Canadian Metallurgical Quarterly

The Canadian Journal of Metallurgy and Materials Science

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PICKLING OF AUSTENITIC STAINLESS STEELS (A

REVIEW)

L.-F. LI & J.-P. CELIS

To cite this article: L.-F. LI & J.-P. CELIS (2003) PICKLING OF AUSTENITIC STAINLESS STEELS (A
REVIEW), Canadian Metallurgical Quarterly, 42:3, 365-376

To link to this article: http://dx.doi.org/10.1179/cmq.2003.42.3.365

Published online: 18 Jul 2013.

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Canadian Metallurgical Quarterly, Vol 42, No 3 pp 365-376, 2003

© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)

L.-F. LI1,2 and J.-P. CELIS1
1
Department MTM, Katholieke Universiteit Leuven,
Kasteelpark Arenberg 44, B-3001 Leuven, Belgium
2
Department of Metallurgy, School of Materials and Metallurgical Engineering,
Northeastern University, Shenyang 110006, China

(Received July, 2002; in revised form February, 2003)

Abstract — The effect of hot and cold rolling on the pickling of austenitic stainless steels is introduced.
The formation of an oxide scale and a chromium-depleted layer during annealing, the composition and
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structure of that oxide scale and their effects on the subsequent pickling process are reviewed. The pre-
liminary pickling methods and the mechanism of electrochemical neutral pickling are discussed in detail.
The dissolution of an oxide scale is facilitated by the oxidation of either metallic cations or oxygen anion.
While chromium and manganese oxides dissolve at first, followed by the dissolution of iron oxides, sil-
icon oxide enriches at the surface. The removal of a chromium-depleted layer is the most important step
during final pickling and the dissolution of the oxide scale is inconsequential. The final pickling opera-
tion with traditional electrolytes based on HNO3 + HF is detailed and compared to the environmentally
friendly electrolytes. The latter operation is more advantageous due to its environmental and economical
aspects.

Résumé — L’effet d’un laminage à chaud ou à froid sur le décapage des aciers inoxydables est présenté.
La formation d’une couche d’oxydes et d’une sous-couche appauvrie en chrome pendant détrempage, la
composition et la structure de cette couche d’oxydes et leurs effets sur le décapage sont passés en revue.
Les phases de pré-conditionnements électrochimiques et chimiques sont discutées ainsi que les
mécanismes de décapage électrochimique en milieu neutre. La dissolution de la couche d’oxydes est
accélérée par l’oxydation soit des cations métalliques soit des anions d’oxygène. Les oxydes de
manganèse et de chrome sont dissous en premier lieu suivi d’une dissolution des oxydes de fer. Des
oxydes de silicium enrichissent la surface. L’élimination de la sous-couche appauvrie en chrome est de
loin l’étape la plus importante pendant le décapage chimique et la dissolution de la couche d’oxydes n’est
pas pertinente. Le décapage chimique en milieu traditionnel HNO3 + HF et dans des solutions plus
acceptables d’un point de vue écologique, sont présentés et comparés. Ce dernier procédé apparaît
comme étant le plus indiqué tenant compte des aspects environnementaux et économiques.

INTRODUCTION to enhance the corrosion resistance. A correct pickling

Stainless steels, especially austenitic stainless steels, are
used increasingly for their excellent mechanical properties
and high corrosion resistance. Austenitic stainless steels
are generally continuously casted, reheated, hot rolled and
annealed in a modern operating process and the alloys are
subjected to elevated processing temperatures throughout
the process. Under such conditions, a continuous oxide
scale film is formed covering the metal and a chromium-
depleted layer grows between the oxide scale and the base
material. The two layers eliminate undesirable inclusions
and defects from the surface, but it is undoubted that a sub-
sequent pickling operation should follow to expose the
substrate metal, to improve the surface finishing and thus,
process is a complex operation that includes annealing,
scale removal, complete dissolution of the chromium-
depleted layer and the recovery of highest surface passivi-
ty.
The first literature mentioning the pickling of chromi-
um-iron alloys appeared in 1924 [1]. Two patents on the
pickling of stainless steel with an electrolyte containing
sulfuric acid and a salt, sodium nitrate or copper sulfate,
respectively [2,3] were approved later.
Pickling in a modern operating route consists of sever-
al processes. A scale breaking at high stresses loosens the
scale layer, disrupts it and results in some cracks inside the

CANADIAN METALLURGICAL QUARTERLY

 366 L.-F. LI and J.-P. CELIS
remaining oxide scale so that the electrolyte can easily
penetrate into the oxide scale during pickling. During shot
blasting, the oxide scales can be removed mechanically.
Electrochemical neutral pickling consists of polarizing the
metal surface alternately anodically and cathodically to
condition the oxide scales that can dissolve in the pickling
electrolytes. The last step is a chemical pickling that oxi-
dizes and dissolves the surface metal so that the remaining
oxide scale is undercut and disrupted. The major task of
this operation is to completely remove the chromium-
depleted layer in such a way that the base metal is dis-
solved as little as possible.
Today, quality, cost and environmental concerns are
the three most important factors guiding a pickling opera-
tion. In a modern pickling line more attention is paid to the
pre-treatment steps than ever before. Subsequently, the
stainless steels are electrochemically pickled in a neutral
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sodium sulfate electrolyte and chemically pickled in a
nitric acid-free acidic electrolyte.
In this paper, the effects of hot rolling, cold rolling and
annealing on pickling are discussed. The preliminary and
final pickling processes of austenitic stainless steels in neu-
tral and nitric acid-free electrolytes are reviewed in detail.
HOT AND COLD ROLLING
Hot and cold rolling operations are used to decrease the
gauge of a product to a certain extent at temperatures
above the recrystallization temperature of the material and
at room temperature, respectively, to meet microstructural
and mechanical requirements.
Hot rolling significantly alters the grain size of metals
and the degree of this alteration depends on the following
factors [4]. The degree of deformation determines the
energy stored in the material that is the driving force for
recrystallization to occur. The number and frequency of
deformation steps and the initial and final temperatures
determine the rate of recrystallization and the occurrence
and rate of grain growth. Lower deformation temperature
and larger amounts of deformation produce a smaller ulti-
mate grain size and thus, induce an oxide scale during
annealing with a smaller grain size and a higher chromium
oxide content. Finally, these parameters will further affect
the composition of a chromium-depleted layer. As a result,
the pickling of the oxide scale and the chromium-depleted
layer are influenced by the hot rolling conditions [4,5].
Cold rolling also increases the stored energy. When
coupled to an annealing step, cold rolling changes grain
size in a way that is similar to hot rolling. However, unless
a deformation induced segregation or a phase transforma-
tion occurs, cold rolling has no specific effect on the pick-
ling behaviour [6].
CANADIAN METALLURGICAL QUARTERLY
ANNEALING
During annealing, austenitic stainless steels are heated up to
about 1150 °C and are kept at this temperature for some time
to soften the metal in order to release the work hardening
induced by hot and cold rolling. A uniform grain structure is
obtained depending on the annealing temperature. The elim-
ination of surface defects by forming an oxide scale is
required to improve the corrosion resistance [7]. On the other
hand, processes are required to remove that oxide scale and
the chromium-depleted layer to obtain technological prod-
ucts, but that has to be achieved with a minimum base mate-
rial loss.
Annealing parameters significantly affect the oxidation
kinetics of base materials and consequently the composition
and structure of the oxide scales formed at the surface of
austenitic stainless steels. The main parameters are the base
metal composition, annealing temperature and atmosphere
and the treatment time, which is time at temperature (TAT).
The TAT depends on the gauge of the steel (the thickness of
coils and the diameter of wires), in industrial applications. A
larger gauge needs a longer annealing time and correspond-
ingly, a lower walking speed in the furnace. Chromium and
silicon oxides hinder the diffusion of both oxygen and metal-
lic ions and are known to increase the resistance to oxidation.
Iron increases the oxidation kinetics. Nickel and molybde-
num do not significantly influence the oxidation behaviour.
The maximum annealing temperature ranges from 1100
to 1180 °C for austenitic stainless steels, but it may reach up
to about 1260 °C during reheating. A gas mixture consisting
of a natural gas fuel and a preheated air is normally used for
annealing austenitic stainless steels. The extra oxygen per-
centage in an industrial annealing furnace is between 3 and 6
vol%. Thus, the air to natural gas ratio before combustion
ranges from about 11 to 14.
Properties of the Oxide Scale Film
Various compositions and structures of the oxide scale have
been reported and most researchers state that the oxide scale
on austenitic stainless steels is composed of Cr2O3, Fe2O3
and (Fe,Cr)3O4 spinel [4,7-11]. Some studies conclude a
more stratified structure containing additional constituents,
such as FeO and Fe3O4 [6,8-10,12,13], NiFe2O4, Fe3O4 and
chromic oxide (Fe,Cr)2O3 [11]. The (Fe,Cr)3O4 spinel is a
non-stoichiometric compound mixture of chromium and
iron oxides including Fe2+, Fe3+ and Cr3+. The properties of
such a spinel are in between those of chromium and iron
oxides. (Fe,Cr)2O3 is a corundum-type non-stoichiometric
oxide phase containing Fe3+ and Cr3+ [14,15]. The Cr2O3
films are fairly adhesive and protective, but the iron oxide
films are quite permeable due to their loose and porous
structure. In some cases, initially protective scales may
become non-protective due to the formation of iron oxides
or spinel after an extended oxidation.
 PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)
Ozturk et al. [7] reported that the oxidation kinetics and
the properties of oxide scales are greatly dependent on the
annealing time and atmosphere. In the atmosphere used in
industrial furnaces, the oxide scale grows at a very low ini-
tial rate during the first 10 minutes and a large increase of
the oxidation rate is noticed at longer annealing times.
At short annealing times in the range of seconds up to a
few minutes, the oxidation rate is very low and nearly inde-
pendent of the annealing atmosphere. A protective layer
rich in Cr2O3 forms on the sample surface [7]. Hildén et al.
[16,17], Matsuhashi et al. [15] and Kiya et al. [18] investi-
gated the oxide scale on the surface of austenitic stainless
steel AISI304 with glow discharge optical emission spec-
troscopy (GDOES) or secondary ion mass spectrometry
(SIMS). They found that oxygen is distributed throughout
the scale film, but is present mostly at the most outer layer
of the scale (Figure 1 [16,17]). The maximum manganese
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content is noticed close to the surface. The maximum
chromium content is farther away from the surface than the
manganese one. The iron content remains very low in this
region. Iron oxides are located in the inner layer of the
oxide scale below a chromium and manganese enriched
region. A slight enrichment in silicon oxide as SiO2 [15] is
found at the interface between the oxide scale and the
metal. Thin film X-ray diffraction (TFXD) is used to deter-
mine the oxide scale structure formed at a short annealing
time, but the technique is difficult to apply. This is the main
reason why the structure of oxide scales in thin scale films
has not yet been pointed out in literature.
At an increasing annealing time, the oxidation kinetics
and the oxide scale properties become significantly depen-
dent on the annealing atmosphere [7]. When the air/fuel
ratio is equal to or less than the stoichiometric ratio of 9.53
for the complete combustion of natural gas, a pure iron
oxide layer rather than a protective one forms at the surface
due to the faster diffusion rate of iron ions to the gas/oxide
interface. Accordingly, the weight gain due to oxidation
Fig. 1. Depth profile of an oxide layer on annealed AISI 304 by GDOES
(Annealing conditions: 1140 °C, 2.5 minutes, 6% O2) [16,17].
367
increases linearly at a rather high initial rate and subse-
quently by a parabolic regime throughout the oxidation
process (Figure 2) [7]. If the air/fuel ratio is above 11, as
used in short time annealing, the initial oxidation rate is
very low. This indicates that a protective layer enriched in
Cr2O3 forms at the surface. The oxidation rate slowly starts
to increase after about 10 minutes due to the formation of
iron oxides. A few minutes later, the surface is completely
covered with iron oxide and a spinel layer and, as a conse-
quence, the scale grows at a very fast rate. At medium
air/fuel ratios ranging from 11 to 13 close to the atmosphere
in industrial furnaces, the scale is composed of two layers
after a long period of oxidation. The outer layer is com-
posed of iron oxides and the inner layer of a spinel. The
topography and cross section of such an oxide scale are
shown in Figure 3. Different layers of oxide scale can be
seen in Figure 3a and the internal oxide scale, mostly in
islands, is indicated in Figure 3b. An inward oxidation also
occurs by diffusion of oxidizing agents through cracks,
grain boundaries, and micro channels. The overall oxida-
tion rate may be controlled by the diffusion of iron upwards
and oxidizing agents downwards through cracks and micro
channels. When the air/CH4 ratio is increased to 18, the
scale is made up of very small crystals, octahedral in shape,
corresponding to the structure of a (Fe,Cr)3O4 spinel. This
scale adheres very well and the transport of chromium, iron
and oxygen ions through this layer is very low. Therefore,
the oxide scale grows at a very low rate. The rate of scale
formation depends on the mass transfer once a thin layer is
Fig. 2. Weight gain as a function of the duration of an oxidation treatment
at 1000 °C for AISI 304 [7].
CANADIAN METALLURGICAL QUARTERLY
 368 L.-F. LI and J.-P. CELIS
a ling solution and this furthermore facilitates the chemical
Lower layer
of external
oxide scale
Upper layer
of external
oxide scale
b less steels takes place at different rates and causes a
Metal
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Internal oxide scale
External oxide scale
Ni deposit
Fig. 3. SEM images of the a) topography and b) cross section of an oxide
scale produced by practical preheating and annealing on AISI 304. (A
nickel top layer has been electrodeposited to enhance the metallographic
cross sectioning).
formed. The mass transfer through the spinel is very low at
temperatures higher than 1000 °C [19,20]. The chromium
content in the protective layer is then much higher than in
the bulk material. As a consequence, the chromium content
in the underlying metal close to the oxide scale is depleted
[21,22].
Properties of the Chromium-Depleted Layer
Chromium is preferentially oxidized to Cr2O3 or a spinel
when stainless steel is exposed to an oxidizing atmosphere
at high temperatures. This results in a region in the base
metal underneath the oxide scale that is significantly
depleted in chromium to an extent depending on the initial
chromium content in the alloy [23]. After the formation of
this chromium-depleted layer, two dissimilar metal layers
are in contact with each other [24]. In this case, an electro-
chemical cell is established with the base alloy as the cath-
ode and the chromium-depleted layer as the anode. This
induces an intergranular corrosion or stress corrosion
cracking in this layer. Therefore, the corrosion resistance of
CANADIAN METALLURGICAL QUARTERLY
the chromium-depleted layer is greatly reduced in a pick-
removal of this layer [4,23].
In anodic polarization curves, a significant increase of
the anodic current density for the chromium-depleted layer
is noticed compared to the bulk alloy [25]. This confirms a
higher corrosion rate of the chromium-depleted alloy in
comparison to the original bulk alloy and supports the need
of a removal of the chromium-depleted layer to obtain an
adequate corrosion resistance which achieved with a final
pickling step.
The formation of metal oxide is related to the diffusion
rate of that particular alloying metal under the annealing
conditions. The diffusion of alloying constituents in stain-
chromium-depleted layer to a different extent. As a conse-
quence, the thickness and composition of the chromium-
depleted layer depend on the annealing conditions. The
thickness of that layer varies generally between a few hun-
dred nanometres and a few micrometres.
Effect of the Oxide Scale on Pickling
The composition and the structure of the oxide scale are
determined by the annealing parameters and they affect the
pickling.
The time required for the dissolution of the oxide scale
decreases with increasing annealing temperatures.
Different reasons have been argued. Lee et al. [11] consid-
ered that the iron content is high in the oxide scale and this
widens the chromium-depleted layer at the oxide/metal
interface at higher temperatures and enhances the ability to
remove the scale. Fernado et al. [26] reported that the oxide
scale annealed at higher temperatures develops a prominent
chromium-rich oxide scale and the bonding between the
oxide scale and steel matrix may be weakened due to the
increased chromium-depleted layer.
Pickling is claimed to be more effective at a higher con-
tent of manganese and chromium oxides and a low content
of silicon oxide in the scale film [18]. Such an oxide scale
can be obtained by annealing at a lower preheating rate
below 400 °C, a rapid heating rate from 400 to 700 °C and
an annealing for more than 10 seconds when the tempera-
ture is above 1000 °C. Such processing results in a thin
scale thickness, high Cr/Fe and Mn/Fe ratios, a low Si/Fe
ratio in the scale and a scale dissolution that is significant-
ly increased during pickling.
The annealing atmosphere can also be optimized to
achieve both a complete combustion of the heating gas and
the formation of a porous, less adhesive spinel-type oxide
scale. This can be achieved since the dissolution of that
type of oxide scale is easier than a compact Cr2O3 layer [7].
 PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)
DESCALING, PICKLING AND PASSIVATION
The pickling of stainless steels is often performed in 4 suc-
cessive steps: mechanical descaling, preliminary pickling,
final pickling and passivation.
Mechanical descaling is usually carried out by scale
breaking and/or shot blasting. Both processes modify the
scale film and make the subsequent pickling more effec-
tive. Shot blasting is one of the fastest descaling techniques
for hot rolled products [27]. Hardened carbon steel or sili-
ca shots are dropped or directed at a rate between 40 and 90
m·s-1 on to the scaled surface [4]. The shape of the shots is
irregular or spherical in diameters ranging from 0.15 to
0.60 mm. Some oxide scales are broken and disrupted dur-
ing shot blasting. However, some surface defects can be
induced and a work hardening can take place. The thick-
ness variation can be up to 200 mm [28] and a contamina-
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tion of the surface can take place. A large amount of silicon
and oxygen was found when silica grids were used [29].
Preliminary and final pickling processes are applied to
remove contaminants from the stainless steel surface. This
results in a metallically clean surface on which a protective
passive layer can form. These processes also remove the
outer surface layer containing mechanically induced tensile
stresses and thus, lower the risk of stress corrosion crack-
ing [30,31].
The different metal oxides obtained at the surface of
austenitic stainless steels after a short period of annealing
and their removal operations are schematically illustrated
in Figure 4. Mechanical descaling and preliminary pickling
contribute mainly to the removal of the oxide scale and the
final pickling removes the chromium-depleted layer.
In some cases, the pickled surface can subsequently be
passivated in a mild oxidizing solution to increase its cor-
rosion resistance. Such solutions are warm dilute nitric
acid, ammonium persulfate, dilute hydrogen peroxide or a
citric acid-sodium nitrate mixture [32,33]. The resulting
*MD: mechanical descaling, PP: preliminary pickling and FP: final pickling
Fig. 4. Schematic illustration of different surface layers after annealing
and their removal methods.
369
transparent passive film is composed of oxides and hydrox-
ides plus adsorbed oxygen. Its thickness is about 0.1 mm
and that thickness can be increased by either exposing the
material to oxidizing solutions or by anodic passivation
using electrochemical techniques. However, this passiva-
tion stage is not required in many applications because
stainless steels are self-passivating in air due to their high
chromium content.
PRELIMINARY PICKLING PROCESSES
There are two objectives for these preliminary pickling
processes. The constituents in the oxide scale are electro-
chemically or chemically altered to increase their solubili-
ty in the pickling solutions. The metallic ions are oxidized
and the oxide scale is loosened to enhance the effectiveness
of the final pickling operation.
Classification of Preliminary Pickling Processes
Taking into account the alloy composition, heat treatment
history, environmental considerations and process costs,
various processes are available for the preliminary pick-
ling. These processes are chemical acid pickling, electro-
chemical acid pickling, salt bath pickling and electrochem-
ical neutral pickling.
In chemical acid pickling, acids are used to reduce or
oxidize the oxides in the scale in order to increase their sol-
ubility in the pickling solutions. Mixtures of H2SO4 and
HCl or mixtures of H2SO4 and NaCl descale a metal by
reducing the oxides and also liberating hydrogen at the
oxide/metal interface [4]. HCl is much more aggressive to
iron oxide than H2SO4. When coupled with H2O2 for pick-
ling austenitic stainless steels, the resulting ferric chlorides
may cause a pitting of the base material. Nitric acid oxi-
dizes the scale to higher oxidation states and thus increases
the solubility of the scale [34].
Electrochemical acid pickling with H2SO4 can be traced
back to the 1920s. Experimental studies have been detailed
in a number of publications [25,35-39]. This pickling
method can be classified into anodic, cathodic and alternat-
ing current pickling operations. Anodic pickling either
electrically oxidizes and dissolves the surface oxide scale
or brings the surface into a passive state. When the surface
is passive, then the base metal undergoes less attack than
the oxide scale, and oxygen gas is released at the surface.
The oxygen gas stirs the solution, uplifts the surface scale
and oxidizes contaminants such as organic impurities. In
cathodic pickling, the work piece acts as a cathode. The
base metal is electrochemically protected, while the oxide
scale is reduced. This process is faster than the anodic one
and hydrogen gas generated at the metal surface contributes
to the stirring of the solution and the lifting off of the
oxides. However, this hydrogen reduction may result in a
CANADIAN METALLURGICAL QUARTERLY
 370 L.-F. LI and J.-P. CELIS

hydrogen embrittlement. In the alternating current pickling,

Fresh
anodic and cathodic polarizations are altered at a certain electrolyte
frequency. This can also be achieved by using two tanks. In
the first tank, the strip is made cathodic with respect to the
counterelectrode. Here the base metal is electrochemically
protected and hydrogen gas lifts off the oxides. The strip
then enters in a second tank where the strip is anodically
polarized. Here, the surface scales oxidize and the release
of oxygen at the surface lifts up the scale.
Circulating Neolyte
For austenitic stainless steels, this electrochemical acid tank recovery Sludge
pickling requires some cautions because of the risk of sur-
face pitting. The probability of pitting increases for thicker Fig. 5. Neolyte pickling system [40].
oxide scales because the metal underneath breaks in the
oxide scale reacts more rapidly than the base metal still
covered with an oxide scale. This results in pitting before
The potential of the steel at the cathodic pole remains at
the bulk of the scale is removed.
-0.5 V when the current density is between 2.2 and 3.3
A·dm-2 [43]. The anodic potential depends not only on the
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Salt bath pickling increases the scale removal of stain-

current density but also on the number of sections. This
less steels, results in a uniform surface finish and decreas-
confirms the dissimilar state of the anodes in different sec-
es the duration of pickling needed to remove the scale
tions. Indeed, the lead anodes undergo corrosion cracking
[4,34]. This pickling operation can be performed in a
to various degrees. As illustrated in Figure 6 [43], the strip
reducing molten bath, an oxidizing molten bath, an oxidiz-
at the cathodic pole has a high negative potential (down to
ing aqueous bath or an electrolytic molten bath.
-2 V) and the strip at the anodic pole has a potential lower
than 2 V. Hydrogen evolves at the cathodic pole of the strip
Electrochemical neutral pickling was developed in
and oxygen at the anodic pole.
Austria [40] and is known as the Ruthener Neolyte Process.
This electrochemical neutral pickling operation involves a
Na2SO4 solution at temperatures between 65 and 85 °C
[41,42]. It is the predominant preliminary pickling process
in modern practices. The main advantages are an excellent
pickled surface, a reduction of the metal losses with avoid-
ance of over pickling, a facility for controlling the pickling
rate by adjusting the current strength, an improvement in
the service life of the plant, lower operating and mainte-
nance costs, better working conditions for operators and
fewer problems arising from effluents [41,43].
Fig. 6. Potential distribution along stainless steel strip during pickling
Since the neutral electrolyte attacks neither the chromi- with a current of 1 kA in each section (vs. SCE) [43].
um-depleted layer nor the base material, a post treatment
with a mixed acid is required for all grades of austenitic
stainless steel to remove the chromium-depleted layer
caused by the annealing.
Surface topography and cross-section views of the sur-
face finish obtained after electrochemical neutral pickling
are shown in Figure 7. The surface is still partly covered
Electrochemical Neutral Pickling
with oxide scale and partly exposed to air. The internal
In an electrochemical neutral pickling bath, pairs of anodic oxide scale (Figure 7b), is not removed by electrochemical
and cathodic electrodes are used to form two half-cells, neutral pickling because this process does dissolve metal
respectively facing the upper and lower surfaces of a stain- and the dissolution of internal oxide scale is, therefore,
less steel strip (Figure 5 [40]). The moving steel strip in the kinetically hindered. The internal oxide scale is distributed
bath passes the gap between upper and lower electrodes. mostly in the Cr-depleted layer and will be removed along
The polarization is achieved without making contact and with this layer in a final pickling operation.
the anodic current density ranges between 5 and 30 A·dm-2
[43]. The current passes through the strip which is essen- Different mechanisms of electrochemical neutral pick-
tially a bipolar electrode. The opposing anodic and cathod- ling have been proposed. Braun [41] reported that during
ic poles of the strip correspond to the bath cathode and the anodic cycle, anions are not discharged, but metal
anode, respectively (Figure 5 [40]). cations are formed on dissolving the scale. The anodic

CANADIAN METALLURGICAL QUARTERLY

 PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)
a Furthermore, Shapovalov et al. [43] pointed out that the
Remaining
oxide scale
Exposed metal
b
Ni deposit
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Non-removed
internal oxide scale
Metal
Fig. 7. SEM images of the a) topography and b) cross section of elec-
trochemically pickled stainless steel AISI 304.
charge is consumed by the oxidation of oxygen in the
scale. Shaprovalov et al. [44] proposed that the scale dis-
integration is due to the electrochemical oxidation of the
metallic species in the scale to higher oxidation valences.
A scale dissolution proceeds at high anodic potentials and
the mechanism is similar to the transpassive behaviour of
stainless steels. A common feature of these mechanisms is
that the dissolution rate is greatly reduced when the scale
is removed and there is no risk of excess pickling or exces-
sive material loss. It was pointed out that during electro-
chemical neutral pickling, chromium, manganese and iron
oxidize to higher valence ions as Cr2O72– [18], MnO –4 [45]
and probably FeO42– [18]. The dissolution rates of chromi-
um and manganese are high at the start of the pickling,
while the dissolution of iron starts rather later and takes
place at a slower rate. Silicon oxidizes to SiO2 and this
oxide is not soluble in the pickling electrolyte. This mech-
anism was also supported by Matsuhashi et al. [15]. On
anodic dissolution of the oxide film, an anodic current aris-
es from the oxidation of Cr3+ in (Fe,Cr)2O3 and FeCr2O4 to
Cr6+ and from the oxidation of Fe2+ in FeCr2O4 to Fe3+.
371
mechanisms of electrochemical acid pickling and electro-
chemical neutral pickling are different. In the former
process, the metal and the oxide scale dissolve at a poten-
tial region where an active dissolution of steel takes place.
The latter process occurs in the transpassive region due to
an anodic current flowing through the metal from an exter-
nal source. Dunaevskii et al. [46] claimed that the main
process of electrochemical neutral pickling is the electro-
chemical dissolution of subscale metal. This causes the
scale to lose its bond to the substrate. This oxide removal
mechanism is resumed by the fact that the oxide scale
remains wholly or partly unchanged. However, this mech-
anism has not yet been supported by other researchers so
far.
More recently, Hildén et al. [16,17] investigated the
electrochemical neutral pickling of stainless steel AISI 304
and 306 L in 15 wt% Na2SO4 with an Avesta cell by using
potentiostatic and galvanostatic polarizations. They pro-
posed a mechanism based on a three-stage dissolution
[16,17]. This model gives a relationship between the dis-
solution sequence of different oxides and the polarization
parameters. Galvanostatic pickling is taken as an example
here. In stage 1, where the scale is enriched with chromi-
um and the outer layer contains a high amount of man-
ganese, the preferential dissolution of chromium and man-
ganese oxides occurs at anodic currents. When the chromi-
um dissolution proceeds, the potential lowers. When the
chromium content lowers, the scale becomes enriched with
iron. The potential required to keep the current constant
then increases or levels off. The iron content is about 25 to
30%, and the chromium content is decreased to below 30%.
In stage 2, the potential increases or stays leveled and the
total chromium and manganese contents in the outer layer
of the scale diminish below 10%, iron increases to about
60%, and silicon enriches at the surface. After this stage,
the thickness of the oxide layer is less than 20 nm and most
of the original oxide scale is dissolved. In stage 3, the
potential decreases and finally levels out at a steady state
value where the base material dissolves by a transpassive
mechanism. As the dissolution of the base material pro-
ceeds, the iron gradient with depth in the surface profile
becomes steeper. Silicon oxide is not electrochemically
oxidized to a higher valence and remains at the surface after
a prolonged polarization. In conclusion, it can be stated that
manganese and chromium oxides dissolve primarily and
iron oxides follow in a neutral electrolyte. Silicon oxide
does not dissolve and concentrates in the remaining thin
scale film. The silicon enriched scale and the chromium-
depleted layer have to be removed in a final pickling step.
The most influential factors in electrochemical neutral
pickling are temperature, Na2SO4 concentration, metallic
ions produced, electrical conductivity of the electrolyte
and polarization parameters. The anodic dissolution of the
oxide films is virtually independent of pH [15].
CANADIAN METALLURGICAL QUARTERLY
 372 L.-F. LI and J.-P. CELIS

FINAL PICKLING PROCESSES

a
The aim of a final pickling process is to remove the remain-
ing silicon enriched oxide scale and the chromium-deplet-
ed layer. This is done in a mixture of acids and oxidizing
agents to maximize the corrosion resistance of the stainless
steel surface as well as to facilitate the further cold rolling
if the steels are hot rolled. At the same time, the dissolution
of a minimum amount of bulk steel is necessary by this
processing to achieve the desired whitening effect.
However, an excessive dissolution of the base metal usual-
ly happens. This results in the loss of chromium and nickel
and increases the consumption of acids in the pickling bath.
Therefore, the ideal final pickling solution is one that easi-
ly penetrates into the remaining scale film, rapidly dis-
solves the chromium-depleted layer and dissolves only a
small amount of bulk steel. The most important parameters
b
for final pickling are the constituents and their concentra-
Ni deposit
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tions in the pickling solution, temperature, pickling time,

dissolved metal concentration and agitation conditions.
According to the Pourbaix diagrams calculated by
Beverskog et al. [47], a lower pH achieved by mixed acids,
a higher redox potential by oxidizing agents and a lower
content of produced metal ions in solution by the use of
complexing agents facilitate the dissolution of metals.
Intergranular corrosion

Ferric sulfate was first introduced as an oxidizing agent. Metal

Its combination with hydrofluoric acid results in a good
pickling finish for a variety of stainless steel products
[48,49]. It is generally accepted in literature that the final
pickling of stainless steels is accomplished by an undercut-
ting of the oxide scale and the high chemical reactivity of the
chromium-depleted layer essentially controls the pickling
rate [17,32]. The dissolution of the oxide scale is inconse-
quential to the actual removal of the chromium-depleted
layer. It is important that the oxide be sufficiently disrupted,
released and flaked to permit the penetration of the pickling
solutions [25,35]. The defects in the scale, such as pores and
cracks promote this penetration. The chromium-depleted
layer that supports the oxide scale plays a very important
role in pickling. It was estimated that a final pickling bath
functions for 85% of the dissolution of the metal and for 10-
15% of the dissolution of the oxide depending on the base
metal composition and the scale formation conditions such
as time, temperature and annealing atmosphere [28]. The
electrochemical characteristics of the dissolution and passi-
vation of this chromium-depleted layer are very different
from those of the base alloy [35,50]. HF is widely used to
increase the dissolution kinetics and to bring the pickling
working conditions to induce the active dissolution of both
the base alloy and the chromium-depleted layer [36].
Fig. 8. SEM images of a) topography and b) cross section of chemically
pickled stainless steel AISI 304.
Traditional Final Pickling with Nitric and Hydrofluoric
Acids
Mixtures of HNO3-HF are the most commonly used final
pickling solutions for austenitic stainless steels in modern
pickling lines due to their high effectiveness. Each chemi-
cal in the pickling bath operates individually without any
synergistic effect. The respective acid concentrations
depend on the type of plant, the type of steel to be pickled,
the steel surface property and the shape of the part to be
treated [51]. The pickling effects of the chemicals on scale
free and oxide covered surfaces are different. This suggests
that while dissolution may be important in pickling, the dis-
solution of the bulk alloy may not be critical. The acid con-
centration varies depending on whether hot or cold rolled
products are involved [28].

An example of a chemically pickled surface finish is
given in Figures 8a and 8b. The surface is completely free
of oxides; however attention has to be given to the inter-
granular corrosion that lowers the corrosion resistance of
the base material.
HF acts as a generator of H+ ions, a complexing agent
for Fe3+ and Cr3+ ions, a redox potential stabilizer of solu-
tions and an effective depassivator of the passive film com-
posed of various mixtures of nitrogen and iron oxides [51-
54]. The presence of iron involves the formation of a vis-

CANADIAN METALLURGICAL QUARTERLY

 PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)
cous layer of the NO2xFey type ferric nitrosyl. The increase
of HF induces the complexing of Fe3+ ions and thus, the
destruction of the passive layer. It was found that the disso-
lution rate of AISI 304 alloy is directly proportional to the
HF concentration in HNO3-HF mixtures [55].
HNO3 acts as a generator of H+ ions, an agent for rais-
ing the redox potential, a passivating agent, an oxidizing
agent of the metal and a dissolution agent of oxide scales.
Its disadvantages are related especially to the presence of
nitric acid which results in nitrates in effluents and nitrous
gas in gas emissions during pickling.
The reactions in HNO3-HF mixed acid solutions were
detailed by Henriet [28]. In HNO3-HF baths, the ionic or
molecular species present are HF, H+, NO–3, NO+2, NF–2, Fe3+,
Cr3+ and N2+. In aqueous solutions and in the presence of
metals, nitric acid contains HNO2 and its dissociation prod-
ucts interact to form NO, NO2, N2O3, N2O4, NO+ and NO+2.
Downloaded by [New York University] at 03:00 09 March 2016
HF reacts with Fe3+ (and Cr3+) to produce the complexing
ions:
Fe3+ + F– Æ FeF2+, Fe3+ +2F– Æ FeF2+, Fe3+ + 3F– Æ FeF3 (1)
An addition of HF to moderately concentrated baths allows
nitric acid to be regenerated.
The chromium-depleted layer is attacked by the follow-
ing reactions:
Fe + 4H+ + NO–3 Æ Fe3+ + NO +2H2O (2)
Cr + 4H+ + NO–3 Æ Cr3+ + NO +2H2O (3)
3Ni + 8H+ + 2NO–3 Æ 3Ni2+ + 2NO +4H2O (4)
The attack of oxides sometimes happens with the same
type of reaction as the formation of cations and the release
of NO. NO produced by Equations 2-4 is then oxidized by
air to NO2.
Environmentally Friendly Final Pickling
The use of mixtures of nitric and hydrofluoric acids during
the pickling operations results in two serious problems, an
environmental pollution and a sludge formation processing.
Nitrate effluents produced during pickling are polluting and
their processing cost is very high. The regulation of the per-
mitted level of nitrate in process effluents becomes increas-
ingly strict. Nitrous gases are emitted during the pickling
(Equations 2-4) and by the following reactions:
Fe + 6H+ + 3NO–3 Æ Fe3+ + 3NO2 + 3H2O (5)
Cr + 6H+ + 3NO–3 Æ Cr3+ + 3NO2 + 3H2O (6)
Ni + 4H+ + 2NO–3 Æ Ni2+ + 2NO2 + 2H2O (7)
373
However, the emission of nitrous gases can be sup-
pressed by an injection of hydrogen peroxide [56]:
2NO2 + H2O2 Æ 2HNO3 (8)
NO + NO2 + 2H2O2 Æ 2HNO3 + H2O (9)
2NO + 3H2O2 Æ 2HNO3 + 2H2O (10)
Moreover, according to the Pourbaix diagrams, it is
possible to replace HNO3 by any viscous substances situat-
ed above the reduction range of nitric acid [28,45]. These
include oxygen, air and hydrogen peroxide (H2O2).
Hydrogen peroxide is completely non-polluting, miscible
with water, weakly acidic in aqueous solution and acts as an
oxidizing agent in pickling solutions with the formation of
water according to the following reaction [57].
H2O2 + 2H+ + 2Fe2+ Æ 2H2O + 2Fe3+ (11)
Hydrogen peroxide was first introduced in the final
pickling of austenitic stainless steels at Daido Steel [58].
Hydrogen peroxide can be induced by injection into the
recirculated pickle liquor through a spurge pipe or a spray
pickling facility [56]. With the introduction of hydrogen
peroxide, the consumption of nitric acid can be significant-
ly reduced or completely avoided. There are no major plant
modifications needed and hydrogen peroxide has no
adverse effect on the stainless steel product quality.
In the UG3P pickling method [28,59], the oxidation of
Fe2+ and its complexes are the main reactions in solution.
The oxidized metal/solution reaction involves two types of
reactions depending on the degree of oxidation of the fer-
rous ions. If Fe3+/Fe2+ >1, then
3Fe3+ + Fe Æ 3Fe2+ (12)
and Fe2+ is then reoxidized to Fe3+ by H2O2. If Fe3+/Fe2+ <1,
then
Fe + 2HF Æ H2 + FeF2 (13)
Electrochemically, the UG3P process may be consid-
ered as a “potentiostatic” process. The baths can be practi-
cally adjusted in such a way that the main variable is the
nature of the metal to be pickled.
Recently the CLEANOX252 pickling process was
developed to suppress the use of nitric acid in a final pick-
ling by using a solution containing H2SO4, Fe(SO4,), HF,
inhibitors, wetting agents and stabilized H2O2 [50]. The
function of hydrogen peroxide is to accept the number of
electrons required to oxidize ferrous ions to ferric ions. An
adequate H2O2 proportion gives the solution a redox poten-
tial, thanks to the Fe3+/Fe2+ balance [54,60], which fulfils
the requirement of a controlled potential pickling where the
CANADIAN METALLURGICAL QUARTERLY
 374 L.-F. LI and J.-P. CELIS
dissolution rate of the chromium-depleted layer is the high-
est [61,62].
Patents on some other final pickling operations with
solutions containing at least one acid and one oxidizing
agent have been reported [51-54,60-66]. Hydrogen perox-
ide is widely used in these operations as an oxidizing agent
of ferrous ions into ferric ions and is used to increase the
bath redox potential [50-52,54,60-66]. Accordingly, the
alloy in the chromium-depleted layer is oxidized and the
scale tightly adhering to the metal is activated and decom-
posed. Hydrochloric [51,62,64,65], hydrofluoric [50-
54,60,61,66] and sulfuric [50,52-54,61,62,65] acids con-
tribute to the total and free acidity of the solution and, in
consequence, to the dissolution of the oxide scales activat-
ed by hydrogen peroxide. The pickling rate in such solu-
tions depends on the steel based constituents, type and
adherence of the oxide to be removed, solution temperature
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and composition, reaction product concentrations, agitation
condition, time of processing and presence or absence of
inhibitors and accelerators [63].
Stainless steels are susceptible to intergranular stress
corrosion cracking (IGSCC) when used in boiling water
containing hydrogen peroxide even at a low concentration
of 0.8 ppm [67-69]. However, the influence of hydrogen
peroxide in an inorganic acid pickling solution on the inter-
granular corrosion is still unknown.
The introduction of nitric acid free pickling processes
presents many advantages. These processes lead to the total
avoidance of nitric acid and thus the suppression of toxic
NOX emissions in vapours and nitrates in effluents. These
processes result in a reduction of the number of treatment
baths and a reduction in the consumption of HF. Moreover,
these processes can be operated at a low temperature, even
at room temperature. Accordingly, the cost of the pickling
operation is decreased. A further advantage is the effect on
the pickling surface finish. In certain cases, the pickling
time can be shortened with these solutions, over-pickling
resulting from HNO3-HF mixture is avoided and the inter-
granular corrosion is greatly reduced. This accounts for an
improvement of product quality. Concequently, the lower
attack on the metal surface reduces the weight loss of the
steel processed.
Dissolution of Metal
The dissolution rate of the chromium-depleted layer in
pickling solutions is higher than that of the bulk stainless
steel. The rate and efficiency of the final pickling operation
are largely determined by this layer [25]. The dissolution
behaviour of the chromium-depleted layer is affected by
factors such as pickling time and temperature, constituents
and their concentrations in pickling solutions and the agita-
tion conditions.
CANADIAN METALLURGICAL QUARTERLY
Price et al.[32] investigated the dissolution kinetics of
the chromium-depleted layer in HNO3-HF mixed acids.
With the increase in pickling time, the weight loss due to
the dissolution of chromium-depleted alloy increases pro-
portionally with the pickling time within 140 seconds. The
weight loss also increases with the decrease of chromium
and nickel contents in the alloys as well as with the increase
of the concentration of nitric and hydrofluoric acids in the
pickling solution. A discontinuity of the dissolution rate is
noticed between the alloys containing 12 and 14% chromi-
um, respectively. This is due to a change in the phase in the
alloy from an austenitic to a ferritic one as the alloying con-
tent decreases[70]. Thus, attempts to optimize the final
pickling must consider the effects of chromium depletion
[23]. This discontinuity also confirms the industrial evi-
dence that an HNO3-HF mixture should rapidly dissolve
any off specification surface alloy and avoid the removal of
the underlying stainless steels.
The dissolution of the bulk steel may not be critical in
determining the rate of pickling; it controls the amount of
bulk steel dissolved. The influencing factors are tempera-
ture, acid concentration, dissolved metal concentration and
agitation [4]. Agitation is very important since it affects
mainly the cathodic reduction of the oxidizing agents.
There is no dissolution of austenitic stainless steels if the
concentration of nitric acid in solution decreases below a
certain amount [24,71]. Moreover, temperature has a sig-
nificant effect on the dissolution of austenitic stainless
steels.
CONCLUSIONS
Hot rolling parameters influence not only the ultimate grain
size of stainless steels but also the properties of the oxide
scale and the chromium-depleted layer. The surface conta-
mination is removed by annealing. The properties of the
oxide scale are greatly dependent on the annealing time and
temperature and influence the pickling efficiency. When
the air/fuel ratio in the annealing furnace ranges between 11
and 13, the maximum content of manganese, chromium
and iron oxides distributes somewhere in sequence from
the air/oxide towards the oxide/metal interfaces SiO2 is
detected mainly at the oxide/metal interface. This situation
prevails at a short annealing time. At an increasing time, the
oxide scale is composed of two layers, namely, iron oxides
in the outer layer and a spinel in the inner layer. The
chromium-depleted layer is less corrosion resistant than the
base material and this facilitates the final pickling.
The pickling of stainless steel is often performed in suc-
cessive processing steps consisting of a mechanical descal-
ing, a preliminary pickling, a final pickling and a passiva-
tion. Electrochemical neutral pickling anodically oxidizes
oxygen and metal ions present in the oxide scale to higher
oxidation valences. In this way, the solubility of the oxide
 PICKLING OF AUSTENITIC STAINLESS STEELS (A REVIEW)
scale is increased. Manganese and chromium oxides dis-
solve preferentially to iron oxides and silicon oxide
remains at the surface. Mixed acid and oxidizing and com-
plexing agents are used in the final pickling step.
Traditional pickling solutions containing HNO3 + HF cause
problems due to environmental pollution and sludge pro-
cessing. Environmentally friendly pickling with a nitric
acid-free electrolyte containing hydrogen peroxide is by far
the best answer to these problems as a viable industrial
process.
ACKNOWLEDGEMENTS
The UGINE & ALZ Belgium NV (Genk, Belgium) is
gratefully acknowledged for financial support.
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REFERENCES
1. J.H. Nead, United States Patent, 1924, No. 1,508,567.
2. N.H. Schermer, United States Patent, 1931, No. 1,824,932.
3. F.C. Elder, United States Patent, 1931, No. 1,837,118.
4. B.S. Covino, J.V. Scalera and P.M. Fabis, Pickling of
Stainless Steels – A Review, 1984, Information Circular
8985, United States Department of the Interior, Bureau of
Mines, pp. 1-15.
5. J.M. Camp and B.C. Francis, The Making, Shaping, and
Treating of Steel, 1951, 6th ed., U.S. Steel Co., pp. 580-586.
6. H.H. Uhlig, Corrosion, 1963, vol. 19, pp. 231t-237t.
7. B. Ozturk and R. Matway, ISIJ Int., 1997, vol. 37(2), pp.
169-175.
8. H.J. Yearian, E.C. Randell and T.A. Longo, Corrosion, 1956,
vol. 12, pp. 515t-525t.
9. J.O. Edstrom, J. Iron Steel I., 1957, vol. 185, pp. 450-466.
10. H.M. McCullough, M.G. Fontana and F.H. Bech, Trans. Am.
Soc. Met., 1951, vol. 43, pp. 404-425.
11. Y.D. Lee, Y.H. Lee, J.S. Lee and J.K. Kim, Proc. Int. Conf.
on Stainless Steels, 1991, Chiba, ISIJ, pp. 952-958.
12. G.H. Meier, W.C. Coon and R.A. Perkins, Oxid. Met., 1982,
vol. 17(3/4), pp. 235-262.
13. P.M. Fabis, R.H. Heidersbach, C.W. Brown and T. Rochett,
Corrosion, 1981, vol. 37, pp. 700-715.
14. S. Jana, R.K. Aiyar and A. Ganguly, Proc. Int. Conf. on
Corrosion (CONCORN’97), 1997, Mumbai, pp. 914-923.
375
15. R. Matsuhashi, S. Ito, M. Nakata, Y. Oikawa and K. Ohmura,
Corrosion Engineering, 1993, vol. 42, pp. 703-714.
16. J.M.K. Hildén, J.V.A. Virtanen and R.L.K. Ruoppa, Mater.
Corros., 2000, vol. 51, pp. 728-739.
17. J. Hildén, J. Virtanen, O. Forsén and J. Aromaa, Electrochim.
Acta, 2001, vol. 46, pp. 3859-3866.
18. S. Kiya, Y. Hayashi, T. Kojima and Y. Hyugaji, Tetsu-to-
Hagané, 1995, vol. 81(10), pp. 1007-1012.
19. I. Kvernes, M. Oliveira and P. Kofstad, Corros. Sci., 1977,
vol. 17(3), pp. 237-252.
20. C. Leygraf and G. Hultquist, Surf. Sci., 1976, vol. 61(1), pp.
60-68.
21. H.E. Evans and R.C. Lobb, Corros. Sci., 1984, vol. 24(3), pp.
223-236.
22. G. Betz, K.G. Wehner and L. Toth, J. Appl. Phys., 1974, vol.
45(12), pp. 5312-5316.
23. F.H. Stott and F.I. Wei, Mater. Sci. Tech., 1989, vol. 5(11),
pp. 1140-1147.
24. M.G. Fontana and N.D. Greene, Corrosion Engineering,
1978, McGraw-Hill, pp. 35-36, 243.
25. B. Vincentini and G. Bombara, Electrochemica Metallica,
1968, vol. 3, pp. 313-322.
26. L.A. Fernando and D.R. Zaremski, Met. Trans. A, 1988, vol.
19A(4), pp. 1083-1100.
27. A.P. Shlyamnev, E.T. Shapovala, E.A. U’Lyanin, V.D.
Nikitin and A.R. Fisher, Steel in the USSR, 1980, vol. 7, pp.
371-373.
28. D. Henriet, Stainless Steels, eds. P. Lacombe, B. Baroux and
G. Beranger, de Physique Les Ulis, 1993, pp. 823-847.
29. T.V. Rao, R.W. Vook and W. Meyer, J. Vac. Sci. Technol. A,
1986, vol. A4 (3), pp. 1604-1607.
30. Theodor Rössel, Chemical Plants and Processing, May
1990, pp. 72-74.
31. P. Gümpel, M. Käber, K. Neumann, W. Racky and H.J.
Grabke, Stainless Steels ’96: Proc. Of the 2nd Europ.
Congress, Dusseldorf, 1996, pp. 79-82.
32. D.M. Price and G.L. Horter, Met. Finish., February 1994, pp.
60-65.
33. C.P. Dillon, Materials Selection & Design, May 1994, MP,
pp. 62-64.
34. AISI Committee of Stainless Steel Producers, Cleaning and
Descaling Stainless Steel, 1982, AISI, Washington DC,
Designers’ Handbook Series, p. 27.
CANADIAN METALLURGICAL QUARTERLY
 376 L.-F. LI and J.-P. CELIS
35. G. Bombara, A. Tamba and N. Azzerri, J. Electrochem. Soc.:
Electrochem. Technol., 1971, vol. 118, pp. 676-681.
36. A. Tamba and N. Azzerri, J. Appl. Electrochem., 1972, vol.
2, pp. 175-181.
37. N. Azzerri and A. Tamba, J. Appl. Electrochem., 1976, vol. 6,
pp. 347-352.
38. K. Tano, S. Abe, T. Murase, T. Okazaki, A. Maruta and S.
Kido, Nippon Steel Technical Report, 1989, vol. 43(10), pp.
1-7.
39. S. Shimada and A. Kawaguchi, Journal of the Metal
Finishing Society of Japan, 1986, vol. 37(3), pp. 115-120.
40. F.H. Baerhold, I. MacKenzie and L.A. Ruiter, MPT
International, 1999, vol. 6, pp. 32-37.
41. Edgar Braun, Iron Steel Eng., 1980, vol. 46(4), pp. 79-81.
Downloaded by [New York University] at 03:00 09 March 2016
42. Y.-U. Kim, D.R. Zaremski and C.S. Hertzler, United States
Patent, 1996, No. 5,490,908.
43. E.T. Shapovalov, A.P. Shlyamney, E.A. Ul’yanin, V.D.
Nikitin, A.R. Fisher, D.B. Gol’dzon, L.V. Popova and I.I.
Milovanov, Steel in the USSR, 1982, vol. 12, pp. 215-219.
44. E.T. Shapovalov, A.P. Shlyamnev, International conference
21st century steel industry of Russia and CIS, Moskow, 1994,
pp. 59-60.
45. P. Pourbaix, Atlas of Electrochemical Equilibria, 1966,
Pergamon Press, Oxford.
46. V.I. Dunaevskii, V.T. Stepanenko, M.Y. Shnol, and L.N.
Bespalko, Prot. Met., 1985, vol. 21(3), pp. 359-363.
47. B. Beverskog and I. Puigdomenech, Corrosion, 1999, vol.
55(11), pp. 1077-1087.
48. L.F. Loutrel, Met. Finish., 1940, vol. 38, pp. 645-646.
49. L.F. Loutrel, Met. Eng. Digest (in Metals & Alloys), 1941,
vol. 13, pp. 210-212.
50. S. Fortunati, E. Novaro, C. Pedrazzini and A. Pollastrelli,
Innovation Stainless Steel, 1993, Florence (Italy), pp. 2.119-
2.128.
51. C. Pedrazzini and P. Giordani, United States Patent, 2001,
No. 6,068,001.
52. M. Bianchi, United States Patent, 1999, No. 5,908,511.
53. C. Pedrazzi and P. Giordani, United States Patent, 1998,
No. 5, 843,240,.
CANADIAN METALLURGICAL QUARTERLY
54. M. Bianchi, United States Patent, 1994, No. 5,364,383.
55. B.S. Covino, J.V. Scalera, T.J. Driscol and J.P. Carter, Metall.
Trans. A, 1986, vol. 17A, pp. 137-149.
56. N.J. Sanders, Anti-corros. Method. M., 1997, vol. 44(1), pp.
20-25.
57. W.C. Schumb, C.N. Satterfield and R.L. Wentworth,
Hydrogen Peroxide, 1955, American Chemical Society, New
York: Reinhold Publishing Corporation, Printed by Waverly
Press, Inc., pp. 355-446.
58. R. Isarai, K. Yanagihara and M. Noma, Japanese Patent,
1975, No.50,133,125.
59. J.P. Malingriaux, La Revue de Métallurgie, 2000, vol. 10, pp.
1177-1185.
60. D. Henriet, United States Patent, 1997, No. 5,690,748.
61. M. Zavattoni, United States Patent, 1998, No. 5,785,765.
62. J.W. Leeker and R.D. Rodabaugh, United States Patent,
1998, No. 5,748,968.
63. P. McKevitt and S.E. Lapek, United States Patent, 1999, No.
5,879,465.
64. B. Wasserbauer, E. Braun and G. Maresch, United States
Patent, 2001, No.6,250,314.
65. R.D. Rodabaugh and R.W. Leeker, United States Patent,
1997, No. 5,702,534.
66. D. Henriet and P. Didier, United States Patent, 1992, No.
5,164,016.
67. S. Uchida, M. Tachibana, A. Watanabe, Y. Wada, N.
Shigenaka and K. Ishigure, J. Nucl. Sci. Technol., 2000, vol.
37(3), pp. 257-266.
68. Y. Wada, A. Watanabe, M. Tachibana, N. Uetake, S. Uchida
and K. Ishigure, J. Nucl. Sci. Technol., 2000, vol. 37(10), pp.
901-912.
69. Y. Wada, A. Watanabe, M. Tachibana, K. Ishida, N. Uetake,
S. Uchida, K. Akamine, M. Sambongi, S. Suzuki and K.
Ishigure, J. Nucl. Sci. Technol., 2001, vol. 33(3), pp. 183-
192.
70. Handbook of Stainless Steel, 1977, D. Peckner and I.M.
Bernstein, eds, New York: McGraw-Hill, Chap. 11, pp. 11-
17.
71. M.W. Wilding and B.E. Paige, Survey on Corrosion of
Metals and Alloys in Solutions Containing Nitric Acid, 1976,
Allied Chemical Corp., ICP-1107, pp. 56.