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Radiation Physics and Chemistry 97 (2014) 212 – 216 Contents lists available at ScienceDirect Radiation Physics

Contents lists available at ScienceDirect

Radiation Physics and Chemistry

journal homepage: www.elsevier.com/locate/radphyschem Structural, optical and thermal properties of PVA/CdS

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

Nastaran Faraji, Roslina Mat Hussin, W. Mahmood Mat Yunus Physics Department, Faculty of Science, University Putra

Physics Department, Faculty of Science, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia

HIGHLIGHTS

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

article info

Article history:

Received 17 July 2013 Accepted 5 December 2013 Available online 17 December 2013

Keywords:

CdS nanoparticles

CdS/PVA nanocomposites

Radiolytic synthesis

Thermal conductivity

abstract

Monodispersed spherical CdS nanoparticles stabilized in PVA solution were synthesized by the gamma radiolytic method and found the average particle size increased from 12 to 13 nm with the increment of dose from 10 to 40 kGy. The XRD results show that it has crystalline planes of cubic structure with crystal lattice parameter of 5.832 Å. The optical re ectance revealed a band-edge of CdS nanoparticles at about 475 nm and the re ectance wavelength red shifted with increasing dose due to increasing particle size. The thermal conductivity of CdS/PVA nanocomposites measured by the transient hot wire method that revealed a decrement of the thermal conductivity with an increase of dose caused by effect of radiation on crystallinity of the polymer structure.

& 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.: þ 60 12 2110976. E-mail address: kharazmi.alireza@hotmail.com (A. Kharazmi) .

0969-806X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.

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

A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212 216

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 gathered by researchers which reveal the enhancement in thermal conductivity of liquids contained nanoparticles such as alumina (Al 2 O 3 ), titanium oxide (TiO 2 ) and copper oxide (CuO) (Wang et al., 1999; Yoo et al., 2007). In this article, we report the structural, optical, and thermal properties of the CdS/PVA nanocomposites synthesized by gamma irradiation method in a single step at room temperature.

2. Materials and methods

CdS nanoparticles stabilized in PVA solution was synthesized by the gamma radiolytic method. 5-wt% PVA solution was pre- pared in 400 ml deionized water at the temperature of 80 1 С by stirring for 2 hours. The solution was divided equally into four different beakers before adding 10 2 M of Cd(NO 3 ) 2 and Na 2 S 2 O 3 into each beaker. The solution samples were bubbled with nitro- gen gas for 2 hours while stirring. The samples were irradiated by gamma rays at doses from 10 to 40 kGy. The Philip X-ray diffractometer (XRD) was used to determine the crystalline structure of CdS nanoparticles at the diffraction angle 2 θ range of 10 1 60 1 with copper K α radiation at 1.5418 Å wavelengths. The morphology of CdS nanoparticles was observed by Transmission Electron Microscopy (TEM) (JEOL 2010F UHR) operated at an accelerating voltage of 20 kV. The optical re ec- tance spectra were collected by a UV-Visible spectrometer (Shi- madzu-UV1650PC) in the wavelength range of 475 to 725 nm, and the uorescence spectra as a function of emission wavelength were recorded by a spectro uorometer (Shimadzu, RF-5301PC). The Decagon devices KD2 Thermal analyzer was used to measure the thermal conductivity of the CdS/PVA nanocompo- sites. The schematic diagram of the thermal conductivity measure- ment is shown in Fig. 1 . This apparatus has 5% accuracy over the 5 to 40 1 C temperature range, and also meets the standards of both ASTM D5334 and IEEE 442-1981. The portable device uses the 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 works as both heat source and thermometer. A single reading took 2 minutes. The probe was heated for 30 seconds by a known amount of current and the rest time was to ensure temperature stability. Besides, the probe also contains a thermistor which measures the changes in temperature while the microprocessor stores the data. At the end of data collection, the thermal conductivity of the sample was computed by the temperature differences versus time data. Due to the constant temperature, room temperature, the sample was placed inside a test-tube. The

temperature, the sample was placed inside a test-tube. The Fig. 1. The schematic for principle of

Fig. 1. The schematic for principle of thermal conductivity measurement.

apparatus probe was then securely placed in the tube and the thermal conductivity measurement of the sample was taken. The theoretical aspect of this measurement in detail can be found in literature ( Kleinstreuer and Feng, 2011 ).

3. Results and discussion

The formation of CdS nanoparticles in the PVA solution can be explained by means of combination of cadmium and sulfur ions. Indeed, the interaction of gamma rays with water causes hydrated

electrons e aq , hydroxyl radical (OH d ) and hydrogen radical (H d ) by radiolysis of water according to Eq. (1) ( Singh et al., 2011 ).

In aqueous solution, radiation decomposes Na 2 S 2 O 3 and form the

sulfur (S 2 ) ions ( Liu et al., 2006 ). Formerly, the cadmium ions

(Cd 2 þ ) were formed by dissolving the cadmium nitrate in the solution. Therefore, the sulfur ions coupled with cadmium ions form the CdS nanoparticles. The reaction of this formation can be described as in the following reactions ( Liu et al., 2006 ):

γ

rays e

H 2 O -

aq ; H þ ; H 3 O ; H ; OH ; H 2 ; H 2 O 2

ð 1 Þ

Na 2 S 2 O 3 - e aq þ S 2 O 3 2

S

2 O 3 2 þ e aq - S

þ SO 3 2

S

þ e aq - S 2

Cd 2 þ þ S 2 - CdS

ð

ð

ð

ð

2

3

4

5

Þ

Þ

Þ

Þ

CdS þ CdS - CdS 2

CdS

þ

CdS n - CdS n þ 1

ð

ð

6

7

Þ

Þ

In the nal term, the used polymer (PVA) as stabilizer prevents the agglomeration of CdS nanoparticles into larger particles. Fig. 2 shows the X-ray diffraction pattern of CdS/PVA nano- composites synthesized at doses from 10 to 40 kGy showing the structural characteristic of CdS nanoparticles conforming CdS nanoparticles formation. The rst observed peak at 19.5 1 is assigned to the crystalline PVA structure ( Faraji et al., 2012 ). The observed peaks at 2 θ values of 26.43 1 , 31.81 1 , 43.76 1 and 51.93 1 are perfectly matched with the (111), (200), (220), and (311), respec- tively crystalline planes of the cubic structure of CdS (ICDD PDF

214

A. Kharazmi et al. / Radiation Physics and Chemistry 97 (2014) 212 216

00-065-2887) with crystal lattice parameters of 5.832 Å and 198.6 Å 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

within the PVA. The size distribution diagrams illustrate Fig. 2. XRD pattern of CdS/PVA nanocomposites irradiated

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 re ectance as a function of wavelength for CdS/PVA nanocomposites. The re ectivity 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 signi cant. 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

peaks from lower doses up to 40 kGy indicates the increment Fig. 3. TEM image and

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

diagram of CdS nanoparticles at 10 kGy radiation dose. Fig. 4. TEM image and size distribution

Fig. 4. TEM image and size distribution diagram of CdS nanoparticles at 40 kGy radiation dose.

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Radiation Physics and Chemistry 97 (2014) 212 – 216 215 Fig. 5. Re fl ectance spectra

Fig. 5. Re ectance spectra of CdS/PVA nanocomposites irradiated from 10 to

40 kGy doses.

CdS/PVA nanocomposites irradiated from 10 to 40 kGy doses. Fig. 6. Fluorescence spectra of CdS/PVA nanocomposites

Fig. 6. Fluorescence spectra of CdS/PVA nanocomposites irradiated from 10 to

40 kGy doses.

CdS/PVA nanocomposites irradiated from 10 to 40 kGy doses. Fig. 7. The value of thermal conductivity

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

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 ¼ 3 ρ C p υ l

ð 8 Þ

where ρ is density, C p is the speci c heat at constant pressure, υ 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; Gutiérrez-Juárez 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 con rmed the forma- tion of cubic crystalline CdS with crystal lattice parameters of 5.832 Å and 198.6 Å 3 volume cell. The average particle size was increased from 12 to 13 nm with increasing dose from 10 to 40 kGy. The optical re ectance revealed a band-edge of CdS nanoparticles at about 475 nm, and the re ectance 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

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