Home Search Collections Journals About Contact us My IOPscience

Ultra-fine polyelectrolyte hydrogel fibres from poly(acrylic acid)/poly(vinyl alcohol)

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

2005 Nanotechnology 16 2852

(http://iopscience.iop.org/0957-4484/16/12/020)

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 169.237.141.15
The article was downloaded on 07/10/2010 at 20:30

Please note that terms and conditions apply.

INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 16 (2005) 2852–2860 doi:10.1088/0957-4484/16/12/020

Ultra-fine polyelectrolyte hydrogel fibres

from poly(acrylic acid)/poly(vinyl alcohol)
Lei Li and You-Lo Hsieh1
University of California at Davis, CA 95616, USA

E-mail: ylhsieh@ucdavis.edu

Received 27 June 2005, in final form 8 September 2005

Published 14 October 2005
Online at stacks.iop.org/Nano/16/2852
Abstract
Ultra-fine fibrous membranes were prepared by electrospinning of aqueous
mixtures of poly(acrylic acid) and poly(vinyl alcohol) at 17%–83% PAA or
0.14–3.5 COOH/OH molar ratios and cross-linked by heat-induced (140 ◦ C,
5 min) esterification. The fibre diameters increased from 270 to 450 nm with
increasing PAA contents. The swelling ratio of the fibrous hydrogels
increased up to 31 times their dry weight with increasing pH from 2 to 7,
and most significantly between pH 4 and pH 5. The liquid uptake of the
fibrous hydrogels was attributed to both the liquid diffused into the fibres
and that held in the inter-fibre pores. About 53%, 35%, 43% and 37% of the
swelling was contributed by the liquid in the inter-fibre pores when the
fibrous hydrogels were swollen at pH 2, 4, 5 and 7, respectively. The fully
swollen fibrous membranes could be triggered by an applied electric field to
swell further. Such additional swelling was dependent upon the polymer
compositions, strength of electric field and pH, and was reversible.

1. Introduction
Hydrogels are three-dimensional hydrophilic polymer net-
works that can swell to many times their mass and volume in
aqueous environments. Polyelectrolyte hydrogels are known
to exhibit additional swelling in response to environmental
stimuli, such as pH, polarity of solvent, ionic strength, or elec-
tric field [1–3], and have been studied for applications such as
sensors and actuators [4–6], drug delivery [7–9] and entrap-
ment of biomolecules [10].
Hydrogels prepared from mixtures of poly(acrylic acid)
(PAA) and poly(vinyl alcohol) (PVA) are among the most
investigated polyelectrolyte hydrogels. As in any polymeric
solids and hydrogels, the stimulus-triggered responses are
diffusion controlled and the kinetics is proportional to the
specific surface. In the case of PAA/PVA hydrogel thin
films [11, 12] and rods [13, 14], the magnitude and speed of
responses to the applied stimuli have been found to be inversely
related to their thickness and diameters [11, 13, 14]. For fully
swollen PAA/PVA hydrogel rods placed in an electric field
(10 V cm−1 ), no deflection was observed when the diameters
exceeded 10 mm [14]. The rate in which the rods deflected
increased 25-fold (from 0.04 to 1 mm s−1 ) when the diameter
1 Author to whom any correspondence should be addressed.
decreased to less than an eighth (from 10 to 1.2 mm) [14]. For
thinner rods, the degree of bending in an electric field (30 V in
0.1 M Na2 SO4 ) increased from 30% to 85% with decreasing
diameters from 1.6 to 0.6 mm [13]. As the diameters of
these rod-shaped hydrogels are 30 or more times the 20–
50 µm diameters of conventional fibres, hydrogel fibres should
exhibit faster responses. Further reducing fibre sizes to the sub-
micrometre range would significantly improve the response.
The capability of making nano- and micro-fibres from
water-soluble polymers including polyelectrolytes [15–18]
by electrospinning offers one way to create hydrogels with
nano-and micro-structures. In our laboratory, we have
successfully generated fibrous hydrogels composed of ultra-
fine fibres with diameters in the range of 500 nm–1.2 µm by
electrospinning of PAA/β-cyclodextrin [3] and PAA/poly(N-
isopropylacrylamide) (PNIPAAm) [19] mixtures followed
by subsequent heat-induced cross-linking. These fibres
were three orders of magnitude finer than the thinnest rods
reported before. They also exhibited pH- and temperature-
responsive behaviour. This article reports our attempt to
generate fibrous hydrogels composed of even finer fibres
by electrospinning PAA/PVA aqueous mixtures followed by
cross-linking via heat-induced esterification. The effects of the
polymer compositions and the cross-linking conditions on the
morphology, packing and stability of the hydrogel fibres were

0957-4484/05/122852+09$30.00 © 2005 IOP Publishing Ltd Printed in the UK 2852

 Ultra-fine polyelectrolyte hydrogel fibres from poly(acrylic acid)/poly(vinyl alcohol)
studied. The swelling behaviours of such ultra-fine fibrous
hydrogels in response to the solution pH, the ionic strength,
and the electric field were also investigated and analysed based
on their porous structures.
2. Experimental details
2.1. Materials
Poly(acrylic acid) (PAA) (average Mv ∼ 450 kDa) and
poly(vinyl alcohol) (PVA) (average Mw 124–186 kDa, 87–89%
hydrolysed) were obtained from Aldrich Chemical Company.
pH buffers were purchased from EM Science. Sodium chloride
(ACS reagent grade) was received from Fisher Scientific. All
solutions were prepared with purified water (Millipore Milli-Q
plus water purification system).
2.2. Electrospinning and film casting
PVA solution was prepared by gently stirring with a magnetic
bar at 80 ◦ C for 30 min, and then cooled down to the room
temperature. PAA solution was prepared under constant
stirring at ambient temperature for 8 h. These two solutions
were mixed to achieve a range of compositions at a constant
6 wt% total polymer concentration. The molar ratios between
PAA carboxylic acid and PVA hydroxyl (assuming 88%
hydrolysis) were 0.14, 0.35, 0.69, 1.4 and 3.5, corresponding
to 0.17, 0.33, 0.50, 0.67 and 0.83 PAA weight fractions,
respectively. About 5 ml of freshly prepared polymer solution
was placed in a glass capillary with the 0.4 mm inner diameter
tip, which was tilted downward at an angle between 0◦ and
30◦ depending on the solution viscosity. A stainless steel
electrode was immersed in the solution and connected to a
positive power supply (Gamma high voltage supply, ES 30-
0.1P). The electrospinning voltage used in this research was
about 8 kV for all the polymer solutions. Aluminium foil
was used as the collector and connected to the ground. The
tip-to-collector distance was 25 cm. All electrospinning was
conducted at room temperature for about 8 h.
Films were cast from the same mixture on a Teflon surface
by the evaporation of water in a vacuum oven at 60 ◦ C for 24 h.
2.3. Measurement and characterization
The solution viscosities were measured according to
ASTM D445 using a Cannon-Fenske viscometer (Cannon
instrument company, USA). Conductivities of the solutions
were determined using a digital conductivity meter (VWR
International). The fibre and fibrous membrane morphology
was observed with a scanning electron microscope (SEM)
(XL30-SFEG, FEI/Philips) at 2 kV accelerating voltage
without gold coating. Differential scanning calorimetry (DSC)
analyses were conducted (DSC-60 Shimadzu, Japan) using
∼5.0 mg samples at a 10 ◦ C min−1 heating rate in nitrogen.
The glass transition temperature (Tg ) was recorded as the
temperature at the midpoint of the baseline shift.
The overall pore volume and the planar pore connectivity
of each fibrous membrane were measured by the membrane’s
capacity to retain a low surface tension and low viscosity liquid,
i.e., hexadecane, using a liquid tensiometer (K14, KRÜSS
USA) [20, 21]. The overall pore volume was estimated by
the maximum liquid retention capacity (Cm , µl mg−1 ), which
was calculated by the membrane mass before (W0 ) and after
(Wm ) complete saturation in hexadecane as follows:
Cm = [(Wm − W0 )/ρ]/ W0 (1)
where ρ is the density of hexadecane. The planar pore volume
(Cv ) was given by the vertical retention capacity (Cv , µl mg−1 ),
measured using a vertical sample with only its lower edge in
contact with the liquid. The sample masses before (W0 ) and
after (Wv ) reaching steady state are used to calculate Cv :
Cv = [(Wv − W0 )/ρ]/ W0 (2)
where ρ is the density of hexadecane. The planar pore
connectivity was indicated by the Cv /Cm ratio.
The swelling ratios of the fibrous membranes and cast
films were obtained by weighing the samples before (W0 ) and
after (Ws ) immersion in pH buffers (at 30 ◦ C for 24 h) and
calculating as follows:
q = (Ws − W0 )/ W0 . (3)
The Wd was obtained after drying the samples in vacuum at
room temperature for 24 h. The mass loss following swelling in
water was obtained by weighing the sample (Wd ) after drying
in vacuum at room temperature for 24 h as follows:
Mass loss = (W0 − Wd )/ W0 × 100%. (4)
The average of three measurements was reported.
The swelling behaviour of cross-linked fibrous mem-
branes was also determined under the electric stimulus. The
30 mm×5 mm×0.35 mm rectangular shaped membranes were
swollen in buffer solutions at room temperature to the equilib-
rium state. Afterwards, the buffer solution was poured into a
plastic case equipped with two parallel carbon electrodes. The
swollen membrane was placed in the middle of a plastic case
filled with the same buffer and centred between two parallel
electrodes (figure 1). The mass before (Ws ) and after (We )
the applied electric field was used to calculate the additional
swelling:
Additional swelling (%) = (We − Ws )/ Ws × 100. (5)
The cyclic swelling behaviour was observed by turning the
electric field on and off while replacing the buffer every hour
to maintain buffer quality since water can be electrolysed.
3. Results and discussion
3.1. Fibre formation
Both PAA and PVA are readily soluble in water. The viscosities
of either aqueous PAA or PVA solutions increased with
increasing polymer concentrations and their concentration
dependence appeared greater above 7 wt% (figure 2). Aqueous
PVA solutions were consistently more viscous than the PAA
solutions at all concentrations.
Mixing PAA and PVA solutions produced homogeneous
solutions. Nine mixtures of PAA and PVA with 17–83 wt%
PAA or at 0.14–3.5 COOH/OH ratios were prepared at a fixed
2853
L Li and Y-L Hsieh

COOH:OH molar ratio 2. 5

V 1800
0.69
1600 0.50
0.35 0.97 2
1400

Conductivity (mS/cm)
0.23
0.14

Viscosity (cp)
1200
0.35mm 1. 5
1000
800
Electrode 1
600 1.4
30mm Buffer solution
400 2.1
Electrode 3.5 0. 5
5mm
200
0 0
0 10 20 30 40 50 60 70 80 90 100
PAA (wt%)
36mm
Figure 3. Viscosities and conductivities of 6 wt% PAA/PVA
Figure 1. Measurement set-up for the electric field effect. aqueous mixtures. The values above the data symbols are the molar
ratios between COOH and OH.

1400
Table 1. Glass transition temperatures (Tg ) and average diameters
1200 of PAA/PVA bicomponent fibres.
PVA
1000 PAA Composition Average
Viscosity (cp)

(weight fraction Experimental Calculated diameter

800 of PAA) ( ◦ C) ( ◦ C) (nm)
600 Pure PAA 129.6
0.83 120.0 116.9 450
400 0.67 110.0 106.7 450
0.58 104.0 101.6 450
200 0.50 95.6 97.5 360
0.33 87.6 89.9 360
0
0 1 2 3 4 5 6 7 8 9 10 11 0.17 84.5 83.8 270
Concentration (wt%) Pure PVA 78.1

Figure 2. Viscosities of PAA and PVA aqueous solutions.

6 wt% total polymer concentration. At 6 wt%, individual
PVA and PAA solutions had viscosities of 94.7 and 74.6 cp,
respectively, whereas all their mixtures had significantly
higher viscosities (figure 3). This behaviour is thought to
be attributed to the strong and abundant hydrogen bonding
between the PAA carboxylic and PVA hydroxyl groups. The
viscosities of the mixtures peaked at the composition of
50 wt% PAA or 0.69 COOH/OH probably due to the possibly
maximized hydrogen bonding between the two polymers. The
composition dependence of the viscosity was not symmetrical
(figure 3). Due to the self-suppression effect, PAA molecules
ionize to a lower extent at higher concentration. For example,
the ionization degree of PAA in its aqueous solution has been
reported to be 16% and 6% at 3% and 10% PAA concentration,
respectively [22]. As a result, PAA molecules are expected to
ionize to a larger extent in the PVA-rich mixtures and therefore
to have a more extended conformation. This may facilitate the
hydrogen bonding interaction between the two polymers and
thus cause the PVA-rich mixtures to be more viscous than the
PAA-rich mixtures. Although PAA molecules may ionize to a
lesser extent at higher concentrations, the conductivity of the
PAA/PVA mixtures still increases from 0.05 to 1.97 mS cm−1
with increasing PAA proportion from 17 to 83 wt% (figure 3).
At 6 wt% total polymer concentration, six mixtures with
17%, 33%, 50%, 58% and 83 wt% PAA or 0.14, 0.35,
0.69, 0.97 and 3.5 COOH/OH ratios were evaluated for
electrospinning. All six could be electrospun continuously
for several hours. The highest fibre collection rate of 80 mg
dry fibres/h was observed with the mixture containing 87 wt%
of PAA, the most conductive and least viscous mixture. The
fibre collection rates were lowered to about 70 and 50 mg h−1
with mixtures containing 50% and 17% PAA, respectively.
Generally, the rates at which fibres were collected were
positively related to the conductivity of the mixtures. As
reported by Shin et al, conductivity is one of the most
important solution properties that affects the fibre formation
during electrospinning [23]. The electric field strength that
is necessary to obtain a stable solution jet is lower for more
conductive polymer solutions. In this work, since a constant
electric field strength was maintained for electrospinning of
all PAA/PVA mixtures and the flow rate was not held constant,
the higher conductivity of the PAA-rich solutions may result in
larger drawing force on the solution jet and thus higher solution
flow rate and fibre collection rate.
The average sizes of bicomponent fibres ranged from 270
to 450 nm (table 1). The fibres generated from mixtures
containing equal or higher PAA contents were larger and
more homogeneous in size, around 450 nm (figures 4(a)–(c)).
Thinner fibres were produced from the more viscous mixtures
in which PVA was the majority (figures 4(d)–(f)). Although
fibres electrospun from the more viscous solutions that were
due to higher concentration were thicker [3, 24], fibre size

2854
 Ultra-fine polyelectrolyte hydrogel fibres from poly(acrylic acid)/poly(vinyl alcohol)
a b
c d
e f
Figure 4. SEM of PAA/PVA bicomponent fibres (bar = 5 µm)
electrospun from 6 wt% total polymer concentration at varying
COOH/OH molar ratio: (a) 3.5 (η = 219.8 cp), (b) 1.4
(η = 531.7 cp), (c) 0.97 (η = 1310.7 cp), (d) 0.69 (η = 1598.3 cp),
(e) 0.35 (η = 1380.5 cp) and (f) 0.14 (η = 1131.4 cp).
dependence on solution viscosity here is more complex. In
this work, the PVA-rich mixtures were more viscous than the
PAA-rich mixtures at the same 6 wt% polymer concentration.
The smaller diameter of fibres electrospun from the PVA-
rich mixtures could be due to the much shorter PVA chains
as reported by others that lower molecular weight polymers
favour thinner fibres [25]. Furthermore, the flow rate of the
mixtures was not held constant so the less viscous and more
conductive PAA-rich mixtures may flow faster and thus give
larger diameter fibres. The equal PAA/PVA bicomponent
fibres were about half of the size of fibres generated from 2:1:1
PNIPAAm/PAA/PVA in DMF [19].
3.2. Compatibility between PAA and PVA in their
bicomponent fibres
Both PAA and PVA are glassy polymers. The compatibility
between two glassy polymers in a mixed solid can be assessed
by whether the glass transition temperature (Tg ) is composition
dependent or obeys the Fox equation [26]. The DSC of the
electrospun PAA, PVA and their bicomponent fibres showed
a single Tg transition (table 1). The Tg of the PAA and PVA
fibres was 129.6 and 78.1 ◦ C, respectively (table 1). The Tg
of the bicomponent fibres was calculated according to the Fox
equation [27].
1/ Tg = W1 / Tg1 + W2 / Tg2
where Tg1 and Tg2 are the glass transition temperatures of PAA
and PVA; W1 and W2 are the weight fractions of PAA and PVA,
respectively. The experimental and calculated values were
Figure 5. Thermal cross-linking mechanism between PAA and PVA
via esterification reaction.
close, indicating that PAA and PVA were highly compatible
solids in the bicomponent fibres.
It has been reported that PAA and PVA are compatible in
the films cast from their aqueous mixtures [28]. Unlike the film
casting method, an electric field is applied in electrospinning.
The evidence of high compatibility between the two polymers
in the bicomponent fibres indicates that the strong voltage
employed in electrospinning did not cause any phase separation
between the partially charged PAA molecules and the neutral
PVA molecules. This could be due to the very strong and
abundant hydrogen bonding between PAA and PVA molecules.
3.3. Cross-linking of PAA/PVA fibres
Heat-induced cross-linking was studied using bicomponent
fibres generated from the mixtures at 3.5 and 0.97 COOH/OH
molar ratios. Upon heating between 120 and 140 ◦ C, all
membranes became insoluble in water, giving evidence of
thermally induced esterification reaction between PAA and
PVA (figure 5). In order to keep the fibrous membrane flat
during thermal cross-linking, the edges of each membrane
were weighed. The cross-linked fibrous membranes shrank
to about half of their initial dimensions and became more
rigid. Although the relaxation times of PAA and PVA
in ethanol/water mixtures were reported to be of the order
of milliseconds [29], the shrinkage may indicate that the
entangled PAA and PVA chains had insufficient time to
relax completely while solidified into very fine fibres.
The Tg values of the cross-linked fibres increased with
increasing heating time (from 5 to 180 min at 120 ◦ C)
(figure 6(a)) and temperatures (from 120 to 140 ◦ C for 5 min)
(figure 6(b)), showing increased cross-linking with both
increasing temperature and length of heating. The increase
in Tg with increasing heating time was more significant when
the reactive carboxyl and hydroxyl groups in the bicomponent
fibres are nearly equal (figure 6(a)), which indicated that the
cross-linking reaction was more efficient at this composition.
All the membranes (COOH/OH molar ratio = 0.97)
retained the fibrous structure (figures 7(a) and (b)) after
heating. However, only those heated at 140 ◦ C for 5 min
could retain their fibrous structure after extended (24 h) water
immersion (figure 7(d)). The extended water immersion
caused those membranes heated at 120 ◦ C for 5 min to partially
lose their fibrous integrity and became film-like at random
locations of the membrane (figure 7(c)). The mass losses after
the water immersion were about 5% and 10% for the fibrous
membranes heated at 140 or 120 ◦ C for 5 min, respectively.
Similar extents of mass loss were observed on the membranes
with a 3.5 COOH/OH molar ratio. These results showed that
the best cross-linked fibrous membrane was the one consisting
of near equal molar PAA/PVA and optimally heated at 140 ◦ C
for 5 min.
2855
L Li and Y-L Hsieh

130 Table 2. Vertical (Cv ) and maximum liquid retention capacity

(a)
(Cm ), of PAA/PVA bicomponent fibrous membranes.
COOH:OH Cured
120 molar 140 ◦ C/ Water Cv b Cm b
ratio 5 min exposurea (µl mg−1 ) (µl mg−1 ) Cv /Cm
Tg ( C)
o

0.97 No No 6.94(0.15) 8.98(0.45) 0.77

COOH:OH = 3.5 Yes No 5.46(0.45) 8.04(0.18) 0.68
110 Yes Yes 2.09(0.30) 5.12(0.12) 0.41
COOH:OH = 0.97
3.5 No No 10.18(1.81) 14.44(0.31) 0.70
Yes No 5.77(0.17) 9.06(0.46) 0.64
100 Yes Yes 1.98(0.09) 4.99(0.36) 0.40
0 50 1 00 150 200 a
Exposed in water for 1 day then dried.
Time (min) b
Standard deviation in parenthesis.
112
(b)
lowing the extended water immersion and drying, fibres were
110 enlarged and most of them merged together (figures 7(c) and
(d)), which significantly decreased the inter-fibre pore sizes.
Tg ( C)

The overall pore volume and planar pore connectivity

o

108
in the membranes were estimated by their liquid retention
capacities, i.e., the maximum liquid retention capacity (Cm )
106 and the vertical (Cv ) to Cm ratio or Cv /Cm , respectively. The
COOH:OH = 0.97 overall (Cm ) and planar (Cv ) pore volumes appeared to be
104 composition dependent (table 2). The as-spun membrane from
115 120 125 130 135 140 1 45 the mixture at a 3.5 COOH/OH molar ratio had significantly
o
Temperature ( C) higher overall (61%) and planar (46%) pore volume. The
planar pore connectivity, or Cv /Cm , of these original fibrous
Figure 6. Glass transition temperatures (Tg ) of bicomponent fibres
cross-linked at (a) 120 ◦ C and (b) for 5 min.
membranes was 77% and 70% for the membranes with 3.5 and
0.97 COOH/OH molar compositions, respectively (table 2).
This indicated that most of the inter-fibre pores were connected
a b
to each other in both membranes and this pore connectivity
a b characteristic appears not to be composition dependent.
The exposure to heat during cross-linking reduced the
overall pore volume by 10% and 37% for the membranes
with 0.97 and 3.5 COOH/OH ratio, respectively, resulting
in only slight difference in their pore volume. Exposure
to water further reduced their overall pore volume by 36%
c
and 45%, yielding insignificant difference between the two
d

d compositions. Both the cross-linking and water exposure

Figure 7. SEM (bar = 5 µm) of PAA/PVA bicomponent fibres
(COOH/OH molar ratio = 0.97) cross-linked under different
conditions, exposed to water and dried in vacuum at ambient
temperature: (a) 120 ◦ C/5 min, (b) 140 ◦ C/5 min, (c) 120 ◦ C/5 min
and (d) 140 ◦ C/5 min, water.
3.4. Effect of cross-linking and water immersion on overall
pore volume and pore connectivity
Compared with the as-spun membrane (figure 4(c)), the
heat-induced cross-linking caused the fibres in membranes
(COOH/OH molar ratio = 0.97) to become more closely
packed (figures 7(a) and (b)). These changes were more sig-
nificant at the higher temperature, where some fibres merged
together. The thermal cross-linking caused little change on the
fibres but appeared to reduce the spaces between fibres. Fol-
reduced the vertical liquid retention (Cv ) of both membranes
to greater extents than their Cm values. Again, the reduction
in Cv was more significant on the membrane containing
predominantly PAA, i.e., 3.5 COOH:OH, i.e., by 43% and
66%, in comparison to the 21% and 62% for the equal molar
composition. The proportionally higher reduction in Cv than
Cm led to the slightly lowered pore connectivity (Cv /Cm )
by thermal cross-linking. Far more significant decreases in
Cv /Cm were observed after the extended water treatment of
the fibrous membranes. The final pore characteristics (Cv ,
Cm , Cv /Cm ) resulting from cross-linking and water exposure
were similar between the two compositions, however. This
suggested that heat and water treatments exhibited greater
effects on the inter-fibre pore structures of the membranes
composed of more loosely packed fibres.
This pore volume and structural information derived
from the liquid retention data not only confirmed the SEM
observations, but also provided insight into the porous
structure. From the SEM images, the fibre packing and inter-
fibre pore sizes of the bicomponent fibrous membranes with
different compositions appeared similar (figures 4(a) and (c)).
The overall pore volume measured by liquid retention indicated

2856
 Ultra-fine polyelectrolyte hydrogel fibres from poly(acrylic acid)/poly(vinyl alcohol)
35 Fibrous COOH:OH=3.5
Fibrous COOH:OH=0.97
30 Fibrous COOH:OH=0.14
Cast film COOH:OH=3.5
25
Swelling ratio
20
15
10
5 pores within each layer have been found to be highly
0 linking conditions [31]. Starting with the same original
1 2 3 4 5 6 7 8
pH
Figure 8. PH-responsive swelling behaviour of hydrogel fibres and
cast film with varying COOH/OH molar ratio.
that the fibres were packed differently in the membranes with
different compositions. The differences appeared to be in the
thickness direction, which was not observable by the SEM
due to the limited depth of field. The much larger decrease
in the overall pore volume for the membranes with the higher
PAA content from thermal cross-linking could be caused by
the more significant thickness reduction.
3.5. pH- and ionic-strength-responsive swelling behaviours
The cross-linked fibrous membranes exhibited pH-responsive
swelling behaviour (figure 8). At pH 2 and 4, the membranes
took up to 6 and 11 times of liquid, respectively. Significantly
more liquid was absorbed at pH 5, up to 29 times, followed
by a slight increase to 31 times at pH 7. Higher absorption
was observed with fibrous membranes that contained more
PAA at all pH values. The compositional effect was also pH
dependent, i.e., negligible below pH 4 and more distinct at
pH above 4. At a 3.5 COOH/OH molar composition, the
fibrous membrane absorbed almost twice as much liquid as
the cast film at all pH values between 2 and 7. In fact, the
fibrous membrane with less PAA (0.97 COOH/OH) could still
swell 50% more than the cast films with higher PAA proportion
(COOH/OH molar ratio = 3.5).
In a swollen hydrogel, the repulsion among the negatively
charged carboxylate ions on PAA molecules increases the
free volume, thus expanding its capability to take in water.
At the same time, the hydroxide ions in the buffer solutions
could diffuse into hydrogel, react with the protons dissociated
from the carboxyl groups of PAA to form water and swell the
hydrogel [30]. The dissociation of carboxyl groups of PAA is
much more significant when pH is higher than its pK a , 4.7, and
therefore the hydrogel composition showed a greater effect at
pH above 4.
The liquid uptake in fibrous membranes consists of the
liquid held in the inter-fibre pores as well as that diffused
into the fibres. The contribution between the two to the
total liquid uptake, or the swelling ratio measured, depends
on how the fibres pack and swell. In electrospinning, the
fibres were deposited layer by layer into a fibrous membrane.
Table 3. Swelling ratios of fibrous membranes and cast films
(COOH:OH = 3.5) before (qbc ) and after (qac ) centrifugation.
Fibrous membrane Cast film
pH qbc qac qbc qac
2 6.6 1.5 3.1 3.0
4 11.9 8.8 7.7 7.5
5 27.9 26.2 15.8 15.5
7 31.0 30.0 19.4 18.9
The spaces between the fibre layers and in the inter-fibre
dependent upon the electrospinning process and the cross-
dimensions, a fibrous membrane swelled like a flattened
sponge to become several times thicker than the cast film, while
expended similarly in lengths and widths. It is this ability
to expand significantly in thickness that makes these fibrous
hydrogels exhibit much higher swelling capacities than the cast
film.
To estimate the contributions of the liquid held in the
inter-fibre pores and that diffused into the fibres to the overall
swelling ratios, fully swollen membranes (COOH:OH = 3.5)
were centrifuged at 3000 rpm for 10 min to remove the liquid
in the inter-fibre pores. The swelling ratios of the fibrous
hydrogels before and after the centrifugation were compared
with those of cast films (table 3). As expected, the hydrogels
from the cast films lost a negligible amount of liquid (∼2%)
from centrifugation. The fibrous membranes fully swollen at
pH 2, 4, 5 and 7, on the other hand, lost 77%, 26%, 6% and 3%
of liquids from centrifugation, respectively. This observation
indicated that the inter-fibre pores of swollen membranes were
much smaller at pH 5 and above. This is consistent with higher
swelling of the fibres with increasing pH, reducing the inter-
fibre pore sizes of the swollen membranes. Assuming the
amount of liquid diffused into the fibres is the same as that
in the cast film of the same composition, the proportion of
liquid held in the inter-fibre pores could be calculated from the
difference in their swelling ratios. Based on this assumption,
the proportion of the liquid in the inter-fibre pores was 53%,
35%, 44% and 38% for the fibrous membranes fully swollen at
pH 2, 4, 5 and 7, respectively. This indicates that the proportion
of liquid held in the inter-fibre pores was slightly higher than
that diffused into the fibres at pH 2. With greater swelling of
the fibres at the higher pHs, a minority of liquid absorbed by
the fibrous membranes was attributed to the liquid diffused into
the spaces in between the swollen fibres. The swelling ratios
of the fibrous membranes and cast films increased with pH in
similar patterns (figure 8), indicating that the contribution of
fibre swelling to the liquid uptake in the fibrous membranes was
similarly pH dependent to the hydrogel film. However, their
differences showed that liquid retained in the pores increased
significantly between pH 4 and 5, but was essentially the same
below and above this range. This major increase of liquid taken
up by the pores between swollen fibres suggested the enlarged
pore structure in the thickness direction might have occurred
between pH 4 and 5. It should be noted that the centrifugation
force employed may not be strong enough to overcome the
capillary force to remove the liquid inside the very small inter-
fibre pores.
2857
L Li and Y-L Hsieh

10 40
(a)
9
8 COOH:OH = 3.5
7 30 with electric field
Swelling ratio

6 without electric field

Swelling ratio
5
20
4
3 Fibrous membrane
2 Cast film
10
1
0
-3 -2 -1 0
log µ (M) 0
2 4 5 7
Figure 9. Ionic strength responsive swelling behaviour of hydrogel pH
fibres and cast film with the same composition (COOH/OH molar
ratio = 3.5). 100
(b) pH=4, COOH:OH=3.5
pH=5
pH=7
pH=4, COOH:OH=0.97
80
The swelling behaviour in response to ionic strength

Additional Swelling (%)

adjusted by the concentration of sodium chloride (NaCl) was
also evaluated. The swelling ratios did not change at increasing
ionic strengths of 0.001–0.01, and 0.1 M. However 44.2%
and 30.9% decreases in swelling were observed at the highest
ionic strength studied, i.e., 1.0 M, for hydrogel fibres and cast
films, respectively (figure 9). At this concentration, it appeared
that sufficient Na cations and Cl anions could diffuse into
the hydrogel to shield the electrostatic repulsion between the
partially ionized and negatively charged PAA molecules. This
reduced the free volumes inside the hydrogel, thus squeezed
out water and made the hydrogel de-swell. Because of the
higher specific surface of hydrogel fibres, the ions in the
surrounding solution could diffuse into the hydrogel fibres
more easily, thus exhibiting greater effect.
3.6. Electric field responsive swelling behaviours
The swelling behaviour of the fully swollen fibrous membranes
under the influence of an electric field was investigated
using the membrane with the highest amount of PAA (3.5
COOH:OH). A 10 V cm−1 electric field was shown to trigger
additional swelling at pH 4–7, but not at pH 2 (figure 10(a)).
Additional swelling was highest, exceeding 80%, at pH 4, and
was much lower (<20%) at pH 5 and 7. It took 5 min to reach
a new equilibrium at the low extents of additional swelling (pH
5 and 7) and much longer (30 min) to reach the proportionally
higher additional swelling at pH 4 (figure 10(b)). The
additional swelling (pH 4, and 10 V cm−1 ) was found to be
much lower (10%) for the membrane with nearly equal COOH
and OH molar compositions.
Under the electric field, the increased swelling ratios of the
fibrous membranes at pH between 4 and 7 were accompanied
with increased width and thickness of the membrane. For
example, about 50% increases were visually observed at pH 4.
The two freely suspended ends of the fibrous membrane also
bent toward the cathode of the electric field. When subjected
to a dc electric field, the cations in the PAA hydrogel such as
the protons dissociated from the carboxyl groups are driven
toward the cathode, while the polyanionic PAA backbones
remain immobile due to the cross-linked polymeric network.
As a result, the osmotic pressure of the anode side increases
and becomes larger than that of the cathode side. Therefore the
60
40
20
0
0 10 20 30 40 50 60
Time (min)
Figure 10. Additional swelling of hydrogel fibres: (a) with and
without the electric field (10.0 V cm−1 ); (b) kinetics in buffers with
different pH.
pressure difference occurs in the hydrogel, and the hydrogel
is bent toward the cathode [14]. The deflection of a fibrous
hydrogel (figure 1) was expressed in terms of the distance
between the ends of the hydrogel before and after bending.
The magnitude and velocity of the deflection of the hydrogel
with a 3.5 COOH/OH molar ratio (10.0 V cm−1 electric field
and pH 4) was about 12 mm and 0.8 mm s−1 , respectively.
With lowering of the COOH/OH molar ratio to 0.97, the
deflection magnitude and velocity decreased to about 5 mm
and 0.2 mm s−1 , respectively. The ultra-fine fibrous hydrogels
prepared by electrospinning did not exhibit obvious differences
in the deflection magnitude and velocity when compared with
the hydrogel rod [14]. It may be due to the fact that the ultra-
fine hydrogel fibres are entangled together inside the fibrous
hydrogel, which compromises the deflection of the individual
hydrogel fibres. However, it should also be noted that the
fibrous hydrogel and the hydrogel rod have different length,
thickness, cross-section shape, swelling media and polymer
composition.
The external electric field may also facilitate the
dissociation of the carboxylic acid groups of PAA, further
expanding the polymer network. The extent of additional
swelling appeared to be inversely related to the extent of
dissociated carboxylic acid in the swollen hydrogel fibres.

2858

100 (a)
Additional swelling (%)
80
60
40
10V/cm
4.9V/cm
20 3.3V/cm
2.0V/cm
0 0
0 20 40
Time (min)
20
(b)
Additional swelling (%)
15
10
5 10V/cm
4.9V/cm
3.3V/cm
2.0V/cm
0
0 10 20
Time (min)
Figure 11. Effect of electric field strength on the additional swelling
of hydrogel fibres (COOH/OH molar ratio = 3.5) in (a) pH 4 and (b)
pH 7 buffer, respectively.
The highly dissociated structures at pH 5 and 7 were less
affected by the applied electric field than the less dissociated
hydrogel fibres at pH 4. The absence of electric field effects
at pH 2 suggests a lack of dissociation of the carboxyl groups.
The additional swelling generally increased with increasing
electric field strengths at both pH 4 (figure 11(a)) and pH 7
(figure 11(b)). Between 3.3 and 10.0 V cm−1 , the additional
swelling at pH 4 was consistently higher than that at pH 7.
However, under a weaker electric field of 2.0 V cm−1 , no
further swelling was detected at pH 4 whereas an 8% swelling
increase was shown at pH 7. At pH 4, it took about 20
min for the membranes to reach equilibrium (figure 11(a)).
Within the first three minutes from exposing to the electric
field, the membranes absorbed at 0.6%, 1.4% and 2.4% per
min at 3.3, 4.9 and 10.0 V cm−1 , respectively. Beyond 3 min,
the swelling rates became similar, i.e., 3.5%, 4.0% and 3.3%
per min at 3.3, 4.9 and 10.0 V cm−1 , respectively. At pH
7, equilibrium swelling was reached in about 5 min under
electric fields between 3.3 and 10.0 V cm−1 and at a similar
swelling rate of about 3.5% per min (figure 11(b)). However,
at 2.0 V cm−1 , reaching the equilibrium took twice as long and
had a much lower speed of 0.9% per min. At pH 4, the lower
initial swelling rate, in particular under weaker electric field,
was again attributed to less dissociated carboxylic acid.
The electric field triggered additional swelling of
PAA/PVA hydrogel fibrous membranes was largely reversible.
In ten repetitive exposures to the 10.0 V cm−1 electric field at
Ultra-fine polyelectrolyte hydrogel fibres from poly(acrylic acid)/poly(vinyl alcohol)
90
80
Additional swelling (wt%)
70
60
50
40
30
20
10
0
2 4 6 8 10 12 14 16 18 20
60 Time (hr)
Figure 12. Cyclic swelling (1 h) and de-swelling (1 h) behaviour of
hydrogel fibres (COOH/OH molar ratio = 3.5) in pH 4 buffer
solution and 10.0 V cm−1 electric field.
pH 4, additional swelling between 72% and 83% were reached
(figure 12). The swelling nearly reversed when the electric field
was turned off each time. A permanent 8% additional swelling
remained after the first cycle, suggesting certain irreversible
swelling in the hydrogel fibres caused by initial exposure to the
electric field. This swelling and de-swelling cycle could be re-
peated for at least 20 times while retaining the membrane form.
30 4. Conclusions
Ultra-fine fibrous membranes were generated by electrospin-
ning of PAA and PVA aqueous mixtures containing 17%–83%
PAA or COOH/OH molar ratios from 0.14 to 3.5. Generally,
the fibre formation rates were positively related to the PAA
contents. The average fibre diameters also increased from 270
to 450 nm with increasing PAA contents or COOH/OH ra-
tios. Cross-linking via esterification was best achieved on the
fibrous membranes containing near equal COOH/OH molar
composition (58% PAA) and optimally heated at 140 ◦ C for
5 min.
These hydrogel fibrous membranes took up different
extents of aqueous liquids in response to the pH, ionic strength
and electric field. The hydrogel fibrous membranes took up
liquid up to 31 times their dry weight and their ability to absorb
liquid increased with increasing PAA contents and pH, most
significantly between pH 4 and 5. The swelling ratio, or liquid
uptake, in the fibrous hydrogel was attributed to the liquid held
in the inter-fibre pores as well as that diffused into the fibres.
The contribution of the two to the total liquid uptake depends
on how the fibres layout and swell. About 53%, 35%, 44%
and 38% of the fibrous hydrogel swelling was contributed by
the liquid held in the inter-fibre pores when swollen at pH
2, 4, 5 and 7, respectively. The fibrous hydrogel reduced
swelling by 44.2% when the ionic strength increased from 0.1
to 1.0 M (pH 4), but showed no change in swelling at low
ionic strengths between 0.001 and 0.1 M. This could be the
critical NaCl concentration where the diffusion of Na cations
and Cl anions into the hydrogel fibres was maximized to shield
the electrostatic repulsion among PAA polyanions and reduces
the free volumes inside the hydrogel.
The fully swollen fibrous hydrogel could be triggered
by applied electric field (10 V cm−1 ) to swell further.
2859
L Li and Y-L Hsieh
Under the electric field, the fibrous hydrogel membrane
with a 3.5 COOH/OH molar composition showed the largest
additional swelling of 80% at pH4. The additional swelling
increased with increasing PAA contents in the membranes and
the strengths of the electric fields, and was reversible with the
application and removal of the electric field.
Because of their stimulus-responsive swelling behaviour
and the ultra-high specific surface, these hydrogel fibrous
membranes are being further investigated for their potential
for controlled release and immobilization of chemical and
biological significant agents.
References
[1] Seki T and Okahata Y 1984 Macromolecules 17 1880–2
[2] Cleary J, Bromberg L E and Magner E 2003 Langmuir 19
9162–72
[3] Li L and Hsieh Y-L 2005 Polymer 46 5133–9
[4] Kim S J, Yoon S G, Lee Y M, Kim H C and Kim S I 2004
Biosensors Bioelectron. 19 531–6
[5] Fernandez E, Lopez D, Lopez-Cabarcos E and
Mijangos C 2005 Polymer 46 2211–7
[6] Elliott J E, Macdonald M, Nie J and Bowman C N 2004
Polymer 45 1503–10
[7] Mandal T K, Bostanian L A, Graves R A and
Chapman S R 2002 Pharmaceutical Res. 19 1713–9
[8] Panayiotou M and Freitag R 2005 Polymer 46 615–21
[9] Zhang X-Z, Lewis P J and Chu C-C 2005 Biomaterials 26
3299–309
[10] Di Benedetto F, Biasco A, Pisignano D and Cingolani R 2005
Nanotechnology 16 S165–70
2860
[11] Gerlach G, Guenther M, Suchaneck G, Sorber J, Arndt K-F and
Richter A 2004 Macromol. Symp. 210403–10
[12] Matsuyama H, Teramoto M, Matsui K and Kitamura Y 2001
J. Appl. Polym. Sci. 81 936–42
[13] Fei J, Zhang Z and Gu L 2002 Polym. Int. 51 502–9
[14] Shiga T, Hirose Y, Okada A and Kurauchi T 1992 J. Appl.
Polym. Sci. 44 249–53
[15] Jin H-J, Fridrikh S V, Rutledge G C and Kaplan D L 2002
Biomacromolecules 3 1233–9
[16] Ohkawa K, Cha D, Kim H, Nishida A and Yamamoto H 2004
Macromol. Rapid Commun. 25 1600–5
[17] Yao L, Haas T W, Guiseppi-Elie A, Bowlin G L,
Simpson D G and Wnek G E 2003 Chem. Mater. 15 1860–4
[18] Reneker D H and Chun I 1996 Nanotechnology 7 216–23
[19] Chen H and Hsieh Y-L 2004 J. Polym. Sci. A 42 6331–9
[20] Hsieh Y L 1995 Textile Res. J. 65 299–307
[21] Hsieh Y L, Miller A and Thompson J 1996 Textile Res. J. 66
1–10
[22] Inzelt G and Grof P 1977 Acta Chim. Acad. Sci. Hung. 93
117–22
[23] Shin Y M, Hohman M M, Brenner M P and
Rutledge G C 2001 Polymer 42 09955–67
[24] Deitzel J M, Kleinmeyer J, Harris D and Beck Tan N C 2000
Polymer 42 261–72
[25] Koski A, Yim K and Shivkumar S 2003 Mater. Lett. 58 493–7
[26] M’Bareck C O, Nguyen Q T, Metayer M, Saiter J M and
Garda M R 2004 Polymer 45 4181–7
[27] Fox T G 1956 Bull. Am. Phys. Soc. 1 123
[28] Vazqueztorres H, Cauichrodriguez J V and
Cruzramos C A 1993 J. Appl. Polym. Sci. 50 777–92
[29] Theron S A, Zussman E and Yarin A L 2004 Polymer 45
2017–30
[30] De S K, Aluru N R, Johnson B, Crone W C, Beebe D J and
Moore J 2002 J. Microelectromech. Syst. 11 544–55
[31] Jin X and Hsieh Y-L 2005 Polymer 46 5149–60