Zero valent iron (ZVI) nanoparticles are versatile in their ability to remove a wide variety of water contaminants, and ZVI-based bimetallic nanoparticles show increased reactivity above that of ZVI alone. ZVI nanoparticles degrade contaminants through the reactive species (e.g., OH*, H(2(g)), H(2)O(2)) that are produced during iron oxidation. Measurement and modeling of aqueous ZVI nanoparticle oxidation kinetics are therefore necessary to optimize nanoparticle design. Stabilized ZVI and iron-nickel nanoparticles of approximately 150 nm in diameter were synthesized through solution chemistry, and nanoparticle oxidation kinetics were determined via measured mass change using a quartz crystal microbalance (QCM). Under flowing aerated water, ZVI nanoparticles had an initial exponential growth behavior indicating surface-dominated oxidation controlled by migration of species (H(2)O and O(2)) to the surface. A region of logarithmic growth followed the exponential growth which, based on the Mott-Cabrera model of thin oxide film growth, suggests a reaction dominated by movement of species (e.g., iron cations and oxygen anions) through the oxide layer. The presence of ethanol or a nickel shell on the ZVI nanoparticles delayed the onset of iron oxidation and reduced the extent of oxidation. In oxygenated water, ZVI nanoparticles oxidized primarily to the iron oxide-hydroxide lepidocrocite.

Polymer-derived ceramic composites are being investigated as environmental barrier coatings to protect stainless steel from oxidation and carburization. Coatings have been produced using poly(hydridomethylsiloxane) as a preceramic polymer and titanium disilicide as an expansion agent. Processing parameters have been optimized and a relationship has been derived to predict the final coating thickness based on slurry viscosity and dip coating withdrawal speed. Microstructural analysis reveals a composite coating of oxidized filler particles in a silica matrix. A diffusion layer is visible at the coating-steel interface, indicating good bonding. The optimized coatings are B18 lm thick, and have some residual porosity and a density of 2.56 g/cm 3 .

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Polymer-derived ceramics have shown promise as a novel way to process low-dimensional ceramics such as environmental barrier coatings. Composite coatings have been developed as oxidation and carburization barriers on steel using poly(hydridomethylsiloxane) matrix and titanium disilicide as reactive fillers. A systematic study of the phase transformations and microstructural changes in the coatings and their components during pyrolysis in air is presented here. The system evolves from an amorphous polymer filled with a binary metal at room temperature to an inorganic amorphous network of oxidized silicon and titanium at the target temperature of 800 °C. Crystallization of the composite occurs at higher temperatures to reach cristobalite and rutile by 1600 °C. The polymer-to-ceramic conversion occurs between 200 and 600 °C. The oxidation of the expansion agent and the densification of the composite take place between 300 and 800 °C.

Precise materials integration in nanostructures is fundamental for future electronic and photonic devices. We demonstrate Si, Ge, and SiGe nanostructure direct-write with deterministic size, geometry, and placement control. The biased probe of an atomic force microscope (AFM) reacts diphenylsilane or diphenylgermane to direct-write carbon-free Si, Ge, and SiGe nano and heterostructures. Parallel direct-write is available on large areas by substituting the AFM probe with conducting microstructured stamps. This facile strategy can be easily expanded to a broad variety of semiconductor materials through precursor selection.