International Journal of Emerging Technology and Advanced Engineering

Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
62

Performance of Polypyrrole Coatings Against the Corrosion of
Low Carbon Steel in Various Corrosive Environments
Pritee Raotole
1
, P. P. Patil
2
, Mahesh Raotole
3
1
MGSMs, Arts, Science and Commerce College, Chopda, Dist: Jalgaon 425107, Maharashtra, INDIA
2
Department of Physics, North Maharashtra University, Jalgaon 425 001, Maharashtra, INDIA
3
Smt. Sharchchandrika Suresh Patil Istitute of Technology, Polytechnic, Chopda, Dist: Jalgaon 425107, Maharashtra, INDIA
AbstractThe polypyrrole (PPY) coatings were
electrochemically synthesized on low carbon steel (LCS)
substrates by cyclic voltammetric method from an aqueous
solution of sodium oxalate.
The corrosion protection performance of PPY coatings on
LCS were studied in different corrosive environments such
as, aqueous 3% NaCl, 0.01 M Na
2
SO
4
and tap water. This
corrosion protection performance was evaluated by
potentiodynamic polarization measurement. The result of the
potentiodynamic polarization demonstrates that the PPY
coating has ability to protect the LCS against corrosion. The
corrosion potential (E
corr
) was about 256 mV more positive in
aqueous 3% NaCl for the PPY coated LCS than that of bare
LCS and significantly reduces the corrosion rate of LCS. It
was also observed that the PPY coating has ability to protect
LCS against corrosion in aqueous Na
2
SO
4
and tap water.
Keywords Conducting polymer coatings, Polypyrrole
coatings, Corrosion, Corrosive media ..
I. INTRODUCTION
Conducting polymers have received the great attention
due to their many diversified technological applications and
their outstanding properties and new application areas for
these materials have also been explored [1-7]. One of the
most important applications of these materials which is
attracting considerable attention is in corrosion protection
of metals [7-11]. The conducting polymer must be in the
coating form and it should be strongly adherent to the metal
surface so far as corrosion protection is concerned. The
electrochemical polymerization (ECP) is a simple,
relatively inexpensive and most convenient route for the
synthesis of such a coating structures [1,2]. The most
salient feature of this route is that the process of
polymerization and the coating formation takes place
simultaneously.
Following the pioneering work of DeBerry [12],
considerable efforts have been made in probing polyaniline
(PANI) for corrosion protection of steels and aluminum.
The polypyrrole (PPY) has also been investigated [13] for
their suitability to provide corrosion protection.

The PPY has several attractive characteristics suitable
for corrosion protection application such as (i) The
monomer pyrrole (PY) has essentially the same structure as
many efficient corrosion inhibitors. (ii) The synthesized
PPY is insoluble in almost all solvents and therefore it can
be used in many chemical environments. However, the
main disadvantage of PPY is that the non-aqueous bath is
usually required for its deposition.
Recently, Irohs group [14] has extensively studied the
electrochemical synthesis of PPY on mild steel from
aqueous solution of oxalic acid. It has been shown that the
aqueous oxalic acid medium allows the passivation of the
steel surface via formation of iron oxalate interphase
without preventing the ECP of PY. Further it is proved that
the formation of the passive interphase and its subsequent
decomposition is necessary for the ECP of PY to occur on
the LCS substrates. Thus, it is now possible to formulate
the appropriate ECP recipes to synthesize PPY coating on
oxidizable metals from aqueous solutions.
In the studies reported in this paper, we have synthesized
the PPY coatings on LCS by ECP of PY under cyclic
voltammetric conditions from aqueous solution of sodium
oxalate. The ability of PPY to serve as a corrosion
protective coating on LCS in different corrosive solutions
such as NaCl, Na
2
SO
4
and tap water was assessed by the
potentiodynamic polarization measurements .
II. EXPERIMENTAL
The LCS substrates ( size ~ 1 x 1.5 cm and 0.5 mm
thick) were polished with a series of emery papers,
followed by thorough rinsing in acetone and double
distilled water and dried in air. Prior to any experiment, the
substrates were treated as described and freshly used with
no further storage.The corrosion studies were performed at
room temperature in 3% NaCl, 0.01 M Na
2
SO
4
and tap
water by using potentiodynamic polarization technique.
The substrates were immersed into the electrolyte solution
and the open circuit potential (OCP) was monitored until a
constant value was reached prior to the polarization
measurements.

International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
63

The polarization measurements were performed by
sweeping the potential between 250 mV and 250 mV
from the OCP at the scan rate of 2 mV/sec. All the
measurements were repeated at least four times and good
reproducibility of the results was observed. The corrosion
potential (E
corr
) and corrosion current density (I
corr
) were
obtained from the slopes of linear polarization curves. The
corrosion rate (CR) was calculated by using the following
expression [15]
Where I
corr
is corrosion current density (A/cm
2
), EW is
equivalent weight of LCS (gm) and is the density of LCS
(gm/cm
3
).
III. RESULTS AND DISCUSSION
A. Corrosion protection performance of the PPY coating
in aqueous 3% NaCl Solution
The potentiodynamic polarization curves for bare and
PPY coated LCS (20 cycles) in aqueous solution of
3% NaCl are shown in Figure1. The values of the corrosion
potentials, corrosion current densities and corrosion rates
obtained from these curves are given in Table 1. It is seen
that the values of corrosion potential (E
corr
) and corrosion
current density (I
corr
) are far lower than the corresponding
values for bare LCS indicating the corrosion resistant
feature of the coating. The I
corr
decreases from 26.75
A/cm
2
for bare LCS to 5.13 A/cm
2
for PPY coated LCS.
The E
corr
increases from -710 mV for bare LCS to - 454
mV for PPY coated LCS. The positive shift of 256 mV in
E
corr
indicates the protection of the LCS surface by the PPY
coating. The corrosion rate of LCS is found to be ~ 0.05
mm/year which is ~ 6 times lower than that of bare LCS.































Figure 1 Potentiodynamic polarization curves for (a) bare LCS and
(b) PPY coated on LCS in aqueous 3% NaCl.
These results reveal that the PPY acts as a protective
layer on LCS and inhibits the corrosion of LCS in aqueous
3% NaCl.
Table 1
Potentiodynamic polarization measurement results















EW I
x yr mm CR
corr 3
10 268 . 3 /

International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
64



















The SEM micrograph of the PPY coated LCS after the
potentiodynamic polarization measurement in aqueous 3%
NaCl is shown in Figure2. It is clearly observed that there
is no apparent change in the surface morphology of the
coating after the potentiodynamic polarization
measurements. Indeed, the visual observation revealed no
cracks in the coating and the coating remains strongly
adherent to the LCS substrate. Thus, PPY coating has
strong adherence to the LCS substrate and it is resistant to
the corrosion in aqueous 3 % NaCl.
In order to investigate the influence of the coating
thickness on the corrosion protection properties of the PPY
coatings, we have synthesized the coatings by 5, 10, 15 and
20 cycles from -500 mV to 1500 mV at a scan rate of 20
mV/sec and the potentiodynamic polarization resistance
measurements were performed in an aqueous solution of
3% NaCl. It is found that the corrosion rate does not
change significantly (cf. Table 1) when the coating was
deposited with more than 5 cycles. However, the E
corr

decreases when the deposition time (i.e. the number of
cycles) is varied. Even though the corrosion rate is higher
for the PPY coating deposited with 5 cycles, it is low
compared to that of bare LCS.
In order to further reveal the corrosion protection ability
of the PPY coating, we have studied the electrochemical
behavior of the PPY coated LCS electrode in a 0.1 M
aqueous solution of sodium oxalate (in absence of PY).




The CVs recorded for bare and PPY coated LCS in the
potential range between -500 and 1500 mV at a scan rate of
20 mV/sec in a 0.1 M aqueous solution of sodium oxalate
are shown in Figure 3. The first scan of the CV recorded
for bare LCS Figure 3(a), it reveals the dissolution of LCS
electrode.
The first scan of the CV recorded for PPY coated LCS
Figure 3(b) is significantly different than that for bare LCS.
The anodic peak A, the oxidation wave B and peak C are
not observed. Thus, the observation of negligibly small
current densities at all potentials indicates that the
dissolution of the underlying LCS substrate is inhibited due
to the PPY coating.




















To gain further insight into corrosion protection
property, we have carried out short term immersion studies
on PPY coated LCS (deposited with 20 cycles) in aqueous
3% NaCl and the corresponding potentiodynamic
polarization curves are shown in Figure 4. The values of
the E
corr
, I
corr
, Tafel constants (
a
and
c
) and corrosion rate
obtained from these curves are given in Table 2.










Figure 2 SEM micrograph of PPY coating synthesized on
LCS substrate after potentiodynamic measurements.

Figure 3 Cyclic voltammograms of (a) bare LCS and
(b) PPY coated LCS recorded in 0.1 M sodium
oxalate solution.

International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
65






























Table 2
Results of the potentiodynamic polarization measurements for short-
term immersion study
The potentiodynamic polarization curves indicate that
the PPY layer provides a steady cathodic and anodic
polarization in the initial immersion stages. In addition, the
E
corr
shifts to more negative values, but the I
corr
and
corrosion rate remains at the same level. The Tafel slopes
of both cathodic and anodic curves show no apparent
variation during the initial immersion times. Moreover, the
ratio of cathodic to anodic Tafel constants (
c
/
a
) is close
to 1 indicating the excellent corrosion protection. When
immersed for 120 minutes, a high value of Tafel constant
ratio indicates that the corrosion protection is dominated by
cathodic protection and Icorr increases by less than a factor
of 3.

We have also performed the potentiodynamic
polarization measurements by using the PPY coated LCS
substrates after storing them in air at 25
o
C for 7 days and
the corresponding polarization curve is shown in Figure
5(b). This curve clearly reveals that there is no indication of
any substantial loss in corrosion protection properties of the
PPY coatings. The higher shift (~ 22 mV) in E
corr
as
compared with the freshly prepared and dried coating
reveals the increase in the corrosion resistance offered by
the PPY coatings to LCS. This may be attributed to the
dehydration of the polymer during the storage process.
Thus, the PPY coating shows the high chemical as well as
physical stability because the coating keeps its adherence to
LCS substrate even after the storage.





















B. Corrosion protection performance of the PPY coating
in aqueous 0.01M Na
2
SO
4
Solution and Tap water
The capability of PPY coating to protect LCS in sulfate
medium and tap water was also assessed and the
corresponding results are presented in Figures 6 and 7. The
potentiodynamic polarization curves for bare and PPY
coated LCS (20 cycles) in aqueous solution of 0.01 M
Na
2
SO
4
are shown in Figure 6. It is observed that the E
corr
shows a shift in the positive direction when the surface is
covered by the PPY coating and at the same time, the I
corr

decreases from 31.93 A/cm
2
to 1.97A/cm
2
.



Figure 4 Potentiodynamic polarization curves for PPY
coated on LCS in aqueous 3% NaCl as a function of
immersion time (a) 30, (b) 60and (c) 120 minutes.

Figure 5 Potentiodynamic polarization curves for PPY coated
LCS (a) freshly prepared and (c) after storing in air for 7
days at 25
o
C recorded in aqueous 3% NaCl.

International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
66

The positive shift of 133 mV in E
corr
indicates the
protection of the LCS surface by the PPY coating in sulfate
medium. The corrosion rate of PPY coated LCS is found be
0.02 mm/yr which is ~ 18 times lower than that observed
for bare LCS.
The potentiodynamic polarization curves for bare and
PPY coated LCS (20 cycles) in tap water are shown in
Figure7. The I
corr
decreases from 4.84 A/cm
2
to
0.73A/cm
2
when the LCS is coated with PPY.










































The positive shift of 81 mV in E
corr
indicates the
protection of the LCS surface in tap water by the PPY
coating. The corrosion rate of PPY coated LCS is found to
be ~ 0.008 mm/year which is ~ 6 times lower than that
observed for bare LCS.
IV. CONCLUSIONS
In summary, following conclusions have been drawn
form the present study
1. It is possible to deposit uniform and strongly
adherent PPY coating on LCS using sodium
oxalate as a supporting electrolyte.
2. The formation of PPY coatings occurs after the
passivation of the LCS substrate via formation of
FeC
2
O
4
interphase.
3. The deposited PPY has been found to act as a
corrosion protective layer on LCS in aqueous
NaCl, Na
2
SO
4
and tap water.
4. The corrosion protection properties of these
coatings are retained even after storing them in air
at 25
o
C for 7 days.
Acknowledgement
The financial support from Defence Research and
Development Organization (DRDO), India through
DRDO/ISRO-PUNE University Interaction Cells,
University of Pune, India is gratefully acknowledged.
REFERENCES
[1] H.S. Nalwa, Handbook of Organic Conductive Molecules and
Polymers, Vols.1-4, John Wiley and Sons Ltd., 1997.
[2] T.A. Skotheim ( Ed.), Handbook of Conducting Polymers, Vols. I
and II, Marcel Dekker Inc., New York, 1986.
[3] W.R. Salaneck, D.T. Clark, E.J. Samuelsen, Science and
Applications of Conducting Polymers, Adam Hilger, Bristol, 1991.
[4] M. Aldissi, Intrinsically Conducting Polymers : An emerging
Technology, Kluwer Academic Publishers, Dordrecht, Holland,
1993.
[5] P. Chandrasekhar, Conducting Polymers : Fundamentals and
Appplications, Kluwer Academic Publishers, Dordrecht,
Holland, 1999.
[6] B. Scrosati, Application of Electroactive Polymers, Chapman and
hall, London (1993).
[7] Wencheng Su, Jude O. Iroh, Synthetic Metals 95 (1998) 159-167
[8] W. S. Araujo, I.C.P. Margarit, M. Ferreira, O. R. Mattos, P. Lima
Neto, Electrochimica Acta 46 (2001) 1307.
[9] H. Nguyen Thi Le, B. Garcia, C. Deslouis and Q. Le Xuan,
Electrochimica Acta, 46 (2001) 4259.
[10] P. Herrasti and P. Ocon, Appl. Surf. Sci., 172 (2001) 276
[11] A. Mirmohseni and A. Oladegaragoze, Synth. Met., 114 (2000) 105.
[12] D.W.DeBerry and A. Viehback, in E. Mccaffetry, C.R. Clayton and
J. Oudar (Eds.), The Electrochemical Society
Figure7 Potentiodynamic polarization curves for (a) bare LCS
and (b) PPY coated on LCS in tap water.
Figure6 Potentiodynamic polarization curves for (a) bare
LCS and (b) PPY coated on LCS in aqueous 0.01 M Na2SO4.


International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 11, November 2013)
67

[13] Softbound proceedings Series, Pennington, NJ (1984), pp.308.
[14] F. Beck, R. Michaelis, F. Schloten and B. Zinger, Electrochim Acta
39(2) (1994) 229.
[15] W. Su and J.O.Iroh, Electrchimica Acta 46 (2000) 1.
[16] Electrochemistry and Corrosion - Overview and Techniques,
Application Note CORR -4, EG and G, Princeton Applied Research,
U.S.A.
[17] G. Mengoli and M.M. Musiani, Electrochim. Acta 31 (1986) 201.
[18] E.M. Genies, G. Bidan and A.F.Diaz, J. Electroanal. Chem. 149
(1983) 101
[19] G. Socrates, Infrared Characteristic Group Frequencies, 2
nd
Edition,
John Wiley and Sons, Inc., New York, 1994.
[20] R. A. Jones (Ed.), Heterocyclic Compounds, Polypyrroles, Vol. 48,
part 1, John Wiley ans Sons Inc., New York, 1990.
[21] Preeti Pawar, M.G. Wankhede, S.R. Sainkar and P.P. Patil, Materials
Sci. and Engineering A, 347 (2003) 365.




















AUTHOR PROFILE
Name : Dr. Mrs. Pritee Mahesh Raotole
Designation : Assistant Professor in MGSMs
Arts, Science & Commerce
College Chopda Dist: Jalgaon.
Education : Ph. D. (Physics)
Publications : 05 Papers in Reputed
International Journals.
Research Area : Conducting Polymers ,
Corrosion, Nano Materials
and Sensors.
Experience : Total Professional Experience
is Seven & Five years in
Research Field.