560 research outputs found
Effect of entropy on the dynamics of supercooled liquids: New results from high pressure data
We show that for arbitrary thermodynamic conditions, master curves of the
entropy are obtained by expressing S(T,V) as a function of TV^g_G, where T is
temperature, V specific volume, and g_G the thermodynamic Gruneisen parameter.
A similar scaling is known for structural relaxation times,tau = f(TV^g);
however, we find g_G < g. We show herein that this inequality reflects
contributions to S(T,V) from processes, such as vibrations and secondary
relaxations, that do not directly influence the supercooled dynamics. An
approximate method is proposed to remove these contributions, S_0, yielding the
relationship tau = f(S-S_0).Comment: 10 pages 7 figure
What can we learn by squeezing a liquid
Relaxation times for different temperatures, T, and specific volumes, V,
collapse to a master curve versus TV^g, with g a material constant. The
isochoric fragility, m_V, is also a material constant, inversely correlated
with g. From these we obtain a 3-parameter function, which fits accurately
relaxation times of several glass-formers over the supercooled regime, without
any divergence below Tg. Although the 3 parameters depend on the material, only
g significant varies; thus, by normalizing material-specific quantities related
to g, a universal power law for the dynamics is obtained.Comment: 12 pages, 4 figure
Glass transition of an epoxy resin induced by temperature, pressure and chemical conversion: a configurational entropy rationale
A comparative study is reported on the dynamics of a glass-forming epoxy
resin when the glass transition is approached through different paths: cooling,
compression, and polymerization. In particular, the influence of temperature,
pressure and chemical conversion on the dynamics has been investigated by
dielectric spectroscopy. Deep similarities are found in dynamic properties. A
unified reading of our experimental results for the structural relaxation time
is given in the framework of the Adam-Gibbs theory. The quantitative agreement
with the experimental data is remarkable, joined with physical values of the
fitting parameters. In particular, the fitting function of the isothermal
tau(P) data gives a well reasonable prediction for the molar thermal expansion
of the neat system, and the fitting function of the isobaric-isothermal tau(C)
data under step- polymerization conforms to the prediction of diverging tau at
complete conversion of the system.Comment: 16 pages, 8 figures, from the talk given at the 4th International
Discussion Meeting on Relaxations in Complex Systems (IDMRCS), Hersonissos,
Helaklion, Crete (Greece), 17-23 June 200
Thermodynamic Scaling of the Viscosity of Van Der Waals, H-Bonded, and Ionic Liquids
Viscosities and their temperature, T, and volume, V, dependences are reported
for 7 molecular liquids and polymers. In combination with literature viscosity
data for 5 other liquids, we show that the superpositioning of relaxation times
for various glass-forming materials when expressed as a function of TV^g, where
the exponent g is a material constant, can be extended to the viscosity. The
latter is usually measured to higher temperatures than the corresponding
relaxation times, demonstrating the validity of the thermodynamic scaling
throughout the supercooled and higher T regimes. The value of g for a given
liquid principally reflects the magnitude of the intermolecular forces (e.g.,
steepness of the repulsive potential); thus, we find decreasing g in going from
van der Waals fluids to ionic liquids. For strongly H-bonded materials, such as
low molecular weight polypropylene glycol and water, the superpositioning
fails, due to the non-trivial change of chemical structure (degree of
H-bonding) with thermodynamic conditions.Comment: 16 pages 7 figure
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