US2259270A - Solution for electrolytic deposition of tarnish-resisting silver alloys - Google Patents
Solution for electrolytic deposition of tarnish-resisting silver alloys Download PDFInfo
- Publication number
- US2259270A US2259270A US190600A US19060038A US2259270A US 2259270 A US2259270 A US 2259270A US 190600 A US190600 A US 190600A US 19060038 A US19060038 A US 19060038A US 2259270 A US2259270 A US 2259270A
- Authority
- US
- United States
- Prior art keywords
- solution
- silver
- tarnish
- hydroxide
- electrolytic deposition
- 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
- 229910001316 Ag alloy Inorganic materials 0.000 title description 5
- 230000008021 deposition Effects 0.000 title description 2
- 239000000243 solution Substances 0.000 description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- FJNQSTUXQFLBIS-UHFFFAOYSA-H [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[U+6] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[U+6] FJNQSTUXQFLBIS-UHFFFAOYSA-H 0.000 description 6
- 239000008121 dextrose Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 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 description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229940096017 silver fluoride Drugs 0.000 description 3
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 3
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 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 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- KUKDDTFBSTXDTC-UHFFFAOYSA-N uranium;hexanitrate Chemical compound [U].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUKDDTFBSTXDTC-UHFFFAOYSA-N 0.000 description 2
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 2
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000332 continued effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000007983 food acid Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- -1 uranium tartaric acid Chemical compound 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
Definitions
- This'invention relatesto a solution for use, as an electroplating bath and has for its principal 1 object the provision of a solution which will deposit a silver alloy on the cathode of type which will resist tarnish. All commercial silver plating solutions deposit an electrolytically pure silver plate. Electrolytic silver, due to its extreme purity is more susceptible to tarnish than any alloy of silver. Therefore, silver plated ware is objectionable due to its extreme susceptibility to tarnish from exposure to the atmosphere,and to food products containing sulphur or sulphur compounds.
- the electrolytic bath to which this invention is directed deposits an alloy of silver which is more brilliant and desirable than pure silver and yet which is so tarnish resistant that it might be termed tarnish proof.
- Articles plated by the use of this invention have been subjected to every conceivable food product and food acid and to all types of sulphur and sulphur compounds without the slightest trace of resulting tarnish thereon.
- Another object of the present'invention is-to provide a silver electroplating bath which will deposit a bright plate on all surfaces so that all polishing and burnishing may be eliminated if desired.
- a further object is to provide a silver electrolite havingall of the above noted advantages which will be economical to use; which can be used with present electroplating equipment without change; which will not require specialized training in experience; and which will be non poisonous and absolutely safe to use.
- the preferred improved plating solution comprises the following reagents in substan-' tially the following proportions:
- the above bath is preferably prepared by first dissolving the silver fluoride and the stannic fluoride in approximately two thirds of the water, then dissolving the tartaric acid, dextrose and uranium hydroxide in the remainder of the water.
- the tartaric acid, dextrose and uranium solution is then added-to the silver-stannic fluoride solution.
- the entire solution is constantly stirred boric acid is now added, the stirring being con tinued until the latter is'completely dissolved;
- the resulting solution is now allowed to settle for period of several hours to allow complete dissolution of and any chemical reaction that may take place, and toallow all inert matter to settle out. It is then filtered or decanted, and is ready for use in the plating tank.
- the admixed solution may be stored indefinitely. as a stock solution.
- the plating operation is the usual electroplating procedure and the tank and equipment may be of any standard or desired type. With this solution, however,insoluble anodes are employed, preferably but not necessarily of carbon.
- the work to be'plated,- of course, constitutes the oathode and the metals deposited thereon are drawn from the solution which must be replenished at suitable intervals from the stock solution to maintain the metal ion content of the bath.
- the plating is done at ordinary room temperatures (70 to 80 .F.) and it has been found that a current density of from 2 to 3 amps. per square foot is highly satisfactory.
- uranium hydroxide Precipitate uranium hydroxide from a solution of uranium nitrate by the addition of ammonium hydroxide to the uranium nitrate solution.
- the silver fluoride salt supplies the argenticion' (Ag+) in the solution.
- the stannic fluoride salt supplies the tin-ion Sa++++) in the solution.
- the uranium hydroxide being soluble in water in the presence of an organic a-hydroxy acid (tartaric acid) gives a complex compound and supplies the uranium-ion (U++) in the solution.
- the dextrose is incorporated in the solution as an additional agent, its useful action is mainly to reduce treeing and cause the metals to be deposited in small crystals.
- Boric acid is an additional agent incorporated to serve as a bufier'to regulate the acidity of the solution. 4
- An-electroplating solution comprising: silver fluoride; stannic fluoride; tartaric acid; uranium hydroxide; dextrose; boric acid; and water.
- An electroplating solution consisting of 3 oz. silver fluoride; 2 oz. stannlc fluoride: .4 oz. tartarlc acid; and 2 oz. uranium hydroxide; oz.
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)
Description
Patented Oct. 14, 1941 SOLUTION FOR ELECTROLYTIC DEPOSITION OF TARNISH-RESISTING SILVER ALLOYS James Ryder, Denver, 0010., assignor of one-half to L. Bernard Davis and R. H. Galbreath,
of Denver, Colo.
No Drawing.
both
Application February 15, 1938, Serial No. 190,600
2 Claims. f (01. 204-43) This'invention relatesto a solution for use, as an electroplating bath and has for its principal 1 object the provision of a solution which will deposit a silver alloy on the cathode of type which will resist tarnish. All commercial silver plating solutions deposit an electrolytically pure silver plate. Electrolytic silver, due to its extreme purity is more susceptible to tarnish than any alloy of silver. Therefore, silver plated ware is objectionable due to its extreme susceptibility to tarnish from exposure to the atmosphere,and to food products containing sulphur or sulphur compounds.
The electrolytic bath to which this invention is directed deposits an alloy of silver which is more brilliant and desirable than pure silver and yet which is so tarnish resistant that it might be termed tarnish proof. Articles plated by the use of this invention have been subjected to every conceivable food product and food acid and to all types of sulphur and sulphur compounds without the slightest trace of resulting tarnish thereon.
Another object of the present'invention is-to provide a silver electroplating bath which will deposit a bright plate on all surfaces so that all polishing and burnishing may be eliminated if desired.
A further object is to provide a silver electrolite havingall of the above noted advantages which will be economical to use; which can be used with present electroplating equipment without change; which will not require specialized training in experience; and which will be non poisonous and absolutely safe to use.
Briefly, the preferred improved plating solution comprises the following reagents in substan-' tially the following proportions:
The above bath is preferably prepared by first dissolving the silver fluoride and the stannic fluoride in approximately two thirds of the water, then dissolving the tartaric acid, dextrose and uranium hydroxide in the remainder of the water.
The tartaric acid, dextrose and uranium solution is then added-to the silver-stannic fluoride solution. The entire solution is constantly stirred boric acid is now added, the stirring being con tinued until the latter is'completely dissolved;
The resulting solution is now allowed to settle for period of several hours to allow complete dissolution of and any chemical reaction that may take place, and toallow all inert matter to settle out. It is then filtered or decanted, and is ready for use in the plating tank. The admixed solution may be stored indefinitely. as a stock solution.
The plating operation is the usual electroplating procedure and the tank and equipment may be of any standard or desired type. With this solution, however,insoluble anodes are employed, preferably but not necessarily of carbon. The work to be'plated,- of course, constitutes the oathode and the metals deposited thereon are drawn from the solution which must be replenished at suitable intervals from the stock solution to maintain the metal ion content of the bath.
The plating is done at ordinary room temperatures (70 to 80 .F.) and it has been found that a current density of from 2 to 3 amps. per square foot is highly satisfactory.
The above described method for making the bath is for use when and where the fluorides of silver and tin are available for use. These salts, however, are not usually available on the market as such and it is preferred to prepare the bath from standard available, chemicals as follows:
Precipitate silver hydroxide from a solution of silver nitrate by the addition ofsodium hydroxide to the silver nitrate solution.
Filter the solution and recover the precipitate (silver hydroxideAgzO+HzO AgOH) Precipitate stannous hydroxide from a solution of stannous chloride by the addition of sodium carbonate to the stannous chloride solution.
Filter the solution and recover the precipitate (stannous hydroxide).-
Precipitate uranium hydroxide from a solution of uranium nitrate by the addition of ammonium hydroxide to the uranium nitrate solution.
Filter the solution and recover the precipitate (uranium hydroxide).
Then 'mix the silver hydroxide and the stannous hydroxide together and digest with'hydrofluoric acid, then dilute with water. a
I Dissolve the uraniumhydroxide in a tartari acid solution and add dextrose.
Add the uranium tartaric acid dextrose soluboric acid to the solution and stir until all of the boric acid is dissolved. and agitated during the mixing operation. The Allow the solution to stand for several hours to allow the. complete dissolution of and any chemical reaction that may take place and to allow all inert matter to settle out.
Filter, decanter or syphon oi! the clear liquid.
The silver fluoride salt supplies the argenticion' (Ag+) in the solution. The stannic fluoride salt supplies the tin-ion Sa++++) in the solution. The uranium hydroxide being soluble in water in the presence of an organic a-hydroxy acid (tartaric acid) gives a complex compound and supplies the uranium-ion (U++) in the solution.
The dextrose is incorporated in the solution as an additional agent, its useful action is mainly to reduce treeing and cause the metals to be deposited in small crystals.
Boric acid is an additional agent incorporated to serve as a bufier'to regulate the acidity of the solution. 4
While a preferred form of the invention has claimed anddesired secured by Letters Patent is:
1. An-electroplating solution comprising: silver fluoride; stannic fluoride; tartaric acid; uranium hydroxide; dextrose; boric acid; and water. 2. An electroplating solution consisting of 3 oz. silver fluoride; 2 oz. stannlc fluoride: .4 oz. tartarlc acid; and 2 oz. uranium hydroxide; oz.
boric acid in solution in approximately 1 gallon been described in some detail together with the 20 of water.-
theories which it is believed to best explain its JAMES RYDER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US190600A US2259270A (en) | 1938-02-15 | 1938-02-15 | Solution for electrolytic deposition of tarnish-resisting silver alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US190600A US2259270A (en) | 1938-02-15 | 1938-02-15 | Solution for electrolytic deposition of tarnish-resisting silver alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2259270A true US2259270A (en) | 1941-10-14 |
Family
ID=22702008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US190600A Expired - Lifetime US2259270A (en) | 1938-02-15 | 1938-02-15 | Solution for electrolytic deposition of tarnish-resisting silver alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2259270A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754258A (en) * | 1951-02-07 | 1956-07-10 | Platers Res Corp | Gold alloy plating |
| US3076752A (en) * | 1958-10-17 | 1963-02-05 | Minnesota Mining & Mfg | Developer |
| US4749626A (en) * | 1985-08-05 | 1988-06-07 | Olin Corporation | Whisker resistant tin coatings and baths and methods for making such coatings |
-
1938
- 1938-02-15 US US190600A patent/US2259270A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754258A (en) * | 1951-02-07 | 1956-07-10 | Platers Res Corp | Gold alloy plating |
| US3076752A (en) * | 1958-10-17 | 1963-02-05 | Minnesota Mining & Mfg | Developer |
| US4749626A (en) * | 1985-08-05 | 1988-06-07 | Olin Corporation | Whisker resistant tin coatings and baths and methods for making such coatings |
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