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Effects of inorganic nanofillers on the thermal degradation and UV-

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Article in Journal of Thermal Analysis and Calorimetry · January 2013

DOI: 10.1007/s10973-011-2153-x

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J Therm Anal Calorim
DOI 10.1007/s10973-011-2153-x
Effects of inorganic nanofillers on the thermal degradation
and UV-absorbance properties of polyvinyl acetate
Manoj Kumar Pal • Jaiswar Gautam
Received: 21 July 2011 / Accepted: 12 December 2011
Ó Akadémiai Kiadó, Budapest, Hungary 2012
Abstract The effects of calcium carbonate (CaCO3) and
calcium sulfate (CaSO4) nanoparticles on the thermal and
UV-absorbing properties of polyvinyl acetate (PVAc) were
analyzed in this study. Nanoparticles of CaCO3 and CaSO4
were synthesized by in situ deposition technique. The size
and shape of nanoparticles were recognized by X-ray dif-
fraction and scanning electron microscope (SEM) analyses
which confirmed that the particle was having a diameter of
25–33 nm. In this technique, the surface modification of
nanoparticles was done by non-ionic polymeric surfactant.
PVAc/CaCO3 and PVAc/CaSO4 nanocomposites film
samples with an average thickness of 30 lm and in the mass
ratio of nanoparticles (0–4% (w/w)) were prepared by
solution mixing technique. Chemical, structural, and ele-
mental characterizations of nanocomposites were done by,
fourier transform infrared, SEM, and energy dispersive
X-ray spectroscopy analyses, respectively. Thermal prop-
erties of pure polymer and nanocomposites were charac-
terized through differential scanning calorimetric,
thermogravimetric, and differential thermogravimetry
techniques. The glass transition temperature of nanocom-
posites increases with increase in content of nanoparticles.
It may be due to the interaction between inorganic and
organic components. The thermogravimetric analysis
results indicate that the thermal degradation temperatures of
nanocomposites were enhanced upon the addition of
nanosized inorganic fillers. The thermal results show that
PVAc/CaSO4 nanocomposites were more thermally stable
than PVAc/CaCO3 nanocomposites. The addition of nano-
particles affects degradation mechanism and consequently
M. K. Pal  J. Gautam (&)
Department of Chemistry, Dr. B.R. Ambedkar University,
Agra, India
e-mail: gjaiswar@gmail.com
improves thermal stability of PVAc. The reduction of
polymer chain mobility and the tendency of nanoparticles to
eliminate free radicals were the principal effects responsible
for these enhancements. The ultraviolet–visible (UV–Vis)
absorbance spectra of PVAc and its nanocomposites films
show that the intensity of absorbance increases with
increasing filling content, suggesting that nanocomposites
films have greater UV-shielding property.
Keywords CaCO3 nanoparticles  CaSO4 nanoparticles 
PVAc  DSC  TG/DTG
Introduction
Polymer nanocomposites are now well known in the field
of polymer science and engineering. These materials have
been found to attract great interest because of their
improved properties with very less nano-material loading
compared with conventional composite systems where
fillers are incorporated in large amounts. The primary
reasons for this enormous improvement in case of the
material performance are the incorporation and dispersion
of the highly anisotropic nanoscale reinforcement com-
pared with conventional particulate mesoscale fillers [1].
One of the most interesting ways to modify the polymer
properties was the addition of nanofillers. This addition
improves polymer properties, and in some cases, it leads to
a unique combination of properties [2]. Moreover, only a
low content, between 1 and 5% by weight of these fillers,
was needed to improve the polymer properties, whereas to
achieve the same effect in conventional fillers, it requires a
considerably higher amount [3–5].
Composition and modification of polymeric materials
with inorganic particles have been proved to be the
123

effective methods to improve the mechanical, thermal,
rheological, optical, and other properties [6–9]. The
improvement capability depends significantly upon type,
size, contents, and surface treatment of the fillers [10–13].
As an alternative to the in situ preparation of the inorganic
particles, colloids with a strongly bound surface layer of
organic molecules may be used if they can be isolated and
if the primary particles can be redispersed. In the present
case, agglomeration is suppressed by the surface layer
which markedly diminishes the specific surface free energy
and, therefore, tends to decrease the attraction between the
particles. Inorganic nanoparticles are commonly used for
the preparation of polymer nanocomposites. The prepara-
tion of nanocomposites can be carried out by in situ
polymerization [14], solution intercalation [15], solution
mixing [16, 17], melt intercalation [18], etc. Among these,
solution mixing technique is the most environmentally
benign method for producing polymer nanocomposites. In
this method, the excellent compatibility between nanopar-
ticles and organic matrix was achieved by selecting a
suitable liquid medium and a surfactant on nanoparticles to
form solution of nanoparticles, which effectively prevented
the phase separation in organic medium evaporation.
Poly (vinyl acetate) (PVAc) is a petroleum-derived
polymer usually obtained by emulsion polymerization. It
features excellent adhesion to various substrates. Thus,
large quantities of PVAc latex are produced for use as
binder in emulsion paints, adhesives, and various textile-
finishing operations. Some of this material is chemically
converted into poly (vinyl alcohol) and poly (vinyl butyral).
Owing to its inherent high cold flow, PVAc is of little value
in moldings and extrusions [19]. PVAc is rather brittle and
rigid but compounding it with other polymers frequently
improves physical properties [20–22]. Poly (vinyl acetate)
has been blended with various polymers, including poly
(e-caprolactone) and poly (vinyl chloride) [20, 21], poly
(L-lactide) [23], and epoxy and poly (4-vinyl phenol) [24]
to modify mainly their mechanical and thermal properties.
While little attention has been paid on the PVAc-based
nanocomposites to improve its mechanical, thermal prop-
erties, etc. [25–28]. Mohsen and Doulabi [29] prepared
PVAc/montmorillonite nanocomposites by in situ emulsion
polymerization technique. The synthesized PVAc/MMT
nanocomposites were characterized by X-ray diffraction
(XRD), scanning electron microscope (SEM), transmission
electron microscope (TEM), and atomic force microscope
(AFM). TEM images showed good dispersion of MMT in
PVAc matrix, resulting in an exfoliated structure. Thermal
properties of the nanocomposites were studied by using
DSC technique. According to the obtained results, the glass
transition temperature, (Tg), for the synthesized PVAc/
MMT nanocomposites increased with the content of MMT.
Masturi et al. [30] succeeded in making composites with
123
M. K. Pal, J. Gautam
high compressive strength using dry home waste, silica
nanoparticles, and PVAc. These nanocomposites can be
compared to the compressive strength of hard brick or slate,
and better than that of limestone and dolomite.
In this study, we used novel and simple technique for the
preparation of calcium carbonate (CaCO3) and calcium
sulfate (CaSO4) nanoparticles, PVAc/CaCO3, and PVAc/
CaSO4 nanocomposites with homogenous distribution of
inorganic nanoparticles in a polymer matrix. The interaction
of nanoparticles and polymer matrix was improved by
modification of nanoparticles surface through nonionic
polymeric surfactant. The nanoparticles size and chemical
bonding in nanocomposites was confirmed by XRD, and
fourier transform infrared (FT-IR), respectively. The mor-
phology and elemental composition of the prepared nano-
particles, and PVAc nanocomposites was investigated by
SEM-EDS. The thermal properties were investigated using
differential scanning calorimetric (DSC) and thermogravi-
metric/differential thermogravimetric (TG/DTG) tech-
niques. UV–Vis-absorbance spectra were evaluated by
UV–Vis double beam spectrophotometer. In this study, we
attempt to demonstrate the thermal stability and UV-absor-
bance properties of PVAc polymer, which can be enhanced
by the incorporation of CaCO3 and CaSO4 nanoparticles.
Experimental
Materials used
The analytical graded calcium chloride (CaCl2), potassium
carbonate (K2CO3), ammonium sulfate ((NH4)2SO4), and
polyethylene glycol (PEG, MW = 6,000 gmol-1) were
procured from Merck, India. Stabilized vinyl acetate liquid
monomer was obtained from Alfa Aeasar, Germany. The
vinyl acetate monomer was purified by treating it with 10%
NaOH to remove the inhibitor. Benzoyl peroxide (BPO)
initiator was purchased from CDH, Laboratory reagent,
India and used after recrystallization by methanol. Organic
solvents like methyl alcohol, toluene, chloroform, acetone
etc., supplied by Merck, India were used after double dis-
tillation. Deionized water was used throughout the reaction.
Nanoparticles synthesis and nanocomposites formation
The nanosized CaCO3 and CaSO4 were synthesized by in
situ deposition technique which was also reported in pre-
vious studies [31, 32]. 11.1 gm (0.1 M) CaCl2 was added
into 100 mL double-distilled water. 37.2 gm (0.0062 M) of
PEG was also diluted adding into 100 mL hot double-
distilled water, and the complex of CaCl2 and PEG was
prepared by proper mixing on mild heat (Step 1 solution).
Another solution of sodium carbonate (10.6 gm, 0.1 M) for
Effects of inorganic nanofillers
CaCO3 nanoparticles formation while for the preparation of
CaSO4 nanoparticles, 13.2 gm (0.1 M) of ammonium sul-
fate dissolved in 100 mL of distilled water (Step 2 solu-
tion). The above step 2 solutions were added into the step 1
solution separately for both nanoparticles by stirring gently
for 12 h. Then, these solutions were kept overnight and
finally the nanoparticles were filtered, washed thoroughly
with double-distilled water, till freed from PEG traces, and
then dried at 383 K for 2 h. The filler was heated to 523 K
to remove traces of moisture before compounding.
After preparation of polyvinyl acetate (PVAc) polymer
by solution polymerization using BPO as initiator, the
preparation of thin films of PVAc/CaCO3 and PVAc/
CaSO4 nanocomposites, the following process containing
important steps was followed for the preparation of mother
solutions:
1. In this technique, the nanoparticles of known mass
ratio were added into 20 mL of chloroform, and then
solutions were kept at 343 K in magnetic stirrer for a
period of 30 min. The milky solutions (e.g., solution 1)
were prepared.
2. The PVAc was dissolved in 100 mL of chloroform.
The solution was kept at 343 K in a magnetic stirrer
for 30 min. A transparent homogeneous solution (e.g.,
solution 2) was obtained.
3. In order to prepare mother solutions, the solution 1 was
added drop by drop in step 2 solutions, and these new
solutions were stirred again for 30 min. The mother
solutions were thus prepared.
The nanocomposites films were cast on a Petri dish and
kept at 383 K for 1 h under vacuum to remove trace of the
solvent present in the samples, and PVAc/CaCO3 and
PVAc/CaSO4 nanocomposites films with concentrations of
three different sample codes are listed in Table 1.
The thickness of all the films were controlled to around
30 lm by adjusting the concentration and amount of
solution utilized.
Characterization
X-Ray diffraction (XRD)
The sizes and crystal phases of the particles were con-
firmed by XRD analysis using a Bruker AXS D8 Advance
Table 1 Composition and sample code of PVAc/CaCO3 and PVAc/
CaSO4 nanocomposites used in this investigation
PVAc/CaCO3/wt% 0 1 2 4
Sample code PVAc 0 PVAc 1 PVAc 2 PVAc 3
PVAc/CaSO4/wt% 0 1 2 4
Sample code PVAc 0 PVAc 4 PVAc 5 PVAc 6
XRD instrument applying Cu Ka (k = 0.15406 nm) radi-
ation under the accelerating voltage of 40 kV, current-
35 mA, and scanning rate of 0.020°s-1 (scan range
2h = 3°–70°).
FT-IR
The chemical structures of the synthesized PVAc/CaCO3
and PVAc/CaSO4 nanocomposites were analyzed by FT-IR
spectroscopy using Thermo Nicolet, Avatar 370, HATR-
assembled instrument.
Scanning electron microscopy (SEM) and Energy
dispersive spectrometer (EDS)
The SEM analyses of CaCO3 and CaSO4 nanoparticles, and
their distributions in PVAc matrix were done using JEOL
Model JSM - 6390LV SEM instrument. The detection of
elemental compositions of nanoparticles and their nano-
composites were carried out by EDS using JEOL Model
JED–2300 instrument.
Thermal degradation (TG/DTG)
Thermal degradation measurements were carried out on
Perkin Elmer Diamond TG/DTA instrument. Thermal
stabilities of the pure polymer and composites were
determined by TG and DTG analyses under flowing N2
(80 mL min-1) and at a heating rate of 293 K min-1.
Differential scanning calorimeter
Glass transition temperature, Tg, measurements were car-
ried out on DSC instrument (Netzsch DSC 204). All
measurements on DSC instrument were performed with the
temperature ranging from 303 to 473 K under nitrogen
atmosphere (heating rate 283 K min-1).
UV–Vis spectrophotometer
UV–Vis-absorption spectra of nanocomposites in chloro-
form were obtained using a Systronics Double Beam
Spectrophotometer 2201.
Results and discussion
X-Ray powder diffraction characterizations of CaCO3
and CaSO4 nanoparticles
Figure 1 shows the XRD patterns of CaCO3 and CaSO4
nanoparticles. The calculated main diffraction peaks
123
 M. K. Pal, J. Gautam

Fig. 1 XRD pattern of CaCO3 13000

and CaSO4 nanoparticles 12000
11000
10000
9000

Lin/counts
8000
7000
6000
5000
4000
3000
2000
1000
0
3 10 20 30 40 50 60 70

5000

4000
Lin/counts

3000

2000

0
3 10 20 30 40 50 60 70
2θ /°

(29.391°, 35.946°, 39.396°, and 48.499°) were observed at
2h values for CaCO3 nanoparticles (as calcite), and in
CaSO4 nanoparticles (as orthorhombic), these diffraction
peaks were observed at 14.957°, 25.814°, 29.932°, 32.120°,
and 49.534°. These positions of all diffraction peaks were
consistent with standard CaCO3 and CaSO4 powder dif-
fraction data reported in the literature (JCPDS card
No.- 47-1743 and JCPDS card No.-26-0392 for CaCO3 and
CaSO4 nanoparticles, respectively) [33, 34] ,and no other
peak could be identified. In addition, the crystalline size of
synthesized nanoparticles could be obtained from their
XRD peaks using Debye–Scherrer’s formula [35] which is
given in Eq. 1:
D ¼ 0:9k=bcosh
where k = wavelength of X-ray (0.1541 nm), b =
FWHM, h = diffraction angle in radian, and D = particles
diameter. The CaCO3 nanoparticles have an average par-
ticles diameter of 33 nm, and CaSO4 nanoparticles have an
average particles size of 25 nm.
FT-IR spectra of the PVAc/CaCO3 and PVAc/CaSO4
nanocomposites
Figure 2 illustrates the FT-IR spectra of the PVAc/CaCO3
(PVAc 2) nanocomposites. Bands ranging from 2,925 to
2,892 cm-1 correspond to the CH, CH2, and CH3 group
stretching vibrations of PVAc. A band at 1,725 cm-1
appeared because of the presence of ester carbonyl group
stretching vibration of PVAc. Band at 1,218 cm-1 repre-
sents the C–C(=O)–O group of PVAc. A band at
1,428 cm-1 explains the asymmetric bending, while bands
at 945 and 794 cm-1 show out-of-plane bending of CH3
group. The bands at 1,490, 875, and 711 cm-1 [36] in
PVAc/CaCO3 nanocomposites show the dispersion of
CaCO3 nanoparticles in the PVAc matrix. In the PVAc/
CaSO4 (PVAc 5), nanocomposites show all the relative
bands for PVAc along with bands at 658, 604, and
433 cm-1 for sulfate group [32]. This shows that CaSO4 is
present in the PVAc polymer matrix (Fig. 3). These results
clearly indicated that nanoparticles are present in the
ð1Þ polymer matrix. The details of all the bands are shown in
Table 2.
SEM morphology and element detection
of nanoparticles and nanocomposites
Figures 4 and 5 show the morphologies and elemental
compositions of CaCO3, and CaSO4 nanoparticles, and the
dispersion of nanoparticles in PVAc polymer matrix. SEM
analysis shows that the pure CaCO3 and CaSO4 nanopar-
ticles have a diameter of at least one dimension in the range
of 25–35 nm. These were in good concurrence with the
XRD studies. In the nanocomposites SEM graphs, we
observe that the nonionic surfactant-modified nanoparticles
are uniformly dispersed in the polymer matrix. PEG was

123
Effects of inorganic nanofillers

Fig. 2 FTIR spectra of PVAc/

CaCO3 nanocomposites 90
(PVAc 2)
80

2890.61
70

2981.68

2359.17
60

3426.93

2925.52
50

%T
40

1725.52
1630.12

1490.74

794.54
1428.08

1218.08

1025.52

711.27
30

875.00

604.61
20

945.74
10

0
–10
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers/cm–1

Fig. 3 FTIR spectra of PVAc/ 100

CaSO4 nanocomposites
90
(PVAc 5)
80

795.03
70

709.45
604.92

433.81
60

945.48
2143.31
50

658.93
1276.27
%T

1382.52
2882.52
3888.13

1624.74
40

1727.65

1430.95
30
2985.52
2925.34

20

10
3449.02

–10
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers/cm–1

used as a surfactant agent to reduce the size of the particles
and to improve the dispersion. The presence of surfactant-
modified nanofiller surface confers hydrophobic properties
on nanoparticles, which can improve its compatibility with
the polymeric matrix and prevents particles’ aggregation
by reducing their surface energy. The shifts in the positions
of peaks of various groups of PVAc from their respective
main position in the FT-IR spectra of the nanocomposites
reveal the existence of bonding interaction between inor-
ganic filler and polymer. Hence, the structure of the inor-
ganic particles can be maintained during the preparation of
nanocomposites.
EDS graphs confirmed the formation of the nanocom-
posites by showing that the metal compositions of nano-
particles were not maintained after the preparation of
nanocomposites. The Count versus KeV graphs show the
calcium percentage in CaCO3 and CaSO4 nanoparticles,
and the sulfur percentage in CaSO4 nanoparticles was not
maintained after the preparation of nanocomposites. The
less-intense peaks of calcium and sulfur particles’ counts in
the nanocomposites may be because nanoparticles were
deeply seated or enveloped in the polymer matrices as
revealed from SEM micrographs, which proved difficult to
remove the particles’ electrons from the surface of polymer
nanocomposites films. However, the increase in carbon
peak in polymer nanocomposites shows a good adhesion
between the surface of nanoparticles and polymer matrices.
Thermal properties
Glass transition behavior (Tg)
The DSC curves obtained during heating (283 K min-1) of
pure PVAc and PVAc-based nanocomposites containing 1,

123
 M. K. Pal, J. Gautam

Table 2 FT-IR spectroscopic data of PVAc/CaCO3 nanocomposites (PVAc 2), and PVAc/CaSO4 nanocomposites (PVAc 5)
Wavenumber/cm-1 Group Assignment

PVAc/CaCO3 2,981, 2,925, 2,890 CH3–, –CH2–, [ CH– m(–C–H)

nanocomposites 1,725 C=O (carbonyl) m(–C–O)
1,218 C–C(=O)–O m(–C–O)
1,428 CH3– (asymmetrical) d(–C–H)
945, 794 CH3–, –CH2– d(–C–H) out of plane
1,490, 875, 711 C=O bond in the carbonate ion m(–C–O)
PVAc/CaSO4 2,985, 2,925, 2,882 CH3–, –CH2–, [ CH– m(–C–H)
nanocomposites 1,727 C=O (carbonyl) m(–C–O)
1,276 C–C(=O)–O m(–C–O)
1,430 CH3– (asymmetrical) d(–C–H)
1,382 CH3– (symmetrical) d(–C–H)
945, 795 CH3–, –CH2– d(–C–H) out of plane
658, 604, 433 S=O bond in the sulfate ion m(–S–O)
m- Stretching vibrations, d- bending vibrations in plain

Fig. 4 SEM micrographs and 1000

EDS spectra of a CaCO3 (a) 900
Atom% in CaCO3 nanoparticles
Ca K, 9.6, 10% C K, 33.17, 33%
nanoparticles, and b PVAc/ 800
CaCO3 nanocomposites 700
(PVAc 2)

CaKa
600

Counts
500 O K, 57.23, 57%

400

OKa
300
CKa

CaKb
200

100

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
KeV
1000
Atom% in PVAc/CaCO3 nanocomposites
(b) 900
CKa

Ca K, 0.17, 0%
O K, 32.25, 32%
800

700

600
Counts

OKa

500
C K, 67.58, 68%
400

300

200
SiKa

CaKa
CaKb

100

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
KeV

2, and 4 wt% of CaCO3 and CaSO4 nanoparticles under
inert nitrogen atmosphere are presented in Figs. 6 and 7.
The relative Tg’s (exothermic peak) of pure PVAc and its
nanocomposites computed from DSC results given in
Table 3 were used to study the roles of incorporated
nanoparticles on the thermal stability of PVAc. All the
investigated materials show that Tg’s were determined at
the midpoint of the transition point. The Tg’s of PVAc/
CaCO3, and PVAc/CaSO4 nanocomposites were higher
compared to pure PVAc. The high melting point of CaSO4
nanoparticles contributes to the higher Tg’s of PVAc/
CaSO4 nanocomposites in comparison to the PVAc/CaCO3
nanocomposites. It is also obvious that Tg increases with
nano-inorganic filling, suggesting that the nanoparticles
play a role in inhibiting polymer segmental motion. The
interaction of polymer chains with nanoinorganic reduces

123
Effects of inorganic nanofillers

Fig. 5 SEM micrographs and 1000

(a) Atom% of CaSO4 nanoparticles
EDS spectra of a CaSO4 900
S K, 12.87, 13%
Ca K, 8.36, 8%

nanoparticles, and b PVAc/ 800

CaSO4 nanocomposites 700
(PVAc 5)

SKa
600

Counts
500

CaKa
O K, 78.77, 79%

OKa
400

300

200

CaKb
SKb
100

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
KeV
(b) 1000
Atom% of PVAc/CaSO4 nanocomposites
900 Ca K, 0.58, 1%

800 S K, 0.87, 1%

CKa
O K, 29.7, 30%
700

600

Counts
500

400

OKa
300 C K, 68.85, 68%

SKa

CaKa
200

CaKb
SKb
100

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
KeV

Fig. 6 DSC curves (exothermic DSC/(mW/mg) DSC/(mW/mg) Glass Transition:

Exo Exo Onset: 320.6 K
peak) of a pure PVAc (PVAc 0), Glass Transition: Mid: 327.3 K
Onset: 325.3 K
and PVAc/CaCO3 0.40 PVAc 0 0.40 Inflection: 331.3 K PVAc 1
Mid: 326.4 K End: 340.0 K
nanocomposites (PVAc1, 0.35
Inflection: 338.9 K
0.35
Delta Cp*: 0.355 J/(g*K)
End: 344.3 K
PVAc 2, and PVAc 3) Delta Cp*: 0.120 J/(g*K)
0.30 0.30

0.25
0.25 [1]

0.20
0.20
0.15
0.15
0.10
0.10

DSC/(mW/mg) DSC/(mW/mg) Glass Transition:

Exo Exo
0.50 Onset: 327.2 K
Glass Transition: PVAc 2 PVAc 3
Onset: 326.4 K Mid: 331.5 K
0.6 0.45 Inflection: 337.7 K
Mid: 327.7 K
Inflection: 327.7 K End: 346.3 K
End: 329.5 K 0.40 Delta Cp*: 0.328 J/(g*K)
0.5
Delta Cp*: 0.099 J/(g*K)
0.35
[1]
0.4
0.30

0.25
0.3

0.20
0.2
0.15

0.1 0.10

40 60 80 100 120 140 1 40 60 80 100 120 140 160 180

273 + Temperature/K 273 + Temperature/K

the mobility of polymer chains and leads to the formation stiffness to the polymer matrix at high temperatures. Owing
of immobilized and restricts the mobility of polymer chain to the large surface area of nanoparticles, large amounts of
around the filler particles [37–39], and the improvements in polymer chain have strong interaction with the particles
Tg’s of nanocomposites suggest that the nanofillers cause surface and prevent segmental motion of the polymeric

123
 M. K. Pal, J. Gautam

Fig. 7 DSC curves (exothermic DSC/(mW/mg) DSC/(mW/mg) Glass Transition:

Onset: 330.3 K
Exo Exo
peak) of a pure PVAc (PVAc 0), Glass Transition: Mid: 334.9 K
PVAc 4
0.40 Onset: 325.3 K PVAc 0 0.45 Inflection: 343.1K
and PVAc/CaSO4 Mid: 326.4 K End: 348.8 K
nanocomposites (PVAc 4, 0.35
Inflection: 338.9 K
End: 344.3 K
0.40 Delta Cp*: 0.223 J/(g*K)

PVAc 5, and PVAc 6) Delta Cp*: 0.120 J/(g*K) 0.35

0.30
0.30 [1]

0.25
0.25

0.20 0.20

0.15
0.15

0.10
0.10
0.05
Glass Transition:
DSC/(mW/mg) DSC/(mW/mg)
Exo
PVAc 5 Exo
Onset: 340.3 K
PVAc 6
0.55 Mid: 372.6 K
Glass Transition: 0.40 Inflection: 353.8 K
0.50 Onset: 320.7 K
End: 379.7 K
Mid: 347.0 K 0.35 Delta Cp*: 0.699 J/(g*K)
0.45 Inflection: 336.9 K
End: 384.3 K
0.30
0.40 Delta Cp*: 1.433 J/(g*K)
[1]
0.35 0.25

0.30 0.20

0.25
0.15
0.20
0.10
0.15
0.05
0.10

40 60 80 100 120 140 160 180 40 60 80 100 120 140 160 180
273 + Temperature/K 273 + Temperature/K

Table 3 Tg’s of PVAc/CaCO3 and PVAc/CaSO4 nanocomposites chains [40]. The DSC spectra clearly indicate the restricted
with 0–4 wt% loading of CaCO3 and CaSO4 nanoparticles segmental motion and polymer–nanoparticle interaction.
Fillers/wt% Tg/K of PVAc/CaCO3 Tg/K of PVAc/CaSO4 These results are concurrent with those of SEM-EDS and
nanocomposites nanocomposites FT-IR.
0 326.4 326.4
Thermogravimetric analysis
1 327.3 334.9
2 327.7 347.0
The thermal decomposition profiles of the pure PVAc,
4 331.5 372.6
PVAc/CaCO3, and PVAc/CaSO4 nanocomposite films

Fig. 8 TG/DTG graph of pure 8.477 0.1353

PVAc (PVAc 0) 8 0.0

7
–0.5
713.92 K
6 –0.445 mg/min
Derivative mass/mg min–1

5 –1.0
Mass/mg

–1.5
3

2
–2.0

1 614.70 K
–2.375 mg/min

0.1843 –2.496
38.57 100 200 300 400 500 600 708.9
273 + Temperature/K

123
Effects of inorganic nanofillers

Fig. 9 TG/DTG graph of 7.313 0.06872

nanocomposites (PVAc 1) 7 0.0

–0.2
6

–0.4
5 717.84 K
–0.378 mg/min

Derivative mass/mg min–1

–0.6

Mass/mg
–0.8

3 –1.0

2 –1.2

–1.4
1

–1.6
614.78 K
0 –1.718 mg/min

–0.5197 –1.806
37.33 100 200 300 400 500 600 707.6
273 + Temperature/K

Fig. 10 TG/DTG graph of 10.24 0.3028

nanocomposites (PVAc 2) 0.2

9 0.0

–0.2
8
–0.4

Derivative mass/mg min–1

7
–0.6
716.25 K
Mass/mg

–0.595 mg/min
6 –0.8

–1.0
5

–1.2
4
–1.4

3 –1.6
615.88 K
2 –1.818 mg/min –1.8
1.592 –1.92
50.9 100 200 300 400 500 600 707.9
273 + Temperature/K

under nitrogen flow are given in Figs. 8, 9, 10, 11, 12, 13,
and 14. The TG/DTG curves of pure PVAc have strong
peaks at 614.70 K and show a two-stage degradation pro-
cess, which was consistent with the literature [41]. In the
first stage, de-acetylation occurs and conjugated double
bonds are formed along the polymer backbone. In the
second stage, structural degradation of the polymer pro-
ceeds leading to the evolution of aromatic compounds.
With an increase of nanoparticles loading, the decompo-
sition temperature (Td) was shifted toward higher values.
For example, in the case of PVAc/CaCO3 nanocomposites
with 1, 2, and 4 wt% loadings of nanoparticles, the Td’s
were shifted at 614.78, 615.88, and 617.10 K, respectively.
While in the PVAc/CaSO4 nanocomposites, the corre-
sponding decomposition temperatures were 615.24,
616.22, and 617.52 K with same wt% loadings of nano-
particles. From these results, it is clear that PVAc/CaSO4
nanocomposites were finally more thermally stable than
PVAc/CaCO3 nanocomposites by 0.40 K. The beneficial
improvements in the thermal properties of both the nano-
composite films could be derived because of the large
surface area and surface modification of CaCO3 and CaSO4

123
 M. K. Pal, J. Gautam

Fig. 11 TG/DTG graph of 14.23 0.2372

nanocomposites (PVAc 3) 0.0

12 –0.5

792.82 K
705.74 K –0.553 mg/min –1.0

Derivative mass/mg min–1

10 –0.775 mg/min

–1.5

Mass/mg
8
–2.0

6 –2.5

–3.0
4
–3.5

2 617.10 K
–4.037 mg/min –4.0
0.8685 –4.241
42.42 100 200 300 400 500 600 709.5
273 + Temperature/K

Fig. 12 TG/DTG graph of 5.23 0.1162

nanocomposites (PVAc 4) 5.0
0.0
4.5
–0.2
4.0

Derivative mass/mg min–1

3.5 –0.4

3.0
–0.6
Mass/mg

2.5

–0.8
2.0

1.5
–1.0

1.0
–1.2
0.5
615.24 K
0.0 –1.4
–1.464 mg/min

–0.423 –1.54
34.86 100 200 300 400 500 600 709.4
273 + Temperature/K

nanoparticles, which enable the nanoparticles to bind the
individual polymer chain and further cross-link the matrix
polymer chains. The further cross-linking in the PVAc/
CaCO3 and PVAc/CaSO4 nanocomposites film hindered
the movement of the pure PVAc strand and prevented the
decomposition of the pure PVAc at a relatively higher
temperature.
UV–Vis spectra
Figures 15 and 16 show the UV–Vis-absorbance spectra
containing various concentration (0–4 wt %) of CaCO3
and CaSO4 nanoparticles in PVAc matrix. The UV
absorbance increased as the nanoparticles content
increased in polymer matrix. For all the nanocomposites,
the absorption band appeared near at 335 nm. The
intensity of this band increase with nanoparticles.
However, the absorbance intensity of PVAc/CaSO4
nanocomposites was higher than PVAc/CaCO3 nano-
composites. This may be due to the lower energy band
gap of CaSO4 nanoparticles (*4.7 eV) [42] in compari-
son with CaCO3 nanoparticles (*5.0 eV) [43]. By the
addition of nanoparticles, the energy band gap of nano-
composites was *4.4 eV which was lower in comparison

123
Effects of inorganic nanofillers

Fig. 13 TG/DTG graph of 8.376 0.09657

nanocomposites (PVAc 5) 8 –0.0

–0.2
7
417.15 K
–0.4
–0.152 mg/min
6
–0.6

Derivative mass/mg min–1

712.95 K
–0.515 mg/min –0.8
5

–1.0

Mass/mg
4
–1.2
3
–1.4

2 –1.6

–1.8
1
–2.0
0
616.22 K –2.2
–2.285 mg/min
–0.9824 –2.399
28.23 100 200 300 400 500 600 709.4
273 + Temperature/K

Fig. 14 TG/DTG graph of 22.63 0.2039

nanocomposites (PVAc 6) 22 0.0

20 –0.5

–1.0
18 723.73 K
–0.844 mg/min
–1.5

Derivative mass/mg min–1

16
–2.0
Mass/mg

14
–2.5
12
–3.0

10
–3.5

8 –4.0

6 617.52 K –4.5
–4.623 mg/min
4.735 –4.853
40.61 100 200 300 400 500 600 708.1
273 + Temperature/K

with pure PVAc (*4.6 eV). This was because the addi-
tion of high-energy band gap semi-conducting nanopar-
ticles causes the localized states of different color centers
to overlap and extend in the mobility gap [44]. Thus,
from the above results, it can be concluded that the
UV-shielding property of nanocomposites can be con-
trolled by the addition of CaCO3, and CaSO4 nanoparti-
cles in the PVAc matrix. These optical properties may
endow the nanocomposites advantages for application in
optical fields.

123
 M. K. Pal, J. Gautam

2.575 matrix and nanoparticles. The thermal degradation tem-

perature (Td) and glass transition temperature (Tg) of the
PVAc were improved by the addition of both CaCO3 and
2.033
CaSO4 nanoparticles, although the greatest increase was
observed for PVAc/CaSO4 nanocomposites. The prepared
Absorbance

1.490 nanocomposites have good and adjustable UV-shielding

property according to their UV–Vis-absorbance spectra.
0.948
PVAc 3 This study not only presents a promising strategy for
industrial production of UV-shielding nanocomposites, but
also contributes to the understanding and design of inor-
0.406 PVAc 2
PVAc 1
ganic–polymer nanocomposites with preferred properties.
PVAc 0

–0.136 Acknowledgements This research study was supported by the

200.00 260.00 320.00 380.00 440.00 500 University Grant Commission, New Delhi (India). The authors
Wavelength/nm gratefully acknowledge the facilities provided by the Department of
Chemistry, Dr. B. R. Ambedkar University, Agra, India to carry out
Fig. 15 UV–Vis spectra of PVAc/CaCO3 nanocomposites this study successfully. The authors thank the Director, STIC (SAIF)
Kochi, and IIT Chennai (SAIF) Chennai for providing FT-IR, XRD,
DSC, TG/DTG, SEM, and EDS characterization facilities.
2.575

PVAc 6 References
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