Effect of 60Co γ-radiation on the tetrafluoroethylene/perfluoro(methyl vinyl ether) copolymer

Allayarov, Sadulla R.; Confer, Matthew P.; Demidov, Sergey V.; Nikolskii, Vadim G.; Olkhov, Yurii A.; Dixon, David A.

doi:10.1016/j.jfluchem.2020.109671

Effect of ⁶⁰Co γ-radiation on the tetrafluoroethylene/perfluoro(methyl vinyl ether) copolymer

Journal Article · Fri Oct 16 00:00:00 EDT 2020 · Journal of Fluorine Chemistry

DOI:https://doi.org/10.1016/j.jfluchem.2020.109671· OSTI ID:1852701

Allayarov, Sadulla R. ^[1]; ^[2]; Demidov, Sergey V. ^[3]; Nikolskii, Vadim G. ^[4]; Olkhov, Yurii A. ^[3]; ^[5]

Russian Academy of Sciences (RAS), Chernogolovaka (Russian Federation). Inst. of Problems of Chemical Physics; Univ. of Alabama, Tuscaloosa, AL (United States)
Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry and Biochemistry; Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering
Russian Academy of Sciences (RAS), Chernogolovaka (Russian Federation). Inst. of Problems of Chemical Physics
Russian Academy of Sciences (RAS), Moscow (Russian Federation). Institute for Chemical Physics
Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering

The chemical and paramagnetic composition of the surface of the tetrafluoroethylene / perfluoro(methyl vinyl ether) copolymer (MFA) was investigated before and after γ-irradiation. The content of fluorine and carbon decreases at radiolysis of MFA, as well as the proportion of oxygen increases as a result of the oxidation reaction of radicals formed during γ-irradiation. The electron paramagnetic resonance (EPR) spectrum of the copolymer irradiated at 77 K contains the radicals ~CF₂C∙FCF₂~ (1) and >CFOC∙F₂ (2). The absence of ~CF₂C∙F₂ radicals, which can be formed at radiolytic rupture of the C—C bond of the copolymer main chain is associated with the effect of recombination of the resulting radical pair. The EPR spectrum of irradiated MFA at 300 K only recorded radical (1), which transform into peroxide radicals when air oxygen is introduced into the irradiated sample. Thermomechanical curves of native and radiolyzed MFA show three structural states of the amorphous block (glass, transition region, plateau of highly elastic deformation), as well as melting and molecular flow of the copolymer. The radio thermoluminescence curve shows five maxima associated with the emission of light during the recombination of stabilized ions and radicals during heating of the pre-irradiated MFA at 77 K. The temperature of the luminescence peak maximum at 336 K is close to the temperature of the onset of the devitrification of the chains of the amorphous block of MFA on the thermomechanical curve at 341 K. Irradiation leads to an increase in crystallinity of MFA. The heat of fusion of irradiated MFA on the Differential Scanning Calorimeter (DSC) curve is 50 % higher than the fusion heat of native copolymer. During the heating of γ-irradiated MFA, the relative content of COF molecules in the thermal decomposition products increases by an order of magnitude.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Russian Academy of Sciences

Grant/Contract Number:: SC0018921

OSTI ID:: 1852701

Alternate ID(s):: OSTI ID: 1775941

Journal Information:: Journal of Fluorine Chemistry, Journal Name: Journal of Fluorine Chemistry Journal Issue: C Vol. 240; ISSN 0022-1139

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
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copolymer of tetrafluoroethylene and perfluoro(methyl vinyl ether)
radiothermoluminescence
thermomechanical spectrometry
γ-irradiation

Effect of 60Co γ-radiation on the tetrafluoroethylene/perfluoro(methyl vinyl ether) copolymer

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Effect of ⁶⁰Co γ-radiation on the tetrafluoroethylene/perfluoro(methyl vinyl ether) copolymer