University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 5-2020 Development and Applications of the Rapid Analysis of Post- Irradiation Debris (RAPID) Method to Nuclear Materials Emilie Fenske University of Tennessee, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Recommended Citation Fenske, Emilie, "Development and Applications of the Rapid Analysis of Post-Irradiation Debris (RAPID) Method to Nuclear Materials. " PhD diss., University of Tennessee, 2020. https://trace.tennessee.edu/utk_graddiss/5883 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Emilie Fenske entitled "Development and Applications of the Rapid Analysis of Post-Irradiation Debris (RAPID) Method to Nuclear Materials." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Nuclear Engineering. Howard Hall, Major Professor We have read this dissertation and recommend its acceptance: Steven Skutnik, Alan Icenhour, Robert Counce, Benjamin Roach, Cole Hexel Accepted for the Council: Dixie L. Thompson Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Development and Applications of the Rapid Analysis of Post-Irradiation Debris (RAPID) Method to Nuclear Materials A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Emilie Fenske May 2020 Copyright © 2020 by Emilie Kiersten Fenske All rights reserved. ii ACKNOWLEDGEMENTS I would first like to thank my mentors at Oak Ridge National Laboratory, Dr. Ben Roach and Dr. Cole Hexel, who helped guide me through my research, as well as Joe Giaquinto for his willingness to support my PhD in his group and Dr. Vince Jodoin for his mentorship and advice. Their experience and guidance have been of great assistance, and I would not be where I am today without them. I would further like to thank my UTK advisor and committee members, Dr. Howard Hall, Dr. Steve Skutnik, Dr. Alan Icenhour, and Dr. Robert (Pete) Counce, for their enthusiasm in the classroom and time spent helping me to further develop and enhance this research. I would also like to thank the staff members of NACIL in 4501; without their areas of expertise, and willingness to teach a nuclear engineer analytical chemistry, this research would have taken much longer to complete. Additionally, I would like to thank Dan Archer and Michael Willis for their assistance as my local ORNL radiation detection experts who never tired of me asking questions and using their espresso machine. Lastly, my gratitude would not be complete without the acknowledgement of my friends and family who formed my support network throughout this period. I would particularly like to thank my mom and dad for their unending support and love. I would also like to thank Ian Stewart, Alex Braatz, Adam Stratz, Jon Gill, Matthew Duchene, Josh Chandler, Lloyd Ramey, and David Glasgow for their ever-present encouragement and motivation. iii PREFACE This dissertation is an original intellectual product of the author, Emilie K. Fenske, and was performed under contract No. DE AC05-00OR22725. This work was sponsored by the Defense Threat Reduction Agency (DTRA). This research was supported in part by an appointment to the Oak Ridge National Laboratory Post-Master’s Research Associate Program, sponsored by the U.S. Department of Energy and administered by the Oak Ridge Institute for Science and Education. The views and conclusions contained in this document are those of the author and should not be interpreted as representing the official policies, either expressed or implied, of the supporting entities. Portions of the text, as specified within the chapters, elaborate on scientific articles of which I am an author. All of the work presented henceforth was conducted at Oak Ridge National Laboratory. iv ABSTRACT Chemical analysis of nuclear materials is a well-developed area of research, through use of mass spectrometers and other destructive analysis techniques. These analyses are applicable to several nuclear fields, such as nuclear forensics, fuel characterization and modeling, and environmental monitoring. For nuclear forensics particularly, a rapid analytical chemistry technique can be useful, given the need for a quick turn-around of data in certain attribution cases for nuclear forensics. An analytical technique for low-level nuclear material analyses has been developed and applied to various samples at Oak Ridge National Laboratory (ORNL), named Rapid Analysis of Post- Irradiation Debris (RAPID). This technique combines a high-pressure ion chromatography unit and an inductively-coupled plasma mass spectrometer for a rapid, direct separation-detection method, with a turn-around of less than four hours per sample, including dissolution, analysis, and data processing. Analyzed samples include irradiated highly-enriched uranium, ORNL-developed, and UTK-developed surrogate nuclear “debris”. This dissertation will present the development of RAPID and its subsequent evolution and application to nuclear forensics, obtaining the sensitivity and accuracy for operational usage at ORNL. Additionally, a novel inline gamma detection technique was developed as an extension of RAPID and will be presented, demonstrating the feasibility of elementally-isolated gamma spectrometry and the benefit of having two complementary analytical techniques to fully characterize fission products in a short timeframe. v Table of Contents ACKNOWLEDGEMENTS ...................................................................................................................... iii PREFACE ................................................................................................................................................... iv ABSTRACT ................................................................................................................................................. v CHAPTER 1: INTRODUCTION .............................................................................................................. 1 1.1 Background: Post-detonation Nuclear Forensics .............................................................................. 1 1.2 Current Analytical Challenges ........................................................................................................... 2 1.3 The Rapid Analysis of Post-Irradiation Debris Protocol ................................................................... 4 1.4 Post-Detonation Debris Samples ........................................................................................................ 5 1.4.1 ORNL Debris Generation ............................................................................................................ 5 1.4.2 UTK Surrogate Debris Generation .............................................................................................. 6 1.5 Dissertation Objective ........................................................................................................................ 7 CHAPTER 2: LITERATURE SURVEY .................................................................................................. 8 2.1 Focus of this Review ........................................................................................................................... 8 2.1.1 Materials of Interest .................................................................................................................... 9 2.1.2 Overview of the Sample Analysis Process ................................................................................ 11 2.1.3 Rapid Analytical Techniques for Post-Detonation Nuclear Forensics ...................................... 13 2.2 Overview of Mass Spectrometry Techniques .................................................................................... 15 2.2.1 Inductively-Coupled Plasma Mass Spectrometry ..................................................................... 15 2.2.2 Secondary Ionization Mass Spectrometry (SIMS) .................................................................... 17 2.2.3 Thermal Ionization Mass Spectrometry (TIMS) ....................................................................... 18 vi 2.3 Chemical Separation Techniques ..................................................................................................... 18 2.3.1 Chemical Separations Overview ............................................................................................... 18 2.3.2 Ion Chromatography (IC) .......................................................................................................... 20 2.4 Inline Radiation Detectors ................................................................................................................ 23 CHAPTER 3: THEORY .......................................................................................................................... 25 3.1 Scope ................................................................................................................................................