Research Article

Received: 21 December 2021 Revised: 9 February 2022 Accepted article published: 21 February 2022 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/pi.6385

Study of the preparation and properties of

polyvinyl chloride/nitrocellulose polymer
blends
Pratibha S Jadhav,a Girish M Joshi,a* Shankar S Humbe,a
Raghvendra S Dubeyb and Shaik Kaleemullac

Abstract
In this study, we prepared Polyvinyl chloride (PVC)/Nitrocellulose (NC) polymer blend by the solution casting technique. The
structural properties and decreased interplanar spacing and crystalline nature of the PVC/NC blends were confirmed by an
XRD technique. Basic chemical fingerprint regions of PVC/NC blends were confirmed by the Fourier transform IR method. Opti-
cal properties correlated with a decreased direct and indirect bandgap energy of PVC/NC were estimated using UV–visible spec-
tra. They exhibited a shift in the absorption spectra towards the longer wavelength region due to process of charge transfer in
the blend system. An increased microporous nature of the blends was demonstrated by SEM. Based on the Maxwell–Wagner
model the dielectric constant and relative loss were found to have a maximum in the low frequency region which may be con-
tributed by the polar nature of NC. We confirmed the hydrophilic nature of the PVC/NC blends due to the presence of hydroxyl
groups by the goniometer technique. The thermophysical properties of the blends were measured by Lee's disc method. NC
loading in the blend system increased the thermal conductivity from 0.12 to 0.18 W/(m.K). The Shore A softness test of the
blends exhibited an 18% increase. We quantified structure, bandgap, morphology, and dielectric, surface and thermal proper-
ties as a function of NC blending. This new emerging blend may be a remedy for various engineering applications.
© 2022 Society of Industrial Chemistry.

Keywords: polyvinyl chloride; nitrocellulose; polymer blend; contact angle; surface energy; thermal conductivity

INTRODUCTION proton acceptor solvents like tetrahydrofuran (THF) and cyclohex-

Optimised properties of a new class of polymer blends contribute
towards desirable domestic and industrial applications. The grow-
ing need for polymer materials with tailored multifunctional fea-
tures has resulted in a variety of blends.1 The development of
polymer blends is aimed at obtaining appropriate and synergistic
qualities of known polymer components.1 The scope for polymer
mixing is a huge and limitless field of study that necessitates most
careful theoretical and experimental consideration. Polymer
blends offer better qualities than their virgin component polymer
system.2 Blending has received a lot of interest as a simple and
cost-effective way to generate polymeric materials with a wide
range of commercial uses. Based on the proposed applications,
polymer blends with unique features can be easily designed by
increasing it's physical and chemical properties.3 Several charac-
teristics such as glass transition temperature or thermophysical
properties have been explored to optimise the thermal conduc-
tivity, thermal diffusion, specific heat capacity, dielectric constant,
surface energy (SE) and elastic moduli that can be achieved by
polymer blends.4
Polyvinyl chloride (PVC) is a domestic polymer that has 10
branches per molecule and the presence of more than one long
chain per molecule is unlikely.5 It stands out due to its high chem-
ical and atmospheric pollutant resistance, as well as favourable
mechanical and functional qualities, fire resistance and low
manufacturing costs.6 For complete dissolution, it requires weak
ane because PVC can operate as a weak proton donor. Its utilisa-
tion is limited to some extent because of its low thermal
resistance. It requires the use of thermal stabilisers when proces-
sing for enhancing thermal performance. The blending purpose
of PVC with other polymers is improved impact strength, process-
ability and other mechanical, thermal, electrical and optical
properties.7
Nitrocellulose (NC) is often known as cellulose nitrate. It is a cel-
lulose derivative that has been used in a variety of commercial
and military applications. It has a comparable appearance to cot-
ton. NC is water-insoluble but rapidly dissolves in a nonpolar
organic solution.8 It is manufactured from cellulose as the primary
* Correspondence to: GM Joshi, Department of Engineering Physics and Engi-
neering Materials, Institute of Chemical Technology Mumbai, Marathwada
Campus, Jalna 431203, Maharashtra, India. E-mail: gm.joshi@marj.
ictmumbai.edu.in
a Department of Engineering Physics and Engineering Materials, Institute of
Chemical Technology Mumbai, Marathwada Campus, Jalna, India
b Centre for Functional Materials, VIT, Vellore, India
c Advanced Research Laboratory for Nanomaterials and Devices, Department of
Nanotechnology, Swarnandhra College of Engineering and Technology,
Narsapur, India
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 www.soci.org PS Jadhav et al.

raw material. The nitration of natural cellulose from cotton linter
or wood pulp produces NC by cooking, bleaching, washing, dry-
ing and other processes, which have a wide range of characteris-
tics and applications.9 Sulfuric acid is the best additive to the
nitrating mixture and delivers a great result, according to the ideal
circumstances of cellulose nitration.10 The manufacturing
methods of NC are different for different applications. The utilisa-
tion of NC is highly dependent on its nitrogen content; for exam-
ple, NC with a nitrogen content of 10.7%–12.3% is used in
coatings and printing inks,11 while 12.6%–13.5% of nitrogen con-
tent is used as an explosive for gun propellants. It was first devel-
oped for use in explosives and propellants which is still one of the
most important markets for materials today.12 Generally, 14.14%
is the highest concentration of nitrogen in NC when all three
hydroxyl groups of the glucose units of cellulose are replaced with
NO2. But experimentally, the maximum nitrogen content cannot
exceed 13.8%. If the nitrogen content exceeds this then the repul-
sion forces of electronegative groups found on base rings
decrease compound stability.13 Mohamed et al. reviewed the
properties and various applications of nitrogen based organic
frameworks. Nitrogen doping demonstrated the mesoporous
nature of the block copolymer system.14
In addition to cotton fibres, NC and refined NC can be produced
from cellulose fibres, bamboo fibres, bagasse fibres and cellulose
derived from other stalk plants.15 The cotton rod, Eulaliopsis
binata, bagasse and other plant extracts were investigated and
refined into cellulose to make a thin paper.16 It can be used in
smokeless gunpowder NC products after nitration treatment. It
has also been utilised for a variety of coating applications, includ-
ing coating components, stabilisers, coating membranes, paints,
lacquers, varnishes for wood, paper metal, inks for package print-
ing, and celluloid printing. It is versatile and efficient in a variety of
fields in medicine, including water filtration, power generation,
catalysis coatings.17 Recently various reports showed the applica-
tion of NC and derived blends as a propellant due to its explosive
nature. Liu C et al. prepared graphene oxide/NC membrane and
further, they used as as solid propellant micro thruster by using
laser ignition combustion treatment.18 Touidjine et al. prepared
polyurethane/NC blends and further proved their suitable appli-
cation as solid propellants.19 With this motivation, we selected
NC for polymer blending with the PVC system.
This research aims to prepare a new polymer blend from two
extensively used thermoplastics PVC and NC by the solution cast-
ing method. PVC and NC are both employed in a variety of fields
since they are considered long lasting, inexpensive, air stable, and
are widely available. The unique features of NC combined with
PVC will open up new opportunities for advanced polymer blends
with unique physicochemical properties that have never been
explored and reported before. Qualitative and quantitative ana-
lyses of NC blends were examined by spectral, microscope, sur-
face and thermal conductivity investigation.
LITERATURE SURVEY OF PVC DERIVED
POLYMER BLENDS
Polymers exhibit interesting electrical and conductive properties
correlated to the structure of the polymer system. These proper-
ties may be optimised by modification of the pristine polymer sys-
tem. Modification can be achieved by loading a filler, forming a
nanocomposite or blending two or more polymer systems.20 Var-
ious roots or alternative methods can be used to achieve the
desired chemical moieties. Polymer blends have different physical
and chemical properties depending on their structure and com-
position suitable for the desired applications. Recently reported
PVC polymer blends and the choice of proposed properties with
a literature survey are tabulated in Table 1.
EXPERIMENTAL DETAILS
Materials
PVC polymer granules with molecular weight 233 000 g mol−1
used for preparation were supplied by Technovinyl Polymers
Ltd, Mumbai (Maharashtra), India, with tensile strength of
22.8 MPa, volume resistivity 8 × 1014 Ω cm−1 and specific gravity
1.38 (± 0.03). A high molecular weight PVC polymer system is
deployable across a broad temperature range.31–33 NC of HM
10/25 grade was supplied by GRN Cellulose PVT Ltd, Ramnagar,
Chandauli (Maharashtra), India, in cotton form with high nitrogen
content and medium viscosity grade. The solvent THF of AR
grade with molecular weight 72.11 was procured from S.D. Fine-
Chemicals Ltd, Mumbai (Maharashtra), India, and used as is.
Preparation of PVC/NC blends
PVC/NC blends obtained as a function of varying NC wt% were
prepared by the mix solution method. Initially, PVC and NC were
dissolved in THF separately (by constant stirring at 900 rpm for 4
and 2 h respectively at room temperature, 30 °C) to obtain com-
plete dissolution. The mixed solution of PVC/NC was poured into
a glass Petri dish. Further, to obtain blend samples the solution
was kept at room temperature for 10 h as shown in Fig. 1. The

Table 1. Literature survey of PVC polymer blends and nanocomposites

Polymer system Filler Enhanced property Reference

PVC CdS Thermal conductivity 21

PVC MnCl2 Dielectric properties 22
PMMA/PVC LiTFSI Dielectric properties 23
PMMA/PVC BmImTFSI Electrical properties 24
PVK/PVC SiC Structural, thermal, electrical and AC impedance properties 25
PVC/PEMA Zn(CF3SO3)2 Dielectric, thermal electrochemical properties 26
PVC/PS — Optical and dielectric properties 27
PVC/CA — Thermal, electrical properties 28
PVC/PMMA NiO Dielectric properties 29
PVC GO Surface properties 30
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Polyvinyl chloride/nitrocellulose polymer blends
Figure 1. Basic protocol to obtain the PVC/NC blends.
polymer blend sample obtained was used for further characterisa-
tion. Figures 2(a) and 2(b) show the 2D and 3D schemes of the
proposed model of the blend samples. Sample configuration
details are tabulated in Table 2.
CHARACTERIZATION TECHNIQUES
Fourier transform infrared spectroscopy (FTIR) analysis
The FTIR spectra of PVC/NC samples were determined in the
region 4000–400 cm−1 using a Jasco FTIR spectrophotometer
6600 (Jasco FT/IR-6600). An appropriate PVC/NC blend was vali-
dated with its fingerprint region.
UV–visible analysis
The optical measurements of the PVC and PVC/NC blends were
done by using a UV–visible–near IR spectrophotometer (JASCO
V-670, Japan).
XRD analysis
The XRD of the PVC/NC blends was performed using Cu K⊍ radia-
tion having a wavelength of ⊗ = 1.54 Å produced by the Bruker
AXS D8 Focus Advance XRD meter (Rigaku, Tokyo, Japan), with a
potential difference of 40 kV and a current of 40 mA. The reflected
angle 2⊔ ranges from 10° to 80°.
Scanning electron microscopy
A Zeiss scanning electron microscope (EV108) was used to inves-
tigate SEM pictures of PVC/NC blends using energy dispersive X-
ray (EDX) analysis. At 5–10 kV accelerating potential, surface
photos were acquired in a 10 μm scale range.
Electrical study
The dielectric properties were investigated using a dry tempera-
ture calibrator and a PSM-1735 (Newtons4th, UK) impedance ana-
lyser (frequency and temperature range 10 Hz to 10 kHz and 30 to
150 °C respectively) (ALAB Instrument). For the test, a sample with
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a diameter of 10 mm and a thickness of 50–60 μm of the polymer
blend was kept in a fixture.
Surface contact angle
A contact angle goniometer (DMe-211 Plus, Kyowa Interface Sci-
ence Co. Ltd) was used to measure the contact angle of the PVC
and PVC/NC blends by using different probe liquids (water, form-
amide, ethylene glycol, diiodomethane) and pouring 2.5 μL of liq-
uid onto the blend surface. A computer-controlled camera
captured the liquid droplet contact angle data automatically.
Total five trials were taken, and the mean values were used to plot
a graph.
Thermal conductivity measurement by Lee's disc method
The thermal conductivity of the prepared blend samples was
measured using the portable Lee's disc method exclusively cali-
brated with a temperature gradient.
Digital Shore 'A' durometer tester
The softness property of the polymer blend was tested with a dig-
ital Shore A tester (with a 4 digit display 10 mm LCD system,
Indi6179 series with resolution 0.1). Pin of intender was pressed
on sample surface and values were digitally calibrated with con-
stant fixed at stand at room temperature 28 °C with base pro-
vided block. We took the mean of three tests.
RESULTS AND DISCUSSION
XRD analysis of the PVC/NC blend
XRD is one of the most effective characterisation techniques
determining crystallinity in polymer blends. Figures 3(a)–3(c)
depict XRD patterns of pure PVC and PVC/NC blends. The PVC
grade we used in the present work shows a more crystalline
nature which is the best compared with the literature.28,34 The
degree and nature of the crystallinity in PVC has been a point of
controversy on an intermolecular scale. Other reports concluded
that commercial PVC is primarily an amorphous glassy polymer
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Figure 2. Proposed model of PVC/NC polymer blends: (a) 2D view; (b) 3D view.

the PVC/NC blend due to the amount of semicrystalline NC. These

Table 2. Composition of PVC and NC in different weight fractions
shifted peaks and decreased intensity of peaks demonstrate the
Polymer blend wide distribution of hydrogen bond distances and geometries in
the blends. Reduced peak intensity was quite good compared to
Sample code PVC NC the reported literature.
NC0 100 —
Moreover, the crystallinity, crystallite size and interplanar spac-
NC100 — 100
ing of PVC and PVC/NC blends were obtained. The crystallite size
NC1 95 5
of pristine PVC and PVC/NC blend was determined using the
NC2 90 10
Debye–Scherrer formula
NC3 85 15
NC4 80 20 D=K⊗=⊎ cos ⊔

Beyond 20 wt% of NC samples become stickier and it is challenging to
get free standing film.
with a small percentage of crystalline structure and is therefore
referred to as semicrystalline. On other hand, NC has a semicrys-
talline nature.35,36 Figure 3(a) shows the XRD diffractogram of
pure PVC. The main diffraction peaks are observed at 2⊔ = 29.5°,
25.1° and 39.63° of PVC which is in good agreement with recent
reports.28 The broad diffraction peak obtained at 2⊔ = 20.3° corre-
sponding to the amorphous phase of NC (shown in Fig. 3(b)) is
quite similar to NC fibre.37 In the case of PVC/NC blends the peaks
were shifted towards lower 2⊔, as shown in Fig. 3(c). It can be
clearly seen that peaks at 2⊔ = 48.20°, 43.34°, 39.48°, 29.65° and
25.04° shifted to 2⊔ = 44.64°, 40.43°, 36.97°, 27.80° and 21.98°
respectively. Moreover, the intensity of peaks observed at
2⊔ = 11.15°, 13°, 14.81°, 36.22° was found to be decreased in
4
where D is the crystallite size, K is the Debye constant (K = 0.9), ⊗
is the X-ray wavelength (⊗ = 1.5406 Å), ⊔ is the peak angle and ⊎ is
the full width at half maximum. Evaluation of the positions and
shapes of diffraction peaks provides information about the inter-
planar spacing (d) and crystallinity (in percentage) of polymer
blends. The interplanar spacing (d) was estimated using the Bragg
equation.38 It was observed that d decreased with increased load-
ing of NC corresponding to a decrease in the number of PVC
chains packed together. Furthermore, the decreased crystallite
size and crystallinity were confirmed by XRD data using the dif-
fraction Eva software. Crystallite size and crystallinity were
observed to be in the range of 42–23 nm and 70%–60% respec-
tively. A small crystallite size and decreased crystallinity may be
beneficial for improvement in the micro hardness property for
the development of coating materials. It exhibited a smooth sur-
face texture.39 Calculated values of the interplanar spacing and
crystallinity are summarised in Table 3.

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Figure 3. XRD pattern of (a) pure PVC, (b) pure NC and (c) PVC/NC blends.

all characteristic peaks of PVC and NC. The major changes

Table 3. Structural parameters evaluated from XRD spectra of PVC/
NC blends observed in the band range 500–1500 cm−1 demonstrate PVC/
NC blend formation. The band observed at 2919 cm−1 is attrib-
Sample details Crystallite Interplanar Degree of uted to the C–H stretch of PVC. This peak intensity (C–H stretch)
(wt%) size D (nm) spacing d (Å) crystallinity (%) decreased further with NC loading which may be due to the func-
tionality changes in the blend system. The band observed at
Virgin NC (0/100) 1.27 5.39 56.3
1636 cm−1 is attributed to an asymmetric stretch of NO2 due to
Virgin PVC (100/0) 42 3.63 73.8
presence of NC in the blend system. The peak observed at
PVC/NC (95/5) 41 2.68 72.6
1636 cm−1 in NC was found to be shifted to 1657 cm−1. The band
PVC/NC (90/10) 38 2.77 72
present at 2960 cm−1 in pure PVC completely disappeared in the
PVC/NC (85/15) 34 2.26 70.3
PVC/NC blend as NC loading increased. These changes may be
PVC/NC (80/20) 23 2.25 65.4
due to functionalities inside the blend formation.28 The intensity
of the band around 1073 cm−1 in the spectrum of PVC/NC
increased in the PVC/NC blend. Moreover, the bands present at
713 and 607 cm−1 in PVC shifted to 707 and 610 cm−1 respec-
FTIR fingerprint analysis of PVC/NC polymer blends tively due to C–H wagging in PVC. All bond assignments with their
The chemical functionalities of polymer blends can be evaluated corresponding wavenumbers are tabulated in Table 4.
using FTIR spectroscopy, which has been demonstrated to pro-
vide useful information about specific interactions between poly- UV–visible study of PVC/NC blends
mer segments. In the present study, the chemical composition of Exploration of the absorption spectrum can reveal information
prepared PVC, NC and PVC/NC blend samples was confirmed by about a solid's band structure. The UV–visible absorbance spectra
using FTIR spectroscopy between wavenumbers 4000 and of the PVC and PVC/NC films incorporated with various concentra-
500 cm−1 as shown in Figs 4(a)–4(c). For virgin PVC the character- tions were recorded in the region 200–800 nm, as shown in Fig. 5
istic bands observed at 2919, 2854 and 1391 cm−1 can be (a). The formation of new peaks for all samples and broadening of
assigned to C–H stretching and C–H aliphatic bending vibrations these peaks with increasing NC is an indication of change in the
respectively, as shown in Fig. 4(a). The bands at 1285 and molecular structure of PVC such as degradation, polymer frag-
967 cm−1 are assigned to C–H rocking and C–H trans wagging ments, or free radicals; also the absorption intensity increased
respectively. Also, the band at 872 cm−1 corresponds to stretch- with decreased peak width due to the chemical bond formation
ing of the C–Cl band.30 The band at 628 cm−1 is assigned to cis between PVC/NC blend concentration. The absorption spectrum
CH wagging vibrations. The band at 1285 cm−1 is attributed to at 400–460 nm is assigned to the π to π* transition from unsatu-
the bending vibration of C–H from CH–Cl groups of the PVC poly- rated bonds. The absorption spectra slightly shift towards the lon-
mer and the band at 1075 cm−1 is assigned to C–C stretching ger wavelength side with increasing NC content due to
vibrations.40 The FTIR spectrum of NC shows strong absorption interaction between the PVC and NC. This result indicates interac-
characteristic peaks at 1636, 1277 and 835 cm−1 attributed to tion in the PVC/NC blend system.
nitric ester.41 Two distinct strong peaks are found at 1636 and
1277 cm−1 corresponding to NO2 asymmetric and symmetric Determination of the optical energy gap
stretching, respectively, as shown in Fig. 4(b). The peaks present The basic study of optical absorption can reveal information
at 835 and 741 cm−1 are attributed to O–NO2 stretching and O– about a solid's band structure. Insulators/semiconductors are
NO2 asymmetric bending, and the band at 670 cm−1 is assigned divided into two types of energy bandgap, a direct bandgap
to O–NO2 symmetric bending. In particular, the IR spectrum of and an indirect bandgap. The top of the valence band and the
NC contains all the nitro group peaks.42 The absorption band at bottom of the conduction band both reside at zero crystal
2955 cm−1 is attributed to the C–H stretching vibration. The band momentum in direct bandgap semiconductors (wave vector).
at 3334 cm−1 is attributed to the O–H stretching vibration of the An indirect bandgap semiconductor is one in which the bottom
free hydroxyl group present in NC.43 of the conduction band does not correlate with zero crystal
The chemical composition of the PVC/NC blends is shown in momentum.44 The optical variables such as the optical bandgap
Fig. 4(c). PVC/NC blending with different loading of NC combines (Eg) and the position of the fundamental band edge were
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Figure 4. FTIR spectra for (a) pure PVC, (b) pure NC and (c) 95%/5%, 90%/10%, 85%/15% and 80%/20% (d) IR band in 500-1500 cm−1 wavenumber PVC/
NC polymer blends.

determined by optical absorption studies on pure PVC and PVC/
NC polymer blends.
The energy gap is obtained by using the Tauc plot, fitting the
linear part of the curve and finding the intersection of the straight
line with the hν axis.45 A variation in optical bandgap was
obtained for different loadings of NC. The bandgap was calcu-
lated using the following mathematical expression referred to in
the literature.
⊍hν=Aðhν-EgÞn
where ⊍ is a constant, ‘hν’ is the photon energy and ‘Eg’ is the
optical band gap of the semiconductor and ‘n’ is index related
to the density of states for the energy band.
Figures 5(b) shows the direct bandgap of pure PVC and PVC/
NC polymer blends estimated using a plot of (⊍hν)2 with pho-
ton energy hν. For pure PVC the direct bandgap lies at
3.14 eV while on adding NC it is found to decrease from 3.14
to 2.94 eV. Similarly, the indirect bandgap was also calculated
using the Tauc plot of (⊍hν)1/2 with photon energy hν. How-
ever, the indirect bandgap varies from 2.71 to 2.21 eV for pure
6
PVC and PVC/NC as the NC loading increases from 5% to 20%,
as shown in Fig. 5(c).
The values of both the direct and indirect bandgaps decrease as
NC concentrations rise, as shown in the discrete plot in Fig. 5(d).
This decrease implies the creation of charge transfer complexes
in the polymer blend, which could lead to defects in the polymeric
matrices.
The localised states in the optical bandgap are caused by these
imperfections. When NC concentrations in the polymer matrix are
raised, the overlaps cause the energy bandgap to decrease. Fur-
thermore, as the optical gap values drop, the degree of disorder
increases (due to the amorphous nature of the produced films)
or local crosslinking occurs inside the amorphous phase of the
mix.46
SEM of the PVC/NC blend
SEM was used to precisely explore the interaction between PVC/
NC polymer blends. At smaller loadings of NC, it reveals good
dimensional homogeneity and a uniform distribution of the pores
in PVC/NC. A small crater has formed on the surface of PVC/NC
attributed to solvent evaporation during blend formation. As a

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Polyvinyl chloride/nitrocellulose polymer blends www.soci.org

result, PVC and NC coordinate and create a complex. Comparing

Table 4. FTIR for PVC/NC polymer blend
Figs 6(a) and 6(b), it can be seen that the pore size of PVC/NC is
Sample Wavenumber (cm−1) Bond assignments substantially smaller at higher loadings of NC. The semicrystalline
phase of NC was found to be partially present in PVC.42 Figure 7
PVC 2919 cm−1, 2854 cm−1, C–H stretching, C–H shows the decreased trend of pore size from lower to higher load-
1391 cm−1, 1285 cm−1, aliphatic bending ing of NC. The diameter of the pores was approximately 17.43 μm.
967 cm−1, 872 cm−1, vibrations, C–H rocking, At higher loading of NC, it can be observed that the uniformity of
628 cm−1, 1075 cm−1 C–H trans wagging, the pores was conserved by reducing the pore diameter to
stretching of C–Cl band, around 6.53 μm due to the increased amount of NC.
cis CH wagging, C–C Furthermore, an elemental analysis was done using the EDX
stretching vibrations spectrum. Elemental chemical mapping for the PVC/NC blend by
NC 1636 cm−1, 1277 cm−1, C–H stretching, NO2 EDX is shown in Figs 8(a)and 8(b). The elemental composition
835 cm−1 and asymmetric, symmetric analysis indicated a remarkable point density of elements (car-
1280 cm−1, 835 cm−1 stretching, O–NO2 bon, chlorine, nitrogen, oxygen) from both PVC and NC, which
and 741 cm−1, stretching, O–NO2 are homogeneously dispersed throughout the surface of the poly-
670 cm−1, 2955 cm−1, asymmetric bending, O– meric blends. The strongest signal is near 0.05 to 0.5 keV which
3334 cm−1 NO2 symmetric bending, shows the absorption of NC in the PVC polymer matrix.47 Also, sig-
C–H stretching, O–H nals for chlorine and oxygen were obtained, which indicate the
stretching presence of NC in PVC. At higher loading of NC (20%) elemental
PVC/ 2919 cm−1, 1650 cm−1, C–H stretch of PVC, elimination was observed. It was observed that the chlorine group
NC 1636 cm−1, 1073 cm−1, asymmetric stretch of started to disappear from the blend system as shown in Fig. 8(b).
713 cm−1, 607 cm−1 NO2, O–NO2 stretching in These elemental changes also show dispersion of semicrystalline
NC, C–H wagging in PVC NC in amorphous PVC.

Figure 5. (a) UV–visible absorption (b) direct band gap (c) indirect band gap and (d) relation curve between direct and indirect band gap of pure PVC and
PVC/NC polymer blends.
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Figure 6. SEM micrographs of (a) 95%/5% and (b) 80%/20% PVC/NC blends.
Figure 7. Pore size of PVC/NC blends.
Dielectric constant of the PVC/NC blend
A dielectric study is a versatile approach that is commonly used to
investigate the ionic and molecular interactions that occur within
polymer blends, polymer composite materials. Polymer based
dielectric materials are used as potentially promising alternatives
to commonly used inorganic and ceramic derived dielectric mate-
rials due to their appealing properties including greater flexibility;
simple, cost-effective processing feasibility; chemical stability; and
readily changeable character. With this motivation, the study of
electrical ion exchange in dielectric properties is reported, which
was investigated in the present work in the frequency range
10 Hz to 10 MHz. Figures 9(a)–9(e) illustrate plots of the dielectric
constant (εr) of (a) PVC, with a loading of (b) 5% NC, (c) 10% NC, (d)
15% NC and (e) 20% NC.48 The dielectric constant and dielectric
loss were calculated using the formulae referred to in the litera-
ture.49 For PVC the dielectric constant obtained is ca 4. The maxi-
mum value of the dielectric constant for PVC/NC (90%/10%) blend
is ca 17 at 200 °C, 10 Hz. It was observed from the plot that the
trend of εr decreases with increase in frequency. This is because,
at low frequencies, mobile ions will have enough time to diffuse
and migrate under the influence of the applied electric field; as
a result, the charge increases in the interface region. Ions are
unable to be transported to the external circuit due to the block-
ing stainless steel electrodes. A greater εr observed in the low fre-
quency domain is due to space charge effects coming from the
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PS Jadhav et al.
interfacial polarisation phenomenon at the electrode–electrolyte
interface.26 The polar groups (NO2) present in the polymeric
chains due to NC are the second source of dipole orientation.
These dipoles orient somewhat away from their equilibrium con-
dition, where positively and negatively charged regions displace
towards and away from the field direction respectively, further
supporting the polarisation effect. As a result of these two distinct
occurrences, at low frequency εr is high.22
On the other hand, the quick periodic reversal of the electric
field reduces both the dielectric constant and dielectric loss at
high frequency. This quick cyclic reversal may cause dipole orien-
tation to slow down, resulting in a drop in charge density at the
interface. As a result, excessive ion diffusion in the electric field
direction is absent, resulting in a naked polarisation effect in the
high frequency domain.1 These noticeable changes of dielectric
properties for the prepared blend may be a choice for applica-
tions in dielectric media for low frequency capacitors.
Dielectric loss of the polymer PVC/NC blend
Dielectric loss is a measurement of electromagnetic energy dissi-
pation in a material. Figures 10(a)–10(e) show tan ⊐ versus fre-
quency at different temperatures. For PVC tan ⊐ is observed to
be very high, ca 10. The maximum value of tan ⊐ for PVC/NC is
ca 6 (200 °C, 10 Hz) and it decreased further to ca 2.4 as NC load-
ing increased. It is clear from the plot that tan ⊐ is high in the lower
frequency region and decreased for higher frequency. The
charges and polar groups in the polymer blend may vibrate at
lower frequencies. Heat is generated through the polar torque
when ions overcome the resistance they face during each oscilla-
tion. This may cause a decrease in dielectric loss.24 In addition to
this effect, the oscillating dipoles and charges have a phase lag
about the frequency of the applied voltage. Decreased dielectric
loss of PVC/NC blend may enhance the electrical conductivity,
and this may lead to applications in various electronic domains.
Contact angle study of PVC/NC blend
For many years, contact angle measurement has been used to
analyse surface wettability and roughness. It aids in the compre-
hension of material compatibility. Wettability is essential in the
preparation of polymer blends. We employed sessile droplets in
this study for contact angle measurement. Figure 11(a) shows
contact angle values for PVC and the PVC/NC polymer blend with
respect to four different probe liquids (water, formamide, ethyl-
ene glycol, diiodomethane). We observed a decreased contact
angle for the PVC/NC blends with respect to the four liquids. This
may be due to hydroxyl groups and polar groups present in the
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Polyvinyl chloride/nitrocellulose polymer blends www.soci.org

Figure 8. EDX analysis spectrum of (a) 95%/5% and (b) 80%/20% PVC/NC blends.

Figure 9. Dielectric constant of (a) pure PVC and (b) 95%/5%, (c) 90%/10%, (d) 85%/15%, (e) 80%/20% PVC/NC blends, as a function of NC (wt%)
blending.

PVC/NC blend. Hydroxyl groups show affinity towards the liquid,
which results in improved hydrophilicity of the PVC/NC polymer
blend over the pristine PVC sample.
Furthermore, the SE for the prepared blend sample was also
measured. For the SE measurement a proper choice of liquid is
very important. Liquids with γ lv ≤ γ sv become flat on a solid sur-
face immediately. Because of this, such liquids cannot be used
to determine the contact angle.30 The Owens–Wendt model was
used to estimate the SE for solid surfaces, including dispersive
and polar components. Diiodomethane and water were used as
the dispersive and polar components respectively for measure-
ment of the SE. The SE components for PVC and the PVC/NC blend
were calculated using the equations described in previous
reports.50 The contact angles of water and diiodomethane on
the blend surface were measured for calculations of SE. The
results showed an increased SE for the PVC/NC blend compared
to pristine PVC with respect to decreased contact angles, as
shown in Fig. 11(b). The rise in SE of the modified samples over
the pure sample was accompanied by a decrease in contact angle.
Thermal conductivity of the PVC/NC blend
The thermal conductivity k of a solid substance is used to deter-
mine its heat transmission characteristics. It is a measure of a sub-
stance's ability to transfer heat by conduction through a medium.
Thermal conductivity is measured by using various techniques.
We used Lee's disc method and adopted the process used in pre-
vious reports.51,52 It is a quick, easy approach and a cost-effective
method to figure out the k of materials of low thermal conductiv-
ity compared to other methods.51 Figure 12(a) shows Lee's disc
apparatus for the purpose of calculating heat conductivity using
readily available parts. Figure 12(b) shows a heat transfer model
for pure PVC and PVC/NC blend material. The thermal conductiv-
ity k was calculated using the mathematical equation
9

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 www.soci.org PS Jadhav et al.

Figure 10. Dielectric loss of (a) pure PVC and (b) 95%/5%, (c) 90%/10%, (d) 85%/15%, (e) 80%/20% PVC/NC blends, as a function of NC (wt%) blending.

Figure 11. (a) Contact angle of PVC/NC blend as a function of NC loading (wt%). (b) Relation curve between surface energy and contact angle of the PVC/
NC blends.

phonon mean free path is controlled due to its amorphous

msl dT
k=
ðT 2 –T 1 ÞA dt
where m is the mass of a given sample, s is the specific heat of
the material, l is the thickness of the material, A is the area of
the material, T2 − T1 is the temperature gradient which is calcu-
lated by measuring the steady temperatures, and dT/dt is the rate
of cooling of mild steel at T2 in kelvins per second. The effective
thermal conductivity k for PVC and PVC/NC blends was investi-
gated at room temperature; the effective k of PVC was measured
to be 0.12 W/(m.K) which is comparable with the reported value
of 0.17 W/(m.K). k of PVC ranges from 0.04 to 0.35 W/(m.K) in the
literature.52 The results show an increased k for the PVC/NC blend.
k values for the PVC/NC blend varied from 0.12 to 0.18 W/(m.K) as
the NC loading increased. In PVC for k at room temperature the
10
regions. The presence of numerous defects in amorphous
regions lowers the phonon mean free path in polymers.53,54
The resultant increased thermal conductivity is due to the pres-
ence of a higher nitrogen content in NC as shown in Fig. 13
(a).55 Recently the same effect of nitrogen on thermal properties
has been reported.56,57 As a result, modification of the phonon
mean free path is due to elastic disorder and chain defect scat-
tering of the phonons caused by weak hydrogen bonding in
the polymer blend.21
Along with thermal conductivity (k), the thermal diffusivity (⊍)
and specific heat capacity (Cp) are also significant for thermal
transport qualities; in the polymer sector these thermophysical
parameters play a big role in calculating heat transfer.58 ⊍ is a
measure of how efficiently heat propagates through a material.
It is an essential factor in all non-steady-state heat conduction

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Polyvinyl chloride/nitrocellulose polymer blends www.soci.org

Figure 12. (a) Lee's disc apparatus. (b) Heat transfer model for PVC and the PVC/NC blends.

Figure 13. (a) Thermal conductivity of the PVC/NC blend as a function of NC loading (wt%). (b) Relation curve between thermal conductivity and specific
heat of PVC/NC blends.

situations. ⊍ increased as the mean free path increased due to
increased NC loading, as shown in the curve of Fig. 13(a). The spe-
cific heat capacity (Cp) is an evaluation of a material's capacity to
absorb heat from its environment. It signifies the quantity of
shows increased absorption capacity for the PVC/NC blend com-
pared to PVC. The Cp curve of the PVC/NC blend is illustrated in
Fig. 13(b). The results show the importance of dispersion and suit-
able compatibility between the NC and PVC blend. This enhanced
11

energy needed to produce a temperature rise. The increased Cp thermal conductivity, diffusivity and specific heat capacity is

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 www.soci.org
Figure 14. Shore A test of PVC/NC 95%/5%, 90%/10%, 85%/15%, 80%/
20% blends.
addressed by structural changes occurring in PVC and the PVC/NC
blend during heating.
Shore 'A' durometer test of PVC and PVC/NC blends
To investigate mechanical performance, polymers, foams and
rubbers are tested using a Shore A durometer. In the present
study, the softness of PVC and PVC/NC polymer blends was mea-
sured. A constant pressure was applied over the blend sample by
the tip of the durometer.59 Thermoplastics containing fluoro and
vinyl group polymers show excellent durometer performance.28
For pure PVC film softness was measured as 51.6 which is further
increased by loading of NC into PVC. Softness was increased by ca
19% by 20 wt% loading of NC, as shown in Fig. 14. Increased soft-
ness for all the samples observed may be due to chemical func-
tionality changes because of NC loading, confirmed by FTIR.
Structural properties have been changed, confirmed by XRD anal-
ysis. Softness was increased due to decreased interplanar spacing
of blends with increased loading of NC.60 Enhanced softness of
prepared polymer blends demonstrated their suitability for engi-
neering and industrial applications.
CONCLUSION
PVC/NC blends were prepared successfully by using the solution
casting method and characterised by different sophisticated tech-
niques. The XRD spectra showed a decreased crystallinity and
interplanar spacing which confirmed the presence of semicrystal-
line NC in the PVC. From the FTIR study, it was observed that PVC
and NC have good compatibility. The SEM morphological study
confirmed the porous nature of the blend sample at higher NC
(20%) loading and a combined effect of immiscibility was
observed. The optical study revealed decreased bandgap ener-
gies (direct and indirect) for the PVC/NC blend due to a conjuga-
tion effect. The dielectric constant and loss are both high at a
lower frequency and decreased at a higher frequency. This may
be due to a variation in charge density at the interface following
the Maxwell–Wagner model. Surface studies revealed decreased
contact angle and increased SE for the PVC/NC blend system,
while the increased hydroxyl groups increased the hydrophilicity
of the PVC system as demonstrated by goniometer. Increased
12
thermal conductivity and specific heat capacity were quantified
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PS Jadhav et al.
by Lee's disc method due to the presence of nitrogen in NC. The
Shore A durometer showed 18% improved softness of the blends.
Hence, we conclude that all the enhanced properties of modified
PVC/NC blends demonstrate that they may be further developed
for domestic applications.
ACKNOWLEDGEMENTS
The authors would like to gratefully acknowledge the Institute of
Chemical Technology Mumbai Marathwada Jalna for providing a
doctoral fellowship. Research scholar Pratibha S. Jadhav is grateful
to the Vellore Institute of Technology, Vellore (India), for providing
the SEM characterisation facility.
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