Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.     

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.     

Effect of Ta2O5 Substituting on Thermal and Optical Properties of High Refractive Index La2O3–Nb2O5 Glass System Prepared by Aerodynamic Levitation Method

High refractive index glasses with nominal composition of 0.35La₂O₃–(0.65?x)Nb₂O₅–xTa₂O₅ (x ≤ 0.35) were prepared by aerodynamic levitation method. The effect of Ta₂O₅ substituting on their thermal and optical properties was investigated. All the glasses obtained were colorless and transparent. Differential thermal analyzer results show that as the content of Ta₂O₅ increased, the thermal stability of the glasses increased but the glass‐forming ability decreased. The transmittance spectra of all the obtained glasses exhibited a wide transmittance window ranging from 380 to 5500 nm. As the content of Ta₂O₅ increased, the refractive index of the glasses was enhanced from 2.15 to 2.21 and the dispersion was reduced with the Abbe number increasing from 20 to 27.     

BaO-TiO2-SiO2系统高折射率光学玻璃

以BaO-TiO2-SiO2-RmOn系统为研究对象。在SiO2质量百分含量分别为15%、12%、10%时,改变BaO/TiO2的比值,得到一组高折射率光学玻璃。测试玻璃的密度、折射率、阿贝数和紫外到红外波段的透过率等物化性质,研究密度和折射率与组成的关系及影响阿贝数、透过率大小的因素。结果表明,密度随BaO/TiO2比值的增加先增加后减小,折射率随BaO/TiO2比值的增加而减小,折射率和密度变化趋势不一致。TiO2含量是影响阿贝数和透过率大小的主要因素。     

Enhanced Thermostability,Thermo‐Optics,and Thermomechanical Properties of Barium Gallo‐Germanium Oxyfluoride Glasses and Glass‐Ceramics

Serial substitutions of BaF₂ for BaO in BaO–Ga₂O₃–GeO₂ glasses were performed, and the effects of the substitutions on the glass properties were investigated. The glass transition temperature, density, refractive index, thermo‐optics coefficient, and figure of merit for thermal shock decreased with the replacement of oxygen by fluorine. On the other hand, the glass‐forming ability increased. Fluorine substitution removed the absorption band of hydroxyl near 2.9 μm. Raman scattering spectroscopy was used to characterize the fluorogermanate glasses. The crystallization process of the glass‐ceramics under different heat‐treatment conditions was also investigated using differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and atomic force microscopy. The thermal and mechanical properties were improved by controlling the crystal size of the near‐ and middle‐infrared transparent glass‐ceramics.     

Quantitative prediction of the glass-forming region and luminescence properties in Tm3+-doped germanate laser glasses

Germanate laser glasses have received much attention as a promising host materials for mid-infrared fiber lasers in recent years because of the outstanding infrared transparency, low phonon energy, and high rare earth solubility of such glasses. However, the development of high-performance germanate laser glasses is usually based on intuition and a trial-and-error method, which can involve long experimental periods and high costs, and thus, this approach is highly inefficient. Recently, with proposals for materials genome engineering, the concept of the “glass genome” has grown of interest to us. Herein, the structures of Tm³⁺-doped germanate laser glasses (BaO–GeO₂ and BaO–La₂O₃–GeO₂) were investigated by Fourier transform infrared spectra (FTIR) and Raman spectra analyses, which revealed that the resulting glass contains similar structural groups to the neighboring congruently melted glassy compounds (NCMGCs) in the composition diagram. What is more, the structure and properties of the resulting laser glasses largely depend on NCMGCs. Then, the glass-forming region, physical properties, and luminescence properties were calculated via the use of NCMGCs in Tm³⁺-doped BaO–GeO₂ binary and BaO–La₂O₃–GeO₂ ternary laser glass systems. The calculated results were in good agreement with the experimental results, thus demonstrating that our approach is practical for predicting the glass-forming region, physical properties, and luminescence properties in Tm³⁺-doped BaO–GeO₂ binary and BaO–La₂O₃–GeO₂ ternary laser glass systems. This work may provide an effective method to develop Tm³⁺-doped germanate laser glasses rapidly and at low cost.     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Thermal properties of ecological phosphate and silicate glasses

The present work deals with ecological phosphate and silicate glasses that belong to the oxide systems: Li₂O-MgO-P₂O₅, Li₂O-CaO-P₂O₅, Li₂O-MgO-P₂O₅-Fe₂O₃; Li₂O-CaO-P₂O₅-Fe₂O₃ and SiO₂-R₂O-R′O (R = Na, K; R′ = Mg, Ca), the last system contains certain amounts of ZrO₂, ZnO, TiO₂. These ecological glasses do not contain toxic substances as BaO, PbO, As₂O₃, As₂O₅, fluorine, CdS, CdSe and they have applications as regards the retention and counteracting action of the harmful compounds resulted from the nuclear plants. The replacement of MgO by CaO leads to an insignificant increasing of the thermal expansion index and a slight decreasing of the characteristic temperatures, except the softening point where the effect is opposite. Adding of iron oxide in the phosphate glass composition causes the increasing of characteristic temperatures and the decreasing of thermal expansion index, both in MgO and CaO-containing phosphate glasses. The ecological silicate glasses are used as opal glasses free of fluorine as well as for lead-free crystal glass (CFP) where BaO and PbO are replaced by non-toxic oxides as K₂O, MgO, ZrO₂, and TiO₂. The paper presents different glass compositions and the technological parameters to prepare the ecological glass samples. Both ecological phosphate and silicate glasses have been characterized as regards the characteristic temperatures (vitreous transition point, low and high annealing points, softening point) and the thermal expansion coefficient. This study presents the changes of the thermal parameters when CaO replaces MgO in phosphate glass samples and the role of iron oxide in the vitreous network. In the case of silicate glasses, the viscosity and wetting angle dependency of temperature are presented. The elemental analysis of the ecological glasses was made by XPS (X-ray photoelectron spectroscopy) which also put in evidence the iron species from the vitreous network.     

Optical Properties of Silver Halide Photochromic Glasses Doped with Cobalt Oxide

Photochromic glasses having composition (SiO₂)₄₅(B₂ O ₃)₃₅(Al₂O₃)_7.5(Na₂O)_12.5(AgBr), (Cu₂O) doped with (CoO) _x , in which, x = 0, 0.006, 0.02 and 0.07 g were prepared using the conventional melt technique. The amorphous nature of these glass samples was confirmed using X-ray diffraction analysis at room temperature. The absorption measurements in the infrared region of the spectrum were recorded in the wave number range (4000–400) cm^?1. Spectral reflectance and transmittance at normal incidence of the prepared glass samples were recorded with a spectrophotometer in the spectral range 200–2500 nm. Experimental and theoretical densities of the prepared glass samples were measured, calculated and compared. Analytical expressions were used to calculate the real and imaginary parts of the refractive indices. Dispersion parameters such as: single oscillator energy, dispersion energy, average oscillator wavelength, and Abbe’s number were deduced and compared. Absorption dispersion parameters such as: optical energy gap for direct and indirect transitions, Urbach energy and steepness parameter were calculated. Effects of doping with cobalt oxide CoO as a transition metal on linear and predicted nonlinear optical parameters were investigated and interpreted. Experimental results indicate that there is an optimum concentration of cobalt doping around 0.006 g. The optical band gap decreases with increasing doping and causes an increase in nonlinear optical parameters. Doping with cobalt oxide improves the linear and nonlinear optical properties of the prepared glasses.     

Characterization of the low temperature firing BaO–B2O3–SiO2 glass: The effect of BaO content

In the low temperature sinterable glass system of BaO–B₂O₃–SiO₂, the structural changes of the glasses and the resultant changes in the properties of the glasses were examined as a function of BaO content. ¹¹B MAS-NMR analysis was conducted in order to examine the coordination number of borons in the glass. It showed that the amount of O₄ was greatest at 35 mol% of BaO. The glass transition temperature, hardness, thermal expansion coefficient and dielectric constant of the glasses were examined and the results were explained on the basis of the structural change.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Optical properties of novel oxyfluoride glasses on the systems of LaF3–LaO3/2–NbO5/2 and LaF3–LaO3/2–NbO5/2–AlO3/2

Oxyfluoride glasses of xLaF₃–(60 − x)LaO_3/2–40NbO_5/2 (x = 0, 5, 10, 35) and xLaF₃–(60 − x)LaO_3/2–30NbO_5/2–10AlO_3/2 (x = 0, 10, 20, 30) were prepared using a levitation technique. Both the glass-transition temperature, T_g, and onset crystallization temperature, T_c, were lowered by substituting a part of the oxygen with fluorine in the glasses. An appropriate amount of fluorine maximized the difference between the temperatures, ΔT (= T_c − T_g), indicating the improvement in the glass-forming ability. The atomic packing densities of the glasses were approximately 60%, which gradually increased with the fluorine content. The absorption edge of the glasses shifted toward the shorter wavelength region in the ultraviolet spectra and toward the longer region in the infrared spectra by fluorine substitution. In addition, in one of the oxyfluoride glasses, a wide transparency from 307 nm to 9.2 µm was realized. Furthermore, the glass exhibited superior optical properties, with a combination of a high refractive index, n_d, of 2.020 and low wavelength dispersion, v_d, of 30.1. The effect of fluorine substitution on the n_d and its v_d was analyzed using the Lorentz–Lorenz dispersion formula.     

High Glass Transition Temperature Barium Silicophosphate Glasses Designed with Topological Constraint Theory

Alkali‐free glasses have attracted tremendous attentions for their high glass transition temperature (T_g). Such a feature broadens their potential applications, especially in the area of high‐density and high‐power laser glasses. BaO–P₂O₅ glasses, as one of the major matrix materials due to its high‐T_g, can be applied in high‐power laser glasses. Introducing SiO₂ is an effective method to improve the thermal, refractive index, and mechanical properties of phosphate glasses. Herein, we studied the barium silicophosphate glasses with MAS NMR and the T_g was successfully calculated by the topological constraint theory. The designed glass (20BaO–26.7SiO₂–53.3P₂O₅, mol%) with a high T_g (789K) was prepared and it also exhibited high refractive index and high Vickers hardness, suggesting the barium silicophosphate glasses have widespread applications in high‐power laser glasses and optical fibers.     

Influence of fluorine source and TiO2 on glass ceramics based on red clay and magnesite

Abstract

Within the Fe₂O₃–BaO–Al₂O₃–SiO₂ glass system, the influence of different fluorine source and TiO₂ on the crystallisation behaviour and thermal expansion characteristics has been investigated. These aluminosilicate glasses, with different nucleation catalysts (TiO₂, AlF₃ and NH₄F), were successfully prepared from Saudi Arabia raw materials (red clay and magnesite). Thermal behaviour, crystalline phases, microstructures, and thermal expansion coefficient were studied by DTA, XRD, SEM techniques, as well as a dilatometer. Spinel, hexacelsian, monocelsian, kinoshitalite, and Ba-osumilite were developed in glass ceramic samples. Spinel was the early phase formed in all glasses; however, with increasing temperature, hexacelsian and kinoshitalite were developed in fluorine free glasses and fluorine containing glasses respectively. Ba-osumilite was developed and hexacelsian was converted into monocelsian during lengthy heat treatment at 1150°C. A bulk crystalline microstructure was obtained; however, a microscale structure was observed in fluorine free samples and a homogeneous nanoscale microstructure was developed in fluorine containing samples. The coefficient of thermal expansion (CTE) varied according to the phases and the heat treatment parameters. Development of spinel, hexacelsian and kinoshitalite in glass ceramic samples gave CTE values between 86·44 × 10^?7 and 52·53 × 10^?7°C^?1, whereas crystallisation of Ba-osumilite and monocelsian gave CTE values between 51·29 × 10^?7 and ?7·35 × 10^?7°C^?1.     

Eu‐, Tb‐, and Dy‐Doped Oxyfluoride Silicate Glasses for LED Applications

Luminescence glass is a potential candidate for the light‐emitting diodes (LEDs) applications. Here, we study the structural and optical properties of the Eu‐, Tb‐, and Dy‐doped oxyfluoride silicate glasses for LEDs by means of X‐ray diffraction, photoluminescence spectra, Commission Internationale de L'Eclairage (CIE) chromaticity coordinates, and correlated color temperatures (CCTs). The results show that the white light emission can be achieved in Eu/Tb/Dy codoped oxyfluoride silicate glasses under excitation by near‐ultraviolet light due to the simultaneous generation of blue, green, yellow, and red‐light wavelengths from Tb, Dy, and Eu ions. The optical performances can be tuned by varying the glass composition and excitation wavelength. Furthermore, we observed a remarkable emission spectral change for the Tb³⁺ single‐doped oxyfluoride silicate glasses. The ⁵D₃ emission of Tb³⁺ can be suppressed by introducing B₂O₃ into the glass. The conversion of Eu³⁺ to Eu²⁺ takes place in Eu single‐doped oxyfluoride aluminosilicate glasses. The creation of CaF₂ crystals enhances the conversion efficiency. In addition, energy transfers from Dy³⁺ to Tb³⁺ and Tb³⁺ to Eu³⁺ ions occurred in Eu/Tb/Dy codoped glasses, which can be confirmed by analyzing fluorescence spectra and energy level diagrams.     

Effect of Glass Refractive Index on Light Extraction Efficiency of Light‐Emitting Diodes

Light‐emitting‐diode (LED) encapsulants, such as epoxy and silicone resin, have a lower refractive index than YAG:Ce phosphor, and this is usually one of the major causes of LED inefficiency. To improve LED performance, a glass encapsulant is considered. In this study, the SiO₂–B₂O₃–ZnO glass system containing La₂O₃ and WO₃ was investigated as an encapsulant to minimize total internal reflection and to increase the light extraction efficiency of LED packages. The characterization of glass encapsulants was performed using a differential scanning calorimeter, a pycnometer, a prism coupler, X‐ray photoelectron spectroscopy, and integrating spheres. The refractive index increased linearly with increasing molar volume of glass because La₂O₃ and WO₃ act as modifiers in the glass, creating more nonbridging oxygen. The refractive index of glass increases with the content of La₂O₃ and WO₃, which is attributed to the increase in polarizability of oxide ions in the glass. When the refractive index between glass and phosphor matched, light extraction efficiency was maximized because total internal reflection decreased.     

Composition Dependence of Thermal Expansion and Glass Transition Temperature for Barium Aluminoborate Glasses

The glass transition temperatures and the thermal expansion coefficients below and above the glass transition range are determined for barium aluminoborate glasses over a wide range of compositions containing up to 60 mol % BaO and 35 mol % Al₂O₃. The behavior of these characteristics is studied depending on the Al₂O₃ concentration at constant BaO/B₂O₃ ratios (from 0.2 to 1) and upon replacement of B₂O₃ by BaO at constant Al₂O₃ contents (up to 30 mol %). The influence of composition on the properties is interpreted within the concepts of the barium aluminoborate glass structure.     

Interpreting the optical properties of oxide glasses with machine learning and Shapely additive explanations

Due to their excellent optical properties, glasses are used for various applications ranging from smartphone screens to telescopes. Developing compositions with tailored Abbe number (V_d) and refractive index at 587.6 nm (n_d), two crucial optical properties, is a major challenge. To this extent, machine learning (ML) approaches have been successfully used to develop composition–property models. However, these models are essentially black boxes in nature and suffer from the lack of interpretability. In this paper, we demonstrate the use of ML models to predict the composition-dependent variations of V_d and n_d. Further, using Shapely additive explanations (SHAP), we interpret the ML models to identify the contribution of each of the input components toward target prediction. We observe that glass formers such as SiO₂, B₂O₃, and P₂O₅ and intermediates such as TiO₂, PbO, and Bi₂O₃ play a significant role in controlling the optical properties. Interestingly, components contributing toward increasing the n_d are found to decrease the V_d and vice versa. Finally, we develop the Abbe diagram, using the ML models, allowing accelerated discovery of new glasses for optical properties beyond the experimental pareto front. Overall, employing explainable ML, we predict and interpret the compositional control on the optical properties of oxide glasses.     

Synthesis, structure, and dynamics of fluorine ions in glasses based on indium and bismuth trifluorides

The glass formation in the InF₃-BiF₃-BaF₂ system is investigated. It is shown that the introduction of BiF₃ into the glass composition brings about an increase in the chemical durability and the refractive index (up to 1.611 for the 35InF₃ · 30BiF₃ · 35BaF₂ glass). This makes it possible to consider these glasses as promising materials for cores of IR transparent optical fibers with a high aperture. The dynamics of fluorine ions in the temperature range 250–430 K and possible models for the structure of glasses containing indium, bismuth, and fluorine are analyzed.