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Journal of Magnesium and Alloys 7 (2019) 681–695

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Corrosion behavior of AZ31-WC nano-composites
Sudip Banerjee a, Suswagata Poria b, Goutam Sutradhar a,c, Prasanta Sahoo a,∗
a Department of Mechanical Engineering, Jadavpur University, Kolkata 700032, India
b Department of Mechanical Engineering, Heritage Institute of Technology, Kolkata 700107, India
c National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India

Received 6 May 2019; received in revised form 12 July 2019; accepted 17 July 2019
Available online 9 December 2019

Abstract
In this study, the effects of WC nano-particles amount and surface roughness on corrosion behavior of magnesium metal matrix nano-
composites in 3.5% NaCl solution are examined with the help of electrochemical test. Varying wt% of WC nano-particles (0.5, 1, 1.5 and
2) are used to fabricate metal matrix nano-composites through ultrasonic vibration assisted stir casting method. Basic characterizations of
fabricated composites are performed by using scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDAX). SEM
images show that nano-particles are well distributed throughout the magnesium matrix while EDAX results confirm the presence of WC
particles in nano-composites. Micro-hardness result shows increasing trend with increasing weight percentage of WC. Mg nano-composite
containing 0.5 wt% WC nano-particles is found to be the most corrosion resistive one followed by base alloy, Mg-2 wt%WC, Mg-1.5 wt%WC
and Mg-1 wt%WC. Additionally, corrosion behavior of Mg-2WC with different surface quality is examined and it is observed that sample
with lowest surface roughness shows better corrosion resistance. In the end, corrosion mechanisms are assessed with the help of SEM and
EDAX study of corroded surfaces.
© 2019 Published by Elsevier B.V. on behalf of Chongqing University.
This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Peer review under responsibility of Chongqing University

Keywords: Mg-WC; Nano-composite; Corrosion; Roughness; Electrochemical test.

1. Introduction is being considered as a promising alternative of aluminum

The ever increasing need of emission reduction and perfor-
mance improvement of transportation industry have spurred
the development of new lightweight high performance ma-
terials. At the basic stage, design criterion of transportation
industry is concerned with the strength, mechanical stiffness,
density and corrosion resistance of the operating material.
Lower density provides higher payload, while higher strength
and stiffness provide adequate performances and safety char-
acteristics.Additionally, higher corrosion resistance of materi-
als ensures its high operational life [1]. In this context magne-
sium metal matrix composites are being considered with great
interest due to its low density (1.74 g/cm3 ), high strength to
weight ratio and high stiffness [2,3]. In industry, magnesium
∗ Corresponding author.
E-mail address: prasanta.sahoo@jadavpuruniversity.in (P. Sahoo).
https://doi.org/10.1016/j.jma.2019.07.004
2213-9567/© 2019 Published by Elsevier B.V. on behalf of Chongqing University. This is an open access article under the CC BY-NC-ND license.
(http://creativecommons.org/licenses/by-nc-nd/4.0/) Peer review under responsibility of Chongqing University
as magnesium has 35% lower specific gravity than aluminum
and magnesium weighs ∼25% lesser than aluminum counter-
parts having equal stiffness [4]. However, all these advantages
are contrasted by corrosion rate of pure magnesium and mag-
nesium alloys. Magnesium and magnesium alloys are highly
active and receptive to galvanic corrosion which affects the
mechanical stability of the system and shows unattractive ap-
pearances [4]. Accordingly, improvement of corrosion behav-
ior of magnesium and its alloys have attracted researchers for
the last decade. It is reported that corrosion resistance of mag-
nesium alloys can be improved by using high purity alloying
element, incorporating reinforcement and improving surface
quality of contacting surfaces [5]. Though alloying of mag-
nesium generates better corrosion performance compared to
pure magnesium but it is not sufficient to solve the galvanic
corrosion problem when magnesium alloys are in electrolytic
environment [6]. To solve this issue, magnesium metal ma-
682 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
trix composites are targeted for attaining improved corrosion
property even in electrolytic environments. Till now, litera-
tures are majorly available on corrosion performance of mag-
nesium matrix where ceramic particles like SiC, Al2 O3 , ZnO,
CNT, TiC, Y2 O3 etc. are incorporated and those studies are
specially focused on the effect of reinforcements on corrosion
performance [7]. With increasing attention and progression
in nano-science, nano-sized particles are being incorporated
in the base matrix replacing micron sized particles. Simul-
taneously, corrosion performance of nano-particles reinforced
MMCs should be studied to identify any sort of change in
the performance due to particle size reduction. Accordingly
in the present study, an attempt has been taken to study the
corrosion behavior of Mg-metal matrix nano-composites.
In the current study, tungsten carbide (WC) nano-particles
are considered as reinforcement phase due to its high modu-
lus of elasticity (630 GPa), high oxidation resistance at high
temperature (up to 600 °C), high melting point (2870 °C) and
high hardness (1400 HV) [8]. WC as reinforcing phase is be-
ing used in Al/Mg base matrix by the researchers during last
few years. Positive contribution of nano-WC phase in me-
chanical and tribological performance of Al/Mg MMCs is al-
ready reported which is encouraging advanced study on nano-
WC reinforced composites. Recently, Lekatou et al. [9] have
studied the effect of dry sliding wear and corrosion behav-
ior of Al-WC/TiC composites and revealed positive impact
of reinforcement phases on corrosion behavior. Flores et al.
[10] have studied the effect of WC particles on corrosion
behavior of Ni/Fe matrix with conclusion that MMCs show
better corrosion resistance than base matrix. Similarly, Anaee
[11] has examined the corrosion behavior of Al-WC compos-
ites and reported that 1 wt.% WC reinforced Al-MMC shows
poor corrosion resistance than base alloy where (2–3) wt%
WC has better corrosion resistance.
Unlike WC-reinforced Al particles, reported corrosion be-
havior on Mg-MMC does not follow any linear trend. Even
researchers are divided into two poles regarding the corrosion
behavior of Mg-MMCs. Chan et al. [12] showed that incor-
poration of Al2 O3 short fiber in AZ91C reduced the corrosion
resistance than the base alloy in 3.5% NaCl solution. Li et al.
[13] have observed that MWCNT (Multi-Walled Carbon Nan-
otube) has detrimental effect on corrosion resistivity of com-
posites. Pardo et al. [14] have shown that presence of SiC
particles in magnesium alloy have negative effect on corro-
sion resistance because SiC promotes spalling and cracking of
tribolayer. Tiwari et al. [15] have found that increasing vol-
ume percentage of SiC deteriorates the corrosion resistance
of magnesium in freely aerated 1 M NaCl solution. Similarly,
Rashad et al. [16] have studied the electrochemical behavior
of AZ31/AZ61-graphene nano-platelets (GNPs) in 3.5% NaCl
solution and observed that GNPs decrease the corrosion re-
sistance of magnesium matrix. Jia et al. [17] have studied
the corrosion behavior of Mg-TiC composites in saline envi-
ronment and concluded that local corrosion rate and galvanic
corrosion of composites are higher than AZ91 alloy. Fukuda
et al. [18] have observed that presence of CNT have increased
the galvanic corrosion of AZ31B alloy. Aung et al. [19] have
also found similar result by reinforcing CNT in magnesium
alloy in 3.5% NaCl solution.
On the other hand, some researchers have found that the
corrosion resistance of magnesium and magnesium alloys
have improved with the presence of reinforcement. Endo et
al. [6] have observed that multi-walled carbon nano-tube have
improved the anticorrosive characteristics of AZ91D magne-
sium alloy in 3.5% NaCl solution. Falcon et al. [20] have
shown that incorporation of TiC particles in AZ91E alloy have
decreased the corrosion rate of AZ91E alloy and improved
the pitting resistance of base matrix. Zhang et al. [21] have
found that micro-galvanic corrosion of AZ91 significantly de-
crease with increase volume fraction of SiC particles. Simi-
larly, Hamid et al. [22] have observed that incorporation of
ZrO2 reduces the corrosion rate of AM50 magnesium alloy.
Lei et al. [23] have studied the effect of MgO ceramics and
Mg–Zn intermetallics on corrosion behavior of pure magne-
sium. It is found that reinforcements enhance the corrosion
resistance of base matrix by refining the grains and strength-
ening the second phase. Funatsu et al. [24] have shown that
initial galvanic corrosion resistance of AZ61B-CNT have im-
proved significantly than AZ61B alloy due to formation of
gradient distribution. Gobara et al. [25] have shown that in-
corporation of TiC and TiB2 have improved corrosion resis-
tance of AZ91D in 3.5% NaCl solution. Xi et al. [26] have
examined the corrosion property of Mg/O/PCL/ZnO compos-
ite in stimulated body fluid and concluded that composite has
outstanding corrosion resistance. Ghasali et al. [27] have ob-
served that Mg–Al2 O3 and Mg–Si3 N4 nano-composites have
higher polarization resistance than pure magnesium.
From literature survey, additionally it is found that surface
roughness immensely affects the corrosion potential and pit-
ting phenomenon. In case of alloy it is widely reported how
surface roughness affects the corrosion performance other
than alloying element. As an example, it is noticed that, when
two smooth surfaces of stainless steel are polished using two
different grit papers and corrosion potential is tested, general
corrosion rate and pitting susceptibility of smoother surface
have decreased noticeably [1]. Similar trend of rough surface
being more corroded than the smoother surface is observed
for pure aluminum, copper and titanium based alloys [28].
Alvarez et al. [1] have studied the effect of time and surface
roughness on corrosion behavior of AE44 magnesium alloy.
However, only a few literatures are available on the effect of
roughness on corrosion behavior and pitting susceptibility of
magnesium composites. Walter and Kannan [28] have studied
the effect of surface roughness on pitting corrosion and passi-
vation of AZ91 magnesium alloy with the help of EIS study
and potentiodynamic polarization tests. It is found that pitting
tendency and corrosion current have increased with increase
in roughness of the material surface.
In the current study, corrosion tests are performed on nano-
particles reinforced Mg-matrix. However, wettability and ag-
glomeration tendency of nano-particles creates problem at the
time of fabrication. Hence proper fabrication process must be
selected to achieve proper distribution of nano-particles. Re-
cent literatures on Mg-MMCs have shown that majorly pow-
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695 683

der metallurgy, disintegrated melt deposition (DMD) and ul- Table 1

trasonic vibration assisted stir casting method have been used Chemical composition of AZ31.
to develop Mg-MMCs [7]. But powder metallurgy products Element Al Zn Si Mn Fe Mg
faces porosity related problems. While ultrasonic vibration Wt% 3.20 1.20 0.10 0.28 0.22 Balance
assisted stir casting method is useful for solving dispersion
related issues and also economical. Dieringa et al. [29] have Table 2
reported that ultrasonic assisted stir casting method is useful Details of WC powder.
to provide proper distribution of AlN nano-particles in AM60
Product name Tungsten carbide nano-powder
magnesium alloy. Habibnejad-Korayem et al. [30] have ob-
served uniform dispersion of Al2 O3 nano-particles in pure Particle size 80 nm
Color Black
Mg and AZ31 alloy. Similarly, Nie et al. [31] have observed
Form Hexagonal
equal dispersion of nano-particles in Mg-alloy by using ul- Specific surface area (SSA) 3–8 m2 /g
trasonic vibration assisted stir casting method. In ultrasonic Purity of WC 99.9%
vibration, high frequency ultrasonic waves are transmitted to Composition of WC Tungsten-93.8%
liquid metal. These waves generate acoustic streaming, mil- Carbon-6.1%
lion shock waves and intense heating. As a result, particles
will disperse uniformly in the matrix [32].
ment. Mg-alloy ingots are put into the stainless steel crucible
From the existing literatures, it is seen that corrosion be-
and furnace temperature is set at 750 °C. Details of the fur-
havior of magnesium composites are an important area of re-
nace with picture are reported elsewhere [33]. A thermocouple
search but reports on corrosion behavior of magnesium nano-
(K-type) is placed in the main furnace to continuously mon-
composites are scanty. To satisfy that literature gap present
itor the melt temperature. At the mean time, desired wt% of
investigation aims to develop Mg-WC nano-composites by
WC nano-particles is pre-heated (300 °C) to avoid the wetta-
ultrasonic vibration assisted stir casting method and study the
bility issues. After a certain time, the AZ31 ingots get melted
corrosion behavior of fabricated composites with the help of
and the mechanical stirrer is dip into the melt with a high ro-
potentiodynamic polarization and EIS tests in 3.5% NaCl so-
tational speed (500 rpm) to create vortex in the molten alloy.
lution. Effect of WC nano-particles wt% and surface rough-
Then WC nano-particles are fed into the vortex at a constant
ness on corrosion behavior is evaluated. In previously pub-
rate and speed of stirrer is increased to 600 rpm. Mechanical
lished paper [33] it is observed that Mg-2WC nano-composite
stirring is continued for another 5 min. Then high frequency
is the most wear resistive material in dry sliding condition
(20 kHz) ultrasonic vibration is applied in the melt for 5 min.
within the operating range. Thus in order to achieve good
After that, the die is placed under the bottom pouring hole
wear resistance as well as good corrosion resistance mate-
by putting it into the vacuum arrangement and high vacuum
rial, Mg-2WC nano-composite samples are chosen for study-
condition (10−2 mbar) is created by switching on the vac-
ing surface roughness effect on corrosion. Mg-2WC samples
uum pump. Now, the mixed slurry is poured into the die
are polished with 240, 320 and 400 SiC grit paper. Surface
through the bottom pouring hole. Following same procedure,
roughness of differently polished samples is studied using
all composites are fabricated. After solidification, composite
3D surface profiler. After that corrosion tests of the polished
bars are collected from die and machined with the help of
surfaces are performed and corrosion results are tried to co-
lathe, shaper, grinder to prepare samples of desired size and
relate with the roughness parameters. Concurrently, transition
shape.
of corrosion mechanisms due to reinforcing phases and differ-
ent surface roughness are attained with the help of scanning
electron microscope (SEM) and energy dispersive X-ray anal- 2.2. Microhardness test
ysis (EDAX).
Microhardness test of base alloy and Mg-WC composites
2. Experimental details are carried out with the help of a UHL Vicker’s microhardness
tester (VMHT MOT, Technische Mikroskopie) by following
2.1. Materials and methods ASTM standard E384-99. A diamond indenter is used for
indentation while 50 gf load and 10 s dwell time is considered
Mg–3Al–Zn alloy (popularly known as AZ31) is chosen as as indentation parameter. Five readings are taken for each
the matrix metal and WC nano-particles (Average size 80 nm) sample at different points on surface and average of them is
are chosen as reinforcement phase. Chemical composition de- taken as the microhardness value of each sample.
tails of base alloy and reinforcement phase are shown in
Tables 1 and 2, respectively. 2.3. Surface roughness test
Mg-WC metal matrix nano-composites are fabricated in
a specially designed resistance furnace which has mechani- Samples of size (15 mm × 15 mm × 8 mm) are prepared
cal stirrer, powder pre-heating arrangement, mold pre-heating from Mg-2WC metal matrix nano-composite bar. The samples
arrangement, inert gas supply, bottom pouring arrangement, are polished with three different graded SiC emery papers
vacuum pouring attachment and ultrasonic vibration attach- (240 grit, 320 grit and 400 grit) to find the effect of surface
684 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
roughness on corrosion behavior. Surface roughness of the
polished samples is measured with the help of a 3D surface
profiler (Contour X surface profiler, Bruker). Five different
points of the surface are analysed for each sample and average
roughness is taken as the final roughness of that sample. The
roughness tester is connected with a computerized system. 3D
surface plots and 2D surface plots of the samples are captured
by the attachment of the surface plotter and recorded in the
computer.
2.4. Corrosion test
A potentiostat (Gill AC, ACM Instruments, UK) is used
to conduct the electro-chemical impedance spectroscopy and
potentiodynamic polarization tests of AZ31 base alloy and
Mg-WC nano-composites. Tests are performed at room tem-
perature (30 °C) and 3.5 wt% NaCl solution as electrolytic
medium. Contact area of samples with electrolyte solution
is kept fixed as 1 cm2 for all tests. For conducting corro-
sion tests, three electrodes are used. At first, composite sam-
ples are rinsed with acetone and attached to the potentiostat
as working electrode. Other two electrodes are one reference
electrode and one auxiliary electrode. Saturated calomel elec-
trode is used as reference electrode as it provides a stable
potential. Platinum electrode is taken as auxiliary electrode
because platinum electrode provides alternate way to the ap-
plied current in electrolyte solution. All electrodes are dip into
the partially filled glass cylinder and 1 cm2 of samples are
kept in touch with electrolyte solution. After that, 15 min time
is given to settle down and stabilize the open circuit poten-
tial (OCP). Potentiostat is operated by the attached computer
and output curves are analysed by the dedicated software in-
stalled in the computer. Output parameters like Ecorr (corro-
sion potential) and icorr (current density) are obtained by Tafel
extrapolation techniques of anodic and cathodic parts of the
Tafel plot. Corrosion test are conducted by considering start
and reverse potential as −250 mV and 250 mV respectively
Fig. 1. SEM micrographs of composites (a) Mg-1WC, (b) Mg-2WC.
while scan rate is taken as 1 mV/s for both the direction. On
the other hand, EIS study provides exhaustive data on corro-
sion behavior of selected material which helps to understand
the rate of corrosion of that material in the form corrosion
parameters (double layer capacitance and charge transfer re-
sistance). Double layer capacitance (Cdl ) and charge transfer
resistance (Rct ) are measured by analysing (using best fitting
semi-circle) the Nyquist plot with the help of the dedicated
software.
2.5. Surface morphology
Characterizations of the composite samples and corroded
surfaces are carried with the help of scanning electron micro-
scope (SEM) (JSM-6360, JEOL, Japan). Compositional anal-
yses of the fabricated composites and corrosion products of
the surfaces are also studied with the energy dispersive X-ray
analysis set up which is attached with the SEM set up.
3. Results and discussion
3.1. Surface characterization
SEM images of AZ31-WC nano-composites with 1 wt%
and 2 wt% of WC nano-particles are presented in Fig. 1.
Fig. 1 shows compact structures for these two composites and
almost uniform distribution of reinforcements all through the
matrix. Though some amount of agglomeration is observed in
Fig. 1(b) for Mg-2WC nano-composite, still it is observed that
WC nano-particles have sufficiently refined the grain struc-
tures of the composites. EDAX results of AZ31-1WC and
AZ31-2WC are shown in Fig. 2. It is observed that all the
elements of base alloy (Table 1) are present in EDAX spec-
trum and weight percentage of tungsten has increased with
increase in percentage of WC. However, exact percentage of
each constituent is not matching with the EDAX results be-
cause reinforcement phase is of nano-metric size and small
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695 685

Fig. 2. EDAX pattern of Mg-WC nano-composites: (a) 1% WC, (b) 2% WC.

Table 3 particles. Hardness value is enhanced 42.86% when 2 wt%

Micro-hardness of WC powder. WC is added into AZ31 alloy. Such effects of nano-WC are
Material Micro-hardness (HV) increasing load bearing capacity of base matrix which is pre-
Base alloy 68.35 viously reported [7]. Current results are in line with those
Mg-0.5WC 80.90 reports.
Mg-1WC 85.00
Mg-1.5WC 95.65
Mg-2WC 104.20 3.3. Corrosion test

3.3.1. Corrosion test of base alloy and composites

area of the sample is scanned only for the study. Meanwhile,
EDAX results firmly ratify the inclusion of WC in fabricated
nano-composites.
3.2. Microhardness
Hardness of the fabricated nano-composites is affected by
the inclusion of ceramic WC nano-particles. Microhardness
values of the nano-composites are shown in Table 3 which in-
dicates that hardness values of nano-composites are increased
continuously with increase in weight percentage of WC nano-
Potentiondynamic polarization curves of base alloy and
fabricated composites are presented in Fig. 3. Each Potention-
dynamic polarization curve is consisted of cathodic part and
anodic part. Srinivasan et al. [34] have reported that anodic
part explains the transformation mechanism (passive to break-
down) of material surface while main electrochemical reaction
of cathodic part is hydrogen evolution (H+ + e− → ½ H2 ). Ac-
cordingly, study on anodic part will be of more importance to
understand the corrosion behavior and corrosion mechanism
occurred in Mg-alloy and Mg-MMCs at 3.5% NaCl solution.
Fig. 3 shows that corrosion performance and weight percent-
686 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
Fig. 3. Potentiodynamic polarization curve of base alloy and Mg-WC nano-
composites.
Table 4
Electrochemical corrosion parameters of base alloy and nano-composites ob-
tained from potentiodynamic polarization curves.
Material icorr (mA/cm2 ) Corrosion potential (V)
Base alloy 0.0713916 −1.430
Mg-0.5WC 0.0551655 −1.375
Mg-1WC 0.1555669 −1.530
Mg-1.5WC 0.1467948 −1.520
Mg-2WC 0.1161543 −1.500
age of tungsten carbide is not following a linear relation. Kav-
imani et al. [35] have reported that such phenomenon appears
due to different behavior of anodic and cathodic part while
scanning for different reinforcement percentage. Therefore,
precise and clear calculation of corrosion potential and current
density are required for each curve. Tafel extrapolation of po-
tentiodynamic polarization curves helps to find the corrosion
potential (Ecorr ) and current densities (icorr ). Tafel extrapola-
tion results are tabulated in Table 4. As per literature, higher
value of Ecorr and lower value of icorr is desired for attaining
better corrosion resistance [16]. From Table 4, it can be con-
cluded that Mg-0.5WC is the most corrosion resistant material
followed by base alloy, Mg-2WC, Mg-1.5WC and Mg-1WC
composites. In Table 4, it is observed that corrosion poten-
tial of base alloy is about −1.43 V in 3.5% NaCl solution
whereas corrosion potential of Mg-0.5WC nano-composite is
−1.375 V. Such trend indicates that corrosion resistance in-
creases by incorporating 0.5 wt% WC nano-particles in AZ31
alloy. Meanwhile corrosion potential of Mg-1WC, Mg-1.5WC
and Mg-2WC are −1.53 V, −1.52 V and −1.50 V respectively.
It implies that corrosion rate increases when 1, 1.5 and 2 wt%
of WC nano-particles are added to AZ31 magnesium alloy.
In Fig. 3, it is notified that current density of anodic part for
base alloy and composites increases suddenly after a certain
value of the potential. This sudden increment in current den-
sity signifies severe corrosion and pitting tendency. But the
rate of increment of current density for base alloy and Mg-
Fig. 4. Nyquist plot of base alloy and Mg-WC nano-composites.
0.5WC is slower than Mg-1WC, Mg-1.5WC and Mg-2WC
composite.
Typical Nyquist plots of EIS study for AZ31 base alloy and
Mg-WC nano-composites in 3.5% NaCl solution are shown
in Fig. 4. It is observed that each EIS plot consists of one
high frequency capacitive semicircle, one medium frequency
capacitive semicircle and one low frequency inductance loop
when operated between a start potential of −250 mV and re-
verse potential of 250 mV. Basic nature of EIS curves are
similar in base alloy and fabricated composites except the di-
ameter of the curves. Similar observations are reported by Wu
et al. [36] for AZ31 alloy. They stated that diameter of to-
tal capacitance arc is directly proportional to the polarization
resistance and higher value of polarization resistance implies
higher corrosion resistance. Hence it is clear from Fig. 4 that
nano-composite containing 0.5 wt% WC nano-particle is the
most corrosion resistive one followed by base alloy, Mg-
2WC, Mg-1.5WC and Mg-1WC. Previously, Srinivasan et al.
[34] reported that the presence of high frequency capacitive
curve attributes the surface film-electrolyte interface and low
frequency capacitive curve is the reflection of ion diffusion
between generated film and material interface. Hence, low fre-
quency inductive curve denotes electrolyte diffusion at mate-
rial interface and film which causes localized corrosion. Fig.
4 also shows that addition of WC nano-particles up to 0.5 wt%
increases the diameter of capacitive arc than base alloy which
necessarily implies that more protective surface film is present
at film-electrolyte interface with increased impedance value.
Such film protects the material surface from corrosive ions.
But no particular trend of corrosion behavior with respect to
time is found. It is observed that with further addition of WC
nano-particles, diameter of capacitive arc reduces and pres-
ence of inductive loop becomes prominent as a consequence
of anodic potential. Mg-1WC nano-composite shows least ca-
pacitive arc diameter followed by Mg-1.5WC and Mg-2WC
nano-composites. Reduction in capacitive arc diameter with
continuous increment in anodic potential indicates electrolyte
diffusion and attack of aggressive ions on material surface.
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695 687

Fig. 5. 3D Optical surface profile of Mg-2WC samples (a) normal polished, (b) 240 grit paper polished, (c) 320 grit paper polished, (d) 400 grit paper
polished.
688 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695

Fig. 5. Continued
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
Table 5
Surface roughness of Mg-2WC composites with different surface finish.
Sample finish
Normal finish
240 grit
320 grit
400 grit
Fig. 6. Potentiodynamic polarization curve of Mg-2WC samples with differ-
ent surface roughness.
3.3.2. Corrosion test of Mg-2WC composites with different
roughness values
Before performing corrosion tests on Mg-2WC composites
with different surface roughness, surface profiles are obtained
and presented in Fig. 5. In Fig. 5, there is surface profile of
Mg-2WC composite sample (normal polished) which is used
in the study of Figs. 3 and 4, along with surface profile of
three differently polished Mg-2WC composites. Each image
in Fig. 5 consists of 3D optical profile, 2D plot and corre-
sponding roughness profile of each operating surface.It is evi-
dent that Mg-2WC normal polished sample has better surface
quality than the sample polished with 240 grit paper. Further-
more, Mg-2WC samples polished with 320 and 400 SiC grit
paper show smoother surfaces, respectively. Measured surface
roughness values are tabulated in Table 5. Ra value of 400 grit
emery paper polished sample is minimum which is followed
by 320 grit paper polished sample, normal polished sample
and 240 grit polished sample.
Now potentiodynamic polarization curves of Mg-2WC
nano-composite with all these surface characteristics are
presented in Fig. 6. Other operating conditions are kept
same. Tafel extrapolation results of the polarization curves in
Fig. 6 are tabulated in Table 6. It is observed that icorr value
is decreased significantly when surface roughness value is de-
creased. However no significant change in cathodic current is
found with respect to roughness values which implies that the
corrosion behavior of the tested samples are mainly depen-
dent on the anodic behavior of the material. Mg-2WC nano-
composite polished with 400 grit SiC paper having lowest sur-
689
Table 6
Electrochemical corrosion parameters of Mg-2WC composites with differ-
entsurface finish obtained from potentiodynamic polarization curves.
Ra (μm)
Material icorr (mA/cm2 ) Corrosion potential (V)
0.916
1.140 240 grit 0.1242453 −1.51
0.805 320 grit 0.0986514 −1.48
0.568 400 grit 0.0687437 −1.42
Fig. 7. Nyquist plot of Mg-2WC samples with different surface roughness.
face roughness (Ra = 0.568 μm) shows highest value of Ecorr .
Meanwhile, samples polished with 240 grit (Ra = 1.16 μm)
and 320 grit (Ra = 0.916 μm) show sudden increase in cur-
rent density (anodic) just after Ecorr which is not present in
Mg-2WC nano-composite polished with 400 grit paper. Ex-
istence of pitting potential results in such sudden increase in
current density. Fig. 6 shows that the corrosion potential of
lowest surface roughness sample is −1.42 V which is better
than the corrosion potential of base alloy (−1.43 V). This re-
sult indicates that good corrosion resistant as well as good
wear resistant material can be developed by controlling the
surface roughness of selected material.
Fig. 7 shows the Nyquist plots of differently polished
Mg-2WC nano-composite samples tested at 3.5 wt% NaCl
solutions. In polished sample also, Fig. 5 like Nyquist plot is
observed, i.e., one high frequency capacitive loop, one low
frequency capacitive loop and one low frequency inductive
loop. Fig. 7 shows that the diameter of the high frequency
capacitive loop increases and radius of inductive loop de-
creases with increase in surface quality. High frequency
capacitive loop indicates the presence of ion transfer and
film generation, low frequency capacitive loop indicates mass
transfer from sample surface and inductive loop signifies pit-
ting tendency [28]. Hence it can be said that materials having
better surface quality possess better corrosion resistance.
3.5. Corrosion morphology
Overall corrosion morphologies of AZ31 base alloy and
AZ31-WC metal matrix nano-composites are provided in
Fig. 8 with lower magnification (100×, Fig. 8(a), (c), (e), (g)
690 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695

Fig. 8. SEM images of corrosion surfaces of nanocomposites: lower magnification view ((a): base alloy, (c): Mg-0.5WC, (e): Mg-1WC, (g): Mg-1.5WC, (i):
Mg-2WC); higher magnification view ((b): base alloy, (d): Mg-0.5WC, (f): Mg-1WC, (h): Mg-1.5WC, (j): Mg-2WC).
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695 691

Fig. 9. EDAX analysis of corroded surface (a) base alloy, (b) Mg-0.5WC, (c) Mg-1WC, (d) Mg-1.5WC, (e) Mg-2WC, (f) needle like shape, (g) loose filament.
692 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
and (i)) and higher magnification (500×, 1.0 KX and 3.0 KX,
Fig. 8(b), (d), (f), (h) and (j)) SEM images of corroded sur-
faces. Lower magnification SEM images provide an overall
view of the composite surface affected by 3.5% NaCl solu-
tion while magnified views provide minute details of it. In
Fig. 8(a), considerable amount of corroded area is observed
on AZ31 surface while in Fig. 8c percentage of corroded area
has decreased significantly with addition of 0.5 wt% WC. In
lower magnified images related to 1, 1.5 and 2 wt% WC com-
posites (Fig. 8(e), (g) and (i)), greater corroded area than base
alloy and Mg-0.5WC composites is distinguishable. Mean-
while corroded area of 1, 1.5 and 2 wt% WC composites lies
in the order of Mg-1WC> Mg-1.5WC> Mg-2WC. On the
other hand, higher magnification SEM images (Fig. 8(b), (d),
(f), (h) and (j)) show volcano-like deposit of insoluble corro-
sion product over the corroded surface. Similar findings were
reported by Kavimani et al. [35] and Ascencio et al. [37].
Fig. 8 also shows the presence of cracks within corrosion de-
posits. Bakhsheshi et al. [38] reported that cracks of deposited
layer are formed in atmospheric condition due to dehydration
of the layer. Electrolyte solution comes in contact with ma-
Fig. 10. SEM images of corroded surfaces of Mg-2WC samples with different surface finish (a) 240 grit paper polished, (b) 320 grit paper polished,
(c) 400 grit paper polished.
trix material through these cracks and speed up the corrosion
rate. Hence the corrosion characteristics of base alloy and
nano-composites can be predicted by studying the nature and
position of the generated cracks. However, it is also observed
that surface of Mg-0.5WC nano-composite (Fig. 8(d)) pos-
sess lesser cracks and pores than the surface of AZ31 base
alloy (Fig. 8(b)) which completely correlates the advancement
in corrosion resistance of AZ31-0.5WC nano-composite. Ad-
dition of 1 wt% WC nano-particles contributes in formation
of large cracks, pores and pits on corroded surface. Further
addition of WC up to 2 wt% results in decrease of the inten-
sity of cracks and pits formation.Visual inspection of Fig. 8(f)
and (h) shows needle like structure within the corroded sur-
face. Higher magnification view of these structures revealed a
sunflower or ‘sand rose’ like morphology. This type of mor-
phology was found previously by Pathak et al. [39]. In the
inset of Fig. 8(j), image at 3000× magnification is presented
which shows the formation of loose filaments in the corroded
layers.
Corroded surfaces are further analysed with the help of
energy dispersive X-ray analysis (EDAX). In SEM images
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695 693

Fig. 11. EDAX analysis of corroded surface Mg-2WC samples with different surface finish (a) 240 grit paper polished, (b) 320 grit paper polished,
(c) 400 grit paper polished.
694 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
(Fig. 8), corrosion deposited layers comprises of loosely
bonded outer layer and porous inner layer are clearly ob-
served. EDAX analysis (Fig. 9) discloses that main constituent
of these surface layers are Mg and O. In most of the cases Mg
and O maintains a constant atomic ratio of 1:2 which clearly
indicates the presence of Mg(OH)2 and MgO in surface lay-
ers. Song and Gamon [40] have also reported the presence
of Mg(OH)2 and MgO in surface layers and Bakhsheshi-Rad
et al. [38] have found that the disintegration of magnesium
alloy and composites in NaCl solution occurs by following
mechanism:
Mg + 2H2 O → Mg(OH )2 + H2
Mg(OH )2 + 2Cl− → MgCl2 + 2OH−
Cl peak is also observed in EDAX spectra. Literature sug-
gests that the presence of chlorine ion in corrosive layers
mainly signifies the presence of MgCl2 in these layers [40].
EDAX of base alloy (Fig. 9(a)) and Mg-0.5WC (Fig. 9(b))
nano-composites corrosion product reveal that intensity of
chlorine peak is reduced in Mg-0.5WC nano-composites. This
decrement in chlorine percentage suggests that 0.5 wt% rein-
forcement have increased the stability of corrosion layer and
protected the surface from the corrosive attack of Cl− ion.
Similar finding was reported by Turhan et al. [41] for Mg-
MWCNT composites. But EDAX spectra of Mg-1WC, Mg-
1.5WC and Mg-2WC nano-composites corrosive layer (Fig.
9(c), (d) and(e), respectively) show more intensity in oxy-
gen and chlorine peak than base alloy and Mg-0.5WC nano-
composite. Chlorine percentages remain in the order of Mg-
1WC > Mg-1.5WC > Mg-2WC. SEM images of base al-
loy and composites reveal similar order in crack generation.
Hence it is clear from the SEM and EDAX results that chlo-
rine ions infiltrate through cracks of the corrosive layer and
corrode the material surface. This finding is in line with the
report of Thirumalaikumarasamy et al. [42]. They suggested
that more amounts of Cl− ion and crack mean more corro-
sion of the material surface. EDAX [Fig. 9(f)] of needle-like
structures (sand-rose) reveal the presence of high percentage
of oxygen and chlorine, which is generated by formation of
Mg(OH)2 and MgCl2 through Eq 2. In literatures such ac-
cumulated needle-like structures and presence of Mg(OH)2
(Brucite) was noted [39]. Cl− ions of NaCl solution convert
the generated Mg(OH)2 into MgCl2 and surge the corrosion
rate of nano-composite surface. Overall it is also observed
that with the increasing percentage of needle-like structure,
percentage of pit formation has increased. Hence it can be
said that MgCl2 is a major reason of pit generation on Mg-
MMNC surface. Wang et al. [43] have also observed similar
behavior of chloride ion on magnesium like needle-like struc-
ture. EDAX study [Fig. 4(g)] of filament like structure shows
large oxygen and chlorine peak suggesting the presence of
Mg(OH)2 and dissolution of this layer in chloride solution.
In this case it can be said that typical filaments are proba-
bly formed due to rapid dissolution of magnesium in chloride
solution. Song and Gannon [40] have also drawn similar con-
clusion in their study.
SEM morphology of corroded surfaces of Mg-2WC nano-
composites with different surface roughness are presented
in Fig. 10. It is observed that nano-composite surface hav-
ing highest roughness value (Fig. 10(a)) shows volcano-like
deposit and large surface cracks on the corrosion deposit,
whereas nano-composite with mid-range (Fig. 10(b)) and low-
est roughness value (Fig. 10(c)) show comparatively smooth
corrosive layer over the material surface with less amount
of cracks. In case of medium and finest composites some
volcano-like corrosion product are spalled abruptly over the
corroded surface but that percentage is much lesser compared
to the coarser sample. In another perspective, corrosive pits
(1)
and pores are observed in coarser and medium roughness
samples but interestingly no significant pitting is observed
(2)
in lowest roughness sample. It is known that corrosive Cl−
ions of NaCl solution enter through the generated cracks of
bi-product layer and corrode the material surface. Scope for
entering Cl− ions are more in coarser sample because it con-
tains larger cracks. Simply it results in larger corrosion rate
at roughest sample compared to other two samples. Similar
observations are reported by Walter and Kannan [28].
Corroded surfaces of samples with different roughness are
further studied with the help of EDAX analysis. EDAX spec-
trums and corresponding weight percentage of different ele-
ments are shown in Fig. 11. It is seen that atomic ratio of Mg
and O of samples having highest surface roughness is nearly
equal to unity while that ratio for other samples is in the order
of 1:2. This result indicates that the bi-product layers of less
roughness samples (Fig. 11(b) and (c)) are more protective
and stable. Additionally, percentage of corrosive Cl− ion in
protective layer of highest roughness sample (Fig. 11(a)) is
much higher than other two samples. Increase in amount of
Cl− ion with increase in roughness value confirms the spec-
ulation done in the previous paragraph.
4. Conclusion
Ultrasonic vibration assisted stir casting method is suc-
cessfully employed to develop AZ31 magnesium alloy based
nano-composites containing 0.5, 1, 1.5 and 2 wt% WC.
SEM shows that WC nano-particles are almost uniformly
distributed over the matrix phase. Microhardness of nano-
composites is escalated with the addition of WC nano-
particles. Electro-chemical impedance spectroscopy and po-
tentiodynamic polarization tests of the base AZ31 alloy and
AZ31-WC composites are examined in 3.5 wt% NaCl solu-
tion. Nyquist plot consists of one high frequency capacitive
loop, one low frequency capacitive loop and one low fre-
quency inductive loop which are representing film generation,
mass transfer and pitting formation respectively. Tafel extrap-
olation of potentiodynamic polarization plot provides the val-
ues of corrosion potential and corrosion current density which
disclose that Mg-0.5WC nano-composite is the most corrosion
resistance material. Electrochemical impedance spectroscopy
and potentiodynamic polarization tests are done for different
polished Mg-2WC composites. Nyquist plot shows that diam-
eter of high frequency capacitance curve of samples polished
 S. Banerjee, S. Poria and G. Sutradhar et al. / Journal of Magnesium and Alloys 7 (2019) 681–695
with 400 grit is the largest than other two polished sam-
ples which iterates that corrosion resistance increases with
decrease in surface roughness. Potentiodynamic polarization
curve for different roughness samples also confirmthe same
relation between roughness and corrosion resistance. Corro-
sion morphology shows that cracks and pores are present on
corrosion surface and Cl− ions infiltrates through the cracks
and accelerate the corrosion rate. Among different wt% com-
posites, surface of Mg-0.5WC has lowest cracks while among
different roughness composites of same amount reinforce-
ment, fine polished composite has lowest cracks. More num-
ber of cracks at the corroded surface of composites becomes
co-related linearly with reduction in corrosion resistance.
Declaration of Competing Interest
None.
Acknowledgment
The authors gratefully acknowledge the support of DST
(GOI) through Smart Foundry 2020 program.
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