Abstract.
The properties of amorphous polymers and of organic compounds under pressure are interpreted in the framework of the modified Van der Walls Equation of State (mVW-EOS) the Vogel-Fulcher-Tamann (VFT) law and of the compensation law. We have shown recently that polymers and organic compounds in amorphous liquid and crystalline states verify the mVW-EOS which depends on three parameters, \(P^{\ast}\) \(V^{\ast}\) and \(T^{\ast}\). In this paper we compare the characteristic pressure \(P^{\ast}\) of the mVW-EOS to the various pressures \(P_{X}= \Delta H_{X}/\Delta V_{X}\) deduced from thermodynamic and kinetic properties of polymers in the liquid and solid states. \(\Delta H_{X}\) and \(\Delta V_{X}\) are: a) the enthalpy and volume change at the melting and glass transitions (the glass being isotropic or oriented and annealed below \(T_{g}\) at various aging conditions); b) the activation parameters of individual \(\beta\) and cooperative \(\alpha\) motions in crystalline liquid and amorphous polymers studied by dielectric or mechanical spectroscopy; and c) the activation parameters of amorphous (solid and liquid) polymers submitted to a deformation depending on the time frequency temperature and strain rate. For a same material, whatever its state and whatever the experimental properties analyzed (dielectric and mechanical relaxation, viscosity, auto-diffusion, yielding under hydrostatic pressure), we demonstrate that \(P_{X}=P^{\ast}=1/\gamma\kappa\), (\(\gamma\) Grüneisen parameter, \(\kappa\) compressibility). In all polymers and organic compounds (and water), these pressures, weakly dependent on T and P near \(T_{g}\) and \( T_{m}\) at low pressure are characteristic of the H-H inter-molecular interactions. It is shown that the two empirical Lawson and Keyes relations of the compensation law can be deduced from the mVW-EOS.
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Rault, J. The equation of state of polymers. Part III: Relation with the compensation law. Eur. Phys. J. E 40, 82 (2017). https://doi.org/10.1140/epje/i2017-11565-9
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DOI: https://doi.org/10.1140/epje/i2017-11565-9