Crystallite Size Dependency of the Pressure and Temperature Response in Nanoparticles of Ceria and Other Oxides

Philip Porter Rodenbough
2017
The short title of this dissertation is Size Matters. And it really does. Before diving into the original findings of this dissertation, this abstract starts by contextualizing their significance. To that end, recall that some of the earliest concepts learned by sophomore organic chemistry students include explaining physical properties based on carbon chain length, for example, and polymer length has enormous influence on macroscopic material properties. In the 1980s it was found that the
more » ... found that the electronic properties of small inorganic semiconductor crystallites can be rigorously tied to the physical size of the crystallites, and this understanding has led directly to the successful integration of so-called quantum dots into readily available technologies today, including flat screen televisions, as well as emerging technologies, such as quantum dot solar cells. Oxides, for their part, are important components of many technologies, from paints and cosmetics to microelectronics and catalytic converters. The crystallite size dependency of fundamental mechanical properties of oxides is the topic of this dissertation. First, this dissertation reports that consistent preparation methods were used to produce batches of specific crystallite sizes for a diverse family of five cubic oxides: CeO2 (ceria), MgO (magnesia), Cu2O (cuprite), Fe3O4 (magnetite), and Co3O4. The size-based lattice changes for small crystallites was carefully measured with X-ray diffraction. Expanded lattice parameters were found in small crystallites of all five oxides (notably for the first time in Fe3O4). This behavior is rationalized with an atomic model reliant on differing coordination levels of atoms at the surface, and fundamental calculations of physical properties including surface stress and expansion energy are derived from the measured lattice expansion for these oxides. Then, the size dependency of the pressure response in ceria nanoparticles was measured using diamond anvil cells and synchrotron radiation. In a study unmatched i [...]
doi:10.7916/d8qn66wh fatcat:csywmp4bjjcmpk44uoevda4h34