Dyes and Pigments 121 (2015) 282e289

Contents lists available at ScienceDirect

Dyes and Pigments

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

Synthesis of ZnO nanoparticles and studying its inuence on the

antimicrobial, anticorrosion and mechanical behavior of polyurethane
composite for surface coating
Ashraf M. El Saeed a, M. Abd El-Fattah b, *, Ahmed M. Azzam c
a
b
c

Petroleum Applications Department, Egyptian Petroleum Research Institute (EPRI), Cairo, Egypt
Production Department, Egyptian Petroleum Research Institute (EPRI), Cairo, Egypt
Environmental Researches Department, Theodor Bilharz Research Institute (TBRI), Giza, Egypt

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 5 March 2015
Received in revised form
27 May 2015
Accepted 28 May 2015
Available online 6 June 2015

Zinc oxide nanoparticles (ZnO NPs) were obtained by a direct precipitation method. The TEM photograph
demonstrated that the synthesized ZnO NPs were of a pseudo-spherical shape and the average diameter
of the particles is 20.0 nm. ZnO polyurethane nanocomposite (ZPN) coating lms were fabricated by
uniformly dispersing ZnO NPs in varying loading levels 0.1 to 2.0 wt.% in commercial two component
polyurethane by ultrasonication. The antimicrobial activity of ZPN coating lms was screened against
Gram-negative and Gram-positive bacteria. Corrosion performance, physical and mechanical properties
of ZPN coating lms was evaluated. The resulting perfect dispersion of ZnO NPs in polyurethane coating
was revealed by SEM. The results showed slowdown, the growth of organisms on the ZPN coating
surface, and also showed an improvement in the corrosion resistance, mechanical resistance at lower
concentration, and this improvement increases with increase ZnO NPs wt.%.
2015 Elsevier Ltd. All rights reserved.

Keywords:
ZnO nanoparticles
Polyurethane nanocomposite
Antimicrobial activity
Corrosion resistance
Mechanical properties
Surface wettability

1. Introduction
The use of nanoparticles (NPs) as additives in coatings has been
found to improve the thermal stability of the polymer [1,2], enhance
scratch and abrasion resistance, barrier properties including
corrosion resistance of the coatings without disturbing their other
properties [3,4]. Nanoparticles most commonly used in coatings are
SiO2 [3,5e7], TiO2 [2,8], ZnO [9,10], Al2O3 [11], Fe2O3 [12] and CaCO3
[13]. Use of nano-particles are most commonly based on the
inherent properties they posses. For example, nano-titania and
nano-zinc oxide is most commonly used as UV blocking agents,
whereas nano-alumina and nano-silica are used to improve scratch
and abrasion resistance of the coating. The enhanced properties are
the result of the much greater surface to volume ratio of the nanopigment that is often characterized by very high aspect ratios [14].
There are a lot of different methods for ZnO nanostructure preparation, like mechanochemical process [15,16], precipitation process
[17e19], solegel [20], solvothermal hydrothermal and microwave
techniques [21], emulsion [22] and microemulsion process [23].

* Corresponding author. Tel.: 20 1006425240; fax: 20 2 22747433.

E-mail address: eprimaf68@yahoo.com (M.A. El-Fattah).
http://dx.doi.org/10.1016/j.dyepig.2015.05.037
0143-7208/ 2015 Elsevier Ltd. All rights reserved.

Zinc oxide can be called a multifunctional material thanks to its

unique physical and chemical properties. Very prospective area of
usable nanocomposite systems is paint industry, the addition of a
small amount of suitable nanoparticles leads to positive affecting
several properties of the paint lm at once. The heat, scratch,
abrasion resistance and thermal stability properties of the coatings
improved signicantly as a function of ZnO NPs addition, is attributed to the interaction between the resin and large surface area of
ZnO NPs, which forming a stable nanocomposite [24,25]. ZnO NPs
are useful as antibacterial and antifungal agents when incorporated
into materials, such as surface coatings (paints), textiles, and plastics. The enhanced surface area of ZnO NPs allows a much stronger
interaction with bacteria [26]. This permits using a smaller amount
of ZnO for the same or improved biostatic behavior. The antifungal
behavior for a set of ZnO NPs based polyurethanes was envisaged
[27]. Present study refers to the synthesis of ZnO NPs via a direct
precipitation method, and study the effect of its addition into a two
component polyurethane coating system at different loading levels.
The performance behavior of the ZnO polyurethane nanocomposite
(ZPN) coating lms with respect antimicrobial activity, corrosion
resistance, physical and mechanical properties was investigated.
Polyurethane was selected because of its excellent durability as a
top coat.

A.M. El Saeed et al. / Dyes and Pigments 121 (2015) 282e289

2. Experimental
2.1. Materials
Commercial two components, glossy, acrylic aliphatic polyurethane nish produced by SIGMA COATINGS, Protective & Marine
Coatings was used as the polymer matrix. The typical characteristics of the polyurethane coating are as follows: volume solid is
55 2%, mass density is 1.2 g/cm3, and mixing ratio by volume of
base to hardener is 88:12 and its touch dry after 1 h. All materials
used during the research project were sourced internationally, or
from local companies, and were of pure grade quality.
2.2. Methods and techniques
2.2.1. Synthesis of zinc oxide nanoparticles (ZnO NPs)
ZnO NPs were prepared by a direct precipitation method followed by thermal decarbonation. Zn (NO3)2 6H2O, (NH4)2CO3,
ethanol, and de-ionized water was used as the starting materials to
prepare ZnO NPs. Zn (NO3)2 6H2O and (NH4)2CO3 were rstly dissolved in de-ionized water to form solutions with a 1 .5 and
2.25 mol/L concentration, respectively. The Zn (NO3)2 solution was
slowly dropped into the (NH4)2CO3 solution with vigorous stirring
at 40  C. The stirring was kept for 60 min, then; the precipitates
derived from the reaction were collected by ltration using a
micrometer lter paper and rinsed three times with de-ionized
water and ethanol respectively. The washed precipitates were
dried at 80  C. Finally, the precipitates were calcined at a temperature of 550  C for 2 h in the mufe furnace to obtain white nanosized ZnO particles [17].
2.3. Characterization study of ZnO NPs
2.3.1. Transmission electron microscope (TEM) analysis
Transmission electron microscopy (TEM) of ZnO NPs was conducted at an accelerated voltage of 200 KV electron microscopes
(JEM2100 LaB6, Japan). In the TEM the solid sample was dispersed
in ethanol solution using an ultrasonicator and then dropped on a
copper grid coated with carbon lm prior to inserting the samples
in the TEM column, the grid was vacuum dried for 15 min.
2.3.2. X-ray diffraction (XRD) analysis
X-ray diffraction (XRD) patterns of ZnO NPs were measured by
using a Panlytical X'pent PRO (Netherlands) with monochromated
CuKa radiation with scattering reections recorded for 2 angle
between 4 and 70 corresponding to d-spacing between 1.47 and
3.26 A . To conrm the resolution of the diffraction peaks with
standard reproducibility in 2-theta (0.005), the sample measurement was recorded by using monochromator and detector
which were used to generate focusing beam geometry and parallel
primary beam. The standard diffraction data were identied according to the International Centre for Diffraction Data (ICDD)
software with PDF-4 release 2011 database.
2.4. Preparation of ZnO polyurethane nanocomposite (ZPN) coating
lms
ZPN coating lms were prepared by dispersing different loadings of ZnO NPs in the polyurethane matrix. The rst step was
dispersed of ZnO NPs at different loading levels 0.1 to 2.0 wt.% by
continuously sonicated in xylene solvent by ultrasonic waves using
sonicator model Sonics & Materials, VCX-750, USA; with a frequency of 20 kHz equipped with a titanium probe with a
diameter 13 mm for 25 min. The second step was mixing the
dispersed ZnO NPs with polyurethane base for 30 min, by means of

283

stirring. The prepared samples were mixed with the correct ratio of
polyurethane hardener under continuous stirring. The resulting
solution was degassed for 15e20 min, to remove any dissolved
gases and any air bubbles formed during mixing of the solution. The
degassed solution was applied by conventional spraying on steel
panels. All efforts were made to maintain a uniform lm thickness
of 100 5 mm for evaluating the antimicrobial, anticorrosion,
physical and mechanical properties.
2.5. Scanning electron microscope (SEM) of ZPN
The cross-sectional morphologies of the ZPN coated lms were
measured by the environmental scanning electron microscope
model Quanta 250 FEG (eld Emission Gun), FEI company
Netherlands, attached to the EDX unit (Energy dispersive X-ray
analyses), with accelerating voltage 30 KV, magnication 14 up to
1,000,000 and resolutions for Gun. 1n. Before insertion into the
chamber, the sputter coating standard method was used for preparing specimens for observation in a scanning electron microscope by using EMITECH sputter coater model K550X England. The
SEM micrographs were operated at 20 KV.
2.6. Antimicrobial efciency of ZnO NPs
The antimicrobial activity of ZnO NPs was observed according to
Zheng and Zhu [28].
2.6.1. Preparation of the microbial suspension
The bacteria, Gram-negative (Escherichia coli RCMB) and Grampositive (Bacillus subtilis RCMB 010067) were inoculated into 75-ml
peptone liquid culture medium. Having been incubated in air bath
shaker (37  C, 130 RPM) for 12 h, the string entered the exponential
period of growth and the culture broth was diluted. The concentration of each tested bacteria was about 1.2  103 cells/ml.
2.6.2. Condition of incubation
The peptone culture plates were prepared, in which 0.25 ml
solution of microbe suspension was rst added and then 0.25 ml
solution of ZPN coatings with different ZnO NPs concentrations (0.1,
0.5, 1.0, 1.5 and 2.0 wt.%) were spread uniformly. Blank polyurethane without ZnO NPs was also prepared for comparison. All
the plates were incubated at 37  C for 20 h. Then the plates were
taken out and the inhibition rate was calculated. The inhibition rate
(h) was dened as

N1  N2
 100%
N1

where N1 and N2 mean the number of colonies on the plates before

and after inhibition, respectively.
2.7. Corrosion resistant property of ZPN coating lms
Cross line in the middle of each steel panel was made using a
cutter to permit the salt solution to penetrate the panel to examine
adherence of paint over the painted area. A salt spray (fog) cabinet
manufactured by CW Specialist equipment Ltd. model SF/450, England was utilized for evaluation, corrosion resistance of the
coating composites; coated panels being placed in the salt spray
cabinet at a temperature of 35  C, relative humidity 95% and test
solution 5% NaCl according to ASTM B117-03. The corrosion resistance was evaluated in terms of blistering, scribe failure and a degree of rusting, in relation to ASTM standards, i.e. ASTM D714-02,
D1654-00 and D610-01 respectively.

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2.8. Physical and mechanical resistance property of ZPN coating

lms

particles are approximately spherical and the average diameter of

the particles is 20.0 nm.

The surface tension of the ZPN coating lms was measured by

using contact angle measurement (ASTM D 7490-08). A range of
mechanical evaluations of the coated lms was undertaken according to appropriate ASTM standard test methods. The prepared
steel panels (ASTM D 609-00) were used for measuring i) the lm
coating thickness (ASTM D 1005-07); ii) adhesion cross hatch test
(ASTM D 3359-02) by Sheen cross hatch cutter Ref 750/1 mm, 6
teeth, UK; iii) the adhesion pull-off test (ASTM D 4541-02), was
measured by a hydraulic pull-off adhesion tester by using Paint test
equipment, England, in the range of (0e25) MPa; iv) exibility
bend test (ASTM D 522-08), was determined by using a inch
Mandrel bend tester from Sheen UK; v) the resistance to mechanical damage impact resistance (ASTM D2794-04) was measured
using tubular impact tester, model (806/40), Sheen UK; vi) hardness (ASTM D 3363-00) was determined by using Erichsen hardness test pencil, Model 318S, scratching force in the range of
(0.5e20) N and vii) abrasion resistance (ASTM D 4060e01) was
measured by using Taber Abraser model 5131, Taber Industries,
USA.

3.1.2. X-ray diffraction (XRD) of ZnO NPs

XRD patterns of ZnO NPs obtained by direct precipitation
method are shown in Fig. 2. The good agreement between the
standard diffraction peaks and the obtained peaks reveals that the
method of synthesis and purication of the ZnO NPs was performed
successfully. Diffraction peaks related to the impurities were not
observed in the XRD pattern, conrming the high purity of the
synthesized product. Furthermore, it could be seen that the
diffraction peaks shown in Fig. 2 were more intensive and narrower, implying a good crystalline nature of the synthesized ZnO
NPs. In addition, the broadening at the bottom of diffraction peaks
also denotes that the crystalline sizes were small and in good
agreement with the characteristic of nano-sized particles reported
in literature [17].

3. Results and discussion

3.1. Characterization of the prepared ZnO NPs
The structure of the obtained ZnO NPs was characterized by
transmission electron microscopy (TEM) and X-ray diffraction
(XRD).
3.1.1. Transmission electron microscope (TEM) of ZnO NPs
The transmission electron microscope image provides a unique
opportunity to directly visualize nano-particle morphology. Fig. 1
shows that the ZnO NPs powder is non-agglomerated and the

3.2. Morphology of the fractured surface of ZnO polyurethane

nanocomposite (ZPN) coating lms
Microstructure studies were carried out in order to detect voids
or agglomerates which can be formed through polymer composite
coating processing. SEM micrographs prepared from the fractured
surface of polyurethane coating contains ZnO NPs have been obtained as shown in Fig. 3. It clearly shows that the coating is uniform without any heterogeneity on the surface indication proper
dispersion of ZnO NPs. Such an even and uniform distribution of the
ZnO NPs in the matrix play important role in improving the mechanical performance of the composite lms. The gray colored regions indicate the bulk of the polyurethane polymer matrix and the
brighter regions indicate the distribution of ZnO NPs into the
polyurethane coating, and the number of bright particles increased
with the increasing ZnO NPs concentrations. The addition of the
ZnO NPs was successful up to 2.0 wt.%, where the bright particles

Fig. 1. TEM micrograph for ZnO NPs powder.

A.M. El Saeed et al. / Dyes and Pigments 121 (2015) 282e289

285

Fig. 2. X-ray diffraction patterns for the ZnO NPs powder.

Fig. 3. SEM images of ZPN coated lms containing ZnO NPs at different loading levels.

embedded in the polyurethane matrix exhibited uniform dispersion and homogenous distribution without any agglomeration.
Also, coating system with lower concentration of ZnO NPs (0.1wt.%)
show little change in the surface roughness and microstructure of
the coating as compared to the coating system with higher loading
level (2.0 wt.%), suggesting the improvement in the resistance to
crack start and propagation.

3.3. Antimicrobial property of ZnO polyurethane nanocomposite

(ZPN) coating lms
The antimicrobial effect of the ZnO NPs dispersed in the ZPN
coating against two bacteria was conducted by the peptone culture
medium. The results shown in Table 1 and Fig. 4 clearly indicate
that, the blank polyurethane does not show antibacterial activity.
On the other hand, it was also observed that the antibacterial activity for Gram-positive bacteria (B. subtilis) was much greater than

to Gram-negative bacteria (E. coli) at the loading level of ZnO NPs

less than 2.0 wt.%. However, at 2.0 wt.% ZnO NPs concentration
showed obvious inhibitory effects of the growth of both bacteria.
Concerning the mechanism of the antibacterial activity of ZnO NPs,

Table 1
The antimicrobial effect of the loading level of ZnO NPs wt.% on bacterial growth.
Coating design

Blank polyurethane (PU)

PU/ZnO NPs (0.1 wt.%)
PU/ZnO NPs (0.5 wt.%)
PU/ZnO NPs (1.0 wt.%)
PU/ZnO NPs (1.5 wt.%)
PU/ZnO NPs (2.0 wt.%)

Inhibition rate

h (%)

E. coli

B. subtilis

0
15
40
65
80
100

0
20
50
75
90
100

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3.5. Physical and mechanical behavior of ZnO polyurethane

nanocomposite (ZPN) coating lms
The physical and mechanical properties of ZPN coating lms are
shown in Tables 3 and 4 and Figs. 6 and 7.

Fig. 4. Inhibition rates for ZnO NPs against E. coli and B. subtilis.

several mechanisms have been proposed: (1) the release of Zn2

ions from the powder, (2) mechanical destruction of the cell
membrane caused by penetration of the nanoparticles, (3) active
oxygen generated from the powder, (4) the generation of hydrogen
peroxide (H2O2) from the surface of ZnO [29,30].
3.4. Anticorrosive properties of ZnO polyurethane nanocomposite
(ZPN) coating lms
Paints containing ZnO powder have long been utilized as anticorrosive coatings for metals. Therefore, the corrosion resistance
was also studied to investigate the effect of ZnO NPs on the protective performances of a polyurethane topcoat. Results of salt
spray laboratory tests after 500 h of exposure are shown in Table 2
and Fig. 5. It can be seen that the coating degradation after exposure to salt spray is more distinct in blank polyurethane than those
modied with ZnO NPs. Visual comparison of photographic reference standards used to evaluate the degree of blistering and the
percentage of the area rusted showed that, the blank polyurethane
surface shows the presence of blisters and a degree of rusting, this
indicates that the blank polyurethane coating has undergone
drastic chemical changes during exposure leading to the failure.
With the incorporation of ZnO NPs in the coating system, no such
defect was observed. The performance was better for the coating
modied with 2.0 wt.% ZnO NPs than for coating modied with
0.1 wt.% ZnO NPs. This improvement which be attributed to, ZnO
NPs at 2.0 wt.% loading level are well-dispersed in the polyurethane
coating, which restrict the diffusion of the corrosive electrolyte
through the ZPN coating lms acting as an effective barrier. It may
be also attributed to, the well-dispersed ZnO NPs having a large
surface area and the small size absorb more resin on its surface
which enhances the density of the ZPN coating lms, thereby
increasing the transport paths for the corrosive electrolyte to pass
through the coating and consequently reducing the corrosion
process [31e33].

3.5.1. Contact angle and wetting properties

Contact angles are commonly used to describe surface wettability.
The hydrophobic/hydrophilic character of the blank polyurethane
and ZPN coating lms was evaluated by measuring the contact angle
between the surface of the coating and drops of test liquid, using a
Tantec line of contact angle meter apparatus (Germany) and the
sessile drop technique. The test liquid was water (JT Baker, HPLC
grade). The obtained results are shown in Table 3 and Fig. 6. A contact
angle less than 90 (low contact angle) usually indicates that wetting
of the surface is very favorable, and the uid will spread over a large
area of the surface, a wettable surface may also be termed hydrophilic.
Contact angles greater than 90 (high contact angle) generally means
that wetting of the surface is unfavorable so the uid will minimize
contact with the surface and form a compact liquid droplet, a nonwettable surface may also be termed hydrophobic [34]. It is clear
that with an increase in the concentration of ZnO NPs in coated
sample, the contact angle (q) is gradually being increased and the
wettability decreased. The coated lm surface became a non-wettable
(hydrophobic-water repellent) surface at loading level, 1.0% of ZnO
NPs, which allows water droplets to run off the coating surface and
reducing the coating from corrosion damage. This improvement may
be attributed to the presence of an oxide layer on the solid surface
which can signicantly increase the contact angle.
3.5.2. Scratch hardness
The results with varying concentrations of ZnO NPs are presented in Table 4. It was observed that the blank polyurethane
coating is resistant to scratch hardness at loads of 3N, while polyurethane lled with ZnO NPs at loading level 1.5 wt.% showed
resistance to scratch at loads of 7N, beyond which the scratch
hardness was found to decrease. This improvement in hardness is
attributed to the strong bonding network between the functionalities of polyurethane and ZnO NPs along with their proper
dispersion, which provides more resistance to scratches causing
less deformation in the coating [24]. The decrease in the scratch
resistance at higher loading 2.0 wt.% may be attributed to the
interference of ZnO NPs with the crosslinking reaction between
polymer chains, resulting a relatively softer surface, and thereby
decreased scratch hardness.
3.5.3. Pull-off adhesion & resistance to mechanical damage (impact
resistance)
Both pull-off adhesion and impact were shown to improve with
the increased ZnO NPs content, this is a positive result can be
attributed to the reinforcement provided by the good dispersion
and high compatibility between polyurethane coating and ZnO NPs.

Table 2
Corrosion resistance performance of blank polyurethane and ZPN coating lms after 500 h of exposure in salt spray cabinet.
Coating design

Blistering
Size

Frequency

Blank polyurethane (PU)

PU/ZnO NPs (0.1 wt.%)
PU/ZnO NPs (0.5 wt.%)
PU/ZnO NPs (1.0 wt.%)
PU/ZnO NPs (1.5 wt.%)
PU/ZnO NPs (2.0 wt.%)

4
4
6
6
8
8

Medium dense
Medium
Medium dense
Medium
Medium
Few

Scribe failure rating no.

Rust grades

4
5
5
6
7
7

3
4
5
5
7
8

A.M. El Saeed et al. / Dyes and Pigments 121 (2015) 282e289

287

Fig. 5. Blank polyurethane and ZPN coating lms contain different loading levels of ZnO NPs after 500 h of salt spray exposure.

Table 3
Contact angle and wetting properties of blank polyurethane and ZPN coating lms.
Coating design

Contact angle (q)

Wetability and adhesiveness

Property

Blank polyurethane (PU)

PU/ZnO NPs (0.1 wt.%)
PU/ZnO NPs (0.5 wt.%)
PU/ZnO NPs (1.0 wt.%)
PU/ZnO NPs (1.5 wt.%)
PU/ZnO NPs (2.0 wt.%)

80
85
90
100
110
115

Good
Good
Neutral
Poor
Poor
Poor

Hydrophilic
Hydrophilic
Pinning
Hydrophobic
Hydrophobic
Hydrophobic

Table 4
Mechanical resistance performance of blank polyurethane and ZPN coating lms.
Coating design

Hardness
(N)

Pull-off adhesion
(MPa)

Impact (J)

Abrasion resistance
Weight loss (mg)/500 cycles

Blank polyurethane (PU)

PU/ZnO NPs (0.1 wt.%)
PU/ZnO NPs (0.5 wt.%)
PU/ZnO NPs (1.0 wt.%)
PU/ZnO NPs (1.5 wt.%)
PU/ZnO NPs (2.0 wt.%)

3
5
5
6
7
6

4
4
6
7
8
8

4
5
6
8
10
11

7.47
6.93
5.87
5.33
4.95
4.80

I.e. Increasing the ZnO NPs content, the interface between the
polyurethane and the ZnO NPs also increases.
3.5.4. Adhesion crosshatch and exibility (bend)
Based on these qualitative measurements, it can be stated that
all the lms showed reasonably good adhesion and exibility. In the
case of the cross ecut test, the edges of the cuts are completely
smooth without detachment of akes for all samples. And in the
case of the exibility (bend) test, there was no signicant difference
between blank polyurethane and ZPN coating lms.

Fig. 6. Contact angle measurements of blank polyurethane and ZPN coating lms at
different loading level of ZnO NPs.

3.5.5. Abrasion resistance

The Taber abrasion test was carried out to determine the abrasion resistance of ZPN coating lms. The weight loss as a function of
concentration of ZnO NPs is shown in Table 4. It is clear that with an

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Fig. 7. Mechanical tests of blank polyurethane and ZPN coating lms: a) adhesion crosshatch, b) adhesion pull-off, c) scratch resistance, d) impact resistance and e) abrasion
resistance.

increase in the concentration of ZnO NPs in coated sample, the

weight loss is gradually being reduced. This improvement may be
attributed to the incorporation of ZnO NPs into the polyurethane
coating changes the morphology of the coating due to enhanced
interaction of ZnO NPs with coating structure, as a result of which
coating seems to be more compact and less abraded as compared to
the coating without ZnO NPs. This compactness of coating goes on
increasing with an increase in concentration of ZnO NPs. This indicates that the interface surface interaction between ZnO NPs and
the base matrix providing strength against abrasive action.
4. Conclusions
Zinc oxide nanoparticles (ZnO NPs) with the average diameters
of 20 nm were obtained via a direct precipitation method. Perfect
dispersion of ZnO NPs conrmed by SEM, the ZnO NPs was uniformly dispersed and embedded in the two component polyurethane matrix when its concentration was max 20 g/l. It was
found that the ZnO NPs at 2.0 wt.% loading level, showed the
obvious inhibitory effect of the growth of both Gram-positive
bacteria and Gram-negative bacteria. It was also found that, the
ZnO NPs signicantly enhance the corrosion resistance, mechanical
resistance and reduce surface wettability of polyurethane coating,
and this improvement increases with increase ZnO NPs wt.%.
References
[1] Cho KS, Hong J-I, Chung CI. Effects of ZnO nano particles on thermal stabilization of polymers. Polym Eng Sci 2004;44(9):1702e6.
[2] Allen NS, Edge M, Ortega A, Sandoval G, Liauw CM, Verran J, et al. Degradation
and stabilization of polymers and coatings: nano versus pigmentary titania
particles. Polym Degrad Stab 2004;85(3):927e46.
[3] Zhou Shuxue, Wu Limin, Sun Jian, Shen Weidian. Effect of nanosilica on the
properties of polyester based polyurethane. J Appl Polym Sci 2003;88(1):
189e93.
[4] Fernando Ray. Nanomaterial technology applications in coatings. J Coat
Technol 2004;1(5):32e8.
[5] Zhou S, Wu L, Sun J, Shen W. The change of the properties of acrylic-based
polyurethane via addition of nano-silica. Prog Org Coat 2002;45(1):33e42.
[6] Jalili MM, Moradian S, Dastmalchian H, Karbasi A. Investigating the variations
in the properties of 2-pack polyurethane clear coat through separate incorporation of hydrophilic and hydrophobic nano-silica. Prog Org Coat
2007;59(1):81e7.
[7] Petrovi ZS, Cho YJ, Javni I, Magonov S, Yerina N, Schaefer DW, et al. Effect of
silica nanoparticles on the morphology of segmented polyurethanes. Polym J
2004;45(12):4285e95.
[8] Ashraf M, Saeed El, Abd El- Fattah M, Dardir MM. Synthesis and characterization of titanium oxide nanotubes and its performance in epoxy nanocomposite coating. Prog Org Coat 2015;78(January):83e9.
[9] Zheng J, Ozisik R, Siegel RW. Disruption of self-assembly and altered mechanical behavior in polyurethane/zinc oxide nanocomposites. Polym J
2005;46(24):10873e82.

[10] Ammala A, Hill AJ, Meakin P, Pas SJ, Turney TW. Degradation studies of
polyolens incorporating transparent nanoparticulate zinc oxide UV stabilizer. J Nanopart Res 2002;4(1e2):167e74.
[11] Brickweg LJ, Floryancic BR, Sapper ED, Fernando Rd H. Shear-induced 1-D
alignment of alumina nanoparticles in coatings. J Coat Technol 2007;4(1):
107e10.
[12] Dhoke SK, Khanna AS. Effect of nano-Fe2O3 particles on the corrosion behavior
of alkyd based waterborne coatings. Corros Sci 2009;51(1):6e20.
[13] Li Bin, Li Song-Mei, Liu Jian-Hua, Yu Mei. . The heat resistance of a polyurethane coating lled with modied nano-CaCO3. Appl Surf Sci
2014;315(10):241e6.
[14] Baer DR, Burrows PE, El-Azab Anter A. Enhancing coating functionality using
nanoscience and nanotechnology. Prog Org Coat 2003;47(3e4):342e56.
[15] Aghababazadeh R, Mazinani B, Mirhabibi A, Tamizifar M. ZnO nanoparticles
synthesized by mechanochemical processing. JPCS 2006;26(1):312e4.
[16] Stankovi
c A, Veselinovi
c Lj, Skapin SD, Markovi
c S, Uskokovi
c D. Controlled
mechanochemically assisted synthesis of ZnO nanopowders in the presence of
oxalic acid. J Mater Sci 2011;46(11):3716e24.
[17] Chun C, Liu P, Lu C. Synthesis and characterization of nano-sized ZnO powders
by direct precipitation method. Chem Eng 2008;144(3):509e13.
[18] Khoshhesab ZM, Sarfaraz M, Houshyar Z. Inuence of urea on precipitation of
zinc oxide nanostructures through chemical precipitation in ammonium
hydrogen carbonate solution. Synth React Inorg Met.-Org. Chem 2012;42(10):
1363e8.
[19] Lanje AS, Sharma SJ, Ningthoujam RS, Ahn JS, Pode RB. Low temperature
dielectric studies of zinc oxide (ZnO) nanoparticles prepared by precipitation
method. Adv Powder Technol 2013;24(1):331e5.
[20] Risti
c M, Musi
c S, Ivanda M, Popovi
c S. Solegel synthesis and characterization
of nanocrystalline ZnO powders. J Alloys Compd 2005;397(1e2):L1e4.
[21] DemYanets LN, Li LE, Uvarova TG. Zinc oxide: hydrothermal growth of nanoand bulk crystals and their luminescent properties. J Mater Sci 2006;41(5):
1439e44.
[22] Radzimska AK, Markiewicz E, Jesionowski T. Structural characterization of
ZnO particles obtained by the emulsion precipitation method. J Nanomate
2012;2012. Article ID 656353, http://dx.doi.org/10.1155/2012/656353.
[23] Li X, He G, Xiao G, Liu H, Wang M. Synthesis and morphology control of ZnO
nanostructures in microemulsions. J Colloid Interface Sci 2009;333(2):
465e73.
[24] Dhoke SK, Bhandari R, Khanna AS. Effect of nano-ZnO addition on the siliconemodied alkyd- based waterborne coatings on its mechanical and heat e
resistance properties. Prog Org Coat 2009;64(1):39e46.
[25] Chrissas K, Antoniadis G, Paraskevopoulos KM, Vassiliou A, Bikiaris DN.
Comparative study of the effect of different nanoparticles on the mechanical properties and thermal degradation mechanism of in situ prepared
poly (-caprolactone) nanocomposites. Compos Sci Technol 2007;67(10):
2165e74.
[26] Guo C, Zheng Z, Zhu Q, Wang X. Preparation and characterization of polyurethane/ZnO nanoparticle composite. Polym Plast Technol Eng 2007;46(12):
1161e6.
[27] Vlad S, Tanase C, Macocinschi D, Ciobanu C, Balaes T, Filip D, et al. Antifungal
behavior of polyurethane membrane with zinc oxide nanoparticles. Dig J
Nanomater Bios 2012;7(1):51e8.
[28] Zheng LY, Zhu JF. Study on antimicrobial activity of chitosan with different
molecular weights. Carbohydr Polym 2003;54(4):527e30.
[29] Heinlaan M, Ivask A, Blinova I, Dubourguier H, Kahru A. Toxicity of nanosized
and bulk ZnO, CuO and TiO2 to bacteria Vibrio scheri and crustaceans
Daphnia magna and Thamnocephalus platyurus. Chemosphere 2008;71(7):
1308e16.
[30] Brayner R, Ferrari-Iliou R, Brivois N, Djediat S, Benedetti MF, Fievet F. Toxicological impact studies based on Escherichia coli bacteria in ultrane ZnO
nanoparticles colloidal medium. Nano Lett 2006;6(4):866e70.

A.M. El Saeed et al. / Dyes and Pigments 121 (2015) 282e289

[31] Yang LH, Liu FC, Han EH. Effects of P/B on the properties of anticorrosive
coatings with different particle size. Prog Org Coat 2005;53(2):91e8.
[32] Kalendova A. Effects of particle sizes and shapes of zinc metal on the
properties of anticorrosive coatings. Prog Org Coat 2003;46(4):324e32.

289

[33] Shi Hongwei, Liu Fuchun, Han Enhou, Wei Yinghua. Effect of nano pigments on the
corrosion resistance of alkyd coatings. J Mater Sci Technol 2007;23(4):551e8.
[34] Yuan Y, Lee TR. Contact angle and wetting properties. Surf Sci Tech Springer
Ser Surf Sci 2013;51(Chapter 1):3e34.