Electrospinning of Poly(vinyl pyrrolidone): Effects of

Solvents on Electrospinnability for the Fabrication of

Poly(p-phenylene vinylene) and TiO2 Nanofibers

Surawut Chuangchote, Takashi Sagawa, Susumu Yoshikawa

Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan

Received 2 February 2009; accepted 27 April 2009

DOI 10.1002/app.30637
Published online 16 July 2009 in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Seven different solvents (methanol, ethanol, vent with a high dielectric constant, low surface tension,
2-propanol, 1,2-dichloroethane, water, chloroform, and and low viscosity could increase the electrospinnability of
dichloromethane) were used to prepare electrospun poly the solution. The effects of solution properties and spin-
(vinyl pyrrolidone) (PVP) fibers. The dielectric constant, ning conditions on the morphological appearance and
viscosity, and surface tension of the solvents essentially diameter of electrospun PVP fibers were also carefully
affected the electrospinnability, morphological appearance, investigated. Under all investigated conditions for the elec-
and size of the as-spun fibers. Small and uniform as-spun trospinning of a PVP solution in ethanol, the average
fibers could be fabricated from PVP solutions in solvents diameters of the as-spun fibers ranged from 200 nm to
with a significantly high dielectric constant, low surface 1.5 lm. Well-aligned PVP fibers were also produced with
tension, and low viscosity. In three alcohol solutions (e.g., a rotating-drum collector technique. Lastly, PVP was used
methanol, ethanol, and 2-propanol), the diameters of as- in the fabrication of poly[2-methoxy-5-(20 -ethylhexyloxy)-
spun PVP fibers decreased with the dielectric constant, 1,4-phenylene-vinylene] and TiO2 fibers by acting as a
dipole moment, and density of the solvents increasing and polymer carrier or guide. VC 2009 Wiley Periodicals, Inc. J Appl

with the viscosity of the solvents decreasing. Among these Polym Sci 114: 2777–2791, 2009
solvents, methanol was the best solvent, providing fibers
with an optimal morphological appearance and a small Key words: fibers; nanotechnology; solution properties;
fiber diameter. Mixing an unspinnable solvent with a sol- surfaces; viscosity

INTRODUCTION The electric field is generated between a syringe

with a capillary tip and a grounded collector by a
One-dimensional nanomaterials have attracted inter-
high-voltage power supply. Electrostatic charging at
est and have been widely investigated for potential
the tip of the nozzle results in the formation of the
applications in mechanics, electronics, optoelec-
well-known Taylor cone, and then a single fluid jet
tronics, and catalysis and for medical, biological, and
is ejected from the apex.7,8 As the jet accelerates, ra-
environmental applications1–4 because of several spe-
dial charge repulsion results in bending instability.
cific properties of nanomaterials (e.g., a high surface
The charged jet is thinned in the electric field and
area to volume ratio, a very high aspect ratio,
then solidified. These fibers are collected on the sur-
improved mechanical performance, relatively small
face of a collector as highly impermeable, randomly
pore sizes, and flexibility in surface functionalities).5,6
deposited, and nonwoven mats.
Over the past decade, there has been increasing
So far, more than 40 different types of polymers
interest in electrospinning. Electrospinning is a
have been fabricated into nanofibers by electrospin-
method for preparing continuous one-dimensional
ning.4 Poly(vinyl pyrrolidone) (PVP) is an important
materials in the form of ultrafine fibers from a vari-
synthetic polymer that consists of carbon, hydrogen,
ety of materials, such as polymers, ceramics, inor-
oxygen, and nitrogen in the repeating unit. It was first
ganic complexes, and organic/inorganic hybrid
reported in a patent about 60 years ago, with good
composites, with diameters ranging from the micro-
adhesion and complexation properties, low chemical
scale down to the nanoscale by the acceleration of a
toxicity, high hydrophilicity, excellent physiological
jet of a charged solution (or melt) in an electric field.
compatibility, biocompatibility, and good solubility in
water and various organic solvents.9,10 It is, therefore,
Correspondence to: S. Yoshikawa (s-yoshi@iae.kyoto-u.ac. widely applied in many novel applications such as
jp).
adhesives, paints, detergents, electronics, beverages,
Journal of Applied Polymer Science, Vol. 114, 2777–2791 (2009) cosmetics, pharmaceuticals, and biological engineer-
V
C 2009 Wiley Periodicals, Inc. ing materials.10
2778 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

The electrospinning of ultrafine PVP fibers was first formation of the polymer chain, composition of the
reported by Bognitzki et al.11 in 2001, and the success- polymer (in the case of polymer blends), viscosity
ful fabrication of polylactide/PVP blend fibers was (concentration) of the solution, and composition,
also reported at that time. Because of the various conductivity, surface tension, and polarity of the sol-
advantages of PVP mentioned previously and other vent] and the electrospinning conditions [e.g., the
specific benefits related to electrospinning (e.g., its applied electrical potential, distance between the
ease of spinning, extractability, and ability to act as a capillary and collector (i.e., collection distance), and
non-ionogenic partner for the electrospinning of an feed flow rate].38–40 For the electrospinning of PVP,
ionogenic polymer), PVP is widely used in the fabri- Yang et al.10 reported the influence of solvents
cation of fibers via electrospinning with various other (including ethanol, DCM, DMF, and an ethanol/
materials that are unspinnable or hardly spinnable by DMF mixture) on the formation of uniform PVP
acting as a polymer carrier, a partner, or a guide. nanofibers in 2004. Li et al.41 reported the applica-
Metal oxides (e.g., TiO2, ZnO, and SnO2) and second- tion of patterned electrodes to change the alignment
ary metal-doped/metal oxide nanofibers can be pre- of PVP fibers in 2005. However, to the best of our
pared by the electrospinning of metal oxide knowledge, until now, no investigation about the
precursors and PVP, which is followed by calcination electrospinning of PVP per se from solutions in vari-
at a high temperature to form the crystalline phase of ous alcohols and other organic solvents and the
metal oxides and get rid of PVP at the same time.12–19 influence of various spinning solution properties
Some conductive polymers, hardly spinnable because and electrospinning conditions has been reported. In
of the limitations of suitable solvents and molecular this contribution, the electrospinning of PVP from
weights, can also be successfully fabricated by direct solutions in various solvents, including methanol,
blending with PVP20–24 or through the use of separate ethanol, 2-propanol, DCE, water, chloroform, and
spinning solutions with a coaxial two-capillary DCM, was carried out to systematically study the
spinneret.25,26 These reported conductive polymers effects of the solvents used and the composition of
include polyaniline,20,21 poly(p-phenylene vinylene),22 the solvents in a mixed solvent system on the mor-
and its derivatives poly[2-methoxy-5-(20 -ethylhexy- phological appearance and size of the as-spun prod-
loxy)-1,4-phenylene-vinylene] (MEH–PPV)23–25 and ucts. Moreover, the effects of the molecular weight
blended MEH–PPV/poly(3-hexylthiophene).26 Bio- of PVP, solution concentration, applied electrical
polymers and other compounds for medical and bio- potential, and collection distance on the as-spun
logical applications (e.g., scaffolding, wound-dressing fibers and the potential to align PVP fibers in one
materials, and biosensors) have been reported to have direction were determined. Examples of the utiliza-
been successfully fabricated in fiber form via blending tion of PVP in the fabrication of other electrospun
with PVP.11,27–31 Furthermore, PVP has also been fibers (e.g., conductive polymer and TiO2 fibers)
mixed with small molecules and organic or inorganic were also investigated and discussed.
compounds (e.g., functional organic molecules,32 car-
bon black,33 and metal oxide nanoparticles or nano-
rods34–37) to fabricate various kinds of composite EXPERIMENTAL
fibers by electrospinning. Almost all the spinning sol-
Materials
utions in these reported works were, however, pre-
pared in ethanol; some were prepared in a mixed PVPs with weight-average molecular weight (Mw)
ethanol/water system; and only a few of them were values of 43,000 and 1,300,000 were supplied in
prepared in water31,33 and some organic solvents, powder form from Nacalai Tesque (Kyoto, Japan)
including dichloromethane (DCM), N,N-dimethyl- and Aldrich (St. Louis, MO), respectively. The sol-
formamide (DMF), and their mixtures,10,35 1,2- vents were methanol, ethanol, 2-propanol, DCE,
dichloroethane (DCE)/chlorobenzene (CB),23 and water, chloroform, DCM, toluene, CB, 1,2-dichloro-
CB/methanol.24 The study of the fabrication of elec- benzene (DCB), and tetrahydrofuran (THF). All of
trospun PVP fibers from solutions dissolved in other them were purchased from Wako (Osaka, Japan),
organic solvents and mixed solvents to discover ways except for DCB, which was purchased from Aldrich,
of widening the utilization of PVP in the fabrication of and water, which was filtered in our laboratory.
electrospun fibers from other materials is, therefore, Some important properties of these solvents are
very interesting. summarized in Table I. A conductive polymer,
Generally, uniform fibers without any beads or MEH–PPV [number-average molecular weight (Mn)
droplets and small-diameter fibers are required for
40,000–70,000, Mw/Mn
5], was purchased from
electrospinning. The morphological appearance and Aldrich. For the preparation of the TiO2 precursor,
diameters of the electrospun fibers depend on a titanium(IV) butoxide (TiBu; reagent grade, 97%)
number of parameters, including the properties of and acetylacetone (ACA) were purchased from
the spinning solution [e.g., the type of polymer, con- Aldrich and Nacalai Tesque, respectively.

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2779

TABLE I
Some Properties of the Solvents
Boiling Surface Dipole
point Viscosity tension Density moment Dielectric
Solvent ( C) (mP s) (mN/m) (g/cm3) (D) constant

Methanol 64.7 0.59 22.6 0.792 1.69 32.6

Ethanol 78.4 1.20 22.1 0.789 1.66 24.6
2-Propanol 82.3 2.07 23.0 0.785 1.66 19.9
DCE 83.5 0.84 31.6 1.239 2.94 10.2
Water 100.0 0.88 72.8 0.998 1.87 78.4
Chloroform 61.2 0.54 27.5 1.470 1.15 4.8
DCM 39.8 0.44 26.5 1.326 1.14 10.7
Toluene 110.6 0.59 28.5 0.867 0.31 2.4
CB 131.7 0.80 33.6 1.107 1.54 5.6
DCB 180.3 1.32 26.8 1.306 2.14 9.8
THF 66.0 0.48 26.4 0.875 1.75 7.6

Electrospinning of pure PVP nol mixing ratios of 85 : 15, 80 : 20, and 75 : 25 v/v
were prepared under vigorous stirring. The obtained
To study the effects of the molecular weight of PVP,
solutions were sonicated for 10 min and heated to
the solution concentration, and the applied electrical
40 C to exceed the dissolubility of MEH–PPV. The
potential, PVP solutions were prepared to attain con-
electrospinning of as-prepared solutions was carried
centrations of 40, 50, and 60% w/v and 6, 8, and
out with the typical procedure described previously.
10% w/v from PVPs with Mw values of 43,000 and
1,300,000, respectively. In DCE solutions, to study
the effects of the solution concentration, PVP (Mw ¼ Fabrication of TiO2 fibers with PVP as a
1,300,000) solutions were prepared with concentra- polymer guide
tions in the range of 4–10% w/v. In other experi-
ments, without another mention, only PVP with an For the preparation of the TiO2 precursor, 5.45 g of
Mw value of 1,300,000 was used, and the concentra- TiBu was first introduced into equimolar ACA. The
tion of PVP was fixed at 8% w/v. mixed solution was then gently stirred until intimate
The electrospinning of these as-prepared solutions mixing to obtain a solution of the TiO2 precursor.
was carried out by the loading of each of the as-pre- The TiO2 precursor solution (0.6 g) was added to
pared solutions into a 3-mL plastic syringe. The noz- 1 mL of an 8% w/v PVP (Mw ¼ 1,300,000) solution
zle was a blunt-end, stainless steel, gauge 22 needle in ethanol. The resulting mixture was constantly
(1.5 cm long). An aluminum sheet wrapped around stirred for 10 min. The as-prepared solution was
a hard plastic backing plate was used as the collec- called the spinning solution.
tor. To study the alignment of the as-spun PVP Electrospinning was carried out with the typical
fibers, an aluminum sheet wrapped around a rotat- procedure described previously. The obtained fibers
ing drum rotated at a speed of 3000 rpm was used were left exposed to moisture for approximately 5 h
as the collector instead. A gamma high-voltage to allow complete hydrolysis of TiBu and conse-
research power supply was used to charge the solu- quently subjected to calcination at a high tempera-
tion across an electrode in solution. In a typical pro- ture of 450 C for 3 h to remove residual PVP and
cedure, without another mention, as-prepared impurities and increase the crystallinity of TiO2.
solutions were electrospun under an applied electri-
cal potential of 15 kV over a fixed collection distance
of 15 cm at room temperature ( 18 C). The flow Characterization
rate and the collection time were fixed for all experi- The morphological appearance of the as-spun fibers
ments at 1 mL/h and 1 min, respectively. The sam- was examined with a JEOL (Tokyo, Japan) JSM-
ples were then dried overnight at 60 C in a vacuum 6500FE scanning electron microscope operating at
oven before further characterization. an acceleration voltage of 10 kV. Diameters of the
as-spun fibers were measured directly from scanning
electron microscopy (SEM) images, with the average
Electrospinning of a conductive polymer with PVP value being calculated from at least 50 measure-
as a polymer carrier
ments for each spinning condition. The crystalline
Solutions of 7% w/v MEH–PPV/PVP (1 : 6 w/w) in phase of the TiO2 fibers was identified with a Rigaku
mixed solvents of CB and methanol with CB/metha- (Tokyo, Japan) Rint 2100 X-ray diffractometer.

Journal of Applied Polymer Science DOI 10.1002/app

2780 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

RESULTS AND DISCUSSION Effects of the molecular weight of PVP,

the solution concentration, and the applied
Electrospinning of PVP in single solvents electrical potential
Many attempts to fabricate ultrafine fibers of PVP Tables II and III show SEM images illustrating the
and its blends by the electrospinning of PVP solu- morphological appearance of the as-spun fibers from
tions in ethanol have been reported. Before the elec- 40–60 and 6–10% w/v PVP solutions in ethanol; the
trospinning of PVP solutions in other solvents was Mw values of PVP were 43,000 and 1,300,000, respec-
carried out, the influences of various solution prop- tively. Quantitative results in terms of the average
erties and electrospinning conditions were systemati- diameters of the as-spun fibers are summarized in
cally investigated with ethanol as the solvent. To Figure 1. The applied electrical potential varied in
straightforwardly explain the reasons for the results, the range of 5–30 kV over a fixed collection distance
six types of forces involved in electrospinning of 15 cm. Ultrafine fibers with average diameters in
should be mentioned,6 including the gravitational or the range of 200 nm to 1.5 lm could obviously be
body force; the electrostatic force (the force exerted produced.
on charges carried within a jet segment when the jet In most of the reported works related to the elec-
is in an electrostatic field), which carries the charged trospinning of PVP and its blends (or composites),
jet from the needle to the collector; the Coulombic PVP with an Mw value of 1,300,000 has been
stretching force (the repulsion force between charges extremely investigated. Only a few have reported
of mutual polarities), which tries to push apart adja- the use of PVP with an Mw value of 360,00029,31 or
cent charged species carried within the jet segment 55,000.35 Therefore, it was interesting to carry out
and is responsible for the thinning or stretching of the electrospinning of PVPs of very different molec-
the charged jet during its flight to the target; the ular weights and study the effects on the electrospin-
viscoelastic force, which tries to prevent the charged ning behavior. According to Tables I and II, for each
jet from being stretched; the surface tension, which molecular weight, a uniform fibrous structure was
also acts against the stretching of the surface of the stabilized above a minimum concentration. This cer-
charged jet; and the drag force from the friction tain concentration of PVP with an Mw value of
between the charged jet and the surrounding air. 43,000 was between 6 and 8% w/v, whereas that

TABLE II
SEM Images of the As-Spun Fibers from Solutions of 40, 50, and 60% w/v PVP (Mw 5 43,000) in Ethanol
Applied electrical potential (kV)

10 15 20 25 30

40% w/v

50% w/v

60% w/v

The applied potentials for electrospinning were varied between 10 and 30 kV (in 5-kV increments) over a collection dis-
tance of 15 cm. The feed flow rate was 1 mL/h. The scale bar in each image equals 1 lm.

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2781

TABLE III
SEM Images of the As-Spun Fibers from Solutions of 6, 8, and 10% w/v PVP (Mw 5 1,300,000) in Ethanol
Applied electrical potential (kV)

5 10 15 20 25 30

6% w/v

8% w/v

10% w/v

The applied potentials for electrospinning were varied between 5 and 30 kV (in 5-kV increments) over a collection dis-
tance of 15 cm. The feed flow rate was 1 mL/h. The scale bar in each image equals 1 lm.

with an Mw of 1,300,000 was between 40 and 50% formed, as the charged jet experiences instability
w/v. At these concentrations, higher molecular leading to the formation of droplets; this is called
weight PVP showed a little bit larger fiber diameter electrospraying.42 Conversely, if the solution concen-
than lower molecular weight PVP (see Fig. 1). In tration is too great, a prohibition of continuous flow
other words, to obtain the same morphological of the polymer liquid from the nozzle tip will be
appearance and same range of fiber diameters achieved.6 As a result, there is a processing window
obtained with spinning solutions of higher molecu- in terms of the concentration or viscosity range
lar weight PVP (Mw ¼ 1,300,000) at a concentration within which the polymer solutions are electrospin-
of 6–10% w/v, the concentration of the solution nable and beyond which discrete droplets are likely
from lower molecular weight PVP (Mw ¼ 43,000; to occur.6,43 For this work, regardless of the mol-
 30 times lower) had to be increased to 40–60% w/ ecular weight and applied electrical potential, elec-
v ( 6–7 times higher). The results from viscosity trospinning of the solution with the lowest
measurements (RC-100 viscometer controller, Toki concentration (6 and 40% w/v for PVPs with Mw
Sangyo Co., Ltd., Tokyo, Japan) showed that the values of 1,300,000 and 43,000, respectively) resulted
same range of solution viscosities with both molecu- only in the formation of beaded fibers because of the
lar weights was the cause of this. In particular, the low viscosity of the solution; hence, the low visco-
viscosities of PVP (Mw ¼ 43,000) solutions at 40, 50, elastic force was not enough to prevent Coulombic-
and 60% w/v were 200, 418, and 636 mPa s, respec- repulsion-caused partial breakup of the charged jet.
tively, whereas those of PVP (Mw ¼ 1,300,000) solu- A further increase in the solution concentration
tions at 6, 8, and 10% w/v were 93, 221, and 425 resulted in the formation of uniform fibers because
mPa s, respectively. of the increased viscosity; hence, the increased visco-
To obtain uniform ejection of the charged jet in elastic force was enough to completely prevent the
electrospinning, a solution with an appropriate con- partial breakup of the charged jet and allowed the
centration or viscosity is required to be exceeded as Coulombic stress to elongate the charged jet.6
extensive molecular entanglements are prerequisites Increasing the solution concentration of PVP caused
for the formation of a stable and continuous charged the fiber diameters to increase monotonically with a
jet. If the concentration of the solution is too low, a broader distribution. This is in general accordance
continuous stream of the charged jet cannot be with the literature.10 For the fiber diameter, according

Journal of Applied Polymer Science DOI 10.1002/app

2782 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

respectively [for an electrostatic field strength (EFS)

of 8 kV/12 cm].10 Obviously, for PVP with an Mw
value of 1,300,000, our results were in line with
those of this previous report. Interestingly, flat and
twisted (ribbon-like) fibers could be observed at a
high solution concentration (see Tables II and III) as
a result of a broader distribution of the fiber diame-
ters at a higher concentration. Moreover, it was
observed that, at a higher concentration, the electro-
spinning of lower molecular weight PVP resulted in
more flat and twisted fiber structures than the elec-
trospinning of high-molecular-weight PVP. This may
be due to the fact that a charged jet from the low-
molecular-weight PVP could be stretched during
bending instability more than that from the high-
molecular-weight PVP.
For any given molecular weight and solution con-
centration, increasing the applied electrical potential
caused the number of the as-spun fibers (or beaded
fibers) per unit of area to increase. Increasing the
applied electrical potential also caused the number of
beads per unit of area to decrease or disappear; this
was an indication of the increased stretching force
exerted on a jet segment (see Tables II and III).
According to Figure 1, for any given molecular
weight and solution concentration, the average diam-
eters of the as-spun PVP fibers as well as their varia-
tions were generally found to decrease with an initial
increase in the applied electrical potential, reach a
minimum value at about 15 kV, then increase with a
further increase in the applied electrical potential,
reach a maximum value, and decrease again at the
Figure 1 Average diameters of the as-spun fibers from highest applied electrical potential (at 30 kV). The
(l) 40, (~) 50, (^) 60, (!) 6, (n) 8, and (^) 10% w/v
PVP solutions in ethanol. The Mw values of PVP were (a)
increase in the applied electrical potential should
43,000 and (b) 1,300,000. The electrical potential in electro- cause the number of charges carried within a jet seg-
spinning was applied in the ranges of 10–30 and 5–30 kV ment to increase and hence an increase in both the
for solutions of PVP with Mw values of 43,000 and electrostatic and Coulombic repulsion forces. The
1,300,000, respectively, over a fixed collection distance of increased Coulombic repulsion force should cause
15 cm. The feed flow rate was 1 mL/h.
the diameters of the as-spun fibers to decrease
(because of increased stretching force exerted on the
to Figure 1, regardless of the applied electrical jet segment), whereas the increased electrostatic force
potential investigated, at the lowest concentration should cause the diameters of the as-spun fibers to
investigated (6 and 40% w/v for PVPs with Mw val- increase (because of both the increase in the speed of
ues of 1,300,000 and 43,000, respectively), the aver- the jet segment and the increase in the mass flow
age diameter of the as-spun fibers ranged between rate, the phenomena that cause the onset of bending
326 and 472 and between 210 and 281 nm for PVPs instability to occur closer to the screen collector).6 On
with Mw values of 1,300,000 and 43,000, respectively. the basis of this statement, the observed decrease in
However, at the highest concentration investi- the fiber diameters with the initial increase in the
gated (10 and 60% w/v for PVPs with Mw values of applied electrical potential could be due to a contri-
1,300,000 and 43,000, respectively), it ranged bution from the increase in the Coulombic repulsion
between 734 nm and 1.29 lm and between 844 nm force, whereas the observed increase in the fiber
and 1.50 lm for PVPs with Mw values of 1,300,000 diameters with a further increase in the applied elec-
and 43,000, respectively. Yang et al.10 reported that trical potential could be due to a contribution from
the average diameters of as-spun fibers from PVP the increase in the electrostatic force, and the
(Mw ¼ 1,300,000) ethanol solutions increased from decrease in the fiber diameter again at the highest
120 to 250, 400, 750, and 1500 nm with the PVP con- applied electrical potential could be due to a contri-
centration increasing from 2 to 4, 6, 8, and 10%, bution from the increase in the Coulombic repulsion

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2783

force, which was too high to overcome the electro- w/v) and caused the fiber diameters to increase
static force. For reported works related to the electro- monotonically with a broader distribution. The elec-
spinning of pristine PVP, there has been no report on trospinnability became more difficult with the con-
the effects of the applied electrical potential; how- centration increasing to 10% w/v [see Fig. 2(d)], and
ever, there are various conflicting results reported in at a higher concentration over 10% w/v, the electro-
the literature for the electrospinning of other poly- spinning was inhibitive because of the high viscos-
mers and also PVP blends and composites.12,22,29,32,40 ity. As shown in Figures 1(b) and 2(e), even with the
Competing effects of two forces should be the reason same concentration and applied electrical potential,
for these conflicting results. In the case of the electro- electrospun PVP fibers from DCE solutions showed
spinning of another polymer, poly(vinyl alcohol) significantly larger average diameters than those
(PVA), the average diameter of the as-spun PVA from ethanol solutions (e.g., 610 nm and 2.11 lm,
fibers as well as their variation was also reported to respectively, at the concentration of 8% w/v and at
decrease with the initial increase in the applied elec- the applied electrical potential of 15 kV).
trical potential, reach a minimum value, and increase
with a further increase in the applied electrical
Effects of the solvents
potential to 25 kV.7 In accordance with this, we
obtained similar results, except for the last decrease Among the 11 solvents used, that is, methanol, etha-
in the diameter at the maximum applied electrical nol, 2-propanol, DCE, water, chloroform, DCM, tolu-
potential, because a higher applied electrical poten- ene, CB, DCB, and THF, it was found that toluene,
tial (30 kV) was also investigated. CB, DCB, and THF were not able to dissolve PVP to
The effects of the solution concentration in another form a clear solution at room temperature ( 18 C).
organic solvent (i.e., DCE), not just in ethanol solu- Interestingly, solvents that were able to dissolve PVP
tions, were also investigated and are shown in Fig- and were able to fabricate fibers by electrospinning
ure 2 (Mw of PVP ¼ 1,300,000). The results showed have quite high dipole moments and low boiling
the same trend in comparison with the electrospin- points (100 C). Moreover, their dielectric constants
ning of PVP solutions in ethanol; that is, increasing are higher than those of the solvents that were not
the solution concentration of PVP caused a change able to dissolve PVP, and those values are higher
in the morphological appearance from beaded fibers than 10, except for chloroform (see Table I). To study
to uniform fibers at a certain concentration (6–8% the effects of the solvents, 8% w/v PVP (Mw ¼

Figure 2 (a–d) SEM images and (e) quantitative results in terms of the average diameters of (~) beads and (l) as-spun
fibers from solutions of (a) 4, (b) 6, (c) 8, and (d) 10% w/v PVP (Mw ¼ 1,300,000) in DCE. The applied potential for elec-
trospinning was 15 kV over a collection distance of 15 cm. The feed flow rate was 1 mL/h. The scale bar in each image
equals 1 lm, except for the inset in part d, for which it equals 100 lm.

Journal of Applied Polymer Science DOI 10.1002/app

2784 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

1,300,000) in methanol, ethanol, 2-propanol, DCE, reduced from 82.3 to 78.4 and 64.7 C, respectively
water, chloroform, and DCM was electrospun with a (see Table I). The diameter of as-spun fibers from a
fixed electrical potential, collection distance, and feed PVP solution in 2-propanol was larger than that
flow rate of 15 kV, 15 cm, and 1 mL/h, respectively. from an ethanol solution, which was also larger than
The obtained results are shown in Figure 3. Accord- that from a methanol solution; that is, the average
ing to Figure 3(a–c), smooth fibers without the pres- diameters of as-spun fibers from solutions in 2-pro-
ence of beads were obtained from the electrospinning panol, ethanol, and methanol were 1250, 638, and
of all three PVP alcohol solutions. At a high magnifi- 274 nm, respectively. Obviously, it can be concluded
cation, it was revealed that the cross-sectional geome- that the diameters of as-spun PVP fibers decreased
try was quite round because of the low boiling point with the dielectric constant, dipole moment, and
of the solvent used. The charged jets could be dry density of the solvents increasing and with the vis-
enough before being collected on a grounded target. cosity and boiling point of the solvents decreasing.
In three alcohol solutions (methanol, ethanol, and When we consider each property of the solvents,
2-propanol), the three solvents are a good system to we find that a greater dielectric constant is responsi-
determine the effect of a solvent on the morphologi- ble for the observed smaller diameters of the obtained
cal appearance and fiber diameter. Because all of PVP fibers because a greater dielectric constant leads
them have the same functional (hydroxyl) group, the to greater Coulombic repulsion force (which is re-
type of molecular interaction between the solvent sponsible for the stretching of the charged jet) and
and the polymer can be observed for comparison. electrostatic force (which is responsible for carrying
According to the properties of the three alcohols, if the charged jet to the collector).6 Lee et al.44 found the
the type of alcohol solvent is changed from 2-propa- dielectric constant to be one of the key factors in the
nol to ethanol or methanol, the dielectric constant electrospinning process. The dielectric constant is
will be remarkably increased from 19.9 to 24.6 and related to the dipole moment and generally reflects
32.6, respectively; the dipole moment will be quite the polarity of the molecules; that is, methanol has
constant (constant at 1.66 D and increasing to 1.69 greater polarity than ethanol and 2-propanol. For the
D). The solvent density will increase from 0.785 to density of solvents, Wannatong et al.45 reported that
0.789 and 0.792 g/cm3, respectively; the surface ten- the fiber diameter of polystyrene fibers decreased
sion will be quite constant (decreasing from 23.0 to with the density of the solvents increasing, and this
22.1 mN/m and increasing to 22.6 mN/m). The vis- corresponds with our results. The effects of the vis-
cosity will be remarkably reduced from 2.07 to 1.20 cosity of the solvent are directly related to the visco-
and 0.59 mP s, respectively; the boiling point will be elastic force. This force tries to prevent the charged jet

Figure 3 SEM images of the as-spun fibers from 8% w/v PVP (Mw ¼ 1,300,000) solutions in various solvents: (a) metha-
nol, (b) ethanol, (c) 2-propanol, (d) DCE, (e) water, (f) chloroform, and (g) DCM. The applied potential for electrospinning
was 15 kV over a collection distance of 15 cm. The feed flow rate was 1 mL/h. The scale bar in each image in the second
row equals 10 lm, whereas those in the first row equal (a–e) 1 or (f,g) 100 lm.

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2785

from being stretched, as discussed previously; as a flat beads [see Fig. 3(f)]. The average diameters of the
result, the diameter of PVP fibers was found to fibers and beads were 1.45 and 31.9 lm, respectively.
decrease with the viscosity of the solvent decreasing. However, ribbon-like fibers with flat beads could be
On the contrary, it has been reported in the literature observed from the electrospinning of an 8% w/v PVP
that the observed fiber diameter decreases with an solution in DCM [see Fig. 3(g)]. The average width of
increase in the boiling point of the solvents,45 and this the fibers and the average diameter of the beads were
is inconsistent with our results. The reason for the 15.7 and 34.9 lm, respectively. As-spun PVP fibers
conflicting observations is the large difference in the from DCM solutions appeared to be wet as they were
ranges of boiling points of the investigated solvents, fused to adjacent fibers at touching points. Fong et
which were 65–203 C (a 138 C difference) and 65– al.38 attributed the formation of beads to the low vis-
82 C (an approximately 17 C difference) for the refer- cosity and high surface tension of the solutions and
ence45 and our experiment, respectively. Therefore, the high boiling point of the solvent (low evaporation
for the three alcohols investigated, other properties of rate). In other words, when we consider the aforemen-
the solvent, that is, the dielectric constant, dipole tioned forces, the formation of beads could be ascribed
moment, density, and viscosity, as described previ- to the viscoelastic and surface tension forces. In this
ously, played more important roles in the diameter case, chloroform and DCM have low boiling points.
changes of as-spun PVP fibers than the slight change Therefore, a bead structure is most likely a result of
in the boiling point. higher surface tension in comparison with that of
As remarked previously, an 8% w/v PVP solution alcohols. Another possible reason is that there was not
in DCE could be electrospun to form uniform fibers enough viscoelastic force in the PVP solutions at the
with quite large diameters (or widths;  1.25 lm). In concentration of 8% w/v because chloroform and
comparison with alcohols, the fact that DCE has a DCM have low viscosities (see Table I). This concentra-
much lower dielectric constant and a significantly high tion is too low to exceed molecular entanglements,
surface tension may be responsible for the larger fiber which are prerequisites for the formation of a stable
diameter. The role of the dielectric constant has been and continuous charged jet. The composition of the
already discussed. For surface tension, it acts against solvent in the charged jets was high, and the even
the stretching of the surface of the charged jet. The evaporation rate was not low, but the charged jets
size of the charged jets from a high surface tension could not be dry enough before being collected on a
solution could not be reduced much during bending grounded collector. In this sense, some parts of the
instability as a result of the large diameter of the damp fibers would be flat during very rapid
obtained as-spun fibers. Moreover, the cross-sectional deposition.
geometry of the as-spun fibers was c-shaped [see
Fig. 3(d)], and this could be a result of the collapse of
Effects of the collection distance
the fibers upon the evaporation of the solvent.
An 8% w/v PVP aqueous solution was spun out Figure 4 shows SEM images of electrospun fibers pre-
to form ultrafine fibers ( 33 nm in diameter) with pared under conditions with several collection dis-
spherical beads or globs of PVP [1.35 lm in diame- tances. The 8% w/v PVA solutions in 2-propanol and
ter; see Fig. 3(e)]. It is believed that the very high in chloroform were electrospun under a fixed applied
surface tension of water made the droplets of the electrical potential of 15 kV. The collection distances
solutions form spherical beads during drying, for the electrospinning of PVP solutions in 2-propo-
whereas the very high dielectric constant led to the nal and chloroform were 9.5 and 15 cm and 15, 20,
formation of ultrafine fibers with a very small diam- and 25 cm, respectively. As shown in Figure 4(a),
eter. To obtain uniform electrospun fibers, a reduc- from the electrospinning of the PVP solution in 2-pro-
tion of the surface tension in aqueous solutions panol at the collection distance of 9.5 cm, nonsmooth,
should be carried out. One easy way is the mixing wet-like fibers with a large diameter ( 3.25 lm)
of water with a solvent that has a lower surface ten- were obtained, and the adjacent fibers appeared to
sion. Fong et al.38 reported that increasing the etha- fuse to one another at touching points; this was an
nol composition in a poly(ethylene oxide) (PEO) indication of the incomplete drying of the jet before
solution in a mixture of water and ethanol could deposition on the collector. A further increase in the
reduce the surface tension of obtained solutions, and collection distance to 15 cm resulted in the formation
the electrospinning of those solutions resulted in of smooth fibers with a much smaller diameter
uniform as-spun PEO fibers. The electrospinning of ( 1.25), which indicated that the jets were stretched
some materials from solutions in a mixture of water and dried enough before deposition on the collector.
and ethanol with PVP as the polymer carrier has From this observation, it can be deduced that an
also been reported.13,25,26,29,30,34 insufficient collection distance in the electrospinning
Electrospinning of an 8% w/v PVP solution in of 8% PVP solutions in chloroform may be another
chloroform resulted in bead-on-string structures with cause of the formation of flat bead structures, as

Journal of Applied Polymer Science DOI 10.1002/app

2786 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

Figure 4 SEM images of the as-spun fibers from 8% w/v PVP (Mw ¼ 1,300,000) solutions in (a) 2-propanol (scale bar ¼
10 lm) and (b) chloroform (scale bar ¼ 100 lm). The applied potential for electrospinning was 15 kV. Suffixes 1–4 repre-
sent collection distances of 9.5, 15, 20, and 25 cm, respectively. The feed flow rate was 1 mL/h. The scale bar in each
image equals 10 lm.

described previously. Therefore, the electrospinning Figure 5 illustrates the effects of the applied potential
of PVP solutions in chloroform at various collection on the alignment of the as-spun PVP fibers in the
distances was also carried out. As shown in Figure machine direction. These fibers were fabricated from
4(b), the shapes of beads in beaded fibers were found a 10% w/v PVP solution in ethanol. The applied
to change from flat to spindle-like. The diameters of potential was varied from 5 to 25 kV over a collection
the as-spun fibers and beads were found to decrease distance of 1 cm. The rotational speed of the collector
with the collection distance decreasing. Specifically, was also fixed at 3000 rpm. Clearly, the alignment in
the diameter of as-spun fibers decreased from about the machine direction of the as-spun fibers from the
1.45 to 1.12 and 1.04 lm with the collection distance electrostatic potential of 5 kV was much better than
increasing from 15 to 20 and 25 cm, respectively. The that of the fibers from the applied potential of 15 kV.
observed decrease in the diameters of the fibers and This can be explained on the basis of the relation-
beads with the collection distance increasing must be ships between the three major forces (i.e., the body,
a result of the increase in the total path trajectory of electrostatic, and drag forces). At a lower applied
the jet, which allowed more stretching of the jet dur- electrical potential (e.g., 5 kV), the lateral speed at
ing its flight to the collector. the points of contact between the depositing charged
jets and the collector screen was fit to the approach-
ing speed of the charged jets, and this finally resulted
Alignment of the electrospun PVP fibers
in well-aligned as-spun fibers. At a higher applied
One characteristic feature of electrospun fibers that electrical potential (e.g., 15 kV), the approaching
has received much interest recently is the possibility speed of the charged jets was much greater than the
of aligning fibers in one direction. For the prepara- lateral speed at the points of contact between the
tion of aligned PVP fibers, Li et al. reported aligned depositing charged jets and the collector screen, and
arrays of pure PVP fibers via the collection of as- this resulted in partial alignment of the charged jets
spun fibers with patterned electrodes10 and aligned on the collector screen.45 At a given applied electrical
ceramic fibers fabricated with PVP as a polymer potential, it was observed that a change in the collec-
guide and with two parallel pieces of electrodes as a tor from an aluminum sheet wrapped around a hard
collector.13 In this work, a rotating-drum collector plastic plate to a rotting drum did not affect the
technique was applied to align electrospun fibers. diameters of the as-spun fibers.

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2787

reported.23 Unfortunately, with our best trial, the

mixed CB/DCE solvent could not dissolve PVP to
form a clear solution at room temperature. Among
all the solvents investigated, the electrospinning of
PVP in a methanol solution resulted in the smallest
diameter fibers; thus, we tried to add methanol to 8%
w/v PVP solutions in a mixed solvent of CB and
DCE (50 : 50 v/v) as the third solvent. Surprisingly,
the solution became clear. Therefore, the electrospin-
ning of PVP solutions in a mixture of methanol, CB,
and DCE was systematically carried out.
Figure 6(a) shows SEM images of the as-spun
fibers from 8% w/v PVP solutions in a mixture of
methanol, CB, and DCE with various contents (100,
250, and 500 lL) of methanol added to 1 mL of
8% w/v PVP (Mw ¼ 1,300,000) solutions in the mixed
solvent of CB and DCE (50 : 50 v/v). The results sug-
gest that the addition of methanol to PVP solutions
in the mixed solvent of CB and DCE helped to
improve the electrospinnability of the resulting solu-
tions. At the lowest content of methanol (i.e., 100 lL),
electrospun PVP fibers could be fabricated with a
rough surface morphological appearance and a large
diameter (i.e., 6.18 lm). Evidently, with the content
of methanol increasing to 250 lL, uniform as-spun
fibers with a smooth surface and a smaller diameter
(i.e., 1.451 lL) were obtained. However, as-spun
fibers (diameter  697 nm) with some parts of a cap-
sular structure were found with the content of meth-
anol increasing up to 500 lL. This was a direct result
of the extremely greater dielectric constant, lower
viscosity, and lower surface tension of methanol in
comparison with those of CB and DCE (see Table I).
The capsular structure of as-spun fibers from a 500 lL
Figure 5 SEM images of aligned as-spun fibers from solu- methanol-added solution may be due to the greater
tions of 10% w/v PVP (Mw ¼ 1,300,000) in ethanol. The col-
lector was a rotating drum rotated at a speed of 3000 rpm.
contents of solvents with different boiling points as a
The applied potential for electrospinning was varied as (a) 5 result of the collapse of some parts of the fibers upon
and (b) 15 kV over a collection distance of 15 cm. The feed the evaporation of the high-boiling-point solvent af-
flow rate was 1 mL/h. The scale bar equals 100 lm. ter the deposition of a collector. Instead of a mixture
of CB with DCE and methanol, a direct mixture of
CB with methanol or ethanol (solvents that also have
Electrospinning of PVP in mixed solvents
high dielectric constants and low surface tension)
As mentioned previously, some organic solvents that was also found to be usable as a suitable solvent for
have low dielectric constants and surface tension the fabrication of as-spun fibers. For example, as
(e.g., toluene, CB, DCB, and THF) were not able to shown in Figure 6(b), the electrospinning of 8% w/v
dissolve PVP to form clear solutions at room temper- PVP solutions in mixed solvents of CB and ethanol
ature; thus, as-spun fibers from PVP solutions in (50 : 50 v/v) resulted in uniform fibers with an aver-
those solvents could not be fabricated. However, age diameter of 0.671 lm. The electrospinning of
those solvents may be good solvents for dissolving PVP solutions in mixed solvents of CB and methanol
various organic compounds. To fabricate those or- is discussed in the next section.
ganic compounds in a fiber form with PVP as a poly-
mer carrier or guide, a mixed solvent system had to
be used. We selected CB as a solvent model because Fabrication of electrospun conductive polymer
fibers with PVP as a polymer carrier
it has a very low dielectric constant and high surface
tension. Last year, the successful fabrication of ultra- MEH–PPV was chosen to be the model for the fabri-
fine fibers from PVP/MEH–PPV blended solutions cation of conductive polymer fibers with PVP
in a mixture of CB and DCE (50 : 50 v/v) was because it is not a water-soluble polymer that can be

Journal of Applied Polymer Science DOI 10.1002/app

2788 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

Figure 6 SEM images of the as-spun fibers from 8% w/v PVP (Mw ¼ 1,300,000) solutions in mixed solvents of (a) metha-
nol, CB, and DCE (CB/DCE ¼ 50 : 50 v/v with various contents of methanol) or (b) CB and ethanol (50 : 50 v/v). Suffixes
1–3 represent 100, 250, and 500 lL, respectively, of methanol added to 1 mL of an 8% w/v PVP (Mw ¼ 1,300,000) solution
in a mixed solvent of CB and DCE (50 : 50 v/v). The applied potential for electrospinning was 15 kV over a collection dis-
tance of 15 cm. The feed flow rate was 1 mL/h. The scale bar in each image equals 1 lm, except for the inset in part a1,
for which it equals 10 lm.

dissolved in only a limited number of organic sol- 1.89 and 1.45 lm with the content of methanol
vents. Therefore, the electrospinning of a pure increasing (i.e., CB/methanol ¼ 85 : 15, 80 : 20, and
MEH–PPV solution resulted in the formation of only 75 : 25 v/v, respectively). This was attributed again
many beads on fibers.46 To fabricate uniform electro- to the extremely greater dielectric constant, signifi-
spun MEH–PPV fibers, the blending of MEH–PPV cantly lower viscosity, and significantly lower sur-
with a polymer carrier that is easily spinnable and face tension of methanol in comparison with CB (see
extractable before electrospinning is one promising Table I). At the highest content of methanol (i.e.,
technique.24 CB/methanol ¼ 75 : 25 v/v), a small-wrinkle surface
CB is a good solvent for MEH–PPV, whereas the could be observed because of the collapse of the sur-
electrospinning of PVP solutions in methanol face upon the evaporation of CB after the deposition
resulted in uniform fibers with the smallest diame- of a collector. For a fixed applied electrical potential
ter, as reported previously. Therefore, a mixture of of 15 kV, only the density of the as-spun fibers was
CB and methanol was chosen as the solvent for elec- found to decrease, and a more twisted structure was
trospinning. Both MEH–PPV and PVP were able to found to increase with increasing collection distance,
be dissolved in the mixed solvent of CB and metha- whereas it did not affect the diameter of the as-spun
nol in a limited range. Before the study of the elec- fibers (not shown here).
trospinning of MEH–PPV/PVP solutions, the Figure 7(b) shows SEM images of the as-spun
electrospinning of PVP solutions in the mixed sol- fibers from 7% w/v MEH–PPV/PVP (1 : 6 w/w) sol-
vent of CB and methanol was carried out. utions in mixed solvents of CB and methanol with
Figure 7(a) shows SEM images of the as-spun mixing ratios in the range of 75 : 25–80 : 20. Follow-
fibers from 7% w/v PVP solutions in mixed solvents ing the same trend found for the electrospinning of
of CB and methanol with mixing ratios in the range pure PVP, with an increasing content of methanol
of 75 : 25–80 : 20. Obviously, ultrafine, uniform PVP (i.e., CB/methanol ¼ 85 : 15, 80 : 20, and 75 : 25 v/
fibers could be fabricated. The diameter of the as- v), the diameter of the as-spun PVP fibers was found
spun PVP fibers was found to decrease from 3.08 to to decrease from 1.55 to 1.44 lm and 936 nm,

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2789

Figure 7 SEM images (scale bar ¼ 10 lm) of (a,b) as-spun fibers from (a) 7% w/v PVP (Mw ¼ 1,300,000) solutions and
(b) 7% w/v MEH–PPV/PVP (1 : 6 w/w) solutions in mixed solvents of CB and methanol with various mixing ratios,
respectively, and (c) MEH–PPV fibers after the removal of PVP from MEH–PPV/PVP electrospun fibers. Suffixes 1–3 rep-
resent CB/methanol mixing ratios of 85 : 15, 80 : 20, and 75 : 25 v/v, respectively. The applied potential for electrospin-
ning was 15 kV over a collection distance of 15 cm. The feed flow rate was 1 mL/h.

respectively. The removal of PVP from the as-spun PPV/PVP fibers were reported in another contribu-
MEH–PPV/PVP fibers could be carried out with tion24,47 and will be reported further elsewhere.
Soxhlet extraction. MEH–PPV fibers obtained after
the removal of PVP are shown in Figure 7(c). The
complete removal of PVP was confirmed with UV–
vis spectroscopy. After the removal of PVP, pure Fabrication of TiO2 fibers with PVP
as a polymer guide
MEH–PPV fibers showed an aligned, wrinkled, sur-
face-ribbon-like structure with a smaller diameter To the best of our knowledge, all reported works
than the MEH–PPV/PVP fibers before extraction. related to the fabrication of fibers of TiO2 and other
Because the main objective of this section is to show metal oxides with PVP as a polymer guide used
the usefulness of the study of the effects of solvents ethanol as the solvent.12–19 According to our results,
and the potential to use PVP as a polymer carrier in the electrospinning of PVP solutions in methanol
a mixed solvent system for the fabrication of MEH– resulted in a smaller fiber diameter than electrospin-
PPV fibers, the issues regarding the effects of the so- ning in ethanol. Therefore, methanol might be a
lution properties, spinning conditions, and addition promising candidate for the fabrication of ultrafine
of an organic salt to spinning solutions on the mor- TiO2 fibers with PVP as a polymer guide.
phological appearance, fiber diameter, crystallinity, Figure 8 shows SEM images of the as-spun PVP/
and optical properties of obtained as-spun MEH– TiO2 precursor and calcined TiO2 fibers from the

Journal of Applied Polymer Science DOI 10.1002/app

2790 CHUANGCHOTE, SAGAWA, AND YOSHIKAWA

Figure 8 SEM images (scale bar ¼ 1 lm) of (a) the as-spun PVP/TiO2 precursor and (b) calcined TiO2 fibers from the
electrospinning of 8% w/v PVP (Mw ¼ 1,300,000) solutions in ethanol and methanol (suffixes 1 and 2, respectively) with
the TiO2 precursor. The amount of the TiO2 precursor was 0.6 in 1-mL PVP solutions. The applied potential for electro-
spinning was 15 kV over a collection distance of 15 cm. The feed flow rate was 1 mL/h. The average diameters of the
fibers were (a1) 1107, (a2) 654, (b1) 545, and (b2) 201 nm, respectively.

electrospinning of 8% w/v PVP solutions in ethanol CONCLUSIONS

and methanol with the TiO2 precursor. In compari-
The effects of solution properties and spinning con-
son with pure PVP, at the same PVP concentration
ditions, including the molecular weight of PVP, solu-
and spinning conditions, the electrospinning of
PVP/TiO2 precursor solutions resulted in larger di- tion concentration, applied electrical potential, and
ameter fibers [cf. Fig. 3(a,b) with Fig. 8(a1,a2)]. The collection distance, on the morphological appearance
increase in the viscosity caused by the addition of and diameter of electrospun PVP fibers were investi-
the TiO2 precursor may be responsible for the gated. At the lowest concentration of the solutions
observed larger diameters of the obtained fibers. Fol- studied, beaded fibers were observed. A uniform fi-
lowing the same trend found for the electrospinning brous structure was stabilized (with a change from
of pure PVP, as-spun fibers from solutions in metha- beaded fibers to more uniform fibers) above a mini-
nol showed a smaller diameter than those from etha- mum concentration, which was related to the molec-
nol solutions. After calcination at 450 C for 3 h, the ular weight of PVP. A solution from the lower
obtained fibers from the electrospinning of methanol molecular weight PVP (Mw ¼ 43,000) needed a
still showed lower diameter fibers than those from higher concentration to stabilize uniform fibers than
ethanol solutions (201 and 545 nm, respectively). X- that from the higher molecular weight PVP (Mw ¼
ray diffraction patterns of calcined TiO2 fibers indi- 1,300,000; 40–50 and 6–8% w/v, respectively). Inter-
cated the formation of a high anatase phase in the estingly, flat and twisted (ribbon-like) fibers could
obtained fibers (not shown here). In conclusion, be observed at a high solution concentration. The av-
methanol has shown the potential to be used as a erage diameters of the as-spun PVP fibers were in
suitable solvent instead of ethanol, which has been the range of 200 nm to 1.5 lm. The average diame-
frequently reported,12–19 for the fabrication of ultra- ters increased with the solution concentration
fine TiO2 fibers by electrospinning with PVP as a increasing but decreased with the collection distance
polymer guide. increasing. Furthermore, the average diameters

Journal of Applied Polymer Science DOI 10.1002/app

ELECTROSPINNING OF POLY(VINYL PYRROLIDONE) 2791

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Journal of Applied Polymer Science DOI 10.1002/app