ZINC ELECTROPLATING

Zinc Electroplating
CHOOSING THE BEST PROCESS FOR YOUR OPERATION

By Clifford Biddulph
Pavco Inc.

Zinc and its alloys have been used for over After fully evaluating how these factors
a hundred years as protective and decorative affect your circumstances and referring to
coatings over a variety of metal substrates, Table 1, the choice of the most applicable
primarily steel. Over the years there have process should be considerably narrowed
been a number of processes developed for down. The following sections present
applying zinc coatings depending on the more specific information for each of the
substrate, coating requirements and cost. Of different basic zinc plating processes.
these, electroplating is the most prevalent
for functional and decorative applications. ALKALINE CYANIDE ZINC PLATING
When choosing a zinc plating process, it is Cyanide zinc plating was for a long time
important to know what processes are avail- the workhorse of the industry. Its popularity
able and each of their particular advantages has significantly decreased over the years in
and disadvantages. Table 1 compares some the U.S. and other countries. The cyanide
of the more important factors related to processes are presented here because there
these processes. is still a fair amount of cyanide zinc plating
done in a number of countries and cyanide
FACTORS TO CONSIDER processes are still considered by many to be
Listed below, in order of importance, are the benchmark to which all other processes
the primary factors that must be considered are compared.
when choosing a zinc plating process: Operating requirements for a cyanide
n Does the plating specification for the zinc plating process are really minimal when
part require a zinc or a zinc alloy deposit? compared to the other zinc plating processes.
n Substrate(s) to be plated? Bath analysis, Hull cell testing, and other plat-
PLATING/ANODIZING

n Required corrosion protection? ing tests should be done on a weekly basis.

n Required deposit thickness uniformity? Cleaning and pickling requirements are not
very stringent but should be corrected if an
Considering these questions should some- obvious preparation problem exists.
what reduce the number of usable plating Bath makeup. Two options are available
processes. The next step is to consider the for bath makeup: Using caustic, sodium
secondary factors. These factors are listed cyanide and zinc oxide; or using caustic,
below in no particular order because their sodium cyanide and zinc cyanide. Option
importance will vary from shop to shop: A is labor-intensive, but material costs are
n Deposit characteristics (appearance, low. Caution must be exercised with this
ductility, adhesion, etc.) option as the reaction is highly exothermic
n Make-up and operating costs (more than 250°F).
n Operating factors (efficiency, pre-plate Option B has higher material costs, but
requirements, corrosivity, etc.) is less labor-intensive and faster.
n Environmental restrictions (air quality, Process steps. Soak alkaline cleaning
heavy metal removal, ammonia, etc.) followed by electro-cleaning is preferred to
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 PLATING/ANODIZING

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 ZINC ELECTROPLATING

  TABLE I— Attributes of Zinc Electroplating Processes

5 = Excellent Alkaline Zinc Acid Zinc

3 = Good
1 = Poor CN NCN CHLORIDE SO4

LC HC LC HC* NAm LAm Am

Substrate 1
2 3 3 4 5 5 5 4
Ecological Concerns2 2 1 5 5 5 4 4 5
Make-up Cost 5 3 5 4+ 3 4 4 3
Operating Cost3 3 2 4 4+ 3 3 3 3
Pre-Plate4 5 5 2 3 3 3 3 3
Soln. Corrosivity 4 4 4 4 3 2 2 1
Soln. Conductivity 2 3 2 3 4 4 4 3
Soln. Rinsability 2 2 4 3+ 3 3 3 3
Ease of Operation 4 5 4 3 3 3 4 4
Plating Speed 2 3 2 4 5 5 5 5
Throwing Power 4 4 3 5 3 3 3 2
Covering Power 2 2 3 3 4 4 5 3
Deposit Ductility 4 5 4 4 3 3 3 3
Deposit Adhesion 5 5 3 3 4 4 4 4
Appearance 3 3 3 4 5 5 5 2
Chromate Receptivity 5 5 4 5 4 4 4 4
Corrosion Protection 2 2 2 3 2 2 2 2
1) Ability to plate a wide variety of substrates i.e. hardened steels, cast iron or low carbon stampings
2) Toxicity, waste-treatability, etc.
3) Direct bath operating cost including waste treatment, not pre or post plating costs or equipment costs.
PLATING/ANODIZING

4) Bath's ability to tolerate or compensate for poor preparation.

*Sodium and potassium baths are available. Using a potassium based bath can affect the values shown below. The
superscript (+ or -) indicates the effect of using a potassium based bath over a sodium based bath.

avoid contamination of the plating bath. If line is preferred to avoid the introduction
parts are not completely cleaned, however, of chromium contamination and to extend
the plating bath itself will clean them so the life of the acid. Parts can, however be
cleaner maintenance is not quite as critical stripped on-line if necessary. Proprietary
as with other plating processes. Cleaning acid additives and/or fluoride salts may be
should be followed by pickling in hydro- beneficial in cleaning and activating parts,
chloric acid (20–30%) at room tempera- as well as increasing acid longevity.
ture or sulfuric acid (5–15%) at 105–120ºF Chromate and passivate coatings and
(40–50°C) to activate, descale, etc. steel parts lacquers are the usual post plate treatments
prior to plating. Stripping rejected parts off- for any zinc deposit. Chromate conversion

108 2011 PF DIRECTORY

coatings that can provide up to 500 hr to
white salt formation are available, as are
a wide variety of passivates in colors from
clear to black.
Equipment and operating parameters.
Tanks for zinc cyanide plating can be made
of either low-carbon steel, polypropylene,
PVC or rubber-lined steel. Low-carbon steel
tanks should be insulated from the electri-
cal circuit to avoid stray current. For barrel
plating, rectifiers operating at 6–15 V, 5–10
asf are recommended. Operating range for
rack operations is 3–9 V, 10–40 asf.
Most baths operate at a range of tem-
peratures, but cooling equipment is rec-
ommended and heating equipment may
be desirable in colder climates. Steel is the
material of choice for any equipment in
contact with the plating solution. Agitation
is optional for zinc rack operations. Zinc generation tank—overhead view.
Special high-grade zinc anodes are pre-
ferred, but lower grades have been used thus making the deposit less ductile and
with moderate success by some platers. If more stressed. Thus brighter parts may look
anode bags are used to avoid roughness be better but their performance in other areas
sure that the tops of the bags remain above may suffer. This observation is true for all of
the plating solution. the zinc plating systems.
Covering power, throwing power and bath
efficiency. Covering power is the ability of ALKALINE NON-CYANIDE ZINC
a plating bath to deposit metal in a deeply In early cyanide-free alkaline zinc plating
recessed area. Throwing power is the abil- systems, cyanide was replaced by complexing
ity of a plating bath to deposit a uniform or chelating agents such as sodium glucon-

PLATING/ANODIZING
thickness of metal on areas of high and low ate, triethanolamine, or polymeric amines.
current density. The throwing power of a The resulting baths presented problems with
cyanide bath is significantly better than that both waste treatment and co-deposition of
of a chloride zinc bath. Plating efficiency of iron. A second generation of organic addi-
cyanide zinc baths varies greatly depending tion agents eliminated chelating agents, but
on the bath chemistry, plating temperature had other drawbacks.
and the plating current. The efficiency can Most of the currently available processes
vary anywhere from 40–85%. have eliminated these problems with the
Deposit properties. Zinc deposit ductil- use of an entirely new family of organic
ity, uniformity, and chromate receptivity reaction products. Platers have a choice
from a cyanide zinc bath is better than that of low-chemistry alkaline non-cyanide zinc
achieved by chloride zinc baths and in some (low-metal bath) or high-chemistry alkaline
cases better than an alkaline non-cyanide non-cyanide (high-metal bath). In addition,
baths. The deposit exhibits no chipping or potassium-based baths have been introduced
star-dusting. The brighter the zinc deposit, that offer faster plating speeds and higher
the higher the organic level in the deposit, efficiencies.

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 ZINC ELECTROPLATING

Operating requirements for alkaline tanks are preferred but should be insulated
non-cyanide zinc plating processes are as from the electrical circuit. For barrel opera-
follows: tions, power of 6–15 V at density of 5–10 asf
n Perform bath analysis, Hull cell testing, is recommended; for rack operations, 3–9 V
and other plating tests daily. and 10–40 asf. Most baths operate at a broad
n Analyze, maintain and dump cleaners range of temperatures, but cooling equip-
and acids on a regular basis. ment is essential and heating equipment
n Perform preventive maintenance to may be needed in colder climates. Steel is
reduce production problems and mini- the material of choice for any equipment in
mize costs. contact with the plating solution.
n Install automatic feeders for liquid com- Filters are essential for an alkaline non-
ponents to eliminate human error. cyanide zinc process. One to two turnovers
n For troubleshooting, follow the supplier’s of the plating solution per hour are practical
recommendations carefully. in most installations using polypropylene
cartridges and 10–15 μm screens. Paper or
Bath makeup. Three options are available cellulose-type filter screens can be attacked
for bath makeup: using caustic and zinc by the alkalinity of the system and should
oxide; using ready-made zinc concentrate; be avoided. Use of a filtration system that
and using zinc anodes and caustic. Option can be carbon-packed is recommended.
A is labor-intensive. Material costs are mod- Mechanical agitation is optional for alkaline
erate. Caution must be exercised because zinc rack operations. Air agitation is not
the reaction is highly exothermic; however, generally recommended.
these high temperatures cannot be avoided Anodes are ideally made of low-carbon
because they are required to dissolve the zinc steel, perforated, and with a thickness of
oxide. Option B has higher material costs, 0.125–0.375 inch. Thicker steel has a higher
but is the least labor-intensive and the fastest. current carrying capacity than thinner steel.
Option C is the least expensive overall, but Titanium baskets are not recommended
requires a delay for zinc dissolution, as well due to their high resistivity. Make sure that
as possible low-current-density electrolysis to low-carbon steel baskets are filled appro-
remove unwanted metallic impurities. priately as per supplier’s suggestion when
Process steps. Cleaning and pickling as zinc anodes are used. Knife-edge anode
PLATING/ANODIZING

described above for alkaline cyanide zinc hooks make better contact than other
processes activates and prepares steel parts designs. Polypropylene material is recom-
for plating. After plating, chromate conver- mended for anode bags. Cotton bags will
sion coatings that can provide up to 1,000 be attacked by high alkalinity and dissolve
hrs to white salt formation per ASTM B 117 in the plating bath. Ensure that the tops of
are available and may provide a cost-effective the bags remain above the plating solution
alternative to alloy plating. A wide variety of to avoid roughness. Anode-to-cathode ratio
trivalent passivates ranging in colors from should be about 1:1; zinc metal consump-
clear to black are now available. These pas- tion is 2.7 lb/1,000 A/hr at 100% plating
sivates are normally used by themselves or efficiency.
with topcoats or sealers and provide from An off-line zinc generation tank that is
12 to 200+ hr of protection to white salt 10-20 % of the volume of the plating tank
corrosion. makes control of zinc concentration easy.
Equipment. The plating tank can be made The zinc generation tank is a low-carbon
of either low-carbon steel, polypropylene, steel tank with steel and zinc in contact.
PVC or rubber-lined steel. Low-carbon steel The zinc anodes are galvanically dissolved

110 2011 PF DIRECTORY

in the steel tank (low-carbon steel anodes iron and, more importantly, steels that
are recommended in the plating tank). New have been hardened using any number
technology is available that may reduce the of different methods.
size of or eliminate auxiliary tanks. Figure
1 shows an overview of the galvanic genera- Disadvantages. Unfortunately, associ-
tor setup. ated with these advantages are two major
Covering power, throwing power and disadvantages:
efficiency. The alkaline bath’s throwing n The solutions are corrosive, and therefore
power is approximately 40-65% (Haring more expensive, due to the need for
cell), depending on the bath chemistry and/ corrosion-resistant equipment.
or type of additives used. Nearly any part n Throwing power of the systems is only fair,
plated in an alkaline plating bath will have resulting in poor plate distribution.
thicker deposits in the low-current-density In some instances, one just has to live with
areas when compared to chloride zinc. these disadvantages or work around them in
The bath efficiency of alkaline non-cyanide order to make use of the advantages.
zinc decreases with current density. Higher The three most commonly used chloride
efficiency can be achieved with higher zinc zinc plating bath chemistries are shown in
concentrations and higher temperatures. Table II.
Deposit properties. Zinc deposit ductil- Operating requirements. Suggested
ity, uniformity, and chromate receptivity in requirements for trouble-free operation of
an alkaline non-cyanide bath is better than a chloride zinc plating operation include
that achieved by chloride zinc baths. Unlike monitoring and adjustment of pH as
chloride zinc, the alkaline bath does not frequently as possible, at least every two
exhibit chipping or star-dusting when oper- hours. The bath should be analyzed once
ated properly. The brighter the zinc deposit, per shift or at least once a day, and cleaners
the higher the occlusion of organics in the and acids must be analyzed, maintained,
deposit. This makes the deposit less ductile and dumped on a regular basis. Preventive
and highly stressed. maintenance can reduce production prob-
lems and minimize costs, while automatic
CHLORIDE ZINC PLATING feeders for liquid components eliminate
Chloride zinc plating processes have been human error and smooth out operating

PLATING/ANODIZING
available for more than 40 years and have performance.
changed considerably over this period. They Bath makeup. No matter which bath
have evolved from processes that were very chemistry is chosen, zinc chloride is the
sensitive to bath chemistry, temperature, source of the zinc in the bath and is available
current density, etc. to processes that can be as either a liquid or a solid. Zinc chloride is
operated over a wide range of conditions. normally only used for bath make-up unless
Over the last five or so years, however, there an unforeseen problem should occur. It is
have not been any really significant changes very important that the zinc chloride be
in the available systems. lead-free or as lead-free as possible; the
Advantages. The chloride processes presence of lead in the bath will result in a
offer three important advantages over the very dull, dark and unrefined deposit and
alkaline systems: requires “dummying” the bath to remove
n Superior brilliance and leveling, rivaling the lead.
that of nickel-chrome. Potassium chloride provides solution con-
n Plating efficiencies of 95–100%. ductivity. The untreated form of potassium
n Ability to plate substrates such as cast chloride is preferred. Ammonium chloride

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 ZINC ELECTROPLATING

serves a number of purposes: It provides much the same way as hydrogen peroxide.
conductivity, acts as a buffer and as a com- For rack operations, this material should
plexor for the zinc. Baths using ammonium only be added during down time.
chloride in general have a wider window of Process steps. Parts should be cleaned
operation and are therefore easier to control. and pickled using the steps outlined for the
Ammonium chloride-based baths also pose a alkaline zinc processes above. After plating,
potential waste treatment problem. If nickel chromate conversion coatings and lacquers
or copper waste steams are not segregated, are available in a wide variety of colors to
the ammonia could make removal of the provide white salt corrosion protection of
nickel or copper difficult. In some areas, the anywhere from 12 –500 hr. For additional
discharge of ammonia is also restricted. corrosion protection or lubricity control,
Other possible bath constituents include organic, inorganic or blended topcoats or
boric acid, used only in non-ammonia sealers are available.
systems to provide some buffering action; Equipment and operating parameters.
proprietary grain-refining and brightening Tanks for zinc chloride plating can be made
additives; hydrogen peroxide to treat the of polypropylene, PVC, fiberglass or lined
bath for iron and some contaminants; and steel. All should be leached before use. For
potassium permanganate, which is used in barrel operations, 4–12 V at density of 3–10

  TABLE II—Common Chloride Zinc Bath Chemistries

Chloride Zinc Bath Type All Potassium Low Ammonium All Ammonium
Zinc (oz/gal)/(g/L) 3–5 / 22.5–37.5 2.5–4.5 / 18.7–33.7 2.0–4.5 / 15–33.7
Ammonium Chloride (oz/gal)/(g/L)    4–8 / 30–60 18–22 / 135–165
Potassium Chloride (oz/gal)/(g/L)  25–30 / 187–225  16–20 / 120–150
Boric Acid (oz/gal)/(g/L) 3–5 / 22.5–37.5
Proprietary Additives As recommended As recommended As recommended
PLATING/ANODIZING

pH  4.5–5.2 5.5–6.0 5.5–6.0

Temperature, °F (°C) 70–130 (21–55) 80–140 (27–60) 85–140 (29–60)
Agitation Recommended Recommended Recommended
for rack for rack
Filtration Yes Yes Yes
Type of Operation Rack or barrel Rack or barrel Rack or barrel
Voltage (V) 2–13 2–12 2–12
Current Density, asf 1–25 1–30 1–35
Plating Efficiency, % 95–100 95–100 95–100
Plate Distribution Fair Fair Fair

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asf is recommended; for rack operations, is a lot of making and breaking of contact
3–9 V at 10–40 asf. Most baths operate over will exhibit chipping or star-dusting. High
a broad range of temperatures, but cooling brightener or organic levels can also make
is essential and heating equipment may be the deposit less receptive to chromates which
needed in colder climates. Any equipment will result in unacceptable appearance and
coming into contact with the plating solution poor corrosion performance.
must be constructed of corrosion-resistant
materials. ZINC ALLOY PLATING
Filters are also essential, operated at one Zinc alloy plating, not including brass, did
to two turnovers of plating solution per hour not receive meaningful recognition until the
using polypropylene cartridges with 10–25 early 1980s. Since then, the range of alloys has
μm filter screens. Some form of agitation in increased and the production processes have
required for rack operations. Special high- been refined considerably. However, it was
grade zinc anodes must be used, and titanium within the last ten years that these processes
baskets with slab or ball anodes can be used gained any commercial acceptance. This
as can slabs hung from hooks. Polypropyl- delay was the result of several factors:
ene or cotton material is recommended n No compelling need had developed
for anode bags; napped polypropylene is for the advantages offered by the alloy
preferred. The bag weave should not be deposits.
too tight since this could result in the bags n The processes were difficult to operate
plugging prematurely. Be sure that the tops consistently.
of the bags remain above the plating solution n The cost of operating the alloy baths was
to avoid roughness. At 100% efficiency, zinc too high.
metal consumption in a chloride zinc bath n No general consensus on which alloy
is 2.7 lbs/1,000 A/hr. was most suited for any specific applica-
Covering power, throwing power and effi- tion.
ciency. Chloride zinc deposits have excellent
covering power but poor throwing power. These factors were either overcome or
A chloride plating bath can plate deeper at least became acceptable because of two
into the inside of a tube than an alkaline developments in the automotive and elec-
non-cyanide bath. Deposit thickness distri- tronics industries. The first was the push

PLATING/ANODIZING
bution, however, is poorer. In past editions for an environmentally acceptable method
of this article, the deposit distribution was to obtain increased corrosion protection.
rated in the tables for chloride zinc as a 2 The second was the pursuit of an acceptable
out of 5 and called fair. New technology has replacement for cadmium deposits. The
allowed the chloride zinc systems to plate zinc alloy baths available today are capable
with much improved distribution, better of satisfying both of these needs, producing
conversion coating receptivity, and no star- deposits that provide enhanced corrosion
dusting, while maintaining all the deposit protection and increased lubricity, ductility
properties of chloride zinc, including its and hardness.
laminar deposition. Available processes. There are a number
Deposit properties. Chloride zinc deposits of commercially available zinc alloy pro-
from baths run under normal conditions cesses, including zinc/nickel (Zn/Ni),
are full bright with very good leveling and zinc/nickel/iron (Zn/Ni/Fe), zinc/cobalt
acceptable ductility, uniformity, and chro- (Zn/Co), zinc/cobalt/iron (Zn/Co/Fe),
mate receptivity. The deposits particularly zinc/iron (Zn/Fe), tin/zinc (Sn/Zn) and
from barrel plating processes or where there zinc/manganese (Zn/Mn). Of these, the

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 ZINC ELECTROPLATING

nickel, cobalt, tin and iron alloys are cur- New technology has developed chloride
rently the only ones of any real commercial zinc-nickel alloy systems that have alloy
prominence. The Zn/Mn alloys will not be distribution properties almost as uniform
presented here. Table III lists the different as alkaline zinc-nickel. The metal replen-
alloy compositions and their associated ishment of chloride zinc-nickel baths can
processes. be from one of four methods: 1)zinc and
The plating processes for the iron and nickel anode on the same anode bar; 2)inert
cobalt alloys are operated and have additive anodes with zinc generation and nickel salts;
systems similar to their non-alloy counter- 3)zinc anodes and nickel salts, and; 3)zinc
parts. The Zn/Ni systems, however, require and nickelanodes on separate rectifiers.
processes that are quite different from their Tin zinc is more of a tin alloy than a zinc
non-alloy counterparts. alloy, since the tin is present in the deposit at
Zinc/nickel alloy deposits can be pro- 70–75% while the zinc is present at 25–30%.
duced using either an alkaline or chloride While the tin-zinc alloy bath is plated in
process. Regardless of process, the zinc/ acidic as well as alkaline bath formulations,
nickel alloy is by far the most expensive to the most user-friendly are generally plated
operate of any of the alloys discussed here. at a near neutral pH range of 6.0–7.0. The
But, it provides the best corrosion protec- anodes used are usually 75/25 tin/zinc.
tion, maintains a majority of its corrosion Cathode agitation is mandatory, and "no-air"
protection at elevated temperatures and agitation is specified.
provides greater wear resistance. Zinc/cobalt. Alkaline systems for plating
The alkaline plating process gives good zinc/cobalt alloys are easy and economi-
plate distribution but has very low efficiency. cal to operate and produce a deposit with
The complexors used can adversely affect exceptional alloy and thickness uniformity.
waste treatment. It is because of these com- Like the alkaline nickel alloy process it is
plexors that a zinc/nickel/iron tri-alloy not unusual to actually plate a tri-alloy of
is the usual result. This co-deposition of zinc/cobalt/iron because of the presence
iron, however, seems to have no affect on of complexors. The alkaline plating process
deposit performance. The zinc and nickel is preferred, but the chloride system can be
are replenished using either zinc anodes or used where it is necessary to plate hardened
a galvanic zinc generator and nickel salts. or cast metal parts.
PLATING/ANODIZING

If a zinc generator is used, the anodes are Zinc/iron deposits are currently produced
nickel, but nickel salts are still normally using only an alkaline non-cyanide process;
required. chloride processes to produce Zn/Fe alloys

TABLE III—Zinc Alloy Processes

Alloy Type Alloy Composition Plating Processes

Zn/Ni 5–10% nickel (low) Alkaline non-cyanide or acid chloride

Zn/Ni 10–16% nickel (high) Alkaline non-cyanide or acid chloride

Zn/Co 0.2–1.2% Alkaline non-cyanide or acid chloride

Zn/Fe 0.2–1.2% Alkaline non-cyanide

Sn/Zn 70–80% tin Neutral non-cyanide

114 2011 PF DIRECTORY

are not yet widely used commercially. The coating, the corrosion characteristics of
Zn/Fe baths are the most economical and the iron and cobalt alloys are not sig-
easiest of the zinc alloy systems to oper- nificantly different than those of pure
ate. The deposit has very good corrosion zinc. In the case of nickel alloys, with no
resistance, ductility and weldability. Iron chromate or passivate, the onset of white
alloy deposits have only one real negative: salt corrosion is about the same as for
they lose substantial corrosion protection pure zinc but the progression of the cor-
when exposed to elevated temperatures. rosion is slowed depending on the nickel
Thus they are not recommended for use at content. n
temperatures greater than 200°F.
Choosing the right zinc alloy process.
There are only two choices to be made.
The first is the type of alloy required. The LEARNMORE
second, in the case of nickel and cobalt alloys,
is whether to use an alkaline or chloride Plating for Growth
plating bath. The first choice is easy, since This article provies the fundamentals on zinc plating
this is usually spelled out in the customer’s processes. Follow the link to learn how one zinc barrel
specifications. The choice of bath types can plating shop expanded by installing a rack line:
be a little more involved. There are several pfonline.com/articles/110401.html.
considerations:
n Some substrates, such as cast iron, hard-
ened or carbonitrided parts, require
chloride type baths to plate correctly.
n Chloride baths necessitate the use of
corrosion-resistant equipment. The
alkaline alloy baths contain complexors
of one kind or another that can also be
corrosive to equipment. Depending on
the alloy bath and the complexors used,
it may be necessary to use more corro-
sion resistant equipment than would

PLATING/ANODIZING
be required for a normal alkaline zinc
plating bath.
n In the case of nickel alloys, waste treat-
ment modifications may be needed to
handle nickel and (in alkaline baths)
high levels of strong complexors.

Topcoats and sealers. Because of the alloy

content of the deposit, special chromate
or passivate formulations are required
for each of the different alloy deposits.
There are currently both hexavalent and
trivalent chromates available in a range
of colors for most of the zinc alloys. With-
out a chromate or passivate conversion

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