 Eight grams of ZnO were dissolved in 200 milliliters of water, and sodium hydroxide was added until the pH of the solution was 9. The resulting precipitate was filtered and washed with water.
- This precipitate was then dissolved in a solution of 200 milliliters of water and 25 grams of Z-mercaptoethanol. The pH of this solution was adjusted to 10 with sodium hydroxide and the solution was then made to 267 milliliters with water.
- This solution was used as an electroplating bath, using a steel cathode, a zinc anode and a current of 0.5 ampere and volts.
- the resulting zinc plate was bright in the intermediate current density range.
- An improved electroplating bath consisting essentially of an aqueous solution of a metal salt of a compound of the formula where R is selected from the group consisting of hydrogen, COOH, alkyl radicals containing from 1 to 4 carbon atoms, and hydroxyalkyl radicals containing from 1 to 5 carbon atoms; and
- X is selected from the group consisting of (CHR),,OH,
- R' is selected from the group consisting of hydrogen, COOH, hydroxyalkyl radicals containing from 1 to 4 carbon atoms and alkyl radicals containing from 1 to 4 carbon atoms;
- n is a whole positive number less than 3 the metal in said salt being selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
- An electroplating bath consisting essentially of an aqueous solution of a Z-mercaptoethanol salt of a metal selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
- a method for the electrodeposition of tin, copper, silver, gold, cadmium and zinc comprising passing an electric current from a suitable anode to a cathode to be plated, through a bath consisting essentially of an aqueous solution of a metal salt of a compound of the formula where R is selected from the group consisting of hydrogen,
- X is selected from the group consisting of (CHR'),,OH,
- R is selected from the group consisting of hydrogen, COOH, hydr-oxyalkyl radicals containing from 1 to 4 carbon atoms and alkyl radicals containing from 1 to 4 carbon atoms;
- n is a whole positive number less than 3 the metal in said salt being selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
- a method for the electrodeposition of tin, copper, silver, gold, cadmium and Zinc comprising passing an electric current from a suitable anode to a cathode to be plated, through an aqueous bath consisting essentially of a Z-mercaptoethanol salt of the metal to be thus deposited.
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- 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)
Description
United States Patent 3,238,112 ELECTROPLATIN G OF METALS USING MER- CAPTO-METAL COMPLEX SALTS John H. Haslam, Landenberg, P2,, assignor to E. I. du
Pont de Nemours and Company, Wilmington, Del., a
corporation of Delaware No Drawing. Filed July 3, 1962, Ser. No. 207,401
4 Claims. (Cl. 20445) {This invention relates to compositions and processes for the electrodeposition of metals. It is more particularly directed to electroplating methods using baths containing mecapto compounds.
It has been found that plating baths containing mercapto compounds have a number of advantages not possessed by conventional plating baths. For example, the need for using such highly toxic substances as cyanide in the baths is eliminated. The baths give high efiiciency, both at the anode and at the cathode. They can be used at high pH levels, with their attendant advantages. These baths have excellent throwing power, give a high quality plate, and have good conductivity. They also permit the use of copper and tin in their lower valence states, thereby saving plating current.
The mercapto compounds which can be used according to this invention are those of the formula where R is hydrogen, COOH, an alkyl radical containing from 1 to 4 carbon atoms, or a hydroyalkyl radical containing from 1 to 5 carbon atoms;
where R is hydrogen, COOH, a hydroxyalkyl radical containing from 1 to 4 carbon atoms, or an alkyl radical containing from 1 to 4 carbon atoms; and
n is 1 or 2.
Preferred for use are Z-mercaptoethanol Z-mercaptopropanol l-mercaptopropanol-Z Z-mercaptobutanol 2-mercaptobutanol-3 l-thioglycerol 2 thioglycerol a-Thiosorbitol Mercaptoacetic acid Z-mercaptosuccinic acid Mercaptoethylamine The metals which can be electrically deposited according to this invention are copper, tin, silver, gold, cadmium and zinc. Alloys of these metals, such as brass, can also be deposited. These metals can be deposited on such other metals as steel, copper and brass.
The electroplating bath is prepared by dissolving a conventional amount of a salt of the metal to be deposited in an aqueous solution of a mercapto compound which has been previously brought to pH l011 with a stoichiometric amount of sodium or potassium hydroxide. The mercapto compound should ordinarily be present at a concentration of from 2 to moles per mole of the metal to be deposited. In the baths, the metals to be deposited are naturally present as salts with the mercapto compound. Excess sodium or potassium hydroxide in the bath generally improves plate quality and increases the conductivity of the bath. Conventional brightening 3,238,112 Patented Mar. 1, 1966 agents, such as Rochelle salts or sodium hydroxyacetate and other additives, can also be added if desired.
The plating is then carried out with conventional electr oplating equipment, using ordinary electroplating techmques.
In order that this invention be better understood, the following examples are submitted:
Example 1 A solution of 45 grams of SnC1 -2H O, milliliters of water and 10 milliliters of concentrated hydrochloric acid was prepared and then diluted to 500 milliliters and adjusted to pH 7 with sodium hydroxide. The resulting precipitate of stannous hydroxide which formed was filtered under vacuum and washed several times with distilled water to remove sodium chloride.
This precipitate was dissolved in a solution of 75 grams of 2-mercaptoethanol and 150 milliliters of water, previously adjusted to pH 10 with sodium hydroxide.
This solution was then diluted to 267 milliliters with water and placed in a Hull cell. Five grams of sodium hydroxide were added to the bath.
Steel plates were used as a cathode and a tin plate was used as an anode. These plates were immersed in the bath and a current of 1 /2 volts Was passed through.
The resulting tin plate was matte-white. Both cathode and anode efliciency were These steel plates were then brightened by dipping them into hot tallow, maintained at 207 C., for approximately 15 seconds.
i This method can also be used to plate silver and gold on brass or copper by substituting 30 grams of Ag(NO or 20 grams of HAuCl -3H O for the SnCl' -2H O. The tallow treatment is omitted.
Example 2 An electroplating bath was prepared by dissolving 15 grams of cupr-ous oxide in a solution of 75 grams of mercaptoacetic acid in milliliters of water, previously adjusted to pH 10 with sodium hydroxide.
This solution was then placed in a Hull cell, 10 grams of sodium hydroxide were added, and the resulting bath was used to electroplate copper on steel, using a copper anode and a current of 2 /2 volts and 1 ampere.
The resulting copper was bright and attractive over the whole current density range.
Mercaptoethylamine can be substituted for mercaptoacetic acid in this process, in equivalent amounts, with similar results.
Example 3 A solution of 20 grams of l-thioglycerol and 20 milliliters of water was adjusted to pH 10 with sodium hydroxide. Ten grams of cadmium oxide were then added to this solution in small quantities and the whole was made up to 267 milliliters with water.
This solution was then placed in a Hull cell, 5 grams of sodium hydroxide were added, and the bath was electrolyzed using a steel cathode, a cadmium anode and a current of 0.5 ampere and 1 volt. The resulting plate was bright and the anode and cathode plating efficiencies were essentially 100%.
Example 4 Eight grams of ZnO were dissolved in 200 milliliters of water, and sodium hydroxide was added until the pH of the solution was 9. The resulting precipitate was filtered and washed with water.
This precipitate was then dissolved in a solution of 200 milliliters of water and 25 grams of Z-mercaptoethanol. The pH of this solution was adjusted to 10 with sodium hydroxide and the solution was then made to 267 milliliters with water.
This solution was used as an electroplating bath, using a steel cathode, a zinc anode and a current of 0.5 ampere and volts.
The resulting zinc plate was bright in the intermediate current density range.
The embodiments of the invention in which an exclusive property or privilege is claimed are:
1. An improved electroplating bath consisting essentially of an aqueous solution of a metal salt of a compound of the formula where R is selected from the group consisting of hydrogen, COOH, alkyl radicals containing from 1 to 4 carbon atoms, and hydroxyalkyl radicals containing from 1 to 5 carbon atoms; and
X is selected from the group consisting of (CHR),,OH,
(CHR'),,'NH and (OHR),, COOH where R' is selected from the group consisting of hydrogen, COOH, hydroxyalkyl radicals containing from 1 to 4 carbon atoms and alkyl radicals containing from 1 to 4 carbon atoms; and
n is a whole positive number less than 3 the metal in said salt being selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
2. An electroplating bath consisting essentially of an aqueous solution of a Z-mercaptoethanol salt of a metal selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
3. A method for the electrodeposition of tin, copper, silver, gold, cadmium and zinc, said method comprising passing an electric current from a suitable anode to a cathode to be plated, through a bath consisting essentially of an aqueous solution of a metal salt of a compound of the formula where R is selected from the group consisting of hydrogen,
COOH, alkyl radicals containing from 1 to 4 carbon atoms, and hydroxyalkyl radicals containing from 1 to 5 carbon atoms; and
X is selected from the group consisting of (CHR'),,OH,
(CHRO NH and (CHR) COOH where R is selected from the group consisting of hydrogen, COOH, hydr-oxyalkyl radicals containing from 1 to 4 carbon atoms and alkyl radicals containing from 1 to 4 carbon atoms; and
n is a whole positive number less than 3 the metal in said salt being selected from the group consisting of tin, copper, silver, gold, cadmium and zinc.
4. A method for the electrodeposition of tin, copper, silver, gold, cadmium and Zinc, said method comprising passing an electric current from a suitable anode to a cathode to be plated, through an aqueous bath consisting essentially of a Z-mercaptoethanol salt of the metal to be thus deposited.
References Cited by the Examiner UNITED STATES PATENTS 1,857,507 5/1932 Hichman et al. 20446 2,113,517 4/1938 Powell et al. 20446 2,495,668 1/1950 Wilson et al 204-52.l
FOREIGN PATENTS 690,978 4/ 1953 Great Britain.
JOHN H. MACK, Primary Examiner.
JOHN R. SPECK, Examiner.
Claims (1)
1. AN IMPROVED ELECTROPLATING BATH CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF A METAL SALT OF A COMPOUND OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US207401A US3238112A (en) | 1962-07-03 | 1962-07-03 | Electroplating of metals using mercapto-metal complex salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US207401A US3238112A (en) | 1962-07-03 | 1962-07-03 | Electroplating of metals using mercapto-metal complex salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3238112A true US3238112A (en) | 1966-03-01 |
Family
ID=22770400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US207401A Expired - Lifetime US3238112A (en) | 1962-07-03 | 1962-07-03 | Electroplating of metals using mercapto-metal complex salts |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3238112A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3520785A (en) * | 1969-04-14 | 1970-07-14 | Robert Duva | Electroplating gold and thiomalate electrolyte therefor |
| JPS5148731A (en) * | 1974-10-24 | 1976-04-27 | Nippon Dento Kogyo Kk | Kin parajiumugokinmetsukiho |
| JPS5337149A (en) * | 1976-09-20 | 1978-04-06 | Toho Kasei Kougiyou Kk | Gold plating method |
| US4126524A (en) * | 1975-03-12 | 1978-11-21 | Technic, Inc. | Silver complex, method of making said complex and method and electrolyte containing said complex for electroplating silver and silver alloys |
| DE2829979A1 (en) * | 1977-07-08 | 1979-01-18 | Systemes Traitements Surfaces | ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY |
| US4246077A (en) * | 1975-03-12 | 1981-01-20 | Technic, Inc. | Non-cyanide bright silver electroplating bath therefor, silver compounds and method of making silver compounds |
| US4247372A (en) * | 1978-08-29 | 1981-01-27 | Learonal, Inc. | Silver plating |
| US4399006A (en) * | 1978-08-29 | 1983-08-16 | Learonal, Inc. | Silver plating |
| US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| USH1136H (en) | 1991-11-29 | 1993-02-02 | The United States Of America As Represented By The Secretary Of The Air Force | Electrolytic deposition and recovery of silver |
| WO2010142437A1 (en) * | 2009-06-09 | 2010-12-16 | Coventya S.P.A. | Cyanide-free electrolyte for galvanic deposition of gold or alloys thereof |
| WO2012076174A3 (en) * | 2010-12-07 | 2013-02-14 | Coventya S.P.A. | Electrolyte for the electrochemical deposition of gold alloys and process for the production thereof |
| CN105648486A (en) * | 2014-11-28 | 2016-06-08 | 李婧 | Preparation method of electroplating liquid of mercapto carboxylic acid metal complex and surface treatment method thereof |
| US20210009785A1 (en) * | 2018-02-19 | 2021-01-14 | Arkema Inc. | Accelerator solutions useful for resin curing |
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| US1857507A (en) * | 1929-10-22 | 1932-05-10 | Eastman Kodak Co | Process for the separation of silver by electrolysis |
| US2113517A (en) * | 1935-01-26 | 1938-04-05 | Johnson Matthey Co Ltd | Electrodeposition of silver |
| US2495668A (en) * | 1946-12-21 | 1950-01-24 | Harshaw Chem Corp | Electrodeposition of copper |
| GB690978A (en) * | 1950-09-15 | 1953-04-29 | Hanson Van Winkle Munning Co | Bright silver plating |
-
1962
- 1962-07-03 US US207401A patent/US3238112A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1857507A (en) * | 1929-10-22 | 1932-05-10 | Eastman Kodak Co | Process for the separation of silver by electrolysis |
| US2113517A (en) * | 1935-01-26 | 1938-04-05 | Johnson Matthey Co Ltd | Electrodeposition of silver |
| US2495668A (en) * | 1946-12-21 | 1950-01-24 | Harshaw Chem Corp | Electrodeposition of copper |
| GB690978A (en) * | 1950-09-15 | 1953-04-29 | Hanson Van Winkle Munning Co | Bright silver plating |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3520785A (en) * | 1969-04-14 | 1970-07-14 | Robert Duva | Electroplating gold and thiomalate electrolyte therefor |
| JPS5148731A (en) * | 1974-10-24 | 1976-04-27 | Nippon Dento Kogyo Kk | Kin parajiumugokinmetsukiho |
| US4126524A (en) * | 1975-03-12 | 1978-11-21 | Technic, Inc. | Silver complex, method of making said complex and method and electrolyte containing said complex for electroplating silver and silver alloys |
| US4246077A (en) * | 1975-03-12 | 1981-01-20 | Technic, Inc. | Non-cyanide bright silver electroplating bath therefor, silver compounds and method of making silver compounds |
| JPS5337149A (en) * | 1976-09-20 | 1978-04-06 | Toho Kasei Kougiyou Kk | Gold plating method |
| DE2829979C3 (en) * | 1977-07-08 | 1990-06-21 | Systemes Traitements Surfaces | AQUEOUS BATH FOR GALVANIC DEPOSITION OF GOLD COPPER CADMIUM ALLOYS |
| DE2829979A1 (en) * | 1977-07-08 | 1979-01-18 | Systemes Traitements Surfaces | ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY |
| US4247372A (en) * | 1978-08-29 | 1981-01-27 | Learonal, Inc. | Silver plating |
| US4399006A (en) * | 1978-08-29 | 1983-08-16 | Learonal, Inc. | Silver plating |
| US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| USH1136H (en) | 1991-11-29 | 1993-02-02 | The United States Of America As Represented By The Secretary Of The Air Force | Electrolytic deposition and recovery of silver |
| WO2010142437A1 (en) * | 2009-06-09 | 2010-12-16 | Coventya S.P.A. | Cyanide-free electrolyte for galvanic deposition of gold or alloys thereof |
| WO2012076174A3 (en) * | 2010-12-07 | 2013-02-14 | Coventya S.P.A. | Electrolyte for the electrochemical deposition of gold alloys and process for the production thereof |
| CN105648486A (en) * | 2014-11-28 | 2016-06-08 | 李婧 | Preparation method of electroplating liquid of mercapto carboxylic acid metal complex and surface treatment method thereof |
| CN105646305A (en) * | 2014-11-28 | 2016-06-08 | 李婧 | Preparation method of mercapto carboxylic acid metal complex |
| US20210009785A1 (en) * | 2018-02-19 | 2021-01-14 | Arkema Inc. | Accelerator solutions useful for resin curing |
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