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https://doi.org/10.1007/s11665-018-3664-4 1059-9495/$19.00

Effect of Scale Spallation During Coiling

on the Electrochemical and Pickling Behavior
of a Hot-Rolled Dual-Phase Steel
S. Choudhary, K. Mondal, S. Mukherjee, and Sundara Bharathy R.

(Submitted April 6, 2018; in revised form June 25, 2018)

Tertiary oxide scale consists of magnetite and hematite, and in dual-phase steel strips were observed after
the exit of final rolling stand in a thin slab casting rolling (TSCR) mill. Microscopic observation confirmed
that these scales cracked and spalled off from many places of surface during coiling causing a non-uniform
oxide layer on the steel surface. The present work discusses the synergistic effect of such non-uniform oxide
layer and run-out-table cooling water on the electrochemical behavior of the dual-phase steel. The elec-
trochemical response was assessed with the help of dynamic and linear polarization tests considering
cooling water as electrolyte. The presence of non-uniform scale produced high cathodic (scaled zone) to
anodic (spalled-off zone) area ratio that eventually led to extensive pitting corrosion in the present steel.
Furthermore, the pickling behavior of the steel was also studied in detail. It was observed that the steel
surface, with spalled-off area of about one-tenth of total surface area, corroded preferentially 3-4 times
faster at spalled-off area than that of the uniformly pickled surface. The characterization study was
performed using scanning electron microscopy, confocal laser 3D scanning microscopy, x-ray diffraction
and Raman spectroscopy in order to establish the reasons for pitting corrosion due to the scale spallation.

promotes the formation of secondary oxide scale. Descaling of

Keywords corrosion, electron microscope, steel, tertiary oxide
scale
1. Introduction
During hot rolling of steel, slabs are normally reheated to a
temperature range of about 1100-1300 °C. The hot slab is then
transferred to roughing mill followed by finishing mill, where it
is deformed at temperature around 1050-850 °C. Subsequently,
the strip is cooled in run-out-table (ROT) using laminar water
jet and finally coiled at a temperature range of 700-200 °C
depending on the requirement of desired properties (Ref 1).
Inevitably, oxide scale is generated on the surface of strip
during various stages of hot rolling due to synergistic effect of
high temperature, the presence of atmospheric oxygen and
water vapor (Ref 2). Surface quality and downstream process-
ing of the hot-rolled coil, such as acid pickling, forming,
coating, largely depend on the mechanical and electrochemical
properties of the scale (Ref 3). Initially, primary oxide scale
with thickness of about 2-6 mm is generated during reheating
stage (Ref 4). Descaling of the slab is carried out by a high-
pressure water jet just before its entrance to roughing mill.
Furthermore, during successive reduction in roughing stand,
hot metal sheet is exposed to work roll cooling water, which
S. Choudhary and S. Mukherjee, Research and Development, Tata
Steel Limited, Jamshedpur 831001, India; K. Mondal, Department of
Materials Science and Engineering, IIT Kanpur, Kanpur 208016, India;
Sundara Bharathy R., Flat Product Technology Group, Tata Steel
Limited, Jamshedpur 831001, India. Contact e-mail: Sanjay.
Choudhary@monash.edu.
sheet is again carried out before entering to the finishing mill.
However, complete removal of scale is not possible before
coiling as the strip is still exposed to high temperature and
water after finishing mill. Thus, it reacts with oxygen and water
vapor and generates tertiary oxide scale on the surface of the
steel sheet. Researchers reported that thickness of secondary as
well as tertiary oxide scale is around 10-15 lm (Ref 5, 6).
Tertiary oxide scale is adhesive to the surface even after the
cooling down of the coil to room temperature. Therefore, final
product of the hot rolling process is the steel sheet covered with
thin tertiary oxide scale layer.
The tertiary oxide scale formed at the exit of the finishing
mill comprises of three different oxide layers, namely a thick
wustite (FeO) layer adjacent to the steel substrate, an interme-
diate magnetite (Fe3O4) layer and a thin outermost hematite
(Fe2O3) layer (Ref 2). However, wustite is unstable below
570 °C and it decomposes to magnetite with fine a-iron
particles (Ref 7).
4FeO ) a-Fe þ Fe3 O4
This transformation increases the scale adhesiveness to the
steel substrate (Ref 8). However, it is not possible to avoid
cracking/spalling-off tendency of scales, when they are sub-
jected to bending during coiling, due to strain mismatch
between scale layer and the steel substrate. Later on, pickling
performance would also depend on the occasional cracking/
spalling-off of the oxide cover formed during hot rolling
process. The outer Fe2O3 layer is known to dissolve only
slowly in acid, while the lower FeO and Fe3O4 layers dissolve
faster in comparison (Ref 9). Therefore, scale adhesiveness also
depends on the volume fraction of different constituents in the
scale.
Scale adhesiveness is one of the critical properties of the
hot-rolled dual-phase steel products. According to world

Journal of Materials Engineering and Performance

autosteel, majority of autobody parts is designed using dual-
phase steels (Ref 10). Moreover, many components, such as the
body of an excavator, a chassis of a pick-up truck, are made
with the dual-phase steel sheet without removal of oxide scale.
A proper bonding between the scale and the steel is necessary
in these applications. On the other side, poor scale adhesion is
required for cold-rolled and coated dual-phase steels, which are
used for cabin structural parts. In these applications, hot-rolled
coil is sent for pickling followed by cold rolling (Ref 11).
However, non-uniform scale on the surface during acid pickling
may lead to excess removal of metal from many places on the
surface (Ref 12). Similar localized corrosion attack due to scale
spallation is also possible for many hot-rolled coils, which are
directly used without pickling. Hot-rolled dual-phase steel is
coiled at the temperature below 300 °C. Low-temperature
coiling leads to incomplete removal of water from the surface
of the steel sheet as temperature varies from 300 °C to below
100 °C (normal water vaporization point). Coiling temperature
above the vaporization point can also lead to incomplete
removal of water as water vapor in inner wrap will be
condensed below 100 °C. This water will act as an electrolyte
and can lead to localized corrosion attack on the surface due to
scale spallation.
While scale spallation mechanism has been extensively
studied in the context of strain mismatch between scale and the
steel substrate (Ref 13-16), the studies on the electrochemical
behavior of steel surface due to scale spallation would also have
huge practical implication and importance. However, it is not
studied in detail in the open literature. Hence, it is a necessity to
study the scale protectiveness in run-out-table water environ-
ment due to scale spallation and concurrent effect on the
electrochemical behavior of the surface. In addition, the present
work analyzes the effect of cracked/spalled oxide layer at
localized regions of a hot-rolled dual-phase steel (DP600 steel
sheet) on the pickling of the scale and surface appearance.
2. Experimentation
The material under investigation was a hot-rolled dual-phase
steel with the tensile strength of 600 MPa. Chemical compo-
sition and mechanical properties are given in Table 1. This hot-
rolled dual-phase steel was produced in TSCR (thin slab casting
and rolling) mill at Tata Steel Limited, Jamshedpur (India).
Thin slab with thickness of around 60 mm was reheated at
1200 °C for 30 min followed by hot rolling. Roughing mill
entering temperature and finishing mill temperature were 1015
and 815 °C, respectively. Coiling was done at temperature
range of around 200-250 °C with the final thickness of 3.9 mm.
Samples were collected just after the coiling to minimize the
primary mechanical and electrochemical damage. Test speci-
mens were cut into 20 mm 9 20 mm 9 3.9 mm coupons for
Table 1 Chemical composition and mechanical properties of dual-phase steel
Chemical composition, wt.%
C Mn Si Al P V
0.053 1.173 0.03 0.034 0.022 0.002
scale characterization and electrochemical experimentation, and
coupons with dimension 20 mm 9 10 mm 9 3.9 mm were
used for cross-sectional microstructural analysis. All the
specimens were carefully immersed in acetone to remove oil,
grease and dust on the surface followed by distilled water
immersion and drying. Run-out-table (ROT) water was col-
lected for conducting the electrochemical experiments of the
samples. Initially, chemical analysis of the water was carried
out to determine pH and concentration of Cl and SO2 4 ions.
Chloride ion concentration was determined using VolhardÕs
method (Ref 17), while inductively coupled plasma-atomic
emission spectrometry (ICP-AES) was used to determine the
sulfate ion concentration (Ref 18). VolhardÕs method used the
back-titration with titanium thiocyanate to determine the
chloride concentration in a solution.
Microstructures of the rolling surface as well as the cross
section were analyzed using scanning electron microscope
(Quanta FEG 650). Energy-dispersive spectroscopy analysis of
the oxide scale was carried out to identify the morphology and
possible composition of different oxide layers across the scale
thickness. The scale was also characterized using grazing angle
x-ray diffraction and Raman spectroscopy. X-ray diffraction
was carried out using XÕPert PRO PANalytical system with a
step size of 0.016°/s and changing the grazing angle from 0.5°
to 20° to investigate the structure of the oxide layer in the scale.
Raman spectroscopy was carried out in an Acton SpectraPro
SP-2500 system. Scale surface was excited with the 532-nm
Nd: YAG laser. Raman intensity ratio could also be used to
calculate the concentration of the components in a sample.
However, this method might be prone to errors as the intensities
are affected by various experimental factors, such as laser
power, sample homogeneity, sample positioning (Ref 19).
Electrochemical tests were carried out using a PARSTAT
2263 system in a flat-bottom cell consisting of a specimen, a
saturated calomel electrode with saturated calomel
(E° = + 0.2444 V versus standard hydrogen electrode (SHE))
and a platinum wire mesh as working, reference and counter
electrode, respectively. All the electrochemical experiments
were performed at room temperature ( 30 °C) in 300 ml ROT
water mentioned above. Initially, open-circuit potential (OCP)
was measured after 1 h of its stabilization, followed by linear
polarization and potentiodynamic polarization. Linear polar-
ization was carried out between electrode potential rang-
ing ± 20 mV versus OCP at the scan rate of 0.166 mV/s.
However, potentiodynamic polarization scan was done from
 250 mV versus OCP to 1.6 V at the scan rate of 0.5 mV/s.
All the samples were tested without disturbing the scale layer.
Thereafter, the same electrochemical experimentation was done
with the acid pickled sample to compare the electrochemical
importance of scale spallation with completely descaled
surface. Pickling process involved passing the scaled surface
from five different acid baths having increasing hydrochloric
acid concentration (6, 9, 12, 14 and 16 wt.%) followed by
Mechanical properties
Nb Cr YS, MPa UTS, MPa %El
0.024 0.704 453 660 23
Journal of Materials Engineering and Performance
water rinsing. It was ensured that sample was immersed for 10-
14 s in each bath, while the baths were held at 80°C. Just after
all the electrochemical measurements, surfaces were analyzed
using SEM and confocal laser 3D scanning microscope (OLS
4000).
3. Results and Discussion
Chloride concentration, sulfate concentration and pH of the
ROT water were 30 ppm, 91.4 ppm and 8.9, respectively.
Although water is basic in nature, pH 8.9 is not enough to form
a stable protective oxide layer on the surface (Ref 20, 21).
Researchers have reported that most waters have less than
50 ppm chloride; however, concentration as low as 3 ppm has
an immediate effect on corrosion of steel (Ref 22). Further-
more, Niu et al. (Ref 23) have found that 100 ppm sulfate ions
have adverse effect on pitting. At higher potential, pit growth
rate is mainly controlled by diffusion of cations (Fe2+). While
diffusing out from inside the pit, these cations interact with
anions (Cl, SO42) and form a salt cover over the pit mouth.
As a result, pit growth rate decreases due to suppression of the
cation diffusion. However, an increase in concentration of
SO42 from 50 to 100 ppm (in the presence of 100 ppm Cl)
increases the solubility of the salt cover. This further leads to
the fracture of salt film, facilitating the diffusion of metal
cations and accelerating the rate of pit growth. Therefore,
present water could adversely affect the pitting behavior of the
steel surface.
Figure 1 shows the SEM micrographs of the rolling surface
(Fig. 1a) and cross section of the sheet (Fig. 1b, c and d).
Figure 1(a) reveals that the tertiary scale is discontinuous
throughout the surface and it has been chipped off from many
locations on the surface (as shown by arrows). Oxide scale is
under compression during cooling in ROT due to differential
Fig. 1 SEM micrographs of hot-rolled dual-phase steel after coiling: (a) rolling surface, (b) cross section: oxide scale, (c) full cross section:
decarburization near the surface, (d) cross section: microstructure of dual-phase steel
Journal of Materials Engineering and Performance
thermal expansion with respect to steel (Ref 13-16). This results
in compressive shear through-thickness cracks in oxide scale,
leading to scale spallation during coiling. Scale thickness has
been measured from the cross-sectional image (Fig. 1b) and
found to be uniform ( 10 lm).
Figure 1(c) shows that phase fraction of martensite near the
surface ( 50 lm depth) is substantially low. However,
martensite is uniformly distributed at the center with phase
fraction of around  15% (Fig. 1d). This microstructural
gradient evolution could be attributed to the decarburization
(Ref 24-26) and smaller prior austenite grain size (Ref 27) at the
surface of the steel during hot rolling. It is well known that
decarburization is unavoidable during high-temperature rolling.
Although this kind of microstructure gradient during hot rolling
is not reported in open literature till date, many researchers
observed similar microstructural evolution due to depletion of
carbon during decarburization. Jing et al. (Ref 25) have studied
the decarburization mechanism during hydrogen reduction
descaling of hot-rolled strip steel. They have observed equiaxed
ferritic grain with depletion of pearlite near the surface due to
decarburization. Castaneda et al. (Ref 26) have also reported
similar microstructural changes of hot-rolled steel due to
decarburization.
Decarburization leads to the diffusion of free carbon from
the bulk to the surface, which subsequently reacts with the
wustite (FeO) at high temperature and forms CO (Ref 11). This
gas layer at the interface between scale and the steel substrate
helps in descaling. On the other hand, surface layer of steel is
subjected to shear force and roll chilling effect leading to
reduction of the prior austenite grain size in the surface region
(Ref 27). Therefore, faster kinetics of ferrite formation at the
surface could lead to lower amount of martensite. However,
detailed study is required to establish the exact reasons behind
this microstructural gradient at the surface. This microstructural
variation leads to undesirable electrochemical and mechanical
properties of the surface (Ref 28).
 The scale at the surface comprises of different iron oxide
layers, i.e., wustite (inner layer), magnetite (intermediate) and
hematite (outer most layer). Although wustite is not stable be-
low 570 °C, it transforms into magnetite and free a-Fe particles
making magnetite as inner most layer (Ref 7). This layering
phenomenon can be confirmed from the elemental mass
fraction analysis using SEM–EDS (Fig. 2). Mass fraction of
Fe has been found out to be around 73 and 70 mass% in the
inner and the outer scale layers, respectively. Theoretically,
magnetite and hematite contain 73 and 70 mass% Fe, respec-
tively. Average thickness of the magnetite layer has been found
out to be 8 lm, while that of the hematite layer is 2 lm thick.
However, hematite layer was not compact and continuous. It is
very clear that the hematite layer has wide cracks, which could
act as sites for electrolyte access. Man et al. (Ref 29) have
analyzed the oxide scale with the help of focused ion beam
(FIB). They have also reported similar scale morphology
including microcracks. These cracks are generated during
cooling due to surface stresses caused by differential thermal
expansion coefficient between different oxides within the oxide
scale.
Grazing angle XRD result also confirms the presence of
magnetite and hematite (Fig. 3). Figure 3(a) shows the XRD
peaks of the scale with increasing grazing angle from 0.5° to
20°. Grazing angle is directly related to the depth of penetra-
tion, and therefore, grazing angle can be increased to analyze
inner most layer (Ref 30, 31). Intensity of the peaks of
magnetite increases with increasing grazing angle (Fig. 3b)
confirming the result of SEM–EDS. However, quantitative
analysis from XRD analysis is difficult due to layered structure
of the scale as fraction of scale constituent is changed with
depth of penetration. Figure 4 shows the Raman spectrum of
the steel, and it shows mainly hematite peaks and few lower
intensity peaks have been identified as magnetite (Ref 32). This
is due to the low penetration depth of laser because low-
intensity 532-nm laser has been used. Researchers have shown
that 532-nm laser reaches only up to around 0.7 lm depth
Fig. 2 SEM-EDS analysis of scale layers
making it impossible to give the bulk data (Ref 33). Therefore,
data obtained from Raman spectroscopy mainly confirm the
outer layer as hematite.
Figure 5 shows the linear polarization (a) and potentiody-
namic polarization curves (b) of the samples with scale and
pickled surface, respectively, in ROT water environment. It is
important to mention that the analysis
 ofthe pickling has been
mentioned in later sections. Slope dðDEÞ
at zero overpotential
di
(or zero current) gives the linear polarization resistance (Rp),
and it is inversely related to the corrosion current density (Ref
34).
dðDEÞ
¼ Rp
di DE¼0
It is important to mention that linear polarization test was
carried out after 1 h wait for the requirement of stabilization of
OCP. At stable OCP, both cathodic and anodic reaction rates or
cathodic and anodic current densities are the same as per the
principle of mixed potential theory. Therefore, net current is
zero at OCP. This linear plot is obtained when a small
overvoltage is applied. The slope dðDEÞ
di was calculated by fitting
straight line through a set of 5-7 data points including (0, 0) as
the center point. Rp is the resistance for the charge transfer
between sample surface and the electrolyte. However, corrosion
current density cannot be determined only using linear
polarization method.
Tafel extrapolation method (ASTM G3-14) was used to
measure the corrosion current density and corresponding
corrosion potential. FaradayÕs law (ASTM G102-89) has been
used to calculate the corrosion rate:
3:27  icorr  E:W:
Corrosion Rate ðmm/yearÞ ¼
q
where icorr is the corrosion current density (mA/cm2), E.W. is
equivalent weight in gram (= 27.92 for carbon steel), and q
Journal of Materials Engineering and Performance
Fig. 3 (a) Grazing angle XRD spectrums of the scale layer and (b) magnified peak in the range of 2h = 34°-37° (H hematite, M magnetite)
Fig. 4 Raman spectrum of the scale layer (H hematite, M magnetite)
denotes the density of the material in g/cm3 (= 7.85 for carbon
steel). Values of the electrochemical parameters for the samples
with the scale as well as pickled surface are given in Table 2.
Linear polarization resistance with the scale surface is
higher than that of the pickled surface (Fig. 5a and Table 2).
This is the indication of the surface protectiveness due to the
scale formation. This can also be seen from the potentiody-
namic polarization results that the corrosion rate of the pickled
surface is 3-4 times higher than that of the sample with scale
surface (Fig. 5b and Table 2). However, the sample with scale
surface gets intensely pitted only from spalled-off areas.
Confocal 3D micrographs with the scale surface, before and
after polarization test, are shown in Fig. 6(a) and (b), respec-
Journal of Materials Engineering and Performance
tively. It is important to mention that Fig. 6(a) and (b) is not the
same spot as it is difficult to identify the same spot after
electrochemical test. However, more than three spots were
analyzed in both the cases for sound comparison. Line profiles
show that depth of the spalled-off zone from scaled surface
increased from around  10 to  60 lm after potentiody-
namic polarization test.
However, surface covered with scales is unaffected. It shows
that the localized spalled zones are electrochemically more
active than the scaled area. It also reflects that the dissolution is
only concentrated in the spalled-off zone, increasing the
possibility of intense pitting on these regions. Confocal 3D
micrographs of pickled surface, before and after polarization
Fig. 5 (a) Linear polarization and (b) potentiodynamic polarization curves with scale and pickled surface

Table 2 Electrochemical properties with scale and pickled surface from the linear and potentiodynamic polarization
curves
Electrochemical properties With scale surface Pickled surface

Linear polarization resistance, X-cm2 9923 2750

Corrosion potential, V  0.415  0.517
Corrosion rate, mm/year 0.029 0.119

Fig. 6 Confocal 3D scanning micrographs of steel surface with scale surface: (a) before potentiodynamic, (b) after potentiodynamic
polarization (shown values are in lm)

Journal of Materials Engineering and Performance

Fig. 7 Confocal 3D scanning micrographs of steel surface with pickled surface: (a) before potentiodynamic, (b) after potentiodynamic
polarization (shown values are in lm)

test, are shown in Fig. 7(a) and (b), respectively. Similar to

Fig. 6, Fig. 7(a) and (b) does not reflect the same spot on the
surface. However, the same sample surface was analyzed
before and after polarization test. Minimum 5 readings were
taken to get the average roughness value. Pickled surface shows
roughness of 1.16 ± 0.16 lm with few shallow points (arrow-
heads). Surface roughness increased to 1.29 ± 0.32 lm after
potentiodynamic polarization test. Depth of few locations has
also increased insignificantly to around 10 lm (arrowheads).
This is the indication of uniform corrosion after pickling as
surface dissolves uniformly. Uniform corrosion of pickled
surface has resulted in higher material loss than that of scaled
surface as corrosion current density is much higher for pickled
surface (Fig. 5b).
The current density used for calculation of corrosion rate
listed in Table 2 represents the current with respect to whole
exposed area during electrochemical tests. However, for scaled
surface, dissolution is concentrated only at the spalled area. Fig. 8 Corrosion rate on the steel surface with scale (WS), pickled
Therefore, current density should be recalculated with respect steel surface and estimated pitting growth rate of steel surface with
to the spalled area in order to determine the ‘‘dissolution rate scaled calculated by Tafel plot
for spalled area’’ or ‘‘pit growth rate.’’
Pit growth rate ¼ calculated corrosion rate captured in Fig. 9(a, b, c, d, e and f). Although micrographs
Whole exposed area shown in Fig. 9 do not show the same spot, micrographs of
 different spots have been added to explain the pitting growth
Spalled off area
mechanism. Figure 9(a) shows the initiation of pitting, which
As shown in Fig. 1(a), approximately one-tenth of total further grows within the spalled-off area (Fig. 9b and c). When
surface area has been spalled off. Therefore, pit growth rate due electrolyte inside the pit becomes saturated with metal cations,
to the scale spallation is approximately ten times higher than crevice corrosion takes place just in the surrounding region
overall corrosion rate with scale surface and 3-4 times higher followed by spallation (Fig. 9d). This provides more space for
than that of pickled surface as shown in Fig. 8. the growth of the pits horizontally (Fig. 9b). Chloride ions in
Nucleation of a pit on the chipped-off area followed by the electrolyte result in vertical growth of any pit, while poor
growth during the course of potentiodynamic polarization is scale adhesiveness leads to horizontal growth (Ref 35).

Journal of Materials Engineering and Performance

Fig. 9 Growth of a pit on steel surface with scale surface during potentiodynamic polarization: (a) nucleation, (b) growth, (c) complete
dissolution of spalled-off area, (d, e) crevice corrosion followed by scale spallation just in the surrounding area, (f) cross-sectional view of
crevice corrosion

Horizontal growth of the pits also allows the electrolyte to (i) Oxidation of scale spalled-off steel surface:
come in contact with subsurface magnetite layer, which are
cathodic sites for cathodic reactions. When surface with scale Fe ) Fe2þ þ 2e
spalled-off area comes in contact with any electrolyte contain- (ii) Combination and hydrolysis reactions
ing oxidizing ions, an electrochemical cell would form due to
the potential difference between spalled-off region and the Fe2+ ions would form FeCl2 and FeSO4 salts, which
scaled area. subsequently hydrolyze to Fe(OH)2 and H+Cl or 2H+SO42
Hematite is non-conductive and therefore will not partici- acids, increasing the pH in the pit region.
pate in the electrochemical reaction during pitting of scale
spalled-off zone. However, this outermost hematite layer is Fe2þ þ 2Cl ) FeCl2
porous, loose and discontinuous, which completes the electro-
chemical circuit between scale spalled-off zone and magnetite Fe2þ þ SO2
4 ) FeSO4
(Ref 36). In the present case also, there are segments, where FeCl2 þ 2H2 O ) FeðOHÞ2 þ 2Hþ 2Cl
oxide scale has spalled off (Fig. 1) as well as the outer hematite
FeSO4 þ 2H2 O ) FeðOHÞ2 þ 2Hþ SO2
4
oxide layer has also wide cracks (Fig. 2). Hence, non-
conducting nature of hematite is not going to prevent electro-
chemical reactions since there is already a contact between the (iii) Cathodic reactions.
subsurface cathodic magnetite with the metal surface via the
sipped in electrolyte. Therefore, electrochemical reactions in O2 þ 2H2 O þ 4e ) 4ðOHÞ
the presence of ROT water electrolyte resulting in concentrated
corrosion comprise of the following redox, combination and This reaction happens in the beginning of the electrochem-
hydrolysis reactions: ical process in ROT water. However, there is generation of H+

Journal of Materials Engineering and Performance

Fig. 10 Corrosion and pit growth mechanism for dual-phase steel after coiling
ions near the pit regions due to hydrolysis of the chloride and
sulfate salts, which would react with Fe3O4 to give another
cathodic reaction, which would further accelerate the dissolu-
tion of Fe from the pit region.
Fe3 O4 þ 8Hþ þ 2e ) 3Fe2þ þ 4H2 O
Potential difference can also be seen from the potentiody-
namic plots as equilibrium potential of the pickled surface is
more negative than that of the surface covered with scale
(Fig. 5b). Therefore, descaled area is anodic with respect to
scaled area. Furthermore, higher cathode/anode area ratio
makes anodic area to dissolve faster, as corrosion current
density increases with increasing cathode/anode area ratio (Ref
37, 38). The larger the cathodic area compared with anodic
area, the more reduction reaction or cathodic reaction can occur
and, therefore, greater will be the galvanic current. This area
effect causes the surface to get pitted in the presence of an
electrolyte containing anions, such as chloride and sulfate.
Cation (Fe2+) concentration increases inside the pit due to
oxidation, and it attracts the chloride and sulfate ions to move
inside the pit. It increases the acidity of electrolyte inside the
pit, and therefore, dissolution aggravates and results in rapid
vertical growth of any pit (Ref 39). Therefore, the present
experimental evidence clearly points at the nucleation and
growth of pits being governed by high cathodic/anodic area
ratio and the presence of chloride and sulfate ions in the
electrolyte. Oxidizing agents (chloride, sulfate and dissolve
oxygen) present in the cooling water aggravate the oxidation
reaction of the scale spalled-off zone, and subsequently,
reduction rate of scale also increases. There are a number of
redox reactions, whereas there is one oxidation reaction of Fe
forming soluble Fe2+ ions. There is combination of hydrolysis
reactions which would increase the acidity in the pit region
even if the ROT water is basic in nature. This follows basic
mechanism of pit growth and Pourbaix diagram. Hence, pit
growth is a combined action of large cathodic to anodic area
Journal of Materials Engineering and Performance
ratio and more number of reduction reactions (oxygen reduc-
tion as well as reduction of Fe3O4 in the presence of increased
H+ ions generated due to hydrolysis reaction inside the pit
region). A single oxidation reaction (Fe = Fe2+ + 2e) would
need to supply equivalent amount of electrons for the two
cathodic reactions. Hence, rate of dissolution or growth of pit
increases substantially in the exposed section.
Figure 10 shows the sequence of events and finally
generation of pits and remaining trace of pits after acid
pickling. Scale formed after finish rolling called tertiary scale
was  10 lm thick. However, scale got cracked and chipped
off from many places due to the strain mismatch with steel
substrate during bending during coiling. Decarburization could
also have been played a role in descaling as it forms CO gas
bubble at the interface causing blistering (Ref 40). Dual-phase
steels are processed by very low coiling temperature, and
therefore, quenching water does not vaporize completely from
the surface during coiling. This water acts as an electrolyte and
makes the surface more susceptible to pitting corrosion due to
scale spallation. Scale chipped-off area became anode with
respect to scaled area (mainly magnetite scale) and surface gets
pitted extremely due to high cathodic/anodic area ratio. Surface
was pickled to eliminate the effect of high cathode/anode area
ratio, and corrosion happens by uniform dissolution mode as
observed in the present case. Therefore, after pickling results
show an increase in corrosion rate (Fig. 5b). However, pickled
surface has insignificant shallow impression than that of with
the scale surface. Therefore, severity of pitting is much higher
in case of non-uniform scaled surface than that of pickled
surface. Thus, proper control over coiling temperature is
required to avoid the incomplete water removal and subse-
quently to avoid pitting for dual-phase steels. Moreover, a
systematic study of scale adhesiveness with respect to chemical
composition and thermomechanical processing parameters is
also necessary to provide a protective atmosphere for the steel
sheets, which are directly used without pickling.
4. Conclusions
The present work has investigated the electrochemical
behavior of hot-rolled dual-phase steel in cooling water due
to scale spallation during coiling, and the following conclusions
are drawn from the above study:
1. Layered tertiary oxide scale of  10 lm thickness was
observed in the dual-phase steel under investigation.
2. EDS, grazing angle XRD and Raman spectroscopy con-
firmed that the layered structure consists of inner mag-
netite layer ( 8 mm thickness) and outer hematite layer
( 2 mm thickness). The outer hematite layer contains
many microcracks, which later act as access points for
the electrolyte for an electrical contact between magnetite
and metal surface.
3. SEM images confirmed that the tertiary scale got cracked
and spalled off sporadically from the steel surface primar-
ily due to strain mismatch.
4. Lower ( 250 °C) coiling temperature during dual-phase
steel processing leads to incomplete removal of cooling
water. The non-uniform scale on the surface with high
cathodic (scaled zone) to anodic (spalled-off zone) area
ratio and the presence of an electrolyte (cooling water)
leads to pitting corrosion of the dual-phase steels.
5. Scaled surface with spalled-off area of about one-tenth of
total surface area gets corroded preferentially at spalled-off
area and 3-4 times slower than that of uniformly getting
corroded pickled surface. However, growth rate of pitting
due to formation of microelectrochemical cell was 3-4
times higher than that of corrosion rate of pickled surface.
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