United States Patent (19) (11) 4,119,502

Arcilesi 45) Oct. 10, 1978

(54) ACID ZINCELECTROPLATING PROCESS 4,070,256 l/1978 Hsu et al. ........................... 204/55 R
AND COMPOSITION FOREIGN PATENT DOCUMENTS
(75) Inventor: Donald A. Arcilesi, Mount Clemens, 602,591 5/1948 United Kingdom .............. 204/DIG. 2
Mich.
Primary Examiner-G. L. Kaplan
(73) Assignee: M&T Chemicals Inc., Stamford, Attorney, Agent, or Firm-Kenneth G. Wheeless; Robert
Conn. Spector
(21) Appl. No.: 825,402 57 ABSTRACT
(22 Filed: Aug. 17, 1977 This invention relates to a method of producing lustrous
(51) Int. Cl.’................................................ C25D 3/22 to brilliant zinc electrodeposits, which comprises pass
52 U.S. Cl. .................................................. 204/55 R ing current from a zinc anode to a metal cathode for a
58) Field of Search .................. 204/55 R, 55 Y, 43 Z time period sufficient to deposit a lustrous to brilliant
Zinc electrodeposit upon said cathode; the current pass
56 References Cited ing through an aqueous acidic bath composition con
U.S. PATENT DOCUMENTS taining at least one zinc compound providing zinc cati
2,674,619 4/1954 Lundsted ..................... 106/308 QX ons for tlectroplating zinc, said zinc compound selected
3,594,291 7/1971 Todt et al. ...........................204/55 R from the group consisting of zinc sulfate, zinc chloride
3,694,330 9/1972 Korpiun et al ... 204/55 R and zinc sulfamate; chloride anions added as salts of
3,729,394 4/1973 Hsu et al. ........................... 204/55 R bath compatible cations excepting ammonium; in the
3,730,855 5/1973 Poor et al. ......................... 204/55 R absence of complexing or chelating agents of organic
3,778,359 12/1973 Popescu ... ... 204/55 R nature; and containing as cooperating additives at least
3,855,085 12/1974 Rushmere. ... 204/55 R one alkyl propoxyethoxy polyether, at least one aro
3,878,069 4/1975 Todt.......... ... 204/55 R matic sulfonate emulsifying agent, and at least one aro
3,891,520 6/1975 Todt et al. ... 204/55 R matic carbonyl compound.
3,928,149 12/1975 Steeg..... ... 204/55 R
3,972,788 8/1976 Passal .... ... 204/55 R
4,014,761 3/1977 Passal ................................. 204/55 R 6 Claims, No Drawings
4,119,502
1. 2
baths, certain organic aromatic carbonyl compounds
ACID ZINCELECTROPLATING
COMPOSITION
PROCESS AND are generally used as brighteners.
These brighteners provide fairly satisfactory zinc
BRIEF DESCRIPTION deposits, but the deposits tend to be dull in the low
5 current density regions, and they have a limited solubil
This invention relates to the electrodeposition of ity in mildly acidic zinc electrolytes,
bright zinc from an acidic electrolyte. More particularly
this invention relates to improved zinc plating bath DETAILED DESCRIPTION
compositions, to methods of using and preparing such This invention relates to a method of producing
bath compositions and to improved surfaces having O bright zinc electrodeposits over a wide current density
bright zinc electrodeposits thereon. range, which comprises passing current from a zinc
BACKGROUND OF THE INVENTION anode to a metal cathode for a time period sufficient to
The enactment and enforcement of various environ deposit a bright Zinc electrodeposit upon said cathode;
mental protection laws, especially those designed to 15 the current passing through an aqueous acidic bath
improve water quality, have made it desirable to signifi composition containing at least one zinc compound
cantly reduce or eliminate the discharge of cyanides, providing zinc cations for electroplating zinc, said zinc
phosphates, and a number of metal ions, from the efflu compound selected from the group consisting of zinc
ents of electroplating plants. As a result, non-polluting sulfate, zinc choride and zinc sulfamate; chloride anions
bright zinc plating processes have been sought as alter 20 added as salts of bath compatible cations, in the absence
natives to the classical zinc cyanide baths. of complexing or chelating agents of organic nature;
Alkaline solutions containing complex compounds of and containing as cooperating additives at least one
zinc and alkaline metal pyrophosphates have been pro alkyl propoxyethoxy polyether, at least one aromatic
posed as a replacement for cyanide baths and cyanide sulfonate dispersing or emulsifying agent, and, at least
processes for the electrodeposition of bright zinc. The 25 one aromatic carbonyl compound. The alkyl propoxye
electrodeposition of zinc using a pyrophosphate bath, thoxy polyether carrier brighteners of this invention
however, may give relatively poor low current density provide such a high degree of luster and ductility when
coverage. Spore formation, roughness, insufficient used with auxiliary brighteners and primary brighten
brightness, and relatively non-uniform deposits. In addi ers, that ammonium salts are completely unnecessary.
tion, passivation of the anodes may produce undesirable 30 The zinc deposits of this invention are lustrous to
precipitates which in turn can clog filter systems and brilliant, smooth, relatively ductile, low in internal
sometimes results in intermittent operation necessitated stress, have low tarnishing tendencies and good recep
by frequent changes of filter media. tivity to conversion coatings.
The use of phosphates may also produce waste dis Carrier brighteners of the general type:
posal problems since phosphates are not easily removed 35
and may promote the growth of undesirable aquatic C.H. --OCH3(OCH), OH
plant life if discharged into streams. These disposal
disadvantages further limit the acceptance of pyrophos where n = 6 to 14, n = 1 to 6, n = 10 to 20
phate zinc plating bath compositions in industrial appli exemplified by propoxylated ethoxylated lauryl alcohol
cations. (MW 1020), having the following structure:
Non-cyanide zincate zinc plating baths have also
been proposed as substitutes for cyanide containing
systems. However, the bright plating current density
range of these baths is quite limited, making the plating (H,
CH,-(CH)-(OCH-CH (OCHCH-OH
of articles of complex shape difficult, if not impossible. 45
Since the addition of cyanide to these non-cyanide zinc
ate baths greatly improves the bright plate current den give superior results when used in combination with
sity range of the deposits, platers tend to add cyanides auxiliary brighteners such as the condensation products
to their zincate systems, thus negating the non-cyanide of naphthalene sulfonic acid and formalin e.g.
feature of the original bath. 50
Highly acidic zinc plating baths have been known for
some time and such baths are cyanide-free. These sys
tems do not produce bright decorative deposits, (in the
currently accepted usage of the word "bright'), have
extremely poor low current density coverage and find
their chief application in the strip line plating of wire
55 SONa
"CC SONa

and sheet steel using very high but narrow current or alkyl aromatic ether sulfonates such as sodium n
density ranges. Thus, they are not suited for plating decyl diphenyl ether disulfonate:
objects of complex shape or for normal decorative, or
rustproofing application. -
Neutral, mildly alkaline or mildly acidic non-cyanide
zinc plating baths containing large amounts of buffering
and complexing agents to stabilize pH and solubilize the
zinc ions at the pH values involved have been employed SONa SONa)
to overcome the objections of using cyanide-based zinc 65
plating processes. M m
In order to improve and increase the brightness, lus and aromatic carbonyl primary brighteners of the gen
ter and throwing power of zinc deposits from these eral type
4,119,502
3 4.
gistically produce a very high degree of brightness - in
combination with the other components of the system,
RCH=CH-R,
O
are added to the electrolyte which is mixed until they
are dissolved.
5
where R is an alkyl radical of 1 to 3 carbons and R is an PLATING
aromatic or heteroaromatic radical which may be un The examples of this invention were evaluated in 267
substituted or carry substituents such as -OH, ml. Hull Cells and in 4 liter rectangular plating cells as
-OCH, -OCH5, -OCH, -OCH2O-, -OC. follows:
HOH, -COOH, -NO, -NH, -N(CH2) 10
where n is 1 to 6, -NCHCH-OH), etc. HULL CELL TESTS
The superiority of this process can be illustrated by Hull Cell tests were run under conditions described
comparing the examples of this invention to those ob as follows:
tained with carrier brighteners of prior art. A polished steel or brass panel was scribed with a
The carrier brighteners of this invention also function 15 horizontal single pass of 4/0 grit emery to give a band
as solubilizing agents for brightening agents, such as width of about 1 cm. at a distance of about 2.5 cm. from
benzal acetone, that would normally be difficult to
dissolve in the electrolyte of subsequent Example #1. the bottom of the panel. After suitably cleaning the
Also, permitting the use of high concentrations of these panel, it was plated in a 267 m. Hull Cell, at a 2 ampere
additives in the electrolyte without deleterious effects. cell current for 5 minutes, at a temperature of 20° C.
using magnetic stirring and a 99.99.--pure zinc sheet as
EXAMPLES an anode.
The acid zinc examples of this invention were pre 4. LITER PLATING CELL
pared as follows:
Acid Zinc Electrolyte 25 The 4 liter plating cell tests were run under the fol
lowing conditions:
First a mixing vessel was filled half-way to the de Plating cell - 5 liter rectangular cross-section (13
sired final volume with distilled water. cm. X 15 cm.) made of Pyrex.
Then a zinc compound, such as zinc chloride, was Solution volume - 4 liters to give a solution depth, in
mixed into the water so as to function as a source of absence of anode, of about 20.5 cm.
metal ions for subsequent electrodeposition. Temperature - 20 F. (maintained by immersing cell
Next an alkali metal salt, such as potassium chloride, in a thermostatically controlled water bath).
was added to the above mixture to provide high electri Agitation - bubbling air.
cal conductivity to the electrolyte during subsequent Anode - 99.99.--zinc balls, 5 cm. in diameter strung
electrodeposition. 35 on titanium wire - 5 balls per cell.
To the above mixture a buffering agent, such as boric Cathode - brass strip (2.54 cm. X 20.3 cm. x 0.071
acid, was then added so that the pH of the final electro
lyte could ultimately be easily maintained between ap cm.) depth
buffed and polished on one side and immersed to a
of about 17.8 cm. - horizontal bend 2.54 cm.
proximately 5 and 6. The pH should be maintained from bottom and the next 2.54 cm. bent to give an inter
between approximately 5 and 6 because as the pH of the 40 nal angle on the polished side of cathode of about 45
electrolyte drops below about 5, the zinc anodes begin polished side facing
to dissolve excessively, and at a pH of about 6 zinc 10.2 cm. and scribedanode at an approximate distance of
vertically in center with a 1 cm.
hydroxide forms and precipitates out of the electrolyte. wide band of a single pass of 4/0 grit emery paper
It should be noted that as the bath is electrolyzed the scratches.
pH will slowly rise. It can be lowered by adding con 45 Cell current - 2.0 to 5.0 amperes.
centrated hydrochloric acid. If it is necessary to raise Time - 5 minutes to 8 hours per day.
the pH, it can be raised by adding a solution of sodium Some deposits were plated for 5 to 15 minutes to give
hydroxide.
After the zinc compound, the conducting salt and the normally utilized thicknesses of zinc (0.2 to 0.5 mils or
buffering agent are mixed together, the mixture is raised 5.1 to 12.7 microns) while other deposits were plated for
to its final volume, and after all of the constituents are 50 as long as 7 to 8 hours to observe physical properties
dissolved, the mixture is filtered. This filtered mixture is such as ductility, tensile stress, etc. and to provide suffi
an acid zinc electrolyte without grain refining additives. cient electrolysis to deplete some of the organic addi
tives.
Acid Zinc Grain Refining Agents
GENERAL OPERATING CONDITIONS
To the acid zinc electrolyte, grain refining additives 55
are added in the following order: Cathode current densities may range from about 0.1
First, the carrier brighteners are added to the electro to 5.0 amperes per square decimeter (ASD) depending
lyte which is mixed until they are dissolved. The carrier on whether the plating is done in barrels or on racks and
brighteners of this invention not only produce primary on such factors as concentration of bath zinc metal,
grain refining, but also help to solubilize subsequent 60 conducting salts, buffers, etc., and on the degree of
primary brighteners which would normally have a low cathode agitation. Anode current densities also may
solubility in an acid zinc electrolyte. range from about 0.5 to 3.0 ASD depending on bath
Next, the auxiliary brighteners, which produce sec ingredient concentrations, degree of solution circula
ondary grain refining and also help to solubilize subse tion around the anodes, etc.
quent primary brighteners, are added to the electrolyte 65 The operating temperature of the baths are ambient
which is mixed until they are dissolved. temperatures ranging from about 15 to 40° C. Agitation
Finally, the primary brighteners, which produce ter is of the moving cathode rod type or involving the use
tiary grain refining - i.e., these compounds can syner of air.
5.
4,119,502 6
Anodes generally consist of 99.99-i-pure zinc which Bent cathodes or Hull Cell panels electroplated in the
may be immersed in the plating bath in baskets made of solution of example #1 are bright and ductile over cur
an inert metal such as titanium or which may be sus rent densities ranging from about 0 to 20 ASD.
pended in the bath by hooks hanging on the anode bar
made of an inert metal such as titanium. EXAMPLE II
The plating baths may be used for rack or barrel The same as example #1 but instead of the auxiliary
plating purposes. The basis metals generally plated are brightener of example #1, 10 g/l of the following auxil
ferrous metals such as steel or cast iron to be zinc plated iary brightener was used:
for protection against rusting by a cathodic protection
mechanism and also for providing decorative eye ap 10
peal. To further enhance the protective action of the
zinc, the zinc after plating may be subjected to a con CH(CH,
version coating treatment, generally by immersion or
anodic electrolytic action in baths containing hexava 15
lent chromium, catalysts, accelerators, etc. The conver SONa SONa
sion coating treatment may enhance the luster of the
zinc as plated by a chemical or electropolishing action Bent cathodes or Hull Cell panels electroplated in the
as well as providing a conversion coating film consist solution of example #2 are bright and ductile over cur
ing of a mixture of Cr VI, CR III and Zn compounds rent densities ranging from about 0 to 20 ASD.
ranging in color from very light iridescent, to blue, to 20 EXAMPLE III
iridescent yellow to olive drab etc. The more highly
colored coatings are thicker and may provide better Same as example # 1 except that 5 g/l of the auxiliary
corrosion protection in humid saline atmospheres. To brightener of example #1, in addition to 5 g/l of the
further enhance protective action, usually on the more 25 auxiliary brightener of example #2 was used.
transparent, lighter colored films, there may be applied Bent cathodes or Hull Cell panels electroplated in the
lacquer coatings, air dried or baked. To some of the solution of example #3 are unusually bright and uni
thinner, lighter-colored conversion coating there may form, as well as ductile, over current densities ranging
be applied a more intense and varied color by immer from about 0 to 20 ASD.
sion in solutions of suitable dyestuffs to give pure jet 30 What is claimed is:
black to pastel range of colors which may then be fol 1. A method for producing lustrous to brilliant zinc
lowed by lacquer coatings to apply protection against electrodeposits which comprises passing current from a
abrasion, finger staining etc., in use. zinc anode to a metal cathode for a time period suffi
During the plating operation, it is desirable to keep cient to deposit a lustrous to brilliant zinc electrodeposit
metallic contaminants at very low concentration levels 35 upon said cathode, the current passing through an aque
in order to insure a bright zinc electrodeposit. Such ous acidic bath compositing containing at least one zinc
contamination from metal ions, (such as cadmium, cop compound providing zinc cations for electroplating
per, iron, and lead) may be reduced or eliminated zinc, said zinc compound selected from the group con
through conventional purification methods. Other types sisting of zinc sulfate, zinc chloride and zinc sulfamate;
of contaminants (such as organic contaminants) may chloride anions added as salts of bath compatible cati
also be eliminated or reduced by circulation of the zinc ons excepting ammonium; in the absence of complexing
electroplating solution through a suitable filter media or chelating agents of organic nature; and containing as
such as activated carbon or types of ion exchange or cooperating additives at least one alkyl propoxyethoxy
absorption media. polyether exhibiting the formula:
The following examples are submitted to further the 45
understanding of the operation of the invention and C.H. --OCH)-(OCH)-OH
should not be construed so as to limit its scope.
EXAMPLE I
where n is an integer of from 6 to 14, n is an integer of
from 1 to 6, and mis an integer of from 10 to 20, at least
An acid zinc bath was prepared having the following 50 one aromatic sulfonate emulsifying agent, and at least
composition: one aromatic carbonyl compound.
2. The process of claim 1 wherein at least one zinc
ZnCl 100 g/1 compound is selected from zinc sulfate, zinc chloride
KCl 200 g/1 and mixtures thereof.
HBO, 20 g/l 55 3. The process of claim 1 wherein said zinc com
(H, 10 g/1 pound is zinc sulfamate.
4. An aqueous acidic plating solution containing at
CH,-(CHOCH-CHS (OCHCH;13 OH least one zinc compound providing zinc cations for
CH 10 g/l electroplating zinc, said zinc compound selected from
the group consisting of zinc sulfate, zinc chloride and
SO, SOH zinc sulfamate; chloride anions added as salts of bath
compatible cations excepting ammonium; in the absence
O 0.5 g/1 of complexing or chelating agents of organic nature;
and containing as cooperating additives at least one
()-CH=CH-2-CH, alkyl propoxyethoxy polyether exhibiting the formula:
pH: Adjusted to 5.5
7
4,119,502 8
where n is an integer of from 6 to 14, m is an integer of zinc compound is selected from zinc sulfate, zinc chlo
from 1 to 6, and mis an integer of from 10 to 20, at least ride and mixtures thereof.
one aromatic sulfonate emulsifying agent, and at least 6. The composition of claim 4 wherein said zinc com
one aromatic carbonyl compound. pound is zinc sulfamate.
5. The composition of claim 4 wherein at least one 5 k is

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