Abstract
The adsorption-induced bridging of polymer chains between adjacent nanoparticles was studied in poly(vinyl acetate)/silica nanocomposites with different polymer molecular weights, interaction strengths, nanoparticle sizes, and silica loading fractions. The polymer bridging contribution is successfully decoupled from the apparent rubbery plateau modulus by subtracting the hydrodynamic and trapped chain entanglement contributions. The bridging modulus depends on the nearest interparticle surface distance through a power-law relation with a universal exponent −3. Polymer molecular weight can enhance the bridging modulus only when nanoparticles have a high density of adsorption sites due to the emergence of direct bridging of multiple particles by one chain in addition to the regular bridging through self-similar carpets. Our results illustrate that bridging chains can dominate modulus enhancement at nanoparticle's loading at about 10 vol% in polymer nanocomposites with long polymer chains and high surface silanol density.
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