APRL 2001 323

Functional Modifications of Nylon: Antimicrobial Func- 10. Sun, G., and Xu, X., Durable and Regenerable Antibacte-
tions, Textile Rex J. 70, 728-733 (2000).
6. Kruse, R. H., Puckett, W. H., and Richardson, J. H.,
Biological Safety Cabinetry, Clinical Microbiol. Rev. 4 ,
207-241 (1991).
7. Scott, E., and Bloomfield, S. F., The Survival and Transfer
of Microbial Contamination Via Cloths, Hands, and Uten-
sils, J. Appl. Bacteriol. 68, 271-278 (1990).
8. Slaughter, S., Hayden, M. K., Nathan, C., Hu, T-C., et al.,
A Comparison of the Effect of Universal Use of Gloves
and Gowns with That of Glove Use Alone on Acquisition
of Vancomycin-Resistant Enterolocci in a Medical Inten-
sive Care Unit, Ann. Infern.Med. 125, 448-56 (1996).
9. Sun, G., and Xu, X., Durable and Regenerable Antibacte-
j a l Finishing of Fabrics: Biocidal Properties, Texrile
Clietn. Color. 30 (6), 26 (1998).
rial Finishing of Fabrics: Chemical Structures, Textile
Chern. Color. 31 (3,3 1 (1 999).
11. Sun, G., and Xu, X., Durable and Regenerable Antibacte-
rial Finishing of Fabrics: Fabric Properties, Textile Chetn.
Color. 31 (l), 21-24 (1999).
12. “Technical Manual of American Association of Textile
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13. Tweden, K. S., Cameron, J. D., Razzouk, A. J., Bianco,
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M475-481 (1997).
hfanuscript received December 29, 1999; accepted h f q 1. 2000.

Electrospinning and Properties of Some Nanofibers

A. BUER,S. C. UGBOLUE,
AND S. B. WARNER
Departriieiit of Textile Sciences, University of Massachusetts, Dartinorith, Massachiisetts 02747, U.S.A.

ABSTRACT
Electrospinning is a unique process that is capable of producing fibers with diameters
ranging over several orders of magnitude, from the micrometer range typical of conven-
tional fibers down to the nanometer range. Electrospun fibers possess unusually large
surface-to-volume ratios and are expected io display morphologies and material properties
different from their conventional counterparts. In this paper, details of recent designs and
construction of equipment for controllable and reproducible electrospinning or electro-
static spinning are presented. An understanding of the electrospinning process is linked to
processing conditions and polymer fluid characteristics, as well as the structure and
properties of the final electrospun nanofibers.

Electrospinning is a fundamentally different approach
to fiber production. Electrostatic forces alone are used to
produce fibers. Although the idea dates back at least 60
years [4],there is only limited quantitative technical and
scientific information available about the theoretical
foundation of this process. Interest has renewed in recent
years with the work of Reneker and co-workers, who
have demonstrated electrospinning for a wide variety of
polymer solutions, including rigid rod polymers [I 1, 12,
131. St. John Manley and co-workers had previously
demonstrated electrospinning of polyethylene and
polypropylene fibers from the melt [ S , 91; in that work,
they obtained properties similar to weakly oriented con-
ventional fibers. Most recent investigations have focused
on the structure and morphology of electrospun fibers [2,
3, 6, 1 1 , 131. Indications are that crystallites in electro-
spun PEO fibers are somewhat smaller than in conven-
tional fibers, and birefringence confirms molecular ori-
entation; however, all of the fibers produced to date have
necessarily been generated without control over the
forces driving orientation and crystallization. Conse-
quently, electrospun fibers have been collected as webs
and used chiefly in nonwoven applications [I, 51.
With low molecular weight liquids, the fluid stream
breaks up into small, charged droplets. This process is
known as “electrospraying” and has enjoyed widespread

Texrile Res. J. 71(4), 323-328 (2001) 0040-5115fS2.~

324 TEXTILE
RESEARCH
JOURNAL

commercial success in various applicatio.nssuch as paint stream, or jet, from the tip of the cone. The fibers are
spraying and fuel atomization [7]. typically laid down in a random fashion on the collecting
screen to form a'nonwoven web or mat.
Experimental Our electrospinners are equipped with an inclined
pipette, Figure 1, or a syringe pump as a feed system.
SOLUTION
PREPARATION
With the inclined pipette (tip diameter 0.8 mm), the
Poly(acrylonitri1e) (PAN)and polyethylene oxide (PEO) solution is gravity-fed to the capillary tip at a rate
polymers of varying molecular weights were supplied by dependent upon the angle of inclination of the pipette
Polysciences and are detailed in Tables I and 11. Viscos- and the head of fluid within the pipette. Although it
ity measurements involved a Brookfield DV-11+ pro- permits relatively little control over the feed rate, this
grammable viscometer, conductivity was measured on a configuration offers the significant advantage of sim-
Mahlo textometer model DMB-6F, and an instrument plicity for preliminary trials, and has been instrumen-
was designed and constructed to measure surface ten- tal in identifying relevant operating parameters. Using
sion. a syringe pump in place of the pipette provides better
control over the feed rate through a digitally con-
TABLE
1. hlaterials. trolled electric motor that ensures a constant volumet-
ric feed rate. Each pump is connected to a feed cap-
hlolecular weight, Concentration
Polymer ghol Solvent wt 56 illary with 1 mm inner diameter. The capillary itself
may be either conducting or insulating (in which case
~ ~~

PEO 100,000 Water, chloroform 1-20

2,000,000 Water, chloroform
PAN solubilized DralonT dimethyl formamide
PEO 300,000 isopropanol :water ( 61)
1,000,OOO isopropanol :water (6:l)
4.000.000 isoorooanol :water (6:l)
ELECTROSPINNING
The basic configuration of an electrospinning process
is illustrated in Figure 1. It consists of a high voItage
power supply capable of 0-30 kV DC, a charged capillary
fed with polymer solution or melt, and a grounded col-
lection device. Feed of the polymer liquid to the tip of the
capillary results in the formation of a droplet at the
capillary tip, whose size and shape are dictated by sur-
face tension and gravitational forces. Applying high volt-
age to the capillary produces a charge on the droplet that
overcomes the forces of surface tension, resulting in
elongation of the drop, formation of a Taylor cone [14]
and, at sufficiently high voltage, ejection of a continuous
0.5-3 the high voltage electrode is fed directly to the solu-
6, 10, 15 tion entering the capillary). Choice of capillary mate-
3, 4, 6, 9 rial may affect both electrode efficiency and flow
3, 4, 6, 9
3. 4. 6. 9 characteristics within the capillary.
We also configured the electrospinners [ 161 with
Plexiglas isolation boxes to minimize extraneous air cur-
rents. In addition, we equipped our apparatus with a
Faraday cage, consisting of 0.635-cm mesh metal screen
surrounding the Plexiglas box, to provide isolation from
extraneous electromagnetic disturbances. Collection was
on a static or moving screen or plate at a lower potential
(typically connected to ground). The spinneret-to-collec-
tor distance varied from approximately 1-20 cm, with
10-15 cm separation distance typical. The construction
material of the collector could influence the electric field
lines in the vicinity of the collector, as well as the ease of
fiber, yarn, or web release; candidates we considered
included aluminum, steel, copper, carbon, woven, and
nonwoven fabrics.

TABLE
11. Composition and properties of polymer solutions.

Solution composition, wt lo
Polymer Viscosity, Temp.," Resistivity, Surface tension,
designation Polymer Isopropanol Water CP "C hlnm mN/m

PEO 0.3hl-6 6.0 82 12 1320 25.5 0 23

PEO 0.3h1-4 4.0 0 96 246 20.9 0 69
PEO 1.011-6 6.0 82 12 1 I500 20.3 0.10 39
PEO 4.011-3 3.0 85 12 4300 22.8 0.10 31
dimethyl
formamide
PAN 6 6.0 93 - very viscous NA - 15
PAN 10 10.0 90 - 1720 21.7 - 46
a Temperature of the polymer solution during the viscosity measurement.
APRIL2001 325

150-250 tion currents. From measurements of the current as a

capillary function of flow rate, the surface charge density of the
Electrode jet, which plays a major role in determining jet stability,
may be extracted.
There are two common techniques for measuring elec-
tric currents in electrospinning. In the first method, a
resistor is inserted in line between the collector and
ground, and the voltage drop is measured across it. From
-
-
this, the current is calculated using Ohm’s law. Since the
- Taylor Cone jet currents are believed to be small, high impedance is
Cdledion Screen required to observe a signal. In the second method, a
sensitive current meter (e.g.,Fluke 88 digital Inultimeter)
FIGURE1. Prototypical electrospinning unit. between the collector and ground is used to measure
current directly.

LASERVELOCIhlETRY AND FIBER

MICROSCOPY TENSILE
TESTING
Spinline properties involved a laser Doppler velocim-
Electrospun web samples were carefully transferred
etry (LDV) system (Dantec LDA EduSys 3 system) de-
from the collector to a scanning electron microscope
signed for fonvard scatter operations and fitted with a 10
stub covered with adhesive. A drop of silver paint was
mW coaxial He-Ne laser (632 nm). The transmission
placed on the side to insure electrical grounding. The
optics included a neutral beam-splitter, a Bragg cell, a
samples were plated with gold palladium in a Denton
beam displacer, and a 300 mm focal length front lens.
Vacuum Desk I1 sputtering machine and observed
The collection optics, set up in a fonvard scattering
with an Amray 1200B SEhf at the voltages indicated on
position, included a 300-mm close-up lens and a photo-
the photomicrographs. To measure the diameter of the
multiplier.
fibers viewed on a photomicrograph, a line was drawn
The signal processing system consisted of a frequency
across the photomicrograph and the diameter of the
tracker and a counter. However, one experiment in-
fibers measured at each crossing point. The results
volved simultaneous. use of both the original system
were used to compile fiber diameter distributign pro-
equipment and an m spectrum analyzer. The results
files. The electrospun web samples were also observed
confirmed the high reliability of the frequency tracker/
with a Leica DXIRX polarized optical microscope fitted
counter, but the length of time necessary to complete a
with a Sernamont compensator, a green interference
measurement was one order of magnitude longer when
filter of 546 nm wavelength, and a Leitz Microfilar
using the original equipment rather than the m spectrum
Microcode I1 eyepiece, which was calibrated with a
analyzer. The velocity measurements were recorded after
microscope ruler.
a good confidence level was achieved, as indicated on an
The path difference between the ordinary and ex-
oscilloscope by a constant burst signal. Velocity mea-
traordinary rays was measured using the Sernamont
surements, configuration 2, involved a 10 ml syringe and
compensator technique, and the diameter of the fibers
18 gauge stainless steel needle. The feed system was set
was measured with the Microfilar Microcode. The
on an X-Y table to permit precise alignment of the
refractive index of the mounting liquid used for the
electrospinning jet in the LDV measuring volume. Five
measurement was 1.546. Single fiber tenacity was
sets of 5000 or 10,000 counts were recorded for each of
measured using the cantilever technique: A 30 p m
the positions.
diameter glass fiber, the cantilever, was glued at one
end onto a microscope slide and a 15-pm nylon fiber
OPERATING PARAhIETERS
was attached at the free end of the glass fiber. The fiber
Three important operating parameters identified for to be tested was epoxied to the free end of the nylon
process characterization are flow rate, electric field fiber. While the sample fiber was stretched, the deflec-
strength, and electric current [17]. The first two are tion of the cantilever was measured with a calibrated
controlled primarily through equipment design, as de- eyepiece. A chart converted deflection into true val-
scribed above, but electric current is a parameter that ues. A part of the fiber was cut and deposited on a stub
must be measured during operation. The total current for diameter measurement with the SEhf. The elonga-
contains contributions from both convection and conduc- tion-to-break of electrospun PAN fibers was estimated
326 TEXTILE JOURNAL
RESEARCH

”
with a caliper: a bundle of fibers was stretched by hand
and the extension was directly calipered.
25.00
0
Results 20.00 0
0
0
PROCESS DYNAMICS
AND OPTIXlIZATION 0
/

The PEO and PAN fibers spun using configurations 1

and 2 are typical of electrospinning products used in
many laboratories. The stream exiting the Taylor cone
formed a stable jet, which then fanned out into a cone, -. ---.-,
presumably as a result of.splaying. As the driving voltage
increased, the length of the single jet decreased slightly
and the apex angle of the Taylor cone increased. For 0.0 20.0 40.0 60.0 80.0
polymer concentrations between 14 and 18 wt c/o, about Distance from the Cone Apex (mm)
4.5 kV was required to initiate dripping and 6 kV to
obtain a steady jet. These threshold voltages were rela-
tively insensitive to polymer concentration in this range. FIGURE2. Velocity of electrospunjet of 15% PANlDXlF at 12 kV.
A lower bound estimate of the spinning velocity exiting
the spinneret based on volumetric flow rate was 40 d s .
The fibers were typically “wet” at the collection screen
a 15 wt 5% solution of PAN in D m . The minimum velocity
and exhibited a 30% weight loss over ten minutes due to
is computed as
continued solvent evaporation. A nonwoven fabric con-
sisting of wet PET or PAN fibers can be readily stretched
about 100%;the strain-at-failure is significantly less for
Vmin= V, - 2 a a n d V,, = V , +2a ,
a nonwoven fabric of dry PET fibers. Molecular orienta- where V , is the experimental mean velocity and a is the
tion increases substantially upon stretching. standard deviation of the velocity.
In the stable region near the spinneret, we saw an
JET CURRENT approximately Gaussian distribution and the sampling
rate was high. In the unstable region, the jet’s rapid
Thejet currents were measured out for 2 wt % PEO hlW
motion was problematic for LDV measurements, resulting
= 2,000,000 g/mole in water. At the high voltages used
in only intermittent sampling and a low sampling rate.
during electrospinning, even small fluctuations (about
The average velocity of the jet was 15 d s in this
1%) in the power supply can produce a measurable AC
experiment.
signal superimposed on the DC current determining sur-
The data presented in Figure 2 show the strong accel-
face charge density in the jet. For low conductivity
eration and low variance of the velocity in the stable
fluids, the AC displacement current signal can be a sig-
region, close to the tip of the cone. The data also indicate
nificant fraction of the measured current, and care must
a strong change in the behavior of the jet from the stable
be taken to correct for it. Most previous investigators
region to the unstable region. One explanation might
have failed to take this effect into account [17].
involve a change of the aerodynamic forces acting on the
jet. When considering the mechanics and dynamics in the
LASERDOPPLERVELOCIXIETRY unstable region, aerodynamic forces can produce torque
The laser Doppler velocimetry experiments [ 161 pro- that rotates the fiber in a manner similar to when a fiber
vided information about the velocity of the jet at various rotates during gravity falling in air. The rotation gives the
distances from the apex. Close to the Taylor cone, the fibers a different cross section to the relative flow of air,
measurement gave the speed of the fluid in a relatively which in turn results in a huge increase in the drag forces
steady jet. Further from the apex, the data took a long on the fibers, leading to deceleration of the jet.
time to collect, since either the jet was moving or mul-
tiple jets were present. The jet entered the volume of FIBER
CHARACTERIZATION
AND MORPHOLOGY
measuring only at random moments, and velocity infor-
mation was collected and analyzed only at this time. We used scanning electron microscopy to obtain quan-
Figure 2 shows the velocity as a function of the distance titative measurements of fiber diameters. Scanning elec-
of the measured point from the tip of the Taylor cone for tron photomicrographs of PAN’fibers are shown in Figure
APRIL2001 327

3a, with similar resolution for PEO fibers in Figure 3b.
The fiber diameter distribution of a typical electrospun
PAN web, shown in Figure 4, follows a normal log
distribution.
efficient of variation of about 20% versus 40% for melt-
blown polypropylene fibers [ 151. The mean diameter of
the electrospun fibers we have produced is also about
five times smaller than that of typical meltblown
polypropylene fibers [15].
A 1.0 cm length of 1.25 p m diameter electrospun PAN
fiber tested using the cantilever principle exhibited fail-
ure at 41 rng of force. Assuming a round cross section
and density of 1.18 g/cm, the computed denier was
0.014, giving a tenacity of 2.9 g/den. The mean elonga-
tion-at-break of the same electrospun fiber was 190%,
with a standard deviation of 16%. The birefringence of
various diameter PEO fibers is presented in Figure 5 . The
birefringence of the electrospun fiber was below 0.005,
whereas that of the drawn fiber was roughly 0.040. As
with meltblown fibers, the birefringence of electrospun
fibers likely increases with decreasing diameter [ 151.

0.025 1
a 0.02
0

5 0.015
*.-.-2
EI)
C
0.01
* 0.005
0
0 1 2 3 4 5 6
. FIGURE3. Scanning electron micrograph of electrospun fibers: Diameter (um)
(a) PAN 1 5 8 DXIF, (b) PEO 2,000,000 @mole.

5. Birefringence of PEO electrospun fibers.

FIGURE
20 , I
18 -
16 - p=280nm
0-6onm
Conclusions
14 -
12- Electrospinning is a fast and simple process. Since it
a 10- requires only a small quantity of polymer, it can right-
8 8- fully be termed a nzicroprocessing technique. Both elec-
6- trostatic and fluid dynamic instabilities can contribute to
4- the basic operation of the process.
2- With polymeric fluids, viscoelastic forces stabilize the
0- T
jet, permitting the formation of small diameter, charged
. , I ,

0 0 0 0 0 0 0 0 0 0 0
a.03 b m .t v ma aN ~ 0
r filaments. Under certain conditions, electrostatic insta-
(0 l-
- ~ a - w n
Diameter (nm) bilities are believed to result in the break-up of the main
filament into many smaller filaments, a process called
FIGURE4. Diameter distribution of PAN fibers electrospun at 15 kV “splaying” [2, 11, 131. The current evidence [12, 161
from a 15 wt 9 DXIF solution. suggests that the path of the electrospinning jet is best
described as bending, looping, and spiraling. This phe-
Compared to meltblown fibers, the diameter distribu- nomenon is thought to be caused by exceeding a critical
tion of electrospun fibers is much narrower, with a co- charge density and may be responsible for the unusually