Mi cro- and Nanostructured Surface Morphol ogy on El ectrospun Pol ymer

Fi bers
Silke Megelski,

J ean S. Stephens,

D. Bruce Chase,

and J ohn F. Rabolt*

,
Department of Material Scienceand Engineering and DelawareBiotechnology I nstitute, University of
Delaware, Newark, Delaware19716; and Central Research and Development, Experimental Station,
Dupont, Wilmington, Delaware19880
Received March 21, 2002
ABSTRACT: El ectrospun fi bers were produced usi ng a vari ety of sol vents to i nvesti gate the i nfl uence of
pol ymer/sol vent properti es on the fi ber surface morphol ogy. El ectrospi nni ng i s a novel processi ng techni que
for the producti on of fi bers wi th di ameters i n the range of a few nanometers to tens of mi crometers. We
have been abl e to produce pol ymeri c fi bers wi th a hi gh surface area through the i ntroducti on of a mi cro-
and nanostructured surface structure, whi ch we refer to as a porous morphol ogy. These features coul d
be i ntroduced i n several di fferent pol ymeri c fi bers i ncreasi ng thei r range of appl i cati on si gni fi cantl y.
The pores vary from densel y packed, wel l -formed nanopores wi th di ameters i n the range 20-350 nm to
l arger fl at pores of about 1 m. The i ncreased surface area of pol ymeri c fi bers was correl ated wi th hi gh
vol ati l i ty sol vents used i n the el ectrospi nni ng process. The effect of processi ng parameters on the fi ber
surface morphol ogy was al so i nvesti gated usi ng opti cal mi croscopy, fi el d emi ssi on scanni ng el ectron
mi croscopy (FESEM), transmi ssi on el ectron mi croscopy (TEM), and atomi c force mi croscopy (AFM).
Introduction
The abi l i ty to shape materi al s on di fferent l ength
scal es i ncl udi ng the nanoscal e i s i mportant for many
appl i cati ons. When hi gh surface-to-vol ume rati o materi -
al s are requi red, nanoparti cl es are often the fi rst choi ce,
but i ntroduci ng nanoscal e texture/features on nano- or
mi crosi zed materi al s wi l l al so further i ncrease the
surface-to-vol ume rati o.
Spontaneousl y assembl ed submi cron structures have
been descri bed previ ousl y i n a vari ety of materi al sys-
tems. Recentl y Sri ni vasarao et al . reported the for-
mati on of a three-di mensi onal l y ordered array of ai r
bubbl es i n a pol ystyrene (PS) fi l m based on evaporati ve
cool i ng and the formati on of breath fi gures.
1
Porous PS
membranes have al so been created by a thermal l y
i nduced phase separati on (TI PS) techni que.
2,3
Porous
membranes from di fferent pol ymeri c materi al s have
been prepared by other phase separati on techni ques,
but al so recentl y by el ectrospi nni ng pol ymers onto a
grounded target to create a mat.
4-6
Nanoscal e struc-
tures on el ectrospun pol ymer fi bers of pol y-L-l acti de
(PLLA), pol ycarbonate (PC), and pol y(vi nyl carbazol e)
fi bers usi ng di chl oromethane as a sol vent were bri efl y
descri bed by Bogni tzki et al .
7
Recentl y they reported the
preparati on of nanostructured pol yl acti de (PLA) and
pol y(vi nyl pyrrol i done) (PVP) fi bers by sel ecti ve removal
of one of the pol ymer phases after el ectrospi nni ng the
fi bers from a ternary sol uti on.
8
Tradi ti onal mel t spun fi bers range i n di ameter from
about 5 to 200 m, whereas el ectrospun fi bers can have
di ameters i n the nanometer range.
9-11
El ectrospi nni ng
of a vari ety of syntheti c as wel l as natural pol ymer fi bers
for di fferent appl i cati ons has al so been reported i n the
l i terature.
7,9,12-21
El ectrospi nni ng, deri ved from el ec-
trosprayi ng,
22,23
empl oys a pi pet or syri nge and needl e
that contai ns a pol ymer sol uti on whi ch can be charged
by an el ectrode hangi ng i n the sol uti on or by a hi gh
vol tage appl i ed to a needl e at the end of the syri nge. A
pol ymer dropl et suspended from the end of the needl e
becomes deformed from a hemi spheri cal shape to a
coni cal shape, cal l ed a Tayl or cone, by el ectri cal forces.
When the accumul ated charge on the surface of the
dropl et overcomes the surface tensi on, a pol ymer jet i s
ejected from the ti p of the cone. The jet reaches an
i nstabi l i ty poi nt after a few centi meters of travel from
i ts ori gi n and the jet begi ns to whi p or spl i ts i nto bun-
dl es of smal l er fi bers. There are a number of works de-
scri bi ng the el ectri cal l y forced jet and i ts i nstabi l i -
ti es.
24-29
The el ectrospun fi bers are then col l ected on
an opposi tel y charged or grounded target, produci ng a
macroscopi cal l y i sotropi cal l y ori ented fi ber mat. Re-
centl y, Theron and co-workers have demonstrated the
col l ecti on of al i gned fi bers on a rotati ng di sk.
30
The goal of thi s work i s to i nvesti gate the di fferent
pol ymer/sol vent systems i n whi ch mi cro- and nanopores
can be produced on el ectrospun fi ber surfaces. By
varyi ng pol ymer archi tecture and processi ng param-
eters, pol ymeri c fi bers can be spun wi th a l arge surface
area for di fferent appl i cati ons such as membranes for
speci al texti l es, fi l ter systems, bi ol ogi cal sensors, scaf-
fol ds, and transport medi a. The i nfl uence of the materi al
characteri sti cs and the processi ng parameters on the
surface morphol ogy of el ectrospun fi bers was i nvesti -
gated usi ng several techni ques, i ncl udi ng opti cal mi -
croscopy, FESEM, TEM, and AFM. Our studi es have
concentrated on the mi cro- and nanostructured surface
morphol ogy as a functi on of sol uti on concentrati on, spi n-
ni ng vol tage, fl ow rate of the sol uti on, and the needl e
to target di stance (worki ng di stance). A vari ety of crys-
tal l i ne and amorphous pol ymers, i ncl udi ng pol ycarbon-
ate (PC), pol y(ethyl ene oxi de) (PEO), and pol y(methyl
methacryl ate) (PMMA), were el ectrospun from di fferent
sol vent systems to compare thei r surface morphol ogy.
I n addi ti on the i nfl uence of sol vent vapor pressure was
i nvesti gated on el ectrospun PS i n detai l .
* To whom correspondence shoul d be addressed. E-mai l :
rabol t@UDEL.edu.

Uni versi ty of Del aware.

Dupont.
8456 Macromolecules 2002, 35, 8456-8466
10.1021/ma020444a CCC: $22.00 2002 Ameri can Chemi cal Soci ety
Publ i shed on Web 09/27/2002
Experimental Section
Materials. To prepare el ectrospun fi bers of PS, di fferent
wei ght concentrati ons (Mw ) 190 000; Sci enti fi c Pol ymer
Products) i n tetrahydrofuran (THF) (HPLC; Fi sher Sci enti fi c),
di methyl formami de (DMF) (certi fi ed A.C.S.; Fi sher Sci enti fi c),
carbon di sul fi de (CS
2) (reagent A.C.S.; Fi sher Sci enti fi c), and
tol uene (certi fi ed A.C.S.; Fi sher Sci enti fi c) were used. Other
pol ymer/sol vent systems i nvesti gated were PEO (M
w ) 300 000;
BDH l aboratory reagents) i n water, chl oroform (CHCl 3) (HPLC;
Fi sher Sci enti fi c), and acetone (HPLC; Fi sher Sci enti fi c);
PMMA (M
w ) 540 000; Sci enti fi c Pol ymer Products) i n THF,
acetone, and CHCl 3; and PC (Mw ) 60 000; Sci enti fi c Pol ymer
Products) i n CHCl 3 and THF. Al l the pol ymers, except PC,
di ssol ved at room temperature wi th 1-2 h of sti rri ng. PC
di ssol ved i n THF i n a warm water bath after a mi ni mum of 4
h of strong sti rri ng. The properti es of the pol ymers and
sol vents used are l i sted i n Tabl es 1 and 2, respecti vel y.
Electrospinning Experiments. A schemati c of the el ec-
trospi nni ng apparatus i s shown i n Fi gure 1. A pol ymer sol uti on
was pl aced i n a 5 mL syri nge attached to a syri nge pump
(Ori on SAGE) i n a verti cal mount. The potenti al was appl i ed
to the hypodermi c needl e (Hami l ton) on the end of the syri nge
usi ng a hi gh vol tage power suppl y (Gl assman Hi gh Vol tage).
A grounded al umi num sheet was pl aced on the surface of an
adjustabl e l ab jack and used as the target. The di stance
between the needl e and target was opti mi zed for each set of
experi ments. The spi nni ng condi ti ons for each pol ymer are
l i sted i n Tabl e 3.
Characterization. Vi scosi ty measurements of the pol ymer
sol uti ons were performed wi th a stress-control l ed rheometer
at 25 ( 0.1 C (Rheometri c SR 500). The di ameter and mor-
phol ogy of the el ectrospun pol ymer fi bers were determi ned by
opti cal mi croscopy (Ol ympus BX60), fi el d emi ssi on scanni ng
el ectron mi croscopy (FESEM, JEOL JSM-6330F), and AFM
(Nanoscope I I I , Di gi tal I nstruments). Si nce most el ectrospun
fi bers observed i n these experi ments do not have a round cross
secti on but appear more ri bbonl i ke, we wi l l use the l argest
measurement of the aspect rati o (of a fi ber cross secti on) as
the di ameter for compari son purposes. To obtai n FESEM
i mages the fi bers were col l ected on an al umi num SEM di sk
then coated wi th carbon or gol d. The accel erati on vol tages and
the worki ng di stances for each i mage are stated i n the fi gure
capti ons. The cross secti ons of the fi bers were determi ned
usi ng TEM (JEOL JEM 2000FX). For each sampl e a mi cro-
tomed sl i ce of fi ber embedded i n an epoxy resi n pl aced on a
copper gri d was used. The fi bers were stai ned before anal ysi s
i n a RuO
4 atmosphere for 105 mi n, pl aced i n epoxy resi n
(embeddi ng ki t DER 332-732; El ectron Mi croscopy Sci ence),
and hardened i n an oven at 45 C for 14 h and then at 60 C
for 3 days.
Results
VaryingElectrospinningConditions. El ectrospi n-
ni ng processi ng parameters (such as sol uti on concentra-
ti on, spi nni ng vol tage, worki ng di stance, and sol uti on
feedi ng rate) i nfl uence the morphol ogy of the pol ymeri c
fi bers as shown previ ousl y.
15,31
These parameters have
been i nvesti gated i n order to el ectrospi n PS from THF
and to fi nd the opti mum condi ti ons for obtai ni ng
beadl ess fi bers. Moreover the i nfl uence of these process-
i ng parameters on the surface morphol ogy and pore
formati on on PS fi bers have al so been i nvesti gated and
wi l l be di scussed bel ow.
A. SolutionConcentration.The concentrati on of PS
i n THF was vari ed from 18 to 35 wt % i n order to study
i ts effect on the fi ber morphol ogy and pore formati on.
The vi scosi ty of the sol uti on i ncreased as the PS
concentrati on i ncreased. Al l other spi nni ng parameters
were kept constant as shown i n Tabl e 4. Opti cal
mi crographs show an i ncrease i n fi ber di ameter from
0.8 to 20 ((10) m wi th i ncreasi ng sol uti on concentra-
ti on. The PS fi bers are beaded up to a concentrati on of
30 wt % wi th the occurrence of beads decreasi ng wi th
i ncreasi ng sol uti on vi scosi ty. The si ze of the beads as
wel l as the si ze of the fi bers i ncreases wi th hi gher PS
concentrati on, as shown i n Fi gure 2.
Al l PS fi bers observed i n thi s work have a ri bbon-
shaped cross secti on and a surface wi th nanoporous
features, as shown by the FESEM i mages i n Fi gure 3.
The shape and the si ze of these nanopores were ob-
served to change wi th concentrati on. The 18 wt % PS
sampl e has two ki nds of pores, smal l er mostl y rounded
pores about 20 nm i n di ameter and l arger el ongated
pores wi th di mensi ons of approxi matel y 200 nm i n the
l ong axi s di recti on (Fi gure 3a). The pores i n fi bers spun
at hi gher PS concentrati ons are approxi matel y round
and have a narrower si ze di stri buti on of 50-180 nm.
At 25 wt % PS, the pores have a rounder shape and are
about 50-100 nm i n di ameter. PS fi bers spun from a
35 wt %sol uti on di spl ay round pores that are somewhat
overl apped wi th each other and have di ameters that
range from about 50 to 180 nm. Typi cal l y these fi bers
Table 1. Polymer Data
pol ymer
Tg
(C)
Tm
(C)
Mw
(g mol
-1
) r/1 kHz
F
(g cm
-3
)
PS 100 240 190 000 2.4-2.65 1.04
PC 150 265 60 000 3.0 (25 C) 1.20
PMMA 105 540 000 3.0-3.6 1.20
PEO -67 65 300 000 1.21
Table 2. Solvent Data
sol vent Tb (C) Tm (C)
pv/25 C
(kPa)
F
(g cm
-3
)
/20 C
(mPa s) /20 C
cp
(J g
-1
K
-1
) (D)
/25 C
(mN m
-1
)
CS2 46 -100 48.2 1.2632 2.6 1.00 0 31.58
acetone 56 -94 30.8 0.7899 0.324 20.7 (25 C) 2.18 2.88 23.46
CHCl 3 62 -63.5 26.2 1.4832 0.568 4.806 0.96 1.04 26.67
THF 66 -108 21.6 0.8892 0.468 7.6 1.72 1.75 23.97 (?)
cycl ohexane 81 7 13 0.7785 0.979 2.023 1.84 0 24.65
water 100 0 2.3388 0.998 23 1 78.54 1.00 1.84 71.99
tol uene 111 -95 3.79 0.8669 0.59 2.379 (25 C) 1.70 0.37 27.93
DMF 153 -61 2.7 0.944 (25 C) 0.92 36.7 2.06 3.82
Figure 1. Schemati c di agram of el ectrospi nni ng apparatus.
Macromolecules, Vol. 35, No. 22, 2002 El ectrospun Pol ymer Fi bers 8457
are twi sted as shown i n Fi gure 3e. Fi gure 3f shows a
hi gh contrast FESEM mi crograph, whi ch represents the
mi crotexture of the fi ber surface.
B. Spinning Voltage. The vol tage appl i ed duri ng
el ectrospi nni ng was al so vari ed and i ts i nfl uence on the
PS fi bers i nvesti gated. The fi ber si ze decreases from
about 20 to 10 m wi th i ncreasi ng spi nni ng vol tage
(5-12 kV), keepi ng al l other condi ti ons constant. The
PS fi bers have a ri bbon-shaped cross secti on and are
twi sted. Some beads occur, but onl y at 5 and 12 kV. I n
addi ti on, the surfaces of these PS fi bers are rough, and
nanopores wi th pore di ameters i n the range 50-350 nm
appear to be densel y packed on the surface. The pore
si ze di stri buti on i s not affected by changi ng the vol tage.
A TEM i mage, shown i n Fi gure 4, of a PS fi ber cross
secti on spun at 7.5 kV confi rms the ri bbon shape of the
fi ber and the roughened surface wi th densel y packed
nanopores. The doubl e bonds of the phenyl ri ng on the
PS fi ber surface combi ne wi th RuO
4
and appear as dark
areas i n the TEM due to thei r hi gher scatteri ng capaci ty
for el ectrons. I t i s very cl ear that these pores are l ocated
onl y on the fi ber surface and have a depth of about
50-75 nm, whi ch has al so been i ndependentl y veri fi ed
by AFM.
C. WorkingDistance. To assess the effect of work-
i ng di stance on fi ber morphol ogy, the gap between the
hi ghl y charged needl e and the grounded target was
narrowed from 35 to 15 cm i n 5 cm steps, keepi ng al l
other parameters constant. I t was found that, al though
the fi ber si ze does not change si gni fi cantl y, i nhomoge-
neousl y di stri buted el ongated beads start to form al ong
the PS fi bers after reduci ng the worki ng di stance by
onl y 5 cm. The morphol ogy of the ri bbon-shaped PS
fi bers i s al so not i nfl uenced by changi ng the worki ng
di stance. Al l fi bers have mi crostructure textured sur-
faces and nanopores, whi ch range i n si ze from 70 to 200
nm i n di ameter.
D. Flow Rate. The pump speed and hence the fl ow
rate of the PS sol uti on was changed to determi ne i ts
effect on fi ber si ze and morphol ogy. Bead formati on i s
observed when the fl ow rate i s 0.10 mL/mi n and hi gher.
The ri bbon-shaped fi bers i ncrease i n si ze from about 5
to 20 m and show the typi cal mi crotexture and nano-
pores. The pore si zes range i n di ameter from 50 to 250
nm. The mean pore si ze i s observed to i ncrease from
about 90 to 150 nm wi th i ncreasi ng fl ow rate. I n Fi gure
5 are shown the FESEM i mages of these fi bers as a
functi on of fl ow rate.
Table 3. Conditions for Electrospinning
pol ymer Mw (g/mol ) sol vent c (wt %) U (kV) d (cm)
fl ow rate
(mL/mi n)
needl e
o.d. (mm)
fi ber o.d./pore
o.d. (m/nm)
PS 190 000 CS2 30 20 12 0.10 0.35 4-25/<100-750
THF 18-35 10 35 0.07 0.51 5-15/50-150
acetone/cycl ohexane 30 10 35 0.07 0.51 15-30/300-1000
tol uene 30 14 15 0.07 0.16 5/no pores
DMF 30 10 35 0.07 0.51 10/no pores
THF/DMF 30 10 35 0.07 0.51 10/50-
PEO 300 000 H2O 10 7 15 0.0025 0.51 0.2-0.8/no pores
CHCl 3 10 8 25 0.19 0.51 10/no pores
acetone 10 8 20 0.24 0.51 0.8-14/no pores
PC 60 000 CHCl 3 20 10 35 0.09 0.51 10-12/100-250
THF 20 10 35 0.07 0.35 20/mi cropores
PMMA 540 000 THF 10 10 35 0.07 0.51 10-35/mi cropores
acetone 10 10 35 0.07 0.51 7.5/250
CHCl 3 10 10 35 0.09 0.51 0.75-13/75-250
Table 4. Processing Parameter of Electrospinning PS
fromTHF
c
(wt %)
vi scosi ty
(Pa s)
U
(kV)
d
(cm)
fl ow rate
(mL/mi n)
needl e o.d.
(mm)
18 0.085 10 35 0.07 0.51
20 0.116
25 0.214
28 0.258
30 0.360
35 0.614
35 0.614 5 35 0.07 0.51
7.5
10
12
35 0.614 10 30 0.07 0.51
25
20
15
35 0.614 10 35 0.004 0.51
0.07
0.10
0.14
0.24
Figure2. Opti cal mi croscope i mages (5 enl argement) of PS
fi bers el ectrospun from THF as a functi on of PS concentra-
ti on: (a) 18 wt %; (b) 20 wt %; (c) 25 wt %; (d) 28 wt %; (e) 30
wt %; (f) 35 wt %.
8458 Megel ski et al . Macromolecules, Vol. 35, No. 22, 2002
The condi ti ons to produce beadl ess ri bbon-shaped
fi bers of PS el ectrospun from THF were found to be as
fol l ows: 30 to 35 wt % concentrati on, 7.5 to 10 kV, 35
cm worki ng di stance, and 0.07 mL/mi n fl ow rate. PS
fi bers el ectrospun under these condi ti ons have di am-
eters i n the range of 20 ( 10 m wi th a mi crotextured
surface and densel y packed nanopores wi th di ameters
i n the 50-200 nm range. The bead formati on i s a
functi on of the PS concentrati on as wel l as of the
spi nni ng vol tage, the worki ng di stance, and the feed
rate. A l ower concentrati on or devi ati on of the vol tage
from the opti mum as wel l as a smal l er di stance between
needl e and target or faster fl ow rate resul ted i n beaded
fi bers wi th di fferent di ameters. The si ze range of PS
fi bers produced i n thi s work ranges from 0.8 to 20 ((
10) m. An i ncreasi ng sol uti on concentrati on or i ncreas-
i ng fl ow rate as wel l as a decrease i n spi nni ng vol tage
resul ted i n i ncreased fi ber si ze. The i nfl uence of these
parameters on the pore formati on i s not as obvi ous as
i t i s for bead formati on and fi ber si ze. The pores range
i n si ze from 20 to 350 nm. They vary i n si ze and shape
wi th changi ng PS concentrati on. There are even pores
of di fferi ng si ze and shape i n one PS fi ber el ectrospun
from THF (18 wt %).
Electrospinning PS fromVarying Solvents. Al -
though many syntheti c and natural pol ymers have been
el ectrospun usi ng a vari ety of sol vents, the formati on
of pores was bri efl y descri bed onl y by Bogni tzki et al .
7
Work has al so appeared on PS membranes, where the
pores are ei ther a functi on of sol vent densi ty or are
createdby thermally inducedphaseseparationtechniques.
1-3
I n thi s work, we bel i eve that the physi cal properti es of
the sol vents pl ay an i mportant rol e i n thi s process and
hypothesi ze that the sol vent vol ati l i ty pl ays a cri ti cal
rol e i n the pore formati on process. Therefore, for com-
pari son, a vari ety of sol vents wi th di fferent boi l i ng
Figure3. FESEM i mages of PS fi bers el ectrospun from THF as a functi on of PS concentrati on: (a) 18 wt % (15 kV, WD 6.1 mm);
(b) 25 wt % (15 kV, WD 5.8 mm); (c) 28 wt % (15 kV, WD 5.8 mm); (d) 30 wt % (2.0 kV, WD 8.6 mm); (e) 35 wt % (15 kV, WD 5.5
mm); (f) hi gher magni fi cati on of part e (15 kV, WD 5.5 mm).
Macromolecules, Vol. 35, No. 22, 2002 El ectrospun Pol ymer Fi bers 8459
poi nts and vapor pressures (Tabl e 2) were used to
el ectrospi n PS fi bers.
A. Carbon Disulfide (CS
2
). The most vol ati l e sol -
vent used was CS
2
. I ts vapor pressure was so hi gh that
the pol ymer dropl et on the needl e formed a ski n on i ts
surface al most i mmedi atel y. Therefore, jet formati on
was onl y possi bl e after renewi ng the dropl et frequentl y.
El ectrospun fi bers were created between l arge dropl ets
(see condi ti ons i n Tabl e 3) and were i nvesti gated wi th
FESEM.
The fi bers (4-25 m i n di ameter) shown i n Fi gure 6
al so have a ri bbon-shaped cross secti on and exhi bi t
addi ti onal ri bbonl i ke textures al ong the fi bers. The
surface of these fi bers i s smooth wi th pores rangi ng from
about 100 to 750 nm that are not packed as densel y as
those observed on PS fi bers spun from THF.
B. Toluene. I t was more di ffi cul t to el ectrospi n PS
from tol uene than from THF. Wi th the condi ti ons l i sted
i n Tabl e 3, a smal l jet was formed for onl y a few seconds.
The col l ected fi bers were approxi matel y 5 m i n di am-
eter and were ri bbon shaped. The fi ber surface i s very
rough, showi ng no defi ned pores but rather l arge
el ongated hol es of about 1 m, pri mari l y on the fl at si de
of the fi ber.
C. Tetrahydrofuran/Dimethylformamide (THF/
DMF). I n a more detai l ed experi ment we i nvesti gated
THF/DMF mi xtures wi th sol vent rati os of 90/10, 75/25,
50/50, 25/75, and 10/90%. Fi gure 7 shows the effect of
the decreasi ng vapor pressure of the sol vent mi xture
on the observed mi crotexture for PS fi bers spun from
100% THF, THF/DMF rati os of 75/25 and 50/50%, and
100% DMF. Li ke PS el ectrospun from THF onl y, the
fi bers are ri bbon shaped and are approxi matel y 10 m
i n di ameter. At a rati o of 75/25%THF/DMF (Fi gure 7b)
the pores become l arger, l ess uni form, and shal l ower
than those on fi bers el ectrospun from 100%THF (Fi gure
7a). Surface roughness and/or mi crotexture i s observed
at 50/50% THF/DMF (Fi gure 7b), but these features
di sappear when the fi bers are spun from 100% DMF
(Fi gure 7d). The mi crotexture di mi ni shes unti l i t fi nal l y
di sappears, l eavi ng a smooth surface wi th decreasi ng
sol vent vol ati l i ty.
I n general , a very hi gh densi ty of pores was observed
on PS fi bers el ectrospun from THF, and the resul ti ng
mi crotexture i nduced at the fi ber surface i ncreases the
surface area by as much as 20 to 40% dependi ng on the
di ameter of the fi ber. The i nfl uence of the sol vent vapor
pressure coul d be observed by substi tuti on of THF wi th
DMF wi th the mi crotexture and nanopores of the PS
fi bers di sappeari ng as the vol ati l i ty of the mi xed sol vent
system decreased. To be sure of the effect of sol vent
vol ati l i ty, we have al so i nvesti gated mi xtures of acetone
and cycl ohexane to el ectrospi n PS. These fi bers showed
an i ncrease i n surface roughness and pores wi th i n-
creasi ng boi l i ng poi nt of the sol vent mi xture. However,
both sol vents form an azeotrope at 67/33%wi th a l ower
boi l i ng poi nt of 53 C, whi ch makes an i nterpretati on
more compl ex.
Investigation of Different Polymers. I n addi ti on
to PS, the i nfl uence of the sol vent on el ectrospi nni ng of
other pol ymers was al so i nvesti gated. The ai m was to
determi ne whether a l arge vari ety of porous pol ymer
fi bers wi th a tai l orabl e surface morphol ogy coul d be
produced for di fferent appl i cati ons. The pol ymers i n-
cl uded PMMA, PC, and PEO, and the el ectrospi nni ng
condi ti ons used are l i sted i n Tabl e 3. The sol uti on
concentrati on was adjusted so that el ectrospi nni ng coul d
take pl ace under al most i denti cal i nstrument condi ti ons
for each pol ymer.
A. Atactic Poly(methyl methacrylate) (PMMA).
PMMA i s an amorphous pol ymer wi th hi gh opti cal
cl ari ty maki ng i t i mportant for appl i cati ons where
l i ght transmi ssi on i s necessary. I t i s al so resi stant to
many aqueous-based i norgani c reagents, i ncl udi ng di -
l ute al kal i s and aci ds.
32
I n thi s study, we i nvesti gated
the surface morphol ogy of PMMA fi bers el ectrospun
from acetone, CHCl
3
, and THF, whi ch are shown i n
Fi gure 8.
Li ke al l el ectrospun PS fi bers studi ed thus far, the
PMMA fi bers had a ri bbon-shaped cross secti on i nde-
pendent of the sol vent (acetone, CHCl
3
, THF) used.
Those fi bers spun from the most vol ati l e sol vent,
acetone, have a di ameter of about 7.5 m. The fi ber
surface contai ns a smal l amount of texture wi th some
broadl y di stri buted pores that were el ongated al ong the
fi ber di recti on and were about 250 nm i n si ze (Fi gure
8a). There was a bi modal di stri buti on of fi bers created
duri ng el ectrospi nni ng PMMA from CHCl
3
. The smal l er
fi bers had a di ameter of approxi matel y 750 nm and were
very beaded, whereas the l arger fi bers had a di ameter
of about 13 m and appeared more uni form. No beads
were present but the fi bers di d contai n a mi crotextured
surface di sti nctl y di fferent from that produced from
acetone. Onl y the l arger fi bers exhi bi ted very densel y
packed pores of about 75 to 250 nm (Fi gure 8, parts b
and c). Fi bers of about 10 m i n di ameter wi th a
mi crotextured surface morphol ogy were observed for
PMMA spun from THF (Fi gure 8d). Thi s mi crotexture
appeared as l arge fl at pores of about 1 m or l arger.
Figure 4. TEM i mage (2000 kV) of a cross secti on of a PS
fi ber el ectrospun from THF (35 wt %, 7.5 kV, 0.07 mL/mi n,
35 cm, 0.51 mm needl e di ameter).
8460 Megel ski et al . Macromolecules, Vol. 35, No. 22, 2002
PMMA el ectrospun from CHCl
3
produces fi bers wi th
the l argest surface area and most di sti ncti ve pores
therefore maki ng CHCl
3
best sol vent for produci ng a
hi ghl y textured PMMA fi ber (Fi gure 8). However, i t
seems that other factors i n addi ti on to vapor pressure
must al so be consi dered to expl ai n the formati on of
surface textures and nanopores on el ectrospun pol ymer
fi bers.
B. Polycarbonate (PC). PC i s a semi crystal l i ne
pol ymer wi th very good mechani cal properti es i ncl udi ng
hi gh i mpact strength, good heat resi stance and good
thermal and oxi dati ve stabi l i ty i n the mel t. We have
i nvesti gated the fi ber formati on of PC el ectrospun from
CHCl
3
and THF to compare the surface morphol ogy
wi th that of PS and PMMA.
PC fi bers spun from CHCl
3
have a di ameter of
about 10 m wi th some observabl e texture i n the fl at
part of the ri bbon-shaped fi bers. Round and sl i ghtl y
el ongated nanopores of about 100-250 nm that are
broadl y di stri buted appeared on the fi ber surface (Fi g-
ure 9a). PC fi bers formed from THF are al so ri bbon
shaped but wi th a very pronounced mi crotexture,
whi ch can al so be descri bed as i rregul arl y shaped
mi cropores wi th di ameters of approxi matel y 20 m.
FESEM i mages of both fi ber sampl es are shown i n
Fi gure 9.
C. Poly(ethylene oxide) (PEO). PEO i s of great
commerci al i nterest, because i t combi nes thermopl asti c
behavi or and mechani cal properti es of a hi ghl y crystal -
l i ne, hi gh-mol ecul ar-wei ght pol ymer wi th compl ete wa-
ter sol ubi l i ty.
32
I ts use for syntheti c fi bers, thi ckeners,
and stabi l i zers i n di fferent materi al s makes PEO a
favori te choi ce for el ectrospi nni ng as al ready i l l ustrated
by others.
27,31,33,34
The ai m of our experi ments was to
determi ne the sol vent effect on the PEO fi ber surface
morphol ogy. When acetone, CHCl
3
and water are used
as sol vents, the el ectrospun fi bers exhi bi t a round cross
secti on i n contrast to al l the other pol ymer fi bers studi ed
thus far. The smal l est PEO fi bers were formed from
aqueous sol uti on and were about 200-800 nm i n
Figure5. FESEM i mages of PS fi bers as a functi on of fl ow rate: (a) 0.004 mL/mi n (5 kV, WD 9.5 mm); (b) 0.07 mL/mi n (15 kV,
WD 5.5 mm); (c) 0.1 mL/mi n (15 kV, WD 5.2 mm); (d) 0.14 mL/mi n (15 kV, WD 5.5 mm); (e) 0.24 mL/mi n (15 kV, WD 5.5 mm).
Macromolecules, Vol. 35, No. 22, 2002 El ectrospun Pol ymer Fi bers 8461
di ameter. When PEO fi bers were el ectrospun from
acetone and CHCl
3
the fi ber di ameter vari ed from about
800 to 1400 nm. The surface of the fi bers are smooth
when el ectrospun from acetone and water, but they
exhi bi t a sl i ghtl y rough surface i f el ectrospun from
CHCl
3
. Pores are not observed on any of these el ectro-
spun PEO fi bers, even though i n some cases they were
el ectrospun from vol ati l e sol vents. Currentl y we do not
have an expl anati on for thi s, but note that PEO has a
qui te di fferent gl ass transi ti on temperature, T
g
, of -67
C compared to PS (T
g
) 100 C), PMMA (T
g
) 105 C),
and PC (T
g
) 150 C).
I n general , a broad range of porous pol ymer fi bers or
fi bers wi th l arge surface areas have been produced by
el ectrospi nni ng from several hi ghl y vol ati l e sol vents.
El ectrospun PMMA fi bers from CHCl
3
and al so from
THF exhi bi t a nanoporous surface texture. As the
boi l i ng poi nts of the sol vents (acetone, CHCl
3
, and THF)
used to el ectrospi n PMMA are very si mi l ar, i t was not
possi bl e to determi ne thei r i nfl uence on the formati on
of surface mi crotextures and nanopores. I t has al so been
shown that i t i s possi bl e to form PC fi bers wi th a very
di sti nct mi crotexture from THF, whereas PC fi bers
el ectrospun from CHCl
3
showed a smooth fi ber surface
wi th nanopores present. I n addi ti on, el ectrospi nni ng
PEO from water, acetone, and CHCl
3
as wel l as el ec-
trospi nni ng PS from THF at the l owest concentrati on
coul d produce submi crometer fi bers. However no nano-
pores were observed on el ectrospun PEO fi bers under
any processi ng condi ti ons. When PEO was spun from
CHCl
3
, a sl i ghtl y rough fi ber surface was formed, and
i n contrast to al l the other i nvesti gated materi al s, PEO
fi bers al ways had a round cross secti on.
Discussion
El ectrospi nni ng pol ymer sol uti ons i nvol ves a rapi d
evaporati on of the sol vent whi l e the jet i s accel erated
to the counter el ectrode.
35
Wi thi n mi l l i seconds the
surface area of the jet i s i ncreased dramati cal l y. Thi s
coul d l ead to a number of thermodynami cal l y dri ven
events. For exampl e, a crossi ng of phase boundari es and
a resul ti ng structure formati on by phase separati on can
occur as noted by Bogni tzki and co-workers.
7
They
postul ate that thi s favors a spi nodal phase separati on,
because nucl eati on phenomena requi re more ti me than
the i ni ti al growth of unstabl e concentrati on fl uctuati ons.
Furthermore, the phase-separated regi ons woul d not
have the ti me to coarsen strongl y before vi tri fi cati on.
As a resul t they found that very fi ne phase morphol ogi es
are preserved and thi s l eads to the fol l owi ng questi on:
Why do these phase morphol ogi es exi st onl y on the
surface of the el ectrospun fi bers?
The formati on of nano- and mi crostructures by phase
separati on i n membrane preparati on processes i s very
wel l -known and wi del y di scussed i n the l i terature.
4,5,36-39
There are di fferent phase separati on techni ques such
as i mmersi on preci pi tati on, ai r-casti ng of the pol ymer
sol uti on, vapor-i nduced phase separati on, and thermal l y
i nduced phase separati on (TI PS). An understandi ng of
these techni ques may al so hel p to expl ai n the pore
formati on i n el ectrospun fi bers. I n addi ti on, evaporati ve
cool i ng at the surface of the fi bers coul d l ead to the
condensati on of moi sture and the formati on of breath
fi gures as di scussed by Sri ni vasarao et al . I t i s cl ear that
the el ectrospi nni ng process i s more compl ex si nce the
fi bers are carryi ng charge, whi ch i s not present i n the
formati on of other porous structures.
I f a pol ymer sol uti on (pol ymer and sol vent) i s cast on
a support, evaporati on takes pl ace under convecti ve
condi ti ons. Duri ng sol vent evaporati on the sol uti on
becomes thermodynami cal l y unstabl e and phase sepa-
rati on occurs i nto a pol ymer ri ch and a pol ymer l ean
phase. The concentrated phase sol i di fi es shortl y after
phase separati on and forms the matri x, whereas the
pol ymer l ean phase forms the pores. A phase di agram
coupl ed wi th thermodynami c and ki neti c aspects pro-
vi des i nformati on about structure formati on i n mem-
branes. Al l these general aspects may be transferabl e
to the formati on of porous pol ymer fi bers.
Another mechani sm to be consi dered i n the formati on
of porous el ectrospun fi bers i s that of breath fi gures
recentl y descri bed by Sri ni vasarao et al . Breath fi gures
occur as a resul t of evaporati ve cool i ng due to rapi d
sol vent evaporati on therefore si gni fi cantl y cool i ng the
surface of the el ectrospi nni ng jet as i t travel s from the
syri nge to the target. As the surface cool s moi sture i n
the ai r condenses and grows i n the form of dropl ets. The
dropl ets remai n as i ndi vi dual enti ti es acti ng as hard
spheres due to convecti on currents on the surface of the
jet. As the jet dri es, l eavi ng dri ed fi bers, the water
dropl ets l eave an i mpri nt on the surface of the fi bers i n
the form of pores.
1
Prel i mi nary studi es have shown that
humi di ty does pl ay a rol e on the formati on of porous
el ectrospun fi bers as shown i n Fi gure 10, and therefore,
thi s mechani sm may pl ay a domi nate rol e i n descri bi ng
how and why pores form of these fi bers.
However most of the l i terature descri bes very uni form
ci rcul ar densel y packed pore formati on as the resul t of
breath fi gures.
9,40
As i ndi cated throughout thi s paper
we observe a vari ety of structures on the fi ber surfaces
from densel y packed i rregul ar shaped pores (PS/THF)
Figure 6. (a) FESEM i mage of PS fi ber el ectrospun from
CS2 at 30 wt %; (b) hi gher magni fi cati on of part a (15 kV, WD
8.0 mm).
8462 Megel ski et al . Macromolecules, Vol. 35, No. 22, 2002
to extremel y rough surfaces wi th l oosel y packed el on-
gated pores (PMMA/acetone). These di fferences may
ari se because of vari ati ons i n experi mental condi ti ons
between these experi ments and tradi ti onal breath fi gure
Figure7. FESEM i mages of PS fi bers as a functi on of sol uti on vol ati l i ty: (a) 100% THF (15 kV, WD 8.9 mm); (b) 75/25% THF/
DMF (15 kV, WD 9.3 mm); (c) 50/50% THF/DMF (15 kV, WD 8.8 mm); (d) 100% DMF (15 kV, WD 9.0 mm).
Figure 8. FESEM i mages of PMMA fi bers el ectrospun from (a) acetone, (b) CHCl 3, (c) l arger magni fi cati on of part b (a,b,c: 15
kV, WD 4.8 mm), and (d) THF (15 kV, WD 4.5 mm). I n al l cases, 10 wt % PMMA sol uti ons were used; for condi ti ons, see
Tabl e 3.
Macromolecules, Vol. 35, No. 22, 2002 El ectrospun Pol ymer Fi bers 8463
experi ments. For exampl e i n the el ectrospi nni ng process
the concentrated pol ymer sol uti on i s accel erated through
the humi d ai r whereas i n the work by Sri ni vasarao et
al . the humi d ai r i s movi ng across the surface of the
sol uti on.
1
Due to these di fferences, phase separati on
mechani sms must al so be consi dered i n the expl anati on
of pore formati on of el ectrospun fi bers.
A. Thermally InducedPhaseSeparation(TIPS).
Phase separati on occurs by l oweri ng the temperature
of the sol uti on i n TI PS. The sol uti on then passes
through the bi nodal curve of the phase di agram to enter
the metastabl e regi on. Amorphous pol ymers are known
to produce mi croporous structures by l i qui d/l i qui d phase
separati on, whi ch i s fol l owed by the gel ati on of the
pol ymer.
41
Mi croporous structure formati on has been
observed i n semi crystal l i ne pol ymers due to combi ned
crystal l i zati on and l i qui d/l i qui d phase separati on.
42
Al though the temperature was kept constant duri ng
the el ectrospi nni ng process, evaporati ve cool i ng occurs
as the fi ber traverses the di stance between the syri nge
and the target. Thi s coul d cause TI PS duri ng fi ber
formati on. I f the evaporati ve cool i ng affects onl y the
temperature of the fi ber surface, thi s mi ght expl ai n the
occurrence of pores on the surface onl y. At thi s poi nt i t
i s not known whether the temperature i s changed al ong
the cross secti on of the fi ber. Measurements of temper-
ature di fferences al ong the fi ber duri ng el ectrospi nni ng
wi th an ul trafast heat sensi ti ve camera woul d provi de
addi ti onal i nformati on but i s beyond the scope of the
current i nvesti gati on.
PS and PMMA are amorphous pol ymers, whereas
PEO and PC are semi crystal l i ne. Thi s coul d effect some
di fferences i n the surface morphol ogy of the i nvesti gated
materi al s when TI PS occurs. Al so as i ndi cated earl i er,
the T
g
of these pol ymers vari es from -67 (PEO) to +150
C (PC), and thus pl asti ci zati on of the PC fi bers coul d
effect the pore formati on and, as the sol vent evaporates,
be responsi bl e for freezi ng i n the porous surface mor-
phol ogy.
B. Vapor-InducedPhaseSeparation. During vapor-
i nduced phase separati on the pol ymer sol uti on under-
goes phase separati on by penetrati on of nonsol vent from
the vapor phase. Si nce the mass transfer i s very sl ow,
onl y a fl at concentrati on profi l e i s obtai ned i n the
membrane. The rate-l i mi ti ng step for the nonsol vent
Figure 9. FESEM i mages of PC fi bers el ectrospun from (a)
CHCl 3 and (b) THF (15 kV, WD 4.5 mm).
Figure10. FESEM i mages of PS fi bers el ectrospun from THF
(35 wt % PS/THF) at di fferent rel ati ve humi di ti es: (a) 50%
rel ati ve humi di ty (15 kV, WD 5.5 mm), (b) 30% rel ati ve
humi di ty (15 kV, WD 6.7 mm), and (c) 20% rel ati ve humi di ty
(15 kV, WD 5.8 mm).
8464 Megel ski et al . Macromolecules, Vol. 35, No. 22, 2002
transport i nto the pol ymer sol uti on i s the sl ow di ffusi on
i n the vapor phase adjacent to the fi l m surface.
43
I f the
vapor phase i s saturated wi th sol vent, ski n formati on
can be hi ndered, whi ch i s possi bl e for hi gh vol ati l e
sol vents. I n thi s case, the pore formati on i s determi ned
by the vapor pressure of the nonsol vent and the pol ymer
concentrati on. I ncreasi ng rel ati ve humi di ty or decreas-
i ng pol ymer concentrati on woul d i ncrease the pore
formati on.
I n addi ti on to condensi ng on the fi ber surface due to
evaporati ve cool i ng, water i n the atmosphere al so works
as a nonsol vent for al l i nvesti gated pol ymers, except for
PEO. Thi s mi ght al so contri bute to some of the di ffer-
ences i n surface morphol ogy observed when PS fi bers
are el ectrospun from THF at di fferent rel ati ve humi di -
ti es. We have al so observed that the pore formati on i s
cl earl y decreased wi th i ncreasi ng PMMA concentrati on
from 10 to 30 wt % i n an experi ment where di fferent
PMMA concentrati ons were el ectrospun from THF. Thi s
mi ght al so refl ect an effect of vapor-i nduced phase
separati on. The occurrence of pores onl y on the fi ber
surfaces al so supports vapor-i nduced phase separati on
rather than a TI PS process.
Conclusion
Thi s work descri bes i nvesti gati ons on four di fferent
pol ymers el ectrospun from vari ous sol vents to create a
broad range of fi bers wi th di fferent surface morphol o-
gi es. The abi l i ty to produce pol ymeri c fi bers or materi al s
wi th a tai l orabl e surface morphol ogy i ncreases thei r
range of appl i cati on si gni fi cantl y. When a nanoporous
morphol ogy, as shown i n these studi es, i s combi ned wi th
the excepti onal l y smal l di ameters (10-1000 nm) of
the smal l est fi bers, i t can gi ve ri se to an extremel y
l arge surface area (100-1000 m
2
/g). The surface
area of these smal l fi bers can easi l y surpass that of
si l i ca gel (400 m
2
/g) i f a nanoporous texture i s added.
Thi s property makes them i deal candi dates for cel l
adhesi on, catal ysi s, fi l ter, and fuel cel l membrane
appl i cati ons.
The process of pore formati on ari si ng from rapi d
sol vent evaporati on most l i kel y occurs due to the forma-
ti on of water dropl ets from atmospheri c water due to
evaporati ve cool i ng of the pol ymer sol uti on as they
travel the di stance from the syri nge to the target.
Currentl y, i t i s cl ear that the sol vent vapor pressure
has a cri ti cal i nfl uence on the process of pore formati on.
TEM measurements of a cross secti on of PS fi bers
cl earl y i ndi cated that the pores appear onl y on the
surface of the fi bers, whi ch are known to be dry when
they reach the target.
11
Sol vent di ffusi on i n pol ymers pl ays an i mportant rol e
i n the evaporati on process as al ready menti oned. The
di ffusi on coeffi ci ents of the sol vents and the sol ubi l i ty
parameters of the pol ymers and of the sol vents as wel l
as the i nteracti on parameters between pol ymer and
sol vent are parameters of i nfl uence. More detai l ed
i nvesti gati ons need to be done i n order to take more
speci fi c pol ymer and sol vent properti es i nto consi der-
ati on. However, there are many more sol vent and
pol ymer properti es i ncl udi ng el ectri cal and thermal
effects that al so need to be consi dered for a compl ete
descri pti on of thi s compl ex el ectrospi nni ng process.
Acknowledgment. The authors woul d l i ke to ac-
knowl edge parti al support for thi s work from NSF
(DMR-9812088 and DMR-0210223) and DOE PAI R. We
al so want to thank Nancy Tassi for her i nsi ght and
experti se i n SEM, TEM, and AFM, Geral d Poi ri er for
hi s FESEM experti se i n i magi ng the nanoporous fi bers,
Dr. Darri n Pochan and Dr. Chou Ni for prepari ng the
mi crotomed sampl es and doi ng the TEM measurements,
Beth Schubert for performi ng the vi scosi ty measure-
ments, and Dr. Mei Wei Tsao and Dr. Ri chard I keda
for the many hel pful di scussi ons.
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