Proposed physical mechanism that gives rise to cosmic inflation.

Early in the Universe a chemical equilibrium exists between photons and electron-positron ([Formula: see text]) pairs. In the electron Born self-energy (eBse) model the [Formula: see text] plasma falls out of equilibrium above a glass transition temperature [Formula: see text] determined by the maximum electron/positron number density of [Formula: see text] where [Formula: see text] is the electron radius. In the glassy phase ([Formula: see text]) the Universe undergoes exponential acceleration, characteristic of cosmic inflation, with a constant potential energy density [Formula: see text]. At lower temperatures [Formula: see text] photon-[Formula: see text] chemical equilibrium is restored and the glassy phase gracefully exits to the [Formula: see text] cosmological model when the equation of state [Formula: see text], corresponding to a cross-over temperature [Formula: see text]. In the eBse model the inflaton scalar field is temperature [Formula: see text] where the potential energy density [Formula: see text] is a plateau potential, in agreement with Planck collaboration 2013 findings. There are no free parameters that require fine tuning to give cosmic inflation in the eBse model.

Nonclassical Surface Nucleation of 6CB at the Air-Liquid Interface of a 6CB Oil-in-Water Nanoemulsion.

The surface tension of a freshly extruded pendant drop of a nanoemulsion, 4-cyano-4'-hexylbiphenyl or 6CB (a liquid crystal) in water, exhibits an unusual surface nucleation phenomenon. Initially the surface tension is that of pure water; however, after a surface nucleation time, the surface tension decreases suddenly in magnitude. This nucleation time, of hundreds to thousands of seconds, depends strongly upon (i) the 6CB concentration in water, (ii) the 6CB nanodroplet size, and (iii) the temperature. Similar behavior is observed in both the isotropic and nematic phases of 6CB; thus, this surface nucleation phenomenon is unrelated to this system's liquid crystalline properties. The observed surface nucleation behavior can be explained via considerations of the nanoemulsion's bulk entropy together with the number of 6CB nanodroplets in the vicinity of the surface.

Pickering Emulsion Transitions in 2,6-Lutidine Plus Water Critical Liquid Mixtures.

Silica particle (S) stabilized oil-in-water Pickering emulsions are observed in the two-phase region of the critical liquid mixture 2,6-lutidine (L) plus water (W). De-emulsification is found at temperatures below a particle wetting transition temperature Tw(R) where Tw(R) decreases toward the lower critical temperature Tc for smaller particle radii R. The presence of a Pickering emulsion transition and its dependence upon particle radius can be explained by a competition between destabilizing gravitational forces and stabilizing forces originating from the critical interfacial tension. As a corollary to these observations, the line tension τ at the three-phase SLW contact line is determined as a function of temperature.

Finite-Size and Solvent Dependent Line Tension Effects for Nanoparticles at the Air-Liquid Surface.

The line tension for a nanoparticle (NP) at the air-liquid surface can be determined by examining the variation in NP solution surface tension with bulk NP concentration. In this publication the variation in line tension with liquid solvent is examined for the homologous series of liquids from n-decane through to n-octadecane. Finite-size line tension effects are also studied by examining the variation in line tension with NP size for NPs at the air-octadecane surface. Both the line tension variation with solvent and NP size can be qualitatively explained using an interface displacement model for the line tension.

Atomic force phase imaging for dynamic detection of adsorbed hydrogen on a catalytic palladium surface under liquid.

Dynamic observation of hydrogen on catalytic metal surfaces is a challenging aspect of studying liquid-phase heterogeneous catalysis. Current methods suffer from one or more of the following limitations: the requirement to observe the surface in high vacuum, the inability to provide nanometer-level spatial resolution, the inability to deal with opaque catalysts and/or liquid immersion phase, the lack of real-time scanning of the surface area, and the inability to assess pronounced topographies or mixed materials. Atomic force microscopy (AFM) phase-shift imaging remedies these issues and provides an opportunity for dynamic direct observation of catalyst surfaces at or near actual reaction conditions immersed in liquid. Hydrogen was delivered to a palladium surface immersed in water by diffusion through a support film of dense polycarbonate. The palladium surface was continuously probed by tapping-mode AFM. The theoretically predicted time-dependent appearance of hydrogen on the water-covered palladium surface matched the experimental observation reasonably well. The technique demonstrated here is unique in that the appearance of hydrogen is dynamically detected in real time on a catalyst surface immersed in water with nanometer-scale spatial resolution. The results presented here supply a new level of information for heterogeneous catalysis that is not available with existing techniques. This work opens new avenues in the study of heterogeneous catalysis, a field with tremendous practical importance and serious analytical challenges.

Electrowetting actuated microfluidic transport in surface grooves with triangular cross section.

Liquids show different static wetting morphologies in open triangular grooves depending upon the wedge angle (ψ) of the groove and the liquid contact angle (θ) with the substrate. Switching between different morphologies can be achieved either by varying the contact angle of the liquid or by changing the wedge angle of the groove. In the present work we manipulate the apparent contact angle of a liquid by electrowetting to switch between liquid morphologies, from droplet to filament, to achieve microfluidic transport of the liquid into open triangular grooves. The static length of liquid filaments in grooves is analyzed as a function of applied voltage for different applied ac frequencies. The dynamic advancement of the filament lengths in grooves is analyzed as a function of time for different applied voltages for two different liquids: first with contact angle greater than the wedge angle and second with contact angle smaller than the wedge angle. Later an exact electrical model is derived to explain the liquid transport in triangular grooves actuated by electrowetting which includes the precise geometry of the liquid morphology.

Liquid droplet coalescence and fragmentation at the aqueous-air surface.

For hexadecane oil droplets at an aqueous-air surface, the surface film in coexistence with the droplets exhibits two-dimensional gaseous (G), liquid (L), or solid (S) behavior depending upon the temperature and concentration of the cationic surfactant dodecyltrimethylammonium bromide. In the G (L) phase, oil droplets are observed to coalesce (fragment) as a function of time. In the coalescence region, droplets coalesce on all length scales, and the final state is a single oil droplet at the aqueous-air surface. The fragmentation regime is complex. Large oil droplets spread as oil films; hole nucleation breaks up this film into much smaller fluctuating and fragmenting or metastable droplets. Metastable droplets are small contact angle spherical caps and do not fluctuate in time; however, they are unstable over long time periods and eventually sink into the bulk water phase. Buoyancy forces provide a counterbalancing force where the net result is that small oil droplets (radius r < 80 µm) are mostly submerged in the bulk aqueous medium with only a small fraction protruding above the liquid surface. In the G phase, a mechanical stability theory for droplets at liquid surfaces indicates that droplet coalesce is primarily driven by surface tension effects. This theory, which only considers spherical cap shaped surface droplets, qualitatively suggests that in the L phase the sinking of metastable surface droplets into the bulk aqueous medium is driven by a negative line tension and a very small spreading coefficient.

Analysis of atomic force microscopy phase data to dynamically detect adsorbed hydrogen under ambient conditions.

Characterization of the interactions of hydrogen with catalytic metal surfaces and the mass transfer processes involved in heterogeneous catalysis are important for catalyst development. Although a range of technologies for studying catalytic surfaces exist, much of it relies on high-vacuum conditions that preclude in situ research. In contrast, atomic force microscopy (AFM) provides an opportunity for direct observation of surfaces under or near actual reaction conditions. Tapping-mode AFM was explored here because it expands AFM beyond the usual topographic information toward speciation and other more subtle surface information. This work describes using phase-angle information from tapping-mode AFM to follow the interactions of hydrogen with palladium, polycarbonate, and iron. Real-time AFM phase-angle information allowed for the observation of multiphase mass transfer to and from the surface of palladium at atmospheric pressure and room temperature without the need for complex sample preparation. The AFM observations are quantitatively benchmarked against and confirm mass transfer predictions based on bulk hydrogen diffusion data. Additionally, they support recent studies that demonstrate the existence of multiple hydrogen states during interactions with palladium surfaces.

Line tension of alkane lenses on aqueous surfactant solutions at phase transitions of coexisting interfaces.

Alkane droplets on aqueous solutions of surfactants exhibit a first-order wetting transition as the concentration of surfactant is increased. The low-concentration or "partial wetting" state corresponds to an oil lens in equilibrium with a two-dimensional dilute gas of oil and surfactant molecules. The high-concentration or "pseudo-partial wetting" state consists of an oil lens in equilibrium with a mixed monolayer of surfactant and oil. Depending on the combination of surfactant and oil, these mixed monolayers undergo a thermal phase transition upon cooling, either to a frozen mixed monolayer or to an unusual bilayer structure in which the upper leaflet is a solid layer of pure alkane with hexagonal packing and upright chains while the lower leaflet remains a disordered liquid-like mixed monolayer. Additionally, certain long-chain alkanes exhibit a surface freezing transition at the air-oil interface where the top monolayer of oil freezes above its melting point. In this review, we summarize our previous studies and discuss how these wetting and surface freezing transitions influence the line tension of oil lenses from both an experimental and theoretical perspective.

Influence of line tension on spherical colloidal particles at liquid-vapor interfaces.

Atomic force microscopy (AFM) imaging of isolated submicron dodecyltrichlorosilane coated silica spheres, immobilized at the liquid polystyrene- (PS-) air interface at the PS glass transition temperature, T(g), allows for determination of the contact angle θ versus particle radius R. At T(g), all θ versus R measurements are well described by the modified Young's equation for a line tension τ = 0.93 nN. The AFM measurements are also consistent with a minimum contact angle θ(min) and minimum radius R(min), below which single isolated silica spheres cannot exist at the PS-air interface.

Long reach cantilevers for sub-cellular force measurements.

Maneuverable, high aspect ratio poly(3,4-ethylene dioxythiophene) (PEDOT) fibers are fabricated for use as cellular force probes that can interface with individual pseudopod adhesive contact sites without forming unintentional secondary contacts to the cell. The straight fibers have lengths between 5 and 40 µm and spring constants in the 0.07-23.2 nN µm(-1) range. The spring constants of these fibers were measured directly using an atomic force microscope (AFM). These AFM measurements corroborate determinations based on the transverse vibrational resonance frequencies of the fibers, which is a more convenient method. These fibers are employed to characterize the time dependent forces exerted at adhesive contacts between apical pseudopods of highly migratory D. discoideum cells and the PEDOT fibers, finding an average terminal force of 3.1 ± 2.7 nN and lifetime of 23.4 ± 18.5 s to be associated with these contacts.

Solubility of gold nanoparticles as a function of ligand shell and alkane solvent.

The solubility of ca. 5.0 nm gold nanoparticles was studied systematically as a function of ligand shell and solvent. The ligands were octane-, decane-, dodecane- and hexadecanethiols; the solvents were the n-alkanes from hexane to hexadecane and toluene. Supernatant concentrations in equilibrium with precipitated superclusters of nanoparticles were measured at room temperature (23 °C) with UV-Vis spectrophotometry. The solubility of nanoparticles ligated with decane- and dodecanethiol was greatest in n-decane and n-dodecane, respectively. In contrast, the solubility of nanoparticles ligated with octane- and hexadecanethiol showed decreasing solubility with increasing solvent chain length. In addition the solubility of the octanethiol ligated system showed a nonmonotonic solvent carbon number functionality with even numbered solvents being better solvents than neighboring odd numbered solvents.

Nanoparticle adsorption at liquid-vapor surfaces: influence of nanoparticle thermodynamics, wettability, and line tension.

We developed a statistical mechanical theory that describes the adsorption of nanoparticles (NPs) at liquid-vapor surfaces. This theory accounts for the surface to bulk NP thermodynamic equilibrium, as well as the NP mechanical equilibrium, wettability, and line tension at liquid-vapor surfaces. The theory is tested by examining the adsorption of 5 nm diameter dodecanethiol-ligated gold NPs at the liquid-vapor surface of a homologous series of n-alkane solvents, from n-nonane to n-octadecane, where the NP wettability decreases with an increasing n-alkane chain length.

Wetting morphologies and their transitions in grooved substrates.

When exposed to a partially wetting liquid, many natural and artificial surfaces equipped with complex topographies display a rich variety of liquid interfacial morphologies. In the present article, we focus on a few simple paradigmatic surface topographies and elaborate on the statics and dynamics of the resulting wetting morphologies. It is demonstrated that the spectrum of wetting morphologies increases with increasing complexity of the groove structure. On elastically deformable substrates, additional structures in the liquid morphologies can be observed, which are caused by deformations of the groove geometry in the presence of capillary forces. The emergence of certain liquid morphologies in grooves can be actively controlled by changes in wettability and geometry. For electrically conducting solid substrates, the apparent contact angle can be varied by electrowetting. This allows, depending on groove geometry, a reversible or irreversible transport of liquid along surface grooves. In the case of irreversible liquid transport in triangular grooves, the dynamics of the emerging instability is sensitive to the apparent hydrodynamic slip at the substrate. On elastic substrates, the geometry can be varied in a straightforward manner by stretching or relaxing the sample. The imbibition velocity in deformable grooves is significantly reduced compared to solid grooves, which is a result of the microscopic deformation of the elastic groove material close to the three phase contact line.

Improved in situ spring constant calibration for colloidal probe atomic force microscopy.

In colloidal probe atomic force microscopy (AFM) surface forces cannot be measured without an accurate determination of the cantilever spring constant. The effective spring constant k depends upon the cantilever geometry and therefore should be measured in situ; additionally, k may be coupled to other measurement parameters. For example, colloidal probe AFM is frequently used to measure the slip length b at solid/liquid boundaries by comparing the measured hydrodynamic force with Vinogradova slip theory (V-theory). However, in this measurement k and b are coupled, hence, b cannot be accurately determined without knowing k to high precision. In this paper, a new in situ spring constant calibration method based upon the residuals, namely, the difference between experimental force-distance data and V-theory is presented and contrasted with two other popular spring constant determination methods. In this residuals calibration method, V-theory is fitted to the experimental force-distance data for a range of systematically varied spring constants where the only adjustable parameter in V-theory is the slip length b. The optimal spring constant k is that value where the residuals are symmetrically displaced about zero for all colloidal probe separations. This residual spring constant calibration method is demonstrated by studying three different liquids (n-decanol, n-hexadecane, and n-octane) and two different silane coated colloidal probe-silicon wafer systems (n-hexadecyltrichlorosilane and n-dodecyltrichlorosilane).

Dissipation mechanisms in ionic liquids.

The spreading of ionic liquids on molecularly smooth solid surfaces has been little studied in the past. We show that the spreading behaviors of the two ionic liquids, [EMIM] ethyl sulfate and ECOENG 500, are well described by the combined molecular kinetic and hydrodynamic model of de Ruijter, de Coninck, and Oshanin [M.J. de Ruijter, J. de Coninck, G. Oshanin, Langmuir 15 (1999) 2209] with reasonable values for the molecular friction coefficient zeta, molecular displacement lambda, and frequency K0 associated with contact line motion, as well as reasonable values for the microscopic cutoff a associated with hydrodynamic dissipation.

Viscosity-dependent liquid slip at molecularly smooth hydrophobic surfaces.

Colloidal probe atomic force microscopy is used to study the slip behavior of 18 Newtonian liquids from two homologous series, the n-alkanes and n-alcohols, at molecularly smooth hydrophobic n-hexadecyltrichlorosilane coated surfaces. We find that the slip behavior is governed by the bulk viscosity eta of the liquid, specifically, the slip length b approximately etax with x approximately 0.33. Additionally, the slip length was found to be shear rate independent, validating the use of Vinogradova slip theory in this work.

Switching liquid morphologies on linear grooves.

The morphology of liquids confined to linear micrometer-sized grooves of triangular and rectangular cross section is studied for different substrate wettabilities. Depending on the wettability and exact geometry, either droplike morphologies or elongated liquid filaments represent the generic equilibrium structures on the substrate. Upon changing the apparent contact angle of aqueous drops by electrowetting, we are able to trigger the transition between elongated filaments and droplets. In the case of rectangular grooves, this transition allows us to advance liquid reversibly into the grooves while crossing a certain threshold contact angle. In triangular grooves, however, these elongated filaments undergo a dynamic instability when the contact angle returns to a value above the filling threshold. The different filling and drainage behavior is explained by specific aspects of the triangular and rectangular groove geometry.