HIGH TEMPERATURE STEAM OXIDATION OF TITANIUM-COATED ZIRCALOY-2 AND TITANIUM-ZIRCONIUM ALLOYS BY JORDAN RYSZARD BACZYNSKI THESIS Submitted in partial fulfillment of the requirements for the degree of Master of Science in Nuclear, Plasma, and Radiological Engineering in the Graduate College of the University of Illinois at Urbana-Champaign, 2014 Urbana, Illinois Master’s Committee: Professor James F. Stubbins, Chair Professor Brent J. Heuser ABSTRACT In March 2011, the Fukushima Daiichi Nuclear Disaster changed the course of nuclear power production worldwide. Though most people have focused on the negatives of the events, there have been major advantageous outcomes. An industry, which general consensus would say is extremely safe, has become even safer based on the events that took place. Plenty of new research ideas have sprouted out of the findings and events that took place during those critical few months. One such area that is currently being studied is the reduction of hydrogen gas production due to the exothermic reaction of high temperature steam and the Zircaloy fuel cladding within the reactor during a Loss-of -Coolant Accident (LOCA). The hydrogen, which collected in the reactor vessel and containment buildings, caused devastating hydrogen gas explosions which lead to the release of radioactive isotopes into the atmosphere. Cladding material for nuclear fuel pellets must contain three major characteristics: 1) high thermal conductivity as to not reduce overall efficiency 2) relatively long period of time from the initiation of LOCA scenario and the manifestation of uncontrolled oxidation of zirconium and 3) strong resilience against nuclear bombardment (alpha, beta, gamma, fission products, etc.). The research project was centered on selecting a potential additive not previously looked into for solving the problem of high temperature oxidation of zirconium. After analyzing a variety of potential elements, Titanium was selected and tested in a variety of different ways to see the metal’s resilience under high temperature steam conditions. Along with Zirconium-Titanium (Zr-Ti) Alloy, several Zircaloy-2 ii specimens were coated with titanium layers of various thickness in the hopes of determining a positive correlation between thickness size and reduction of hydrogen production. After obtaining a 95%Zi-5%Ti Alloy and depositing titanium layers of different thicknesses onto Zircaloy-2 using magnetron sputtering, the specimens were oxidized using a STA 449 F1 Jupiter. These tests specimens were subjected to 700°C steam for a 10 hour timeframe. In a surprising twist, the Zr-Ti Foil performed surprisingly poor compared to both the coated and un-coated Zircaloy-2 samples. It is hypothesized that the reason for this was due to an uncontrollable expansion from a phase change during oxidation. For the Ti-coated Zircaloy-2 sample, the titanium began to have an effect on the overall oxidation with a thickness beginning at 64 nanometers. The results of these experiments validate the initial hypothesis that titanium, along with additional research and isotopic refinement, has the potential to be a viable coating for both current and future reactor fuel cladding designs. iii For my Mother and Father; Amare et sapere vix deo conceditur. iv ACKNOWLEDGMENTS I would like to express profound gratitude to my advisor Dr. James Stubbins for all his guidance, support, and the freedom to create a Master’s Thesis centered on my interests. As Department Head for Nuclear, Plasma, and Radiological Engineering at The University of Illinois at Urbana-Champaign, Dr. Stubbins is not only responsible for running a department that has well over 200 students (Undergraduates and Graduates), he is traveling to conferences and seminars around the country and the world. His dedication to the profession and his intense commitment to his work have had a profound effect on my work. I know I could not have completed this work without him. On that note, I also want to thank Dr. Brent Heuser who served as a second reader and an important advisor along the way. Subsequently I have been a student at The University of Illinois at Urbana- Champaign since 2008, I feel there are many people within the Nuclear, Plasma, and Radiological (NPRE) Department that have be instrument during my Undergraduate and Graduate Studies. First and foremost, I want to thank the administrative staff, namely Becky Meline, Gail Krueger, and Idell Dollison. From advising on which classes students should to take to scheduling meeting with professors, they are the unsung heroes within our department. They were always available to talk and would go out of their way in order to help out me and my fellow students. During my time as a Graduate Students, I was fortunate enough to serve as a Teaching Assistant for several classes within the NPRE Department. Dr. Madgi Ragheb and v I have been responsible for teaching eight course these past two years. This experience has been extremely crucial for my public speaking, time management, and critical thinking development. There were also several graduate students within the Nuclear, Plasma, and Radiological Engineering Department that assisted me along the way. First and foremost, the bulk of the experimental data would not have been obtained without the help of Peter Mouche. His help and advice during the experimentation process ultimately allowed me to finish on time and, for that, I will be eternally grateful. I also could not have done it without my fellow Teaching Assistants (Nick O’Shea, Travis Mu, and George Mckenzie) who helped me grade stacks upon stacks of assignments, held office hours, and answered hundreds of student emails. Last, but certainly not least, above all I want to thank my two families. The first one is my biological family living in the southwest suburbs of Chicago. My Mom and Dad are, to this very day, the single greatest influences that I have in my life. They taught me the value of hard work, to be grateful for what I have, and to live life to the fullest. Their support and love fuels my desire to be the best possible individual. My brothers and sisters are always there to deal with my crazy ideas and to offer me guidance. The second family that I referred to was the one that I found here on campus. My friends and colleagues that I have been truly honored to work and interact with on a daily basis. These very special men and women have given me the opportunity of a lifetime; which I will cherish for as long as I live. vi TABLE OF CONTENTS CHAPTER 1 – INTRODUCTION.........................................................................1 CHAPTER 2 – LITERATURE REVIEW..............................................................13 CHAPTER 3 – ADDITIVE SELECTION PROCESS..........................................36 CHAPTER 4 – EXPERIMENTAL PROCESS.....................................................53 CHAPTER 5 – PRESENTATION OF EXPERIMENTAL RESULTS ………….....62 CHAPTER 6 – INTERPRETATION OF EXPERIMENTAL RESULTS.............67 CHAPTER 7 – RECOMMENDED FUTURE STRATEGY.................................75 CHAPTER 8 – CONCLUSION..........................................................................78 REFERENCES.....................................................................................................79 vii CHAPTER 1 INTRODUCTION 1.1 Current Worldwide State of Nuclear Power In the September 13th ,1999 Edition of the Wall Street Journal, Mark Yost wrote an article discussing the future outlook of the nuclear power industry. After presenting many diagrams and descriptions of current energy price fluctuations, Mark ended the article ended with a simple yet powerful message: “Not long ago, nuclear energy looked headed for extinction. Those days are over. With production costs dropping and regulations for fossil-fuel-burning plants rising, there’s a renaissance taking place in nuclear power that would have been unthinkable five years ago.” (Yost 1999) From that point on, the term “nuclear renaissance” took a life of its own; changing the very nature and foundation of a once potentially dominate energy source that, for some time, was viewed as dormant or without a pulse. Nuclear reactor applications started to be formally finalized and new sites broke ground throughout the world at a pace not seen in well over thirty years. Driven by rising fossil fuel prices and new concerns about meeting greenhouse gas emissions, the future prospects for nuclear power looked very promising. 1 Moving from speculations and hypotheticals to reality and actuality, the major historical consensus would clearly show that the nuclear renaissance never came to fruition. Granted, there was a short-lived period of increased applications and proposals, but there has actually been a decrease in worldwide production of nuclear energy. A report published by the International Atomic Energy Agency showed that the total electricity produced by nuclear power reactors in 2009 was about 2346 terawatt-hours – a seven percent decrease year-over-year from 2008 (IAEA 2009). The effects of the Fukushima Daiichi Accidents has had a huge impact not only slowing down the number of companies interested in building nuclear plants, but at the same time has created a lot of negative publicity for the industry as a whole. There are many countries (for example: Germany, Switzerland, Belgium, France, Malaysia, and Taiwan) that have plans to either reduce its dependence or completely abandon nuclear power production. The Fukushima Daiichi Accident is not the only mechanism