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Synthetic Metals 157 (2007) 454459

A study on the preparation of poly(vinyl alcohol) nanofibers


containing silver nanoparticles
Wen-Ji Jin a , Hyun Jeong Jeon a , Jung Hyun Kim b , Ji Ho Youk a,
b

a Department of Advanced Fiber Engineering, Division of Nano-Systems, Inha University, Incheon 402-751, Republic of Korea
Department of Chemical Engineering, Yonsei University, 134 Shinchon-Dong, Sudaemoon-Ku, Seoul 120-749, Republic of Korea

Received 26 December 2006; accepted 3 May 2007


Available online 12 July 2007

Abstract
In this study, two practical methods for the facile and controlled preparation of poly(vinyl alcohol) (PVA) nanofibers containing Ag nanoparticles were investigated for use in antimicrobial applications. In the first method, PVA nanofibers containing Ag nanoparticles were successfully
electrospun from PVA/silver nitrate (AgNO3 ) aqueous solutions after first refluxing them. The Ag nanoparticles in the PVA/AgNO3 aqueous
solutions were generated by refluxing them. Interestingly, it was found that the Ag nanoparticles were also spontaneously generated during the
electrospinning process. In the second method, Ag nanoparticles were generated by annealing the PVA nanofibers electrospun from PVA/AgNO3
aqueous solutions. Residual Ag+ ions and the Ag nanoparticles generated during the electrospinning process in the PVA nanofibers were diffused
and aggregated into larger Ag nanoparticles during the annealing process. All of the Ag nanoparticles were sphere shaped and evenly distributed
in the PVA nanofibers prepared by the two methods.
2007 Elsevier B.V. All rights reserved.
Keywords: Electrospinning; Poly(vinyl alcohol) (PVA); Silver nanoparticles; Reflux; Annealing

1. Introduction
Polymer nanofiber mats prepared by the electrospinning of
polymer solutions have unique properties, such as a high surface
area-to-volume ratio and high porosity. Recently, the incorporation of metal nanoparticles into polymer nanofibers has drawn
a great deal of attention, because these metal nanoparticles
can endow the polymer nanofibers with distinctive properties,
such as optical, electronic, catalytic, and antimicrobial properties, which enable them to be used in novel applications such
as sensors, catalysts, nanoelectronic devices, etc. [15]. The
incorporation of metal nanoparticles into polymer nanofibers
can be achieved either by electrospinning polymer solutions
containing the metal nanoparticles or by reducing metal salts
or complexes in electrospun polymer nanofibers.In our previous study [68], a simple one-step method of preparing
poly(N-vinylpyrrolidone) (PVP), poly(acrylonitrile) (PAN), and

Corresponding author.
E-mail address: youk@inha.ac.kr (J.H. Youk).

0379-6779/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2007.05.011

polyurethane (PU) nanofibers containing silver (Ag) nanoparticles was developed for use in antimicrobial filter applications.
N,N-dimethylformamide (DMF) was used as a solvent for
these polymers, as well as a reducing agent for the Ag+
ions. The Ag+ ions in these polymer solutions were directly
reduced to produce Ag nanoparticles and the resulting solution was electrospun. Also, in another previous study [9],
poly(vinyl alcohol) (PVA) nanofibers containing Ag nanoparticles were prepared by the short heat treatment of electrospun
PVA/silver nitrate (AgNO3 ) nanofiber mats at 155 C for
use in wound dressing applications. After the short heat
treatment, the Ag+ ions therein were reduced to produce a
large number of Ag nanoparticles, however, this was not
a controllable process. The polymer nanofibers containing
Ag nanoparticles showed very strong antimicrobial activities
[9,10].
In this study, for the facile and controlled preparation of PVA
nanofibers containing Ag nanoparticles for use in antimicrobial applications, the following two methods were investigated.
In the first method, the reduction of Ag+ ions in PVA/AgNO3
aqueous solutions was attempted by refluxing them without any chemical reducing agents and, then, the resulting

W.-J. Jin et al. / Synthetic Metals 157 (2007) 454459

PVA solutions containing Ag nanoparticles were directly


electrospun. In the second method, electrospun PVA/AgNO3
nanofibers were annealed for the controlled generation of Ag
nanoparticles in the PVA nanofibers. It was reported that
PVA could be used as a reducing agent as well as a stabilizer of Ag nanoparticles [1117], and it was therefore
expected that it would enable the generation and agglomeration of the Ag nanoparticles in the PVA nanofibers to be
controlled.
2. Experimental
2.1. Materials
PVA (>99% hydrolyzed, Mw = 89,00098,000) and AgNO3
(99.998%) were purchased from Aldrich Co.

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3. Results and discussion


3.1. Electrospinning of reuxed PVA/AgNO3 aqueous
solutions
Fig. 1(a) shows the changes in the UVvis absorption spectra
of the 12 wt% PVA aqueous solutions containing 1 wt% AgNO3
after being refluxed at various temperatures for 1 h. The intensities of the surface plasmon resonance (SPR) absorption of the
Ag nanoparticles at 425 nm increased as the reflux temperature
increased, however, the positions of the peak maximum did not
shift to a longer wavelength, indicating that the Ag nanoparticles
were well stabilized by the PVA, and their average sizes were
not increased with increasing reflux temperature. PVA was used
as a reducing agent as well as a stabilizer of the Ag nanoparticles
[1117]. PVA has lone pair electrons on the hydroxyl oxygen,
which can coordinate with the Ag+ ions and Ag nanoparticles.
The PVA chains sterically inhibit particle nucleation and growth.

2.2. Electrospinning
In the first method, 12 wt% aqueous PVA solutions with various amounts of AgNO3 were refluxed under different conditions
and then directly electrospun. In the second method, 12 wt%
aqueous PVA solutions with different amounts AgNO3 were
electrospun, and the Ag+ ions contained in the resulting PVA
nanofiber mats were reduced via the annealing process. The
weight percentage of AgNO3 in the solutions was calculated
on the basis of the weight of PVA. The electrospinning setup
used in this study consisted of a hypodermic syringe, a plastic
tip (ID = 0.95 mm), a graphite electrode (black lead), an aluminum collecting drum, and a high voltage supply (Chungpa
EMI, Korea). The syringe pump connected to the hypodermic syringe controlled the flow rate. The PVA/AgNO3 aqueous
solution was electrospun at a positive voltage of 20 kV, a tipto-collector distance of 11.5 cm, and a solution flow rate of
0.66 mL/h.
2.3. Characterization
UVvis absorption spectra were obtained on a Shimadzu
UVvis spectrometer (UV-1601PC). The morphologies of the
electrospun nanofibers were observed using scanning electron
microscopy (SEM, Hitachi S-4200) after applying a gold coating. The average diameter of the electrospun nanofibers was
determined by analyzing the SEM images using a custom code
image analysis program. The transmission electron microscopy
(TEM) images were obtained with a Philips CM 200 transmission electron microscope using the samples deposited on
carbon-coated copper grids. The conductivities of the PVA
solutions were measured using a conductivity meter (Isteck
Model 455C) at 25 C. The amount of the solution sample
was in the range of 2050 mL, so that the sensor part of
the detector was completely immersed in the solution. The
surface tensions and viscosities of the PVA solutions were measured using an interfacial tension meter (Kruss Model K8)
at 25 C.

Fig. 1. UVvis absorption spectra of PVA aqueous solutions containing 1 wt%


of AgNO3 after being refluxed (a) at different temperatures for 1 h and (b) at
80 C for different times.

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W.-J. Jin et al. / Synthetic Metals 157 (2007) 454459

Fig. 2. SEM images of the PVA nanofibers electrospun from 12 wt% PVA aqueous solutions containing (a) 0 wt%, (b) 0.5 wt%, (c) 1 wt%, and (d) 2 wt% of AgNO3 .
The PVA aqueous solutions were refluxed at 80 C for 1 h.

Patakfalvi et al. [15] reported that the rate of particle formation


and the average sizes of the Ag nanoparticles in the PVA/AgNO3
aqueous solutions decreased with increasing PVA concentration.
In practice, a yellow coloration was observed with the naked eye
after a certain time period when the solutions were refluxed at
temperatures above 50 C, indicating that the reduction of the
Ag+ ions and the subsequent formation of Ag nanoparticles in
the PVA solutions require a certain minimum time period and
reflux temperature.
Fig. 1(b) shows the changes in the UVvis absorption spectra
of the 12 wt% PVA aqueous solutions containing 1 wt% AgNO3
after being refluxed at 80 C for different times. The intensities
of the SPR absorption of the Ag nanoparticles increased with
increasing reflux time, indicating that more Ag nanoparticles
were generated. The slight shift of the peak maximum to longer
wavelengths implies that the average sizes of the Ag nanoparticles slightly increased with increasing reflux time. The Ag+
ions were reduced by the refluxing process and PVA acted as
a stabilizing agent to inhibit further agglomeration of the Ag
nanoparticles.
Fig. 2 shows the SEM images of the PVA nanofibers electrospun from the 12 wt% PVA aqueous solutions containing
different amounts of AgNO3 after being refluxed at 80 C for
1 h. The average diameters of the PVA nanofibers electrospun
with 0, 0.5, 1, and 2 wt% of AgNO3 were 200, 170, 160, and
120 nm, respectively, but their morphologies were quite similar. The surface tensions of the PVA/AgNO3 aqueous solutions
measured after being refluxed were 60.0 mN/m, whereas the
conductivities of the PVA aqueous solutions were almost linearly
increased from 720 to 1300 S/cm according to the amount of
AgNO3 added. The average diameters of the PVA nanofibers
decreased with increasing conductivity of the PVA solutions. It

was reported that the addition of salts increases the charge density in the ejected jets and, thus, stronger elongation forces are
imposed on them, due to the self-repulsion of the excess charges
under the electrical field, resulting in the electrospun fibers having a substantially straighter shape and smaller diameter [18].
The conductivity of the PVA solution was found to be a more
effective factor than the other parameters in reducing the fiber
diameter.
Fig. 3 shows the TEM images of the PVA nanofibers electrospun from the 12 wt% PVA aqueous solutions with 1 wt%
AgNO3 without refluxing and after being refluxed at 80 C. The
Ag nanoparticles were all sphere shaped and their size distributions were very narrow. The average size of the Ag nanoparticles
in the PVA nanofibers electrospun without the refluxing process
was 3.1 nm (Fig. 3(a)), while those of the Ag nanoparticles in
the PVA nanofibers electrospun after being refluxed at 80 C
for 1 and 2 h were both 3.6 nm. Interestingly, a large number
of Ag nanoparticles were observed in the PVA nanofibers electrospun without the refluxing process. It was assumed that these
Ag nanoparticles were generated during the electrospinning process. In effect, when a metallic needle and/or an electrode are
employed for the electrospinning of a polymer/AgNO3 aqueous
solution, Ag and/or silver oxides (Ag2 O) are susceptible to be
generated and grown on the surface of the metallic parts. Ag+
ions can be electrochemically reduced to the metallic form by
metals such as iron and copper [9]. In the present study, these
by-products often precipitated into the polymer solution and
blocked the electrospinning needle. However, the effective generation of Ag nanoparticles during the electrospinning process
was not observed from the electrospinning of PVP, PNA, and
PU [68], implying that the generation of Ag nanoparticles is
dependent on the type of electrospinning solution system. The

W.-J. Jin et al. / Synthetic Metals 157 (2007) 454459

Fig. 3. TEM images of the PVA nanofibers electrospun from 12 wt% PVA solutions containing 1 wt% of AgNO3 : (a) not refluxed, (b) refluxed at 80 C for 1 h,
and (c) refluxed at 80 C for 2 h.

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Fig. 4. TEM images of the PVA nanofibers electrospun from 12 wt% PVA solutions containing 1 wt% of AgNO3 after being annealed at (a) 50 C, (b) 80 C,
and (c) 110 C for 14 h.

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W.-J. Jin et al. / Synthetic Metals 157 (2007) 454459

number and average size of the Ag nanoparticles in the PVA


nanofibers did not increase with increasing reflux time. Therefore, it is assumed that this invariance of the number and average
size of the Ag nanoparticles with respect to the reflux time
is associated with their generation during the electrospinning
process.
3.2. Annealing of electrospun PVA/AgNO3 nanobers
In order to observe the effects of annealing on the generation of Ag nanoparticles in PVA nanofibers, electrospun
PVA/AgNO3 nanofibers were annealed at different temperatures. Fig. 4 shows the TEM images of the PVA fibers
electrospun from the 12 wt% PVA aqueous solutions with 1 wt%
AgNO3 after being annealed at 50, 80 and 110 C for 14 h.
The Ag nanoparticles were all sphere shaped and their size
distributions were very narrow. The average sizes of the Ag

nanoparticles obtained after annealing the nanofibers at 50, 80,


and 110 C for 14 h were 3.2, 3.5, and 3.6 nm, respectively. The
average sizes of the Ag nanoparticles slightly increased with
increasing annealing temperature, but their size distributions
became narrower. Although the PVA nanofibers were annealed
above the Tg value of the PVA (110 C), the average size and
number of the Ag nanoparticles were not significantly changed,
indicating that a lot of the Ag+ ions were already reduced to Ag
nanoparticles during the electrospinning process and that PVA
acted as a stabilizer of the Ag nanoparticles.
Fig. 5 shows the TEM images of the PVA nanofibers electrospun from the 12 wt% PVA aqueous solutions with 2 wt%
AgNO3 before and after being annealed at 80 C for 14 h. The
average sizes of the Ag nanoparticles in the PVA nanofibers
before and after annealing were 3.5 and 5.8 nm, respectively.
As shown in Fig. 5(a), the Ag nanoparticles were readily generated during the electrospinning process and their number and
size in the PVA nanofibers increased as the amount of AgNO3
added increased (see Fig. 3(a)). After the annealing process, the
size of the Ag nanoparticles was increased, but their number
was decreased. The Ag nanoparticles were still sphere shaped
and evenly distributed in the PVA nanofibers after the annealing process. This implies that the residual Ag+ ions and the Ag
nanoparticles in the PVA nanofibers diffused and aggregated to
form larger Ag nanoparticles during the annealing process. This
simple annealing process provided fine control over the size of
the Ag nanoparticles in the PVA nanofibers by varying the extent
of the reduction and ripening process, as reported in the case of
PVA/AgNO3 thin films [12]. The Ag nanoparticles produced
are stable, and comparable in size and distribution with those
produced by other typical methods.
4. Conclusions
PVA nanofibers containing Ag nanoparticles were electrospun from refluxed PVA/AgNO3 aqueous solutions. The Ag+
ions in the PVA/AgNO3 aqueous solutions were reduced via the
refluxing process without any chemical reducing agents. The
average diameters of the PVA nanofibers electrospun with 0,
0.5, 1, and 2 wt% of AgNO3 after being refluxed at 80 C for
1 h were 200, 170, 160, and 120 nm, respectively. The average
diameters decreased as the conductivities of the PVA solutions
increased. It was found that Ag nanoparticles were also spontaneously generated during the electrospinning process. When
the PVA nanofibers electrospun from the 12 wt% PVA aqueous
solutions with 2 wt% AgNO3 were annealed at 80 C for 14 h,
the average size of the Ag nanoparticles was increased, but their
number was decreased. It was found that this simple annealing process could provide fine control over the size of the Ag
nanoparticles in the PVA nanofibers.
Acknowledgement

Fig. 5. TEM images of the PVA nanofibers electrospun from 12 wt% PVA solutions containing 2 wt% of AgNO3 : (a) not annealed and (b) annealed at 80 C
for 14 h.

The authors of this study would like to thank the Korea


Science and Engineering Foundation (KOSEF) for sponsoring
this research through the SRC/ERC Program of MOST/KOSEF
(R11-2005-065) and Ministry of Commerce, Industry and

W.-J. Jin et al. / Synthetic Metals 157 (2007) 454459

Energy (MOCIE) through the project of NGNT (No. 100241352005-11).


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