US3219558A - Bright silver plating bath and process - Google Patents
Bright silver plating bath and process Download PDFInfo
- Publication number
- US3219558A US3219558A US181793A US18179362A US3219558A US 3219558 A US3219558 A US 3219558A US 181793 A US181793 A US 181793A US 18179362 A US18179362 A US 18179362A US 3219558 A US3219558 A US 3219558A
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- United States
- Prior art keywords
- antimony
- silver
- bath
- bright
- soluble
- 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
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052709 silver Inorganic materials 0.000 title claims description 21
- 239000004332 silver Substances 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 10
- 238000007747 plating Methods 0.000 title description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 16
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 229940098221 silver cyanide Drugs 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 150000001463 antimony compounds Chemical class 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- LVAOBEYIJJPYNL-UHFFFAOYSA-N 2-[(1-sulfonaphthalen-2-yl)methyl]naphthalene-1-sulfonic acid Chemical compound C1=CC2=CC=CC=C2C(S(=O)(=O)O)=C1CC1=CC=C(C=CC=C2)C2=C1S(O)(=O)=O LVAOBEYIJJPYNL-UHFFFAOYSA-N 0.000 description 5
- -1 alkali metal salt Chemical class 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 208000006558 Dental Calculus Diseases 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000002895 emetic Substances 0.000 description 3
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 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
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- SZXAQBAUDGBVLT-UHFFFAOYSA-H antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SZXAQBAUDGBVLT-UHFFFAOYSA-H 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VORRFUUQXVSQOQ-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 VORRFUUQXVSQOQ-UHFFFAOYSA-N 0.000 description 1
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Definitions
- the electrodeposition of bright silver has economic advantages in that bufiing is not necessary after plating which results in savings in time and in silver as well in that the usual bufling losses are eliminated.
- This invention is based on the discovery that antimony in combination with an alkali metal salt of methylene bis naphthalene sulfonic acid, when added to a conventional silver plating solution makes it possible for one to obtain fully bright deposits over a wide range of plating conditions.
- the method of addition of the antimony is relatively unimportant.
- halides are not particularly desirable in a silver bath, so the next most common antimony compounds, tartar emetic (potassium automonyl tartrate) and antimony oxide are considered most suitable from the standpoint of availability.
- the potassium salts are most suitable although sodium and lithium salts may be substituted.
- the presence of free caustic soda or potassium hydroxide militates against the addition of ammonium salts.
- the baths may be operated at current densities of 0.1- 5.0 amperes per square decimeter.
- the simple silver bath containing antimony trioxide, antimony potassium tartrate or even the complex antimony ethylene diamine tetraacetic acid or antimony nitriloacetate does not produce full bright deposits over wide current density ranges.
- the simple silver bath containing methylene bis naphthalene sulfonic acid sodium salt produces hazy deposits.
- the presence of both ingredients results in a surprisingly bright electrodeposit.
- a suitable electrolyte for silver plating consists of a soluble silver cyanide and excess alkali cyanide or alternately a silver salt is added to a bath containing excess alkali cyanide resulting in the formation in situ of the complex silver cyanide.
- Cyanide silver plating solutions may vary over rather wide ranges of complex silver cyanide and alkali cyanide. Table I discloses the preferred composition, but for special cases the range may be extended much above and below the optimum. Of course, it is customary toadd carbonates and hydroxides to increase the conductivity and for other reasons. These salts are used in the bright plating process herein described but in no way should they be considered essential to the working of the process, except, as stated previously, the presence of free alkali is helpful in maintaining the antimony in solution.
- Example 1 To a silver bath containing 34 g./l. of silver as potassium silver cyanide and g./l. of potassium cyanide along with 15 g./l. of potassium hydroxide was added 0.2 g./l. of antimony as antimony tartrate. The panel was semi-bright to 2.0 amp./dm. whereas a panel plated in the plain silver bath was semi-bright to 1.3 amp./dm.
- Example 2 With a basic bath of the same composition as in Example I, 0.006 g./l. of the sodium salt of methylene bis naphthalene sulfonic acid produced a panel with a semibright range (to 0.8 amp/dm?) less than that obtained in the bath without the organic sulfonate. Additional methylene bis sulfonic acid, sodium salt, decreased rather than improved the range, showing a semi-bright range of up to only 0.3 amp./dm. with 12 g./l. However, when 0.4 g./l. of antimony was added a full-bright, haze-free deposit was obtained.
- Example 3 To the same basic silver hath given in Example 1 was added 3 g./l. of antimony and 4 g./l. of methylene bis sulfonic acid, sodium salt, whereupon a brilliant deposit, from 0 to 4.0 amp/dim was obtained. The addition of another 0.5 g./l. of naphthalene bis sulfonic acid, sodium salt, had no etfect and it appears there is no practical upper limit for this compound other than economies which dictate using as little as necessary to get full brightness. However, if one adds more than 3 g./l. of antimony the high current density range will show darkening but still bright, areas.
- Example 4 To the standard silver solution (of Example 1, for example) was added 1 g./l. of sodium methylene bis naphthalene sulfonate and 0.2 -g./ l. of antimonous oxide. A brilliant deposit was obtained with a range up to about 3.5 amperes/dmfi.
- Example 5 To the standard silver solution of Example 1 was added 1 g./ 1. of methylene bis naphthalene sulfonate and 0.2 g./l. of antimony chloride. Some precipitation occurred, most of which redissolved. A Hull cell panel plated in the bath shows a bright range from 03.5 amperes/dmfi.
- a process for the deposition of silver consisting of immersing a conductive workpiece in a solution consisting essentially of about 7.5 g./1. to about 112 g./l. of a soluble alkali silver cyanide, about 25 g./l. to about 450 g./l. of a soluble alkali cyanide, about 0.25 g./l. to about 12 g./l. of antimony added as a soluble antimony compound and about .006 to about 38 g./l. of a soluble salt of methylene bis naphthalene sulfonic acid, and
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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 3,219,558 BRIGHT SILVER PLATING BATH AND PROCESS Donald Gardner Foulke, Watchung, Plainfield, N.J.,
assignor to Sel-Rex Corporation, Nutley, N .J., a corporation of New Jersey No Drawing. Filed Mar. 22, 1962, Ser. No. 181,793 4 Claims. (Cl. 204-46) This invention is concerned with the electrodeposition of silver and primarily with the electrodeposition of bright silver.
The electrodeposition of bright silver has economic advantages in that bufiing is not necessary after plating which results in savings in time and in silver as well in that the usual bufling losses are eliminated.
This invention is based on the discovery that antimony in combination with an alkali metal salt of methylene bis naphthalene sulfonic acid, when added to a conventional silver plating solution makes it possible for one to obtain fully bright deposits over a wide range of plating conditions. The method of addition of the antimony is relatively unimportant. However, halides are not particularly desirable in a silver bath, so the next most common antimony compounds, tartar emetic (potassium automonyl tartrate) and antimony oxide are considered most suitable from the standpoint of availability.
A typical bath, showing the possible variations in concentration, is shown in Table I.
The potassium salts are most suitable although sodium and lithium salts may be substituted. The presence of free caustic soda or potassium hydroxide militates against the addition of ammonium salts.
Previously disclosed bright silver processes have employed antimony as a brightener. In one instance, it has beenistipulated that considerable alkali tartrate must be present in the bath and in another, it was stipulated that tartar emetic was unsuitable and that the antimony had to be present in the bath in a very complexed form. Ac cording to the process of this invention excess tartrates are not necessary and a simple antimony compound in conjunction with methylene bis naphthalene sulfonic acid operates to give exceptionally bright deposits. Complex antimony compounds may be employed, however. This simple bath is much less apt to lose its brightening power during operation of the process.
The baths may be operated at current densities of 0.1- 5.0 amperes per square decimeter.
There appears to be a synergistic action with the two additives. The simple silver bath containing antimony trioxide, antimony potassium tartrate or even the complex antimony ethylene diamine tetraacetic acid or antimony nitriloacetate (which is another method for introducing antimony into the bath) does not produce full bright deposits over wide current density ranges. The simple silver bath containing methylene bis naphthalene sulfonic acid sodium salt, produces hazy deposits. However, the presence of both ingredients results in a surprisingly bright electrodeposit.
In order for the bath to yield the brightest deposits over a wide range of current densities it is necessary to maintain an alkalinity equivalent to 5 grams per liter of caustic potash, preferably at 7.5 to 8 grams per liter. At these concentrations, the antimony is kept in solution in the bath.
A number of other addition agents were tried in conjunction with the preferred combination of antimony and naphthalene bis sulfonic acid, sodium salt, including butynediol, ethoxylated butynediol, butenediol ethylene glycol, with no noticeable improvement. As a matter of fact, these as well as selenium compounds and thiocarbamates tend to produce a haze, apparently interfering with the synergistic effect of the antimony-methylene bis sodium naphthalene sulfonate combination.
Specific examples of some of the baths successfully employed to give bright sliver deposits to follow will indicate the broad nature of this discovery and emphasize the importance of the presence of both brighteners in the bath.
It should be stated that a suitable electrolyte for silver plating consists of a soluble silver cyanide and excess alkali cyanide or alternately a silver salt is added to a bath containing excess alkali cyanide resulting in the formation in situ of the complex silver cyanide. Cyanide silver plating solutions may vary over rather wide ranges of complex silver cyanide and alkali cyanide. Table I discloses the preferred composition, but for special cases the range may be extended much above and below the optimum. Of course, it is customary toadd carbonates and hydroxides to increase the conductivity and for other reasons. These salts are used in the bright plating process herein described but in no way should they be considered essential to the working of the process, except, as stated previously, the presence of free alkali is helpful in maintaining the antimony in solution.
Example 1 To a silver bath containing 34 g./l. of silver as potassium silver cyanide and g./l. of potassium cyanide along with 15 g./l. of potassium hydroxide was added 0.2 g./l. of antimony as antimony tartrate. The panel was semi-bright to 2.0 amp./dm. whereas a panel plated in the plain silver bath was semi-bright to 1.3 amp./dm.
Increasing the antimony to 0.4 g./l. improved the brightness and extended the range to 4 amp/rim The addition of 1.2 g./l. of methylene bis sulfonic acid, sodium salt, eliminated all haze producing a brilliant deposit from essentially 0 to 4.0 amp./dm.
Example 2 With a basic bath of the same composition as in Example I, 0.006 g./l. of the sodium salt of methylene bis naphthalene sulfonic acid produced a panel with a semibright range (to 0.8 amp/dm?) less than that obtained in the bath without the organic sulfonate. Additional methylene bis sulfonic acid, sodium salt, decreased rather than improved the range, showing a semi-bright range of up to only 0.3 amp./dm. with 12 g./l. However, when 0.4 g./l. of antimony was added a full-bright, haze-free deposit was obtained.
Example 3 To the same basic silver hath given in Example 1 was added 3 g./l. of antimony and 4 g./l. of methylene bis sulfonic acid, sodium salt, whereupon a brilliant deposit, from 0 to 4.0 amp/dim was obtained. The addition of another 0.5 g./l. of naphthalene bis sulfonic acid, sodium salt, had no etfect and it appears there is no practical upper limit for this compound other than economies which dictate using as little as necessary to get full brightness. However, if one adds more than 3 g./l. of antimony the high current density range will show darkening but still bright, areas.
Example 4 To the standard silver solution (of Example 1, for example) was added 1 g./l. of sodium methylene bis naphthalene sulfonate and 0.2 -g./ l. of antimonous oxide. A brilliant deposit was obtained with a range up to about 3.5 amperes/dmfi.
Example 5 To the standard silver solution of Example 1 was added 1 g./ 1. of methylene bis naphthalene sulfonate and 0.2 g./l. of antimony chloride. Some precipitation occurred, most of which redissolved. A Hull cell panel plated in the bath shows a bright range from 03.5 amperes/dmfi.
I claim: 1. An aqueous bath for the deposition of silver consisting essentially of from about 7.5 g./l. to about 112 g./l. of a soluble silver cyanide, from about 25 g./l. to 450 g./l. of a soluble cyanide, from about .006 to about 38 g./l. of a soluble salt of methylene bis naphthalene sulfonic acid and from about 0.25 g./l. to about 12 g./ 1. of antimony added as a compound soluble in the bath. 2. An aqueous bath as claimed in claim 1 in which the antimony compound is tartar emetic.
3. An aqueous bath as claimed in claim 1 in which the antimony compound is antimony oxide.
4. A process for the deposition of silver consisting of immersing a conductive workpiece in a solution consisting essentially of about 7.5 g./1. to about 112 g./l. of a soluble alkali silver cyanide, about 25 g./l. to about 450 g./l. of a soluble alkali cyanide, about 0.25 g./l. to about 12 g./l. of antimony added as a soluble antimony compound and about .006 to about 38 g./l. of a soluble salt of methylene bis naphthalene sulfonic acid, and
passing an electric current through the bath in such a fashion that the workpiece is the cathode and the current density thereon is about 0.1-5 .0 amperes per square decimeter.
References Cited by the Examiner UNITED STATES PATENTS 2,701,234 2/1955 Wernlund 20452.1 2,735,808 2/1956 Greenspan 20446 2,771,411 11/1956 Chester et al. 20455.1 2,777,810 1/ 1957 Ostrow 20446 2,787,590 4/1957 Rinker 204 55.1
JOHN H. MACK, Primary Examiner.
JOHN R. SPECK, Examiner.
Claims (1)
1. AN AQUEOUS BATH FOR THE DEPOSITION OF SILVER CONSISTING ESSENTIALLY OF FROM ABOUT 7.5 G/L. TO ABOUT 112 G./L. OF A SOLUBLE SILVER CYANIDE, FROM ABOUT 25 G./L. TO 450 G./L. OF A SOLUBLE CYANIDE, FROM ABOUT .006 TO ABOUT 38 G./L. OF A SOLUBLE SALT OF METHYLENE BIS MAPHTHALENE SULFONIC ACID AND FROM ABOUT 0.25 G./L. TO ABOUT 12 G./L. OF ANTIMONY ADDED AS A COMPOUND SOLUBLE IN THE BATH.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL136511D NL136511C (en) | 1962-03-22 | ||
| NL290554D NL290554A (en) | 1962-03-22 | ||
| US181793A US3219558A (en) | 1962-03-22 | 1962-03-22 | Bright silver plating bath and process |
| GB6054/63A GB955648A (en) | 1962-03-22 | 1963-02-14 | Bright silver plating |
| CH298163A CH415226A (en) | 1962-03-22 | 1963-03-08 | Process for the electrolytic deposition of silver and aqueous bath for the implementation of this process |
| FR928391A FR1357205A (en) | 1962-03-22 | 1963-03-18 | Aqueous bath and method for the electrolytic deposition of silver |
| BE670818D BE670818A (en) | 1962-03-22 | 1965-10-12 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US181793A US3219558A (en) | 1962-03-22 | 1962-03-22 | Bright silver plating bath and process |
| GB6054/63A GB955648A (en) | 1962-03-22 | 1963-02-14 | Bright silver plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3219558A true US3219558A (en) | 1965-11-23 |
Family
ID=26240376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US181793A Expired - Lifetime US3219558A (en) | 1962-03-22 | 1962-03-22 | Bright silver plating bath and process |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3219558A (en) |
| BE (1) | BE670818A (en) |
| CH (1) | CH415226A (en) |
| GB (1) | GB955648A (en) |
| NL (2) | NL290554A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3425917A (en) * | 1964-04-10 | 1969-02-04 | Schering Ag | Electrodeposition of silver antimony alloys |
| US3446716A (en) * | 1966-01-05 | 1969-05-27 | Max Schlotter Dr Ing | Electrodeposition of bright silver |
| US4465564A (en) * | 1983-06-27 | 1984-08-14 | American Chemical & Refining Company, Inc. | Gold plating bath containing tartrate and carbonate salts |
| WO2013142765A1 (en) * | 2012-03-23 | 2013-09-26 | Technic, Inc. | Silver antimony coatings and connectors |
| CN103981548A (en) * | 2014-05-20 | 2014-08-13 | 西安西光表面精饰有限公司 | Silver plating process |
| CN103981549A (en) * | 2014-05-20 | 2014-08-13 | 西安西光表面精饰有限公司 | Silver-plating solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2701234A (en) * | 1951-07-11 | 1955-02-01 | Du Pont | Addition agent for copper plating |
| US2735808A (en) * | 1955-01-31 | 1956-02-21 | Mirror bright silver plating | |
| US2771411A (en) * | 1951-05-10 | 1956-11-20 | Poor & Co | Cyanide compositions suitable for electroplating baths and method for the preparation thereof |
| US2777810A (en) * | 1956-10-03 | 1957-01-15 | Elechem Corp | Bath for electroplating silver |
| US2787590A (en) * | 1954-06-15 | 1957-04-02 | Sel Rex Precious Metals Inc | Electroplating bath purification |
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0
- NL NL136511D patent/NL136511C/xx active
- NL NL290554D patent/NL290554A/xx unknown
-
1962
- 1962-03-22 US US181793A patent/US3219558A/en not_active Expired - Lifetime
-
1963
- 1963-02-14 GB GB6054/63A patent/GB955648A/en not_active Expired
- 1963-03-08 CH CH298163A patent/CH415226A/en unknown
-
1965
- 1965-10-12 BE BE670818D patent/BE670818A/xx unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2771411A (en) * | 1951-05-10 | 1956-11-20 | Poor & Co | Cyanide compositions suitable for electroplating baths and method for the preparation thereof |
| US2701234A (en) * | 1951-07-11 | 1955-02-01 | Du Pont | Addition agent for copper plating |
| US2787590A (en) * | 1954-06-15 | 1957-04-02 | Sel Rex Precious Metals Inc | Electroplating bath purification |
| US2735808A (en) * | 1955-01-31 | 1956-02-21 | Mirror bright silver plating | |
| US2777810A (en) * | 1956-10-03 | 1957-01-15 | Elechem Corp | Bath for electroplating silver |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3425917A (en) * | 1964-04-10 | 1969-02-04 | Schering Ag | Electrodeposition of silver antimony alloys |
| US3446716A (en) * | 1966-01-05 | 1969-05-27 | Max Schlotter Dr Ing | Electrodeposition of bright silver |
| US4465564A (en) * | 1983-06-27 | 1984-08-14 | American Chemical & Refining Company, Inc. | Gold plating bath containing tartrate and carbonate salts |
| WO2013142765A1 (en) * | 2012-03-23 | 2013-09-26 | Technic, Inc. | Silver antimony coatings and connectors |
| CN103981548A (en) * | 2014-05-20 | 2014-08-13 | 西安西光表面精饰有限公司 | Silver plating process |
| CN103981549A (en) * | 2014-05-20 | 2014-08-13 | 西安西光表面精饰有限公司 | Silver-plating solution |
Also Published As
| Publication number | Publication date |
|---|---|
| NL290554A (en) | |
| BE670818A (en) | 1966-01-31 |
| CH415226A (en) | 1966-06-15 |
| NL136511C (en) | |
| GB955648A (en) | 1964-04-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
| AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |