Surfaces and Interfaces 25 (2021) 101198

Contents lists available at ScienceDirect

Surfaces and Interfaces

journal homepage: www.sciencedirect.com/journal/surfaces-and-interfaces

Crosslinked poly (vinyl alcohol): Structural, optical and

mechanical properties
Sanjib Sau, Subhankar Pandit, Sarathi Kundu *
Soft Nano Laboratory, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam
781035, India

A R T I C L E I N F O A B S T R A C T

Keywords: Poly (vinyl alcohol) (PVA) is a water-soluble, transparent, semi-crystalline polymer with excellent mechanical
Poly (vinyl alcohol) (PVA) properties, chemical resistance, and biocompatibility. The crystallinity, optical and mechanical properties of PVA
Crosslinking can be modified by the crosslinking process. In this work, a simple heat treatment method is used to fulfil this
X-Ray diffraction
purpose. Prepared films are heated at different temperatures and time intervals, and their various properties
Fluorescence spectroscopy
IR spectroscopy
were studied. Due to heating, PVA becomes more crystalline, and as a result, some weak peaks become more
Stress-strain behaviour pronounced in X-ray diffraction data. Fourier transform infrared studies are incorporated to show structural
modification and the presence of covalent bonds. Smooth surface morphology of PVA films is obtained from
scanning electron microscopy images, except for the film treated at a higher temperature. Optical properties of
pure and heat-treated films are explored using UV-Vis absorption and photoluminescence spectroscopy. UV-Vis
absorption peaks of pure PVA are located at around 284 nm and 325 nm, and the corresponding fluorescence
emission is observed at around 416 nm. From all the experimental observations, an improved crosslinked
structure is obtained for the film heated at 140◦ C for 40 min. In this condition, the improved mechanical property
is also obtained from the stress-strain curves. This crosslinked PVA prepared by simple heat treatment can have
potential applications in the textile industry, food packaging, etc.

1. Introduction existing polymer and modifies its surface, chemical, thermal and me­
chanical properties. Crosslinking is of two types: intramolecular (within
Poly (vinyl alcohol) (PVA) [CH2CH(OH)]n is a well-known biode­ the same molecule) and intermolecular (with different molecules) [16,
gradable, synthetic, hydrophilic polymer with various potential uses. 17]. Like other polymers, different methods are available for PVA
PVA is produced by the hydrolysis of polyvinyl acetate obtained by the crosslinking. The methods are classified into two categories: physical
polymerization of vinyl acetate [1,2]. Properties of PVA generally rely and chemical. Physical crosslinking occurs between the same PVA
on its parent polymer, i.e., poly (vinyl acetate), its polymerization molecules via hydrogen bonding between hydroxyl groups or simply
conditions, and degree of hydrolysis [3-5]. Due to low toxicity and entanglements. In contrast, PVA can be crosslinked chemically in the
biocompatibility, PVA obtains excellent attention in drug delivery [6] presence of a chemical agent, which shows good reactivity with func­
and biomedical applications such as wound dressing, arthroplasty, and tional groups of the polymer [18-20]. Different types of well-known
tissue engineering [7,8]. Due to its water solubility, optical trans­ physical crosslinking methods are freeze-thawing, heat treatment, and
parency, biodegradability, thermal properties, adhesiveness, etc., PVA is methanol treatment [18,21-23]. Whereas chemical crosslinkers such as
extensively employed in paper, textile, and food industries [9,10]. Due glutaraldehyde, formaldehyde, maleic acid, methacrylate, and multi­
to high water permeation and film-forming properties, PVA is used as a functional agents that form covalent bonds between the polymer chains,
membrane material [4, 11]. PVA is also used to prepare various com­ create chemical crosslinking of PVA [20,24-25]. Physical crosslinking
posite films with graphene oxides, cellulose, carbon nanotubes, and has an advantage over the chemical crosslinking as the physical cross­
different nanoparticle, etc., to improve their inherent unique properties linking happens in the absence of any additional crosslinker [26]. Heat
like uniaxial tensile, optical, and electrical properties, etc. [12-15]. treatment is an extensively used effective method to obtain crosslinking
Crosslinking is an exciting tool that modifies the structure of an of PVA [27,28]. Heat treatment of PVA has a considerable effect on its

* Corresponding author.
E-mail address: [email protected] (S. Kundu).

https://doi.org/10.1016/j.surfin.2021.101198
Received 16 November 2020; Received in revised form 23 April 2021; Accepted 30 April 2021
Available online 18 May 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Fig. 1. (a) Schematic diagram of preparation of PVA films. (b) Photograph of few PVA films: (i) Pure PVA film; PVA films heated for 30 min at (ii) 120◦ C (iii) 140◦ C
(iv) 160◦ C (v) 180◦ C and (vi) 200◦ C.

solubility in water. Heat treatment of PVA is extensively used by the of the films were also studied to investigate the mechanical properties.
textile industry [29]. PVA-poly(acrylic acid) (PAA) blended All the results are compared to obtain the optimal crosslinking condition
thermo-crosslinked hydrogel possess pH-sensitive properties in electro­ for PVA using heat treatment.
lyte solution for a pH range from 2.5 to 12.5 [30]. PVA crosslinked by
heating, in the presence of crosslinker glutaraldehyde, shows excellent 2. Experimental procedure
disintegration activity [31]. Due to hydrophilicity, PVA holds some
amount of water that stays in their films from aqueous solutions, and 2.1. Materials
these films also absorb water from the external medium, which affects
their physical properties [32]. The elastic modulus of PVA reduces if it Poly (vinyl alcohol) (PVA) (Catalogue No. 8.43866.1000, M.W. =
contains a relatively more amount of water. High-temperature anneal­ 60000, 99% purity) was purchased from Merck. Double-distilled water
ing leads to the ejection of water molecules and the crystallization of of resistivity of approximately 18.2 MΩ-cm from the Millipore Milli-Q
PVA film [29,33,34]. Each hydroxyl group of completely dehydrated system was used throughout the experiments.
PVA film makes hydrogen bonds with two different hydroxyl groups
[27,32]. Furthermore, optical properties, i.e., absorption and emission
spectra, are also modified during heat treatment [35]. 2.2. Film preparation
In this article, specific structural, spectroscopic, and mechanical
behaviours of pure and heat-treated PVA films are described. PVA films PVA films were prepared using the solution casting method. First,
were prepared by solution casting method, and heat-treatment was done aqueous 10% (w/v) PVA solution was prepared by dissolving PVA in
at different conditions. Structures and crystallinity of pure as well as Milli-Q water at 90◦ C under continuous stirring using a magnetic stirrer.
heat-treated PVA films were studied using X-ray diffraction (XRD), and The aqueous PVA solution was then cast on a polystyrene petri dish to
structural modifications were also investigated by FTIR spectroscopy. prepare uniform films. After that, the films were dried overnight at room
Optical properties were studied using UV-Vis absorption spectroscopy temperature. The heat treatment of as-prepared PVA films was done in
and photoluminescence spectroscopy techniques. Scanning electron two ways: (a) a fixed time and varying temperature; (b) fixed temper­
microscopy (SEM) was used to observe the surface morphology of the ature and varying time. For the first case, the PVA films were heated at
films. Stress-strain relation and the corresponding hysteresis behaviour different temperatures, viz. 120, 140, 160, 180, and 200◦ C for 30 min.
For the second case, heating of the PVA films was done for different

Fig. 2. XRD spectra of (a) pure PVA and T30 PVA films; (b) Pure PVA and H140 PVA films. The values in percentage indicate crystallinity of the corresponding films.
The spectra are shifted vertically for clarity.

2
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Table 1 Table 1 (continued )

Parameters related to the deconvoluted curves of the XRD spectra of the PVA Sample name Peak position Line width Area under the R2
films. (peak shape) with error with error curve with error
Sample name Peak position Line width Area under the R2 22.91 ± 0.024 2.06 ± 431.17 ± 16.840
(peak shape) with error with error curve with error 0.069
Pure PVA 19.44 ± 0.002 2.17 ± 7244.36 ± 13.910 0.965 41.07± 0.037 4.76 ± 1059.93 ± 18.807
(Gaussian) 0.005 0.088
40.76 ± 0.059 6.80 ± 1684.69 ± 24.636
0.140
T30_120 C◦
19.48 ± 0.002 1.68 ± 5286.03 ± 13.170 0.968 times, viz. 20, 30, 40, 50, 60, 70, and 80 min at a temperature of 140◦ C.
(Gaussian) 0.005 The films were heated in an oven in normal atmospheric condition and
22.75 ± 0.018 1.81 ± 667.41 ± 13.636 all the characterizations were performed at room temperature (22◦ C). It
0.043
40.53 ± 0.044 4.81 ± 1164.01 ± 21.796
is considered that the structure and properties of PVA films are modified
0.104 permanently after the heat treatment [4,21]. The schematic diagram of
T30_140◦ C 19.58 ± 0.001 1.64 ± 12056.55 ± 0.985 the preparation of PVA films is shown in Fig. 1(a). The photograph of
(Gaussian) 0.003 20.406 pure PVA film and some heat-treated PVA films are shown in Fig. 1(b).
22.72 ± 0.015 1.42 ± 851.66 ± 18.980
The film thickness was almost uniform, and the value was between
0.037
40.85 ± 0.044 3.99 ± 1402.83 ± 31.676 0.199 to 0.217 mm. The films heated at different temperatures from 120
0.104 to 200◦ C, for a fixed heating time of 30 min are designated as T30,
T30_160◦ C 19.59 ± 0.001 1.60 ± 13159.79 ± 0.984 whereas H140 indicates the films heated at fixed temperatures of 140◦ C
(Gaussian) 0.003 23.032 but for different heating times from 20 to 80 min, in our further
22.75 ± 0.010 1.19 ± 1172.58 ± 19.864
0.023
discussion.
40.73 ± 0.036 3.32 ± 1517.91 ± 33.121
0.084
T30_180◦ C 19.61 ± 0.001 1.49 ± 10710.96 ± 0.984 2.3. Characterizations
(Gaussian) 0.003 18.677
22.66 ± 0.007 1.22 ± 1384.89 ± 16.939 The structural, optical, and mechanical properties of as-prepared
0.017
films were characterised using standard techniques.
40.83 ± 0.041 3.97 ± 1440.29 ± 30.557
0.098
T30_200◦ C 19.67 ± 0.002 1.37 ± 4719.58 ± 15.851 0.941 2.3.1. X-ray diffraction
(Gaussian) 0.005 The crystalline nature of the PVA films was studied using a D8
22.63 ± 0.008 1.10 ± 972.817 ± 14.189 Advanced, Bruker, AXS X-ray diffractometer (XRD). The diffractometer
0.018
40.58 ± 0.054 2.23 ± 714.91 ± 24.405
consists of a Cu source operating at 40 kV and 40 mA (sealed tube) and
0.128 followed by a Göbel mirror to select and enhance Cu Kα radiation (λ =
H140_20 min 19.49 ± 0.002 1.83 ± 9843.91 ± 24.755 0.968 1.54 Å), and NaI scintillation (point) detector was used to detect the
(Gaussian) 0.005 scattered beam. The scanning was performed with a 1◦ /min speed in a
22.96 ± 0.024 2.02 ± 1038.90 ± 25.960
range of 2-theta from 5◦ to 60◦ .
0.060
40.76 ± 0.052 5.01 ± 1870.83 ± 39.584
0.122 2.3.2. Fourier transform infrared spectroscopy (FTIR)
H140_30 min 19.59 ± 0.002 1.69 ± 7421.24 ± 14.901 0.979 The chemical structure of PVA films was evaluated using the Nicolet-
(Gaussian) 0.004 6700 Fourier transform infrared (FTIR) spectrophotometer from Thermo
22.78 ± 0.021 1.72 ± 591.77 ± 15.011
0.051
Scientific, taking averaged over 64 scans and at resolution of 4 cm− 1.
40.81 ± 0.073 6.91 ± 1357.81 ± 29.460 The spectra were recorded in attenuated total reflection (ATR) mode
0.173 over the range of 400 - 4000 cm− 1.
H140_40 min 19.58 ± 0.002 1.64 ± 12057.52 ± 0.985
(Gaussian) 0.003 20.406
2.3.3. Absorbance and fluorescence characterizations
22.73 ± 0.017 1.43 ± 851.76 ± 18.980
0.036 UV-Vis absorption spectra of the films were collected by Shimadzu
40.83 ± 0.043 3.99 ± 1401.85 ± 31.676 UV-1800 spectrometer in the range of 190–1000 nm. Photo­
0.104 luminescence spectra were recorded on JASCO FP-8500 Fluorescence
H140_50 min 19.51 ± 0.003 1.42 ± 4242.62 ± 13.157 0.952 Spectrometer over the range of 290–650 nm.
(Gaussian) 0.005
22.73 ± 0.027 1.66 ± 496.48 ± 14.149
0.056 2.3.4. Scanning electron microscopy (SEM)
40.77 ± 0.061 4.25 ± 869.85 ± 21.724 The surface morphology of the PVA films was obtained by Field
0.123 Emission Scanning Electron Microscopy (FESEM) technique with the
H140_60 min 19.49 ± 0.002 1.66 ± 4745.08 ± 12.909 0.975
help of SIGMA 300 from ZEISS. Energy-dispersive X-ray (EDX) analysis
(Gaussian) 0.005
22.63 ± 0.016 1.70 ± 568.89 ± 17.301 was also carried out for the elemental analysis. The samples were gold
0.044 coated and fixed with double adhesive carbon tape on stainless steel
40.75 ± 0.041 4.07 ± 864.30 ± 20.383 supports. Images and corresponding elemental mapping were taken at
0.098 randomly selected locations.
H140_70 min 19.71 ± 0.002 1.74 ± 3910.28 ± 11.299 0.968
(Gaussian) 0.005
22.87 ± 0.016 1.53 ± 421.01 ± 13.25 2.3.5. Mechanical measurements
0.043 Mechanical properties of the PVA films were studied using the model
41.19 ± 0.046 4.95 ± 1029.94 ± 27.377 H5KL from Tinius Olsen with a sample size of 20 × 8 mm2. ASTM
0.111
D638–10 standard was used for the tensile test. Gage length of 10 mm
H140_80 min 19.67 ± 0.003 1.71 ± 3056.75 ± 10.178 0.954
(Gaussian) 0.006 was kept constant, and the deformation rate was set at 3 mm/min.
Hysteresis loops were taken below the yield point for four successive
cycles. For tensile measurements each kind of specimen was tested for

3
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Fig. 3. UV-Vis absorption spectra of (a) Pure PVA and T30 PVA films; (b) H140 PVA films. Insets: corresponding emission spectra for two different excitation
wavelengths of 284 nm (upper) and 325 nm (lower) of respective PVA films.

three times. Here the crystallinity of the films increases with the increase in heating
time up to 40 min and then again decreases for further heating. There­
3. Results and discussion fore, maximum crystallinity is observed for PVA films heated at 140◦ C
for 40 min. The baseline corrected XRD spectra are shown in Fig. S1. The
3.1. X-ray diffraction analysis main crystalline peaks of the XRD spectra were deconvoluted with
Gaussian distribution (see supplementary file) for better understanding
To study the crystallinity of the pure and heat-treated PVA films, X- and the related parameters are shown in Table 1. The three prominent
Ray diffraction (XRD) study was done. XRD spectra of pure PVA and T30 peaks located at 2θ ≈ 19.5◦ , 40.5◦ , 22.5◦ were fitted during deconvo­
PVA films, i.e., PVA films heated for 30 min at different temperatures are lution, and the peak position, peak width and peak area of the fitted
shown in Fig. 2(a). The spectra are shifted vertically for clarity. PVA is curves with their errors were calculated. Apart from crosslinking,
known as a semi-crystalline polymer and it has monoclinic lattice increment of crystallinity also indicates the generation of linear polyene
structure with cell parameters a = 7.81 Å, b = 2.52 Å, c = 5.51 Å, β = 91◦ structure inside PVA samples [4]. At higher temperatures or heating
42′ [36]. As shown in Fig. 2(a), pure PVA shows mainly three charac­ time, crystallinity decreases. This occurs because of the obstruction in
teristic diffraction peaks. One strong peak is observed at 2θ = 19.5◦ (d = the formation of more ordered structural units due to film degradation.
4.54 Å), and one weak peak is observed at 40.5◦ (d = 2.22 Å), which are
assigned to (101) and (202) reflection planes respectively corresponding 3.2. Optical properties
to the crystalline phase of PVA. The crystallinity of PVA depends on the
presence of hydroxyl groups in every repeating unit of PVA chains and Optical absorption and emission behaviors of the PVA films were also
the strong intramolecular interaction between PVA chains via hydrogen studied. UV-Vis absorption spectra and the corresponding fluorescence
bonding [36,37]. Heat treatment leads to the evolution of one strong emission spectra are presented in Fig. 3. UV-visible absorption spectra
peak at 2θ = 22.5◦ (d = 3.95 Å) and few weak peaks at 2θ = 11.3◦ (d are used to understand and compare the optical activity of the samples.
=7.82 Å), 27.5◦ (d = 3.24 Å) and 32.3◦ (d = 2.77 Å) which are desig­ Fig. 3(a) corresponds to the UV-Vis absorption spectra of pure PVA film
nated as (200), (100), (201) and (002) planes respectively [37]. The and T30 PVA films. The UV-Vis absorption spectra of H140 PVA films
crystallinity of the films which are mentioned in the respective spectra are shown in Fig. 3(b). From the absorption spectra, it is evident that
are calculated using the following equation, pure PVA has absorption bands at around 284 and 325 nm, which can be
AC attributed to π → π* and n → π* transitions due to the resonating
Crystallinity (%) = × 100 (1) carbonyl group (>C = O) [39,40]. There is no absorption band in the
AC + AA
visible region. From absorption spectra, it is vivid that absorbance for
where, AC and AA refer to the crystalline area and the amorphous area T30 PVA films increases gradually with an increase in temperature, but
respectively. AC + AA indicates total area under the XRD spectra [38]. for H140 PVA films, absorbance increases up to 40 min, and after that, it
It is observed that the crystallinity for T30 films, as shown in Fig. 2 decreases. For the PVA film heated at 200◦ C, absorption intensity gets
(a), increases with an increase in temperature up to a particular value saturated, and as a result, we get a smooth curve without any absorption,
and then decreases. Maximum crystallinity is obtained for PVA film as in Fig. 3(a). This indicates the burning of PVA film at that very high
heated at 140◦ C for 30 min. Due to the heat treatment, PVA chains temperature. For the proper analysis of the overlapped peaks found in
undergo intramolecular crosslinking. As molecular conformation the UV -Vis absorption spectra, the peaks were deconvoluted and the
changes, crystallinity also modifies. Keeping the temperature constant at obtained parameters are tabulated in the Table-S1 (see supplementary
140◦ C, PVA films were also heated for different times, which are indi­ file). The deconvoluted curves of T30 films including pure PVA, and
cated by H140. The XRD spectra of H140 PVA films are shown in Fig. 2 H140 films are shown in Fig. S2 and Fig. S3, respectively. The variation
(b). The crystallinity of the films is mentioned in the respective spectra. of the peak position and peak width with respect to the time and

4
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Fig. 4. Variation in (a) peak position and (b) peak width of the deconvoluted UV-Vis absorption spectra of PVA films heated for a fixed time of 30 min. Variation in
(c) peak position and (d) peak width of the deconvoluted UV-Vis absorption spectra of PVA films heated at a fixed temperature of 140◦ C. Black lines are for the peak
at around 284 nm, whereas red lines are for the peak at around 325 nm.

Fig. 5. FTIR spectra of (a) pure PVA and selected T30 films, i.e., PVA films heated at 120, 140 and 180◦ C for 30 min; (b) pure PVA and few H140 films, i.e., PVA films
heated at 140◦ C for 20, 40 and 80 min.

5
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Fig. 6. SEM images of (a) pure PVA film and PVA films heated for 30 min at constant temperature of around (b) 120◦ C, (c) 140◦ C and (d) 180◦ C. Arrow direction
indicates the C mapping, O mapping, and overlap of C and O mapping of the corresponding SEM image.

Fig. 7. The tensile stress-strain curves of (a) pure PVA and selected T30 PVA films, i.e., PVA films heated for 30 min at around 120, 140 and 180◦ C; (b) H140 PVA
films, i.e., PVA films heated for 20, 40 and 80 min at around 140◦ C.

temperature are plotted, which are shown in Fig. 4. The variation of the gradually up to 40 min and decreases with further increment of heating
peak position and peak width for constant heating time, i.e., pure PVA time. Therefore, PVA film, which was heated at 140◦ C for 40 min, can be
and T30 films are shown in Fig. 4(a) and 4(b) respectively. Similarly, chosen as an optimal condition, where maximum intramolecular
Fig. 4(c) and 4(d) corresponds to the variation of the peak position and crosslinking is taking place via hydrogen bond formation. Beyond that
peak width respectively for a constant heating temperature, i.e., for pure temperature or time, emission intensity decreases due to gradual ma­
PVA and H140 films. It is clear that the variation in the peak width is terial degradation of the films. On the other hand, it can be stated that
observed but the position of the absorption bands of the pure and the heat-treated PVA films have UV shielding properties as the films are
heat-treated PVA films remains nearly unchanged. absorbing UV light, and emissions are taking place in the visible region.
The emission spectra corresponding to both the absorptions are
shown in the insets of the corresponding figures. The upper and lower
3.3. Chemical structure analysis
insets of each figure are for the excitation wavelengths (λex) of 284 and
325 nm, respectively. For both the excitations, maximum emission in­
To observe the structural modifications at the molecular level, FTIR
tensity is observed at around 416 nm. From the emission spectra cor­
spectra of the samples were recorded for the energy range of 800-4000
responding to T30 films, it is clear that the emission intensity increases
cm− 1. FTIR absorption spectra of pure PVA and heat-treated PVA films
gradually up to 140◦ C and decreases with the further increment of the
are shown in Fig. 5. FTIR spectra of pure PVA film and selected T30 PVA
temperature for the excitations. For H140 films, the same trend is also
films, i.e., PVA films heated at 120, 140, and 180◦ C for 30 min are
observed. For both the excitations, emission intensity increases
displayed in Fig. 5(a), whereas, Fig. 5(b) represents the FTIR spectra

6
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Table 2 roughness increases at higher temperatures as the lower molecular

Summary of different parameters of the tensile testing results of pure PVA and weight products migrate in the gaseous state due to degradation [33,
few heat-treated PVA films. 41]. The elemental mapping of the respective SEM images is also shown
Sample Young’s Tensile Strain Toughness Hysteresis in Fig. 6. From elemental mappings, it is evident that carbon is the
Details modulus strength at break (MPa) loop area for 4 significant component compared to oxygen for all the samples. Pure PVA
(GPa) (MPa) (%) cycles (MPa) shows the amount of carbon and oxygen ≈ 55 and 45 %, respectively.
× 10− 2
However, (T30, 120◦ C) and (T30, 140◦ C) films show the amount of
Pure 0.24 ± 31.9 ± 229 ± 57.8 ± 7.0 29.6 ± 4.2 carbon is ≈ 56 % and oxygen is ≈ 44 %. The (T30, 180◦ C) film shows
PVA 0.04 2.35 11.4
carbon and oxygen amounts are ≈ 57 and 43% respectively. Therefore,
T30, 0.35 ± 28.1 ± 158 ± 37.4 ± 4.2 -
120◦ C 0.05 0.05 8.9 it is found that the oxygen content is reduced with the heat treatment as
T30, 0.48 ± 36.1 ± 2.8 177 ± 57.3 ± 6.5 - some water molecules are ejected.
140◦ C 0.02 10.1
T30, 0.57 ± 31.8 ± 180 ± 50.5 ± 5.3 -
180◦ C 0.01 2.45 9.3
3.5. Mechanical properties
H140, 0.89 ± 42.1 ± 1 211 ± 76.5 ± 6.7 26.7 ± 1.0
20 0.07 7.5
min The mechanical property of the PVA films was examined by tensile
H140, 1.23 ± 46.8 ± 200 ± 81.2 ± 0.6 14.3 ± 1.8 testing. Typical stress-strain behavior of the pure and heat-treated PVA
40 0.02 0.75 11.5 films is shown in Fig. 7. The stress-strain behavior of pure PVA and few
min
T30 films, i.e., PVA films heated for 30 min at 120, 140, and 180◦ C, are
H140, 1.12 ± 41.4 ± 159 ± 57.6 ± 1.2 26.4 ± 2.1
80 0.08 2.25 12.5 shown in Fig. 7(a). The stress-strain behaviour of H140 films, i.e., PVA
min films heated at around 140◦ C for 20, 40 and 80 min, are presented in
Fig. 7(b). Different tensile parameters are also calculated and presented
in Table 2. Young’s modulus of the films is calculated from the slope of
corresponding to selected H140 films, i.e., PVA films heated at 140◦ C for
the linear portion of the stress-strain curve, and the toughness of the
20, 40 and 80 min. For pure PVA, a broad absorption band is observed
films is calculated using the area under the stress-strain graph. From
from 3000 to 3600 cm− 1 centering at 3355 cm− 1, which can be ascribed
Fig. 7(a) and calculated values, it is clear that the pure PVA has low
to ‒OH stretching vibration owing to intramolecular strong hydrogen
tensile strength but among T30 films, which were heated at 140◦ C,
bond interactions [4]. The peak at around 2901 cm− 1 represents ‒CH
possess high tensile strength. For H140 films, maximum tensile strength
stretching vibration [11]. The peaks at around 1021 and 1650 cm− 1 are
is obtained for the film heated for 40 min. The same film also shows the
attributed to ‒C‒O and ‒C=O stretching vibrations, respectively, which
highest toughness compared to all the films, which can be attributed to
occur due to absorption of the residual acetate content persist in the PVA
dense network structure formation due to intramolecular crosslinking
at the time of hydrolysis of vinyl acetate [41,42]. The absorption peak at and ejection of water molecules. Almost all the heat-treated films show
1314 cm− 1 is assigned to ‒CH‒ and ‒OH bending [4]. Due to heating,
higher Young modulus compared to pure PVA film, which indicates the
the ‒OH broadband becomes narrower, which may be due to the formation of brittle-like behaviour of the heat-treated films. This may be
reduction of hydroxyl groups as water molecules are eliminated [4]. At
due to the reduction of the mobility of PVA chains owing to partial
the same time, due to heating ‒CH stretching peak becomes prominent.
dehydration of hydroxyl groups that happened upon heating. As the heat
For better understanding the overlapped FTIR peaks are deconvoluted in
treatment makes the PVA films rigid, therefore, all the heat-treated films
the region of interest, i.e., within 2000-800 cm− 1 and are shown in
show lower strain value at breaking point compared to the pure PVA.
Fig. S4. The parameters namely peak position, peak width, peak area
This improved mechanical property can be illustrated on the basis of the
and peak height are obtained and tabulated (see supplementary file) in
Haward–Thackray model [45,46]. This model consists of a Hookean
Table-S2. The deconvoluted FTIR spectra shows that the intensity of the
spring connected in series with a parallel combination of dashpot and
peak at around 1650 cm− 1 increases and the full width at half maximum
another spring. Thus, this model contains three parameters, i.e., the
(FWHM) of the peak also increases with heat treatment which indicates
tensile modulus E, the shear modulus of the network G and the viscosity
the formation of more numbers of C=O groups. Probably due to heating,
η. G is calculated from the slope at the post–yield region. From the
some double carbon bonds (C=C) are formed. However, heating in
theory of rubber elasticity, the crosslinking density νe can be calculated
normal atmospheric condition, i.e., in presence of oxygen, makes such
from the following equation [47],
double carbon bonds unstable and undergo further oxidation to form
C=O bonds. Due to this reason, the FTIR peak for C=C bond is also not νe =
G
(2)
observed [43]. Moreover, due to heat treatment, some hydrogen bonds RT
are also formed between C=O and ‒OH groups of PVA molecules and as
where, T is absolute temperature, G is the shear modulus of the network
a result the absorbance of C=O group is modified [44].
and R is the gas constant. The calculated values of crosslinking density
are approximately 2467, 2497, 2502 and 2171 mol/m3 for pure PVA and
3.4. Surface morphology T30 films of 120◦ C, 140◦ C and 180◦ C respectively. The calculated values
of crosslinking density are approximately 2566, 3295 and 2673 mol/m3
The surface morphology of PVA films is studied using scanning for H140 films of 20 min, 40 min and 80 min respectively. Therefore, it is
electron microscopy. SEM images and their corresponding elemental obvious that the crosslinking density increases with increasing the
(carbon and oxygen) mappings of pure PVA and T30 films are shown in heating temperature or time. But at higher temperature or time, it de­
Fig. 6. Fig. 6(a) corresponds to the smooth surface morphology of the creases due to film degradation. This increment of crosslinking density
pure PVA films. Fig. 6(b), 6(c), and 6(d) correspond to the surface also indicates the increment of degree of polymerization. The film
morphology of PVA films heated at 120, 140, and 180◦ C for 30 min. For heated for 40 min at 140◦ C displays the highest tensile strength,
the PVA films corresponding to heating at 120 and 140◦ C for 30 min, toughness and Young modulus of ≈ 46.8 MPa, 81.2 MPa and 1.23 GPa
surface smoothness remains the same as pure PVA films. However, the respectively among all the films. Therefore, the film heated for 40 min at
surface of the film becomes rough for the film heated at 180◦ C for 30 140◦ C exhibits an improved mechanical property which is owing to
min. Therefore, films remain smooth and homogeneous up to a specific nearly 34% higher crosslinking density compared to pure PVA. Due to
temperature, but at higher temperature the films degrade and obstruct the combined effect of crosslinking density and ejection of water mol­
the formation of more ordered structural units. Generally, surface ecules, all the heat-treated films show lower strain at breaking point (i.

7
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

Fig. 8. Hysteresis plots of (a) pure PVA film and PVA films heated at 140◦ C for (b) 20 min, (c) 40 min and (d) 80 min for four cycles.

Fig. 9. Schematic representation of probable crosslinking structure of PVA after heat treatment.

e., film flexibility decreases) compared to pure PVA film. Thus, the good mechanical behaviour than those heated at other temperatures.
improved mechanical properties of the heat-treated films are attributed Therefore, we have studied the hysteresis behaviour of H140 films along
to increasing crosslinking density or degree of polymerization [48-50]. with pure PVA film. Hysteresis behaviour of pure PVA film is shown in
The above results suggest that PVA films, heated at 140◦ C, show Fig. 8(a), whereas, for H140 PVA films heated at 140◦ C for 20, 40, and

8
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

80 min are presented in Fig. 8(b), 8(c) and 8(d) respectively. Measure­ structural, optical, and mechanical properties are improved compared to
ments are taken for four successive cycles, which are composed of pure PVA film by only heat treatment. Due to heat treatment, PVA
loading curves and immediately followed by unloading curves. molecules arrange among themselves by H-bond formation to form a
The hysteresis loop areas as mentioned in Table 2 are the total area stable, crosslinked structure, and the study reveals the optimal cross­
under the stress-strain curve obtained from the consecutive four cycles. linking condition as heating at 140◦ C for 40 min. Therefore, heat-
Unloading curves for all the films do not coincide with their corre­ treatment is an effective method to obtain physical crosslinking
sponding loading curves, indicating gradual structural deformation of without any addition of a crosslinker.
the films from their original shape. Among all the films, less hysteresis
loop area is observed for H140 PVA film with 40 min heating. Therefore, Author’s contribution
it has less structural deformation after performing four hysteresis loops.
SS and SP per-formed all the ex-per-i-ments and jointly collected and
3.6. Crosslinking mechanism analyzed the data. SS, SP and SK validated the work and wrote the man-
u-script. SK su-per-vised the work.
Thus, from all the characterizations mentioned earlier and corre­
sponding results, it is found that pure PVA film properties are modified
due to the heat treatment. From the T30 films, it is clear that the Declaration of Competing Interest
improvement in different properties, i.e., crystallinity, optical response,
stress-strain behavior, etc., are observed for the film heated at around The authors declare that they have no known competing financial
140◦ C. Again, fixing the heating temperature at 140◦ C, when heating interests or personal relationships that could have appeared to influence
time is varied, maximum performance is obtained for the film heated for the work reported in this paper.
40 min. Due to heating, PVA samples undergo a dehydration reaction.
This heat treatment reduces the number of hydroxyl groups on the PVA Acknowledgements
chains and results in the ejection of water molecules from the PVA
chains. At the same time, formation of intramolecular hydrogen bonds S. Sau acknowledges the Department of Science and Technology,
occurs due to the presence of unreacted hydroxyl groups. Intermolecular Govt. of India for financial support through INSPIRE Fellowship
hydrogen bonds may also form between two PVA chains [4,42,51]. (IF180888). S. Pandit acknowledges the Department of Science and
Some hydrogen bonds also form between C=O groups and –OH groups Technology, Govt. of India for financial support through INSPIRE
of PVA [44]. These conditions are well known as crosslinking. The film Fellowship (IF 160402). S. Kundu acknowledges financial support from
heated for 40 min at 140◦ C exhibits tensile strength and toughness at Department of Science and Technology, Govt. of India. Authors
around 46.8 and 81.2 MPa respectively, which is approximately 47% acknowledge IASST, Guwahati for the financial and all experimental
and 40% higher than the corresponding values obtained from the pure facilities. We are also thankful to Sophisticated Analytical Instrument
PVA. This film also displays nearly 52% decrement of hysteresis loop Facility (SAIF), Gauhati University for SEM facilities.
area and 34% higher crosslinking density than the pure PVA. For the
film heated for 40 min at 140◦ C, fluorescence emission spectra exhibit Supplementary materials
maximum emission intensity and FTIR spectroscopy also gives the
indication of crosslinking. Therefore, this improved mechanical behav­ Supplementary material associated with this article can be found, in
iour is mainly owing to crosslinking via hydrogen bonds. It can be the online version, at doi: 10.1016/j.surfin.2021.101198.
depicted through a schematic diagram as in Fig. 9. Therefore, both inter-
and intra-molecular crosslinking may occur during heating, and the References
arrangement of PVA molecules becomes stable and improved. In this
present study, maximum crosslinking, as well as improved properties, [1] B.K. Tan, Y.C. Ching, S.C. Poh, L.C. Abdullah, S.N. Gan, A review of natural fiber
reinforced poly(vinyl alcohol) based composites: application and opportunity,
are obtained due to heating of the PVA film for 40 min at 140◦ C. This
Polymers 7 (2015) 2205–2222, https://doi.org/10.3390/polym7111509.
crosslinked PVA has potential applications in the field of filtration, [2] M. Teodorescu, M. Bercea, S. Morariu, Biomaterials of poly(vinyl alcohol) and
packaging, food industry, etc. natural polymers, Polym. Rev. 58 (2018) 247–287, https://doi.org/10.1080/
15583724.2017.1403928.
[3] T. Kimura, K. Urayama, Multiaxial stress relaxation of dual-cross-link poly(vinyl
4. Conclusions alcohol) hydrogels, ACS Macro Lett. 9 (2020) 1–6, https://doi.org/10.1021/
acsmacrolett.9b00896.
In this article, the optimal crosslinking condition of polyvinyl alcohol [4] J.M. Gohil, A. Bhattacharya, P. Ray, Studies on the cross-linking of poly (vinyl
alcohol), J. Polym. Res. 13 (2006) 161–169, https://doi.org/10.1007/s10965-005-
(PVA) films is reported, and the related structural, optical, and me­ 9023-9.
chanical properties are discussed. The PVA films are prepared via the [5] C. M. Hassan, N. A. Peppas, Structure and applications of poly (vinyl alcohol)
solution casting method, and after that, heat treatments are done. hydrogels produced by conventional crosslinking or by freezing/thawing methods,
Adv. Polym. Sci. 153 (1999) 37-65. DOI: 10.1007/3-540-46414-x_2.
Structural, morphological, spectroscopic, and mechanical studies are [6] E-R. Kenawy, E.A. Kamoun, M.S.M. Eldin, M.A. El-Meligy, Physically crosslinked
performed for pure PVA and heat-treated PVA films. XRD spectra show poly (vinyl alcohol)-hydroxyethyl starch blend hydrogel membranes: synthesis and
the evolution of some weak peaks due to heat treatment, and as a result, characterization for biomedical applications, Arab. J. Chem. 7 (2014) 372–380,
https://doi.org/10.1016/j.arabjc.2013.05.026.
crystallinity modifies and increases for the specific condition of the heat [7] L. Coluccino, R. Gottardi, F. Ayadi, A. Athanassiou, R.S. Tuan, L. Ceseracciu,
treatment. Due to heating, ejection of water molecules happens and Porous poly (vinyl alcohol)-based hydrogel for knee meniscus functional repair,
crosslinking occurs, which increases the crystallinity of PVA films. The ACS Biomater. Sci. Eng. 4 (2018) 1518–1527, https://doi.org/10.1021/
acsbiomaterials.7b00879.
maximum crystallinity is obtained for the PVA film heated at 140◦ C for [8] S. Feiz, A.H. Navarchian, O.M. Jazani, Poly (vinyl alcohol) membranes in
40 min. UV-Vis, as well as fluorescence spectroscopy studies also support wound‑dressing application: microstructure, physical properties, and drug release
the results of XRD. Both UV-visible and fluorescence spectra are modi­ behavior, Iran Polym. J. 27 (2018) 193–205, https://doi.org/10.1007/s13726-
018-0600-2.
fied with heat treatment, and superior results are obtained for the film
[9] J. Babu, Z.V.P. Murthy, Treatment of textile dyes containing wastewaters with
with maximum crystallinity. Smooth surface morphology obtains from PES/PVA thin film composite nanofiltration membranes, Sep. Purif. Technol. 183
the SEM study for pure PVA as well as heat-treated PVA. However, at (2017) 66–72, https://doi.org/10.1016/j.seppur.2017.04.002.
higher temperature surface become rough, which may be owing to [10] F. Luzi, E. Fortunati, A.D. Michele, E. Pannucci, E. Botticella, L. Santi, J.M. Kenny,
L. Torre, R. Bernini, Nanostructured starch combined with hydroxytyrosol in poly
material degradation. Among all the films, the film heated at 140◦ C for (vinyl alcohol) based ternary films as active packaging system, Carbohydr. Polym.
40 min shows overall superior mechanical behavior. Therefore, 193 (2018) 239–248, https://doi.org/10.1016/j.carbpol.2018.03.079.

9
S. Sau et al. Surfaces and Interfaces 25 (2021) 101198

[11] J.H. Kim, E.J. Moon, C.K. Kim, Composite membranes prepared from poly (m- [30] F. Jianqi, G. Lixia, PVA/PAA thermo-crosslinking hydrogel fiber: preparation and
animostyrene-co-vinyl alcohol) copolymers for the reverse osmosis process, pH-sensitive properties in electrolyte solution, Eur. Polym. J. 38 (2002)
J. Membr. Sci. 216 (2003) 107–120, https://doi.org/10.1016/s0376-7388(03) 1653–1658, https://doi.org/10.1016/S0014-3057(02)00032-0.
00063-2. [31] A.R. Patel, P.R. Vavia, Evaluation of synthesized cross linked polyvinyl alcohol as
[12] A. Bozdogan, B. Aksakal, O. Yargi, U. Sahinturk, Structural and tensile potential disintegrant, J. Pharm. Pharm. Sci. 13 (2010) 114–127, https://doi.org/
characteristics of reduced graphene oxide/poly (vinyl alcohol) composite films: 10.18433/J3XS3D.
influence of ultraviolet irradiation, Polym. Compos. 41 (2020) 3087–3100, https:// [32] M.G. Katz, T. Wydeven Jr., Selective permeability of PVA membranes. I. Radiation-
doi.org/10.1002/pc.25600. crosslinked membranes, J. Appl. Polym. Sci. 26 (1981) 2935–2946, https://doi.
[13] A.G. El-Shamy, W. Attia, K.M.A. El-Kader, The optical and mechanical properties of org/10.1002/app.1981.070260910.
PVA-Ag nanocomposite films, J. Alloys Compd. 590 (2014) 309–312, https://doi. [33] B. Aksakal, O. Yargi, U. Sahinturk, Uniaxial tensile and structural properties of poly
org/10.1016/j.jallcom.2013.11.203. (vinyl alcohol) films. The influence of heating and film thickness, J. Appl. Polym.
[14] A.A.M. Alfayyadh, S. Lotfy, A.A. Basfar, M.I. Khalil, Influences of poly (vinyl Sci. 134 (2017) 44915, https://doi.org/10.1002/APP.44915.
alcohol) molecular weight and carbon nanotubes on radiation crosslinking shape [34] N.A. Peppas, Crystallization of polyvinyl alcohol-water films by slow dehydration,
memory polymers, Progress Nat. Sci. 27 (2017) 316–325, https://doi.org/ Eur. Polym. J. 12 (1976) 495–498, https://doi.org/10.1016/0014-3057(76)90004-
10.1016/j.pnsc.2017.04.015. 5.
[15] M.N. Tousignant, N.A. Rice, A. Peltekoff, C. Sundaresan, C. Miao, W.Y. Hamad, B. [35] K. Maruyama, H. Akahoshi, M. Kobayashi, Y. Tanizaki, Assignment of conjugate
H. Lessard, Improving thin-film properties of poly (vinyl alcohol) by the addition of double bond systems produced in heated PVA film by absorption and excitation
low-weight percentages of cellulose nanocrystals, Langmuir 36 (2020) 3550–3557, spectra, Bull. Chem. Soc. Jpn. 58 (1985) 2923–2928, https://doi.org/10.1246/
https://doi.org/10.1021/acs.langmuir.0c00068. bcsj.58.2923.
[16] B. Gebben, H.W.A. van den Berg, D. Bargeman, C.A. Smolders, Intramolecular [36] C.W. Bunn, Crystal structure of polyvinyl alcohol, Nature 161 (1948) 929–930,
crosslinking of poly (vinyl alcohol), Polymer 26 (1985) 1737–1740, https://doi. https://doi.org/10.1038/161929a0.
org/10.1016/0032-3861(85)90295-2. [37] R.C.L. Mooney, An X-ray Study of the structure of polyvinyl alcohol, J. Am. Chem.
[17] B. Bolto, T. Tran, M. Hoang, Z. Xie, Crosslinked poly (vinyl alcohol) membranes, Soc. 63 (1941) 2828–2832, https://doi.org/10.1021/ja01855a095.
Progress in polymer science 34 (2009) 969-981. DOI:10.1016/j.progpolymsci.200 [38] L.E. Alexander, X-ray Diffraction Methods in Polymer Science, Wiley-interscience,
9.05.003. New York, 1970, https://doi.org/10.1107/S0021889870006969.
[18] A.K. Sonker, V. Verma, Influence of crosslinking methods toward poly (vinyl [39] G. Attia, M.F.H.A. El-kader, Structural, optical and thermal characterization of
alcohol) properties: microwave irradiation and conventional heating, J. Appl. PVA/2HEC polyblend films, Int. J. Electrochem. Sci. 8 (2013) 5672–5687.
Polym. Sci. 135 (2018) 46125, https://doi.org/10.1002/APP.46125. [40] M. Banerjee, A. Jain, G.S. Mukherjee, Microstructural and optical properties of
[19] A. Hasimi, A. Stavropoulou, K.G. Papadokostaki, M. Sanopoulou, Transport of polyvinyl alcohol/manganese chloride composite film, Polym. Compos. 40 (2019)
water in polyvinyl alcohol films: effect of thermal treatment and chemical 765–775, https://doi.org/10.1002/pc.25017.
crosslinking, Eur. Polym. J. 44 (2008) 4098–4107, https://doi.org/10.1016/j. [41] Y. Wang, C. Xiang, T. Li, P. Ma, H. Bai, Y. Xie, M. Chen, W. Dong, Enhanced
eurpolymj.2008.09.011. thermal stability and UV shielding properties of poly(vinyl alcohol) based on
[20] K. Kamemaru, S. Usui, Y. Hirashima, A. Suzuki, Irreversible swelling behavior and esculetin, J. Phys. Chem. B 121 (2017) 1148–1157, https://doi.org/10.1021/acs.
reversible hysteresis in chemically crosslinked poly(vinyl alcohol) gels, Gels 4 jpcb.6b11453.
(2018) 45. DOI:10.3390/gels4020045. [42] A. Sonker, A. Teotia, A. Kumar, R.K. Nagarale, V. Verma, Development of polyvinyl
[21] K. Kumeta, I. Nagashima, S. Matsui, K. Mizoguchi, Crosslinking reaction of poly alcohol based high strength biocompatible composite films, Macromol. Chem.
(vinyl alcohol) with poly (acrylic acid) (PAA) by heat treatment: effect of Phys. 218 (2017), 1700130, https://doi.org/10.1002/macp.201700130.
neutralization of PAA, J. Appl. Polym. Sci. 90 (2003) 2420–2427, https://doi.org/ [43] I. Yu. Prosanov, A.A. Matvienko, Study of PVA thermal destruction by means of IR
10.1002/app.12910. and Raman spectroscopy, Phys. Solid State 52 (2010) 2203–2206, https://doi.org/
[22] J. Tavakoli, J. Gascooke, N. Xie, B.Z. Tang, Y. Tang, Enlightening freeze− thaw 10.1134/S1063783410100318.
process of physically cross-linked poly(vinyl alcohol) hydrogels by aggregation- [44] D.K. Buslov, N.I. Sushko, O.N. Tretinnikov, IR investigation of hydrogen bonds in
induced emission fluorogens, ACS Appl. Polym. Mater. 1 (2019) 1390–1398, weakly hydrated films of poly(vinyl alcohol), Polym. Sci. 53 (2011) 1121–1127,
https://doi.org/10.1021/acsapm.9b00173. https://doi.org/10.1134/S0965545X11120030.
[23] M. Miraftab, A.N. Saifullah, A. Cay, Physical stabilisation of electrospun poly (vinyl [45] R. Hiss, S. Hobeika, C. Lynn, G. Strobl, Network stretching, slip processes, and
alcohol) nanofibres: comparative study on methanol and heat-based crosslinking, fragmentation of crystallites during uniaxial drawing of polyethylene and related
J. Mater. Sci. 50 (2015) 1943–1957, https://doi.org/10.1007/s10853-014-8759-1. copolymers. A comparative study, Macromolecules 32 (1999) 4390–4403, https://
[24] K. Kumeta, I. Nagashima, S. Matsui, K. Mizoguchi, Crosslinking of poly(vinyl doi.org/10.1021/ma981776b.
alcohol) via bis(β-hydroxyethyl) sulfone, Polym. J. 36 (2004) 472–477, https:// [46] R.N. Haward, Strain hardening of thermoplastics, Macromolecules 26 (1993)
doi.org/10.1295/polymj.36.472. 5860–5869, https://doi.org/10.1021/ma00074a006.
[25] M. Song, H. Yu, J. Gu, S. Ye, Y. Zhou, Chemical cross-linked polyvinyl alcohol/ [47] D. Liu, L. Yuan, H. Xu, H. Tian, A. Xiang, PVA grafted POSS hybrid for high
cellulose nanocrystal composite films with high structural stability by spraying performance polyvinyl alcohol films with enhanced thermal, hydrophobic and
fenton reagent as initiator, Int. J. Biol. Macromol. 113 (2018) 171–178, https:// mechanical properties, Polym. Compos. 40 (2019) 2768–2778, https://doi.org/
doi.org/10.1016/j.ijbiomac.2018.02.117. 10.1002/pc.25084.
[26] S. Gupta, A.K. Pramanik, A. Kailath, T. Mishra, A. Guha, S. Nayar, A. Sinha, [48] E. Rynkowska, K. Fatyeyeva, S. Marais, J. Kujawa, W. Kujawski, Chemically and
Composition dependent structural modulations in transparent poly (vinyl alcohol) thermally crosslinked PVA-based membranes: effect on swelling and transport
hydrogels, Colloids Surf. B 74 (2009) 186–190, https://doi.org/10.1016/j. behavior, Polymers 11 (2019) 1799, https://doi.org/10.3390/polym11111799.
colsurfb.2009.07.015. [49] S. Kim, J. Jang, Effect of degree of polymerization on the mechanical properties of
[27] P.R. Byron, R.N. Dalby, Effects of heat treatment on the permeability of polyvinyl regenerated cellulose fibers using synthesized 1-allyl-3-methylimidazolium
alcohol films to a hydrophilic solute, J. Pharm. Sci. 76 (1987) 65–67, https://doi. chloride, Fibers Polym. 14 (2013) 909–914, https://doi.org/10.1007/s12221-013-
org/10.1002/jps.2600760118. 0909-6.
[28] F.J. Liou, Y.J. Wang, Preparation and characterization of crosslinked and heat- [50] H. Jiang, W. Su, P.T. Mather, T.J. Bunning, Rheology of highly swollen chitosan/
treated PVA-MA films, J. Appl. Polym. Sci. 59 (1996) 1395–1403, https://doi.org/ polyacrylate hydrogels, Polymer 40 (1999) 4593–4602, https://doi.org/10.1016/
10.1002/(SICI)1097-4628(19960228)59:9<1395::AID-APP7>3.0.CO;2-6. s0032-3861(99)00070-1.
[29] M.G. Katz, T. Wydeven Jr., Selective permeability of PVA membranes. II. heat- [51] A.K. Sonker, H.D. Wagner, R. Bajpai, R. Tenne, X.M. Sui, Effects of tungsten
treated membranes, J. Appl. Polym. Sci. 27 (1982) 79–87, https://doi.org/ disulphide nanotubes and glutaric acid on the thermal and mechanical properties
10.1002/app.1982.070270109. of polyvinyl alcohol, Compos. Sci. Technol. 127 (2016) 47–53, https://doi.org/
10.1016/j.compscitech.2016.02.030.

10