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Denis Morineau

Publications and source records attributed to Denis Morineau.

28 records · Page 2Linked to original sources

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.

cond-mat.soft↗

Incoherent Quasielastic Neutron Scattering Study of Molecular dynamics of 4-n-cyano-4'-octylbiphenyl

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-cyano-4'-octylbiphenyl. The combination of time-of-flight and backscattering data allows analyzing the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in respectively the nanosecond and picosecond time scales. The comparison with literature data obtained by other techniques is discussed.

physics.chem-ph↗

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 membranes

cond-mat.soft↗

Sliding and translational diffusion of molecular phases confined into nanotubes

The remaining dynamical degrees of freedom of molecular fluids confined into capillaries of nano to sub-nanometer diameter are of fundamental relevance for future developments in the field of nanofluidics. These properties cannot be simply deduced from the bulk one since the derivation of macroscopic hydrodynamics most usually breaks down in nanoporous channels and additional effects have to be considered. In the present contribution, we review some general phenomena, which are expected to occur when manipulating fluids under confinement and ultraconfinement conditions.

cond-mat.soft↗

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.

cond-mat.mtrl-sci↗

Structure and relaxation processes of an anisotropic molecular fluid confined into 1D nanochannels

Structural order parameters of a smectic liquid crystal confined into the columnar form of porous silicon are studied using neutron scattering and optical spectroscopic techniques. It is shown that both the translational and orientational anisotropic properties of the confined phase strongly couple to the one-dimensional character of the porous silicon matrix. The influence of this confinement induced anisotropic local structure on the molecular reorientations occuring in the picosecond timescale is discussed.

cond-mat.soft↗

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 length

cond-mat.soft↗

First evidence of anisotropic quenched disorder effects on a smectic liquid crystal confined in porous silicon

We present a neutron scattering analysis of the structure of the smectic liquid crystal octylcyanobiphenyl (8CB) confined in one-dimensional nanopores of porous silicon films (PS). The smectic transition is completely suppressed, leading to the extension of a short-range ordered smectic phase aligned along the pore axis. It evolves reversibly over an extended temperature range, down to 50 K below the \textit{N-SmA} transition in pure 8CB. This behavior strongly differs from previous observations of smectics in different one-dimensional porous materials. A coherent picture of this striking behavior requires that quenched disorder effects are invoked. The strongly disordered nature of the inner surface of PS acts as random fields coupling to the smectic order. The one-dimensionality of PS nano-channels offers new perspectives on quenched disorder effects, which observation has been restricted to homogeneous random porous materials so far.

cond-mat.soft↗

Structure of liquid and glassy methanol confined in cylindrical pores

We present a neutron scattering analysis of the density and the static structure factor of confined methanol at various temperatures. Confinement is performed in the cylindrical pores of MCM-41 silicates with pore diameters D=24 angstrom and D=35 angstrom. A change of the thermal expansivity of confined methanol at low temperature is the signature of a glass transition, which occurs at higher temperature for the smallest pore. This is an evidence of a surface induced slowing down of the dynamics of the fluid. The structure factor presents a systematic evolution with the pore diameter, which has been analyzed in terms of excluded volume effects and fluid-matrix cross-correlation. Conversely to the case of Van der Waals fluids, it shows that stronger fluid-matrix correlations must be invoked most probably in relation with the H-bonding character of both methanol and silicate surface.

cond-mat.soft↗

Experimental Indication of Structural Heterogeneities in Fragile Hydrogen-bonded Liquids

We present the first experimental characterization in molecular fragile glassformers of a 'prepeak that appears significantly below the main peak of the static structure factor. The temperature and density dependences of this prepeak are studied via elastic neutron scattering experiments under high pressure (up to 300 MPa) in m-toluidine and m-fluoroaniline. The prepeak intensity increases with decreasing temperature, but it remains constant with increasing pressure while its position and width stay roughly the same. These features are opposite to those observed for the 'first sharp diffraction peak' of network glasses. The origin of the phenomenon is analyzed with the help of Monte Carlo simulations. We associate the prepeak to hydrogen-bond-induced heterogeneities (or clusters) whose limited size results from exclusion effect between benzene rings that prevents the extension of a hydrogen-bond network. Implications for the dynamics of the liquid close to the glass transition are finally considered.

physics.chem-ph↗