title: Direct Evidence for Percolation of Immobilized Polymer Layer around Nanoparticles Accounting for Sol-Gel Transition in Fumed Silica Dispersions.
abstract: Immobilized polymer fractions have been claimed to be of vital importance for sol-gel transitions generally observed in nanoparticle dispersions but remain a matter of debate regarding mechanism and difficulty for prediction. Here we investigate the immobilized layer structures of trifunctionality polyether polyol (PPG) near the surfaces of hydrophilic and hydrophobic fumed silica (FS) nanoparticles to reveal the role of surface chemistry on the molecular dynamics and sol-gel transitions of the dispersions. Using modulated differential scanning calorimetry, we measure the specific heat capacity during glass transition and the enthalpy during cold-crystallization. Comparing with hydrophobic FS that forms a fully immobilized (glassy) layer, we find that hydrophilic FS immobilizes more PPG, forming a partially immobilized outer layer being unable to crystallize next to the inner glassy layer. By correlating the thickness of the glassy layer with half of the minimum spacing between nanoparticles, we directly evidence the percolation of this layer along the nearest neighbor nanoparticles responsible for the sol-gel transition. Using effective volume fraction including the glassy layer, we successfully construct master curves of relative viscosity of both hydrophilic and hydrophobic FS dispersions, pointing to a common sol-gel transition mechanism mediated by the surface chemistry.
authors.affiliation: Department of Polymer Science and Engineering and ‡MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University , Hangzhou 310027, China.
authors.forename: Zhong
authors.initials: Z
authors.lastname: Zheng
authors.affiliation: Department of Polymer Science and Engineering and ‡MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University , Hangzhou 310027, China.
authors.forename: Yihu
authors.initials: Y
authors.lastname: Song
authors.affiliation: Department of Polymer Science and Engineering and ‡MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University , Hangzhou 310027, China.
authors.forename: Ruiquan
authors.initials: R
authors.lastname: Yang
authors.affiliation: Department of Polymer Science and Engineering and ‡MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University , Hangzhou 310027, China.
authors.forename: Qiang
authors.initials: Q
authors.lastname: Zheng