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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.more » « less
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Trevenen, Samuel; Rahman, Md_Anisur; Hamilton, Heather_SC; Ribbe, Alexander_E; Bradley, Laura_C; Beltramo, Peter_J (, ACS Nano)
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