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Swelling Resistance and Mechanical Performance of Physical Crosslink-

Based Poly(Vinyl Alcohol) Hydrogel Film with Various Molecular Weight

Wenzhong Ma ,1,2 Peng Zhang,1 Bao Zhao,3 Siyuan Wang,1 Jing Zhong,3 Zheng Cao,1
Chunlin Liu,1 Fanghong Gong,1 Hideto Matsuyama4
1
Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials, School of Materials Science and Engineering, Jiangsu
Collaborative Innovation Center of Photovolatic Science and Engineering, Changzhou University, Changzhou, Jiangsu, 213164,
People’s Republic of China
2
National Experimental Demonstration Center for Materials Science and Engineering (Changzhou University), Changzhou 213164,
People’s Republic of China
3
School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China
4
Research Center for Membrane and Film Technology, Department of Chemical Science and Engineering, Kobe University, 1-1
Rokkodai, Nada-ku, Kobe 657-8501, Japan
Correspondence to: W. Ma (E-mail: wenzhong-ma@cczu.edu.cn); J. Zhong (E-mail: zjwyz@cczu.edu.cn)

Received 30 August 2019; revised 25 October 2019; accepted 28 October 2019; published online 29 November 2019
DOI: 10.1002/polb.24902

ABSTRACT: The present work aimed to develop polyvinyl alcohol
(PVA) hydrogel films with physically crosslinking through con-
trollable entanglement density of the polymer chains. The visco-
elasticity of PVA aqueous solutions was investigated over a
broad range in molecular weight. The chain length between the
crosslinks in the hydrogel (M e ) and entanglement density was
determined by the plateau modulus (G’). The value of (M e )
increased with the PVA molecular weight, which can be attrib-
uted to the enhanced entanglement associated with the hydro-
gen bonds between inter- and interchains. The melting and
crystallization of the transparent PVA hydrogel films showed
that the crystallinity was below 30%, which indicated that
microcrystallites formed. Therefore, the entanglement effect and
microcrystallization enhanced the stable crosslinked hydrogel
network, which further improved by an increase in the molecu-
lar weight. Altogether, the PVA with the molecular weight higher
than 88,000 g/mol can be envisioned as a promising material for
preparing the hydrogel film possessing excellent performance.
© 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym.
Phys. 2019, 57, 1673–1683
KEYWORDS: entanglement; hydrogel film; physical crosslinking;
polyvinyl alcohol; rheological property

INTRODUCTION Polyvinyl alcohol (PVA) is a biodegradable and
environmentally friendly polymer material with good water sol-
ubility and membrane forming properties. Recently, PVA hydro-
gels with a three-dimensional network built by crosslinked
chain networks (physical or chemical one) have received much
attention on its excellent biocompatibility and feasibility in many
biomedical applications, such as agricultural application,1,2 bio-
medical applications,3–8 food packaging,9–11 separation and
purification,12–14 catalytic chemistry,15 electrochemistry,16
adsorption chemistry,17 and so on. These numerous applications
can be based on the specific hydrogen bonding between inter
and intramolecular hydrogen bonds in PVA chains, whose
strength has an influence of structure and mechanical properties
of PVA gel.18 Usually, chemical and physical types can crosslink
these hydrogen bonds. The swelling, osmotic natures, and
mechanical strength of a gel product triggered by environmental
changes are universal in gels, which determined by crosslinking
type and crosslinking degree. However, the PVA gels with limited
crosslinking between these weak hydrogen bonds would result
in reduced water resistance and low mechanical strength.19,20
Chemically crosslinked hydrogel in which covalent bonding
occurs between polymer chains can be created by adding
chemical crosslinking agents, such as boric acid, epichlorohy-
drin, and glutaraldehyde (GA).21 The gel network structure,
formed by the chemically crosslinking reaction can determine
the hydrogel properties, such as mechanical properties, water
absorbency, swelling, and crosslinking density. However, the
chemically crosslinked PVA hydrogel has some residual chem-
ical agent (e.g., GA), and its toxicity should be considered,
especially for the biomaterials applications. Ghorpade et al.
used a nontoxic citric acid (CA) as a crosslinking agent to

Additional Supporting Information may be found in the online version of this article.

© 2019 Wiley Periodicals, Inc.

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prepare a carboxymethyl cellulose (CMC)-polyvinyl alcohol
(PVA) hydrogel film with a network structure. The hydrogel
film had a mechanical strength of around 30 MPa and a swell-
ing degree higher than 50%.22 Another method of chemical
crosslinking without chemically reactive compounds can be
conducted by irradiation with a γ or electron beam. The
change of the radiation dose can control the crosslink density
of the hydrogel.23 Zhai et al. prepared a PVA/starch hydrogel
film using gamma rays and electron beam radiation.24 The
strength of the PVA hydrogel was significantly improved, but
the swelling property was slightly decreased due to poor
hydrophilicity of the starch. They found that a chemical reac-
tion between PVA and starch molecules or PVA molecules is
enhanced by amylose addition when exposed to radiation.
Singh and Pal prepared a sterculia polysaccharide/PVA/PVP
hydrogel film by radiation crosslinking.25 They showed that
the swelling medium affected the network structure of the
hydrogel. As the radiation dose increases, the swelling ability
of the hydrogel decreases. Although the hydrogel prepared by
radiation crosslinking has excellent performance, there are
still problems that refer to the limits of equipment require-
ments and high energy radiation consuming.
Physical crosslinking includes repeated freeze-melting and
freeze-part dehydration methods,26–28 which is currently the
most studied method. Peppas (1975) first attempted to prepare
physically crosslinked PVA hydrogels using the freeze-melting
method.29 A physically crosslinked PVA hydrogel is formed by
exposing the PVA aqueous solution to the repetitive freeze–
thaw cycles, and the repeated freeze–thaw cycles induce PVA
crystallization and form a three-dimensional network hydrogel
structure. In this physical hydrogel, the crystallites and hydro-
gen bonds make the gel networks. As reported, the crystallinity,
mechanical strength, and swelling degree of PVA hydrogel were
determined by the number of freeze–thaw cycles. The highest
crystallinity, Young’s modulus, and swelling degree were 36%,
1.46 GPa, and 470%, respectively.30 In recent decades, the
physically crosslinked gels have attracted more attention, to
avoid using chemical crosslinking agents and reagents.31,32
Although aqueous PVA solutions can form a hydrogel by
quenching method, this method cannot meet with any applica-
tion requirements because of low mechanical properties.
Otsuka and Suzuki developed a simple way to obtain a physi-
cally crosslinked PVA gel (named as PVA cast gel) at room
temperature without using any particular chemical.33 They
conclude that the physically crosslinked polymer network was
due to the formation of hydrogen bonds and microcrystals
during the dehydration process. The gelation induced by
hydrogen bonds and microcrystals, which is affected by the
gel structure, decides the properties of the hydrogel film.
Therefore, to comprehend the formation mechanism gelation
of PVA in the aqueous solution during the drying process, it is
necessary to study the relationship between the properties of
the hydrogel solution and the hydrogel film.
The present work deals with the preparation of physically
crosslinked PVA hydrogel films using the high alcoholysis
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degree type with different PVA molecular weights. Our objec-
tive was to develop hydrogel films with excellent stability in
water and mechanical strength so that they can be applied in
the planting field. As the crosslinks consist of the hydrogen
bonds and microcrystalline, so they can be used for planting
materials. Along with an improvement in the extent of
crosslinking, the large molecular weight with a large number
of OH groups in PVA chains also contributes toward the
chain enhancement. Taking these aspects into account, we
hypothesize that the crosslinked PVA hydrogel films may be
attributed to the crosslink density in the hydrogel solutions.
The PVA hydrogel solution is obtained by quenching the PVA
aqueous solutions to a decreased temperature. After drying
the hydrogel solution via evaporating, a physical crosslinked
PVA hydrogel film was formed. The gelation mechanism of the
PVA aqueous solution was investigated systematically based
on the rheological data and thermal analysis data. The effect
of molecular weight on the average molecular weight between
the effective crosslinks, entanglement density, critical concen-
tration for gel formation, crystallinity, mechanical properties,
swelling, and stability in water was also studied.
EXPERIMENTAL
Materials
The specifications of PAV materials provided by Sinopec Great
Wall Energy and Chemical Co., Ltd (China). The detailed infor-
mation is summarized in Table 1. Dimethyl sulfoxide (DMSO)
used was of an analytical grade that purchased from Shanghai
Lingfeng Chemical Reagent Co., Ltd. (China). Distilled water
was used in the preparation of the PVA solutions.
Preparation of PVA Solutions and Hydrogel Films
A series of aqueous PVA solutions were prepared by dispers-
ing PVA powders into distilled water under stirring mixing
conditions at 90
C for at least 3 h. When the homogeneous
solutions were obtained, stopped stirring and held for 24 h to
remove the air bubble in solutions. An appropriate amount of
PVA solution was spread over a glass plate, to a height of
250 μm using a casting knife (Elcometer Ltd., Manchester,
UK). After water evaporation at 40
C for ~12 h, PVA hydrogel
films were obtained. Two series of samples are designated as
TABLE 1 Specifications of PVA Materials
Degree of Degree of Molecular
Symbol alcoholysis polymerization weight (g/mol)a
PVA1399 99 1300 57,200
PVA1499 99 1400 61,600
PVA1799 99 1700 74,800
PVA2099 99 2000 88,000
PVA2499 99 2400 105,600
PVA2699 99 2600 114,400
a
Molecular weight of PVA is calculated from the value of the degree of
polymerization and the degree of alcoholysis provided by suppliers.

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S_X and F_X, where notations S and F serve to indicate that
the solution and film samples, respectively, and X means the
PVA molecular weight.
Apparent Viscosity Measurements for Aqueous PVA
Solutions
Viscosities of series of aqueous PVA solutions with different
concentrations were measured with a rotary viscometer
(model NDJ-79; Shanghai Pingxuan Scientific Instrument,
China) at 90
C. As the viscosity kept almost stable at the
shearing rate, the values of viscosities were recorded. Then,
the reduced viscosity can be obtained to determine the critical
concentration for gel formation.
Rheological Analysis for the Quenched Aqueous PVA
Solutions
0
The complex viscosity (η*) and the storage (G ) and loss (G00 )
moduli as functions of the frequency (ω) were determined by
the Physica MCR301 rheometer (Anton Paar, Germany). All
the measurements were performed with a constant strain
of 1.0%.
For the PVA gel solution, in the high-frequency region
(i.e., high shear rate), the PVA chains are not significantly
entangled, and the stress cannot relax in time. In this condi-
tion, we considered the physical entangled chain points like
the one kind of physical crosslinkage. Thus, in the rheological
behavior, the storage modulus (G’) of the high-frequency
region appears as a plateau region, which is due to the resid-
ual stress in the entangled chains. According to the rubber
elastic dynamics theory, the average molecular weight
between the effective crosslinks (entanglements) can be
expressed as34
ρRT
M
e = 0 ð1Þ
G
where ρ represents the density, T represents the absolute
temperature, and G’ represents the rubbery plateau modulus.
Then, the crosslinking density ρχ can be calculated by the
equation as follows35:
1
ρχ =
ð2Þ
ν
M e
where ν represents the specific volume of polyvinyl alcohol
(0.788 cm3/g).
Since the viscosity of an aqueous PVA solution would increase
gradually during storage, all viscosity measurements of these
PVA solutions were carried out 1 day after preparation of the
solution except where it is specifically stated otherwise in
the text.
Thermal Analysis for the PVA Hydrogel Films
The melt behaviors of PVA hydrogel films were determined
using a differential scanning calorimeter (DSC-214; Netzsch,
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Germany) at a heating rate of 10
C/min. Crystallinity was
estimated from the melting peak area, using 138.6 J/g (ΔH0m )
as the heat of fusion of the pure PVA crystal.36 When the melt-
ing enthalpy (ΔHm) of was obtained in the melting curve, ΔXc
can be measured by
ΔH m
ΔX c = × 100% ð3Þ
ΔH 0m
Gel Fraction of the PVA Hydrogel Films
As reported, the gel fraction can be measured gravimetri-
cally by37
Gel content ð%Þ = W e =W o × 100% ð4Þ
where Wo and We are the initial weight of the sample and dry
gel after extraction by DMSO, respectively.
Swelling Test for the PVA Hydrogel Films
The sample first dried at 50
C for 12 h and weighed as Wd.
Then, the dried sample was immersed in distilled water and
maintained at room temperature (25
C). After that, the swol-
len films were weighted at specific time intervals (15 min)
(before weighting, the surface was wiped by absorbent paper).
When achieving the equilibrium swelling (i.e., there is no
weight change after swelling), the final weight Wx was
obtained. So, the equilibrium degree of swelling of the PVA
hydrogel film was calculated as
Swelling ð%Þ = ½ðW x − W d Þ=W d  × 100% ð5Þ
The Stability of the Crosslinked PVA Hydrogel Films in
Water
Before testing, the sample first dried at 50
C for 12 h and
weighed as W0 and then immersed in distilled water at differ-
ent temperatures for different periods. Then, the film was
taken out and washed with water to remove the dissolved
PVA. The washed sample was dried in an oven at 50
C for
12 h and weighed as Ws. The weight loss of PVA hydrogel film
in water was calculated as:
Weight loss ð%Þ = ½ðW s −W 0 Þ=W 0  × 100% ð6Þ
Mechanical Properties of the PVA Hydrogel Films
The prepared PVA hydrogel films were cut into a specific
dumbbell shape (width 4 mm) and measured using the Elec-
tronic Universal Testing Machine (WDT30, Shenzhen KaiJiang
Machinery Co., Ltd, China) at a tensile speed of 20 mm/min.
RESULTS AND DISCUSSION
Rheological Behavior Analysis of PVA Aqueous Solution
To determine the effect of PVA molecular weight on the for-
mation of the PVA molecular chain crosslinked network, the
rheological behavior of the PVA aqueous solution was tested
at 10
C. The complex viscosities of PVA aqueous solutions
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(10 wt % and 15 wt % PVA concentration) with different (a)

molecular weights are shown in Figure 1. In this work, a very

Complex Viscosity η* (Pa·s )

15 wt%PVA aqueous solution S_1399
high degree of alcoholysis was used for aqueous solution S_1499
preparation, which made strong inter- and intrachain hydro- S_1799
gen bonding. When cooling to a lower temperature, this inter- 100 S_2099
and intrachain hydrogen bonding in this kind of PVA aqueous S_2499
S_2699
solution created a gel structure and made the viscosity
increased.38 For both two concentrations, the complex viscosi-
ties rise in low-frequency fast with the increasing molecular 10
weight, and decrease as the frequency increases, especially for
S_2499 and S_2699 solutions. Visible shear thinning behavior
is in the solutions prepared from the high-molecular weight, 1
which proves that the higher molecular weight makes the PVA
chains entangle more severe.39 Comparing the results in
1 10 100 1000
Figure 1(a) and Figure 1(b), the lower the concentration of
PVA, the more significant shear thinning behavior occurs. ω (rad/s)
Therefore, the enhanced chain entanglements were formed in (b)
the solution with higher PVA concentration, especially in the

Complex Viscosity η* (Pa·s)

15 wt % case.
Figure 2 shows the storage (elastic) modulus G’ and loss (vis-
coelastic) modulus G’’ of PVA solutions prepared from differ-
ent molecular weights. The single plot for the modulus curve
(G’, G’’ vs. ω) for 15 wt % and 10 wt % PVA concentration is
shown in the Supporting Information Figure 1 and S2, respec-
tively. G’ and G’’ of higher molecular weights have higher
values in the low frequency, which indicates that the solutions
behave like solids in the higher molecular weight case.40 So,
the solution state with higher molecular weight has more ten-
dency to form a gel structure by chain entanglement effect. As
for the solutions prepared with 10 wt % concentration, the
modulus curve of all the solutions only showed the viscous-
like behavior (G’ < G’’) within the accessible ω window, even
for the high-molecular weight case (S_2699). However, when
the PVA concentration reached to 15 wt %, the elastic-like
behavior (G’’ < G’) occurred and gradually moved to the lower
ω region. The crossover point (G’ = G’’) indicates the enhance-
ment of the elasticity and stiffness of the hydrogel formed by
the entanglement crosslinked network.41 Therefore, those
PVA aqueous solutions with 15 wt % concentration can get a
more crosslinked hydrogel network.
Analysis of the Entanglement Density of PVA Molecules in
Aqueous Solution
Based on the previous results of the rheology analysis, PVA
aqueous solutions with 15 wt % concentration have a gel net-
work caused by entanglement. The chain length between
entanglement crosslinks, Me , is calculated from the rubbery
plateau modulus through the theory of the rubber elasticity.42
Thus, the effect of molecular weight on the entanglement net-
work in the PVA hydrogel can be investigated quantitatively.
Crosslinking density refers to the number of crosslinks in the
crosslinked polymer. It usually is used to analyze the size of
the crosslinked grid and is a substantial physical quantity to
characterize the degree of crosslinking of the polymer. The
entanglement density of PVA can approximate the crosslink
density of PVA in the aqueous solution. Table 2 shows the
entanglement density of the aqueous solution of different
10 wt% PVA aqueous solution
S_1399
S_1499
S_1799
10 S_2099
S_2499
S_2699
1
1 10 100 1000
ω (rad/s)
FIGURE 1 Complex viscosity of PVA aqueous solution (10 wt %
and 15 wt %) with different molecular weights at 10
C. [Color
figure can be viewed at wileyonlinelibrary.com]
molecular weight PVA at 10
C, and the concentration of the
aqueous solution was 15%.
For all the PVA hydrogel solutions, the molecular weight is
always higher than the value of M e . As reported,42 the entan-
glement network in polystyrene solution gave rise to an
instantaneous network modulus, and Me is independent of
chain length as the molecular weight is higher than Me . How-
ever, in this work, the value of M e increases with the PVA
molecular weight, which can be attributed to the enhanced
entanglement associated with the hydrogen bonds between
inter- and interchains. Thus, the entanglement density also
increases with an increase in the molecular weight.
Measurement of Critical Gel Concentration of PVA
Aqueous Solution
To further determine the critical concentration of gel forma-
tion, the dependence of the viscosity of different molecular
weight PVA aqueous solutions on the solution concentration
was analyzed, and the viscosity of PVA aqueous solution with

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FIGURE 2 G’ and G’’ of PVA aqueous solution (10 wt % and 15 wt %) with different molecular weights at 10
C, as a function of
frequency. [Color figure can be viewed at wileyonlinelibrary.com]

different concentrations was measured. As shown in Figure 3, which solutions begin to form a coherent network, and gels
the viscosity dependence of the PVA aqueous solution in the could be built above c*.43
low concentration region is significantly lower than that in
the high concentration region. Below a specific concentration, The value of c* decreases with an increase in the molecular
the viscosity of the PVA aqueous solution increases gently weight. The c* for S_1399, S_1799, and S_2499 samples is
with increasing concentration, but above this concentration,
the viscosity of the PVA aqueous solution rises sharply. The
intersection of two lines (by linearly fitting method) in
Figure 3 could determine the critical concentration (c*) at

TABLE 2 Characteristics of PVA Hydrogel Solution Prepared

with Different Molecular Weight (PVA Concentration = 15 wt %)

Rubbery Chain length Entanglement

plateau between density
modulus crosslinks (ρχ × 103)
Symbol (G’) (Pa) (M
e ) (g/mol) (mol/cm3)

S_1399 269 8845 0.143

S_1499 1970 1318 0.962
S_1799 1800 1684 0.754
S_2099 3400 1023 1.240
S_2499 6110 682 1.862 FIGURE 3 Concentration dependence of reduced viscosity of
S_2699 4230 985 1.288 PVA aqueous solutions at 90
C. [Color figure can be viewed at
wileyonlinelibrary.com]

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10.2, 9.8, and 8.2 g/100 ml. The decreased c* indicates the gel
facilitated by an increase in the molecular weight. In this
work, the PVA solutions prepared with 10 wt % and 15 wt %
PVA is near or higher than the critical concentration, which
confirms the PVA gel crosslinked network formed in those
solutions, especially for the solutions with 15 wt % concentra-
tion. The critical concentration (c*) result agrees well with the
rheology data in Figure 2.
weight.44 As aforementioned, the entanglement density in the
PVA aqueous solutions increases with the PVA molecular
weight (Table 2), which indicates more crosslink degree in the
final hydrogel film. The decreased crystallinity of the PVA
hydrogel film can be attributed to the limited chain moving
ability by the crosslinked hydrogel network. The higher the
crosslinking density, the lower the probability of crystallite
formation.

As the PVA molecular weight is higher than 88,000 (F_2099,

Thermal Properties PVA Hydrogel Films
Figure 4 shows the cooling and second heating DSC curves of the
transparent PVA hydrogel films prepared with different molecu-
lar weights. Table 3 gathers the detailed data of DSC results
including the onset of melting temperature (T on m ), melting peak
temperature (T pm ), final melting temperature (T mf ), melting
enthalpy (ΔHm), degree of crystallization (Xc), crystallization
temperature (Tc), and crystallization enthalpy (ΔHc). When
the molecular weight is lower than 74,800 (F_1799), the melt-
ing temperatures (including T on p f
m , T m , and T m ) and crystallinity
decrease with the PVA molecular weight. This depression of
the melting temperature can be related to the increase of the
crosslinking degree in the hydrogel film with higher molecular
Endo Up
F_2499, and F_2699), the melting temperatures increase to
some extent, but the crystallinity kept at around 30%. For
these PVA hydrogel films with higher molecular weight, the
entanglement density is more than 1.24 (Table 2), the higher
amount of the hydrogel network crosslink sites makes the
self-nucleation effect more remarkable, although the chain
movement restricted in this condition. It has been reported
that self-nucleation behavior is closely related to melting
memory effects caused by entanglement density. The higher
the molecular weight of the polymer, the more significant the
impact of self-nucleation.45 Thus, the enhancement of crystal-
lization in F_2099, F_2499, and F_2699 samples result in
higher melting temperature and crystallinity. Besides, the
F_1399 sample has high melting and crystallization tempera-
tures, which is similar to the one obtained from the higher
molecular weight. This could be attributed to the more active

Melting curves
Tg chain motions in the low-molecular weight condition, but this
F_1399
effect would be reduced by the molecular weight rising.
F_1499
F_1799 In the melting curves in Figure 4 top, the glass-transition tem-
perature (Tg) of the PVA in the hydrogel films can be
Heat flow

F_2099 observed. All the values of Tg for the hydrogel films have no
F_2499 change (onset point around 65
C), which seems independent
of the molecular weight.
F_2699
The trends for the crystallization behaviors in Figure 4 are
similar to melting behavior. The crystallization temperature
30 60 90 120 150 180 210 240 (Tc) is decreased with the molecular weight for the films pre-
pared with lower molecular weight but increases to some
Temperature (°C)
extent without obvious change after the molecular weight
higher than 88,000 (F_2099). The crystalline enthalpy (ΔHc)
Crysallization curves values for F_1399, F_1499, and F_1799 are nearly the same
Endo Up

F_1399 (around 43 J/g) but lower than those for the other three
F_1499 hydrogel films with higher molecular weight (around 48 J/g).
ΔHc is expected to vary somewhat with crosslinking density
F_1799
(especially for very densely crosslinked networks). As
predicted, the higher the crosslinking density, the higher the
F_2099 ΔHc will be because of the self-nucleation enhancement of the
Heat flow

F_2499 networks and because the probability that a crystallite will

F_2699 form will be more.

Gel Concentration of PVA Hydrogel Films

30 60 90 120 150 180 210 240 The changes in the gel concentration of PVA hydrogel films
versus the PVA molecular weight are shown in Figure 5. The
Temperature (°C)
gel concentration of PVA hydrogel film increases slowly as the
FIGURE 4 DSC curves for the PVA hydrogel films prepared with molecular weight is lower than 88,000 (F_2099), sharply
different molecular weights. [Color figure can be viewed at increases to 45% and levels off above 105,600 (F_2499). The
wileyonlinelibrary.com] difference in the gel concentration for the hydrogel films

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TABLE 3 Thermal Properties of PVA Hydrogel Films Prepared with Different Molecular weight (PVA Concentration = 15 wt%)

Symbol T on
m ( C) T pm (
C) T mf (
C) ΔTm (
C) ΔHm (J/g) ΔXc (%) Tc (
C) ΔHc (J/g)

F_1399 226.6 233.4 236.7 9.2 36.1 26.0 233.3 42.8

F_1499 219.5 225.0 229.3 9.6 37.5 27.1 224.6 42.8
F_1799 217.7 223.4 226.3 8.2 33.1 23.9 219.5 42.9
F_2099 224.7 230.2 232.6 7.3 40.4 29.1 229.4 48.0
F_2499 220.0 226.0 229.8 9.3 41.0 29.6 226.1 48.8
F_2699 223.9 229.8 231.8 7.4 42.0 30.3 230.2 49.5

T on p f
m , onset of melting temperature; T m , melting peak temperature; T m , final melting temperature; ΔHm, melting enthalpy; Xc, the degree of crystalliza-
tion; Tc, crystallization temperature; ΔHc, crystallization enthalpy.

suggests the different crosslinking degrees in these samples.
The main cause of the crosslinkage is due to the PVA chain
entanglement effect. The higher molecular weight in PVA
hydrogel film, the more significant entanglements occurred.
Thus, the higher gel concentration is obtained in F_2499 and
F_2699 hydrogel films, in which around 45% gel concentra-
tion is obtained. The higher gel concentrations in F_2499 and
F_2699 hydrogel films indicate that a stable junction point in
these physically crosslinked hydrogels formed.
As reported,38 the higher degree of alcoholysis, the lower solu-
bility of PVA in water, because of the higher degree of
alcoholysis results in the higher crystallinity and stronger inter-
and intra-chain hydrogen bonding. In this work, the degree of
alcoholysis for all the PVA materials is 99%. Thus, the molecu-
lar weight effect would predominate the gel concentration in
the PVA hydrogel films. In Table 2, the crystallinity of PVA
hydrogel films increases with the molecular weight increase.
The improved crystallinity by increasing the molecular weight
enhanced the physical hydrogel formation. So, the different gel
concentration in those PVA hydrogel films can be attributed to
the two factors which include the entanglement effect and the
crystallites of PVA which caused by the PVA molecular weight.
Swelling Behavior of PVA Hydrogel Crosslinkage Network
The change of swelling behavior of PVA hydrogel films with
different molecular weights is shown in Figure 6. The swelling
propensity of PVA hydrogel film depends on the diffusion
coefficient of water, the relaxation of polymer chains in the
amorphous phase, and its crystallinity.46 The lower entangle-
ment extent and lower crystallinity would result in a facile
penetration of water in the PVA hydrogel networks. As men-
tioned in the previous section, a physical gel network exists in
the PVA hydrogel films, which mainly formed by the chain
entangled junction points and the presence of crystallinity. All
the PVA hydrogel films possess a high alcoholysis degree (99%).
The enormous amount of hydroxyl group in PVA chains would
enhance the strength of the chain entangled junction point,
which results in a lower degree of swelling (<10% in Fig. 6). The
swelling of PVA hydrogel films decreases with the increasing of
the molecular weight. All the equilibrium swelling time is more
than 60 min, as shown in Figure 6. For the PVA hydrogel films
with lower molecular weight (F_1399 and F_1499), the swelling
occurred a short period and got a relatively high swelling degree
(7% for F_1399 and 10% for F_1499 samples). The F_1700 sam-
ple has a less swelling degree (2%), and other films with higher
molecular weight have closed swelling degree (1 wt %). In

16

100 14 Black F_1399 Blue F_2099

Red F_1499 Cyan F_2499
90 Black: F_1399
12 Green F_1799 Magenta F_2699
Gel Concentration (%)

80 Read: F_1499
Green: F_1799 10
Swelling(%)

70
Blue: F_2099
60
Cyan: F_2499 8
50 Magenta: F_2699
40
6

30 4
20
2
10
0 0
50 60 70 80 90 100 110 120×103 0 20 40 60 80 100 120 140 160 180
Molecular weight of PVA in its hydrogel films Time(min)

FIGURE 5 Gel concentration of PVA hydrogel films prepared FIGURE 6 Swelling study of PVA hydrogel films in the water at
from different molecular weights. [Color figure can be viewed at 25
C (the swelling value in the y-axis should be multiplied by
wileyonlinelibrary.com] 100). [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 6, the PVA hydrogel film with a molecular weight of more
than 75,000 (F_1799) has a very short swelling extent, but after
the molecular weight continues to decrease, the film sample
swells significantly. The PVA hydrogel film with a molecular
weight of more than 75,000 (F_1799) has a fast water absorp-
tion rate because of quickly reaching the equilibrium swelling
state, but after the molecular weight continues to decrease, the
water absorption rate also drops. The water absorption rate of
F_1399 is lower than F_1499, but its maximum swelling degree
is higher than F_1499, so the intersection point appears in the
swelling degree curve.
The swelling test again shows the physical crosslinkage
formed in the PVA hydrogel films. The higher the molecular
weight, the more significant the number of entanglement
points and crystallites obtained. When the PVA hydrogel
films interact with cold water (at 25
C), the water pene-
trates throughout the interspace between the PVA chains,
which results in swelling even dissolution. The crosslinkage
network formed by the intense entanglement and PVA crys-
tallites may lead to an interlocking of the PVA chains. So, all
the PVA hydrogel films with a high alcoholysis degree hin-
der the penetration of the water.

FIGURE 7 Weight loss curve of PVA hydrogel films with different molecular weights in the water as a function of temperature. [Color
figure can be viewed at wileyonlinelibrary.com]

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Stability of PVA Hydrogel Crosslinkage Network

Elongation at break (%)

100 100
The stability of the PVA hydrogel films obtained from different

Tensile Strength (MPa)

molecular weights was studied by keeping them immersed in
80 80
water for varying periods and temperatures. The samples
show various weight losses, which means the difference in the 60 60
stability of the PVA hydrogel crosslinkage network arisen by
Black: F_1399
the different molecular weight. 40 Read: F_1499 40
Green: F_1799
The weight loss results support the observation that there is a Blue: F_2099
20 20
Cyan: F_2499
significant change in weight when immersing the PVA hydro- Magenta: F_2699
gel films in water, especially at different temperatures. As 0 0
50 60 70 80 90 100 110 120×103
shown in Figure 7, the crosslinked PVA hydrogel films are rel-
Molecular weight of PVA in its hydrogel films
atively stable in the water when the temperature below 40
C.
For the PVA hydrogel films with lower molecular weight FIGURE 8 Tensile strength and elongation at break of PVA
(F_1399 and F_1499), the weight loss still increases with the hydrogel films prepared with different molecular weights. [Color
immersion time, even at the temperature below 40
C. When figure can be viewed at wileyonlinelibrary.com]
the temperature increases, the physical crosslink sites
decrease because of the weakened physical bonding by heat
energies. When the temperature is closed to the dissolved networks (physical crosslink sites), the microcrystallites, and
temperature, the crystallite would be melt, resulting in the hydrogen bonds between PVA interchains. As discussed ear-
break up of the hydrogel networks. For the F_1799 sample, lier, the crosslinking and gel network formation arose from
the physical hydrogel network can be stable in water at the chain entanglement in the solution (ρχ), and the crystallinity
temperature below 60
C. As for the PVA hydrogel films with in the film (Xc) is significantly influenced by the molecular
higher molecular weight (F_2099, F_2499, and F_2699), there weight, which confirmed that only physically crosslinked PVA
is a small weight loss (<30%) in the water even at 90
C. gelation occurred. The hydrogen bonds between the PVA
Therefore, the higher entanglement density and crystallinity interchain would assist the chain entanglement and further
in the PVA hydrogel films prepared with a high-molecular self-nucleation crystallization. At high degrees of alcoholysis,
weight enhances the physical hydrogel networks. where inter and intrachain hydrogen bonding is dominant in
the solutions, the PVA solutions show a pronounced shear-
Mechanical Properties of PVA Hydrogel Films thinning behavior and apparent viscosity progressively
Figure 8 shows tensile strengths and elongations at break of increases with storage time due to the formation of energetic
the PVA hydrogel films prepared with different molecular chain entanglements and associations.38
weight. The tensile strength gradually increases with an PVA aqueous solution with low-molecular weight, because of
increase in the PVA molecular weight (ranging from 50 to its short chain length, is more freely relaxed in aqueous solu-
70 MPa), which can be attributed to the increased entangle- tion. In this case, the number of entanglement crosslink points
ment density and crystallinity. The F_1799 sample exhibits and hydrogen bonds, which only cause by interchains, is
the highest elongation at break (100%), and other samples
have a similar value at around 80%. The decrease in the elon-
gation at break of the hydrogel films with a molecular weight
higher than 61,600 (F_1499) can be due to the increased the
crosslinked chain entanglement density and crystallinity,
which make the hydrogel film stiffer.

Gelation Mechanism of the PVA Aqueous Solution

All PVA aqueous solutions made at 90
C with various molecu-
lar weights were transparent within measurement ranges,
regardless and polymer concentrations. When the tempera-
ture decreased to temperature (below Tg = 65
C), the gelation
would be conducted during the water evaporation. During
drying at the evaluated temperature (40
C), the transparent
hydrogel film was obtained, which is independent of the PVA
molecular weight. The gelation mechanism of the PVA aque-
ous, which affected by the PVA molecular weight can be
shown in Figure 9. A homogeneous solution of PVA aqueous
solutions was poured on a glass plate to form the PVA hydro- FIGURE 9 Schematic diagram of microstructural changes of PVA
gel films. During the water evaporation process, there are pre- from gel solutions to hydrogel films by evaporation process
dominant three factors that would determine the hydrogel (at the same concentration of the solution). [Color figure can be
film formation, which includes the PVA chain entanglement viewed at wileyonlinelibrary.com]

JOURNAL OF POLYMER SCIENCE, PART B: POLYMER PHYSICS 2019, 57, 1673–1683 1681

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small. When the PVA molecular weight is higher, the number
of entanglement crosslink points and hydrogen bonds are
larger because of both the inter- and intrachain hydrogen
bond formation. Thus, the gel concentration, the entanglement
density, swelling, stability, and crystallinity abruptly increased
when the molecular weight is higher than 8800 (F_2099).
CONCLUSIONS
In this study, we prepared transparent PVA hydrogel films
with a physical crosslinking method through controlling the
entanglement density. We used the PVA with a high
alcoholysis degree type (99%) to prepare the hydrogel solu-
tions because the higher hydrogen bond effect happened in
this case. The viscoelasticity of PVA aqueous solutions was
investigated over a wide range of molecular weight (57,200 to
114,400 g/mol). The rheological behavior of the aqueous PVA
solution was tested in the experimental system, and the ther-
mal analysis of the hydrogel films confirmed the physical
crosslinking occurred by the entanglements and micro-
crystallites. The aqueous PVA solution had a critical concen-
tration (c*) for gel formation. The value of c* decreased with
an increase in the molecular weight. The c* for S_1399,
S_1799, and S_2499 samples was 10.2, 9.8 and 8.2 g/100 ml.
The chain length between the crosslinks in the hydrogel (Me )
and entanglement density was determined by the plateau
modulus (G’). The value of (Me ) increased with the PVA
molecular weight, which can be attributed to the enhanced
entanglement associated with the hydrogen bonds between
inter- and interchains. When the molecular weight > 88,000 g/
mol, the entanglement density abruptly increased above
1.2 × 103 mol/cm3. The melting and crystallization of the
transparent PVA hydrogel films showed that the crystallinity
was below 30%, which indicated that microcrystallites
formed. Therefore, the entanglement effect and micro-
crystallization enhanced the stable crosslinked hydrogel net-
work, which improved by the increase in the molecular
weight. The PVA hydrogel films had a gel concentration rang-
ing from 10 to 45% and increased with an increase in the
molecular weight. The results of swelling in water also
dereased with an increasing of the PVA molecular weight,
ranging from 1 to 10%. The mechanical property showed that
the PVA hydrogel films had a tensile strength higher than
50 MPa and increased with an increase in the molecular
weight. As for the PVA hydrogel films with higher molecular
weight (F_2099, F_2499, and F_2699), there is a small weight
loss (< 30%) in the water even at 90
C. It is noteworthy to
observe that when the molecular weight of PVA was higher
than 88,000 g/mol, the hydrogel films reached a performance
of the swelling, water stability, and mechanical properties.
ACKNOWLEDGMENTS
This research was supported by the National Natural Science
Foundation of China (21406017); China Petroleum & Chemical
Corporation Science and Technology Project (218024-11);
The Natural Science Foundation of the Jiangsu Higher Institutions
of China (18KJA430005); Postgraduate Research & Practice
1682 JOURNAL OF POLYMER SCIENCE, PART B: POLYMER PHYSICS 2019, 57, 1673–1683
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JOURNAL OF
POLYMER SCIENCE
Innovation Program of School of Materials Science and Engineer-
ing Changzhou University; The Priority Academic Program Devel-
opment of Jiangsu Higher Education Institutions (PAPD), and the
Top-notch Academic Programs Project of Jiangsu Higher Educa-
tion Institutions (TAPP); Advanced Catalysis and Green
Manufacturing Collaborative Innovation Center, Changzhou
University.
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