Darryl P. Butt

Effects of proton irradiation on structural and electrochemical charge storage properties of TiO2 nanotube electrodes for lithium-ion batteries

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the materials electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformation to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ∼240 mA h g−1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.

Detecting the Oxidation of Zircaloy Claddings by Infrared Interference

As the expected life of dry cask storage installations increases, it becomes increasingly desirable to monitor the state and performance of the cask internals to ensure that they continue to safely contain the radioactive materials in the fuel. One aspect of this task is the monitoring of oxidation of the cladding. With this consideration in mind, Zircaloy-4 (Zr-4) cladding samples were exposed to air at 500∘C for various duration times to create thin corrosion oxide layers on the surface. The surfaces of the oxidized samples were then systematically scanned by Fourier Transform Infrared (FT-IR) spectroscopy to achieve the infrared (IR) interference spectra and study the relationship between the optical interference and the various thicknesses of the oxide layers. The profiles of the oxide layers were verified througth cross-sectional examination by Scanning Electron Microscopy. The IR interference patterns varied with oxide layer thickness, enabling the determination of oxide layer thickness of values, i...

Proton irradiation effect on thermoelectric properties of nanostructured n-type half-Heusler Hf0.25Zr0.75NiSn0.99Sb0.01

Thermoelectric properties of nanostructured half-Heusler Hf0.25Zr0.75NiSn0.99Sb0.01 were characterized before and after 2.5 MeV proton irradiation. A unique high-sensitivity scanning thermal microprobe was used to simultaneously map the irradiation effect on thermal conductivity and Seebeck coefficient with spatial resolution less than 2 μm. The thermal conductivity profile along the depth from the irradiated surface shows excellent agreement with the irradiation-induced damage profile from simulation. The Seebeck coefficient was unaffected while both electrical and thermal conductivities decreased by 24%, resulting in no change in thermoelectric figure of merit ZT. Reductions in thermal and electrical conductivities are attributed to irradiation-induced defects that act as scattering sources for phonons and charge carriers.Thermoelectric properties of nanostructured half-Heusler Hf0.25Zr0.75NiSn0.99Sb0.01 were characterized before and after 2.5 MeV proton irradiation. A unique high-sensitivity scanning thermal microprobe was used to simultaneously map the irradiation effect on thermal conductivity and Seebeck coefficient with spatial resolution less than 2 μm. The thermal conductivity profile along the depth from the irradiated surface shows excellent agreement with the irradiation-induced damage profile from simulation. The Seebeck coefficient was unaffected while both electrical and thermal conductivities decreased by 24%, resulting in no change in thermoelectric figure of merit ZT. Reductions in thermal and electrical conductivities are attributed to irradiation-induced defects that act as scattering sources for phonons and charge carriers.