Toughening fragile matter: mechanical properties of particle solids assembled from polymer-grafted hybrid particles synthesized by ATRP

The effect of polymer-graft modification on the structure formation and mechanical characteristics of inorganic (silica) nanoparticle solids is evaluated as a function of the degree of polymerization of surface-grafted chains. A transition from 'hard-sphere-like' to 'polymer-like' mechanical characteristics of particle solids is observed for increasing degree of polymerization of grafted chains. The elastic modulus of particle solids increases by about 200% and levels off at intermediate molecular weights of surface-grafted chains, a trend that is rationalized as a consequence of the elastic modulus being determined by dispersion interactions between the polymeric grafts. A pronounced increase (of about one order of magnitude) of the fracture toughness of particle solids is observed as the degree of polymerization of grafted chains exceeds a threshold value that is similar for both polystyrene and poly(methyl methacrylate) grafts. The increased resistance to fracture is interpreted as a consequence of the existence of entanglements between surface-grafted chains that give rise to energy dissipation during fracture through microscopic plastic deformation and craze formation. Within the experimental uncertainty the transition to polymer-like deformation characteristics is captured by a mean field scaling model that interprets the structure of the polymer shell of polymer-grafted particles as effective 'two-phase' systems consisting of a stretched inner region and a relaxed outer region. The model is applied to predict the minimum degree of polymerization needed to induce polymer-like mechanical characteristics and thus to establish 'design criteria' for the synthesis of polymer-modified particles that are capable of forming mechanically robust and formable particle solid structures.