CA1134317A - Zinc electroplating bath - Google Patents
Zinc electroplating bathInfo
- Publication number
- CA1134317A CA1134317A CA000316708A CA316708A CA1134317A CA 1134317 A CA1134317 A CA 1134317A CA 000316708 A CA000316708 A CA 000316708A CA 316708 A CA316708 A CA 316708A CA 1134317 A CA1134317 A CA 1134317A
- Authority
- CA
- Canada
- Prior art keywords
- quaternary
- butyl nicotinate
- electroplating bath
- zinc
- bath
- 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
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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/22—Collecting emitted gases
Abstract
Case U-10,744 BFC/pr ABSTRACT OF THE DISCLOSURE
A non-cyanide zinc electroplating bath containing an effective amount of a leveling and brightening agent comprising a bath soluble butyl nicotinate quaternary salt. The electro-plating bath may further advantageously incorporate an effective amount of a polyether compound as a supporting brightening agent and methane sulfonic acid and salts thereof as a supporting level-ing agent. The improved leveling of the bright electrodeposited zinc plate in accordance with the process aspects is attained over a relatively broad range of pH and current density.
A non-cyanide zinc electroplating bath containing an effective amount of a leveling and brightening agent comprising a bath soluble butyl nicotinate quaternary salt. The electro-plating bath may further advantageously incorporate an effective amount of a polyether compound as a supporting brightening agent and methane sulfonic acid and salts thereof as a supporting level-ing agent. The improved leveling of the bright electrodeposited zinc plate in accordance with the process aspects is attained over a relatively broad range of pH and current density.
Description
~343~7 BACKGROUND OF THE INV:E:NTI ON
::
Because of its effectiveness and comparatively low cost, zinc plating has received wide spread commercial application for the corrosion protection of ferrous substrates and also as a deco~
rative finish. Zinc electroplating baths and processes of the types heretofore ]cnown have incorporated various brighteners to enhance the brightness of the deposited zinc plate further enhanc-ing the appearance of the plated article. While such prior art compositions and techniques have been effective in producing re-latively bright zinc deposits, a continuing problem has been the lack of achieving a desired degree of leveling or smoothness of the deposit. This problem is further aggravated by the fact that such bright zinc deposits are frequentIy applied on surfaces of ~ ;
articles which are relatively unfinished, rough and uneven thereby `
further magnifying surface roughness.
The improved non-cyanide zinc electropla-ting bath com-posi-tion and process of the present invention provides for a leveling heretofore unattainable with l~ath compositions and pro-cesses previously known, and further provides a smooth, bright and adherent zinc plating deposit of excellent corrosion and aesthetic appearance.
SUMM~RY OF THE INVENTION "~
The benefits and advantages of the present invention are achieved by a non-cyanide zinc electroplating bath composition of the so-called acid or neutral type adapted to operate over a ~-pH range of from about 2.0 to about 9.0 which contains a controlled e-Efective amount of a leveling and brightening agent comprising a -.~
bath soluble butyl nicotinate quaternary salt of the formula: -~
~ '.
~2- ` :
, -~l~a3~
o l+
~ .C-O~ (~2)3-CH3 .~ . .
_ ' _ :
Wherein.
R is CH3, C2Hs or C6H5CH2~ and X is Cl, Br, I, R-O-S03 or R-S03 The butyl nicotinate quarternary salts are efEective when employed in amounts as low as about 0.5 mg/l and can be em `~ .
ployed in concentrations as high as about 10.0 g/l depending upon the specific bath composition and the presence and concentration of supplemental supporting agents used.
.
In accordance with a preferred embodiment of the com-position and process of this invention, the use of the leveling and brightening agent in acid zinc chloride electroplating baths i~ further enhanced by the addition of controlled amolmts of p~l~ethe.rs as a supporting brightener agent and controlled effec-tive amounts of methane sulfonic acid and the salts thereof as a supplemental supporting leveling agent~ When operating the zinc plating bath at pM I5 generally above about 6.8, an organic chelating agent is advantageously incorporated to prevent zinc metal from precipitating from the bath.
In accordance with the p.rocess aspects of the present invention~ smooth, bright and adherent zinc deposits on metal substrates are attained by subjectin~ the articles to a electro-plating bath composit;on incorporating the aforementionçd butyl nicotinate quaternary salt at temperatures rang.inc~ from about ~3~3~
60F to about 140F and at current densities broadly ranging from about 5 ASF up to about 200 ASF.
Additional benefits and advantages of the present inven- ;
tion will beeome appa.rent upon a reading of the description of ;
the preferred embodiments taken in conjunction with the specific examples herein provided.
DESCRIPTION OF THE PRE:FERRED EMBODIMENTS
The improved electroplating bath of the present inven~
tion comprises an aqueous, cyanide-free, neutral or acid-type -~
zinc electroplating bath having a pH ranging from about 2.0 up to about 9.0 ineorporating the hutyl nicotinate quaternary salt in an ef~ective amount in addition to appropriate amounts of other eonventional constituents employed in acid zinc baths. In aecordanee with eonventional praetice, the bath comprises an .
a~ueous solution containing an aqueous soluble zine ~alt, sueh as zinc sulfate, zinc chloride, zinc fluoroborate, zinc aeetate ~ :
or the like às well as mixtures thereof to provide a eoncentration of z.ine rangin~ from about 5.0 up to approximately 105 g/l with . .
eoneentrations of æinc from about 5.0 to about 70 g/l being pre-f~rred.
In accordance with conventional practice, the aqueous soll:ltion may further contain inert salts from improving the con-ductivity o~ the bath sueh as sodium ehloride, potassiwll chloride, ` ~:~
ammonium ehloride, ammonium sulfate, magnesium chloride, magnesium su1fate and the like which are employed in concentrations ranging from about l.Q g/l up to approximately 500 g/l. In addition to the foregoing any one of a variety of wetting agents in accordance ~-with conventional practice ean also be satisfactorily employed with -;
eoncentrations thereof typically ranging from about 0.1 up to .
about 30 g/l. Buffering agents of the types also con~entionally -``
employed in commercial practice can al50 be advantageously ~.
, ,...,, , .,,, i ~.3L3~
employed such as boric acid or i.ts salts, acetic acid on its salts, or like compounds which are typically present in concentrations of from about 0.5 up to approximately 100 g/l.
In addition to the foreyoing conventional constituents, the improved bright zinc electroplating bath incorporates a con-trolled effective amount of a leveliny and brlghtening agent com-prising a butyl nicotinate quaternary salt of the formula:
_ _ : :
- ~C~ -C~3 X-_ Wherein:
R is CH3, C2Hs r C6~15CH2' and X is C1, Br, I, R-0-503 or R-503 .
The butyl nicotinate quaternary salt as the primary l~v~llnc~ and brightening agent is employed in concentrations as low as about 0.5 mg~l to amounts as high as about 10 g/l, while .
concentrations ranginy from about 10 my/1 to about 100 mg/l are pre:Ee:rred in most instances. Included among the primary leveling ayents which have prov.ided satisfactory performance are butyl nicotinate benzyl chloride quaternary, butyl nicotinate dimethyl ~ ~
sulfate quaternary, butyl nicotinate methyl methane sulfonate ~-quaternary, butyl nicotinate methyl iodide quaternary, butyl .. :
nicotinate ethyl iodide quaternary, butyl nicotinate methyl chloride quaternary, butyl nicotinate ethyl bromide quaternary, butyl nicotinate di.ethy1 sullate quaternary, and butyl nicotinate p-metllyl tosylate ~uaternary.
, . ~5 ~.
1.3~3~
In addition to the primary leveling and brightening ; `
agent, the aqueous plating solution can advantageously contain secondary or supporting brighteners such as a polyether having a .~
molecular weight ranging from about 100 up to about 1,000,000 and ~ ;
selected from the group consisting o polyalkylene glycols, poly-ethylene glycols, polypropylene glycols, polyglycidols,ethoxylated phenols, ethoxylated naphthols, ethoxylated acetylenic glycols, ethoxylated ~le~in glycols, and mixtures thereof. The secondary brightener can advantageously be employed in amounts ranging from ~.
about 0.25 up to approximately 20 g/l. Particularly satisfactory xesults have been obtained in acid zinc chloride plating baths employing a secondary polyether brightener comprising acetylenic gl.ycol 2,3,7,9 -tetramethyl -5-decyne-4, 7 diol-ethoxylated, or ethoxylated naphthol.
The improved leveling attained by employing the primary ~-~
leveling agent oan stlll be further enhanced in most instances by incorporating controlled effective amounts of methane sulfonic :
acid~as well as salts thereof includlng sodium salt, potassium salt, ma~nesium salt, zinc salt, and the like. The secondary methane sulfonic acid l.eveling agent can be employed in amounts rancJilly from about 0.005 up to about 5.0 g/l while concentrations of about 0.05 to about 0.02 g/l are satisfactory in most instances.
The pH operating range from about 2.0 to about 9.0 of the plating bath can be adjusted by the addition of sulfuric acid to the sulfate, sulfate-chloride, and hydrochloric acid to the chloride bath which is facilitated by the addition of conventional .
bu~fering agents thereto. In si-tuati.ons where the bath pH operat~ ~ .
ing range is above about 6.8, a sui.table organic chelating agent is advantageously employed such as NTA, ~DTA, citric acid, or the :
like in amounts conventionally ranging from approximately 0.5 up to about 250 g/l for preventing the zinc metal ions from p.recipi-~ ~ 3,~3~ ~7 tating out of the bath.
The advantages of the bath composition of the present ~`
invention are attainable in accordance with its process aspects employing barrel, tank as well as continuous plating facilities and equipment. The bath solution can be satisEactorily employed at temperatures ra~ging from about room temperature up to about 140F with temperatures of from about 60F to about 90F usually being preferred.
In order to further illustrate the present invention, the following specific examples are provided. It will be under-stood that the examples are provided for illustrative purposes and are not intended as being restrictive of the present invention as herein described and as set forth in the subjoined claims.
A J-shaped steel test specimen is plated for a period `~
of 15 minutes at a current density of 40 ASF employing a bath com-position as follows:
ConstltuentConcelltrstL_ r ZillC chloride 60 potassium chloride 195 boric acld 30
::
Because of its effectiveness and comparatively low cost, zinc plating has received wide spread commercial application for the corrosion protection of ferrous substrates and also as a deco~
rative finish. Zinc electroplating baths and processes of the types heretofore ]cnown have incorporated various brighteners to enhance the brightness of the deposited zinc plate further enhanc-ing the appearance of the plated article. While such prior art compositions and techniques have been effective in producing re-latively bright zinc deposits, a continuing problem has been the lack of achieving a desired degree of leveling or smoothness of the deposit. This problem is further aggravated by the fact that such bright zinc deposits are frequentIy applied on surfaces of ~ ;
articles which are relatively unfinished, rough and uneven thereby `
further magnifying surface roughness.
The improved non-cyanide zinc electropla-ting bath com-posi-tion and process of the present invention provides for a leveling heretofore unattainable with l~ath compositions and pro-cesses previously known, and further provides a smooth, bright and adherent zinc plating deposit of excellent corrosion and aesthetic appearance.
SUMM~RY OF THE INVENTION "~
The benefits and advantages of the present invention are achieved by a non-cyanide zinc electroplating bath composition of the so-called acid or neutral type adapted to operate over a ~-pH range of from about 2.0 to about 9.0 which contains a controlled e-Efective amount of a leveling and brightening agent comprising a -.~
bath soluble butyl nicotinate quaternary salt of the formula: -~
~ '.
~2- ` :
, -~l~a3~
o l+
~ .C-O~ (~2)3-CH3 .~ . .
_ ' _ :
Wherein.
R is CH3, C2Hs or C6H5CH2~ and X is Cl, Br, I, R-O-S03 or R-S03 The butyl nicotinate quarternary salts are efEective when employed in amounts as low as about 0.5 mg/l and can be em `~ .
ployed in concentrations as high as about 10.0 g/l depending upon the specific bath composition and the presence and concentration of supplemental supporting agents used.
.
In accordance with a preferred embodiment of the com-position and process of this invention, the use of the leveling and brightening agent in acid zinc chloride electroplating baths i~ further enhanced by the addition of controlled amolmts of p~l~ethe.rs as a supporting brightener agent and controlled effec-tive amounts of methane sulfonic acid and the salts thereof as a supplemental supporting leveling agent~ When operating the zinc plating bath at pM I5 generally above about 6.8, an organic chelating agent is advantageously incorporated to prevent zinc metal from precipitating from the bath.
In accordance with the p.rocess aspects of the present invention~ smooth, bright and adherent zinc deposits on metal substrates are attained by subjectin~ the articles to a electro-plating bath composit;on incorporating the aforementionçd butyl nicotinate quaternary salt at temperatures rang.inc~ from about ~3~3~
60F to about 140F and at current densities broadly ranging from about 5 ASF up to about 200 ASF.
Additional benefits and advantages of the present inven- ;
tion will beeome appa.rent upon a reading of the description of ;
the preferred embodiments taken in conjunction with the specific examples herein provided.
DESCRIPTION OF THE PRE:FERRED EMBODIMENTS
The improved electroplating bath of the present inven~
tion comprises an aqueous, cyanide-free, neutral or acid-type -~
zinc electroplating bath having a pH ranging from about 2.0 up to about 9.0 ineorporating the hutyl nicotinate quaternary salt in an ef~ective amount in addition to appropriate amounts of other eonventional constituents employed in acid zinc baths. In aecordanee with eonventional praetice, the bath comprises an .
a~ueous solution containing an aqueous soluble zine ~alt, sueh as zinc sulfate, zinc chloride, zinc fluoroborate, zinc aeetate ~ :
or the like às well as mixtures thereof to provide a eoncentration of z.ine rangin~ from about 5.0 up to approximately 105 g/l with . .
eoneentrations of æinc from about 5.0 to about 70 g/l being pre-f~rred.
In accordance with conventional practice, the aqueous soll:ltion may further contain inert salts from improving the con-ductivity o~ the bath sueh as sodium ehloride, potassiwll chloride, ` ~:~
ammonium ehloride, ammonium sulfate, magnesium chloride, magnesium su1fate and the like which are employed in concentrations ranging from about l.Q g/l up to approximately 500 g/l. In addition to the foregoing any one of a variety of wetting agents in accordance ~-with conventional practice ean also be satisfactorily employed with -;
eoncentrations thereof typically ranging from about 0.1 up to .
about 30 g/l. Buffering agents of the types also con~entionally -``
employed in commercial practice can al50 be advantageously ~.
, ,...,, , .,,, i ~.3L3~
employed such as boric acid or i.ts salts, acetic acid on its salts, or like compounds which are typically present in concentrations of from about 0.5 up to approximately 100 g/l.
In addition to the foreyoing conventional constituents, the improved bright zinc electroplating bath incorporates a con-trolled effective amount of a leveliny and brlghtening agent com-prising a butyl nicotinate quaternary salt of the formula:
_ _ : :
- ~C~ -C~3 X-_ Wherein:
R is CH3, C2Hs r C6~15CH2' and X is C1, Br, I, R-0-503 or R-503 .
The butyl nicotinate quaternary salt as the primary l~v~llnc~ and brightening agent is employed in concentrations as low as about 0.5 mg~l to amounts as high as about 10 g/l, while .
concentrations ranginy from about 10 my/1 to about 100 mg/l are pre:Ee:rred in most instances. Included among the primary leveling ayents which have prov.ided satisfactory performance are butyl nicotinate benzyl chloride quaternary, butyl nicotinate dimethyl ~ ~
sulfate quaternary, butyl nicotinate methyl methane sulfonate ~-quaternary, butyl nicotinate methyl iodide quaternary, butyl .. :
nicotinate ethyl iodide quaternary, butyl nicotinate methyl chloride quaternary, butyl nicotinate ethyl bromide quaternary, butyl nicotinate di.ethy1 sullate quaternary, and butyl nicotinate p-metllyl tosylate ~uaternary.
, . ~5 ~.
1.3~3~
In addition to the primary leveling and brightening ; `
agent, the aqueous plating solution can advantageously contain secondary or supporting brighteners such as a polyether having a .~
molecular weight ranging from about 100 up to about 1,000,000 and ~ ;
selected from the group consisting o polyalkylene glycols, poly-ethylene glycols, polypropylene glycols, polyglycidols,ethoxylated phenols, ethoxylated naphthols, ethoxylated acetylenic glycols, ethoxylated ~le~in glycols, and mixtures thereof. The secondary brightener can advantageously be employed in amounts ranging from ~.
about 0.25 up to approximately 20 g/l. Particularly satisfactory xesults have been obtained in acid zinc chloride plating baths employing a secondary polyether brightener comprising acetylenic gl.ycol 2,3,7,9 -tetramethyl -5-decyne-4, 7 diol-ethoxylated, or ethoxylated naphthol.
The improved leveling attained by employing the primary ~-~
leveling agent oan stlll be further enhanced in most instances by incorporating controlled effective amounts of methane sulfonic :
acid~as well as salts thereof includlng sodium salt, potassium salt, ma~nesium salt, zinc salt, and the like. The secondary methane sulfonic acid l.eveling agent can be employed in amounts rancJilly from about 0.005 up to about 5.0 g/l while concentrations of about 0.05 to about 0.02 g/l are satisfactory in most instances.
The pH operating range from about 2.0 to about 9.0 of the plating bath can be adjusted by the addition of sulfuric acid to the sulfate, sulfate-chloride, and hydrochloric acid to the chloride bath which is facilitated by the addition of conventional .
bu~fering agents thereto. In si-tuati.ons where the bath pH operat~ ~ .
ing range is above about 6.8, a sui.table organic chelating agent is advantageously employed such as NTA, ~DTA, citric acid, or the :
like in amounts conventionally ranging from approximately 0.5 up to about 250 g/l for preventing the zinc metal ions from p.recipi-~ ~ 3,~3~ ~7 tating out of the bath.
The advantages of the bath composition of the present ~`
invention are attainable in accordance with its process aspects employing barrel, tank as well as continuous plating facilities and equipment. The bath solution can be satisEactorily employed at temperatures ra~ging from about room temperature up to about 140F with temperatures of from about 60F to about 90F usually being preferred.
In order to further illustrate the present invention, the following specific examples are provided. It will be under-stood that the examples are provided for illustrative purposes and are not intended as being restrictive of the present invention as herein described and as set forth in the subjoined claims.
A J-shaped steel test specimen is plated for a period `~
of 15 minutes at a current density of 40 ASF employing a bath com-position as follows:
ConstltuentConcelltrstL_ r ZillC chloride 60 potassium chloride 195 boric acld 30
2,3,7,9 te~ramethyl 5-decyne ~, 7 diol 30 moles ethoxylated 5 butyl nicotinate dimethyl sulfate quaternary 0O06 The pH of the plating bath is 5.8. The ~-shaped steel test specimen upon completion of platin~ is provided with a smooth uniEorm bright zlnc electrodeposit.
:
..
. . ~ : . , : . : : ~, , .: ~, . . . ::
:~3~3~
EX~MPLE 2 A J-shaped steel test specimen is electroplated at a current density of 30 ASF for a period of 20 minutes in a bat.h composition having a pH of 5.5 as follows:
ConstituentConcentration g/l zinc chloride 5 ammonium chloride 100 -:~
ethoxyla-ted B-naphthol (avg. MW 900) 10 butylnicotine benzyl . ..
chloride quaternary . 0.015 -The electroplated specimen has a smooth bright zinc el~ctrodeposit on the surface thereof.
A J~shaped steel test specimen is electroplated in a -bath at a temperature of 78F at a current density o~ 25 ASF for a period o about 30 minutes. The bath has a pH o 5.2 and a~ .
composition as follows: ..
Constituent Concentxation g/l zinc sulfate 10 zinc chloride .25 ammonium chloride. 224 polyethylene glycol -(MW 1000) 2 ~ :
butyl nicotlnate ethyl :`~
bromide quaternary 0.05 . At the completion of the electroplating the test speci~
men was observed as having a smooth adherent bri~ht ~inc electro-deposit thereover.
While it wi.ll be apparent that the invention herein disclosed is well cal.culated to achieve the beneflts and advan-tac~es as hereinabove set ~orth, it will be appreciated that the inve~ltion is susceptible to modification, variation and chan~e
:
..
. . ~ : . , : . : : ~, , .: ~, . . . ::
:~3~3~
EX~MPLE 2 A J-shaped steel test specimen is electroplated at a current density of 30 ASF for a period of 20 minutes in a bat.h composition having a pH of 5.5 as follows:
ConstituentConcentration g/l zinc chloride 5 ammonium chloride 100 -:~
ethoxyla-ted B-naphthol (avg. MW 900) 10 butylnicotine benzyl . ..
chloride quaternary . 0.015 -The electroplated specimen has a smooth bright zinc el~ctrodeposit on the surface thereof.
A J~shaped steel test specimen is electroplated in a -bath at a temperature of 78F at a current density o~ 25 ASF for a period o about 30 minutes. The bath has a pH o 5.2 and a~ .
composition as follows: ..
Constituent Concentxation g/l zinc sulfate 10 zinc chloride .25 ammonium chloride. 224 polyethylene glycol -(MW 1000) 2 ~ :
butyl nicotlnate ethyl :`~
bromide quaternary 0.05 . At the completion of the electroplating the test speci~
men was observed as having a smooth adherent bri~ht ~inc electro-deposit thereover.
While it wi.ll be apparent that the invention herein disclosed is well cal.culated to achieve the beneflts and advan-tac~es as hereinabove set ~orth, it will be appreciated that the inve~ltion is susceptible to modification, variation and chan~e
3~ `
without departing from the spirlt thereof.
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i;
,~
. .
.
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~ ~.
Z .~
Z
.
.
, 9~ .
., ~ ~':': .
without departing from the spirlt thereof.
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Claims (8)
1. An aqueous non-cyanide zinc electroplating bath having a pH of from about 2.0 to about 9.0 containing an effective amount of a leveling and brightening agent comprising a bath soluble butyl nicotinate quaternary salt of the formula:
wherein:
R is CH3, C2H5 or C6H5CH2, and X is C1, Br, I, R-O-SO3 or R-SO3, an organic chelating agent being present when the pH is above 6.8.
wherein:
R is CH3, C2H5 or C6H5CH2, and X is C1, Br, I, R-O-SO3 or R-SO3, an organic chelating agent being present when the pH is above 6.8.
2. An electroplating bath as defined in claim 1, in which there is included an effective amount of a poly-ether compound as a supporting brightening agent.
3. An electroplating bath as defined in claim 1, in which there is included an effective amount of methane sulfonic acid and salts thereof as a supporting leveling agent.
4. An electroplating bath as defined in claim 1, in which there are included effective amounts of a poly-ether compound as a brightening agent and methane sulfonic acid and salts thereof as a leveling agent.
5. An electroplating bath as defined in claim 1, in which the butyl nicotinate quaternary salt is selected from the group consisting of butyl nicotinate benzyl chloride quaternary, butyl nicotinate dimethyl sulfate quaternary, butyl nicotinate methyl methane sulfonate quaternary, butyl nicotinate methyl iodide quaternary, butyl nicotinate ethyl iodide quaternary, butyl nicotinate methyl chloride quaternary, butyl nicotinate ethyl bromide quaternary, butyl nicotinate diethyl sulfate quaternary, and butyl nicotinate p-methyl tosylate quaternary.
6. An electroplating bath as defined in claim 2, in which the polyether compound is selected from the group consisting of polyalkylene glycols, polyethylene glycols, polypropylene glycols, polyglycidols, ethoxylated phenols, ethoxylated naphthols, ethoxylated acetylenic glycols, ethoxylated olefin glycols, and mixtures thereof.
7. An electroplating bath as defined in claim 4, in which the butyl nicotinate quaternary salt is present in the amount of about 0.5 mg/l to approximately 10.0 g/l, the poly-ether compound is present in an amount ranging from 0.25 to 20.0 g/l approximately, and the methane sulfonic acid is present in an amount ranging from about 0.005 to approximately 5.0 g/l.
8. A process for depositing a bright, smooth, adherent zinc plating on a substrate, which comprises the step of electrodepositing zinc from an aqueous non-cyanide zinc electroplating bath as defined in claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/869,967 US4170526A (en) | 1978-01-16 | 1978-01-16 | Electroplating bath and process |
| US869,967 | 1978-01-16 | ||
| US87219078A | 1978-01-25 | 1978-01-25 | |
| US872,190 | 1978-01-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134317A true CA1134317A (en) | 1982-10-26 |
Family
ID=27128141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000316708A Expired CA1134317A (en) | 1978-01-16 | 1978-11-22 | Zinc electroplating bath |
Country Status (9)
| Country | Link |
|---|---|
| AR (1) | AR219787A1 (en) |
| AU (2) | AU521274B2 (en) |
| BR (2) | BR7900282A (en) |
| CA (1) | CA1134317A (en) |
| DE (1) | DE2900501C2 (en) |
| GB (3) | GB2062009B (en) |
| IT (1) | IT1114331B (en) |
| MX (2) | MX152015A (en) |
| SE (1) | SE435399B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH662583A5 (en) * | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS. |
| US4699696A (en) * | 1986-04-15 | 1987-10-13 | Omi International Corporation | Zinc-nickel alloy electrolyte and process |
| US6238542B1 (en) | 1998-09-15 | 2001-05-29 | Thomas Helden | Water soluble brighteners for zinc and zinc alloy electrolytes |
| DE19941765A1 (en) * | 1998-09-15 | 2000-03-16 | Lpw Chemie Gmbh | Electroplating process for high-gloss zinc coatings on metal involves using aqueous acid electrolyte containing zinc salt and heterocyclic aromatic, especially N-alkyl-pyridine compound, as brightener |
| DE10033433A1 (en) * | 2000-07-10 | 2002-01-24 | Basf Ag | Process for electrolytic galvanizing from electrolytes containing alkanesulfonic acid |
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| WO2016105359A1 (en) | 2014-12-23 | 2016-06-30 | Colgate-Palmolive Company | Oral care implement |
| BR112017010947A2 (en) | 2014-12-23 | 2018-07-03 | Colgate Palmolive Co | oral hygiene instrument |
| CN107105873B (en) | 2014-12-23 | 2020-01-14 | 高露洁-棕榄公司 | Oral care implement having a multi-component handle |
| US10709533B2 (en) | 2017-12-12 | 2020-07-14 | Colgate-Palmolive Company | Oral care implement and handle and refill head thereof |
| US10631964B2 (en) | 2017-12-12 | 2020-04-28 | Colgate-Palmolive Company | Oral care implement |
| USD891784S1 (en) | 2018-12-18 | 2020-08-04 | Colgate-Palmolive Company | Electric toothbrush handle |
| USD960582S1 (en) | 2020-12-10 | 2022-08-16 | Colgate-Palmolive Company | Oral care refill head |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821095A (en) * | 1972-09-26 | 1974-06-28 | M & T Chemicals Inc | Zinc electroplating process and electrolyte therefor |
-
1978
- 1978-11-22 CA CA000316708A patent/CA1134317A/en not_active Expired
-
1979
- 1979-01-08 DE DE2900501A patent/DE2900501C2/en not_active Expired
- 1979-01-15 GB GB8036467A patent/GB2062009B/en not_active Expired
- 1979-01-15 SE SE7900338A patent/SE435399B/en unknown
- 1979-01-15 GB GB791398A patent/GB2012306B/en not_active Expired
- 1979-01-15 GB GB8038947A patent/GB2062010A/en not_active Withdrawn
- 1979-01-16 MX MX176305A patent/MX152015A/en unknown
- 1979-01-16 BR BR7900282A patent/BR7900282A/en unknown
- 1979-01-16 AR AR275188A patent/AR219787A1/en active
- 1979-01-16 MX MX176306A patent/MX152135A/en unknown
- 1979-01-16 AU AU43396/79A patent/AU521274B2/en not_active Ceased
- 1979-01-16 BR BR7900283A patent/BR7900283A/en unknown
- 1979-01-16 AU AU43395/79A patent/AU523965B2/en not_active Ceased
- 1979-01-16 IT IT47654/79A patent/IT1114331B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| IT1114331B (en) | 1986-01-27 |
| GB2012306A (en) | 1979-07-25 |
| IT7947654A0 (en) | 1979-01-16 |
| AU4339679A (en) | 1979-07-26 |
| BR7900283A (en) | 1979-08-14 |
| MX152015A (en) | 1985-05-24 |
| BR7900282A (en) | 1979-08-14 |
| GB2062010A (en) | 1981-05-20 |
| DE2900501C2 (en) | 1982-10-21 |
| MX152135A (en) | 1985-05-31 |
| AU523965B2 (en) | 1982-08-26 |
| GB2012306B (en) | 1982-08-04 |
| SE7900338L (en) | 1979-07-17 |
| AU4339579A (en) | 1979-07-26 |
| SE435399B (en) | 1984-09-24 |
| DE2900501A1 (en) | 1979-08-02 |
| AR219787A1 (en) | 1980-09-15 |
| GB2062009B (en) | 1982-09-08 |
| AU521274B2 (en) | 1982-03-25 |
| GB2062009A (en) | 1981-05-20 |
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