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International audience; We have investigated the dynamics of liquid water confined in mesostructured porous silica (MCM-41) and periodic mesoporous organosilicas (PMOs) by incoherent quasielastic neutron scattering experiments. The effect of tuning the water/surface interaction from hydrophilic to more hydrophobic on the water mobility, while keeping the pore size in the range 3.5-4.1 nm, was assessed from the comparative study of three PMOs comprising different organic bridging units and the purely siliceous MCM-41 case. An extended dynamical range was achieved by combining time-of-flight (IN5B) and backscattering (IN16B) quasielastic neutron spectrometers providing complementary energy resolutions. Liquid water was studied at regularly spaced temperatures ranging from 300 K to 243 K. In all systems, the molecular dynamics could be described consistently by the combination of two independent motions resulting from fast local motion around the average molecule position and the confined translational jump diffusion of its center of mass. All the molecules performed local relaxations, whereas the translational motion of a fraction of molecules was frozen on the experimental timescale. This study provides a comprehensive microscopic view on the dynamics of liquid water confined in mesopores, with distinct surface chemistries, in terms of non-mobile/mobile fraction, self-diffusion coefficient, residence time, confining radius, local relaxation time, and their temperature dependence. Importantly, it demonstrates that the strength of the water/surface interaction determines the long-time tail of the dynamics, which we attributed to the translational diffusion of interfacial molecules, while the water dynamics in the pore center is barely affected by the interface hydrophilicity.

International audience; Preface : In September 2016, the “Third International Seminar on Aerogels”, co-organized with the International Society for the Advancement of Supercritical Fluids (ISASF) and Technical University of Hamburg-Harburg (TUHH) was hosted by MINES ParisTech in Sophia Antipolis (Alpes-Maritimes, France). This Special Issue gathers 17 full original articles related to topics and presentations of this event.

We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasi-static case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and X-ray scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC based nanocomposites., Comment: 8 pages, 3 figures

International audience; Semiconducting nanowires made of discotic columnar liquid crystals can be obtained by impregnation into solid nanoporous templates, and provide new opportunities to tailor devices for organic electronics with promising charge carriers transport properties. These properties are tightly related to the self-assembly and molecular dynamics of the discotic columns inside the nanowires. We recently studied and rationalized the formation of different nanostructures in the columnar phase of pyrene derivative discotics nanoconfined in anodic alumina and porous silicon templates ([Cerclier et al., J. Phys. Chem. C, 2012, 116, 18990–18998, Kityk et al., Soft Matter, 2014, 10, 4522–4534]). We now present the molecular dynamics of nano-confined pyrene derivative mesogenic phases as studied by incoherent quasielastic neutron scattering over a broad range of correlation times. The combination of backscattering and time-of-flight techniques has allowed to describe the nature of the molecular motions at play on the pico to nanosecond time scale. The dynamics of the columnar phase is dominated by fluctuations of the lateral chains, while the onset of larger amplitude motions like whole-body reorientations and slow center-of-mass translational diffusion occurs at high temperature in the isotropic phase. Interestingly, nano-confinement does not qualitatively alter the nature of the molecular dynamics, but essentially blocks the long range translational motions and induces broader distributions of correlation times of the fastest local relaxations.

A hybrid experimental–numerical methodology is presented for the parameter identification of a mixed nonlinear hardening anisotropic plasticity model fully coupled with isotropic ductile damage accounting for microcracks closure effects. In this study, three test materials are chosen: DP1000, CP1200, and AL7020. The experiments involve the tensile tests with smooth and notched specimens and two types of shear tests. The tensile tests with smooth specimens are conducted in different directions with respect to the rolling direction. This helps to determine the plastic anisotropy parameters of the material when the ductile damage is still negligible. Also, in-plane torsion tests with a single loading cycle are used to determine separately the isotropic and kinematic hardening parameters. Finally, tensile tests with notched specimens and Shouler and Allwood shear tests are used for the damage parameters identification. These are conducted until the final fracture with the triaxiality ratio η lying between 0 and [Formula: see text] (i.e. [Formula: see text]). The classical force–displacement curves are chosen as the experimental responses. However, for the tensile test with notched specimens, the distribution of displacement components is measured using a full field measurement technique (ARAMIS system). These experimental results are directly used by the identification methodology in order to determine the “best” values of material parameters involved in the constitutive equations. The inverse identification methodology combines an optimization algorithm which is coded within MATLAB together with the finite element (FE) code ABAQUS/Explicit. After optimization, good agreement between experimental and numerically predicted results in terms of force–displacement curves is obtained for the three studied materials. Finally, the applicability and validity of the determined material parameters are proved with additional validation tests.

The confinement of discotic columnar liquid crystal in nanoporous templates is a promising strategy to design nanofibers with potential applications in organic electronics. However, for many materials, geometric nanoconfinement has been shown to induce significant modifications of the physical properties, such as structure or phase behavior. We address the case of a discotic columnar liquid crystal confined in various templates. The influence of the size, the roughness, and the chemical nature of pores was investigated for a pyrene derivative by small-angle neutron scattering, X-ray diffraction, and calorimetry on a wide range of temperatures. A homeotropic anchoring (face-on orientation of the disk-shape molecules at the interface) is favored in all smooth cylindrical nanochannels of porous alumina while surface roughness of porous silicon promotes more disordered structures. The hexagonal columnar–isotropic phase transition is modified as a result of geometrical constraints and interfacial interactions.

International audience; We report on the measurement of the electro-optic coefficient r33 of poled polymers at k = 1.55 lm via the non-linear ellipsometry technique (or Teng and Man technique). Since the measurements rely on the use of sandwich structures with transparent electrodes, different types of aluminium doped zinc oxide (ZnO:Al) are taken into account in order to ensure transparency at the infrared range wavelength. Results on the disperse red 1/poly-methyl-metacrylate (DR1–PMMA) based side-chain benchmark system, with several different concentrations of active groups from 0.05 to 0.58 molar, are reported and demonstrate the reliability of the technique. The measurement technique was then used to evaluate the r33 coefficient of copolymers derived from DR1–PMMA by partial fluorination (FATRIFE). In this case, we measured copolymers with three concentrations of active groups, 0.30, 0.37 and 0.56 molar.

C. Katan present address: CNRS UMR6082 FOTON, INSA de Rennes, 20 avenue des Buttes de Coësmes, CS 70839, 35708 RENNES cedex 7, France; International audience; Structurally related chromophores of different symmetry (dipolar, V-shaped, octupolar) are investigated and compared for elucidation of the combined role of branching and charge symmetry on absorption, photoluminescence and two-photon absorption (TPA). Their design is based on the assembly of one, two or three -conjugated dipolar branches on a central core. Two series of branched structures obtained from a central triphenylamine core and dipolar branches having different charge-transfer characters are investigated: photophysical properties are studied and TPA spectra are determined through two-photon excited fluorescence experiments using fs pulses in the 700-1000 nm range. Calculations based on time-dependent quantum-chemical approaches, as well as the Frenkel exciton model, complement experimental findings. Experiments and theory reveal that a multidimensional intramolecular charge transfer takes place from the central electron-donating moiety to the periphery of the branched molecules upon excitation, whereas fluorescence stems from a dipolar branch. Symmetry and inter-branch electronic coupling are found to be responsible for amplification of the TPA response of branched compounds with respect to their monomeric analogues. In particular, an enhancement is observed in regions where the TPA bands overlap, and TPA activation is obtained in spectral regions where the dipolar analogue is almost two-photon transparent. Thus, appropriate tuning of the number of branches, of the coupling between them, and modulation of intramolecular charge transfer from core to periphery open the way for substantial improvement of TPA efficiency or TPA induction in desired spectral regions.