Fabrication and characterization of silver

nanoparticles/PVA composites for flexible

electronic application
Cite as: AIP Conference Proceedings 2267, 020046 (2020); https://doi.org/10.1063/5.0016135
Published Online: 21 September 2020

Y. Z. N. Htwe, and M. Mariatti

AIP Conference Proceedings 2267, 020046 (2020); https://doi.org/10.1063/5.0016135 2267, 020046

© 2020 Author(s).
 Fabrication and Characterization of Silver
nanoparticles/PVA Composites for Flexible Electronic
Application
Y.Z.N.Htwe1, M. Mariatti1*
1*
School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia,
14300 Nibong Tebal, Pulau Pinang, Malaysia

*Corresponding author: mariatti@usm.my

Abstract. The use of silver nanoparticles/ polyvinyl alcohol (PVA) composites for flexible electronic has attracted
enormous attention due to its prominent mechanical and electrical properties. In the present study, AgNPs produced
from chemical reduction method were used to fabricate AgNPs/PVA composite with different amount of AgNPs
loadings (0.1 – 0.5 wt%). The effect of trisodium citrate concentration on the properties of AgNPs was investigated.
The structure and morphology of the synthesized AgNPs were characterised using X-ray diffraction (XRD), UV-
visible (UV), and transmission electron microscopy (TEM). It was found that increasing concentration of trisodium
citrate resulted in decreasing size of AgNPs. The as-prepared AgNPs were then dispersed into an PVA matrix, to form
electrically conductive flexible thin film. Addition of AgNPs in PVA results in 3 order increased in electrical
conductivity of composite film from 0.1 wt% to 0.5 wt% AgNPs.

1. INTRODUCTION
Silver nanoparticles combined with polymers have attracted great consideration because of the widened
application goal offered by these hybrid materials [1]. Particularly, silver nanoparticles and polymer composites
are promising functional materials in several field such as optical, electrical, and mechanical properties. Many
reports in the literature show attempts to synthesize silver nanoparticles-based polymer nanocomposites, with
their application in high performance capacitors, conductive inks, and other electronic components [2,3]. Silver
nanoparticles have received considerable attention due to their attractive physical and chemical properties and it
has been combined with polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polymethyl
methacrylate (PMMA). PVA could be considered as a good host material for metal due to its excellent
thermostability, chemical resistance, high mechanical strength, water solubility, and moderate and dopant
dependent electrical conductivity along with its consideration among the best polymers as host matrix for silver
nanoparticles [4].
The chemical and physical properties of the metal nanoparticles are dependent on their size as well as their
structure, shape and size distribution. Many methods have been reported for the synthesis of silver nanoparticles
[5]. Among them, chemical reduction method is the most common approach for the synthesis of silver
nanoparticles. This method enables variation in the molar concentration of the reactant, dispersant and feed rate
of reactant in order to produce silver nanoparticles with controlled particle sizes, shapes and particle size
distribution [6]. The selection of an appropriate reducing agent is also a crucial factor, as the size, shape and
particle size distribution are strongly depended on the nature of the reducing agent to redox potential of the metal.
During the synthesis process, if the reaction rate is too fast, rapid formation of large amount of metal nuclei will
occur and result in particles that are too small [7]. On the other hand, agglomeration of particles will take place if
the reaction rate is too slow. Moreover, the choice of the surfactant is critical since it determines the stability,
solubility, reactivity, dispersibility and even the size and shape of the nanoparticles during the synthesis. The
present study describes a simple, low-cost, and partially green method to synthesize silver nanoparticles. This
synthesis method is considered partially green as it used ascorbic acid which is one form of vitamin C [8].
In the present study, the effect of trisodium citrate concentrations on the properties of silver nanoparticles was
investigated. Silver nanoparticles produced from chemical reduction method was used to fabricate silver

1
3rd International Postgraduate Conference on Materials, Minerals & Polymer (MAMIP) 2019
AIP Conf. Proc. 2267, 020046-1–020046-7; https://doi.org/10.1063/5.0016135
Published by AIP Publishing. 978-0-7354-2030-4/$30.00

020046-1
nanoparticles and PVA composites. Relationship between silver nanoparticles concentration and electrical
conductivity of silver nanoparticles was determined.

2. EXPERIMENTAL

2.1 Materials
Silver nitrate (AgNO3), trisodium citrate (C6H5O7Na3) and ascorbic acid (C6H8O6) were supplied by
Merck assay and used as precursor, reducing agent and surfactant respectively. Polyvinyl alcohol (PVA) powder
used in the study was purchased from Sigma-Aldrich. Ethanol and acetone were supplied by J.T. Baker and were
used as cleaning agent. Deionized water was used in all of the synthesis processes.

2.2 Synthesis of silver nanoparticles by chemical reduction method

In this study, silver nitrate (AgNO3) was used as a starting material while trisodium citrate (C6H5O7Na3)
and ascorbic acid (C6H8O6) were used as the reducing agent and surfactant, respectively. Concentrations of
trisodium citrate were varied by 2 mM, 4 mM, 6 mM, 8 mM and 10 mM in order to observe the effect of these
parameters especially on the size and morphology of silver nanoparticles produced. In detail, 80 ml of AgNO3
was first heated to 60°C and was then added (with vigorous stirring) to 20 ml of C 6H5O7Na3 and C6H8O6 solution
that pre-heated to 60°C. The mixture was then stirred for 20 minutes. After that, the heating was stopped and the
solution was cooled at room temperature with continuous stirring. Figure 1 shows a schematic diagram of the
synthesis process.

FIGURE 1. Schematic illustration of the synthesis of silver nanoparticles by chemical reduction method

2.3 Preparation of silver nanoparticles/PVA composite

Silver nanoparticles/PVA composites with different amount of silver nanoparticles loadings varying
from 0.1 to 0.5 wt% were synthesized by a simple solution casting method. 1g of PVA was dissolved in 50 ml of
deionized water then the desired amount of silver nanoparticles was slowly added into the PVA solution. The
mixture was mixed with vigorous stirring using magnetic stirring for about 30 min at 90°C. Subsequently, the
obtained homogeneous solution was slowly casted onto a plate and dried at room temperature for 24 hours. Finally,
the film was peeled off.

2.4 Characterizations
X-ray diffraction (XRD) patterns were obtained using a Bruker D8 X-ray diffractometer with a Ni-
filtered Cu-Kα (λ= 1.54021 Å) radiation source and were used to identify the crystallographic structure of silver
nanoparticles and its composite. The size and morphology of the silver nanoparticles produced were studied by
Transmission electron microscopy (TEM) (model Philips CM12 equipped with Docu Vesion 3.2 image analysis
system). Ultraviolet-visible Spectroscopy (UV-vis) was performed in a Perkin-Elmer 35 spectrophotometer.
Fourier transform infrared (FTIR) spectra were obtained with a Perkin Elmer FTIR spectrometer at room
temperature with a typical wave number of 4000-500 cm-1 in open air and transmittance. The electrical
conductivity of silver nanoparticles/PVA was measured using a resistance meter measurement system, model
Prostat-812.

3. RESULTS AND DISCUSSION

020046-2
 The crystal structure and the formation of silver nanoparticles were analysed by XRD. Figure 2 (a-e)
shows XRD spectrum of silver nanoparticles produced by using different concentrations of trisodium citrate
dihydrate 2.0 mM, 4.0 mM, 6.0 mM, 8.0 mM and 10.0 mM, respectively. By using JCPDS database, five
characteristic peaks correspond to Miller indices (111), (200), (220), (311) and (222), were detected at 38°, 44°,
64°, 77° and 82°, respectively, which can be indexed according to the facets of face-centered cubic crystal
structure of silver. Similar peaks were reported by other researchers including Agnhotri et al., [7] and Ajitha et
al., [9] in their works on the synthesis of AgNPs.

FIGURE 2. XRD spectrum of silver nanoparticles prepared at different concentration of trisodium

citrate dihydrate (a) 2.0 mM, (b) 4.0 mM, (c) 6.0 mM, (d) 8.0 mM and (e) 10 mM

Table 1 records the crystallite sizes obtained from the XRD analysis. From the table, synthesis portrayed
the progression of decreasing values with the average crystallite sizes. The results are in accordance with the
average particle sizes measured using TEM observations (Figure 3). In the synthesis of AgNPs, as the
concentrations of trisodium citrate dihydrate increased i.e 2.0 mM, 4.0 mM, 6.0 mM, 8.0 mM and 10.0 mM, the
average crystallite sizes of the AgNPs decreased, i.e., 38.72 nm, 30.69 nm, 28.62 nm, 24.59 nm, 20.06 nm,
respectively.
TABLE 1. Crystallite sizes and average particle sizes of silver nanoparticles with increasing concentrations of
trisodium citrate dihydrate.
Trisodium citrate Crystallite size (nm) Average particle size
dihydrate concentration from XRD from TEM (nm)
2.0 mM 38.72 49.65±5.83

4.0 mM 30.69 43.31±7.46

6.0 mM 28.62 35.56±8.37

8.0 mM 24.59 31.33±6.64

10.mM 20.06 27.75±7.06

The results showed that the increasing concentration of trisodium citrate dihydrate in synthesis has
caused the decreasing of AgNPs crystallite sizes. Since the nanosized forms are physically very aggregative, the
stabilization of metal colloids is indeed an important aspect of the bottom-up synthesis in order to preserve the
fine dispersed state of metal nanoparticles. Therefore, stabilizing agents are often employed to passive and limit
the growth of nanoparticles at an early stage thereby protects and stabilizes them against agglomeration [10]. The
morphologies and size distributions of the synthesized AgNPs with different concentrations of trisodium citrate
dehydrate were analysed by TEM. Morphologically, the TEM results in Figure 3 indicated that all AgNPs samples
are quasi-spherical with a present of other shapes for example polygon and they are well-dispersed. In terms of
size, the average sizes of the AgNPs were measured using Image Analyst Software based on approximately 100

020046-3
particles. By referring to the results in Figure 3, the average sizes of silver nanoparticles show an increasing trend
with 49.65 nm at 2.0 mM to 27.75 nm at 10 mM of trisodium citrate dihydrate. As the concentration of trisodium
citrate dihydrate increased from 2.0 mM to 10 mM, the particles size histograms of silver nanoparticles also show
narrowing of particle size distribution from 20-65 nm to 15-55 nm, respectively. Reasons for this phenomenon
could be because of the rate of reaction is directly proportional to the concentration of reactant according to the
Law of mass action. Therefore, it can be suggested that with increasing of trisodium citrate dihydrate
concentration, the rate of reaction increased. As the rate increased, the silver ions are consumed faster thus leaving
less possibility for particles size growth.

a a(a
Quasi-spherical shape

b b
polygon

c c

d d

e e

FIGURE 3. TEM micrograph and size distribution histogram of silver nanoparticles prepared at different
concentration of trisodium citrate (a) 2.0 mM, (b) 4.0 mM, (c) 6.0 mM, (d) 8.0 mM, and (e) 10 mM

020046-4
 UV-Vis is an important analytical technique to ascertain the formation and stability of metal
nanoparticles in aqueous solution. Also, among various properties, the optical characteristics of AgNPs have
received particular attention due to their marked size and shape dependence especially in terms of their surface
plasmon resonance (SPR). Figure 4 shows the UV-vis absorption spectrum of synthesized AgNPs at different
concentrations of trisodium citrate dihydrate. From Figure 4, it is found that the absorption band centred of AgNPs
is in the range of 419-424 nm. In addition, the symmetric absorption peak of the UV-vis spectrum implies the
narrow size distribution of the silver nanoparticles obtained in the present study. This is in accordance with the
previous work by Baláž et al. [11].

FIGURE 4. UV-vis spectrum of silver nanoparticles as function of trisodium citrate concentration

The composition and phase structures of the PVA and silver nanoparticles/PVA composites were
investigated by XRD. As shown in Figure 5, curve (b) indicates that PVA had significant diffraction peaks at 2θ
of 11.7, 19.7 and 41.5°. The one at 19.7° is the main crystal peak, corresponding to a (101) reflection of the
monoclinic crystal. The silver nanoparticles/PVA composites, as shown in curve (c-f), exhibit strong peaks from
Braggs reflection at 2θ = 12, 32, and 38. It is well known that the peaks at 2θ less than 20° are due to the crystalline
nature of the PVA polymer molecule. The X-ray diffraction peak corresponding to 38° and above are due to silver
nanoparticles corresponding to the lattice plane (111). The peaks at 30° might be due to the presence of certain
impurities while bonding between the PVA and the silver molecule. The same peaks also can be found in the
composites with various amount of silver nanoparticles loading. The same observation was reported by Mahendia
et al., [12] in their study on mechanical properties of graphene based PVA composites.

(a) (b)

FIGURE 5. XRD patterns of (a) silver nanoparticles, (b) PVA, (e) 0.1 wt% silver nanoparticles/PVA, (d) 0.2 wt%
silver nanoparticles/PVA, (e) 0.3 wt% silver nanoparticles/PVA, (f) 0.5 wt% silver nanoparticles/PVA composites

020046-5
 Figure 6 represents the FTIR spectra of pure PVA and silver nanoparticles/PVA composite with different
loading of silver nanoparticles contents. FTIR spectra of PVA showed a very broad and intense peak at 3286 cm-
1
as a result of stretching vibration of hydroxyl groups. This strong absorption is typical of the polymeric
association of hydroxyl groups. But this band is shifted to 3289 cm-1 in the silver nanoparticles/PVA composite
due to hydrogen bonding interactions between the hydroxyl groups of PVA and silver nanoparticles. The other
vibrational peaks at 2926, 1646, 1417, and 845 cm-1 are assigned to O-H stretching, C-H stretching, C=O
stretching, C-H bend of CH2, and CH rocking of PVA, respectively. Furthermore, the vibrational peaks found in
the range 1080-500 cm-1 may be attributed to Ag-O, which indicate that silver nanoparticles mixed in the PVA
polymer matrix. The experimental data given in Figure 6 indicate an decrease in the vibrations of C-H and C=O
groups in the PVA matrix after adding silver nanoparticles directly in the PVA film. Such changes in C-H and
C=O vibrations have been observed in other reports [13]. After adding silver nanoparticles, some polymers chains
have been broken and some other chains have been formed instead. Interestingly, the observed FTIR peaks of
the obtained silver nanoparticles/PVA composite conforms to previous report [14], which indicates the
successful preparation of silver nanoparticles/ PVA composite in this study.

FIGURE 6. FTIR spectrum of (a) PVA, (b) 0.1 wt% silver nanoparticles/PVA, (c) 0.2 wt% silver
nanoparticles/PVA, (d) 0.3 wt% silver nanoparticles/PVA, (e) 0.5 wt% silver nanoparticles/PVA composite

Table 2 summarizes the electrical conductivity values of pure PVA and silver nanoparticles/PVA
composites with different amount of silver nanoparticles loading. From the table, it is apparent that the electrical
conductivities of the composites film are higher than those of pure PVA film and it is increases with increase in
silver nanoparticles content in the composites. The conductivity of the composites film increased by 3 orders of
magnitude from 1.642×10-6 to 5.869×10-2 as the ratio of silver nanoparticles loading increased from 0.1 wt% to
0.5 wt%. The increase in conductivity is justified due to electronic tunnelling effect in the polymer through silver
nanoparticles. For lower amount of silver nanoparticles loaded composite, the conductivity is marginal; however,
as higher amount of silver nanoparticles is added, the increase in conductivity is significantly high that might be
due to increase in the mobility of electron that leads to tunnelling probability [15].

TABLE 2. Electrical conductivity of PVA and silver nanoparticles/PVA composite with different amount of
silver nanoparticles loading

Silver nanoparticles/PVA Electrical conductivity (Scm-1)

composite
PVA 2.189×10-8
0.1 wt% 1.642×10-5
0.2 wt% 4.926×10-4
0.3 wt% 9.181×10-4
0.5 wt% 5.869×10-2

020046-6
 CONCLUSIONS
Summary, we have successfully synthesized silver nanoparticles by chemical reduction method with different
amount of trisodium citrate. The TEM analysis revealed that generated nanoparticles are almost spherical, and
their average particles size was 27-50 nm and the size of nanoparticles is decreased with increasing concentrations
of trisodium citrate. The chemical reduction silver nanoparticles at 10 mM concentrations of trisodium citrate was
used to produce silver nanoparticles/PVA composites. The electrical conductivity of silver nanoparticles/PVA
composites increased 3 order with 0.5 wt% of silver nanoparticles loading compared to unfilled PVA.

ACKNOWLEDGEMENT
We are very grateful to the Malaysian Ministry of Education for awarding us a Fundamental Research
Grant (MRSA with grant no. 6071284), Universiti Sains Malaysia for the USM fellowship scheme granted to the
first author. They would also would like to thank Universiti Sains Malaysia (USM) and School of Materials and
Mineral Resources Engineering for the use of their facilities.

REFERENCES
[1] Ghanipour, M., & Dorranian, D, Journal of Nanomaterials 2, (2013)
[2] Ananth, A. N., Umapathy, S., Sophia, J., Mathavan, T., & Mangalaraj, D. Applied Nanoscience, 1(2), 87-96
(2011)
[3] Sadasivuni, K. K., Rattan, S., Waseem, S., Brahme, S. K., Kondawar, S. B., Ghosh, S., & Mazumdar, P. In
Polymer Nanocomposites in Biomedical Engineering (Springer, Cham., 2019), pp. 331-373.
[4] Priya, B., Gupta, V. K., Pathania, D., & Singha, A. S. Carbohydrate polymers, 109, 171-179 (2014)
[5] Premkumar, J., Sudhakar, T., Dhakal, A., Shrestha, J. B., Krishnakumar, S., & Balashanmugam, P.,
Biocatalysis and agricultural biotechnology 15, 311-316 (2018).
[6] Tran, Q. H., & Le, A. T. Advances in Natural Sciences: Nanoscience and Nanotechnology, 4(3), 033001
(2013)
[7] Agnihotri, S., Mukherji, S., & Mukherji, RSC Advances, 4(8), 3974-3983 (2014)
[8] Ealias, A. M., & Saravanakumar, M. P. In IOP Conf. Ser. Mater. Sci. Eng. 263-032019 (2017)
[9] Ajitha, B., Divya, A., Harish, G. S., & Sreedhara Reddy, P. Res. J. Physical Sci, 1(7), 11-14 (2013)
[10] Cushing, B. L., Kolesnichenko, V. L., & O'Connor, C. J. Chemical reviews, 104(9), 3893-3946 (2004)
[11] Baláž, M., Daneu, N., Balážová, Ľ., Dutková, E., Tkáčiková, Ľ., Briančin, J., & Baláž, P. Advanced Powder
Technology, 28(12), 3307-3312 (2017)
[12] Mahendia, S., Tomar, A. K., & Kumar, S. Journal of Alloys and Compounds, 508(2), 406-411 (2010)
[13] Zhang, Z., Wu, Y., Wang, Z., Zou, X., Zhao, Y., & Sun, L. Materials Science and Engineering: C, 69, 462-
469 (2016)
[14] Kutsenko, A. S., & Granchak, V. M. Theoretical and Experimental Chemistry, 45(5) 313-318 (2009)
[15] Mahendia, S., Tomar, A. K., & Kumar, S. Journal of Alloys and Compounds, 508(2) 406-411 (2010)

020046-7