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Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility, local disorder, and thermal equilibration in hydrogen-bonded poly(methacrylic acid)

Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility, local disorder, and thermal equilibration in hydrogen-bonded poly(methacrylic acid)
Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility, local disorder, and thermal equilibration in hydrogen-bonded poly(methacrylic acid)

The 1H–13C cross-polarization with magic-angle spinning (CP MAS) kinetics was studied in poly(methacrylic acid) (PMAA) having the purpose to track the links between the local order in the main chain and the proton dynamics in peripheral hydrogen bond networks. The experimental CP MAS kinetic curves were analyzed applying the models of isotropic and anisotropic spin-diffusion with thermal equilibration. The fractal dimension Dp ≈ 3 was deduced that indicates that PMAA behaves as an isotropic 3D-system. No proton conductivity in the neat PMAA was deduced from the impedance spectroscopy data analyzing the frequency dependences of the complex dielectric permittivity. The value of local order parameter S = 0.70 for CH2 in PMAA occupies an intermediate position between 0.63 and 0.85 deduced for CH2 sites in the main chains of poly(vinyl phosphonic acid) and poly(2-hydroxyethyl methacrylate), that is, the true proton conductor and the polymer that contains the H-bond network, however, no proton conductivity, respectively.

CP MAS, fractal dimension, impedance spectroscopy, poly(methacrylic acid) (PMAA), proton conductivity
2642-4150
3253-3263
Dagys, Laurynas
0de61597-b152-4bee-a934-123a9d2de883
Klimkevičius, Vaidas
e9309f53-e886-4e5c-9cab-6a3e2ba7ff91
Klimavicius, Vytautas
d33e6f1b-2dd3-471e-9597-8a2a55ec3f1e
Balčiūnas, Sergejus
04ed4e31-50af-4336-acae-d7e7d7d724c3
Banys, Jūras
6b2ade3e-811d-4187-8947-76e03365fc0e
Balevicius, Vytautas
e9ec95d9-9ead-4834-aa18-32fa4b3c080a
Dagys, Laurynas
0de61597-b152-4bee-a934-123a9d2de883
Klimkevičius, Vaidas
e9309f53-e886-4e5c-9cab-6a3e2ba7ff91
Klimavicius, Vytautas
d33e6f1b-2dd3-471e-9597-8a2a55ec3f1e
Balčiūnas, Sergejus
04ed4e31-50af-4336-acae-d7e7d7d724c3
Banys, Jūras
6b2ade3e-811d-4187-8947-76e03365fc0e
Balevicius, Vytautas
e9ec95d9-9ead-4834-aa18-32fa4b3c080a

Dagys, Laurynas, Klimkevičius, Vaidas, Klimavicius, Vytautas, Balčiūnas, Sergejus, Banys, Jūras and Balevicius, Vytautas (2020) Cross-polarization with magic-angle spinning kinetics and impedance spectroscopy study of proton mobility, local disorder, and thermal equilibration in hydrogen-bonded poly(methacrylic acid). Journal of Polymer Science, 58 (23), 3253-3263. (doi:10.1002/pol.20200592).

Record type: Article

Abstract

The 1H–13C cross-polarization with magic-angle spinning (CP MAS) kinetics was studied in poly(methacrylic acid) (PMAA) having the purpose to track the links between the local order in the main chain and the proton dynamics in peripheral hydrogen bond networks. The experimental CP MAS kinetic curves were analyzed applying the models of isotropic and anisotropic spin-diffusion with thermal equilibration. The fractal dimension Dp ≈ 3 was deduced that indicates that PMAA behaves as an isotropic 3D-system. No proton conductivity in the neat PMAA was deduced from the impedance spectroscopy data analyzing the frequency dependences of the complex dielectric permittivity. The value of local order parameter S = 0.70 for CH2 in PMAA occupies an intermediate position between 0.63 and 0.85 deduced for CH2 sites in the main chains of poly(vinyl phosphonic acid) and poly(2-hydroxyethyl methacrylate), that is, the true proton conductor and the polymer that contains the H-bond network, however, no proton conductivity, respectively.

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More information

Accepted/In Press date: 2 October 2020
e-pub ahead of print date: 15 October 2020
Published date: 1 December 2020
Keywords: CP MAS, fractal dimension, impedance spectroscopy, poly(methacrylic acid) (PMAA), proton conductivity

Identifiers

Local EPrints ID: 447780
URI: http://eprints.soton.ac.uk/id/eprint/447780
ISSN: 2642-4150
PURE UUID: 80781eaf-a0f0-4b51-a2ad-e7e7c45c2877

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Date deposited: 19 Mar 2021 17:37
Last modified: 16 Mar 2024 09:54

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Contributors

Author: Laurynas Dagys
Author: Vaidas Klimkevičius
Author: Vytautas Klimavicius
Author: Sergejus Balčiūnas
Author: Jūras Banys
Author: Vytautas Balevicius

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