188 research outputs found
Plasticization and antiplasticization of polymer melts diluted by low molar mass species
An analysis of glass formation for polymer melts that are diluted by
structured molecular additives is derived by using the generalized entropy
theory, which involves a combination of the Adam-Gibbs model and the direct
computation of the configurational entropy based on a lattice model of polymer
melts that includes monomer structural effects. Antiplasticization is
accompanied by a "toughening" of the glass mixture relative to the pure
polymer, and this effect is found to occur when the diluents are small species
with strongly attractive interactions with the polymer matrix. Plasticization
leads to a decreased glass transition temperature T_g and a "softening" of the
fragile host polymer in the glass state. Plasticization is prompted by small
additives with weakly attractive interactions with the polymer matrix. The
shifts in T_g of polystyrene diluted by fully flexible short oligomers are
evaluated from the computations, along with the relative changes in the
isothermal compressibility at T_g to characterize the extent to which the
additives act as antiplasticizers or plasticizers. The theory predicts that a
decreased fragility can accompany both antiplasticization and plasticization of
the glass by molecular additives. The general reduction in the T_g and
fragility of polymers by these molecular additives is rationalized by analyzing
the influence of the diluent's properties (cohesive energy, chain length, and
stiffness) on glass formation in diluted polymer melts. The description of
glass formation at fixed temperature that is induced upon change the fluid
composition directly implies the Angell equation for the structural relaxation
time as function of the polymer concentration, and the computed "zero mobility
concentration" scales linearly with the inverse polymerization index N.Comment: 12 pages, 15 figure
Entropy Crisis, Ideal Glass Transition and Polymer Melting: Exact Solution on a Husimi Cactus
We introduce an extension of the lattice model of melting of semiflexible
polymers originally proposed by Flory. Along with a bending penalty, present in
the original model and involving three sites of the lattice, we introduce an
interaction energy that corresponds to the presence of a pair of parallel bonds
and a second interaction energy associated with the presence of a hairpin turn.
Both these new terms represent four-site interactions. The model is solved
exactly on a Husimi cactus, which approximates a square lattice. We study the
phase diagram of the system as a function of the energies. For a proper choice
of the interaction energies, the model exhibits a first-order melting
transition between a liquid and a crystalline phase. The continuation of the
liquid phase below this temperature gives rise to a supercooled liquid, which
turns continuously into a new low-temperature phase, called metastable liquid.
This liquid-liquid transition seems to have some features that are
characteristic of the critical transition predicted by the mode-coupling
theory.Comment: To be published in Physical Review E, 68 (2) (2003
Dielectric spectroscopy on aging glasses
In the present work, we provide further evidence for the applicability of a
modified stretched-exponential behavior, proposed recently for the description
of aging-time dependent data below the glass temperature [P. Lunkenheimer et
al., Phys. Rev. Lett. 95 (2005) 055702]. We analyze time-dependent dielectric
loss data in a variety of aging glasses, including new data on Salol and
propylene carbonate, using a conventional stretched exponential and the newly
proposed approach. Also the scaling of aging data obtained at different
measuring frequencies, which was predicted on the basis of the new approach, is
checked for its validity.Comment: 6 pages, 5 figures, submitted to proceedings of 5th IDMRCS, Lille,
200
Glassy dynamics in mono-, di-, and tri-propylene glycol: From the alpha- to the fast beta-relaxation
We present a thorough characterization of the glassy dynamics of three
propylene glycols (mono-, di- and trimer) by broadband dielectric spectroscopy.
By covering a frequency range of more than 15 decades, we have access to the
entire variety of dynamic processes typical for glassy dynamics. These results
add three more molecular glass formers to the sparse list of materials for
which real broadband spectra, including the region of the fast beta-process,
are available. Some first analyses of the various observed dynamic processes
are provided
Mechanical Relaxation in Glasses and at the Glass Transition
The Gilroy-Phillips model of relaxational jumps in asymmetric double-well
potentials, developed for the Arrhenius-type secondary relaxations of the glass
phase, is extended to a formal description of the breakdown of the shear
modulus at the glass transition, the flow process.Comment: 13 pages, 11 figures, 49 ref
Landscape equivalent of the shoving model
It is shown that the shoving model expression for the average relaxation time
of viscous liquids follows largely from a classical "landscape" estimation of
barrier heights from curvature at energy minima. The activation energy involves
both instantaneous bulk and shear moduli, but the bulk modulus contributes less
than 8% to the temperature dependence of the activation energy. This reflects
the fact that the physics of the two models are closely related.Comment: 4 page
Dynamics in a supercooled molecular liquid: Theory and Simulations
We report extensive simulations of liquid supercooled states for a simple
three-sites molecular model, introduced by Lewis and Wahnstr"om [L. J. Lewis
and G. Wahnstr"om, Phys. Rev. E 50, 3865 (1994)] to mimic the behavior of
ortho-terphenyl. The large system size and the long simulation length allow to
calculate very precisely --- in a large q-vector range --- self and collective
correlation functions, providing a clean and simple reference model for
theoretical descriptions of molecular liquids in supercooled states. The time
and wavevector dependence of the site-site correlation functions are compared
with detailed predictions based on ideal mode-coupling theory, neglecting the
molecular constraints. Except for the wavevector region where the dynamics is
controlled by the center of mass (around 9 nm-1), the theoretical predictions
compare very well with the simulation data.
Broadband Dielectric Spectroscopy on Glass-Forming Propylene Carbonate
Dielectric spectroscopy covering more than 18 decades of frequency has been
performed on propylene carbonate in its liquid and supercooled-liquid state.
Using quasi-optic submillimeter and far-infrared spectroscopy the dielectric
response was investigated up to frequencies well into the microscopic regime.
We discuss the alpha-process whose characteristic timescale is observed over 14
decades of frequency and the excess wing showing up at frequencies some three
decades above the peak frequency. Special attention is given to the
high-frequency response of the dielectric loss in the crossover regime between
alpha-peak and boson-peak. Similar to our previous results in other glass
forming materials we find evidence for additional processes in the crossover
regime. However, significant differences concerning the spectral form at high
frequencies are found. We compare our results to the susceptibilities obtained
from light scattering and to the predictions of various models of the glass
transition.Comment: 13 pages, 9 figures, submitted to Phys. Rev.
Statistical Mechanics of Glass Formation in Molecular Liquids with OTP as an Example
We extend our statistical mechanical theory of the glass transition from
examples consisting of point particles to molecular liquids with internal
degrees of freedom. As before, the fundamental assertion is that super-cooled
liquids are ergodic, although becoming very viscous at lower temperatures, and
are therefore describable in principle by statistical mechanics. The theory is
based on analyzing the local neighborhoods of each molecule, and a statistical
mechanical weight is assigned to every possible local organization. This
results in an approximate theory that is in very good agreement with
simulations regarding both thermodynamical and dynamical properties
Feasibility studies of the time-like proton electromagnetic form factor measurements with PANDA at FAIR
The possibility of measuring the proton electromagnetic form factors in the
time-like region at FAIR with the \PANDA detector is discussed. Detailed
simulations on signal efficiency for the annihilation of into a
lepton pair as well as for the most important background channels have been
performed. It is shown that precision measurements of the differential cross
section of the reaction can be obtained in a wide
angular and kinematical range. The individual determination of the moduli of
the electric and magnetic proton form factors will be possible up to a value of
momentum transfer squared of (GeV/c). The total cross section will be measured up to (GeV/c).
The results obtained from simulated events are compared to the existing data.
Sensitivity to the two photons exchange mechanism is also investigated.Comment: 12 pages, 4 tables, 8 figures Revised, added details on simulations,
4 tables, 9 figure
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