Robert L. Leheny

Evolution of particle-scale dynamics in an aging clay suspension.

Multispeckle x-ray photon correlation spectroscopy was employed to characterize the slow dynamics of a suspension of highly charged, nanometer-sized disks. At wave vectors q corresponding to interparticle length scales, the dynamic structure factor follows a form f(q,t) approximately exp([-(t/tau)(beta)], where beta approximately 1.5. The relaxation time tau increases with the sample age t(a) approximately as tau approximately t(1.8)(a) and decreases with q as tau approximately q(-1). Such behavior is consistent with models that describe the dynamics in disordered elastic media in terms of strain from random, local structural rearrangements. The measured amplitude of f(q,t) varies with q in a manner that implies caged particle motion. The decrease in the range of this motion and an increase in suspension conductivity with increasing t(a) indicate a growth in interparticle repulsion as the mechanism for internal stress development implied by these models.

Beyond simple exponential correlation functions and equilibrium dynamics in x-ray photon correlation spectroscopy

We discuss the complex dynamics in condensed matter studied with x-ray photon correlation spectroscopy (XPCS) in which non-exponential correlation functions and dispersion relations deviating from the simple diffusion law are observed. Results are presented for two systems whose dynamics are characterized by compressed, faster-than-exponential correlation functions associated with hyper-diffusive motion. In the first case, the microscopic response of an aerogel following sectioning is investigated. In the second, the out-of-equilibrium dynamics in a dense colloidal gel recovering from shear is analyzed. In both cases, the dynamics, which can be associated with relaxation of internal stress, exhibits ageing. Included in the analyses are calculations of two-time correlation functions and the variance of the instantaneous degree of correlation, yielding the dynamical susceptibility.

STRUCTURAL STUDIES OF AN ORGANIC LIQUID THROUGH THE GLASS TRANSITION

We have performed neutron diffraction experiments on deuterated propylene glycol, an organic glass former, at temperatures ranging from where its dynamical response approaches that of normal liquids to below the point where relaxation times appear to diverge. Our studies extend over a very broad range of scattering wave vector (0.01<Q<30 A−1). In contrast to models which predict clustering, we find no evidence in the liquid at any temperature for heterogeneities large on molecular scales. However, we do note subtle changes at shorter lengths. Using molecular dynamics simulations to model our results, we identify these changes with increasing density and increasing orientational order induced by hydrogen bonding in the liquid as it cools. Analysis of the orientational correlations between molecules reveals a strong dependence on their relative positions.

Combined Passive and Active Microrheology Study of Protein-Layer Formation at an Air—Water Interface

We investigate the mechanical properties of layers of the protein beta-lactoglobulin during their formation at the air-water interface using a combination of passive and active microrheological techniques. The passive microrheology, which employs multiple particle tracking measurements using spherical colloids, indicates that the interfacial rheology evolves over time through three stages as protein adsorbs at the interface: (i) an increase in viscosity, (ii) a period of spatial heterogeneity in which the interface contains elastic and viscous regions, and (iii) the development of a uniformly rigid elastic film. Varying solution pH between pH = 5.2, the isoelectric point of beta-lactoglobulin, and pH = 7.0 has no qualitative effect on this mechanical evolution. The active microrheology, which employs ferromagnetic nanowires rotating in response to magnetic torques, similarly shows an increasing interfacial viscosity at early times and evidence of mechanical heterogeneity at intermediate times. However, at late times, the nanowire mobility becomes strongly pH dependent. For pH = 5.2, the layer responds as a rigid elastic film to the stress imposed by the wire. For pH = 7.0, it displays a viscous response that contrasts with the passive measurements. We associate this contrast with a nonlinear response to the wire at late times that reflects a low yield stress of the film at higher pH. This ability to compare passive and active measurements demonstrates the advantage of applying multiple microrheological methods to resolve ambiguity in any single approach.

Gel formation and aging in weakly attractive nanocolloid suspensions at intermediate concentrations

We report x-ray photon correlation spectroscopy (XPCS) and rheometry experiments to study the temporal evolution of gel formation and aging in suspensions of silica nanocolloids possessing a tunable short-range attraction. The colloid volume fractions, φ = 0.20 and 0.43, are below the glass regime at high concentration and above the fractal regime at low concentration. Following a sudden initiation of the interparticle attraction, the suspensions display a protracted latency period in which they remain fluid before acquiring a measurable elastic shear modulus. The duration of the latency period and the subsequent rate of increase of the modulus vary strongly with the strength of the attraction. The XPCS results indicate dynamic heterogeneity among the colloids during this gel formation in which a growing fraction of the particles become localized. The temporal evolution of this localization correlates with that of the rheology. In particular, the time scale over which the fraction of localized particles increases tracks the duration of the latency period. Also, at φ = 0.20 the localization length characterizing the motion of the localized fraction scales onto the shear modulus with no free parameters as predicted by a self-consistent theory based on mode coupling [K. S. Schweizer and G. Yatsenko, J. Chem. Phys. 127, 164505 (2007)], while deviations from the predicted scaling at φ = 0.43 are observed near the gel point. The XPCS results also reveal slow, hyperdiffusive motion of the colloids in the newly formed gels that is attributed to strain from the relaxation of internal stress. While some features of this motion correlate with the evolving rheology, others appear decoupled from the macroscopic mechanical behavior.

Smectic ordering in liquid-crystal-aerosil dispersions. I. X-ray scattering.

Comprehensive x-ray scattering studies have characterized the smectic ordering of octylcyanobiphenyl (8CB) confined in the hydrogen-bonded silica gels formed by aerosil dispersions. For all densities of aerosil and all measurement temperatures, the correlations remain short range, demonstrating that the disorder imposed by the gels destroys the nematic (N) to smectic-A (SmA) transition. The smectic correlation function contains two distinct contributions. The first has a form identical to that describing the critical thermal fluctuations in pure 8CB near the N-SmA transition, and this term displays a temperature dependence at high temperatures similar to that of the pure liquid crystal. The second term, which is negligible at high temperatures but dominates at low temperatures, has a shape given by the thermal term squared and describes the static fluctuations due to random fields induced by confinement in the gel. The correlation lengths appearing in the thermal and disorder terms are the same and show a strong variation with gel density at low temperatures. The temperature dependence of the amplitude of the static fluctuations further suggests that nematic susceptibility becomes suppressed with increasing quenched disorder. The results overall are well described by a mapping of the liquid-crystal-aerosil system onto a three-dimensional XY model in a random field with disorder strength varying linearly with the aerosil density.

Capillary bond between rod-like particles and the micromechanics of particle-laden interfaces

Rod-like microparticles assemble by capillarity at fluid interfaces to make distinctively different microstructures depending on the details of the particle shape. Ellipsoidal particles assemble in side-to-side orientations to form flexible chains, whereas cylinders assemble end-to-end to form rigid chains. To understand these differences, we simulate the near-field capillary interactions between pairs of rod-like particles subject to bond-stretching and bond-bending deformations. By comparing ellipsoids, cylinders, and cylinders with smooth edges, we show that geometric details dramatically affect the magnitude and shape of the capillary energy landscape. We relate this energy landscape to the mechanics of the chains, predicting the flexural rigidity for chains of ellipsoids, and a complex, non-elastic response for chains of cylinders. These results have implications in the design of particle laden interfaces for emulsion stabilization and encapsulation, and for oriented assembly of anisotropic materials.

Slow dynamics, aging, and glassy rheology in soft and living matter

Abstract We explore the origins of slow dynamics, aging and glassy rheology in soft and living matter. Non-diffusive slow dynamics and aging in materials characterised by crowding of the constituents can be explained in terms of structural rearrangement or remodelling events that occur within the jammed state. In this context, we introduce the jamming phase diagram proposed by Liu and Nagel to understand the ergodic–nonergodic transition in these systems, and discuss recent theoretical attempts to explain the unusual, faster-than-exponential dynamical structure factors observed in jammed soft materials. We next focus on the anomalous rheology (flow and deformation behavior) ubiquitous in soft matter characterised by metastability and structural disorder, and refer to the Soft Glassy Rheology (SGR) model that quantifies the mechanical response of these systems and predicts aging under suitable conditions. As part of a survey of experimental work related to these issues, we present x-ray photon correlation spectroscopy (XPCS) results of the aging of laponite clay suspensions following rejuvenation. We conclude by exploring the scientific literature for recent theoretical advances in the understanding of these models and for experimental investigations aimed at testing their predictions.

Smectic ordering in liquid-crystal-aerosil dispersions. II. Scaling analysis.

Liquid crystals offer many unique opportunities to study various phase transitions with continuous symmetry in the presence of quenched random disorder (QRD). The QRD arises from the presence of porous solids in the form of a random gel network. Experimental and theoretical work supports the view that for fixed (static) inclusions, quasi-long-range smectic order is destroyed for arbitrarily small volume fractions of the solid. However, the presence of porous solids indicates that finite-size effects could play some role in limiting long-range order. In an earlier work, the nematic-smectic-A transition region of octylcyanobiphenyl (8CB) and silica aerosils was investigated calorimetrically. A detailed x-ray study of this system is presented in the preceding paper, which indicates that pseudocritical scaling behavior is observed. In the present paper, the role of finite-size scaling and two-scale universality aspects of the 8CB+aerosil system are presented and the dependence of the QRD strength on the aerosil density is discussed.

Application of ferromagnetic nanowires to interfacial microrheology

Experiments are reported to characterize the viscous drag on Ni wires of diameter of 350nm and lengths of 5μm<L<30μm confined to the air interface of glycerol/water mixtures upon which very thin (30–150nm thick) silicone oil films are deposited. The sensitivity of the observed drag to the film viscosity demonstrates the utility of the wires as highly sensitive probes of interfacial shear rheology. The dependence of the drag on wire length is analyzed in terms of recent theoretical predictions for the hydrodynamic drag on an anisotropic particle confined to an interfacial film.