Preparation and Characterization of B2S3-Based Chalcogenide Glasses Jaephil Cho Iowa State University
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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1995 Preparation and characterization of B2S3-based chalcogenide glasses Jaephil Cho Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Condensed Matter Physics Commons, Inorganic Chemistry Commons, and the Materials Science and Engineering Commons Recommended Citation Cho, Jaephil, "Preparation and characterization of B2S3-based chalcogenide glasses " (1995). Retrospective Theses and Dissertations. 10890. https://lib.dr.iastate.edu/rtd/10890 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. 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Ml 48106-1346 USA 313/761-4700 800/521-0600 Preparation and characterization of B2S3 - based chaicogenide glasses by Jaephil Cho A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements of the Degree of DOCTOR OF PHILOSOPHY Department: Materials Science and Engineering Major: Ceramic Engineering Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1995 UHI Number: 9531726 OMI Microform 9531726 Copyright 1995r by OHI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17# United States Code. UMI 300 North Zeeb Road Ann Arbor, HI 48103 ii Dedicated to my parents and my wife, Sharon for their love and support during my education iii TABLE OF CONTENTS CHAPTER 1. INTRODUCTION 1 CHAPTER 2. BACKGROUND 3 2.1. Structure and properties of alkali borate glasses 3 2.1.1. Structure of B2O3 3 2.1.2. Binary MjO + B2O3 glasses (M = Li, Na, K, Rb and Cs) 4 2.2. Structure and properties of alkali thioborate glasses 16 2.2.1.Structure of B2S3 16 2.2.2. Bianry sodium thioborate glasses 21 CHAPTER 3. OBJECTIVES OF THE DISSERTATION 27 CHAPTER 4. EXPERIMENTAL METHODS 29 4.1. Synthesis of high purity MjS (M = K, Rb and Cs) powders 29 4.2. Preparation of high purity v-BjSj 31 4.3. Preparation of M2S + B2S3 glasses and polycrystals (M = Li, K, Rb and Cs) 34 4.4. Preparation of MS + B2S3 glasses and polycrystals (M = Sr and Be) 34 4.5. Infrared (IR) spectroscopy measurement 35 4.6. Density measurement 35 4.7. Glass transition temperature measuremnt 36 4.8. "B NMR spectroscopy Measurement 38 CHAPTER 5. RESULTS AND DISCUSSION 39 5.1. Glass forming ranges 39 5.1.1. M2S + B2S3 glasses (M = Li, K, Rb and Cs) 39 5.1.2. MS + B2S3 glasses (M = Brand Ba) 40 5.2. X-ray diffraction data of c-MS;B2S3 polycrystals (M = Sr and Ba) 42 5.3. '^B NMR spectroscopy 45 5.3.1. Rb2S + B2S3 system 45 5.3.2. CS2S -I- B2S3 system 56 5.4. IR spectroscopy 65 iv 5.4.1. LijM + B2M3 (M = O, S) systems 65 5.4.1.1. IR spectra of the polycrystalline lithium borate and thioborate compounds 65 5.4.1.2. IR spectra of the lithium borate and thioborate glasses 73 5.4.2. KjS + B2S3 system 80 5.4.2.1. IR spectra of polycrystalline compounds 80 5.4.2.2. IR spectra of the glasses 86 5.4.3. RbjS + B2S3 system 93 5.4.3.1. IR spectra of polycrystalline compounds 93 5.4.3.2. IR spectra of the glasses 105 5.4.4. CSjS + B2S3 system 105 5.4.4.1. IR spectra of polycrystalline compounds 108 5.4.4.2. IR spectra of the glasses 114 5.4.5. SrS + B2S3 system 114 5.4.5.1. IR spectra of polycrystalline compounds 118 5.4.5.2. IR spectra of the glasses 122 5.4.6. BaS + B2S3 system 122 5.4.6.1. IR spectra of polycrystalline compounds 122 5.4.6.2. IR spectra of the glasses 125 5.5. Glass transition temperature 128 5.5.1. KjS + B2S3 glasses 129 5.5.2. RbzS + B2S3 and CS2S + B2S3 glasses 136 5.6. Density analysis 146 5.6.1. Na2S + B2S3 glasses 147 5.6.1.1. A model for densities and correlation with structural groups 147 5.6.1.2. Molar volumes of individual SRO groups 150 5.6.1.3. Composition dependence of the fractions of the individual SRO groups 152 5.6.1.4. Calculation of density 155 5.6.2. K2S + B2S3 glasses 156 5.6.2.1. Molar volumes of individual SRO groups 158 5.6.2.2. Composition dependence of the fractions of the individual SRO groups 160 5.6.2.3. Calculation of density 163 V 5.6.3. RbjS + B2S3 glasses 164 5.6.3.1. Composition dependence of the fractions of the Individual SRO groups 166 5.6.3.2. Molar volumes of individual SRO groups 170 5.6.3.3. Calculation of density 174 5.6.4. CSjS + B2S3 glasses 176 5.6.4.1. Composition dependence of the fractions of the individual SRO groups 179 5.6.4.2. Molar volumes of individual SRO groups 181 5.6.4.3. Calculation of density 184 CHAPTER 6. SUMMARY AND CONCLUSIONS 186 BIBLOGRAPHY 188 ACKNOWLEDGMENTS 194 1 CHAPTER I. INTRODUCTION The structure of crystals is clearly defined and can be described by the symmetry properties and the geometrical parameters of the unit cell. For these types of solids, x-ray crystallography can be used to completely determine the positions of all atoms In the crystalline lattices. However, the lack of long-range order in glasses prevents the use of such methods in studying their structures. Techniques have been developed in which one determines the radial distribution functions of electron densities about specific atoms. The results of this type of investigation are somewhat limited because the symmetry and extent of short range ordering cannot be adequately resolved. Analysis of vibrational spectra, however, can provide this type of structural information when a thorough theoretical analysis of the spectra is carried out. Infrared spectroscopy has also been used to identify low-concentration impurities such as water, hydroxyl ions, carbonate ions in glass. With the development of solid state electrochemical technology [1-111, the importance of maximizing the ionic conductivity of solid materials has come into focus. In recent years, considerable progress has been made in understanding the structural chemistry of many binary and ternary fast ionic conducting glasses as well as in the knowledge of their physical properties. The discovery of high lithium ionic conductivity in a new class of sulfide-based glasses has been one of the most significant developments in the field of solid electrolytes recently. Figure 1 shows the most common constituent elements of such glasses. 2 Li Be B Na Mg Al Si P S CI K Ca Cu Zn Ga Ge As Se Br Rb Sr Y Ag Cd In Sn Sb Te I Cs Ba La Hg T1 Pb Bi Figure 1. Elements that are found in the formation of covalent non-oxide glasses. Those elements within the high bold lines occur most commonly in such glasses. Glasses formed from melts containing the salts LijS and Lil, and glass formers such as B2S3, SiSj, and PjSgll-l 1] have conductivities at room temperature of 10® to 10'® (Q-cm) ' and show many specific and interesting structural features. In the case of sulfide compounds, the sulfur atom, which has a larger atomic radius than oxygen, tends to weaken the electrostatic interactions with the alkali cations and for this reason, the cation motion is facilitated by the lower potential barrier between alkali sites. Our recent studies [12-17] of BjSj-based glasses are motivated by the search to fully understand their structures and properties and to understand their high ionic conductivity as well as to determine the similarity or differences of these glasses to the corresponding oxide glasses. In particular, the existence and nature of the boron anomaly has not been thoroughly studied in the thioborate glasses. In this dissertation, a study is planned that seeks to develop a structural model that can be used to correlate the structure of thioborate glasses with their physical properties.