256 research outputs found
Methyl group dynamics in a confined glass
We present a neutron scattering investigation on methyl group dynamics in
glassy toluene confined in mesoporous silicates of different pore sizes. The
experimental results have been analysed in terms of a barrier distribution
model, such a distribution following from the structural disorder in the glassy
state. Confinement results in a strong decreasing of the average rotational
barrier in comparison to the bulk state. We have roughly separated the
distribution for the confined state in a bulk-like and a surface-like
contribution, corresponding to rotors at a distance from the pore wall
respectively larger and smaller than the spatial range of the interactions
which contribute to the rotational potential for the methyl groups. We have
estimated a distance of 7 Amstrong as a lower limit of the interaction range,
beyond the typical nearest-neighbour distance between centers-of-mass (4.7
Amstrong).Comment: 5 pages, 3 figures. To be published in European Physical Journal E
Direct. Proceedings of the 2nd International Workshop on Dynamics in
Confinemen
Rich polymorphism of a rod-like liquid crystal (8CB) confined in two types of unidirectional nanopores
We present a neutron and X-rays scattering study of the phase transitions of
4-n-octyl-4'-cyanobiphenyl (8CB) confined in unidirectional nanopores of porous
alumina and porous silicon (PSi) membranes with an average diameter of 30 nm.
Spatial confinement reveals a rich polymorphism, with at least four different
low temperature phases in addition to the smectic A phase. The structural study
as a function of thermal treatments and conditions of spatial confinement
allows us to get insights into the formation of these phases and their relative
stability. It gives the first description of the complete phase behavior of 8CB
confined in PSi and provides a direct comparison with results obtained in bulk
conditions and in similar geometric conditions of confinement but with reduced
quenched disorder effects using alumina anopore membranesComment: Accepted in EPJ E - Soft Matte
Evolution of the magnetic phase transition in MnO confined to channel type matrices. Neutron diffraction study
Neutron diffraction studies of antiferromagnetic MnO confined to MCM-41 type
matrices with channel diameters 24-87 A demonstrate a continuous magnetic phase
transition in contrast to a discontinuous first order transition in the bulk.
The character of the magnetic transition transforms with decreasing channel
diameter, showing the decreasing critical exponent and transition temperature,
however the latter turns out to be above the N\'eel temperature for the bulk.
This enhancement is explained within the framework of Landau theory taking into
consideration the ternary interaction of the magnetic and associated structural
order parameters.Comment: 6 pages pdf file, including 4 figures, uses revtex4.cl
ESR of MnO embedded in silica nanoporous matrices with different topologies
Electron spin resonance (ESR) experiments were performed with
antiferromagnetic MnO confined within a porous vycor-type glass and within
MCM-type channel matrices. A signal from confined MnO shows two components from
crystallized and amorphous MnO and depends on the pore topology. Crystallized
MnO within a porous glass shows a behavior having many similarities to the
bulk. In contrast with the bulk the strong ESR signal due to disordered
"surface" spins is observed below the magnetic transition. With the decrease of
channel diameter the fraction of amorphous MnO increases while the amount of
crystallized MnO decreases. The mutual influence of amorphous and crystalline
MnO is observed in the matrices with a larger channel diameter. In the matrices
with a smaller channel diameter the ESR signal mainly originates from amorphous
MnO and its behavior is typical for the highly disordered magnetic system.Comment: 7 pages pdf file, 5 figure
Influence of Elastic Strains on the Adsorption Process in Porous Materials. An Experimental Approach
The experimental results presented in this paper show the influence of the
elastic deformation of porous solids on the adsorption process. With p+-type
porous silicon formed on highly boron doped (100) Si single crystal, we can
make identical porous layers, either supported by or detached from the
substrate. The pores are perpendicular to the substrate. The adsorption
isotherms corresponding to these two layers are distinct. In the region
preceding capillary condensation, the adsorbed amount is lower for the membrane
than for the supported layer and the hysteresis loop is observed at higher
pressure. We attribute this phenomenon to different elastic strains undergone
by the two layers during the adsorption process. For the supported layer, the
planes perpendicular to the substrate are constrained to have the same
interatomic spacing as that of the substrate so that the elastic deformation is
unilateral, at an atomic scale, and along the pore axis. When the substrate is
removed, tridimensional deformations occur and the porous system can find a new
configuration for the solid atoms which decreases the free energy of the system
adsorbate-solid. This results in a decrease of the adsorbed amount and in an
increase of the condensation pressure. The isotherms for the supported porous
layers shift toward that of the membrane when the layer thickness is increased
from 30 to 100 microns. This is due to the relaxation of the stress exerted by
the substrate as a result of the breaking of Si-Si bonds at the interface
between the substrate and the porous layer. The membrane is the relaxed state
of the supported layer.Comment: Accepted in Langmui
Structure of MnO nanoparticles embedded into channel-type matrices
X-ray diffraction experiments were performed on MnO confined in mesoporous
silica SBA-15 and MCM-41 matrices with different channel diameters. The
measured patterns were analyzed by profile analysis and compared to numerical
simulations of the diffraction from confined nanoparticles. From the lineshape
and the specific shift of the diffraction reflections it was shown that the
embedded objects form ribbon-like structures in the SBA-15 matrices with
channels diameters of 47-87 {\AA}, and nanowire-like structures in the MCM-41
matrices with channels diameters of 24-35 {\AA}. In the latter case the
confined nanoparticles appear to be narrower than the channel diameters. The
physical reasons for the two different shapes of the confined nanoparticles are
discussed.Comment: 8 pages, including 9 postscript figures, uses revtex4.cl
On the correlation between fragility and stretching in glassforming liquids
We study the pressure and temperature dependences of the dielectric
relaxation of two molecular glassforming liquids, dibutyl phtalate and
m-toluidine. We focus on two characteristics of the slowing down of relaxation,
the fragility associated with the temperature dependence and the stretching
characterizing the relaxation function. We combine our data with data from the
literature to revisit the proposed correlation between these two quantities. We
do this in light of constraints that we suggest to put on the search for
empirical correlations among properties of glassformers. In particular, argue
that a meaningful correlation is to be looked for between stretching and
isochoric fragility, as both seem to be constant under isochronic conditions
and thereby reflect the intrinsic effect of temperature
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.
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