PHASE DEVELOPMENTS BETWEEN XENOTIME (YPO4) REFRACTORY AND AN ALKALI ALUMINOSILICATE GLASS MELT BY DALE M. FISHER JR. A THESIS SUBMITTED TO THE FACULTY OF ALFRED UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN GLASS SCIENCE ALFRED, NEW YORK OCTOBER, 2015 Alfred University theses are copyright protected and may be used for education or personal research only. Reproduction or distribution in part or whole is prohibited without written permission from the author. Signature page may be viewed at Scholes Library, New York State College of Ceramics, Alfred University, Alfred, New York. PHASE DEVELOPMENTS BETWEEN XENOTIME (YPO4) REFRACTORY AND AN ALKALI ALUMINOSILICATE GLASS MELT BY DALE M. FISHER JR. B.S. ALFRED UNIVERSITY (1995) SIGNATURE OF AUTHOR APPROVED BY ALEXIS CLARE, ADVISOR WILLIAM LACOURSE, ADVISORY COMMITTEE MATTHEW HALL, ADVISORY COMMITTEE CHAIR, ORAL THESIS DEFENSE ACCEPTED BY DOREEN D. EDWARDS, DEAN KAZUO INAMORI SCHOOL OF ENGINEERING ACKNOWLEDGEMENTS My deepest gratitude goes to my parents without whom none of what I have achieved would have been possible. Your guidance and faith through these many years led me to be the person I am today and for that, there will never be a way to say thank you. My heartfelt thanks to my wife and daughter who have supported me through many difficult and challenging times throughout the course of this work. None of this would have been possible without the support of many individuals in my professional life. Within Corning Inc., my boss, David Sonnefeld, deserves much credit and thanks for seeing in me a desire to go further and for his offer of support throughout this effort. Technically, Dr. Joe McIntosh, Joe Cukjati, Dr. William Mattingly, Dr. Bryan Wheaton, Dr. Ben Hanson, Dr. Nicolas LeBlond, Jeff Davis and Brett Abel all have provided me the greatest support in developing an understanding of the many subject areas and deserve praise for helping me through challenging questions. Finally, through the coursework and this thesis, Dr. Alexis Clare deserves profound credit for guiding me, helping me and for the many on and off subject conversations, which I have enjoyed immensely. Your guidance, tolerance and critical thinking made this journey a valuable one. iii TABLE OF CONTENTS Page Acknowledgements ................................................................................................ iii Tale of Contents ...................................................................................................... iv List of Tables ........................................................................................................... v List of Figures ........................................................................................................vii Abstract ................................................................................................................ xiii INTRODUCTION ......................................................................................................... 1 LITERATURE REVIEW.............................................................................................. 4 EXPERIMENTAL PROCEDURE ............................................................................... 9 A. Glass Preparation .................................................................................................9 B. SEM/EDS .......................................................................................................... 11 C. Powder XRD...................................................................................................... 20 D. HTXRD ............................................................................................................. 26 E. Sessile Drop ....................................................................................................... 31 F. EPMA ................................................................................................................ 39 G. DSC-TGA .......................................................................................................... 42 RESULTS .................................................................................................................... 43 A. SEM/EDS .......................................................................................................... 43 B. Line Scans ......................................................................................................... 67 C. Chemical Recalculation...................................................................................... 82 D. Powder XRD and HTXRD ................................................................................. 85 E. Sessile Drop ....................................................................................................... 98 F. EPMA .............................................................................................................. 104 G. DSC-TGA ........................................................................................................ 107 DISCUSSION ............................................................................................................ 110 CONCLUSIONS ........................................................................................................ 118 FUTURE WORK....................................................................................................... 119 REFERENCES .......................................................................................................... 121 APPENDIX ................................................................................................................ 122 iv LIST OF TABLES Page Table I. 727XW Glass Composition Data ............................................................. 9 Table II. Comparison of Glass Composition Data .................................................11 Table III. Matrix for Xenotime and Glass Thermal Gradient Experiment................12 Table IV. Sequence of Polishing Abrasives used During Sample Preparation .............................................................................................20 Table V. Six Samples Were Prepared for XRD Samples .......................................25 Table VI. Xenotime XRD Powder Samples Firing Schedule ..................................25 Table VII. Firing Schedule for Sheet Fusing ............................................................34 Table VIII. Seven Samples run During the Sessile Drop Tests ..................................37 Table IX. Isothermal Sessile Drop Tests at 950 °C .................................................39 Table X. Nine Species Scanned for in the Samples on the JEOL Superprobe .............................................................................................41 Table XI. Nine Species Matched to Three Standards ..............................................41 Table XII. Point Spectrum Data from Region of Devitrification...............................53 Table XIII. Point Spectrum Data from Region of Devitrification...............................55 Table XIV. Line Scan Parameters ............................................................................67 Table XV. Estimated Elemental Concentrations in Regions 3 and 4 .........................72 Table XVI. Line Scan Data at 5 µm is Compared to Point Spectrum Data .................75 Table XVII. Line Scan Data at 10 µm is Compared to Point Spectrum Data ...............76 v Table XVIII. Line Scan Data at 27 µm is Compared to Point Spectrum Data ..............77 Table XIX. Line Scan Data at 33 µm is Compared to Point Spectrum Data ...............78 Table XX. Chemical Recalculation for Sampled Data ..............................................82 Table XXI. Long Duration Chemical Data ................................................................84 Table XXII. Commercial Chemical Recalculation Software .......................................85 Table XXIII. Phases Identified in XRD Samples .........................................................86 vi LIST OF FIGURES Page Figure 1. Isopipe design for the fusion glass process as referenced in US8028544 B2. ....................................................................................... 2 Figure 2. Geometric configuration for an isopipe. ................................................... 3 Figure 3. For ABX4 REE compounds, crystal structure stability is represented as a function of A and B ionic radius. .................................... 5 Figure 4. Creep rate as a function of TiO2 content. ................................................. 6 Figure 5. Glass forming region in the yttrium aluminosilicate system. .................... 8 Figure 6. Micrographs taken from two samples used to characterize glass composition. ...........................................................................................10 Figure 7. Refractory sample positioned in the Pt/Rh 20 mil boat in cross section. ...................................................................................................13 Figure 8. Gradient boat cross section with cullet added. .........................................13 Figure 9. Lateral and longitudinal cross sections of gradient furnace......................14 Figure 10. Tube furnace arrangement with thermocouple probe inserted into the sample tube (a.). .........................................................................15 Figure 11. The platinum boat with glass and refractory sample in the line transfer device. .......................................................................................15