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Investigation of corrosion behavior of polypyrrole-

coated Ti using dynamic electrochemical
Cite this: RSC Adv., 2016, 6, 80275
impedance spectroscopy (DEIS)
Bhavana Rikhari, S. Pugal Mani and N. Rajendran*

Received 8th April 2016
Accepted 14th August 2016
DOI: 10.1039/c6ra09100h
www.rsc.org/advances
In the present work, dynamic electrochemical impedance spectroscopy (DEIS) was used to investigate the
corrosion behavior of polypyrrole (PPy)-coated titanium (Ti) in simulated body fluid (SBF) solution. The
deposition of PPy on Ti was carried out using the cyclic voltammetry (CV) technique. The formation of
the PPy coating was confirmed by infrared and Raman spectroscopy. Scanning electron microscopy
(SEM) studies revealed the deposition of a 7 mm-thick PPy coating with a cauliflower-like morphology.
The surface roughness and wettability of the coating were confirmed by atomic force microscopy (AFM)
and water contact angle studies. The corrosion behavior of uncoated and PPy-coated Ti was
investigated in SBF using DEIS and polarization studies. DEIS was carried out from the open circuit
potential (OCP) to dissolution regions of the uncoated and PPy-coated Ti with a step potential of 0.5 V.
The variation in the charge transfer resistance (Rct) value as a function of potential exhibited distinctive
impedance behavior for the uncoated and coated substrates. The PPy-coated Ti showed a higher Rct at
each potential thereby indicating the higher corrosion resistance of the coating. The highest polarization
resistance (Rp) and lowest corrosion current density (icorr) of PPy-coated Ti obtained from the
potentiodynamic polarization studies revealed the enhanced corrosion resistance. The potentiostatic
polarization studies for the PPy-coated substrate showed a low current density value at the OCP and
dissolution potential and it can be attributed to the enhanced protection ability of the coating. Additional
evidence in support of the enhanced corrosion protection performance of PPy was obtained from the
Bode-phase angle maximum value at the OCP and dissolution potential.

polymerization is more preferred because it provides better

1 Introduction
Ti metal and its alloys are extensively used in implantology,
especially as orthopedic implants due to their excellent corro-
sion resistance in bio-uids, and the desirable mechanical
properties play very important roles in improving the quality of
human life.1–6 These excellent properties of Ti metal are attrib-
uted to the presence of a stable lm of titanium dioxide (TiO2)
with small quantities of TiO and Ti2O3 sub-oxides. It is well
known that the excellent properties of TiO2 lm are responsible
for its long term stability in bio-uids and play a key role for the
biocompatibility of Ti and its implants.
Surface modication of Ti and its alloys is normally done to
improve several types of properties like biological, chemical and
mechanical ones to meet the desired expectations. A wide
variety of techniques are available for surface modication7–10 of
Ti and its alloys, such as thermal treatment,11,12 laser deposi-
tion,13–15 anodizing,16–18 spraying19 and electrochemical poly-
merization.20 Among the available techniques, electrochemical
Department of Chemistry, Anna University, Chennai-600 025, India. E-mail:
nrajendran@annauniv.edu; Fax: +91-44-2220-0660; Tel: +91-44-2235-8659
control of the lm thickness and uniformity in the coating.
Conducting polymers, because of their high stability and
ease of synthesis are used as promising materials for many
applications like in polymer light-emitting diodes (LEDs),21 for
corrosion resistance,22,23 thin lm transistors,24 electromagnetic
shielding,25 molecular electronics,26 supercapacitors,27,28 elec-
trochromic devices29 and sensor technology30–34 etc.
Among the various types of conducting polymers, PPy has
been used for wider applications.35–37 PPy has been extensively
used because of its attractive properties e.g. ease of preparation
either by chemical or electrochemical polymerization and due
to its good adherent property on to the metal thereby providing
high stability at the polymer lm/metal interface and more
electrical contact.38 PPy deposition over metal shows the prop-
erty of excellent corrosion resistance due to its high stability,
which helps to prevent electron exchange between the adsorbed
biological species and the metal.39 The lower oxidation potential
(0.8 V) of pyrrole in comparison to other heterocyclic monomers
may probably help in the easy formation of PPy lm on active
metal to provide promising anti-corrosion properties. The
biocompatibility of PPy has been studied extensively and re-
ported in the literature.40,41 For example, PPy lm has been used

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as protective coatings for Ti–Al–V substrates to improve
osseointegration performances.42 Moreover, a recent study on
PPy lm-coated implants in experiments with animals showed
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promising results for in vivo and in vitro studies.43 Therefore, the
present investigation mainly focuses on the corrosion behavior
of PPy-coated titanium in SBF solution for biomedical
applications.
Electrochemical impedance spectroscopy (EIS) is a tech-
nique to investigate the phenomenon between the metal/
solution interface in the electrochemical system i.e. detection
and monitoring of pitting corrosion, passivation of the metal
surface etc. Darowicki and co-workers44,45 developed a new
impedance method termed as DEIS. It is one of the versatile and
recently used electrochemical techniques to study the degra-
dation of metallic materials, pit initiation, propagation and
passivation.46,47 DEIS helps in the measurement of impedance,
which is carried out under potentiodynamic conditions and can
be used to nd out the point of passivation and degradation of
a protective coating on metal. Passivation and surface oxide lm
dissolution are the two important key factors, which can affect
the biocompatibility of metal. Hence, it is essential to study the
different stages involved in the corrosion behavior of Ti and its
alloys or PPy coatings on them to understand the surface
chemistry. However, only very few published works are available
involving DEIS measurement with respect to corrosion studies
of Ti and its alloys. For example, the corrosion behavior of NiTi
and NiTiNb alloys in physiological medium using DEIS was
studied.48 Some other literature is also available for under-
standing the process involved in DEIS studies of coated mate-
rials on AZ31 magnesium alloy.49
In this paper, an attempt has been made to evaluate the
corrosion behavior of uncoated and PPy-coated Ti using the
DEIS technique. In order to assess their corrosion resistance,
DEIS experiments were conducted from the OCP to dissolution
regions of both uncoated and PPy-coated Ti as a function of
applied potential.
2 Materials and methods
2.1 Preparation of substrate
Ti sheets with a size of 25 mm
15 mm
2 mm were used as
substrates, ground using SiC emery paper up to 1200 # grit and
polished. Ti samples were cleaned with double-distilled water
and sonicated with acetone. The ground sheets were chemically
etched using Kroll’s reagent (25 mL H2O + 2 mL conc. HNO3 + 1
mL conc. HF) for 15 s. This enabled the removal of the oxide
layer present on the as-received material. Aer etching, the
samples were cleaned and dried in air at room temperature and
subsequently used for electrodeposition.
2.2 Film deposition
Pyrrole (monomer) was purchased from Aldrich Chemical. It
was distilled twice and stored in the dark, at 0  C. Polymeriza-
tion of pyrrole over the Ti substrate was done by cyclic vol-
tammetry in the potential range between 0.1 and 1.2 V vs. SCE,
with 20 cycles with a sweep rate of 0.05 V s1 in an aqueous
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oxalic acid solution (0.2 M) containing pyrrole (0.2 M)50 with
nitrogen purging. The electrochemical polymerization was
carried out in a three-electrode system consisting of platinum
foil and a saturated calomel electrode (SCE) as the counter and
reference electrodes and Ti as the working electrode. Aer
electrodeposition the sample was rinsed with acetone and
distilled water and dried in air.
2.3 Surface characterization
Attenuated total reectance Fourier transform infrared spec-
troscopy (ATR-FTIR) was recorded in the range between 400 and
4000 cm1 using Perkin Elmer Spectrum II, USA to conrm the
PPy coating. The formed PPy coating was conrmed by Raman
spectroscopy using a FT Raman, Bruker RFS 27 instrument with
1064 nm, and a Nd:YAG source was used for the analysis.
Raman spectra were recorded with a 500 s data point acquisi-
tion time in the spectral range of 200–1200 cm1. To observe the
morphological features, scanning electron microscopy (Hitachi
Model-S 3400, Japan) with an accelerating voltage of 10–30 kV
was employed. The surface topography and roughness were
determined by atomic force microscopy (XE 70), model Park
system, Korea. The water contact angle value for the uncoated
and PPy-coated specimens was calculated with the help of
UTHSHCSA image tool soware using Euromex optical micro-
scope equipment with a CCD camera.
2.4 Electrochemical characterization
All electrochemical studies of the uncoated and polymer-coated
Ti samples were conducted using an electrochemical worksta-
tion, Autolab, PGSTAT-12. The electrochemical studies were
carried out in the conventional three-electrode glass cell. SBF
solution was used as physiological medium and its composi-
tion51 is given in Table 1. The Ti sample was used as the working
electrode. Pt foil and a saturated calomel electrode (SCE) were
used as the counter and reference electrodes, respectively. The
stabilized OCP was obtained aer 45 min of immersion, then
the potentiodynamic polarization studies were carried out from
1.0 to 1.5 V at a scan rate of 1 mV s1. DEIS was studied using
a frequency response analyzer (FRA), starting from the OCP to
dissolution region with a 50 mV step potential in the frequency
range between 0.01 Hz and 100 kHz with 10 mV amplitude. The
Table 1 Composition used for the preparation of SBF solution
Reagents Amount in 1000 mL
NaCl 8.031 g
NaHCO3 0.358 g
KCl 0.223 g
K2HPO4$3H2O 0.233 g
MgCl2$6H2O 0.314 g
1.0 M HCl 39.0 mL
CaCl2 0.290 g
Na2SO4 0.074 g
(HOCH2)3CNH2 6.116 g
1.0 M HCl Appropriate amount for adjusting the pH
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potentiostatic polarization was studied at the OCP and disso-

lution potential for uncoated and PPy-coated Ti.
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3 Results and discussion

3.1 Electrochemical deposition of PPy on Ti electrode
The PPy lm was deposited by potentiodynamic polymerization
using aqueous solution containing oxalic acid as the supporting
electrolyte in the presence of pyrrole monomer. Fig. 1 shows the
cyclic voltammogram of Ti metal in 0.2 M oxalic acid with PPy
monomer. It can be observed that the addition of pyrrole
monomer (0.2 M) in the presence of (0.2 M) oxalic acid solution
changed the behavior of Ti metal. The increase in current
density indicates that the polymerization of pyrrole starts at
about 0.7 V vs. SCE. On increasing the number of scans, the
current density is decreased. Aer completion of all cycles,
a uniform thickness of the adherent black homogenous PPy
lm was deposited on Ti.

3.2 ATR-FTIR and Raman spectral studies

The ATR-FTIR spectrum of the electropolymerized PPy coating
on Ti is shown in Fig. 2(a). In the spectrum of PPy, the char-
acteristic peaks at 3412 and 1074 cm1 are assigned to N–H and
C–H stretching vibrations in the pyrrole ring.52 The peak at 1409
cm1 corresponds to C–N stretching vibration.53 The peak
position at 1031 cm1 is related to the N–H deformation band.
The peak at 1600 cm1 corresponds to the C]C stretching
vibration of the pyrrole ring. The peaks at 1641 and 1571 cm1
represent the symmetric and anti-symmetric stretching modes
in the aromatic ring, respectively. The C–H out-of-plane
bending vibrations are observed at 964 and 956 cm1,
respectively.
The Raman spectrum of the PPy coating is shown in Fig. 2(b).
The strong band at 1592 cm1 represents the oxidized state of
the polymer and it corresponds to the C]C stretching
Fig. 2 (a) ATR-FTIR spectrum of PPy-coated Ti and (b) Raman spec-
trum of PPy-coated Ti.
vibrations of PPy. The absorption peak at 1383 cm1 is assigned
to the C–N stretching vibration of PPy.54 The absorption peak at
1491 cm1 is assigned to C–C stretching vibration. This proves
that PPy has been coated on Ti metal through electro-
polymerization. The peaks appearing at 932 cm1 and 971 cm1
are dened as ring deformation and the peak at 1080 cm1
indicates the in-plane bending vibration in the pyrrole ring.

Fig. 1 Cyclic voltammogram of Ti metal with pyrrole monomer in Fig. 3 SEM images of (a) uncoated Ti, (b) PPy-coated Ti, and (c) cross-
oxalic acid. section of PPy-coated Ti.

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Fig. 4 2D and 3D AFM images of (a) uncoated Ti and (b) PPy-coated Ti.
Fig. 5 Water contact angle images of (a) uncoated Ti and (b) PPy-
coated Ti.
3.3 Scanning electron microscopy studies
The SEM images of the uncoated and PPy-coated Ti and
a cross-section image of PPy-coated Ti are shown in Fig. 3. The
surface morphology of uncoated Ti shows the presence of
grooves due to grinding and mechanical polishing. The SEM
image of the PPy-coated surface reveals a cauliower-like
morphology,55 which shows microspherical grains with vari-
able particle sizes and seems to be compact without porosity
i.e. characteristic of polypyrrole. From the cross-section image,
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it can be observed that the thickness of the PPy coating is
7 mm.
3.4 Atomic force microscopy studies
The topography images of the uncoated and PPy-coated Ti are
shown in Fig. 4. The AFM image of the uncoated Ti was found to
have a at surface consisting of nodules appearing along the
polishing direction with a lower surface roughness value of
about 32.47 nm. The PPy coating shows uniform deposition
along with variable grains over the surface. The AFM 3D image
of the PPy coating shows a well-dened cauliower-like pattern,
which has a perfect correlation with the SEM images with a high
surface roughness value of about 54.96 nm. The high roughness
value of the coating inuences the bone bonding ability and
bioactivity. An increase in the roughness value increases the cell
behaviour viz. cell attachment and osseointegration.
3.5 Water contact angle studies
The surface wettability of implant material plays a crucial role in
inuencing the bioactivity and cell adhesion. The contact angle
value depends on the surface roughness, which is also attrib-
uted to the chemical effect and surface energy of the coating. A
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coated Ti conrmed the hydrophilicity. This may be probably

due to the presence of amine groups present in the PPy polymer
matrix. The hydrophilic nature of the PPy coating improves the
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ion exchange property of the implant material in SBF and will

lead to the existence of apatite growth.57

3.6 Potentiodynamic polarization studies

Potentiodynamic polarization curves of uncoated and PPy-
coated Ti aer exposure in SBF solution were obtained and
are shown in Fig. 6(a). Electrochemical parameters such as icorr
(current density), Ecorr (corrosion potential) and polarization
resistance (Rp) are summarized in Table 2. The Ecorr value of
uncoated Ti was found to be low i.e. 0.496 V, due to the presence
of low conducting TiO2 lm formed on the surface which is
replaced by the corrosion process. In the case of the PPy coating,
there is a positive shi of 0.100 V because the PPy chain carries
more charge and helps to make a stable potential for the
working electrode. Accordingly, the icorr value of the PPy coating
is decreased by one order of magnitude compared to that of the
uncoated Ti. The value of the PPy coating is 0.088 mA cm2,
which is lower than that of the uncoated substrate (0.14 mA
cm2). It may be due to the formation of the PPy coating, which
contains a greater number of conjugated double bonds, and
carries a high number of electrons, which helps in adsorption to
the working electrode. Hence, the coating is more stable. The Rp
value of the coated sample is found to be higher than that of the
uncoated Ti, which conrms the increase in corrosion resis-
tance. These results indicate that the coated sample possess
better corrosion resistance than the uncoated metal. The
polarization resistance of the uncoated and PPy-coated Ti was
determined using the Stern–Geary equation (eqn (1)):
ba
bc
icorr ¼ (1)
2:3Rp ðba þ bc Þ

where ba and bb are the anodic and cathodic Tafel slopes, icorr is
the corrosion current density and Rp is the polarization
resistance.58,59
Fig. 6 (a) The potentiodynamic polarization curves of uncoated Ti and The dissolution behavior or onset of corrosion for uncoated
PPy-coated Ti in SBF. (b) The anodic polarization curves of uncoated Ti
and PPy-coated Ti was explained on the basis of the anodic
and PPy-coated Ti in SBF.
polarization curve, which is shown in Fig. 6(b). Anodic polari-
zation basically provides information about the passivation and
dissolution behavior of the metal and metal/coating surface.
Table 2 Corrosion parameters of uncoated and PPy-coated Ti ob-
tained by the Tafel plot in SBF From the plot, it can be observed that the increased current
density for uncoated and PPy-coated Ti is around 1.2 V and 1.25
icorr (mA ba bc V, respectively. The reason behind this is that the degradation
Sample Ecorr (V) cm2) Rp (kohm cm2) (V dec1) (V dec1) started at these regions for both the uncoated and PPy-coated
Ti. Therefore, the corrosion resistance decreased for both
Uncoated Ti 0.496 0.14 283.252 4.603 6.264
PPy-coated Ti 0.397 0.088 535.998 2.708 6.309 substrates.

3.7 DEIS studies

metal surface that is hydrophilic in nature increases the
biocompatibility of the implant material in SBF.56 Fig. 5 shows
the contact angle value of uncoated Ti, which was found to be 87
 2 , which indicates the hydrophobic nature of the material,
whereas the PPy-coated Ti exhibited a lower contact angle value
of about of 57  2 . The decreased contact angle value of PPy-
In anodic polarization (Fig. 6(b)), we can see that the nature of
the polarization curves of both the uncoated and PPy-coated Ti
has exhibited a stable passive behavior without exhibiting an
active passive behavior. The passive behavior is associated with
the increased current because of the localized corrosion. From
the plot, a sudden increase in the anodic current was evident for

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Fig. 7 DEIS Nyquist plots of uncoated Ti as a function of applied potential in SBF solution.

the onset of the corrosion or dissolution region at around 1.2 V

for uncoated and 1.25 V for PPy-coated Ti.
Fig. 7 shows the DEIS plots of uncoated Ti as a function
applied potential. At the OCP, incomplete semicircle impedance
behavior was observed followed by a distinctive impedance
response up to 1 V which aer that decreases with increasing
potential. The results show a high resistance nature at initial
potentials, indicating high corrosion resistance, and the metal
surface is fully covered with a stable oxide lm of Ti. The
decrease in the resistance value aer 1 V indicated the thinning Fig. 9 Equivalent circuit diagram for (a) uncoated Ti and (b) PPy-
of the oxide lm when the potential increased from a lower to coated Ti.
a higher extent.60 The lm dissolution, onset of corrosion at 1.2

Fig. 8 DEIS Nyquist plots of PPy-coated Ti as a function of applied potential in SBF solution.

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Table 3 EIS parameters for uncoated and PPy-coated Ti at the OCP and dissolution regions obtained by equivalent circuits

OCP Dissolution
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Potential
Material Uncoated Ti PPy-coated Ti Uncoated Ti PPy-coated Ti

Rs (U cm2) 1.9 1.6 2.6 3.1

Q1 (S sn cm2) 1.919
105 5.653
108 5.17
104 4.757
105
R1 (U cm2) 1.431
105 2.626
105 5.982
104 6.509
104
n 0.89 0.94 0.76 0.83
Q2 (S sn cm2) — 6.051
106 — 4.104
105
R2 (U cm2) — 109.3 — 52.31
n — 0.91 — 0.81

V, and the surface exposure in the electrolyte medium increase
the corrosion rate. The appearance of this trend might be due to
the adsorption of corrosive ions on the metal surface from the
electrolyte solution. Comparing with the anodic polarization
results, the increase in current density is also evidence for the
dissolution of the passive lm at 1.2 V. In order to characterize
the passive lm formed on Ti, an equivalent circuit is used and
the tted results showed a single time constant for all the
potentials as shown in Fig. 9(a), where Rs is the electrolyte
solution resistance, R1 is the charge transfer resistance of the
passive lm and Q1 is the double-layer capacitance of the
passive lm that gives information about the polarity and
charge separation of the oxide layer/electrolyte interface.
Generally in titanium oxide lms, distributed relaxation
phenomena are observed, and due to this reason here Q was
replaced with a constant phase element (CPE) and this is
written as ZCPE ¼ [Q(jw)n]1, where Q is the CPE constant, j is the
imaginary number, u is the angular frequency and 1 < n < 1.
The n values are in the range of 0.5 to 1 and are associated with
a non-uniform current behaviour due to the surface porosity
and surface roughness.61,62 If n ¼ 1 the substrate behaves with
ideal capacitive behavior. If n is less than one, the substrate
behaves with non-ideal capacitive behavior and a constant
phase element exists.
Fig. 8 shows the DEIS plots of the PPy coating in SBF. A
higher magnitude of impedance was observed at lower poten-
tials (0.55 to 0.3 V) for the PPy coating compared to that of the
uncoated Ti. This is due to the lower number of surface defects
as well as surface homogeneity, which could be due to the
existence of the stable coating that protects the movement of
corrosive ions from the electrolyte solution. The gradual
increase in the impedance values in the potential range region
between 0.3 and 0.8 V is due to the conjugated double bonds
and polar N–H group present in the pyrrole ring.63 Conse-
quently, there is a strong bonding interface between the metal
and coating. The gradual decrease in the resistance value at
higher potentials, 0.85 to 1.25 V, was attributed to the increased
porosity of the coating. The coating is exposed in the electrolyte
medium and the low progressive degradation ability of the
coating results in a decrease in thickness, which might allow
more corrosive ions to easily go to the surface leading to the
breakdown of the lm. This is in good agreement with the trend
observed from the anode polarization with an increased current
density at 1.25 V. All the spectra for the coated substrate show
a high magnitude of impedance compared to that of the
uncoated Ti because the charge conduction in PPy favours
delocalization of charge. Hence, the coating is more stable and
prevents the corrosion reaction, which needs a localization of

Fig. 10 Bode-phase angle plots for uncoated Ti and PPy-coated Ti metal at (a) the OCP and (b) the dissolution region in SBF solution.

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Fig. 11 EIS Bode impedance plot for uncoated Ti and PPy-coated Ti metal at (a) the OCP and (b) the dissolution region in SBF solution.
charge. At the OCP to dissolution region, the increased charge
transfer resistance (Rct) for the PPy-coated Ti compared to that
of the uncoated Ti indicated a low corrosion rate. The equiva-
lent circuit used for the PPy-coated Ti is shown in Fig. 9(b)
where Rs represents the electrolyte solution resistance between
the working and reference electrodes, R1 is the charge transfer
resistance of the coating, Q1 is the double-layer capacitance of
the metal/coating interface and Q2 is the capacitance of the
coating/electrolyte interface. The existence of a higher charge
transfer resistance value of the PPy-coated Ti also includes the
lm resistance (R2) as shown by the equivalent circuit in
Fig. 9(b). The PPy coating acts as a physical barrier between the
metal and electrolyte. Distinctive impedance behavior was
observed for PPy-coated Ti from the OCP to dissolution region
as a function of potential. The decreased corrosion resistance at
the dissolution region compared to the OCP region for the
Fig. 12 The change in current density for uncoated and PPy-coated Ti metal at (a) the OCP and (b) the dissolution region in SBF solution.
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coated substrate is attributed to the coating defects that arise
from corrosion reactions by the inuence of a high positive
potential. The circuit used for the coated substrate at the
dissolution region included the elements R2, which represents
the pore resistance, and Q2, which is the pore capacitance, and
these are replaced by the coating resistance (R1) and coating
capacitance (Q2), respectively.
The EIS parameters of the uncoated and PPy-coated Ti were
obtained from the equivalent circuits and are given in Table 3.
From the table values, a higher charge transfer resistance (Rct)
of the PPy coating than that of the uncoated substrate at the
OCP and dissolution potential regions gives more protection by
improving the corrosion resistance of Ti metal in SBF. This is
attributed to the homogeneous, compact and relatively less
porous surface for the PPy-coated Ti, as conrmed by SEM and
AFM analysis. Therefore, the coatings showed enhanced
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Fig. 13 SEM images of corroded surfaces of (a) uncoated Ti, (b) PPy-
coated Ti at the OCP, (c) uncoated Ti, and (d) PPy-coated Ti at
dissolution in SBF solution.
corrosion resistance for all potentials. The double-layer capac-
itance values of the uncoated and PPy-coated Ti are higher in
the dissolution region than in the OCP region. This is due to the
adsorption of corrosive ions being more on the surface when
the potential is raised to a higher extent. The capacitance of the
passive lm on the substrate and coating was increased in the
dissolution regions because of the higher conductivity between
the substrate/electrolyte and coating/electrolyte interfaces. The
n values of the uncoated and PPy-coated Ti at the OCP and
dissolution regions are close to ideal capacitive behavior. The
higher n values of the PPy-coated Ti indicates more resistance of
corrosive ion penetration and impedes the corrosion process
even at high potential.
Fig. 10 shows the Bode-phase angle plots of the uncoated
and PPy-coated Ti at the OCP and dissolution regions. At the
OCP, the phase angle plots of the uncoated and PPy-coated
substrates started at almost the same regions in the high
frequency region followed by reaching around 80 in the mid
frequency region. Aer that there is a decrease in the phase
angle value for the uncoated substrate in the low frequency
region. In general, the low frequency region of the phase angle
plots is used to determine the corrosion resistance of the
material. The higher phase angle value of PPy-coated Ti in the
low frequency region revealed enhanced corrosion resistance.
The higher phase angle shi for PPy-coated Ti compared to
that of uncoated Ti indicated the presence of a highly stable
and compact coating and less interaction of corrosive ions
present in SBF. At the dissolution region, the phase angle
values in the low frequency region dropped to 20 for both the
uncoated and PPy-coated Ti. These results showed evidence for
the decrease in impedance magnitude with increasing poten-
tial. The uncoated and PPy-coated substrates behaved as a non-
ideal capacitive system and there exists a constant phase
element (CPE) for all the potentials because the n values
observed from the CPE are less than one for all the applied
potentials.
Bode impedance plots for uncoated and PPy-coated Ti at the
OCP and dissolution regions are shown in Fig. 11(a) and (b). In
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the Bode impedance plots, the high frequency region explains
the local surface defects formed on the coating by corrosion,
the mid frequency region represents the reaction involved
within the lm, and the low frequency region reveals the
behavior occurring because of corrosion in the metal/lm
interface. At the OCP, the low frequency spectrum of
uncoated Ti is quite low compared to that of the PPy-coated Ti,
which revealed that the low conducting TiO2 passive lm was
replaced due to the distribution of ions towards the substrate
from the electrolyte solution. The high impedance was
consistent with the insulating nature of the coating against
corrosion which provides a greater barrier property to the
metal, even when the potential increased from a lower to
a higher region, which impedes the access of anions in SBF for
further attack to the metal/coating interface. At dissolution
regions, the decrease in the Bode impedance behavior for both
the uncoated and PPy-coated Ti is related to the degradation
ability by the inuence of potential resulting in the increased
capacitance values for both the substrates. This may be due to
the increased conductivity between the substrates and elec-
trolyte medium.
A potentiostatic polarization test was carried out for
uncoated and PPy-coated Ti at the OCP and dissolution poten-
tials as a function of time, and the results are shown in Fig. 12.
At the OCP, the current density values of the uncoated and PPy-
coated Ti decreased rapidly in the beginning followed by
stabilization in the range of 7.13
105 (A cm2) for uncoated
and 7.45
105 (A cm2) for PPy-coated Ti. There is no
signicant difference in the current density values on
comparing both substrates but the slightly decreased value for
PPy-coated Ti indicated increased corrosion resistance.
The SEM images (Fig. 13(a) and (b)) also prove that not
much corrosion occurred on the surface of the uncoated and
PPy-coated Ti. Subsequently, a higher corrosion resistance of
the PPy coating was related to the low passive current density
during the test. At the dissolution region, the passive TiO2
lm on metal degraded gradually because of lm breakdown
and a greater number of corrosive ions entering the surface
by the inuence of high potential, resulting in the high
current density value of about 1.07
104 (A cm2) for
uncoated Ti. The generation of a higher current density value
of uncoated Ti revealed an increased corrosion rate at higher
potential. These results demonstrated that the passive lm
formed on metal is no longer resistant by the inuence of
high potential stress. The SEM image of uncoated Ti
(Fig. 13(c)) also supports the fact that more corrosion takes
place at higher potential and decreases the protective effi-
ciency of the material. Interestingly, there is a slight increase
in the current density value for PPy-coated Ti because of the
low degradation followed by stabilization at 7.187
105 (A
cm2). There is not much difference in the current density
value in comparison with the current density observed at the
OCP region. There is low reduction stability of the coating at
higher potential, and the low current is due to the presence of
a stable polymer lm with less morphological change, which
can be seen in Fig. 13(d).
RSC Adv., 2016, 6, 80275–80285 | 80283

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4 Conclusions
A PPy coating was deposited successfully by the electro-
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polymerization technique using CV. ATR-FTIR and Raman
studies conrmed the deposition of PPy on Ti by the presence of
N–H and C]C stretching vibrations. SEM and AFM images of
the coated substrate revealed the deposition of PPy with
a cauliower morphology and its high roughness value. A low
contact angle value revealed the hydrophilic nature of the
coated substrate. The higher Rp and reduced icorr values
demonstrated the enhanced corrosion resistance for the PPy-
coated Ti. DEIS studies conrmed the changes in the imped-
ance value as a function of potential and the PPy coating gave
more protection even at higher potentials. These results are in
good agreement with the current trend observed from the
polarization curves. High Bode impedance and phase angle
maximum values were observed for the coated substrate at the
OCP and dissolution region. The low current density value
observed from the potentiostatic polarization studies conrmed
the less corroded surface and hence the more protective effi-
ciency of the PPy coating.
Acknowledgements
One of the authors, Bhavana Rikhari, is grateful to Anna
University for the nancial assistance under Anna Centenary
Research Fellowship Scheme. The author is also very much
thankful to Department of Science and Technology Fund for
improvement of S & T infrastructure in higher education insti-
tutions and University Grant Commission Departmental
Research Support Scheme.
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