Resolving Salt-Induced Agglomeration of Laponite Suspensions Using X-ray Photon Correlation Spectroscopy and Molecular Dynamics Simulations

Linking the physics of the relaxation behavior of viscoelastic fluids as they form arrested gel states to the underlying chemical changes is essential for developing predictive controls on the properties of the suspensions. In this study, 3 wt.% laponite suspensions are studied as model systems to probe the influence of salt-induced relaxation behavior arising from the assembly of laponite nanodisks. X-ray Photon Correlation Spectroscopy (XPCS) measurements show that laponite suspensions prepared in the presence of 5 mM concentrations of CaCl₂, MgCl₂ and CsCl salts accelerate the formation of arrested gel states, with CaCl₂ having a significant impact followed by CsCl and MgCl₂ salts. The competing effects of ion size and charge on relaxation behavior are noted. For example, the relaxation times of laponite suspensions in the presence of Mg²⁺ ions are slower compared to Cs+ ions despite the higher charge, suggesting that cation size dominates in this scenario. The faster relaxation behavior of laponite suspensions in the presence of Ca²⁺ ions compared to Cs⁺ ions shows that a higher charge dominates the size of the ion. The trends in relaxation behavior are consistent with the cluster formation behavior of laponite suspensions and the electrostatic interactions predicted from MD simulations. Charge balance is achieved by the intercalation of the cations at the negatively charged surfaces of laponite suspensions. These studies show that the arrested gel state of laponite suspensions is accelerated in the presence of salts, with ion sizes and charges having a competing effect on relaxation behavior.