The role of capillary and surface forces in the crossover behavior of solid nanoparticles at liquid interfaces

We investigate the interaction between a nanoparticle and an oil-water interface with particular emphasis on the particle crossing through the interface. The formation of a three-phase contact line is investigated in two cases, namely in the presence and in the absence of surface forces. We carefully examine the interplay between capillary and surface forces in such systems. Two instabilities of the interface (snap-in/snap-out) as the particle is moved through the interface are identified and quantitatively described. While the snap-in instability was observed in some AFM studies, the precise interface position and configuration relative to the particle at the instability depends on the nature of the surface forces present in the system. After the snap-in, the particle is adsorbed and must overcome an energy barrier due to the interface deformation in order to cross-over to the other liquid. We make quantitative predictions on the interface configuration at the instabilities and the free energy barrier height. The roles of particle size and different interaction parameters characterizing the system in determining the magnitude of the energy barrier for crossing and in the formation of a three-phase contact line are discussed. Ultimately, this study will enable us to make quantitative predictions on capillary effects in nanoparticle-microemulsions mixtures and other colloidal systems. For particles in the micrometer range and larger the capillary forces dominate over the surface forces and dictate how the snap-in occurs. However, the situation becomes different for particle sizes smaller than about 100 nm. The presence of surface forces modifies the interface configuration and the free energy jump at the snap-in instability.     

Competing forces in the interaction of polyelectrolytes with charged interfaces

In this review, we discuss the competition of non-DLVO forces in the adsorption of polyelectrolytes onto charged surfaces. We consider two particularly illustrative problems, namely the adsorption of polyelectrolytes onto similarly charged surfaces and the reversal of surface charge by adsorption of polyelectrolytes. Emphasis is made on how simulation results help to understand relevant experimental situations.     

On the role of electrostatic forces in the adhesion of polymer particles to solid surfaces

Simultaneous measurements have been made of the adhesive force and double electric charge of particles after their removal from a metal surface. For the systems investigated, the adhesive force and charge on the particles increase with particle diameter according to a power law with an exponent close to 2. Such dependence can be explained on the basis of the electrostatic nature of the adhesive forces. A double electric layer exists at the interface between the particles and the metal surface. A calculation was made of the surface density of charge for the polyvinyl chloride particle-steel system.     

Non-equilibrium thermodynamics and kinetic theory of gas mixtures in the presence of interfaces

A broad range of the boundary value problems of the kinetic theory of gases and gas mixtures is considered based on kinetic theory and non-equilibrium thermodynamics. The interrelation of the kinetic theory and non-equilibrium thermodynamics is discussed. The balance equations at the interface are obtained for the case of the boundary layers with peculiar properties. Procedures for deriving the boundary conditions for slightly rarefied gas mixtures are outlined. The problems of calculating slip coefficients are discussed. The specificity of the kinetic effects in the boundary conditions is shown. A set of general relations related to gas mixture flows in capillaries is deduced. The possibility of non-equilibrium kinetic effects in the form of a paradoxical distribution of non-equilibrium temperature is shown. Methods of non-equilibrium thermodynamics are used to obtain the phenomenological equations describing the thermophoresis and diffusiophoresis of particles and cross phenomena. The growth and evaporation of droplets is considered based on kinetic theory and non-equilibrium thermodynamics.     

Investigations on the migration behaviour of purines and pyrimidines in capillary electromigration techniques with UV detection and mass spectrometric detection

Different approaches for the separation of a set of nucleosides and nucleobases using capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) are described. Several electrolyte compositions have been tested for this purpose. The addition of appropriate amounts of borate to the carrier electrolyte allowed manipulating migration orders in CZE and MEKC by selective complexation of the nucleosides. For detection either UV or two different modes of mass spectrometric (MS) detection were employed. The latter approach included a comparison of two ion sources namely electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) with respect to their potential in the detection of the selected compounds. Thereby it could be demonstrated that, in particular when it comes to the analysis of real samples, APPI-MS is the better choice if MS detection of purines and pyrimidines after separation by CZE is required.     

Discussion of problems of nonequilibrium thermodynamics of polymers as presented in the paper by Sommer and Reiter

A number of discussion points are raised concerning the nonequilibrium melting and crystallization as described in the paper by Sommer and Reiter.¹     

Chemical displacements at solid interfaces. Easy cathodic reduction of alkyl bromides in the presence of iodide ions at palladized surfaces

Solid electrodes such as glassy carbon and platinum modified by “palladization” (galvanostatic deposits from acidic solutions of Pd²⁺) may exhibit exceptional catalytic capabilities, especially in the cathodic cleavage of alkyl bromides when achieved in the presence of traces of iodide ions. The use of such chemically modified surfaces leads to important potential shifts compared to the use of glassy carbon or smooth palladium in the absence of iodide. The catalytic behaviour is assigned to a nucleophilic-like displacement at the adsorbed state, between the organic bromide and iodide ion. Thus palladium surfaces can be successfully employed for cleaving carbon–halogen bonds at very moderate negative potentials. Preliminarily results have revealed that all palladized electrodes give an adsorption-like peak assigned to the corresponding alkyl iodide adsorbed on (or reacting with) the surface. The influence of different parameters like the organic substrate and the iodide concentration, the thickness of the palladium deposit, and the stand-by time before reduction are preliminarily presented. Such processes were found to be one-electron. However, electrodes were shown to readily age, presumably by strong adsorption of generated alkyl radicals.     

Effect of local environment on nanoscale dynamics at electrochemical interfaces: anisotropic growth and dissolution in the presence of a step providing evidence for a schwoebel-ehrlich barrier at solid/liquid interfaces

The dynamics of nanoscale islands in the vicinity of a monoatomic step on a metal electrode surface under potential control have been investigated by potential pulse perturbation time-resolved scanning tunneling microscopy (P3 TR-STM). As the metastable islands decay, a clear anisotropy develops in the spatial distribution of islands, relative to the monoatomic step. Islands appear to be stabilized above the step, while a denuded region develops below the step over a distance of about 100 nm. Vacancy islands are observed to be more stable than adatom islands. These results provide evidence for an electrochemical Schwoebel-Ehrlich barrier to diffusion of atoms across the step.     

The drop size in membrane emulsification determined from the balance of capillary and hydrodynamic forces

Here, we investigate experimentally and theoretically the factors that determine the size of the emulsion droplets produced by membrane emulsification in "batch regime" (without applied crossflow). Hydrophilic glass membranes of pore diameters between 1 and 10 mum have been used to obtain oil-in-water emulsions. The working surfactant concentrations are high enough to prevent drop coalescence. Under such conditions, the size of the formed drops does not depend on the surfactant type and concentration, on the interfacial tension, or on the increase of viscosity of the inner (oil) phase. The drops are monodisperse when the working transmembrane pressure is slightly above the critical pressure for drop breakup. At higher pressures, the size distribution becomes bimodal: a superposition of a "normal" peak of monodisperse drops and an "anomalous" peak of polydisperse drops is observed. The theoretical model assumes that, at the moment of breakup, the hydrodynamic ejection force acting on the drop is equal to the critical capillary force that corresponds to the stability-instability transition in the drop shape. The derived equations are applied to predict the mean size of the obtained drops in regimes of constant flow rate and constant transmembrane pressure. Agreement between theory and experiment is established for the latter regime, which corresponds to our experimental conditions. The transition from unimodal to bimodal drop size distribution upon increase of the transmembrane pressure can be interpreted in terms of the transition from "dripping" to "jetting" mechanisms of drop detachment.     

Self-organization of substituted 1,3,4-oxadiazoles in the solid state and at surfaces

Different aspects of the structure formation for a class of molecules containing the diphenyl-1,3,4-oxadiazole fragment are discussed. Starting from the bulk state with the ideal crystal lattice and the derivation of some common packing motifs the formation of liquid-crystalline states are described. This leads to the consideration of structures found in Langmuir-Blodgett films and those obtained by organic molecular beam deposition. These structures may again be compared to those for the bulk crystalline state. Common features as well as characteristic differences due to peculiarities of the individual molecular structures are discussed.     

星型高分子共混体系的相平衡、相分离和相界面的统计力学理论

在平均场近似下求得了星型高分子共混体系的混合自由能及其相分离动力学方程。本文的理论结果表明,型高分子共混体系与线型高分子共混体系相比具有更快的相分离速度。而且,因其相界面张力较低,体系较易形成更多的相界面,浓度涨落的临界波矢也更大。除此之外,由于在相同分子量的条件下星型高分子的尺寸要小,因此其相界面更窄,当星型高分子的臂数为1或2时,所有结果均合理地还原到熟知的线型高分子共混体系的结果。因此,本文的结果具有更大的普遍性。     

Quantum-chemical investigation of the interaction of propene and oxygen with solid CoO?MgO surfaces

The interaction of propene and oxygen with Co²⁺, Co³⁺ and Mg²⁺ ions on the MgO lattice surface, as well as the adsorption of charged forms of O ₂ ^– and -allyl radical have been studied by a quantum-chemical method. Propene adsorption has been found to be stronger on Co³⁺ than on Co²⁺ and Mg²⁺ ions. Unlike propene, oxygen is adsorbed more strongly on Co²⁺ ions with subsequent electron transfer to an oxygen molecule. The data obtained are compared with experimental results.

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- Co²⁺, Co³⁺ Mg²⁺ MgO, O ₂ ^– - . , Co³⁺, Co²⁺ Mg²⁺. - Co²⁺ . .

     

Application of programmed thermodesorption of the liquid under quasi-isothermal conditions to investigate physicochemical properties of liquid layers and solid surfaces

This paper presents the results of measurements of the programmed thermodesorption of polar and nonpolar liquids from the surface of different types of solids. The course of thermodesoption was found to depend on the properties of the solid and the wetting liquid. Thermodesorption occurred not exponentially but in steps, which reflects the noncontinuous changes in the properties of the surface layer with the distance from the solid surface. This effect intensified with the increase in polarity of the wetting liquid and the heterogeneity of the solid surface. The earlier investigations showed that application of the method of differential thermal analysis allowed determination of the distribution of the adsorption potential of the liquid on the solid surface.The author is indebted to Prof. M. Jaroniec for very fruitful discussions and to Prof. J. Choma for the activated carbon samples.     

Molecular dynamics study of thermal phenomena in an ultrathin liquid film sheared between solid surfaces: the influence of the crystal plane on energy and momentum transfer at solid-liquid interfaces

A molecular dynamics study has been performed on a liquid film sheared between moving solid walls. Thermal phenomena that occur in the Couette-like flow were examined, including energy conversion from macroscopic flow energy to thermal energy, i.e., viscous heating in the macroscopic sense, and heat conduction from the liquid film to the solid wall via liquid-solid interfaces. Four types of crystal planes of fcc lattice were assumed for the surface of the solid wall. The jumps in velocity and temperature at the interface resulting from deteriorated transfer characteristics of thermal energy and momentum at the interface were observed. It was found that the transfer characteristics of thermal energy and momentum at the interfaces are greatly influenced by the types of crystal plane of the solid wall surface which contacts the liquid film. The mechanism by which such a molecular scale structure influences the energy transfer at the interface was examined by analyzing the molecular motion and its contribution to energy transfer at the solid-liquid interface.     

The use of multidimensional capillary chromatography in conjunction with a triple quadropule mass-spectrometer in the analysis of complex mixtures (GC-GC-MS-MS)

The analysis of complex mixtures, such as essential oils requires high resolution chromatographic separation and even the use of very efficient columns cannot prevent the overlapping of certain peaks. This means that it is very difficult to obtain high quality mass spectra when the sample contains numerous constituants. The pre-separation by column or preparative GC leads to a considerable loss of material and, often, to the formation of artefacts. In order to overcome some of these difficulties, we have built a simple multi-column system that is connected to an MS-MS instrument. Two independent chromatographs equipped with capillary columns were connected. The interface, which consists of a modified PTV injector, gives the possibilities of direct transfer, back-flushing, heart-cutting, intermediate cold trapping, trace enrichment and selective sample introduction. These operations are controlled by a switching valve system (DANI-MFC 393 unit). The chromatographic system was first connected to a MS-MS instrument which may result in high MS and collision activated MS spectra.     

Extracting stoichiometry, thermodynamics, and kinetics for the interaction of DNA with cadmium ion by capillary electrophoresis on-line coupled with electrothermal atomic absorption spectrometry

Understanding the binding of cadmium with DNA is of great importance for elucidating the mechanism of cadmium genotoxicity and carcinogenicity. In the present work, CE on-line coupled with electrothermal atomic absorption spectrometry was employed to study the binding electrophoretic behaviors, stoichiometry, thermodynamics, and kinetics for the interaction of cadmium cation (Cd(II)) with DNA. The stoichiometry (Cd(II) to DNA (as the concentration of base pairs)) for the interaction was determined to be 1:5. Two types of binding sites on DNA were observed with the binding constants of 10(6) and 10(5) L/mol, respectively, showing strong affinity of Cd(II) to DNA. The interaction of Cd(II) with both types of binding sites on DNA were driven by negative enthalpy change with a large positive entropy change. The binding of Cd(II) to DNA followed a first-order kinetics for Cd(II) with the apparent activation energy of 45.7 +/- 1.9 kJ/mol. The results obtained in present investigation would be helpful to understanding the genotoxicity and carcinogenicity of cadmium.     

Implications of the phase rule for capillary systems containing surfaces and three-phase contact lines with surface and linear constraint relations

The phase rule is generalized to heterogeneous systems with moderately curved surfaces and linear or line-phase boundaries. It will be shown that the number of degrees of freedom or variancef of a capillary sysem is, in general, larger than that predicted by the classical Gibbs' phase rule. Restrictions on the value off for capillary systems is intimately connected with the imposition of mechanical constraints like the Laplace and Young equations of capillarity. As a direct consequence, it may be shown that the variance for anr-component, three-phase solid-liquid-vapour system (i.e., a liquid drop on a solid surface) is different from that of anr-component, liquid-liquid-vapour system. This conclusion has important implications for the existence or possible existence of equation-of-state type relations.     

The effect of surface roughness on the adhesion of solid surfaces for systems with and without liquid lubricant

We present molecular dynamics results for the interaction between two solid elastic walls during pull-off for systems with and without octane (C(8)H(18)) lubricant. We used two types of substrate--flat and corrugated--and varied the lubricant coverage from approximately 1/8 to approximately 4 ML (monolayers) of octane. For the flat substrate without lubricant the maximum adhesion was found to be approximately three times larger than for the system with the corrugated substrate. As a function of the octane coverage (for the corrugated substrate) the pull-off force first increases as the coverage increases from 0 to approximately 1 ML, and then decreases as the coverage is increased beyond monolayer coverage. It is shown that at low octane coverage, the octane molecules located in the substrate corrugation wells during squeezing are pulled out of the wells during pull-off, forming a network of nanocapillary bridges around the substrate nanoasperities, thus increasing the adhesion between two surfaces. For greater lubricant coverages a single capillary bridge is formed. The adhesion force saturates for lubricant coverages greater than 3 ML. For the flat substrate, during pull-off we observe discontinuous, thermally activated changes in the number n of lubricant layers (n-1-->n layering transitions), whereas for the corrugated substrate these transitions are "averaged" by the substrate surface roughness.