Effects of the polymer glass transition on the stability of nanoparticle dispersions

Abstract

In addition to the repulsive and attractive interaction forces described by Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, many charged colloid systems are stabilized by non-DLVO contributions stemming from specific material attributes. Here, we investigate non-DLVO contributions to the stability of polymer colloids stemming from the intra-particle glass transition temperature (T_g). Flash nanoprecipitation is used to fabricate nanoparticles (NPs) from a library of polymers and dispersion stability is studied in the presence of both hydrophilic and hydrophobic salts. When adding KCl, stability undergoes a discontinuous decrease as T_g increases above room temperature, indicating greater stability of rubbery NPs over glassy NPs. Glassy NPs are also found to interact strongly with hydrophobic phosphonium cations (PR₄⁺), yielding charge inversion and intermediate aggregation while rubbery NPs resist ion adsorption. Differences in the lifetime of ionic structuration within mobile surface layers is presented as a potential mechanism underlying the observed phenomenon.