Nanoscale structural characterization is critical to understanding the physical underpinnings of properties and behavior in materials with technological applications. The work herein shows how the pair distribution function technique can be applied to x-ray total scattering data for material systems which weakly scatter x-rays, a typically difficult task due to the poor signal-to-noise obtained from the structures of interest. Characterization and structural modeling are demonstrated for a variety of molecular and porous systems, along with the detection and characterization of disordered, minority phases and components. In particular, reliable detection and quantitative analysis are demonstrated for nanocrystals of an active pharmaceutical ingredient suspended in dilute solution down to a concentration of 0.25 wt. %, giving a practical limit of detection for ordered nanoscale phases within a disordered matrix. Further work shows that minority nanocrystalline phases can be detected, fingerprinted, and modeled for mixed crystalline and amorphous systems of small molecules and polymers. The crystallization of amorphous lactose is followed under accelerated aging conditions. Melt quenching is shown to produce a different local structure than spray drying or freeze drying, along with increased resistance to crystallization. The initial phases which form in the spray dried formulation are identified as a mixture of polymorphs different from the final α-lactose monohydrate form. Hard domain formation in thermoplastic polyurethanes is also characterized as a function of methylene diphenyl diisocyanate and butanediol component ratio, showing that distinct and different hard phase structures can form and are solved by indexing with structures derived from molecular dynamics relaxation. In both cases, phase fractions can be quantified in the mixed crystalline and amorphous systems by fitting with both standards or structure models.
Later chapters, demonstrate pair distribution characterization of particle incorporation, structure, and synthesis of nanoporous materials. Nanoparticle size distributions are extracted from platinum nanoparticles nucleating within a zeolite matrix through structural modeling, and validated by transmission electron microscope studies. The structure of zirconium phosphonate-phosphate unconventional metal organic framework is determined to consist of turbostratically disordered nanocrystalline layers of Zr-phenylphosphonate, and the local environment of terbium intercalated between the layers is found to resemble the local environment in scheelite-type terbium phosphate. Finally, the early stages of reaction between aqueous zinc dinitrate hexahydrate and methanolic 2-methylimidazole are characterized using in situ total scattering measurements, showing that secondary building units of tetrahedrally coordinated by 2-methylimidazole initially form upon reaction. Overall, the methodologies are developed and applied toward phase detection, identification, solution, and behavior in pharmaceuticals, polymers, and nanoporous materials along with advice for carrying out experiments and analysis on such materials such that they can be extended to other similar systems.
| Identifer | oai:union.ndltd.org:columbia.edu/oai:academiccommons.columbia.edu:10.7916/D8GB2GNW |
| Date | January 2018 |
| Creators | Terban, Maxwell |
| Source Sets | Columbia University |
| Language | English |
| Detected Language | English |
| Type | Theses |
Page generated in 0.0023 seconds