Partition of Coating Agents between Nanoparticle Interfaces and the Polymer in Nanocomposites

TL;DR

This study investigates how silane coating agents distribute between nanoparticle interfaces and the polymer matrix in nanocomposites, using dielectric spectroscopy and calorimetry to quantify partitioning and adsorption behaviors.

Contribution

It provides a quantitative analysis of silane partitioning and adsorption on silica NPs in polymer nanocomposites, revealing the initial coating mechanisms before grafting reactions.

Findings

Silane coating agents adsorb onto silica surfaces, reaching a plateau consistent with industrial formulations.

Partitioning of silanes into the polymer matrix occurs before grafting reactions, affecting material properties.

Adsorption levels are comparable to grafted amounts, indicating saturation in initial formulation stages.

Abstract

Industrial and model polymer nanocomposites are often formulated with coating agents to improve polymer-nanoparticle (NP) compatibility. Here the localization of silane coating agents in styrene-butadiene nanocomposite is investigated through the segmental dynamics of the polymer matrix by broadband dielectric spectroscopy (BDS), allowing the detection of silanes in the matrix through their plasticization effect. This acceleration of dynamics was followed via the shift of $\tau$max of the $\alpha$-relaxation induced by the presence of coating agents of different molecular weight and quantity, for different amounts of incorporated colloidal silica NPs (R $\approx$ 12.5 nm, polydispersity 12%). Any noteworthy contribution of interfacial polymer layers on $\tau$max has been excluded by reference measurements with bare NPs. Our approach allowed quantifying the partition between the matrix and the NP interfaces, and was confirmed independently by calorimetry. As a control parameter, the silane grafting reaction could be activated or not, which was confirmed by the absence (resp. presence) of partitioning with the matrix. Our main result is that in the first steps of material formulation, before any grafting reaction, coating agents both cover the silica surface by adsorption and mix with the polymer matrix-in particular if the latter has chemical compatibility via its functional groups. Silane adsorption was found to be comparable to the grafted amount (1.1 nm-2), and does not increase further, confirming that the plateau of the adsorption isotherm is reached in industrial formulations. These results are hoped to contribute to a better understanding of the surface reactions taking place during complex formulation processes of nanocomposites, namely the exact amounts at stake, e.g., in industrial mixers. Final material properties are affected both through NP-matrix compatibility and plasticization of the latter by unreacted molecules. 2