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.