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Lhermitte, Julien

Publications and source records attributed to Lhermitte, Julien.

Nanoconfinement and Salt Synergistically Suppress Crystallization in Polyethylene Oxide

Suppressing the crystallization of polyether-based solid electrolytes is a widely sought-after strategy to improve ionic conductivity. We report the effects of nanoconfinement on polyethylene oxide electrolytes. We find that neat polyethylene oxide responds to nanoconfinement by adopting a preferred orientation, yet is able to crystallize even in nanoconfinement volumes with widths as small as 8 nm. However the combination of nanoconfinement and salt addition does suppress polymer crystallization at room temperature, even though either factor alone cannot. Such synergistic suppression of crystallization has implications for polymer electrolytes, since amorphous rather than crystalline domains predominantly contribute to ionic conduction. Our results suggest that salts previously discounted due to their inability to suppress crystallinity in bulk materials could be made viable when combined with nanoconfinement, thereby opening new possibilities for high-performance solid polymer electrolytes.

36 MATERIALS SCIENCE↗

Nanoscale viscosity of confined polyethylene oxide

Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ~500 times the bulk viscosity. Here, this enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.

36 MATERIALS SCIENCE↗

Supra-Nanoparticle Functional Assemblies through Programmable Stacking

The quest for the by-design assembly of material and devices from nanoscale inorganic components is well recognized. Conventional self-assembly is often limited in its ability to control material morphology and structure simultaneously. We report a general method of assembling nanoparticles in a linear “pillar” morphology with regulated internal configurations. Our approach is inspired by supramolecular systems, where intermolecular stacking guides the assembly process to form diverse linear morphologies. Programmable stacking interactions were realized through incorporation of DNA coded recognition between the designed planar nanoparticle clusters. This resulted in the formation of multilayered pillar architectures with a well-defined internal nanoparticle organization. Furthermore, by controlling the number, position, size, and composition of the nanoparticles in each layer, a broad range of nanoparticle pillars were assembled and characterized in detail. In addition, we demonstrated the utility of this stacking assembly strategy for investigating plasmonic and electrical transport properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Healing X-ray scattering images

X-ray scattering images contain numerous gaps and defects arising from detector limitations and experimental configuration. Here, we present a method to heal X-ray scattering images, filling gaps in the data and removing defects in a physically meaningful manner. Unlike generic inpainting methods, this method is closely tuned to the expected structure of reciprocal-space data. In particular, we exploit statistical tests and symmetry analysis to identify the structure of an image; we then copy, average and interpolate measured data into gaps in a way that respects the identified structure and symmetry. Importantly, the underlying analysis methods provide useful characterization of structures present in the image, including the identification of diffuse versus sharp features, anisotropy and symmetry. The presented method leverages known characteristics of reciprocal space, enabling physically reasonable reconstruction even with large image gaps. The method will correspondingly fail for images that violate these underlying assumptions. The method assumes point symmetry and is thus applicable to small-angle X-ray scattering (SAXS) data, but only to a subset of wide-angle data. Our method succeeds in filling gaps and healing defects in experimental images, including extending data beyond the original detector borders.

77 NANOSCIENCE AND NANOTECHNOLOGY↗