US2732336A - Electroplating composition for copper - Google Patents
Electroplating composition for copper Download PDFInfo
- Publication number
- US2732336A US2732336A US2732336DA US2732336A US 2732336 A US2732336 A US 2732336A US 2732336D A US2732336D A US 2732336DA US 2732336 A US2732336 A US 2732336A
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- US
- United States
- Prior art keywords
- per liter
- copper
- bath
- soluble
- bright
- Prior art date
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 16
- 229910052802 copper Inorganic materials 0.000 title description 16
- 239000010949 copper Substances 0.000 title description 16
- 238000009713 electroplating Methods 0.000 title description 4
- 150000003343 selenium compounds Chemical class 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 24
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052787 antimony Inorganic materials 0.000 claims description 20
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 10
- 150000003346 selenoethers Chemical class 0.000 claims description 10
- IYKVLICPFCEZOF-UHFFFAOYSA-N Selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- 101700018994 ARYL Proteins 0.000 claims 2
- 238000007747 plating Methods 0.000 description 30
- 125000000217 alkyl group Chemical group 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 229940065287 selenium compounds Drugs 0.000 description 18
- QYHFIVBSNOWOCQ-UHFFFAOYSA-L selenate Chemical class [O-][Se]([O-])(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-L 0.000 description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 16
- DOBRDRYODQBAMW-UHFFFAOYSA-N Copper(I) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 14
- 239000011669 selenium Substances 0.000 description 14
- 229910052711 selenium Inorganic materials 0.000 description 14
- 125000004432 carbon atoms Chemical group C* 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 8
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 6
- 150000001462 antimony Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- RTVFYQXEHKQMKO-UHFFFAOYSA-N sodium cyanide Chemical compound [Na]C#N RTVFYQXEHKQMKO-UHFFFAOYSA-N 0.000 description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229940095064 tartrate Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene (PE) Substances 0.000 description 4
- 229940082569 Selenite Drugs 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 4
- YWBHROUQJYHSOR-UHFFFAOYSA-N $l^{1}-selanylbenzene Chemical compound [Se]C1=CC=CC=C1 YWBHROUQJYHSOR-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 241000282461 Canis lupus Species 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N DETA Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N Nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N Silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229960001124 Trientine Drugs 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N Triethylenetetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 230000002079 cooperative Effects 0.000 description 2
- 230000001627 detrimental Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KEBHLNDPKPIPLI-UHFFFAOYSA-N hydron;2-(3H-inden-4-yloxymethyl)morpholine;chloride Chemical compound Cl.C=1C=CC=2C=CCC=2C=1OCC1CNCCO1 KEBHLNDPKPIPLI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- CRDYSYOERSZTHZ-UHFFFAOYSA-M selenocyanate Chemical class [Se-]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-M 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229940098221 silver cyanide Drugs 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 235000012976 tarts Nutrition 0.000 description 2
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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
- C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+
Definitions
- This invention relates to electroplating from cyanide baths, more particularly to a bath composition which is particularly adapted to produce bright coatings of soft, ductile elcctroplates of copper.
- the present application is a continuatiomin part of my co-pending application Serial No. 242,04l ,filed August 15, 1951, entitled Electrolytic Bath for Copper and Silver, and now abandoned and is also a continuation-in-part of copending application Serial No. 126,679, now Patent No. 2,694,677, dated November 16, 1954. V
Description
Uflltd States BarnetD. osnow, North Bellmore, N. Y., assignor to Elechem Corp., Jersey City, N. L, a corporation of New Jersey No Drawing. Application April 20, 1953,
Serial No. 349,935
5 Claims. (Cl. 204-52) This invention relates to electroplating from cyanide baths, more particularly to a bath composition which is particularly adapted to produce bright coatings of soft, ductile elcctroplates of copper. The present application is a continuatiomin part of my co-pending application Serial No. 242,04l ,filed August 15, 1951, entitled Electrolytic Bath for Copper and Silver, and now abandoned and is also a continuation-in-part of copending application Serial No. 126,679, now Patent No. 2,694,677, dated November 16, 1954. V
Numerous attempts to obtain such bright coatings have been made. For instance, it has been proposed to use alkali metal selenite as an addition agent to an electrolytic bath in relatively large amounts. Such baths had a number of disadvantages in that the selenites tended to break down with a resultant adverse effect onthe bright plating range. During the electrolysis the anodes became blackened, forming insoluble selenium compounds which were loosened from the anodes and tended to co-deposit with the desired metal, resulting in rough deposits which were commercially unusable. Also in commercial operation, due to the resulting very narrow bright plating range, nonuniform appearance of the deposits resulted, and the platings were in many cases insufliciently bright so that buffing was necessary. 7
It has also been proposed to provide a bath composition containing as one of the plating metals antimony or the like, as for example, in providing a plated alloy of copper, zinc and antimony. However, such coatings were not at all bright and required further operations in order to obtain a bright surface. The addition of lead or antimony in soluble form to copper plating baths resulted in hard and brittle deposits.
The present invention is intended and adapted to overcome the difiiculties and disadvantages inherent in prior baths of the type described, it being among the objects of the present invention to provide a bath composition into which a relatively small amount of addition agents is introduced and which results in greatly increased brightness of the plated surface, with a wider, more uniform and bright plating range.
It is also among the objects of the present invention to provide abath composition which results in a plate which is brilliant, soft and ductile and which 'may be readily buffed if desired to cause the coating to flow, as for example, on steel.
The invention is based on the discovery that the addition to a copper cyanide bath of very small amounts of selenium in soluble form together with small amounts of lead or antimony in soluble form, gives a plate which is bright and does not require bulfing. It is the cooperative action of the additives which is necessary to obtain the full benefits of the invention.
In practicing the present invention there is provided an alkaline cyanide bath composition which is usually of the ordinary type and containing cyanides of copper. There is added thereto a selenium compound which may be a metal selenide or an organic selenium compound or 2,732,336 Patented Jan. 24, 1956 mixtures thereof. The amounts so added are extremely small, being from .0001 to .01 gram per liter; It is highly desirable to have present together with the selenium, a small amount of a metal in the form of its water soluble salts, the metal being lead or antimony. The amounts thereof may varyconsiderably and usually there isprescut an amount of lead equal to about .001 to 1.0' gram per liter, the antimony being usedin greater amounts, usually from about .01 to 5.0 grams per liter. g
The active brightening agents infthe present high speed copper cyanide plating baths are controlled quantities of organic selenium compounds or 'selenides which are converted into organic form in the bath. Less efiective, but useable, are the soluble selenites and selenates. Care must be taken to maintain a small and less than critical amount of such "selenium compounds in the bath, as otherwise the bright plating range will be reduced. Such selenium compounds are effective in the presence of lead or antimony salts. Preferably, those soluble selenium compounds having a valence of -2 are used.
The following are specific examples of the operation of the present invention. In said examples the stated amounts are in grams per liter and water.
I 1 I Example 1 The composition is as follows:
KOH NazSe .002 Pb (as nitrate) .001
The article is plated at a temperature of to F. with a current density of 10 to 60 amperes per square foot. During the plating -the bath is continuously agitated. The resulting coating is smooth, brilliant and ductile.
The plating is conducted at 140-180 F. with a current density of 20 to 50 amperes per square foot with continuous agitation.
Example 3 The following composition is provided;
CuCN 75.0 Total NaCN 90.0 Rochelle salts 45.0 KOH 15.0 Free NaCN 7.5 Selenophenol .005 Sb (a's tartrate) .003 Pb (as tart'rate) .001
The plating is accomplished at about. F. with a current of 60 amperes per square foot and continuous agitation.
The selenides used are the ordinary alkali metal compounds or such other salts of selenium as are soluble in the bath. The organic selenium compounds may be the alkali metal s'elen'ocyanates or other soluble compounds. Also selenou're'as or selenophenols may be used. In addi- 'tion, compounds having the formula RSeH Which are analogous to the mercaptans are suitable for 'the present purpose; R represents aryl or'alkyl, the aryl groups being mono or polynuclear and the alkyl groups having 1 to 6 carbon atoms.
Also suitable for the purpose are the water soluble selenites and selenates although they are considerably inferior to the above named compounds andrelatively large amounts thereof are necessary. Such selenites and selenates when added to the bath in the absence of lead or antimony in the form of their salts, break down during the plating operation and fail to give bright deposits ove. a wide range of current densities. However, in combination with soluble compounds of lead or antimony, or both, satisfactory results in plating are obtained. However, relatively large amounts of the selenites or selenates are used up to, say, grams of selenium per litre. When the selenites or selenates are used, larger amounts of the lead or antimony salts are added to the b ath'than when selenium compounds having a valence of -2 are used. Also, baths containing selenites or selenates which have broken down, may be made operable by the addition of relatively large amounts of leador antimony salts; for instance, more than .01 gram per liter of lead salts. The following are specific examples of such baths.
Example 4 The following bath is prepared:
CuCN 45 gm. per liter. Free KCN 9.5 gm. per liter. K2C4H40s 45 gm. per liter. KOH gm. per liter. KzSeOa 1 gm. per liter.
Pb (as acetate) 0.002 gm. per liter.
The bath is maintained at a temperature of about 150 F. and a current density of to amperes per square foot is used. A bright deposit not requiring bufling is obtained.
Example 5 The following bath is prepared:
CuCN 8 oz. per gal.
Free NaCN .5 oz. per gal. Rochelle salts 6 oz. per gal.
KOH 2 oz. per gal. KzSeO4 1 gm. per liter.
Pb (as chloride) 0.002 gm. per liter.
The bath is maintained at 160 to 170 F. with a current density of about 35 amperes per square foot. The plating is a satisfactorily bright plate.
The lead and antimony are used in the form of soluble salts either organic or inorganic, such as the tartrate, nitrate or chloride. While these metals would ordinarily render the coating brittle, in the presence of said selenium compounds the deposits are not only ductile but also more uniform and brilliant. These effects are obtained over all current densities ordinarily used in the plating of copper, thereby insuring uniform brightness over the entire plated area.
Example 6 Selenium in the form of organic substances having a valence of 2 and in the form of selenides, also having avalence of -2, are capable of giving bright deposits in small quantities in copper and silver cyanide baths. A bath having the following composition in grams per litre of solution is typical:
Copper cyanide Total KCN 72 Free KCN 9-12 KOH l5 Rochelle salts 45 KCNSe .002
Plating is conducted at 140 to 170 F. with a current density of 10 to amperes per square foot. The cathode is agitated and the deposit is bright and ductile. While the deposit is not as brilliant as those of Examples l and 2, it is sufficiently bright for an undercoat for bright nickel deposits. The bath is somewhat less tolerant to inorganic impurities than those of Examples 1, 2 and 3 but is sufficiently tolerant for commercial use.
The effectiveness of this bath continues over long periods of time, in contrast to baths containingv the selenium having valences of +4 or +6, such as selenites or selenates, which are either ineffective or lose their effectiveness in the bath after a short time; they are unstable compounds which form dark deposits on the anode, cause the cathode to become dull, have a narrow bright range and give rough deposits, whereas those selenium compounds having a valence of 2 do not show such defects.
Although the invention has been described setting forth several specific examples of the operation thereof, the invention is not to be limited thereto as many changes may be made in the details thereof. For instance, the composition of the baths may be considerably altered and other substances may be added thereto, such as alkyl polyamines, including ethylene diamine, diethylene triamine, triethylene tetramine, and others up to alkyl groups having 5 carbon atoms, the number of amino groups being from 2 to 5, in amounts of about .25 to 50 grams per litre, although preferably smaller amounts up to 10.0 are used.
In place of the polyethylene compound set forth in Example 5, substances such as the polyglycols and esters thereof may be used, for instance, nonyl phenol polyethylene glycol, wherein the polyethylene radical has a molecular weight of at least 400. The tartrate of Examples 4 and 5 is usually represented by the formula K(SbO)C4H40s. The selenophenols include compounds of the type RSeH, wherein R is monoor poly-nuclear aryl and alkyl having 2 to 12 carbon atoms. The conditions of operation may be varied within usual practice.
Larger amounts of the additives may be used, even above the maxima stated herein. However, such excess does not usually give beneficial effects, and too much excess may even be detrimental. This applies particularly to large amounts of selenium having a valence of +4, namely, the selenites.
These and other variations are possible within the spirit of the invention, which is to be broadly construed and not to be limited except by the claims appended hereto.
I claim:
1. An electrolytic bath comprising an aqueous alkaline solution of a cyanide of copper, a soluble selenium compound taken from the class consisting of selenides, selenoureas, selenocyanates, selenites, selenates, and compounds of the formula RSeH wherein R is an organic radical taken from the class consisting of alkyl radicals of 1.to 6 carbon atoms and aryl radicals of 6 to 12 carbon atoms said selenium compound being present in an amount from .0001 to5 grams per liter, together with a soluble compound of a metal taken from the class consisting of lead and antimony in which the metal is present in an amount from .001 to 5 grams per liter.
2. An electrolytic bath according to claim 1 in which there is present an alkyl polyamine in the amount of .25 to 50 grams per liter.
3. An electrolytic bath according to claim 1 in which there is present an alkyl polyamine in the amount of .25 to 50 grams per liter, the alkyl group having from 2 to 5 carbon atoms.
4. An electrolytic bath according to claim 1 in which there is present an alkyl polyamine in the amount of .25 to 50 grams per liter, the number of amino groups being from 2 to 5.
5. An electrolytic bath comprising an aqueous alkaline solution of a cyanide of copper, a soluble selenite in an amount from 1 to 5 grams per liter, together with a soluble compound of a metal taken from the class consisting of lead in an amount from .001 to .018 gram per liter and OTHER REFERENCES antmwny m an ammmt 8mm Per llter- Ser. No. 351,241, Weiner (A. P. 0. published May References Cited in the filc of this patent Gilbertson et aL: Transactions Electrochemical Society,
UNITED STATES PATENTS vol. 79 (1941) pp. 439-442. 2,125,229 Harshaw et aL July 2 19 3 Meyer et aL: Transactions Electrochemical Society, 2,513 179 wolf n t O t, 7, 1952 73 PP- 377, 384, 392,
2,694,677 Ostrow Nov. 16, 1954
Claims (1)
1. AN ELECTROLYTIC BATH COMPRISING AN AQUEOUS ALKALINE SOLUTION OF A CYANIDE OF COPPER, SOLUBLE SELENIUM COMPOUND TAKEN FROM THE CLASS CONSISTING OF SELENIDES, SELENOUREAS, SELENOCYANATES, SELENITES, SELENATES, AND COMPOUNDS OF THE FORMULA RSEH WHEREIN R IS AN ORGANIC RADICAL TAKEN FROM THE CLASS CONSITING OF ALKYL RADICALS OF 1 TO 6 CARBON ATOMS AND ARYL RADICALS OF 6 TO 12 CARBON ATOMS SAID SELENIUM COMPOUND BEING PRESENT IN AN AMOUNT FROM .0001 TO 5 GRAMS PER LITER, TOGETHER WITH A SOLUBLE COMPOUND OF A METAL TAKEN FROM THE CLASS CONSISTING OF LEAD AND ANTIMONY IN WHICH THE METAL IS PRESENT IN AN AMOUNT FROM .001 TO 5 GRAMS PER LITER.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2732336A true US2732336A (en) | 1956-01-24 |
Family
ID=3442043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2732336D Expired - Lifetime US2732336A (en) | Electroplating composition for copper |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2732336A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2774728A (en) * | 1955-09-29 | 1956-12-18 | Du Pont | Addition agent for copper plating |
| US2814590A (en) * | 1954-07-20 | 1957-11-26 | Lloyd B Portzer | Electrodeposition of copper |
| US2825684A (en) * | 1956-10-09 | 1958-03-04 | Du Pont | Bright copper plating |
| US2848394A (en) * | 1956-05-04 | 1958-08-19 | Hanson Van Winkle Munning Co | Bright copper plating |
| US2854389A (en) * | 1956-04-30 | 1958-09-30 | Du Pont | Bright copper plating process |
| US2870709A (en) * | 1955-10-28 | 1959-01-27 | Du Pont | Electroformed articles and process for their manufacture |
| US2873234A (en) * | 1957-06-19 | 1959-02-10 | Metal & Thermit Corp | Electrodeposition of copper |
| US2881122A (en) * | 1957-03-14 | 1959-04-07 | Hanson Van Winkle Munning Co | Electroplating |
| US3021266A (en) * | 1957-08-12 | 1962-02-13 | Barnet D Ostrow | Additive for copper plating bath |
| US3492135A (en) * | 1967-02-01 | 1970-01-27 | Schering Ag | Stabilized bath for deposition of copper by chemical reduction |
| US3532610A (en) * | 1967-10-27 | 1970-10-06 | Kewanee Oil Co | Selenium compounds as brighteners in copper plating baths |
| US4199417A (en) * | 1978-11-13 | 1980-04-22 | Mariano Borruso | Electrodeposition of black deposit and electrolytes therefor |
| US4417956A (en) * | 1980-07-17 | 1983-11-29 | Electrochemical Products, Inc. | Alkaline plating baths and electroplating process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2125229A (en) * | 1936-04-14 | 1938-07-26 | Harshaw Chem Corp | Electrodeposition of metals |
| US2613179A (en) * | 1946-06-20 | 1952-10-07 | Int Standard Electric Corp | Silver plating |
| US2694677A (en) * | 1949-11-10 | 1954-11-16 | Barnet D Ostrow | Bright copper plating bath |
-
0
- US US2732336D patent/US2732336A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2125229A (en) * | 1936-04-14 | 1938-07-26 | Harshaw Chem Corp | Electrodeposition of metals |
| US2613179A (en) * | 1946-06-20 | 1952-10-07 | Int Standard Electric Corp | Silver plating |
| US2694677A (en) * | 1949-11-10 | 1954-11-16 | Barnet D Ostrow | Bright copper plating bath |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2814590A (en) * | 1954-07-20 | 1957-11-26 | Lloyd B Portzer | Electrodeposition of copper |
| US2774728A (en) * | 1955-09-29 | 1956-12-18 | Du Pont | Addition agent for copper plating |
| US2870709A (en) * | 1955-10-28 | 1959-01-27 | Du Pont | Electroformed articles and process for their manufacture |
| US2854389A (en) * | 1956-04-30 | 1958-09-30 | Du Pont | Bright copper plating process |
| US2848394A (en) * | 1956-05-04 | 1958-08-19 | Hanson Van Winkle Munning Co | Bright copper plating |
| US2825684A (en) * | 1956-10-09 | 1958-03-04 | Du Pont | Bright copper plating |
| US2881122A (en) * | 1957-03-14 | 1959-04-07 | Hanson Van Winkle Munning Co | Electroplating |
| US2873234A (en) * | 1957-06-19 | 1959-02-10 | Metal & Thermit Corp | Electrodeposition of copper |
| US2861929A (en) * | 1957-06-20 | 1958-11-25 | Du Pont | Copper plating with addition agents |
| US3021266A (en) * | 1957-08-12 | 1962-02-13 | Barnet D Ostrow | Additive for copper plating bath |
| US3492135A (en) * | 1967-02-01 | 1970-01-27 | Schering Ag | Stabilized bath for deposition of copper by chemical reduction |
| US3532610A (en) * | 1967-10-27 | 1970-10-06 | Kewanee Oil Co | Selenium compounds as brighteners in copper plating baths |
| US4199417A (en) * | 1978-11-13 | 1980-04-22 | Mariano Borruso | Electrodeposition of black deposit and electrolytes therefor |
| US4417956A (en) * | 1980-07-17 | 1983-11-29 | Electrochemical Products, Inc. | Alkaline plating baths and electroplating process |
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