Progress in Organic Coatings 67 (2010) 405–413

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Progress in Organic Coatings

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Effect of nano ZnO on the phase mixing of polyurethane hybrid dispersions

Aswini K. Mishra, Rama Shanker Mishra, Ramanuj Narayan, K.V.S.N. Raju ∗
Organic Coatings and Polymer Division, Indian Institute of Chemical Technology, Hyderabad, 500 607, India

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

Article history: In the present study series of aqueous polyurethane (PU)/ZnO hybrid dispersions were prepared using
Received 9 September 2009 dimethylolpropionic acid (bis-MPA) as an ionic center. For this, NCO terminated PU prepolymers with pen-
Received in revised form 5 December 2009 dent acid groups were prepared first, then different concentrations of nano ZnO powder was incorporated
Accepted 14 December 2009
into the PU matrix. The hybrid dispersions were prepared by adding required amount of triethylamine
(TEA), water and chain extender. The prepared PU/ZnO hybrid dispersions were casted in a Teflon petri
Keywords:
dish and the dried films were used for TGA, DMTA, SEM, gel content and contact angle measurements.
Polyurethane dispersion
The phase mixing behavior was studied from FT-IR peak deconvolution technique and DMTA analysis
Hybrid coatings
TGA
and the result suggests that phase mixing increases with ZnO content. The DMTA data suggest that the
FT-IR phase mixing and soft segment glass transition increases but storage modulus decreases with increasing
DMTA with ZnO content. The FT-IR deconvolution result supports to the DMTA analysis. The coating properties
like adhesive strength, water absorption, contact angle, gel content and corrosion resistance of the hybrid
coatings were also evaluated.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction the possibilities of preparing materials with unique physical and

Polyurethane (PU) based materials are widely used in coatings,
adhesives, binders, sealants, textiles and medical industries [1–5].
These materials offer high performance properties with better
toughness, abrasion resistance, mechanical flexibility and chemical
resistance. Because of environmental restrictions water borne PU
has become one of the major research and development fields in
recent years [6–8]. Thus the most booming topic in today’s coat-
ing research is to reduce the VOC by using water as a solvent.
These products present many of the features related to conven-
tional solvent borne coatings with the advantage of presenting low
viscosity at high molecular weight and good applicability [9,10].
Song et al. [11] has reported the effect of urea content on the aver-
age particles size and observed the increase of particle size at higher
urea content in the medium. Delpech and Coutinho [12] studied
the influence of chain extender on the mechanical and adhesive
properties of PUDs. Lee et al. [13] has prepared a series of aqueous
PU dispersions by a modified dispersion procedure and observed
that the PUDs formed by this modified process possess higher
molecular weight and better tensile property. Yang et al. [14] and
Nanda et al. [15] synthesized two different waterborne PU hybrid
coatings by incorporating colloidal silica and diamino/dihydroxy
functional polyhedral oligomeric silsesquioxanes (POSS) monomer
as filler. These hybrid coatings are gaining importance because of
∗ Corresponding author. Tel.: +91 40 27193208; fax: +91 40 27193991.
E-mail addresses: kvsnraju@iict.res.in, drkvsnraju@gmail.com (K.V.S.N. Raju).
chemical properties such as; improved thermal, mechanical and
barrier properties, decreased gas permeability, reduced flamma-
bility and improved corrosion resistance [16]. These improved
properties are due to the combined effect of organic polymers
(e.g., flexibility, ductility, dielectric property) and inorganic mate-
rials (e.g., rigidity, high thermal stability, strength, hardness, high
refractive index) as well as large interfacial coupling between the
nanosized particles [17–19]. It has been also observed that at rel-
atively low volume fraction nanoparticles based hybrid coatings
show better properties than that of the commercial fillers [20]. The
different types of nanoparticles (TiO2 , ZnO, SiO2 , ZrO2 and CeO)
are available commercially but nano ZnO possess many significant
properties like high chemical stability, easy to disperse, low dielec-
tric constant and no surface water [21–23]. PU hybrid dispersions
prepared by using silica colloid, nano silica and clay as a reinforcing
material to improve the thermal, mechanical and barrier properties
were reported [24]. But aqueous PU hybrid dispersion prepared by
using ZnO nano powder and their application for coating is rarely
reported.
Thus to gain more insight on the contribution of ZnO nanopar-
ticles to the properties of aqueous hybrid dispersions, a series
of PU/ZnO hybrid films were prepared. For this initially, the
monomers along with the ZnO nano filler (different wt.%) were
charged into the reaction flask in a stepwise process. The urethani-
fication reaction was carried out in presence of 0.5 wt% of DBTL
as catalyst. The %NCO content in the prepolymer was monitored
in a regular interval of time by a standard dibutylamine titration
method and the reaction was stopped when it reaches below 4%.

0300-9440/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2009.12.008
406 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413
The prepolymer was cool down to room temperature and diluted
with acetone to reduce the viscosity. Then calculated amount of
triethylamine (TEA) was added to the acetone diluted prepoly-
mer with stirring. Finally, the PU/ZnO hybrid dispersions with 30%
solid content was obtained by adding required amount of water
and chain extender with vigorous stirring. The hybrid films were
obtained by casting the material on a Teflon petri dish followed by
complete air drying for about 24 h and these films were used for
further characterization like TGA, DMTA, gel contact, contact angle
and water absorption measurement. The samples were coded as
PU, PU/ZnO(0.25), PU/ZnO(0.5), PU/ZnO(0.75) and PU/ZnO(1) for 0,
0.25, 0.5, 0.75 and 1% ZnO nano powder containing hybrid disper-
sion films, respectively.
2. Experimental
2.1. Materials
Isophorone diisocyanate (IPDI: Z and E isomer in 3:1
ratio), polypropylene glycol (PPG-2000), 2,2-bis(hydroxymethyl)
Scheme 1. The various steps involved in the synthesis of aqueous PU/ZnO hybrid dispersions.
propionic acid (bis-MPA), isophorone diamine (IPDA), dibutyltindi-
laurate (DBTL) and ZnO nano powder (Particle Size 50–70 nm) were
purchased from Aldrich (Milwaukee, WI). Triethyl amine (TEA) and
acetone (dried over 4◦ A molecular sieves) was purchased from S.D.
Fine chemicals (Mumbai, India).
2.2. Synthesis of aqueous PU/ZnO hybrid dispersion films
IPDI (4 moles) and Bis-MPA (1 mole) were first added into a dry
vessel equipped with a reflux condenser, a mechanical stirrer and a
thermometer. The prepolymerization of polyurethane was carried
out at 90 ◦ C under N2 atmosphere until the NCO content reached a
theoretical value. Then PPG-2000 (1 moles), DBTL (0.5 wt.% of total
solid content) were added along with nano ZnO (0.25, 0.5, 0.75 and
1 wt.%) into the system and reacted at 80 ◦ C until the NCO content
reached a theoretical value. Then the prepolymer was neutralized
with TEA at 35 ◦ C and diluted with dry distilled acetone. Finally,
water and chain extender was added step wise to the reaction
mixture with vigorous stirring to get an aqueous PU/ZnO hybrid
dispersion of 30% solid content. The synthesized hybrid dispersion
 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413
was put on a Teflon disc and the film was extracted after 24 h of
complete air drying. These hybrid films were used for different
characterization purpose. The detail reaction process along with
the conditions was shown in Scheme 1.
2.3. Characterization
FT-IR spectra of the PU/ZnO hybrid thin films coated on dry KBr
disc were recorded on Thermo Nicolet Nexus 670 spectrometer
with resolution setting 4 cm−1 and range of 400–4000 cm−1 . Each
sample was scanned 68 times. Curve fitting simulations were per-
formed using Origin software program. TGA 7 with Pyris software
(PerkinElmer Inc., USA) was used to study the thermal decomposi-
tion profile of different hybrid coatings at a constant heating rate
of 10 ◦ C min−1 in an inert nitrogen atmosphere from 25 to 600 ◦ C.
DMTA IV instrument (Rheometric Scientific, United States) in ten-
sile mode at a frequency of 1 Hz and heating rate of 3 ◦ C min−1
was used to study the viscoelastic behavior of the hybrid coat-
ings. Contact angle was measured by using G10 (KRUSS) system
and adhesion strength by Pull-off test (Microtech Tensiometer, UK).
The surface of the hybrid films was studied with SEM Hitachi-S520
(Oxford Link ISIS-SEM model), Japan. The electrochemical polar-
ization study of the coatings on mild steel panel was done in three
electrode method by IM6ex (ZAHNER Elektrik, Germany) Instru-
ment. The electrolyte used is 5% NaCl solution.
3. Results and discussion
3.1. FT-IR analysis
Fig. 1 shows the representative infrared spectra of PU/ZnO
hybrid materials coated on KBr disc in the zone 400–4000 cm−1 and
the different characteristic absorption bands are given in Table 1.
The amide I mode is a highly complex vibration and involves the
contribution of the C O stretching, the CN stretching and the
C C N deformation vibrations. The complexity and multiplicity
of inter- or intramolecular environments surrounding the carbonyl
groups in polymers make the amide I range considerably broader in
polymers. Amide II mode is seen at 1545 cm−1 and is a mixed con-
tribution of the NH in-plane bending, the C N stretching, and
the C C stretching vibrations. It is sensitive to both chain con-
formation and intermolecular hydrogen bonding. Amide III mode
involves the stretching vibration of the C N group. Amide III is
Fig. 1. Representative infrared spectra of the synthesized PU/ZnO thin films coated
on KBr disc in the zone 400–4000 cm−1 .
407
Table 1
FT-IR data of the synthesized different PU/ZnO hybrid coatings.
Peak position in cm−1 Characteristic absorption bands
3150–3500 cm −1
NH stretching vibrations
2800–3000 cm−1 CH stretching vibrations: anti-symmetric and
symmetric stretching modes of methylene groups
2795 cm−1 O CH2 stretching
1600–1800 cm−1 Amide I: C O stretching vibrations
1540 cm−1 amide II, ␦N–H + ␯C–N + ␯C–C [26]
1462 cm−1 CH2 and CH3 deformation vibrations
1455 cm−1 CH2 scissoring
1376–1388 cm−1 ␯C N
1368 cm−1 CH2 bending vibration of the methylene groups ␣
to the oxygen atom of ether function [27]
1226–1292 cm−1 Amide III,
1110 cm−1 C O C stretching vibration, ether group
1067 cm−1 CH3 deformation. O C O stretching in the hard
urethane segment + O C NH (urethane, urea)
766 cm−1 Amide IV
695 cm−1 Amide V
highly mixed and complicated by coupling with NH deformation
modes and is observed between 1226 and 1292 cm−1 . Amide IV,
V and VI bands are produced by highly mixed modes containing
a significant contribution from the NH out-of-plane deformation
mode. They are expected to be in the 800–400 cm−1 region [25–27].
The major differences in the FT-IR spectra of different PU sam-
ples were found in the NH and C O stretching zone. This is
because the properties of PU are significantly influenced by the
type and ratio of hard and soft segments and their average seg-
ment lengths. The absorbance bands of the urethane, urea and
amide groups in the free and hydrogen bonded state are shown in
Scheme 2. In all cases, the hydrogen atom of the NH group in the
urea or urethane linkages is the donor, while the acceptor will be
the carbonyl group of the amide, urethanes or urea hard segments
or the oxygen atom of the ether/ester soft segments. The hydrogen
bonding between the NH group (hard segment: HS) and urethane,
urea or amide C O groups (HS) is responsible for the phase sep-
aration behavior, whereas the same between the NH group (hard
segment: HS) and ether/ester soft segments favors a phase mixing
characteristic [28,29]. Therefore, estimation of segregation effects
of hard and soft segments in PU systems can be used for knowing
the extent of hydrogen bonding. In the present study a special type
of hydrogen bonding between the C O group of urethane/urea
linkage and OH group of ZnO nanoparticles can account for the
phenomenon of phase mixing behavior.
Thus to understand the effect of nano ZnO content on the phase
mixing behavior of hybrid coatings, we have deconvoluted the
NH and C O stretching zone of different PU/ZnO hybrid sam-
ples and a representative spectrum for PU/ZnO (0.75) is shown
in Fig. 2(a) and (b). A flat baseline was chosen for the deconvo-
lution of C O and NH zone. The peak deconvolution study of
C O zone indicates the presence of four overlapping bands at peak
value of 1720–1730, 1700–1710, 1660–1680 and 1640–1650 cm−1
and they are assigned as free urethane, free urea, bonded ure-
thane and bonded urea respectively [30–32]. The fraction of free
and hydrogen bonded carbonyl groups can be calculated by com-
paring the area of these four peaks as shown in Fig. 2(a). The
data (Table not shown) suggest that the peak contribution for
the hydrogen bonded carbonyls from urea as well as urethane
zone was highest for the sample PU/ZnO (0.75) and lowest for
PU/ZnO (0.25). Fig. 2(b) shows the deconvoluted FT-IR spectra of
the NH stretching region of the hybrid film PU/ZnO (0.75). It is
well known that, for stronger hydrogen bonding the frequency shift
() towards the lower wavenumber region will be higher. In this
study we have observed four deconvoluted bands at around 3521,
3410, 3358 and 3160 cm−1 and are assigned as free NH, hydro-
gen bonded NH (type I) [ NH· · ·O C], hydrogen bonded NH
408 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413

Scheme 2. The different types of possible hydrogen bondings in case of urethane, urea and amide structure.

Fig. 2. Representative FT-IR peak deconvolution of (a) carbonyl zone and (b) N H zone in PU/ZnO (0.75) hybrid coatings.

(type II) [ NH· · ·C O C ] and overtone due to Fermi resonance
respectively [33]. The peak contribution from type I and type II
hydrogen bonding structure in PU/ZnO (0.75) suggests that, the
amount of phase mixing was higher compared to phase separa-
tion [see the peak area at 3358 and 3410 cm−1 in Fig. 2(b)]. This
is due to the more interaction between the ZnO surface hydroxy
groups and PU polymer (shown in Scheme 3), which disrupts the
phase separation phenomenon and thus decreases the hard phase
formation in the PU matrix. The disruption of the phase separation
phenomenon with increasing ZnO content, is due to the ZnO surface
geometry which constrains the NH groups of the hard segments
in the reacting PU polymer to form hydrogen bondings with the
other hard segment C O groups [i.e., NH· · ·O C (type I)]. Thus
there is a more possibility of formation of phase mixing structures
with increasing the ZnO content [i.e., NH· · ·C O C (type II)]. The
similar behavior is also observed in our DMTA study.
3.2. TGA study

TGA thermograms of different aqueous PU/ZnO hybrid films

Scheme 3. The probable hydrogen bondings present in the urethane/urea groups
and ZnO nanoparticles.
along with the pure polymer is shown in Fig. 3 and the different TGA
data [initial decomposition temperature (T1ON ), final decomposi-
tion temperature (T1END ), 10 wt% loss temperature (Td10% ), 50 wt%
loss temperature (Td50% ) and the mass remaining at 380 ◦ C] are
given in Table 2. All the thermograms showed a two-step decom-
position profile with an initial decomposition temperature around
260 ◦ C. The data in Table 2 suggest that the thermal stability of the
hybrid films is higher than the mother polymer and it increases
with increasing the ZnO filler content. For instant, the T1ON , Td10%
and Td50% for the samples PU, PU/ZnO(0.25) and PU/ZnO(0.5) are
 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413 409

Tg2 ), storage modulus (E ) and mixed phase transition temperature

Fig. 3. TGA thermograms of different aqueous dispersed PU/ZnO hybrid films along
with the pure polymer.
260, 263, 298; 270, 275, 297 and 338, 341, 350 ◦ C respectively.
This increase of thermal stability is due to the formation of strong
network structures by the surface hydroxyl groups of ZnO nanopar-
ticles through hydrogen bonding which acts as a thermal insulator
and mass transport barrier to the volatile products generated dur-
ing decomposition and thus increases the degradation temperature
[34,35].
3.3. DMTA study
The dynamic mechanical and thermal analyzer (DMTA) is an
excellent tool to study the relaxation behavior, change in loss
or storage modulus and glass transition temperature (Tg ) of the
polymeric materials. In case of urethane polymers the structure,
concentration and organization of the hard/soft segments and
their interaction have a dominant influence on the physical and
mechanical properties. The DMTA curves of pure PU and different
PU/ZnO hybrid films are shown in Fig. 4(a) and (b) and the data such
as glass transition temperature for hard and soft segment (Tg1 and
(TgM ) are given in Table 3. The result suggests that the storage
modulus and Tg2 values decreases whereas Tg1 values increases
with increasing ZnO content as reported by Zheng et al. [36]. For
instance, the trend in E , Tg1 and Tg2 values for the hybrid disper-
sions are as follows: PU/ZnO(0.75) < PU/ZnO(0.5) < PU/ZnO(0.25);
PU/ZnO(0.25) < PU/ZnO(0.5) < PU/ZnO(0.75) and PU/ZnO(0.75) <
PU/ZnO(0.5) < PU/ZnO(0.25), respectively. The above result sug-
gests that there is more phase mixing and less phase separation in
case of the sample PU/ZnO(0.75), which is clearly indicated from
its large mixed phase area [shown in Fig. 4(b)]. The increasing
order of phase mixing in case of hybrid samples are as follows:
PU/ZnO(0.25) < PU/ZnO(0.5) < PU/ZnO(0.75). The lower E value
and more phase mixing characteristic in case of PU/ZnO(0.75)
might be due to the presence of less quantity of hard phases in the
sample. This may be due to the disruption of the phase separation
phenomenon in case of PU/ZnO hybrid formulations as the content
of ZnO is increased because of the special interactions between
the ZnO surface hydroxy groups and the PU prepolymers. The data
in Table 3 also suggest that the Tg1 value increases and Tg2 value
decreases with increasing the ZnO content. This phenomenon is
due to the ZnO surface geometry, which constrains the NH groups
of the PU polymer from hydrogen bonding with C O groups of
the hard segments thus limits the phase separation phenomenon
and increases the soft segment glass transition values (Tg1 ) due to
restricted chain mobility [36].
3.4. SEM analysis
The SEM micrographs of representative PU/ZnO hybrid films
with increasing ZnO nano powder content along with their cross cut
area are shown in Fig. 5(a)–(d). It is well known that the efficiency
of the nanoparticles in improving the properties of hybrid materi-
als is mainly depends on their degree of dispersion in the polymer
matrix [24,37]. The SEM micrograms suggest that the nanoparti-
cles are uniformly distributed in the PU matrix in case of lower
ZnO containing hybrid films, whereas some cluster like structures

Fig. 4. The DMTA plot of E and tan ␦ vs. temperature curves of (a) the pure polymer and (b) the different hybrid coatings.

Table 2
TGA data of different hybrid films along with the pure polymer.

Sample code T1ON (◦ C) T1END (◦ C) Td10% (◦ C) Td50% (◦ C) Wt.% remaining at 380 ◦ C

PU 260 337 270 338 30.1

PU/ZnO (0.25) 263 340 275 341 37.5
PU/ZnO (0.5) 298 352 297 350 40.2
PU/ZnO (0.75) 304 358 305 368 43.3
PU/ZnO (1.0) 312 363 311 374 45.1
410 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413

Table 3
DMTA data of pure PU and different hybrid films.

Sample code PU PU/ZnO (0.25) PU/Zn (O 0.5) PU/ZnO (0.75)

◦
Tg1 ( C) a
−54.6 −58.4 −57.1 −40.6
Tg2 (◦ C)b 132.4 131.7 124.3 110.7
TgM (◦ C)c – 49.5 52.8 53.0
Tan ␦ at Tg1 0.21 0.22 0.22 0.21
E at Tg1 1.81 × 108 4.50 × 108 3.68 × 108 2.09 × 107
E at (Tg1 + 5◦ C) in [Pa] 1.58 × 108 3.85 × 108 3.06 × 108 1.67 × 107
C × 103 (mole/cm3 ), at (Tg1 + 5◦ C) 28.2 × 103 70.2 × 103 55.5 × 103 2.3 × 103
a
Soft segment glass transition temperature.
b
Hard segment glass transition temperature.
c
Mixed phase glass transition temperature.

are formed at higher label of ZnO loading. The homogeneity of the
surface indicates that there is a good compatibility between the PU
matrix and ZnO nanoparticles surface [38].
3.5. Contact angle study
The hydrophilicity of the samples with different weight per-
centage of ZnO content were evaluated by measuring the contact
angle formed between the water drops and the surface of the
samples using contact angle measuring system G 10 (KRUSS).
For this experiment, 5 data points for each sample were mea-
sured. The mean and standard deviation were calculated and
given in the Table 4. The data suggest that the contact angle
increases with increasing the ZnO content and the difference
between the standard deviation values are significant. This might
be due to the formation of more crosslinked structures in the
PU matrix (formed between the C O C soft segments and
the surface hydroxyl groups of the ZnO nanoparticles) with
increasing ZnO content. This effect reduces the amount of soft
C O C segments in the surface by phase mixing phenom-
ena. The resulting phase mixed structure [ OH· · ·O C ] cannot
remain on the surface of the coating because of high surface energy,
thus the surface polarity decreases and contact angle increases
[39].

Fig. 5. The SEM micrographs of PU/ZnO(0.25), PU/ZnO(0.5) along with their cross cut areas.

Table 4
Contact angle, adhesive strength, gel content and water absorption data of different hybrid films along with the pure polymer.

Sample code Contact angle in degree (mean ± SD) Adhesive strength (kg/cm2 ) Gel content (%) Maximum water absorption (%)

PU 51.6 ± 1.01 71.6 46.8 12.4

PU/ZnO (0.25) 49.2 ± 1.72 84.8 62.3 10.6
PU/ZnO (0.5) 51.4 ± 1.02 114.7 78.7 7.2
PU/ZnO (0.75) 55.0 ± 1.41 122.5 91.5 5.6
PU/ZnO (1) 59.6 ± 2.72 154.6 95.4 3.9
 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413
3.6. Adhesive strength
Interfacial adhesion plays an important role from the coat-
ing application point of view since good adhesion protects the
substrate in a better way. Therefore, it is necessary to develop
coatings with better adhesion property for corrosion protection
of metals. In this study the adhesion property of the different
PU/ZnO hybrid coatings were analyzed. For this the metal discs
were pretreated with acid cleaning (chemical pickling), washed
with distilled water and acetone before application of coatings with
spin coater. The adhesive strength of polymers on the metal sur-
face was determined by Pull-off test (Microtech Tensiometer, UK).
Adhesion mainly depends on chemical interaction and mechani-
cal interlocking at the interface. In our earlier publication [40], we
have shown that the surface segregation behavior of coatings is
due to the phase separation behavior of hard and soft segment. In
the present study, as the ZnO content increases in the formulation
the adhesive strength increases. For instance, the adhesive strength
data given in Table 4 for the samples PU, PU/ZnO(0.25), PU/ZnO(0.5)
and PU/ZnO(0.75) are 71.6, 84.8, 114.7 and 122.5 kg/cm2 respec-
tively. This is due to the ZnO surface geometry which constrains
the NH groups of urethane/urea moities from making hydro-
gen bonds with the C O groups of hard segments thus more
mixed phase structures were formed at the bulk, with increas-
ing the ZnO content. The free C O groups of these phase mixed
structures (present at the polymer/metal interface) form strong
coordinate bonds with the metal ions, thus increases the adhesive
strength.
3.7. Water absorption and gel content measurement
The water absorption (W%) was calculated by using different
PU/ZnO hybrid films of 3 cm × 1 cm size and dried in a vacuum
oven for 24 h to determine their dry weight (Wa). Water absorp-
tion was measured by immersing the film in distilled water for
24 h. The weight of the films after 24 h immersion was (Wb). Then
the water absorption was calculated by the following formula
[41].
Wb − Wa
W (%) = × 100
Wa
A known weight of oven-dried film (W1) was put into a Soxhlet
extractor for continuous extraction with toluene for 24 h at 100◦ C.
The polymer gel remained after extraction was dried (W2) and the
degree of crosslinking was measured in terms of gel content (%).
Three test specimens were used for each sample and the average
was taken as gel content.
W2
Gel content % = × 100
W1
The data in Table 4 suggest that the minimum water absorp-
tion and maximum gel content (%) of the hybrid films increases
with increasing the ZnO content [42,43]. This may be due to more
crosslinked structures were formed with increasing the ZnO con-
tent, as already explained in our earlier part of FT-IR and DMTA
analysis.
3.8. Electrochemical test and salt spray results
Electrochemical test is a technique used for studying the
corrosion performance of coated metals exposed to aqueous envi-
ronments [44,45]. Organic coatings are effectively used for the
protection of metals due to their ability to act as a physical bar-
rier between the metal surface and the corrosive environment.
All polymers are permeable to potentially corrosive species such
as oxygen, water and ions. Thus, the water molecules present at
411
Fig. 6. The polarization curves of different PU/ZnO hybrid coatings along with the
pure coating and bare metal valuated by the Tafel method in a 5% NaCl solution.
the metal/coating interface may reduce the coating adhesion, and
favoring corrosion of the metal underneath the film. Thus, prior
to coating the mild steel panels were subjected to a sequence of
chemical cleaning and surface preparation steps to remove any
trace of surface oxides. Then, the panels were washed with ace-
tone, ethanol, and doubly distilled water to remove surface oils
and dust particles. Finally, the coating was applied with the help
of a spin coater and the coupons were allowed to dry for about
24 h at room temperature. The thickness of the dry coating was
in the range 50–70 ␮m. The corrosion protection properties of dif-
ferent PU/ZnO hybrid coatings evaluated by the Tafel method in
a 5% NaCl solution and 30 min immersion time is shown in Fig. 6,
and the data are given in Table 5. The data suggest that the cor-
rosion resistance of different PU/ZnO hybrid coatings is higher
than the base polymer and bare metal and its value increases with
increasing the ZnO content [46]. For instance, the Ecorr and Icorr
values of the bare metal, PU, PU/ZnO(0.25) and PU/ZnO(0.5) are
−0.441, −0.474, −0.553, −0.457 V and −5.4 × 10−6 , −5.9 × 10−6 ,
−4.7 × 10−7 , −7.8 × 10−7 A/cm2 , respectively. The above result
implies that the ZnO nano powder based hybrid coatings are more
inert towards the electrochemical corrosion. This might be due to
the formation of more crosslinked structures with increasing the
ZnO content, which restricts the penetration of corrosive species
by acting as a strong physical barrier. Thus improves the rate of
corrosion resistance. The similar observations were also observed
by the fog test. The fog test results of different PU/ZnO hybrid coat-
ings over the mild steel panels are shown in Fig. 7(a)–(e). Fig. 7(a)
and (b), shows the salt spray result of different PU/ZnO hybrid coat-
ings before and after 200 h of salt fog test using 5% NaCl solution.
Fig. 7(c) and (d), shows the enlarged view of only PU/ZnO(0.75)
hybrid coating before and after 200 h of test, whereas the Fig. 7(e),
shows the condition of the knife cut mark PU/ZnO(0.75), hybrid
coating panel after 200 h. The observed result suggests that ZnO
Table 5
The electrochemical parameters measured from the Tafel plots of different PU/ZnO
hybrid coatings along with the pure polymer and bare metal.
Sample code Coating thickness (␮m) Ecorr (V) Icorr (A/cm2 )
Bare mild steel panel – −0.441 −5.4 × 10−6
PU 53 −0.474 −5.9 × 10−6
PU/ZnO (0.25) 58 −0.553 −4.7 × 10−7
PU/ZnO (0.5) 64 −0.457 −7.8 × 10−7
PU/ZnO (0.75) 61 −0.422 −8.9 × 10−7
PU/ZnO (1) 62 −0.524 −2.3 × 10−8
412 A.K. Mishra et al. / Progress in Organic Coatings 67 (2010) 405–413

Fig. 7. The 200 h salt spray results of different hybrid coatings in 5% NaCl solution.

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