Surface & Coatings Technology 206 (2011) 1319–1326

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

The production of a multi-walled carbon nanotube/hexamethylene diisocyanate

nanocomposite coating on copper by electrophoretic deposition
Bimal P. Singh ⁎, Samata Samal, Sasmita Nayak, Sanjit M. Majhi, Laxmidhar Besra, Sarama Bhattacharjee
Colloids & Materials Chemistry Department, Institute of Minerals & Materials Technology, (Council of Scientific & Industrial Research), Odisha, Bhubaneswar-751 013, India

a r t i c l e i n f o a b s t r a c t

Article history: A multi-walled carbon nanotube (MWCNT)/hexamethylene diisocyanate (HDI) composite coating with ex-
Received 27 January 2011 cellent microstructural homogeneity was produced on copper substrate from aqueous suspensions using
Accepted in revised form 27 August 2011 electrophoretic deposition (EPD). The concentrations of different additives were optimized to obtain stable
Available online 2 September 2011
suspensions of MWCNT. At the optimum EPD condition, a coating of thickness 170 μm was obtained at volt-
age of 30 V and deposition time of 3 min with well dispersed MWCNT in the polymer matrix. The deposit
Keywords:
Electrophoretic deposition
yield increased linearly with deposition time. The adhesive strength of the MWCNT/HDI composite coating
MWCNTs was assessed qualitatively by peel test. The composite coated specimen showed greater resistance to corro-
Nanocomposite coating sion in the chloride containing environment with inhibiting efficiency 96.65%. The mechanism for adhered
Surface charge coating is due to better wetting of HDI on copper substrate followed by acid-base reaction between metal hy-
Corrosion test droxide and polymeric resin. The potential application of the nanocomposite coatings could be protecting
copper based metallic structure in marine environment.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Carbon nanotubes (CNTs) are the most sought after materials for the
scientific community of materials science throughout the world and are
viewed as most ideal candidates for preparation of high performance
polymer composite with unique mechanical and other physical proper-
ties [1–3]. The elastic modulus (stiffness) and tensile strength (strength)
of CNT can be as high as 1 TPa and 200 GPa respectively, which is higher
than the strongest steel at a fraction of the weight [4]. Therefore, CNT
could be employed as very light, strong and tough fibers for composite
structure [5]. There are number of reviews on the mechanical properties
of CNT-polymer composite highlighting its importance and exciting po-
tential applications [6–11]. The effective utilization of CNT for composite
application primarily depends on homogeneous dispersion of CNT as
filler throughout the polymer matrix. Aggregates act as defect sites
and will seriously limit the mechanical performance apart from adverse-
ly effecting physical properties of the composite [3]. However, uniform
dispersion of CNT in polymer matrix is restricted presumably due to
(a) high surface energy which makes it difficult to suspend them in liq-
uid but helps in formation of aggregates [12] (b), the high polarizability
of the π-electrons of graphene sheets leads to powerful van der Waals
attractive forces, and (c) axial geometry, which provides a large surface
area of contact facilitating high attractive energy between CNT [13].
⁎ Corresponding author. Tel./fax: + 91 674 2581637.
E-mail address: bpsingh99@yahoo.com (B.P. Singh).
Therefore, a significant challenge critical for processing CNT for compos-
ite application is to form uniform dispersion of CNT within the polymer
matrix, improve nanotube/matrix wetting, and enhance their mutual
adhesion [14,15].
The overall aim of this investigation is to produce uniform deposits
of multi-walled carbon nanotube (MWCNT) and polymer as thin film
from its colloidal suspensions, by electrophoretic deposition (EPD).
EPD is a colloidal forming technique where charged, colloidal particles
in a stable suspension are deposited onto an oppositely charged sub-
strate by the application of electric field [16]. It is commonly employed
in processing of ceramics, coating, and composite [17–20]. EPD is very
versatile, fast, and cost effective to produce coating of controlled micro-
structure on a wide range of substrates. The process can be applied, in
general to any solid in particulate form with small particles (b30 μm)
and to colloidal suspensions [21]. EPD is a very powerful tool for the or-
dered deposition of CNT and CNT-based nanostructures for a variety of
applications, including (i) catalyst supports (ii) structural composites
and coating (iii) gas sensor (iv) capacitor (v) biomedical scaffold
(vi) electrode for fuel cells (vii) actuators and (viii) field emission de-
vices, [19,21–24]. Most of the above research used organic solvents or
mixture of organic solvent and resin to prepare composite [23,24]. Re-
cently, Thomas et.al, [20] used aqueous EPD to obtain MWCNT coating
of about 10 micron thickness at 40 V and 4 min deposition time. In ma-
jority of cases, EPD is reported to use organic/mixture of organic solvent
as vehicle, which is not only hazardous but also polluting the environ-
ment and dangerous for sea species, when it is used in seawater. Re-
search effort is being made to develop aqueous based EPD [20,25,26]
to minimize the uses of organic solvent. Present investigation is an

0257-8972/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2011.08.054
1320 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326

attempt in that direction, it not only involved aqueous processing but

also used dispersant which is a natural polysaccharide of plant origin.
A major part of metallic constructions exposed to seawater and
marine atmospheres are destroyed, due to the corrosion phenomena.
Copper is one of the essential structural engineering materials widely
used in chemical industry, pipelines for domestic and industrial utili-
ties, heat conductors, heat exchangers, electronic industry, communi-
cation industry including seawater (marine environment) owning to
its mechanical workability and other properties [27]. Under intense
seawater/marine environment, the copper form thin layers of corro-
sion products, generally dark-brown to green-bluish colour, chemi-
cally known as copper hydroxide and copper carbonate, copper
sulphate etc. depending upon exposure time, and presence of pollut-
ants in the surrounding environment, which is technically also known
as patina [28]. Copper ions being very sensitive to chloride ions, even
presence of trace amount can cause corrosion at very significant rate
in sea water and form unstable films of CuCl and soluble chloride
complexes [27]. The conventional treatment approach is based on hy-
drophobic polymer paints coating or self assembled monolayer [27];
however, they have their own limitations, first and foremost is very
short life span of coating and therefore, one has to go for coating
very often, multistep, and tedious. Sometimes polymeric resin paints
contains toxic substances like (chromium etc) which is very harmful
to the environment. Nanostructure materials engineering extends the
possibility of designing environmentally friendly anti-corrosion engi-
neering ‘smart’ coatings which can last much longer compared to tra-
ditional coatings. CNT-reinforced polymer nanocomposite based
protective coatings are attractive options for marine environment ap-
plications due to their excellent properties and unlimited possibilities
of tailoring their chemical, physical and processing behavior to meet
the requirement. CNT-reinforced nanocomposite coatings guard the
substrate by providing a tough protective shield that can lock out de-
structive elements and keeping it resilient and durable for very longer
period of time, which cannot be met by the traditional micrometer
hydrophobic polymer/self-assembled monolayer coatings. Fig. 1. a. SEM image of as received pristine MWCNT with very large number of cross-
The specific aim of the present work is to fabricate MWCNT/ linking and entanglement. b. SEM micrograph of well dispersed MWCNT in presence
of dispersant GA.
hexamethylene diisocyanate (HDI) composite coating by EPD from
aqueous suspensions for possible potential application in stringent
marine environment to protect copper based structure from oxida-
tion and further corrosion. In this study HDI has been reported as 2.2. Preparation of MWCNT/HDI suspension for EPD
polymeric matrix for the first time. The influence of dispersant
and polymeric resin on improving the adhesive strength of the Preparation of well dispersed suspension, free from agglomerates,
MWCNT/HDI composite coating on copper substrate will be exam- is a prerequisite for obtaining uniform, homogeneous and crack free
ined. The most plausible mechanism of coatings by combination of deposit by EPD. 0.1 wt.% of MWCNT suspension was prepared in
MWCNT and polymeric resin (HDI) on copper substrate has been aqueous solution by adding pre-optimized quantities of GA and HDI,
proposed. combination (600 mg/g) and (0.27 mg/g) respectively. Dispersant is

2. Experimental

2.1. Materials

MWCNT was purchased from Sigma-Aldrich Chemie, GmbH, Stein-

heim, Germany, with diameter range of 110–170 nm and average
length 5–9 μm as reported by the supplier (Fig. 1). The Scanning elec-
tron microscopy (SEM) image of pristine MWCNT showed large num-
ber of cross-linking and entanglements. The entanglement could be
broken to large extent by addition of dispersant. Fig. 2 shows well dis-
persed MWCNT in presence of dispersant Gum Arabic (GA). GA used
as dispersant is a highly branched polysaccharide and is known for
its dispersion property. HDI is an organic polymeric resin generally
used in special applications such as enamel coating which are resis-
tant to abrasion and degradation from UV light. The as received
MWCNT was further characterized by the Raman spectroscopy (Fig.
2). The D-band (1353 cm− 1), G-band (1575 cm− 1) and D’-band, the
second order overtone of D-band (2696 cm− 1), confirms the typical
characteristics of multiwall carbon nanotube. Fig. 2. Raman spectra of multi-walled carbon nanotube.
 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326
selected in such a manner so that there should be synergy between
dispersant and polymeric resin. The suspension was ultrasonicated
at 160 kW for 30 min to break the agglomerates. Sedimentation of
the particles was prevented by mild stirring by using a magnetic
stirrer.
2.3. Electrophoretic deposition of MWCNT/HDI on copper substrate
Electrophoretic deposition of MWCNT/HDI on the copper substrate
was carried out using the deposition set up as shown in Fig. 3. Two par-
allel copper plates (9 mm× 30 mm) separated by 10 mm gap were used
as the electrodes. One of them works as depositing substrate (cathode)
and other as the counter electrode. The suspension was ultrasonicated
for about 20 min just before the EPD experiments. EPD was carried
out at constant voltage mode at DC voltage between 10 and 30 V,
using a source meter (Model: 2410, Keithley Instruments, Inc, USA)
for deposition time of 0.5–5 min. Once deposition is over, the deposit
was taken out carefully vertically along with the substrate. The sample
was then allowed to dry upright position overnight at room tempera-
ture and weighed to determine the deposit yield and the products are
ready for characterization.
2.4. Electrochemical corrosion test Ag/AgCl electrode as reference
electrode
The electrochemical experiments were carried out using potentio-
stat (Model: Versastat-3, Prinston Applied Research, USA) with a
three electrode electrochemical cell. The Cu-electrode embedded in
the epoxy resin served as the working electrode, Pt as counter elec-
trode and standard Ag/AgCl as reference electrode. The working elec-
trode with exposed area 1 cm 2 was stabilized in 3.5% NaCl solution at
room temperature (35 °C). The open circuit potential (OCP) was
monitored continuously till the steady state was reached. The polari-
zation plot was recorded at a scan rate of 1 mV/s within a scan range
of +1 V to −1 V. The corrosion potential (Ecorr) and corrosion current
density (Icorr) was computed by Tafel extrapolaration technique from
polarization plot.
2.5. Characterization
The microstructural and morphological characterization of
MWCNT and composite samples were carried out using Scanning
Electron Microscope (Model: Hitachi, S-3400 N,Tokyo, Japan). The
Fig. 3. Schematic diagram of EPD set up.
1321
Raman scattering experiments were carried out using a Renishaw Im-
aging Microscope WiRE spectroscopy (Model: Invia Reflex-H33197,
Incoterm, UK) equipped with air cooled CCD detector. The spectra of
powder samples of MWCNT were measured over a scanning range
of 0–3250 cm − 1 with incident argon laser excitation wavelength of
514 nm. The specific surface charge of MWCNT suspension measure-
ments were carried out with Particle Charge Detector (PCD), Model:
PCD-04-pH from Herrsching, Muteck, Germany. The anti-corrosion
property of MWCNT reinforced polymer coating films were investi-
gated using potentiostat (Model: Versastat-3, Prinston Applied Re-
search, USA).
3. Results and Discussion
3.1. Determination of stability maxima and optimum dispersant (GA)
and HDI dosages
Fig. 4.(a, b and c) shows the optimization of concentration of dis-
persant GA, polymeric resin, HDI and combination thereof using Par-
ticle Charge Detector (PCD), the details of which described elsewhere
[29,30]. The variation of PCD potential as function of different concen-
tration is plotted and the inflection point in the graph gives the opti-
mum concentration required for stable dispersion. The initial increase
in PCD potential occurs due to increase in specific charge due to
adsorbed additives on MWCNT surface with increasing concentration
of dispersant. Once the surface is covered completely (monolayer
coverage), that quantity gives the overall maximum stability and op-
timized chemical additives dosages. The unadsorbed excess remains
in the solution and may affect viscosity of the solution without affect-
ing PCD potential. The measured optimum dosages of GA, HDI and GA
and HDI combination were 600 mg/g (Fig. 4.a), 0.2 mg/g (Fig. 4.b) and
0.27 mg/g (Fig. 4.c), respectively. This technique is very easy, accurate
and useful for the assessment of stability of nanoparticles suspensions
and determination of optimum dispersant concentration for nano-
ceramics and polyelectrolyte systems. [31–33].
3.2. Measurement of surface charge and stability of suspensions
The quantum of surface charge density on any particulate matter
in aqueous suspension is an important particle characteristic and
helpful for knowing dispersability of suspension. A very high surface
charge density is an indicative of strong repulsive forces between
the particles and results in good dispersion. Fig. 5 shows the results
of surface charge measurement of pristine MWCNT, treated MWCNT
with dispersant GA and MWCNT in presence of dispersant GA and
polymeric resin HDI in aqueous suspension at different pH. The pris-
tine MWCNT is slightly positively charged at acidic pH and slightly
negatively charged at alkaline pH. The isoelectric point (iep) of pris-
tine MWCNT is found to be at pH 4.5. The isoelectric point (iep) is
the pH value where surface concentration of H + and OH − ions are
equal. The isoelectric point (iep) is a material property. In conclusion,
we can say that the surface charge is positive at pH less than pHiep
and negative at pH greater than pHiep. When MWCNTs are treated
with anionic dispersant GA (optimum dosage 600 mg/g of MWCNT),
it shows very high negative surface charge throughout the pH range
investigated and practically no isoelectric point was observed. The
negative magnitude of surface charge increased concomitantly with
increase in pH due to the adsorption of anionic GA on MWCNTs sur-
face. The adsorption of GA on MWCNT surface structure was also con-
firmed by Raman spectroscopy (Fig. 9). The surface charge was as
high as − 63.5 C/g at pH around 10, thereby making MWCNT surface
highly negatively charged and hence promoting dispersion of
MWCNTs in the suspensions.
The surface charge density of MWCNTs in presence of optimized
dosages (0.27 mg/g) of HDI (cationic polymeric resin) is positive
throughout the pH range investigated and varies from +38.6 C/g at
1322 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326
Fig. 4. a. Optimization of concentration of GA for MWCNT. b. Optimization of concen-
tration of HDI in aqueous suspensions of MWCNT. c. Optimization of concentration of
HDI at optimized dosages of MWCNT and GA.
pH 2.5 to 40.5 C/g at pH 11. In this case also, we did not observe iso-
electric point. When highly cationic HDI is added to the MWCNT sus-
pension in water, it first neutralizes the negative charge developed
due to addition of dispersant GA, (GA is used before addition of
HDI to disperse MWCNT) followed by reversal of charge to highly
positive side. Such a high positive surface charge of HDI adsorbed
MWCNT particles cause steric repulsion and lead to separation of
the bundled nanotubes resulting in better dispersion and stability
[34,35].
Fig. 5. pH vs. surface charge measurement of aqueous suspensions of MWCNT, GA and
HDI at different pH.
3.3. EPD coating of MWCNT and polymeric resin HDI
Fig. 6.(a and b) shows the SEM images of MWCNT/HDI composite
coating on copper substrate at the optimal applied potential of 30 V
and deposition time 3 min. Surface morphology of MWCNT/HDI com-
posite coating is shown in Fig. 6.a clearly depicts well dispersed
MWCNT throughout the polymer matrix. It was observed that higher
applied voltages during EPD produced very uniform and homogeneous
deposits of controlled and appreciable thickness (170 μm) at deposition
time 3 min and above. The microstructural analysis of thin coating did
not show any micro cracks. However, MWCNT film produced at 1 min
deposition time at any applied potential were non-uniform and inho-
mogeneous, but adherence was quite good with the substrate, presum-
ably due to stronger interaction between polymeric resin and copper
substrate. It was also observed that with increasing deposition time,
there is a linear increase in thickness of the MWCNT film. The deposi-
tion yield of MWCNT film with varying deposition time (0.5–5 min)
from 0.1 wt.% aqueous suspension at a constant applied voltage of
30 V is shown in Fig. 7. It is apparent from the Fig. 7. that the amount
of deposition increases linearly with increasing deposition time. The lin-
earity in yield is generally observed at short deposition time and since
we got good uniform, homogeneous, crack free deposition at 3 min of
deposition time, therefore we choose 3 min deposition time for all the
experiments. The relative green density of the deposited film was
around 75%. The high relative density may be due to strong interaction
between positively charged MWCNT and polymeric resin with negative
conducting copper substrate.
The adhesive strength of MWCNT reinforced polymeric (HDI)
nanocomposite coating to the substrate was qualitatively examined
by ‘Peel Test’ using adhesive tape following the literature [20,36]. In
this test adhesive tape is stuck to the EPD coating of MWCNT. While
detaching/removing the tape, it was observed that the MWCNT coat-
ing remained adhered to the substrate and did not stick to the tape
implying good adhesion of the composite coating to the substrate.
This may be due to better wetting of HDI on copper substrate,
which is further discussed later.
Fig. 6.b depicts fracture surface of cross-sections of thin film com-
posite coating of CNT-polymer resin (interface of coating and sub-
strate), which clearly shows there is not any macroscopic porosity
within the thin film and the reinforcement of MWCNT evenly embed-
ded into the polymer matrix.
Fig. 8 shows the optical photograph of MWCNT-polymer resin thin
film deposited on copper substrate by EPD. The coating is very
smooth and of uniform thickness. The coating did not peel out from
the substrate even after bending the substrate.
 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326
Fig. 6. a. Surface morphology of MWCNT/HDI composite coating by electrophoretic de-
position. b. Fracture surface of MWCNT/HDI composite showing reinforcement of
MWCNT evenly embedded into the polymer matrix.
Fig. 9 shows typical Raman spectra's of MWCNT, MWCNT with GA,
and MWCNT with GA and HDI. The D-band peaks 1300–1400 cm− 1 spec-
tral range also known as the disorder band is due to scattering from sp2
carbon containing defects. The strength of the peak is related to the
amount of disordered graphite and the degree of conjugation disruption
Fig. 7. Thickness of the deposited layer vs. deposition time at applied voltage 30 V.
1323
Fig. 8. Optical photograph of MWCNT/HDI composite coating on copper substrate.
in the graphene sheet [37,38]. It precisely appeared at 1353 cm− 1. The
peak between 1500 and 1600 cm− 1 region called the G-band, and also
known as the graphite or tangential band resulting from graphite sheet
(the C–C stretching vibrations on the CNTs axis) [39], which exactly
appeared at 1575 cm− 1. A very strong peak at 2696 cm− 1 is also
obtained and commonly written as D’ or 2D band, which depends upon
the strain or stress applied to the nanotube by the surrounding media.
There is a sharp change in the intensity and sharpness of D-band
after modification with polymeric resin. The appearance of D-band
shows less ordered structure. There is visible trend in the spectral posi-
tion of the G-band before and after the adsorption of polymeric resin.
The untreated nanotubes show G-band peak at 1575 cm− 1, whereas
in polymer treated samples, band is shifted to higher wave number
1585 cm− 1. The G-band shift is due to strong adsorption of the poly-
meric resin to MWCNT, and in turn increase in the elastic constant of
the harmonic oscillator of the polymer coated MWCNT [38]. The hydro-
phobic and van der Waals attraction forces between the polymer and
the graphite sheet increase the energy essentially required for vibration
to occur, which is reflected in the higher frequency peaks [37]. It has
been reported that the position of the D-band and D/G band intensity
ratio changes when there is covalent modification [40,41]. No signifi-
cant change in the D/G band intensity ratio (0.083 for only MWCNT
and 0.324 for MWCNT and polymeric resin) clearly indicates that the
polymeric resin do not covalently adsorbed to the CNT [42,43]. D/G
band intensity ratio (ID/IG), gives very important structural disorder
originating from the formation of defects in the graphene layers.
Fig. 9. Raman spectra's of MWCNT before (plot-1) and after coating with MWCNT & GA
(plot-2), and MWCNT, GA & HDI (plot-3).
1324 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326
A very sharp change in the spectral position of D’-band is observed
due to polymeric resin coating of MWCNT. The pristine nanotube
showed D’-band peak at 2696 cm − 1, while in polymer coated nano-
tube, band is shifted to distinctly higher wave numbers. The most sig-
nificant shift is seen from 2696.57 to 2709.65 cm − 1 (i.e. a shift of
13.08 cm − 1). The wrapping of the MWCNT by dispersant is strongly
supported by the sharp shift in the position of the D’-band, which pri-
marily depends on the strain or stress on the nanotubes by the sur-
rounding media. If we compare Raman spectra of pristine MWCNT
with polymer adsorbed MWCNT, the up shifts of around
13.08 cm − 1 are observed in the D’-band which is due to hydrostatic
compression force on the MWCNT [43–47].
3.4. Electrochemical corrosion measurement test results
Fig. 10.(a and b) shows an open circuit potential (OCP) variation
with time and potentiodynamic polarization curves of copper sub-
strate with and without MWCNT reinforced nanocomposite coating
films respectively. It has been observed that it took almost 2 h to sta-
bilize the OCP data, which is reported in this work. It has also been
observed that compared with bare copper (OCP = −0.165 V), the
OCP of coated copper substrate significantly shifted towards noble di-
rection and reached the potentials of − 0.015 V (Fig. 10.a). The OCP
value of coated substrate is order of magnitude lesser than the
uncoated copper substrate.
Fig. 10. a. Open circuit potential vs. time plot of copper with and without MWCNT coat-
ed films in 3.5% NaCl solution. b. Potentiodynamic polarization curves of the copper
with and without MWCNT coated films in 3.5% NaCl solution.
Fig. 10.b shows the potentiodynamic polarization curves of bare
copper substrate and coated copper substrate. It is evident from the
curves that the coated copper substrate has the lowest anodic current
density compared to uncoated copper substrate, showing thereby
that coated substrate has much better corrosion resistance compared
to uncoated one. These results further indicated that the nanocompo-
site films acted as protective layers and improved the corrosion resis-
tance of the MWCNT reinforced polymer coated copper substrate.
The corrosion potential (Ecorr) and corrosion current density (Icorr)
obtained by the extrapolation of Tafel curves [48] is presented in
Table 1. The corrosion potential (Ecorr) of coated copper substrate
shifted to less negative values, −162.888 mV (Table 1), indicating
thereby that this surface has a very smaller tendency to corrode. The
corrosion current density (Icorr) of coated surface (1.28 μA/cm2) is
also significantly lower than bare copper substrate (38.25 μA/cm2).
The corrosion resistance of coated material increased by the order of
magnitude than the bare copper substrate in the environment con-
taining 3.5% NaCl solution. It, therefore, clearly signifies that corrosion
behavior of coated materials are nobler having lowest Ecorr and Icorr
values in comparison to without composite coated materials. From
the results shown in Table 1, the corrosion inhibition efficiency (η)
of the coated films covering the copper substrate was calculated
using Eq. (2)[49].
η ¼ ½ Iwithout film –Iwith film =Iwithout film x100 ½2
where I is the electric current density values presented in Table 1. The
inhibiting efficiency of the MWCNT reinforced polymer coating was
computed to be 96.65%, which is supposed to be excellent.
Fig. 11.(a,b and c) shows the SEM images of Cu-substrate (A),
copper substrate after corrosion test (B), and MWCNT reinforced
polymer coated composite after corrosion (C) respectively. It is clear-
ly shown that the copper substrate is quite uniform without any de-
fects in the tested area (Fig. 11.a), whereas same copper substrate
after corrosion test is completely destroyed, evident by the cracks de-
veloped during corrosion testing (Fig. 11.b). Fig. 11.c shows the
image of MWCNT reinforced composite coated copper substrate
after corrosion test, which clearly shows that the coated sample is
not much affected by corrosion phenomena during corrosion testing.
Therefore, coated materials offer better corrosion protection in the
environment containing chloride ions. This not only shows the ad-
hered coating is strongly corrosion resistant but also shows efficacy
of the technique developed for the protection of copper substrate
for destruction under stringent marine environment.
3.5. Mechanism of adhered coating
The mechanism for adhered coating of MWCNT reinforced poly-
meric resin with copper substrate may be due to better wetting and
the formation of metal hydroxide at the electrode surface during
EPD [20,50]. The reaction can be described as follows [51]:
2Cu þ H2 O þ CO2 þ O2 ➙CuðOHÞ2 þ CuCO3 ½1
Good wetting of HDI on copper substrate can be explained as fol-
lows. In presence of moist air, a mixture of copper hydroxide Cu(OH)2
and copper carbonate CuCO3 is formed. The metal hydroxide interacted
with HDI through amine group, in which HDI is an electron donor,
whereas OH acts as acceptor and the proton of the surface hydroxyl
Table 1
Corrosion test results.
Surface OCP (mV) Ecorr (mV/cm2) Icorr (μA/cm2)
Bare copper substrate. − 164.0 − 691.456 38.25
Coated copper substrate. − 16.0 − 162.888 1.28
 B.P. Singh et al. / Surface & Coatings Technology 206 (2011) 1319–1326
Fig. 11. Scanning electron micrographs of (a) copper substrate (b) copper substrate
after corrosion (c) MWCNT reinforced polymer coated composite after corrosion test.
groups of metal hydroxide are transferred to the basic nitrogen atoms of
the adsorbed HDI molecules and become positively charged. Therefore,
metal hydroxide and HDI undergo acid-base reaction [52–54]. The over-
all reaction mechanism can be represented as:
ðM−OHÞsurface þ O ¼ C ¼ N  CH2  CH2  CH2  CH2  CH2  CH2  N ¼ C ¼ O
 þ
ðM  O Þsurface þ O ¼ C ¼ NH  CH2  CH2  CH2  CH2  CH2  CH2  HN ¼ C ¼ O
1325
4. Conclusions
• The optimized dosages of GA, HDI and combination of GA and HDI
for dispersion of MWCNT suspensions were found to be 600 mg/g,
0.2 mg/g and 0.27 mg/g, respectively.
• The isoelectric point (iep) of MWCNT without any additive was pH
4.5. In presence of GA, surface charge on the MWCNT surface be-
came strongly negative, and addition of HDI overall surface charge
becomes positive. Therefore, cathodic EPD was performed for final
MWCNT/HDI composite coating.
• Based on optimized process parameters, the MWCNT/HDI composite
coating of thickness 170 μm at constant applied voltage 30 V and de-
position time of 3 min were obtained with well dispersed MWCNT in
polymer matrix.
• In the range of present investigation, there is a linear increase in de-
posit yield with increasing deposition time.
• Cathodic constant voltage EPD has been developed to create uniform,
homogeneous crack free deposits having controlled thickness on cop-
per substrates. The coatings had packing efficiency around 75%. The
potential application of developed composite coatings on Cu-
substrate is in the area of protection of metallic construction exposed
to marine environment under seawater. Other budding application
could be in heat exchanger devices, where high thermal conductivity
of CNT can be exploited.
• There was no significant change in G/D band intensity ratio in
Raman spectroscopic analysis, confirming that the structure of
nanotubes remain intact during sonication. Raman spectroscopic
analysis further revealed the existence of the specific interaction in-
volving polymeric resin and MWCNT due to peak shift/peak width
changes, which is also clear from surface charge measurement of
MWCNT in presence of GA and HDI.
• Potentiodynamic polarization studies showed that the CNT reinforced
composite coated specimens can better protect Cu-substrate surfaces
exposed to chloride containing environment against corrosion. The
corrosion inhibition efficiency (η) of coated copper substrate deter-
mined by potentiodynamic polarization was found to be 96.65%.
• The mechanism of adhered coatings of MWCNT and polymeric resin
HDI with substrate copper is supposed to be due to adsorption of
amino group containing HDI on the oxide surface due to better wet-
ting followed by acid-base reaction with copper hydroxide and HDI.
The hydroxyl group of metal oxide transferred proton to the basic
nitrogen atom of the adsorbed HDI molecules forming strong bond-
age as depicted in Eqs. (3)and (4).
• The developed process is environmentally benign as it involves
aqueous processing in presence of dispersant which is also natural
polysaccharide produced from Acacia trees. The advantages of com-
posite coating over traditional polymeric resins paints coating is
that it does not contains any toxic substances like chromium com-
pounds etc. that are harmful to the environment.
Acknowledgements
The authors would like to thank the Director, Institute of Minerals
& Materials Technology, Bhubaneswar, for according permission to
publish this paper. The authors would also like to thank Mr. Ajit
Dash, Central Characterization Cell for Raman spectroscopic analysis
of CNT samples.
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