Preparation and Characterization of Transparent ZnO/Polymethyl methacrylate

Nanocomposites
Sarla Sharma, Rishi Vyas, Subodh Srivastava, and Y. K. Vijay

Citation: AIP Conference Proceedings 1391, 627 (2011); doi: 10.1063/1.3643631

View online: http://dx.doi.org/10.1063/1.3643631
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 Preparation and Characterization of Transparent
ZnO/Polymethyl methacrylate Nanocomposites
Sarla Sharma1*, Rishi Vyas2, Subodh Srivastava1, Y. K. Vijay1
1
Thin films and Membrane Science Lab, Department of Physics, University of Rajasthan, Jaipur-302055, India.
2
Department of Physics, Malaviya National Institute of Technology, Jaipur-302017, India
(Corresponding author e-mail : mail2sarlasharma@gmail.com)

Abstract. Transparent ZnO/PMMA (Poly methyl methacrylate) nanocomposites with high-UV shielding efficiency
were reported in this paper. The zinc oxide (ZnO) nanoparticles were synthesized chemically via the homogeneous
precipitation method using different concentration of capping agent (2-Mercaptoethanol). The structural properties of the
as-prepared ZnO nanoparticles were characterized by X-ray diffractometer (XRD) and transmission electron microscopy
(TEM) measurements. The transparent ZnO/PMMA nanocomposites were subsequently prepared by dispersing as-
prepared ZnO nanoparticles in PMMA via solution mixing and then solution casting method. The optical properties of
ZnO/PMMA nanocomposites, namely visible light transparency and UV light shielding efficiency, were studied using an
ultraviolet–visible (UV–Vis) spectrophotometer. The optical properties of the as-obtained nanocomposites were shown
to depend on ZnO particle size. The nanocomposite containing small sizes ZnO nanoparticles with an average particle
size of (~10 nm) possessed the most optimal optical properties, namely high-visible light transparency and high-UV light
shielding efficiency, which are desirable for many important applications.
Keywords: Nanocomposite, TEM, UV-Vis.
PACS: 78.67.Sc, 68.37.Lp, 07.60.Rd

INTRODUCTION
In recent past, there have been many a reports on
the LED applications using inorganic particle/polymer
nanocomposite to enhance the structural and optical
properties of packaging material. Packaging materials
for ultraviolet light-based white light emitting diodes
(UV-WLED) are required to posses high-visible light
transparency and high-ultraviolet resistance. The
modifications in the structural design of the packaging
material may lead to production of superior packaging
materials for LED applications.
It is known that inorganic UV absorbent can
enhance UV light resistance via UV light shielding.
ZnO is also a UV absorbent and the ZnO/PMMA
nanocomposite exhibit transparency due to a little
difference in their refractive index which use to be a
critical parameter for the selection of proper filler in
packaging material for LED applications [1].
In the present paper, the ZnO nanoparticles of
different particle sizes were prepared which were used
to obtain ZnO/PMMA nanocomposites. These
nanocomposites were then tested for their UV light
transparency and UV shielding efficiency.
EXPERIMENTAL
Zinc acetate dihydrate (Zn(CH3COO)2.2H2O)
solution in dimethylsulpoxide (DMSO) and potassium
hydroxide (KOH) solution in ethanol were used to
synthesize ZnO in the presence of 2-mercaptoetahnol
as a capping agent. Zinc acetate dehydrate solution
was prepared in 20 ml DMSO and stirred till it formed
a clear solution. Potassium hydroxide solution in
ethanol was added drop-wise to the above solution till
the solution turned milky white under continuous slow
stirring condition. The required concentration of
intended capping agent- thioglycerol (2-
mercaptoethanol) was added to it and the resultant
solution was stirred till the milky white solution
appeared. This whole process was carried out at room
temperature. The obtained precipitate was separated by
filtration and then washed at least 3-4 times with
methanol. The precipitate dried in air and vacuum at
room temperature. Different concentrations of capping
agent were used to achieve the variation in particle
size of ZnO. Using above method three type of
specimen were prepared: ZnO nanoparticles

Optics: Phenomena, Materials, Devices, and Characterization

AIP Conf. Proc. 1391, 627-629 (2011); doi: 10.1063/1.3643631
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 synthesized without using 2- mercaptoethanol (Z1),
ZnO nanoparticles synthesized using 0.24 ml
mercaptoethanol (Z2) and ZnO nanoparticles
synthesized using 0.5 ml mercaptoethanol (Z3). All
the chemicals used in this process were purchased
from the leading suppliers and used without further
purification.
The ZnO/PMMA nanocomposite films were
prepared by using solution cast method. ZnO
nanoparticles (5 wt. %) were dispersed in 20 ml of
PMMA solution where dichloromethane was used as
solvent [2]. The samples were named in the similar
way using the concentration of 2-mercaptoethanol as
reference: ZnO/PMMA nanocomposite films
synthesized using Z1 (ZP1), ZnO/PMMA
nanocomposite films synthesized using Z2 (ZP2) and FIGURE 1. XRD pattern for as prepared ZnO
nanoparticles (a) Z1 (b) Z2 (c) Z3
ZnO/PMMA nanocomposite films synthesized using
Z3 (ZP3). The ZnO/PMMA composite prepared using
bulk ZnO is named as ZP4.
The structural properties were studied by XRD and
XRD patterns were recorded on PANalytical's X'Pert
PRO Diffractometer with monochromatic Cu-Kα
(λ=1.54Ǻ) radiation. The optical properties of the
ZnO/PMMA nanocomposite films were studied using
Hitachi-3300 double beam UV-Vis spectrophotometer
in range from 300 nm to 600 nm and TEM
measurements were carried out using Technai G20-S-
TWIN (200kV).

RESULTS AND CONCLUSION

(a) X-ray Diffraction and TEM Studies

FIGURE 2. XRD pattern for as prepared ZnO
Fig. 1 shows the XRD patterns of the ZnO nanocomposite (ZP3)
nanoparticles prepared by using different
concentration of capping agent. All the diffraction TABLE 1. Comparison of particles sizes estimated
peaks for Z1, Z2 and Z3 could be indexed to pure from XRD and TEM
wurtzite phase of ZnO [3]. Particle size of these ZnO Size of ZnO Size of ZnO
Sample
nanoparticles is estimated using Scherer’s relation [4] particles by XRD particles by
Name
(nm) TEM (nm)
and tabulated in table 1 which shows a continuous
Z1 23 ± 3 25 ± 3
decrease in particle size with increasing concentration
of 2-mercaptoethanol. This is in agreement with Z2 11 ± 2 13 ± 2
reports from Chimanpure et. al [5] and Singh et. al [6]. Z3 7±2 10 ± 2
The XRD pattern for ZnO/PMMA nanocomposite
films shows the formation of nanocomposites and The TEM micrographs of the ZnO/PMMA
could be indexed in similar fashion. One of the nanocomposite films are given in fig. 3(a), 3(b) and
3(c) which are for specimens, ZP3, ZP2 and ZP1
patterns is shown in fig. 2 for specimen ZP3. The
respectively. The figure 3(d) is for ZnO/PMMA
pattern shows a hump at 2θ ≈ 110 which is the composite (ZP4). TEM analysis of ZnO nanoparticles
characteristic peak of PMMA [7] whereas the other also reveals the formation of hexagonal ZnO.
peaks appearing are indexed to pure wurtzite phase of
ZnO.

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 The particle sizes for specimen Z1, Z2 and
Z3obtained from XRD and TEM is given in table 1
which show a good agreement.
FIGURE 3. TEM images of ZnO nanocomposite
films (a) ZP3 (b) ZP2 (c) ZP1 (d) ZP4.
(B) UV-VIS STUDIES
The typical absorption curves are shown in fig. 4
for ZP1, ZP2, ZP3 and ZP4. From absorption
spectroscopy, it is found that all the nanocomposite
films lead to blue shift in absorption band from 378
nm to 342 nm. This blue shift in the absorption band
indicates the presence of smaller ZnO nanoparticles in
the nanocomposite films. It was also seen from the
absorption curves that as the particle size was
deceasing in ZnO/PMMA nanocomposites, the UV
absorption as well as the visible transparency was
increasing. This supports ZnO/PMMA nanocomposite
as a candid packaging material for LED applications
[1].
FIGURE 4. UV-Vis spectrum of ZnO nanocomposite
films (a) ZP4 (b) ZP1 (c) ZP2 (d) ZP3.
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CONCLUSION
This paper reports on the high UV-shielding
efficiency and high visible transparency of
ZnO/PMMA nanocomposites and proposes them to be
a candid material for LED packaging. Different sized
ZnO nanoparticles were prepared and then dispersed in
PMMA matrix to study the optical properties. From
UV-Vis measurements a blue shift in absorption was
obtained due to the presence of smaller particles in
PMMA matrix. It is found that the smaller ZnO
nanoparticles in PMMA matrix lead to high visible
transparency and high UV shielding efficiency.
ACKNOWLEDGMENT
The authors are thankful to IUAC New Delhi for
the financial support to carry out this work.
REFERENCES
1. Y. Q. Li, S. Y. Fu, Y. W. Mai, Polymer 47, 2127-2132,
2006.
2. K. Awasthi, V. Kulshrestha, B. Tripathi, , N.K. Acharya,
M. Singh and Y. K. Vijay, Eur. Polym. J. 42, 883-887,
2006
3. Y.Z. Lv, Y.H. Zhang, C.P. Li, L.R. Ren, L. Guo, H.B.
Xu, L. Ding, C. L. Yang, W.K. Ge, S.H. Yang, J. Lumin.
122-123, 816-818, 2007.
4. B.D.Cullity, Elements of X-ray Diffraction, Addition-
Wesley, Reading, MA, 1978.
5. J.Chimanpure , S. Ashtaputre , S. Marathe , N.
Hebalkar, S. Kharrazi, R. Pasricha, S.K.Kulkarni,
Metal-Organic and Nano- Metal Chemistry 36, 65-69,
2006.
6. A.K. Singh, V. Viswanath, V.C. Janu, J. Lumi,. 129,
874-878, 2009.
7. S. Agarwal, S. Shrivastava, S. Kumar, S.S. Sharma,
B.Tripathi, M. Singh, Y.K. Vijay, Bull. Mater. Sci. 32(6),
569-573, 2009.