On De Gennes narrowing of fluids confined at the molecular scale in nanoporous materials.

Beyond well-documented confinement and surface effects arising from the large internal surface and severely confining porosity of nanoporous hosts, the transport of nanoconfined fluids remains puzzling in many aspects. With striking examples such as memory, i.e.

Topological Metadefects: Tangles of Dislocations.

The concept of topological defects is universal. In condensed matter, it applies to disclinations, dislocations, or vortices that are fingerprints of symmetry breaking during phase transitions. Using as a generic example the tangles of dislocations, we introduce the concept of topological metadefects, i.

Gas Adsorption in Zeolite and Thin Zeolite Layers: Molecular Simulation, Experiment, and Adsorption Potential Theory.

Molecular simulations and experiments are used to investigate methane adsorption in bulk and thin layers of MFI zeolite (silicalite-1). After comparing the theoretical adsorption data obtained using Grand Canonical Monte Carlo simulations for bulk MFI at various temperatures against experiments, zeolite layers with different crystalline orientations and levels of surface flexibility are considered. The data obtained for such prototypical systems allow us to rationalize both the qualitative and quantitative impact of external surface in nanoporous solids.

Interplay of vitrification and ice formation in a cryoprotectant aqueous solution at low temperature.

The proneness of water to crystallize is a major obstacle to understanding its putative exotic behavior in the supercooled state. It also represents a strong practical limitation to cryopreservation of biological systems. Adding some concentration of glycerol, which has a cryoprotective effect preventing, to some degree, water crystallization, has been proposed as a possible way out, provided the concentration is small enough for water to retain some of its bulk character and/or for limiting the damage caused by glycerol on living organisms.

Interplay of Structure and Dynamics in Lithium/Ionic Liquid Electrolytes: Experiment and Molecular Simulation.

Despite their promising use in electrochemical and electrokinetic devices, ionic-liquid-based electrolytes often exhibit complex behavior arising from a subtle interplay of their structure and dynamics. Here, we report a joint experimental and molecular simulation study of such electrolytes obtained by mixing 1-butyl 3-methylimidazolium tetrafluoroborate with lithium tetrafluoroborate. More in detail, experiments consisting of X-ray scattering, pulsed field gradient NMR, and complex impedance spectroscopy are analyzed in the light of molecular dynamics simulations to probe the structural, dynamical, and electrochemical properties of this ionic-liquid-based electrolyte.

Perfluorosulfonyl Imide versus Perfluorosulfonic Acid Ionomers in Proton-Exchange Membrane Fuel Cells at Low Relative Humidity.

Designing highly conductive ionomers at high temperature and low relative humidity is challenging in proton-exchange membrane fuel cells. Perfluorosulfonyl imide ionomers were believed to achieve this goal, owing to their exceptional acidity and excellent thermal stability. Perfluorosulfonyl imide ionomers are less conductive than the analogous perfluorosulfonic acids despite similar membrane microstructure.

Communication: Investigation of ion aggregation in ionic liquids and their solutions with lithium salt under high pressure.

X-ray scattering measurements were utilized to probe the effects of pressure on a series of ionic liquids, N-alkyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr-TFSI) (A = 3, 6, and 9), along with mixtures of ionic liquid and 30 mol. % lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. No evidence was found for crystallization of the pure ionic liquids or salt mixtures even at pressures up to 9.

Ionic Liquids: evidence of the viscosity scale-dependence.

Ionic Liquids (ILs) are a specific class of molecular electrolytes characterized by the total absence of co-solvent. Due to their remarkable chemical and electrochemical stability, they are prime candidates for the development of safe and sustainable energy storage systems. The competition between electrostatic and van der Waals interactions leads to a property original for pure liquids: they self-organize in fluctuating nanometric aggregates.

Low-field single-sided NMR for one-shot 1D-mapping: Application to membranes.

Many single-sided permanent magnet NMR systems have been proposed over the years allowing for 1D proton-density profiling, diffusion measurements and relaxometry. In this manuscript we make use of a recently published unilateral magnet for low-field NMR exhibiting an extremely uniform magnetic field gradient with moderate strength and cylindrical symmetry, allowing for a well-defined sweet spot. Combined with a goniometer, our system is used to characterize precisely the uniformity of its gradient and to achieve micrometric precision 1D profiling, as well as spatially localized relaxometry and diffusometry on thick (∼150μm) membrane samples.

Anisotropic charge transport in ion-conductive photoresponsive polyethylene oxide-based mesomorphic materials.

The mechanism of charge motion in conductive and photosensitive mesogenic block copolymers containing polyethylene oxide (PEO) segments is investigated over a wide frequency and temperature range with the broadband dielectric spectroscopy technique. It is found that the ultraviolet (UV) irradiation, the UV intensity, and the anchoring conditions of mesogenic unit in the cells produce changes in conductivity properties and in the molecular arrangement. The anisotropic nature of the conductivity is established.

Nanostructuration of ionic liquids: impact on the cation mobility. A multi-scale study.

When probed at the macroscopic scale, Ionic Liquids (ILs) behave as highly dissociated (i.e. strong) electrolytes while, at the molecular scale, they show clear characteristics of weak ionic solutions.

Controlling Microstructure-Transport Interplay in Highly Phase-Separated Perfluorosulfonated Aromatic Multiblock Ionomers via Molecular Architecture Design.

Proton-conducting multiblock polysulfones bearing perfluorosulfonic acid side chains were designed to encode nanoscale phase-separation, well-defined hydrophilic/hydrophobic interfaces, and optimized transport properties. Herein, we show that the superacid side chains yield highly ordered morphologies that can be tailored by best compromising ion-exchange capacity and block lengths. The obtained microstructures were extensively characterized by small-angle neutron scattering (SANS) over an extended range of hydration.

Water in Carbon Nanotubes: The Peculiar Hydrogen Bond Network Revealed by Infrared Spectroscopy.

A groundbreaking discovery in nanofluidics was the observation of the tremendously enhanced water permeability of carbon nanotubes, those iconic objects of nanosciences. The origin of this phenomenon is still a subject of controversy. One of the proposed explanations involves dramatic modifications of the H-bond network of nanoconfined water with respect to that of bulk water.

Competing coexisting phases in 2D water.

The properties of bulk water come from a delicate balance of interactions on length scales encompassing several orders of magnitudes: i) the Hydrogen Bond (HBond) at the molecular scale and ii) the extension of this HBond network up to the macroscopic level. Here, we address the physics of water when the three dimensional extension of the HBond network is frustrated, so that the water molecules are forced to organize in only two dimensions. We account for the large scale fluctuating HBond network by an analytical mean-field percolation model.

Large-Scale Diffusion of Entangled Polymers along Nanochannels.

Changes in large-scale polymer diffusivity along interfaces, arising from transient surface contacts at the nanometer scale, are not well understood. Using proton pulsed-gradient NMR, we here study the equilibrium micrometer-scale self-diffusion of poly(butadiene) chains along ∼100 μm long, 20 and 60 nm wide channels in alumina, which is a system without confinement-related changes in segmental relaxation time. Unlike previous reports on nonequilibrium start-up diffusion normal to an interface or into particulate nanocomposites, we find a reduction of the diffusivity that appears to depend only upon the pore diameter but not on the molecular weight in a range between 2 and 24 kg/mol.

Proton diffusion in the hexafluorophosphoric acid clathrate hydrate.

The hexafluorophosphoric acid clathrate hydrate is known as a "super-protonic" conductor: its proton conductivity is of the order of 0.1 S/cm at ca. room temperature.

Diffusion Coefficients from (13)C PGSE NMR Measurements-Fluorine-Free Ionic Liquids with the DCTA(-) Anion.

Pulsed-field gradient spin-echo (PGSE) NMR is a widely used method for the determination of molecular and ionic self-diffusion coefficients. The analysis has thus far been limited largely to (1)H, (7)Li, (19)F, and (31)P nuclei. This limitation handicaps the analysis of materials without these nuclei or for which these nuclei are insufficient for complete characterization.

Large-scale dynamics of a single polymer chain under severe confinement.

We address the dynamical behavior of a single polymer chain under nanometric confinement. We show how neutron spin-echo, combined with contrast matching and zero average contrast, makes it possible to, all at once, (i) match the intense porous detrimental elastic small angle neutron scattering contribution to the total intermediate scattering function I(Q,t) and (ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The method presented here has a general relevance when probing the large scale dynamics of a system of large molecular mass under confinement.

Structure-properties relationships of lithium electrolytes based on ionic liquid.

Low-melting ionic liquid, IL, based on small aliphatic quaternary ammonium cations ([R(1)R(2)R(3)NR](+), where R(1), R(2), R(3) = CH(3) or C(2)H(5), R = C(3)H(7), C(4)H(9), C(6)H(13), C(8)H(17), CF(3)C(3)H(6)) and imide anion were prepared and characterized. The physicochemical and electrochemical properties of these ILs, including melting point, glass transition, and degradation temperatures; viscosity; density; ionic conductivity; diffusion coefficient; and electrochemical stability, were determined. Heteronuclear Overhauser NMR spectroscopy experiments were also performed to point out the presence of pair correlation between the different moieties.

A PGSE-NMR study of molecular self-diffusion in lamellar phases doped with polyoxometalates.

Using pulsed gradient spin-echo NMR, we studied molecular self-diffusion in aligned samples of a hybrid lyotropic lamellar L(alpha) phase. This composite organic-inorganic material was obtained by doping the lamellar phase of the nonionic surfactant Brij-30 with the [PW(12)O(40)](3-) polyoxometalate (POM). Both water and POM self-diffusion display a large anisotropy, as diffusion is severely restricted along the normal to the bilayers.

Polyepichlorhydrin membranes for alkaline fuel cells: sorption and conduction properties.

Polymer electrolytes, using a poly(epichlorhydrin-allyl glycidyl ether) copolymer as matrix, are shown to perform well in alkaline fuel cell electrolyte. An anion-conducting network is obtained by the incorporation of cyclic diamines, 1,4-diazabicyclo[2.2.

Diffusion processes in homogeneous and phase-separated binary fluid mixtures.

Diffusion processes in dynamically asymmetric binary fluid mixtures made of monodisperse polystyrene (PS) and a rodlike nematogen molecule (5CB) are studied by pulsed-field gradient spin echo NMR in the vicinity of the phase-separation/phase-dissolution temperature. The phase-separation process and the loss of mobility of polymer chains at Tg take place simultaneously evidencing the strong effect of elasticity on the sample morphology. Below the instability point of the mixture, two self-diffusion coefficients, named Dfast and Dslow, are observed and assigned to mobile molecules i) dissolved in the polymeric matrix and ii) phase-separated in isolated or interconnected domains, respectively.

Proton conducting ionic liquid organization as probed by NMR: self-diffusion coefficients and heteronuclear correlations.

The structure and local organization of new proton conducting ionic liquids (PCILs) obtained by reacting alkylamine with various acids were deciphered by complementary 1- and 2-D heteronuclear NMR experiments. One the one hand, PFG NMR yielded the self-diffusion coefficients of the PCIL components (and thus information on their possible concerted translational motions), while on the other hand, 13C, 1H, and 15N, 1H correlation and intermolecular Overhauser experiments gave insight into the nature of protonic species and ion-pairing behavior.

NMR and electrochemical study on lithium oligoether sulfate in polymeric and liquid electrolytes.

Electrolytes based on lithium oligoether sulfate, and dissolved in liquid or polymer solvents, are studied. Their properties in term of ionic conductivities, transference numbers, diffusion coefficients, and electrochemical stabilities are reported. The comparison between NMR and electrochemical data, that is, transference numbers and conductivities, provides important information about the existence of ion pairs and aggregates.