Clemson University TigerPrints All Dissertations Dissertations 12-2009 NUCLEATION AND GROWTH BEHAVIOR OF TELLURITE-BASED GLASSES SUITABLE FOR MID-INFRARED APPLICATIONS Jonathan Massera Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Part of the Materials Science and Engineering Commons Recommended Citation Massera, Jonathan, "NUCLEATION AND GROWTH BEHAVIOR OF TELLURITE-BASED GLASSES SUITABLE FOR MID- INFRARED APPLICATIONS" (2009). All Dissertations. 463. https://tigerprints.clemson.edu/all_dissertations/463 This Dissertation is brought to you for free and open access by the Dissertations at TigerPrints. It has been accepted for inclusion in All Dissertations by an authorized administrator of TigerPrints. For more information, please contact [email protected]. NUCLEATION AND GROWTH BEHAVIOR OF TELLURITE-BASED GLASSES SUITABLE FOR MID-INFRARED APPLICATIONS A Thesis Presented to the Graduate School of Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Materials Science and Engineering by Jonathan Massera December 2009 Accepted by: Dr. Kathleen Richardson, Committee Chair Dr. Stephen Foulger Dr. John Ballato Dr. Yaw Obeng Dr. Mark Davis ABSTRACT Optical fibers transmitting in the 2-5 µm mid-infrared (MIR) spectral region are highly desirable for a variety of military and civilian applications including super- continuum generation, infrared countermeasures (IRCM), and MIR laser sources. These new applications in the mid-infrared require novel optical materials that transmit in this window and can be fabricated into fiber. As tellurite glasses are known to have good transparency in the (NIR) region, tellurite-based glasses are the material of choice for this study due to their high linear and nonlinear refractive index, their low glass transition temperature and the ability to form them into optical fiber. This dissertation summarizes findings on tellurite-based glasses with the composition (90-x)TeO 2-10Bi 2O3-xZnO with x = 15, 17.5, 20 and 25 that were processed and characterized for their potential application as novel optical fibers. Different techniques were deployed for characterization purposes, which include primarily linear refractive index measurements, structural characterization using Raman spectroscopy, and nucleation and growth behaviors, among others. The viscosity of the glasses was measured using a beam bending and parallel plate viscometers. The kinetics of crystallization of the bulk glasses and fiber with x =20 were studied using a differential scanning analyzer (DTA), a hot stage XRD and an optical microscope. The influence of compositional variation on the physical, thermal and optical properties of the glasses in the TeO 2-Bi 2O3-ZnO family was established. The parameters i such as the thermal properties, activation energy for crystallization, Johnson-Mehl- Avrami exponent, or nucleation and growth domains and rates were determined and were found to depend on the glass composition. We correlated the composition-dependent variation of these parameters to the structure of the glasses via Raman spectroscopy. Key physical, thermal, structural and optical differences were observed and quantified between bulk glasses and their corresponding core and core-clad fibers. Also reported are the processing and characterization of modified tellurite-based glass in the TeO 2-Bi 2O3-ZnO glass family and efforts to reduce their absorption loss due to residual hydroxyl (OH) content. We discuss the impact of this OH reduction in the tellurite network on the physical, thermal and structural properties as well as nucleation and growth behavior of bulk glass and fiber. ii ACKNOWLEDGMENTS This thesis would not have been completed without the help and support of many people. First and foremost I owe my sincere gratitude to Dr. Kathleen Richardson for her constant support, guidance and enthusiasm throughout the course of the past four years. Thank you for providing me with the unique opportunity to join the GPCL group. Dr. Richardson provided me the freedom to pursue my research interests and to collaborate with other research groups around the globe. Besides sharing her extensive knowledge, she gave me through the years the fantastic opportunity to interact with some amazingly interesting scientists, some of them whom became dear friends, and to go to multiple conferences in different parts of the world. Kathleen, your experience, vision and leadership will be invaluable assets I will always admire, learn from and refer to in my career. Thank you so much for all your help, your support, and your guidance! For all this, you have my eternal gratitude. I would also like to express immense gratitude to the rest of my PhD committee members. My thesis (academic and industrial) committee has given me a lot of help to my research work; not only to review this work but also for their support during all these years. Dr. Mark Davis from SCHOTT, his industrial eyes and experience helped me taking into account factors I was unaware of. I deeply appreciate his guidance. He gave me directions when I was lost, taught me life principles, and kept giving often without taking. Dr. John Ballato at Clemson University, a leader in optical fiber, has guided me iii to the optical fiber drawing process. Thank you, Dr. Stephen Foulger at Clemson University for giving me many insightful suggestions that have helped me to think deeper into and perfect my research. Dr. Yaw Obeng at NIST, his advice has been very helpful in improving not only my thesis work but also my personal life. It is an honor to include all of you on my committee. I am very fortunate to have worked with the people at COMSET who share the same passion and fascination with optical fibers. I had the great opportunity to draw the fibers with Dr. Paul Foy and Wade Hawkins at COMSET and to characterize them with Dr. Roger Stolen . I benefited a lot from the fruitful interactions with them dealing with the intriguing scientific problems. I am also grateful to the staff of the School of Materials Science and Engineering, especially Shelby Sheriff and Tonya Bledsoe , for their kindness and efficiency, and the teachers who gave me one of the greatest gifts of all: knowledge. In particular, I thank Dr. Henry Rack for many insightful conversations during the development of this thesis. I enjoyed also my short trip to Alfred University and express my gratitude to Dr. Scott Misture for his input regarding the analysis of the XRD patterns. Another group that did a lot for me is the Laser Plasma Laboratory led by Dr. Martin Richardson at CREOL: Jiyeon Choi and Troy Anderson . Thank you for your constant support and knowledge in optics. I am glad to have the opportunity to work with Dr. Clara Rivero-Baleine at Lockheed Martin, the “Raman Girl”. iv A special “Kiitos” to Teemu Kokki at nLight (Finland) for the measurement of the losses in these “weird” non-silica fibers. Thank you for showing me the equipments and for the fruitful discussions on the losses in optical fiber I also need to thank my current and former “workmates” of the GPCL for dealing with me and my jokes through the years: Matthew O’Donnell, Scott Gaylord, Adam Haldeman, Ben Tincher, Jessica Jackson, Nathan (Alison and Charlotte) Carlie, Dave (and Jess) Musgraves, Iona Moog, Charmayne Smith, Jean Remond, Pete (Teresa and Alicia) Watchel. I will miss our BBQ parties and all the fun we had together. Friends have been made, among the COMSET, CREOL or REU students, without any order of preference, and all those that I forget, and 4 years of a lifetime is not insignificant. I am thankful to all of you for sharing your friendship and making everyday life a constant travel through the World cultures. I will miss you above everything else! Merci enfin a mes parents, ma «belle belle-maman», mon frère et ma sœur d’être toujours la pour moi. Merci surtout à ma femme, Laeticia sans qui rien n’aurait été possible…. If some of you are looking for me, I will be back in Europe…. in the cold and sunny Finland for a new episode of my life… v TABLE OF CONTENTS NUCLEATION AND GROWTH OF TELLURITE-BASED GLASSES SUITABLE FOR MID-INFRARED APPLICATIONS ........................................................................ i ABSTRACT ..................................................................................................................... i ACKNOWLEDGMENTS .............................................................................................. iii LIST OF FIGURES ......................................................................................................... x LIST OF TABLES ..................................................................................................... xviii CHAPTER I: INTRODUCTION ..................................................................................... 1 CHAPTER II: BACKGROUND ..................................................................................... 5 II.1 Fundamentals of glass formation.................................................................... 5 II.1.1 Glasses ....................................................................................................... 5 II.1.2 Glass-Ceramics .......................................................................................... 8 II.1.2.1 Phase separation (spinodal/droplet and nucleation and growth) ................ 11 II.1.2.2 Nucleation and growth ............................................................................