Surface & Coatings Technology 201 (2007) 5836 5842

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Corrosion studies of carbon nanotubesZn composite coating

B.M. Praveen a , T.V. Venkatesha a,, Y. Arthoba Naik a , K. Prashantha b
a
Department of studies in Chemistry, school of chemical sciences, Kuvempu University, Shankaraghatta-577451, Karnataka, India
b
Division of Advanced Materials Engineering, Chonbuk National University, Dockjin-Dong, 1Ga 664-14, Jeonju, South Korea 561756

Received 21 May 2006; accepted in revised form 20 October 2006

Available online 29 November 2006

Abstract

Zncarbon nanotubes composite coatings were obtained from a sulphate bath containing dispersed carbon nanotubes (CNTs). The
electrochemical and weight loss measurements were made to find the corrosion behavior of composite coating. The presence of carbon nanotubes
shifts the potential of zinc deposit to more positive values. The composite coatings were porous free and the service life of coating was examined
by salt spray test. The electrochemical studies revealed higher resistance of composite coatings to corrosion. The surface morphology was
investigated by recording the SEM images of coating before and after corrosion. The mechanism of action against corrosion was established.
2006 Elsevier B.V. All rights reserved.

Keywords: Carbon nanotubes; Corrosion; Electrochemical measurements; Zn-composite coating

1. Introduction modification the treatment and solution have to be optimized

Zinc electroplating is an industrial process and is widely used
to coat on steel for enhancing its service life [15]. The zinc
coated steel articles exhibit higher resistance to corrosion,
generally, known as white rust corrosion. The white rust
formation on these articles are controlled by chromating their
surfaces [6]. The chromating is obtained by dipping zinc-coated
articles in chromic acid solution. The effluent of this process
contains chromium ions, which are prone to produce pollution
of water and health hazard [7]. The alternating way of
increasing the service life of zinc coated materials is to modify
the surface by treating it with solutions of electro active
compounds. These compounds possess functional groups
containing N, S and/or O elements in them [8]. In most of the
cases these compounds forms complex with zinc metal or
exhibit strong interaction with metal and thereby forming
molecular layer on the surface [9]. This layer provides a barrier
between corrosion medium and the metal. Thus reduced the
formation of white rust. However in intense corrosive medium,
the protective layer get damaged resulting in severe corrosion.
Both chromation and surface modification methods are referred
as post-plating process. To get chrome passivation surface
Corresponding author. Tel.: +91 9448855079; fax: +91 08282 256255.
E-mail address: drtvvenkatesha@yahoo.co.uk (T.V. Venkatesha).
0257-8972/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2006.10.034
and requires expert skills.
Zinc composite coating is another promising field wherein
zinc metal is coated along with ceramic, polymers and metal
oxides. The composite coating is obtained from aqueous
solutions containing zinc salts, dispersed composite powders
and suitable surfactant or addition agents. The coating
properties of the composite coating depend on electrochemical
parameters such as electrodeposition potential, current density
etc. Composite coating gives various functional properties such
as wear resistance, corrosion resistance etc. [1014]. The
composite coating when contains micro-semi micro sized
particles, shows somewhat porous structure of the matrix.
Also there may not be size uniformity of dispersed solid
powders resulting in irregularities in the texture of the coating.
In order to make the composite coating attractive, nowadays,
there is growing interest in the co-deposition of the nanopar-
ticles because of their increasing availability. There are other
areas, in addition to classical plating applications, like electrode
modifications, photoactive materials, electro catalysis, adsorp-
tion materials etc. [15].
The carbon nanotubes have attracted tremendous interest
from fundamental and applied perspectives [16]. The discovery
of carbon nanotubes have led to the applications in nanodevices
such as nanodiodes, nanotransistors, nanocars for special as
well as other important applications [17,18]. The multiwalled
 B.M. Praveen et al. / Surface & Coatings Technology 201 (2007) 58365842
carbon nanotubes are stiffest among all and hence they have
found applications in the fabricating needle like tips of atomic
imaging instruments. However very few investigations have
been made on the corrosion behavior of CNTsmetal
composites and no studies especially on CNTsZn composites.
This composite coating could be used on steel components as
substitute for pure zinc coating to enhance their service life by
controlling or preventing the formation of white zinc rust.
Further CNTsZn composite could find application in marine
atmosphere in place of Cd and other composite coatings. In
addition this composite coating can be obtained from aqueous
electrolyte containing CNTs with simple salts and operated at
ambient temperature. This makes CNTsZn composite more
attractive and economically viable than other zinc composite
coatings. In the present study the electrodeposition of CNTsZn
composite and its corrosion behavior have been investigated.
2. Experimental
2.1. Plating process
The CNTsZn composite coating is obtained from acid
sulphate bath. To get good deposit the nanoparticles CNTs are
dispersed uniformly in the plating solution and must be stable
suspension. The CNTs have high surface energy and get
agglomerate easily. So complete dispersion of CNTs in a plating
solution is a key problem. Also the formation of dispersion cluster
of CNTs is very important to get good nanostructural composite
coating. In many cases, acid treatment is given to get effective
utilization of CNTs. The acid treatment removes most of the metal
and also produces carboxyl, aldehydes and other functional
groups [19] on the surface of CNTs. This will allow the complete
dispersion by giving negative charge to the surface of CNTs. In
addition, the cetyl trimethyl ammonium bromide present in the
bath is cationic surfactant and improves hydrophilic ability of
Fig. 1. Infra-red spectrum of carbon nanotubes after acid treatment.
5837
CNTs. Also the solution is continuously agitated using mechan-
ical stirrer with 1000 rpm.
Analytical reagents and distilled water were used to prepare
the plating solution. The multiwalled CNTs were supplied by
Iljin Nanotech Co., Ltd. with a diameter of 1020 nm and length
of 1050 m. The plating baths used to prepare the CNTsZn
composite coating was composed of 200 g/l ZnSO4 6H2O, 80 g/
l Na2SO4, 40 g/l NaCl 1 g/l CNTs and 4 g/l cetyl trimethyl
ammonium bromide as surfactant. The cathode is mild steel and
anode is pure zinc (99.99%). The mild steel before subject in
plating tank, was polished mechanically, and degreased with
trichloroethylene in degreased plant followed by water wash.
The anode was pure zinc and each time its surface was activated
by dipping in 10% HCl for few seconds and was washed with
water. Equal area of anode and cathode was maintained through
out electrodeposition process. The bath temperature was held at
308 K and pH of the bath was 3. The cathodic current density
was controlled at 4 A/dm2. The electrodeposition process is
carried out under mechanical stirring.
2.2. Coating characterization
The morphology study of coated samples, before and after
corrosion tests, was conducted by scanning electron microscopy
(SEM). The cross-section SEM images are taken for studying
the distribution of CNTs in coating. The SEM images of the
coated specimens before and after corrosion tests were used to
assess their corrosion performance in NaCl solution.
2.3. Weight loss measurements
The corrosion behavior of pure zinc and CNTsZn composite
coatings of steel specimens were followed by weight loss
measurements. The area of the specimen was 3 4 cm2. The
coating thickness was in the range 1520 m. The corrosive
5838 B.M. Praveen et al. / Surface & Coatings Technology 201 (2007) 58365842
Fig. 2. TEM (a) and SEM (b) images of carbon nanotubes.
medium was 3.5 wt.% NaCl. The temperature of the corrosive
medium was at 298 K. The coated samples were immersed in
NaCl solution and the plates were weighed periodically for every
24 h in 15 days. The loss in weight so obtained was used to
determine the corrosion velocity.
2.4. Salt spray test
The porous nature of the coated specimens were examined
by adopting porosity test. The steel samples of pure zinc coated
and CNTsZn coated samples of 5 5 cm2 area were taken for
this study. The specimens after plating were subjected to bright
dip in 1% nitric acid followed by water wash. The porosity of
Fig. 3. Variation of the corrosion rate with immersion time for pure zinc coated
and CNTsZn coated samples in 3.5 wt.% NaCl solution.
Fig. 4. Variation of anode polarization curves for pure zinc coated and CNTs
zinc coated samples in 3.5 wt.% NaCl solution.
the deposit was assessed by ferroxyl test [20]. This test
indicated porous free nature of the deposit. Further the salt spray
test as per (ASTM B 117) was carried out in a chamber [21].
The deposited plates were subjected to continuous spray of
neutral 5% sodium chloride vapours. The specimens were
observed carefully and the duration of the time for the formation
of the white rust was noted.
2.5. Electrochemical measurements
A conventional three-electrode system was used for
electrochemical measurements. The steel specimens coated
with pure zinc and CNTsZn was used as working electrode.
The surface area of coating exposed for corrosion study was
1 cm2. The saturated calomel electrode and platinum foil were
used as reference and auxiliary electrodes. The electrolyte was
3.5 wt.% NaCl and was at 298 K. The polarization curves for
the electrolyte at a sweep rate of 0.1 mV/s were recorded on the
273 A potentiogalvanostat device controlled by PC. The anodic
polarization was carried out for both pure zinc and CNTsZn
composite coatings. Also the corrosion potentials were
measured in every 30 min interval for a period of 15 h.
Fig. 5. Variation of the corrosion potential (Ecorr) with the immersion time in
3.5 wt.% NaCl solution for pure zinc coated and CNTsZn coated samples.
 B.M. Praveen et al. / Surface & Coatings Technology 201 (2007) 58365842
Fig. 6. Impedance diagrams for pure zinc coated and CNTsZn coated samples
in 3.5 wt.% NaCl solution.
The electrochemical impedance measurements were per-
formed using AUTOLAB from Eco-chemie made in Nether-
lands. The steel specimens coated with pure zinc and CNTsZn
were used as working electrode. The exposed surface area for
corrosion study was 1 cm2. The EIS acquired in the frequency
range from 100 M Hz to 10 M Hz with 5 mv AC amplitude
sine wave generated by a frequency response analyzer.
3. Results
3.1. Characterization of CNTs
The FT-IR spectrum (Fig. 1) of the acid treated CNTs show
that the presence of many groups on the surface of the CNTs,
Fig. 7. SEM images for the two samples. (a) high magnification of zinc coated, (b) low magnification of zinc coated, (c) high magnification of CNTsZn coated, (d)
low magnification of CNTsZn coated.
5839
such as carbonyl group, CO bonds etc. The TEM and SEM
images of CNTs are shown in the Fig. 2a,b.
3.2. Corrosion rate results
Fig. 3 shows corrosion rate of coated specimens in 3.5 wt.%
NaCl solution. In both the cases the corrosion rate slightly
increased in the beginning and remains constant after 100 h of
immersion. The corrosion rate was higher for zinc coating when
compared to CNTsZn composites. Further it was inferred that
the CNTsZn composite coating exhibit higher resistance to
corrosion. During corrosion rate measurements the weight loss
was more in pure zinc coating and hence the inclusion of CNTs in
zinc enhances its corrosion resistance property. The corrosion rate
was significantly reduced in presence of CNTs in the coating.
3.3. Salt spray test results
The industrial method of testing the corrosion behavior of
zinc-plated objects was salt spray test. The test was conducted by
spraying 5% NaCl solution in a chamber. The fog of drops
accumulated on the surface of the articles and facilitates the
corrosion resulting in zinc salts called white rust. The number of
hours for the formation of white rust was the indication of the
corrosion resistance. The higher corrosion resistance delays the
production of white rust. In the present case the pure zinc
produced the white rust after 20 h and the CNTsZn
nanocomposite produced the white rust after 42 h. This test
also confirms the enhancement of corrosion resistance of zinc in
the presence of CNTs in its coating.
5840 B.M. Praveen et al. / Surface & Coatings Technology 201 (2007) 58365842

Fig. 8. SEM images for two samples After 15 days weight loss measurements (a)
zinc coated, (b)CNTsZn composite coated.

3.4. Electrochemical results

Fig. 4 shows the anodic polarization behavior of pure zinc

coated and CNTsZn coated sample in NaCl solution. It was
observed that the potential of the CNTsZn coated samples was
less negative than that of pure zinc coated sample at all current
densities. This indicates that the addition of CNTs in zinc Fig. 9. SEM images for two samples after anodic polarization. (a) Low
magnification for zinc coated, (b) high magnification for zinc coated, (c) CNTs
coating increase the resistance to corrosion.
Zn coated sample.
Fig. 5 shows the variation of Ecorr with immersion time in
3.5 wt.% NaCl solution. It was observed that both coating
surfaces were modified during immersion. With increase of Zn composites showed difference in morphology at lower as
immersion time the Ecorr for composite coating was always more well as higher magnification. (Fig. 7a,b,c,d). It can be seen that
positive than that of pure zinc coating. After 1 h of immersion the the CNTs appear well dispersed in the deposit. The electroplat-
composite coating showed stationary values in Ecorr. This in- ing bath and the conditions maintained were able to produce
dicated a good chemical stability of composite coating. well-dispersed CNTs in the deposit.
The Nyquist plots for pure zinc and CNTsZn are shown in
Fig. 6. The larger loop was produced by CNTsZn coatings
whereas smaller semicircle was obtained for pure zinc. It can be
easily observed from the figure that Rp values are high in
composite coating than pure zinc coating. This indicates that
composite coating is more corrosion resistant than pure zinc
coating.

3.5. Corrosion morphology

The steel specimens were polished before subjecting them

into plating process. The deposit of pure zinc and CNTsZn
composite was similar in appearance except in color. The gray
color was noted in CNTsZn composite. Both deposits were
semi bright and porous free. The images of pure zinc and CNTs Fig. 10. SEM cross-section of CNTsZn composite coated sample.
 B.M. Praveen et al. / Surface & Coatings Technology 201 (2007) 58365842
In Fig. 8, the images of the corrosion morphology of pure
zinc and CNTZn composite coating were shown after weight
loss measurements in 3.5 wt.% NaCl solution for 15 days. The
large number of corrosion spots and its products were noticed
on the SEM image of pure zinc coated samples (Fig. 8a). Very
little corrosion was observed on the surface of CNTsZn
composites, which showed only few small pits (Fig 8b).
The coated specimens were kept for about 1015 min in the
3.5 wt.% NaCl solution before anodic polarization. The
polarization curves for the electrolyte at a sweep rate of
0.1 mV/s were recorded. The SEM images of surfaces of the
coating were shown in Fig. 9, (Fig. 9a,b,c).
The thickness of the composite coating was uniform and
supported by SEM cross-section image in Fig. 10.
The SEM images study results indicated that the CNTsZn
composite had higher corrosion resistance similar to the results
obtained by weight loss method and electrochemical measurements.
4. Discussion
The main experimental results of the present study revealed
that the CNTsZn composite coating possesses higher resis-
tance to corrosion when compared to zinc coating. The results
of weight loss measurements, salt spray test and electrochemical
methods were matching with each other. The porosity test
indicated that CNTs inclusion in the zinc deposit reduces the
porous nature of pure zinc coating. This reveals that CNTs
played a major role in providing corrosion resistance property to
CNTsZn coatings. The recent studies on the corrosion
behavior of metal deposits containing nanoparticles reports
that the incorporation of CNTs in the deposits improved the
corrosion resistance [22]. In many cases the CNTs acting as
physical barrier to the corrosion process by filling in crevices,
gaps, and micro holes on the surface of deposit. CNTs also
significantly improve the electrochemical properties of electro
less coating of NiPCNTs [23]. The CNTs enhances the
mechanical and tribiological behavior of composites. The metal
surface possess defects, cracks, gaps, crevices and micro holes
which were generally larger than micron. It was obvious that the
nanoparticles can easily enter and fill these defects. In the
present case also the CNTs enter and fill these gaps of the
surface of zinc. More over this micro hole behaves as active
sites for dissolution of metal during corrosion. Thus these holes
were covered in CNTsZn composite by CNTs thereby bring
down the corrosion rate in weight loss measurements.
The impedance measurements further supported that the
resistance of CNTsZn was higher when compared to pure zinc
coatings. This also suggested the barrier formation on CNTsZn
coating by CNTs. Thus the CNTs inclusion in the zinc coating
produced higher resistance to corrosion. In accelerated
corrosion test by salt spray method, the CNTsZn composite
does not show white rust before 42 h (20 h for pure zinc coating)
indicated that CNTs modified the surface of zinc. This
modification enhances the service life of zinc deposit.
The CNTs inclusion in the zinc deposit shifts the potential
towards a more positive direction. Thus the composite possess
more reducing power and thus the dissolution process is
5841
hindered obviously and the resistance to corrosion increased.
The images of SEM revealed the uniform distribution of CNTs
in the zinc deposit. This makes the CNTsZn composite to
undergo uniform corrosion rather than localized corrosion. Also
during corrosion process the zinc is etched away slowly leaving
CNTs on the metal surface (Fig. 9c). This hinders the further
dissolution of zinc metal. Overall the CNTs inclusion in zinc
deposit brings down the corrosion rate and thus reducing the
metal loss.
5. Conclusions
Zinccarbon nanotubes composite coating was prepared by
electrodeposition from sulphate bath. The CNTs were well
dispersed in the solution and co-deposited along with zinc. The
CNTs were uniformly dispersed in the coating. The thickness
was uniform in zinc-composite coating. The corrosion study of
these composites inferred significant increase in corrosion
resistance. Further the delay in the formation of white rust
revealed the enhancement of service life of the CNTsZn
composites. The CNTs provide physical barrier to the corrosion
medium. These nanoparticles easily get filled in the micro hole
of the metal surface otherwise these holes are active sites for
metal dissolution. The electrochemical polarization study
inferred the uniform corrosion of composite coating. This
study highlights the use of nanoparticles for the control of zinc
coating corrosion and the electrolyte could be used to generate
zincCNTs composite coating in plating industry.
Acknowledgements
The authors are grateful to Kuvempu University and
National Institute of Technology Karnataka, India for providing
the financial assistance and facilities to bring about this work.
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