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John Y Walz

Publications and source records attributed to John Y Walz.

10 recordsLinked to original sources

Investigation of short-time particle dynamics near an interface in the presence of nonadsorbed macro-ions.

The optical technique of total internal reflection microscopy was used to study the normal Brownian motion of a single colloidal particle near an interface. The measurements were made using a recently developed technique in which the diffusion coefficient was determined by the variance of the short-time (Deltat --> 0) motion of the particle. Experiments were performed in solutions containing either silica nanospheres or clay platelets (Laponite RD) to investigate the effect of nonadsorbed material on the dynamics of near-contact particle motion. The change in the diffusion coefficient with separation distance between the particle and plate in solutions containing nonadsorbed macro-ions was well-described by the theory developed for simple fluids. These results suggest that, in dilute solutions of nonadsorbed material in which the bulk rheological properties remain similar to those of the pure fluid, the mobility and diffusion coefficient correction factors developed for simple fluids remain valid.

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Simultaneous investigation of sedimentation and diffusion of a single colloidal particle near an interface.

We describe here a new procedure for the simultaneous investigation of sedimentation and diffusion of a colloidal particle in close proximity to a solid, planar wall. The measurements were made using the optical technique of total internal reflection microscopy, coupled with optical radiation pressure, for dimensionless separation distances (gap width/radius of particle) ranging from 0.01 to 0.05. In this region, the hydrodynamic mobility and diffusion coefficient are substantially reduced below bulk values. The procedure involved measuring the mean and the variance of vertical displacements of a Brownian particle settling under gravity toward the plate. The spatially varying diffusion coefficient was calculated from the displacements at small times (where diffusive motion was dominant). The mobility relationship for motion normal to a flat plate was tested by measuring the average distance of travel versus time as the particle settled under the constant force of gravity. For the simple Newtonian fluid used here (aqueous salt solution), the magnitude of the diffusion coefficient and mobility, plus their dependence on separation distance, showed excellent agreement with predictions. This new technique could be of great value in measuring the mobility and diffusion coefficient for near-contact motion in more complex fluids for which the hydrodynamic correction factors are not known a priori, such as shear-thinning fluids.

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Structuring of macroions confined between like-charged surfaces.

We investigate the structuring of charged spherical nanoparticles and micelles (i.e., "macroions") between two surfaces as a function of bulk macroion concentration. Structuring is deduced from measured force profiles between a silica particle and a silica plate in the presence of an aqueous macroion (Ludox silica nanoparticle or sodium dodecyl sulfate micelle) solution, obtained with an atomic force microscope. We observe oscillatory force profiles that decay with separation. We find that the wavelength of the force profiles scales with the bulk number density as rho(-)(1/3), rather than with the effective macroion size. Only at very high silica nanoparticle concentration (above 10 vol %) in a low ionic strength solution does the wavelength become smaller than that predicted by the simple rho(-)(1/3) scaling; however, the original scaling is recovered upon the addition of a small amount of electrolyte. A comparison between the measured wavelength and the predicted spacing between the macroions in the bulk shows that the two variables differ in both magnitude and bulk density scaling. This finding suggests that confined macroions are more ordered than those in the bulk and the nature of this ordering is maintained over a relatively wide range of bulk concentration.

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Relationship between scattered intensity and separation for particles in an evanescent field.

We describe measurements of the scattering of visible light from an evanescent field by both spherical particles (R = 1-10 mum) that are glued to atomic force microscopy (AFM) cantilevers, and by sharp tips (R < 60 nm) that were incorporated onto the cantilevers during manufacture. The evanescent wave was generated at the interface between a flat plate and an aqueous solution, and an atomic force microscope was used to accurately control the separation, h, between the particle and the flat plate. We find that, for sharp tips, the intensity of scattered light decays exponentially with separation between the tip and the plate all the way down to h approximately 0. The measured decay length of scattered intensity, delta, is the same as the theoretical decay length of the evanescent intensity in the absence of the sharp tip. For borosilicate particles, (R = 1-10 mum), the scattering also decays exponentially with separation at large separations. However, when the separation is less than roughly 3delta, the measured scattering intensity is smaller in magnitude than that which would be predicted by extrapolating the exponential decay observed at large separations. For these particles, the scattering approximately fits the sum of two exponentials. The magnitude of the deviation from exponential at contact was roughly 10-15% for R = 1 mum particles and about 30% for larger particles and is larger for s-polarized light. Preliminary experiments on polystyrene particles shows that the scattering is also smaller than exponential at small separations but that the deviation from exponential is larger for p-polarized light. In evanescent wave AFM (EW-AFM) the scattering-separation can be calibrated for situations where the scattering is not exponential. We discuss possible errors that could be introduced by assuming that exponential decay of scattering continues down to h = 0.

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A new approach for analyzing particle motion near an interface using total internal reflection microscopy.

A new method was developed for analyzing the normal motion of a single colloidal particle near an interface. The optical technique of total internal reflection microscopy (TIRM) was used to determine the distribution of vertical displacements of a particle from a specific starting position as a function of time. At very small displacement times, the displacements are normally distributed with a variance that is proportional to the diffusion coefficient times the displacement time. The change in the diffusion coefficient with separation distance between the particle and plate was found to match that predicted by Brenner (Chem. Eng. Sci. 16 (1961) 242). As the sampling time becomes very large, the variance reaches a constant value determined strictly by the shape of the local potential energy profile holding the particle. A major advantage of this approach, relative to other measurement methods, is that the particle's spatially variant diffusion coefficient can be determined without any knowledge of the forces acting on the particle.

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Atomic force microscopy colloid-probe measurements with explicit measurement of particle-solid separation.

We describe the use of evanescent wave scattering to measure the separation between the surface of a solid and a particle that is attached to an atomic force microscope (AFM) cantilever. Termed evanescent wave atomic force microscopy, our approach involves measuring the intensity of the light scattered from an evanescent field formed by the total internal reflection of a laser beam at a solid/fluid interface. In a conventional AFM "colloid probe" measurement, this separation must be inferred from an examination of the surface forces. Direct measurement of this separation with an evanescent wave atomic force microscope (EW-AFM) removes some ambiguity in the surface force measurement and, in addition, allows new types of measurements. For example, the force can be monitored at a constant separation. Our evanescent scattering apparatus is essentially identical to that used in total internal reflection microscopy (TIRM), except that we collect the light that scatters back into the incident medium, because the AFM partly obscures the forward scattered light (i.e., light scattered into the transmitted region). Compared to a conventional TIRM measurement, where the particle moves freely, attaching the particle to the cantilever in an EW-AFM gives much greater control of the particle position.

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An approximate method for calculating depletion and structural interactions between colloidal particles.

An approximate method is evaluated for calculating the second virial coefficient in a dilute macromolecular solution bounded by two interfaces. The approximation is essentially the superposition of the coefficients calculated independently for each surface. To test this approach, the depletion interaction between two particles in a solution of nonadsorbing, spherical macromolecules is calculated in systems with either hard-wall or long-range electrostatic interactions. In all systems tested, the interparticle interaction energy calculated with the approximation is found to be in good agreement with that calculated using the exact approach (e.g., error less than 2% at the smallest separations). The primary advantage of this approximation is a significant reduction in the computation time required for calculating the depletion interaction, especially in charged systems. The paper also shows that the expressions for predicting the depletion interaction in purely hard-sphere systems can be used in dilute ionic systems, provided the appropriate effective macromolecule size is used. For the attractive depletion interaction, this effective size is determined by the range of the particle-macromolecule interaction (as opposed to the macromolecule-macromolecule interaction).

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Effect of depletion interactions on transport of colloidal particles in porous media.

The influence of depletion interactions on the transport of micrometer-sized, negatively charged polystyrene latex particles through porous media was studied by analysis of particle breakthrough curves as a response to short-pulse particle injections to the inlet of a packed column of glass beads. The column outlet latex particle concentration profiles and the total amount of particles exiting the column were determined as a function of the concentration of small, silica nanoparticles in the solution and the bulk flow rate. Because of similar charges, the silica particles do not adsorb to either the latex particles or glass beads and thus induce an attractive depletion force between the latex particles and glass bead collectors. The total column outlet latex particle amount was calculated by integrating the measured breakthrough concentration curve and compared to the known amount of injected particles at the column inlet. It was found that the particle recovery was a decreasing function of the silica nanoparticle concentration and the carrier fluid residence time, and an increasing function of the velocity in the bed. In addition, removing the silica nanoparticles from the flowing solution caused a second outlet peak to appear, suggesting that some of the polystyrene particles were captured in secondary energy wells. The experimental data were interpreted using the predicted potential energy profile between a single particle and a glass bead, which was assumed to consist of electrostatic, van der Waals, and depletion components. The results indicate that secondary energy wells significantly affect particle transport behavior through porous media.

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Direct measurement of depletion and structural forces in polydisperse, charged systems.

The effect of polydispersity in macromolecule size or surface potential on the depletion interaction between a spherical silica particle and a silica flat in solutions containing two different types of nonadsorbing charged spherical macromolecules was studied with an atomic force microscope (AFM). The macromolecules used here were negatively charged nanospheres of either polystyrene or silica. To investigate the effect of size polydispersity, experiments were performed under the condition of either constant macromolecule number density or constant volume fraction as the relative proportions of smaller and larger polystyrene nanospheres in the suspension were varied. Similarly, for the experiments with surface potential polydispersity, the suspensions contained varying fractions of more highly charged (polystyrene) and less highly charged (Ludox silica) nanospheres at constant number density. The experimental results were compared to the predictions of the modified force-balance model of Piech and Walz and semiquantitative agreement was found. In particular, the maximum attraction and repulsion observed in the measured force profiles were found to agree with the predicted trends as the makeup of the macromolecules was varied. The trend in the maximum attraction was also consistent with predictions made using a simple "scaling" analysis derived using the equation for hard-sphere interactions.

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Prediction and measurement of the interparticle depletion interaction next to a flat wall.

A theoretical and experimental study was performed to investigate the depletion interaction between two colloidal particles next to a solid wall in a solution of nonadsorbing macromolecules. By calculating the change in free volume available to the macromolecules upon approach of the two particles, a relatively simple expression was developed for the interparticle depletion attraction in hard sphere systems as a function of the particle-particle and particle-plate spacing. Perhaps the most useful result obtained from this analysis was that the wall has no effect whenever the ratio of the particle radius to the macromolecule radius is greater than four. (In charged systems, this ratio would apply to the effective particle and macromolecule sizes.) A series of experiments was then performed in which the hydrodynamic force balance (HFB) apparatus was used to measure the shear force needed to separate a colloidal doublet consisting of two particles trapped in a secondary energy well formed by a repulsive electrostatic force and an attractive depletion force. The macromolecules used here were small, nanometer-sized spheres of either silica or polystyrene. Agreement between the measured separation forces and those predicted using the force balance model of J. Y. Walz and A. Sharma (J. Colloid Interface Sci. 168, 485 (1994)) was within a factor of 1.3 using no adjustable parameters and accounting for polydispersity and uncertainty in the macromolecule size. It is shown that this remaining discrepancy could be caused by the Brownian (stochastic) nature of the doublet breakup process.

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