Phase transition and gelation in cellulose nanocrystal-based aqueous suspensions studied by SANS

Aqueous suspensions of cellulose nanocrystals (CNC) form a re-entrant liquid crystal (LC) phase with increasing salinity. Phase separation occurs in this LC state leading to a biphasic gel with a flow programmable structure that can be used to form anisotropic soft materials. We term this state a Liquid Crystal Hydroglass (LCH). Defining the mechanisms by which the LCH forms requires detailed structural analysis at the mesoscopic length scale.

By utilising Small Angle Neutron Scattering (SANS), we investigated the microstructure transitions in CNC suspensions, with a particular focus on the unique LC re-entrancy and gelation into the biphasic LCH.

Scattering from LCH gels comprises contributions from a dispersed liquid state and static heterogeneity, characterised using a Lorentzian-Gaussian model of inhomogeneity. This conceptually supports a gelation mechanism (spinodal decomposition) in CNC suspensions towards a biphasic structure of the LCH. It also demonstrates that, with increasing salinity, the non-monotonic variation in effective volume fraction of CNC rods fundamentally causes the LC re-entrancy. This work provides the first experimental characterisation of the LC-re-entrancy and formation of an anisotropic LCH gel. The proposed mechanism can be extended to understanding the general behaviour of anisotropic colloids.