Defense Date

2019

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Mechanical and Nuclear Engineering

First Advisor

Supathorn Phongikaroon

Abstract

A feasibility of rapid setting cement (RSC) as an agent of immobilization for certain elements such as fission products or radioactive materials was explored. Cerium (Ce) and cesium (Cs) have been selected as a surrogate for U and/or Pu and fission products, respectively, in this study in three phases. In Phase I, RSC was evaluated for physical properties (e.g., porosity, density, pH values, etc.) using two groups methods—the cement powder at different concentrations of Ce (2 – 10 wt%) with deionized water (DIW) and artificial seawater (ASW). The results showed that the final setting time and compressive strength of RSC in DIW and ASW solutions decreased as Ce content increased. The X-ray diffraction patterns revealed two newly identified phases, namely CeAl11O18 and Ce4.667 (SiO4)3O. The morphology of matrix samples showed that the existence of Ce distributed on the pore wall or clustered with Si, Al, Mg, K, P, Fe, and O. In Phase II, laser-induced breakdown spectroscopy (LIBS) technique together with univariate and multivariate analyses of the principal component analysis (PCA) and partial least squares (PLS) were applied to detect the surrogate elements (Ce (0.5 – 8 wt%) and Cs (0.5 – 4 wt%)) for nuclear materials captured in ceramic materials. The best calibration curves for Ce and Cs in samples were created using the peak areas of the Ce 571.8 nm line and Cs 697.1 nm line, respectively. PCA method was applied to explain 85.5 % for Ce-cement samples in DIW and 91.4 % for those in ASW. Samples with Cs indicated similar PCA trends. The PLS calibration curves for Ce and Cs samples in DIW and those in ASW were made using seven and eight latent variables (LV). In Phase III, the leaching behaviors of Ce and Cs mixture with DIW and ASW under both dynamic and static leach conditions were investigated according to the ANSI/ANS 16.1-2003 standard method. Elemental compositions were analyzed using an inductively coupled plasma-mass spectrometry (ICP-MS) for the leaching periods of 2, 7, and 24 hours and 2, 3, 4, 5, 14, 28, 43, and 90 days. Three mathematical models—first-order reaction model (FRM), diffusion model (DM), and first-order reaction/diffusion model (FRDM)—were fitted to assess the leaching parameters of immobilized radionuclides in the RSC matrix. Results showed that leaching of 140Ce and 133Cs from RSC matrices with (DIW and ASW) under both dynamic and static leach conditions was less than 20%. It was found that the leaching phenomena of 140Ce and 133Cs was dominantly controlled by FRM with a weak effect of DM, which was best fitted by FRDM. Here, the average leachability index (L) for 140Ce and 133Cs, are greater than the recommended minimum of 6 that allowed their acceptance for disposal. These studies indicated a good feasibility of using RSC with DIW and ASW for immobilizing non-radioactive Ce and Cs and RSC had a potential for applying to actual radioactive materials.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

4-26-2019

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