ANNUAL PROGRESS REPORT Project Title: Synthesis and Optimization of the Sintering Kinetics of Actinide Nitrides Covering Period: July 2005 – December 2008 Date of Report: 03/31/2009 Recipient: Boise State University Award Number: DE-FC07 – 05ID14650 Subcontractors: University of Florida Other Partners: None Contact(s): Darryl P. Butt, 208-426-1054, [email protected] Boise State University 1910 University Drive Boise, ID 83725-2075 Project Team: John Carmack, INL (not funded); Ken McClellan, LANL (not funded); Ron Baney, UF (funded); James Tulenko, UF (funded); Tim Gerhardt, UF (funded); Le Song, UF (funded); Ravi Kumar Vasudevin, UF (funded); Brian M. Marx, BSU (funded); A. S. Hamdy (not funded); Patrick Callahan, BSU (funded); Brian Jaques, BSU (funded); Dan Osterberg BSU (funded). Authors: Darryl P. Butt and Brian Jaques i TABLE OF CONTENTS TABLE OF CONTENTS................................................................................................................. i LIST OF TABLES......................................................................................................................... iii LIST OF FIGURES ....................................................................................................................... iv NOMENCLATURE AND ACRONYMS ................................................................................... xiv CHAPTER I: OBJECTIVE AND EXECUTIVE SUMMARY.....................................................16 1. Objective..............................................................................................................................16 2. Executive Summary.............................................................................................................16 CHAPTER II: PROJECT OVERVIEW ........................................................................................18 1. Introduction..........................................................................................................................18 2. Surrogate Fuels ....................................................................................................................20 CHAPTER III: FACILITIES........................................................................................................23 1. Gloveboxes ..........................................................................................................................23 2. Process Gas Capabilities......................................................................................................24 3. High Temperature Tube Furnaces .......................................................................................24 4. Powder Milling System........................................................................................................27 5. Particle Size Analyzer..........................................................................................................27 6. Green Pellet Forming Capabilities.......................................................................................28 7. Balance with the Immersion Density Measurement Kit......................................................29 8. Simultaneous DSC/TGA Equipment ...................................................................................30 CHAPTER IV: SYNTHESIS OF NITRIDE MATERIALS ........................................................32 1. Synthesis of Uranium Mononitride (UN) ............................................................................33 1.1. Carbothermic Reduction Prior to Nitridation Synthesis Route to UN........................37 1.2. Hydride prior to Nitridation Synthesis Route to UN ..................................................40 1.3. Novel Reactive Milling Synthesis Route to UN.........................................................43 1.4. Discussion of Uranium Nitride Synthesis Routes.......................................................50 2. Synthesis of Dysprosium Mononitride (DyN).....................................................................57 2.1. Carbothermic Reduction Prior to Nitridation Synthesis Route to DyN......................59 2.2. Hydride prior to Nitridation Synthesis Route to DyN ................................................61 2.3. Direct Nitridation Synthesis Route to DyN ................................................................65 2.4. Novel Reactive Milling Synthesis Route to DyN.......................................................67 2.5. Solution Synthesis Route Analogous to Sol Gel Processing for Synthesizing DyN........................................................................................................................72 2.6. Discussion of the Dysprosium Nitride Synthesis Routes ...........................................76 3. Synthesis of Cerium Mononitride (CeN).............................................................................78 3.1. Carbothermic Reduction Prior to Nitridation Synthesis Route to CeN ......................78 3.2. Hydride prior to Nitridation Synthesis Route to CeN.................................................81 3.3. Novel Reactive Milling Synthesis Route to CeN .......................................................86 3.4. Solution Synthesis Routes Analogous to Sol Gel Processing for Synthesizing CeN ........................................................................................................................89 ii CHAPTER V: SINTERING OF NITRIDE MATERIALS ..........................................................96 1. Sintering of Pure Zirconium Nitride (ZrN)..........................................................................96 1.1. Experimental Procedures for Sintering Pure ZrN.......................................................96 1.2. Results of Sintering Pure ZrN.....................................................................................97 2. Sintering of Zirconium and Dysprosium Nitride (Zr, Dy)N................................................99 2.1. Experimental Procedures for Sintering (Zr, Dy)N....................................................100 2.2. Results of Sintering (Zr, Dy)N..................................................................................100 3. Sintering of Pure Uranium Mononitride (UN)...................................................................107 3.1. Experimental Procedures for Sintering Pure UN......................................................116 3.2. Results of Sintering Pure UN....................................................................................128 4. Sintering of Uranium and Dysprosium Nitride (U,Dy)N ..................................................128 4.1. Experimental Procedures for Sintering (U, Dy)N.....................................................129 4.2. Results of Sintering (U, Dy)N ..................................................................................130 CHAPTER VI: OXIDATION STUDY OF DYSPROSIUM MONONITRIDE .........................132 1. Characterization of the DyN Powder used for the Oxidation Studies ...............................132 2. Experimental Procedures for the Oxidation of DyN..........................................................133 3. Results of the Oxidation of DyN .......................................................................................134 CHAPTER VII: ECONOMIC ANALYSIS ...............................................................................139 CHAPTER VIII: ACCOMPLISHMENTS.................................................................................146 1. Project Details....................................................................................................................146 2. Publications and Presentations...........................................................................................147 REFERENCES ............................................................................................................................150 APPENDIX A: Physical and Thermodynamic Properties of Various Nitrides, Oxides, and Metals....................161 APPENDIX B: Compilation of Initial, Intermediate, and Final Stage Sintering Models.....................................170 APPENDIX C: Error Propagation Calculations for Density Determinations.......................................................175 APPENDIX D: Thermodynamic Calculations of Uranium Nitride Reactions .....................................................177 APPENDIX E: Discussion and Review of Nitrogen Diffusion in Uranium.........................................................178 APPENDIX F: Standard Operating Procedure for: Synthesis of Depleted-UN Pellets by Carbothermic Reduction from Depleted-UO2 ........................................................................................185 iii LIST OF TABLES Table 1: Available UREX+ Processes and the Extracted Products [4]. ........................................19 Table 2: Candidate Non-Fertile and Low-Fertile Fuels for AFCI [5-7]. .......................................19 Table 3: A table showing characteristics of the six Generation IV reactor candidates. Adapted from [51, 52]........................................................................................................32 Table 4: Sample identification and the respective process parameters for sintering of 99.5% pure ZrN. ................................................................................................................97 Table 5: Geometric density measurements obtained from the sintered ZrN pellets by varying parameters such as temperature,