J.

of Supercritical Fluids 31 (2004) 329–333

Supercritical CO2 -assisted electrospinning

Natalia Levit a,b , Gary Tepper a,b,∗
a Department of Chemical Engineering, Virginia Commonwealth University, Richmond, VA 23284, USA
b Sentor Technologies Inc., Glen Allen, VA 23060, USA

Received in revised form 17 December 2003; accepted 27 December 2003

Abstract

Polymer fibers of high molecular weight polydimethylsiloxane (PDMS) and poly (d,l-lactic acid) (PLA) were produced using only
electrostatic forces and without the use of a liquid solvent. The fibers were formed between two electrodes in a high-pressure view cell. A
polymer sample was placed on a grounded electrode and a second, counter electrode was placed at high potential. The polymer was observed
as the thermodynamic conditions (e.g. temperature, CO2 pressure) and potential difference were varied. At a CO2 temperature and pressure
above the critical point, but well below the single-phase region, polymer fibers formed between the grounded electrode and the high voltage
counter electrode. It is surmised that the supercritical CO2 reduces the polymer viscosity sufficiently to allow fibers to be electrostatically
pulled from an un-dissolved bulk polymer sample.
© 2004 Published by Elsevier B.V.

Keywords: Electrospinning; Supercritical CO2 ; Polymer fiber

1. Introduction
Electrospinning of polymeric fibers is an area receiving
increasing attention and small diameter (<1 ␮m) fibers
have been produced using this method from a wide variety
of polymers including biomaterials and composites [1–3].
Potential applications for these fibers include breathable,
weather-resistant and bullet-proof garments, telecommuni-
cations, structural engineering and medicine. Typically, an
electrospinning apparatus consists of a hypodermic syringe
or needle filled with a polymer solution and placed at a
high (∼15 kV) potential with respect to a ground plane. The
sharp tip of the needle concentrates the electrostatic force
and fibers emerge from the tip of a Taylor cone formed at
the surface of the solution through a competition between
electrostatic forces and surface tension. The fibers are
collected at the counter electrode and typical electrospun
structures consist of a non-woven mat of very fine fibers.
The theoretical model for the electrospinning process has
evolved over time and the fiber formation mechanisms have
been described in several recent papers [4–6].
We recently demonstrated that the physical laws of elec-
trostatics driving the conventional electrospinning fiber
∗ Corresponding author. Tel.: +1-804-827-4079.
E-mail address: gtepper@vcu.edu (G. Tepper).
formation process are quite general and the entire process
can be scaled to achieve directed nanoscale polymer fiber
growth on the surface of a microchip without the need for
high voltage, pumps or needles [7]. In fact, the fiber for-
mation process actually appears to be favored at reduced
dimensions due to electric field concentration effects. In
our initial experiments, a polymer was dissolved in a liquid
solvent and microscale droplets were applied to the surface
of an interdigitated microelectrode. A small (∼6 V) voltage
was immediately applied between the electrodes and fibers
were observed to form from droplets on one electrode to the
opposite polarity electrode. Thus, it is possible to produce
controlled nanoscale polymer fiber structures and intercon-
nections directly on the surface of a chip for numerous ap-
plications including; intrachip optical interconnections for
the computer industry, chip-scale biocompatible fiber-based
scaffolds and highly sensitive microsensors.
One of the challenges faced when applying electrospin-
ning fiber formation technology to the surface of a mi-
croelectrode is solvent evaporation. Unlike a conventional
electrospinning process where the liquid solvent is replen-
ished through a hypodermic needle connected to a syringe
pump, the isolated droplets applied to the microelectrode
contain a limited amount of liquid solvent, which evaporates
leaving behind a dry polymer microdot. Thus, either the
fibers must be formed very quickly before the liquid solvent

0896-8446/$ – see front matter © 2004 Published by Elsevier B.V.

doi:10.1016/j.supflu.2003.12.008
330 N. Levit, G. Tepper / J. of Supercritical Fluids 31 (2004) 329–333
has evaporated, or the solvent must somehow be replen-
ished or maintained. However, while it is possible to apply a
prescribed amount of liquid solvent onto a dry polymer mi-
crodot using a micropipette, for example, this method is not
practical on a large scale. For mass production, it is more
practical to uniformly apply a solvent to the entire surface
of the microelectrode. However, we have found that this ap-
proach often destroys the integrity of the polymer microdots.
Here we report on our initial investigation on the use of
a supercritical fluid solvent to reduce the viscosity of an
un-dissolved polymer for electrospinning. The preliminary
results reported here were performed on a macroscale in a
high-pressure view cell and our primary objective was to
demonstrate the feasibility of using a supercritical fluid sol-
vent to reduce the viscosity of a polymer so that fibers can
be electrostatically pulled from the un-dissolved bulk poly-
mer. Because the solubility of a supercritical solvent can be
tuned by controlling the temperature and pressure, we found
that it is possible to form fibers within a thermodynamic
window where the polymer has been softened, but not dis-
solved. As an additional advantage, the supercritical solvent
reduces the polymer viscosity at much lower temperatures
than are necessary when using melt processing and CO2 is
an environmentally benign processing aid.
2. Experimental
High molecular weight PDMS was obtained commer-
cially from United Chemical Technologies and has an av-
erage molecular weight of about 300,000 according to the
manufacturer. It is an amorphous polymer and is highly vis-
cous at room temperature (Tg = −120 ◦ C). Poly (d,l-lactic
acid) (PLA) was from PURAC Biochem and has an average
molecular weight of 17,300 according to the manufacturer.
It is an amorphous polymer with a Tg = 67 ◦ C.
Fig. 1 is a schematic diagram of the modified high-pressure
view cell used to study both the phase behavior of polymers
TV
monitor
Top View
Video
camera
Phase
Monitor
V 10
Upper
Electrode
Front View
Lower
Electrode
Fig. 1. Schematic diagram of the apparatus and a side view illustrating
the electrode configuration.
in supercritical CO2 and to investigate electrostatic polymer
fiber formation in a compressed CO2 environment. Two
electrodes (upper and lower) separated by a distance of about
3 mm were inserted into the pressure vessel. The upper elec-
trode was connected to a high voltage power supply using a
high-pressure electrical feedthrough and the lower electrode
was grounded. The PDMS polymer was attached to the lower
grounded electrode and the pressure vessel was loaded with
CO2 at a pressure and temperature above the critical point. A
potential was applied to the upper electrode and the polymer
sample was observed using a CCD camera and TV monitor.
3. Results and discussion
Supercritical and near-critical carbon dioxide as a polymer
swelling agent has been used in many applications, including
synthesis in CO2 –swollen polymers, polymer foam forma-
tion, polymer impregnation, and particle production [8–11].
For the experiment described here it was important to take
advantage of the solubility of the supercritical solvent in the
polymers in order to adequately reduce the polymer viscosity
for fiber “spinning”, but without dissolving or liquefying the
polymer. Therefore, we first established the polymer–CO2
phase behavior. The PDMS–CO2 cloud point curve is shown
in Fig. 2 at a PDMS concentration of 0.4 wt.%. The cloud
point curve shown in Fig. 2 separates the single-phase region
from the two-phase region and occurs at pressures of about
40 MPa and at temperatures higher than 50 ◦ C. The PDMS
polymer also exhibits solidification behavior at temperatures
around 45 ◦ C as can be seen from the data of Fig. 2. For
comparison, the critical point of the CO2 solvent is at a tem-
perature of 31.3 ◦ C and a pressure of about 7 MPa. The PLA
did not dissolve in high-pressure CO2 at temperatures of
25–100 ◦ C and pressure up to 70 MPa. Only the low molecu-
lar weight fraction of PLA was extracted at these conditions.
The PLA polymer showed no liquefaction in CO2 up to
100 ◦ C and exhibited good overall physical integrity. These
findings are in a good agreement with the results published
earlier on the solubility of PLA in CO2 [12].
60
PDMS-CO2
50 one phase
Pressure, MPa
40
30
PDMS fiber forming
20 conditions
CO2 saturation
curve
0
20 30 40 50 60 70 80
Temperature, C
Fig. 2. Cloud point data for PDMS polymer in supercritical CO2 indicating
the fiber processing conditions.
 N. Levit, G. Tepper / J. of Supercritical Fluids 31 (2004) 329–333 331

Fig. 3. Photograph of a PDMS fiber formed by electric forces in supercritical CO2 .

For fiber formation it is important to select processing
conditions that reduce the polymer viscosity sufficiently to
allow rapid shear flow, but do not destroy the physical in-
tegrity of the fiber in the CO2 environment. Although many
studies have been published on high-pressure gas sorp-
tion by polymers and polymer swelling [13–16], very little
quantitative information is available on the change in poly-
mer viscosity under gas sorption [15,16]. For PDMS-based
polymers CO2 sorption can be as great as 30 wt.% at tem-
peratures near 50 ◦ C and pressures around 13 MPa [15].
Significant viscosity reduction was reported for PDMS with
a concentration of CO2 higher than 10 wt.% [15].
A 0.01–0.02 g polymer sample was attached to the lower
grounded electrode and the vessel was filled with liquid CO2 .
The upper electrode was then placed at a high potential and
the polymer sample was equilibrated in near critical or su-
percritical CO2 by gradually increasing the temperature and
pressure. Although it was difficult to quantitatively establish
the equilibration time between the CO2 and the polymer
sample during this process, we estimate from optical changes
in the polymer induced by the CO2 that equilibrium times
were less than 1 min. The polymer was observed visually us-
ing a CCD camera and a monitor. The pressure and temper-
ature were recorded when a polymer fiber formed between
the grounded electrode and the high voltage counter elec-
trode. Fig. 3 is a photograph of a typical PDMS fiber formed
in a supercritical CO2 environment at a temperature of 40 ◦ C
and a pressure of 14 MPa. This thermodynamic state is
above the CO2 critical point, but well below the PDMS–CO2
single-phase region illustrated in Fig. 2. The potential placed
on the upper electrode was +2500 V. The solid PDMS
polymer fiber shown in Fig. 3 is approximately 250 ␮m in
diameter, was formed against gravity and was pulled up by
electrostatic forces alone. The fiber remained intact after
removal of the voltage and CO2 . No fiber formation was
observed from the PDMS polymer without CO2 (in air) at
temperatures ranging from 23 to 50 ◦ C and at potentials up
to ±2500 V.

Fig. 4. Photograph of small and large diameter PLA fibers formed by electric forces in supercritical CO2 .
332 N. Levit, G. Tepper / J. of Supercritical Fluids 31 (2004) 329–333
2000
1800
1600
1400
1200
Voltage, V
first fiber
1000
stable fiber
800
600
400
200
0 polymer samples, we believe that supercritical fluids can
23C 42C
Fig. 5. Comparison of PLA fiber formation by increasing the voltage in
near-critical (T = 23 ◦ C) and supercritical (T = 42 ◦ C) CO2 at a constant
pressure of 14 MPa.
Similar trends in fiber formation were observed for the
PLA polymer. Photographs of two typical PLA fibers formed
in the supercritical CO2 environment are presented in Fig. 4.
The larger diameter fiber (Fig. 4b) was produced at a tem-
perature of 42 ◦ C and a pressure of 14 MPa at a potential
of −2000 V and was stable after removal of the CO2 . The
smaller diameter fiber shown in Fig. 4a was unstable over
time and disintegrated under its own weight in the CO2 envi-
ronment. In order to understand the fiber formation process,
the CO2 temperature and pressure and the potential differ-
ence were systematically varied. No PLA fiber formation
was observed without CO2 assistance (in air) at tempera-
tures from 23 to 42 ◦ C and potentials up to −2000 V. Stable
PLA fibers were produced in near-critical carbon dioxide at
CO2 pressures from 6.5 to 15 MPa at room temperature and
a potential of −2000 V. The influence of the electric field
magnitude on the fiber production was studied by gradually
increasing the field strength at a constant system pressure
and temperature. Small fibers (as shown in Fig. 4a) were pro-
duced at lower field strengths (beginning around −800 V),
but were unstable in the high-pressure CO2 environment.
Larger fibers (as shown in Fig. 4b) were formed at higher
field strengths (above −1400 V) and were stable both in and
after removal of the CO2 . From the PLA fiber images we
estimate that the smaller fibers had a diameter of less than
100 ␮m and the largest fiber was about 350 ␮m.
Fig. 5 is a plot of the critical voltage necessary to form
both small, but unstable fibers and large stable PLA fibers
at two different temperatures at a CO2 pressure of 14 MPa.
At lower temperatures, the critical fiber production voltage
was reduced and we believe that this is due to the higher
CO2 density at the lower temperatures at a fixed pressure
resulting in a higher gas concentration in the polymer-rich
phase. This is consistent with what has been reported in the
literature for other polymers, such as PDMS [15].
In this initial report we have made no any attempt to model
the fiber formation mechanisms or determine the process
window or fiber formation kinetics, but we suspect that, un-
der the influence of the relatively strong electric field, the
insulating polymer sample becomes electrically charged due
to charge injection from the grounded electrode. The fiber
forms along electric field lines when the polymer viscosity is
lowered sufficiently to promote shear flow. It is well known
that the average diameter of electrospun fibers increases with
solution concentration. Therefore, the relatively large diam-
eter of the fibers pulled from the un-dissolved bulk samples
and shown in Figs. 3 and 4 were expected and are consistent
with the trends reported in the literature.
In addition to fiber formation from un-dissolved bulk
play an important role in the general electroprocessing of
polymers. For example, it should be possible to form electro-
spun fibers directly from the single-phase region (i.e. com-
pletely dissolved polymer). In addition, supercritical CO2
can potentially be used as an anti-solvent to enhance the
fiber formation process in systems employing conventional
liquid solvents. We are continuing and extending our inves-
tigations to include other polymers and processing condi-
tions and will present these results and model calculations
in a future publication.
4. Conclusions
Polymer fibers were produced using only electrostatic
forces and without the use of a liquid solvent. This new su-
percritical fluid assisted electrospinning (SAES) technique
could find applications in areas ranging from microelectron-
ics to sensor and filter development.
Acknowledgements
This work was supported by a contract from the Air Force
Office of Scientific Research (#F49620-02-C-0056).
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