251 research outputs found
Dynamics of 8CB confined into porous silicon probed by incoherent neutron backscattering experiments
Confinement in the nanochannels of porous silicon strongly affects the phase
behavior of the archetype liquid-crystal 4-n-octyl-4-cyanobiphenyl (8CB). A
very striking phenom- enon is the development of a short-range smectic order,
which occurs on a very broad temperature range. It suggests in this case that
quenched disorder effects add to usual finite size and surface interaction
effects. We have monitored the temperature variation of the molecular dynamics
of the confined fluid by incoherent quasielastic neutron scat- tering. A
strongly reduced mobility is observed at the highest temperatures in the liquid
phase, which suggests that the interfacial molecular dynamics is strongly
hindered. A continuously increasing slowdown appears on cooling together with a
progressive growth of the static correlation lengt
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
Molecular dynamics of glycerol and glycerol-trehalose bioprotectant solutions nanoconfined in porous silicon
Glycerol and trehalose-glycerol binary solutions are glass-forming liquids
with remarkable bioprotectant properties. Incoherent quasielastic neutron
scattering (QENS) is used to reveal the different effects of nanoconfinement
and addition of trehalose on the molecular dynamics in the normal liquid and
supercooled liquid phases, on a nanosecond timescale. Confinement has been
realized in straight channels of diameter D=8 nm formed by porous silicon. It
leads to a faster and more inhomogeneous relaxation dynamics deep in the liquid
phase. This confinement effect remains at lower temperature where it affects
the glassy dynamics. The glass transitions of the confined systems are shifted
to low temperature with respect to the bulk ones. Adding trehalose tends to
slow down the overall glassy dynamics and increases the non-exponential
character of the structural relaxation. Unprecedented results are obtained for
the binary bioprotectant solution, which exhibits an extremely non-Debye
relaxation dynamics as a result of the combination of the effects of
confinement and mixing of two constituents
Continuous Paranematic-to-Nematic Ordering Transitions of Liquid Crystals in Tubular Silica Nanochannels
The optical birefringence of rod-like nematogens (7CB, 8CB), imbibed in
parallel silica channels with 10 nm diameter and 300 micrometer length, is
measured and compared to the thermotropic bulk behavior. The orientational
order of the confined liquid crystals, quantified by the uniaxial nematic
ordering parameter, evolves continuously between paranematic and nematic
states, in contrast to the discontinuous isotropic-to-nematic bulk phase
transitions. A Landau-de Gennes model reveals that the strength of the
orientational ordering fields, imposed by the silica walls, is beyond a
critical threshold, that separates discontinuous from continuous
paranematic-to-nematic behavior. Quenched disorder effects, attributable to
wall irregularities, leave the transition temperatures affected only
marginally, despite the strong ordering fields in the channels.Comment: 4 pages, 3 figures, Physical Review Letters (in press
Molecular dynamics of a short range ordered smectic phase nanoconfined into porous silicon
4-n-octyl-4-cyanobiphenyl (8CB) has been recently shown to display an unusual
sequence of phases when confined into porous silicon (PSi). The gradual
increase of oriented short-range smectic (SRS) correlations in place of a phase
transition has been interpreted as a consequence of the anisotropic quenched
disorder induced by confinement in PSi. Combining two quasielastic neutron
scattering experiments with complementary energy resolutions, we present the
first investigation of the individual molecular dynamics of this system. A
large reduction of the molecular dynamics is observed in the confined liquid
phase, as a direct consequence of the dynamical boundary conditions imposed by
the confinement. Temperature fixed window scans (FWS) reveal a continuous
'glass-like' reduction of the molecular dynamics of the confined liquid and SRS
phases on cooling down to 250 K, where a solid-like behavior is finally reached
by a two steps crystallization process
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
Neutron scattering and molecular correlations in a supercooled liquid
We show that the intermediate scattering function for neutron
scattering (ns) can be expanded naturely with respect to a set of molecular
correlation functions that give a complete description of the translational and
orientational two-point correlations in the liquid. The general properties of
this expansion are discussed with special focus on the -dependence and hints
for a (partial) determination of the molecular correlation functions from
neutron scattering results are given. The resulting representation of the
static structure factor is studied in detail for a model system using
data from a molecular dynamics simulation of a supercooled liquid of rigid
diatomic molecules. The comparison between the exact result for and
different approximations that result from a truncation of the series
representation demonstrates its good convergence for the given model system. On
the other hand it shows explicitly that the coupling between translational
(TDOF) and orientational degrees of freedom (ODOF) of each molecule and
rotational motion of different molecules can not be neglected in the
supercooled regime.Further we report the existence of a prepeak in the
ns-static structure factor of the examined fragile glassformer, demonstrating
that prepeaks can occur even in the most simple molecular liquids. Besides
examining the dependence of the prepeak on the scattering length and the
temperature we use the expansion of into molecular correlation
functions to point out intermediate range orientational order as its principle
origin.Comment: 13 pages, 7 figure
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