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Coile, Matthew

Publications and source records attributed to Coile, Matthew.

Identification of Known and Novel Monomers for Poly(hydroxyurethanes) from Biobased Materials

Sourcing polymers from biobased materials is desirable for a transition to a more sustainable world. However, finding new monomers sourced from biobased molecules requires extensive experimental effort, due to the fact that most biomolecules lack the functional groups or properties needed to serve as a monomer in a particular polymeric system without chemical modification. In this work, we demonstrate a computational screening method to obtain monomers of a non-isocyanate polyurethane (NIPU), polyhydroxyurethane (PHU), from biomolecules. Our method generates candidate monomers from a list of 15 selected biobased starting molecules by performing chemical transformations that are standard to chemical catalysis and organic synthesis on these starting molecules and then screening the results for molecules with moieties that can be used as monomers for a PHU. Product molecules from two generations of reaction, a total number of 20,057, were analyzed automatically to identify molecules that have two or more epoxy or cyclic carbonate functional groups as candidates for further derivatization. These 21 candidate molecules were then subjected to another two generations of reaction, producing a set of 17,913 additional molecules. Further scrutiny of this set for desired functional groups characterizing PHUs and querying against the PubChem database was carried out, and 15 known molecules that are commercially available were identified, with the desirable features that they are predicted to be derived from biobased starting molecules in four or fewer steps. Moreover, molecule space generated from this process was primarily comprised of molecules that were not known to PubChem, indicating the framework also has the ability to generate novel candidate monomers that originate from biobased starting points.

36 MATERIALS SCIENCE↗

Nanometer-Thick Sr 2 IrO 4 Freestanding Films for Flexible Electronics

In this article, we report the structural and optical properties of nanoscale Sr 2 IrO 4 freestanding thin-films fabricated using a water-soluble Sr 3 Al 2 O 6 layer. The coherent lattice structure, phonon modes, two-magnon Raman scattering, and optical absorption spectra of the Sr 2 IrO 4 nanomembrane are analogous to those of the layered iridate epitaxial thin-films and single crystals. Remarkably, the formation of 3-unit-cell-thick SrIrO 3 and interfacial composite layers alleviates the antiphase boundaries at the Sr 2 IrO 4 /Sr 3 Al 2 O 6 interface, resulting in structurally-robust nanomembranes. Our experimental results show that this freestanding thin-film approach of layered oxides can provide techniques for tuning or realizing unprecedented states beyond conventional thin-film methods, suggesting a pathway in achieving flexible layered-oxide electronics.

36 MATERIALS SCIENCE↗

Probing the Atomic-Scale Structure of Amorphous Aluminum Oxide Grown by Atomic Layer Deposition

Atomic layer deposition (ALD) is a well-established technique for depositing nanoscale coatings with pristine control of film thickness and composition. The trimethylaluminum (TMA) and water (H 2 O) ALD chemistry is inarguably the most widely used and yet to date, we have little information about the atomic-scale structure of the amorphous aluminum oxide (AlO x ) formed by this chemistry. This lack of understanding hinders our ability to establish process-structure-property relationships and ultimately limits technological advancements employing AlOx made via ALD. In this work, we employ synchrotron high-energy X-ray diffraction (HE-XRD) coupled with pair distribution function (PDF) analysis to characterize the atomic structure of amorphous AlO x ALD coatings. We combine ex situ and in operando HE-XRD measurements on ALD AlO x and fit these experimental data using stochastic structural modeling to reveal variations in the Al-O bond length, Al and O coordination environment, and extent of Al vacancies as a function of growth conditions. In particular, the local atomic structure of ALD AlO x is found to change with the substrate and number of ALD cycles. The observed trends are consistent with the formation of bulk Al 2 O 3 surrounded by an O-rich surface layer. We deconvolute these data to reveal atomic-scale structural information for both the bulk and surface phases. Overall, this work demonstrates the usefulness of HE-XRD and PDF analysis in improving our understanding of the structure of amorphous ALD thin films and provides a pathway to evaluate how process changes impact the structure and properties of ALD films.

36 MATERIALS SCIENCE↗