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      On Viscous Flow in Glass-Forming Organic Liquids

      research-article
      1 , 2
      ,
      Molecules
      MDPI
      glass-forming liquids, viscous flow, viscosity, activation energy, glass transition temperature

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          Abstract

          The two-exponential Sheffield equation of viscosity η(T) = A 1·T·[1 + A 2·exp(H m/RT)]·[1 + C·exp(H d/RT)], where A 1, A 2, H m, C, and H m are material-specific constants, is used to analyze the viscous flows of two glass-forming organic materials—salol and α-phenyl- o-cresol. It is demonstrated that the viscosity equation can be simplified to a four-parameter version: η(T) = A·T·exp(H m/RT)]·[1 + C·exp(H d/RT)]. The Sheffield model gives a correct description of viscosity, with two exact Arrhenius-type asymptotes below and above the glass transition temperature, whereas near the T g it gives practically the same results as well-known and widely used viscosity equations. It is revealed that the constants of the Sheffield equation are not universal for all temperature ranges and may need to be updated for very high temperatures, where changes occur in melt properties leading to modifications of A and H m for both salol and α-phenyl- o-cresol.

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          Most cited references49

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          Relaxation in glassforming liquids and amorphous solids

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            Heterogeneous dynamics in liquids: fluctuations in space and time

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              Viscosity of glass-forming liquids.

              The low-temperature dynamics of ultraviscous liquids hold the key to understanding the nature of glass transition and relaxation phenomena, including the potential existence of an ideal thermodynamic glass transition. Unfortunately, existing viscosity models, such as the Vogel-Fulcher-Tammann (VFT) and Avramov-Milchev (AM) equations, exhibit systematic error when extrapolating to low temperatures. We present a model offering an improved description of the viscosity-temperature relationship for both inorganic and organic liquids using the same number of parameters as VFT and AM. The model has a clear physical foundation based on the temperature dependence of configurational entropy, and it offers an accurate prediction of low-temperature isokoms without any singularity at finite temperature. Our results cast doubt on the existence of a Kauzmann entropy catastrophe and associated ideal glass transition.
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                Author and article information

                Contributors
                Role: Academic Editor
                Role: Academic Editor
                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                03 September 2020
                September 2020
                : 25
                : 17
                : 4029
                Affiliations
                [1 ]Department of Materials, Imperial College London, South Kensington Campus, Exhibition Road, London SW7 2AZ, UK; m.ojovan@ 123456imperial.ac.uk or m.i.ojovan@ 123456gmail.com ; Tel.: +44-747-828-9098
                [2 ]Department of Radiochemistry, Moscow State University Named after M.V. Lomonosov, Leninskie Gory 1, Bd.3, 119991 Moscow, Russia
                Author information
                https://orcid.org/0000-0001-8928-4879
                Article
                molecules-25-04029
                10.3390/molecules25174029
                7504771
                32899408
                bc87c3bf-75c9-463f-9445-890a5ff48c60
                © 2020 by the author.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 22 July 2020
                : 01 September 2020
                Categories
                Article

                glass-forming liquids,viscous flow,viscosity,activation energy,glass transition temperature

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