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Sample records for aux interfaces liquide

  1. PREFACE: Functionalized Liquid Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Girault, Hubert; Kornyshev, Alexei A.; Monroe, Charles W.; Urbakh, Michael

    2007-09-01

    Most natural processes take place at interfaces. For this reason, surface science has been a focal point of modern research. At solid-liquid interfaces one can induce various species to adsorb or react, and thus may study interactions between the substrate and adsorbates, kinetic processes, optical properties, etc. Liquid-liquid interfaces, formed by immiscible liquids such as water and oil, have a number of distinctive features. Both sides of the interface are amenable to detailed physical and chemical analysis. By chemical or electrochemical means, metal or semiconductor nanoparticles can be formed or localised at the interface. Surfactants can be used to tailor surface properties, and also to place organic molecular or supermolecular constructions at the boundary between the liquids. Electric fields can be used to drive ions from one fluid to another, or even change the shape of the interface itself. In many cases, both liquids are optically transparent, making functionalized liquid-liquid interfaces promising for various optical applications based on the transmission or reflection of light. An advantage common to most of these systems is self-assembly; because a liquid-liquid interface is not mechanically constrained like a solid-liquid interface, it can easily access its most stable state, even after it has been driven far from equilibrium. This special issue focuses on four modes of liquid-liquid interfacial functionalization: the controlled adsorption of molecules or nanoparticles, the formation of adlayers or films, electrowetting, and ion transfer or interface-localized reactions. Interfacial adsorption can be driven electrically, chemically, or mechanically. The liquid-liquid interface can be used to study how anisotropic particles orient at a surface under the influence of a field, how surfactants interact with other adsorbates, and how nanoparticles aggregate; the transparency of the interface also makes the chirality of organic adsorbates amenable to

  2. Réactions aux interfaces de bicristaux compatibles et incompatibles

    NASA Astrophysics Data System (ADS)

    Taisne, A.; Décamps, B.; Priester, L.

    2003-03-01

    La rupture intergranulaire peut apparaître suite à la non accommodation des contraintes au voisinage de l'interface. La transmission du glissement au travers d'une interface est un des modes de relaxation possible qui dépend des paramètres suivants : facteurs géométriques (caractéristiques de l'interface et systèmes de glissement activés), constantes élastiques de chacune des phases. Dans cette étude, la microscopie électronique à transmission (MET) est utilisée pour analyser les configurations de dislocations résultant d'une déformation par fatigue de bicristaux d'acier austénoferritique de désorientations contrôlées. Deux types de bicristaux sont étudiés, compatible et incompatible plastiquement. Pour chacun d'eux, la déformation est initiée soit dans la phase ferritique α soit dans la phase austénitique γ selon la localisation d'une entaille préalable à l'essai mécanique. Les résultats permettent de remonter aux mécanismes élémentaires qui régissent le transfert “direct” ou “indirect” des dislocations à travers l'interface. Une corrélation avec le comportement des bicristaux à l'échelle macroscopique est également tentée.

  3. Reaction Dynamics at Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Benjamin, Ilan

    2015-04-01

    The liquid interface is a narrow, highly anisotropic region, characterized by rapidly varying density, polarity, and molecular structure. I review several aspects of interfacial solvation and show how these affect reactivity at liquid/liquid interfaces. I specifically consider ion transfer, electron transfer, and SN2 reactions, showing that solvent effects on these reactions can be understood by examining the unique structure and dynamics of the liquid interface region.

  4. Reaction dynamics at liquid interfaces.

    PubMed

    Benjamin, Ilan

    2015-04-01

    The liquid interface is a narrow, highly anisotropic region, characterized by rapidly varying density, polarity, and molecular structure. I review several aspects of interfacial solvation and show how these affect reactivity at liquid/liquid interfaces. I specifically consider ion transfer, electron transfer, and SN2 reactions, showing that solvent effects on these reactions can be understood by examining the unique structure and dynamics of the liquid interface region.

  5. Redox chemistry at liquid/liquid interfaces

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Deamer, D. W.

    1997-01-01

    The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

  6. Pattern formation at liquid interfaces

    NASA Astrophysics Data System (ADS)

    Heidel, Barbara; Knobler, Charles M.

    1990-01-01

    Quantitative experimental investigations of pattern formation at a liquid interface are described. The reaction studied is the photoreduction of Fe 3+ in aqueous solution and the subsequent formation of Turnbull's Blue. Both the wavelength of the pattern and the time at which the break in homogeneity occurs have been studied as functions of the concentrations of the reactants and the viscosity of the solvent. Many of the features of the process are consistent with a mechanism in which autocatalysis is enhanced by double diffusion. Preliminary studies of pattern formation in the KI/starch/chloralhydrate system are also presented.

  7. Self-diffusion in liquid interfaces.

    PubMed

    Herth, Simone; Ye, Feng; Eggersmann, Martin; Gutfleisch, Oliver; Würschum, Roland

    2004-03-05

    For studying self-diffusion in liquid interfaces, 59Fe tracer diffusion was measured on ultrafine-grained Nd2Fe14B which undergoes an intergranular melting transition for low Nd excess. The diffusion coefficient in the intergranular liquid layers is found to be lower than in bulk melts indicating a hampered atomic mobility due to confinement. Well above the intergranular melting transition, the diffusivity in the liquid interfaces approaches a value characteristic for bulk melts.

  8. Polymer Crystallization at Curved Liquid/Liquid Interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda

    Liquid/liquid interface, either flat or curved, is a unique template for studying self-assembly of a variety of nanomaterials such as nanoparticles and nanorods. The resultant monolayer films can be ordered or disordered depending on the regularity of the nanomaterials. Integration of nanoparticles into two-dimensional structure leads to intriguing collective properties of the nanoparticles. Crystallization can also be guided by liquid/liquid interface. Due to the particular shape of the interface, crystallization can happen in a different manner comparing to the normal solution crystallization. In this dissertation, liquid/liquid interface is employed to guide the crystallization of polymers, mainly focusing on using curved liquid/liquid interface. Due to the unique shape of the interface and feasibility to control the curvature, polymer crystallization can take place in different manner and lead to the formation of curved or vesicular crystals. Curved liquid/liquid interface is typically created through o/w emulsions. With the presence of surfactant, the emulsions are controlled to be stable at least for the polymer crystallization periods. The difference to normal solution crystallization is: the nuclei will diffuse to the curved interface due to the Pickering effect and guide the crystallization along the curved liquid/liquid interface. If the supercooling can be controlled to be very small, crystal growth in the bulk droplets can be avoided. The advantages of this strategy are: 1) the formation process of vesicular type crystals can be monitored by controlling the polymer supply; 2) curved crystals, bowl-like structures and enclosed capsules can be easily obtained comparing to the self-assembly method for vesicle formation; 3) the obtained vesicles will be made of polymer crystals, which will possess the extraordinary mechanical properties. Based on the nucleation type, this dissertation is divided into two parts. The first part is focused on the self

  9. Nanomaterials at Liquid/Liquid Interfaces-A Review.

    PubMed

    Divya, V; Sangaranarayanan, M V

    2015-09-01

    The charge transfer processes occurring at the interface between two immiscible electrolyte solutions are of considerable importance in diverse fields of chemistry and biology. The introduction to nanoparticles and analysis of nanostructures in diverse branches of science and engineering are provided. The chemical and electrochemical techniques pertaining to the synthesis of metal nanoparticles, polymeric nanostructures and metal-polymer nanocomposites at liquid/liquid interfaces are surveyed. The unique features pertaining to the chemical synthesis of metal nanoparticles while employing diverse electrolytes and solvents are outlined. The advantages of various electrochemical synthetic protocols such as four-electrode assembly, thin film electrode, Scanning Electrochemical Microscopy and Solid/liquid/liquid interfaces for the study of nanoparticles at liquid/liquid interfaces are emphasized. The crucial role played by the liquid/liquid interfaces in altering the morphological patterns of metal nanoparticles, conducting polymers and metal-polymer nanocomposites is indicated. A few typical novel applications of these nanomaterials in fabrication of biosensors, electrochemical supercapacitors, and electrocatalysts have been outlined.

  10. Low frequency ionic conduction across liquid interfaces

    NASA Astrophysics Data System (ADS)

    Solis, Francisco J.; Guerrero, Guillermo Ivan; Olvera de La Cruz, Monica

    Ionic conduction in liquid media is a central component of many recently proposed technologies. As in the case of solid state systems, the presence of heterogeneous media gives rise to interesting nonlinear phenomena. We present simulations and theoretical analysis of the low frequency ionic conduction in a two-liquid system. In the case analyzed, the conduction is driven by an electric field perpendicular to the liquid-liquid interface. We show that the dielectric contrast between the liquids produces non-linear effects in the effective conductivity of the system and discuss the effects of the ion solubility in the media.

  11. Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Gugeshashvili, M. I.; Deamer, D. W.

    1995-01-01

    This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

  12. Reactions and Polymerizations at the Liquid-Liquid Interface.

    PubMed

    Piradashvili, Keti; Alexandrino, Evandro M; Wurm, Frederik R; Landfester, Katharina

    2016-02-24

    Reactions and polymerizations at the interface of two immiscible liquids are reviewed. The confinement of two reactants at the interface to form a new product can be advantageous in terms of improved reaction kinetics, higher yields, and selectivity. The presence of the liquid-liquid interface can accelerate the reaction, or a phase-transfer catalyst is employed to draw the reaction in one phase of choice. Furthermore, the use of immiscible systems, e.g., in emulsions, offers an easy means of efficient product separation and heat dissipation. A general overview on low molecular weight organic chemistry is given, and the applications of heterophase polymerization, occurring at or in proximity of the interface, (mostly) in emulsions are presented. This strategy can be used for the efficient production of nano- and microcarriers for various applications.

  13. Structural Transitions at Ionic Liquid Interfaces.

    PubMed

    Rotenberg, Benjamin; Salanne, Mathieu

    2015-12-17

    Recent advances in experimental and computational techniques have allowed for an accurate description of the adsorption of ionic liquids on metallic electrodes. It is now well-established that they adopt a multilayered structure and that the composition of the layers changes with the potential of the electrode. In some cases, potential-driven ordering transitions in the first adsorbed layer have been observed in experiments probing the interface on the molecular scale or by molecular simulations. This perspective gives an overview of the current understanding of such transitions and of their potential impact on the physical and (electro)chemical processes at the interface. In particular, peaks in the differential capacitance, slow dynamics at the interface, and changes in the reactivity have been reported in electrochemical studies. Interfaces between ionic liquids and metallic electrodes are also highly relevant for their friction properties, the voltage-dependence of which opens the way to exciting applications.

  14. Liquid crystal interfaces: Experiments, simulations and biosensors

    NASA Astrophysics Data System (ADS)

    Popov, Piotr

    Interfacial phenomena are ubiquitous and extremely important in various aspects of biological and industrial processes. For example, many liquid crystal applications start by alignment with a surface. The underlying mechanisms of the molecular organization of liquid crystals at an interface are still under intensive study and continue to be important to the display industry in order to develop better and/or new display technology. My dissertation research has been devoted to studying how complex liquid crystals can be guided to organize at an interface, and to using my findings to develop practical applications. Specifically, I have been working on developing biosensors using liquid-crystal/surfactant/lipid/protein interactions as well as the alignment of low-symmetry liquid crystals for potential new display and optomechanical applications. The biotechnology industry needs better ways of sensing biomaterials and identifying various nanoscale events at biological interfaces and in aqueous solutions. Sensors in which the recognition material is a liquid crystal naturally connects the existing knowledge and experience of the display and biotechnology industries together with surface and soft matter sciences. This dissertation thus mainly focuses on the delicate phenomena that happen at liquid interfaces. In the introduction, I start by defining the interface and discuss its structure and the relevant interfacial forces. I then introduce the general characteristics of biosensors and, in particular, describe the design of biosensors that employ liquid crystal/aqueous solution interfaces. I further describe the basic properties of liquid crystal materials that are relevant for liquid crystal-based biosensing applications. In CHAPTER 2, I describe the simulation methods and experimental techniques used in this dissertation. In CHAPTER 3 and CHAPTER 4, I present my computer simulation work. CHAPTER 3 presents insight of how liquid crystal molecules are aligned by

  15. A molecular theory of liquid interfaces.

    PubMed

    Kovalenko, Andriy; Hirata, Fumio

    2005-04-21

    We propose a site site generalization of the Lovett-Mow-Buff-Wertheim integro-differential equation for the one-particle density distributions to polyatomic fluids. The method provides microscopic description of liquid interfaces of molecular fluids and solutions. It uses the inhomogeneous site-site direct correlation function of molecular fluid consistently constructed by nonlinear interpolation between the homogeneous ones. The site site correlations of the coexisting bulk phases are obtained from the reference interaction site model (RISM) integral equation with our closure approximation. For illustration, we calculated the structure of the planar liquid-vapor as well as liquid-liquid interfaces of n-hexane and methanol at ambient conditions.

  16. Particle Behavior at Anisotropically Curved Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    McEnnis, Kathleen; Zeng, Chuan; Davidovitch, Benny; Dinsmore, Anthony; Russell, Thomas

    2011-03-01

    A particle bound to an anisotropically curved liquid interface, such as a cylinder or catenoid, cannot maintain a constant contact angle without deforming the interface. Theory suggests that the particles will experience a force that depends on the interfacial shape and migrate to minimize the total interfacial energy. To test these predictions, particles were deposited on top of liquid semi-cylinders of ionic liquid or melted polystyrene confined on chemically patterned surfaces. Particles were also deposited on liquid catenoid structures created by placing a melted polymer film under an electric field. The location of the particles on these structures was observed by optical, confocal, and scanning electron microscopy. The implications for the directed assembly of particles and stability of Pickering emulsions are also discussed.

  17. Gas-liquid interface of room-temperature ionic liquids.

    PubMed

    Santos, Cherry S; Baldelli, Steven

    2010-06-01

    The organization of ions at the interface of ionic liquids and the vacuum is an ideal system to test new ideas and concepts on the interfacial chemistry of electrolyte systems in the limit of no solvent medium. Whilst electrolyte systems have numerous theoretical and experimental methods used to investigate their properties, the ionic liquids are relatively new and our understanding of the interfacial properties is just beginning to be explored. In this critical review, the gas-liquid interface is reviewed, as this interface does not depend on the preparation of another medium and thus produces a natural interface. The interface has been investigated by sum frequency generation vibrational spectroscopy and ultra-high vacuum techniques. The results provide a detailed molecular-level view of the surface composition and structure. These have been complemented by theoretical studies. The combinations of treatments on this interface are starting to provide a somewhat convergent description of how the ions are organized at this neat interface (108 references).

  18. Second harmonic studies of liquid interfaces

    SciTech Connect

    Ong, S.

    1992-12-31

    This thesis reports on experimental studies of kinetics and equilibria at liquid interfaces using the technique of Second Harmonic Generation (SHG). In the first part, SHG was used to study the kinetics of adsorption of p-nitrophenol at the air/water interface of a flowing liquid jet. Measurements of the SH signal strength and the polarization of the SH light at various distances (times) along the jet axis yield information about the development of the density and orientation of p-nitrophenol at the air/water interface. The kinetics of adsorption was interpreted in terms of the Langmuir theory and was found to be consistent with this model. The free energy of adsorption obtained from the jet experiments was found to be the same as that obtained from static (equilibrium) experiments. The orientation of p-nitrophenol at the jet air/solution interface was the same as for the static (equilibrium) interface,which indicates that orientational equilibrium was rapidly achieved. It was also found that adsorption of nitrophenol to the air/water interface is not diffusion controlled, but rather is kinetically controlled by a barrier. SHG was then used to probe the silica/water interface.

  19. Solid-Liquid Interface Characterization Hardware

    NASA Technical Reports Server (NTRS)

    Peters, Palmer N.

    2000-01-01

    The objective is to develop enabling technology to characterize the solid-liquid interface during directional solidification to unprecedented levels with real-time measurement hardware. Existing x-ray imaging hardware is combined with compact Seebeck furnaces and thermal profiling hardware, under development, to accomplish the measurements. Furnace thermal profiles are continuously measured in addition to the sample characteristics.

  20. Microrheology and Particle Dynamics at Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Song, Yanmei

    The rheological properties at liquid-liquid interfaces are important in many industrial processes such as manufacturing foods, pharmaceuticals, cosmetics, and petroleum products. This dissertation focuses on the study of linear viscoelastic properties at liquid-liquid interfaces by tracking the thermal motion of particles confined at the interfaces. The technique of interfacial microrheology is first developed using one- and two-particle tracking, respectively. In one-particle interfacial microrheology, the rheological response at the interface is measured from the motion of individual particles. One-particle interfacial microrheology at polydimethylsiloxane (PDMS) oil-water interfaces depends strongly on the surface chemistry of different tracer particles. In contrast, by tracking the correlated motion of particle pairs, two-particle interfacial microrheology significantly minimizes the effects from tracer particle surface chemistry and particle size. Two-particle interfacial microrheology is further applied to study the linear viscoelastic properties of immiscible polymer-polymer interfaces. The interfacial loss and storage moduli at PDMS-polyethylene glycol (PEG) interfaces are measured over a wide frequency range. The zero-shear interfacial viscosity, estimated from the Cross model, falls between the bulk viscosities of two individual polymers. Surprisingly, the interfacial relaxation time is observed to be an order of magnitude larger than that of the PDMS bulk polymers. To explore the fundamental basis of interfacial nanorheology, molecular dynamics (MD) simulations are employed to investigate the nanoparticle dynamics. The diffusion of single nanoparticles in pure water and low-viscosity PDMS oils is reasonably consistent with the prediction by the Stokes-Einstein equation. To demonstrate the potential of nanorheology based on the motion of nanoparticles, the shear moduli and viscosities of the bulk phases and interfaces are calculated from single

  1. Liquid film/polymer interfaces

    SciTech Connect

    Allara, David L.

    2003-06-12

    The objectives were: (1) Through experimental studies, advance the fundamental understanding of the principles that govern adsorption and wetting phenomena at polymer and organic surfaces. (2) Establish a firm scientific basis for improving the design of coatings for metal fin cooling surfaces used to control the wetting of water condensate for optimum energy efficiency. Several important findings were: (1) water adsorbed at hydrophobic surfaces has a liquid-like structure, in contrast to the generally held view of an ordered structure; (2) Correlations of large amounts of contact angle wetting data of grafted alkyl chain compounds showed a distinct link between the contact angle and the conformational ordering of the chains; (3) water adsorption at long chain alkysiloxane films showed a strong pH dependence on the film stability, which can be attributed to interfacial chemical effects on the siloxane network.

  2. Liquid-vapor interfaces of patchy colloids

    NASA Astrophysics Data System (ADS)

    Oleksy, A.; Teixeira, P. I. C.

    2015-01-01

    We investigate the liquid-vapor interface of a model of patchy colloids. This model consists of hard spheres decorated with short-ranged attractive sites ("patches") of different types on their surfaces. We focus on a one-component fluid with two patches of type A and nine patches of type B (2 A 9 B colloids), which has been found to exhibit reentrant liquid-vapor coexistence curves and very low-density liquid phases. We have used the density-functional theory form of Wertheim's first-order perturbation theory of association, as implemented by Yu and Wu [J. Chem. Phys. 116, 7094 (2002), 10.1063/1.1463435], to calculate the surface tension, and the density and degree of association profiles, at the liquid-vapor interface of our model. In reentrant systems, where A B bonds dominate, an unusual thickening of the interface is observed at low temperatures. Furthermore, the surface tension versus temperature curve reaches a maximum, in agreement with Bernardino and Telo da Gama's mesoscopic Landau-Safran theory [Phys. Rev. Lett. 109, 116103 (2012), 10.1103/PhysRevLett.109.116103]. If B B attractions are also present, competition between A B and B B bonds gradually restores the monotonic temperature dependence of the surface tension. Lastly, the interface is "hairy," i.e., it contains a region where the average chain length is close to that in the bulk liquid, but where the density is that of the vapor. Sufficiently strong B B attractions remove these features, and the system reverts to the behavior seen in atomic fluids.

  3. Systems and methods for monitoring a solid-liquid interface

    DOEpatents

    Stoddard, Nathan G; Lewis, Monte A.; Clark, Roger F

    2013-06-11

    Systems and methods are provided for monitoring a solid-liquid interface during a casting process. The systems and methods enable determination of the location of a solid-liquid interface during the casting process.

  4. Interface for liquid chromatograph-mass spectrometer

    DOEpatents

    Andresen, B.D.; Fought, E.R.

    1989-09-19

    A moving belt interface is described for real-time, high-performance liquid chromatograph (HPLC)/mass spectrometer (MS) analysis which strips away the HPLC solvent as it emerges from the end of the HPLC column and leaves a residue suitable for mass-spectral analysis. The interface includes a portable, stand-alone apparatus having a plural stage vacuum station, a continuous ribbon or belt, a drive train magnetically coupled to an external drive motor, a calibrated HPLC delivery system, a heated probe tip and means located adjacent the probe tip for direct ionization of the residue on the belt. The interface is also capable of being readily adapted to fit any mass spectrometer. 8 figs.

  5. Interface for liquid chromatograph-mass spectrometer

    DOEpatents

    Andresen, Brian D.; Fought, Eric R.

    1989-01-01

    A moving belt interface for real-time, high-performance liquid chromatograph (HPLC)/mass spectrometer (MS) analysis which strips away the HPLC solvent as it emerges from the end of the HPLC column and leaves a residue suitable for mass-spectral analysis. The interface includes a portable, stand-alone apparatus having a plural stage vacuum station, a continuous ribbon or belt, a drive train magnetically coupled to an external drive motor, a calibrated HPLC delivery system, a heated probe tip and means located adjacent the probe tip for direct ionization of the residue on the belt. The interface is also capable of being readily adapted to fit any mass spectrometer.

  6. Solidification along the interface between demixed liquids in monotectic systems.

    PubMed

    Hüter, C; Boussinot, G; Brener, E A; Temkin, D E

    2011-05-01

    The steady-state solidification along the liquid-liquid interface in the monotectic system is discussed. A boundary-integral formulation describing the diffusion in the two liquid phases is given and the corresponding equations for the three interfaces (two solid-liquid interfaces and one liquid-liquid interface) are solved. Scaling relations are extracted from the results and supported by analytic arguments in the limit of small deviation from the monotectic temperature. We present also a complementary phase-field simulation, which proves the stability of the process.

  7. Electroviscoelasticity of liquid/liquid interfaces: fractional-order model.

    PubMed

    Spasic, Aleksandar M; Lazarevic, Mihailo P

    2005-02-01

    A number of theories that describe the behavior of liquid-liquid interfaces have been developed and applied to various dispersed systems, e.g., Stokes, Reiner-Rivelin, Ericksen, Einstein, Smoluchowski, and Kinch. A new theory of electroviscoelasticity describes the behavior of electrified liquid-liquid interfaces in fine dispersed systems and is based on a new constitutive model of liquids. According to this model liquid-liquid droplet or droplet-film structure (collective of particles) is considered as a macroscopic system with internal structure determined by the way the molecules (ions) are tuned (structured) into the primary components of a cluster configuration. How the tuning/structuring occurs depends on the physical fields involved, both potential (elastic forces) and nonpotential (resistance forces). All these microelements of the primary structure can be considered as electromechanical oscillators assembled into groups, so that excitation by an external physical field may cause oscillations at the resonant/characteristic frequency of the system itself (coupling at the characteristic frequency). Up to now, three possible mathematical formalisms have been discussed related to the theory of electroviscoelasticity. The first is the tension tensor model, where the normal and tangential forces are considered, only in mathematical formalism, regardless of their origin (mechanical and/or electrical). The second is the Van der Pol derivative model, presented by linear and nonlinear differential equations. Finally, the third model presents an effort to generalize the previous Van der Pol equation: the ordinary time derivative and integral are now replaced with the corresponding fractional-order time derivative and integral of order p<1.

  8. Single Fusion Events at Polarized Liquid-Liquid Interfaces.

    PubMed

    Laborda, Eduardo; Molina, Angela; Espín, Vanesa Fernández; Martínez-Ortiz, Francisco; García de la Torre, José; Compton, Richard G

    2017-01-16

    A new electrochemical framework for tracking individual soft particles in solution and monitoring their fusion with polarized liquid-liquid interfaces is reported. The physicochemical principle lies in the interfacial transfer of an ionic probe confined in the particles dispersed in solution and that is released upon their collision and fusion with the fluid interface. As a proof-of-concept, spike-like transients of a stochastic nature are reported in the current-time response of 1,2-dichloroethane(DCE)|water(W) submilli-interfaces after injection of DCE-in-W emulsions. The sign and potential dependence of the spikes reflect the charge and lipophilicity of the ionic load of the droplets. A comparison with dynamic light scattering measurements indicates that each spike is associated with the collision of a single sub-picoliter droplet. This opens a new framework for the study of single fusion events at the micro- and nanoscale and of ion transport across biomimetic soft interfaces.

  9. Layerless fabrication with continuous liquid interface production

    PubMed Central

    Janusziewicz, Rima; Tumbleston, John R.; Quintanilla, Adam L.; Mecham, Sue J.; DeSimone, Joseph M.

    2016-01-01

    Despite the increasing popularity of 3D printing, also known as additive manufacturing (AM), the technique has not developed beyond the realm of rapid prototyping. This confinement of the field can be attributed to the inherent flaws of layer-by-layer printing and, in particular, anisotropic mechanical properties that depend on print direction, visible by the staircasing surface finish effect. Continuous liquid interface production (CLIP) is an alternative approach to AM that capitalizes on the fundamental principle of oxygen-inhibited photopolymerization to generate a continual liquid interface of uncured resin between the growing part and the exposure window. This interface eliminates the necessity of an iterative layer-by-layer process, allowing for continuous production. Herein we report the advantages of continuous production, specifically the fabrication of layerless parts. These advantages enable the fabrication of large overhangs without the use of supports, reduction of the staircasing effect without compromising fabrication time, and isotropic mechanical properties. Combined, these advantages result in multiple indicators of layerless and monolithic fabrication using CLIP technology. PMID:27671641

  10. Layerless fabrication with continuous liquid interface production.

    PubMed

    Janusziewicz, Rima; Tumbleston, John R; Quintanilla, Adam L; Mecham, Sue J; DeSimone, Joseph M

    2016-10-18

    Despite the increasing popularity of 3D printing, also known as additive manufacturing (AM), the technique has not developed beyond the realm of rapid prototyping. This confinement of the field can be attributed to the inherent flaws of layer-by-layer printing and, in particular, anisotropic mechanical properties that depend on print direction, visible by the staircasing surface finish effect. Continuous liquid interface production (CLIP) is an alternative approach to AM that capitalizes on the fundamental principle of oxygen-inhibited photopolymerization to generate a continual liquid interface of uncured resin between the growing part and the exposure window. This interface eliminates the necessity of an iterative layer-by-layer process, allowing for continuous production. Herein we report the advantages of continuous production, specifically the fabrication of layerless parts. These advantages enable the fabrication of large overhangs without the use of supports, reduction of the staircasing effect without compromising fabrication time, and isotropic mechanical properties. Combined, these advantages result in multiple indicators of layerless and monolithic fabrication using CLIP technology.

  11. Wave-based liquid-interface metamaterials

    NASA Astrophysics Data System (ADS)

    Francois, N.; Xia, H.; Punzmann, H.; Fontana, P. W.; Shats, M.

    2017-02-01

    The control of matter motion at liquid-gas interfaces opens an opportunity to create two-dimensional materials with remotely tunable properties. In analogy with optical lattices used in ultra-cold atom physics, such materials can be created by a wave field capable of dynamically guiding matter into periodic spatial structures. Here we show experimentally that such structures can be realized at the macroscopic scale on a liquid surface by using rotating waves. The wave angular momentum is transferred to floating micro-particles, guiding them along closed trajectories. These orbits form stable spatially periodic patterns, the unit cells of a two-dimensional wave-based material. Such dynamic patterns, a mirror image of the concept of metamaterials, are scalable and biocompatible. They can be used in assembly applications, conversion of wave energy into mean two-dimensional flows and for organising motion of active swimmers.

  12. Wave-based liquid-interface metamaterials

    PubMed Central

    Francois, N; Xia, H; Punzmann, H; Fontana, P W; Shats, M

    2017-01-01

    The control of matter motion at liquid–gas interfaces opens an opportunity to create two-dimensional materials with remotely tunable properties. In analogy with optical lattices used in ultra-cold atom physics, such materials can be created by a wave field capable of dynamically guiding matter into periodic spatial structures. Here we show experimentally that such structures can be realized at the macroscopic scale on a liquid surface by using rotating waves. The wave angular momentum is transferred to floating micro-particles, guiding them along closed trajectories. These orbits form stable spatially periodic patterns, the unit cells of a two-dimensional wave-based material. Such dynamic patterns, a mirror image of the concept of metamaterials, are scalable and biocompatible. They can be used in assembly applications, conversion of wave energy into mean two-dimensional flows and for organising motion of active swimmers. PMID:28181490

  13. Dispersion of Particles on Fluid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Dalal, B.; Gurupatham, S.; Hossain, M.; Fischer, I.; Singh, P.; Joseph, D.

    2011-11-01

    This talk is concerned with the dispersion of particles on the fluid-liquid interface. In our previous studies we have shown that when small particles, e.g., flour, pollen, etc., come in contact with an air-liquid interface, they disperse in a manner that appears explosive. This is due to the fact that the capillary force pulls particles into the interface causing them to accelerate to a relatively-large velocity. The motion of particles in the direction normal to the interface is inertia dominated, and so they oscillate vertically about the equilibrium position before coming to a stop under viscous drag. This causes a radially-outward lateral flow on the interface that causes nearby particles to move away. In experiments the strength of the lateral flow was measured using tracer particles that were placed on the interface for this purpose. The dispersion on a liquid-liquid interface was relatively weaker than on an air-liquid interface, and occurred over a longer period of time. This partly was a consequence of the fact that particles became separated while sedimenting through the upper liquid and reached the interface over a time interval that lasted for several seconds. The rate of dispersion depended on the size of particles, the particle and liquids densities, the viscosities of the liquids involved, and the contact angle.

  14. Phase Segregation at the Liquid-Air Interface Prior to Liquid-Liquid Equilibrium.

    PubMed

    Bermúdez-Salguero, Carolina; Gracia-Fadrique, Jesús

    2015-08-13

    Binary systems with partial miscibility segregate into two liquid phases when their overall composition lies within the interval defined by the saturation points; out of this interval, there is one single phase, either solvent-rich or solute-rich. In most systems, in the one-phase regions, surface tension decreases with increasing solute concentration due to solute adsorption at the liquid-air interface. Therefore, the solute concentration at the surface is higher than in the bulk, leading to the hypothesis that phase segregation starts at the liquid-air interface with the formation of two surface phases, before the liquid-liquid equilibrium. This phenomenon is called surface segregation and is a step toward understanding liquid segregation at a molecular level and detailing the constitution of fluid interfaces. Surface segregation of aqueous binary systems of alkyl acetates with partial miscibility was theoretically demonstrated by means of a thermodynamic stability test based on energy minimization. Experimentally, the coexistence of two surface regions was verified through Brewster's angle microscopy. The observations were further interpreted with the aid of molecular dynamics simulations, which show the diffusion of the acetates from the bulk toward the liquid-air interface, where acetates aggregate into acetate-rich domains.

  15. (The physics of pattern formation at liquid interfaces)

    SciTech Connect

    Not Available

    1990-01-01

    This paper discusses pattern formation at liquid interfaces and interfaces within disordered materials. The particular topics discussed are: a racetrack for competing viscous fingers; an experimental realization of periodic boundary conditions; what sets the length scale for patterns between miscible liquids; the fractal dimension of radial Hele-Shaw patterns; detailed analyses of low-contrast Saffman-Taylor flows; and the wetting/absorption properties of polystyrene spheres in binary liquid mixtures. (LSP)

  16. LSPR properties of metal nanoparticles adsorbed at a liquid-liquid interface.

    PubMed

    Yang, Zhilin; Chen, Shu; Fang, Pingping; Ren, Bin; Girault, Hubert H; Tian, Zhongqun

    2013-04-21

    Unlike the solid-air and solid-liquid interfaces, the optical properties of metal nanoparticles adsorbed at the liquid-liquid interface have not been theoretically exploited to date. In this work, the three dimensional finite difference time domain (3D-FDTD) method is employed to clarify the localized surface plasmon resonance (LSPR) based optical properties of gold nanoparticles (NPs) adsorbed at the water-oil interface, including near field distribution, far field absorption and their relevance. The LSPR spectra of NPs located at a liquid-liquid interface are shown to differ significantly from those in a uniform liquid environment or at the other interfaces. The absorption spectra exhibit two distinct LSPR peaks, the positions and relative strengths of which are sensitive to the dielectric properties of each liquid and the exact positions of the NPs with respect to the interface. Precise control of the particles' position and selection of the appropriate wavelength of the excitation laser facilitates the rational design and selective excitation of localized plasmon modes for interfacial NPs, a necessary advance for the exploration of liquid-liquid interfaces via surface enhanced Raman spectroscopy (SERS). According to our calculations, the SERS enhancement factor for Au nanosphere dimers at the water-oil interface can be as high as 10(7)-10(9), implying significant promise for future investigations of interfacial structure and applications of liquid-liquid interfaces towards chemical analysis.

  17. Polarity of the interface in ionic liquid in oil microemulsions.

    PubMed

    Andújar-Matalobos, María; García-Río, Luis; López-García, Susana; Rodríguez-Dafonte, Pedro

    2011-11-01

    Ionic liquid based microemulsions were characterized by absorption solvatochromic shifts, (1)H NMR and kinetic measurements in order to investigate the properties of the ionic liquid within the restricted geometry provided by microemulsions and the interactions of the ionic liquid with the interface. Experimental results show a significant difference between the interfaces of normal water and the new ionic liquid microemulsions. Absorption solvatochromic shift experiments and kinetic studies on the aminolysis of 4-nitrophenyl laurate by n-decylamine show that the polarity at the interface of the ionic liquid in oil microemulsions (IL/O) is higher than at the interface of water in oil microemulsions (W/O) despite the fact that the polarity of [bmim][BF(4)(-)] is lower than the polarity of water. (1)H NMR experiments showed that an increase in the ionic liquid content of the microemulsion led to an increase in the interaction between [bmim][BF(4)(-)] and TX-100. The reason for the higher polarity of the microemulsions with the ionic liquid can be explained in terms of the incorporation of higher levels of the ionic liquid at the interface of the microemulsions, as compared to water in the traditional systems.

  18. Thermal Convection Affects Shape Of Solid/Liquid Interface

    NASA Technical Reports Server (NTRS)

    Mennetrier, C.; Chopra, M. A.; Yao, M.; De Groh, H. C., III; Yeoh, G. H.; De Vahl Davis, G.; Leonardi, E.

    1994-01-01

    Report describes experimental and theoretical study of effect of thermal convection on shape of interface between solid and liquid succinonitrile, clear commercially available plastic, in Bridgman (directional-solidification) apparatus in vertical and horizontal orientations.

  19. Probing Electrochemical Reactions at a Plasma-Liquid Interface

    DTIC Science & Technology

    2015-03-16

    SECURITY CLASSIFICATION OF: The goal of this ARO STIR was to conduct preliminary investigations toward understanding electrochemical reactions...Mar-2015 Approved for Public Release; Distribution Unlimited Final Report: STIR: Probing Electrochemical Reactions at a Plasma-Liquid Interface (7.2...in peer-reviewed journals: Final Report: STIR: Probing Electrochemical Reactions at a Plasma-Liquid Interface (7.2 Electrochemistry) Report Title The

  20. Computer modelling of the surface tension of the gas-liquid and liquid-liquid interface.

    PubMed

    Ghoufi, Aziz; Malfreyt, Patrice; Tildesley, Dominic J

    2016-03-07

    This review presents the state of the art in molecular simulations of interfacial systems and of the calculation of the surface tension from the underlying intermolecular potential. We provide a short account of different methodological factors (size-effects, truncation procedures, long-range corrections and potential models) that can affect the results of the simulations. Accurate calculations are presented for the calculation of the surface tension as a function of the temperature, pressure and composition by considering the planar gas-liquid interface of a range of molecular fluids. In particular, we consider the challenging problems of reproducing the interfacial tension of salt solutions as a function of the salt molality; the simulations of spherical interfaces including the calculation of the sign and size of the Tolman length for a spherical droplet; the use of coarse-grained models in the calculation of the interfacial tension of liquid-liquid surfaces and the mesoscopic simulations of oil-water-surfactant interfacial systems.

  1. Enzyme Activity and Biomolecule Templating at Liquid and Solid Interfaces

    SciTech Connect

    Harvey W. Blanch

    2004-12-01

    There are two main components of this research program. The first involves studies of the adsorption and catalytic activity of proteins at fluid-fluid and fluid-solid interfaces; the second employs biological macromolecules as templates at the solid-liquid interface for controlled crystallization of inorganic materials, to provide materials with specific functionality.

  2. Nanofluidic transport governed by the liquid/vapour interface.

    PubMed

    Lee, Jongho; Laoui, Tahar; Karnik, Rohit

    2014-04-01

    Liquid/vapour interfaces govern the behaviour of a wide range of systems but remain poorly understood, leaving ample margin for the exploitation of intriguing functionalities for applications. Here, we systematically investigate the role of liquid/vapour interfaces in the transport of water across apposing liquid menisci in osmosis membranes comprising short hydrophobic nanopores that separate two fluid reservoirs. We show experimentally that mass transport is limited by molecular reflection from the liquid/vapour interface below a certain length scale, which depends on the transmission probability of water molecules across the nanopores and on the condensation probability of a water molecule incident on the liquid surface. This fundamental yet elusive condensation property of water is measured under near-equilibrium conditions and found to decrease from 0.36 ± 0.21 at 30 °C to 0.18 ± 0.09 at 60 °C. These findings define the regime in which liquid/vapour interfaces govern nanofluidic transport and have implications for understanding mass transport in nanofluidic devices, droplets and bubbles, biological components and porous media involving liquid/vapour interfaces.

  3. Self-assembly of a surfactin nanolayer at solid-liquid and air-liquid interfaces.

    PubMed

    Onaizi, Sagheer A; Nasser, M S; Al-Lagtah, Nasir M A

    2016-05-01

    Surfactin, a sustainable and environmentally friendly surface active agent, is used as a model to study the adsorption of biosurfactants at hydrophobic and hydrophilic solid-liquid interfaces as well as the air-liquid interface. Surfactin adsorption was monitored as a function of time and concentration using surface plasmon resonance (SPR) technique in the case of the solid-liquid interfaces or the drop shape analysis (DSA) technique in the case of the air-liquid interface. The results obtained in this study showed that surfactin adsorption at the "hard" hydrophobic (functionalized with octadecanethiol) solid-liquid and the "soft" air-liquid interface were 1.12 ± 0.01 mg m(-2) (area per molecule of 157 ± 2 Å(2)) and 1.11 ± 0.05 mg m(-2) (area per molecule of 159 ± 7 Å(2)), respectively, demonstrating the negligible effect of the interface "hardness" on surfactin adsorption. The adsorption of surfactin at the hydrophilic (functionalized with β-mercaptoethanol) solid-liquid interface was about threefold lower than its adsorption at the hydrophobic-liquid interfaces, revealing the importance of hydrophobic interaction in surfactin adsorption process. The affinity constant of surfactin for the investigated interfaces follows the following order: air > octadecanethiol > β-mercaptoethanol. Biosurfactants, such as surfactin, are expected to replace the conventional fossil-based surfactants in several applications, and therefore the current study is a contribution towards the fundamental understanding of biosurfactant behavior, on a molecular level, at hydrophobic and hydrophilic solid-liquid interfaces in addition to the air-liquid interface. Such understanding might aid further optimization of the utilization of surfactin in a number of industrial applications such as enhanced oil recovery, bioremediation, and detergency.

  4. Superhydrophobic-like tunable droplet bouncing on slippery liquid interfaces

    PubMed Central

    Hao, Chonglei; Li, Jing; Liu, Yuan; Zhou, Xiaofeng; Liu, Yahua; Liu, Rong; Che, Lufeng; Zhou, Wenzhong; Sun, Dong; Li, Lawrence; Xu, Lei; Wang, Zuankai

    2015-01-01

    Droplet impacting on solid or liquid interfaces is a ubiquitous phenomenon in nature. Although complete rebound of droplets is widely observed on superhydrophobic surfaces, the bouncing of droplets on liquid is usually vulnerable due to easy collapse of entrapped air pocket underneath the impinging droplet. Here, we report a superhydrophobic-like bouncing regime on thin liquid film, characterized by the contact time, the spreading dynamics, and the restitution coefficient independent of underlying liquid film. Through experimental exploration and theoretical analysis, we demonstrate that the manifestation of such a superhydrophobic-like bouncing necessitates an intricate interplay between the Weber number, the thickness and viscosity of liquid film. Such insights allow us to tune the droplet behaviours in a well-controlled fashion. We anticipate that the combination of superhydrophobic-like bouncing with inherent advantages of emerging slippery liquid interfaces will find a wide range of applications. PMID:26250403

  5. Superhydrophobic-like tunable droplet bouncing on slippery liquid interfaces

    NASA Astrophysics Data System (ADS)

    Hao, Chonglei; Wang, Zuankai

    2015-11-01

    Droplet impacting on solid or liquid interfaces is a ubiquitous phenomenon in nature. Although complete rebound of droplets is widely observed on superhydrophobic surfaces, the bouncing of droplets on liquid is usually vulnerable due to easy collapse of entrapped air pocket underneath the impinging droplet. Here, we report a superhydrophobic-like bouncing regime on thin liquid film, characterized by the contact time, the spreading dynamics, and the restitution coefficient independent of underlying liquid film. Through experimental exploration and theoretical analysis, we demonstrate that the manifestation of such a superhydrophobic-like bouncing necessitates an intricate interplay between the Weber number, the thickness and viscosity of liquid film. Such insights allow us to tune the droplet behaviors in a well-controlled fashion. We anticipate that the combination of superhydrophobic-like bouncing with inherent advantages of emerging slippery liquid interfaces will find a wide range of applications.

  6. Superhydrophobic-like tunable droplet bouncing on slippery liquid interfaces

    NASA Astrophysics Data System (ADS)

    Hao, Chonglei; Li, Jing; Liu, Yuan; Zhou, Xiaofeng; Liu, Yahua; Liu, Rong; Che, Lufeng; Zhou, Wenzhong; Sun, Dong; Li, Lawrence; Xu, Lei; Wang, Zuankai

    2015-08-01

    Droplet impacting on solid or liquid interfaces is a ubiquitous phenomenon in nature. Although complete rebound of droplets is widely observed on superhydrophobic surfaces, the bouncing of droplets on liquid is usually vulnerable due to easy collapse of entrapped air pocket underneath the impinging droplet. Here, we report a superhydrophobic-like bouncing regime on thin liquid film, characterized by the contact time, the spreading dynamics, and the restitution coefficient independent of underlying liquid film. Through experimental exploration and theoretical analysis, we demonstrate that the manifestation of such a superhydrophobic-like bouncing necessitates an intricate interplay between the Weber number, the thickness and viscosity of liquid film. Such insights allow us to tune the droplet behaviours in a well-controlled fashion. We anticipate that the combination of superhydrophobic-like bouncing with inherent advantages of emerging slippery liquid interfaces will find a wide range of applications.

  7. Superhydrophobic-like tunable droplet bouncing on slippery liquid interfaces.

    PubMed

    Hao, Chonglei; Li, Jing; Liu, Yuan; Zhou, Xiaofeng; Liu, Yahua; Liu, Rong; Che, Lufeng; Zhou, Wenzhong; Sun, Dong; Li, Lawrence; Xu, Lei; Wang, Zuankai

    2015-08-07

    Droplet impacting on solid or liquid interfaces is a ubiquitous phenomenon in nature. Although complete rebound of droplets is widely observed on superhydrophobic surfaces, the bouncing of droplets on liquid is usually vulnerable due to easy collapse of entrapped air pocket underneath the impinging droplet. Here, we report a superhydrophobic-like bouncing regime on thin liquid film, characterized by the contact time, the spreading dynamics, and the restitution coefficient independent of underlying liquid film. Through experimental exploration and theoretical analysis, we demonstrate that the manifestation of such a superhydrophobic-like bouncing necessitates an intricate interplay between the Weber number, the thickness and viscosity of liquid film. Such insights allow us to tune the droplet behaviours in a well-controlled fashion. We anticipate that the combination of superhydrophobic-like bouncing with inherent advantages of emerging slippery liquid interfaces will find a wide range of applications.

  8. Methods and systems for monitoring a solid-liquid interface

    DOEpatents

    Stoddard, Nathan G.; Clark, Roger F.; Kary, Tim

    2010-07-20

    Methods and systems are provided for monitoring a solid-liquid interface, including providing a vessel configured to contain an at least partially melted material; detecting radiation reflected from a surface of a liquid portion of the at least partially melted material that is parallel with the liquid surface; measuring a disturbance on the surface; calculating at least one frequency associated with the disturbance; and determining a thickness of the liquid portion based on the at least one frequency, wherein the thickness is calculated based on.times. ##EQU00001## where g is the gravitational constant, w is the horizontal width of the liquid, and f is the at least one frequency.

  9. Interfacing dielectric elastomer actuators with liquids

    NASA Astrophysics Data System (ADS)

    Poulin, Alexandre; Maffli, Luc; Rosset, Samuel; Shea, Herbert

    2015-04-01

    Methods and materials for liquid encapsulation in thin (19 μm) silicone membranes are presented in this work. A set of 12 liquids including solvents, oils, silicone pre-polymers and one ionic liquid are experimentally tested. We show that all selected liquids are chemically inert to silicone and that vapor pressure is the key parameter for stable encapsulation. It is demonstrated that encapsulated volume of silicone pre-polymers and ionic liquids can stay stable for more than 1 month. The actuation of dielectric elastomer actuators (DEAs) in conductive liquids is also investigated. An analysis of the equivalent electrical circuits of immersed DEAs shows that non-overlapping regions of the electrodes should be minimized. It also provides guidelines to determine when the electrodes should be passivated. The effects of immersion in a conductive liquid are assessed by measuring the actuation strain and capacitance over periodic actuation. The experimental results show no sign of liquid-induced degradation over more than 45k actuation cycles.

  10. Ultrastable Liquid-Liquid Interface as Viable Route for Controlled Deposition of Biodegradable Polymer Nanocapsules.

    PubMed

    Vecchione, Raffaele; Iaccarino, Giulia; Bianchini, Paolo; Marotta, Roberto; D'autilia, Francesca; Quagliariello, Vincenzo; Diaspro, Alberto; Netti, Paolo A

    2016-06-01

    Liquid-liquid interfaces are highly dynamic and characterized by an elevated interfacial tension as compared to solid-liquid interfaces. Therefore, they are gaining an increasing interest as viable templates for ordered assembly of molecules and nanoparticles. However, liquid-liquid interfaces are more difficult to handle compared to solid-liquid interfaces; their intrinsic instability may affect the assembly process, especially in the case of multiple deposition. Indeed, some attempts have been made in the deposition of polymer multilayers at liquid-liquid interfaces, but with limited control over size and stability. This study reports on the preparation of an ultrastable liquid-liquid interface based on an O/W secondary miniemulsion and its possible use as a template for the self-assembly of polymeric multilayer nanocapsules. Such polymer nanocapsules are made of entirely biodegradable materials, with highly controlled size-well under 200 nm-and multi-compartment and multifunctional features enriching their field of application in drug delivery, as well as in other bionanotechnology fields.

  11. Study of a liquid bridge subjected to interface shear stresses

    NASA Astrophysics Data System (ADS)

    Gaponenko, Yu.; Glockner, S.; Mialdun, A.; Shevtsova, V.

    2011-08-01

    We report on numerical and experimental study of two-phase flows in a tall annulus. The geometry corresponds to a cylindrical liquid column co-axially placed into an outer cylinder with solid walls. The internal column consists of solid supports at the bottom and top, while the central part is a liquid zone filled with viscous liquid and kept in its position by surface tension. Gas enters into the annular duct and entrains initially quiescent liquid. The liquid bridge interface is deformed by gravity and by a co-axial gas flow which is co- and counter directed with respect to gravity. A new experimental set-up including an optical system for precise measurements of the interface displacement has been designed and developed. In the experiments silicone oil 5cSt was used as a test liquid and air as gas. On numerical side the dynamical response of an isothermal liquid bridge to a coaxial gas flow is examined by simulations of the Navier-Stokes equations. The attention is focused on the following points: time-dependent formation of the equilibrium shape of a liquid bridge in gravity conditions and its deformation by a gas flow, simulation of a flow pattern in a liquid/gas system with deformed free surface. The comparison of the numerical and experimental results for the interface deformation exhibits a satisfactory agreement.

  12. Vapor condensation on a turbulent liquid interface

    NASA Technical Reports Server (NTRS)

    Helmick, M. R.; Khoo, B. C.; Sonin, A. A.

    1987-01-01

    An experimental investigation which seeks the fundamental relationship between the interfacial condensation rate and the parameters which control it when the liquid side is turbulent is discussed. The scaling laws for free-surface condensation are discussed for this case. It is argued that the condensation of cryogenic liquids can, in principle, be simulated in experiments using steam and water. Data are presented for the condensation rate in terms of the dimensionless scaling parameters which involve the fluid properties and the liquid-side turbulence velocity and length scales.

  13. Multiple liquid bridges with non-smooth interfaces

    NASA Astrophysics Data System (ADS)

    Fel, Leonid G.; Rubinstein, Boris Y.; Ratner, Vadim

    2016-08-01

    We consider a coexistence of two axisymmetric liquid bridges LB i and LB m of two immiscible liquids i and m which are immersed in a third liquid (or gas) e and trapped between two smooth solid bodies with axisymmetric surfaces S 1, S 2 and free contact lines. Evolution of liquid bridges allows two different configurations of LB i and LB m with multiple (five or three) interfaces of non-smooth shape. We formulate a variational problem with volume constraints and present its governing equations supplemented by boundary conditions. We find a universal relationship between curvature of the interfaces and discuss the Neumann triangle relations at the singular curve where all liquids meet together.

  14. Chemical Identification at the Solid-Liquid Interface.

    PubMed

    Söngen, Hagen; Marutschke, Christoph; Spijker, Peter; Holmgren, Eric; Hermes, Ilka; Bechstein, Ralf; Klassen, Stefanie; Tracey, John; Foster, Adam S; Kühnle, Angelika

    2017-01-10

    Solid-liquid interfaces are decisive for a wide range of natural and technological processes, including fields as diverse as geochemistry and environmental science as well as catalysis and corrosion protection. Dynamic atomic force microscopy nowadays provides unparalleled structural insights into solid-liquid interfaces, including the solvation structure above the surface. In contrast, chemical identification of individual interfacial atoms still remains a considerable challenge. So far, an identification of chemically alike atoms in a surface alloy has only been demonstrated under well-controlled ultrahigh vacuum conditions. In liquids, the recent advent of three-dimensional force mapping has opened the potential to discriminate between anionic and cationic surface species. However, a full chemical identification will also include the far more challenging situation of alike interfacial atoms (i.e., with the same net charge). Here we demonstrate the chemical identification capabilities of dynamic atomic force microscopy at solid-liquid interfaces by identifying Ca and Mg cations at the dolomite-water interface. Analyzing site-specific vertical positions of hydration layers and comparing them with molecular dynamics simulations unambiguously unravels the minute but decisive difference in ion hydration and provides a clear means for telling calcium and magnesium ions apart. Our work, thus, demonstrates the chemical identification capabilities of dynamic AFM at the solid-liquid interface.

  15. Direct measurements of ionic liquid layering at a single mica-liquid interface and in nano-films between two mica-liquid interfaces.

    PubMed

    Griffin, Lucy R; Browning, Kathryn L; Clarke, Stuart M; Smith, Alexander M; Perkin, Susan; Skoda, M W A; Norman, Sarah E

    2016-12-21

    The layering of ionic liquids close to flat, charged interfaces has been identified previously through theoretical and some experimental measurements. Here we present evidence for oscillations in ion density ('layering') in a long chain ionic liquid (1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) near the interface with mica using two complementary approaches. Neutron reflection at the ionic liquid-mica interface is used to detect structure at a single interface, and surface force balance (SFB) measurements carried out with the same ionic liquid reveal oscillatory density in the liquid confined between two mica sheets. Our findings imply the interfacial structure is not induced by confinement alone. Structural forces between two mica surfaces extend to approximately twice the distance of the density oscillations measured at a single interface and have similar period in both cases.

  16. Real Space Imaging of Nanoparticle Assembly at Liquid-Liquid Interfaces with Nanoscale Resolution.

    PubMed

    Costa, Luca; Li-Destri, Giovanni; Thomson, Neil H; Konovalov, Oleg; Pontoni, Diego

    2016-09-14

    Bottom up self-assembly of functional materials at liquid-liquid interfaces has recently emerged as method to design and produce novel two-dimensional (2D) nanostructured membranes and devices with tailored properties. Liquid-liquid interfaces can be seen as a "factory floor" for nanoparticle (NP) self-assembly, because NPs are driven there by a reduction of interfacial energy. Such 2D assembly can be characterized by reciprocal space techniques, namely X-ray and neutron scattering or reflectivity. These techniques have drawbacks, however, as the structural information is averaged over the finite size of the radiation beam and nonperiodic isolated assemblies in 3D or defects may not be easily detected. Real-space in situ imaging methods are more appropriate in this context, but they often suffer from limited resolution and underperform or fail when applied to challenging liquid-liquid interfaces. Here, we study the surfactant-induced assembly of SiO2 nanoparticle monolayers at a water-oil interface using in situ atomic force microscopy (AFM) achieving nanoscale resolved imaging capabilities. Hitherto, AFM imaging has been restricted to solid-liquid interfaces because applications to liquid interfaces have been hindered by their softness and intrinsic dynamics, requiring accurate sample preparation methods and nonconventional AFM operational schemes. Comparing both AFM and grazing incidence X-ray small angle scattering data, we unambiguously demonstrate correlation between real and reciprocal space structure determination showing that the average interfacial NP density is found to vary with surfactant concentration. Additionally, the interaction between the tip and the interface can be exploited to locally determine the acting interfacial interactions. This work opens up the way to studying complex nanostructure formation and phase behavior in a range of liquid-liquid and complex liquid interfaces.

  17. Snap-in of particles at curved liquid interfaces

    NASA Astrophysics Data System (ADS)

    Li, Chao; Moradiafrapoli, Momene; Marston, Jeremy

    2016-11-01

    The contact of particles with liquid interfaces constitutes the first stage in the formation of a particle-laden interface, the so-called "snap-in effect". Here, we report on an experimental study using high-speed video to directly visualize the snap-in process and the approach to the equilibrium state of a particle at a curved liquid interface (i.e. droplet surface). We image the evolution of the contact line, which is found to follow a power-law scaling in time, and the dynamic contact angle during the snap-in. Both hydrophilic and hydrophobic particles are explored and we match the lift-off stage of the particles with a simple force balance. We also explore some multi-particle experiments, eluding to the dynamics of particle-laden interface formation.

  18. Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

    2016-05-01

    Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

  19. Enzyme structure and activity at liquid-liquid interfaces

    SciTech Connect

    Beverung, C.J.; Tupy, M.J.; Radke, C.J.; Blanch, H.W.

    1997-12-31

    Understanding the behavior of proteins interaction at oil/water interfaces is crucial to the design of two-phase bioprocesses (aqueous/organic). An examination of the mechanism of protein adsorption at the oil/water interface was undertaken using tensiometry, transmission electron microscopy (TEM) and a novel total internal reflection fluorescence spectrometer (TIRFS), constructed to monitor adsorption dynamics. Dynamic interfacial tension measurements of protein adsorption show three regimes which can be described by diffusion to the interface, adsorption and denaturation of the adsorbed protein. TEM micrographs show a network of proteins in the adsorbed layer at long times. TIRFS data show that this network formation or protein entanglement in the adsorbed state requires a long period of time to occur. A series of two-monomer random polyamino acids used as model proteins demonstrate many of the adsorption characteristics observed for natural proteins.

  20. Particle self-assembly at ionic liquid-based interfaces.

    PubMed

    Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil

  1. Ionic structure in liquids confined by dielectric interfaces

    NASA Astrophysics Data System (ADS)

    Jing, Yufei; Jadhao, Vikram; Zwanikken, Jos W.; Olvera de la Cruz, Monica

    2015-11-01

    The behavior of ions in liquids confined between macromolecules determines the outcome of many nanoscale assembly processes in synthetic and biological materials such as colloidal dispersions, emulsions, hydrogels, DNA, cell membranes, and proteins. Theoretically, the macromolecule-liquid boundary is often modeled as a dielectric interface and an important quantity of interest is the ionic structure in a liquid confined between two such interfaces. The knowledge gleaned from the study of ionic structure in such models can be useful in several industrial applications, such as in the design of double-layer supercapacitors for energy storage and in the extraction of metal ions from wastewater. In this article, we compute the ionic structure in a model system of electrolyte confined by two planar dielectric interfaces using molecular dynamics simulations and liquid state theory. We explore the effects of high electrolyte concentrations, multivalent ions, dielectric contrasts, and external electric field on the ionic distributions. We observe the presence of non-monotonic ionic density profiles leading to a layered structure in the fluid which is attributed to the competition between electrostatic and steric (entropic) interactions. We find that thermal forces that arise from symmetry breaking at the interfaces can have a profound effect on the ionic structure and can oftentimes overwhelm the influence of the dielectric discontinuity. The combined effect of ionic correlations and inhomogeneous dielectric permittivity significantly changes the character of the effective interaction between the two interfaces.

  2. Liquid-vapor interface of a polydisperse fluid.

    PubMed

    Buzzacchi, Matteo; Wilding, Nigel B

    2005-06-01

    We report a grand canonical Monte Carlo simulation study of the liquid-vapor interface of a model fluid exhibiting polydispersity in terms of the particle size sigma. The bulk density distribution, rho0(sigma), of the system is controlled by the imposed chemical potential distribution mu(sigma), the form of which is specified such that rho0(sigma) assumes a Schulz form with associated degree of polydispersity approximately = 14%. By introducing a smooth attractive wall, a planar liquid-vapor interface is formed for bulk state points within the region of liquid-vapor coexistence. Owing to fractionation, the pure liquid phase is enriched in large particles, with respect to the coexisting vapor. We investigate how the spatial variation of the density near the liquid-vapor interface affects the evolution of the local distribution of particle sizes between the limiting pure phase forms. We find [as previously predicted by density-functional theory, Bellier-Castella, Phys. Rev. E 65, 021503 (2002)] a segregation of smaller particles to the interface. The magnitude of this effect as a function of sigma is quantified via measurements of the relative adsorption. Additionally, we consider the utility of various estimators for the interfacial width and highlight the difficulty of isolating the intrinsic contribution of polydispersity to this width.

  3. Universal fluctuations of growing interfaces: evidence in turbulent liquid crystals.

    PubMed

    Takeuchi, Kazumasa A; Sano, Masaki

    2010-06-11

    We investigate growing interfaces of topological-defect turbulence in the electroconvection of nematic liquid crystals. The interfaces exhibit self-affine roughening characterized by both spatial and temporal scaling laws of the Kardar-Parisi-Zhang theory in 1+1 dimensions. Moreover, we reveal that the distribution and the two-point correlation of the interface fluctuations are universal ones governed by the largest eigenvalue of random matrices. This provides quantitative experimental evidence of the universality prescribing detailed information of scale-invariant fluctuations.

  4. Charge-Controlled Colloids on Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Kunz, Daniel A.; Reck, Bernd; Manoharan, Vinothan N.

    2014-03-01

    The tendency of colloidal particles to stabilize interfaces has been exploited for many years to generate Pickering emulsions with a variety of industrial applications. However, the exact stabilization mechanism and its dependence on the surface properties of the colloidal particles are not yet fully understood. We provide new interfacial studies on the nonequilibrium dynamics of a colloidal system with tunable surface charge density. We push individual sub-micron colloidal particles towards an oil-water interface and track their motion in three-dimensions using holographic microscopy to examine the influence of zeta potential on the dynamics of the system. This project was funded by the BASF Advanced Research Initiative, BASF SE, Germany.

  5. Alkyl Chain Ordering of Asymmetric Phosphatidyicholines Adsorbed at a Liquid-Liquid Interface

    DTIC Science & Technology

    2007-11-02

    polarizability when COIR is tuned across allowed molecular vibrational transitions. Our measurements are sensitive only to this resonant component of the second...nonzero for the particular vibration. As COIR approaches the frequency of an allowed vibrational transition, ot(2) in Eq. 2 becomes very large and a...the CCU-water interface utilizing a total internal reflection geometry, ©vis and COIR are incident on the liquid-liquid interface at their respective

  6. Molecular structure of the coalescence of liquid interfaces

    NASA Technical Reports Server (NTRS)

    Koplik, Joel; Banavar, Jayanth R.

    1992-01-01

    When two bodies of liquid merge, their interfaces must also rupture and rearrange into one. Virtually no information is available concerning the small-scale dynamics of this process. Molecular dynamics simulations of coalescence in systems of about 10,000 Lennard-Jones particles have been performed, arranged so as to mimic laboratory experiments on dense liquids. The coalescence event begins when molecules near the boundary of one liquid body thermally fluctuate into the range of attraction of the other, forming a string of mutually attracting molecules. These molecules gradually thicken into a tendril, which continues to thicken as the bodies smoothly combine in a zipper-like merger.

  7. Laser triangulation for liquid film thickness measurements through multiple interfaces.

    PubMed

    Peterson, Jerrod P; Peterson, Richard B

    2006-07-10

    Laser triangulation is used to measure the thickness of a liquid film in a test section consisting of a quartz viewing window, a water layer, and a hydrophobic membrane. The triangulation sensor acquires measurements to the bounding surfaces of the film while peering through multiple interfaces. This allows the difference between the two measurements to constitute the local film thickness. A refraction model is developed and applied to the analysis of data collected from the experiment. For verification, an empirical method is also developed and compared to the analytical approach. The measurement technique is intended to assess the stability of liquid films for use as gas-liquid contactors.

  8. Measuring the optical chirality of molecular aggregates at liquid-liquid interfaces.

    PubMed

    Watarai, Hitoshi; Adachi, Kenta

    2009-10-01

    Some new experimental methods for measuring the optical chirality of molecular aggregates formed at liquid-liquid interfaces have been reviewed. Chirality measurements of interfacial aggregates are highly important not only in analytical spectroscopy but also in biochemistry and surface nanochemistry. Among these methods, a centrifugal liquid membrane method was shown to be a highly versatile method for measuring the optical chirality of the liquid-liquid interface when used in combination with a commercially available circular dichroism (CD) spectropolarimeter, provided that the interfacial aggregate exhibited a large molar absorptivity. Therefore, porphyrin and phthalocyanine were used as chromophoric probes of the chirality of itself or guest molecules at the interface. A microscopic CD method was also demonstrated for the measurement of a small region of a film or a sheet sample. In addition, second-harmonic generation and Raman scattering methods were reviewed as promising methods for detecting interfacial optical molecules and measuring bond distortions of chiral molecules, respectively.

  9. LIQUID AIR INTERFACE CORROSION TESTING FOR FY2010

    SciTech Connect

    Zapp, P.

    2010-12-16

    An experimental study was undertaken to investigate the corrosivity to carbon steel of the liquid-air interface of dilute simulated radioactive waste solutions. Open-circuit potentials were measured on ASTM A537 carbon steel specimens located slightly above, at, and below the liquid-air interface of simulated waste solutions. The 0.12-inch-diameter specimens used in the study were sized to respond to the assumed distinctive chemical environment of the liquid-air interface, where localized corrosion in poorly inhibited solutions may frequently be observed. The practical inhibition of such localized corrosion in liquid radioactive waste storage tanks is based on empirical testing and a model of a liquid-air interface environment that is made more corrosive than the underlying bulk liquid due to chemical changes brought about by absorbed atmospheric carbon dioxide. The chemical changes were assumed to create a more corrosive open-circuit potential in carbon in contact with the liquid-air interface. Arrays of 4 small specimens spaced about 0.3 in. apart were partially immersed so that one specimen contacted the top of the meniscus of the test solution. Two specimens contacted the bulk liquid below the meniscus and one specimen was positioned in the vapor space above the meniscus. Measurements were carried out for up to 16 hours to ensure steady-state had been obtained. The results showed that there was no significant difference in open-circuit potentials between the meniscus-contact specimens and the bulk-liquid-contact specimens. With the measurement technique employed, no difference was detected between the electrochemical conditions of the meniscus versus the bulk liquid. Stable open-circuit potentials were measured on the specimen located in the vapor space above the meniscus, showing that there existed an electrochemical connection through a thin film of solution extending up from the meniscus. This observation supports the Hobbs-Wallace model of the development

  10. Liquid-Vapor Interface Configurations Investigated in Low Gravity

    NASA Technical Reports Server (NTRS)

    Concus, Paul; Finn, Robert; Weislogel, Mark M.

    1998-01-01

    The Interface Configuration Experiment (ICE) is part of a multifaceted study that is exploring the often striking behavior of liquid-vapor interfaces in low-gravity environments. Although the experiment was posed largely as a test of current mathematical theory, applications of the results should be manifold. In space almost every fluid system is affected, if not dominated, by capillarity (the effects of surface tension). As a result, knowledge of fluid interface behavior, in particular an equilibrium interface shape from which any analysis must begin, is fundamental--from the control of liquid fuels and oxygen in storage tanks to the design and development of inspace thermal systems, such as heat pipes and capillary pumped loops. ICE has increased, and should continue to increase, such knowledge as it probes the specific peculiarities of current theory upon which our present understanding rests. Several versions of ICE have been conducted in the drop towers at the NASA Lewis Research Center, on the space shuttles during the first and second United States Microgravity Laboratory missions (USML-1 and USML-2), and most recently aboard the Russian Mir space station. These studies focused on interfacial problems concerning the existence, uniqueness, configuration, stability, and flow characteristics of liquid-vapor interfaces. Results to date have clearly demonstrated the value of the present theory and the extent to which it can predict the behavior of capillary systems.

  11. Near Axisymmetric Partial Wetting Using Interface-Localized Liquid Dielectrophoresis.

    PubMed

    Brabcova, Zuzana; McHale, Glen; Wells, Gary George; Brown, Carl V; Newton, Michael Ian; Edwards, Andrew M J

    2016-10-03

    The wetting of solid surfaces can be modified by altering the surface free energy balance between the solid, liquid, and vapour phases. Liquid dielectrophoresis (L-DEP) can produce wetting on normally non-wetting surfaces, without modification of the surface topography or chemistry. L-DEP is a bulk force acting on the dipoles of a dielectric liquid and is not normally considered to be a localized effect acting at the interface between the liquid and a solid or other fluid. However, if this force is induced by a non-uniform electric field across a solid-liquid interface, it can be used to enhance and control the wetting of a dielectric liquid. Recently, it was reported theoretically and experimentally that this approach can cause a droplet of oil to spread along parallel interdigitated electrodes thus forming a stripe of liquid. Here we show that by using spiral shaped electrodes actuated with four 90º successive phase shifted signals, a near axisymmetric spreading of droplets can be achieved. Experimental observations show that the induced wetting can achieve film formation, an effect not possible with electrowetting. We show that the spreading is reversible thus enabling a wide range of partial wetting droplet states to be achieved in a controllable manner. Furthermore, we find that the cosine of the contact angle has a quadratic dependence on applied voltage during spreading and deduce a scaling law for the dependence of the strength of the effect on the electrode size. .

  12. Hydrodynamical entrapment of ciliates at the air-liquid interface

    NASA Astrophysics Data System (ADS)

    Ferracci, Jonathan; Ueno, Hironori; Numayama-Tsuruta, Keiko; Imai, Yohsuke; Yamaguchi, Takami; Ishikawa, Takuji

    2012-11-01

    We found the new phenomenon of the entrapment of ciliates at the air-water interface, though they are not trapped by a solid interface. We first characterize the behaviours of cells at the interface by comparing it to those away from interfaces. The results showed that the cell's swimming velocity is considerably reduced at the air-water interface. In order to experimentally verify the possible physiological causes of the entrapment, we observed their behaviours in absence of positive chemotaxis for oxygen and the negative geotaxis. The results illustrated that the entrapment phenomenon was not dependent on these physiological conditions. The experiments using surfactant revealed that the entrapment phenomenon was strongly affected by the velocity-stress conditions at the interface. This fact was confirmed numerically by a boundary element method, i.e. the stress-free condition at the air-liquid interface is one of the main mechanisms of the entrapment phenomenon found in the experiments. Since the entrapment phenomenon found in this study affects the cell-cell interactions and the mass transport at the interface, the knowledge obtained in this study is useful for better understanding the complex behaviours of swimming microorganisms in nature. PhD student in the Physiological Flow Studies Laboratory.

  13. Interfaces Select Specific Stereochemical Conformations: The Isomerization of Glyoxal at the Liquid Water Interface.

    PubMed

    Zhu, Chongqin; Kais, Sabre; Zeng, Xiao Cheng; Francisco, Joseph S; Gladich, Ivan

    2017-01-11

    Interfacial chemistry involving glyoxal at aerosol surfaces is postulated to catalyze aerosol growth. This chemistry remains speculative due to a lack of detailed information concerning the physicochemical behavior of glyoxal at the interface of atmospheric aerosols. Here, we report results from high-level electronic structure calculations as well as both classical and Born-Oppenheimer ab initio molecular dynamics simulations of glyoxal solvation at the air/liquid water interface. When compared to the gas phase, the trans to cis isomerization of glyoxal at the liquid water interface is found to be catalyzed; additionally, the trans conformation is selectively solvated within the bulk to a greater degree than is the cis conformation. These two processes, i.e., the catalytic effect at the water interface and the differentially selective solvation, act to enhance the concentration of the cis isomer of glyoxal at the water interface. This has important consequences for the interpretation of experiments and for the modeling of glyoxal chemistry both at the interface of water clouds and at aerosols. Broader implications of this work relate to describing the role of interfaces in selecting specific stereo molecular structures at interfacial environments.

  14. Experiments on the impact and turbulent coalescence of a blob at a liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Landeau, Maylis; Olson, Peter; Deguen, Renaud; Hirsh, Ben; Earth; Planetary Sciences Team

    2015-11-01

    We present experiments on finite liquid volumes, hereafter referred to as blobs, of variable densities impacting an interface between two immiscible liquids at high Reynolds and Weber numbers. Such processes occurred on a massive scale during the giant impacts that formed terrestrial planets and satellites, including the Earth and the Moon. We find that the fall distance of the blob controls an abrupt transition in coalescence regime and in the amount of mixing with the lower liquid. This transition coincides with a brief and global breakup of the impacting blob into drops. For small fall distances, the large-scale flow following impact behaves as a turbulent fountain: a mixture of immiscible liquids penetrates in the lower liquid, collapses and spreads along the immiscible interface. We derive an experimental scaling relation for turbulent mixing of the impacting blob with the lower liquid as a function of a Richardson number.

  15. Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

    SciTech Connect

    Miranda, Paulo B.

    1998-12-14

    Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayer are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayer at Iiquidhapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the confirmational order of surfactant monolayers.

  16. Relaxation of surface tension in the liquid-solid interfaces of Lennard-Jones liquids.

    PubMed

    Lukyanov, Alex V; Likhtman, Alexei E

    2013-11-19

    We have established the surface tension relaxation time in the liquid-solid interfaces of Lennard-Jones (LJ) liquids by means of direct measurements in molecular dynamics (MD) simulations. The main result is that the relaxation time is found to be almost independent of the molecular structures and viscosity of the liquids (at 70-fold change) used in our study and lies in such a range that in slow hydrodynamic motion the interfaces are expected to be at equilibrium. The implications of our results for the modeling of dynamic wetting processes and interpretation of dynamic contact angle data are discussed.

  17. A moving mesh interface tracking method for simulation of liquid-liquid systems

    NASA Astrophysics Data System (ADS)

    Charin, A. H. L. M.; Tuković, Ž.; Jasak, H.; Silva, L. F. L. R.; Lage, P. L. C.

    2017-04-01

    This manuscript presents a moving mesh interface tracking procedure, with a novel treatment for phase coupling. The new coupling strategy allows accurate predictions for the interface behaviour in a wide range of macroscopic properties with great potential to explore liquid-liquid systems. In this approach, governing equations are applied to each phase individually while the interface is represented by a zero-thickness surface that contemplates inter-phase jumps. These equations are described in an arbitrary Lagrangian-Eulerian finite volume framework. Computations consider the pressure-corrector PISO method. The new treatment for phase coupling incorporates the interfacial jump updates within the pressure/velocity calculations. Additionally, cell-centred values from both phases are considered when calculating convective and diffusive terms at the interface. The employment of GGI (Generalized Grid-Interface) interpolation provides conservative data mapping between surfaces for non-conformal meshes. The prediction capability of the new formulation is evaluated under different dominant effects governing interface motion. Simulated cases include gravity and capillary waves in a sloshing tank, three-dimensional drop oscillation for liquid-liquid systems and drop deformation due to shear flow. The numerical results show good agreement with analytical transient profiles of interface position. The procedure is able to successfully represent systems with similar macroscopic properties, i.e. density and viscosity ratios approaching unity, and a broad range of interfacial tensions.

  18. Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface.

    PubMed

    Izquierdo, Daniel; Martinez, Alberto; Heras, Aranzazu; Lopez-Palacios, Jesus; Ruiz, Virginia; Dryfe, Robert A W; Colina, Alvaro

    2012-07-03

    Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.

  19. Final Report: Thermal Conductance of Solid-Liquid Interfaces

    SciTech Connect

    Cahil, David, G.; Braun, Paul, V.

    2006-05-31

    Research supported by this grant has significantly advanced fundamental understanding of the thermal conductance of solid-liquid interfaces, and the thermal conductivity of nanofluids and nanoscale composite materials. • The thermal conductance of interfaces between carbon nanotubes and a surrounding matrix of organic molecules is exceptionally small and this small value of the interface conductance limits the enhancement in thermal conductivity that can be achieved by loading a fluid or a polymer with nanotubes. • The thermal conductance of interfaces between metal nanoparticles coated with hydrophilic surfactants and water is relatively high and surprisingly independent of the details of the chemical structure of the surfactant. • We extended our experimental methods to enable studies of planar interfaces between surfactant-coated metals and water where the chemical functionalization can be varied between strongly hydrophobic and strongly hydrophilic. The thermal conductance of hydrophobic interfaces establishes an upper-limit of 0.25 nm on the thickness of the vapor-layer that is often proposed to exist at hydrophobic interfaces. • Our high-precision measurements of fluid suspensions show that the thermal conductivity of fluids is not significantly enhanced by loading with a small volume fraction of spherical nanoparticles. These experimental results directly contradict some of the anomalous results in the recent literature and also rule-out proposed mechanisms for the enhanced thermal conductivity of nanofluids that are based on modification of the fluid thermal conductivity by the coupling of fluid motion and the Brownian motion of the nanoparticles.

  20. Particles adsorbed at various non-aqueous liquid-liquid interfaces.

    PubMed

    Fernandez-Rodriguez, Miguel Angel; Binks, Bernard P; Rodriguez-Valverde, Miguel Angel; Cabrerizo-Vilchez, Miguel Angel; Hidalgo-Alvarez, Roque

    2017-02-07

    Particles adsorbed at liquid interfaces are commonly used to stabilise water-oil Pickering emulsions and water-air foams. The fundamental understanding of the physics of particles adsorbed at water-air and water-oil interfaces is improving significantly due to novel techniques that enable the measurement of the contact angle of individual particles at a given interface. The case of non-aqueous interfaces and emulsions is less studied in the literature. Non-aqueous liquid-liquid interfaces in which water is replaced by other polar solvents have properties similar to those of water-oil interfaces. Nanocomposites of non-aqueous immiscible polymer blends containing inorganic particles at the interface are of great interest industrially and consequently more work has been devoted to them. By contrast, the behaviour of particles adsorbed at oil-oil interfaces in which both oils are immiscible and of low dielectric constant (ε<3) is scarcely studied. Hydrophobic particles are required to stabilise these oil-oil emulsions due to their irreversible adsorption, high interfacial activity and elastic shell behaviour.

  1. Emulsification at the Liquid/Liquid Interface: Effects of Potential, Electrolytes and Surfactants.

    PubMed

    Chowdhury, Mehrin; Kataky, Ritu

    2016-01-04

    Emulsification of oils at liquid/liquid interfaces is of fundamental importance across a range of applications, including detergency. Adsorption and partitioning of the anionic surface active ions at the interface between two immiscible solutions is known to cause predictable chaos at the transfer potential region of the surfactant. In this work, the phenomenon that leads to the chaotic behaviour shown by sodium dodecylbenzene sulfonate (SDBS) at the water/1,2-dichloroethane interface is applied to commercial surfactants and aqueous/glyceryl trioleate interface. Electrochemical methods, electrocapillary curves, optical microscopy and conductivity measurements demonstrated that at 1.5 mm of SDBS, surfactants are adsorbed at the interface and assemble into micelles, leading to interfacial instability. As the concentration of the anionic surfactant was enhanced to 8 and 13.4 mm, the Marangoni effect and the interfacial emulsification became more prominent. The chaotic behaviour was found to be dependent on the surfactant concentration and the electrolytes present.

  2. Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface.

    PubMed

    Matsuoka, Ryota; Sakamoto, Ryota; Hoshiko, Ken; Sasaki, Sono; Masunaga, Hiroyasu; Nagashio, Kosuke; Nishihara, Hiroshi

    2017-02-15

    Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm).

  3. Vibration-Induced Gas-Liquid Interface Breakup

    NASA Astrophysics Data System (ADS)

    O'Hern, Timothy; Torczynski, John; Romero, Ed; Shelden, Bion

    2010-11-01

    Gas-liquid interfaces can be forced to break up when subjected to vibrations within critical ranges of frequency and amplitude. This breakup mechanism was examined experimentally using deep layers of silicone oils over a range of viscosity and sinusoidal, primarily axial vibration conditions that can produce dramatic disturbances at the gas-liquid free surface. Although small-amplitude vibrations produce standing Faraday waves, large-amplitude vibrations produce liquid jets into the gas, droplets pinching off from the jets, gas cavities in the liquid from droplet impact, and bubble transport below the interface. Experiments used several different silicone oils over a range of pressures and vibration conditions. Computational simulations exhibiting similar behavior will be included in the presentation. Applications include liquid fuel rockets, inertial sensing devices, moving vehicles, mixing processes, and acoustic excitation. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  4. Hydrogen-bonding molecular ruler surfactants as probes of specific solvation at liquid/liquid interfaces.

    PubMed

    Siler, A Renee; Brindza, Michael R; Walker, Robert A

    2009-10-01

    Resonance-enhanced, second harmonic generation (SHG) is used to measure the electronic structure of solutes sensitive to specific solvation adsorbed to liquid/liquid and liquid/solid interfaces. Here, specific solvation refers to solvent-solute interactions that are directional and localized. N-methyl-p-methoxyaniline (NMMA) is a solute whose first allowed electronic transition wavelength remains almost constant (approximately 315 nm) in non-hydrogen-bonding solvents regardless of solvent polarity. However, in hydrogen-bond-accepting solvents such as dimethylsulfoxide, NMMA's absorbance shifts to longer wavelengths (320 nm), whereas in hydrogen-bond-donating solvents (e.g., water), the absorbance shifts to shorter wavelengths (approximately 300 nm). SHG experiments show that at alkane/silica interfaces, surface silanol groups serve as moderately strong hydrogen-bond donors as evidenced by NMMA's absorbance of 307 nm. At the carbon tetrachloride/water interface, NMMA absorbance also shifts to slightly shorter wavelengths (298 nm) implying that water molecules at this liquid/liquid interface are donating strong hydrogen bonds to the adsorbed NMMA solutes. In contrast, experiments using newly developed molecular ruler surfactants with NMMA as a model hydrophobic solute and a hydrophilic, cationic headgroup imply that, as NMMA migrates across an aqueous/alkane interface, it carries with it water that functions as a hydrogen-bond-accepting partner.

  5. Nanoscale thermal transport at solid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Ge, Zhenbin

    This thesis focuses on the experimental study of nanoscale thermal transport across solidliquid interfaces in both nanoparticle system and planar thin film system. Thermal conductance of solid-liquid interfaces, G, will be measured using time-domain thermo-reflectance and pump-probe transient absorption. Interface thermal conductance, G, relates the temperature drop DeltaT at an interface to the flux of heat F that crosses the interface, F = GDeltaT. In nanoparticle systems, using pump-probe transient absorption measurement, we find that nanoparticles, ranging in size from 3-24 rim. with widely varying hydrophilic surface chemistry, give thermal conductances G ˜ 100-300 MW m-2 K-1 for the particle-water interfaces, approximately an order of magnitude larger than the conductance of the interfaces between alkanethiol-terminated AuPd nanoparticles and toluene. The relatively large thermal conductances between particle-water interfaces indicate that the thermal coupling between hydrophilic nanoparticles and water is strong regardless of the self-assembled stabilizing group. In planar systems, using time-domain thermoreflectance, we find that the thermal conductance between water and planar hydrophilic surfaces ranges between 100 and 180 MW m-2 K-1, which is in good agreement with the nanoparticles systems. While in hydrophobic-water interfaces, interface thermal conductance is smaller, ranging between 45 and 65 MW m-2 K-1 indicating that the thermal coupling between hydrophobic surfaces and water is weaker than with hydrophilic surfaces. The Kapitza length---the thermal conductivity of water divided by the thermal conductance per unit area of the interface---at hydrophobic interfaces (10-12 nm) is a factor of 2-3 larger than the Kapitza length at hydrophilic interfaces (3-6 nm). We also utilized the pump-probe transient absorption measurement to probe thermal transport in Au-core polymer-shell nanoparticles. The addition of an organic co-solvent to the suspension

  6. Additive manufacturing. Continuous liquid interface production of 3D objects.

    PubMed

    Tumbleston, John R; Shirvanyants, David; Ermoshkin, Nikita; Janusziewicz, Rima; Johnson, Ashley R; Kelly, David; Chen, Kai; Pinschmidt, Robert; Rolland, Jason P; Ermoshkin, Alexander; Samulski, Edward T; DeSimone, Joseph M

    2015-03-20

    Additive manufacturing processes such as 3D printing use time-consuming, stepwise layer-by-layer approaches to object fabrication. We demonstrate the continuous generation of monolithic polymeric parts up to tens of centimeters in size with feature resolution below 100 micrometers. Continuous liquid interface production is achieved with an oxygen-permeable window below the ultraviolet image projection plane, which creates a "dead zone" (persistent liquid interface) where photopolymerization is inhibited between the window and the polymerizing part. We delineate critical control parameters and show that complex solid parts can be drawn out of the resin at rates of hundreds of millimeters per hour. These print speeds allow parts to be produced in minutes instead of hours.

  7. Interaction of Porosity with a Planar Solid/Liquid Interface

    NASA Technical Reports Server (NTRS)

    Catalina, Adrian V.; Stefanescu, Doru M.; Sen, Subhayu; Kaukler, William K.; Curreri, Peter A. (Technical Monitor)

    2002-01-01

    In this paper, an investigation of the interaction between gas porosity and a planar solid/liquid (SL) interface is reported. A two-dimensional numerical model able to accurately track sharp SL interfaces during solidification of pure metals and alloys is proposed. The finite difference method and a rectangular undeformed grid are used for computation. The SL interface is described through the points of intersection with the grid lines. Its motion is determined by the thermal and solute gradients at each particular point. Changes of the interface temperature because of capillarity or solute redistribution as well as any perturbation of the thermal and solute field produced by the presence of non-metallic inclusions can be computed. To validate the model, the dynamics of the interaction between a gas pore and a solidification front in metal alloys was observed using a state of the art X-ray Transmission Microscope. The experiments included observation of the distortion of the SL interface near a pore, real-time measurements of the growth rate and the change in shape of the porosity during interaction with an advancing SL interface in pure Al and Al-0.25 wt% Au alloy. In addition, porosity induced solute segregation patterns surrounding a pore were also quantified.

  8. Interaction of Porosity with a Planar Solid/Liquid Interface

    NASA Technical Reports Server (NTRS)

    Catalina, Adrian V.; Stefanescu, Doru M.; Sen, Subhayu; Kaukler, William F.

    2004-01-01

    In this article, an investigation of the interaction between gas porosity and a planar solid/liquid (SL) interface is reported. A two-dimensional numerical model able to accurately track sharp SL interfaces during solidification of pure metals and alloys is proposed. The finite-difference method and a rectangular undeformed grid are used for computation. The SL interface is described through the points of intersection with the grid lines. Its motion is determined by the thermal and solute gradients at each particular point. Changes of the interface temperature because of capillarity or solute redistribution as well as any perturbation of the thermal and solute field produced by the presence of non-metallic inclusions can be computed. To validate the model, the dynamics of the interaction between a gas pore and a solidification front in metal alloys was observed using a state of the art X-ray transmission microscope (XTM). The experiments included observation of the distortion of the SL interface near a pore, real-time measurements of the growth rate, and the change in shape of the porosity during interaction with the SL interface in pure Al and Al-0.25 wt pct Au alloy. In addition, porosity-induced solute segregation patterns surrounding a pore were also quantified.

  9. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    SciTech Connect

    Perahia, Dvora, Dr.; Pierce, Flint; Tsige, Mesfin; Grest, Gary Stephen, Dr.

    2008-08-01

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  10. Active colloids at liquid-liquid interfaces: dynamic self-assembly and functionality

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor

    2012-02-01

    Self-assembled materials must actively consume energy and remain out of equilibrium in order to support structural complexity and functional diversity. Colloids of interacting particles suspended at liquid-liquid interfaces and maintained out of equilibrium by external alternating electromagnetic fields develop nontrivial collective dynamics and self-assembly. We use ferromagnetic colloidal micro-particles (so the magnetic moment is fixed in each particle and interactions between colloids is highly anisotropic and directional) suspended over an interface of two immiscible liquids and energized by vertical alternating magnetic fields to demonstrate novel dynamic and active self-assembled structures (``asters'') which are not accessible through thermodynamic assembly. Structures are attributed to the interplay between surface waves, generated at the liquid/liquid interface by the collective response of magnetic microparticles to the alternating magnetic field, and hydrodynamic fields induced in the boundary layers of both liquids forming the interface. Two types of magnetic order are reported. We demonstrate that asters develop self-propulsion in the presence of a small in-plane dc magnetic field. We show that asters can capture, transport, and position target microparticles.

  11. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    PubMed

    Pierce, Flint; Tsige, Mesfin; Perahia, Dvora; Grest, Gary S

    2008-12-18

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  12. Ultrasonic fluid densitometer having liquid/wedge and gas/wedge interfaces

    DOEpatents

    Greenwood, Margaret S.

    2000-01-01

    The present invention is an ultrasonic liquid densitometer that uses a material wedge having two sections, one with a liquid/wedge interface and another with a gas/wedge interface. It is preferred that the wedge have an acoustic impedance that is near the acoustic impedance of the liquid, specifically less than a factor of 11 greater than the acoustic impedance of the liquid. Ultrasonic signals are internally reflected within the material wedge. Density of a liquid is determined by immersing the wedge into the liquid and measuring reflections of ultrasound at the liquid/wedge interface and at the gas/wedge interface.

  13. Adsorption of nanoparticles at the solid-liquid interface.

    PubMed

    Brenner, Thorsten; Paulus, Michael; Schroer, Martin A; Tiemeyer, Sebastian; Sternemann, Christian; Möller, Johannes; Tolan, Metin; Degen, Patrick; Rehage, Heinz

    2012-05-15

    The adsorption of differently charged nanoparticles at liquid-solid interfaces was investigated by in situ X-ray reflectivity measurements. The layer formation of positively charged maghemite (γ-Fe(2)O(3)) nanoparticles at the aqueous solution-SiO(2) interface was observed while negatively charged gold nanoparticles show no adsorption at this interface. Thus, the electrostatic interaction between the particles and the charged surface was determined as the driving force for the adsorption process. The data analysis shows that a logarithmic particle size distribution describes the density profile of the thin adsorbed maghemite layer. The size distribution in the nanoparticle solution determined by small angle X-ray scattering shows an average particle size which is similar to that found for the adsorbed film. The formed magehemite film exhibits a rather high stability.

  14. Boundary conditions on the vapor liquid interface at strong condensation

    NASA Astrophysics Data System (ADS)

    Kryukov, A. P.; Levashov, V. Yu.

    2016-07-01

    The problem of the formulation of boundary conditions on the vapor-liquid interface is considered. The different approaches to this problem and their difficulties are discussed. Usually, a quasi-equilibrium scheme is used. At sufficiently large deviations from thermodynamic equilibrium, a molecular kinetics approach should be used for the description of the vapor flow at condensation. The formulation of the boundary conditions at the vapor liquid interface to solve the Boltzmann kinetic equation for the distribution of molecules by velocity is a sophisticated problem. It appears that molecular dynamics simulation (MDS) can be used to provide this solution at the interface. The specific problems occur in the realization of MDS on large time and space scales. Some of these problems, and a hierarchy of continuum, kinetic and molecular dynamic time scales, are discussed in the paper. A description of strong condensation at the kinetic level is presented for the steady one-dimensional problem. A formula is provided for the calculation of the limiting condensation coefficient. It is shown that as the condensation coefficient approaches the limiting value, the vapor pressure rises significantly. The results of the corresponding calculations for the Mach number and temperature at different vapor flows are demonstrated. As a result of the application of the molecular kinetics method and molecular dynamics simulation to the problem of the determination of argon condensation coefficients in the range of temperatures of vapor and liquid ratio 1.0-4.0, it is concluded that the condensation coefficient is close to unity.

  15. Molecular dynamics of the water liquid-vapor interface

    NASA Technical Reports Server (NTRS)

    Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

    1987-01-01

    The results of molecular dynamics calculations on the equilibrium interface between liquid water and its vapor at 325 K are presented. For the TIP4P model of water intermolecular pair potentials, the average surface dipole density points from the vapor to the liquid. The most common orientations of water molecules have the C2 nu molecular axis roughly parallel to the interface. The distributions are quite broad and therefore compatible with the intermolecular correlations characteristic of bulk liquid water. All near-neighbor pairs in the outermost interfacial layers are hydrogen bonded according to the common definition adopted here. The orientational preferences of water molecules near a free surface differ from those near rigidly planar walls which can be interpreted in terms of patterns found in hexagonal ice 1. The mean electric field in the interfacial region is parallel to the mean polarization which indicates that attention cannot be limited to dipolar charge distributions in macroscopic descriptions of the electrical properties of this interface. The value of the surface tension obtained is 132 +/- 46 dyn/cm, significantly different from the value for experimental water of 68 dyn/cm at 325 K.

  16. Use of the liquid-liquid interface for generating ultrathin nanocrystalline films of metals, chalcogenides, and oxides.

    PubMed

    Rao, C N R; Kulkarni, G U; Agrawal, Ved Varun; Gautam, Ujjal K; Ghosh, Moumita; Tumkurkar, Usha

    2005-09-15

    The air-water interface has traditionally been employed to prepare particle assemblies and films of metals and semiconductors. The interface between water and an organic liquid, however, has not been investigated sufficiently for possible use in preparing nanocrystals and thin films of materials. In this article, we demonstrate the use of the liquid-liquid interface as a medium for preparing ultrathin films of metals, chalcogenides and oxides. The method involves the reaction at the interface between a metal-organic compound in the organic layer and an appropriate reagent for reduction, sulfidation, etc. in the aqueous layer. Some of the materials discussed are nanocrystalline films of gold, CuS, CuSe, CuO, and Cu(OH)2 formed at the liquid-liquid interface. The results reported in this article should demonstrate the versatility and potential of the liquid-liquid interface for preparing nanomaterials and ultrathin films and encourage further research in this area.

  17. Manipulation of liquid-liquid interfaces for tunable optics on a chip in microfluidic systems

    NASA Astrophysics Data System (ADS)

    Tan, Kam Yan Sindy

    This thesis describes the design and development of optofluidics: a new class of optical components based on dynamic liquid-liquid interfaces between liquids possessing different optical properties in microfluidic systems. Devices with optical interfaces formed by liquids possess characteristics that are quite different from solid-gas and solid-liquid systems commonly used in conventional optics. Advantages of optofluidic systems include the simplicity to reconfigure optical properties and functions in real time. Examples of devices include liquid waveguides, lenses, and multi-color droplet dye laser. Potential applications include biochemical characterization and optical spectroscopy in micro-total analytical systems. Chapter 1 describers the motivation, general configuration and characteristics of devices with optical interfaces formed by liquids in microchannels. Chapter 2 describes the soft lithographic techniques used to make optofluidic devices. Chapter 3 describes the use of co-fabrication to design and fabricate multiple functional components in microfluidic systems in a single step. Chapters 4 to 6 describe the design and operation of three optofluidic devices: waveguides, lenses, and dye lasers.

  18. Floating and sinking of self-assembled spheres on liquid-liquid interfaces: Rafts versus stacks

    NASA Astrophysics Data System (ADS)

    Jones, Steven G.; Abbasi, Niki; Ahuja, Abhinav; Truong, Vivian; Tsai, Scott S. H.

    2015-07-01

    The floating and sinking of objects on fluid-fluid interfaces occurs in nature and has many important implications in technology. Here, we study the stability of floating self-assembled spheres on an oil-water interface, and how the sphere deposition geometry affects the size limits of the assemblies before they collapse and sink through the interface. Specifically, we compare the critical size of particle rafts to particle stacks. We show that, on liquid-liquid interfaces, monolayer rafts and stacked spheres exhibit different scaling of the critical number of spheres to the Bond number—the dimensionless ratio of buoyancy to interfacial tension effects. Our results indicate that particle stacks will sink with a lower threshold number of particles than particle rafts. This finding may have important implications to engineering applications where interfacial assemblies are not monolayers.

  19. Mixing and transient interface condensation of a liquid hydrogen tank

    NASA Technical Reports Server (NTRS)

    Lin, C. S.; Hasan, M. M.; Nyland, T. W.

    1993-01-01

    Experiments were conducted to investigate the effect of axial jet-induced mixing on the pressure reduction of a thermally stratified liquid hydrogen tank. The tank was nearly cylindrical, having a volume of about 0.144 cu m with 0.559 m in diameter and 0.711 m length. A mixer/pump unit, which had a jet nozzle outlet of 0.0221 m in diameter was located 0.178 m from the tank bottom and was installed inside the tank to generate the axial jet mixing and tank fluid circulation. Mixing tests began with the tank pressures at which the thermal stratification results in 4.9-6.2 K liquid subcooling. The mixing time and transient vapor condensation rate at the liquid-vapor interface are determined. Two mixing time correlations, based on the thermal equilibrium and pressure equilibrium, are developed and expressed as functions of system and buoyancy parameters. The limited liquid hydrogen data of the present study shows that the modified steady state condensation rate correlation may be used to predict the transient condensation rate in a mixing process if the instantaneous values of jet sub cooling and turbulence intensity at the interface are employed.

  20. Thermocapillary Convection at the Interface of Two Liquids --

    NASA Astrophysics Data System (ADS)

    van Hook, Stephen J.; Andre, Carrie; McCormick, W. D.; Swift, J. B.; Swinney, Harry L.

    1997-11-01

    While convection due to surface tension (thermocapillary) effects at a liquid-gas interface has received much theoretical and experiment attention (S. J. Van Hook et al.), to appear in J. Fluid Mech.; A. A. Golovin, A. A. Nepomnyashchy, & L. M. Pismen, Phys. Fluids 6, 34--48 (1994); D. A. Goussis & R. E. Kelly, Int. J. Heat Mass Trans. 33, 2237--2245 (1990); S. Davis, Annu. Rev. Fluid Mech. 19, 403--435 (1987)., the problem of two-layer (liquid-liquid) surface-tension-driven convection has been relatively ignored. Stability theory predicts a wide range of instabilities---short- and long-wavelength, stationary and oscillatory---for heating the system from above or below. We examine the conditions under which these different instabilities can be observed in real fluid systems. While the short wavelength instabilities are analogous to convection in buoyancy-driven convection, the long-wavelength instabilities are exclusively a feature of thermocapillary flow.

  1. Resolving amorphous solid-liquid interfaces by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Burson, Kristen M.; Gura, Leonard; Kell, Burkhard; Büchner, Christin; Lewandowski, Adrian L.; Heyde, Markus; Freund, Hans-Joachim

    2016-05-01

    Recent advancements in liquid atomic force microscopy make it an ideal technique for probing the structure of solid-liquid interfaces. Here, we present a structural study of a two-dimensional amorphous silica bilayer immersed in an aqueous solution utilizing liquid atomic force microscopy with sub-nanometer resolution. Structures show good agreement with atomically resolved ultra-high vacuum scanning tunneling microscopy images obtained on the same sample system, owing to the structural stability of the silica bilayer and the imaging clarity from the two-dimensional sample system. Pair distance histograms of ring center positions are utilized to develop quantitative metrics for structural comparison, and the physical origin of pair distance histogram peaks is addressed by direct assessment of real space structures.

  2. Methods and systems for monitoring a solid-liquid interface

    DOEpatents

    Stoddard, Nathan G [Gettysburg, PA; Clark, Roger F [Frederick, MD

    2011-10-04

    Methods and systems are provided for monitoring a solid-liquid interface, including providing a vessel configured to contain an at least partially melted material; detecting radiation reflected from a surface of a liquid portion of the at least partially melted material; providing sound energy to the surface; measuring a disturbance on the surface; calculating at least one frequency associated with the disturbance; and determining a thickness of the liquid portion based on the at least one frequency, wherein the thickness is calculated based on L=(2m-1)v.sub.s/4f, where f is the frequency where the disturbance has an amplitude maximum, v.sub.s is the speed of sound in the material, and m is a positive integer (1, 2, 3, . . . ).

  3. Capillary freezing of ionic liquids confined between metallic interfaces

    NASA Astrophysics Data System (ADS)

    Comtet, Jean; Niguès, Antoine; Kaiser, Vojtech; Bocquet, Lydéric; Siria, Alessandro

    2016-11-01

    Using a quartz tuning fork based AFM, we investigate the behavior of ionic liquids under confinement. Using nanorheological measurements, we show that nanometric confinements can lead to solidification and capillary freezing of the ionic liquid. We find that the critical confinement at which the liquid-solid transition occurs depends strongly on the bulk electronic properties of the confining substrate, with stronger effects observed for more metallic surfaces. This behavior is rationalized on the basis of a Gibbs-Thompson framework for the shift of the freezing transition, taking into account surface energies with the imperfect metal at the level of a Thomas-Fermi model. Finally, we show that capillary freezing can also be tuned by electrifying the confining interfaces.

  4. Electrical control of Faraday rotation at a liquid-liquid interface.

    PubMed

    Marinescu, Monica; Kornyshev, Alexei A; Flatté, Michael E

    2015-01-01

    A theory is developed for the Faraday rotation of light from a monolayer of charged magnetic nanoparticles at an electrified liquid-liquid interface. The polarization fields of neighboring nanoparticles enhance the Faraday rotation. At such interfaces, and for realistic sizes and charges of nanoparticles, their adsorption-desorption can be controlled with a voltage variation<1 V, providing electrovariable Faraday rotation. A calculation based on the Maxwell-Garnett theory predicts that the corresponding redistribution of 40 nm nanoparticles of yttrium iron garnet can switch a cavity with a quality factor larger than 10(4) for light of wavelength 500 nm at normal incidence.

  5. Surface vibrational structure at alkane liquid/vapor interfaces.

    PubMed

    Esenturk, Okan; Walker, Robert A

    2006-11-07

    Broadband vibrational sum frequency spectroscopy (VSFS) has been used to examine the surface structure of alkane liquid/vapor interfaces. The alkanes range in length from n-nonane (C(9)H(20)) to n-heptadecane (C(17)H(36)), and all liquids except heptadecane are studied at temperatures well above their bulk (and surface) freezing temperatures. Intensities of vibrational bands in the CH stretching region acquired under different polarization conditions show systematic, chain length dependent changes. Data provide clear evidence of methyl group segregation at the liquid/vapor interface, but two different models of alkane chain structure can predict chain length dependent changes in band intensities. Each model leads to a different interpretation of the extent to which different chain segments contribute to the anisotropic interfacial region. One model postulates that changes in vibrational band intensities arise solely from a reduced surface coverage of methyl groups as alkane chain length increases. The additional methylene groups at the surface must be randomly distributed and make no net contribution to the observed VSF spectra. The second model considers a simple statistical distribution of methyl and methylene groups populating a three dimensional, interfacial lattice. This statistical picture implies that the VSF signal arises from a region extending several functional groups into the bulk liquid, and that the growing fraction of methylene groups in longer chain alkanes bears responsibility for the observed spectral changes. The data and resulting interpretations provide clear benchmarks for emerging theories of molecular structure and organization at liquid surfaces, especially for liquids lacking strong polar ordering.

  6. Crystallization of Polymers at liquid/liquid interface templated by single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Li, Christopher

    2012-02-01

    Nanosized single-walled carbon nanotube rings were fabricated by using a Pickering emulsion-based method. By tuning a water/oil/SWNT miniemulsion system, SWNT rings with a diameter of ˜200 nm can be readily achieved. The formation mechanism is attributed to the bending force induced by the curved liquid/liquid interface. Crystallization of polyethylene homo- and copolymers using this unique SWNT rings as the nucleation agent was conducted at the curved liquid/liquid interface. Crystal structure, hybrid morphology and crystallization kinetics were systematically studied. The structure of controlled alternating patterns on SWNT rings has great potential in various applications in large-scale integrated circuits and single-electron devices.

  7. Electric double layer at the interface of ionic liquid-dielectric liquid under electric field.

    PubMed

    Lee, D W; Im, D J; Kang, I S

    2013-02-12

    The structure of the electric double layer (EDL) is analyzed in order to understand the electromechanical behavior of the interface of ionic liquid-dielectric liquid. The modified Poisson-Boltzmann equation proposed by Bazant et al. is solved to see the crowding and the overscreening effects that are the characteristics of an ionic liquid (Bazant, M. Z.; Storey, B. D.; Kornyshev, A. A. Double layer in ionic liquids: Overscreening versus crowding. Phys. Rev. Lett. 2011, 106, 046102.). From the simple one-dimensional (1-D) analysis, it is found that the changes of the composition and the material properties in the EDL are negligible except under some extreme conditions such as strong electric field over O(10(8)) V/m. From the electromechanical view points, an ionic liquid behaves like a pure conductor at the interface with a dielectric liquid. Based on these findings, three specific application problems are considered. In the first, a new method is suggested for measuring the interfacial tension of an ionic liquid-dielectric liquid system. The deformation of a charged ionic liquid droplet translating between two electrodes is used for this measurement. The second is for the Taylor cone problem, which includes an extreme electric field condition near the tip. The size of the critical region, where the EDL effect should be considered, is estimated by using the 1-D analysis result. Numerical computation is also performed to see the profiles of electric potential and the electric stress along the interface of the Taylor cone. Lastly, the electrowetting problem of the ionic liquid is considered. The discrepancies in the results of previous workers are interpreted by using the results of the present work. It is shown that all the results might be consistent if the leaking of the dielectric layer and/or the adsorption of ions is considered.

  8. Non-capillary binding of colloidal particles to liquid interfaces

    NASA Astrophysics Data System (ADS)

    Kaz, David; McGorty, Ryan; Manoharan, Vinothan

    2012-02-01

    We observe colloidal polystyrene particles binding reversibly to an oil-water interface through the combination of a repulsive electrostatic force and an attractive van der Waals force. Previously studied interactions of an aqueous colloidal particle and a liquid interface have generally fallen into two categories: 1) electrostatic repulsion indicated by the dependence on salt and 2) capillary adsorption where surface tension brings the particle in contact with both phases and is indicated by practically irreversible binding. With our technique of pushing individual colloidal particles towards a planar oil-water interface and observing their motion in three-dimensions with holographic microscopy we have observed both interactions. However, our observations indicate that under certain conditions the electrostatic repulsion, which is due to repulsive image charges, is weak enough for a particle to experience a van der Waals attraction while strong enough to prevent a particle from penetrating the interface and becoming bound through capillary action. We observe individual particles transition between repulsive and attractive interactions with the interface suggesting that these colloidal particles have a heterogeneous surface charge.

  9. Production of Self-Assembled Fullerene (C60) Nanocrystals at Liquid-Liquid Interface.

    PubMed

    Shrestha, Rekha Goswami; Shrestha, Lok Kumar; Abe, Masahiko; Ariga, Katsuhiko

    2015-03-01

    Here we present self-assembled nanostructure of functional molecule fullerene (C60) at liquid-liquid interface. The nanostructured nanocrystals were grown at liquid-liquid interface of isopropyl alcohol (IPA) and C60 solution in butylbenzene under ambient condition of temperature and pressure, and characterized by Raman scattering, power X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The crystal formation mechanism is driven by supersaturation related to the low solubility of C60 in IPA. A slow diffusion of IPA towards the C60 solution causes unsaturation of C60 at the liquid-liquid interface and consequently small clusters of C60 is formed at the interface, which acts as the nucleation site. Further diffusion of IPA supplies the C60 molecules from bulk to the interface promoting the crystal growth. Based on SEM and TEM observation, the average size of the individual hexagonal bipyramid nanocrystal is found to be ca. 1.4 µm and the average size of their assembly is found to be approximately 2 µm. XRD measurements have shown that these materials are crystalline with mixed face-centered cubic (cell dimension: a = 1.352 nm, and V = 2.475 nm3) and hexagonal (cell dimension: a = 1.452 nm, c = 1.207 nm, c/a = 0.831, and V = 2.475 nm3) structures. Raman scattering measurements showed two Ag and six Hg vibration bands, which are similar to those obtained in the pristine C60.

  10. Probing Hydrophilic Interface of Solid/Liquid-Water by Nanoultrasonics

    PubMed Central

    Mante, Pierre-Adrien; Chen, Chien-Cheng; Wen, Yu-Chieh; Chen, Hui-Yuan; Yang, Szu-Chi; Huang, Yu-Ru; -Ju Chen, I.; Chen, Yun-Wen; Gusev, Vitalyi; Chen, Miin-Jang; Kuo, Jer-Lai; Sheu, Jinn-Kong; Sun, Chi-Kuang

    2014-01-01

    Despite the numerous devoted studies, water at solid interfaces remains puzzling. An ongoing debate concerns the nature of interfacial water at a hydrophilic surface, whether it is more solid-like, ice-like, or liquid-like. To answer this question, a complete picture of the distribution of the water molecule structure and molecular interactions has to be obtained in a non-invasive way and on an ultrafast time scale. We developed a new experimental technique that extends the classical acoustic technique to the molecular level. Using nanoacoustic waves with a femtosecond pulsewidth and an ångström resolution to noninvasively diagnose the hydration structure distribution at ambient solid/water interface, we performed a complete mapping of the viscoelastic properties and of the density in the whole interfacial water region at hydrophilic surfaces. Our results suggest that water in the interfacial region possesses mixed properties and that the different pictures obtained up to now can be unified. Moreover, we discuss the effect of the interfacial water structure on the abnormal thermal transport properties of solid/liquid interfaces. PMID:25176017

  11. Mixing and transient interface condensation of a liquid hydrogen tank

    NASA Technical Reports Server (NTRS)

    Lin, C. S.; Hasan, M. M.; Nyland, T. W.

    1993-01-01

    Experiments were conducted to investigate the effect of axial jet-induced mixing on the pressure reduction of a thermally stratified liquid hydrogen tank. The tank was nearly cylindrical, having a volume of about 0.144 cu m with 0.559 m in diameter and 0.711 m long. A mixer/pump unit, which had a jet nozzle outlet of 0.0221 m in diameter was located 0.178 m from the tank bottom and was installed inside the tank to generate the axial jet mixing and tank fluid circulation. The liquid fill and jet flow rate ranged from 42 to 85 percent (by volume) and 0.409 to 2.43 cu m/hr, respectively. Mixing tests began with the tank pressure ranging from 187.5 to 238.5 kPa at which the thermal stratification results in 4.9 to 6.2 K liquid sub cooling. The mixing time and transient vapor condensation rate at the liquid-vapor interface are determined. Two mixing time correlations, based on the thermal equilibrium and pressure equilibrium, are developed. Both mixing time correlations are expressed as functions of system and buoyancy parameters and compared well with other experimental data. The steady state condensation rate correlation of Sonin et al. based on steam-water data is modified and expressed as a function of jet subcooling. The limited liquid hydrogen data of the present study shows that the modified steady state condensation rate correlation may be used to predict the transient condensation rate in a mixing process if the instantaneous values of jet sub cooling and turbulence intensity at the interface are employed.

  12. Self-instability of finite sized solid-liquid interfaces

    PubMed Central

    Wu, L.K.; Xu, B.; Li, Q.L.; Liu, W.

    2015-01-01

    In solid-liquid systems, macroscopic solids lose their equilibrium and melt in a manner that results in overall movement of the solid-liquid interface. This phenomenon occurs when they are subjected to temperature gradients or external stress, for example. However, many experiments suggest that the melting of nano- and micro-sized metallic nuclei follows a different process not described by traditional melting theory. In this paper, we demonstrate through simulation that the melting of solid nuclei of these sizes occurs via random breaches at the interfaces. Moreover, this breaching process occurs at the exact solid-liquid equilibrium temperature and in the absence of any external disturbance, which suggests the name “self-instability” for this melting process. We attribute this spontaneous instability to the curvature of the samples; based on the relationship between the sample’s instability and its curvature, we propose a destabilizing model for small systems. This model fits well with experimental results and leads to new insights into the instability behavior of small-sized systems; these insights have broad implications for research topics ranging from dendrite self-fragmentation to nanoparticle instability. PMID:26685800

  13. The Atomic scale structure of liquid metal-electrolyte interfaces

    NASA Astrophysics Data System (ADS)

    Murphy, B. M.; Festersen, S.; Magnussen, O. M.

    2016-07-01

    Electrochemical interfaces between immiscible liquids have lately received renewed interest, both for gaining fundamental insight as well as for applications in nanomaterial synthesis. In this feature article we demonstrate that the atomic scale structure of these previously inaccessible interfaces nowadays can be explored by in situ synchrotron based X-ray scattering techniques. Exemplary studies of a prototypical electrochemical system - a liquid mercury electrode in pure NaCl solution - reveal that the liquid metal is terminated by a well-defined atomic layer. This layering decays on length scales of 0.5 nm into the Hg bulk and displays a potential and temperature dependent behaviour that can be explained by electrocapillary effects and contributions of the electronic charge distribution on the electrode. In similar studies of nanomaterial growth, performed for the electrochemical deposition of PbFBr, a complex nucleation and growth behaviour is found, involving a crystalline precursor layer prior to the 3D crystal growth. Operando X-ray scattering measurements provide detailed data on the processes of nanoscale film formation.

  14. Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand.

    PubMed

    Scoppola, Ernesto; Watkins, Erik B; Campbell, Richard A; Konovalov, Oleg; Girard, Luc; Dufrêche, Jean-Francois; Ferru, Geoffroy; Fragneto, Giovanna; Diat, Olivier

    2016-08-01

    Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid-liquid interface exist. Here, the combined application of X-ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.

  15. [The physics of pattern formation of liquid interfaces

    SciTech Connect

    Not Available

    1993-05-01

    Energy consumption in fabrication of materials for all applications is process dependent. Improvements in the ability to process materials are of great importance to the DOE mission. This project addresses basic science questions related to the processing of materials and is aimed at understanding growth of interfaces and evolution of patterns on interfaces, both macroscopic and microscopic. Three laboratory experiments are proposed: A study of the changes in patterns available to the growth of a macroscopic interface when that interface is grown over one of a variety of ``microscopic`` lattices; a study of reversible aggregation of colloidal particles in a mixed solvent, and of the interactions and relaxations of both solvent and suspended particles when thermodynamic conditions are changed for a liquid matrix with suspended particles or fibres; and, an investigation of the sedimentation of particles in a quasi-two-dimensional viscous fluid, with attention both to the dynamics of the flow and to the roughness of the resulting surface of settled particles.

  16. [The physics of pattern formation of liquid interfaces

    SciTech Connect

    Not Available

    1993-01-01

    Energy consumption in fabrication of materials for all applications is process dependent. Improvements in the ability to process materials are of great importance to the DOE mission. This project addresses basic science questions related to the processing of materials and is aimed at understanding growth of interfaces and evolution of patterns on interfaces, both macroscopic and microscopic. Three laboratory experiments are proposed: A study of the changes in patterns available to the growth of a macroscopic interface when that interface is grown over one of a variety of microscopic'' lattices; a study of reversible aggregation of colloidal particles in a mixed solvent, and of the interactions and relaxations of both solvent and suspended particles when thermodynamic conditions are changed for a liquid matrix with suspended particles or fibres; and, an investigation of the sedimentation of particles in a quasi-two-dimensional viscous fluid, with attention both to the dynamics of the flow and to the roughness of the resulting surface of settled particles.

  17. Interface Superconductivity in Cuprates Defies Fermi-Liquid Description

    SciTech Connect

    Radović, Zoran; Vanević, Mihajlo; Wu, Jie; Bollinger, Anthony T.; Božović, Ivan

    2016-07-26

    La2-xSrxCuO4/La2CuO4 bilayers show interface superconductivity that originates from accumulation and depletion of mobile charge carriers across the interface. Surprisingly, the doping level can be varied broadly (within the interval 0.15 < x < 0.47) without affecting the transition temperature, which stays essentially constant and equal to that in optimally doped material, Tc ≈ 40 K. Here we argue that this finding implies that doping up to the optimum level does not shift the chemical potential, unlike in ordinary Fermi liquids. Lastly, we discuss possible physical scenarios that can give doping-independent chemical potential in the pseudogap regime: electronic phase separation, formation of charge-density waves, strong Coulomb interactions, or self-trapping of mobile charge carriers.

  18. Interface Superconductivity in Cuprates Defies Fermi-Liquid Description

    DOE PAGES

    Radović, Zoran; Vanević, Mihajlo; Wu, Jie; ...

    2016-07-26

    La2-xSrxCuO4/La2CuO4 bilayers show interface superconductivity that originates from accumulation and depletion of mobile charge carriers across the interface. Surprisingly, the doping level can be varied broadly (within the interval 0.15 < x < 0.47) without affecting the transition temperature, which stays essentially constant and equal to that in optimally doped material, Tc ≈ 40 K. Here we argue that this finding implies that doping up to the optimum level does not shift the chemical potential, unlike in ordinary Fermi liquids. Lastly, we discuss possible physical scenarios that can give doping-independent chemical potential in the pseudogap regime: electronic phase separation, formationmore » of charge-density waves, strong Coulomb interactions, or self-trapping of mobile charge carriers.« less

  19. Low-reflection-coefficient liquid interfaces for system characterization.

    PubMed

    Hall, T J; Madsen, E L; Dong, F; Medina, I R; Frank, G R

    2001-07-01

    The use of liquid brominated hydrocarbons to form a planar reflecting interface with water is described. Gravity-based planar reflecting surfaces with known reflection coefficients can be used in system characterization for quantitative ultrasonics, and a set of surfaces with a range of reflection coefficients allows calibration of the output power and receiver gain of ultrasonic imaging systems. The substances reported here are immiscible in water and form interfaces with water, resulting in a broad range of acoustic reflection coefficients. Reflection coefficients were measured at temperatures from 18-24 degrees C for "pure" substances and for mixtures of two brominated hydrocarbons. Results show that reflection coefficients are weakly dependent on temperature and that, at a specific temperature, a significant range of arbitrarily small reflection coefficients is available, in the case of the mixtures, by the appropriate choice of weight-percents of the two brominated hydrocarbons.

  20. Biofilm formation at the solid-liquid and air-liquid interfaces by Acinetobacter species

    PubMed Central

    2011-01-01

    Background The members of the genus Acinetobacter are Gram-negative cocobacilli that are frequently found in the environment but also in the hospital setting where they have been associated with outbreaks of nosocomial infections. Among them, Acinetobacter baumannii has emerged as the most common pathogenic species involved in hospital-acquired infections. One reason for this emergence may be its persistence in the hospital wards, in particular in the intensive care unit; this persistence could be partially explained by the capacity of these microorganisms to form biofilm. Therefore, our main objective was to study the prevalence of the two main types of biofilm formed by the most relevant Acinetobacter species, comparing biofilm formation between the different species. Findings Biofilm formation at the air-liquid and solid-liquid interfaces was investigated in different Acinetobacter spp. and it appeared to be generally more important at 25°C than at 37°C. The biofilm formation at the solid-liquid interface by the members of the ACB-complex was at least 3 times higher than the other species (80-91% versus 5-24%). In addition, only the isolates belonging to this complex were able to form biofilm at the air-liquid interface; between 9% and 36% of the tested isolates formed this type of pellicle. Finally, within the ACB-complex, the biofilm formed at the air-liquid interface was almost 4 times higher for A. baumannii and Acinetobacter G13TU than for Acinetobacter G3 (36%, 27% & 9% respectively). Conclusions Overall, this study has shown the capacity of the Acinetobacter spp to form two different types of biofilm: solid-liquid and air-liquid interfaces. This ability was generally higher at 25°C which might contribute to their persistence in the inanimate hospital environment. Our work has also demonstrated for the first time the ability of the members of the ACB-complex to form biofilm at the air-liquid interface, a feature that was not observed in other

  1. High temperature interaction behavior at liquid metal-ceramic interfaces.

    SciTech Connect

    McDeavitt, S. M.; Billings, G. W.; Indacochea, J. E.; Chemical Engineering; Integrated Thermal Sciences, Inc.

    2002-08-01

    Liquid metal/ceramic interaction experiments were undertaken at elevated temperatures with the purpose of developing reusable crucibles for melting reactive metals. The metals used in this work included zirconium (Zr), Zr-8 wt.% stainless steel, and stainless steel containing 15 wt.% Zr. The ceramic substrates include yttria, Zr carbide, and hafnium (Hf) carbide. The metal-ceramic samples were placed on top of a tungsten (W) dish. These experiments were conducted with the temperature increasing at a controlled rate until reaching set points above 2000 C; the systems were held at the peak temperature for about five min and then cooled. The atmosphere in the furnace was argon (Ar). An outside video recording system was used to monitor the changes on heating up and cooling down. All samples underwent a post-test metallurgical examination. Pure Zr was found to react with yttria, resulting in oxygen (O) evolution at the liquid metal-ceramic interface. In addition, dissolved O was observed in the as-cooled Zr metal. Yttrium (Y) was also present in the Zr metal, but it had segregated to the grain boundaries on cooling. Despite the normal expectations for reactive wetting, no transition interface was developed, but the Zr metal was tightly bound to yttria ceramic. Similar reactions occurred between the yttria and the Zr-stainless steel alloys. Two other ceramic samples were Zr carbide and Hf carbide; both carbide substrates were wetted readily by the molten Zr, which flowed easily to the sides of the substrates. The molten Zr caused a very limited dissolution of the Zr carbide, and it reacted more strongly with the Hf carbide. These reactive wetting results are relevant to the design of interfaces and the development of reactive filler metals for the fabrication of high temperature components through metal-ceramic joining. Parameters that have a marked impact on this interface reaction include the thermodynamic stability of the substrate, the properties of the modified

  2. Temperature and Depth Dependence of Order in Liquid Crystal Interfaces

    SciTech Connect

    Martinez-Miranda,L.; Hu, Y.

    2006-01-01

    We have studied the depth dependence and temperature behavior of the ordering of smectic-A films close to the smectic A-nematic transition, deposited on grated glass. X-ray grazing incidence geometry in reflection mode through the glass substrate was used to characterize the samples. Our results indicate the presence of a structure similar to the helical twist grain boundary phase. The structure has two maxima, one close to the glass-liquid crystal interface and another about 8 {mu}m above the surface. The structure at 8 {mu}m is the one that dominates at higher temperatures. In addition, we find that order is preserved to temperatures close to the nematic-isotropic transition temperature for the deeper gratings. We find also a dependence of the orientation of the structure with the depth of the grating and the elastic constant of the liquid crystal.

  3. Non-lamellar lipid liquid crystalline structures at interfaces.

    PubMed

    Chang, Debby P; Barauskas, Justas; Dabkowska, Aleksandra P; Wadsäter, Maria; Tiberg, Fredrik; Nylander, Tommy

    2015-08-01

    The self-assembly of lipids leads to the formation of a rich variety of nano-structures, not only restricted to lipid bilayers, but also encompassing non-lamellar liquid crystalline structures, such as cubic, hexagonal, and sponge phases. These non-lamellar phases have been increasingly recognized as important for living systems, both in terms of providing compartmentalization and as regulators of biological activity. Consequently, they are of great interest for their potential as delivery systems in pharmaceutical, food and cosmetic applications. The compartmentalizing nature of these phases features mono- or bicontinuous networks of both hydrophilic and hydrophobic domains. To utilize these non-lamellar liquid crystalline structures in biomedical devices for analyses and drug delivery, it is crucial to understand how they interact with and respond to different types of interfaces. Such non-lamellar interfacial layers can be used to entrap functional biomolecules that respond to lipid curvature as well as the confinement. It is also important to understand the structural changes of deposited lipid in relation to the corresponding bulk dispersions. They can be controlled by changing the lipid composition or by introducing components that can alter the curvature or by deposition on nano-structured surface, e.g. vertical nano-wire arrays. Progress in the area of liquid crystalline lipid based nanoparticles opens up new possibilities for the preparation of well-defined surface films with well-defined nano-structures. This review will focus on recent progress in the formation of non-lamellar dispersions and their interfacial properties at the solid/liquid and biologically relevant interfaces.

  4. The liquid-liquid interface as a medium to generate nanocrystalline films of inorganic materials.

    PubMed

    Rao, C N R; Kalyanikutty, K P

    2008-04-01

    Unlike the air-water interface, the organic-aqueous (liquid-liquid) interface has not been exploited sufficiently for materials synthesis. In this Account, we demonstrate how ultrathin nanocrystalline films of metals such as gold and silver as well as of inorganic materials such as semiconducting metal chalcogenides (e.g., CdS, CuS, CdSe) and oxides are readily generated at the liquid-liquid interface. What is particularly noteworthy is that single-crystalline films of certain metal chalcogenides are also obtained by this method. The as-prepared gold films at the toluene-water interface comprise fairly monodisperse nanocrystals that are closely packed, the nature and properties of the films being influenced by various reaction parameters such as reaction temperature, time, reactant concentrations, mechanical vibrations, and the viscosity of the medium. The surface plasmon band of gold is markedly red-shifted in the films due to electronic coupling between the particles. The shift of the surface plasmon band of the Au film toward higher wavelengths with an accompanying increase in intensity as a function of reaction time marks the growth of the film. Depending on the reaction temperature, the Au films show interesting electrical transport properties. Films of metals such as gold are disintegrated by the addition of alkanethiols, the effectiveness depending on the alkane chain length, clearly evidenced by shifts of the surface plasmon bands. A time evolution study of the polycrystalline Au and CdS films as well as the single-crystalline CuS films is carried out by employing atomic force microscopy. X-ray reflectivity studies reveal the formation of a monolayer of capped clusters having 13 gold atoms each, arranged in a hexagonal manner at the toluene-water interface. The measurements also reveal an extremely small value of the interfacial tension. Besides describing features of such nanocrystalline films and their mode of formation, their rheological properties have

  5. Liquid chromatography/Fourier transform IR spectrometry interface flow cell

    DOEpatents

    Johnson, C.C.; Taylor, L.T.

    1985-01-04

    A zero dead volume (ZDV) microbore high performance liquid chromatography (..mu.. HPLC)/Fourier transform infrared (FTIR) interface flow cell includes an IR transparent crystal having a small diameter bore therein through which a sample liquid is passed. The interface flow cell further includes a metal holder in combination with a pair of inner, compressible seals for directly coupling the thus configured spectrometric flow cell to the outlet of a ..mu.. HPLC column end fitting to minimize the transfer volume of the effluents exiting the ..mu.. HPLC column which exhibit excellent flow characteristics due to the essentially unencumbered, open-flow design. The IR beam passes transverse to the sample flow through the circular bore within the IR transparent crystal, which is preferably comprised of potassium bromide (KBr) or calcium fluoride (CaF/sub 2/), so as to minimize interference patterns and vignetting encountered in conventional parallel-plate IR cells. The long IR beam pathlength and lensing effect of the circular cross-section of the sample volume in combination with the refractive index differences between the solvent and the transparent crystal serve to focus the IR beam in enhancing sample detection sensitivity by an order of magnitude.

  6. Thermoelectric energy recovery at ionic-liquid/electrode interface

    NASA Astrophysics Data System (ADS)

    Bonetti, Marco; Nakamae, Sawako; Huang, Bo Tao; Salez, Thomas J.; Wiertel-Gasquet, Cécile; Roger, Michel

    2015-06-01

    A thermally chargeable capacitor containing a binary solution of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide in acetonitrile is electrically charged by applying a temperature gradient to two ideally polarisable electrodes. The corresponding thermoelectric coefficient is -1.7 mV/K for platinum foil electrodes and -0.3 mV/K for nanoporous carbon electrodes. Stored electrical energy is extracted by discharging the capacitor through a resistor. The measured capacitance of the electrode/ionic-liquid interface is 5 μF for each platinum electrode while it becomes four orders of magnitude larger, ≈36 mF, for a single nanoporous carbon electrode. Reproducibility of the effect through repeated charging-discharging cycles under a steady-state temperature gradient demonstrates the robustness of the electrical charging process at the liquid/electrode interface. The acceleration of the charging by convective flows is also observed. This offers the possibility to convert waste-heat into electric energy without exchanging electrons between ions and electrodes, in contrast to what occurs in most thermogalvanic cells.

  7. Universal electrode interface for electrocatalytic oxidation of liquid fuels.

    PubMed

    Liao, Hualing; Qiu, Zhipeng; Wan, Qijin; Wang, Zhijie; Liu, Yi; Yang, Nianjun

    2014-10-22

    Electrocatalytic oxidations of liquid fuels from alcohols, carboxylic acids, and aldehydes were realized on a universal electrode interface. Such an interface was fabricated using carbon nanotubes (CNTs) as the catalyst support and palladium nanoparticles (Pd NPs) as the electrocatalysts. The Pd NPs/CNTs nanocomposite was synthesized using the ethylene glycol reduction method. It was characterized using transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, voltammetry, and impedance. On the Pd NPs/CNTs nanocomposite coated electrode, the oxidations of those liquid fuels occur similarly in two steps: the oxidations of freshly chemisorbed species in the forward (positive-potential) scan and then, in the reverse scan (negative-potential), the oxidations of the incompletely oxidized carbonaceous species formed during the forward scan. The oxidation charges were adopted to study their oxidation mechanisms and oxidation efficiencies. The oxidation efficiency follows the order of aldehyde (formaldehyde) > carboxylic acid (formic acid) > alcohols (ethanol > methanol > glycol > propanol). Such a Pd NPs/CNTs nanocomposite coated electrode is thus promising to be applied as the anode for the facilitation of direct fuel cells.

  8. Liquid chromatography/Fourier transform IR spectrometry interface flow cell

    DOEpatents

    Johnson, Charles C.; Taylor, Larry T.

    1986-01-01

    A zero dead volume (ZDV) microbore high performance liquid chromatography (.mu.HPLC)/Fourier transform infrared (FTIR) interface flow cell includes an IR transparent crystal having a small diameter bore therein through which a sample liquid is passed. The interface flow cell further includes a metal holder in combination with a pair of inner, compressible seals for directly coupling the thus configured spectrometric flow cell to the outlet of a .mu.HPLC column end fitting to minimize the transfer volume of the effluents exiting the .mu.HPLC column which exhibit excellent flow characteristics due to the essentially unencumbered, open-flow design. The IR beam passes transverse to the sample flow through the circular bore within the IR transparent crystal, which is preferably comprised of potassium bromide (KBr) or calcium fluoride (CaF.sub.2), so as to minimize interference patterns and vignetting encountered in conventional parallel-plate IR cells. The long IR beam pathlength and lensing effect of the circular cross-section of the sample volume in combination with the refractive index differences between the solvent and the transparent crystal serve to focus the IR beam in enhancing sample detection sensitivity by an order of magnitude.

  9. Thermoelectric energy recovery at ionic-liquid/electrode interface

    SciTech Connect

    Bonetti, Marco; Nakamae, Sawako; Huang, Bo Tao; Wiertel-Gasquet, Cécile; Roger, Michel; Salez, Thomas J.

    2015-06-28

    A thermally chargeable capacitor containing a binary solution of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide in acetonitrile is electrically charged by applying a temperature gradient to two ideally polarisable electrodes. The corresponding thermoelectric coefficient is −1.7 mV/K for platinum foil electrodes and −0.3 mV/K for nanoporous carbon electrodes. Stored electrical energy is extracted by discharging the capacitor through a resistor. The measured capacitance of the electrode/ionic-liquid interface is 5 μF for each platinum electrode while it becomes four orders of magnitude larger, ≈36 mF, for a single nanoporous carbon electrode. Reproducibility of the effect through repeated charging-discharging cycles under a steady-state temperature gradient demonstrates the robustness of the electrical charging process at the liquid/electrode interface. The acceleration of the charging by convective flows is also observed. This offers the possibility to convert waste-heat into electric energy without exchanging electrons between ions and electrodes, in contrast to what occurs in most thermogalvanic cells.

  10. Computer simulation of liquid/liquid interfaces. I. Theory and application to octane/water

    NASA Astrophysics Data System (ADS)

    Zhang, Yuhong; Feller, Scott E.; Brooks, Bernard R.; Pastor, Richard W.

    1995-12-01

    Statistical ensembles for simulating liquid interfaces at constant pressure and/or surface tension are examined, and equations of motion for molecular dynamics are obtained by various extensions of the Andersen extended system approach. Valid ensembles include: constant normal pressure and surface area; constant tangential pressure and length normal to the interface; constant volume and surface tension; and constant normal pressure and surface tension. Simulations at 293 K and 1 atm normal pressure show consistent results with each other and with a simulation carried out at constant volume and energy. Calculated surface tensions for octane/water (61.5 dyn/cm), octane/vacuum (20.4 dyn/cm) and water/vacuum (70.2 dyn/cm) are in very good agreement with experiment (51.6, 21.7, and 72.8 dyn/cm, respectively). The practical consequences of simulating with two other approaches commonly used for isotropic systems are demonstrated on octane/water: applying equal normal and tangential pressures leads to an instability; and applying a constant isotropic pressure of 1 atm leads to a large positive normal pressure. Both results are expected for a system of nonzero surface tension. Mass density and water polarization profiles in the liquid/liquid and liquid/vapor interfaces are also compared.

  11. Nematic liquid crystals at rough and fluctuating interfaces.

    PubMed

    Elgeti, J; Schmid, F

    2005-12-01

    Nematic liquid crystals at rough and fluctuating interfaces are analyzed within the Frank elastic theory and the Landau-de Gennes theory. We study specifically interfaces that locally favor planar anchoring. In the first part we reconsider the phenomenon of Berreman anchoring on fixed rough surfaces, and derive new simple expressions for the corresponding azimuthal anchoring energy. Surprisingly, we find that for strongly aligning surfaces, it depends only on the geometrical surface anisotropy and the bulk elastic constants, and not on the precise values of the chemical surface parameters. In the second part, we calculate the capillary waves at nematic-isotropic interfaces. If one neglects elastic interactions, the capillary wave spectrum is characterized by an anisotropic interfacial tension. With elastic interactions, the interfacial tension, i.e., the coefficient of the leading q(2) term of the capillary wave spectrum, becomes isotropic. However, the elastic interactions introduce a strongly anisotropic cubic q(3) term. The amplitudes of capillary waves are largest in the direction perpendicular to the director. These results are in agreement with previous molecular dynamics simulations.

  12. Advanced Technology Development: Solid-Liquid Interface Characterization Hardware

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Characterizing the solid-liquid interface during directional solidification is key to understanding and improving material properties. The goal of this Advanced Technology Development (ATD) has been to develop hardware, which will enable real-time characterization of practical materials, such as aluminum (Al) alloys, to unprecedented levels. Required measurements include furnace and sample temperature gradients, undercooling at the growing interface, interface shape, or morphology, and furnace translation and sample growth rates (related). These and other parameters are correlated with each other and time. A major challenge was to design and develop all of the necessary hardware to measure the characteristics, nearly simultaneously, in a smaller integral furnace compatible with existing X-ray Transmission Microscopes, XTMs. Most of the desired goals have been accomplished through three generations of Seebeck furnace brassboards, several varieties of film thermocouple arrays, heaters, thermal modeling of the furnaces, and data acquisition and control (DAC) software. Presentations and publications have resulted from these activities, and proposals to use this hardware for further materials studies have been submitted as sequels to this last year of the ATD.

  13. Giant Deformations of a Liquid-Liquid Interface Induced by the Optical Radiation Pressure

    SciTech Connect

    Casner, Alexis; Delville, Jean-Pierre

    2001-07-30

    Because of the small momentum of photons, very intense fields are generally required to bend a liquid interface with the optical radiation pressure. We explore this issue in a near-critical phase-separated liquid mixture to vary continuously the meniscus softness by tuning the temperature. Low power continuous laser waves become sufficient to induce huge stationary bulges. Using the beam size to build an ''optical'' Bond number, Bo , we investigate the crossover from low to large Bo . The whole set of data collapses onto a single master curve which illustrates the universality of the phenomenon.

  14. A general strategy for self-assembly of nanosized building blocks on liquid/liquid interfaces.

    PubMed

    Liu, Jian-Wei; Zhang, Shao-Yi; Qi, Hao; Wen, Wu-Cheng; Yu, Shu-Hong

    2012-08-06

    A family of water/oil interfaces is introduced to provide effective platforms for rapid fabrication of large-area self-assembled nanofilms composed of various nanosized building blocks, including nanoparticles (NPs), nanocubes (NC), nanowires (NWs), and nanosheets, at room temperature. As a general interfacial assembly method, NWs and NPs are co-assembled at the liquid/liquid interface. The as-prepared co-assembled Ag NW and Ag NC films show high surface-enhanced Raman spectroscopy (SERS) intensity, the SERS performance being strongly dependent on the number ratio of the two kinds of nanosized building blocks. The results demonstrate that this interfacial system provides a general method for the assembly of various nanosized building blocks with different shapes and dimensionalities, and thus paves an alternative pathway for further applications of macroscopic assemblies with different functionalities.

  15. Electrostatic Assembly of Polymers and Nanoparticles at Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Hoagland, David

    The electrostatic attraction between charged solutes on opposite sides of the interface between immiscible liquids offers an efficient route to the self-assembly of two-dimensional films. As implemented by us, a hydrophobic polymer with amine end(s) or block(s) is presented in an oil phase, and a negatively charged nanoparticle is presented in an aqueous phase; both solutes are insoluble in the opposite phase but efficiently driven to the liquid-liquid interface by mutual electrostatically attraction to the solute in the opposite phase. Depending on experimental conditions (salt concentration, pH, solute concentrations, etc.), a continuous, nanoscopically thin composite film builds at the oil-water interface over the timescale of minutes, often accompanied by a dramatic reduction of interfacial tension akin to that observed for a surfactant. Film formation and properties by the new route will be discussed, as principally probed through pendant drop interfacial tensiometry and pendant drop interfacial rheometry. Components of model system are toluene-dissolved amine end-capped polystyrene and water-dispersed acid-treated carbon nanotubes or citrate-treated gold nanospheres. Film structures are complicated, as are crucial electrostatic interactions near the interface. With amine end-capped polystyrene partnered with acid-treated carbon nanotubes, high pH (above 5) and high polystyrene molecular weight (above 5000 g/mol) strongly hinder film formation. These films, which are liquid-like, show two viscoelastic relaxations, a fast relaxation (about 10 s) associated with polystyrene chain rearrangements (slightly impacted by carbon nanotube association) and a slow relaxation (about 20 min) associated with polystyrene adsorption/desorption; at intermediate times (or frequencies), the two-dimensional storage and loss moduli follow approximately the same power law dependences. Support by NSF through the Univ. of Massachusetts MRSEC.

  16. Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand

    SciTech Connect

    Scoppola, Ernesto; Campbell, Richard A.; Konovalov, Oleg; Girard, Luc; Fragneto, Giovanna; Diat, Olivier

    2016-06-20

    Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid–liquid interface exist. Here, the combined application of X-ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.

  17. Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface.

    PubMed

    Armao Iv, Joseph J; Nyrkova, Irina; Fuks, Gad; Osypenko, Artem; Maaloum, Mounir; Moulin, Emilie; Arenal, Raul; Gavat, Odile; Semenov, Alexander; Giuseppone, Nicolas

    2017-02-15

    The study of supramolecular polymers in the bulk, in diluted solution, and at the solid-liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid-liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform-water interface. The resulting interfacial nematic layer of these 1D supramolecular polymers is further used as a template for the precise alignment of spherical gold nanoparticles coming from the water phase. These hybrid thin films are spontaneously formed in a single process, without chemical prefunctionalization of the metallic nanoparticles, and their ordering is improved by centrifugation. The resulting polymer chains and strings of nanoparticles can be co-aligned with high anisotropy over very large distances. By using a combination of experimental and theoretical investigations, we decipher the full sequence of this oriented self-assembly process. In such a highly anisotropic configuration, electron energy loss spectroscopy reveals that the self-assembled nanoparticles behave as plasmonic waveguides.

  18. Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces

    DTIC Science & Technology

    2016-01-13

    AFRL-AFOSR-VA-TR-2016-0067 Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces Michael Fayer LELAND STANFORD JUNIOR...2016 4. TITLE AND SUBTITLE Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces 5a. CONTRACT NUMBER 5b. GRANT...were performed. Room temperature ionic liquids were also investigated. Room temperature ionic liquids (RTIL) are intrinsically interesting because

  19. Thermodynamics and intrinsic structure of the Al-Pb liquid-liquid interface: a molecular dynamics simulation study.

    PubMed

    Yang, Yang; Laird, Brian B

    2014-07-17

    We examine the thermodynamics and intrinsic structure of the Al-Pb liquid-liquid interface using molecular dynamics simulation and embedded atom method potentials. The instantaneous interfacial positions, from which the intrinsic structure and the capillary fluctuation spectrum are determined, are calculated using a grid-based method. The interfacial free energy extracted from the capillary fluctuation spectrum is shown to be in excellent agreement with that calculated mechanically by integrating the stress profile. The intrinsic liquid-liquid interfacial density profile shows structural oscillations in the liquid phases in the interfacial region that are shown to be quantitatively similar to the radial distribution functions of the bulk liquid, consistent with theoretical predictions from classical density functional theory and with earlier simulations on liquid-liquid and liquid-vapor interfaces. In addition, we show the mean interfacial density profile for this system is well described as a convolution of the intrinsic density profile and the probability distribution of interfacial position.

  20. Solid-Liquid Interface Characterization Hardware: Advanced Technology Development (ATD)

    NASA Technical Reports Server (NTRS)

    Peters, Palmer N.; Sisk, R. C.; Sen, S.; Kaukler, W. F.; Curreri, Peter A.; Wang, F. C.; Rose, M. Franklin (Technical Monitor)

    2000-01-01

    This ATD has the goal of enabling the integration of three separate measurement techniques to characterize the solid-liquid interface of directionally solidified materials in real-time. Arrays of film-based metal thermocouple elements are under development along with compact Seebeck furnaces suitable for interfacing with separately developed X-ray Transmission Microscopes. Results of applying film arrays to furnace profiling are shown, demonstrating their ability to identify a previously undetected hardware flaw in the development of a second-generation compact furnace. Results of real-time furnace profiling also confirmed that the compact furnace design effectively isolates the temperature profiles in two halves of the furnace, a necessary feature. This isolation had only been inferred previously from the characteristics of Seebeck data reported. Results from a 24-thermocouple array successfully monitoring heating and isothermal cooling of a tin sample are shown. The importance of non-intrusion by the arrays, as well as furnace design, on the profiling of temperature gradients is illustrated with example measurements. Further developments underway for effectively combining all three measurements are assessed in terms of improved x-ray transmission, increased magnification, integral arrays with minimum intrusion, integral scales for velocity measurements and other features being incorporated into the third generation Seebeck furnace under construction.

  1. Liquid-gated interface superconductivity on an atomically flat film.

    PubMed

    Ye, J T; Inoue, S; Kobayashi, K; Kasahara, Y; Yuan, H T; Shimotani, H; Iwasa, Y

    2010-02-01

    Liquid/solid interfaces are attracting growing interest not only for applications in catalytic activities and energy storage, but also for their new electronic functions in electric double-layer transistors (EDLTs) exemplified by high-performance organic electronics, field-induced electronic phase transitions, as well as superconductivity in SrTiO(3) (ref. 12). Broadening EDLTs to induce superconductivity within other materials is highly demanded for enriching the materials science of superconductors. However, it is severely hampered by inadequate choice of materials and processing techniques. Here we introduce an easy method using ionic liquids as gate dielectrics, mechanical micro-cleavage techniques for surface preparation, and report the observation of field-induced superconductivity showing a transition temperature T(c)=15.2 K on an atomically flat film of layered nitride compound, ZrNCl. The present result reveals that the EDLT is an extremely versatile tool to induce electronic phase transitions by electrostatic charge accumulation and provides new routes in the search for superconductors beyond those synthesized by traditional chemical methods.

  2. Fluctuation Analysis of Liquid/Liquid and Gel/Liquid Interfaces

    DTIC Science & Technology

    1989-03-17

    gel/water interface were determined by using cyclic voltammetry and zero current potentiometric methods in a four-electrode system. It has been...interface is due to the difference of the diffusion coefficients in the gel-nitrobenzene as opposed to pure nitrobenzene. In the present study an...and the real part of the diffusional impedance is calculated ; its absolute values can be obtained by multiplying the numbers in the Table by 12 e

  3. Behavior of solute adsorbed at the liquid-liquid interface during solvent extraction with porous-membrane phase separators

    SciTech Connect

    Persaud, G.; Xiu-min, T.; Cantwell, F.F.

    1987-01-01

    Porous membranes are used effectively as phase separators in analytical solvent extraction. When the solute involved can be adsorbed at the liquid-liquid interface, it is found that more vigorous agitation of the mixture causes a decrease in concentration of solute in the liquid flowing through the porous membrane. It is shown experimentally for the interfacially adsorbed component methylene blue perchlorate that the distribution isotherm between chloroform and water is the same in stirred and unstirred mixtures. This suggests that the interfacially adsorbed solute remains at the interface and does not enter the bulk liquid phases during the membrane-induced coalescence and phase separation. Hydrodynamic and diffusion rate calculations confirm this conclusion by showing that the residence time of the solute deposited at the liquid-liquid interface near the membrane (0.1 s) is too short for solute to diffuse through the stagnant Nernst diffusion layer.

  4. Adsorption kinetics of surfactants at liquid-solid and liquid-vapor interfaces from atomic-scale simulations

    NASA Astrophysics Data System (ADS)

    Iskrenova, Eugeniya K.; Patnaik, Soumya S.

    2012-02-01

    Nucleate pool boiling of pure liquid is a complex process involving different size- and time-scale phenomena. The appearance of the first nanobubble in the liquid at the bottom of a hot pan, the detachment of the bubble from the solid surface, its subsequent coalescence with other bubbles, all represent complex multiscale phenomena. Surfactants added to water increase the complexity of the process by contributing to the dynamic surface tension at the liquid-vapor and liquid-solid interfaces and thus affecting the heat and mass transfer at those interfaces. We apply molecular dynamics simulations to study the adsorption kinetics of anionic, cationic, and non-ionic surfactants at liquid/solid and liquid/vapor interfaces. The all-atom vs. united-atom approaches for the solid and surfactants are surveyed in view of their applicability at near boiling temperatures and a range of model water potentials is assessed for reproducing the thermal properties of water at boiling conditions.

  5. Effect of Surfactants on Drop Coalescence at Liquid/liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Weheliye, Weheliye Hashii; Dong, Teng; Angeli, Panagiota

    2016-11-01

    In this paper the coalescence of a drop with a liquid-liquid interface was investigated experimentally using Particle Image Velocimetry (PIV). Initially the drop rest on the interface was studied. It was found that during drop rest the interface deformed before rupture, and the deformation increased with increasing surfactant concentration. The results from PIV showed that two counter-rotating vortices formed inside the droplet during the rupture process which moved from the bottom to the top of the drop. The evolutions of vortices for three surfactant concentrations will be presented. The vortices moved faster in lower surfactant concentrations compared to the higher ones. The intensities of the vortices in different concentrations were also calculated. After the rupture, for low surfactant concentrations, the intensities increased with time and reached a maximum while at later times they decreased. At high surfactant concentrations, the increase and subsequent decrease in intensity was not as pronounced. The work is support by the MEMPHIS program and the University College London. The author Teng Dong would like to thank the Chinese Scholarship Council (CSC) for providing funds for his overseas research.

  6. Exposure of Mammalian Cells to Air-Pollutant Mixtures at the Air-Liquid Interface

    EPA Science Inventory

    It has been widely accepted that exposure of mammalian cells to air-pollutant mixtures at the air-liquid interface is a more realistic approach than exposing cell under submerged conditions. The VITROCELL systems, are commercially available systems for air-liquid interface expo...

  7. Evolution of the Inner Liquid-Solid Interface During Metal Freezing

    NASA Astrophysics Data System (ADS)

    Ivanova, A. G.; Fuksov, V. M.; Gerasimov, S. F.; Pokhodun, A. I.

    2017-02-01

    The influence of the inner interface initiation method on the interface shape (formation of the planar interface or the interface with the dendrites growing into the liquid metal) was studied both theoretically and experimentally. The results of numerical simulation of the process of heat removal from the metal, corresponding to different initiation methods, revealed the existence of different species of the inner interface. The interface modification during freezing arises from the inequality of temperature gradients on opposite sides of the interface, i.e., from imbalance of heat fluxes on the interphase boundary (Stefan problem). For indium point, the results of numerical simulation were confirmed experimentally.

  8. Liquid-vapor interface of the Stockmayer fluid in a uniform external field.

    PubMed

    Moore, Stan G; Stevens, Mark J; Grest, Gary S

    2015-02-01

    The effect of a uniform (nonspatially varying) external field on the liquid-vapor interface of the Stockmayer fluid (Lennard-Jones particles embedded with a point dipole) has been investigated by molecular-dynamics simulations. The long-ranged parts of both the dipole and Lennard-Jones interactions are treated using an Ewald summation, which removes the effects of the cutoff. The direction of the field shifts the critical point and interfacial properties in different directions. For an external field parallel to the interface, the critical temperature increases, while for a field applied perpendicular to the interface, it decreases. The effects of the field on surface tension and interfacial width are also investigated. For zero field, dipoles near the liquid-vapor interface show a weak orientation parallel to the interface. For fields parallel to the interface, ordering in the liquid phase is greater than the vapor, while for fields perpendicular to the interface, the opposite is true.

  9. Ion-transfer voltammetric determination of folic acid at meso-liquid-liquid interface arrays.

    PubMed

    Jiang, Xuheng; Gao, Kui; Hu, Daopan; Wang, Huanhuan; Bian, Shujuan; Chen, Yong

    2015-04-21

    Voltammetric studies on the simple ion transfer (IT) behaviors of an important water-soluble B-vitamin, folic acid (FA), at the liquid-liquid (L-L) interface were firstly performed and then applied as a novel detection method for FA under physiological conditions. Meso-water-1,6-dichlorohexane (W-DCH) and meso-water-organogel interface arrays were built by using a hybrid mesoporous silica membrane (HMSM) with a unique structure of pores-in-pores and employed as the new platforms for the IT voltammetric study. In view of the unique structure of the HMSM, the impact of the ionic surfactant cetyltrimethylammonium bromide (CTAB), self-assembled within the silica nanochannels of the HMSM, was investigated. In particular, its effect on the IT voltammetric behavior and detection of FA at meso-L-L interface arrays was systematically examined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and differential pulse stripping voltammetry (DPSV). It was found that all the voltammetric responses of CV, DPV, and DPSV and the corresponding detection limit of FA at such meso-L-L interface arrays are closely related to the CTAB in the HMSM. Significantly, the calculated detection limit of FA could be improved to 80 nM after the combination of the DPSV technique with the additional preconcentration of FA in the silica-CTAB nanochannels, achieved through an anion-exchange process between FA(-) and the bromide of CTAB in HMSM. This provides a new and attractive strategy for the detection of those biological anions.

  10. Reduced graphene oxide based silver sulfide hybrid films formed at a liquid/liquid interface

    SciTech Connect

    Bramhaiah, K. John, Neena S.

    2014-04-24

    Free-standing, ultra-thin films of silver sulfide and reduced graphene oxide (RGO) based silver sulfide hybrids are prepared at a liquid/liquid interface employing in situ chemical reaction strategy. Ag{sub 2}S and RGO−Ag{sub 2}S hybrid films are characterized by various techniques such as UV-visible and photo luminescence spectroscopy, X-ray diffraction and scanning electron microscopy. The morphology of hybrid films consists of Ag{sub 2}S nanocrystals on RGO surface while Ag{sub 2}S films contains branched network of dendritic structures. RGO−Ag{sub 2}S exhibit interesting optical and electrical properties. The hybrid films absorb in the region 500–650 nm and show emission in the red region. A higher conductance is observed for the hybrid films arising from the RGO component. This simple low cost method can be extended to prepare other RGO based metal sulfides.

  11. Copper phthalocyanine films deposited by liquid-liquid interface recrystallization technique (LLIRCT).

    PubMed

    Patil, K R; Sathaye, S D; Hawaldar, R; Sathe, B R; Mandale, A B; Mitra, A

    2007-11-15

    The simple recrystallization process is innovatively used to obtain the nanoparticles of copper phthalocyanine by a simple method. Liquid-liquid interface recrystallization technique (LLIRCT) has been employed successfully to produce small sized copper phthalocyanine nanoparticles with diameter between 3-5 nm. The TEM-SAED studies revealed the formation of 3-5 nm sized with beta-phase dominated mixture of alpha and beta copper phthalocyanine nanoparticles. The XRD, SEM, and the UV-vis studies were further carried out to confirm the formation of copper phthalocyanine thin films. The cyclic voltametry (CV) studies conclude that redox reaction is totally reversible one electron transfer process. The process is attributed to Cu(II)/Cu(I) redox reaction.

  12. Solid-liquid interface free energy in binary systems: theory and atomistic calculations for the (110) Cu-Ag interface.

    PubMed

    Frolov, T; Mishin, Y

    2009-08-07

    We analyze thermodynamics of solid-liquid interfaces in binary systems when the solid is in a nonhydrostatic state of stress. The difficulty lies in the fact that chemical potential of at least one of the chemical components in a nonhydrostatic solid is an undefined quantity. We show, nevertheless, that the interface free energy gamma can be defined as excess of an appropriate thermodynamic potential that depends on the chemical potentials in the liquid phase. We derive different forms of the adsorption equation for solid-liquid interfaces, with differential coefficients representing excesses of extensive properties. This leads, in particular, to the formulation of interface stress tau(ij) as an appropriate excess over nonhydrostatic bulk stresses. The interface stress is not unique unless the solid is in a hydrostatic state of stress. We also derive Gibbs-Helmholtz type equations that can be applied for thermodynamic integration of gamma. All thermodynamic relations derived here are presented in forms suitable for atomistic simulations. In particular, the excess quantities can be computed without constructing interface profiles. As an application, we perform semigrand canonical Monte Carlo simulations of the (110) solid-liquid interface in the Cu-Ag system. We show that gamma computed by thermodynamic integration along a coexistence path decreases with increasing composition difference between the phases. At the same time, tau(ij) remains negative (i.e., the interface is in a state of compression), drastically increases in magnitude, and becomes highly anisotropic. Some of the interface excess properties are computed by different methods and demonstrate accurate agreement with each other, confirming the correctness of our analysis.

  13. Nonlinear laser-induced deformations of liquid-liquid interfaces: An optical fiber model

    NASA Astrophysics Data System (ADS)

    Birkeland, Ole Jakob; Brevik, Iver

    2008-12-01

    Experimentally, it turns out that radiation forces from a cw laser on a liquid-liquid interface are able to produce giant deformations (up to about 100μm ), if the system is close to the critical point where the surface tension becomes small. We present a model for such a fingerlike deformation, implying that the system is described as an optical fiber. One reason for introducing such a model is that the refractive index difference in modern experiments, such as those of the Bordeaux group, is small, of the same order as in practical fibers in optics. It is natural therefore to adopt the hybrid HE11 mode, known from fiber theory as the fundamental mode for the liquid system. We show how the balance between hydrodynamical and radiation forces leads to a stable equilibrium point for the liquid column. Also, we calculate the narrowing of the column radius as the depth increases. Comparison with experimental results of the Bordeaux group yields quite satisfactory agreement as regards the column width.

  14. Pyroelectric energy harvesting using liquid-based switchable thermal interfaces

    SciTech Connect

    Cha, G; Ju, YS

    2013-01-15

    The pyroelectric effect offers an intriguing solid-state approach for harvesting ambient thermal energy to power distributed networks of sensors and actuators that are remotely located or otherwise difficult to access. There have been, however, few device-level demonstrations due to challenges in converting spatial temperature gradients into temporal temperature oscillations necessary for pyroelectric energy harvesting. We demonstrate the feasibility of a device concept that uses liquid-based thermal interfaces for rapid switching of the thermal conductance between a pyroelectric material and a heat source/sink and can thereby deliver high output power density. Using a thin film of a pyroelectric co-polymer together with a macroscale mechanical actuator, we operate pyroelectric thermal energy harvesting cycles at frequencies close to 1 Hz. Film-level power densities as high as 110 mW/cm(3) were achieved, limited by slow heat diffusion across a glass substrate. When combined with a laterally interdigitated electrode array and a MEMS actuator, the present design offers an attractive option for compact high-power density thermal energy harvesters. (C) 2012 Elsevier B.V. All rights reserved.

  15. Liquid-film assisted formation of alumina/niobium interfaces

    SciTech Connect

    Sugar, Joshua D.; McKeown, Joseph T.; Marks, Robert A.; Glaeser, Andreas M.

    2002-06-16

    Alumina has been joined at 1400 degrees C using niobium-based interlayers. Two different joining approaches were compared: solid-state diffusion bonding using a niobium foil as an interlayer, and liquid-film assisted bonding using a multilayer copper/niobium/copper interlayer. In both cases, a 127-(mu)m thick niobium foil was used; =1.4-(mu)m or =3-(mu)m thick copper films flanked the niobium. Room-temperature four-point bend tests showed that the introduction of a copper film had a significant beneficial effect on the average strength and the strength distribution. Experiments using sapphire substrates indicated that during bonding the initially continuous copper film evolved into isolated copper-rich droplets/particles at the sapphire/interlayer interface, and extensive regions of direct bonding between sapphire and niobium. Film breakup appeared to initiate at either niobium grain boundary ridges, or at asperities or irregularities on the niobium surface that caused localized contact with the sapphire.

  16. Long DNA Molecules at Liquid-Solid Interfaces

    NASA Astrophysics Data System (ADS)

    Samuilov, Vladimir; Li, B.; Sokolov, J.; Rafailovich, M.; Chu, B.

    2006-03-01

    The electrophoresis of long DNA molecules was studied using a newly developed method of electrophoresis on flat surfaces [1] in the regime of strong electrostatic interaction. The mobility of lambda- DNA molecules on this surface was found to scale as the square root of the persistent length with the ionic strength at high buffer. This experimental result indicates that at high buffer concentration the separation mechanism of solid-liquid interface electrophoresis is expected to be due to surface friction rather than biased reptation [2-4]. At low buffer concentrations the DNA chains are stretched .The electric double layer is responsible for a velocity profile of the electroosmotic flow. The net electrophoretic mobility of longer DNA, being trapped closer to the surface as found to be higher then for the shorter ones in the electric field. [1]. N. Pernodet, V. Samuilov, K. Shin, et al. Physical Review Letters, 85 (2000) 5651-5654. [2] Y.-S. Seo, V.A. Samuilov, J. Sokolov, et al. Electrophoresis, 23 (2002) 2618-2625. [3] Y.-S. Seo, H.. Luo, V. A. Samuilov, et al. DNA Electrophoresis on nanopatterned surfaces, Nano Letters, 4, 2004, 659-664.

  17. Numerical simulation of drop impact on a liquid-liquid interface with a multiple marker front-capturing method

    NASA Astrophysics Data System (ADS)

    Coyajee, Emil; Boersma, Bendiks Jan

    2009-07-01

    The gravity-driven motion of a droplet impacting on a liquid-liquid interface is studied. The full Navier-Stokes equations are solved on a fixed, uniform grid using a finite difference/front-capturing method. For the representation of fluid-fluid interfaces, a coupled Level-Set/Volume-Of-Fluid method [M. Sussman, E.G. Puckett, A coupled Level-Set and Volume-of-Fluid method for computing 3D and axisymmetric incompressible two-phase flows, J. Comp. Phys. 162 (2000) 301-337] is used, in which we introduce the novel approach of describing separate interfaces with different marker functions. As a consequence, we prevent numerical coalescence of the droplet and the liquid-liquid interface without excessive (local) grid refinement. To validate our method, numerical simulations of the drop impact event are compared with experiments [Z. Mohamed-Kassim, E.K. Longmire, Drop impact on a liquid-liquid interface, Phys. Fluids 15 (2003) 3263-3273]. Furthermore, a comparison is made with the numerical results of [A. Esmaeeli, G. Tryggvason, Direct numerical simulations of bubbly flows. Part 2. Moderate Reynolds number arrays, J. Fluid Mech. 385 (1999) 325-358] for an array of rising bubbles. The investigation shows that the multiple marker approach successfully prevents numerical coalescence of interfaces and adequately captures the effect of surface tension.

  18. Vibrational sum frequency spectroscopy of surfactants and phospholipid monolayers at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Smiley, Beth L.; Walker, R. A.; Gragson, D. E.; Hannon, T. E.; Richmond, Geraldine L.

    1998-04-01

    Work from our laboratory on vibrational sum frequency spectroscopic investigations of molecular ordering at the carbon tetrachloride-water interface is reviewed. Simple charged surfactants adsorbed at the liquid-liquid interface are seen to induce alignment of interfacial water molecules to a degree which is dependent on the induced surface potential. Saturation of water molecule alignment occurs at a surfactant surface concentration corresponding to a calculated surface potential of approximately 160 mV. In complementary studies, the relative degree of hydrocarbon chain ordering within monolayers of symmetric phosphatidylcholines of different chain lengths is inferred by the relative signal contributions of the methyl and methylene symmetric stretch modes. The degree of hydrocarbon chain disorder observed depends strongly on the method of monolayer preparation. By one method, a decrease in hydrocarbon chain order is seen with increasing chain length. Another method of monolayer formation yielded very well ordered hydrocarbon chains for the longest chain phosphatidylcholine studied, and showed much greater disorder in shorter chain species which was comparable to the other preparation method. These studies are a foundation for further work with this technique geared towards understanding molecular-level structural features in membrane-like assemblies and surface biochemical interactions of relevance to biomedical research.

  19. Development of a liquid-junction/low-flow interface for phosphate buffer capillary electrophoresis mass spectrometry.

    PubMed

    Li, Fu-An; Huang, Ju-Li; Shen, Shang-Yu; Wang, Che-Wei; Her, Guor-Rong

    2009-04-01

    To alleviate ion suppression from phosphate buffer and to preserve separation integrity, a new capillary electrophoresis mass spectrometry (CE-MS) interface was developed. The interface consisted of a low-flow interface and a liquid junction. In this design, both the inlet reservoir and the liquid-junction reservoir were filled with phosphate running buffer. Because the phosphate anions in the column migrated toward the inlet reservoir (away from the electrospray ionization (ESI) source) the problem of ion suppression in ESI was avoided. The liquid junction was incorporated to eliminate issues of degraded separation observed when sheath liquid interfaces use different buffers for separation and MS analysis attributed to differences in anion velocity. The utility of the interface was demonstrated by the analysis of antihistamines at pH 3.5 and the analysis of perfluorocarboxylic acid at pH 9.5.

  20. Dynamic single-interface hollow fiber liquid phase microextraction of Cr(VI) using ionic liquid containing supported liquid membrane.

    PubMed

    Pimparu, Rungaroon; Nitiyanontakit, Sira; Miró, Manuel; Varanusupakul, Pakorn

    2016-12-01

    The concept of dynamic single-interface hollow fiber membrane liquid-phase microextraction (HF-LPME), where the target analyte was extracted on-line and eluted inside the lumen of the HF membrane, was explored. An ionic liquid containing supported liquid membrane was used for the trace determination of Cr(VI) as a model compound. Since the extraction took place on-line inside the hollow fiber membrane, the mass transfer behavior was described and discussed in comparison with the conventional HF-LPME. The extraction efficiency was improved by a recirculation configuration of the sample solution at relatively high sampling flow rates as a result of the increased effective contact area. The positive pressure observed to be built up during extraction was overcome by a flow-balancing pressure design. The dynamic single-interface HF-LPME method with an enrichment factor of 41, a detection limit of 1.2µgL(-1) and determination limit of 4.0µgL(-1) was successfully applied to the reliable determination of Cr(VI) from environmental water samples. The quantification limit is below the maximum contaminant level in drinking water, set at 10µgL(-1) of hexavalent chromium by the California Environmental Protection Agency.

  1. Interaction of a sodium ion with the water liquid-vapor interface

    NASA Technical Reports Server (NTRS)

    Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

    1989-01-01

    Molecular dynamics results are presented for the density profile of a sodium ion near the water liquid-vapor interface at 320 K. These results are compared with the predictions of a simple dielectric model for the interaction of a monovalent ion with this interface. The interfacial region described by the model profile is too narrow and the profile decreases too abruptly near the solution interface. Thus, the simple model does not provide a satisfactory description of the molecular dynamics results for ion positions within two molecular diameters from the solution interface where appreciable ion concentrations are observed. These results suggest that surfaces associated with dielectric models of ionic processes at aqueous solution interfaces should be located at least two molecular diameters inside the liquid phase. A free energy expense of about 2 kcal/mol is required to move the ion within two molecular layers of the free water liquid-vapor interface.

  2. Preparation and attachment of liquid-infused porous supra-particles to liquid interfaces.

    PubMed

    Al-Shehri, Hamza; Horozov, Tommy S; Paunov, Vesselin N

    2016-10-12

    We prepared model porous composite supra-particles and investigated the effect of the initial infused fluid phase on their attachment at the liquid-fluid interface. We used a simple method for fabrication of millimetre-sized spherical porous supra-particles from much smaller monodisperse latex microparticles as building blocks by evaporation of a polystyrene sulphate latex suspension on a hot super-hydrophobic surface. We annealed the dried supra-particles at the polymer's glass transition temperature to fuse partially their latex particle building blocks. Spherical porous supra-particles were produced above 40 wt% initial concentration of the latex particles in the suspension, which had a rough surface, with a porous and amorphous structure. We controlled the supra-particle size by varying the initial volume of the latex suspension drop, the latex particle concentration and the drop evaporation temperature. This preparation technique allowed limited control over the porosity of the supra-particles by varying the initial concentration of the latex particle suspension, the rate of evaporation and the annealing temperature. We characterised the surface morphology and the inner structure of supra-particles by SEM imaging. We report for the first time results of an MRI study of supra-particles attached to an air-water or an oil-water interface, which indicated that only the surface layer of the building block particles attaches to the liquid interface while the pore fluid was not displaced by the outer fluid. We observed that supra-particles infused with water had different wettability and attachment positions at the oil-water interface compared with the same particles infused with oil. Similarly, the infusion of the porous supra-particles with water led to a different attachment at the air-water interface compared to the attachment of the same supra-particle when dry. The fundamental importance of this result is that the porous particles (or colloid particle

  3. Nematic liquid crystals confined in microcapillaries for imaging phenomena at liquid-liquid interfaces.

    PubMed

    Zhong, Shenghong; Jang, Chang-Hyun

    2015-09-21

    Here, we report the development of an experimental system based on liquid crystals (LCs) confined in microcapillaries for imaging interfacial phenomena. The inner surfaces of the microcapillaries were modified with octadecyltrichlorosilane to promote an escaped-radial configuration of LCs. We checked the optical appearance of the capillary-confined LCs under a crossed polarizing microscope and determined their arrangement based on side and top views. We then placed the capillary-confined LCs in contact with non-surfactant and surfactant solutions, producing characteristic textures of two bright lines and a four-petal shape, respectively. We also evaluated the sensitivity, stability, and reusability of the system. Our imaging system was more sensitive than previously reported LC thin film systems. The textures formed in microcapillaries were stable for more than 120 h and the capillaries could be reused at least 10 times. Finally, we successfully applied our system to image the interactions of phospholipids and bivalent metal ions. In summary, we developed a simple, small, portable, sensitive, stable, and reusable experimental system that can be broadly applied to monitor liquid-liquid interfacial phenomena. These results provide valuable information for designs using confined LCs as chemoresponsive materials in optical sensors.

  4. Temperature dependence of local solubility of hydrophobic molecules in the liquid-vapor interface of water.

    PubMed

    Abe, Kiharu; Sumi, Tomonari; Koga, Kenichiro

    2014-11-14

    One important aspect of the hydrophobic effect is that solubility of small, nonpolar molecules in liquid water decreases with increasing temperature. We investigate here how the characteristic temperature dependence in liquid water persists or changes in the vicinity of the liquid-vapor interface. From the molecular dynamics simulation and the test-particle insertion method, the local solubility Σ of methane in the liquid-vapor interface of water as well as Σ of nonpolar solutes in the interface of simple liquids are calculated as a function of the distance z from the interface. We then examine the temperature dependence of Σ under two conditions: variation of Σ at fixed position z and that at fixed local solvent density around the solute molecule. It is found that the temperature dependence of Σ at fixed z depends on the position z and the system, whereas Σ at fixed local density decreases with increasing temperature for all the model solutions at any fixed density between vapor and liquid phases. The monotonic decrease of Σ under the fixed-density condition in the liquid-vapor interface is in accord with what we know for the solubility of nonpolar molecules in bulk liquid water under the fixed-volume condition but it is much robust since the solvent density to be fixed can be anything between the coexisting vapor and liquid phases. A unique feature found in the water interface is that there is a minimum in the local solubility profile Σ(z) on the liquid side of the interface. We find that with decreasing temperature the minimum of Σ grows and at the same time the first peak in the oscillatory density profile of water develops. It is likely that the minimum of Σ is due to the layering structure of the free interface of water.

  5. Swimming of a model ciliate near an air-liquid interface

    NASA Astrophysics Data System (ADS)

    Wang, S.; Ardekani, A. M.

    2013-06-01

    In this work, the role of the hydrodynamic forces on a swimming microorganism near an air-liquid interface is studied. The lubrication theory is utilized to analyze hydrodynamic effects within the narrow gap between a flat interface and a small swimmer. By using an archetypal low-Reynolds-number swimming model called “squirmer,” we find that the magnitude of the vertical swimming velocity is on the order of O(ɛlnɛ), where ɛ is the ratio of the gap width to the swimmer's body size. The reduced swimming velocity near an interface can explain experimental observations of the aggregation of microorganisms near a liquid interface.

  6. Swimming of a model ciliate near an air-liquid interface.

    PubMed

    Wang, S; Ardekani, A M

    2013-06-01

    In this work, the role of the hydrodynamic forces on a swimming microorganism near an air-liquid interface is studied. The lubrication theory is utilized to analyze hydrodynamic effects within the narrow gap between a flat interface and a small swimmer. By using an archetypal low-Reynolds-number swimming model called "squirmer," we find that the magnitude of the vertical swimming velocity is on the order of O(εlnε), where ε is the ratio of the gap width to the swimmer's body size. The reduced swimming velocity near an interface can explain experimental observations of the aggregation of microorganisms near a liquid interface.

  7. Total internal reflection resonance light scattering at solid/liquid interfaces.

    PubMed

    Tang, Yao-Ji; Chen, Ying; Yao, Min-Na; Li, Yao-Qun

    2008-08-05

    Total internal reflection (TIR) technique is an interface-specific tool and resonance light scattering (RLS) is of high sensitivity. The combination of both approaches is introduced into the solid/liquid interface for the first time. The behaviors of mixture of TPPS and BSA at the interface have been studied with total internal reflection resonance light scattering (TIR-RLS). The preliminary experimental results indicate that TIR-RLS is a good approach to study the interaction and distinguish the states of macromolecules at the solid/liquid interface.

  8. Green-Kubo relation for friction at liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Huang, Kai; Szlufarska, Izabela

    2014-03-01

    We have developed a Green-Kubo relation that enables accurate calculations of friction at solid-liquid interfaces directly from equilibrium molecular dynamics (MD) simulations and that provides a pathway to bypass the time-scale limitations of typical nonequilibrium MD simulations. The theory has been validated for a number of different interfaces and it is demonstrated that the liquid-solid slip is an intrinsic property of an interface. Because of the high numerical efficiency of our method, it can be used in the design of interfaces for applications in aqueous environments, such as nano- and microfluidics.

  9. Isolating Reactions at the Picoliter Scale: Parallel Control of Reaction Kinetics at the Liquid-Liquid Interface.

    PubMed

    Phan-Quang, Gia Chuong; Lee, Hiang Kwee; Ling, Xing Yi

    2016-07-11

    Miniaturized liquid-liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid-liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water-in-decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface-enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p-dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min(-1) for the first-order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.

  10. Particle separation by a moving air-liquid interface in a microchannel.

    PubMed

    Wang, Fengkun; Chon, Chan Hee; Li, Dongqing

    2010-12-15

    Particle separation is an important topic in microfluidic field and has recently gained significant attention in sample preparations for biological and chemical studies. In this paper, a novel particle separation method was proposed. In this method, the particles were separated by the air-liquid interface in a microchannel. The motion of the air-liquid interface was controlled with a syringe pump. Depending on the air-liquid interface speed, the liquid film thickness and the viscous force on particles were changed and the particles were separated by sizes. We observed the separation of 1.01 μm particles from the larger particles when the air-liquid interface speed was less than 11 μm/s, and the separation of both 1.01 μm and 5.09 μm particles from the larger particles when the interface speed was between 11 μm/s and 120 μm/s. When the speed was higher than 120 μm/s, the drag force of the liquid flow generated by the advancing interface on particles was so strong that the flow removed all particles off from the bottom channel wall and there were no particles left behind the advancing interface.

  11. Segregation of ions at the interface: molecular dynamics studies of the bulk and liquid-vapor interface structure of equimolar binary mixtures of ionic liquids.

    PubMed

    Palchowdhury, Sourav; Bhargava, B L

    2015-08-14

    The structures of three different equimolar binary ionic liquid mixtures and their liquid-vapor interface have been studied using atomistic molecular dynamics simulations. Two of these binary mixtures were composed of a common cation 1-n-butyl-3-methylimidazolium and varying anions (chloride and hexafluorophosphate in one of the mixtures and chloride and trifluoromethanesulfonate in the other) and the third binary mixture was composed of a common anion, trifluoromethanesulfonate and two imidazolium cations with ethyl and octyl side chains. Binary mixtures with common cations are found to be homogeneous. The anions are preferentially located near the ring hydrogen atoms due to H-bonding interactions. Segregation of ions is observed at the interface with an enrichment of the liquid-vapor interface layer by longer alkyl chains and bigger anions with a distributed charge. The surface composition is drastically different from that of the bulk composition, with the longer alkyl tail groups and bigger anions populating the outermost layer of the interface. The longer alkyl chains of the cations and trifluoromethanesulfonate anions with a smaller charge density show orientational ordering at the liquid-vapor interface.

  12. Understanding Atomic-Scale Behavior of Liquid Crystals at Aqueous Interfaces.

    PubMed

    Ramezani-Dakhel, Hadi; Sadati, Monirosadat; Rahimi, Mohammad; Ramirez-Hernandez, Abelardo; Roux, Benoît; de Pablo, Juan J

    2017-01-10

    The ordered environment presented by liquid crystals at interfaces enables a range of novel functionalities that is only now beginning to be exploited in applications ranging from light focusing devices to biosensors. One key feature of liquid crystals is that molecular events occurring at an interface propagate over large distances through the bulk. In spite of their importance, our fundamental understanding of liquid crystal-water and liquid crystal-air interfaces remains limited. In this work, we present results from large-scale atomistic molecular dynamics simulations on the organization of the nematic and isotropic phases of the nitrile-containing mesogenic molecule 4-cyano-4'-pentylbiphenyl (5CB) in the vicinity of vacuum and aqueous interfaces. Hybrid boundary conditions are imposed by confining 5CB films between vacuum and an aqueous medium to examine how those two types of interfaces influence the specific structural arrangement and ordering of 5CB. Consistent with experiments, our results indicate that 5CB exhibits homeotropic anchoring at the vacuum interface, and planar alignment at aqueous interfaces. Two-dimensional molecular dynamics potential of mean force calculations and average polarization densities show that the polar nitrile group of 5CB remains hydrated near the aqueous interface, where it modulates the orientation of water molecules. Estimates of the anchoring strength reveal an oscillatory decay and a semilinear decay with distance from the interface in vacuum and water, respectively.

  13. Nematicons across interfaces: anomalous refraction and reflection of solitons in liquid Crystals.

    PubMed

    Peccianti, Marco; Assanto, Gaetano

    2007-06-25

    The robustness of nematicons, i. e. spatial solitons in nematic liquid crystals, can be exploited to implement counter-intuitive negative reflection and refraction schemes for optical signal manipulation at interfaces.

  14. Redistribution of fluorescent molecules at the solid/liquid interface with total internal reflection illumination.

    PubMed

    Wei, Lin; Ye, Zhongju; Luo, Wenjuan; Chen, Bo; Xiao, Lehui

    2016-08-01

    Many intriguing physical and chemical processes commonly take place at the solid/liquid interface. Total internal reflection illumination, together with single molecule spectroscopy, provides a robust platform for the selective exploration of kinetic processes close the interface. With these techniques, it was observed that the distribution of Rhodamine B molecules close to a solid/liquid interface could be regulated in a photo-induced route. The laser-induced repulsion force at this interface is enough to compromise the Brownian diffusion of single molecules in a range of several hundred nanometers normal to the solid/liquid interface. This observation is fundamentally and practically interesting because moderate laser intensity is enough to initiate this repulsion effect. Therefore, it might display extensive applications in the development of photo-modulation technique with high throughput capability.

  15. Dynamic Mass Transfer of Hemoglobin at the Aqueous/Ionic-Liquid Interface Monitored with Liquid Core Optical Waveguide.

    PubMed

    Chen, Xuwei; Yang, Xu; Zeng, Wanying; Wang, Jianhua

    2015-08-04

    Protein transfer from aqueous medium into ionic liquid is an important approach for the isolation of proteins of interest from complex biological samples. We hereby report a solid-cladding/liquid-core/liquid-cladding sandwich optical waveguide system for the purpose of monitoring the dynamic mass-transfer behaviors of hemoglobin (Hb) at the aqueous/ionic liquid interface. The optical waveguide system is fabricated by using a hydrophobic IL (1,3-dibutylimidazolium hexafluorophosphate, BBimPF6) as the core, and protein solution as one of the cladding layer. UV-vis spectra are recorded with a CCD spectrophotometer via optical fibers. The recorded spectra suggest that the mass transfer of Hb molecules between the aqueous and ionic liquid media involve accumulation of Hb on the aqueous/IL interface followed by dynamic extraction/transfer of Hb into the ionic liquid phase. A part of Hb molecules remain at the interface even after the accomplishment of the extraction/transfer process. Further investigations indicate that the mass transfer of Hb from aqueous medium into the ionic liquid phase is mainly driven by the coordination interaction between heme group of Hb and the cationic moiety of ionic liquid, for example, imidazolium cation in this particular case. In addition, hydrophobic interactions also contribute to the transfer of Hb.

  16. Electric Field Effect on Phospholipid Monolayers at an Aqueous-Organic Liquid-Liquid Interface.

    PubMed

    Yu, Hao; Yzeiri, Irena; Hou, Binyang; Chen, Chiu-Hao; Bu, Wei; Vanysek, Petr; Chen, Yu-Sheng; Lin, Binhua; Král, Petr; Schlossman, Mark L

    2015-07-23

    The electric potential difference across cell membranes, known as the membrane potential, plays an important role in the activation of many biological processes. To investigate the effect of the membrane potential on the molecular ordering of lipids within a biomimetic membrane, a self-assembled monolayer of 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC) lipids at an electrified 1,2-dichloroethane/water interface is studied with X-ray reflectivity and interfacial tension. Measurements over a range of electric potential differences, -150 to +130 mV, that encompass the range of typical biomembrane potentials demonstrate a nearly constant and stable structure whose lipid interfacial density is comparable to that found in other biomimetic membrane systems. Measurements at higher positive potentials, up to 330 mV, illustrate a monotonic decrease in the lipid interfacial density and accompanying variations in the interfacial configuration of the lipid. Molecular dynamics simulations, designed to mimic the experimental conditions, show that the measured changes in lipid configuration are due primarily to the variation in area per lipid with increasing applied electric field. Rotation of the SOPC dipole moment by the torque from the applied electric field appears to be negligible, except at the highest measured potentials. The simulations confirm in atomistic detail the measured potential-dependent characteristics of SOPC monolayers. Our hybrid study sheds light on phospholipid monolayer stability under different membrane potentials, which is important for understanding membrane processes. This study also illustrates the use of X-ray surface scattering to probe the ordering of surfactant monolayers at an electrified aqueous-organic liquid-liquid interface.

  17. Chiral induction and amplification in supramolecular systems at the liquid-solid interface.

    PubMed

    Xu, Hong; Ghijsens, Elke; George, Subi J; Wolffs, Martin; Tomović, Željko; Schenning, Albertus P H J; De Feyter, Steven

    2013-06-03

    Chiral induction and amplification in surface-confined supramolecular monolayers are investigated at the liquid-solid interface. Scanning tunneling microscopy (STM) proves that achiral molecules can self-assemble into globally chiral patterns through a variety of approaches, including induction by chiral solvents or by a novel chiral amplification method. Our study demonstrates the aptness of both approaches, which have already been applied to (supramolecular) polymers in solution, to create chiral supramolecular monolayers at the liquid-solid interface.

  18. Effect of thermal convection on the shape of a solid-liquid interface

    NASA Technical Reports Server (NTRS)

    Mennetrier, C.; Chopra, M. A.; De Groh, H. C., III

    1991-01-01

    The effect of thermal convection on the shape of solid-liquid interface was investigated in experiments conducted in a transparent Bridgman-type directional solidification furnace. The relationship was numerically modeled using a standard 2D finite-difference approach, with the solid-liquid deformable interface approximated by a blocking-off technique. The directional solidification furnace was used with pure succinonitrile (which is also transparent) contained in a long square ampoule made of borosilicate glass. With the furnace in the vertical configuration, a flat interface was observed, in agreement with the model. On the other hand, a highly distorted interface was obtained in the horizontal configuration; the numerical results showed a strong recirculating cell in front of the interface due to natural thermal convection. The results indicate that thermal convection is responsible for the interface distortion.

  19. Electrochemical behaviour and voltammetric sensitivity at arrays of nanoscale interfaces between immiscible liquids.

    PubMed

    Rimboud, Mickaël; Hart, Robert D; Becker, Thomas; Arrigan, Damien W M

    2011-11-21

    Arrays of nanoscale interfaces between immiscible electrolyte solutions were formed using silicon nitride nanopore array membranes. Nanopores in the range from 75 nm radius down to 17 nm radius were used to form the nano-interfaces. It was found that the liquid organic phase electrolyte solution filled the pores so that inlaid nano-interfaces were formed with the aqueous phase. Cyclic voltammetry at these nano-interface arrays demonstrated steady-state behaviour at the larger interfaces but the voltammetric wave-shape became progressively worse as the interface size decreased. It was found that the ion transfer currents were ca. 50% of those expected based on theoretical calculations, which is attributed to overlap of diffusion zones at adjacent nano-interfaces. Here, the separation between adjacent nano-interfaces was 20-times the interface radius. The analytical sensitivity for ion transfer from the aqueous to the 1,6-dichlorohexane organic phase was estimated from calibration plots of current density versus concentration of aqueous tetraethylammonium cation. The sensitivity was in the range of 65 μA cm(-2) μM(-1) (at 75 nm radius interfaces) to 265 μA cm(-2) μM(-1) (at 17 nm radius interfaces). The sensitivity depended directly on the inverse of the nano-interface radius, implying that smaller interfaces will provide better sensitivity, due to the enhanced flux of analyte arising from convergent diffusion to smaller electrochemical interfaces.

  20. Insulin Aggregation at a Dynamic Solid-Liquid-Air Triple Interface.

    PubMed

    Frachon, Thibaut; Bruckert, Franz; Le Masne, Quentin; Monnin, Emmanuel; Weidenhaupt, Marianne

    2016-12-13

    Therapeutic proteins are privileged in drug development because of their exquisite specificity, which is due to their three-dimensional conformation in solution. During their manufacture, storage, and delivery, interactions with material surfaces and air interfaces are known to affect their stability. The growing use of automated devices for handling and injection of therapeutics increases their exposure to protocols involving intermittent wetting, during which the solid-liquid and liquid-air interfaces meet at a triple contact line, which is often dynamic. Using a microfluidic setup, we analyze the effect of a moving triple interface on insulin aggregation in real time over a hydrophobic surface. We combine thioflavin T fluorescence and reflection interference microscopy to concomitantly monitor insulin aggregation and the morphology of the liquid as it dewets the surface. We demonstrate that insulin aggregates in the region of a moving triple interface and not in regions submitted to hydrodynamic shear stress alone, induced by the moving liquid. During dewetting, liquid droplets form on the surface anchored by adsorbed proteins, and the accumulation of amyloid aggregates is observed exclusively as fluorescent rings growing eccentrically around these droplets. The fluorescent rings expand until the entire channel surface sweeped by the triple interface is covered by amyloid fibers. On the basis of our experimental results, we propose a model describing the growth mechanism of insulin amyloid fibers at a moving triple contact line, where proteins adsorbed at a hydrophobic surface are exposed to the liquid-air interface.

  1. Fast Responsive and Controllable Liquid Transport on a Magnetic Fluid/Nanoarray Composite Interface.

    PubMed

    Tian, Dongliang; Zhang, Na; Zheng, Xi; Hou, Guanglei; Tian, Ye; Du, Yi; Jiang, Lei; Dou, Shi Xue

    2016-06-28

    Controllable liquid transport on surface is expected to occur by manipulating the gradient of surface tension/Laplace pressure and external stimuli, which has been intensively studied on solid or liquid interface. However, it still faces challenges of slow response rate, and uncontrollable transport speed and direction. Here, we demonstrate fast responsive and controllable liquid transport on a smart magnetic fluid/nanoarray interface, i.e., a composite interface, via modulation of an external magnetic field. The wettability of the composite interface to water instantaneously responds to gradient magnetic field due to the magnetically driven composite interface gradient roughness transition that takes place within a millisecond, which is at least 1 order of magnitude faster than that of other responsive surfaces. A water droplet can follow the motion of the gradient composite interface structure as it responds to the gradient magnetic field motion. Moreover, the water droplet transport direction can be controlled by modulating the motion direction of the gradient magnetic field. The composite interface can be used as a pump for the transport of immiscible liquids and other objects in the microchannel, which suggests a way to design smart interface materials and microfluidic devices.

  2. The molecular structure of the interface between water and a hydrophobic substrate is liquid-vapor like.

    PubMed

    Willard, Adam P; Chandler, David

    2014-11-14

    With molecular simulation for water and a tunable hydrophobic substrate, we apply the instantaneous interface construction [A. P. Willard and D. Chandler, "Instantaneous liquid interfaces," J. Phys. Chem. B 114, 1954-1958 (2010)] to examine the similarity between a water-vapor interface and a water-hydrophobic surface interface. We show that attractive interactions between a hydrophobic surface and water affect capillary wave fluctuations of the instantaneous liquid interface, but these attractive interactions have essentially no effect on the intrinsic interface. The intrinsic interface refers to molecular structure in terms of distances from the instantaneous interface. Further, the intrinsic interface of liquid water and a hydrophobic substrate differs little from that of water and its vapor. The same is not true, we show, for an interface between water and a hydrophilic substrate. In that case, strong directional substrate-water interactions disrupt the liquid-vapor-like interfacial hydrogen bonding network.

  3. A Method To Measure Protein Unfolding at an Air-Liquid Interface.

    PubMed

    Leiske, Danielle L; Shieh, Ian C; Tse, Martha Lovato

    2016-10-04

    Proteins are surface-active molecules that have a propensity to adsorb to hydrophobic interfaces, such as the air-liquid interface. Surface flow can increase aggregation of adsorbed proteins, which may be an undesirable consequence depending on the application. As changes in protein conformation upon adsorption are thought to induce aggregation, the ability to measure the folded state of proteins at interfaces is of particular interest. However, few techniques currently exist to measure protein conformation at interfaces. Here we describe a technique capable of measuring the hydrophobicity, and therefore the conformation and folded state, of proteins at air-liquid interfaces by exploiting the environmentally sensitive fluorophore Nile red. Two monoclonal antibodies (mAbs) with high (mAb1) and low (mAb2) surface activity were used to highlight the technique. Both mAbs showed low background fluorescence of Nile red in the liquid subphase and at a glass-liquid interface. In contrast, at the air-liquid interface Nile red fluorescence for mAb1 increased immediately after protein adsorption, whereas the Nile red fluorescence of the mAb2 film evolved more slowly in time even though the adsorbed quantity of protein remained constant. The results demonstrate that hydrophobicity upon mAb adsorption to the air-liquid interface evolves in a time-dependent manner. Interfacial hydrophobicity may be indicative of protein conformation or folded state, where rapid unfolding of mAb1 upon adsorption would be consistent with increased protein aggregation compared to mAb2. The ability to measure protein hydrophobicity at interfaces using Nile red, combined with small sample requirements and minimal sample preparation, fills a gap in existing interfacial techniques.

  4. Critical Evaluation of Air-Liquid Interface Exposure Devices for In Vitro Assessment of Atmospheric Pollutants

    EPA Science Inventory

    Exposure of cells to atmospheric pollutants at the air-liquid interface (ALI) is a more realistic approach than exposures of attached cells submerged in liquid medium. However, there is still limited understanding of the ideal ALI device design features that permit reproducible a...

  5. Thermodynamic and kinetic solid-liquid interface properties from transition path sampling

    NASA Astrophysics Data System (ADS)

    Şopu, Daniel; Rogal, Jutta; Drautz, Ralf

    2016-12-01

    We perform transition path sampling simulations to determine two of the key quantities in solidification, the solid-liquid interface energy and velocity, in a Lennard-Jones system. Our approach is applicable to a wide range of temperature and pressure conditions, at the melting temperature and out-of-equilibrium. We show that small system sizes are sufficient for good values of interface energies and velocities. The transition path sampling method thus offers an attractive and robust alternative for the evaluation of solid-liquid interface properties.

  6. Towards active microfluidics: Interface turbulence in thin liquid films with floating molecular machines

    NASA Astrophysics Data System (ADS)

    Alonso, Sergio; Mikhailov, Alexander S.

    2009-06-01

    Thin liquid films with floating active protein machines are considered. Cyclic mechanical motions within the machines, representing microscopic swimmers, lead to molecular propulsion forces applied to the air-liquid interface. We show that when the rate of energy supply to the machines exceeds a threshold, the flat interface becomes linearly unstable. As a result of this instability, the regime of interface turbulence, characterized by irregular traveling waves and propagating machine clusters, is established. Numerical investigations of this nonlinear regime are performed. Conditions for the experimental observation of the instability are discussed.

  7. A Microscopic Model for the Liquid Metal - Ionic Solution Interface.

    DTIC Science & Technology

    1983-02-10

    Chemistry 1. Laboratoire de Physique des Liquides et Electrochimie , Universite Pierre et Marie Curie, 4 place Jussieu, 752?0 PARIS CEDEX 05, FRANCE...Laboratoire de Physique des Liquides et Electrochimie , Universita Pie=re at Marie Curie, 4 place Jussieu, 75230 PARIS CEDEX 05, FRANCE. F. VERICAI 0

  8. Dynamic Self-Assembly and Self-Propulsion in Nonequilibrium Magnetic Colloidal Ensembles at a Liquid/Liquid Interface

    NASA Astrophysics Data System (ADS)

    Snezhko, Alexey; Aranson, Igor

    2011-03-01

    Ensembles of interacting particles subject to external periodic energy fluxes often develop nontrivial dynamics. Magnetic colloidal particles suspended over an interface of two immiscible liquids and energized by vertical alternating magnetic fields give rise to novel dynamic self-assembled structures (``asters'') which are not accessible at the liquid/air interfaces. Ferromagnetically ordered nickel spherical particles have been used in our experiments. Novel structures are attributed to the interplay between surface waves, generated at the liquid/liquid interface by the collective response of magnetic microparticles to the alternating magnetic field, and hydrodynamic fields induced in the boundary layers of both liquids forming the interface. Two types of magnetic order is reported. We show that self-assembled aster structures become distorted in the presence of a small in-plane dc magnetic field and develop self-propulsion. The speed of locomotion can be effectively tuned by the amplitude of the dc field. The research was supported by the U.S. DOE, Office of Basic Energy Sciences, Division of Materials Science and Engineering, under the Contract No. DE AC02-06CH11357.

  9. Quantitative assessment of radiation force effect at the dielectric air-liquid interface

    PubMed Central

    Capeloto, Otávio Augusto; Zanuto, Vitor Santaella; Malacarne, Luis Carlos; Baesso, Mauro Luciano; Lukasievicz, Gustavo Vinicius Bassi; Bialkowski, Stephen Edward; Astrath, Nelson Guilherme Castelli

    2016-01-01

    We induce nanometer-scale surface deformation by exploiting momentum conservation of the interaction between laser light and dielectric liquids. The effect of radiation force at the air-liquid interface is quantitatively assessed for fluids with different density, viscosity and surface tension. The imparted pressure on the liquids by continuous or pulsed laser light excitation is fully described by the Helmholtz electromagnetic force density. PMID:26856622

  10. Nonequilibrium kinetic boundary condition at the vapor-liquid interface of argon.

    PubMed

    Ishiyama, Tatsuya; Fujikawa, Shigeo; Kurz, Thomas; Lauterborn, Werner

    2013-10-01

    A boundary condition for the Boltzmann equation (kinetic boundary condition, KBC) at the vapor-liquid interface of argon is constructed with the help of molecular dynamics (MD) simulations. The KBC is examined at a constant liquid temperature of 85 K in a wide range of nonequilibrium states of vapor. The present investigation is an extension of a previous one by Ishiyama, Yano, and Fujikawa [Phys. Rev. Lett. 95, 084504 (2005)] and provides a more complete form of the KBC. The present KBC includes a thermal accommodation coefficient in addition to evaporation and condensation coefficients, and these coefficients are determined in MD simulations uniquely. The thermal accommodation coefficient shows an anisotropic behavior at the interface for molecular velocities normal versus tangential to the interface. It is also found that the evaporation and condensation coefficients are almost constant in a fairly wide range of nonequilibrium states. The thermal accommodation coefficient of the normal velocity component is almost unity, while that of the tangential component shows a decreasing function of the density of vapor incident on the interface, indicating that the tangential velocity distribution of molecules leaving the interface into the vapor phase may deviate from the tangential parts of the Maxwell velocity distribution at the liquid temperature. A mechanism for the deviation of the KBC from the isotropic Maxwell KBC at the liquid temperature is discussed in terms of anisotropic energy relaxation at the interface. The liquid-temperature dependence of the present KBC is also discussed.

  11. Dynamics of a solid sphere bouncing on or penetrating through a liquid-air interface

    NASA Astrophysics Data System (ADS)

    Kim, Seong Jin; Jung, Sunghwan; Lee, Sungyon

    2014-11-01

    In this study, we investigate the dynamics of a solid particle moving from liquid to air through a liquid-air interface. The experimental setup consists of an air-piston system that shoots a solid particle into water towards the free surface from below. Experimental results indicate that the particle either penetrates or bounces back depending on the particle size, impact speed, and surface tension. In particular, the particle needs to overcome the resistive interfacial forces in order to penetrate through the liquid-air interface. This transition from bouncing to penetration regimes is captured theoretically by conducting a simple force balance and is further compared with experiments.

  12. Mobile Interfaces: Liquids as a Perfect Structural Material for Multifunctional, Antifouling Surfaces

    SciTech Connect

    Grinthal, A; Aizenberg, J

    2014-01-14

    Life creates some of its most robust, extreme surface materials not from solids but from liquids: a purely liquid interface, stabilized by underlying nanotexture, makes carnivorous plant leaves ultraslippery, the eye optically perfect and dirt-resistant, our knees lubricated and pressure-tolerant, and insect feet reversibly adhesive and shape-adaptive. Novel liquid surfaces based on this idea have recently been shown to display unprecedented omniphobic, self-healing, anti-ice, antifouling, optical, and adaptive properties. In this Perspective, we present a framework and a path forward for developing and designing such liquid surfaces into sophisticated, versatile multifunctional materials. Drawing on concepts from solid materials design and fluid dynamics, we outline how the continuous dynamics, responsiveness, and multiscale patternability of a liquid surface layer can be harnessed to create a wide range of unique, active interfacial functions able to operate in harsh, changing environments not achievable with static solids. We discuss how, in partnership with the underlying substrate, the liquid surface can be programmed to adaptively and reversibly reconfigure from a defect-free, molecularly smooth, transparent interface through a range of finely tuned liquid topographies in response to environmental stimuli. With nearly unlimited design possibilities and unmatched interfacial properties, liquid materials as long-term stable interfaces yet in their fully liquid state may potentially transform surface design everywhere from medicine to architecture to energy infrastructure.

  13. Mobile interfaces: Liquids as a perfect structural material for multifunctional, antifouling surfaces

    SciTech Connect

    Grinthal, Alison; Aizenberg, Joanna

    2013-10-14

    Life creates some of its most robust, extreme surface materials not from solids but from liquids: a purely liquid interface, stabilized by underlying nanotexture, makes carnivorous plant leaves ultraslippery, the eye optically perfect and dirt-resistant, our knees lubricated and pressure-tolerant, and insect feet reversibly adhesive and shape-adaptive. Novel liquid surfaces based on this idea have recently been shown to display unprecedented omniphobic, self-healing, anti-ice, antifouling, optical, and adaptive properties. In this Perspective, we present a framework and a path forward for developing and designing such liquid surfaces into sophisticated, versatile multifunctional materials. Drawing on concepts from solid materials design and fluid dynamics, we outline how the continuous dynamics, responsiveness, and multiscale patternability of a liquid surface layer can be harnessed to create a wide range of unique, active interfacial functions-able to operate in harsh, changing environments-not achievable with static solids. We discuss how, in partnership with the underlying substrate, the liquid surface can be programmed to adaptively and reversibly reconfigure from a defect-free, molecularly smooth, transparent interface through a range of finely tuned liquid topographies in response to environmental stimuli. In conclusion, with nearly unlimited design possibilities and unmatched interfacial properties, liquid materials-as long-term stable interfaces yet in their fully liquid state-may potentially transform surface design everywhere from medicine to architecture to energy infrastructure.

  14. Mobile interfaces: Liquids as a perfect structural material for multifunctional, antifouling surfaces

    DOE PAGES

    Grinthal, Alison; Aizenberg, Joanna

    2013-10-14

    Life creates some of its most robust, extreme surface materials not from solids but from liquids: a purely liquid interface, stabilized by underlying nanotexture, makes carnivorous plant leaves ultraslippery, the eye optically perfect and dirt-resistant, our knees lubricated and pressure-tolerant, and insect feet reversibly adhesive and shape-adaptive. Novel liquid surfaces based on this idea have recently been shown to display unprecedented omniphobic, self-healing, anti-ice, antifouling, optical, and adaptive properties. In this Perspective, we present a framework and a path forward for developing and designing such liquid surfaces into sophisticated, versatile multifunctional materials. Drawing on concepts from solid materials design andmore » fluid dynamics, we outline how the continuous dynamics, responsiveness, and multiscale patternability of a liquid surface layer can be harnessed to create a wide range of unique, active interfacial functions-able to operate in harsh, changing environments-not achievable with static solids. We discuss how, in partnership with the underlying substrate, the liquid surface can be programmed to adaptively and reversibly reconfigure from a defect-free, molecularly smooth, transparent interface through a range of finely tuned liquid topographies in response to environmental stimuli. In conclusion, with nearly unlimited design possibilities and unmatched interfacial properties, liquid materials-as long-term stable interfaces yet in their fully liquid state-may potentially transform surface design everywhere from medicine to architecture to energy infrastructure.« less

  15. Liquid-vapor interface locations in a spheroidal container under low gravity

    NASA Technical Reports Server (NTRS)

    Carney, M. J.

    1986-01-01

    As a part of the general study of liquid behavior in low gravity environments, an experimental investigation was conducted to determine if there are equilibrium liquid-vapor interface configurations that can exist at more than one location in oblate spheroidal containers under reduced gravity conditions. Static contact angles of the test liquids on the spheroid surface were restricted to near 0 deg. The experiments were conducted in a low gravity environment. An oblate spheroidal tank was tested with an eccentricity of 0.68 and a semimajor axis of 2.0 cm. Both quantitative and qualitative data were obtained on the liquid-vapor interface configuration and position inside the container. The results of these data, and their impat on previous work in this area, are discussed. Of particular interest are those equilibrium interface configurations that can exist at multiple locations in the container.

  16. Scale effect of slip boundary condition at solid–liquid interface

    NASA Astrophysics Data System (ADS)

    Nagayama, Gyoko; Matsumoto, Takenori; Fukushima, Kohei; Tsuruta, Takaharu

    2017-03-01

    Rapid advances in microelectromechanical systems have stimulated the development of compact devices, which require effective cooling technologies (e.g., microchannel cooling). However, the inconsistencies between experimental and classical theoretical predictions for the liquid flow in microchannel remain unclarified. Given the larger surface/volume ratio of microchannel, the surface effects increase as channel scale decreases. Here we show the scale effect of the boundary condition at the solid–liquid interface on single-phase convective heat transfer characteristics in microchannels. We demonstrate that the deviation from classical theory with a reduction in hydraulic diameters is due to the breakdown of the continuum solid–liquid boundary condition. The forced convective heat transfer characteristics of single-phase laminar flow in a parallel-plate microchannel are investigated. Using the theoretical Poiseuille and Nusselt numbers derived under the slip boundary condition at the solid–liquid interface, we estimate the slip length and thermal slip length at the interface.

  17. Scale effect of slip boundary condition at solid–liquid interface

    PubMed Central

    Nagayama, Gyoko; Matsumoto, Takenori; Fukushima, Kohei; Tsuruta, Takaharu

    2017-01-01

    Rapid advances in microelectromechanical systems have stimulated the development of compact devices, which require effective cooling technologies (e.g., microchannel cooling). However, the inconsistencies between experimental and classical theoretical predictions for the liquid flow in microchannel remain unclarified. Given the larger surface/volume ratio of microchannel, the surface effects increase as channel scale decreases. Here we show the scale effect of the boundary condition at the solid–liquid interface on single-phase convective heat transfer characteristics in microchannels. We demonstrate that the deviation from classical theory with a reduction in hydraulic diameters is due to the breakdown of the continuum solid–liquid boundary condition. The forced convective heat transfer characteristics of single-phase laminar flow in a parallel-plate microchannel are investigated. Using the theoretical Poiseuille and Nusselt numbers derived under the slip boundary condition at the solid–liquid interface, we estimate the slip length and thermal slip length at the interface. PMID:28256536

  18. Universal adsorption at the vapor-liquid interface near the consolute point

    NASA Technical Reports Server (NTRS)

    Schmidt, James W.

    1990-01-01

    The ellipticity of the vapor-liquid interface above mixtures of methylcyclohexane (C7H14) and perfluoromethylcyclohexane (C7F14) has been measured near the consolute point T(c) = 318.6 K. The data are consistent with a model of the interface that combines a short-ranged density-vs height profile in the vapor phase with a much longer-ranged composition-versus-height profile in the liquid. The value of the free parameter produced by fitting the model to the data is consistent with results from two other simple mixtures and a mixture of a polymer and solvent. This experiment combines precision ellipsometry of the vapor-liquid interface with in situ measurements of refractive indices of the liquid phases, and it precisely locates the consolute point.

  19. Scale effect of slip boundary condition at solid-liquid interface.

    PubMed

    Nagayama, Gyoko; Matsumoto, Takenori; Fukushima, Kohei; Tsuruta, Takaharu

    2017-03-03

    Rapid advances in microelectromechanical systems have stimulated the development of compact devices, which require effective cooling technologies (e.g., microchannel cooling). However, the inconsistencies between experimental and classical theoretical predictions for the liquid flow in microchannel remain unclarified. Given the larger surface/volume ratio of microchannel, the surface effects increase as channel scale decreases. Here we show the scale effect of the boundary condition at the solid-liquid interface on single-phase convective heat transfer characteristics in microchannels. We demonstrate that the deviation from classical theory with a reduction in hydraulic diameters is due to the breakdown of the continuum solid-liquid boundary condition. The forced convective heat transfer characteristics of single-phase laminar flow in a parallel-plate microchannel are investigated. Using the theoretical Poiseuille and Nusselt numbers derived under the slip boundary condition at the solid-liquid interface, we estimate the slip length and thermal slip length at the interface.

  20. Preparation of a smooth GaN-Gallium solid-liquid interface

    NASA Astrophysics Data System (ADS)

    de Jong, A. E. F.; Vonk, V.; Ruat, M.; Boćkowski, M.; Kamler, G.; Grzegory, I.; Honkimäki, V.; Vlieg, E.

    2016-08-01

    We discuss the preparation of an atomically flat solid-liquid interface between solid gallium nitride and liquid gallium using in situ surface X-ray diffraction to probe the interface roughness. For the creation of this interface it is necessary to start the experiment with liquid gallium which first etches into the solid at a temperature of 823 K in a nitrogen free ambient. After this rigorous cleaning procedure there is perfect wetting between solid and liquid. The roughness created due to the fast etching of the solid has to be repaired at a nitrogen pressure of 10-20 bar and a temperature around 1150 K. The (2,1) crystal truncation rod data are excellently described by a surface model having 0±0.1 Å roughness, which indicates a successful repair. The lateral length scale on which the roughness is determined has a lower limit of 750±50 Å.

  1. Adsorption Kinetics at Silica Gel/Ionic Liquid Solution Interface.

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Małgorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-12-10

    A series of imidazolium and pyridinium ionic liquids with different anions (Cl(-), Br(-), BF₄(-), PF₆(-)) has been evaluated for their adsorption activity on silica gel. Quantification of the ionic liquids has been performed by the use of RP-HPLC with organic-aqueous eluents containing an acidic buffer and a chaotropic salt. Pseudo-second order kinetic models were applied to the experimental data in order to investigate the kinetics of the adsorption process. The experimental data showed good fitting with this model, confirmed by considerably high correlation coefficients. The adsorption kinetic parameters were determined and analyzed. The relative error between the calculated and experimental amount of ionic liquid adsorbed at equilibrium was within 7%. The effect of various factors such as initial ionic liquid concentration, temperature, kind of solvent, kind of ionic liquid anion and cation on adsorption efficiency were all examined in a lab-scale study. Consequently, silica gel showed better adsorptive characteristics for imidazolium-based ionic liquids with chaotropic anions from aqueous solutions in comparison to pyridinium ionic liquids. The adsorption was found to decrease with the addition of organic solvents (methanol, acetonitrile) but it was not sensitive to the change of temperature in the range of 5-40 °C.

  2. Ripples on a rising bubble through an immiscible two-liquid interface generate numerous micro droplets

    NASA Astrophysics Data System (ADS)

    Uemura, T.; Ueda, Y.; Iguchi, M.

    2010-11-01

    The mass transfer between immiscible two liquid phases can be greatly accelerated by bubbling gas through a reactor (Bird R. B., Stewart W. E. and Lightfoot E. N., Transport Phenomena, 2nd edition (John Wiley and Sons) 2002). Therefore, the physical phenomenon occurring during the passage of a rising bubble through an immiscible two-liquid interface is of particular interest. The passage of the bubble through the oil (upper phase)/water (lower phase) interface starts with an upward lifting of the interface, and the bubble attracts a column of the water phase upwards keeping a film of the water phase around itself. In the present study, a particular remark is given to the influence of different interface tensions retracting the water film, after the water film ruptured, which lays on the interface between air and silicone oil. Unlike the previous studies on the rupture of a single liquid film in a gas which is pulled due to the identical surface tension, this system can form concentric ripples on the outer interface of the water film (oil/water interface) around the bubble due to the weak interface tension. Then, numerous micro water droplets break out from the fully grown ripples.

  3. Physical ageing of the contact line on colloidal particles at liquid interfaces.

    PubMed

    Kaz, David M; McGorty, Ryan; Mani, Madhav; Brenner, Michael P; Manoharan, Vinothan N

    2011-12-04

    Young's law predicts that a colloidal sphere in equilibrium with a liquid interface will straddle the two fluids, its height above the interface defined by an equilibrium contact angle. This has been used to explain why colloids often bind to liquid interfaces, and has been exploited in emulsification, water purification, mineral recovery, encapsulation and the making of nanostructured materials. However, little is known about the dynamics of binding. Here we show that the adsorption of polystyrene microspheres to a water/oil interface is characterized by a sudden breach and an unexpectedly slow relaxation. The relaxation appears logarithmic in time, indicating that complete equilibration may take months. Surprisingly, viscous dissipation appears to play little role. Instead, the observed dynamics, which bear strong resemblance to ageing in glassy systems, agree well with a model describing activated hopping of the contact line over nanoscale surface heterogeneities. These results may provide clues to longstanding questions on colloidal interactions at an interface.

  4. Atomic Resolution Images of Solid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Giambattista, Brian; McNairy, W. W.; Slough, C. G.; Johnson, A.; Bell, L. D.; Coleman, R. V.; Schneir, J.; Sonnenfeld, R.; Drake, B.; Hansma, P. K.

    1987-07-01

    A scanning tunneling microscope (STM) can provide atomic-resolution images of solids covered with a variety of liquids, including cryogenic fluids, both polar and nonpolar solvents, conductive aqueous solutions, oils, and even greases. This short overview includes images of solids covered with liquid nitrogen, liquid helium, paraffin oil, silicone oil, microscope immersion oil, silicone vacuum grease, fluorocarbon grease, glycerol, and salt water. These images show atoms, charge-density waves, grains in an evaporated metal film, and even corrosion processes as they occur in real time. The future includes not only basic research in surface science but also applied research in lithography, lubrication, catalysis, corrosion, electrochemistry, and perhaps even biology.

  5. Interaction of monovalent ions with the water liquid-vapor interface - A molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Pohorille, Andrew

    1991-01-01

    Results of molecular dynamics calculations are presented for a series of ions at infinite dilution near the water liquid-vapor interface. The free energies of ion transfer from the bulk to the interface are discussed, as are the accompanying changes of water structure at the surface and ion mobilities as a function of their proximity to the interface. It is shown that simple dielectric models do not provide an accurate description of ions at the water surface. The results of the study should be useful in the development of better models incorporating the shape and molecular structure of the interface.

  6. Study on Orbital Liquid Transport and Interface Behavior in Vane Tank

    NASA Astrophysics Data System (ADS)

    Kang, Qi; Rui, Wei

    2016-07-01

    Liquid propellant tank is used to supply gas free liquid for spacecraft as an important part of propulsion system. The liquid behavior dominated by surface tension in microgravity is obviously different with that on the ground, which put forward a new challenge to the liquid transport and relocation. The experiments which are investigated at drop tower in National Microgravity Lab have concentrated on liquid relocation following thruster firing. Considered that the liquid located at the bottom in the direction of the acceleration vector, a sphere scale vane tank is used to study the liquid-gas interface behaviors with different acceleration vector and different filling independently and we obtain a series of stable equilibrium interface and relocation time. We find that there is an obvious sedimentation in the direction of acceleration vector when fill rate greater than 2% fill. Suggestions have been put forward that outer vanes transferring liquid to the outlet should be fixed and small holes should be dogged at the vane close to the center post to improve the liquid flow between different vanes when B0 is greater than 2.5. The research about liquid transport alone ribbon vanes is simulated though software Flow3D. The simulation process is verified by comparing the liquid lip and vapor-liquid interface obtained from drop tower experiment and simulation result when fill rate is 15%. Then the influence of fill rate, numbers of vanes and the gap between vane and wall is studied through the same simulate process. Vanes' configurations are also changed to study the effect on the lip and liquid volume below some section. Some suggestions are put forward for the design of vanes.

  7. Temporally Anticorrelated Motion of Nanoparticles at a Liquid Interface.

    PubMed

    Wang, Dapeng; Hu, Renfeng; Skaug, Michael J; Schwartz, Daniel K

    2015-01-02

    Quantum dots at the hexane-glycerol interface exhibited unexpected behavior including highly dynamic adsorption/desorption, where the lateral nanoparticle motion was anomalously fast immediately after adsorption and prior to desorption. At the interface, particles exhibited pseudo-Brownian lateral motion, in which the instantaneous diffusion coefficient was temporally anticorrelated, in agreement with our simulations involving fractional Brownian motion in the surface-normal direction. These phenomena suggest that, in contrast to the conventional picture for colloidal particles, nanoparticles explore a landscape of metastable interfacial positions, with different exposures to the two adjacent phases.

  8. Using silicon diodes for detecting the liquid-vapor interface in hydrogen

    NASA Technical Reports Server (NTRS)

    Dempsey, Paula J.; Fabik, Richard H.

    1992-01-01

    Tests were performed using commercially available silicon diode temperature sensors to detect the location of the liquid-vapor interface in hydrogen during ground test programs. Results show that by increasing the current into the sensor, silicon diodes can be used as liquid level point sensors. After cycling the sensors from liquid to vapor several times, it was found that with a 30 mA (milliamps) input current, the sensors respond within 2 seconds by measuring a large voltage difference when transitioning from liquid to vapor across the interface. Nearly instantaneous response resulted during a transition form vapor to liquid. Detailed here are test procedures, experimental results, and guidelines for applying this information to other test facilities.

  9. Using silicon diodes for detecting the liquid-vapor interface in hydrogen

    NASA Technical Reports Server (NTRS)

    Dempsey, Paula J.; Fabik, Richard H.

    1992-01-01

    Tests were performed using commercially available silicon diode temperature sensors to detect the location of the liquid-vapor interface in hydrogen during ground test programs. Results show that by increasing the current into the sensor, silicon diodes can be used as liquid level point sensors. After cycling the sensors from liquid to vapor several times, it was found that with a 30 mA (milliamps) input current, the sensors respond within 2 seconds by measuring a large voltage difference when transitioning from liquid to vapor across the interface. Nearly instantaneous response resulted during a transition from vapor to liquid. Detailed here are test procedures, experimental results, and guidelines for applying this information to other test facilities.

  10. Detachment force of particles from air-liquid interfaces of films and bubbles.

    PubMed

    Ally, Javed; Kappl, Michael; Butt, Hans-Jürgen; Amirfazli, A

    2010-12-07

    The detachment force required to pull a microparticle from an air-liquid interface is measured using atomic force microscopy (AFM) and the colloidal probe technique. Water, solutions of sodium dodecyl sulfate (SDS), and silicone oils are tested in order to study the effects of surface tension and viscosity. Two different liquid geometries are considered: the air-liquid interface of a bubble and a liquid film on a solid substrate. It was shown that detaching particles from liquid films is fundamentally different than from bubbles or drops due to the restricted flow of the liquid phase. Additional force is required to detach a particle from a film, and the maximum force during detachment is not necessarily at the position where the particle breaks away from the interface (as seen in bubble or drop systems). This is due to the dynamics of meniscus formation and viscous effects, which must be considered if the liquid is constrained in a film. The magnitude of these effects is related to the liquid viscosity, film thickness, and detachment speed.

  11. Synthesis of pure iron nanoparticles at liquid-liquid interface using pulsed plasma

    NASA Astrophysics Data System (ADS)

    Kelgenbaeva, Zhazgul; Omurzak, Emil; Takebe, Shintaro; Sulaimankulova, Saadat; Abdullaeva, Zhypargul; Iwamoto, Chihiro; Mashimo, Tsutomu

    2014-09-01

    Pure α-Fe nanoparticles with ≤10 nm size were synthesized using a simple method—pulsed plasma in liquid. This is the first time that pure metallic nanoparticles were prepared by arc discharge method using water-toluene interface as a medium. Several experiments made evident that toluene-water ratio in emulsion influences the purity and size of Fe nanoparticles. The purity of the nanoparticles gradually increased from 48 to 98 %, while particle size decreased from 21 to 9.5 nm with smaller toluene volume fraction (from 40 to 5 %) in the microemulsions. Finally, toluene:water with 95:5 (%) ratio was found to be the most appropriate medium for pure Fe nanoparticle formation. Lattice parameters of the obtained Fe samples calculated from XRD found to be larger ( a = 0.2927 nm) than those previously reported Fe ( a (BCC-Fe) = 0.2866 nm). HRTEM showed spherical-shaped Fe nanoparticles with partial aggregation. Vibrating sample magnetometer indicated superparamagnetic properties of particles with high-saturation magnetization ( M s = 125 emu g-1) at room temperature.

  12. Pressurized nano-liquid-junction interface for coupling capillary electrochromatography and nano-liquid chromatography with mass spectrometry.

    PubMed

    D'Orazio, Giovanni; Fanali, Salvatore

    2013-11-22

    A new nano-liquid-junction interface for coupling both capillary electrochromatography (CEC) or nano-liquid chromatography (nano-LC) with mass spectrometry (MS) was studied. The interface was a small T piece of polymeric material where capillary column and tip capillary were positioned at 180° while the third exit (at 90°) was occupied by a capillary delivering a liquid-assisting spray ionization for CEC experiments or by the electrode for the high voltage spray for nano-LC. Experiments were carried out analyzing mixtures of some organophosphorus pesticides (OPPs) or anti-inflammatory and related acidic drugs with MS detection in positive or negative ion mode, respectively. Analyzed OPPs compounds were baseline resolved utilizing the novel interface in both nano-LC and CEC obtaining good sensitivity and repeatability. For CEC-MS, the limits of detection ranged between 0.03 and 6.80 μg/mL and the intra-day repeatability was RSD <3.8% and <13% for the retention times and peak areas, respectively. The interface was easy to handle and good reproducibility, between 2.5 and 3.5% for the retention time and <10% for the efficiencies, was obtained when the interface was installed by two different analysts. Furthermore, it could be used for both CEC and nano-LC.

  13. Influence of process parameters to composite interface organization and performance of liquid/solid bimetal

    NASA Astrophysics Data System (ADS)

    Rong, S. F.; Zhu, Y. C.; Wu, Y. H.; Yang, P. H.; Duan, X. L.; Zhou, H. T.

    2015-12-01

    The liquid-solid composite technique was used to prepare the high carbon high chromium steel (HCHCS) and low alloy steel (LCS) bimetal composite materials by means of insert casting method. The influence of some process parameters such as liquid-solid ratio, preheat temperature, pouring temperature on the interface microstructure and mechanical properties were studied. Interface microstructure and element distribution were analyzed. The results show that the interface microstructure becomes better, and bonding area becomes thicker with the increase of the volume of liquid to solid ratio, preheating temperature and pouring temperature. When the liquid-solid ratio is 8:1, the preheating temperature is 300 °C and the pouring temperature is 1565 °C, a good metallurgical bonding area without any hole can be obtained with the interface combination of diffusion and fusion. The composite interface structure was composed of a core material diffusion layer, a cooling solidification layer, a direction growth layer and some cell particles. The elements of C, Cr and Mn diffuse from the HCHCS side to the alloy steel side. The microhardness increased in the gradient from the LCS side to the HCHCS. The microhardness of the interface is significantly higher than that of LCS.

  14. Electrohydrodynamic Displacement of Polarizable Liquid Interfaces in an Alternating Current Electric Field

    NASA Astrophysics Data System (ADS)

    Gagnon, Zachary

    2015-11-01

    In this work, we investigate Maxwell-Wagner polarization at electrically polarizable liquid interfaces. An AC electric field is applied across a liquid electrical interface created between two co-flowing microfluidic fluid streams with different electrical properties. When potentials as low as 2 volts are applied, we observe a frequency dependent interfacial displacement that is dependent on the relative differences in the electrical conductivity and dielectric constant between the two liquids. At low frequency this deflection is dependent on electrical conductivity, and only depends on dielectric constant at high frequency. At intermediate frequencies, we observe a crossover that is independent of applied voltage, sensitive to both fluid electrical properties, and where no displacement is observed. An analytical polarization model is presented that predicts the liquid interfacial crossover frequency, the dependence of interfacial displacement on liquid electrical conductivity and dielectric constant, and accurately scales the interface displacement measurements. The results show that liquid interfaces are capable of polarizing under AC electric fields and being precisely deflected in a direction and magnitude that is dependent on the applied electric field frequency.

  15. Modeling the Interface Instability and Mixing Flow During the Process of Liquid Explosion Dissemination

    NASA Astrophysics Data System (ADS)

    Li, L.; Xu, S. L.; Ren, Y. J.; Liu, G. R.; Ren, X. B.; Xie, W. J.; Li, Y. C.; Wang, Z. L.

    The liquid flow during the process of liquid explosion dissemination is a typical complex high-speed unsteady motion with multi-scale in space and time. The motion of liquid flow may be partitioned to several stages. The first is initial liquid expansion by the action of shock wave and explosive gaseous products. The second is breakup of liquid annulus and turbulent mixing, which is called near-field flow. The third is two-phase mixing flow of gas and liquid drops, which is called far-field flow. To first stage, a compressible inviscid liquid model was used, while an elastic and plastic model was used to depict the expansion of solid shell. Numerical study in two dimensional has been made by using the Arbitrary Euler-Lagrange (ALE) methods. In near-field, the unstable flow of liquid annulus is dominated by many factors. (1) The shock action of gaseous expansive products. (2) The geometric structure of wave system in liquid. (3) The local bubble and cavitating flow in annulus, induce much of local unstable interface, tear up interfaces, and enhance the instability and breakup of liquid annulus. In this paper, some postulations are proposed that the cavitations in liquid annulus are induced by shock wave and the flow of liquid annulus is a two phase flow (liquid and a discrete bubble groups). Some experimental results will be presented that the breakup of interface and turbulent mixing is visualized qualitatively and measured quantitatively by using shadow photography method. The primary results are some flow patten of interfaces and some transient flow parameters by which the nonlinear character will be obtained, and provide an experiential support for modeling to unstable interface flow and turbulent mixing. The two-phase mixing flow between liquid drops and gas in far-field can be studied by numerical methods where the turbulent motion of gas phase is represented with k-ɛ model in Euler system, the motion of particle phase is represented with particle stochastic

  16. Liquid-liquid interfaces as potentiometric ion-sensors-I The n-butanol-water interface as indicating sensor for the potentiometric titration of some acids and bases.

    PubMed

    Liteanu, C; Mioşcu, M

    1972-07-01

    The property that liquid-liquid interfaces modify their electrical charge as a function of the composition of the two phases in contact has been used to detect the end-points in a series of acid-base titrations in the aqueous phase. Although the titration curves are not classical in shape, the equivalence points can be located if the solutions are not too dilute. Good results for concentrations down to 10(-3)N have been obtained. The electrode has a fast response. The influence of surface-active substances on the titration has also been investigated.

  17. Potentiostat for Characterizing Microstructures at Ionic Liquid/Electrode Interfaces

    DTIC Science & Technology

    2015-10-10

    systems via simultaneous electrochemical and spectroscopic studies. These data are pertinent to understanding the microscopic (molecular and ionic...characterize ionic liquid-based (IL-based) electrolyte systems via simultaneous electrochemical and spectroscopic studies. These data are pertinent to...spectrometer to perform surface enhanced infrared absorption (SEIRA) spectroscopy with electrochemical control. The multichannel instrument has also

  18. Understanding the lateral movement of particles adsorbed at a solid-liquid interface.

    PubMed

    Savaji, Kunal; Li, Xue; Couzis, Alexander

    2015-09-01

    In this paper we study the phenomenon of lateral movement of particles that are electrostatically adsorbed at a solid-liquid interface. The experimental system involves negatively charged silica particles of two different sizes (65 nm and 90 nm) that are exposed to the positively charged solid surface (silane coated silicon wafer) in sequential steps. The particle-adsorbed wafers are analyzed under a scanning electron microscope and the images are processed to determine the pair-correlation function for the particles adsorbed in the first step. From the pair correlation data and the particle surface coverage data we show that the adsorbed particles are mobile at the solid-liquid interface. In specific, we show that the adsorbed particles are mobile at the solid-liquid interface when there is a driving force for the adsorbed particles to move. The driving force in the scheme of experiments discussed in this paper is the reduction in the free energy of the system.

  19. Influence of Melt Convection on Solid-Liquid Interface Under Terrestrial and Reduced Gravity Environments

    NASA Technical Reports Server (NTRS)

    Glicksman, M. E.

    1985-01-01

    Solidification and crystal growth processes involve thermal and solutal gradients within a molten phase. In the presence of gravity, such gradients result in convective flows which interact with diffusion fields at the solid-liquid interface. Dendritic growth kinetics was studied in transparent model systems which freeze similarily to most metals. Succinonitrile shows a strong influence of convection at supercoolings below about 1K. Fluid flows adjacent to solid-liquid interfaces and the behavior of shear flows in vertical annular geometries are studied. Novel low-frequency eigenstates were discovered and classified as coupled modes, for their involvement with interfacial deformation coupled to the fluid flow, and are unknown in systems without deformable interfaces. The dependence of coupled convection modes on interfacial geometry, gravity, fluid properties, and transformation characteristics studied for several annual flow arrangements with nominally pure solid-liquid systems.

  20. Interface reorientation of cryogenic liquids under non-isothermal boundary conditions

    NASA Astrophysics Data System (ADS)

    Kulev, Nikolai; Basting, Steffen; Bänsch, Eberhard; Dreyer, Michael

    2014-07-01

    We investigate the capillary driven oscillations of the liquid-vapor interface in cryogenic systems under non-isothermal boundary conditions. The oscillations took place in a partly filled cylinder during the interface reorientation from its 1 g equilibrium position to the microgravity equilibrium position after a step reduction of gravity. The latter was achieved by dropping the experimental device in the drop tower of Bremen, providing 4.7 s of microgravity. Liquid argon (Tsat=87.3 K at 1013 hPa) and liquid methane (Tsat=111.7 K at 1013 hPa) were used as experimental liquids. Axial wall temperature gradients, corresponding to a linear increase of the wall temperature, were applied above the interface position prior to the experiments with values varying between 0.2 K/mm and 2.9 K/mm. Both liquids showed a qualitatively similar reorientation behavior. The reorientation characteristics were found to depend on the value of the applied gradient and on the material properties of the experimental liquids. Numerical simulation showed a good qualitative agreement with a previous experiment with 1.34 K/mm using liquid argon, demonstrating main characteristic features of the experiment.

  1. Self-healing gold mirrors and filters at liquid-liquid interfaces.

    PubMed

    Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D; Gumy, Frederic; Girault, Hubert H

    2016-04-14

    The optical and morphological properties of lustrous metal self-healing liquid-like nanofilms were systematically studied for different applications (e.g., optical mirrors or filters). These nanofilms were formed by a one-step self-assembly methodology of gold nanoparticles (AuNPs) at immiscible water-oil interfaces, previously reported by our group. We investigated a host of experimental variables and herein report their influence on the optical properties of nanofilms: AuNP mean diameter, interfacial AuNP surface coverage, nature of the organic solvent, and nature of the lipophilic organic molecule that caps the AuNPs in the interfacial nanofilm. To probe the interfacial gold nanofilms we used in situ (UV-vis-NIR spectroscopy and optical microscopy) as well as ex situ (SEM and TEM of interfacial gold nanofilms transferred to silicon substrates) techniques. The interfacial AuNP surface coverage strongly influenced the morphology of the interfacial nanofilms, and in turn their maximum reflectance and absorbance. We observed three distinct morphological regimes; (i) smooth 2D monolayers of "floating islands" of AuNPs at low surface coverages, (ii) a mixed 2D/3D regime with the beginnings of 3D nanostructures consisting of small piles of adsorbed AuNPs even under sub-full-monolayer conditions and, finally, (iii) a 3D regime characterised by the 2D full-monolayer being covered in significant piles of adsorbed AuNPs. A maximal value of reflectance reached 58% in comparison with a solid gold mirror, when 38 nm mean diameter AuNPs were used at a water-nitrobenzene interface. Meanwhile, interfacial gold nanofilms prepared with 12 nm mean diameter AuNPs exhibited the highest extinction intensities at ca. 690 nm and absorbance around 90% of the incident light, making them an attractive candidate for filtering applications. Furthermore, the interparticle spacing, and resulting interparticle plasmon coupling derived optical properties, varied significantly on replacing

  2. Spectral mapping of heat transfer mechanisms at liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Sääskilahti, K.; Oksanen, J.; Tulkki, J.; Volz, S.

    2016-05-01

    Thermal transport through liquid-solid interfaces plays an important role in many chemical and biological processes, and better understanding of liquid-solid energy transfer is expected to enable improving the efficiency of thermally driven applications. We determine the spectral distribution of thermal current at liquid-solid interfaces from nonequilibrium molecular dynamics, delivering a detailed picture of the contributions of different vibrational modes to liquid-solid energy transfer. Our results show that surface modes located at the Brillouin zone edge and polarized along the liquid-solid surface normal play a crucial role in liquid-solid energy transfer. Strong liquid-solid adhesion allows also for the coupling of in-plane polarized modes in the solid with the liquid, enhancing the heat-transfer rate and enabling efficient energy transfer up to the cutoff frequency of the solid. Our results provide fundamental understanding of the energy-transfer mechanisms in liquid-solid systems and enable detailed investigations of energy transfer between, e.g., water and organic molecules.

  3. Surfactant-Triggered Nanoarchitectonics of Fullerene C60 Crystals at a Liquid-Liquid Interface.

    PubMed

    Shrestha, Lok Kumar; Shrestha, Rekha Goswami; Hill, Jonathan P; Tsuruoka, Tohru; Ji, Qingmin; Nishimura, Toshiyuki; Ariga, Katsuhiko

    2016-11-29

    Here, we report the structural and morphological modulation of fullerene C60 crystals induced by nonionic surfactants diglycerol monolaurate (C12G2) and monomyristate (C14G2). C60 crystals synthesized at a liquid-liquid interface comprising isopropyl alcohol (IPA) and a saturated solution of C60 in ethylbenzene (EB) exhibited a one-dimensional (1D) morphology with well-defined faceted structure. Average length and diameter of the faceted rods were ca. 4.8 μm and 747 nm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a hexagonal-close packed (hcp) structure with cell dimensions ca. a = 2.394 nm and c = 1.388 nm. The 1D rod morphology of C60 crystals was transformed into "Konpeito candy-like" crystals (average diameter ca. 1.2 μm) when the C60 crystals were grown in the presence of C12G2 or C14G2 surfactant (1%) in EB. The pXRD spectra of "Konpeito-like" crystals could be assigned to the face-centered cubic (fcc) phase with cell dimensions ca. a = 1.4309 nm (for C12G2) and a = 1.4318 nm (for C14G2). However, clusters or aggregates of C60 lacking a uniform morphology were observed at lower surfactant concentrations (0.1%), although these crystals exhibited an fcc crystal structure. The self-assembled 1D faceted C60 crystals and "Konpeito-like" C60 crystals exhibited intense photoluminescence (PL) (∼35 times greater than pC60) and a blue-shifted PL intensity maximum (∼15 nm) compared to those of pC60, demonstrating the potential use of this method for the control of the optoelectronic properties of fullerene nanostructures. The "Konpeito-like" crystals were transformed into high surface area nanoporous carbon with a graphitic microstructure upon heat-treatment at 2000 °C. The heat-treated samples showed enhanced electrochemical supercapacitance performance (specific capacitance is ca. 175 F g(-1), which is about 20 times greater than pC60) with long cyclic stability demonstrating the potential of the materials in supercapacitor device

  4. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creating a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.

  5. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    DOE PAGES

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creatingmore » a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.« less

  6. Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface

    NASA Astrophysics Data System (ADS)

    Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

    2015-07-01

    The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

  7. Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface.

    PubMed

    Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

    2015-07-07

    The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

  8. Ion-specific induced fluctuations and free energetics of aqueous protein hydrophobic interfaces: toward connecting to specific-ion behaviors at aqueous liquid-vapor interfaces.

    PubMed

    Cui, Di; Ou, Shuching; Peters, Eric; Patel, Sandeep

    2014-05-01

    We explore anion-induced interface fluctuations near protein-water interfaces using coarse-grained representations of interfaces as proposed by Willard and Chandler ( J. Phys. Chem. B 2010 , 114 , 1954 - 1958 ). We use umbrella sampling molecular dynamics to compute potentials of mean force along a reaction coordinate bridging the state where the anion is fully solvated and one where it is biased via harmonic restraints to remain at the protein-water interface. Specifically, we focus on fluctuations of an interface between water and a hydrophobic region of hydrophobin-II (HFBII), a 71 amino acid residue protein expressed by filamentous fungi and known for its ability to form hydrophobically mediated self-assemblies at interfaces such as a water/air interface. We consider the anions chloride and iodide that have been shown previously by simulations as displaying specific-ion behaviors at aqueous liquid-vapor interfaces. We find that as in the case of a pure liquid-vapor interface, at the hydrophobic protein-water interface, the larger, less charge-dense iodide anion displays a marginal interfacial stability compared with that of the smaller, more charge-dense chloride anion. Furthermore, consistent with the results at aqueous liquid-vapor interfaces, we find that iodide induces larger fluctuations of the protein-water interface than chloride.

  9. Determinative factors of competitive advantage between aerobic bacteria for niches at the air-liquid interface.

    PubMed

    Yamamoto, Kyosuke; Haruta, Shin; Kato, Souichiro; Ishii, Masaharu; Igarashi, Yasuo

    2010-01-01

    We focused on bacterial interspecies relationships at the air-liquid interface where the formation of pellicles by aerobes was observed. Although an obligate aerobe (Brevibacillus sp. M1-5) was initially dominant in the pellicle population, a facultative aerobe (Pseudoxanthomonas sp. M1-3) emerged and the viability of M1-5 rapidly decreased due to severe competition for oxygen. Supplementation of the medium with carbohydrates allowed the two species to coexist at the air-liquid interface. These results indicate that the population dynamics within pellicles are primarily governed by oxygen utilization which was affected by a combination of carbon sources.

  10. Dynamic Evolution of the Evaporating Liquid-Vapor Interface in Micropillar Arrays.

    PubMed

    Antao, Dion S; Adera, Solomon; Zhu, Yangying; Farias, Edgardo; Raj, Rishi; Wang, Evelyn N

    2016-01-19

    Capillary assisted passively pumped thermal management devices have gained importance due to their simple design and reduction in energy consumption. The performance of these devices is strongly dependent on the shape of the curved interface between the liquid and vapor phases. We developed a transient laser interferometry technique to investigate the evolution of the shape of the liquid-vapor interface in micropillar arrays during evaporation heat transfer. Controlled cylindrical micropillar arrays were fabricated on the front side of a silicon wafer, while thin-film heaters were deposited on the reverse side to emulate a heat source. The shape of the meniscus was determined using the fringe patterns resulting from interference of a monochromatic beam incident on the thin liquid layer. We studied the evolution of the shape of the meniscus on these surfaces under various operating conditions including varying the micropillar geometry and the applied heating power. By monitoring the transient behavior of the evaporating liquid-vapor interface, we accurately measured the absolute location and shape of the meniscus and calculated the contact angle and the maximum capillary pressure. We demonstrated that the receding contact angle which determines the capillary pumping limit is independent of the microstructure geometry and the rate of evaporation (i.e., the applied heating power). The results of this study provide fundamental insights into the dynamic behavior of the liquid-vapor interface in wick structures during phase-change heat transfer.

  11. Nanoparticle self-assembly at the interface of liquid crystal droplets.

    PubMed

    Rahimi, Mohammad; Roberts, Tyler F; Armas-Pérez, Julio C; Wang, Xiaoguang; Bukusoglu, Emre; Abbott, Nicholas L; de Pablo, Juan J

    2015-04-28

    Nanoparticles adsorbed at the interface of nematic liquid crystals are known to form ordered structures whose morphology depends on the orientation of the underlying nematic field. The origin of such structures is believed to result from an interplay between the liquid crystal orientation at the particles' surface, the orientation at the liquid crystal's air interface, and the bulk elasticity of the underlying liquid crystal. In this work, we consider nanoparticle assembly at the interface of nematic droplets. We present a systematic study of the free energy of nanoparticle-laden droplets in terms of experiments and a Landau-de Gennes formalism. The results of that study indicate that, even for conditions under which particles interact only weakly at flat interfaces, particles aggregate at the poles of bipolar droplets and assemble into robust, quantized arrangements that can be mapped onto hexagonal lattices. The contributions of elasticity and interfacial energy corresponding to different arrangements are used to explain the resulting morphologies, and the predictions of the model are shown to be consistent with experimental observations. The findings presented here suggest that particle-laden liquid crystal droplets could provide a unique and versatile route toward building blocks for hierarchical materials assembly.

  12. Anharmonicity, solvation forces, and resolution in atomic force microscopy at the solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Voïtchovsky, Kislon

    2013-08-01

    Solid-liquid interfaces are central to nanoscale science and technology and control processes as diverse as self-assembly, heterogeneous catalysis, wetting, electrochemistry, or protein function. Experimentally, measuring the structure and dynamics of solid-liquid interfaces with molecular resolution remains a challenge. This task can, in principle, be achieved with atomic force microscopy (AFM), which functions locally, and with nanometer precision. When operated dynamically and at small amplitudes, AFM can provide molecular-level images of the liquid solvation layers at the interfaces. At larger amplitudes, results in the field of multifrequency AFM have shown that anharmonicities in the tip motion can provide quantitative information about the solid's mechanical properties. The two approaches probe opposite aspects of the interface and are generally seen as distinct. Here it is shown that, for amplitudes Aliquid, and subnanometer resolution can be achieved through solvation forces. For A>d, the tip trajectory becomes rapidly anharmonic due to the tip tapping the solid, and the resolution decreases. A nonlinear transition between the two regimes occurs for A˜d and can be quantified with the second harmonic of the tip oscillation. These results, confirmed by computer simulations, remain valid in most experimental conditions. Significantly, they provide an objective criterion to enhance resolution and to decide whether the results are dominated by the properties of the solid or of the liquid.

  13. Self-healing gold mirrors and filters at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D.; Gumy, Frederic; Girault, Hubert H.

    2016-03-01

    The optical and morphological properties of lustrous metal self-healing liquid-like nanofilms were systematically studied for different applications (e.g., optical mirrors or filters). These nanofilms were formed by a one-step self-assembly methodology of gold nanoparticles (AuNPs) at immiscible water-oil interfaces, previously reported by our group. We investigated a host of experimental variables and herein report their influence on the optical properties of nanofilms: AuNP mean diameter, interfacial AuNP surface coverage, nature of the organic solvent, and nature of the lipophilic organic molecule that caps the AuNPs in the interfacial nanofilm. To probe the interfacial gold nanofilms we used in situ (UV-vis-NIR spectroscopy and optical microscopy) as well as ex situ (SEM and TEM of interfacial gold nanofilms transferred to silicon substrates) techniques. The interfacial AuNP surface coverage strongly influenced the morphology of the interfacial nanofilms, and in turn their maximum reflectance and absorbance. We observed three distinct morphological regimes; (i) smooth 2D monolayers of ``floating islands'' of AuNPs at low surface coverages, (ii) a mixed 2D/3D regime with the beginnings of 3D nanostructures consisting of small piles of adsorbed AuNPs even under sub-full-monolayer conditions and, finally, (iii) a 3D regime characterised by the 2D full-monolayer being covered in significant piles of adsorbed AuNPs. A maximal value of reflectance reached 58% in comparison with a solid gold mirror, when 38 nm mean diameter AuNPs were used at a water-nitrobenzene interface. Meanwhile, interfacial gold nanofilms prepared with 12 nm mean diameter AuNPs exhibited the highest extinction intensities at ca. 690 nm and absorbance around 90% of the incident light, making them an attractive candidate for filtering applications. Furthermore, the interparticle spacing, and resulting interparticle plasmon coupling derived optical properties, varied significantly on replacing

  14. Economizer Based Data Center Liquid Cooling with Advanced Metal Interfaces

    SciTech Connect

    Timothy Chainer

    2012-11-30

    A new chiller-less data center liquid cooling system utilizing the outside air environment has been shown to achieve up to 90% reduction in cooling energy compared to traditional chiller based data center cooling systems. The system removes heat from Volume servers inside a Sealed Rack and transports the heat using a liquid loop to an Outdoor Heat Exchanger which rejects the heat to the outdoor ambient environment. The servers in the rack are cooled using a hybrid cooling system by removing the majority of the heat generated by the processors and memory by direct thermal conduction using coldplates and the heat generated by the remaining components using forced air convection to an air- to- liquid heat exchanger inside the Sealed Rack. The anticipated benefits of such energy-centric configurations are significant energy savings at the data center level. When compared to a traditional 10 MW data center, which typically uses 25% of its total data center energy consumption for cooling this technology could potentially enable a cost savings of up to $800,000-$2,200,000/year (assuming electricity costs of 4 to 11 cents per kilowatt-hour) through the reduction in electrical energy usage.

  15. Acoustic radiation forces at liquid interfaces impact the performance of acoustophoresis.

    PubMed

    Deshmukh, Sameer; Brzozka, Zbigniew; Laurell, Thomas; Augustsson, Per

    2014-09-07

    Acoustophoresis is a method well suited for cell and microbead separation or concentration for downstream analysis in microfluidic settings. One of the main limitations that acoustophoresis share with other microfluidic techniques is that the separation efficiency is poor for particle-rich suspensions. We report that flow laminated liquids can be relocated in a microchannel when exposed to a resonant acoustic field. Differences in acoustic impedance between two liquids cause migration of the high-impedance liquid towards an acoustic pressure node. In a set of experiments we charted this phenomenon and show herein that it can be used to either relocate liquids with respect to each other, or to stabilize the interface between them. This resulted in decreased medium carry-over when transferring microbeads (4% by volume) between suspending liquids using acoustophoresis. Furthermore we demonstrate that acoustic relocation of liquids occurs for impedance differences as low as 0.1%.

  16. Synergistic effect of dicarbollide anions in liquid-liquid extraction: a molecular dynamics study at the octanol-water interface.

    PubMed

    Chevrot, G; Schurhammer, R; Wipff, G

    2007-04-28

    We report a molecular dynamics study of chlorinated cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)Cl(3))(2)Co](-)"CCD(-)" in octanol and at the octanol-water interface, with the main aim to understand why these hydrophobic species act as strong synergists in assisted liquid-liquid cation extraction. Neat octanol is quite heterogeneous and is found to display dual solvation properties, allowing to well solubilize CCD(-), Cs(+) salts in the form of diluted pairs or oligomers, without displaying aggregation. At the aqueous interface, octanol behaves as an amphiphile, forming either monolayers or bilayers, depending on the initial state and confinement conditions. In biphasic octanol-water systems, CCD(-) anions are found to mainly partition to the organic phase, thus attracting Cs(+) or even more hydrophilic counterions like Eu(3+) into that phase. The remaining CCD(-) anions adsorb at the interface, but are less surface active than at the chloroform interface. Finally, we compare the interfacial behavior of the Eu(BTP)(3)(3+) complex in the absence and in the presence of CCD(-) anions and extractant molecules. It is found that when the CCD(-)'s are concentrated enough, the complex is extracted to the octanol phase. Otherwise, it is trapped at the interface, attracted by water. These results are compared to those obtained with chloroform as organic phase and discussed in the context of synergistic effect of CCD(-) in liquid-liquid extraction, pointing to the importance of dual solvation properties of octanol and of the hydrophobic character of CCD(-) for synergistic extraction of cations.

  17. The physics of pattern formation at liquid interfaces

    SciTech Connect

    Maher, J.V.

    1992-06-01

    During the past year we have submitted six papers for publication, three related to the dynamics of macroscopic interfaces, and ultimately all related to solidification, and three related to the internal structure of disorderly materials, with possible applications to the processing of composite materials. In addition to completing all these projects during the past year, we have begun two new projects, one on pattern formation and one on aggregation within a composite system. A brief description is given of this research in this paper.

  18. Note: Sample cells to investigate solid/liquid interfaces with neutrons

    SciTech Connect

    Rennie, Adrian R. Hellsing, Maja S.; Lindholm, Eric; Olsson, Anders

    2015-01-15

    The design of sample cells to study solid/liquid interfaces by neutron reflection is presented. Use of standardized components and a modular design has allowed a wide range of experiments that include grazing incidence scattering and conventional small-angle scattering. Features that reduce background scattering are emphasized. Various flow arrangements to fill and replenish the liquid in the cell as well as continuous stirring are described.

  19. Liquid-liquid extraction assisted by a carbon nanoparticles interface. Electrophoretic determination of atrazine in environmental samples.

    PubMed

    Caballero-Díaz, Encarnación; Simonet, Bartolomé; Valcárcel, Miguel

    2013-10-21

    A novel method for the determination of atrazine, using liquid-liquid extraction assisted by a nanoparticles film formed in situ and composed of organic solvent stabilized-carbon nanoparticles, is described. The presence of nanoparticles located at the liquid-liquid interface reinforced the extraction of analyte from matrix prior to capillary electrophoresis (CE) analysis. Some influential experimental variables were optimized in order to enhance the extraction efficiency. The developed procedure confirmed that carbon nanoparticles, especially multi-walled carbon nanotubes, are suitable to be used in sample treatment processes introducing new mechanisms of interaction with the analyte. The application of the proposed preconcentration method followed by CE detection enabled the determination of atrazine in spiked river water providing acceptable RSD values (11.6%) and good recoveries (about 87.0-92.0%). Additionally, a similar extraction scheme was tested in soil matrices with a view to further applications in real soil samples.

  20. PREFACE: Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations Liquid-solid interfaces: structure and dynamics from spectroscopy and simulations

    NASA Astrophysics Data System (ADS)

    Gaigeot, Marie-Pierre; Sulpizi, Marialore

    2012-03-01

    Liquid-solid interfaces play an important role in a number of phenomena encountered in biological, chemical and physical processes. Surface-induced changes of the material properties are not only important for the solid support but also for the liquid itself. In particular, it is now well established that water at the interface is substantially different from bulk water, even in the proximity of apparently inert surfaces such as a simple metal. The complex chemistry at liquid-solid interfaces is typically fundamental to heterogeneous catalysis and electrochemistry, and has become especially topical in connection with the search for new materials for energy production. A quite remarkable example is the development of cheap yet efficient solar cells, whose basic components are dye molecules grafted to the surface of an oxide material and in contact with an electrolytic solution. In life science, the most important liquid-solid interfaces are the water-cell-membrane interfaces. Phenomena occurring at the surface of phospholipid bilayers control the docking of proteins, the transmission of signals as well as transport of molecules in and out of the cell. Recently the development of bio-compatible materials has lead to research on the interface between bio-compatible material and lipid/proteins in aqueous solution. Gaining a microscopic insight into the processes occurring at liquid-solid interfaces is therefore fundamental to a wide range of disciplines. This special section collects some contributions to the CECAM Workshop 'Liquid/Solid interfaces: Structure and Dynamics from Spectroscopy and Simulations' which took place in Lausanne, Switzerland in June 2011. Our main aim was to bring together knowledge and expertise from different communities in order to advance our microscopic understanding of the structure and dynamics of liquids at interfaces. In particular, one of our ambitions was to foster discussion between the experimental and theoretical

  1. Reduction in the surface energy of liquid interfaces at short length scales

    PubMed

    Fradin; Braslau; Luzet; Smilgies; Alba; Boudet; Mecke; Daillant

    2000-02-24

    Liquid-vapour interfaces, particularly those involving water, are common in both natural and artificial environments. They were first described as regions of continuous variation of density, caused by density fluctuations within the bulk phases. In contrast, the more recent capillary-wave models assumes a step-like local density profile across the liquid-vapour interface, whose width is the result of the propagation of thermally excited capillary waves. The model has been validated for length scales of tenths of micrometres and larger, but the structure of liquid surfaces on submicrometre length scales--where the capillary theory is expected to break down--remains poorly understood. Here we report grazing-incidence X-ray scattering experiments that allow for a complete determination of the free surface structure and surface energy for water and a range of organic liquids. We observe a large decrease of up to 75% in the surface energy of submicrometre waves that cannot be explained by capillary theory, but is in accord with the effects arising from the non-locality of attractive intermolecule interactions as predicted by a recent density functional theory. Our data, and the results of comparable measurements on liquid solutions, metallic alloys, surfactants, lipids and wetting films should thus provide a stringent test for any new theories that attempt to describe the structure of liquid interfaces with nanometre-scale resolution.

  2. Appropriate Formulations for Velocity and Pressure Calculations at Gas-liquid Interface with Collocated Variable Arrangement

    NASA Astrophysics Data System (ADS)

    Ito, Kei; Kunugi, Tomoaki

    A high-precision simulation algorithm for gas-liquid two-phase flows on unstructured meshes has been developed to simulate gas entrainment phenomenon in a sodium-cooled fast reactor. In this study, it became clear that unphysical behaviors near gas-liquid interfaces were caused by conventional algorithms. Then, physics-basis considerations were conducted for mechanical balances at gas-liquid interfaces to derive appropriate formulations. By defining momentum and velocity independently and developing the momentum transport equations for both gas and liquid phases, the physically appropriate formulation of momentum transport was derived, which eliminated the unphysical pressure distribution caused by the conventional formulation. In addition, the physically appropriate formulation was derived for the pressure gradient to satisfy the mechanical balances between pressure and surface tension at gas-liquid interfaces. As the validation test, the rising gas bubble in liquid was simulated by the developed simulation algorithm with the physically appropriate formulations, and the simulated terminal bubble shapes on the structured and highly-distorted unstructured meshes coincided with the experimental data under each simulation condition determined by the Morton and Eötvös numbers.

  3. Instructional Review: An Introduction to Optical Methods for Characterizing Liquid Crystals at Interfaces

    PubMed Central

    Miller, Daniel S.; Carlton, Rebecca J.; Mushenheim, Peter C.; Abbott, Nicholas L.

    2013-01-01

    This Instructional Review describes methods and underlying principles that can be used to characterize both the orientations assumed spontaneously by liquid crystals (LCs) at interfaces and the strength with which the LCs are held in those orientations (so-called anchoring energies). The application of these methods to several different classes of LC interfaces is described, including solid and aqueous interfaces as well as planar and non-planar interfaces (such as those that define a LC-in-water emulsion droplet). These methods, which enable fundamental studies of the ordering of LCs at polymeric, chemically-functionalized and biomolecular interfaces, are described in this article at a level that can be easily understood by a non-expert reader such as an undergraduate or graduate student. We focus on optical methods because they are based on instrumentation that is found widely in research and teaching laboratories. PMID:23347378

  4. Morphological stability of a solid-liquid interface growing in a cylindrical mold

    NASA Astrophysics Data System (ADS)

    Kato, Hiroshi

    2016-12-01

    The morphological stability of the planar interface of dilute alloys solidifying in a cylindrical mold is analyzed based on the perturbation model presented by Mullins and Sekerka under the assumption that the interface crosses the mold wall at right angles, to examine the effect of the inside diameter of the mold. When the interface grows in a mold of a larger inside diameter, the stability-instability criterion of the planar interface is coincident with the MS criterion. On the other hand, in a mold of a smaller diameter, the rippled interface is permitted to take a frequency of discrete values (the permitted frequency), and the planar interface grows stably under thermal conditions slightly exceeding the MS criterion. Also, there exists a minimum permitted frequency ωmin, and the critical inside diameter dc is derived from ωmin. When the alloy solidifies in a mold of an inside diameter less than dc, the interface grows stably under thermal conditions in which the MS model predicts unstable growth of the interface. Moreover, there is a lower limit dG in dc, and when the alloy solidifies in a mold of an inside diameter less than dG, the interface grows stably even at a zero temperature gradient in the liquid.

  5. Possible fossil H2O liquid-ice interfaces in the Martian crust

    NASA Technical Reports Server (NTRS)

    Soderblom, L. A.; Wenner, D. B.

    1978-01-01

    The extensive chaotic and fretted terrains in the equatorial regions of Mars are explained on the basis of the vertical distribution of H2O liquid and ice which once existed in the crust. This account assumes that below the permafrost containing water ice, there was a second zone in which liquid water resided for at least a time. Diagenetic alteration and cementation characterized the material in the subpermafrost zone; above, pristine fragmented material with various ice concentrations was found. Later, the ice-laden zone was stripped away by a number of erosional processes, exposing the former ice-liquid water interface.

  6. Coarse-Graining the Liquid-Liquid Interfaces with the MARTINI Force Field: How Is the Interfacial Tension Reproduced?

    PubMed

    Ndao, Makha; Devémy, Julien; Ghoufi, Aziz; Malfreyt, Patrice

    2015-08-11

    We report two-phase coarse-grained (CG) simulations of organic-water liquid-liquid interfaces with the MARTINI force field. We discuss the ability of the CG force field to predict quantitatively the interfacial tension of alkanes-water, benzene-water, chloroform-water, and alcohol-water systems. The performance of the prediction of the interfacial tension is evaluated through its dependence on temperature and alkane length. This study contributes to the challenging discussion about the robustness and the transferability of the MARTINI force field to interfacial properties. We have also used the distributions of the molecules along the direction normal to the interface to investigate the composition of the interfacial region and to compare the simulated densities of the coexisting phases with experiments.

  7. Pattern formation at liquid interfaces II. The KI/chloral hydrate/starch system

    NASA Astrophysics Data System (ADS)

    Liu, Cliff Zeh-Wen; Knobler, Charles M.

    1992-02-01

    Measurements are reported of pattern formation at a liquid interface produced by a photochemical reaction involving the system KI/chloral hydrate/ starch. The dependence of the wavelength on the concentrations of the reactants, the viscosity, and the height of the sample has been examined. It is concluded that the pattern is produced by a hydrodynamic mechanism.

  8. Thermocapillary Interaction between a Solid Particle and a Liquid-Gas Interface

    NASA Astrophysics Data System (ADS)

    Golovin, A. A.; Leshansky, A. M.; Nir, A.

    1996-11-01

    Interaction between solid particles and a free liquid-gas interface is very important for flotation processes and for various processes involving multiphase flows. In the present contribution, interaction between a hot solid particle submerged into an ambient fluid, and a free liquid-gas interface is considered. A non-uniform temperature field around the solid particle produces surface tension gradients at the liquid-gas interface which generate a thermocapillary flow in the surrounding fluid. This flow yields the motion of the solid particle itself. Three cases are considered: (i) interaction between a solid particle and a spherical gas bubble at a finite separation distance; (ii) thermocapillary motion of a solid particle and an attached gas bubble; (iii) interaction between a solid particle and a plane undeformable liquid-gas interface. In all cases the velocity of the thermocapillarity induced motion of the solid particle is calculated in the approximation of the Stokes flow and a low Peclet number as a function of the separation distance and the bubble-to-particle radii ratio. Some preliminary results of the present work have been published in (A.A.Golovin, Int. J. Multiphase Flow 21), 715 (1995)..

  9. Monitoring the solid-liquid interface in tanks using profiling sonar and 3D visualization techniques

    NASA Astrophysics Data System (ADS)

    Sood, Nitin; Zhang, Jinsong; Roelant, David; Srivastava, Rajiv

    2005-03-01

    Visualization of the interface between settled solids and the optically opaque liquid above is necessary to facilitate efficient retrieval of the high-level radioactive waste (HLW) from underground storage tanks. A profiling sonar was used to generate 2-D slices across the settled solids at the bottom of the tank. By incrementally rotating the sonar about its centerline, slices of the solid-liquid interface can be imaged and a 3-D image of the settled solids interface generated. To demonstrate the efficacy of the sonar in real-time solid-liquid interface monitoring systems inside HLW tanks, two sets of experiments were performed. First, various solid objects and kaolin clay (10 μm dia) were successfully imaged while agitating with 30% solids (by weight) entrained in the liquid. Second, a solid with a density similar to that of the immersed fluid density was successfully imaged. Two dimensional (2-D) sonar images and the accuracy and limitations of the in-tank imaging will be presented for these two experiments. In addition, a brief review of how to utilize a 2-D sonar image to generate a 3-D surface of the settled layer within a tank will be discussed.

  10. Evaluation of air-liquid interface exposure systems for in vitro assessment of airborne pollutants

    EPA Science Inventory

    Exposure of cells to airborne pollutants at the air-liquid interface (ALI) is a more realistic approach than exposures of submerged cells. The published literature, however, describes irreproducible and/or unrealistic experimental conditions using ALI systems. We have compared fi...

  11. Mean-Field Approximation to the Hydrophobic Hydration in the Liquid-Vapor Interface of Water.

    PubMed

    Abe, Kiharu; Sumi, Tomonari; Koga, Kenichiro

    2016-03-03

    A mean-field approximation to the solvation of nonpolar solutes in the liquid-vapor interface of aqueous solutions is proposed. It is first remarked with a numerical illustration that the solvation of a methane-like solute in bulk liquid water is accurately described by the mean-field theory of liquids, the main idea of which is that the probability (Pcav) of finding a cavity in the solvent that can accommodate the solute molecule and the attractive interaction energy (uatt) that the solute would feel if it is inserted in such a cavity are both functions of the solvent density alone. It is then assumed that the basic idea is still valid in the liquid-vapor interface, but Pcav and uatt are separately functions of different coarse-grained local densities, not functions of a common local density. Validity of the assumptions is confirmed for the solvation of the methane-like particle in the interface of model water at temperatures between 253 and 613 K. With the mean-field approximation extended to the inhomogeneous system the local solubility profiles across the interface at various temperatures are calculated from Pcav and uatt obtained at a single temperature. The predicted profiles are in excellent agreement with those obtained by the direct calculation of the excess chemical potential over an interfacial region where the solvent local density varies most rapidly.

  12. Molecular dynamics of phenol at the liquid-vapor interface of water

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; Benjamin, Ilan

    1991-01-01

    Results of molecular dynamics calculations on phenol at the water liquid-vapor interface are presented. The density profile of the center of mass of phenol exhibits a maximum 1 A from the Gibbs surface toward the vapor phase, indicating that the molecule is surface-active. Changes in the profile caused by the interface extend 6 A from the Gibbs surface into the liquid, significantly more than change in the density profile of water. The most probable orientation of the solute at the surface is such that its symmetry axis is perpendicular to the interface with the OH substituent pointing toward the liquid. An additional simulation with benzene shows that this molecule at the surface most often adopts orientations parallel to the interface. Deeper in the liquid all the solutes are preferentially ordered perpendicular to the surface. In the interfacial region the orientational preferences of the solute are primarily determined by cavity formation needed to accommodate the hydrophobic portion of the dissolved molecule.

  13. The Assembly of DNA Amphiphiles at Liquid Crystal-Aqueous Interface

    PubMed Central

    Zhou, Jingsheng; Dong, Yuanchen; Zhang, Yiyang; Liu, Dongsheng; Yang, Zhongqiang

    2016-01-01

    In this article, we synthesized a type of DNA amphiphiles (called DNA-lipids) and systematically studied its assembly behavior at the liquid crystal (LC)—aqueous interface. It turned out that the pure DNA-lipids at various concentrations cannot trigger the optical transition of liquid crystals from planar anchoring to homeotropic anchoring at the liquid crystal—aqueous interface. The co-assembly of DNA-lipid and l-dilauroyl phosphatidylcholine (l-DLPC) indicated that the DLPC assembled all over the LC-aqueous interface, and DNA-lipids prefer to couple with LC in certain areas, particularly in polarized and fluorescent image, forming micron sized net-like structures. The addition of DNA complementary to DNA-lipids forming double stranded DNA-lipids caused de-assembly of DNA-lipids from LC-aqueous interface, resulting in the disappearance of net-like structures, which can be visualized through polarized microscope. The optical changes combined with DNA unique designable property and specific interaction with wide range of target molecules, the DNA-lipids decorated LC-aqueous interface would provide a new platform for biological sensing and diagnosis.

  14. Capillary-driven interface oscillations of cryogenic liquids under non-isothermal boundary conditions

    NASA Astrophysics Data System (ADS)

    Kulev, Nikolai; Dreyer, Michael

    2012-11-01

    Experiments were conducted in the Drop Tower in Bremen for 4.7 s under conditions, similar to the end of thrust in a rocket tank when the cold propellant flows along the warmer tank wall driven by capillary forces. The interface oscillations of liquid argon and liquid methane were investigated in a partly filled cylinder. The oscillations take place during the interface reorientation from its normal gravity (1g) position towards a new position upon step transition to microgravity (10-6g). Axial wall temperature gradients of 0.15 K/mm - 1.93 K/mm were applied above the 1g interface position. The contact line motion changed from aperiodic to oscillatory and the dynamic contact angle increased with the increasing value of the wall temperature gradient. The frequency of the interface center point oscillation increased too. The vapor pressure evolution followed the contact line motion, presumably due to relation of the evaporation to the contact line motion. The vapor temperature above the interface decreased (up to 3.5 K), apparently because of the enhanced evaporation by the contact line motion. The wall temperature in the region of the contact line motion decreased too (up to 8.5 K), hinting to an increased heat transfer by the evaporation between liquid and wall. The funding by the German Federal Ministry of Education and Research (BMBF) through the German Aerospace Center (DLR) under grant number 50 RL 0921 is gratefully acknowledged.

  15. Formative evaluation of a mobile liquid portion size estimation interface for people with varying literacy skills

    PubMed Central

    Connelly, Kay; Siek, Katie A.; Welch, Janet L.

    2012-01-01

    Chronically ill people, especially those with low literacy skills, often have difficulty estimating portion sizes of liquids to help them stay within their recommended fluid limits. There is a plethora of mobile applications that can help people monitor their nutritional intake but unfortunately these applications require the user to have high literacy and numeracy skills for portion size recording. In this paper, we present two studies in which the low- and the high-fidelity versions of a portion size estimation interface, designed using the cognitive strategies adults employ for portion size estimation during diet recall studies, was evaluated by a chronically ill population with varying literacy skills. The low fidelity interface was evaluated by ten patients who were all able to accurately estimate portion sizes of various liquids with the interface. Eighteen participants did an in situ evaluation of the high-fidelity version incorporated in a diet and fluid monitoring mobile application for 6 weeks. Although the accuracy of the estimation cannot be confirmed in the second study but the participants who actively interacted with the interface showed better health outcomes by the end of the study. Based on these findings, we provide recommendations for designing the next iteration of an accurate and low literacy-accessible liquid portion size estimation mobile interface. PMID:24443659

  16. Using Si Diodes To Detect H2 Liquid/Vapor Interfaces

    NASA Technical Reports Server (NTRS)

    Dempsey, Paula Jean; Fabik, Richard

    1994-01-01

    Commercially available silicon-diode temperature sensors used to detect interfaces between hydrogen liquid and hydrogen vapor at steady-state saturation conditions. Sensors mounted at short intervals along rod to form rake-like array. Array inserted in tank with rod oriented vertically, where it senses level of liquid hydrogen to resolution equal to interval between sensors. Basic idea to measure voltage across sensor while supplying small electric current that heats sensor. Because vapor cools sensor less effectively than liquid does, sensor's steady-state temperature greater when sensor surrounded by vapor than when immersed in liquid. Voltage output decreases as temperature increases for silicon diodes. Thus, temperature (voltage) reading used to determine whether liquid level above or below sensor.

  17. Gradual improvements of charge carrier mobility at ionic liquid/rubrene single crystal interfaces

    NASA Astrophysics Data System (ADS)

    Yokota, Yasuyuki; Hara, Hisaya; Morino, Yusuke; Bando, Ken-ichi; Ono, Sakurako; Imanishi, Akihito; Okada, Yugo; Matsui, Hiroyuki; Uemura, Takafumi; Takeya, Jun; Fukui, Ken-ichi

    2016-02-01

    We report evolution of electric characteristics of an electric double layer field-effect transistor based on the ionic liquid/rubrene single crystal interfaces. In contrast to usual devices, the field effect mobility was found to gradually increase with time for a day, followed by minor long-term fluctuations. Although the details of the evolution were somewhat device dependent, the final values of the mobility turned out to be 3-4 times larger irrespective of the initial values. These observations are explained by the evolution of the flat interface by defect-induced spontaneous dissolution of rubrene molecules at the ionic liquid/rubrene single crystal interfaces, revealed by frequency modulation atomic force microscopy.

  18. Reversible Photoresponsive Molecular Alignment of Liquid Crystals at Fluid Interfaces with Persistent Stability.

    PubMed

    Tian, Tongtong; Hu, Qiongzheng; Wang, Yi; Gao, Yanan; Yu, Li

    2016-04-25

    This work demonstrates a noninvasive approach to control alignment of liquid crystals persistently and reversibly at fluid interfaces by using a photoresponsive azobenzene-based surfactant dissolved in an ionic liquid (IL), ethylammonium nitrate (EAN). As the first report on the orientational behavior of LCs at the IL/LC interface, our study also expands current understanding of alignment control of LCs at the aqueous/LC interface by adding electrolytes into aqueous solutions. The threshold concentration for switching the optical responses of LCs can be changed just by simply manipulating the ratio of EAN to H2 O. This work will inspire fundamental studies and novel applications of using the LC-based imaging technique to investigate various chemical and biological events in ILs.

  19. Study of surface charge density on solid/liquid interfaces by modulating the electrical double layer

    NASA Astrophysics Data System (ADS)

    Pak, Hyuk Kyu; Moon, Jong Kyun

    2014-11-01

    A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid/liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid/liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a DC bias voltage across the plates, an AC electric current can be generated. By measuring the voltage difference between the plates as a function of bias voltage, we can study the surface charge density on solid/liquid interfaces. Our experimental results agree very well with the simple equivalent circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. This work was supported by Center for Soft and Living Matter through IBS program in Korea.

  20. Thermal-hydraulic behaviors of vapor-liquid interface due to arrival of a pressure wave

    SciTech Connect

    Inoue, Akira; Fujii, Yoshifumi; Matsuzaki, Mitsuo

    1995-09-01

    In the vapor explosion, a pressure wave (shock wave) plays a fundamental role for triggering, propagation and enhancement of the explosion. Energy of the explosion is related to the magnitude of heat transfer rate from hot liquid to cold volatile one. This is related to an increasing rate of interface area and to an amount of transient heat flux between the liquids. In this study, the characteristics of transient heat transfer and behaviors of vapor film both on the platinum tube and on the hot melt tin drop, under same boundary conditions have been investigated. It is considered that there exists a fundamental mechanism of the explosion in the initial expansion process of the hot liquid drop immediately after arrival of pressure wave. The growth rate of the vapor film is much faster on the hot liquid than that on the solid surface. Two kinds of roughness were observed, one due to the Taylor instability, by rapid growth of the explosion bubble, and another, nucleation sites were observed at the vapor-liquid interface. Based on detailed observation of early stage interface behaviors after arrival of a pressure wave, the thermal fragmentation mechanism is proposed.

  1. Numerical studies of the effects of jet-induced mixing on liquid-vapor interface condensation

    NASA Technical Reports Server (NTRS)

    Lin, Chin-Shun

    1989-01-01

    Numerical solutions of jet-induced mixing in a partially full cryogenic tank are presented. An axisymmetric laminar jet is discharged from the central part of the tank bottom toward the liquid-vapor interface. Liquid is withdrawn at the same volume flow rate from the outer part of the tank. The jet is at a temperature lower than the interface, which is maintained at a certain saturation temperature. The interface is assumed to be flat and shear-free and the condensation-induced velocity is assumed to be negligibly small compared with radial interface velocity. Finite-difference method is used to solve the nondimensional form of steady state continuity, momentum, and energy equations. Calculations are conducted for jet Reynolds numbers ranging from 150 to 600 and Prandtl numbers ranging from 0.85 to 2.65. The effects of above stated parameters on the condensation Nusselt and Stanton numbers which characterize the steady-state interface condensation process are investigated. Detailed analysis to gain a better understanding of the fundamentals of fluid mixing and interface condensation is performed.

  2. Delivery of minimally dispersed liquid interfaces for sequential surface chemistry.

    PubMed

    Ostromohov, N; Bercovici, M; Kaigala, G V

    2016-08-02

    We present a method for sequential delivery of reagents to a reaction site with minimal dispersion of their interfaces. Using segmented flow to encapsulate the reagents as droplets, the dispersion between reagent plugs remains confined in a limited volume, while being transmitted to the reaction surface. In close proximity to the target surface, we use a passive array of microstructures for removal of the oil phase such that the original reagent sequence is reconstructed, and only the aqueous phase reaches the reaction surface. We provide a detailed analysis of the conditions under which the method can be applied and demonstrate maintaining a transition time of 560 ms between reagents transported to a reaction site over a distance of 60 cm. We implemented the method using a vertical microfluidic probe on an open surface, allowing contact-free interaction with biological samples, and demonstrated two examples of assays implemented using the method: measurements of receptor-ligand reaction kinetics and of the fluorescence response of immobilized GFP to local variations in pH. We believe that the method can be useful for studying the dynamic response of cells and proteins to various stimuli, as well as for highly automated multi-step assays.

  3. Density functional theory for crystal-liquid interfaces of Lennard-Jones fluid.

    PubMed

    Wang, Xin; Mi, Jianguo; Zhong, Chongli

    2013-04-28

    A density functional approach is presented to describe the crystal-liquid interfaces and crystal nucleations of Lennard-Jones fluid. Within the theoretical framework, the modified fundamental measure theory is applied to describe the free energy functional of hard sphere repulsion, and the weighted density method based on first order mean spherical approximation is used to describe the free energy contribution arising from the attractive interaction. The liquid-solid equilibria, density profiles within crystal cells and at liquid-solid interfaces, interfacial tensions, nucleation free energy barriers, and critical cluster sizes are calculated for face-centered-cubic and body-centered-cubic nucleus. Some results are in good agreement with available simulation data, indicating that the present model is quantitatively reliable in describing nucleation thermodynamics of Lennard-Jones fluid.

  4. Effect of asymmetric gravity jitter excited slosh waves at liquid-vapor interface under microgravity

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Pan, H. L.; Lee, C. C.; Leslie, F. W.

    1992-01-01

    The dynamical behavior of fluids affected by the asymmetric gravity jitter oscillations, in particular the effect of surface tension on partially-filled rotating fluids (cryogenic liquid helium and helium vapor) in a sub-scale Gravity Probe-B Spacecraft propellant dewar tank imposed by time-dependent various directions of background gravity environment have been investigated. Results show that lower frequency gravity jitter imposed on the time-dependent variations of the direction of background gravity induced a greater amplitude of oscillations and a stronger degree of asymmetry in liquid-vapor interface geometry than that made by the higher frequency gravity jitter. Furthermore, the greater the components of background gravity in radial and circumferential directions will provide a greater contribution in driving more to the increasing amplitude and degrees of symmetry of liquid-vapor interface profiles which, in turn, modify the disturbance of moment of inertia and angular momentum of spacecraft.

  5. Modeling of ultrasound transmission through a solid-liquid interface comprising a network of gas pockets

    NASA Astrophysics Data System (ADS)

    Paumel, K.; Moysan, J.; Chatain, D.; Corneloup, G.; Baqué, F.

    2011-08-01

    Ultrasonic inspection of sodium-cooled fast reactor requires a good acoustic coupling between the transducer and the liquid sodium. Ultrasonic transmission through a solid surface in contact with liquid sodium can be complex due to the presence of microscopic gas pockets entrapped by the surface roughness. Experiments are run using substrates with controlled roughness consisting of a network of holes and a modeling approach is then developed. In this model, a gas pocket stiffness at a partially solid-liquid interface is defined. This stiffness is then used to calculate the transmission coefficient of ultrasound at the entire interface. The gas pocket stiffness has a static, as well as an inertial component, which depends on the ultrasonic frequency and the radiative mass.

  6. Water distribution at solid/liquid interfaces visualized by frequency modulation atomic force microscopy

    PubMed Central

    Fukuma, Takeshi

    2010-01-01

    Interfacial phenomena at solid/water interfaces play an important role in a wide range of industrial technologies and biological processes. However, it has been a great challenge to directly probe the molecular-scale behavior of water at solid/water interfaces. Recently, there have been tremendous advancements in frequency modulation atomic force microscopy (FM-AFM), enabling its operation in liquids with atomic resolution. The high spatial and force resolutions of FM-AFM have enabled the visualization of one-dimensional (1D) profiles of the hydration force, two-dimensional (2D) images of hydration layers and three-dimensional (3D) images of the water distribution at solid/water interfaces. Here I present an overview of the recent advances in FM-AFM instrumentation and its applications to the study of solid/water interfaces. PMID:27877337

  7. Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface

    SciTech Connect

    von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M.; Blumberger, Jochen

    2016-04-07

    The interface between transition-metal oxides and aqueous solutions plays an important role in biogeochemistry and photoelectrochemistry, but the atomistic structure is often elusive. Here we report on the surface geometry, solvation structure, and thermal fluctuations of the hydrogen bonding network at the hematite (001)–water interface as obtained from hybrid density functional theory-based molecular dynamics. We find that the protons terminating the surface form binary patterns by either pointing in-plane or out-of-plane. The patterns exist for about 1 ps and spontaneously interconvert in an ultrafast, solvent-driven process within 50 fs. This results in only about half of the terminating protons pointing toward the solvent and being acidic. The lifetimes of all hydrogen bonds formed at the interface are shorter than those in pure liquid water. The solvation structure reported herein forms the basis for a better fundamental understanding of electron transfer coupled to proton transfer reactions at this important interface.

  8. Electrochemical Investigation of Adsorption of Single‐Wall Carbon Nanotubes at a Liquid/Liquid Interface

    PubMed Central

    Rabiu, Aminu K.; Toth, Peter S.; Rodgers, Andrew N. J.

    2016-01-01

    Abstract There is much interest in understanding the interfacial properties of carbon nanotubes, particularly at water/oil interfaces. Here, the adsorption of single‐wall carbon nanotubes (SWCNTs) at the water/1,2‐dichloroethane (DCE) interface, and the subsequent investigation of the influence of the adsorbed nanotube layer on interfacial ion transfer, is studied by using the voltammetric transfer of tetramethylammonium (TMA+) and hexafluorophosphate (PF6 −) as probe ions. The presence of the interfacial SWCNT layer significantly suppresses the transfer of both ions across the interface, with a greater degree of selectivity towards the PF6 − ion. This effect was attributed both to the partial blocking of the interface by the SWCNTs and to the potential dependant adsorption of background electrolyte ions on the surface of the SWCNTs, as confirmed by X‐ray photoelectron spectroscopy, which is caused by an electrostatic interaction between the interfacial SWCNTs and the transferring ion. PMID:28168151

  9. Electrochemical Investigation of Adsorption of Single-Wall Carbon Nanotubes at a Liquid/Liquid Interface.

    PubMed

    Rabiu, Aminu K; Toth, Peter S; Rodgers, Andrew N J; Dryfe, Robert A W

    2017-02-01

    There is much interest in understanding the interfacial properties of carbon nanotubes, particularly at water/oil interfaces. Here, the adsorption of single-wall carbon nanotubes (SWCNTs) at the water/1,2-dichloroethane (DCE) interface, and the subsequent investigation of the influence of the adsorbed nanotube layer on interfacial ion transfer, is studied by using the voltammetric transfer of tetramethylammonium (TMA(+)) and hexafluorophosphate (PF6(-)) as probe ions. The presence of the interfacial SWCNT layer significantly suppresses the transfer of both ions across the interface, with a greater degree of selectivity towards the PF6(-) ion. This effect was attributed both to the partial blocking of the interface by the SWCNTs and to the potential dependant adsorption of background electrolyte ions on the surface of the SWCNTs, as confirmed by X-ray photoelectron spectroscopy, which is caused by an electrostatic interaction between the interfacial SWCNTs and the transferring ion.

  10. AUX: a scripting language for auditory signal processing and software packages for psychoacoustic experiments and education.

    PubMed

    Kwon, Bomjun J

    2012-06-01

    This article introduces AUX (AUditory syntaX), a scripting syntax specifically designed to describe auditory signals and processing, to the members of the behavioral research community. The syntax is based on descriptive function names and intuitive operators suitable for researchers and students without substantial training in programming, who wish to generate and examine sound signals using a written script. In this article, the essence of AUX is discussed and practical examples of AUX scripts specifying various signals are illustrated. Additionally, two accompanying Windows-based programs and development libraries are described. AUX Viewer is a program that generates, visualizes, and plays sounds specified in AUX. AUX Viewer can also be used for class demonstrations or presentations. Another program, Psycon, allows a wide range of sound signals to be used as stimuli in common psychophysical testing paradigms, such as the adaptive procedure, the method of constant stimuli, and the method of adjustment. AUX Library is also provided, so that researchers can develop their own programs utilizing AUX. The philosophical basis of AUX is to separate signal generation from the user interface needed for experiments. AUX scripts are portable and reusable; they can be shared by other researchers, regardless of differences in actual AUX-based programs, and reused for future experiments. In short, the use of AUX can be potentially beneficial to all members of the research community-both those with programming backgrounds and those without.

  11. Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface.

    PubMed

    Williamson, M J; Tromp, R M; Vereecken, P M; Hull, R; Ross, F M

    2003-08-01

    Dynamic processes at the solid-liquid interface are of key importance across broad areas of science and technology. Electrochemical deposition of copper, for example, is used for metallization in integrated circuits, and a detailed understanding of nucleation, growth and coalescence is essential in optimizing the final microstructure. Our understanding of processes at the solid-vapour interface has advanced tremendously over the past decade due to the routine availability of real-time, high-resolution imaging techniques yielding data that can be compared quantitatively with theory. However, the difficulty of studying the solid-liquid interface leaves our understanding of processes there less complete. Here we analyse dynamic observations--recorded in situ using a novel transmission electron microscopy technique--of the nucleation and growth of nanoscale copper clusters during electrodeposition. We follow in real time the evolution of individual clusters, and compare their development with simulations incorporating the basic physics of electrodeposition during the early stages of growth. The experimental technique developed here is applicable to a broad range of dynamic phenomena at the solid-liquid interface.

  12. Sample cells for probing solid/liquid interfaces with broadband sum-frequency-generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Verreault, Dominique; Kurz, Volker; Howell, Caitlin; Koelsch, Patrick

    2010-06-01

    Two sample cells designed specifically for sum-frequency-generation (SFG) measurements at the solid/liquid interface were developed: one thin-layer analysis cell allowing measurement of films on reflective metallic surfaces through a micrometer layer of solution and one spectroelectrochemical cell allowing investigation of processes at the indium tin oxide/solution interface. Both sample cells are described in detail and data illustrating the capabilities of each are shown. To further improve measurements at solid/liquid interfaces, the broadband SFG system was modified to include a reference beam which can be measured simultaneously with the sample signal, permitting background correction of SFG spectra in real time. Sensitivity tests of this system yielded a signal-to-noise ratio of 100 at a surface coverage of 0.2 molecules/nm2. Details on data analysis routines, pulse shaping methods of the visible beam, as well as the design of a purging chamber and sample stage setup are presented. These descriptions will be useful to those planning to set up a SFG spectrometer or seeking to optimize their own SFG systems for measurements of solid/liquid interfaces.

  13. Interaction between a disclination and a uniaxial-isotropic phase interface in a nematic liquid crystal.

    PubMed

    Shklyaev, Oleg E; Fried, Eliot

    2008-01-01

    We consider the interaction between a disclination line of strength +/-1/2 and an interface between the uniaxial and isotropic phases of a nematic liquid crystal. We apply a recently developed set of interface conditions including a configurational force balance which generalizes the Gibbs-Thomson equation to account for the curvature elasticity of the uniaxial phase and the orientation dependence of the interfacial free-energy density. We consider a rectangular vessel containing both phases and a disclination. We formulate a relevant free-boundary problem and use numerical methods to determine equilibrium shapes of the interface. When the interfacial free-energy is constant, the shape of the interface is insensitive to whether the strength of the defect is +1/2 or -1/2 and to rotations of the director field consistent with the boundary conditions. Accounting for the dependence of the interfacial free-energy density on the angle between the interfacial unit normal field and the director field eliminates these degeneracies. In particular, when such dependence is taken into account, different solution branches are found, indicating the presence of a bifurcation. We find also that, depending on the magnitude of the anisotropic contribution to the interfacial free-energy density, the interaction between the disclination and the interface may be repulsive or attractive. When the interaction is repulsive, the disclination line positions itself at an energetically optimal distance adjacent to the interface. Otherwise, the uniaxial phase expels the disclination to the interface where a cusp forms.

  14. Adsorption of the natural protein surfactant Rsn-2 onto liquid interfaces.

    PubMed

    Brandani, Giovanni B; Vance, Steven J; Schor, Marieke; Cooper, Alan; Kennedy, Malcolm W; Smith, Brian O; MacPhee, Cait E; Cheung, David L

    2017-03-22

    To stabilize foams, droplets and films at liquid interfaces a range of protein biosurfactants have evolved in nature. Compared to synthetic surfactants, these combine surface activity with biocompatibility and low solution aggregation. One recently studied example is Rsn-2, a component of the foam nest of the frog Engystomops pustulosus, which has been predicted to undergo a clamshell-like opening transition at the air-water interface. Using atomistic molecular dynamics simulations and surface tension measurements we study the adsorption of Rsn-2 onto air-water and cyclohexane-water interfaces. The protein adsorbs readily at both interfaces, with adsorption mediated by the hydrophobic N-terminus. At the cyclohexane-water interface the clamshell opens, due to the favourable interaction between hydrophobic residues and cyclohexane molecules and the penetration of cyclohexane molecules into the protein core. Simulations of deletion mutants showed that removal of the N-terminus inhibits interfacial adsorption, which is consistent with the surface tension measurements. Deletion of the hydrophilic C-terminus also affects adsorption, suggesting that this plays a role in orienting the protein at the interface. The characterisation of the interfacial behaviour gives insight into the factors that control the interfacial adsorption of proteins, which may inform new applications of this and similar proteins in areas including drug delivery and food technology and may also be used in the design of synthetic molecules showing similar changes in conformation at interfaces.

  15. Fabrication of composite polymer foam films at the liquid/liquid interface through emulsion-directed assembly and adsorption processes.

    PubMed

    Geng, Yuanyuan; Liu, Mei; Tong, Kun; Xu, Jian; Lee, Yong-Ill; Hao, Jingcheng; Liu, Hong-Guo

    2014-03-04

    The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(II) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.

  16. Interaction of Porosity with an Advancing Solid/Liquid Interface: a Real-Time Investigation

    NASA Technical Reports Server (NTRS)

    Sen, S.; Kaukler, W.; Catalina, A.; Stefanescu, D.; Curreri, P.

    1999-01-01

    Problems associated with formation of porosity during solidification continue to have a daily impact on the metal forming industry. Several past investigations have dealt with the nucleation and growth aspects of porosity. However, investigations related to the interaction of porosity with that of a solidification front has been limited mostly to organic analogues. In this paper we report on real time experimental observations of such interactions in metal alloys. Using a state of the art X-Ray Transmission Microscope (XTM) we have been able to observe and record the dynamics of the interaction. This includes distortion of the solid/liquid interface near a poro.sity, solute segr,egation patterns surrounding a porosity and the change in shape of the porosity during interaction with an advancing solid/liquid interface. Results will be presented for different Al alloys and growth conditions. The experimental data will be compared to theory using a recently developed 2D numerical model. The model employs a finite difference approach where the solid/liquid interface is defined through the points at which the interface intersects the grid lines. The transport variables are calculated at these points and the motion of the solidification front is determined by the magnitude of the transport variables. The model accounts for the interplay of the thermal and solutal field and the influence of capilarity to predict the shape of the solid/liquid interface with time in the vicinity of porosity. One can further calculate the perturbation of the solutal field by the presence of porosity in the melt.

  17. Instability of the Liquid Metal-Pattern Interface in the Lost Foam Casting of Aluminum Alloys

    NASA Astrophysics Data System (ADS)

    Griffiths, W. D.; Ainsworth, M. J.

    2016-06-01

    The nature of the liquid metal-pattern interface during mold filling in the Lost Foam casting of aluminum alloys was investigated using real-time X-ray radiography for both normal expanded polystyrene, and brominated polystyrene foam patterns. Filling the pattern under the action of gravity from above or below had little effect on properties, both cases resulting in a large scatter of tensile strength values, (quantified by their Weibull Modulus). Countergravity filling at different velocities demonstrated that the least scatter of tensile strength values (highest Weibull Modulus) was associated with the slowest filling, when a planar liquid metal-pattern interface occurred. Real-time X-ray radiography showed that the advancing liquid metal front became unstable above a certain critical velocity, leading to the entrainment of the degrading pattern material and associated defects. It has been suggested that the transition of the advancing liquid metal-pattern interface into an unstable regime may be a result of Saffman-Taylor Instability.

  18. Marangoni instability at a contaminated liquid-vapor interface of a burning thin film

    NASA Astrophysics Data System (ADS)

    Armendáriz, Javier; Matalon, Moshe

    2003-05-01

    We consider the evaporation and subsequent burning of thin films of liquid fuels on which a nonsoluble surface active agent (surfactant) is present. This work complements a previous study where we have considered the same problem but in the absence of surfactant. Surfactant may result from impurities of the liquid fuel or from backward diffusion of unoxidized combustion intermediaries and heavy soot precursors. When burning occurs in a quiescent ambient, the mathematical problem can be systematically reduced to a pair of nonlinear evolution equations for the film's thickness and surfactant's concentration. These equations contain, in particular, the temperature and mass flux at the liquid-vapor interface as additional parameters, determined from full consideration of the gas-phase processes. We show that in the absence of combustion or, when the heat released by the chemical reactions is relatively small, thermo-capillary effects tend to destabilize a nominally planar interface. The presence of surfactant brings about a slower growth and can possibly stabilize the film. Combustion generally acts to reverse these trends: When the heat release is large, thermo-capillary effects stabilize the liquid-vapor interface while the presence of surfactant leads to destabilization.

  19. Heat flow at solid-liquid interfaces: confrontation between experiment and simulation

    NASA Astrophysics Data System (ADS)

    Cahill, David

    2007-03-01

    Heat transport in nanostructures and nanostructured materials provides a novel paradigm for direct comparisons between the results of experiment and simulation. Time-resolved, pump-probe optical techniques enable measurements of the evolution of temperature on time scales from ps to ns. Our pump-probe experiments take two basic forms: measurements of heat transport across planar interfaces using time-domain thermoreflectance and measurements of heat flow from a metal or semiconductor nanostructure into its surroundings using transient absorption. The systems that we are studying are directly accessible to simulation by classical molecular dynamics on the same time and length scales that are encountered in the experiments. Working with our collaborators, P. Keblinski and his colleagues at RPI, we have made quantitative comparisons between experiment and simulation for heat transport from carbon nanotubes and fullerene molecules into a surrounding fluid; and heat transport across hydrophilic and hydrophobic interfaces with water. Any such comparison must take into account i) non-idealities in the experiments; ii) uncertainties in the potentials and atomic geometries in the computational model; and iii) the fact that classical simulations may include high frequency vibrational modes that are not thermally excited in the experiments. Despite the fact that transport at solid-liquid interfaces is more difficult to measure than more commonly studied solid-solid interfaces, we argue that solid-liquid interfaces provide a more reliable system for quantitative comparisons between experiment and simulation.

  20. Computational study of ion distributions at the air/liquid methanol interface

    SciTech Connect

    Sun, Xiuquan; Wick, Collin D.; Dang, Liem X.

    2011-06-16

    Molecular dynamic simulations with polarizable potentials were performed to systematically investigate the distribution of NaCl, NaBr, NaI, and SrCl2 at the air/liquid methanol interface. The density profiles indicated that there is no substantial enhancement of anions at the interface for the NaX systems in contrast to what was observed at the air/aqueous interface. The surfactant-like shape of the larger more polarizable halide anions is compensated by the surfactant nature of methanol itself. As a result, methanol hydroxy groups strongly interacted with one side of polarizable anions, in which their induced dipole points, and methanol methyl groups were more likely to be found near the positive pole of anion induced dipoles. Furthermore, salts were found to disrupt the surface structure of methanol, reducing the observed enhancement of methyl groups at the outer edge of the air/liquid methanol interface. With the additional of salts to methanol, the computed surface potentials increased, which is in contrast to what is observed in corresponding aqueous systems, where the surface potential decreases with the addition of salts. Both of these trends have been indirectly observed with experiments. This was found to be due to the propensity of anions for the air/water interface that is not present at the air/liquid methanol interface. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  1. Interface for the rapid analysis of liquid samples by accelerator mass spectrometry

    DOEpatents

    Turteltaub, Kenneth; Ognibene, Ted; Thomas, Avi; Daley, Paul F; Salazar Quintero, Gary A; Bench, Graham

    2014-02-04

    An interface for the analysis of liquid sample having carbon content by an accelerator mass spectrometer including a wire, defects on the wire, a system for moving the wire, a droplet maker for producing droplets of the liquid sample and placing the droplets of the liquid sample on the wire in the defects, a system that converts the carbon content of the droplets of the liquid sample to carbon dioxide gas in a helium stream, and a gas-accepting ion source connected to the accelerator mass spectrometer that receives the carbon dioxide gas of the sample in a helium stream and introduces the carbon dioxide gas of the sample into the accelerator mass spectrometer.

  2. In situ X-ray studies of adlayer-induced crystal nucleation at the liquid-liquid interface

    SciTech Connect

    Elsen, Annika; Festersen, Sven; Runge, Benjamin; Koops, Christian T.; Ocko, Benjamin M.; Deutsch, Moshe; Seeck, Oliver H.; Murphy, Bridget M.; Magnussen, Olaf M.

    2013-05-29

    Crystal nucleation and growth at a liquid–liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb2+, F-, and Br- ions. In the regime negative of the Pb amalgamation potential Φrp = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb2+ from the Hg bulk at Graphic, the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å–thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their Graphic axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell–thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.

  3. Molecular electrocatalysis for oxygen reduction by cobalt porphyrins adsorbed at liquid/liquid interfaces.

    PubMed

    Su, Bin; Hatay, Imren; Trojánek, Antonín; Samec, Zdenek; Khoury, Tony; Gros, Claude P; Barbe, Jean-Michel; Daina, Antoine; Carrupt, Pierre-Alain; Girault, Hubert H

    2010-03-03

    Molecular electrocatalysis for oxygen reduction at a polarized water/1,2-dichloroethane (DCE) interface was studied, involving aqueous protons, ferrocene (Fc) in DCE and amphiphilic cobalt porphyrin catalysts adsorbed at the interface. The catalyst, (2,8,13,17-tetraethyl-3,7,12,18-tetramethyl-5-p-amino-phenylporphyrin) cobalt(II) (CoAP), functions like conventional cobalt porphyrins, activating O(2) via coordination by the formation of a superoxide structure. Furthermore, due to the hydrophilic nature of the aminophenyl group, CoAP has a strong affinity for the water/DCE interface as evidenced by lipophilicity mapping calculations and surface tension measurements, facilitating the protonation of the CoAP-O(2) complex and its reduction by ferrocene. The reaction is electrocatalytic as its rate depends on the applied Galvani potential difference between the two phases.

  4. Atomically Abrupt Liquid-Oxide Interface Stabilized by Self-Regulated Interfacial Defects: The Case of Al/Al2O3 Interfaces

    SciTech Connect

    Kang, J.; Zhu, J. Y.; Curtis, C.; Blake, D.; Glatzmaier, G.; Kim, Y. H.; Wei, S. H.

    2012-06-01

    The atomic and electronic structures of the liquid Al/(0001) {alpha}-Al{sub 2}O{sub 3} interfaces are investigated by first-principles molecular dynamics simulations. Surprisingly, the formed liquid-solid interface is always atomically abrupt and is characterized by a transitional Al layer that contains a fixed concentration of Al vacancies ({approx}10 at.%). We find that the self-regulation of the defect density in the metal layer is due to the fact that the formation energy of the Al vacancies is readjusted in a way that opposes changes in the defect density. The negative-feedback effect stabilizes the defected transitional layer and maintains the atomic abruptness at the interface. The proposed mechanism is generally applicable to other liquid-metal/metal-oxide systems, and thus of significant importance in understanding the interface structures at high temperature.

  5. Understanding Charge Transfer Reactions at the Interface of Plasmas in Contact with Liquids

    NASA Astrophysics Data System (ADS)

    Go, David

    2015-09-01

    Plasmas in and in contact with liquids offer a very rich physical and chemical environment where a multitude of species (electrons, ions, neutrals) and physical phenomena (light, electric fields) intersect. With emerging applications in medicine, environmental remediation, and materials synthesis, it has become paramount to understand the many processes occurring at the interface in order to design and optimize new technologies. Perhaps the most important plasma species is the electron, and it thus reasonable to assume it can play a critical role when plasmas are brought in contact with liquids as well. Over the past several years, our group has focused on deciphering the nature of electron transfer from a plasma to liquid and the subsequent chemistry the electrons induce. Our experimental configuration is the plasma equivalent of an electrochemical or electrolytic cell, where the cathode and anode are submerged in an electrolyte solution and current is carried by reduction reactions at the cathode and oxidation reactions at the anode. When the cathode is replaced by a plasma, the circuit is explicitly completed by the injection of plasma electrons into the solution where they stably solvate before inducing reduction reactions. Recently, we have demonstrated the first direct detection of these stably solvated electrons using a novel total internal reflection absorption spectroscopy experiment, resulting in the first measurement of the optical absorption spectrum for plasma-solvated electrons. Further, we have shown that the lifetime of these electrons can be significantly reduced if suitable solution- and plasma-phase scavengers are used to react quickly with these electrons. These results highlight the complexity of the plasma-liquid interface and how charge-transfer processes often compete with other chemistry that occurs at the plasma-liquid interface, such as the dissolution of plasma species into the liquid. This work was supported by the U.S. Army Research

  6. Quantum chemical approach in the description of the amphiphile clusterization at the air/liquid and liquid/liquid interfaces with phase nature accounting. I. Aliphatic normal alcohols at the air/water interface.

    PubMed

    Vysotsky, Yuri B; Belyaeva, Elena A; Kartashynska, Elena S; Fainerman, Valentine B; Smirnova, Natalia A

    2015-02-19

    A new model based on the quantum chemical approach is proposed to describe structural and thermodynamic parameters of clusterization for substituted alkanes at the air/liquid and liquid/liquid interfaces. The new model by the authors, unlike the previous one, proposes an explicit account of the liquid phase (phases) influence on the parameters of monomers, clusters and monolayers of substituted alkanes at the regarded interface. The calculations were carried out in the frameworks of the quantum chemical semiempirical PM3 method (Mopac 2012), using the COSMO procedure. The new model was tested in the calculations of the clusterization parameters of fatty alcohols under the standard conditions at the air/water interface. The enthalpy, Gibbs' energy and absolute entropy of formation for alcohol monomers alongside with clusterization parameters for the cluster series including the monolayer at air/water interface were calculated. In our calculations the sinkage of monomers, molecules in clusters and monolayers was varied from 1 up to 5 methylene groups. Thermodynamic parameters calculated using the proposed model for the alcohol monolayers are in a good agreement with the corresponding experimental data. However, the proposed model cannot define the most energetically preferable immersion of the monolayer molecules in the water phase.

  7. Proton-coupled oxygen reduction at liquid-liquid interfaces catalyzed by cobalt porphine.

    PubMed

    Hatay, Imren; Su, Bin; Li, Fei; Méndez, Manuel Alejandro; Khoury, Tony; Gros, Claude P; Barbe, Jean-Michel; Ersoz, Mustafa; Samec, Zdenek; Girault, Hubert H

    2009-09-23

    Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O(2) reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O(2). The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O(2).

  8. Diffuse-interface modeling of liquid-vapor coexistence in equilibrium drops using smoothed particle hydrodynamics.

    PubMed

    Sigalotti, Leonardo Di G; Troconis, Jorge; Sira, Eloy; Peña-Polo, Franklin; Klapp, Jaime

    2014-07-01

    We study numerically liquid-vapor phase separation in two-dimensional, nonisothermal, van der Waals (vdW) liquid drops using the method of smoothed particle hydrodynamics (SPH). In contrast to previous SPH simulations of drop formation, our approach is fully adaptive and follows the diffuse-interface model for a single-component fluid, where a reversible, capillary (Korteweg) force is added to the equations of motion to model the rapid but smooth transition of physical quantities through the interface separating the bulk phases. Surface tension arises naturally from the cohesive part of the vdW equation of state and the capillary forces. The drop models all start from a square-shaped liquid and spinodal decomposition is investigated for a range of initial densities and temperatures. The simulations predict the formation of stable, subcritical liquid drops with a vapor atmosphere, with the densities and temperatures of coexisting liquid and vapor in the vdW phase diagram closely matching the binodal curve. We find that the values of surface tension, as determined from the Young-Laplace equation, are in good agreement with the results of independent numerical simulations and experimental data. The models also predict the increase of the vapor pressure with temperature and the fitting to the numerical data reproduces very well the Clausius-Clapeyron relation, thus allowing for the calculation of the vaporization pressure for this vdW fluid.

  9. The production of drops by the bursting of a bubble at an air liquid interface

    NASA Technical Reports Server (NTRS)

    Darrozes, J. S.; Ligneul, P.

    1982-01-01

    The fundamental mechanism arising during the bursting of a bubble at an air-liquid interface is described. A single bubble was followed from an arbitrary depth in the liquid, up to the creation and motion of the film and jet drops. Several phenomena were involved and their relative order of magnitude was compared in order to point out the dimensionless parameters which govern each step of the motion. High-speed cinematography is employed. The characteristic bubble radius which separates the creation of jet drops from cap bursting without jet drops is expressed mathematically. The corresponding numerical value for water is 3 mm and agrees with experimental observations.

  10. Formation of H-type liquid crystal dimer at air-water interface

    SciTech Connect

    Karthik, C. Gupta, Adbhut Joshi, Aditya Manjuladevi, V. Gupta, Raj Kumar; Varia, Mahesh C.; Kumar, Sandeep

    2014-04-24

    We have formed the Langmuir monolayer of H-shaped Azo linked liquid crystal dimer molecule at the air-water interface. Isocycles of the molecule showed hysteresis suggesting the ir-reversible nature of the monolayer formed. The thin film deposited on the silicon wafer was characterized using Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM). The images showed uniform domains of the dimer molecule. We propose that these molecules tend to take book shelf configuration in the liquid phase.

  11. The DNA Adsorption by the Charged Cholesterol Monolayer at the Air-liquid Interface

    NASA Astrophysics Data System (ADS)

    Lin, Tsang-Lang; Hu, Yuan; Wu, Jui-Ching; Yang, Chun-Pang; Jeng, U.-Ser; Shih, M.-C.

    2004-04-01

    The adsorption of DNA by the 3-,-[N-(N',N'-dimethyl amino ethane) carbamoyl] cholesterol (DC-Chol) monolayer at the air-liquid interface was studied by using the Langmuir-Blodgett film balance. With the presence of 1 μ M DNA in the subphase, the surface pressure increases right at the beginning of the compression. The liquid expanded phase of the DC-Chol disappears due to the adsorption of DNA. The AFM image of the prepared DC-Chol/DNA film has tree-branch-like fractal structure with a height of 2 nm that correspond to the diameter of DNA.

  12. Effect of Schmidt number on mass transfer across a sheared gas-liquid interface in a wind-driven turbulence

    NASA Astrophysics Data System (ADS)

    Takagaki, Naohisa; Kurose, Ryoichi; Kimura, Atsushi; Komori, Satoru

    2016-11-01

    The mass transfer across a sheared gas-liquid interface strongly depends on the Schmidt number. Here we investigate the relationship between mass transfer coefficient on the liquid side, kL, and Schmidt number, Sc, in the wide range of 0.7 ≤ Sc ≤ 1000. We apply a three-dimensional semi direct numerical simulation (SEMI-DNS), in which the mass transfer is solved based on an approximated deconvolution model (ADM) scheme, to wind-driven turbulence with mass transfer across a sheared wind-driven wavy gas-liquid interface. In order to capture the deforming gas-liquid interface, an arbitrary Lagrangian-Eulerian (ALE) method is employed. Our results show that similar to the case for flat gas-liquid interfaces, kL for the wind-driven wavy gas-liquid interface is generally proportional to Sc‑0.5, and can be roughly estimated by the surface divergence model. This trend is endorsed by the fact that the mass transfer across the gas-liquid interface is controlled mainly by streamwise vortices on the liquid side even for the wind-driven turbulence under the conditions of low wind velocities without wave breaking.

  13. Effect of Schmidt number on mass transfer across a sheared gas-liquid interface in a wind-driven turbulence

    PubMed Central

    Takagaki, Naohisa; Kurose, Ryoichi; Kimura, Atsushi; Komori, Satoru

    2016-01-01

    The mass transfer across a sheared gas-liquid interface strongly depends on the Schmidt number. Here we investigate the relationship between mass transfer coefficient on the liquid side, kL, and Schmidt number, Sc, in the wide range of 0.7 ≤ Sc ≤ 1000. We apply a three-dimensional semi direct numerical simulation (SEMI-DNS), in which the mass transfer is solved based on an approximated deconvolution model (ADM) scheme, to wind-driven turbulence with mass transfer across a sheared wind-driven wavy gas-liquid interface. In order to capture the deforming gas-liquid interface, an arbitrary Lagrangian-Eulerian (ALE) method is employed. Our results show that similar to the case for flat gas-liquid interfaces, kL for the wind-driven wavy gas-liquid interface is generally proportional to Sc−0.5, and can be roughly estimated by the surface divergence model. This trend is endorsed by the fact that the mass transfer across the gas-liquid interface is controlled mainly by streamwise vortices on the liquid side even for the wind-driven turbulence under the conditions of low wind velocities without wave breaking. PMID:27841325

  14. Effect of Schmidt number on mass transfer across a sheared gas-liquid interface in a wind-driven turbulence.

    PubMed

    Takagaki, Naohisa; Kurose, Ryoichi; Kimura, Atsushi; Komori, Satoru

    2016-11-14

    The mass transfer across a sheared gas-liquid interface strongly depends on the Schmidt number. Here we investigate the relationship between mass transfer coefficient on the liquid side, kL, and Schmidt number, Sc, in the wide range of 0.7 ≤ Sc ≤ 1000. We apply a three-dimensional semi direct numerical simulation (SEMI-DNS), in which the mass transfer is solved based on an approximated deconvolution model (ADM) scheme, to wind-driven turbulence with mass transfer across a sheared wind-driven wavy gas-liquid interface. In order to capture the deforming gas-liquid interface, an arbitrary Lagrangian-Eulerian (ALE) method is employed. Our results show that similar to the case for flat gas-liquid interfaces, kL for the wind-driven wavy gas-liquid interface is generally proportional to Sc(-0.5), and can be roughly estimated by the surface divergence model. This trend is endorsed by the fact that the mass transfer across the gas-liquid interface is controlled mainly by streamwise vortices on the liquid side even for the wind-driven turbulence under the conditions of low wind velocities without wave breaking.

  15. Conventional and microwave hydrothermal synthesis of monodispersed metal oxide nanoparticles at liquid-liquid interface

    EPA Science Inventory

    Monodispersed nanoparticles of metal oxide including ferrites MFe2O4 (M=, Ni, Co, Mn) and γ-Fe2O3, Ta2O5 etc. have been synthesized using a water-toluene interface under both conventional and microwave hydrothermal conditions. This general synthesis procedure uses readily availab...

  16. Numerical formulation of composition segregation at curved solid-liquid interface during steady state solidification process

    NASA Technical Reports Server (NTRS)

    Wang, Jai-Ching

    1994-01-01

    The lateral solute segregation that results from a curved solid-liquid interface shape during steady state unidirectional solidification of a binary alloy system has been studied both analytically and numerically by Coriell, Bosivert, Rehm, and Sekerka. The system under their study is a two dimensional rectangular system. However, most real growth systems are cylindrical systems. Thus, in a previous study, we have followed Coriell etc. formalism and obtained analytical results for lateral solute segregation for an azimuthal symmetric cylindrical binary melt system during steady state solidification process. The solid-liquid interface shape is expressed as a series combination of Bessel functions. In this study a computer program has been developed to simulate the lateral solute segregation.

  17. Quantification of ordering at a solid-liquid interface using plasmon electron energy loss spectroscopy

    SciTech Connect

    Gandman, Maria; Kauffmann, Yaron; Kaplan, Wayne D.

    2015-02-02

    We present an in situ electron energy loss spectroscopy (EELS) study of ordering of liquid Al at various Al-Al{sub 2}O{sub 3} interfaces. This technique utilizes precise measurements of the shifts in bulk plasmon resonance and their sensitivity to the valence electron density. Plasmon EELS combined with high resolution transmission electron microscopy provides information regarding the chemical composition in liquid Al at Al-Al{sub 2}O{sub 3} interfaces. Preferential oxygen segregation to the (0006) Al{sub 2}O{sub 3} plane was verified, and the (101{sup ¯}2) Al{sub 2}O{sub 3} plane was found to contain the lowest amount of segregated species.

  18. Asymmetric gravity jitter excited slosh waves at a liquid-vapor-solid interface in microgravity

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Pan, H. L.; Leslie, F. W.

    1992-01-01

    The dynamical behavior of fluids affected by the asymmetric gravity jitter oscillations is investigated focusing on the surface tension effect on partially filled rotating fluids in a sub-scale gravity probe-B spacecraft propellant dewar tank. Data obtained revealed that the lower frequency gravity jitter imposed on the time-dependent variations of the background gravity direction induced a greater amplitude of oscillations and a stronger degree of asymmetry in liquid-vapor interface geometry than that caused by the higher frequency gravity jitter. It is also found that the greater the components of background gravity in radial and circumferential directions the greater the contribution to driving more toward increasing amplitude and degrees of asymmetry of the liquid-vapor interface profiles, which in turn modify the disturbance of moment of inertia and angular momentum of spacecraft.

  19. Adsorption and solvation of ethanol at the water liquid-vapor interface: a molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Wilson, M. A.; Pohorille, A.

    1997-01-01

    The free energy profiles of methanol and ethanol at the water liquid-vapor interface at 310K were calculated using molecular dynamics computer simulations. Both alcohols exhibit a pronounced free energy minimum at the interface and, therefore, have positive adsorption at this interface. The surface excess was computed from the Gibbs adsorption isotherm and was found to be in good agreement with experimental results. Neither compound exhibits a free energy barrier between the bulk and the surface adsorbed state. Scattering calculations of ethanol molecules from a gas phase thermal distribution indicate that the mass accommodation coefficient is 0.98, and the molecules become thermalized within 10 ps of striking the interface. It was determined that the formation of the solvation structure around the ethanol molecule at the interface is not the rate-determining step in its uptake into water droplets. The motion of an ethanol molecule in a water lamella was followed for 30 ns. The time evolution of the probability distribution of finding an ethanol molecule that was initially located at the interface is very well described by the diffusion equation on the free energy surface.

  20. A new interface for coupling solid phase microextraction with liquid chromatography.

    PubMed

    Chen, Yong; Sidisky, Leonard M

    2014-03-19

    A modified Rheodyne 7520 microsample injector was used as a new solid phase microextraction (SPME)-liquid chromatography (LC) interface. The modification was focused on the construction of a new sample rotor, which was built by gluing two sample rotors together. The new sample rotor was further reinforced with 3 pieces of stainless steel tubing. The enlarged central flow passage in the new sample rotor was used as a desorption chamber. SPME fiber desorption occurred in static mode. But all desorption solvent in the desorption chamber was injected into LC system with the interface. The analytical performance of the interface was evaluated by SPME-LC analysis of PAHs in water. At least 90% polycyclic aromatic hydrocarbons (PAHs) were desorbed from a polyacrylonitrile (PAN)/C18 bonded fuse silica fiber in 30s. And injection was completed in 20s. About 10-20% total carryovers were found on the fiber and in the interface. The carryover in the interface was eliminated by flushing the desorption chamber with acetonitrile at 1mL min(-1) for 2min. The repeatability of the method was from 2% to 8%. The limit of detection (LOD) was in the mid pg mL(-1) range. The linear ranges were from 0.1 to 100ng mL(-1). The new SPME-LC interface was reliable for coupling SPME with LC for both qualitative and quantitative analysis.

  1. Fully coupled simulation of the plasma liquid interface and interfacial coefficient effects

    NASA Astrophysics Data System (ADS)

    Lindsay, Alexander D.; Graves, David B.; Shannon, Steven C.

    2016-06-01

    There is a growing interest in the study of coupled plasma-liquid systems because of their applications to biomedicine, biological and chemical disinfection, agriculture, and other areas. Optimizing these applications requires a fundamental understanding of the coupling between phases. Though much progress has been made in this regard, there is still more to be done. One area that requires more research is the transport of electrons across the plasma-liquid interface. Some pioneering works (Rumbach et al 2015 Nat. Commun. 6, Rumbach et al 2015 J. Phys. D: Appl. Phys. 48 424001) have begun revealing the near-surface liquid characteristics of electrons. However, there has been little work to determine the near-surface gas phase electron characteristics. Without an understanding of the near-surface gas dynamics, modellers are left to make assumptions about the interfacial conditions. For instance it is commonly assumed that the surface loss or sticking coefficient of gas-phase electrons at the interface is equal to 1. In this work we explore the consequences of this assumption and introduce a couple of ways to think about the electron interfacial condition. In one set of simulations we impose a kinetic condition with varying surface loss coefficient on the gas phase interfacial electrons. In a second set of simulations we introduce a Henry’s law like condition at the interface in which the gas-phase electron concentration is assumed to be in thermodynamic equilibrium with the liquid-phase electron concentration. It is shown that for a range of electron Henry coefficients spanning a range of known hydrophilic specie Henry coefficients, the gas phase electron density in the anode can vary by orders of magnitude. Varying reflection of electrons by the interface also has consequences for the electron energy profile; increasing reflection may lead to increasing thermalization of electrons depending on choices about the electron energy boundary condition. This variation

  2. Video-microscopic observation of ionic liquid/alcohol interface and the corresponding molecular simulation study

    NASA Astrophysics Data System (ADS)

    Zhu, Peixi

    This research is aimed at studying the ionic liquid/n-pentanol interface via video-microscopy and molecular dynamic simulations. Understanding the interfacial phenomena and interfacial transport between ionic liquids and other liquids is of interest to the development and application of ionic liquids in a number of areas. One such area is the biphasic hydroformylation of alkenes to obtain alcohol and aldehyde, in which case ionic liquid is the reaction medium where a catalyst resides. The dissolution of an ionic liquid into an alcohol was studied by microscopically observing and measuring the shrinking of a micropipette-produced droplet in real time. Although microscopic investigation of droplet dissolution has been studied before, no attempt had been made to measure the diffusion coefficient D of the droplet species in the surrounding medium. A key finding of this work is that the Epstein-Plesset mathematical model, which describes the dissolution of a droplet/bubble in another fluid medium, can be used to measure D. Other experimental studies of the ionic liquid/alcohol system include electrical conductivity and UV-visible spectroscopy measurements of solutions of 1-hexyl-3-methylimidazolium tetrafluoroborate in n-pentanol. Those experiments were done in order to understand the molecular state of the particular ionic liquid in n-pentanol, as well as obtaining the dissociation constant K of such weak electrolyte solution. The experimental results provide an entry to the assessment of ionic liquid interaction with n-pentanol at molecular scale. Subsequently, molecular dynamics simulation was implemented for the investigation of such interaction. The computation started with simulation of the bulk phase of 1-butyl-3-methylimidazolium tetrafluoroborate, an affine ionic liquid on which molecular simulations had already been reported. A generalized probability based on Fuoss approximation for the closest ion to a distinguished countercharge ion was developed. In

  3. Emergent phenomena in far-from-equilibrium magnetic granular ensembles at a liquid-air interface.

    SciTech Connect

    Snezhko, A.; Aranson, I.; Belkin, M.; Materials Science Division

    2009-01-01

    Remarkable nontrivially ordered self-assembled structures are formed in ensembles of magnetic microparticles suspended at a liquid/air interface and energized by an alternating magnetic field. These dynamic structures emerge as a result of a competition between magnetic and hydrodynamic forces. Each structure (snake) is accompanied by a hydrodynamic vortex quadrupole. Under certain conditions snakes spontaneously break the symmetry of surface flows and turn into swimmers. Observed phenomena have been successfully described by a phenomenological model.

  4. Break-down of a planar liquid-solid interface during directional solidification - Influence of convection

    NASA Technical Reports Server (NTRS)

    Tewari, S. N.; Chopra, M. A.

    1992-01-01

    The influence of convection on the development of morphological instability at the liquid-solid interface during directional solidification in a positive thermal gradient has been examined in Pb-10 wt pct Sn and succinonitrile-1.9 wt pct acetone. The onset of interfacial breakdown occurs at higher growth speeds in the presence of convection. The linear stability analysis due to Favier and Rouzaud which uses the 'deformable' mass flow boundary layer concept shows a good agreement with the experimentally observed behavior.

  5. Binary Solvent Organization at Silica/Liquid Interfaces: Preferential Ordering in Acetonitrile-Methanol Mixtures.

    PubMed

    Gobrogge, Eric A; Walker, Robert A

    2014-08-07

    Nonlinear vibrational spectroscopy experiments examined solvent organization at the silica/binary solvent interface where the binary solvent consisted of methanol and acetonitrile in varying mole fractions. Data were compared with surface vibrational spectra acquired from silica surfaces exposed to a vapor phase saturated with the same binary solvent mixtures. Changes in vibrational band intensities suggest that methanol ideally adsorbs to the silica/vapor interface but acetonitrile accumulates in excess relative to vapor-phase composition. At the silica/liquid interface, acetonitrile's signal increases until a solution phase mole fraction of ∼0.85. At higher acetonitrile concentrations, acetonitrile's signal decreases dramatically until only a weak signature persists with the neat solvent. This behavior is ascribed to dipole-paired acetonitrile forming a bilayer with the first sublayer associating with surface silanol groups and a second sublayer consisting of weakly associating, antiparallel partners. On the basis of recent simulations, we propose that the second sublayer accumulates in excess.

  6. Numerical Calculation of the Morphology of a Solid/Liquid Interface Near an Insoluble Particle

    NASA Technical Reports Server (NTRS)

    Catalina, Adrian V.; Stefanescu, Doru M.; Sen, Subhayu

    2003-01-01

    A numerical mathematical model capable of accurately describing the evolution of the shape of the solid/liquid interface in the proximity of a foreign particle is presented in this paper. The model accounts for the influence of the temperature gradient and the Gibbs-Thomson and disjoining pressure effects. It shows that for the systems characterized by k(sub P) < k(sub L) the disjoining pressure causes the interface curvature to change its sign in the close-contact particle/interface region. It also shows that the increase of the temperature gradient diminishes the effect of the disjoining pressure. Calculated critical solidification velocities for the pushing/engulfment transition are compared with experimental measurements performed in microgravity conditions.

  7. On the Electronic Nature of the Surface Potential at the Vapor-Liquid Interface of Water

    SciTech Connect

    Kathmann, S M; Kuo, I; Mundy, C J

    2008-02-05

    The surface potential at the vapor-liquid interface of water is relevant to many areas of chemical physics. Measurement of the surface potential has been experimentally attempted many times, yet there has been little agreement as to its magnitude and sign (-1.1 to +0.5 mV). We present the first computation of the surface potential of water using ab initio molecular dynamics. We find that the surface potential {chi} = -18 mV with a maximum interfacial electric field = 8.9 x 10{sup 7} V/m. A comparison is made between our quantum mechanical results and those from previous molecular simulations. We find that explicit treatment of the electronic density makes a dramatic contribution to the electric properties of the vapor-liquid interface of water. The E-field can alter interfacial reactivity and transport while the surface potential can be used to determine the 'chemical' contribution to the real and electrochemical potentials for ionic transport through the vapor-liquid interface.

  8. UV-Vis reflection spectroscopy under variable angle incidence at the air-liquid interface.

    PubMed

    Roldán-Carmona, Cristina; Rubia-Payá, Carlos; Pérez-Morales, Marta; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2014-03-07

    The UV-Vis reflection spectroscopy (UV-Vis-RS) in situ at the air-liquid interface provides information about tilt and aggregation of chromophores in Langmuir monolayers. This information is particularly important given in most cases the chromophore is located at the polar region of the Langmuir monolayer. This region of the Langmuir monolayers has been hardly accessible by other experimental techniques. In spite of its enormous potential, the application of UV-Vis-RS has been limited mainly to reflection measurements under light normal incidence or at lower incidence angles than the Brewster angle. Remarkably, this technique is quite sensitive to the tilt of the chromophores at values of incidence angles close to or larger than the Brewster angle. Therefore, a novel method to obtain the order parameter of the chromophores at the air-liquid interface by using s- and p-polarized radiation at different incidence angles is proposed. This method allowed for the first time the experimental observation of the two components with different polarization properties of a single UV-Vis band at the air-liquid interface. The method of UV-Vis spectroscopy under variable angle incidence is presented as a new tool for obtaining rich detailed information on Langmuir monolayers.

  9. Reduced equations of motion of the interface of dielectric liquids in vertical electric and gravitational fields

    NASA Astrophysics Data System (ADS)

    Kochurin, Evgeny A.; Zubarev, Nikolay M.

    2012-07-01

    The dynamics of the interface between two dielectric fluids in the presence of vertical electric and gravitational fields is studied theoretically. It is shown that, in the particular case where the rate of change of the electric field is proportional to the effective gravitational acceleration, a special flow regime can be realized for which the velocity and electric potentials are linearly dependent functions. This means that there exists a frame of reference in which liquids move along the electric field lines. We derive and analyze the corresponding reduced equations of motion of a liquid-liquid interface. For small density ratio, they turn into the equations describing the Laplacian growth. In the case of two spatial dimensions, we show that these equations determine the asymptotic behavior of the system. For arbitrary density ratios, the Laplacian growth equations adequately describe the initial (weakly nonlinear) stage of the interface instability development. The integrability of these equations makes it possible to investigate the evolution of nonlinear waves at the boundary and, in particular, to demonstrate the tendency to the formation of singularities (cusps).

  10. Manifestations of non-planar adsorption geometries of lead pyrenocyanine at the liquid-solid interface.

    PubMed

    Mali, Kunal S; Zöphel, Lukas; Ivasenko, Oleksandr; Müllen, Klaus; De Feyter, Steven

    2013-10-01

    In this work, we provide evidence for multiple non-planar adsorption geometries of a novel pyrenocyanine derivative at the liquid-solid interface under ambient conditions. When adsorbed at the organic liquid-solid interface, lead pyrenocyanine forms well-ordered monolayers that exhibit peculiar non-periodic contrast variation. The different contrast of the adsorbed molecules is attributed to dissimilar adsorption geometries which arise from the non-planar conformation of the molecules. The non-planarity of the molecular backbone in turn arises due to a combination of the angularly extended pyrene subunits and the presence of the large lead ion, which is too big to fit inside the central cavity and thus is located out of the aromatic plane. The two possible locations of the lead atom, namely below and above the aromatic plane, could be identified as depression and protrusion in the central cavity, respectively. The manifestation of such multiple adsorption geometries on the structure of the resultant monolayer is discussed in detail. The packing density of these 2D arrays of molecules could be tuned by heating of the sample wherein the molecular packing changes from a low-density, pseudo six-fold symmetric to a high-density, two-fold symmetric arrangement. Finally, a well-ordered two-component system could be constructed by incorporating C60 molecules in the adlayer of lead pyrenocyanine at the liquid-solid interface.

  11. Combined Gravity Gradient and Jitter Accelerations Acting on Liquid-Vapor Interface Oscillations in Reduced Gravity

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Pan, H. L.

    1995-01-01

    The dynamical behavior of fluids affected by the asymmetric combined gravity gradient and jitter accelerations, in particular the effect of surface tension on partially-filled rotating fluids applicable to a full-scale Gravity Probe-B Spacecraft dewar tank, have been investigated. Three different cases of accelerations, one gravity gradient-dominated, one equally weighted between gravity gradient and jitter, and the others gravity jitter-dominated are studied. Results of slosh wave excitation along the liquid-vapor interface induced by gravity gradient-dominated acceleration indicate that the gravity gradient-dominated acceleration is equivalent to the combined effect of a twisting force and torsional moment acting on the spacecraft. Results of the slosh wave excitation along the liquid vapor interface induced by gravity jitter-dominated acceleration indicate that the gravity jitter-dominated acceleration is equivalent to time-dependent oscillatory forces which push the bubble in the combined directions of down-and-up and sideward -and-middleward as the bubble is rotating with respect to rotating dewar axis. This study discloses the slosh wave excitation along the liquid-vapor interface driven by the combined effects of gravity gradient and jitter accelerations which are two major driving forces affecting the stability of the fluid system in microgravity.

  12. Density-functional theory of the water liquid-vapour interface

    NASA Astrophysics Data System (ADS)

    Yang, B.; Sullivan, D. E.; Tjipto-Margo, B.; Gray, C. G.

    An extended mean-field density-functional theory of the liquid-vapour interface of water is described. The theory generalizes standard mean-field theories of inhomogeneous molecular fluids by including quadratic orders of the anisotropic component of the intermolecular pair potential in the free energy functional. The pair interaction is modelled by an isotropic plus point dipolar and quadrupolar potential. Analysis shows that dipole-quadrupole coupling terms in the potential are responsible for inducing spontaneous polarization at the liquid-vapour interface. The direction of the surface polarization is determined by the sign of the axial component of the molecular quadrupole tensor, as in the earlier phenomenological theory of Stillinger and Ben-Naim. Explicit calculations are performed using molecular interaction parameters given by the TIP4P potential model for water, employed in recent computer simulations of the water interface by Wilson, Pohorille and Pratt. The preferred molecular orientations at the interface predicted by the theory are analysed in detail and compared with previous simulation results.

  13. Real Time Characterization of Solid/Liquid Interfaces During Directional Solidification

    NASA Technical Reports Server (NTRS)

    Sen, S.; Kaukler, W. K.; Curreri, P. A.; Peters, P.

    1997-01-01

    A X-Ray Transmission Microscope (XTM) has been developed to observe in real time and in-situ solidification phenomenon at the solid/liquid interface. Recent improvements in the horizontal Bridgman furnace design provides real-time magnification (during solidification) up to 12OX. The increased magnification has enabled for the first time the XTM imaging of real-time growth of fibers and particles with diameters of 3-6 micrometers. Further, morphological transitions from planar to cellular interfaces have also been imaged. Results from recent XTM studies on Al-Bi monotectic system, Al-Au eutectic system and interaction of insoluble particles with s/I interfaces in composite materials will be presented. An important parameter during directional solidification of molten metal is the interfacial undercooling. This parameter controls the morphology and composition at the s/I interface. Conventional probes such as thermocouples, due to their large bead size, do not have sufficient resolution for measuring undercooling at the s/I interface. Further, the intrusive nature of the thermocouples also distorts the thermal field at the s/I interface. To overcome these inherent problems we have recently developed a compact furnace which utilizes a non-intrusive technique (Seebeck) to measure undercooling at the S/I interface. Recent interfacial undercooling measurements obtained for the Pb-Sn system will be presented. The Seebeck measurement furnace in the future will be integrated with the XTM to provide the most comprehensive tool for real time characterization of s/I interfaces during solidification.

  14. Correlated Diffusion of Colloidal Particles near a Liquid-Liquid Interface

    PubMed Central

    Zhang, Wei; Chen, Song; Li, Na; Zhang, Jia zheng; Chen, Wei

    2014-01-01

    Optical microscopy and multi-particle tracking are used to investigate the cross-correlated diffusion of quasi two-dimensional colloidal particles near an oil-water interface. The behaviors of the correlated diffusion along longitudinal and transverse direction are asymmetric. It is shown that the characteristic length for longitudinal and transverse correlated diffusion are particle diameter and the distance from particle center to the interface, respectively, for large particle separation . The longitudinal and transverse correlated diffusion coefficient and are independent of the colloidal area fraction when , which indicates that the hydrodynamic interactions(HIs) among the particles are dominated by HIs through the surrounding fluid for small . For high area fraction , the power law exponent for the spatial decay of begins to decrease, which suggests the HIs are more contributed from the 2D particle monolayer self for large . PMID:24465498

  15. Interaction of magnetic nanoparticles with phospholipid films adsorbed at a liquid/liquid interface.

    PubMed

    Cámara, C I; Monzón, L M A; Coey, J M D; Yudi, L M

    2015-01-07

    The interaction of Co hexagonal magnetic nanoparticles (MNPs) with distearoyl phosphatidyl glycerol (DSPG) and distearoyl phosphatidic acid (DSPA) films adsorbed at a water/1,2-dichloroethane interface is studied employing cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), capacity curves and interfacial pressure-area isotherms. DSPA and DSPG adsorb at the interface forming homogenous films and producing a blocking effect on the transfer process of tetraethyl ammonium (TEA(+)), used as a probe cation. In the presence of Co NPs this effect is reversed and the reversible transfer process for TEA(+) is reestablished, to a greater or lesser extent depending on the structuration of the film. Co-DSPA hybrid films have a homogeneous structure while Co-DSPG films present different domains. Moreover, the presence of Co on DSPA film modifies the partition coefficient of the organic electrolyte into the hydrocarbon layer.

  16. Two-Phase Model of Liquid-Liquid Interactions With Interface Capturing: Application to Water Assisted Injection Molding

    NASA Astrophysics Data System (ADS)

    Silva, Luisa; Lanrivain, Rodolphe; Zerguine, Walid; Rodriguez-Villa, Andrès; Coupez, Thierry

    2007-05-01

    In this paper, a two phase model to compute liquid-liquid flows is presented. We consider that one phase is a highly viscous thermodependent liquid (polymer phase), whereas the second one is a low viscosity low temperature fluid (water). The first part of this paper concerns capture of the interface between the water and the polymer (or determination of the phase field function). Classical VOF and Level set techniques have been implemented and were ameliorated using mesh adaptation techniques. To accurately determine the velocity field, a two-phase formulation is considered, based in the theory of mixtures, and we introduce a scalar parameter, the phase fraction quantifying the presence of each phase in each point of the computational domain. A friction type coupling between both phases is retained. Using the mixed finite element method within an eulerian framework, we calculate in a single system the whole kinematic variables for both liquids (velocity and pressure of each phase). Results are shown, for 2D and 3D parts.

  17. Observation of Charge Inversion of an Ionic Liquid at the Solid Salt-Liquid Interface by Sum Frequency Generation Spectroscopy.

    PubMed

    Peñalber, Chariz Y; Baldelli, Steven

    2012-04-05

    Sum frequency generation (SFG) vibrational spectroscopy of the ionic liquid, 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA], in contact with two different solid salt surfaces, BaF2(111) single crystal and solid NaCl{100}, are discussed in this Letter. This investigation describes the nature of an ionic liquid-(solid) salt interface using SFG, contributing a new understanding to the molecular-level interactions involved in salts, which are conceptually similar compounds (of purely ionic character) but of different physical properties (liquid versus solid at room temperature). Results show the presence of [BMIM](+) at the NaCl{100} surface and [DCA](-) at the BaF2(111) surface. [BMIM](+) cations adhere closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [DCA](-) anions subsequently have a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorb to the solid salt surface to form a Helmholtz-like electric double layer.

  18. A polarized liquid-liquid interface meets visible light-driven catalytic water oxidation.

    PubMed

    Rastgar, Shokoufeh; Pilarski, Martin; Wittstock, Gunther

    2016-09-15

    Hyperbranched nanostructured bismuth vanadate at a chemically polarized water/organic interface is applied for efficient visible light-driven catalytic oxidation of water in the presence of [Co(bpy)3](PF6)3 as an organic soluble electron acceptor. The photocurrent response originating from the transfer of photo-excited electrons in BiVO4 to [Co(bpy)3](3+) is measured by scanning electrochemical microscopy.

  19. UV-Vis Reflection-Absorption Spectroscopy at air-liquid interfaces.

    PubMed

    Rubia-Payá, Carlos; de Miguel, Gustavo; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-11-01

    UV-Visible Reflection-Absorption Spectroscopy (UVRAS) technique is reviewed with a general perspective on fundamental and applications. UVRAS is formally identical to IR Reflection-Absorption Spectroscopy (IRRAS), and therefore, the methodology developed for this IR technique can be applied in the UV-visible region. UVRAS can be applied to air-solid, air-liquid or liquid-liquid interfaces. This review focuses on the use of UVRAS for studying Langmuir monolayers. We introduce the theoretical framework for a successful understanding of the UVRAS data, and we illustrate the usage of this data treatment to a previous study from our group comprising an amphiphilic porphyrin. For ultrathin films with a thickness of few nm, UVRAS produces positive or negative bands when p-polarized radiation is used, depending on the incidence angle and the orientation of dipole absorption. UVRAS technique provides highly valuable information on tilt of chromophores at the air-liquid interface, and moreover allows the determination of optical parameters. We propose UVRAS as a powerful technique to investigate the in situ optical properties of Langmuir monolayers.

  20. Diffusivity and hydrodynamic drag of nanoparticles at a vapor-liquid interface

    NASA Astrophysics Data System (ADS)

    Koplik, Joel; Maldarelli, Charles

    2017-02-01

    Measurements of the surface diffusivity of colloidal spheres translating along a vapor-liquid interface show an unexpected decrease in diffusivity, or increase in surface drag (from the Stokes-Einstein relation), when the particles situate further into the vapor phase. However, direct measurements of the surface drag from the colloid velocity due to an external force find the expected decrease with deeper immersion into the vapor. We perform molecular dynamics simulations of the diffusivity and force experiments for a nanoparticle with a small surface roughness at a vapor-liquid interface to examine the effect of contact line fluctuations. The drag calculated from both calculations agree and decrease as the particle positions further into the vapor. The surface drag is smaller than the bulk liquid drag due to the partial submersion into the liquid and the finite thickness of the interfacial zone relative to the nanoparticle size. We observe weak contact line fluctuations and transient pinning events, but these do not give rise to an anomalous increase in drag in this system.

  1. An Interface for the Direct Coupling of Small Liquid Samples to AMS.

    PubMed

    Ognibene, T J; Thomas, A T; Daley, P F; Bench, G; Turteltaub, K W

    2015-10-15

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL's Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography. Discrete samples containing at least a few 10s of nanograms of carbon and as little as 50 zmol (14)C can be measured with a 3-5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targets for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of (14)C. Liquid Sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.

  2. Self-aligning subatmospheric hybrid liquid junction electrospray interface for capillary electrophoresis.

    PubMed

    Krenkova, Jana; Kleparnik, Karel; Grym, Jakub; Luksch, Jaroslav; Foret, Frantisek

    2016-02-01

    We report a construction of a self-aligning subatmospheric hybrid liquid junction electrospray interface for CE eliminating the need for manual adjustment by guiding the capillaries in a microfabricated liquid junction glass chip at a defined angle. Both the ESI and separation capillaries are inserted into the microfabricated part until their ends touch. The distance between the capillary openings is defined by the angle between the capillaries. The microfabricated part contains channels for placement of the capillaries and connection of the external electrode reservoirs. It was fabricated using standard photolithographic/wet chemical etching techniques followed by thermal bonding. The liquid junction is connected to a subatmospheric electrospray chamber inducing the flow inside the ESI needle and helping the ion transport via aerodynamic focusing.

  3. Designing icephobic surfaces by passively sustaining liquid film at ice-substrate interface

    NASA Astrophysics Data System (ADS)

    Zhao, Tom; Jones, Paul; Patankar, Neelesh

    2016-11-01

    Ice formation poses a significant barrier to transportation, energy generation and transport, gas extraction, etc. We propose to design icephobic surfaces that reduce ice formation and lower ice adhesion by sustaining a film of liquid water at the interface between bulk ice and the substrate. The liquid layer is in phase equilibrium with the surrounding bulk ice, and thus exists without constant energy input. Using molecular dynamic simulations, we show this liquid film can be maintained indefinitely by exploiting the phenomena of interfacial premelting and the freezing point depression of ice confined in surface texture due to the Gibbs Thomson effect. We demonstrate the reduction of both the work and strength of ice adhesion as a function of surface wettability and geometric parameters of the surface texture.

  4. Preliminary drop-tower experiments on liquid-interface geometry in partially filled containers at zero gravity

    NASA Technical Reports Server (NTRS)

    Smedley, G.

    1990-01-01

    Plexiglass containers with rounded trapezoidal cross sections were designed and built to test the validity of Concus and Finn's existence theorem (1974, 1983) for a bounded free liquid surface at zero gravity. Experiments were carried out at the NASA Lewis two-second drop tower. Dyed ethanol-water solutions and three immiscible liquid pairs, with one liquid dyed, were tested. High-speed movies were used to record the liquid motion. Liquid rose to the top of the smaller end of the containers when the contact angle was small enough, in agreement with the theory. Liquid interface motion demonstrated a strong dependence on physical properties, including surface roughness and contamination.

  5. Shape-Selectivity with Liquid Crystal and Side-Chain Liquid Crystalline Polymer SAW Sensor Interfaces

    SciTech Connect

    FRYE-MASON,GREGORY CHARLES; OBORNY,MICHAEL C.; PUGH,COLEEN; RICCO,ANTONIO; THOMAS,ROSS C.; ZELLERS,EDWARD T.; ZHANG,GUO-ZHENG

    1999-09-23

    A liquid crystal (LC) and a side-chain liquid crystalline polymer (SCLCP) were tested as surface acoustic wave (SAW) vapor sensor coatings for discriminating between pairs of isomeric organic vapors. Both exhibit room temperature smectic mesophases. Temperature, electric-field, and pretreatment with self-assembled monolayers comprising either a methyl-terminated or carboxylic acid-terminated alkane thiol anchored to a gold layer in the delay path of the sensor were explored as means of affecting the alignment and selectivity of the LC and SCLCP films. Results for the LC were mixed, while those for the SCLCP showed a consistent preference for the more rod-like isomer of each isomer pair examined.

  6. Viscoelasticity measurement of gel formed at the liquid-liquid reactive interfaces

    NASA Astrophysics Data System (ADS)

    Ujiie, Tomohiro

    2012-11-01

    We have experimentally studied a reacting liquid flow with gel formation by using viscous fingering (VF) as a flow field. Here, two systems were employed. In one system, sodium polyacrylate (SPA) solution and ferric ion solution were used as the more and less viscous liquids, respectively. In another system, xthantan gum (XG) solution and the ferric ion solution were used as the more and less viscous liquids, respectively. We showed that influence of gel formation on VF were qualitatively different in these two systems. We consider that the difference in the two systems will be caused by the difference in the properties of the gels. Therefore, we have measured the rheological properties of the gels by means of a rheometer. In the present study, viscoelasticity measurement was performed by two methods. One is the method which uses Double Wall Ring sensor (TA instrument) and another is the method using parallel plate. In both viscoelasticity measurements, the behavior of the formed gel was qualitatively consistent. We have found that the gel in the SPA system shows viscoelastic fluid like behavior. Moreover, we have found that the gel in the XG system shows solid like behavior.

  7. Influence of Simple Electrolytes on the Orientational Ordering of Thermotropic Liquid Crystals at Aqueous Interfaces

    PubMed Central

    Carlton, Rebecca J.; Gupta, Jugal K.; Swift, Candice L.; Abbott, Nicholas L.

    2011-01-01

    We report orientational anchoring transitions at aqueous interfaces of a water-immiscible, thermotropic liquid crystal (LC; nematic phase of 4′-pentyl-4-cyanobiphenyl) that are induced by changes in pH of the aqueous solution and the addition of simple electrolytes (NaCl) to the aqueous phase. Whereas measurements of the zeta potential on the aqueous side of the interface of LC-in-water emulsions prepared with 5CB confirm pH-dependent formation of an electrical double layer extending into the aqueous phase, quantification of the orientational ordering of the LC leads to the proposition that an electrical double layer is also formed on the LC-side of the interface with an internal electric field that drives the LC anchoring transition. Further support for this conclusion is obtained from measurements of the dependence of LC ordering on pH and ionic strength, as well as a simple model based on the Poisson-Boltzmann equation from which we calculate the contribution of an electrical double layer to the orientational anchoring energy of the LC. Overall, the results presented herein provide new fundamental insights into ionic phenomena at LC-aqueous interfaces, and expand the range of solutes known to cause orientational anchoring transitions at LC-aqueous interfaces beyond previously examined amphiphilic adsorbates. PMID:22106820

  8. Systematic Approach to Electrostatically Induced 2D Crystallization of Nanoparticles at Liquid Interfaces

    SciTech Connect

    Fukuto, M.; Kewalramani, S.; Wang, S.; Lin, Y.; Nguyen, G.; Wang, Q.; Yang, L.

    2011-02-07

    We report an experimental demonstration of a strategy for inducing two-dimensional (2D) crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situ X-ray scattering measurements at the liquid-vapor interface. The assembly was studied as a function of the solution pH, which was used to vary the charge on CPMV, and of the mole fraction of the cationic lipid in the binary lipid monolayer, which set the interface charge density. The 2D crystallization of CPMV occurred in a narrow pH range just above the particle's isoelectric point, where the particle charge was weakly negative, and only when the cationic-lipid fraction in the monolayer exceeded a threshold. The observed 2D crystals exhibited nearly the same packing density as the densest lattice plane within the known 3D crystals of CPMV. The above electrostatic approach of maximizing interfacial adsorption may provide an efficient route to the crystallization of nanoparticles at aqueous interfaces.

  9. A model of blind zone for in situ monitoring the solid/liquid interface using ultrasonic wave.

    PubMed

    Peng, Song; Ouyang, Qi; Zhu, Z Z; Zhang, X L

    2015-07-01

    To in situ monitor a solid/liquid interface to control metal qualities, the paper analysis blind models of the ultrasonic propagation in the solidifying molten metal with a solid/liquid interface in the Bridgman type furnace, and a mathematical calculation model of blind zone with different source locations and surface concavities is built. The study points out that the blind zone I is caused by ray bending in the interface edge, and the blind zone II is caused by totally reflection which is related with initial ray angle, critical refraction angle of solid/liquid media. A serial of simulation experiments are operated on the base of the model, and numerical computation results coincide with model calculated results very well. Therefore, receiver should locate beyond these blind zones in the right boundary to obtain time of flight data which is used to reconstruct the solid/liquid interface.

  10. Self-assembly of microscopic chiplets at a liquid-liquid-solid interface forming a flexible segmented monocrystalline solar cell.

    PubMed

    Knuesel, Robert J; Jacobs, Heiko O

    2010-01-19

    This paper introduces a method for self-assembling and electrically connecting small (20-60 micrometer) semiconductor chiplets at predetermined locations on flexible substrates with high speed (62500 chips/45 s), accuracy (0.9 micrometer, 0.14 degrees), and yield (> 98%). The process takes place at the triple interface between silicone oil, water, and a penetrating solder-patterned substrate. The assembly is driven by a stepwise reduction of interfacial free energy where chips are first collected and preoriented at an oil-water interface before they assemble on a solder-patterned substrate that is pulled through the interface. Patterned transfer occurs in a progressing linear front as the liquid layers recede. The process eliminates the dependency on gravity and sedimentation of prior methods, thereby extending the minimal chip size to the sub-100 micrometer scale. It provides a new route for the field of printable electronics to enable the integration of microscopic high performance inorganic semiconductors on foreign substrates with the freedom to choose target location, pitch, and integration density. As an example we demonstrate a fault-tolerant segmented flexible monocrystalline silicon solar cell, reducing the amount of Si that is used when compared to conventional rigid cells.

  11. Stability analysis of the interface between two weak viscoelastic liquids under periodic oscillations

    NASA Astrophysics Data System (ADS)

    Garcia-Gonzalez, Sergio; Fernandez-Feria, Ramon

    2017-01-01

    We consider the motion and the linear hydrodynamic instabilities of two immiscible viscoelastic liquids above a horizontal solid surface induced by the periodic oscillations of the horizontal plate along its plane. A planar interface, parallel to the oscillating plate, separates the lower layer from the other viscoelastic fluid that extends vertically to infinity. The two-dimensional motion of these fluids is studied together with the conditions under which the flow becomes unstable, deforming the planar interface and promoting the mixing of both liquids. The study extends the previous work by Isakova et al. ["A model for the linear stability of the interface between aqueous humor and vitreous substitutes after vitreoretinal surgery," Phys. Fluids 26, 124101 (2014)] by considering non-Newtonian fluids, particularly liquids with weak viscoelasticity (neglecting normal stress differences), which may model more accurately the physical behavior of the aqueous humor and, especially, the vitreous humour substitute in the vitreous chamber of the eye after vitrectomy. A novel approach to the quasi-steady stability analysis of unsteady flows of Maxwell liquids is developed in the present paper. We focus on the effect of the small Deborah numbers on the motion and on the hydrodynamic instability of the two fluids as the other non-dimensional parameters are varied within the range of interest for the biofluiddynamics of the eye. The special case in which the lower layer modelling the aqueous humor is a Newtonian liquid and the upper vitreous substitute is a Maxwell liquid is considered with detail. We find that, even for a very small Deborah number of the vitreous substitute, the dynamics and the hydrodynamic stability of the two fluids can be qualitatively very different to the Newtonian case, especially as the viscosity ratio is varied, showing that weak viscoelasticity may change dramatically the dynamics of the eye. An exhaustive characterization of the influence of the

  12. Structural ordering at solid-liquid interfaces in Al-Sm system: A molecular-dynamics study

    DOE PAGES

    Sun, Yang; Zhang, Feng; Ye, Zhuo; ...

    2016-07-12

    The structural ordering at solid-liquid interfaces far from equilibrium is studied with molecular dynamics simulations for the Al-Sm system. Using the van-Hove self-correlation function as the criterion to identify attachment/detachment events that occur at the interface, we are able to determine the time-dependent interface position, and characterize the detailed interfacial structure ordering surrounding the attached atoms. For the interface between an undercooled Al90Sm10 liquid and a metastable cubic structure, the solid induces the crystalline order of the cubic phase in the liquid layers, promoting the continuous growth of the crystal phase. When the same liquid is put in contact withmore » f.c.c. Al, Sm from the liquid can still attach to the solid interface despite its insolubility in the Al lattice. Non-f.c.c. order is revealed surrounding the attached Sm atoms. Lastly, we show that the local structure ordering at interface is highly correlated to solid packing and liquid ordering.« less

  13. Structural ordering at solid-liquid interfaces in Al-Sm system: A molecular-dynamics study

    SciTech Connect

    Sun, Yang; Zhang, Feng; Ye, Zhuo; Ding, Zejun; Mendelev, Mikhail I.; Kramer, Matthew J.; Wang, Cai -Zhuang; Ho, Kai -Ming

    2016-07-12

    The structural ordering at solid-liquid interfaces far from equilibrium is studied with molecular dynamics simulations for the Al-Sm system. Using the van-Hove self-correlation function as the criterion to identify attachment/detachment events that occur at the interface, we are able to determine the time-dependent interface position, and characterize the detailed interfacial structure ordering surrounding the attached atoms. For the interface between an undercooled Al90Sm10 liquid and a metastable cubic structure, the solid induces the crystalline order of the cubic phase in the liquid layers, promoting the continuous growth of the crystal phase. When the same liquid is put in contact with f.c.c. Al, Sm from the liquid can still attach to the solid interface despite its insolubility in the Al lattice. Non-f.c.c. order is revealed surrounding the attached Sm atoms. Lastly, we show that the local structure ordering at interface is highly correlated to solid packing and liquid ordering.

  14. Surface thermodynamics of planar, cylindrical, and spherical vapour-liquid interfaces of water.

    PubMed

    Lau, Gabriel V; Ford, Ian J; Hunt, Patricia A; Müller, Erich A; Jackson, George

    2015-03-21

    The test-area (TA) perturbation approach has been gaining popularity as a methodology for the direct computation of the interfacial tension in molecular simulation. Though originally implemented for planar interfaces, the TA approach has also been used to analyze the interfacial properties of curved liquid interfaces. Here, we provide an interpretation of the TA method taking the view that it corresponds to the change in free energy under a transformation of the spatial metric for an affine distortion. By expressing the change in configurational energy of a molecular configuration as a Taylor expansion in the distortion parameter, compact relations are derived for the interfacial tension and its energetic and entropic components for three different geometries: planar, cylindrical, and spherical fluid interfaces. While the tensions of the planar and cylindrical geometries are characterized by first-order changes in the energy, that of the spherical interface depends on second-order contributions. We show that a greater statistical uncertainty is to be expected when calculating the thermodynamic properties of a spherical interface than for the planar and cylindrical cases, and the evaluation of the separate entropic and energetic contributions poses a greater computational challenge than the tension itself. The methodology is employed to determine the vapour-liquid interfacial tension of TIP4P/2005 water at 293 K by molecular dynamics simulation for planar, cylindrical, and spherical geometries. A weak peak in the curvature dependence of the tension is observed in the case of cylindrical threads of condensed liquid at a radius of about 8 Å, below which the tension is found to decrease again. In the case of spherical drops, a marked decrease in the tension from the planar limit is found for radii below ∼ 15 Å; there is no indication of a maximum in the tension with increasing curvature. The vapour-liquid interfacial tension tends towards the planar limit for large

  15. A Molecular Dynamics Study on the Local Structure of Liquid-Vapor Interface of Water and L-J Fluid

    NASA Astrophysics Data System (ADS)

    Kikugawa, Gota; Takagi, Shu; Matsumoto, Yoichiro; Ohara, Taku

    Microscopic structures of a liquid-vapor interface are investigated by molecular dynamics simulations. In the previous studies, we proposed the local and instantaneous definition of the interface at the molecular level, which can capture the thermal fluctuation of the interface. By using this definition, the layering structure of water molecules at the interface was found, in other words, the structurization phenomena of water at the molecular level were clearly seen as usually found at the liquid-solid interface. In this study, we investigated the liquid-vapor interface of Lenard-Jones fluid. The effect of well depth of L-J potential parameter on the structure was also studied. Although the structurization was found at the L-J fluid as well as water, characteristic of this structure was clearly different from that of water. We consider that the difference is ascribed to the intrinsic structure of liquid and associative trend of molecules. We also discussed the anisotropic characteristics of the molecular diffusion at the interface. The anisotropy of the translational diffusion at the interface of water is stronger than that of the L-J fluid.

  16. Topological defects in electric double layers of ionic liquids at carbon interfaces

    DOE PAGES

    Black, Jennifer M.; Okatan, Mahmut Baris; Feng, Guang; ...

    2015-06-07

    The structure and properties of the electrical double layer in ionic liquids is of interest in a wide range of areas including energy storage, catalysis, lubrication, and many more. Theories describing the electrical double layer for ionic liquids have been proposed, however a full molecular level description of the double layer is lacking. To date, studies have been predominantly focused on ion distributions normal to the surface, however the 3D nature of the electrical double layer in ionic liquids requires a full picture of the double layer structure not only normal to the surface, but also in plane. Here wemore » utilize 3D force mapping to probe the in plane structure of an ionic liquid at a graphite interface and report the direct observation of the structure and properties of topological defects. The observation of ion layering at structural defects such as step-edges, reinforced by molecular dynamics simulations, defines the spatial resolution of the method. Observation of defects allows for the establishment of the universality of ionic liquid behavior vs. separation from the carbon surface and to map internal defect structure. In conclusion, these studies offer a universal pathway for probing the internal structure of topological defects in soft condensed matter on the nanometer level in three dimensions.« less

  17. Topological defects in electric double layers of ionic liquids at carbon interfaces

    SciTech Connect

    Black, Jennifer M.; Okatan, Mahmut Baris; Feng, Guang; Cummings, Peter T.; Kalinin, Sergei V.; Balke, Nina

    2015-06-07

    The structure and properties of the electrical double layer in ionic liquids is of interest in a wide range of areas including energy storage, catalysis, lubrication, and many more. Theories describing the electrical double layer for ionic liquids have been proposed, however a full molecular level description of the double layer is lacking. To date, studies have been predominantly focused on ion distributions normal to the surface, however the 3D nature of the electrical double layer in ionic liquids requires a full picture of the double layer structure not only normal to the surface, but also in plane. Here we utilize 3D force mapping to probe the in plane structure of an ionic liquid at a graphite interface and report the direct observation of the structure and properties of topological defects. The observation of ion layering at structural defects such as step-edges, reinforced by molecular dynamics simulations, defines the spatial resolution of the method. Observation of defects allows for the establishment of the universality of ionic liquid behavior vs. separation from the carbon surface and to map internal defect structure. In conclusion, these studies offer a universal pathway for probing the internal structure of topological defects in soft condensed matter on the nanometer level in three dimensions.

  18. Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

    NASA Astrophysics Data System (ADS)

    Falk von Rudorff, Guido; Jakobsen, Rasmus; Rosso, Kevin M.; Blumberger, Jochen

    2016-10-01

    The atom-scale characterisation of interfaces between transition metal oxides and liquid water is fundamental to our mechanistic understanding of diverse phenomena ranging from crystal growth to biogeochemical transformations to solar fuel production. Here we report on the results of large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface. A specific focus is placed on understanding how different terminations of the same surface influence surface solvation. We find that the two dominant terminations for the hematite(001) surface exhibit strong differences both in terms of the active species formed on the surface and the strength of surface solvation. According to present simulations, we find that charged oxyanions (-O-) and doubly protonated oxygens (-OH2+ ) can be formed on the iron terminated layer via autoionization of neutral -OH groups. No such charged species are found for the oxygen terminated surface. In addition, the missing iron sublayer in the iron terminated surface strongly influences the solvation structure, which becomes less well ordered in the vicinity of the interface. These pronounced differences are likely to affect the reactivity of the two surface terminations, and in particular the energetics of excess charge carriers at the surface.

  19. Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

    SciTech Connect

    von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M.; Blumberger, Jochen

    2016-07-28

    The atom-scale characterisation of interfaces between transition metal oxides and liquid water is fundamental to our mechanistic understanding of diverse phenomena ranging from crystal growth to biogeochemical transformations to solar fuel production. Here we report on the results of large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface. A specific focus is placed on understanding how different terminations of the same surface influence surface solvation. We find that the two dominant terminations for the hematite(001) surface exhibit strong differences both in terms of the active species formed on the surface and the strength of surface solvation. According to present simulations, we find that charged oxyanions (-O-) and doubly protonated oxygens (-OH$_{2}^{+}$ ) can be formed on the iron terminated layer via autoionization of neutral -OH groups. No such charged species are found for the oxygen terminated surface. In addition, the missing iron sublayer in the iron terminated surface strongly influences the solvation structure, which becomes less well ordered in the vicinity of the interface. These pronounced differences are likely to affect the reactivity of the two surface terminations, and in particular the energetics of excess charge carriers at the surface.

  20. Solid mesostructured polymer-surfactant films at the air-liquid interface.

    PubMed

    Pegg, Jonathan C; Eastoe, Julian

    2015-08-01

    Pioneering work by Edler et al. has spawned a new sub-set of mesostructured materials. These are solid, self-supporting films comprising surfactant micelles encased within polymer hydrogel; composite polymer-surfactant films can be grown spontaneously at the air-liquid interface and have defined and controllable mesostructures. Addition of siliconalkoxide to polymer-surfactant mixtures allows for the growth of mesostructured hybrid polymer-surfactant silica films that retain film geometry after calcinations and exhibit superior mechanical properties to typically brittle inorganic films. Growing films at the air-liquid interface provides a rapid and simple means to prepare ordered solid inorganic films, and to date the only method for generating mesostructured films thick enough (up to several hundred microns) to be removed from the interface. Applications of these films could range from catalysis to encapsulation of hydrophobic species and drug delivery. Film properties and mesostructures are sensitive to surfactant structure, polymer properties and polymer-surfactant phase behaviour: herein it will be shown how film mesostructure can be tailored by directing these parameters, and some interesting analogies will be drawn with more familiar mesostructured silica materials.

  1. A novel method for pulmonary research: assessment of bioenergetic function at the air-liquid interface.

    PubMed

    Xu, Weiling; Janocha, Allison J; Leahy, Rachel A; Klatte, Ryan; Dudzinski, Dave; Mavrakis, Lori A; Comhair, Suzy A A; Lauer, Mark E; Cotton, Calvin U; Erzurum, Serpil C

    2014-01-01

    Air-liquid interface cell culture is an organotypic model for study of differentiated functional airway epithelium in vitro. Dysregulation of cellular energy metabolism and mitochondrial function have been suggested to contribute to airway diseases. However, there is currently no established method to determine oxygen consumption and glycolysis in airway epithelium in air-liquid interface. In order to study metabolism in differentiated airway epithelial cells, we engineered an insert for the Seahorse XF24 Analyzer that enabled the measure of respiration by oxygen consumption rate (OCR) and glycolysis by extracellular acidification rate (ECAR). Oxidative metabolism and glycolysis in airway epithelial cells cultured on the inserts were successfully measured. The inserts did not affect the measures of OCR or ECAR. Cells under media with apical and basolateral feeding had less oxidative metabolism as compared to cells on the inserts at air-interface with basolateral feeding. The design of inserts that can be used in the measure of bioenergetics in small numbers of cells in an organotypic state may be useful for evaluation of new drugs and metabolic mechanisms that underlie airway diseases.

  2. A fully automated liquid–liquid extraction system utilizing interface detection

    PubMed Central

    Maslana, Eugene; Schmitt, Robert; Pan, Jeffrey

    2000-01-01

    The development of the Abbott Liquid-Liquid Extraction Station was a result of the need for an automated system to perform aqueous extraction on large sets of newly synthesized organic compounds used for drug discovery. The system utilizes a cylindrical laboratory robot to shuttle sample vials between two loading racks, two identical extraction stations, and a centrifuge. Extraction is performed by detecting the phase interface (by difference in refractive index) of the moving column of fluid drawn from the bottom of each vial containing a biphasic mixture. The integration of interface detection with fluid extraction maximizes sample throughput. Abbott-developed electronics process the detector signals. Sample mixing is performed by high-speed solvent injection. Centrifuging of the samples reduces interface emulsions. Operating software permits the user to program wash protocols with any one of six solvents per wash cycle with as many cycle repeats as necessary. Station capacity is eighty, 15 ml vials. This system has proven successful with a broad spectrum of both ethyl acetate and methylene chloride based chemistries. The development and characterization of this automated extraction system will be presented. PMID:18924693

  3. Nanocrystalline Janus films of inorganic materials prepared at the liquid-liquid interface.

    PubMed

    Biswas, Kanishka; Rao, C N R

    2009-05-01

    The interface between toluene and water has been employed to prepare ultrathin Janus nanocrystalline films of metal oxides, metal chalcogenides and gold, wherein the surface on the organic-side is hydrophobic and the aqueous-side is hydrophilic. We have changed the nature of the metal precursor or capping agent in the organic layer to increase the hydrophobicity. The strategy employed for this purpose is to increase the length of the alkane chain in the precursor or use a perfluroalkane derivative as precursor or as a capping agent. The hydrophobicity and hydrophilicity of the Janus films have been determined by contact angle measurements. The morphology of hydrophobic and hydrophilic sides of the film have been examined by field emission scanning electron microscopy.

  4. Crystallization induced block copolymer assembly at curved liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Qi, Hao; Zhou, Tian; Zhou, Hao; Li, Christopher; Soft Materials Lab Team

    In a selected solvent, amphiphilic block copolymers can self-assemble into various micelle structures which find widespread applications in nanomedicine. Herein we report a directed assembly of poly (l-lactide acid)-b-poly (ethylene glycol) (PLLA-b-PEG) at curved oil/water interfaces. Oil droplets were dispersed in water phase upon sonication with amphiphilic PLLA-b-PEG as the surfactant. Subsequent crystallization of PLLA segments resulted in the formation of lamellasomes consisting of crystalline PLLA shell and densely-grafted (approx.1chain/nm2) PEG layer. The structure, morphology, and mechanical properties of these unique polymer ensembles were investigated using transmission electron microscopy and atomic force microscopy. Detailed formation mechanism will be discussed in detail.

  5. Evidence of contact epitaxy in the self-assembly of HgSe nanocrystals formed at a liquid-liquid interface.

    PubMed

    Maiti, Santanu; Sanyal, Milan K; Jana, Manoj K; Runge, Benjamin; Murphy, Bridget M; Biswas, Kanishka; Rao, C N R

    2017-03-08

    The grazing incidence x-ray scattering results presented here show that the self-assembly process of HgSe nanocrystals formed at a liquid-liquid interface is quite different along the in-plane direction and across the interface. In situ x-ray reflectivity and ex situ microscopy measurements suggest quantized out-of-plane growth for HgSe nanoparticles of a size of about [Formula: see text] nm initially. Grazing incidence small-angle x-ray scattering measurements for films transferred from the water-toluene interface at various stages of reaction show that these nanoparticles first form random clusters with an average radius of 2.2 nm, giving rise to equally spaced rings of several orders. Finally, these clusters self-organize into face-centered cubic superstructures, giving sharp x-ray diffraction peaks oriented normal to the liquid-liquid interface with more than 100 nm-coherent domains. We also observed the x-ray diffraction pattern of the HgSe crystalline phase, with the superlattice peaks in these grazing incidence measurements of the transferred films. The electron microscopy and atomic force microscopy results support the x-ray observation of the self-organization of HgSe nanocrystals into close-packed superlattices. These results show that capillary wave fluctuation promotes the oriented attachment of clusters at the liquid-liquid interface, giving direct experimental evidence of contact epitaxy.

  6. Langmuir Films of Flexible Polymers Transferred to Aqueous/Liquid Crystal Interfaces Induce Uniform Azimuthal Alignment of the Liquid Crystal

    PubMed Central

    Kinsinger, Michael I.; Buck, Maren E.; Meli, Maria-Victoria; Abbott, Nicholas L.; Lynn, David M.

    2009-01-01

    We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4’-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4’-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films

  7. Effect of surface tension, viscosity, and process conditions on polymer morphology deposited at the liquid-vapor interface.

    PubMed

    Haller, Patrick D; Bradley, Laura C; Gupta, Malancha

    2013-09-17

    We have observed that the vapor-phase deposition of polymers onto liquid substrates can result in the formation of polymer films or particles at the liquid-vapor interface. In this study, we demonstrate the relationship between the polymer morphology at the liquid-vapor interface and the surface tension interaction between the liquid and polymer, the liquid viscosity, the deposition rate, and the deposition time. We show that the thermodynamically stable morphology is determined by the surface tension interaction between the liquid and the polymer. Stable polymer films form when it is energetically favorable for the polymer to spread over the surface of the liquid, whereas polymer particles form when it is energetically favorable for the polymer to aggregate. For systems that do not strongly favor spreading or aggregation, we observe that the initial morphology depends on the deposition rate. Particles form at low deposition rates, whereas unstable films form at high deposition rates. We also observe a transition from particle formation to unstable film formation when we increase the viscosity of the liquid or increase the deposition time. Our results provide a fundamental understanding about polymer growth at the liquid-vapor interface and can offer insight into the growth of other materials on liquid surfaces. The ability to systematically tune morphology can enable the production of particles for applications in photonics, electronics, and drug delivery and films for applications in sensing and separations.

  8. Orientation dependence of heterogeneous nucleation at the Cu-Pb solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Palafox-Hernandez, J. Pablo; Laird, Brian B.

    2016-12-01

    In this work, we examine the effect of surface structure on the heterogeneous nucleation of Pb crystals from the melt at a Cu substrate using molecular-dynamics (MD) simulation. In a previous work [Palafox-Hernandez et al., Acta Mater. 59, 3137 (2011)] studying the Cu/Pb solid-liquid interface with MD simulation, we observed that the structure of the Cu(111) and Cu(100) interfaces was significantly different at 625 K, just above the Pb melting temperature (618 K for the model). The Cu(100) interface exhibited significant surface alloying in the crystal plane in contact with the melt. In contrast, no surface alloying was seen at the Cu(111) interface; however, a prefreezing layer of crystalline Pb, 2-3 atomic planes thick and slightly compressed relative to bulk Pb crystal, was observed to form at the interface. We observe that at the Cu(111) interface the prefreezing layer is no longer present at 750 K, but surface alloying in the Cu(100) interface persists. In a series of undercooling MD simulations, heterogeneous nucleation of fcc Pb is observed at the Cu(111) interface within the simulation time (5 ns) at 592 K—a 26 K undercooling. Nucleation and growth at Cu(111) proceeded layerwise with a nearly planar critical nucleus. Quantitative analysis yielded heterogeneous nucleation barriers that are more than two orders of magnitude smaller than the predicted homogeneous nucleation barriers from classical nucleation theory. Nucleation was considerably more difficult on the Cu(100) surface-alloyed substrate. An undercooling of approximately 170 K was necessary to observe nucleation at this interface within the simulation time. From qualitative observation, the critical nucleus showed a contact angle with the Cu(100) surface of over 90°, indicating poor wetting of the Cu(100) surface by the nucleating phase, which according to classical heterogeneous nucleation theory provides an explanation of the large undercooling necessary to nucleate on the Cu(100) surface

  9. Simulation and Theory of Ions at Atmospherically Relevant Aqueous Liquid-Air Interfaces

    SciTech Connect

    Tobias, Douglas J.; Stern, Abraham C.; Baer, Marcel D.; Levin, Yan; Mundy, Christopher J.

    2013-04-01

    Chemistry occurring at or near the surfaces of aqueous droplets and thin films in the atmosphere influences air quality and climate. Molecular dynamics simulations are becoming increasingly useful for gaining atomic-scale insight into the structure and reactivity of aqueous interfaces in the atmosphere. Here we review simulation studies of atmospherically relevant aqueous liquid-air interfaces, with an emphasis on ions that play important roles in the chemistry of atmospheric aerosols. In addition to surveying results from simulation studies, we discuss challenges to the refinement and experimental validation of the methodology for simulating ion adsorption to the air-water interface, and recent advances in elucidating the driving forces for adsorption. We also review the recent development of a dielectric continuum theory that is capable of reproducing simulation and experimental data on ion behavior at aqueous interfaces. MDB and CJM acknowledge support from the US Department of Energy's Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle. MDB is supported by the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.

  10. Metastable nanobubbles at the solid-liquid interface due to contact angle hysteresis.

    PubMed

    Nishiyama, Takashi; Yamada, Yutaka; Ikuta, Tatsuya; Takahashi, Koji; Takata, Yasuyuki

    2015-01-27

    Nanobubbles exist at solid-liquid interfaces between pure water and hydrophobic surfaces with very high stability, lasting in certain cases up to several days. Not only semispherical but also other shapes, such as micropancakes, are known to exist at such interfaces. However, doubt has been raised as to whether or not the nanobubbles are gas-phase entities. In this study, surface nanobubbles at a pure water-highly ordered pyrolytic graphite (HOPG) interface were investigated by peak force quantitative nanomechanics (PF-QNM). Multiple isolated nanobubbles generated by the solvent-exchange method were present on the terraced areas, avoiding the steps of the HOPG surface. Adjacent nanobubbles coalesced and formed metastable nanobubbles. Coalescence was enhanced by the PF-QNM measurement. We determined that nanobubbles can exist for a long time because of nanoscale contact angle hysteresis at the water-HOPG interface. Moreover, the hydrophilic steps of HOPG were avoided during coalescence, providing evidence that the nanobubbles are truly gas phase.

  11. Mathematical modeling of planar and spherical vapor-liquid phase interfaces for multicomponent fluids

    NASA Astrophysics Data System (ADS)

    Celný, David; Vinš, Václav; Planková, Barbora; Hrubý, Jan

    2016-03-01

    Development of methods for accurate modeling of phase interfaces is important for understanding various natural processes and for applications in technology such as power production and carbon dioxide separation and storage. In particular, prediction of the course of the non-equilibrium phase transition processes requires knowledge of the properties of the strongly curved phase interfaces of microscopic droplets. In our work, we focus on the spherical vapor-liquid phase interfaces for binary mixtures. We developed a robust computational method to determine the density and concentration profiles. The fundamentals of our approach lie in the Cahn-Hilliard gradient theory, allowing to transcribe the functional formulation into a system of ordinary Euler-Langrange equations. This system is then split and modified into a shape suitable for iterative computation. For this task, we combine the Newton-Raphson and the shooting methods providing a good convergence speed. For the thermodynamic roperties, the PC-SAFT equation of state is used. We determine the density and concentration profiles for spherical phase interfaces at various saturation factors for the binary mixture of CO2 and C9H20. The computed concentration profiles allow to the determine the work of formation and other characteristics of the microscopic droplets.

  12. Studies of momentum and energy transfer across wavy gas-liquid interfaces. Final report

    SciTech Connect

    Dukler, A.E.

    1993-06-01

    Two phase gas-liquid flow and its associated interfaces exist in a wide variety of situations of importance to the Navy and this has prompted the study of the basic flow mechanics which underlie this complex process. The existence of wind-wave interactions over large bodies of water have long been recognized as a special case of two phase flow where the presence of the deformable interface plays a complex role in the generation of waves due to the action of the wind. Less well recognized, but of great importance, are situations of two phase flow which are found in components of power systems such as condensers, boilers refrigeration loops and cryogen lines. Here the characteristics of two phase flow are critical to the reliable design and safe operation of such systems.

  13. Interfacial Phase Transitions at Solid-Fluid and Liquid-Vapor Interfaces

    NASA Astrophysics Data System (ADS)

    Cornelisse, P. M. W.; Peters, C. J.; de Swaan Arons, J.

    1998-11-01

    To study the interface between a solid surface and nitrogen vapor, the theory of Cahn was applied. The Peng-Robinson equation of state (PREOS) was incorporated in the theory of Cahn to model the thermodynamic functions of the fluid. In this study the wetting transition, as earlier reported by Cahn, was shown. In addition, wetting transitions occurring at a liquid-vapor interface of the three-phase LLV equilibrium of the binary mixtures hexane/water and benzene/water were examined. It was found that by making use of the gradient theory of van der Waals, in which the PREOS was incorporated, the transitions seem to be of third order. For the case where the PREOS was replaced by the Associated-Perturbed-Anisotropic-Chain-Theory, no wetting region was found. It was argued that, in principle, it should he possible to model first-order wetting transitions with the square gradient theory.

  14. Lattice boltzmann study on the contact angle and contact line dynamics of liquid-vapor interfaces.

    PubMed

    Zhang, Junfeng; Kwok, Daniel Y

    2004-09-14

    The moving contact line problem of liquid-vapor interfaces was studied using a mean-field free-energy lattice Boltzmann method recently proposed [Phys. Rev. E 2004, 69, 032602]. We have examined the static and dynamic interfacial behaviors by means of the bubble and capillary wave tests and found that both the Laplace equation of capillarity and the dispersion relation were satisfied. Dynamic contact angles followed the general trend of contact line velocity observed experimentally and can be described by Blake's theory. The velocity fields near the interface were also obtained and are in good agreement with fluid mechanics and molecular dynamics studies. Our simulations demonstrated that incorporating interfacial effects into the lattice Boltzmann model can be a valuable and powerful alternative in interfacial studies.

  15. Analysis of stability of a planar solid-liquid interface in a dilute binary alloy

    NASA Technical Reports Server (NTRS)

    Laxmanan, V.

    1990-01-01

    This paper reconsiders the question of stability of a planar solid-liquid interface in an undercooled alloy melt without making the restrictive assumption of no heat flow in the solid (i.e., Gs = 0). The results of this analysis indicate that, provided the thermal gradient on the solid side of the interface, Gs, is positive, stability can be achieved in an undercooled alloy melt for growth rates R greater than Ra (where Ra is the absolute stability limit of Mullins and Sekerka, 1964). Thus, the absolute stability criterion for steady-state planar growth in an undercooled alloy melt is the same as derived earlier by Mullins and Sekerka for directional solidification. Relaxing the restrictive assumption of Gs = 0 also reveals that there is a regime of stability for low growth rates and low supercoolings.

  16. Localized single molecule isotherms of DNA molecules at confined liquid-solid interfaces.

    PubMed

    Liang, Heng; Cheng, Xiaoliang; Ma, Yinfa

    2009-03-15

    The study of dynamics and thermodynamics of single biological molecules at confined liquid-solid interfaces is crucially important, especially in the case of low-copy number molecules in a single cell. Using a high-throughput single molecule imaging system and Lagrangian coordinates of single molecule images, we discovered that the local equilibrium isotherms of single lambdaDNA molecules at a confined liquid-solid interface varied from a stair type for the regions of single or double molecular DNA to a mild "S" type for the regions of triple molecular DNA spots, which does not agree with the conventional equilibrium isotherms in the literature. Single molecule images in time sequence for different lambdaDNA concentrations were statistically analyzed by measuring preferential partitioning from shearing effects, which were used to measure the local velocity of DNA molecules by directly observing the migration of DNA fluorescence spots for the 12 continuous images. The local linear velocity of hydrodynamic flow was calculated by the Hagen-Poiseuille equation in different microregions with a local Lagrangian approach. The local single molecule isotherms for the tracked molecules in the regions of single, double, or triple molecular DNA layers within the laminar flows were obtained according to the average local velocities of both the stochastic molecule events and the corresponding local Poiseuille flows. A millisecond and microvolume approach to directly determine local single molecule isotherms at confined liquid-solid interfaces was established, and the microspace scale effects on the types of isotherms were discovered. This study may have significant impact on preparations of low-copy number proteins in a single cell, membrane separations, and other bioseparation studies.

  17. Understanding the influence of capillary waves on solvation at the liquid-vapor interface.

    PubMed

    Rane, Kaustubh; van der Vegt, Nico F A

    2016-03-21

    This work investigates the question if surface capillary waves (CWs) affect interfacial solvation thermodynamic properties that determine the propensity of small molecules toward the liquid-vapor interface. We focus on (1) the evaluation of these properties from molecular simulations in a practical manner and (2) understanding them from the perspective of theories in solvation thermodynamics, especially solvent reorganization effects. Concerning the former objective, we propose a computational method that exploits the relationship between an external field acting on the liquid-vapor interface and the magnitude of CWs. The system considered contains the solvent, an externally applied field (f) and the solute molecule fixed at a particular location. The magnitude of f is selected to induce changes in CWs. The difference between the solvation free energies computed in the presence and in the absence of f is then shown to quantify the contribution of CWs to interfacial solvation. We describe the implementation of this method in the canonical ensemble by using a Lennard-Jones solvent and a non-ionic solute. Results are shown for three types of solutes that differ in the nature of short-ranged repulsive (hard-core) interactions. Overall, we observe that CWs have a negligible or very small effect on the interfacial solvation free energy of a solute molecule fixed near the liquid-vapor interface for the above systems. We also explain how the effects of pinning or dampening of CWs caused by a fixed solute are effectively compensated and do not contribute to the solvation free energy.

  18. Effect of Imidazolium-Based Surface-Active Ionic Liquids on the Orientation of Liquid Crystals at Various Fluid/Liquid Crystal Interfaces.

    PubMed

    Tian, Tongtong; Hu, Qiongzheng; Wang, Yi; Gao, Yan'an; Yu, Li

    2016-11-15

    A series of imidazolium-based surface-active ionic liquids (IM-SAILs), viz., single-chained IM-SAILs, 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br, n = 12, 14, 16), 1-dodecyl-3-methylimidazolium salicylate ([C12mim]Sal), 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate ([C12mim]HNC), 1-dodecyl-3-methylimidazolium cinnamate ([C12mim]CA), 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim]PCA), gemini IM-SAIL, and 1,2-bis(3-dodecylimidazolium-1-yl)ethane bromide ([C12-2-C12im]Br2), along with three short-chained ionic liquids (ILs) [ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and butylammonium nitrate (BAN)] were synthesized and applied to nematic liquid crystal (LC)/fluid interfaces. First, we evaluated the influence of the length and number of aliphatic chains as well as the counterion in the IM-SAIL structures on the anchoring of LCs at the aqueous/LC interface. It was observed that the threshold concentration of [Cnmim]Br (n = 12, 14, 16) decreased with the increase in aliphatic chain length. And double-chained [C12-2-C12im]Br2 has a far lower threshold concentration than single-chained [C12mim]Br. But the alteration of counterions (e.g., Br(-) and aromatic counterions) scarcely affected the anchoring of LCs at the interface. Second, we investigated the alignment of LCs at the diverse IL/LC interfaces in the presence of IM-SAILs. It is found that the variations in both aliphatic chain length and number can remarkably change the trigger points of the orientational transition of LCs at the EAN/LC interface. Specifically, with a slight increase in the alkyl chain length of short-chained ILs, as the fluid medium, the orientation of LCs varied tremendously at the IL/LC interface. Therefore, the higher threshold concentration of IM-SAILs and the corresponding greater stability in the optical appearance of LCs at the EAN/LC interface compared to that of the aqueous/LC interface can be ascribed to the discrepancy in the microstructure of

  19. Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Qi, Hao; Zhou, Tian; Mei, Shan; Han, Lin; Higuchi, Takeshi; Jinnai, Hiroshi; Li, Christopher Y.

    2016-02-01

    Lipids and amphiphilic block copolymers spontaneously self-assemble in water to form a plethora of micelles and vesicles. They are typically fluidic in nature and often mechanically weak for applications such as drug delivery and gene therapeutics. Mechanical properties of polymeric materials could be improved by forming crystalline structures. However, most of the self-assembled micelles and vesicles have curved surfaces and precisely tuning crystallization within a nanoscale curved space is challenging, as the curved geometry is incommensurate with crystals having three-dimensional translational symmetry. Herein, we report using a miniemulsion crystallization method to grow nanosized, polymer single-crystal-like capsules. We coin the name crystalsome to describe this unique structure, because they are formed by polymer lamellar crystals and their structure mimics liposomes and polymersomes. Using poly(L-lactic acid) (PLLA) as the model polymer, we show that curved water/p-xylene interface formed by the miniemulsion process can guide the growth of PLLA single crystals. Crystalsomes with the size ranging from ~148 nm to over 1 μm have been formed. Atomic force microscopy measurement demonstrate a two to three orders of magnitude increase in bending modulus compared with conventional polymersomes. We envisage that this novel structure could shed light on investigating spherical crystallography and drug delivery.

  20. Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.

    PubMed

    Peljo, Pekka; Murtomäki, Lasse; Kallio, Tanja; Xu, Hai-Jun; Meyer, Michel; Gros, Claude P; Barbe, Jean-Michel; Girault, Hubert H; Laasonen, Kari; Kontturi, Kyösti

    2012-04-04

    Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co(2)(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen.

  1. Oxygen reduction catalyzed by a fluorinated tetraphenylporphyrin free base at liquid/liquid interfaces.

    PubMed

    Hatay, Imren; Su, Bin; Méndez, Manuel A; Corminboeuf, Clémence; Khoury, Tony; Gros, Claude P; Bourdillon, Mélanie; Meyer, Michel; Barbe, Jean-Michel; Ersoz, Mustafa; Zális, Stanislav; Samec, Zdenek; Girault, Hubert H

    2010-10-06

    The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB(-)) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.

  2. Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface

    PubMed Central

    Wang, Wenda; Qi, Hao; Zhou, Tian; Mei, Shan; Han, Lin; Higuchi, Takeshi; Jinnai, Hiroshi; Li, Christopher Y.

    2016-01-01

    Lipids and amphiphilic block copolymers spontaneously self-assemble in water to form a plethora of micelles and vesicles. They are typically fluidic in nature and often mechanically weak for applications such as drug delivery and gene therapeutics. Mechanical properties of polymeric materials could be improved by forming crystalline structures. However, most of the self-assembled micelles and vesicles have curved surfaces and precisely tuning crystallization within a nanoscale curved space is challenging, as the curved geometry is incommensurate with crystals having three-dimensional translational symmetry. Herein, we report using a miniemulsion crystallization method to grow nanosized, polymer single-crystal-like capsules. We coin the name crystalsome to describe this unique structure, because they are formed by polymer lamellar crystals and their structure mimics liposomes and polymersomes. Using poly(L-lactic acid) (PLLA) as the model polymer, we show that curved water/p-xylene interface formed by the miniemulsion process can guide the growth of PLLA single crystals. Crystalsomes with the size ranging from ∼148 nm to over 1 μm have been formed. Atomic force microscopy measurement demonstrate a two to three orders of magnitude increase in bending modulus compared with conventional polymersomes. We envisage that this novel structure could shed light on investigating spherical crystallography and drug delivery. PMID:26837260

  3. First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent

    NASA Astrophysics Data System (ADS)

    Sánchez, Verónica M.; Sued, Mariela; Scherlis, Damián A.

    2009-11-01

    Continuum solvent models have become a standard technique in the context of electronic structure calculations, yet no implementations have been reported capable to perform molecular dynamics at solid-liquid interfaces. We propose here such a continuum approach in a density functional theory framework using plane-wave basis sets and periodic boundary conditions. Our work stems from a recent model designed for Car-Parrinello simulations of quantum solutes in a dielectric medium [D. A. Scherlis et al., J. Chem. Phys. 124, 074103 (2006)], for which the permittivity of the solvent is defined as a function of the electronic density of the solute. This strategy turns out to be inadequate for systems extended in two dimensions: the dependence of the dielectric function on the electronic density introduces a new term in the Kohn-Sham potential, which becomes unphysically large at the interfacial region, seriously affecting the convergence of the self-consistent calculations. If the dielectric medium is properly redefined as a function of the atomic coordinates, a good convergence is obtained and the constant of motion is conserved during the molecular dynamics simulations. The Poisson problem is solved using a multigrid method, and in this way Car-Parrinello molecular dynamics simulations of solid-liquid interfaces can be performed at a very moderate computational cost. This scheme is employed to investigate the acid-base equilibrium at the TiO2-water interface. The aqueous behavior of titania surfaces has stimulated a large amount of experimental research, but many open questions remain concerning the molecular mechanisms determining the chemistry of the interface. Here we make an attempt to answer some of them, putting to the test our continuum model.

  4. How to distinguish various components of the SHG signal recorded from the solid/liquid interface?

    NASA Astrophysics Data System (ADS)

    Gassin, Pierre-Marie; Martin-Gassin, Gaelle; Prelot, Benedicte; Zajac, Jerzy

    2016-11-01

    Second harmonic generation (SHG) may be an important tool to probe buried solid/liquid interfaces because of its inherent surface sensitivity. A detailed interpretation of dye adsorption onto Si-SiO2 wafer is not straightforward because both adsorbent and adsorbate contribute to the overall SHG signal. The polarization resolved SHG analysis points out that the adsorbent and adsorbate contributions are out of phase by π/2 in the present system. The surface nonlinear susceptibility χ(2) represents thus a complex tensor in which its real part is related to the adsorbent contribution and its imaginary part to the adsorbate one.

  5. External electric field dependence of the structure of the electric double layer at an ionic liquid/Au interface

    NASA Astrophysics Data System (ADS)

    Yamamoto, Ryosuke; Morisaki, Hazuki; Sakata, Osami; Shimotani, Hidekazu; Yuan, Hongtao; Iwasa, Yoshihiro; Kimura, Tsuyoshi; Wakabayashi, Yusuke

    2012-07-01

    In order to clarify its electric double layer (EDL) structure under external voltage, an interface between the ionic liquid N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide and a Au (111) surface was studied by x-ray reflectometry. A clear change in reflectivity was observed as a function of applied voltage. The electron density profile of the ionic liquid around the interface was calculated using liquid structure models. Switching of the external electric field reversed the polarity of the EDL, and the magnitude of the applied voltage controlled the magnitude of the layering structure as well as molecular position fluctuation.

  6. Lamellar Bodies Form Solid Three-dimensional Films at the Respiratory Air-Liquid Interface*

    PubMed Central

    Ravasio, Andrea; Olmeda, Bárbara; Bertocchi, Cristina; Haller, Thomas; Pérez-Gil, Jesús

    2010-01-01

    Pulmonary surfactant is essential for lung function. It is assembled, stored and secreted as particulate entities (lamellar body-like particles; LBPs). LBPs disintegrate when they contact an air-liquid interface, leading to an instantaneous spreading of material and a decline in surface tension. Here, we demonstrate that the film formed by the adsorbed material spontaneously segregate into distinct ordered and disordered lipid phase regions under unprecedented near-physiological conditions and, unlike natural surfactant purified from bronchoalveolar lavages, dynamically reorganized into highly viscous multilayer domains with complex three-dimensional topographies. Multilayer domains, in coexistence with liquid phases, showed a progressive stiffening and finally solidification, probably driven by a self-driven disassembly of LBPs from a sub-surface compartment. We conclude that surface film formation from LBPs is a highly dynamic and complex process, leading to a more elaborated scenario than that observed and predicted by models using reconstituted, lavaged, or fractionated preparations. PMID:20558742

  7. Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface

    SciTech Connect

    Braga, Carlos Muscatello, Jordan Lau, Gabriel Müller, Erich A. Jackson, George

    2016-01-28

    We calculate an atomistically detailed free-energy profile across a heterogeneous system using a nonequilibrium approach. The path-integral formulation of Crooks fluctuation theorem is used in conjunction with the intrinsic sampling method to calculate the free-energy profile for the liquid-vapour interface of the Lennard-Jones fluid. Free-energy barriers are found corresponding to the atomic layering in the liquid phase as well as a barrier associated with the presence of an adsorbed layer as revealed by the intrinsic density profile. Our findings are in agreement with profiles calculated using Widom’s potential distribution theorem applied to both the average and the intrinsic profiles as well as the literature values for the excess chemical potential.

  8. Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface

    NASA Astrophysics Data System (ADS)

    Braga, Carlos; Muscatello, Jordan; Lau, Gabriel; Müller, Erich A.; Jackson, George

    2016-01-01

    We calculate an atomistically detailed free-energy profile across a heterogeneous system using a nonequilibrium approach. The path-integral formulation of Crooks fluctuation theorem is used in conjunction with the intrinsic sampling method to calculate the free-energy profile for the liquid-vapour interface of the Lennard-Jones fluid. Free-energy barriers are found corresponding to the atomic layering in the liquid phase as well as a barrier associated with the presence of an adsorbed layer as revealed by the intrinsic density profile. Our findings are in agreement with profiles calculated using Widom's potential distribution theorem applied to both the average and the intrinsic profiles as well as the literature values for the excess chemical potential.

  9. Adaptive-mesh-refinement simulation of partial coalescence cascade of a droplet at a liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Fakhari, Abbas; Bolster, Diogo

    2016-11-01

    A three-dimensional (3D) adaptive mesh refinement (AMR) algorithm on structured Cartesian grids is developed, and supplemented by a mesoscopic multiphase-flow solver based on state-of-the-art lattice Boltzmann methods (LBM). Using this in-house AMR-LBM routine, we present fully 3D simulations of partial coalescence of a liquid drop with an initially flat interface at small Ohnesorge and Bond numbers. Qualitatively, our numerical simulations are in excellent agreement with experimental observations. Partial coalescence cascades are successfully observed at very small Ohnesorge numbers (Oh 10-4). The fact that the partial coalescence is absent in similar 2D simulations suggests that the Rayleigh-Plateau instability may be the principle driving mechanism responsible for this phenomenon.

  10. Communication: Evaporation: Influence of heat transport in the liquid on the interface temperature and the particle flux

    NASA Astrophysics Data System (ADS)

    Heinen, Matthias; Vrabec, Jadran; Fischer, Johann

    2016-08-01

    Molecular dynamics simulations are reported for the evaporation of a liquid into vacuum, where a Lennard-Jones type fluid with truncated and shifted potential at 2.5σ is considered. Vacuum is enforced locally by particle deletion and the liquid is thermostated in its bulk so that heat flows to the planar interface driving stationary evaporation. The length of the non-thermostated transition region between the bulk liquid and the interface Ln is under study. First, it is found for the reduced bulk liquid temperature Tl/Tc = 0.74 (Tc is the critical temperature) that by increasing Ln from 5.2σ to 208σ the interface temperature Ti drops by 17% and the evaporation flux decreases by a factor of 4.4. From a series of simulations for increasing values of Ln, an asymptotic value Ti ∞ of the interface temperature for Ln → ∞ can be estimated which is 21% lower than the bulk liquid temperature Tl. Second, it is found that the evaporation flux is solely determined by the interface temperature Ti, independent on Tl or Ln. Combining these two findings, the evaporation coefficient α of a liquid thermostated on a macroscopic scale is estimated to be α ≈ 0.14 for Tl/Tc = 0.74.

  11. Communication: Evaporation: Influence of heat transport in the liquid on the interface temperature and the particle flux.

    PubMed

    Heinen, Matthias; Vrabec, Jadran; Fischer, Johann

    2016-08-28

    Molecular dynamics simulations are reported for the evaporation of a liquid into vacuum, where a Lennard-Jones type fluid with truncated and shifted potential at 2.5σ is considered. Vacuum is enforced locally by particle deletion and the liquid is thermostated in its bulk so that heat flows to the planar interface driving stationary evaporation. The length of the non-thermostated transition region between the bulk liquid and the interface Ln is under study. First, it is found for the reduced bulk liquid temperature Tl/Tc = 0.74 (Tc is the critical temperature) that by increasing Ln from 5.2σ to 208σ the interface temperature Ti drops by 17% and the evaporation flux decreases by a factor of 4.4. From a series of simulations for increasing values of Ln, an asymptotic value Ti (∞) of the interface temperature for Ln → ∞ can be estimated which is 21% lower than the bulk liquid temperature Tl. Second, it is found that the evaporation flux is solely determined by the interface temperature Ti, independent on Tl or Ln. Combining these two findings, the evaporation coefficient α of a liquid thermostated on a macroscopic scale is estimated to be α ≈ 0.14 for Tl/Tc = 0.74.

  12. Chronoamperometry at micropipet electrodes for determination of diffusion coefficients and transferred charges at liquid/liquid interfaces.

    PubMed

    Yuan, Yi; Wang, Lei; Amemiya, Shigeru

    2004-09-15

    Chronoamperometry was carried out at liquid/liquid interfaces supported at the tip of micropipet electrodes for direct determination of the diffusion coefficient of a species in the outer solution. The diffusion coefficient was used for subsequent determination of the transferred charges per species from the diffusion-limited steady-state current. A large tip resistance of the micropipets causes prolonged charging current so that the faradic current can be measured accurately only at a long-time regime (typically t > 5 ms). At the same time, the long-time current response at the interfaces surrounded by a thin glass wall of the pipets is enhanced by diffusion of the species from behind the pipet tip. Therefore, numerical simulations of the long-time chronoamperometric response were carried out using the finite element method for accurate determination of diffusion coefficients. Validity of the simulation results was confirmed by studying simple transfer of tetraethylammonium ion. The technique was applied for transfer/adsorption reactions of the natural polypeptide protamine and also for Ca2+ and Mg2+ transfers facilitated by ionophore ETH 129. With the diffusion coefficient of protamine determined to be (1.2 +/- 0.1) x 10(-6) cm(2)/s, the ionic charge transferred by each protamine molecule was obtained as +20 +/- 1, which is close to the excess positive charge of protamine. Also, the diffusion coefficient of ETH 129 was determined to demonstrate that each ionophore molecule transfers +0.67 and +1 charge per Ca2+ and Mg2+ transfer, respectively, which corresponds to formation of 1:3 and 1:2 complexes with the respective ions.

  13. Preparation of the initial solid liquid interface and melt in directional solidification

    NASA Astrophysics Data System (ADS)

    Nguyen Thi, H.; Drevet, B.; Debierre, J. M.; Camel, D.; Dabo, Y.; Billia, B.

    2003-06-01

    The preparation of the initial conditions (solid-liquid interface morphology and solute segregation in the liquid phase) on which growth is started is a very critical step in directional-solidification experiments. Dedicated experiments on Al-1.5 wt% Ni consisting in directional melting followed by thermal stabilisation with different lengths, show that precise control is in practice not straightforward. Indeed, in the mushy zone created by melting the original solid sample, temperature gradient zone melting (TGZM) causes migration of solute-rich liquid droplets and channels. A model is proposed to describe this process and validate the physical interpretation of the experiments through numerical simulation. Knowing the status of the preparation, the intriguing observations in the partially melted region of the Al-1.5 wt% Ni alloys solidified in the Advanced Gradient Heating Facility of European Space Agency during the LMS and STS-95 space missions can now be explained. Finally, the influence of initial interface morphology and melt segregation on directional-solidification transient is discussed, based on a comparison of Al-Ni alloys with hypoeutectic Al-Li alloys previously grown on Earth and in space. It follows that for experiments achieved on original rods with equiaxed microstructure, the efficiency of the preparatory melting and stabilisation phases can be evaluated from the solute macrosegregation profile in the region in between the non-melted solid and directional solidification. The major conclusion is that when the melt is mixed by fluid flow, the initial conditions are near to their asymptotic state at the end of TGZM whereas, when solute diffusion is the mode of transport into the bulk liquid, the condition of homogeneous melt becomes limiting and too much time-consuming to be fulfilled, which in particular holds for the 3D-experiments carried out in the reduced-gravity environment of space.

  14. Equilibrium orientations of non-spherical and chemically anisotropic particles at liquid-liquid interfaces and the effect on emulsion stability.

    PubMed

    Ballard, Nicholas; Bon, Stefan A F

    2015-06-15

    The effective stabilization of emulsions by solid particles, a phenomenon known as Pickering stabilization, is well known to be highly dependent on the wettability and the adhesion energy of the stabilizer employed at the liquid-liquid interface. We present a user-friendly computational model that can be used to determine equilibrium orientations and the adhesion energy of colloidal particles at interfaces. The model determines the free energy profile of particle adsorption at liquid-liquid interfaces using a triangular tessellation scheme. We demonstrate the use of the model, using a variety of anisotropic particles and demonstrate its ability to predict and explain experimental observations of particle behaviour at interfaces. In particular, we show that the concept of hydrophilic lipophilic balance commonly applied to molecular surfactants is insufficient to explain the complexity of the activity of colloidal particles at interfaces. In addition, we show the importance of the knowledge of the free energy adsorption profile of single particles at interfaces and the impact on overall free energy of emulsification of packed ensembles of particles. The delicate balance between optimization of adhesion energy, adsorption dynamics and particle packing is shown to be of great importance in the formation of thermodynamically stable emulsions. In order to use the model, the code is implemented by freely available software that can be readily deployed on personal computers.

  15. Molecular dynamics simulation analysis of ion irradiation effects on plasma-liquid interface

    NASA Astrophysics Data System (ADS)

    Minagawa, Yudai; Shirai, Naoki; Uchida, Satoshi; Tochikubo, Fumiyoshi

    2013-09-01

    Nonthermal atmospheric plasmas are used in a wide range of fields because the high-density plasma can be easily irradiated to various substances such as solid, liquid, biological object and so on. On the other hand, the mechanisms of physical and chemical phenomena at the plasma-liquid interface are not well understood yet. To investigate the effects of ion impact from plasma on water surface, we analyzed behavior of liquid water by classical molecular dynamics simulation. Simulation system consists of an irradiation particle in gas phase and 2000 water molecules in liquid phase. O+ ion with 10 eV or 100 eV was impinged on the water surface. Ion impact induced increasing water temperature and ejection of water molecules. The averaged number of evaporated water molecules by ion impact is 0.6 molecules at 10 eV and 7.0 molecules at 100 eV. The maximum ion penetration depth was 1.14 nm at 10 eV and 2.75 nm at 100 eV. Ion entering into water disturbs the stable hydrogen bonding configurations between water molecules and gives energy to water molecules. Some water molecules rotated and moved by ion interaction impact on other water molecules one after another. When the water molecule near the surface received strongly repulsive force, it released into gas phase. This work was supported financially in part by a Grant-in-Aid for Scientific Research on Innovation Areas (No21110007) from MEXT, Japan.

  16. Liquid/liquid interface layering of 1-butanol and [bmim]PF6 ionic liquid: a nonlinear vibrational spectroscopy and molecular dynamics simulation study.

    PubMed

    Iwahashi, Takashi; Ishiyama, Tatsuya; Sakai, Yasunari; Morita, Akihiro; Kim, Doseok; Ouchi, Yukio

    2015-10-14

    IR-visible sum-frequency generation (IV-SFG) vibrational spectroscopy and a molecular dynamics (MD) simulation were used to study the local layering order at the interface of 1-butanol-d9 and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6), a room-temperature ionic liquid (RTIL). The presence of a local non-polar layer at the interface of the two polar liquids was successfully demonstrated. In the SFG spectra of 1-butanol-d9, we observed significant reduction and enhancement in the strength of the CD3 symmetric stretching (r(+)) mode and the antisymmetric stretching (r(-)) mode peaks, respectively. The results can be well explained by the presence of an oppositely oriented quasi-bilayer structure of butanol molecules, where the bottom layer is strongly bound by hydrogen-bonding with the PF6(-) anion. MD simulations reveal that the hydrogen-bonding of butanol with the PF6(-) anion causes the preferential orientation of the butanols; the restriction on the rotational distribution of the terminal methyl group along their C3 axis enhances the r(-) mode. As for the [bmim](+) cations, the SFG spectra taken within the CH stretch region indicate that the butyl chain of [bmim](+) points away from the bulk RTIL phase to the butanol phase at the interface. Combining the SFG spectroscopy and MD simulation results, we propose an interfacial model structure of layering, in which the butyl chains of the butanol molecules form a non-polar interfacial layer with the butyl chains of the [bmim](+) cations at the interface.

  17. Molecular dynamics study of the processes in the vicinity of the n-dodecane vapour/liquid interface

    NASA Astrophysics Data System (ADS)

    Xie, Jian-Fei; Sazhin, Sergei S.; Cao, Bing-Yang

    2011-11-01

    Molecular dynamics (MD) simulation is used to study the evaporation and condensation of n-dodecane (C12H26), the closest approximation to Diesel fuel. The interactions in chain-like molecular structures are modelled using an optimised potential for liquid simulation (OPLS). The thickness of the transition layer between the liquid and vapour phases at equilibrium is estimated. It is shown that molecules at the liquid surface need to obtain relatively large translational energy to evaporate. The vapour molecules with large translational energy can easily penetrate deeply into the transition layer and condense in the liquid phase. The evaporation/condensation coefficient is estimated and the results are shown to be compatible with the previous estimates based on the MD analysis and the estimate based on the transition state theory. The velocity distribution functions of molecules at the liquid-vapour equilibrium state are found in the liquid phase, interface, and the vapour phase. These functions in the liquid phase and at the interface are shown to be close to isotropic Maxwellian for all velocity components. The velocity distribution function in the vapour phase is shown to be close to bi-Maxwellian with the temperature for the distribution normal to the interface being larger than the one for the distribution parallel to the interface.

  18. Experimental and Theoretical Studies of Liquid-Solid and Liquid-Vapor Interfaces of Metals and Alloys, Grant DE-FG02-06ER46321

    SciTech Connect

    Rice, Stuart

    2012-09-27

    The research supported by ER46321 was designed to understand in microscopic detail the structures of the interfaces between liquid metals and alloys and solid media. The system chosen for study, because of detailed knowledge of the structure of the corresponding liquid alloy-vapor interface, was the interface between a Si crystal and a dilute alloy of Pb in Ga. Experimental study of the Si:PbGa interface was anticipated to be very difficult; it requires preparation of an interface between a liquid metal and a solid surface that is flat to better than a nanometer on the scale length of the x-ray coherence, alignment of the x-ray beam and the surface in the sub-micro radian regime, and the use of high energy x-rays to penetrate the window and reach the interface without disastrous loss of intensity. The experimental design was subject to compromises forced by the limit to the highest x-ray energy available at the ChemMatCARS beam-line, namely 30 keV, which reduced the scattered signal relative to what can be obtained with higher x-ray energy. Although considerable progress was achieved during the support period and its no-cost extension, the difficulties encountered prevented completion of the studies and the data collected are incomplete. These data hint at the existence of unexpected structural features of the interface, in particular that Pb dimers play an important role in the interfacial structure. These data provide a different picture of the interface from the pentagonal structure inferred to be present in the interface between pure Pb and Si 001 (Nature 408, 839 (2000)), but much like the Ga dimers in the interface between liquid Ga and the 100 face of diamond (Nature 390, 379 (1997), J. Chem. Phys. 123, 104703 (2005)). However, during the latter part of the support period significant progress was made in the theoretical description of the liquid metal-crystal interface. In particular, stimulated by the results of an experimental study of the interface

  19. Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions

    SciTech Connect

    Brown, M A; D'Auria, R; Kuo, I W; Krisch, M J; Starr, D E; Bluhm, H; Tobias, D J; Hemminger, J C

    2008-04-23

    X-ray photoemission spectroscopy operating under ambient pressure conditions is used to probe ion distributions throughout the interfacial region of a free-flowing aqueous liquid micro-jet of 6 M potassium fluoride. Varying the energy of the ejected photoelectrons by carrying out experiments as a function of x-ray wavelength measures the composition of the aqueous-vapor interfacial region at various depths. The F{sup -} to K{sup +} atomic ratio is equal to unity throughout the interfacial region to a depth of 2 nm. The experimental ion profiles are compared with the results of a classical molecular dynamics simulation of a 6 M aqueous KF solution employing polarizable potentials. The experimental results are in qualitative agreement with the simulations when integrated over an exponentially decaying probe depth characteristic of an APPES experiment. First principles molecular dynamics simulations have been used to calculate the potential of mean force for moving a fluoride anion across the air-water interface. The results show that the fluoride anion is repelled from the interface, and this is consistent with the depletion of F{sup -} at the interface revealed by the APPES experiment and polarizable force field-based molecular dynamics simulation. Together, the APPES and MD simulation data provide a detailed description of the aqueous-vapor interface of alkali fluoride systems. This work offers the first direct observation of the ion distribution at a potassium fluoride aqueous solution interface. The current experimental results are compared to those previously obtained for saturated solutions of KBr and KI to underscore the strong difference in surface propensity between soft/large and hard/small halide ions in aqueous solution.

  20. Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions.

    PubMed

    Brown, Matthew A; D'Auria, Raffaella; Kuo, I-F William; Krisch, Maria J; Starr, David E; Bluhm, Hendrik; Tobias, Douglas J; Hemminger, John C

    2008-08-28

    X-Ray photoemission spectroscopy operating under ambient pressure conditions is used to probe ion distributions throughout the interfacial region of a free-flowing aqueous liquid micro-jet of 6 M potassium fluoride. Varying the energy of the ejected photoelectrons by carrying out experiments as a function of X-ray wavelength measures the composition of the aqueous-vapor interfacial region at various depths. The F(-) to K(+) atomic ratio is equal to unity throughout the interfacial region to a depth of 2 nm. The experimental ion profiles are compared with the results of a classical molecular dynamics simulation of a 6 M aqueous KF solution employing polarizable potentials. The experimental results are in qualitative agreement with the simulations when integrated over an exponentially decaying probe depth characteristic of an APPES experiment. First principles molecular dynamics simulations have been used to calculate the potential of mean force for moving a fluoride anion across the air-water interface. The results show that the fluoride anion is repelled from the interface, consistent with the depletion of F(-) at the interface revealed by the APPES experiment and polarizable force field-based molecular dynamics simulation. Together, the APPES and MD simulation data provide a detailed description of the aqueous-vapor interface of alkali fluoride systems. This work offers the first direct observation of the ion distribution at an aqueous potassium fluoride solution interface. The current experimental results are compared to those previously obtained for saturated solutions of KBr and KI to underscore the strong difference in surface propensity between soft/large and hard/small halide ions in aqueous solution.

  1. A two-dimensional-reference interaction site model theory for solvation structure near solid-liquid interface.

    PubMed

    Iida, Kenji; Sato, Hirofumi

    2011-12-28

    We develop a new equation to describe solvation structure near solid-liquid interface at the atomic-level. The developed equation focuses on anisotropy of solvation structure near the interface by using two-dimensional density distribution of solvent along two directions, one of which is perpendicular to the interface and the other is parallel to the interface. As a first application of the equation, we treat a system where a solid modeled by an atomistic wall is immersed in solvent water. The preferential adsorption position of water molecules and the change of water orientation by charging the wall are discussed.

  2. Manipulation of small particles at solid liquid interface: light driven diffusioosmosis

    PubMed Central

    Feldmann, David; Maduar, Salim R.; Santer, Mark; Lomadze, Nino; Vinogradova, Olga I.; Santer, Svetlana

    2016-01-01

    The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area. PMID:27808170

  3. Manipulation of small particles at solid liquid interface: light driven diffusioosmosis

    NASA Astrophysics Data System (ADS)

    Feldmann, David; Maduar, Salim R.; Santer, Mark; Lomadze, Nino; Vinogradova, Olga I.; Santer, Svetlana

    2016-11-01

    The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area.

  4. Satellite formation during bubble transition through an interface between immiscible liquids

    NASA Astrophysics Data System (ADS)

    Li, Erqiang; Al-Otaibi, Shabbab; Vakarelski, Ivan; Thoroddsen, Sigurdur

    2014-11-01

    A bubble can pass through the interface between two immiscible liquids if it is energetically favourable. Once the intermediate film has drained sufficiently, the bubble makes contact with the interface, forming a triple-line and producing strong capillary waves which travel around the bubble and can pinch off a satellite on the opposite side, akin to the coalescence cascade dynamics. We identify the critical Ohnesorge number where such satellites are produced and characterize their sizes. The total transition time scales with the bubble size and differential surface tension, while the satellite pinch-off time scales with the capillary-inertial time of the pool liquid which originally surrounds the bubble. We also use high-speed video imaging to study the contact neck motion. For low viscosity it grows in time with a power-law exponent between 0.44 and 0.50, with a prefactor modified by the net sum of the three interfacial tensions. Increasing the receiving drop viscosity drastically slows down the triple-line motion, when the Ohnesorge number exceeds around 0.08. This differs qualitatively from the coalescence of two miscible drops of different viscosities, where the lower viscosity sets the coalescence speed. We thereby propose a strong resistance from the triple-line.

  5. Determination of protein surface excess on a liquid/solid interface by single-molecule counting.

    PubMed

    Li, Nan; Tang, Hui; Gai, Hongwei; Dong, Xiuling; Wang, Qi; Yeung, Edward S

    2009-08-01

    Determination of protein surface excess is an important way of evaluating the properties of biomaterials and the characteristics of biosensors. A single-molecule counting method is presented that uses a standard fluorescence microscope to measure coverage of a liquid/solid interface by adsorbed proteins. The extremely low surface excess of lysozyme and bovine serum albumin (BSA), in a bulk concentration range from 0.3 nmol L(-1) (0.02 microg mL(-1)) to 3 nmol L(-1) (0.2 microg mL(-1)), were measured by recording the counts of spatially isolated single molecules on either hydrophilic (glass) or hydrophobic (polydimethylsiloxane, PDMS) surfaces at different pH. The differences observed in amounts of adsorbed proteins under different experimental conditions can be qualitatively explained by the combined interactions of electrostatic and hydrophobic forces. This, in turn, implies that single-molecule counting is an effective way of measuring surface coverage at a liquid/solid interface.

  6. Temperature Dependence and Energetics of Single Ions at the Aqueous Liquid-Vapor Interface

    PubMed Central

    Ou, Shuching; Patel, Sandeep

    2014-01-01

    We investigate temperature-dependence of free energetics with two single halide anions, I− and Cl−, crossing the aqueous liquid-vapor interface through molecular dynamics simulations. The result shows that I− has a modest surface stability of 0.5 kcal/mol at 300 K and the stability decreases as the temperature increases, indicating the surface adsorption process for the anion is entropically disfavored. In contrast, Cl− shows no such surface state at all temperatures. Decomposition of free energetics reveals that water-water interactions provide a favorable enthalpic contribution, while the desolvation of ion induces an increase in free energy. Calculations of surface fluctuations demonstrate that I− generates significantly greater interfacial fluctuations compared to Cl−. The fluctuation is attributed to the malleability of the solvation shells, which allows for more long-ranged perturbations and solvent density redistribution induced by I− as the anion approaches the liquid-vapor interface. The increase in temperature of the solvent enhances the inherent thermally-excited fluctuations and consequently reduces the relative contribution from anion to surface fluctuations, which is consistent with the decrease in surface-stability of I−. Our results indicate a strong correlation with induced interfacial fluctuations and anion surface stability; moreover, resulting temperature dependent behavior of induced fluctuations suggests the possibility of a critical level of induced fluctuations associated with surface stability. PMID:23537166

  7. Manipulation of small particles at solid liquid interface: light driven diffusioosmosis.

    PubMed

    Feldmann, David; Maduar, Salim R; Santer, Mark; Lomadze, Nino; Vinogradova, Olga I; Santer, Svetlana

    2016-11-03

    The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area.

  8. Two-dimensional DNA-programmable assembly of nanoparticles at liquid interfaces.

    PubMed

    Srivastava, Sunita; Nykypanchuk, Dmytro; Fukuto, Masafumi; Halverson, Jonathan D; Tkachenko, Alexei V; Yager, Kevin G; Gang, Oleg

    2014-06-11

    DNA-driven assembly of nanoscale objects has emerged as a powerful platform for the creation of materials by design via self-assembly. Recent years have seen much progress in the experimental realization of this approach for three-dimensional systems. In contrast, two-dimensional (2D) programmable nanoparticle (NP) systems are not well explored, in part due to the difficulties in creating such systems. Here we demonstrate the use of charged liquid interfaces for the assembly and reorganization of 2D systems of DNA-coated NPs. The absorption of DNA-coated NPs to the surface is controlled by the interaction between a positively charged lipid layer and the negatively charged DNA shells of particles. At the same time, interparticle interactions are switchable, from electrostatic repulsion between DNA shells to attraction driven by DNA complementarity, by increasing ionic strength. Using in situ surface X-ray scattering methods and ex situ electron microscopy, we reveal the corresponding structural transformation of the NP monolayer, from a hexagonally ordered 2D lattice to string-like clusters and finally to a weakly ordered network of DNA cross-linked particles. Moreover, we demonstrate that the ability to regulate 2D morphology yields control of the interfacial rheological properties of the NP membrane: from viscous to elastic. Theoretical modeling suggests that the structural adaptivity of interparticle DNA linkages plays a crucial role in the observed 2D transformation of DNA-NP systems at liquid interfaces.

  9. Removing pinhole shorts during large scale ferroelectric switching through ionic liquid interfaces

    NASA Astrophysics Data System (ADS)

    Wong, Anthony; Herklotz, Andreas; Wisinger, Nina; Rack, Philip; Ward, Thomas

    Ferroelectrics are a classification of materials that spontaneously polarize, accumulating charge at interfaces, and have non-linear hysteretic polarization curves. Switching fields required for ferroelectric materials are often very high, requiring thin insulating layers and high applied voltages. This commonly leads to electric pinholes and limits the areal sizes that can be polarized at a time. Ionic liquids have recently received heavy interest for the formation of electronic double layers which lead to huge electric fields at interfacial regions with low applied biases, and without the thickness constraint associated with conventional capacitors. We will show recent results which demonstrate that ionic liquid gating may offer the ideal solution to switch large regions of a ferroelectric film without limitations associated with pinhole defects. This has great importance to practical applications and fundamental interface studies that require large sample regions to be uniformly polarized. Supported by the US DOE Office of Basic Energy Sciences, Materials Sciences and Engineering Division and under US DOE Grant DE-SC0002136.

  10. Simulation of drag reduction in superhydrophobic microchannels based on parabolic gas-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Li, Chunxi; Zhang, Shuo; Xue, Quanxi; Ye, Xuemin

    2016-10-01

    Based on the given parabolic gas-liquid interfaces, a two-dimensional fluid flow in superhydrophobic microchannels is numerically simulated with the steady volume of fluid model in the laminar regime. The influence of several crucial parameters on drag reduction effect is discussed. The results indicate that the superhydrophobic microchannel containing rectangular cavities displays significant drag reduction effect. With increasing inlet velocity, the pressure drop reduction decreases slightly. Augments in the pressure drop reduction tend to be large with the increase of the cavity fraction or the decrease of the channel height. The results also reveal that the variation of the normalized slip length with the cavity fraction tends to be more dramatic when the channel height is smaller. As the parabolic height of the gas-liquid interface is enlarged, both the pressure drop reduction and the normalized slip length decrease linearly, while fRe increases linearly. The impact of the cavity depth on the normalized slip length, fRe, and the pressure drop reduction is minimal supposing the depth of the cavity is greater than 40% of its width. The drag reduction effect corresponding to the dovetail cavity model is the best, and the consequence of the rectangular, trapezoidal, and triangular cavity models sequentially worsens.

  11. Experimental investigations of stability of static liquid fillets and liquid-gas interface in capillary passages for gas-free liquid acquisition in zero gravity

    NASA Astrophysics Data System (ADS)

    Purohit, Ghanshyam Purshottamdas

    Experimental investigations of static liquid fillets formed between small gaps of a cylindrical surface and a flat surface are carried out. The minimum volume of liquid required to form a stable fillet and the maximum liquid content the fillet can hold before becoming unstable are studied. Fillet shapes are captured in photographs obtained by a high speed image system. Experiments were conducted using water, UPA and PF 5060 on two surfaces-stand-blasted titanium and polished copper for different surface inclinations. Experimental data are generalized using appropriate non-dimensional groups. Analytical model are developed to describe the fillet curvature. Fillet curvature data are compared against model predictions and are found to be in close agreement. Bubble point experiments were carried out to measure the capillary pressure difference across the liquid-gas interface in the channels of photo-chemically etched disk stacks. Experiments were conducted using titanium stacks of five different geometrical configurations. Both well wetting liquids (IPA and PF5060) and partially wetting liquid (water) were used during experiments. Test results are found to be in close agreement with analytical predictions. Experiments were carried out to measure the frictional pressure drop across the stack as a function of liquid flow rate using two different liquids (water and IPA) and five stacks of different geometrical configurations. A channel pressure drop model is developed by treating the flow within stack channels as fully developed laminar flow between parallel plates and solving the one-dimensional Navier Stokes equation. An alternate model is developed by treating the flow in channels as flow within porous media. Expressions are developed for effective porosity and permeability for the stacks and the pressure drop is related to these parameters. Pressure drop test results are found to be in close agreement with model predictions. As a specific application of this work, a

  12. Assembly, cross-linking and encapsulation using functionalized nanoparticles at liquid interfaces

    NASA Astrophysics Data System (ADS)

    Tangirala, Ravisubhash

    The assembly of nanoparticles at the interface of immiscible fluids holds promise for the preparation of new materials that benefit from both the physical properties of the nanoparticles and the chemistry associated with the ligands. Shaking nanoparticle solutions in organic solvents with water, results in the formation of nanoparticle-coated droplets that range in size from 10 microm to 200 microm. A strategy to control the size of these emulsions is described, by passing the droplets through commercial track-etch membranes with known pore sizes. Extrusion reduces the droplet size by breaking the droplets while passing theough the membrane pores, and reforming in the presence of excess nanoparticles in solution to form droplets as small as 1-5 microm. Crosslinking of nanoparticles at a liquid interface lends greater stability to the interfacial assembly, leading to ultrathin nanoparticle-based capsules, which possess mechanical integrity even after removal of the interface. Two approaches towards crosslinking are used in this thesis. Norbornene-functionalized CdSe/ZnS are used to afford facile capsule visualization by fluorescence confocal microscopy, as well as ease of crosslinking in mild conditions by means of ring-opening metathesis polymerization (ROMP). The crosslinked capsules can be used to encapsulate materials, and display size-selective retention capability, governed by the interstitial spaces between the nanoparticles. In a second approach to making hybrid capsules and sheets, horse spleen ferritin bionanoparticles and aldehyde-functionalized CdSe quantum dots are co-assembled at an oil-water interface. The cross-linked materials formed by reaction of the aldehyde functionality on the quantum dots with the surface-available amines on the ferritin bionanoparticles can be disrupted by addition of acid, thus leading to pH-degradable capsules and sheets. The driving force for assembly of nanoparticles at liquid interfaces is the reduction of the

  13. Highly sensitive detection of molecules at the liquid/liquid interface using total internal reflection-optical beam deflection based on photothermal spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujinami, Masanori; Murakawa, Hiromi; Sawada, Tsuguo

    2003-01-01

    In this study, a highly sensitive and versatile method based on photothermal spectroscopy has been developed to monitor the molecular density at a liquid/liquid interface. The excitation under the total internal reflection (TIR) condition results in a formation of a thin thermal lens elongated along the interface. In order to measure the thermal lens effects effectively and to reduce the background, the probe beam is irradiated parallel to the interface and its deflection is detected, which is called an TIR-optical beam deflection (TIR-OBD). As a result, the detection limit in TIR-OBD is about 2 orders lower than that of TIR-thermal lens spectroscopy, in which the irradiation of the probe beam is perpendicular to the interface.

  14. Phase conversion and interface growth in phase-separated 3He - 4He liquid mixtures

    NASA Astrophysics Data System (ADS)

    Abe, Haruka; Satoh, Takeo; Burmistrov, Serguei N.

    2005-10-01

    We have developed a method for measuring the transmission coefficient of a sound propagating through the interface in phase-separated He3-He4 liquid mixtures. The method and the results are described with discussions by examining the phase-conversion process of He3 quasiparticles driven to flow across the interface. From the data, we have determined the kinetic growth coefficient of the interface, ξ(T,P,ω) , as a function of temperature, pressure, and frequency. The temperature range of the present investigation is about 2-100mK at the pressure mainly around 1bar with sound frequency 9.64, 14.4, and 32.4MHz . The main specific features observed for the kinetic growth coefficient are, as follows: (i) there is a maximum at some temperature Tm(ω) depending on the frequency, (ii) above Tm(ω) , ξ decreases with the increase of temperature as ∝ω5/2T-3 , and (iii) below Tm(ω) , ξ becomes frequency independent and diminishes as a cube of temperature, T3 .

  15. DNA Hybridization-Mediated Liposome Fusion at the Aqueous Liquid Crystal Interface

    PubMed Central

    Noonan, Patrick S.; Mohan, Praveena; Goodwin, Andrew P.

    2014-01-01

    The prominence of receptor-mediated bilayer fusion in cellular biology motivates development of biomimetic strategies for studying fusogenic mechanisms. An approach is reported here for monitoring receptor-mediated fusion that exploits the unique physical and optical properties of liquid crystals (LC). PEG-functionalized lipids are used to create an interfacial environment capable of inhibiting spontaneous liposome fusion with an aqueous/LC interface. Then, DNA hybridization between oligonucleotides within bulk phase liposomes and a PEG-lipid monolayer at an aqueous/LC interface is exploited to induce receptor-mediated liposome fusion. These hybridization events induce strain within the liposome bilayer, promote lipid mixing with the LC interface, and consequently create an interfacial environment favoring re-orientation of the LC to a homeotropic (perpendicular) state. Furthermore, the bi-functionality of aptamers is exploited to modulate DNA hybridization-mediated liposome fusion by regulating the availability of the appropriate ligand (i.e., thrombin). Here, a LC-based approach for monitoring receptor (i.e., DNA hybridization)-mediated liposome fusion is demonstrated, liposome properties that dictate fusion dynamics are explored, and an example of how this approach may be used in a biosensing scheme is provided. PMID:25506314

  16. Self-assembly of DNA functionalized gold nanoparticles at the liquid-vapor interface

    DOE PAGES

    Zhang, Honghu; Wang, Wenjie; Hagen, Noah; ...

    2016-05-30

    Here, surface sensitive synchrotron X-ray scattering and spectroscopy are used to monitor and characterize the spontaneous formation of 2D Gibbs monolayers of thiolated single-stranded DNA-functionalized gold nanoparticles (ssDNAAuNPs) at the vapor–solution interface by manipulating salt concentrations. Grazing incidence small-angle X-ray scattering and X-ray refl ectivity show that the noncomplementary ssDNA-AuNPs dispersed in aqueous solution spontaneously accumulate at the vapor–liquid interface in the form of a single layer by increasing MgCl2 or CaCl2 concentrations. Furthermore, the monoparticle layer undergoes a transformation from short- to long-range (hexagonal) order above a threshold salt-concentration. Using various salts at similar ionic strength to those ofmore » MgCl2 or CaCl2 such as, NaCl or LaCl3, it is found that surface adsorbed NPs lack any order. X-ray fluorescence near total reflection of the same samples provides direct evidence of interfacial gold and more importantly a significant surface enrichment of the cations. Quantitative analysis reveals that divalent cations screen the charge of ssDNA, and that the hydrophobic hexyl-thiol group, commonly used to functionalize the ssDNA (for capping the AuNPs), is likely the driving force for the accumulation of the NPs at the interface.« less

  17. Self-assembly of DNA functionalized gold nanoparticles at the liquid-vapor interface

    SciTech Connect

    Zhang, Honghu; Wang, Wenjie; Hagen, Noah; Kuzmenko, Ivan; Akinc, Mufit; Travesset, Alex; Mallapragada, Surya; Vaknin, David

    2016-05-30

    Here, surface sensitive synchrotron X-ray scattering and spectroscopy are used to monitor and characterize the spontaneous formation of 2D Gibbs monolayers of thiolated single-stranded DNA-functionalized gold nanoparticles (ssDNAAuNPs) at the vapor–solution interface by manipulating salt concentrations. Grazing incidence small-angle X-ray scattering and X-ray refl ectivity show that the noncomplementary ssDNA-AuNPs dispersed in aqueous solution spontaneously accumulate at the vapor–liquid interface in the form of a single layer by increasing MgCl2 or CaCl2 concentrations. Furthermore, the monoparticle layer undergoes a transformation from short- to long-range (hexagonal) order above a threshold salt-concentration. Using various salts at similar ionic strength to those of MgCl2 or CaCl2 such as, NaCl or LaCl3, it is found that surface adsorbed NPs lack any order. X-ray fluorescence near total reflection of the same samples provides direct evidence of interfacial gold and more importantly a significant surface enrichment of the cations. Quantitative analysis reveals that divalent cations screen the charge of ssDNA, and that the hydrophobic hexyl-thiol group, commonly used to functionalize the ssDNA (for capping the AuNPs), is likely the driving force for the accumulation of the NPs at the interface.

  18. Emulsions stabilised by food colloid particles: role of particle adsorption and wettability at the liquid interface.

    PubMed

    Paunov, Vesselin N; Cayre, Olivier J; Noble, Paul F; Stoyanov, Simeon D; Velikov, Krassimir P; Golding, Matt

    2007-08-15

    We study the effect of the particle wettability on the preferred type of emulsion stabilised solely by food colloid particles. We present results obtained with the recently developed gel trapping technique (GTT) for characterisation of wettability and surface structuring of individual food colloid particles adsorbed at air-water and oil-water interfaces. This method allows us to replicate a particle monolayer onto the surface of polydimethylsiloxane (PDMS) without altering the position of the particles. By observing the polymer surface with scanning electron microscopy (SEM), we are able to determine the contact angle of the individual particles at the initial liquid interface. We demonstrate that the GTT can be applied to fat crystal particles, calcium carbonate particles coated with stearic acid and spray-dried soy protein/calcium phosphate particles at air-water and oil-water interfaces. Subsequently, we prepare emulsions of decane and water stabilised by the same food colloid particles and correlate the wettability data obtained for these particles to the preferred type of emulsions they stabilise.

  19. Engineering the Electrode-Electrolyte Interface: From Electrode Architecture to Zinc Redox in Ionic Liquid Electrolytes

    NASA Astrophysics Data System (ADS)

    Engstrom, Erika

    2011-12-01

    The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic

  20. Synthetic Polymers at Interfaces: Monodisperse Emulsions Multiple Emulsions and Liquid Marbles

    NASA Astrophysics Data System (ADS)

    Sun, Guanqing

    The adsorption of polymeric materials at interfaces is an energetically favorable process which is investigated in much diversified fields, such as emulsions, bubbles, foams, liquid marbles. Pickering emulsion, which is emulsion stabilized by solid particles has been investigated for over one century and preparation of Pickering emulsion with narrow size distribution is crucial for both the theoretical study of the stabilization mechanism and practical application, such as templated fabrication of colloidosomes. The precise control over the size and functionality of polymer latices allows the preparation of monodisperse Pickering emulsions with desired sizes through SPG membrane emulsification at rather rapid rate compared to microfludic production. Double or multiple emulsions have long been investigated but its rapid destabilization has always been a major obstacle in applying them into practical applications. The modern living polymerization techniques allow us to prepare polymers with designed structure of block copolymers which makes it possible to prepare ultra-stable multiple emulsions. The precise tuning of the ratio of hydrophobic part over the hydrophilic can unveil the stabilization mechanism. Liquid marble is a new type of materials of which liquid droplets are coated by dry particles. The coating of an outer layer of dry particles renders the liquid droplets non-sticky at solid surface which is useful in transportation of small amount of liquid without leakage at extreme low friction force. The property of liquid marbles relies largely on the stabilizers and the drying condition of polymeric latices is shown to have great influence on the property of liquid marbles. Firstly, an introduction to the interfacial and colloidal science with special attention to topics on emulsions, multiple emulsion and liquid marbles is given in Chapter 1. The unique features of an interface and a discussion on the definition of colloids are introduced prior to the

  1. Effects of temperature on the location of the gas-liquid interface in a PEM fuel cell

    NASA Astrophysics Data System (ADS)

    Lee, Chun-I.; Chu, Hsin-Sen

    The objective of this study is to investigate the location of the gas-liquid interface at various temperatures in a polymer electrolyte membrane fuel cell under non-isothermal conditions. A mathematical model, coupled with the electrochemical process, two-phase flows, species transfer, and heat transfer is employed. A finite volume-based CFD approach is applied to investigate the species transport behavior in a fuel cell. The effects of two model parameters, namely cell temperature (T cell) and humidification temperature (T h), on the gas-liquid interface and cell performance are presented. Simulation results indicate that variations of these two parameters influence the location of the gas-liquid interface, the cell performance, and the distribution of liquid water saturation. At lower cell temperatures, the gas-liquid interface moves toward the inlet port of the channel when the humidification temperature is greater than the cell temperature. Therefore, the cell performance decreases as the liquid water clogs the passage for the transport of oxygen. Furthermore, these two factors are closely related to the membrane temperature distribution. Obvious variations in magnitude are seen at a cell temperature of 323 K and a humidification temperature of 343 K.

  2. Monte Carlo simulation of the liquid-vapor interface of water using an ab initio potential

    NASA Astrophysics Data System (ADS)

    Lie, George C.; Grigoras, Stelian; Dang, Liem X.; Yang, Dah-Yen; McLean, A. Douglas

    1993-09-01

    Monte Carlo calculations have been carried out to study the interfacial properties of liquid water, using the Matsuoka-Clementi-Yoshimine (MCY) potential for the water-water interaction. The surface tension calculated at 298 K is 23.7±3.4 dyn/cm, to be compared with the experimental value of 72 dyn/cm. The interfacial 10-90 thickness is 4.70 Å, with the dipoles of the water molecules near the liquid phase pointing slightly towards the liquid phase and those near the gas phase pointing towards the gas phase. The interfacial water molecules are found to be more restricted in their rotation, as evidenced by the smaller root-mean-squared fluctuations of the dipole directions. The Volta potential difference across the interface arising from the permanent dipoles is estimated to be 0.024 V. A new and efficient method is proposed to calculated the surface excess energy. The excess energy calculated for the MCY water is 119 erg/cm2, to be compared with the experimental value of 120 erg/cm2. From the calculated surface excess energy, the temperature variation of the surface tension, or the surface entropy, for the MCY water is estimated to be -0.32 dyn/(cm2 K). This temperature variation is confirmed by another Monte Carlo study at 310 K to within the calculated uncertainty.

  3. Distribution of binding energies of a water molecule in the water liquid-vapor interface

    SciTech Connect

    Chempath, Shaji; Pratt, Lawrence R

    2008-01-01

    Distributions of binding energies of a water molecule in the water liquid-vapor interface are obtained on the basis of molecular simulation with the SPC/E model of water. These binding energies together with the observed interfacial density profile are used to test a minimally conditioned Gaussian quasi-chemical statistical thermodynamic theory. Binding energy distributions for water molecules in that interfacial region clearly exhibit a composite structure. A minimally conditioned Gaussian quasi-chemical model that is accurate for the free energy of bulk liquid water breaks down for water molecules in the liquid-vapor interfacial region. This breakdown is associated with the fact that this minimally conditioned Gaussian model would be inaccurate for the statistical thermodynamics of a dilute gas. Aggressive conditioning greatly improves the performance of that Gaussian quasi-chemical model. The analogy between the Gaussian quasi-chemical model and dielectric models of hydration free energies suggests that naive dielectric models without the conditioning features of quasi-chemical theory will be unreliable for these interfacial problems. Multi-Gaussian models that address the composite nature of the binding energy distributions observed in the interfacial region might provide a mechanism for correcting dielectric models for practical applications.

  4. An interface for the direct coupling of small liquid samples to AMS

    SciTech Connect

    Ognibene, T. J.; Thomas, A. T.; Daley, P. F.; Bench, G.; Turteltaub, K. W.

    2015-05-28

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL’s Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography (HPLC). Discrete samples containing at least a few 10 s of nanograms of carbon and as little as 50 zmol 14C can be measured with a 3–5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targets for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of 14C. As a result, liquid sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.

  5. Microscopic thin film optical anisotropy imaging at the solid-liquid interface.

    PubMed

    Miranda, Adelaide; De Beule, Pieter A A

    2016-04-01

    Optical anisotropy of thin films has been widely investigated through ellipsometry, whereby typically an optical signal is averaged over a ∼1 cm(2) elliptical area that extends with increasing angle-of-incidence (AOI). Here, we report on spectroscopic imaging ellipsometry at the solid-liquid interface applied to a supported lipid bilayer (SLB). We detail how a differential spectrally resolved ellipsometry measurement, between samples with and without optically anisotropic thin film on an absorbing substrate, can be applied to recover in and out of plane refractive indices of the thin film with known film thickness, hence determining the thin film optical anisotropy. We also present how optimal wavelength and AOI settings can be determined ensuring low parameter cross correlation between the refractive indices to be determined from a differential measurement in Δ ellipsometry angle. Furthermore, we detail a Monte Carlo type analysis that allows one to determine the minimal required optical ellipsometry resolution to recover a given thin film anisotropy. We conclude by presenting a new setup for a spectroscopic imaging ellipsometry based on fiber supercontinuum laser technology, multi-wavelength diode system, and an improved liquid cell design, delivering a 5 ×-10 × ellipsometric noise reduction over state-of-the-art. We attribute this improvement to increased ellipsometer illumination power and a reduced light path in liquid through the use of a water dipping objective.

  6. An interface for the direct coupling of small liquid samples to AMS

    DOE PAGES

    Ognibene, T. J.; Thomas, A. T.; Daley, P. F.; ...

    2015-05-28

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL’s Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography (HPLC). Discrete samples containing at least a few 10 s of nanograms of carbon and as little as 50 zmol 14C can be measured with a 3–5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targetsmore » for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of 14C. As a result, liquid sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.« less

  7. Possible fossil H2O liquid-ice interfaces in the Martian crust

    USGS Publications Warehouse

    Soderblom, L.A.; Wenner, D.B.

    1978-01-01

    Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H2O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H2O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H2O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H2O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9

  8. Atomic study on the ordered structure in Al melts induced by liquid/substrate interface with Ti solute

    SciTech Connect

    Zhang, H. L.; Han, Y. F. E-mail: bdsun@sjtu.edu.cn; Zhou, W.; Dai, Y. B.; Wang, J.; Sun, B. D. E-mail: bdsun@sjtu.edu.cn

    2015-01-26

    Atomic ordering in Al melts induced by liquid/substrate interface with Ti solute was investigated by ab initio molecular dynamics simulations and in-situ synchrotron X-ray diffraction. It is predicted that deformed nanoscale ordering Al layers with a rhombohedral-centered hexagonal structure (R3{sup ¯}m space group) instead of the intrinsic fcc structure (Fm3{sup ¯}m space group) form on substrate at temperature above Al liquids. With Al atoms stacking away from the interface, the ordering structure reaches a critical thickness, which inhibits the consecutive stacking of Al atoms on substrates. The locally stacking reconstruction induced by Ti atom relieves the accumulated elastic strain energy in ordered Al layers, facilitating fully heterogeneous nucleation on substrate beyond the deformed ordering Al layer around the melting point. The roles of liquid/substrate interface with Ti solute in the physical behavior of heterogeneous nucleation on substrate were discussed.

  9. Liquid-Gated High Mobility and Quantum Oscillation of the Two-Dimensional Electron Gas at an Oxide Interface.

    PubMed

    Zeng, Shengwei; Lü, Weiming; Huang, Zhen; Liu, Zhiqi; Han, Kun; Gopinadhan, Kalon; Li, Changjian; Guo, Rui; Zhou, Wenxiong; Ma, Haijiao Harsan; Jian, Linke; Venkatesan, Thirumalai; Ariando

    2016-04-26

    Electric field effect in electronic double layer transistor (EDLT) configuration with ionic liquids as the dielectric materials is a powerful means of exploring various properties in different materials. Here, we demonstrate the modulation of electrical transport properties and extremely high mobility of two-dimensional electron gas at LaAlO3/SrTiO3 (LAO/STO) interface through ionic liquid-assisted electric field effect. With a change of the gate voltages, the depletion of charge carrier and the resultant enhancement of electron mobility up to 19 380 cm(2)/(V s) are realized, leading to quantum oscillations of the conductivity at the LAO/STO interface. The present results suggest that high-mobility oxide interfaces, which exhibit quantum phenomena, could be obtained by ionic liquid-assisted field effect.

  10. In vitro toxicity testing of cigarette smoke based on the air-liquid interface exposure: A review.

    PubMed

    Li, Xiang

    2016-10-01

    Cigarette smoke is a complex aerosol comprising particulate phase and gaseous vapour phase. The air-liquid interface exposure provides a possible technical means to implement whole smoke exposure for the assessment of tobacco products. In this review, the research progress in the in vitro toxicity testing of cigarette smoke based on the air-liquid interface exposure is summarized. The contents presented involve mainly cytotoxicity, genotoxicity, oxidative stress, inflammation, systems toxicology, 3D culture and cigarette smoke dosimetry related to cigarette smoke, as well as the assessment of electronic cigarette aerosol. Prospect of the application of the air-liquid interface exposure method in assessing the biological effects of tobacco smoke is discussed.

  11. Analytical model for the effects of wetting on thermal boundary conductance across solid/classical liquid interfaces

    SciTech Connect

    Caplan, Matthew E.; Giri, Ashutosh; Hopkins, Patrick E.

    2014-04-21

    We develop an analytical model for the thermal boundary conductance between a solid and a liquid. By infusing recent developments in the phonon theory of liquid thermodynamics with diffuse mismatch theory, we derive a closed form model that can predict the effects of wetting on the thermal boundary conductance across an interface between a solid and a classical liquid. We account for the complete wetting (hydrophilicity), or lack thereof (hydrophobicity), of the liquid to the solid by considering varying contributions of transverse mode interactions between the solid and liquid interfacial layers; this transverse coupling relationship is determined with local density of states calculations from molecular dynamics simulations between Lennard-Jones solids and a liquids with different interfacial interaction energies. We present example calculations for the thermal boundary conductance between both hydrophobic and hydrophilic interfaces of Al/water and Au/water, which show excellent agreement with measured values reported by Ge et al. [Z. Ge, D. G. Cahill, and P. V. Braun, Phys. Rev. Lett. 96, 186101 (2006)]. Our model does not require any fitting parameters and is appropriate to model heat flow across any planar interface between a solid and a classical liquid.

  12. The vapor-liquid interface potential of (multi)polar fluids and its influence on ion solvation.

    PubMed

    Horváth, Lorand; Beu, Titus; Manghi, Manoel; Palmeri, John

    2013-04-21

    The interface between the vapor and liquid phase of quadrupolar-dipolar fluids is the seat of an electric interfacial potential whose influence on ion solvation and distribution is not yet fully understood. To obtain further microscopic insight into water specificity we first present extensive classical molecular dynamics simulations of a series of model liquids with variable molecular quadrupole moments that interpolates between SPC/E water and a purely dipolar liquid. We then pinpoint the essential role played by the competing multipolar contributions to the vapor-liquid and the solute-liquid interface potentials in determining an important ion-specific direct electrostatic contribution to the ionic solvation free energy for SPC/E water-dominated by the quadrupolar and dipolar parts-beyond the dominant polarization one. Our results show that the influence of the vapor-liquid interfacial potential on ion solvation is strongly reduced due to the strong partial cancellation brought about by the competing solute-liquid interface potential.

  13. The micro-flow reaction system featured the liquid-liquid interface created with ternary mixed carrier solvents in a capillary tube.

    PubMed

    Masuhara, Yuji; Jinno, Naoya; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

    2012-01-01

    A micro-flow reaction system was developed in which liquid-liquid interface was created based on the tube radial distribution of ternary mixed carrier solvents. The system was constructed from double capillary tubes having different inner diameters (100 and 250 µm i.d.). The smaller tube was inserted into the larger one through a T-type joint. The reaction of a protein with a fluorescence derivatizing reagent was adopted as a model. A water-acetonitrile mixture (3:1 volume ratio) including bovine serum albumin (hydrophilic) was delivered into the large tube from the inside through the small tube and an acetonitrile-ethyl acetate mixture (7:4 volume ratio) containing fluorescamine (hydrophobic) as a derivatizing reagent was delivered from the outside through the joint. Solutions were mixed through the double capillary tubes to promote ternary mixed carrier solvents (water-acetonitrile-ethyl acetate; 1:2:1 volume ratio). The liquid-liquid interface was created based on the tube radial distribution of ternary solvents in the larger tube. The derivatization reaction was performed in the larger, or reaction, tube in the micro-flow system. The fluorescence intensity of the fluorescamine-derivatized bovine serum albumin obtained by the system, which specifically included the kinetic liquid-liquid interface in the tube, was greater than that obtained through a batch reaction using a homogeneous solution of water-acetonitrile (1:2 volume ratio).

  14. Extended Vofire algorithm for fast transient fluid-structure dynamics with liquid-gas flows and interfaces

    NASA Astrophysics Data System (ADS)

    Faucher, Vincent; Kokh, Samuel

    2013-05-01

    The present paper is dedicated to the simulation of liquid-gas flows with interfaces in the framework of fast transient fluid-structure dynamics. The two-fluid interface is modelled as a discontinuity surface in the fluid property. We use an anti-dissipative Finite-Volume discretization strategy for unstructured meshes in order to capture the position of the interface within a thin diffused volume. This allows to control the numerical diffusion of the artificial mixing between components and provide an accurate capture of complex interface motions. This scheme is an extension of the Vofire numerical solver. We propose specific developments in order to handle flows that involved high density ratio between liquid and gas. The resulting scheme capabilities are validated on basic examples and also tested against large scale fluid-structure test derived from the MARA 10 experiment. All simulations are performed using EUROPLEXUS fast transient dynamics software.

  15. Analysis of Bacterial Detachment from Substratum Surfaces by the Passage of Air-Liquid Interfaces

    PubMed Central

    Gómez-Suárez, Cristina; Busscher, Henk J.; van der Mei, Henny C.

    2001-01-01

    A theoretical analysis of the detachment of bacteria adhering to substratum surfaces upon the passage of an air-liquid interface is given, together with experimental results for bacterial detachment in the absence and presence of a conditioning film on different substratum surfaces. Bacteria (Streptococcus sobrinus HG1025, Streptococcus oralis J22, Actinomyces naeslundii T14V-J1, Bacteroides fragilis 793E, and Pseudomonas aeruginosa 974K) were first allowed to adhere to hydrophilic glass and hydrophobic dimethyldichlorosilane (DDS)-coated glass in a parallel-plate flow chamber until a density of 4 × 106 cells cm−2 was reached. For S. sobrinus HG1025, S. oralis J22, and A. naeslundii T14V-J1, the conditioning film consisted of adsorbed salivary components, while for B. fragilis 793E and P. aeruginosa 974K, the film consisted of adsorbed human plasma components. Subsequently, air bubbles were passed through the flow chamber and the bacterial detachment percentages were measured. For some experimental conditions, like with P. aeruginosa 974K adhering to DDS-coated glass and an air bubble moving at high velocity (i.e., 13.6 mm s−1), no bacteria detached upon passage of an air-liquid interface, while for others, detachment percentages between 80 and 90% were observed. The detachment percentage increased when the velocity of the passing air bubble decreased, regardless of the bacterial strain and substratum surface hydrophobicity involved. However, the variation in percentages of detachment by a passing air bubble depended greatly upon the strain and substratum surface involved. At low air bubble velocities the hydrophobicity of the substratum had no influence on the detachment, but at high air bubble velocities all bacterial strains were more efficiently detached from hydrophilic glass substrata. Furthermore, the presence of a conditioning film could either inhibit or stimulate detachment. The shape of the bacterial cell played a major role in detachment at high

  16. Formation of Multicomponent Star Structures at the Liquid/Solid Interface.

    PubMed

    Tahara, Kazukuni; Kaneko, Kyohei; Katayama, Keisuke; Itano, Shintaro; Nguyen, Chi Huan; Amorim, Deborah D D; De Feyter, Steven; Tobe, Yoshito

    2015-06-30

    To demonstrate key roles of multiple interactions between multiple components and multiple phases in the formation of an uncommon self-assembling pattern, we present here the construction of a porous hexagonal star (h-star) structure using a trigonal molecular building block at the liquid/solid interface. For this purpose, self-assembly of hexaalkoxy-substituted dehydrobenzo[12]annulene derivatives DBA-OCns was investigated at the tetradecane/graphite interface by means of scanning tunneling microscopy (STM). Monolayer structures were significantly influenced by coadsorbed tetradecane molecules depending on the alkyl chains length (C13-C16) of DBA-OCn. However, none of DBA-OCn molecules formed the expected trigonal complexes, indicating that an additional driving force is necessary for the formation of the trigonal complex and its assembly into the h-star structure. As a first approach, we employed the "guest induced structural change" for the formation of the h-star structure. In the presence of two guest molecules, nonsubstituted DBA and hexakis(phenylethynyl)benzene which fit the respective pores, an h-star structure was formed by DBA-OC15 at the tetradecane/graphite interface. Moreover, a tetradecane molecule was coadsorbed between a pair of alkyl chains of DBA-OC15, thereby blocking the interdigitation of the alkyl chain pairs. Therefore, the h-star structure results from the self-assembly of the four molecular components including the solvent molecule. The second approach is based on aggregation of perfluoroalkyl chains via fluorophilicity of DBA-F, in which the perfluoroalkyl groups are substituted at the end of three alkyl chains of DBA-OCn via p-phenylene linkers. A trigonal complex consisting of DBA-F and three tetradecane molecules formed an h-star structure, in which the perfluoroalkyl groups that orient into the alkane solution phase aggregated at the hexagonal pore via fluorophilicity. The present result provides useful insight into the design and

  17. SO{sub 2} uptake on ice spheres: Liquid nature of the ice-air interface

    SciTech Connect

    Conklin, M.H.; Bales, R.C.

    1993-09-20

    The amount of SO{sub 2} gas absorbed by ice of known surface area at equilibrium was used to estimate the volume of liquid water present at the ice-air interface at temperatures from {minus}1 to {minus}60{degrees}C. Calculations were based on Henry`s law and acid dissociation equilibrium. The liquid volume is lowest at lower temperatures and ionic strength and under most conditions was greater than the volumes calculated based on freezing-point depression. The equivalent layer thickness, assuming that liquid water is uniformly distributed around the grains, ranged from 3-30 nm at {minus}60{degrees}C to 500-3000 nm at {minus}1{degrees}C. Corresponding ionic strengths for the two temperatures were 1.7-0.0012 M and 0.005-0.00009 M. Lower values were for ice made from distilled water, and higher values were for ice made from 10{sup {minus}3} M NaCl. Estimated pH values were from 2.9 at {minus}60{degrees}C to 4.1 at {minus}1{degrees}C. Results demonstrate that gas absorption can be used to estimate an equivalent liquid volume and thickness for the ice-air interfacial region. While not directly comparable to physical measurements, the estimated values should be directly applicable to modeling uptake of SO{sub 2} and other trace gases by ice. Lack of good thermodynamic data for temperature below 0{degrees}C is the main limitation to applying this method. 23 refs., 3 figs., 1 tab.

  18. Fabrication of composite thin films with microstructures of honeycomb, foam, and nanosphere arrays through adsorption and self-assembly of block copolymers at the liquid/liquid interface.

    PubMed

    Liu, Yanan; Chen, Lifang; Geng, Yuanyuan; Lee, Yong-Ill; Li, Ying; Hao, Jingcheng; Liu, Hong-Guo

    2013-10-01

    The adsorption and self-organization behaviors of two kinds of block copolymers, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(4-vinylpyridine)-block-polystyrene-block-poly(4-vinylpyridine) (P4VP-b-PS-b-P4VP), at planar liquid/liquid interfaces were investigated. A gel film decorating with honeycomb-like microstructures forms at the liquid/liquid interface between PS-b-P4VP chloroform solution and chloroauric acid aqueous solution. However, foam films were developed when the chloroauric acid aqueous solution was replaced by a chloroplatinic acid solution or a silver nitrate solution. Furthermore, a free-standing film containing the ordered arrays of nanospheres appeared at the liquid/liquid interface between P4VP-b-PS-b-P4VP chloroform solution and chloroauric acid aqueous solution. The formation of these microstructures was attributed to the adsorption of polymer molecules, combining with inorganic ions and the self-assembly of the composite species at the interface. The doped metal ions and complex ions were transformed to metal nanoparticles after further treatment. This is a facile and convenient method to prepare polymer/inorganic nanoparticle composites. These results also indicate the great influences of the polymer structures and the inorganic species in the aqueous phases on the self-assembly behaviors of the polymers at the interfaces, the final morphology, and structure of the composites. In addition, the formed thin composite films doped with well-dispersed, homogeneous small noble metal nanoparticles exhibit great and durable catalytic activities for the reduction of 4-nitrophenol (4-NP) by potassium borohydride.

  19. Molecular dynamics study of nanoparticle stability at liquid interfaces: Effect of nanoparticle-solvent interaction and capillary waves

    NASA Astrophysics Data System (ADS)

    Cheung, David L.

    2011-08-01

    While the interaction of colloidal particles (sizes in excess of 100 nm) with liquid interfaces may be understood in terms of continuum models, which are grounded in macroscopic properties such as surface and line tensions, the behaviour of nanoparticles at liquid interfaces may be more complex. Recent simulations [D. L. Cheung and S. A. F. Bon, Phys. Rev. Lett. 102, 066103 (2009)], 10.1103/PhysRevLett.102.066103 of nanoparticles at an idealised liquid-liquid interface showed that the nanoparticle-interface interaction range was larger than expected due, in part, to the action of thermal capillary waves. In this paper, molecular dynamics simulations of a Lennard-Jones nanoparticle in a binary Lennard-Jones mixture are used to confirm that these previous results hold for more realistic models. Furthermore by including attractive interactions between the nanoparticle and the solvent, it is found that the detachment energy decreases as the nanoparticle-solvent attraction increases. Comparison between the simulation results and recent theoretical predictions [H. Lehle and M. Oettel, J. Phys. Condens. Matter 20, 404224 (2008)], 10.1088/0953-8984/20/40/404224 shows that for small particles the incorporation of capillary waves into the predicted effective nanoparticle-interface interaction improves agreement between simulation and theory.

  20. Interfaces of semi-infinite smectic liquid crystals and equations of state of infinite smectic stacks of semiflexible manifolds.

    PubMed

    Gao, Lianghui; Golubović, Leonardo

    2003-02-01

    In this paper, we first elucidate the classical problem of the elastic free energy of a semi-infinite smectic-A liquid crystals, that fills the semispace above an interface (a boundary smectic layer) of a given shape. For the free energy of this interface, we obtain an effective interface Hamiltonian that takes into account the system discreteness introduced by the layered character of smectic-A liquid crystals. It is thus applicable to both short and long wavelength fluctuations of the interface shape. Next, we use our interface Hamiltonian to develop an efficient approach to the statistical mechanics of stacks of N semiflexible manifolds, such as two-dimensional smectic phases of long semiflexible polymers and three-dimensional lamellar fluid membrane phases. Within our approach, doing the practically interesting thermodynamic limit N--> infinity is reduced to considering a small stack, with just a few interacting manifolds, representing a subsystem of an infinite smectic. This dramatic reduction in the number of degrees of freedom is achieved by treating the first (the last) manifold of the small stack as an interface with the semi-infinite smectic medium below (above) the small stack. We illustrate our approach by considering in detail two-dimensional sterically stabilized smectic liquid crystals of long semiflexible polymers with hard-core repulsion. Smectic bulk (N= infinity ) equation of state and the universal constant characterizing entropic repulsion in these phases are obtained with a high accuracy from numerical simulations of small subsystems with just a few semiflexible polymers.

  1. Structure and dynamics of single hydrophobic/ionic heteropolymers at the vapor-liquid interface of water.

    PubMed

    Vembanur, Srivathsan; Venkateshwaran, Vasudevan; Garde, Shekhar

    2014-04-29

    We focus on the conformational stability, structure, and dynamics of hydrophobic/charged homopolymers and heteropolymers at the vapor-liquid interface of water using extensive molecular dynamics simulations. Hydrophobic polymers collapse into globular structures in bulk water but unfold and sample a broad range of conformations at the vapor-liquid interface of water. We show that adding a pair of charges to a hydrophobic polymer at the interface can dramatically change its conformations, stabilizing hairpinlike structures, with molecular details depending on the location of the charged pair in the sequence. The translational dynamics of homopolymers and heteropolymers are also different, whereas the homopolymers skate on the interface with low drag, the tendency of charged groups to remain hydrated pulls the heteropolymers toward the liquid side of the interface, thus pinning them, increasing drag, and slowing the translational dynamics. The conformational dynamics of heteropolymers are also slower than that of the homopolymer and depend on the location of the charged groups in the sequence. Conformational dynamics are most restricted for the end-charged heteropolymer and speed up as the charge pair is moved toward the center of the sequence. We rationalize these trends using the fundamental understanding of the effects of the interface on primitive pair-level interactions between two hydrophobic groups and between oppositely charged ions in its vicinity.

  2. Measurement of lateral adhesion forces at the interface between a liquid drop and a substrate.

    PubMed

    Tadmor, Rafael; Bahadur, Prashant; Leh, Aisha; N'guessan, Hartmann E; Jaini, Rajiv; Dang, Lan

    2009-12-31

    A novel instrument allows for the first time measurements of the lateral adhesion forces at a solid-liquid interface, f(parallel), in a way that is decoupled from the normal forces, f(perpendicular). We use it to measure how f(parallel) between a drop and a surface is influenced by different f(perpendicular) and different histories of drop resting periods on the surface prior to sliding, t(rest). The variation of f(parallel) with t(rest) is similar for different f(perpendicular) and always plateaus as t(rest)-->infinity. We show that the f(parallel) plateau value is higher when f(perpendicular) is lower. This seemingly counterintuitive result is in agreement with recent theories.

  3. Model of dynamic self-assembly in ferromagnetic suspensions at liquid interfaces

    NASA Astrophysics Data System (ADS)

    Piet, D. L.; Straube, A. V.; Snezhko, A.; Aranson, I. S.

    2013-09-01

    Ferromagnetic microparticles suspended at the interface between immiscible liquids and energized by an external alternating magnetic field show a rich variety of self-assembled structures, from linear snakes to radial asters. In order to obtain insight into the fundamental physical mechanisms and the overall balance of forces governing self-assembly, we develop a modeling approach based on analytical solutions of the time-averaged Navier-Stokes equations. These analytical expressions for the self-consistent hydrodynamic flows are then employed to modify effective interactions between the particles, which in turn are formulated in terms of the time-averaged quantities. Our method allows effective computational verification of the mechanisms of self-assembly and leads to a testable prediction, e.g., on the transitions between various patterns versus viscosity of the solvent.

  4. Physics of solid-liquid interfaces: From the Young equation to the superhydrophobicity (Review Article)

    NASA Astrophysics Data System (ADS)

    Bormashenko, Edward

    2016-08-01

    The state-of-art in the field of physics of phenomena occurring at solid/liquid interfaces is presented. The notions of modern physics of wetting are introduced and discussed including: the contact angle hysteresis, disjoining pressure and wetting transitions. The physics of low temperature wetting phenomena is treated. The general variational approach to interfacial problems, based on the application of the transversality conditions to variational problems with free endpoints is presented. It is demonstrated that main equations, predicting contact angles, namely the Young, Wenzel, and Cassie-Baxter equations arise from imposing the transversality conditions on the appropriate variational problem of wetting. Recently discovered effects such as superhydrophobicity, the rose petal effect and the molecular dynamic of capillarity are reviewed.

  5. Molecular threading: mechanical extraction, stretching and placement of DNA molecules from a liquid-air interface.

    PubMed

    Payne, Andrew C; Andregg, Michael; Kemmish, Kent; Hamalainen, Mark; Bowell, Charlotte; Bleloch, Andrew; Klejwa, Nathan; Lehrach, Wolfgang; Schatz, Ken; Stark, Heather; Marblestone, Adam; Church, George; Own, Christopher S; Andregg, William

    2013-01-01

    We present "molecular threading", a surface independent tip-based method for stretching and depositing single and double-stranded DNA molecules. DNA is stretched into air at a liquid-air interface, and can be subsequently deposited onto a dry substrate isolated from solution. The design of an apparatus used for molecular threading is presented, and fluorescence and electron microscopies are used to characterize the angular distribution, straightness, and reproducibility of stretched DNA deposited in arrays onto elastomeric surfaces and thin membranes. Molecular threading demonstrates high straightness and uniformity over length scales from nanometers to micrometers, and represents an alternative to existing DNA deposition and linearization methods. These results point towards scalable and high-throughput precision manipulation of single-molecule polymers.

  6. Poly(ethylene oxide) Mushrooms Adsorbed at Silica-Ionic Liquid Interfaces Reduce Friction.

    PubMed

    Sweeney, James; Webber, Grant B; Atkin, Rob

    2016-03-01

    The adsorbed layer conformation and lubricity of 35, 100, and 300 kDa PEO adsorbed to ionic liquid (IL)-silica interfaces from 0.01 wt % solutions have been investigated using colloid probe atomic force microscopy. The ILs used were propylammonium nitrate (PAN) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), which are protic and aprotic ILs, respectively. Normal force curves reveal steric interactions consistent with adsorbed polymer layers which are best fit using the mushroom model. Friction measurements show that the adsorbed polymer layer markedly reduces friction compared to surfaces sliding in the pure ILs and that lubricity increases with polymer length. When polymer is adsorbed to the sliding surfaces, friction is controlled by the creation and disruption of intermolecular interactions between entangled chains and the dragging of polymer chains through the interpenetration region. These experiments show that added polymer can reduce friction while maintaining the useful properties of ILs as lubricants.

  7. Neutron reflectivity studies on the DNA adsorption on lipid monolayers at the air liquid interface

    NASA Astrophysics Data System (ADS)

    Wu, Jui-Ching; Lin, Tsang-Lang; Jeng, U.-Ser; Torikai, Naoya

    2006-11-01

    In situ neutron reflectivity was used to study the DC-Chol and TC-Chol monolayers at the air-liquid interface in the presence and absence of DNA in the subphase. It was found that the DC-Chol is more effective in adsorbing the DNA than the TC-Chol. It was also found that a compact DNA layer formed beneath the DC-Chol monolayer with a DNA gap spacing around 20 Å and a less compact DNA layer adsorbed to the TC-Chol monolayer with a DNA spacing around 60 Å, as estimated from the determined neutron scattering length density. From the determined neutron scattering length density profiles, the adsorbed DNA somewhat penetrates into the head group region of the charged lipids.

  8. Studying dissolution with a model integrating solid-liquid interface kinetics and diffusion kinetics.

    PubMed

    Gao, Jeff Y

    2012-12-18

    A dissolution model that integrates the solid-liquid interface kinetics and the mass transport kinetics is introduced. Such a model reduces to the Noyes-Whitney equation under special conditions, but offers expanded range of applicability and flexibility fitting dissolution profiles when interfacial kinetics and interfacial concentration deviate from the assumptions implied in the Noyes-Whitney equation. General solutions to the integrated dissolution model derived for noninteractive solutes as well as for solutes participating in ionization equilibrium are discussed. Parameters defining the integrated dissolution model are explained conceptually along with practical ways for their determinations. Conditions under which the model exhibits supersaturation features are elaborated. Simulated dissolution profiles using the integrated dissolution model for published experimental data exhibiting supersaturation features are illustrated.

  9. Effect of thermosolutal convection on the solid-liquid interface in Pb-Au alloy

    NASA Technical Reports Server (NTRS)

    Tewari, S. N.; Chopra, M. A.

    1990-01-01

    Liquid-solid interface distortion in the region of primary dendrite tips has been investigated in directionally solidified Pb-8 wt pct Au alloy. The distortions are caused by thermosolutal convection despite choice of growth conditions which should have been thermally and solutally stabilizing. The convection produces clustering of primary dendrites on a plane perpendicular to the growth direction. It produces a mushy zone, where the primary dendrites do not protrude with a uniform length, across the specimen cross section, resulting in large macrosegregation in the transverse direction. However, little macrosegregation is observed along the growth direction. The mushy zone, with uneven dendrite lengths, forms in the beginning of directional solidification. Its shape and dendrite distribution do not show much change during subsequent solidification. Tip morphologies of primary dendrites, within the dendrite clusters, appear to follow the morphological stability relationship.

  10. Polarization-modulation infrared reflection-absorption spectroscopy affording time-resolved simultaneous detection of surface and liquid phase species at catalytic solid-liquid interfaces.

    PubMed

    Meier, Daniel M; Urakawa, Atsushi; Baiker, Alfons

    2009-09-01

    Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) combined with concentration modulation allows simultaneous monitoring of dynamic evolutions of surface and liquid phase species during reactions at catalytic interfaces as demonstrated for the Pt-catalysed oxidation of CO by O2 in cyclohexane.

  11. Design and Testing of a Solid-Liquid Interface Monitor for High-Level Waste Tanks

    SciTech Connect

    McDaniel, D.; Awwad, A.; Roelant, D.; Srivastava, R.

    2008-07-01

    A high-level waste (HLW) monitor has been designed, fabricated and tested at full-scale for deployment inside a Hanford tank. The Solid-Liquid Interface Monitor (SLIM) integrates a commercial sonar system with a mechanical deployment system for deploying into an underground waste tank. The system has undergone several design modifications based upon changing requirements at Hanford. We will present the various designs of the monitor from first to last and will present performance data from the various prototype systems. We will also present modeling of stresses in the enclosure under 85 mph wind loading. The system must be able to function at winds up to 15 mph and must withstand a maximum loading of 85 mph. There will be several examples presented of engineering tradeoffs made as FIU analyzed new requirements and modified the design to accommodate. We will present our current plans for installing into the Cold Test Facility at Hanford and into a double-shelled tank at Hanford. Finally, we will present our vision for how this technology can be used at Hanford and Savannah River Site to improve the filling and emptying of high-level waste tanks. In conclusion: 1. The manually operated first-generation SLIM is a viable option on tanks where personnel are allowed to work on top of the tank. 2. The remote controlled second-generation SLIM can be utilized on tanks where personnel access is limited. 3. The totally enclosed fourth-generation SLIM, when the design is finalized, can be used when the possibility exists for wind dispersion of any HLW that maybe on the system. 4. The profiling sonar can be used effectively for real-time monitoring of the solid-liquid interface over a large area. (authors)

  12. Stability and minimum size of colloidal clusters on a liquid-air interface

    NASA Astrophysics Data System (ADS)

    Pergamenshchik, V. M.

    2012-02-01

    A vertical force applied to each of two colloids, trapped at a liquid-air interface, induces their logarithmic pairwise attraction. I recently showed [Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.79.011407 79, 011407 (2009)] that in clusters of size R much larger than the capillary length λ, the attraction changes to that of a power law and is much stronger due to a many-body effect, and I derived two equations that describe the equilibrium coarse-grained meniscus profile and colloid density in such clusters. In this paper, this theory is shown also to describe small clusters with R≪ λ provided the number N of colloids therein is sufficiently large. An analytical solution for a small circular cluster with an arbitrary short-range power-law pairwise repulsion is found. The energy of a cluster is obtained as a function of its radius R and colloid number N. As in large clusters, the attraction force and energy universally scale with the distance L between colloids as L-3 and L-2, respectively, for any repulsion forces. The states of an equilibrium cluster, predicted by the theory, are shown to be stable with respect to small perturbations of the meniscus profile and colloid density. The minimum number of colloids in a circular cluster, which sustains the thermal motion, is estimated. For standard parameters, it can be very modest, e.g., in the range 20-200, which is in line with experimental findings on reversible clusterization on a liquid-air interface.

  13. A Computational Study of Dicationic Ionic Liquids/CO2 Interfaces

    SciTech Connect

    Li, Song; Zhao, Wei; Feng, Guang; Cummings, Peter T.

    2015-02-09

    Our recent studies on CO2 capture using dicationic ionic liquids (DILs) demonstrated that DILs are promising absorbents for CO2 uptake especially compared with monocationic ionic liquids (MILs) analogues, in which each cation carries single positive charge in contrast to two unit charges of a dication. However, DILs/CO2 interfacial properties at the molecular level are still unknown. This work investigated the CO2 absorption properties of representative DILs, 1-alkyl-3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [Cn(mim)2](Tf2N)2 (n = 3, 6, 12), using molecular dynamics (MD) simulations. The higher interfacial CO2 density at DIL than that at MIL interfaces suggests the increased CO2 interaction sites in DILs. The interfacial CO2 density also exhibits an alkyl chain length dependence which decreases with the elongation of alkyl chain and proportionally correlates with the content of fluorine atoms at interfaces. Different alkyl chain orientations in DILs were illustrated in contrast to those of MILs; both DILs and CO2 inside DILs exhibit lower diffusivity than MILs, in agreement with the stronger cation–anion binding energy of DILs. Moreover, DILs show a lower H2O and N2 uptake from flue gas compared with MILs, implicating the higher CO2/H2O and CO2/N2 selectivity.

  14. Scanning tunneling microscopy study of molecular order at liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Magonov, S. N.; Wawkuschewski, A.; Cantow, H.-J.; Liang, W.; Whangbo, M.-H.

    1994-08-01

    Adsorbates of normal alkane C36H74, cycloalkanes (CH2)48 and (CH2)72, decanol C10H21OH, 4-hexyl-4'-CyanoBiphenyl (6CB) and 4-octyl-4t'-CyanoBiphenyl (8CB) on graphite and β-Nb3I8 were studied by Scanning Tunneling Microscopy (STM), and the molecular arrangements at the liquid-solid interface were examined. Large-scale STM images show that the adsorbates possess complex multilayered structures, and that molecular ordering at the liquid-solid interfaces occurs primarily in the immediate vicinity of the substrate. Molecular-scale STM images are primarily determined by the electronic contributions of the most protruded atoms of the topmost overlayer. The underlying overlayers and the substrate affect the images indirectly by perturbing the topography of the topmost overlayer. The STM images of the adsorbates on graphite show that the atomically flat surface of graphite leads organic molecules to form lamella-like structures, while on the grooved surface of β-Nb3I8, long chain-like molecules are trapped in the grooves. We were unable to image the cycloalkanes on β-Nb3I8, which suggests that the cycloalkanes cannot assemble on the grooved surface due to a mismatch between the molecular shape and surface topography. The layers of 6CB and 8CB adsorbed on β-Nb3I8 exhibit two types of domains, which may be related to how the grooves of the β-Nb3I8 surface are occupied by the organic molecules. The STM images of decanol adsorbed on β-Nb3I8 show two domains of different brightness. The relative brightness of these domains switches reversibly as the gap resistance is changed in the region around -60 MΩ.

  15. Liquid-Air Interface Corrosion Testing Simulating The Environment Of Hanford Double Shell Tanks

    SciTech Connect

    Wiersma, B.; Gray, J. R.; Garcia-Diaz, B. L.; Murphy, T. H.; Hicks, K. R.

    2014-01-30

    Coupon tests on A537 carbon steel materials were conducted to evaluate the Liquid-Air Interface (LAI) corrosion susceptibility in a series of solutions designed to simulate conditions in the radioactive waste tanks located at the Hanford Nuclear Facility. The new stress corrosion cracking requirements and the impact of ammonia on LAI corrosion were the primary focus. The minimum R value (i.e., molar ratio of nitrite to nitrate) of 0.15 specified by the new stress corrosion cracking requirements was found to be insufficient to prevent pitting corrosion at the LAI. The pH of the test solutions was 10, which was actually less than the required pH 11 defined by the new requirements. These tests examined the effect of the variation of the pH due to hydroxide depletion at the liquid air interface. The pits from the current testing ranged from 0.001 to 0.008 inch in solutions with nitrate concentrations of 0.4 M and 2.0 M. The pitting and general attack that occurred progressed over the four-months. No significant pitting was observed, however, for a solution with a nitrate concentration of 4.5 M. The pitting depths observed in these partial immersion tests in unevaporated condensates ranged from 0.001 to 0.005 inch after 4 months. The deeper pits were in simulants with low R values. Simulants with R values of approximately 0.6 to 0.8 appeared to significantly reduce the degree of attack. Although, the ammonia did not completely eliminate attack at the LAI, the amount of corrosion in an extremely corrosive solution was significantly reduced. Only light general attack (< 1 mil) occurred on the coupon in the vicinity of the LAI. The concentration of ammonia (i.e., 50 ppm or 500 ppm) did not have a strong effect.

  16. Bubble Induced Disruption of a Planar Solid-Liquid Interface During Controlled Directional Solidification in a Microgravity Environment

    NASA Technical Reports Server (NTRS)

    Grugel, Richard N.; Brush, Lucien N.; Anilkumar, Amrutur V.

    2013-01-01

    Pore Formation and Mobility Investigation (PFMI) experiments were conducted in the microgravity environment aboard the International Space Station with the intent of better understanding the role entrained porosity/bubbles play during controlled directional solidification. The planar interface in a slowing growing succinonitrile - 0.24 wt% water alloy was being observed when a nitrogen bubble traversed the mushy zone and remained at the solid-liquid interface. Breakdown of the interface to shallow cells subsequently occurred, and was later evaluated using down-linked data from a nearby thermocouple. These results and other detrimental effects due to the presence of bubbles during solidification processing in a microgravity environment are presented and discussed.

  17. Adsorption of hydrophobin/β-casein mixtures at the solid-liquid interface.

    PubMed

    Tucker, I M; Petkov, J T; Penfold, J; Thomas, R K; Cox, A R; Hedges, N

    2016-09-15

    The adsorption behaviour of mixtures of the proteins β-casein and hydrophobin at the hydrophilic solid-liquid surface have been studied by neutron reflectivity. The results of measurements from sequential adsorption and co-adsorption from solution are contrasted. The adsorption properties of protein mixtures are important for a wide range of applications. Because of competing factors the adsorption behaviour of protein mixtures at interfaces is often difficult to predict. This is particularly true for mixtures containing hydrophobin as hydrophobin possesses some unusual surface properties. At β-casein concentrations ⩾0.1wt% β-casein largely displaces a pre-adsorbed layer of hydrophobin at the interface, similar to that observed in hydrophobin-surfactant mixtures. In the composition and concentration range studied here for the co-adsorption of β-casein-hydrophobin mixtures the adsorption is dominated by the β-casein adsorption. The results provide an important insight into how the competitive adsorption in protein mixtures of hydrophobin and β-casein can impact upon the modification of solid surface properties and the potential for a wide range of colloid stabilisation applications.

  18. Liquid-vapor interfaces in XY -spin fluids: an inhomogeneous anisotropic integral-equation approach.

    PubMed

    Omelyan, I P; Folk, R; Kovalenko, A; Fenz, W; Mryglod, I M

    2009-01-01

    An integral-equation approach is developed to study interfacial properties of anisotropic fluids with planar spins in the presence of an external magnetic field. The approach is based on the coupled set of the Lovett-Mou-Buff-Wertheim integro-differential equation for the inhomogeneous anisotropic one-particle density and the Ornstein-Zernike equation for the orientationally dependent two-particle correlation functions. Using the proposed inhomogeneous angle-harmonics expansion formalism we show that these integral equations can be reduced to a much simpler form similar to that inherent for a system of isotropic fluids. The interfacial orientationally dependent direct correlation function can be consistently constructed by means of a nonlinear interpolation via its values obtained in the coexisting anisotropic bulk phases. A soft mean spherical approximation is employed for the closure relation. This has allowed us to solve the complicated integral equations in the situation when both spatial inhomogeneity and orientational anisotropy are present simultaneously. The approach introduced is applied to an XY fluid model with ferromagnetic spin interactions. As a result, the density-orientation and magnetization profiles at the liquid-vapor interfaces are calculated in a wide range of temperatures up to subcritical regions. The influence of the external field on the microscopic structure of the interfaces and the surface tension is also analyzed in detail.

  19. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    SciTech Connect

    Soniat, Marielle; Rick, Steven W.; Kumar, Revati

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  20. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    NASA Astrophysics Data System (ADS)

    Soniat, Marielle; Kumar, Revati; Rick, Steven W.

    2015-07-01

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water's liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  1. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water.

    PubMed

    Soniat, Marielle; Kumar, Revati; Rick, Steven W

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water's liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  2. A control volume study of the pressure tensor across a liquid-vapour interface

    NASA Astrophysics Data System (ADS)

    Braga, Carlos; Yatsyshin, Petr; Smith, Edward; Nold, Andreas; Goddard, Benjamin; Savva, Nikos; Schmuck, Markus; Duncan, Andrew; Sibley, David; Kalliadasis, Serafim

    2015-11-01

    The presence of an interface renders the properties of the system position dependent. The pressure tensor will no longer be uniform nor isotropic giving rise to the surface tension. The theory of Kirkwood-Buff gives a formal description of the surface tension based on the analysis of the local pressure tensor while capillary wave theory assumes the existence of an instantaneous intrinsic surface separating the liquid and vapour. Analysis of its Fourier components gives both structural and dynamical routes to compute the surface based on hydrodynamic theory. The defining equation of a capillary surface is given by the stress balance between the pressure tensors and the surface tension. Here, we employ the instantaneous interface as a representative surface across which we compute the local pressures following the seminal work of Irving and Kirkwood. The control volume approach to the Irving-Kirkwood expressions provides an exact balance between the stress and momentum transfer across the surface element allowing the study of the surface tension from a mechanical standpoint. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.

  3. Getting in shape: molten wax drop deformation and solidification at an immiscible liquid interface.

    PubMed

    Beesabathuni, Shilpa N; Lindberg, Seth E; Caggioni, Marco; Wesner, Chris; Shen, Amy Q

    2015-05-01

    The controlled production of non-spherical shaped particles is important for many applications such as food processing, consumer goods, adsorbents, drug delivery, and optical sensing. In this paper, we investigated the deformation and simultaneous solidification of millimeter size molten wax drops as they impacted an immiscible liquid interface of higher density. By varying initial temperature and viscoelasticity of the molten drop, drop size, impact velocity, viscosity and temperature of the bath fluid, and the interfacial tension between the molten wax and bath fluid, spherical molten wax drops impinged on a cooling water bath and were arrested into non-spherical solidified particles in the form of ellipsoid, mushroom, disc, and flake-like shapes. We constructed cursory phase diagrams for the various particle shapes generated over a range of Weber, Capillary, Reynolds, and Stefan numbers, governed by the interfacial, inertial, viscous, and thermal effects. We solved a simplified heat transfer problem to estimate the time required to initiate the solidification at the interface of a spherical molten wax droplet and cooling aqueous bath after impact. By correlating this time with the molten wax drop deformation history captured from high speed imaging experiments, we elucidate the delicate balance of interfacial, inertial, viscous, and thermal forces that determine the final morphology of wax particles.

  4. Effect of interface fertilization on biodegradation of polycyclic aromatic hydrocarbons present in nonaqueous-phase liquids.

    PubMed

    Tejeda-Agredano, M C; Gallego, S; Niqui-Arroyo, J L; Vila, J; Grifoll, M; Ortega-Calvo, J J

    2011-02-01

    The main goal of this study was to use an oleophilic biostimulant (S-200) to target possible nutritional limitations for biodegradation of polycyclic aromatic hydrocarbons (PAHs) at the interface between nonaqueous-phase liquids (NAPLs) and the water phase. Biodegradation of PAHs present in fuel-containing NAPLs was slow and followed zero-order kinetics, indicating bioavailability restrictions. The biostimulant enhanced the biodegradation, producing logistic (S-shaped) kinetics and 10-fold increases in the rate of mineralization of phenanthrene, fluoranthene, and pyrene. Chemical analysis of residual fuel oil also evidenced an enhanced biodegradation of the alkyl-PAHs and n-alkanes. The enhancement was not the result of an increase in the rate of partitioning of PAHs into the aqueous phase, nor was it caused by the compensation of any nutritional deficiency in the medium. We suggest that biodegradation of PAH by bacteria attached to NAPLs can be limited by nutrient availability due to the simultaneous consumption of NAPL components, but this limitation can be overcome by interface fertilization.

  5. A dose-controlled system for air-liquid interface cell exposure and application to zinc oxide nanoparticles

    PubMed Central

    2009-01-01

    Background Engineered nanoparticles are becoming increasingly ubiquitous and their toxicological effects on human health, as well as on the ecosystem, have become a concern. Since initial contact with nanoparticles occurs at the epithelium in the lungs (or skin, or eyes), in vitro cell studies with nanoparticles require dose-controlled systems for delivery of nanoparticles to epithelial cells cultured at the air-liquid interface. Results A novel air-liquid interface cell exposure system (ALICE) for nanoparticles in liquids is presented and validated. The ALICE generates a dense cloud of droplets with a vibrating membrane nebulizer and utilizes combined cloud settling and single particle sedimentation for fast (~10 min; entire exposure), repeatable (<12%), low-stress and efficient delivery of nanoparticles, or dissolved substances, to cells cultured at the air-liquid interface. Validation with various types of nanoparticles (Au, ZnO and carbon black nanoparticles) and solutes (such as NaCl) showed that the ALICE provided spatially uniform deposition (<1.6% variability) and had no adverse effect on the viability of a widely used alveolar human epithelial-like cell line (A549). The cell deposited dose can be controlled with a quartz crystal microbalance (QCM) over a dynamic range of at least 0.02-200 μg/cm2. The cell-specific deposition efficiency is currently limited to 0.072 (7.2% for two commercially available 6-er transwell plates), but a deposition efficiency of up to 0.57 (57%) is possible for better cell coverage of the exposure chamber. Dose-response measurements with ZnO nanoparticles (0.3-8.5 μg/cm2) showed significant differences in mRNA expression of pro-inflammatory (IL-8) and oxidative stress (HO-1) markers when comparing submerged and air-liquid interface exposures. Both exposure methods showed no cellular response below 1 μg/cm2 ZnO, which indicates that ZnO nanoparticles are not toxic at occupationally allowed exposure levels. Conclusion The ALICE

  6. Solid-liquid interface free energies of pure bcc metals and B2 phases

    SciTech Connect

    Wilson, S. R.; Gunawardana, K. G. S. H.; Mendelev, M. I.

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3¯m ; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic “Na” potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observed in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of “Na” potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Thus, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.

  7. Dynamic covalent chemistry of bisimines at the solid/liquid interface monitored by scanning tunnelling microscopy

    NASA Astrophysics Data System (ADS)

    Ciesielski, Artur; El Garah, Mohamed; Haar, Sébastien; Kovaříček, Petr; Lehn, Jean-Marie; Samorì, Paolo

    2014-11-01

    Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.

  8. Stable silicon-ionic liquid interface for next-generation lithium-ion batteries.

    PubMed

    Molina Piper, Daniela; Evans, Tyler; Leung, Kevin; Watkins, Tylan; Olson, Jarred; Kim, Seul Cham; Han, Sang Sub; Bhat, Vinay; Oh, Kyu Hwan; Buttry, Daniel A; Lee, Se-Hee

    2015-02-25

    We are currently in the midst of a race to discover and develop new battery materials capable of providing high energy-density at low cost. By combining a high-performance Si electrode architecture with a room temperature ionic liquid electrolyte, here we demonstrate a highly energy-dense lithium-ion cell with an impressively long cycling life, maintaining over 75% capacity after 500 cycles. Such high performance is enabled by a stable half-cell coulombic efficiency of 99.97%, averaged over the first 200 cycles. Equally as significant, our detailed characterization elucidates the previously convoluted mechanisms of the solid-electrolyte interphase on Si electrodes. We provide a theoretical simulation to model the interface and microstructural-compositional analyses that confirm our theoretical predictions and allow us to visualize the precise location and constitution of various interfacial components. This work provides new science related to the interfacial stability of Si-based materials while granting positive exposure to ionic liquid electrochemistry.

  9. Observation of gaseous films at solid-liquid interfaces: removal by ultrasonic action.

    PubMed

    Zbik, Marek S; Du, Jianhua; Pushkarova, Rada A; Smart, Roger St C

    2009-08-15

    The critical role of dissolved gas nano-bubbles at solid surfaces in particle association, aggregation, adsorption and flotation has been recognised in the recent literature. The principles of mineral processing, fine particle separation, and water recovery depend upon changing the surface properties at the solid-liquid interface. It has been assumed that the solid surfaces are either in direct contact with the liquid or may have nano-bubbles attached only at hydrophobic surfaces. This paper shows that gaseous layers 50-100 nm thick can be attached surrounding high proportions of solid clay mineral surfaces restricting reagent access, producing buoyancy and aggregation. Ultrasonic treatment before flocculant addition effectively removes these gaseous layers as well as dispersed micro-bubbles. Re-aggregation after brief ultrasonication produces denser (less buoyant) flocs, demonstrated with cryo-SEM statistical analysis, giving more complete access of the flocculant to the aggregate surfaces. In the subsequent flocculant addition, the settling rates of the denser flocs can be increased up to 40%. If ultrasonic action is continued, the bridged flocs are disturbed with some redispersion of smaller flocs and individual platelets and consequent slower settling rates.

  10. Contact-angle hysteresis on periodic microtextured surfaces: Strongly corrugated liquid interfaces.

    PubMed

    Iliev, Stanimir; Pesheva, Nina

    2016-06-01

    We study numerically the shapes of a liquid meniscus in contact with ultrahydrophobic pillar surfaces in Cassie's wetting regime, when the surface is covered with identical and periodically distributed micropillars. Using the full capillary model we obtain the advancing and the receding equilibrium meniscus shapes when the cross-sections of the pillars are both of square and circular shapes, for a broad interval of pillar concentrations. The bending of the liquid interface in the area between the pillars is studied in the framework of the full capillary model and compared to the results of the heterogeneous approximation model. The contact angle hysteresis is obtained when the three-phase contact line is located on one row (block case) or several rows (kink case) of pillars. It is found that the contact angle hysteresis is proportional to the line fraction of the contact line on pillars tops in the block case and to the surface fraction for pillar concentrations 0.1-0.5 in the kink case. The contact angle hysteresis does not depend on the shape (circular or square) of the pillars cross-section. The expression for the proportionality of the receding contact angle to the line fraction [Raj et al., Langmuir 28, 15777 (2012)LANGD50743-746310.1021/la303070s] in the case of block depinning is theoretically substantiated through the capillary force, acting on the solid plate at the meniscus contact line.

  11. Solid-liquid interface free energies of pure bcc metals and B2 phases.

    PubMed

    Wilson, S R; Gunawardana, K G S H; Mendelev, M I

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3̄m; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic "Na" potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observed in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of "Na" potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Moreover, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.

  12. Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening.

    PubMed

    Comtet, Jean; Niguès, Antoine; Kaiser, Vojtech; Coasne, Benoit; Bocquet, Lydéric; Siria, Alessandro

    2017-03-27

    Room-temperature ionic liquids (RTILs) are new materials with fundamental importance for energy storage and active lubrication. They are unusual liquids, which challenge the classical frameworks of electrolytes, whose behaviour at electrified interfaces remains elusive, with exotic responses relevant to their electrochemical activity. Using tuning-fork-based atomic force microscope nanorheological measurements, we explore here the properties of confined RTILs, unveiling a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to capillary freezing in confinement. This threshold is related to the metallic nature of the confining materials, with more metallic surfaces facilitating freezing. This behaviour is interpreted in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces. Our findings provide fresh views on the properties of confined RTIL with implications for their properties inside nanoporous metallic structures, and suggests applications to tune nanoscale lubrication with phase-changing RTILs, by varying the nature and patterning of the substrate, and application of active polarization.

  13. Processing of alumina-niobium interfaces via liquid-film-assistedjoining

    SciTech Connect

    McKeown, Joseph T.; Sugar, Joshua D.; Gronsky, Ronald; Glaeser,Andreas M.

    2005-02-15

    Alumina-niobium interfaces were fabricated at 1400 C via solid-state diffusion brazing of a 127-{micro}m-thick niobium foil between alumina blocks. Prior to brazing, some of the alumina mating surfaces, both polished and unpolished, were evaporation-coated with copper films {approx}1.4 {micro}m, {approx}3.0 {micro}m, and {approx}5.5 {micro}m thick to induce liquid-film-assisted joining at the brazing temperature. The effects of copper film thickness and surface roughness on fracture characteristics and ceramic-metal interfacial microstructure were investigated by room-temperature four-point bend tests, optical microscopy, profilometry, and atomic force microscopy. The average strength of bonds between niobium and polished alumina substrates increased with the introduction of copper film interlayers, and the scatter in strength tended to decrease, with an optimum combination of strength and Weibull modulus arising for a copper film thickness of 3.0 {micro}m. The strength characteristics of niobium bonded to unpolished alumina substrates were also improved by liquid-film-assisted joining, but were unaffected by the thickness of the copper interlayers.

  14. Solid-liquid interface free energies of pure bcc metals and B2 phases

    DOE PAGES

    Wilson, S. R.; Gunawardana, K. G. S. H.; Mendelev, M. I.

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3¯m ; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic “Na” potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observedmore » in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of “Na” potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Thus, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.« less

  15. Contact-angle hysteresis on periodic microtextured surfaces: Strongly corrugated liquid interfaces

    NASA Astrophysics Data System (ADS)

    Iliev, Stanimir; Pesheva, Nina

    2016-06-01

    We study numerically the shapes of a liquid meniscus in contact with ultrahydrophobic pillar surfaces in Cassie's wetting regime, when the surface is covered with identical and periodically distributed micropillars. Using the full capillary model we obtain the advancing and the receding equilibrium meniscus shapes when the cross-sections of the pillars are both of square and circular shapes, for a broad interval of pillar concentrations. The bending of the liquid interface in the area between the pillars is studied in the framework of the full capillary model and compared to the results of the heterogeneous approximation model. The contact angle hysteresis is obtained when the three-phase contact line is located on one row (block case) or several rows (kink case) of pillars. It is found that the contact angle hysteresis is proportional to the line fraction of the contact line on pillars tops in the block case and to the surface fraction for pillar concentrations 0.1 -0.5 in the kink case. The contact angle hysteresis does not depend on the shape (circular or square) of the pillars cross-section. The expression for the proportionality of the receding contact angle to the line fraction [Raj et al., Langmuir 28, 15777 (2012), 10.1021/la303070s] in the case of block depinning is theoretically substantiated through the capillary force, acting on the solid plate at the meniscus contact line.

  16. Chemistry at the square nanometer: reactivity at liquid/solid interfaces revealed with an STM.

    PubMed

    Münninghoff, Joris A W; Elemans, Johannes A A W

    2017-02-02

    For more than three decades the scanning tunnelling microscope (STM) has proven to be an indispensable tool to image molecules adsorbed at a surface at the highest detail possible. In addition to simply imaging molecules, STM can also be applied to monitor dynamic surface phenomena, including chemical reactions. By studying reactions at a surface at the single molecule level, unique information about reaction mechanisms can be obtained which remains hidden when conventional ensemble techniques are used. Many STM studies of chemical reactions have been performed in extreme environments like ultrahigh vacuum or high pressure chambers, but these are far removed from conditions in which most chemical and biological processes take place, i.e., in a liquid at ambient atmospheres. This feature paper highlights the developments in the relatively unexplored research area of investigating chemical reactions with an STM at a liquid/solid interface under ambient conditions. Covalent couplings between molecules, light-induced isomerisations, reactions under electrochemical control, and complex multistep processes and catalysis are discussed.

  17. Long-wave theory of bounded two-layer films with a free liquid-liquid interface: Short- and long-time evolution

    NASA Astrophysics Data System (ADS)

    Merkt, D.; Pototsky, A.; Bestehorn, M.; Thiele, U.

    2005-06-01

    We consider two layers of immiscible liquids confined between an upper and a lower rigid plate. The dynamics of the free liquid-liquid interface is described for arbitrary amplitudes by an evolution equation derived from the basic hydrodynamic equations using long-wave approximation. After giving the evolution equation in a general way, we focus on interface instabilities driven by gravity, thermocapillary and electrostatic fields. First, we study the linear stability discussing especially the conditions for destabilizing the system by heating from above or below. Second, we use a variational formulation of the evolution equation based on an energy functional to predict metastable states and the long-time pattern morphology (holes, drops or maze structures). Finally, fully nonlinear three-dimensional numerical integrations are performed to study the short- and long-time evolution of the evolving patterns. Different coarsening modes are discussed and long-time scaling exponents are extracted.

  18. Properties of the solid-liquid interface of growing salol crystals: A dynamic light scattering investigation

    NASA Astrophysics Data System (ADS)

    Dürig, U.; Bilgram, J. H.; Känzig, W.

    1984-08-01

    The freezing process has been studied by means of quasielastic light scattering at the solid-liquid interface of growing salol crystals. In the range of the investigated growth velocities, 0.2 μms<=vk<=0.8 μms, we observe two different dynamical processes at the interface, which can be distinguished by the scattered light. In a first process intense Rayleigh scattering sets in if a critical growth velocity is exceeded, which for growth along the [010] axis is in the range of 0.2 μms<=vcrit<=0.8 μms. Intensity measurements suggest that the scattering arises from fluctuations in an interface layer of a thickness of the order of 1μm. The spectrum of the scattered light can be fitted by a single Lorenzian with a linewidth Γ=Diq2 (q--> is the scattering vector). The thus obtained value of the diffusion constant, Di=(1.0+/-0.25)×10-9 cm2 s-1, is by 6 orders of magnitude smaller than the thermal diffusivity of liquid salol. In a second process the light is scattered by a propagating line-grating-like structure, which we interpret in terms of almost equidistant steps of growth spirals originating at screw dislocations. The step spacing d was determined from the angular distribution of the scattered intensity, and the step velocity vs from the Doppler shift. For a growth velocity vk=0.5 μm/s perpendicular to the (001) facet typical values are d=0.4 μm and vs=40 μm/s. For the step height h=vkdvs we obtain values of the order of 2.5 lattice constants. The product vsd is independent of vk and has a value of (1.8+/-0.4)×10-7 cm2 s-1, whereas vs is proportional to the square root of vk. An interpretation of the data is presented.

  19. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy.

    PubMed

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons

    2014-08-01

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.

  20. Ultrasonic measurement of solid/liquid interface position during solidification and melting of metals

    NASA Astrophysics Data System (ADS)

    Parker, R. L.

    1982-05-01

    The use of pulse-echo ultrasonic flaw detectors to detect the presence and location of cracks, voids, and other discontinuities in metals and non-metal is well known. The solid-liquid interface in a melting or freezing metal can also be considered as a discontinuity, in that there is a measurable difference in both sound velocity and density across the interface. For normal incidence of longitudinal waves in a typical case, about 10% of the pressure amplitude of the incident wave would be expected to be reflected. Thus such a technique, if it worked, could be considered as a method for measurement, feedback, and closed-loop process control in such applications as continuous casting of metals. To examine the feasibility of this technique, the melting and freezing of 99.9 Sn has been studied at NBS using pulse-echo equipment at a nominal frequency of 5MHz. The transducer contacts the cold end of a 5/16″ × 8″ specimen in a graphite mold in a Bridgman gradient furnace (unidirectional melting/solidification). Sharp echoes easily locate the interface position, in both freezing and melting, to ±1 mm, over the range of interface velocities tested (up to˜4mm/min). A literature search showed that similar or related tests have been made by at least 5 other groups in the U. S. and abroad, in a number of materials and geometries. Most of them were also successful in locating the interface. In the relatively difficult case of steel, while interfaces could be located under certain conditions, there were also found some substantial problems involving signal attenuation and poor signal/noise ratios. Some possible causes for this could be poor reflection of the incident beam from the dendritic ″mushy zone″ in the case of alloys, as well as bulk attenuation effects due to grain size or other scattering centers. In the case of continuous castings, the coupling of the acoustic energy into hot, rough and scaly surfaces presents additional problems. However, much progress has

  1. Computational Studies of Structures and Dynamics of 1, 3-Dimethylimidazolim Salt Liquid and their Interfaces Using Polarizable Potential Models

    SciTech Connect

    Chang, Tsun-Mei; Dang, Liem X.

    2009-03-12

    The structures, thermodynamics, dynamical properties of bulk and air/liquid interfaces of three ionic liquids, 1,3-dimethylimidazolium [dmim]+, Cl-, Br-, and I- are studied using molecular dynamics techniques. In bulk melts, the radial distribution functions reveal a significant long-range structural correlation in these ionic liquids. From the angular distribution analysis, the imidazolium rings are found to lie parallel to each other at short distances, consistent with the structures observed in the crystal state. The single-ion dynamics are studied via mean-square-displacements, velocity and orientational correlation functions. The diffusion coefficients and reorientational times are found to be much smaller than H2O. We also observe that anion size plays an important role in the dynamics of ionic liquids. The computed density profiles of the ionic liquid/vapor interface exhibit oscillatory behavior, indicative of surface layering at the interface. Further analysis reveals that the [dmim]+ ions show preferred orientation at the interface with the ring parallel to the surface and methyl group attached to the ring pointing into the vapor phase. The computed surface tensions indicated small differences between these ionic liquids and are inline with recent experimental measurements. The calculated potential drops of these ionic liquids are found to be small and negative. These results could imply that the cation dipoles are likely to orient in the plane that parallel to the surface normal axis. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  2. Growth of human bronchial epithelial cells at an air-liquid interface alters the response to particle exposure

    EPA Science Inventory

    Abstract: We tested the hypothesis that relative to submerged cells, airway epithelial cells grown at an air-liquid interface would have an altered response to particle exposure. RNA for IL-8, IL-6, heme oxygenase 1 and cyclooxygenase 2 increased following exposure of submer...

  3. Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

    DOEpatents

    Yu, Xiao-Ying; Liu, Bingwen; Yang, Li; Zhu, Zihua; Marshall, Matthew J.

    2016-03-01

    A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

  4. Polysaccharide films at an air/liquid and a liquid/silicon interface: effect of the polysaccharide and liquid type on their physical properties.

    PubMed

    Taira, Yasunori; McNamee, Cathy E

    2014-11-14

    We investigated the effect of the polysaccharide type, the subphase on which the Langmuir monolayers were prepared, and the liquid in which the properties of the transferred monolayers were measured on the physical properties of the polysaccharide films at an air/aqueous interface and at a silicon substrate, and the forces and friction of the polysaccharide transferred films when measured in solution against a silica probe. Chitosan was modified with a silane coupling agent to make chitosan derived compounds with a low and a medium molecular weight. Chitin and the chitosan-derived compounds were used to make Langmuir monolayers at air/water and air/pH 9 buffer interfaces. The monolayers were transferred to silicon substrates via Langmuir-Blodgett deposition, and the chitosan-derived compounds subsequently chemically reacted with the silicon substrates. Atomic force microscope force and friction measurements were made in water and in the pH 9 buffer, where the water and the pH 9 buffer acted as a good and a bad solvent for the polysaccharides, respectively. The polysaccharide type affected the friction of the polysaccharide film, where the physically adsorbed chitin gave the lowest friction. The friction of L-chitosan was higher than that of M-chitosan in water, suggesting that the molecular weight of the polymer affects its lubricating ability. The forces and friction of the polysaccharide films changed when the subphase on which the Langmuir monolayers were formed was changed or when the liquid in which the properties of the films adsorbed at the silicon substrate were measured was changed. The friction increased significantly when the liquid was changed from water to the pH 9 buffer. This increase was explained by the reduced charge of the chitin and chitosan-derived materials due to the pH increase, the screening of the charges by the salts in the buffer, and the possible hardening of the monolayer caused by the adsorption of salts from the buffer.

  5. Reflection at a liquid-solid interface of a transient ultrasonic field radiated by a linear phased array transducer.

    PubMed

    Maghlaoui, Nadir; Belgroune, Djema; Ourak, Mohamed; Djelouah, Hakim

    2016-09-01

    In order to put in evidence the specular reflection and the non-specular reflection in the transient case, we have used a model for the study of the transient ultrasonic waves radiated by a linear phased array transducer in a liquid and reflected by a solid plane interface. This method is an extension of the angular spectrum method to the transient case where the reflection at the plane interface is taken into account by using the reflection coefficient for harmonic plane waves. The results obtained highlighted the different components of the ultrasonic field: the direct and edge waves as well as the longitudinal head waves or leaky Rayleigh waves. The transient representation of these waves have been carefully analyzed and discussed by the rays model. Instantaneous cartographies allowed a clear description of all the waves which appear at the liquid-solid interface. The obtained results have been compared to those obtained with a finite element method package.

  6. Formation and characterization of phospholipid monolayers spontaneously assembled at interfaces between aqueous phases and thermotropic liquid crystals.

    PubMed

    Brake, Jeffrey M; Daschner, Maren K; Abbott, Nicholas L

    2005-03-15

    This paper reports an experimental investigation of the self-assembly of phospholipids (l-alpha-phosphatidylcholine-beta-oleoyl-gamma-palmitoyl (l-POPC), dipalmitoyl phosphatidylcholine (DPPC), and l-alpha-dilauroyl phosphatidylcholine (l-DLPC)) at interfaces between aqueous phases and the nematic liquid crystal (LC) 4'-pentyl-4-cyanobiphenyl. Stable planar interfaces between the aqueous phases and LCs were created by hosting the LCs within gold grids (square pores with widths of 283 microm and depths of 20 microm). At these interfaces, the presence and lateral organization of the phospholipids leads to interface-driven orientational transitions within the LC. By doping the phospholipids with a fluorescently labeled lipid (Texas Red-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (TR-DPPE)), quantitative epifluorescence microscopy revealed the saturation coverage of phospholipid at the interface to be that of a monolayer with an areal density of approximately 49 +/- 8% relative to hydrated lipid bilayers. By adsorbing phospholipids to the aqueous-LC interface from either vesicles or mixed micelles of dodecyltrimethylammonium and phospholipid, control of the areal density of phospholipid from 42 +/- 10 to 102 +/-18% of saturation monolayer coverage was demonstrated. Fluorescence recovery after photobleaching (FRAP) experiments performed by using laser scanning confocal microscopy (LSCM) revealed the lateral mobility of fluorescently labeled DPPE in l-DLPC assembled at the interface with the liquid crystal to be (6 +/- 1) x 10(-12) m(2)/s for densely packed monolayers. Variation of the surface coverage and composition of phospholipid led to changes in lateral diffusivity between (0.2 +/- 0.1) x 10(-12) and (15 +/- 2) x 10(-12) m(2)/s. We also observed the phospholipid-laden interface to be compartmentalized by the gold grid, thus allowing for the creation of patterned arrays of phospholipids at the LC-aqueous interface.

  7. A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces

    SciTech Connect

    Starr, David E.; Wong, Ed K.; Worsnop, Douglas R.; Wilson, Kevin R.; Bluhm, Hendrik

    2008-05-01

    We describe a combined ambient pressure photoelectron spectroscopy/droplet train apparatus for investigating the nature and heterogeneous chemistry of liquid/vapor interfaces. In this instrument a liquid droplet train with typical droplet diameters from 50...150 {micro}m is produced by a vibrating orifice aerosol generator (VOAG). The droplets are irradiated by soft X-rays (100...1500 eV) in front of the entrance aperture of a differentially pumped electrostatic lens system that transfers the emitted electrons into a conventional hemispherical electron analyzer. The photoemission experiments are performed at background pressures of up to several Torr, which allows the study of environmentally important liquid/vapor interfaces, in particular aqueous solutions, under equilibrium conditions. The exposure time of the droplet surface to the background gases prior to the XPS measurement can be varied, which will allow future kinetic measurements of gas uptake on liquid surfaces. As an example, a measurement of the surface composition of a {chi} = 0.21 aqueous methanol solution is presented. The concentration of methanol at the vapor/liquid interface is enhanced by a factor of about 3 over the bulk value, while the expected bulk value is recovered at depths larger than about 1.5 nm.

  8. Ionic Liquid Films at the Water-Air Interface: Langmuir Isotherms of Tetra-alkylphosphonium-Based Ionic Liquids.

    PubMed

    Shimizu, Karina; Canongia Lopes, José N; Gonçalves da Silva, Amélia M P S

    2015-08-04

    The behavior of ionic liquids trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide and trihexyl(tetradecyl)phosphonium dicyanamide, [P6 6 6 14][Ntf2] and [P6 6 6 14][N(CN)2], respectively, at the water-air interface was investigated using the Langmuir trough technique. The obtained surface pressure versus mean molecular area (MMA) isotherms, π-A, and surface potential versus MMA isotherms, ΔV-A, show distinct interfacial behavior between the two systems. The results were interpreted at a molecular level using molecular dynamics simulations: the different compression regimes along the [P6 6 6 14][Ntf2] isotherm correspond to the self-organization of the ions at the water surface into compact and planar monolayers that coalesce at an MMA value of ca. 1.85 nm(2)/ion pair to form an expanded liquidlike layer. Upon further compression, the monolayer collapses at around 1.2 nm(2)/ion pair to yield a progressively thicker and less organized layer. These transitions are much more subdued in the [P6 6 6 14][N(CN)2] system because of the more hydrophilic nature of the dicyanamide anion. The numerical density profiles obtained from the MD simulation trajectories are also able to emphasize the very unusual packing of the four long alkyl side chains of the cation above and below the ionic layer that forms at the water surface. Such a distribution is also different for the two studied systems during the different compression regimes.

  9. Studies of molecular monolayers at air-liquid interfaces by second harmonic generation: question of orientational phase transition

    SciTech Connect

    Rasing, T.; Shen, Y.R.; Kim, M.W.; Grubb, S.; Bock, J.

    1985-06-01

    Insoluble molecular monolayers at gas-liquid interfaces provide an insight to the understanding of surfactants, wetting, microemulsions and membrane structures and offer a possibility to study the rich world of 2-dimensional phase transitions. In the interpretation of the observed properties of these systems various assumptions about the molecular orientation are often made, but so far few clear experimental data exist. In this paper we will show how optical second harmonic generation (SHG) can be used to measure the molecular orientation of monolayers of surfactant molecules at water-air interfaces. By simultaneously measuring the surface pressure versus surface molecular area we can show for the first time that the observed liquid condensed-liquid expanded transition is an orientational phase transition. 7 refs., 4 figs.

  10. Floating and Sinking of a Pair of Spheres at a Liquid-Fluid Interface.

    PubMed

    Cooray, Himantha; Cicuta, Pietro; Vella, Dominic

    2017-02-14

    Spheres floating at liquid-fluid interfaces cause interfacial deformations such that their weight is balanced by the resultant forces of surface tension and hydrostatic pressure while also satisfying a contact angle condition. Determining the meniscus shape around several floating spheres is a complicated problem because the vertical locations of the spheres and the horizontal projections of the three-phase contact lines are not known a priori. Here, a new computational algorithm is developed to simultaneously satisfy the nonlinear Laplace-Young equation for the meniscus shape, the vertical force balance, and the geometric properties of the spheres. We implement this algorithm to find the shape of the interface around a pair of floating spheres and the horizontal force required to keep them at a fixed center-center separation. Our numerical simulations show that the ability of a pair of spheres to float (rather than sink) depends on their separation. Similar to previous work on horizontal cylinders, sinking may be induced at close range for small spheres that float when isolated. However, we also discover a new and unexpected behavior: at intermediate inter-particle distances, spheres that would sink in isolation can float as a pair. This effect is more pronounced for spheres of radius comparable to the capillary length, suggesting that this effect is a result of hydrostatic pressure, rather than surface tension. An approximate solution confirms these phenomena and shows that the mechanism is indeed the increased supporting force provided by the hydrostatic pressure. Finally, the horizontal force of capillary attraction between the spheres is calculated using the results of the numerical simulations. These results show that the classic linear superposition approximation (due to Nicolson) can lose its validity for relatively heavy particles at close range.

  11. Anisotropy and roughness of the solid-liquid interface of BCC Fe.

    PubMed

    Sun, Yongli; Wu, Yongquan; Lu, Xiuming; Li, Rong; Xiao, Junjiang

    2015-02-01

    Melting point T m and kinetic coefficient μ (a proportional constant between the interfacial velocity ν and undercooling ΔT), along with the structural roughness of the solid-liquid interface for body centered cubic (BCC) Fe were calculated by molecular dynamics (MD) simulation. All simulations applied the Sutton-Chen potential, and adopted average bond orientational order (ABOO) parameters together with Voronoi polyhedron method to characterize atomic structure and calculate atomic volume. Anisotropy of T m was found through about 20~40 K decreasing from [100] to [110] and continuously to [111]. Anisotropy of μ with three low index orientations was found as: μ s,[100] > > μ s,[110] > μ s,[111] for solidifying process and μ m,[100] > > μ m,[111] > μ m,[110] for melting process. Slight asymmetry between melting and solidifying was discovered from that the ratios of μ m/μ s are all slightly larger than 1. To explain these, interfacial roughness R int and area ratio S/S 0 (ratio of realistic interfacial area S and the ideal flat cross-sectional area S 0) were defined to verify the anisotropy of interfacial roughness under different supercoolings/superheatings. The results indicated interfacial roughness anisotropies were approximately [100] > [111] > [110]; the interface in melting process is rougher than that in solidifying process; asymmetry of interfacial roughness was larger when temperature deviation ΔT was larger. Anisotropy and asymmetry of interfacial roughness fitted the case of kinetic coefficient μ very well, which could give some explanations to the anisotropies of T m and μ.

  12. Thermostability analysis of line-tension-associated nucleation at a gas-liquid interface

    NASA Astrophysics Data System (ADS)

    Singha, Sanat Kumar; Das, Prasanta Kumar; Maiti, Biswajit

    2017-01-01

    The influence of line tension on the thermostability of a droplet nucleated from an oversaturated vapor at the interface of the vapor and another immiscible liquid is investigated. Along with the condition of mechanical equilibrium, the notion of extremization of the reversible work of formation is considered to obtain the critical parameters related to heterogeneous nucleation. From the energetic formulation, the critical reversible work of formation is found to be greater than that of homogeneous nucleation for high value of the positive line tension. On the other hand, for high value of the negative line tension, the critical reversible work of formation becomes negative. Therefore, these thermodynamic instabilities under certain substrate wettability situations necessitate a free-energetics-based stability of the nucleated droplet, because the system energy is not minimized under these conditions. This thermostability is analogous to the transition-based stability proposed by Widom [B. Widom, J. Phys. Chem. 99, 2803 (1995)], 10.1021/j100009a041 in the case of partial wetting phenomena along with the positive line tension. The thermostability analysis limits the domain of the solution space of the present critical-value problem as the thermodynamic transformation in connection with homogeneous and workless nucleation is considered. Within the stability range of the geometry-based wetting parameters, three limiting modes of nucleation, i.e., total-dewetting-related homogeneous nucleation, and total-wetting-associated and total-submergence-associated workless nucleation scenarios, are identified. Either of the two related limiting wetting scenarios of workless nucleation, namely, total wetting and total submergence, is found to be favorable depending on the geometry-based wetting conditions. The line-tension-associated nucleation on a liquid surface can be differentiated from that on a rigid substrate, as in the former, the stability based on mechanical

  13. Influence of Specific Anions on the Orientational Ordering of Thermotropic Liquid Crystals at Aqueous Interfaces

    PubMed Central

    Carlton, Rebecca J.; Ma, C. Derek; Gupta, Jugal K.; Abbott, Nicholas L.

    2012-01-01

    We report that specific anions (of sodium salts) added to aqueous phases at molar concentrations can trigger rapid, orientational ordering transitions in water-immiscible, thermotropic liquid crystals (LCs; e.g., nematic phase of 4′-pentyl-4-cyanobiphenyl, 5CB) contacting the aqueous phases. Anions classified as chaotropic, specifically iodide, perchlorate and thiocyanate, cause 5CB to undergo continuous, concentration-dependent transitions from planar to homeotropic (perpendicular) orientations at LC-aqueous interfaces within 20 s of addition of the anions. In contrast, anions classified as relatively more kosmotropic in nature (fluoride, sulfate, phosphate, acetate, chloride, nitrate, bromide, and chlorate) do not perturb the LC orientation from that observed without added salts (i.e., planar orientation). Surface pressure-area isotherms of Langmuir films of 5CB supported on aqueous salt solutions reveal ion-specific effects ranking in a manner similar to the LC ordering transitions. Specifically, chaotropic salts stabilized monolayers of 5CB to higher surface pressures and areal densities (12.6 mN/m at 27 Å2/molec. for NaClO4) and thus smaller molecular tilt angles (30° from the surface normal for NaClO4) than kosmotropic salts (5.0 mN/m at 38 Å2/molec. with a corresponding tilt angle of 53° for NaCl). These results and others reported herein suggest that anion-specific interactions with 5CB monolayers lead to bulk LC ordering transitions. Support for the proposition that these ion-specific interactions involve the nitrile group was obtained by using a second LC with nitrile groups (E7; ion-specific effects similar to 5CB were observed) and a third LC with fluorine-substituted aromatic groups (TL205; weak dipole and no ion-specific effects were measured). Finally, we also establish that anion-induced orientational transitions in micrometer-thick LC films involve a change in the easy axis of the LC. Overall, these results provide new insights into ionic

  14. Ordering Transitions Triggered by Specific Binding of Vesicles to Protein-Decorated Interfaces of Thermotropic Liquid Crystals

    PubMed Central

    Tan, Lie Na; Orler, Victor J.; Abbott, Nicholas L.

    2012-01-01

    We report that specific binding of ligand-functionalized (biotinylated) phospholipid vesicles (diameter = 120 ± 19 nm) to a monolayer of proteins (streptavidin or anti-biotin antibody) adsorbed at an interface between an aqueous phase and an immiscible film of a thermotropic liquid crystal (LC) (nematic 4′-pentyl-4-cyanobiphenyl (5CB)) triggers a continuous orientational ordering transition (continuous change in the tilt) in the LC. Results presented in this paper indicate that, following the capture of the vesicles at the LC interface via the specific binding interaction, phospholipids are transferred from the vesicles onto the LC interface to form a monolayer, reorganizing and partially displacing proteins from the LC interface. The dynamics of this process are accelerated substantially by the specific binding event relative to a protein-decorated interface of a LC that does not bind the ligands presented by vesicles. The observation of the continuous change in the ordering of the LC, when combined with other results presented in this paper, is significant as it is consistent with the presence of sub-optical domains of proteins and phospholipids on the LC interface. An additional significant hypothesis that emerges from the work reported in this paper is that the ordering transition of the LC is strongly influenced by the bound state of the protein adsorbed on the LC interface, as evidenced by the influence on the LC of (i) “crowding” of the protein within a monolayer formed at the LC interface and (ii) aging of the proteins on the LC interface. Overall, these results demonstrate that ordering transitions in LCs can be used to provide fundamental insights into the competitive adsorption of proteins and lipids at oil-water interfaces, and that LC ordering transitions have the potential to be useful for reporting specific binding events involving vesicles and proteins. PMID:22372743

  15. Control of Selective Ion Transfer across Liquid–Liquid Interfaces: A Rectifying Heterojunction Based on Immiscible Electrolytes

    PubMed Central

    2016-01-01

    The current rectification displayed by solid-state p–n semiconductor diodes relies on the abundance of electrons and holes near the interface between the p–n junction. In analogy to this electronic device, we propose here the construction of a purely ionic liquid-state electric rectifying heterojunction displaying an excess of monovalent cations and anions near the interface between two immiscible solvents with different dielectric properties. This system does not need any physical membrane or material barrier to show preferential ion transfer but relies on the ionic solvation energy between the two immiscible solvents. We construct a simple device, based on an oil/water interface, displaying an asymmetric behavior of the electric current as a function of the polarity of an applied electric field. This device also exhibits a region of negative differential conductivity, analogous to that observed in brain and heart cells via voltage clamp techniques. Computer simulations and mean field theory calculations for a model of this system show that the application of an external electric field is able to control the bulk concentrations of the ionic species in the immiscible liquids in a manner that is asymmetric with respect to the polarity or direction of the applied electric field. These properties make possible to enhance or suppress selective ion transport at liquid−liquid interfaces with the application of an external electric field or electrostatic potential, mimicking the function of biological ion channels, thus creating opportunities for varied applications. PMID:27924315

  16. A Diffuse Interface Model for solid-liquid-air dissolution problems based on a porous medium theory

    NASA Astrophysics Data System (ADS)

    Luo, H.; Quintard, M.; Debenest, G.; Laouafa, F.

    2011-12-01

    The underground cavities may be dissolved by the flows of groundwater where the dissolution mainly happens at the liquid-solid interface. In many real cases, the cavities are not occupied only by the water, but also the gas phase, e.g., air, or other gases. In this case, there are solid-liquid-gas three phases. Normally, the air does not participate the dissolution. However, it may influence the dissolution as the position of the solid-liquid interface may gradually lower down with the dissolution process. Simulating the dissolution problems with multi- moving interfaces is a difficult task but rather interesting to study the evolution of the underground cavities. In this paper, we propose a diffuse interface model (DIM) to simulate the three-phase dissolution problem, based on a porous medium theory and a volume averaging theory te{Whitaker1999,Golfier2002,Quintard1994}. The interface is regarded as a continuous layer where the phase indicator (mainly for solid-liquid interface) and phase saturation (mainly for liquid-gas interface) vary rapidly but smoothly. The DIM equations enable us to simulate the moving interface under a fixed mesh system, instead of a deformed or moving mesh. Suppose we have three phases, solid, liquid and gas. The solid phase contains only species A. The gas phase contains only the air. The volume averaging theory is used to upscale the balance equations. The final DIM equations are presented below. The balance equation of solid phase can be written as {partialrho_{s}(1-\\varepsilon_{f})}/{partial t}=-K_{sl} where \\varepsilonf represents the volume fraction of the fluids (liquid+gas) and Ksl refers to the mass exchange between the solid phase and the liquid phase. Ksl cam be expressed as K_{sl}=rho_{l}alpha(omega_{eq}-Omega_{Al}). The balance equations of liquid phase can be written as {partialrho_{l}\\varepsilon_{f}S_{l}}/{partial t}+nabla\\cdot(rho_{l}{V}_{l})= K_{sl}. The balance equation of liquid phase can be written as {partialrho

  17. Exceptionally Slow Movement of Gold Nanoparticles at a Solid/Liquid Interface Investigated by Scanning Transmission Electron Microscopy.

    PubMed

    Verch, Andreas; Pfaff, Marina; de Jonge, Niels

    2015-06-30

    Gold nanoparticles were observed to move at a liquid/solid interface 3 orders of magnitude slower than expected for the movement in a bulk liquid by Brownian motion. The nanoscale movement was studied with scanning transmission electron microscopy (STEM) using a liquid enclosure consisting of microchips with silicon nitride windows. The experiments involved a variation of the electron dose, the coating of the nanoparticles, the surface charge of the enclosing membrane, the viscosity, and the liquid thickness. The observed slow movement was not a result of hydrodynamic hindrance near a wall but instead explained by the presence of a layer of ordered liquid exhibiting a viscosity 5 orders of magnitude larger than a bulk liquid. The increased viscosity presumably led to a dramatic slowdown of the movement. The layer was formed as a result of the surface charge of the silicon nitride windows. The exceptionally slow motion is a crucial aspect of electron microscopy of specimens in liquid, enabling a direct observation of the movement and agglomeration of nanoscale objects in liquid.

  18. Improvement of sugar analysis sensitivity using anion-exchange chromatography-electrospray ionization mass spectrometry with sheath liquid interface.

    PubMed

    Xu, Xian-Bing; Liu, Ding-Bo; Guo, Xiao Ming; Yu, Shu-Juan; Yu, Pei

    2014-10-31

    A novel interface that enables high-performance anion-exchange chromatography (HPAEC) to be coupled with electrospray ionization (ESI) mass spectrometry (MS) is reported. A sheath liquid consisting of 50mM NH4Ac in isopropanol with 0.05% acetic acid, infused at a flow rate of 3μL/min at the tip of the electrospray probe, requires less ESI source cleaning and promotes efficient ionization of mono- and di-carbohydrates. The results suggest that use of a sheath liquid interface rather than a T-joint allows volatile ammonium salts to replace non-volatile metal salts as modifiers for improving sugar ESI signals. The efficient ionization of mono- and di-carbohydrates in the ESI source is affected by the sheath liquid properties such as buffer concentration and type of organic solvent. HPAEC-ESI-MS was used for the analysis of monocarbohydrates in pectins, particularly co-eluted sugars, and the performance was evaluated. Addition of a make-up solution through the sheath liquid interface proved to be an efficient tool for enhancing the intensities of sugars analyzed using HPAEC-ESI-MS.

  19. Mechanical and thermodynamic properties of surfactant aggregates at the solid-liquid interface.

    PubMed

    Rabinovich, Yakov I; Vakarelski, Ivan U; Brown, Scott C; Singh, Pankaj K; Moudgil, Brij M

    2004-02-01

    Surfactants are widely used to stabilize colloidal systems in a variety of industrial applications through the formation of self-assembled aggregates at the solid-liquid interface. Previous studies have reported that the control of surfactant-mediated slurry stability can be achieved through the manipulation of surfactant chain length and concentration. However, a fundamental understanding of the mechanical and energetic properties of these aggregates, which may aid in the molecular-level design of these systems, is still lacking. In this study, experimentally measured force/distance curves between an atomic force microscope (AFM) tip and self-assembled surfactant aggregates on mica or silica substrates at concentrations higher than the bulk critical micelle concentration (CMC) were used to determine their mechanical and thermodynamic properties. The experimental curves were fitted to a model which describes the interaction between a hard sphere (tip) and a soft substrate (surfactant structures) based on a modified Hertz theory for the case of a thin elastic layer on a rigid substrate. The calculated mechanical properties were found to be in the same order of magnitude as those reported for rubber-like materials (e.g., polydimethylsiloxane (PDMS)). By integrating the force/distance curves, the energy required for breaking the surface aggregates was also calculated. These values are close to those reported for bulk-micelle formation.

  20. Characterisation of pellicles formed by Acinetobacter baumannii at the air-liquid interface.

    PubMed

    Nait Chabane, Yassine; Marti, Sara; Rihouey, Christophe; Alexandre, Stéphane; Hardouin, Julie; Lesouhaitier, Olivier; Vila, Jordi; Kaplan, Jeffrey B; Jouenne, Thierry; Dé, Emmanuelle

    2014-01-01

    The clinical importance of Acinetobacter baumannii is partly due to its natural ability to survive in the hospital environment. This persistence may be explained by its capacity to form biofilms and, interestingly, A. baumannii can form pellicles at the air-liquid interface more readily than other less pathogenic Acinetobacter species. Pellicles from twenty-six strains were morphologically classified into three groups: I) egg-shaped (27%); II) ball-shaped (50%); and III) irregular pellicles (23%). One strain representative of each group was further analysed by Brewster's Angle Microscopy to follow pellicle development, demonstrating that their formation did not require anchoring to a solid surface. Total carbohydrate analysis of the matrix showed three main components: Glucose, GlcNAc and Kdo. Dispersin B, an enzyme that hydrolyzes poly-N-acetylglucosamine (PNAG) polysaccharide, inhibited A. baumannii pellicle formation, suggesting that this exopolysaccharide contributes to pellicle formation. Also associated with the pellicle matrix were three subunits of pili assembled by chaperon-usher systems: the major CsuA/B, A1S_1510 (presented 45% of identity with the main pilin F17-A from enterotoxigenic Escherichia coli pili) and A1S_2091. The presence of both PNAG polysaccharide and pili systems in matrix of pellicles might contribute to the virulence of this emerging pathogen.

  1. Characterisation of Pellicles Formed by Acinetobacter baumannii at the Air-Liquid Interface

    PubMed Central

    Nait Chabane, Yassine; Marti, Sara; Rihouey, Christophe; Alexandre, Stéphane; Hardouin, Julie; Lesouhaitier, Olivier; Vila, Jordi; Kaplan, Jeffrey B.; Jouenne, Thierry; Dé, Emmanuelle

    2014-01-01

    The clinical importance of Acinetobacter baumannii is partly due to its natural ability to survive in the hospital environment. This persistence may be explained by its capacity to form biofilms and, interestingly, A. baumannii can form pellicles at the air-liquid interface more readily than other less pathogenic Acinetobacter species. Pellicles from twenty-six strains were morphologically classified into three groups: I) egg-shaped (27%); II) ball-shaped (50%); and III) irregular pellicles (23%). One strain representative of each group was further analysed by Brewster’s Angle Microscopy to follow pellicle development, demonstrating that their formation did not require anchoring to a solid surface. Total carbohydrate analysis of the matrix showed three main components: Glucose, GlcNAc and Kdo. Dispersin B, an enzyme that hydrolyzes poly-N-acetylglucosamine (PNAG) polysaccharide, inhibited A. baumannii pellicle formation, suggesting that this exopolysaccharide contributes to pellicle formation. Also associated with the pellicle matrix were three subunits of pili assembled by chaperon-usher systems: the major CsuA/B, A1S_1510 (presented 45% of identity with the main pilin F17-A from enterotoxigenic Escherichia coli pili) and A1S_2091. The presence of both PNAG polysaccharide and pili systems in matrix of pellicles might contribute to the virulence of this emerging pathogen. PMID:25360550

  2. Observations of the liquid/solid interface in low-gravity melting

    NASA Technical Reports Server (NTRS)

    Otto, G. H.; Lacy, L. L.

    1974-01-01

    Time-lapsed photography of the liquid/solid interface of a melting ice cylinder was taken on Skylab 3 over a period of three hours. The same experiment was simulated on earth such that morphological and thermodynamic differences could be noted. A study of the returned color film clearly shows the dominance of surface tension effects in low-gravity melting. In the Skylab experiment, the ends of the ice cylinder melted first with the water being driven by surface tension onto the cylindrical surfaces. At any time, the principle of minimum surface area governs the overall appearance of the water-ice globule which changed from a cylindrical to a spherical shape. The latent heat of melting in low-gravity is supplied only by radiation (81%) and conduction (19%); whereas in one-g, the convective (55%) and radiative (38%) mode of heat transfer dominates over the conductive portion (7%). Information is also provided on containerless melting and heat transfer in space in the absence of convective air currents.

  3. Cigarette smoke alters primary human bronchial epithelial cell differentiation at the air-liquid interface.

    PubMed

    Schamberger, Andrea C; Staab-Weijnitz, Claudia A; Mise-Racek, Nikica; Eickelberg, Oliver

    2015-02-02

    The differentiated human airway epithelium consists of different cell types forming a polarized and pseudostratified epithelium. This is dramatically altered in chronic obstructive pulmonary disease (COPD), characterized by basal and goblet cell hyperplasia, and squamous cell metaplasia. The effect of cigarette smoke on human bronchial epithelial cell (HBEC) differentiation remains to be elucidated. We analysed whether cigarette smoke extract (CSE) affected primary (p)HBEC differentiation and function. pHBEC were differentiated at the air-liquid interface (ALI) and differentiation was quantified after 7, 14, 21, or 28 days by assessing acetylated tubulin, CC10, or MUC5AC for ciliated, Clara, or goblet cells, respectively. Exposure of differentiating pHBEC to CSE impaired epithelial barrier formation, as assessed by resistance measurements (TEER). Importantly, CSE exposure significantly reduced the number of ciliated cells, while it increased the number of Clara and goblet cells. CSE-dependent cell number changes were reflected by a reduction of acetylated tubulin levels, an increased expression of the basal cell marker KRT14, and increased secretion of CC10, but not by changes in transcript levels of CC10, MUC5AC, or FOXJ1. Our data demonstrate that cigarette smoke specifically alters the cellular composition of the airway epithelium by affecting basal cell differentiation in a post-transcriptional manner.

  4. Single-Step Fabrication of Computationally Designed Microneedles by Continuous Liquid Interface Production

    PubMed Central

    Johnson, Ashley R.; Caudill, Cassie L.; Tumbleston, John R.; Bloomquist, Cameron J.; Moga, Katherine A.; Ermoshkin, Alexander; Shirvanyants, David; Mecham, Sue J.; Luft, J. Christopher; DeSimone, Joseph M.

    2016-01-01

    Microneedles, arrays of micron-sized needles that painlessly puncture the skin, enable transdermal delivery of medications that are difficult to deliver using more traditional routes. Many important design parameters, such as microneedle size, shape, spacing, and composition, are known to influence efficacy, but are notoriously difficult to alter due to the complex nature of microfabrication techniques. Herein, we utilize a novel additive manufacturing (“3D printing”) technique called Continuous Liquid Interface Production (CLIP) to rapidly prototype sharp microneedles with tuneable geometries (size, shape, aspect ratio, spacing). This technology allows for mold-independent, one-step manufacturing of microneedle arrays of virtually any design in less than 10 minutes per patch. Square pyramidal CLIP microneedles composed of trimethylolpropane triacrylate, polyacrylic acid and photopolymerizable derivatives of polyethylene glycol and polycaprolactone were fabricated to demonstrate the range of materials that can be utilized within this platform for encapsulating and controlling the release of therapeutics. These CLIP microneedles effectively pierced murine skin ex vivo and released the fluorescent drug surrogate rhodamine. PMID:27607247

  5. Open, microfluidic flow cell for studies of interfacial processes at gas-liquid interfaces.

    PubMed

    Hoang, Khanh C; Malakhov, Dmitry; Momsen, William E; Brockman, Howard L

    2006-03-01

    Interfacial processes involving peripheral proteins depend on the composition and packing density of the interfacial lipid molecules. As a biological membrane model, lipid monolayers at the gas-liquid interface allow independent control of these parameters. However, measuring protein adsorption to monolayers has been difficult. To aid in this and other studies of the interfacial processes, we have developed an open, microfluidic flow cell with which surface physical properties can be controlle