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Primary and secondary relaxation processes in poly(propylene glycol) monobutyl ether: a broadband dielectric spectroscopy investigation

Polymer Journal volume 55, pages 141–151 (2023)Cite this article

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Abstract

Several relaxation modes present in poly(propylene glycol) monobutyl ether [PPGMBE] were explored over a wide temperature range (120–310 K) and frequency band range (10 mHz–1.0 GHz) using wideband dielectric spectroscopy. Two resolvable secondary relaxations (β- and γ-processes) were observed below Tg, along with a structural relaxation mode (α-) above Tg. The β-relaxation process was well fitted with the Cole–Cole equation and was identified as true Johari Goldstein relaxation based on an aging experiment and a coupling model prediction. The spectra for the γ-process showed asymmetric behavior below Tg, hence it was well described by the Havriliak-Negami equation and did not show any of the peculiar behavior seen with many PPG families. The T-dependences of several dielectric properties, e.g., τα, τβ, τγ, τσ, and σdc, were thoroughly investigated. It was noticed that the T-variation of the relaxation time for the α-mode was not satisfactorily described with only one VFT equation, and the derivative plot indicated a crossover temperature of ~240 K. Our experimental findings demonstrated that a logarithmic plot of the σdc versus τα data showed nonlinear dependency and thus were expressed by the fractional Stokes-Einstein–Debye law, with a change in the exponent from ζ = −0.70 to −0.85 for high-T (>240 K) and low-T behavior (<240 K), respectively.

Broadband dielectric spectroscopy was employed to study the relaxation dynamics in poly(propylene glycol) monobutyl ether [PPGMBE]. Two relaxation processes (β- and γ-) were observed in the sub-Tg region, in addition to the α-process above Tg. The physical aging experiment performed below Tg suggested that the observed β-process is the genuine Johari Goldstein relaxation process and the γ-process is of intramolecular origin.

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Acknowledgements

The author acknowledges Masaryk University, Brno, Czech Republic for a visiting research specialist grant. The author also acknowledges the support of the Central Instrumental Facility of the Department of Material Science and Engineering, IITB, India, and Dr. Priti Yadav for her critical reading and valuable comments on the manuscript.

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  1. Department of Physics, Madanapalle Institute of Technology & Science, Madanapalle, Chittoor, 517325, Andhra Pradesh, India

    Lokendra P. Singh

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Singh, L.P. Primary and secondary relaxation processes in poly(propylene glycol) monobutyl ether: a broadband dielectric spectroscopy investigation. Polym J 55, 141–151 (2023). https://doi.org/10.1038/s41428-022-00728-7

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