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Electrospinning of Nanofibers:
Reinventing the Wheel?**
By Dan Li and Younan Xia*
Electrospinning provides a simple and versatile method for generating
ultrathin fibers from a rich variety of materials that include polymers,
composites, and ceramics. This article presents an overview of this
technique, with focus on progress achieved in the last three years. After a
brief description of the setups for electrospinning, we choose to concentrate on the mechanisms
and theoretical models that have been developed for electrospinning, as well as the ability to
control the diameter, morphology, composition, secondary structure, and spatial alignment of
electrospun nanofibers. In addition, we highlight some potential applications associated with the
remarkable features of electrospun nanofibers. Our discussion is concluded with some personal
perspectives on the future directions in which this wonderful technique could be pursued.
1. Introduction
One-dimensional (1D) nanostructures have been a subject
of intensive research due to their unique properties and
intriguing applications in many areas.[1] A large number of
synthetic and fabrication methods have already been demonstrated for generating 1D nanostructures in the form of fibers,
wires, rods, belts, tubes, spirals, and rings from various materials.[2] Among these methods, electrospinning (a drawing process based on electrostatic interactions) seems to provide the
simplest approach to nanofibers with both solid and hollow
interiors that are exceptionally long in length, uniform in
diameter, and diversified in composition.[3] Unlike other
methods for generating 1D nanostructures, the formation of a
thin fiber via electrospinning is based on the uniaxial stretching (or elongation) of a viscoelastic jet derived from a polymer solution or melt. This technique is similar to the commercial processes for drawing microscale fibers except for the use
DOI: 10.1002/adma.200400719
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early 1990s, several research groups (in particular, the Reneker group at the University of Akron) revived interest in this
technique by demonstrating the fabrication of thin fibers from
a broad range of organic polymers. At this time the term
electrospinning was coined and is now widely used in the
literature.[3,8] These timely demonstrations triggered a lot of
experimental and theoretical studies related to electrospinning. It is notable that the number of publications in this field
(see Fig. 1) has been increasing exponentially in the past few
years, on account of the remarkable simplicity, versatility, and
potential uses of this technique.
Figure 1. The annual number of publications on the subject of electrospinning, as provided by the search engine of SciFinder Scholar. For
2004, there are already 71 publications before April 30.
Younan Xia was born in Jiangsu, China, in 1965. He received a B.S. degree in chemical physics from
the University of Science and Technology of China (USTC) in 1987, and then worked as a graduate
student studying nonlinear optical materials for four years at the Fujian Institute of Research on the
Structure of Matter, Academia Sinica. He came to the United States in 1991, received an M.S. degree
in inorganic chemistry from the University of Pennsylvania (with Professor Alan G. MacDiarmid)
in 1993, and a Ph.D. degree in physical chemistry from Harvard University (with Professor George
M. Whitesides) in 1996, after which he stayed at Harvard and worked as a postdoctoral fellow with
Profs. George M. Whitesides and Mara Prentiss. He moved to Seattle in 1997 and started as an
Assistant Professor of Chemistry at the University of Washington. He was promoted to the rank of
tenured Associate Professor in 2001 and to the rank of Professor in 2003. His research interests
include nanostructured materials, self-assembly, photonic crystals, colloidal chemistry, microfabrication, surface modification, electrospinning, conducting polymers, microfluidic and
microanalytical systems, and novel devices for photonics, optoelectronics, and displays.
Dan Li was born in Sichuan, China, in 1971. He received a Ph.D. degree in Materials Physics and
Chemistry from the University of Electronic Science and Technology of China (with Prof. Yanrong
Li and Prof. Yadong Jiang) in 1999. Subsequently, he spent two years as a postdoctoral fellow with
Prof. Xin Wang and one year as Associate Professor at Nanjing University of Science and
Technology, China. He joined Prof. Younan Xia's group at the University of Washington in Seattle
as a postdoctoral fellow in 2002. His research interests include electrospinning nanostructured
materials, conjugated organic polymers, and nanostructure-based electronic devices.
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woven mat, see the inset of Figure 2 for the scanning electron
microscope (SEM) image of a typical sample. With the use of
this relatively simple and straightforward technique, more
than 50 different types of organic polymers have already been
processed as fibers with diameters ranging from tens of nanometers to a few micrometers.[3]
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shaped, instability region is composed of multiple jets. However, a closer examination using high-speed photography
(Fig. 3B) establishes that the conical envelope contains only a
single, rapidly bending or whipping thread. In some cases,
splaying of the electrified jet might also be observed, though
it was never a dominant process during spinning.[10] The frequency of whipping is so high that conventional photography
cannot properly resolve it, giving the impression that the original liquid jet splits into multiple branches as it moves toward
the collector.
Based on experimental observations and electrohydrodynamic theories, mathematical models have been developed by
several groups to investigate the electrospinning process.
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ing uniform fibers. In the same vein, a number of other methods can also be explored to fabricate the arrayed capillaries.
For example, one can take a commercial alumina membrane,
sputter one of its surfaces with gold and glue the other side to
the tube of a syringe to form an array of nozzles whose diameters can be readily varied in the range from hundreds of nanometers to tens of micrometers. For this system, it is necessary
to derivatize the gold surface of the membrane with an alkanethiolate monolayer terminated in CH3 or CF3 group to
confine the liquid within each individual pore and thus to
eliminate the coalescence of individual droplets.[15] In another
approach, silicon micromachining can be used to fabricate
porous membranes with patterned arrays of micrometer-sized
channels.[16] By varying the mask design, one can also easily
control the spacing between adjacent holes to avoid coalescence of liquid droplets coming out from different pores. In a
third approach, the rigid needles made of stainless steel that
are commonly used for electrospinning can be replaced with
flexible, polyimide-coated glass capillaries commercially
available for use in capillary electrophoresis.[17] The diameters
of such glass capillaries can be varied from a few to several
hundred micrometers. They can also be easily assembled into
a hexagonal array that may contain tens to hundreds of capillaries. By connecting each capillary to a different solution, it
will be possible to simultaneously electrospin nanofibers with
a range of different compositions and to obtain assemblies of
nanofibers that will exhibit various unique combinations of
functionalities. It is believed that the adoption of an array of
nozzles can significantly increase the production rate while
simultaneously increasing considerably the compositional and
structural complexities associated with electrospun nanofibers
and their assemblies.
In addition to the use of capillaries having hollow interiors,
spinnerets can also be fabricated with solid tips. For example,
Craighead and co-workers have demonstrated that a microfabricated, pyramidal silicon tip could serve as the spinneret
for electrospinning when it was integrated with a microfluidic
device.[18] A combination of electrospinning and microfluidics
may provide an exciting opportunity to directly process functional materials on miniaturized chips. In a related study,
Kessick and Tepper demonstrated that the setup for electrospinning could be miniaturized to produce single polymer
fibers (or their networks) on the surface of a microchip without using high voltage, a syringe pump, or a metal needle.[19]
In this case, they placed a drop of polymer solution on the surface of an interdigitated array of metal electrodes and found
that fibers could be formed between drops sitting on adjacent
electrodes if a potential difference was applied between the
two sets of electrodes or if the drops were charged in advance
via electrospray. These two demonstrations imply that electrospinning can probably be integrated with the conventional
lithographic techniques to form a new fabrication platform
for generating patterned microstructures from various materials and on a broad range of length scales.
Similar to electrospray, the conventional setup for electrospinning also involves the use of a single capillary as the spin-
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neret, and thus is only suitable for generating fibers with one
particular composition in each run of fabrication. To overcome this limitation, a number of new designs for the spinneret have recently been demonstrated. In one approach, Wilkes
and Balkus Jr. and their co-workers showed that a spinneret
containing two needles (attached to each other in a side-byside fashion) could be used to electrospin composite nanofibers.[20] In another approach, a spinneret consisting of two
coaxial capillaries has been demonstrated by several groups
to fabricate fibers with core/sheath or hollow structures.[21] In
particular, the spinneret design demonstrated by Xia and Li is
simple enough that it can be conveniently fabricated at essentially no cost by any research group (see Sec. 3.3.2 for a
detailed discussion). Larsen et al. have also demonstrated that
the use of a coaxial spinneret could provide a good control
over the structure and morphology of resultant fibers, and
prevent blockade of the nozzle by flowing a suitable solvent
vapor through the outer capillary during an electrospinning
process.[22]
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The morphology and diameter of electrospun fibers are dependent on a number of processing parameters that include:
a) the intrinsic properties of the solution such as the type of polymer, the
conformation of polymer chain, viscosity (or concentration), elasticity, electrical conductivity, and the polarity and
surface tension of the solvent; and
b) the operational conditions such as
the strength of applied electric field, the
distance between spinneret and collector, and the feeding rate for the polymer
solution.[3] In addition to these variables, the humidity and temperature of
the surroundings may also play an important role in determining the morphology and diameter of electrospun
nanofibers (see Sec. 3.3.3).
The presence of beads in electrospun
fibers is a common problem.[23] With
poly(ethylene oxide) (PEO) as a model
system, Reneker and co-workers have
systematically investigated the influence
of solution properties on the density of
beads contained in the electrospun
fibers.[23a] It was found that the viscosity,
surface tension, and the density of net
charges carried by the liquid jet all
Figure 4. SEM images of poly(vinyl pyrrolidone) (PVP) nanofibers that were electrospun from PVP
influenced the morphology of resultant
solutions in a mixture of ethanol and water (16:3 by volume). The weight percentage of PVP in the
fibers. However, formation of beads
solution was: A) 3, B) 5, C) 7, and D) 5. In preparation of sample D, 0.35 mg mL1 of tetramethylammonium chloride was added to the solution before electrospinning.
could be attributed mainly to the action
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Figure 5. SEM (A) and TEM (B) images of anatase nanofibers prepared
by electrospinning from ethanol solutions that contained 0.03 g mL1
poly(vinyl pyrrolidone) (PVP) and different amounts of titanium tetraisopropoxide: A) 1.5 and B) 0.25 g mL1, respectively. Both samples were
calcined in air at 500 C before imaging [40a].
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post-spinning treatment.[43] For instance, Greiner and coworkers added palladium diacetate to a PLA solution to
increase the electrical conductivity of this solution in an effort
to produce thinner nanofibers.[43a] Annealing of the as-spun
nanofibers at an elevated temperature led to the formation of
Pd nanoparticles within each fiber. Reneker and Hou have
also demonstrated the incorporation of iron salts into a poly(acrylonitrile) (PAN) solution to be used for electrospinning.[43b] Calcination of the resultant fibers in an appropriate
atmosphere resulted in the carbonization of PAN polymer
and the reduction of iron salts to iron nanoparticles. These
iron nanoparticles could be further used as catalysts to direct
the growth of carbon nanotubes (CNTs) on the carbon nanofibers. In general, it is non-trivial to achieve a homogeneous
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fibers containing a fluorescent indicator as the active component.[29] The sensitivities of such devices to metal ions (Fe3+ or
Hg2+) and 2,4-dinitrotoluene were two to three orders of magnitude greater than those based on continuous thin films. The
improvement was mainly caused by the availability of a larger
surface area and the relatively easy transport of analytes to
the active sites on each nanofiber. Gas sensors based on individual polyaniline nanofibers were recently fabricated by
Craighead and co-workers using their microfabricated electrospinning tip.[85] These authors also investigated the relationship between the response times and the diameters of
their nanofibers. Compared with film-based polyaniline sensors, both response time and sensitivity could be greatly improved. These demonstrations clearly indicate that electrospun nanofibers and their assemblies hold the promise as
active components for the sensing technology.
5.2.6. Nanofiber-Based Electrode Materials
Jo and co-workers have demonstrated that porous membranes made of electrospun fibers were good matrices for
holding polymer electrolytes and might find immediate use in
the fabrication of high-performance lithium batteries.[28a]
They have also found that the porous membrane (when
soaked with an electrolyte solution) exhibits an enhanced
ionic conductivity. In comparison, the polymer film made of
PVDF gel showed a relatively low value. This difference can
be attributed to the peculiar pore structure associated with
membranes composed of electrospun nanofibers. Both threedimensionally interconnected pore structure and the high
porosity associated with a mat of nanofibers facilitate the
transport of ions through the membrane. The high surface
area also improves the wettability of fibers by the electrolyte
solution, as well as the affinity between these two heterogeneous components. Yang and Kim have also evaluated the
performance of carbon nanofibers as an electrode material
for making supercapacitor.[86] The carbon nanofibers were
prepared by carbonization of electrospun fibers of PAN. They
observed a maximum capacitance of 175 F g1. By controlling
the activation temperature, the pore density, and structure
within the nanofibers could be varied to further improve the
performance of such a supercapacitor at higher current
densities.
5.2.7. Nanofiber-Based Electronic and Optical Devices
Like the semiconducting or metallic nanowires synthesized
using other methods, electrospun nanofibers with electrical
and electro-optical activities have also received much interest
in recent years because of their potential application in fabricating nanoscale electronic and optoelectronic devices. In this
regard, Wang and Santiago-Aviles have measured the electrical properties of partially graphitized carbon nanofibers prepared from electrospun nanofibers of PAN and a large negative magnetoresistance (75 %) was observed at 1.9 K.[87a]
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6. Concluding Remarks
The past few years have witnessed tremendous progress in
the area of electrospinning. Thanks to the efforts of many
research groups, electrospinning has now emerged as a technique capable of processing a rich variety of organic polymers,
ceramics, and composite materials into ultrathin fibers with
controllable diameters. The morphologies and internal structures of these fibers could also be tailored using a number of
physical and/or chemical methods. Furthermore, the setup for
electrospinning has been modified to directly generate nanofibers with coreshell or hollow structures, and as uniaxially
aligned arrays or layer-by-layer stacked films. In addition to
the advancement in experimental studies, theoretical model-
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