Effect of initial γ-irradiation on infrared laser ablation of poly(vinyl alcohol) studied by infrared spectroscopy

Allayarov, Sadulla R.; Confer, Matthew P.; Dixon, David A.; Rudneva, Tatyana N.; Kalinin, Leonid A.; Tolstopyatov, Evgenii M.; Frolov, Ivan A.; Ivanov, Leonid F.; Grakovich, Petr N.; Golodkov, Oleg N.

doi:10.1016/j.polymdegradstab.2020.109331

Effect of initial γ-irradiation on infrared laser ablation of poly(vinyl alcohol) studied by infrared spectroscopy

Journal Article · Wed Aug 12 00:00:00 EDT 2020 · Polymer Degradation and Stability

DOI:https://doi.org/10.1016/j.polymdegradstab.2020.109331· OSTI ID:1852702

^[1]; Confer, Matthew P. ^[2]; ^[2]; Rudneva, Tatyana N. ^[3]; Kalinin, Leonid A. ^[4]; Tolstopyatov, Evgenii M. ^[4]; Frolov, Ivan A. ^[3]; Ivanov, Leonid F. ^[4]; Grakovich, Petr N. ^[4]; Golodkov, Oleg N. ^[3]

Russian Academy of Sciences, Chernogolovka (Russia); Univ. of Alabama, Tuscaloosa, AL (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)
Russian Academy of Sciences, Chernogolovka (Russia)
National Academy of Sciences of Belarus, Gomel (Belarus)

We report the effect of initial γ-irradiation of poly(vinyl alcohol) (PVA) on the kinetics of polymer ablation under CO₂ laser irradiation was studied using infra-red spectroscopy. The rate of laser ablation rapidly decreases with increasing time of laser ablation up to 10 s. Initial γ-irradiation of a dose up to 100 kGy reduces the rate of the laser ablation, just like the effect of laser exposure. The number of OH and CH groups decrease in PVA both with laser irradiation and with γ-irradiation. The number of OH groups decreases more under laser irradiation. Unsaturated bonds are formed in γ–irradiated PVA on the surface of the crater formed by laser ablation of the polymer that has undergone radiolysis. Increasing the dose of initial γ-irradiation from 100 to 2300 kGy leads to an increase in the intensity of the IR bands of the unsaturated bonds. The number of IR bands in the spectra of the laser ablation crater of PVA does not change with the dose of initial γ-irradiation. A dose of radiolysis of 3500 kGy significantly changes the IR spectra of both the ablation crater and the coating formed from the ablation products. Many bands characteristic for PVA are no longer present and the intensities of bands corresponding to unsaturated bonds are increased. A computational model for loss of water and ketone formation was developed for PVA and PVA including a diol using G3(MP2). The highest activation energy barrier step in the decomposition reaction was formation of the enol species and water was shown to catalyze all decomposition steps.

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 Foundation for Basic Research

Grant/Contract Number:: SC0018921

OSTI ID:: 1852702

Alternate ID(s):: OSTI ID: 1648157

Journal Information:: Polymer Degradation and Stability, Journal Name: Polymer Degradation and Stability Journal Issue: C Vol. 181; ISSN 0141-3910

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ablation by continuous CO2 laser
correlated G3(MP2) molecular orbital theory
infrared spectra
initial γ-irradiation
poly(vinyl alcohol)
predicted decomposition thermodynamics.

Effect of initial γ-irradiation on infrared laser ablation of poly(vinyl alcohol) studied by infrared spectroscopy

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