Effect of X-ray beam on the molecular–topological structure of the surface of kynar® polyvinylidene fluoride resin

Olkhov, Yurii A.; Allyarov, Sadulla R.; Vasiliu, Monica; Dixon, David A.; Frolov, Ivan A.; Demidov, Sergei V.

doi:10.1016/j.jfluchem.2019.06.004

Effect of X-ray beam on the molecular–topological structure of the surface of kynar® polyvinylidene fluoride resin

Journal Article · Tue Jul 09 00:00:00 EDT 2019 · Journal of Fluorine Chemistry

DOI:https://doi.org/10.1016/j.jfluchem.2019.06.004· OSTI ID:1803469

Olkhov, Yurii A. ^[1]; Allyarov, Sadulla R. ^[2]; Vasiliu, Monica ^[3]; Dixon, David A. ^[3]; Frolov, Ivan A. ^[4]; Demidov, Sergei V. ^[4]

Russian Academy of Sciences (RAS), Moscow (Russian Federation); OSTI
Russian Academy of Sciences (RAS), Moscow (Russian Federation); Univ. of Alabama, Tuscaloosa, AL (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)
Russian Academy of Sciences (RAS), Moscow (Russian Federation)

Thermomechanical analysis of poly(vinylidene fluoride) (PVDF) film shows that, unlike the completely amorphous structure of the native polymer, after irradiation with X-rays, the weight fraction of the crystalline modification in the polymer is 0.5. The initial PVDF film had a linear thermal expansion coefficient of $α_{1}$ = 11.33х10⁵ K^-1 and a glass transition temperature of $T_{g}$ =256 K. An efficient conversion of the amorphous structures of the polymer pseudo-network into crystalline networks occurs under X-ray irradiation. The irradiated polymer exhibits amorphous ( $T_{g}$ =239 K) and crystalline topological blocks ( $T_{m}$ =385 K). The presence of polyenyl and alkyl radicals is found in the electron paramagnetic resonance (EPR) spectra of the irradiated polymer. Lines with a splitting of 3.3 m T can be observed at the edges of the EPR spectra, consistent with radical centers like -CF₂-C^•H-CF_2^-. At high doses of radiolysis, polyenyl radicals are the main observed radicals. The macromolecular chains contain all three (α, β, γ) morphologies of the polymer. The Raman spectra show that X-ray irradiation can lead to carbonization and the formation of unsaturated bonds. Electronic structure calculations were used to aid in the analysis of the observed spectra.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Alabama, Tuscaloosa, AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018921

OSTI ID:: 1803469

Alternate ID(s):: OSTI ID: 1542677

Journal Information:: Journal of Fluorine Chemistry, Journal Name: Journal of Fluorine Chemistry Vol. 226; ISSN 0022-1139

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X–ray irradiation
electron paramagnetic resonance
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Effect of X-ray beam on the molecular–topological structure of the surface of kynar® polyvinylidene fluoride resin

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