Shear induced tuning and memory effects in colloidal gels of rods and spheres.

Shear history plays an important role in determining the linear and nonlinear rheological response of colloidal gels and can be used for tuning their structure and flow properties. Increasing the colloidal particle aspect ratio lowers the critical volume fraction for gelation due to an increase in the particle excluded volume. Using a combination of rheology and confocal microscopy, we investigate the effect of steady and oscillatory preshear history on the structure and rheology of colloidal gels formed by silica spheres and rods of length L and diameter D (L/D = 10) dispersed in 11 M CsCl solution.

Colloidal Rod-Like Particles with Temperature-Driven Tunable Interactions.

Temperature-sensitive rod-like colloidal particles were synthesized by grafting a temperature-responsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMA), on the surface of high aspect ratio silica rods by surface-initiated atom transfer radical polymerization. The stability of the grafted polymer on the surface of the particles in aqueous solutions was found to deteriorate with time, leading to a gradual decrease of the polymer content of the hybrid colloids, which was attributed to the mechanically activated hydrolysis of the labile bonds at the polymer-silica interface. The polymer degrafting was significantly suppressed by first growing a hydrophobic poly(methyl methacrylate) block onto the particle surface to act as a barrier layer for the penetration of water molecules at the polymer-particle interface, followed by chain-extension with the hydrophilic PDMA chains.

A microstructural investigation of an industrial attractive gel at pressure and temperature.

Oil-continuous drilling fluids used in the oil and gas industry are formulated to be pseudoplastic with a relatively weak yield stress. These fluids are required to maintain their properties over wide temperature and pressure ranges yet there are few methods that can sensitively study the inherent structure and mechanical properties in the fluids under such conditions. Here we study a model oil-continuous drilling fluid formulation as a function of both temperature (up to 153 °C) and pressure (up to 1330 bar) with Diffusive Wave Spectroscopy (DWS).

Tuning local microstructure of colloidal gels by ultrasound-activated deformable inclusions.

Colloidal gels possess a memory of previous shear events, both steady and oscillatory. This memory, embedded in the microstructure, affects the mechanical response of the gel, and therefore enables precise tuning of the material properties under careful preparation. Here we demonstrate how the dynamics of a deformable inclusion, namely a bubble, can be used to locally tune the microstructure of a colloidal gel.

Deformation profiles and microscopic dynamics of complex fluids during oscillatory shear experiments.

Oscillatory shear tests are widely used in rheology to characterize the linear and non-linear mechanical response of complex fluids, including the yielding transition. There is an increasing urge to acquire detailed knowledge of the deformation field that is effectively present across the sample during these tests; at the same time, there is mounting evidence that the macroscopic rheological response depends on the elusive microscopic behavior of the material constituents. Here we employ a strain-controlled shear-cell with transparent walls to visualize and quantify the dynamics of tracers embedded in various cyclically sheared complex fluids, ranging from almost-ideal elastic to yield stress fluids.

Yielding and resolidification of colloidal gels under constant stress.

We examine the macroscopic deformation of a colloidal depletion gel subjected to a step shear stress. Three regimes are identified depending on the magnitude of the applied stress: (i) for stresses below yield stress, the gel undergoes a weak creep in which the bulk deformation grows sublinearly with time similar to crystalline and amorphous solids. For stresses above yield stress, when the bulk deformation exceeds approximately the attraction range, the sublinear increase of deformation turns into a superlinear growth which signals the onset of non-linear rearrangements and yielding of the gel.

Shear driven vorticity aligned flocs in a suspension of attractive rigid rods.

A combination of rheology, optical microscopy and computer simulations was used to investigate the microstructural changes of a semi-dilute suspension of attractive rigid rods in an imposed shear flow. The aim is to understand the relation of the microstructure with the viscoelastic response, and the yielding and flow behaviour in different shear regimes of gels built from rodlike colloids. A semi-dilute suspension of micron sized, rodlike silica particles suspended in 11 M CsCl salt solution was used as a model system for attractive rods' gel.

Structure and dynamics in suspensions of soft core-shell colloids in the fluid regime.

We report on a detailed experimental study of the structure and short-time dynamics in fluid-regime suspensions of soft core-shell spherical particles with different molecular weights of the chains forming the soft outer shell, and therefore different degrees of particle softness, using 3D dynamic light scattering (3D-DLS). Owing to the particle softness, the liquid-crystal coexistence regime is found to be broader than that of hard-sphere (HS) suspensions. Static light scattering in the dilute regime yields form factors that can be described using a spherical core-shell model and second virial coefficients A > 0 indicative of purely repulsive interactions.

Binary colloidal glasses: linear viscoelasticity and its link to the microscopic structure and dynamics.

We study the relation between the microscopic structure and dynamics and the macroscopic rheological response of glass-forming colloidal suspensions, namely binary colloidal hard-sphere mixtures with large size asymmetry (1 : 5) that span a large range of mixture compositions close to the glass transition. The dynamical shear moduli are measured by oscillatory rheology and the structure and dynamics on the single-particle level by confocal microscopy. The data are compared with Brownian Dynamics simulations and predictions from mode-coupling theory based on the Percus-Yevick approximation.

A Precisely Flow-Controlled Microfluidic System for Enhanced Pre-Osteoblastic Cell Response for Bone Tissue Engineering.

Bone tissue engineering provides advanced solutions to overcome the limitations of currently used therapies for bone reconstruction. Dynamic culturing of cell-biomaterial constructs positively affects the cell proliferation and differentiation. In this study, we present a precisely flow-controlled microfluidic system employed for the investigation of bone-forming cell responses cultured on fibrous collagen matrices by applying two flow rates, 30 and 50 μL/min.

Residual stresses in colloidal gels.

A combination of experiments and Brownian Dynamics (BD) simulations is utilized to examine internal stresses in colloidal gels brought to rest from steady shear at different shear rates. A model colloidal gel with intermediate volume fraction is chosen where attractions between particles are introduced by adding non-adsorbing linear polymer chains. After flow cessation, the gel releases the stress in two distinct patterns: at high shear rates, where shear forces dominate over attractive forces, the shear-melted gel behaves as a liquid and releases stresses to zero after flow cessation.

Colloidal gels tuned by oscillatory shear.

We examine the microstructural and mechanical changes which occur during oscillatory shear flow and reformation after flow cessation of an intermediate volume fraction colloidal gel using rheometry and Brownian Dynamics (BD) simulations. A model depletion colloid-polymer mixture is used, comprising a hard sphere colloidal suspension with the addition of non-adsorbing linear polymer chains. The results reveal three distinct regimes depending on the strain amplitude of oscillatory shear.

Creep and aging of hard-sphere glasses under constant stress.

We investigate the aging behavior of glassy suspensions of nearly hard-sphere colloids submitted to a constant shear stress. For low stresses, below the yield stress, the system is subject to creep motion. As the sample ages, the shear rate exhibits a power-law decrease with time with exponents that depend on the sample age.

Convective Cage Release in Model Colloidal Glasses.

The mechanism of flow in glassy materials is interrogated using mechanical spectroscopy applied to model nearly hard sphere colloidal glasses during flow. Superimposing a small amplitude oscillatory motion orthogonal onto steady shear flow makes it possible to directly evaluate the effect of a steady state flow on the out-of-cage (α) relaxation as well as the in-cage motions. To this end, the crossover frequency deduced from the viscoelastic spectra is used as a direct measure of the inverse microstructural relaxation time, during flow.

Manipulating the kinetics and mechanism of phase separation in dynamically asymmetric LCST blends by nanoparticles.

The addition of nanoparticles in dynamically asymmetric LCST blends is used to induce preferred phase-separating morphology by tuning the dynamic asymmetry, and to control the kinetics of phase separation by slowing down (or even arresting) the domain growth. For this purpose, we used hydrophobic and hydrophilic fumed silica, which self-assemble during phase separation into the bulk of the slow (PS-rich) and fast (PVME-rich) dynamic phases, respectively. Both types of nanoparticles slow down considerably nucleation and growth (NG), spinodal decomposition (SD), and viscoelastic phase separation (VPS) at volume fractions as low as 0.

Tuning colloidal gels by shear.

Using a powerful combination of experiments and simulations we demonstrate how the microstructure and its time evolution are linked with mechanical properties in a frustrated, out-of-equilibrium, particle gel under shear. An intermediate volume fraction colloid-polymer gel is used as a model system, allowing quantification of the interplay between interparticle attractions and shear forces. Rheometry, confocal microscopy and Brownian dynamics reveal that high shear rates, fully breaking the structure, lead after shear cessation to more homogeneous and stronger gels, whereas preshear at low rates creates largely heterogeneous weaker gels with reduced elasticity.

Controlling the kinetics of viscoelastic phase separation through self-assembly of spherical nanoparticles or block copolymers.

Viscoelastic phase separation (VPS) can produce a network structure of the minor phase, which needs to be stabilized for designing a heterogeneous structure with desired mechanical and electrical functions. In this work, we investigate the stabilization of the VPS-induced network structure in a dynamically asymmetric PS/PVME blend by incorporation of a SEBS-g-MA block copolymer or dimethyldichlorosilane modified nanosilica. The addition of SEBS-g-MA retards the volume shrinking process and slows down the kinetics of phase separation due to its localization at the PS/PVME interfaces.

Anisotropic diffusion of concentrated hard-sphere colloids near a hard wall studied by evanescent wave dynamic light scattering.

Evanescent wave dynamic light scattering and Stokesian dynamics simulations were employed to study the dynamics of hard-sphere colloidal particles near a hard wall in concentrated suspensions. The evanescent wave averaged short-time diffusion coefficients were determined from experimental correlation functions over a range of scattering wave vectors and penetration depths. Stokesian dynamics simulations performed for similar conditions allow a direct comparison of both the short-time self- and collective diffusivity.

Residual stresses in glasses.

The history dependence of glasses formed from flow-melted steady states by a sudden cessation of the shear rate γ[over ˙] is studied in colloidal suspensions, by molecular dynamics simulations and by mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of γ[over ˙]t, even though no flow is present.

Complex oscillatory yielding of model hard-sphere glasses.

The yielding behavior of hard sphere glasses under large-amplitude oscillatory shear has been studied by probing the interplay of Brownian motion and shear-induced diffusion at varying oscillation frequencies. Stress, structure and dynamics are followed by experimental rheology and Browian dynamics simulations. Brownian-motion-assisted cage escape dominates at low frequencies while escape through shear-induced collisions at high ones, both related with a yielding peak in G''.

Transient dynamics in dense colloidal suspensions under shear: shear rate dependence.

A combination of confocal microscopy and rheology experiments, Brownian dynamics (BD) and molecular dynamics (MD) simulations and mode coupling theory (MCT) have been applied in order to investigate the effect of shear rate on the transient dynamics and stress-strain relations in supercooled and glassy systems under shear. Immediately after shear is switched on, the microscopic dynamics display super-diffusion and the macroscopic rheology a stress overshoot, which become more pronounced with increasing shear rate. MCT relates both to negative sections of the generalized shear modulus, which grow with increasing shear rate.

Yielding of hard-sphere glasses during start-up shear.

Concentrated hard-sphere suspensions and glasses are investigated with rheometry, confocal microscopy, and Brownian dynamics simulations during start-up shear, providing a link between microstructure, dynamics, and rheology. The microstructural anisotropy is manifested in the extension axis where the maximum of the pair-distribution function exhibits a minimum at the stress overshoot. The interplay between Brownian relaxation and shear advection as well as the available free volume determine the structural anisotropy and the magnitude of the stress overshoot.

Shear banding and flow-concentration coupling in colloidal glasses.

We report experiments on hard-sphere colloidal glasses that show a type of shear banding hitherto unobserved in soft glasses. We present a scenario that relates this to an instability due to shear-concentration coupling, a mechanism previously thought unimportant in these materials. Below a characteristic shear rate γ(c) we observe increasingly nonlinear and localized velocity profiles.

Osmotic shrinkage in star/linear polymer mixtures.

Multiarm star polymers were used as model grafted colloidal particles with long hairs, to study their size variation due to osmotic forces arising from added linear homopolymers of smaller size. This is the origin of the depletion phenomenon that has been exploited in the past as a means to melt soft colloidal glasses by adding linear chains and analyzed using dynamic light scattering experiments and an effective interactions analysis yielding the depletion potential. Shrinkage is a generic phenomenon for hairy particles, which affects macroscopic properties and state transitions at high concentrations.

Slow dynamics, aging, and crystallization of multiarm star glasses.

Multiarm star polymers are model systems with tunable intermediate colloid to polymerlike character, exhibiting rich phase behavior, internal relaxations, and flow properties. An important puzzle for several years has been the lack of clear experimental proof of crystalline states despite strong theoretical predictions. We present unambiguous evidence via multispeckle dynamic light scattering (MSDLS) and small-angle neutron scattering (SANS) for such crystallization in a solvent of intermediate quality.