US3871974A - Alkaline bright zinc plating - Google Patents

Alkaline bright zinc plating Download PDF

Info

Publication number
US3871974A
US3871974A US400240A US40024073A US3871974A US 3871974 A US3871974 A US 3871974A US 400240 A US400240 A US 400240A US 40024073 A US40024073 A US 40024073A US 3871974 A US3871974 A US 3871974A
Authority
US
United States
Prior art keywords
electroplating bath
bath
aldehyde
heterocyclic compound
electroplating
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
Application number
US400240A
Other languages
English (en)
Inventor
Joseph R Duchene
Phillip J Dechristopher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Richardson Chemical Co
Original Assignee
Richardson Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Richardson Chemical Co filed Critical Richardson Chemical Co
Priority to US400240A priority Critical patent/US3871974A/en
Priority to GB4083774A priority patent/GB1433716A/en
Priority to FR7432053A priority patent/FR2244838B1/fr
Priority to DE19742445360 priority patent/DE2445360A1/de
Application granted granted Critical
Publication of US3871974A publication Critical patent/US3871974A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • Zinc electroplating has conventionally been conducted in a plating bath employing alkali metal cyanide salts such as sodium cyanide as a complexing agent to achieve the desired plating operation and to produce bright zinc deposits.
  • alkali metal cyanide salts such as sodium cyanide
  • other plating methods have been sought which avoid and do not require the use of these cyanide salts.
  • alkaline bath systems which also utilize polyamines although generally of more complex nature, and usually in polymeric form and/or interacted with other compounds such as aldehydes and heterocyclic compounds.
  • One of these systems which has achieved some degree of success, involves the use ofa reaction product or a polymeric condensate of an alkylene polyamine and an epihalohydrin. While this particular polymeric condensate, particularly as a quarternary salt produces smooth, fine grained deposits, such deposits are generally dull or only semi-bright and do not have the degree of brightness or luster desired for most commercial applications.
  • the deficiency of this system can be corrected and the brightness of the plating deposit substantially improved through the use of conventional zinc brighteners and particularly those ofthe aldehyde type.
  • This improvement usually occurs only when plating at relatively high current densities with the plating deposits produced at low current densities within the range of from 0 to 20 to 40 amperes per square foot remaining dull or semi-bright.
  • This limitation or inability to achieve desirable plating over a broad current density range substantially restricts the usefulness of this system and limits its application to plating objects which are relatively uniform in shape and configuration and precludes its use in plating objects which are irregular or in barrel plating where the plating must be conducted over a broad current density range.
  • an objective of this invention is to provide an alkaline, bright zinc plating bath which does not require or utilize cyanide salts. Another object is to provide such a bath employing a quarternized polymeric condensate of an alkylene polyamine and a hydrin compound in combination with brightening agents which produces a bright, mirror like deposit. A further object is to provide such a bath with the addition ofcertain mercapto substituted heterocyclic compounds capable of producing the bright zinc deposit over a broad current density range. Still another object is to provide a method of zinc electroplating employing such improved bath and capable of effectively operating in a commercially desirable manner completely free of any cyanides.
  • the electroplating of zinc in an aqueous alkaline bath in the presence of a polymeric condensate of an alkylene polyamine and a epihalohydrin together with a zinc brightener is effected in accordance with this invention by adding a mercapto substituted nitrogen containing heterocyclic compound to such bath so as to achieve a bright deposit over a broad current density range.
  • This mercapto substituted heterocyclic compound may generally be described as an ortho mercapto substituted pyridine or pyrimidine, that is where the mercapto substituent is positioned on the 2 ring carbon atom.
  • These mercapto substituted pyridines or pyrimidines have the following general formula:
  • X is selected from the group consisting of N and CR wherein R is selected from the group consisting of hydrogen, hydroxy, mercapto and acyl and wherein R R and R are each independently selected from the group consisting of hydrogen, hydroxy, mercapto, acyl, amino, alkyl, carboxy and carbamoyl.
  • Examples of mercapto substituted heterocyclic compounds which may be employed either individually or in admixture according to this invention includes pyridines, that is where X of the formula is CR and pyrimidines, that is, where the X is nitrogen. These compounds may be substituted as indicated in the formula and where any of the various R substituents is alkyl or acyl such substituents can contain from one to about five and more preferably from one to three carbon atoms such as methyl, ethyl or propyl, or where acyl such groups as formyl, acetyl or propionyl. Typical examples of these compounds include pyridines such as Z-mercaptopyridine;
  • pyrimidines such as Z-mercaptopyrimidine; 2,6-dimercaptopyrimidine; Z-mercapto4-aminopyrimidine; 2-mercapto-4,6-dihydroxypyrimidine; 2-mercapto-4-ethylpyrimidine; 2-mercapto-4-hydroxy-6-methylpyrimidine; 2-mercapto-6-acetylpyrimidine; 2-mercapto-4-hydroxy-5,6-diethylpyrimidine; 2,4-dimercaptopyrimidine; or Z-mercapto-6-hydroxypyrimidine.
  • the mercapto pyridines or pyrimidines represented by the above formula may also in many instances exist in tautomeric or isomeric form.
  • one of the preferred compounds according to this invention is Z-thiouracil and such compound can exist as Z-mercapto-4-hydroxypyrimidine or 2-thio-4- oxopyrimidine or as an intermediate tautomer as 2-thioxo-4-hydroxypyrimldine and 2,4-dithiouracil can exist as 2,4-dimercaptopyrimidine or 2,4- dithiopyrimidine. All of these tautomeric compounds are accordingly embraced within the compounds which may be used in accordance with this invention as represented by the above formula.
  • the preferred compounds are pyridines or pyrimidines of the formula where the mercapto group is substituted in the 2 ring position and generally also with a hydroxy group in one of the 4 or 6 position.
  • the pyrimidines are especially preferred and an example of one of these compounds having particular utility in the bath ofthe invention is 2-thiouracil or Z-mercapto-4,6-dihydroxy pyrimidine.
  • the mercapto heterocyclic compounds of the above formula are used in accordance with this invention to improve alkaline plating baths which employ polymeric condensates of alkylene polyamines and epihalohydrin compounds.
  • these polymeric condensates are produced by reacting the alkylene polyamine and epihalohydrin compound in a condensation reaction to produce a substantially uncrosslinked, aqueous soluble polymeric condensate.
  • the polymeric condensate is employed as a quarternary salt which involves a further reaction of the polymeric condensate with a suitable quarternizing agent.
  • these polymeric condensates and their quarternary salts may be prepared in accordance with the procedures described i US. Pat. No. 3,642,663.
  • the epihalohydrin compounds which may be interracted with the alkylene polyamines include epibromohydrin or epichlorohydrin with the epichlorohydrin being particularly preferred in most instances.
  • the alkylene polyamines which may be reacted with the epihalohydrin have at least one tertiary amino group such as dimethylaminopropylamine (N,N- dimethylpropylenediamine), diethylaminopropylamine (N,N-diethylpropylenediamine), N-aminopropylmorpholine, dimethylaminoethylamine, diethylaminoethylamine, N-aminopropyldiethanolamine, or N- methyliminobispropylamine.
  • tertiary amino group such as dimethylaminopropylamine (N,N- dimethylpropylenediamine), diethylaminopropylamine (N,N-diethylpropylenediamine), N-aminopropylmorpholine, dimethylaminoethylamine, diethylaminoethylamine, N-aminopropyldiethanolamine, or N
  • alkylene polyamines containing at least one tertiary amino group and at least one secondary amino group may also be employed such as N,N-dimethyl-N- methylpropylenediamine; N,N-dimethyl-N-methyl ethylenediamine; or N,N-diethyl-N-ethylethylenediamine.
  • the lower alkylene polyamines where the alkylene bridge contains from two to five carbon atoms and where the tertiary amino group is substituted with alkyl groups of from one to about five carbon atoms are preferred particularly when the epihalohydrin is epichlorohydrin with a particularly preferred alkylene polyamine being dimethylaminopropylamine.
  • the alkylene polyamine should be condensed with the epihalohydrin compound in a mol ratio of from about 0.5 to 1.75 mols of the amine per 1 mol of the epihalohydrin.
  • the mol ratio of the polyamine to epichlorohydrin advantageous ranges from about 0.8 to about 1.5 mols of polyamine to 1 mol of epichlorohydrin, that is the mol ratio of the polyamine to the epichlorohydrin ranges from about 0.8:1 to about 1.511, respectively.
  • the polymeric condensates employed in accordance with this invention in combination with the mercapto heterocyclic compound and brightener is utilized as a quarternary salt.
  • Suitable quarternizedagents for the polymeric condensates are the lower alkyl halides such as methyl-chloride, -bromide,' or -iodide, ethyl-chloride, -bromideor alpha chloroglycerol, diloweralkyl sulfates such as dimethyl, -diethyl, -dipropyl, or -dibutyl-sulfates; lower alkyl esters of aryl sulfonates such as methyl toluene sulfonate and methyl benzene sulfonate; alkyhalo esters such as ethyl-chloroacetate; alkylene halohydrins such as ethylenechlorohydrin or alkylene oxides such as ethylene
  • the zinc electroplating bath of this invention contains the polymeric condensate in admixture with brightening agents. While these brightening agents as previously discussed improve the luster or brightness of the zinc plating they have a tendency to increase the luster only at the higher current density ranges generally above about 40 or more usually above about 20 amperes per square foot up to about 200 amperes per square foot and do not without the additional presence of the mercapto substituted compounds of this invention produce a bright deposit throughout the entire current density range and particularly at the lower current density ranges conventionally employed in most commercial operations and generally below about 40 or more usually below about 20 down to O amperes per square foot.
  • These brighteners include those materials conventionally employed in zinc plating and typically contain a carbonyl group of aldehyde functionality which generally may be represented by the formula wherein R and R are independently selected from the group consisting of hydrogen, alkyl, generally containing from one to about carbon atoms, aryl and heterocyclic oxygen and sulfur containing radicals and include, for example, m-hydroxy benzaldehyde, phydroxy benzaldehyde, piperonal, o-hydroxy benzaldehyde, (salicylaldehyde), veratraldehyde, benzaldehyde, B-methoxy propionaldehyde, furfural, glyceraldehyde, anisaldehyde, vanillin, thiophene-2-aldehyde.
  • R and R are independently selected from the group consisting of hydrogen, alkyl, generally containing from one to about carbon atoms, aryl and heterocyclic oxygen and sulfur containing radicals and
  • aldehyde materials which may be employed the aryl aldehydes and particularly the benzaldehydes such as anisic aldehyde (pmethoxybenzaldehyde) or vanillin (p-hydroxy-mmethoxybenzaldehyde) or various combinations thereof are preferred.
  • benzaldehydes such as anisic aldehyde (pmethoxybenzaldehyde) or vanillin (p-hydroxy-mmethoxybenzaldehyde) or various combinations thereof are preferred.
  • These aldehydes brighteners may be employed in the bath of this invention as addition products with such materials as sodium bis'ulfite to increase their alkaline solubility if desired.
  • the electroplating bath of this invention may be prepared and operated in accordance with the general procedures conventionally employed for alkaline bright zinc plating.
  • the bath is prepared as an aqueous solution and rendered alkaline by the addition of a suitable alkaline material such an alkali metal hydroxide or carbonate for example sodium or potassium hydroxide.
  • a suitable alkaline material such as an alkali metal hydroxide or carbonate for example sodium or potassium hydroxide.
  • the quantity of alkaline material added should be capable of dissolving the zinc compound employed as the source of the zinc ion in the bath and generally should be in excess of that required to create the desired alkali metal zincate such as sodium zincate as well as to maintain the pH of the solution alkaline and generally above 7 and preferably above l4.
  • the source of the zinc ion in the bath can be varied and generally any of the zinc compounds conventionally employed in alkaline bright zinc baths may be utilized. Typically such compounds include zinc salts or oxides such as zinc sulfate, zinc acetate or zinc oxide with the zinc sulfate generally being preferred.
  • the amount of zinc in the bath can be varied depending upon the desired results and operating condition but generally is maintained within the range of from about 3 to about grams per liter.
  • the quantity of the quarternized polymeric condensate utilized in the bath will in general be a function of the particular brightener and mercapto substituted compound employed as well as the particular polymeric condensate utilized.
  • the quantity of the condensate in the bath should range from about 0.25 to about 5 grams per liter with a more limited range of from about 0.3 to about 0.75 grams per liter being preferred especially when used in combination with such mercapto compounds as Z-thiouracil.
  • the quantity of the mercapto substituted compound employed in the bath in similar fashion is also interrelated to the specific polymeric condensate and aldehyde brightener employed as well as the particular mercapto substituted compound or combination of compounds utilized.
  • the mercapto compound is maintained in the bath within the range of from about 0.01 to about 0.2 grams per liter with a more limited range being preferred of from about 0.025 to about 0.075 grams per liter particularly when employing the preferred mercapto compounds such as 2-thiouracil or 2-mercapto-2,4-dihydroxy pyrimidine.
  • the brighten'ers used in combination with the quarternized polymeric condensate typically will be present in the bath within the ranges conventionally utilized for alkaline zinc plating baths. Typically this will range from about 0.1 to about 5 grams per liter with a more limited range from about 0.2 to about 0.5 grams per liter being more advantageously employed particularly when employing the preferred benzaldehyde type brighteners.
  • the electroplating of zinc conducted in accordance with the method of this invention is effected in conventional fashion basically by passing a direct current from a zinc anode through the aqueous alkaline, noncyanide bath of this invention containing essentially the polymeric condensate, brightener and mercapto substi tuted compound to the desired cathode article which is to be electroplated with the zinc.
  • This method may be conducted at temperatures from about 60 to about 100 F.
  • the current densities employed may range from above 0 to about 200 amperes per square foot with a more limited range of from about 0.5 to about amperes per square foot being satisfactory for most plating operations.
  • the plating bath of this invention may contain further additives of the type conventionally employed in alkaline zinc electroplating baths and include such materials as polyvinyl alcohols, gelatine, polyether alcohols, polyesters, glue and peptone. Of these various materials polyvinyl alcohol or its various derivatives are especially preferred and appear to greatly enhance the mirror like deposits of the platings produced in accordance with this invention. When so employed these polyvinyl alcohols should be utilized in the bath within a range offrom about 0.02 to about 0.2 grams per liter.
  • EXAMPLE 11 A series of zinc electroplating tests were conducted in various aqueous alkaline noncyanide, electroplating baths to zinc plate Hull test panels.
  • the plating was carried out in a standard Hull cell (267 ml) with the Hull cell panel in each test run connected as the cathode in the bath.
  • the plating was conducted at an operating current of 1 ampere representing a current density range on the test panel varying from a high range of from about 40 to about 60 amperes per square foot (a.s.f.) to a low range of from about 0.1 to about 0.5 (a.s.f.).
  • the plating time was minutes with the bath operated at a temperature of about 75 F.
  • EXAMPLE III A series of aqueous alkaline, non-cyanide zinc electroplating baths were prepared to zinc plate Hull test panels. The plating was conducted in a standard Hull cell (267 ml) with the Hull cell panel in each test connected as the cathode of the bath. The plating was conducted at an operating current of l ampere representing a current density range on the test panel varying from a high range of from about 40 to about 60 amperes per square foot (a.s.f.) and a low range of from about 0.2 to about 0.5 (a.s.f.). The plating time was minutes with the bath being maintained at a temperature of about 75 F. The bath in each run had the components and concentrations as shown in Table III.
  • blank bath was used without the mercapto substituted compound to compare the plating deposit produced with and Without the mercapto substituted compound.
  • a bright zinc, cyanide free electroplating bath' comprising an aqueous alkaline solution containing a source of zinc ions, from about 0.1 to about 5 grams per liter of a brightener containing a carbonyl group of aldehyde functionality, from about 0.01 to about 0.2 grams per liter of a heterocyclic compound selected from the group consisting of a 2-mercapto substituted pyridine or pyrimidine and from about 0.25 to about 5 grams per liter of a quarternary salt of a polymeric condensate of an alkylene polyamine having at least one tertiary amino group and an epihalohydrin wherein the mol ratio of the polyamine to the epihalohydrin ranges from about 0.521 to 1.75:1, respectively.
  • heterocyclic compound has the formula or tautomers thereof wherein X is selected from the group consisting of N and CR where R, is selected from the group consisting of hydrogen, hydroxy, mercapto and acyl; R R and R are each independently selected from the group consisting of hydrogen, hydroxy, mercapto, acyl, amino, alkyl. carboxy and carbamoyl.
  • heterocyclic compound is 2-mercapto-4-amino-6- hydroxypyrimidine.
  • heterocyclic compound is 5-carboxy-2-mercaptopyridine.
  • heterocyclic compound is 2-mercapto-4,6- dihydroxypyrimidine.
  • the brightener is an aldehyde having the formula wherein R, and R are independently selected from the group consisting of hydrogen, alkyl, aryl and heterocyclic oxygen and sulfur containing radicals.
  • the alkylene polyamine is dimethylaminopropylamine and the epihalohydrin is enichlorohydrin and the mol ratio of the polyamine to the epichlorohydrin ranges from about 0.811 to about 1.511, respectively and the condensate is substantially uncrosslinked.
  • heterocyclic compound is 2-mercapto-4,6-dihydroxypyrimidine
  • the brightener is an aldehyde of a mixture of anisic aldehyde and vanillin.

Landscapes

  • 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)
US400240A 1973-09-24 1973-09-24 Alkaline bright zinc plating Expired - Lifetime US3871974A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US400240A US3871974A (en) 1973-09-24 1973-09-24 Alkaline bright zinc plating
GB4083774A GB1433716A (en) 1973-09-24 1974-09-19 Alkaline bright zinc electro plating
FR7432053A FR2244838B1 (enrdf_load_stackoverflow) 1973-09-24 1974-09-23
DE19742445360 DE2445360A1 (de) 1973-09-24 1974-09-23 Cyanidfreies galvanisierungsbad

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US400240A US3871974A (en) 1973-09-24 1973-09-24 Alkaline bright zinc plating

Publications (1)

Publication Number Publication Date
US3871974A true US3871974A (en) 1975-03-18

Family

ID=23582790

Family Applications (1)

Application Number Title Priority Date Filing Date
US400240A Expired - Lifetime US3871974A (en) 1973-09-24 1973-09-24 Alkaline bright zinc plating

Country Status (4)

Country Link
US (1) US3871974A (enrdf_load_stackoverflow)
DE (1) DE2445360A1 (enrdf_load_stackoverflow)
FR (1) FR2244838B1 (enrdf_load_stackoverflow)
GB (1) GB1433716A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957595A (en) * 1975-01-10 1976-05-18 Nalco Chemical Company Zinc electroplating
US4007098A (en) * 1975-09-04 1977-02-08 Columbia Chemical Corporation Baths and additives for the electrodeposition of bright zinc
DE2643898A1 (de) * 1975-09-29 1977-03-31 Du Pont Glanzbildner fuer galvanische zinkbaeder und seine verwendung
US4166778A (en) * 1978-05-17 1979-09-04 Simeon Acimovic Cyanide-free alkaline zinc baths
US4730022A (en) * 1987-03-06 1988-03-08 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths
US4792383A (en) * 1987-10-27 1988-12-20 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths and processes
US6143160A (en) * 1998-09-18 2000-11-07 Pavco, Inc. Method for improving the macro throwing power for chloride zinc electroplating baths
CN101555609B (zh) * 2009-04-28 2010-08-04 武汉风帆电镀技术有限公司 有氰转无氰碱性环保镀锌组合物光亮剂
CN101565839B (zh) * 2009-04-28 2011-04-06 武汉风帆电镀技术有限公司 有氰转无氰碱性环保镀锌光亮剂
EP2881389A1 (en) * 2013-12-06 2015-06-10 Rohm and Haas Electronic Materials LLC Additives for electroplating baths

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1507095A (en) * 1975-04-15 1978-04-12 Canning & Co Ltd W Electro-deposition of zinc
GB2285716B (en) * 1992-09-02 1997-08-20 Otter Controls Ltd Connection system for cordless appliances

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3672971A (en) * 1969-07-15 1972-06-27 Riedel & Co Fa Bright-zinc plating bath

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3672971A (en) * 1969-07-15 1972-06-27 Riedel & Co Fa Bright-zinc plating bath

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957595A (en) * 1975-01-10 1976-05-18 Nalco Chemical Company Zinc electroplating
US4007098A (en) * 1975-09-04 1977-02-08 Columbia Chemical Corporation Baths and additives for the electrodeposition of bright zinc
DE2643898A1 (de) * 1975-09-29 1977-03-31 Du Pont Glanzbildner fuer galvanische zinkbaeder und seine verwendung
US4166778A (en) * 1978-05-17 1979-09-04 Simeon Acimovic Cyanide-free alkaline zinc baths
US4730022A (en) * 1987-03-06 1988-03-08 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths
US4792383A (en) * 1987-10-27 1988-12-20 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths and processes
US6143160A (en) * 1998-09-18 2000-11-07 Pavco, Inc. Method for improving the macro throwing power for chloride zinc electroplating baths
CN101555609B (zh) * 2009-04-28 2010-08-04 武汉风帆电镀技术有限公司 有氰转无氰碱性环保镀锌组合物光亮剂
CN101565839B (zh) * 2009-04-28 2011-04-06 武汉风帆电镀技术有限公司 有氰转无氰碱性环保镀锌光亮剂
EP2881389A1 (en) * 2013-12-06 2015-06-10 Rohm and Haas Electronic Materials LLC Additives for electroplating baths
CN104694981A (zh) * 2013-12-06 2015-06-10 罗门哈斯电子材料有限公司 用于电镀液的添加剂
CN104694981B (zh) * 2013-12-06 2017-08-25 罗门哈斯电子材料有限公司 用于电镀液的添加剂
US9783903B2 (en) 2013-12-06 2017-10-10 Rohm And Haas Electronic Materials Llc Additives for electroplating baths

Also Published As

Publication number Publication date
GB1433716A (en) 1976-04-28
FR2244838B1 (enrdf_load_stackoverflow) 1979-02-16
FR2244838A1 (enrdf_load_stackoverflow) 1975-04-18
DE2445360A1 (de) 1975-04-03

Similar Documents

Publication Publication Date Title
US5405523A (en) Zinc alloy plating with quaternary ammonium polymer
US4134802A (en) Electrolyte and method for electrodepositing bright metal deposits
US4169772A (en) Acid zinc plating baths, compositions useful therein, and methods for electrodepositing bright zinc deposits
US3871974A (en) Alkaline bright zinc plating
US3655534A (en) Alkaline bright zinc electroplating
US4075066A (en) Electroplating zinc, ammonia-free acid zinc plating bath therefor and additive composition therefor
US3884774A (en) Electrolytic deposition of zinc
US3972789A (en) Alkaline bright zinc plating and additive composition therefore
US4699696A (en) Zinc-nickel alloy electrolyte and process
US4229268A (en) Acid zinc plating baths and methods for electrodepositing bright zinc deposits
US4168223A (en) Electroplating bath for depositing tin or tin alloy with brightness
US4002543A (en) Electrodeposition of bright nickel-iron deposits
US3824158A (en) Composition of baths for electrodeposition of bright zinc
US3821095A (en) Zinc electroplating process and electrolyte therefor
US3886054A (en) Alkaline bright zinc plating
CA1083078A (en) Alloy plating
US3919056A (en) Zinc plating process and electrolytes therefor
CA1108088A (en) Alkaline bright zinc plating
US4101387A (en) Composition for electrodeposition of metal deposits, its method of preparation and uses thereof
CA1058553A (en) Electrodeposition of alloys of nickel, cobalt, or nickel and cobalt with iron
US4188271A (en) Alkaline zinc electroplating baths and additive compositions therefor
US2862861A (en) Copper cyanide plating process and solution therefor
US4496439A (en) Acidic zinc-plating bath
US3734839A (en) Alkaline cyanide zinc electroplating
US4270990A (en) Acidic electroplating baths with novel surfactants