Heterogeneous materials in which the characteristic length scale of the filler material is in the nanometer range—i.e., nanocomposites—is currently one of the fastest growing areas of materials research. Polymer nanocomposites have expanded beyond the original scope of polymer–nanocrystal dispersions for refractive‐index tuning or clay‐filled homopolymers primarily pursued for mechanical reinforcement, to include a wide range of applications. This article highlights recent research efforts in the field of structure formation in block copolymer‐based nanocomposite materials, and points out opportunities for novel materials based on inclusion of different types of nanoparticles. The use of block copolymers instead of homopolymers as the matrix is shown to afford opportunities for controlling the spatial and orientational distribution of the nanoelements. This, in turn, allows much more sophisticated tailoring of the overall properties of the composite material.

Dependent on the relative particle core size, two distinct types of particle topologies in block copolymer/nanocrystal blends have been identified, that is, the localization of particles along the intermaterial dividing surface or at the center of the respective polymer domain. In ternary systems consisting of block copolymer and two different-sized nanocrystal species, the distinct morphological types are conserved, resulting in autonomous size-selective separation and organization of the respective nanocrystals within alternating arrays and sheets.

Surface-initiated atom transfer radical polymerization (SI-ATRP) has become an indispensable tool for engineering the structure and properties of polymer/inorganic and polymer/organic interfaces. This article describes the progress and challenges that are associated with the application of SI-ATRP to precisely control the molecular characteristics of polymer chains tethered to nanoparticle surfaces and explores the properties and potential applications of the resulting particle brush materials. Even for the conceptually most “simple” particle brush systemsthat is, spherical particles uniformly grafted with amorphous nonpolar polymersthe complex superposition of interactions as well as time- and length-scales related to particle core and tethered chains provides a rich and largely unexplored parameter space for the design of novel functional materials. The application of the particle brush approach to the development of materials for applications ranging from photonic inks and paints to advanced high “k” dielectrics for energy storage and advanced nanocomposite materials with improved optical, mechanical, or transport characteristics is discussed.

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.