GALVANIZING NOTES

PROCESS AND DESIGN NOTES ON HOT-DIP GALVANIZING

American Galvanizers Association (720) 554-0900 FAX: (720) 554-0909 email:technical@galvanizeit.org

SKIMMINGS AND DROSS

BY JOHN KRZYWICKI AND THOMAS LANGILL, PHD
Figure 1: Skimming inclusions on a galvanized sur-
INTRODUCTION face.
Galvanizing residues, skimmings and dross, are costly
by-products formed in the kettle. The molten zinc in
the kettle reacts with air and with impurities/chemicals
that are transported into the kettle from earlier stages of
the process. Skimmings float on the top of the kettle,
dross sinks to the bottom. Residues, or by-products, of
the process are of importance because they are of sig-
nificant tonnage and they contain high levels of zinc
that would otherwise be used to coat products.

Skimmings are a solid product of zinc oxides and zinc

chlorides. A portion of the skimmings are formed Generally dross particles form and settle to the bottom
from the reaction between the flux coating on the work of the kettle resulting in dross build-up, which requires
and the molten zinc during the immersion and cook- frequent removal. Small dross particles can become
ing off stages of galvanizing. Most of the skimmings, incorporated into the coating. This usually occurs
however, are formed from reactions between the when bottom dross is stirred up. The affected product
molten zinc and air. An idle kettle forms a thin coating is often described by consumers as looking like it has
of skimmings immediately. This layer does not deep- been rolled in sand (Figure 2). Under the right set of
en appreciably unless the kettle surface is disturbed. circumstances, floating dross can occur. This can be
Skimming of the kettle either before or after immersion a major problem because it is found at various heights
exposes new pure molten zinc to the air. More skim- within the zinc bath and can stick onto the coating
mings are immediately formed. The immersion of the
work and any boiling/bubbling action exposes more
Figure 2: Dross protrusions on a galvanized surface.
molten zinc to the air with the subsequent formation of
more skimmings. Skimmings formed below the kettle
surface float to the top and may become entrapped on
the work (generally the skimmings are on top of the
coating and may be brushed off, see Figure 1).
Skimmings account for approximately 14% of the total
zinc used. Skimmings are commonly referred to as
ash by the galvanizing industry, but for the content
of this paper it will be referred to as skimmings.

Dross is the product of multiple reactions between iron

and zinc. Most of the dross is formed during immer-
sion when iron in the flux layer reacts with the zinc.

Serving The Galvanizing Industry Since 1935

Volume 5, Number 1 April 2001
during withdrawal. It should be noted that dross parti-
cles do not affect overall corrosion protection but can FORMATION OF SKIMMINGS
be aesthetically unpleasing. Dross accounts for
approximately 15% of the zinc used. Zinc skimming formation is the result of metal oxida-
tion that takes place at the temperature of the zinc melt
Over 25% of the zinc used in the kettle is converted to when zinc metal is exposed to the atmosphere. Since
dross and skimmings. Therefore, special care must be zinc's natural form, or lowest energy state, is an oxide,
taken in order to limit the formation of these by-prod- a layer of zinc oxide forms on the surface of the molten
ucts. The formation of dross and skimmings is zinc. Every time an article is withdrawn from the ket-
inevitable and the recovery of the residue is essential in tle this layer of zinc oxide is removed from the bath
order to acquire the large amounts of zinc they contain. surface, thus exposing more molten zinc to the atmos-
phere. This new layer of zinc reacts with the oxygen
SKIMMINGS and any metal chlorides on the bath surface to form
skimmings.
Zinc skimmings are mostly a mixture of zinc oxides
and free metallic zinc. The chemical composition of Increasing contact of molten zinc with the atmosphere
skimmings varies within the following ranges1: results in increasing skimming formation. Therefore it
is apparent that skimming formation is more prevalent
Zinc Oxides 60.0-85.0% in dry galvanizing processes where there is no flux
Chlorides 2.0-12.0% blanket on the surface of the zinc. In wet galvanizing
Lead 0.3-2.5% processes, a 2"-3" flux cover floats on the surface and
Iron 0.2-1.5% limits the contact time of the molten zinc to the atmos-
Aluminum 0.0-0.3% phere. Disturbances of the bath surface increase the
amount of molten zinc exposed to the atmosphere, thus
Zinc skimmings may also contain trace amounts of increasing the amount of skimmings formed. The sur-
nickel and bismuth, depending on the bath composi- face to volume ratio of the article to be galvanized has
tion. The zinc in the skimmings is most obviously a been found to be the dominating factor in skimming
result of the molten zinc present in the kettle. The formation, if the other reacting constituents are avail-
metallic zinc component of skimmings can vary able. Other factors that increase the formation of skim-
depending on how much bath metal is entrapped dur- mings include temperature, zinc purity, and the supply
ing formation. The flux, whether it be applied in the of reacting materials. The oxidation of zinc increases
wet or dry process, contains chlorides in the form of proportionally to increasing kettle temperature. High
ammonium and zinc which are also found in the skim- grades of zinc form oxides according to the formula g
mings. According to Cephanecigil2, 70 -90 % of the = k*t1/2 where g is the weight of oxide formed, k is a
flux ends up in the zinc skimmings. The iron in the
constant that increases with temperature, and t is time4.
kettle walls and the steel to be galvanized are the
This equation shows how temperature and time
sources of iron in the zinc bath. Lead added to the ket-
increase the formation of zinc oxides, or skimmings.
tle, to increase work drainage and to facilitate dross
Oxidation also increases with increasingly pure zinc.
settling, is also present in the skimmings waste.
Since the skimmings are not solely composed of zinc,
but also other metals and chemicals mentioned above,
Zinc skimmings are silver to dark gray solids, even at
the supply of these chemicals also affects the formation
galvanizing temperatures (450-480 C). At these tem-
of skimmings.
peratures, the skimmings are pasty due to the network
of zinc/iron alloy spike crystals that entrain a large vol- Skimmings are also produced from the entrainment of
ume of molten zinc. Some other physical characteris- flux by the zinc. Upon the initial immersion of the
tics of zinc skimmings that may be of interest include steel article in the molten zinc, the zinc immediately
a bulk density of 1.2 to 2.2 t/m3 and a grain size that is solidifies on the surface of the steel entrapping the
usually less than 0.75mm3. adhering flux. During the boiling off stages, the
solidified zinc layer remelts and releases entrapped
flux globules that float to the surface and form skim-
American Galvanizers Association 2
Volume 5, Number 1 April 2001
mings5. mation during off times is to reduce the heat of the ket-
tle or use a kettle cover. Utilizing a cover will limit the
CONTROLLING THE FORMATION OF SKIMMINGS molten zinc surface exposure to the atmosphere, limit-
ing the oxidation of the zinc. Kettle temperature must
Bath disturbance is the controlling factor in the amount be monitored more closely when covered because of
of skimmings formed. It is essential to avoid any the significant reduction in heat losses at the zinc melt
unnecessary disturbance to the surface of the zinc melt. surface.
This applies particularly to skimming6. Broad, steady
sweeps of the skimmer should be employed while Monitoring and controlling the flux parameters can
avoiding paddling motions that break up the surface of limit the formation of skimmings. Using a flux with
the zinc. A skimming blade with low heat conductivi- the lowest possible concentration without affecting the
ty (to avoid cooling of the zinc) that is light and easy to activity is desirable. Excess amounts of flux carried
handle is preferred. These blades can be in the form of over to the kettle increases the amount of reaction con-
a long, thin steel sheet or wood. Small-headed skim- stituents available for forming skimmings. Limiting
mers are suggested for the use of skimming in confined the iron content of the flux is also of major concern.
spaces such as corners. Perforated shallow ladles are The iron content of the flux should be kept at levels
recommended for the removal of skimmings, because below 0.5% to prevent excess carry over into the zinc
they limit the amount of zinc removed with the skim- bath. Maintaining the pH of the flux between 4 and 5
mings. Special care must be used in the actual dipping is recommended7.
of the steel. The work must be immersed and with-
drawn as slowly and steadily as possible to avoid any ZINC RECOVERY FROM SKIMMINGS
unnecessary surface disturbance. The dryness of the
work being immersed into the molten zinc has a large Skimmings recovery is essential to maintaining an effi-
part to play in disturbing the surface. If the surface is cient galvanizing process. Skimmings contains as
wet, the water is flashed to steam upon immersion and much as 85% zinc oxide and accounts for 14% of the
causes additional surface disturbance. Care must also total zinc consumed in the process.
be taken to vent holes in certain articles to be galva-
nized. Drain-holes should be immersed first into the Most of the zinc in skimmings is removed by skim-
ming the surface of the zinc bath, thus moving all of
molten zinc so that upon withdrawal, dripping zinc
the skimmings to one end and then removing it from
running off the part does not cause any undue bath dis-
the surface. Care must be taken so that 'good zinc' is
turbance. Venting in accordance with ASTM A 385
not removed from the kettle. Methods for skimming
will reduce the disturbance of the bath.
treatment to reclaim entrapped bath metal include:
Operating the kettle at the lowest operating tempera- sweating, liquation, cylinder method, static crucible
method, and rotary crucible method. If the current
ture suitable for galvanizing will also limit the amount
method that is in use at your plant is satisfactory,
of skimmings formed. As discussed earlier, the oxida-
change would not be suggested. Another factor that
tion of zinc and thus the formation of skimmings are
affects the recovery of zinc is the storage time of the
increased with increasing bath temperature. During
skimmings that you treat. For the highest yields in zinc
stand-by periods or off-operation time, oxidation of the recovery it is important to treat the skimmings as soon
molten zinc may occur. In wet galvanizing, the molten as possible, as changes to the skimmings occur over
zinc surface is covered by a flux blanket that limits the time, reducing the amount of recoverable zinc.
oxidation. When utilizing dry galvanizing, the surface
is continually exposed to the atmosphere leading to an The recovered zinc skimmings from your process can
increase in skimming formation. Adding small either be sold to a zinc-recycling firm or the zinc may
amounts (2.5 g/ton of zinc6) of aluminum to the zinc be recycled on site, as is done in a few plants.
bath can alleviate this. The addition of aluminum However, there are several advantages and disadvan-
forms a protective aluminum oxide film on the surface tages to recycling the skimmings on-site. One advan-
of the zinc. Other ways to reduce the skimming for- tage is very good recovery of zinc due to the short stor-
American Galvanizers Association 3
Volume 5, Number 1
age time of the skimmings. As much as 70% of the
skimmings can be converted to ingot zinc with the
other 30% converted to powdered zinc oxide, which
has good market value. A zinc recycling process also
requires little floor space (100 m2) and low operational
and treatment costs. As an example, one process
shows that the recovery process can be operated by
one person and has a short amount of payback time on
the initial investment8. The calculated payback period
for this process is as low as 6 months for the treatment
of 15 tons/month. Disadvantages to the on-site recov-
ery of zinc include the initial investment to build the
recycling unit and the fact that the skimmings can be
sold to a recycling firm without having to deal with
time and labor associated with on-site recycling.
DROSS
Dross formation is another major source of zinc loss in
the galvanizing process. It can exist as 'bottom dross'
or the more troublesome 'floating dross.' Dross parti-
cles usually form and settle to the bottom. Factors
such as the temperature gradient of the bath influence
FIGURE 4: Illustrative Diagram of Dross Formation9.
American Galvanizers Association
April 2001
the formation of floating dross, which can be present at
various heights in the zinc bath. Dross is the combina-
tion of zinc/iron intermetallic alloys and free zinc. It
can contain more than 94% zinc, depending on
process conditions. Therefore, controlling the amount
of dross is extremely important to the financial stabili-
ty of the galvanizing industry.
FORMATION OF DROSS
Dross is formed from three distinct sources9 (Figure
4):
Iron salts formed by a reaction between pick-
ling agents and steel (pickle salts)
Iron salts formed by a reaction between flux
and steel
Zinc/iron alloys formed by a direct reaction
between steel and molten zinc
Iron salts are formed in the pickling stage of the
process. The acid in the pickling tank combines with
the iron and iron oxide, forming iron salts that adhere
to the steel surface. These salts can then be transferred
to later stages in the process if the steel is not properly
4
Volume 5, Number 1 April 2001
rinsed. These salts will accumulate in later stages of FLOATING DROSS
the process (flux tank) and eventually end up being
carried into the kettle. Iron salts are also formed by a Floating dross consists of long intermetallic spikes that
reaction between flux and steel. Fluxing agents such are usually interwoven together in clumps as shown in
as ammonium chloride and zinc chloride readily form Figure 5. The size and shape of the particles suggests
iron salts. When the iron salts come in contact with the that they are formed across a temperature gradient.
zinc they quickly form dross. The hollow-like structure of the dross particles may
explain why they tend to float in the zinc bath. Dross
Dross is also formed by a direct reaction between steel that floats poses the same problem that skimmings do.
and molten zinc. When steel is submerged in the zinc, When articles are being withdrawn from the bath, the
a reaction between the molten zinc and any loose iron floating dross may adhere to the surface, causing unde-
particles occurs, forming zinc-iron alloy particles. sirable coating defects called 'dross pimples.' The
During dipping, the temperature of the molten zinc ASTM Specification recognizes these dross inclu-
drops a few degrees and decreases the solubility of iron sions. ASTM A 123 stating:
in the bath. Iron precipitates out of the molten zinc, "Galvanized articles shall be free from un-
and is available to react with the zinc. The same reac- coated area, blisters, flux deposits, and gross
tion between the steel kettle wall and the molten zinc dross inclusions."
Although rejections from dross inclusions are rarely
also occurs. When filling a new kettle, the kettle
enforced, customers generally dislike galvanized prod-
quickly develops an inner lining of protective zinc/iron
ucts with excessive dross inclusions.
alloy layers, which in time limits further reaction
between molten zinc and the wall. At kettle tempera-
Floating dross particles are mainly caused by tempera-
tures above 480 C, the protective alloy layers break ture gradients that allow cooler (upper) regions of the
down thus allowing further zinc/iron reaction at a rapid zinc bath to precipitate iron. As the iron precipitates
rate. Zinc reacting with the kettle wall at normal gal- out of the solution it reacts with molten zinc forming
vanizing temperatures makes a relatively small contri- dross particles. The thermal gradient of the bath often
butions to the overall production of dross but it could occurs during 'low burn' or off operational hours (holi-
be significant if the bath temperature stays high. A days, weekends, etc.). When the bath is undisturbed
hole in the wall of the kettle could also develop in a during off hours, the upper surface of the zinc is
short period of time. cooler than during operational hours. Dross crystals
that form on the cooler upper kettle wall and at the zinc
The composition of the steel has significant effects on bath surface can grow quite large.
the formation of the intermetallic Zn-Fe alloy layers.
In general, the gamma and delta layers that form are There are only a few ways that the floating dross prob-
the most compact, and tightly adhere to the surface of lem may be solved. Bubbling nitrogen gas into the
the steel. The zeta layer, which is formed after the zinc bath may reduce the amount of floating dross.
gamma and delta layers, is not as compact and has the Oddly enough, potatoes have been found to reduce the
tendency to float away into the zinc. For cold rolled amount of floating dross present in the bath. Potatoes
steels the delta layer is well formed and thus the zeta are immersed in the bath and upon boiling release
layer is more compact and few crystals float away steam and nitrogen. If potatoes seem like an unlikely
forming small amounts of dross. In the case of silicon solution, the best method of reducing floating dross
killed steels, the delta layer is not well formed and the may be to wait and let the particles settle to the bottom
and form bottom dross or to find the source of floating
zeta layer grows rapidly, and is not as compact as zeta
dross and correct it.
layers found in cold rolled steel. Many zeta crystals
are formed by reactive steels and float away into the
zinc forming dross. Therefore the galvanizing of reac-
tive steels can increase the amount of dross formed5.

American Galvanizers Association 5

Volume 5, Number 1 April 2001

FIGURE 5: Micropicture of Floating Dross.

Agitation in the fluxing stage of the dry process
CONTROLLING THE FORMATION OF DROSS reduces dross by converting the dissolved iron to
sludge. When the iron concentration of the flux bath is
The formation of dross is largely dependent on process above 2 g/L, the iron salts precipitate. This can be
conditions. Temperature not only has adverse affects achieved by heating the solution to a very high tem-
on the formation of skimmings but on dross as well. perature and precipitating the iron with the addition of
Increasing kettle bath temperatures leads to the aqua ammonia until a pH value of below 5.0 is
increase in dross formation. This is especially appar- reached. About 90% of the iron contained in the solu-
ent in the temperature range from 430-470 C, where tion is precipitated in this manner as sludge4.
dross formation increases dramatically. As shown by
Figure 6 this forty-degree increase causes a four-fold Adequate rinsing between stages (especially between
increase in the amount of dross formed from the direct pickling and fluxing) can dramatically reduce the
zinc/steel reaction. This figure also shows a more sub- amount of dross formed. A double rinse may be
stantial increase in the flux/steel reaction for the wet imposed between the pickling and the flux bath to
galvanizing process. ensure that only a small amount of iron salts are carried
into the kettle. Frequent inspection of iron salt build-
It is recommended to use an inhibitor in the pickling up in the pickling and fluxing stage of the process is
process, which may reduce the amount of dross required to reduce contamination of the kettle.
formed. The acids used in the pickling stages (sulfuric
acid and hydrochloric acid) may attack the iron and The chemistry of the molten bath also has significant
iron oxide, forming numerous iron salts. An inhibitor effects on the formation of dross. Small additions of
may be used to limit the attack of the acid on the steel lead (1%) at 450 C with a five minute immersion time
while not sacrificing the dissolving action of the acid have shown to reduce the dross formation from 1/2
on the iron oxide and/or mill scale. This may limit the oz./sq. ft. surface galvanized to 1/3 oz./sq. ft. surface
contamination of later process stages, which will galvanized9. The presence of lead also decreases the
reduce the formation of dross. coating weight by allowing the zinc to flow freely from
the steel as it is being removed. Lead has also shown
American Galvanizers Association 6
Volume 5, Number 1 April 2001

FIGURE 6: Amount of Iron Removed vs. Temperature For Different Reaction Types.9
to help settle the dross particles to the bottom of the aged and could increase the amount of dross formed.
kettle. The addition of nickel to the kettle bath is
sometimes necessary to suppress the reactivity of Dross formation is greater in wet galvanizing than in
steels containing silicon and to also improve surface dry galvanizing. The flux/steel reaction is much more
appearance of the zinc coating. Another advantage to prominent when utilizing wet galvanizing as previous-
nickel additions is that the formation of floating dross ly shown by Figure 6. Larger concentrations of iron
remain present in the wet flux because the purpose of
is rarely observed10. However, nickel also decreases
the flux is to remove any iron oxides that may have
the solubility of iron and may tend to increase the
formed on the steel before the part is brought to the
amount of bottom dross. If aluminum is added to the
galvanizing kettle. The iron removed by the wet flux
bath to reduce surface oxidation of the zinc, the pres-
ence of nickel will negate the effectiveness of the alu- FIGURE 7: Iron solubility curve5.
minum.

The iron content of the zinc bath can have significant

effects on the amount of dross produced as well as
skimmings. It is desirable to keep the iron content of
the bath at approximately 0.1%. Monitoring the flux
bath and maintain levels of iron less than 0.5% should
be adequate in reducing the amount of iron carry over.

The solubility of iron increases exponentially with

increasing temperature as shown in Figure 7.
Increasing the galvanizing temperature from 440 C to
480 C doubles the solubility of iron. More iron thus
dissolves from the steel into the zinc melt. Upon
reducing the temperature of the bath back down to 440
C, will cause the excess iron to fall back out of solution
and become readily available for reaction with zinc to
form dross. Large temperature changes are discour-

American Galvanizers Association 7

Volume 5, Number 1 April 2001
is larger regardless of temperature thus increasing the intended as a representation or warranty on the part of
formation of dross particles in this type of galvanizing. the AGA. Anyone making use of this information
assumes all liability arising from such use.
TECHNIQUES FOR BOTTOM DROSS REMOVAL
REFERENCES
The build-up of bottom dross must be moni-
tored closely. A build-up of dross may cause 'hot spots' (1) Agrawal, B. C. Ash and Flux Skimmings.
in the kettle wall due to the lower rate of heat transfer Indian Hot-Dip Galvanizers Association. Presented
through the layer of dross. The level of the dross can during Zinc Wastes and Their Utilization Seminar.
be checked by immersing a rod in the kettle while tak- September 1965.
ing note of the surface level of the dross and the actu-
al depth of the kettle. The level of build-up required (2) Cephanecigal, C. Investigations for Reducing
for removal is mainly dependent on kettle depth. Environmental Pollution in Hot Dip Galvanizing of
When the dross is at a level that may hinder the galva- Steel Components. Thesis, Technical University,
nizing process, it must be removed. The hardness of Berlin. 1983.
the dross may also affect the removal. If dross has
become hard, it must first be broken up using mechan- (3) Schultz, W. D. Reducing Ash Formation During
ical means. Once the dross is soft enough for removal Hot-Dip Galvanizing. Intergalva Edited Proceedings.
it can be scraped to one side and scooped out. Other 1991.
methods of removal may include bailing the kettle
completely or pumping out the dross (rare, but dross (4) Bablik, Heinz. Galvanizing (Hot-Dip). 3rd
pumps are available). Special care must be taken not edition. E.&F.N. Spon Ltd, London, England. 1950.
to contaminate or remove too much 'good zinc' from
the bath. (5) Sjoukes, F. The Role of Iron in the Hot Dip
Galvanizing Process. Intergalva Edited Proceedings.
SUMMARY 1976.

Solid residues that are formed during the galvanizing
process contain large amounts of free zinc. The main
by-products, skimmings and dross, can consume 14
and 15% of zinc, respectively. These residues can
cause undesirable coatings on the steel that can hinder
appearance and corrosion protection. Recycling of
these wastes provides a means to recover the lost zinc
and make the galvanizing industry more efficient. The
formation of these residues are unavoidable, but efforts
to control the formation must be made to ensure an
efficient and profitable operation.
(6) General Galvanizing Practices. Galvanizers
Association. London, England. 1979.
(7) Woods, Robert. Case Studies in Preflux
Purification. Presented at American Galvanizers
Association Technical Forum. 1999.
(8) Dominguez, A. In-Plant Treatment of Zinc
Ash. Edited Proceedings from the Thirteenth
International Galvanizing Conference. London,
England. 1982.

DISCLAIMER (9) Hiscock, S. A. The Sources and Control of

2001 American Galvanizers Association. The
material provided herein has been developed to pro-
vide accurate and authoritative information about
after-fabrication hot-dip galvanized steel. This mater-
ial provides general information only and is not
intended as a substitute for competent professional
examination and verification as to suitability and
applicability. The information provided herein is not
Dross Formation in Hot-Dip Galvanizing. British
Non-Ferrous Metals Research Association. 3rd
International Conference on Hot-Dip Galvanizing,
Oxford. p 169-200. July 1954.
(10) Reumont, G. & Perrot, P. Fundamental Study
of Lead Additions in Industrial Zinc Baths.
Intergalva Edited Proceedings. 1997.

American Galvanizers Association 8