Barbara Ruzicka

Observation of empty liquids and equilibrium gels in a colloidal clay

The relevance of anisotropic interactions in colloidal systems has recently emerged in the context of the rational design of new soft materials. Patchy colloids of different shapes, patterns and functionalities are considered the new building blocks of a bottom-up approach toward the realization of self-assembled bulk materials with predefined properties. The ability to tune the interaction anisotropy will make it possible to recreate molecular structures at the nano- and micro-scales (a case with tremendous technological applications), as well as to generate new unconventional phases, both ordered and disordered. Recent theoretical studies suggest that the phase diagram of patchy colloids can be significantly altered by limiting the particle coordination number (that is, valence). New concepts such as empty liquids—liquid states with vanishing density—and equilibrium gels—arrested networks of bonded particles, which do not require an underlying phase separation to form—have been formulated. Yet no experimental evidence of these predictions has been provided. Here we report the first observation of empty liquids and equilibrium gels in a complex colloidal clay, and support the experimental findings with numerical simulations.

A fresh look at the Laponite phase diagram

By reviewing experimental and theoretical works, we discuss the phase diagram of Laponite suspensions, with the aim of clarifying several issues that have caused a long-time controversy on the system. We claim that, if aging and sample preparation are correctly taken into account, a unifying picture emerges from different experimental studies. Multiple non-ergodic states are identified, including a low concentration equilibrium gel and a high concentration Wigner glass in the absence of salt. These findings are critically discussed also with respect to recent evidence of phase separation at extremely low densities and to existing theoretical and numerical works.

Routes to Gelation in a Clay Suspension

The gelation of water suspension of a synthetic clay (Laponite) has been studied by dynamic light scattering in a wide range of clay weight concentration (C(w)=0.003-0.031). At variance with previous determination, indicating a stable liquid phase for C(w)<C(*)(w) approximately 0.015-0.018, we find that gelation actually takes place in the whole examined C(w) range. We find also that C(*)(w) marks the transition between two different routes to gelation. We hypothesize that at low concentration Laponite suspension behaves as an attractive colloid and that the slowing down of the dynamics is attained by the formation of larger and larger clusters while at high concentration the basic units of the arrested phase could be the Debye Huckel spheres associated with single Laponite plates.

Competing interactions in arrested states of colloidal clays

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at high concentrations is stabilized by screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modeling and simulations at high concentrations reproduce the measured small angle x-ray scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different time scales controlling the competing attractive and repulsive interactions.

Glass–glass transition during aging of a colloidal clay

Colloidal suspensions are characterized by a variety of microscopic interactions, which generate unconventional phase diagrams encompassing fluid, gel and glassy states and offer the possibility to study new phase and/or state transitions. Among these, glass-glass transitions are rare to be found, especially at ambient conditions. Here, through a combination of dilution experiments, X-ray photon correlation spectroscopy, small angle X-ray scattering, rheological measurements and Monte Carlo simulations, we provide evidence of a spontaneous glass-glass transition in a colloidal clay. Two different glassy states are distinguished with evolving waiting time: a first one, dominated by long-range screened Coulombic repulsion (Wigner glass) and a second one, stabilized by orientational attractions (Disconnected House of Cards glass), occurring after a much longer time. These findings may have implications for heterogeneously charged systems out-of-equilibrium and for applications where a fine control of the local order and/or long term stability of the amorphous materials are required.

Arrested state of clay-water suspensions: gel or glass?

The aging of a charged colloidal system has been studied by small-angle x-ray scattering, in the exchanged momentum range Q=0.03-5 nm(-1) , and by dynamic light scattering, at different clay concentrations (C(w)=0.6-2.8%) . The static structure factor S(Q) has been determined as a function of both aging time and concentration. This is the direct experimental evidence of the existence and evolution with aging time of two different arrested states in a single system simply obtained only by changing its volume fraction: an inhomogeneous state is reached at low concentrations, while a homogeneous one is found at high concentrations.

Evidence of anomalous dispersion of the generalized sound velocity in glasses

The dynamic structure factor S(Q,ω), of vitreous silica, has been measured by inelastic x-ray scattering in the exchanged wave-vector (Q) region Q=4-16.5 nm - 1 and up to energies ∞ω= 115 meV in the Stokes side. The unprecedented statistical accuracy in such an extended energy range allows us to accurately determine the longitudinal current spectra and the energies of the vibrational excitations. The simultaneous observation of two excitations in the acoustic region and the persistence of propagating sound waves up to Q values comparable with the (pseudo-)Brillouin-zone edge allow us to observe a positive dispersion in the generalized sound velocity that, around Q5 nm - 1 , varies from 6500 to 9000 m/s; this phenomenon was never experimentally observed in a glass.

Chemical and physical hydrogels: two casesystems studied by quasi elastic light scattering

A chemical hydrogel based on telechelic poly(vinyl alcohol) and a physical synergic hydrogel, xanthan–glucomannan, were studied by means of dynamic light scattering technique. Two different nonergodic methods, due to Pusey et al. (Physica A 157 (1989) 705, Phys. Rev. A 42 (1990) 2161) and Xue et al. (Phys. Rev. A 46 (1992) 6550), were used to obtain the correct dynamic structure factors f(q,t). Good agreement between the results obtained with the two procedures was found. The behavior of the f(q,t) for different q vectors is consistent with the hypothesis that the nonfluctuating component in the scattered light is not due to microscopic heterogeneities but to restricted motion of the scatterers. The model of Krall et al. (Phys. Rev. Lett. 80 (1998) 778, Physica A 235 (1997) 19) was successfully applied to both hydrogels to extract the characteristic parameters of the network from the f(q,t) functions.

Ergodic to non-ergodic transition in low concentration Laponite

At variance with previous determinations, recent investigations on water suspension of a synthetic clay (Laponite) have shown the presence of an arrested phase also at very low clay concentrations (down to Cw = 0.003). This surprising behaviour has been studied in a wide clay concentration range. As a result the existence of two different routes towards the arrested phase, applying to low and high Laponite concentrations, has been found. We can speculate that at high clay concentration the system would form a Wigner glass whose elementary units are single Laponite platelets, as already indicated in previous works. At low clay concentrations, in contrast, the Wigner glass is supposed to be composed of clusters of Laponite platelets; in this case the clusters would be stabilized by the competition of long-range electrostatic repulsion and short-range attractive interactions. A similar behaviour has been recently found in a simulation work (Sciortino et al 2003 Preprint cond-mat/0312161).

Ageing dynamics in Laponite dispersions at various salt concentrations

The ageing dynamics of a charged colloidal system, Laponite suspended in water, have been investigated by photon correlation technique. The samples covered a novel and very wide range of clay concentrations (C w = 0.3–3.1 wt%) and four different NaCl concentrations (C s = 1 × 10−4 M, 1 × 10−3 M, 2 × 10−3 M and 5 × 10−3 M) and were studied to investigate the phase diagram, which has been a subject of discussion in recent literature. A clear picture of the Laponite phase diagram has been obtained. The measurements show the existence of two different dynamical routes to reach a final arrested state and the presence of a transition line between them in the C w−C s plane.