Terminal stage of highly viscous flow

Abstract

The shear misfit model for the highly viscous flow is based upon a theoretical prediction for its terminal stage in terms of irreversible Eshelby relaxations in the five-dimensional shear space. The model is shown to predict a small delta-function (Debye peak) in the dielectric spectrum, in agreement with experimental evidence. It is extended from shear fluctuations to density fluctuations, a new relation between adiabatic and isothermal compressibility jumps at the glass transition is derived, and the model is brought into a form which requires only three temperature-dependent parameters for the fit of shear relaxation data of a glass former with a secondary relaxation peak. The model is applied to high precision measurements of the shear, dielectric and bulk relaxation data in two vacuum pump oils and in squalane, a short chain polymer with a strong secondary relaxation peak. In all three substances, the adiabatic compressibility equilibrates much earlier than the isothermal one. The terminal stage of aging data in squalane demonstrate that one sees also the adiabatic density fluctuations in the thermal expansion, explaining why it seems to equilibrate a bit faster than the dynamic heat capacity.

arXiv comment9 pages, 6 figures

References in corpus (12)

• Dynamics of Viscoplastic Deformation in Amorphous Solids
• Theoretical perspective on the glass transition and amorphous materials
• Supercooled Liquids for Pedestrians
• The role of local structure in dynamical arrest
• Perspective: Configurational entropy of glass-forming liquids
• Prevalence of approximate square root t relaxation for the dielectric alpha process in viscous organic liquids
• Approximate square-root-time relaxation in glass-forming liquids
• Identical temperature dependence of the time scales of several linear-response functions of two glass-forming liquids
• Time-scale coupling in hydrogen- and van der Waals-bonded liquids
• Model for the alpha and beta shear-mechanical properties of supercooled liquids and its comparison to squalane data
• Eshelby description of highly viscous flow -- half model, half theory
• Structural relaxation and highly viscous flow