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Infrared spectroscopic studies on crystalline phase transition of PVDF and PVDF/hyperbranched polyester blend ultrathin films
Affiliation:1. Department of Chemistry, Faculty of Science & Humanities, SRM University, Kattankulathur, Kanchipuram District, Tamil Nadu State 603203, India;2. Department of Chemistry, School of Advanced Sciences, VIT University, Vellore, Tamil Nadu State 632014, India;3. Department of Advanced Materials Engineering for Information and Electronics, College of Engineering, Kyung Hee University, Gyeonggi-do 446-701, Republic of Korea;1. Key Lab of Process Analysis and Control of Sichuan Universities, Yibin University, Yibin, Sichuan, 644000, China;2. Hospital, Yibin University, Yibin, Sichuan, 644000, China;1. Faculdade de Educação Ciências e Letras do Sertão Central, Universidade Estadual do Ceará Quixadá, CE 63.900-000, Brazil;2. Deparamento de Física, Universidade Federal do Ceará, Fortaleza, CE 60455-760, Brazil;3. Instituto de Ciências Exatas, Universidade Federal do Sul e Sudeste do Pará, CEP 68.505-080 Marabá, PA, Brazil;4. Universidade Federal do Cariri, 63000-000 Juazeiro do Norte, CE, Brazil;1. School of Instrument Science and Opto-electronics Engineering, Hefei University of Technology, Hefei, 230009, China;2. Beijing Engineering Research Center of Optoelectronic Information and Instrument, Beijing Key Laboratory of Optoelectronics Measurement Technology, Beijing Information Science and Technology University, Beijing, 100192, China;1. Department of Chemistry and Biology and INSTM Research Unit, University of Salerno, Via Giovanni Paolo II 132, I-84084 Fisciano, SA, Italy;2. D3 CompuNet, Istituto Italiano di Tecnologia, via Morego 30, I-16163 Genova, Italy;3. Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, F-75005 Paris, France
Abstract:In this study, as cast (AC, at 30 °C) and annealed (AN, at 130 °C, 3 h) samples of polyvinylidene fluoride (PVDF) and PVDF/hyperbranched polyester (HBP) (90/10) blend ultrathin films were subjected to heating-cooling (30 → 210 → 30 °C) cycle, and studied for their changes in crystalline phase transition behavior using in-situ Fourier transform infrared-transmission spectroscopy (FTIR-TS) and grazing incident reflection absorption spectroscopy (FTIR-GIRAS) techniques. Factor analysis was employed to extract the pure crystalline and amorphous spectra as well as the percentage content of ferroelectric crystallinity for both the samples. Irrespective of the thermal treatment (AC or AN) and spectral measurement (FTIR-TS or GIRAS) techniques, neat PVDF sample exhibited irreversible phase transitions during heating-cooling cycle associated with the transformation from ordered β-crystalline (1276 cm−1) into disordered amorphous (1234 cm−1) form. Interestingly, annealed PVDF/HBP blend sample measured using FTIR-GIRAS exhibited reversible crystalline phase transition behavior similar to a ‘dipole memory effect’ even after heating to 210 °C (>Tm) and then cooled to 30 °C. Compared to neat PVDF, higher ferroelectric crystallinity and reversible phase transition in PVDF/HBP blend may be attributed to (i) the existence of H-bonding between HBP (Cdouble bondO and OH groups) and PVDF (single bondCH2 and single bondCF2) and/or (ii) HBP acting as a nanoparticle in PVDF matrix.
Keywords:Polyvinylidene fluoride  Hyperbranched polyester  Heat treatment  FTIR spectroscopy  Factor analysis  Crystalline phase
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