Unravelling the polyethylenimine mediated non-monotonic stability behaviour of silica colloids: the role of competing electrostatic and entropic interactions.

Polymer-mediated interactions play an important role in the stability of colloids and are therefore paramount for both fundamental as well as scientific interests. The stability of colloids in the presence of neutral polymers depends on several parameters such as the adsorbing/non-adsorbing nature, molecular weight, concentration and temperature, and such systems are well studied. However, the stability behaviour of charged colloids in the presence of charged polyelectrolyte involves complex interaction mechanisms and hence needs attention. The present work reports the study of the stability behaviour of negatively charged silica colloids in the presence of cationic polyethylenimine (PEI) polyelectrolyte using small-angle neutron and X-ray scattering. The intriguing non-monotonic stability behaviour of silica colloids is observed with varying concentrations of PEI. In the low and intermediate PEI concentration regimes, electrosorption of PEI on the silica colloids causes partial screening of charges, leading to aggregation of colloids. The DLVO interaction potential at low and intermediate concentrations of PEI exhibit a reduced repulsion barrier which is responsible for aggregation. In the high concentration regime, the entropic interaction between the free PEI molecules and PEI decorated silica colloids leads to depletion re-stabilization. The combination of DLVO potential and adsorbed PEI mediated enhanced depletion repulsion in the presence of free PEI gives rise to an increased repulsion barrier responsible for the re-stabilization at high PEI concentrations.