Density profile of water confined in cylindrical pores in MCM-41 silica

Recently, water absorbed in the porous silica material MCM-41-S15 has been used to demonstrate an apparent fragile to strong dynamical crossover on cooling below ～220 K, and also to claim that the density of confined water reaches a minimum at a temperature around 200 K. Both of these behaviours are purported to arise from the crossing of a Widom line above a conjectured liquid-liquid critical point in bulk water. Here it is shown that traditional estimates of the pore diameter in this porous silica material (of order 15 ?) are too small to allow the amount of water that is observed to be absorbed by these materials (around 0.5 g H(2)O/g substrate) to be absorbed only inside the pore. Either the additional water is absorbed on the surface of the silica particles and outside the pores, or else the pores are larger than the traditional estimates. In addition the low Q Bragg intensities from a sample of MCM-41-S15 porous silica under different dry and wet conditions and with different hydrogen isotopes are simulated using a simple model of the water and silica density profile across the pore. It is found the best agreement of these intensities with experimental data is shown by assuming the much larger pore diameter of 25 ? (radius 12.5 ?). Qualitative agreement is found between these simulated density profiles and those found in recent empirical potential structure refinement simulations of the same data, even though the latter data did not specifically include the Bragg peaks in the structure refinement. It is shown that the change in the (100) peak intensity on cooling from 300 to 210 K, which previously has been ascribed to a change in density of the confined water on cooling, can equally be ascribed to a change in density profile at constant average density. It is further pointed out that, independent of whether the pore diameter really is as large as 25 ? or whether a significant amount of water is absorbed outside the pore, the earlier reports of a dynamic crossover in supercooled confined water could in fact be a crystallization transition in the larger pore or surface water.     

Supercooled confined water and the mode coupling crossover temperature

We present a molecular dynamics study of the single-particle dynamics of supercooled water confined in a silica pore. Two dynamical regimes are found. Close to the hydrophilic substrate molecules are below the mode coupling crossover temperature, T(C), already at ambient temperature. The water closer to the center of the pore (free water) approaches upon supercooling T(C) as predicted by mode coupling theories. For free water the crossover temperature and crossover exponent gamma are extracted from power-law fits to both the diffusion coefficient and the relaxation time of the late alpha region.     

Estimation of pore pressure and phase transitions of water confined in nanopores with non-local density functional theory

In this paper, the non-local density functional theory is used in combination with SAFT-VR, to investigate the pore pressure behaviour of water confined in various nanopores. Due to the efficiency and low computational cost of the method, many configurations and thermodynamic conditions are explored. In particular, capillary condensation and evaporation of water, their impact on the pore pressure, and the effect of surface activation are evaluated. Successive first-order phase transitions of ultra-confined water monolayer are also highlighted.     

Dynamics of water in molecular sieves by dielectric spectroscopy

We present recent dielectric data on the dynamics of water confined in molecular sieves with pore sizes 5 and 10 A. The dielectric measurements in the frequency and temperature ranges 10(-2)-10(6) Hz and 120-300 K show three relaxation processes for both samples. In the case of the 10 A pore the slowest process shows an Arrhenius temperature dependence at low temperatures (<220 K), while at high temperatures the relaxation appears to follow a more Vogel-Fulcher-Tammann (VFT) like behaviour. The relaxation time for this process is 100 s at about 170 K. The second slowest process is at low temperatures very similar to the main process of (bulk-like) water in a fully hydrated clay, but also this process seems to exhibit some kind of dynamical transition, in this case at T approximately 185 K. All the three processes in the 5 A pore exhibit Arrhenius temperature dependence, and two of them are considerably slower than the main relaxation in the hydrated clay. Thus, dynamics of bulk-like water is only observed in the 10 A molecular sieves, and most of the water molecules in both 5 and 10 A pores have considerably slower dielectric relaxation than has been observed for water confined in clay, most likely due to strong interactions with the considerably more hydrophilic inner surfaces of molecular sieves.     

Temperature dependence of structure and density for D?O confined in MCM-41-S

Using neutron diffraction, we have tracked the temperature dependence of structural properties for heavy water confined in the nanoporous silica matrix MCM-41-S. By observing the correlation peak corresponding to the pore-pore distance, which is determined by the scattering contrast between the silica and the water, we monitored the density of the confined water. Concurrently, we studied the prominent first diffraction peak of D(2)O at ≈ 1.8 ?(-1), which furnishes information on the microscopic arrangement of the water molecules. The data show the presence of a density maximum at ≈ 275 K (± 10 K), a property similar to bulk water, and the occurrence of a density minimum at ≈ 180 K (± 10 K). The prominent diffraction peak of D(2)O is found to shift and sharpen over a wide T range from 200 to 270 K, reflecting structural changes that are strongly correlated with the changes in density. We also observe the continuous formation of external ice, arising from water expelled from the pores while expansion takes place within the pores. An efficient method for monitoring the density of the confined D(2)O using a triple-axis spectrometer is demonstrated.     

Liquid-liquid critical point in heavy water

According to the liquid-liquid critical-point hypothesis about water, two liquid waters exist at low temperatures and are supposed to be merged at a critical point. The low-temperature metastable melting curves of D2O ices have been measured. It is found that the melting curve of D2O ice III is smoothly curved around 25 MPa and 238 K, whereas the melting curve of D2O ice IV undergoes an abrupt change of slope at 100 MPa and 220 K. This is consistent with the existence of a liquid-liquid critical point in the region between the melting curve of D2O ice III and the melting curve of D2O ice IV.     

Structure and dynamic properties of liquids confined in MCM-41 mesopores

The microscopic structure and dynamic properties of water, methanol, and acetonitrile confined in mesoporous MCM-41 materials have been investigated under monolayer and capillary-condensation conditions as a function of pore size and temperature by in situ FTIR and X-ray diffraction and quasi-elastic neutron scattering techniques. Both interfacial and confinement effects on the structure and dynamics of the liquids in hydrophilic pores are discussed at the molecular level.     

Computer simulations of dynamic crossover phenomena in nanoconfined water

In order to study dynamic crossover phenomena in nanoconfined water we performed a series of molecular dynamics (MD) computer simulations of water clusters adsorbed in zeolites, which are microporous crystalline aluminosilicates containing channels and cavities of nanometric dimensions. We used a sophisticated empirical potential for water, including the full flexibility of the molecule and the correct response to the electric field generated by the cations and by the charged atoms of the aluminosilicate framework. In addition, the full flexibility of the aluminosilicate framework was included in the calculations. Previously reported and new simulations of water confined in a number of different types of zeolites in the temperature range 100-300 K and at various coverage are discussed in connection with the experimental data. Dynamic crossover phenomena are found in all the considered cases, in spite of the different shape and size of the clusters, even when the confinement hinders the formation of tetrahedral hydrogen bonds for water molecules. Hypotheses about the possible dynamic crossover mechanisms are proposed.     

Colloidal monolayer trapped near a charged wall: a synchrotron x-ray diffraction study

Using x-ray diffraction from microfluidic channel arrays, we have determined concentration profiles of charge-stabilized silica colloids (radius 60+/-2 nm) confined between two like-charged dielectric walls at a few hundred nanometer distance. In solutions of very low ionic strength, strongly repulsive Coulomb interactions drive the colloids toward the central region between the walls. The addition of a small quantity of salt ions (0.2 mM) causes a dense colloidal monolayer to be trapped near the walls.     

Two-dimensional condensation of water and alcohols on NaF

On the surface of NaF the adsorption isotherms of H₂O, D₂O, CH₃OH, C₃H₃OH and 1-C₃H₇OH as well as the infrared spectra of H₃O, D₂O, dilute HDO, CH₃OH and CH₃OD were measured. The adsorption temperatures of H₃O (253–308 K) were within the phase transition region where two phases of low and high density coexist, while those of CH₃OH, C₂H₅OH and 1-C₃H₃OH were yet within a super-critical region. The entropy of the 2D condensed H₂O on NaF was found to be 14.0 cal K^?1 mol^?1, which suggests that the condensed phase of water on NaF is liquid-like. The OD stretching band of dilute HDO in the 2D condensed water gives a maximum adsorption at ca. 2530 cm^?1 with a half width of ca. 150 cm^?1, being in good agreement with that in liquid water. Comparison of the integrated absorbance of the D₂O bending mode with that of the OD stretching mode suggests that the cluster size of the 2D condensed water on NaF decreases with increasing temperature. The 2D critical temperature and the occupied areas of these adsorbates enable us to conclude that the compatibility of the molecular size with the surface lattice is not important in the occurrence of the 2D condensation of the hydrogen-bonding molecules on NaF and that adsorbed molecules are randomly oriented on the surface to the extent similar to that in 3D liquid state.     

Small‐angle Scattering Studies of Adsorption and of Capillary Condensation in Porous Solids

Small‐angle scattering (SAS) studies are reviewed of adsorption and capillary condensation of water, hydrocarbons and halogenated hydrocarbons near room temperature, and of nitrogen at 78 K in some mesoporous solids, mainly silicas. The theory needed for the interpretation of SAS data is briefly covered. Calculations of the scattered intensity I(q) for a model porous medium show that I(q) depends markedly on the film thickness t. Adsorption and capillary condensation of nitrogen at 78 K in mesoporous silicas was studied by use of in situ SANS, and t as function of the relative pressure P/P_s was estimated. Adsorption of N₂ in defects within the silica skeleton at P/P_s<0.1 lead to a significant increase in I(q). Isolated vapor bubbles in capillary condensed nitrogen in a Gelsil^® appeared on adsorption near saturation of the pore system. The kinetics of capillary condensation and of drainage were followed. Power law scattering at low q indicated the formation of ramified clusters of voids on drainage of liquid nitrogen from the xerogel Gelsil^®. Similar clusters were observed on drainage of water from Vycor^® glass. Provided the clusters indicate a percolation process, the desorption branch should not be used for the estimation of a pore size distribution for materials with networked pores. The adsorptive smoothing by benzene was observed of a rough interface in a controlled pore glass.     

Dynamics of the BCS-BEC crossover in a degenerate Fermi gas

We study the short-time dynamics of a degenerate Fermi gas positioned near a Feshbach resonance following an abrupt jump in the atomic interaction resulting from a change of magnetic field. We investigate the dynamics of the condensate order parameter and pair wave function for a range of field strengths. When the jump is sufficient to span the BCS to Bose-Einstein condensation crossover, we show that the rigidity of the momentum distribution precludes any atom-molecule oscillations in the entrance channel dominated resonances observed in 40K and 6Li. Focusing on material parameters tailored to the 40K Feshbach resonance at 202.1 G, we comment on the integrity of the fast sweep projection technique as a vehicle to explore the condensed phase in the crossover region.     

Mössbauer spectroscopy and magnetic studies of orientated textured Fe3O4 ferrofluid

Nano scale magnetite based ferrofluid is synthesized by chemical co pre cipitation technique and stabilized with oleic acid. Magnetization and viscosity measurements were used to optimize for texturing purpose. The freeze-textured ferrofluid in two configurations, namely, (1) field texture system (FTS) and (2) zero field texture system (ZTS) are investigated by magnetization measurements at 298 K and Mössbauer spectroscopy measurements at 77 and 298 K. These results are analysed on the basis of the contributions from collective superparamagnetic reversal and the strength of the inter particle interactions.     

Fluidity of hydration layers nanoconfined between mica surfaces

We perform molecular dynamics simulations to investigate the shear dynamics of hydration water nanoconfined between two mica surfaces at 1 bar pressure and 298 K. Newtonian plateaus of shear viscosity comparable to the bulk value for different hydration layers D=0.92-2.44 nm are obtained. The origin of this persistent fluidity of the confined aqueous system is found to be closely associated with the rotational dynamics of water molecules, accompanied by fast translational diffusion under this confinement.     

Water-filled MCM-41 characterized by double-quantum-filtered2H NMR spectral analysis

The dynamics of water molecules confined in adsorbed layers of siliceous MCM-41 with a pore diameter of 2.8 nm is investigated at 230 K by deuteron nuclear magnetic resonance (NMR) relaxation studies including line shapes of theT ₁ process and double quantum filtered (DQF) spectral analyses.²H DQF NMR is a particularly sensitive tool for the determination of the adsorbate dynamics resulting from residual quadrupolar interaction due to the local order. The amount of monolayer water is determined. The monolayer water is composed of two different water components characterized by water, with isotropic reorientational motions, exchanging with water displaying a solid-like spectrum with 4 kHz edge splitting. One may expect that the latter water is situated on surface sites in MCM-41. The restricted wobbling motion of the D-O bond is used to describe its dynamics which is one order of magnitude slower than the isotropic reorientational motion. The order parameter, the motional correlation time, and the exchange rate thus determined provide useful information on the structure and the adsorptive properties of the mesoporous system.     

Conductivity in hydrated proteins: no signs of the fragile-to-strong crossover

Dielectric spectroscopy studies of hydrated protein demonstrate smooth temperature variations of conductivity. This observation suggests no cusplike fragile-to-strong crossover (FSC) in the protein's hydration water. The FSC at T approximately 220 K was postulated recently on the basis of neutron scattering studies [Chen, Proc. Natl. Acad. Sci. U.S.A. 103, 9012 (2006)] and was proposed to be the main cause for the dynamic transition in hydrated proteins. Following Swenson et al. , we ascribe the neutron results to a secondary relaxation. We emphasize that no cusplike solvent behavior is required for the protein's dynamic transition.     

Changes in dynamical behavior of ionic liquid in silica nano-pores

Dielectric relaxation measurement has been carried out on an ionic liquid (1-butyl-3-methyl imidazolium hexafluorophosphate, [BMIM][PF₆]) confined in nano-porous silica matrix. Two dielectric relaxation peaks have been observed in the confined ionic liquid (IL) while there is only one relaxation peak for bulk IL. Confinement results in layering of some IL molecules near the pore wall while other molecules, less affected by pore wall interaction, remain in the central core. The two relaxation peaks are assigned to the different dynamical behaviors of the central core and layered IL molecules.     

Probing interfacial dynamics of water in confined nanoporous systems by NMRD

The confined dynamics of water molecules inside a pore involves an intermittence between adsorption steps near the interface and surface diffusion and excursions in the pore network. Depending on the strength of the interaction in the layer(s) close to the surface and the dynamical confinement of the distal bulk liquid, exchange dynamics can vary significantly. The average time spent in the surface proximal region (also called the adsorption layer) between a first entry and a consecutive exit allows estimating the level of ‘nanowettablity’ of water. As shown in several seminal works, NMRD is an efficient experimental method to follow such intermittent dynamics close to an interface. In this paper, the intermittent dynamics of a confined fluid inside nanoporous materials is discussed. Special attention is devoted to the interplay between bulk diffusion, adsorption and surface diffusion on curved pore interfaces. Considering the nano or meso length scale confinement of the pore network, an analytical model for calculating the inter-dipolar spin–lattice relaxation dispersion curves is proposed. In the low-frequency regime (50?KHz–100?MHz), this model is successfully compared with numerical simulations performed using a 3D-off lattice reconstruction of Vycor glass. Comparison with experimental data available in the literature is finally discussed.     

Molecular mobility of confined phases in model mesoporous (MCM-41) and microporous (AlPO(4)-5 zeolite) host materials

The considered host materials are well suited to confine quasi-(1d) molecular phases, seeing that their porosities are composed of parallel unconnected cylindrical pores. For such a simple geometry, confinement effects can be simply described by a single parameter, the pore diameter phi. Our study concerns medium and ultra confinement ranges ( 40 A >or= ? >or= 7.3 A). The primary effect of such confinements is the decrease of the molecular interactions within the confined phase. As a consequence, we have observed strong triple point depressure Delta T(3t) effects for hydrogen and water confined phases in MCM-41 samples. In the limit case of (1d) phase (the neopentane/AlPO(4)-5 system) it seems that a molecular mobility is observed even at very low temperature T=5 K. The secondary confinement effect is an increase of the interactions between the host inner surface and the confined molecular assembly induced by the pore diameter decreasing. Such host material influence gives rise, for medium range confinement to the physisorption of a curved solid film on the inner surface before the capillary phase condensation (hydrogen/MCM-41 (24 A)) and for ultra confinement to the solidification of the confined phase when the molecular species are commensurate with the inner surface sites (methane/AlPO(4)-5).     

Capillary force on colloidal particles in a freely suspended liquid thin film

The dynamic behavior of micron-sized polystyrene latex particles confined in a free-standing liquid film is experimentally studied. When the thickness of the film is less than the particle diameter and varies depending on position, the particles are accelerated toward the thicker region. Using a simple geometrical model and hydrodynamic theory, we calculate the capillary force on the particle. The drag coefficient of the particle is found to depend on the thickness of the film from the value of near zero to the Stokes' drag coefficient.