Spectrochimica Acta Part A 66 (2007) 1237–1242

FTIR studies of PVC/PMMA blend based polymer electrolytes

S. Ramesh a,∗ , Koay Hang Leen a , K. Kumutha b , A.K. Arof c
a Faculty of Engineering & Science, Universiti Tunku Abdul Rahman, Jalan Genting Kelang, Setapak, 53300 Kuala Lumpur, Malaysia
b Chemistry Department, University of Malaya, 50603 Kuala Lumpur, Malaysia
c Physics Department, University of Malaya, 50603 Kuala Lumpur, Malaysia

Received 17 December 2005; received in revised form 11 May 2006; accepted 19 June 2006

Abstract
The polymer electrolytes composing of the blend of polyvinyl chloride–polymethyl methacrylate (PVC/PMMA) with lithium triflate (LiCF3 SO3 )
as salt, ethylene carbonate (EC) and dibutyl phthalate (DBP) as plasticizers and silica (SiO2 ) as the composite filler were prepared. FTIR stud-
ies confirm the complexation between PVC/PMMA blends. The C Cl stretching mode at 834 cm−1 for pure PVC is shifted to 847 cm−1 in
PVC–PMMA–LiCF3 SO3 system. This suggests that there is interaction between Cl in PVC with Li+ ion from LiCF3 SO3 . The band due to OCH3
at 1150 cm−1 for PVC–PMMA blend is shifted to 1168 cm−1 in PVC–PMMA–LiCF3 SO3 system. This shift is expected to be due to the interaction
between Li+ ion and the oxygen atom in PMMA. The symmetric vibration band and the asymmetric vibration band of LiCF3 SO3 at 1033 and
1256 cm−1 shifted to 1075 and 1286 cm−1 in the DBP–EC plasticized PVC–PMMA–LiCF3 SO3 complexes. The interaction between Li+ ions and
SiO2 will lead to an increase in the number of free plasticizers (which does not interact with Li+ ions). When the silica content increases from 2% to
5%, the intensity of the peak at 896 cm−1 (due to the ring breathing vibration of free EC) increases in PVC–PMMA–LiCF3 SO3 –DBP–EC system.
© 2006 Elsevier B.V. All rights reserved.

Keywords: PVC; PMMA; FTIR; Silica

1. Introduction pressure, such as propylene carbonate (PC) (ε = 64.4) and ethy-

Polymer electrolytes are of technological interest due to
their possible application as solid electrolytes in various elec-
trochemical devices such as energy conversion units (batter-
ies/fuel cells), electrochromic display devices, photochemical
solar cells, supercapacitors and sensors [1–3]. Among the var-
ious applications, the use of polymer electrolytes in lithium
batteries has been most widely studied. In a secondary battery,
a polymer electrolyte will function as a separator as well as an
electrolyte [4].
Initial work on polymer electrolytes was mostly based on the
complexes of poly(ethylene oxide) (PEO) with inorganic salts
[5–9]. This kind of polymer electrolyte is usually referred to
as the first generation solid polymer electrolytes (SPE). How-
ever, the main drawback of this first generation SPE is the high
degree of crystallization of PEO. One of the approaches to over-
come the above drawback is to use low molecular weight aprotic
plasticizers having high dielectric constant (ε) and low vapour
∗ Corresponding author. Tel.: +60 3 4107 9802; fax: +60 3 4107 9803.
E-mail address: ramesh@mail.utar.edu.my (S. Ramesh).
lene carbonate (EC) (ε = 89.6) [10–12]. The polymer electrolytes
with plasticizers are known as the second generation PE. The
plasticizers impart salt-solvating power and high ion mobility
to the polymer electrolytes. However, the use of plasticizers
tend to decrease the mechanical strength of the electrolytes, par-
ticularly at a high degree of plasticization [3,13]. Composite
polymer electrolytes with inorganic fillers can be considered as
the third generation SPE. Inorganic fillers are used to improve
the electrochemical and mechanical characteristics of the second
generation SPE [14–17]. Another approach towards producing
polymer electrolytes that have high ionic conductivity and strong
mechanical strength would be to use polymers in modified forms
like polymer blends [18–22].
Studies on polymer electrolytes have attracted great attention
in the efforts to clarify the mechanism of conductivity enhance-
ment in such systems. The complexation, nature and concen-
tration of the various ionic species are important to understand
the overall mechanism of conductivity. Infrared spectroscopy
is a method to confirm the complexation between the salt and
the polymer or between the plasticizer and the polymer or even
between the plasticizer and salt. Several researchers used this
technique to study the interaction between polymer, salt and

1386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.06.012
1238 S. Ramesh et al. / Spectrochimica Acta Part A 66 (2007) 1237–1242

plasticizers. In all these work, the interaction is determined by

the shift in the IR spectrum [23,24].
The present work is aimed at describing a comparative IR
spectroscopic study involving PVC–PMMA blend based poly-
mer electrolytes which have been made in order to examine
interactions within the systems.

2. Experimental

The starting materials, PVC was obtained from Fluka, while

poly(methyl methacrylate) (PMMA) was obtained from Aldrich.
The PVC/PMMA blends have been prepared by mixing with
tetrahydrofuran (THF) that was obtained from J.T. Baker. THF
was selected as the solvent on the basis of its efficacy for disso-
lution of polymers and excellent film formability [25].
Fig. 1. FTIR spectra of pure PVC.
In this study, lithium triflate (LiCF3 SO3 ), obtained from
Aldrich, was used as the doping salt. The plasticizers, dibutyl
phthalate (DBP) and ethylene carbonate (EC) were both pro-
cured from Aldrich and Fluka respectively. Fumed silica (SiO2 )
which was kindly supplied by Wacker Chemie was used as the
ceramic filler. SiO2 is a loose white powder with particle size of
10–30 nm.
Prior to the preparation of polymer electrolytes, LiCF3 SO3
was dried at 100 ◦ C for 1 h in order to eliminate trace amounts of
water in the material. Desired amounts of PVC//PMMA blend
and LiCF3 SO3 were dissolved separately in THF and these solu-
tions were then mixed together and stirred. After incorporating
the required amounts of plasticizers (DBP and EC), inorganic
filler SiO2 powder was suspended in the solution and stirred for
24 h to achieve a homogeneous, viscous solution. The solutions
thus obtained were cast on a glass plate and allowed to evaporate Fig. 2. FTIR spectra of pure PMMA.
slowly inside a dessicator. This procedure yields mechanically
stable and free standing films.
In this work, IR was carried out using the FTIR Spectrometer
Spectrum RX1 in the wave region between 4000 to 500 cm−1 ,
resolution 4 cm−1 .

3. Results and discussion

Infrared (IR) radiation refers broadly to the part of the electro-

magnetic spectrum between the visible and microwave regions.
Of great practical use is the wavenumber region between 4000
and 400 cm−1 . FTIR spectroscopy is an important tool in the
investigation of polymer structure. The IR spectra of these mate-
rials vary according to their compositions and may be able to
show the occurrence of complexation and interaction between
the various constituents. The resolution is 4 cm−1 . Fig. 3. FTIR spectra of PVC:PMMA (30:70) blend.

Table 1
3.1. PVC–PMMA spectra
Vibrational modes and wavenumbers exhibited by PVC

FTIR spectra were recorded in the transmittance mode. The Description of vibrations Wavenumbers (cm−1 ) References
FTIR spectra of pure PVC, pure PMMA and PVC–PMMA sam- C H stretching 2890–2958 [27]
ples are shown in Figs. 1–3, respectively. The band assignments CH2 deformation 1339 [27,30]
for PVC and PMMA have already been reported in the literature CH rocking 1240–1257 [27,30]
trans CH wagging 961 [27]
[26–28] and are listed in Tables 1 and 2, respectively.
C Cl stretching 844 [32]
These bands can also be observed in Fig. 1 (for PVC) and cis CH wagging 600 [30]
Fig. 2 (for PMMA). For PVC, C H stretching mode can be
 S. Ramesh et al. / Spectrochimica Acta Part A 66 (2007) 1237–1242 1239

Table 2
Vibrational modes and wavenumbers exhibited by PMMA
Description of vibrations Wavenumbers (cm−1 ) References

C H stretching 2927–2986 [30,32]

C O stretching 1700–1744 [30,32]
CH3 stretching 1439 [32]
OCH3 stretching 1195 [32]

observed at 2911 cm−1 , CH2 deformation mode at 1333 cm−1 ,

CH-rocking mode at 1254 cm−1 , trans CH wagging mode at
959 cm−1 , C Cl stretching mode at 834 cm−1 and cis CH wag-
ging mode at 616 cm−1 . The peaks at 2951, 1721, 1449 and
1159 cm−1 are assigned to CH stretching, C O stretching, CH3
stretching and O CH3 stretching vibrations, respectively, in Fig. 5. The FTIR spectra of pure LiCF3 SO3 .
PMMA.
Complexation may shift the polymer cage peak frequencies.
at wavenumbers 1271 and 1242 cm−1 . The relative intensity of
FTIR would be sensitive both in situations where complexation
the shoulder increases with increasing PMMA content. When
has occurred in crystalline or amorphous phase [27]. The char-
the PMMA content is 70% the shoulder intensity is higher com-
acteristic peaks of pure PVC 1254, 959, 834 cm−1 are shifted to
pared to that of the original band. The above analysis established
1244, 966, 841 cm−1 in the PVC–PMMA blend. The peaks of
the complexation of PVC–PMMA blends.
pure PMMA at 1721, 1449 and 1159 cm−1 are shifted to 1732,
1435 and 1150 cm−1 , respectively.
3.2. PVC–PMMA–LiCF3 SO3 spectra
Fig. 4 shows the FTIR spectra of pure PVC, pure PMMA
and PVC–PMMA blends in the wavenumber range 1400 to
The FTIR spectra of pure LiCF3 SO3 and PVC–PMMA–
1200 cm−1 . The peak at 1333 cm−1 of pure PVC is assigned to
LiCF3 SO3 system are shown in Figs. 5 and 6, respectively.
CH2 deformation. The relative intensity of the peak decreases
The triflate ion has a vibrational spectrum, which is very
with decreasing PVC content. The band at 1254 cm−1 is assigned
sensitive to its state of co-ordination, producing a series of
to CH-rocking vibration. When PVC is blended with PMMA a
different IR active bands as its environment changes [29].
small shoulder appears in the spectrum at the longer wavenum-
The bands at 1263 and 1033 cm−1 are assigned to asymmet-
ber side. It has found a doublet with increasing PMMA content
ric SO3 and symmetric SO3 vibrations of LiCF3 SO3 , respec-
tively. Fig. 6 shows the existence of this “free triflate” ions
in the PVC–PMMA–LiCF3 SO3 complex (bands at 1256 and
1035 cm−1 ). The characteristic frequencies of LiCF3 SO3 at
3481, 1641 and 1182 cm−1 are shifted to 3548, 1649 and
1168 cm−1 in the polymer complex, respectively. This can be
attributed to the change in environment for the CF3 SO3 − ions
in the complex.
The peaks of PVC–PMMA blend at 841, 966, 1149, 1732 and
2950 cm−1 are shifted to 847, 988, 1168, 1726 and 2955 cm−1

Fig. 4. FTIR spectra of (a) pure PVC, (b) pure PMMA, (c) PVC:PMMA (70:30),
(d) PVC:PMMA (50:50) and (e) PVC:PMMA (30:70) complexes. Fig. 6. FTIR spectra of PVC–PMMA:LiCF3 SO3 (60:40) system.
1240 S. Ramesh et al. / Spectrochimica Acta Part A 66 (2007) 1237–1242
Fig. 7. Changes to the CH-rocking vibration of PVC in (a) PVC:PMMA (30:70)
and (b) PVC–PMMA:LiCF3 SO3 (60:40).
in the PVC–PMMA–LiCF3 SO3 , respectively. This confirms the
complexation between PVC–PMMA blends and LiCF3 SO3 .
The peak at 1244 cm−1 , assigned to the CH-rocking vibra-
tion of PVC in PVC–PMMA blend is observed to have shifted to
1256 cm−1 in the PVC–PMMA–LiCF3 SO3 complex. In addi-
tion, a shoulder appears in the higher wavenumber side, sug-
gesting that the Li ion may be located on the vinyl chloride of
the polymer chain [CH2 CHCl ]n . Fig. 7 illustrates this.
In addition, the C Cl stretching mode at 834 cm−1 for pure
PVC shifted to 847 cm−1 in PVC–PMMA–LiCF3 SO3 system.
This implies that there is interaction between Cl in the PVC with
Li+ ion from the salt. The 1150 cm−1 band due to OCH3 in
the PVC–PMMA blend is shifted to 1168 and the 1732 cm−1
band due to C O is shifted to 1726 cm−1 . These shifts are
expected to be due to interaction between Li+ ion and the
oxygen atoms in PMMA. Hence complexation occurs in the
PVC–PMMA–LiCF3 SO3 system.
3.3. PVC–PMMA–LiCF3 SO3 –DBP and
PVC–PMMA–LiCF3 SO3 –DBP–EC spectra
The FTIR spectra of PVC–PMMA–LiCF3 SO3 –DBP and
PVC–PMMA–LiCF3 SO3 –DBP–EC systems are shown in
Figs. 8 and 9, respectively. The characteristic peaks of PVC
and PMMA in PVC–PMMA–LiCF3 SO3 system at 2955, 1726,
Fig. 8. The FTIR spectrum of PVC–PMMA–LiCF3 SO3 :DBP (60:40) system.
Fig. 9. The FTIR spectrum of PVC–PMMA–LiCF3 SO3 –DBP:EC (70:30) sys-
tem.
1438, 1168, 988 and 847 cm−1 are shifted to 2874, 1734, 1460,
1161, 992 and 749 cm−1 , respectively, in the presence of DBP
as a plasticizer. These shifts are probably due to the interaction
between lithium cation in the salted blends with the oxygen
atoms at the carbonyl group (C O) and at the ether group
(C O C). This is because oxygen atoms have lone pair elec-
trons.
With the incorporation of EC to the PVC–PMMA–
LiCF3 SO3 –DBP complex, the characteristic peaks of PVC and
PMMA in PVC–PMMA–LiCF3 SO3 system at 847, 988, 1256,
1387 and 1438 cm−1 are shifted to 777, 973, 1286, 1393 and
1484 cm−1 , respectively. This may be due to the association
through the redistribution of charge accompanying the formation
of ionic pairs and aggregation [27,30]. This could be attributed
to the carbonyl group (C O) and oxygen atoms in the EC ring.
The symmetric SO3 vibration band of LiCF3 SO3 at
1033 cm−1 is shifted to 1075 cm−1 in the DBP plasti-
cized system. In addition to the shift, broadening of the
peak is also observed. In PVC–PMMA–LiCF3 SO3 –DBP–EC
system the asymmetric SO3 vibration band of LiCF3 SO3
is shifted from 1256 to 1286 cm−1 as shown in Fig. 9.
The characteristic frequencies of LiCF3 SO3 at 3548, 1649
and 1168 cm−1 are shifted to 3447, 1672 and 1161 cm−1
in the PVC–PMMA–LiCF3 SO3 –DBP complex, respectively.
The characteristic frequencies of LiCF3 SO3 at 3548 and
1649 cm−1 are shifted to 3534 and 1645 cm−1 in the
PVC–PMMA–LiCF3 SO3 –DBP–EC system, respectively. The
shoulder that appears in PVC–PMMA–LiCF3 SO3 system at
1168 cm−1 disappears with the addition of DBP and EC as
shown in Fig. 10. This broadening and shifting of the peaks
indicates the interaction of LiCF3 SO3 with DBP and EC.
From FTIR studies a detailed picture about the possible
interactions between the polymers, salt and plasticizers can be
understood. These results may help us to explain why the ionic
conductivity value of polymer electrolytes increases on addition
of plasticizers. The plasticizers serve to provide a new conduc-
tion pathway along which the lithium ions can hop through the
polymer with low activation energy.
 S. Ramesh et al. / Spectrochimica Acta Part A 66 (2007) 1237–1242
Fig. 10. Changes to the characteristic frequency of LiCF3 SO3 at
1168 cm−1 in (a) PVC–PMMA:LiCF3 SO3 (60:40) and (b) PVC–PMMA–
LiCF3 SO3 –DBP:EC (70:30).
Fig. 11. The FTIR spectra of silica.
3.4. PVC–PMMA–LiCF3 SO3 –DBP–EC–SiO2 spectra
Figs. 11 and 12 show the FTIR spectra of silica
and PVC–PMMA–LiCF3 SO3 –DBP–EC–SiO2 system, respec-
tively. A strong Si O band is observed at 1104 cm−1 in the
FTIR of silica. This strong band is shifted to 1168 cm−1 in the
PVC–PMMA–LiCF3 SO3 –DBP–EC–SiO2 system. In order to
confirm the presumption that the interaction between the lithium
cation and the silica makes the plasticizer free, the environ-
ment of EC in composite polymer electrolytes was studied by
Fig. 12. FTIR spectra of PVC–PMMA–LiCF3 SO3 –DBP–EC:SiO2 (95:5).
1241
Fig. 13. FTIR spectra of PVC–PMMA–LiCF3 SO3 –DBP–EC:SiO2 system with
(a) 2% SiO2 and (b) 5% SiO2 .
FTIR spectroscopy. Fig. 13 shows the FTIR spectra of the com-
posite polymer electrolytes with different silica content in the
region 800–950 cm−1 . There is evidence to show that the peak at
896 cm−1 is due to the ring breathing vibration of free EC [31].
As is shown in Fig. 13, when the silica content increases from
2% to 5% the intensity of the peak at 896 cm−1 increase. This
indicates that the amount of free EC, which does not interact
with lithium cation, is increased with the silica content.
4. Conclusions
At the molecular level, FTIR studies provide strong evidence
that there is a specific interaction between the PVC/PMMA
blends that favors the miscibility of the blends. The change in
intensity, shape and position of the peaks confirms the complex-
ation of PVC–PMMA blends with LiCF3 SO3 , DBP, EC and
SiO2 . The addition of plasticizers introduces a new ionic path-
way along which the Li+ ions can hop through the polymer with
low activation energy.
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