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Nearly monodisperse nanoparticle (NP) spheres attached to a nonvolatile ionic liquid surface were tracked by in situ scanning electron microscopy to obtain the tracer diffusion coefficient D-tr as a function of the areal fraction phi. The in situ technique resolved both tracer (gold) and background (silica) particles for similar to 1-2 min, highlighting their mechanisms of diffusion, which were strongly dependent on phi. Structure and dynamics at low and moderate phi paralleled those reported for larger colloidal spheres, showing an increase in order and a decrease in D-tr by over 4 orders of magnitude. However, ligand interactions were more important near jamming, leading to different caging and jamming dynamics for smaller NPs. The normalized D-tr at ultrahigh phi depended on particle diameter and ligand molecular weight. Increasing the PEG molecular weight by a factor of 4 increased D-tr by 2 orders of magnitude at ultrahigh phi, indicating stronger ligand lubrication for smaller particles. 

Abstract Visualizing the network of a solvent‐swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1‐ethyl‐3‐methyl imidazolium ethyl sulfate [EMIM][EtSO₄]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent‐permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Recognizing that a network's three dimensionality is ambiguous when assessed through two‐dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three‐dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections. 

ABSTRACT Crystals of poly(ethylene glycol) grown in thin films of the room temperature ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium ethyl sulfate were examined by electron microscopy as a first step toward exploiting nonvolatile liquids for nanoscale imaging of solvated/dissolved polymeric materials. The crystals were generated by cooling supported (over surfaces of varied polarity) and freestanding solution films to room temperature. This “open,” that is, without liquid cell, microscopy was performed on unstained, as‐grown crystals in the presence of the IL. A variety of nearly two‐dimensional crystal morphologies were observed, including rods, fibers, spherulites, compact faceted single crystals, and interconnected networks, with characteristic sizes ranging from tens of nanometers to tens of microns. Electron diffraction patterns for the rods and fibers revealed single crystal‐like long‐range order. The nature of the IL support little affected the morphology, but film thickness and cooling rate proved important. To assess the role of solvent polarity, crystals were also grown from 1‐ethyl‐3‐methylimidazolium ethyl sulfate mixed with the second IL, the less polar ethyl‐tributyl‐phosphonium diethyl phosphate; here, although the morphologies were similar to those made with pure IL, fibrillar morphologies were more prevalent. © 2020 Wiley Periodicals, Inc. J. Polym. Sci.2020,58, 478–486