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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
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
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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.
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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.
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
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.
458
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.
459
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