US3186926A - Electroplating solution containing a diester of selenious acid - Google Patents
Electroplating solution containing a diester of selenious acid Download PDFInfo
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- US3186926A US3186926A US216317A US21631762A US3186926A US 3186926 A US3186926 A US 3186926A US 216317 A US216317 A US 216317A US 21631762 A US21631762 A US 21631762A US 3186926 A US3186926 A US 3186926A
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- United States
- Prior art keywords
- acid
- diester
- selenious acid
- bright
- bath
- 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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- 229940000207 selenious acid Drugs 0.000 title claims description 16
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 title claims description 15
- 150000005690 diesters Chemical class 0.000 title description 11
- 238000009713 electroplating Methods 0.000 title description 8
- 238000000576 coating method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 6
- 239000010695 polyglycol Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229940082569 selenite Drugs 0.000 description 5
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- -1 selenious acid ester Chemical class 0.000 description 4
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229940065287 selenium compound Drugs 0.000 description 2
- 150000003343 selenium compounds Chemical class 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- FPIXVMBTONUESS-UHFFFAOYSA-N NC(S)=S.NC(S)=S.[SeH2] Chemical compound NC(S)=S.NC(S)=S.[SeH2] FPIXVMBTONUESS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YVOFKSGFOGNJHF-UHFFFAOYSA-N [SH2]=N.C(C1=CC=CC=C1)(=O)O Chemical compound [SH2]=N.C(C1=CC=CC=C1)(=O)O YVOFKSGFOGNJHF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- NTEFHFJOCXLHIX-UHFFFAOYSA-N dimethyl selenite Chemical compound CO[Se](=O)OC NTEFHFJOCXLHIX-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction 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
Definitions
- selenious acid and salts thereof as additives, together with an albumen condensation product, for silver baths for the production of bright silver coatings.
- selenious acid in combination with various wetting agents in copper baths, as a brightener.
- Selenium dioxide is also known as an active brightener in nickel baths, and selenium compounds, namely selenium dithiocarbamate, and selenium in a form providing divalent negative ions have also already been proposed as additives for silver, gold and copper-plating baths.
- any desirable properties required for any specific electroplating bath can be obtained.
- further substituents for example amino groups, sulpho-acid groups, it is possible to improve the water-solubility of the compounds in the various pH ranges, and with appropriate active groups to, improve the brightening eitect for the various metals.
- Example 1 Very bright copper precipitates were deposited from a cyanidic bath of the following composition:
- the bright range is extended to a current density of 5 a./-dm.
- Example 2 Uniform. very bright copper deposits were produced on a moving cathode from a cyanidic bath of the following composition:
- the cathode current yield is 9S-l00%.
- Example 3 Mirror-bright completely cloud-free silver coatings were obtained from a silver bath of the following composition:
- the resultant silver deposits have a hardness of kgJmmP.
- Example 4 A bath for the deposition of gold has the following composition:
- Very bright gold deposits were obtained at 20-50 C., in current density ranges of 0.1-3 a./dm.
- Example 5 From a nickel bath of the following composition: MiSO -7H O g./l 280 NiCl 61-1 0 g./1 40 H 80 g./l 40 Benzoic acid sulphimide g./l 1 Bis-(o-aminophenol-sulph-onic acid) diseleni-te mol/l 000005-01 Lauryl sulphate g./l 0.5 Acetylene amine -g./1 0.015
- mirror-bright ductile nickel deposit-s having a good leveling action were obtained at 60 C., in a current density range of 01-10 a./dm.
- mirror bright deposits were also obtained at 20 C., without movement of the article in the current density range from 0.1-2 a./dm.
- Example 6 7 From a nickel bath of the following composition:
- Example 8 Very bright deposits were obtained from a cyanidic cadmium bath of the following composition:
- An aqueous bath for the electrolytic deposition of bright metal coatings including an ionizable compound of the metal to be deposited, and as a brightener, an effective amount of a stable diester of selenious acid.
- An aqueous bath for the electrolytic deposition of bright nickel including an ionizable nickel compound and, as a brightener, an effective amount of a stable diester of selenious acid.
- An aqueous bath for the electrolytic deposition of bright nickel including an ionizable nickel compound and,
- An electroplating solution comprising, in aqueous solution, an ionizable compound of a metal to be deposited electrolytically, said solution containing, as a brightener, a stable diester of selenious acidin a concentration between 0.00005 and 0.2 mol per liter.
- An aqueous electroplating solution comprising a cyanide salt of a metal to be deposited electrolytically, said solution containing, as a brightener, an effective amount of a stable diester of selenious acid.
- a method of depositing a bright metal coating which comprises electrolyzing an equeous solution of an ionizable compound of said metal, said solution including an effective amount of a stable diester of selenious acid as a biightener.
- An electroplating bath comprising an aqueous solution of a source of a metal to be electrodeposited, said source being selected from the group consisting of the complex cyanides of copper, silver, gold, zinc, and cadmium, and the sulfate and chloride of nickel, said solution containing, as a brightener, an effective amount of a stable diester of selenious acid with a compound selected from the group consisting of the lower alkanols, phenosulfonic acid, 2-naphthol-3,6-sulfonic acid, o-aminophcnol-sulfonic acid, glycerine, and polyglycol.
- a method of electrodepositing bright nickel which comprises electrolyzing an aqueous medium containing nickel sulfate, as a source of nickel ions and, as a brightener, an effective amount of a stable diester of selenious acid with a compound selected from the group consisting of the lower alkanols, phenol-sulfonic acid, 2- naphthol-3 ,6-sulfonic acid, o-a-minophenolsulfonic acid, glycerine, and polyglycol.
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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 3,136,925 ELECTRGPLATHJG SGLUTEQN @ONTAiNiNG A DETER 0F SEiENiOUS ACID Hans Hofrnann, Neuss (Rhine), Germany (Gustav Klein Strasse 8, Stuttgart-Feuerbach, Germany), and Karl Wilhelm Sassenroth, Dusseldorf, Germany (Roonstrasse 65, Bielefeld, Germany) No Drawing. Filed Aug. 13, 1962, Star. No. 216,317 9 Claims. (Cl. 204-49) This invention relates to electrolytic deposition of bright metal coatings using electroplating baths to which brighteners are added. It is already known that additions of selenium compounds, preferably selenious acid or salts thereof, are active as brighteners in various electroplating baths.
Thus, it has already been proposed, a relatively long time ago, to use selenious acid and salts thereof as additives, together with an albumen condensation product, for silver baths for the production of bright silver coatings. Recently, it has also been proposed to use selenious acid in combination with various wetting agents in copper baths, as a brightener. Selenium dioxide is also known as an active brightener in nickel baths, and selenium compounds, namely selenium dithiocarbamate, and selenium in a form providing divalent negative ions have also already been proposed as additives for silver, gold and copper-plating baths.
We have found, unexpectedly, that selenium in the form of its very readily accessible selenious acid ester together with alcohols, phenols, thiophenols and thioalcohols, when used as an additive in the most diverse galvanic baths, gives a substantial improvement of the brightness, better throwing power, higher permissible current density and, in acid nickel baths, not only excellent brightness but also very considerable leveling eifect. From a large number of tests with the esters of selenious acid with a wide variety of alcohols, phenols, thioalcohols and thiophenols, we have found that apparently all the stable selenious acid esters, of which practically only the diesters exist, have the above-mentioned outstanding effects as brighteners in electroplating baths.
By selection of the compounds serving for the esteriz'ication and bearing OH or SH groups, by their constitution, and by further substitution, any desirable properties required for any specific electroplating bath can be obtained. Thus, by the introduction of further substituents, for example amino groups, sulpho-acid groups, it is possible to improve the water-solubility of the compounds in the various pH ranges, and with appropriate active groups to, improve the brightening eitect for the various metals.
Furthermore, by altering the size and structure of the molecule carrying the esterifiable groups, it is possible to obtain very good properties for the deposited metal coatings. The use of brighteners with high molecular weights according to the invention is advisable in electrolytic baths of the kind in which the metals deposited are not very sensitive to inhibitors, for example zinc and cadmium.
Apart from the selenious acid diesters, known brightening and leveling agents, hardening binders, pore-inhibiting agents, Wetting agents and so on may be added to the baths for further improvement and it special effects are required.
It is surprising that even very small quantities of selenious acid diest'ers give a high eiiect. Additions of about 0.00005 mol/litre to 0.2 mol/litre are used. In the case of baths for nickel deposition, it is advantageous also to add a small quantity of an acetylene amine.
The following examples illustrate the invention and the manner in which it is carried into effect:
Example 1 Very bright copper precipitates were deposited from a cyanidic bath of the following composition:
COpper as Na Cu(CN) g./l 50 NaCN (free cyanide) g./l 12 Seignette salt g./l 30 Dimethyl selenite m01/l 0.00005-01 Polyglycol ether g./l 0.5
at a bath temperature of 65 C., and with a moving cathode in the current density range from 0.2-3 a./dm.
Using a 30:1 current reversal cycle, the bright range is extended to a current density of 5 a./-dm.
Example 2 Uniform. very bright copper deposits were produced on a moving cathode from a cyanidic bath of the following composition:
Copper as Na Cu(CN) g./l 60 NaCN (free cyanide) g./l 15 Sodium citrate g./l 40 Bi-s-(phenosulfonic acid) selenite mol/l 000005-01 Polyglycol ether g./l 0.5 Acid amide sulpho-acids g./l 0.025
at 70 C., in a current density range from 0.2-4 a./drn. without current reversal. The cathode current yield is 9S-l00%.
Example 3 Mirror-bright completely cloud-free silver coatings were obtained from a silver bath of the following composition:
Silver in the form of KAg(CN) g./l 30 KCN (free cyanide) g./l K CO g./l 40 Bis-(2-naphthol-3,6-sulfonic acid) selenite "moi/1-- 000005-01 Turkey red oil g./l 1
and the brightness of these coatings is fully retained even with high coating thicknesses. The resultant silver deposits have a hardness of kgJmmP.
Example 4 A bath for the deposition of gold has the following composition:
Gold as KAu(CN) g./l 8 KCN (free cyanide) g./l 100 KgHPO g./1 Bis-(2-naphthol3,6-sultonic acid) 'selenite rnol/l 000005-01 Turkey red oil g./l 1
Very bright gold deposits were obtained at 20-50 C., in current density ranges of 0.1-3 a./dm.
Example 5 From a nickel bath of the following composition: MiSO -7H O g./l 280 NiCl 61-1 0 g./1 40 H 80 g./l 40 Benzoic acid sulphimide g./l 1 Bis-(o-aminophenol-sulph-onic acid) diseleni-te mol/l 000005-01 Lauryl sulphate g./l 0.5 Acetylene amine -g./1 0.015
mirror-bright ductile nickel deposit-s having a good leveling action were obtained at 60 C., in a current density range of 01-10 a./dm.
From the same bath, mirror bright deposits were also obtained at 20 C., without movement of the article in the current density range from 0.1-2 a./dm.
Example 6 7 From a nickel bath of the following composition:
NiSO '-7H O g./l 280 NiCl -6H O g./l 40 H3803 g./l Naphthalene trisulfonic acid g./l 10 Diethyl selenite mol/l 0.000050.l Lauryl sulphate g./l 0.5 Acetylene amine g./l 0.015
nickel deposits were obtained as in Example 5.
' Example 7 Very bright zinc deposits were obtained from a cyanidic zinc bath of the following composition:
Zinc as Na Zn(CN) g./l 30 NaCN (total cyanide) g./l 50 NaOH g./l 90 Diglycerine selenite ml/l (100005-01 at 20 C., in current density ranges of from 0.1 6 a./dm. Example 8 Very bright deposits were obtained from a cyanidic cadmium bath of the following composition:
Cadmium as Na Cd(CN) g./l 25 NaCN (total cyanide) g./l 100 NiSO -7H O g./l. 1 Di-polyglycol (M.W. 600) selenite mol/l 0.000050.1 Polyglycol ether g./l 1
at 20 0., in current density ranges of from 0.5-10 a./ dm. and with cathode movement.
7 We claim:
1. An aqueous bath for the electrolytic deposition of bright metal coatings, including an ionizable compound of the metal to be deposited, and as a brightener, an effective amount of a stable diester of selenious acid.
2. An aqueous bath for the electrolytic deposition of bright nickel including an ionizable nickel compound and, as a brightener, an effective amount of a stable diester of selenious acid. I
3. An aqueous bath for the electrolytic deposition of bright nickel including an ionizable nickel compound and,
4 as a brightener, a stable diester of selenious acid in a concentration between 0.00005 and 0.2 mol per liter.
4. An electroplating solution comprising, in aqueous solution, an ionizable compound of a metal to be deposited electrolytically, said solution containing, as a brightener, a stable diester of selenious acidin a concentration between 0.00005 and 0.2 mol per liter.
5. An aqueous electroplating solution comprising a cyanide salt of a metal to be deposited electrolytically, said solution containing, as a brightener, an effective amount of a stable diester of selenious acid.
6. A method of depositing a bright metal coating which comprises electrolyzing an equeous solution of an ionizable compound of said metal, said solution including an effective amount of a stable diester of selenious acid as a biightener.
7. An electroplating bath comprising an aqueous solution of a source of a metal to be electrodeposited, said source being selected from the group consisting of the complex cyanides of copper, silver, gold, zinc, and cadmium, and the sulfate and chloride of nickel, said solution containing, as a brightener, an effective amount of a stable diester of selenious acid with a compound selected from the group consisting of the lower alkanols, phenosulfonic acid, 2-naphthol-3,6-sulfonic acid, o-aminophcnol-sulfonic acid, glycerine, and polyglycol.
8. A method of electrodepositing bright nickel which comprises electrolyzing an aqueous medium containing nickel sulfate, as a source of nickel ions and, as a brightener, an effective amount of a stable diester of selenious acid with a compound selected from the group consisting of the lower alkanols, phenol-sulfonic acid, 2- naphthol-3 ,6-sulfonic acid, o-a-minophenolsulfonic acid, glycerine, and polyglycol.
9. A method as set forth in claim 8, wherein the concentration of said diester in said aqueous medium is bc-- tween 0.00005 and 0.2 mol per litter.
References Cited by the Examiner UNITED STATES PATENTS 2,701,234 2/55 Wernlund 204-52.l 2,770,587 11/56 Ostro-w 20452.1 2,777,810 1/57 Ostrow 20446 JOHN H. MACK, Primary Examiner. MURRAY TILLMAN, Examiner.
Claims (1)
1. AN AQUEOUS BATH FOR THE ELECTROLYTIC DEPOSITION OF BRIGHT METAL COATING, INCLUDING AN IONIZABLE COMPOUND OF THE METAL TO BE DEPOSITED, AND AS A BRIGHTNER, AN EFFECTICE AMOUNT OF A STABLE DIESTER OF SELENIOUS ACID.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US216317A US3186926A (en) | 1962-08-13 | 1962-08-13 | Electroplating solution containing a diester of selenious acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US216317A US3186926A (en) | 1962-08-13 | 1962-08-13 | Electroplating solution containing a diester of selenious acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3186926A true US3186926A (en) | 1965-06-01 |
Family
ID=22806589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US216317A Expired - Lifetime US3186926A (en) | 1962-08-13 | 1962-08-13 | Electroplating solution containing a diester of selenious acid |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3186926A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532610A (en) * | 1967-10-27 | 1970-10-06 | Kewanee Oil Co | Selenium compounds as brighteners in copper plating baths |
| US3793079A (en) * | 1971-11-18 | 1974-02-19 | Occidental Energy Dev Co | Battery electrolyte composition |
| US3945894A (en) * | 1975-04-11 | 1976-03-23 | Oxy Metal Industries Corporation | Bath composition and method of electrodepositing utilizing the same |
| US4155817A (en) * | 1978-08-11 | 1979-05-22 | American Chemical And Refining Company, Inc. | Low free cyanide high purity silver electroplating bath and method |
| US4416740A (en) * | 1981-03-06 | 1983-11-22 | Langbein-Pfanhauser Werke Ag | Method and bath for the electrodeposition of palladium/nickel alloys |
| US4428804A (en) | 1980-11-10 | 1984-01-31 | Omi International Corporation | High speed bright silver electroplating bath and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2701234A (en) * | 1951-07-11 | 1955-02-01 | Du Pont | Addition agent for copper plating |
| US2770587A (en) * | 1956-06-04 | 1956-11-13 | Elechem Corp | Bath for plating bright copper |
| US2777810A (en) * | 1956-10-03 | 1957-01-15 | Elechem Corp | Bath for electroplating silver |
-
1962
- 1962-08-13 US US216317A patent/US3186926A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2701234A (en) * | 1951-07-11 | 1955-02-01 | Du Pont | Addition agent for copper plating |
| US2770587A (en) * | 1956-06-04 | 1956-11-13 | Elechem Corp | Bath for plating bright copper |
| 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 |
|---|---|---|---|---|
| US3532610A (en) * | 1967-10-27 | 1970-10-06 | Kewanee Oil Co | Selenium compounds as brighteners in copper plating baths |
| US3793079A (en) * | 1971-11-18 | 1974-02-19 | Occidental Energy Dev Co | Battery electrolyte composition |
| US3945894A (en) * | 1975-04-11 | 1976-03-23 | Oxy Metal Industries Corporation | Bath composition and method of electrodepositing utilizing the same |
| US4155817A (en) * | 1978-08-11 | 1979-05-22 | American Chemical And Refining Company, Inc. | Low free cyanide high purity silver electroplating bath and method |
| US4428804A (en) | 1980-11-10 | 1984-01-31 | Omi International Corporation | High speed bright silver electroplating bath and process |
| US4416740A (en) * | 1981-03-06 | 1983-11-22 | Langbein-Pfanhauser Werke Ag | Method and bath for the electrodeposition of palladium/nickel alloys |
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