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Polyvinyl alcohol: A review of research status and use of polyvinyl alcohol

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Polyvinyl Alcohol: A Review of Research Status and Use of
Polyvinyl Alcohol Based Nanocomposites
Muhammad Aslam,1,2 Mazhar Ali Kalyar,1 Zulfiqar Ali Raza 2
1
Department of Physics, University of Sargodha, Sargodha 40100, Pakistan
2
Department of Applied Sciences, National Textile University, Faisalabad 37610, Pakistan
This review presents the nature, fundamental structure,
and various morphologies of native poly(vinyl alcohol)
(PVA) matrix. It highlights recent advances in pure PVA
and its composites containing various nanofillers that
have potential applications in various fields. Over half a
century, PVA is known as an auspicious material for
diverse applications. The review focuses on the structural,
mechanical, optical, and electrical properties of PVA-
based nanocomposites. The study highlights a new prom-
ising area of optoelectronics for possible applications of
PVA nanocomposites. The challenges and opportunities in
working with various PVA nanocomposites are discussed
along with some future recommendations are presented
to strengthen this area of research. POLYM. ENG. SCI.,
00:000–000, 2018. V
C 2018 Society of Plastics Engineers
INTRODUCTION
Nanotechnology is a multidisciplinary field that has been
blooming recently [1]. Its significance is increasing in various
fields including biomedical, sensors, and computing [2]. Poly-
meric materials are being used as a replacement for conven-
tional materials because they are light weight, and inexpensive
with excellent physicochemical properties [3]. Attempts are
being made to fabricate various polymeric nanocomposites and
to understand their fundamental principles for their applications
in various fields of science and engineering. The structural, opti-
cal, mechanical, and electrical properties of polymers can easily
be tuned by incorporating small quantities of nanofillers in the
polymer matrices [4, 5]. Various types of polymers (like poly-
ethylene, polyvinylidine fluoride, polypropylene, polymethyl
methacrylate, polyaniline, polyvinyl chloride, polyamide, poly-
ethylene terephthalate, polystyrene, etc.) composites loaded with
different types of nanofillers (like CuO, ZnO, ZnS, CuS, CdSe,
Cds, GO, FeO, etc.) have been fabricated for structural, optical,
mechanical and electrical properties enhancements [3, 6]. In this
study, PVA polymer is selected due to its amazing properties
such as high optical transmission, water solubility, stable ther-
mal, and noncorrosive nature that makes it a good matrix for
optoelectronic and a variety of other applications [7–9].
In this review, the nature, physicochemical properties, mor-
phologies, and means of modification of various nanocomposites
of PVA have been discussed. A short overview of this review is
presented here. Vinyl acetate as monomer is used for commer-
cial PVA production. Various grades of PVA are available on
the market [7]. Completely hydrolyzed PVA has properties
Correspondence to: M. Aslam; e-mail: aslamfaridipk@gmail.com or Z.A.
Raza; e-mail: zarazapk@yahoo.com
DOI 10.1002/pen.24855
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2018 Society of Plastics Engineers
V and chemical resistant fiber (also called Juche fiber) fabricated
POLYMER ENGINEERING AND SCIENCE—2018
different from partially hydrolyzed PVA [10]. In order to mod-
ify the properties of PVA, abundant hydroxyl groups play an
important role [11]. The semicrystalline nature of PVA is due to
hydrogen bonding between PVA chains [3]. PVA exists in dif-
ferent morphologies for variety of applications including phar-
maceutical, biomedical and others [12]. For instance, PVA gel
beads may be used in water filtration systems [13]. The high
optical quality of PVA films is useful in optical sensors and
devices. Polymeric nanofiber membranes are being used in vari-
ety of applications including batteries, filter materials, biomedi-
cal scaffolds, fuel cells, and osmotic power plants [1, 12]. Due
to the hydrophilic nature of PVA, crosslinkers are used to syn-
thesize hydrogels for a number of applications [12]. To make
PVA fibers, various spinning techniques are being used. The
PVA matrix plays an essential role in the formation of such valu-
able membranes. PVA is being used to fabricate controlled inter-
connected micro porous three dimensional (3D) scaffolds for
various applications [14]. Commonly used conventional modifica-
tion reactions include acetalization, carbamation, etherification, or
esterification of hydroxyl group of PVA. The modern chemical
modification method is the click chemistry. The modified PVA
may be used in a wide range of applications such as molecular
sensing in biological and biomedical fields, membranes of fuel
cells, chemo sensors, absorption of toxic metals, and optoelec-
tronic devices [15]. Nanofillers expose their larger surface area
for interaction with polymer that is the key concept in the
enhancement of functional properties of polymeric nanomaterials.
The biomedical uses of PVA include embolization particles, eye
drops, contact lenses, meniscus, artificial cartilage, and adhesion
barrier [16]. PVA behaves as an embedding mat and matrix for
metal/inorganic nanofiller for sensing, optoelectronic devices and
many other applications [15]. PVA nanocomposites may include
nanofillers made from metals, nonmetals, metal oxides, metal sul-
fides, inorganic or combinations of these materials. Their applica-
tions are discussed in detail in this review.
NATURE OF POLY(VINYL ALCOHOL)
PVA is a creamy or whitish, tasteless, odorless, nontoxic,
biocompatible, thermostable, granular or powdered semi crystal-
line or linear synthetic polymer [3, 9, 17]. It possesses astonish-
ing optical properties, large dielectric strength, and excellent
charge storage ability [9]. Its mechanical, optical and electrical
attributes can readily be tailored by doping with nanofillers.
PVA is available on the market in different grades on the basis
of viscosity and degree of hydrolysis [7, 18]. PVA is most
widely used in the synthesis of poly(vinyl butyral) (PVB) and
vinylon fibers. PVB is a low cost flexible thermoplastic, being
used as strong adhesive in multiple applications and might be
used in shape memory devices [19]. Vinylon is manmade heat

FIG. 1. Representative (a) PVA monomeric structure/completely hydro-
lyzed PVA, (b) vinyl alcohol structure, (c) PVA structure, and (d) partially
hydrolyzed PVA. [Color figure can be viewed at wileyonlinelibrary.com]
from PVA and is widely used in textiles, quilts wadding, ropes,
and shoes [20]. Other consumers of PVA include the textile
industry, paper making, coatings, adhesives, medicines, optics,
3D printing and so on [8, 10]. The major PVA producers are
Europe, Japan, USA, and China. In 2016, worldwide production
of plastics and PVA was about 335 million metric tons and
1124 kilo metric tons, respectively. For the same year, contribu-
tion in PVA production of Asia pacific and USA was about 580
and 172.8 kilo tons, respectively [21, 22].
CHEMISTRY OF PVA
The monomeric structure of PVA is shown in Fig. 1a. It was
first synthesized in 1924 by Hermann and Haehnel by saponify-
ing poly(vinyl ester) with sodium hydroxide solution resulting in
a PVA solution [23]. The physicochemical and mechanical
attributes of PVA are governed by the number of hydroxyl
groups present in the PVA polymer [11]. PVA is synthesized
not by polymerization of its structural monomer (i.e., vinyl alco-
hol) due to its unstable nature. For commercial production of
PVA, the basic raw material for the polymerization of PVA is
vinyl acetate (as monomer). The controlled partial alkaline
hydrolysis (saponification) of vinyl acetate is performed where
the ester group of vinyl acetate is partially replaced with
hydroxyl group in an environment of aqueous sodium hydrox-
ide. The precipitate of this reaction is called PVA. The structure
of vinyl alcohol and PVA is shown in Fig. 1b and c, respectively.
The time period length of the saponification reaction determines
the degree of hydrolysis of PVA [10]. PVA of low molecular mass
is prepared by polymerization of acetaldehyde at low temperature
of 2808C to 2208C with sodium amalgam [24]. Fig. 1a represents
completely hydrolyzed and Fig. 1d represents partially hydrolyzed
PVA structures. Based on hydrolysis (%) and molecular mass, dif-
ferent grades of PVA are available on the market having different
characteristics including melting point, viscosity, pH, refractive
index, and band gap [10]. The effect of variation in vinyl acetate
length and degree of hydrolysis under acidic or alkaline conditions
results in various congeners of PVA having different flexibility,
tensile strength, dispersing power, emulsification index, adhesive-
ness, and solubility [23]. Some of the chemical properties of pure
PVA are listed in Table 1.
2 POLYMER ENGINEERING AND SCIENCE—2018
PHYSICS OF PVA
The physical attributes (density, crystallinity, film formation,
water solubility, molar volume, degree of polymerization, etc.)
of PVA depend upon the degree of hydrolysis, crystal precipita-
tion, molecular mass and moisture [8, 24]. PVA is flexible,
strong and hard, and possesses oxygen/aroma barrier properties.
To prevent any PVA disruption in gas permeability, moisture
must be avoided. Physical modification of PVA is possible
through crystallization process. The reason for PVA crystalliza-
tion is due to hydrogen bonding between PVA chains. When
some exogenous nanoparticles (NPs) are introduced into the
polymer matrix, they act as nucleating agents during crystalliza-
tion [25]. Some physical properties of pure PVA are listed in
Table 2.
Different physical, mechanical, chemical, and optical proper-
ties of PVA can be tuned using a variety of nanofillers. Ahn
et al. [26] investigated PVA as reducing agent in graphene oxide
(GO) dispersion. The patterns of reduced graphene oxide (RGO)
nanosheets at different contents of PVA were verified through
advanced analytical techniques. The FTIR analysis showed that
reduction temperature of GO was decreased to 708C using PVA.
This decrease in reduction temperature could allow GO to be
used in soft electronics [26]. Ramalingam et al. [27] prepared
PVA–graphene nanofibers via electrospinning technique that
showed enhanced electrical conductivity of 10.7 3 1026 S/cm
as compared to pure PVA (3.7 3 10212 S/cm). The nanofibers
might be used for transparent electrode material for supercapaci-
tors and optoelectronic devices [27]. Aziz [28] used a solution
of black tea extract (60 mL extract in 1 g of PVA) and suc-
ceeded in reducing the band gap to 1.85 eV (from 5.38 eV of
pure PVA) and dispersion in refractive index was increased
from 1.22 (of pure PVA) to 2.61 of composite. The researcher
suggested that PVA based composite might be used in organic
solar cells and optoelectronic devices [28]. Elkomy et al. [29]
doped PVA–polypyrrol (PPY) with cobalt chloride (CoCl2), and
investigated the optical properties of nanocomposites. The band
gap of PVA–PPY composite (2.68 eV) was decreased to
2.03 eV after adding 1 wt% CoCl2 [29]. Hamdalla et al. [30]
doped PVA with erbium chloride (ErCl3) and obtained compos-
ite films by casting method. The FTIR studies showed complex
formation of Er13 in PVA structure. The 9 wt% ErCl3 doped
sample decreased energy band gap of PVA to 5.1 eV and
enhanced refractive index to 1.72. The composites were
TABLE 1. Chemical properties of pure PVA.
Parameters Description Refrences
Molecular weight 20,000 to 400,000 g/mol [23]
Structural formula (ACH2CHOH)-n-(CH2CHOCOCH3A)-m [23]
Empirical formula (C2H4O)n(C4H6O2)m [23]
Partially hydrolyzed 84.2%–89% [7]
PVA
Moderately hydrolyzed 92.2%–96.5% [7]
PVA
Completely hydrolyzed 98%–99% [7]
PVA
Solubility Soluble in water. [10]
Insoluble in aliphatic and
aromatic hydrocarbons,
oils, ketones, and esters
DOI 10.1002/pen
 TABLE 2. The physical properties of pure PVA.
Physical property Description
Appearance Creamy to whitish, granular, powder
Bulk density 641 kg s/m3
Density 1.19–1.31 g/cm3
Specific gravity 1.3 (for partially hydrolyzed, highly
viscous) [24]
Stability to sunlight Excellent
Flammability Burns like paper
All values are taken from [35], otherwise stated.
suggested to be useful as new materials for optical devices [30].
Muhammad et al. [31] explored the optical properties of sodium
nitrate (NaNO3) doped PVA nanocomposites. Doping contents
of 12 wt% NaNO3 in PVA changed the refractive index of PVA
(from 1.14) to 2.25, real part of dielectric constant from 1.30 (of
PVA) to 5.10, band gap from 5.71 eV (of PVA) to 5.05 eV.
The analysis of imaginary part of dielectric constant also have
proved that higher doping (9 and 12 wt%) of NaNO3 dissipated
more energy than at lower doping (0–6 wt%) [31]. Abdelaziz
and Ghannam [32] investigated the effect of titanium chloride
(TiCl3) on optical and dielectric properties of PVA based com-
posites. Incorporating 25 wt% TiCl3 resulted in decrease in
impedance of PVA (from 17.3 MX) to 3.8 MX, increase in
dielectric constant of PVA (from 11.3) to 157 at 1 kHz, and
decrease in optical band gap of PVA of 5.2 to 3.5 eV [32].
Abdullah and Saleem [33] doped PVA with copper sulfide
(CuS) NPs and investigated their electrical and optical behavior.
The values of optical band gap was decreased from 6.27 (PVA)
to 4.77 eV on addition of 0.04 molar concentration of CuS NPs.
On increasing frequency from 1 Hz to 1 MHz, the dielectric
constant and dielectric loss were decreased whereas, electrical
conductivity increased. Temperature dependence (308C–1108C)
behavior of dielectric loss, dielectric constant, and electrical
conductivity were also studied. The researchers suggested that
nanocomposites are useful in optoelectronic devices [33]. The
PVA composite materials could be utilized in different types of
sensors including mechanical, chemical, and biological ones [34].
MORPHOLOGIES OF PVA
Since the exploration of PVA matrix, it has been found in
various morphologies for a variety of applications. Different
morphologies of PVA have been studied by various researchers.
Some morphological assemblies are possible with the native
PVA matrix like films formation other depends on their modi-
fied composition and on the processing of prepared polymer
composites. Some of such morphologies are summarized as
follows:
Bulk PVA
PVA is commercially available in bulk form. It can also be
found in combination with other materials for some particular
applications. In bulk form, abundance of hydroxyl groups
attached to its carbon backbone originates a big source of
hydrogen bonding that has a major effect on its physicochemical
DOI 10.1002/pen
Physical property Description
Melting point 2308C for fully hydrolyzed,
1808C–1908C for partially hydrolyzed
Boiling point 2288C
Thermal stability Discoloration at 1008C,
darkens at above 1508C, decomposition
at 2008C
Specific gravity 1.3 (for completely hydrolyzed, highly
viscous) [24]
Glass transition temperature 758C–858C
Specific heat 1.5 J/(g K)
bulk properties. Due to hydrogen bonding in the matrix, PVA
has a high melting point. Interfaces play an important role in
understanding the behavior of materials like PVA. One disad-
vantage of working with materials in bulk form is the availabil-
ity of a small fraction of atoms at the interfacial surface.
PVA Hydrogels
A hydrogel may be defined as a crosslinked hydrophilic
polymer that swells in aqueous media [35]. Due to hydrophilic
nature of PVA, it requires crosslinks to prepare hydrogels for a
variety of applications [12]. The chemical crosslinkers that can
be used in the preparation of PVA hydrogels include formalde-
hyde, acetaldehyde, glutaraldehyde and other monoaldehydes
[12]. A variety of physical crosslinkers are available for the pro-
duction of PVA hydrogels for different purposes [13]. When
chemical crosslinkers are used with acetic acid, methanol or sul-
furic acid, acetal bridges are created in the suspended OH
groups of PVA chains [12]. By using a crosslinker, residual
amounts may be found in the subsequent PVA hydrogel. Extrac-
tion procedures may be adopted to remove the residue material
to avoid harmful and toxic effects for PVA hydrogel applica-
tions. The solubility of PVA and its resistance to most organic
solvents makes it suitable for a wide range of applications [11].
PVA Beads
Spherical PVA beads are prepared by using a saturated solu-
tion of boric acid as crosslinker and then by esterification of
PVA with phosphate for solidification. A pH range of 4–6 is
required for both bead strength and bead formation. A high pH
is better for strength and stability of PVA beads [36]. In order
to remove nitrogenous toxic waste, Jeong et al. [37] conducted a
study to evaluate the ability of water purification system made
from PVA gel beads using photosynthetic bacteria. The study
concluded that the immobilization of photosynthetic bacterial
system might be used in circulatory filtration system as one of
its working components [37].
PVA Fibers
Synthetic fibers can be fabricated by extrusion of a viscous
fluid from the outlet of a spinneret. Various types of polymer
spinning techniques are known today such as wet spinning, dry
jet-wet spinning, dry spinning, extrusion spinning, direct spin-
ning and gel spinning [38]. The other types are electrospraying,
POLYMER ENGINEERING AND SCIENCE—2018 3
electrospinning, and nanospidering [27, 38]. The wet spinning
technique is the oldest and requires the polymer to be dissolved
in a solvent to be spun. In this process, the spinneret is
immersed in a chemical tub where the fibers are precipitated
and then solidified. Acrylic, rayon and aramid fibers are made
from wet spinning [39]. In dry jet-wet spinning, the solution is
extruded outside the liquid tub and then immersed. Lyocell was
developed using this technique [40]. The spinning conditions of
dry spinning are the same as that of wet spinning, but solidifica-
tion in dry spinning is obtained via solvent evaporation. Acetate,
acrylic, and vinyon are fabricated by this technique [39]. Vinyon
(a copolymer of acetate and vinyl chloride) polymer is strong
resilient to sunlight and chemicals (alkalies and acids), so they
are recommended for heat scaling of clothes, fabrics and related
belongings [41]. The melt spinning technique is employed for
meltable polymers. Nylon, polyester and sulfur fibers are made
using melt spinning [39]. For the extrusion spinning technique,
polymer granules are compressed and melted and then fed into
the spinneret. The direct spinning technique is used for mass
production of polyester fibers. Gel spinning is adopted to obtain
high strength fibers. The gel state polymer retains bounded poly-
mer chains that results in production of high strength fibers.
Aramid and polyethylene fibers are produced using this tech-
nique [39].
Electrospraying uses electricity to produce fine aerosols from
polymeric solutions. The coulombs repulsive forces play a vital
role in aerosol formation. Chiu and Lin [42] prepared a nonwo-
ven nanohybrid substrate mat using coaxial electrospraying that
might be useful in biosensing applications. The nanohybrid mats
contained silver NPs and silicate nanoplates along with triblock
copolymer dispersant. PVA solution and silver-silicate disper-
sion were electrospun. The resulting nanohybrid mats showed
enhanced signal intensity (5.1 3 105) for surface enhanced
Raman spectroscopic biosensor [42].
PVA fibers can be made using a simple electrospinning tech-
nique. Micro to nanometer size fibers can be fabricated using a
simple setup. Figure 2 shows the setup for the electrospinning
process. The setup comprises a solution feeding pump, conduc-
tive nozzle connected to a high voltage terminal and a collector
connected to the ground terminal. The electrostatic forces are
responsible for converting the charged PVA solution into fine
fibers. The solution in the form of Taylor cone can be observed
suspended at the tip of the conductive nozzle. The electrostatic
potential draws the polymer jet from the Taylor cone apex to
FIG. 2. Diagram of fiber formation via electrospinning process.
4 POLYMER ENGINEERING AND SCIENCE—2018
collector. Reneker et al. [43] reported fiber mass flow rate of
water based polyethylene composite as 10–50 ng/s through a
single jet nozzle [43]. The available setups of electrospinning
are not suitable for large scale production. The nozzle-less (or
free surface) electrospinning techniques are being investigated
as a mean of overcoming this limitation [14]. Multiple polymer
solution jets from numerous locations are ejected simultaneously
in nozzle-less spinning devices working at more than 50 kV
(potential difference) in order to get mass production of polymer
fibers [14]. Cengiz et al. [44] fabricated roller electrospun PVA
nanofibers and investigated the effect of solution concentration,
viscosity, surface tension, conductivity, and molecular mass on
the quality and diameter of nanofibers. They concluded that sur-
face tension and electric conductivity do not have a significant
effect on the diameter of nanofibers; however, molecular mass
has a significant effect on the diameter of nanofibers. Meng
et al. [45] prepared good optical quality graphene loaded PVA
(G-PVA) nanofibers. The diameter and length of nanofibers
were in nanometers and centimeter range, respectively. The
interaction of light with these nanofibers was enhanced due to
their confined structure. For 1350 nm femtosecond pulses the
absorption saturation threshold was calculated as 0.25 pJ/pulse.
The prepared nanofibers showed good mechanical and optical
properties. The G-PVA nanofibers might be used in nanophoton-
ics and optical communication [45]. Ramalingam et al. [27] syn-
thesized graphene–PVA nanofibers for electrode material via
electrospinning. The electrospun fibers are widely used in flexi-
ble photocells, photonic crystals, optoelectronic devices, micro-
electronics, protective clothing, composite materials, and filter
media [2].
The nanospider technique is a modified version of the elec-
trospinning technique for commercial production of polymeric
nonwoven web and nanofibers. This technique requires a high
voltage electric field that can produce a charged polymeric
stream of electrospun solution. Using this technique, the Taylor
cone is produced on a rotating collector drum surface sub-
merged in polymer solution. As the Taylor streams are produced
next to one another along the length of the collector drum for
the commercial production of nanofibers or web [46]. Babinec
and Jirsak [47] prepared nonwoven fabric from PVA nanofibers
(100–300 nm size) with embedded magnetic NPs by using the
nanospider technique. The magnetization response measured
using magnetometer showed superparamagnetic behavior of the
samples. The behavior was attributed to thermally activated spin
rotation. The value of saturation magnetization was calculated
as 15 emu/g indicating excellent magnetic properties. The
microwave reflection loss was about 225 dB at 5 GHz, reflect-
ing good microwave absorption of the samples [47]. The pre-
pared nonwoven fabric might be used for electromagnetic
shielding (in GHz range) and electromagnetic heating (in MHz
range) applications [47]. Such a fine thickness nonwoven fabric
[47] could never be produced using nozzle less spinning [14]
and electrospinning technique [27].
PVA Films
PVA possesses the ability to form a uniform film of high
optical quality that can be used for nonlinear optical devices
and optical sensors. PVA has got increasing interest in the field
of photoluminescence [48]. Mieloszyk et al. [49] showed that
DOI 10.1002/pen
PVA exhibits phosphorescence at 103 K temperature in wave-
length range of 410–660 nm. They observed luminescence prop-
erties of PVA at room and low temperatures in the wavelength
of 400–510 nm. They also observed that PVA films exhibited
luminescence less behavior for exciting wavelengths less than
420 nm [49]. Goumri et al. [50] fabricated PVA nanocomposite
films using GO and partial RGO as the nanofiller and investi-
gated optical and electronic properties. They showed that 1 wt%
nanofiller had pH dependent fluorescence and significant lumi-
nescence effects [50]. Roy et al. [51] prepared PVA–ZnO nano-
composite films using the casting method. They investigated
dielectric and charge transport properties of the samples. Dielec-
tric constant and dielectric loss, both were reduced on increasing
nanofiller contents and frequency of input signal. AC conductiv-
ity was increased on increasing nanofiller contents and fre-
quency. The prepared nanocomposite films behaved as a
lossless material in the 1 MHz range indicating the usefulness
of the materials in microwave applications [51].
PVA Membranes
Membranes can be used in the separation process without
involving heat and are much more efficient than conventional
processes. The most widely utilized membranes are synthesized
of polymeric structures. Polymer nanofiber membranes are being
used in variety of applications including batteries, filter materi-
als, biomedical scaffolds, fuel cells, and osmotic power plants
[14]. Fuel cell membranes are considered an alternative tool for
converting chemical energy into electrical energy. The PVA
matrix plays an essential role in the formation of such valuable
membranes [15]. The electrospinning technique is considered as
a cost effective tool for producing web like membranes made
up of small fibers of large surface area for a number of possible
applications in producing sensors. Nanoscale fibrous membranes
can be fabricated using this technique. Such fibrous membranes
have almost two times the surface area as compared to continu-
ous thin films. The large surface areas of fibrous membranes
contribute greater sensitivity and rapid response time for electro-
spun sensors [48]. Arumugum et al. [52] developed large fiber
mats from a PVA solution but the fibers merged together. The
merging of fibers was proposed due to fiber collisions because
various points of the jet were collided and aggregated during
the thinning process. Wang et al. [53] fabricated PVA/4-vinyl-
pyridine graft polymer and was adsorbed on a nonwoven fabric
of poly(propylene) membrane surface. The grafted polymer was
used to improve the antibacterial and hydrophilic nature of the
membrane. On increasing the grafted polymer content
(0–1.5 wt%), the contact angle decreased (from 1238 to 33.48),
water permeate flux decreased, rejection rate increased and anti-
fouling attributes were improved [53]. Gu et al. [54] fabricated
a proton exchange membrane by employing PVA as a cross-
linker for sulfonated poly(phthalazinone ether sulfone ketone),
having a sulfonation degree greater than 81%. The ion exchange
capacity of the prepared membrane was 0.88 to 1.85 mmol/g
and determined to be dependent on PVA content [54].
PVA Scaffolds
One of the aims of tissue engineering is to make a biological
substitute that can restore damaged tissue by using the funda-
mental principles of biomedical engineering, material science
DOI 10.1002/pen
and cell biology. The scaffold is a key component in tissue
regeneration. A scaffold provides a mechanical platform as well
as favorable environment according to biomedical requirements
[55, 56]. Different techniques have been employed to fabricate
scaffolds for tissue engineering. Conventional techniques, such
as electrospinning, gas foaming, melt modeling, and solvent
casting are being successfully employed to fabricate scaffolds
that fulfill the biomedical criteria [17]. Scaffolds that were
made from prototype oriented methods showed good intercon-
nected and tractable pore structures [57]. However, prototype
based methods have limitations on the choice of building mate-
rials and cost of fabrication [58]. Thus, scaffold fabrication with
the desired biocompatible material strength, controllable pore
structure, high porosity and estimated degradation rate is a
major challenge [17]. The PVA has already been utilized in bio-
medical and pharmaceutical applications [59]. Ye et al. [17]
used PVA to fabricate controlled interconnected micro porous
3D scaffolds. They stirred PVA solution to generate pores then
freeze-dried the solution to make scaffolds. They showed that
on increasing stirring speed, stirring time, surfactant concentra-
tion, and molecular mass yielded improved porosity. They also
measured the rate of degradation, swelling ratio and mechanical
properties of the prepared scaffolds. Roy et al. [60] fabricated
stable, insoluble, lightweight fibrous multifunctional 3D PVA
scaffolds. Their mechanical and physical properties could be
altered by boosting the crosslinking conditions. Coating the
scaffolds with polydopamine (pDA) causes an enhancement in
surface chemical reactivity without affecting stability and other
native attributes of PVA fibers. The prepared highly absorbent
pDA–PVA scaffolds might be used as potential materials for
drug delivery, purification and tissue regeneration processes
[60]. Shuai et al. [61] prepared PVA–GO scaffolds using selec-
tive laser sintering technique. The objective of GO loading was
to improve mechanical strength of PVA for which they were
succeeded in getting 60% rise in compressive strength, 152%
rise in Young’s modulus, and 69% rise in tensile strength on
2.5 wt% GO loading. The enhancement is mechanical properties
attributed to uniform dispersion and robust hydrogen bonding of
GO nanosheets with PVA matrix. The prepared scaffolds might
be used in bone tissue engineering [61].
NATIVE PROPERTIES OF PVA
The effect of increasing molecular mass of PVA include an
increase in tensile strength, crystallinity, adhesion whereas flexi-
bility decreases, viscosity changes from low to high, the high
solubility in organic solvent is changed into high aqueous solu-
bility, the specific gravity increases from 1.19 to 1.31 [7]. The
other physical properties of PVA are listed in Table 2. The crys-
tal structure of PVA depends upon hydrogen bonding patterns.
Isotactic and syndiotactic PVAs exhibit an extended crystal sys-
tem and a helix crystal structure, respectively; the stability of
both the crystal structures is due to hydrogen bonding [16].
NEED FOR MODIFICATIONS OF PVA
The development of novel polymeric materials relies mainly
on compounding, blending and modification rather than chemi-
cal synthesis of a new polymer. PVA is an ideal matrix for mak-
ing flexible devices in electronics, optoelectronics,
bioengineering, and various other fields due to its lack of
POLYMER ENGINEERING AND SCIENCE—2018 5
 FIG. 3. Chemical modifications of PVA with possible applications.
toxicity, biocompatibility, high hydrophilicity and easy process-
ability. Hence, it is very important to modify PVA properties
for various targeted applications. PVA can be modified chemi-
cally through the hydroxyl groups on the backbone. Commonly
used conventional modification reactions include acetalization,
carbamation, etherification, or esterification of the hydroxyl
groups of PVA [62]. The modern chemical modification method
may be click chemistry. The modified PVA material may be
used in wide range of applications including molecular sensing,
biological and biomedical, the membrane of fuel cells, chemo
sensors, absorption of toxic metals and optoelectronic devices
[15]. Figure 3 represents the chemical modifications of PVA
having different degrees of hydrolysis and molecularmass.
Awada and Daneault [62] prepared chemically modified PVA
containing tosyl, azide, and amin functional groups that were
attached to the carbon backbone. Various analytical techniques
were employed to confirm the presence of these chemical modi-
fications [62].
One major problem in fabricating polymeric nanocomposites
is uniform dispersion of nanofillers in polymer matrix. Uniform
dispersion plays a vital role in making multifunctional compo-
sites and could be achieved by compounding techniques. Com-
pounding means mixing of different materials and these
materials may be either mixture of additives–polymers or poly-
mer–polymer. The resultant product may be a so-called blend or
composite [63]. Generally, three types of compounding techni-
ques are observed including melt compounding, in situ polymer-
ization and solution blending [64].
The PVA matrix contains abundant hydroxyl groups attached
to its carbon chain to allow other materials to be incorporated
FIG. 4. Hydrogen bonding of metal oxide with PVA matrix.
6 POLYMER ENGINEERING AND SCIENCE—2018
via hydrogen bonding. Figure 4 shows the hydrogen bonding
mechanism of metal oxides such as CuO, ZnO, Al2O3, or others
with the PVA matrix. Figure 5 shows the hydrogen bonding
mechanism of GO nanosheets with the PVA matrix.
PVA NANOCOMPOSITES
A polymer composite comprises of reinforcing filler and
polymer matrix. The dimension of fillers may be in micrometer
or in nanometer. A polymer composite delivers such properties
that are absent in both filler and matrix. The incorporation of
fillers can modify the physicochemical properties of polymers.
The type, size, shape, concentration, and mutual interaction
have a strong effect on the modified polymer composite. Fillers
may be of various kinds including metal powders, volcanic min-
erals, chalk, polymeric fibers, glass fibers, carbon fibers and
also natural fibers [65]. Fillers with nanodimensions are
regarded as smart dopant materials due to their extraordinary
surface reactivity with polymers. Nanomaterials are normally
classified into 0, 1, 2, and 3 dimensions (D). The 0-D materials
are in the form of quantum dots, nanolenses, nano onions. The
1-D materials are found in the form of nanowires, nanobelts, or
nanotubes. The 2-D materials are found in the form of nano-
sheets, nanoplates, nanodisks or nanowalls, whereas 3-D materi-
als are found in the form of nanocoils, nanocones, nanoballs,
nanoflowers, or nanopillers [66, 67]. The combinations of nano-
materials with polymers are known as polymer nanocomposites.
Nanofillers (<5 wt%) are most widely used to enhance the
properties of polymers including toughness, strength, modulus,
heat and scratch resistance, dimensional stability, thermal, and
electrical conductivity due to their high aspect ratio [68]. Nano-
fillers have advantage of possessing large surface area for inter-
action with surrounding matrix that is the key concept for the
enhancement of the properties of polymeric nanomaterials. In
addition, nanofillers possess a quantum confinement effect
which makes nanofiller–polymer interaction of great importance.
Over the last 50 years, PVA has been a candidate material for
diverse applications. PVA nanocomposites may include nanofil-
lers made from metals, nonmetals, metal oxides, metal sulfides,
inorganic, or combinations of these materials. Inorganic nanofil-
lers may include carbon nanofibers, carbon nanotubes, clays, sil-
icates and others. PVA is used as an embedding mat and matrix
for metal/inorganic nanofillers for sensing, designing of opto-
electronic devices and many other applications [15]. A few
PVA nanocomposites are discussed here.
DOI 10.1002/pen
 FIG. 5. Representative hydrogen bonding of GO nanosheets with PVA matrix.
PVA Based Biocomposites
PVA plays an important role in biomedical devices because
of its good water solubility, biodegradability in human tissue,
biocompatibility, low protein absorption property, and chemical
resistance. Mohanty et al. [69] fabricated biocomposites of
PVA–date palm leaf fiber (DPL) via melt mixing route. In order
to increase mechanical strength, compatibility, and dispersion in
PVA, DPL fibers were treated chemically with different chemi-
cal (using maleic anhydride, peroxide, permanganate, benzoyla-
tion, alkaline, and acrylic acid) procedures and mechanical
strength was tested after every procedure. Acrylic acid chemical
procedure proved the best one. The 28 wt% contents of DPL
fiber enhanced Young’s modulus value of the biocomposite
from 362.5 (pure PVA) to 1183 MPa and the enhancement was
attributed to strong interfacial adhesion of fibers with the PVA
matrix. Storage and loss moduli observed same decreasing trend
with increasing temperature. Storage modulus of 28 wt% DPL
composite was decreased from 550.5 (41.48C) to 50 MPa
(1608C). The study showed that degradation temperature was
increased from 490 (of pure PVA) to 5808C (of prepared bio-
composite) indicating enhancement in thermal stability. The
date palm leaves proved good mechanical and thermal reinforce-
ment filler, and the prepared biocomposites might be used in
automotive, housing, and industrial usage [69]. Singha et al.
[70] reported corn starch (St)-PVA biocomposites, in which lig-
nin free Grewia optiva fibers and grafted methyl methacrylate
were incorporated for reinforcement purpose. During preparation
glutaraldehyde crosslinker and citric acid plasticizer were used.
Antibacterial activity against Staphylococcus aureus and Escher-
ichia coli was observed. The tensile strength was increased from
33 to 40.6 MPa on incorporating 5–20 wt% lignin free fibers.
Grafted fibers (5–15 wt%) enhanced the tensile strength of com-
posites from 36.4 to 45.6 MPa. The films were deteriorated
DOI 10.1002/pen
when exposed to soil. Thermogravimetric analysis (TGA)
proved good thermal properties of the biocomposites. The bio-
composites might be used as food packaging and agriculture
materials [70]. Tran et al. [71] fabricated microalgae ash–PVA
biocomposites. Raw ash was achieved using Nannochloropsis
salina biomass and activated with sodium hydroxide. To
improve interfacial interactions, surface modifications were
made using (3-aminopropyl) triethoxysilane. Thermal and
mechanical properties of biocomposites were enhanced by using
fillers attributed to bolstering hydrogen bonding between ANH2
group of filler and AOH group of PVA. The study suggested
that ash of microalgae is suitable to enhance feasibleness of
microalgae oriented biorefinery [71]. The study suggest that
PVA based biocomposites are stronger, thermally stable, and
antimicrobial ones.
Metal PVA Nanocomposites
Metal NPs fall into an exciting research area due to their
magnetic, electronic, and optical properties that can be used in
technological applications. Silver possesses the highest thermal
and electrical conductivity. Silver NPs have potential applica-
tions in photonics, photography, adhesives for electronic compo-
nents, thick film paste and conductive inks. Polymers are now
known to be excellent host matrices for metallic and semicon-
ductor NPs. On incorporating (or encapsulating) NPs in poly-
mers they behave like surface capping agents. So film casting
becomes easy and size of the particle becomes controllable
within the required range. For the applications in electronics and
optoelectronics, controlled size of NPs and their uniform disper-
sion in the polymer matrix are important features for further
technological applications. Krkljes et al. [72] prepared silver
doped PVA nanocomposites loaded with various contents. This
was achieved by reducing silver ions in a PVA aqueous solution
POLYMER ENGINEERING AND SCIENCE—2018 7
using gamma irradiation. The nanocomposite films were pre-
pared using the solution casting approach. The radiation dose of
cobalt 60 was varied (from 0.27 to 12.04 kGy) at a rate 12 kGy/
h, in order to reduce 0.17 to 5.79 mM silver ions. The structural
and optical properties were investigated. The infrared spectra
showed that silver NPs interact with the OH groups of PVA
[72]. Ghanipour and Dorranian [73] investigated PVA based
nanocomposites with different doping contents of silver NPs.
Laser ablation method was adopted to prepare silver NPs. On
incorporating 0.65 mg of silver NPs in 1 g of PVA powder,
refractive index of PVA (1.56) was decreased to 1.19 and band
gap of PVA (5.19 eV) was decreased to 4.87 eV. The nanocom-
posites might be used for optical dispersion devices [73]. Nasar
et al. [74] fabricated copper NPs by chemical reduction of cop-
per nitrate. The NPs were dispersed in a PVA matrix and used
to prepare Cu-PVA nanocomposite films at various composi-
tions. An impedance analyzer showed that Cu NPs conveyed
electrical conductivity to the PVA matrix and the conductivity
increased on increasing Cu NPs contents. The Young’s modulus
and elongation at break were increased while tensile strength
decreased at higher Cu contents. It was suggested that the pre-
pared films might be used in charge storage devices [74]. Perez
et al. [75] incorporated gold nanorods homogenously in thin
PVA films and aligned the nanorods using physical means of
heating and stretching the films. The alignment of nanorods was
observed using transmission electron microscopy. The alignment
might be attributed to elongation of PVA molecules upon heat-
ing and stretching. The optical response of dispersed nanorods
was calculated and the results agreed with the dipole model.
The dispersed gold nanorods were of different aspect ratio.
When the films were irradiated with a pulsed laser (1064 nm),
the gold nanorods were reshaped into nanospheres. The effect
suggested micropatterning the optical structures into composite
films [75]. Kumar et al. [4] prepared cobalt doped ZnO loaded
PVA nanocomposite films using the sol–gel method. Optical
properties of the prepared nanocomposites were studied by ultra-
violet visible spectroscopy and photoluminescence, and the ther-
mal properties using thermogravimetric analysis. Band gap was
reduced and thermal stability enhanced. The studies suggested
the applications of the prepared nanocomposites in UV shield-
ing, nanophotonic devices, and visible light emitting diodes [4].
PVA Based Graphene, Zinc, and Copper Oxides Nanocomposites
In this section, a brief review of some selected PVA nano-
composites is presented.
GO–PVA Nanocomposites. The allotropes of carbon family are
fullerene (0-D), nanotubes (1-D), graphene (2-D), and graphite
(3-D). Researchers have also explored the other forms of carbon
such as cokes, synthetic graphite, carbon black, synthetic dia-
monds, etc. [76]. The ground state electron configuration of car-
bon atom is 1s2 2s2 2p2. Carbon can form up to four covalent
bonds that can be explained using orbital hybridization concept.
The hybridization of carbon atomic orbitals depends on the
number of atoms bound to the carbon atom. The hybridized con-
figurations of carbon may be sp3, sp2, or sp and leads to molec-
ular structures, such as tetrahedral, trigonal, or planer.
Graphite occurs in nature in the form of flakes or powder.
Natural graphite flakes are thin sheets of less than 100 nm
8 POLYMER ENGINEERING AND SCIENCE—2018
FIG. 6. Graphite flake showing arrangement of graphene nanosheets.
thickness [77]. The layered structure of graphite is due to the
presence of covalent bonds between carbon atoms that shape
them into hexagonal sheets. The van der Waals’ interactions
hold the hexagonal sheets together [78]. Graphite is a good con-
ductor of heat and electricity in the planar direction because of
the presence of r bonds and p-delocalized bands; whereas, it is
a poor conductor of heat and electricity in the stacking direction
because of the occurrence of van der Waals’ interactions in
layers. The distance between two consecutive graphite hexago-
nal sheets is 3.358A whereas two carbon atoms in the hexagonal
sheet are 1.428A apart [79]. Each graphite hexagonal sheet is
sp2 hybridized and is called a graphene sheet. The graphite
structure is shown in the Fig. 6. The intercalation of graphene
sheets in graphite layers is very hard due to minute interlayer
distance. So a physical or chemical route is adopted to create
modifications in graphite flakes. Graphite oxide is usually fabri-
cated by oxidation of natural graphite flakes and acquires the
shape of pseudo 2-D thin sheet [79].
Normally, graphite oxide is prepared by the chemical route
proposed by Hummers, Staudenmaier, and Brodie, where oxida-
tion is performed using strong acids and oxidants. The oxidation
level is determined by graphite precursor, fabrication route, and
the conditions of the chemical reaction [80]. After oxidation,
oxygen containing groups such as hydroxyl, epoxy, carboxyl,
and carbonyl are attached to each graphene layer in carbon ali-
phatic regions [79]. Among these polar groups, hydroxyl group
lies above; whereas, epoxy group lies below the graphene sheet.
Carbonyl and carboxyl groups are attached near edges of gra-
phene sheets. As a consequence of these groups, the nature of
graphite oxide is converted to robust hydrophilic and its disper-
sion in water is very easy. The exfoliation of graphite oxide
using ultrasonication waves or thermal shocks may result in GO
nanosheets [81].
As graphene is a new material, there is lot of scope for
exploring the mechanical, optical and electrical properties of
graphene based PVA nanocomposite. Liang et al. [82] prepared
PVA–graphene composites, employing the solvent evaporation
method. The XRD peak of GO (10.98) was completely exfoli-
ated as discrete graphene nanosheets in PVA matrix. The
0.7 wt% GO doping of PVA resulted in the enhancement of ten-
sile strength and Young’s modulus by 62% and 76%, respec-
tively. This was attributed to hydrogen bonding and uniform
DOI 10.1002/pen
dispersion of GO in the PVA matrix. Zhao et al. [83] fabricated
PVA–exfoliated graphene composites using the solution casting
approach. The XRD pattern revealed that the graphene peak is
dispersed due to disappearance of this peak in the nanocompo-
sites. Tensile strength was enhanced 150% at 1.8 vol% doping
of graphene in the PVA matrix. Morimune et al. [84] fabricated
PVA–GO films using ordinary solution casting process. They
observed that on increasing GO nanofiller loadings, Young’s
modulus, tensile strength, thermal and barrier properties were
improved, significantly. The enhanced properties were attributed
to stiff structure and large aspect ratio of individual GO sheets
[84]. Goumri et al. [50] prepared GO and graphene nanosheets
using the chemical route. They prepared PVA–graphene and
PVA–GO films using solution mixing in aqueous medium. They
reported strong luminescence when the nanocomposites were
dispersed in acidic medium. Band gap energy of the nanocom-
posites was decreased [50]. Pawar et al. [85] prepared GO–PVA
nanocomposites using a simple solvent evaporation method. The
0.5 wt% GO-doped PVA composite showed enhanced specific
capacitance of 400 F/g (a much higher value than other car-
bon-nanocomposites). The nanocomposite was stable and
retained a value of about 92% specific capacitance after many
cycles. The researchers suggested the nanocomposite to be suit-
able as an electrode material for supercapacitors [85].
Deshmukh et al. [86] reinforced PVA/poly(4-styrenesulfonic
acid) (PSSA) blend with GO and calculated electrical parame-
ters such as dielectric constant and dielectric loss. On incorpo-
rating 3 wt% GO, contact angle of PVA–PSSA blend decreased
from 78.18 to 66.28, surface energy increased from 36.6 (PVA)
to 44 mJ/m2, dielectric constant increased from 82.6 (PVA) to
297.9 (at 50 Hz, 1508C), dielectric loss increased from 1.56
(PVA) to 2.64 (at 50 Hz, 1508C). The prepared flexible nano-
composites are strong candidates for energy storage devices
[86]. Pandele et al. [87] prepared Chitosan (CS)-PVA and GO
based nanocomposites. The prepared nanocomposites were
mechanically strong (tensile modulus increased 1.83–5.78 GPa
on 6 wt% GO addition), thermally stable and showed bioactive
properties that make them suitable candidates for tissue engi-
neering [87]. The 0.5 wt% GO doped PVA nanocomposite film
prepared by Aslam et al. [5] showed increased relative crystal-
linity (23.7% of PVA to 44.4%), increased tensile strength
(25.6 MPa of PVA to 43 MPa), increased Young’s modulus
(144 MPa of PVA to 404 MPa), decreased direct band gap
(5.31 eV of PVA to 4.64 eV) and increased Urbach energy
(0.21 eV of PVA to 0.62 eV). The optical band structure of GO
doped PVA films was investigated in detail. The GO incorpora-
tion enabled PVA matrix to be used in optoelectronics applica-
tions [5].
RGO–PVA Nanocomposites. There are many routes for the
fabrication of graphene nanosheets in the lab. The basic one
was the scotch tape method [88]. This method was primarily
used to obtain pure, defect free graphene nanosheets for labora-
tory research. The other methods include, chemical synthesis,
arc discharge, pyrolysis, chemical vapor deposition (CVD), sol-
vothermal, electrically assisted synthesis, epitaxial growth, exfo-
liation, unzipping of carbon nanotubes and molecular beam
epitaxy [88, 89]. It was first effort made by Novoselov’s group
in 2004, to discover monolayer graphene nanosheets. This group
DOI 10.1002/pen
used adhesive scotch tape method repeatedly, to peel off a thin
graphite layer from a selected graphite crystal. They transferred
the thin layers onto a thin (less than 300 nm) oxidized silicon
sheet. Finally, Andre Geim and Konstantin Novoselov suc-
ceeded and were awarded the 2010 Nobel Prize in Physics for
the discovery of 2-D graphene nanosheets. The discovery led to
large scale graphene production and its applications in various
polymers for the electronics industry.
Among different routes for the synthesis of RGO or graphene
nanosheets, such as thermal, microwave, microbial and chemi-
cal, the chemical route is preferred because it is an inexpensive
for large-scale production. The chemical route comprises of
three stages: the oxidation of graphite flakes, aqueous dispersion
of graphite oxide and finally a reduction reaction to produce
RGO. The oxygen functional groups in GO introduce sp3 lattice
defect sites into the graphene sheets, altering the inherent conju-
gated p-system, thus lowering the electrical conductivity and
strength, generally. On the other hand, reactivity of the intro-
duced functional groups makes GO sheets exceptionally interest-
ing as the building blocks of various macroscopic structures,
because they can readily be amended with various surfactants.
The introduced oxygen functional groups can easily be removed
by reduction mechanisms, improving the mechanical strength
and electrical conductivity of the RGO nanosheets. Graphene
and its derivatives are being explored extensively for their out-
standing mechanical, electrical, optical, chemical, and thermal
properties. These materials have high mechanical strength,
superb electrical and thermal conductivities, exceptional chemi-
cal stability, and an ultrahigh surface area. A large number of
applications for the material are found in nanoelectronics, super-
capacitors, biological and chemical sensors, lubricants, polymer
composites, solar cells, aerosols, corrosion protection and inkjet
printing [90]. Aslam et al. [18] fabricated mechanically strong
and optically tunable RGO doped PVA nanocomposite films.
On incorporating 0.02 wt% RGO in PVA relative crystallinity
of PVA (23.7%) was enhanced to 39.6%, tensile strength
increased 25.6 (PVA) to 45.6 MPa and Young’s modulus
enhanced from 144 (PVA) to 162 MPa. Incorporating
0.012 wt% RGO in PVA, direct band gap was decreased from
5.29 (PVA) to 3.59 eV, indirect band gap decreased from 4.95
(PVA) to 3.20 eV, refractive index increased from 1.37 (PVA)
to 2.62 at 300 nm and optical conductivity enhanced from
6.3 3 109 (PVA) to 6.2 3 1011 S at 300 nm. The nanocompo-
sites might have potential applications in optoelectronic devices
[18]. Yang et al. [91] fabricate layer aligned PVA–graphene
nanocomposites films. Incorporating 3.5 wt% graphene, tensile
strength of PVA (22 MPa) was increased to 29 MPa, Young’s
modulus was increased from 0.45 (PVA) to 0.52 GPa, glass
transition temperature of PVA (76.28C) increased to 90.58C,
crystallinity decreased from 38.3% (PVA) to 5.6%, melting tem-
perature was decreased from 230.28C (PVA) to 228.98C and
crystallization temperature decreased from 2008C (PVA) to
198.48C [91].
ZnO–PVA Nanocomposites. Wurtzite structured, whitish
appearance zinc oxide (ZnO) NPs have attracted researchers due
to its inexpensiveness and belonging to semiconductor group
(II–VI). It is an electrical conductor and possesses a huge piezo-
electric constant that makes it suitable for manufacturing of
POLYMER ENGINEERING AND SCIENCE—2018 9
ultrasonic transducers. This n-type semiconductor is equipped
with exclusive electro-optical properties, excellent electrical and
thermal conductivity, large optical band gap (3.2 eV at 300 K),
good chemical stability and large exiton binding energy
(60 meV). These properties make the multifunctional material
an attractive candidate for the production of nanostructures,
such as nanowires, nanobelts and nanorods, to be used in a vari-
ety of electronic appliances. Nanostructures of ZnO are being
used in lasing and luminescence devices, short wavelength
LEDs, varistors, organic solar cells, gas sensors, translucent thin
transistors, photovoltaic cells, transparent conductors, and cos-
metics [92, 93].
Bouropoulos et al. [94] fabricated ZnO NPs using thermal
decomposition method. They fabricated ZnO doped PVA nano-
composite films using the casting method. The scanning electron
micrographs revealed spherical shaped NPs as 50–150 nm size.
Dielectric spectroscopy was employed to explore the response
of particle size over relaxation aspect at the interface and
showed the dependence of interfacial polarizations on particle
size in all nanocomposites [94]. Rashmi et al. [95] prepared
ZnO NPs using the precipitation approach. The PVA–ZnO films
were fabricated using the solution casting method. Glutaralde-
hyde nanofillers were also added to the composites. Elongation
at break as well as tensile strength with and without incorporat-
ing glutaraldehyde nanofiller were calculated. It was shown that
with the addition of glutaraldehyde nanofiller, both parameters
were improved significantly [95]. Hemalatha et al. [93] prepared
nanocomposites of ZnO and PVA using the casting approach.
The ZnO NPs were prepared using the combustion approach.
The XRD analysis confirmed the Wurtzite structure of ZnO par-
ticles. Crystallite size was measured using both the Scherrer and
Williamson–Hall method. For a composite PVA–ZnO
(20 mol%), crystallite size was increased from 29 (of pure ZnO)
to 32 nm and microstrain increased from 8.13 3 1024 (of pure
ZnO) to 8.43 3 1024. The change in crystallinity was attributed
to variation in crystallite size and presence of aggregation of
NPs. The shift in position of FTIR AOH stretching peak of
PVA was observed on incorporating ZnO nanofiller, indicating
nanofiller–matrix strong interaction. The band gap of ZnO nano-
particles were blue shifted with respect to ZnO bulk material,
due to reduction in size of NPs. Band gap of nanofiller was red
shifted in nanocomposite films due to deformation of band
structure and creation of defect states in the PVA matrix. Band
gap of PVA (4.74 eV) was reduced to 2.38 eV on incorporating
20 mol% ZnO nanofiller in PVA. The prepared nanocomposites
showed UV luminescence and could be used in optoelectronics
applications [93].
CuO–PVA Nanocomposites. In semiconductor physics, copper
oxide is well known. It is found in the form of cuprous oxide
(Cu2O) and cupric oxide (CuO). These have dissimilar physical
and electrical behavior. CuO is a black-brown solid having a
monoclinic crystal structure, whereas Cu2O is a brownish-red
solid having a cubic crystal structure. The lower production
costs and better electrochemical attributes makes CuO a good
choice for making sensors, electrical and optical devices. CuO
is p-type semiconductor with a narrow optical band gap (1.2–
1.9 eV), large dielectric permittivity and good insulating proper-
ties. Due to its small energy band gap, electrons can easily
10 POLYMER ENGINEERING AND SCIENCE—2018
jump from one energy state to another. The material is also
used as a catalyst in the treatment of waste water and for anti-
microbial purposes. CuO NPs have been used in a variety of
applications including supercapacitors, photoconductive materi-
als, nanofluids, bio and gas sensors, solar cells, and magnetic
storage media [96, 97].
There are few reports on CuO doped PVA nanocomposites.
Rao et al. [97] formulated PVA–CuO nanocomposites using the
casting method. The CuO NPs were fabricated via combustion
route using glycine nitrate. They observed a decrease in crystal-
linity of PVA (from 4.39% to 0.07%), decrease in glass transi-
tion temperature (from 81.68C to 72.18C), decrease in melting
temperature (from 224.38C to 158.18C) and decrease in crystalli-
zation temperature (from 189.88C to 114.78C) on incorporating
2 wt% CuO NPs. The value of dielectric constant of the nano-
composites was reduced with increasing frequency due to dipo-
lar orientation of the samples along the external electric field.
The AC conductivity and dielectric loss of the prepared samples
were decreased on increasing nanofiller contents [97]. Abdullah
et al. [98, 99] optically characterized the PVA–CuO samples.
The samples were prepared using the solution casting method.
Incorporating 12 wt% CuO NPs resulted in decrease in band
gap of PVA (from 6.28 eV) to 3.18 eV and dispersion energy
increased from 1.03 (of PVA) to 2.78 eV of composites [98].
Manjunath et al. [99] fabricated CuO NPs, using the precipita-
tion process, and incorporated (1 to 5 wt%) into the PVA
matrix. The average crystallite size was calculated as 8 nm.
They investigated AC conductivity and dielectric constants in
50 Hz to 5 MHz frequency range at 303 to 338 K temperature
range. They observed that by increasing frequency, electrical
conductivity was increased, whereas dielectric constant
decreased. The optical band gap of the nanocomposites was
decreased from 4.97 to 3.03 eV by incorporating 5 wt% CuO.
The full width at half maximum of the main XRD peak was
increased by incorporating the nanofiller, suggesting an increase
in amorphous nature of nanocomposites [99].
Other types of PVA based nanocomposites have also been
reported. Qian et al. [100] prepared PVA based nickel, cobalt,
and iron sulfide nanocomposites via a hydrothermal process.
They observed a decrease in PVA crystallinity after addition of
the metal nanosulfide particles [100]. Saini et al. [9] used PVA
grafted silicon carbide (SiC) nanocrystals to enhance the proper-
ties of PVA. The refractive index of pure PVA was increased
(1.5–2 at 550 nm) and Knoop microhardness number was also
increased (2.4–4.8 kg gf/mm2) after incorporating 0.015 wt%
grafted SiC. Dispersion parameters and dispersion of refractive
index were also analyzed. The voltage–current curve analysis
showed that the Schottky transport mechanism was dominant at
medium to high voltage range whereas, the Poole–Frenkel con-
duction mechanism was dominant at low voltage range [9].
Overall, the significance of nanotechnology is increasing
day-to-day in every field of science and technology. Conven-
tional materials are being replaced with polymeric nanomaterials
due to their light weight and extraordinary physicochemical
properties. Various types of nanofillers have potential to modify
PVA structure to meet the requirements of modern technological
applications. Several studies have been reported in this review
article, a few of them are summarized in Table 3. The effect of
different dopants on mechanical, optical, and electrical proper-
ties of PVA is presented in Table 3, indicating property
DOI 10.1002/pen
DOI 10.1002/pen
TABLE 3. Effect of different dopants on mechanical, optical, and electrical properties of PVA is presented.

Dopant Decreasing parameter values Increasing parameter values Application areas Refs.

Black tea Band gap Dispersion in refractive index Inorganic solar cells, optoelectronics [28]
CoCl2a Band gap – – [29]
ErCl3 Band gap Refractive index Optoelectronics [30]
NaNO3 Band gap Refractive index, dielectric constant, dielectric – [32]
loss
CuS Band gap, dielectric constant, dielectric loss Electrical conductivity Optoelectronics [33]
Ag Band gap, refractive index Signal intensity Biosensors, dispersion devices [41, 75]
Ferrite – Saturation magnetization EMI shielding [46]
DPL Storage modulus Tensile strength, Young’s modulus, thermal Automotive, housing, industrial usage [69]
stability
Grewia optivab – Tensile strength, thermal stability Food packaging, agricultural materials [70]
Micro algae ash – Mechanical properties, thermal properties Microalgae based biorefinery [71]
Copper Tensile strength Young’s modulus, elongation at break Charge storage devices [73]
Co-ZnO Band gap Thermal stability UV-shielding, nanophotonics [4]
Ni, Co, FeS Crystallinity – – [100]
SiC – Refractive index, microharnening – [9]
GO Band gap, contact angle Crystallinity, tensile strength, Young’s Bone tissue engineering, [5, 9, 49, 60, 82–87]
modulus, barrier properties, Urbach energy, supercapacitor electrode material, energy
refractive index, dielectric constant, storage devices, tissue engineering,
dielectric loss, optical conductivity, optoelectronics
luminescence, specific capacitance, surface
energy, thermally stable, bioactivity
RGO/ Crystallinity, band gap, melting temperature, crystallinity, tensile strength, young’s modulus, Soft electronics, supercapacitors, [18, 26, 27, 91]
Graphene crystallization temperature Urbach energy, refractive index, optical optoelectronics
conductivity, electrical conductivity, glass
transition temperature
ZnO Band gap, dielectric loss Tensile strength, elongation at break, dielectric Optoelectronics, EMI, and UV shielding, [50, 93, 95]
constant AC conductivity microwave absorption, UV luminescence
CuO Crystallinity, band gap, dielectric constant, Dispersion energy, optical conductivity – [97–99]
dielectric loss, glass transition temperature,
melting temperature, crystallization
temperature, AC conductivity

Note. Increasing/decreasing parameter values are estimated with respect to corresponding values of native PVA.
a
PVA-PPY.
b
Corn starch-PVA.

POLYMER ENGINEERING AND SCIENCE—2018 11

modifications with possible applications. Some parameter values
are exceeding from corresponding values of pure PVA and
others fall behind. The review indicates that there is lot of
potential to develop new materials for biosensors, biological,
organic solar cells, optical communications and dispersion devi-
ces, microelectronics, EMI shielding, optoelectronic devices,
and for other fields and to evaluate their efficiency.
CONCLUSIONS AND FUTURE PERSPECTIVES
Nanomaterials are alternatives to conventional additive
materials for the enhancement of polymer attributes. The nano-
materials are responsible for recent progress in PVA composites.
The literature shows that PVA nanocomposites find plenty of
potential applications in various fields of science and technol-
ogy. The research premises are now shifted from engineering
based on empirical methods to advanced industrial application
areas which provide basic source of interest. The fundamental
questions related to the synthesis of polymer nanocomposites
are of great attractions for new researchers. Tailoring physico-
chemical properties of polymer nanocomposites is a major chal-
lenge to present synthesis methodologies. Systematic variations
in experimental variables to investigate causes and effects, strict
control over experimental conditions using suitable techniques,
and solid fundamental knowledge about the situation parameters
might help in overcoming the challenges. In the near future,
some possible issues in the developments of PVA nanocompo-
sites may include: diversity in nanofiller types with multifunc-
tionalities, increase in structural complexity, uniform
dispersions, in depth understanding of interfacial interactions,
and better control over synthesis steps with controlled morphol-
ogies. These issues require refinement of experimental techni-
ques, boosting systematic approach, and advanced specific
knowledge. As a consequence, there might be progress in
enabling significant innovation in industry and small-medium
enterprises. Hope the researchers will overcome the issues and
auspicious future of PVA composites can be expected. The mar-
ket economy and entrepreneurship related to high-tech PVA-
based products will be stimulated.
ACKNOWLEDGMENTS
The authors acknowledge the help of Prof. Dr. Rob Briddon
for improving the language of this manuscript.
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