Spatially resolved microrheology through a liquid/liquid interface

We present a light-scattering technique for the measurement of the microrheological properties of viscoelastic liquids in small volumes over a large frequency range (on the order of eight decades). The accuracy of the method for model viscoelastic liquids (polyethylene oxide solutions in water) is demonstrated by comparing the results with conventional mechanical measurements of the loss and storage moduli. Then we show that the method can be used to measure variations in viscoelastic properties in a heterogeneous system by measuring the variation in the moduli with position (and time) across a liquid/liquid interface between a viscoelastic polymer solution and a Newtonian liquid.     

Characteristics of a liquid/liquid optical waveguide using sheath flow and its application to detect molecules at a liquid/liquid interface.

The formation conditions and characteristics of a liquid/liquid optical waveguide (LLW) were studied using a two-phase sheath flow, where the inner organic phase flow acted as the core and the outer aqueous flow acted as the clad. In immiscible solvent systems, i.e., toluene/water and diethyl ether/water systems, the LLWs were formed in the range of higher than ca. 600 of the Reynolds number (Re), where the linear velocity of the organic solvent was much higher than that of the aqueous solution. On the other hand, in a miscible solvent system, i.e., a tetrahydrofuran/water system, a stable LLW was formed in the range of a much lower Re than in immiscible systems. Moreover, the molecules at the toluene/water interface of the LLW were observed with both fluorescence and absorbance measurement systems. In particular, the change in the fluorescence spectrum of 1-anilino-8-naphthalenesulfonate (ANS) at the interface within 1 ms was observed by this method, indicating the usefulness of the LLW for a fast kinetic study of a liquid/liquid interface.     

Freezing of a liquid marble

In this study, we present for the first time the observations of a freezing liquid marble. In the experiment, liquid marbles are gently placed on the cold side of a thermo-electric cooler (TEC), and the morphological changes are recorded and characterized thereafter. These liquid marbles are noticed to undergo a shape transition from a spherical to a flying-saucer-shaped morphology. The freezing dynamics of liquid marbles is observed to be very different from that of a freezing water droplet on a superhydrophobic surface. For example, the pointy tip appearing on a frozen water drop could not be observed for a frozen liquid marble. In the end, we highlight a possible explanation of the observed morphology.     

Modelling a nematic liquid crystal

The bulk phase liquid crystalline behaviour of a cyclic siloxane with a pentamethylcyclosiloxane core and biphenyl-4-allyloxybenzoate mesogens (BCS) was studied using molecular dynamics (MD) and wide angle X-ray analysis. This material exhibits partial crystallinity at room temperature and liquid crystalline behaviour above 120° C. For the MD simulations an ensemble of 27 molecules with 135 mesogenic units was simulated and a molecular mechanics force field was used to model the structural anisotropy of the siloxane molecules. Simulations were carried out both at room temperature and at an elevated temperature (425 K). Room temperature simulations showed that, contrary to our initial assumptions, the low energy molecular conformations were not cylindrical but splayed in shape. During the simulation a smectic-like, tilted layer structure was found to evolve for the cluster when full atom potentials were used, while no such development was observed when electrostatic interactions were neglected. The presence of a tilted layered structure was also suggested by the X-ray data. These results indicate that long range electrostatic interactions are significant for the molecular system under study. In order to calculate the orientational order parameter, the orientation of the molecular axis had to be determined. This was achieved by describing the mesogen shapes to be ellipsoidal and defining the principal axis of the ellipsoids to be the molecular directors. By sampling over 200 ps of simulation at 425 K, the time averaged order parameter (S) was calculated. The calculated S of 0.36 was comparable to the value of 0.4-0.45 found from the experimental data. Apart from providing insight into the relative importance of the various competing forces in the formation of the liquid crystalline phase, these simulations are also expected to be useful in predicting the mesophase behaviour of liquid crystalline systems.     

Adjustment of a GC automatic liquid sampler for high-performance liquid chromatography

Summary An automatic liquid sampler for high-performance liquid chromatography is described.The sampler is based on a GC-injection system from Hewlett-Packard. The HPLC sampler has a unique cleaning system, excellent reproducibility and a plug-in compatibility for sample identification and computer control for Hewlett-Packard integrators and Laboratory Data Systems.     

Confinement effect on the adsorption from a binary liquid system near liquid/liquid phase separation

The preferential adsorption of one component of a binary system at the inner surfaces of mesoporous silica glasses was studied in a wide composition range at temperatures close to liquid/liquid phase separation. Confinement effects on the adsorption were investigated by using three controlled-pore glass (CPG-10) materials of different mean pore size (10 to 50 nm). For the experimental system (2-butoxyethanol+water), which exhibits an upper miscibility gap, strong preferential adsorption of water occurs, as the coexistence curve is approached at bulk compositions, at which water is the minority component. In this strong adsorption regime the area-related surface excess amount of adsorbed water decreases with decreasing pore width, while the shift in the volume-related mean composition of the pore liquid shows an opposite trend, i.e., greatest deviation from bulk composition occurring in the most narrow pores. A simple mean-field lattice model of a liquid mixture confined by parallel walls is adopted to rationalize these experimental findings. This model reproduces the main findings of the confinement effect on the adsorption near liquid/liquid phase separation.     

Room temperature ionic liquid as a novel medium for liquid/liquid extraction of metal ions

Room temperature ionic liquids (RTILs) have been used as novel solvents to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. The hydrophobic character and water immiscibility of certain ionic liquids allow their use in solvent extraction of hydrophobic compounds. In this work, a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent to study liquid/liquid extraction of heavy metal ions. Dithizone was employed as a metal chelator to form neutral metal-dithizone complexes with heavy metal ions to extract metal ions from aqueous solution into [C₄mim][PF₆]. This extraction is possible due to the high distribution ratios of the metal complexes between [C₄mim][PF₆] and aqueous phase. Since the distribution ratios of metal dithiozonates between [C₄mim][PF₆] and aqueous phase are strongly pH dependent, the extraction efficiencies of metal complexes can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation, and preconcentraction of heavy metal ions with the biphasic system of [C₄mim][PF₆] and aqueous phase can be achieved by controlling the pH value of the extraction system. Preliminary results indicate that the use of [C₄mim][PF₆] as an alternate solvent to replace traditional organic solvents in liquid/liquid extraction of heavy metal ions is very promising.     

Decorating a liquid interface promotes splashing

We report on the role of a surfactant monolayer in the impact of small spheres on an air-water interface. We observe that an air cavity (splashing) is induced above a threshold impact velocity. We explore the dependence of this threshold velocity on the bath surface tension and on the bath viscosity using water-ethanol and water-glycerol mixtures, respectively. Interestingly, the threshold velocity for air entrainment is reduced by the presence of a stearic acid monolayer because the hydrophobic tails favor the forced entry of air during the sphere's impact. More generally, we show that this threshold velocity is determined by the wettability of the sphere by the bath, which can equivalently be controlled by tuning the bath properties (presence of a monolayer) or the sphere surface properties (via a surface treatment). These results provide insight into recently developed vesicle production techniques based on the impact of drops or jets on a lipid layer.     

Aerosol preconcentration on a liquid electrode

Electrostatic preconcentration of a dried aerosol is achieved with a water electrode. The system is found to show similar trapping characteristics to those given by wire electrodes, but the subsequent introduction of collected material into a flame atomizer is easier, merely requiring aspiration of the electrode solution after the trapping cycle is complete. The system has been tested for some 40 elements, 5 of which failed to show any response. The failures are attributed to a vapour-phase reaction of the solution aerosol during its passage through the desolvation system, leading to formation of water-insoluble species.     

Thermal conductivity of a polymerizing liquid

Thermal conductivity kappa of seven polymerizing liquids has been measured in real time at different temperatures, and calorimetry and dielectric spectroscopy of one liquid are performed to help interpret the results. As a covalently bonded linear chain or a network structure in the liquid grows, kappa of the Debye equation initially increases with the polymerization time t(polym) as the molecular weight, density, and sound velocity increase, as on cooling a liquid. The measured kappa reaches a maximum and then decreases, thus showing a peak at a certain t(polym) and finally becomes constant, which is not the true behavior of steady state kappa. The dielectric relaxation time of the covalently bonded structure at the t(polym) for the kappa peak is less than 5 s and the extent of polymerization is below the vitrification plateau value. The peak height increases when the pulse time for kappa measurement is increased. An increase in the liquid's temperature shifts the kappa peak to a shorter t(polym). Liquid compositions polymerizing rapidly show a similar shift, and those polymerizing slowly or whose viscosity does not reach a high enough value show a small kappa peak or none. The kappa peak may be an artifact of the time dependence of heat capacity during the pulse time used for the kappa measurement, as proposed for glasses and supercooled liquids, similar to the changes in other properties observed as an artifact of kinetic freezing/unfreezing. For a polymerizing liquid, the peak may additionally arise when the rate of increase in the elastic modulus becomes equal to the rate of decrease in equilibrium Cp. In either case, its appearance does not distinguish the Brownian motions' slowing on polymerization from that on cooling or compressing a liquid.     

Evaporation of a binary liquid mixture

An apparatus was designed to measure the evaporation rates of the components comprising a binary liquid mixture, from a horizontal surface, under condi Evaporation studies were conducted on the ethanol-water system. The effects on the evaporation rate of air velocity and liquid composition were investiThe experimental evaporation rates were shown to depend on vapour pressure driving force. For the pure component, the evaporation exhibited a direct li For ethanol-water mixtures the total and ethanol component evaporation increased with increasing ethanol concentration, while that of the water compone     

Microdroplet deposition under a liquid medium

An experimental and numerical study of the factors affecting the reproducibility of microdroplet depositions performed under a liquid medium is presented. In the deposition procedure, sample solution is dispensed from the end of a capillary by the aid of a pressure pulse onto a substrate with pillar-shaped sample anchors. The deposition was modeled using the convective Cahn-Hilliard equation coupled with the Navier-Stokes equations with added surface tension and gravity forces. To avoid a severe time-step restriction imposed by the fourth-order Cahn-Hilliard equation, a semi-implicit scheme was developed. An axisymmetric model was used, and an adaptive finite element method was implemented. In both the experimental and numerical study it was shown that the deposited volume mainly depends on the capillary-substrate distance and the anchor surface wettability. A critical equilibrium contact angle has been identified below which reproducible depositions are facilitated.     

Colloidal rings in a liquid mixture

We investigate the self-assembly of colloidal particles on microscopic decane droplets in water and show that, by use of paramagnetic colloids, it is possible to assemble ringlike structures that can be controlled with a magnetic field. Moreover, the use of paramagnetic colloids allows us to determine the attractive forces between the colloids located at the three-phase contact line between decane, water, and air. The attractive force is in the femtonewton range and is attributed to capillary interactions due to interface deformations. When the liquid emulsion dries on a glass slide, we observe solid deposits in the form of microscopic rings of varying diameters.     

Lattice model of a polar liquid

The molecular model of a polar liquid based on the lattice gas theory was used to study the liquid—gas phase equilibrium. In this theory, the key unknown variables are the probabilities of various mutual pair positions of the molecules. The molecules are considered as non-polarizable point dipoles. The intermolecular interaction potential includes a dipole—dipole component depending on the molecular orientation and the Lennard-Jones contribution stabilizing the system with dipole interactions. The theory provides qualitative agreement with experimental data on the water—vapor equilibrium.     

Molecular complexes in liquid crystalline structures as a stabilizer at liquid interfaces

Summary Phase equilibria in systems of water/p-xylene/amines have been investigated. The results show that the polar interactions giving rise to molecular complexes in liquids and solids do not have the same structural influence in the liquid crystalline phase.Regarding this the opinion that molecular complexes act as stabilizers for emulsions and foams is criticized. The basic stabilizing element is rather a liquid crystalline phase at the interface and consequently definite molecular ratios of surfactants do not have a decisive effect on the stability. The more general interaction of the stabilizer with both the aqueous and with the nonpolar phase is pointed out.     

Synthesis of a liquid crystalline azobenzene monomer for photoalignment of ferroelectric liquid crystals

A liquid crystalline dimethacrylate-based monomer containing an azobenzene group was synthesized. The miscibility of the azo monomer and its crosslinked polymer network with ferroelectric liquid crystals (FLCs) was improved by the liquid crystallinity of the monomer. By performing thermal polymerization of the azo monomer dissolved in a FLC host under linearly polarized visible light irradiation, following a pre-irradiation with unpolarized UV light at room temperature, bulk alignment of the FLC could be induced in the absence of surface orientation layers, as a result of the photo-orientation of azobenzene moieties related to the reversible trans-cis photoisomerization of the chromophore. The optical and rubbing-free alignment of a FLC could be achieved with as few as 0.5 wt % of the azo polymer network. This represents a step toward the preparation of uniform samples of photoaligned FLC by reducing the amount of the azo polymer network that may be phase-separated from the FLC host.     

Rheology of a pyramidal liquid crystal

We have measured the shear elastic modulus and the viscosity values of a pyramidal liquid crystal both normal and parallel to the columnar axis. It was observed that above frequencies of 50Hz, the sample behaves as a Maxwell solid characterized by constant G and eta values. The shear modulus is in the range of 106-107 N m-2, typical for rubbers and polystyrene foams. The viscosity values are in the range of 103-104 Pas, comparable to polymer melts. The observations can be qualitatively explained by temporary entanglements between the side chains of the bowl-shaped molecules, as observed by previous X-ray studies.     

Water adsorption on a liquid surface

Monolayer adsorption of water onto an ionic liquid in ultra-high vacuum has been demonstrated, revealing a heat of adsorption which exceeds the heat of absorption into the bulk liquid by approximately 40 kJ mol(-1).     

Ultraviolet laser photo-modulation voltammetry of tetraphenylborate at a liquid/liquid interface.

Photo-modulation voltammetry was applied to detecting the photolysis of tetraphenylborate (TPhB) at a water/1,2-dichloroethane (DCE) interface by using a He-Cd laser emitting a beam with a major 325-nm line and minor lines of shorter wavelengths. When the interface was irradiated from the water-phase side, a new wave appeared in the photomodulation voltammogram, suggesting that TPhB was photolyzed and the anionic product was transferred across the interface. The concentration dependence of the photocurrents was successfully explained by a theory based on the photolytic process at the interface.