INTERDIFFUSION BEHAVIOR OF U-Mo ALLOYS IN CONTACT WITH Al AND Al-Si ALLOYS by EMMANUEL PEREZ B.E. Columbia University, 1995 M.S. University of Central Florida, 2005 A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Mechanical, Materials and Aerospace Engineering in the College of Engineering and Computer Science at the University of Central Florida, Orlando, Florida Spring Term 2011 Major Professor: Dr. Y.H. Sohn © 2011 Emmanuel Perez ii ABSTRACT U-Mo dispersion and monolithic fuels embedded in Al-alloy matrix are under development to fulfill the requirements of research reactors to use low-enriched molybdenum stabilized uranium alloys as fuels. The system under consideration in this study consisted of body centered cubic () U-Mo alloys embedded in an Al structural matrix. Significant interaction has been observed to take place between the U-Mo fuel and the Al matrix during manufacturing of the fuel-plate system assembly and during irradiation in reactors. These interactions produce Al-rich phases with physical and thermal properties that adversely affect the performance of the fuel system and can lead to premature failure. In this study, interdiffusion and microstructural development in the U-Mo vs. Al system was examined using solid-to-solid diffusion couples consisting of U-7wt.%Mo, U-10wt.%Mo and U- 12wt.%Mo vs. pure Al, annealed at 600°C for 24 hours. The influence of Si alloying addition (up to 5 wt.%) in Al on the interdiffusion microstructural development was also examined using solid-to-solid diffusion couples consisting of U-7wt.%Mo, U-10wt.%Mo and U-12wt.%Mo vs. pure Al, Al-2wt.%Si, and Al-5wt.%Si annealed at 550°C for 1, 5 and 20 hours. To further clarify the diffusional behavior in the U-Mo-Al and U-Mo-Al-Si systems, Al-rich 85.7Al-11.44U- 2.86Mo, 87.5Al-10U-2.5Mo, 56.1Al-18.9Si-21.9U-3.1Mo and 69.3Al-11.9Si-18.8U (at.%) alloys were cast and homogenized at 500°C to determine the equilibrium phases of the system. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron probe microanalysis (EPMA) and X-ray diffraction (XRD) were employed to examine the phase development in the diffusion couples and the cast alloys. iii In ternary U-Mo-Al diffusion couples annealed at 600°C for 24 hours, the interdiffusion microstructure consisted of finely dispersed UAl , UAl , U Mo Al , and UMo Al phases while 3 4 6 4 43 2 20 the average composition throughout the interdiffusion zone remained constant at approximately 80 at.% Al. The interdiffusion microstructures observed by EPMA, SEM and TEM analyses were correlated to explain the observed morphological development in the interdiffusion zones. The concept of thermodynamic degrees of freedom was used to justify that, although deviations are apparent, the interdiffusion zones did not significantly deviate from an equilibrium condition in order for the observed microstructures to develop. Selected diffusion couples developed periodic bands within the interdiffusion zone as sub-layers in the three-phase regions. Observation of periodic banding was utilized to augment the hypothesis that internal stresses play a significant role in the phase development and evolution of U-Mo vs. pure Al diffusion couples. The addition of Si (up to 5 wt.%) to the Al significantly reduced the growth rate of the interdiffusion zone. The constituent phases and composition within the interdiffusion zone were also modified. When Si was present in the Al terminal alloys, the interdiffusion zones developed layered morphologies with fine distributions of the (U,Mo)(Al,Si) and UMo Al phases. The 3 2 20 U Mo Al phase was observed scarcely in Si depleted regions within the interdiffusion zone. 6 4 43 The phase development and evolution of the interdiffusion zone was described in terms of thermodynamic degrees of freedom with minimal deviations from equilibrium. iv This dissertation is dedicated to my family and friends who guided me through my life and who helped me become the person I am. This document is, above all, dedicated to all the lives and the environments that may be preserved as result of the work presented here. v ACKNOWLEDGMENTS This work was financially supported by Idaho National Laboratory (Contract No. 00051953) under the operation of U.S. Department of Energy – Battelle Energy Alliance, LLC (DE-AC07- 05ID14517). I would like to thank Dr. Yong-ho Sohn for his support, encouragement and advice throughout my career at the University of Central Florida (UCF), for the education he provided and for serving as the chair of the dissertation committee. I would also like to thank Dr. Dennis D. Keiser, Jr. for the opportunity to engage in the work discussed in this document and for his service as a committee member. I would like to express my gratitude to the additional committee members, Dr. Linan An, Dr. Kevin Coffey, Dr. Helge Heinrich and Dr. Challapalli Suryanarayana for all the education they provided me and for taking the time to examine and critique this document. I would like to express my gratitude to all of my coworkers for their continuous help with the laboratory facilities and experiments. Special thanks to Ashley Ewh, who helped set up the laboratory for radioactive materials handling, helped with the initial experiments, and helped develop the experimental procedures that became standard procedures to the laboratory facility. I would also like to thank all of the Advanced Materials Processing and Analysis (AMPAC) faculty and staff for their teachings and support throughout my years of study. vi TABLE OF CONTENTS LIST OF FIGURES.........................................................................................................................x  LIST OF TABLES......................................................................................................................xvii  1. INTRODUCTION.......................................................................................................................1  2. LITERATURE REVIEW............................................................................................................5  2.1 Reduced Enrichment for Research Test Reactors Program..................................................5  2.3 U-Mo Alloys.........................................................................................................................7  2.4 Al and Al-Si alloys.............................................................................................................10  2.5 Al-rich U-Mo-Al and U-Mo-Al-Si Cast Alloys.................................................................11  2.6 U-Mo/Al Dispersion and Monolithic Fuel Systems...........................................................11  2.7 U-Mo vs. Al Diffusion Couple Experiments......................................................................13  2.8 U-Mo vs. Al-Si Diffusion Couple Experiments.................................................................15  2.9 Binary UAl , U Al and Ternary U Mo Al and UMo Al Phases...............................16  3 0.9 4 6 4 43 2 20 2.10 Stress development as a result of phase transformations..................................................17  vii 3. EXPERIMENTAL DETAILS...................................................................................................19  3.1 Laboratory Facility.............................................................................................................19  3.2 U-Mo, Al and Al-Si alloy preparation................................................................................22  3.3 Diffusion couple assembly and characterization................................................................23  3.4 Characterization of 85.7Al-11.44U-2.86Mo, 87.5Al-10U-2.5Mo, 56.1Al-18.9Si-21.9U- 3.1Mo and 69.3Al-11.9Si-18.8U (at.%) Cast Alloys...............................................................24  4. RESULTS..................................................................................................................................27  4.1 Cast 85.7Al-11.44U-2.86Mo and 87.5Al-10U-2.5Mo Alloys characterization [62].........27  4.2. Phase Constituents in 19U-69Al-12Si and 22U-3Mo-56Al-19Si (at.%) Cast Alloys......34  4.3 Diffusion Couples: U-Mo vs. Pure Al Annealed at 600°C for 24 Hours...........................39  4.4 Diffusion couples U-Mo vs. Al and Al-Si alloys annealed at 500°C for 1, 5 and 20 hours59  5. DISCUSSION............................................................................................................................75  5.1 Cast 85.7Al-11.44U-2.86Mo and 87.5Al-10U-2.5Mo Alloys............................................75  5.2 Cast 19U-69Al-12Si and 22U-3Mo-56Al-19Si (at.%) Alloys Characterization................78  5.3 Diffusion couples U-Mo vs. Pure Al annealed at 600°C for 24 hours...............................82  5.4 Diffusion couples U-Mo vs. Al and Al-Si alloys annealed at 500°C for 1, 5 and 20 hours95  viii 5.4.1 U-Mo vs. Al diffusion couples.....................................................................................95  5.4.2 U-Mo vs. Al-Si.............................................................................................................99  6. CONCLUSIONS......................................................................................................................103  APPENDIX: LIST OF PUBLICATIONS AND CONFERENCE PRESENTATIONS.............106  Journal Publications................................................................................................................107  Peer Reviewed Conference Proceedings................................................................................108  Invited Presentations...............................................................................................................108  Contributing Presentations......................................................................................................109  REFERENCES............................................................................................................................111  ix LIST OF FIGURES Figure 1. Binary U-Mo phase diagram [70]....................................................................................8  Figure 2. Time-Temperature-Transformation diagram for U-10 wt.%Mo [21].............................9  Figure 3. Binary Al-Si phase diagram [77]...................................................................................10  Figure 4. Typical cross sections of U-Mo dispersions in Al matrix (a) after fabrication and (b) after irradiation, and U-Mo monolithic fuel in Al matrix (c) after fabrication and (d) after diffusion anneal.............................................................................................................................12  Figure 5. Glove box setup for the handling and storage of materials under a controlled Argon atmosphere....................................................................................................................................20  Figure 6. A schematic diagram showing the Ar flow through the glove box..............................20  Figure 7. Quartz capsule for heat treatment of diffusion couples, and a diffusion couple jig assembly holding a diffusion couple before diffusion anneal......................................................21  Figure 8. A schematic of a diffusion couple inserted in a quartz capsule in preparation for the vacuum flush procedure................................................................................................................21  Figure 9. Custom fabricated high vacuum system for evacuating quartz capsule........................21  x