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ICRAMMCE 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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Mechanical and corrosion behaviors of developed copper-

based metal matrix composites

Manvandra Kumar Singh1*, Rakesh Kumar Gautam1, Rajiv

Prakash2 and Gopal Ji2
1
Department of Mechanical Engineering, Indian Institute of Technology
(Banaras Hindu University), Varanasi-221005, India
2
School of Materials Science and Technology, Indian Institute of Technology
(Banaras Hindu University), Varanasi-221005, India

*Corresponding author E-mail: mksingh.rs.mec13@itbhu.ac.in

Abstract. This work investigates mechanical properties and corrosion resistances of cast
copper-tungsten carbide (WC) metal matrix composites (MMCs). Copper matrix
composites have been developed by stir casting technique. Different sizes of micro and
nano particles of WC particles are utilized as reinforcement to prepare two copper-based
composites, however, nano size of WC particles are prepared by high-energy ball
milling. XRD (X-rays diffraction) characterize the materials for involvement of different
phases. The mechanical behavior of composites has been studied by Vickers hardness
test and compression test; while the corrosion behavior of developed composites is
investigated by electrochemical impedance spectroscopy in 0.5 M H2SO4 solutions. The
results show that hardness, compressive strength and corrosion resistance of copper
matrix composites are very high in comparison to that of copper matrix, which attributed
to the microstructural changes occurred during composite formation. SEM (Scanning
electron microscopy) reveals the morphology of the corroded surfaces.

1. Introduction
Copper contains high electrical conductivity, thermal conductivity and ductility as well as good
corrosion resistance in various media [1, 2]. Due to these effective reasons, copper and its alloys
are widely utilized in many engineering and industrial applications like automobiles, houses,
sanitary system (underground or under sea drinking water pipes), electronic and electrical
devices, and lead frame materials for integrated circuits [3, 4]. In spite of having all the above
listed properties, copper and alloys rapidly lose their mechanical strength and corrosion
resistance in some aggressive environments [5-7]. This can cause complete failure of the copper-
based appliances, which may lead to adverse circumstances. Hence, it becomes important to
improve their anti corrosion and mechanical strength in active working environments [8-10].
One of the most effective methods adapted for enhancing the mechanical strength and corrosion
resistance of copper is alloying [11, 12]. Due to the alloying effect, the mechanical properties of
copper improve; and the span of safe operation period increases [13-15]. The effects of alloying
with the different elements on the properties of copper have been well studied by various
scientists [16-18].

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Published under licence by IOP Publishing Ltd 1
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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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The first aim of the present work is to investigate the changes in mechanical properties of copper
due to alloying with WC particles (micro and nano size). The second aim of this work is to study
the corrosion inhibition behavior of copper matrix composites in 0.5 M H2SO4 solutions.
Ceramic materials, especially carbides [19-21], are widely used as reinforcement particles in
metal matrix composites. However, the ceramic particles have the natural tendency to generate
micro cracks in the composites due to poor wettability with the matrix metal [22]. Hence, we
have selected both micro and nano size (for better dispersion) WC powder as reinforcement
particles in making of copper matrix composites. WC reinforced copper matrix composites are
made by stir casting technique. Hardness, compressive strength and corrosion behavior of
prepared Cu-WC composites have been investigated by Vickers hardness test, compression test
and electrochemical impedance spectroscopy (EIS) techniques. The results show significant
improvement in mechanical and anti corrosion strength of copper due to alloying with WC,
which justify alloying of copper with WC particles.

2. Materials and Methods

2.1. Preparation of micro and nano copper composites

Figure 1. Schematic diagram showing details of a stir- casting process

Matrix material (copper of 99.5 % purity) was purchased from the local shop at Varanasi, India.
WC powder (HIMEDIA with 98.0 % assay, micro size) and chromium powder (LOBA
CHEMIE with 99.0 % assay) were bought from local chemical supplier. Micro size particles of
WC were ball milled for a long period and thus converted into nano size particles. To prepare
micro and nano composites of copper and WC, firstly 1 wt % of WC micro and nano powder,
2.0 wt % of chromium (Cr) and rest copper ( in rod from) were weighed. Then, a graphite
crucible that contains small pieces of copper rod was kept in the electric furnace. The furnace
temperature was raised up to 1200º C. At this high temperature copper melts; and then dry
micro and nano WC particles were poured separately into crucibles followed by addition of Cr,
with the help of powder pouring system (Figure 1). During pouring of powders, the stirrer was
rotated at very slow speed of 50rpm; however, the speed of stirrer was increased to 400 rpm for
10 minutes after completion of the pouring process. Afterwards, the furnace was shutdown and
crucible was taken out from the furnace. Thus, prepared materials were poured into permanent

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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moulds and left for cooling in air. Afterwards, Cu-WC composites were abraded by 1/0 to 6/0
grade of emery paper sequentially and cleaned by acetone followed by washing with double
distilled water. Thus, prepared composites were used for further characterizations.

2.2 XRD analysis of nano WC powder and Cu-WC composite materials

X-ray diffraction patterns for powder samples of Cu, WC and Cu-WC composites were obtained
by 18 kW anode powder X-ray diffractometer, Rigaku, Japan in the range of 20º to 80º with Cu-
Kα radiation at a scan rate of 3º per minute. The powder samples of Cu and Cu-WC composite
were obtained by scraping them with a file. Thus, obtained powders were used for XRD
analysis.

2.3 Microstructural examination of copper and copper-WC composites

The microstructural analysis of the copper and copper matrix micro and nano composites was
performed on the optical microscope of De-winter Optical Inc, India. Prior to investigation, the
test specimen were prepared by grinding them with the emery papers of 200, 400, 600, 800,
1200 and 1600 grit number. The specimens were first grinded with the emery paper of 200 grit
number for 10 minutes. Afterwards, the abrading of the specimen was done for 10 minutes with
the 400 grit number emery paper at 90º angle to the direction of grinding the specimen with 200
grit number emery paper. The same procedure was followed in grinding of the specimen with
the emery paper of 600, 800, 1200 and 1600 grit number. After completion of the grinding
process, the specimens were polished by the velvet cloths having Brasso as a polishing agent.
After polishing, the specimens were washed under the running tap water and dried with the hot
air to remove the stains from the specimen’s surface. In the last step, the specimens were
partially dipped in the ferric chloride solution (etchant) for 6 seconds and drawn out afterwards.
Thus prepared specimens were used for the microstructural analysis.

2.4 Vickers micro hardness test

The Vickers micro hardness test method included indentation of copper and composite materials
(specimen dimension: 15 mm×15 mm×2 mm) with a diamond indenter. The indenter was in the
shape of pyramid with square base and having an angle of 136º between opposite faces. The test
samples were subjected to a load of 0.5 kgf for 10 seconds. Due to application of load, an
impression of indenter appeared on sample’s surfaces. The two diagonals of this indentation (d 1
and d2) were measured with the help of a microscope and arithmetic of these two used in the
formula. Vickers hardness (HV) values of the samples calculated from the following equation:
HV = {2Fsin (136º/2)}/d2 ---------- Eq. 1
Where, F is Load in kgf and d correspond to arithmetic mean of the two diagonals d 1 and d2 in
mm.

2.5 Compression test

The compressive strengths of copper and composite materials were investigated by universal
testing machine (UTM). For compression test, the specimens were prepared in cylindrical form
that was 20 mm in length and 10 mm in diameter. The test specimens were compressed with the
help of UTM until buckling deformation of samples. The load at which samples started to
deform, or crack appeared on sample’s surface, was designated as critical compressive load.
Compressive strengths of samples were obtained by dividing critical compressive load by area of
samples.

2.6 Corrosion testing and surface morphology analysis

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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Corrosion testing of copper and copper-WC composites (sample surface area- 1 cm2) was
performed by electrochemical impedance spectroscopy (EIS) technique with help of an
electrochemical workstation, CH Instrument (USA), in a three electrode glass cell. In this cell
assembly, platinum foil (1 cm×1 cm) as counter electrode, Ag/AgCl as reference electrode and
test samples as working electrodes were employed. The EIS spectra were obtained at open
circuit potentials by applying 5 mV excitation signals in the frequency range of 10 mHz to 100
kHz [23-25]. The active parameters of corrosion process were obtained by fitting of Nyquist
plots with ZSim software (version 3.20).
The effect of alloying on corrosion behavior of copper was monitored by SEM microscope of
Carl Zesis, model- Supra 40, made in Germany. The samples of 1 cm2 surface area were immersed in
beakers having 100 mL of 0.5 M H2SO4 solutions for 2 hours. Afterwards, the specimens were drawn
out; washed with double distilled water; wiped with a tissue paper and dried in a hot oven at 30° C for
10 minutes. Thus, prepared samples were investigated for the surface morphology changes in copper
due to alloying. For a comparison, SEM images of the unexposed samples of copper and composites
were captured.

3. Results and Discussion

3.1. XRD analysis
3.1.1. XRD analysis of high energy ball milled WC powder.

Figure 2. XRD plots of high-energy ball Figure 3. Peak broadening in XRD

milled WC powder spectrum of milled WC powder

X-rays diffraction patterns of high-energy ball milled WC powder at zero hour (pure WC
powder), 20 hours and 40 hours are shown in Figure 2. From analysis of XRD patterns, it is
observed that peak intensities of tungsten powder decreased with the period of ball milling.
However, broadening of peak occurred with the time of ball milling. This fact indicated that WC
powder is converted in nano size particles from micro size powder particles. This statement
could be supported by the fact that XRD peaks became broader due to reduction in particle size
[26] (Figure 3). Furthermore, the size of WC particles is calculated by Scherrer formula [27].
D = 0.9λ/B cosθ ------------- Eq.2

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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Where, D is crystallite size, λ is the wavelength of the X-ray radiation, B is the peak width at
half of maximum intensity and θ correspond to the Bragg angle. The size of WC particles after
40 hours ball milling calculated from scherrer formula is 19 nm.

3.1.2 XRD analysis of composite materials. Figure 4 shows XRD patterns of copper and Cu-WC
micro composite. From analysis of Figure 4, it is observed that there were some common peaks
in XRD patterns of WC and copper. XRD peaks of WC are absent in Figure 4 because they have
already shown in Figure 2; however, we have illustrated some characteristic peaks of WC in text
form. Figure 4 revealed that intensities of XRD peaks of Cu-WC composite are higher than peak
intensities of WC (Figure 2). In addition, these peaks appeared in XRD pattern of copper. Hence,
it could be concluded based on above-mentioned information that Cu-WC composite is
successfully prepared. Here, the x-rays diffraction pattern of the Cu-WC nano composite has
not been shown because the reinforcing element is same, i.e., WC. Also, only difference
between Cu-WC micro and nano composite is size of WC, which will not affect XRD peak
positions very much (Figure 2).

Figure 4. XRD plot of commercial copper and micro composite XRD plot of commercial copper
and micro composite materials

3.2 Micro structural analysis

The optical micrographs of as-cast Cu, Cu-WC micro composite and Cu-WC nano composite
are shown in Figure 5. A quick analysis of Figure 5a revealed that there are some pores present
on the copper surface, which could be considered as a casting defect. Figure 5b showed that WC
particles (black) are well dispersed in copper matrix (white); however, the WC particle size is
not uniform. On the other hand, Figure 5c revealed that nano WC particles are more uniform in
size and finely dispersed in copper matrix. To explain the contributions of nano and micro WC
particles in Cu matrix in a better way, the microstructures of copper and composites (Figure 5)
are studied and shown in Figure 6. It is clear through analysis of Figure 6 that WC particles
assisted in colonization of copper grains. However, finer grains and a dense structure are

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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achieved using nano WC particles in comparison to micro WC particles; which demonstrated

that better reinforcement could be achieved with nano WC particles.

Figure 5. Optical images showing microstructure of (a) cast Cu, (b) Cu-WC micro composite
and (c) Cu-WC nano composite just before etching

Figure 6. Optical images showing microstructure of (a) cast Cu, (b) Cu-WC micro composite
and (c) Cu-WC nano composite obtained after etching

3.3. Vickers hardness test

Vickers hardness tests of copper, copper micro composite and copper nano composite are
performed at 0.5 kgf load; and the results are shown in Figure 7. Analysis of Figure 7 revealed
that the hardness values of nano and micro Cu-WC composites were higher than the hardness
value of copper, which clearly indicated that addition of micro and nano WC particles enhanced
hardness of matrix material (copper). However, hardness of copper-WC nano composite is the
highest among all tested materials. This fact could be effectively described with the help of Hall-
Petch relationship. According to this, distribution of filler material in matrix material increases
with reduction in particle size of metals, which causes increase in hardness value of composite
materials [28]. The grain size is also an important parameter, which has strong influence on
metal strength. This is due to different orientation of adjacent grains and high lattice disorder
characteristics of these regions, which prevents dislocation to move in a continuous slip plane
[29].

3.4. Compression test

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Compression tests of copper and composite materials have been executed on universal testing
machine and results are shown in Figure 8. A careful inspection of Figure 8 revealed that
compressive strengths of copper composites are greater than that of copper alone. However, the
compressive strength of Cu-WC nano composite is the highest among all studied materials in
this work. Such an increase in the compressive strength of both micro and nano composite of Cu
and WC might be occurred due to the combined effects of load transfer, Hall-Petch
strengthening and Orowan strengthening. Compressive strength of composite materials might
increase by strengthening of the base material due to the load transfer from the soft and
compliance matrix to the stiff and hard ceramic WC particles under an applied external load [30-
32]. Fine distribution of the ceramic WC in copper matrix might be one of the reasons for
enhancement of compressive strength of both micro and nano composite materials [27]. In
addition, the strength of composite materials might increase due to pining up of dislocations
crossing over WC particles under external load [29].

Figure 7. Hardness (VHN) of Figure 8. Compressive strengths of

copper and copper composites copper and copper composites

3.5. Electrochemical impedance spectroscopy

Corrosion behaviors of copper and copper-WC composites in 0.5 M H2SO4 solutions are
investigated by EIS technique and shown in Figure 9. It is observed through analysis of Figure 9
that corrosion resistance of copper is significantly increased by addition of ceramic WC powder
particles as a filler material; however, maximum anticorrosion potential is shown by Cu-WC
nano composite. Ceramic materials are well known for its high corrosion resistance. Hence,
addition of ceramic WC particles in copper matrix increased resistance of composite material
against acid corrosion. Furthermore, fine distribution of WC nano particles in copper matrix
enhanced the interaction points (area) between WC particles and copper molecules, which
resulted in high strength of Cu-WC nano composite. This fact is clearly manifested in corrosion
test, which is in good agreement with Vickers hardness test and compression test. Further
analysis of impedance data via Bode plots (Figure 10) revealed that phase angle for copper is
lower than that of copper composites. In other words, it could be said that phase angle was closer
to 90° for Cu-WC composites with respect to copper, which is the artifact of higher corrosion
resistance of Cu-WC composites in sulfuric acid solutions.
To obtain more details from impedance curves, Nyquist plots are fitted with an equivalent
electrical circuit (EEC) as shown in Figure 11 [33-35]. The different elements of EEC could be
described as: solution resistance, Rs; charge transfer resistance, Rt; and constant phase element,

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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CPE. Nyquist plots of copper and copper matrix composites showed that corrosion process is
governed by charge transfer reactions only (one time constant). However, the shape of
impedance spectra is not semicircular; CPE is used to show modified capacitor behavior of
electrodes in sulfuric acid solutions.
A quick analysis of Table 1 revealed that impedance of copper against corrosion in sulfuric
acid solution increased due to alloying with WC particles. However, Cu-WC nano composite
showed more corrosion resistance than Cu-WC micro composite. The first reason for this fact
could be extracted from the changes in “n” values. Table 1 showed that there is increase in “n”
values when nano sized WC particles are used to make copper matrix composites instead of
micro sized WC particles. This means that surface properties of the electrode is modified in a
better way in presence of nano WC particles, which could also be observed in bode phase angle
plots (Figure 10). The second reason could be given as decrease in CPE values. On immersion of
working electrodes in electrolyte solution, corrosion products are formed at the interface. These
corrosion products (preferably oxides) acted as a medium having one side copper and copper
matrix composite electrodes and electrolyte on other side, equivalent to two plates of a capacitor.
A decrease in capacitance might correspond to: increase in the thickness; or decrease in
dielectric constant; or decrease in porosity of protective corrosion products layer formed at
electrode-acid interface [36-39], which resulted in high corrosion resistance of Cu-WC nano
composite.

Figure 9. Nyquist Plots for Copper and Copper composites in 0.5 M H2SO4 solutions

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Figure 10. Bode Plots for Copper (a), Cu-WC micro composite (b) and Cu-WC nano composite
(c) in 0.5 M H2SO4 solutions

Figure 11. Electrochemical circuit and fitting of Nyquist Curves

Table 1. Technical Parameters obtained from Nyquist Plots for copper and copper composites in
0.5 M H2SO4 solutions at room temperature

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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S. No. Materials Rs Rt n CPE

(Ω cm2) (Ω cm2) (µF cm-2)
1- Copper 1.06 285 0.801 108.50
2- Cu-WC micro composite 0.34 845 0.821 34.45
3- Cu-WC nano composite 1.10 1310 0.832 9.94

The corrosion study of copper and copper-WC composites clearly suggested that WC
particles reinforce the corrosion resistance of copper in 0.5 M H2SO4 solution. Similar
information is achieved by the surface morphology analysis of the unexposed and the exposed
samples. A careful analysis of Figure 12 suggests that there is an inherent oxide layer on the
surfaces of unexposed samples, which formed probably due to interaction of the samples with
open air. Yet, the samples show smooth surfaces. On the other hand, the samples exposed in
sulfuric acid illustrated a clear change in the surface morphology with respect to the unexposed
samples. Figure 13 reveals that the greatest surface damage occurred in copper specimen;
however, the copper-WC composites show just a slight degradation of the surface in sulfuric
acid solution. Thus, it could be stated based on surface images that WC particles significantly
enhanced the corrosion resistance of copper.

Figure 12. SEM images of unexposed (a) copper, (b) Cu-WC micro composite, (c) Cu-WC
nano composite

Figure 13. SEM images of exposed (a) copper, (b) Cu-WC micro composite and (c) Cu-WC
nano composite in 0.5 M H2SO4 solutions for 2 hours

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IOP Conf. Series: Materials Science and Engineering 330 (2018) 012021 doi:10.1088/1757-899X/330/1/012021
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3.6 Overall comparison between copper and copper-WC composites

Figure 14. Comparison of mechanical and corrosion behavior of Cu and Cu-WC composites

Figure 14 shows an overall comparison of hardness, compressive strength and corrosion

resistance values of copper and copper composites. It could be stated based on Figure 14 that
mechanical and corrosion behavior of copper significantly improved due to reinforcement of
WC particles. In addition, the comparison between Cu-WC micro composite and Cu-WC nano
composite suggested that size of WC particles played a vital role in the improvement of the
properties of copper. Due to decrease in size of the reinforcing WC particles, this caused better
interaction between matrix and filler martial. Thus, the mechanical properties and corrosion
behavior of Cu-WC nano composite became better that Cu-WC micro composite.

4. Conclusions
We prepared copper, Cu-WC micro composite and Cu-WC nano composite by stir casting
technique in present study. The prepared copper and copper composites are characterized by
XRD analysis, which confirms the formation of Cu-WC composites. Hardness and compressive
strength of the test samples are estimated by Vickers hardness tester and universal testing
machine. It is found from the results that hardness and compressive strength of Cu-WC
composites are greater than that of copper matrix. Furthermore, anticorrosion strengths of cast
copper and copper composites are tested in 0.5 M H2SO4 solutions, which show that copper
composites are having higher corrosion resistance in comparison to alone copper. It could be
concluded based on the results of various techniques that Cu-WC nano composite performed
very well in all the tests followed by Cu-WC micro composite and copper respectively.
Composite formation due to fine dispersion of WC particles in copper matrix could be given as
the reason of above-mentioned fact.

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