US3318787A - Electrodeposition of zinc - Google Patents
Electrodeposition of zinc Download PDFInfo
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- US3318787A US3318787A US343220A US34322064A US3318787A US 3318787 A US3318787 A US 3318787A US 343220 A US343220 A US 343220A US 34322064 A US34322064 A US 34322064A US 3318787 A US3318787 A US 3318787A
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- methyl
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
- C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
Definitions
- This invention relates to improvements in the electrodeposition of zinc, and is particularly concerned with the electrodeposition of bright zinc from alkaline cyanide zinc baths which contain as brightening agents bathsoluble quaternary nitrogen compounds containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamides, carboxy and nitrile groups, hereinafter more fully described.
- the electrodeposition of zinc from alkaline cyanide zinc solutions is widely used to produce coatings which protect iron and steel by sacrificial cathodic protection. It is an outstanding metal for providing this desirable protection.
- the electrodeposited zinc have a pleasing luster that does not tarnish too rapidly, and many brighteners and addition agents have been developed to improve the appearance of the electroplated zinc obtained from cyanide zinc baths which normally yield dull gray plate.
- the bright zinc electrodeposits In the present state of the art, it is quite common to subject the bright zinc electrodeposits to oxidizing acid dips such as chromic acid dips to produce passive films for further protective effects and for superior lacquer and paint adhesion. It is also quite common to also subject the zinc electrodeposits to phosphate type dips to produce films giving rise to improved adhesion of paint coatings to the zinc surface. It is very important in many cases that the bright zinc electrodeposits can be subjected to such dips with no resultant discoloration of the zinc electrodeposit and with good uniformity of the films.
- addition agents for alkaline cyanide zinc electroplating baths used in accordance with the prior art are subject to certain disadvantages.
- inorganic addition agents used in the rather high concentrations found in the prior art have a tendency to cause an undesirable appearance of the zinc electrodeposit when subsequently subjected to the commonly used passivating dips.
- Addition agents such as aromatic aldehydes, polyvinyl alcohol, modified polyvinyl alcohols such as oxidized polyvinyl alcohol, and ethoxylated derivatives, various grades of gelatin and glue, used alone or in combination with each other, still leave much to be desired, in that the current density range at which acceptable bright zinc electroplate is produced is narrow and limited to the lower current density range of the bat Over the years, a great deal of work has been done to promote the increased use of this important metal as an electrodeposited coating. One of the best means to achieve this is by the development of improved addition agents to obtain brighter zinc deposits over a broad plating range from the electroplating bath. The improved addition agents should also provide an electroplating bath that is relatively easy to operate and economical to use.
- bath-soluble quaternary nitrogen compounds containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamides, carboxy and nitrile (cyano) groups make possible the electrodeposition of smooth bright zinc deposits from alkaline cyanide zinc baths over a wide cathode current density range.
- addition agents for alkaline zinc baths such as the aforementioned aryl aldehydes, gelatin and glue of various grades, polyvinyl alcohol and modified polyvinyl alcohol, such as oxidized polyvinyl alcohol, ethoxylated polyvinyl alcohol, peptones, formaldehyde, and very specifically with very small concentrations of the inorganic addition agent manganese, also with molybdenum oxide, trivalent chromium, iron and with combinations of these prior art addition agents, to give very high brightness over a broad current density plating range.
- polyvinyl alcohol and modified polyvinyl alcohol such as oxidized polyvinyl alcohol, ethoxylated polyvinyl alcohol, peptones, formaldehyde, and very specifically with very small concentrations of the inorganic addition agent manganese, also with molybdenum oxide, trivalent chromium, iron and with combinations of these prior art addition agents, to give very high brightness over a broad current density plating range.
- R is a radical selected from the group consisting of hydroxy and alkoxy groups, alkenoxy, alkynoxy and substituted alkoxy, alkenoxy and alkynoxy groups, amide and substituted amide groups.
- R may be NH --NHCH a)2, NHC2H5: 2 5)2, s 5 NH(C H.,O) 'H, NH(C H O),,H, etc.
- R may be alkyl, alkylene, alkene, alkyne, alkyl phenyl, phenyl, and
- alkyl naphthyl radicals and the alkyl and aryl groups may have specific substituting groups such as halogen, nitro, nitroso, hydroxy, alkoxy, carboxy, cyano, sulfo, ester, methyl, ethyl, etc. These same specific substituting groups may be used for R on the carbon of the pyridine rings.
- R represents the cyano radical.
- A represents an anion or an anionic linkage such as chloro, bromo, iodo, fluoro, sultone, methosulfate, ethosulfate, hydroxide, oxide, betaine or sulfobetaine anionic linkage.
- the most important substituting groups on the carbon of the pyridine rings are the carboxylic ester and carboxamide groups, next is the nitrile group.
- the character of the anion A is not important for the brightening action, and wherether A is chloride, bromide, hydroxide, methosulfate, ethosulfate, or is in oxide, sultone or betaine or sulfobetaine form of anionic linkage is not of great significance.
- Allyl bromide, benzyl chloride, methyl or ethyl chloroacetate quaternaries of methyl, ethyl or propyl nicotinates give excellent brightening results in the alkaline zinc baths, and the quaternaries of methyl, ethyl, propyl and allyl chloroacetates or chloropropionates give excellent results not only with pyridine and the substituted pyridines, but also with triethanolamine, triethylamine, triallylamine, tetramethyl ethylene diamine, and other amines.
- Excellent examples of very effective zinc brighteners are Compounds 4 and 16 of Table I C O CH3 0 ONHz which are respectively the benz-yl chloride quaternary of methyl nicotinate and the methyl chloroacetate quaternary of nicotinamide.
- the zinc deposits were plated on panels of cold-rolled steel after which they were removed from the Hull cell, rinsed in clear water, immersed in a solution of about 0.25% by volume of concentrated nitric acid for about 10 seconds to observe the efiect of the bright dip, rinsed in clear water, and dried.
- Other acidic oxidizing bright dips could have, of course, been used instead of the above mentioned nitric acid bright dip to observe the required results.
- novel addition agents of this invention are effective in any commercially operable alkaline cyanide zinc plating bath, as a basic plating solution, it is preferred to use the well known cyanide zinc plating bath composition and operating conditions shown in Table II.
- This bath composition can be varied as required for special purposes in accordance with the now known skill in the art. For example, for better coverage in deep recesses, the metal content can be decreased, and the cyanide content increased. This, however, is accomplished at the expense of an over-all decrease in cathode efficiency.
- Example II To a cyanide zinc plating hath made up and operated as above described in Table II there was added another novel addition agent of this invention, N-benzyl 3-methyl carboxylate pyridinium chloride in a concentration of 0.35 gram/ liter. Zinc deposits plated on Hull cell panels from this bath were bright from current densities of above 100 amps/sq. ft. to about 4 amps/sq. ft. The brightness of the deposit was improved after the as plated deposit was subjected to the previously described dilute nitric acid bright dip.
- Example III To an alkaline cyanide zinc electroplating solution made up and operated as described in Table II there was added the following: 0.37 gram/liter N-allyl 2-ethyl carboxylate pyridinium bromide and 0.11 gram per liter polyvinyl alcohol.
- Zinc deposits plated on Hull cell panels from this bath were superior in brightness to any of those so far described.
- the bright plate range was also superior to any of the deposits so far described, extending from the high current density edge of the Hull cell panel to the low current density edge of the panel. At the very lowest current density area some imperfection in the smoothness of the deposit could be noticed.
- Example IV To the cyanide zinc plating solution made up and operated as described in Table II there was added the following example of yet another novel addition agent of this invention, 0.25 gram/liter bis-1,4-xylylene-3,3-methyl carboxylate pyridinium chloride and 0.11 grams per liter polyvinyl alcohol and 0.37 gram/liter oxidized ethoxylated polyvinyl alcohol.
- Zinc deposits plated on Hull cell panels from this bath were superior to those obtained under Example III in that the zinc deposit in the lowest current density area was now smooth and fully bright. The brightness of the zinc deposit was further improved after subjecting it to the dilute nitric acid bright dip as described above.
- Example V To an alkaline cyanide zinc electroplating solution made up and operated as described in Table II, there was added 0.25 gram/liter N-benzyl 3-carboxamide pyridinium bromide, and 0.12 gram/ liter polyvinyl alcohol. Zinc deposits plated on Hull cell panels from this bath had a bright current density range from the extreme high current density edge of the panel to the low current density edge of the panel.
- Example VI To the cyanide zinc plating solution made up and operated as described in Table II, there was added the following, 0.37 gram/liter N-benzyl 3-ethyl carboxylate pyridinium chloride, and 0.15 gram/liter oxidized polyvinyl alco hol. Zinc deposits plated on Hull cell panels from this bath were bright over abroad current density range. The brightness of the zinc deposit was further improved after subjecting it to the dilute nitric acid bright dip as described above.
- Example VII To a cyanide zinc solution made up and operated as described in Table II, there was added the following to further illustrate the novel features inherent in this invention, 0.28 gram/liter N-benzyl 3-methyl carboxylate pyridinium chloride, and 0.2 gram/liter glue.
- Zinc deposits plated on Hull cell panels from this bath had a bright current density range from about 80 amps/sq. ft. to the lowest current density edge of the panel. .
- the deposit was exceptionally bright at the lowest current density edge of the panel and the coverage was excellent.
- the characteristics of the deposit indicate the use of this combination of addition agents where the electroplating of parts in bulk barrel plating is to be carried out.
- Example VIII To an alkaline cyanide zinc electroplating hath made up and operated as described in Table II there was added 0.28 gram/liter N-allyl 3-ethyl carboxylate pyridinium bromide, 0.17 gram/ liter glue, 0.24 gram per liter anisic aldehyde bisulfite and 0.05 gram/liter gelatin. Zinc deposits plated on Hull cell panels from this bath were superior in brightness to those produced in Example VII and the bright current density range was extended to about amps/sq. ft.
- Metals such as manganese in the form of a manganese salt can be used in conjunction with the quaternaries illustrated in ,Table I, however, only very small concentrations are necessary to secure beneficial effects. For example, only about 0.005 to 0.1 gram/liter of manganese sulfate need be used, unlike the much larger concentrations usually necessary (see Westbrook United States Patent 2,080,520, issued May 18, 1937, and United States Patent 2,218,734, issued Oct. 22, 1940).
- the manganous salt can be used in the low concentrations in any one of the above eight cited bath examples with good results under prolonged use. Iron in the form of a ferrous or ferric salt is also beneficial in conjunction with the quaternaries of Table I.
- the more potent metal brighteners molybdenum oxide, and trivalent chromium cooperate with low conccntrations of the quaternaries of Table I, but do not give much enhanced brightness with the: higher concentrations of the quaternaries.
- the organic compounds that cooperate excellently with the quaternaries exemplified in Table I are the type represented by bath-soluble polyvinyl compounds such as polyvinyl alcohols and modified polyvinyl alcohols such as oxidized polyvinyl alcohol (Wernlund US. 2,928,800, Mar. 15, 1960),
- polyvinyl alcohols and moditied polyvinyl alcohols may be present in the baths in conjunction with the quaternaries exemplified in Table I, in a total concentration of about 0.005 to about 0.5 gram/liter.
- sequestering agents such as the ethylene diamine tetracetates, nitrilotriacetates, glucoheptosaminic acid salts, N,N bis (2 hydroxyethyl) :glycinate, etc., in concentrations of about 0.1 to about 10 grams/liter, to keep the dissolved manganese especially, or dissolved iron or both in solution.
- Gluconates, and citrates also help in sequestering when metal brighteners are used in the alkaline cyanide zinc baths in conjunction with the compounds of Table I.
- the protective colloid gelatin or impure gelatin cooperates with the bath-soluble quaternaries of substituted pyridines when these gelatin materials are used in concentrations of 0.005 to about 0.3 gram/liter.
- the aromatic aldehydes such as anisic aldehyde and piperonal (heliotropin) cooperate with the quaternaries when these aldehydes are used in a concentration of 0.005 to about 0.5 gram/liter.
- All of these quaternaries for use in alkaline cyanide zinc electroplating baths can be classified as bath-soluble quaternary nitrogen compounds containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamides, carboxy and nitrile groups, and to be used in a concentration range of 0.005 to about 5 grams/liter, with 0.1 to 0.8 gram/liter usually the optimum amounts.
- Outstanding among these compounds are the quaternaries of methyl, ethyl, or propyl nicotinate esters.
- a bath for the electrode-position of lustrous zinc comprising an aqueous alkaline cyanide zinc bath containing dissolved therein in a concentration of about 0.005 to about 5 grams per liter of a bath-soluble quaternary nitrogen compound containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamide, carboxy and nitrile groups.
- a bath as claimed in claim 1 wherein said quaternary is N-allyl,3-ethyl carboxylate pyridinium bromide.
- a bath as claimed in claim 1 wherein said quaternary is N-rnethyl carboxymethyl 3-ethyl carboxylate pyridinium chloride.
- a bath as claimed in claim 1 wherein said quaternary is N-benzyl,3-ethyl carboxylate pyridinium chloride.
- a bath as claimed in claim 1 wherein said quaternary is bis-1,4-xylene-3,3-ethyl carboxylate pyridinium chloride.
- a bath as claimed in claim 1 wherein said quaternary is a quaternary of ethyl nicotinate.
- a bath as claimed in claim 1 wherein said quaternary is a quaternary of propyl nicotinate.
- a bath as claimed in claim 1 wherein there is also present in said bath a bath-soluble polyvinyl compound selected from the class of polyvinyl alcohol, oxidized polyvinyl alcohol, ethoxylated polyvinyl alcohol and oxidized ethoxylated polyvinyl alcohol, said bath-soluble poly-vinyl compound being present in a concentration of about 0.005 to about 0.5 gram/liter.
- a method for the electrodeposition of lustrous zinc comprising the step of electrodepositing zinc from an aqueous alkaline cyanide zinc bath containing dissolved therein in a concentration of about 0.005 to about 5 grams/liter of a bath-soluble quaternary nitrogen compound containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamide, carboxy, and nitrile groups.
- a method as claimed in claim 15 and wherein said quaternary is N-allyl,3-ethyl carboxylate pyridinium bromide.
- a method as claimed in claim 15 and wherein said quaternary is N-methyl carboxymethyl 3-ethyl carboxylate pyridinium chloride.
- a bath for electrodeposition of lustrous zinc comprising an aqueous alkaline cyanide zinc bath containing dissolved therein in a concentration of about 0.005 to about 5 grams per liter of a bath soluble pyridinium quaternary compound containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, substituted carboxamide, carboxy and nitrile groups.
- a method for the electrodeposition of lustrous zinc References Cited by the Examiner comprising the step of electrodepositing zinc from an UNITED STATES PATENTS aqueous alkaline cyanide zinc bath containing dissolved 2 842 488 7/1958 S trauss et a1 204-55 X thereln in a concentratlon of ebout 0.005 to about 5 2,900,313 8/1959 Saubestre et a1 204 55 X grams/liter of a bath-soluble pyridinium quaternary com- 5 2 928 800 3/1960 Wemlund X pound containing at least one substituting group selected from the class consisting of carboxylic ester, carboxamide, JOHN MACK, Primary Examlner' substituted carboxamide, carboxy, and nitrile groups.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Pyridine Compounds (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
Claims (1)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US343220A US3318787A (en) | 1964-02-07 | 1964-02-07 | Electrodeposition of zinc |
DE1521069A DE1521069C2 (en) | 1964-02-07 | 1965-01-14 | Galvanic zinc cyanide bath |
FR4515A FR1427282A (en) | 1964-02-07 | 1965-02-05 | Zinc electrolytic deposition processes and new baths used for this purpose |
GB5393/65A GB1049132A (en) | 1964-02-07 | 1965-02-08 | Improvements in or relating to the electrodeposition of zinc |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US343220A US3318787A (en) | 1964-02-07 | 1964-02-07 | Electrodeposition of zinc |
Publications (1)
Publication Number | Publication Date |
---|---|
US3318787A true US3318787A (en) | 1967-05-09 |
Family
ID=23345190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US343220A Expired - Lifetime US3318787A (en) | 1964-02-07 | 1964-02-07 | Electrodeposition of zinc |
Country Status (4)
Country | Link |
---|---|
US (1) | US3318787A (en) |
DE (1) | DE1521069C2 (en) |
FR (1) | FR1427282A (en) |
GB (1) | GB1049132A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3411996A (en) * | 1965-12-02 | 1968-11-19 | Du Pont | Process for brightening zinc and cadmium electroplate using an inner salt of a quaternized pyridine carboxylic acid and compositions containing the same |
DE2111602A1 (en) * | 1970-03-18 | 1971-10-07 | Udylite Corp | Aqueous, cyanide-free galvanic zinc bath |
JPS4842935A (en) * | 1971-09-30 | 1973-06-21 | ||
US3755097A (en) * | 1971-10-27 | 1973-08-28 | Stauffer Chemical Co | Novel process for electrodepositing zinc |
US3769183A (en) * | 1971-06-18 | 1973-10-30 | Du Pont | Cyanide zinc electroplating |
US3769184A (en) * | 1972-05-23 | 1973-10-30 | Du Pont | Acid zinc electroplating |
DE2318985A1 (en) * | 1973-01-05 | 1974-07-18 | Oxy Metal Finishing Corp | PROCESS FOR IMPROVING GALVANIC ZINC DEPOSITION THROUGH THE USE OF MULTIPLE QUARTERLY NITROGEN COMPOUNDS |
US3884774A (en) * | 1973-02-01 | 1975-05-20 | Lea Ronal Inc | Electrolytic deposition of zinc |
US3909373A (en) * | 1972-06-16 | 1975-09-30 | Oxy Metal Industries Corp | Non-cyanide zinc plating |
US3919056A (en) * | 1972-09-26 | 1975-11-11 | M & T Chemicals Inc | Zinc plating process and electrolytes therefor |
US3957595A (en) * | 1975-01-10 | 1976-05-18 | Nalco Chemical Company | Zinc electroplating |
US4113583A (en) * | 1976-04-27 | 1978-09-12 | Dipsol Chemical Company, Ltd. | Method for brightening the electrodeposits of zinc from alkaline zinc electroplating baths |
US4134804A (en) * | 1977-08-29 | 1979-01-16 | Enthone, Incorporated | Cyanide-free zinc plating bath and process |
US4177131A (en) * | 1976-05-20 | 1979-12-04 | The Metalux Corporation | Method for obtaining bright zinc and cadmium electroplates using carboxamide additives |
US4207150A (en) * | 1978-01-25 | 1980-06-10 | Oxy Metal Industries Corporation | Electroplating bath and process |
EP4273303A1 (en) * | 2022-05-05 | 2023-11-08 | Atotech Deutschland GmbH & Co. KG | Method for depositing a zinc-nickel alloy on a substrate, an aqueous zinc-nickel deposition bath, a brightening agent and use thereof |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2167228A1 (en) * | 1972-01-11 | 1973-08-24 | Micsunescu Francine | Nitrogen-contg heterocyclic cpds - brighteners for zinc deposits from galvanic bath |
JP2003511370A (en) * | 1999-10-06 | 2003-03-25 | トレント・ファーマシューティカルズ・リミテッド | Compounds for the treatment of vascular complications associated with diabetes and aging |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2842488A (en) * | 1954-11-05 | 1958-07-08 | Dehydag Gmbh | Process for the production of metal electrodeposits |
US2900313A (en) * | 1956-03-06 | 1959-08-18 | Sylvania Electric Prod | Addition materials for improving plating speeds |
US2928800A (en) * | 1957-03-12 | 1960-03-15 | Du Pont | Zinc plating |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE540564A (en) * | 1954-10-28 |
-
1964
- 1964-02-07 US US343220A patent/US3318787A/en not_active Expired - Lifetime
-
1965
- 1965-01-14 DE DE1521069A patent/DE1521069C2/en not_active Expired
- 1965-02-05 FR FR4515A patent/FR1427282A/en not_active Expired
- 1965-02-08 GB GB5393/65A patent/GB1049132A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2842488A (en) * | 1954-11-05 | 1958-07-08 | Dehydag Gmbh | Process for the production of metal electrodeposits |
US2900313A (en) * | 1956-03-06 | 1959-08-18 | Sylvania Electric Prod | Addition materials for improving plating speeds |
US2928800A (en) * | 1957-03-12 | 1960-03-15 | Du Pont | Zinc plating |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3411996A (en) * | 1965-12-02 | 1968-11-19 | Du Pont | Process for brightening zinc and cadmium electroplate using an inner salt of a quaternized pyridine carboxylic acid and compositions containing the same |
DE2111602A1 (en) * | 1970-03-18 | 1971-10-07 | Udylite Corp | Aqueous, cyanide-free galvanic zinc bath |
US3769183A (en) * | 1971-06-18 | 1973-10-30 | Du Pont | Cyanide zinc electroplating |
JPS4842935A (en) * | 1971-09-30 | 1973-06-21 | ||
JPS549578B2 (en) * | 1971-09-30 | 1979-04-25 | ||
US3755097A (en) * | 1971-10-27 | 1973-08-28 | Stauffer Chemical Co | Novel process for electrodepositing zinc |
US3769184A (en) * | 1972-05-23 | 1973-10-30 | Du Pont | Acid zinc electroplating |
US3909373A (en) * | 1972-06-16 | 1975-09-30 | Oxy Metal Industries Corp | Non-cyanide zinc plating |
US3919056A (en) * | 1972-09-26 | 1975-11-11 | M & T Chemicals Inc | Zinc plating process and electrolytes therefor |
DE2318985A1 (en) * | 1973-01-05 | 1974-07-18 | Oxy Metal Finishing Corp | PROCESS FOR IMPROVING GALVANIC ZINC DEPOSITION THROUGH THE USE OF MULTIPLE QUARTERLY NITROGEN COMPOUNDS |
US3884774A (en) * | 1973-02-01 | 1975-05-20 | Lea Ronal Inc | Electrolytic deposition of zinc |
US3957595A (en) * | 1975-01-10 | 1976-05-18 | Nalco Chemical Company | Zinc electroplating |
US4113583A (en) * | 1976-04-27 | 1978-09-12 | Dipsol Chemical Company, Ltd. | Method for brightening the electrodeposits of zinc from alkaline zinc electroplating baths |
US4177131A (en) * | 1976-05-20 | 1979-12-04 | The Metalux Corporation | Method for obtaining bright zinc and cadmium electroplates using carboxamide additives |
US4134804A (en) * | 1977-08-29 | 1979-01-16 | Enthone, Incorporated | Cyanide-free zinc plating bath and process |
US4207150A (en) * | 1978-01-25 | 1980-06-10 | Oxy Metal Industries Corporation | Electroplating bath and process |
EP4273303A1 (en) * | 2022-05-05 | 2023-11-08 | Atotech Deutschland GmbH & Co. KG | Method for depositing a zinc-nickel alloy on a substrate, an aqueous zinc-nickel deposition bath, a brightening agent and use thereof |
WO2023213866A1 (en) * | 2022-05-05 | 2023-11-09 | Atotech Deutschland GmbH & Co. KG | Method for depositing a zinc-nickel alloy on a substrate, an aqueous zinc-nickel deposition bath, a brightening agent and use thereof |
Also Published As
Publication number | Publication date |
---|---|
DE1521069C2 (en) | 1975-02-06 |
GB1049132A (en) | 1966-11-23 |
FR1427282A (en) | 1966-02-04 |
DE1521069B1 (en) | 1970-04-23 |
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