Available online at SciVerse ScienceDirect

J. Mater. Sci. Technol., 2014, 30(1), 47e53

Corrosion Protective Conversion Coatings on Magnesium Disks

Using a Hydrothermal Technique
R.K. Gupta1)*, K. Mensah-Darkwa2), D. Kumar2)
1) Department of Chemistry, Pittsburg State University, 1701 S. Broadway, Pittsburg, KS 66762, USA
2) Engineering Research Center for Revolutionizing Metallic Biomaterials (ERC-RMB), Department of Mechanical Engineering,
North Carolina A&T State University, 1601 East Market Street, Greensboro, NC 27411, USA
[Manuscript received March 29, 2013, in revised form May 2, 2013, Available online 23 July 2013]

A uniform, compact, and well adherent conversion coating of magnesium hydroxide has been formed on
bioresorbable magnesium disks by means of a hydrothermal technique. Electrochemical results indicate that
the coating brings about a significant reduction in magnesium corrosion in phosphate buffered saline (PBS)
solution. It is also observed that corrosion resistance of the coating increases with an increase in treatment
time, which in turn, increases the coating thickness. The protective behavior of magnesium hydroxide coating
is attributed to its chemical inertness in PBS solution. The coatings are found to be free from pores that
reduce the direct contact between corroding media and underlying magnesium.
KEY WORDS: Magnesium; Polarization; Electrochemical impedance spectroscopy (EIS); Scanning electron microscopy (SEM); Conversion
coating; Corrosion

1. Introduction
Magnesium (Mg) and its alloys have attracted considerable
research interest for biomedical and automobile applications
because of their promising properties such as biocompatibility,
low density, high specic strength, castability, and appropriate
hardness[1e6]. However, the high corrosion rate of Mg severely
limits its usage in almost all of these applications[7,8]. Therefore,
in order to utilize Mg in these applications, the corrosion rate of
Mg needs to be slowed down[9,10]. An effective way to reduce
the corrosion rate of Mg and its alloys is surface modication[7,11,12]. Surface modication includes anodic oxidation[13],
metal coating[14], chemical conversion coating[15], plasma electrolytic oxidation[16], and organic coating[17]. The surface
modication by chemical conversion coating is widely used
because of its easier operation, effectiveness, and lower cost[18].
Among the chemical conversion coatings, chromate conversion
coating is one of the most effective and popular conversion
coating to reduce the corrosion rate of Mg[19]. However, the use
of chromate coating is being progressively restricted due to the
high toxicity of the hexavalent chromium compounds; hence it is

Corresponding author. Ph.D.; Tel.: 1 620 235 4763; Fax: 1 620 235
4003; E-mail address: ramguptamsu@gmail.com (R.K. Gupta).
1005-0302/$ e see front matter Copyright 2013, The editorial ofce of
Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
http://dx.doi.org/10.1016/j.jmst.2013.07.012
*

necessary to develop environment friendly replacements for

chromate conversion coatings[11,20].
Different types of conversion coating such as phosphate[21],
phosphate/permanganate[22], uoride[23], stannate[24], phytic
acid[25], rare earth element based conversion coatings[26,27] have
been emerging as an alternative to chromate conversion coating
to reduce the corrosion rate of the Mg and its alloys. Cui et al.[28]
used neodymium-based conversion coating on Mg alloy as a
substitute for toxic chromate conversion coating. They observed
that post treatment of the phytic acid coating improves the
corrosion resistance of the Mg alloy. Recently, we have also
reported that post heat treatment of phytic acid conversion coated
Mg shows improved corrosion resistance compared to non-heat
treated phytic acid conversion coated Mg[29]. Cerium based
conversion coatings have been used to decrease the corrosion
rate of AZ31 magnesium alloy[30]. The effect of varying Ca2
and PO4 3 concentrations on the formation of calcium phosphate
conversion coatings on Mg alloy was studied[31]. It was observed
that low PO4 3 concentration improves the corrosion resistance
of Mg alloy.
Recently, Ishizaki et al.[32] used magnesium hydroxide/magnesium phosphate compound composite coating for corrosion
protection of Mg alloy by a combination process of chemical
conversion and steam curing. It was found that the corrosion
current density for the coated sample decreased by more than
four orders of magnitude as compared to uncoated sample. Zhu
et al.[33,34] used hydrothermal technique to deposit a protective
coating on the Mg alloy. They observed that the conversion
coating fabricated using the hydrothermal method gives efcient

48

R.K. Gupta et al.: J. Mater. Sci. Technol., 2014, 30(1), 47e53

corrosion protective layer on the Mg alloys. Guo et al.[35]

fabricated zincealuminum layered double hydroxide bilayer
lms on aluminum substrates by one-step hydrothermal crystallization method. The advantage of the hydrothermal technique
is that the coatings are uniform, compact, and have strong
adhesion to substrates and thus, can effectively protect substrates
from corrosion. As the hydrothermal crystallization occurs on a
3-dimensional structure, this method can also be used to coat 3dimensional objects[33].
In the present work, a hydrothermal technique was used to
obtain a corrosion protective conversion coating of magnesium
hydroxide (Mg(OH)2) on the surface of Mg disks. The idea of
Mg(OH)2 coating stems from the fact that if the Mg implant
surfaces are already coated with Mg(OH)2, Mg will not react
with the uid in the body and the release of Mg ions and thereby
evolution of hydrogen will not take place. The structural and
corrosion properties of the hydrothermally coated Mg disks and
uncoated Mg disk (control) were studied. The results indicate
that the hydrothermally coated Mg disks are corrosion protective
compared to uncoated Mg disk which is due to low porosity of
the coatings.
2. Experimental
Mg disks for the hydrothermal treatment were prepared by
cutting Mg (99.9%, Good Fellow, Germany) rod (13 mm in
diameter) with a thickness of w1.5 mm. Each Mg disk was
polished with SiC paper successively up to #1200 grit, followed
by ultrasonic cleaning in acetone and isopropyl alcohol for
5 min, respectively. A hydrothermal technique was applied for
conversion coatings on Mg disks using deionized water. The
deionized water was poured into a hydrothermal reaction vessel,
which was made of Teon lined stainless steel, and lled upto
75% volume of reaction vessel. The Mg disk was kept in the
reaction vessel and heated to 160  C in a furnace. The hydrothermal treatment was carried out for 1, 3, 5, and 7 h. Hereafter,
sample 1 represents uncoated Mg disk (control) whereas sample
2, 3, 4, and 5 represent hydrothermal coated Mg disks in
deionized water for 1, 3, 5, and 7 h, respectively.
The structural characterizations were performed by X-ray
diffraction (XRD) technique. The XRD spectra of the uncoated
Mg disk and hydrothermally coated Mg disks were recorded
with Bruker AXS (D8 Discover) X-ray diffractometer using the
2qeq scan with CuKa (l 0.15405 nm) radiation. The microstructures of the samples were recorded before and after
corrosion process by scanning electron microscopy (SEM,
SU8000, Hitachi). The degradation rate of the uncoated and
coated Mg disks was studied using hydrogen release rate. For
this study, the disks were immersed and kept in the phosphate
buffered saline (PBS) solution (137 mmol/L NaCl, 2.7 mmol/L
KCl, 8 mmol/L Na2HPO4, and 2 mmol/L KH2PO4) and kept in
the solution for 2 weeks at 37  C in a water bath. Hydrogen gas
released due to the corrosion of samples was collected into a
burette. The reading of total volume of evolved hydrogen gas
was recorded at regular time interval.
DC potentiodynamic polarization measurements were performed in 1 PBS solution using Gamry Potentiostat (R600,
Gamry Instruments) with a standard three-electrode conguration. A saturated calomel electrode (SCE) and platinum wire
were used as the reference and counter electrodes, respectively.
Uncoated Mg disk and coated Mg disks were used as working
electrode. The polarization measurements were carried out in the
applied potential range of 300 mV vs. SCE, at a scan rate of

5 mV/s. Corrosion potential (Ecorr) and corrosion current density

(Icorr) were determined using the Echem Analyst software
(Gamry Instruments). The electrochemical impedance spectroscopy (EIS) study was performed in the frequency range of
1e106 Hz under 10 mV amplitude of the perturbation signal.
3. Results and Discussion
3.1. X-ray diffraction study
X-ray diffraction patterns for the uncoated Mg disk and hydrothermally treated Mg disks are shown in Fig. 1. As seen in
Fig. 1, the observed diffraction patterns of the Mg disk showed
polycrystalline nature. All the observed peak positions of the Mg
disk were found to be in good agreement with the hexagonal
phase of Mg (JCPDS le No. 035-0821). Besides the typical
peaks corresponding to Mg, some other diffraction peaks were
also observed in the hydrothermally treated Mg samples. The
presence of other diffraction peaks in the XRD patterns of hydrothermal treated Mg samples indicates the existence of other
phases. The extra diffraction peaks other than those arising from
Mg plate were observed to be due to the formation of Mg(OH)2
during the hydrothermal treatment of the Mg disks. The formation of Mg(OH)2 on the surface of Mg disks during the hydrothermal reaction can be explained on the basis of following
reactions:
H2 Ol/H aq OH aq

(1)

Mgs/Mg2 aq 2e

(2)

2H aq 2e /H2 g

(3)

Mg2 aq 2OH aq/MgOH2 s

(4)

The observed extra peaks in the hydrothermally treated Mg

samples were in good correlation with the hexagonal phase of
Mg(OH)2 (JCPDS le No. 075-1527). It is also evident from the
XRD patterns that the intensity of magnesium hydroxides

Fig. 1 XRD patterns of uncoated Mg disk (control) and hydrothermally

coated Mg disks.

R.K. Gupta et al.: J. Mater. Sci. Technol., 2014, 30(1), 47e53

diffraction peaks increases with increasing the hydrothermal

treatment time, which suggest that the thickness and crystallinity
of Mg(OH)2 coating on Mg disk improve with longer hydrothermal treatment time[34]. The lattice parameters of the hexagonal phase of Mg(OH)2 coating were calculated using the
following expression[36]
1
4 h2 hk k 2 l 2

2
2
3
a2
c
dhkl

(5)

where d is the inter-planar spacing, h, k, and l are the Miller

indices, and a and c are the lattice parameters of the hexagon.
The lattice parameters of Mg(OH)2 were found to be
a 0.3147 nm, and c 0.4779 nm.
3.2. Microstructural properties
The SEM images of the uncoated Mg disk and hydrothermally
Mg(OH)2 coated Mg disks as a function of the hydrothermal
treatment time are shown in Fig. 2. As seen in these SEM images, the surface morphology of the treated Mg samples changes
with the hydrothermal treatment time. The insets show the SEM
images of the same sample with higher magnication. As evident
from these microstructures, the hydrothermally treated Mg
samples have different surface morphology compared to the
untreated Mg disk (control). It is apparent from the surface
morphology of sample 2 (hydrothermal treatment time, 1 h) that

49

the growth of conversion coating has started. In sample 3 (hydrothermal treatment time, 3 h), some signatures of hexagonal
structure of Mg(OH)2 can be seen. Further, with the increase in
the hydrothermal reaction time (5 h and 7 h), the hexagonal
structure of Mg(OH)2 conversion coating is clearly evident in the
sample 4 and sample 5. The presence of hexagonal structure of
Mg(OH)2 conversion coating in the SEM images, has been also
conrmed in the XRD analysis of the hydrothermally treated
samples.
The effect of hydrothermal treatment time on the thickness
of the conversion coating on Mg disks was studied using cross
section SEM imaging. The cross section SEM images of
sample 4 and sample 5 are shown in Fig. 3 as representatives.
It is evident from the cross section SEM images that the
coatings are dense and uniform on the surface of Mg disk. As
evident from the XRD analysis and cross section SEM images,
the thickness of the conversion coating increases with an increase in the hydrothermal treatment time. The increase in the
thickness with increasing hydrothermal treatment time can be
explained on the basis of the effect of temperature and pressure
on ionization of water. The ion product of water increases with
increasing temperature and pressure. With time the production
of hydrogen gas leads to the increase of the pressure in the
hydrothermal vessel. This increment in the pressure leads to
increasing the degree of ionization of water. This increase in
the degree of ionization improves the reaction rate between Mg
disk and water[34].

Fig. 2 SEM images of (a) sample 1, (b) sample 2, (c) sample 3, (d) sample 4, and (e) sample 5 (inset images in each gures show higher magnication).

50

R.K. Gupta et al.: J. Mater. Sci. Technol., 2014, 30(1), 47e53

application and removal of the tape according to the procedure

described in the ASTM tape test. As seen in the optical image
(Fig. 4(b)), almost the whole coating was undetached after the
removal of the tape from the sample. This indicates that the
coating produced by hydrothermal method has strong adhesion
on the surface of the Mg disk.
3.4. Immersion (hydrogen released)

Fig. 3 Cross section SEM images of sample 4 (a) and sample 5 (b).

3.3. Coating adhesion to magnesium disks

The adhesion of a coating on any surface is a very important
factor to determine the quality of the coating. Low quality lms
could peel off from the substrate and hence are of little importance toward their benecial application for substrate. The
adhesion strength of the conversion coatings on Mg disks was
studied according to the standard of American Society for
Testing Materials (ASTM) for coatings. ASTM-D3359-02 tape
test was chosen to study the adhesion of Mg(OH)2 conversion
coating on Mg disk and optical images are shown in Fig. 4, as
representative images[37]. In this test, a cross cut patterns through
the coating having separation of 1 mm were made on the samples. Fig. 4(a) shows the cross cut patterns before the adhesion
test. Fig. 4(b) shows the optical image of the same sample after

The biodegradability of the untreated and hydrothermally

treated Mg disks could be understood in vitro by studying the
hydrogen released during immersion in corroding solution
similar to body uid (in this case PBS solution). The study of
hydrogen gas evolved during immersion test is signicant
because 1 mL of H2 evolved corresponds to 1 mg of Mg dissolved, and thus measuring hydrogen gas evolved is equivalent
to measuring the corrosion rate of Mg[38,39]. Therefore, measurement of hydrogen gas released during the immersion was
employed as an important method to compare the biodegradability of the uncoated and Mg(OH)2 coated Mg disks. Fig. 5
shows the hydrogen gas released vs immersion time for the
samples in 1 PBS solution maintained at 37  C using a water
bath. As seen in Fig. 5, the volume of hydrogen gas released for
uncoated Mg disk is much higher than that of hydrothermally
treated Mg disks. Among the hydrothermally treated Mg samples, the volume of hydrogen gas released was lower for the
samples treated for longer hydrothermal treatment time. The
samples treated for more than 7 h have similar properties
compared to that for 7 h. Frankel et al.[40] studied the hydrogen
gas evaluation in 0.3% NaCl solution from Mg surfaces during
galvanostatic polarization. They observed that the rate of
hydrogen evolution was minimum at the open circuit potential,
and increased with increasing applied anodic or cathodic current.
3.5. DC potentiodynamic polarization
The effect of hydrothermal treatment time on the corrosion
behavior of Mg disks was studied using potentiodynamic polarization measurements. Potentiodynamic polarization curves
for uncoated Mg disk and hydrothermally coated Mg disks were
shown in Fig. 6. As seen in this gure, the hydrothermally coated
Mg samples show lower corrosion current density compared to

Fig. 4 Optical images of sample 4 (a) before and (b) after adhesion test.

R.K. Gupta et al.: J. Mater. Sci. Technol., 2014, 30(1), 47e53

51

treated Mg samples indicate the corrosion protective nature of

the hydrothermally formed conversion coatings on Mg disk.
3.6. Porosity and protection efciency of the coatings
The porosity of the coating is another important parameter for
determining the corrosion protective nature of the coating for any
substrate. If the coatings are highly porous, the pores of the
coatings provide a direct path between the corrosive environment
and the substrate leading to severe corrosion of the substrate. The
porosity of the conversion coatings produced by hydrothermal
treatment on Mg disk was estimated using the following
expression[42]:

Fig. 5 Volume of hydrogen gas released versus immersion time plots
for various Mg samples in 1 PBS solution.

Rps
Rp

 10DEcorr =bA

(7)

where P is the total coating porosity rate, Rps is the polarization

resistance of the uncoated Mg disk, Rp is the polarization
resistance of the coated Mg disks, DEcorr is the difference
potential between the corrosion potentials of the coated Mg
disk and uncoated Mg disk, and bA is the anodic Tafel slope
for the uncoated Mg. The percentage porosity of the samples
is given in Table 1. As seen in Table 1, the porosity of the
coating decreases with increase in reaction time during the
hydrothermal treatment. The low porosity of the coating will
prevent the direct contact of the corrosive environment to the
Mg, thus reducing the corrosion rate of Mg[43]. The protection
efciency (PE) of the conversion coatings on the Mg disk was
estimated using the equation given below[44]:
PE%

Fig. 6 Potentiodynamic polarization curves for uncoated Mg disk

(control) and hydrothermally coated Mg disks.



ba  bc
1
2:303RP ba bc

(8)

where icorr and i0corr are the corrosion current densities of the
uncoated Mg disk and hydrothermally Mg(OH)2 coated Mg
disks, respectively. The protection efciency of the sample 4
was the highest among the others. The protection efciency
and some other parameters obtained from the potentiodynamic
polarization measurements are given in Table 1 for easy
comparison.

uncoated Mg sample. The corrosion potential (Ecorr) and corrosion current density (Icorr) of the samples were calculated using
the SterneGeary equation[41].
Icorr



icorr  i0corr
 100
icorr

(6)

where RP is the corrosion resistance in U cm2, ba is the anodic

Tafel slope in volt/decade, and bc is the cathodic Tafel slope in
volt/decade. The corrosion potential and corrosion current
density for various samples are listed in Table 1. As evident
from Table 1, the corrosion potential of the hydrothermally
treated samples increases with an increase in reaction time. On
the other hand, the corrosion current density of the
hydrothermally treated samples decreases with an increase in
reaction time upto 5 h and then slightly increases. The positive
shift in the corrosion potential and low current density for the

3.7. Electrochemical impedance spectroscopic measurements

The corrosion protective nature of the coatings was further
analyzed using electrochemical impedance spectroscopy (EIS).
The EIS measurements were recorded at the open circuit potential. Fig. 7 shows the Nyquist and Bode plots for the uncoated
Mg disk and hydrothermally coated Mg disks. As seen in the
Nyquist plot, the real and imaginary part of the impedance increases with decrease in the frequency. As seen in Fig. 7(b), the
impedance jZj of the uncoated Mg sample decreases with

Table 1 Some important parameters obtained from polarization measurements

Sample name
Sample
Sample
Sample
Sample
Sample

1
2
3
4
5

Rp (U cm2)
7.76
3.99
5.86
6.34
3.92







10
103
104
104
104

Ecorr (V)
1.67
1.62
1.48
1.41
1.37

Icorr (A cm2)
1.45
1.38
1.00
3.90
6.92







6

10
106
107
108
108

Porosity (%)

Protection efciency (%)

e
10.4
0.12
0.048
0.047

e
4.89
93.1
97.3
95.2

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R.K. Gupta et al.: J. Mater. Sci. Technol., 2014, 30(1), 47e53

Fig. 7 Nyquist (a) and Bode (b, c) plots for uncoated Mg disk (control) and hydrothermally coated Mg disks.

increase in the frequency and became almost constant over

103 Hz. On the other hand, in the Nyquist plots of the hydrothermally coated Mg samples, the real impedance (Zre) and
imaginary impedance (Zim) are much higher than that of uncoated Mg sample. In the Bode plot of the coated Mg samples, it
is seen that the impedance is higher than the uncoated Mg
sample. The higher value of impedance further conrms the
corrosion protective nature of the coating for Mg disk[45]. The
variations of the phase angle with frequency for the samples are
given in Fig. 7(c). The broader peaks observed for the coated Mg
samples showed greater compactness of the coating compared to
the uncoated Mg sample[46]. The greater compactness and thus
low corrosion rate of the hydrothermally coated Mg samples is
evident in the phase angle versus frequency plot where the
maximum of the phase angle is broad for the coated Mg samples.
4. Conclusion
A hydrothermal technique was used to grow Mg(OH)2 conversion coatings on bioresorbable Mg disks. The effect of hydrothermal treatment time on the properties of the conversion
coating was investigated. The tape test revealed a strong adhesion between the coating and the Mg disk. The hydrothermally
treated Mg disks show low degradation than that of uncoated Mg
disk. These results suggest that Mg(OH)2 conversion coating by
hydrothermal method could provide a potential corrosion protective coating on Mg disk.
Acknowledgments
This research was nancially supported by the National
Science Foundation through Engineering Research Center of
Revolutionizing Metallic Biomaterials at NCAT. Authors thank
Dr. J. Sankar, Dr. Z. Xu, and Dr. Y. Yun, for useful discussion
and providing access to their research facilities.
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