Microporous and Mesoporous Materials 218 (2015) 62e68

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

A new strategy based on thermodiffusion of ceramic nanopigments

into metal surfaces and formation of anti-corrosion coatings
Maryam Shaterian a, *, Asma Khoobi b, Morteza Enhessari c, Keyvan Ozaee d
a

Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan 45371-38791, Islamic Republic of Iran
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan P.O. Box 87317-51167, Islamic Republic of Iran
c
Department of Chemistry, Naragh Branch, Islamic Azad University, Naragh, Islamic Republic of Iran
d
Young Researchers and Elite Club, South Tehran Branch, Islamic Azad University, Tehran, Islamic Republic of Iran
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 21 March 2015
Received in revised form
2 June 2015
Accepted 28 June 2015
Available online 11 July 2015

The present paper is the rst report about preparation of anti-corrosion coatings based on thermodiffusion of ceramic nanopigments into metal surfaces. At rst, Cr1.3Fe0.7O3 ceramic nanopigments have
been synthesized by simple and environmentally benign solegel method. Annealing of the gels at
different temperatures ranging from 600 to 1000
C yielded the pure rhombohedral structure. The
structural evolutions and microstructural characteristics of the synthesized nanoceramics were investigated through different methods containing X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Then
Cr1.3Fe0.7O3 ceramic nanopigments were coated on mild steel surface via thermodiffusion method. The
surface morphology and the corrosion behavior of the Cr1.3Fe0.7O3 coatings were evaluated using atomic
force microscopy (AFM), eld-emission scanning electron microscopy (FE-SEM), electrochemical
impedance spectroscopy (EIS), potentiodynamic polarization and weight loss measurements in a solution of 2.0 M HCl. It is found that morphology of diffusion coatings affects the protective properties of
mild steel. On the other hand, in extra-corrosive HCl media Cr1.3Fe0.7O3 nanoceramic coatings provide
mild steel with high protective properties.
2015 Elsevier Inc. All rights reserved.

Keywords:
Ceramic nanopigments
Thermodiffusion
Anti-corrosion coatings

1. Introduction
Corrosion is a natural process that reduces the binding energy in
metals. It occurs at the metal/environment interfaces, and causes a
deterioration of the metals and their properties. During the
corrosion process the metallic ions precipitate on the metal surface
and by forming corrosion lm separates the metal from the
aggressive environment [1]. Iron and its alloys play key roles in our
daily lives because of their excellent properties, such as high mechanical and structural strengths [2]. These materials are used in
different industrial and have various engineering applications. Mild
steel is now the most common form of steel because its price is
relatively low while it presents material properties that are
acceptable for many applications. Low-carbon steel contains
approximately 0.05e0.15% carbon making it ductile and malleable.
Mild steel has a relatively low tensile strength, but it is cheap and

* Corresponding author.
E-mail address: shaterian@znu.ac.ir (M. Shaterian).
http://dx.doi.org/10.1016/j.micromeso.2015.06.039
1387-1811/ 2015 Elsevier Inc. All rights reserved.

easy to form; surface hardness can be increased through carburizing [3]. Therefore, mild steel due to its excellent mechanical
properties is the constructional material of choice in numerous
chemical and petrochemical industries as well as daily life applications. The main drawback of mild steel is its low corrosion
resistance. On the other hand, it is easily attacked and solubilized in
acidic media which are widely used to remove of undesirable rusts
and scales in several industrial sectors [4]. Oil-well acidizing, acidpickling, acid-cleaning and acid-descaling, are usual industrial
processes for cleaning the metals surfaces. Also it is necessary to
apply acid solutions to eliminate undesirable scale and corrosion
products from metals. Sulfuric acid and hydrochloric acid are
generally used for this purpose; but, these acids attack the metal
surface and begin corrosion process. Corrosion can cause drastic
damage to the metal surface and degrade its properties, thus
limiting its applications [5,6].
The use of corrosion inhibitors is very important method for
protecting metals from corrosion, and numerous scientists are
conducting research on this area. In principle, inhibitors prevent
the corrosion process of metal by interacting with the metal surface

M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

by adsorption through the p-orbitals, donor atoms, electron density and the electronic structure of the molecule [7e10]. Hard
coatings with carbide, nitride, boride, or carbonitride of transition
metals are widely used in order to increase corrosion resistance
[10]. The coatings are employed in order to isolate the metal and
steel surfaces from the corrosive environment and prevent the
diffusion of water vapor, oxygen, or ions, which act as a source that
begins the corrosion [11]. Moreover, these ceramic coatings
demonstrate high dielectric strength, which generates the formation of a more noble surface [12,13]. Conventional methods for
making these coatings are thermal welding, spraying, chemical
vapor deposition (CVD), electroplating and physical vapor deposition (PVD) [14,15]. All of the methods are high energy consumption
techniques. Additionally, sometimes toxic elements such as cadmium are used as alloy coating but now require to be replaced with
more environmental friendly materials [16,17]. Coating by composites or polymers is usually not suitable for high temperature
applications because of their polymeric nature. However, oxide
ceramics are suitable candidates as anti-corrosion coatings to be
used under harsh environmental conditions [18,19].
In this study, the surface treatment of mild steel was carried out
by the thermodiffusion of Cr1.3Fe0.7O3 ceramic nanopigments for
the rst time. The theory of thermodiffusion for preparation of anticorrosive coatings was discussed. Various properties such as phase
composition and particle size distribution of the ceramic nanopigments have been evaluated. The effect of Cr1.3Fe0.7O3 thermodiffusion on the corrosion inhibition of mild steel in hydrochloric
acid media was investigated.
2. Experimental
2.1. Chemicals
Iron (III) nitrate decahydrate [Fe(NO3)3$10H2O], ammonium dichromate [(NH4)2Cr2O7], stearic acid, nitric acid and hydrochloric
acid were obtained from Merck company (Darmstadt, Germany).
All reagents were of analytical grade and used as received without
further purication. Deionized water was used throughout this
study.
2.2. Synthesis of the nanopowder
Cr1.3Fe0.7O3 ceramic nanopigments were synthesized via solegel method based on previous work [20]. Briey, stearic acid was
melted in a beaker at a temperature of 73
C. Then, Fe(NO3)3$10H2O
and (NH4)2Cr2O7 were added in stoichiometric proportion to a
mixture of water and nitric acid (1:1%v/v). The Fe(NO3)3$10H2O/
(NH4)2Cr2O7 molar ratio was 0.7:1.3. This solution was added into
the melted stearic acid. The beaker was kept in an oven at 90
C for
48 h until a homogenous light red-brown sol was obtained. The sol
was cooled down to room temperature and subsequently dried in
an oven for 12 h. Finally the nanopowder was calcined at 600, 800,
900 and 1000
C for 2 h.

63

specimens with dimension of 1 cm  1 cm  0.1 cm were used as

substrate. The surface of mild steel electrodes mechanically
abraded prior to use with different emery papers up to 1200 grade.
The mild steel specimens were cleaned with analytical ethanol and
then immersed in analytical acetone and nally washed with
deionized water before coating. Then Cr1.3Fe0.7O3 nanoceramic
coatings were deposited onto mild steel specimen (working electrode) using thermodiffusion process. The process was performed
by diffusion of Cr1.3Fe0.7O3 nanopowder into the working electrode
at 900
C for 4 h. The mechanism of thermodiffusion process is
discussed in Result and discussion section.
In this study, hydrochloric acid (2.0 M) was selected as corrosive
solution and was prepared by dilution of analytical grade 37% HCl
with deionized water.
2.4. Microstructural and electrochemical characterization
The crystal structures of the nanopigments were studied by
X-ray diffraction (XRD) analysis. The diffraction patterns of the
samples were obtained with a Seifert diffractometer (Model PTS
3003). The data were collected within 2q angle from 10
to 80

using Cu Ka line (l 0.15418 nm). Scanning electron microscopy
(SEM) micrographs were obtained by an LEO 1455 UP analyzer
(Oxford, UK). The morphology and crystallite size of the nanoceramics were investigated by transmission electron microscopy
(TEM) using a Philips EM 208 electron microscope operated at an
acceleration voltage of 100 kV.
The surface morphology of each specimen was studied using a
0201/A of ARA atomic force microscopy (AFM) and eld-emission
scanning electron microscopy (FE-SEM) (Mira 3 XMU) before and
after immersion in 2.0 M HCl in the absence and presence of
Cr1.3Fe0.7O3 thermodiffusion.
Corrosion inhibition electrochemical tests of the Cr1.3Fe0.7O3
nanoceramic coatings containing electrochemical impedance
spectroscopy (EIS) and Tafel polarization were performed using an
AUTOLAB model PGSTAT30. EIS studies were performed at corrosion potentials (Ecorr) over a frequency range of 10 kHze0.1 Hz with
a signal amplitude perturbation of 5.0 mV. Then impedance data
were analyzed using a Pentium IV computer and FRA software. The
Tafel polarization experiments were carried out with a scan rate of
0.5 mV s1 and the data were analyzed using GPES electrochemical
software.
3. Results and discussion
3.1. Characterization of the Cr1.3Fe0.7O3 nanopowder

2.3. Electrochemical cell

3.1.1. X-ray diffraction

Fig. 1 represents XRD patterns for Cr1.3Fe0.7O3 nanoceramics at
different temperatures [20]. As can be observed the crystallinity of
the as-prepared products was continuously improved with the
increase of the calcination temperature from 600
C to 1000
C.
Based on Fig. 1a, calcination in 1000
C leads to formation of pure
rhombohedral structure (JCPDS, Card No. 35-1112). There is no peak
that could be attributed to Cr2O3 or Fe2O3.

Corrosion experiments were performed in a three-electrode cell

opened to air under stagnant conditions at a thermostated temperature of 25
C. An Ag/AgCl/KCl (sat.) (Metrohm, Switzerland)
and a platinum sheet (Metrohm, Switzerland) were used as the
reference and counter electrodes, respectively. Corrosion inhibition
tests were performed using specimens prepared from mild steel
as working electrode, having the composition (wt%): C:0.027;
Si:0.0027; Mn:0.34; P:0.009; S:0.003; Cr:0.008; Ni:0.03; Cu:0.007;
Al:0.068; Nb 0.003, Ti 0.003, V 0.003 and Fe balance. The test

3.1.2. Energy dispersive X-ray analysis

The chemical analysis for determination of the ceramic nanopigments composition was performed via energy dispersive X-ray
spectroscopy (EDX). Fig. 2 demonstrates the EDX results of the
ceramic nanopigments [20]. The spectrum shows prominent peaks
of Cr and Fe. From the peaks, it is conrmed that the nanoceramics
synthesized by solegel method. The atomic ratio of Cr/Fe detected
by EDX analyzer was near stoichiometric value in Cr1.3Fe0.7O3,
conrming the expected high purity of the nanopigments.

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M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

Fig. 1. XRD patterns of the nanopowders calcined at (a) 600, (b) 800, (c) 900 and (d)
1000
C for 2 h.

Fig. 3. Microstructure obtained of Cr1.3Fe0.7O3 nanopigments by SEM.

the overall randomness or entropy of the material increases, subsequently the thermodynamic stability of a crystalline material
increases. Vacancies are created into metals and alloys during solidication, at high temperatures. The concentration of vacancies at
room temperature (~298 K), is small, but it increases exponentially
when the temperature increases, according the Arrhenius equation
[21] (Eq. (1)):

Nv nexp

Fig. 2. EDX spectrum recorded for Cr1.3Fe0.7O3 nanoceramic pigments.

3.1.3. SEM and TEM micrographs

The surface morphology of the ceramic nanopigments synthesized by solegel method is presented in Fig. 3 [20]. The SEM micrographs clearly indicate that Cr1.3Fe0.7O3 is composed of spherical
particles. Also, inspection of Fig. 3 discloses that spherical grains
have regular shaped morphology with a homogenous distribution.
The morphology, shape and particle size of calcined powders
were also examined by TEM analysis. The TEM image in Fig. 4
shows that the Cr1.3Fe0.7O3 nanoparticles are spherical in shape
[20]. The average crystalline size of the nanopigments was obtained
about 100 nm that was composed of smaller nanoparticles with
compatible values with SEM analysis.
3.2. Application of Cr1.3Fe0.7O3 nanoceramics as a corrosion
inhibitor
3.2.1. Thermodiffusion mechanism
A vacancy is generated when an ion or an atom is missing from
its normal site in the crystal structure. When vacancies formation

Ev
RT


(1)

where Nv is the number of vacancies per cm3, n is the number of

atoms per cm3, Ev is the energy required to create 1 mol of vacancies (cal mol or Joules mol), R is the gas constant and T is the
absolute temperature (K). There may be produced as many as one
vacancy per 1000 atoms due to the large thermal energy near the
melting temperature. This equation presents the equilibrium concentration of vacancies at a given temperature. Therefore, the
atomic and ionic arrangements in materials are never perfect and
the imperfections are raised with increasing of the temperature.
Also, different types of species such as atoms or ions typically
diffuse or move within the material. Diffusion ascribes to an
observable net ux of atoms, ions or other species that depends
upon the concentration gradient and temperature. The capacity of
atoms and ions to diffuse raises as the temperature, or thermal
energy possessed by the atoms and ions, increases. The dependence
of atom or ion movement rate to temperature or thermal energy is
described by the Arrhenius equation [21,22] (Eq. (2)):




Ea
Rate c0 exp
RT

(2)

where c0 is a constant, R is the gas constant, T is the absolute

temperature (K) and Ea is the activation energy required to cause
1 mol of atoms or ions to move. This equation is derived from a
statistical analysis of the probability that the atoms will have the
additional energy Ea required to cause movement. The rate is
related to the number of atoms that move.
In materials containing vacancies, with increasing of temperature diffusion of unlike atoms in the lattice can be occurred [21]. In
the present study, this theory is the main mechanism for formation
of novel anti-corrosion coatings for the rst time. In fact with
increasing of temperature at rst the vacancies raise in the mild
steel lattice and then gradually the Fe atoms of Cr1.3Fe0.7O3 nanoceramic lattice diffuse in to the mild steel vacancies (Fig. 5) [21].

M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

65

Fig. 4. TEM micrograph of Cr1.3Fe0.7O3 nanoceramic pigments.

nanopigments thermodiffusion as expected due to corrosive attack

by the acid solution. Fig. 7c and d presents the surface morphology
of mild steel obtained after thermodiffusion process before and
after exposure to 2.0 M HCl, respectively. Fig. 7d shows the protected mild steel surface after Cr1.3Fe0.7O3 thermodiffusion,
whereby the surface damage has diminished in comparison to the
blank material (Fig. 7b). This observation clearly proves that thermodiffusion of Cr1.3Fe0.7O3 ceramic nanopigments can exhibit good
inhibiting ability on mild steel surface.

Fig. 5. Diffusion of Fe atoms from Cr1.3Fe0.7O3 nanoceramics into mild steel lattice. (a),
(b) and (c) show the effect increasing of temperature on diffusion. Eventually, the Fe
atoms are randomly distributed throughout the mild steel lattice.

3.2.2. Surface morphological analysis of the anti-corrosion coatings

AFM is a powerful technique to investigation the surface
morphology at nano-to micro-scale and has become a new choice to
study the inuence of inhibitors on the generation and the progress
of the corrosion at the metal/solution interface [9]. To investigate
the effect of the nanoceramic coating on the surface morphology of
the mild steel, surface examination was performed using AFM. Fig. 6
shows the surfaces of mild steel samples before and after exposing
to 2.0 M HCl solution in the absence and presence of Cr1.3Fe0.7O3
thermodiffusion by AFM technique. Figs. 6a and b illustrate the AFM
micrographs of the mild steel surface before and after immersion in
2.0 M HCl solution, respectively. The micrographs demonstrate that
the surface was strongly damaged in the absence of the inhibitor.
Fig. 6c shows image of the surface of the mild steel specimen
immersed in 2.0 M HCl after Cr1.3Fe0.7O3 ceramic nanopigments
thermodiffusion. Comparison of Fig. 6b with others shows that the
cracks on the mild steel surface are clearly due to acid attack. As can
be observed from Fig. 6c, the surface damage has moderated in the
presence of anti-corrosion coating. It was revealed that a good
protective lm is formed on the specimen surface that is responsible for the inhibition of corrosion.
To conrm whether Cr1.3Fe0.7O3 ceramic nanopigments thermodiffusion is accomplished into mild steel lattice, surface analysis
of the specimens was investigated using FE-SEM. The micrographs
of polished mild steel without exposure to Cr1.3Fe0.7O3 ceramic
nanopigments thermodiffusion in the absence and presence of
2.0 M HCl are presented in Fig. 7a and b, respectively. Analysis of
the FE-SEM image in Fig. 7b reveal that the mild steel specimen
displays a very rough surface in the absence of Cr1.3Fe0.7O3 ceramic

3.2.3. Electrochemical impedance spectroscopy

EIS is an informative, powerful and non destructive technique
that commonly used for the evaluation of coatings on metals and
alloys. EIS measurements examined changes in Faradaic and nonFaradaic impedances at the metal-solution interface. The Faradaic
(charge transfer) impedances at low frequencies in the spectrum
initiate from the anodic and cathodic reactions of corrosion, while
the non-Faradaic impedances, observed at high frequencies, have
been attributed to surface charging and occlusion by corrosion
products or passivation [23,24]. EIS data is usually analyzed by
tting it to an equivalent electrical circuit model. The Randle cell as
a simple and useful electrical circuit is combination of a capacitor,
two resistors, and diffusion or Warburg impedance that can be used
to represent a coating or corroding metal, although the values and
meaning of the components are different [25]. The impedance can
be represented by Eq. (3) [24]:

Zu ZRe  jZIm

(3)

where ZRe and ZIm are the real and imaginary parts of the impedance, respectively.
The impedance experiments were carried out for both bare and
coated mild steel electrodes in 2.0 M HCl as corrosive environment.
EIS spectra for coated mild steel were recorded after thermodiffusion of Cr1.3Fe0.7O3 nanoceramics in to the mild steel at 900
C for
4 h in 2.0 M HCl solution. Fig. 8 exhibits changes in Nyquist plots for
mild steel in 2.0 M HCl in the absence and present of Cr1.3Fe0.7O3
nanoceramic coatings. The typical Nyquist plot of the interface mild
steel/HCl demonstrates a single semi circle shifted along the real
impedance (ZRe) axis. The EIS spectra were tted by Randles
equivalent circuit (Fig. 9), which is a combination of the solution
resistance (Rs), double-layer capacitance (Cdl), charge transfer
resistance (Rct) and Warburg impedance (Zw). The double-layer
capacitance value is calculated by Eq. (4) [26]:

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M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

Fig. 6. AFM topography of mild steel (a) before corrosion, (b) after immersion in 2.0 M HCl, and (c) as (b) in the presence of Cr1.3Fe0.7O3 thermodiffusion.

Cdl Y0 umax n1

(4)

where umax is the frequency at which the imaginary part of

impedance (ZIm) is maximum. Also, inhibition efciency h (%) can
be calculated from the Rct values using the Eq. (5) [27]:

h%

Rct0
1
Rcti

!
 100

(5)

where Rct(0) is the charge transfer resistance of mild steel without

inhibitor and Rct(i) is the charge transfer resistance of mild steel
with inhibitor. The values calculated for Rct(0) and Rct(i) were 4.6 and
40.9 U cm2, respectively. Using these data, inhibition efciency h (%)
was obtained 88.7%. From the data it is clear that the charge transfer
resistance of the bare mild steel electrode is very low. But the
charge transfer resistance changes at the presence of nanoceramic
coatings with a magnication of 8.9 times greater than bare mild
steel electrode which indicates the higher efciency. The results
suggest the formation of a protective layer on the electrode surface
that this layer generates a barrier for mass and charge transfer.
3.2.4. Potentiodynamic polarization
In any process of electrochemical corrosion both oxidation and
reduction processes occur on the surface of the metal. In the
studied system these processes occur simultaneously during the
polarization for each of the used potential values but at different

speeds. The characteristics current intensity as function of the

potential is investigated by potentiodynamic polarization curves.
In the present study, Tafel potentiodynamic polarization experiments were performed in order to gain further insight about the
anti-corrosion behavior of Cr1.3Fe0.7O3 nanoceramics. Fig. 10 represents the anodic and cathodic potentiodynamic polarization
curves of mild steel in 2.0 M HCl solution in the absence and the
presence of Cr1.3Fe0.7O3 nanoceramics. As can be observed in
Fig. 10, cathodic current decreases in the presence of the nanoceramic coatings. Also, inspection of Fig. 10 reveals that Ecorr value
in the presence of inhibitor is shifted to more negative direction.
Regarding the polarization curves, the adsorption of the nanoceramics has a pronounced effect on the cathodic parts of the
polarization curves and it is seemed that Cr1.3Fe0.7O3 nanoceramics can be classied as a cathodic inhibitor. This effect is
attributed to the thermodiffusion of the inhibitor on the active
sites of the metal surface. Electrochemical corrosion parameters,
i.e. corrosion potential (Ecorr), corrosion current density (Icorr),
cathodic Tafel slope (bc) and anodic Tafel slope (ba) obtained from
polarization curves and inhibition efciency (h) of the nanoceramics are presented in Table 1. The inhibition efciency in the
presence of Cr1.3Fe0.7O3 nanoceramic coatings can be calculated
from the Eq. (6) [27]:

h%

1

Icorri
Icorr0

!
 100

(6)

M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

67

Fig. 7. FE-SEM images of unexposed and exposed mild steel in 2.0 M HCl in the presence and absence of Cr1.3Fe0.7O3 thermodiffusion. (a) Unexposed mild steel, (b) 2.0 M HCl, (c)
unexposed mild steel in the presence of Cr1.3Fe0.7O3 thermodiffusion, (d) 2.0 M HCl in the presence of Cr1.3Fe0.7O3 thermodiffusion.

Fig. 9. The equivalent electric circuit used to obtain the impedance parameters.

Fig. 8. Nyquist plots of mild steel electrode in the absence and presence of Cr1.3Fe0.7O3
thermodiffusion obtained in 2.0 M HCl solution.

where Icorr(i) and Icorr(0) are the corrosion current densities in the
presence and absence of inhibitor, respectively. The obtained results indicate that Cr1.3Fe0.7O3 nanoceramic coatings on the surface
of mild steel decrease the Icorr value, which indicates the higher
inhibition efciency. For the bare mild steel electrode in corrosive

HCl media the Icorr is 53.2 mA cm2, when thermodiffusion of

Cr1.3Fe0.7O3 nanoceramics is performed into the mild steel, Icorr
decrease to 5.1 mA cm2. The high inhibition efciency observed in
the presence of modied mild steel indicates that iron atoms from
Cr1.3Fe0.7O3 nanoceramics are adsorbed on the metal surface of
mild steel thus providing wider surface coverage and this compound is acting as adsorption inhibitor.
3.2.5. Corrosion rates
Measurements of weight loss were used to calculate the corrosion rates because of its reliability and simple application [28]. To
measure the weight lost by corrosion the mild steel specimens

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M. Shaterian et al. / Microporous and Mesoporous Materials 218 (2015) 62e68

coatings. Table 2 presents the calculated values of corrosion rates

obtained using Eq. (7) and inhibition efciency values evaluated
using the expression given in Eq. (8). It is clear that the inhibition
efciency in the presence of anti-corrosion coating is in good
agreement with obtained results from the EIS and potentiodynamic
polarization methods.
4. Conclusion

Fig. 10. Tafel Polarization curves for mild steel in 2.0 M HCl in the absence and
presence of Cr1.3Fe0.7O3 thermodiffusion.

Table 1
Polarization parameters for mild steel in 2.0 M HCl in the absence and presence of
Cr1.3Fe0.7O3 thermodiffusion at 25
C.
Electrode
Mild Steel
(blank)
Cr1.3Fe0.7O3
coating

-Ecorr
(mV vs. Ag/AgCl)

bc

ba

(mV dec1)

Icorr
(mA cm2)

h (%)

0.42

0.022

0.018

53.2

0.62

0.035

0.095

5.1

(mV dec1)

90.4

Table 2
Weight loss results of mild steel corrosion in 2.0 M HCl in the absence and presence
of Cr1.3Fe0.7O3 thermodiffusion at 25
C.
Inhibitor

Cr1.3Fe0.7O3 coating

2h

h (%)

h (%)

0.29

88.6

0.13

91.8

were weighed before the immersion test. The difference between

the mass of the sample before and after immersing in 2.0 M HCl
solution in the absence and presence of the anti-corrosion coating
was the total mass loss. Corrosion rate that containing measuring
the mass of metal turned into corrosion products per unit area of
surface per unit of time is described by Eq. (7) [29]:

m1  m2
S$t


(7)

where m1 and m2 are coupon weights measured before and after

immersion in the test solutions in (mg), respectively, S is the
exposed area (cm2), t is the exposure time (h) and w is the corrosion
rate (mg cm2 h1)
Additionally, inhibition efciency h(%) is calculated using the
Eq. (8):

h%

Acknowledgments
We are grateful to the council of Iran National Science Foundation for providing nancial support to undertake this work with
Grant 92039044.
References

Immersion time
1h

Solegel method was successfully applied to synthesize

Cr1.3Fe0.7O3 ceramic nanopigments by varying in the calcination
temperature. The experiments showed that calcination in 1000
C
leads to formation of pure rhombohedral structure. The structural,
morphological and optical properties of pure nanoceramics were
analyzed using XRD, EDX, SEM and TEM analyses. Then the performance of Cr1.3Fe0.7O3 ceramic nanopigments was investigated as
a corrosion inhibitor. A novel mechanism was suggested for formation of anti-corrosive coatings for the rst time. This process was
performed based on thermodiffusion of Cr1.3Fe0.7O3 nanoceramics
into the alloy surface. Then the corrosion inhibition mechanism on
mild steel in 2.0 M HCl media before and after thermodiffusion was
investigated by AFM, FE-SEM, EIS, Tafel potentiodynamic polarization and weight loss methods. Results evidenced that Cr1.3Fe0.7O3
nanoceramics on the mild steel surface showed excellent performance as a corrosion inhibitor.

wblank  winh
wblank


 100

(8)

where the subscripts (blank) and (inh) for the corrosion rate w
indicate the absence and presence of the inhibitor in the hydrochloric solution, respectively.
Therefore, a series of weight loss measurements were carried
out in 2.0 M HCl in the absence and presence of the Cr1.3Fe0.7O3

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