US2910413A - Brighteners for electroplating baths - Google Patents

Brighteners for electroplating baths Download PDF

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US2910413A
US2910413A US559519A US55951956A US2910413A US 2910413 A US2910413 A US 2910413A US 559519 A US559519 A US 559519A US 55951956 A US55951956 A US 55951956A US 2910413 A US2910413 A US 2910413A
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electroplating
bath
liter
acid
nickel
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US559519A
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Strauss Wennemar
Wedell Hans
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Dehydag Deutsche Hydrierwerke GmbH
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Dehydag Gmbh
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    • 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

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  • This invention relates to brighteners for electroplating 15 baths, and more particularly to acyclic brightening compounds comprising at least two carbon atoms linked exclusively to heteroatoms one of which is a sulfur atom, said compounds being free from sulfonic groups.
  • acyclic organic compounds used as brighteners for electroplating baths in accordance with the present invention are known chemical compounds and can be produced very readily according to Well known methods. These compounds can be represented by the following general structural formula:
  • R is a lower hydrocarbon radical, preferably a lower aliphatic radical which may carry substituent radicals other than sulfonic groups and/or may be interrupted by heteroatoms such as sulfur, oxygen and nitrogen
  • X, Y and Z are heteroatoms such as oxygen, sulfur and nitrogen or imino groups, at least one of them being a sulfur atom
  • X, Y and Z are also heteroatoms of the type represented by X, Y and Z or imino groups, at least one of them being a sulfur atom
  • Q and Q are hydrogen or lower aliphatic radicals free from sultonic groups.
  • the brightening compounds according to the present invention are primarily bisor poly-thiourea compounds, bisor poly-isothiourea compounds, bisor poly-thiocarbaminates, his or poly-dithiocarbaminates, bisor poly-xanthogenates, bisor poly-trithiocarbonates and the like. However, they also include compounds wherein the and or additional such groupings are not identical.
  • the brighteners disclosed above are effective in all types of electroplating processes, for example for copper-plating, zinc-plating and silver-plating, or also for the production of bright cadmium, bronze and brass electrodeposits. They are especially effective in the production of full-bright, firmly adhering, ductile metal electrodeposits from acidic electroplating baths.
  • the brighteners according to the present invention produce the desired beneficial effects when used as the sole brightener in the electroplating bath, they may readily be employed in conjunction with other types of brightening compounds.
  • the novel brightening agents herein disclosed are fully compatible with other additives usually added to electroplating solutions, namely smoothing agents, anti-porosity agents, Wetting agents or salts which increase the conductivity of the electroplating bath.
  • the brightening agents according to our invention are most advantageously used in conjunction with acid electroplating baths which also comprise aliphatic or aromatic sulfonic acids or their salts which contain halogen atoms or atom groups related to halogen, such as cyano or thiocyano groups, as substituents.
  • acid electroplating baths which also comprise aliphatic or aromatic sulfonic acids or their salts which contain halogen atoms or atom groups related to halogen, such as cyano or thiocyano groups, as substituents.
  • Specific examples of such sulfonic acid substitution products are the following:
  • nickel electroplating baths for example, with a brightening agent according to the present invention as well as with a sulfonic acid substitution product of the type above described, the characteristics of nickel electrodeposits produced therefrom are considerably improved over those produced under similar conditions from electroplating baths modified withadditives heretofore commonly used.
  • nickel electroplates are marked by their extraordinary smoothness, remarkable brightness, high ductility and complete freedom from porosity.
  • electroplating baths in addition with polyvalent alcohols, such as glycerin, butanetriol, pentaerythrite, mannitol and the like, or with polymerization products of unsaturated carboxylic acids or their salts, such as the sodium salt of polyacrylic acid, for example.
  • polyvalent alcohols such as glycerin, butanetriol, pentaerythrite, mannitol and the like
  • polymerization products of unsaturated carboxylic acids or their salts such as the sodium salt of polyacrylic acid
  • the amounts in which the brightening agents according to our invention or mixtures thereof are added to the electroplating bath depend largely upon the composition of the bath in question, but they range generally from 0.01 gm. to 20 gm. per liter of electroplating bath. As a rule, the best results are obtained if the metal is deposited from the modified bath at a temperature between room temperature and about 70 C., and at current densities from 0.5 to amp./dm.
  • novel brighteners disclosed herein are, for all practical purposes, not consumed during the electroplating process and are chemically very stable compounds, so that electroplating baths modified therewith remain operative and effective for extremely long periods .of time.
  • Example 10 1 gm. of ethylene-bis- (dimethylamino-dithiocarbaminate) having the structural formula (Chian if-scH20H2s-en(cnm s s was added to each liter of an acid copper electroplating bath composed of water, 60 gm./liter sulfuric acid and 170 gm./liter crystalline copper sulfate. Sheet iron objects which had previously been provided with a copper base-coat in an alkaline copper cyanide bath, were then electroplated in the modified bath at room temperature and at current densities between 1 and 10 amp./dm. They were provided with full-bright, firmly adhering copper deposits, even when highly profiled. The electrodeposits required no polishing, bufling or any other finishing treatment subsequent to rinsing.
  • Example I l 1 gm. bromoethane-sodium sulfonate and ;0.;l .gm. ethylene-diisothiourea-hydrobromide having the structural formula H2N-C-S-CIIg-CH3SONH5.2H-BI NH NH were added to each liter .of an acid .nickelrelectroplating bath composed of water, 60 gm./liter nickel chloride, 220 gm] liter crystalline nickel sulfate and 35 gm./ lite r.bo1fic acid. Sheet iron objects electroplated in thisrnpd fied bath at a temperature of about 60 C. and a current density of 1 to 8 amp./dm. were provided with very bright, firmly adhering nickel-plates which required no finishing treatment of any kind subsequent to rinsing.
  • Example III 0.2 gm. of l,3-diisothiourea-propanol-2-hydrobromide having the structural formula H N C- s-CH OH-CH SC-NHz.2HBr
  • Example 1 V 1 gm. of ethylene-bis-(thiourea) according to Formula 4 was used instead of the brightener in Example I. A full bright copper deposit was obtained.
  • Example V 1 gm. of ethylene-bis-(dithiomethylcarbaminate) according to Formula 5 was used instead of the first named brightener in Example II. A good nickel plating was obtained.
  • Example VI 1 gm. of ethylene-l-(methylxanthogenate)-2-(methylsulfthiocarbonate according to Formula 6 was substituted for the first named brightener in Example III. A bright nickel deposit was formed.
  • An electroplating bath for producing bright deposits of metals selected from the group consisting of copper, zinc, silver, nickel, cadmium, bronze and brass comprising an aqueous acid solution of an inorganic salt of the metal to be deposited and from about 0.01 to about 20 grams/liter of an acyclic organic compound having the general structural formula it t wherein R is a lower aliphatic radical, Q and Q are selected from the group consisting of hydrogen, lower alkyl and lower hydroxy-alkyl, X, Y and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the imino radical, and X, Y and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the irnino radical.
  • An electroplating bath as in claim 1, comprising in I addition a compound selected from the group consisting of halogenated lower alkyl sulfonic acids, halogenated aryl sulfonic acids and salts of such sulfonic acids.
  • An electroplating bath as in claim 1, comprising in addition a compound selected from the group consisting of bromine-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
  • An electroplating bath as in claim 1, comprising in addition a compound selected from the group consisting of cyanoand thiocyano-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
  • An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of halogenated lower alkyl sulfonic acids, halogenated aryl sulfonic acids and salts of such sulfonic acids.
  • An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of bromine-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
  • An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of cyanoand thiocyano-substituted. lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.

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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)
  • Paints Or Removers (AREA)

Description

2,919,411? Patented Oct. 27, 1959 2,910,413 BRIGHTENERS FOR ELECTROPLATING BATHS Wennemar Strauss and Hans Wedell, Dusseldorf-Holt- 5 hausen, Germany, assignors to Dehydag, Deutsche Hydrierwerke G.m.b.H., Dusseldorf, Germany, a corporation of Germany N0 Drawing. Application January 17, '1956 Serial No. 559,519
Claims priority, application Germany January 19, 1955 12 Claims. (Cl. 204-44) This invention relates to brighteners for electroplating 15 baths, and more particularly to acyclic brightening compounds comprising at least two carbon atoms linked exclusively to heteroatoms one of which is a sulfur atom, said compounds being free from sulfonic groups.
We have found that very bright, firmly adhering, ductile metal electrodeposits are obtained by modifying electroplating baths, containing the metal to be deposited primarily in the form of an acid solution of an inorganic salt of the metal, with water-soluble acyclic organic compounds free from sulfonic groups which have at least two carbon atoms in the molecule, said carbon atoms being linked exclusively to heteroatoms at least one of which is a sulfur atom. The atom groups formed by the carbon atoms and the heteroatoms, which may be identi cal or different, are further linked through one of said heteroatoms to a lower hydrocarbon radical, preferably a bivalent lower alkyl radical, which may be further substituted and/or interrupted by heteroatoms.
The acyclic organic compounds used as brighteners for electroplating baths in accordance with the present invention are known chemical compounds and can be produced very readily according to Well known methods. These compounds can be represented by the following general structural formula:
wherein R is a lower hydrocarbon radical, preferably a lower aliphatic radical which may carry substituent radicals other than sulfonic groups and/or may be interrupted by heteroatoms such as sulfur, oxygen and nitrogen, X, Y and Z are heteroatoms such as oxygen, sulfur and nitrogen or imino groups, at least one of them being a sulfur atom, X, Y and Z are also heteroatoms of the type represented by X, Y and Z or imino groups, at least one of them being a sulfur atom, and Q and Q are hydrogen or lower aliphatic radicals free from sultonic groups.
Thus, the brightening compounds according to the present invention are primarily bisor poly-thiourea compounds, bisor poly-isothiourea compounds, bisor poly-thiocarbaminates, his or poly-dithiocarbaminates, bisor poly-xanthogenates, bisor poly-trithiocarbonates and the like. However, they also include compounds wherein the and or additional such groupings are not identical.
A few representative examples of the types of compounds which we have found to be excellent brightening agents for electroplating baths are the following: i
The brighteners disclosed above are effective in all types of electroplating processes, for example for copper-plating, zinc-plating and silver-plating, or also for the production of bright cadmium, bronze and brass electrodeposits. They are especially effective in the production of full-bright, firmly adhering, ductile metal electrodeposits from acidic electroplating baths.
While the brighteners according to the present invention produce the desired beneficial effects when used as the sole brightener in the electroplating bath, they may readily be employed in conjunction with other types of brightening compounds. Moreover, the novel brightening agents herein disclosed are fully compatible with other additives usually added to electroplating solutions, namely smoothing agents, anti-porosity agents, Wetting agents or salts which increase the conductivity of the electroplating bath.
We have found that the brightening agents according to our invention are most advantageously used in conjunction with acid electroplating baths which also comprise aliphatic or aromatic sulfonic acids or their salts which contain halogen atoms or atom groups related to halogen, such as cyano or thiocyano groups, as substituents. Specific examples of such sulfonic acid substitution products are the following:
Bromoethane sulfonic acid 2-cyanoethane-sulfonic acid Z-thiocyanoethane-sulfonic acid 3-bromopropane-sulfonic acid-l 3-iodopropane-sulfonic acid-1 2,3-dichloropropane-sulfonic acid-1 4-bromobutane-sulfonic acid-1 3-chlorobenzene-sulfonic acid-1 4-bromobenzene-sulfonic acid-1 2,4,5-trichlorobenzene-sulfonic acid-1 2-chlorophenol-sulfonic acid-4 5-bromo-2-nitrobenzene-sulfonic acid-1 4-iodotoluene-sulfonic acid-3 4-bromobenzyl-sulfonic acid 4-chloronaphthalene-sulfonic acid-l 4,4-dibromodiphenyl-disulfonic acid-2,2
and the like. Thus, by modifying an acid nickel electroplating bath, for example, with a brightening agent according to the present invention as well as with a sulfonic acid substitution product of the type above described, the characteristics of nickel electrodeposits produced therefrom are considerably improved over those produced under similar conditions from electroplating baths modified withadditives heretofore commonly used. In particular, such nickel electroplates are marked by their extraordinary smoothness, remarkable brightness, high ductility and complete freedom from porosity.
It is further advantageous to modify such electroplating baths in addition with polyvalent alcohols, such as glycerin, butanetriol, pentaerythrite, mannitol and the like, or with polymerization products of unsaturated carboxylic acids or their salts, such as the sodium salt of polyacrylic acid, for example. The addition of such compounds -to electroplating baths modified in accordance with the present invention makes it possible to reduce the amount of brightening agent necessary to produce the desired brightening effect, and in some instances further to improve the characteristics of the metal electrodeposits.
The amounts in which the brightening agents according to our invention or mixtures thereof are added to the electroplating bath depend largely upon the composition of the bath in question, but they range generally from 0.01 gm. to 20 gm. per liter of electroplating bath. As a rule, the best results are obtained if the metal is deposited from the modified bath at a temperature between room temperature and about 70 C., and at current densities from 0.5 to amp./dm.
The novel brighteners disclosed herein are, for all practical purposes, not consumed during the electroplating process and are chemically very stable compounds, so that electroplating baths modified therewith remain operative and effective for extremely long periods .of time.
The following examples will further illustrate the .present invention and enable others skilled in the ar t to understand our invention more completely. However, the recitation of these .examples should not be construed as an intention on our part to limit our invention to the compounds and conditions mentioned in the examples.
Example] 1 gm. of ethylene-bis- (dimethylamino-dithiocarbaminate) having the structural formula (Chian if-scH20H2s-en(cnm s s was added to each liter of an acid copper electroplating bath composed of water, 60 gm./liter sulfuric acid and 170 gm./liter crystalline copper sulfate. Sheet iron objects which had previously been provided with a copper base-coat in an alkaline copper cyanide bath, were then electroplated in the modified bath at room temperature and at current densities between 1 and 10 amp./dm. They were provided with full-bright, firmly adhering copper deposits, even when highly profiled. The electrodeposits required no polishing, bufling or any other finishing treatment subsequent to rinsing.
Example I l 1 gm. bromoethane-sodium sulfonate and ;0.;l .gm. ethylene-diisothiourea-hydrobromide having the structural formula H2N-C-S-CIIg-CH3SONH5.2H-BI NH NH were added to each liter .of an acid .nickelrelectroplating bath composed of water, 60 gm./liter nickel chloride, 220 gm] liter crystalline nickel sulfate and 35 gm./ lite r.bo1fic acid. Sheet iron objects electroplated in thisrnpd fied bath at a temperature of about 60 C. and a current density of 1 to 8 amp./dm. were provided with very bright, firmly adhering nickel-plates which required no finishing treatment of any kind subsequent to rinsing.
Example III 0.2 gm. of l,3-diisothiourea-propanol-2-hydrobromide having the structural formula H N C- s-CH OH-CH SC-NHz.2HBr
l TH 0H bin 8 gm. 3-b romopropane-sodium sulfonate and 5 gm. glycerin were added to each liter of an acid nickel electroplating bath composed of water, 60 gm./liter nickel chloride, 220 gm./liter crystalline nickel sulfate and 35 gm./liter boric acid. Sheet iron objects electroplated in this modified bath at a temperature of about 60 C. and a current density between 1 and 8 amp/din. were provided with exceptionally bright, firmly adhering nickel electroplates which required no finishing treatment of any kind subsequent to rinsing.
Example 1 V 1 gm. of ethylene-bis-(thiourea) according to Formula 4 was used instead of the brightener in Example I. A full bright copper deposit was obtained.
Example V 1 gm. of ethylene-bis-(dithiomethylcarbaminate) according to Formula 5 was used instead of the first named brightener in Example II. A good nickel plating was obtained.
Example VI 1 gm. of ethylene-l-(methylxanthogenate)-2-(methylsulfthiocarbonate according to Formula 6 was substituted for the first named brightener in Example III. A bright nickel deposit was formed.
While we have illustrated our invention with the aid of certain specific embodiments thereof, it will be apparent to persons skilled in the art that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.
We claim:
1. An electroplating bath for producing bright deposits of metals selected from the group consisting of copper, zinc, silver, nickel, cadmium, bronze and brass comprising an aqueous acid solution of an inorganic salt of the metal to be deposited and from about 0.01 to about 20 grams/liter of an acyclic organic compound having the general structural formula it t wherein R is a lower aliphatic radical, Q and Q are selected from the group consisting of hydrogen, lower alkyl and lower hydroxy-alkyl, X, Y and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the imino radical, and X, Y and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the irnino radical.
2. An electroplating bath as in claim 1, comprising in I addition a compound selected from the group consisting of halogenated lower alkyl sulfonic acids, halogenated aryl sulfonic acids and salts of such sulfonic acids.
3. An electroplating bath as in claim 1, comprising in addition a compound selected from the group consisting of bromine-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
4. An electroplating bath as in claim 1, comprising in addition a compound selected from the group consisting of cyanoand thiocyano-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
5. An electroplating bath as in claim 1, which com- P 'i$S n addition a compound selected from the group imino radical, and X, Y
consisting of polyvalent alcohols, polymerization products of unsaturated carboxylic acids, and salts of such polymerization products.
6. The electroplating bath of claim 1 wherein the aliphatic radical is substituted.
7. The electroplating bath of claim 1 wherein the aliphatic radical is interrupted by hetero atoms.
8. The process of producing bright and lustrous electrodeposits of metals selected from the group consisting of copper, zinc, silver, nickel, cadmium, bronze and brass, which comprises electrodepositing said metal from a bath containing said metal principally in the form of an aqueous acid solution of an inorganic salt of said metal in the presence of from about 0.01 to about 20 grams/liter of a bn'ghtener, said brightener being an organic acyclic compound having the general structural formula wherein R is a lower aliphatic radical, Q and Q are se lected from the group consisting of hydrogen, lower alkyl and lower hydroXy-alkyl, X, Y and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the and Z are selected from the group consisting of oxygen, sulfur, nitrogen and the imino radical.
9. An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of halogenated lower alkyl sulfonic acids, halogenated aryl sulfonic acids and salts of such sulfonic acids.
10. An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of bromine-substituted lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
11. An electroplating process as in claim 8, comprising in addition a compound selected from the group consisting of cyanoand thiocyano-substituted. lower alkyl and aryl sulfonic acids and salts of such sulfonic acids.
12. An electroplating process as in claim 8, which comprises in addition a compound selected. from the group consisting of polyvalent nets of unsaturated carboxylic acids, and salts of such polymerization products.
References Cited in the file of this patent UNITED STATES PATENTS alcohols, polymerization prod-

Claims (1)

1. AN ELECTOPLATING BATH FOR PRODUCING BRIGHT DEPOSITS OF METALS SELECTED FROM THE GOUP CONSISTING OF COPPER, ZINC, SILVER, NICKEL, CADMIUM, BRONZE AND BRASS COMPRISING AN AQUEOUS ACID SOLUTION OF AN INORGANIC SALT OF THE METAL TO BE DEPOSITED AND FROM ABOUT 0.01 TO ABOUT 20 GRAMS/LITER OF AN ACYCLIC ORGANIC COMPOUND HAVING THE GENERAL STRUCTURAL FORMULA
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000799A (en) * 1960-02-10 1961-09-19 Harshaw Chem Corp Nickel plating solutions
US3051634A (en) * 1957-11-30 1962-08-28 Dehydag Gmbh Baths for the production of copper electroplates
US3095362A (en) * 1960-11-21 1963-06-25 Incar Inc Zinc plating composition and process
US3109784A (en) * 1960-11-21 1963-11-05 Incar Inc Copper plating composition and process
US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
US3274080A (en) * 1962-05-25 1966-09-20 Cowles Chem Co Brighteners and process for cyanide zinc electrodeposition
US3400059A (en) * 1964-03-07 1968-09-03 Dehydag Gmbh Acidic copper electroplating baths and method
US3414493A (en) * 1965-10-19 1968-12-03 Lea Ronal Inc Electrodeposition of copper
US3506548A (en) * 1966-09-23 1970-04-14 Allied Res Prod Inc Electrodeposition of nickel
US3518171A (en) * 1969-07-24 1970-06-30 Metalux Corp The Purification of nickel electroplating solutions
US3725220A (en) * 1972-04-27 1973-04-03 Lea Ronal Inc Electrodeposition of copper from acidic baths
US3770599A (en) * 1971-05-24 1973-11-06 Oxy Metal Finishing Corp Acid zinc plating baths
US3923613A (en) * 1972-02-22 1975-12-02 Kampschulte & Cie Dr W Acidic galvanic copper bath
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US5385661A (en) * 1993-09-17 1995-01-31 International Business Machines Corporation Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition
WO2000056952A1 (en) * 1999-03-19 2000-09-28 Technic, Incorporated Electroplating baths
US6179985B1 (en) * 1999-03-19 2001-01-30 Technic, Inc. Metal alloy fluoroborate electroplating baths
US6248228B1 (en) * 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
US6251253B1 (en) * 1999-03-19 2001-06-26 Technic, Inc. Metal alloy sulfate electroplating baths
US6562220B2 (en) * 1999-03-19 2003-05-13 Technic, Inc. Metal alloy sulfate electroplating baths
US6607653B1 (en) * 1999-09-27 2003-08-19 Daiwa Fine Chemicals Co., Ltd. Plating bath and process for depositing alloy containing tin and copper
US7628903B1 (en) * 2000-05-02 2009-12-08 Ishihara Chemical Co., Ltd. Silver and silver alloy plating bath

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DE1271491B (en) * 1964-05-05 1968-06-27 Cowles Chem Co Galvanic alkaline zinc cyanide bath
FR1519645A (en) * 1966-12-30 1968-04-05 Pernix Enthone Electrolytic tinning improvements

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US2644789A (en) * 1951-08-02 1953-07-07 Harshaw Chem Corp Electrodeposition of nickel
DE888493C (en) * 1951-11-03 1953-09-03 Hydrierwerke A G Deutsche Process for the production of firmly adhering and shiny galvanic copper coatings
US2742412A (en) * 1952-07-05 1956-04-17 Metallic Industry Nv Electrolytic deposition of copper

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US2644789A (en) * 1951-08-02 1953-07-07 Harshaw Chem Corp Electrodeposition of nickel
DE888493C (en) * 1951-11-03 1953-09-03 Hydrierwerke A G Deutsche Process for the production of firmly adhering and shiny galvanic copper coatings
US2742412A (en) * 1952-07-05 1956-04-17 Metallic Industry Nv Electrolytic deposition of copper

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3051634A (en) * 1957-11-30 1962-08-28 Dehydag Gmbh Baths for the production of copper electroplates
US3000799A (en) * 1960-02-10 1961-09-19 Harshaw Chem Corp Nickel plating solutions
US3095362A (en) * 1960-11-21 1963-06-25 Incar Inc Zinc plating composition and process
US3109784A (en) * 1960-11-21 1963-11-05 Incar Inc Copper plating composition and process
US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
US3274080A (en) * 1962-05-25 1966-09-20 Cowles Chem Co Brighteners and process for cyanide zinc electrodeposition
US3400059A (en) * 1964-03-07 1968-09-03 Dehydag Gmbh Acidic copper electroplating baths and method
US3414493A (en) * 1965-10-19 1968-12-03 Lea Ronal Inc Electrodeposition of copper
US3506548A (en) * 1966-09-23 1970-04-14 Allied Res Prod Inc Electrodeposition of nickel
US3518171A (en) * 1969-07-24 1970-06-30 Metalux Corp The Purification of nickel electroplating solutions
US3770599A (en) * 1971-05-24 1973-11-06 Oxy Metal Finishing Corp Acid zinc plating baths
US3923613A (en) * 1972-02-22 1975-12-02 Kampschulte & Cie Dr W Acidic galvanic copper bath
US3725220A (en) * 1972-04-27 1973-04-03 Lea Ronal Inc Electrodeposition of copper from acidic baths
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US5385661A (en) * 1993-09-17 1995-01-31 International Business Machines Corporation Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition
US6251253B1 (en) * 1999-03-19 2001-06-26 Technic, Inc. Metal alloy sulfate electroplating baths
US6179985B1 (en) * 1999-03-19 2001-01-30 Technic, Inc. Metal alloy fluoroborate electroplating baths
US6248228B1 (en) * 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
WO2000056952A1 (en) * 1999-03-19 2000-09-28 Technic, Incorporated Electroplating baths
US6562220B2 (en) * 1999-03-19 2003-05-13 Technic, Inc. Metal alloy sulfate electroplating baths
AU773971B2 (en) * 1999-03-19 2004-06-10 Specialty Chemical Systems, Inc. Electroplating baths
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DE1007592B (en) 1957-05-02

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