Doctor of Philosophy
Mechanical and Nuclear Engineering
Sama Bilbao y Leon
The primary objective of this research is to develop an applied technology and provide an assessment for remotely measuring and analyzing the real time or near real time concentrations of used nuclear fuel (UNF) elements in electrorefiners (ER). Here, Laser-Induced Breakdown Spectroscopy (LIBS) in UNF pyroprocessing facilities was investigated. LIBS is an elemental analysis method, which is based on the emission from plasma generated by focusing a laser beam into the medium. This technology has been reported to be applicable in solids, liquids (includes molten metals), and gases for detecting elements of special nuclear materials. The advantages of applying the technology for pyroprocessing facilities are: (i) Rapid real-time elemental analysis; (ii) Direct detection of elements and impurities in the system with low limits of detection (LOD); and (iii) Little to no sample preparation is required. One important challenge to overcome is achieving reproducible spectral data over time while being able to accurately quantify fission products, rare earth elements, and actinides in the molten salt. Another important challenge is related to the accessibility of molten salt, which is heated in a heavily insulated, remotely operated furnace in a high radiation environment within an argon gas atmosphere. This dissertation aims to address these challenges and approaches in the following phases with their highlighted outcomes:
1. Aerosol-LIBS system design and aqueous testing: An aerosol-LIBS system was designed around a Collison nebulizer and tested using deionized water with Ce, Gd, and Nd concentrations from 100 ppm to 10,000 ppm. The average %RSD values between the sample repetitions were 4.4% and 3.8% for the Ce and Gd lines, respectively. The univariate calibration curve for Ce using the peak intensities of the Ce 418.660 nm line was recommended and had an R2 value, LOD, and RMSECV of 0.994, 189 ppm, and 390 ppm, respectively. The recommended Gd calibration curve was generated using the peak areas of the Gd 409.861 nm line and had an R2, LOD, and RMSECV of 0.992, 316 ppm, and 421 ppm, respectively. The partial least squares (PLS) calibration curves yielded similar results with RMSECV of 406 ppm and 417 ppm for the Ce and Gd curves, respectively.
2. High temperature aerosol-LIBS system design and CeCl3 testing: The aerosol-LIBS system was transitioned to a high temperature and used to measure Ce in molten LiCl-KCl salt within a glovebox environment. The concentration range studied was from 0.1 wt% to 5 wt% Ce. Normalization was necessary due to signal degradation over time; however, with the normalization the %RSD values averaged 5% for the mid and upper concentrations studied. The best univariate calibration curve was generated using the peak areas of the Ce 418.660 nm line. The LOD for this line was 148 ppm with the RMSECV of 647 ppm. The PLS calibration curve was made using 7 latent variables (LV) and resulting in the RMSECV of 622 ppm. The LOD value was below the expected rare earth concentration within the ER.
3. Aerosol-LIBS testing using UCl3: Samples containing UCl3 with concentrations ranging from 0.3 wt% to 5 wt% were measured. The spectral response in this range was linear. The best univariate calibration curves were generated using the peak areas of the U 367.01 nm line and had an R2 value of 0.9917. Here, the LOD was 647 ppm and the RMSECV was 2,290 ppm. The PLS model was substantially better with a RMSECV of 1,110 ppm. The LOD found here is below the expected U concentrations in the ER. The successful completion of this study has demonstrated the feasibility of using an aerosol-LIBS analytical technique to measure rare earth elements and actinides in the pyroprocessing salt.
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