Progress in Organic Coatings 99 (2016) 91–102

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Progress in Organic Coatings

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Biopolymers nanocomposite for material protection: Enhancement of

corrosion protection using waterborne polyurethane nanocomposite
coatings
G. Christopher a , M. Anbu Kulandainathan b , G. Harichandran a,∗
a
Department of Polymer Science, University of Madras, Guindy Campus, Chennai 600 025, India
b
Electro-organic Division, Central Electrochemical Research Institute, Karaikudi 630006, India

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

Article history: Low volatile organic content based, cost effective and simple procedural nanocomposite coatings were
Received 8 December 2015 prepared by solution blending technique. Waterborne polyurethane dispersion containing nanoparticles
Received in revised form 22 April 2016 of ZnO, modified with biopolymers were successfully prepared and the resulting nanocomposites were
Accepted 13 May 2016
coated on mild steel. The coatings with different loading levels of nano ZnO, which was modified with
biopolymers of sodium alginate and lignosulfonate were prepared via ultrasonication method. Surface
Keywords:
morphology of these nanomaterials were characterized by scanning electron microscopy (SEM) and high
Biopolymer
resolution transmission electron microscopy (HRTEM); crystallinity by X-ray Diffraction (XRD) analysis.
Nanocomposite
Ultrasonication
The effect of incorporating surface modified ZnO nanoparticles on the corrosion resistance of water-
ZnO borne polyurethane coated steel was investigated by potentiodynamic polarization and electrochemical
Waterborne polyurethane impedance spectroscopy. Also the surface wettability of the composite coating, studied through con-
tact angle suggested that increase in dosages of nanomaterials does not affect the surface wettability of
the coating. The results revealed that the increasing percentage of surface modified ZnO in waterborne
polyurethane not only promotes the dispersion of the particles but also improves the corrosion perfor-
mance of nanocomposite coatings. Corrosion results from Tafel plot and impedance analysis showed that
the 0.3 wt% loading of ZnO surface modified with lignosulfonate gives better protection than sodium
alginate.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction coating [4]. One of the approaches to overcome these problems, is

Coating plays an important role for modifying the metal sur-
faces by its aesthetic and protective purpose which also prevents
degradation of substrate by undesirable natural process of cor-
rosion that occurs from chemical reaction with its environment.
Corrosion is a continuous process, it can be prevented by various
methods like cathodic, anodic and barrier protections [1–3]. Bar-
rier protection reduces the permeability of the corrosive chemicals
and hence these are widely used for corrosion protection for met-
als. It plays as a physical barrier between the metal surface and the
aggressive corrosive environment. In organic coatings, many dif-
ferent types of fillers and micro-sized anticorrosive pigments are
used, but they come with some undesirable defects like decrease
in transparency, flexibility, adhesion and scratch resistance of the
∗ Corresponding author.
E-mail address: umghari@gmail.com (G. Harichandran).
to use nano-sized fillers and pigments instead of micro sized one, as
they are smaller in size and accommodate a larger specific surface
area. The decrease in particle size supports enhancement of bar-
rier and mechanical properties of the coating [5–8]. Apart from the
utility of nano-regime in such methods, the amount of materials
needed for the coating is also considerably less than the coatings
with micron sized particles. Nanoparticles used in organic coat-
ings are SiO2 [9,10], TiO2 [11,12], ZnO [13,14], Al2 O3 [15], Fe2 O3
[16], CaCO3 [17] and clay [18]. Predominantly, the size, shape and
the concentration of these nanomaterials determines the type of
coatings they provide.
In last two decades, the area of research mostly focused on the
developments of polymer based nanocomposite coatings [19–24],
especially in the field of polyurethane anticorrosion coatings which
can be markedly improved by incorporating nanoparticles [25,26]
into them. Polyurethanes (crosslinking of polyol and polyiso-
cyanate) are the new class of polymers with versatile applications.
Recent environmental regulation abides to reduce the usage of

http://dx.doi.org/10.1016/j.porgcoat.2016.05.012
0300-9440/© 2016 Elsevier B.V. All rights reserved.
92 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102
volatile organic contents (VOCs). Hence the use of waterborne
polyurethane (WPU) can replace conventional organic solvent
borne polyurethane, thus reducing its environmental impact con-
siderably. WPU dispersion is a binary colloidal system in which
polyurethane particles are well dispersed in a continuous aqueous
phase. They are non-toxic and non-polluting in nature. WPUs also
finds application in coating, adhesives for textile, paper, wood or
glass fibers, and so forth.
WPU finds applications in various fields, but it cannot be the
exact alternative for solvent borne coatings in automobile and
coating industry, due to its weak thermal, mechanical and barrier
properties. This has been overcome by introduction of nanopar-
ticles into the WPU matrix which enhances the said properties.
Moreover, coatings made up of waterborne polymer supported
with metal oxide nanocomposite, exhibit superior properties
such as corrosion protection, resistance for chemicals, abrasion
resistance, improved barrier properties and resistance to impact,
scratch, etc., [27–31]. Nowadays these coatings are major players
in the area of construction, thermal barriers for aerospace appli-
cations, automobile, pipeline coatings for marine applications, and
decoratives [32–35].
The incorporation of nanoparticles into polymer matrix is diffi-
cult as the dispersion formed are not stable and immediately settles
down. The large sized agglomerates reduce the barrier protection
properties of polymer matrix. Moreover, the lack of functionaliza-
tion of the nanoparticles and its connection to the polymer, results
in a poor performance of the coating. To achieve proper disper-
sion and avoid drawbacks in nanocomposite coatings, the surface
treatment of nanoparticles has been proposed. Dispersing nano-
materials in a polymer medium is a tedious process, now a days
various methods have been developed for stabilizing the particles
in the matrix, such as, using surface active agents, capping agents,
surface modifiers, dopants etc., Many surface modifying agents like
long chain fatty acids, various kind of silanes, polymer encapsula-
tion, surfactants etc., were used [4–6,36–41]. But this field needs
further innovative work to be done to improve the desired particle
dispersion. The coating efficiency can be increased by increasing
the anchoring of modified nanoparticles into the polymer. For sur-
face modification of nanoparticles mostly ultrasonication method
is used to disperse the nano fillers in polymer medium. Ultra sonica-
tion is a greener and economic approach to reduce time and saves
energy also it can significantly improve the reaction efficiency in
chemical synthesis. This is mainly due to cavitation formation when
mechanical vibrations are produced and it can be transmitted into
the liquid as ultrasonic waves. This is a useful technique when com-
pared with other techniques in terms of energy conservation and
waste minimization. Ultrasonic irradiation can enhance reactions
rates and is easy to use. This technique can be extremely efficient
and is applicable to a broad range of applications. There have been
a few reports addressing the influence of ultrasonic irradiation
using surface modification of metal oxide and other nanomaterials
[42–48].
The modern approach is the utilization of biopolymers for
the preparation of inorganic biopolymer nanocomposites which
is extremely important for food and agro-products, due to
their excellent properties, such as non-toxicity, biocompatibil-
ity, renewability, biodegradability and environmental sensitivity
[49–54]. Alginate is a biopolymer, which is present in the cell walls
of brown algae as the calcium, magnesium and sodium salts of
alginic acid which is not dissolve in water but Sodium Alginate (SA)
can dissolve in water [55,56]. Lignosulfonates [LS] are another class
of biopolymers and are brown amorphous powder, odorless, and
non-hygroscopic in nature. They exist as salts of lignosulfonic acid
[57–61]. This is particularly used for inducing powerful surface-
active properties and leads to better binding efficiency with the
substrates. These biopolymers have excellent adhesion on the sub-
strates and it also combines with nanoparticles. Moreover, it has
good control over the nucleation and favor directionally oriented
growth of nanoparticles.
Biopolymers are used to blend with waterborne polymers to
improve the properties of the host polymer in terms of thermal,
mechanical and protection properties. The property enhancement
of the bio-based WPU nanocomposites is due to better com-
patibility between the WPU and biopolymer. WPU-urea/sodium
alginate blends improved the water vapour permeability of the
coating material and WPU loaded with lignosulfonate and its
supramolecular complexes enhanced the mechanical properties
were reported [62,63]. In continuation of this research the prepa-
ration of enhanced properties of polymer materials achieved by
blend with various nanofillers. Biopolymers reinforced nanoparti-
cles are important types of nanofillers that have been successfully
used in the functionalization of polymer materials. Recent report
on WPU modified with bifunctional nanofillers of carboxylated cel-
lulose nanocrystal composed of silver nanocomposite is improved
the mechanical and antimicrobial properties [64]. The introduc-
tion of inorganic nanoparticles is brought new functionalities to
the host polymer. However, the dispersion of the particles and pre-
venting the formation of aggregates or agglomerates will greatly
reduce the applicability. New challenge for this research area is to
prepare inorganic nanoparticles without aggregation during their
integration into the host polymer.
In this article we present a novel method for surface modifica-
tion of ZnO by biopolymers through ultrasonication. The composite
are dispersed in waterborne polyurethane in various dosages using
solution blending technique. The resultant SA and/or LS anchored
ZnO nanocomposites are coated on mild steel (MS) and studied for
their resistance to corrosion using potentiodynamic polarization
and electrochemical impedance spectroscopy (EIS).
2. Materials and methods
2.1. Raw materials
Waterborne polyurethane dispersion (PU-687) was procured
from Piccassian Polymers (Stahl polymers), Argentina and analyt-
ical grades of sodium alginate and lignosulfonate were received
from S.D. Fine chemicals and Aldrich chemicals respectively.
2.2. Syntheses of nano ZnO and surface modified nano ZnO
ZnO nanoparticles (average particle size 120–135 nm) were
prepared using already reported procedure elsewhere [65]. 0.1 M
(50 ml) concentration of NaOH solution with a concentration of
0.2 M (100 ml) solution of Zn(CH3 COO)2 ·3H2 O were added in
ethanol. Then mixtures of this solution were sonicated for 30 min
(150 W) with Ultrasonics waves (150 W, 20 kHz). Finally, the white
precipitate was filtered and washed with methanol. The solid was
dried at 60◦ C for 24 h.
Surface modification of ZnO nanoparticles with biopolymer
were carried out using already reported procedure with slight mod-
ification, which is briefly described as follows [66]: 0.1 g of prepared
ZnO nanoparticles were dispersed in 50 mL of deionized water
using a fixed power sonicator (150 W, 20 kHz) for 3 min. This was
followed by drop wise addition of ammonia till a pH of 8 was
achieved to maintain the alkalinity of the mixture and sonicated
for additional 2 min prior to the further experiments. 0.4 g of SA
and/or LS was added to water and sonicated for 2 min to dissolve
the polymer in 50 ml water in a separate beaker. Then both the solu-
tions were mixed and ultrasonicated. Subsequently, the mixture
was dispersed for 15 min (on/off time: 10/5 min) through probe
and the beaker were immersed in to water to reduce the temper-
 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102
Fig. 1. Nanoparticle dispersion of (a & e) WPU, (b) WPU/0.1% of SA/ZnO, (c) WPU/0.2% of SA/ZnO, (d) WPU/0.3% of SA/ZnO. (f) WPU/0.1% of LS/ZnO, (g) WPU/0.2% of LS/ZnO,
(h) WPU/0.3% of LS/ZnO.
ature while sonicating. The maximum temperature of the solution
reached 45 ◦ C during ultrasonication. Finally, the suspension was
filtrated and washed with methanol. The solid was dried at 60 ◦ C
for 24 h.
2.3. Preparation of nanocomposite coatings
The composition of bare MS is 0.045% P, 0.3% Si, Cr, N, Cu,
0.3–0.65% Mn, 0.05% S, 0.14–0.28% C, reminder is Fe, and the exper-
iments were conducted by dispersing various dosages (0.1, 0.2 and
0.3% (w/w)) of SA/ZnO and LS/ZnO nanofillers into a WPU matrix by
solution blending method. After the preparation of WPU nanocom-
posites, bare MS was dipped into the solution and dried at 75 ◦ C
for 30 min. After 3 days at room temperature, the panels were
subjected to electrochemical studies. Before WPU nanocomposite
coating, MS is cleaned with acetone, ethanol, and double distilled
water to prepare the surface free from dust, oils and surface oxides.
The thickness of the prepared coating is in the range of 15–20 ␮.
Preparation of the nano composites and the subsequent steps were
repeated thrice to confirm consistency of the obtained results.
2.4. Characterization methods
ZnO surface modified with biopolymer nanocomposite struc-
ture of all samples were characterized by a Model Y40 of
PerkinElmer, USA, Fourier transform infrared (FT-IR) spectroscope.
This was performed with pressed pellets made using KBr powder
as diluent. The FT-IR spectrum was collected between the wave
number of 400 and 4000 cm−1 . The XRD pattern of surface modi-
fied ZnO nanoparticles were characterized by Bruker D8 advance
diffractometer, Germany. The diffractometer involved monochro-
matic Cu-K␣1 radiation ( = 1.5418 Å), a voltage of 40 KV and current
of 20 mA. SA-ZnO and LS-ZnO incorporated WPU nanocomposites
before and after corrosion studies were studied using field emis-
sion scanning electron microscopy (SEM) using TESCAN VEGA 3
SBU, Czech Republic, and energy dispersive X-ray spectroscopy
(EDAX) were carried out using SU6600 from Hitachi Ltd, Japan.
Freeze-fractured surfaces of WPU nanocomposites obtained at liq-
uid nitrogen temperature were examined, and all the samples were
coated with gold before observation. HRTEM images SAED pattern
of biopolymer coated ZnO were captured using FEI Technai G2 (T-
30), Netherlands, with an acceleration voltage of 250 kV. The coated
ZnO samples for TEM analysis were prepared by dropping dilute
suspension of modified ZnO nanoparticles onto copper meshes. The
surface wettability of the WPU nanocomposite coating was inves-
tigated by measuring water contact angle (Dataphysics OCA35,
93
Data Physics Instruments GmbH, Germany) with the sessile drop
method (5.0 ␮L).
2.5. Electrochemical impedance spectroscopy
Corrosion resistance of the WPU nanocomposites coated MS and
bare MS were studied by a three electrode cell assembly and an
electrochemical analyzer (BAS-Zahner IM6, Germany) connected
to Thales 4.15 USB software system. The applied alternating poten-
tial had root-mean square amplitude of 10 mV on the EOCP and
frequency range of measurements was 50 mHz–100 kHz. The elec-
trochemical system was including platinum electrode of area 5
square centimeter served as a counter electrode, saturated Ag/AgCl
electrode (reference electrode) and coated MS substrate (area
1 cm2 ) was served as a working electrode. Studies were performed
at room temperature using 3.5% aqueous solution of NaCl. 1sq.cm of
the test panel was immersed in the corrosion medium whereby an
open circuit potential (OCP) was obtained prior to the start of eval-
uation. After reaching a stable OCP, the sweep voltammetry were
set at ± 200 mV (upper and lower potential limits) with respect to
the EOCP. The sweep rate was at 1 mV/s. Tafel plot (log I Vs E) and the
Stern-Geary equations were used to measure the values of corro-
sion potential (Ecorr ) and the corrosion current density (icorr ) from
following equation.
icorr = [ba bc /{2.303(ba + bc )}][1/R p ] (1)
where ba and bc are the Tafel slopes or the Tafel constants,
expressed in V/decade (V/dec) and Rp is the polarization resistance
expressed in k cm2 . Ecorr and Icorr data was taken from Thales soft-
ware of BAS-Zahner IM6, Germany and this will not provide Rp and
capacitance, so we have used the equation to derive the data.
3. Results and discussion
3.1. Nanoparticle dispersion
The SA-ZnO and LS-ZnO incorporated WPU nanocomposites
exhibits a better dispersion than unmodified ZnO. The anchor-
ing effect of ZnO nanoparticles on biopolymers prevents the
agglomeration in the dispersion due to steric repulsive forces
among particles. This effect stabilizes the particles in waterborne
polyurethane medium. TEM micrographs shows that there is no
agglomeration in surface modified ZnO, which supports the effec-
tive dispersion in WPU medium. SEM images also shows that the
biopolymer based nanoparticles are distributed evenly in WPU
medium. Hence, such biopolymer based nano filler has effectively
filled the pores in the coating, that in turn enhanced the resistance
94 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102

Fig. 2. HRTEM images of SA/ZnO (a-c) different magnifications, (d) SAED pattern of SA/ZnO.

of MS to corrosion. WPU dispersion containing various dosages of 3.3. Mechanism of surface functionalization of ZnO
SA/ZnO and LS/ZnO did not settle down (due to uniform dispersion)
for a period of two days (Fig. 1) whereas unmodified nano ZnO set- Ultrasonic surface modification of ZnO nanoparticles are
tled down at the bottom within ten minutes after ultrasonication explained through following plausible mechanism. The biopolymer
[5,67]. Therefore, significant enhancement of ZnO nanoparticles in and ZnO was prepared as a solution in water medium, which acts
WPU dispersion by its anchoring effect in the presence of biopoly- as a solvent. NH3 was used to maintain the basicity of the prepared
mer is confirmed. The water contact angle values increased by the solution containing ZnO to maintain the alkaline pH. The set pH
increase in dosage of nano ZnO, which substantiates that the fillers of all experiment is 8, by varying the pH even up to 10 did not
are filling the pores effectively with a uniformly dispersed film. show significant effect on the coating efficiency. After the addi-
tion of ammonia in the solution, it dissociates into ions and tends
to get adsorbed on ZnO nanoparticles forming a monolayer. The
3.2. Surface morphology of ZnO nanoparticles
adsorption of NH4 + ions on the ZnO nanoparticles enables the sur-
face active groups to anchor the biopolymer in its surface [66]. The
HRTEM images of SA/ZnO and LS/ZnO are shown in Figs. 2 and 3.
nanoparticles dispersed ultrasonically in the medium experiences
The prepared ZnO nano particles are spherical in shape with a size
high-speed microjets in form of bubbles, pushing the biopolymers
fell in the range between 120 and 135 nm (Fig. S1). The spherical
and binding them uniformly onto the ZnO surface. Scheme 1 shows
morphology of SA/ZnO and LS/ZnO are prepared via ultrasonica-
the schematic representation of the biopolymer based ZnO incorpo-
tion method confirmed through HRTEM images. SAED pattern of
rated WPU nanocomposite coating. The coating of biopolymer with
SA/ZnO, LS/ZnO in Figs. 2 and 3 is in line with the XRD pattern.
ZnO might be due to high impact of ultrasonication or via hydrogen
The effect of surface modification and its uniform dispersion
bonding. No significant change in the loading of ZnO was observed
was confirmed through nanoparticle dispersion and contact angle
by increasing the sonication time to 30 min from 15 min. The pre-
analysis. The biopolymer attached on the surface of ZnO is shown
pared material, after drying was incorporated into WPU matrix
in Figs. 2 and 3. So anchoring groups of alginate and lignosul-
by simple sonication with various dosages. Then it was coated on
fonate prevent the agglomeration of nanoparticles by spatial steric
mild steel by dip coating method. The curing of WPU takes place
effect. These nanoparticles are stable under the electron beams
by simple evaporation of water, was aided by increased temper-
used for HRTEM measurements, indicating that a strong binding
ature. Now the dispersed particle come together and coalesces to
between the ZnO and biopolymers. Biopolymers have good interac-
form the cured film. After the addition of biopolymer modified filler
tion with polymers through hydrogen bonding and also with nano
the same mechanism of curing is adopted because the biopolymer
ZnO. The surface modified nano ZnO is incorporated into water-
borne polyurethane medium through solution blending.
 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102 95

Fig. 3. HRTEM images of LS/ZnO (a-b) different magnifications, (c) SAED pattern of LS/ZnO LS/ZnO modified nano structures.

Scheme 1. Schematic diagram of ultrasonic surface modification of nano ZnO and its corrosion protection mechanism using waterborne polyurethane dispersion coated
mild steel.
96 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102
interacts with polymer and ZnO through hydrogen bonding. There
is no specific mechanism defined.
3.4. Morphology and dispersion of WPU/ZnO nanocomposites
The SEM images shows the biopolymer modified nano-ZnO
incorporated WPU nanocomposites before and after corrosion
studies, as shown in Fig. 4 and 5. SEM micrographs of WPU with
0.3% SA/ZnO and 0.3% LS/ZnO exhibited uniform morphology of
coatings which shows the formation of closely packed, dense, uni-
form structure. As prepared, both nanocomposite coatings were
found free from any pores, cracks or defects. WPU nanocompos-
ite coatings in Fig. 4(a, b) shows that the surface modified nano
ZnO evenly distributed in the polymer matrix. The biopolymer bind
over the surface of ZnO and is distributed like particles in the WPU
film. This is evidently seen to form uniform dispersion of coating
in sodium alginate based composite films. Similarly, the particles
of lignosulfonate based composites in Fig. 4(d, e) are also evident
for uniform dispersion. Fig. 5 is the surface of the cured nanocom-
posite after corrosion experiment. It is found that rough surface of
WPU nanocomposite film is formed due to the attack of 3.5% NaCl
electrolyte during electrochemical studies. Apart from the above
results, EDAX spectra (Fig. 4 and 5) of before and after corrosion
studies confirmed the presence of Zn and O in coating is also evident
for uniform distribution of the composite matrix. This indicated
that the surface modified ZnO could disperse well in WPU. The
presence of aluminum peak in the spectrum for before and after
corrosion studies of composite film, is because it peels off from
the substrate and gets attached to aluminum foil used for EDAX
analysis. The addition of biopolymer reduces the particle/particle
interaction by lowering the surface free energy of ZnO and acting
as anchoring groups which leads to better dispersion of ZnO par-
ticles. The above results exhibit a simple route for the preparation
of surface modified nano ZnO in WPU matrix. The homogeneity
of the WPU nanocomposite surface indicates that there is a good
compatibility between the WPU and nano ZnO nanoparticles.
3.5. Contact angle
The surface of the WPU nanocomposites of different weight
percentage containing SA/ZnO and LS/ZnO were evaluated by
measuring the contact angle formed between the water drops
and the surface of the samples using contact angle measur-
ing system (Fig. 6). The data suggest (MS/WPU = 65.78◦ to
WPU/0.3%SA/ZnO = 66.78◦ &WPU/0.3%LS/ZnO = 66.85◦ ) that the
contact angle increases with increasing the nano filler content (no
significant increase).The contact angle values shows that surface
wettability of this coating does not get affected by this modifica-
tion. The external addition of this nanocomposite filler is easily
distributed into the polymer matrix, which fills the pores of the
coating and prevents the penetration of corrosive species [5,67,68].
This might be due to the formation of more crosslinked structures
in WPU matrix with surface modified ZnO. It confirms that the
biopolymer has good compatibility with WPU and ZnO gave more
crosslinked structure. The resulting composites are phase mixed
and cannot remain on the surface of the coating because of high sur-
face energy, thus the surface polarity decreases and contact angle
increases.
3.6. Structural analysis using XRD and FT-IR
The XRD and FTIR analysis suggests well-retained structure of
surface modified ZnO and unmodified ZnO [68,69]. XRD patterns of
ZnO, LS/ZnO and SA/ZnO nanocomposites are shown in Fig. 7. The
diffraction peaks corresponding to (100), (002), (101), (102), (110),
(103), and (112) planes are well indexed to the hexagonal phase
of ZnO (ICSD Ref.code-01-076-0704). Both diffractograms showed
no change in pattern and full width of half maximum for LS and SA
modified ZnO and unmodified ZnO, which is crystalline; And the
size of ZnO were not affected by surface modification. Hence, the
ZnO nanoparticles are well anchored by biopolymers and it helps
to improve the antisettling behaviour after being incorporated into
the waterborne polyurethane dispersions.
FT-IR spectrum of sodium alginate, the bands around 1022 cm−1
(C O C stretching) is attributed to its saccharide structure [Fig. 8a].
The bands at 1593, 1402 cm−1 are assigned to asymmetric and
symmetric stretching peaks of carboxylate salt groups. The peaks
located at 558 cm−1 represent Zn-O stretching. The peaks located at
3288 cm−1 represent OH stretching vibrations of alginate group
which is weaker in SA/ZnO, The above results confirms the presence
of alginate on the surface of ZnO. The FTIR spectra of lignosul-
fonate and SL/ZnO are presented in Fig. 8b. The peaks at 1500 and
1600 cm−1 represents the C C aromatic skeletal vibrations and the
sulfonic acid groups in LS appeared at about 1200 cm−1 . In addition
to all the peaks of the lignosulfonate, in the nanocomposite new
peak corresponding to 543 cm−1 is observed, which is due to the
stretching of ZnO. These results suggest that ZnO is well anchored
by lignosulfonate and alginate was confirmed. Both results supports
that prepared surface modified ZnO exhibits better dispersability
and corrosion protection [56,57,69–71].
3.7. Evaluation of corrosion performance
3.7.1. Potentiodynamic polarization measurements
The potentiodynamic polarization curves of MS and MS coated
with biopolymer modified ZnO/WPU nanocomposites are shown
in Fig. 9. Corrosion potential and corrosion current density derived
from Tafel extrapolation method by accurate evaluation from
cathodic and anodic Tafel slopes is summarized in Table 1. Cor-
rosion potential (Ecorr ) values of bare MS and MS coated with WPU
containing 0.3% SA/ZnO and LS/ZnO increased from −0.778Vvs SCE
and −0.671, −0.599 V vs SCE respectively. This shift towards the
positive region in both biopolymer modified ZnO confirmed that
WPU nanocomposite coated MS has resistance to corrosion. Sim-
ilarly, the decrease in corrosion current density (Icorr ) values of
bare MS, MS coated with WPU containing 0.3% SA/ZnO and LS/ZnO
from 28.4 ␮A/cm2 to 2.26, 0.32 ␮A/cm2 and increase in polariza-
tion resistance (Rp ) from 0.758 to 4.45 and 21.529 k cm2 further
confirms the enhanced resistance of coated MS. The WPU coating
is easy to allow the mobility of ions while electrochemical stud-
ies due to its material nature. So the Rpore value is for WPU is
low compared with WPU nanocomposites. Both biopolymers have
increase in resistance to corrosion but one among them, i.e., LS/ZnO
is superior in resistance than SA/ZnO. The shift in curves of Tafel
slopes is attributed to effective surface modification, which lead to
better dispersion and enhanced filling efficiency, free from aggre-
gation of nano filler. The steric spatial anchoring effect provides
this increased barrier protection. WPU nanocomposite form pas-
sive layers, which restrict the penetration of corrosive species to
reach mild steel surface. The protection efficiency of barrier fillers
in metal coating interface can be understood through its inhibition
efficiency (IE) and is calculated using the formula given below.
%IE = {(Icorr(0) − Icorr(i) )/Icorr(0) } × 100 (2)
%IE = {(R ct(i) − R ct(0) )/R ct(i) } × 100 (3)
where, Icorr(0) is the corrosion current density of bare MS and
Icorr(i) is the corrosion current density of LS and/or SA/ZnO/WPU
nanocomposites coated MS. Rct(0) is the charge transfer resistance
of bare MS and Rct(i) is the charge transfer resistance of LS and/or
SA/ZnO/WPU nanocomposites coated MS. The calculated%IE values
were shown in Tables 1 and 2.
 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102 97

Fig. 4. SEM & EDAX images of before corrosion studies (a–c) WPU/0.3% SA/ZnO & (d–f) WPU/0.3% LS/ZnO.

Table 1
Potentiodynamic polarization data of bare MS and MS coated with different WPU (LS/ZnO & SA/ZnO) nano composites in 3.5% NaCl solution.

Icorr Ecorr ba bc Rp Icorr P CR

Samplea (␮A/cm2 ) (V) (V/dec) (V/dec) k cm2 %IE (%) mm/yr

MS 28.4 −0.778 0.056 −0.435 0.75 – 0.33

WPU/MS 10.5 −0.739 0.076 −0.486 2.71 63.03 5.58 0.12
WPU/0.1% LS/ZnO 1.81 −0.624 0.039 −0.043 4.93 93.62 0.03 0.02
WPU/0.2% LS/ZnO 0.784 −0.604 0.078 −0.053 17.51 97.23 0.004 0.01
WPU/0.3% LS/ZnO 0.32 −0.599 0.023 −0.048 21.52 98.87 0.002 0.004
WPU/0.1% SA/ZnO 2.85 −0.691 0.05 −0.053 3.94 89.96 0.53 0.03
WPU/0.2% SA/ZnO 2.37 −0.686 0.041 −0.046 4.04 91.65 0.41 0.028
WPU/0.3% SA/ZnO 2.26 −0.671 0.038 −0.058 4.45 92.04 0.2 0.026
a
MS – mild steel, WPU – waterborne polyurethane.

Table 2
Impedance data obtained by equivalent circuits of MS and MS coated with different WPU (LS/ZnO & SA/ZnO) nanocomposites coatings studied in the present work was
displayed.

Samplea Rs (cm2 ) Qcoat -yo (␮F/cm2 ) nc Rpore (cm2 ) Qdl -yO (␮F/cm2 ) ndl Rct (cm2 ) Rct IE%

MS 8.59 – – – 364.4 0.87 196.82 –

MS/WPU 9.95 426.02 0.78 137.26 236.08 0.85 491.07 59.92
WPU/0.1%LS/ZnO 29.58 256.78 0.24 222.79 131.8 0.46 1390.02 85.84
WPU/0.2%LS/ZnO 26.48 168.53 0.27 363.49 94.14 0.37 2665.87 92.61
WPU/0.3%LS/ZnO 28.08 147.12 0.22 606.56 61.63 0.58 3687.5 94.66
WPU/0.1%SA/ZnO 17.64 361.15 0.25 295.01 186.15 0.64 1031.66 80.92
WPU/0.2%SA/ZnO 17.47 242.63 0.35 399.3 134.13 0.54 1363.42 85.56
WPU/0.3%SA/ZnO 17.51 180.32 0.28 572.15 80.39 0.56 2046.03 90.38
a
MS – mild steel, WPU – waterborne polyurethane.

The coating porosity and its corrosion rate is an important tection. Porosity of the coating was measured using the following
parameter for this studies. The biopolymer coated ZnO fills the relationship.
pores of the coating and simultaneously increases the barrier pro-
%P = (R pol/ R ∗ pol )(10−(Ecorr/ ba)) × 100 (4)
98 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102

Fig. 5. SEM & EDAX image of after corrosion studies (a & b) WPU/0.3% SA/ZnO & (c & d) WPU/0.3% LS/ZnO.

Fig. 6. Water contact angle of MS/WPU and MS coated with WPU/LS/ZnO and WPU/SA/ZnO nanocomposites.

where P is the total porosity, Rpol and R* pol are the polarization resis-
tance of bare and LS and/or SA/ZnO/WPU nanocomposites, Ecorr is
corrosion potentials differences of bare and LS and/or SA/ZnO/WPU
nanocomposites, and ba is the anodic Tafel slope for bare mild steel.
Corrosionrate(CR) = K1 × (Icorr/ ␳) × EW
where K1 = 3.27 × 10−3 , (mm g/␮A cm yr), Equivalent weight of
mild steel is estimated to be 28.25, Icorr = corrosion current den-
sity, ␳ = density in g/cm3 , EW is equivalent weight for mild steel
(EW is dimensionless in this calculation) and CR is given in mm/yr.
The effect of dispersion of nanofiller in the coating protects the
substrate against corrosion by decreasing in the porosity of the
(5) coatings. The calculated porosity values for LS and/or SA/ZnO/WPU
 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102 99

Fig. 7. XRD pattern of Nano ZnO, LS//ZnO & SA/ZnO.

Fig. 8. FT-IR spectra of (a) SA/ZnO nanocomposites, (b) LS/ZnO nanocomposites.

nanocomposites coatings are given in Table 1. Porosity of the LS
and/or SA/ZnO/WPU nanocomposites decrease from bare MS to
0.3%SA-ZnO and/or LS/ZnO (increasing the dosages of nano filler
which enhance the corrosion resistance but more than the dosage
of 0.3% of LS and/or SA/ZnO was not able to accommodate in
polyurethane medium and the dispersion of nanoparticles and anti-
settling are not improved significantly). So 0.3% SA-ZnO/WPU nano
composite coating on MS was found to be a compact coating and
with porosity values of almost 27, 2.6 and 2 times lower than
porosity in MS/WPU, MS/WPU/0.1%SA/ZnO, MS/WPU/0.2%SA/ZnO.
Moreover, corrosion rate of MS/WPU/0.3%OA-ZnO is almost 12.5
times lower than bare MS. Calculated values are given in Table 1.
Similarly, 0.3% LS/ZnO/WPU nanocomposite coating on MS was
found to be a compact coating and porosity values were almost
2.5 × 103 , 13 and 1.95 times lower than porosity in MS/WPU,
MS/WPU/0.1%LS/ZnO, MS/WPU/0.2%LS/ZnO. The corrosion rate of
MS/WPU/0.3%LS-ZnO is almost 82 times lower than bare MS; Calcu-
lated values are given in Table 1. The above results confirms that, as
the dosage of surface modified ZnO increases, the protection effi-
ciency of mild steel also increases and the filling of the pores in
the coating disallows the corrosive species to enter the substrate.
Both biopolymer/ZnO nano filler resistance was improved still the
LS modified ZnO shows prominent enhancement than SA/ZnO, this
is because of the interaction with nanofiller with polymer matrix
increase the crosslinking and the ZnO also resist the corrosion by
barrier protection mechanism. The results also support the disper-
sion of the fillers in the matrix uniformly throughout the coating
and make it compact for industrial applications. Though both SA
and LS act alone as an inhibitor but it acts as a good surface modifier
for WPU/ZnO nanocomposite coatings.
3.7.2. Impedance measurements
Electrochemical impedance spectroscopy is a non-destructive
technique, as a small amplitude sinusoidal signal is used through-
100 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102

Fig. 9. Potentiodynamic polarization curves of (i) WPU/LS/ZnO nanocomposites coated on MS, (ii) WPU/SA/ZnO nanocomposites coated on MS.

Fig. 10. Electrochemical impedance curves of (i) WPU/LS/ZnO nanocomposites coated on MS, (ii) WPU/SA/ZnO nanocomposites coated on MS.

trolled. These equivalent circuits can provide detailed information

Fig. 11. (a) Equivalent circuit for the EIS data of the Mild Steel substrate, (b) Mild
Steel coated with WPU/LS/ZnO and WPU/SA/ZnO nanocomposites.
out the measurements. Corrosion resistance of mild steel coated
with WPU nanocomposites studied for the effect of NaCl solution
(3.5% in water) by EIS at room temperature after 1 h of immersion.
Nyquist curves provided the detailed understanding the corrosion
protection of barrier coating from the curves as shown in Fig. 10 and
their equivalent circuits represented as R (QR) and R (Q [R (QR)]) in
Fig. 11. It is equivalent to commonly proposed circuit model for
the simple corrosion system which is entirely charge transfer con-
on the electrochemical reactions that takes place on the electrode.
Following data can obtained using this model: resistance of pores in
the coating (Rpore ) and the charge transfer resistance (Rct ), Rs (solu-
tion resistance), as well as the electrical double-layer capacitance
at the electrolyte/substrate interface (Qdl ). The proposed equiva-
lent circuit is for MS and MS coated with WPU nanocomposites
are shown in Fig. 11. Here Qdl represents the substrate/electrolyte
interface and Q stands for constant phase element (CPE). The equa-
tion is written as,
Y(␻) = Y 0 (j␻)n (6)
where CPE can be considered as a real capacitance when n = 1 and
real resistance when n = 0, ␻ is the angular frequency (in rad s−1 ).
Y0 is used in the non-linear least squares fitting and n is the CPE
exponent which always lies in between 0 and 1. Both are adjustable
parameters. When the coated MS is immersed in the electrolyte
the defects in the coating provides the direct diffusion pathway
for the corrosive media which initiates localized corrosion. In this
system, two electrochemical sub interfaces were formed which is
electrolyte/coating and electrolyte/substrate interface. So the elec-
 G. Christopher et al. / Progress in Organic Coatings 99 (2016) 91–102
trochemical equivalent circuits of both have been selected based on
MS with electrolyte interface Fig. 11a and b is WPU and electrolyte
interface and MS surface and electrolyte interface. Based on the
circuit the electrochemical data has been derived. Increase in val-
ues of Rct from bare MS to 0.3% SA/ZnO/WPU and/or LS/ZnO/WPU
nanocomposite coatings are obtained (from 196.82 to 2046.03 and
3687.5  cm2 ) is shown in Table 2. This further supports that the
prepared nanocomposites prominently increase resistance to cor-
rosion. This relates to two main reasons; ZnO nanoparticles could
significantly increase the barrier properties of coating as well as
biopolymer effectively anchor the ZnO and dispersed uniformly
throughout the coating. The nanoparticles are effectively surface
modified with biopolymers using this ultrasonication method in a
short duration of time and the efficiency of modification is clear
evident from HRTEM images, ZnO is modified with SA and the
ZnO modified with LS gave significant improvement. Corrosion
resistance was found to increase with an increase in the dosage
of SA-ZnO and LS/ZnO in WPU matrix, although LS was found
to be having superior resistance than SA. These result explains
WPU nanocomposite coatings are more inert towards the elec-
trochemical corrosion. The resistance to corrosion is explained by
the following mechanism; the flow electrons were restricted from
coating substrate by closing the pores thus movement of corro-
sive species in between metal/coating interface is reduced. So the
following reaction can be prevented [67,72,6].
2Fe2+ (aq) + O2(g) + 2H2 O → 2FeOOH + 2H+
4. Conclusion
The presented work describes the methodology to achieve sur-
face modification of ZnO with biopolymers (SA and LS) using
ultrasonication technique. Ultrasonication method was used to
modify the surfaces of ZnO nanoparticles in a shorter time with
higher efficiently. The LS and/or SA modified ZnO achieved bet-
ter dispersion without settling in WPU polymer medium up to
two days after ultrasonication. Surface morphology obtained from
HRTEM images for SA/ZnO and LS/ZnO revealed that the spher-
ical nature of ZnO was not affected by its surface modification.
Potentiodynamic polarization and EIS measurements confirmed
that MS coated with WPU containing 0.3% LS-ZnO nanocomposite
showed improved resistance to corrosion than 0.3% SA-ZnO. The
Rp values of SA and LS modified ZnO with WPU nanocomposites
are Rp - 4.45 k cm2 & 21.52 k cm2 and Rct values of SA and LS
modified ZnO with WPU nanocomposites are Rct - 2046.03  cm2 &
3687.50  cm2 respectively. Based on the result, LS/ZnO in WPU is
better corrosion protection than SA/ZnO in WPU.
In future, still further efforts are needed to improve the interfa-
cial interactions between nanofillers and waterborne polyurethane
in relation to the dispersion stability using various surface modi-
fiers. This will help to improve the ease of processing in coatings
industry and provide better usage in many applications and act as
a promising novel nanostructured materials.
Acknowledgements
The authors thank Piccassian Polymers, India for providing poly-
mer and National Centre for Nano Science and Nano Technology,
University of Madras, Chennai, for providing HRTEM facilities.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.porgcoat.2016.
05.012.
101
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