Chemical Data Collections 26 (2020) 100338

Contents lists available at ScienceDirect

Chemical Data Collections

journal homepage: www.elsevier.com/locate/cdc

Data Article

Preparation and characterization of PVA-Ge/PEG-400

biodegradable plastic blend films for packaging applications
Ashok M. Sajjan a,∗, Manu L. Naik a, Akshay S. Kulkarni a, Umme Fazal-E-Habiba
Rudgi a, Ashwini M b, Geeta G. Shirnalli b, Sharanappa A c, Prakash B. Kalahal a
a
Department of Chemistry, KLE Technological University, Hubballi 580031, India
b
Department of Food and Industrial Microbiology, University of Agricultural Sciences, Dharwad 580 005, India
c
Department of Biotechnology, KLE Technological University, Hubballi 580031, India

a r t i c l e i n f o a b s t r a c t

Article history: Biodegradable poly(vinyl alcohol) (PVA)-Gelatin (Ge)/polyethylene glycol-400 (PEG-400)

Received 14 October 2019 films were prepared with various mass% of PEG-400 with respect to PVA. These films were
Revised 24 December 2019
then cross-linked using formaldehyde to enhance the barrier properties. Physico-chemical
Accepted 30 December 2019
characteristics of the developed films were analyzed using Fourier transform infrared spec-
Available online 13 January 2020
troscopy (FTIR), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry
Keywords: (DSC), universal testing machine (UTM), scanning electronic microscopy (SEM) and con-
Poly (vinyl alcohol) tact angle analyzer. In order to check the efficiency of the developed films for packaging
Gelatin applications, barrier properties such as water vapor transmission rate (WVTR), moisture
PEG-400 retention capability (MRC), swelling measurement and film solubility were analyzed. FTIR
Formaldehyde and WAXD confirmed the cross linking between the PVA and Ge components, and the ef-
Tensile strength fect of hydrogen bonds on the crystallization. Formaldehyde cross-linking has immensely
Film solubility influenced the tensile strength and elongation at break of the films. Further, it has also im-
proved the film solubility and water barrier properties when compared to uncross linked
films. These biodegradable films can be used in the field of packaging as a material to
produce bags for daily use.
© 2020 Elsevier B.V. All rights reserved.

Specifications Table

Subject area Biodegradable polymers

Compounds Poly(vinyl alcohol), Gelatin, Polyethylene glycol-400, Formaldehyde
Data category Spectral, Physico-chemical, Experimental
Data acquisition FTIR, WAXD, DSC, UTM, SEM, Experimental analysis
format
Data type Analyzed
Procedure Gelatin cross-linked poly(vinyl alcohol) films were incorporated with polyethylene glycol-400 in different mass%. The
resulting films were subjected to physico-chemical investigations using FTIR, WAXD, DSC and SEM. Developed films were
then cross-linked using formaldehyde. The effects of PEG-400 on packaging performance of the cross-linked films were
systematically studied. The film containing 5 mass% of PEG-400 exhibited 79.66 MPa of tensile strength, 0.144 g/cm2 h
water vapor transmission rate, and 95.85% moisture retention capability. The film solubility values are almost overlapping
each other manifesting that these films could be used effectively for packaging applications.
Data accessibility All the data are provided in the article.

∗
Corresponding author.
E-mail address: ashokmsajjan@gmail.com (A.M. Sajjan).

https://doi.org/10.1016/j.cdc.2020.100338
2405-8300/© 2020 Elsevier B.V. All rights reserved.
2 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

Nomenclature

Mw Molecular weight
WVTR Water vapor transmission rate
DS Degree of swelling (%)
A Area of the mouth of the bottle
MRC Moisture retention capability
Ws and Wd Weight of the swollen and dry films
FS Film solubility
Mw Molecular weight
T Time (h)
T temperature
Wt and Wi Final and initial weight of the Films

1. Rationale

Packaging is done in order to maintain product quality and safety. Various materials have been used to develop the
packaging films but plastic plays a major role. Plastic stand second most widely used material for packaging applications,
among which polypropylene, polyethylene, polystyrene, and polyethylene terephthalate have been used for the production of
packaging materials which are not biodegradable but their potential properties such as flexibility, strength, stability, trans-
parency, and permeability which make them suitable for packaging applications [1–3]. However, these plastics which take
millennia to degrade gives out harmful greenhouse gases when it is buried or in a landfill have a greater impact on the
environment [4,5]. On large scale, the disposal of 500 billion plastic bags that are being used on a daily base, whereas only
3% of it is being recycled has marked an increase in the demand for the production of ‘biodegradable plastics’ which can
help in order to reduce the pollution. Materials that can be decomposed by microorganisms like bacteria, yeasts and fungi
are “Biodegradable” materials [6].
Biodegradable polymers offer many advantages over non-biodegradable; they have excellent mechanical properties
along with the degradation. Number of materials that has been used for the preparation of packaging materials which
have biodegradable property are starch, PVA, polylactic acid (PLA), poly(butylene adipate) (PBA), poly(butylene succinate)
(PBS), poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(propylene carbonate) and poly-3-hydroxybutyrate [7–
17]. Some of the biodegradable films have greater degradation ability but exhibits lesser mechanical strength [18]. Among
these, PVA is a biodegradable polymer with excellent properties such as chemical resistance, film-forming ability, hydrophilic
and high crystalline nature but doesn’t exhibit high mechanical and thermal stability [19,20]. To accomplish enhanced per-
formance from the PVA film as a packaging material, it requires alteration [21–24]. Many alteration methods like cross-
linking, plasticizing, and incorporation of nanoparticles are used to improve the mechanical properties, barrier properties,
and thermal stability [25,26].
In order to meet the global requirement of a biodegradable property with high strength, this research has been carried
out wherein PVA-Ge films were prepared in the presence of various mass% of PEG-400 as a plasticizer. These films were
further cross-linked using formaldehyde in order to make them insoluble in water. The Physico-chemical properties of the
prepared films were analyzed using the Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD),
scanning electronic microscopy (SEM), contact angle measurements and universal testing machine (UTM). Further, the pack-
aging performance of the films was tested by water vapor transmission rate (WVTR), moisture retention capability (MRC),
film solubility (FS) and swelling measurement.

2. Procedure

2.1. Materials

Poly(vinyl alcohol) molecular weight~125,0 0 0 and degree of hydrolysis (86–89%), gelatin, polyethylene glycol-400 and
formaldehyde were purchased from s. d. fine Chemicals Ltd., Mumbai, India. Hydrochloric acid was procured from E. Merck
Ltd., Mumbai, India. Acetone was purchased from RFCL Ltd., New Delhi, India. All the chemicals were of reagent grade and
used without further purification. Double distilled water was used for the experiments.

2.2. Film preparation

PVA (8 g) was dissolved in 100 ml of de-aerated double distilled water at 60 °C with a constant stirring for about 24 h
and then filtered using a fritted glass disc filter to remove un-dissolved residue particles and the solution was left overnight
 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338 3

to release the air bubbles. The resulting homogeneous solution was cast onto a glass plate with the help of a casting knife
in a dust-free environment. The film was allowed to dry at room temperature for 2–3 days. The completely dried film was
subsequently peeled-off from the glass plate and it was designated as F-0.
Ge cross-linked PVA film was prepared by adding a known amount of Ge (10 mass% with respect to PVA) and 0.1 ml
HCl to the above-prepared solution and kept for steady stirring at 60 °C for 3 h [25]. The solution was then filtered and the
remaining procedure was similar to the preparation method of film F-0 and the resultant film was named as F-1.
In order to prepare PEG-400 incorporated PVA-Ge films, the various quantity of PEG-400 was added to the above PVA-Ge
homogenous solution and stirred at 60 °C for 3 h. The solution was then filtered and the remaining procedure was similar
to the preparation method of film F-1. The quantity of PEG-400 was varied as 5, 10, 15 and 20 mass% with respect to PVA
and developed films were designated as F-2, F-3, F-4, and F-5 respectively.
All the films were further cross-linked using formaldehyde in the presence of acetone as solvent and HCl catalyst at
ambient temperature for 10 min. The films were washed and rinsed repeatedly using distilled water. The thickness of the
films was measured at different points using a Peacock dial thickness gauge (Model G. Ozaki, MFG Co. Ltd., Japan) with an
accuracy of ± 2 μm. The thickness of the films was found to be 107 ± 2 μm. The chemical structure and reaction route of
the film is shown in Fig. 1.

2.3. Fourier transform infrared (FTIR) spectroscopy

Confirmation of reaction between PVA–10 mass% Ge and incorporated PEG-400 was done by FTIR Spectrometer
(PerkinElmer spectrum, Singapore). Analysis was done using diamond ATR and a spectrum was recorded in the range of
50 0–40 0 0 cm−1 . In each scan, it was analyzed to know the changes in the intensities of the characteristic bands with re-
spect to the Ge and PEG-400.

2.4. Wide-angle X-ray diffraction (WAXD)

The X-ray diffractogram pattern of PVA–10 mass% Ge and different mass% of PEG-400 incorporated films were recorded
using a Philips Analytical X-ray Diffractometer. For recognition of dried film crystal phases, samples having even thickness
(~107 μm) were mounted on the sample holder and scanned in the reflection mode at an angle 2ϴ over a range of 5°–50°
at a speed of 8°/min.

2.5. Differential scanning calorimetry (DSC)

Differential scanning calorimeter (DSCQ 20, TA Instruments, Waters LLC, and New Castle, DE, USA) was used to study the
thermal properties of PVA–10 mass% Ge and incorporated PEG-400 films. Weight of samples ranging from 9 to 10 mg which
were subjected to heat from atmospheric temperature to 250 °C under nitrogen atmosphere at a heating rate of 10 °C/min.

2.6. Scanning electron microscopy (SEM)

Scanning electron microscope (JEOL, JSM-400 o A, Tokyo, Japan) was used to examine the surface and cross sectional
views of the PVA and PVA–10 mass% Ge. Film samples were completely dried in order to take photograph coated with a
conductive layer (400 o A) of sputtered gold.

2.7. Contact angle measurements

The sessile droplet method was used to analyze static contact angles of water of PVA–10 mass% Ge and incorporated
PEG-400 films with the help of a contact angle analyzer (Phoenix 300, South Korea) attached with a video camera. Each
sample was tested for contact angle of the water droplet with a time period of 10 s after placing it on the prepared films.
With precision and accuracy provided by the software, the contact angle was measured with respect to the shape of the
water droplet formed on the films.

2.8. Water vapor transmission rate (WVTR)

10 ml of distilled water was taken in a glass bottle with a diameter of 29.5 mm. The opening of the bottle was wrapped
with film and was tightened with Teflon tape. Initial weight of the bottle was measured followed by incubation in oven at
40 °C for 24 h. After the incubation period bottle was taken out and final weight was measured.
The WVTR was measured from the following formula:
W − W 
i t
WV T R = ×T (1)
A
where, T = 24 h; Wi = initial weight of glass bottle; Wt = final weight of glass bottle; A = area of the circular mouth of
glass bottle in cm2
4 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

Fig. 1. Scheme for the preparation and structural representation of PVA-Ge/PEG-400 biodegradable blend film.
 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338 5

2.9. Moisture retention capability (MRC)

To calculate the moisture retention capability (MRC), pieces of equally thick film were taken and weighed. Then films
were kept in the oven for 6 h at 40 °C. MRC was calculated by using the following formula:
W 
t
MRC % = × 100 (2)
Wi
Where Wi is the initial weight before incubating in the oven and Wt is the final weight after the films were taken out from
an oven.

2.10. Film water solubility

Wet method was used to determine the film water solubility (FS) with minor modifications. 50 ml centrifuge tube con-
taining 10 ml of distilled water with 0.1% (w/v) sodium azide and weighed film samples (1 cm × 1 cm) was stirred at
room temperature for 24 h followed by centrifugation at 30 0 0 rpm for 15 min at 25 °C. The undissolved film was dried at
60 °C for 24 h and weighed again. Minimization of error was done by triplicate test and the film solubility was determined
according to the following equation:
 
Wi − W f
F S (% ) = × 100 (3)
Wf
Where, Wi was the initial weight expressed as dry film and Wf was the dry weight of the undissolved film.

2.11. Swelling measurement

A known quantity of dried film samples were taken to estimate the degree of swelling. These film samples were im-
mersed in distilled water in sealed vessels at 40 °C for 24 h. Weight of the swollen films were taken immediately on a
digital microbalance (Mettler, B204-S, Toledo, Switzerland) with an accuracy of ± 0.01 mg. Experiments were performed in
triplicate and the average of the triplicate readings were taken.
W − W 
s d
DS (% ) = × 100 (4)
Wd
Where Wd and Ws are the masses of the dry and swollen films respectively.

2.12. Degradability test

To examine the biodegradability of PVA-Ge/PEG-400 film, soil burial test was carried out on a laboratory scale. Square
shaped specimens of definite sizes were cut from each of the film. Moist soil was placed into plastic containers with tiny
holes that were perforated at the bottom and on the body of the container to increase air, and water circulation. The test
was carried out outside the room and lasted for 70 days. The specimens were buried in the soil at a depth of 10 cm from the
surface and thus subjected to the action of microorganisms in which soil is their major habitat. After the test, the samples
were removed, washed with distilled water and dried in an oven at 70 °C for 24 h and weighed to analyze the weight loss.

3. Data, value, and validation

3.1. Film characterization

3.1.1. FTIR studies

Fig. 2 shows the FTIR spectra of the PVA, Ge, PVA-Ge, PEG-400 and 10 mass% PEG-400 incorporated PVA-Ge films. A
pristine PVA film (F-0) demonstrates O–H stretching vibration band at around 3330 cm−1 , C=O and C–O stretching from
acetate group and C–O stretching vibration peaks appeared between 10 0 0 cm−1 and 1248 cm−1 [27,28]. Further, the spec-
trum of pure Ge exhibits a typical absorption peak at 3279 cm−1 which represents N–H stretching and hydroxyl group
(O–H). The peak visible at 2922 cm−1 was due to asymmetric –CH2 stretching. The characteristic sharp peak appeared at
1244 cm−1 was due to C–N stretching vibration. The peak at 1628 cm−1 indicates the presence of –C=O stretching and
hydrogen bonding coupled with COO– stretching [29,30]. However, in PVA–Ge film, the O–H band was marginally shifted to
lower wavenumbers (3288 cm−1 ) which indicates the interaction between secondary amide group of Ge and hydroxyl group
of PVA. Further, the band was broadened which is due to the overlapping of O–H band of PVA with N–H band of Ge. Simi-
larly, peak appeared in Ge at 1628 cm−1 corresponding to the –COO– group is disappeared in the spectrum of PVA-Ge. This
disappearance of peak at 1628 cm−1 indicating the esterification reaction between the carboxylic group of Ge and hydroxyl
group of PVA [23]. On the contrary, the peak at 1628 cm−1 has been shifted to 1733 cm−1 which clearly ascertain that the
free carboxylic groups of Ge underwent esterification, leading to crosslinks between OH groups of PVA and COOH groups of
Ge.
6 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

Fig. 2. FTIR spectra of PVA, Ge, PVA-10 mass% gelatin and its incorporated PEG-400 film: Pure PVA (F-0); Pure gelatin (Ge); PVA-10 mass% gelatin (F-1);
Pure PEG-400; 5 mass% of PEG-400 (F-2).

Spectrum of pristine PEG-400 showed that the characteristics broad band exhibited at 3450 cm−1 which indicates the
presence of an O–H stretching vibration, the peak appeared at 2863 and 1456 cm−1 were due to CH2 stretching and
bending vibrations respectively [31]. In 10 mass% of PEG-400 incorporated PVA-Ge film, the O–H stretching vibration peak
(3450 cm−1 ) of PEG-400 was shifted towards the lower wavenumber (3282 cm−1 ) which indicates that there is hydrogen
bonding between the PVA, Ge, and PEG-400 [24].

3.1.2. Wide-angle X-ray diffraction studies (WAXD)

Fig. 3 illustrates WAXD patterns of pure PVA, PVA-10 mass% Ge and its PEG-400 incorporated films. The diffraction of
pure PVA shows a typical peak around 2ϴ = 20° indicating that the pure PVA contains both crystalline and amorphous
domains in the film matrix. In film F-1, the intensity of the diffraction peak at 2ϴ = 20° was found enhanced.
This is due to the rearrangement of PVA chains by the reaction between PVA and Ge which enhances the crystalline
nature of the film. However, from the films F-2 to F-5, as the incorporation of PEG-400 into the PVA-Ge matrix increased,
the intensity of the peak 2ϴ = 20° was found declining. This was expected as the PEG-400 acts as a plasticizer and disorders
the PVA-Ge chains which makes the amorphous nature predominate in the films F-2 to F-5.

3.1.3. Differential scanning calorimetry (DSC)

Glass transition temperature (Tg) plays a vital role in the analysis of the thermal properties of the developed films [32].
DSC analysis of the developed films was carried out in the temperature range of 45–400 °C. The resulting thermograms of
crosslinked PVA-Ge and its PEG-400 incorporated films are shown in Fig. 4. From the figure, it is observed that, the Tg of
pure PVA (F-0) is 85 °C [25], when 10 mass% of Ge was added into the PVA matrix, the Tg of PVA-Ge film was drastically
increased from 85 to 105 °C. This is because of the compactness of the film matrix owing to the 3D network like structure
formed after the cross-linking reaction between PVA and Ge. However, the addition of 5 mass% PEG-400 into the PVA-
Ge film, the Tg value increased slightly to 106 °C which is due to hydrogen bonding. For the films, F-3 to F-5, a higher
concentration of PEG-400 leads to the disturbance in the arrangement of PVA-Ge chains which overcomes the hydrogen
bonding and makes the amorphous nature predominate in the films F-3 to F-5. Further, melting temperature peak (Tm )
is appearing around 187 °C in PVA film. However, for the films F-1 to F-5 it was slightly increased (187 to 191 °C). The
decomposition endothermic peak for the PVA-Ge film was 309 °C. In the case of PEG-400 incorporated films, decomposition
 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338 7

Fig. 3. Wide-angle X-ray diffraction patterns of pure PVA, PVA-10 mass% Ge and its incorporated PEG-400 films: pure PVA (F-0); PVA-10 mass% Ge (F-1);
5 mass% of PEG-400 (F-2); 10 mass% of PEG-400 (F-3); 15 mass% of PEG-400 (F-4); 20 mass% of PEG-400 (F-5).

Table 1
Tensile strength and elongation at break values of de-
veloped films.

Before crosslinking After crosslinking

Films TS (MPa) (%)EAB TS (MPa) (%)EAB

F-0 18.59 151.89 53.86 64.55

F-1 25.31 195.88 61.33 17.76
F-2 27.09 255.92 79.66 16.54
F-3 24.93 228.67 64.06 18.46
F-4 12.76 114.418 54.00 63.45
F-5 17.36 177.147 53.86 65.75

endothermic peak decreased and also the area under the curve is decreased. This clearly shows that F-1 and F-2 exhibit
high thermal stability.

3.1.4. Mechanical strength

Mechanical strength is a vital factor in deciding the viability of the films in packaging applications. Generally, biodegrad-
able films exhibit lower mechanical strength compared to non-biodegradable plastic [18]. The mechanical strength of the
films generally depends on the chemical structure and the nature of the film-forming materials [33]. The tensile strength
and elongation at break values of the developed films were analyzed and listed in Table 1.
From the results, it was clearly observed that the effect of formaldehyde cross-linking was prominent on the tensile
strength and elongation at break of the films. The values demonstrate that the tensile strength was drastically increased
for the formaldehyde cross-linked films compared to uncrosslinked films. In uncross linked films; F-0 exhibited the tensile
strength of 18.59 MPa. Further, in F-1 the tensile strength increased to 25.31 MPa. This is due to the rearrangement of
PVA chains by the reaction between PVA and Ge which enhances the crystalline nature of the film. As the addition of 5
8 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

Fig. 4. Thermograms of pure PVA, PVA-10 mass% Ge and its incorporated PEG-400 films: pure PVA (F-0); PVA-10 mass% Ge (F-1); 5 mass% of PEG-400
(F-2); 10 mass% of PEG-400 (F-3); 15 mass% of PEG-400 (F-4); 20 mass% of PEG-400 (F-5).

mass% PEG-400 into PVA-Ge film (F-2) demonstrated the highest tensile strength (27.09 MPa) which is due to the hydrogen
bonding. However, for the films F-3 to F-5 the tensile strength was decreased continuously as the content of PEG-400 in
the PVA-Ge matrix increased, which is due to the disturbance in the arrangement of PVA-Ge chains which makes the films
more amorphous in nature. The tensile strength and elongation at break values of the formaldehyde cross-linked films were
also listed in Table 1. From the table, it is clear that F-2 exhibited the highest tensile strength (79.66 MPa) compared to
all other films with the percentage elongation at break of 16.54, which suggests that formaldehyde cross-linked 5 mass%
PEG-400 incorporated PVA-Ge film is suitable for preparation of shopping bags.

3.1.5. Scanning electron microscopy (SEM)

From SEM photographs (Fig. 5), it can be spotted that surface views of PVA and PVA-Ge films are even and homogenous.
There is no sign of phase separation and voids in the film matrix of F-1 which indicates complete interaction between PVA
and Ge and shows good compatibility between the two moieties

3.1.6. Contact angle analysis

Hydrophilicity of the film surface is one of the crucial properties, which can influence the antifouling ability and water
vapor transmission rate of the film [34]. Contact angle values of the developed films are shown in Fig. 6.
From the Figure, it was noticed that the film F-0 has shown the lower contact angle value of 43° but film F-1 has shown
53°, this sharp increase in the surface contact angle of film F-1 is mainly because of formation of network structure through
cross-linking reaction between –OH group of PVA and –COOH group of Ge which would cause decrease in contact angle.
Further, from film F-2 to F-5 the contact angle values gradually increased as the concentration of PEG-400 was enhanced in
the film matrix. This enhancement in the contact angle was obvious as the plasticizing nature of the PEG-400 will increase
the hydrophobicity of the films.

3.1.7. Water vapor transmission rate (WVTR) of developed films

Films are considered suitable for packaging if they possess the property of inhibiting moisture from getting inside from
the environment. Films with lower water vapor transmission rate are considered ideal for packaging applications. Table 2
shows the WVTR values of developed films. From the values, it was noticed that the WVTR decreased as the content of
PEG-400 increased in the film matrix. This is due to the decreased hydrophilicity of the films [29]. As the content of the
plasticizer was increased, the structure of the film became more and more compact and the tortuously was enhanced.
 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338 9

Fig. 5. The SEM images of pure PVA (F-0) and PVA-10% Ge (F-1).

Table 2
Water vapor transmission rate, moisture retention capability, film solubility and swelling analysis of developed films.

Water Vapor Transmission Moisture Retention Capability Film solubility (dissolution Swelling in
Film Rate(WVTR) in (g/cm2 h) (MRC) in (%) rate) in (%) (%)

F-0 0.227 95.64 10.89 36.66

F-1 0.183 95.70 10.80 20.16
F-2 0.144 95.85 10.69 19.12
F-3 0.087 95.98 10.28 18.09
F-4 0.081 96.20 10.17 17.86
F-5 0.075 96.29 10.37 16.14

Enhanced tortuous path and the compactness of the film made the diffusion of water vapors difficult. Moreover, due to
covalent cross-linking and plasticizing effect intermolecular spacing in the matrix of the films was also reduced. All these
factors affected the WVTR values of the prepared films.

3.1.8. Moisture retention capability

Moisture retention capability illustrates the loss of water vapors from the films. Controlling moisture movement from the
films is vital to sustain the taste, texture, and quality of the packaged products [4]. Table 2 illustrates the moisture retention
capability of the developed films. From the observed values, it is clearly noticed that the moisture retention capability of the
10 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

Fig. 6. Contact angle measurement of composite films: pure PVA, PVA-10 mass% Ge and its incorporated PEG-400 films: pure PVA (F-0); PVA-10 mass% Ge
(F-1); 5 mass% of PEG-400 (F-2); 10 mass% of PEG-400 (F-3); 15 mass% of PEG-400 (F-4); 20 mass% of PEG-400 (F-5).

developed films is high. The results ranged from 95.64% to 96.29% which shows that the developed films have almost the
same moisture retention capability irrespective of their composition. These good moisture retention capability values were
expected due to water holding groups present in the developed films. The hydroxyl groups have the capability of holding the
water molecules inside the developed films. Multiple –OH and –NH groups present in the Ge makes it an excellent water
absorber and holder. Hence Ge acts as water-holding agent and plays a vital role in good moisture retention capability values
of the developed films [27].

3.1.9. Swelling measurements

Swelling measurement values of the developed films are shown in Table 2. From the values, it was noticed that the film
F-0 has shown 36.66% of swelling but film F-1 has shown 20.16% of swelling. This sharp decrease in the swelling of film
F-1 can be attributed to the formation of the bond between PVA and Ge due to reaction between –OH group of PVA and
–COOH group of Ge. Further, from film F-2 to F-5 the swelling gradually decreased as the content of PEG-400 was enhanced
in the film matrix. This decrease in the swelling was obvious as the plasticizing nature of the PEG-400 will increase the
hydrophobicity of the films. These results are also reflected in the contact angle analysis of the films.

3.1.10. Film solubility

Lower solubility values are suitable for the films to be used for storage purposes [34]. Solubility values of developed
films are shown in Table 2. The cross-linked films demonstrated very low film solubility value which is obvious as the
crosslinking using formaldehyde not only stabilize the films but also decrease their solubility in the aqueous medium. All
the values mentioned in the table are almost similar to each other with minimal differences with F-4 demonstrating the
lowest value (10.17%). The lower solubility values indicate that all the films exhibit good stability in aqueous medium and
are suitable for packaging applications.

3.1.11. Degradability test

The degradability test helps us to understand the amount of the sample degrades in the soil due to microbial degradation.
The Fig. 7 shows the degradation of the film. Degradation of the film showed an increasing nature revealing that as the
number of days increases % of weight loss increases proportionally. PVA and PEG-400 acts as a source of carbon and energy
for the microorganisms and the enzymes oxidizes and hydrolyses will help in the degradation [24,35]. But the Ge material
of the film which serves as a nutrient to the various fungi and bacteria promotes the growth and help enzyme production.
Microorganisms excrete the extracellular enzymes, which then adheres to the surface of the polymer and cleave the polymer
chain resulting in fragments that readily loses its property and degrade the material. Hence, these actions of the extracellular
enzymes produced by the microorganisms found in flora of the soil degrade the film. The % of weight loss was less at the
initial 20 days which was in the range of 0.5–2%. Whereas 30 days and after, % of weight loss was in the range of 2–4%
due to suitable adjustment of the material in the environment and maximum degradation by the microbes. However, after
 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338 11

Fig. 7. Degradation of PVA-Ge/5 mass% PEG-400 film in the soil.

the 50th day, the % of weight loss was constant hence indicating that the average % of weight loss for 10 days was 2.5%.
Therefore we can conclude that the film degrades approximately in a year.

4. Conclusions

In this research work, PVA–Ge/PEG-400 biodegradable films were developed. FTIR confirmed the interaction between
PVA, Ge, and PEG-400. WAXD analysis illustrated that the amorphous nature of the films was enhanced due to the incorpo-
ration of PEG-400 as a plasticizer. DSC analysis revealed that PVA-Ge/ 5 mass% PEG-400 films demonstrated higher Tg value
(106 °C) compared to all films which indicate that films possess excellent thermal stability. Cross-linked film F-2 has shown
excellent mechanical strength as it has a good tensile strength (79.66 MPa) which is on par with non-biodegradable plas-
tics. Formaldehyde cross-linked films exhibited low water solubility (10.89 to 10.17%), water vapor transmission rate (0.227
to 0.075 g/cm2 h) and high moisture retention capability (95.64 to 96.29%). Hence, the developed films can be potentially
used for the preparation of shopping bags.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Acknowledgments

One of the authors (Dr. Ashok M. Sajjan) gratefully acknowledges financial support from Vision Group on Science and
Technology, Karnataka, India (no. K-FIST (L2)/2016-17/GRD-540/2017-18/103/130).

References

[1] J. Muller, C.G. Martinez, A. Chiralt, Combination of poly(lactic acid) and starch for biodegradable food packaging, MTL 10 (2017) 952.
[2] R.B. Pearson, PVC as a food packaging material, Food Chem. 8 (1982) 85–96.
[3] A. Sangroniz, J.B. Zhu, X. Tang, A. Etxeberria, E.Y.X. Chen, H. Sardon, Packaging materials with desired mechanical and barrier properties and full
chemical recyclability, Nat. Commun. (2019).
[4] M.S. Salman, M.B.K. Niazi, Z. Jahan, T. Ahmad, A. Hussain, Preparation and characterization of PVA/nanocellulose/Ag nanocomposite films for antimi-
crobial food packaging, Carbohydr. Polym. 184 (2017) 453–464.
[5] L. Lopusiewicz, F. Jedra
˛ , A. Bartkowiak, New active packaging films made from Ge modified with fungal melanin, WSN 101 (2018) 1–30.
[6] L.R. Krupp, W.J. Jewell, Biodegradability of modified plastic films in controlled biological environments, Environ. Sci. Technol. 26 (1992) 193–198.
[7] S. Tunc, O. Duman, Preparation and characterization of biodegradable methyl cellulose/montmorilonite nanocomposites films, Appl. Clay Sci. 48 (2010)
414–424.
[8] C. Chen, L. Dong, M.K. Cheung, Preparation and characterization biodegradable poly(L-Lactide)/chitosan blend, Eur. Polym. J. 41 (2005) 958–966.
[9] N. Follian, C. Joly, P. Dole, C. Bliard, Properties of starch based blends. Part 2. Influence of poly vinyl alcohol addition and photo crosslinking on starch
based materials mechanical properties, Carbohydr. Polym. 60 (2005) 185–192.
[10] N. Tudorachi, C.N. Cascaval, M. Rusu, M. Pruteanu, Testing of polyvinyl alcohol and starch mixtures as biodegradable polymeric materials, Polym. Test.
19 (20 0 0) 785–799.
[11] S. Godbole, S. Gote, M. Latkar, T. Chakrabarti, Preparation and characterization of biodegradable poly-3-hydroxybutyrate–starch blend films, Bioresour.
Technol. 86 (2003) 33–37.
[12] S.H. Imam, P. Cinelli, S.H. Gordon, E. Chiellini, Characterization of biodegradable composite films prepared from blends of poly(vinyl alcohol), corn-
starch, and lingo cellulosic fiber, J. Polym. Environ. 13 (2005) 47–55.
[13] R. Muthuraj, T. Mekonnen, Carbon dioxide–derived poly(propylene carbonate) as a matrix for composites and nanocomposites: performances and
applications, Macromol. Mater. Eng. (2018) 1800366.
12 A.M. Sajjan, M.L. Naik and A.S. Kulkarni et al. / Chemical Data Collections 26 (2020) 100338

[14] F. Parvin, M.A. Rahman, J.M.M. Islam, Preparation and characterization of starch/pva blend for biodegradable packaging material, Adv. Mater. Res.
123-125 (2010) 351–354.
[15] P. Zhao, W. Liu, Q. Wu, J. Ren, Preparation, mechanical, and thermal properties of biodegradable polyesters/poly(lactic acid) blends, J. Nanomater.
(2010) 1–8.
[16] R. Muthuraj, M. Misra, A.K. Mohanty, Biodegradable poly(butylene succinate) and poly(butylene adipate-co-terephthalate) blends: reactive extrusion
and performance evaluation, J. Polym. Environ. (2014).
[17] I. Vroman, L. Tighzert, Biodegradable polymers, Materials. 2 (2009) 307–344.
[18] C. Pires, C. Ramos, G. Teixeira, L. Batista, R. Memdes, L. Nunes, A. Marques, Characterization of biodegradable films prepared with hake proteins and
thyme oil, J. Food Eng. 105 (2011) 423–428.
[19] T.S. Gaaz, A.B. Sulong, M.N. Akhtar, A.A.H. Kadhum, A.B. Mohamad, A.A. Al- Amiery, Properties and applications of polyvinyl alcohol, halloysite nan-
otubes and their nanocomposites, Molecules 20 (2015) 22833–22847.
[20] A.D. Campos, J.C. Marconato, S.M.M. Franchetti, Biodegradation of blend films PVA/PVC, PVA/PCL in soil and soil with landfill leachate, Braz. Arch. Biol.
Technol. 54 (2011) 1367–1378.
[21] M.S.N. Salleh, N.N.M. Nor, N. Mohammed, S.F.S. Draman, Water resistance and thermal properties of polyvinyl alcohol-starch fiber blend film, AIP Conf.
Proc. 1809 (2017) 020 045–1-020 045 -10.
[22] D.R. Lu, C.M. Xiao, S.J. Xu, Starch-based completely biodegradable polymer materials, Express Polym. Lett. 3 (2009) 366–375.
[23] K. Qiu, A.N. Netravali, Polyvinyl alcohol based biodegradable polymer nanocomposites, Biodegradable Polym. 1 (2016) 325–379.
[24] N.B. Halima, Poly(vinyl alcohol): review of its promising applications and insights into biodegradation, RSC Adv. 6 (2016) 39823–39832.
[25] A.M. Sajjan, M.Y. Kariduraganavar, Development of novel membranes for PV separation of water-isopropanol mixtures using poly(vinyl alcohol) and
gelatin, J. Memb. Sci. 438 (2017) 8–17.
[26] S. Duan, T. Kai, T. Saito, K. Yamazaki, K. Ikeda, Effect of cross-linking on the mechanical and thermal properties of poly(amidoamine) den-
drimer/poly(vinyl alcohol) hybrid membranes for CO2 separation, Membranes 4 (2014) 200–209.
[27] A.S. kulkarni, S.M. Badi, A.M. Sajjan, N.R. Banapurmath, M.Y. Kariduraganavar, A.S. Shettar, Preparation and characterization of B2SA grafted hybrid
poly(vinyl alcohol) membranes for pervaporation separation of water-isopropanol mixtures, Chem. Data Collec. 22 (2019) 100245.
[28] H.S. Mansur, C.M. Sadahira, A.N. Souza, A.A.P. Mansur, FTIR spectroscopy characterization of poly (vinyl alcohol) hydrogel with different hydrolysis
degree and chemically crosslinked with glutaraldehyde, Mater. Sci. Eng. C 28 (2008) 539–548.
[29] Y. Wang, Z. Guo, Y. Qian, Z. Zhang, L. Lyu, Y. Wang, F. Ye, Study on the electrospinning of ge/pullulan composite nanofibers, Polymers (Basel) 11 (2019)
1424.
[30] Y. Liua, L.M. Geever, J.E. Kennedy, C.L. Higginbotham, P.A. Cahill, G.B. McGuinness, Thermal behaviour and mechanical properties of physically
crosslinked PVA/gelatin hydrogels, J. Mech. Behav. Biomed. Mater. 3 (2010) 203–209.
[31] M.A. Marcos, D. Cabaleiro, M.J.G. Guimarey, M.J.P. Comuñas, L. Fedele, J. Fernández, L. Lugo, PEG 400-based phase change materials nano-enhanced
with functionalized graphenenanoplatelets, Polymers (Basel) 8 (2017) 16.
[32] F.H. Falqi, O.A. Bin-Dahman, M. Hussain, M.A. Al-Harthi, Preparation of miscible pva/peg blends and effect of graphene concentration on thermal,
crystallization, morphological, and mechanical properties of pva/peg (10wt%) blend, Int. J. Polym. Sci. (2018) 1–10.
[33] P. Rachipudi, M.Y. Kariduraganavar, A.A. Kittur, A.M. Sajjan, Synthesis and characterization of sulfonated-poly(vinyl alcohol) membranes for the perva-
poration dehydration of isopropanol, J. Membr. Sci. 383 (2011) 224–234.
[34] S.M.M. Dadfar, G. Kavoosi, S.M.A. Dadfar, Investigation of mechanical properties, antibacterial features, and water vapor permeability of polyvinyl
alcohol thin films reinforced by glutaraldehyde and multiwalled carbon nanotube, Polym. Compos. 35 (2014) 1736–1743.
[35] F. Kawai, Biodegradation of polyethers (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and others), in: A. Steinbüchel (Ed.),
Biopolymers Online, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2005, doi:10.1002/3527600035.bpol9012.