Thin Solid Films 517 (2009) 1672–1676

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t s f

Formation and characterization of bi-layer oxide coating on carbon-steel for

improving corrosion resistance
V.K. Mittal a, Santanu Bera a,⁎, T. Saravanan a, S. Sumathi a, R. Krishnan b, S. Rangarajan a,
S. Velmurugan a, S.V. Narasimhan a
a
Water and Steam Chemistry Division, BARC Facilities, Kalpakkam 603 102, Tamil Nadu, India
b
Materials Science Division, IGCAR, Kalpakkam 603 102, Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Attempts were made to improve the corrosion resistance of carbon steel by developing an additional barrier
Received 31 January 2008 layer of magnesium ferrite (MgFe2O4) on magnetite (Fe3O4) film formed at high temperature in aqueous
Received in revised form 25 September 2008 medium. The magnetite film was developed by exposing the carbon steel specimen in LiOH solution at 265°C
Accepted 25 September 2008
for 10days. Subsequently, the magnesium ferrite (MgFe2O4) film was deposited by pulsed laser deposition
Available online 7 October 2008
(PLD) technique. X-ray diffraction analysis of the film revealed the formation of spinel phase of MgFe2O4.
PACS:
Relative atomic ratio of Mg and Fe estimated from X-ray photoelectron spectroscopy further confirmed the
81.05.Je spinel phase of MgFe2O4. Scanning electron microscopy and atomic force microscopy techniques were used
81.65.Kn to analyze the film surface morphology. The corrosion behavior of the coated specimens was studied
81.15.Fg electrochemically. Impedance measurements showed an increase in impedance by more than two times in
PLD coated samples compared to the Fe3O4 coated carbon-steel.
Keywords: © 2008 Elsevier B.V. All rights reserved.
Corrosion
Carbon-steel
PLD
XPS
Spinel oxides

1. Introduction
It is the composition of the alloys that could be modified for
improving their corrosion resistance. But it is found better to apply an
adherent coating on the alloy surface to improve the corrosion
resistance of the base alloy without changing its mechanical property.
Several methods such as sol–gel [1], metal ion implantation [2], and
physical vapor deposition [3] are found promising for developing
coatings on alloys. Bi-metallic coatings on carbon steel surfaces are of
special interest for the protection in specific environments [4,5]. In
nuclear power plants (e.g. PHWR: pressurized heavy water reactor)
though the corrosion rate of carbon steel is reduced by forming a
passive magnetite (Fe3O4) layer, the radioactivity transport problems
necessitate further reduction in the metal ion release.
In Fe3O4 coated carbon steel, corrosion at high temperature occurs
by two concurrent processes. Metal ions from carbon steel are
released into water by outward diffusion through the Fe3O4 grain
boundaries. Simultaneously, the oxygen carrying species move
towards the carbon steel-Fe3O4 interface through nano-pores. The
nano-pores are created due to lattice mismatch of carbon steel and the
⁎ Corresponding author. Tel.: +91 44 2748 0203; fax: +91 44 2748 0097.
E-mail address: bera@igcar.gov.in (S. Bera).
Fe3O4 coating [6]. So, attention has been given to modify the pores and
grain boundaries to improve the corrosion resistance of alloys. In
nuclear power plants, metal ion passivation (MIP) is one of the
potential methods practiced to modify the oxide films on alloy
surfaces to control corrosion. Though the role of MIP in reducing
corrosion is not very clear, one cannot rule out the probability of the
grain boundaries or the nano-pores being sealed in the passivation
process. In boiling water reactor it was observed that the addition of
Zn2+ at ppb level reduced the release of corrosion products into the
coolant by modifying the oxide layer over the structural materials [7].
As Zn and Mg have similar chemical properties because of their
position in the periodic table, Mg was used as a substitute for Zn ion in
reducing the radioactivity build up [8]. Reduction in corrosion product
release of carbon steel was observed due to Mg ion passivation in
simulated PHWR-primary heat transport (PHT) coolant conditions [8].
In this report, an attempt is made to form an additional MgFe2O4
coating on Fe3O4 for further improvement of corrosion resistance of
carbon steel. It is unlikely to form an adhesive and compact Mg-ferrite
coating directly over carbon-steel. So Fe3O4 coating was first formed
on carbon steel in an autoclave under PHT system condition. MgFe2O4
coating over the Fe3O4 film was formed by the pulsed laser deposition
(PLD) technique. The film stoichiometry and the surface morphology
were characterized by X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS) and scanning electron microscopy (SEM)

0040-6090/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2008.09.094
 V.K. Mittal et al. / Thin Solid Films 517 (2009) 1672–1676
measurements. The corrosion resistance behavior of the film was
monitored by recording the impedance spectra of the specimens.
2. Experimental details
2.1. Formation of Fe3O4 on carbon steel
Diamond polished carbon steel samples of size 1cm × 1cm (% com-
position: C-0.16, Mn—0.85, Si—0.35, Cr b 0.3, Ni b 0.14 and balance iron)
were used for this study. Fe3O4 coating over the carbon-steel was
developed in a pre-conditioned autoclave by keeping the coupons for
10days in LiOH solution (pH 10 at room temperature) at 265°C. The
autoclave solution was de-aerated by purging argon gas before heating
and 25ppm of hydrazine was added to take care of remaining oxygen.
The thickness of the Fe3O4 layer was measured by de-scaling it in
Clarke's solution (5% w/w SnCl2, 2% w/w Sb2O3 in concentrated HCl) and
was calculated to be around 0.45μm.
2.2. Pulsed laser deposition of MgFe2O4
PLD technique was used to deposit MgFe2O4 on Fe3O4 coated carbon
steel. MgFe2O4 was prepared in a solid-state route. MgO and α-Fe2O3 was
mixed in stoichiometric ratio and then sintered at 1200°C for 30h with
intermittent grinding [9]. The powder obtained was made into pellets.
The pellet was used as the target material for the PLD deposition. Thin
film of MgFe2O4 was prepared by using Nd-YAG laser (M/S Quanta
System, Italy) operating at 1064nm with pulse width and energy of 5ns
and 500mJ respectively. The beam was focused to 2mm on a rotating
target. The substrate was kept at a distance 5cm from the rotating target.
The MgFe2O4 films were deposited on Fe3O4 under two conditions. In one
condition, the substrate temperature was 600°C and oxygen pressure was
kept at 1.0Pa. In the other case, the substrate was heated to 500°C and
oxygen pressure was kept at 0.1Pa during the pulsed laser deposition of
MgFe2O4. Thickness of the ferrite film was measured by stylus profi-
lometry and was about 0.4μm.
It is to be mentioned here that when MgFe2O4 was directly
deposited on carbon-steel, the coating was non-adherent and peeled
off from the carbon-steel substrate (Fig. 1a). It might be due to the
mismatch in lattice parameters of carbon-steel and MgFe2O4 which
restricted the formation of the grains of MgFe2O4 on the alloy. Since
Fe3O4 and MgFe2O4 have common spinel structure with almost similar
lattice parameters, MgFe2O4 coating formed over Fe3O4 film was found
to be adherent and smooth (Fig. 1b).
2.3. Characterization of the deposited films
Glancing angle XRD (M/S STOE X-ray θ–θ diffractometer, Germany)
studies were carried out on these films to know the crystal structures
using Cu kα as the incident radiation. The surface morphology and the
Fig. 1. Optical microscopy pictures of MgFe2O4 film on (a) C-steel where a discontinuous
film was formed; (b) a continuous film was formed on Fe3O4 coated C-steel under the
same conditions of deposition.
1673
Table 1
Abbreviation of different samples used in the experiment
Sample name Abbreviated Sample name Abbreviated
name name
Carbon-steel CS Fe3O4 coated carbon-steel MCS
PLD coated MgFe2O4 on FMCS-1 PLD coated MgFe2O4 on FMCS-2
Fe3O4 coated carbon steel Fe3O4 coated carbon steel
at 600 °C, 1 Pa O2 pressure at 500 °C, 0.1 Pa O2 pressure
particle size of the films were measured by SEM (Philips Model 501)
using 30keV electron beam energy. Atomic force microscopy (AFM)
(Solver Pro, NT-MDT) technique was operated in semi-contact mode to
get the surface morphology using tip of radius 10nm with the scan size of
5μm. Oxidation states of Fe and Mg in coatings as well as relative amount
of Fe and Mg were obtained with the help of XPS (Model VG ESCALAB
MK200X) technique. Al kα X-ray source was used for photoemission and
the spectra were collected by a 150mm hemispherical analyzer at 20eV
pass energy. The spectrometer was calibrated with Au 4f7/2 line at 84.0eV
[10]. C 1s peak at 285.1eV was used as an internal standard for charge
correction in insulating samples. However in-situ sample cleaning by Ar
ion etching was avoided to avoid beam induced damages which was
observed for ferrites and magnetite [9].
2.4. Electrochemical studies of the oxide coated carbon steel
The electrochemical studies on the samples of carbon-steel, Fe3O4
coated carbon-steel and bi-layered oxide coated carbon-steel (MgFe2O4
and Fe3O4 coated) were carried out in 0.1M sodium sulphate test solution
in a conventional three-electrode cell with a platinum foil as counter
electrode and a saturated calomel through a luggin capillary as reference
electrode. The experiments were performed at room temperature in de-
aerated sodium sulphate solution using an Eco Chemie Autolab PG STAT
30 system. The samples were allowed to attain stable open-circuit
potential (OCP) before starting the electrochemical measurements. The
potentiodynamic anodic polarization (PDAP) behaviors of the samples
were obtained by polarizing the working electrode from − 1V to + 1.5V
with respect to corrosion potential (Ecorr) at a scan rate of 0.5mV per
second. The corrosion current (icorr) was determined from the intersec-
tion of anodic and cathodic Tafel lines or from that of Ecorr with the
suitable Tafel line. The magnitude of the corrosion current was taken to
be representative of the corrosion resistance of the composite material.
Impedance spectra from different samples were recorded at OCP by
applying a sinusoidal voltage of ± 10mV in the frequency range of 104–
Fig. 2. XRD patterns of (a) MCS, (b) FMCS-1 and (c) FMCS-2 samples.
1674 V.K. Mittal et al. / Thin Solid Films 517 (2009) 1672–1676

(Fig. 2b), diffraction peaks of base alloy (carbon-steel), MgO, α-Fe2O3,

MgFe2O4 and Fe3O4 were identified. Peaks for MgFe2O4 and Fe3O4
occur at the same positions because of their spinel crystal structure.
The result suggested a need for changing the PLD coating conditions.
PLD coating developed at 1.0Pa oxygen pressure led oxidation of
Fe3O4 to α-Fe2O3. Diffraction pattern for FMCS-2 sample (formed
under 0.1Pa oxygen pressure) is shown in Fig. 3c. The diffraction
pattern showed only the base metal (carbon-steel) and spinel phase
and, no α-Fe2O3 could be seen. This result was further corroborated
with XPS measurements.

3.2. Surface morphology

The surface morphology was studied by SEM technique and the

micrographs are shown in Fig. 3. The SEM picture of Fe3O4 coated
specimen (Fig. 3a) showed the presence of small particulates on
compact layer. This indicated the initiation of the second layer on the
compact first layer. The MgFe2O4 coating on Fe3O4, shown in Fig. 3b, was
found to be very smooth and non porous. The atomic level surface
morphology was carried out using AFM. The micrograph showed the
presence of oxide grains on the coated specimens (Fig. 3c). From the AFM
picture, Fe3O4 particle size was estimated of the order of 200–300nm. In
FMCS-1 sample, particle size was reduced to the range of 100–200nm,
while in FMCS-2 coupon the particle size was observed (Fig. 3d) to be
below 100nm. This was expected as coating temperature was lowered
compared to that in FMCS-1. Thus, MgFe2O4 grains were smaller than
that of the Fe3O4 grains on which the former grew.

3.3. X-ray photoelectron spectroscopy

Fe 2p3/2 photoelectron peak obtained from MCS sample is shown

Fig. 4(a). The peak binding energy was observed at 710.6eV with peak

Fig. 3. SEM and AFM images of (a, c) MCS and (b, d) FMCS-2 samples, respectively.

0.005Hz. In general, the impedance measurements can represent the

different processes like charge-transfer, diffusion controlled or Warburg
impedance that are taking place during the corrosion reaction.

3. Results and discussion

3.1. X-ray diffraction of the films

The abbreviated nomenclatures of different specimens are men-

tioned in Table 1. XRD pattern of the MCS samples showed peaks
corresponding to Fe3O4 spinel structure along with prominent peak of Fig. 4. XPS spectra of Fe 2p peaks showing the peak position (width) obtained from
carbon steel as indicated in Fig. 2a. In the XRD pattern of FMCS-1 sample (a) MCS, (b) FMCS-1 and (c) FMCS-2.
 V.K. Mittal et al. / Thin Solid Films 517 (2009) 1672–1676 1675

Table 2
PDAP parameters of different carbon steel coupons immersed in 0.1 M sodium sulphate
test solution

Materials Ecorr ba bc Icorr

(V vs SCE) (V (dec)− 1) (V (dec)− 1) (μA cm− 2)
CS −0.771 0.072 −0.159 3.885
MCS −0.639 0.082 −0.393 0.976
FMCS-1 −0.688 0.107 −0.247 0.498
FMCS-2 −0.644 0.072 −0.317 0.333

From the above XRD and XPS analyses it appears that the FMCS-1
sample is possibly composed of Fe2O3, MgO, Fe3O4 or/and MgFe2O4.
But the FMCS-2 sample is composed of MgFe2O4 only.

3.4. Electrochemical studies

The potentiodynamic current-potential curves were recorded for

the samples in test solutions to observe the general corrosion behavior
of the specimens. Fig. 6 shows the PDAP curve for CS, MCS, FMCS-1
and FMCS-2 samples in the Na2SO4 medium. It can be seen in Table 2
that the Ecorr has shifted towards the noble side as the carbon steel is
protected by either with Fe3O4 or any type of coating. The ferrite
Fig. 5. XPS spectra of Fe 3p and Mg 2p peaks of (a) MCS, (b) FMCS-1 and (c) FMCS-2. coated carbon steels showed an active to passive transition, probably due
to the formation of Ferric sulphate/Ferric hydroxide film at more anodic
potentials. The transition region was observed in the range + 0.574 to
width 5.0eV, which matches well with the literature value for Fe3O4
[11]. Fe 2p3/2 peaks from FMCS-1 and FMCS-2 specimens are shown in
the Fig. 4(b) and (c) respectively. The peak width in both specimens
was found to be reduced to 3.6–3.8eV in comparison to that from
Fe3O4 film. Higher peak width of Fe 2p3/2 in Fe3O4 was due to the
presence of Fe2+ and Fe3+. The narrower peak width in FMCS-1 and
FMCS-2 samples indicated the presence of single oxidation state of Fe.
The binding energy of Fe2p3/2 peak recorded from FMCS-1 and FMCS-
2 was found to be 711.0eV and 711.3eV respectively that corresponds
to Fe3+ state [11] in MgFe2O4 coated specimens.
Mg 2p peaks from FMCS-1 and FMCS-2 were observed at around
49.9eV, as indicated in Fig. 5(b) and (c). This corresponds to Mg2+ state
as expected. Atomic concentration of Fe and Mg was estimated from
the area under the Fe 3p and Mg 2p peaks. The quantification of
sample FMCS-1 showed 27% and 73% for Mg and Fe, respectively. In
FMCS-2 sample, the analysis showed 38% and 62% of Mg and Fe
respectively which closely resembles the atomic ratio in MgFe2O4.

Fig. 6. Potentiodynamic polarization curves in 0.1 M sodium sulphate solution for (a) CS, Fig. 7. Impedance spectra of coated specimens in 0.1 M sodium sulphate solution for
(b) MCS, (c) FMCS-1 and (d) FMCS-2. (a) CS, (b) MCS, (c) FMCS-1 and (d) FMCS-2.
1676 V.K. Mittal et al. / Thin Solid Films 517 (2009) 1672–1676
Fig. 8. Randle's Equivalent Circuit Model; (a) represents the non-porous model and
(b) represents the porous model.
+ 1.344V for FMCS-1 and + 0.794V to + 1.371V for FMCS-2 specimens. The
polarization curves were similar for coated carbon steels. The passivation
current for these specimens were in decreasing order CS, MCS, FMCS1,
FMCS2 showing increasing protectivity. The curve obtained for plain CS
and MCS showed higher corrosion current compared to the ferrite-coated
specimen either FMCS1 or FMSC2. Based on the values of corrosion
current, the corrosion resistance was found to be in the following order:
FMCS2 N FMCS1 N MCS N CS.
The Nyquist plots of the impedance spectra obtained at Ecorr are
shown in Fig. 7. Existence of single semicircle in the impedance
diagram indicates that the corrosion behavior is controlled by charge
transfer process. Dispersed data points observed in FMCS2 samples
has been attributed to the inhomogeneity/roughness of the surface.
The spectra were analyzed using two equivalent circuit models as
shown in the Fig. 8a and b respectively. Fig. 8b is the model for porous
specimens. Fig. 8a shows the equivalent circuit for non-porous
specimens where solution resistance (Rs), charge transfer resistance
[(Rct) / (Rco)] (Rct corresponds to metal solution interface and Rco
corresponds to coated specimens) and an interfacial capacitance value
[(Cdl) / (Cco)] (Cdl corresponds to metal solution interface and Cco
corresponds to coated specimens) were found to fit the impedance
data satisfactorily. It can be seen from the impedance diagrams that
the diameter of the semicircle in case of FMCS2 sample was highest
one. The impedance parameters fitted from the curve are presented in
Table 3. This implies that high charge transfer resistance is achieved in
the double coated specimen and hence the better corrosion resistance.
This behavior was also confirmed in the potentiodynamic polarization
measurements.
It can be seen from Table 3 that the FMCS-2 specimen showed the
highest polarization resistance (Rco) than the other specimens. Higher
Rco value is an indication of better corrosion resistance. The constant
phase element Cdl in the equivalent circuit implied a non-homo-
geneous surface layer of the coating. The [(Rct) / (Rco)] values for the
various specimens followed the order as below: FMCS-2 N FMCS-
1 N MCS N CS. Order of [(Rct) / (Rco)] values shows the better corrosion
resistance for FMCS-2 sample.
Corrosion current for MCS was observed to be higher than that for
both PLD coated specimens (Table 2). It is expected that the
interconnected nano-pores in the Fe3O4 layer are responsible for
corrosion of the base metal. Though the MgFe2O4 coated specimens
(FMCS-1, FMCS-2) showed better corrosion resistance compared to
Table 3
Impedance measurements of different carbon steel coupons, immersed in 0.1 M sodium
sulphate test solution
Materials Rs (Ω cm2) [(Rct) / (Rco)] (KΩ cm2) [(Cdl) / (Cco)] (μF cm− 2)
CS 24.09 4.94 52.90
MCS 7.89 15.32 89.10
FMCS-1 36.60 39.60 29.80
FMCS-2 1.37 98.50 1.25
MCS, the specimen FMCS-2 showed the lowest corrosion current. In
FMCS-2 specimen, MgFe2O4 coating on Fe3O4 possibly reduced the
number of pores at the Fe3O4/MgFe2O4 interface due to their lattice
matching. The reduction in the number of nano-pores might restrict
the inward movement of the oxygen carrying species in this sample
resulting in lower corrosion current. In the case of FMCS-1 sample, the
coating was composed of several oxides like MgO, Fe2O3 and MgFe2O4.
Presence of various oxides possibly did not allow the number of pores
at the interface of the second layer to be reduced to the extent as in the
case of FMCS-2 sample.
4. Conclusions
In this report, a thin film of MgFe2O4 was developed on Fe3O4
coated carbon-steel to improve the protectiveness of the film. The film
deposited by laser ablation was found to be adhesive with Fe3O4
coated specimen rather than over plain carbon-steel specimen. XRD of
the film confirmed the spinel structure formation. Based on the
measured relative atomic ratio of Mg and Fe on the film, XPS studies
determined the chemical composition of spinel structure as MgFe2O4.
The SEM micrograph of the film showed the coating to be very
smooth. Particle size of MgFe2O4 coating was found below 100 nm by
AFM. Impedance measurements of the coating showed enhancement
in corrosion resistance property. It is concluded from these studies
that the MgFe2O4 coated films offer a barrier for the movement of the
ionic species through nano pores and grain boundaries and as a result
better corrosion resistant product could be obtained.
Acknowledgements
The authors thank Dr. S. Kalavathi and Dr. G. Mangamma of MSD,
Kalpakkam for carrying out XRD and AFM analysis of the samples.
They are thankful to Mr. P. Gangopadhaya for carefully going through
the manuscript.
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