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.

The aging dynamics of a colloidal glass has been studied by multiangle dynamic light scattering, neutron spin echo, X-ray photon correlation spectroscopy and molecular dynamics simulations. The two relaxation processes, microscopic (fast) and structural (slow), have been investigated in an unprecedentedly wide range of time and length scales covering both ergodic and nonergodic regimes. The microscopic relaxation time remains diffusive at all length scales across the glass transition scaling with wavevector Q as Q(-2). The length-scale dependence of structural relaxation time changes from diffusive, characterized by a Q(-2)-dependence in the early stages of aging, to a Q(-1)-dependence in the full aging regime which marks a discontinuous hopping dynamics. Both regimes are associated with a stretched behaviour of the correlation functions. We expect these findings to provide a general description of both relaxations across the glass transition.

Clay-polymer compounds have recently attracted increasing attention due to their intriguing physical properties in colloidal science and their rheological non-trivial behaviour in technological applications. Aqueous solutions of Laponite clay spontaneously age from a liquid up to an arrested state of different nature (gel or glass) depending on the colloidal volume fraction and ionic strength. We have investigated, through dynamic light scattering, how the aging dynamics of Laponite dispersions at fixed clay concentration (Cw = 2.0%) is modified by the addition of various amounts of poly(ethylene oxide) (PEO) (CPEO = (0.05 ÷ 0.50) %) at two different molecular weights (Mw = 100 kg mol(-1) and Mw = 200 kg mol(-1)). A surprising and intriguing phenomenon has been observed: the existence of a critical polymer concentration C that discriminates between two different aging dynamics. With respect to pure Laponite systems the aging will be assisted (faster) or hindered (slower) for PEO concentrations respectively lower (CPEO < C) or higher (CPEO > C) than the critical concentration. In this way a control on the aging dynamics of PEO-Laponite systems is obtained. A possible explanation based on the balance of competitive mechanisms related to the progressive saturation of the clay surface by polymers is proposed. This study shows how a real control on the aging speed of the PEO-Laponite system is at hand and renders possible a real control of the complex interparticle interaction potential.

The time evolution of both dynamic and static structure factors of a charged colloidal clay, Laponite, dispersed in both HO and DO solvents has been investigated through multiangle dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) as a function of weight concentration. The aging phenomenology and the formation of arrested states, both gel and glass, are preserved in DO, while the dynamics is slowed down with respect to water. These findings are important to understand the role played by the solvent in the interparticle interactions and for techniques such as neutron scattering and nuclear magnetic resonance that allow for the extension of the accessible scattering vectors and time scales.