Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3-22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.

We explore the optical birefringence of the nematic binary mixtures 6CB1−x7CBx (0 ≤ x ≤ 1) imbibed into parallel-aligned nanochannels of mesoporous alumina and silica membranes for channel radii of 3.4 ≤ R ≤ 21.0 nm. The results are compared with the bulk behavior and analyzed with a Landau-de-Gennes model. Depending on the channel radius the nematic ordering in the cylindrical nanochannels evolves either discontinuously (subcritical regime, nematic ordering field σ < 1/2) or continuously (overcritical regime, σ > 1/2), but in both cases with a characteristic paranematic precursor behavior. The strength of the ordering field, imposed by the channel walls, and the magnitude of quenched disorder varies linearly with the mole fraction x and scales inversely proportional with R for channel radii larger than 4 nm. The critical pore radius, Rc, separating a continuous from a discontinuous paranematic-to-nematic evolution, varies linearly with x and differs negligibly between the silica and alumina membranes. We find no hints of preferred adsorption of one species at the channels walls. By contrast, a linear variation of the nematic-to-paranematic transition point TPN and of the nematic ordering field σ vs. x suggest that the binary mixtures of cyanobiphenyls 6CB and 7CB keep their homogeneous bulk stoichiometry also in nanoconfinement, at least for channel diameters larger than ∼7 nm.

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 longtime 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.

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We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores.