Journal of King Saud University – Engineering Sciences (2016) 28, 246–250

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ORIGINAL ARTICLE

Corrosion behavior of duplex coatings

a,*
K. Raghu Ram Mohan Reddy , N. Ramanaiah b, M.M.M. Sarcar b

a
Department of Mechanical Engineering, GITAM University, Visakhapatnam, India
b
Department of Mechanical Engineering, Andhra University, Visakhapatnam, India

Received 1 March 2014; accepted 14 April 2014

Available online 24 April 2014

KEYWORDS Abstract The titanium alloys are used in defense, aerospace, automobile, chemical plants and
Duplex coatings; biomedical applications due to their very high strength and lightweight properties. However,
Corrosion; corrosion is a life-limiting factor when Ti alloys are exposed to different chemical environments
Ti6Al4V at high temperatures. In the present paper, duplex NiCrAlY/WC–Co coating is coated onto
Ti6Al4V substrate to investigate the corrosion behavior of both coated samples and the substrate.
The duplex coating was performed with NiCrAlY as the intermediate coat of 200 lm thickness
deposited by HVOF process and WC–Co ceramic top coat with varying thicknesses of 250 lm,
350 lm and 450 lm deposited by DS process. Potentiodynamic polarization tests were employed
to investigate the corrosion performance of duplex coated samples and substrate in Ringer’s
solution at 37 C and pH value was set to 5.7. Finally the results reveal that 350 lm thick coated
samples showed highest corrosion resistance compared to 250 lm thick samples as well as bare
substrate. However, the 450 lm thick coated sample showed poor corrosion resistance compared
to the substrate. The scale formed on the samples upon corrosion was characterized by using
SEM analysis to understand the degree of corrosion behavior.
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1. Introduction Among various titanium alloys, Ti6Al4V is extensively used

Titanium alloys are widely sought after materials for biomedical
applications, as they possess better corrosion resistance and
biocompatibility as compared to stainless steel, Co–Cr alloys.
* Corresponding author. Tel.: +91 9912168971; fax: +91
8912790399.
E-mail address: raghukappa@gmail.com (K. Raghu Ram Mohan
Reddy).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
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This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
due to its useful mechanical and electrochemical properties
(Goldberga and Gilbertb, 2004). A thorough understanding of
high temperature corrosion behavior of Ti–6Al–4V is very
essential for its viable applications in gas turbine components.
It is essential to understand the degradation mechanism of tita-
nium alloys under hot corrosion conditions and, subsequently,
to apply appropriate coatings to effectively combat hot corro-
sion. Also, various surface modification methodologies such
as plasma ion implantation (Mandl and Rauschenbach, 2002),
laser melting (Singh et al., 2006) and laser surface alloying
(Man et al., 2005), thermal oxidation (Garcia-Alonso et al.,
2003), have been tried out to improve wear, corrosion, and
fretting resistance of orthopedic implant materials including
Ti6Al4V. Raghu Ram Mohan Reddy et al. (2013a,b) studied
Corrosion behavior of duplex coatings
the tribological behavior of duplex coatings on Ti6Al4V alloy
using HVOF and DS.
In general, the corrosion/erosion/wear resistance of thermal
spray coatings depends on the chemistry and morphology of
coatings. Microstructural features which enhance the coating
performance include high density and low porosity, small grain
size, good adhesion and absence of cracks (Wang and Lee,
1997). Wang et al. (2013) deposited WC coatings consisting
of different binders by HVOF and found that the corrosion
resistance of WC–Co–Cr coating was superior to that of
WC–Co coating. Also Jafari et al. (2013) investigated the oxi-
dation behavior of HVOF-sprayed WC–12Co and WC–10Co–
4Cr coatings. The authors reported that the higher oxidation
resistance of WC–10Co–4Cr coating probably results from
the formation of compact chromium oxide layers and higher
MWO4 type tungstate (M: Co and/or Cr) to tungsten trioxide
(WO3) ratios which provide lower porosity.
In the present investigation duplex coatings were employed
on the Ti6Al4V substrate to enhance the corrosion resistance.
The NiCrAlY bond coat was deposited with 200 lm thickness
by using HVOF and WC–Co top coat was deposited with vary-
ing thicknesses (250 lm, 350 lm and 450 lm) by using DS.
2. Experimentation
2.1. Coating deposition
Thermal spray duplex coatings were deposited on Ti6Al4V
substrate. NiCrAlY and WC–Co were used as coating
materials. The chemical compositions of NiCrAlY powder
and WC–Co powder are presented in Tables 1 and 2 respec-
tively with an average particle size of 30 lm. In the present
investigation, duplex coating was performed with NiCrAlY
as the intermediate coat of 200 lm thickness deposited by
HVOF process and WC–Co as the top coat with varying
thicknesses of 250 lm, 350 lm and 450 lm deposited by DS
process. Prior to deposition the substrate surfaces were grit
blasted with alumina grits, followed by an ultrasonic cleaning
in acetone. The grit blasting was performed to get an optimum
surface roughness and promote the best attainable adhesion
between coating and substrate. The standard spraying process
parameters are followed for HVOF and DS (Raghu Ram
Mohan Reddy et al., 2013a,b). JSM-6610LV Scanning electron
microscope (SEM) equipped with energy dispersive X-ray
Table 1 Chemical composition of NiCrAlY
powder.
Constituent % After equilibration, polarization started at a rate of 1 mV/s.
Cr 22
Al 10
Y 1
Ni Bal.
Table 2 Chemical composition of WC–Co
powder.
Constituent %
WC 88
Co 12
247
analyzer (EDX) is used to study the microstructure of the sam-
ples. X-ray diffraction patterns of the powders and coatings
were taken using an Ultima IV X-ray diffractometer with
CuKa radiation and Ni filter.
2.2. Residual stress measurements
Residual stress measurements are made using PANalytical X-
Pert Pro MRD system for untreated and heat treated samples.
2.3. Microhardness test
Microhardness tester model VMHT auto was used to find
microhardness of substrate and coated material. Microhard-
ness tests were performed by using the Vickers Microhardness
tester (model VMHT auto) on a cross section of coatings with
a load of 300 g and dwell period of 10 s. An average of three
readings is reported.
2.4. Pull-out test
The pull-out tests were performed to those coated specimens
under an increasing load with a stretching rate of 2 mm/min
using a tensile test machine (Instron materials tester – Model
1121) until the shearing failure occurred. The failure mode is
recorded gradually, and the bonding strength is calculated as
the load at failure divided by the coated bonded area.
2.5. Potentiodynamic polarization test
The corrosion behavior of duplex coatings and uncoated sam-
ples was investigated by potentiodynamic polarization tech-
nique. All the electrochemical measurements were carried out
in accordance with ASTM standard of G107-95 A. The elec-
trochemical behaviors of the materials have been analyzed in
deaerated Ringer’s solutions (NaCl = 8.60 g/L, CaCl2Æ2H2-
O = 0.33 g/L and KCl = 0.30 g/L) in a Pyrex glass cell. The
pH of the test solution was 5.7 at room temperature. The
potentiodynamic polarization curves were obtained by an
Ag/AgCl reference electrode and a platinum (Pt) counter elec-
trode. The exposed area of the working electrodes was about
(0.785) cm2. The corrosion tests were performed by using a
GILL AC electrochemical apparatus (ACM instruments, Uni-
ted Kingdom). The solution was deaerated to remove oxygen
with nitrogen (N2), and the process was started 1 h prior to
the measurement. The specimens were immersed into the solu-
tion until obtaining a steady open circuit potential (OCP).
The cycle began at the cathodic over potential, according to
OCP, and the scan was stopped when the specimens reached
the anodic current density of approximately 1 mA/cm2. After
polarization, the examinations of the corroded surfaces were
carried out by using a JSM-6610LV model SEM.
3. Results and discussion
3.1. Characterization of coatings
Fig. 1 shows the SEM microstructure of powder samples and
Fig. 2 shows the SEM micrographs of cross sectional duplex
248 K. Raghu Ram Mohan Reddy et al.

Figure 1 SEM microstructure of (a) WC–Co and (b) NiCrAlY powders.

Figure 2 SEM cross sectional duplex coating of varying thicknesses (a) 250 lm, (b) 350 lm and (c) 450 lm.

coating of varying thicknesses (250 lm, 350 lm and 450 lm)
on Ti6Al4V. The XRD pattern of the ceramic top coat is
shown in Fig. 3. The peaks corresponding to ceramic coating
have been observed in the pattern. The as-sprayed WC–Co
top coat results hard WC particles and during the deposition
the decarburization occurs which results in the formation of
W2C (Raghu Ram Mohan Reddy et al., 2013a,b).
3.2. Porosity and microhardness measurements
It could be observed that the porosity decreases with the
increase in coating thickness (Gu et al., 2012), the decrease
in porosity is probably due to the dense coating by the detona-
tion spray process. The microhardness increases with the
increase in coating thickness. The increase in microhardness
can be attributed to the decrease in the porosity as the coating
thickness increases. The variation of porosity and microhard-
ness is given in Table 3.
3.3. Residual stresses
It has been found that the residual stress increases with
increasing of the coating thickness. The corresponding values
were found to be 168 MPa, 172 MPa and 190 Mpa for the
ceramic thicknesses of 250 lm 350 lm and 450 lm
respectively.
3.4. Bonding strength

It was observed that the bonding strengths decrease with coat-

ing thickness. The corresponding values were found to be
38.3 MPa, 36.65 MPa and 32.31 MPa for the ceramic thick-
nesses of 250 lm 350 lm and 450 lm respectively. This can
be attributed to the increasing tensile residual stresses during
the deposition process with increasing of the coating thickness.

Table 3 Variation of porosity and microhardness with coat-

ing thickness.
Coating Porosity (lm) Vickers Microhardness,
thickness (lm) VHN (GPa)
250 6.51 1215
350 6.23 1257
450 6.11 1294
Figure 3 X-ray diffraction pattern of WC–Co top coat.
Corrosion behavior of duplex coatings 249

substrate is shown in Fig. 5, the primary a phase and trans-

formed b phase are marked with 1 and 2, the porosity with 3
which initiates the corrosion and this feature is shown in
Fig. 5b.
It can be clearly seen from Fig. 4 that the highest corrosion
resistance was exhibited by the 350 lm thick coated samples
over the 250 lm thick coated samples in the Ringer’s solution
at room temperature, which can be attributed to the decrease
in porosity. The porosity values are tabulated in Table 3. How-
ever 350 lm and 250 lm thick coated samples showed better
corrosion resistance than Ti6Al4V substrate. But, surprisingly
the 450 lm thick coated specimen exhibits lower corrosion

Figure 4 Potentiodynamic polarization curves for uncoated and

coated samples.

3.5. Corrosion analysis

The potentiodynamic polarization tests were undertaken in

Ringer’s solution, and the related curves of varying thick
WC–Co coated and uncoated Ti6Al4V substrates, in compar-
ison, are given in Fig. 4. The corrosion behavior is the function
of the most critical parameter, i.e. corrosion potential (Ecorr).
Higher value of Ecorr indicates the more positive in corrosive
behavior. The corrosion behavior of uncoated Ti6Al4V

Figure 5 The SEM graphs after corrosion test (a) Ti6Al4V and Figure 6 The SEM graphs after corrosion test for (a) 250 lm, (b)
(b) magnification of (a). 350 lm and (c) 450 lm.
250
potential compared to the substrate material, this can be due
to an increase in tensile stresses which causes spallation where
the fluid medium stagnates and does not allow the oxygen con-
tent to the substrate surface.
From Fig. 4 the potentiodynamic polarization curves pre-
sented that the Ecorr value is 472.59 mV for Ti6Al4V sub-
strate. The Ecorr values for 250 lm and 350 lm thick coated
samples are 395.28 and 280.52 respectively, which are
higher than the value of Ti6Al4V. But the Ecorr value is
530 mV for 450 lm thick coated sample which was found
to be lower than the value of Ti6Al4V. Also, it is obvious that
the 350 lm thick coated samples are more positive Ecorr value
compared to all coated samples and substrate.
In the present study it is clear that the hardness increases
with increasing of the coating thickness due to a decrease in
porosity. Though, the 350 lm thick coated samples have lower
bond strength than 250 lm thick samples, the porosity influ-
ences more in improving the corrosion resistance. From
Fig. 6a it is evident that the 250 lm thick samples having more
pores and subsequently the electrolyte ions penetrate into sub-
strate through such pores, reported by Zhao et al. (2005),
which results in little delamination and is in agreement with
this work. Also the delamination of coating material increases
with increasing of the coating thickness, the thicker coatings
(450 lm) cause weakening of bond strength. In the other
words; increasing the coating thickness, increases the tensile
stress and reduces the bond strength there by the corrosion
can be initiated and so rendering the WC–Co coating liable
to severe attack (Fig. 6c). The passivation is high for 350 lm
thick coats which can be attributed to delamination free coat-
ing structure as shown in Fig. 6b and the passivation is mod-
erate for 250 lm thick coating which can be attributed to
only a little delamination of coating as shown in Fig. 6a. But
for 450 lm thick coatings the passivation is very low which
is lower than Ti6Al4V substrate because of significant delam-
ination and it can be clearly observed in Fig. 6c.
4. Conclusions
In the present study, the duplex coatings were employed on
Ti6Al4V substrate with varying thicknesses and the corrosion
behavior was studied. From the analysis the following conclu-
sions are drawn.
 Thermal spray WC–Co/NiCrAlY duplex coatings were
deposited successfully on Ti6Al4V substrate with varying
ceramic thicknesses.
 The porosity decreased with increasing of the coating thick-
ness due to dense thermal spray coatings.
 The hardness increased with increasing of the coating thick-
ness and this can be attributed to the lower porosity.
 The pull off test revealed that the bond strength decreased
with increasing of the coating thickness. This can be attrib-
uted to the increasing tensile residual stresses during the
deposition process.
 The thicker coated sample (450 lm) showed less corrosion
resistance than the Ti6Al4V substrate material. This could
K. Raghu Ram Mohan Reddy et al.
be due to the higher tensile stress formed during the depo-
sition which causes reduction in bond strength or spallation
of coating material from the substrate, thereby the corrosive
medium attacks the substrate severely. The potentiodynam-
ic polarization test proved that the inappropriate coating
thickness cannot improve the corrosion resistance of the
substrates.
 The thinner coated samples (250 lm) showed the better cor-
rosion resistance compared to the substrate. Though the
residual stress is more for 350 lm thick coated sample com-
pared to 250 lm thick coated sample, the porosity influ-
ences greatly in this case, hence showed better corrosion
resistance than other two coated samples as well as the
substrate.
 The potentiodynamic polarization test revealed that the
optimum coating thickness is 350 lm for the best corrosion
resistance.
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