Ionics (2019) 25:2183–2193

https://doi.org/10.1007/s11581-018-2661-9

ORIGINAL PAPER

Development and electrical conductivity of PVA/MF-based

nanocomposite doped with NiO nanoparticles
Shahnawaz Ahmad Bhat 1 & Abdul Kareem 1 & Abdulrahman Mohammad 1 & Fahmina Zafar 1 & Nahid Nishat 1

Received: 6 February 2018 / Revised: 18 May 2018 / Accepted: 18 July 2018 / Published online: 7 August 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Development of PVA-MF blends encapsulated with NiO nanoparticles to prepare moisture-resistant polymer nanocomposite
films. The preparation of PVA-MF blend was carried out by blending of MF resin and prepared PVA solutions in various ratios
(2% PVA and different volumes of MF, i.e., 1.3 ml (N1), 2.2 ml (N2), 2.7 ml (N3), 3.6 ml (N4), and 4.4 ml (N5)] to optimize their
ratio for nanocomposite preparation. The nanocomposite films were prepared by dispersion of NiO nanoparticles in the different
ratio [N3 (0.03), N3 (0.06), N3 (0.09), and N3 (0.1)] in the optimized PVA-MF blend (N3) system. The structure, physicochem-
ical properties, and morphology of a prepared blend and polymer nanocomposites were characterized by Fourier transform
infrared (FTIR), ultraviolet-visible (UV-visible) spectroscopy, X-ray powder diffraction (XRD), and field emission scanning
electron microscopy (FE-SEM). The analysis reveals that the blend and polymer nanocomposite was successfully synthesized.
Electrical conductivity of PVA-MF blend (N3) has been dramatically enhanced from 0.0258 ± 0.00129 to 0.3355 ± 0.01678 S/m
and reduction in the band gap of nanocomposite from 5.1 to 4.8 eV as compared to blend by doping NiO nanoparticles. The
synthesized polymer nanocomposite will be used for the development of new material in electrical fields.

Keywords Nickel oxide nanoparticle . Polyvinyl alcohol/melamine formaldehyde-blend . Nanocomposite . Chemical stability .
Electrical conductivity

Introduction PVA is a synthetic polymer which is biodegradable, biocom-

Development of advanced material based on polymer nano-
composites that exhibit electrical and optical properties of
metals and semiconductors have presented advanced proper-
ties and applications due to their unique architectural diversity
and flexibility, low cost, and easy to prepare.
Conventional polymer composites and virgin polymers en-
capsulating with different % of metal oxide nanoparticles dem-
onstrates the advanced enhancement in the multidisciplinary
areas such as photoelectrochemical [1], electrical conductivity
[2], optical property [3], and electrochemical solar cells [4].
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11581-018-2661-9) contains supplementary
material, which is available to authorized users.
* Nahid Nishat
nishat_nchem08@yahoo.com
1
Department of Chemistry, Inorganic Material Research Laboratory,
Jamia Millia Islamia, New Delhi 110025, India
patible [5], non-toxic [6], and exhibits swelling in water. But
some limitations associated with PVA that diminishes stability
in water due to plasticizing action of water [7] mechanical
(stress, strain, tensile) properties, chemical, and thermal stabil-
ity with their negligible electrical conductivity [8]. These draw-
backs are overcome by cross-linking with various
biodegradable/non-biodegradable polymers for attaining the
desired properties and applications. Resistance against the dis-
integration of polyvinyl alcohol in water and high temperature
leading to the flow of electrolyte within polymer matrix which
causes internal short and fire [9] has been improved by the
addition of melamine-formaldehyde. Melamine-formaldehyde
resin usually increases stability and compatibility with polyvi-
nyl alcohol. Addition of melamine formaldehyde resin in dif-
ferent polymers and nanoparticles improves structure and prop-
erties [10] like temperature sensing and intracellular thermom-
etry [11]. The thermal stability, mechanical properties, resis-
tance against hydrolysis, adsorption, and fire retardation im-
proved by the melamine-formaldehyde resin in PVA [12]
[13].The polyvinyl alcohol when undergoing modification with
MF and NiO nanoparticles by a feasible method where the
2184
polymer acts as a carrier facilitated transport [14] [15]. Metal
oxide nanofillers generally enhance the electrical, mechanical,
optical, and thermal stability of resulting polymer nanocompos-
ites as compared to respective virgin or blended polymers. Co-
precipitation method was the versatile route used to synthesize
NiO nanoparticles [16]. The metal oxide nanoparticles tend to
irreversibly aggregate over time but they are stable in suspen-
sions. The aggregation of NiO nanoparticles reduces their
nanoscale properties and limits their applications and interac-
tion with glucose [17]. As the overall polymers, most of them
have either zero or negligible electrical conductivity, and they
have to be modified to procure structure and properties of poly-
vinyl alcohol (PVA)-derived nanocomposite with coveted
properties and application [18]. The embedment of semicon-
ducting or metal oxide nanoparticles inside the conducting
polymers, such as polyaniline, is of interest because of the
strong electronic interaction between the polymer and nanopar-
ticles in the matrix [19]. The particle size, morphology, struc-
tural aspects, and electrical conductivity of the metal oxide
nanoparticle unveil the latest material properties that are incom-
parable to those of their parent materials [20] [21]. The nano-
particles have diverted the attention of the researchers because
of the cutting-edge nature and the use of nanoparticles in elec-
tronic properties [22]; photo-induced light reflectivity alters
with size and morphology of ZnO nanoparticles [23]. The ab-
solute drift of the thermal, structural, and electrical properties of
polyethylene oxide/polypropylene glycol (PEO/PPG) nano-
composite after addition of Al2O3 nanoparticle [24] morpholo-
gy, structure, and electrical conductivity amendment of
polyvinylidene difluoride-co-hexafluoropropylene (PVdF-
HFP) by encapsulation of ZnO nanoparticles [25].
Literature search reveals that MF resin affects the proper-
ties of PVA such as thermal stability, resistances in abrasion,
surface smoothness, moisture resistance, and flame retardant
which diverted the attention of industrialists [26]. The positive
effect on electrical conductivity on PVA doped by multiwalled
carbon nanotubes [27] and decreasing optical band gap by
encapsulation of CuO nanoparticles in PVA nanocomposite
[28]. To the best of our knowledge, no work has been reported
on chemical stability in different pH media, band gap, and
electrical conductivity of PVA-MF/NiO nanocomposite. The
aim of the work is the development of nanocomposites based
on PVA-MF blend and NiO nanoparticles to explore their
application as moisture-resistant films. The objectives of the
work are (i) preparation and characterization of PVA-MF
blend films to optimize their composition for nanocomposite;
(ii) preparation and characterization of PVA-MF/NiO nano-
composite by dispersing NiO nanoparticles (0.03–0.1%) in
PVA-MF blend (N3) for said application; (iii) to find out the
effect of NiO dispersion on chemical stability in different pH
media, thermal stability, band gap, and electrical conductivity
of the PVA-MF/NiO nanocomposite films that is the novelty
of the present work.
Ionics (2019) 25:2183–2193
Materials and methods
NiCl2·6H2O and NaHCO3, polyvinyl alcohol M.W.1, 15, 000,
(LR grade), and formaldehyde (37%w/v, LR) were purchased
from Merck. Melamine powder (AR grade) and NaOH were
purchased from Gujarat Natural Fertilizers Limited (GNFC),
and double-distilled water was used as solvent for all
solutions.
Synthesis
NiO synthesis
NiO nanoparticles were synthesized as per previously report-
ed method with slight modification; the average size of NiO
nanoparticle was 10–50 nm [29] [30]. In this synthesis, the
molar ratio was changed; NiCl2.6H2O (3 g) and NaHCO3
(1.8 g) were dissolved in 20 ml distilled water separately in
a conical flask. The stirring of the NiCl2·6H2O solution was
increased from 20 to 40 min on a magnetic stirrer. The
NaHCO3 solution was added drop wise into the NiCl2·6H2O
solution with constant stirring at room temperature. When the
gas formation was stopped from reaction mixture, the stirring
was put off. The precipitate from the solution was collected by
centrifugation at high speed (10,000 rpm) for 15 min and
washed with double-distilled water and ethanol for five times.
The filtered product was dried at 100 °C for 1 h; after drying,
the calcination temperature and time were increased for 6 h at
400 °C.
Synthesis of MF
The MF was prepared by the well-known method with some
modifications [31] where 1:1 molar ratios of formaldehyde
and melamine reacted in the presence of 2 N NaOH base
catalyst and molecular weight increases by increasing concen-
tration of formaldehyde. The double-necked round-bottom
flask was filled with formaldehyde, and the pH 8–9 was con-
trolled by the addition of 2 N NaOH solution. The RB flask
with formaldehyde solution was put on a magnetic stirrer
followed by addition of 8 g melamine powder and 20 ml dis-
tilled water. The uninterrupted heating 80–90 °C and stirring
of reaction mixture till a clear solution was obtained. The MF
resin formation was confirmed by colorless and increase in
viscosity of the solution. The water tolerance of the MF resin
was analyzed after every 10 min of taking samples from reac-
tion mixture until 30 °C dropped to 1:4. The heating and
stirring were put off, and the solution was cooled at 25 °C,
properties like viscosity and water tolerance were standard-
ized to viscosity: at 23 °C is 30–40 s, water tolerance at
230 °C is 1:2–1:4, and gel formation was observed at
150 °C 1–2 min. To increase, the shelf life of MF resin,
Ionics (2019) 25:2183–2193
methanol was added and the solution was stored for 1 month
or in a refrigerator.
Synthesis of PVA- MF blend
To prepare polyvinyl alcohol, 2% PVA was added to double-
distilled water and the solution was heated on a magnetic
stirrer at 90 °C for 2 h. The MF resin and prepared PVA
solutions were blended in various ratios [(2% PVA and differ-
ent volumes of MF, i.e., 1.3 ml (N1), 2.2 ml (N2), 2.7 ml (N3),
3.6 ml (N4), and 4.4 ml (N5)] by using an electrical blender
while during heating at about 90 °C, the appearance of white
color confirms the formation of PVA-MF polymer blend [32].
Synthesis of PVA-MF/NiO nanocomposite
For the preparation of nanocomposite films, PVA-MF blend
(N3) system was synthesized as mentioned above at 80 °C till
white color appeared followed by the addition of dispersed
NiO nanoparticles in the different ratio [N3 (0.03), N3
(0.06), N3 (0.09), and N3 (0.1)]. The dispersion of NiO nano-
particles was carried out before the addition. Firstly, NiO
nanoparticles dispersed in distilled water then dispersed into
PVA-MF blend (N3). The resulting reaction mixture was heat-
ed at the same temperature under continuous stirring. The
stirring was continued for 30 min at 95 °C temperature. The
formation of the PVA-MF/NiO nanocomposite was confirmed
when homogenous greenish color appeared and viscosity
increased.
Preparation of film
PVA-MF blend and nanocomposite films
To obtain best and air bubble-free thin uniform free-standing
films, the desired amount of reaction mixture was poured on
Teflon sheet. The PVA-MF blend films with labels N1 to N5
were prepared by blending of 20 ml of 10% PVA solution and
different volumes of MF, i.e., 1.3 ml (N1), 2.2 ml (N2), 2.7 ml
(N3), 3.6 ml (N4), 4.4 ml (N5). PVA-MF/NiO nanocomposite
films were prepared by dispersion of NiO nanoparticles (0.03,
0.06, 0.09, and 0.1wt) % in optimized PVA-MF blend (N3)
system. The synthesis of nanocomposites was coded as PVA-
MF/NiO N3 (0.03%) nanocomposite, PVA-MF/NiO N3
(0.06%) nanocomposite, PVA-MF/NiO N3 (0.09%) nano-
composite, PVA-MF/NiO N3 (0.1%) nanocomposite. Then,
they were kept undisturbed and allowed to dry at 30 °C for
12 h. After drying, the samples were put in an oven for 30 min
at 80 °C temperature. Once the films were removed from the
oven, they were peeled off and stored at room temperature in
zip-lock bags.
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Characterization
The FTIR spectra of the nanocomposite in the range of 300–
3500 cm−1 region were taken on a PerkinElmer 1750 FTIR
spectrophotometer. Shimadzu UV 2550 UV visible spectro-
photometer was used for UV-visible absorption in the range of
200–800 nm. Powder X-ray diffraction (XRD) studies have
been carried out using RigakuUltima IV X-ray diffractometer
fitted with nickel-filtered Cu-Kα radiation (λ = 1.5416 Ǻ).
The diffraction pattern blends and nanocomposite were ob-
served in the 2θ range of 20°—80°. The morphology and
structural analysis of blend and nanocomposite were analyzed
by field emission scanning electron microscope (FE-SEM
model FEI.Quanta 200 FIE 250 X Max 80) at SAIF research
laboratory, All India Institute of Medical Science, New Delhi,
India. Thermal stability of blend and nanocomposite films was
studied by Metter Toledo AG Analytical CH860
(Schwerzenbach, Switzerland) performed in a range of 40–
800 °C at a heating rate of 10 °C/m under nitrogen atmo-
sphere, 20 ml/min, in Jamia Millia Islamia, New Delhi, India.
The chemical resistance of the blend and nanocomposite
films in different pH 4, 7, and 9.2 solutions was studied. The
degree of weight loss was determined (w/w %) by the follow-
ing equation:
Weight loss% ¼ ðWi−Wf Þ%Wi  100
where Wi is initial weight and wf is final weight.
For electrical conductivity measurements, the blend and
nanocomposites were dried at 40–50 °C and then electrical
conductivity was measured by a four-in-line probe of pellets
prepared from PVA-MF blend and PVA-MF/NiO nanocom-
posite. The electrical conductivity of the blend and nanocom-
posite was calculated by the following equation:
ρ ¼ ρo=G7 ðW=SÞ ð1Þ
G7 ðW=SÞ ¼ ð2S=WÞIn2 ð2Þ
where G7 (W/S) denoted correction divisor which is a func-
tion of the thickness of N3 blend and N3 (0.1) nanocomposite.
The spacing denoted as I, W, and S are current (A), the thick-
ness of the film (cm), and probe spacing (cm), respectively.
Results and discussion
Synthesis
The MF resin was prepared in 1:1 M ratios of formaldehyde
and melamine in presence of a base as a catalyst according to
the reported method with some modifications [31]. Numerous
methods were used for preparing PVA-MF blends; the present
work was reported by method [32]. The synthesized NiO par-
ticles were initially dispersed in distilled water before their
2186
addition to PVA-MF blend (N3) solution to obtain homoge-
nous nanocomposite [33] [34] [35]. It was noted that
crosslinking of PVA begins even the smallest addition of
MF. As the concentration of MF was increased, the films were
brittle, and water resistance and the transparency of the films
decreased. The opacity of the films obtained changed from
transparent to white opaque films with reduced elasticity as
the composition changed from N1 to N5. From all the blends,
N1, N2, and N3 were soft, transparent, and flexible, but N4
andN5 were too brittle and completely opaque. The N3 sam-
ple was the most suitable, neither too brittle nor too opaque,
and was the best transparent film for the synthesis of polymer
nanocomposite from blending of PVA-MF (2.7 ml).
Spectral analysis
The formation of PVA-MF blend (N3) and PVA-MF/NiO
nanocomposite shown in Fig. 1 was confirmed by comparing
the spectra of PVA [36], MF [31], and NiO [30]. FTIR of the
peak at 3392 cm−1 assigned to stretching vibration of O–H
group of pure PVA [37] was shifted to 3412 cm−1 in PVA-MF
blend (N3) [36]. Figure 1 (N3) shows that strong absorption
peak at 2920 cm−1 was shifted to 3129 cm−1 which is attrib-
uted to C–H stretching and 1062 cm−1 corresponding to C–O–
C stretching vibration confirms the formation of the blend
[31]. A small peak at 469 cm−1 corresponds to Ni–O band
that confirms the formation of PVA-MF/NiO nanocomposite
[30] [38] shown in detail in Fig. 1 (N3, 0.1). FTIR of a peak at
3392 cm−1 assigned to stretching vibration of O–H group of
pure PVA [37] was shifted to 3422 cm−1 (PVA-MF/NiO)
nanocomposite which confirms the crosslinking of the poly-
mer systems. The C–H stretching vibration at 2920 cm−1 has
been shown by PVA [22] and was shifted to 2929 cm−1. The
Fig. 1 FTIR of PVA-MF blend
(N3) and PVA-MF/NiO N3 (0.1)
nanocomposite
Ionics (2019) 25:2183–2193
peak at 1443 cm−1 corresponds to C–H bending of PVA but
peak was shifted to 1463 and 1463 cm−1 in blend and nano-
composite respectively [15]. The vibration peak at 1383 cm−1
referred to C–H wagging of CH2 group, and the peak shifts to
higher wavenumber in blend and nanocomposite [39]. C–O
stretching in PVA at 1067 cm−1 and a new peak that appeared
in the nanocomposite at 1679 cm−1 corresponding to C–O–C
stretching confirm the encapsulation of NiO nanoparticles
PVA-MF blend (N3) as shown in Fig. 1 (N3, 0.1) [40]. The
strong peak at 813 cm−1 attributed to triazine of MF resin and
the peak appeared broad and short in blend and nanocompos-
ite [31].
UV-visible spectroscopy
UV-Vis absorption is an important technique to determine the
optical properties, band gap, and structure of PVA-MF blend
(N3) and PVA-MF/NiO nanocomposite by ultrasonically dis-
persing in distilled water. The UV absorbance region of NiO
nanoparticle at a wavelength of 284 nm, 320 nm was reported
[41]. Figure 2 PVA/MF blend (N3) and PVA-MF/NiO N3
(0.1) nanocomposite can compare the results with the shifting
of the peak with nano silicate nanoparticles encapsulated in
PVA nanocomposite from 250 to 350 nm [42]. The UV of
PVA-MF blend 175 nm and PVA-MF/NiO nanocomposite
shows the peaks at the wavelength 225 nm shows a redshift
which proves the presence of NiO nanoparticles in the nano-
composite. The reduction of band gap from PVA-MF blend
(N3) (5.1 eV) to PVA-MF N3 (0.1) nanocomposite (4.8 eV) in
the ultraviolet region was associated with the electronic tran-
sition from valence band to the conduction band due to en-
capsulation of NiO and CuO nanoparticles in PVA-based
nanocomposites [43] [22].The quantum confinement effect
Ionics (2019) 25:2183–2193
Fig. 2 UV-Vis spectra and band
gap of PVA-MF blend (N3) PVA/
MF/NiO N3 (0.1) nanocomposite
is due to blue shift which indicates that the wavelength of the
nanocomposite decreases with a decrease in NiO nanoparticle
size in the nanocomposite. Sufficiently small size of semicon-
ducting nanoparticle in nanocomposite approaches the radius
of the first excited-state orbital of the conduction band to ob-
serve the quantum size effect; blue and red shift were observed
in CdS/polyvinyl alcohol nanocomposite [44]. The shift ob-
served in PVA-MF/NiO nanocomposite increases as the con-
centration of NiO nanoparticle in PVA-MF blend.
X-ray diffraction
XRD study is a good technique which is recycled to analyze the
crystalline structure of the particles, as well as phase purity and
phase analysis. The 2θ values of PVA-MF blend film at 19.66°
are characteristic of amorphous nature of blend (Fig. 3 (N3)).
As shown by the XRD spectra of NiO nanoparticle, five sharp
peaks are observed at about 37.25_ (111), 43_ (200), and
62.85_ (220) [40]. The XRD of nanocomposite (PVA-MF/
NiO) shows that a broad peak at 2θ = 20.12 of PVA markedly
decreases, and the other two disappeared by addition of mela-
mine formaldehyde resin and three new narrow peaks of NiO
nanoparticles 2θ and indexed values at 37.66° (111), 43.67°
(200), and 63.38° (220) (Fig. 3 (N3(0.1)), which confirms the
formation of (PVA-MF/NiO) nanocomposite [45].
Morphological analysis
Scanning electron microscopy and histogram The surface
morphology of PVA-MF blend (N3) film was analyzed by
2187
viewing FE-SEM Fig. 4a. The SEM observation shows the
smoothness and uniform surface of the PVA-MF blend. The
surface morphology of PVA-MF/NiO nanocomposite films
was analyzed by viewing FESEM. The nanocomposite with
uniform dispersion and average size of 0.1% of NiO nanopar-
ticle in PVA-MF blend (N3) was determined by FESEM
(Fig. 5a). The data obtained by FESEM micrographs, the his-
togram can be drawn, and the average size of the NiO nano-
particles has been determined [46]. The NiO nanoparticles are
spherical in shape with a mean particle size of 10 nm as shown
in Fig. 5a. SEM micrograph shows a homogeneous distribu-
tion of NiO nanoparticles within the PVA-MF/NiO nanocom-
posite. The SEM studies reveal uniform surface and smooth
morphology. The NiO nanoparticles retain their shape and
enhance the crystalline behavior in the polymer
nanocomposite.
Thermal analysis
Thermal behavior of the prepared blend and nanocomposite
samples were analyzed by thermal gravimetric analyzer at a
heating rate of 10 °C/m from 25 to 800 °C under a nitrogen
atmosphere. In Fig. 6, PVA-MF blend (N3) shows first that the
11% weight loss in PVA-MF starting from 90 to 166 °C is due
to the evaporation of water and other moieties. The weight
loss (32%) at 231–286 °C is the second weight loss due to
the melting of PVA side chains, and the extensive thermal
degradation occurred at the third stage which showed 70%
weight loss at 380–440 °C [47].The MF resin condensate went
through degradation and formation of volatile products like
2188
Fig. 3 XRD micrograph PVA/
MF blend (N3) and PVA-MF/NiO
N3 (0.1) nanocomposite
CO2, HCN, and CO. The thermal properties of PVA-MF
blend film mainly depend on network structure, stability,
and extent of cross-linking with MF, as well as the number
of the remaining groups, the concentration of the remaining
groups, and molecular chain rigidity interaction between the
molecular chain and the structural factors such as conforma-
tional adjustment of groups and steric stress.
Thermal gravimetric analysis (TGA) and differential ther-
mal analysis (DTA) curves of PVA-MF/NiO nanocomposite
are shown with varying concentrations, i.e., N3 0.03, 0.04,
Fig. 4 a SEM images of the PVA-
MF blend (N3)
Ionics (2019) 25:2183–2193
0.06, and 0.1 mg samples in Fig. 6. The thermal gravimetric
curves shown by various nanocomposite samples occur in one
stage with weight loss of 13% at 150 °C. The major thermal
degradation occurred with weight of 31% at 232–286 °C and
the maximum weight loss of 65% shown at 372–440 °C
N3(0.03). The nanocomposite film N3 (0.06) showed initial
weight loss of 12% at 90–166 °C, the second weight loss of
31% at 231–285 °C, and major weight loss of 64% at 840–
440 °C. The nanocomposite film N3 (0.09) showed initial
degradation weight loss of 13% starting at about 90–166 °C,
Ionics (2019) 25:2183–2193
Fig. 5 SEM micrographs (a) and
histogram (b) showing the
distribution of NiO nanoparticles
in PVA-MF/NiO N3 (0.1)
nanocomposite
the second weight loss of 31% at 232–294 °C, and the third
weight loss of 64% at 377–440 °C. The initial weight loss of
the nanocomposite film N3 (0.1) of 14% occurred at 90–
166 °C, the second weight loss of 58% at 231–296 °C, and
the third weight loss at 340–440 °C as shown in Fig. 6. The
decomposition at this temperature which is closer to the de-
composition temperature of fully hydrolyzed PVA at 230 °C is
also due to the loss of PVA component in the composite films
showing comparable results of TGA and DTA curves [48].
The initial weight loss is comparatively less in a blend where-
as more in PVA-MF/NiO nanocomposite films. The final
Fig. 6 TGA of PVA-MF blend (N3), PVA-MF/NiO N3 (0.03%) nano-
composites, PVA-MF/NiO N3 (0.06%) nanocomposite, PVA-MF/NiO
N3 (0.09%) nanocomposite, and PVA-MF/NiO N3 (0.1%)
nanocomposite
2189
weight loss calculated was more in blend films than in poly-
mer nanocomposite because as the concentration of NiO
nanoparticles increased, the weight loss also reduced from
N3 (0.03) to N3 (0.1), which confirms that nanoparticles
entrapped in PVA-MF blend increase the thermal stability as
observed in Fig. 6.
The DTA shows one endothermic peak at 428 °C and two
exothermic peaks at 314 and 475 °C in PVA/MF blend film
(N3); one endothermic peak at 207 °C and exothermic peak at
464 °C in nanocomposite film N3 (0.03); one endothermic
peak at 202 °C and one exothermic peak at 459 °C in nano-
composite film N3 (0.06); endothermic peaks at 203 °C and
one exothermic peak at 458 °C in nanocomposite film N3
(0.09); but N3 (0.1) polymer nanocomposite film shows three
endothermic peaks at 70, 315, and 545 °C and one exothermic
peak at 505 °C as shown in Fig. 7. The melting temperature
and vaporization of moieties are shown by the endothermic
reaction and breaking of bonds in the exothermic reaction
studied by differential thermal analysis (DTA). The data ob-
tained from DTA analysis clearly shows increasing thermal
stability from blend to polymer nanocomposite.
Chemical stability
MF loading greatly improves the chemical stability of
PVA fibers [49]. The chemical stability of (N3) PVA-MF
blend and PVA-MF/NiO composite films with different
concentrations N3(0.03), N3(0.06), N3 (0.09), and
N3(0.1) % of NiO nanoparticles in the PVA-MFR blend,
like solution stability of polyvinyl alcohol-based films.
Weight loss in pH 4, 7, and 9.2 shows that the overall
2190
Fig. 7 DTA of PVA-MF blend (N3), PVA-MF/NiO N3 (0.03%) nano-
composite, PVA-MF/NiO N3 (0.06%) composite, PVA-MF/NiO N3
(0.09%) nanocomposite, and PVA-MF/NiO N3 (0.1%) nanocomposite
chemical stability increases with increasing concentration
of NiO nanoparticles. Figure 8 clearly shows that polymer
nanocomposite films have greater chemical stability as
compared to blend as the NiO content increases. After
24 h, maximum swelling was attained by all the samples;
the effect of pH on PVA-MF blend is that it lost more
weight than did the other nanocomposite samples in
5 months. The weight loss was analyzed after 5 months
in different media pH 4, 7, and 9.2 solutions. The weight
loss of a blend and nanocomposite might be due to rear-
rangement in a structure of protonated amine sites of
Fig. 8 Chemical stability tests of PVA-MF blend (N3), PVA-MF/NiO N3
(0.03%) composites, PVA-MF/NiO N3 (0.06%) nano composite, PVA-
MF/NiO N3 (0.09%) nano composite, and PVA-MF/NiO N3 (0.1%)
nanocomposite
Ionics (2019) 25:2183–2193
melamine formaldehyde during neutralization, which in-
creases the coherence of polymer components and miti-
gated solubility [50]. The pores and empty spaces in the
PVA-MF blend are filled with NiO nanoparticles, and hy-
drogen bonding between NiO nanoparticles and hydroxyl
groups increases. So, that is the reason the chemical sta-
bility increases as we increase the amount of NiO nano-
particles. Samples of PVA-MF blends and nanocomposite
were placed in swelling solutions for 6 days in different
acidic and basic medium to determine the long-term
chemical stability of the films. The blend and nanocom-
posite were weighed before and after time interval for the
7 days, then every month, the duration of the study shows
the results of the experiment. Comparing the results after
5 months, the highest weight loss by blend and nanocom-
posite carrier could be calculated. When the films have
attained equilibrium, then the loss of weight indicates that
polymer chains are leaching out of the network. From Fig.
8, the result reveals that PVA-MF blend is the least stable
among all the samples as compared to nanocomposite.
Electrical conductivity
For the electrical conductivity measurements of PVA-MF
blend (N3) and the PVA-MF/NiO N3 (0.1) nanocompos-
ite, the standard four-in-line probe method was used. The
calculated data of blend and polymer nanocomposite sug-
gests that nanocomposite is semiconducting in nature.
Inorganic-organic hybrid nanocomposite shows that en-
hancement of electrical conductivity reported in nanocom-
posite NiO nanoparticles embedded in polyaniline/
polyvinyl alcohol blend [27] affect the morphology and
electrical conductivity of polyvinyl alcohol/ZnO-CeO
nanocomposite films [51]. The improved electrical con-
ductivity of polymer films by filling nanoparticles as
fillers using electron spinning procedure like optical and
electrical properties of PVA increases by the filling of
titanium plate nanoparticles [15]. The electrical conduc-
tivity values increased from 0.0258 ± 0.00129 to 0.3355 ±
0.01678 at 30 °C in PVA-MF blend (N3) and PVA-MF-
NiO nanocomposite at room temperature as shown in
Fig. 9a, b. The effect of temperature on electrical conduc-
tivity on blend and nanocomposite was studied from 10 to
100 °C as observed in Fig. 10a, b.The electrical conduc-
tivity of PVA-MF/NiO nanocomposite increases with in-
creases in temperature as compared to blend and remains
consistent at 100 °C. A phonon is quantum mechanical
quantization of elementary modes of vibrational motion in
which a lattice of molecules and nanoparticles oscillates
constantly at a fixed frequency. Thermal conductance oc-
curred in terms of phonon communication across the
polymer nanocomposite interface. In a harmonic system,
a phonon is transported elastically through elastic
Ionics (2019) 25:2183–2193
Fig. 9 Electrical conductivity of a PVA-MF blend (N3) and b PVA-MF/
NiO N3 (0.1) nanocomposite
transport medium, but anharmonicity which increases
with temperature allows phonons to transmit through the
inelastic transport channel and improves the electrical
conductivity [52]. The characteristic of conductivity is
temperature-reliant attributable to the thermally stimulated
behavior. The conduction in polymer nanocomposite can
be analyzed in terms of the formation of polaron and
bipolaron, due to alteration in polymer nanocomposite
oxidation state. The polaron and bipolaron formation in
nanocomposite is responsible for conduction due to alter-
ation in nanocomposite oxidation state. A higher degree
of freedom in polaron and bipolarons moves along the
polymeric chain; polaron and bipolaron have conjugated
single-double bond system, a higher degree of freedom,
because they move along the polymeric chain.
Fig. 10 Temperature dependence electrical conductivity of a PVA-MF
blend (N3) and b PVA-MF/NiO N3 (0.1) nanocomposite
2191
Conclusion
This study allows us to conclude the successful synthesis of
PVA-MF blend (N3) and PVA-MF/NiO nanocomposites.
FTIR determines the electrostatic interaction between PVA-
MF blend and NiO nanoparticles. Reduction in band gap has
been observed from 5.1 to 4.8 eV in nanocomposite as com-
pared to blend determined by UV-visible spectrophotometer.
The crystalline behavior of the nanocomposite was analyzed
by X-ray powder diffraction (XRD). The uniform distribution
of NiO nanoparticles in a range of 10–50 nm in the nanocom-
posite was observed by FE-SEM. In addition, the incorpora-
tion of NiO nanoparticles in PVA-MF blend increases the
hydrophobicity, chemical stability, and thermal stability of
nanocomposite. PVA-MF blend (N3) doped with 0.1% NiO
nanoparticle has shown positive drift in electrical conductivity
from 0.0258 ± 0.00129 to 0.3355 ± 0.01678 at 30 °C in PVA-
MF blend (N3) and nanocomposite (PVA-MF/NiO), respec-
tively. Thus, the result showed the significant effect of NiO
nanoparticles on the structural, chemical, thermal, and electri-
cal properties of the nanocomposite.
Acknowledgements Dr Fahmina Zafar is thankful to Dept. of Science &
Technology, New Delhi, India for the postdoc fellowship under the women
scientists scheme (WOS) for research in Basic/applied science (Ref.no.SR/
WOSA/CS-97/2016).
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