It is now well-accepted that hydrophilic nanoparticles (NPs) lightly grafted with polymer chains self-assemble into a variety of superstructures when placed in a hydrophobic homopolymer matrix or in a small molecule solvent. Currently, it is thought that a given NP sample should only assemble into one kind of superstructure depending on the relative balance between favorable NP core–core attractions and steric repulsion between grafted polymer chains. Surprisingly, we find that each sample shows the simultaneous formation of a variety of NP-assemblies, e.g., well-dispersed particles, strings, and aggregates. We show through the generalization of a simple geometric model that accounting for the distributions of the NP core size and the number of grafted chains on each NP (which is especially important at low coverages) allows us to quantitatively model the aggregate shape distribution. We conclude that, in contrast to molecular surfactants with well-defined chemistries, the self-assembly of these NP analogues is dominated by such fluctuation effects.

Fused filament fabrication (FFF) three-dimensional (3D) printing of semicrystalline polymers such as high-density polyethylene (HDPE) is challenging because crystallization-induced shrinkage of the filament, as it cools, results in stresses that warp the printed part and debond it from the print substrate. Here, we demonstrate that waste-derived HDPE can be successfully 3D printed by (i) blending with a small fraction (<0.5% by weight) of dimethyl dibenzylidene sorbitol (DMDBS) and (∼10%) linear low density polyethylene (LLDPE) and (ii) printing the object with a thin “brim” around it that is adhered to the print substrate using common polyvinyl acetate-based glue. We match our experimental results with FEM simulations that provide insight into the origin of the stresses developed during printing. Because HDPE forms a significant fraction of the plastic waste stream, conversion of waste-derived HDPE to 3D printing filament has important technological implications.

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In polymer-grafted nanoparticles (PGN), covalent tethering of apolar polymer chains to a polar inorganic nanoparticle core induces the formation of self-assembled aggregates. Since the nature of these aggregates determines bulk mechanical and transport properties, it is of importance to understand the factors that determine the underlying assembly processes. In the literature, the solution assembly of PGNs has been understood in analogy to small-molecule amphiphiles. However, in any experimental realization, PGNs are invariably characterized by additional structural complexity, such as the distributions in the inorganic core size and in the grafted chains (both in their length and grafting density). These strongly influence the assembly of amphiphilic PGNs. We have previously demonstrated that dispersity in core size qualitatively affects the structure of PGN aggregates, and Jayaraman et al. demonstrated the effect of grafted chain-length dispersity. The combined effects of dispersity in the size of the core and grafted chains have not been explored previously. Here, we develop a model that builds on the work of Daoud and Cotton to explore a wide parameter space of PGN with dispersity simultaneously in core size and grafted chain length. We demonstrate that dispersity in core size is the dominant factor affecting the self-assembled solution structure of PGN aggregates. Our work suggests the importance of focusing on synthetic strategies for control of core-size dispersity to control aggregate structure in PGN.