Self-assembly of a non-ionic surfactant onto a clay mineral for the preparation of hybrid layered materials

International audienceThe adsorption of the tri-ethylene glycol mono-n-decyl ether (C10E3) nonionic surfactant, characterized by its self-assembled lamellar phase above the critical micelle concentration (cmc), in a wide range of concentration, onto a layered clay mineral (montmorillonite) has been studied. C10E3 exhibits a high affinity for the montmorillonite (Mt) surface with an adsorption isotherm that differs strictly from previous studies on the adsorption of nonionic surfactants onto clay minerals for which a maximum of adsorption was reached below cmc. The self-organization in a lamellar phase changes the interaction potential between C10E3 and Mt, a surface that favors the aggregation of normal bilayers which expands the interlayer space at wide values (>40 °A) while keeping the exchangeable Na+ cations conferring dual hydrophilic-hydrophobic behavior for the hybrid layered materials. Depending on the C10E3 phase state (in monomers or in a lamellar phase), the adsorption leads to four distinct surfactant arrangements (lateral layers to normal tilted bilayers) within the interlayer space of Mt. The hybrid layered materials show a thermal stability at 350 C with a collapse of their interlayer space at 13 °A due to the degradation of the hydrocarbon chains of C10E3. FTIR during thermogravimetry analysis permits the identification of the portions of C10E3 corresponding to ethylene oxide groups in close interaction with the Mt surface

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

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.Comment: version March 12 200

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.Comment: Submitted to Phys. Rev.

Zinc-rich clays in supergene non-sulfide zinc deposits

International audienceThe nature and the origin of zinc clays are poorly understood. With the example of the Bou Arhous Zn-Pb ore deposit in the Moroccan High Atlas, this study presents new data for the mineralogical and chemical characterization of barren and zinc clays associated with non-sulfide zinc ores. In the field, white to ocher granular clays are associated with willemite (Zn2SiO4), while red clays fill karst-related cavities cutting across the non-sulfide ore bodies. Red clays (kaolinite, chlorite, illite, and smectite) present evidence of stratification that reflects internal sedimentation processes during the karst evolution. White clays contain 7-Å clay mineral/smectite irregular interstratified minerals with less than 20 % of smectite layers. Willemite is partially dissolved and is surrounded by authigenic zinc clay minerals. Together with XRD results, WDS analyses on newly formed clay aggregates suggest that this interstratified mineral is composed of fraipontite and sauconite. CEC measurements support that zinc is only located within the octahedral sheets. These new results support the following process: (i) dissolution of willemite, leading to release of Si and Zn, (ii) interaction between Zn-Si-rich solutions and residual-detrital clays, and (iii) dissolution of kaolinite and formation of interstratified zinc clay minerals that grew over detrital micas

Sandwich organization of non-ionic surfactant liquid crystalline phases as induced by large inorganic K4Nb6O17 nanosheets

International audienceWhile keeping its lamellar liquid crystal phase, K4Nb6O17 nanosheets were used as a template to sandwich and stabilize an alkylpoly(ethylene oxide) nonionic surfactant-water system showing a monodomain (lamella) formation within the inorganic niobate sheets that appears to not be depend to the surfactant liquid crystalline state in solution but more its concentration

NH4-smectite: Characterization, hydration properties and hydro mechanical behaviour

International audienceLeachates in waste landfills are characterized by the presence of ammonium ions in large excess. These ammonium ions can be exchanged with the interlayer cations in clay and modify the physical and chemical properties of clay geochemical barriers in waste landfills and drive to environmental problems. The purpose of this study was to understand the hydro-physical changes of a smectite in the presence of ammonium ions. An ammonium smectite was prepared by cation exchange from a natural montmorillonite (Wyoming). The samples were characterized and their properties were compared by the use of a set of complementary techniques (X-ray diffraction, infrared spectroscopy, N2 adsorption-desorption BET technique, thermal analysis, and percolation experiments). The main effect was a modification of the porosity and its network, and reduced crystalline swelling. These effects changed the hydraulic conductivity and macroscopic swelling of the clay. The oedometer experiments, which allow simulating the pressure on small amounts of samples, proved the strong increase of the permeability of NH4-smectite. This last point is of great importance in an environment point of view and raises questions on the impermeability behaviour on the long term of the clay geochemical barriers with the presence of ammonium ions in waste landfills

Relation between static short-range order and dynamic heterogeneities in a nanoconfined liquid crystal

International audienceWe analyze the molecular dynamics heterogeneity of the liquid crystal 4-n-octyl-4'-cyanobiphenyl nanoconfined in porous silicon. We show that the temperature dependence of the dynamic correlation length wall, which measures the distance over which a memory of the interfacial slowing down of the molecular dynamics persists, is closely related to the growth of the short-range static order arising from quenched random fields. More generally, this result may also shed some light on the connection between static and dynamic heterogeneities in a wide class of condensed and soft matter systems