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Sample records for aux interfaces liquide

  1. Continuous Liquid Interface Production (CLIP)

    NASA Astrophysics Data System (ADS)

    Tumbleston, John

    Continuous liquid interface production (CLIP) can rapidly produce 3D parts using a range of polymeric materials. A DLP-based form of additive manufacturing, CLIP proceeds via projecting a sequence of UV images through an oxygen-permeable, UV-transparent window below a liquid resin bath. A thin uncured liquid layer, or dead zone, is created above the window and maintains a liquid interface below the advancing part. Above the dead zone, the curing part is drawn out of the resin bath creating suction forces that renew reactive liquid resin. The dead zone is created due to oxygen inhibition of photopolymerization, a process that is traditionally a nuisance in other photopolymerization applications. However, for CLIP oxygen inhibition and creation of the dead zone allows for a continuous mode of printing where UV exposure, resin renewal, and part elevation are conducted simultaneously. This continual process is fundamentally different from traditional bottom-up stereolithography printers where these steps must be conducted in separate and discrete steps. Furthermore, the relatively gentle nature of CLIP due to the established dead zone enables the use of unique materials with a wide range of mechanical properties. This presentation will showcase the CLIP technology and provide a detailed picture of interactions between different resin and process parameters. New applications for 3D printing that span the micro- to macro-scale enabled by CLIP's combination of unique materials and part production speed will also be presented.

  2. Transport of microspheres across liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Hardt, Steffen; Sinha, Ashok; Mollah, Amlan; Ganguly, Ranjan

    2013-11-01

    Experiments with magnetic microspheres crossing the interface between two immiscible polymer solutions under the influence of a magnetic field are reported. The liquids form a bilaminated configuration in a microchannel, allowing a detailed inspection of the liquid-liquid interface. The trajectories of the particles close to the interface are examined using bright-field microscopy and a high-speed camera. During the interaction phase the interface gets deformed and the particles ``snap in,'' indicating that a three-phase contact line is formed. The dependence of the particle-interface interaction on the size of the microspheres is studied, showing that via transfer across a liquid-liquid interface a size separation of particles can be achieved. Comparing the results for 1.29 micron diameter spheres with those for 4.69 micron spheres, it is found that the small particles are able to cross the interface more easily than what is expected from a simple scaling analysis taking into account the balance between magnetic and interfacial forces on the particles. The most likely explanation for this phenomenon involves the line tension that destabilizes smaller particles adsorbed to a liquid-liquid interface more than larger particles.

  3. Electrophoretic transport of biomolecules across liquid-liquid interfaces.

    PubMed

    Hahn, Thomas; Münchow, Götz; Hardt, Steffen

    2011-05-11

    The mass transfer resistance of a liquid-liquid interface in an aqueous two-phase system composed of poly(ethylene glycol) and dextran is investigated. Different types of proteins and DNA stained with fluorescent dyes serve as probes to study the transport processes close to the interface. A microfluidic device is employed to enable the electrophoretic transport of biomolecules from one phase to another. The results obtained for proteins can be explained solely via the different electrophoretic mobilities and different affinities of the molecules to the two phases, without any indications of a significant mass transfer resistance of the liquid-liquid interface. By contrast, DNA molecules adsorb to the interface and only desorb under an increased electric field strength. The desorption process carries the signature of a thermally activated escape from a metastable state, as reflected in the exponential decay of the fluorescence intensity at the interface as a function of time. PMID:21508474

  4. Phenomena on Plasma-Liquid Interface

    NASA Astrophysics Data System (ADS)

    Takeuchi, Nozomi

    Recent researches on plasma-liquid interface are introduced. One is about plasma-water interaction at the interface of pulsed dielectric-barrier plasma in gas-liquid two-phase flow for water treatment. Acetic acid in water is decomposed as a persistent material. Numerical calculation indicates that plasma-water interaction which is O-radical-induced generation of liquid-phase-OH radical occurs. The other reports highly-concentrated adsorption of a surfactant at plasma-water interface, and an interfacial reaction decomposing the surfactant. Perfluorooctane sulfonic acid is an extremely persistent surfactant, but can be decomposed by plasma attached to the solution. The decomposing reaction occurs at the plasma-water interface. Estimation of the amount of PFOS adsorbing to the plasma-water interface shows much higher mole fraction of PFOS than that in bulk water. Thus, the plasma can effectively react with PFOS at the water surface and exhibits high energy efficiency.

  5. 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

  6. Ionic liquid lubrication at electrified interfaces

    NASA Astrophysics Data System (ADS)

    Kong, Lingling; Huang, Wei; Wang, Xiaolei

    2016-06-01

    The lubrication performances of ionic liquids at electrified interfaces have been investigated by using a reciprocating sliding tribometer. Experimental results indicated that the lubricity of the confined ionic liquids was markedly affected by the application of external electric field and strong interface electric field strength could result in high friction. The influence was more pronounced for the ionic liquid with a shorter alkyl side chain in particular. The main reason of the friction increment might be ascribed to the electrically influenced surface adsorption where the charged ions were structured to form robust and ordered layers.

  7. 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.

  8. Marangoni-driven spreading along liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Berg, S.

    2009-03-01

    Marangoni-driven spreading at gas-liquid interfaces has been studied extensively over the past years but so far the spreading kinetics along the interface between immiscible liquids has not been investigated systematically. In this study, the spreading kinetics of aqueous solutions of sodium dodecyl sulfate and dodecyl trimethyl ammonium bromide along the interface between thick layers of water and decane has been investigated by means of two different optical visualization techniques (dye tracer and laser shadowgraphy). The spreading kinetics follows a power law where the radius r as function of time t scales as r(t )∝t3/4 indicating large similarities with Marangoni-driven spreading at air-liquid interfaces. The existing scaling law for spreading at air-liquid interfaces is based on the balance between an interfacial tension gradient and the viscous stress in the fluid layers beneath the interface. When the viscous dissipation in the two boundary layers below and above the interface is factored into the scaling law, quantitative agreement with experimental data is obtained. Marangoni-driven spreading along an interface is a fast transport mechanism. The velocity of the leading edge lies within the range of group velocities of capillary waves.

  9. Polymers at liquid-liquid interfaces: Photophysics and photoredox chemistry

    SciTech Connect

    Webber, S.E.

    1990-11-01

    Research continued on polymers at liquid-liquid interfaces. This quarter, work concentrated on: preparation of poly(styrene-alt-maleic acid-co-chromophore) polymers; studies of vinylnapthalene-maleic acid polymers as emulsifying agents for water-octane; and assembly of optical fiber reticon-based transient absorption system. 3 refs., 1 fig. (CBS)

  10. Plasmonic ruler at the liquid-liquid interface.

    PubMed

    Turek, Vladimir A; Cecchini, Michael P; Paget, Jack; Kucernak, Anthony R; Kornyshev, Alexei A; Edel, Joshua B

    2012-09-25

    We report on a simple, fast, and inexpensive method to study adsorption and desorption of metallic nanoparticles at a liquid/liquid interface. These interfaces provide an ideal platform for the formation of two-dimensional monolayers of nanoparticles, as they form spontaneously and are defect-correcting, acting as 2D "nanoparticle traps". Such two-dimensional, self-assembled nanoparticle arrays have a vast range of potential applications in displays, catalysis, plasmonic rulers, optoelectronics, sensors, and detectors. Here, we show that 16 nm diameter gold nanoparticles can be controllably adsorbed to a water/1,2-dichloroethane interface, and that we can control the average interparticle spacing at the interface over the range 6-35 nm. The particle density and average interparticle spacing are experimentally assessed by measuring the optical plasmonic response of the nanoparticles in the bulk and at the interface and by comparing the experimental data with existing theoretical results. PMID:22900717

  11. [Charge generation and separation at liquid interfaces

    SciTech Connect

    Eisenthal, K.B.

    1992-01-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C[double bond]N and CD[sub 3] chromosphores (head group and tail) on lipid monolayers CD[sub 3](CH[sub 2])[sub 21]CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50[Angstrom]) were strongly polarized by SiO[sup [minus

  12. Liquid-vapor interfaces of patchy colloids.

    PubMed

    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 (2A9B 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)], 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 AB 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)]. If BB attractions are also present, competition between AB and BB 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 BB attractions remove these features, and the system reverts to the behavior seen in atomic fluids. PMID:25679617

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Polymer single crystal membrane from liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Li, Christopher; Soft Matter Research Group-Drexel University Team

    2013-03-01

    Vesicles, mimicking the structure of cell membrane at the molecular scale, are small membrane-enclosed sacks that can store or transport substances. The weak mechanical properties and the nature of environment-sensitivity of the current available vesicles: liposomes, polymersomes, colloidsomes limit their applications as an excellent candidate for targeting delivery of drugs/genes in biomedical engineering and treatment. Recently, we developed an emulsion-based method to grow curved polymer single crystals. Varying the polymer concentration and/or the emulsification conditions (such as surfactant concentration, water-oil volume ratio), curved crystals with different sizes and different openness could be obtained. This growing process was attributed to polymer crystal growth along the liquid/liquid interface. In addition, the liquid/liquid interfacial crystal growth is promising for synthesis of enclosed hollow sphere.

  20. Electron transfer kinetics at polarized nanoscopic liquid/liquid interfaces.

    PubMed

    Cai, Chenxin; Mirkin, Michael V

    2006-01-11

    Rapid kinetics of electron transfer (ET) reactions across the interface between water and 1,2-dichloroethane were measured by steady-state voltammetry at nanopipet electrodes (50- to 400-nm orifice radius). The origins of previously reported imperfect voltammetric responses of ET reactions at micropipets were investigated. Several new experimental systems were explored, and two of them yielded high-quality voltammograms suitable for kinetic experiments. The determined standard rate constants were compared to those measured previously at polarized and nonpolarized liquid/liquid interfaces. The effect of the interfacial dimensions on the magnitude of the apparent ET rate constant is discussed. A new approach to ET kinetic measurements based on the use of the scanning electrochemical microscope with a nanopipet tip and a metallic substrate has been developed and employed to check the validity of determined kinetic parameters. PMID:16390144

  1. Computational Investigations of Solid-Liquid Interfaces

    SciTech Connect

    Mark Asta

    2011-08-31

    In a variety of materials synthesis and processing contexts, atomistic processes at heterophase interfaces play a critical role governing defect formation, growth morphologies, and microstructure evolution. Accurate knowledge of interfacial structure, free energies, mobilities and segregation coefficients are critical for predictive modeling of microstructure evolution, yet direct experimental measurement of these fundamental interfacial properties remains elusive in many cases. In this project first-principles calculations were combined with molecular-dynamics (MD) and Monte-Carlo (MC) simulations, to investigate the atomic-scale structural and dynamical properties of heterophase interfaces, and the relationship between these properties and the calculated thermodynamic and kinetic parameters that influence the evolution of phase transformation structures at nanometer to micron length scales. The topics investigated in this project were motivated primarily by phenomena associated with solidification processing of metals and alloys, and the main focus of the work was thus on solid-liquid interfaces and high-temperature grain boundaries. Additional efforts involved first-principles calculations of coherent solid-solid heterophase interfaces, where a close collaboration with researchers at the National Center for Electron Microscopy was undertaken to understand the evolution of novel core-shell precipitate microstructures in aluminum alloys.

  2. Predicting apparent slip at liquid-liquid interfaces without an interface slip condition

    NASA Astrophysics Data System (ADS)

    Poesio, Pietro; Damone, Angelo; Matar, Omar

    2015-11-01

    We show that if we include a density-dependent viscosity into the Navier-Stokes equations then we can describe, naturally, the velocity profile in the interfacial region, as we transition from one fluid to another. This requires knowledge of the density distribution (for instance, via Molecular Dynamics [MD] simulations, a diffuse-interface approach, or Density Functional Theory) everywhere in the fluids, even at liquid-liquid interfaces where regions of rapid density variations are possible due to molecular interactions. We therefore do not need an artificial interface condition that describes the apparent velocity slip. If the results are compared with the computations obtained from MD simulations, we find an almost perfect agreement. The main contribution of this work is to provide a simple way to account for the apparent slip at liquid-liquid interfaces without relying upon an additional boundary condition, which needs to be calculated separately using MD simulations. Examples are provided involving two immiscible fluids of varying average density ratios, undergoing simple Couette and Poisseuille flows. MIUR through PRIN2012-NANOBridge; Royal Society International Exchange Scheme (IE141486).

  3. Compartmentalized Droplets for Continuous Flow Liquid-Liquid Interface Catalysis.

    PubMed

    Zhang, Ming; Wei, Lijuan; Chen, Huan; Du, Zhiping; Binks, Bernard P; Yang, Hengquan

    2016-08-17

    To address the limitations of batch organic-aqueous biphasic catalysis, we develop a conceptually novel method termed Flow Pickering Emulsion, or FPE, to process biphasic reactions in a continuous flow fashion. This method involves the compartmentalization of bulk water into micron-sized droplets based on a water-in-oil Pickering emulsion, which are packed into a column reactor. The compartmentalized water droplets can confine water-soluble catalysts, thus "immobilizing" the catalyst in the column reactor, while the interstices between the droplets allow the organic (oil) phase to flow. Key fundamental principles underpinning this method such as the oil phase flow behavior, the stability of compartmentalized droplets and the confinement capability of these droplets toward water-soluble catalysts are experimentally and theoretically investigated. As a proof of this concept, case studies including a sulfuric acid-catalyzed addition reaction, a heteropolyacid-catalyzed ring opening reaction and an enzyme-catalyzed chiral reaction demonstrate the generality and versatility of the FPE method. Impressively, in addition to the excellent durability, the developed FPE reactions exhibit up to 10-fold reaction efficiency enhancement in comparison to the existing batch reactions, indicating a unique flow interface catalysis effect. This study opens up a new avenue to allow conventional biphasic catalysis reactions to access more sustainable and efficient flow chemistry using an innovative liquid-liquid interface protocol. PMID:27429173

  4. 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. PMID:26189700

  5. 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. PMID:23376970

  6. Fluorinated monolayers at liquid-liquid and liquid-vapor interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Zhongjian

    Microscopic structure of several fluorinated monolayers at water-vapor and water-oil interfaces were examined using x-ray specular reflectivity and grazing incidence diffraction (GID) techniques. Grazing incidence x-ray diffraction measurements of monolayers of perfluoro-n-eicosane (F(CFsb2)sb{20}F) and F(CFsb2)sb{m}(CHsb2)sb{n}H (denoted as Fsb{m}Hsb{n}) supported at the air-water interface demonstrated that even without the conventional polar head group, the surfactant molecules are capable of forming ordered in-plane structures defined by hexagonal close packing of the fluorinated blocks of adsorbed molecules due to the stronger chain-chain interaction between fluorocarbon chains than the corresponding hydrocarbons. The specular reflectivity data reveals a hydrocarbon-down, fluorocarbon-up orientation for Fsb{12}Hsb{18}. In contrast to the conventional expectation that soluble surfactants form disordered monolayers at the liquid-liquid interface, the studies on a fluoroalcohol (F(CFsb2)sb{10}(CHsb2)sb2OH) monolayer at water-hexane interface indicate that the surfactants are in a close packed hexagonal phase, similar to the in-plane structure of other fluorocarbon molecules at water-air interface. Above a transition temperature the monolayer is in a low density gas phase. Preliminary study shows that hysteresis effect occurs around the transition temperature. The first measurements of microscopic structure at common high interfacial tension liquid-liquid interfaces such as a simple oil-water (hexane-water) interface is also reported. Thermal expansion coefficient measurements indicate subtle structural differences in these monolayers.

  7. Shear melting at the crystal-liquid interface: Erosion and the asymmetric suppression of interface fluctuations

    NASA Astrophysics Data System (ADS)

    Ramsay, Malcolm; Harrowell, Peter

    2016-04-01

    The influence of an applied shear on the planar crystal-melt interface is modeled by a nonlinear stochastic partial differential equation of the interface fluctuations. A feature of this theory is the asymmetric destruction of interface fluctuations due to advection of the crystal protrusions on the liquid side of the interface only. We show that this model is able to qualitatively reproduce the nonequilibrium coexistence line found in simulations. The impact of shear on spherical clusters is also addressed.

  8. 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. PMID:21820124

  9. 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.

  10. 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

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

    SciTech Connect

    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.

  12. Electroless deposition of palladium at bare and templated liquid/liquid interfaces.

    PubMed

    Dryfe, Robert A W; Simm, Andrew O; Kralj, Brett

    2003-10-29

    A simple, electroless approach to metallize the liquid/liquid interface is reported. The method is illustrated with the deposition of Pd at the bare water/1,2-dichloroethane interface, and for the "templated" deposition of Pd within the 100 nm diameter pores of gamma-alumina membranes. PMID:14570460

  13. 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.

  14. 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. PMID:27060934

  15. Nanoparticles at liquid interfaces: Rotational dynamics and angular locking

    SciTech Connect

    Razavi, Sepideh; Kretzschmar, Ilona; Koplik, Joel; Colosqui, Carlos E.

    2014-01-07

    Nanoparticles with different surface morphologies that straddle the interface between two immiscible liquids are studied via molecular dynamics simulations. The methodology employed allows us to compute the interfacial free energy at different angular orientations of the nanoparticle. Due to their atomistic nature, the studied nanoparticles present both microscale and macroscale geometrical features and cannot be accurately modeled as a perfectly smooth body (e.g., spheres and cylinders). Under certain physical conditions, microscale features can produce free energy barriers that are much larger than the thermal energy of the surrounding media. The presence of these energy barriers can effectively “lock” the particle at specific angular orientations with respect to the liquid-liquid interface. This work provides new insights on the rotational dynamics of Brownian particles at liquid interfaces and suggests possible strategies to exploit the effects of microscale features with given geometric characteristics.

  16. 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.

  17. 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. PMID:27571473

  18. Developing interface localized liquid dielectrophoresis for optical applications

    NASA Astrophysics Data System (ADS)

    McHale, Glen; Brown, Carl V.; Newton, Michael I.; Wells, Gary G.; Sampara, Naresh

    2012-11-01

    Electrowetting charges the solid-liquid interface to change the contact area of a droplet of a conducting liquid. It is a powerful technique used to create variable focus liquid lenses, electronic paper and other devices, but it depends upon ions within the liquid. Liquid dielectrophoresis (L-DEP) is a bulk force acting on the dipoles throughout 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. In this work, we show theoretically how non-uniform electric fields generated by interdigitated electrodes can effectively convert L-DEP into an interface localized form. We show that for droplets of sufficient thickness, the change in the cosine of the contact angle is proportional to the square of the applied voltage and so obeys a similar equation to that for electrowetting - this we call dielectrowetting. However, a major difference to electrowetting is that the strength of the effect is controlled by the electrode spacing and the liquid permittivity rather than the properties of an insulator in a sandwich structure. Experimentally, we show that that this dielectrowetting equation accurately describes the contact angle of a droplet of oil viewed across parallel interdigitated electrodes. Importantly, the induced spreading can be complete, such that contact angle saturation does not occur. We then show that for thin films, L-DEP can shape the liquid-air interface creating a spatially periodic wrinkle and that such a wrinkle can be used to create a voltage programmable phase diffraction grating.

  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. Detection of food additives by voltammetry at the liquid-liquid interface.

    PubMed

    Herzog, Grégoire; Kam, Victor; Berduque, Alfonso; Arrigan, Damien W M

    2008-06-25

    Electrochemistry at the liquid-liquid interface enables the detection of nonredoxactive species with electroanalytical techniques. In this work, the electrochemical behavior of two food additives, aspartame and acesulfame K, was investigated. Both ions were found to undergo ion-transfer voltammetry at the liquid-liquid interface. Differential pulse voltammetry was used for the preparation of calibration curves over the concentration range of 30-350 microM with a detection limit of 30 microM. The standard addition method was applied to the determination of their concentrations in food and beverage samples such as sweeteners and sugar-free beverages. Selective electrochemically modulated liquid-liquid extraction of these species in both laboratory solutions and in beverage samples was also demonstrated. These results indicate the suitability of liquid-liquid electrochemistry as an analytical approach in food analysis. PMID:18512937

  1. 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.

  2. Ionic structure in liquids confined by dielectric interfaces.

    PubMed

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

    2015-11-21

    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. PMID:26590543

  3. 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.

  4. Liquid?solid helium interface: some conceptual questions

    NASA Astrophysics Data System (ADS)

    Leggett, A. J.

    2003-12-01

    I raise, and discuss qualitatively, some conceptual issues concerning the interface between the crystalline solid and superfluid liquid phases of 4He emphasizing, in particular, the fact that the ground-state wave functions of the two phases are prima facie qualitatively quite different, in that the superfluid liquid phase possesses off-diagonal long-range order (ODLRO), while the crystalline solid does not. The fact that the statics and dynamics of the interface do not appear to be particularly sensitive to the presence of ODLRO in the liquid is tentatively explained by the fact that because of a subtlety associated with the Bose statistics obeyed by the atoms, the solid and liquid wave functions are not locally very different.

  5. Bubble departure in the direct-contact boiling field with a continuous liquid-liquid interface

    SciTech Connect

    Kadoguchi, Katsuhiko

    2007-01-15

    Behavior of vapor bubbles was experimentally investigated in the boiling field where a volatile liquid layer of per-fluorocarbon PF5050 (boiling point 306K) was directly in contact with an immiscible hot liquid layer of water above it. Heat was supplied to the continuous liquid-liquid interface by the impingement of the downward hot water jet. Vapor bubbles were generated not only from this continuous interface but from a large number of PF5050 droplets floating on it. According to precise observation, incipience of boiling did not occur at the liquid-liquid interface but in the PF5050 liquid close to the interface in both cases of continuous and dispersed interfaces. As a result, the bubbles broke up the thin PF5050 liquid film above them and rose up into the water layer. This bubble departure phenomenon, which does not occur in the ordinary pool boiling field on the solid heating wall, is very important to evaluate the heat transfer performance in the present direct-contact boiling system. For modeling this behavior, sizes of the bubbles were measured at the moment just after they were released into the water pool. Volumes of the bubbles were larger in the case of departing from the continuous liquid-liquid interface than from the droplets. This tendency could be explained by taking into account the buoyancy force acting on unit area of the thin PF5050 liquid film above the bubble before departure, which was one of the most important parameters for the liquid film breakdown. (author)

  6. Surface potential of the water liquid-vapor interface

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Pohorille, Andrew; Pratt, Lawrence R.

    1988-01-01

    An analysis of an extended molecular dynamics calculation of the surface potential (SP) of the water liquid-vapor interface is presented. The SP predicted by the TIP4P model is -(130 + or - 50) mV. This value is of reasonable magnitude but of opposite sign to the expectations based on laboratory experiments. The electrostatic potential shows a nonmonotonic variation with depth into the liquid.

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

    PubMed

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

    2016-03-01

    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. PMID:26744846

  8. Electroanalytical Ventures at Nanoscale Interfaces Between Immiscible Liquids

    NASA Astrophysics Data System (ADS)

    Arrigan, Damien W. M.; Liu, Yang

    2016-06-01

    Ion transfer at the interface between immiscible electrolyte solutions offers many benefits to analytical chemistry, including the ability to detect nonredox active ionized analytes, to detect ions whose redox electrochemistry is accompanied by complications, and to separate ions based on electrocontrolled partition. Nanoscale miniaturization of such interfaces brings the benefits of enhanced mass transport, which in turn leads to improved analytical performance in areas such as sensitivity and limits of detection. This review discusses the development of such nanoscale interfaces between immiscible liquids and examines the analytical advances that have been made to date, including prospects for trace detection of ion concentrations.

  9. Electroanalytical Ventures at Nanoscale Interfaces Between Immiscible Liquids.

    PubMed

    Arrigan, Damien W M; Liu, Yang

    2016-06-12

    Ion transfer at the interface between immiscible electrolyte solutions offers many benefits to analytical chemistry, including the ability to detect nonredox active ionized analytes, to detect ions whose redox electrochemistry is accompanied by complications, and to separate ions based on electrocontrolled partition. Nanoscale miniaturization of such interfaces brings the benefits of enhanced mass transport, which in turn leads to improved analytical performance in areas such as sensitivity and limits of detection. This review discusses the development of such nanoscale interfaces between immiscible liquids and examines the analytical advances that have been made to date, including prospects for trace detection of ion concentrations. PMID:27049634

  10. [Charge generation and separation at liquid interfaces]. Technical progress report

    SciTech Connect

    Eisenthal, K.B.

    1992-12-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C{double_bond}N and CD{sub 3} chromosphores (head group and tail) on lipid monolayers CD{sub 3}(CH{sub 2}){sub 21}CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50{Angstrom}) were strongly polarized by SiO{sup {minus}} charges at the interface. In summary, a new spectroscopic technique is being applied to study of neutral and charged lipid monolayers, interface pKa values, interface potential and orientational structure and vibrational spectroscopy of lipids.

  11. Detachment of particles and particle clusters from liquid/liquid interfaces.

    PubMed

    Sinn, N; Alishahi, M; Hardt, S

    2015-11-15

    The detachment of microspheres from a liquid/liquid interface triggered by body forces is studied experimentally, both for the case of single particles and for particle clusters. The values of the critical force required to detach particles from the interface are in agreement with the maximum values of the wetting force keeping a particles at the interface. In the case of particle clusters, a rearrangement of the cluster configuration from a raft to a more compact structure is observed when the body force is increased. Clusters detach from the liquid/liquid interface at smaller acceleration values than single particles. The critical accelerations required to detach particle clusters are consistent with models assuming that the wetting force acts at the circumference of a spherical or hemispherical densely packed particle cluster. These models predict that the critical acceleration for particle clusters scales as n(-2/3), where n is the number of particles in a cluster. PMID:26207586

  12. 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

  13. 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.

  14. 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.

  15. Bouncing of polymeric droplets on liquid interfaces.

    PubMed

    Gier, S; Dorbolo, S; Terwagne, D; Vandewalle, N; Wagner, C

    2012-12-01

    The effect of polymers on the bouncing behavior of droplets in a highly viscous, vertically shaken silicone oil bath was investigated in this study. Droplets of a sample liquid were carefully placed on a vibrating bath that was maintained well below the threshold of Faraday waves. The bouncing threshold of the plate acceleration depended on the acceleration frequency. For pure water droplets and droplets of aqueous polymer solutions, a minimum acceleration amplitude was observed in the acceleration threshold curves as a function of frequency. The bouncing acceleration amplitude for a droplet of a dilute aqueous polymer solution was higher than the acceleration amplitude for a pure water droplet. Measurements of the center of mass trajectory and the droplet deformations showed that the controlling parameter in the bouncing process was the oscillating elongational rate of the droplet. This parameter can be directly related to the elongational viscosity of the polymeric samples. The large elongational viscosity of the polymer solution droplets suppressed large droplet deformations, resulting in less chaotic bouncing. PMID:23368045

  16. Nematic liquid crystal interfaces for chemical and biological detection

    NASA Astrophysics Data System (ADS)

    Most, Darrin R.; VanTreeck, Heidi J.; Grinwald, Bart A.; Kupcho, Kurt A.; Sen, Avijit; Bonds, Michael D.; Anhalt, Karla; Israel, Barbara A.; Acharya, Bharat R.

    2011-03-01

    Nematic liquid crystals (NLCs) have traditionally been used in displays and other electro-optical applications where the orientation of NLC is manipulated by using an external electric field to display the information. In recent years, there have been significant advances in unconventional applications of NLCs in photonics, sensors, and diagnostics. In this paper, the application of NLCs for detection of vapor phase chemicals and biological entities is presented. When NLCs are in contact with another medium (solid, liquid or air) the delicate interplay between the properties of medium and NLCs determines the nature of the alignment assumed by NLCs at the interface. Interfaces functionalized with select chemical or biological entities promote alignment of NLCs in predetermined orientations (perpendicular or parallel to that interface) that are primarily dictated by local interactions at the interface. When these interfaces are exposed to target analytes, the interactions at the interfaces are perturbed and the NLC films undergo orientational transitions from perpendicular to parallel alignment, or vice versa. The orientational transition can be detected by viewing the film of NLCs between crossed polarizers (optical signal) or by measuring the differential capacitance associated with the change in alignment of NLCs (electrical signal). By engineering surfaces with different interfacial properties, sensors based on this principle have been demonstrated to selectively detect a wide variety of chemical and biological analytes that have relevance in industrial hygiene, environmental monitoring, homeland security, diagnostics, and biomedical applications.

  17. 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.

  18. Structure and Depletion at Fluorocarbon and Hydrocarbon/Water Liquid/Liquid Interfaces

    SciTech Connect

    Kashimoto,K.; Yoon, J.; Hou, B.; Chen, C.; Lin, B.; Aratono, M.; Takiue, T.; Schlossman, M.

    2008-01-01

    The results of x-ray reflectivity studies of two oil/water (liquid/liquid) interfaces are inconsistent with recent predictions of the presence of a vaporlike depletion region at hydrophobic/aqueous interfaces. One of the oils, perfluorohexane, is a fluorocarbon whose superhydrophobic interface with water provides a stringent test for the presence of a depletion layer. The other oil, heptane, is a hydrocarbon and, therefore, is more relevant to the study of biomolecular hydrophobicity. These results are consistent with the subangstrom proximity of water to soft hydrophobic materials.

  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. Wetting, spreading and reactions at liquid/solid interfaces

    NASA Astrophysics Data System (ADS)

    Pask, J. A.; Tomsia, A. P.

    1980-07-01

    Chemical reactions of glass metal interfaces are investigated. Chemical (thermodynamic) stable equilibrium at glass metal interfaces is established when the liquid glass becomes saturated with the low valence oxide of the metal. Stable or metastable equilibrium conditions at glass metal interfaces result in a constant contact angle in a sessile drop experiment. If chemical equilibrium is absent, then a driving force exists for the occurrence of a reaction to attain equilibrium. All reactions that take place contribute to the maintenance of the necessary saturation of the liquid and solid at the interface with the solid substrate oxide in order to realize chemical bonding across the interface. Spreading always occurs when the solid metal is an active participant in these reactions. Examples showing the development of these principles are based on systems of sodium disilicate with Fe, Co, Ni, Fe-Ni alloys, Pt, Ag, Au, Cu, Ta, W, Mo, Nb, Zr and Cr. The final structure and composition of the glass metal interfacial zone are determined by the kinetics and thermodynamics of the reactions that occur.

  1. Coherent X-ray Scattering from Liquid-Air Interfaces

    NASA Astrophysics Data System (ADS)

    Shpyrko, Oleg

    Advances in synchrotron x-ray scattering techniques allow studies of structure and dynamics of liquid surfaces with unprecedented resolution. I will review x-ray scattering measurements of thermally excited capillary fluctuations in liquids, thin polymer liquid films and polymer surfaces in confined geometry. X-ray Diffuse scattering profile due to Debye-Waller like roughening of the surface allows to probe the distribution of capillary fluctuations over a wide range of length scales, while using X-ray Photon Correlation Spectroscopy (XPCS) one is able to directly couple to nanoscale dynamics of these surface fluctuations, over a wide range of temporal and spacial scales. I will also discuss recent XPCS measurements of lateral diffusion dynamics in Langmuir monolayers assembled at the liquid-air interface. This research was supported by NSF CAREER Grant 0956131.

  2. Colloidal Particles and Liquid Interfaces: A Spectrum of Interactions

    NASA Astrophysics Data System (ADS)

    Kaz, David Martin

    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 equilibrium analysis has been used to explain why colloids often bind to liquid interfaces, an effect first observed a century ago by Ramsden and Pickering and later exploited in a wide range of material processes, including emulsification, water purification, mineral recovery, encapsulation, and the making of nanostructured materials. But little is known about the dynamics of binding, or any aspect of the interaction between a particle and an interface outside of equilibrium. This thesis explores the spectrum of particle-interface interactions, from non-binding to non-adsorptive binding and finally adsorptive binding and the relaxation toward equilibrium that ensues. Chapter 2 reviews the importance of interfacial particles in materials science, and serves as a partial motivation for the work presented here. Chapter 3 describes the apparatus and experimental procedures employed in the acquisition of our data, with a short review of experiments that led to the current set. Special attention is paid to the optical apparatus and the custom sample cells we designed. Chapter 4 deals with non-adsorptive interactions between colloidal particles and liquid interfaces. A theoretical discussion founded on (but not wedded to) classical DLVO theory is presented before the results of our experiments are analyzed. It is shown that particle-interface interactions may be purely repulsive or contain an attractive component that results in binding to the interface that is not associated with breach. In chapter 5 the adsorption of polystyrene microspheres to a water-oil interface is shown to be characterized by a sudden breach and an unexpectedly slow relaxation. Particles do not reach equilibrium even after 100 seconds, and the relaxation appears logarithmic in time, suggesting that complete

  3. Ordered ionic liquid structure observed at terraced graphite interfaces.

    PubMed

    He, Xing; Wu, Chengyi; Rajagopal, Karjini; Punpongjareorn, Napat; Yang, Ding-Shyue

    2016-02-01

    Reflection high-energy electron diffraction is presented as a contactless, surface-specific method to probe the ion organization and layering at the ionic liquid-solid interfaces. Three regimes can be identified for the structure of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]) on highly oriented pyrolytic graphite, which is strongly dependent on the distances of ions from the surface. Direct observations showed that the ultrathin ionic liquid (IL) assembly can exhibit bulk-like phase-transition behaviours as a result of the structural matching between the IL and graphite layers and the confinement template effect due to the surface topography of graphite. The present study illustrates the opportunities for conducting further studies of the structures and ultrafast dynamics of IL-solid interfaces. PMID:26775813

  4. Harnessing Nanoparticles to Control Evaporation at Liquid-Vapor Interfaces

    NASA Astrophysics Data System (ADS)

    Yong, Xin

    2015-11-01

    It is well known that nanoparticles with appropriate size and surface chemistry adsorb to liquid-vapor interfaces and consequently modify the mechanical properties of the interfaces. However, little has been explored about the effect of nanoparticles on the heat transfer occurring at the interfaces. Using many-body dissipative particle dynamics (MDPD), we model an evaporating interface with adsorbed nanoparticles. Homogeneous and amphiphilic Janus nanoparticles, which contain hydrophobic and hydrophobic surface regions, are considered in this study. We measure the variation in the evaporation rates of the interface by gradually increasing particle loading until a hexagonal-close-packed monolayer is achieved. We explore the effect of surface chemistry and surface composition of the particles and demonstrate that evaporation can be readily adjusted by tuning the interaction parameters and amphiphilic ratio. Importantly, we observe that the evaporation suppression by adsorbed nanoparticles occurs only when the ambient vapor pressure is low. This study provides a fundamental understanding of the phase transition in multiphase interfacial systems and opens up new routes to additional control over evaporating interfaces.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Local order of liquid water at the electrochemical interface

    NASA Astrophysics Data System (ADS)

    Fernandez Serra, Marivi; Pedroza, Luana

    2014-03-01

    Understanding the aqueous electrochemical interface in an atomic level is of fundamental importance in many areas, such as catalysis and materials science. In this work we analyze in detail the structural, dynamic and energetic properties of liquid-water interacting with (111) Pd and Au surfaces at ambient temperature, using first principles molecular dynamics, with and without van der Waals interactions. We show that, contrary to what was found when studying ice-like water layers, van der Waals interactions play a critical role in modeling the aqueous/electrode interface. We show the differences in the ordering of water at the interface for Pd and Au, and we explain the change in work functions of these two metals in aqueous solution. DOE Early Career Award No. DE-SC0003871.

  10. 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. PMID:22386203

  11. 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.

  12. 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.

  13. 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.

  14. A polymer microgel at a liquid-liquid interface: theory vs. computer simulations.

    PubMed

    Rumyantsev, Artem M; Gumerov, Rustam A; Potemkin, Igor I

    2016-08-10

    We propose a mean-field theory and dissipative particle dynamics (DPD) simulations of swelling and collapse of a polymer microgel adsorbed at the interface of two immiscible liquids (A and B). The microgel reveals surface activity and lowers A-B interfacial tension. Attempting to occupy as large an interfacial area as possible, the microgel undergoes anisotropic deformation and adopts a flattened shape. Spreading over the interface is restricted by polymer subchain elasticity. The equilibrium shape of the microgel at the interface depends on its size. Small microgels are shown to be more oblate than the larger microgels. Increasing microgel cross-link density results in stronger reduction of the surface tension and weaker flattening. As the degree of immiscibility of A and B liquids increases, the microgel volume changes in a non-monotonous fashion: the microgel contraction at moderate immiscibility of A and B liquids is followed by its swelling at high incompatibility of the liquids. The segregation regime of the liquids within and outside the microgel is different. Being segregated outside the microgel, the liquids can be fully (homogeneously) mixed or weakly segregated within it. The density profiles of the liquids and the polymer were plotted under different conditions. The theoretical and the DPD simulation results are in good agreement. We hope that our findings will be useful for the design of stimuli responsive emulsions, which are stabilized by the microgel particles, as well as for their practical applications, for instance, in biocatalysis. PMID:27460037

  15. 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.

  16. 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.

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

    SciTech Connect

    Stoddard, Nathan G.; Clark, Roger F.

    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, . . . ).

  18. Surface order at surfactant-laden interfaces between isotropic liquid crystals and liquid phases with different polarity

    NASA Astrophysics Data System (ADS)

    Feng, Xunda; Bahr, Christian

    2011-03-01

    We present an ellipsometry study of the interface between thermotropic liquid crystals and liquid phases consisting of various binary mixtures of water and glycerol. The liquid-crystal samples contain a small constant amount of a surfactant which induces a homeotropic anchoring at the interface. We determine the smectic or nematic order at the interface in the temperature range above the liquid-crystal-isotropic transition while the water to glycerol ratio is varied, corresponding to a systematic modification of the polarity of the liquid phase. The surface-induced order becomes less pronounced with increasing glycerol concentration in the liquid phase. The observed behavior is compared with previous studies in which the surfactant concentration in the liquid-crystal bulk phase was varied. The results indicate that in both cases the magnitude of the surfactant coverage at the interface is the key quantity which determines the liquid-crystal surface order at the interface.

  19. Dependence of solid-liquid interface free energy on liquid structure

    SciTech Connect

    Wilson, S R; Mendelev, M I

    2014-09-01

    The Turnbull relation is widely believed to enable prediction of solid–liquid interface (SLI) free energies from measurements of the latent heat and the solid density. Ewing proposed an additional contribution to the SLI free energy to account for variations in liquid structure near the interface. In the present study, molecular dynamics (MD) simulations were performed to investigate whether SLI free energy depends on liquid structure. Analysis of the MD simulation data for 11 fcc metals demonstrated that the Turnbull relation is only a rough approximation for highly ordered liquids, whereas much better agreement is observed with Ewing’s theory. A modification to Ewing’s relation is proposed in this study that was found to provide excellent agreement with MD simulation data.

  20. Bioinspired One-Dimensional Nano-Wrinkles Guide Liquid Behaviors at the Liquid-Solid Interfaces.

    PubMed

    Li, Jing; Sun, Quanmei; Chen, Long; Feng, Jiantao; Han, Dong

    2016-01-01

    Learning from nature concerning how nanostructured surfaces interact with liquids may provide insight into better understanding of inside living biological interfaces bearing these nanostructures and further development of innovative materials contacting water. Here we investigate the dynamic behaviour of water droplet interacting with one-dimensional nano-wrinkles of different size on polydimethylsiloxane (PDMS) surface. The structure design of the variationally one-dimensional nano-wrinkles is inspired by in vivo responding topographic changes in aortic intima, which was characterized with liquid-phase atomic force microscopy. We show here that increasing the amplitude of the wrinkles promotes the spreading and energy dissipation of liquid droplets on the wrinkled interfaces. This result suggests a possible bio-protection mechanism of blood vessels via its structural changes on the aortic intima against elevated flowing blood, and provides a basis for tuning interfacial nanostructure of optimal durability against wearing by the liquid behaviors. PMID:27398541

  1. A search for the prewetting line. [in binary liquid system at vapor-liquid interface

    NASA Technical Reports Server (NTRS)

    Schmidt, J. W.; Moldover, M. R.

    1986-01-01

    This paper describes efforts to locate the prewetting line in a binary liquid system (isopropanol-perfluoromethylcyclohexane) at the vapor-liquid interface. Tight upper bounds were placed on the temperature separation (0.2 K) between the prewetting line and the line of bulk liquid phase separation. The prewetting line in systems at equilibrium was not detected. Experimental signatures indicative of the prewetting line occurred only in nonequilibrium situations. Several theories predict that the adsorption of one of the components (the fluorocarbon, in this case) at the liquid-vapor interface should increase abruptly, at a temperature sightly above the temperature at which the mixture separates into two liquid phases. A regular solution calculation indicates that this prewetting line should have been easily detectable with the instruments used in this experiment. Significant features of the experiment are: (1) low-gradient thermostatting, (2) in situ stirring, (3) precision ellipsometry from the vapor-liquid interface, (4) high resolution differential index of refraction measurements using a novel cell design, and (5) computer control.

  2. Size-dependent Assembly and Segregation of Nanoparticles at Liquid-liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Böker, Alexander; Lin, Yao; Skaff, Habib; Emrick, Todd; Russell, Thomas P.; Cookson, David; Dinsmore, A. D.; Zettl, Heiko; Krausch, Georg

    2004-03-01

    The self-assembly of nanoparticles at fluid-fluid interfaces, driven by the reduction in interfacial energy was investigated. With nanoparticles (2-6nm), thermal fluctuations compete with the interfacial segregation giving rise to a size-dependent self-assembly of the nanoparticles and a two-dimensional phase separation at the fluid interface. Studies on the dynamics of the nanoparticles and the self-assembled structures formed at the interface, using a pendant drop tensiometer, fluorescence photobleaching methods and in-situ grazing incidence small angle x-ray scattering (GISAXS), suggest a liquid-like behavior and ordering at the interfaces. This allows for effective cross-linking of the assembled particles at the interface in order to generate nanoporous capsules and membranes.

  3. Optical switch based on the electrically controlled liquid crystal interface.

    PubMed

    Komar, Andrei A; Tolstik, Alexei L; Melnikova, Elena A; Muravsky, Alexander A

    2015-06-01

    The peculiarities of the linearly polarized light beam reflection at the interface within the bulk of a nematic liquid crystal (NLC) cell with different orientations of the director are analyzed. Two methods to create the interface are considered. Combination of the planar and homeotropic orientations of the NLC director is realized by means of a spatially structured electrode under the applied voltage. In-plane patterned azimuthal alignment of the NLC director is created by the patterned rubbing alignment technique. All possible orthogonal orientations of the LC director are considered; the configurations for realization of total internal reflection are determined. The revealed relationship between the propagation of optical beams in a liquid crystal material and polarization of laser radiation has enabled realization of the spatial separation for the orthogonally polarized light beams at the interface between two regions of NLC with different director orientations (domains). Owing to variations in the applied voltage and, hence, in the refractive index gradient, the light beam propagation directions may be controlled electrically. PMID:26192675

  4. 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

  5. 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.

  6. 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.

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

    PubMed

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

    2016-08-01

    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. PMID:27301317

  8. 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

  9. [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.

  10. [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.

  11. Interface Superconductivity in Cuprates Defies Fermi-Liquid Description

    DOE PAGESBeta

    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, formationmore » of charge-density waves, strong Coulomb interactions, or self-trapping of mobile charge carriers.« less

  12. 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. PMID:27320727

  13. Kinetics of Protein Adsorption at liquid/solid interfaces

    NASA Astrophysics Data System (ADS)

    Bellion, Markus; Santen, Ludger; Nagel, Armin; Mantz, Hubert; Quinn, Anthony; Jacobs, Karin

    2006-03-01

    Protein adsorption processes are of crucial importance in many biomedical processes. From a physical point of view these processes raise a number of challenging questions, e.g.: How does the surface influence the conformation of proteins at the surface? What are the characteristics of the protein film at the liquid/solid interface? In this work we investigate the adsorption kinetics of salivary proteins on different kinds of surfaces in a liquid environment. The adsorbed protein layers are analyzed by means of ellipsometry, plasmon resonance, and SPM. It turns out that the adsorbed amount of proteins is sensitive to the long ranged interactions of the solid surface. The experimental data are compared to extensive Monte Carlo simulation of a colloidal protein model. The Monte Carlo results strongly suggest that induced conformal changes lead to the experimentally observed three step kinetics of amylase.

  14. 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. PMID:25435157

  15. 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.

  16. 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.

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

    PubMed

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

    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. PMID:26133450

  18. 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.

  19. 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.

  20. Toxicity of Silver Nanoparticles at the Air-Liquid Interface

    PubMed Central

    Holder, Amara L.; Marr, Linsey C.

    2013-01-01

    Silver nanoparticles are one of the most prevalent nanomaterials in consumer products. Some of these products are likely to be aerosolized, making silver nanoparticles a high priority for inhalation toxicity assessment. To study the inhalation toxicity of silver nanoparticles, we have exposed cultured lung cells to them at the air-liquid interface. Cells were exposed to suspensions of silver or nickel oxide (positive control) nanoparticles at concentrations of 2.6, 6.6, and 13.2 μg cm−2 (volume concentrations of 10, 25, and 50 μg ml−1) and to 0.7 μg cm−2 silver or 2.1 μg cm−2 nickel oxide aerosol at the air-liquid interface. Unlike a number of in vitro studies employing suspensions of silver nanoparticles, which have shown strong toxic effects, both suspensions and aerosolized nanoparticles caused negligible cytotoxicity and only a mild inflammatory response, in agreement with animal exposures. Additionally, we have developed a novel method using a differential mobility analyzer to select aerosolized nanoparticles of a single diameter to assess the size-dependent toxicity of silver nanoparticles. PMID:23484109

  1. Enhancement of Magnetization in Liquid 3He at Aerogel Interface

    NASA Astrophysics Data System (ADS)

    Fukui, A.; Kondo, K.; Kato, C.; Obara, K.; Yano, H.; Ishikawa, O.; Hata, T.

    2013-05-01

    A novel feature of condensate state in liquid 3He is predicted theoretically, which consists of spin triplet s-wave Cooper pairs (Higashitani et al. in J. Low. Temp. Phys. 155:83-97, 2009). Such a spin triplet s-wave state will appear inside aerogel near the surface boundary contacting with superfluid 3He-B, and the enhancement of magnetization due to s-wave state is theoretically expected (Nagato et al. in J. Phys. Soc. Jpn. 78:123603, 2009; Higashitani et al. in Phys. Rev. B 85:024524, 2012). In order to detect this proximity effect, we made the interface in columnar glass tube which coated with 2.5 layer 4He, and set a saddle shape NMR coil very near the interface. At 7 bar, we found that superfluidity in liquid 3He inside aerogel never occurred, even at considerably low temperatures. At 24 bar below T/ T c =0.392, we observed no decrease of magnetization with decreasing temperatures. This phenomenon might be due to spin triplet s-wave Cooper pairs.

  2. Ordered and disordered colloidal particle monolayers at liquid crystal interfaces

    NASA Astrophysics Data System (ADS)

    Wei, Wei-Shao; Lohr, Matthew; Gharbi, Mohamed Amine; Stebe, Kathleen; Yodh, A. G.

    2014-03-01

    In this work, we investigate ordered colloidal particle monolayers at the air/liquid-crystal (LC) interface. Specifically, silica microparticles are treated with DMOAP to create homeotropic anchoring of LC mesogens at their surfaces. These particles are then spread on an air-exposed interface of the LC 5CB. Macroscopic ordered patterns of these microparticles form due to long-range interactions between particles that are mediated by elastic deformations of the underlying LC. Different confinement conditions lead to various self-assembled patterns ranging from hexagonal lattices to chain-like dipole formations. Using dark-field video microscopy, we track and analyze the dynamics of the colloidal particles in the hexagonal crystal packing, deriving mean squared displacements, phonon modes and density of states, etc., under several conditions. Further, heating of the nematic LC into its isotropic phase enables us to observe melting dynamics of this unusual quasi-2D crystal. The investigations provide insight into crystalline packings controlled by liquid-crystal mediated colloidal interactions. This work is funded by NSF Grant DMR12-05463, PENN MRSEC Grant DMR11-20901, and NASA Grant NNX08AO0G.

  3. Intermolecular interactions of liquid dichloromethane and equilibrium properties of liquid{endash}vapor and liquid{endash}liquid interfaces: A molecular dynamics study

    SciTech Connect

    Dang, L.X.

    1999-05-01

    Extensive molecular dynamics simulations are carried out to study the molecular interactions, liquid states, and liquid/vapor properties of dichloromethane. The study is also extended to the equilibrium properties of the liquid/liquid interface of water-dichloromethane. The intermolecular interactions among water, dichloromethane, and water-dichloromethane are described using our polarizable potential models. The equilibrium properties of liquid dichloromethane, including the radial distribution functions, the intermolecular structural factor, the self-diffusion coefficient, and the dielectric constant, are evaluated. The dielectric constant is computed using Ewald summation techniques and the computed result compared reasonably well with the available experimental data. Properties such as surface tensions and density profiles of liquid/vapor dichloromethane are evaluated. We found that the computed surface tensions for several temperatures are in excellent agreement with experimental data. The computed density profile of the liquid/liquid interface of water-dichloromethane is averaged over 1 ns and we found the computed profile to be quite smooth and stable. The effect of polarization on the liquid/liquid interfacial equilibrium properties is evaluated by computing the dipole moments of water and dichloromethane molecules as a function of the distance normal to the interface. We found that these values deviated significantly from the simulations that are based on nonpolarizable potential models. We attribute these observations to the changes in the electric fields around the water and dichloromethane molecules near the interface. {copyright} {ital 1999 American Institute of Physics.}

  4. Stabilization of Pickering emulsions by generating complex colloidal layers at liquid-liquid interfaces.

    PubMed

    Lee, Geun Ju; Son, Han Am; Cho, Jang Woo; Choi, Sang Koo; Kim, Hyun Tae; Kim, Jin Woong

    2014-01-01

    Typical Pickering emulsions accumulate particles to form a robust colloidal layer at an immiscible liquid-liquid interface. However, if the particles are smaller than tens of nanometers, they have a tendency toward coming off from the interface, thereby destabilizing emulsion drops. To solve this problem, a technique that can make the adsorbed nanoparticles stay at the interface should be developed. This study introduces a practical method that allows us to obtain a mechanically stable Pickering emulsions; n-decane was emulsified to form an oil-in-water emulsion of which interface was stabilized with a complex colloidal layer consisting of 12 nm-sized silica nanoparticles, a poly(vinyl alcohol) binder, and an alkyl-chained silane coupling agent. We have found that in the conditions of high salinity, the emulsion drops attract each other and form an emulsion gel phase. However, even in such harsh conditions, the complex silica layer maintains its original structure at the interface, thus stabilizing the emulsion drop against coalescence. PMID:24183436

  5. Energy transfer at gas-liquid interface: Towards energetic materials

    NASA Astrophysics Data System (ADS)

    Szabo, Tamas

    Physicochemical surface processes have great importance in the different fields of everyday life and science. Computational characterization of collisional energy transfer at a gas-liquid interface is a helpful tool to interpret recent experimental studies and to yield insight into the energy feedback mechanism of multiphase combustion problems. As a first step, a simple Lennard-Jones system was used to investigate the dependence of the collisional energy transfer and the gas atom trapping probabilities on the temperature of the bulk liquid, on the gas/liquid particle mass ratios, on the incident angle of the impinging projectile, and on the gas-liquid interaction strength. We find in accord with the experimental results that the kinematic effects dominate the energy transfer dynamics, but the importance of the role of surface roughening as the temperature of the liquid increases is also seen. The second system, nitromethane was chosen to extend the range of simulations. It is a molecular model system, representing nitramine-type energetic materials. Having had a good potential description for the nitromethane molecule including all internal degrees of freedom, we generated simplified molecular systems based on the original nitromethane model to isolate particular features of the dynamics. We have investigated the effect of the initial incident energy, of the inclusion of the internal degrees of freedom, of the initial incident kinetic energy and of the gas-surface interaction strength. The incorporation of internal degrees of freedom enhanced the collisional energy transfer. These calculations also point to the importance of simple kinematics as it predicts the increase of the ratio of energy transferred with increased initial incident energy of the gas particle.

  6. Levitation of a metallic sphere near gas-liquid and liquid-liquid interfaces by the repulsive Casimir force

    NASA Astrophysics Data System (ADS)

    Inui, Norio

    2014-06-01

    By counteracting gravity, the repulsive Casimir force enables stable levitation of a perfectly conducting particle near a liquid-air interface if the particle exists inside the liquid. In the present study, we examine the levitation of a gold particle near a bromobenzene-air interface and calculate the levitation height using the scattering-matrix formulation. In addition, we consider the Casimir force acting on a gold sphere near the interface between bromobenzene and water. At asymptotically large separations, the Casimir force is attractive because of the large static dielectric permittivity of water. However, the Casimir force changes from attractive to repulsive as the separation decreases. We also found that the gold particle can be levitated in bromobenzene above water.

  7. 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.

  8. Thermal Fluctuations of a Metal Disk Levitated by the Casimir Force above a Liquid-Liquid Interface

    NASA Astrophysics Data System (ADS)

    Inui, Norio; Goto, Kosuke

    2015-04-01

    The thermal fluctuations in the tilt angles of a disk levitated above a liquid-liquid interface by a repulsive Casimir force are compared with those of a disk suspended by surface tension at the interface. By using a proximity force approximation, the probability density function of the tilt angle of a copper disk immersed in cyclohexane in contact with water is calculated. We show that the tilt angle of the levitated disk of micron-order radius exhibits comparatively large fluctuations. Observance of the difference in the amplitude of the fluctuations could be helpful in determining the position of the disk relative to the liquid-liquid interface.

  9. 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.

  10. Stretching and ordering of amyloid fibrils at liquid interfaces

    NASA Astrophysics Data System (ADS)

    Del Gado, Emanuela; Schwenke, Konrad; Jordens, Sophia; Usov, Ivan; Mezzenga, Raffaele; Georgetown University Team; ETH Zurich Team

    We investigate the formation of nematic domains, which might be precursor of plaque formation, in the adsorption of amyloid fibrils at liquid interfaces. Combining experiments and computer simulations we analyse spatial correlations in the nematic order and in apparent persistence length. Non-equilibrium numerical simulations provide new insight into the coupling between those quantities. The emerging scenario is that the out-of-equilibrium adsorption favors the formation of spatial heterogeneities due to the presence of local nematic order that tend to persist upon increasing the surface coverage. Such structural heterogeneities are directly coupled to the apparent straightening of the brils and might affect the density and the mechanical properties of the final self-assembled material.

  11. Metal ion adsorption at the ionic liquid-mica interface

    NASA Astrophysics Data System (ADS)

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G.; Atkin, Rob

    2015-12-01

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ~60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al3+ system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made.Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete

  12. 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.

  13. Hierarchical tubular structures grown from the gel/liquid interface.

    PubMed

    Steenbjerg Ibsen, Casper Jon; Mikladal, Bjørn Fridur; Bjørnholt Jensen, Uffe; Birkedal, Henrik

    2014-12-01

    Three dimensional hierarchical materials are widespread in nature but are difficult to synthesize by using self-assembly/organization. Here, we employ a gel-liquid interface to obtain centimeter-long ∼100 μm diameter tubes with complex mineral wall structures that grow from the interface into solution. The gel, made from gelatin, is loaded with metal chloride salt, whereas the solution is a high pH anion source. Tubes were obtained with a range of cations (Ca(2+) , Sr(2+) , Ba(2+) , Cu(2+) , and Zn(2+) ) and anions (CO3 (2-) and PO4 (3-) ). The crystalline phases found in the tube walls corresponded to expectations from solution chemistries and phase solubilities. The growth mechanism is found to be akin to that of chemical gardens. The divalent cations modify the strength of the gelatin gel in a manner that involves not only simple electrostatic screening, but also ion-specific effects. Thus, tubes were not obtained for those ions and/or concentrations that significantly changed the gel's mechanical structure. At high Cu(2+) loading, for example, vertical convection bands, not Liesegang bands, were observed in the gels. PMID:25336024

  14. Metal ion adsorption at the ionic liquid-mica interface.

    PubMed

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G; Atkin, Rob

    2016-01-14

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ∼60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al(3+) system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made. PMID:26661934

  15. 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.

  16. 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...

  17. 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. PMID:25730302

  18. Rapid Decomposition of Cellulose Dissolved in Ionic Liquid Using Gas-Liquid Interface Discharge

    NASA Astrophysics Data System (ADS)

    Furukawa, Shoichiro; Inoue, Nobuhiro; Ishioka, Toshio; Furuya, Kenji; Harata, Akira

    2012-07-01

    Cellulose was dissolved at 3 wt % in 15 mL of 1-allyl-3-methylimidazolium chloride ([Amim]Cl) together with 2 wt % water, and then gas-liquid interface discharge was carried out at 20 W for 200 s. As a result, 7.6% of initially dissolved cellulose decomposed and 3.9% of initially dissolved cellulose changed into reducing sugar. Adding a small amount of water to the solution was essential for the decomposition of cellulose. [Amim]Cl was stable against the discharge, as determined from the NMR signals measured before and after the discharge.

  19. 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.

  20. The interaction effects on the adsorption properties of an alternating copolymer chain at liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Khattari, Z.; Hamasha, S.

    2014-09-01

    Analytical and numerical methods have been combined to investigate the effect of monomers-interfacial interactions on the behavior of a single alternating polymer chain at liquid-liquid interface. The exact Green's function of a Gaussian copolymer chain at attractive penetrable interface has been employed to determine monomer distribution profiles ρ(z), mean-square end-to-end distance and the interfacial tension Δγ of the alternating copolymer chain. A comparison between the diblock and alternating copolymer chain is presented. Our model shows that, the alternating copolymer adsorbs more readily than the diblock copolymer at liquid-liquid interface. Also, these copolymers are able to reduce the interfacial tension when presented at the interface.

  1. Low-gravity sensing of liquid/vapor interface and transient liquid flow

    NASA Astrophysics Data System (ADS)

    Jacobson, Saul A.; Korba, James M.; Lynnworth, Lawrence C.; Nguyen, Toan H.; Orton, George F.

    1987-03-01

    The work reported here deals mainly with tests on internally vaned cylindrical shell acrylic containers capped by hemispherical acrylic or aluminum end domes. Three different ultrasonic sensor techniques and one nucleonic technique presently are evaluated as possible solutions to the low-gravity liquid gauging problem. The ultrasonic techniques are as follows: use of a torsional wave sensor in which transit time is proportional to the integral of wetted distance x liquid density; integration of the flow rate output signal of a fast-response ultrasonic flowmeter; and use of multiplexed externally mounted 'point-sensor' transducers that sense transit times to liquid-gas interfaces. Using two commercial flowmeters and a thickness gauge modified for this particular project, bench tests were conducted at 1 g on liquids such as water, freon, and solvent 140, including both steady flow and pulsating flow with 40, 80, and 120 ms flow pulses. Subsequently, flight tests were conducted in the NASA KC-135 aircraft in which nearly 0-g conditions are obtainable for up to about 5 s in each of a number of repetitive parabolic flight trajectories. In some of these brief low-gravity flight tests freon was replaced with a higher-viscosity fuel to reduce sloshing and thereby obtain settled surfaces more quickly.

  2. 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.

  3. 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.

  4. Resolving gas-liquid interface geometry using light field imaging

    NASA Astrophysics Data System (ADS)

    Jafek, Alexander; Belden, Jesse; Truscott, Tadd

    2014-11-01

    We present a novel approach for reconstructing the geometry of a three-dimensional specular gas-liquid interface from an image captured by a light-field camera. Whereas the scanning of a diffuse surface can be accomplished with a simple projector-camera system, the local reconstruction of a specular surface is non-unique and requires a more constrained sampling method. In our set-up, a known array of laser points is reflected by the unknown specular surface onto the image plane of a light-field camera. For each illuminated pixel, possible surfaces are generated that are defined by a depth location and local surface normal vector. We show that when the aperture is sufficiently small we can find the exact location and orientation of the local surface. Further, we present an algorithm that allows us to reconstruct a reflective surface from images that are taken with wider apertures. The algorithm searches the possible surfaces for points and normal vectors that are most consistent with each other based on input parameters. We present our simulated results with experimental validation.

  5. 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.

  6. Structural organization of liquid crystals at liquid crystal-air interface: Synchrotron X-ray reflectivity and computational simulations

    NASA Astrophysics Data System (ADS)

    Sadati, Monirosadat; Ramezani-Dakhel, Hadi; Bu, Wei; Sevgen, Emre; Liang, Zhu; Erol, Cem; Taheri Qazvini, Nader; Rahimi, Mohammad; Lin, Binhua; Roux, Benoit; Schlossman, Mark; de Pablo, Juan J.

    Numerous applications of liquid crystals (LC) rely on control of molecular orientation at an interface. However, little is known about the precise molecular structure of such interfaces. In this work, we have performed synchrotron X-ray reflectivity measurements accompanied by an advanced theoretical and computational analysis to study the structural organization of liquid crystals at the air-liquid crystal interface. The X-ray reflectivity was measured from two nematic (5CB) and smectic (8CB) liquid crystals at several temperatures, in the nematic phase and above the nematic-isotropic transition. Our computational simulations and X-ray reflectivity results indicate that in the case of 8CB nematic phase, incipient bulk smectic fluctuations are pinned at the interface to form temperature-dependent multilayers at the interface. Such layers can extend far from the interface. However, the interface of 5CB in the nematic phase exhibits a relatively small number of layers. These measurements will be extended to the study of the LC-aqueous electrolyte interfaces to understand the effects of electrostatic interactions and external stimuli on the interfacial anchoring energy and LC orientational ordering.

  7. Novel method for Ag colloidal cluster formation by laser ablation at the air-liquid interface

    NASA Astrophysics Data System (ADS)

    Nishi, Teppei; Akimoto, Yusuke; Takahashi, Naoko; Kitazumi, Kosuke; Kajiya, Shuji; Watanabe, Yoshihide

    2015-09-01

    We report a novel method for formation of sub-nanoclusters by laser ablation at the air-liquid interface. The density of plasma induced by laser ablation at the air-liquid interface should be lower than that produced by laser ablation in liquid. In the lower density plasma, the produced clusters rarely grow or aggregate into larger clusters because the collision probability is low, resulting in the formation of small clusters. Ag sub-nanoclusters were observed by electrospray ionization mass spectrometry (ESI-MS) and X-ray photoelectron spectroscopy (XPS). These results show that low-density plasma can be applied to small-cluster formation and that laser ablation at the air-liquid interface produces a good reactive field for the formation of sub-nanoclusters. Our results highlight the importance of low-density plasma induced at the air-liquid interface for sub-nanocluster formation.

  8. 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.

  9. Communication: Thermal rectification in liquids by manipulating the solid-liquid interface.

    PubMed

    Murad, Sohail; Puri, Ishwar K

    2012-08-28

    Thermal rectification, the origin of which lies in modifying the thermal resistance in a nonlinear manner, could significantly improve the thermal management of a wide range of nano-devices (both electronic and thermoelectric), thereby improving their efficiencies. Since rectification requires a material to be inhomogeneous, it has been typically associated with solids. However, the structure of solids is relatively difficult to manipulate, which makes the tuning of thermal rectification devices challenging. Since liquids are more amenable to tuning, this could open up new applications for thermal rectification. We use molecular dynamics simulations to demonstrate thermal rectification using liquid water. This is accomplished by creating an inhomogeneous water phase, either by changing the morphology of the surface in contact with the liquid or by imposing an arbitrary external force, which in practice could be through an electric or magnetic field. Our system consists of a bulk fluid that is confined in a reservoir that is bounded by two walls, one hot and the other cold. The interfacial (Kapitza) thermal resistance at the solid-fluid interface and the density gradient of the bulk fluid both influence the magnitude of the thermal rectification. However, we find that the role of the interfacial resistance is more prominent than the application of an external force on the bulk fluid. PMID:22938211

  10. Structure and Mass Transport Characteristics at the Intrinsic Liquid-Vapor Interfaces of Alkanes.

    PubMed

    Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

    2016-07-28

    In this paper, an instantaneous interface definition has been used to study the intrinsic structure and self-diffusion coefficient in the vicinity of the liquid-vapor interfaces of decane and tetracosane at three different temperatures using molecular dynamics simulations, and the results have been compared with those obtained on the basis of the conventional Gibbs dividing surface (time- and space-averaged interface). The alkane molecules were modeled using the united atom NERD force field. Partial layered structures of alkane molecules at the liquid-vapor interface are observed as a pinned structure of alkane liquids based on the intrinsic interface. This kind of characteristic has not been observed in the density profiles obtained based on the Gibbs dividing surface. By examining the orientation order parameter and radius of gyration of the alkane molecules, it was observed that the alkane molecules were preferentially oriented to be more parallel to the intrinsic interface than to the Gibbs dividing surface, and the shape of the alkane molecules is slightly changed in the vicinity of the liquid-vapor interfaces. The self-diffusion coefficient parallel to the intrinsic interface was examined using the Green-Kubo relation, where the projection of the velocity in the parallel direction to the local intrinsic interface is used in the velocity correlation function. It was found that the self-diffusion coefficient in the direction parallel to the intrinsic interface changes as the position approaches the interface in a more obvious manner as compared with the self-diffusion coefficient obtained with respect to the Gibbs dividing surface. These results suggest that the use of an instantaneous interface definition allowed us to capture sharp variations in transport properties which are originating due to steeper structure at the liquid-vapor interfaces. PMID:27387788

  11. 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. PMID:23848775

  12. 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. PMID:27239973

  13. 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. PMID:27216678

  14. Forming Nanoparticle Monolayers at Liquid-Air Interfaces by Using Miscible Liquids.

    PubMed

    Zhang, Datong; Hu, Jiayang; Kennedy, Kathleen M; Herman, Irving P

    2016-08-23

    One standard way of forming monolayers (MLs) of nanoparticles (NPs) is to drop-cast a NP dispersion made using one solvent onto a second, immiscible solvent; after this upper solvent evaporates, the NP ML can be transferred to a solid substrate by liftoff. We show that this previously universal use of only immiscible solvent pairs can be relaxed and close-packed, hexagonally ordered NP monolayers can self-assemble at liquid-air interfaces when some miscible solvent pairs are used instead. We demonstrate this by drop-casting an iron oxide NP dispersion in toluene on a dimethyl sulfoxide (DMSO) liquid substrate. The NPs are energetically stable at the DMSO surface and remain there even with solvent mixing. Excess NPs coagulate and precipitate in the DMSO, and this limits NPs at the surface to approximately 1 ML. The ML domains at the surface nucleate independently, which is in contrast to ML growth at the receding edge of the drying drop, as is common in immiscible solvent pair systems and seen here for the toluene/diethylene glycol immiscible solvent pair system. This new use of miscible solvent pairs can enable the formation of MLs for a wider range of NPs. PMID:27458656

  15. Diffusion transport of negative ions through the interface between cryogenic liquids

    SciTech Connect

    Lebedeva, E. V.; Dyugaev, A. M.; Grigoriev, P. D.

    2010-04-15

    A theory of electron bubble transport through the interface between cryogenic liquids is developed based on a new approach to calculating the potential of interaction of a bubble with the interface. The theory is in good agreement with experiments on the electric-field dependence of the potential barrier near the interface between liquid {sup 4}He, {sup 3}He, and vacuum, as well as at the interface between {sup 3}He and {sup 4}He saturated solutions. It is found that the interaction potential dependence on the distance between the electron bubble and the interface is isotopically invariant to three versions of such an interface. The dependence of the lifetime of negative ions in {sup 4}He and {sup 3}He on the temperature and electric field has been determined using the Kramers theory.

  16. 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. PMID:27199104

  17. Molecular-dynamics simulation of the effect of ions on a liquid-liquid interface for a partially miscible mixture

    NASA Astrophysics Data System (ADS)

    Wardle, Kent E.; Carlson, Eric; Henderson, Douglas; Rowley, Richard L.

    2004-04-01

    Molecular-dynamics simulations were performed to model the effect of added salt ions on the liquid-liquid interface in a partially miscible system. Simulations of the interface between saturated phases of a model 1-hexanol+water system show a bilayer structure of 1-hexanol molecules at the interface with -OH heads of the first layer directed into the water phase and the opposite orientation for the second layer. The alignment of the polar -OH groups at the interface stabilizes a charge separation of sodium and chloride ions when salt is introduced into the aqueous phase, producing an electrical double layer. Chloride ions aggregate nearer the interface and sodium ions move toward the bulk water phase, consistent with the explanation that the -OH alignment presents a region of partial positive charges to which the hydrated chloride atoms are attracted. Ions near the interface were found to be less solvated than those in the bulk phase. An electric field was also applied to drive ions through the interface. Ions crossing the interface tended to shed water molecules as they entered the hexanol bilayer, leaving a trail of water molecules. Stabilization and facilitated transport of the ion by interactions with the second layer of hexanol molecules appeared to be an important step in the mechanism of sodium ion transport.

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

    NASA Astrophysics Data System (ADS)

    Willard, Adam P.; Chandler, David

    2014-11-01

    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.

  19. 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

  20. Low-frequency sound transmission through a gas-liquid interface.

    PubMed

    Godin, Oleg A

    2008-04-01

    Typically, sound speed in gases is smaller and mass density is much smaller than in liquids, resulting in a very strong acoustic impedance contrast at a gas-liquid interface. Sound transmission through a boundary with a strong impedance contrast is normally very weak. This paper studies the power output of localized sound sources and acoustic power fluxes through a plane gas-liquid interface in a layered medium. It is shown that, for low-frequency sound, a phenomenon of anomalous transparency can occur where most of the acoustic power generated by a source in a liquid half-space can be radiated into a gas half-space. The main physical mechanism responsible for anomalous transparency is found to be an acoustic power transfer by inhomogeneous (evanescent) waves in the plane-wave decomposition of the acoustic field in the liquid. The effects of a liquid's stratification and of guided sound propagation in the liquid on the anomalous transparency of the gas-liquid interface are considered. Geophysical and biological implications of anomalous transparency of water-air interface to infrasound are indicated. PMID:18396996

  1. 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...

  2. Surfactant-induced nematic wetting layer at a thermotropic liquid crystal/water interface.

    PubMed

    Bahr, Ch

    2006-03-01

    An ellipsometric study of the interface between a thermotropic liquid crystal and water near the nematic-isotropic phase transition of the liquid crystal is presented. At temperatures above the transition, a nematic wetting layer appears at the interface if the water phase contains a surfactant inducing a homeotropic alignment of the nematic phase. The detailed behavior is significantly influenced by the concentration of the surfactant. The results can be described by a Landau model of nematic wetting in which the surfactant concentration tunes the magnitude of an ordering interface potential. PMID:16605490

  3. 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.

  4. The liquid crystal light valve, an optical-to-optical interface device

    NASA Technical Reports Server (NTRS)

    Jacobson, A. D.; Beard, T. D.; Bleha, W. P.; Margerum, J. D.; Wong, S. Y.

    1972-01-01

    A photoactivated liquid crystal light valve is described as an optical-to-optical interface device (OTTO) which is designed to transfer an optical image from a noncoherent light beam to a spatially coherent beam of light, in real time. Schematics of OTTO in use, the liquid cyrstal cell, and the liquid crystal structure are presented. Sensitivity characteristics and the principles of operation are discussed.

  5. 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

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

    PubMed

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

    2015-01-01

    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. PMID:26690392

  7. Distribution of solute at solid-liquid interface during solidification of melt

    NASA Astrophysics Data System (ADS)

    Fukui, Keisuke; Maeda, Kouji

    1998-11-01

    A model for predicting a distribution coefficient (ki) of solute at the solid-liquid (S-L) interface, when the solid layer is growing, is proposed. The interfacial distribution coefficient is expressed as a function of two gradients of the liquid concentration and equilibrium concentration at the S-L interface. The model is applied to the solidification of a simple eutectic binary liquid of lauric acid and myristic acid in an enclosed rectangular box in which a vertical wall is cooled. The impurity-concentration profile in solid is predicted from the direct numerical computations.

  8. 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.

  9. 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.

  10. 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.

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

    DOE PAGESBeta

    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

  12. 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.

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    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.

  16. Computational Study of ions binding to the liquid interface of water

    SciTech Connect

    Dang, Liem X. )

    2002-08-12

    We have performed extensive classical molecular dynamics simulations to examine the molecular transport mechanisms of the I-, Br-, Cl- and Na+ ions across the liquid/vapor interface of water. The potentials of mean force were calculated using the constrained mean force approach and polarizable potential models were used to describe the interactions among the species. The simulated potentials of mean force were found to be different, depending on the type of anion. The larger I- and Br- anions bind more strongly to the liquid/vapor interface of water than did the smaller Cl-ion. It is important to note here that most of the gas phase and solution phase properties of the Br- anion are quite similar to that of the Cl- ion. At the interface, however, the interactions of the Br- and Cl- anions with the water interface appeared to be significantly different. We found that the anions approach the interface more closely do than cations. We have also studied the transport mechanism of an I- across the water/dichloromethane interface. The computed potential of mean force showed no well-defined minimum as in the liquid/vapor case, but a stabilization free energy of about?1 kcal/mol near the interface with respect to the bulk liquid was observed. The I- anion carried a water molecule with it as it crossed the interface. This result is in agreement with a recent experimental study on a similar system. Our work differs from earlier contributions in that our potential models have taken many-body effects into account, and in some cases, these effects cannot be neglected. To the best of our knowledge, this work significantly advances our understanding of molecular processes at the liquid interfaces.

  17. 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.

  18. 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.

  19. Convection effects at solid-liquid interfaces: Influence of gravity

    NASA Technical Reports Server (NTRS)

    Glicksman, M. E.; Fang, Q. T.; Coriell, S. R.; Boisvert, R. F.

    1983-01-01

    The stability of the flow between two vertical, infinite, rigid, coaxial cylinders held at different temperatures is analyzed by linear stability theory. For a Prandtl number of 22.8 and a radius ratio of 0.02, the flow is unstable to an axisymmetric perturbation at a critical Grashof number of 2150; the wave speed of the instability is comparable to the maximum velocity of the unperturbed flow. When the rigid outer cylinder-fluid interface is replaced by a crystal-melt interface which can change shape, two new modes of instability occur at lower Grashof numbers.

  20. 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.

  1. 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.

  2. Biological membrane modeling with a liquid/liquid interface. Probing mobility and environment with total internal reflection excited fluorescence.

    PubMed Central

    Morrison, L E; Weber, G

    1987-01-01

    Total internal reflection of exciting light, in combination with fluorescence intensity and polarization measurements, was used to selectively study fluorescent compounds adsorbed to the interface region between two immiscible liquids. A fluorometer was constructed which provided excitation at variable angles of incidence and allowed sensitive detection of polarized fluorescence emitted from the interface. The compound 4,4'-bis-1-phenylamino-8-naphthalenesulfonate (bis-ANS) was examined at a decalin/water interface and was found to possess remarkable affinity for the interface region with the bulk of the adsorbed molecule residing in the decalin phase. The adsorbed fluorophore displayed an apparent hindered rotation in the plane of the interface with a rotational diffusion coefficient 3- to 12-fold lower than that expected for bis-ANS in solution. While other dyes examined were not found to be significantly surface active, the addition of cationic surfactant sufficed to induce adsorption of the anionic fluorophore 1-aminonaphthalene-3,6,8-trisulfonic acid. This fluoropore was found to reside in an aqueous environment when bound to the interface, and it also exhibited hindered rotation in the plane of the interface. As the concentrations of the dyes were increased, both adsorbed dyes exhibited polarization reductions consistent with excitation energy transfer. Adsorption of bis-ANS was reversed by addition of bovine serum albumin. The membrane protein cytochrome b5 was found not to bind at the decalin/water interface, indicating that interaction with lipid is required for its adherence to biological membranes. PMID:3651556

  3. 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.

  4. Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

    PubMed

    Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

    2015-05-20

    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 drop across a load resistor 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 electrical 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. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces. PMID:25923410

  5. 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

  6. Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

    PubMed

    de Eulate, Eva Alvarez; Silvester, Debbie S; Arrigan, Damien W M

    2015-12-01

    At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents. PMID:26489692

  7. Thermal resistance at a liquid-solid interface dependent on the ratio of thermal oscillation frequencies

    NASA Astrophysics Data System (ADS)

    Kim, BoHung

    2012-12-01

    Non-equilibrium molecular dynamics simulations of atomic-scale thermal resistance at a solid-liquid interface are theoretically investigated with a simple modal analysis of a one-dimensional lattice system. In the modal analysis, the solid-liquid intermolecular interaction strength between is taken into account as the stiffness constant between the solid and liquid molecular masses, and plays a key role in understanding the interfacial thermal resistance. The results show that the interfacial thermal resistance is proportional to the 4th power of the ratio of the thermal oscillation frequencies for the solid and liquid molecules, which provides a better physical description for the interfacial thermal resistance.

  8. Electron transfer at semiconducting metal dichalcogenide/liquid electrolyte interfaces

    SciTech Connect

    Howard, J.N.

    1992-01-01

    Charge transfer at semiconductor/electrolyte interfaces is the critical process in photoelectrochemical systems. Many aspects of the theory for these interfaces have yet to be experimentally verified. There are few reliable measurements of the fundamental electron transfer rate at nonilluminated semiconductors. This situation stems from experimental limitations imposed by most semiconductor electrode surfaces. Layered metal dichalcogenide semiconductors have excellent properties as semiconductor electrodes, but edge sites and crystal defects must be masked so only the defect-free basal plane of the two-dimensional material is exposed to solution. Conventional epoxy encapsulation of the crystal epoxy can introduce deleterious effects. A minielectrochemical cell was developed to perform experiments in a single drop of electrolyte held against the working electrode. The electrochemical behavior and operational considerations of the cell for aqueous and nonaqueous systems were investigated. Spatially-resolved electrochemistry was demonstrated for n-WSe[sub 2] and highly ordered pyrolytic graphite. The minicell was used to investigate electron transfer at nonilluminated n-WSe[sub 2]/dimethylferrocene[sup +/0] interfaces. This semiconductor is resistant to corrosion and has stable interfacial energetics. Interfaces with excellent diode behavior could be obtained by probing different regions of the surface. Electron transfer at these high quality surfaces was studied over an extensive solution concentration range. The rate of electron transfer was independent of solution acceptor concentration from 5 [mu]M to 0.25 M. The electron transfer data can be explained by assuming a surface-state mediate mechanism. A second metal dichalcogenide, n-SnS[sub 2], was investigated to compare the behavior of this wide band gap material to the narrow band gap n-WSe[sub 2]. The n-SnS[sub 2] electrodes displayed undesirable electrochemical effects in several solvent systems.

  9. 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

  10. 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.

  11. Instability of an interface between air and a low conducting liquid subjected to charge injection

    NASA Astrophysics Data System (ADS)

    Chicón, Rafael; Pérez, Alberto T.

    2006-10-01

    We study the linear stability of an interface between air and a low conducting liquid in the presence of unipolar injection of charge. As a consequence of charge injection, a volume charge density builds up in the air gap and a surface charge density on the interface. Above a certain voltage threshold the electrical stresses may destabilize the interface, giving rise to a characteristic cell pattern known as rose-window instability. Contrary to what occurs in the classical volume electrohydrodynamic instability in insulating liquids, the typical cell size is several times larger than the liquid depth. We analyze the linear stability through the usual procedure of decomposing an arbitrary perturbation into normal modes. The resulting homogeneous linear system of ordinary differential equations is solved using a commercial software package. Finally, an analytical method is developed that provides a solution valid in the limit of small wavenumbers.

  12. Molecular Interactions in Monolayers οf Azo Dye/Liquid Crystal Mixtures at Interfaces

    NASA Astrophysics Data System (ADS)

    Bauman, D.; Płóciennik, A.; Inglot, K.

    2009-08-01

    Full Text PDF A study of azo dye/liquid crystal mixtures in monolayers formed at an air-water interface (the Langmuir films) and at a solid surface (the Langmuir-Blodgett films) has been performed. Five azo dyes with various molecular structure and the liquid crystal 4-octyl-4' cyanobiphenyl (8CB) have been used. The dyes have been added to the liquid crystal at various molar fractions. Surface pressure and surface potential versus mean molecular area isotherms for the Langmuir films have been recorded and information about intermolecular interactions at the air-water interface has been obtained. On the basis of electronic absorption measurements for the Langmuir and Langmuir-Blodgett films the conclusions about the ability of dyes molecules to form self aggregates at the interfaces have been drawn. The influence of the dye molecular structure and its concentration on aggregates' geometry has been found.

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

    PubMed

    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. PMID:27300863

  14. 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.

  15. Ab initio study on the dynamics of furfural at the liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Dang, Hongli; Xue, Wenhua; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2013-03-01

    Catalytic biomass conversion sometimes occurs at the liquid-solid interfaces. We report ab initio molecular dynamics simulations at finite temperatures for the catalytic reactions involving furfural at the water-Pd and water-Cu interfaces. We found that, during the dynamic process, the furan ring of furfural prefers to be parallel to the Pd surface and the aldehyde group tends to be away from the Pd surface. On the other hand, at the water-Cu(111) interface, furfural prefers to be tilted to the Cu surface while the aldehyde group is bonded to the surface. In both cases, interaction of liquid water and furfural is identified. The difference of dynamic process of furfural at the two interfaces suggests different catalytic reaction mechanisms for the conversion of furfural, consistent with the experimental investigations. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSED's and NERSC's supercomputers

  16. Numerical simulation of solid liquid interface behavior during continuous strip casting process.

    PubMed

    Lee, Changbum; Yoon, Wooyoung; Shin, Seungwon; Lee, Jaewoo; Jang, Bo-Yun; Kim, Joonsoo; Ahn, Youngsoo; Lee, Jinseok

    2013-05-01

    A new metal-strip-casting process called continuous strip-casting (CSC) has been developed for making thin metal strips. A numerical simulation model to help understand solid-liquid interface behavior during CSC has been developed and used to identify the solidification morphologies of the strips and to determine the optimum processing conditions. In this study, we used a modified level contour reconstruction method (LCRM) and the sharp interface method to modify interface tracking, and performed a simulation analysis of the CSC process. The effects of process parameters such as heat-transfer coefficient and extrusion velocity on the behavior of the solid-liquid interface were estimated and used to improve the apparatus. A Sn (Tin) plate of dimensions 200 x 50 x 1 mm3 was successfully produced by CSC for a heat-transfer coefficient of 104 W/m2 K and an extrusion velocity of 0.2 m/s. PMID:23858856

  17. Layering of [BMIM]+-based ionic liquids at a charged sapphire interface

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Schramm, Sebastian; Schröder, Heiko; Reichert, Harald; Deutsch, Moshe; De Souza, Emerson J.; Okasinski, John S.; Ocko, Benjamin M.; Honkimäki, Veijo; Dosch, Helmut

    2009-09-01

    The structure of two model room temperature ionic liquids, [BMIM]+[PF6]- and [BMIM]+[BF4]-, near the solid/liquid interface with charged Al2O3(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM]+[PF6]- exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM]+[BF4]-, shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.

  18. On the origin of the electrostatic potential difference at a liquid-vacuum interface

    PubMed Central

    Harder, Edward; Roux, Benoît

    2008-01-01

    The microscopic origin of the interface potential calculated from computer simulations is elucidated by considering a simple model of molecules near an interface. The model posits that molecules are isotropically oriented and their charge density is Gaussian distributed. Molecules that have a charge density that is more negative toward their interior tend to give rise to a negative interface potential relative to the gaseous phase, while charge densities more positive toward their interior give rise to a positive interface potential. The interface potential for the model is compared to the interface potential computed from molecular dynamics simulations of the nonpolar vacuum-methane system and the polar vacuum-water interface system. The computed vacuum-methane interface potential from a molecular dynamics simulation (−220 mV) is captured with quantitative precision by the model. For the vacuum-water interface system, the model predicts a potential of −400 mV compared to −510 mV, calculated from a molecular dynamics simulation. The physical implications of this isotropic contribution to the interface potential is examined using the example of ion solvation in liquid methane. PMID:19102551

  19. 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.

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

    SciTech Connect

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-08-25

    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.

  1. 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.

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

    DOE PAGESBeta

    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

  3. 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

  4. 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.

  5. Protein denaturation by combined effect of shear and air-liquid interface.

    PubMed

    Maa, Y F; Hsu, C C

    1997-06-20

    The effect of shear alone on the aggregation of recombinant human growth hormone (rhGH) and recombinant human deoxyribonuclease (rhDNase) has been found to be insignificant. This study focused on the synergetic effect of shear and gas-liquid interface on these two model proteins. Two shearing systems, the concentric-cylinder shear device (CCSD) and the rotor/stator homogenizer, were used to generate high shear (> 10(6)) in aqueous solutions in the presence of air. High shear in the presence of an air-liquid interface had no major effect on rhDNase but caused rhGH to form noncovalent aggregates. rhGH aggregation was induced by the air-liquid interface and was found to increase with increasing protein concentration and the air-liquid interfacial area. The aggregation was irreversible and exhibited a first-order kinetics with respect to the protein concentration and air-liquid interfacial area. Shear and shear rate enhanced the interaction because of its continuous generation of new air-liquid interfaces. In the presence of a surfactant, aggregation could be delayed or prevented depending upon the type and the concentration of the surfactant. The effect of air-liquid interface on proteins at low shear was examined using a nitrogen bubbling method. We found that foaming is very detrimental to rhGH even though the shear involved is low. The use of anti-foaming materials could prevent rhGH aggregation during bubbling. The superior stability exhibited by rhDNase may be linked to the higher surface tension and lower foaming tendency of its aqueous solution. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 54: 503-512, 1997. PMID:18636406

  6. 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.

  7. Dual harmonic Kelvin probe force microscopy at the graphene–liquid interface

    SciTech Connect

    Collins, Liam; Rodriguez, Brian J.; Kilpatrick, Jason I.; Weber, Stefan A. L.; Vlassiouk, Ivan V.; Tselev, Alexander; Jesse, Stephen; Kalinin, Sergei V.

    2014-03-31

    Kelvin probe force microscopy (KPFM) is a powerful technique for the determination of the contact potential difference (CPD) between an atomic force microscope tip and a sample under ambient and vacuum conditions. However, for many energy storage and conversion systems, including graphene-based electrochemical capacitors, understanding electrochemical phenomena at the solid–liquid interface is paramount. Despite the vast potential to provide fundamental insight for energy storage materials at the nanoscale, KPFM has found limited applicability in liquid environments to date. Here, using dual harmonic (DH)-KPFM, we demonstrate CPD imaging of graphene in liquid. We find good agreement with measurements performed in air, highlighting the potential of DH-KPFM to probe electrochemistry at the graphene–liquid interface.

  8. 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. PMID:26684395

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

    PubMed Central

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

    2015-01-01

    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. PMID:25870304

  10. Water-mediated ion–ion interactions are enhanced at the water vapor–liquid interface

    PubMed Central

    Venkateshwaran, Vasudevan; Vembanur, Srivathsan; Garde, Shekhar

    2014-01-01

    There is overwhelming evidence that ions are present near the vapor–liquid interface of aqueous salt solutions. Charged groups can also be driven to interfaces by attaching them to hydrophobic moieties. Despite their importance in many self-assembly phenomena, how ion–ion interactions are affected by interfaces is not understood. We use molecular simulations to show that the effective forces between small ions change character dramatically near the water vapor–liquid interface. Specifically, the water-mediated attraction between oppositely charged ions is enhanced relative to that in bulk water. Further, the repulsion between like-charged ions is weaker than that expected from a continuum dielectric description and can even become attractive as the ions are drawn to the vapor side. We show that thermodynamics of ion association are governed by a delicate balance of ion hydration, interfacial tension, and restriction of capillary fluctuations at the interface, leading to nonintuitive phenomena, such as water-mediated like charge attraction. “Sticky” electrostatic interactions may have important consequences on biomolecular structure, assembly, and aggregation at soft liquid interfaces. We demonstrate this by studying an interfacially active model peptide that changes its structure from α-helical to a hairpin-turn–like one in response to charging of its ends. PMID:24889634

  11. Two-phase stopped-flow measurement of the protonation of tetraphenylporphyrin at the liquid-liquid interface.

    PubMed

    Nagatani, H; Watarai, H

    1996-04-01

    The formation rate of the protonated form of tetraphenylporphyrin (TPP) in a dispersed two-phase system composed of dodecane and aqueous trichloroacetic acid (TCA) was studied by means of a stopped-flow method. The protonation reaction took place at the liquid-liquid interface, and the diprotonated TPP (H(2)TPP(2+)) formed was adsorbed there. In order to determine the rate-determining process, changes in absorbance at the absorption maximum wavelengths of TPP and H(2)TPP(2+) were analyzed. The obtained rate constant for the decrease of TPP in the organic phase, 21 ± 2 s(-1), was in agreement with that for the increase of diprotonated TPP at the interface, 20 ± 3 s(-1). The observed rate constants did not show any dependence on concentrations of both TPP and the acid. The experimental results suggested the rate-determining step to be the molecular diffusion process of TPP in the stagnant layer in the organic phase side at the liquid-liquid interface, and the thickness of the stagnant layer was estimated as 1.4 × 10(-4) cm. PMID:21619156

  12. The stability of a horizontal interface between air and an insulating liquid subjected to charge injection

    NASA Astrophysics Data System (ADS)

    Chicón, Rafael; Pérez, Alberto T.

    2014-03-01

    This paper presents the linear stability analysis of an interface between air and an insulating liquid subjected to a perpendicular electric field, in the presence of unipolar injection of charge. Depending on the characteristics of the liquid and the depth of the liquid layer two different instability thresholds may be found. One of them is characterized by a wavelength of the order of the liquid layer thickness and corresponds to the well-known volume instability of a liquid layer subjected to charge injection. The other one is characterized by a wavelength some ten times the liquid layer thickness and corresponds to the so-called rose-window instability, an instability associated to the balance of surface stresses.

  13. Solute rotational dynamics at the water liquid/vapor interface

    NASA Astrophysics Data System (ADS)

    Benjamin, Ilan

    2007-11-01

    The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.

  14. Oxidation of oleic acid at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, Laura F.; Bazerbashi, Mohamad F.; Beekman, Christopher P.; Hadad, Christopher M.; Allen, Heather C.

    2007-03-01

    Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both freshwater and saltwater sources. Oleic acid monolayers at the air/water interface and at the air/sodium chloride solution interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. Complementary techniques of infrared reflection adsorption spectroscopy and surface pressure measurements taken during monolayer oxidation confirmed the sum frequency results. Using this nonlinear optical technique coupled with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 M sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous subphase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

  15. 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.

  16. 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

  17. Molecular dynamics simulations of the liquid/vapor interface of SPC/E water

    SciTech Connect

    Taylor, R.S.; Dang, L,X.; Garrett, B.C.

    1996-07-11

    Molecular dynamics computer simulations have been used to explore the structural and dynamical properties of water`s liquid/vapor interface using the simple extended point charge (SPC/E) model. Comparisons to the existing experimental and simulation data suggest that the SPC/E potential energy function provides a semiquantitative description of this interface. The orientation of H{sub 2}O molecules at the interface is found to be bimodal in nature. The self-diffusion constant of water is calculated to be larger at the surface than in the bulk. 46 refs., 10 figs., 1 tab.

  18. Eliminating unwanted nanobubbles from hydrophobic solid/liquid interfaces: a case study using magnetoelastic sensors.

    PubMed

    Feng, Xinjian; Roy, Somnath C; Grimes, Craig A

    2008-04-15

    Air bubbles are known to form at the liquid/solid interface of hydrophobic materials upon immersion in a liquid (Holmberg, M.; Kdühle, A.; Garnaes, J.; Mørch, K. A.; Boisen, A. Langmuir 2003, 19, 10510-10513). In the case of gravimetric sensors, air bubbles that randomly form at the liquid-solid interface result in poor sensor-to-sensor reproducibility. Herein a superhydrophilic ZnO nanorod film is applied to the originally hydrophobic surface of a resonance-based magnetoelastic sensor. The superhydrophilic coating results in the liquid completely spreading across the surface, removing unwanted air bubbles from the liquid/sensor interface. The resonance amplitude of uncoated (bare) and ZnO-modified sensors are measured in air and then when immersed in saline solution, ethylene glycol, or bovine blood. In comparison to the bare, hydrophobic sensors, we find that the standard deviation of the resonance amplitudes of the liquid-immersed ZnO-nanorod-modified sensors decreases substantially, ranging from a 27% decrease for bovine blood to a 67% decrease for saline. The strategy of using a superhydrophilic coating can be applied to other systems having similar interfacial problems. PMID:18307368

  19. 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

  20. Rocket engine coaxial injector liquid/gas interface flow phenomena

    SciTech Connect

    Mayer, W.; Kruelle, G.

    1995-05-01

    Coaxial injectors are used for the injection and mixing of propellants H2/O2 in cryogenic rocket engines. The aim of the theoretical and experimental investigations presented here is to elucidate some of the physical processes in coaxial injector flow with respect to their significance for atomization and mixing. Experiments with the simulation fluids H2O and air were performed under ambient conditions and at elevated counter pressures up to 20 bar. This article reports on phenomenological studies of spray generation under a broad variation of parameters using nanolight photography and high-speed cinematography (up to 3 x 10(exp 4) frames/s). Detailed theoretical and experimental studies of the surface evolution of turbulent jets were performed. Proof was obtained of the impact of internal fluid jet motions on surface deformation. The m = 1 nonaxisymmetric instability of the liquid jet seems to be superimposed onto the small-scale atomization process. A model is presented that calculates droplet atomization quantities as frequency, droplet diameter, and liquid core shape. The overall procedure for implementing this model as a global spray model is also described and an example calculation is presented. 15 refs.

  1. Migration of liquid phase from the primary/peritectic interface in a temperature gradient

    NASA Astrophysics Data System (ADS)

    Peng, Peng; Li, XinZhong; Su, YanQing; Guo, JingJie

    2016-07-01

    The migration of the liquid droplets from the primary α/peritectic β interface at the peritectic temperature TP has been observed and analyzed in a Sn-Ni peritectic alloy. During the isothermal annealing stage of the interrupted directional solidification, a concentration gradient is established across the liquid droplets along the direction of the temperature gradient due to the temperature gradient zone melting. Simultaneous remelting/resolidification at the top/bottom of the liquid droplets by this concentration gradient have been confirmed to lead to migration of these droplets towards higher temperatures. The dependence of the migration distance of the liquid droplets on isothermal annealing time has been well predicted. Furthermore, since the lengths of the liquid droplet are not uniform along the direction of the temperature gradient, the remelting/resolidification rates which are dependent on the local morphology of liquid droplet are different at different local positions of the liquid droplets. It has been demonstrated that the morphology of the liquid droplet was also influenced by the morphologies of the liquid phase themselves. Therefore, the morphology of the liquid droplet itself changes from spherical to some kinds of irregular shapes during its migration.

  2. 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.

  3. Shape and Effective Spring Constant of Liquid Interfaces Probed at the Nanometer Scale: Finite Size Effects.

    PubMed

    Dupré de Baubigny, Julien; Benzaquen, Michael; Fabié, Laure; Delmas, Mathieu; Aimé, Jean-Pierre; Legros, Marc; Ondarçuhu, Thierry

    2015-09-15

    We investigate the shape and mechanical properties of liquid interfaces down to nanometer scale by atomic force microscopy (AFM) and scanning electron microscopy (SEM) combined with in situ micromanipulation techniques. In both cases, the interface is probed with a cylindrical nanofiber with radius R of the order of 25-100 nm. The effective spring constant of the nanomeniscus oscillated around its equilibrium position is determined by static and frequency-modulation (FM) AFM modes. In the case of an unbounded meniscus, we find that the effective spring constant k is proportional to the surface tension γ of the liquid through k = (0.51 ± 0.06)γ, regardless of the excitation frequency from quasi-static up to 450 kHz. A model based on the equilibrium shape of the meniscus reproduces well the experimental data. Electron microscopy allowed to visualize the meniscus profile around the fiber with a lateral resolution of the order of 10 nm and confirmed its catenary shape. The influence of a lateral confinement of the interface is also investigated. We showed that the lateral extension L of the meniscus influences the effective spring constant following a logarithmic evolution k ∼ 2πγ/ln(L/R) deduced from the model. This comprehensive study of liquid interface properties over more than 4 orders of magnitude in meniscus size shows that advanced FM-AFM and SEM techniques are promising tools for the investigation of mechanical properties of liquids down to nanometer scale. PMID:26295187

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

    PubMed

    Abe, Kiharu; Sumi, Tomonari; Koga, Kenichiro

    2016-03-01

    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. PMID:26595441

  5. Simulations of solid-liquid friction at ice-Ih/water interfaces

    NASA Astrophysics Data System (ADS)

    Louden, Patrick B.; Gezelter, J. Daniel

    2013-11-01

    We have investigated the structural and dynamic properties of the basal and prismatic facets of the ice Ih/water interface when the solid phase is drawn through the liquid (i.e., sheared relative to the fluid phase). To impose the shear, we utilized a velocity-shearing and scaling approach to reverse non-equilibrium molecular dynamics. This method can create simultaneous temperature and velocity gradients and allow the measurement of transport properties at interfaces. The interfacial width was found to be independent of the relative velocity of the ice and liquid layers over a wide range of shear rates. Decays of molecular orientational time correlation functions gave similar estimates for the width of the interfaces, although the short- and longer-time decay components behave differently closer to the interface. Although both facets of ice are in "stick" boundary conditions in liquid water, the solid-liquid friction coefficients were found to be significantly different for the basal and prismatic facets of ice.

  6. 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.

  7. 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.

  8. Step free energies at faceted solid-liquid interfaces from equilibrium molecular dynamics simulations.

    PubMed

    Frolov, T; Asta, M

    2012-12-01

    In this work a method is proposed for computing step free energies for faceted solid-liquid interfaces based on atomistic simulations. The method is demonstrated in an application to (111) interfaces in elemental Si, modeled with the classical Stillinger-Weber potential. The approach makes use of an adiabatic trapping procedure, and involves simulations of systems with coexisting solid and liquid phases separated by faceted interfaces containing islands with different sizes, for which the corresponding equilibrium temperatures are computed. We demonstrate that the calculated coexistence temperature is strongly affected by the geometry of the interface. We find that island radius is inversely proportional to superheating, allowing us to compute the step free energy by fitting simulation data within the formalism of classical nucleation theory. The step free energy value is computed to be γ(st) = 0.103 ± 0.005 × 10(-10) J/m. The approach outlined in this work paves the way to the calculation of step free energies relevant to the solidification of faceted crystals from liquid mixtures, as encountered in nanowire growth by the vapor-liquid-solid mechanism and in alloy casting. The present work also shows that at low undercoolings the Stillinger-Weber interatomic potential for Si tends to crystallize in the wurtzite, rather than the diamond-cubic structure. PMID:23231218

  9. Forces between a rigid probe particle and a liquid interface. II. The general case.

    PubMed

    Dagastine, R R; White, L R

    2002-03-15

    The semianalytic theory developed previously (Chan, D. Y. C., Dagastine, R. R., and White, L. R., J. Colloid Interface Sci. 236, 141 (2001)) to predict the force curve of an AFM measurement at a liquid interface using a colloidal probe has been expanded to incorporate a general force law with both attractive and repulsive forces. Expressions for the gradient of the force curve are developed to calculate the point at which the probe particle on the cantilever will spontaneously jump in toward the liquid interface. The calculation of the jump instability is reduced to a straightforward embroidery of the simple algorithms presented in Chan et al. In a variety of sample calculations using force laws including van der Waals, electrostatic, and hydrophobic forces for both oil/water and bubble/water interfaces, we have duplicated the general behaviors observed in several AFM investigations at liquid interfaces. The behavior of the drop as a Hookean spring and the numerical difficulties of a full numerical calculation of F(deltaX) are also discussed. PMID:16290470

  10. 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.

  11. Direct Numerical Simulation of turbulent flows over superhydrophobic surfaces: capillary waves on gas-liquid interface

    NASA Astrophysics Data System (ADS)

    Seo, Jongmin; García-Mayoral, Ricardo; Mani, Ali

    2015-11-01

    Superhydrophobic surfaces under liquid flow can produce significant slip, and thus drag reduction, when they entrap gas bubbles within their roughness elements. Our work aims to explore the onset mechanism to the failure of drag reduction by superhydrophobic surfaces when they are exposed to turbulent boundary layers. We focus on the effect of finite surface tension to the dynamic response of deformable interfaces between overlying water flow and the gas pockets. To this end, we conduct direct numerical simulations of turbulent flows over superhydrophobic surfaces allowing deformable gas-liquid interface. DNS results show that spanwise-coherent, upstream-traveling waves develop on the gas-liquid interface as a result of its interactions with turbulence. We study the nature and scaling of the upstream-traveling waves through semi-analytical modeling. We will show that the traveling waves are well described by a Weber number based on the slip velocity at the interface. In higher Weber number, the stability of gas pocket decreases as the amplitude of interface deformation and the magnitude of pressure fluctuations are augmented. Supported by Office of Naval Research and the Kwanjeong Educational Scholarship Foundation.

  12. 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

  13. Oxidation of oleic acid monolayers at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, L. F.; Bazerbashi, M. F.; Beekman, C. P.; Hadad, C. M.; Allen, H. C.

    2006-12-01

    Field studies of marine and continental aerosols find that fatty acid films form on aqueous tropospheric aerosols. Oxidation of the acyl chains is thought to be key to aerosol growth. Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both fresh and salt water sources. Using vibrational sum frequency generation spectroscopy and reflection absorption infrared spectroscopy, we present a molecular-level investigation of fatty acid monolayers at the air-water and air- sodium chloride solution interface and explore reactions with atmospheric oxidants by these model systems. Using sum frequency generation spectroscopy coupled with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 molar sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous sub-phase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

  14. Oxidation of oleic acid monolayers at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, Laura

    2008-03-01

    Field studies of marine and continental aerosols find that fatty acid films form on aqueous tropospheric aerosols. Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both fresh and salt water sources. Using vibrational sum frequency generation spectroscopy and reflection absorption infrared spectroscopy, we present a molecular-level investigation of fatty acid monolayers at the air-water and air-sodium chloride solution interface and explore reactions with atmospheric oxidants by these model systems. Coupling sum frequency generation spectroscopy with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 molar sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous sub-phase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

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

    PubMed

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

    2016-08-01

    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. PMID:27354032

  16. Impedance spectroscopy investigation of electrophysical characteristics of the electrode-liquid crystal interface

    NASA Astrophysics Data System (ADS)

    Belyaev, B. A.; Drokin, N. A.

    2015-01-01

    The behavior of frequency dependences of the impedance of a capacitive measuring cell with a liquid crystal has been investigated in the frequency range from 10-1 to 105 Hz. A method for determining electrophysical characteristics of the liquid crystal in the bulk and at the liquid crystal-metal electrode interface has been proposed and tested for liquid crystals of the alkyl cyanobiphenyl series, which are doped with ionic surfactants. The method is based on the use of an equivalent electrical circuit, which makes it possible to approximate the impedance spectra with the required accuracy, and also on the determination of the frequency at the singular point in the impedance spectra, at which the reactive component of the electric current flowing through the liquid-crystal cell is negligible compared to the active component.

  17. 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. PMID:27004449

  18. First-principles quantum-mechanical investigations of biomass conversion at the liquid-solid interfaces

    NASA Astrophysics Data System (ADS)

    Dang, Hongli; Xue, Wenhua; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    We report first-principles density-functional calculations and ab initio molecular dynamics (MD) simulations for the reactions involving furfural, which is an important intermediate in biomass conversion, at the catalytic liquid-solid interfaces. The different dynamic processes of furfural at the water-Cu(111) and water-Pd(111) interfaces suggest different catalytic reaction mechanisms for the conversion of furfural. Simulations for the dynamic processes with and without hydrogen demonstrate the importance of the liquid-solid interface as well as the presence of hydrogen in possible catalytic reactions including hydrogenation and decarbonylation of furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  19. Photoinduced Electron Transfer of PAMAM Dendrimer-Zinc(II) Porphyrin Associates at Polarized Liquid|Liquid Interfaces.

    PubMed

    Nagatani, Hirohisa; Sakae, Hiroki; Torikai, Taishi; Sagara, Takamasa; Imura, Hisanori

    2015-06-01

    The heterogeneous photoinduced electron-transfer reaction of the ion associates between NH2-terminated polyamidoamine (PAMAM) dendrimers and 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinato zinc(II) (ZnTPPS(4-)) was studied at the polarized water|1,2-dichloroethane (DCE) interface. The positive photocurrent arising from the photoreduction of ZnTPPS(4-) by a lipophilic quencher, decamethylferrocene, in the interfacial region was significantly enhanced by the ion association with the PAMAM dendrimers. The photocurrent response of the dendrimer-ZnTPPS(4-) associates was dependent on the pH condition and on the generation of dendrimer. A few cationic additives such as polyallylamine and n-octyltrimethyammonium were also examined as alternatives to the PAMAM dendrimer, but the magnitude of the photocurrent enhancement was rather small. The high photoreactivity of the dendrimer-ZnTPPS(4-) associates was interpreted mainly as a result of the high interfacial concentration of photoreactive porphyrin units associated stably with the dendrimer which was preferably adsorbed at the polarized water|DCE interface. The photochemical data observed in the second and fourth generation PAMAM dendrimer systems demonstrated that the higher generation dendrimer which can incorporate a porphyrin molecule more completely in the interior is less efficient for the photocurrent enhancement at the interface. These results indicated that the photoreactivity of ionic reactant at a polarized liquid|liquid interface can readily be modified via ion association with the charged dendrimer. PMID:25989445

  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. Charge transport due to photoelectric interface activation in pure nematic liquid-crystal cells

    NASA Astrophysics Data System (ADS)

    Pagliusi, P.; Cipparrone, G.

    2002-11-01

    We report a study of the crucial role of liquid-crystal-polymer interface on photoinduced transport and redistribution of charges in pure nematic liquid-crystal cells that exhibit a photorefractivelike effect. A stationary photocurrent that is 30% of the dark current has been measured for very low power illumination (few mW) and low applied dc electric field (about 0.1 V/mum). The experimental results indicate a clear dependence of the effect on the light wavelength. The absence of photocurrent in cells with only one component, liquid-crystal, or polymer, suggests that both are not intrinsically photoconductive, rules out light-induced charge injection by the electrodes, and indicates the polymer-liquid-crystal interface as the photoactive element in the effect. The photocurrent dynamics indicate the presence of various mechanisms. We suppose that the effect is due to photoinduced carriers injection through the liquid-crystal-polymer interface and recombination process with the counterions present on the opposite side. Different hypotheses are made and discussed.

  2. Fluorescent DNA probes at liquid/liquid interfaces studied by surface second harmonic generation.

    PubMed

    Licari, Giuseppe; Brevet, Pierre-François; Vauthey, Eric

    2016-01-28

    The properties of a series of oxazole yellow dyes, including the dicationic YOPRO-1 and its homodimeric parent YOYO-1 and two monocationic dyes (YOSAC-1 and YOSAC-3), have been investigated at the dodecane/water interface using stationary and time-resolved surface second harmonic generation (SSHG) combined with quantum chemical calculations. Whereas YOYO-1 exists predominantly as a H-dimer in aqueous solution, the stationary SSHG spectra reveal that such dimers are not formed at the interface. No significant H-aggregation was observed with YOPRO-1, neither in solution nor at the interface. In the case of the monocationic YOSAC dyes, a distinct SSHG band due to H-aggregates was measured at the interface, whereas only weak aggregation was found in solution. These distinct aggregation behaviors can be explained by the different orientations of the dyes at the interface, as revealed from the analysis of polarization-resolved experiments, the doubly-charged dyes lying more flat on the interface than the singly charged ones. Although YOYO-1 and YOPRO-1 do not form H-dimer/aggregates at the interface, time-resolved SSHG measurements point to the occurrence of intra- and intermolecular interactions, respectively, which inhibit the ultrafast non-radiative decay of the excited dyes via large amplitude motion, and lead to a nanosecond excited-state lifetime. The distinct behavior evidenced here for YOYO-1 and YOSAC dyes points to their potential use as fluorescent or SHG interfacial probes. PMID:26740332

  3. Study on the gas-liquid interface and polymer melt front in gas-assisted injection molding

    SciTech Connect

    Shen, Y.K.

    1997-03-01

    The algorithms are developed to predict the gas-liquid interface in gas-assisted injection molding. The simulation of two-dimensional, transient, non-isothermal and high viscous flow between two parallel plates with the generalized Newtonian fluid is presented in detail. The model takes into account the effects of the gas-liquid interface and polymer melt front.

  4. Structural and thermodynamic behavior of alkane chains at the liquid/vapor interface

    NASA Astrophysics Data System (ADS)

    Hernandez, David Alejandro; Domínguez, Hector

    2013-04-01

    Computer simulations for several alkane fluids were carried out to study thermodynamics and structural behavior of the molecules at the liquid-vapor interface. Three different models were used to simulate the fluids, one of them was proposed in this work and we obtained a slightly better agreement than the other models with experimental data. The fluid structure at the interface was analyzed at temperatures close to the melting point using the new model and it was found that molecules at the free surface present more order than those at the bulk liquid phase. By calculating the order of the hydrocarbon chains a strong structure of molecules was observed at the interface than those in bulk, moreover, some of those molecules at the interface were aligned perpendicular to the interface. Previous simulations report stronger structures at the interface by the formation of a monolayer of alkane chains, however, those simulations started at very low temperatures and they did not reproduce thermodynamic properties such as the interfacial tension correctly. The model proposed in the present work not only presents good agreement with surface tension data but also shows evidence that the fluid structured as experiments indicated at temperatures close to the melting temperature.

  5. Performance of an improved monodisperse aerosol generation interface for liquid chromatography/mass spectrometry

    SciTech Connect

    Winkler, P.C.; Perkins, D.D.; Williams, W.K.; Browner, R.F.

    1988-03-01

    An improved monodisperse aerosol generation interface for liquid chromatography/mass spectrometry interfacing (MAG-IC-LC/MS) is described. The interface has an aerodynamically superior momentum separator, which results in decreased analyte loss in passing through the interface. The interface is shown to perform well with a quadrupole mass spectrometer, in addition to earlier studies with a magnetic sector instrument. A new method of forming aerosol has been developed, which reduces the dead volume significantly over earlier designs. The performance of the interface has been evaluated by studying its capabilities for (1) generating electron impact spectra of searchable quality for selected compounds of interest, (2) operating with typical liquid chromatographic separation conditions, including reverse phase and gradient elution, and (3) providing low detection limits for both full scan and selective ion monitoring detection of a range of compounds. Studies include identification of the components of a mixture of cis and trans isomers of the thermally labile compound retinol (vitamin A) acetate. Full scan (m/z 80-350) electron impact spectra were readily obtained with 50-ng injection on-column. Detection limits for this compound were 10 ng full scan and 1 ng with selected ion monitoring. Identification of a free (nonderivatized) fatty acid mixture was also readily obtained, using a reversed-phase separation in gradient mode.

  6. 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.

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

    SciTech Connect

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

    2011-08-15

    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.

  8. Mechanisms of reduced solute diffusivity at nanoconfined solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Mahadevan, T.; Kojic, M.; Ferrari, M.; Ziemys, A.

    2013-06-01

    We report results from molecular simulations that reveal the causes of reduced diffusivity at solid-liquid interfaces in the presence of nanoscale confinement. The diffusion of a 2 M glucose solution was simulated inside a 10 nm silica channel together with the calculated thermodynamic properties of diffusion. A strong energy-entropy compensation mechanism was found at the interface with a free energy minimum of -0.6 kcal/mol. Using the Eyring equation the average jump length was reduced by 15% at interface. The complete loss of solute diffusivity at silica surface was explained by the substantial loss of the probability of productive displacements. The results suggested that glucose molecule diffusivity close to the surface might be related to a stiffer cage of the hydration shell, which affects the probability of cage breaking. These results help in understanding of diffusion mechanisms at interface and predicting mass transport in nanoconfinement for engineering and biomedical applications.

  9. Fast Interconversion of Hydrogen Bonding at the Hematite (001)-Liquid Water Interface.

    PubMed

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

    2016-04-01

    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. PMID:26954334

  10. Atomic-Scale Structure of a Liquid Metal-Insulator Interface

    SciTech Connect

    Ocko, B.M.; Tamam, L.; Pontoni, D.; Hofmann, T.; Reichert, H.; Deutsch, M.

    2010-04-01

    The structure of the liquid Hg/sapphire interface was measured with angstrom-scale resolution by high-energy X-ray reflectivity. The atomic Hg layering found at the interface is less pronounced than at the Hg/vapor interface, showing a twice-shorter decay length with depth, and a weaker peak/valley density contrast. We also find a near-interface, 8 {+-} 3 {angstrom} thick layer, the density of which, although depth-varying, is enhanced, on average, by 10 {+-} 5% relative to the bulk. The enhancement is assigned to a 0.13 {+-} 0.05 e/atom charge transfer from the Hg to the substrate, somewhat less than theory. The unexplained anomalous temperature dependence previously reported for the mercury/vapor density profile is absent here, implying a nonstructural origin for the anomaly.

  11. High-precision measurements of molecular slip at a solid/liquid interface

    NASA Astrophysics Data System (ADS)

    Pye, Justin; Wood, Clay; Burton, Justin

    As fluidic devices get smaller and measurements become more precise and stringent, the need to fully understand the dynamics at interfaces becomes more important. It is now clear that slip near an interface is common at the nanoscale in Newtonian liquids. In simple systems, there is a general trend to larger slip lengths for non-wetting liquid/solid combinations, but many conflicting measurements and interpretations remain. We have developed a novel differential technique using a quartz crystal microbalance (QCM) to measure slip lengths on various substrates. A drop of one liquid is grown on the QCM in the presence of a second, ambient liquid. By choosing the two liquids such that their bulk effects on the QCM frequency and dissipation are identical in the presence of no-slip, we are able to isolate anomalous boundary effects due to interfacial slip. Our data for water on gold (in undecane) are consistent with a slip length of 5nm (for water). A glass surface, wetted by both gold and undecane has also shown strongly anomalous results for the water-undecane pair. In addition to investigating other liquid pairs, future work will include extending this technique to surfaces with independently controllable chemistry and roughness, both of which are known to strongly affect interfacial hydrodynamics.

  12. Efficiency of air/liquid interfaces in detaching bacteria from a surface

    NASA Astrophysics Data System (ADS)

    Khodaparast, Sepideh; Stone, Howard

    2015-11-01

    Gas/liquid interfaces are known to be significantly more effective than shear stress in detaching microscale colloids from substrates by inducing surface tension forces. Providing that a three-phase contact at the interface of a gas bubble, the liquid phase and the particle occurs, the magnitude of the surface tension force can potentially exceed by orders of magnitude the adhesion force, which keeps the micro particles on the surface. We investigate the ability of a moving air/liquid interface to stimulate the detachment of bacteria from a surface. Bacteria are micron-sized living organisms with strong tendency to attach to almost any substrate that they come into contact with. Attachment of bacteria on the surface is a complex process regulated by diverse characteristics of their growth medium, substrate, and cell surface. Moreover, once fixed on the surface, the microorganisms evolve in time to create intricate biofilm structures, which are highly challenging to be removed. The objective of this study to characterise the efficiency of this detachment process as a function of bacterial attachment as well as hydrodynamic parameters such the surface tension and the interface velocity. Swiss National Science Foundation P2ELP2-158896.

  13. Direct numerical simulation of turbulent flows over superhydrophobic surfaces: gas-liquid interface dynamics

    NASA Astrophysics Data System (ADS)

    Seo, Jongmin; García-Mayoral, Ricardo; Mani, Ali

    2013-11-01

    Superhydrophobic surfaces can induce large slip velocities for liquid flows, reducing the skin friction on walls, by entrapping gas pockets within the surface roughness. This work explores the onset mechanism leading to gas depletion through interface breakage under turbulent conditions. We conduct direct numerical simulations of flows over superhydrophobic walls. The superhydrophobic texture is conventionally modeled as a pattern of slip/no-slip boundary conditions for the wall-parallel velocities but, to take into account the dynamic deformation of the gas-liquid interface, we also introduce non-zero boundary conditions for the wall-normal velocity. These conditions are derived from the deformation of the interface in response to the overlying turbulent pressure fluctuations, following the Young-Laplace equation. Surface protrusions in the form of posts and streamwise-aligned ridges are studied, and results are presented as a function of the ``deformability'' of the gas-liquid interfaces, expressed as a Weber number. We will also discuss results for misaligned ridges. Supported by the Office of Naval Research and the Kwanjeong Educational Scholarship Foundation.

  14. Advanced liquid chromatography-mass spectrometry interface based on electron ionization.

    PubMed

    Cappiello, A; Famiglini, G; Pierini, E; Palma, P; Trufelli, H

    2007-07-15

    Major progress in interfacing liquid chromatography and electron ionization mass spectrometry is presented. The minimalism of the first prototype, called the Direct-EI interface, has been widely refined, improved, and applied to modern instrumentation. The simple interfacing principle is based on the straight connection between a nanoHPLC system and a mass spectrometer equipped with an EI source forming a solid and reliable unicum resembling the immediacy and straightforwardness of GC/MS. The interface shows a superior performance in the analysis of small-medium molecular weight compounds, especially when compared to its predecessors, and a unique trait that excels particularly in the following aspects: (1) It delivers high-quality, fully library matchable mass spectra of most sub-1 kDa molecules amenable by HPLC. (2) It is a chemical ionization free interface (unless operated intentionally) with accurate reproduction of the expected isotope ion abundances. (3) Response is never influenced by matrix components in the sample or in the mobile phase (nonvolatile salts are also well accepted). A deep evaluation of these aspects is presented and discussed in detail. Other characteristics of the interface performance such as limits of detections, range of linear response, and intra- and interday signal stability were also considered. The usefulness of the interface has been tested in a few real-world applications where matrix components played a detrimental role with other LC/MS techniques. PMID:17569502

  15. TOPICAL REVIEW: Sensors and actuators based on surface acoustic waves propagating along solid liquid interfaces

    NASA Astrophysics Data System (ADS)

    Lindner, Gerhard

    2008-06-01

    The propagation of surface acoustic waves (SAWs) along solid-liquid interfaces depends sensitively on the properties of the liquid covering the solid surface and may result in a momentum transfer into the liquid and thus a propulsion effect via acoustic streaming. This review gives an overview of the design of different SAW devices used for the sensing of liquids and the basic mechanisms of the interaction of SAWs with overlaying liquids. In addition, applications of devices based on these phenomena with respect to touch sensing and the measurement of liquid properties such as density, viscosity or the composition of mixed liquids are described, including microfabricated as well as macroscopic devices made from non-piezoelectric materials. With respect to the rapidly growing field of acoustic streaming applications, recent developments in the movement of nanolitre droplets on a single piezoelectric chip, the rather macroscopic approaches to the acoustic pumping of liquids in channels and recent attempts at numerical simulations of acoustic streaming are reported.

  16. Accurate Optical Detection of Amphiphiles at Liquid-Crystal-Water Interfaces

    NASA Astrophysics Data System (ADS)

    Popov, Piotr; Mann, Elizabeth K.; Jákli, Antal

    2014-04-01

    Liquid-crystal-based biosensors utilize the high sensitivity of liquid-crystal alignment to the presence of amphiphiles adsorbed to one of the liquid-crystal surfaces from water. They offer inexpensive, easy optical detection of biologically relevant molecules such as lipids, proteins, and cells. Present techniques use linear polarizers to analyze the alignment of the liquid crystal. The resulting images contain information not only about the liquid-crystal tilt with respect to the surface normal, the quantity which is controlled by surface adsorption, but also on the uncontrolled in-plane liquid-crystal alignment, thus making the detection largely qualitative. Here we show that detecting the liquid-crystal alignment between circular polarizers, which are only sensitive to the liquid-crystal tilt with respect to the interface normal, makes possible quantitative detection by measuring the transmitted light intensity with a spectrophotometer. Following a new procedure, not only the concentration dependence of the optical path difference but also the film thickness and the effective birefringence can be determined accurately. We also introduce a new "dynamic" mode of sensing, where (instead of the conventional "steady" mode, which detects the concentration dependence of the steady-state texture) we increase the concentration at a constant rate.

  17. 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.

  18. Strong collective attraction in colloidal clusters on a liquid-air interface.

    PubMed

    Pergamenshchik, V M

    2009-01-01

    It is shown that in a cluster of many colloids, trapped at a liquid-air interface, the well-known vertical-force-induced pairwise logarithmic attraction changes to a strongly enhanced power-law attraction. In large two-dimensional clusters, the attraction energy scales as the inverse square of the distance between colloids. The enhancement is given by the ratio eta = (square of the capillary length) / (interface surface area per colloid) and can be as large as 10;{5} . This explains why a very small vertical force on colloids, which is too weak to bring two of them together, can stabilize many-body structures on a liquid-air interface. The profile of a cluster is shown to consist of a large slow collective envelope modulated by a fast low-amplitude perturbation due to individual colloids. A closed equation for the slow envelope, which incorporates an arbitrary power-law repulsion between colloids, is derived. For example, this equation is solved for a large circular cluster with the hard-core colloid repulsion. It is suggested that the predicted effect is responsible for mysterious stabilization of colloidal structures observed in experiments on a surface of isotropic liquid and nematic liquid crystal. PMID:19257035

  19. 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.

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

    SciTech Connect

    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.

  1. 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.

  2. On the solute coupling at the moving solid/liquid interface during equiaxed solidification

    NASA Astrophysics Data System (ADS)

    Yao, X.

    2006-08-01

    Integral mass conservation was widely accepted for the solute coupling to solve solute redistribution during equiaxed solidification so far. The present study revealed that the integral form was invalid for moving boundary problems as it could not represent the mass balance at the moving interface. Accordingly, differential mass conservation at the solid/liquid interface was used to solve solute diffusion for spherical geometry. The model was applied for hydrogen diffusion in solidification to validate that the hydrogen enrichment was significant and depended on the growth rate.

  3. Two-Dimensional Microfluidics: hydrodynamics of drops and interfaces in flowing smectic liquid crystal channels

    NASA Astrophysics Data System (ADS)

    Qi, Zhiyuan; Nguyen, Zoom; Park, Cheol; Maclennan, Joe; Maclennan, Matt; Clark, Noel

    2012-02-01

    The quantization of film thickness in freely suspended fluid smectic liquid crystal film enables the study of the hydrodynamics of drops and interfaces in 2D. We report microfluidic experiments, in which we observe the hydrodynamics of 2D drops flowing in channels. Using high-speed video microscopy, we track the shape of 2D drops and interfaces, visualizing the deterministic lateral displacement-based separation and pinched flow separation phenomena previously observed only in 3D. Finally, we demonstrate techniques for 2D drop generation and sorting, which will be used for 2D microfluidic applications.

  4. Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor-Liquid Phase Equilibrium.

    PubMed

    Shardt, Nadia; Elliott, Janet A W

    2016-04-14

    The effect of interface curvature on phase equilibrium has been much more studied for single-component than multicomponent systems. We isolate the effect of curvature on multicomponent vapor-liquid equilibrium (VLE) phase envelopes and phase composition diagrams using the ideal system methanol/ethanol and the nonideal system ethanol/water as illustrative examples. An important finding is how nanoscale interface curvature shifts the azeotrope (equal volatility point) of nonideal systems. Understanding of the effect of curvature on VLE can be exploited in future nanoscale prediction and design. PMID:27028744

  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. Co-assembled thin films of Ag nanowires and functional nanoparticles at the liquid-liquid interface by shaking

    NASA Astrophysics Data System (ADS)

    Zhang, Shao-Yi; Liu, Jian-Wei; Zhang, Chuan-Ling; Yu, Shu-Hong

    2013-05-01

    In this paper, we report the fabrication of co-assembled thin films composed of silver nanowires (NWs) and Au nanoparticles (NPs) at the liquid-liquid interface (water-chloroform) by vigorous shaking. The composition of co-assembled thin films can be controlled by adjusting the concentration of the nanosized building blocks. As a versatile interfacial assembly method, other nanoparticles such as Ag2S and Fe3O4 NPs can also be co-assembled with Ag NWs using the same procedure. Meanwhile, the co-assembly state of the obtained Au NPs and Ag NWs makes a significant contribution to the high sensitivity of surface-enhanced Raman scattering (SERS) to model the molecule 3,3'-diethylthiatricarbocyanine iodide (DTTCI). The SERS intensities show high dependence on the molar ratio of Au NPs and Ag NWs and the layer number of the co-assembled thin films. This shaking-assisted liquid-liquid assembly system has been proved to be a facile way for co-assembling nanowires and nanoparticles, and will pave a way for further applications of the macroscopic co-assemblies with novel functionalities.In this paper, we report the fabrication of co-assembled thin films composed of silver nanowires (NWs) and Au nanoparticles (NPs) at the liquid-liquid interface (water-chloroform) by vigorous shaking. The composition of co-assembled thin films can be controlled by adjusting the concentration of the nanosized building blocks. As a versatile interfacial assembly method, other nanoparticles such as Ag2S and Fe3O4 NPs can also be co-assembled with Ag NWs using the same procedure. Meanwhile, the co-assembly state of the obtained Au NPs and Ag NWs makes a significant contribution to the high sensitivity of surface-enhanced Raman scattering (SERS) to model the molecule 3,3'-diethylthiatricarbocyanine iodide (DTTCI). The SERS intensities show high dependence on the molar ratio of Au NPs and Ag NWs and the layer number of the co-assembled thin films. This shaking-assisted liquid-liquid assembly system

  7. 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.

  8. 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. PMID:25640463

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

    NASA Astrophysics Data System (ADS)

    Klapp, Jaime; di G Sigalotti, Leonardo; Troconis, Jorge; Sira, Eloy; Pena, Franklin; ININ-IVIC Team; Cinvestav-UAM-A Team

    2014-11-01

    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. Cinvestav-Abacus.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. 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. PMID:25122383

  12. Effect of polyelectrolyte-surfactant complexation on Marangoni transport at a liquid-liquid interface.

    PubMed

    Dunér, Gunnar; Kim, Michelle; Tilton, Robert D; Garoff, Stephen; Przybycien, Todd M

    2016-04-01

    Complexation of surfactants and oppositely charged polyelectrolytes is expected to alter Marangoni transport at a fluid interface compared to either single component system due to altered interfacial tension isotherms and mass transfer rates as well as adsorption irreversibility effects. We investigate Marangoni transport at the oil/water interface by passing mixtures of the anionic surfactant sodium dodecyl sulfate (SDS) and cationic polyelectrolyte poly(3-(2-methylpropionamide)propyl) trimethylammonium chloride-acrylamide (poly[AM-MAPTAC]), or rinsing solutions, over an oil/water interface in a radial, stagnation point flow. The displacements of adsorbed tracer particles are recorded through optical microscopy. The net displacement, defined as the sum of the displacements occurring during the adsorption and desorption stages of one application and rinsing cycle, is up to 10 times greater for complexing surfactant/polymer mixtures compared to either single component system. The enhanced net displacement is largely determined by the enhanced transport upon adsorption, while the reverse displacement that would normally occur upon rinsing is partially suppressed by partially irreversible polymer adsorption at the oil/water interface. In addition to effects of complexation on interfacial tension gradient induced flow, complexation effects on the bulk, and possibly interfacial, viscosity also influence the interfacial transport. PMID:26775240

  13. 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...

  14. Fabrication of nano-emulsions by bursting bubble at a liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Feng, Jie; Roché, Matthieu; Vigolo, Daniele; Arnaudov, Luben; Stoyanov, Simeon; Stone, Howard A.

    2012-11-01

    Bubbles bursting at interfaces is a familiar everyday occurrence and plays a role in important processes of transport across interfaces. Here we demonstrate that the bursting of air bubbles at an air-oil-water interface in the presence of a surfactant and a co-surfactant leads to the dispersion of nano-droplets in water. Using high-speed imaging we investigate the mechanism for the dispersion of objects and show that small droplets detach from the boundary of the bubble towards the bulk water during collapse of the bubble. We also characterize the size and stability of the dispersed objects with dynamic light scattering and microscopy techniques. The observations indicate that a well-defined population of few-hundred-nm-sized droplets is produced by bubble bursting, along with a broad range of sizes above 1 μm. We propose that the dispersed objects are formed because of the rapid motion of the bubble interface during collapse. By varying experimental conditions, we show that the size of the droplets is influenced mainly by the amount of surfactant in the oil phase.

  15. Thermally excited capillary waves at vapor/liquid interfaces of water-alcohol mixtures

    SciTech Connect

    Vaknin, David; Bu, Wei; Sung, Jaeho; Jeon, Yoonnam; Kim, Doseok

    2009-02-02

    The density profiles of liquid/vapor interfaces of water–alcohol (methanol, ethanol and propanol) mixtures were studied by surface-sensitive synchrotron x-ray scattering techniques. X-ray reflectivity and diffuse scattering measurements, from the pure and mixed liquids, were analyzed in the framework of capillary wave theory to address the characteristic length scales of the intrinsic roughness and the shortest capillary wavelength (alternatively, the upper wavevector cutoff in capillary wave theory). Our results establish that the intrinsic roughness is dominated by average interatomic distances. The extracted effective upper wavevector cutoff indicates capillary wave theory breaks down at distances of the order of bulk correlation lengths.

  16. 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.

  17. Density Profiles of Liquid/Vapor Interfaces Away from Their Critical Points

    SciTech Connect

    Bu, Wei; Kim, Doseok; Vaknin, David

    2014-06-12

    We examine the applicability of various model profiles for the liquid/vapor interface by X-ray reflectivities on water and ethanol and their mixtures at room temperature. Analysis of the X-ray reflecivities using various density profiles shows an error-function like profile is the most adequate within experimental error. Our findings, together with recent observations from simulation studies on liquid surfaces, strongly suggest that the capillary-wave dynamics shapes the interfacial density profile in terms of the error function.

  18. Water permeability of primary mouse keratinocyte cultures grown at the air-liquid interface

    SciTech Connect

    Cumpstone, M.B.; Kennedy, A.H.; Harmon, C.S.; Potts, R.O.

    1989-04-01

    In order to study the development of the epidermal permeability barrier in vitro, tritiated water (HTO) flux was measured across murine keratinocytes cultured at the air-liquid interface. Using a micro-diffusion technique, it was shown that air-liquid cultures form areas where the water diffusion is comparable to that of intact neonatal mouse skin. When water permeability is measured over a large area of the culture surface, however, significantly higher flux is obtained. These results show that under the culture conditions used, areas of water barrier comparable to intact neonatal mouse skin coexist with regions of less complete barrier formation.

  19. 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.

  20. Solid-liquid interfaces of ionic liquid solutions—Interfacial layering and bulk correlations

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Roth, Roland; Schröder, Heiko; Reichert, Peter; Pontoni, Diego; Reichert, Harald

    2015-04-01

    The influence of the polar, aprotic solvent propylene carbonate on the interfacial structure of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate on sapphire was investigated by high-energy x-ray reflectivity. Experiments at solvent concentrations between 17 mol. % and 83 mol. % bridge the gap between diluted electrolytes described by the classical Gouy-Chapman theory and pure ionic liquids. Analysis of our experimental data revealed interfacial profiles comprised of alternating anion and cation enriched regions decaying gradually into the bulk liquid. With increasing solvent concentration, we observed a decrease in correlation length of the interfacial layering structure. At high ion concentrations, solvent molecules were found to accumulate laterally within the layers. By separating like-charged ions, they reduce their Coulomb repulsion. The results are compared with the bulk structure of IL/solvent blends probed by x-ray scattering and predictions from fundamental fluid theory.

  1. DNA hybridization-induced reorientation of liquid crystal anchoring at the nematic liquid crystal/aqueous interface.

    PubMed

    Price, Andrew D; Schwartz, Daniel K

    2008-07-01

    Interactions between DNA and an adsorbed cationic surfactant at the nematic liquid crystal (LC)/aqueous interface were investigated using polarized and fluorescence microscopy. The adsorption of octadecyltrimethylammonium bromide (OTAB) surfactant to the LC/aqueous interface resulted in homeotropic (untilted) LC alignment. Subsequent adsorption of single-stranded DNA (ssDNA) to the surfactant-laden interface modified the interfacial structure, resulting in a reorientation of the LC from homeotropic alignment to an intermediate tilt angle. Exposure of the ssDNA/OTAB interfacial complex to its ssDNA complement induced a second change in the interfacial structure characterized by the nucleation, growth, and coalescence of lateral regions that induced homeotropic LC alignment. Fluorescence microscopy showed explicitly that the complement was colocalized in the same regions as the homeotropic domains. Exposure to noncomplementary ssDNA caused no such response, suggesting that the homeotropic regions were due to DNA hybridization. This hybridization occurred in the vicinity of the interface despite the fact that the conditions in bulk solution were such that hybridization did not occur (high stringency), suggesting that the presence of the cationic surfactant neutralized electrostatic repulsion and allowed for hydrogen bonding between DNA complements. This system has potential for label-less and portable DNA detection. Indeed, LC response to ssDNA target was detected with a lower limit of approximately 50 fmol of complement and was sufficiently selective to differentiate a one-base-pair mismatch in a 16-mer target. PMID:18528984

  2. Characterisation of the solid electrolyte interface during lithiation/delithiation of germanium in an ionic liquid.

    PubMed

    Lahiri, Abhishek; Borisenko, Natalia; Borodin, Andriy; Olschewski, Mark; Endres, Frank

    2016-02-21

    In this paper, we present investigations of the interface of electrodeposited Ge during lithiation/delithiation in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide containing 0.5 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI/[Py1,4]TFSI). Cyclic voltammetry (CV) and infrared spectroscopy were used to study the electrochemistry and the changes in the electrolyte during the Li intercalation/deintercalation processes. From infrared spectroscopic analysis, it was found that the TFSI(-) anion decomposes during the lithiation process, resulting in the formation of a solid-liquid interface (SEI) layer. X-ray photoelectron spectroscopy was used to analyse the composition of the SEI layer and the changes in the electrodeposited germanium. Furthermore, atomic force microscopy (AFM) was used to evaluate the changes in the SEI layer which showed that the SEI layer was inhomogenous and changed during the lithiation/delithiation processes. PMID:26863589

  3. The Improvement of the Characteristics of Liquid Phase-Deposited SiliconDioxide/Silicon Interface

    NASA Astrophysics Data System (ADS)

    Haneji, Nobuo; Chanthamaly, Phonekeo; Mouri, Shigenobu

    Liquid phase deposition (LPD) is the method to deposit SiO2 films on the substrates at room temperature in the super-saturated fluorosilicic acid (H2SiF6) solution. When the SiO2 films are directly deposited on the Si substrates, which are treated with diluted HF to remove the native oxide, the characteristics of the the SiO2/Si interface are poor, because the surface Si atoms are terminated and covered with H atoms. Low temperature (30—500°C) annealing in O2 was found to be effective to improve the interface characteristics, and also the breakdown characteristics. This low temperature annealing in O2 ambient is useful without losing the merit of low temperature process in the liquid-phase deposition method, when the deposited SiO2 films are used as the gate insulators in Si MOS FETs.

  4. 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.

  5. 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.

  6. 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. PMID:24594813

  7. 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.

  8. 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

  9. 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

  10. Instability of interfaces of gas bubbles in liquids under acoustic excitation with dual frequency.

    PubMed

    Zhang, Yuning; Du, Xiaoze; Xian, Haizhen; Wu, Yulin

    2015-03-01

    Instability of interfaces of gas bubbles in liquids under acoustic excitation with dual frequency is theoretically investigated. The critical bubble radii dividing stable and unstable regions of bubbles under dual-frequency acoustic excitation are strongly affected by the amplitudes of dual-frequency acoustic excitation rather than the frequencies of dual-frequency excitation. The limitation of the proposed model is also discussed with demonstrating examples. PMID:25164271

  11. Assembly of Submicron Sized Ag, Co, and Ni Particles Into Thin Films at Liquid/Liquid Interfaces.

    PubMed

    Al Chaghouri, Hanan; Malik, Mohammad Azad; Thomas, P John; O'Brien, Paul

    2016-05-01

    Submicron sized particles of Ag, Co and Ni were synthesised by reducing metal salts in ethylene glycol (EG) in the presence of polyvinylpyrrolidone (PVP). These particles on dispersion in water when held in contact with a toluene layer were found to assemble into dense films extending over large areas at the interface between the two liquids. The effect of reaction conditions (solvent, precursor concentration, temperature) on the synthesis and assembly of the particles was studied. The characteristics of the interfacial deposits and the particulate dispersions were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy and dynamic light scattering (DLS). PMID:27483942

  12. 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

  13. 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.

  14. Capillary Waves at Liquid/Vapor Interfaces: A Molecular Dynamics Simulation

    SciTech Connect

    Sides, Scott W.; Grest, Gary S.; Lacasse, Martin-D.

    1999-07-16

    Evidence for capillary waves at a liquid/vapor interface are presented from extensive molecular dynamics simulations of a system containing up to 1.24 million Lennard-Jones particles. Careful measurements show that the total interfacial width depends logarithmically on L{sub {parallel}}, the length of the simulation cell parallel to the interface, as predicted theoretically. The strength of the divergence of the interfacial width on L{sub {parallel}} depends inversely on the surface tension {gamma}. This allows us to measure {gamma} two ways since {gamma} can also be obtained from the difference in the pressure parallel and perpendicular to the interface. These two independent measures of {gamma} agree provided that the interfacial order parameter profile is fit to an error function and not a hyperbolic tangent, as often assumed. We explore why these two common fitting functions give different results for {gamma}.

  15. Pressure cell for investigations of solid-liquid interfaces by neutron reflectivity

    NASA Astrophysics Data System (ADS)

    Kreuzer, Martin; Kaltofen, Thomas; Steitz, Roland; Zehnder, Beat H.; Dahint, Reiner

    2011-02-01

    We describe an apparatus for measuring scattering length density and structure of molecular layers at planar solid-liquid interfaces under high hydrostatic pressure conditions. The device is designed for in situ characterizations utilizing neutron reflectometry in the pressure range 0.1-100 MPa at temperatures between 5 and 60 °C. The pressure cell is constructed such that stratified molecular layers on crystalline substrates of silicon, quartz, or sapphire with a surface area of 28 cm2 can be investigated against noncorrosive liquid phases. The large substrate surface area enables reflectivity to be measured down to 10-5 (without background correction) and thus facilitates determination of the scattering length density profile across the interface as a function of applied load. Our current interest is on the stability of oligolamellar lipid coatings on silicon surfaces against aqueous phases as a function of applied hydrostatic pressure and temperature but the device can also be employed to probe the structure of any other solid-liquid interface.

  16. Pressure cell for investigations of solid-liquid interfaces by neutron reflectivity.

    PubMed

    Kreuzer, Martin; Kaltofen, Thomas; Steitz, Roland; Zehnder, Beat H; Dahint, Reiner

    2011-02-01

    We describe an apparatus for measuring scattering length density and structure of molecular layers at planar solid-liquid interfaces under high hydrostatic pressure conditions. The device is designed for in situ characterizations utilizing neutron reflectometry in the pressure range 0.1-100 MPa at temperatures between 5 and 60 °C. The pressure cell is constructed such that stratified molecular layers on crystalline substrates of silicon, quartz, or sapphire with a surface area of 28 cm(2) can be investigated against noncorrosive liquid phases. The large substrate surface area enables reflectivity to be measured down to 10(-5) (without background correction) and thus facilitates determination of the scattering length density profile across the interface as a function of applied load. Our current interest is on the stability of oligolamellar lipid coatings on silicon surfaces against aqueous phases as a function of applied hydrostatic pressure and temperature but the device can also be employed to probe the structure of any other solid-liquid interface. PMID:21361606

  17. Convective influence on the stability of a cylindrical solid-liquid interface

    NASA Technical Reports Server (NTRS)

    Fang, Q. T.; Glicksman, M. E.; Coriell, S. R.; Mcfadden, G. B.; Boisvert, R. F.

    1985-01-01

    Experiments in which a long vertical, heated wire is surrounded by concentric annuli of a melt and its crystalline solid show that the convection state changes from a stable unicell surrounded by a stationary cylindrical solid-liquid interface, to a complex time-dependent flow surrounded by a rotating, helical solid-liquid interface. This transition occurs at a Grashof number of approximately 150, which is an order of magnitude less than the critical Grashof number calculated for a liquid annulus surrounded by rigid walls. A linear stability analysis has been carried out for an infinitely tall vertical annulus. When the deformable nature of the crystal-melt interface is taken into account in the boundary conditions, two new modes of instability arise. The most dangerous mode is asymmetrical and corresponds to helical waves travelling vertically upwards. The critical Grashof number and the scaling properties of the eigenstate agree with experiments. The results clearly demonstrate the coupling of convection with crystal-melt interfacial instabilities.

  18. 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.

  19. Universal Regimes in the Relaxation of Stepped Liquid Interfaces near Contact Lines

    NASA Astrophysics Data System (ADS)

    Baeumchen, Oliver; Salez, Thomas; Benzaquen, Michael; Raphael, Elie; Rivetti, Marco

    2015-03-01

    A liquid droplet on a perfectly smooth surface wets or dewets the substrate according to the difference between initial and equilibrium contact angles. Such a scenario, however, becomes much less intuitive whenever the initial shape of the interface is non-spherical. Indeed, the capillary-driven relaxation of the liquid surface may be in competition with the relaxation of the contact angle at the three-phase contact line. Here, we study the dynamics of stepped interfaces of thin polystyrene films on hydrophilic substrates. Annealing the polymeric film above its glass transition temperature induces flow which is precisely monitored using ex- and in-situ atomic force microscopy. Both pinned and receding contact line regimes are observed, corresponding to capillary levelling and dewetting of the liquid film. Rescaling with regard to the viscosity, surface tension and film thickness collapses the data on a master curve, providing a universal time for the transition between both regimes. In addition, we prove that the pinned interface exhibits self-similar height profiles which are captured by a thin film model in lubrication approximation.

  20. 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.

  1. An experimental study of liquid drop - interface coalescence in the presence of surfactants

    NASA Astrophysics Data System (ADS)

    Angeli, Panagiota; Chinaud, Maxime; Li, Kai; Wang, Wei; University College London Team; Beijing Key Laboratory of Urban Oil; Gas Distribution Technology Team

    2014-11-01

    Drop-interface coalescence has been the subject of many studies both theoretical and experimental. It is of particular interest for the oil industries particularly during the transportation of multiphase mixtures where coalescence rates can affect the stability and separation of dispersions. It is well-known that the presence of surfactants can significantly affect the coalescence rates. In this work a silicon oil -water system has been studied in a rectangular coalescence cell. Both rising oil drops and falling water drops coalescing with the water-oil interface have been investigated. A water soluble surfactant, SPAN 80, was used. High speed imaging has been performed to study the coalescence phenomenon and obtain the coalescence time of the drops with the interface with and without the presence of the surfactant. The velocity fields in the bulk fluid and in the liquid film forming between the drop and the interface were studied with shadowgraphy (bright field Particle Image Velocimetry). To increase the spatial resolution particularly in the liquid film microscope lenses were implemented. Results have been compared against existing literature.

  2. 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.

  3. 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

    2012-04-01

    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. PMID:26286408

  4. Colloidal-Particle Monolayers at Liquid Interfaces: Capsules, Membranes and Functional Electronic Junctions

    NASA Astrophysics Data System (ADS)

    Dinsmore, A. D.; McGorty, R.; Edmond, K. V.; Knutson, C. R.; Soyler, S. G.; Marquez, M.

    2004-11-01

    The interface between two liquids, as on the surface of a water droplet in oil, provides a versatile platform for self assembly of functional membranes, capsules, and other devices composed of colloidal particles. Owing to the large liquid interfacial tension, nanometer-to-micron-sized particles in either liquid readily adsorb at the interface, forming a densely packed monolayer. In this way, a shell of cross-linked particles is constructed around water droplets containing nutrients, drugs or, potentially, living cells. The resulting elastic capsules are transferred directly to a continuous aqueous solution, allowing diffusive permeation of macromolecules and small particles while encapsulating the larger objects. Moreover, liquid structures of cylindrical shape are formed by hydrodynamic focusing of a non-Newtonian aqueous solution; these are used as platforms for interfacial assembly. Finally, the assembly of ligand-stabilized nanoparticles on the surfaces of electrically conducting droplets in insulating oil leads to functional electronic devices, including single-electron transistors. We gratefully acknowledge support from Kraft Foods, Inc.

  5. 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. PMID:26385430

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Analytic solution of thermocapillary flow and interface shape in non-isothermal coaxial liquid columns

    NASA Astrophysics Data System (ADS)

    Viviani, A.; Cioffi, M.

    Two coaxial immiscible fluid columns are held between two parallel walls kept at different temperatures; the inner column of liquid (a) forms an axisymmetric interface with the outer fluid, which is bounded by a cylindrical lateral wall that can be moved to infinite ( unbounded outer field). The motion in the two bulk phases arises due to surface gradients of the interface tension, induced by the imposed temperature difference; for the interface tension it is assumed a quadratic dependence, with minimum, on the temperature. Under the hypothesis of non-dimensional transport numbers (Reynolds and Peclet) and capillary number very small, the field equations are expanded in a series of sucessive linear approximations; the zero-th order is the Stokes problem, that is analyically solved via separation of variables in terms of infinite series of modified first order Bessel functions of first and second kind and Papkovitch-Fadle biorthogonal eigenfunctions. The solution is given for the zero-th order temperature, velocity and pressure fields and for first-order deviation of the interface from the hydrostatic shape. Stream-lines, velocity profiles and interface shapes are presented and discussed in terms of the viscosity ratio of the two bulk phases and the aspect ratios of the inner and outer columns.

  12. Diffuse interface analysis of crystal nucleation in hard-sphere liquid

    NASA Astrophysics Data System (ADS)

    Gránásy, László; Pusztai, Tamás

    2002-12-01

    We show that the increase of the interface free energy with deviation from equilibrium seen in recent Monte Carlo simulations [S. Auer and D. Frenkel, Nature (London) 413, 711 (2001)] can be recovered if the molecular scale diffuseness of the crystal-liquid interface is considered. We compare two models, Gránásy's phenomenological diffuse interface theory, and a density functional theory that relies on the type of Ginzburg-Landau expansion for fcc nucleation, that Shih et al. introduced for bcc crystal. It is shown that, in the range of Monte Carlo simulations, the nucleation rate of the stable fcc phase is by several orders of magnitude higher than for the metastable bcc phase, seen to nucleate first in other fcc systems. The nucleation barrier that the diffuse interface theories predict for small deviations from equilibrium is in far better agreement with the simulations than the classical droplet model. The behavior expected at high densities is model dependent. Gránásy's phenomenological diffuse interface theory indicates a spinodal point close to glass transition, while a nonsingular behavior is predicted by the density functional theory with constant Ginzburg-Landau coefficients. Remarkably, a minimum of the nucleation barrier, similar to the one seen in polydisperse systems, occurs if the known density dependence of the Ginzburg-Landau coefficients is considered.

  13. Permselective Ion Transport Across the Nanoscopic Liquid/Liquid Interface Array.

    PubMed

    Huang, Xiao; Xie, Lisiqi; Lin, Xingyu; Su, Bin

    2016-06-21

    Free-standing silica nanochannel membrane (SNM) with perforated channels was utilized to create arrays of nanoscale interfaces between two immiscible electrolyte solutions (nano-ITIES), at which permselective ion transfer and detection were achieved. The SNM consisted of a high density of straight nanochannels with a diameter of 2-3 nm and a length of 70 nm. The silicon wafer coated by 150 nm-thick porous silicon nitride film (p-SiNF) with pores of 5 μm-in-diameter was used to support the SNM in a form of nanochannel-on-micropore. Considering the material surface lipophilicity, the nano-ITIES array was formed at the boundary between SNM and p-SiNF, with a diffusion geometry equivalent to two back-to-back inlaid microdisc interfaces. Thus, the transfer of tetraethylammonium (TEA(+)) across the nano-ITIES array yielded symmetric sigmoidal current responses. In addition, because of the ultrasmall size and negatively charged surface of silica nanochannels, the nano-ITIES displayed obvious size and charge permselectivities. Transfer of ions with a size comparable with or larger than the nanochannel was sterically blocked. Also that of anions with a size smaller than the nanochannels encountered the strong electrostatic repulsion from channel walls, showing obvious dependence on the ionic strength of aqueous solution. The present approach is facile and inexpensive for building a nano-ITIES array with potential applications in ion detection and separation. PMID:27240714

  14. Linear morphological stability analysis of the solid-liquid interface in rapidsolidification of a binary system

    NASA Astrophysics Data System (ADS)

    Galenko, P. K.; Danilov, D. A.

    2004-05-01

    The interface stability against small perturbations of the planar solid-liquid interface is considered analytically in linear approximation. Following the analytical procedure of Trivedi and Kurz [

    R. Trivedi and W. Kurz, Acta Metall. 34, 1663 (1986)
    ], which is advancing the original treatment of morphological stability by Mullins and Sekerka [
    W. W. Mullins and R. F. Sekerka, J. Appl. Phys. 35, 444 (1964)
    ] to the case of rapid solidification, we extend the model by introducing the local nonequilibrium in the solute diffusion field around the interface. A solution to the heat- and mass-transport problem around the perturbed interface is given in the presence of the local nonequilibrium solute diffusion. Using the developing local nonequilibrium model of solidification, the self-consistent analysis of linear morphological stability is presented with the attribution to the marginal (neutral) and absolute morphological stability of a rapidly moving interface. Special consideration of the interface stability for the cases of solidification in negative and positive thermal gradients is given. A quantitative comparison of the model predictions for the absolute morphological stability is presented with regard to experimental results of Hoglund and Aziz [ D. E. Hoglund and M. J. Aziz, in Kinetics of Phase Transformations, edited by M.O. Thompson, M. J. Aziz, and G. B. Stephenson, MRS Symposia Proceedings No. 205 (Materials Research Society, Pittsburgh, 1991), p. 325 ] on critical solute concentration for the interface breakdown during rapid solidification of Si-Sn alloys.

  15. 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. PMID:20080682

  16. Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction.

    PubMed

    Olaya, Astrid J; Schaming, Delphine; Brevet, Pierre-Francois; Nagatani, Hirohisa; Zimmermann, Tomas; Vanicek, Jiri; Xu, Hai-Jun; Gros, Claude P; Barbe, Jean-Michel; Girault, Hubert H

    2012-01-11

    The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning Electron Microscopy. Density functional theory calculations confirm the possibility of formation of the catalytic CoTMPyP(4+)/ CoTPPS(4-) complex and its capability to bind oxygen. PMID:22107335

  17. 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.

  18. 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. PMID:19232632

  19. Electrochemical Sensing and Imaging Based on Ion Transfer at Liquid/Liquid Interfaces

    PubMed Central

    Amemiya, Shigeru; Kim, Jiyeon; Izadyar, Anahita; Kabagambe, Benjamin; Shen, Mei; Ishimatsu, Ryoichi

    2013-01-01

    Here we review the recent applications of ion transfer (IT) at the interface between two immiscible electrolyte solutions (ITIES) for electrochemical sensing and imaging. In particular, we focus on the development and recent applications of the nanopipet-supported ITIES and double-polymer-modified electrode, which enable the dynamic electrochemical measurements of IT at nanoscopic and macroscopic ITIES, respectively. High-quality IT voltammograms are obtainable using either technique to quantitatively assess the kinetics and dynamic mechanism of IT at the ITIES. Nanopipet-supported ITIES serves as an amperometric tip for scanning electrochemical microscopy to allow for unprecedentedly high-resolution electrochemical imaging. Voltammetric ion sensing at double-polymer-modified electrodes offers high sensitivity and unique multiple-ion selectivity. The promising future applications of these dynamic approaches for bioanalysis and electrochemical imaging are also discussed. PMID:24363454

  20. 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

  1. Surface thermodynamics of planar, cylindrical, and spherical vapour-liquid interfaces of water

    SciTech Connect

    Lau, Gabriel V.; Müller, Erich A.; Jackson, George; Ford, Ian J.; Hunt, Patricia A.

    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

  2. Structural ordering at solid-liquid interfaces in Al-Sm system: A molecular-dynamics study

    DOE PAGESBeta

    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 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

  3. Aggregation of Puroindoline in Phospholipid Monolayers Spread at the Air-Liquid Interface

    PubMed Central

    Dubreil, L.; Vié, V.; Beaufils, S.; Marion, D.; Renault, A.

    2003-01-01

    Puroindolines, cationic and cystine-rich low molecular weight lipid binding proteins from wheat seeds, display unique foaming properties and antimicrobial activity. To unravel the mechanism involved in these properties, the interaction of puroindoline-a (PIN-a) with dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG) monolayers was studied by coupling Langmuir-Blodgett and imaging techniques. Compression isotherms of PIN-a/phospholipid monolayers and adsorption of PIN-a to lipid monolayers showed that the protein interacted strongly with phospholipids, especially with the anionic DPPG. The electrostatic contribution led to the formation of a highly stable lipoprotein monolayer. Confocal laser scanning microscopy and atomic force microscopy showed that PIN-a was mainly inserted in the liquid-expanded phase of the DPPC, where it formed an aggregated protein network and induced the fusion of liquid-condensed domains. For DPPG, the protein partitioned in both the liquid-expanded and liquid-condensed phases, where it was aggregated. The extent of protein aggregation was related both to the physical state of phospholipids, i.e., condensed or expanded, and to the electrostatic interactions between lipids and PIN-a. Aggregation of PIN-a at air-liquid and lipid interfaces could account for the biological and technological properties of this wheat lipid binding protein. PMID:14507728

  4. 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.

  5. Ultrasonically treated liquid interfaces for progress in cleaning and separation processes.

    PubMed

    Radziuk, Darya; Möhwald, Helmuth

    2016-01-01

    Ultrasound and acoustic cavitation enable ergonomic and eco-friendly treatment of complex liquids with outstanding performance in cleaning, separation and recycling of resources. A key element of ultrasonic-based technology is the high speed of mixing by streams, flows and jets (or shock waves), which is accompanied by sonochemical reactions. Mass transfer across the phase boundary with a great variety of catalytic processes is substantially enhanced through acoustic emulsification. Encapsulation, separation and recovery of liquids are fast with high production yield if applied by ultrasound. Here we discuss the state of knowledge of these processes by ultrasound and acoustic cavitation from a perspective of a physico-chemical model in order to predict and control the outcome. We focus on the physical interpretation and quantification of ultrasonic parameters and properties of liquids to understand the chemistry of liquid/liquid interfaces in acoustic fields. The roles of thermodynamic enthalpy and entropy (incl. Laplace and osmotic pressure) in the context of sonochemical reactions (separation, catalysis, degradation, cross-linking, ion exchange and phase transfer) are outlined. The synergy of ultrasound and electric fields or continuous flow chemistry for cleaning and separation via emulsification is highlighted by specific strategies involving polymers and ultrasonic membranes. PMID:26435267

  6. Topological defects in electric double layers of ionic liquids at carbon interfaces

    DOE PAGESBeta

    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 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

  7. Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics.

    PubMed

    von Rudorff, Guido Falk; 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 (-OH[Formula: see text]) 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. PMID:27464954

  8. 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. PMID:25127447

  9. Adsorption Behaviors of Mixed Monolayers of n-Alkanes at the Liquid-Solid Interface.

    PubMed

    Hibino, Masahiro

    2016-05-17

    To understand the self-assembly of monolayers at the liquid-solid interface, a thermodynamic model, which describes the contributions of the molecular interactions, is essential. We present an adapted Zimm-Bragg model of the cooperativity transitions for determining the Gibbs free energy for self-assembly at the liquid-solid interface. Scanning tunneling microscopy was used to observe the monolayers formed on graphite from phenyloctane solutions of binary mixtures of n-hexacosane (C26H54) and n-tetratriacontane (C34H70). This revealed that the sharp transition in the monolayers from the full surface coverage of the long-chain alkane, which is adsorbed preferentially, to the full coverage of the short-chain alkane is a function of the mixture composition. The model allows for the estimation of the free-energy changes associated with the difference in the alkyl chain length and the interface between the two different alkane regions in the monolayers. It is also suitable for understanding more complex systems that exhibit intermolecular interactions. PMID:27124544

  10. A level set method for solid-liquid interface tracking in texturally equilibrated pore networks

    NASA Astrophysics Data System (ADS)

    Ghanbarzadeh, Soheil; Hesse, Marc; Prodanovic, Masa

    2015-04-01

    The properties of some porous media are determined by their evolution towards textural equilibrium. Melt drainage from temperate glacier ice and the accumulation of hydrocarbons beneath rock salt are two examples in natural systems. In these materials, pore geometry evolves to minimize the solid-liquid interfacial energy while maintaining dihedral angle, θ, at solid-liquid contact lines. In this work we present the first computations of 3-D texturally equilibrated pore networks using a novel level set method. Interfacial energy minimization is achieved by evolving interface under surface diffusion to constant mean curvature surface. The porosity and dihedral angle constraints are added to the formulation using virtual velocity terms. A domain decomposition scheme is devised to restrict the computational domain and the coupling between the interfaces is achieved on the original computational domain. For the last 30 years, explicit representation of the interfaces limited the computations to highly idealized geometries. The presented model overcomes these limitations and opens the door to the exploration of the physics of these materials in realistic systems. For example, our results show that the fully wetted grain boundaries exist even for θ>0 which reconciles the theory with experimental observations. This work is sponsored by the Statoil Fellows Program at The University of Texas.

  11. Colloidal particle adsorption at liquid interfaces: capillary driven dynamics and thermally activated kinetics.

    PubMed

    Rahmani, Amir M; Wang, Anna; Manoharan, Vinothan N; Colosqui, Carlos E

    2016-08-14

    The adsorption of single colloidal microparticles (0.5-1 μm radius) at a water-oil interface has been recently studied experimentally using digital holographic microscopy [Kaz et al., Nat. Mater., 2012, 11, 138-142]. An initially fast adsorption dynamics driven by capillary forces is followed by an unexpectedly slow relaxation to equilibrium that is logarithmic in time and can span hours or days. The slow relaxation kinetics has been attributed to the presence of surface "defects" with nanoscale dimensions (1-5 nm) that induce multiple metastable configurations of the contact line perimeter. A kinetic model considering thermally activated transitions between such metastable configurations has been proposed [Colosqui et al., Phys. Rev. Lett., 2013, 111, 028302] to predict both the relaxation rate and the crossover point to the slow logarithmic regime. However, the adsorption dynamics observed experimentally before the crossover point has remained unstudied. In this work, we propose a Langevin model that is able to describe the entire adsorption process of single colloidal particles by considering metastable states produced by surface defects and thermal motion of the particle and liquid interface. Invoking the fluctuation dissipation theorem, we introduce a drag term that considers significant dissipative forces induced by thermal fluctuations of the liquid interface. Langevin dynamics simulations based on the proposed adsorption model yield close agreement with experimental observations for different microparticles, capturing the crossover from (fast) capillary driven dynamics to (slow) thermally activated kinetics. PMID:27373956

  12. 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

  13. Two-mode Ginzburg-Landau theory of crystalline anisotropy for fcc-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Wu, Kuo-An; Lin, Shang-Chun; Karma, Alain

    2016-02-01

    We develop a Ginzburg-Landau (GL) theory for fcc crystal-melt systems at equilibrium by employing two sets of order parameters that correspond to amplitudes of density waves of principal reciprocal lattice vectors and amplitudes of density waves of a second set of reciprocal lattice vectors. The choice of the second set of reciprocal lattice vectors is constrained by the condition that this set must form closed triangles with the principal reciprocal lattice vectors in reciprocal space to make the fcc-liquid transition first order. The capillary anisotropy of fcc-liquid interfaces is investigated by GL theory with amplitudes of <111 > and <200 > density waves. Furthermore, we explore the dependence of the anisotropy of the excess free energy of the solid-liquid interface on density waves of higher-order reciprocal lattice vectors such as <311 > by extending the two-mode GL theory with an additional mode. The anisotropy calculated using GL theory with input parameters from molecular dynamics (MD) simulations for fcc Ni is compared to that measured in MD simulations.

  14. Adsorbed and near surface structure of ionic liquids at a solid interface.

    PubMed

    Segura, Juan José; Elbourne, Aaron; Wanless, Erica J; Warr, Gregory G; Voïtchovsky, Kislon; Atkin, Rob

    2013-03-01

    The structure of solid-ionic liquid (IL) interfaces has been characterised with unprecedented clarity by employing a range of atomic force microscopy (AFM) imaging techniques and tip pressures appropriate for the system under study. Soft contact and amplitude-modulation (AM) AFM imaging have been used to elucidate the lateral structure of ILs adsorbed onto mica, and in the near surface ion layers. Data is presented for ethylammonium nitrate (EAN) and 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide (EMIm TFSI). Whereas EAN is a protic IL that forms a nanostructured sponge phase in the bulk, EMIm TFSI is aprotic and has weak (or absent) bulk association structure. Comparison of results obtained for the two liquids elucidates how the strength of bulk liquid morphology effects lateral organisation at the surface, and any effect of IL class, i.e. protic versus aprotic. Imaging reveals EAN self assembles at the solid surface in a worm-like morphology, whereas EMIm cations adsorb in a more isolated fashion, but still in rows templated by the mica surface. To the authors' knowledge, the wormlike structures present at the EAN-mica interface are the smallest self-assembled aggregates ever imaged on a solid surface. PMID:23361257

  15. 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

  16. Mapping and Tuning the Fluorescence of Perfluorinated Polyanilines Synthesized through Liquid-Liquid Interfaces.

    PubMed

    Dallas, Panagiotis; Rašović, Ilija; Porfyrakis, Kyriakos

    2016-04-01

    A series of light-emitting perfluorinated polyanilines were synthesized by the oxidative polymerization of 3-perfluorooctyl aniline through a variety of aqueous/organic interfaces. According to the interfacial tension between the two solvents (the organic being chloroform, dichloromethane, perfluorinated ether, toluene, or o-dichlorobenzene), we obtain distinctive classes of materials based on the crystal packing, protonation, and oxidation state of the polymeric chains. We distinguish between soluble fractions with a distinctive, strong, and red-shifted photoluminescence pattern and an insoluble precipitate which can be subsequently solubilized in a mixture of acetone and toluene. The emission maximum for the insoluble fraction is located in the ultraviolet or blue region with a small Stokes shift; maxima for the soluble counterparts are in the green to yellow region. The soluble derivatives demonstrate a significantly smaller band gap compared to the monomer and large Stokes shifts up to 163 nm; the emission maximum for the most red-shifted emission was located at λ(em) = 548 nm. Their redox activity toward silver nanoparticles, their sensor reactivity with organic acid and bases, and the subsequent changes in the optical properties were demonstrated and the structure of the materials was evaluated with NMR, X-ray diffraction, and FTIR/Raman spectroscopy. PMID:26963137

  17. Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface.

    PubMed

    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

  18. Electrochemical detection of ractopamine at arrays of micro-liquid | liquid interfaces.

    PubMed

    Sairi, Masniza; Arrigan, Damien W M

    2015-01-01

    The behaviour of protonated ractopamine (RacH(+)) at an array of micro-interfaces between two immiscible electrolyte solutions (micro-ITIES) was investigated via cyclic voltammetry (CV) and linear sweep stripping voltammetry (LSSV). The micro-ITIES array was formed at silicon membranes containing 30 pores of radius 11.09±0.12 µm and pore centre-to-centre separation of 18.4±2.1 times the pore radius. CV shows that RacH(+) transferred across the water |1,6-dichlorohexane µITIES array at a very positive applied potential, close to the upper limit of the potential window. Nevertheless, CV was used in the estimation of some of the drug's thermodynamic parameters, such as the formal transfer potential and the Gibbs transfer energy. LSSV was implemented by pre-concentration of the drug, into the organic phase, followed by voltammetric detection, based on the back-transfer of RacH(+) from the organic to aqueous phase. Under optimised pre-concentration and detection conditions, a limit of detection of 0.1 µM was achieved. In addition, the impact of substances such as sugar, ascorbic acid, metal ions, amino acid and urea on RacH(+) detection was assessed. The detection of RacH(+) in artificial serum indicated that the presence of serum protein interferes in the detection signal, so that sample deproteinisation is required for feasible bioanalytical applications. PMID:25476299

  19. Achievement of Diffusional Independence at Nanoscale Liquid-Liquid Interfaces within Arrays.

    PubMed

    Liu, Yang; Sairi, Masniza; Neusser, Gregor; Kranz, Christine; Arrigan, Damien W M

    2015-06-01

    In this work, independent radial diffusion at arrayed nanointerfaces between two immiscible electrolyte solutions (nanoITIES) was achieved. The arrays were formed at nanopores fabricated by focused ion beam milling of silicon nitride (SiN) membranes, enabling the reproducible and systematic design of five arrays with different ratios of pore center-to-center distance (rc) to pore radius (ra). Voltammetry across water-1,6-dichlorohexane nanoITIES formed at these arrays was examined by the interfacial transfer of tetrapropylammonium ions. The diffusion-limited ion-transfer current increased with the ratio rc/ra, reaching a plateau for rc/ra ≥ 56, which was equivalent to the theoretical current for radial diffusion to an array of independent nanoITIES. As a result, mass transport to the nanoITIES arrays was greatly enhanced due to the decreased overlap of diffusion zones at adjacent nanoITIES, allowing each interface in the array to behave independently. When the rc/ra ratio increased from 13 to 56, the analytical performance parameters of sensitivity and limit of detection were improved from 0.50 (±0.02) A M(-1) to 0.76 (±0.02) A M(-1) and from 0.101 (±0.003) μM to 0.072 (±0.002) μM, respectively. These results provide an experimental basis for the design of arrayed nanointerfaces for electrochemical sensing. PMID:25962586

  20. 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.

  1. Order parameters of the liquid crystal interface layer at a rubbed polymer surface

    NASA Astrophysics Data System (ADS)

    Xuan, Li; Tohyama, Takeshi; Miyashita, Tetsuya; Uchida, Tatsuo

    2004-08-01

    In this paper, the liquid crystal (LC) order parameters of the interface layers at rubbed polymer surfaces were studied. The LC films in this study were made with either polyvinyl alcohol or polyimide and the test LCs were filled into wedge-shaped cells for various measurements. The real distribution of order parameters from LC bulk to the interface was obtained by measuring the anisotropic infrared absorbance of sample films. It was found that the order parameters start to decrease where the LC layer thickness is smaller than 10nm, and the order parameter of LC monolayer at the rubbed polymer surface is only 1/3-1/2 of that of the LC bulk even in a strong rubbing condition. When the temperature was increased to the transition point, the LC interface layer (excluding the adsorption monolayer) completed the phase transition while the bulk layer remained in LC phase. This was a further evidence that the order parameter of the interface layer is lower than that of the bulk.

  2. Charge transfer effects of ions at the liquid water/vapor interface

    SciTech Connect

    Soniat, Marielle; Rick, Steven W.

    2014-05-14

    Charge transfer (CT), the movement of small amounts of electron density between non-bonded pairs, has been suggested as a driving force for a variety of physical processes. Herein, we examine the effect of CT on ion adsorption to the water liquid-vapor interface. Using a CT force field for molecular dynamics, we construct a potential of mean force (PMF) for Na{sup +}, K{sup +}, Cl{sup −}, and I{sup −}. The PMFs were produced with respect to an average interface and an instantaneous interface. An analysis of the PMF relative to the instantaneous surface reveals that the area in which the anions experience a free energy minimum is quite narrow, and the cations feel a steeply repulsive free energy near the interface. CT is seen to have only minor effects on the overall free energy profiles. However, the long-ranged effects of ions are highlighted by the CT model. Due to CT, the water molecules at the surface become charged, even when the ion is over 15 Å away from the surface.

  3. 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.

  4. Bile acid-surfactant interactions at the liquid crystal/aqueous interface.

    PubMed

    He, Sihui; Liang, Wenlang; Cheng, Kung-Lung; Fang, Jiyu; Wu, Shin-Tson

    2014-07-14

    The interaction between bile acids and surfactants at interfaces plays an important role in fat digestion. In this paper, we study the competitive adsorption of cholic acid (CA) at the sodium dodecyl sulfate (SDS)-laden liquid crystal (LC)/aqueous interface formed with cyanobiphenyl (nCB, n = 5-8) and the mixture of 5CB with 4-(4-pentylcyclohexyl)benzonitrile (5PCH). We find that the critical concentration of CA required to displace SDS from the interface linearly decreases from 160 μM to 16 μM by reducing the alkyl chain length of nCB from n = 8 to n = 5 and from 16 μM to 1.5 μM by increasing the 5PCH concentration from 0 wt% to 19 wt% in the 5PCH-5CB binary mixture. Our results clearly demonstrate that the sensitivity of 5PCH-5CB mixtures for monitoring the interaction between CA and SDS at the LC/aqueous interface can be increased by one order of magnitude, compared to 5CB. PMID:24825535

  5. 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.

  6. Direct imaging of complex nano- to microscale interfaces involving solid, liquid, and gas phases.

    PubMed

    Rykaczewski, Konrad; Landin, Trevan; Walker, Marlon L; Scott, John Henry J; Varanasi, Kripa K

    2012-10-23

    Surfaces with special wetting properties not only can efficiently repel or attract liquids such as water and oils but also can prevent formation of biofilms, ice, and clathrate hydrates. Predicting the wetting properties of these special surfaces requires detailed knowledge of the composition and geometry of the interfacial region between the droplet and the underlying substrate. In this work we introduce a 3D quantitative method for direct nanoscale visualization of such interfaces. Specifically, we demonstrate direct nano- to microscale imaging of complex fluidic interfaces using cryostabilization in combination with cryogenic focused ion beam milling and SEM imaging. We show that application of this method yields quantitative information about the interfacial geometry of water condensate on superhydrophilic, superhydrophobic, and lubricant-impregnated surfaces with previously unattainable nanoscale resolution. This type of information is crucial to a fundamental understanding as well as the design of surfaces with special wetting properties. PMID:23020195

  7. Healing of Defects at the Interface of Nematic Liquid Crystals and Structured Langmuir-Blodgett Monolayers

    NASA Astrophysics Data System (ADS)

    Petit-Garrido, Núria; Trivedi, Rahul P.; Ignés-Mullol, Jordi; Claret, Josep; Lapointe, Clayton; Sagués, Francesc; Smalyukh, Ivan I.

    2011-10-01

    We use Langmuir-Blodgett molecular monolayers and nematic liquid crystals as model two- and three-dimensional orientationally ordered systems to study the stability and healing of topological defects at their contact interfaces. Integer-strength defects at the monolayer induce disclinations of similar strength in the nematic that, however, do not propagate deep into the bulk, but rather form single- or double-split arch-shaped loops pinned to the interface. This behavior is qualitatively independent of the far-field director orientation and involves either half-integer singular or twist-escaped unity-strength nonsingular nematic disclinations. These two defect configurations can be selected by varying sample preparation given their comparable free energy, consistently with direct probing by use of laser tweezers.

  8. Depletion at Solid-Liquid Interfaces under Shear: Flowing Hexadecane on Functionalized Surfaces

    SciTech Connect

    Guttfreund, Philipp; Wolff, Max; Maccarini, Marco; Gerth, Stefan; Ankner, John Francis; Browning, Jim; Halbert, Candice E; Wacklin, Hanna; Zabel, Hartmut

    2011-01-01

    We present a neutron reflectivity study on the interface of flowing hexadecane, which is known to exhibit surface slip on functionalized solid surfaces. The single crystalline silicon substrates are either chemically cleaned or covered by octadecyl-trichlorosilane (OTS) which result in different interfacial energies in respect to hexadecane. The liquid is in situ sheared and the reflectivities are compared to the static case. Moreover, the temperature dependence is recorded. For both types of interface, density depleted layers are observed, but shear affects them differently. Whereas at the attractive surface the depletion is enhanced by shear, the low interfacial energy leads to a diminishment of the depleted layer when applying shear. This systematic change of the depletion layer indicates different structural rearrangements under shear load. Finally, the possible link of the depletion layer with surface slip is discussed.

  9. Dynamics of ordered colloidal particle monolayers at nematic liquid crystal interfaces.

    PubMed

    Wei, Wei-Shao; Gharbi, Mohamed Amine; Lohr, Matthew A; Still, Tim; Gratale, Matthew D; Lubensky, T C; Stebe, Kathleen J; Yodh, A G

    2016-05-25

    We prepare two-dimensional crystalline packings of colloidal particles on surfaces of the nematic liquid crystal (NLC) 5CB, and we investigate the diffusion and vibrational phonon modes of these particles using video microscopy. Short-time particle diffusion at the air-NLC interface is well described by a Stokes-Einstein model with viscosity similar to that of 5CB. Crystal phonon modes, measured by particle displacement covariance techniques, are demonstrated to depend on the elastic constants of 5CB through interparticle forces produced by LC defects that extend from the interface into the underlying bulk material. The displacement correlations permit characterization of transverse and longitudinal sound velocities of the crystal packings, as well as the particle interactions produced by the LC defects. All behaviors are studied in the nematic phase as a function of increasing temperature up to the nematic-isotropic transition. PMID:27109759

  10. Understanding the influence of capillary waves on solvation at the liquid-vapor interface

    NASA Astrophysics Data System (ADS)

    Rane, Kaustubh; van der Vegt, Nico F. A.

    2016-03-01

    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.

  11. First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent.

    PubMed

    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 TiO(2)-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. PMID:19894999

  12. Electronic structure and charge injection at interface between electrode and liquid-crystalline semiconductor

    NASA Astrophysics Data System (ADS)

    Toda, Tohru; Hanna, Jun-ichi; Tani, Tadaaki

    2007-01-01

    The measurement and analysis of the current-voltage characteristics of a liquid-crystalline organic semiconductor 2-(4'-octyphenyl)-6-dodecyloxynaphthalene (8-PNP-O12) in contact with electrodes of Pt, Au, ITO, Cr, and Al (in the order of work function) have revealed that the injection of holes from the electrodes of Pt, Au, and indium tin oxide to 8-PNP-O12 takes place according to the Richardson-Schottky model and that an electric double layer is formed at the interface between each of these electrodes and 8-PNP-O12, making it difficult to inject holes from the former to the latter.

  13. Flow-assisted 2D polymorph selection: stabilizing metastable monolayers at the liquid-solid interface.

    PubMed

    Lee, Shern-Long; Yuan, Zhongyi; Chen, Long; Mali, Kunal S; Müllen, Klaus; De Feyter, Steven

    2014-05-28

    Controlling crystal polymorphism constitutes a formidable challenge in contemporary chemistry. Two-dimensional (2D) crystals often provide model systems to decipher the complications in 3D crystals. In this contribution, we explore a unique way of governing 2D polymorphism at the organic liquid-solid interface. We demonstrate that a directional solvent flow could be used to stabilize crystalline monolayers of a metastable polymorph. Furthermore, flow fields active within the applied flow generate millimeter-sized domains of either polymorph in a controlled and reproducible fashion. PMID:24867142

  14. Selectively dissolution-recrystallization of ZnO crystals at the air-liquid interface

    NASA Astrophysics Data System (ADS)

    Hu, Xiulan; Masuda, Yoshitake; Ohji, Tatsuki; Kato, Kazumi

    2009-01-01

    Unique morphologies of ZnO crystals were grown firstly at the air-liquid interface. The formation of bamboo leaf- and morning glory-like morphologies depended on the exposed crystal face. ZnO nanosheets were formed by selective dissolution, random diffusion, and recrystallization with a preferential orientation at the edge of pre-existing ZnO nanowhiskers, due to the local deviation of the pH value, which are derived from the volatile and highly soluble ammonia molecules at different fine regions. The high-resolution TEM and selected area electron diffraction clarified the formation mechanism.

  15. Lattice modulation effect of liquid-solid interface on peptide assemblies

    NASA Astrophysics Data System (ADS)

    Yu, Yue; Hou, Jingfei; Yu, Lanlan; Yang, Yanlian; Wang, Chen

    2016-07-01

    We illustrate the single molecule level analysis of the commensurability of the peptide assemblies with the graphite lattice at liquid-solid interface. The pristine peptide assembly was observed to display commensurate registration to graphite lattice, while the introduction of chaperone molecules induces a slight mismatch of the peptide and graphite lattices leading to Moiré patterns. The detailed analysis of the Moiré pattern could provide information of the structural changes of the peptide assembly and the involved peptide-peptide interactions.

  16. Surface-induced selection during in situ photoswitching at the solid/liquid interface.

    PubMed

    Bonacchi, Sara; El Garah, Mohamed; Ciesielski, Artur; Herder, Martin; Conti, Simone; Cecchini, Marco; Hecht, Stefan; Samorì, Paolo

    2015-04-13

    Here we report for the first time a submolecularly resolved scanning tunneling microscopy (STM) study at the solid/liquid interface of the in situ reversible interconversion between two isomers of a diarylethene photoswitch, that is, open and closed form, self-assembled on a graphite surface. Prolonged irradiation with UV light led to the in situ irreversible formation of another isomer as by-product of the reaction, which due to its preferential physisorption accumulates at the surface. By making use of a simple yet powerful thermodynamic model we provide a quantitative description for the observed surface-induced selection of one isomeric form. PMID:25728405

  17. Adsorption-induced anchoring transitions at nematic-liquid-crystal-crystal interfaces

    NASA Astrophysics Data System (ADS)

    Pieranski, P.; Jérôme, B.

    1989-07-01

    Discontinuous (first-order) anchoring transitions are shown to occur as a function of water adsorption at the nematic-liquid-crystal(E9)-gypsum and E9-mica interfaces. The transitions involve growth of domains with an anchoring a' making a finite angle with the direction a of the parent anchoring. The growth proceeds by motion of walls separating the domains with the new anchoring a' from the matrix with the parental anchoring a. A Landau-type expression for the interfacial energy is proposed and used to classify the anchoring transitions and to explain the behavior of the domains during the first-order anchoring transitions.

  18. 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

  19. Nonequilibrium study of the intrinsic free-energy profile across a liquid-vapour interface.

    PubMed

    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. PMID:26827224

  20. Improving Liquid Chromatography-Mass Spectrometry Sensitivity Using a Subambient Pressure Ionization with Nanoelectrospray (SPIN) Interface

    PubMed Central

    Tang, Keqi; Page, Jason S.; Marginean, Ioan; Kelly, Ryan T.; Smith, Richard D.

    2011-01-01

    In this work, the subambient pressure ionization with nanoelectrospray (SPIN) ion source and interface, which operates at ~15–30 Torr, is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100–400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5- to 12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospray ionization (ESI) source was obtained for detected peptides. PMID:21953185

  1. Diffuse-interface modeling of liquid-vapor phase separation in a van der Waals fluid

    NASA Astrophysics Data System (ADS)

    Lamorgese, A. G.; Mauri, R.

    2009-04-01

    We simulate liquid-vapor phase separation in a van der Waals fluid that is deeply quenched into the unstable range of its phase diagram. Our theoretical approach follows the diffuse-interface model, where convection induced by phase change is accounted for via a nonequilibrium (Korteweg) force expressing the tendency of the liquid-vapor system to minimize its free energy. Spinodal decomposition patterns for critical and off-critical van der Waals fluids are studied numerically, revealing the scaling laws of the characteristic length scale and composition of single-phase microdomains, together with their dependence on the Reynolds number. Unlike phase separation of viscous binary mixtures, here local equilibrium is reached almost immediately after single-phase domains start to form. In addition, as predicted by scaling laws, such domains grow in time like t2/3. Comparison between 2D and 3D results reveals that 2D simulations capture, even quantitatively, the main features of the phenomenon.

  2. Effect of throttling on interface behavior and liquid residuals in weightlessness. [in flat-bottomed tank

    NASA Technical Reports Server (NTRS)

    Symons, E. P.

    1974-01-01

    An experimental investigation was conducted to study liquid-vapor interface behavior and subsequent vapor ingestion in a flat-bottomed cylindrical tank following a single-step throttling in outflow rate in a weightless environment. A throttling process in which the final Weber number was one-tenth of the initial Weber number tended to excite large-amplitude symmetric slosh, with the amplitude generally increasing as initial Weber number increased. As expected, liquid residuals were lower than those obtained without throttling and, for moderate values of initial Weber number, could be adequately predicted by assuming that all draining took place at the final Weber number. At large values of Weber number, residuals tended to be lower than this predicted value.

  3. Probing Ion Transfer across Liquid-Liquid Interfaces by Monitoring Collisions of Single Femtoliter Oil Droplets on Ultramicroelectrodes.

    PubMed

    Deng, Haiqiang; Dick, Jeffrey E; Kummer, Sina; Kragl, Udo; Strauss, Steven H; Bard, Allen J

    2016-08-01

    We describe a method of observing collisions of single femtoliter (fL) oil (i.e., toluene) droplets that are dispersed in water on an ultramicroelectrode (UME) to probe the ion transfer across the oil/water interface. The oil-in-water emulsion was stabilized by an ionic liquid, in which the oil droplet trapped a highly hydrophobic redox probe, rubrene. The ionic liquid also functions as the supporting electrolyte in toluene. When the potential of the UME was biased such that rubrene oxidation would be possible when a droplet collided with the electrode, no current spikes were observed. This implies that the rubrene radical cation is not hydrophilic enough to transfer into the aqueous phase. We show that current spikes are observed when tetrabutylammonium trifluoromethanesulfonate or tetrahexylammonium hexafluorophosphate are introduced into the toluene phase and when tetrabutylammonium perchlorate is introduced into the water phase, implying that the ion transfer facilitates electron transfer in the droplet collisions. The current (i)-time (t) behavior was evaluated quantitatively, which indicated the ion transfer is fast and reversible. Furthermore, the size of these emulsion droplets can also be calculated from the electrochemical collision. We further investigated the potential dependence on the electrochemical collision response in the presence of tetrabutylammonium trifluoromethanesulfonate in toluene to obtain the formal ion transfer potential of tetrabutylammonium across the toluene/water interface, which was determined to be 0.754 V in the inner potential scale. The results yield new physical insights into the charge balance mechanism in emulsion droplet collisions and indicate that the electrochemical collision technique can be used to probe formal ion transfer potentials between water and solvents with very low (ε < 5) dielectric constants. PMID:27387789

  4. 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. PMID:27586895

  5. Versatile Side-Illumination Geometry for Tip-Enhanced Raman Spectroscopy at Solid/Liquid Interfaces.

    PubMed

    Martín Sabanés, Natalia; Driessen, Leonie M A; Domke, Katrin F

    2016-07-19

    In situ characterization of surfaces with tip-enhanced Raman spectroscopy (TERS) provides chemical and topographic information with high spatial resolution and submonolayer chemical sensitivity. To further the versatility of the TERS approach toward more complex systems such as biological membranes or energy conversion devices, adaptation of the technique to solid/liquid working conditions is essential. Here, we present a home-built side-illumination TERS setup design based on a commercial scanning tunneling microscope (STM) as a versatile, cost-efficient solution for TERS at solid/liquid interfaces. Interestingly, the results obtained from showcase resonant dye and nonresonant thiophenol monolayers adsorbed on Au single crystals suggest that excitation beam aberrations due to the presence of the aqueous phase are small enough not to limit TER signal detection. The STM parameters are found to play a crucial role for solid/liquid TERS sensitivity. Raman enhancement factors of 10(5) at μW laser power demonstrate the great potential the presented experimental configuration holds for solid/liquid interfacial spectroscopic studies. PMID:27299508

  6. 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. PMID:25792476

  7. 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.

  8. 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

  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. 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

  11. Label-free biomolecular detection at electrically displaced liquid interfaces using interfacial electrokinetic transduction (IET).

    PubMed

    Mavrogiannis, Nicholas; Crivellari, Francesca; Gagnon, Zachary R

    2016-03-15

    Biosensors require a biorecognition element that specifically binds to a target analyte, and a signal transducer, which converts this targeted binding event into a measurable signal. While current biosensing methods are capable of sensitively detecting a variety of target analytes in a laboratory setting, there are inherent difficulties in developing low-cost portable biosensors for point-of-care diagnostics using traditional optical, mass, or electroanalytical-based signal transducers. It is therefore important to develop new biosensing transducer elements for recognizing binding events at low cost and in portable environments. Here, we demonstrate a novel electrokinetic liquid biosensing method for the sensitive label-free detection of a model biomolecule against a background of serum protein. The biosensor is based on the motion of a microfluidic-generated electrical liquid interface when subjected to an external alternating current electrical field. We demonstrate that the electric field-induced motion of the interface can be used as a sensitive and specific transducer for the detection of avidin at femtomolar concentrations in solution. This new detection strategy does not require surface functionalization or fluorescent labels, and has the potential to serve as a sensitive low-cost method for portable biomarker detection. PMID:26513285

  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. 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

  14. Mechanisms of microstructure development at metallic-interlayer/ceramic interfaces during liquid-film-assisted bonding

    SciTech Connect

    Sugar, Joshua D.

    2003-12-01

    Alumina has been bonded via copper/niobium/copper interlayers, and correlations have been made between various processing conditions (applied load, processing temperature, copper film thickness, surface roughness, etc.) and strength. Four-point bend strengths and micrographs of fracture surfaces have been used to determine the relationship between processing, microstructure, and properties. Transparent sapphire substrates bonded with copper/niobium/copper interlayers were used in model experiments to track the microstructural development of these ceramic/metal interfaces and to identify the important mechanisms that contribute. High interfacial strengths were generally associated with small unbonded regions, extensive breakup of the copper film into isolated particles, ceramic pullout, and regions of niobium/alumina contact where the grain boundary grooves of the alumina are visible on both sides of the fracture surface. Experiments with sapphire substrates showed that asperities in the niobium and grain boundary grooves in the niobium play an important role in the initiation and growth of sapphire/niobium contact. The presence of a liquid film can enhance the kinetics of sapphire/niobium contact and growth by providing a low-temperature high-diffusivity path. The breakup of the copper film was described using two models that were in fairly close agreement. The breakup of the copper film depended on the asperity density in the niobium, niobium grain boundary density, liquid film redistribution, and the breakup of liquid patches via Rayleigh instabilities. The redistribution of the liquid was affected by defect geometry, local film thickness, and local interfacial crystallography. Thermal grooving effects of liquid copper on alumina and niobium were studied using conventional sessile drop experiments. The thermal grooving of one particular grain boundary in alumina when in contact with copper and niobium was studied using a fabricated bicrystal. Both diffusion

  15. Adsorption/aggregation of surfactants and their mixtures at solid-liquid interfaces.

    PubMed

    Somasundaran, P; Huang, L

    2000-12-11

    Adsorption of surfactants and polymers at solid-liquid interfaces is used widely to modify interfacial properties in a variety of industrial processes such as flotation, ceramic processing, flocculation/dispersion, personal care product formulation and enhanced oil recovery. The behavior of surfactants and polymers at interfaces is determined by a number of forces, including electrostatic attraction, covalent bonding, hydrogen bonding, hydrophobic bonding, and solvation and desolvation of various species. The extent and type of the forces involved varies depending on the adsorbate and the adsorbent, and also the composition and other characteristics of the solvent and dissolved components in it. The influence of such forces on the adsorption behavior is reviewed here from a thermodynamics point of view. The experimental results from microcalorimetric and spectroscopic studies of adsorbed layers of different surfactant and polymer systems at solid-liquid interfaces are also presented. Calorimetric data from the adsorption of an anionic surfactant, sodium octylbenzenesulfonate, and a non-ionic surfactant, dodecyloxyheptaethoxyethylalcohol, and their mixtures on alumina, yielded important thermodynamic information. It was found that the adsorption of anionic surfactants alone on alumina was initially highly exothermic due to the electrostatic interaction with the substrate. Further adsorption leading to a solloid (hemimicelle) formation is proposed to be mainly an entropy-driven process. The entropy effect was found to be more pronounced for the adsorption of anionic-non-ionic surfactant mixtures than for the anionic surfactant alone. Fluorescence studies using a pyrene probe on an adsorbed surfactant and polymer layers, along with electron spin resonance (ESR) spectroscopy, reveal the role of surface aggregation and the conformation of the adsorbed molecules in controlling the dispersion and wettability of the system. PMID:11185696

  16. 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

  17. Dual analyzer system for surface analysis dedicated for angle-resolved photoelectron spectroscopy at liquid surfaces and interfaces.

    PubMed

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian

    2016-04-01

    The investigation of liquid surfaces and interfaces with the powerful toolbox of ultra-high vacuum (UHV)-based surface science techniques generally has to overcome the issue of liquid evaporation within the vacuum system. In the last decade, however, new classes of liquids with negligible vapor pressure at room temperature-in particular, ionic liquids (ILs)-have emerged for surface science studies. It has been demonstrated that particularly angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) allows for investigating phenomena that occur at gas-liquid and liquid-solid interfaces on the molecular level. The results are not only relevant for IL systems but also for liquids in general. In all of these previous ARXPS studies, the sample holder had to be tilted in order to change the polar detection angle of emitted photoelectrons, which restricted the liquid systems to very thin viscous IL films coating a flat solid support. We now report on the concept and realization of a new and unique laboratory "Dual Analyzer System for Surface Analysis (DASSA)" which enables fast ARXPS, UV photoelectron spectroscopy, imaging XPS, and low-energy ion scattering at the horizontal surface plane of macroscopically thick non-volatile liquid samples. It comprises a UHV chamber equipped with two electron analyzers mounted for simultaneous measurements in 0° and 80° emission relative to the surface normal. The performance of DASSA on a first macroscopic liquid system will be demonstrated. PMID:27131705

  18. Dual analyzer system for surface analysis dedicated for angle-resolved photoelectron spectroscopy at liquid surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian

    2016-04-01

    The investigation of liquid surfaces and interfaces with the powerful toolbox of ultra-high vacuum (UHV)-based surface science techniques generally has to overcome the issue of liquid evaporation within the vacuum system. In the last decade, however, new classes of liquids with negligible vapor pressure at room temperature—in particular, ionic liquids (ILs)—have emerged for surface science studies. It has been demonstrated that particularly angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) allows for investigating phenomena that occur at gas-liquid and liquid-solid interfaces on the molecular level. The results are not only relevant for IL systems but also for liquids in general. In all of these previous ARXPS studies, the sample holder had to be tilted in order to change the polar detection angle of emitted photoelectrons, which restricted the liquid systems to very thin viscous IL films coating a flat solid support. We now report on the concept and realization of a new and unique laboratory "Dual Analyzer System for Surface Analysis (DASSA)" which enables fast ARXPS, UV photoelectron spectroscopy, imaging XPS, and low-energy ion scattering at the horizontal surface plane of macroscopically thick non-volatile liquid samples. It comprises a UHV chamber equipped with two electron analyzers mounted for simultaneous measurements in 0° and 80° emission relative to the surface normal. The performance of DASSA on a first macroscopic liquid system will be demonstrated.

  19. The influence of the solid/liquid interface on the dewetting of ultra thin polymer films

    NASA Astrophysics Data System (ADS)

    Lessel, Matthias; Klos, Mischa; Baeumchen, Oliver; Jacobs, Karin

    2012-02-01

    In recent years, many studies showed that a thin liquid film on a solid surface in air bears more complexity than expected from a simple three-layer-system: e.g. a highly mobile surface layer in case the liquid is an unentangled polystyrene (PS) melt (Yang et al., Science 2010; Seemann et al., J. of Polym. Sci. 2006) or the PS melt can slip over the solid substrate (Baeumchen et al., PRL 2009). Our study focuses on such phenomena and explores their influence on dewetting (speed, morphology, etc.). We use hydrophilic and -phobic Si wafer (either covered by a highly ordered silane layer or by a thin layer of an amorphous fluoropolymer, AF 1600). On each of the substrates, one expects for a certain set of parameters spinodal dewetting for the PS melt. Yet experimentally, a much higher hole density is observed for both types of hydrophobic wafers than is theoretically expected. Moreover, the two hydrophobic coatings induce different dewetting speeds: the PS melt dewets faster on the silane covered Si wafer. The difference is attributed to slip (silane) or to no slip (AF 1600) conditions at the PS/substrate interface, which is also observable in the type of liquid front profile, which in turn changes the dewetting morphology.

  20. An interface for the direct coupling of small liquid samples to AMS

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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. 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.

  1. Surface induced phase separation and pattern formation at the isotropic interface in chiral nematic liquid crystals.

    PubMed

    Zola, R S; Evangelista, L R; Yang, Y-C; Yang, D-K

    2013-02-01

    We study the pattern formation of a chiral nematic liquid crystal under a wetting transition. In the isotropic-liquid crystal transition, a surface-enhanced effect happens and a thin liquid crystal layer forms at the substrates of the cell. In this confined system, chirality, elastic anisotropy, surface anchoring, and wetting strength interplay. A striped pattern is formed due to the chiral nature of the material and the tilted anchoring at the isotropic boundary. As the wetting layer grows from cooling the sample, first the stripes rotate through a process where dislocation defects are formed. As the wetting layer grows further, the periodicity of the stripe structure changes, and finally a splitting of the stripes occurs. Because of the unique properties of this system, new insights about pitch-thickness ratio, interface anchoring, and elastic anisotropy effect are found. Since the anchoring at the isotropic boundary is weak, the critical ratio between the thickness of the wetting layer and the helical pitch is different from that reported in the literature. We also discover that the elastic anisotropy and elastic constant ratios play a critical role in stripe formation. Because of the similarity with biological fibrous composites (twisted plywood), our system may be used as a synthetic version to mimic the naturally occurring one. We carry out a simulation study to explain the experimental results. PMID:23414046

  2. Surface Induced Phase Separation and Pattern Formation at the Isotropic Interface in Chiral Nematic Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Zola, R. S.; Evangelista, L. R.; Yang, Y.-C.; Yang, D.-K.

    2013-02-01

    We study the pattern formation of a chiral nematic liquid crystal under a wetting transition. In the isotropic-liquid crystal transition, a surface-enhanced effect happens and a thin liquid crystal layer forms at the substrates of the cell. In this confined system, chirality, elastic anisotropy, surface anchoring, and wetting strength interplay. A striped pattern is formed due to the chiral nature of the material and the tilted anchoring at the isotropic boundary. As the wetting layer grows from cooling the sample, first the stripes rotate through a process where dislocation defects are formed. As the wetting layer grows further, the periodicity of the stripe structure changes, and finally a splitting of the stripes occurs. Because of the unique properties of this system, new insights about pitch-thickness ratio, interface anchoring, and elastic anisotropy effect are found. Since the anchoring at the isotropic boundary is weak, the critical ratio between the thickness of the wetting layer and the helical pitch is different from that reported in the literature. We also discover that the elastic anisotropy and elastic constant ratios play a critical role in stripe formation. Because of the similarity with biological fibrous composites (twisted plywood), our system may be used as a synthetic version to mimic the naturally occurring one. We carry out a simulation study to explain the experimental results.

  3. An interface for the direct coupling of small liquid samples to AMS

    DOE PAGESBeta

    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 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

  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. Stereodynamics in state-resolved scattering at the gas–liquid interface

    PubMed Central

    Perkins, Bradford G.; Nesbitt, David J.

    2008-01-01

    Stereodynamics at the gas–liquid interface provides insight into the important physical interactions that directly influence heterogeneous chemistry at the surface and within the bulk liquid. We investigate molecular beam scattering of CO2 from a liquid perfluoropolyether (PFPE) surface in vacuum [incident energy Einc = 10.6(8) kcal/mol, incident angle θinc = 60°] to specifically reveal rotational angular-momentum directions for scattered molecules. Experimentally, internal quantum state populations and MJ distributions are probed by high-resolution polarization-modulated infrared laser spectroscopy. Analysis of J-state populations reveals dual-channel scattering dynamics characterized by a two-temperature Boltzmann distribution for trapping–desorption and impulsive scattering. In addition, molecular dynamics simulations of CO2 + fluorinated self-assembled monolayers have been used to model CO2 + PFPE dynamics. Experimental results and molecular dynamics simulations reveal highly oriented CO2 distributions that preferentially scatter with “top spin” as a strongly increasing function of J state. PMID:18678907

  6. Microscopic thin film optical anisotropy imaging at the solid-liquid interface

    NASA Astrophysics Data System (ADS)

    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 cm2 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.

  7. 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. PMID:27131681

  8. 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.

  9. Novel impedance cell for low conductive liquids: determination of bulk and interface contributions.

    PubMed

    Becchi, Marta; Callegaro, Luca; Durbiano, Francesca; D'Elia, Vincenzo; Strigazzi, Alfredo

    2007-11-01

    A plane capacitor cell with variable gap has been designed in order to detect the complex permittivity of low conductive liquids (up to 500 microS/cm) and the impedance of the sample-electrode interface. The novelty of the cell consists of the simultaneous presence of the field uniformity ensured by a guard ring, an adjustable gap between 300 microm and 6.75 mm (the electrode axial motion avoiding any rotation), and the immersion of the capacitor in the sample reservoir. The size of the capacitor electrodes and the gap values have been tested via the capacitance detection of the in-air cell at 1 kHz. The sample measurements have been performed by scanning the frequency range between 15 Hz and 2 MHz at four different capacitor gap values. In the paper a method to directly extract the bulk complex permittivity and the interface impedance versus frequency is presented. It is based on the assumption that the interface contribution is independent of the electrode gap, as confirmed (within the measurement accuracy) from measurements on all samples investigated. As samples of interest, we have chosen two certified electrolytic conductivity standards, KCl aqueous solutions having conductivity traceable to SI units; and two polymer latex aqueous dispersions of microspheres. Regarding KCl solutions, the conductivity measurements are compatible with the reference values within the specified uncertainty; the measured permittivities are consistent with the literature. For all samples, we have recovered the expected result that the interface impedance mainly affects the low frequency range (f<10 kHz). PMID:18052483

  10. 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. PMID:26974812

  11. 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.

  12. 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.

  13. Analysis of bacterial detachment from substratum surfaces by the passage of air-liquid interfaces.

    PubMed

    Gómez-Suárez, C; Busscher, H J; van der Mei, H C

    2001-06-01

    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 x 10(6) 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

  14. 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

  15. Exploring the complexity of supramolecular interactions for patterning at the liquid-solid interface.

    PubMed

    Mali, Kunal S; Adisoejoso, Jinne; Ghijsens, Elke; De Cat, Inge; De Feyter, Steven

    2012-08-21

    The use of self-assembly to fabricate surface-confined adsorbed layers (adlayers) from molecular components provides a simple means of producing complex functional surfaces. The molecular self-assembly process relies on supramolecular interactions sustained by noncovalent forces such as van der Waals, electrostatic, dipole-dipole, and hydrogen bonding interactions. Researchers have exploited these noncovalent bonding motifs to construct well-defined two-dimensional (2D) architectures at the liquid-solid interface. Despite myriad examples of 2D molecular assembly, most of these early findings were serendipitous because the intermolecular interactions involved in the process are often numerous, subtle, cooperative, and multifaceted. As a consequence, the ability to tailor supramolecular patterns has evolved slowly. Insight gained from various studies over the years has contributed significantly to the knowledge of supramolecular interactions, and the stage is now set to systematically engineer the 2D supramolecular networks in a "preprogrammed" fashion. The control over 2D self-assembly of molecules has many important implications. Through appropriate manipulation of supramolecular interactions, one can "encode" the information at the molecular level via structural features such as functional groups, substitution patterns, and chiral centers which could then be retrieved, transferred, or amplified at the supramolecular level through well-defined molecular recognition processes. This ability allows for precise control over the nanoscale structure and function of patterned surfaces. A clearer understanding and effective use of these interactions could lead to the development of functional surfaces with potential applications in molecular electronics, chiral separations, sensors based on host-guest systems, and thin film materials for lubrication. In this Account, we portray our various attempts to achieve rational design of self-assembled adlayers by exploiting the

  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. Nonlinear vibrational spectroscopic studies of molecular interaction and charging behavior at solid/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Luning

    Solid-liquid interfaces have been the focus of different communities of scientists due to its importance in industrial applications and chemical processes in nature. Molecular interactions and surface charges affect the physicochemical properties of these interfaces and a thorough understanding is still lacking now. This thesis describes our work in studying several model solid-liquid interfaces using sum-frequency vibrational spectroscopy. Through the studies of interfacial vibrational spectra, we hope to gain better understanding of molecular interactions in competitive adsorption process and also surface charging behavior at different pH and salt concentrations. We start by studying alcohol-water mixture and the adsorption behavior at both hydrophilic and hydrophobic surfaces. In both cases, alcohol adsorbs preferentially from water. The tendency for water to form strong hydrogen-bonding network is the driving force for preferential adsorption of alcohol. We proposed two different interfacial molecular structures on hydrophilic and hydrophobic surfaces. We move on to study the interaction of pure water with a solid surface. Single crystal alumina is used as a model system. At different pH, the surface can undergo protonation and deprotonation reactions and accumulates surface charge. Both the hydrogen-bonding with water and the surface field created by surface charge can affect interfacial water structure. Combining the information obtained with intensity and phase spectra, we find water molecules have two types of bonding within the interfacial layer: weakly hydrogen-bonded species near 3450 cm-1 that does not flip with switching surface charge, and strongly hydrogen-bonded species at 3200 cm-1 that readily flips with switching surface field. One other system we have studied is nanoporous silica-water interface. We found that signal from interfacial water is reduced due to the porous nature of the film. The water spectral features tell us about the interfacial

  18. 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.

  19. Magnetic-field-induced crossover from non-Fermi to Fermi liquid at the quantum critical point of YbCu5-xAux

    NASA Astrophysics Data System (ADS)

    Carretta, P.; Pasero, R.; Giovannini, M.; Baines, C.

    2009-01-01

    The temperature (T) dependence of the muon and C63u nuclear spin-lattice relaxation rates 1/T1 in YbCu4.4Au0.6 is reported over nearly four decades. It is shown that for T→0 1/T1 diverges following the behavior predicted by the self-consistent renormalization (SCR) theory for a ferromagnetic quantum critical point. On the other hand, the static uniform susceptibility χs is observed to diverge as T-2/3 and 1/T1T∝χs2 , a behavior which is not accounted for by SCR theory. The application of a magnetic field H is observed to induce a crossover to a Fermi-liquid behavior and for T→0 1/T1 is found to obey the scaling law 1/T1(H)=1/T1(0)[1+(μBH/kBT)2]-1 .

  20. Primary Air-Liquid Interface Culture of Nasal Epithelium for Nasal Drug Delivery.

    PubMed

    Ong, Hui Xin; Jackson, Claire L; Cole, Janice L; Lackie, Peter M; Traini, Daniela; Young, Paul M; Lucas, Jane; Conway, Joy

    2016-07-01

    Nasal drug administration is a promising alternative to oral and parenteral administration for both local and systemic delivery of drugs. The benefits include its noninvasive nature, rapid absorption, and circumvention of first pass metabolism. Hence, the use of an in vitro model using human primary nasal epithelial cells could be key to understanding important functions and parameters of the respiratory epithelium. This model will enable investigators to address important and original research questions using a biologically relevant in vitro platform that mimics the in vivo nasal epithelial physiology. The purpose of this study was to establish, systematically characterize, and validate the use of a primary human nasal epithelium model cultured at the air-liquid interface for the study of inflammatory responses and drug transport and to simultaneously quantify drug effects on ciliary activity. PMID:27223825

  1. A Janus-paper PDMS platform for air-liquid interface cell culture applications

    NASA Astrophysics Data System (ADS)

    Rahimi, Rahim; Ochoa, Manuel; Donaldson, Amy; Parupudi, Tejasvi; Dokmeci, Mehmet R.; Khademhosseini, Ali; Ghaemmaghami, Amir; Ziaie, Babak

    2015-05-01

    A commercially available Janus paper with one hydrophobic (polyethylene-coated) face and a hygroscopic/hydrophilic one is irreversibly bonded to a polydimethylsiloxane (PDMS) substrate incorporating microfluidic channels via corona discharge surface treatment. The bond strength between the polymer-coated side and PDMS is characterized as a function of corona treatment time and annealing temperature/time. A maximum strength of 392 kPa is obtained with a 2 min corona treatment followed by 60 min of annealing at 120 °C. The water contact angle of the corona-treated polymer side decreases with increased discharge duration from 98° to 22°. The hygroscopic/hydrophilic side is seeded with human lung fibroblast cells encapsulated in a methacrylated gelatin (GelMA) hydrogel to show the potential of this technology for nutrient and chemical delivery in an air-liquid interface cell culture.

  2. Local conformational switching of supramolecular networks at the solid/liquid interface.

    PubMed

    Cometto, Fernando P; Kern, Klaus; Lingenfelder, Magalí

    2015-05-26

    We use the electric field in a scanning tunneling microscope to manipulate the transition between open and close packed 2D supramolecular networks of neutral molecules in nonpolar media. We found that while the magnitude of the applied field is not decisive, it is the sign of the polarization that needs to be maintained to select one particular polymorph. Moreover, the switching is independent of the solvent used and fully reversible. We propose that the orientation of the surface dipole determined by the electric field might favor different conformation-depended charge transfer mechanisms of the adsorbates to the surface, inducing open (closed) structures for negative (positive) potentials. Our results show the use of local fields to select the polymorphic outcome of supramolecular assemblies at the solid/liquid interface. The effect has potential to locally control the capture and release of analytes in host-guest systems and the 2D morphology in multicomponent layers. PMID:25857528

  3. Passive micromixer using by convection and surface tension effects with air-liquid interface

    PubMed Central

    Ju, Jongil; Warrick, Jay

    2014-01-01

    This article describes a passive micromixer that utilizes an air-liquid interface and surface tension effects to enhance fluid mixing via convection and Marangoni effects. Performance of the microfluidic component is tested within a passive-pumping-based device that consists of three microchannels connected in succession using passive micro-mixers. Mixing was quantified at 5 key points along the length of the device using microscope images of patterned streams of Alexa 488 fluorescent-dyed water and pure DI water flowing through the device. The passive micro-mixer mixed fluid 15–20 times more effectively than diffusion between laminar flow streams alone and is a novel micro-mixer embodiment that provides an additional strategy for removing external components from microscale devices for simpler, autonomous operation. PMID:25104979

  4. Influence of interface stabilisers and surrounding aqueous phases on nematic liquid crystal shells.

    PubMed

    Noh, JungHyun; Reguengo De Sousa, Kevin; Lagerwall, Jan P F

    2016-01-14

    We investigate the nematic-isotropic (N-I) transition in shells of the liquid crystal 5CB, surrounded by aqueous phases that conventionally are considered to be immiscible with 5CB. The aqueous phases contain either sodium dodecyl sulfate (SDS) or polyvinyl alcohol (PVA) as stabiliser, the former additionally promoting homeotropic director alignment. For all shell configurations we find a depression of the clearing point compared to pure 5CB, indicating that a non-negligible fraction of the constituents of the surrounding phases enter the shell, predominantly water. In hybrid-aligned shells, with planar outer and homeotropic inner boundary (or vice versa), the N-I transition splits into two steps, with a consequent three-step textural transformation. We explain this as a result of the order-enhancing effect of a monolayer of radially aligned SDS molecules adsorbed at the homeotropic interface. PMID:26512764

  5. 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. PMID:26844589

  6. Design of a monochromatic ellipsometer for studies at the solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Pai-Panandiker, R. S.; Dorgan, J. R.

    1995-02-01

    A new design for a monochromatic ellipsometer used for studies at the solid-liquid interface is described. The design of the ellipsometer incorporates two novel features—a special optical glass cell and a thermally controlled sample oven. The ellipsometer design allows for in situ kinetic studies through use of the optical glass cell. Furthermore, the apparatus is modified to allow thermal equilibration over a range of temperatures. The temperature response of the cell assembly is presented and the response time is seen to be approximately 1 h. Data on the adsorption of a diblock copolymer [poly(ethylene oxide)-block-polystyrene] are presented; the analyzed data agree with previous studies on the same system.

  7. Dynamics at the Liquid-Vapor Interface of a Supercooled Organic Glass Former

    NASA Astrophysics Data System (ADS)

    Sikorski, M.; Gutt, C.; Chushkin, Y.; Lippmann, M.; Franz, H.

    2010-11-01

    We investigated the dynamics near the liquid-vapor interface of the supercooled model organic glass former dibutyl phthalate by using surface-sensitive x-ray scattering techniques. Our results reveal significant enhancement of the relaxation rate over a wide length-scales range. The analysis of the dispersion relation of long-wavelength surface fluctuations yields a nonzero value of the share modulus near the free surface. At the molecular level, the dynamics in the near surface region (10-15 nm) is inhomogeneous. The mobility is decreasing with increasing distance from the free surface. Below the bulk glass transition, two distinct relaxation times were observed differing by 1 order of magnitude. The observed fast relaxation proves the existence of a high mobility liquidlike surface layer of 10 nm thickness on top of a frozen in bulk system.

  8. 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.

  9. Model of dynamic self-assembly in ferromagnetic suspensions at liquid interfaces.

    PubMed

    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. PMID:24125361

  10. A wave packet model for electron transfer and its implications for the semiconductor-liquid interface

    SciTech Connect

    Smith, B.B.; Nozik, A.J.

    1999-11-11

    This paper establishes the computational feasibility and examines the implications of a particular technique for simulations of time dependent electron transfer (ET) at semiconductor-liquid interfaces (SLIs). The methodology uses a one electron formalism employing wave packets, pseudopotentials, and molecular dynamics, which the authors dub WPMD. They describe a detailed mechanism for SLI ET by using the methodology. The model is versatile enough to address conventional SLI ET, surface state and adsorption mediated ET, photoexcited ET, and ET between quantum dots and other microstructures. They contrast the perspectives of their WPMD model of SLI ET with those in traditional literature and find substantial differences. The use of standard Landau-Zener theory for SLI ET is found particularly problematic.

  11. Non-monotonic changes in critical solidification rates for stability of liquid-solid interfaces with static magnetic fields

    PubMed Central

    Ren, W. L.; Fan, Y. F.; Feng, J. W.; Zhong, Y. B.; Yu, J. B.; Ren, Z. M.; Liaw, P. K.

    2016-01-01

    We report the magnetic field dependence of the critical solidification rate for the stability of liquid-solid interfaces. For a certain temperature gradient, the critical solidification rate first increases, then decreases, and subsequently increases with increasing magnetic field. The effect of the magnetic field on the critical solidification rate is more pronounced at low than at high temperature gradients. The numerical simulations show that the magnetic-field dependent changes of convection velocity and contour at the interface agree with the experimental results. The convection velocity first increases, then decreases, and finally increases again with increasing the magnetic field intensity. The variation of the convection contour at the interface first decreases, then increases slightly, and finally increases remarkably with increasing the magnetic field intensity. Thermoelectromagnetic convection (TEMC) plays the role of micro-stirring the melt and is responsible for the increase of interface stability within the initially increasing range of magnetic field intensity. The weak and significant extents of the magneto-hydrodynamic damping (MHD)-dependent solute build-up at the interface front result, respectively, in the gradual decrease and increase of interfacial stability with increasing the magnetic field intensity. The variation of the liquid-side concentration at the liquid-solid interface with the magnetic field supports the proposed mechanism. PMID:26846708

  12. Non-monotonic changes in critical solidification rates for stability of liquid-solid interfaces with static magnetic fields.

    PubMed

    Ren, W L; Fan, Y F; Feng, J W; Zhong, Y B; Yu, J B; Ren, Z M; Liaw, P K

    2016-01-01

    We report the magnetic field dependence of the critical solidification rate for the stability of liquid-solid interfaces. For a certain temperature gradient, the critical solidification rate first increases, then decreases, and subsequently increases with increasing magnetic field. The effect of the magnetic field on the critical solidification rate is more pronounced at low than at high temperature gradients. The numerical simulations show that the magnetic-field dependent changes of convection velocity and contour at the interface agree with the experimental results. The convection velocity first increases, then decreases, and finally increases again with increasing the magnetic field intensity. The variation of the convection contour at the interface first decreases, then increases slightly, and finally increases remarkably with increasing the magnetic field intensity. Thermoelectromagnetic convection (TEMC) plays the role of micro-stirring the melt and is responsible for the increase of interface stability within the initially increasing range of magnetic field intensity. The weak and significant extents of the magneto-hydrodynamic damping (MHD)-dependent solute build-up at the interface front result, respectively, in the gradual decrease and increase of interfacial stability with increasing the magnetic field intensity. The variation of the liquid-side concentration at the liquid-solid interface with the magnetic field supports the proposed mechanism. PMID:26846708

  13. Non-monotonic changes in critical solidification rates for stability of liquid-solid interfaces with static magnetic fields

    NASA Astrophysics Data System (ADS)

    Ren, W. L.; Fan, Y. F.; Feng, J. W.; Zhong, Y. B.; Yu, J. B.; Ren, Z. M.; Liaw, P. K.

    2016-02-01

    We report the magnetic field dependence of the critical solidification rate for the stability of liquid-solid interfaces. For a certain temperature gradient, the critical solidification rate first increases, then decreases, and subsequently increases with increasing magnetic field. The effect of the magnetic field on the critical solidification rate is more pronounced at low than at high temperature gradients. The numerical simulations show that the magnetic-field dependent changes of convection velocity and contour at the interface agree with the experimental results. The convection velocity first increases, then decreases, and finally increases again with increasing the magnetic field intensity. The variation of the convection contour at the interface first decreases, then increases slightly, and finally increases remarkably with increasing the magnetic field intensity. Thermoelectromagnetic convection (TEMC) plays the role of micro-stirring the melt and is responsible for the increase of interface stability within the initially increasing range of magnetic field intensity. The weak and significant extents of the magneto-hydrodynamic damping (MHD)-dependent solute build-up at the interface front result, respectively, in the gradual decrease and increase of interfacial stability with increasing the magnetic field intensity. The variation of the liquid-side concentration at the liquid-solid interface with the magnetic field supports the proposed mechanism.

  14. 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.

  15. 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)

  16. Liquid interfaces in viscous straining flows: Numerical studies of the selective withdrawal transition

    NASA Astrophysics Data System (ADS)

    Berkenbusch, Marko Kleine

    In selective withdrawal, the interface between two liquid layers is deformed by an imposed withdrawal flow. A shape transition occurs at a threshold flow rate that changes the topology of the interface from a steady-state hump to an entrained spout. Near the transition a very sharp hump tip occurs, with the minimum tip radius far smaller than the characteristic lateral length-scale. Previous measurements [Cohen et al., Phys. Rev. Lett. 88, 2002] suggest the sharp hump is created via an approach towards a singular steady-state shape which is cut off at a small lengthscale. To help unfold the mechanism underlying the shape transition and to determine the origin of the cutoff lengthscale, we construct a numerical model and compare its results against experimental measurements. The increased resolution in the simulation enables us to identify the shape transition both in the experiment and the numerics as a saddle-node bifurcation. The transition does not involve an approach towards a singular shape as the hump radius never becomes much smaller than the hump height. Results from different boundary conditions collapse when appropriately rescaled. The collapsed curves show that the tip curvature remains coupled to the tip height, showing an approximately exponential dependence.

  17. 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.

  18. 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.

  19. 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. PMID:27288573

  20. 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.

  1. Nitrous oxide supersaturation at the liquid/air interface of animal waste.

    PubMed

    Makris, Konstantinos C; Andra, Syam S; Hardy, Michael; Sarkar, Dibyendu; Datta, Rupali; Bach, Stephan B H; Mullens, Conor P

    2009-12-01

    Concentrated animal feeding operations around the globe generate large amounts of nitrous oxide (N(2)O) in the surrounding atmosphere. Liquid animal waste systems have received little attention with respect to N(2)O emissions. We hypothesized that the solution chemistry of animal waste aqueous suspensions would promote conditions that lead to N(2)O supersaturation at the liquid/air interface. The concentration of dissolved N(2)O in poultry litter (PL) aqueous suspensions at 25 degrees C was 0.36 microg N(2)O mL(-1), at least an order of magnitude greater than that measured in water in equilibrium with ambient air, suggesting N(2)O supersaturation. There was a nonlinear increase in the N(2)O Henry constants of PL from 2810 atm/mole fraction at 35 degrees C to 17 300 atm/mole fraction at 41 degrees C. The extremely high N(2)O Henry constants were partially ascribed to N(2)O complexation with aromatic moieties. Complexed N(2)O structures were unstable at temperatures > 35 degrees C, supplying the headspace with additional free N(2)O concentrations. PMID:19573962

  2. 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.

  3. 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.

  4. 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.

  5. Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Piper, Daniela Molina; 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

    2015-02-01

    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.

  6. Solid-liquid interface free energies of pure bcc metals and B2 phases

    DOE PAGESBeta

    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

  7. 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.

  8. Air-Liquid Interface Biofilms of Bacillus cereus: Formation, Sporulation, and Dispersion▿

    PubMed Central

    Wijman, Janneke G. E.; de Leeuw, Patrick P. L. A.; Moezelaar, Roy; Zwietering, Marcel H.; Abee, Tjakko

    2007-01-01

    Biofilm formation by Bacillus cereus was assessed using 56 strains of B. cereus, including the two sequenced strains, ATCC 14579 and ATCC 10987. Biofilm production in microtiter plates was found to be strongly dependent on incubation time, temperature, and medium, as well as the strain used, with some strains showing biofilm formation within 24 h and subsequent dispersion within the next 24 h. A selection of strains was used for quantitative analysis of biofilm formation on stainless steel coupons. Thick biofilms of B. cereus developed at the air-liquid interface, while the amount of biofilm formed was much lower in submerged systems. This suggests that B. cereus biofilms may develop particularly in industrial storage and piping systems that are partly filled during operation or where residual liquid has remained after a production cycle. Moreover, depending on the strain and culture conditions, spores constituted up to 90% of the total biofilm counts. This indicates that B. cereus biofilms can act as a nidus for spore formation and subsequently can release their spores into food production environments. PMID:17209076

  9. 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

  10. GEC Student Award for Excellence Finalist: Creation of Stable Plasma-Liquid Interfaced Reactive Field using Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Baba, Kazuhiko; Kaneko, Toshiro; Hatakeyama, Rikizo

    2008-10-01

    The gas-liquid interfacial region which is the boundary between plasmas and liquids, activating physical and chemical reactions, has attracted much attention as novel reactive field in nano-bio material creation. Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we succeeded in creating the reactive gas (plasmas)-liquid (ionic liquids) interfacial field under a low gas pressure condition, where the plasma ion behavior can be controlled. The effects of plasma ion irradiation on the liquid medium are for the first time quantitatively revealed. In connection with the plasma ion irradiation, the potential structure and optical emission properties of the gas-liquid interfacial plasma are investigated by changing a polarity of the ionic liquid electrode in order to evaluate the ionic liquid-plasma interactions. These results would contribute to systematizing the field of gas-liquid interfacial plasma physics for its applications.

  11. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    SciTech Connect

    Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad; Baiker, Alfons

    2014-08-15

    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.

  12. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

  13. 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.

  14. 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.

  15. INTERFACE OF A REVERSE-PHASE HIGH-PERFORMANCE LIQUID CHROMATOGRAPH WITH A DIFFUSE REFLECTANCE FOURIER TRANSFORM INFRARED SPECTROMETER

    EPA Science Inventory

    An approach to the interface of a reverse-phase high-performance liquid chromatograph and a Fourier transform infrared spectrometer has been developed in which the solutes eluting from the column are continuously extracted into dichloromethane. The application of both flow cell a...

  16. Time-resolved analytical methods for liquid/solid interfaces. Progress report, March 1, 1993--November 15, 1993

    SciTech Connect

    Harris, J.M.

    1993-11-15

    Chemical phenomena occurring at boundaries between insulating solids and liquids (adsorption, partition, monolayer self-assembly, catalysis, and chemical reactions) are important to energy-related analytical chemistry. These phenomena are central to chromatography, solid-phase extraction, immobilized analytical reagents, and optical sensors. Chemical interactions in these processes cannot generally be identified solely by equilibrium surface concentrations, since the steady-state behavior does not reveal the mechanism or rates of surface reactions. Goal therefore is to develop surface-sensitive spectroscopies by which chemical kinetics at liquid/solid interfaces can be observed on time-scales from nanoseconds to seconds. In the first year, we have used Joule-discharge heating kinetics to study pore structure of silica gels; effects of pore diameter, particle size, and chemical modification on pore connectivity were investigated. Temperature-jump relaxation measurements of sorption/desorption kinetics at liquid/solid interfaces were also carried out using Joule heating; kinetic barriers to sorption of ions from solution were found for both C18 and Cl surfaces. Through a collaboration with Fritz-Haber Institute in Berlin, we were able to acquire laser temperature-jump data on kinetics at liquid/solid interfaces using a colloidal sample. We also quantified the rate of migration of covalently attached ligands on silica surfaces; from the temperature dependence, the large energy barrier to migration was estimated. A review of applications of electronic spectroscopy (absorption and fluorescence) to reversed-phase chromatographic interfaces was published.

  17. 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. PMID:27290651

  18. Diffuse scattering from the liquid-vapor interfaces of dilute Bi:Ga, Tl:Ga, and Pb:Ga alloys

    SciTech Connect

    Li, Dongxu; Jiang, Xu; Lin, Binhua; Meron, Mati; Rice, Stuart A.

    2010-07-19

    As part of a study of the in-plane wave-vector (q{sub xy}) dependence of the effective Hamiltonian for the liquid-vapor interface, H(q), the wave-vector dependences of diffuse x-ray scattering from the liquid-vapor interfaces of dilute alloys of Bi in Ga, Tl in Ga, and Pb in Ga have been measured. In these dilute alloys the solute component segregates as a monolayer that forms the outermost stratum of the liquid-vapor interfaces, and the density distribution along the normal to the interface is stratified. Over the temperature ranges that the alloy interfaces were studied, the Tl and Pb monolayers exhibit both crystalline and liquid phases while the Bi monolayer is always liquid. The diffuse scattering from the liquid-vapor interfaces of these alloys displays interesting differences with that from the liquid-vapor interface of pure Ga. The presence of a segregated monolayer of solute in the liquid-vapor interface of the alloy appears to slightly suppress the fluctuations in an intermediate wave-vector range in a fashion that preserves the validity of the macroscopic capillary wave model to smaller wavelengths than in pure liquid Ga, and there is an increase in diffuse scattering when the Tl and Pb monolayers melt. The surface intrinsic roughness from fitting the wave-vector dependence of surface tension is 5.0 pm for the Tl:Ga alloy and 1.4 pm for the Bi:Ga alloy. Also, a mode of excitation that contributes to diffuse scattering from the liquid-vapor interface of Pb in Ga, but does not contribute to diffuse scattering from the liquid-vapor interface of Ga, has been identified. It is proposed that this mode corresponds to the separation of the Pb and Ga layers in the regime 1 nm{sup -1} {le} q{sub xy} {le} 10 nm{sup -1}.

  19. 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.

  20. Interface between platinum(111) and liquid isopropanol (2-propanol): A model for molecular dynamics studies

    NASA Astrophysics Data System (ADS)

    Tarmyshov, Konstantin B.; Müller-Plathe, Florian

    2007-02-01

    A molecular dynamics model and its parametrization procedure are devised and used to study adsorption of isopropanol on platinum(111) (Pt(111)) surface in unsaturated and oversaturated coverages regimes. Static and dynamic properties of the interface between Pt(111) and liquid isopropanol are also investigated. The magnitude of the adsorption energy at unsaturated level increases at higher coverages. At the oversaturated coverage (multilayer adsorption) the adsorption energy reduces, which coincides with findings by Panja et al. in their temperature-programed desorption experiment [Surf. Sci. 395, 248 (1998)]. The density analysis showed a strong packing of molecules at the interface followed by a depletion layer and then by an oscillating density profile up to 3nm. The distribution of individual atom types showed that the first adsorbed layer forms a hydrophobic methyl "brush." This brush then determines the distributions further from the surface. In the second layer methyl and methine groups are closer to the surface and followed by the hydroxyl groups; the third layer has exactly the inverted distribution. The alternating pattern extends up to about 2nm from the surface. The orientational structure of molecules as a function of distance of molecules is determined by the atom distribution and surprisingly does not depend on the electrostatic or chemical interactions of isopropanol with the metal surface. However, possible formation of hydrogen bonds in the first layer is notably influenced by these interactions. The surface-adsorbate interactions influence the mobility of isopropanol molecules only in the first layer. Mobility in the higher layers is independent of these interactions.

  1. Barrier function of human keratinocyte cultures grown at the air-liquid interface.

    PubMed

    Mak, V H; Cumpstone, M B; Kennedy, A H; Harmon, C S; Guy, R H; Potts, R O

    1991-03-01

    Stratum corneum (SC), the outermost and least permeable layer of skin, is the major barrier to passive transepidermal water loss. In the research described in this paper, we have used human keratinocyte cultures, grown at the air-liquid (A/L) interface, to examine the relationship between epidermal differentiation (including SC formation) and barrier function. Histologically, the A/L culture showed several markers of complete differentiation, including the presence of well-organized and defined epidermal cell layers, keratohyalin granules, and a multilayered SC. The permeability of tritiated water through epidermal cultures, which had grown for 3 weeks at the A/L interface, was measured with a microdiffusion apparatus. The results of these experiments demonstrated that: a) the human keratinocyte cultures developed a substantial barrier (i.e., a multilayered SC) to water diffusion across the entire surface. If the relative humidity of the culturing environment was lowered from 100% to around 75%, the barrier was significantly improved; b) the differentiation promoter, 1.25-dihydroxy-vitamin-D3, increased the number of SC layers and reduced water permeation through the culture; c) the nature of the keratinocyte support matrix could be altered to improve the morphology as well as the barrier function of the epidermal cultures. Overall, the observations are consistent with the relationship that is believed to exist between SC intercellular lipid content and percutaneous penetration. Confirmation of this hypothesis will further the considerable potential of human keratinocyte A/L cultures as a valuable and relevant model in which to study drug absorption and metabolism. PMID:2002253

  2. 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

  3. Wetting of liquid-crystal surfaces and induced smectic layering at a nematic-liquid interface: an x-ray reflectivity study.

    PubMed

    Fukuto, Masafumi; Gang, Oleg; Alvine, Kyle J; Ocko, Benjamin M; Pershan, Peter S

    2008-03-01

    We report the results of a synchrotron x-ray reflectivity study of bulk liquid-crystal surfaces that are coated by thin wetting films of an immiscible liquid. The liquid-crystal subphase consisted of the nematic or isotropic phase of 4-octyl- 4;{'} -cyanobiphenyl (8CB), and the wetting film was formed by the fluorocarbon perfluoromethylcyclohexane (PFMC), a volatile liquid. The thickness of the wetting film was controlled by the temperature difference DeltaT(micro) between the sample and a reservoir of bulk PFMC, contained within the sealed sample cell. Phase information on the interfacial electron density profiles has been extracted from the interference between the scattering from the PFMC-vapor interface and the surface-induced smectic order of the 8CB subphase. The liquid-crystal side of the nematic-liquid (8CB-PFMC) interface is characterized by a density oscillation whose period corresponds to the smectic layer spacing and whose amplitude decays exponentially toward the underlying nematic subphase. The decay length xi of the smectic amplitude is independent of the PFMC film thickness but increases as the nematic-smectic- A transition temperature T(NA) is approached, in agreement with the longitudinal correlation length xi(parallel) proportional, variant(T-T(NA))(-0.7} for the smectic fluctuations in the bulk nematic. The results indicate that the homeotropic orientation of the 8CB molecules is preferred at the 8CB-PFMC interface and that the observed temperature dependence of the smectic layer growth is consistent with the critical adsorption mechanism. The observed DeltaT(micro) dependence of the PFMC film thickness, L proportional, variant(DeltaT(micro))(-1/3) , implies that PFMC completely wets the 8CB surface and is dominated by the nonretarded dispersion interactions between hydro- and fluorocarbons. The complete wetting behavior of PFMC is nearly independent of the degree of interfacial smectic order in the subphase. PMID:18517395

  4. 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

  5. Cigarette smoke alters primary human bronchial epithelial cell differentiation at the air-liquid interface

    PubMed Central

    Schamberger, Andrea C.; Staab-Weijnitz, Claudia A.; Mise-Racek, Nikica; Eickelberg, Oliver

    2015-01-01

    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. PMID:25641363

  6. 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

  7. 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.

  8. Band offsets across solid-liquid interfaces from continuum solvation methods

    NASA Astrophysics Data System (ADS)

    Sundararaman, Ravishankar; Ping, Yuan; Galli, Giulia A.; Goddard, William A., III

    2015-03-01

    The band edge positions of photo-electrodes relative to water redox potentials play an important role in determining the efficiency of the photo-electrochemical cell. Direct theoretical calculations of solid-liquid interfaces are expensive and simplified models are desirable for rapid theoretical screening of new materials. However, traditional solvation models are extensively fit to describe organic solutes and hence extrapolate poorly to highly-polar inorganic surfaces. We develop minimally-empirical continuum solvation models suitable for treating such surfaces and present theoretical predictions of the band positions of rutile TiO2 (110) and WO3 (001) surfaces in water. We obtain non-negligible solvation effects ~ 1-2 eV, in good agreement with experimental results. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993.

  9. Single-Step Fabrication of Computationally Designed Microneedles by Continuous Liquid Interface Production.

    PubMed

    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

  10. 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. PMID:25360550

  11. 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. PMID:26050969

  12. 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. PMID:25246101

  13. A vacuum assisted dynamic evaporation interface for two-dimensional normal phase/reverse phase liquid chromatography.

    PubMed

    Ding, Kun; Xu, Yuan; Wang, Hua; Duan, Chunfeng; Guan, Yafeng

    2010-08-20

    A vacuum assisted dynamic solvent evaporation interface for coupling of two-dimensional normal phase/reverse phase liquid chromatography was developed and evaluated. A normal-phase liquid chromatographic (NPLC) column of a 250mmx4.6mm I.D. 5microm CN phase was used as the first dimension, and a reversed-phase liquid chromatographic (RPLC) column of 250mmx4.6mm I.D. 5micromC(18) phase was used as the second dimension. The eluent from the first dimension flowed into a fraction loop, and the solvent in the eluent was dynamically evaporated and removed by vacuum as it was entering the fraction loop of the interface. The non-evaporable analytes was retained and enriched in about 5-25microL solution within the loop. Up to 1mL/min of mobile phase from the first dimension can be evaporated and removed dynamically by the interface. The mobile phase from the second dimension then entered the loop, and dissolved the concentrated analytes retained inside the loop, and carried them onto the second dimension column for further separation. The operation conditions of the two dimensions were independent from each other, and both dimensions were operated at their optimal chromatographic conditions. We evaluated the interface by controlling the loop temperature in a water bath at normal temperature, and investigated the sample losses by using standard samples with different boiling points. It was found that the sample loss due to evaporation in the interface was negligible for non-volatile samples or for components with boiling point above 340 degrees C. The interface realizes fast solvent removal of mL volume of fraction and concentration of the fraction into tenth of microL volume, and injection of the concentrated fraction on the secondary column. The chromatographic performance of the two-dimensional LC system was enhanced without compromise of separation efficiency and selectivity on each dimension. PMID:20630530

  14. In-Situ Observations of Interaction Between Particulate Agglomerates and an Advancing Planar Solid/Liquid Interface: Microgravity Experiments

    NASA Technical Reports Server (NTRS)

    Sen, S.; Juretzko, F.; Stefanescu, D. M.; Dhindaw, B. K.; Curreri, P. A.

    1999-01-01

    Results are reported of directional solidification experiments on particulate agglomerate pushing and engulfment by a planar solid/liquid (s/1) interface. These experiments were conducted on the Space Shuttle Columbia during the United States Microgravity Payload 4 (USMP-4) Mission. It was found that the pushing to engulfment transition velocity, V(sub ct),, for agglomerates depends not only on their effective size but also their orientation with respect to the s/l interface. The analytical model for predicting V(sub cr) of a single particle was subsequently enhanced to predict V(sub cr) of the agglomerates by considering their shape factor and orientation.

  15. In Situ Observations of Interaction Between Particulate Agglomerates and an Advancing Planar Solid/Liquid Interface: Microgravity Experiments

    NASA Technical Reports Server (NTRS)

    Sen, S.; Juretzko, F.; Stafanescu, D. M.; Dhindaw, B. K.; Curreri, P. A.

    1999-01-01

    Results are reported of directional solidification experiments on particulate agglomerate pushing and engulfment by a planar solid/liquid (s/l) interface. These experiments were conducted on the Space Shuttle Columbia during the United States Microgravity Payload 4 (USMP-4) Mission. It was found that the pushing to engulfment transition velocity, V(sub cr) for agglomerates depends not only on their effective size but also their orientation with respect to the s,1 interface. The analytical model for predicting V(sub cr) of a single particle was subsequently enhanced to predict V(sub cr) of the agglomerates by considering their shape factor and orientation.

  16. Real-time single-molecule observations of proteins at the solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Langdon, Blake Brianna

    Non-specific protein adsorption to solid surfaces is pervasive and observed across a broad spectrum of applications including biomaterials, separations, pharmaceuticals, and biosensing. Despite great interest in and considerable literature dedicated to the phenomena, a mechanistic understanding of this complex phenomena is lacking and remains controversial, partially due to the limits of ensemble-averaging techniques used to study it. Single-molecule tracking (SMT) methods allow us to study distinct protein dynamics (e.g. adsorption, desorption, diffusion, and intermolecular associations) on a molecule-by-molecule basis revealing the protein population and spatial heterogeneity inherent in protein interfacial behavior. By employing single-molecule total internal reflection fluorescence microscopy (SM-TIRFM), we have developed SMT methods to directly observe protein interfacial dynamics at the solid-liquid interface to build a better mechanistic understanding of protein adsorption. First, we examined the effects of surface chemistry (e.g. hydrophobicity, hydrogen-bonding capacity), temperature, and electrostatics on isolated protein desorption and interfacial diffusion for fibrinogen (Fg) and bovine serum albumin (BSA). Next, we directly and indirectly probed the effects of protein-protein interactions on interfacial desorption, diffusion, aggregation, and surface spatial heterogeneity on model and polymeric thin films. These studies provided many useful insights into interfacial protein dynamics including the following observations. First, protein adsorption was reversible, with the majority of proteins desorbing from all surface chemistries within seconds. Isolated protein-surface interactions were relatively weak on both hydrophobic and hydrophilic surfaces (apparent desorption activation energies of only a few kBT). However, proteins could dynamically and reversibly associate at the interface, and these interfacial associations led to proteins remaining on the

  17. Three-Dimensional Structure of a Simple Liquid at a Face-Centered-Cubic (001) Solid Surface Interface

    PubMed Central

    Bao, Luyao; Hu, Haibao; Wen, Jun; Sepri, Paavo; Luo, Kai

    2016-01-01

    A liquid in the vicinity of a solid-liquid interface (SLI) may exhibit complex structures. In this study, we used molecular dynamics simulations demonstrating for the first time that the liquid adjacent to the SLI can have a two-level structure in some cases: a major structure and a minor structure. Through a time-averaging process of molecular motions, we identified the type of the liquid structure by calculating positions of the maximum liquid density in three spatial dimensions, and these positions were found to distribute in many dispersed zones (called high-density zones (HDZs)). The major structure appears throughout the SLI, while the minor structure only occurs significantly within the third layer. Instead of the previously reported body-centered cubic (BCC) or face-centered-cubic (FCC) types, the major structure was found to show a body-centered tetragonal (BCT) type. The adjacent HDZs are connected by specific junctions, demonstrating that atoms diffuse along some particular high probability paths from one HDZ to another. By considering the three-dimensional liquid density distribution from the continuum point of view, more complete details of the structure and diffusive behavior of liquids in the SLI are also possible to be revealed. PMID:27430188

  18. Three-Dimensional Structure of a Simple Liquid at a Face-Centered-Cubic (001) Solid Surface Interface

    NASA Astrophysics Data System (ADS)

    Bao, Luyao; Hu, Haibao; Wen, Jun; Sepri, Paavo; Luo, Kai

    2016-07-01

    A liquid in the vicinity of a solid-liquid interface (SLI) may exhibit complex structures. In this study, we used molecular dynamics simulations demonstrating for the first time that the liquid adjacent to the SLI can have a two-level structure in some cases: a major structure and a minor structure. Through a time-averaging process of molecular motions, we identified the type of the liquid structure by calculating positions of the maximum liquid density in three spatial dimensions, and these positions were found to distribute in many dispersed zones (called high-density zones (HDZs)). The major structure appears throughout the SLI, while the minor structure only occurs significantly within the third layer. Instead of the previously reported body-centered cubic (BCC) or face-centered-cubic (FCC) types, the major structure was found to show a body-centered tetragonal (BCT) type. The adjacent HDZs are connected by specific junctions, demonstrating that atoms diffuse along some particular high probability paths from one HDZ to another. By considering the three-dimensional liquid density distribution from the continuum point of view, more complete details of the structure and diffusive behavior of liquids in the SLI are also possible to be revealed.

  19. Isotope-Ratio-Monitoring Liquid Chromatography Mass Spectrometry (IRM-LCMS): First Results from a Moving Wire Interface System.

    PubMed

    Brand, W A; Dobberstein, P

    1996-08-01

    Abstract A Liquid Chromatography-Combustion (LC-C) Interface, based on a moving wire technique, has been built and tested. The LC effluent is deposited onto a transport wire, which carries the sample through solvent evaporation and combustion ovens. CO(2) from the combustion step is analysed in an isotope ratio mass spectrometer. Performance of the interface was tested by loop injections of sucrose and glucose into a liquid flow of methanol/water (80/20). Accuracy and precision of δ(13)C(PDB) < 1‰ was achieved for sample concentrations > 500 ng/ul (5μl loop), sufficient for studies at natural isotope ratios. In case of (13)C tracer applications the detection limit was determined to be about 20 pg carbon tracer (on wire). PMID:22088119

  20. Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

    NASA Technical Reports Server (NTRS)

    Benjamin, Ilan; Pohorille, Andrew

    1993-01-01

    The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

  1. Hot Electrons at Solid-Liquid Interfaces: A Large Chemoelectric Effect during the Catalytic Decomposition of Hydrogen Peroxide.

    PubMed

    Nedrygailov, Ievgen I; Lee, Changhwan; Moon, Song Yi; Lee, Hyosun; Park, Jeong Young

    2016-08-26

    The study of energy and charge transfer during chemical reactions on metals is of great importance for understanding the phenomena involved in heterogeneous catalysis. Despite extensive studies, very little is known about the nature of hot electrons generated at solid-liquid interfaces. Herein, we report remarkable results showing the detection of hot electrons as a chemicurrent generated at the solid-liquid interface during decomposition of hydrogen peroxide (H2 O2 ) catalyzed on Schottky nanodiodes. The chemicurrent reflects the activity of the catalytic reaction and the state of the catalyst in real time. We show that the chemicurrent yield can reach values up to 10(-1) electrons/O2 molecule, which is notably higher than that for solid-gas reactions on similar nanodiodes. PMID:27374493

  2. A study of the solid-liquid interface in cobalt base alloy (Stellite) coatings deposited by fusion welding (TIG)

    SciTech Connect

    Molleda, F. . E-mail: fmolleda@etsin.upm.es; Mora, J.; Molleda, F.J.; Mora, E.; Carrillo, E.; Mellor, B.G.

    2006-12-15

    Microstructural features present at the interface between a weld deposited Stellite 6 hard facing and an austenitic stainless steel substrate are described. Elemental X-ray maps indicate that diffusion of carbon from the liquid Stellite to the austenitic stainless steel takes place along grain boundaries resulting in the formation of chromium carbide 'arms' that penetrate along the austenite grain boundaries in the interfacial region.

  3. Exfoliation at the liquid/air interface to assemble reduced graphene oxide ultrathin films for a flexible noncontact sensing device.

    PubMed

    Wang, Xuewen; Xiong, Zuoping; Liu, Zheng; Zhang, Ting

    2015-02-25

    Reduced graphene oxide ultrathin films are fabricated by a reproducible exfoliation method at the liquid/air interface, and they show high transparency, tunable sheet resistance, uniform electric conductivity, and structural homogeneity over a large area. A flexible relative humidity sensing matrix is demonstrated and it is shown to be excellent for close proximity sensing without touching it. This method opens up a novel avenue for future human-machine interaction applications. PMID:25522328

  4. Experimental studies on irreversibility of electrostatic adsorption of silica nanoparticles at solid-liquid interface.

    PubMed

    Li, Xue; Niitsoo, Olivia; Couzis, Alexander

    2014-04-15

    Adsorption of colloidal nanoparticles (NPs) at solid-liquid interface is a scientifically interesting and technologically important phenomenon due to its fundamental importance in many industrial, environmental, and biological processes, such as wastewater treatment, printing, coating of surfaces, chromatography, papermaking, or biocompatibility. The process is well understood theoretically by the random sequential adsorption (RSA) model, based on the assumption of irreversible adsorption. Irreversible adsorption is defined as a process in which, once adsorbed, a particle can neither desorb, nor to move laterally on the surface. However, published experimental data that verifies the irreversibility of particle adsorption are very limited. In this study, we demonstrate the irreversibility of electrostatically driven nanoparticle adsorption utilizing a carefully selected set of experiments. A simple method was employed by uniquely introducing Ag@SiO2 core/shell NPs to perform exchange adsorptions experiments. Stöber SiO2 NPs with a diameter of 50-80 nm were initially electrostatically adsorbed onto amino-functionalized silicon wafer substrates followed by the subsequent adsorption of Ag@SiO2 NPs. The Ag@SiO2 NPs have the same surface chemistry as the neat SiO2 NPs. For the second step the adsorption time was varied from 1 min to 1 week so as to get a thorough understanding of the process irreversibility. Surface coverage quantification has shown that the surface coverage of the initially adsorbed SiO2 NPs stays the same independent of the duration of the second step adsorption using the Ag@SiO2 core/shell NPs. This observation directly confirms the irreversibility of electrostatic adsorption of NPs. PMID:24559699

  5. Optimization of an air-liquid interface exposure system for assessing toxicity of airborne nanoparticles.

    PubMed

    Latvala, Siiri; Hedberg, Jonas; Möller, Lennart; Odnevall Wallinder, Inger; Karlsson, Hanna L; Elihn, Karine

    2016-10-01

    The use of refined toxicological methods is currently needed for characterizing the risks of airborne nanoparticles (NPs) to human health. To mimic pulmonary exposure, we have developed an air-liquid interface (ALI) exposure system for direct deposition of airborne NPs on to lung cell cultures. Compared to traditional submerged systems, this allows more realistic exposure conditions for characterizing toxicological effects induced by airborne NPs. The purpose of this study was to investigate how the deposition of silver NPs (AgNPs) is affected by different conditions of the ALI system. Additionally, the viability and metabolic activity of A549 cells was studied following AgNP exposure. Particle deposition increased markedly with increasing aerosol flow rate and electrostatic field strength. The highest amount of deposited particles (2.2 μg cm(-2) ) at cell-free conditions following 2 h exposure was observed for the highest flow rate (390 ml min(-1) ) and the strongest electrostatic field (±2 kV). This was estimated corresponding to deposition efficiency of 94%. Cell viability was not affected after 2 h exposure to clean air in the ALI system. Cells exposed to AgNPs (0.45 and 0.74 μg cm(-2) ) showed significantly (P < 0.05) reduced metabolic activities (64 and 46%, respectively). Our study shows that the ALI exposure system can be used for generating conditions that were more realistic for in vitro exposures, which enables improved mechanistic and toxicological studies of NPs in contact with human lung cells.Copyright © 2016 The Authors Journal of Applied Toxicology Published by John Wiley & Sons Ltd. PMID:26935862

  6. A Bottom-Up Approach to Understanding Protein Layer Formation at Solid-Liquid Interfaces

    PubMed Central

    Kastantin, Mark; Langdon, Blake B.; Schwartz, Daniel K.

    2014-01-01

    A common goal across different fields (e.g. separations, biosensors, biomaterials, pharmaceuticals) is to understand how protein behavior at solid-liquid interfaces is affected by environmental conditions. Temperature, pH, ionic strength, and the chemical and physical properties of the solid surface, among many factors, can control microscopic protein dynamics (e.g. adsorption, desorption, diffusion, aggregation) that contribute to macroscopic properties like time-dependent total protein surface coverage and protein structure. These relationships are typically studied through a top-down approach in which macroscopic observations are explained using analytical models that are based upon reasonable, but not universally true, simplifying assumptions about microscopic protein dynamics. Conclusions connecting microscopic dynamics to environmental factors can be heavily biased by potentially incorrect assumptions. In contrast, more complicated models avoid several of the common assumptions but require many parameters that have overlapping effects on predictions of macroscopic, average protein properties. Consequently, these models are poorly suited for the top-down approach. Because the sophistication incorporated into these models may ultimately prove essential to understanding interfacial protein behavior, this article proposes a bottom-up approach in which direct observations of microscopic protein dynamics specify parameters in complicated models, which then generate macroscopic predictions to compare with experiment. In this framework, single-molecule tracking has proven capable of making direct measurements of microscopic protein dynamics, but must be complemented by modeling to combine and extrapolate many independent microscopic observations to the macro-scale. The bottom-up approach is expected to better connect environmental factors to macroscopic protein behavior, thereby guiding rational choices that promote desirable protein behaviors. PMID:24484895

  7. A bottom-up approach to understanding protein layer formation at solid-liquid interfaces.

    PubMed

    Kastantin, Mark; Langdon, Blake B; Schwartz, Daniel K

    2014-05-01

    A common goal across different fields (e.g. separations, biosensors, biomaterials, pharmaceuticals) is to understand how protein behavior at solid-liquid interfaces is affected by environmental conditions. Temperature, pH, ionic strength, and the chemical and physical properties of the solid surface, among many factors, can control microscopic protein dynamics (e.g. adsorption, desorption, diffusion, aggregation) that contribute to macroscopic properties like time-dependent total protein surface coverage and protein structure. These relationships are typically studied through a top-down approach in which macroscopic observations are explained using analytical models that are based upon reasonable, but not universally true, simplifying assumptions about microscopic protein dynamics. Conclusions connecting microscopic dynamics to environmental factors can be heavily biased by potentially incorrect assumptions. In contrast, more complicated models avoid several of the common assumptions but require many parameters that have overlapping effects on predictions of macroscopic, average protein properties. Consequently, these models are poorly suited for the top-down approach. Because the sophistication incorporated into these models may ultimately prove essential to understanding interfacial protein behavior, this article proposes a bottom-up approach in which direct observations of microscopic protein dynamics specify parameters in complicated models, which then generate macroscopic predictions to compare with experiment. In this framework, single-molecule tracking has proven capable of making direct measurements of microscopic protein dynamics, but must be complemented by modeling to combine and extrapolate many independent microscopic observations to the macro-scale. The bottom-up approach is expected to better connect environmental factors to macroscopic protein behavior, thereby guiding rational choices that promote desirable protein behaviors. PMID:24484895

  8. Coupling compositional liquid gas Darcy and free gas flows at porous and free-flow domains interface

    NASA Astrophysics Data System (ADS)

    Masson, R.; Trenty, L.; Zhang, Y.

    2016-09-01

    This paper proposes an efficient splitting algorithm to solve coupled liquid gas Darcy and free gas flows at the interface between a porous medium and a free-flow domain. This model is compared to the reduced model introduced in [6] using a 1D approximation of the gas free flow. For that purpose, the gas molar fraction diffusive flux at the interface in the free-flow domain is approximated by a two point flux approximation based on a low-frequency diagonal approximation of a Steklov-Poincaré type operator. The splitting algorithm and the reduced model are applied in particular to the modelling of the mass exchanges at the interface between the storage and the ventilation galleries in radioactive waste deposits.

  9. Magnetic cylindrical colloids at liquid interfaces exhibit non-volatile switching of their orientation in an external field.

    PubMed

    Newton, Bethany J; Buzza, D Martin A

    2016-06-28

    We study the orientation of magnetic cylindrical particles adsorbed at a liquid interface in an external field using analytical theory and high resolution finite element simulations. Cylindrical particles are interesting since they possess multiple locally stable orientations at the liquid interface so that the orientational transitions induced by an external field will not disappear when the external field is removed, i.e., the switching effect is non-volatile. We show that, in the absence of an external field, as we reduce the aspect ratio α of the cylinders below a critical value (αc≈ 2) the particles undergo spontaneous symmetry breaking from a stable side-on state to one of two equivalent stable tilted states, similar to the spontaneous magnetisation of a ferromagnet going through the Curie point. By tuning both the aspect ratio and contact angle of the cylinders, we show that it is possible to engineer particles that have one, two, three or four locally stable orientations. We also find that the magnetic responses of cylinders with one or two stable states are similar to that of paramagnets and ferromagnets respectively, while the magnetic response of systems with three or four stable states are even more complex and have no analogs in simple magnetic systems. Magnetic cylinders at liquid interfaces therefore provide a facile method for creating switchable functional monolayers where we can use an external field to induce multiple non-volatile changes in particle orientation and self-assembled structure. PMID:27200513

  10. Semiconductor nanorod self-assembly at the liquid/air interface studied by in situ GISAXS and ex situ TEM.

    PubMed

    Pietra, Francesca; Rabouw, Freddy T; Evers, Wiel H; Byelov, Dima V; Petukhov, Andrei V; de Mello Donegá, Celso; Vanmaekelbergh, Daniël

    2012-11-14

    We study the self-assembly of colloidal CdSe/CdS nanorods (NRs) at the liquid/air interface combining time-resolved in situ grazing-incidence small angle X-ray scattering (GISAXS) and ex situ transmission electron microscopy (TEM). Our study shows that NR superstructure formation occurs at the liquid/air interface. Short NRs self-assemble into micrometers long tracks of NRs lying side by side flat on the surface. In contrast, longer NRs align vertically into ordered superstructures. Systematic variation of the NR length and initial concentration of the NR dispersion allowed us to tune the orientation of the NRs in the final superstructure. With GISAXS, we were able to follow the dynamics of the self-assembly. We propose a model of hierarchical self-organization that provides a basis for the understanding of the length-dependent self-organization of NRs at the liquid/air interface. This opens the way to new materials based on NR membranes and anisotropic thin films. PMID:23038984

  11. Janus Solid-Liquid Interface Enabling Ultrahigh Charging and Discharging Rate for Advanced Lithium-Ion Batteries.

    PubMed

    Zheng, Jiaxin; Hou, Yuyang; Duan, Yandong; Song, Xiaohe; Wei, Yi; Liu, Tongchao; Hu, Jiangtao; Guo, Hua; Zhuo, Zengqing; Liu, Lili; Chang, Zheng; Wang, Xiaowei; Zherebetskyy, Danylo; Fang, Yanyan; Lin, Yuan; Xu, Kang; Wang, Lin-Wang; Wu, Yuping; Pan, Feng

    2015-09-01

    LiFePO4 has long been held as one of the most promising battery cathode for its high energy storage capacity. Meanwhile, although extensive studies have been conducted on the interfacial chemistries in Li-ion batteries,1-3 little is known on the atomic level about the solid-liquid interface of LiFePO4/electrolyte. Here, we report battery cathode consisted with nanosized LiFePO4 particles in aqueous electrolyte with an high charging and discharging rate of 600 C (3600/600 = 6 s charge time, 1 C = 170 mAh g(-1)) reaching 72 mAh g(-1) energy storage (42% of the theoretical capacity). By contrast, the accessible capacity sharply decreases to 20 mAh g(-1) at 200 C in organic electrolyte. After a comprehensive electrochemistry tests and ab initio calculations of the LiFePO4-H2O and LiFePO4-EC (ethylene carbonate) systems, we identified the transient formation of a Janus hydrated interface in the LiFePO4-H2O system, where the truncated symmetry of solid LiFePO4 surface is compensated by the chemisorbed H2O molecules, forming a half-solid (LiFePO4) and half-liquid (H2O) amphiphilic coordination environment that eases the Li desolvation process near the surface, which makes a fast Li-ion transport across the solid/liquid interfaces possible. PMID:26305572

  12. Interaction mechanism of in-situ nano-TiN-AlN particles and solid/liquid interface during solidification.

    PubMed

    Cui, Chunxiang; Li, Yanchun; Shen, Yutian; Sun, Jibing; Wang, Ru

    2003-10-01

    This paper deals with the interaction mechanism between in situ nanometer-grade TiN-AlN particles and the solid/liquid (S/L) interface during the solidification of an in situ TiN-AlN/Al composite. According to the setting of a force balance for the particles in front of the S/L interface during solidification, F = F(buoyant) + F(repulsive) + F(viscous). We obtained the relationship between the critical cooling velocity of the liquid composite, Vr, and the size of the ceramic particle, rp. By this relationship formula, we can know that the S/L interface engulfs particles or pushes them to the crystal grain boundary during the solidification of a TiN-AlN/Al composite. It is found that Vr is proportional to the radius of ceramic particles by transmission electron microscope (TEM) observation. The TEM test indicates that the smaller the particle is, the more easily the S/L interface engulfs particles. PMID:14733152

  13. Davisson-Germer Prize in Atomic or Surface Physics Lecture: Line 'Em All Up: Macromolecular Assembly at Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Richmond, Geraldine

    2013-03-01

    Advances in our molecular level understanding of the ubiquitous fluid interface comprised of a hydrophobic fluid medium, and an aqueous solution of soluble ions and solutes has been slow until recently. This more recent upsurge in interest and progress comes from advances in both experimental and computational techniques as well as the increasingly important role that this interface is playing in such areas as green chemistry, nanoparticle synthesis, improved oil and mineral recovery and water purification. The presentation will focus on our most recent efforts in understanding (1) the molecular structure of the interface between two immiscible liquids, (2) the penetration of aqueous phase ions into the interfacial region and their effect on its properties, and (3) the structure and dynamics of the adsorption of surfactants, polymers and nanoparticles at this interface. To gain insights into these processes we use a combination of vibrational sum frequency spectroscopy, surface tension measurements using the pendant drop method, and molecular dynamics simulations. The results demonstrate that weak interactions between interfacial oil and water molecules create an interface that exhibits a high degree of molecular structuring and ordering, and with properties quite different than what is observed at the air-water interface. As a consequence of these interfacial oil-water interactions, the interface provides a unique environment for the adsorption and assembly of ions, polymers and nanoparticles that are drawn to its inner-most regions. Examples of our studies that provide new insights into the unique nature of adsorption, adsorption dynamics and macromolecular assembly at this interface will be provided.

  14. Sum frequency generation spectroscopy of imidazolium-based ionic liquids with cyano-functionalized anions at the solid salt-liquid interface.

    PubMed

    Peñalber, Chariz Y; Baker, Gary A; Baldelli, Steven

    2013-05-16

    A surface-sensitive nonlinear vibrational spectroscopic technique, sum frequency generation (SFG), has been used to study cyano-containing ionic liquids in contact with two different solid salt surfaces. Specifically, the interfacial chemistry of BaF2(111) single-crystal and solid NaCl{100} surfaces in contact with ionic liquids such as [BMIM][SCN], [BMIM][DCA], [BMIM][TCM], and [EMIM][TCB] has been investigated. Spectral features in both C-H and C-N stretching regions were assigned, with a detailed discussion of the nature of surface interactions and ordering of the ionic liquid ions at the interface of the different crystals. Results showed that [BMIM](+) cations adhered closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [SCN](-), [TCM](-), and [DCA](-) anions revealed a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorbed to the solid salt surface to form a Helmholtz-like electric double layer. The linear [SCN](-) anion has a particularly strong affinity to the BaF2(111) surface, resulting in a first layer of anions directly in contact with BaF2(111) containing an effective negative surface excess charge. This promoted ordering of the cations in the second layer to counter the charge excess. At the BaF2(111)-[EMIM][TCB] interface, however, a strongly bound layer of anions populating the first layer resulted in a much larger counterion charge delivered near the crystal salt surface than required to effectively neutralize the initial surface charge from the crystal. As a result, strong resonances from the cation were observed at the BaF2(111) surface, suggesting a more complicated structure of the double layer at the interface than a simple Helmholtz-type model. PMID:23650965

  15. Anomalous effect of flow rate on the electrochemical behavior at a liquid|liquid interface under microfluidic conditions.

    PubMed

    Kaluza, Dawid; Adamiak, Wojciech; Kalwarczyk, Tomasz; Sozanski, Krzysztof; Opallo, Marcin; Jönsson-Niedziolka, Martin

    2013-12-23

    We have investigated the oxidation of ferrocene at a flowing organic solvent|aqueous electrolyte|solid electrode junction in a microfluidic setup using cyclic voltammetry and fluorescent laser scanning confocal microscopy. At low flow rates the oxidation current decreases with increasing flow, contrary to the Levich equation, but at higher flow rates the current increases linearly with the cube root of the flow rate. This behavior is explained using a simple model postulating a smallest effective width of the three-phase junction, which after fitting to the data comes to be ca. 20 μm. The fluorescence microscopy reveals mixing of the two phases close to the PDMS cover, but the liquid|liquid junction is stable close to the glass support. This study shows the importance of the solid|liquid|liquid junctions for the behavior of multiphase systems under microfluidic conditions. PMID:24328179

  16. IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

    SciTech Connect

    Ni, Yicun; Skinner, J. L.

    2015-07-07

    Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm{sup −1} and a positive band centered at 1670 cm{sup −1}. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

  17. IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively.

    PubMed

    Ni, Yicun; Skinner, J L

    2015-07-01

    Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm(-1) and a positive band centered at 1670 cm(-1). We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface. PMID:26156483

  18. Increased Transfer of a Multidrug Resistance Plasmid in Escherichia coli Biofilms at the Air-Liquid Interface

    PubMed Central

    Król, Jaroslaw E.; Nguyen, Hung Duc; Rogers, Linda M.; Beyenal, Haluk; Krone, Stephen M.; Top, Eva M.

    2011-01-01

    Although biofilms represent a common bacterial lifestyle in clinically and environmentally important habitats, there is scant information on the extent of gene transfer in these spatially structured populations. The objective of this study was to gain insight into factors that affect transfer of the promiscuous multidrug resistance plasmid pB10 in Escherichia coli biofilms. Biofilms were grown in different experimental settings, and plasmid transfer was monitored using laser scanning confocal microscopy and plate counting. In closed flow cells, plasmid transfer in surface-attached submerged biofilms was negligible. In contrast, a high plasmid transfer efficiency was observed in a biofilm floating at the air-liquid interface in an open flow cell with low flow rates. A vertical flow cell and a batch culture biofilm reactor were then used to detect plasmid transfer at different depths away from the air-liquid interface. Extensive plasmid transfer occurred only in a narrow zone near that interface. The much lower transfer frequencies in the lower zones coincided with rapidly decreasing oxygen concentrations. However, when an E. coli csrA mutant was used as the recipient, a thick biofilm was obtained at all depths, and plasmid transfer occurred at similar frequencies throughout. These results and data from separate aerobic and anaerobic matings suggest that oxygen can affect IncP-1 plasmid transfer efficiency, not only directly but also indirectly, through influencing population densities and therefore colocalization of donors and recipients. In conclusion, the air-liquid interface can be a hot spot for plasmid-mediated gene transfer due to high densities of juxtaposed donor and recipient cells. PMID:21642400

  19. Photoinduced Directional Motions of Microparticles at Air-Liquid-Crystal Interfaces of Azobenzene-Doped Liquid-Crystal Films with Homeotropic or Homogeneous Alignment Structures

    NASA Astrophysics Data System (ADS)

    Yamamoto, Takahiro; Yoshida, Masaru

    2012-10-01

    We investigated the effects of liquid-crystal (LC) alignments on photoinduced motions of microparticles at air-LC interfaces of azobenzene-doped LC films. In homeotropically aligned LC films, the lattice spacings of pseudo-hexagonal structures of microparticles site-selectively exhibited reversible expansion or contraction on alternating irradiation with ultraviolet and visible light. The particle motions were probably driven by photochemical deformation of LC surfaces. In homogeneously aligned films, alternating irradiation induced macroscopic convective flows followed by rapid gathering or dispersion of linear chains of microparticles. Particle motions were significantly influenced by LC alignments as well as the light wavelength.

  20. Configurational temperature and local properties of the anisotropic Gay-Berne liquid crystal model: Applications to the isotropic liquid/vapor interface and isotropic/nematic transition

    NASA Astrophysics Data System (ADS)

    Ghoufi, Aziz; Morineau, Denis; Lefort, Ronan; Malfreyt, Patrice

    2011-01-01

    Molecular simulations in the isothermal statistical ensembles require that the macroscopic thermal and mechanical equilibriums are respected and that the local values of these properties are constant at every point in the system. The thermal equilibrium in Monte Carlo simulations can be checked through the calculation of the configurational temperature, {k_BT_{conf}={< |nabla _r U({r}^N)|2>}/{< nabla _r{^2} U({r}^N) >}}, where nabla _r is the nabla operator of position vector r. As far as we know, T_{conf} was never calculated with the anisotropic Gay-Berne potential, whereas the calculation of T_{conf} is much more widespread with more common potentials (Lennard Jones, electrostatic, …). We establish here an operational expression of the macroscopic and local configurational temperatures, and we investigate locally the isotropic liquid phase, the liquid / vapor interface, and the isotropic-nematic transition by Monte Carlo simulations.

  1. Thin and transparent films of graphene/silver nanoparticles obtained at liquid-liquid interfaces: preparation, characterization and application as SERS substrates.

    PubMed

    Mehl, Hiany; Oliveira, Marcela Mohallem; Zarbin, Aldo José Gorgatti

    2015-01-15

    We report here the synthesis and characterization of transparent and homogeneous thin films of reduced graphene oxide/silver nanoparticles (rGO/AgNPs) nanocomposites, starting from graphene oxide (GO) or reduced graphene oxide (rGO), directly obtained at a water/toluene liquid-liquid interface. Different films (obtained by varying the Ag/rGO or Ag/GO ratio) were prepared, deposited over glass or plastic substrates, and characterized by X-ray diffraction, UV-Vis and Raman spectroscopy, thermal analysis, transmission and scanning electron microscopy. Samples were evaluated as substrates for surface-enhanced Raman spectroscopy (SERS), using dilute solutions (1×10(-7) mol L(-1)) of a common probe molecule, 4-aminothiophenol (4-ATP). These materials exhibit significant high-quality SERS activity, and enhanced modes could be observed for 4-ATP, which suggested that charge transfer occurred between the Ag nanoparticles and 4-ATP molecules. PMID:25454422

  2. Influence of high voltage electric fields applied across a horizontal liquid-liquid interface on the rate of metal extraction using a rotating diffusion cell

    SciTech Connect

    Kuipa, P.K.; Hughes, M.A.

    1999-09-01

    The effect of an applied electrical field across a plane liquid-liquid interface on the rate of metal extraction using hydroxyoximes and dialkylphosphoric acids as extractants is examined. The results indicate that applied electric fields have no marked influence on the observed rate of metal extraction when aliphatic hydrocarbons are employed as the diluents in the organic phase. Increases in mass transfer rates of up to 250% were observed when mixtures of octanol and an aliphatic hydrocarbon were employed as the diluent in the organic phase. The mechanism of transfer is thought to be a combination of movement of charges in the bulk of the nonconducting organic phase and electrohydrodynamic flows due to local variations in the effective interfacial tension as a result of the applied electric fields.

  3. Surface tension of liquid Al-Cu and wetting at the Cu/Sapphire solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Schmitz, J.; Brillo, J.; Egry, I.

    2014-02-01

    For the study of the interaction of a liquid alloy with differently oriented single crystalline sapphire surfaces precise surface tension data of the liquid are fundamental. We measured the surface tension of liquid Al-Cu contactlessly on electromagnetically levitated samples using the oscillating drop technique. Data were obtained for samples covering the entire range of composition and in a broad temperature range. The surface tensions can be described as linear functions of temperature with negative slopes. Moreover, they decrease monotonically with an increase of aluminium concentration. The observed behaviour with respect to both temperature and concentration is in agreement with a thermodynamic model calculation using the regular solution approximation. Surface tensions were used to calculate interfacial energies from the contact angles of liquid Cu droplets, deposited on the C(0001), A(11-20), R(1-102) surfaces of an α-Al2O3 substrate. The contact angles were measured by means of the sessile drop method at 1380 K. In the Cu/α-Al2O3 system, no anisotropy is evident neither for the contact angles nor for the interfacial energies of different surfaces. The work of adhesion of this system is isotropic, too.

  4. Predicting In-Situ X-ray Diffraction for the SrTiO3/Liquid Interface from First Principles

    NASA Astrophysics Data System (ADS)

    Letchworth-Weaver, Kendra; Gunceler, Deniz; Sundararaman, Ravishankar; Huang, Xin; Brock, Joel; Arias, T. A.

    2013-03-01

    Recent advances in experimental techniques, such as in-situ x-ray diffraction, allow researchers to probe the solid-liquid interface in electrochemical systems under operating conditions. These advances offer an unprecedented opportunity for theory to predict properties of electrode materials in aqueous environments and inform the design of energy conversion and storage devices. To compare with experiment, these theoretical studies require microscopic details of both the liquid and the electrode surface. Joint Density Functional Theory (JDFT), a computationally efficient alternative to molecular dynamics, couples a classical density-functional, which captures molecular structure of the liquid, to a quantum-mechanical functional for the electrode surface. We present a JDFT exploration of SrTiO3, which can catalyze solar-driven water splitting, in an electrochemical environment. We determine the geometry of the polar SrTiO3 surface and the equilibrium structure of the contacting liquid, as well as the influence of the liquid upon the electronic structure of the surface. We then predict the effect of the fluid environment on x-ray diffraction patterns and compare our predictions to in-situ measurements performed at the Cornell High Energy Synchrotron Source (CHESS). This material is based upon work supported by the Energy Materials Center at Cornell (EMC2), an Energy Frontier Research Center funded by the U.S. Department of Energy.

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

    PubMed Central

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

    2013-01-01

    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 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb2+ from the Hg bulk at , 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 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. PMID:23553838

  6. Anisotropy of the solid–liquid interface properties of the Ni–Zr B33 phase from molecular dynamics simulation

    SciTech Connect

    Wilson, S. R.; Mendelev, M. I.

    2015-01-08

    Solid–liquid interface (SLI) properties of the Ni–Zr B33 phase were determined from molecular dynamics simulations. In order to perform these measurements, a new semi-empirical potential for Ni–Zr alloy was developed that well reproduces the material properties required to model SLIs in the Ni50.0Zr50.0 alloy. In particular, the developed potential is shown to provide that the solid phase emerging from the liquid Ni50.0Zr50.0alloy is B33 (apart from a small fraction of point defects), in agreement with the experimental phase diagram. The SLI properties obtained using the developed potential exhibit an extraordinary degree of anisotropy. It is observed that anisotropies in both the interfacial free energy and mobility are an order of magnitude larger than those measured to date in any other metallic compound. Moreover, the [0 1 0] interface is shown to play a significant role in the observed anisotropy. Our data suggest that the [0 1 0] interface simultaneously corresponds to the lowest mobility, the lowest free energy and the highest stiffness of all inclinations in B33 Ni–Zr. This finding can be understood by taking into account a rather complicated crystal structure in this crystallographic direction.

  7. Anisotropy of the solid–liquid interface properties of the Ni–Zr B33 phase from molecular dynamics simulation

    DOE PAGESBeta

    Wilson, S. R.; Mendelev, M. I.

    2015-01-08

    Solid–liquid interface (SLI) properties of the Ni–Zr B33 phase were determined from molecular dynamics simulations. In order to perform these measurements, a new semi-empirical potential for Ni–Zr alloy was developed that well reproduces the material properties required to model SLIs in the Ni50.0Zr50.0 alloy. In particular, the developed potential is shown to provide that the solid phase emerging from the liquid Ni50.0Zr50.0alloy is B33 (apart from a small fraction of point defects), in agreement with the experimental phase diagram. The SLI properties obtained using the developed potential exhibit an extraordinary degree of anisotropy. It is observed that anisotropies in bothmore » the interfacial free energy and mobility are an order of magnitude larger than those measured to date in any other metallic compound. Moreover, the [0 1 0] interface is shown to play a significant role in the observed anisotropy. Our data suggest that the [0 1 0] interface simultaneously corresponds to the lowest mobility, the lowest free energy and the highest stiffness of all inclinations in B33 Ni–Zr. This finding can be understood by taking into account a rather complicated crystal structure in this crystallographic direction.« less

  8. Accommodative Behavior of Non-porous Molecular crystal at Solid-Gas and Solid-Liquid Interface

    PubMed Central

    Mande, Hemant M.; Ghalsasi, Prasanna S.

    2015-01-01

    Molecular crystals demonstrate drastically different behavior in solid and liquid state, mainly due to their difference in structural frameworks. Therefore, designing of unique structured molecular compound which can work at both these interfaces has been a challenge. Here, we present remarkable ‘molecular’ property by non-porous molecular solid crystal, dinuclear copper complex (C6H5CH(X)NH2)2CuCl2, to reversibly ‘adsorb’ HCl gas at solid-gas interface as well as ‘accommodate’ azide anion at solid-liquid interface with crystal to crystal transformation. The latter process is driven by molecular recognition, self-assembly, and anchimeric assistance. The observed transformations are feasible due to breathing of inner and outer coordination sphere around metal center resulting in change in metal polyhedra for ‘accommodating’ guest molecule. These transformations cause changes in optical, magnetic, and/or ferroelectric property offering diversity in ‘sensing’ application. With the proposed underlying principles in these exceptional reversible and cyclic transformations, we prepared a series of compounds, can facilitate designing of novel multifunctional molecular materials. PMID:26411980

  9. Interfacial processes studied by coupling electrochemistry at the polarised liquid-liquid interface with in situ confocal Raman spectroscopy.

    PubMed

    Poltorak, Lukasz; Dossot, Manuel; Herzog, Grégoire; Walcarius, Alain

    2014-12-28

    Interfacial processes controlled by ion transfer voltammetry at the interface between two immiscible electrolyte solutions were studied by in situ Raman spectroscopy. Raman spectra of the interface between a 5 mM NaCl aqueous solution and 10 mM bis(triphenyl-phosphoranydieneammonium) tetrakis(4-chlorophenyl)borate in 1,2-dichloroethane were recorded at open circuit potential and at various interfacial potential differences. At open-circuit potential, Raman peaks assigned to vibrational modes of 1,2-dichloroethane are clearly visible and peaks of weak intensity are measured for the organic electrolyte ions. When a negative interfacial potential difference is applied, the intensity of the peaks of the cation of the organic electrolyte increases, confirming its transfer induced by the interfacial potential difference applied. The electrochemically assisted generation of mesoporous silica deposits was then followed by in situ confocal Raman spectroscopy. The condensation of mesoporous silica was controlled by the transfer of cetyltrimethylammonium (CTA(+)) ions to an aqueous phase containing hydrolysed silanes. The transfer of CTA(+) at the interface was monitored in situ by confocal Raman spectroscopy, and formation of silica was observed. PMID:25377062

  10. Extremely sensitive light-induced reorientation in nondoped nematic liquid crystal cells due to photoelectric activation of the interface

    NASA Astrophysics Data System (ADS)

    Pagliusi, P.; Cipparrone, G.

    2003-06-01

    We report an investigation of the extremely sensitive molecular reorientation in pure nematic liquid crystal film induced by the combined application of low dc electric field (less than 0.1 V/μm) and very low intensity optical irradiation (few mW/cm2). The effect is observed in planar cells of well-known commercial nematic mixture (E7) aligned with rubbed polyvinyl alcohol layers, which exhibit photorefractive-like effect. We analyze the dependence of the photoinduced changes in birefringence upon the applied dc voltage and the light intensity. According to our results we believe that the effect is due to photoinduced recombination of the opposite charged carriers accumulated near the interface. In the low dc voltage regime (a few volts) the voltage mainly drops on the electric double layers at the interfaces as a consequence of dc field collected charge carriers from liquid crystalline and polymeric films to the border surfaces. Irradiation with appropriate wavelength reduces the interfacial charges density, because of photoinduced carrier injection and recombination processes, and consequently, induces a relocation of the electric field from the surface to the liquid crystal bulk. The light-induced additional electric field component in the nematic film results in a lowering of the Fréedericksz threshold or an enhanced molecular reorientation.

  11. Time-resolved analytical methods for liquid/solid interfaces. Progress report, November 1, 1993--October 31, 1994

    SciTech Connect

    Harris, J.M.

    1994-10-31

    A number of chemical phenomena that occur at the boundaries between insulating solids and liquids (adsorption, partition, monolayer self-assembly, catalysis, and chemical reactions) are important to energy-related analytical chemistry. These phenomena are central to the development and understanding of chromatographic methods, solid-phase extraction techniques, immobilized analytical reagents, and optical sensors. The goal of this program, therefore, is to develop surface-sensitive spectroscopies by which chemical kinetics at liquid/solid interfaces can be observed on time-scales from nanoseconds to seconds. In the second year of this program, the authors have used temperature-jump relaxation measurements to monitor adsorption/desorption kinetics at liquid/solid interfaces using Joule heating to compare the adsorption of ions from solution onto C1- and C4-derivatized silica surfaces. They completed a study of rate of migration of covalently-attached ligands on silica surfaces; from the temperature-dependence of the migration, the large energy barrier to migration was estimated. Surface heterogeneity of adsorption sites on silica was characterized by time-resolve fluorescence, and the chemical origins investigated by Si{sup 29} NMR spectroscopy. Surface-enhance Raman and fluorescence spectroscopies were modified to study adsorption and binding to silica surfaces. Molecular dynamics simulations were started to help better understand kinetic barriers to adsorption; ESR probe measurements were launched to measure and compare the chain mobility of silica-attached alkyl ligands.

  12. Phase transitions in the liquid-vapor interface of dilute alloys of Bi in Ga: New experimental studies

    SciTech Connect

    Li, Dongxu; Jiang, Xu; Yang, Bin; Rice, Stuart A.

    2010-07-19

    We report the results of measurements of x-ray reflectivity and grazing incidence x-ray diffraction from the liquid-vapor interfaces of four dilute alloys of Bi in Ga with mole fractions x{sub Bi} = 0.0032, 0.0023, 0.00037, and 0.000037. The monolayer coverage of the alloys with x{sub Bi} = 0.0023, and x{sub Bi} = 0.00037 is about 0.85 and only very slightly temperature dependent. The monolayer coverage in the lowest-concentration alloy, with x{sub Bi} = 0.000037, ranged from 0.82 at 29 C to 0.58 at 110 C. In none of these alloys, down to the lowest temperature used, 29 C, can we find any evidence for crystallization of the Bi monolayer that segregates as the outermost stratum of the liquid-vapor interface. Drawing on theoretical arguments we propose that the transitions inferred from the second-harmonic generation and plasma generation studies of dilute Bi in Ga alloys are from the liquid state to the hexatic state of the Bi monolayer. The data for the alloy with x{sub Bi} = 0.000037 suggest that near 80 C there is a disordered phase-to-disordered phase transition.

  13. Mechanically Enhanced Liquid Interfaces at Human Body Temperature Using Thermosensitive Methylated Nanocrystalline Cellulose.

    PubMed

    Scheuble, N; Geue, T; Kuster, S; Adamcik, J; Mezzenga, R; Windhab, E J; Fischer, P

    2016-02-01

    The mechanical performance of materials at oil/water interfaces after consumption is a key factor affecting hydrophobic drug release. In this study, we methylated the surface of nanocrystalline cellulose (NCC) by mercerization and dimethyl sulfate exposure to produce thermosensitive biopolymers. These methylated NCC (metNCC) were used to investigate interfacial thermogelation at air/water and medium-chain triglyceride (MCT)/water interfaces at body temperature. In contrast to bulk fluid dynamics, elastic layers were formed at room temperature, and elasticity increased significantly at body temperature, which was measured by interfacial shear and dilatational rheology in situ. This unique phenomenon depends on solvent quality, temperature, and polymer concentration at interfaces. Thus, by adjusting the degree of hydrophobicity of metNCC, the interfacial elasticity and thermogelation of the interfaces could be varied. In general, these new materials (metNCC) formed more brittle interfacial layers compared to commercial methylcellulose (MC A15). Thermogelation of methylcellulose promotes attractive intermolecular forces, which were reflected in a change in self-assembly of metNCC at the interface. As a consequence, layer thickness and density increased as a function of temperature. These effects were measured by atomic force microscopy (AFM) images of the displaced interface and confirmed by neutron reflection. The substantial structural and mechanical change of methylcellulose interfaces at body temperature represents a controllable encapsulation parameter allowing optimization of lipid-based drug formulations. PMID:26779953

  14. Design of Biomolecular Interfaces using Liquid Crystals Containing Oligomeric Ethylene Glycol

    PubMed Central

    Yang, Zhongqiang; Gupta, Jugal K.; Kishimoto, Kenji; Shoji, Yoshiko; Kato, Takashi; Abbott, Nicholas L.

    2011-01-01

    We report an investigation of nematic LCs formed from miscible mixtures of 4-cyano-4’-pentylbiphenyl (5CB) and 2-(2-[2-{2-(2,3-difluoro-4-{4-(4-trans-pentylcyclohexyl)-phenyl-phenoxy)ethoxy}ethoxy]ethoxy)ethanol (EG4-LC), the latter being a mesogen with a tetra(ethylene glycol) tail. Quantitative characterization of the ordering of this LC mixture at biologically-relevant aqueous interfaces revealed that addition of EG4-LC (1–5% by weight) to 5CB causes a continuous transition in the ordering of the LC from a planar (pure 5CB) to a perpendicular (homeotropic) orientation. The homeotropic ordering is also seen in aqueous dispersions of micrometer-sized droplets of the LC mixture, which exhibit enhanced stability against coalescence. These observations and others, all of which suggest partitioning of the EG4-LC from the bulk of the LC to its aqueous interface, were complemented by measurements of the adsorption of bovine serum albumin (BSA) to the aqueous-LC interface. Whereas adsorption of BSA to the interface of a LC mixture containing 1% wt/wt of EG4-LC triggered an ordering transition, higher concentrations of EG4-LC (>2% wt/wt) prevented this ordering transition, consistent with a decrease in adsorption of BSA. This conclusion is supported by epifluorescence measurements using fluorescently labeled BSA and comparisons to LC interfaces at which EG4-containing lipids are adsorbed. Overall, these results demonstrate a general and facile approach to the design of LCs with interfaces that present biologically relevant chemical functional groups, assume well-defined orientations at aqueous interfaces, and lower non-specific protein adsorption. The bulk of the LC serves as a reservoir of EG4-LC, thus permitting easy preparation of these interfaces and the potential for spontaneous repair of the EG4-decorated interfaces during contact with biological systems. PMID:22199989

  15. Measuring the internal energy content of molecules transported across the liquid-gas interface

    NASA Astrophysics Data System (ADS)

    Maselli, Olivia J.; Gascooke, Jason R.; Lawrance, Warren D.; Buntine, Mark A.

    2009-09-01

    Many details concerning the mechanism associated with the liberation of molecules from a liquid surface remain to be elucidated. We use the liquid microjet technique coupled with laser spectroscopy to measure the rotational and vibrational energy content of benzene spontaneously evaporating from a water-ethanol solution. These measurements provide molecular level insight into the mass and energy transfer processes associated with evaporation.

  16. Structure of alkylimidazolium-based ionic liquids at the interface with vacuum and water--a molecular dynamics study.

    PubMed

    Konieczny, Jan K; Szefczyk, Borys

    2015-03-01

    Ionic liquid (IL) interfaces with vacuum and water are studied by means of classical molecular dynamics simulations. Five ILs are compared: [C2mim][TfO], [C12mim][TfO], [C2mim][NTf2], [C8mim][NTf2] and [C12mim][NTf2], where [C2mim], [C8mim] and [C12mim] stand for 1-ethyl-, 1-octyl- and 1-dodecyl-3-methylimidazolium cation. Physical properties-density, thermal expansion coefficient, compressibility, surface tension, heat of vaporization, self-diffusion coefficient, electric conductivity and viscosity-are calculated and validated against experimental values. The structure of the interfaces is compared in terms of the orientation of the molecules and segregation into layers. It is observed that ILs with short alkyl chains orient at the surface; however, there is no single preferred orientation. ILs with longer chains, on the other hand, orient with alkyl chains protruding into the vacuum at the IL/vacuum interface and into the bulk IL, at the IL/water interface. Anions and water molecules tend to associate with polar imidazolium groups. PMID:25674908

  17. Crowding and Anomalous Capacitance at an Electrode–Ionic Liquid Interface Observed Using Operando X-ray Scattering

    PubMed Central

    2016-01-01

    Room temperature ionic liquids are widely recognized as novel electrolytes with properties very different from those of aqueous solutions, and thus with many potential applications, but observing how they actually behave at electrolytic interfaces has proved to be challenging. We have studied the voltage-dependent structure of [TDTHP]+[NTF2]− near its interface with an electrode, using in situ synchrotron X-ray reflectivity. An anion-rich layer develops at the interface above a threshold voltage of +1.75 V, and the layer thickness increases rapidly with voltage, reaching ∼6 nm (much larger that the anion dimensions) at +2.64 V. These results provide direct confirmation of the theoretical prediction of “crowding” of ions near the interface. The interfacial layer is not purely anionic but a mixture of up to ∼80% anions and the rest cations. The static differential capacitance calculated from X-ray measurements shows an increase at higher voltages, consistent with a recent zero-frequency capacitance measurement but inconsistent with ac capacitance measurements. PMID:27163044

  18. Crowding and Anomalous Capacitance at an Electrode-Ionic Liquid Interface Observed Using Operando X-ray Scattering.

    PubMed

    Chu, Miaoqi; Miller, Mitchell; Dutta, Pulak

    2016-03-23

    Room temperature ionic liquids are widely recognized as novel electrolytes with properties very different from those of aqueous solutions, and thus with many potential applications, but observing how they actually behave at electrolytic interfaces has proved to be challenging. We have studied the voltage-dependent structure of [TDTHP](+)[NTF2](-) near its interface with an electrode, using in situ synchrotron X-ray reflectivity. An anion-rich layer develops at the interface above a threshold voltage of +1.75 V, and the layer thickness increases rapidly with voltage, reaching ∼6 nm (much larger that the anion dimensions) at +2.64 V. These results provide direct confirmation of the theoretical prediction of "crowding" of ions near the interface. The interfacial layer is not purely anionic but a mixture of up to ∼80% anions and the rest cations. The static differential capacitance calculated from X-ray measurements shows an increase at higher voltages, consistent with a recent zero-frequency capacitance measurement but inconsistent with ac capacitance measurements. PMID:27163044

  19. The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces

    NASA Astrophysics Data System (ADS)

    Cheng, H.-W.; Dienemann, J.-N.; Stock, P.; Merola, C.; Chen, Y.-J.; Valtiner, M.

    2016-07-01

    Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations.

  20. The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces.

    PubMed

    Cheng, H-W; Dienemann, J-N; Stock, P; Merola, C; Chen, Y-J; Valtiner, M

    2016-01-01

    Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations. PMID:27452615

  1. The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces

    PubMed Central

    Cheng, H.-W.; Dienemann, J.-N.; Stock, P.; Merola, C.; Chen, Y.-J.; Valtiner, M.

    2016-01-01

    Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations. PMID:27452615

  2. ELECTRON TRANSFER MECHANISM AT THE SOLID-LIQUID INTERFACE OF PHYLLOSILICATES

    EPA Science Inventory

    Interfacial electron transfer processes on clay minerals have significant impact in natural environments and geochemical systems. Nitrobenzene was used as molecular probes to study the electron transfer mechanism at the solid-water interfaces of Fe-containing phyllosicates. For...

  3. Superfluid interfaces in liquid He-3: Superconducting cosmic domain walls in the laboratory

    NASA Astrophysics Data System (ADS)

    Salomaa, M. M.

    The interface between superfluid He-3-A and He-3-B, as the most novel surface known to exist in condensed matter physics, was studied. The most important (and most surprising) finding is the discovery of completely new classes of A-A interphasons displaying a fractional quantum jump in the phase psi of the superfluid condensate: for these novel interphasons, the phase difference delta(psi) between the left and the right A-phase vacua, is only pi/2 (or -pi/2 congruence 3pi/2), not pi. These half soliton vacuum interfaces provide the most elementary possible processes of phase slippage in superfluid He-3-A. Symmetry analysis and numerical calculations have revealed that the number of superfluid A-B interfaces is doubled in the presence of an external magnetic field. In particular, the rotating A-B interface is intriguing, since it is theoretically predicted to contain a plenitude of different hedgehogs: Dirac monopoles with fractional charge.

  4. Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid-Crystal/ZnO Nanocrystals.

    PubMed

    Paczesny, Jan; Wolska-Pietkiewicz, Małgorzata; Binkiewicz, Ilona; Wróbel, Zbigniew; Wadowska, Monika; Matuła, Kinga; Dzięcielewski, Igor; Pociecha, Damian; Smalc-Koziorowska, Julita; Lewiński, Janusz; Hołyst, Robert

    2015-11-16

    The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy. PMID:26427916

  5. A fluorosurfactant and photoreducible Cu(II)-tren click catalyst: surfactant and catalytic properties at liquid/liquid interfaces.

    PubMed

    Jochyms, Quentin; Guillot, Pierre; Mignard, Emmanuel; Vincent, Jean-Marc

    2015-12-01

    The fluorous copper(ii) complex [Cu(II)(trenRf6)3-benzoylbenzoate]3-benzoylbenzoate 2, composed of a highly fluorophilic tris(2-aminoethyl)amine ligand and two 3-benzoylbenzoates as counterions and photosensitizers, was synthesized from the dinuclear complex [Cu(3-benzoylbenzoate)4(H2O)2] 1 which was characterized by X-ray analysis. Complex 2, which is highly soluble in perfluorocarbons, moderately soluble in organic solvents while insoluble in water, was found to be a very effective fluorosurfactant. At the air/water interface it formed a Langmuir film, which upon compression slowly collapsed at about 28 mN m(-1), which corresponds to a surface area of about 220 Å(2) per molecule. Tensiometric measurements revealed that 2 is more rapidly adsorbed at the diisopropyl ether (DIPE)/water interface than the perfluorodecalin (PFD)/water one, leading to a decrease of the interfacial tensions of about 14 mN m(-1) and 40 mN m(-1), respectively. Photoreduction of 2 occurs effectively in H-donating solvents such as THF and DIPE, or even in PFD ensuring that an electron donor, such as propargyl alcohol, is present in a separate aqueous phase. Complex 2, when combined with light (365 nm), catalyzes the click reaction between the azide 3 and alkyne 4 under homogeneous conditions (methanol), to afford the disaccharide 5. Under emulsified biphasic DIPE/water or PFD/water conditions, the reactions proceeded well. However, it was shown that a fast and significant amount of copper and 3-benzoylbenzoate counterion was transferred into the aqueous phase, and that most of the catalysis could be ascribed to a copper species solubilised in the aqueous phase, and not to the fluorous copper complex accumulated at the interface. PMID:26489534

  6. Self-assembly of cholesterol DNA at liquid crystal/aqueous interface and its application for DNA detection

    NASA Astrophysics Data System (ADS)

    Lai, Siok Lian; Hartono, Deny; Yang, Kun-Lin

    2009-10-01

    In this letter, we report a strategy of detecting the DNA targets by using a thin layer of self-assembled cholesterol-labeled DNA probes at the liquid crystal (LC)/aqueous interface. When the system is exposed to 51 μg/ml of complementary DNA targets, the optical appearance of LC shows a continuous change from dark to bright under the crossed polars within 15 min. No obvious change can be observed when the system is exposed to one or two base-pair mismatch DNA targets. This system provides a principle for label-free and real-time detection of DNA targets without any fluorescent labeling.

  7. Semiempirical self-consistent polarization description of bulk water, the liquid-vapor interface, and cubic ice.

    PubMed

    Murdachaew, Garold; Mundy, Christopher J; Schenter, Gregory K; Laino, Teodoro; Hutter, Jürg

    2011-06-16

    We have applied an efficient electronic structure approach, the semiempirical self-consistent polarization neglect of diatomic differential overlap (SCP-NDDO) method, previously parametrized to reproduce properties of water clusters by Chang, Schenter, and Garrett [ J. Chem. Phys. 2008 , 128 , 164111 ] and now implemented in the CP2K package, to model ambient liquid water at 300 K (both the bulk and the liquid-vapor interface) and cubic ice at 15 and 250 K. The SCP-NDDO potential retains its transferability and good performance across the full range of conditions encountered in the clusters and the bulk phases of water. In particular, we obtain good results for the density, radial distribution functions, enthalpy of vaporization, self-diffusion coefficient, molecular dipole moment distribution, and hydrogen bond populations, in comparison to experimental measurements. PMID:21370904

  8. Aircraft Measurements of Temperature and Liquid Water Content in Entrainment Interface Layer of Stratocumulus Clouds.

    NASA Astrophysics Data System (ADS)

    Haman, K. E.; Gerber, H.; Kumala, W.; Malinowski, S. P.

    2009-09-01

    Entrainment of dry, warm air from above the cloud and its mixing with the colder cloudy air is an important process in dynamics of inversion topped stratocumulus, leading to formation of a transition layer of complex structure - Entrainment Interface Layer (EIL). It consists of mutual filaments if cloudy and clear air of various thickness at different stages of stirring, mixing and homogenization. Borders between these filaments are often very sharp, with temperature jumps of few kelvins and liquid water content (LWC) jumps of up to 0.5 gmE-3 over distance of few centimeters, which cannot be resolved by means of standard aircraft instrumentation. This layer is an area of various specific dynamic and thermodynamic phenomena; in particular it is a source of downdrafts penetrating the cloud as the so called "cloud holes". Small scale structure of EIL has been investigated in 2001 during DYCOMS II campaign in marine stratocumulus over Eastern Pacific, by means of Ultrafast Aircraft Thermometer (UFT-F) from University of Warsaw and PVM-100A LWC-meter from Gerber Scientific, Inc. Some results of this research has been published in 2007 in Quarterly Journal of RMS. UFT-F has a thermoresistive sensing element protected against impact of cloud droplets and response time constant of order 10E-4s. PVM-100A is an optical instrument and has spatial resolution of order 10 cm. For recording a sampling rate of 1kHz has been typically applied with 10 kHz (for UFT-F only) on selected fragments of flights. Unfortunately, for some technical reasons, these two instruments, installed on the NCAR C-130 aircraft, were separated by about 6 meters what limited possibilities and precision of comparing their indications. There were also some failures during the flights due to which many potentially interesting measurements and observations have been lost. Opportunity to get improved observations of EIL appeared in 2008 at POST (Physics of Stratocumulus Top) Project. During POST a number of

  9. Effects of liquid VOC concentration and salt content on partitioning equilibrium of hydrophilic VOC at air-sweat interface

    NASA Astrophysics Data System (ADS)

    Cheng, Wen-Hsi; Chu, Fu-Sui; Su, Tzy-I.

    Volatile organic compounds (VOCs) must initially be absorbed by sweat on the surface of skin for human VOC dermal exposure. The partitioning equilibrium at the air-sweat interface is given by p=Cg*/C, where pc is the partitioning coefficient, and Cg* is the gaseous concentration in equilibrium with the aqueous VOC concentration ( CL) at a constant water temperature ( Tw). A series of thermodynamic functions of Cg*(C,T) are presented, as well as the values of pc, and the heat of gaseous-liquid phase transfer (Δ Htr) for tested VOCs, including iso-propanol (IPA, CL=12-120 mg L -1) and methyl ethyl ketone (MEK, CL=10-80 mg L -1) to determine the effects of liquid VOC concentration and salt contents of sweat on pc of hydrophilic VOCs. Experimental data reveal that the pc values of IPA and MEK drop as the liquid VOC concentrations increasing from 10 to 120 mg L -1. However, sodium salt content in human sweat (sodium chloride and sodium lactate) induces the effect of salt, indicating the increase in pc. Notably, neither urea nor ammonia in human sweat increase pc. Artificial sweat, consisting of sodium chloride 0.47%, urea 0.05%, ammonia 0.004% and sodium lactate 0.6%, was used to evaluate the increase in the pc values of IPA and MEK. The liquid VOC concentration effect simultaneously develops together with the salt effect on the partition at the interface of air-sweat for hydrophilic VOC solutions. The pc values of IPA for artificial sweat decrease as much as 32.5% as CL increases from 12 to 120 mg L -1 at 300 K, and those of MEK drop by as much as 70.9% as CL increases from 10 to 80 mg L -1 at 300 K. This investigation provides a basis for elucidating the assessment of human dermal exposure to hydrophilic VOCs.

  10. Vapor condensation rate at a turbulent liquid interface, for application to cryogenic hydrogen

    NASA Technical Reports Server (NTRS)

    Helmick, M. R.; Khoo, B. C.; Brown, J. S.; Sonin, A. A.

    1988-01-01

    The condensation of hydrogen vapor onto turbulent liquid hydrogen is simulated experimentally using steam and water at elevated pressure, where water has a Prandtl number comparable to that of liquid hydrogen. A correlation is presented for the condensation rate in terms of the intensity and macroscale of the turbulence on the liquid side. The rate correlation should be applicable to low-gravity conditions at the higher turbulence intensities; at the lower turbulence intensities, however, the data are affected by thermal stratification resulting from buoyancy effects.

  11. Microjets and coated wheels: versatile tools for exploring collisions and reactions at gas-liquid interfaces.

    PubMed

    Faust, Jennifer A; Nathanson, Gilbert M

    2016-07-01

    This tutorial review describes experimental aspects of two techniques for investigating collisions and reactions at the surfaces of liquids in vacuum. These gas-liquid scattering experiments provide insights into the dynamics of interfacial processes while minimizing interference from vapor-phase collisions. We begin with a historical survey and then compare attributes of the microjet and coated-wheel techniques, developed by Manfred Faubel and John Fenn, respectively, for studies of high- and low-vapor pressure liquids in vacuum. Our objective is to highlight the strengths and shortcomings of each technique and summarize lessons we have learned in using them for scattering and evaporation experiments. We conclude by describing recent microjet studies of energy transfer between O2 and liquid hydrocarbons, HCl dissociation in salty water, and super-Maxwellian helium evaporation. PMID:27126211

  12. Ionic Liquid-Based Polymer Electrolytes via Surfactant-Assisted Polymerization at the Plasma-Liquid Interface.

    PubMed

    Tran, Quoc Chinh; Bui, Van-Tien; Dao, Van-Duong; Lee, Joong-Kee; Choi, Ho-Suk

    2016-06-29

    We first report an innovative method, which we refer to as interfacial liquid plasma polymerization, to chemically cross-link ionic liquids (ILs). By this method, a series of all-solid state, free-standing polymer electrolytes is successfully fabricated where ILs are used as building blocks and ethylene oxide-based surfactants are employed as an assisted-cross-linking agent. The thickness of the films is controlled by the plasma exposure time or the ratio of surfactant to ILs. The chemical structure and properties of the polymer electrolyte are characterized by scanning electron microscopy (SEM), Fourier transformation infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy (EIS). Importantly, the underlying polymerization mechanism of the cross-linked IL-based polymer electrolyte is studied to show that fluoroborate or halide anions of ILs together with the aid of a small amount of surfactants having ethylene oxide groups are necessary to form cross-linked network structures of the polymer electrolyte. The ionic conductivity of the obtained polymer electrolyte is 2.28 × 10(-3) S·cm(-1), which is a relatively high value for solid polymer electrolytes synthesized at room temperature. This study can serve as a cornerstone for developing all-solid state polymer electrolytes with promising properties for next-generation electrochemical devices. PMID:27281115

  13. Triangular tessellation scheme for the adsorption free energy at the liquid-liquid interface: Towards nonconvex patterned colloids.

    PubMed

    de Graaf, Joost; Dijkstra, Marjolein; van Roij, René

    2009-11-01

    We present a numerical technique, namely, triangular tessellation, to calculate the free energy associated with the adsorption of a colloidal particle at a flat interface. The theory and numerical scheme presented here are sufficiently general to handle nonconvex patchy colloids with arbitrary surface patterns characterized by a wetting angle, e.g., amphiphilicity. We ignore interfacial deformation due to capillary, electrostatic, or gravitational forces, but the method can be extended to take such effects into account. It is verified that the numerical method presented is accurate and sufficiently stable to be applied to more general situations than presented in this paper. The merits of the tessellation method prove to outweigh those of traditionally used semianalytic approaches, especially when it comes to generality and applicability. PMID:20364983

  14. Fast contact of solid-liquid interface created high strength multi-layered cellulose hydrogels with controllable size.

    PubMed

    He, Meng; Zhao, Yanteng; Duan, Jiangjiang; Wang, Zhenggang; Chen, Yun; Zhang, Lina

    2014-02-12

    Novel onion-like and multi-layered tubular cellulose hydrogels were constructed, for the first time, from the cellulose solution in a 7% NaOH/12% urea aqueous solvent by changing the shape of the gel cores. In our findings, the contacting of the cellulose solution with the surface of the agarose gel rod or sphere loaded with acetic acid led to the close chain packing to form immediately a gel layer, as a result of the destruction of the cellulose inclusion complex by acid through inducing the cellulose self-aggregation. Subsequently, multi-layered cellulose hydrogels were fabricated via a multi-step interrupted gelation process. The size, layer thickness and inter-layer space of the multi-layered hydrogels could be controlled by adjusting the cellulose concentrations, the gel core diameter and the contacting time of the solid-liquid interface. The multi-layered cellulose hydrogels displayed good architectural stability and solvent resistance. Moreover, the hydrogels exhibited high compressive strength and excellent biocompatibility. L929 cells could adhere and proliferate on the surface of the layers and in interior space, showing great potential as tissue engineering scaffolds and cell culture carrier. This work opens up a new avenue for the construction of the high strength multi-layered cellulose hydrogels formed from inner to outside via a fast contact of solid-liquid interface. PMID:24405277

  15. The amorphous silica-liquid water interface studied by ab initio molecular dynamics (AIMD): local organization in global disorder.

    PubMed

    Cimas, Álvaro; Tielens, Frederik; Sulpizi, Marialore; Gaigeot, Marie-Pierre; Costa, Dominique

    2014-06-18

    The structural organization of water at a model of amorphous silica-liquid water interface is investigated by ab initio molecular dynamics (AIMD) simulations at room temperature. The amorphous surface is constructed with isolated, H-bonded vicinal and geminal silanols. In the absence of water, the silanols have orientations that depend on the local surface topology (i.e. presence of concave and convex zones). However, in the presence of liquid water, only the strong inter-silanol H-bonds are maintained, whereas the weaker ones are replaced by H-bonds formed with interfacial water molecules. All silanols are found to act as H-bond donors to water. The vicinal silanols are simultaneously found to be H-bond acceptors from water. The geminal pairs are also characterized by the formation of water H-bonded rings, which could provide special pathways for proton transfer(s) at the interface. The first water layer above the surface is overall rather disordered, with three main domains of orientations of the water molecules. We discuss the similarities and differences in the structural organization of the interfacial water layer at the surface of the amorphous silica and at the surface of the crystalline (0 0 0 1) quartz surface. PMID:24863440

  16. Sum-frequency generation analyses of the structure of water at amphoteric SAM-liquid water interfaces.

    PubMed

    Nomura, Kouji; Nakaji-Hirabayashi, Tadashi; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei

    2014-09-01

    Surfaces of both a cover glass and the flat plane of a semi-cylindrical quartz prism were modified with a mixture of positively and negatively charged silane coupling reagents (3-aminopropyltriethoxysilane (APTES) and 3-(trihydroxysilyl)propylmethylphosphonate (THPMP), respectively). The glass surface modified with a self-assembled monolayer (SAM) prepared at a mixing ratio of APTES:THPMP=4:6 was electrically almost neutral and was resistant to non-specific adsorption of proteins, whereas fibroblasts gradually adhered to an amphoteric (mixed) SAM surface probably due to its stiffness, though the number of adhered cells was relatively small. Sum frequency generation (SFG) spectra indicated that total intensity of the OH stretching region (3000-3600cm(-1)) for the amphoteric SAM-modified quartz immersed in liquid water was smaller than those for the positively and negatively charged SAM-modified quartz prisms and a bare quartz prism in contact with liquid water. These results suggested that water molecules at the interface of water and an amphoteric SAM-modified quartz prism are not strongly oriented in comparison with those at the interface of a lopsidedly charged SAM-modified quartz prism and bare quartz. The importance of charge neutralization for the anti-biofouling properties of solid materials was strongly suggested. PMID:25001187

  17. Frozen wave induced by high frequency horizontal vibrations on a CO2 liquid-gas interface near the critical point.

    PubMed

    Wunenburger, R; Evesque, P; Chabot, C; Garrabos, Y; Fauve, S; Beysens, D

    1999-05-01

    We used the liquid-vapor equilibrium of CO2 near its critical point (T(C)-T=1 to 150 mK) in order to study the stability of an interface between a gas and a liquid having close densities rho(L) approximately rho(V) when submitted to high frequency f (3-57.5 Hz) horizontal vibrations (of amplitude a from 0.1 to 2.5 mm). Above a given velocity threshold (2piaf )(0) we observed a "frozen wave," corresponding to an interface profile of sinelike shape which is stationary in the reference frame of the vibrated sample cell. By varying the vibration parameters, the surface tension, and the density difference between the two phases via the temperature, it was found that the wavelength and the amplitude of the stationary profile are both increasing functions of the frequency and of the amplitude of the vibration and that they are proportional to the capillary length. Our measurements are consistent with a model of inviscid and incompressible flow averaging the effect of the vibration over a period and leading to a Kelvin-Helmholtz-like instability mechanism due to the relative motion of the two fluids. PMID:11969523

  18. Numerical determination of the interfacial energy and nucleation barrier of curved solid-liquid interfaces in binary systems

    NASA Astrophysics Data System (ADS)

    Kundin, Julia; Choudhary, Muhammad Ajmal

    2016-07-01

    The phase-field crystal (PFC) technique is a widely used approach for modeling crystal growth phenomena with atomistic resolution on mesoscopic time scales. We use a two-dimensional PFC model for a binary system based on the work of Elder et al. [Phys. Rev. B 75, 064107 (2007), 10.1103/PhysRevB.75.064107] to study the effect of the curved, diffuse solid-liquid interface on the interfacial energy as well as the nucleation barrier. The calculation of the interfacial energy and the nucleation barrier certainly depends on the proper definition of the solid-liquid dividing surface and the corresponding nucleus size. We define the position of the sharp interface at which the interfacial energy is to be evaluated by using the concept of equimolar dividing surface (re) and the minimization of the interfacial energy (rs). The comparison of the results based on both radii shows that the difference re-rs is always positive and has a limit for large cluster sizes which is comparable to the Tolman length. Furthermore, we found the real nucleation barrier for small cluster sizes, which is defined as a function of the radius rs, and compared it with the classical nucleation theory. The simulation results also show that the extracted interfacial energy as function of both radii is independent of system size, and this dependence can be reasonably described by the nonclassical Tolman formula with a positive Tolman length.

  19. Experimental study of the solid-liquid interface in a yield-stress fluid flow upstream of a step

    NASA Astrophysics Data System (ADS)

    Luu, Li-Hua; Pierre, Philippe; Guillaume, Chambon

    2014-11-01

    We present an experimental study where a yield-stress fluid is implemented to carefully examine the interface between a liquid-like unyielded region and a solid-like yielded region. The studied hydrodynamics consists of a rectangular pipe-flow disturbed by the presence of a step. Upstream of the step, a solid-liquid interface between a dead zone and a flow zone appears. This configuration can both model geophysical erosion phenomenon in debris flows or find applications for industrial extrusion processes. We aim to investigate the dominant physical mechanism underlying the formation of the static domain, by combining the rheological characterization of the yield-stress fluid with local measurements of the related hydrodynamic parameters. In this work, we use a model fluid, namely polymer micro-gel Carbopol, that exhibits a Hershel-Bulkley viscoplastic rheology. Exploiting the fluid transparency, the flow is monitored by Particle Image Velocimetry thanks to internal visualization technique. In particular, we demonstrate that the flow above the dead zone roughly behaves as a plug flow whose velocity profile can successfully be described by a Poiseuille equation including a Hershel-Bulkley rheology (PHB theory), with exception of a thin zone at the close vicinity of the static domain. The border inside the flow zone above which the so-called PHB flow starts, is found to be the same regardless of the flow rate and to move with a constant velocity that increases with the flow rate. We interpret this feature as a slip frontier.

  20. Tunable synergism/antagonism in a mixed nonionic/anionic surfactant layer at the solid/liquid interface.

    PubMed

    Lu, Shaohua; Somasundaran, Ponisseril

    2008-04-15

    The use of mixed surfactants for modification of solid surfaces is important for many applications, since beneficial synergism often occurs depending on the surfactant type and mixing conditions. Systematical information on the properties of surfactant mixtures at the solid/liquid interface can be helpful for optimizing the interactions between the surfactants and then their corresponding performance. In this work, a nonionic/anionic surfactant combination, n-dodecyl beta-d-maltoside (DM) and sodium dodecyl sulfonate (SDS), was selected for the study of adsorption on an oxide solid, alumina. Interestingly, the mixture of the two surfactants with opposite pH-dependence of adsorption on alumina exhibits some unique synergistic or antagonistic features that were found to be tunable in the region of pH 4-10. In addition, the DM/SDS molar ratio in the adsorbed layer was found to decrease with concentration in the saturated region at all the pH and mixing ratios tested. The decrease is attributed to the monomer concentration changes in solution due to the difference in surface activities of the two surfactants. The tunable features of this mixture at the solid/liquid interface provide a way to optimize the properties by changing the mixing conditions. This can be valuable in many applications, such as enhanced oil recovery, flotation, and solubilization. PMID:18324849