Luca Cipelletti

Jamming phase diagram for attractive particles

A wide variety of systems, including granular media, colloidal suspensions and molecular systems, exhibit non-equilibrium transitions from a fluid-like to a solid-like state, characterized solely by the sudden arrest of their dynamics. Crowding or jamming of the constituent particles traps them kinetically, precluding further exploration of the phase space. The disordered fluid-like structure remains essentially unchanged at the transition. The jammed solid can be refluidized by thermalization, through temperature or vibration, or by an applied stress. The generality of the jamming transition led to the proposal of a unifying description, based on a jamming phase diagram. It was further postulated that attractive interactions might have the same effect in jamming the system as a confining pressure, and thus could be incorporated into the generalized description. Here we study experimentally the fluid-to-solid transition of weakly attractive colloidal particles, which undergo markedly similar gelation behaviour with increasing concentration and decreasing thermalization or stress. Our results support the concept of a jamming phase diagram for attractive colloidal particles, providing a unifying link between the glass transition, gelation and aggregation.

Direct experimental evidence of a growing length scale accompanying the glass transition

Understanding glass formation is a challenge, because the existence of a true glass state, distinct from liquid and solid, remains elusive: Glasses are liquids that have become too viscous to flow. An old idea, as yet unproven experimentally, is that the dynamics becomes sluggish as the glass transition approaches, because increasingly larger regions of the material have to move simultaneously to allow flow. We introduce new multipoint dynamical susceptibilities to estimate quantitatively the size of these regions and provide direct experimental evidence that the glass formation of molecular liquids and colloidal suspensions is accompanied by growing dynamic correlation length scales.

Dynamical heterogeneities in glasses, colloids, and granular media

1. Scientic interview on the glass transition 2. An overview of the theories of the glass transition 3. Overview of different characterisations of dynamic heterogeneity 4. Glassy dynamics and dynamical heterogeneity in colloids 5. Experimental Approaches to Heterogeneous Dynamics 6. Dynamical Heterogeneities in Grains and Foams 7. The Length Scales of Dynamic Heterogeneity: Results from Molecular Dynamics Simulations 8. Heterogeneities in amorphous systems under shear 9. The jamming scenario an introduction and outlook 10. Kinetically Constrained Models 11. Growing length scales in aging systems 12. Analytical approaches to time and length scales in models of glasses

Slow dynamics in glassy soft matter

Measuring, characterizing, and modelling the slow dynamics of glassy soft matter is a great challenge, with an impact that ranges from industrial applications to fundamental issues in modern statistical physics, such as the glass transition and the description of out-of-equilibrium systems. Although our understanding of these phenomena is still far from complete, recent simulations and novel theoretical approaches and experimental methods have shed new light on the dynamics of soft glassy materials. In this paper, we review the work of the last few years, with an emphasis on experiments in four distinct and yet related areas: the existence of two different glass states (attractive and repulsive), the dynamics of systems very far from equilibrium, the effect of an external perturbation on glassy materials, and dynamical heterogeneity.

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, � � , including equilibrium measurements above ’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 ’c and enters a new dynamical regime where � � 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 � � , as found in molecular glass formers close to the glass transition.

Ultralow-angle dynamic light scattering with a charge coupled device camera based multispeckle, multitau correlator

We use a charge coupled device (CCD) camera and a multi-tau software correlator to measure dynamic light scattering (DLS) at many angles simultaneously, from 0.07° to 5.1°. Real-time autocorrelation functions are calculated by averaging both over time and over CCD pixels, each corresponding to a different coherence area. In order to cover the wide spectrum of decay times associated with the large range of accessible angles, we adopt the multitau scheme, where the correlator channel spacing is quasilogarithmic rather than linear. A detailed analysis is presented of the effects of dark noise, stray light, and finite pixel area, and methods to correct the data for these effects are developed, making a CCD camera a viable alternative for a DLS detector. We test the apparatus on a dilute suspension of colloidal particles. Very good agreement is found between the particle radius derived from the CCD data, and that obtained with a conventional DLS setup.

Universal non-diffusive slow dynamics in aging soft matter

We use conventional and multispeckle dynamic light scattering to investigate the dynamics of a wide variety of jammed soft materials, including colloidal gels, concentrated emulsions, and concentrated surfactant phases. For all systems, the dynamic structure factor f(q,t) exhibits a two-step decay. The initial decay is due to the thermally activated diffusive motion of the scatterers, as indicated by the q(-2) dependence of the characteristic relaxation time, where q is the scattering vector. However, due to the constrained motion of the scatterers in jammed systems. the dynamics are arrested and the initial decay terminates in a plateau. Surprisingly, we find that a final, ultraslow decay leads to the complete relaxation of f(q,t), indicative of rearrangements on length scales as large as several microns or tens of microns. Remarkably, for all systems the same very peculiar form is found for the final relaxation of the dynamic structure factor: f(q,t) approximately exp[-(t/tau s)p], with p approximately equal to 1.5 and tau s approximately q(-1), thus suggesting the generality of this behavior. Additionally, for all samples the final relaxation slows down with age. although the aging behavior is found to be sample dependent. We propose that the unusual ultraslow dynamics are due to the relaxation of internal stresses, built into the sample at the jamming transition, and present simple scaling arguments that support this hypothesis.

Length scale dependence of dynamical heterogeneity in a colloidal fractal gel

We use time-resolved dynamic light scattering to investigate the slow dynamics of a colloidal gel. The final decay of the average intensity autocorrelation function is well described by g2(q,τ) − 1 ~ exp [ − (τ/τf)p], with τf ~ q−1 and p decreasing from 1.5 to 1 with increasing q. We show that the dynamics is not due to a continuous ballistic process, as proposed in previous works, but rather to rare, intermittent rearrangements. We quantify the dynamical fluctuations resulting from intermittency by means of the variance χ(τ,q) of the instantaneous autocorrelation function, the analogous of the dynamical susceptibility χ4 studied in glass formers. The amplitude of χ is found to grow linearly with q. We propose a simple—yet general—model of intermittent dynamics that accounts for the q-dependence of both the average correlation functions and χ.

Transient gelation by spinodal decomposition in colloid-polymer mixtures

We have investigated with small angle light scattering and optical microscopy transient gelation phenomena which occur in phase-separating colloid-polymer mixtures. The scattering intensity distribution shows a peak at non-zero wave vector and satisfies the asymptotic q−4 Porod behaviour. Consistent with these observations, optical micrographs show an alternating pattern of dark and bright domains. These findings suggest that the polymer-induced depletion forces lead to the formation of a bicontinuous network of colloid-rich and colloid-poor domains, via a spinodal decomposition process. This bicontinuous network rapidly attains a gel-like character as indicated by the arrest of speckle fluctuations. The occurrence of the gel is ascribed to polymer-induced aggregation between the colloids in the colloid-rich phase. Due to the reversible nature of the aggregation the network restructures and eventually the gel collapses, as is manifested by the rapid separation of the colloid-rich phase from the colloid-poor phase.

Ultraslow dynamics and stress relaxation in the aging of a soft glassy system.

We use linear rheology and multispeckle dynamic light scattering (MDLS) to investigate the aging of a gel composed of multilamellar vesicles. Light scattering data indicate rearrangement of the gel through an unusual ultraslow ballistic motion. A dramatic slowdown of the dynamics with sample age t(w) is observed for both rheology and MDLS, the characteristic relaxation time scaling as t(mu)w. We find the same aging exponent mu = 0.78 for both techniques, suggesting that they probe similar physical processes, that is the relaxation of applied or internal stresses for rheology or MDLS, respectively. A simple phenomenological model is developed to account for the observed dynamics.