Optical Basicity and Nepheline Crystallization in High Alumina Glasses

The purpose of this study was to find compositions that increase waste loading of high-alumina wastes beyond what is currently acceptable while avoiding crystallization of nepheline (NaAlSiO4) on slow cooling. Nepheline crystallization has been shown to have a large impact on the chemical durability of high-level waste glasses. It was hypothesized that there would be some composition regions where high-alumina would not result in nepheline crystal production, compositions not currently allowed by the nepheline discriminator. Optical basicity (OB) and the nepheline discriminator (ND) are two ways of describing a given complex glass composition. This report presents the theoretical and experimental basis for these models. They are being studied together in a quadrant system as metrics to explore nepheline crystallization and chemical durability as a function of waste glass composition. These metrics were calculated for glasses with existing data and also for theoretical glasses to explore nepheline formation in Quadrant IV (passes OB metric but fails ND metric), where glasses are presumed to have good chemical durability. Several of these compositions were chosen, and glasses were made to fill poorly represented regions in Quadrant IV. To evaluate nepheline formation and chemical durability of these glasses, quantitative X-ray diffraction (XRD) analysis and the Product Consistency Test were conducted. A large amount of quantitative XRD data is collected here, both from new glasses and from glasses of previous studies that had not previously performed quantitative XRD on the phase assemblage. Appendix A critically discusses a large dataset to be considered for future quantitative studies on nepheline formation in glass. Appendix B provides a theoretical justification for choice of the oxide coefficients used to compute the OB criterion for nepheline formation.

[1]  E. Bordes.  The role of structural chemistry of selective catalysts in heterogeneous mild oxidation catalysis of hydrocarbons , 2000 .

[2]  Aron Walsh,et al.  Experimental and theoretical study of the electronic structure of HgO and Tl2O3 , 2005 .

[3]  R. Egdell,et al.  A study of core and valence levels in β-PbO2 by hard X-ray photoemission , 2009 .

[5]  J. Yamashita,et al.  The Theory of the Dielectric Constant of Ionic Crystals III , 1955 .

[6]  S. Sakka,et al.  Electronic oxide polarizability and optical basicity of simple oxides. I , 1996 .

[7]  T. Komatsu,et al.  Electronic polarizability, optical basicity and non-linear optical properties of oxide glasses , 1999 .

[8]  G. Chryssikos,et al.  Trends in Local Optical Basicity in Sodium-Borate Glasses and Relation to Ionic Mobility , 1993 .

[9]  M. Ingram,et al.  Establishment of an optical scale for Lewis basicity in inorganic oxyacids, molten salts, and glasses , 1971 .

[10]  N. Kreidl,et al.  STABILITY OF LEAD GLASSES AND POLARIZATION OF IONS , 1948 .

[11]  H. Schmidt,et al.  Structural, optical, and electronic properties of magnetron‐sputtered platinum oxide films , 1996 .

[12]  J. M. Toguri,et al.  A New Development of the Optical Basicity , 1986 .

[13]  Linus Pauling,et al.  THE NATURE OF THE CHEMICAL BOND. IV. THE ENERGY OF SINGLE BONDS AND THE RELATIVE ELECTRONEGATIVITY OF ATOMS , 1932 .

[14]  W. M. Haynes.  CRC Handbook of Chemistry and Physics , 1990 .

[15]  John A. Duffy,et al.  The electronic polarisability of oxygen in glass and the effect of composition , 2002 .

[16]  Xinyu Zhao,et al.  A new approach to estimate refractive index, electronic polarizability, and optical basicity of binary oxide glasses , 2008 .

[17]  C. C. Chen,et al.  Growth and characterization of OsO2 single crystals , 2004 .

[18]  A. Bergman.  Representation of Phosphorus and Vanadium Equilibria between Liquid Iron and Complex Steelmaking Type Slags , 1988 .

[19]  J. Duffy.  Ionic-covalent character of metal and nonmetal oxides. , 2006, The journal of physical chemistry. A.

[20]  K. Mills.  The Influence of Structure on the Physico-chemical Properties of Slags. , 1993 .

[21]  A R Plummer,et al.  Introduction to Solid State Physics , 1967 .

[22]  Derek Sleeman,et al.  Optical basicity of metallurgical slags: new computer based system for data visualisation and analysis , 1997 .

[23]  J. Celis,et al.  The Lubricity of Oxides Revised Based on a Polarisability Approach , 2004 .

[24]  Keyan Li,et al.  Estimation of electronegativity values of elements in different valence states. , 2006, The journal of physical chemistry. A.

[25]  T. Komatsu,et al.  Interionic Interactions, Electronic Polarizability and Optical Basicity of Oxide Glasses , 2000 .

[26]  P. Courtine,et al.  Improvement of a Bulk Optical Basicity Table for Oxidic Systems , 1998 .

[27]  J. Portier,et al.  A simple model for the estimation of electronegativities of cations in different electronic states and coordinations , 1994 .

[28]  T. Edwards,et al.  Control of Nepheline Crystallization in Nuclear Waste Glass , 2008 .

[29]  J. Duffy.  Electronic polarisability and related properties of the oxide ion , 1989 .

[30]  M. Ingram,et al.  Acid–base properties of molten oxides and metallurgical slags , 1978 .

[31]  L. Ono,et al.  Formation and Thermal Stability of Au2O3 on Gold Nanoparticles: Size and Support Effects , 2008 .

[32]  J. Duffy.  Optical basicity of sulfide systems , 1992 .

[33]  W. Plieth,et al.  Kramers-Kronig analysis for the determination of the optical constants of thin surface films: II. Application to platinum oxide films , 1975 .

[34]  T. Komatsu,et al.  Thermal stability, electronic polarisability and optical basicity of ternary tellurite glasses , 2001 .

[35]  K. Morinaga,et al.  Measurements of Refractive Indexes and Factors Affecting Dispersion in Oxide Glasses , 1995 .

[36]  P. Courtine,et al.  Correlations between the optical basicity of catalysts and their selectivity in oxidation of alcohols, ammoxidation and combustion of hydrocarbons , 2000 .

[37]  J. Duffy,et al.  Ionicity of simple binary oxides , 1985 .

[38]  P. Hrma,et al.  Glass Property Data and Models for Estimating High-Level Waste Glass Volume , 2009 .

[39]  H. Bach,et al.  Electrochemistry of Glasses and Glass Melts, Including Glass Electrodes , 2001 .

[40]  Y. Makino,et al.  Correlation between refraction basicity and theoretical optical basicity Part I. Alkaline and alkaline-earth silicate glasses , 1984 .

[41]  T. Komatsu,et al.  Effect of Interionic Interaction on the Electronic Polarizability, Optical Basicity and Binding Energy of Simple Oxides , 1999 .

[42]  J. Duffy.  Optical basicity analysis of glasses containing trivalent scandium, yttrium, gallium and indium , 2005 .

[43]  R. Finkelman,et al.  Downeyite, the first verified natural occurrence of SeO 2 , 1977 .

[44]  R. Jagannathan,et al.  Optical and electrical properties of PbO-TiO2, PbO-TeO2, and PbO-CdO glass systems , 1997 .

[45]  Y. Makino,et al.  Determination of ionic distributions of three sorts of oxygens in a few binary silicate glasses from molar refractivity , 1979 .

[46]  Nathan E. TeGrotenhuis,et al.  Effect of glass-batch makeup on the melting process , 2010 .

[47]  M. Schweiger,et al.  The Predictive Power of Electronic Polarizability for Tailoring the Refractivity of High Index Glasses Optical Basicity Versus the Single Oscillator Model , 2010 .

[48]  M. Ingram,et al.  An interpretation of glass chemistry in terms of the optical basicity concept , 1976 .

[49]  J. Duffy.  The refractivity and optical basicity of glass , 1986 .

[50]  Xinyu Zhao,et al.  Electronic polarizability and optical basicity of lanthanide oxides , 2007 .

[51]  Y. N. Ahammed,et al.  Correlation between optical basicity, electronegativity and electronic polarizability for some oxides and oxysalts , 1999 .

[52]  M. Lenglet.  Ligand field spectroscopy and chemical bonding in Cr3+-, Fe3+-, Co2+- and Ni2+-containing oxidic solids: Influence of the inductive effect of the competing bonds and magnetic interactions on the degree of covalency of the 3d M–O bonds , 2000 .

[53]  Y. N. Ahammed,et al.  Electronic polarizability and optical basicity properties of oxide glasses through average electronegativity , 2001 .

[54]  J. Duffy.  Relationship between Optical Basicity and Thermochemistry of Silicates , 2004 .

[55]  J. Duffy.  Chemical bonding in the oxides of the elements: A new appraisal , 1986 .

[56]  J. Duffy.  Polarisability and polarising power of rare earth ions in glass: an optical basicity assessment , 2005 .

[57]  John D. Vienna,et al.  Effects of Al2O3, B2O3, Na2O, and SiO2 on nepheline formation in borosilicate glasses: chemical and physical correlations , 2003 .

[58]  Manjula.,et al.  Correlation between electronegativity and superconductivity. , 1988, Physical Review B (Condensed Matter).

[59]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[60]  Xinyu Zhao,et al.  Average electronegativity, electronic polarizability and optical basicity of lanthanide oxides for different coordination numbers , 2008 .

[61]  W. Bohne,et al.  Optical properties and structure of HfO2 thin films grown by high pressure reactive sputtering , 2007 .

[62]  K. Fox,et al.  Refinement of the Nepheline Discriminator: Results of a Phase II Study , 2008 .

[63]  K. Morinaga,et al.  Effect of PbO, Bi2O3 and Tl2O on Optical Properties of Heavy Metal Gallate Glasses , 1995 .

[64]  M. Lenglet.  IONO-COVALENT CHARACTER OF THE METAL OXYGEN BONDS IN OXIDES: A COMPARISON OF EXPERIMENTAL AND THEORETICAL DATA , 2004 .

[65]  M. Ingram,et al.  Comments on the application of optical basicity to glass , 1992 .

[66]  Ivan Fanderlik,et al.  Optical properties of glass , 1983 .

[67]  F. Pollak,et al.  Optical properties of single-crystal rutile RuO2and IrO2in the range 0.5 to 9.5 eV , 1981 .

[68]  Carol M. Jantzen,et al.  Characterization of projected DWPF glasses heat treated to simulate canister centerline cooling , 1992 .

[69]  K. Nagata,et al.  Determination of refractive index and absorption coefficient of iron- oxide-bearing slags , 1992 .

[70]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[71]  K. Fox,et al.  INTERNATIONAL STUDY OF ALUMINUM IMPACTS ON CRYSTALLIZATION IN U.S. HIGH LEVEL WASTE GLASS , 2008 .

[72]  F. P. Koffyberg.  Optical bandgaps and electron affinities of semiconducting Rh2O3(I) and Rh2O3(III) , 1992 .

[73]  J. Beckett.  Role of basicity and tetrahedral speciation in controlling the thermodynamic properties of silicate liquids, part 1: the system CaO-MgO-Al 2 O 3 -SiO 2 , 2002 .

[74]  J. Duffy.  A common optical basicity scale for oxide and fluoride glasses , 1989 .

[75]  A. H. Kahn,et al.  Electronic Polarizabilities of Ions in Crystals , 1953 .

[76]  A. Ritchie.  The kinetics and mechanism of the uranium-water vapour reaction — an evaluation of some published work , 1984 .

[77]  Hiromichi Takebe,et al.  Compositional Dependence of Absorption Spectra of Ti3+ in Silicate, Borate, and Phosphate Glasses , 1994 .

[78]  Takayuki Komatsu,et al.  Classification of Simple Oxides: A Polarizability Approach , 2002 .

[79]  V. Birss,et al.  A multi-technique study of compact and hydrous Au oxide growth in 0.1 M sulfuric acid solutions , 2001 .

[80]  J. Duffy.  Optical basicity of titanium(IV) oxide and zirconium(IV) oxide , 1989 .

[81]  T. Komatsu,et al.  Electronic polarizability, optical basicity, and interaction parameter of La2O3 and related glasses , 2002 .

[82]  M. Ingram,et al.  Nephelauxetic effect and Pauling electronegativity , 1973 .

[83]  J. Portier,et al.  A simple approach to materials design: role played by an ionic-covalent parameter based on polarizing power and electronegativity , 1994 .

[84]  D. Peeler.  Nepheline Formation Study for Sludge Batch 4 (SB4): Phase 2 Experimental Results , 2006 .