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Anisotropic tough poly(vinyl alcohol) hydrogels

Article in Soft Matter · October 2012

DOI: 10.1039/c2sm26102b

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Anisotropic tough poly(vinyl alcohol) hydrogels
Lin Zhang,ab Jing Zhao,a Jintang Zhu,a Changcheng Hea and Huiliang Wang*a
Received 12th May 2012, Accepted 7th August 2012
DOI: 10.1039/c2sm26102b

Anisotropic tough hydrogels are of great importance in biomedical fields. Tough poly(vinyl alcohol)
(PVA) hydrogels with anisotropic porous structure and mechanical properties are obtained with a facile
directional freezing–thawing (DFT) technique. The PVA gels have an aligned porous structure, with
long aligned channels in the direction parallel to the freezing direction and pores with similar sizes in the
perpendicular direction. The degree of crystallinity of the freeze-dried PVA hydrogels increases with
number of DFT cycles, and it can reach 55.8%. The PVA hydrogels have excellent mechanical
properties, as exhibited by the high tensile strengths (0.3–1.2 MPa), medium moduli (0.03–0.10 MPa)
and high fracture energies (160–420 J m
2) of the gels with solid contents of 10–12%. More importantly,
the gels exhibit significant anisotropy in the mechanical properties, and their tensile strengths, moduli
and fracture energies are higher in the perpendicular direction than those in the parallel direction.
Anisotropic mechanical behaviors can also be found in the cyclic tensile tests of the PVA hydrogels. The
anisotropic mechanical properties of the DFT PVA hydrogels could be attributed to the oriented
arrangement of crystalline regions along the direction perpendicular to the direction of freezing.

Introduction micelles as the polyfunctional initiating and crosslinking centers

Normal synthetic hydrogels are generally mechanically weak,
due to the structural inhomogeneity in their network, i.e. the
uneven distribution of cross-linking points and chain lengths
between cross-linking points. On the other hand, biological gels
such as some soft tissues in human beings and other animals, e.g.
tendons and ligaments, usually exhibit excellent mechanical
properties owing to their well-developed microstructures, which
can effectively dissipate the applied force.1 In the last decade, gel
scientists have achieved significant progress in developing novel
hydrogels with unique microstructures and high mechanical
strength.2–4 The typical tough hydrogels are: topological (TP) gel
or slide-ring (SR) gel,5 nanocomposite (NC) gel,6 double-
network (DN) gel,7 tetra-arm polyethylene glycol (PEG) based
gel,8,9 and macromolecular microsphere composite (MMC) gel.10
Biological gels usually have anisotropic microstructures and
hence anisotropic mechanical behaviors and functions.11,12
However, synthetic hydrogels are generally isotropic in both
microstructure and properties. Some hydrogels with anisotropic
microstructures and/or physical properties have been developed
in recent years,13–16 but only a few hydrogels developed by
Gong’s group based on the DN gel concept exhibit high
mechanical strength.17–19 We have also observed an oriented
microstructure in the hydrogels synthesized by using peroxidized
a
College of Chemistry, Beijing Normal University, Beijing, China. E-mail:
wanghl@bnu.edu.cn; Fax: +86 10 58800267; Tel: +86 10 58808081
b
Yingkou University Zone, 46 Bowen Road, Yingkou, Liaoning 115014,
China
(PFICC).20
Poly(vinyl alcohol) (PVA) hydrogel holds tremendous promise
in pharmaceutical and biomedical fields because of its many
desirable characteristics, such as non-toxicity, biocompatibility,
high mechanical strength, and rubber-like elasticity. PVA
hydrogels can be prepared by various chemical crosslinking
methods21 or simply by exposing aqueous solutions of PVA to
repeated freezing and thawing.22 Cyclic freezing–thawing (FT)
processing produces stable hydrogels that are physically cross-
linked by the presence of crystalline regions. The frozen–thawed
gels have demonstrated enhanced mechanical properties.23
However, the hydrogels prepared by the FT method show
isotropic mechanical properties on a macroscopic scale. A few
anisotropic PVA hydrogels have been prepared by applying
stress to the hydrogels during the FT process24,25 or under a
magnetic field by using PVA solutions containing micron-sized
carbonyl iron particles.26
Directional freezing–thawing (DFT) is a cheap and simple
technique to prepare materials with aligned porous struc-
tures.27,28 A solvent is frozen unidirectionally and the pore
structure is templated from the aligned solvent crystals that are
formed. Since 2005, Zhang and Cooper have applied this method
to produce several kinds of polymeric materials and polymer
composites.27,28 For example, they have prepared aligned mac-
roporous polymeric structures by the directional freezing of
aqueous solutions of water-soluble polymers such as PVA.27 But
they have not paid any attention to the hydrogels and their
mechanical properties. Actually, the application of the DFT
method to prepare anisotropic hydrogels with agar and agarose

This journal is ª The Royal Society of Chemistry 2012 Soft Matter, 2012, 8, 10439–10447 | 10439
has been reported by Tong et al.29 in 1984 and by Yokoyama
et al.30 in 1990, respectively. However, after then no reports can
be found, until very recently Wu et al. reported the preparation
of anisotropic poly(ethylene glycol) (PEG) hydrogels by unidi-
rectional freezing and cryopolymerization.31
In this work, we applied the DFT method to prepare PVA
hydrogels. Through characterization of the microstructure and
the testing of the mechanical properties of the DFT PVA
hydrogels, we show that gels have an aligned porous micro-
structure and anisotropic mechanical properties.
Experimental
Materials and hydrogel preparation
A weighed amount of PVA (polymerization degree 1750, Sino-
pharm Chemical Reagent Co, Ltd., Shanghai, China) was added
in a fixed amount of deionized water, the mixture was mechan-
ically stirred for 30 min, and was then heated to 100  C and
stirred for about 6 h to ensure the PVA was dissolved, to form a
homogeneous transparent solution. 20 mL PVA solution was
transferred into a mold made by placing a silicone spacer with a
height of 2 or 4 mm between two polytetrafluoroethylene (PTFE)
plates. The mold was immersed into liquid nitrogen at a speed of
10 mm min
1 until it was fully immersed. The frozen sample was
then thawed at ambient temperature for 2 h. Repeating the DFT
process could get samples with different DFT cycles.
PVA hydrogels were also fabricated with normal freezing–
thawing (FT) by freezing the PVA solution in the mold in a
refrigerator (
10  C) and thawing at ambient temperature.
Characterizations
For SEM investigations, cubic samples (6 mm  4 mm  2 mm)
were cut from the PVA hydrogels and were immediately plunged
into liquid nitrogen for about 15 min, and then freeze-dried for
24 h to ensure that all water was removed. The dried samples
were sputter coated with a thin layer of gold and then investi-
gated with a Hitachi S-4800 scanning electron microscope
(Tokyo, Japan) along the directions parallel and perpendicular
to the freezing direction.
The PVA hydrogels obtained by the DFT method and a PVA
solution (10 wt%) were vacuum dried, and then the dried films were
characterized by X-ray diffractometry (XRD, PANalytical Co.
Ltd., Netherlands) using Cu-Ka radiation in the 2q range 10–60 .
Tensile tests
An Instron 3366 electronic universal testing machine (Instron
Corporation, MA, USA) was used for all mechanical tests; 100 N
or 1 kN load cells were used according to the load required.
Dumbbell shaped gel specimens standardized as DIN-53504 S2
(overall length: 75 mm; width: 10 mm; inner width: 4 mm, gauge
length: 20 mm, thickness: 2 mm) for tensile tests were cut from gel
samples in both directions parallel and perpendicular to the
freezing direction. At least 5 specimens were tested for each
sample to obtain the average value.
Tensile tests were performed at a cross-head speed of 800 mm
min
1. The tensile stress st is calculated as follows: st ¼ load/tw
(t and w are the initial thickness and width of the dumbbell
10440 | Soft Matter, 2012, 8, 10439–10447
shaped gel sample, respectively). The tensile strain 3t is defined as
the change in the length relative to the gauge length of the free-
standing specimen, and the fracture tensile strain 3b is the tensile
strain on a sample when it breaks. Stress and strain between 3t ¼
10–30% were used to calculate the initial elastic modulus (E). The
gel specimens were coated with silicone oil to prevent water loss
during the tests.
Cyclic tensile tests were performed by performing subsequent
trials immediately following the initial loading at a crosshead
speed of 400 mm min
1.
Tearing tests
The fracture energies G of the gels were measured by tearing tests
introduced by Gong et al.32,33 The gels were cut into trousers-
shaped samples (Scheme 1), standardized as the JIS-K6252 1/2
size (4 mm in thickness, 50 mm in length with an initial notch of
20 mm, and 7.5 mm in width). All the samples were measured at a
constant tearing rate (velocity) of 10 mm min
1. The fracture
energy G, defined as the energy required for creating a unit area
of fracture surface in a sample, was calculated by the following
equation,4,19,33
2Fave
G¼
w
where Fave is the average force during the tear and w is the width
of the gel specimens.
Results and discussion
PVA hydrogels with different solid contents (10 wt% and 12
wt%) and different DFT cycles were prepared. Meanwhile, for
comparison, hydrogels fabricated by the normal FT method
were also prepared. To simplify the expressions, DFT-x-y and
FT-x-y are used to express the hydrogels made by the DFT and
FT methods, respectively, where x is the solid content of gel
(wt%) and y is the number of DFT or FT cycles. In addition, for
the DFT gels, the direction parallel (//) or perpendicular (t) to
the freezing direction is indicated.
Microstructures
The freeze-dried DFT-10-1, DFT-10-3 and DFT-10-5 PVA
hydrogels were investigated by SEM from both the parallel and
Scheme 1 The diagram of the specimens for the tearing tests, cut from a
gel sample in both directions parallel and perpendicular to the freezing
direction. The long arrow shows the freezing direction, and the short
arrows show the directions in which the arms are peeled.
This journal is ª The Royal Society of Chemistry 2012
perpendicular directions, and the SEM micrographs are shown
in Fig. 1.
SEM investigations show that the obtained PVA gels have
anisotropic porous microstructures. Long aligned channels are
found in the parallel direction (Fig. 1a–c); they are almost the
same as the ‘‘fish-bone’’ morphology reported by Zhang et al.27
Pores with similar sizes are found in the perpendicular direction
(Fig. 1d–f). The size of the pores increased with increasing
number of DFT cycles. It is mainly 1–2 mm for the DFT-10-1 gel
(Fig. 1d), 2–5 mm for the DFT-10-3 gel, and >5 mm for the DFT-
10-5 gel.
The X-ray diffraction profiles of the dried DFT PVA films and
a PVA film obtained by directly drying the 10 wt% PVA solution
(reference) are presented in Fig. 2. Strong crystalline reflections Fig. 2 XRD profiles of the DFT-10 PVA films and a normal PVA film
(reference).
in the 2q range 18–21 and two weak peaks centered at 2q z 28
and 41 , which correspond to the diffraction reflections of crys-
talline PVA,34 are present. Tensile mechanical properties
The degrees of crystallinity (cc) of the PVA hydrogel samples
were approximately evaluated from Fig. 2 as the ratio between The DFT PVA gel specimens for tensile tests were cut from the
the area of the crystalline reflection in the 2q range 18–21 (A1) directions parallel and perpendicular to the freezing direction.
and the area subtending the whole diffraction profile of the gel The typical tensile stress–strain (st–3t) curves of the DFT-10
sample (A2): PVA gels are demonstrated in Fig. 3.
Fig. 3 shows that the tensile properties of the gels vary with the
A1
cc ¼  100% number of DFT cycles. The tensile strength at break (sb), frac-
A2 ture strain (3b) and elastic modulus (E) of the gels were obtained
and summarized in Fig. 4. In the parallel direction, sb increases
The cc of the dried DFT PVA films increases with increasing significantly with increasing number of DFT cycles, i.e. from 0.28
number of DFT cycles; they are 53.7% (DFT-10-1), 55.6% (DFT- MPa at 3 DFT cycles to 0.62 MPa at 9 cycles. In the perpen-
10-3) and 55.8% (DFT-10-5), respectively. They are higher than dicular direction, sb is about 0.4 MPa after only 3 DFT cycles; it
that of the PVA film (43.0%) obtained by directly drying the increases to 0.63 MPa at 5 DFT cycles and after that remains
PVA solution, and are a little higher than those obtained by almost constant. The 3b of the DFT PVA gels is relatively low, in
the normal FT method (ca. 50% when the PVA solid content is the range 250–375%; it decreases with number of DFT cycles in
10 wt%).23,34 the perpendicular direction but remains almost constant in the

Fig. 1 SEM micrographs of DFT PVA hydrogels investigated from the directions parallel (a–c) and perpendicular (d and e) to the freezing direction.
(a, b and d) DFT-10-1; (c and e) DFT-10-3; and (f) DFT-10-5.

This journal is ª The Royal Society of Chemistry 2012 Soft Matter, 2012, 8, 10439–10447 | 10441
Fig. 3 Typical tensile stress–strain curves of DFT-10 PVA hydrogels in
the directions parallel (a) and perpendicular (b) to the freezing direction.

parallel direction. The E of the DFT PVA gels increases with

increasing number of DFT cycles.
More interestingly, from both Fig. 3 and 4, there are obvious
differences between the mechanical properties of the DFT gels
along the directions parallel and perpendicular to the freezing
direction, suggesting the DFT PVA hydrogels have anisotropic
mechanical properties. For the hydrogel prepared with the same
number of DFT cycles, the sb, 3b and E in the perpendicular
direction are usually higher than those in the parallel direction,
but the difference becomes less with increasing number of DFT
cycles and is even negligible after 9 DFT cycles.
Normal tough synthetic hydrogels usually have ‘‘S’’ shaped
st–3t curves, i.e. st firstly increases almost linearly and rapidly
with 3t, and then at a lower rate, at last increases quicker again till
fracture.35–37 The elastic modulus (E) of a hydrogel is usually
calculated in the low strain range (e.g. 10–30%). However, the
DFT PVA gels showed ‘‘J’’ shaped st–3t curves, the st firstly
increases with 3t linearly but slowly, and then at a faster rate to an
almost linear range until fracture (Fig. 3). This kind of st–3t curve
has been reported for many biomaterials.12,38 The E values of the
DFT PVA gels calculated in the 10–30% strain range (E1) are
quite low (Fig. 4c). We have also calculated the E of the DFT
PVA gels in the second linear range (E2), and the calculated
values are also included in Fig. 4c. E2 is about 3–4 times higher
than E1. Similarly to E1, E2 also increases with increasing number
of DFT cycles, and the E2 in the perpendicular direction is higher
than that in the parallel direction.
For comparison, PVA hydrogels fabricated by the normal FT
method were also cut from two directions and tested. The sb and E
of the FT-10-3 and FT-10-5 PVA gels are also included in Fig. 4a
and c, respectively. Not surprisingly, no significant difference in sb
and E can be found between the two directions, indicating the
isotropic nature of the FT gels. In addition, there are some
Fig. 4 The sb (a), 3b (b) and E (c) of the DFT-10 PVA gels as a function
of number of DFT cycles. The sb and E1 of the FT-10-3 and FT-10-5
PVA gels are also included.
differences between the mechanical properties of the FT and DFT
gels. The sb and E of the FT-10-3 PVA gel are lower than those of
the DFT-10-3 gel, and the sb and E of the FT-10-5 PVA gel are
higher than those of the DFT-10-5 gel from the parallel direction,
but lower than those from the perpendicular direction.
DFT PVA gels with a higher solid content (12 wt%) exhibit
higher sb and E1 (Fig. 5). Both sb and E increase with increasing
number of DFT cycles, and they are higher in the perpendicular
direction than those in the parallel direction for the gel with the
same number of DFT cycles.
These tensile test results show that the DFT PVA hydrogels
have very good mechanical properties, similar to those of FT
gels.39,40 The sb of the gels with solid contents of 10% and 12%
are in the range 0.3–1.2 MPa, which is higher than most NC gels,
and just a little lower than some of the toughest DN gels.3,17,41
Fracture energy
The fracture energies of the DFT PVA gels were measured by
tearing tests on specimens cut from the directions parallel and

10442 | Soft Matter, 2012, 8, 10439–10447 This journal is ª The Royal Society of Chemistry 2012

Fig. 5 The sb (solid symbols) and E (open symbols) of the DFT-12 PVA
gels as a function of number of DFT cycles.
perpendicular to the freezing direction (Scheme 1). A significant
difference can be found in the peeling curves and the specimens
after the tests (Fig. 6a). When the specimen cut from the
perpendicular direction was peeled, the notch on the specimen
could propagate to the end, and a typical peeling curve is present.
However, when the specimen cut from the parallel direction was
peeled, the notch could not propagate, and the force increased
rapidly until fracture occurred in one arm of the specimen.
Fig. 6b shows the fracture energies (G) of the DFT-10 PVA
hydrogels. G generally increases with increasing number of DFT
cycles. G is in the range 160–420 J m
2, these values are
much bigger than those of conventional synthetic hydrogels
Fig. 6 Tearing test results of DFT-10 PVA hydrogels. (a) The load–
displacement curves of the specimens cut from the parallel and perpen-
dicular directions of the DFT-10-7 PVA hydrogel; the inset photos show
the specimens after tearing tests; (b) the fracture energies of the gels with
different numbers of DFT cycles in the parallel and perpendicular
directions.
This journal is ª The Royal Society of Chemistry 2012
(100 J m
2), and similar to or less than those of DN gels (102
to 103 J m
2).42
The tearing test results also indicate that the DFT PVA gels
have anisotropic mechanical properties. For a given hydrogel
sample, the fracture energy of the specimen cut from the parallel
direction is higher than that from the perpendicular direction.
Seemingly, it is different to the cases of sb and E, which are
higher in the perpendicular direction than those in the parallel
direction. However, they are in fact consistent with each other,
since when the specimen cut from the parallel direction is peeled,
the force is applied to the direction perpendicular to the freezing
direction, and vice versa. Therefore, the DFT PVA gels also have
a higher G in the perpendicular direction.
Cyclic tensile loading–unloading behavior
Cyclic tensile tests to the same maximum strain (3max) for 10
cycles were carried out on the hydrogels in different directions.
During each cyclic tensile test, the loading and unloading cycles
were performed in immediate succession with the same specimen.
The typical loading–unloading curves for the DFT-10-7 PVA
hydrogel to a 3max of 100% for different runs are shown in
Fig. 7a. A hysteresis loop is always present in the loading–
unloading curves of the cyclic tensile tests of the DFT-10-7 PVA
hydrogel (Fig. 7a) and other DFT samples. When the gels were
stretched to the same 3max for several cycles, a significant
hysteresis could be found in the first loading–unloading cycle,
and the hysteresis became much less significant in the following
ones. A hysteresis ratio, hr, which can be defined by evaluating
the ratio of the area of the hysteresis loop to the integrated area
of the loading curve,35 was used to determine the hysteresis
quantitatively. The calculated hr of the DFT-10-3 and DFT-10-7
PVA samples stretched to 100% strain for 10 cycles is shown in
Fig. 7b. A significant decrease in hr is observed after the first run
cycle, and hr decreases slowly with increasing run cycle. It can
also be found that hr increases with increasing number of DFT
cycles. Anisotropic hr can also be found in the DFT gels, i.e. the
hr in the perpendicular direction is always higher than that in the
parallel direction.
It can also be found from Fig. 7a that there is a decrease in the
st of the DFT-10-7 gel with the increase in run cycles. The st
values at 100% strain after different run cycles for the gels from
different directions are shown in Fig. 7c. For the gel made by 3
DFT cycles, the decrease in st is very little, but the decrease in st
becomes more significant for the gel fabricated with more DFT
cycles. However, the difference between the two directions
cannot be distinguished by this method. Therefore, we calculated
the relative ratio of st of each run cycle (st,n) to the first cycle
(st,1) at 100% strain [100  (st,n/st,1) (%)] (Fig. 7d). Only a very
slight decrease can be observed in the DFT-10-3 gel sample in the
second run cycle, and there is no obvious difference between the
two directions. However, with the increase in number of DFT
cycles, the decrease becomes more significant and gradually
increases with the run cycles. Anisotropy can also be found in the
DFT gels; the decrease in the perpendicular direction is always
higher than that in the parallel direction.
Two types of cyclic tensile tests of the gels to different 3max
were also carried out. For the first type, the tests with different
3max were carried out with different specimens, i.e., each loading
Soft Matter, 2012, 8, 10439–10447 | 10443
Fig. 7 Cyclic tensile tests of the DFT-10 PVA hydrogels to 100% strain for 10 cycles. (a) The typical loading–unloading curves for the DFT-10-7 PVA
hydrogel to the strain of 100% for 1, 2 and 10 runs in the perpendicular direction; (b) the hysteresis ratio (hr) with the run cycles; (c) the change in tensile
strength (st) at 100% strain, and (d) the relative ratio of st of each run cycle to the first cycle at 100% strain [100  (st,n/st,1) (%)].
and unloading cycle was performed with an original specimen.
For the second type, however, the loading and unloading cycles
were performed in immediate succession with the same specimen
at increasing levels of 3max. The typical loading–unloading curves
of the two types of tests are shown in Fig. 8a and c, and the hr
values of the loading and unloading cycles are shown in Fig. 8b
and d, respectively. In both cases, the hr of the gels increases with
increasing 3max. In addition, for the same sample and at the same
strain, the hr in the perpendicular direction is always higher than
that in the parallel direction.
Discussion
The above results show that PVA hydrogels with anisotropic
microstructure and mechanical properties can be obtained with
the directional freezing and thawing (DFT) method.
The aligned porous structure of the DFT PVA gels is formed
during the directional freezing process, in which the solvent,
water, is frozen into ice from the bottom of the vessel and the ice
grows along the freezing direction, and the growing ice crystals
exclude the PVA molecules from the freezing front. The phase
separation results in PVA-rich and PVA-poor regions. The
excluded PVA molecules aggregate to form the aligned pore
walls. Due to the ease of forming strong hydrogen bonding
among PVA molecules and the formation of crystalline regions
in the polymer-rich regions, stable hydrogels that are physically
crosslinked can be obtained.43 In freeze–thawed gels, crystallite
formation occurs due to the folding of PVA chains.44 During the
following thawing at ambient temperature, part of the PVA
molecules can be dissolved and some crystallites can be melted
10444 | Soft Matter, 2012, 8, 10439–10447
out,44 forming some weak regions. In the following freezing
process, larger ice crystals can be formed along the freezing
direction due to the presence of previously formed channels, in
which there is a much lower concentration of PVA molecules and
hence a lower resistance for ice crystal growth, and the weak
regions in the former hydrogel can be broken by the ice crystals,
leading to an increase in the size of the pores with increasing
number of DFT cycles. With increasing number of DFT cycles,
more and more PVA chains are excluded from the PVA solution
to form stronger interactions among PVA molecules and hence
more crystalline regions, leading to the increase in cc in the
hydrogel. Of course, when a balance between the binding and the
dissolution of the PVA chains has been built up, further DFT
cycles do not lead to an increase in cc.
Due to the presence of the anisotropic microstructure, the
DFT PVA hydrogels should exhibit anisotropic mechanical
properties. In addition, the difference in cc should also affect the
mechanical properties of the gels, since crystallites act as knots
interconnected by portions of PVA chains swollen by the
solvent.43
The PVA hydrogels contain both crystalline and amorphous
regions, i.e. hard and soft regions. There is an interesting parallel
with thermoplastic polyurethanes, which are copolymers
composed of hard and soft segments, in which the hard and soft
segments phase separate to form a microstructure of hard and
soft domains, and the hard domains are thought to govern the
hysteresis, permanent deformation, high modulus, and tensile
strength.45
With the increase in DFT cycles, more crystalline regions and
stronger interactions, i.e. physical entanglement and hydrogen
This journal is ª The Royal Society of Chemistry 2012
Fig. 8 Cyclic tensile testing of the DFT-10 PVA hydrogel to different strains. (a) The typical tensile loading–unloading curves for the DFT-10-5 (t)
PVA hydrogel to different strains; (b) the hysteresis ratios (hr) of the gels; each loading and unloading cycle was performed with an original specimen; (c)
the typical successive loading–unloading curves for the DFT-10-7 (k) PVA hydrogel to different strains; and (d) the corresponding hysteresis ratios (hr);
the loading and unloading cycles were performed in immediate succession with the same specimen.

bonding formed among PVA chains, lead to an increase in E and
sb of the gels. When a DFT PVA gel is stretched to a low strain,
the applied force is possibly mainly sustained by the soft regions
through the movement of the flexible polymer chains, leading to
the slow increase of stress with strain and hence a low E1. With
the increase in applied strain, after reaching the full length of the
flexible polymer chains, the applied force should be sustained
mainly by the crystalline regions, leading to higher E2. The
almost linear increase of stress with strain in the high strain range
(>100%) is very possibly due to the gradual damage (unfolding)
of the crystalline regions.
The mechanical properties of an oriented, anisotropic sample
are different in different directions.46 Generally, an oriented
crystalline polymeric material has a higher E and sb but a lower
3b when it is stretched in the oriented direction, due to breaking
of the strong covalent bonds of the polymer chains; but when it is
stretched in a transverse direction where only weak intermolec-
ular interactions need to be broken, its behavior is similar to that
of an unoriented material. Therefore, the oriented material
usually shows a lower E and sb but a higher 3b in the transverse
direction.
As proven by the SEM investigations (Fig. 1), DFT induces an
oriented distribution of polymer along the freezing direction.
However, the DFT PVA hydrogels do not exhibit higher
mechanical strength in the direction parallel to the oriented
direction; on the contrary the hydrogels exhibit higher E and sb
but lower 3b in the direction perpendicular to the freezing
direction. We think that there is another kind of orientation
present in the hydrogels, i.e. orientation of the crystalline regions,
which plays an important role in the anisotropic mechanical
properties of the DFT PVA hydrogels. During the DFT process,
in a given region the formation and growth of ice crystals occurs
in advance of the formation of crystalline PVA regions, since the
latter occurs only after the PVA molecules have been excluded
from the solution by the growing ice crystals, and the crystalli-
zation of PVA molecules is a slower process due to the low
mobility of the macromolecular chains. In addition, due to the
much higher thermal conductivity of ice (2.18 W m
1 K
1, 0  C)
than PVA (0.2 W m
1 K
1), a temperature gradient that is
perpendicular to the freezing direction is present between the ice
crystals and the vicinal PVA-rich regions, leading to the folding
and crystallization of PVA chains along this temperature
gradient (Scheme 2).
The directional freezing process leads to the directional
arrangement of crystalline regions along the direction perpen-
dicular to the freezing direction. Therefore, similarly to oriented
crystalline polymeric materials, the DFT PVA gels have higher E
and sb when they are stretched in the oriented direction, since the
crystalline region is tougher than the amorphous region and its
breakage requires a higher force. However, differently to the
oriented crystalline polymers, the DFT PVA gels also have a
higher 3b in the perpendicular direction. Possibly, the easier
occurrence of deformation of the evenly distributed pores with a
similar size in the perpendicular direction and the unfolding of
the crystalline regions under applied stress provide the gels with a
higher 3b.
The viscoelasticity and resilience of the DFT PVA hydrogels
can be understood through the cyclic tensile testing. The PVA
hydrogels demonstrate stress softening (Mullins effect)47 during
the cyclic tensile tests, namely after being uniaxially stretched to a

This journal is ª The Royal Society of Chemistry 2012 Soft Matter, 2012, 8, 10439–10447 | 10445

Scheme 2 Schematic presentation of the formation of directionally
arranged crystalline regions in DFT PVA hydrogels. The small arrow
indicates the freezing direction (i.e. direction of ice crystal growth).
certain strain, the sample requires a smaller stress to maintain the
same strain in the unloading process. In the cyclic tests to the
same maximum strain, the Mullins effect is much more obvious
in the first loading–unloading cycle (Fig. 7a) than in the
following ones. In addition, the Mullins effect is more
pronounced with increasing maximum strain (Fig. 8a).
Mullins softening has been observed in filled rubbers, pure
crystallizing gums (e.g. NBR) and DN hydrogel. There is no
general agreement on the physical source of this effect. Several
theories have been proposed for filled rubbers, including bond
ruptures, molecule slipping, filler-cluster rupture, chain disen-
tanglement, chain retraction, network rearrangement, and
composite microstructure formation.47 For pure crystallizing
gums, the presence of crystallites seems necessary for the
occurrence of Mullins softening. Creton et al. attributed the
Mullins softening of DN hydrogels to the fracture of covalent
bonds in the first highly crosslinked network.48
The physical source of Mullins softening in our DFT PVA
hydrogels must be different from that for DN hydrogels, since
the PVA gels are physically crosslinked and hence mainly phys-
ical crosslinking is broken in the loading process. As discussed
above, the presence of crystalline regions and strong physical
interactions among PVA chains is the main reason for the high
mechanical strengths of the PVA gels. The occurrence of Mullins
softening in the DFT PVA hydrogels might be attributed to the
breakage of the crystalline regions and the physical interactions.
The decrease in the st of the DFT PVA gels with the increasing
number of loading–unloading cycles suggests the presence of
permanent damage to the structure of the gels. When a specimen
is cyclically stretched to the same strain for several cycles, an
obvious Mullins softening and hysteresis can only be found in the
first loading–unloading cycle, and in the following cycles the
Mullins softening and hysteresis become less significant, sug-
gesting that the breakage of the crystalline regions and the
physical interactions occurred mainly in the first cycle. When a
specimen is cyclically stretched to a higher maximum strain,
Mullins softening and hysteresis become more pronounced
(Fig. 8), suggesting more breakage of the crystalline regions and
the physical interactions.
It is also observed that the Mullins softening, hysteresis and
decrease in st become more significant with the increase in
number of DFT cycles. XRD analysis results show that the cc of
the dried DFT PVA films increases with increasing number of
10446 | Soft Matter, 2012, 8, 10439–10447
DFT cycles. We think that there is a correlation between the
Mullins softening and the cc of the gels, and possibly the damage
of the crystalline regions is the main reason for the Mullins
softening. The fact that the loading curve of the next cycle does
not overlap but deviates positively with the unloading curve of
the previous cycle (Fig. 7a and 8c) suggests that part of the
damage can be recovered during the unloading process and
possibly some of the crystalline regions damaged in the loading
process can recrystallize.
The gels show more significant Mullins softening and hyster-
esis, as well as higher hr and a greater decrease in st in the
direction perpendicular to the freezing direction. These aniso-
tropic behaviors are also caused by the oriented arrangement of
the crystalline regions along the direction perpendicular to the
freezing direction, and the oriented crystalline regions are easier
to unfold under an applied load in the oriented direction rather
than in the transverse direction.
It is necessary to mention that parts of the crystalline regions
are very possibly not oriented. One reason is the complexity of
the DFT process, which cannot precisely control the crystallizing
direction of the PVA chains. The other reason is that the previ-
ously formed oriented crystalline regions may impede the further
formation of oriented crystalline regions, leading to the forma-
tion of unoriented crystalline regions. The latter may become
more pronounced with the increase in number of DFT cycles.
Conclusions
This study demonstrates that PVA hydrogels with anisotropic
microstructure mechanical properties can be fabricated using the
DFT method. The DFT PVA hydrogels have excellent
mechanical properties, and more importantly they exhibit
significant anisotropy in their mechanical properties. The gels
usually exhibit higher tensile strength, modulus and fracture
energy, but lower fracture strain in the perpendicular direction
than those in the parallel direction. Anisotropic mechanical
behaviors can also be found in the cyclic tensile tests of the PVA
hydrogels. The origin of the mechanical properties of the DFT
PVA hydrogels has been discussed from the anisotropic micro-
structure formed during the directional freezing process, and the
anisotropic mechanical properties of the DFT PVA hydrogels
might be attributed to the oriented arrangement of crystalline
regions along the direction perpendicular to the freezing direc-
tion, which need to be proved in future study.
The microstructure and the mechanical properties of the gels
can be adjusted by controlling the DFT conditions, polymer
content, etc. Therefore various hydrogels with required proper-
ties can be obtained. The anisotropic DFT PVA hydrogels may
find more practical applications than those hydrogels prepared
by the normal FT method. The hydrogel materials with aligned
porosity in the micrometer range may be used as a scaffold for
tissue engineering and biomimetic bone scaffold materials.
Acknowledgements
We thank the financial support from the National Science
Foundation of China (no. 21074014), the Fundamental Research
Funds for the Central Universities and Beijing Municipal
Commission of Education.
This journal is ª The Royal Society of Chemistry 2012
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