arXiv subjects

George Petekidis

Publications and source records attributed to George Petekidis.

12 recordsLinked to original sources

arXiv2026

Orthogonal Superposition Rheometry of soft core-shell microgels

The mechanisms of flow in suspensions of soft particles above the glass-transition volume fraction and in the jammed state were probed using Orthogonal Superposition Rheometry (OSR). A small amplitude oscillatory shear flow is superimposed orthogonally onto a steady shear flow, which allows monitoring the viscoelastic spectra of sheared jammed core-shell microgels during flow. The characteristic crossover frequency ωc, deduced from the viscoelastic spectrum, provides information about the shear induced structural relaxation time, which is connected to the microscopic yielding mechanism of cage breaking. The shear rate evolution of the crossover frequency is used to achieve a superposition of all spectra and get a better insight of the flow mechanism. Despite their inherent softness, the hybrid core-shell microgels exhibit similarities with hard sphere-like flow behavior, with the main difference that for the microgels the transition from a glassy to a jammed state introduces a volume fraction dependence of the scaling of ωc with shear rate. We further check the application of the Kramers-Kronig relations on the experimental low strain amplitude OSR data finding a good agreement. Finally, the low frequency response at high strain rates was investigated with open bottom cell geometry and instrumental limits were identified. Based on these limits, we discuss previous OSR data and findings in repulsive and attractive colloidal glasses, and compared them with the current soft particle gels.

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arXiv2024

Tuning the mechanical properties of organophilic clay dispersions: particle composition and preshear history effects

Clay minerals are abundant natural materials used widely in coatings, construction materials, ceramics, as well as being a component of drilling fluids. Here, we present the effect of steady and oscillatory preshear on organophilic modified clay gels in synthetic oil. Both platelet and needle-like particles are used as viscosifiers in drilling fluid formulations. For both particles the plateau modulus exhibits a similar concentration dependence, G_P ~ c^3.9, whereas the yield strain is γ_y ~ c^(-1) for the platelets and γ_y ~ c^-1.7 for the needles. Mixtures of the two follow an intermediate behavior: at low concentrations their elasticity and yield strain follows that of needle particles while at higher concentrations it exhibits a weaker power law dependence. Furthermore, upon varying the preshear history, the gel viscoelastic properties can be significantly tuned. At lower (higher) clay concentrations, preshear at specific oscillatory strain amplitudes or steady shear rates, may induce a hardening (softening) of the dispersions and, at all concentrations, a lowering of the shear strain. Hence, in needle dispersions preshear resulted in changes in the volume fraction dependence of the elastic modulus from G_P ~ c^3.9 to G_P ~ c^2.5 and of the yield strain from γ_y ~ c^-1.7 to γ_y ~ c^-1. However, small angle X-ray scattering showed not much structural changes, within the q-range covered. Our findings indicate ways to design colloidal organoclay dispersions with a mechanical response that can be tuned at will.

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arXiv2024

High-frequency Optimally Windowed Chirp rheometry for rapidly evolving viscoelastic materials: application to a crosslinking thermoset

Abstract Knowledge of the evolution of mechanical properties of the curing matrix is of great importance in composite parts or structure fabrication. Conventional rheometry, based on small amplitude oscillatory shear is limited by long interrogation times. In rapidly evolving materials, time sweeps can provide a meaningful measurement albeit at a single frequency. To overcome this constraint we utilize a combined frequency and amplitude-modulated chirped strain waveform in conjunction with a home-made sliding plate piezo-operated (PZR) and a dual-head commercial rotational rheometer (Anton Paar MCR 702) to probe the linear viscoelasticity of these time-evolving materials. The direct controllability of the PZR resulting from the absence of any kind of firmware and the microsecond actuator-sensor response renders this device ideal for exploring the advantages of this technique. The high frequency capability allows us to extend the upper limits of the accessible linear viscoelastic spectrum and most importantly, to shorten the length of the interrogating strain signal (OWCh-PZR) to sub-second scales, while retaining a high time-bandwidth product. This short duration ensures that the mutation number (NMu) is kept sufficiently low, even in fast curing resins. The method is validated via calibration tests in both instruments and the corresponding limitations are discussed. As a proof of concept the technique is applied to a curing vinylester resin. The linear viscoelastic (LVE) spectrum is assessed every 20 seconds to monitor the rapid evolution of the time- and frequency-dependence of the complex modulus. Finally, FTIR spectroscopy is utilized to gain insights on the evolution of the chemical network while the gap-dependence of the evolving material properties in these heterogeneous systems is also investigated.

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arXiv2023

On the Nature of Flow Curve and Categorization of Thixotropic Yield Stress Materials

Thixotropy is a phenomenon related to time dependent change in viscosity in presence or absence of flow. The yield stress, on the other hand, represents the minimum value of stress above which steady flow can be sustained. In addition, the yield stress of a material may also change as a function of time. Both these characteristic features in a material strongly influence the steady state flow curve of the same. This study aims to understand the interrelation between thixotropy, yield stress and their relation with the flow curve. In this regard, we study five thixotropic materials that show yield stress. The relaxation time of all the five systems shows power-law dependence on aging time with behaviors ranging from weaker than linear, linear to stronger than linear. Furthermore, the elastic modulus and yield stress has been observed to be constant for some systems while time dependent for the others. We also analyze the experimental behavior through a viscoelastic thixotropic structural kinetic model that predicts the observed experimental behavior of constant as well as time-dependent yield stress quite well. These findings indicate that a non-monotonic steady-state flow curve in a structural kinetic formalism necessarily leads to time-dependent yield stress, while constant yield stress is predicted by a monotonic steady-state flow curve with stress plateau in the limit of low shear rates. The present work, therefore, shows that thixotropic materials may exhibit either monotonic or non-monotonic flow curves. Consequently, thixotropic materials may show no yield stress, constant yield stress or time-dependent yield stress.

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arXiv2022

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 colloidal particle aspect ratio lowers the critical volume fraction for gelation due to an increase of the particle excluded volume. Using a combination of rheology and confocal microscopy we investigate the effect of steady and oscillatory pre-shear 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. We use a non-dimensional Mason number, Mn (= F_visc./F_attr.) to compare the effect of steady and oscillatory pre-shear on gel viscoelasticity. We show that after pre-shearing at intermediate Mn, attractive sphere gel exhibits strengthening whereas attractive rod gel exhibits weakening. Rheo-imaging of gels of attractive rods shows that at intermediate Mn, oscillatory pre-shear induces large compact rod clusters in the gel microstructure, compared to steady pre-shear. Our study highlights the impact of particle shape on gel structuring under flow and viscoelasticity after shear cessation.

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arXiv2021

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. We examine two different phenomena of bubble dynamics that apply a local strain to the surrounding material: dissolution due to mass transfer, with a characteristic strain rate of $10^{-3}$ s$^{-1}$; and volumetric oscillations driven by ultrasound, with a characteristic frequency of $10^4$ s$^{-1}$. We characterise experimentally the microstructure of a model colloidal gel around bubbles in a Hele-Shaw geometry using confocal microscopy and particle tracking. In bubble dissolution experiments, we observe the formation of a pocket of solvent next to the bubble surface, but marginal changes to the microstructure. In experiments with ultrasound-induced bubble oscillations, we observe a striking rearrangement of the gel particles into a microstructure with increased local ordering. High-speed bright-field microscopy reveals the occurrence of both high-frequency bubble oscillations and steady microstreaming flow; both are expected to contribute to the emergence of the local order in the microstructure. These observations open the way to local tuning of colloidal gels based on deformable inclusions controlled by external pressure fields.

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arXiv2021

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. For each sample, we use image correlation processing to measure the macroscopic deformation field, and echo-Differential Dynamic Microscopy to probe the microscopic irreversible sample dynamics in reciprocal space; finally, we devise a simple scheme to spatially map the rearrangements in the sheared sample, once again without tracking the tracers. For the yield stress sample, we obtain a wave-vector dependent characterization of shear-induced diffusion across the yielding transition, which is accompanied by a three-order-of-magnitude speed-up of the dynamics and by a transition from localized, intermittent rearrangements to a more spatially homogeneous and temporally uniform activity. Our tracking free approach is intrinsically multi-scale, can successfully discriminate between different types of dynamics, and can be automated to minimize user intervention. Applications are many, as it can be translated to other imaging modes, including fluorescence, and can be used with sub-resolution tracers and even without tracers, for samples that provide intrinsic optical contrast.

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arXiv2020

Dilatancy in dense suspensions of model hard-sphere-like colloids under shear and extensional flow

Dense suspensions of model hard-sphere-like colloids, with different particle sizes, are examined experimentally in the glass state, under shear and extensional rheology. Under steady shear flow we detect Discontinuous Shear Thickening (DST) above a critical shear rate. Start-up shear experiments show stress overshoots in the vicinity of the onset of DST related with a change in microscopic morphology, as the sample shows dilatancy effects. The analysis of the normal stress together with direct sample observation by high speed camera, indicates the appearance of positive N1 and dilation behavior at the shear thickening onset. Dilatancy effects are detected also under extensional flow. The latter was studied through capillary breakup and filament stretching experimental setups, where liquid-like response is seen for strain rate lower than a critical strain rate and solid like-behavior for higher strain rates. Monitoring the filament thinning processes under different conditions (volume fractions and strain rates) we have created a state diagram where all responses of a hard-sphere suspension (Newtonian, shear thinning, shear thickening, dilatant) are shown. We finally compare the shear thickening response of these hard-sphere-like suspensions and glasses in shear with that in extensional flow.

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arXiv2016

Amorphous and ordered states of concentrated hard spheres under oscillatory shear

Hard sphere colloidal particles are a basic model system for general research into phase behavior, ordering and out-equilibrium glass transitions. Experimentally it has been shown that oscillatory shearing of a monodisperse hard sphere glass, produces two different crystal orientations; a Face Centered Cubic (FCC) crystal with the close packed direction parallel to shear at high strains and an FCC crystal with the close packed direction perpendicular to shear at low strains. Here, using Brownian dynamics simulations of hard sphere particles, we have examined high volume fraction shear-induced crystals under oscillatory shear as well as the same volume fraction glass counterparts. We find that, while the displacements under shear of the glass are isotropic, the sheared FCC crystal structures oriented parallel to shear, are anisotropic due to the cooperative motion of velocity-vorticity layers of particles sliding over each other. These sliding layers generally result in lower stresses and less overall particle displacements. Additionally, from the two crystal types, the perpendicular crystal exhibits less stresses and displacements at smaller strains, however at larger strains, the sliding layers of the parallel crystal are found to be more efficient in minimizing stresses and displacements, while the perpendicular crystal becomes unstable. The findings of this work suggest that the process of shear-induced ordering for a colloidal glass is facilitated by large out of cage displacements, which allow the system to explore the energy landscape and find the minima in energy, stresses and displacements by configuring particles into a crystal oriented parallel to shear.

cond-mat.soft↗

arXiv2010

Brambilla, et al. Reply

Brambilla, et al. Reply: van Megen and Williams (vMW) question our recent claim that dense colloidal hard spheres enter at large volume fraction ϕa dynamical regime not observed in earlier work and not described by the mode-coupling theory (MCT) of the glass transition.

cond-mat.soft↗

arXiv2009

Probing the equilibrium dynamics of colloidal hard spheres above the mode-coupling glass transition

We use dynamic light scattering and computer simulations to study equilibrium dynamics and dynamic heterogeneity in concentrated suspensions of colloidal hard spheres. Our study covers an unprecedented density range and spans seven decades in structural relaxation time, $\ta$, including equilibrium easurements above $ϕ_{\rm c}$, the location of the glass transition deduced from fitting our data to mode-coupling theory. Instead of falling out of equilibrium, the system remains ergodic above $ϕ_{\rm c}$ and enters a new dynamical regime where $\ta$ increases with a functional form that was not anticipated by previous experiments, while the amplitude of dynamic heterogeneity grows slower than a power law with $\ta$, as found in molecular glass-formers close to the glass transition.

cond-mat.soft↗

arXiv2009

Dynamic light scattering measurements in the activated regime of dense colloidal hard spheres

We use dynamic light scattering and numerical simulations to study the approach to equilibrium and the equilibrium dynamics of systems of colloidal hard spheres over a broad range of density, from dilute systems up to very concentrated suspensions undergoing glassy dynamics. We discuss several experimental issues (sedimentation, thermal control, non-equilibrium aging effects, dynamic heterogeneity) arising when very large relaxation times are measured. When analyzed over more than seven decades in time, we find that the equilibrium relaxation time, tau_alpha, of our system is described by the algebraic divergence predicted by mode-coupling theory over a window of about three decades. At higher density, tau_alpha increases exponentially with distance to a critical volume fraction phi_0 which is much larger than the mode-coupling singularity. This is reminiscent of the behavior of molecular glass-formers in the activated regime. We compare these results to previous work, carefully discussing crystallization and size polydispersity effects. Our results suggest the absence of a genuine algebraic divergence of tau_alpha in colloidal hard spheres.

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