# Structural and Complex Formation of PVC – LiNO3 – CdO

P Karthika, R Karthigai Selvi, P S Devi Prasadh

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P Karthika, R Karthigai Selvi, P S Devi Prasadh. Structural and Complex Formation of PVC – LiNO3 – CdO. Mechanics, Materials Science & Engineering MMSE Journal. Open Access, 2017, 9, 10.2412/mmse.65.100.626. [https://hal.science/hal-01504680](https://hal.science/hal-01504680)

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Submitted on 10 Apr 2017

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# Structural and Complex Formation of PVC – LiNO₃ – CdO

P. Karthika¹, a, R. Karthigai Selvi¹, P.S. Devi Prasadh², b

1 – Research Scholars, Department of Physics, Ayya Nadar Janaki Ammal College, Sivakasi – 626 124, Tamilnadu, India

2 – Department of Physics, Dr. Mahalingam College of Engineering & Technology, Pollachi – 642 003, Coimbatore, India

a – pkarthikaa@gmail.com

b – psdprasadh@gmail.com

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DOI 10.2412/mmse.65.100.626 provided by [Seo4U.link](https://link.springer.com/10.2412/mmse.65.100.626)

**Keywords:** PVC, LiNO₃, CdO, XRD, FTIR.

**ABSTRACT.** Solid polymer electrolyte films based on Polyvinyl Chloride (PVC) complexed with different concentrations of Lithium Nitrate (LiNO₃) salt using solvent cast technique is prepared. The polymer salt complex formations are confirmed by FTIR studies. The surface morphology of polymer electrolyte is studied by XRD analysis. It provides that the electrolytes are more amorphous in nature and CdO acts as plasticizers. The composite polymer electrolytes show good thermal property, which are confirmed by DSC. This analysis provides information on the glass transition temperature of polymer electrolytes.

**Introduction.** Importance of polymer research focused mainly to develop the polymer electrolyte. These materials were lighter and exhibited mechanical strength. Investigation on complex formation was due to application of solid state batteries, sensors, fuel cells and electrochemical windows cellular telephones etc., However in this process, due to the use of large amount of expensive and harmful. Hence in the present invention, a simple, reliable, time saving and industrially feasible process developed for fabrication of micro – porous polymer membrane. Moreover these membranes detached from the substrate and used for Li battery applications or many other applications depending upon the type of dopant to be used. The membrane morphology was investigated by XRD analysis and complex formation by FTIR.

**Experimental Description.** Polyvinyl chloride used without further purification for the preparation of micro porous membranes. AR/BDH grade lithium nitrate (LiNO₃) used. The different composition of PVC – LiNO₃ and nanofiller CdO prepared by solvent casting technique corresponding constituents in THF. After stirring, a homogeneous solution obtained and poured on to a glass plate and tetrahydrofuran allowed to evaporate in air at room temperature in dust free atmosphere. The films dried for another one day to remove any trace of THF. The films were prepared.

**Result and Discussion**

**XRD Analysis.** X – ray diffraction was useful to examine the nature of sample, particle size analysis of mixture of phases. The amount of amorphous phase of a polymer was also important because the electrical transport occurred through atmosphere phase rather than the crystalline nature.

XRD of pure PVC revealed the amorphous nature of the polymer electrolyte. [1]. It was evident that XRD pattern of PVC, Bragg's peak at 9.5°,22.5° and 28.5° for its partially crystalline nature. When concentration of CdO increased, amorphous character of the sample also increased and it inferred by
shifting of peaks, increasing of intensity and narrowing of peak in this system. In Fig.1, the peak at
22.5° for PVC shifted to 24° for PVC - LiNO₃ system similarly the same for other systems.
Appearance of shifted peaks confirmed the complexation in polymer electrolytes.[3]. The composite
polymer electrolytes exhibited only broad peak, which was the typical characteristics of atmorphous
materials. The increase in atmosphere phase supported conductivity.[2]. The d – spacing for the
system calculated from diffractogram. The d- spacing for PVC is 0.42 Å and 3.66 Å for PVC -
LiNO₃ – CdO(10 Wt %). It was noticed that the d- spacing increased with the increasing von concentration
of CdO. This result provided that the polymer electrolytes were more amorphous in nature as CdO
served like a plasticizer [3].

<figure><img src="image_3.png" /><figcaption>Fig. 1. XRD plots for (c) PVC + LiNO3 + CdO2 (3 Wt %), (d) PVC + LiNO3 + CdO2 (5 Wt %), (e) PVC + LiNO3 + CdO2 (8 Wt %) and (f) PVC + LiNO3 + CdO2 (10 Wt %).</figcaption></figure>

**FTIR Analysis:** It was an efficient technique to analyse the loads structural changes in polymer. Fig 2.1 showed the FTIR spectrum for pure PVC and was agreement with that reported by early investigations. The C-Cl stretching bonds of PVC occurred normally at ∝ (692.47 cm-1), β (639.53 cm-1) and γ (615.31 cm-1) and sensitive to crystalline nature, stereo regularity and configuration of the polymer chain.[1]. In Fig.2, it noticed that the peak 692.47 cm-1 of PVC cording to C – Cl stretching disappeared in the spectrum of PVC – LiNO3.CH2 rocking of PVC at 692.47 cm-1 shifted to 960.58 cm-1 in PVC – LiNO3. The wave numbers 1435.09 cm-1 and 1332.88 cm-1 of PVC corresponding to CH2 wagging and deformation of C – H of CHCl disappeared in the spectrum of PVC – LiNO3. Stretching of C- H of CHCl at 2972.40 cm-1 and asymmetric stretching of C – H of CH2 at 2910.68 cm-1 remains at the same position in PVC – LiNO3. C – C stretching occurred at 1066 cm-1 shifted to 1064.74 cm-1 in PVC – LiNO3. Further, the C-Cl vibration modes of PVC had undergone broadening, disappearance and intensity reduction while adding LiNO3.The vibration mode 651 cm-1 of NO2-(Nitrite anion) of LiNO3[2] appeared with the shift as 1631.83 cm-1 in PVC – LiNO3.This confirmed that there was good complex formation between PVC and LiNO3.
**DSC Analysis:** From Fig. 3 it was seen that PVC - LiNO₃ – CdO (3 Wt %), the endothermic peaks started to appear and the subsequent exothermic peaks found to be shifted. This indicated that the added CdO changed the thermal transition behavior of PVC – LiNO₃ system. It found that there was less broader and small endothermic peak around 124.33° C and exothermic peaks at 268.62° C, 345.53° C and 536.82° C. The exothermic peaks showed a shift towards lower temperature. When compared with pure PVC – LiNO₃, a positively shifted endothermic peak appeared at 100.26° C for CdO added complex. This indicated the increase in rigid nature of the complex PVC – LiNO₃ due to the addition of 3 Wt % of CdO. Degradation found to be started at 268.62° C. It indicated the enhancement of thermal stability due to addition of CdO.

<figure><img src="image_4.png" /><figcaption>Fig. 2. FTIR Spectrum for pure PVC – LiNO₃.</figcaption></figure>

<figure><img src="image_5.png" /><figcaption>Fig. 3. DSC plot for pure PVC – LiNO₃ – CdO₂ (3 Wt %).</figcaption></figure>
**Summary.** The samples were prepared using solvent casting technique. In order to understand the role of nanofiller on the thermal and the electrical properties, the nanofiller of different concentration of CdO added to the PVC-LiNO3 complex and nanocomposite polymer electrolyte prepared using the same solution casting technique. The complex formation of the solid polymer electrolyte has confirmed through the FTIR studies. XRD study also ascertains the complexation between the salt and heteroaction of polymer. Appearance of shifted Bragg's peaks in complex confirm the complexation in polymer electrolyte which increases in d-spacing, proves that the electrolytes are more amorphous in nature and CdO2 acts as a plasticizer. DSC studies reveal that the crystallinity of PVC reduces due to the addition of the LiNO3. The addition of CdO2 leads to the change in endothermic/exothermic reaction.

**References**

[1] S.Rajendran, Shanker Babu and K.Renuka Devi, "Ionic conduction behavior in PVC – PEG blend polymer electrolytes upon the addition of TiO₂", Ionics, Vol. 15, 2009, pp. 61-66. doi: 10.1007/s11581-008-0222-3

[2] Palanisamy Vickraman, Vanchiappan Aravindan, Yan-Sung Lee, "Lithium ion transport in PVC/PEG 2000 blend polymer electrolytes complexed with LiX (X= ClO₄⁻, BF₄⁻ and CF₃SO₃⁻)", Ionics, Vol. 15, 2009, pp. 433-437. doi:10.1007/s11581-009-0387-4

[3] S.Ramesh and A.K.Arof, "A study incorporating nano-sized silica into PVC-blend-based polymer electrolytes for lithium batteries", Journal of Materials Science, Vol. 44, 2009, pp. 6404-6407. doi:10.1007/s10853-009-3883-z

[4] G P Pandey, S A Hashmi and R.C Agarwal, "Experimental investigations on a proton conducting nanocomposite polymer electrolyte", Journal of Physics D: Applied Physics, Vol. 41, 2008, pp. 0554409 (6pp). doi: Published 14 February 2008

[5] S.Ramesh and A.k.Akof, "Ionic conductivity studies of plasticized poly (vinyl chloride) polymer electrolytes", Materials Science Engineering B, Vol. 85, No.1, 2001, pp. 11-15. doi: 6 August 2001

Cite the paper

P. Karthika, R. Karthigai Selvi, PS Devi Prasadh (2017). *Structural and Complex Formation of PVC – LiNO3 – CdO*, Vol 9. Doi 10.2412/mmse.65.100.626