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Bimodal surface ligand engineering: the key to tunable nanocomposites.

Langmuir : the ACS journal of surfaces and colloids (2012-10-25)
Ying Li, Peng Tao, Anand Viswanath, Brian C Benicewicz, Linda S Schadler
ABSTRACT

Tuning the dispersion of inorganic nanoparticles within organic matrices is critical to optimizing polymer nanocomposite properties and is intrinsically difficult due to their strong enthalpic incompatibility. Conventional attempts to use polymer brushes to control nanoparticle dispersion are challenged by the need for high graft density to reduce particle core-core attractions and the need for low graft density to reduce the entropic penalty for matrix penetration into the brush. We validated a parametric phase diagram previously reported by Pryamtisyn et al. (Pryamtisyn, V.; Ganesan, V.; Panagiotopoulos, A. Z.; Liu, H.; Kumar, S. K. Modeling the Anisotropic Self-Assembly of Spherical Polymer-Grafted Nanoparticles. J. Chem. Phys.2009, 131, 221102) for predicting dispersion of monomodal-polymer-brush-modified nanoparticles in polymer matrices. The theoretical calculation successfully predicted the experimental observation that the monomodal-poly(dimethyl siloxane) (PDMS)-brush-grafted TiO(2) nanoparticles can only be well dispersed within a small molecular weight silicone matrix. We further extended the parametric phase diagram to analyze the dispersion behavior of bimodal-PDMS-brush-grafted particles, which is also in good agreement with experimental results. Utilizing a bimodal grafted polymer brush design, with densely grafted short brushes to shield particle surfaces and sparsely grafted long brushes that favor the entanglement with matrix chains, we dispersed TiO(2) nanoparticles in high molecular weight commercial silicone matrices and successfully prepared thick (about 5 mm) transparent high-refractive-index TiO(2)/silicone nanocomposites.

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tert-Butylamine, ≥99.5%