Available online at www.sciencedirect.

com

ScienceDirect
Materials Today: Proceedings 3 (2016) 37133718 www.materialstoday.com/proceedings

ICMRA 2016

X-RD, SEM, FT-IR, DSC Studies of Polymer Blend Films of

PMMA and PEO
M. Ravindar Reddya, A. R. Subrahmanyama, M. Maheshwar Reddyb,
J. Siva Kumarc , V. Kamalakerd and M. Jaipal Reddyd *
a
Department of Sciences & Humanities, MVSR Engineering College,
Nadergul, Hyderabad - 501510, Telangana, India
b
Department of Scince & Humanities, Sreenidhi Institute of Science & Technology,
Yamnampet, Ghatkesar, R. R. (Dist.)-501301, Telangana, India
c
Department of Physics, Osmania University, Hyderabad 500007, India
d
Department Of Physics and Chemistry, Mahathma Gandi institute of Technology,
Gandipet, Hyderabad - 500 07, Telangana., India

Abstract

Poly (methylmetacrylate)-Poly(ethylene oxide) (PMMA-PEO) polymers blend films were prepared using the solution casting
method. The polymer thin films were characterized by X-ray difraction (XRD), Scanning Electron Microscopy (SEM), FTIR and
differential scanning calorimetry (DSC) technique. The amorphous or crystalline nature of polymers has been confirmed by XRD
analysis. The PMMA surface morphology shows rough surface and micro pore structure. Appearance of rough surface in SEM
micrograph of pure PEO was suggested several crystalline domains. The surface morphology changes severely when PEO added
to PMMA polymer, which shows the development of surface morphology from smooth to rough with increasing of PEO
concentration in PMMA. FT-IR data shows that some of the bands found to be shifted and intensities of some of the bands are
decreased and some are disappeared with the addition of PEO to PMMA when compared to pure PMMA and PEO, which
suggests the coordination/ interaction between PMMA and PEO matrixes. DSC results showed that the melting temperatures
(Tm) of PMMA and PEO blend decreases when compared to pure PEO, PMMA.

2016 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of International conference on materials research and applications-2016.

Keywords: PMMA; PEO; XRD; SEM; FTIR; DSC

*
mjaipalreddy@gmail.com

2214-7853 2016 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of International conference on materials research and applications-2016.
3714 M. Ravindar Reddy/ Materials Today: Proceedings 3 (2016) 37133718

1. Introduction

Properties of different polymers will determine the application to which it is appropriate. The chief advantages of
polymers are low cost, easy processability, good chemical resistance, and low specific gravity. On the other hand,
low strength, low modulus, and low operating temperatures limit their use [1]. To achieve the required valuable
properties, blending is suitable technique, in which two/more polymers uniformly mixed with each other. The
blending process is very attractive because of its versa-tility, simplicity, inexpensiveness and producing new
polymeric materials with modified properties such as morphological, thermal, mechanical, and electrical or
degradation behavior can be change by a favorable choice of the second component of the blend without having to
synthesize totally new materials. Blending technology has important and valuable applications in various fields of
science and engineering. The characterization of interface gives relevant information on interactions between two
polymer matrixes in blend polymer system. The mechanical properties of the polymer blends are dependent upon the
stability of interfacial region. It is very interesting to study the properties such as specific interactions, miscibility,
phase behavior and structure to material properties and performance.

Many researchers have worked on several host polymers e.g. poly (ethylene oxide) (PEO), poly (methyl
methacrylate) (PMMA), poly (vinyl chloride) (PVC) and poly (vinyl acetate) (PVA) etc. Among various homo-
polymers studied, Rigid PMMA chains provide sufficient mechanical stability for the soft PEO segments to achieve
improved mechanical performance for solid-state electrolyte applications. Poly(ethylene oxide) (PEO) exhibits
excellent ion transport properties due to its high concentration of electron pairs and rapid segmental dynamics. PEO
attains high degree of crystallinity, approximately 60%, at room temperature [2-4]. The studies generally incorporate
the development of PMMA-based electrolyte composites, copolymers, and blends [5-7]. Polymer blends offer a
practical and efficient way to fulfill novel requirements for material properties and applications. Physical properties
of polymer blends can be constantly varied among those of the pure components without synthesis of new materials.
As the amorphous phase is the major contributor to the conductivity, then reducing the degree of crystallinity of PEO
systems. In the present paper authors presented the results of preliminary investigation mainly interface/ interaction
between PMMA and PEO polymers matrixes.

2. Experimental Techniques

The blend solid polymer films of Poly(methyl methacrylate), (PMMA), (M.W~15000 SD fine chemicals) and
poly(ethylene oxide), PEO (M. W. 2 10 5 Sigma Aldrich) have been prepared by the solution cast technique.
Polymers PMMA and PEO were added accordingly and dissolved in tetra- hydrofuran (THF). The solutions were
stirred for several hours until homogeneous solutions were obtained. The solutions were cast onto glass petri dishes
and evaporated slowly at room temperature. The films were then transferred into a desiccator for continuous drying.
The XRD patterns of the polymer thin films were recorded using an X-ray Diffractometer. The diffraction data were
taken at room temperature with the Braggs angles (2) varying from 10 to 80 degrees. FTIR Spectroscopy
measurements of pure PMMA, pure PEO and PMMA/ PEO blend films were recorded with the help of
Spectrophotometer-Series II. SEM micrographs of pure PMMA, pure PEO and PMMA/ PEO blend films were taken
by using the scanning electron microscopy (SEM). The differential scanning calorimetry (DSC) of the different
polymer films were carried out using DSCQ20 instrument. About 12 mg of each sample was heated for the
temperature range varying from 500C to 2000C at a heating rate of 100C.min-1.

3. Results and discussion

3.1. XRD Studies

In the present study, the XRD method has been used to study amorphous, crystalline or semi-crystalline nature of
the polymers. The XRD pattern of pure PMMA, PMMA+PEO(90:10),PMMA+PEO(80:20) and PMMA+PEO
 M. Ravindar Reddy / Materials Today: Proceedings 3 (2016) 37133718 3715

(70:30) is shown in Fig.1. The semicrystalline phase of PMMA is evident at 17.30 and 20.70 (Fig.1(a)). The sharp
peaks at 19.20 and 23.40in the pure PEO implies that pure PEO has a high degree of crystallinity [8]. It is observed
that by increasing the concentration of PEO to PMMA, decreases relative intensity of the peaks observed in pure
PMMA which is indicates that the amorphous phase increases in blend films. At higher content of PEO (at 30 wt.%)
in PMMA is found to be sharp peaks, which evidenced the phase separation within the blend of PMMA and PEO
films.

Fig.1. XRD pattern of (a) Pure PMMA, (b) PMMA+PEO (90:10), (c) PMMA+PEO(80:20) and (d) PMMA+PEO (70:30).

3.2. SEM Analysis

Fig.2. (x2500) magnification SEM images of (a) Pure PMMA, (b) PMMA+PEO(90:10),
3716 M. Ravindar Reddy/ Materials Today: Proceedings 3 (2016) 37133718

(c) PMMA+PEO (80:20) and (d) PMMA+PEO (70:30)

Surface morphology of pure PMMA and PMMA/PEO blend films of different compositions are presented as in
Figure 2. Appearance of rough surface in SEM micrograph of pure PEO was suggested several crystalline domains
[9]. The PMMA surface morphology shows rough surface and micro pore structure. The surface morphology
changes severely when PEO added to polymer PMMA. Figure 2(b - d) shows the development of surface
morphology from smooth to rough with increasing of PEO concentration to PMMA. The surface morphology at 10
wt.% PEO in PMMA is appeared to be smooth matrix of the blend film (See Figure 2b), which is the evidence of
satisfactory miscibility between the two polymer matrixes. The smooth morphology is closely related to the
interaction/ coordination between the two matrixes of PEO and PMMA due to cross linking, which indicates that
the blend is compatible. At higher content of PEO (at 30 wt.%) in PMMA is found to be rough surface with
inhomogeneous composite matrix and phase separation was noticed.

3.3. FT-IR Spectroscopy Analysis

FT-IR Spectroscopy is very important spectroscopic tool in the investigation of polymer structures as it
determines the occurrence of complexation/ interaction between two polymer matrixes [10-11]. Infrared spectra
reported in this work were taken with a Spectrophotometer in the wave number region between 3500 and 500 cm-1.
The FTIR spectra of pure PMMA, pure PEO and PMMA/PEO polymer blend are shown in Fig. 3. From Fig. 3 it is
clear the addition of PEO to PMMA shows that the some of the bands found to be shifted and intensities of some of
the bands are decreased and some are disappeared. It is clear that the characteristic bands of PMMA appeared at
2911 cm-1 (C-H stretching mode), 1333 cm-1 (CH2 deformation), 1254 cm-1 (CH rocking), 959 cm-1 (trans-CH
wagging mode), 833 cm-1 (C-Cl stretching mode) and 616 cm-1 (Cis CH waging) are modified or shifted with the
addition of PEO Polymer.

Fig.3.FT-IR Spectra of (a) Pure PMMA, (b)Pure PEO, (c)PMMA+PEO(90:10), (d)PMMA+PEO(80:20) and (e) PMMA+PEO(70:30).

The COC symmetric and asymmetric stretching mode observed around 1100 cm-1 in PEO is found to
prominently and modified in its width by blending with PMMA. The apparent COC band of PEO are found to be
dominant and also it shifts to higher wave number, when compared to Pure PMMA with PMMA/PEO blend films,
which may be due to interaction of PEO and PMMA. If the PEO get coordinated/ interacted with the PMMA, the
 M. Ravindar Reddy / Materials Today: Proceedings 3 (2016) 37133718 3717

spectral changes are expected to be in COC stretching and deformation modes. The increase in the width of 1100
cm-1 band which is assigned to COC symmetrical and asymmetrical stretching [12-15] suggests the coordination/
interaction between PMMA and PEO matrixes.

3.4. DSC Analysis

Figure 4 shows the DSC results of pure PMMA, PEO, and different ratios of blend films of PMMA and PEO.
The DSC studies indicated that the melting temperatures (T m) values are listed in Table 1. The melting temperature
of PEO and PMMA are found to be 72 and 152 C respectively. The melting temperatures of blend films are found to
decreases with blending of PMMA with PEO. The decrease in T m indicates the interaction/ interface between the
two matrixes of PEO and PMMA. At higher content of PEO (at 30 wt.%) in PMMA is found to be higher heat flow,
which may be due to phase separation. These results corroborates with the results observed in X-RD and SEM
studies which evidence of satisfactory miscibility between the two polymer matrixes of PEO and PMMA due to
cross linking and at higher content of PEO (at 30 wt.%) in PMMA is found to be phase separation.

Table.1. DSC data for pure PEO, PMMA and different ratios of PMMA and PEO.

Code Wt% Melting temperature Tm(0C)

Pure PEO 100 72
Pure PMMA 100 152
PMMA+PEO 90:10 68
PMMA+PEO 80:20 60
PMMA+PEO 70:30 54

Fig.4. DSC Curves of (a) Pure PEO, (b) Pure PMMA, (c) PMMA+PEO(90:10), (d) PMMA+PEO(80:20) and (e) PMMA+PEO(70:30).
 3718 M. Ravindar Reddy/ Materials Today: Proceedings 3 (2016) 37133718

4. Conclusions

The amorphous or crystalline nature of polymer PMMA and PEO blends has been confirmed by XRD analysis. The
SEM micrographs suggest that the surface morphology changes severely when PEO added to PMMA polymer, which
indicated the interaction/ interface between the two matrixes of PEO and PMMA due to cross linking. FT-IR data
also suggested the coordination/ interaction between PMMA and PEO matrixes in PMMA/ PEO blend films. Melting
temperatures of polymer PMMA shows decrease when PEO added.

Acknowledgements

The authors would like to thank Head, BOS, Department of physics, Osmania University, Head, BOS, Department
of physics, JNTUH for their encouragement and one of the author MRR thank the Principal, Head(S&H), MVSR
Engineering college for their constant support to carryout this work.

References

[1] Huang, H. and Talreja, R. (2006) Composites Science and Technology, 66, 2743
[2] P.V. Wright, Polymer ElectrolytesThe Early Days, Electrochimica Acta, Vol. 43, No. 10-11, 1998, pp. 1137- 1143
[3] V. D. Noto, S. Lavina, G. A. Giffin and E. Negro, Polymer Electrolytes: Present, Past and Future, Elec-trochimica Acta,57, 2011, pp. 4- 13
[4] J. Evans and C. A. Vincent, Electrochemical Measurement of Transference Numbers in Polymer Electrolytes, Polymer,Vol. 28, No. 13,
1987, pp. 2324-2328
[5] Manoratne, C. H.; Rajapakse, R. M. G.; Dissanayake, M.Int. J. Electrochem. Sci.2006,1, 32
[6] Young, W. -S.; Epps, T. H. Macromolecules 2009, 42, 2672
[7] Chiu, C. -Y.; Chen, H. -W.; Kuo, S. -W.; Huang, C. -F.;Chang, F. -C. Macromolecules 2004, 37, 8424
[8] YU YingHao, JIANG Peng, WANG FuRong, WANG Lefu & LI XueHui, SCIENCE CHINA, 1608-1613 (2012)
[9] M. Jaipal Reddy, PP Chu, J. Siva Kumar, U V Subba Rao, J. Power Sources, 161 (2006) 535
[10] W. Wieczorek, J. R. Stevens, Z. Florjanczyk, Solid State Ionics,85 (1996) 76
[11] F. Croce, L. Persi, B. Scrosati,; Serraino-Fiory, F.; Plichta, E.;Hendrickson, M. A. Electrochimica Acta, 46 (2001) 2457
[12] S. H. Chung, Y. Wang, L. Persi, F. Croce, S. G. Greenbaum, B.Scrosati, E. Plichta, J. Power Sources, 97-98 (2001) 644
[13] B. L. Papke, M. A. ratner and D. F. Shriver, J. Electrochem.Soc. 129 (1982) 1434
[14] B. L. Papke, M. A. ratner and D. F. Shriver, J. Phys. Chem.Solids, 42 (1981) 493
[15] S. A. Hashmi, A. Kumar, K. K. Maurya and S. Chandra, J.Phys. D, 23 (1990) 1307