Interfacial transport of evaporating water confined in nanopores

A semianalytical, continuum analysis of evaporation of water confined in a cylindrical nanopore is presented, wherein the combined effect of electrostatic interaction and van der Waals forces is taken into account. The equations governing fluid flow and heat transfer between liquid and vapor phases are partially integrated analytically, to yield a set of ordinary differential equations, which are solved numerically to determine the flow characteristics and effect on the resulting shape and rate of evaporation from the liquid-vapor interface. The analysis identifies three important parameters that significantly affect the overall performance of the system, namely, the capillary radius, pore-wall temperature, and the degree of saturation of vapor phase. The extension of meniscus is found to be prominent for smaller nanoscale capillaries, in turn yielding a greater net rate of evaporation per unit pore area. The effects of temperature and ambient vapor pressure on net rate of evaporation are shown to be analogous. An increase in pore-wall temperature, which enhances saturation pressure, or a decrease in the ambient vapor pressure result in enhancing the net potential for evaporation and increasing the curvature of the interface.     

Fragile-to-strong liquid transition in deeply supercooled confined water

Confining water in lab synthesized nanoporous silica matrices MCM-41-S with pore diameters of 18 and 14 A, we have been able to study the molecular dynamics of water in deeply supercooled states, down to 200 K. Using quasielastic neutron scattering and analyzing the data with the relaxing cage model, we determined the temperature variation of the average translational relaxation time and its Q-dependence. We find a clear evidence of an abrupt change of the relaxation time behavior at T approximately equal to 225 K, which we interpreted as the predicted fragile-to-strong liquid-liquid transition.     

Structure and dynamics of water confined in silica nanopores

We report the results of molecular simulation of water in silica nanopores at full hydration and room temperature. The model systems are approximately cylindrical pores in amorphous silica, with diameters ranging from 20 to 40 ?. The filled pores are prepared using grand canonical Monte Carlo simulation and molecular dynamics simulation is used to calculate the water structure and dynamics. We found that water forms two distinct molecular layers at the interface and exhibits uniform, but somewhat lower than bulk liquid, density in the core region. The hydrogen bond density profile follows similar trends, with lower than bulk density in the core and enhancements at the interface, due to hydrogen bonds between water and surface non-bridging oxygens and OH groups. Our studies of water dynamics included translational mean squared displacements, orientational time correlations, survival probabilities in interfacial shells, and hydrogen bond population relaxation. We found that the radial-axial anisotropy in translational motion largely follows the predictions of a model of free diffusion in a cylinder. However, both translational and rotational water mobilities are strongly dependent on the proximity to the interface, with pronounced slowdown in layers near the interface. Within these layers, the effects of interface curvature are relatively modest, with only a small increase in mobility in going from the 20 to 40 ? diameter pore. Hydrogen bond population relaxation is nearly bulk-like in the core, but considerably slower in the interfacial region.     

Phase diagram and glass transition of confined benzene

We used differential scanning calorimetry, neutron scattering, and proton NMR to investigate the phase behavior, the structure, and the dynamics of benzene confined in a series of cylindrical mesoporous materials MCM-41 and SBA-15 with pore diameters, d, between 2.4 and 14 nm. With this multitechnique approach, it was possible to determine the structure and, for the first time to our knowledge, the density of confined benzene as a function of temperature and pore size. Under standard cooling rates, benzene partially crystallizes in SBA-15 matrixes (4.7 相似文献   

Structural transformations of supercooled water in nanopores, studied by microwave radiation

It is shown that the state of supercooled water in nanoporous materials can be studied by measuring the attenuation of microwave radiation. By analyzing variations in the intensity of radiation transmitted through a moistened medium during the supercooling of water in the range of ?37 to ?190°C, the temperatures at which structural transformations take place can be determined. Using the example of KSKG silica gel with a mean pore size of 8 nm, it is shown that at a moisture of 3?C18%, water is found in the liquid state up to a temperature of ?130°C, at which the transition to glass occurs.     

Proton quantum coherence observed in water confined in silica nanopores

Deep inelastic neutron scattering measurements of water confined in nanoporous xerogel powders, with average pore diameters of 24 and 82 A, have been carried out for pore fillings ranging from 76% to nearly full coverage. DINS measurements provide direct information on the momentum distribution n(p) of protons, probing the local structure of the molecular system. The observed scattering is interpreted within the framework of the impulse approximation and the longitudinal momentum distribution determined using a model independent approach. The results show that the proton momentum distribution is highly non-Gaussian. A bimodal distribution appears in the 24 A pore, indicating coherent motion of the proton over distances d of approximately 0.3 A. The proton mean kinetic energy W of the confined water molecule is determined from the second moment of n(p). The W values, higher than in bulk water, are ascribed to changes of the proton dynamics induced by the interaction between interfacial water and the confining surface.     

Phase behavior of binary blends of diblock copolymer/homopolymer confined in spherical nanopores

Binary blends of a diblock copolymer (AB) and an incompatible homopolymer (C) confined in spherical cavities are studied using a simulated annealing technique. The phase behavior of the blends is examined for four typical cases, representing the different selectivity of the pore surface to the A, B, and C species. The internal morphology of the spherical polymeric particles is controlled by the homopolymer volume fraction, the degree of confinement, and the composition of the copolymer. Inside a particle, the homopolymers segregate to form one or, under some conditions, two domains; thus, the homopolymers may act as an additional controlling parameter of the shape and symmetry of the copolymer domain. A rich array of confinement-induced novel diblock copolymer morphologies is predicted. In particular, core-shell particles with the copolymers as the shell wrapping around a homopolymer core or a copolymer-homopolymer combined core and Janus-like particles with the copolymers and the homopolymers on different sides are obtained.     

Phase diagram of water between hydrophobic surfaces

Molecular dynamics simulations demonstrate that there are at least two classes of quasi-two-dimensional solid water into which liquid water confined between hydrophobic surfaces freezes spontaneously and whose hydrogen-bond networks are as fully connected as those of bulk ice. One of them is the monolayer ice and the other is the bilayer solid which takes either a crystalline or an amorphous form. Here we present the phase transformations among liquid, bilayer amorphous (or crystalline) ice, and monolayer ice phases at various thermodynamic conditions, then determine curves of melting, freezing, and solid-solid structural change on the isostress planes where temperature and intersurface distance are variable, and finally we propose a phase diagram of the confined water in the temperature-pressure-distance space.     

Transport properties and distribution of water molecules confined in hydrophobic nanopores and nanoslits

The transport properties, including the diffusivity and viscosity, of water confined in hydrophobic nanopores and nanoslits were studied by molecular dynamics simulations. The results show that the diffusion coefficient in nanopores and nanoslits is markedly lower than that in the bulk. But the viscosity is much larger than that in bulk. The parallel diffusion coefficient is obviously larger than the perpendicular ones. The diffusion coefficient in the channel pore is ever less than that in the slit pore at the same pore width, but the viscosity is larger. The temperature and density affect significantly the diffusivity and viscosity in nanopores and nanoslits. Lower density water exhibits some special characteristics on density profiles in nanopores and nanoslits at lower temperatures, and the density profiles show a change from homogeneous to inhomogeneous as the pore width is reduced. Even clusters occurred in micropores.     

Ultrafast optical Kerr effect spectroscopy of water confined in nanopores of the gelatin gel

We report on the investigation of a short-time collective dynamics of water confined in the pores of the gelatin gel, using the femtosecond optical Kerr effect spectroscopy. The ultrafast responses of water molecules obtained in bulk liquid and in three concentrations of gelatin gels are explained theoretically, both in a long time and in a short time regime, taking into account all molecular motions. We prove that the contribution of molecules involved in tetrahedral, strongly H-bonded structures stabilizing the gel network increases with the gel concentration. On the other hand the long-time relaxation of water molecules is significantly slowed down in the gel pores.     

Phase diagram of the hexamethylenetetramine: water system

Phase diagram of the hexamethylenetetramine–water system was studied with use of differential thermal analysis and powder X-ray diffraction methods. The only polyhydrate, with the composition (CH₂)₆N₄·6H₂O (m.p. = 12.9 °C), was found. New experimental data on the solubility of (CH₂)₆N₄ in water were obtained by different methods that show decreasing the (CH₂)₆N₄ solubility with increasing temperature.     

Phase diagram of the water–monoethanolamine system

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Aqueous electrolytes confined within functionalized silica nanopores

Molecular dynamics simulations have been carried out to investigate structural and dynamical characteristics of NaCl aqueous solutions confined within silica nanopores in contact with a "bulk-like" reservoir. Two types of pores, with diameters intermediate between 20 A? and 37.5 A?, were investigated: The first one corresponded to hydrophobic cavities, in which the prevailing wall-solution interactions were of the Lennard-Jones type. In addition, we also examined the behavior of solutions trapped within hydrophilic cavities, in which a set of unsaturated O-sites at the wall were transformed in polar silanol Si-OH groups. In all cases, the overall concentrations of the trapped electrolytes exhibited important reductions that, in the case of the narrowest pores, attained 50% of the bulk value. Local concentrations within the pores also showed important fluctuations. In hydrophobic cavities, the close vicinity of the pore wall was coated exclusively by the solvent, whereas in hydrophilic pores, selective adsorption of Na(+) ions was also observed. Mass and charge transport were also investigated. Individual diffusion coefficients did not present large modifications from what is perceived in the bulk; contrasting, the electrical conductivity exhibited important reductions. The qualitative differences are rationalized in terms of simple geometrical considerations.     

Dynamics of small-molecule glass formers confined in nanopores

We report a comparative neutron scattering study of the molecular mobility and nonexponential relaxation of three structurally similar glass-forming liquids, isopropanol, propylene glycol, and glycerol, both in bulk and confined in porous Vycor glass. Confinement reduces molecular mobility in all three liquids, and suppresses crystallization in isopropanol. High-resolution quasielastic neutron scattering spectra were fit to Fourier transformed Kohlrausch functions exp[-(t∕τ)(β)], describing the α-relaxation processes in these liquids. The stretching parameter β is roughly constant with wavevector Q and over the temperature range explored in bulk glycerol and propylene glycol, but varies both with Q and temperature in confinement. Average relaxation times <τ(Q)> are longer at lower temperatures and in confinement. They obey a power law <τ(Q)> ∝ Q(-γ), where the exponent γ is modified by confinement. Comparison of the bulk and confined liquids lends support to the idea that structural and∕or dynamical heterogeneity underlies the nonexponential relaxation of glass formers, as widely hypothesized in the literature.     

Phase diagram of androsterol-dipalmitoylphosphatidylcholine mixtures dispersed in excess water

The effect of androsterol, whose structure resembles that of cholesterol but without the alkyl side chain, on the phase behavior of aqueous dispersions of dipalmitoylphosphatidylcholine has been studied to understand the role of the side chain played in the formation of ordered phases of the type observed in membrane rafts. Thermotropic changes in the structure of mixed dispersions and transition enthalpies have been examined by synchrotron X-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. From these results a partial phase diagram of the binary system has been constructed. The three-phase line is determined to be 34.5 degrees C, which is 3-5 degrees C lower than that observed in binary mixtures of cholesterol, ergosterol, or stigmasterol with dipalmitoylphosphatidylcholine. The proportions of androsterol in mixtures representing the "left end point" and "right end point" of the three-phase line are 11.1 and 30.9 mol %, respectively. These proportions are greater than that seen in phase diagrams of other sterols codispersed with dipalmitoylphosphatidylcholine. We conclude that androsterol is less effective in promoting the formation of an ordered phase, and furthermore, this ordered phase is less compact than the normal lamellar liquid-ordered phase.     

NMR investigation of the porosity of hypercrosslinked polystyrene and the properties of water confined in its nanopores

The melting of water frozen preliminarily at 180 K in a free internal volume of water-swollen hypercrosslinked polystyrene networks with degrees of crosslinking ranging from 43 to 500% is studied by NMR. It is found that ice melts within a narrow range of low temperatures, 195?C225 K, demonstrating that the pores in the networks are small and uniform in size. It is, however, impossible to calculate the pore size via the Gibbs-Thomson equation, since the structure of water (and hence its properties) depend on a sample??s rate of freezing. We conclude that the activation of the orientational motions of water molecules starts to manifest itself already at 200 K; upon reaching 220?C230 K, the total mobility of water molecules is due largely to translational motions with an activation energy of 27?C28 kJ/mol.     

Thermodynamics of supercooled water

We review the available experimental information on the thermodynamic properties of supercooled water and demonstrate the possibility of modeling these thermodynamic properties on a theoretical basis. We show that by assuming the existence of a liquid-liquid critical point in supercooled water, the theory of critical phenomena can give an accurate account of the experimental thermodynamic-property data up to a pressure of 150 MPa. In addition, we show that a phenomenological extension of the theoretical model can account for all currently available experimental data in the supercooled region, up to 400 MPa. The stability limit of the liquid state and possible coupling between crystallization and liquid-liquid separation are also discussed. It is concluded that critical-point thermodynamics describes the available thermodynamic data for supercooled water within experimental accuracy, thus establishing a benchmark for further developments in this area.