Thermodynamic assessment of the pseudoternary Na2O–Al2O3–SiO2 system

Vitrified high‐level radioactive waste that contains high concentrations of Na₂O and Al₂O₃, such as the waste stored at the Hanford site, can cause nepheline to precipitate in the glass upon cooling in the canisters. Nepheline formation removes oxides such as Al₂O₃ and SiO₂ from the host glass, which can reduce its chemical durability. Uncertainty in the extent of precipitated nepheline necessitates operating at an enhanced waste loading margin, which increases operational costs by extending the vitrification mission as well as increasing waste storage requirements. A thermodynamic evaluation of the Na₂O–Al₂O₃–SiO₂ system that forms nepheline was conducted by utilizing the compound energy formalism and ionic liquid model to represent the solid solution and liquid phases, respectively. These were optimized with experimental data and used to extrapolate phase boundaries into regions of temperature and composition where measurements are unavailable. The intent is to import the determined Gibbs energies into a phase field model to more accurately predict nepheline phase formation and morphology evolution in waste glasses to allow for the design of formulations with maximum loading.     

Thermal Conductivity of Molten B2O3, B2O3–SiO2, Na2O–B2O3, and Na2O–SiO2 Systems

With the aid of the transient hot‐wire method, the thermal conductivity of molten B₂O₃, B₂O₃–SiO₂, Na₂O–SiO₂, and Na₂O–B₂O₃ systems was measured along with their temperature and composition. It was observed that the thermal conductivity of pure B₂O₃ increased with temperature, until about 1400 K, and then decreased subsequently. Using the MAS‐NMR, 3Q‐MAS, and Raman spectroscopy, the structure of B₂O₃ and SiO₂ in the B₂O₃–SiO₂ system was confirmed. Findings show that an addition of B₂O₃ into the pure SiO₂ system causes a significant decrease in thermal conductivity, due to the formation of boroxol rings. The thermal conductivity of the Na₂O–SiO₂ system was measured and its phonon mean free path was calculated. In addition, a positive linear relation between viscosity and thermal conductivity was observed. In the Na₂O–B₂O₃ system, it was found that a change in the relative fraction of 4‐coordinated boron has an influence on the thermal conductivity when the concentration of Na₂O is between 10 and 30 mol%, in which case the tetraborate unit is dominant.     

Crystal Growth of F‐Phlogopite from Glasses of the SiO2–Al2O3–MgO–K2O–F System

A study on the devitrification of fluorophyllosilicate glass precursors is presented. The research has been focused on the early stages of the crystallization process and shows the variation in the crystallization mechanism with increasing the fluorine content. The devitrification process has been studied by means of differential scanning calorimetry (DSC) and field‐emission scanning electron microscopy (FESEM). These complementary techniques established that both surface (heterogeneous nucleation) and volume (internal homogeneous nucleation) mechanisms are present in the crystallization process of fluorophlogopite‐based glasses, the latter being predominant. By increasing the percentage of fluorine in the parent glass, a variation in the location of the first crystals developed from the internal volume of the glass toward the external surface was observed. Such an alteration in the crystallization mechanism was also checked by examining the microstructure of crystallized samples prepared under short‐time treatments.     

Y3Al5O12–SiO2 Glasses: Structure and Polyamorphism

Aerodynamic levitation and CO₂ laser melting have been used to synthesize the yttrium aluminosilicate glasses zY₂O₃–yAl₂O₃–xSiO₂ with z/y = 3/5 corresponding to the YAG (Y₃Al₅O₁₂) composition and x between ~5 and ~45 mol%. The low‐ and high‐density (LDA inclusion and HDA matrix) polyamorphic phases in glasses with less than ~14 mol% SiO₂ were identified with backscattering electron imaging. Polarized and depolarized Raman spectra show the formation of various Qⁿ SiO₄ species whose relative populations change smoothly as the SiO₂ content is altered. The AlOs (s = 4–6) and YOz (z = 6–9) polyhedra formed in the YAG glass are preserved upon silica additions while the terminal oxygens of the Q²AlO₄ tetrahedra are gradually bridged to the Qⁿ‐SiO₄ species. The low‐frequency Boson Peak overlaps with the vibrational spectrum and its maximum is redshifted with increasing silica content. Micro‐Raman spectra measured for the LDA and HDA amorphous phases are found to be similar to the spectra of the bulk glass indicating common structural characteristics. The stability of the LDA phase against crystallization appears to be lower than that of the HDA phase. The crystallinity on certain inclusions consisted of YAG microcrystals and a new unidentified microcrystalline phase within Y₄Al_2(1?x)Si_2xO_(9+x) solid solution.     

Effect of Nitrogen on Properties of Na2O–CaO–SrO–ZnO–SiO2 Glasses

Glasses in the Na₂O–CaO–SrO–ZnO–SiO₂ system have previously been investigated for suitability as a reagent in Al‐free glass polyalkenoate cements (GPCs). These materials have many properties that offer potential in orthopedics. However, their applicability has been limited, to date, because of their poor strength. This study was undertaken with the aim of increasing the mechanical properties of a series of these Zn‐based GPC glasses by doping with nitrogen to give overall compositions of: 10Na₂O–10CaO–20SrO–20ZnO–(40?3x)SiO₂–xSi₃N₄ (x is the no. of moles of Si₃N₄). The density, glass‐transition temperature, hardness, and elastic modulus of each glass were found to increase fairly linearly with nitrogen content. Indentation fracture resistance also increases with nitrogen content according to a power law relationship. These increases are consistent with the incorporation of N into the glass structure in threefold coordination with silicon resulting in extra cross‐linking of the glass network. This was confirmed using ²⁹Si MAS‐NMR which showed that an increasing number of Q² units and some Q³ units with extra bridging anions are formed as nitrogen content increases at the expense of Q¹ units. A small proportion of Zn ions are found to be in tetrahedral coordination in the base oxide glass and the proportion of these increases with the presence of nitrogen.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Phase Equilibrium Studies of “Cu2O”–SiO2–Al2O3 System in Equilibrium with Metallic Copper

Phase equilibria of the “Cu₂O”–Al₂O₃–SiO₂ system have been experimentally investigated at metallic copper saturation. High‐temperature equilibration, rapid quenching, and electron probe X‐ray microanalysis (EPMA) techniques have been used. Containerless equilibration technique has been developed to enable the phase equilibrium of this chemically reactive system to be investigated. The microstructures and compositions of all phases present in the quenched sample were measured accurately using EPMA. The isothermals between 1150°C and 1300°C have been determined in the “Cu₂O”–Al₂O₃–SiO₂ system at metallic copper saturation. The following primary phase fields were identified in the system: SiO₂ (tridymite), Cu₂O (cuprite), Cu₂O^.Al₂O₃ (delafossite), Al₂O₃ (corundum), and 3Al₂O₃·2SiO₂ (mullite). The implications of the phase diagram on making of the copper aluminosilicate glass have been demonstrated.     

New calcium‐free Na2O–Al2O3–P2O5 bioactive glasses with potential applications in bone tissue engineering

Sodium aluminophosphate glasses were evaluated for their bone repair ability. The glasses belonging to the system 45Na₂O–xAl₂O₃‐(55‐x)P₂O₅, with x = (3, 5, 7, 10 mol%) were prepared by a melt‐quenching method. We assessed the effect of Al₂O₃ content on the properties of Na₂O–Al₂O₃–P₂O₅ (NAP) glasses, which were characterized by density measurements, DSC analyses, solubility, bioactivity in simulated body fluid and cytocompatibility with MG‐63 cells. To the best of our knowledge, this is the first investigation of calcium‐free Na₂O–Al₂O₃–P₂O₅ system glasses as bioactive materials for bone tissue engineering.     

Coupled Experimental and Thermodynamic Optimization of the Na2O–FeO–Fe2O3–Al2O3 System: Part 1. Phase Diagram Experiments

As part of the complete thermodynamic modeling of the Na₂O–FeO–Fe₂O₃–Al₂O₃ system, the Na₂O–FeO–Fe₂O₃–Al₂O₃ phase diagrams in air (1583 and 1698 K) and at Fe saturation (1573 and 1673 K) were investigated using the quenching method followed by Electron Probe Micro‐Analyzer (EPMA) and X‐ray Diffraction (XRD) phase analysis. General features of the phase diagrams in this system were well revealed for the first time. A complete meta‐oxide solid solution between NaAlO₂ and NaFeO₂ was observed. An extensive solid solution of Na₂(Al,Fe)₁₂O₁₉ Na‐β?‐alumina was found and the existence of a miscibility gap in this solution was confirmed. Several compatibility triangles of three‐phase assemblages were also identified in air and at Fe saturation.     

Selected Phase Equilibria Studies in the Al2O3–CaO–SiO2 System

The Al₂O₃–CaO–SiO₂ system provides the basis for describing many important chemical processes. Although the system has previously been extensively studied, recent advances in experimental technique have provided the opportunity to obtain accurate liquidus measurements in the low‐silica region at fixed temperatures. The experimental procedures involve equilibration of high‐purity oxide powder mixtures at selected temperatures, rapid quenching, and accurate measurement of phase compositions using electron probe X‐ray microanalysis. The liquidus isotherms have been determined at selected temperatures between 1503 and 1873 K in the anorthite, gehlenite, pseudowollastonite, corundum, CaAl₁₂O₁₉, CaAl₂O₆, lime, Ca₃SiO₃, and Ca₂SiO₄ primary phase fields. The results are compared with currently available thermodynamic model predictions of the phase chemistry.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

Microwave Processing for Improved Ionic Conductivity in Li2O–Al2O3–TiO2–P2O5 Glass‐Ceramics

Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) was synthesized using a glass‐ceramics approach through crystallization in a conventional box furnace and a modified microwave furnace. The microstructure of samples that were microwave processed at 1000°C showed a larger average grain size (0.87 μm) when compared with the grain size of conventionally processed samples (0.30 μm) at the same temperature. Microwave processing led to significant enhancement of the conductivity when compared with conventional processing for all crystallization temperatures investigated. The highest total conductivity achieved was of glass microwave processed at 1000°C, with a conductivity of 5.33 × 10^?4 S/cm. This conductivity was five times higher than that of LATP crystallized conventionally at the same temperature.     

Discharged Energy Properties of SrO–PbO–Na2O–Nb2O5–SiO2 Glass‐Ceramics with Different Crystallization Time

Discharged energy properties of PbO–SrO–Na₂O–Nb₂O₅–SiO₂ glass‐ceramics with crystallization time from 1 to 1000 min were investigated by measuring their hysteresis loops (described as quasi‐static measuring method) and pulse‐discharge current‐time curves (described as dynamic measuring method). The results show the same trend for both measuring methods: With the increment of crystallization time, the discharged energy density increases gradually, while the energy efficiency decreases. The highest energy efficiencies were obtained in the sample with crystallization time of 1 min, which are 96.3% and 82.4%, corresponding quasi‐static and dynamic measurement, respectively. The reduction of energy efficiency with crystallization time is attributed to combined effect of ferroelectric polarization and interfacial polarization, and part of the corresponding energy could not release in the pulse‐discharge process.     

Sintering and Dielectric Properties of Li2O–B2O3–Al2O3–SiO2 Glass‐Added (Ca0.7Sr0.3O)1.03(Ti0.1Zr0.9)O2 for Copper Electrode

When 1.5 wt% of Li₂O–B₂O₃–SiO₂ and 1.5 wt% of Li₂O–B₂O₃–Al₂O₃ glass‐added (Ca_0.7Sr_0.3O)_1.03(Ti_0.1Zr_0.9)O₂ batch was ball milled for 10~30 h followed by sintering at 950°C in flowing N₂‐10%H₂ atmosphere, an apparent density of approximately 4.5 g/cm³, a dielectric constant of approximately 26, and a quality factor of roughly about 3300 GHz were demonstrated. A prolonged ball mill time thereafter significantly decreased both of the dielectric properties because of the enhanced reduction of the specimens during sintering. The apparent evidence of a material reaction between the dielectric material and the copper electrode was not observed.     

Joining of Porous Alumina with a CaO–Al2O3–SiO2 Glass‐Ceramic

A CaO–Al₂O₃–SiO₂ (CAS)‐based glass interlayer was developed for joining of porous alumina membrane tubes with dense alumina in this work. The results indicated that the interfacial microstructure of the joint was highly sensitive to the quench rate from the joining temperature, which rendered crystallization of CaTiSiO₅ at a fast quench rate but CaAl₂Si₂O₈ at a slow quench rate due to the interfacial reaction between the CAS glass interlayer and the substrate. An extra crystallization treatment during quench, i.e., dwelling at 800°C–900°C for 2 h, produced a multiphase interlayer consisting of LiAlSi₂O₆, CaTiSiO₅, and CaAl₂Si₂O₈. All joints were evaluated by the thermal shock test. The results showed that the LiAlSi₂O₆‐containing joint interlayer had much lower thermal shock resistance than those without LiAlSi₂O₆.     

Thermodynamic Modeling of the HfO2–La2O3–Al2O3 System

Based on phase equilibria, thermodynamic, and crystal structure data, the thermodynamic modeling of HfO₂–La₂O₃–Al₂O₃ system is presented. Liquid phase is described by the modified quasichemical model considering the short‐range ordering in liquid solution. Solid solutions are described by the ionic sublattice model considering respective crystal structure. The model (La³⁺, Hf⁴⁺)₂(Hf⁴⁺, La³⁺)₂(O^2?, Va)₆(O^2?)₁(Va, O^2?)₁ successfully describes the structure defect, homogeneity range, and thermodynamic property of pyrochlore solid solution. A set of optimized model parameters is obtained which reproduces most experimental data well. Isothermal sections, liquidus and solidus projections, and Scheil reaction scheme are constructed.     

Energetics of Silica‐Poor Glasses in the Systems MgO–SiO2 and Mg0.5Ca0.5O–SiO2

A series of alkaline‐earth silicate glasses, with compositions ranging from the metasilicate to the ortho‐ and suborthosilicate, have been synthesized by aerodynamic levitation and CO₂ laser melting. They have been studied by high‐temperature oxide melt solution calorimetry with 2PbO·B₂O₃ as solvent. The enthalpies of formation from the oxides at room temperature () have been calculated from the solution enthalpies. Glasses in the Ca_0.5Mg_0.5O–SiO₂ system show greater energetic stability than those in the MgO–SiO₂ system, with a more pronounced negative enthalpy of mixing near the orthosilicate composition. This stabilization may explain why it is possible to prepare glasses poorer in silica (suborthosilicate) in the Ca_0.5Mg_0.5O–SiO₂ system but not in the MgO–SiO₂ system. The thermodynamic observations support earlier structural studies in these systems.     

Influence of the Eu2+ on the Silver Aggregates Formation in Ag+–Na+ Ion‐Exchanged Eu3+‐Doped Sodium–Aluminosilicate Glasses

Europium‐doping sodium–aluminosilicate glasses are prepared by melt‐quenching method, in which europium ions were spontaneously reduced from their trivalent to divalent state. The silver was introduced into glasses by Ag⁺–Na⁺ ion exchange and the interactions between europium ions and silver species were investigated. Owing to energy transfer (ET) from Ag⁺/silver aggregates to Eu³⁺, significant enhancements of Eu³⁺ emission were observed for 285/350‐nm excitation, respectively. The divalent europium ions promote the formation of silver aggregates in the process of ion exchange.     

Thermal Conductivity of Molten Li2O–B2O3 and K2O–B2O3 Systems

Using the transient hot‐wire method, the thermal conductivity properties of the molten Li₂O–B₂O₃ and K₂O–B₂O₃ systems were measured. The thermal conductivity increases with decreasing the temperature due to the borate structure change. In addition, calculations of the one‐dimensional Debye temperature and the phonon mean free paths as a function of temperature of the alkali borate systems were made. At a fixed temperature of 1273 K, the effect of the alkali oxide concentration on the thermal conductivity was evaluated. Within a range of 10–30 mol% Li₂O (or K₂O), a positive relationship between the thermal conductivity and 4‐coordinate boron was obtained. However, below 10 mol% Li₂O (or K₂O), the change in the intermediate‐range order of the borate structure had a more dominant effect on the thermal conductivity. Finally, the effect of cations on the thermal conductivity in the various molten R₂O–B₂O₃ (R=Li, Na and K) systems was considered. Depending on the type of cation, the change in the ionization potential had an effect on the thermal conductivity and also resulted in a change in the bond strength.