Determining the colloidal behavior of ionically cross-linked polyelectrolytes with isothermal titration calorimetry

Mixtures of polyelectrolytes and multivalent counterions can self-assemble into colloidal complexes. These complexes attract widespread interest in applications such as medicine, household product formulations, and separation processes. To facilitate the development of these colloidal dispersions, we examined isothermal titration calorimetry (ITC) as an automated screening tool for identifying the polymer and multivalent counterion compositions that (1) form ionically cross-linked colloidal complexes and (2) lead to their rapid coagulation (and macroscopic phase separation). By studying various polyelectrolyte/multivalent counterion mixtures, we have identified and generalized the features in the ITC data that indicate colloidal complex formation and coagulation. The limitations of this calorimetric screening method were also elucidated. These analyses suggest that ITC can be effective for screening the short-term colloidal behavior of polyelectrolyte/multivalent counterion mixtures but are unreliable in revealing their long-term (equilibrium) properties.