Chapter 2.

9
Other Methods of Surface Preparation

For most industrial painting jobs, abrasive blast cleaning is the method of choice to prepare the surface
for painting. The next most popular methods of surface preparation are wet abrasive blast cleaning and
waterjetting. There are situations, however, where problems exist with the more conventional methods. This
chapter consists of short summaries of a few alternative methods of surface preparation, some of which may be
applicable in certain situations.

Chapter 2.9.1
Pickling
Dr. Thomas J. Langill and John W. Krzywicki

Introduction
Pickling in the metal finishing industry is a
process in which iron or steel is immersed in acidic
solutions to remove oxides or scale. Normally, all
ferrous metals have a surface oxide from atmospheric
exposure or scale from high temperature rolling and
annealing. Various acids can be used in commercial
pickling including sulfuric, hydrochloric, muriatic, nitric,
hydroflouric, phosphoric, or mixtures of acids. For
efficient pickling, these acids should be active enough
to remove only oxides and scale from the iron or steel
while minimizing the metal wasted through base metal
dissolution. Inhibitors added to the acid solution are
used to reduce the amount of acid attack on the base
metal.
Metal finishers typically encounter two types of
scale. The first type, high-temperature scale, is a
composition of three layers of iron oxide, FeO, Fe3O4,
and Fe2O3, and develops after rolling operations at
temperatures above 1070°F (577°C).1 The second
type, low-temperature scale, consists of two iron oxide
layers, Fe3O4 and Fe2O3, and develops when steel is
heated in an annealing or finishing operation at
temperatures below 1070°F (577°C). Since the steel
and the iron oxides contract at different rates, the iron
oxide layers develop cracks from the outer surface
down to the interface between the iron oxide layer and
the base steel as it cools.
The many cracks in the scale permit the
pickling acid to penetrate to the inner layers of the
scale and to the metal itself. The inner layer, being
more soluble in some acids, dissolves more rapidly,
allowing the bulk of the scale to fall off in the form of
iron oxide flakes. As part of the acid chemical reaction,
hydrogen gas is evolved, thereby helping to blow off
the upper layers of oxygen-rich scale.
If all the scale were blown off at one time and
the metal immediately removed from the pickling
solution, there would be minimal acid attack on the
base metal and little need for an inhibitor. This, how-
ever, does not occur. Scale exists in varying degrees
of thickness on an individual piece of steel, and the
light scale is removed very quickly, exposing the bare,
clean steel. Additionally, all the mill scale may be
blown off prior to a thorough cleaning of any localized
rust areas. Uninhibited acid attacks and pits light scale
areas before the remainder of the scale can be
removed.
Rust, or iron oxides, are more soluble in
sulfuric, muriatic, and phosphoric acids than are mill
scales. Rust is removed by dissolution rather than
being blown off. Rust, unlike scale, continues to
develop cyclically, and if it were not removed along
with the chemicals that caused it, it would continue to
form, even under coatings of paint, oil, etc., when
exposed to oxygen.
Sand or shot blasting is more economical for
rust and scale removal from large assembled struc-
tures such as ship hulls, bridge plates, gas holders,
etc., that are too large and, often, too thickly encrusted
with pitted rust to be pickled in acid. On smaller
assemblies, weldments should be abrasive blast or
mechanically cleaned to remove welding slag prior to
pickling.
 In the United States, sulfuric acid, because of
its low cost, high boiling point, availability, and regen-
eration in the plant, has been used extensively in
pickling low carbon steels. Plant operations not
employing acid regeneration and reclamation are
being curtailed due to the high cost of disposing of
waste pickle liquors. Disposal costs are closely related
to increasingly strict environmental regulations.
Hydrochloric acid is becoming more popular
for pickling steels. Unlike sulfuric acid, hydrochloric
acid pickles efficiently at ambient temperatures, which
decreases energy costs. This, in combination with new
technology being developed in regeneration, will
increase its use over the forthcoming years. In-plant
regeneration of hydrochloric acid is expected to be
available by 2005. The pickling process is divided into
three steps:
• Cleaning and preparing metal
• Pickling
• Treating the pickled metal
Cleaning and Preparing Metal
Cleaning is necessary to remove any material
from steel or iron that would prevent pickling acid from
attacking the oxides and removing scale. The material
most frequently encountered is oil. There are a num-
ber of methods that can be used to remove oil. Oil can
be removed with oil solvents, most of which are
volatile and leave a thin film on the surface. Solvents
can be applied by any convenient means and wiped
off with clean rags. The steel or iron can be degreased
by immersion in solvents or solvent vapors. The latter
method leaves metal free of oil but not from particles
or smut held on the surface by oil film.
Alkali cleaning is relatively inexpensive and
should be done when cleaning prior to pickling is
necessary. This is employed regularly to remove oils,
greases, cutting or forming compounds, etc. Other
contaminants that should be removed prior to pickling
are heavy rust and paint, which, on new steel, mainly
involves shop and mill marks.
Scraping, wire brushing, or abrasive blast
cleaning can remove heavy rust that might prolong
pickling times. Paint and other types of marking can
normally be removed mechanically or with solvents.
Pickling
Sulfuric and hydrochloric acid are commonly
used for steel pickling. Almost identical pickling rates
140
can be obtained from sulfuric and hydrochloric acids
by suitable selection of bath temperature and pickling
bath strength. Hot, dilute solutions of sulfuric acid are
generally used for pickling, while hydrochloric acid is
mostly used at ambient temperature to avoid undesir-
able fuming.
Typical sulfuric acid pickling for low carbon
structural steels may not be suitable for some high-
strength constructional alloy and heat-treated alloy
steels. Some higher carbon and alloy steels burn in
acid very easily, making surface smut more problem-
atic. Test work sampling should occur before pickling
large quantities of fabricated special steels, for which
prior experience or test data is not available. Steel
composition affects the time required for pickling.
Hydrochloric acid is highly volatile and gener-
ates fumes, even at room temperature. Fuming
becomes worse with increasing solution temperatures.
Fumes can cause severe corrosion of equipment and
building structures in the vicinity of the pickle tank.
Therefore, hydrochloric acid solutions are not heated
unless ventilation is available.
Since sulfuric acid pickling solutions are
heated, the process consumes more energy than
hydrochloric acid pickling tanks. Pickling in sulfuric
acid will produce a rougher steel surface than hydro-
chloric acid. However, either acid in combination with
an inhibitor in the pickling bath can yield a smooth
surface finish.
Tanks constructed of mild steel plate, wood, or
polypropylene can be used for both cold and hot rinse,
but ordinary steel, unlined, cannot be used to contain
any of the acid solutions used in pickling. Wood tanks
can be used temporarily to contain sulfuric, muriatic,
hydrofluoric or phosphoric acids, but more permanent
equipment, steel tanks lined with materials that resist
the acids or propylene tanks, should be used to
contain them.
A pickle tank suitably lined and constructed
should be equipped with a large bottom drain for rapid
emptying and easy cleaning, heating coils or another
source of heat, water for diluting acid and for washing
the empty tank, and provisions for adding concen-
trated acid to the bath.
Water should never be added to strong acids.
Even when properly adding concentrated sulfuric acid
to water, enough heat generates to boil and disperse
the acid about. Workers should stay a safe distance
from acid while it mixes with water. In small installa-
tions, steel chutes or pipes should be provided to aid
in the addition of acid. In large installations, the acid
should be pumped through a steel or lead pipe from
the storage or measuring tank to the pickle tank.
It is advisable to have a separate tank for
monitoring the amount of acid added to each pickle
tank. For concentrated sulfuric acid, the storage tank
may be safely constructed of mild steel, since concen-
trated sulfuric acid does not attack mild steel. How-
ever, other acids in concentrated form will attack mild
steel. The acid storage tanks must use material or
linings suitable for the acid being stored.
It is desirable to provide adequate ventilation
around the pickling tanks. Warm air and exhaust ducts
located over or near the tanks are helpful in ridding the
atmosphere of fumes and acid mists. Also, structural
steel within an enclosed pickling area should be
properly coated with an acid-resistant corrosion
protection system.
The rate of steel pickling is affected by the
type of acid used for scale removal, the acid concen-
tration, temperature, inhibitor concentration, and
amount of agitation. Figure 1 shows the effect of
hydrochloric acid concentration on pickling time at
various temperatures. Figure 2 shows the same plot
for sulfuric acid.
Figure 1. Effect of hydrochloric acid concentration on
pickling time at various temperatures.
Sulfuric acid pickling takes place very slowly at
room temperature, whereas hydrochloric acid pickles
effectively at that temperature. The reaction rates for
141
Figure 2. Effect of sulfuric acid concentration on
pickling time at various temperatures.
both acids increase as the temperature is increased.
Faster pickling rates can be obtained with hot sulfuric
acid than with ambient temperature hydrochloric acid.
Sulfuric acid baths are usually maintained at a tem-
perature between 150 and 185°F (66 and 85°C), while
hydrochloric baths are kept at ambient temperatures
between 50 and 100°F (10 and 38°C).1
Figures 1 and 2 also show the effect of acid
concentration. Hydrochloric acid is commercially
available in concentrations up to 35% of 22 Baumé.1
The rate of attack of hydrochloric acid is somewhat
influenced by temperature, but the concentration of the
acid plays a more important role. Hydrochloric acid
becomes increasingly more corrosive with increasing
acid concentration. For sulfuric acid pickling, a concen-
tration of approximately 40% by volume of 66 Baumé
acid is most corrosive to mild steel. However, for
sulfuric acid pickling, the best economics are usually
obtained by operating within a range of 2 to 20% by
volume of 66 Baumé acid. Although the rate of scale
removal and of attack on steel by sulfuric acid is
somewhat dependent upon acid concentration, bath
temperature rather than acid concentration primarily
controls pickling times under normal pickling condi-
tions.
When using hydrochloric acid for pickling, the
desired pickling time obtained by using a particular
acid concentration with the amount of fume produced
by that concentration must be balanced. Lower acid
concentration produces fewer fumes but also produces
longer pickling times. Occasionally, the hydrochloric
Figure 3. Time in the pickling bath is related to the amount of scale removed.
acid baths are slightly heated in order to use even
lower concentrations of acid and reduce fuming. The
tradeoff is, of course, higher energy bills to heat the
acid.
Figure 3 illustrates how the effect of time in
the pickling bath is related to the amount of scale
removed. The shaded region is the ideal region for
scale removal and suggests a longer immersion time.
The effect of dissolved iron on the pickling rate
of steel also depends on the choice of acid. The
corrosion rate of uninhibited hydrochloric acid in-
creases dramatically as acid and iron concentrations
increase. Corrosion rates of uninhibited sulfuric acid
solutions fluctuate very little over wide acid and iron
concentrations. Increasing amounts of dissolved iron
in sulfuric acid eventually have a significant effect on
pickling by delaying scale removal.
Scale removal can be increased with bath
agitation. A stationary film of acid next to the scale
surface decreases in free acid concentration while it
increases in dissolved iron concentration. Both
changes decrease the pickling rate. Faster pickling will
result if fresh acid is brought to the steel surface and
the weak acid contaminated with dissolved iron is
circulated throughout the bath and away from the
metal. Agitation may be obtained by mechanical
142
means or by blowing air or steam up through the bath.
It is necessary on a periodic basis to monitor
the pickling solution to determine the free acid content
and the iron content. These checks should indicate
when acid additions are needed and when the acid
should be discarded or regenerated because excess
iron is found in the bath. Iron content of the acid can
adversely affect the efficiency of the pickling solutions
when it becomes too high. Although hydrochloric acid
pickling solutions are less affected by iron content than
sulfuric pickling solutions, the upper limit can be
anywhere from 85 g/liter to above 20% by weight,
depending on the type of pickling solution.
Over-pickling can occur when the pickling
solution attacks and dissolves the base metal after
scale removal. It usually results because the scale
layers are not uniform. Thicker or more deeply embed-
ded materials require more time for removal. Proper
selection and use of an inhibitor will minimize over-
pickling.
A piece of metal is rarely uniformly covered
with scale. The bare metal areas or areas with very
light scale are attacked at once during acid pickling
while no attack takes place on the heavily scaled
areas. As a result, more metal is removed from the
areas that are bare or are lightly covered with scale
without an inhibitor.
While adequate pickling is necessary, it is
undesirable to over-pickle. This will cause a roughen-
ing or pitting of the base metal. Over-pickling also
causes unnecessary consumption of the pickling acid.
Inhibitors minimize the loss of iron, protect the metal
against over-pitting, reduce acid fumes resulting from
excessive reaction between the acid and the base
metal, and reduce acid consumption.
Both natural and synthetic organic compounds
are used as inhibitors. Natural compounds include low-
grade bran, flour, gelatin, glue, sludge from petroleum,
sulfonated coal-tar products, asphaltum, and wood
tars. The synthetic materials are nitrogen-based
materials such as pyridines, quinidines, aldehydes,
and other compounds containing sulfur.1
Inhibitors are added to isolate the base metal
once the oxides and other contaminants have been
stripped away, preventing the attack on the base
metal. Some inhibitors accomplish this by laying down
a thin film, isolating the acid away from the metal.
Other inhibitors stop the passage of galvanic cell
current and the corrosion process by an action known
as cathodic polarization, essentially preventing the
release of hydrogen at the cathode and stopping the
metal attack at the anode.
The use of an inhibitor with a wetting agent will
provide better drainage of the pickling solution. This
not only will conserve pickling acid but also will mini-
mize the possibility of carrying acid and dissolved iron
into any following processes. Wetting agents can
actually increase the speed of oxide removal. Acid
inhibitors must be stable at all possible operating
temperatures and conditions and must not decompose
in solution, stain, or contaminate the steel. An ad-
equate inhibitor keeps maintenance costs down and
does not emit offensive odors.
Over-pickling causes a roughening of the
whole surface, discoloration of the steel and a de-
crease in size and weight of the part. Over-pickling can
be avoided by removing the material from the bath
promptly when complete removal of scale has been
accomplished. Inhibitors aid in preventing over-
pickling, but do not provide a sure guarantee.
Hydrogen embrittlement can occur when high-
strength steels with very small steel grains are pickled.
Steels in excess of 150,000 psi (1035 MPa) tensile
strength should be cleaned using shot or grit blasting
followed by a very quick immersion in a pickling bath.
143
The proper choice of inhibitor can minimize acid attack
on the bare steel and thus reduce the amount of
absorbed hydrogen gas.
Spent acid is the name given to a pickling
solution that has a chemical content of iron and scale
that renders the acid ineffective. At this point, the iron
starts to crystallize in the bath or the pickling is too
slow. The spent acid must be responsibly discarded or
recycled.
Neutralization is the most common and
simplest way to treat spent acid. The spent acid, or
pickle liquor, is treated with an alkaline chemical such
as caustic soda or lime. An economical neutralizer
would be residual chemicals in alkaline cleaning
solutions. Neutralization of the spent solutions forms
iron hydroxide, which is gelatinous and slow to settle
out. After the spent pickle solution is neutralized, some
method of disposal is required.
Hauling to a disposal site entails contracting a
company to pump out spent liquor into a special tank
carrier for transportation to a site. This site can either
be an authorized disposal facility for this material, a
central recycling plant, or another company able to
utilize the spent pickle solution. Whatever the end
destination, the user is legally liable to ensure that the
material is not disposed of in violation to environmental
laws.
Discharging spent pickle solution in deep wells
is one means of off-site disposal; however, local and
state authorities must permit this.
The alternative to neutralization or disposal
would be an acid recovery by crystallization of the
spent acid solution. Several methods of regenerating
hydrochloric and sulfuric acid are commercially
available for use in plants where the volume and cost
make them viable.
Treating the Pickled Material
When steel or iron are removed from the
pickle bath they are coated with a thin film of pickling
acid and salts, resulting from reaction of acid with iron.
The acid and salts, with the exception of some salts
produced from phosphoric acid, actually stimulate rust
formation and must be completely removed before
they dry on the steel. An ample supply of clean water
must be available for rinsing. Steel, wood, polypropy-
lene, or concrete tanks provided with a skimming
trough to take care of an ample overflow of water are
generally used, although water can be applied liberally
with a hose.
Pickled work should be rinsed promptly,
particularly if the acid is hot. If the film dries, it is
difficult to rinse away and may cause difficulty in many
subsequent operations.
When pickling acid and iron salts are removed
or diluted, metal must be suitably treated in prepara-
tion for the operations that follow. Treatment prevents
steel from rusting and prepares it for painting or other
coating operations such as hot-dip galvanizing. When
pickled steel parts are to be stored, weak alkali
solutions, such as 1/4 to 1/2 ounce per gallon (1.9-3.7
g/L) of sodium carbonate or trisodium phosphate, are
used in a boiling rinse following a cold rinse. The
alkaline surface does not rust rapidly, but if the pickled
steel part is to be stored indefinitely or exposed to
weather it should be passivated in some manner. Alkali
cleaning solutions after pickling are suitable for the
subsequent application of oil but are not suited for the
subsequent application of paint. There are other
treatments that can be used to prevent rusting after
pickling.
Most paints do not adhere well and form
blisters in a humid atmosphere if applied to an alkaline
or neutral surface. For best painting results, the
surface pH should be slightly acidic. When using
special paints, such as inorganic zinc, the best results
occur when paint is applied to a neutral surface. In
pickling processes for inorganic zinc applications, no
further treatment is normally used after the hot water
rinse.
For most paints, other than inorganic zinc, it is
important that the proper acid be used to produce the
correct pH. Phosphoric or chromic acids produce the
best results. Muriatic or sulfuric acids should not be
used because their residues stimulate steel surface
rust under paint.
It is desirable to further clean and treat pickled
and rinsed steel in a phosphoric acid solution prior to
painting. Good results can be obtained by adding
approximately 0.25% by weight of concentrated
phosphoric acid to the hot rinse bath contained in a
steel tank, and maintaining this rinse at a pH of 3 to 5
by addition of acid as small quantities are needed.
The cleanliness of the boiling rinse is impor-
tant, since it is here that a satisfactorily cleaned
surface can be spoiled for painting. For best results
the bath should be discarded daily and the tank
cleaned before making a new bath. This is not practi-
144
cal for large-scale structural pickling operations and
good painting results can be obtained by merely
maintaining a water rinse temperature at 140ºF (60ºC)
or higher and painting promptly while the steel is warm
and dry.
References
1. Hydrochloric Acid Pickling; American Galvanizers
Association: Technical Services Committee, 1979.
2. Anderson, J. D. Pickling: An Art or a Science;
Amchem Products, Inc.
Suggested Reading
The Galvanizing Handbook; Zaclon, Inc., 1996.
Metals Handbook—Volume 5: Surface Cleaning,
Finishing, and Coating, 9th Edition; American Society
for Metals, 1994.
Viljoen, C.L. et al. A Comparative Study of the Use of
HCl and H2SO4 in Acid Pickling in the South African
Hot Dip Galvanizing Industry; Galvanizers Party Ltd.,
1991.
Hudson, R.M.; Warning, C.J. Factors Influencing the
Pickling Rate of Hot-Rolled Low Carbon Steel in
Sulfuric and Hydrochloric Acids. In Metal Finishing;
U.S. Steel Corporation, 1980.
Kleingarn, J.P. Pickling in Hydrochloric Acid.
Intergalva ‘88; VDF, Germany FR., 1988.
About the Authors
Dr. Thomas L. Langill
Thomas J. Langill is technical director of the American
Galvanizers Association (AGA), 6881 South Holly
Circle, Suite 108, Englewood, CO 80112. He has 20
years of experience in materials development and
research and assisted in packaging a laser-diode
system for military uses. Mr. Langill has represented
the hot-dip galvanizing industry at the AGA for the past
7 years. He has a PhD in materials science and
engineering and is a member of NACE.
John W. Krzywicki
A graduate of the University of Wyoming with a degree
in chemical engineering, John W. Krzywicki joined
AGA as a corrosion engineer in 2001. While working
for there, he has become a member of NACE and has
published numerous articles and papers on the hot-dip
galvanizing process, which include its various applica-
tions and corrosion protection.