Engineering topics

Strachan, Denis M

Publications and source records attributed to Strachan, Denis M.

6 records

DOE OSTI2012

Metal-Organic Frameworks for Removal of Xe and Kr from Nuclear Fuel Reprocessing Plants

Removal of Xenon (Xe) and Krypton (Kr) from in parts per million (ppm) levels were demonstrated for the first time using two well known metal-organic frameworks (MOFs), HKUST-1 and Ni/DOBDC. Results of an activated carbon were also included for comparison. Ni/DOBDC has higher Xe/Kr selectivities than those of the activated carbon. Moreover, results show that the Ni/DOBDC and HKUST-1 can selectively adsorb Xe and Kr from air even at 1000 ppm concentration. This shows a promising future for MOFs in a radioactive nuclides separation from spent fuel.

activated carbon↗

DOE OSTI2012

Switching Kr/Xe Selectivity with Temperature in a Metal-Organic Framework

Krypton (Kr) and xenon (Xe) adsorption on two partially fluorinated metal-organic frameworks (FMOFCu and FMOFZn) with different cavity size and topologies were reported. FMOFCu shows an inversion in sorption selectivity toward Kr at temperatures below 0 C while FMOFZn does not. The 1D microtubes packed along the (101) direction connected through small bottleneck windows in FMOFCu appear to be the reason for this peculiar behavior. The FMOFCu shows an estimated Kr/Xe selectivity of 36 at 0.1 bar.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Chalcogen-based aerogels as a multifunctional platform for remediation of radioactive iodine

Aerogels employing chalcogen-based (i.e., S, Se, and/or Te) structural units and interlinking metals are termed chalcogels and have many emerging applications. Here, chalcogels are discussed in the context of nuclear fuel reprocessing and radioactive waste remediation. Motivated by previous work on removal of heavy metals in aqueous solution, we explored the application of germanium sulfide chalcogels as a sorbent for gas-phase I2 based on Pearson's Hard/Soft Acid-Base (HSAB) principle. This work was driven by a significant need for high-efficiency sorbents for I-129, a long-lived isotope evolved during irradiated UO2 nuclear fuel reprocessing. These chalcogel compositions are shown to possess an affinity for iodine gas, I2(g), at various concentrations in air and the affinity is attributed to a strong chemical attraction between the chalcogen and I2(g), according to the HSAB principle. The high sorption efficiency is facilitated by the high porosity as well as the exceptionally large surface area of the chalcogels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2011

GLAMOR – OR HOW WE ACHIEVED A COMMON UNDERSTANDING ON THE DECREASE OF GLASS DISSOLUTION KINETICS THROUGH INTERNATIONAL COOPERATION

The objective of the EC funded GLAMOR project was to achieve a common understanding of the processes that control the decrease of the dissolution rate of high-level waste glass in water when silica becomes saturated. Is affinity control or a protective layer dominating? The following steps were taken: (1) review of the literature, (2) selection ofselect an experimental dataset, and selection of the models r(t) and GM2003, and (3) application apply by the GLAMOR partners of the models to the datasets. The main focus has beenwas on dissolution tests in pure water at different values of surface-to-volume and pH. Some of the main conclusions were: (1) both affinity and protective layer concepts must be considered in the interpretation of the rate decreasing stage, (2) the residual dissolution rate observed beyond the silica saturation stage is far more important in view of the long-term performance of the glass, and deserves more attention in future R&D. In the GLAMOR final report, we also discussed in detail the modeling parameters, such as the silica saturation concentration, the silica diffusion coefficient, the silica retention factor in the reaction layer, and the water diffusion coefficient.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2011

Summary Report on the Volatile Radionuclide and Immobilization Research for FY2011 at PNNL

The materials development summarized here is in support of the Waste Forms campaign, Volatile Radionuclide task. Specifically, materials are being developed for the removal and immobilization of iodine and krypton, specifically 129I and 85Kr. During FY 2011, aerogel materials were investigated for removal and immobilization of 129I. Two aerogel formulations were investigated, one based on silica aerogels and the second on chalcogen-based aerogels (i.e., chalcogels). A silica aerogel was tested at ORNL for total I2 sorption capacity. It was determined to have 48 mass% capacity while having little physisorbed I2 (I2 not taken up in the aerogel pores). For 85Kr, metal organic framework (MOF) structures were investigated and a new MOF with about 8 mass% capacity for Xe and Kr. The selectivity can be changed from Xe > Kr to Xe < Kr simply by lowering the temperature below 0 C. A patent disclosure has been filed. Lastly, silicon carbide (SiC) was loaded with Kr. The diffusion of Kr in SiC was found to be less than detectable at 500 C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2011

Engineering Glass Passivation Layers -Model Results

The immobilization of radioactive waste into glass waste forms is a baseline process of nuclear waste management not only in the United States, but worldwide. The rate of radionuclide release from these glasses is a critical measure of the quality of the waste form. Over long-term tests and using extrapolations of ancient analogues, it has been shown that well designed glasses exhibit a dissolution rate that quickly decreases to a slow residual rate for the lifetime of the glass. The mechanistic cause of this decreased corrosion rate is a subject of debate, with one of the major theories suggesting that the decrease is caused by the formation of corrosion products in such a manner as to present a diffusion barrier on the surface of the glass. Although there is much evidence of this type of mechanism, there has been no attempt to engineer the effect to maximize the passivating qualities of the corrosion products. This study represents the first attempt to engineer the creation of passivating phases on the surface of glasses. Our approach utilizes interactions between the dissolving glass and elements from the disposal environment to create impermeable capping layers. By drawing from other corrosion studies in areas where passivation layers have been successfully engineered to protect the bulk material, we present here a report on mineral phases that are likely have a morphological tendency to encrust the surface of the glass. Our modeling has focused on using the AFCI glass system in a carbonate, sulfate, and phosphate rich environment. We evaluate the minerals predicted to form to determine the likelihood of the formation of a protective layer on the surface of the glass. We have also modeled individual ions in solutions vs. pH and the addition of aluminum and silicon. These results allow us to understand the pH and ion concentration dependence of mineral formation. We have determined that iron minerals are likely to form a complete incrustation layer and we plan to look more closely at Vivianite [Fe3(PO4)2-8(H2O)] and Siderite [FeCO3] in the next stage of the project.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗