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Sample records for aux interfaces liquide

  1. PREFACE: Functionalized Liquid Liquid Interfaces

    NASA Astrophysics Data System (ADS)

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

    2007-09-01

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

  2. Probing interfaces involving liquids.

    PubMed

    Robinson, A L

    1987-04-10

    Last month in Washington, D.C., the National Academy of Sciences held the first of what it hopes will be a series of seminars in forefront fields of science, technology, and medicine. The idea is to bring the academy closer to the frontlines of research and to help spread the word to federal science policy-makers. The subject of the 23 and 24 March seminar was interfaces and thin films, and the talks, though tutorial in nature, contained a pleasantly large number of still unpublished results. Interfaces, such as the surface of a solid exposed to a liquid or gas, and thin films, whose properties are heavily influenced by interfaces, have long been of considerable technological importance and have always been so in biological processes, but researchers are now getting access to the experimental and theoretical tools needed to explore these complex physical systems that are neither ideally two-dimensional nor fully three-dimensional. The briefings that follow give a peek at three ways to probe interfaces involving liquids.

  3. Electrokinetics over liquid/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Squires, Todd M.

    2011-11-01

    Since liquid-liquid interfaces flow in response to an applied stress, one might expect electrokinetic flows at liquid-liquid interfaces to be significantly higher than over liquid-solid interfaces. The earliest predictions for the electrophoretic mobility of charged mercury drops - distinct approaches by Frumkin and Levich (1946), and Booth (1951) - differed by O (a /λD) , where a is the radius of the drop and λD is the Debye screening length. Seeking to reconcile this rather striking discrepancy, Levine (1973) showed double-layer polarization to be the key ingredient. Without a physical mechanism by which electrokinetic effects are enhanced, however, it is difficult to know how general the enhancement is - whether it holds only for liquid metal surfaces, or more generally, for all liquid/liquid surfaces. By considering a series of systems in which a planar metal strip is coated with either a liquid metal or liquid dielectric, we show that the central physical mechanism behind the enhancement predicted by Frumkin and Levich (1946) is the presence of an unmatched electrical stress upon the electrolyte-liquid interface, which establishes a Marangoni stress on the droplet surface and drives it into motion. The source of the unbalanced electrokinetic stress on a liquid metal surface is clear - metals represent equipotential surfaces, so no field exists to drive an equal and opposite force on the surface charge. This might suggest that liquid metals represent a unique system, since dielectric liquids can support finite electric fields, which might be expected to exert an electrical stress on the surface charge that balances the electric stress. We demonstrate, however, that electrical and osmotic stresses on relaxed double-layers internal to dielectric liquids precisely cancel, so that internal electrokinetic stresses generally vanish in closed, ideally polarizable liquids. The enhancement for liquid mercury drops can thus be expected quite generally over clean

  4. 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.

  5. One-particle microrheology at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Wu, Jian; Dai, Lenore L.

    2006-08-01

    The authors use Pickering emulsions as a model system to investigate the dynamics of charged microparticles at polydimethylsiloxane (oil)-water interfaces using confocal laser scanning microscopy. More importantly, they have explored the potential of developing one-particle microrheology at liquid-liquid interfaces. The complex, loss, and storage moduli of oil-water interfaces as a function of frequency measured from microrheology are compared with those of bulk oils measured from a conventional rheometer and developed bulk microrheology. The nature of the tracer particles plays an important role in one-particle microrheology at liquid-liquid interfaces.

  6. Gas enrichment at liquid-wall interfaces.

    PubMed

    Dammer, Stephan M; Lohse, Detlef

    2006-05-26

    Molecular dynamics simulations of Lennard-Jones systems are performed to study the effects of dissolved gas on liquid-wall and liquid-gas interfaces. Gas enrichment at walls, which for hydrophobic walls can exceed more than 2 orders of magnitude when compared to the gas density in the bulk liquid, is observed. As a consequence, the liquid structure close to the wall is considerably modified, leading to an enhanced wall slip. At liquid-gas interfaces gas enrichment which reduces the surface tension is found.

  7. Hydrogen evolution at liquid-liquid interfaces.

    PubMed

    Hatay, Imren; Su, Bin; Li, Fei; Partovi-Nia, Raheleh; Vrubel, Heron; Hu, Xile; Ersoz, Mustafa; Girault, Hubert H

    2009-01-01

    Blowing bubbles: Hydrogen evolution by proton reduction with [(C(5)Me(5))(2)Fe] occurs at a soft interface between water and 1,2-dichloroethane (DCE). The reaction proceeds by proton transfer assisted by [(C(5)Me(5))(2)Fe] across the water-DCE interface with subsequent proton reduction in DCE. The interface essentially acts as a proton pump, allowing hydrogen evolution by directly using the aqueous proton.

  8. 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.

  9. 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

  10. Low frequency ionic conduction across liquid interfaces

    NASA Astrophysics Data System (ADS)

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

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

  11. 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.

  12. 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.

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

    PubMed

    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.

  14. 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)

  15. Structural Transitions at Ionic Liquid Interfaces.

    PubMed

    Rotenberg, Benjamin; Salanne, Mathieu

    2015-12-17

    Recent advances in experimental and computational techniques have allowed for an accurate description of the adsorption of ionic liquids on metallic electrodes. It is now well-established that they adopt a multilayered structure and that the composition of the layers changes with the potential of the electrode. In some cases, potential-driven ordering transitions in the first adsorbed layer have been observed in experiments probing the interface on the molecular scale or by molecular simulations. This perspective gives an overview of the current understanding of such transitions and of their potential impact on the physical and (electro)chemical processes at the interface. In particular, peaks in the differential capacitance, slow dynamics at the interface, and changes in the reactivity have been reported in electrochemical studies. Interfaces between ionic liquids and metallic electrodes are also highly relevant for their friction properties, the voltage-dependence of which opens the way to exciting applications. PMID:26722704

  16. Particle Behavior at Anisotropically Curved Liquid Interfaces

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  17. 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

  18. Crosslinked nanoparticle assemblies at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Tangirala, Ravisubhash; Skaff, Habib; Lin, Yao; Russell, Thomas; Emrick, Todd

    2006-03-01

    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. The weak confinement of nanoparticles to the liquid-liquid interface enables the formation of particle-based assemblies that possess unique features relative to assemblies of micron-scale particles. Crosslinking of nanoparticles at a liquid-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. Norbornene-functionalized CdSe/ZnS core/shell quantum dots are used in this study 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) using a unique amphiphilic ruthenium benzylidene metathesis catalyst. The crosslinked capsules display a size-selective encapsulation capability, dictated by the interstitial spaces between the nanoparticles. The porosity of the capsules can be further tuned by the addition of small amounts of uncrosslinkable nanoparticles prior to crosslinking.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Ion distributions near a liquid-liquid interface.

    PubMed

    Luo, Guangming; Malkova, Sarka; Yoon, Jaesung; Schultz, David G; Lin, Binhua; Meron, Mati; Benjamin, Ilan; Vanysek, Petr; Schlossman, Mark L

    2006-01-13

    Mean field theories of ion distributions, such as the Gouy-Chapman theory that describes the distribution near a charged planar surface, ignore the molecular-scale structure in the liquid solution. The predictions of the Gouy-Chapman theory vary substantially from our x-ray reflectivity measurements of the interface between two electrolyte solutions. Molecular dynamics simulations, which include the liquid structure, were used to calculate the potential of mean force on a single ion. We used this potential of mean force in a generalized Poisson-Boltzmann equation to predict the full ion distributions. These distributions agree with our measurements without any adjustable parameters. PMID:16410522

  4. Polymer Crystallization at Curved Liquid-Liquid Interface

    NASA Astrophysics Data System (ADS)

    Li, Christopher; Wang, Wenda; Qi, Hao; Huang, Ziyin

    2013-03-01

    Curved space is incommensurate with typical ordered structures with three-dimensional (3D) translational symmetry. However, upon assembly, soft matter, including colloids, amphiphiles, and block copolymers (BCPs), often forms structures depicting curved surface/interface. Examples include liposomes, colloidosomes, spherical micelles, worm-like micelles, and vesicles (also known as polymersomes). For crystalline BCPs, crystallization oftentimes overwrites curved geometries since the latter is incommensurate with crystalline order. On the other hand, twisted and curved crystals are often observed in crystalline polymers. Various mechanisms have been proposed for these non-flat crystalline morphologies. In this presentation, we will demonstrate that curved liquid/liquid (L/L) interface can guide polymer single crystal growth. The crystal morphology is strongly dependent on the nucleation mechanism. A myriad of controlled curved single crystals can be readily obtained.

  5. Layerless fabrication with continuous liquid interface production

    PubMed Central

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

    2016-01-01

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

  6. 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.

  7. Self-assembly of nanoparticles at liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Du, Kan

    In this thesis, we studied the self-assembly of nanoparticles at liquid metal-water interfaces and oil-water interfaces. We demonstrated a simple approach to form nanostructured electronic devices by self-assembly of nanoparticles at liquid metal surfaces. In this approach, two liquid-metal droplets, which were coated with a monolayer of ligand-stabilized nanoparticles, were brought into contact. They did not coalesce but instead remained separated by the nanoparticles assembled at the interface. Devices formed by this method showed electron transport between droplets that was characteristic of the Coulomb blockade, where current was suppressed below a tunable threshold voltage because of the energy of charging individual nanoparticles. Further studies of this approach demonstrated the potential of interfacial assembly in fabricating microscopic electronic devices over a large area in a cost-effective and time-efficient fashion. Micrometer-scale Ga droplets coated with nanoparticles were fabricated using ultrasonication and then deposited on patterned substrates to form microscopic devices. I-V measurements showed Coulomb blockade effect in the devices containing more than one nanoparticle junction. The measured threshold voltages increased with number of junctions as expected for devices arranged in series. We also studied experimentally the energy of adsorption, Delta E, of nanoparticles and microparticles at the oil-water and Ga-water interfaces by monitoring the decrease of interfacial tension as the particles bind. For citrate-stabilized gold nanoparticles assembling on a droplet of octafluoropentyl acrylate, we found DeltaE=-5.1 kBT for particle radius R=2.5 nm, and Delta E ∝ R2 for larger sizes. Gold nanoparticles with (1-mercaptoundec-11-yl) tetra(ethylene glycol) ligand had a much larger binding energy (DeltaE=-60.4 kBT) and an energy barrier against adsorption. For polystyrene spheres with R=1.05 microm, we found DeltaE=-0.9x10 6 kBT. We also found that

  8. 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).

  9. 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

  10. 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

  11. Liquid effluent services and solid waste disposal interface control document

    SciTech Connect

    Carlson, A.B.

    1994-10-27

    This interface control document between Liquid Effluent Services (LES) and Solid Waste Disposal (SWD) establishes the functional responsibilities of each division where interfaces exist between the two divisions. The document includes waste volumes and timing for use in planning the proper waste management capabilities. The interface control document also facilitates integration of existing or planned waste management capabilities of the Liquid Effluent Services and Solid Waste divisions.

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

    SciTech Connect

    Not Available

    1990-01-01

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

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Nanofluidic transport governed by the liquid/vapour interface

    NASA Astrophysics Data System (ADS)

    Lee, Jongho; Laoui, Tahar; Karnik, Rohit

    2014-04-01

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

  18. Interfacing dielectric elastomer actuators with liquids

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  19. 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

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

    DOEpatents

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

    2010-07-20

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

  1. Fluctuations at a constrained liquid-solid interface.

    PubMed

    Chaudhuri, Abhishek; Chaudhuri, Debasish; Sengupta, Surajit

    2007-08-01

    We study the interface between a solid trapped within a bath of liquid by a suitably shaped nonuniform external potential. Such a potential may be constructed using lasers, external electric or magnetic fields, or a surface template. We study a two-dimensional case where a thin strip of solid, created in this way, is surrounded on either side by a bath of liquid with which it can easily exchange particles. Since height fluctuations of the interface cost energy, this interface is constrained to remain flat at all length scales. However, when such a solid is stressed by altering the depth of the potential beyond a certain limit, it responds by relieving stress by novel interfacial fluctuations, which involve addition or deletion of entire lattice layers of the crystal. This "layering" transition is a generic feature of the system regardless of the details of the interaction potential. We show how such interfacial fluctuations influence mass, momentum, and energy transport across the interface. Tiny momentum impulses produce weak shock waves, which travel through the interface and cause the spallation of crystal layers into the liquid. Kinetic and energetic constraints prevent spallation of partial layers from the crystal, a fact which may be of some practical use. We also study heat transport through the liquid-solid interface and obtain the resistances in liquid, solid, and interfacial regions (Kapitza resistance) as the solid undergoes such layering transitions. Heat conduction, which shows strong signatures of the structural transformations, can be understood using a free volume calculation. PMID:17930047

  2. 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.

  3. 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.

  4. Nanoparticles at liquid interfaces: rotational dynamics and angular locking.

    PubMed

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

    2014-01-01

    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.

  5. Liquid organization and solvation properties at polar solid/liquid interfaces.

    PubMed

    Gobrogge, Eric A; Woods, B Lauren; Walker, Robert A

    2013-01-01

    Second order nonlinear optical spectroscopy has been employed to examine the organization of four different liquids at the hydrophilic silica/liquid interface. The liquids - cyclohexane, methylcyclohexane, 1-propanol, and 2-propanol - were chosen to isolate how intermolecular forces between the liquid and the substrate competed with steric effects to control liquid structure and solvating properties across the interfacial region. Vibrational sum frequency generation (VSFG) data showed that cyclohexane structure at the silica/liquid cyclohexane interface closely resembled the structure of a cyclohexane monolayer adsorbed to the silica/vapor interface. Methylcyclohexane, however, showed evidence of large structural reorganization between the silica/liquid and silica/monolayer/vapor interfaces. 1-Propanol at a silica/vapor interface formed a well-ordered, Langmuir-like monolayer due to strong hydrogen bonding with the surface silanols and cohesive van der Waals interactions between carbon chains. 1-Propanol at the silica/liquid interface retained the same ordered structure. In contrast, 2-propanol adopted different structures adsorbed to the solid/vapor and at the solid/ liquid interfaces. Specifically, the plane defined by 2-propanol's three carbon atoms changed orientation from being perpendicular to the surface (silica/vapor) to parallel to the surface (silica/liquid). Surface mediated liquid structure affected the solvation of adsorbed solutes. Resonance enhanced second harmonic generation (SHG) data showed that silica/alkane interfaces were significantly more polar than would be expected based on a solute's bulk solution solvatochromic behavior. Both silica/alcohol interfaces exhibited alkane-like polarity, a result that was interpreted in terms of a reduction in hydrogen bonding opportunities for adsorbed solutes.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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)

  15. 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.

  16. 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.

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

    PubMed

    Takeuchi, Kazumasa A; Sano, Masaki

    2010-06-11

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

  18. Charge-Controlled Colloids on Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

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

    PubMed

    Watarai, Hitoshi; Adachi, Kenta

    2009-10-01

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

  20. 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

  1. 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.

  2. 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.

  3. Density distribution in the liquid Hg-sapphire interface.

    PubMed

    Zhao, Meishan; Rice, Stuart A

    2011-04-28

    We present the results of a computer simulation study of the liquid density distribution normal to the interface between liquid Hg and the reconstructed (0001) face of sapphire. The simulations are based on an extension of the self-consistent quantum Monte Carlo scheme previously used to study the structure of the liquid metal-vapor interface. The calculated density distribution is in very good agreement with that inferred from the recent experimental data of Tamam et al. (J. Phys. Chem. Lett. 2010, 1, 1041-1045). We conclude that, to account for the difference in structure between the liquid Hg-vapor and liquid-Hg-reconstructed (0001) Al(2)O(3) interfaces, it is not necessary to assume there is charge transfer from the Hg to the Al(2)O(3). Rather, the available experimental data are adequately reproduced when the van der Waals interactions of the Al and O atoms with Hg atoms and the exclusion of electron density from Al(2)O(3) via repulsion of the electrons from the closed shells of the ions in the solid are accounted for.

  4. Ordering of solid microparticles at liquid crystal-water interfaces.

    PubMed

    Lin, I-Hsin; Koenig, Gary M; de Pablo, Juan J; Abbott, Nicholas L

    2008-12-25

    We report a study of the organization of solid microparticles at oil-water interfaces, where the oil is a thermotropic liquid crystal (LC). The study was motivated by the proposition that microparticle organization and LC ordering would be coupled at these interfaces. Surfactant-functionalized polystyrene microparticles were spread at air-water interfaces at prescribed densities and then raised into contact with supported films of nematic 4-pentyl-4'-cyanobiphenyl (5CB). Whereas this method of sample preparation led to quantitative transfer of microparticles from the air-water interface to an isotropic oil-water interface, forces mediated by the nematic order of 5CB were observed to rapidly displace microparticles laterally across the interface of the water upon contact with nematic 5CB, thus leading to a 65% decrease in the density of microparticles at the LC-water interface. These lateral forces were determined to be caused by microparticle-induced deformation of the LC, the energy of which was estimated to be approximately 10(4) kT. We also observed microparticles transferred to the LC-water interface to assemble into chainlike structures that were not seen when using isotropic oils, indicating the presence of LC-mediated interparticle interactions at this interface. Optical textures of the LC in the vicinity of the microparticles were consistent with formation of topological defects with dipolar symmetry capable of promoting the chaining of the microparticles. The presence of microparticles at the interface also impacted the ordering of the LCs, including a transition from parallel to perpendicular ordering of the LC with increasing microparticle density. These observations, when combined, demonstrate that LC-mediated interactions can direct the assembly of solid microparticles at LC-water interfaces and that the ordering of the LC is also strongly coupled to the presence of microparticles.

  5. 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

  6. 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.

  7. Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

    NASA Astrophysics Data System (ADS)

    Miranda, Paulo Barbeitas

    Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayers are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayers at liquid/vapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the conformational order of surfactant monolayers. The first part of the Thesis is concerned with surfactant monolayers at the air/water interface (Langmuir films). Surface crystallization of an alcohol Langmuir film and of liquid alkanes are studied and their phase transition behaviors are found to be of different nature, although driven by similar intermolecular interactions. The effect of crystalline order of Langmuir monolayers on the interfacial water structure is also investigated. It is shown that water forms a well-ordered hydrogen-bonded network underneath an alcohol monolayer, in contrast to a fatty acid monolayer which induces a more disordered structure. In the latter case, ionization of the monolayer becomes more significant with increase of the water pH value, leading to an electric-field-induced ordering of interfacial water molecules. We also show that the orientation and conformation of fairly complicated molecules in a Langmuir monolayer can be completely mapped out using a combination of SFG and second harmonic generation (SHG). For a quantitative analysis of molecular orientation at an interface, local-field corrections must be included. The second part is a study of self-assembled surfactant monolayers at the

  8. X-ray Reflectivity Study of the Adsorption of Azacrown Ether at Liquid-liquid Interface

    SciTech Connect

    Wojciechowski, Kamil; Gutberlet, Thomas; Tikhonov, Aleksey; Kashimoto, Kaoru; Schlossman, Mark

    2010-03-16

    Adsorption of diaza-18-crown-6 ether substituted with two tetracosane (-C{sub 24}H{sub 49}) alkyl chains (ACE-24) was investigated at the liquid-liquid interface. X-ray reflectivity measurements determined the structure of a close-packed monolayer at the hexane-water interface, which is consistent with conclusions drawn indirectly from earlier interfacial tension measurements on similar molecules. These data provide further insights into the role of interfacial processes involving azacrown ethers in ion separation techniques such as the permeation liquid membrane.

  9. 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.

  10. Nanoscale analysis of defect shedding from liquid crystal interfaces.

    PubMed

    Wincure, Benjamin M; Rey, Alejandro D

    2007-06-01

    A new defect-forming mechanism is predicted for liquid crystals undergoing an isotropic-to-nematic phase transition. A continuum theory characterizes how +1/2 defects (D<30 nm) evolve within and then shed from the interface (cross section approximately 100 nm) of a growing 5CB (4-n-4'-pentyl-4-cyanobiphenyl) nanodroplet (20 nmliquid crystal anisotropy and orientation during interfacial defect shedding.

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

    PubMed

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

    2009-10-01

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

  12. 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.

  13. 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.

  14. 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.

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

    PubMed

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

    2015-03-20

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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. 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.

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

    DOEpatents

    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, . . . ).

  5. 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.

  6. 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

  7. 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.

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

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Li, Christopher

    2012-02-01

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

  9. Instability of Liquid-liquid Interface Inhibited by Net under Electric Field

    NASA Astrophysics Data System (ADS)

    Fujimoto, Masanori; Tochitani, Hiro

    This paper deals with the stabilization of the formation of conic waves on a liquid-liquid interface under electric field. It is known that the interface becomes unstable when the electric field is perpendicularly applied to the interface, and the conic waves that are sometimes called Taylor cone are formed. The liquid drops are generated from these waves. In this study, the stabilization of the interface behavior has been achieved by setting up the metal-net of square mesh or rectangular mesh which restrains the movement of the interface, so that the wave is periodically generated in mesh. Distilled water and silicone oil are used in the experiment. A positive electrode of 80 mm×80 mm is set in the oil, and a negative one in water. Pictures of the phenomena of the interface are taken with the video camera of normal-speed or high-speed, and analyzed precisely on the monitor. As a result, the waves and drops formed are steady and uniform. The size of the mesh influences the formation period of the waves. When the size increases, the period lengthens. The mechanism of the drop formation divides into two types. One type is generated from the tip of the conic wave generated in a mesh. In the other type, the liquid column which results from the growth of the conic wave disintegrates, and becomes drops of comparatively large diameter. It is also shown that a liquid column can be formed by composing two reflection waves in a rectangular mesh.

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

    PubMed Central

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

    2014-01-01

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

  11. 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

  12. 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.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  15. 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.

  16. 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

  17. 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.

  18. [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.

  19. [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.

  20. 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

  1. Reflection and Transmission of Acoustic Waves at Semiconductor - Liquid Interface

    NASA Astrophysics Data System (ADS)

    Sharma, J. N.; Sharma, A.

    2011-09-01

    The study of reflection and transmission characteristics of acoustic waves at the interface of a semiconductor halfspace underlying an inviscid liquid has been carried out. The reflection and transmission coefficients of reflected and transmitted waves have been obtained for quasi-longitudinal (qP) wave incident at the interface from fluid to semiconductor. The numerical computations of reflection and transmission coefficients have been carried out with the help of Gauss elimination method by using MATLAB programming for silicon (Si), germanium (Ge) and silicon nitride (Si3N4) semiconductors. In order to interpret and compare, the computer simulated results are plotted graphically. The study may be useful in semiconductors, seismology and surface acoustic wave (SAW) devices in addition to engines of the space shuttles.

  2. 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

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

    NASA Astrophysics Data System (ADS)

    McDeavitt, S. M.; Billings, G. W.; Indacochea, J. E.

    2002-08-01

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

  4. 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.

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

    SciTech Connect

    Martinez-Miranda,L.; Hu, Y.

    2006-01-01

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

  6. Cu nanoparticles electrodeposited at liquid-liquid interfaces: a highly efficient catalyst for the hydrogen evolution reaction.

    PubMed

    Aslan, Emre; Patir, Imren Hatay; Ersoz, Mustafa

    2015-03-16

    The electrochemical deposition of Cu nanoparticles with an average diameter of approximately 25-35 nm has been reported at liquid-liquid interfaces by using the organic-phase electron-donor decamethylferrocene (DMFc). The electrodeposited Cu nanoparticles display excellent catalytic activity for the hydrogen evolution reaction (HER); this is the first reported catalytic effect of Cu nanoparticles at liquid-liquid interfaces.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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.}

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

    NASA Technical Reports Server (NTRS)

    2003-01-01

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

  18. 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.

  19. 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.

  20. 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.

  1. Ultrafast electronic spectroscopy for chemical analysis near liquid water interfaces: concepts and applications

    NASA Astrophysics Data System (ADS)

    Link, O.; Lugovoy, E.; Siefermann, K.; Liu, Y.; Faubel, M.; Abel, B.

    2009-07-01

    Electron spectroscopy for chemical analysis (ESCA) being conceptually a photoelectron spectroscopy is established as a chemically specific probe mostly for surface analysis. Liquid phase ESCA for volatile liquids has become possible through the development of the liquid microjet technique in vacuum enabling the measurement of liquid interface photoelectron emission at the high vapor pressure of volatile liquids. Recently we have been able to add the dimension of time to the liquid interface ESCA technique employing high-harmonics soft X-ray and UV/near IR femtosecond pulses in combination with liquid water micro beams in vacuum. The concepts as well as technical details are outlined and several characteristic applications are highlighted.

  2. Molecular vibrations at a liquid-liquid interface observed by fourth-order Raman spectroscopy.

    PubMed

    Fujiyoshi, Satoru; Ishibashi, Taka-aki; Onishi, Hiroshi

    2006-05-18

    Interface-selective, Raman-based observation of molecular vibrations is demonstrated at a liquid-liquid interface. An aqueous solution of oxazine 170 dye interfaced with hexadecane is irradiated with pump and probe light pulses of 630-nm wavelengths in 17-fs width. The ultrashort pulses are broadened due to group velocity dispersion when traveling through the hexadecane layer. The dispersion is optically corrected to give an optimized instrumental response. The pump pulse induces a vibrational coherence of the dye via impulsive stimulated Raman scattering. The probe pulse generates second-harmonic light at the interface. The efficiency of the generation is modulated as a function of the pump-probe delay by the coherently excited molecules. Fourier transformation of the modulated efficiency presents the frequency spectrum of the vibrations. Five bands are recognized at 534, 557, 593, 619, and 683 cm(-1). The pump-and-probe process induces a fourth-order optical response that is forbidden in a centrosymmetric media. The contribution of an undesired, cascaded optical process is quantitatively considered and excluded.

  3. Proteins at fluid interfaces: adsorption layers and thin liquid films.

    PubMed

    Yampolskaya, Galina; Platikanov, Dimo

    2006-12-21

    A review in which many original published results of the authors as well as many other papers are discussed. The structure and some properties of the globular proteins are shortly presented, special accent being put on the alpha-chymotrypsin (alpha-ChT), lysozyme (LZ), human serum albumin (HSA), and bovine serum albumin (BSA) which have been used in the experiments with thin liquid films. The behaviour of protein adsorption layers (PAL) is extensively discussed. The dynamics of PAL formation, including the kinetics of adsorption as well as the time evolution of the surface tension of protein aqueous solutions, are considered. A considerable place is devoted to the surface tension and adsorption isotherms of the globular protein solutions, the simulation of PAL by interacting hard spheres, the experimental surface tension isotherms of the above mentioned proteins, and the interfacial tension isotherms for the protein aqueous solution/oil interface. The rheological properties of PAL at fluid interfaces are shortly reviewed. After a brief information about the experimental methods for investigation of protein thin liquid (foam or emulsion) films, the properties of the protein black foam films are extensively discussed: the conditions for their formation, the influence of the electrolytes and pH on the film type and stability, the thermodynamic properties of the black foam films, the contact angles film/bulk and their dynamic hysteresis. The next center of attention concerns some properties of the protein emulsion films: the conditions for formation of emulsion black films, the formation and development of a dimpling in microscopic, circular films. The protein-phospholipid mixed foam films are also briefly considered.

  4. 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

  5. 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

  6. 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

  7. 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.

  8. 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...

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

    PubMed

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

    2007-11-15

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

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

    SciTech Connect

    Bramhaiah, K. John, Neena S.

    2014-04-24

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

  11. Label-free detection of DNA hybridization at a liquid|liquid interface.

    PubMed

    Vagin, Mikhail Yu; Trashin, Stanislav A; Karyakin, Arkady A; Mascini, Marco

    2008-02-15

    A novel electrochemical approach for label-free detection of DNA primary sequence has been proposed. The flow of nonelectroactive ions across a liquid|liquid interface was used as an electrochemical probe for detection of DNA hybridization. Disposable graphite screen-printed electrodes shielded with a thin layer of inert polymer plasticized with water-immiscible polar organic solvent were modified by probe oligonucleotide and used as a DNA sensor. The specific DNA coupling has been detected with impedance spectroscopy by decrease of ion-transfer resistance. The detection limit was of 10-8 M of target oligonucleotide. The reported sensor was suitable for discrimination of a single mismatch oligonucleotide from the full complementary one. The reported DNA sensor was advantageous over known physicochemical approaches, providing the most significant changes in the measured parameters.

  12. 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.

  13. 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.

  14. Temperature driven assembly of like-charged nanoparticles at non-planar liquid-liquid or gel-air interfaces

    NASA Astrophysics Data System (ADS)

    Zhuang, Qiang; Walker, David A.; Browne, Kevin P.; Kowalczyk, Bartlomiej; Beniah, Goliath; Grzybowski, Bartosz A.

    2014-04-01

    Gold nanoparticles (NPs) functionalized with 2-fluoro-4-mercaptophenol (FMP) ligands form densely packed NP films at liquid-liquid interfaces, including surfaces of liquid droplets. The process is driven by a gradual lowering of temperature that changes the solution's pH, altering both the energy of interfacial adsorption for NPs traveling from solution to the interface as well as the balance between electrostatic and vdW interactions between these particles. Remarkably, the system shows hysteresis in the sense that the films remain stable when the temperature is increased back to the initial value. The same phenomena apply to gel-air interfaces, enabling patterning of these wet materials with durable NP films.Gold nanoparticles (NPs) functionalized with 2-fluoro-4-mercaptophenol (FMP) ligands form densely packed NP films at liquid-liquid interfaces, including surfaces of liquid droplets. The process is driven by a gradual lowering of temperature that changes the solution's pH, altering both the energy of interfacial adsorption for NPs traveling from solution to the interface as well as the balance between electrostatic and vdW interactions between these particles. Remarkably, the system shows hysteresis in the sense that the films remain stable when the temperature is increased back to the initial value. The same phenomena apply to gel-air interfaces, enabling patterning of these wet materials with durable NP films. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05113g

  15. 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.

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

    PubMed

    Zhong, Shenghong; Jang, Chang-Hyun

    2015-09-21

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

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

    PubMed

    Abe, Kiharu; Sumi, Tomonari; Koga, Kenichiro

    2014-11-14

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

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. 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

  3. 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

  4. 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.

  5. (Electron transfer rates at semiconductor/liquid interfaces)

    SciTech Connect

    Lewis, N.S.

    1992-01-01

    Work has focused on several aspects of the fundamental chemistry and physics semiconductor/liquid junction behavior. These projects have been directed primarily towards GaAs/liquid contacts, because GaAs/liquid systems provide high energy conversion efficiencies and offer an opportunity to gain mechanistic understanding of the factors that are important to control in an efficient photoelectrochemical energy conversion system.

  6. [Electron transfer rates at semiconductor/liquid interfaces]. Progress report

    SciTech Connect

    Lewis, N.S.

    1992-08-01

    Work has focused on several aspects of the fundamental chemistry and physics semiconductor/liquid junction behavior. These projects have been directed primarily towards GaAs/liquid contacts, because GaAs/liquid systems provide high energy conversion efficiencies and offer an opportunity to gain mechanistic understanding of the factors that are important to control in an efficient photoelectrochemical energy conversion system.

  7. Self-assembly of an asymmetrically functionalized [6]helicene at liquid/solid interfaces.

    PubMed

    Balandina, Tatyana; van der Meijden, Maarten W; Ivasenko, Oleksandr; Cornil, David; Cornil, Jérôme; Lazzaroni, Roberto; Kellogg, Richard M; De Feyter, Steven

    2013-03-18

    STM brings to light chirality aspects of the self-assembly of a functionalized helicene at the interface between a liquid and the solid substrates, gold and graphite. This reveals conditions for conglomerate formation.

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

    PubMed

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

    2015-08-01

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

  9. Influence of surfactant tail branching and organization on the orientation of liquid crystals at aqueous-liquid crystal interfaces.

    PubMed

    Lockwood, Nathan A; de Pablo, Juan J; Abbott, Nicholas L

    2005-07-19

    We have examined the influence of two aspects of surfactant structure--tail branching and tail organization--on the orientational ordering (so-called anchoring) of water-immiscible, thermotropic liquid crystals in contact with aqueous surfactant solutions. First, we evaluated the influence of branches in surfactant tails on the anchoring of nematic liquid crystals at water-liquid crystal interfaces. We compared interfaces that were laden with one of three linear surfactants (sodium dodecyl sulfate, sodium dodecanesulfonate, and isomerically pure linear sodium dodecylbenzenesulfonate) to interfaces laden with branched sodium dodecylbenzenesulfonate. We carried out these experiments at 60 degrees C, above the Krafft temperatures of all the surfactants studied, and used the liquid crystal TL205 (a mixture of cyclohexane-fluorinated biphenyls and fluorinated terphenyls), which forms a nematic phase at 60 degrees C. Linear surfactants caused TL205 to assume a perpendicular orientation (homeotropic anchoring) above a threshold concentration of surfactant and parallel orientation (planar anchoring) at lower concentrations. In contrast, branched sodium dodecylbenzenesulfonate caused planar anchoring of TL205 at all concentrations up to the critical micelle concentration of the surfactant. Second, we used sodium dodecanesulfonate and a commercial linear sodium dodecylbenzenesulfonate to probe the influence of surfactant tail organization on the orientations of liquid crystals at water-liquid crystal interfaces. Commercial linear sodium dodecylbenzenesulfonate, which comprises a mixture of ortho and para isomers, has been previously characterized to form less ordered monolayers than sodium dodecanesulfonate at oil-water interfaces at room temperature. We found sodium dodecanesulfonate to cause homeotropic anchoring of both TL205 and 4'-pentyl-4-cyanobiphenyl (5CB, nematic at room temperature), whereas commercial linear sodium dodecylbenzenesulfonate caused predominantly

  10. Liquid-Liquid Interface Study of Hydrocarbons, Alcohols, and Cationic Surfactants with Water

    NASA Astrophysics Data System (ADS)

    Singh, Man; Matsuoka, Hideki

    Molecular interaction dynamics at liquid-liquid interface (LLI), involved nondispersive solution as compared with the interaction in bulk phase. Thereby, interfacial tension (IFT, mN/m) of LLI for four saturated hydrocarbons, six alcohols, and three cationic surfactants are reported at 298.15 K. The pentane, hexane, heptane, octane hydrocarbons and pentanol, hexanol, heptanol, 1-octanol, 2-octanol, and 1-decanol alcohols were used and IFT data were compared with 4 mm kg-1 dodecyltrimethylammoniumbromide (DTAB), trimethylsulfoxoniumiodide (TMSOI), methyltrioctylammoniumchloride (MTOAC) surfactants studied in benzene-water LLI. The IFT data are noted as hydrocarbons > DTAB > TMSOI > alcohols > MTOAC. The hydrocarbons and alcohols decreased IFT within 16 to 49% and 87 to 92%, respectively, whereas the surfactants within 78.3 to 95.9%. The alcohols developed interaction similar to surfactants and are denoted as nonionic surfactants for making mixtures of low IFT with hydrophilic and hydrophobic interactions to the level of the surfactants. The pentanol and MTOAC caused similar decrease in IFT so the pentanol developed the hydrophilic and hydrophobic interactions of the strength of MTOAC. Comparatively, the hydrocarbons showed lower decrease but the octane showed 49% decrease in IFT. Thus, the hydrocarbon with longer alkyl chain and the alcohol with shorter behave as good surfactants. The hydrocarbons with inductive effect on sigma bond between carbon atoms in alkyl chain also weakened the IFT and influenced the hydrophobic interactions. The MTOAC with four octyl units reduced 96% IFT so inductive effects monitor LLI dynamics.

  11. 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

  12. 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

  13. Behavior of ceramic particles at the solid-liquid metal interface in metal matrix composites

    NASA Technical Reports Server (NTRS)

    Stefanescu, D. M.; Dhindaw, B. K.; Kacar, S. A.; Moitra, A.

    1988-01-01

    Directional solidification results were obtained in order to investigate particle behavior at the solid-liquid interface in Al-2 pct Mg (cellular interface) and Al-6.1 pct Ni (eutectic interface) alloys. It is found that particles can be entrapped in the solid if adequate solidification rates and temperature gradients are used. Model results showed critical velocity values slightly higher than those obtained experimentally.

  14. 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

  15. 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...

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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

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

    PubMed

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

    2013-10-01

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

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

    PubMed

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

    2013-10-01

    A boundary condition for the Boltzmann equation (kinetic boundary condition, KBC) at the vapor-liquid interface of argon is constructed with the help of molecular dynamics (MD) simulations. The KBC is examined at a constant liquid temperature of 85 K in a wide range of nonequilibrium states of vapor. The present investigation is an extension of a previous one by Ishiyama, Yano, and Fujikawa [Phys. Rev. Lett. 95, 084504 (2005)] and provides a more complete form of the KBC. The present KBC includes a thermal accommodation coefficient in addition to evaporation and condensation coefficients, and these coefficients are determined in MD simulations uniquely. The thermal accommodation coefficient shows an anisotropic behavior at the interface for molecular velocities normal versus tangential to the interface. It is also found that the evaporation and condensation coefficients are almost constant in a fairly wide range of nonequilibrium states. The thermal accommodation coefficient of the normal velocity component is almost unity, while that of the tangential component shows a decreasing function of the density of vapor incident on the interface, indicating that the tangential velocity distribution of molecules leaving the interface into the vapor phase may deviate from the tangential parts of the Maxwell velocity distribution at the liquid temperature. A mechanism for the deviation of the KBC from the isotropic Maxwell KBC at the liquid temperature is discussed in terms of anisotropic energy relaxation at the interface. The liquid-temperature dependence of the present KBC is also discussed. PMID:24229188

  3. 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.

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

    PubMed

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

    2015-12-10

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

  5. 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.

  6. 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.

  7. 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

  8. Templated synthesis of amphiphilic nanoparticles at the liquid-liquid interface.

    PubMed

    Andala, Dickson M; Shin, Sun Hae Ra; Lee, Hee-Young; Bishop, Kyle J M

    2012-02-28

    A simple and reliable method is described to produce inorganic nanoparticles functionalized asymmetrically with domains of hydrophobic and hydrophilic ligands on their respective hemispheres. These amphiphilic, Janus-type particles form spontaneously by a thermodynamically controlled process, in which the particle cores and two competing ligands assemble at the interface between two immiscible liquids to reduce the interfacial energy. The asymmetric surface chemistry resulting from this process was confirmed using contact angle measurements of water droplets on nanoparticle monolayers deposited onto hydrophobic and hydrophilic substrates-particles presenting their hydrophobic face give contact angles of ∼96°, those presenting their hydrophilic face ∼19°. The spontaneous assembly process is rationalized by a thermodynamic model, which accounts both for the energetic contributions driving the assembly and for the entropic penalties that must be overcome. Consistent with the model, amphiphilic NPs form only when there is sufficient interfacial area to accommodate them; however, this potential limitation is easily overcome by mechanical agitation of the two-phase mixture. While it is straightforward to vary the ratio of hydrophobic and hydrophilic ligands, the accumulation of amphiphilic particles at the interface is maximal for ligand ratios near 1:1. In addition to gold nanoparticles and thiolate ligands, we demonstrate the generality of this approach by extending it to the preparation of amphiphilic iron oxide nanoparticles using two types of diol-terminated ligands. Depending on the material properties of the inorganic cores, the resulting amphiphilic particles should find applications as responsive particle surfactants that respond dynamically to optical (plasmonic particles) and/or magnetic (magnetic particles) fields.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Interface width and bulk stability: requirements for the simulation of deeply quenched liquid-gas systems.

    PubMed

    Wagner, A J; Pooley, C M

    2007-10-01

    Simulations of liquid-gas systems with interface terms evaluated by central difference discretizations are observed to fail to give accurate results for two reasons: the interface can get "stuck" on the lattice or a density overshoot develops around the interface. In the first case, the bulk densities can take a range of values, dependent on the initial conditions. In the second case, inaccurate bulk densities are found. We derived the minimum interface width required for the accurate simulation of liquid-gas systems with a diffuse interface. This criterion is demonstrated for lattice Boltzmann simulations of a van der Waals gas. Combining this criterion with predictions for the bulk stability defines the parameter range for stable and accurate simulation results even for high density ratios of over 1000.

  14. 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.

  15. 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.

  16. Mephisto - Research equipment for the study of solid/liquid interface destabilization in metal alloys

    NASA Astrophysics Data System (ADS)

    Favier, J. J.; Malmejac, Y.; Praizey, J. P.; Cambon, G.; Barillot, R.; Changeart, F. J.

    1982-09-01

    Preliminary results of a feasiblity study of space apparatus intended for solid/liquid destabilization in metal alloys, the Mephisto project, are presented. The phenomena that Mephisto will observe, the parameters it will measure, and the scientific studies that it will perform are stated. A general description is given of the instrument, its experimental tubes, and the experiment process. The environmental and thermal constraints, electrical characteristics, and the characteristics of the different signals are outlined. Finally, the requirements of the payload interfaces on which the equipment will be mounted are set forth, including mechanical/geometrical interfaces, thermal interfaces, and electrical interfaces.

  17. Holographic optical tweezers: manipulations at an air-liquid interface

    NASA Astrophysics Data System (ADS)

    Jesacher, Alexander; Fürhapter, Severin; Maurer, Christian; Bernet, Stefan; Ritsch-Marte, Monika

    2006-08-01

    By performing experiments at an air-water interface, we operate Holographic Optical Tweezers in a qualitatively new environment. In this regime, trapping and moving of micro particles may allow access to parameters like local viscosity and surface tension. Polystyrene micro beads are naturally stabilized in the interface due to a minimum in surface energy. For this reason, they can also be manipulated by light patterns with small axial field gradients, without causing the particles to escape due to scattering forces. In this manner, the interface provides a true two-dimensional "working environment", where particles can be manipulated with high effciency. For example, we demonstrate different optical "micro tools", which utilize scattering and gradient forces to enable controlled transport of matter within the surface.

  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. Molecular Mechanism of Transporting a Polarizable Iodide Anion Across the Water-CCl4 Liquid/Liquid Interface

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2007-04-07

    The result of transferring a polarizable iodide anion across the H2O-CCl4 liquid/liquid interface was investigated. The computed transfer free energy profile or potential of mean force exhibits a minimum near the Gibbs dividing surface, and its characteristics are similar to those of found in a corresponding water vapor/liquid interface study involving a smaller minimum free energy. Molecular dynamics simulations also were carried out to compare the concentrations of NaCl, NaBr, and NaI at H2O-vapor and H2O-CCl4 interfaces. While the concentration of bromide and iodide ions were lower at the H2O-CCl4 interface when compared to the H2O-vapor interface, the chloride ion concentrations were similar at both interfaces. Analysis of the solvation structures of iodide and chloride ions revealed that the more polarizable iodide ion was less solvated than the chloride ion at the interface. This characteristic brought the iodide ion in greater contact with CCl4 than the chloride ion, resulting in repulsive interactions with CCl4, which reduced its propensity for the interface. This work was performed at the Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The DOE Division of Chemical Sciences and the Scientific Computing Staff, Office of Science provided computer resources at the National Energy Research Supercomputer Center (Berkeley, California) that supported this research.

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

    PubMed

    D'Orazio, Giovanni; Fanali, Salvatore

    2013-11-22

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

  2. 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

  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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage 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.

  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. Brownian motion near a liquid-gas interface

    NASA Astrophysics Data System (ADS)

    Benavides-Parra, Juan Carlos; Jacinto-Méndez, Damián; Brotons, Guillaume; Carbajal-Tinoco, Mauricio D.

    2016-09-01

    By using digital video microscopy, we study the three-dimensional displacement of fluorescent colloidal particles that are located close to a water-air interface. Our technique takes advantage of the diffraction pattern generated by fluorescent spheres that are found below the focal plane of the microscope objective. By means of image analysis software, we are able to determine the spatial location of a few beads in a sequence of digital images, which allows us to reconstruct their trajectories. From their corresponding mean square displacements, we get the diffusion coefficients in the directions parallel and perpendicular to the interface. We find a qualitatively different kind of diffusion between the two directions, in agreement with theoretical predictions that are obtained from established models as well as our own proposals. Quite interesting, we observe the enhanced Brownian motion in the parallel direction.

  8. 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

  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. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. On the theory of electron transfer reactions at semiconductor electrode/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Gao, Yi Qin; Georgievskii, Yuri; Marcus, R. A.

    2000-02-01

    Electron transfer reaction rate constants at semiconductor/liquid interfaces are calculated using the Fermi Golden Rule and a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the electronic structures of semiconductors with surfaces and are compared. The maximum electron transfer rate constants at Si/viologen2+/+ and InP/Me2Fc+/0 interfaces are computed using the tight-binding type calculations for the solid and the extended-Hückel for the coupling to the redox agent at the interface. These results for the bulk states are compared with the experimentally measured values of Lewis and co-workers, and are in reasonable agreement, without adjusting parameters. In the case of InP/liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

  16. 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

  17. 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.

  18. Electron transport across metal/discotic liquid crystal interfaces

    NASA Astrophysics Data System (ADS)

    Boden, N.; Bushby, R. J.; Clements, J.; Movaghar, B.

    1998-03-01

    Electron transport across micron thick films of columnar hexagonal discotic liquid crystal phases homeotropically aligned between metal electrode surfaces has been studied both experimentally and theoretically. These molecules are unique in their combination of charge transport along individual molecular columns with liquidlike self-organization. Typical of organic insulators, a high resistance Ohmic regime is evident at fields of less than 0.05 MV cm-1, due to a low concentration of chemical impurities (n<109cm-3), and a space-charge injection regime at higher fields. Breakdown fields are reasonably high: in hexakis(hexyloxy)triphenylene they reach ˜5 MV cm-1 at room temperature. Our results show that triphenylene-based discotics form an excellent class of highly ordered optically transparent insulators. At high temperatures and high fields the current is injection controlled and exhibits typical tunneling and space charge limited, nonlinear I-V characteristics. Dramatic jumps in injection currents are observed at phase transitions. The change at the crystalline to liquid crystalline phase transition is mainly due to more efficient "wetting" of the electrode surface in the liquid crystalline phase, whilst at the liquid crystalline to isotropic phase transition it arises from the enhancement in the molecular mobility. The concepts of semiconducting gaps, band mobilities, and carrier injection rates are extended to these new materials. The experimental observations are interpreted in a framework which takes into account the important role played by liquidlike dynamics in establishing the microscopic structural order in, what is, otherwise a highly anisotropic and weakly bonded "molecular crystal."

  19. 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.

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

    PubMed

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

    2015-07-01

    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.

  1. 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.

  2. Aqueous interfaces with hydrophobic room-temperature ionic liquids: a molecular dynamics study.

    PubMed

    Chaumont, A; Schurhammer, R; Wipff, G

    2005-10-13

    We report a molecular dynamics study of the interface between water and (macroscopically) water-immiscible room-temperature ionic liquids "ILs", composed of PF6(-) anions and butyl- versus octyl-substituted methylimidazolium+ cations (noted BMI+ and OMI+). Because the parameters used to simulate the pure ILs were found to exaggerate the water/IL mixing, they have been modified by scaling down the atomic charges, leading to better agreement with the experiment. The comparison of [OMI][PF6] versus [BMI][PF6] ILs demonstrates the importance of the N-alkyl substituent on the extent of solvent mixing and on the nature of the interface. With the most hydrophobic [OMI][PF6] liquid, the "bulk" IL phase is dryer than with the [BMI][PF6] liquid. At the interface, the OMI+ cations retain direct contacts with the bulk IL, whereas the more hydrophilic PF6(-) anions gradually dilute in the local water micro-environment and are thus isolated from the "bulk" IL. The interfacial OMI+ cations are ordered with their imidazolium moiety pointing toward the aqueous side and their octyl chains toward the IL side of the interface. With the [BMI][PF6] liquid, the system gradually evolves from an IL-rich to a water-rich medium, leading to an ill-defined interfacial domain with high intersolvent mixing. As a result, the BMI+ cations are isotropically oriented "at the interface". Because the imidazolium cations are more hydrophobic than the PF6(-) anions, the charge distribution at the interface is heterogeneous, leading to a positive electrostatic potential at the interface with the two studied ILs. Mixing-demixing simulations on [BMI][PF6]/water mixtures are also reported, comparing Ewald versus reaction field treatments of electrostatics. Phase separation is very slow (at least 30 ns), in marked contrast with mixtures involving classical organic liquids, which separate in less than 0.5 ns at the microscopic level. The results allow us to better understand the specificity of the aqueous

  3. Enhancing solid-liquid interface thermal transport using self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Tian, Zhiting; Marconnet, Amy; Chen, Gang

    2015-05-01

    The thermal conductance across solid-liquid interfaces is of interest for many applications. Using time-domain thermoreflectance, we measure the thermal conductance across self-assembled monolayers, grown on Au, to ethanol. We systematically study the effect of different functional groups and the alkyl chain length on the thermal conductance. The results show that adding this extra molecular layer can enhance the thermal transport across the solid-liquid interface. While the enhancement is up to 5 times from hexanedithiol, the enhancement from hexanethiol, undecanethiol, and hexadecanethiol is approximately a factor of 2.

  4. 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

  5. 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.

  6. 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

  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. 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

  9. 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

  10. Intrusion of fluids into nanogrooves: how geometry determines the shape of the gas-liquid interface.

    PubMed

    Bohlen, H; Parry, A O; Díaz-Herrera, E; Schoen, M

    2008-01-01

    We study the shape of gas-liquid interfaces forming inside rectangular nanogrooves (i.e., slit-pores capped on one end). On account of purely repulsive fluid-substrate interactions the confining walls are dry (i.e., wet by vapor) and a liquid-vapor interface intrudes into the nanogrooves to a distance determined by the pressure (i.e., chemical potential). By means of Monte Carlo simulations in the grand-canonical ensemble (GCEMC) we obtain the density rho(z) along the midline (x = 0) of the nanogroove for various geometries (i.e., depths D and widths L) of the nanogroove. We analyze the density profiles with the aid of an analytic expression which we obtain through a transfer-matrix treatment of a one-dimensional effective interface Hamiltonian. Besides geometrical parameters such as D and L , the resulting analytic expression depends on temperature T , densities of coexisting gas and liquid phases in the bulk rho g,l(x) and the interfacial tension gamma. The latter three quantities are determined in independent molecular dynamics simulations of planar gas-liquid interfaces. Our results indicate that the analytic formula provides an excellent representation of rho(z) as long as L is sufficiently small. At larger L the meniscus of the intruding liquid flattens. Under these conditions the transfer-matrix analysis is no longer adequate and the agreement between GCEMC data and the analytic treatment is less satisfactory.

  11. 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.

  12. 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.

  13. Two-Dimensional Crystals of Icosahedral Viruses at Liquid interfaces

    NASA Astrophysics Data System (ADS)

    Fukuto, Masafumi; Yang, Lin; Checco, Antonio; Kuzmenko, Ivan; Nguyen, Quyen; Mank, Nick; Wang, Qian

    2012-02-01

    Two-dimensional (2D) assembly of turnip yellow mosaic virus (TYMV) on cationic lipid monolayers is investigated at the air-water interface. TYMV, an icosahedral virus with a diameter of 28 nm, exhibits well-defined roughness, charge distribution, and hydrophilic/hydrophobic patches on its surface. The electrostatic attraction to the lipid-coated aqueous interface provides means to impose a specific virus orientation and hence reduce the number of possible inter-particle interactions. The 2D geometry is particularly advantageous in dissecting the role of anisotropy in aqueous-media assembly, which involves various types of similarly weak interactions. We show that the assembly approach used not only facilitates crystallization but also provides insights on how complex anisotropic interactions can be exploited to generate long-range order. Specifically, we report an in situ x-ray scattering observation of novel 2D crystal forms of TYMV that reflect the virus' icosahedral symmetry. The symmetry, shape, and surface heterogeneities of TYMV suggest a mechanism by which these crystals are stabilized by a combination of hydrophobic, electrostatic, and steric interactions.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment.

    PubMed

    Price, Andrew D; Schwartz, Daniel K

    2007-02-01

    The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  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.

  4. 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.

  5. 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.

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

    PubMed

    Kwon, Bomjun J

    2012-06-01

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

  7. 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.

  8. 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.

  9. Dynamic equilibrium under vibrations of H2 liquid-vapor interface at various gravity levels

    NASA Astrophysics Data System (ADS)

    Gandikota, G.; Chatain, D.; Lyubimova, T.; Beysens, D.

    2014-06-01

    Horizontal vibration applied to the support of a simple pendulum can deviate from the equilibrium position of the pendulum to a nonvertical position. A similar phenomenon is expected when a liquid-vapor interface is subjected to strong horizontal vibration. Beyond a threshold value of vibrational velocity the interface should attain an equilibrium position at an angle to the initial horizontal position. In the present paper experimental investigation of this phenomenon is carried out in a magnetic levitation device to study the effect of the vibration parameters, gravity acceleration, and the liquid-vapor density on the interface position. The results compare well with the theoretical expression derived by Wolf [G. H. Wolf, Z. Phys. B 227, 291 (1969), 10.1007/BF01397662].

  10. Dynamic equilibrium under vibrations of H₂ liquid-vapor interface at various gravity levels.

    PubMed

    Gandikota, G; Chatain, D; Lyubimova, T; Beysens, D

    2014-06-01

    Horizontal vibration applied to the support of a simple pendulum can deviate from the equilibrium position of the pendulum to a nonvertical position. A similar phenomenon is expected when a liquid-vapor interface is subjected to strong horizontal vibration. Beyond a threshold value of vibrational velocity the interface should attain an equilibrium position at an angle to the initial horizontal position. In the present paper experimental investigation of this phenomenon is carried out in a magnetic levitation device to study the effect of the vibration parameters, gravity acceleration, and the liquid-vapor density on the interface position. The results compare well with the theoretical expression derived by Wolf [G. H. Wolf, Z. Phys. B 227, 291 (1969)].

  11. Dynamic equilibrium under vibrations of H₂ liquid-vapor interface at various gravity levels.

    PubMed

    Gandikota, G; Chatain, D; Lyubimova, T; Beysens, D

    2014-06-01

    Horizontal vibration applied to the support of a simple pendulum can deviate from the equilibrium position of the pendulum to a nonvertical position. A similar phenomenon is expected when a liquid-vapor interface is subjected to strong horizontal vibration. Beyond a threshold value of vibrational velocity the interface should attain an equilibrium position at an angle to the initial horizontal position. In the present paper experimental investigation of this phenomenon is carried out in a magnetic levitation device to study the effect of the vibration parameters, gravity acceleration, and the liquid-vapor density on the interface position. The results compare well with the theoretical expression derived by Wolf [G. H. Wolf, Z. Phys. B 227, 291 (1969)]. PMID:25019875

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Pak, Hyuk Kyu; Moon, Jong Kyun

    2014-11-01

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

  15. 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.

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

    NASA Technical Reports Server (NTRS)

    Lin, Chin-Shun

    1989-01-01

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

  17. 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.

  18. 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.

  19. 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

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

    PubMed

    Wang, Xin; Mi, Jianguo; Zhong, Chongli

    2013-04-28

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

  1. 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.

  2. 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.

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

    PubMed

    Wang, Xin; Mi, Jianguo; Zhong, Chongli

    2013-04-28

    A density functional approach is presented to describe the crystal-liquid interfaces and crystal nucleations of Lennard-Jones fluid. Within the theoretical framework, the modified fundamental measure theory is applied to describe the free energy functional of hard sphere repulsion, and the weighted density method based on first order mean spherical approximation is used to describe the free energy contribution arising from the attractive interaction. The liquid-solid equilibria, density profiles within crystal cells and at liquid-solid interfaces, interfacial tensions, nucleation free energy barriers, and critical cluster sizes are calculated for face-centered-cubic and body-centered-cubic nucleus. Some results are in good agreement with available simulation data, indicating that the present model is quantitatively reliable in describing nucleation thermodynamics of Lennard-Jones fluid. PMID:23635162

  4. A mean field approach for computing solid-liquid surface tension for nanoscale interfaces.

    PubMed

    Chiu, Chi-cheng; Ranatunga, R J K Udayana; Torres Flores, David; Pérez, D Vladimir; Moore, Preston B; Shinoda, Wataru; Nielsen, Steven O

    2010-02-01

    The physical properties of a liquid in contact with a solid are largely determined by the solid-liquid surface tension. This is especially true for nanoscale systems with high surface area to volume ratios. While experimental techniques can only measure surface tension indirectly for nanoscale systems, computer simulations offer the possibility of a direct evaluation of solid-liquid surface tension although reliable methods are still under development. Here we show that using a mean field approach yields great physical insight into the calculation of surface tension and into the precise relationship between surface tension and excess solvation free energy per unit surface area for nanoscale interfaces. Previous simulation studies of nanoscale interfaces measure either excess solvation free energy or surface tension, but these two quantities are only equal for macroscopic interfaces. We model the solid as a continuum of uniform density in analogy to Hamaker's treatment of colloidal particles. As a result, the Hamiltonian of the system is imbued with parametric dependence on the size of the solid object through the integration limits for the solid-liquid interaction energy. Since the solid-liquid surface area is a function of the size of the solid, and the surface tension is the derivative of the system free energy with respect to this surface area, we obtain a simple expression for the surface tension of an interface of arbitrary shape. We illustrate our method by modeling a thin nanoribbon and a solid spherical nanoparticle. Although the calculation of solid-liquid surface tension is a demanding task, the method presented herein offers new insight into the problem, and may prove useful in opening new avenues of investigation.

  5. Diffusion at the liquid-vapor interface of an aqueous ionic solution utilizing a dual simulation technique

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2005-07-21

    The recently proposed dual simulation technique [J. Phys. Chem. B 2004, 108, 6595.] is used to determine the diffusion coefficients for a variety of regions of a 2.2 sodium chloride aqueous solution with a vapor-liquid interface. For the calculation of the diffusion coefficient perpendicular to the interface, a modest modification to the dual simulation method was applied, while values parallel to the interface were determined without any modification to the method. Tests were performed, verifying the quality of modified method, showing it to be a well-defined self-consistent technique for the determination of the diffusion coefficient perpendicular to the interface. The diffusion of all species was shown to be isotropic far away from the interface, as expected, but at different regions in the interface, the diffusion coefficients parallel and perpendicular to the interface were not the same. Specifically, for water the diffusion coefficient perpendicular to the interface was higher in the liquid edge of the interface, but at the low density region, an opposite trend could be observed. For sodium and chloride ions, the diffusion parallel to the interface was higher than the values perpendicular to the interface near their concentration peaks. The diffusion of all species was generally higher at the vapor-liquid interface than in the middle of the liquid.

  6. Simulation and theory of ions at atmospherically relevant aqueous liquid-air interfaces.

    PubMed

    Tobias, Douglas J; Stern, Abraham C; Baer, Marcel D; Levin, Yan; Mundy, Christopher J

    2013-01-01

    Chemistry occurring at or near the surface 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 capable of reproducing simulation and experimental data on ion behavior at aqueous interfaces.

  7. The [BMI][Tf2N] ionic liquid/water binary system: a molecular dynamics study of phase separation and of the liquid-liquid interface.

    PubMed

    Sieffert, N; Wipff, G

    2006-07-01

    We report molecular dynamics (MD) simulations of the aqueous interface of the hydrophobic [BMI][Tf2N] ionic liquid (IL), composed of 1-butyl-3-methylimidazolium cations (BMI+) and bis(trifluoromethylsulfonyl)imide anions (Tf2N-). The questions of water/IL phase separation and properties of the neat interface are addressed, comparing different liquid models (TIP3P vs TIP5P water and +1.0/-1.0 vs +0.9/-0.9 charged IL ions), the Ewald vs the reaction field treatments of the long range electrostatics, and different starting conditions. With the different models, the "randomly" mixed liquids separate much more slowly (in 20 to 40 ns) than classical water-oil mixtures do (typically, in less than 1 ns), finally leading to distinct nanoscopic phases separated by an interface, as in simulations which started with a preformed interface, but the IL phase is more humid. The final state of water in the IL thus depends on the protocol and relates to IL heterogeneities and viscosity. Water mainly fluctuates in hydrophilic basins (rich in O(Tf2N) and aromatic CH(BMI) groups), separated by more hydrophobic domains (rich in CF3(Tf2N) and alkyl(BMI) groups), in the form of monomers and dimers in the weakly humid IL phase, and as higher aggregates when the IL phase is more humid. There is more water in the IL than IL in water, to different extents, depending on the model. The interface is sharper and narrower (approximately 10 A) than with the less hydrophobic [BMI][PF6] IL and is overall neutral, with isotropically oriented molecules, as in the bulk phases. The results allow us to better understand the analogies and differences of aqueous interfaces with hydrophobic (but hygroscopic) ILs, compared to classical organic liquids.

  8. 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.

  9. Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces.

    PubMed

    Maldonado-Valderrama, Julia; Fainerman, Valentin B; Galvez-Ruiz, M José; Martín-Rodriguez, Antonio; Cabrerizo-Vílchez, Miguel A; Miller, Reinhard

    2005-09-22

    The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.

  10. 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.

  11. 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.

  12. Contact-line deformation around a spherical particle at an anisotropic liquid interface

    NASA Astrophysics Data System (ADS)

    Senbil, Nesrin; He, Wei; Dinsmore, Anthony

    2015-03-01

    The shape of the contact line around a particle determines its interaction with other particles at liquid interfaces. Thus, the shape of the interface and contact line is significant for self-assembly and many other applications of colloids. In our experiments, we used PDMS-coated millimeter-sized glass spheres to avoid pinning. The contact line around the sphere is observed at initially flat, cylindrical-like and saddle-like shapes with a camera placed perpendicular to the plane of the initially flat interface. Unlike flat interfaces, at anisotropic interfaces, the contact line around the sphere is not circular. Our results demonstrate that the quadrupolar deformation of the contact line (z2) increases with deviatoric curvature (anisotropy) of the interface (D0) . For instance, for a PDMS-coated glass sphere with a diameter 3.2mm, as D0 increases from 0 to 0.12mm-1, z2 increases from 0 to about 0.3mm. We will discuss the relation among z2, D0, mean contact radius, particle radius, and contact angle and compare to theory. Our results are important to understand the assembly of particles at anisotropically curved interfaces. This work is funded by the NSF through CBET-0967620 and by the Gulf of Mexico Research Initiative through the C-MEDS consortium.

  13. Coupling capillary electrochromatography with mass spectrometry by using a liquid-junction nano-spray interface.

    PubMed

    D'Orazio, Giovanni; Fanali, Salvatore

    2010-06-18

    Capillary electrochromatography (CEC) was coupled with mass spectrometry (MS) for the separation of some selected pesticides and drug enantiomers. CEC separations were carried out in fused silica capillaries packed with either 5microm RP(18) silica or 5microm silica modified vancomycin particles. The capillary column was connected with the MS utilizing a laboratory-made liquid-junction interface equipped with a 50microm I.D. capillary-tip positioned at a few mm from the orifice of the MS. The CEC-MS set-up was operated without external pressure assistance during the electrochromatographic run commonly used to avoid bubble formation. However a hydrostatic pressure of a few kPa was applied only to the liquid-junction interface to optimize the ion-spray due to the low I.D. of the capillary-tip. In order to optimize the CEC-MS method, several experimental parameters were studied, namely the inlet pressure, the hydrostatic pressure into the liquid-junction interface, the type of sheath-liquid and the mobile phase. The application of an inlet pressure influenced only analyte retention times that were shortened by increasing the pressure. On the contrary the hydrostatic pressure applied to the interface increased the flow rate into the tip also increasing the ion-signal recorded in the mass spectrometry. The ion-signal raised almost linearly by increasing the outlet pressure till 3.5kPa and then decreased. The separation of the selected pesticides was not influenced at all changing the hydrostatic pressure on the interface. Some basic enantiomeric compounds of pharmaceutical interest were successfully separated by CEC achieving good resolution. They were detected by MS with limit of detection in a range of 0.24-0.60microg/mL.

  14. 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.

  15. 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.

  16. Structure and dynamics of interfaces between two coexisting liquid-crystalline phases.

    PubMed

    Praetorius, Simon; Voigt, Axel; Wittkowski, Raphael; Löwen, Hartmut

    2013-05-01

    A phase-field-crystal model is used to access the structure and thermodynamics of interfaces between two coexisting liquid-crystalline phases in two spatial dimensions. Depending on the model parameters, there is a variety of possible coexistences between two liquid-crystalline phases, including a plastic triangular crystal (PTC). Here, we numerically calculate the profiles for the mean density and for the nematic order tensor across the interface for isotropic-PTC and columnar-PTC (or equivalently smectic-A-PTC) phase coexistence. As a general finding, the width of the interface with respect to the nematic order parameter characterizing the orientational order is larger than the width of the mean-density interface. In approaching the interface from the PTC side, at first, the mean density goes down, and then the nematic order parameter follows. The relative shift in the two profiles can be larger than a full lattice constant of the plastic crystal. Finally, we also present numerical results for the dynamic relaxation of an initial order-parameter profile towards its equilibrium interfacial profile. Our predictions for the interfacial profiles can, in principle, be verified in real-space experiments of colloidal dispersions.

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

    SciTech Connect

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

    2011-06-16

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

  18. 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.

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

    PubMed Central

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

    2015-01-01

    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

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Steady thermocapillary flows in a two-layer liquid system with flat interfaces

    NASA Astrophysics Data System (ADS)

    del Arco, E. Crespo; Extremet, G. P.; Sani, R. L.

    1993-01-01

    Steady thermocapillary convection is studied in a system of two flat, superposed layers of immiscible liquids with two fluid-fluid interfaces in a configuration similar to that of an encapsulated crystal growth. The layers are bounded on the sides by isothermal vertical walls maintained at different constant temperatures. A simplified analytical solution is used initially to explore different potential flow regimes in a parameter space of large dimensionality. Then the coupled Navier-Stokes and heat transfer equations are solved numerically with a finite element method via FIDAP, in a rectangular cavity filled with two immiscible liquids in the absence of a gravitational field.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  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.

  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. 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.

  15. 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

  16. 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.

  17. Crystalline Gibbs monolayers of DNA-capped nanoparticles at the air-liquid interface.

    PubMed

    Campolongo, Michael J; Tan, Shawn J; Smilgies, Detlef-M; Zhao, Mervin; Chen, Yi; Xhangolli, Iva; Cheng, Wenlong; Luo, Dan

    2011-10-25

    Using grazing-incidence small-angle X-ray scattering in a special configuration (parallel SAXS, or parSAXS), we mapped the crystallization of DNA-capped nanoparticles across a sessile droplet, revealing the formation of crystalline Gibbs monolayers of DNA-capped nanoparticles at the air-liquid interface. We showed that the spatial crystallization can be regulated by adjusting both ionic strength and DNA sequence length and that a modified form of the Daoud-Cotton model could describe and predict the resulting changes in interparticle spacing. Gibbs monolayers at the air-liquid interface provide an ideal platform for the formation and study of equilibrium nanostructures and may afford exciting routes toward the design of programmable 2D plasmonic materials and metamaterials.

  18. 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.

  19. Formation of Organic Peroxides and Ethers at Post-Discharge Plasma Plume-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Begliarbekov, Milan; Kotowich, Steven; Tarnovsky, Vladimir

    2009-03-01

    A direct current (DC) micro-hollow cathode plasma source operating in a mixed glow-streamer regime was used to generate an atmospheric pressure N2 discharge. The post-discharge plume / afterglow was interfaced with a target liquid-phase solution, and caused a change in the chemistry of the target solution. In the present work we study the interaction of an N2 plume with a mixture of 2-methyl-1-propanol and hexane, which results in the formation of organic peroxides and ethers at the plume-liquid interface. The presence of the peroxide and ether functional groups is established by ^1H-NMR, FTIR, and Raman spectra of the reaction products. Fast Atom Bombardment (FAB) mass spectrometry is also used to further characterize the reaction products.

  20. 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

  1. 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.

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

    NASA Astrophysics Data System (ADS)

    Zhu, Peixi

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

  3. 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

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

    PubMed

    Gobrogge, Eric A; Walker, Robert A

    2014-08-01

    Nonlinear vibrational spectroscopy experiments examined solvent organization at the silica/binary solvent interface where the binary solvent consisted of methanol and acetonitrile in varying mole fractions. Data were compared with surface vibrational spectra acquired from silica surfaces exposed to a vapor phase saturated with the same binary solvent mixtures. Changes in vibrational band intensities suggest that methanol ideally adsorbs to the silica/vapor interface but acetonitrile accumulates in excess relative to vapor-phase composition. At the silica/liquid interface, acetonitrile's signal increases until a solution phase mole fraction of ∼0.85. At higher acetonitrile concentrations, acetonitrile's signal decreases dramatically until only a weak signature persists with the neat solvent. This behavior is ascribed to dipole-paired acetonitrile forming a bilayer with the first sublayer associating with surface silanol groups and a second sublayer consisting of weakly associating, antiparallel partners. On the basis of recent simulations, we propose that the second sublayer accumulates in excess. PMID:26277964

  5. 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.

  6. 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.

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

    PubMed

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

    2013-10-01

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

  8. 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.

  9. 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.

  10. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

  12. X-ray and neutron surface scattering for studying lipid/polymer assemblies at the air-liquid and solid-liquid interfaces.

    PubMed

    Majewski, J; Kuhl, T L; Wong, J Y; Smith, G S

    2000-09-01

    Simple mono- and bilayers, built of amphiphilic molecules and prepared at air-liquid or solid-liquid interfaces, can be used as models to study such effects as water penetration, hydrocarbon chain packing, and structural changes due to head group modification. In the paper, we will discuss neutron and X-ray reflectometry and grazing incidence X-ray diffraction techniques used to explore structures of such ultra-thin organic films in different environments. We will illustrate the use of these methods to characterize the morphologies of the following systems: (i) polyethylene glycol-modified distearoylphosphatidylethanolamine monolayers at air-liquid and solid-liquid interfaces; and (ii) assemblies of branched polyethyleneimine polymer and dimyristoylphophatidylcholine lipid at solid-liquid interfaces.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Influence of magnetic field on the orientation of anisotropic magnetic particles at liquid interfaces.

    PubMed

    Newton, Bethany J; Brakke, Kenneth A; Buzza, D Martin A

    2014-12-21

    We study theoretically the influence of an external magnetic field on the orientation of an ellipsoidal magnetic particle adsorbed at a liquid interface. Using the finite element program Surface Evolver, we calculate the equilibrium meniscus shape around the ellipsoidal particle and its equilibrium tilt angle with respect to the undeformed interface θt when a magnetic field B is applied perpendicular to the interface. We find that as we increase field strength, θt increases and at a critical magnetic field Bc1 and tilt angle θc1, the particle undergoes a discontinuous transition to the 'perpendicular' orientation (θt = 90°). Our results agree qualitatively with the simplified theory of Bresme and Faraudo [F. Bresme and J. Faraudo, J. Phys.: Condens. Matter, 2007, 19, 375110] which assumes that the liquid interface is flat, while they agree quantitatively with recent lattice-Boltzmann simulations of Davies et al. [G. Davies et al., Soft Matter, 2014, 10, 6742] which account for the deformation of the liquid meniscus. We also show for the first time that upon reducing the external magnetic field, at a critical magnetic field Bc2 < Bc1, the particle undergoes a second discontinuous transition from the perpendicular orientation to a finite tilt angle θc2 < θc1. In other words, for micron-sized particles where the thermal energy kBT is negligible compared to the interfacial energy, the tilt angle vs. magnetic field curve exhibits hysteresis behaviour. Due to the higher degree of accuracy of the Surface Evolver method, we are able to analyse the behaviour of the particles near these orientational transitions accurately and study how the critical quantities Bc1, Bc2, θc1 and θc2 vary with particle aspect ratio and contact angle.

  19. 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.

  20. Liquid-liquid interface assisted synthesis of size- and thickness-controlled Ag nanoplates

    SciTech Connect

    Jin Mingshang; Kuang Qin; Han Xiguang; Xie Shuifen; Xie Zhaoxiong; Zheng Lansun

    2010-06-15

    Here we proposed a synthetic method of high-purity Ag nanoplates by the reduction of aqueous Ag{sup +} ions at the aqueous-organic interface with the reductant ferrocene. We demonstrated that the as-prepared Ag nanoplates can be widely tunable from 600 nm to 7 {mu}m in size and from 10 to 35 nm in thickness, simply by adjusting the component of organic phase. To our knowledge, there are few methods to tailor the size and the thickness of metal nanoplates in such a large range although many efforts have been made aiming to realize it. Our proposed synthetic strategy is rapid, template-free, seed-less, and high-yield, and could be applied to synthesize analogous two-dimensional nanostructures of other noble metals, such as Pt, Au, and Pd. - Graphical abstract: High-purity Ag nanoplates were synthesized by the reduction of aqueous Ag{sup +} ions at the aqueous-organic interface with the reductant ferrocene, the size and thickness of which were widely tunable.

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

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

    PubMed

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

    2013-11-01

    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.

  7. 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.

  8. Bioinspired super-antiwetting interfaces with special liquid-solid adhesion.

    PubMed

    Liu, Mingjie; Zheng, Yongmei; Zhai, Jin; Jiang, Lei

    2010-03-16

    Super-antiwetting interfaces, such as superhydrophobic and superamphiphobic surfaces in air and superoleophobic interfaces in water, with special liquid-solid adhesion have recently attracted worldwide attention. Through tuning surface microstructures and compositions to achieve certain solid/liquid contact modes, we can effectively control the liquid-solid adhesion in a super-antiwetting state. In this Account, we review our recent progress in the design and fabrication of these bioinspired super-antiwetting interfaces with special liquid-solid adhesion. Low-adhesion superhydrophobic surfaces are biologically inspired, typically by the lotus leaf. Wettability investigated at micro- and nanoscale reveals that the low adhesion of the lotus surface originates from the composite contact mode, a microdroplet bridging several contacts, within the hierarchical structures. Recently high-adhesion superhydrophobic surfaces have also attracted research attention. These surfaces are inspired by the surfaces of gecko feet and rose petals. Accordingly, we propose two biomimetic approaches for the fabrication of high-adhesion superhydrophobic surfaces. First, to mimic a sticky gecko's foot, we designed structures with nanoscale pores that could trap air isolated from the atmosphere. In this case, the negative pressure induced by the volume change of sealed air as the droplet is pulled away from surface can produce a normal adhesive force. Second, we constructed microstructures with size and topography similar to that of a rose petal. The resulting materials hold air gaps in their nanoscale folds, controlling the superhydrophobicity in a Wenzel state on the microscale. Furthermore, we can tune the liquid-solid adhesion on the same superhydrophobic surface by dynamically controlling the orientations of microstructures without altering the surface composition. The superhydrophobic wings of the butterfly (Morpho aega) show directional adhesion: a droplet easily rolls off the surface

  9. 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.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    The atom-scale characterisation of interfaces between transition metal oxides and liquid water is fundamental to our mechanistic understanding of diverse phenomena ranging from crystal growth to biogeochemical transformations to solar fuel production. Here we report on the results of large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface. A specific focus is placed on understanding how different terminations of the same surface influence surface solvation. We find that the two dominant terminations for the hematite(001) surface exhibit strong differences both in terms of the active species formed on the surface and the strength of surface solvation. According to present simulations, we find that charged oxyanions (-O-) and doubly protonated oxygens (-OH2+ ) can be formed on the iron terminated layer via autoionization of neutral -OH groups. No such charged species are found for the oxygen terminated surface. In addition, the missing iron sublayer in the iron terminated surface strongly influences the solvation structure, which becomes less well ordered in the vicinity of the interface. These pronounced differences are likely to affect the reactivity of the two surface terminations, and in particular the energetics of excess charge carriers at the surface.

  12. 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

  13. 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

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. Fundamental measure density functional theory study of liquid-vapor interface of dipolar and quadrupolar fluids.

    PubMed

    Warshavsky, V B; Zeng, X C

    2013-10-01

    We have studied interfacial structure and properties of liquid-vapor interfaces of dipolar fluids and quadrupolar fluids, respectively, using the classical density functional theory (DFT). Towards this end, we employ the fundamental measure DFT for a reference hard-sphere (HS) part of free energy and the modified mean field approximation for the correlation function of dipolar or quadrupolar fluid. At low temperatures we find that both the liquid-vapor interfacial density profile and orientational order parameter profile exhibit weakly damped oscillatory decay into the bulk liquid. At high temperatures the decay of interfacial density and order parameter profiles is entirely monotonic. The scaled temperature τ = 1 - T/T(c) that separates the two qualitatively different interfacial structures is in the range 0.10-0.15. At a given (dimensionless) temperature, increasing the dipolar or quadrupolar moment enhances the density oscillations. Application of an electric field (normal to the interface) will damp the oscillations. Likewise, at the given temperature, increasing the strength of any multipolar moment also increases the surface tensions while increasing the strength of the applied electric field will reduce the surface tensions. The results are compared with those based on the local-density approximations (LDA) for the reference HS part of free energy as well as with results of numerical experiments.

  19. Isolation of mouse respiratory epithelial cells and exposure to experimental cigarette smoke at air liquid interface.

    PubMed

    Lam, Hilaire C; Choi, Augustine M K; Ryter, Stefan W

    2011-01-01

    Pulmonary epithelial cells can be isolated from the respiratory tract of mice and cultured at air-liquid interface (ALI) as a model of differentiated respiratory epithelium. A protocol is described for isolating and exposing these cells to mainstream cigarette smoke (CS), in order to study epithelial cell responses to CS exposure. The protocol consists of three parts: the isolation of airway epithelial cells from mouse trachea, the culturing of these cells at air-liquid interface (ALI) as fully differentiated epithelial cells, and the delivery of calibrated mainstream CS to these cells in culture. The ALI culture system allows the culture of respiratory epithelia under conditions that more closely resemble their physiological setting than ordinary liquid culture systems. The study of molecular and lung cellular responses to CS exposure is a critical component of understanding the impact of environmental air pollution on human health. Research findings in this area may ultimately contribute towards understanding the etiology of chronic obstructive pulmonary disease (COPD), and other tobacco-related diseases, which represent major global health problems. PMID:21372793

  20. 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.

  1. Fundamental measure density functional theory study of hard spheres solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Warshavsky, Vadim

    2005-03-01

    Interfacial free energy is an important characteristic of solid-liquid interface as it is one of the crucial parameters in many formula of interface thermodynamics such the nucleation theory. Previously different aspects of crystal-melt interfaces were intensively studied with simulations [1,2,3], but theoretical studies with Density Functional Theories (DFT) are inconclusive [4,5]. In this report the structure of hard spheres fcc crystal-melt interfaces and the anisotropy of the interfacial free energies are studied using the Rosenfeld's Fundamental Measure DFT as such a functional leads to reliable coexistence results not only for the hard sphere system but also for the Lennard-Jones systems [6]. The parameters of interfacial density profile were calculated by a proper minimization procedure. For the equilibrium density profile the interfacial free energies were compared with simulation results. 1. R.L.Davidchak and B.B.Laird, Phys.Rev.Lett., 85, 4751(2000). 2. J.J. Hoyt, M. Asta and A. Karma, Phys.Rev.Lett., 86, 5530 (2001). 3. J.R.Morris and X.Song, J.Chem.Phys., 119, 3920 (2003). 4. W.A.Curtin, Phys.Rev.B, 39, 6775(1989). 5. R.Ohnesorge, H.Lowen, and H.Wagner, Phys.Rev.E, 50, 4801 (1994). 6. V.Warshavsky and X.Song, Phys.Rev.E, 69, 061113 (2004).

  2. Metastable nanobubbles at the solid-liquid interface due to contact angle hysteresis.

    PubMed

    Nishiyama, Takashi; Yamada, Yutaka; Ikuta, Tatsuya; Takahashi, Koji; Takata, Yasuyuki

    2015-01-27

    Nanobubbles exist at solid-liquid interfaces between pure water and hydrophobic surfaces with very high stability, lasting in certain cases up to several days. Not only semispherical but also other shapes, such as micropancakes, are known to exist at such interfaces. However, doubt has been raised as to whether or not the nanobubbles are gas-phase entities. In this study, surface nanobubbles at a pure water-highly ordered pyrolytic graphite (HOPG) interface were investigated by peak force quantitative nanomechanics (PF-QNM). Multiple isolated nanobubbles generated by the solvent-exchange method were present on the terraced areas, avoiding the steps of the HOPG surface. Adjacent nanobubbles coalesced and formed metastable nanobubbles. Coalescence was enhanced by the PF-QNM measurement. We determined that nanobubbles can exist for a long time because of nanoscale contact angle hysteresis at the water-HOPG interface. Moreover, the hydrophilic steps of HOPG were avoided during coalescence, providing evidence that the nanobubbles are truly gas phase.

  3. 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.

  4. 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.

  5. 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.

  6. Estimation of the curvature of the solid liquid interface during Bridgman crystal growth

    NASA Astrophysics Data System (ADS)

    Barat, Catherine; Duffar, Thierry; Garandet, Jean-Paul

    1998-11-01

    An approximate solution for the solid/liquid interface curvature due to the crucible effect in crystal growth is derived from simple heat flux considerations. The numerical modelling of the problem carried out with the help of the finite element code FIDAP supports the predictions of our analytical expression and allows to identify its range of validity. Experimental interface curvatures, measured in gallium antimonide samples grown by the vertical Bridgman method, are seen to compare satisfactorily to analytical and numerical results. Other literature data are also in fair agreement with the predictions of our models in the case where the amount of heat carried by the crucible is small compared to the overall heat flux.

  7. Highly Sensitive Capacitive Gas Sensing at Ionic Liquid-Electrode Interfaces.

    PubMed

    Wang, Zhe; Guo, Min; Mu, Xiaoyi; Sen, Soumyo; Insley, Thomas; Mason, Andrew J; Král, Petr; Zeng, Xiangqun

    2016-02-01

    We have developed an ultrasensitive gas-detection method based on the measurement of a differential capacitance of electrified ionic liquid (IL) electrode interfaces in the presence and absence of adsorbed gas molecules. The observed change of differential capacitance has a local maximum at a certain potential that is unique for each type of gas, and its amplitude is related to the concentration of the gas molecules. We establish and validate this gas-sensing method by characterizing SO2 detection at ppb levels with less than 1.8% signal from other interfering species (i.e., CO2, O2, NO2, NO, SO2, H2O, H2, and cyclohexane, tested at the same concentration as SO2). This study opens a new avenue of utilizing tunable electrified IL-electrode interfaces for selective sensing of molecules with a kinetic size resolution of 0.1 Å.

  8. 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

  9. Assessment of ion transfer amperometry at liquid-liquid interfaces for detection in CE.

    PubMed

    Sisk, Garry D; Herzog, Grégoire; Glennon, Jeremy D; Arrigan, Damien W M

    2009-10-01

    In this research, ion transfer across the interface between two immiscible electrolyte solutions (ITIES) was used as a method of detection in a CE separation system. This method allows for the electrochemical detection of ionic analytes that cannot be easily oxidized or reduced. Method development revealed that the optimal separation conditions for three model ions (tetraethylammonium, tetrabutylammonium, and benzensulfonate) were found to be 5 mM sodium tetraborate buffer pH 9.2 with a separation voltage of 20 kV using a 40 cm, 50 microm id fused silica capillary. Constant potential amperometry and pulsed amperometric detection were applied at the ITIES in which the organic phase was gelled. A miniaturized ITIES within a pipette tip was investigated, which resulted in improved separation efficiency and LOD. To demonstrate the ability of the system to detect substances of bioanalytical interest, the beta-adrenergic receptor blockers timolol and propranolol were detected. The simplicity of the detection platform means that it may be useful for analytical situations not requiring trace or ultratrace detection capabilities.

  10. 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

  11. 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

  12. 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.

  13. Peculiarity of the liquid/vapour interface of an ionic liquid: study of surface tension and viscoelasticity of liquid BMImPF6 at various temperatures

    NASA Astrophysics Data System (ADS)

    Halka, V.; Tsekov, R.; Freyland, W.

    2005-03-01

    We have measured the surface tension and the capillary wave spectra at the liquid/vapour interface of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate at various temperatures up to 400 K. From the weak temperature dependence of the surface tension a low value of the surface excess entropy of 3.5 × 10-5 J K-1 m-2 results which is consistent with a strongly aligned surface layer of imidazolium cations previously predicted by MD-calculations. The capillary wave spectra recorded at different wave numbers in the range 170 cm-1q 500 cm-1 exhibit strong deviations from the behaviour expected for the free surface of simple liquids. With an extended dispersion relation including the contributions of surface dipole moment density and shear surface excess viscosity - the spectra have been analyzed. It is found that - is negligibly small, whereas substantially influences the capillary wave spectra. The electrostatic potential across the interface, which corresponds to the measured dipole moment densities, qualitatively agrees with simulation calculations. The distinct temperature dependence of suggests that with increasing temperature an order-disorder transformation occurs in the surface layer.

  14. 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.

  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. Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

    PubMed

    Beniwal, Vijay; Manna, Arpan; Kumar, Anil

    2016-07-01

    The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

    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.

  19. 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.

  20. Improving liquid chromatography-mass spectrometry sensitivity using a subambient pressure ionization with nanoelectrospray (SPIN) interface

    SciTech Connect

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

    2011-04-22

    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 5-12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospray ionization (ESI) source was obtained for detected peptides.

  1. Molecularly clean ionic liquid/rubrene single-crystal interfaces revealed by frequency modulation atomic force microscopy.

    PubMed

    Yokota, Yasuyuki; Hara, Hisaya; Morino, Yusuke; Bando, Ken-ichi; Imanishi, Akihito; Uemura, Takafumi; Takeya, Jun; Fukui, Ken-ichi

    2015-03-14

    The structural properties of ionic liquid/rubrene single-crystal interfaces were investigated using frequency modulation atomic force microscopy. The spontaneous dissolution of rubrene molecules into the ionic liquid was triggered by surface defects such as rubrene oxide defects, and the dissolution rate strongly depended on the initial conditions of the rubrene surface. Dissolution of the second rubrene layer was slower due to the lower defect density, leading to the formation of a clean interface irrespective of the initial conditions. Molecular-resolution images were easily obtained at the interface, and their corrugation patterns changed with the applied force. Force curve measurements revealed that a few solvation layers of ionic liquid molecules formed at the interface, and the force needed to penetrate the solvation layers was an order of magnitude smaller than typical ionic liquid/inorganic solid interfaces. These specific properties are discussed with respect to electric double-layer transistors based on the ionic liquid/rubrene single-crystal interface. PMID:25669665

  2. 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

  3. Communication: Evaporation: Influence of heat transport in the liquid on the interface temperature and the particle flux

    NASA Astrophysics Data System (ADS)

    Heinen, Matthias; Vrabec, Jadran; Fischer, Johann

    2016-08-01

    Molecular dynamics simulations are reported for the evaporation of a liquid into vacuum, where a Lennard-Jones type fluid with truncated and shifted potential at 2.5σ is considered. Vacuum is enforced locally by particle deletion and the liquid is thermostated in its bulk so that heat flows to the planar interface driving stationary evaporation. The length of the non-thermostated transition region between the bulk liquid and the interface Ln is under study. First, it is found for the reduced bulk liquid temperature Tl/Tc = 0.74 (Tc is the critical temperature) that by increasing Ln from 5.2σ to 208σ the interface temperature Ti drops by 17% and the evaporation flux decreases by a factor of 4.4. From a series of simulations for increasing values of Ln, an asymptotic value Ti ∞ of the interface temperature for Ln → ∞ can be estimated which is 21% lower than the bulk liquid temperature Tl. Second, it is found that the evaporation flux is solely determined by the interface temperature Ti, independent on Tl or Ln. Combining these two findings, the evaporation coefficient α of a liquid thermostated on a macroscopic scale is estimated to be α ≈ 0.14 for Tl/Tc = 0.74.

  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. 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.

  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. 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.

  8. 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.

  9. 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

  10. 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.

  11. Molecular dynamics simulations of thermal resistance at the liquid-solid interface.

    PubMed

    Kim, Bo Hung; Beskok, Ali; Cagin, Tahir

    2008-11-01

    Heat conduction between parallel plates separated by a thin layer of liquid Argon is investigated using three-dimensional molecular dynamics (MD) simulations employing 6-12 Lennard-Jones potential interactions. Channel walls are maintained at specific temperatures using a recently developed interactive thermal wall model. Heat flux and temperature distribution in nanochannels are calculated for channel heights varying from 12.96 to 3.24 nm. Fourier law of heat conduction is verified for the smallest channel, while the thermal conductivity obtained from Fourier law is verified using the predictions of Green-Kubo theory. Temperature jumps at the liquid/solid interface, corresponding to the well known Kapitza resistance, are observed. Using systematic studies thermal resistance length at the interface is characterized as a function of the surface wettability, thermal oscillation frequency, wall temperature, thermal gradient, and channel height. An empirical model for the thermal resistance length, which could be used as the jump coefficient of a Navier boundary condition, is developed. Temperature distribution in nanochannels is predicted using analytical solution of continuum heat conduction equation subjected to the new temperature jump condition. Analytical predictions are verified using MD simulations.

  12. 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

  13. Morphology control of surfactant-assisted graphene oxide films at the liquid-gas interface.

    PubMed

    Kim, Hyeri; Jang, Young Rae; Yoo, Jeseung; Seo, Young-Soo; Kim, Ki-Yeon; Lee, Jeong-Soo; Park, Soon-Dong; Kim, Chan-Joong; Koo, Jaseung

    2014-03-01

    Control of a two-dimensional (2D) structure of assembled graphene oxide (GO) sheets is highly desirable for fundamental research and potential applications of graphene devices. We show that an alkylamine surfactant, i.e., octadecylamine (ODA), Langmuir monolayer can be utilized as a template for adsorbing highly hydrophilic GO sheets in an aqueous subphase at the liquid-gas interface. The densely packed 2-D monolayer of such complex films was obtained on arbitrary substrates by applying Langmuir-Schaefer or Langmuir-Blodgett technique. Morphology control of GO sheets was also achieved upon compression by tuning the amount of spread ODA molecules. We found that ODA surfactant monolayers prevent GO sheets from sliding, resulting in formation of wrinkling rather than overlapping at the liquid-gas interface during the compression. The morphology structures did not change after a graphitization procedure of chemical hydrazine reduction and thermal annealing treatments. Since morphologies of graphene films are closely correlated to the performance of graphene-based materials, the technique employed in this study can provide a route for applications requiring wrinkled graphenes, ranging from nanoelectronic devices to energy storage materials, such as supercapacitors and fuel cell electrodes. PMID:24499257

  14. Experimental investigations of stability of static liquid fillets and liquid-gas interface in capillary passages for gas-free liquid acquisition in zero gravity

    NASA Astrophysics Data System (ADS)

    Purohit, Ghanshyam Purshottamdas

    Experimental investigations of static liquid fillets formed between small gaps of a cylindrical surface and a flat surface are carried out. The minimum volume of liquid required to form a stable fillet and the maximum liquid content the fillet can hold before becoming unstable are studied. Fillet shapes are captured in photographs obtained by a high speed image system. Experiments were conducted using water, UPA and PF 5060 on two surfaces-stand-blasted titanium and polished copper for different surface inclinations. Experimental data are generalized using appropriate non-dimensional groups. Analytical model are developed to describe the fillet curvature. Fillet curvature data are compared against model predictions and are found to be in close agreement. Bubble point experiments were carried out to measure the capillary pressure difference across the liquid-gas interface in the channels of photo-chemically etched disk stacks. Experiments were conducted using titanium stacks of five different geometrical configurations. Both well wetting liquids (IPA and PF5060) and partially wetting liquid (water) were used during experiments. Test results are found to be in close agreement with analytical predictions. Experiments were carried out to measure the frictional pressure drop across the stack as a function of liquid flow rate using two different liquids (water and IPA) and five stacks of different geometrical configurations. A channel pressure drop model is developed by treating the flow within stack channels as fully developed laminar flow between parallel plates and solving the one-dimensional Navier Stokes equation. An alternate model is developed by treating the flow in channels as flow within porous media. Expressions are developed for effective porosity and permeability for the stacks and the pressure drop is related to these parameters. Pressure drop test results are found to be in close agreement with model predictions. As a specific application of this work, a

  15. Static and dynamic properties of poly(3-hexylthiophene) films at liquid/vacuum interfaces.

    PubMed

    Yimer, Yeneneh Y; Tsige, Mesfin

    2012-11-28

    All-atom molecular dynamics simulations are used to study static and dynamic properties of poly(3-hexylthiophene) (P3HT) films at liquid/vacuum interfaces with regards to their dependence on both temperature and molecular weight. The static properties of the films are characterized by calculating specific volume, interfacial width, orientational ordering of the hexyl groups, and surface tension. The specific volume found to be a monotonically decreasing function of the molecular weight while its dependence on temperature follows the Simha-Somcynsky's equation of state. The orientational ordering calculations show the hexyl groups protruding from the vacuum side of the interface, where the degree of order at the interface is found to be strongly dependent on both temperature and molecular weight. The surface tension values show a linear dependence on temperature and the molecular weight dependence is equally described by both M(-2∕3) and M(-1) power law models. The dynamic properties are quantified by calculating diffusion coefficients for the chain centers-of-mass and thiophene ring segments as well as first-order and second-order end-to-end vector autocorrelations and chain backbone torsion autocorrelation. All calculated dynamic properties show strong dependence on both temperature and molecular weight. All the autocorrelations are well described by Kohlrausch-Williams-Watts equation. Our detailed analysis of the static and dynamic properties of P3HT films show that the calculated static and dynamic properties data can be fit with well-known polymer models.

  16. Molecular dynamics simulations of aqueous ions at the liquid-vapor interface accelerated using graphics processors.

    PubMed

    Bauer, Brad A; Davis, Joseph E; Taufer, Michela; Patel, Sandeep

    2011-02-01

    Molecular dynamics (MD) simulations are a vital tool in chemical research, as they are able to provide an atomistic view of chemical systems and processes that is not obtainable through experiment. However, large-scale MD simulations require access to multicore clusters or supercomputers that are not always available to all researchers. Recently, scientists have returned to exploring the power of graphics processing units (GPUs) for various applications, such as MD, enabled by the recent advances in hardware and integrated programming interfaces such as NVIDIA's CUDA platform. One area of particular interest within the context of chemical applications is that of aqueous interfaces, the salt solutions of which have found application as model systems for studying atmospheric process as well as physical behaviors such as the Hoffmeister effect. Here, we present results of GPU-accelerated simulations of the liquid-vapor interface of aqueous sodium iodide solutions. Analysis of various properties, such as density and surface tension, demonstrates that our model is consistent with previous studies of similar systems. In particular, we find that the current combination of water and ion force fields coupled with the ability to simulate surfaces of differing area enabled by GPU hardware is able to reproduce the experimental trend of increasing salt solution surface tension relative to pure water. In terms of performance, our GPU implementation performs equivalent to CHARMM running on 21 CPUs. Finally, we address possible issues with the accuracy of MD simulaions caused by nonstandard single-precision arithmetic implemented on current GPUs. PMID:20862755

  17. Phase conversion and interface growth in phase-separated 3He - 4He liquid mixtures

    NASA Astrophysics Data System (ADS)

    Abe, Haruka; Satoh, Takeo; Burmistrov, Serguei N.

    2005-10-01

    We have developed a method for measuring the transmission coefficient of a sound propagating through the interface in phase-separated He3-He4 liquid mixtures. The method and the results are described with discussions by examining the phase-conversion process of He3 quasiparticles driven to flow across the interface. From the data, we have determined the kinetic growth coefficient of the interface, ξ(T,P,ω) , as a function of temperature, pressure, and frequency. The temperature range of the present investigation is about 2-100mK at the pressure mainly around 1bar with sound frequency 9.64, 14.4, and 32.4MHz . The main specific features observed for the kinetic growth coefficient are, as follows: (i) there is a maximum at some temperature Tm(ω) depending on the frequency, (ii) above Tm(ω) , ξ decreases with the increase of temperature as ∝ω5/2T-3 , and (iii) below Tm(ω) , ξ becomes frequency independent and diminishes as a cube of temperature, T3 .

  18. 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

  19. Dynamic interface tension of a smectic liquid crystal in anionic surfactant solutions.

    PubMed

    Harth, Kirsten; Shepherd, Larissa M; Honaker, James; Stannarius, Ralf

    2015-10-21

    The interface tension of a smectic liquid crystal with respect to a surrounding ionic surfactant solution is investigated at concentrations above and below the critical micelle concentration (cmc). A simple measurement technique has been developed recently [Phys. Chem. Chem. Phys., 2013, 15, 7204], based on the geometrical analysis of the shape of smectic bubbles in water that are deformed by the buoyancy of trapped air bubbles. After preparation of the smectic membranes in the solution, we measure both the time dependence of their dynamic interface tension as well as the asymptotically reached static tension values. These are established about 15 minutes after the membrane preparation. At large enough concentrations of the surfactant (above the critical micelle concentration), the interface tension drops to 6 mN m(-1). At the lowest possible surfactant concentrations in our experiment, the equilibrium tension reaches 20 mN m(-1), which is almost equal to the smectic surface tension respective to air. The tension of a freshly drawn film exceeds this value by far.

  20. Engineering the Electrode-Electrolyte Interface: From Electrode Architecture to Zinc Redox in Ionic Liquid Electrolytes

    NASA Astrophysics Data System (ADS)

    Engstrom, Erika

    2011-12-01

    The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic

  1. 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

  2. Slow and fast capacitive process taking place at the ionic liquid/electrode interface.

    PubMed

    Roling, Bernhard; Drüschler, Marcel; Huber, Benediki

    2012-01-01

    Electrochemical impedance spectroscopy was used to characterise the interface between the ultrapure room temperature ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and a Au(111) working electrode at electrode potentials more positive than the open circuit potential (-0.14 V vs. Pt pseudo-reference). Plots of the potential-dependent data in the complex capacitance plane reveal the existence of a fast and a slow capacitive process. In order to derive the contribution of both processes to the overall capacitance, the complex capacitance data were fitted using an empirical Cole-Cole equation. The differential capacitance of the fast process is almost constant between -0.14 V and +0.2 V (vs. Pt pseudo-reference) and decreases at more positive potentials, while the differential capacitance of the slower process exhibits a maximum at +0.2 V. This maximum leads to a maximum in the overall differential capacitance. We attribute the slow process to charge redistributions in the innermost ion layer, which require an activation energy in excess of that for ion transport in the room temperature ionic liquid. The differential capacitance maximum of the slow process at +0.2 V is most likely caused by reorientations of the 1-butyl-1l-methylpyrrolidinium cations in the innermost layer with the positively charged ring moving away from the Au(111) surface and leaving behind voids which are then occupied by anions. In a recent Monte Carlo simulation by Federov, Georgi and Kornyshev (Electrochem. Commun. 2010, 12, 296), such a process was identified as the origin of a differential capacitance maximum in the anodic regime. Our results suggest that the time scales of capacitive processes at the ionic liquid/metal interface are an important piece of information and should be considered in more detail in future experimental and theoretical studies.

  3. {sup 4}He liquid-vapor interface below 1 K studied using x-ray reflectivity

    SciTech Connect

    Penanen, Konstantin; Fukuto, Masafumi; Heilmann, Ralf K.; Silvera, Isaac F.; Pershan, Peter S.

    2000-10-01

    The free surface of thin films of liquid helium adsorbed on a solid substrate has been studied using x-ray reflectivity. The film thickness and interfacial profile are extracted from the angular dependence of measured interference between signals reflected from the liquid-vapor and liquid-substrate interfaces. Polished silicon wafers, chemically cleaned and passivated, were used as substrates. Results are reported for measurements for {sup 4}He films 35 to 130 Aa thick in the temperature range 0.44 to 1.3 K. The 10%/90% interfacial width for temperature T=0.45 K varies from 5.3{+-}0.5 Aa for 36{+-}1.5 Aa thick films to 6.5{+-}0.5 Aa for 125{+-}1.5 Aa thick films. The profile width at zero temperature should not differ significantly from that measured at T=0.45 K. For T=1.22 K, the width is 7.8{+-}1.0 Aa.

  4. 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.

  5. 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

  6. 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.

  7. Phase-field crystal modeling of equilibrium bcc-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Wu, Kuo-An; Karma, Alain

    2007-11-01

    We investigate the equilibrium properties of bcc-liquid interfaces modeled with a continuum phase-field crystal (PFC) approach [K. R. Elder and M. Grant, Phys. Rev. E 70, 051605 (2004)]. A multiscale analysis of the PFC model is carried out which exploits the fact that the amplitudes of crystal density waves decay slowly into the liquid in the physically relevant limit where the freezing transition is weakly first order. This analysis yields a set of coupled equations for these amplitudes that is similar to the set of equations derived from Ginzburg-Landau (GL) theory [K.-A. Wu , Phys. Rev. B 73, 094101 (2006)]. The two sets only differ in the details of higher order nonlinear couplings between different density waves, which is determined by the form of the nonlinearity assumed in the PFC model and by the ansatz that all polygons with the same number of sides have equal weight in GL theory. Despite these differences, for parameters (liquid structure factor and solid density wave amplitude) of Fe determined from molecular dynamics (MD) simulations, the PFC and GL amplitude equations yield very similar predictions for the overall magnitude and anisotropy of the interfacial free-energy and density wave profiles. These predictions are compared with MD simulations as well as numerical solutions of the PFC model.

  8. 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

  9. 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.

  10. Electronic functionalization of solid-to-liquid interfaces between organic semiconductors and ionic liquids: Realization of very high performance organic single-crystal transistors

    NASA Astrophysics Data System (ADS)

    Uemura, T.; Hirahara, R.; Tominari, Y.; Ono, S.; Seki, S.; Takeya, J.

    2008-12-01

    High-performance electronic function of current amplification is realized with the use of solid-to-liquid interfaces between organic semiconductors and ionic liquid. To hold in place the ionic liquid of 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide known for low viscosity and high ionic conductivity, an elastomeric well structure is fabricated with polydimethylsiloxane on which organic single crystals of rubrene are electrostatically attached. As the result of rapid formation of electric double layers in the ionic liquid interfacing, the high-mobility organic semiconductor crystals' fast-switching transistor function is demonstrated with the application of gate voltage, realizing the highest sheet transconductance, namely, amplifying performance, ever achieved.

  11. Novel impedance cell for low conductive liquids: Determination of bulk and interface contributions

    NASA Astrophysics Data System (ADS)

    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 500μS/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 300μm and 6.75mm (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 1kHz. The sample measurements have been performed by scanning the frequency range between 15Hz and 2MHz 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<10kHz).

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

    USGS Publications Warehouse

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

    1978-01-01

    Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H2O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H2O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H2O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H2O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9

  13. 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.

  14. 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.

  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. 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

  18. SO{sub 2} uptake on ice spheres: Liquid nature of the ice-air interface

    SciTech Connect

    Conklin, M.H.; Bales, R.C.

    1993-09-20

    The amount of SO{sub 2} gas absorbed by ice of known surface area at equilibrium was used to estimate the volume of liquid water present at the ice-air interface at temperatures from {minus}1 to {minus}60{degrees}C. Calculations were based on Henry`s law and acid dissociation equilibrium. The liquid volume is lowest at lower temperatures and ionic strength and under most conditions was greater than the volumes calculated based on freezing-point depression. The equivalent layer thickness, assuming that liquid water is uniformly distributed around the grains, ranged from 3-30 nm at {minus}60{degrees}C to 500-3000 nm at {minus}1{degrees}C. Corresponding ionic strengths for the two temperatures were 1.7-0.0012 M and 0.005-0.00009 M. Lower values were for ice made from distilled water, and higher values were for ice made from 10{sup {minus}3} M NaCl. Estimated pH values were from 2.9 at {minus}60{degrees}C to 4.1 at {minus}1{degrees}C. Results demonstrate that gas absorption can be used to estimate an equivalent liquid volume and thickness for the ice-air interfacial region. While not directly comparable to physical measurements, the estimated values should be directly applicable to modeling uptake of SO{sub 2} and other trace gases by ice. Lack of good thermodynamic data for temperature below 0{degrees}C is the main limitation to applying this method. 23 refs., 3 figs., 1 tab.

  19. Phase interface effects in the total enthalpy-based lattice Boltzmann model for solid-liquid phase change

    NASA Astrophysics Data System (ADS)

    Huang, Rongzong; Wu, Huiying

    2015-08-01

    In this paper, phase interface effects, including the differences in thermophysical properties between solid and liquid phases and the numerical diffusion across phase interface, are investigated for the recently developed total enthalpy-based lattice Boltzmann model for solid-liquid phase change, which has high computational efficiency by avoiding iteration procedure and linear equation system solving. For the differences in thermophysical properties (thermal conductivity and specific heat) between solid and liquid phases, a novel reference specific heat is introduced to improve the total enthalpy-based lattice Boltzmann model, which makes the thermal conductivity and specific heat decoupled. Therefore, the differences in thermal conductivity and specific heat can be handled by the dimensionless relaxation time and equilibrium distribution function, respectively. As for the numerical diffusion across phase interface, it is revealed for the first time and found to be induced by solid-liquid phase change. To reduce such numerical diffusion, multiple-relaxation-time collision scheme is exploited, and a special value (one fourth) for the so-called "magic" parameter, a combination of two relaxation parameters, is found. Numerical tests show that the differences in thermophysical properties can be correctly handled and the numerical diffusion across phase interface can be dramatically reduced. Finally, theoretical analyses are carried out to offer insights into the roles of the reference specific heat and "magic" parameter in the treatments of phase interface effects.

  20. 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

  1. Physics of solid-liquid interfaces: From the Young equation to the superhydrophobicity (Review Article)

    NASA Astrophysics Data System (ADS)

    Bormashenko, Edward

    2016-08-01

    The state-of-art in the field of physics of phenomena occurring at solid/liquid interfaces is presented. The notions of modern physics of wetting are introduced and discussed including: the contact angle hysteresis, disjoining pressure and wetting transitions. The physics of low temperature wetting phenomena is treated. The general variational approach to interfacial problems, based on the application of the transversality conditions to variational problems with free endpoints is presented. It is demonstrated that main equations, predicting contact angles, namely the Young, Wenzel, and Cassie-Baxter equations arise from imposing the transversality conditions on the appropriate variational problem of wetting. Recently discovered effects such as superhydrophobicity, the rose petal effect and the molecular dynamic of capillarity are reviewed.

  2. 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.

  3. 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

  4. Adsorption of solutes at liquid-vapor interfaces: insights from lattice gas models.

    PubMed

    Vaikuntanathan, Suriyanarayanan; Shaffer, Patrick R; Geissler, Phillip L

    2013-01-01

    The adsorption behavior of ions at liquid-vapor interfaces exhibits several unexpected yet generic features. In particular, energy and entropy are both minimum when the solute resides near the surface, for a variety of ions in a range of polar solvents, contrary to predictions of classical theories. Motivated by this generality, and by the simple physical ingredients implicated by computational studies, we have examined interfacial solvation in highly schematic models, which resolve only coarse fluctuations in solvent density and cohesive energy. Here we show that even such lattice gas models recapitulate surprising thermodynamic trends observed in detailed simulations and experiments. Attention is focused on the case of two dimensions, for which approximate energy and entropy profiles can be calculated analytically. Simulations and theoretical analysis of the lattice gas highlight the role of capillary wave-like fluctuations in mediating adsorption. They further point to ranges of temperature and solute-solvent interaction strength where surface propensity is expected to be strongest.

  5. Bilayer molecular assembly at a solid/liquid interface as triggered by a mild electric field.

    PubMed

    Zheng, Qing-Na; Liu, Xuan-He; Liu, Xing-Rui; Chen, Ting; Yan, Hui-Juan; Zhong, Yu-Wu; Wang, Dong; Wan, Li-Jun

    2014-12-01

    The construction of a spatially defined assembly of molecular building blocks, especially in the vertical direction, presents a great challenge for surface molecular engineering. Herein, we demonstrate that an electric field applied between an STM tip and a substrate triggered the formation of a bilayer structure at the solid-liquid interface. In contrast to the typical high electric-field strength (10(9)  V m(-1) ) used to induce structural transitions in supramolecular assemblies, a mild electric field (10(5)  V m(-1) ) triggered the formation of a bilayer structure of a polar molecule on top of a nanoporous network of trimesic acid on graphite. The bilayer structure was transformed into a monolayer kagome structure by changing the polarity of the electric field. This tailored formation and large-scale phase transformation of a molecular assembly in the perpendicular dimension by a mild electric field opens perspectives for the manipulation of surface molecular nanoarchitectures.

  6. 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.

  7. Molecular Threading: Mechanical Extraction, Stretching and Placement of DNA Molecules from a Liquid-Air Interface

    PubMed Central

    Kemmish, Kent; Hamalainen, Mark; Bowell, Charlotte; Bleloch, Andrew; Klejwa, Nathan; Lehrach, Wolfgang; Schatz, Ken; Stark, Heather; Marblestone, Adam; Church, George; Own, Christopher S.; Andregg, William

    2013-01-01

    We present “molecular threading”, a surface independent tip-based method for stretching and depositing single and double-stranded DNA molecules. DNA is stretched into air at a liquid-air interface, and can be subsequently deposited onto a dry substrate isolated from solution. The design of an apparatus used for molecular threading is presented, and fluorescence and electron microscopies are used to characterize the angular distribution, straightness, and reproducibility of stretched DNA deposited in arrays onto elastomeric surfaces and thin membranes. Molecular threading demonstrates high straightness and uniformity over length scales from nanometers to micrometers, and represents an alternative to existing DNA deposition and linearization methods. These results point towards scalable and high-throughput precision manipulation of single-molecule polymers. PMID:23935923

  8. 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.

  9. 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)

  10. 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.

  11. 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

  12. Getting in shape: molten wax drop deformation and solidification at an immiscible liquid interface.

    PubMed

    Beesabathuni, Shilpa N; Lindberg, Seth E; Caggioni, Marco; Wesner, Chris; Shen, Amy Q

    2015-05-01

    The controlled production of non-spherical shaped particles is important for many applications such as food processing, consumer goods, adsorbents, drug delivery, and optical sensing. In this paper, we investigated the deformation and simultaneous solidification of millimeter size molten wax drops as they impacted an immiscible liquid interface of higher density. By varying initial temperature and viscoelasticity of the molten drop, drop size, impact velocity, viscosity and temperature of the bath fluid, and the interfacial tension between the molten wax and bath fluid, spherical molten wax drops impinged on a cooling water bath and were arrested into non-spherical solidified particles in the form of ellipsoid, mushroom, disc, and flake-like shapes. We constructed cursory phase diagrams for the various particle shapes generated over a range of Weber, Capillary, Reynolds, and Stefan numbers, governed by the interfacial, inertial, viscous, and thermal effects. We solved a simplified heat transfer problem to estimate the time required to initiate the solidification at the interface of a spherical molten wax droplet and cooling aqueous bath after impact. By correlating this time with the molten wax drop deformation history captured from high speed imaging experiments, we elucidate the delicate balance of interfacial, inertial, viscous, and thermal forces that determine the final morphology of wax particles.

  13. 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.

  14. 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.

  15. Milliscale Self-Integration of Megamolecule Biopolymers on a Drying Gas-Aqueous Liquid Crystalline Interface.

    PubMed

    Okeyoshi, Kosuke; Okajima, Maiko K; Kaneko, Tatsuo

    2016-06-13

    A drying environment is always a proposition faced by dynamic living organisms using water, which are driven by biopolymer-based micro- and macrostructures. Here, we introduce a drying process for aqueous liquid crystalline (LC) solutions composed of biopolymer with extremely high molecular weight components such as polysaccharides, cytoskeletal proteins, and DNA. On controlling the mobility of the LC microdomain, the solutions showed milliscale self-integration starting from the unstable gas-LC interface during drying. In particular, we first identified giant rod-like microdomains (∼1 μm diameter and more than 20 μm length) of the mega-molecular polysaccharide, sacran, which is remarkably larger than other polysaccharides. These microdomains led to the formation of a single milliscale macrodomain on the interface. In addition, the dried polymer films on a solid substrate also revealed that such integration depends on the size of the microdomain. We envision that this simple drying method will be useful not only for understanding the biopolymer hierarchization at the macroscale level but also for preparation of surfaces with direction controllability, as seen in living organisms, for use in various fields such as diffusion, mechanics, and photonics.

  16. Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

    SciTech Connect

    Vaknin, David; Bu, Wei

    2010-07-23

    Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in small domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Contact-angle hysteresis on periodic microtextured surfaces: Strongly corrugated liquid interfaces.

    PubMed

    Iliev, Stanimir; Pesheva, Nina

    2016-06-01

    We study numerically the shapes of a liquid meniscus in contact with ultrahydrophobic pillar surfaces in Cassie's wetting regime, when the surface is covered with identical and periodically distributed micropillars. Using the full capillary model we obtain the advancing and the receding equilibrium meniscus shapes when the cross-sections of the pillars are both of square and circular shapes, for a broad interval of pillar concentrations. The bending of the liquid interface in the area between the pillars is studied in the framework of the full capillary model and compared to the results of the heterogeneous approximation model. The contact angle hysteresis is obtained when the three-phase contact line is located on one row (block case) or several rows (kink case) of pillars. It is found that the contact angle hysteresis is proportional to the line fraction of the contact line on pillars tops in the block case and to the surface fraction for pillar concentrations 0.1-0.5 in the kink case. The contact angle hysteresis does not depend on the shape (circular or square) of the pillars cross-section. The expression for the proportionality of the receding contact angle to the line fraction [Raj et al., Langmuir 28, 15777 (2012)LANGD50743-746310.1021/la303070s] in the case of block depinning is theoretically substantiated through the capillary force, acting on the solid plate at the meniscus contact line.

  2. 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.

  3. Long-wave theory of bounded two-layer films with a free liquid-liquid interface: Short- and long-time evolution

    NASA Astrophysics Data System (ADS)

    Merkt, D.; Pototsky, A.; Bestehorn, M.; Thiele, U.

    2005-06-01

    We consider two layers of immiscible liquids confined between an upper and a lower rigid plate. The dynamics of the free liquid-liquid interface is described for arbitrary amplitudes by an evolution equation derived from the basic hydrodynamic equations using long-wave approximation. After giving the evolution equation in a general way, we focus on interface instabilities driven by gravity, thermocapillary and electrostatic fields. First, we study the linear stability discussing especially the conditions for destabilizing the system by heating from above or below. Second, we use a variational formulation of the evolution equation based on an energy functional to predict metastable states and the long-time pattern morphology (holes, drops or maze structures). Finally, fully nonlinear three-dimensional numerical integrations are performed to study the short- and long-time evolution of the evolving patterns. Different coarsening modes are discussed and long-time scaling exponents are extracted.

  4. 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.

  5. 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.

  6. 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.

  7. Polysaccharide films at an air/liquid and a liquid/silicon interface: effect of the polysaccharide and liquid type on their physical properties.

    PubMed

    Taira, Yasunori; McNamee, Cathy E

    2014-11-14

    We investigated the effect of the polysaccharide type, the subphase on which the Langmuir monolayers were prepared, and the liquid in which the properties of the transferred monolayers were measured on the physical properties of the polysaccharide films at an air/aqueous interface and at a silicon substrate, and the forces and friction of the polysaccharide transferred films when measured in solution against a silica probe. Chitosan was modified with a silane coupling agent to make chitosan derived compounds with a low and a medium molecular weight. Chitin and the chitosan-derived compounds were used to make Langmuir monolayers at air/water and air/pH 9 buffer interfaces. The monolayers were transferred to silicon substrates via Langmuir-Blodgett deposition, and the chitosan-derived compounds subsequently chemically reacted with the silicon substrates. Atomic force microscope force and friction measurements were made in water and in the pH 9 buffer, where the water and the pH 9 buffer acted as a good and a bad solvent for the polysaccharides, respectively. The polysaccharide type affected the friction of the polysaccharide film, where the physically adsorbed chitin gave the lowest friction. The friction of L-chitosan was higher than that of M-chitosan in water, suggesting that the molecular weight of the polymer affects its lubricating ability. The forces and friction of the polysaccharide films changed when the subphase on which the Langmuir monolayers were formed was changed or when the liquid in which the properties of the films adsorbed at the silicon substrate were measured was changed. The friction increased significantly when the liquid was changed from water to the pH 9 buffer. This increase was explained by the reduced charge of the chitin and chitosan-derived materials due to the pH increase, the screening of the charges by the salts in the buffer, and the possible hardening of the monolayer caused by the adsorption of salts from the buffer. PMID:25248865

  8. Polysaccharide films at an air/liquid and a liquid/silicon interface: effect of the polysaccharide and liquid type on their physical properties.

    PubMed

    Taira, Yasunori; McNamee, Cathy E

    2014-11-14

    We investigated the effect of the polysaccharide type, the subphase on which the Langmuir monolayers were prepared, and the liquid in which the properties of the transferred monolayers were measured on the physical properties of the polysaccharide films at an air/aqueous interface and at a silicon substrate, and the forces and friction of the polysaccharide transferred films when measured in solution against a silica probe. Chitosan was modified with a silane coupling agent to make chitosan derived compounds with a low and a medium molecular weight. Chitin and the chitosan-derived compounds were used to make Langmuir monolayers at air/water and air/pH 9 buffer interfaces. The monolayers were transferred to silicon substrates via Langmuir-Blodgett deposition, and the chitosan-derived compounds subsequently chemically reacted with the silicon substrates. Atomic force microscope force and friction measurements were made in water and in the pH 9 buffer, where the water and the pH 9 buffer acted as a good and a bad solvent for the polysaccharides, respectively. The polysaccharide type affected the friction of the polysaccharide film, where the physically adsorbed chitin gave the lowest friction. The friction of L-chitosan was higher than that of M-chitosan in water, suggesting that the molecular weight of the polymer affects its lubricating ability. The forces and friction of the polysaccharide films changed when the subphase on which the Langmuir monolayers were formed was changed or when the liquid in which the properties of the films adsorbed at the silicon substrate were measured was changed. The friction increased significantly when the liquid was changed from water to the pH 9 buffer. This increase was explained by the reduced charge of the chitin and chitosan-derived materials due to the pH increase, the screening of the charges by the salts in the buffer, and the possible hardening of the monolayer caused by the adsorption of salts from the buffer.

  9. 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.

  10. Measurement and control of the liquid/solid interface temperature during the directional solidification by using the Seebeck effect

    NASA Astrophysics Data System (ADS)

    Cambon, G.; Cadet, G.; Favier, J. J.; Rouzaud, A.; Comera, J.

    The morphological stability and the segregation in the vicinity of the solid/liquid interface moving during the directional solidification of a metallurgical sample are depending on the undercooling phenomena which occurs during the growth. An interesting means to know this undercooling effect is to measure the Seebeck signal produced by the solid/liquid interface moving, with comparison with another static S/L interface of the sample. The in situ measurement techniques developed by CEA/CENG/LES and CNES/GERME gives the possibility to measure this temperature with 0.01 K differential accuracy in the severe mechanical, thermal and electromagnetic environment of the MEPHISTO space instrument on board of the U.S. Space Shuttle. After a brief scientific description of the interest of such undercooling measurement, a technical description of the adequate hardware, with the performance obtained during scientific tests, is presented in this paper.

  11. 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

  12. Ionic Liquid Films at the Water-Air Interface: Langmuir Isotherms of Tetra-alkylphosphonium-Based Ionic Liquids.

    PubMed

    Shimizu, Karina; Canongia Lopes, José N; Gonçalves da Silva, Amélia M P S

    2015-08-01

    The behavior of ionic liquids trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide and trihexyl(tetradecyl)phosphonium dicyanamide, [P6 6 6 14][Ntf2] and [P6 6 6 14][N(CN)2], respectively, at the water-air interface was investigated using the Langmuir trough technique. The obtained surface pressure versus mean molecular area (MMA) isotherms, π-A, and surface potential versus MMA isotherms, ΔV-A, show distinct interfacial behavior between the two systems. The results were interpreted at a molecular level using molecular dynamics simulations: the different compression regimes along the [P6 6 6 14][Ntf2] isotherm correspond to the self-organization of the ions at the water surface into compact and planar monolayers that coalesce at an MMA value of ca. 1.85 nm(2)/ion pair to form an expanded liquidlike layer. Upon further compression, the monolayer collapses at around 1.2 nm(2)/ion pair to yield a progressively thicker and less organized layer. These transitions are much more subdued in the [P6 6 6 14][N(CN)2] system because of the more hydrophilic nature of the dicyanamide anion. The numerical density profiles obtained from the MD simulation trajectories are also able to emphasize the very unusual packing of the four long alkyl side chains of the cation above and below the ionic layer that forms at the water surface. Such a distribution is also different for the two studied systems during the different compression regimes.

  13. 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}.

  14. A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces

    SciTech Connect

    Starr, David E.; Wong, Ed K.; Worsnop, Douglas R.; Wilson, Kevin R.; Bluhm, Hendrik

    2008-05-01

    We describe a combined ambient pressure photoelectron spectroscopy/droplet train apparatus for investigating the nature and heterogeneous chemistry of liquid/vapor interfaces. In this instrument a liquid droplet train with typical droplet diameters from 50...150 {micro}m is produced by a vibrating orifice aerosol generator (VOAG). The droplets are irradiated by soft X-rays (100...1500 eV) in front of the entrance aperture of a differentially pumped electrostatic lens system that transfers the emitted electrons into a conventional hemispherical electron analyzer. The photoemission experiments are performed at background pressures of up to several Torr, which allows the study of environmentally important liquid/vapor interfaces, in particular aqueous solutions, under equilibrium conditions. The exposure time of the droplet surface to the background gases prior to the XPS measurement can be varied, which will allow future kinetic measurements of gas uptake on liquid surfaces. As an example, a measurement of the surface composition of a {chi} = 0.21 aqueous methanol solution is presented. The concentration of methanol at the vapor/liquid interface is enhanced by a factor of about 3 over the bulk value, while the expected bulk value is recovered at depths larger than about 1.5 nm.

  15. A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces.

    PubMed

    Starr, David E; Wong, Ed K; Worsnop, Douglas R; Wilson, Kevin R; Bluhm, Hendrik

    2008-06-01

    We describe a combined ambient pressure photoelectron spectroscopy/droplet train apparatus for investigating the nature and heterogeneous chemistry of liquid/vapor interfaces. In this instrument a liquid droplet train with typical droplet diameters from 50-150 mum is produced by a vibrating orifice aerosol generator (VOAG). The droplets are irradiated by soft X-rays (100-1500 eV) in front of the entrance aperture of a differentially pumped electrostatic lens system that transfers the emitted electrons into a conventional hemispherical electron analyzer. The photoemission experiments are performed at background pressures of up to several Torr, which allows the study of environmentally important liquid/vapor interfaces, in particular aqueous solutions, under equilibrium conditions. The exposure time of the droplet surface to the background gases prior to the XPS measurement can be varied, which will allow future kinetic measurements of gas uptake on liquid surfaces. As an example, a measurement of the surface composition of a chi = 0.21 aqueous methanol solution is presented. The concentration of methanol at the vapor/liquid interface is enhanced by a factor of about 3 over the bulk value, while the expected bulk value is recovered at depths larger than about 1.5 nm.

  16. Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

    NASA Astrophysics Data System (ADS)

    Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic

  17. Nanobubbles do not sit alone at the solid-liquid interface.

    PubMed

    Peng, Hong; Hampton, Marc A; Nguyen, Anh V

    2013-05-21

    The unexpected stability and anomalous contact angle of gaseous nanobubbles at the hydrophobic solid-liquid interface has been an issue of debate for almost two decades. In this work silicon-nitride tipped AFM cantilevers are used to probe the highly ordered pyrolytic graphite (HOPG)-water interface with and without solvent-exchange (a common nanobubble production method). Without solvent-exchange the force obtained by the single force and force mapping techniques is consistent over the HOPG atomic layers and described by DLVO theory (strong EDL repulsion). With solvent-exchange the force is non-DLVO (no EDL repulsion) and the range of the attractive jump-in (>10 nm) over the surface is grouped into circular areas of longer range, consistent with nanobubbles, and the area of shorter range. The non-DLVO nature of the area between nanobubbles suggests that the interaction is no longer between a silicon-nitride tip and HOPG. Interfacial gas enrichment (IGE) covering the entire area between nanobubbles is suggested to be responsible for the non-DLVO forces. The absence of EDL repulsion suggests that both IGE and nanobubbles are not charged. The coexistence of nanobubbles and IGE provides further evidence of nanobubble stability by dynamic equilibrium. The IGE cannot be removed by contact mode scanning of a cantilever tip in pure water, but in a surfactant (SDS) solution the mechanical action of the tip and the chemical action of the surfactant molecules can successfully remove the enrichment. Strong EDL repulsion between the tip and nanobubbles/IGE in surfactant solutions is due to the polar heads of the adsorbed surfactant molecules.

  18. Dry-Surface Simulation Method for the Determination of the Work of Adhesion of Solid-Liquid Interfaces.

    PubMed

    Leroy, Frédéric; Müller-Plathe, Florian

    2015-08-01

    We introduce a methodology, referred to as the dry-surface method, to calculate the work of adhesion of heterogeneous solid-liquid interfaces by molecular simulation. This method employs a straightforward thermodynamic integration approach to calculate the work of adhesion as the reversible work to turn off the attractive part of the actual solid-liquid interaction potential. It is formulated in such a way that it may be used either to evaluate the ability of force fields to reproduce reference values of the work of adhesion or to optimize force-field parameters with reference values of the work of adhesion as target quantities. The methodology is tested in the case of water on a generic model of nonpolar substrates with the structure of gold. It is validated through a quantitative comparison to phantom-wall calculations and against a previous characterization of the thermodynamics of the gold-water interface. It is found that the work of adhesion of water on nonpolar substrates is a nonlinear function of the microscopic solid-liquid interaction energy parameter. We also comment on the ability of mean-field approaches to predict the work of adhesion of water on nonpolar substrates. In addition, we discuss in detail the information on the solid-liquid interfacial thermodynamics delivered by the phantom-wall approach. We show that phantom-wall calculations yield the solid-liquid interfacial tension relative to the solid surface tension rather than the absolute solid-liquid interfacial tension as previously believed.

  19. Influence of specific anions on the orientational ordering of thermotropic liquid crystals at aqueous interfaces.

    PubMed

    Carlton, Rebecca J; Ma, C Derek; Gupta, Jugal K; Abbott, Nicholas L

    2012-09-01

    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 Å(2)/molecule for NaClO(4)) and thus smaller molecular tilt angles (30° from the surface normal for NaClO(4)) than kosmotropic salts (5.0 mN/m at 38 Å(2)/molecule 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

  20. 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

  1. 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

  2. A Diffuse Interface Model for solid-liquid-air dissolution problems based on a porous medium theory

    NASA Astrophysics Data System (ADS)

    Luo, H.; Quintard, M.; Debenest, G.; Laouafa, F.

    2011-12-01

    The underground cavities may be dissolved by the flows of groundwater where the dissolution mainly happens at the liquid-solid interface. In many real cases, the cavities are not occupied only by the water, but also the gas phase, e.g., air, or other gases. In this case, there are solid-liquid-gas three phases. Normally, the air does not participate the dissolution. However, it may influence the dissolution as the position of the solid-liquid interface may gradually lower down with the dissolution process. Simulating the dissolution problems with multi- moving interfaces is a difficult task but rather interesting to study the evolution of the underground cavities. In this paper, we propose a diffuse interface model (DIM) to simulate the three-phase dissolution problem, based on a porous medium theory and a volume averaging theory te{Whitaker1999,Golfier2002,Quintard1994}. The interface is regarded as a continuous layer where the phase indicator (mainly for solid-liquid interface) and phase saturation (mainly for liquid-gas interface) vary rapidly but smoothly. The DIM equations enable us to simulate the moving interface under a fixed mesh system, instead of a deformed or moving mesh. Suppose we have three phases, solid, liquid and gas. The solid phase contains only species A. The gas phase contains only the air. The volume averaging theory is used to upscale the balance equations. The final DIM equations are presented below. The balance equation of solid phase can be written as {partialrho_{s}(1-\\varepsilon_{f})}/{partial t}=-K_{sl} where \\varepsilonf represents the volume fraction of the fluids (liquid+gas) and Ksl refers to the mass exchange between the solid phase and the liquid phase. Ksl cam be expressed as K_{sl}=rho_{l}alpha(omega_{eq}-Omega_{Al}). The balance equations of liquid phase can be written as {partialrho_{l}\\varepsilon_{f}S_{l}}/{partial t}+nabla\\cdot(rho_{l}{V}_{l})= K_{sl}. The balance equation of liquid phase can be written as {partialrho

  3. Intermolecular network analysis of the liquid and vapor interfaces of pentane and water: microsolvation does not trend with interfacial properties.

    PubMed

    Ghadar, Yasaman; Clark, Aurora E

    2014-06-28

    Liquid:vapor and liquid:liquid interfaces exhibit complex organizational structure and dynamics at the molecular level. In the case of water and organic solvents, the hydrophobicity of the organic, its conformational flexibility, and compressibility, all influence interfacial properties. This work compares the interfacial tension, width, molecular conformations and orientations at the vapor and aqueous liquid interfaces of two solvents, n-pentane and neopentane, whose varying molecular shapes can lead to significantly different interfacial behavior. Particular emphasis has been dedicated toward understanding how the hydrogen bond network of water responds to the pentane relative to the vapor interface and the sensitivity of the network to the individual pentane isomer and system temperature. Interfacial microsolvation of the immiscible solvents has been examined using graph theoretical methods that quantify the structure and dynamics of microsolvated species (both H2O in C5H12 and C5H12 in H2O). At room temperature, interfacial water at the pentane phase boundary is found to have markedly different organization and dynamics than at the vapor interface (as indicated by the hydrogen bond distributions and hydrogen bond persistence in solution). While the mesoscale interfacial properties (e.g. interfacial tension) are sensitive to the specific pentane isomer, the distribution and persistence of microsolvated species at the interface is nearly identical for both systems, irrespective of temperature (between 273 K and 298 K). This has important implications for understanding how properties defined by the interfacial organization are related to the underlying solvation reactions that drive formation of the phase boundary.

  4. Modeling of Flow Field and Slag/liquid Interface in the Crystallizer System of a Thin Slab Steel Continuous Casting

    NASA Astrophysics Data System (ADS)

    Mahmodi, S.; Meisami, A. H.; Atabaki, M. Mazar; Aboutalebi, M. R.

    2012-03-01

    In the present investigation, a three dimensional steady flow field model inside crystallizer system of a thin slab steel continuous caster is presented using real geometrical dimension starting from the inlet port of the nozzle. The nozzle flow was modeled considering the minimum casting defects. In addition, a new numerical model is developed for a thin slab casting mold. The velocity of the liquid from the inlet and outlet of the nozzle was considered as the boundary condition. The liquid flow field was computed with main concern on the velocities exiting the nozzle ports for the flow in the liquid pool. It was shown that the fluid pattern in the liquid pool has four main fluid rings including two fluid rings provided by the outer fluid coming from the bottom outlets into the liquid pool and two small fluid rings prepared by the fluid coming from the upper inlets into the liquid pool. The flow pattern agrees well with real measurements obtained by water model. The pool simulation shows asymmetries between two sides of the flow, mainly in the lower recirculation zone. The predictions of slag/liquid interface at the top side of the nozzle and its fluctuations show good agreement with the experimental results. The maximum upward wave flow occurred because of the liquid contact to the upper ports. Hence, a maximum upward flow wave was defined to prevent any unsteady state at the highest casting speed and lowest submergence depth.

  5. 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.

  6. 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.

  7. Analysis of the gas states at a liquid/solid interface based on interactions at the microscopic level.

    PubMed

    Li, Zhaoxia; Zhang, Xuehua; Zhang, Lijuan; Zeng, Xiaocheng; Hu, Jun; Fang, Haiping

    2007-08-01

    The states of gas accumulated at the liquid/solid interface are analyzed on the basis of the continuum theory, in which the Hamaker constant is used to describe the long-range interaction at the microscopic scale. The Hamaker constant is always negative, whereas the "gas" spreading coefficient can be either negative or positive. Despite the complexity of gas, including that the density profile may not be uniform due to absorption on both solid and liquid surfaces, we predict three possible gas states at the liquid/solid interface, that is, complete "wetting", partial "wetting", and pseudopartial "wetting". These possible gas states correspond, respectively, to a gas pancake (or film) surrounded by a wet solid, a gas bubble with a finite contact angle, and a gas bubble(s) coexisting with a gas pancake. The typical thickness of the gas pancakes is at the nano scale within the force range of the long-range interaction, whereas the radius of the gas bubbles can be large. The state of a gas bubble(s) coexisting with a gas film is predicted theoretically for the first time. Our theoretical results can contribute to the development of a unified picture of gas nucleation at the liquid/solid interface.

  8. Receptor-Mediated Liposome Fusion Kinetics at Aqueous/Liquid Crystal Interfaces.

    PubMed

    Macri, Katherine M; Noonan, Patrick S; Schwartz, Daniel K

    2015-09-16

    Membrane fusion events are essential to cell biology, and a number of reductionist systems have been developed to mimic the behavior of these biological motifs. One such system monitors the DNA hybridization-mediated fusion of liposomes with the liquid crystal (LC) interface by observing changes in LC orientation using a simple optical detection scheme. We have systematically explored key parameters of this system to determine their effects on individual elementary steps of the complex fusion mechanism. The liposome composition, specifically the degree of lipid unsaturation and PE content, decreased the bilayer rigidity, thereby increasing the rate of vesicle rupture under the stress applied by DNA hybridization. In contrast, the presence of cholesterol had the opposite effect on the mechanical properties of the bilayer, and hence of the membrane fusion rates. The accessibility of receptor moieties (i.e., complementary DNA oligonucleotides) affected the fusion kinetics by modulating the rate of hybridization events. DNA accessibility was controlled by systematic variation of the length of the DNA receptor molecules and the thickness of the steric barrier comprised of adsorbed PEGylated lipids. These results provide design rules for understanding the trade-offs between response kinetics and other important system properties, such as nonspecific adsorption. Moreover, these findings improve our understanding of the biophysical properties of membrane fusion, an important process in both natural and model systems used for bioassay and bioimaging applications. PMID:26317496

  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.

  10. On the behaviour of foreign particles at an advancing solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Pötschke, Jürgen; Rogge, Volker

    1989-03-01

    The present paper describes a theoretical approach to the behaviour at advancing solid-liquid interfaces of foreign particles present in the melt as a separate phase. The temperature field and the influence of a contaminant in the melt were taken into account. The equations which arose were solved numerically. The numerical data can be described with satisfactory accuracy by a function, so that the result can be communicated in the form of a self-contained expression. The use of this equation is found to be in good agreement with recent measurements of latex particles in water: the model gives the critical solidification velocity at which the latex particles of a specific size are only just pushed along by the ice front. An assessment of other measured values given in the literature is not possible since the material values and experimental parameters are not completely known. To consolidate the theory, therefore, further quantitative measurements of systems with known material values, interfacial free energies in particular, are required.

  11. 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

  12. 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

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

    PubMed Central

    Johnson, Ashley R.; Caudill, Cassie L.; Tumbleston, John R.; Bloomquist, Cameron J.; Moga, Katherine A.; Ermoshkin, Alexander; Shirvanyants, David; Mecham, Sue J.; Luft, J. Christopher; DeSimone, Joseph M.

    2016-01-01

    Microneedles, arrays of micron-sized needles that painlessly puncture the skin, enable transdermal delivery of medications that are difficult to deliver using more traditional routes. Many important design parameters, such as microneedle size, shape, spacing, and composition, are known to influence efficacy, but are notoriously difficult to alter due to the complex nature of microfabrication techniques. Herein, we utilize a novel additive manufacturing (“3D printing”) technique called Continuous Liquid Interface Production (CLIP) to rapidly prototype sharp microneedles with tuneable geometries (size, shape, aspect ratio, spacing). This technology allows for mold-independent, one-step manufacturing of microneedle arrays of virtually any design in less than 10 minutes per patch. Square pyramidal CLIP microneedles composed of trimethylolpropane triacrylate, polyacrylic acid and photopolymerizable derivatives of polyethylene glycol and polycaprolactone were fabricated to demonstrate the range of materials that can be utilized within this platform for encapsulating and controlling the release of therapeutics. These CLIP microneedles effectively pierced murine skin ex vivo and released the fluorescent drug surrogate rhodamine. PMID:27607247

  14. Receptor-Mediated Liposome Fusion Kinetics at Aqueous/Liquid Crystal Interfaces.

    PubMed

    Macri, Katherine M; Noonan, Patrick S; Schwartz, Daniel K

    2015-09-16

    Membrane fusion events are essential to cell biology, and a number of reductionist systems have been developed to mimic the behavior of these biological motifs. One such system monitors the DNA hybridization-mediated fusion of liposomes with the liquid crystal (LC) interface by observing changes in LC orientation using a simple optical detection scheme. We have systematically explored key parameters of this system to determine their effects on individual elementary steps of the complex fusion mechanism. The liposome composition, specifically the degree of lipid unsaturation and PE content, decreased the bilayer rigidity, thereby increasing the rate of vesicle rupture under the stress applied by DNA hybridization. In contrast, the presence of cholesterol had the opposite effect on the mechanical properties of the bilayer, and hence of the membrane fusion rates. The accessibility of receptor moieties (i.e., complementary DNA oligonucleotides) affected the fusion kinetics by modulating the rate of hybridization events. DNA accessibility was controlled by systematic variation of the length of the DNA receptor molecules and the thickness of the steric barrier comprised of adsorbed PEGylated lipids. These results provide design rules for understanding the trade-offs between response kinetics and other important system properties, such as nonspecific adsorption. Moreover, these findings improve our understanding of the biophysical properties of membrane fusion, an important process in both natural and model systems used for bioassay and bioimaging applications.

  15. Research on the relation between the contact angle and the interface curvature radius of electrowetting liquid zoom lens

    NASA Astrophysics Data System (ADS)

    Zhao, Cunhua; Liang, Huiqin; Cui, Dongqing; Hong, Xinhua; Wei, Daling; Gao, Changliu

    2011-08-01

    In the ultralight or ultrathin applied domain of zoom lens, the traditional glass / plastic lens is limited for manufacture technology or cost. Therefore, a liquid lens was put forward to solve the problems. The liquid zoom lens has the merits of lower cost, smaller volume, quicker response, lower energy consumption, continuous zoom and higher accuracy. In liquid zoom lens the precise focal length is obtained by the contact angle changing to affect the curvature radius of interface. In our works, the relations of the exerted voltage, the contact angle, the curvature radius and the focal length were researched and accurately calculated. The calculation of the focal length provides an important theoretical basis for instructing the design of liquid zoom lens.

  16. 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.

  17. 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.

  18. Optimization of the Hewlett-Packard particle-beam liquid chromatography-mass spectrometry interface by statistical experimental design.

    PubMed

    Huang, S K; Garza, N R

    1995-06-01

    Optimization of both sensitivity and ionization softness for the Hewlett-Packard particle-beam liquid chromatography-mass spectrometry interface has been achieved by using a statistical experimental design with response surface modeling. Conditions for both optimized sensitivity and ionization softness were found to occur at 55-lb/in.(2) nebulizer flow, 35°C desolvation chamber temperature with approximately 45% organic modifier in the presence of 0.02-F ammonium acetate and a liquid chromatography flow rate of 0.2 mL/min.

  19. Optical non-contact localization of liquid-gas interfaces on disk during rotation for measuring flow rates and viscosities.

    PubMed

    Hoffmann, Jochen; Riegger, Lutz; Bundgaard, Frederik; Mark, Daniel; Zengerle, Roland; Ducrée, Jens

    2012-12-21

    We present a novel technique for the spatio-temporally resolved localization of liquid-gas interfaces on centrifugal microfluidic platforms based on total internal reflection (TIR) at the channel wall. The simple setup consists of a line laser and a linear image sensor array mounted in a stationary instrument. Apart from identifying the presence of usually unwanted gas bubbles, the here described online meniscus detection allows to measure liquid volumes with a high precision of 1.9%. Additionally, flow rates and viscosities (range: 1-12 mPa s, precision of 4.3%) can be sensed even during rotation at frequencies up to 30 Hz.

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

    PubMed

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

    2016-07-19

    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.

  1. 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

  2. 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.

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

    PubMed

    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

  4. Liquid phase sintered composite solders for next generation thermal interface applications

    NASA Astrophysics Data System (ADS)

    Liu, Jia

    It is undeniable that electronics are becoming increasingly powerful and that there is continual effort towards miniaturization of these devices and thus increasing heat generation requires a new paradigm in thermal interface materials (TIM) design. This work was aimed at optimizing the processing parameters and characterizing the performance of Cu-In composite solders produced by liquid phase sintering (LPS). These composites comprise a high-melting phase (HMP) such as Cu embedded in a matrix of a low-melting phase (LMP) such as In. Copper contributes to high thermal and electrical conductivity of composites, whereas the soft In matrix helps maintain high shear compliance. This combination of high electrical/thermal conductivities and high shear compliance makes these solders suitable for a range of next-generation thermal interface material (TIM) and interconnect (IC) applications. After considering a range of compositions, a solder with 60 volume percent In was found to possess the requisite combination of high compliance and high conductivity. During the study, interfacial engineering was introduced to slow down the reaction between Cu and In, and hence further improve the performance of composite solders. A dual interfacial layer consisting of Al 2O3 and Au was used to mitigate the reaction between Cu and In. A 1 nm Al2O3 layer was used as a diffusion barrier to prohibit the inter-diffusion between Cu and In, while a 20 nm Au layer was coated on top of the ceramic Al2O3 for wetting enhancement. The dual layer increased the thermal conductivity of the solder by a factor of ˜2 while reducing the yield strength to make the solder more compliant. The effects of particle size, shape and volume fraction was also studied, and a simple model was utilized to explain the trends in the mechanical and the thermal properties. The optimized Cu-In composite solders were further used to study the performance of solder joints. Mechanical properties under shear and joint

  5. Interface Development in Cu-Based Structures Transient Liquid Phase (TLP) Bonded with Thin Al Foil Intermediate Layers

    NASA Astrophysics Data System (ADS)

    Chen, Ke; Meng, Wen Jin; Eastman, J. A.

    2014-08-01

    Proper bonding and assembly techniques are essential for fabrication of functional metal-based microdevices. Transient liquid phase (TLP) bonding is a promising technique for making enclosed metallic microchannel devices. In this paper, we report results of TLP bonding of Cu-based structures at temperatures between 823 K and 883 K (550 °C and 610 °C) with thin elemental Al foils as intermediate boding layers. In situ X-ray diffraction was utilized to examine the structure of Cu/Al interface in real time, resulting in a proposed sequence of structural evolution of the Cu/Al/Cu TLP bonding interface region. Three different types of bonding interface structures, the " γ 1 structure," the "eutectoid structure" ("E structure"), and the "E/ γ 1/E structure," were observed through electron microscopy, and related to the proposed sequence of interfacial structural evolution. Tensile fracture tests were conducted on TLP-bonded Cu/Al/Cu coupon assemblies. Hardness of the various phases within the bonding interface region was probed with instrumented nanoindentation. Results of mechanical testing were correlated to the structure of the bonding interface region. The present results provide an understanding of the structural evolution within the Cu/Al/Cu TLP bonding interface region, and offer guidance to future bonding of Cu-based microsystems.

  6. Behavior of nonmetallic inclusions in front of the solid-liquid interface in low-carbon steels

    NASA Astrophysics Data System (ADS)

    Kimura, Sei; Nabeshima, Y.; Nakajima, K.; Mizoguchi, S.

    2000-10-01

    The present study is concerned with the interaction phenomena of nonmetallic inclusions in front of a moving solid-liquid interface. The in situ observation was done in a high-temperature experiment by using a laser microscope. Alumina inclusions in an aluminum-killed steel with low oxygen content exhibited the well-known clustering behavior. The velocity of the advancing interface first increased while approaching the particle, but became stagnant during engulfment and increased again after that. Alumina-magnesia complex inclusions in a magnesium-added steel with high oxygen content were very finely dispersed in the molten pool. These inclusions escaped from the advancing interface during solidification, but gathered again at the retreating interface during remelting. The tiny inclusions were thought to behave just as tracer particles of a local flow. The velocity of particles was measured on a video image, and the significant acceleration or deceleration was found near the interface. It was concluded that the flow was induced by the Marangoni effect due to the local difference in temperature and oxygen content in front of the interface, particularly in the case of a higher oxygen content. However, the flow was weak in the case of a low oxygen content.

  7. 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.

  8. 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.

  9. Tailoring the interfaces between nematic liquid crystal emulsions and aqueous phases via layer-by-layer assembly.

    PubMed

    Tjipto, Elvira; Cadwell, Katie D; Quinn, John F; Johnston, Angus P R; Abbott, Nicholas L; Caruso, Frank

    2006-10-01

    We report the assembly of polyelectrolyte multilayer (PEM) films at the interfaces of thermotropic liquid crystal (LC) droplets dispersed in an aqueous phase. Exposure of PEM-coated droplets to surfactant slowed the bipolar-to-radial ordering transition of the LCs by 2 orders of magnitude relative to naked droplets. This shows that PEMs can be used to influence the interactions of analytes with the LC cores of the droplets, allowing tuning of the LC emulsion sensing properties.

  10. 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.

  11. Optimization of an air–liquid interface exposure system for assessing toxicity of airborne nanoparticles

    PubMed Central

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

    2016-01-01

    Abstract 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

  12. 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

  13. Culturing of Human Nasal Epithelial Cells at the Air Liquid Interface

    PubMed Central

    Müller, Loretta; Brighton, Luisa E.; Carson, Johnny L.; Fischer, William A.; Jaspers, Ilona

    2013-01-01

    In vitro models using human primary epithelial cells are essential in understanding key functions of the respiratory epithelium in the context of microbial infections or inhaled agents. Direct comparisons of cells obtained from diseased populations allow us to characterize different phenotypes and dissect the underlying mechanisms mediating changes in epithelial cell function. Culturing epithelial cells from the human tracheobronchial region has been well documented, but is limited by the availability of human lung tissue or invasiveness associated with obtaining the bronchial brushes biopsies. Nasal epithelial cells are obtained through much less invasive superficial nasal scrape biopsies and subjects can be biopsied multiple times with no significant side effects. Additionally, the nose is the entry point to the respiratory system and therefore one of the first sites to be exposed to any kind of air-borne stressor, such as microbial agents, pollutants, or allergens. Briefly, nasal epithelial cells obtained from human volunteers are expanded on coated tissue culture plates, and then transferred onto cell culture inserts. Upon reaching confluency, cells continue to be cultured at the air-liquid interface (ALI), for several weeks, which creates more physiologically relevant conditions. The ALI culture condition uses defined media leading to a differentiated epithelium that exhibits morphological and functional characteristics similar to the human nasal epithelium, with both ciliated and mucus producing cells. Tissue culture inserts with differentiated nasal epithelial cells can be manipulated in a variety of ways depending on the research questions (treatment with pharmacological agents, transduction with lentiviral vectors, exposure to gases, or infection with microbial agents) and analyzed for numerous different endpoints ranging from cellular and molecular pathways, functional changes, morphology, etc. In vitro models of differentiated human nasal epithelial

  14. Culturing of human nasal epithelial cells at the air liquid interface.

    PubMed

    Müller, Loretta; Brighton, Luisa E; Carson, Johnny L; Fischer, William A; Jaspers, Ilona

    2013-10-08

    In vitro models using human primary epithelial cells are essential in understanding key functions of the respiratory epithelium in the context of microbial infections or inhaled agents. Direct comparisons of cells obtained from diseased populations allow us to characterize different phenotypes and dissect the underlying mechanisms mediating changes in epithelial cell function. Culturing epithelial cells from the human tracheobronchial region has been well documented, but is limited by the availability of human lung tissue or invasiveness associated with obtaining the bronchial brushes biopsies. Nasal epithelial cells are obtained through much less invasive superficial nasal scrape biopsies and subjects can be biopsied multiple times with no significant side effects. Additionally, the nose is the entry point to the respiratory system and therefore one of the first sites to be exposed to any kind of air-borne stressor, such as microbial agents, pollutants, or allergens. Briefly, nasal epithelial cells obtained from human volunteers are expanded on coated tissue culture plates, and then transferred onto cell culture inserts. Upon reaching confluency, cells continue to be cultured at the air-liquid interface (ALI), for several weeks, which creates more physiologically relevant conditions. The ALI culture condition uses defined media leading to a differentiated epithelium that exhibits morphological and functional characteristics similar to the human nasal epithelium, with both ciliated and mucus producing cells. Tissue culture inserts with differentiated nasal epithelial cells can be manipulated in a variety of ways depending on the research questions (treatment with pharmacological agents, transduction with lentiviral vectors, exposure to gases, or infection with microbial agents) and analyzed for numerous different endpoints ranging from cellular and molecular pathways, functional changes, morphology, etc. In vitro models of differentiated human nasal epithelial

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Finite-element simulations of the influence of pore wall adsorption on cyclic voltammetry of ion transfer across a liquid-liquid interface formed at a micropore.

    PubMed

    Ellis, Jonathan S; Strutwolf, Jörg; Arrigan, Damien W M

    2012-02-21

    Adsorption onto the walls of micropores was explored by computational simulations involving cyclic voltammetry of ion transfer across an interface between aqueous and organic phases located at the micropore. Micro-interfaces between two immiscible electrolyte solutions (micro-ITIES) have been of particular research interest in recent years and show promise for biosensor and biomedical applications. The simulation model combines diffusion to and within the micropore, Butler-Volmer kinetics for ion transfer at the liquid-liquid interface, and Langmuir-style adsorption on the pore wall. Effects due to pore radius, adsorption and desorption rates, surface adsorption site density, and scan rates were examined. It was found that the magnitude of the reverse peak current decreased due to adsorption of the transferring ion on the pore wall; this decrease was more marked as the scan rate was increased. There was also a shift in the half-wave potential to lower values following adsorption, consistent with a wall adsorption process which provides a further driving force to transfer ions across the ITIES. Of particular interest was the disappearance of the reverse peak from the cyclic voltammogram at higher scan rates, compared to the increase in the reverse peak size in the absence of wall adsorption. This occurred for scan rates of 50 mV s(-1) and above and may be useful in biosensor applications using micropore-based ITIES.

  1. Influence of ionic liquid film thickness on ion pair distributions and orientations at graphene and vacuum interfaces.

    PubMed

    Wang, Yong-Lei; Laaksonen, Aatto; Lu, Zhong-Yuan

    2013-08-28

    Microscopic structures, orientational preferences together with mass, number and electron density distributions of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been studied on a neutral hydrophobic graphene surface, and at the IL-vacuum interface using atomistic Molecular Dynamics simulations. At the IL-graphene interface, distinct mass, number and electron density distributions are observed oscillating into the bulk region with several compact structural layers. The imidazolium ring of [BMIM] cations lies preferentially flat on the graphene surface, with its methyl and butyl side chains elongated along the graphene surface. At the IL-vacuum interface, however, the distributions of [BMIM][PF6] ion pairs are strongly influenced by the thickness of IL film. With the increase of IL film thickness, the orientations of [BMIM] cations at the IL-vacuum interface change gradually from dominant flat distributions along the graphene surface to orientations where the imidazolium rings are either parallel or perpendicular to the IL-vacuum interface with tilted angles. The outmost layers are populated with alkyl groups and imparted with distinct hydrophobic character. The calculated radial distribution functions suggest that ionic structures of [BMIM][PF6] ion pairs in IL-graphene and IL-vacuum interfacial regions are significantly different from each other and also from that in bulk regions.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. 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

  5. Free energy partitioning analysis of the driving forces that determine ion density profiles near the water liquid-vapor interface.

    PubMed

    Arslanargin, Ayse; Beck, Thomas L

    2012-03-14

    Free energy partitioning analysis is employed to explore the driving forces for ions interacting with the water liquid-vapor interface using recently optimized point charge models for the ions and SPC/E water. The Na(+) and I(-) ions are examined as an example kosmotrope/chaotrope pair. The absolute hydration free energy is partitioned into cavity formation, attractive van der Waals, local electrostatic, and far-field electrostatic contributions. We first compute the bulk hydration free energy of the ions, followed by the free energy to insert the ions at the center of a water slab. Shifts of the ion free energies occur in the slab geometry consistent with the SPC/E surface potential of the water liquid-vapor interface. Then the free energy profiles are examined for ion passage from the slab center to the dividing surface. The profiles show that, for the large chaotropic I(-) ion, the relatively flat total free energy profile results from the near cancellation of several large contributions. The far-field electrostatic part of the free energy, largely due to the water liquid-vapor interface potential, has an important effect on ion distributions near the surface in the classical model. We conclude, however, that the individual forms of the local and far-field electrostatic contributions are expected to be model dependent when comparing classical and quantum results. The substantial attractive cavity free energy contribution for the larger I(-) ion suggests that there is a hydrophobic component important for chaotropic ion interactions with the interface.

  6. Molecular dynamics simulations of the aqueous interface with the [BMI][PF6] ionic liquid: Comparison of different solvent models.

    PubMed

    Chevrot, G; Schurhammer, R; Wipff, G

    2006-09-28

    We report a Molecular Dynamics (MD) study of the interface between water and the hygroscopic room temperature Ionic Liquid "IL" [BMI][PF6] (1-butyl-3-methyl-imidazolium hexafluorophosphate), comparing the TIP3P, SPC/E and TIP5P models for water and two IL models where the ions are +/-1 or +/-0.9 charged. A recent MD study (A. Chaumont, R. Schurhammer and G. Wipff, J. Phys. Chem. B, 2005, 109, 18964) showed that using TIP3P water in conjunction with the IL(+/-1) model led to water-IL mixing without forming an interface, whereas a biphasic system could be obtained with the IL(+/-0.9) model. With the TIP5P and SPC/E models, the juxtaposed aqueous and IL phases are found to remain distinct for at least 20 ns. The resulting IL humidity, exaggerated with the IL(+/-1) model, is in better agreement with experiment using the IL(+/-0.9) model. We also report demixing simulations on the "randomly mixed" liquids, using the IL(+/-0.9) model for the ionic liquid. With the three tested water models, the phases separate very slowly ( approximately 20 ns or more) compared to "classical" chloroform-water mixtures (less than 1 ns), leading to biphasic systems similar to those obtained after equilibration of the juxtaposed liquids. The characteristics of the interface (size, polarity, ion orientation, electrostatic potential) are compared with the different models. Possible reasons why, among the three tested water models, the widely-used TIP3P model exaggerates the inter-solvent mixing, are analyzed. The difficulty in computationally and experimentally equilibrating water-IL mixtures is attributed to the slow dynamics and micro-heterogeneity of the IL and to the different states of water in the IL phase.

  7. Capillary interactions between particles bound to interfaces, liquid films and biomembranes.

    PubMed

    Kralchevsky, P A; Nagayama, K

    2000-03-31

    This article is devoted to an overview, comparison and discussion of recent results (both theoretical and experimental) about lateral capillary forces. They appear when the contact of particles or other bodies with a fluid phase boundary causes perturbations in the interfacial shape. The capillary interaction is due to the overlap of such perturbations which can appear around floating particles, vertical cylinders, particles confined in a liquid film, inclusions in the membranes of lipid vesicles or living cells, etc. In the case of floating particles the perturbations are due to the particle weight; in this case the force decreases with the sixth power of the particle size and becomes immaterial for particles smaller than approximately 10 microm. In all other cases the interfacial deformations are due to the particle wetting properties; the resulting 'immersion' capillary forces can be operative even between very small particles, like protein globules. In many cases such forces can be responsible for the experimentally observed two-dimensional particle aggregation and ordering. An analogy between capillary and electrostatic forces enables one to introduce 'capillary charges' of the attached particles, which characterize the magnitude of the interfacial deformation and could be both positive and negative. Moreover, the capillary interaction between particle and wall resembles the image force in electrostatics. When a particle is moving bound to an interface under the action of a capillary force, one can determine the surface drag coefficient and the surface viscosity supposedly the magnitude of the capillary force is known. Alternative (but equivalent) energy and force approaches can be used for the theoretical description of the lateral capillary interactions. Both approaches require the Laplace equation of capillarity to be solved and the meniscus profile around the particles to be determined. The energy approach accounts for contributions due to the increase of

  8. Role of conductivity in the electrohydrodynamic patterning of air-liquid interfaces.

    PubMed

    Gambhire, P; Thaokar, R M

    2012-09-01

    The effect of electrical conductivity on the wavelength of an electrohydrodynamic instability of a leaky dielectric-perfect dielectric (LD-PD) fluid interface is investigated. For instabilities induced by dc fields, two models, namely the PD-PD model, which is independent of the conductivity, and the LD-PD model, which shows very weak dependence on the conductivity of the LD fluid, have been previously suggested. In the past, experiments have been compared with either of these two models. In the present work, experiments, analytical theory, and simulations are used to elucidate the dependence of the wavelength obtained under dc fields on the ratio of the instability time (τs=1/smax) and the charge relaxation time (τc=εε0/σ, where ε0 is the permittivity of vacuum, ε is the dielectric constant, and σ is the electrical conductivity). Sensitive dependence of the wavelength on the nondimensional conductivity S2=σ2μ2h0(2)/(ε0(2)φ0(2)δ2) (where σ2 is the electrical conductivity, μ2 is the viscosity, h0 is the thickness of the thin liquid film, φ0 is the rms value of the applied field, and δ is a small parameter) is observed and the PD-PD and the LD-PD cases are observed only as limiting behaviors at very low and very high values of S2, respectively. Under an alternating field, the frequency of the applied voltage can be altered to realize several regimes of relative magnitudes of the three time scales inherent to the system, namely τc, τs, and the time period of the applied field, τf. The wavelength in the various regimes that result from a systematic variation of these three time scales is studied. It is observed that the linear Floquet theory is invalid in most of these regimes and nonlinear analysis is used to complement it. Systematic dependence of the wavelength of the instability on the frequency of the applied field is presented and it is demonstrated that nonlinear simulations are necessary to explain the experimental results.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    Mande, Hemant M.; Ghalsasi, Prasanna S.

    2015-09-01

    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.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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.

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

    PubMed

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

    2015-01-01

    We present an experimental study investigating the transition zone between a liquid-like unyielded region and a solid-like yielded region in a yield-stress fluid. The configuration consists of a rectangular closed-channel 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. In this study, we use a model fluid, namely polymer micro-gel Carbopol, which exhibits Herschel-Bulkley viscoplastic rheology. Exploiting the fluid transparency, the flow is monitored by particle image velocimetry using an internal visualization technique. The main outcome of this study is to show that, except in a thin transition layer close to the solid-liquid interface, the flow behaves as an apparent Poiseuille flow with an apparent slip condition at the base. The slip frontier is found to be almost independent of the flow rate while the corresponding slip velocity increases with the flow rate.

  19. 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.

  20. 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.

  1. Joint Density Functional Theory for the electrode/electrolyte interface: Benchmarking liquid structure with experiment and ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Letchworth-Weaver, Kendra; Umbright, Christine; Chan, Maria; Fenter, Paul; Arias, T. A.

    Understanding the physics of the interface between a charged electrode surface and a fluid electrolyte would inform design of electrochemical energy storage and conversion devices. However, such studies require a simultaneously accurate yet inherently multi-scale theory. Joint density-functional theory (JDFT) bridges the relevant length-scales by joining a fully ab initio description of the electrode with a low computational cost, yet atomically detailed classical DFT description of the liquid electrolyte structure. Leveraging JDFT within our framework to treat charged systems in periodic boundary conditions, we can predict the voltage-dependent structure and energetics of solvated ions at the interface between graphitic and single-crystalline metallic electrodes and technologically relevant liquid electrolytes. First, we elucidate the physical origin of the experimentally measured voltage-dependent differential capacitance of an Ag(111) electrode in aqueous NaF electrolyte, examining the crucial role of ion de-solvation and physisorption onto the electrode surface. We go on to compare the JDFT-predicted interfacial liquid structure next to a graphitic electrode with results obtained from X-ray reflectivity measurements and ab initio molecular dynamics simulations.

  2. Born-Haber cycle for monolayer self-assembly at the liquid-solid interface: assessing the enthalpic driving force.

    PubMed

    Song, Wentao; Martsinovich, Natalia; Heckl, Wolfgang M; Lackinger, Markus

    2013-10-01

    The driving force for self-assembly is the associated gain in free energy with decisive contributions from both enthalpy and entropy differences between final and initial state. For monolayer self-assembly at the liquid-solid interface, solute molecules are initially dissolved in the liquid phase and then become incorporated into an adsorbed monolayer. In this work, we present an adapted Born-Haber cycle for obtaining precise enthalpy values for self-assembly at the liquid-solid interface, a key ingredient for a profound thermodynamic understanding of this process. By choosing terephthalic acid as a model system, it is demonstrated that all required enthalpy differences between well-defined reference states can be independently and consistently assessed by both experimental and theoretical methods, giving in the end a reliable value of the overall enthalpy gain for self-assembly of interfacial monolayers. A quantitative comparison of enthalpy gain and entropy cost reveals essential contributions from solvation and dewetting, which lower the entropic cost and render monolayer self-assembly a thermodynamically favored process.

  3. Probing charge screening dynamics and electrochemical processes at the solid-liquid interface with electrochemical force microscopy.

    PubMed

    Collins, Liam; Jesse, Stephen; Kilpatrick, Jason I; Tselev, Alexander; Varenyk, Oleksandr; Okatan, M Baris; Weber, Stefan A L; Kumar, Amit; Balke, Nina; Kalinin, Sergei V; Rodriguez, Brian J

    2014-05-20

    The presence of mobile ions complicates the implementation of voltage-modulated scanning probe microscopy techniques such as Kelvin probe force microscopy (KPFM). Overcoming this technical hurdle, however, provides a unique opportunity to probe ion dynamics and electrochemical processes in liquid environments and the possibility to unravel the underlying mechanisms behind important processes at the solid-liquid interface, including adsorption, electron transfer and electrocatalysis. Here we describe the development and implementation of electrochemical force microscopy (EcFM) to probe local bias- and time-resolved ion dynamics and electrochemical processes at the solid-liquid interface. Using EcFM, we demonstrate contact potential difference measurements, consistent with the principles of open-loop KPFM operation. We also demonstrate that EcFM can be used to investigate charge screening mechanisms and electrochemical reactions in the probe-sample junction. We further establish EcFM as a force-based imaging mode, allowing visualization of the spatial variability of sample-dependent local electrochemical properties.

  4. 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.

  5. 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

  6. 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

  7. 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

  8. 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

  9. 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

  10. 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

    2016-07-25

    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.

  11. 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.

  12. The influence of a solid/liquid interface on the fluorescence kinetics of the triphenylmethane dye malachite green

    NASA Astrophysics Data System (ADS)

    Bell, M. A.; Crystall, B.; Rumbles, G.; Porter, G.; Klug, D. R.

    1994-04-01

    Time-resolved fluorescence measurements are reported of a triphenylmethane dye (malachite green), adsorbed at and aqueous/quartz interface, studied by evanescent wave excitation. The importance of internal conversion as the dominant deactivation pathway from the first excited singlet state of malachite green is observed to be greatly reduced for molecules at a solid/liquid interface compared to those in low viscosity solvents. Surface coverage dependent decay kinetics are observed, and at the lowest surface coverages studied, the excited singlet state lifetime of the dye is more than two orders of magnitude greater than the value observed for the dye in aqueous solution. Fluorescence decay kinetics are found to be non mono-exponential under all conditions, and the limitations of simple sum-of-exponentials fitting are discussed in light of other models currently available. It is possible to distinguish at least two populations of malachite green adsorbed at the surface.

  13. Self-assembly of a catechol-based macrocycle at the liquid-solid interface: experiments and molecular dynamics simulations.

    PubMed

    Saiz-Poseu, Javier; Martínez-Otero, Alberto; Roussel, Thomas; Hui, Joseph K-H; Montero, Mavis L; Urcuyo, Roberto; MacLachlan, Mark J; Faraudo, Jordi; Ruiz-Molina, Daniel

    2012-09-14

    This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial sol