Hysteresis, force oscillations and non-equilibrium effects in the adhesion of spherical nanoparticles to atomically smooth surfaces

Molecular dynamics simulations are used to examine hysteretic effects and distinctions between equilibrium and non-equilibrium aspects of particle adsorption on the walls of nano-sized fluidfilled channels. The force on the particle and the system's Helmholtz free energy are found to depend on the particle's history as well as on its radial position and the wetting properties of the fluid, even when the particle's motion occurs on time scales much longer than the spontaneous adsorption time. The hysteresis is associated with changes in the fluid density in the gap between the particle and the wall, and these structural rearrangements persist over surprisingly long times. The force and free energy exhibit large oscillations with distance when the lattice of the structured nanoparticle is held in register with that of the tube wall, but not if the particle is allowed to rotate freely. Adsorbed particles are trapped in free energy minima in equilibrium, but if the particle is forced along the channel the resulting stick-slip motion alters the fluid structure and allows the particle to desorb

Forced Convection and Sedimentation Past a Flat Plate

The steady laminar flow of a well-mixed suspension of monodisperse solid spheres, convected steadily past a horizontal flat plate and sedimenting under the action of gravity, is examined. It is shown that, in the limit as Re approaches infinity and epsilon approaches 0, where Re is the bulk Reynolds number and epsilon is the ratio of the particle radius a to the characteristic length scale L, the analysis for determining the particle concentration profile has several aspects in common with that of obtaining the temperature profile in forced-convection heat transfer from a wall to a fluid stream moving at high Reynolds and Prandtl numbers. Specifically, it is found that the particle concentration remains uniform throughout the O(Re(exp -1/2)) thick Blasius boundary layer except for two O(epsilon(exp 2/3)) thin regions on either side of the plate, where the concentration profile becomes non-uniform owing to the presence of shear-induced particle diffusion which balances the particle flux due to convection and sedimentation. The system of equations within this concentration boundary layer admits a similarity solution near the leading edge of the plate, according to which the particle concentration along the top surface of the plate increases from its value in the free stream by an amount proportional to X(exp 5/6), with X measuring the distance along the plate, and decreases in a similar fashion along the underside. But, unlike the case of gravity settling on an inclined plate in the absence of a bulk flow at infinity considered earlier, here the concentration profile remains continuous everywhere. For values of X beyond the region near the leading edge, the particle concentration profile is obtained through the numerical solution of the relevant equations. It is found that, as predicted from the similarity solution, there exists a value of X at which the particle concentration along the top side of the plate attains its maximum value phi(sub m) and that, beyond this point, a stagnant sediment layer will form that grows steadily in time. This critical value of X is computed as a function of phi(sub s), the particle volume fraction in the free stream. In contrast, but again in conformity with the similarity solution, for values of X sufficiently far removed from the leading edge along the underside of the plate, a particle-free region is predicted to form adjacent to the plate. This model, with minor modifications, can be used to describe particle migration in other shear flows, as, for example, in the case of crossflow microfiltration

Roles of Particle-Wall and Particle-Particle Interactions in Highly Confined Suspensions of Spherical Particles Being Sheared at Low Reynolds Numbers

The roles of particle-wall and particle-particle interactions are examined for suspensions of spherical particles in a viscous fluid being confined and sheared at low Reynolds numbers by two parallel walls moving with equal but opposite velocities. Both particle-wall and particle-particle interactions are shown to decrease the rotational velocity of the spheres, so that in the limit of vanishingly small gaps between the spheres and the walls, the spheres acquire a rotational slip relative to the walls. The presence of the walls also increases the particle stresslet and, therefore, the total viscous dissipation. In the limit of vanishingly small gaps, the increased viscous dissipation in the gaps between pairs of spheres aligned in the flow direction is largely compensated by the reduction in the dissipation in the gaps between the spheres and the walls due to a reduction in the rotational velocity of the spheres. As a result, the effect of short-range particle interactions on the stresslet is generally insignificant. On the other hand, the channel-scale particle interactions in the shear flow induced by the moving walls decrease the particle stresslet, primarily because the fraction of pairs of spheres that are aligned parallel to the flow (the presence of which in a shear flow reduces the stresslet) is relatively higher than in unbounded suspensions. Expressions are also derived for the total stress in dilute random suspensions that account for both the particle-wall and the channel-scale particle-particle interactions in determining the rotational velocities and stresses. The latter are shown to be consistent with recent numerical [Y. Davit and P. Peyla, Europhys. Lett. 83, 64001 (2008)] and experimental [P. Peyla and C. Verdier, Europhys. Lett. 94, 44001 (2011)] findings according to which, for a range of sphere radius to gap width ratios, the effect of particle-particle interactions is to decrease the total dissipation

Wetting and particle adsorption in nanoflows

Molecular dynamics simulations are used to study the behavior of closely-fitting spherical and ellipsoidal particles moving through a fluid-filled cylinder at nanometer scales. The particle, the cylinder wall and the fluid solvent are all treated as atomic systems, and special attention is given to the effects of varying the wetting properties of the fluid. Although the modification of the solid-fluid interaction leads to significant changes in the microstructure of the fluid, its transport properties are found to be the same as in bulk. Independently of the shape and relative size of the particle, we find two distinct regimes as a function of the degree of wetting, with a sharp transition between them. In the case of a highly-wetting suspending fluid, the particle moves through the cylinder with an average axial velocity in agreement with that obtained from the solution of the continuum Stokes equations. In contrast, in the case of less-wetting fluids, only the early-time motion of the particle is consistent with continuum dynamics. At later times, the particle is eventually adsorbed onto the wall and subsequently executes an intermittent stick-slip motion.We show that van der Walls forces are the dominant contribution to the particle adsorption phenomenon and that depletion forces are weak enough to allow, in the highly-wetting situation, an initially adsorbed particle to spontaneously desorb

Microsystem strategies for sample preparation in biological detection.

The objective of this LDRD was to develop microdevice strategies for dealing with samples to be examined in biological detection systems. This includes three sub-components: namely, microdevice fabrication, sample delivery to the microdevice, and sample processing within the microdevice. The first component of this work focused on utilizing Sandia's surface micromachining technology to fabricate small volume (nanoliter) fluidic systems for processing small quantities of biological samples. The next component was to develop interfaces for the surface-micromachined silicon devices. We partnered with Micronics, a commercial company, to produce fluidic manifolds for sample delivery to our silicon devices. Pressure testing was completed to examine the strength of the bond between the pressure-sensitive adhesive layer and the silicon chip. We are also pursuing several other methods, both in house and external, to develop polymer-based fluidic manifolds for packaging silicon-based microfluidic devices. The second component, sample processing, is divided into two sub-tasks: cell collection and cell lysis. Cell collection was achieved using dielectrophoresis, which employs AC fields to collect cells at energized microelectrodes, while rejecting non-cellular particles. Both live and dead Staph. aureus bacteria have been collected using RF frequency dielectrophoresis. Bacteria have been separated from polystyrene microspheres using frequency-shifting dielectrophoresis. Computational modeling was performed to optimize device separation performance, and to predict particle response to the dielectrophoretic traps. Cell lysis is continuing to be pursued using microactuators to mechanically disrupt cell membranes. Novel thermal actuators, which can generate larger forces than previously tested electrostatic actuators, have been incorporated with and tested with cell lysis devices. Significant cell membrane distortion has been observed, but more experiments need to be conducted to determine the effects of the observed distortion on membrane integrity and cell viability. Finally, we are using a commercial PCR DNA amplification system to determine the limits of detectable sample size, and to examine the amplification of DNA bound to microspheres. Our objective is to use microspheres as capture-and-carry chaperones for small molecules such as DNA and proteins, enabling the capture and concentration of the small molecules using dielectrophoresis. Current tests demonstrated amplification of DNA bound to micron-sized polystyrene microspheres using 20-50 microliter volume size reactions

The Rheology of Concentrated Suspensions

Research program on the rheological properties of flowing suspensions. The primary purpose of the research supported by this grant was to study the flow characteristics of concentrated suspensions of non-colloidal solid particles and thereby construct a comprehensive and robust theoretical framework for modeling such systems quantitatively. At first glance, this seemed like a modest goal, not difficult to achieve, given that such suspensions were viewed simply as Newtonian fluids with an effective viscosity equal to the product of the viscosity of the suspending fluid times a function of the particle volume fraction. But thanks to the research findings of the Principal Investigator and of his Associates, made possible by the steady and continuous support which the PI received from the DOE Office of Basic Energy Sciences, the subject is now seen to be more complicated and therefore much more interesting in that concentrated suspensions have been shown to exhibit fascinating and unique rheological properties of their own that have no counterpart in flowing Newtonian or even non-Newtonian (polymeric) fluids. In fact, it is generally acknowledged that, as the result of these investigations for which the PI received the 2001 National Medal of Science, our understanding of how suspensions behave under flow is far more detailed and comprehensive than was the case even as recently as a decade ago. Thus, given that the flow of suspensions plays a crucial role in many diverse physical processes, our work has had a major and lasting impact in a subject having both fundamental as well as practical importance