Interfacial properties of polymeric liquids

We show that the variations of the surface tension of polymeric solutions gamma with the molecular weight of the sample M(n), the temperature T, and the volume fraction of monomers straight phi(b) are explained by the self-organization of the long flexible chains that are present in the immediate vicinity of the interface. Within a scaling functional theory we find a simple law gamma(straight phi(b),M(n),T) which accounts quantitatively for the experimental data available in the literature with a very high accuracy.     

Interfacial properties of hybrid nanomaterials

A brief summary of our ongoing efforts to understand the surface properties of nanoparticles using fluorophores, namely pyrene alkanethiols, is presented. Excited state interactions were investigated by varying the length of the spacer group and the concentration of fluorophore. The flexible long alkyl chain tethering pyrene inAu-P2/Au-P3 allows free interaction between fluorophores resulting in excimer formation whereas the intermolecular interactions are limited in theAu-P 1 system due to the restriction imposed by the curvature of spherical gold nanoparticle. A gradual increase in the peak intensity ratio of III/I band of the normal fluorescence of pyrene was observed indicating that the surface of nanoparticle is more polar than the bulk solvent (toluene)     

Resonant tunneling properties of inverted Morse double quantum barrier

We study resonant tunneling characteristics of inverted Morse double quantum barrier structures. The effect of electric bias and structure parameters is calculated by using non-equilibrium Green's function method. Results for the transmission coefficients are compared with the structure parameters. Our results show that the widths of the wells and heights of barriers have a significant effect on the transmission properties. We found that the resonant peak of the transmission coefficient decreases with increasing electric field bias. Moreover, resonant energy level increases with increasing barrier height and increasing width parameters.     

Interfacial properties in solid-stabilized emulsions

We prepared concentrated monodisperse oil-in-water emulsions stabilized by solid particles. The osmotic resistance, , of the emulsions was measured for different oil volume fractions above the random close packing ( ). The dimensionless osmotic resistance, /(/R) ( being the interfacial tension and R being the undeformed drop radius), was always substantially higher than the corresponding values obtained for surfactant-stabilized emulsions. It can be concluded that droplet deformation in solid-stabilized emulsions is not controlled by the capillary pressure, /R, of the non-deformed droplets but rather by 0/R, 0 being a parameter characterizing the rigidity of the droplets surfaces. The data can be interpreted considering that the interfacial layers are elastic at small deformations and exhibit plasticity at intermediate deformations. 0 corresponds to the surface yield stress, i.e. the transition between elastic and plastic regimes. We discuss the origin of the surface behavior considering the strong lateral interactions that exist between the adsorbed solid particles. We propose an independent measurement of 0 based on the critical bulk stress that produces droplet fragmentation in dilute emulsions submitted to shear. Finally, the bulk shear elastic modulus was measured as a function of and confirms many of the features revealed by the osmotic resistance.     

Interfacial properties of elastically strained materials

Equations are derived which generalize the Laplace-Kelvin laws of force and chemical potential balance for a curved interface between a solid and its melt. The main difference from previous treatments are strain corrections in the equation of melting equilibrium, for which a simple physical picture is developed. These corrections are usually small, but they are essential in order to achieve an internally consistent formulation. When applied to sound transmission at the solid-superfluid interface of⁴He, they guarantee energy conservation thereby answering a paradox raised by Maris.     

Thermodynamic properties of inhomogeneous fluids

A general method, the method of variation under extension, is presented for expressing the thermodynamic properties of an inhomogeneous fluid as functionals of the local number density, when given a density functional for the total thermodynamic grand potential of the fluid. The method is demonstrated in detail for the van der Waals square-gradient density functional and for the nonlocal density functional which arises in the theory of fluids with long-ranged pair potentials or in the mean-field theory of penetrable-sphere models. As specific examples, we consider the planar and spherical interface between two fluid phases, the line of contact of three fluid phases, the contact line between two surface phases and the planar interface between a solid and fluid.     

Optical properties of magneto-nonlocal fluids

General optical properties of the polarizable linear magneto-nonlocal fluids are investigated. A set of nonlocal constitutive equations for the dielectric tensor are proposed. The general expression for the refractive index is derived and the effects of nonlocality and magnetic field are discussed. The special case when the speed of fluid motion is much smaller than that of light is also considered while the corresponding birefringence is derived and discussed.     

Interfacial properties of a driven diffusive system

A study is made of the low-temperature interfacial properties of a driven system with a single conserved density whose bulk properties were first analyzed, using computer simulations, by Katz, Lebowitz, and Spohn in 1983. The system corresponds to a nearest neighbor interacting lattice gas of charged particles (henceconserved order parameter), which are acted upon by a uniform, constant external electric fieldE. Starting from a bulk kinetic equation, an integral equation for the interface is derived. Nonlocal coupling between different parts of the interface arises from local particle conservation. The interface at any angle is shown to be stable against small deformations ofall wavelengths that are large compared to the interfacial width. However, the relaxation rate(k) for the interface exhibits a strongorientational dependence, which can be understood in terms of the modification of nonlocality byE. The wandering of the interface is considered. Also, the possible stabilizing effect of periodic boundary conditions on the orientation toward the direction ofE is discussed.     

NMR properties of petroleum reservoir fluids

NMR well logging of petroleum reservoir require the measurement of the NMR response of water, oil, and gas in the pore space of rocks at elevated temperatures and pressures. The viscosity of the oil may range from less than 1 cp to greater than 10,000 cp. Also, the oil and gas are not a single component but rather a broad distribution of components. The log mean T1 and T2 relaxation time of dead (gas free) crude oils are correlated with viscosity/temperature and Larmor frequency. The relaxation time of live oils deviate from the correlation for dead crude oils. This deviation can be correlated with the methane content of the oil. Natural gas in the reservoir has components other than methane. Mixing rules are developed to accommodate components such as ethane, propane, carbon dioxide, and nitrogen. Interpretation of NMR logs uses both relaxation and diffusion to distinguish the different fluids present in the formation. Crude oils have a broad spectrum of components but the relaxation time distribution and diffusion coefficient distribution are correlated. This correlation is used to distinguish crude oil from the response of water in the pores of the rock. This correlation can also be used to estimate viscosity of the crude oil.     

Equilibrium properties of hard non-sphere fluids

Derivation of the thermodynamic properties of fluids of hard non-spherical molecules of arbitrary symmetry is based on the decoupling approximation. Theoretical expressions are given and calculations made for the equation of state and virial coefficients for hard ellipsoids. These results are compared with Monte Carlo values and show fair agreement in all cases. The theoretical predictions for the equation of state for binary mixtures are compared with the Monte Carlo results for hard spheres and hard prolate spherocylinders. Theoretical expressions for the first order quantum correction to the free energy, pressure and virial coefficients are also given. The quantum effects increase with increase of density and with increase of anisotropy parameter.     

Magnetic properties of undecane-based magnetic fluids

The magnetic properties of magnetic fluids based on n-undecane have been presented. The temperature dependences of the magnetic susceptibility in the absence and presence of a bias field have been analyzed. A step change in the specific heat of the medium, which is characteristic of magnetic phase transitions, has been discovered.     

Magnetohydrodynamic properties of incompressible Meissner fluids

We consider a superconducting material that exists in the liquid state, more precisely, in which the Meissner-Ochsenfeld effect persists in the liquid state. First, we investigate how the shape of such a hypothetical Meissner liquid will adapt to accomodate for an applied external field. In particular, we analyse the case of a droplet of Meissner fluid, and compute the elongation of the droplet and its quadrupole frequency as a function of the applied field. Next, the influence of an applied field on the flow of the liquid is studied for the case of a surface wave. We derive the dispersion relation for surface waves on an incompressible Meissner fluid. We discuss some candidate realizations of the Meissner fluids and for the case of a superconducting colloid discuss which regime of wave lengths would be most affected by the Meissner effect.     

Static dielectric properties of Stockmayer fluids

Dielectric constants for the Stockmayer fluid are computed both from the equilibrium fluctuations of the polarization and from the polarization response to an applied field in a molecular dynamics simulation with periodic boundary conditions and with the dipole interactions treated by the Ewald method. The dielectric constant at finite wavelength is obtained from a Kirkwood-like expression, while for uniform polarization fluctuations a different expression applies due to the absence of surface effects in the Ewald calculation. The results are nearly independent of the number (up to 500) of particles investigated, even at large values of the dipole moment. The dielectric constants obtained from the approximate solution of the hypernetted chain integral equation are considerably larger than the molecular dynamics results except at low dielectric constants. The external field simulation permits study of the non-linear dependence of the dielectric constant on the magnitude of the applied electric field.     

Coexistence and interfacial properties of triangle-well fluids

Coexistence and interfacial properties of triangle-well fluids are determined by combining the slab technique and the replica exchange algorithm for different interaction ranges (λ = 1.5, 1.75, 2.0, 2.5, and 3). This is implemented using both Monte Carlo and molecular dynamics methods. We make use of a recently proposed substitution of the hard-core repulsion by a linear function with a large negative slope. This makes possible to gain access through the virial route to thermodynamical properties and to employ widely spread packages such as Gromacs. Coexistence curves of these systems were calculated with both implementations and compared to those previously reported in the literature. A good agreement was found among them. Surface tension data obtained from Monte Carlo and molecular dynamics techniques also show a good agreement.     

Static dielectric properties of polarizable Stockmayer fluids

The effect on the thermodynamics and distribution functions in including point polarizability in the Stockmayer fluid is evaluated. A large effect on the dielectric constant is found. As in the non-polarizable case, the single super chain integral equation gives dielectric constants in excess of the computed values except at low dielectric constants.     

Magnetic properties and magneto-birefringence of magnetic fluids

Static magnetic properties of a large variety of magnetic fluids with magnetite particles is studied. A qualitative study of magnetization curves was performed to establish the influence of interactions or the presence of agglomerations in each sample. Improved equations for magneto-granulometric analysis, for ideal ferrofluids, were proposed. Better results for the mean magnetic diameter than in the case of using the known equations were obtained. A quantitative study using several models for ideal and interacting particles was performed to select the best method and dimensional distribution function for magneto-granulometric analysis as well as for accurately determining macroscopic quantities of samples (initial susceptibility, saturation magnetization, particle number density or magnetic volume fraction) and properties of nanoparticles (mean magnetic diameter, thickness of the nonmagnetic layer and particle distribution). A new model for magneto-birefringence was proposed and discussed as well as applied for diluted and concentrated ferrofluids. The Langevin behaviour of samples was investigated and compared with the investigation based on magnetic properties. Nanoparticles parameters like mean “magneto-optical” diameter, effective anisotropy constant, Shliomis diameter and the real part of the electrical permittivity of particles were accurately determined. Received 18 July 1999 and Received in final form 13 January 2000