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Raman spectroscopic studies of calcium-phosphate, aluminum metaphosphate-sodium fluoride and calcium metaphosphate-calcium fluoride glasses Item Type text; Thesis-Reproduction (electronic) Authors Latifzadeh, Lida, 1956- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 27/09/2021 07:48:35 Link to Item http://hdl.handle.net/10150/278549 INFORMATION TO USERS The most advanced technology has been used to photograph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. 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RAMAN SPECTROSCOPIC STUDIES OF CALCIUM-PHOSPHATE, ALUMINUM METAPHOSPHATE - SODIUM FLUORIDE AND CALCIUM METAPHOSPHATE - CALCIUM FLUORIDE GLASSES by Lida Latifzadeh A Thesis Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of MASTER OF SCIENCE In the Graduate College THE UNIVERSITY OF ARIZONA 19 9 0 2 STATEMENT BY AUTHOR This thesis has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowl edgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in1part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: APPROVAL BY THESIS DIRECTOR This thesis has been approved on the date below: la-10'ô JEANNE E.ÊMBERTON Date As5 iate Professor of Chemistry 3 DEDICATION To my parents and brothers 4 ACKNOWLEDGMENTS I would like to thank Dr. Jeanne E. Pemberton for her support, encouragement, and guidance during this research. I greatly appreciate her for giving me the opportunity to advance in my career. I would like to thank Dr. Subhash H. Risbud for giving me the opportunity to prepare the glass samples. I would like to say thanks to Dr. Joseph P. Fletcher for preparing the fluorophosphate glasses and his help in preparing the calcium-phosphate and calcium metaphosphate-calcium fluoride glasses. Many thanks to Dr. James Kirkpatrick at the University of Illinois for obtaining the NMR spectra. Finally, special thanks to the people in the Pemberton research group for their encouragement and inspiration. 5 TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS 7 LIST OF TABLES 9 ABSTRACT 11 CHAPTER 1. INTRODUCTION: PHOSPHATE AND FLUOROPHOSPHATE GLASSES 12 Phosphate Glass Structure . 13 Characterization of Phosphate Glasses . 21 Raman Spectroscopy 21 X-ray Diffraction 23 NMR Spectroscopy 24 Characterization of Fluorophosphate Glasses 26 Raman Spectroscopy 26 X-ray Diffraction 28 NMR Spectroscopy 28 Description of Research Problem 29 Research Objectives 30 2. EXPERIMENTAL PROCEDURES 31 Glass Preparation ...... 31 Preparation of Calcium Metaphosphate Glasses 31 Preparation of Fluorophosphate Glasses 33 Raman Spectroscopy 38 Raman Spectroscopy of Ca Phosphate Glasses 38 Raman Spectroscopy of Fluorophos phate Glasses 40 Curve Fitting Procedures 40 Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy . 46 3. MOLECULAR STRUCTURAL STUDIES OF PHOSPHATE GLASSES WITH VARYING CaO MODIFIER CONCENTRATIONS 47 6 TABLE OF CONTENTS—Continued Page Raman Spectral Results 51 NMR Spectral Results 66 Conclusions 66 4. MOLECULAR STRUCTURAL STUDIES OF FLUORO- PHOSPHATE GLASSES WITH VARYING NaF CONCENTRATIONS 70 Al(POo >3-NaF Glass Series . 70 Fluorophosphate Glasses 71 Aluminophosphate Glasses 74 Raman Spectral Results 74 NMR Spectral Results 91 Conclusions 93 Calcium Fluoride-Calcium Metaphosphate Glasses 93 5. CONCLUSIONS AND FUTURE WORK 98 APPENDIX: CURVE FITTING ROUTINES ON THE DEC LSI-11/23 COMPUTER 103 REFERENCE 106 7 LIST OF ILLUSTRATIONS Figure Page 1.1 The structure of phosphate glass with calcium 15 1.2 The structural changes of phosphate glass upon adding a divalent ion modifier ..... 17 1.3 The structural changes of phosphate glasses upon addition of fluoride ions 18 1.4 Phosphate species with varying fluorine content 20 2.1 Schematic of the Raman spectrometer ..... 39 2.2 Important parameters of a spectral band ... 41 2.3 Spectroscopic line shapes . 43 2.4 Residuals for curve fitting 44 3.1 Vibrational modes of phosphate glasses active in Raman spectroscopy 49 3.2 Raman spectral results for Ca phosphate glasses 54 3.3 Curve fitting results for Ca phosphate glasses 56 3.4 vs(P0P) band frequency as a function of CaO concentration 61 3.5 Structure of Y- and ct_calcium pyrophosphates 64 3.6 Variation of I{P02)/I(POP) as a function of CaO concentration 65 3.7 ^1P NMR spectral results for the calcium phosphate glasses 67 4.1 Raman spectral results for Al(P03)3_NaF glasses 78 4.2 ÂlNMR spectral results for Al(P03)3~NaF glasses 87 8 LIST OF ILLUSTRATIONS--Continued Figure Page 4.3 "^P NMR spectral results for Al(P03)3~NaF glasses 92 4.4 Raman spectral results for the calcium fluoride-calcium metaphosphate glasses ... 95 5.1 The combination of size exclusion chromato graphy and Raman spectroscopy for the structural studies of phosphate glasses ... 100 5.2 Schematic of the combination of three techniques for the structural studies of fluorophosphate glasses 102 9 LIST OF TABLES Table Page 1. Batched wt% for calcium phosphate glasses . 32 2. Elemental analysis and water content results for calcium phosphate glasses .... 32 3. Starting compositions for AltPC^^-NaF glasses 34 4. Batched compositions of the AlfFC^^-NaF glasses 34 5. Chemical analysis of the AlfPOg^-NaF glass series 36 6. Molar ratios of Na/P and F/P for fluorophosphate glasses 37 7. Batched compositions for calcium metaphosphate-calciurn fluoride glasses 37 8. Water content and batch weight loss of cal cium metaphosphate-calcium fluoride glasses . 37 9. Average chain length (n~) for calcium- phosphate glasses 52 10. Vibrational band assignments and their qualitative intensities for the Ca-phosphate glasses 7...... 58 11. Vibrational band assignments and their qualitative intensities for a-calcium pyrophosphate ..... 62 12. Vibrational band assignments and their qualitative intensities for y-calcium pyrophosphate 62 13. Average chain length (n~) for sodium phosphate glasses 72 14. The average chain length (m) for sodium fluorophosphate glasses 72 10 LIST OF TABLES—Continued Table Page 1 5 Vibrational band assignments and their quali tative intensities for sodium fluorophosphate glasses in the v(P-O-P) and v(-P-O) region . 79 16. Vibrational band assignments and their qualitative intensities for sodium fluorophosphate glasses in the v(P02> region ... 81 27 17. Al NMR assignments for aluminophosphate glasses 88 18. Other vibrational bands and their qualitative intensities for Al(P03)3~NaF glasses .... 90 19. Vibrational band assignments and their qualitative intensities for the calcium metaphosphate-calcium fluoride glasses ... 96 11 ABSTRACT The role of modifier on the molecular structure of Ca-phosphate, sodium fluorophosphate and sodium aluminophosphate glasses have been investigated by Raman spectro scopy. Ca-phosphate glasses for this study have the molar ratio of Ca0/P205 from 1.00 to 1.50. Curve fitting proce dures have been used to resolve the overlapped peaks for accurate interpretation. Amorphous species with varying chain lengths and two crystalline phases of y- and a-Ca2P2°7 have been identified. Sodium fluorophosphate glasses have been prepared from the reaction between Al(P03)3 and NaF. The molar ratio of Na/P is varied from 0.900 to 2.00 and the F/P ratio is from 0.510 to 1.61. By studying the vibrational frequency shifts, species with varying phosphorus and fluorine contents and aluminophosphate compounds have been identified. 12 CHAPTER ONE INTRODUCTION: PHOSPHATE AND FLUOROPHOSPHATE GLASSES Phosphate glasses are of interest for applications in optical data transmission, biological materials and electronic packaging.

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