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Materials Letters 61 (2007) 4027 4030

www.elsevier.com/locate/matlet

Preparation of ultra-fine polyimide fibers containing silver


nanoparticles via in situ technique
Qian Zhang, Dezhen Wu , Shengli Qi, Zhanpeng Wu, Xiaoping Yang, Riguang Jin
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China
Received 28 July 2006; accepted 5 January 2007
Available online 13 January 2007

Abstract
Ultra-fine polyimide fibers containing silver nanoparticles were prepared by electrospinning from poly(amic acid)/(trifluoroacetylacetonoto)
silver(I) (PAA/AgTFA) solution. Thermal curing of the silver(I)-containing fibers led to cycloimidization of the poly(amic acid) into polyimide
with concomitant silver(I) reduction. The polyimidesilver fibers were characterized by FT-IR, X-ray diffraction, scanning electron microscopy,
and transmission electron microscopy. The average diameters of silver nanoparticles and ultra-fine PI fibers electrospun from solutions with
different amounts of AgTFA were studied, and the crystal structure of silver nanoparticles was also presented.
2007 Elsevier B.V. All rights reserved.
Keywords: Polyimide; Silver; Nanoparticles; Electrospun fibers

1. Introduction
Silver nanoparticles are widely used due to their superior
optical [1,2], electrical, catalytic [3] and antimicrobial [4]
properties. Polymer/silver nanoparticles composites, combining
the advantages of the silver nanoparticles and the processability
of the polymers, opened a new gateway in developing
nanocomposite systems with improved performances [5].
Generally speaking, there are two approaches to prepare
polymer/silver nanocomposites. One is to disperse silver
nanoparticles into polymer matrices, being simple but difficult
to obtain well-dispersed nanoparticles due to easy aggregation
of nanoparticles. The other is in situ chemical formation of
silver nanoparticles by the reduction of silver ions which are
introduced into polymer matrices. The tailored size and size
distribution of silver particles can be achieved by choosing
some parameters such as reduction method, concentration of
precursor and temperature in this chemical process [69].
In recent years, ultra-fine polymer fibers prepared by
electrospinning of a polymer solution have been drawing

Corresponding author.
E-mail address: wdz@mail.buct.edu.cn (D. Wu).
0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.01.011

great attention because of their unique properties, such as high


surface area-to-volume and ease of fabrication [10]. Some
researches on ultra-fine polymer fibers containing silver
nanoparticles have been reported in various polymer matrices:
cellulose acetate [4], poly (N-vinylpyrrolidone) [6], polyacrylonitrile [9,11,12] and poly(4-vinylpyridine) [13]. Polyimide
(PI) constitutes an important class of polymers due to its
superior thermal and chemical resistance as well as mechanical
properties. Nah et al. [14] have reported the preparation of PI
ultra-fine fibers through electrospinning.
In this paper, we present an effective method to prepare ultrafine PI fibers containing silver nanoparticles via electrospinning
poly(amic acid) (PAA)/AgTFA solution followed by thermal
imidization as well as silver reduction. Their morphological
characterization was carried out by X-ray diffraction, SEM and
TEM.
2. Experimental
Pyromellitic dianhydride (PMDA, 99%) and 4,4-Oxydianiline (4,4-ODA, 99%) were purchased from Shanghai Research
Institute of Synthetic Resins and used as received. N,Ndimethylformamide (DMF, analytic pure, 99.5%) was
purchased from Tianjin Fine Chemical Co., China and used as

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Q. Zhang et al. / Materials Letters 61 (2007) 40274030

3. Results and discussion

Fig. 1. FT-IR spectra of PAA/AgTFA, PI/Ag fibers electrospun from 10 wt.%


PAA solution with 7 wt.% Ag and pure PI electrospun fibers.

received. Silver(I) acetate (AgAC, analytic pure, 99.0%) was


obtained from Shanghai Shiyi Chemicals Reagent Co. Ltd. and
used as received. 1,1,1-Trifluoro-2,4-pentanedione (TFAH,
98%) was purchased from Acros Organics and used as received.
The poly(amic acid) (PAA) solution of 10 wt.%, a precursor
of PI, was synthesized from its monomers, PMDA and ODA in
DMF. The resin was stirred for a minimum of 2 h before
incorporating the silver complex. The AgTFA complex was
freshly produced by dissolving AgAC in a small volume of
DMF containing TFAH with three times mole equivalent to the
silver acetate.
After incorporating different amounts of AgTFA (Ag was 1
7 wt.% of the amount of PI/Ag fiber) into PAA resin, the
solution was electrospun using an electrostatic spinning
apparatus. The apparatus consisted of a syringe and a needle
(ID = 6.5 mm), an aluminum collecting plate and a high voltage
supply. A syringe pump (TOP5300) connected to the syringe
controlled the flow rate. The PAA/AgTFA solution was
electrospun at a positive voltage of 15 kV, a working distance
of 10 cm (the distance between the needle tip and the collecting
plate), and a solution flow rate of 0.2 ml/h.
Thermal curing was performed in a forced air oven to
accomplish the conversion of the PAA fibers into PI ones as
well as the formation of silver nanoparticles. The cure cycle was
heating over 1 h from normal temperature to 135 C and
remaining at 135 C for 1 h, followed by heating to 300 C over
2 h and remaining at 300 C for 3 h.
The PAA/AgTFA and PI/Ag fibers obtained were characterized by FT-IR spectroscopy (Nexus 670) to identify the
molecular structure. X-ray photoelectron spectra were obtained
using an ESCALAB 250 spectrometer (Thermo Electron
Corporation) in the fixed analyzer transmission mode. The
morphologies of the ultra-fine PI fibers were observed on a
scanning electron microscopy (SEM) (HITACHI S-800) after
platinum coating. Transmission electron microscopy (TEM)
images were obtained with a HITACHI H-800TEM instrument
using samples deposited on carbon coated copper grids.

Thermal curing leads to the cycloimidization of PAA into PI with


concomitant silver reduction and aggregation yielding ultra-fine
polyimidesilver fibers. Fig. 1 shows the FT-IR spectra of the asdeposited electrospun PAA/AgTFA fibers, the final PI/Ag fibers and
pure PI fibers. Prior to heating, the IR spectrum for PAA/AgTFA fibers
exhibits characteristic bands at 29003200 cm 1, 1660 cm 1 and
1550 cm 1, which respond to COOH and NH2, C_O in a CONH
group and the CNH stretch bands, respectively. Following thermal
treatment, there are four absorbance peaks at 1780 cm 1, 1725 cm 1,
1380 cm 1 and 725 cm 1 on the PI/Ag spectrum, responding to C_O
symmetric stretch, C_O asymmetric stretch, CN stretch and C_O
bending respectively, which indicate the formation of the polyimide
matrix. It is noteworthy to mention that the relative intensity of the peak
at 1780 cm 1 in the PI/Ag fibers is lower than in pure PI fibers,
implying the decrease of electron density of the carboxyl (C_O)
oxygen atom, probably due to the interaction between Ag nanoparticles
and the C_O group [15] of the polyimide.
X-ray diffraction pattern for the 7 wt.% silver doped fibers is shown
in Fig. 2. Four obvious peaks are detected at 2 = 38.1, 44.3, 64.4
and 77.5, which are corresponding to the crystal faces of (111), (200),
(220), and (311) of silver, consistent with the formation of facecentered-cubic silver crystallite in the polyimide ultra-fine fibers after
heating. The full width at half-maximum (FWHM) of the strongest
characteristic peak (111) is used to estimate the average crystallite size
by applying the Scherrer equation: D = / cos. Here X-ray
wavelength is 1.54056, is the shape factor which is often assigned
a value of 0.89 if the shape is unknown, D is the average diameter of
the crystals in angstroms, is the Bragg angle in degrees, and is the
full width at half-maximum of the strongest characteristic peak in
radians. The result shows that the average silver particle size in the
ultra-fine fibers is approximately 20.2 nm.
SEM micrographs for the typical non-woven fabric PI/Ag fibers
electrospun with different silver content are shown in Fig. 3. It is clear that
the average diameters of the ultra-fine PI/Ag fibers decreased gradually
with increasing silver concentration, with fiber diameters on the order of
200 nm, 190 nm, 180 nm and 60 nm for the pure, 1 wt.%, 2 wt.% and 7 wt.
% silver doped polyimide fibers, respectively. It is suggested that the
addition of a salt would increase the charge density of the polymer
solution, which will cause stronger elongation forces on the ejected jets

Fig. 2. X-ray diffraction peaks of PI fiber mat electrospun from 10 wt.% PAA
solution with 7 wt.% Ag.

Q. Zhang et al. / Materials Letters 61 (2007) 40274030

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Fig. 3. SEM images of PI/Ag fibers electrospun from 10 wt.% PAA solution with different amounts of AgTFA: Ag (a) 0 wt.%, (b) 1 wt.%, (c) 2 wt.% and (d) 7 wt.%.

under the same electrical field, resulting in the formation of substantially


straighter and finer fibers [16]. In addition, as Ag amount increases, more
silver particles can be observed on SEM images.
Fig. 4 shows the corresponding TEM images of the ultra-fine PI/Ag
fibers containing different Ag. It can be clearly seen that the silver
nanoparticles are embedded on the fiber surface. Nearly spherical silver
particles were observed on the TEM images for the 1 wt.% and 2 wt.%
silver doped polyimide fibers, with average diameters of 10 and 12 nm,
respectively. When the silver concentration increased to 7 wt.%, the
average diameter of silver particles increased in the range of 1420 nm,
in agreement with the XRD result presented above. However, the silver
particles become irregular and non-spherical, which is attributed to the

massive silver migration and aggregation. The migration and


aggregation of silver particles are probably driven largely by the
instability of silver atoms due to their high surface free energy. Their
aggregation would produce thermodynamically stable particles with
bigger sizes [17,18].

4. Conclusion
Ultra-fine polyimide (PI) fibers containing Ag nanoparticles
were prepared by electrospinning from PAA/AgTFA solution
followed by thermal curing as well as silver reduction. The Ag

Fig. 4. TEM images of PI/Ag fibers electrospun from 10 wt.% PAA solution with different amounts of AgTFA: Ag (a) 1 wt.%, (b) 2 wt.% and (c) 7 wt.%.

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Q. Zhang et al. / Materials Letters 61 (2007) 40274030

nanoparticles in the PI fibers possessed a face-centered-cubic


structure. The average diameters of the ultra-fine PI fibers with
different amounts of AgTFA, in which Ag were 0, 1, 2, and
7 wt.%, were 200, 190, 180, and 60 nm, respectively. The
number of Ag nanoparticles in the ultra-fine PI fibers increased
as the amount of AgTFA increased and the average diameters of
the Ag nanoparticles were 10, 12, and 1420 nm when 1, 2 and
7 wt.% Ag were doped, respectively.
Acknowledgements
This research was supported by the Program for New
Century Excellent Talents in University (NCET) and the
National Natural Science Foundation of China (NSFC, Project
No. 50573007).
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