Résumé
A combined small-angle scattering of neutrons (SANS) and X-rays (SAXS) study of thestructure of polymer layers pre-adsorbed on silica nanoparticles (NP) which are subsequentlyincorporated into polymer nanocomposites (PNCs) is presented. Pre-adsorbed chains are foundto promote ideal dispersion, before desorption in the late stages of nanocomposite formation.The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-rayand neutron scattering. Only in ideally well-dispersed systems a static interfacial layer ofreduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with aform-free density profile optimized using reverse Monte Carlo simulations. This interfacialgradient layer is found to be independent of the thickness and mass of the initially adsorbedpolymer, but appears to be generated by out-of-equilibrium packing and folding of the preadsorbedlayer. The impact of annealing is investigated to study the approach of equilibrium,showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure,while the static interfacial layer disappears.In parallel, SANS and the use of zero average contrast conditions allow the measurement ofchain conformation in the PNCs with and without pre-adsorption. Surprisingly, we evidenced thespontaneous formation of thermally-stable adsorbed layers in PNCs containing matrix chains ofdifferent mass, whereas a symmetric matrix of identical chain masses does not show this effect.This study contributes thus to the fundamental understanding of the interplay betweeneffects which are decisive for macroscopic material properties: polymer-mediated interparticleinteractions, and particle interfacial effects on surrounding polymer.