Hydrodynamic origin of diffusion in nanopores

We study the transport of a subcritical Lennard-Jones fluid in a cylindrical nanopore, using a combination of equilibrium and nonequilibrium as well as dual control volume grand canonical molecular dynamics methods. We show that all three techniques yield the same value of the transport coefficient for diffusely reflecting pore walls, even in the presence of viscous transport. We also demonstrate that the classical Knudsen mechanism is not manifested, and that a combination of viscous flow and momentum exchange at the pore wall governs the transport over a wide range of densities.     

Evidence for viscoelastic effects in surface capillary waves of molten polymer films

The surface dynamics of supported ultrathin polystyrene films with thickness comparable to the radius of gyration were investigated by surface sensitive x-ray photon correlation spectroscopy. We show for the first time that the conventional model of capillary waves on a viscous liquid has to be modified to include the effects of a shear modulus in order to explain both static and dynamic scattering data from ultrathin molten polymer films.     

The effects of chain segment motion on ionic diffusion in solid polymer electrolytes

The “vehicular effects” of chain segment motion on ionic diffusion in solid polymer electrolytes have been investigated via numerical simulation on a two-dimensional square lattice where the dynamical variation of chain configuration is presented by translational or rotational bond movement. It is found that (a) both types of bond motion promote continuous diffusion when the fraction (p) of available bonds is below the static percolation threshold of p=0.5 in two dimensions; (b) translational motion of bonds parallel to the direction of diffusion produces larger diffusion coefficients (D) than that by random renewal of the dynamic bond percolation model (DBPM), while the perpendicular motion or rotational motion gives smaller values of D; (c) Smooth lines instead of “stair-case like” curves generated by DBPM are obtained in the mean-squared displacement versus time plot, when bonds are shifting along the diffusion route. The dependence of diffusion coefficients on the variation of motion patterns of bonds is expected to be related to the temperature change under which these patterns are excited accordingly, such that VTF behavior of certain polymer electrolytes may be deduced.     

Hydrodynamic interactions of dilute polymer solutions in elongational flow

Dumbbell models are only crude representations of actual polymer molecules, but their simplicity allows for explicit calculations which in many instances have shed light on the connection between molecular properties and rheological behavior. On the other hand, hydrodynamic interactions are known to strongly influence the dynamic response of polymer solutions and this makes the representation of the hydrodynamic drag an important aspect in the calculations. In the present work, the effects of the state of flow are incorporated explicitly in the frictional properties of the FENE model of a dilute polymer solution. Results for the steady elongational viscosity and the mean square end-to-end distance arc presented.     

Cooperative diffusion in concentrated polymer solutions

Summary Concentrated solutions of polystyrene in dioctylphthalate have been examined as a function of temperature over the concentration range 0.2 to 0.9 g/ml. The static screening length and the hydrodynamic screening length evaluated from the cooperative-diffusion coefficient are compared with the predictions of current models. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Unusual thermal diffusion in polymer solutions

Thermal diffusion forced Rayleigh scattering results on thermal diffusion of poly(ethylene oxide) (PEO) in ethanol/water mixtures are presented. In water-rich solvent mixtures, PEO is found to migrate towards regions of lower temperature. This is typical for polymer solutions and corresponds to a positive Soret coefficient of PEO. In solvent mixtures with low water content, however, the polymer is found to migrate towards higher temperatures, corresponding to a negative Soret coefficient of PEO in ethanol-rich solutions. To our knowledge, this is the first observed sign change of the Soret coefficient of a polymer in solution. We also present a simple lattice model for the polymer solvent system and calculate Soret coefficients with statistical mechanics methods. The calculated values agree qualitatively with the experimental results.     

A viscoelastic model of polarization switching in polymer ferroelectrics

The theoretical aspects of the viscoelastic model for polarization switching in ??soft?? organic ferroelectrics have been considered. The model describes the amplitude-frequency dependences of the hysteresis loops obtained upon polarization switching in thin films of the ferroelectric copolymer poly(vinylidene fluoride-trifluoroethylene).     

Hydrodynamic self-consistent field theory for inhomogeneous polymer melts

We introduce a mesoscale technique for simulating the structure and rheology of block-copolymer melts and blends in hydrodynamic flows. The technique couples dynamic self-consistent field theory with continuum hydrodynamics and flow penalization to simulate polymeric fluid flows in channels of arbitrary geometry. We demonstrate the method by studying phase separation of an ABC triblock copolymer melt in a submicron channel with neutral wall wetting conditions. We find that surface wetting effects and shear effects compete, producing wall-perpendicular lamellae in the absence of flow and wall-parallel lamellae in cases where the shear rate exceeds some critical Weissenberg number.     

Magnetorotational-type instability in Couette-Taylor flow of a viscoelastic polymer liquid

We describe an instability of viscoelastic Couette-Taylor flow that is directly analogous to the magnetorotational instability (MRI) in astrophysical magnetohydrodynamics, with polymer molecules playing the role of magnetic field lines. By determining the conditions required for the onset of instability and the properties of the preferred modes, we distinguish it from the centrifugal and elastic instabilities studied previously. Experimental demonstration and investigation should be much easier for the viscoelastic instability than for the MRI in a liquid metal. The analogy holds with the case of a predominantly toroidal magnetic field such as is expected in an accretion disk, and it may be possible to access a turbulent regime in which many modes are unstable.     

Hydrodynamic cavitation for sonochemical effects

A comparative study of hydrodynamic and acoustic cavitation has been made on the basis of numerical solutions of the Rayleigh-Plesset equation. The bubble/cavity behaviour has been studied under both acoustic and hydrodynamic cavitation conditions. The effect of varying pressure fields on the collapse of the cavity (sinusoidal for acoustic and linear for hydrodynamic) and also on the latter's dynamic behaviour has been studied. The variations of parameters such as initial cavity size, intensity of the acoustic field and irradiation frequency in the case of acoustic cavitation, and initial cavity size, final recovery pressure and time for pressure recovery in the case of hydrodynamic cavitation, have been found to have significant effects on cavity/bubble dynamics. The simulations reveal that the bubble/cavity collapsing behaviour in the case of hydrodynamic cavitation is accompanied by a large number of pressure pulses of relatively smaller magnitude, compared with just one or two pulses under acoustic cavitation. It has been shown that hydrodynamic cavitation offers greater control over operating parameters and the resultant cavitation intensity. Finally, a brief summary of the experimental results on the oxidation of aqueous KI solution with a hydrodynamic cavitation set-up is given which supports the conclusion of this numerical study. The methodology presented allows one to manipulate and optimise of specific process, either physical or chemical.     

Hydrodynamic effects in interacting Fermi electron jets

We theoretically study hydrodynamic phenomena originating from electron-electron collisions in a two-dimensional Fermi system. We demonstrate that an electron beam sweeping past an aperture creates a pumping effect, attracting carriers from this aperture. This pumping effect originates from the specific electric potential distribution induced by the injected electrons. In the regions near the main stream of injected electrons, a positive potential is induced by the injected electrons. Thus, the normally repulsive Coulomb interaction leads to an attractive force in the Fermi system. This quantum pumping mechanism in a Fermi system differs qualitatively from the Bernoulli pumping effect in classical liquids. We also discuss possible experimental realizations.     

On the mechanics of rim instabilities in viscoelastic polymer thin films

We determine appropriate attractors for higher than third-order central moments for the relaxation process in three-dimensional lattice Boltzmann methods. It was previously assumed that the appropriate attractors for the relaxation of these moments were their equilibria values as derived from a Maxwell-Boltzmann distribution. However, when the attractor for fourth-order central moments is derived that way, the solution of three-dimensional lattice Boltzmann differs significantly from the analytical solution of the Navier-Stokes equation for simple test cases like Poiseuille flow. We show that the Navier-Stokes solution is recovered when we chose products of low order central moments as the attractors of the higher order central moments.     

Theory of spin diffusion in liquid-phase polymer systems

A general theory of spin diffusion in condensed media is constructed by the method of Zwanzig-Mori projection operators using the superpositional approximation to decouple the many-particle correlation functions. The spin diffusion coefficient is expressed in the form D _sp=D _tr+D _f , where D _tr is the contribution associated with translational displacements of the molecules and D _f is the contribution caused by intermolecular flip-flop processes. The expression for D _tr differs from the well-known Kubo-Green formula for the self-diffusion coefficient D _sd in that the integrand contains an additional factor P _f (t), which is the probability of the molecular spins not participating in intermolecular flip-flop transitions over the time t. A microscopic expression is obtained for D _f in the form of a time integral of the intermolecular dipole-dipole dynamic correlation functions. For liquid-phase polymer system with fairly high molecular mass the condition D _sp≫D _sd is satisfied. Zh. éksp. Teor. Fiz. 114, 538–554 (August 1998)     

Radiotracer diffusion and ionic conduction in a PEO-NaI polymer electrolyte

We studied ion transport in amorphous PEO30NaI consisting of poly(ethylene oxide) and sodium iodide in a Na-to-O ratio of 30. Diffusion coefficients of the radiotracers 22Na and 125I were measured for temperatures between 67 and 180 degrees C and compared with the overall charge diffusivity deduced from dc conductivity data. To explain the observed discrepancy between the sum of the tracer diffusivities and the charge diffusivity we propose a detailed model which is based on the formation of neutral ion pairs. Evaluating simultaneously all experimental data within this model yields not only the true diffusion coefficient of all individual species but also the ion-pairing reaction constant as a function of temperature.     

Study of polymer dissolution and diffusion by laser interferometry

A Mickelson laser interferometer is used to study the polymer dissolution and diffusion in the system of cellulose diacetate fiber and nitromethane solvent. Digital interferograms at different stages of the diffusion mixing are obtained. The kinetics of the diffusion parameters (refractive index distribution and concentration of the medium) is considered. The diffusion coefficients of the polymer in the mass transfer process are determined, and their temperature dependences are constructed.