Thermophysical property measurement and characterization of glass ceramic waste forms
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Engineering topics
Publications and source records attributed to Tang, Ming.
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Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).
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A radiation stability study was performed on glass ceramic and crystalline ceramic waste forms. These materials are candidate host materials for immobilizing alkali/alkaline earth (Cs/Sr-CS) + lanthanide (LN) + transition metal (TM) fission product waste streams from nuclear fuel reprocessing. In this study, glass ceramics were fabricated using a borosilicate glass as a matrix in which to incorporate CS/LN/TM combined waste streams. The major phases in these multiphase materials are powellite, oxyaptite, pollucite, celsian, and durable residual glass phases. Al2O3 and TiO2 were combined with these waste components to produce multiphase crystalline ceramics containing hollandite-type phases, perovskites, pyrochlores and other minor metal titanate phases. For the radiation stability test, selected glass ceramic and crystalline ceramic samples were exposed to different irradiation environments including low fluxes of high-energy (~1–5 MeV) protons and alpha particles generated by an ion accelerator, high fluxes of low-energy (hundreds of keV) krypton particles generated by an ion implanter, and in-situ electron irradiations in a transmission electron microscope. These irradiation experiments were performed to simulate self-radiation effects in a waste form. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction and transmission electron microscopy. Our preliminary results reveal different radiation tolerance in different crystalline phases under various radiation damage environments. However, their stability may be rate dependent which may limit the waste loading that can be achieved.
Multiphase borosilicate glass-ceramics represent one candidate to contain radioactive nuclear waste separated from used nuclear fuel. In this work, the thermophysical properties from room temperature to 1273 K were investigated for four different borosilicate glass-ceramic compositions containing waste loadings from 42 to 60 wt% to determine the sensitivity of these properties to waste loading, as-fabricated microstructure, and potential evolutions in microstructure brought about by temperature transients. The thermal expansion, specific heat capacity, thermal diffusivity, and thermal conductivity are presented. The impact of increasing waste loading is shown to have a small but measurable effect on the thermophysical properties between the four compositions, contrasted to a much greater impact observed when transitioning from predominantly crystalline to amorphous systems. Thermal cycling below 1273 K was not found to measurably impact the thermophysical properties of the compositions investigated here.
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Cs is one of the more problematic fission product radionuclides to immobilize due to its high volatility at elevated temperatures, ability to form water soluble compounds, and its mobility in many host materials. The hollandite structure is a promising crystalline host for Cs immobilization and has been traditionally fabricated by solid state sintering methods. This study presents the structure and performance of Ba{sub 1.0}Cs{sub 0.3}A{sub 2.3}Ti{sub 5.7}O{sub 16}; A = Cr, Fe, Al hollandite fabricated by melt processing. Melt processing is considered advantageous given that melters are currently in use for High Level Waste (HLW) vitrification in several countries. This work details the impact of Cr additions that were demonstrated to i) promote the formation of a Cs containing hollandite phase and ii) maintain the stability of the hollandite phase in reducing conditions anticipated for multiphase waste form processing.
Detailed ion-probe data are reported on Murchison and Murray C2 chondrites, along with noble-gas data on Murchison, with the purpose of characterizing the number and isotopic composition of independent SiC components and to link them to their stellar sources. Results show that coarse-grained and fine-grained SiC (totaling about 6-9 ppm of the two meteorites) contains record concentrations of two exotic components: Ne-E(H) (nearly monoisotopic Ne-22) and Se-S (enriched in isotopes 128, 130, and 132), respectively. The Ne-21 content was found to exceed up to 40-fold the content expected from the recent cosmic-ray irradiation, implying a presolar cosmic-ray exposure age of about 39 Ma. This age is much shorter that the predicted 500 Ma lifetime of refractory interstellar grains and implies either a selective interstellar destruction process for SiC, enhanced supernova activity in the protosolar neighborhood, or late outgassing of greater than 90 percent of the SiC.