Advanced Composites and Hybrid Materials

https://doi.org/10.1007/s42114-018-0051-4

ORIGINAL RESEARCH

Dynamic mechanical analysis of PVC/TiO2 nanocomposites

Vishal Mathur 1,2 & Pramod Kumar Arya 1

Received: 9 April 2018 / Accepted: 26 July 2018

# Springer Nature Switzerland AG 2018

Abstract
The PVC/TiO2 nanocomposite samples were structurally characterized by scanning electron microscope that ascertains its
polymer nanocomposite nature. The dynamic mechanical response, i.e., storage moduli and phase transition temperature accom-
panied by temperature have been studied through Dynamic Mechanical Analyzer (Tritec 2000 DMA). The intrinsic viscosity and
phase transition activation energy is resolute in using these data. The results reveal that TiO2 nanoparticle dispersion in PVC
causes prominent enhancement in observed properties. However, the enhancement depends on proportion of nanoparticles.

Keywords PVC/TiO2 . Nanocomposite . Dynamic mechanical properties . Activation energy

1 Introduction montmorillonite (MMT) within 0.5–3 wt% content improves

Polyvinyl chloride (PVC) is among the eminent plastics used in
different fields evinces as plastics moldings, building materials,
and electrical insulators owing to its valuable attributes, like
effective manufacturing cost, comfort processability, amenable
modification, and outstanding fire and chemical retardation
properties [1, 2]. The fundamental, user friendly PVC applica-
tions rely on its permanence to defend against disintegration
from their esthetic and mechanical properties over time-
consuming phase of continuous exposure which requires a cau-
tious compounding [3, 4]. Nowadays, PVC has been commer-
cially modified through various impact modifiers like
acrylonytrile butadiene styrene (ABS), chlorinated
polyetyhylene (CPE), etc. [5–7] in order to enhance its tough-
ness and heat-softening temperature. Beside this, fillers of
nanolevel have also been extensively used to realize superior
mechanical aspects. In comparison with conventional
microfillers, nanofillers exhilarate interfacial area and surface
energy that affects the overall properties of the composites [7,
8]. Wan et al. [9] reported that the addition of organic
* Vishal Mathur
wishalmathur@gmail.com
1 dynamic mechanical behavior through Dynamic Mechanical
Faculty of Science & Technology, ICFAI Tech School, The ICFAI
University, Jaipur, India
2 of PVC/TiO2 nanocomposite samples significantly enhances
Semiconductor and Polymer Science Laboratory, Department of
Physics, University of Rajasthan, 302004, Jaipur, India
the process ability of the PVC/MMT nanocomposites. Xie et
al. [10] reported that the calcium carbonate nanopowder appre-
ciably ameliorate stiffness of PVC, whereas the materials have
to sacrifices with its tensile strength. Wang et al. [11] prepared
multiwall carbon nanotube (MWNT) and poly caprolactone
(PCL) mixed PVC composites and found that MWNT-PCL
increases the tensile strength, modulus, and toughness of PVC.
Literature reveals that titanium dioxide (TiO2) nanofiller-
doped polymeric matrices have attracted much attention due
to possibility of achieving desirable physical and chemical
properties that accelerate its extensive applications in various
sectors like catalytic supports, photocatalysts, gas sensors, etc.
[12–14]. Liu et al. [15] reported reinforced photocatalytic prop-
erties and antibacterial activities of TiO2/Ag/PVC. Yoo et al.
[16] suggested that TiO2-encapsulated PVC can be used as an
eco-friendly substitute of PVC. Yang et al. [17] developed pho-
todegradable PVC/TiO2/vitamin C nanocomposite, which turn
up with high photodegradation competence under UV irradia-
tion than the both PVC and PVC/TiO2 nanocomposite.
In actual practice, TiO2 is a cardinal constituent for the
enduring unalterable PVC. The main concern is the extrane-
ous enduring of white PVC parts for window profiles, i.e.,
resilience to yellowness and sheen retention [18].
Nevertheless, it is also beneficial to know their mechanistic
aspects before evaluating optical profile. In this study, we have
prepared PVC/TiO2 nanocomposite samples and studied their
Analyzer (DMA). The study shows that mechanical properties
and depends on concentration of nanofillers.
 Adv Compos Hybrid Mater

2 Experimental

2.1 Material preparation

The TiO2 nanofillers (particle size 20 nm), PVC (Mw =

43,000), and solvent tetrahydrofuran (THF) (99.9% purity)
of research grade were purchased through Sigma-Aldrich.
PVC/TiO2 nanocomposite films of thickness ~ 0.12 are pre-
pared by solution casting approach at various (0, 2, 4, 6, and
8) wt% of TiO2 nanofiller in PVC. Initially, PVC is liquefied
in THF solvent, stirred for 24 h, and then TiO2 nanoparticles
were dispersed in this solution while continuing stirring for
another 24 h. Then solution is splashed into petri dishes and
placed in dry atmosphere over a period of 24 h for the evap-
oration of the solvent. The sample comes out in the form of Fig. 1 FTIR spectrum of PVC/TiO2 nanocomposites
thin film which is peeled off. In order to ensure the removal of
the solvent, the films are dried out through vacuum annealing
near about 50 °C [19]. because of CH2 deformation of PVC [24]. A peak associated
to the C–C stretching appeared at 1095 cm−1. Two peaks at
2.2 Experiment systems 1249 and 1331 cm−1 represent deformation of C–H of CHCl3.
The rocking CH2 of PVC appeared at 960 cm−1. Two bands
Perkin Elmer FTIR Spectrum-2 spectrometer is used for the appeared at 692 and 611 cm−1 that is caused by the stretching
structural characterization of PVC/TiO2 nanocomposites over of C–Cl [23]. A peak at 449 cm−1 is observed, which is evi-
the range of 4000–400 cm−1. dence for Ti–O–Ti network structure [25]. The addition of
The mechanical retract of specimens with reference to the nanoparticles into the PVC made some polymer chains broken
sinusoidal stress and temperature is characterized through and some other chains formed. The nanoparticles also restrict
Dynamic Mechanical Analyzer (DMA TRITEC-2000). The the mobility of PVC chains through the interactions between
DMA samples are generally taken between 4 and 6 mm the nanoparticles and polymer chain segments which strength-
(W) × 10 mm (L) × 100 mm (T). For temperature scan, ened mechanical properties of nanocomposites.
DMA is adjusted in tension mode. The heating/ramp rate is
adjusted at 2 °C/min while keeping strain amplitude 0.01 mm 3.2 Storage modulus
and frequency of oscillations at 1 Hz. The loss modulus E″,
storage modulus E′, and loss factor (Tan δ) is evaluated as a Figure 2 evinces the storage modulus versus temperature be-
function of escalating temperature [20–22]. havior of PVC/TiO2 at different filler content. The lessening
Scanning Electron Microscope Carl Zeiss EVO 18 SEM
model is used for SEM observations The sample to be char-
acterized through SEM placed on a specimen stub and after
that, gold is plated on the upper surface of the sample in order
to make it conductive. Conductive silver paste is used to attach
the specimen to the sample holder.

3 Results and discussion

3.1 Fourier transform infrared spectroscopy analysis

The chemical structure of prepared PVC/TiO2 nanocompos-

ites are evaluated through Perkin Elmer FTIR Spectrum-2
spectrometer. Figure 1 shows the FTIR spectra of PVC/TiO2
nanocomposites at different (0, 2, 4, 6, and 8) wt% of TiO2
nanoparticles over the range of 4000–400 cm−1. The bands at
2974 and 2910 cm−1 are assigned to the C–H stretching vibra- Fig. 2 Storage modulus variation with temperature of pure PVC and
tion ofCHCl3 and CH2 [23]. A peak appeared at 1435 cm−1 PVC/TiO2 nanocomposites
Adv Compos Hybrid Mater
of storage modulus with the temperature enhancement is
clearly observed which become saturated beyond a certain
elevated temperature for each nanocomposite. This behavior
is explicated on the basis of polymeric molecular segmental
agitation ability. At room temperature, the molecular vibrates
with low energy about their mean posture and offers promi-
nent storage modulus as depicted in Fig. 2. However, as ther-
mal energy made to increase polymeric molecular segments
agitates at great intense and creates free volume within the
samples that causes loss of storage modulus at superior tem-
perature [26].
Figure 3 shows loss factor (Tan δ) versus temperature be-
havior of PVC/TiO2 at different filler content. In view of
thermomechanical applications of polymer nanocomposite,
Tan δ measurements are reasonably important because the
temperature corresponding to its highest value is the direct
measure of its phase transition temperature (Tg) at which ma-
terial starts softening. It is also observed that the Tan δ and Tg
both are much sensitive toward entrenched nanofiller volume
fraction [27].
3.3 Viscosity and activation energy
Viscosity of the specimen from room temperature to elevated
temperature can be evaluated through storage and loss modu-
lus (E′ and E″) [24], which are related to each other by the
relation as the following:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 η ¼ ηο exp½1=K fðT =T ο Þ−1g
η ¼ E′ 2 þ E ′′ =2π f ð1Þ
where Bf^ is the frequency.
The evaluated viscosities at different elevated temperatures
for PVC/TiO2 nanocomposites are plotted in Fig. 4. It is
Fig. 3 Variation of Tan δ of pure PVC and PVC/TiO2 nanocomposites
with temperature
Fig. 4 Variation of viscosity of pure PVC and PVC/TiO2 nanocomposites
with temperature
observed that viscosity also decreases on increasing tempera-
ture for each of studied sample and viscosity profile increases
on dispersing of TiO2 up to 6 wt% and beyond this, it lessens.
The observed results of storage modulus, viscosity at room
temperature, and Tg temperatures of the studied samples are
tabulated in Table 1, respectively.
The activation phase transition energy (Ea) can be evaluat-
ed through Vogel–Fulcher–Tammann (VFT) equation [28]:
ð2Þ
and
K ¼ E a =RT g ð3Þ
where R is Boltzmann gas constant (8.314 J/mol K) and To is
defined as the VFT temperature.
Processing with Eq. (2), a graph is plotted between ln(η)
and [1/{(T/To) − 1}] and then corresponding slope is deter-
mined through linear fit tool that resolve activation phase
transition energy (Ea) through substituting required data in
Eq. (3). Figure 5 depicts different evaluated Ea values with
TiO2 filler concentration and it is observed that Ea increases
with increasing TiO2 concentration up to 6 wt% in the PVC
matrix and beyond that, it also decreases.
The values of storage modulus, viscosity, Tg, and activation
energy for PVC/TiO2 nanocomposites are observed higher as
compared to pure PVC. However, on higher filler concentra-
tion (8 wt%), values of these decrease.
The increase in these properties for PVC/TiO2 nanocom-
posites clearly indicates the appropriate diffusion of TiO2
nanofillers that resonate with great interfacial surface region
among inferiorly mobilized chain segments.
The decrement in observed properties of PVC/TiO 2
8 wt% proclaims the agglomeration of nanofillers, the stage
beyond the saturation dispersion level that originates
 Adv Compos Hybrid Mater

Table 1 Storage modulus, viscosity, phase transition temperature, and phase transition activation energy of studied samples

Sample Storage modulus (GPa) Viscosity (at room Phase transition Phase transition activation
(at room temperature 33 °C) temperature 33 °C) temperatures (°C) energy (kJ/mol)

Pure PVC 1.8486 0.7425 58 26.9512

PVC + TiO2 2 wt% 2.3368 0.9518 64 92.0815
PVC + TiO2 4 wt% 2.7549 1.1201 66 160.6409
PVC + TiO2 6 wt% 2.9182 1.1485 72 527.8165
PVC + TiO2 8 wt% 2.0639 0.8311 64 115.1826

interfaces among constituent molecules of the specimen
[29]. The culmination decline in the Tan δ peak for
nanodispersed samples is attributed due to the presence of
immobile restricted molecular chain segments in the envi-
rons of phase transition region [30, 31].
Overall, polymer nanocomposite’s properties differ on
the basis of three mechanisms: first, the level of energetic
interaction in between nanofillers and polymer molecules;
second, concentration of nanofillers; and third, size of
nanofillers. In the present study, TiO2nanoparticles of
20 nm size are used. Therefore, remaining two mecha-
nisms stand as dominating factors for the observed results
that can be resolved through their morphological
attributes.
3.4 Morphology attributes
Surface morphological attribute of PVC/TiO2 nanocompos-
ites is accomplished by scanning electron microscopy
(SEM) technique as shown in Fig. 6a–e at different wt% of
Fig. 5 Variation of activation energy of PVC/TiO2 nanocomposites with
TiO2 wt%
TiO2 nanofillers in PVC which clearly depicts that TiO2
nanofillers vary the morphology of the unmixed PVC phase.
The TiO2-embedded PVC phase evinces evenly and con-
densed amorphous structure that further enhances on increas-
ing wt% of TiO2 nanoparticles.
In fact, as TiO2 nanofillers introduced in polymer, they
accompanied void sites and tend to derive proximities of sim-
ilar molecules. In order to evaluate exact allocation of these
molecules proximities, watershed segmentation algorithm
[32] using MATLAB tool is applied on SEM micrographs of
PVC/TiO2 nanocomposites. In this simulation approach, a
distance map is generated through binary image. In subse-
quent step, a topological surface is obtained in which the
deeper parts represent as brighter pixels and for each of the
interspacing molecule in the SEM micrograph of respective
nanocomposite, a basin is created as shown in Fig. 7a–d.
Figure 7a, b reveals different proximities regions with differ-
ent colors in accordance with percentage of similar proximity
index. It is observed that Fig. 7c represent smoother, evenly,
and fine topological surface morphology among the others in
which all the proximity regions are small, segmental inter-
faces, and void positions are clearly observed through white
lines and spots.
Furthermore, the energetic interaction among TiO 2
nanofillers and PVC is estimated through surface plots using
MATLAB tool applied on SEM micrographs of respective
nanocomposites. Figure 8a–d represents 3d surface plot of
such nanocomposites. Figure 8a, b reveals that intensity of
energetic interaction increases on increasing concentration of
TiO2 nanoparticles. The level of energetic interaction be-
comes too vibrant for the PVC/TiO2 6 wt% nanocomposite
as depicted in Fig. 8c among others.
Actually, the energetic interaction among TiO2 nanofillers
and PVC transforms fragile interfaces into sturdy interfaces on
increasing nanofiller concentration that further constrained the
movement of nanofiller lodged PVC molecular chain seg-
ments [29] and enhances the thermal energy acquaintance
capacity. Such specimens soften at consequently higher tem-
perature and require more activation energy for their phase
transition state as discussed above. However, storage
Adv Compos Hybrid Mater

Fig. 6 a–e Scanning electron

micrographs of pure PVC and
PVC/TiO2 nanocomposites

Fig. 7 a–d Watershed

segmentation micrographs of
PVC/TiO2 nanocomposites

Fig. 8 a–d Surface plot of PVC/TiO2 nanocomposites
modulus, viscosity, Tg, and its activation energy values tends
to decrease at higher nanofiller concentration (like in our case,
i.e., beyond 6 wt%) that is endorsed only due to doping be-
yond saturation level which causes accumulation of
nanofillers at interfacial surface proximities resulting to het-
erogeneity in the system [31, 33, 34] as observed in watershed
segmental plot and surface plot shown in Fig. 7d. In such
systems, nanofiller–nanofiller interaction dominates
nanofiller-polymer interaction, thereby energetic interaction
among nanofillers and polymer molecular chain segments de-
creases that further resolute reason of phase transition temper-
ature and corresponding activation energy decrement.
4 Conclusion
In this study, a simple route is described to obtain PVC/TiO2
nanocomposites. The SEM characterization reveal that TiO2
nanofiller accumulated PVC shows the consistent dispersion
up to 6 wt% of TiO2.The storage modulus, viscosity, phase
transition temperature, and its activation energy for PVC/TiO2
nanocomposites are found to be increased as compared to pure
PVC, that is explicated on the basis of energetic intervention
among nanofillers and polymer molecular chain segments.
Adv Compos Hybrid Mater
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
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