Facile fabrication of poly(vinyl alcohol) gels and derivative aerogels

Hong-Bing Chen
a, b
, Erin Hollinger
b
, Yu-Zhong Wang
a,
*
, David A. Schiraldi
b,
*
a
Center for Degradable and Flame-Retardant Polymeric Materials, College of Chemistry, State Key Laboratory of Polymeric Materials Engineering,
Sichuan University, Chengdu 610064, China
b
Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH 44106-7202, USA
a r t i c l e i n f o
Article history:
Received 24 March 2013
Received in revised form
28 July 2013
Accepted 30 July 2013
Available online 6 August 2013
Keywords:
Poly(vinyl alcohol)
Hydrogel
Aerogel
a b s t r a c t
A facile preparation of poly(vinyl alcohol) (PVOH) hydrogels and their derivative PVOH/montmorillonite
clay aerogels is reported, using water as solvent and divinylsulfone as crosslinking agent, making use of
an environmentally friendly freeze drying process. The materials exhibit signicantly increased me-
chanical properties after crosslinking. The compressive modulus of an aerogel prepared from an aqueous
suspension containing 2 wt% PVOH/8 wt% clay increased 29-fold upon crosslinking, for example.
Crosslinking of the polymer/clay aerogels decreased the onset decomposition temperature as measured
by thermogravimetric analysis, and generated a more continuous structure at higher clay contents. Such
polymer/clay aerogels are promising materials for low ammability applications.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Poly(vinyl alcohol) (PVOH) is a highly hydrophilic and water-
soluble polymer, synthesized by partial or complete hydrolysis of
poly(vinyl acetate) (PVAc) [1]. The low toxicity, high water content,
good mechanical properties and biocompatibility of PVOH hydro-
gels make result in their wide use in drug delivery [2], contact
lenses [3], wound bandages and dressings [4] tissue engineering
[5], and cell immobilization [6]. PVOH hydrogels can be fabricated
via different techniques, such as the freeze-thaw inducement of
crystallization [7e14], acid-catalyzed dehydration [15], irradiation
[4,5], radical production [16,17] and chemical crosslinking (diacid,
aldehyde and alkoxysilanes) [18e22]; these methods require long
treatment times, or harsh reaction conditions, limiting their utility.
Mackenzie [23] and Call [24] rst reported montmorillonite clay
aerogels prepared using a freeze-drying method. The resultant
brous montmorillonite structures possessed some rigidity, but
poor thermal stability; other non-swelling clays, such as kaolin,
only form ne powders under these processing conditions. Van
Olphen proposed that the walls within clay aerogels are linked
edge-to-face much like a house of cards owing to opposite surface
and edge charges that exist in clays [25]. The interpretation of the
structural data is that during freezing, ice crystals grow radially,
pushing clay particles aside to promote parallel platelet alignment.
Nakazawa et al. investigated the effects of process parameters, such
as clay concentration and freezing rates, which showthat decreases
in clay concentration and freezing rates result in morphological
shape changes from polygonal cells to thin lenses [26,27]. The au-
thors proposed that pores remaining in the freeze-dried aerogel
structure are negatives of the ice crystals once formed and later
sublimed. Alhassan et al. [28] prepared polymer/clay aerogel with
the addition of PVOH; mechanical properties of these aerogels
show power law dependence on aerogel density, which depends
mainly on polymer loading. The resulting mechanically robust
aerogel composites have the potential to be of value in applications
including packaging, insulation and absorbent products [29].
Crosslinking methods are commonly used to further increase
mechanical properties of clay aerogel. Pojanavaraphan et al. [30]
prepared crosslinked casein/clay aerogels using DL-glyceraldehyde
as the chemical crosslinking agent, resulting in greatly enhanced
structural integrity and compressive moduli of the modied aero-
gels. Crosslinked natural rubber clay aerogel composites have also
been reported [31], making use of solution crosslinking of the
freeze-dried aerogel samples using sulfur monochloride as the
chemical agent. The compressive moduli of resultant aerogels were
again signicantly increased compared with the uncrosslinked
controls.
In the present work we describe a facile production of PVOH
hydrogels with divinylsulfone as crosslinker, followed by addition
of clay, then conversion of these materials into PVOH/clay aerogels,
via a freeze-drying method. The crosslinking not only increases the
* Corresponding authors.
E-mail addresses: yzwang@scu.edu.cn (Y.-Z. Wang), das44@case.edu, das44@
cwru.edu (D.A. Schiraldi).
Contents lists available at ScienceDirect
Polymer
j ournal homepage: www. el sevi er. com/ l ocat e/ pol ymer
0032-3861/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymer.2013.07.078
Polymer 55 (2014) 380e384
modulus and the strength of these lightweight, foam-like materials,
but because of their increased strength, the PVOH content in the
aerogels can be decreased, leading to less fuel content and reduced
ammability compared to the starting aerogel.
2. Experimental
2.1. Materials
Poly(vinyl alcohol) (PVOH, Mw 31,000e50,000, 99% hydrolyzed,
SigmaeAldrich), divinylsulfone (DVS) and sodium hydroxide
(NaOH) (Fisher Scientic), and montmorillonite (PGWgrade with a
cation exchange capacity of 145 mequiv/100 g, Nanocor Inc.) were
all used as received. Deionized (DI) water was prepared using
Barnstead RoPure low-pressure, reverse osmosis system.
2.2. Hydrogel and aerogel preparation
The PVOH suspensions were prepared by stirring PVOH solid in
DI water at 70

C overnight until completely dissolved. To prepare
the crosslinked samples, varying amounts of DVS and 1 M aq NaOH
were stirred into the polymer suspension at room temperature
until homogeneously dispersed; the mixtures were then poured
into polystyrene vials to create gelled cylindrical samples (no NaOH
was added in the uncrosslinked control samples). To prepare
the clay-containing samples, a 10 wt% clay suspension in water
was produced by blending clay and DI water at high speed
(22,000 rpm), and the resulting suspension was then mixed at
room temperature with the desired PVOH solution with magnetic
stirring overnight to produce a homogeneous suspension. The DVS
and NaOH solutions were added to the polymer/clay suspensions,
then the mixtures were poured into polystyrene vials to create
cylindrical gelled samples.
The aqueous samples were immediately frozen in a solid carbon
dioxide/ethanol bath (w80

C), then freeze-dried using a VirTis
Advantage EL-85 lyophilizer with a shelf temperature of 25

C and
ultimate pressure of 10 m bar. The resulting aerogel samples are
identied as P
x
C
y
, where P
x
and C
y
correspond to x and y wt% PVOH
and clay in the preparation suspensions, respectively.
2.3. Characterization
Densities of the aerogel samples were calculated by measuring
the mass and dimensions using a Mettler Toledo AB204-S analytical
balance and a digital caliper.
Compression testing of PVOH hydrogels and the derivative
aerogels were conducted on the cylindrical specimens (w20 mm in
diameter and height) using an Instron model 5565 universal testing
machine, tted with a 5 kN load cell, at a crosshead speed of
10 mm min
1
. Five samples for each composition were tested for
reproducibility, compressing from the direction of the open end of
the cylindrical vials used as molds in every case. The initial
compressive moduli and toughness were calculated from the slope
of and area under the linear portion of the stressestrain curves.
Samples for scanning electron microscopy (SEM) were freeze
fractured in liquid nitrogen rst, then sputter-coated with a thin
layer of palladium before being tested. The imaging was carried out
with HITACHI S-4500 scanning electron microscope at acceleration
voltage of 5 kV.
The thermal stabilities (by thermogravimetric analysis, TGA)
were measured on a TGA Q500 (TA Instruments) under a nitrogen
ow (40 mL min
1
). About 5 mg of samples were placed in a
platinum pan and heated from ambient temperature to 600

C at a
rate of 10

C min
1
. T
d10%
and T
dmax
, the temperatures at which 10%
mass loss, and at which maximum weight loss occur, respectively,
are reported, along with the residual mass after the TGA experi-
ment is concluded. The mass loss plots and the differential gravi-
metric analysis (DTG rate of weight loss) are reported herein.
3. Results and discussion
3.1. Hydrogel
The chemical reaction of PVOHand DVS is illustrated in Scheme 1.
Different combinations of PVOH suspension concentration, DVS
content and NaOH content were investigated in order to optimize
the crosslinking reaction. The concentrations of PVOH hydroxyl
groups and carbonecarbon double bonds from DVS were calculated
by dividing the mass of PVOH by 44 (assumes fully hydrolyzed
material) and by dividing the mass of DVS by (2/118) respectively;
the PVOH, DVS and NaOH ratios used in this study are listed in
Table 1:
The crosslinking reaction is very sensitive to the base concen-
tration, as can be seen in the data presented in Table 1. At least
2.0 10
2
mol/l NaOH is required for initiation of the crosslinking
reaction, but 2.4 10
2
mol/l leads to substantially faster cross-
linking. For suspensions containing 10 wt% PVOH, the gel can form
over a DVS content range from 0.04 to 0.25 equivalents based on
polymer hydroxyl group content, indicating that 0.04 DVS provides
a sufcient level of crosslinking. When a PVOH concentration of
5 wt% was used, useful gels could again be produced in the pres-
ence of 2.4 10
2
mol/l NaOH and 0.12 equivalents of DVS. Further
decreasing the PVOHsuspension concentration to 2.5 wt%, only soft
gels, lacking the ability to retain their shape as monoliths, could be
produced, even with 0.25 equivalents of DVS crosslinker, indicating
that a minimum quantity of PVOH is necessary to form network
structure, consistent with our earlier ndings [32].
Based on the above results, PVOH hydrogels were produced
from 10% polymer suspensions, and their compressive moduli
tested. The results (Table 2) show that the gels were mechanically
robust, collapsing but not fully fracturing at ultimate strain. Among
the three compositions evaluated, PVOH crosslinked with 0.12
equivalents of DVS proved to be the strongest, with a stress at break
of 67 kPa. It is not clear why the higher, 0.25 equivalent DVS
hydrogels reproducibly (n 3) exhibited lower modulus and
strength than that obtained with 0.12 equivalent of crosslinking
agent. Figs. 1 and 2 show that the transparent PVOH gels are ex-
ible, which can even be compressed to 25% of their original height.
3.2. Aerogel
3.2.1. Mechanical properties
The neat PVOH hydrogels produced from 10% polymer suspen-
sions were freeze-dried to produce aerogels. In the absence of
added clay, and with low levels of crosslinking, the PVOH polymer
aerogels exhibited poor mechanical properties and were difcult to
handle. Such instability in uncrosslinked aerogels is known in silica
aerogels as well. With increasing DVS levels in the PVOH aerogels,
crack-free aerogels were obtained; these materials did exhibit
noticeable shrinkage during the drying step, probably due to the
strong interactions between the molecular chains, and concomitant
increases in density from theoretical value of 0.10 g/cm
3
to around
0.16 g/cm
3
.
Scheme 1. Chemical reaction of PVOH and DVS.
H.-B. Chen et al. / Polymer 55 (2014) 380e384 381
Crosslinked PVOH/clay aerogels were prepared. The total weight
of PVOH and clay were maintained at 10 wt% of solution, the
amount of DVS was xed at 0.12 equivalents based on free OH
groups from PVOH. The mechanical property and density data are
listed in Table 3, and show that for the uncrosslinked samples,
modulus and strength are comparable in the range of 10:0 and 4:6
polymer:clay, but as the polymer concentration is further reduced,
these properties are diminished e these results are consistent with
previous reports for such systems [33]; the mechanical properties
of such cellular materials are generally determined by their den-
sities [27], but when the amount of lm-forming polymer drops
below a critical value, insufcient polymer coverage exists, and
catastrophic loss of properties result. The compressive moduli of all
the samples increased (2e30) after crosslinking, providing ma-
terials with disproportional increases in modulus compared to
density e hence the specic moduli of the crosslinked materials
exceeded those of the starting aerogels, consistent with higher
modulus composites rather than simply denser composites. It
should be noted that the compressive moduli and specic moduli
obtained with these composite aerogels are similar to the values of
1e40 MPa and 8e240 PMa-cm
3
/g reported for commercially
available rigid polyurethane foams [34].
3.2.2. Morphology
The dimensional stability of aerogels increased with increasing
the clay content, while their densities decreased from 0.16 g/cm
3
to
around 0.10 g/cm
3
. The SEM images of P8C2 and P2C8, with and
without crosslinking are given in Fig. 3. Both of the two unmodied
PVOH/clay aerogels adopted architecture that followed the direc-
tion of ice crystal growth, similar to previous reports [32,33,35,36].
With decreasing polymer content, the distance between aerogel
layers becomes much larger, reecting less matter per unit volume
in the starting aqueous gels. It has been proposed that the structure
of the aerogels is determined by solution viscosity [36], with higher
solution viscosities generally producing more compact structures.
Crosslinking will of course increase solution viscosity, and it is
known that with cation-driven crosslinking of alginate aerogels,
the aerogel structures move to increasingly ner grain network
structures, away from coarse, lamellar morphologies [36]. The
current results appear to be at odds with this explanation. Cross-
linked P8C2 exhibits a layered structure with layer distances up to
hundreds of microns; upon further magnication of structural
layers, a ne network structure with pores on the micron scale are
apparent. It is plausible that ice crystals grow within pores of
crosslinked hydrogels without much resistance. Such loose struc-
tures would shrink when freeze-dried, deteriorating the mechan-
ical properties and increasing the bulk densities. Cation-driven
crosslinking, which allows for repeated formation and breaking of
links, is different fromchemical crosslinking, whose linkages are far
more persistent. The small pores in the P8C2 layers are probably
attributed to the crosslinking of PVOH. With increasing clay con-
tent, the crosslinked samples possess integrated network struc-
tures, with pore size on the order of a micron or less (Fig. 3, D2). The
incorporation of clay contributes extra resistance to ice crystals,
resulting aerogels with compact morphological structures. An
overall point to note is that hydrogel and aerogels structures are
very sensitive to both compositional and processing conditions e a
recent report shows, for example, that merely changing the
freezing rate of polymer/clay solutions results in signicantly
different morphologies and compressive properties [37].
3.2.3. Thermal stability
The thermal stabilities of PVOHaerogels and PVOH/clay aerogels
with and without crosslinking were investigated by TGA. The cor-
responding curves are given in Fig. 4, and the data are summarized
in Table 4. PVOH easily absorbs water due to the existence of
Table 2
Compressive moduli of aerogels produced from crosslinked 10% PVOH suspensions.
Molar ratio
(OH/DVS)
Hydrogel Aerogel
Modulus
(MPa)
Fracture
or not?
Modulus
(MPa)
Density
(g/cm
3
)
Specic
modulus
(Mpa * cm
3
/g)
12 0.056 0.003 Partly 7.9 1.0 0.160 0.007 49.3 7.4
5 0.039 0.002 Partly 11.3 2.3 0.166 0.002 67.7 13.4
Fig. 1. Stressestrain curves of PVOH hydrogels (10 wt%) with different DVS levels.
Fig. 2. Flexible gels from PVOH/DVS.
Table 1
PVOH crosslinked with different ratios of DVS and NaOH (tested 4 h after prepared).
PVOH concentration (wt%) DVS (% equiv)
a
NaOH (mol/L) Gel state
10 12 8 10
3
No
10 12 1.2 10
2
No
10 12 1.6 10
2
No
10 12 2.0 10
2
Soft
10 4 2.4 10
2
Yes
10 6 2.4 10
2
Yes
10 8 2.4 10
2
Yes
10 10 2.4 10
2
Yes
10 12 2.4 10
2
Yes
10 25 2.4 10
2
Yes
5 12 2.4 10
2
Yes
2.5 12 2.4 10
2
Soft
2.5 25 2.4 10
2
Soft
a
Mole ratio of DVS double bonds to PVOH hydroxyl groups.
H.-B. Chen et al. / Polymer 55 (2014) 380e384 382
hydroxyl groups in its molecules, a common phenomenon in hy-
drophilic materials. The rst weight loss stage is caused by
desorption of water between 70 and 120

C. There are two
decomposition stages of PVOH, occurring at 220e320

C and 420e
520

C; the onset decomposition was evaluated by T
d10%
. With
incorporation of 20% clay, the shape of TG curve is almost un-
changed, with only a slight increase in the char residue. The
crosslinking of polymeric materials usually contributes to their
thermal stability [36,38,39]. However, the onset decomposition
temperatures of the crosslinked polymer/clay aerogels decreased
unexpectedly, which may be attributed to the pyrolysis of
incorporated crosslinker, or possibly to the effect of added sodium
hydroxide; this point to be addressed in future work. It is inter-
esting to note that the clay-free aerogel exhibits a char yield of
approximately 10%; incorporation of clay to this might well be
expected to increase the char yield in a simple, additive manner.
The actual char yields of all of the polymer/clay aerogels examined
in this work are less than would be expected, suggesting loss of clay
itself. The most likely explanation of this phenomenon is that at
elevated temperatures, the clay structure breaks down, releasing
the substantial quantities of waters of hydration within the crystal
structure, resulting in the lower than expected char yields.
Table 3
Mechanical properties of PVOH/clay aerogels (moduli in MPa, densities in g/cm
3
, specic moduli (M/d) in MPa-cm
3
/g).
Sample P10 P8C2 P6C4 P4C6 P2C8
Control Modulus 3.8 0.6 5.1 1.7 4.1 0.8 4.2 0.7 0.26 0.06
Density 0.122 0.001 0.119 0.004 0.098 <0.001 0.089 <0.001 0.092 0.001
M/d 30.9 4.7 42.813.5 41.8 8.4 47.1 8.0 2.78 0.67
Crosslinked Modulus 11.3 2.3 14.0 1.6 22.9 3.7 8.4 1.3 7.6 0.9
Density 0.166 0.002 0.149 0.003 0.121 0.007 0.110 0.001 0.097 <0.001
M/d 67.7 13.4 93.911.6 188.9 29.3 76.1 12.5 77.2 9.4
Fig. 3. SEM micrographs of PVOH/clay aerogels: (A) P8C2; (B) P2C8; (C) crosslinked P8C2; (D) crosslinked P2C8; C1/C2 and D1/D2 denote different magnications of the same
samples.
H.-B. Chen et al. / Polymer 55 (2014) 380e384 383
4. Conclusions
The facile fabrication of PVOH hydrogels and derivative aerogels
was demonstrated, using water as solvent and DVS as crosslinker,
and through an environmentally friendly freeze drying process. The
crosslinking method was conrmed to improve the mechanical
properties of the aerogels. These materials exhibit mechanical
properties similar to those of rigid PU foams. With unchanged total
solid content, the materials densities and compressive moduli are
relatively insensitive to composition down to a critical level of
polymer, below which insufcient lm-forming material is present
and catastrophic loss in properties results. TGA testing surprisingly
shows that thermal stability of the aerogels decreases with cross-
linking, perhaps due to pyrolysis of the crosslinking agent itself.
Should ammability of the crosslinked samples follow the trends
for uncrosslinked polymer/clay aerogels, and low polymer/high
clay compositions, with their decreased fuel content, show mini-
mumammability, then the combination of relatively low polymer
contents, coupled with crosslinking, may represent an ideal
method for maximizing mechanical properties while minimizing
ammability, necessary for many structural and consumer uses of
foam-like products.
Acknowledgments
The authors of this paper would like to thank China Scholarship
Council for nancial support. Author Schiraldi, and Case Western
Reserve University have a nancial interest in a company which
could benet from commercialization of materials similar to those
described herein.
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Fig. 4. TGA weight loss and DTG curves of PVOH/clay aerogels.
Table 4
TGA data of freeze dried PVOH/clay aerogels.
Samples T
d10%
(

C) T
dmax
(

C) Residue (%)
P10 253.7 275.0 9.9
P8C2 249.6 273.7 13.8
P2C8 277.2 286.6 74.6
C-P8C2
a
195.2 276.4 28.2
C-P2C8
a
244.4 255.9 71.2
a
0.12 Euivalents of DVS based on PVOH hydroxyl groups.
H.-B. Chen et al. / Polymer 55 (2014) 380e384 384