Laponite Clay in Homopolymer and Tri-block Copolymer Matrices. Thermal and Structural Investigations

Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments of the adsorbed macromolecule are anchored to the laponite (RD) particles and the remaining segments are radiating away from the surface. The portion of the macromolecule in contact with RD does not contribute to ΔH m whereas that radiating away from the clay does. Once that the RD surface is saturated, the excess of the macromolecule behaves like the pure one. The proposed model allowed to compute successfully the ΔH m values. The X-ray diffraction experiments ruled out the polymer intercalation between the silicate sheets.