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.