Radiation Physics and Chemistry 97 (2014) 212216

Contents lists available at ScienceDirect

Radiation Physics and Chemistry

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

Structural, optical and thermal properties of PVA/CdS nanocomposites

synthesized by radiolytic method
Alireza Kharazmi n, Elias Saion, Nastaran Faraji, Roslina Mat Hussin,
W. Mahmood Mat Yunus
Physics Department, Faculty of Science, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia

H I G H L I G H T S

CdS/PVA nanocomposite was synthesized by radiolytic method from 10 to 40 kGy doses.

The structure of nanocomposite and the effect of dose on structure were investigated by X-ray powder diffraction.

The morphology of nanoparticles and the effect of dose on nanoparticles were observed by transmission electron microscope.

The optical properties of nanocomposite and the effect of radiation were studied by UVvisible spectroscopy and uorescence spectroscopy.

The thermal properties of nanocomposite and the effect of dose were investigated by the transient hot wire method.

art ic l e i nf o a b s t r a c t

Article history: Monodispersed spherical CdS nanoparticles stabilized in PVA solution were synthesized by the gamma
Received 17 July 2013 radiolytic method and found the average particle size increased from 12 to 13 nm with the increment of
Accepted 5 December 2013 dose from 10 to 40 kGy. The XRD results show that it has crystalline planes of cubic structure with crystal
Available online 17 December 2013
lattice parameter of 5.832 . The optical reectance revealed a band-edge of CdS nanoparticles at about
Keywords: 475 nm and the reectance wavelength red shifted with increasing dose due to increasing particle size.
CdS nanoparticles The thermal conductivity of CdS/PVA nanocomposites measured by the transient hot wire method that
CdS/PVA nanocomposites revealed a decrement of the thermal conductivity with an increase of dose caused by effect of radiation
Radiolytic synthesis on crystallinity of the polymer structure.
Thermal conductivity
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Nanocomposites are referred to as the combination of two or more
different materials forming a blend to have the best properties of the
components in which at least one of them is in the nanoscale
dimension usually less than 100 nm (Twardowski, 2007). They are
one of the most attractive topics owing to their many optical and
optoelectronic applications such as solar cells (Huynh et al., 2002; Ong
and Levitsky, 2010), transistors (Muccini, 2006), light emitting diodes
(Rogach et al., 2008) and biological imaging (Akerman et al., 2002; Nie
et al., 2007). The inorganic (semiconductor) and organic (polymer)
nanocomposites have gained a great deal of interest since polymers as
a host provides long term stability, exibility and processability
coupled with the functional tunability and control growth of nano-
particles; in addition, nanosized particles enhance their optoelectronic
properties, allowing coupling between mechanical and optoelectronic
properties, for future devices. (Antolini et al., 2012; Elashmawi et al.,
2009; Kharazmi et al., 2013; Wang et al., 2007). Hence, the
n
Corresponding author. Tel.: 60 12 2110976.
E-mail address: kharazmi.alireza@hotmail.com (A. Kharazmi).
incorporation of these phases leads to possess and enhance the useful
properties such as light weight and good mobility of polymers in
addition to high strength, heat stability and chemical resistance of
inorganic materials (Khanna et al., 2005; Salavati-Niasari et al., 2009;
Shao et al., 2003).
Among inorganic semiconductors, cadmium sulde (CdS) nano-
particles as one the most important IIVI semiconducting nanoma-
terials have been investigated by many researchers, attributable to
their promising potential in optics, electronic and optoelectronic
applications (Cao et al., 2010; Peng et al., 1997; Venkatram et al.,
2006). The modication of the physical properties is an important
key to improve the performance of these materials; therefore,
choosing a polymer as capping and blending component can be
signicant in which the polymer does not change the inherit
characteristics of the inorganic phase (Chahal et al., 2012). The poly
(vinyl alcohol) (PVA) is considered as a good choice due to wide
spectral range of optical transparency and lack of sensitivity to higher
temperatures which can help in fabrication of useful devices in
various environmental conditions (Kityk et al., 1997).
The optical and thermal properties are considered as two major
characteristics in many applications of devices. The optical properties
of CdS/PVA nanocomposites have been investigated by many

0969-806X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.radphyschem.2013.12.003
 A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212216 213

researchers (Antolini et al., 2012; Cao et al., 2010; Elashmawi et al.,

2009; Khanna et al., 2005; Lai et al., 2009; Li et al., 2003; Liu et al.,
2006; Salavati-Niasari et al., 2009; Wang et al., 2007). Nevertheless,
to the best of our knowledge there is no report on optoelectronic-
thermal properties of CdS/PVA nanocomposites. Indeed, the thermal
conductivity is considered as the most complex characteristic among
the major physical properties in many applications (Kleinstreuer and
Feng, 2011). Considerable research in the last decade have been
devoted to study the thermal conductivity measurement at the
steady-state conditions which are used to imply enhanced energy
transport capabilities (Trisaksri and Wongwises, 2007). The transient
hot wire (THW) method is found to be the most accurate, reliable and
robust technique for measuring the thermal conductivity of uids
and solids (Vadasz, 2010). Moreover, the most attractive advantages
of this method are its capacity for, experimentally, eliminating the
error due to natural convection (Paul et al., 2010) in addition to a very
fast measurement, simple apparatus set up, easy implementation and
low cost compared to other techniques (Kleinstreuer and Feng, 2011).
Over the decade, many data on thermal conductivity have been
Fig. 1. The schematic for principle of thermal conductivity measurement.
gathered by researchers which reveal the enhancement in thermal
conductivity of liquids contained nanoparticles such as alumina
(Al2O3), titanium oxide (TiO2) and copper oxide (CuO) (Wang et al., apparatus probe was then securely placed in the tube and the
1999; Yoo et al., 2007). thermal conductivity measurement of the sample was taken. The
In this article, we report the structural, optical, and thermal theoretical aspect of this measurement in detail can be found in
properties of the CdS/PVA nanocomposites synthesized by gamma literature (Kleinstreuer and Feng, 2011).
irradiation method in a single step at room temperature.

3. Results and discussion

2. Materials and methods
The formation of CdS nanoparticles in the PVA solution can be
CdS nanoparticles stabilized in PVA solution was synthesized explained by means of combination of cadmium and sulfur ions.
by the gamma radiolytic method. 5-wt% PVA solution was pre- Indeed, the interaction of gamma rays with water causes hydrated

pared in 400 ml deionized water at the temperature of 80 1 by electrons eaq , hydroxyl radical (OHd) and hydrogen radical (Hd)
stirring for 2 hours. The solution was divided equally into four by radiolysis of water according to Eq. (1) (Singh et al., 2011).
different beakers before adding 10  2 M of Cd(NO3)2 and Na2S2O3 In aqueous solution, radiation decomposes Na2S2O3 and form the
into each beaker. The solution samples were bubbled with nitro- sulfur (S  2) ions (Liu et al., 2006). Formerly, the cadmium ions
gen gas for 2 hours while stirring. The samples were irradiated by (Cd2 ) were formed by dissolving the cadmium nitrate in the
gamma rays at doses from 10 to 40 kGy. solution. Therefore, the sulfur ions coupled with cadmium ions
The Philip X-ray diffractometer (XRD) was used to determine form the CdS nanoparticles. The reaction of this formation can be
the crystalline structure of CdS nanoparticles at the diffraction described as in the following reactions (Liu et al., 2006):
angle 2 range of 101601 with copper K radiation at 1.5418 rays
wavelengths. The morphology of CdS nanoparticles was observed

H2 O - eaq ; H ; H3 O  ; H
; OH
; H2 ; H2 O2 1
by Transmission Electron Microscopy (TEM) (JEOL 2010F UHR)
operated at an accelerating voltage of 20 kV. The optical reec-

Na2 S2 O3 -eaq S2 O3 2  2
tance spectra were collected by a UV-Visible spectrometer (Shi-
madzu-UV1650PC) in the wavelength range of 475 to 725 nm, and S2 O3 2  eaq

-S  SO3 2  3
the uorescence spectra as a function of emission wavelength
were recorded by a spectrouorometer (Shimadzu, RF-5301PC). S  eaq

-S2  4
The Decagon devices KD2 Thermal analyzer was used to
measure the thermal conductivity of the CdS/PVA nanocompo- 2
sites. The schematic diagram of the thermal conductivity measure- Cd S2  -CdS 5
ment is shown in Fig. 1. This apparatus has 5% accuracy over the
CdS CdS-CdS2 6
5 to 40 1C temperature range, and also meets the standards of both
ASTM D5334 and IEEE 442-1981. The portable device uses the
CdS CdSn -CdSn 1 7
transient line heat source to determine the thermal properties.
It basically comprises a handheld readout unit with a single-
needle sensor. The sensor was inserted into the specimen that In the nal term, the used polymer (PVA) as stabilizer prevents
works as both heat source and thermometer. A single reading took the agglomeration of CdS nanoparticles into larger particles.
2 minutes. The probe was heated for 30 seconds by a known Fig. 2 shows the X-ray diffraction pattern of CdS/PVA nano-
amount of current and the rest time was to ensure temperature composites synthesized at doses from 10 to 40 kGy showing the
stability. Besides, the probe also contains a thermistor which structural characteristic of CdS nanoparticles conforming CdS
measures the changes in temperature while the microprocessor nanoparticles formation. The rst observed peak at 19.51 is
stores the data. At the end of data collection, the thermal assigned to the crystalline PVA structure (Faraji et al., 2012). The
conductivity of the sample was computed by the temperature observed peaks at 2 values of 26.431, 31.811, 43.761 and 51.931 are
differences versus time data. Due to the constant temperature, perfectly matched with the (111), (200), (220), and (311), respec-
room temperature, the sample was placed inside a test-tube. The tively crystalline planes of the cubic structure of CdS (ICDD PDF
214 A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212216

00-065-2887) with crystal lattice parameters of 5.832 and
198.6 3 volume cell.
Figs. 3 and 4 show the TEM image and size distribution of CdS
nanoparticles synthesized at 10 and 40 kGy doses, respectively.
The Gaussian curve is tted to the results. The results demonstrate
a uniform and homogenous distribution of spherical CdS nano-
particles within the PVA. The size distribution diagrams illustrate
Fig. 2. XRD pattern of CdS/PVA nanocomposites irradiated from 10 to 40 kGy doses.
that the size of CdS nanoparticles is varied from 8 to 22 nm.
In addition, the average size of nanoparticles is increasing from 12
to 13 nm while the dose is increased from 10 to 40 kGy. The height
of the tted Gaussian curve is decreased from 33.65 to 27.92.
In contrast, the full width at half maximum (FWHM) is increased
from 3.61 to 5.43; therefore, the size and size distribution of CdS
nanoparticles are increased while dose increases.
Fig. 5 shows the optical reectance as a function of wavelength
for CdS/PVA nanocomposites. The reectivity of CdS/PVA nano-
composites is decreased by increasing dose due to the enhance-
ment in distribution of CdS nanoparticles. The observed band-edge
of CdS/PVA nanocomposites is varied from 475 to 480 nm which is
blue shifted compared to the bulk CdS (512 nm) because of the
size effect (Wang et al., 2007). Thus, the size of CdS nanoparticles
is increased by increasing doses and this increment is not very
signicant.
The uorescence spectra of CdS/PVA nanocomposites are
shown in Fig. 6. The results show sharp peaks centered at the
wavelength of 470 nm for all samples and indicates a red shifted
with respect to the emission wavelength of bulk CdS (515 nm)
(Lai et al., 2009). These peaks were assigned to the band to band
transition or band-edge recombination (Kharazmi et al., 2013). The
peaks are shifted toward higher wavelength slightly because of
decreasing band gap as the particle size increased slightly.
Furthermore, the increasing in the intensity and broadening of
the peaks from lower doses up to 40 kGy indicates the increment

Fig. 3. TEM image and size distribution diagram of CdS nanoparticles at 10 kGy radiation dose.

Fig. 4. TEM image and size distribution diagram of CdS nanoparticles at 40 kGy radiation dose.
 A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212216
Fig. 5. Reectance spectra of CdS/PVA nanocomposites irradiated from 10 to
40 kGy doses.
Fig. 6. Fluorescence spectra of CdS/PVA nanocomposites irradiated from 10 to
40 kGy doses.
Fig. 7. The value of thermal conductivity as a function of dose.
of size distribution and distribution of nanoparticles at higher
doses.
Fig. 7 shows the thermal conductivity of CdS/PVA nanocomposites
as a function of absorbed dose from 0 to 40 kGy. The result illustrates
that with the addition of CdS nanoparticles the value of thermal
215
conductivity is increased. However, the thermal conductivity is
decreased due to modication of PVA structure while dose increases.
In principle the heat is transported by phonons (Choy et al.,
1985) and the thermal conductivity (k) can be expressed by the
Eq. (2) (Mergenthaler et al., 1992)
1
k Cp l 8
3
where is density, C p is the specic heat at constant pressure, is
the phonon velocity and l is the phonon mean free path. The
changes in either crystallinity or polymer chain can affect the
phonon mean free path (l) and so thermal conductivity, as
reported earlier (George et al., 2001; Gutirrez-Jurez et al.,
1996). In this work, the CdS/PVA nanocomposites show higher
value of thermal conductivity compared to the PVA solution due to
the Brownian motion, convection, and heat diffusion in the
presence of nanoparticles (Raykar and Singh, 2011). The reduction
of the thermal conductivity from 10 to 40 kGy doses may be
explained by means of the breakdown of PVA structure upon
gamma irradiation. Indeed, the PVA undergoes bond scission upon
gamma irradiation with increasing dose which leads to decrement
in crystallinity and length of the polymer chain (Bhat et al., 2005).
4. Conclusion
In conclusion, CdS/PVA nanocomposites were synthesized by
the gamma radiolytic method and their structural, optical, and
thermal properties were studied. The XRD conrmed the forma-
tion of cubic crystalline CdS with crystal lattice parameters of
5.832 and 198.6 3 volume cell. The average particle size was
increased from 12 to 13 nm with increasing dose from 10 to
40 kGy. The optical reectance revealed a band-edge of CdS
nanoparticles at about 475 nm, and the reectance wavelength
red shifted with increasing dose due to increasing particle size.
The high uorescence characteristic was observed for CdS/PVA
nanocomposites. The thermal conductivity of CdS/PVA nanocom-
posites measured by the transient hot wire method revealed a
decrement of the thermal conductivity with the increase of dose
caused by radiation effects on crystallinity of the polymer struc-
ture. In other words, thermal conductivity was decreased with
increasing dose due to the phonon mean free path reduction
caused by the bond scission of PVA chains. The thermal conduc-
tivity of the nanocomposites is higher than that of PVA solution
due to the Brownian motion.
Acknowledgments
This study was supported by the Ministry of Education of
Malaysia under the FRGS and RUG grants. The authors would also
like to thank the staff of the Faculty of Science, Universiti Putra
Malaysia and the Nuclear Agency of Malaysia for contributing to
this study.
References
Akerman, M.E., Chan, W.C., Laakkonen, P., Bhatia, S.N., Ruoslahti, E., 2002.
Nanocrystal targeting in vivo. Proc. Natl. Acad. Sci. USA 99, 1261712621.
Antolini, F., Burresi, E., Stroea, L., Morandi, V., Ortolani, L., Accorsi, G., Blosi, M., 2012.
Time and temperature dependence of CdS nanoparticles grown in a
polystyrene matrix. J. Nanomater. 2012, 111.
Bhat, N.V., Nate, M.M., Kurup, M.B., Bambole, V.A., Sabharwal, S., 2005. Effect of
-radiation on the structure and morphology of polyvinyl alcohol lms. Nucl.
Instrum. Methods Phys. Res. Sect. B 237, 585592.
Cao, A., Liu, Z., Chu, S., Wu, M., Ye, Z., Cai, Z., Chang, Y., Wang, S., Gong, Q., Liu, Y.,
2010. A facile one-step method to produce GrapheneCdS quantum dot
nanocomposites as promising optoelectronic materials. Adv. Mater. 22,
103106.
216 A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212216
Chahal, R.P., Mahendia, S., Tomar, A., Kumar, S., 2012. -Irradiated PVA/Ag
nanocomposite lms: materials for optical applications. J. Alloy. Compd. 538,
212219.
Choy, C.L., Wong, S.P., Young, K., 1985. Model calculation of the thermal conductiv-
ity of polymer crystals. J. Polym. Sci. Part B: Polym. Phys. 23, 14951504.
Elashmawi, I.S., Hakeem, N.A., Selim, M.S., 2009. Optimization and spectroscopic
studies of CdS/poly(vinyl alcohol) nanocomposites. Mater. Chem. Phys. 115,
132135.
Faraji, N., Younus, W.M.M., Kharazmi, A., Saion, E., Shahmiri, M., Tamchek, N., 2012.
Synthesis, characterization and nonlinear optical properties of silver/PVA
nanocomposites. J. Europ. Opt. Soc. Rap. Public. 7, 12040(1)12040(7).
George, N.A., Vallabhan, C., Nampoori, V., George, A., Radhakrishnan, P., 2001.
Photoacoustic evaluation of the thermal effusivity in the isotropic phase of
certain comb-shaped polymers. J. Phys. Condens. Matter 13, 365371.
Gutirrez-Jurez, G., Zelaya-Angel, O., Alvarado-Gil, J.J., Vargas, H., Pastore, H.d.O.,
Barone, J.S., Hernandez-Velez, M., Baos, L., 1996. Thermal, structural and
optical properties of {CdS}Na86X composites. J. Chem. Soc. Faraday Trans. 92,
26512657.
Huynh, W.U., Dittmer, J.J., Alivisatos, A.P., 2002. Hybrid nanorod-polymer solar cells.
Science 295, 24252427.
Khanna, P.K., Gokhale, R.R., Subbarao, V.V.V.S., Singh, N., Jun, K.W., Das, B.K., 2005.
Synthesis and optical properties of CdS/PVA nanocomposites. Mater. Chem.
Phys. 94, 454459.
Kharazmi, A., Saion, E., Faraji, N., Soltani, N., Dehzangi, A., 2013. Optical properties of
CdS/PVA nanocomposite lms synthesized using the Gamma-irradiation-
induced method. Chin. Phys. Lett. 30, 057803(1)057803(5).
Kityk, I., Kasperczyk, J., Sahraoui, B., Yasinskii, M., Holan, B., 1997. Low temperature
anomalies in polyvinyl alcohol photopolymers. Polymer 38, 48034806.
Kleinstreuer, C., Feng, Y., 2011. Experimental and theoretical studies of nanouid
thermal conductivity enhancement: a review. Nanoscale Res. Lett. 6, 113.
Lai, S., Chang, X., Fu, C., 2009. Cadmium sulde quantum dots modied by chitosan
as uorescence probe for copper (II) ion determination. Microchim. Acta 165,
3944.
Li, H.-l., Zhu, Y.-c., Chen, S.-g., Palchik, O., Xiong, J.-p., Koltypin, Y., Gofer, Y.,
Gedanken, A., 2003. A novel ultrasound-assisted approach to the synthesis of
CdSe and CdS nanoparticles. J. Solid State Chem. 172, 102110.
Liu, W., He, W., Zhang, Z., Zheng, C., Li, J., Jiang, H., Ge, X., Liu, H., 2006. Fabrication of
CdS nanorods in inverse microemulsion using HEC as a template by a
convenient -irradiation technique. J. Cryst. Growth 290, 592596.
Mergenthaler, D., Pietralla, M., Roy, S., Kilian, H., 1992. Thermal conductivity in
ultraoriented polyethylene. Macromolecules 25, 35003502.
Muccini, M., 2006. A bright future for organic eld-effect transistors. Nat. Mater. 5,
605613.
Nie, S., Xing, Y., Kim, G.J., Simons, J.W., 2007. Nanotechnology applications in
cancer. Annu. Rev. Biomed. Eng. 9, 257288.
Ong, P.-L., Levitsky, I.A., 2010. Organic/IV, IIIV semiconductor hybrid solar cells.
Energies 3, 313334.
Paul, G., Chopkar, M., Manna, I., Das, P., 2010. Techniques for measuring the thermal
conductivity of nanouids: a review. Renew. Sustainable Energy Rev. 14,
19131924.
Peng, X., Schlamp, M.C., Kadavanich, A.V., Alivisatos, A., 1997. Epitaxial growth of
highly luminescent CdSe/CdS core/shell nanocrystals with photostability and
electronic accessibility. J. Am. Chem. Soc. 119, 70197029.
Raykar, V.S., Singh, A.K., 2011. Photoacoustic method for measurement of thermal
effusivity of Fe3O4 nanouid. J. Thermophys. 2011, 15.
Rogach, A.L., Gaponik, N., Lupton, J.M., Bertoni, C., Gallardo, D.E., Dunn, S., Li Pira, N.,
Paderi, M., Repetto, P., Romanov, S.G., 2008. Lightemitting diodes with
semiconductor nanocrystals. Angew. Chem. Int. Ed. 47, 65386549.
Salavati-Niasari, M., Loghman-Estarki, M.R., Davar, F., 2009. Synthesis, thermal
stability and photoluminescence of new cadmium sulde/organic composite
hollow sphere nanostructures. Inorg. Chim. Acta 362, 36773683.
Shao, C., Kim, H.-Y., Gong, J., Ding, B., Lee, D.-R., Park, S.-J., 2003. Fiber mats of poly
(vinyl alcohol)/silica composite via electrospinning. Mater. Lett. 57, 15791584.
Singh, S., Rath, M., Singh, A., Mukherjee, T., Jayakumar, O., Tyagi, A., Sarkar, S., 2011.
CdSe nanoparticles grown via radiolytic methods in aqueous solutions. Radiat.
Phys. Chem. 80, 736741.
Trisaksri, V., Wongwises, S., 2007. Critical review of heat transfer characteristics of
nanouids. Renew. Sustainable Energy Rev. 11, 512523.
Twardowski, T.E., 2007. Introduction to nanocomposite materials: properties,
processing, characterization. Destech Publications, Lancaster.
Vadasz, P., 2010. Rendering the transient hot wire experimental method for thermal
conductivity estimation to two-phase systemstheoretical leading order
results. J. Heat Transfer. 132, 081601.
Venkatram, N., Kumar, R., Narayana Rao, D., 2006. Nonlinear absorption and
scattering properties of cadmium sulphide nanocrystals with its application
as a potential optical limiter. J. Appl. Phys. 100, 074309(1)074309(8).
Wang, H., Chen, Z., Fang, P., Wang, S., 2007. Synthesis, characterization and optical
properties of hybridized CdS-PVA nanocomposites. Mater. Chem. Phys. 106,
443446.
Wang, X., Xu, X., Choi, S.U.S., 1999. Thermal conductivity of nanoparticle-uid
mixture. J. Thermophys. Heat Transf. 13, 474480.
Yoo, D.-H., Hong, K., Yang, H.-S., 2007. Study of thermal conductivity of nanouids
for the application of heat transfer uids. Thermochim. Acta 455, 6669.