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 Chatterjee: Hot Dip Galvanizing 1

Hot Dip Galvanizing

By Benu Chatterjee

Steel with high strength-weight ratio as well being reasonably cheaper than other exotic materials is frequently
chosen for engineering applications in areas such as building and automotive industries. However, the major
drawback of steel is its natural tendency to rust in humid atmosphere. The situation can be improved by pro-
tecting the steel surface with zinc coating which would act as a sacrificial anode to steel and physically
provide a barrier film to rust. Among the various zinc coating processes, hot dip galvanizing method provides
a very thick coating normally between 35 to 70 µm. The technique involves immersion of steel articles for about
4 to 5 minutes in a molten zinc bath maintained around 440 to 460 °C. In the present review, various aspects
of hot dip galvanizing are updated which include pre-treatment, process details, applications, metallurgical
characteristics and corrosion resistance of the coating, cost and effect of the operation on environment.

1 Introduction mance. Among the various zinc coating methods,

Steel has been a frequent choice of engineering mate- hot dip galvanizing provides a protective coating by
rials in today’s economy for various construction/ immersion of iron or steel articles in molten zinc.
manufacturing industries such as building and auto- The technique has been an accepted as a commercial
motive sectors. It offers ease of formability, high process since year 1850 to provide a durable, eco-
strength-to-weight ratio, and is abundant and rela- nomical, long term protection to steel without the
tively inexpensive compared to other more exotic need for regular maintenance (e. g. see BS 5493).
materials. But steel has a natural affinity towards In fact, history of the process goes back to 1742
rusting. The only way to prevent rust formation is when a French chemist Melouin presented a paper
to isolate the steel from the corrosive effects of the on hot dip galvanizing, but the process really started
environment. Zinc coatings have been used to pro- to draw attention with patents mainly in the 1830’s
tect steel from corrosion for more than 250 years [5]. The technique has wide applications for zinc
[1–4]. Zinc’s first use in construction (roofing) was in coatings which include street furniture, architectural
1811 in Belgium. However, it was not until 1829 that steelwork, agricultural implements, exterior hinges,
the galvanic action of zinc protecting iron was dis- roofing nails and some automotive components and
covered. In an experiment by Michael Faraday, he structures. The basic procedures for galvanizing have
found that zinc protects iron by sacrificial corrosion not changed much over the years. The process itself
to itself when the two metals are in contact in the is, however, not as well – known as the other coating
presence of an electrolyte. This phenomenon known methods. It seems that the hot-dip galvanizers, in
later on as cathodic protection, occurs because zinc spite of providing one of the most important and
is electrochemically anodic to steel. This important widely used anti-corrosion coatings for steel, tend
benefit of applying zinc coating insures cathodic to operate outside the mainstream of metal finishing
protection of steel at cut edges or damaged areas of community. A recent report [6] based on North
the coating. Furthermore, as zinc weathers, it forms American Galvanizers Process Survey among the
stable hydroxides and carbonates, which would members of American Galvanizers Association in
slow down the corrosion rate and thereby providing early 1997 and again in 2000, provides an excellent
excellent resistance against atmospheric corrosion. sampling of the entire North American batch hot
The performance of zinc against corrosion is con- dip galvanizing industry. The information shows the
sistent, because most coating methods applying zinc, trends in the changes happening in the galvanizing
namely hot dip galvanizing, sherardizing, mecha- industry and the improvements in production effi-
nical plating and electroplating, start essentially with ciency. Galvanized sheet steel can now be considered,
a reasonably pure zinc and presence of most impu- by reason of the technologies developed and used in
rities do not significantly alter corrosion perfor- production today, as a class of materials with a range

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 2 Chatterjee: Hot Dip Galvanizing

of attractive properties, such as corrosion resistance, coated with oil, grease or paint, solvent degreasing or
deformability and paintability. In a recent overview, hot alkaline cleaning is required. Alkaline cleaners
the cost factors and fatigue behaviour of galvanized are normally used since they are less expensive
steel in the automotive industry were examined [7]. than vapour degreasers using costly organic sol-
A dictionary definition of galvanizing is “to coat vents, which are only employed for particular cases
(iron or steel) with zinc”. Among the conventional where they have been considered to be the preferable
coatings with zinc, hot dip galvanizing accounts option. Recent advancement of blast cleaning of
for zinc’s primary use which is estimated to be over iron and steel castings with steel or glass shots has
90 % of the total zinc used for coatings world wide been a great innovation in cleaning technology by
[1]. The main reason for such heavy usage of zinc reducing the cleaning time and lowering the number
in galvanizing method compared to other coating of rejects considerably. Thus iron castings (grey
systems is due to the application of very thick or malleable) or steel substrates can be treated for
coating by the process. There has been development galvanizing directly after shot blasting without
of several innovative methods to enhance the cor- necessarily going through the pickling stage [30]. In
rosion resistance property of galvanized coating. fact, cost of shot blasting a large number of castings, is
These include incorporation of TiO2 into the coating offset by saving in time, elimination of acid pickling,
[8], uses of aqueous inorganic-organic hybrid sols lowering coating weights and lessening dross forma-
on the coating by sol-gel method [9], application tion in the galvanizing bath. It is, however, impor-
of dense silica layer onto galvanized steel using a tant to point out that the normal cleaning steps are
colloidal silica/silicate formulations [10], galvanized not normally capable of removing any welding slag,
coating containing dispersed nickel in the under paint or heavy grease on steel articles, which must
layer [11] and pre-treatment of galvanized steel with be, therefore, treated elsewhere more vigorously
silanes modified with microparticles of silica [12, prior to sending off for galvanizing treatment.
13]. Besides applying pure molten zinc, there have The steel surface is normally first treated with acid
been other hot dip processes, such as Galvalume/ (pickle) to remove iron oxides present as rust and/or
Galvalium (55 % Al, 1.6 % Si and the rest zinc), mill scale. Pickling process is commonly carried out
Galfan (4.7–6.2 % Al, 0.02–0.05 % Ce, La and the using warm/hot acid solutions, such as hydrochloric
rest zinc) where molten alloys of zinc are applied acid (HCl) and sulphuric acid (H2SO4). Although
[14–26]. the two acids exhibit very nearly the same pickling
effectiveness, it is HCl which is normally chosen in
2 System evaluation preference to H2SO4. The advantages of HCl include
In conventional hot dip galvanizing, parts are cleaned, use of lower temperature, lower volume and easier
pickled (usually in hydrochloric acid) and fluxed disposal of spent acid; it is also easy to inhibit and
before finally immersing into the molten zinc, which easy to see in pickled condition, avoids sulphate
is sometimes followed by quenching in water. There contamination of flux solution, and moreover, the
are alternative methods to the conventional practice, workpiece may not require prior caustic treatment
namely electrostatic deposition of zinc powder on [31]. Furthermore, unlike H2SO4 which is normally
a ferrous substrate, followed by creating zinc-iron used hot, HCl can be also used cold [28]. Neverthe-
interface by liquefying the powder via reflowing less, there are some advantages with sulphuric acid,
operation [27]. In the present text, factors affecting such as generation of much less corrosive fumes,
the conventional practice are only considered. need for smaller storage of “raw” (bulk) acid, better
for countercurrent rinses and lower cost recovery.
2.1 Pre-treatment The limitation of the cleaning operation with either
The galvanizing reaction will only occur on a che- of these acids, iron salts generated from the reaction
mically clean surface that should be free of grease, between the acid and iron articles, increase until a
dirt and scale prior to galvanizing. A thorough point is reached where the pickling bath is no longer
cleaning of the workpieces can be achieved by a effective. This stage is reached when the iron content
variety of processes [4, 28, 29]. If the workpieces are of the bath is up to about 80 to 100 g/L. By proper

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 Chatterjee: Hot Dip Galvanizing 3

selection and correct use of pickling acid inhibitors, any depth in the technical literature. Density in terms
some galvanizers have dramatically reduced acid of Baume or g/mL unit is a rough measure of the
fumes, greatly extended rack life, significantly pro- total zinc chloride in the fluxing solution in presence
longed bath life and still maintained adequate pick- of ammonium chloride only [33]. It is the ammonium
ling speed. chloride (measured accurately by Kjeldahl method)
An alternative pre-treatment [29] involves degreasing, which acts as the active ingredient in a galvanizing
etching, washing and passivation by consecutive flux, promotes drying of the flux prior to entry of
treatment first at room temperature in solution con- the workpiece into the molten zinc pot/kettle. Zinc
taining 2 to 4 % nitric acid and 3 to 10 % Chromic chloride in the flux is moderately active to help
acid (CrO3), washing in warm water at 60 to 80 °C, preventing rusting of steel prior to its entry into the
and then at room temperature in solution containing molten zinc. Laboratory trials indicate that altering
5 to 10 wt.% HCl, 0.2 to 2.0 wt.% sodium nitrate the pre-flux ammonium chloride content has no
with a final wash in water at 70 to 90 °C. It is to be significant effect on the galvanized coating weight
pointed out that any of the above pre-treatment is [34]. The precise composition of the flux has, how-
always followed by adequate rinsing prior to the next ever, a dramatic effect on the consumption of zinc. It
operation. There is also a non-chemical pre-treatment is a myth that flux composition does not give thinner
method as mentioned earlier, which involves surface zinc coating on the steel. The truth is that a properly
blasting such as shot blasting to remove surface layers formulated and maintained flux solution would allow
prior to hot dipping [30]. A method of heat treatment shorter residence time for steel in the molten zinc,
under controlled atmosphere is also quoted in the and thereby resulting in thinner zinc coatings [31].
literature whereby oxidation of the sheets is con- Usually a small quantity of wetting agent is also
trolled prior to a continuous hot dip process of added to the flux bath. A recent quotation on flux
galvanizing steel strip [32]. composition [37] mentions 60 to 80 wt.% of ZnCl2
The next step prior to galvanizing involves fluxing of and 7 to 20 % NH4Cl with 2 to 20 % of a fluidity
the steel surface [4, 28, 31, 33–37] to provide modifying agent comprising at least one alkali or
a) good adherence of liquid zinc on the workpiece alkaline earth metal.
as it is pulled out of the coating bath, and A more active flux (i. e. one with higher ammonium
b) satisfactory metallurgical interaction between chloride content) can be expected to react more
zinc and steel. aggressively with steel workpiece with subsequent
acceleration of dross formation [34]. In the so-called
The use of a proper flux composition should provide
dry process, fluxes are applied as hot ( around 65–
a good control on zinc consumption during galva-
80 °C) aqueous pre-flux solution on to a dried work-
nizing and thereby making the process cost-effective.
piece for subsequent immersion in molten zinc [4].
The two basic functions of flux include:
The latent heat from the hot fluxing solution helps to
a) elimination of oxide that forms on the workpiece dry up the articles when removed from the solution.
after pickling or abrasive cleaning, and Further drying of the flux coated article is carried out
b) prevention of any interference of oxide film pre- on hot plates or ovens at temperature not exceeding
sent on the surface of the molten zinc bath. 120 °C since the flux decomposes at about 150 °C.
An efficient fluxing action would ensure complete The use of pre-flux in the dry process contributes
contact between the steel surface and molten zinc to the generation of dross in two ways. Any iron
by removing last traces of oxide from the surface of present in the pre-flux is transferred to the zinc bath
the component, and thereby allowing the molten zinc forming intermetallic zinc-iron compounds which
to subsequently wet the steel surface for coating settle to the bottom of the galvanizing kettle as a
reaction to occur satisfactorily. slush of bottom dross to be removed periodically.
Fluxes are generally a mixture of zinc chloride This is why it is important to maintain a low iron
(ZnCl2) and ammonium chloride (NH4Cl) in 1:3 mole content in the flux. Secondly, the pre-flux itself reacts
ratio [34]. The possible influence of flux compo- with the steel surface, generating iron salts in the
sition on coating weight has not been addressed in interval period between fluxing and hot dipping. In

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 4 Chatterjee: Hot Dip Galvanizing

contrast, some galvanizing plants operate using a wet galvanizing temperature, dross is in a semi-solid
process where a blanket of molten flux layer, which state and sinks to the bottom of the bath. Studies of
is black and frothy, is already floating on top of the various means of reducing dry ash (skimmings) and
galvanizing bath. dross [33] as well as composition, testing and control
There are some benefits and disadvantages of both of hot dip galvanizing flux have been detailed else-
dry and wet processes [31, 33, 35]. Compared with where [38].
the wet method, the advantages of the dry process
include thinner and brighter zinc coatings, faster 2.2 Process details
throughput, lesser dross formation and lower usage The quality of coating on a properly prepared work
of flux. Formation of thinner coating also means depends on the quality of molten zinc used, com-
lesser consumption of zinc. The disadvantages of the position of steel substrate, temperature of the gal-
dry process include more spatters from the pot with vanizing bath, time of immersion and the rate of
certain types of work (hollowware) and requiring withdrawal. Based on researches, in-plant consul-
more care in pickling and solution fluxing. Advan- tancy and workshop experience, a guide to some
tages of the wet process primarily include fewer practical information on galvanizing is available
rejects from improperly pickled and poorly solution- in the literature [36]. Conditions in the galvanizing
fluxed steel, less spatter and easier galvanization of plant such as temperature, humidity and air quality
the burn line on double dipped work. Nevertheless, would not affect the quality of the galvanized coating.
most of the continuous sheet galvanizers, if not By contrast, these factors are critically important
all, however, adopt the dry process because of the to achieve good quality on subsequent painting of
substantially less total flux being required, resulting the galvanized surface [4]. It is worth mentioning
in considerably less drossy coating than the wet here that a review of the chemistry of the molten zinc
process. Also, the wet process is likely to provide a bath for galvanizing considered the iron balance in
thicker coating than required. the bath [39].
The fluxed, dried work should be galvanized within
an hour of its preparation; otherwise the flux coating 2.2.1 Quality of molten zinc
tends to absorb moisture from the air and becomes Zinc slab from the smelter containing ~ 1 % lead is
oxidized. Flux solutions are maintained at their normally used for galvanizing [1, 28]. Studies have
optimum by maintaining its specific gravity with shown that the surface tension of pure metallic zinc
addition of more flux crystals, and by adding water at its melting point (419.5 °C) is reduced by 40 %
to make up for drag out losses. An addition of exces- when alloyed with 1 % lead in an inert atmosphere
sive flux does not necessarily remedy a drossy bath. [40]. Experienced galvanizers prefer zinc alloyed
Research work has shown that presence of low iron with 1 % or more lead for the galvanizing bath
(0.5 %) in the flux along with an addition of a trace because of better drainage of molten zinc from steel
amount of aluminium (up to ~ 0.005 %) can be workpieces afterwards. In fact, it is generally con-
helpful in avoiding deposition of excess zinc on the sidered difficult to galvanize satisfactorily if lead
workpiece [34]. However, sludge will build up if the level is below 0.5 %. It is also reported that thinner
iron content in the flux becomes too high, namely zinc coatings are associated with fewer and thinner
exceeding 3.75 g/L when a “flux spotting” defect zinc icicles and a more pleasing appearance of large
becomes more prevalent. At pH of 5.4 or above, flowery grains termed “spangles” originating from
over 90 % of iron precipitates as a sludge and can the solidification pattern of the zinc layer. In con-
be removed. struction industry and certain other applications, the
Besides forming the coating itself, zinc is also con- spangle pattern is considered desirable as it gives
sumed in producing dross, skimmings, splatter and the product an attractive appearance. It is worth
droplets of molten metal removed by centrifuging or mentioning here that simply dropping lead into the
“blow out” of pipe interiors [34]. Dross refers to a molten zinc pot for galvanizing does not cause the
wasteful alloy of iron and zinc consisting of about lead to alloy with zinc. Alloying has to be accom-
1 to 4 % iron with the remainder as zinc. At the plished externally first. Otherwise, the bottom dross

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 Chatterjee: Hot Dip Galvanizing 5

sandwiched between the zinc and lead, acts as a growth of iron-zinc intermetallics, and thus become
formidable barrier to prevent lead from alloying with useful in treating reactive steel [44]. Also, additions
zinc [40]. Lead added to the bath should not contain of manganese (0.5 %) and titanium (0.05 %) to the
antimony, copper or other elements which would zinc bath seem to control the fast growing thick-
otherwise dissolve in zinc and contaminate the ness of coating on reactive steels to even less than
coating. A recent study of hot dip galvanizing baths expected rate from conventional galvanizing bath
of innovative as well as traditional compositions [45].
containing lead (1.1 %), nickel (0.05 %) and/or
bismuth (0.1 %) showed interesting results. The 2.2.2 Composition of steel substrate
reactivity of steel was slower with subsequent lower Besides bath temperature, immersion time etc. (dealt
coating thickness in the presence of nickel and in next section), thickness of the galvanized coating
bismuth in the bath which would thus be suitable to is also greatly affected by the composition of the
control the galvanizing reaction of “reactive” steel substrate which could be steel or cast iron [1, 2, 46].
(mentioned in next section in terms of semi- or fully- Composition of steel for galvanizing can be broadly
killed steel) containing high silicon. Furthermore, classified into two groups, namely low carbon, non-
bismuth which is not hazardous to health or environ- killed steel with low silicon (< 0.05 %), and “reac-
ment unlike lead or nickel, is suggested to be a very tive” steel which could be killed or semi-killed steel
good alternative to lead in improving fluidity of the with high silicon content (above 0.25 %) which is
bath [41]. normally added as a deoxidiser during production of
Aluminium is generally added to the molten zinc steel. For non-killed steel, the relationship between
in small amounts (0.005 %) which tends to reduce coating weight and immersion time is parabolic i. e.
the rate of oxidation of molten zinc, brighten up the coating weight is relatively insensitive to immersion
appearance of the galvanized workpiece and reduce time after an initial period of reaction; any pick-up
the size of spangles so that an improved unifor- of zinc declines to a negligible amount after first 2 to
mity of the coating is attained. Presence of excessive 3 minutes in a parabolic relationship. However,
amounts of aluminium will, however, reduce the rate presence of silicon (more than 0.25 %) in steel,
of zinc-iron alloy formation, making the working of greatly changes its reaction with molten zinc, and
the bath difficult. To safeguard against an excess of a thick galvanized coating is produced typically
aluminium, addition should be made in the form of in about five minutes. Galvanizing of high silicon
zinc-aluminium master alloy in very small quantities. steels such as the most high grade low strength
A quick test of the optimum amount can be carried steels (HSLA), almost maintains a linear relationship
out by scattering a few crystals of ammonium between zinc pick-up and immersion time [1, 2, 47].
chloride on the surface of the zinc bath. At alu- Since the kinetics of metallurgical reaction is a
minium level below 0.007 %, the oxide on the sur- function of time and temperature, an equal mass of
face dissolves and the crystals move about freely, but high silicon (“reactive”) steel compared with non-
will remain inert at higher aluminium content and killed steels, will produce a heavier coating (up to
gradually volatilize. about 200 mm). The claim of good adhesion to the
There are other elements which are added to the basis steel is, however, arguable [48]. The reaction
zinc bath in very small quantities to develop special rate of reactive steel can be so high that the pure
properties of the coating or to assist the processing zinc layer adhering to the galvanized article on with-
method [42, 43]. For example, tin and antimony drawal is transformed completely to zinc-iron alloy
lower the surface tension, titanium and zirconium before the article has time to cool down. A much
act as refiners, and magnesium (and even copper) darker (gray) galvanized coating is produced on
when alloyed with zinc can improve corrosion such reactive steel which, however, should not alter
resistance of the coating. Addition of vanadium along the corrosion resistance property of the coating. The
with nickel to molten zinc is claimed to be suitable speed, with which the coated steel is withdrawn from
for controlling the reaction of semi-killed steels [1]. the molten zinc bath, also contributes to the coating
An addition of tin to the bath is claimed to reduce weight. The slower the withdrawals speed, the lower

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 6 Chatterjee: Hot Dip Galvanizing

the coating weight [2]. Also, steel fabrications con- parts to enter the bath may be considerable. A heavy
taining light and heavy sections should be avoided to coating would be produced if the workpiece is left
preclude development of very heavy coatings on the in the bath until “boiling off ” stops and then with-
lighter weight sections. Cast irons like silicon-killed drawn immediately. An alternative method [52]
steel also react vigorously with molten zinc during involves changing the orientation of the steel sheet
hot dip galvanizing [33]. immersed in the molten zinc bath, by adopting an
orientation changing device that will pull the steel
2.2.3 Bath temp sheet out of the bath. This is followed by adjusting
With zinc melting ~ 420 °C, the normal working the amount of molten metal adhering to the steel
temperature of the bath is usually maintained in the sheet by means of a gas wiping device. The use of an
range 440 to 460 °C. A lowest possible temperature electromagnetic set up will finally correct the warp
consistent with the drainage of zinc from the work- of the steel sheet via its magnetic force in a contact-
piece, is always to be aimed for efficient galvanizing less manner. The surface properties of the finished
in order to keep ash and dross to a minimum, con- article are claimed to be excellent.
serve fuel and prevent damage to the zinc pot [28]. The period of immersion varies with companies, but,
The critical temperature for reaction between iron- as a general rule, malleable cast iron pipe fittings
zinc alloy coatings and molten zinc is 480 °C. Below are immersed for a minimum of 40 seconds, steel
480 °C, a compact zinc-iron alloy is formed at the on an average of 25 seconds and cast iron for about
surface of the work with the alloying action even- a minute. The alloying action on castings starts off
tually ceasing up. Above the critical temperature, after about 15 seconds of immersion. A typical
two effects come into play, namely immersion time is about 4 or 5 minutes, but it can
a) break down of the alloy layer, allowing zinc to be longer for heavy articles that have high thermal
penetrate into the basis metal with the resulting inertia or where zinc is required to penetrate internal
formation of very large amount of dross, and space [4]. If castings do not galvanize satisfactorily
b) likely attack of the pot itself by the molten zinc. within the normal time, the cleaning system in the
Recently, a two-stage process of galvanizing followed pre-treatment stage must be investigated. Other-
by heating in the range 420 to 800 °C is claimed to wise, a longer immersion in the zinc bath used as a
improve composition of coating [49]. A new method cleaning bath could result in excessive dross pro-
is devised for galvanizing hot rolled steel strip [50]. duction.
It involves preheating the strip after normal cleaning,
up to the galvanizing temperature under a protective 2.2.5 Withdrawal of galvanized work
atmosphere, followed by immersion in a galvanizing When the reaction between iron and zinc has virtually
bath. In another work [51], both the quality and self- ceased, the workpiece is taken out of the galvanized
healing property of coating (25–80 µm) are claimed bath. On withdrawal from the galvanizing bath,
to be superior to that from conventional galvanizing. a layer of molten zinc will be taken out on top of
It is based on an innovative process which utilizes the coated layer, which often cools down to exhibit
the special properties of zinc-iron alloys at 560 to a bright shiny appearance (“spangles”) typically
600 °C or more forming a homogeneous δ-phase associated with galvanized products [2, 4]. The speed
coating. of withdrawal controls the thickness of the unalloyed
top layer of zinc on the workpiece [28]. Although
2.2.4 Immersion of workpiece an optimum rate of withdrawal is expected around
The workpiece should be submerged as rapidly as 1.5 m (5 feet) per minute, the rate varies with
possible with due caution for safety [28]. In wet customers’ specifications. If the coated articles are
fluxing process, quantity of dross during galvanizing withdrawn at a rate slower than the rate at which
increases depending on the time the work is in con- the zinc drains freely from the surface, a uniform
tact with the flux blanket. The speed of immersion unalloyed zinc layer will result. However, if the
affects the uniformity of coating, particularly with withdrawal rate is too fast, the surplus zinc carried
long articles where the time between the first and last clear of the bath, will run and solidify in droplets,

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 Chatterjee: Hot Dip Galvanizing 7

producing a lumpy, uneven coating. Factors affecting Some of the specialist applications are considered
the energy balance of galvanizing furnaces of various next. It is worth pointing out here that one should
types and sizes have been discussed elsewhere [53]. be aware of the various general factors that could
In wet fluxing process, withdrawal of coated steel affect the characteristics and appearance of hot dip
through a blanket of flux on the zinc surface helps galvanized coatings. These include size and shape
to wipe off excess molten metal, which in turn aids of item, steel chemistry, surface condition of steel,
to increase the withdrawal rate. But any withdrawal design of article with respect to galvanizing, and
through flux should be followed by quenching the metallurgy of the galvanizing process. Coating
coated parts in water to remove flux residues, and defects such as embrittlement, distortion, pickling
thereby avoiding the danger of corrosion from the corrosion, blow outs and bleeding, flaking, white
flux. Water quenching also helps to solidify the zinc rust formation, pinholig etc. are discussed elsewhere
coating quicker and minimises any presence of grey [54, 55].
coating, which can arise from the growth of alloy
layer during slow cooling. Sometimes addition of 2.3.1 Galvanizing tubes
soft soap or light oil to the quench water improves The two most common methods of applying zinc
the smoothness and brightness of the coating. In metal to steel handrail tubing for the purpose of pro-
cases where water quenching is not practical, with- tection from corrosion are batch hot-dip galvanizing
drawal must be accomplished by skimming back the and in-line continuous galvanizing [56–58]. The
flux blanket, or blowing off the flux with compressed zinc coating of steel pipes is a function of base metal
air before withdrawal. Water quenching is not chemistry, surface condition, addition of elements
pursued with cast iron components, particularly such as lead and aluminium, dipping time, tempera-
malleable iron with high phosphorus contents. This ture of zinc bath, angle and speed of withdrawal, out-
is because rapid cooling of high phosphorus irons side wiping pressure, inside blowing media, time and
tends to cause the metal to become brittle at or above pressure. For the batch process, thoroughly cleaned
room temperature. The worst condition for embrittle- steel tubes (usually 6 or 12 m long) are immersed into
ment occurs when susceptible cast irons are quenched a molten zinc bath from a hoist. For standard tubing
from about 455 °C which is around the same tem- of 6.3-mm (0.25-in.) wall thickness, it is normal
perature as hot dip galvanizing [28]. practice to apply a minimum thickness of 75 mm
No post-treatment of galvanised articles is necessary. (micron) or about 519 g/m2 (1.7 oz/ft2) as weight of
However, chemical conversion coatings and other protective coating of zinc. Once the newly produced
barrier systems may be applied to minimise the galvanized tubing cools, it is ready for shipment. In
occurrence of wet storage stain. Also, paint or a the case of in-line galvanizing, tubes are fed through
powder coating may be applied to enhance aesthetics a molten bath of zinc, followed by application of
or for additional protection where the environment is a conversion coating to prevent the formation of
extremely aggressive. naturally occurring zinc oxide and hydroxide.
It applies only to about 23 mm or ~ 160 g/m2
2.3 Specific applications (0.5 oz/ft2). This means that the service life against
Galvanizing is a versatile process, which could treat corrosion using a zinc coating produced by a batch
a wide variety of articles ranging from nuts, and process can be, as expected, about three times longer
bolts to long structural sections. Together with the than by in-line produced coating. Usually, a final
ability to bolt or weld fabrications after galvanizing, coat of a clear inorganic polymeric paint is applied on
the process allows almost any size of structure to be top of the chromate conversion coating of galvanized
galvanized. A wide range of fabricated steel articles zinc on the outside of the tubing, while the inside
is galvanized for their appearance as well as pro- of tubing receives only a coating of zinc-rich paint.
tection against outdoor environments. Roofing and For either process of galvanizing, proper venting of
sheet siding, cans, pails, tanks, nails, outdoor hard- hollow materials and proper drainage of structural
ware, pipe and conduit are among the many articles shapes are important since the coating thickness is
protected from weathering and rust by galvanizing. determined by dwell time in the bath. Also, tubular

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 8 Chatterjee: Hot Dip Galvanizing

fabricated items must be vented internally to permit directly to a bare steel surface, fail quickly because
the molten zinc to flow freely through the tubing rust from steel’s corrosion occupies a larger volume
without forming pockets of trapped air or moisture than the original steel. As a result, once the rust is
during immersion as well as withdrawal operation. formed, it lifts the paint by blistering that allows the
A metallurgical reaction occurs between the molten rust to show through with subsequent acceleration
zinc and iron in the steel tubing during the galva- of further corrosion. A simple system with improved
nizing process. This results in the formation of three corrosion performance can be expected by applying
layers of zinc-iron alloys metallurgically bonded to special paints on galvanized steel. Based on
the base metal with a strength ~ 3,600 psi, topped accelerated corrosion testing, it was identified that
by an impact-resistant outer layer of pure zinc. This chlorinated rubber and epoxy paint are the most cor-
magnitude of bond strength is important for im- rosion resistant paints [59]. Weathering of galvanized
proving corrosion resistance of the interior surface steel does not seem to affect its paintablity as long
of batch galvanizing tubing where water or moisture as a suitable pre-treatment is given. There is another
may be trapped. In comparison, the corresponding system widely used in North America on small
bond strength in zinc-rich paint applied to the inside diameter tubing for automotive and refrigeration
of tubing produced by in-line galvanizing, is about applications, which involves an alloy coating (8–
an order of magnitude less, namely around 300 to 15 mm) of zinc – 5 % aluminium alloy (Galfan)
500 psi, and, therefore, perform far less effectively followed by an organic top coat (5–10 mm) of say
against corrosion. Thus batch-galvanized tubing and Dorrfex – an aluminium-rich epoxy-phenolic com-
pipe are often used as parts of fabrications of hot- pound [57]. Galfan is applied by a hot-dip process
dip galvanized vessels and tanks for storing a wide that ensures good adhesion by creating an interface
range of liquids. Furthermore, the thick zinc in the with greater strength between a properly prepared,
zinc-iron alloy layers by a batch process is also clean steel surface and the molten alloy. Galfan inter-
harder (250 DPN) than the base steel (160 DPN). faces with the steel tubing by forming a very thin
Thus it is quite difficult to damage such zinc coating, layer (0.1 mm) of aluminium-rich Fe2Al5Znx inter-
which ultimately enhances its resistance against metallic. It is claimed that the thicker iron-zinc alloys
corrosion. In comparison, the inorganic polymer formed at the interface in conventional hot dip gal-
paint covering the thin layer of zinc produced by vanizing are hard and brittle with limited formability
an in-line process damages as easily as any other compared with the thinner Galfan interface which is
paint and is particularly susceptible to deterioration as ductile as steel.
caused by ultraviolet rays from the sun.
Adoption of a duplex anticorrosion system appears 2.3.2 Galvanizing nails
to fulfil the increasing demand for longer-life of steel A large percentage of the nail volume is coated to
tubing used in the automotive industry for fuel and prevent them from corroding and deteriorating the
brake line applications. A duplex system is a com- surrounding wood [60]. It is well known that steel
bination of a metallic anticorrosion coating of nor- nails in contact with wet wood or other corrosive
mally zinc and zinc alloys on the steel surface with a environments will form rust that would promote
top layer of an organic coating. This approach takes chemical reactions causing the cellulose of the wood
advantage of the generally accepted best metallic to hydrolyze or weaken. Thus corrosion of nail with
coatings of zinc and zinc alloys, which protect steel deterioration of the wood would lead to losses of
against corrosion via physical barrier and sacrificial strength to the joint as well as the structural integ-
anode action. The new technology of a duplex system rity of the assembly. Among the various protective
offers better corrosion protection than the arith- coatings on nails to prevent corrosion, metallic
metic sum of the individual protection system. The coatings of zinc appear to provide a truly imperme-
metallic coating gives longer life to the organic able layer, resulting in good resistance to atmospheric
coating by preventing formation of rust, which occurs corrosion and abrasion. There are four major pro-
due to diffusion of oxygen and water through the cesses of coating zinc onto small parts such as nails
paint onto the steel surface. Organic coatings applied and threaded components; they include spin or cen-

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 Chatterjee: Hot Dip Galvanizing 9

trifuge galvanizing, electroplating, sherardizing and Bolts produced by normal temperature hot dip gal-
mechanical plating of zinc. Hot dip galvanizing is vanizing, showed clean threads that would allow nuts
the oldest zinc coating process where nails are to mate easily and securely. As a general rule, nuts,
placed inside a dip perforated basket and then bolts and washers down to M8 size can readily be
immersed in a molten zinc bath. After the coating has galvanized.
formed, the basket is centrifuged at a high speed so Galvanized fasteners usually have a bright, light grey
that the spinning action throws off the surplus zinc appearance, but characteristically rough. With cer-
and ensures a clean profile. The uniformity of the tain grades of high yield and high tensile bolts, the
coating depends upon how soon the batch is removed coating can be matt grey; this is because the higher
from the molten bath, time delays, batch size and silicon content of such components makes them
configuration of nails. It is obvious that smaller the more reactive towards the molten zinc. Studies have
nail, the more difficult it is to remove the excess shown that high temperature hot dip galvanizing
zinc. The high temperature of the molten zinc may exaggerates imperfections in the original uncoated
temper hardened steel nails. The molten zinc also, bolt, and produces thicker coatings in those areas via
unless careful, may fill the threads of nails. Indus- very rapid growth of zinc-iron alloy.
trial experiments have shown that for best quality Initially, the coefficient of friction with galvanized
centrifuging, satisfactory results are obtained by contact surfaces is low at an average of ~ 0.19.
using thick walled centrifuge baskets to hold the However, as slip commences in service, friction
heat, and spinning the parts at about 500 rpm for 5 to rapidly builds up and “lock-up” occurs due to cold
8 seconds, followed by an abrupt jolting reversal to welding between the coated surfaces. If no slip can
centrifuge in the opposite direction for similar time be tolerated, the coefficient of friction can be raised
period. Although the chemical costs are relatively by roughening the surface of the galvanized coating
low, energy costs are high to keep the zinc bath with wire brushing, light grit blasting or even with
molten at 440 to 460 °C. With regard to the assess- a pneumatic chisel hammer or needle gun [4]. On
ment of corrosion protection, the first sign of red installation, galvanized high strength bolts should be
rust in a 5 % neutral salt spray test is reported to lubricated to prevent galling in the threads.
appear after about 300 hours for a coating thickness The initial cost of hot dip galvanizing fasteners with
~ 40 mm. 43 mm as the minimum thickness, is higher than
zinc electroplating (8 mm), but somewhat lower than
2.3.3 Galvanizing nuts and bolts Sherardizing (15 mm). However, as the coating life
Smaller steel parts, such as threaded fasteners, can is proportional to its thickness, hot dip galvanizing
benefit from the protection of a hot dip galvanized would turn out to be quite economical in terms of
coating using a centrifuge or spin technique as cost per year of rust-free life of protection of steel
described above for galvanizing nails. The thickness fasteners and similar small parts.
and uniformity of coating are important because
they determine nut/bolt thread fit, lifetime of the 3 Process specification
nut/bolt connection, and economical use of coating The basic specification for hot dip galvanized
materials [4, 61]. If the coatings were too thick or too coatings on iron and steel articles was for many years
rough, the bolt would not be able to mate with the defined by a single standard BS 729: 1971 (1986)
nut. On the other hand, if the coating is too thin, the which was withdrawn during 1999 and replaced
bolt mates too loosely, resulting in a weak connec- with a new international standard BS EN ISO 1461.
tion. An improper nut/bolt fit can lead to premature Although both standards are similar, work should
failure of the bolted product. For parts coated with refer to the new standard whose requirements in-
zinc by electroplating, the coating builds up on the clude process of cleaning, preparation of steelwork as
crests of the threads with a marked thinning out in well as procedure for galvanizing [4]. Whenever hot
the roots. Whilst there is some tendency for hot dip dip galvanizing is specified for a job, the surface of
galvanizing to be thicker in the roots, a very uniform steel is expected to be covered with a uniform coating
coating can be obtained with modern equipment [4]. of galvanized layer whose thickness is determined

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 10 Chatterjee: Hot Dip Galvanizing

primarily by the thickness of the steel being gal- use in particularly aggressive environments and can
vanized. This is an important advantage of the pro- be specified in conjunction with the above specifica-
cess when a standard coating thickness is applied tion. It is worth emphasising that for most applica-
almost automatically. The actual thickness of gal- tions, thicker coatings that are, of course, costly, are
vanized coating varies with size, surface profile and rarely necessary. For fasteners and their accessories,
surface composition of steel. the specification should conform to BS 7371:1998:
A thin or thick coating can be achieved in the Part 3 for coating thickness around 8 mm, and Part 6
following ways. A minimum average coating thick- for 43 mm minimum.
ness/weight can be obtained by centrifugal technique
whereby parts after being galvanized are spun at 4 Metallurgical characteristics of coating
high speed to throw off surplus zinc to ensure clean Most ferrous materials can be hot-dip galvanized.
profile (BS EN ISO 1461 and BS 7371 Part 6) [4]. When a clean iron or steel component is dipped into
The galvanizing process together with corrosion the molten zinc, a series of zinc-iron alloy layers are
property of the coating and the key elements of formed by a metallurgical reaction between iron and
BS EN ISO 1461A have been discussed elsewhere zinc [2, 4, 64–66]. The metallurgical characteristic
[62]. Thick coating can be produced by using steel of the galvanized coating is a function of the chemi-
whose surface is roughened by grit blasting and cal composition of the substrate steel. In accordance
thereby increasing the surface area of contact with with the binary phase diagram, a typical galvanized
the molten zinc. The use of steel with some controlled coating on plain carbon steel should consist of three
pattern of surface roughness for galvanizing is also zinc-iron alloy layers with increasing iron content
claimed to enhance protective property of the coating by moving towards the surface of steel substrate,
[63]. Alternatively, a reactive steel containing silicon, namely a top layer of 94%Zn-6%Fe (ζ – 179 DPN
which is frequently added as a deoxidiser during hardness) is followed by 90%Zn-10%Fe (δ – 244
the production of steel, can affect the composition DPN hardness) with a final bottom layer of 75%Zn-
of zinc-iron alloy layers in such a way as to allow 25%Fe (Γ – 250 DPN hardness) covering the sub-
them to grow linearly with time. Since the figures strate steel (α – 159 DPN hardness) [4a]. These
for coating life expectancy are quoted on the basis layers are mostly covered by a top, outer layer of
of minimum coating thickness, they are, therefore, 100 % solidified zinc layer (η – 70 DPN hardness)
usually very conservative. Actual coating weights with almost similar composition as the zinc bath.
are often much more than the minimum specified in Various zinc-iron phases are formed when zinc
the standard. Thicker coatings than those set out in comes into contact with iron at about 200 °C. At this
BS EN ISO 1461 can give additional protection for temperature, the rate of alloy formation is although

Fig. 1: Structure of zinc layer applied by hot dipping: ζ-layer on flat surface is compact
whereas at edge it is loose and grown out

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 Chatterjee: Hot Dip Galvanizing 11

very slow, it accelerates with increasing temperature.

The rate could thus suddenly increase by a factor
of 200 at the melting point of zinc (419.5 °C) i. e.
temperature of the galvanizing bath when all three
alloy phases are formed within a few seconds. The
volume of ζ-crystals is greater than that of the iron
crystals from which this layer is formed [67]. In a
compact ζ-layer, the crystals stay under pressure,
and the growth in thickness of the layer follows
approximately a parabolic rate with time:growth
effectively ceases within a few minutes [1, 66]. Once
the reaction rate starts to slow down, the coating
thickness does not increase significantly, even if the
article is left in the bath for a longer length of time.
However, for a less compact (loose) structure of the
ζ-layer, the crystals will have room to grow roughly
at a linear rate with the alloy layers mainly con- Fig. 2: Coating thickness of galvanized (@ 460 °C for
9 minutes) steel with various silicon content
sisting of ζ-crystals, start to form in a short period.
This happens, for example, with reactive steel con-
taining high silicon.
anomalous behaviour up to ~ 0.15 % Si, beyond
In reality, there is no sharp demarcation between which coating thickness increases more or less
layers, but a gradual transition through the series of linearly with increasing silicon content [4]. There has
zinc-iron alloy phases that would make the coating been some attempts to put forward explanations of
an integral part of the steel surface with excellent the accelerating effect of silicon on the galvanizing
cohesion via metallurgical bond. It is this metallur- reaction [48, 69]. Based on electron diffraction
gical bond between zinc, zinc-iron layers and steel studies, fast growth of Zn-Fe layers in reactive steel
that distinguishes galvanizing from other coatings. is believed to result in excessive accumulation of
Steels with carbon in excess of 0.25 % and man- silicon on the surface of steel substrate due to
ganese more than 1.35 % can produce coatings which limited solubility of silicon in the Γ-layer. With the
are all or nearly all zinc-iron alloys. Steels con- movement of the α-Fe/Γ interface towards the sub-
taining silicon at levels exceeding 0.05 % typically strate, silicon-rich α-Fe breaks into particles and
will produce galvanized coatings with a dull, move towards the δ-layer through the Γ-layer due to
mat finish rather than a more conventional highly low solubility of (silicon-rich α-Fe) particles in the
spangled coating which can be expected with steels Γ-layer. On reaching the δ/Γ interface, the particles
containing silicon less than 0.05 %. Recent in- dissolve in the δ-layer and accelerate the growth of
vestigation of the thermodynamics of multi-com- the layer toward steel substrate with gradual dis-
ponent alloys, such as Fe-Zn, Fe-Zn-Al, Fe-Zn-Ni appearance of the Γ-layer. At this stage, the coating
systems, has led to the development of thermo- starts to become loose by being too thick via trans-
chemical software that could be useful tool for gal- port of silicon in steels into the coating [48]. An
vanizing [68]. alternative suggestion considers that a thin layer of
The reaction rate of reactive steel i. e. steel with liquid zinc saturated with silicon on the steel surface,
high silicon content is fast enough to ensure com- leads to the loose and overly thick coating during
plete transformation of pure zinc layer to zinc-iron galvanization [70, 71].
alloys before the article has time to cool. As a result, The metallurgical bond in galvanized coating is
a thick coating is produced which would appear superior to normal barrier coatings of electroplated
much darker than normal. The effect of silicon con- zinc in terms of adhesion and abrasion resistance.
tent of steel on the thickness of galvanized coating is The outer layer of pure zinc is relatively soft with
shown in Figure 2 which illustrates an unusual hardness around 70 DPN, which can absorb much of

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 12 Chatterjee: Hot Dip Galvanizing

the shock of an initial impact during handling. The rolling after galvanizing to facilitate zinc diffusion to
alloy layers beneath zinc are much harder, some- the base for better adhesive strength [77]. The pro-
times even harder than the base steel itself. Thus the duct is claimed to provide improved wear resistance,
hardness increases from a zeta layer of 179 DPN weldability, and corrosion resistance with elimina-
to about 244 DPN for a delta layer, which is much tion of coating defects such as powdering. Another
harder than the base steel [2]. This combination of unusual innovative method of producing galvanized
soft zinc with hard alloy layers underneath provides steel plate comprises steps of hot dip galvanizing,
a tough, abrasion resistant coating. The use of high skin pass temper rolling and oxidation treatment
strength bainitic steel containing 1 to 3 % Mn for [78]. The plating layer consists of eta phase of
galvanizing, is reported to provide excellent ductility zinc-iron alloy with an oxide layer on the surface.
and anti-fatigue properties [72, 73]. These charac- The product is claimed to provide excellent press
teristics render such hot dip galvanized steel its very formability.
high degree of durability in terms of resistance to
mechanical damage of the protective coatings during 5 Corrosion resistance of coating
handling, storage, transport and erection and essen- Galvanized steel can be considered as a class of
tially eliminate the need for costly operation of field/ materials that has been developed under the ever
on-site “touch up” of the coating. The outstanding growing demand for quality products capable of
durability of hot dipped material renders them better offering good resistance to corrosion in normal use,
to withstand deformation than electroplated zinc or i. e. atmospheric corrosion in rural, marine and in-
iron – zinc alloy. As a result, superior resistance to dustrial environments [66, 79] (Fig. 3). The service
corrosion can be expected from galvanized articles life of a structure beyond its intrinsic nature depends
[74]. largely on its ability to withstand the corrosive im-
A study of high temperature hot dip galvanizing pact of the environment it operates. Zinc’s corro-
(HT HDG) of reactive steel in the range 520 to sion rate is inherently slower than steel corrosion,
560 °C produced fully alloyed coatings. Surface of making it an ideal coating candidate. When the two
the coatings had microporous character and consisted are exposed in similar environments, zinc corrodes
primarily of omega (?) alloy with small amounts at 1/10 to 1/40 the rate of steel [4b]. More precise
of zeta and gamma phases [75. 76]. Such coatings exposure tests have shown that the corrosion rate
with microporous surface enhanced paintability and of unprotected steel compared to zinc can be seven-
rendered suitable for applications where abrasion and teen times in arid climate, and about eighty times in
wear resistance are important. Recently, a method a marine atmosphere [2]. For zinc coatings, the low
of producing a galvanized coating on steel strip corrosion rate is linear over time for most atmo-
describes introduction of annealing and temper spheric exposure, and is nearly always proportional

Fig. 3: Corrosion of zinc coatings on steel substrate

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 Chatterjee: Hot Dip Galvanizing 13

to the amount of zinc present. A major advantage Although heavier galvanized coating weights are
of this is that it allows predictions of ultimate life to intrinsically desirable from a corrosion protection
be made on the basis of interim assessments of point of view, such thick coating would, however
coating thickness. be more liable to brittleness and handling-induced
On withdrawal from a galvanizing bath, the top damage [2]. Besides the accelerating effect of high
coating of zinc on steel always has a clean, bright, silicon steel on galvanizing reaction, and thereby pro-
shiny surface [4], which, however, changes with ducing a very thick coating, other factors which can
time to a dull grey patina as the surface reacts with result in heavy galvanized coating, such as proper
oxygen, water and carbon dioxide in the atmosphere. pre-galvanizing storage, pickling time, withdrawal
Thus after initial brightness, a thin oxide layer is rate etc. need to be controlled as allowed by the
formed on every zinc coating in a humid atmosphere. process. It is important to mention here that thick zinc
The oxide is subsequently converted into a double coatings on silicon steels (so-called reactive steel) are
salt of carbonate and hydroxide: 2 ZnCO3 · 3 Zn(OH)2 mostly dull with brown staining [66]. An explana-
which is a compact, tough and stable complex, in- tion of brown staining considers that the ζ-crystals
soluble in water, and tightly adheres to the zinc layer which mostly constitute the coating, grow very fast
to provide protection for zinc against any atmo- on such steels, even after the article has been taken
spheric attack [66]. The protective layer can only be out of the zinc bath. At some stage when the outer
formed when the zinc oxide comes into contact with layer is missing the ζ-crystals, the free iron extends
sufficient carbon dioxide and moisture. If little or no to the surface. In moist surroundings, this iron cor-
carbon dioxide were present, as might be the case rodes and stains the surface brown, sometimes
for zinc covered with water of condensation, which within a few days. Such staining is not, however,
contains little carbon dioxide, sufficient ZnCO3 observed in other coating methods, such as electro-
would not be formed. Instead, voluminous white rust plating, and does not adversely affect the corrosion
of Zn(OH)2 will be formed. There is, of course, no resistance property of the galvanized coating [66].
reason to reject a galvanized surface with only a little It is claimed that the composition of molten zinc used
white rust present, since a protective layer is likely to for galvanizing is apparently not critical to affect
be formed in due course, provided sufficient carbon corrosion resistance of the coating [28]. However,
dioxide is present [80]. depending on the solidification condition of the gal-
Zinc coatings would protect steel against corrosion vanized article, the beneficial effect of the presence
by of elements, such as lead, antimony and aluminium
a) producing a physical barrier film and in molten zinc (sec. 2.2.1) may be eroded in some
b) acting as sacrificial anode to steel. cases by having dull finish due to high percentage
Hot dip galvanized steel with entire coating com- of rough and poor reflectivity (dull spangles). The
posed of zinc and its alloys with iron, provides a dull spangles compared to smooth, reflective, bright
good example of cathodic protection of steel struc- spangles, not only detract the galvanized coating
tures. For example, a galvanized steel may be appearance, but also adversely affect surface reac-
damaged due to rough handling during its erection tivity which can lead to premature darkening with
as a building structure whereby the galvanized greater susceptibility to corrosion (white rusting)
coating is partly removed exposing a small area of [81–83]. It is worth pointing out here that although
base steel. The surrounding zinc will cathodically an aesthetic finish with large, smooth spangles is
protect the exposed bare steel. Also, besides catho- acceptable in construction industry and some house-
dic protection, hot dip galvanizing process com- hold appliances, this is not the case in automotive
pared to other coating methods, provides a thicker or similar applications where the surface roughness
coating, and hence better corrosion resistance by and differences in crystal orientation associated with
generating thicker barrier to corrosion of steel sub- spangles can impair the appearance of galvanized
strate (Fig. 3) [4a]. In ASTM A123, a range of mini- sheets after paininting [84]. Minimum spangled
mum thickness of galvanized coating is stipulated material with very fine spangle pattern is required for
depending upon the environment. exposed panel in automotive industry.

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 14 Chatterjee: Hot Dip Galvanizing

The difference in surface appearance and hence the formation of white rust on zinc. There are also
reactivity suggests that the dull spangles have dif- several other references in the literature to improve
ferent surface composition than bright spangles A corrosion resistance of galvanized coating by appli-
survey of literature [81, 82, 84–88] indicates direct cation of an overcoat of paints of organic or in-
effect of the amounts of lead, aluminium and anti- organic nature [91–93].
mony on the population and sizes of dull rather than Among the contaminants in the atmosphere affecting
the highly reflective bright spangles. Their presence the nature of the protective film on zinc, the most
in dull spangles causes premature darkening of the important one is sulphur dioxide (SO2). In fact, it is
galvanized sheet by generating galvanic cell with the presence of SO2 which largely controls the atmo-
zinc. It is explained that the solubility of these ele- spheric corrosion of zinc. A thicker coating by hot
ments in solid zinc decreases as the amounts of them dip galvanizing compared to other zinc coating
in molten zinc increases, and thereby reducing the methods, results in better corrosion resistance. In
solidification point of unsolidified parts. On the BS 5493 published in 1977, a guideline is provided
other hand, spangle becomes smaller as the soli- on the lifetime of galvanized coatings. However,
dification rate increases due to the increased for- because of the considerable reduction in the SO2
mation rate of solidified crystal cores at a higher level since 1977, BS 5493 is now out-of-date and
solidification rate. Recent work suggests that both replaced by the new guidance document BS EN
the surface texture and corrosion resistance of gal- ISO 14713:1999. Recently, the UK Galvanizers
vanized steel sheets are more adversely affected by Association have produced a “Millenium Map”
lead than antimony [89]. showing how various parts of the UK are sensi-
Measurement of spangle ratio showed that a gal- tive to corrosion [4b]. Their results on atmospheric
vanized coating with overall brightness can con- exposures in Europe (Fig. 4) illustrate a clear and a
tain bright spangles ~ 70 % compared to ~ 30 % in very significant drop in corrosion rate for zinc from
coatings with dull appearance [81]. The use of ~15 g/m2/year in 1978 to ~ 4 g/m2/year in 1992,
conventional chromate passivating solution for post- which implies a drop in atmospheric sulphur dioxide
galvanized treatment, did not prevent premature concentrations.
darkening. However, a laboratory formulated chro- Performance of hot dip galvanizing to protect steel
mating passivating solution containing nitric acid in environments other than SO2, has been discussed
for preferential dissolution of lead, and fluorosilicic elsewhere [4b]. Presence of scale-forming salts in
acid to take care of aluminium and antimony, seem cold water helps to improve the life of galvanized
to minimise the darkening problem with improved water distribution system by forming a protective
corrosion resistance [81]. layer on the inside surface. However, exposure to hot
The basic layers of a hot-dip galvanized coating as water may not always be beneficial, because zinc may
described earlier, namely alloy layers of
zinc and iron in contact with the surface
of galvanized steel article, and an outer
layer of unalloyed zinc, contribute to the
corrosion resistance of the coating. The
resistance can be further improved by
applying a combination of self-assembling
molecules (SAM) and silicate layers on
top of the coating [90]. Such molecules
basically consist of three components: a
head group which reacts with the zinc sur-
face, a long straight carbon chain and an
end group. The combined layers are
expected to improve corrosion resistance Fig. 4: Improved life of galvanized steel due to reduced sulphur
of hot-dip galvanized steel by inhibiting dioxide pollution in Europe

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 Chatterjee: Hot Dip Galvanizing 15

become cathodic to steel above 60 °C in some waters. be rectified quickly and efficiently. The thickness
In such situation, a sacrificial protection can be measurements should be taken at points as wide
assured by installing a magnesium anode as “back- apart as possible so as to represent average thick-
up” to the zinc coating. Protection of steelwork in ness over the entire article. One should bear in mind
harsh interior environments, such as swimming pools that coating thickness is the result of interaction of
and breweries is increased by more than 40 years the steel chemistry, surface condition of the steel
by using hot dip galvanized steel. The life of buried as it enters the galvanized bath, the bath tempera-
galvanized steel varies with the acidity of the soil; ture, time in the bath and the rate of withdrawal of
a change in pH range from 5.5 to 12.5 i. e. weakly the workpiece from the bath [2]. The coating should
acidic to alkaline is favourable. Regarding thermal be continuous, adherent, as smooth and evenly
properties, galvanized coating is likely to withstand distributed as possible, and free from any defect that
continuous exposure to temperatures of ~ 200 °C is detrimental to the stated end use of the coated
with occasional excursions to 275 °C. Above these article. Besides using reactive steel with more than
temperatures, the outer zinc layer tends to separate, 0.25 % silicon (sec. 2.2.2), roughening of the sur-
although the zinc-iron alloy layer which comprises face by grit blasting can produce coating thicker
the majority of the coating remains intact. than normal (sec. 3). Roughness increases the sur-
Zinc coating provides excellent protection for steel face area of steel in contact with the molten zinc and
wires in the construction of steel ropes for use in would generally increase the weight per unit area of
marine environments [94]. Ropes are made up of a hot dip galvanized coating by up to 50 %. For
cold-drawn eutectoid steel wires wound into strands, example, a nominal coating thickness of 1000 g/m2
which may then be wound into the finished rope. It (140 µm) has been successfully attained on grit
is usual to galvanize the wires prior to making them blasted steel of > 6 mm section thickness [4].
up into the rope. In hot dip galvanizing, as the wire Coating thickness’ are normally determined by the
continuously passes through the molten bath of steel thickness and are set out in BS EN ISO 1461
zinc, it emerges from the bath normally consisting [4]. It is important to check the coating thickness,
of Fe-Zn alloy layer of thickness ~ 10 mm with an normally between 35 to 70 µm on galvanized steel,
outer thicker layer of zinc. A major cause of failure which would ensure cost-effectiveness and assurance
of wires making the ropes is fretting fatigue. of coating quality for optimum corrosion protec-
Although hot-dip galvanized ropes are shown to tion. The various standard methods of measuring
lower the fretting fatigue strengths in air, they are the thickness of galvanized zinc coatings include
better than electrodeposited coatings of same thick- magnetic, coulometric and profilographic methods
ness exposed to seawater. The difference is attributed [97–99]. It is known [97, 100] that the iron content
to the presence of alloy layer in the galvanized of the intermetallics at the zinc-steel interface of
coating. The poor result in air for the galvanized a galvanized coating may change from 0.003 % to
wire is considered to be related to the hard, brittle 28 %. As a result of this large variation in iron con-
Zn-Fe layer rather than the beneficial effect of the tents, the error and hence the possible chance of
process in reducing residual stress. A recent study acceptance of a magnetic method to measure the
of the effects of zinc-iron intermetallics on the stress thickness of galvanized coating needs to be looked
corrosion behaviour of hot-dip galvanized steel at carefully. For thicker coating with thickness in
showed the brittle fracture to be similar to hydrogen the range of 25 to 85 mm, the measurement error
embrittlement [95]. in using the magnetic method is not higher than ±
10 % which is generally acceptable [97]. However,
6 Coating thickness and its measurements nowadays thinner coatings around 10 to 20 mm
The integrity of hot dip galvanized coating is deter- are being used in some industry. As a result, the
mined by visual inspection and coating thickness measurement error using magnetic method becomes
measurement [96]. It would be economical if in- unacceptable because it may increase 2 to 3 folds
spection is carried out at the premises of galva- due to the presence of intermetallics. A coulomet-
nizing operation, so that any defects detected could ric or a profilograhic method appears to be an alter-

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 16 Chatterjee: Hot Dip Galvanizing

native, more reliable method of measuring the hot The tensile properties of structural steels are not
dip coatings [97]. affected by galvanizing [2, 4].
Galvanized coatings on cast irons can be like silicon- When articles of combined steels of different com-
killed steels, thick, gray and rough with poor positions are galvanized, different pickling and
adherence to the substrate [33]. Commercial gray coating rates and hence different thickness and
iron castings are usually specified for an average appearance on the structure can be expected because
coating of 549 g of zinc per square meter of surface of difference in the chemistry of different steels. If
(ASTM A-153 - 47T) [4]. Malleable iron or white steel is welded prior to galvanizing, any welding flux
iron castings seem to pick up a heavier coating of residues must be removed mechanically. Otherwise,
zinc on an average than a cast iron for the same any leftover residues being non-reactive in pickling
immersion period. Pipe fittings generally are speci- solutions would subsequently hinder adherence of
fied for a coating of 612 g per square meter/side, zinc to the weld. It is, therefore, important to use
or an average coating thickness of 85 mm (coating uncoated electrodes in order to avoid build up of
thickness in micron X 7.2 = coating weight in g per such flux deposits. Alternatively, MIG, TIG or CO2
square meter/side). Coating thickness of plumbing shielded arc welding techniques may be used which
and hardware items are determined by weighing the would essentially produce no welding slag.
articles before and after zinc immersion. Coating The general aspects of designing a plant for hot
on steel sheet is specified over a range from 381 to dip galvanizing of both general open dip and auto-
839 g per square meter/side. matic pipes are briefly discussed elsewhere [47]. It
describes a typical plant layout, cost of chemicals &
7 Designing articles for galvanizing
heating, percentage gross usage of zinc as a function
Certain rules must be followed when designing com- of steel composition and the required thickness of
ponents for galvanizing which in many cases simply zinc, and good storage practice for finish products.
involve good practice to ensure maximum corrosion
protection. A good design requires 8 Cost and economics
a) means for access and drainage of molten zinc, and Galvanizing fortunately enjoys considerable environ-
b) means for escape of gases from internal com- mental cleanliness and product cost stability. The
partment (venting) [2, 4]. cost of the process is not calculated on tonnage or
Basically, in order to provide complete protection surface area alone, but on a combination of plant
by galvanizing, molten zinc must be able to flow utilization and the necessary degree of handling
freely to all surfaces of a fabrication. With hollow of the work. As a consequence of this, together
sections or where there are internal compartments, with continuous development of the process and a
galvanizing of the internal surfaces with easy flow modest labour component, galvanizing is generally
of molten zinc eliminates any danger of hidden competitive in its initial cost as well as in life-cycle
corrosion during service. Vessels and hollow sections cost. It is claimed that no coating is superior to com-
must be vented to atmosphere for the safety of gal- bined hot dip and paint for cost saving with mini-
vanizing personnel and to prevent possible damage mum risk [101]. Usually, the largest cost reductions
to the article. At galvanizing temperatures around result from lower zinc usage which will lead to lower
450 °C, moisture trapped in closed sections is con- energy costs, thinner coatings of zinc on the work,
verted rapidly to superheated steam, generating lower dross and fewer rejects [33]. An important
explosive forces unless vented. More extensive aspect of the economics of galvanizing is the chance
guidance on design for hot dip galvanizing is of a much longer period to first maintenance than
available in BS EN ISO 14713. Of course, clean is possible with paint coatings only. A comparison
steel surfaces are an essential requirement for good of initial coating costs and expected service lives of
hot dip galvanizing. Almost any component can be hot dip galvanizing with those of several commonly
galvanized by designing and building in modules to used paint systems shows that the initial cost is
suit available galvanizing facilities i. e. to be able cheaper with galvanizing than any of the competitive
to physically accommodate in a galvanizing bath. paint systems [1, 2, 4]. The main reason for this dif-

Jahrbuch Oberflächentechnik Band 70 | Eugen G. Leuze Verlag

 Chatterjee: Hot Dip Galvanizing 17

ference is that painting is more labour intensive than 10 Conclusion

galvanizing which is highly mechanised and closely Among the various zinc coating methods, hot dip
controlled factory process. Electroplating has not galvanizing process protects steel surface from
been included in the survey, but the technique cannot rusting by covering it with a very thick (up to
be competitive in price with galvanizing for thicker ~ 100 µm) coating of zinc. This is achieved by
coating with thicknesses greater than about 15 to immersing steel articles in molten zinc. The process
20 mm, due to high cost of electricity involved. is one of the most important and widely used anti-
9 Environmental effect corrosion coating method for protection of steel over
the years. Hot dip galvanizing accounting for zinc’s
In the present time, attention of the authorities and
primary use is estimated to be over 90 % of total
the public at large is becoming increasingly focused
on the environmental performance of industrial pro- zinc consumed for coatings worldwide. Despite all
ducts. This situation makes it necessary to perform these facts, the process is, however, unlike electro-
an analysis on the entire life of the galvanized steel plating of zinc, still not accepted as a well-known,
product from the extraction of the raw materials popular technique outside the mainstream of metal
through the production processes up to the end of finishing industry. The present review updates various
their life and beyond, taking into consideration of aspects of hot dip galvanizing in an effort to im-
the recycling and environmental wastage costs. The prove the existing knowledge of the method and
initial results on Life Cycle Assessment (LCA) in thereby hopefully stimulating resurgence of interest
line with recent comments from the European Com- for the technique in the coating industry.
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Eugen G. Leuze Verlag | Jahrbuch Oberflächentechnik Band 70

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