Electro Baños Alcalinos Teoria PDF

A paper 2resented at the Eightieth General
Meeting, held at Chicago, II1., October 3,

7947, H, J. Read ~residlnq.
CYANIDE ZINC PLATING BATHS t
By R. O. HUt.L2 AND C. J. WERNLUNI~
ABSTRACT
On account of their high throwing power and their capacity to pro-
duce an attractive bright plate, the new zinc cyanide baths introduced
in 1935 have made rapid strides in the past several years and their
place is now thoroughly established in industry. The protection of
steel against corrosion continues to be the main purpose of
zinc plate. Detailed formulas and standard zinc plating procedures
are presented and discuss.ed at length. Bright zinc plating, to
be commercially successful, requires that the plating bath be free from
heavy metal impurities, and that the ratio of zinc to cyanide in solu-
tion be maintained within close limits. Finally, addition agent selection
and control of its concentration are essential. Numerous literature
references are included.
I. I N T R O D U C T I O N
Zinc has for many years been one of the most widely eleetrodeposited
or electroplated metals, the chief function of the zinc plate being the
protection of iron and steel against rust. For this purpose, zinc has
long remained the preeminent low-cost metal coating, whether applied
by electroplating, from acid or cyanide baths, or by hot dipping,
sherardizing or spraying.
Most of the tonnage of zinc 'consumed in electroplating is through
the medium of plating baths of the acid type in the application to steel
strip, wire, wire cloth and similar products. For such purposes, a white
matte deposit is produced, since appearance is usually secondary in
importance to thickness, adherence and ductility of coating.
Cyanide zin'c plating baths possess several inherent advantages over
the acid baths, e.g., high throwing power, and more recently the ca-
pacity for production of truly bright deposits which make them ap-
plicable to plating of finished articles. For such purposes, the cyanide
baths have made rapid forward strides in the past several years, until
their place is now thoroughly established in industry.
Most of the development of cyanide zinc baths has taken place since
1919, although as early as 1907 R. C. Snowden 4 deposited zinc from
x Manuscript received August 18, 1941.
Electroplating Div., E. I. duPont de Nemours 8: Co., Cleveland, Ohio.
a Eleetroplating Div., E. I. duPont de Nemours & Co., Niagara Falls, N. Y.
Trans. Eleetroehem. Soe. 11, 131-33 (1907).
407
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408 R.O. H U L L A N D C. I. W E R N L U N D
a zinc sulfate solution containing enough potassium cyanide to redis-

solve the precipitate. C. H. Froctor ~ was among the first to recommend
cyanide zinc baths, giving three formulas for specific uses. T. C.
Eichstaedt 6 described a solution composition for zinc-tin deposits. A
few other investigators reported on cyanide formulas at about the same
time.
Probably the first authoritative investigation of cyanide zinc baths
was that of Blum, Liscomb and Carson 7 who developed the pertinent
fundamental chemistry and gave definite recommendations with respect
to bath composition and operating conditions. Their bath remains one
of the best from the standpoint of operating characteristics, although
it is not readily amenable to production of bright deposits.
One of the authors s reported the results of an extended study of
addition agents for cyanide zinc baths and recommended a formula
that produces deposits at high throwing power. Horsch and Fuwa 9
made an intensive study of throwing power and 'current efficiencies of
zinc plating solutions, concluding that the cyanide type of bath is su-
perior in these respects to the acid bath.
One of the most important contributions to improvement of cyanide
zinc plating was the study of alloy deposition of zinc with other metals,
using alloyed zinc anodes. The first successful alloying metal used for
this purpose was mercury. ~~ Aluminum is also used in anodes as an
alloying metal with zinc or with added mercury, n Aluminum, when
present in the zinc anodes, offers the advantage of uniform anode cor-
rosion and minimum sludge formation, but aluminum does not co-
deposit with the zinc. Anodes made of alloys of zinc with nickel and
with mercury or aluminum 12 are said to possess a fine-grained struc-
ture and are capable of electrolysis at high anode current densities. A
still later improvement in zinc anodes was the alloying of the zinc with
magnesium or calcium 1~ for the purposes of reducing the anode cur-
rent efficiency to approximate the cathode current efficiency and of
improving uniformity of corrosion.
The m~st recent important line of development in cyanide zinc baths
has been the introduction of several bright plate processes that give
deposits ranging from a bright luster to a brilliant surface resembling
chromium. This development has resulted in new applications for zinc
plating in which good appearance must be combined with excellent
rust protective qualities.
It is expected that cyanide zinc plating will continue to expand in the
future, as the advantages of the cyanide bath are more fully appre-
ciated. Cyanide baths are now used to a limited extent for continuous
6Metal Ind. N. Y. IS, 152 (1917); 18, 478 (1920); 19, 199 (1921).
Metal Ind. N. Y. 17, 22.24 (1919).
7 "Zinc Cyanide Plating Solutions," Nail. Bur. Standards Technol. Paper ~195 (Aug. 17, 1921).
a "l'r~ma. ]~Ie~trochera. Soc. 40, 257-85 (I921).
a T r a n s . ]~le.c.trochem. Soc. 41, 363-388 (1922).
l a A b r a h a m V a n Winkle, U. S. Pat. 901,758; Proctor and Wernlund, U. S. Pat. 1,435,875;
J. Haas, Jr., U. S. Pat. 1,451,543 and 1,497,265.
a G . B. Hogaboom, U. S. Pat. 1,887,841; A. K. Graham, U. S. Pat. 1,888,202; Trans.
Electroehem. Soe. 63, 121-133 (1933).
2a G. B. Hogaboom, U. S. Pat. 2,064,307.
3aR. O. Hull, Cony. Proc. Am. Electroplaters' Soe. (1940); U. S. Pat. 2,214,33I; Ferm.
U. S. Pat. 2,243,696.
CVANI1)E ZINC PI,ATIN(" IIA'|'t:IS 409
steel strip plating, m!d this use should continue to grow. Bright zinc
plating exclusively from cyanide baths has filled an important industrial
need as a companion process to bright cadmium plating, which it has
in some instances replaced to good advantage. Many more metal parts
are now plated than ever before, and the rust protective value of zinc
combined with the added excellent appearance of bright zinc offer an
e!ectroplated finish of wide application.
II. PRINCIPLES
The cyanide zinc bath has the following advantages and disadwm-
tages as compared with the acid type of zinc bath :
Advantages of Cyanide Type. Disadvantages of Cyanide Type.
1. Ability to plate semi-bright to 1. Slower possible speed of deposition.
mirror-bright deposits. 2. Higher initial solution cost and
2. Exceptionally high throwing power maintenance.
of cyanide baths resulting in de- 3. Not applicable for coating certain
posits of uniform thickness. types of basis metals, e.g., malleable
3. Adaptability to low-cost equipment; and cast iron.
steel tanks may be used.
Cyanide zinc baths in present successful use may be divided into three
general classes: (1) the straight cyanide bath; (2) the zinc-mercury
bath; and (3) the bright zinc baths.
The straight cyanide bath is used to advantage for applications in
which rust protective value is of first importance, and appearance of
deposit is of little consequence. This type of bath offers the highest
cathode efficiency when properly used, although this desirable condi-
tion can be maintained only by close chemical control. The high-effi-
ciency, straight cyanide bath is usually not capable of producing de-
posits of good appearance and with this bath it is particularly difficult to
apply zinc coatings to malleable or cast iron having a low hydrogen
overvoltage. For general application, the operable current densities
can be varied quite widely, and bath composition can be modified to
maintain good cathode efficiencies up to 100 amp./sq, ft. (11
amp./dm.2), at which rate deposits are produced approximately 0.005
to 0.006 in. (0.13 to 0.15 mm.) in thickness per hour. This speed of
deposition is not as great as is possible from the acid type of zinc
bath but, for any except rapid travelling steel strip or wire plating,
the above plating speed usually is ample for production requirements.
The zinc-mercury type of bath is used because of its versatility in
plating over a large variety of basis metals and its ability to produce
uniformly white deposits over a wide range of current densities. This
bath has excellent covering power at low current densities and hence
plates into deep recesses, although this bath is not usually recommended
for zinc plating over cast iron or malleable iron. Its operation is not
difficult, bath maintenance being required with respect to only the
essential zinc, mercury, cyanide and caustic soda contents. Excessive
mercury must be avoided as it results in so-called "mercury spots" in the
plate which may develop only after a period of time following plating.
The bright zinc baths are essentially variations in solution composi-
tion of the straight cyanide bath, with the additional requirements of
410 ~. o . H U L L A N D C. J . W E R N L U N D
brightening and rapid-covering agents. Maintenance of tile bright type

of bath must be carefully controlled in order to insure good cathode
efficiency combined with operable bright current density ranges. High
purity materials must be used exclusively, since the bright bath is ex-
tremely susceptible to exceedingly small amounts of heavy metals or
other impurities. The applications and value of bright zinc result from
its combination of bright appearance and rust protective value. In
many cases bright zinc is now applied, in large part, even to metal
articles not requiring a bright finish but whose sales appeal is thereby
augmented. In recent years, the control of the bright zinc plating baths
has been simplified, and ample experience now enables accurate pre-
dictions as to their applicability in the case of almost all industrial metal
articles.
III. FUNCTIONS OF CONSTITUENTS OF BATHS
The fundamental chemistry of cyanide zinc baths has been discussed
by Blum, Liscomb and Carson, I~ and by Blum and Hogaboom. ~5 Their
concept was that, since (from cyanide solutions) zinc can be deposited
satisfactorily only from a mixture of sodium zincate and sodium zinc
cyanide, with an excess of sodium hydroxide or sodium cyanide or
both, all of the following components may be considered present in
such solutions: sodium zinc cyanide [Na2Zn(CN)4], sodium zincate
(Na2ZnO2), sodium cyanide, sodium hydroxide, and more or less
sodium carbonate resulting from cyanide decomposition.
As it is impossible to determine the exact proportions of zinc in
the double cyanide and in the zincate complexes, the zinc content may
arbitrarily be calculated as sodium zinc cyanide, Na2Zn(CN)4, up to
the limit of the sodium cyanide present, and the remainder of the zinc
calculated as sodium zincate. On this basis, free sodium cyanide and
sodium zincate do not both appear in expressing the composition of the
bath. It is obvious, moreover, that zinc ions are furnished in a solu-
tion by dissociation of both sodium zincate and sodium zinc cyanide
as follows :
(1) Na2Zn(CN)4 + 4NaOH = Na2ZnO-_, + 4NaCN + 2H20
(2) Na,_,ZnO2 = 2Na + q- ZnO2
ZnO2-- + 2H20 = Zn +§ + 4 ( O H ) -
(3) Na._,Zn(CN)4 ---= 2Na + + Z n ( C N ) 4 -
Zn(CN)~-- = Zn ~+ -1- 4(CN)-
There are definite indications (from unpublished conductivity and
pH data) that in the normal composition of bright cyanide zinc baths
about 75 to 90% of the zinc is present as sodium zincate and the re-
mainder as sodium zinc cyanide. This probability is also substantiated
by cathode current efficiency measurements.
It is evident from the above that the cyanide zinc plating solution is
very complex, since the various solution components are in equilibrium
14 See footnote 7.
io-"Principles of Electroplating and Electroformlng," 2nd Ed. (1930).
CYANIDE ZINC PLATING b'ATHS 411
with o'ne another, and the states of equilibrium are dependent upon the
respective concentrations of these components. While few studies have
been made of the equilibria involved in cyanide zinc plating baths and
would be essential to a fundamental, theoretical study of such plating
systems, it is possible empirically to control solution constituents for
which chemical analytical determinations can be made with sufficient
facility to insure continuously satisfactory bath operation. These con-
stituents are: (1) sodium cyanide; (2) zinc metal; (3) sodium hydrox-
ide or caustic soda; and (4) inorganic metal addition agents. The first
three of these are interdependent, and hence Graham 16 proposed the
expression for the ratio R:
NaCN (normality) q- NaOH (normality)
R=
Zn(CN)o normality
This ratio was then specified to be within definite limits for proper
operation.
It is possible to simplify the expression for composition of solution
still further, as developed later for bright zinc baths, by specifying a
definite range of concentration for sodium hydroxide, together with a
prescribed range of the arbitrary ratio M of total sodium cyanide
(which equals the sodium cyanide plus the sodium cyanide equivalent
of zinc cyanide) to zinc metal. Experience has shown that all zinc
cyanide baths, expecially the bright baths, can best be controlled by this
means. A few fundamental facts may be considered and associated with
solution control as determined by these conditions.
It is possible to deposit zinc from a sodium zincate-sodium hydroxide
solution in the absence of cyanide, provided a sufficient excess of sodium
hydroxide is present both to maintain the zinc in solution and to counter-
act the strong tendency toward hydrolysis of sodium zincate. Such a
solution used as a plating bath produces zinc deposits at high current
efficiencies (above 95%) at low current densities, but the deposits tend
to be spongy and of poor quality. It is likewise possible to deposit zinc
from a zinc cyanide-sodium cyanide solution (which must necessarily
contain some sodium zincate), but such deposits are white matte in color
and are produced at low current efficiencies, usually under 15%. It is
therefore essential for all three primary constituents, i.e., zinc, sodium
cyanide and sodium hydroxide, to be present to produce good-quality
deposits at high cathode efficiency. The functions of the sodium cyanide
are: (1) to combine with zinc compounds to form soluble complexes;
and (2) to provide a control medium for appearance of deposit. Since
current efficiency is also closely dependent upon the sodium cyanide
concentration, careful regulation of the sodium cyanide content is
necessary to combine good deposit quality with high current efficiency.
The principal function of sodiunl hydroxide is to provide the primary
source of zinc ions and to permit operation at high current efficiency.
Its concentration is easily controlled because sodium hydroxide parallds
i~ Trans. Electrochern. Soe. 63, I29 (1933).
412 it. o. IIULL AND C. J. WERNLUND
and is roughly proportional to the zinc metal content as it may change

due to differences between anode and cathode efficiencies. Caustic soda
increases or decreases to the extent that anode and cathode efficiencies
are not equal. Thus, if the anode efficiency exceeds the cathode effi-
ciency, hydrogen is liberated, hydroxyl ions are formed by resulting
dissociation of water, and the sodium hydroxide concentration and pit
increase. Both sodium cyanide (total) and sodium hydroxide are
readily determined by direct analysis, detailed hereinafter.
Gray 17 utilized the high alkaline type glass electrode in studying the
effect of pH and alkalinity on the operation of cyanide zinc plating
baths, and the results showed that the operation of the bath with too
high a pH value from caustic additions invariably gave a white matte
deposit, while the use of low pH values gave poor anode corrosion.
The best range for operation of cyanide zinc plating baths was found
to be represented by the fairly well defined pH region intermediate
between these two limiting conditions, which in general is a pH range of
12.2 to 12.7. Measurement and control of pH may ultimately prove to be
an important factor in the operation of all cyanide zinc plating baths.
The zinc metal concentration must be controlled in cyanide zinc baths,
since this factor not only establishes the rate of deposition and current
efficiency, but the two complexes that zinc forms determine the con-
centration of the cyanide and hydroxide components of the bath. Thus
experience has shown that the ratio M of total sodium cyanide to zinc
is of greater significance than the actual zinc metal content, assuming
the customary sodium hydroxide limits of concentration. It is there-
fore apparent that cyanide zinc baths can best be controlled by main-
taining a definite range of sodium hydroxide concentration which is
not critical within that range, together with a definite ratio M which
is quite critical, as will be shown later.
In cyanide zinc baths few additions of salts are used other than the
primary ones mentioned, and even these few are little used at present.
Proposals have been made to add small amounts of sodium fluoride or
of aluminum salts to whiten the deposit; however, the beneficial effects
so obtained are of minor degree in comparison with the effects of
mercury compounds or of other inorganic and organic brighteners.
Because a high concentration of sodium hydroxide is essential to good
cathode efficiency, no other salts need be added to improve bath con-
ductivity or to buffer the solution with respect to pH changes.
IV. P L A T I N G BATH FORMULAS, OPERATING CONDITIONS

AND MAINTENANCE
The formulas recommended for cyanide zinc plating baths may con-
veniently be divided into: (1) the conventional cyanide, as described by
Blum and HogaboomlS; (2) tbe zinc-mercury process; and (3) the
bright zinc processes.
17Proe. Am. Electroplaters' Soe. (1941:).
18 See footnote 15.
CYAN[I)I,: ZINC. I ' I , A T I N G bATIIS 413
1. d'yanide Bath withoul .,ldditio, .4d~'uls.

a. 5'olution Coenposition: ~./I . . . . z./g,:tl.
Zinc cyanide, Zn (CN),~ . . . . 60 8
Sodium cyanide, NaCN . . . . 23 3
Sodium hydroxide, NaOH
(caustic soda) . . . . . . . . . 53 7
Operatin 9 Conditions:
Temperature . . . . . . . . . . . . 400-50 ~ C. (104~ ~ F.)
Current density . . . . . . . . . . 1-2 amp./dm. 2 (9.3-19 amp./sq, ft.)
Cathode current efficiency.90-95%
Anodes--High Grade . . . . . 99.75% @ zinc
The solution composition should be maintained within • 10%, and

the ratio M of total sodium 'cyanide to zinc should be within the range
of 2.0 to 2.5. The throwing power and covering power are good, as
the result of the low ratio M. The bath is used for production of zinc
primarily for rust protection and serves admirably for this purpose.
'['he zinc coatings are of good quality and of high ductility.
To improve the whiteness and stain resistance of deposits from this
type of bath, gum arabic with sodium fluoride and lead salt have been
patented19 as additions to the bath.
The above cyanide bath, without addition agents, has recently been
modified to permit rapid deposition up to 13.5 amp./dm3 (125 amp./sq.
ft.) at high cathode current efficiency. The composition recommended
for this purpose is as follows:
b. Solution Composition: g./L. oz./aal.
Zinc cyanide, Zn(CN)2 . . . . 90 12
Sodium cyanide, NaCN . . . . 37.5 5
Sodium hydroxide, N a O H . . 90 12
(caustic soda)
Operating Conditions:
Temperature . . . . . . . . . . . . 400-700 C. (104~ ~ F.)
Current density . . . . . . . . . . 6-12 amp./dm? (55-110 amp./sq, ft.)
Current efficiency . . . . . . . . 85-95%
(cathode)
Anodes--High Grade . . . . . . . 99.75% q- zinc
As in the lower speed bath, composition (la), constituents should

be maintained within • 10% of the amounts given, and the ratio M
of total sodium cyanide to zinc should be within the limits of 2.2 to 2.6.
It must be emphasized that adequate control of these baths is no less
important than for the bright zinc baths described hereinafter, if bath
operation is expected at high efficiency within the prescribed current
density ranges.
~J Mason, U. S. Pat. 2,136,629.
414 R.o. I t I J L L A N t ) C. J . W E R N L U N D
2. Zinc Mercury Process.

The zinc-mercury process ~~ operates on the principle of production
of a zinc-mercury alloy deposit which is smooth, white and more pleas-
ing in appearance than the straight cyanide bath deposits, comparing
favorably with acid zinc in this respect.
Still Barrel
Solution Composition
g./L. oz./gal. g./L. oz./gal.
Zinc cyanide, Zn(CN) . . . . . 37.5 5 60 8

Sodium cyanide. NaCN .... 22.5 3 30 4
Caustic soda, NaOH . . . . . . . 30.0 4 45 6
Mercury salt* . . . . . . . . . . . . . 0.25 0.03 0.25 0.03
Any mercuric salt such as tlgCl=, or }lgO is dissolved in sodium cyanide.
Operating Conditions.
Temperature . . . . . . . . . . . . . . . . . . . 30~ ~ C. (86~ ~ F.),
optimum 40 ~ C. = 104 ~ F.
Anodes (Intermediate or Prime
Western) . . . . . . . . . . . . . . . . . . . . 98.25 zinc plus 0.5-1% mercury
Anode current density . . . . . . . . . . . 1.1 to 1.6 amp./dm3
(10 to 15 amp./sq, ft.)
Ratio anode to cathode surface . . . 2 : 1
Cathode current density . . . . . . . . . . up to 4.3 amp./dm3
(40 amp./sq, ft.)
Voltage . . . . . . . . . . . . . . . . . . . . . . 4-6 v. at tank bus bars
Cathode current efficiency,
2.7 amp./dm3 (25 amp./sq, f t . ) . . 9 0 %
Throwing power . . . . . . . . . . . . . . . . 35-40%
Bath Maintenance and Control. For good anode corrosion, not less
than 4 v. must be maintained across the plating tank bus bars and an
anode current density of 10 amp./sq, ft. (1.1 amp./dm. ~) should be
used. If, under normal load, the tank voltage is less than 4, anodes
are removed until the desired voltage is secured.
When properly operated, the solution contains from 0.1 to 0.2 g./L.
(0.013 to 0.027 oz./gal.) of mercury cyanide. During weekend or other
longer shutdowns, most of this mercury deposits out on the anodes
(by displacement), making it necessary to replenish the mercury in
the bath by adding mercury salts before operation is resumed. During
electrolysis mercury codeposits with the zinc. The mercury in the
anode forms amalgams with the metallic impurities present. These dis-
solve anodically and quantitatively with the zinc without appreciable
sludge formation. Accordingly, either low grade or high purity
zinc can be used as anode without danger of anode polarization or
objectionable bath contamination. If the bath builds up in zinc, about
one-third of the zinc anodes may be replaced by steel anodes, preferably
case-hardened. Under normal operation, a brown film covers the zincl
anodes, and uniform corrosion is maintained. The chief precaution to
See footnote 10.
CYANIDI,; ZINC PLATING BATHS 415
observe so as to ensure efficient anode performance is to avoid low anode

current densities or excessive mercury salts in the bath, as either may
result in mercury spots in the plate.
Since the bath is "self-purifying," only intermittent filtration of the
solution is required to remove ferric hydroxide and other insoluble
salts. As in the case of the plain cyanide bath, all constituents of the
bath should be maintained within ___ 10% of the recommended con-
centrations.
The zinc-mercury bath possesses not only good throwing power, but
good covering power or ability to plate readily at low current densities.
The rust protective value of the alloy deposit is about the same as that
of an unalloyed zinc deposit.
3. Bright Plating Baths.
The bright cyanide baths were introduced to the plating industry in
1935 and came into widespread use shortly thereafter, until at the pres-
ent time they may be 'considered among our essential plating processes.
The immediate popularity of bright zinc resulted largely from an
acute shortage of cadmium which originated from its use for auto-
mobile bearings. With this impetus, bright zinc assumed its place
perhaps more rapidly than any other new plating process or principle,
because it is the obvious substitute for bright cadmium for rustproofing
purposes. The basic principles of bright cyanide zinc were developed as
the result of extensive research work, several years after preliminary
indications of the possibility of producing bright zinc deposits were
observed.
The first principle in bright zinc plating is the use of a plating bath
virtually free from heavy metal impurities and employing high purity
zinc anodes31 The fact has long been recognized that even minute
amounts of some metals affect the physical and chemical properties of
zinc metal to a marked degree, and this was likewise found true in
bright zinc plating, in which minute amounts of heavy metals markedly
affect the color and brightness of deposits. Thus it is believed that
molybdenum, used as an inorganic brightener in zin'c baths, may exercise
its effectiveness in sequestering small amounts of lead by combining
with it to form a complex compound.
There are two methods of purification in general use: (1) addition
of 0.25 to 2.5 g./L. (0.033 to 0.33 oz./gal.) sodium sulfide in the form
of a concentrated solution (sodium bisulfite or sodium thiosulfate may
be used instead of or with sulfide), which precipitates lead but not
copper; or (2) addition of zinc dust, 0.25 to 2.5 g./L. (0.033 to 0.33
oz./gal.), followed by thorough stirring and filtering.
The second principle in bright zinc plating is rigorous control of
solution composition, the most critical factor being the ratio M of total
sodium cyanide to zinc metal. Table I gives experimental results of
this factor as related to bright plate current density range and cathode
efficiency and shows in a 'concrete manner the narrow M range within
which practical current densities can be used with high cathode ef-
ficiencies.
~UOplinger, U. S. Pat. 2,075,623; 2,146,439.
416 R.O. HULL AND C. J . WERNLUND
From Table I it is clear that M must be between 2.5 and 2.7 for
operation with high efficiency at normal current densities and room
temperatures.
In general, a low M value necessitates using a high current density,
and increasing M lowers the bright plate current density range.
The ratio M is also dependent upon the temperature of the bath,
if all of the operating factors are to be maintained at their optimum
value. Experience has shown that the values of M, as given in Table
II, must be used for various operating temperatures.
TABLE I
Total NaCN
Effect of Ratio M -= on Bright Plate Current Density
Zn (metal)
Range and Efficiency.
Approx. Bright Plate Current Density Range Cathode Efficiency at 35

Ratio ]VI amp./sq, ft. (3.8 amp./
Amp./dm. 2 Amp./sq. ft. din)) and 85 ~ F. (29 ~ C.)
2.25 4-10 37-93 92%

2.5 2-10 18-93 88%
2.7 1-10 9-93 82%
3.0 0.5-8.0 4.7-75 69%
3.2 0.3-8.0 2.8-75 54%
TABLE II
Optimum M Values vs. Temperatures.
Ratio M Temperature
Optimum ~
~
2.6 27.8-30.6 82-87

2.8 31.1-33.3 88-92
3.0 33.9-37.8 93-100
The caustic soda concentration is less critical than the M ratio, but
a minimum concentration is no less important. A minimum concentra-
tion of 60 g./L. (8 oz./gal.) of caustic soda is essential, not only for
brightness but for good efficiency, and bright deposits can be obtained
with concentrations up to 150 g./L. (20 oz./gal.). The optimum
values (given below) in the solution compositions insure a sufficiently
high concentration and are well within the operable limits. The con-
centration of zinc metal is not critical within the range of 30 g./L.
(4.0 oz./gal.) to 45 g./L. (6.0 oz./gal.) provided it is maintained in
the proper ratio to total sodium cyanide.
The third principle of bright plating applicable to most processes is
the use of a dilute oxidizing acid bright dip after plating to remove the
brown surface film that appears almost inevitably upon removal of the
work from the plating bath. This film, however, does not occur with
some brightening agents, in which case bright dipping is optional. A
CYANIDE ZINC PLATING BATItS 417
second desirable effect of a bright dip after plating is to improve

resistance of the zinc plate to tarnish and finger staining, although zinc
deposits produced from old baths free from heavy metals possess, in
general, excellent resistance to staining.
Until the above three principles are recognized and followed religi-
ously, bright zinc plating baths may be found difficult to maintain and to
operate satisfactorily as compared with the simpler cyanide cadmium
plating baths. This fact is probably largely responsible for the con-
tinued wide use of the latter at a higher metal cost. However, when
the operating principles of bright zinc plating are understood and
practiced, the process is no more troublesome than most of the other
plating processes.
The result of improper bath maintenance in bright zinc plating is
either lack of brightness, or low cathode efficiency, or both, and these
effects do not develop gradually but are noted immediately; whereas
with dull zinc plating baths, the prin'cipal effect of improper bath main-
te~ance is low cathode efficiency, apparent only upon determining zinc
deposit thickness. Hence, proper operation of any cyanide zinc bath,
whether bright or dull, necessitates analysis and adjustment of the
bath composition at frequent intervals.
The several bright zinc processes are the subject of numerous patents
covering addition agents, purifying agents and alloy anodes. However,
the fundamental bath compositions are approximately the same and
fall within the following ranges of concentration:
Ranges of Bath Composition for Bright Zinc Plate.
for StilI Plating for Barrel Plating
g. / L. oz./gal. g./L. oz./gal.
Zinc cyanide, Zn(CN) . . . . . . . . . . . 60-82 8.0-11 60-82 8.0-11

Sodium cyanide, NaCN . . . . . . . . . 18.7-64 2.5-8.5 34-75 4.5-10
Sodium hydroxide
(caustic soda, NaOH) . . . . . . . . . 75-112 10-15 75-97 10-13
Corresponding zinc metal . . . . . . . . ~ 34-45 4.5-6.0 34-45 4.5-6.0
Corresponding total sodium cyanide 68-135 9-18 68-135 11-19
Total NaCN |2.0-3.0 (still)
Ratio M --
Zn =(2.5-3.2 (barrel)
Use low ratio for low temp., high ratio for high temp.
As discussed heretofore, the exact concentrations of bath components
are not critical and may be varied quite widely, provided they are main-
tained in the proper balance.
Operating Conditio~zs
The operating conditions for the various bright zinc processes are
likewise quite similar and can be conveniently summarized as follows:
Temperature .............. 200-45 ~ C. (68~ ~ F.) extreme
27.80-37.8 ~ C. (82~ ~ F.) preferred
(see second principle for values of M
for different temperatures)
418 R. 0. H U L L A N D C. J . W E R N L U N D
Cathode current density . . . . . 0.2-10.7 anap./dm. 2 (2-100 amp./sq, ft.)

extreme limits
1.07-5.4 amp./dm? (10-50 amp./sq, ft.)
average limits
Tank voltage . . . . . . . . . . . . . . 1.5 to 6 v. (still)
10 to 15 v. (barrel)
Cathode current efficiency ...75 to 95%
Throwing power :
Haring cell, 5:1 ratio . . . . 35 to 55%
Solution conductivity . . . . . . . 4.5-5.5 ohm-cm.
Anode current density . . . . . . 1.07-3.2 amp./dm. 2 (10-30 amp./sq, ft.)
t Special High Grade zinc ball anodes of high purity 22
Anodes or High Grade 99.8% -t- zinc bar anodes
zinc-aluminum also with mercury ~3
zinc-calcimn or zinc-magnesium ~4
Addition Agents
The proper operation of bright zinc baths depends in large part upon
addition agents which are effective in one or more of several categories:
(1) brightening effect upon deposits; (2) improvement in covering
power at low current density, particularly for barrel plating; (3)
lowering of the current density limit at which bright deposits are ob-
tainable, thus permitting a low ratio of M and increasing the cathode
efficiency; and finally (4) permitting production of bright deposits
without bright dipping. Table III summarizes the effects of those ad-
dition agents that are in common use, all of which are the subject of
patents as indicated.
The rates of depletion of the above addition agents vary with the
conditions obtaining in each plating plant. The inorganic addition salts,
such as molybdic oxide, can be determined by chemical analysis, whereas
there are no published methods for determining the concentration of
organic brightening agents or of the covering agents other than by
direct plating tests and comparing for brightness range or for degree
of brilliance. Optimum addition agent concentrations are usually dif-
ferent for still and for barrel plating. Some prepared addition agents
differ in composition, depending upon the specific application. When
the plating bath is in operation, the rate of depletion of addition agent
can readily be established in each instance and thereafter readily main-
tained on the basis of the weight of zinc deposited or number of
ampere-hours passed through the bath. The selection of addition agents
(and hence the particular process) depends in large part upon the
degree of brightness desired, whether or not bright dipping is feasible,
economy of operation, and various other factors.
Operation and Maintenance of Bright Zinc Plating Baths
In general, bright zinc coatings are obtained by depositing very pure
zinc from a cyanide bath of controlled composition at a cathode ef-
ficiency somewhat below 100%, giving either a smooth, bright surface
~r~Stewart and Urban, U. S. Pat. Reissue 19,328; DubpernelI, U. S. Pat. 1,868,052.
m See footnote 11.
e* See footnote 13.
CYANII~I,; Z I N C I'I,A'flNG I;ATIIS 419
directly from the bath (c,mlaining prnpcr additi,m agt:ms) or a smooth,

clark surface which c;m be bri~zhteucd by ,lipping for 5 to 30 seconds in
0.25 t~, ().5~S, 11itric acid ,,r acidiIh.d ]ly,ll~ogeu :u peroxide (0.25%
H2SO.t, 4'/~ tf.~O2).
An important point in the operation of bright zinc plating is the
necessity for adequate rinsing of work before and after plating and
after bright dipping, the final steps consisting of at least two cold water
rinses and one hot water rinse.
For operation in barrel plating, in which as much as 1 a m p . / L .
TABLE I I I
Effects of Addition Agents in Bri, lht Zinc Baths.
Coneelltration
Addition Agents Purpose or Effect
g./L. oz./gal.
1. Ammonium thiocyanate- 0.5-1.0 0.06-0.13 Improves brightness; in-

formaldehyde resin ~ creases tolerance of Cu,
Phenol-thiocyanate '-'~ Ni, Pb and Cd in bath.
Thiourea-formaldehyde
resin~
2. Methyl ethyl ketone 10 cc./L. 1.3 ft. oz./gal. Improves brightness.
(conditioned with
H~SO,) ~ ;
or not conditioned~ 25 cc./L. 3.3 ft. oz./gal.
3. Molybdic oxide and 2.5-7.5 0.33-1.0 Produces bright deposits di-
similar compounds~ rectly from bath.
4. Piperonal or other 3.0 0.4 Improves brightness, espe-
methylene dioxyphenyl cially with molybdenum, at
compound~ low current density.
5. Gelatin with certain 1.0 0.13 Improves rate of covering.
oxyheterocyclic
compounds~
6. Thiourea with metal 7.5 1.0 I Improves brightness.
brighteners 3~ I
(5 amp./gal.) may be passed, cooling coils must be used to provide

proper temperature 'control. Operation below 21 ~ C. (70 ~ F.) may
polarize the anodes excessively and prevent passage of current sufficient
for normal rates of production.
In the usual operation of bright zinc baths, approximately one part
by weight of sodium cyanide and one-third of caustic soda are con-
sumed for each three parts of zinc metal deposited. Organic addition
agents are added from time to time as determined by appearance of
deposits. The concentrations of inorgani'c metals, such as mercury,
aluminum and molybdenum, are readily determined by chemical analysis
and fresh quantities are added to the bath as required.
U. S. Pat. 2,101,580; 2,101,581 (Henricks) to Odyllte Corp.
U. S. Pat. 2,109,887 (Mattaeotti) to Hanson-Van Winkle-Munnlng Co.
U. S. Pat. 2,080,520 (Westbrook) to E. I. duPont de Nemours & Co.
U. N. Pat. 2,218,734; 2,233,500 (Westbrook) to E. I. duPont de Nemours & Co.
U. S. Pat. 2,196,588 (Hull) to E. I. duPont de Nemours & Co.
*~ S. Pat. 2,080,479 (Hoff); 2,080,483 ( H u l l ) ; 2,080,520 (Westbrook) to 1~. I. duPont de
Nemours & Co.
4,90 ~. o. t I U L I , A N D C. J . W E R N L U N D
The necessity for proper control of the ratio M of total sodium

cyanide to zinc metal should be emphasized and, once the proper rati~
is established for a given bath temperature range, it should be main-
tained rigorously at that value. Two general rules are:
1. A low M value gives a high current density range; increasing M
lowers the bright plate current density range and cathode efficiency,
giving more uniform deposits in re'cesses.
2. Increasing the temperature raises the current density range for
bright plating and also increases the cathode efficiency by about 2.7%
per degree Centigrade (1.5~ per degree F.) at current densities above
3.2 amp./dm. 2 (30 amp./sq, ft.).
Addition agents are quite indispensable in improving the luster of
zinc deposit; in extending the limits of bright current density range;
or in improving the covering power at low current densities, par-
ticularly for barrel plating. Traces of foreign metals have been found
to lower the rate of covering in barrel plating, and therefore these
traces must be eliminated for proper operation. A simple way to detect
certain metal impurities in the zinc plate is by a bright dip, which, for
example, dulls rather than brightens the zinc deposit if copper is pres-
ent, but not if small amounts of lead are present. Impurities such as
these, when present in the bath, are removed by zinc dust, by sodium
sulfide or by electrolysis.
In order to check the plating range of a cyanide zinc bath, a plating
test may be made, using a small volume of solution. Any additions
that may be indicated for the large volume of solution can be checked
on a small scale to verify its effect. Such tests have been described by
Hull a2 and by Pinner and Baker. aa These small-scale plating tests,
aside from visual observation of the deposits from the regular plating
tanks, offer the only practical means for determining concentrations
of the majority of organic addition agents in use in cyanide zinc baths
today, and for determining the amounts of these agents required for
restoring an inferior bath to its optimum operating condition.
The carbonate content of cyanide zinc baths is not critical and seldom
exceeds 30 g./L. (4 oz./gal.). However, if carbonate is present in ex-
cess of 75 g./L. (10 oz./gal.), it can be reduced to 60 g./L. (8 oz./gal.)
by cooling to - - 5 ~ C. (23 ~ F.), and decanting or filtering, or by pre-
cipitation with specially prepared gypsum, a4
Analytical Methods
Determination of Zinc in the Bath.
Reagents: Solution--contains exactly 33.0 g./L. K,Fe(CN)~.3H._,O
and 6 g./L. Na~SO~.
Indicator--saturated solution of uranium acetate.
1. Under a hood, to exactly 5 ml. of cyanide zinc solution in a 250 ml.
beaker, add 5 ml. 1:1 HNO3 and 5 ml. 1:1 H2SO4. Boil until
dense white fumes are liberated. Add about 1 g. of (NH4),.,SO4
and fume about 5 rain. more.
sl Hull, U. S. Pat. 2,154,451; OpIinger, U. S. Pat. 2,154,469.
~a Cony. Proz. Am. Electroplaters' Soc. (1939); U. S. Pat. 2,149,344.
Trans. Electrochern. Soc. 55, 315 (1929).
R. O. Hull, Cony. Proc. Am. E1ectroplaters' Soc. (1937); U. S. Pat. 2,164,924.
CYANIDE ZINC I,I,ATING BATIIS 421
2. Let cool and cautiously add 50 to 75 nal. distilled water, dissolving

precipitate completely.
3. Make ammoniacal (to litmus), add an excess of 5 ml. concd.
NH4OH, filter and wash precipitate with hot distilled water con-
taining 10 ml./L, concd. NH4OH.
4. Make filtrate neutral to litmus with HC1, and 5 ml. coned. HCt
in excess.
5. Add 15 g. NH4C1 and 25 ml. H2S saturated distilled water.
6. Heat to 80 to 85 ~ C. and bring volume to 300 ml.
7. Titrate with potassium ferrocyanide solution, nsing uranium acetate
on a spot plate as an outside indicator, to the first light red-brown
tinge.
Number of ml. of standard potassium ferrocyanide required -- 5
= ~z./gal. of zinc.
7'otal 5odium Cyanide.
Reagents: Solution--contains exactly 26.0 g./L. C.P. AgNO~ plus
12.5 ml./L. C.P. HNO3 solution.
Indicator--dry mixture of 95% NaHCO3 and 5% K2Cr~OT.
1. Dilute exactly 1 ml. of plating solution sample to about 150 ml.
2. Add 5 g. indicator and stir.
3. Titrate, stirring constantly, with silver nitrate solution to the first
permanent brick-red color.
Number of ml. of standard silver nitrate solution required equals
number of oz./gal, of total sodium cyanide.
Sodium Hydroxide (Caustic Soda).

Reagents: Solution--H~SO~ 0.940 N.
Indicator--LaMotte sulfo-orange solution.
1. To exactly 5 ml. of plating solution add 1 g. of NaCN, 10 ml. of
water, and 10 drops of indicator solution.
2. Titrate with the standard sulfuric acid solution to a color change
from orange to yellow, or titrate to a pH of 11.0, using the high
alkaline type glass electrode as described by Gray? 5
Nmnber of ml. of standard sulfuric acid required ~ number of
oz./gal, of caustic soda.
Sodium Carbonate.
Reagents: Solution--BaC12 10%.
Solution--HCl 0.710 N.
Indicator--Methyl orange solution.
1. Dilute exactly 5 ml. of plating solution to about 100 ml. with hot
distilled water, in a 500 rot. erlenmeyer flask.
2. Add 15 ml. barium chloride solution, heat to boiling and allow to
settle on the steam plate for 30 min. after closing the mouth of the
flask with a wad of cotton.
3. Filter through No. 30 Whatman, washing the flask and residue on
the paper with hot distilled water.
4. Return paper and precipitate to the flask, add 100 ml. hot distilled
water, three drops of methyl orange, and shake to pulp the paper.
e"'Cony. Proc. Am. Electroplaters' Soc. (1941).
422 ~. o. IIULL AND C. J-. WERNLUND
5. Titrate with standard hydrochloric acid to the first permanent color

change of methyl orange.
Number of ml. standard hydrochloric acid solution required =
oz./gal, of sodium carbonate.
Molybdenum.
Reagents: Solution--KMnO40.117 N.
Saturate solution of ferric alum 2 parts by
volume + phosphoric acid C.P. 85% 1 part
by volume.
Jones reductor--See Scott's Analysis, Vol. I, or Treadwell and Hall,
Vol. II, for description.
1. Under a hood, to exactly 5 ml. of zinc solution in a 250 ml. beaker,
add 5 ml. 1:1 HNOa and 5 ml. 1:1 H~SO4. Boil until dense
white fumes are liberated. Add about 1 g. of (NH4)2SO4 and fume
about 5 minutes more.
2. Let cool and cautiously add 50 to 75 ml. distilled water, dissolving
precipitate completely.
3. Make ammoniacal (to litmus), add an excess of 5 ml. concd.
NH4OH, filter and wash precipitate with hot distilled water con-
taining 10 ml./L, concd. NH4OH.
4. Make filtrate acid to litmus with H2SO4; add 2 to 3 ml. concd.
H~SO4 in excess. Pass slowly through Jones reductor into 15 ml.
ferric alum-phosphoric acid solution.
5. Wash reductor with 100 ml. 2.5% H2SO4 and titrate with potassium
permanganate solution to a permanent faint pink.
Number of ml. standard potassium permanganate solution -- 10 =
oz./gal, of molybdenum.
Mercury in Solution.
Reagents: S o l u t i o n - - K I 8.300 g . / L .
Indicator--KNO~ C.P.
Starch 1% (freshly prepared solution).
1. Under a hood, acidify exactly 50 ml. of plating solution in a 250
ml. beaker with HNOs, boil until all cyanides are removed. Cool.
2. Neutralize with NH4OH, then add 2 ml. concd. HNOs.
3. Cool to 20 ~ C., add a small crystal of KNO2.
4. Titrate with standard KI solution, using 1% starch solution Oll a
spot-plate as an outside indicator.
M1. standard potassium iodide solution required x 0.0134 -- oz./gal.
Hg.
V. ANODES
A wide variety of shapes and composition of the zinc anodes is used
in cyanide zinc plating, depending upon the type of bath and the kind
of operation. The two main types are the ball type and the customary
bar type anodes, cast from slab zinc or suitable alloys. Each of the
two shapes has several claimed advantages.
High purity zinc anodes such as Special tligh Grade or High Grade :~';
~ F o r analysis see Am. Soc. for Testing Materials Designation B6-37, ASTM Standards
1940, Part I, p. 680.
CYANIDE ZINC'. I'I,A'I'IN(2, B A T t l S 423
are recommended for the straight cyanide bath, since usually no addi-
tion agents are present and no provision is made for removing impurities
from the bath. However, alloy anodes may also be used for this bath
provided they contain no heavy metals that will deposit out with the zinc.
For the zinc-mercury process, either Intermediate or Prime Western
zinc alloyed with 0.5 to 1~'o mercury, as mentioned abovey may be used.
The bright zinc baths necessitate high purity zinc such as Special
ltigh Grade or High Grade anodes free from objectionable metals,
unless recourse is had to purification of the bath at frequent intervals
to remove these heavy metal impurities. If alloys are used in which
metals such as aluminum, calcium, or magnesium (which do not plate
out) are present, these do not influence the character of the zinc de-
posit adversely but, on the contrary, may be advantageous in improving
the corrosion characteristics of the anodes. Experience has shown that
control of zinc metal content in the bath is somewhat difficult and pre-
sents a problem in bright zinc plating, since variations in this bath
constituent influence the current density range and efficiency of bright
zinc baths. Zinc passes into solution both electrochemically and by
chemical attack, and hence it usually tends to accumulate in the bath to
an excessive degree. Aluminum, when present in zinc anodes, increases
the rate of anode corrosion, while mercury together with aluminumas
alloyed with the zinc tend to reduce the chemical attack and to improve
anode corrosion characteristics. Magnesium or calciuma9 alloyed with
zinc is effective in reducing anode efficiency to any predetermined value.
For this purpose, 0.18% magnesium is used in zinc anodes for still
plating and 0.05% magnesium for barrel plating to reduce the anode
efficiency to about 88% which is about equal to the average cathode
efficiency.
With other than specific alloy anodes, the zinc content of the bath
can be controlled, although with difficulty, by using from 25 3 to 50%
inert steel anodes together with pure zinc anodes. However, this scheme
results in a serious complication: The zinc and iron in the alkaline
solution produce an electrolytic or voltaic couple and consequent electro-
chemical corrosion of the zinc when the bath is idle. There is then a
rapid decrease in the zinc content of the bath when in regular operation,
due to the steel anodes. If zinc anodes do not corrode fast enough
under steady operating conditions, it is common practice to use a few
steel anodes, e.g., 5 to I0 N of the effective zinc anode surface, to
accelerate chemical attack.
VI. PREPARATION OF BASIS METALS
No special treatment of basis metal is necessary for plating cyanide

zinc. For steel, the usual alkaline cleaner and acid pickle are used, and
care must be exercised only to prevent overpickling. Zinc plating on
malleable or cast iron is not recommended.
87 See footnote 10.
** See footnote 11.
a~ See footnote 13.
424 R.o. t I U L L AND C. J . \ V E R N L U N D
vu. CESTS of" D>:posn's

The usual thicknesses of zinc deposits recommended are those
specified in "Tentative Specifications for Electrodeposited Coatings of
Zinc on Steel, ''4~ prepared jointly by the American Electroplaters'
Society, the National Bureau of Standards, and the American Society
for Testing Materials. Three types of coatings are specified as follows,
depending upon service and severity of exposure:
(a) Type O.S. minimum thickness 0.001 in. (25 t*) on significant
surfaces ;
(b) Type L.S. minimum thickness 0.0005 in. (13/*) on significant
surfaces ;
(c) Type R.S. minimum thickness 0.00015 in. (3.8 I*) on significant
surfaces.
"Significant surfaces" are those surfaces that are visible and subjected
to wear or corrosion, or both.
Other tests of the zinc plate, such as the Preece test and salt spray
test, are quite widely used but results of these tests give only an ap-
proximate idea of the corrosion resistance and expected life of zinc
coatings. The Farnsworth-Hocker 41 intermittent immersion test con-
sists of immersing the zinc plated article in an ammonium chloride
solution and then allowing to dry in air, then immersing again, etc., at
regular intervals. The test is not sufficiently rapid for shop control
purposes.
The Brenner magnetic test 4= is utilized for determining the thickness
of zinc over steel. The mechanical force required to separate a permanent
magnet from the surface is determined by a sensitive hair-spring attached
to a calibrated scale, and zinc or other non-magnetic metal thickness
is determined by reference to a suitable curve supplied with each
instrument.
The "dropping test" is widely used for determining thickness of zinc
plate. As originally proposed by S. G. Clarke, 4a a solution of iodine in
potassium iodide was used. This test was later modified by Hull and
Strausser, 44 who recommend a solution of 100 g./L. (13.3 oz./gal.)
ammonium nitrate and 55 ml./L. (7.3 ft. oz./gal.) of nitric acid C. P.,
sp. gr. 1.42. This solution is dropped at the rate of 100 __+ 10 drops
per minute on the zinc plated specimen until the basis metal appears.
The rate of stripping is 10 seconds for each 0.0001 inch (2.5/~). To
facilitate the detection of the end-point in the case of zinc plated steel,
the solution freshly prepared may also contain 3 g./L. (0.4 oz./gal.)
potassium ferricyanide which will give a characteristic blue color as
soon as the steel is exposed. A dropping solution for the same test was
more recently proposed by Brenner, 45 consisting of 200 g./L. (27
oz./gal.) chromic acid and 50 g./L. (6.7 oz./gal.) sulfuric acid which
~o Am. Soc. Testing Materials Designation A164-40-T, Revised June, 1940, Am. Soe. Testing
Materials Standards 1940, Supplement Part I, p. 300.
~. Trans. ]~lectrochem. Soc. 45, 281-293 (1924).
~aJ'. Research Natl. Bur. Standards 18, $6S (1937); 20, 357 (1938).
~J'. Electrodepositlon Tech. Soc. 8, No. 11 (1933).
u Monthly Rev. Am. Electroplaters' Soc. 22 (March, 1935).
J. Research Natl. Bur. Standards 23, 387 (1939).
CYANIDE ZINC PLATING BATIIS 425
is dropped at the rate of 100 • 5 drops per minute. The rate of strip-
ping depends upon the temperature, as follows:
Rate of Penetration in
Temperature 10 see.
21 ~ C. ( 7 0 ~ F.) 2.5~ (0.000098 in.)
28 ~ C. (82 ~ F.) 2.8~ (0.00011 in.)
35 ~ C. (95 ~ F.) 3.0~ (0.00012 in.)
VIII. PIIYSICAL CHARACTERISTICS OF DEPOSIT

Zinc electrodeposits from cyanide baths are somewhat less ductile
than from the sulfate bath. However, very ductile zinc deposits may be
produced from the warm, concentrated cyanide bath without addition
agents. Deposits from the cyanide bath appear to be dense and rela-
tively free from pores. Coarse-grained deposits, such as those from
straight acid zinc baths, are very rare from 'cyanide baths. Generally
speaking, electrodeposited zinc coatings whether plated from cyanide or
from acid sulfate baths are of excellent physical quality and are less
brittle than the hot dipped coatings that contain appreciable thicknesses
of zinc-iron alloy layers underneath the outer zinc coat.
Resumen del artlculo: "Bafios de Cianuro para el Cincado Electrolltico."

La aplicacidn principal del cincado es la proteccidn del acero contra
la eorrosidn. Las bafios moderno~ producen un depdsito relativamente
brillante, y tienen buen arrojo, pero el coste es mayor que de un bafio
Acido, la velocidad de deposicidn es menor, y no se puede planehear el
hierro colado.
Para los Anodos se alea el Zn con A1, Hg, o Ni para poder emplear
una densidad de corriente anddica elevada, y con Mg o Ca para dis-
minuir la eficieneia anddica al nivel de la eatddica. Se debe mantener
constante la razdn de la normalidad total de eianuro e hidrdxido sddicos
a la del ciamlro de cinc. H a y muchos agentes que mejoran el briilo
(Tabla I I I ) . Se describen las condiciones de operacidn y m&odos de
an,~lisis.
DISCUSSION
G. SOnF,R~Em;I~: 1 am very pleased to have been asked to discuss this excellen~
paper. My comments will be in the nature of minor additions and. here and there,
from a somewhat different viewpoint.
Our tests with aluminum-zinc anodes indicated that, while almninum assists in
producing smooth zinc castings, it has no effect on the amount of sludge %treed.
This depends entirely on the purity of the zinc and the anode current density em-
ployed, high current density making it possible for heavy metal impurities to dis-
solve in the bath.
While malleable iron ordinarily cannot be plated successfully, recesses not being
covered, one occasionally encounters a foundry which produces metal which can
be plated. A study of the size and distribution of the constituents of malleable
iron may explain this anomaly. Similar difficulties are encountered with shot-
blasted steel having a surface with high carbon content. A change in the heat-
treating cycle permitting some deearburization or the use of sand for blasting
often remedies the trouble.
~e Technical Director, Udylite Corp., Detroit, Mich.
426 DISCUSSION
The mercury-zinc type of bath must not be used for plating brass parts or steel
parts which come into contact with brass. The small amount of mercury present is
capable of causing season-cracking of the brass. Expensive and dangerous fail-
ures are on record. On the whole, this type of bath may be considered obsolete
in view of the bright zinc developments.
Our tests show that about 4 tools N a O H are necessary to keep 1 tool of the
Na2ZnO2 in aqueous solution. If this is true in the cyanide solution, a bath
containing 4.5 oz./gal. Zn (about 0.5 M ) would require 16 oz./gal. N a O H (3.0 M )
for 100% solution, and a bath containing 10 oz./gal. N a O H could hold only
about 63% of the zinc as zincate. The hydrolysis of NaCN may contribute to
the amount of N a O H present.
The parallelism of the N a O H content and the Zn content should be watched
in practice. Drag-in of pickling acid (and perhaps absorption of COs from the air)
lowers the N a O H content and makes additions necessary.
The statement that "for good anode corrosion, not less than 4 volts must be
maintained across the plating tank bus bars and an anode current density of
10 amp./sq, ft. should be used" may be misleading. T a n k voltage is a complex
factor and varies too much with the shape of the parts being plated, the anode-to-
cathode distance, contact resistances, etc., to be used for plating control. Similar
criticism may be leveled at the expression "ratio anode-to-cathode surface." It
is well to consider anode and cathode current densities separately.
The rust-protective value of the mercury-zinc deposit is very low if the mercury
content of the plate goes too high, something which has often happened in
practice.
In the zinc analysis we prefer to use diphenylbenzidine (1 g. in 100 ml. coned.
H~SO0 as an inside indicator instead of uranium acetate as an outside indicator.
The color change from blue to pale-yellowish green is satisfactory, especially if
one drop of 10 g./L. FeC13 is also added. W e do not use Na~SO3 or H~S and
have found no need for a correction factor with this method.
The standard AgNO3 titration with KI as indicator is satisfactory for deter-
mination of total sodium cyanide if N a O H is added to the sample to take up the
zinc.
In practice, the anode efficiency should be 5 to 10% higher than the cathode
efficiency in order that zinc salt additions be unnecessary to replace the zinc lost
by dragout.
The ferricyanide addition to the Hull & Strausser dropping test delays the
appearance of the end-point 1 to 5 seconds when the basis metal is steel, and
10 to 15 seconds when it is cast or malleable iron.
As pointed out in Lyon's paper on acid zinc plating, the Preece test is unsuitable
for any testing of zinc coatings.
R. O. HULL: As far as aluminum-zinc anodes are concerned, I have no infor-
mation to indicate that Mr. Soderberg is not perfectly correct in that aluminum
assists in producing smooth zinc coatings and has no effect on the amount of
sludge formed. Perhaps Messrs. Graham and Hogaboom can enlighten us on
the subject.
The second point made is the plating of malleable iron and cast iron. If, by
using sand-blasted cast iron, or by using cast iron which has been specially heat-
treated, we can consistently and satisfactorily zinc-plate from a cyanide hath.
we will have made another step forward.
Next is the observation, or perhaps difference in opinion, as to the presence of
zinc in a cyanide bath as sodium zincate or sodium zinc cyanide. All the data
we have point to the presence of a large percentage of zinc as sodium zincate in
the bright zinc bath. First, we know from experience that zinc does deposit from
sodium zincate at a very high current efficiency, and from zinc cyanide at a low
current efficiency. Since our customary production baths operate at high current
efficiency, we can assume, at least by analogy, that zinc is present chiefly as
sodium zincate.
I am glad Mr. Soderberg pointed out the hydrolysis of sodium cyanide to
form sodium hydroxide, because the hydrolysis of sodium cyanide to the extent
of 20 to 25% would account for the difference between the 63% that he mentioned
as sodium zincate, and the 75 or 80% that we have proposed.
CYANII,I,; ZI NC I'[,ATING IIATllS 427
Vhla]!y, ~c ha~c c~mducllvi~5 d;Ll;~ ,m zim' c~auhte baths. Without g,,mg inh,
details we can bri~fb" q~te that a zi,!c cyanide, plating bath has considerably less
eonductiviW than w,m!d be indicated hy a similar so!ution in which there is a high
concentration of frec sodimu hydroxide. Therefore we can assume that a great
deal of caustic soda is tied up in the sodium zincate complex, and little caustic soda
is free in the solution.
The next point Mr. Soderberg makes is the parallelism of the caustic soda
content and the zinc content, which does not call for discussion. His observations
on analytical procedures and improvement are well worth while.
The point made relative to anode efficiency (which should be 5 to 10%
higher than the cathode efficiency) is, perhaps, well taken, but we feel that we
accomplish the same result by the normal chemical solution of zinc when the
bath is standing idle. Therefore we attempt to have about the same anode effi-
ciencies as cathode efficiencies during the plating operation. Experience has
shown that the zinc metal content under normal plating conditions remains re-
markably constant.
As far as the dropping test is concerned, I expect to check Mr. Soderberg's
observations as to the delayed end-point in cases of additions of ferricyanide
indicator.
C. J. WERNLUND: Mr. Soderberg's suggestion concerning closer definition of
tank voltages is well taken. W e should have said, "Use 4 to 5 volts at the tank
bus bars, depending on the distance between the work and the anodes." A rela-
tively high tank voltage is essential in the "duozinc" process to insure uniform and
complete solution of the mercury in the anodes and to prevent mercury-spotting
of the plated work.
Mr. Soderberg's remarks concerning the possibility of season-cracking 9f
"duozine" plated brass should not be overlooked, but in practice this situation
has caused serious trouble only when inexperienced or careless operators added
excessive amounts of mercury salts to the solution at one time, with the result
that abnormally high percentages of mercury were thus secured in the coating,
which affected the brass base adversely.
G. B. HOGABOOM, SRY: Mr. Soderberg is correct in his statement that mercury-
zinc deposits on brass tend to cause season-cracking due to the absorption of some
of the mercury by the brass.
It is well known that aluminum added to zinc materially decreases its chemical
solubility. A. K. Graham and I have presented papers before this Society which
bear out that point. It is known that aluminum salts have been added to zinc
solutions to obtain a finer crystal structure of the deposit. A l u m i n u m is not added
to the anode to decrease the grain size or to refine the cathode crystals; it is
added to the anode to prevent a chemical attack of the anode when the current is
not flowing. The advantage of this is borne out by the fact that it is quite
possible to maintain constant pH and a fairly definite anode area by using a ball
anode (composed of zinc plus a little calcium or magnesium) in a spiral wire
cage in a cyanide zinc solution. If there is a protective film of calcium or
magnesium oxide on the zinc to prevent a rapid attack of the anode by the solu-
tion, then that film or blanket is going to increase in thickness as the anode is
dissolved, and will eventually almost completely insulate one zinc ball from an-
other. If the zinc balls are clean, free from insulating films, due to there being
no chemical attack by the solution, then it is quite possible to use ball anodes,
because each ball is in perfect contact with the other.
Dr. Lyons ~ says that the acid zinc solution was improved in 1910. The im-
provement was really made early in 1900.
A n acid zinc solution was developed by the U. S. Galvanizing Company, and
also by the H a n s o n - V a n Winkle Company, which solution was a subject of litiga-
tion. Dr. C. F. Burgess, a past president of this Society, who is here today, was
the expert for the Hanson-Van Winkle Company. The case was carried to the
Supreme Court, and the Hanson-Van Winkle Company was rendered a favorable
decision. T h a t solution contained an aluminum salt.
R. O. HULL: I should like to correct Mr. Hogaboom in one respect--we do not
add magnesium to the zinc anode to prevent chemical attack by the plating solu-
~7Research Engineer, Hanson-Van Winkle-Munning Co., Matawan, N. J.
,t'~See page 389.
428 DISCUSSION
tion. And, as far as we know. magncsimn has no intluence on chemical attack.

It has an influence only on the relative rate at which zinc goes into solution upnn
passage of the current. Observation shows that the anode efficiency is about
85 to 88% when 0.187,, magnesium is added to high-purity zinc. Aluminum is
similarly effective, but to a far lesser extent. Mercury in the anode, however, pre-
vents solution attack. I believe mercury has little influence upon reduction of
anode efficiency.
COLIN G. FiNK~": Mr. Soderberg brought up this matter of cast iron. There
is no trick in plating cast iron if you remember that the material you have to re-
move from the surface is graphite and slag. Many cast irons today are prac-
tically free from graphite and slag. If you remove graphite and slag out of the
surface (and there are various ways of doing it), you will have no trouble in
getting good adherence. Many of the men here I know will agree with me.
R. O. HULL: I agree with you. With certain types of cast iron there is no
difficulty in plating with cyanide zinc, but with other types of cast iron a most
difficult situation arises in plating with zinc, no matter what the preliminary treat-
ment has been.
COLIN G. FINK: The more you pickle ordinary cast iron, the worse the ad-
hesion. Slag and graphite are not removed in pickling.
C. B. F. YOONGS~ Hydrogen embrittlement has not been mentioned in regard
to acid and cyanide baths. I think it has been said that acid zinc produces less
hydrogen embrittlement than does the ordinary cyanide zinc, and the latter pro-
duces less hydrogen embrittlement than the bright zinc solutions. A m I correct in
this, Mr. Hull?
R. O. HULL : I would not say that bright zinc shows more hydrogen embrittle-
ment than dull zinc.
49Head, Division of Electrochemistry, Columbia University, New York City.
r~ Electrometallurgist, P. O. Box 292, Flushing, N. Y.

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A paper 2resented at the Eightieth General

Meeting, held at Chicago, II1., October 3,

CYANIDE ZINC PLATING BATHS t

By R. O. HUt.L2 AND C. J. WERNLUNI~

a zinc sulfate solution containing enough potassium cyanide to redis-

brightening and rapid-covering agents. Maintenance of tile bright type

and is roughly proportional to the zinc metal content as it may change

IV. P L A T I N G BATH FORMULAS, OPERATING CONDITIONS

1. d'yanide Bath withoul .,ldditio, .4d~'uls.

The solution composition should be maintained within • 10%, and

As in the lower speed bath, composition (la), constituents should

2. Zinc Mercury Process.

Zinc cyanide, Zn(CN) . . . . . 37.5 5 60 8

observe so as to ensure efficient anode performance is to avoid low anode

Approx. Bright Plate Current Density Range Cathode Efficiency at 35

2.25 4-10 37-93 92%

2.6 27.8-30.6 82-87

second desirable effect of a bright dip after plating is to improve

g. / L. oz./gal. g./L. oz./gal.

Zinc cyanide, Zn(CN) . . . . . . . . . . . 60-82 8.0-11 60-82 8.0-11

Cathode current density . . . . . 0.2-10.7 anap./dm. 2 (2-100 amp./sq, ft.)

directly from the bath (c,mlaining prnpcr additi,m agt:ms) or a smooth,

1. Ammonium thiocyanate- 0.5-1.0 0.06-0.13 Improves brightness; in-

(5 amp./gal.) may be passed, cooling coils must be used to provide

The necessity for proper control of the ratio M of total sodium

2. Let cool and cautiously add 50 to 75 nal. distilled water, dissolving

Sodium Hydroxide (Caustic Soda).

5. Titrate with standard hydrochloric acid to the first permanent color

No special treatment of basis metal is necessary for plating cyanide

vu. CESTS of" D>:posn's

VIII. PIIYSICAL CHARACTERISTICS OF DEPOSIT

Resumen del artlculo: "Bafios de Cianuro para el Cincado Electrolltico."

tion. And, as far as we know. magncsimn has no intluence on chemical attack.

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