US3723263A - Composition of baths for electrodeposition of bright zinc from aqueous, acid, electroplating baths - Google Patents

Composition of baths for electrodeposition of bright zinc from aqueous, acid, electroplating baths Download PDF

Info

Publication number
US3723263A
US3723263A US00229590A US3723263DA US3723263A US 3723263 A US3723263 A US 3723263A US 00229590 A US00229590 A US 00229590A US 3723263D A US3723263D A US 3723263DA US 3723263 A US3723263 A US 3723263A
Authority
US
United States
Prior art keywords
zinc
baths
acid
aqueous
gms
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
US00229590A
Inventor
W Rosenberg
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.)
Hull R & Co Inc
Hull R & Co Inc us
Original Assignee
Hull R & Co Inc
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 Hull R & Co Inc filed Critical Hull R & Co Inc
Application granted granted Critical
Publication of US3723263A publication Critical patent/US3723263A/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

  • This invention pertains to improvements in the electrodeposition of bright zinc from aqueous acid plating baths.
  • Acid zinc electroplating baths are not new in the plating field and have, in fact, been used with moderate success for quite some time. Prior to this invention, however, certain limitations have in many instances rendered the existing acid zinc plating bath compositions extremely impractical to use and quite often not applicable at all.
  • Another problem that has been common has been the lack of ductility in the zinc plate obtained from existing acid zinc bath compositions. Many parts are bent or shaped after plating either through manufacturing processes or through normal use. If the electrodeposit is not reasonably ductile, chipping, flaking and peeling of the plate can occur, thus causing rejection of the part.
  • This invention comprises an aqueous, acid electroplating bath, for producing a bright, lustrous electrodeposit of zinc containing zinc ions and chloride ions, and dissolved therein, naphthol polyoxyalkylate having the formula:
  • R is hydrogen or methyl, and x is about 8 to 20.
  • polyethylenimine having the formula:
  • R is hydrogen, methyl, ethyl, propyl, hydroxyethyl, Z-hydroxypropyl, 3-hydroxypropyl, 2- aminoethyl, 2-aminopropyl, or 3-aminopropyl, and y is about 10 to 20.
  • the present invention is also an addition agent for an acid zinc electroplating bath consisting of from about 1:100 to :1 parts by weight of naphthol polyoxyalkylate and polyethylenimine of the above formulas.
  • a general purpose bath was made up which contained 30 gms. ZnCl /liter and 200 gms. NH,Cl/liter at a pH of 4.9.
  • the current density area from 0 to about 50 amps per sq. ft. is left as a dark, rough electrodeposit with no trace of brightness.
  • the naphthol polyoxyalkylate and the polyethylenimine act synergistically to provide a bright, lustrous electrodeposit from about 12 amps per sq. ft. to well over 200 amps per sq. ft. In addition to being extremely bright, the deposit is quite ductile.
  • the current densities below 12 amps per sq. ft. can be made bright by the addition of between 0.01 and 10 gms. per liter of a substance selected from the group consisting of anisaldehyde, piperonal, veratraldehyde, benzaldehyde, vanillan, benzylidene acetone, and cinnamic aldehyde.
  • An aqueous, acid electroplating bath for producing a bright, lustrous electrodeposit of zinc containing zinc ions, and chloride ions and dissolved therein naphthol polyoxyalkylate having the formula:
  • R is hydrogen or methyl
  • x is about 8 to 20 and polyethylenimine having the formula:
  • R is hydrogen, methyl, ethyl, propyl, hydroxyethyl, 2 hydroxy propyl, 3-hydroxy propyl, 2- aminoethyl, 2-aminopropyl, or 3-aminopropyl, and y is about 10 to about 20.

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)

Abstract

It has been found that upon addition to an aqueous, acid, zinc electroplating bath, naphthol polyoxyalkylate and polyethylenimine act synergistically to provide smooth, bright, ductile, electrodeposits of zinc.

Description

United States Patent 1 Rosenberg 1 Mar. 27, 1973 COMPOSITION OF BATHS FOR ELECTRODEPOSITION OF BRIGHT ZINC FROM AQUEOUS, ACID, ELECTROPLATING BATHS Inventor: William E. Rosenberg, Parma, Ohio Assignee: R. 0. Hull & Company, Inc., Cleveland, Ohio Filed: Feb. 25, 1972 Appl. No.2 229,590
U.S. Cl. ..204/55 R, 204/DIG. 2 Int. Cl. ..C23b 5/12, C23b 5/46 Field of Search ....204/55 R, 55 Y, 43, 44, 114
References Cited UNITED STATES PATENTS Harford ..204/55 R X Harford Pye et a1 Rosenberg... Wade ..204/55 R X Primary Examiner-G. L. Kaplan Y Attorney-Blythe D. Watts et al.
ABSTRACT 4 Claims, N0 Drawings COMPOSITION OF BATIIS FOR ELECTRODEPOSITION OF BRIGHT ZINC FROM AQUEOUS, ACII), ELECTROPLATING BATI-IS BACKGROUND OF THE INVENTION This invention pertains to improvements in the electrodeposition of bright zinc from aqueous acid plating baths.
Acid zinc electroplating baths are not new in the plating field and have, in fact, been used with moderate success for quite some time. Prior to this invention, however, certain limitations have in many instances rendered the existing acid zinc plating bath compositions extremely impractical to use and quite often not applicable at all.
One of the most limiting factors in the plating of bright zinc from acid plating baths has been that only a rather low current density could be applied to a given part to produce a lustrous zinc deposit. By raising the current density to increase the speed of plating, the plater would encounter dark, coarse, and even spongy deposits of zinc.
Another problem that has been common has been the lack of ductility in the zinc plate obtained from existing acid zinc bath compositions. Many parts are bent or shaped after plating either through manufacturing processes or through normal use. If the electrodeposit is not reasonably ductile, chipping, flaking and peeling of the plate can occur, thus causing rejection of the part.
Many of the addition agents prior to this invention have been considerably intolerant to operating temperatures higher than 90 F. These additives would either be chemically destroyed at higher temperatures or just lose their ability to produce bright deposits.
The addition agents and bath compositions of this invention have overcome these serious limitations. With the use of this invention, much higher current densities and operating temperatures can be used to obtain lustrous, bright, ductile deposits of zinc from acid zinc plating baths. This is possible because these additives provide bright deposits over a very wide current density range, are chemically stable, and are not adversely affected by normal increases in temperature.
SUMMARY OF THE INVENTION This invention comprises an aqueous, acid electroplating bath, for producing a bright, lustrous electrodeposit of zinc containing zinc ions and chloride ions, and dissolved therein, naphthol polyoxyalkylate having the formula:
where R is hydrogen or methyl, and x is about 8 to 20. and polyethylenimine having the formula:
where R is hydrogen, methyl, ethyl, propyl, hydroxyethyl, Z-hydroxypropyl, 3-hydroxypropyl, 2- aminoethyl, 2-aminopropyl, or 3-aminopropyl, and y is about 10 to 20.
The present invention is also an addition agent for an acid zinc electroplating bath consisting of from about 1:100 to :1 parts by weight of naphthol polyoxyalkylate and polyethylenimine of the above formulas.
DETAILED DESCRIPTION Both the naphthol polyoxyalkylates and the polyethylenimines of this invention are available in commerce and are supplied as viscous oils and aqueous solutions.
For ease of handling the addition agents were made up as aqueous solutions, but any other suitable solvent or emulsion will work as well.
All testing was done in a conventional 267 ml. I-Iull Cell using steel cathode panels and a zinc anode. Two ampere panels were run for 10 minutes at temperatures ranging from 70 to F. with mechanical agitation.
A general purpose bath was made up which contained 30 gms. ZnCl /liter and 200 gms. NH,Cl/liter at a pH of 4.9.
Addition of between 0.1 to 20 gms. of naphthol polyoxyalkylate to the general purpose bath produces only a semi-bright cloudy electrodeposit of zinc from 0 to about 40 amps. per sq. ft. The current density area from 40 amps. per sq. ft. up to 200 amps. per sq. ft. is left as a dark, rough and somewhat spongy electrodeposit.
Similarly, the singular addition of about 0.1 to 20 gms. per liter of polyethylenimine to this bath gives only a semibright, gray electrodeposit from about 50 amps. per sq. ft. up to 200 amps per sq. ft.
The current density area from 0 to about 50 amps per sq. ft. is left as a dark, rough electrodeposit with no trace of brightness.
When the naphthol polyoxyalkylate and the polyethylenimine are added together to this general purpose bath, they act synergistically to provide a bright, lustrous electrodeposit from about 12 amps per sq. ft. to well over 200 amps per sq. ft. In addition to being extremely bright, the deposit is quite ductile. The current densities below 12 amps per sq. ft. can be made bright by the addition of between 0.01 and 10 gms. per liter of a substance selected from the group consisting of anisaldehyde, piperonal, veratraldehyde, benzaldehyde, vanillan, benzylidene acetone, and cinnamic aldehyde.
While the addition agents of this invention are effective in many aqueous, acid zinc plating bath formulations, it is preferred to use any of the basic baths described in the following examples. It will be understood that the following examples are just illustrations and are not meant to limit the use of the invention to these bath compositions only:
EX AM PLE I Bath Composition Concentrations in gms/liter Zinc Chloride 30 Ammonium Chloride 200 pH 5.0 Polyethylenimine 4 (600 molecular weight) b-naphthol polyoxyethylene 4 (12 moles of ethylene oxide) EXAM PLE II Bath Composition Concentration in gms/liter Zinc Sulfate 34 Ammonium Chloride 150 pH 4,8 N-hydroxyethyl polyethylenimine (1,200 molecular weight) b-naphthol polyethylene oxide 10 (I5 moles of ethylene oxide) EXAM PLE III Bath Composition Concentration in gms/liter Zinc chloride 60 Ammonium Chloride 200 pH 5.0 Polyethylenimine 4 (600 molecular weight) b-naphthol polyethylene oxide 4 (8 moles of ethylene oxide) Piperonal (added as methanol solution) EX AM PLE IV Bath Composition Concentration in gms/liter Zinc Chloride 30 Ammonium Chloride 200 pH 6.0 2-hydroxy propyl polyethylenimine (I200 molecular weight) 8 a'naphthol polyethylene oxide 5 moles ethylene oxide) Benzaldehyde (added as methanol ([2 moles ethylene oxide) Having thus described this invention in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains to make and use the same, and having set forth the best mode contemplated of carrying out this invention, I state that the subject matter which I regard as being my invention is particularly pointed out and dinstinctly claimed in what is claimed, it being understood that equivalents or modifications of, or substitutions for, parts of the above specifically described embodiment of the invention may be made without departing from the scope of the invention as set forth in what is claimed.
What is claimed is:
1. An aqueous, acid electroplating bath for producing a bright, lustrous electrodeposit of zinc containing zinc ions, and chloride ions and dissolved therein naphthol polyoxyalkylate having the formula:
where R is hydrogen or methyl, and x is about 8 to 20 and polyethylenimine having the formula:
where R is hydrogen, methyl, ethyl, propyl, hydroxyethyl, 2 hydroxy propyl, 3-hydroxy propyl, 2- aminoethyl, 2-aminopropyl, or 3-aminopropyl, and y is about 10 to about 20.
2. A bath composition as set forth in claim 1 wherein the polyethylenimine is dissolved therein at a concentration of about 0.5 to about 20 gms. per liter.
3. A bath composition as set forth in claim I wherein the naphthol polyoxyalkylate is dissolved therein at a concentration of about 0.5 to about 20 gms. per liter.
4. A bath composition as set forth in claim 1 wherein there is also present at least one of the substances selected from the group consisting of anisaldehyde, piperonal, veratraldehyde, benzaldehyde, vanillan, benzylidene acetone, and cinnamic aldehyde, and present in a concentration of about 0.01 to about 10 gms. per liter.

Claims (3)

  1. 2. A bath composition as set forth in claim 1 wherein the polyethylenimine is dissolved therein at a concentration of about 0.5 to about 20 gms. per liter.
  2. 3. A bath composition as set forth in claim 1 wherein the naphthol polyoxyalkylate is dissolved therein at a concentration of about 0.5 to about 20 gms. per liter.
  3. 4. A bath composition as set forth in claim 1 wherein there is also present at least one of the substances selected from the group consisting of anisaldehyde, piperonal, veratraldehyde, benzaldehyde, vanillan, benzylidene acetone, and cinnamic aldehyde, and present in a concentration of about 0.01 to about 10 gms. per liter.
US00229590A 1972-02-25 1972-02-25 Composition of baths for electrodeposition of bright zinc from aqueous, acid, electroplating baths Expired - Lifetime US3723263A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22959072A 1972-02-25 1972-02-25

Publications (1)

Publication Number Publication Date
US3723263A true US3723263A (en) 1973-03-27

Family

ID=22861879

Family Applications (1)

Application Number Title Priority Date Filing Date
US00229590A Expired - Lifetime US3723263A (en) 1972-02-25 1972-02-25 Composition of baths for electrodeposition of bright zinc from aqueous, acid, electroplating baths

Country Status (7)

Country Link
US (1) US3723263A (en)
JP (1) JPS5317980B2 (en)
AU (1) AU458551B2 (en)
BR (1) BR7301360D0 (en)
ES (1) ES410631A1 (en)
FR (1) FR2172969B1 (en)
SE (1) SE386462B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089755A (en) * 1977-07-11 1978-05-16 The Richardson Company Acid bright zinc plating
US4101387A (en) * 1974-04-22 1978-07-18 Oxy Metal Industries Corporation Composition for electrodeposition of metal deposits, its method of preparation and uses thereof
US4162947A (en) * 1978-05-22 1979-07-31 R. O. Hull & Company, Inc. Acid zinc plating baths and methods for electrodepositing bright zinc deposits
FR2422735A1 (en) * 1978-01-16 1979-11-09 Oxy Metal Industries Corp PROCESS FOR ELECTROLYTIC COATING OF ZINC AND ACIDIC OR SENSITIVELY NEUTRAL BATHS, WITHOUT CYANIDE, USED FOR THIS PURPOSE
US4444630A (en) * 1977-07-11 1984-04-24 Richardson Chemical Company Acid bright zinc plating
US4765871A (en) * 1981-12-28 1988-08-23 The Boeing Company Zinc-nickel electroplated article and method for producing the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5826004Y2 (en) * 1980-02-12 1983-06-04 関西電力株式会社 Flowing water screen foreign matter ejector
JPS583607A (en) * 1981-06-26 1983-01-10 Tapuroge Japan Kk Filter with back washing mechanism
DE3246718C1 (en) * 1982-12-17 1984-05-24 Taprogge GmbH, 4000 Düsseldorf Device for the mechanical cleaning of a cooling water flow from power plant condensers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2355070A (en) * 1937-07-03 1944-08-08 Little Inc A Electrolytic deposition of metal
US2384300A (en) * 1937-07-03 1945-09-04 Little Inc A Electrolytic deposition of zinc
US2853444A (en) * 1955-10-18 1958-09-23 Dow Chemical Co Electrowinning of metals
US3393135A (en) * 1965-08-05 1968-07-16 Enthone Bright zinc electro-plating
US3565800A (en) * 1969-02-04 1971-02-23 Ventron Corp Ionic compositions containing hg(ii),zn(ii),cd(ii),ag(i),cu(ii),ni(ii) and/or co(ii),and a polymer of an ethylene imine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2355070A (en) * 1937-07-03 1944-08-08 Little Inc A Electrolytic deposition of metal
US2384300A (en) * 1937-07-03 1945-09-04 Little Inc A Electrolytic deposition of zinc
US2853444A (en) * 1955-10-18 1958-09-23 Dow Chemical Co Electrowinning of metals
US3393135A (en) * 1965-08-05 1968-07-16 Enthone Bright zinc electro-plating
US3565800A (en) * 1969-02-04 1971-02-23 Ventron Corp Ionic compositions containing hg(ii),zn(ii),cd(ii),ag(i),cu(ii),ni(ii) and/or co(ii),and a polymer of an ethylene imine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101387A (en) * 1974-04-22 1978-07-18 Oxy Metal Industries Corporation Composition for electrodeposition of metal deposits, its method of preparation and uses thereof
US4089755A (en) * 1977-07-11 1978-05-16 The Richardson Company Acid bright zinc plating
US4444630A (en) * 1977-07-11 1984-04-24 Richardson Chemical Company Acid bright zinc plating
FR2422735A1 (en) * 1978-01-16 1979-11-09 Oxy Metal Industries Corp PROCESS FOR ELECTROLYTIC COATING OF ZINC AND ACIDIC OR SENSITIVELY NEUTRAL BATHS, WITHOUT CYANIDE, USED FOR THIS PURPOSE
US4162947A (en) * 1978-05-22 1979-07-31 R. O. Hull & Company, Inc. Acid zinc plating baths and methods for electrodepositing bright zinc deposits
FR2426749A1 (en) * 1978-05-22 1979-12-21 Hull & Co R O ACID ZINC PLANTS AND METHODS FOR THE ELECTRODEPOSITION OF BRILLIANT ZINC DEPOSITS
US4765871A (en) * 1981-12-28 1988-08-23 The Boeing Company Zinc-nickel electroplated article and method for producing the same

Also Published As

Publication number Publication date
JPS5317980B2 (en) 1978-06-12
JPS4899042A (en) 1973-12-15
ES410631A1 (en) 1976-01-01
FR2172969A1 (en) 1973-10-05
BR7301360D0 (en) 1974-05-16
FR2172969B1 (en) 1975-03-28
AU458551B2 (en) 1975-02-06
SE386462B (en) 1976-08-09
AU5055672A (en) 1974-07-04
DE2300374B2 (en) 1976-04-08
DE2300374A1 (en) 1973-09-06

Similar Documents

Publication Publication Date Title
US5435898A (en) Alkaline zinc and zinc alloy electroplating baths and processes
US3905878A (en) Electrolyte for and method of bright electroplating of tin-lead alloy
Boto Organic additives in zinc electroplating
CA1051818A (en) Bath and method for the electrodeposition of bright nickel-iron deposits
US3723263A (en) Composition of baths for electrodeposition of bright zinc from aqueous, acid, electroplating baths
US2250556A (en) Electrodeposition of copper and bath therefor
US3669854A (en) Zinc electroplating electrolyte and process
US3824158A (en) Composition of baths for electrodeposition of bright zinc
US4462874A (en) Cyanide-free copper plating process
GB2179676A (en) Zinc alloy electroplating
US3821095A (en) Zinc electroplating process and electrolyte therefor
US3919056A (en) Zinc plating process and electrolytes therefor
US4129482A (en) Electroplating iron group metal alloys
DE2506467A1 (en) BATH FOR GALVANIC DEPOSITION OF PALLADIUM-NICKEL ALLOYS
US3767540A (en) Additive for electrodeposition of bright zinc from aqueous, acid, electroplating baths
US4270990A (en) Acidic electroplating baths with novel surfactants
US4119502A (en) Acid zinc electroplating process and composition
US4673471A (en) Method of electrodepositing a chromium alloy deposit
GB1569250A (en) Alloy plating
US4521282A (en) Cyanide-free copper electrolyte and process
US2495668A (en) Electrodeposition of copper
US3580821A (en) Bright silver electroplating
US4089754A (en) Electrodeposition of nickel-iron alloys
CA1081650A (en) Additive for improved electroplating process
US3672971A (en) Bright-zinc plating bath