1,944 research outputs found
An equation for the description of volume and temperature dependences of the dynamics of supercooled liquids and polymer melts
A recently proposed expression to describe the temperature and volume
dependences of the structural (or alpha) relaxation time is discussed. This
equation satisfies the scaling law for the relaxation times, tau = f(TV^g),
where T is temperature, V the specific volume, and g a material-dependent
constant. The expression for the function f is shown to accurately fit
experimental data for several glass-forming liquids and polymers over an
extended range encompassing the dynamic crossover, providing a description of
the dynamics with a minimal number of parameters. The results herein can be
reconciled with previously found correlations of the isochoric fragility with
both the isobaric fragility at atmospheric pressure and the scaling exponent g.Comment: to be published in the special edition of J. Non-Crystalline Solids
honoring K.L. Nga
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
Volume Effects on the Glass Transition Dynamics
The role of jamming (steric constraints) and its relationship to the
available volume is addressed by examining the effect that certain
modifications of a glass-former have on the ratio of its isochoric and isobaric
activation enthalpies. This ratio reflects the relative contribution of volume
(density) and temperature (thermal energy) to the temperature-dependence of the
relaxation times of liquids and polymers. We find that an increase in the
available volume confers a stronger volume-dependence to the relaxation
dynamics, a result at odds with free volume interpretations of the glass
transition.Comment: 9 pages 5 figure
Determination of the Thermodynamic Scaling Exponent from Static, Ambient-Pressure Quantities
An equation is derived that expresses the thermodynamic scaling exponent, g,
which superposes relaxation times and other measures of molecular mobility
determined over a range of temperatures and densities, in terms of static,
physical quantities. The latter are available in the literature or can be
measured at ambient pressure. We show for 13 materials, both molecular liquids
and polymers, that the calculated g are equivalent to the scaling exponents
obtained directly by superpositioning. The assumptions of the analysis are that
the glass transition is isochronal and that the first Ehrenfest relation is
valid; the first assumption is true by definition, while the second has been
corroborated for many glass-forming materials at ambient pressure. However, we
find that the Ehrenfest relation breaks down at elevated pressure, although
this limitation is of no consequence herein, since the appeal of the new
equation is its applicability to ambient pressure data.Comment: 9 pages, 3 figures, 1 tabl
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
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
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