Reduction of Eu3+ to Eu2+ in Aluminoborosilicate Glasses Prepared in Air

Eu₂O₃-doped aluminoborosilicate glasses were prepared in air at high temperature. Luminescence measurements were used to investigate a valence change from Eu³⁺ to Eu²⁺ ions in the aluminoborosilicate glasses. The results showed that the doped Eu³⁺ ions were partially reduced to Eu²⁺ in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=CaO, SrO, BaO, Li₂O) glasses, but not in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=Na₂O, K₂O) glasses. The changes of Eu reduction with different RO components were discussed with the variation of optical basicity of RO and with different valency of R cations. The effects of co-doping BaO and ZnO in aluminoborosilicate glasses on Eu reduction were also investigated and discussed.     

Long-Lasting Phosphorescence of Transparent Surface-Crystallized Glass-Ceramics

Transparent surface-crystallized glass-ceramics with molar compositions of 43SiO₂–2B₂O₃–30SrO–25MgO–0.05Eu₂O₃–0.8Dy₂O₃ (sample GC-A) and 43SiO₂–2B₂O₃–24SrO–6CaO–25MgO–0.05Eu₂O₃–0.8Dy₂O₃ (sample GC-B) were prepared by heat-treating the mother glasses at 850°C for 10 h. The precipitated phases in both glass-ceramics were (Sr_{1− x} Ca _x )₂MgSi₂O₇, in which Eu²⁺ and Dy³⁺ ions were incorporated. Phosphorescence with emission peaks at 470 and 480 nm that is due to the 4 f ⁶5 d –4 f ⁷ transition of Eu²⁺ ions was observed from samples GC-A and GC-B, respectively. The phosphorescence lasted for >5 h at room temperature.     

Processing and Properties of Eu3+:LiTaO3 TransparentGlass–Ceramic Nanocomposites

We report here the processing and properties of transparent glass and glass–ceramic nanocomposites in the Li₂O–Ta₂O₅–SiO₂–Al₂O₃ system in the presence of Eu₂O₃ as luminescent probe. The formation of the LiTaO₃ crystal phase, the crystallite size, and the morphology with the progression of heat treatment have been examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transformed infrared reflectance spectroscopy measurements. The crystallite sizes obtained from XRD and TEM are found to increase with heat-treatment time and vary in the range of 2–20 nm. The measured photoluminescence spectra exhibit emission transitions of ⁵D_0,1→⁷F _j ( j =0, 1, 2, 3, and 4) of Eu³⁺ ions. From the nature of the emission transitions, the site symmetry in the vicinity of Eu³⁺ ions has been found to be near C_3v in the glass–ceramic nanocomposites. An inverse correlation has been observed between the asymmetric ratio ( I _ED/ I _MD) of Eu³⁺ ions and the dielectric constant (ɛ_r), with an increase in the heat-treatment time of glass, which is caused by the dipole–dipole interaction.     

X-ray Diffraction and 151Eu Mössbauer Spectroscopic Study of the Hf1−xEuxO2−x/2(0 ≤x≤ 1.0) System

Powder X-ray diffractometry (XRD) and ¹⁵¹Eu Mössbauer spectroscopy were performed for samples prepared in the temperature range 1500–1500°C for the hafnia–europia (HfO₂–Eu₂O₃) system Eu _x Hf_{1− x} O_{2− x /2}(0 ≤ x ≤ 1.0). The XRD results showed that two types of solid solution phases formed in the composition range 0.25 ≤ x ≤ 0.725: an ordered pyrochlore-type phase in the middle-composition range (0.45 < x < 0.575) and a disordered fluorite-type phase, enveloping the pyrochlore-type phase on both sides, in the composition ranges 0.25 ≤ x ≤ 0.40 and 0.60 ≤ x ≤ 0.725. ¹⁵¹Eu Mössbauer spectroscopy sensitively probes local environmental changes around trivalent europium (Eu³⁺) caused by the formation of these solid solution phases. In addition to the broad, single Mössbauer spectra observed in this study for the Eu³⁺, the values of isomer shift (IS) exhibited a pronounced minimum in the neighborhood of the stoichiometric pyrochlore phase ( x ≈ 0.5). Such IS behavior of Eu³⁺ was interpreted based on the XRD crystallographic information that the ordered pyrochlore phase has a longer (in fact, the longest) average Eu–O bond length than those of the disordered fluorite phases on both sides or the monoclinic (and C-type) Eu₂O₃at x = 1.0.     

Mössbauer Spectroscopy of Borate Glasses Containing Divalent Europium Ions

Borate glasses containing 0.99–30.0 mol% EuO have been prepared under a reducing atmosphere and ¹⁵¹Eu Mössbauer effect measurements have been carried out at room temperature in order to examine the chemical state of Eu²⁺ ions in these glasses. Mössbauer spectra indicate that most of the europium ions are present as the divalent oxidation state. In dilute Eu²⁺-containing borate glasses, spectra are split due to paramagnetic hyperfine interactions in the glasses with low and high sodium contents. In concentrated Eu²⁺-containing borate glasses, line broadening results from the contribution of quadrupole splitting due to asymmetrical oxygen coordination around Eu²⁺ and the contribution of inhomogeneous broadening due to site-to-site variation. The compositional dependence of isomer shift and quadrupole interaction parameter can be related to the structural changes in the borate glass. The variation of the isomer shift has a good correlation with the optical basicity of glass, and the trend can be explained in terms of the covalent admixture with 6 s character. The Eu-O bond in the borate glasses is more ionic than that in EuTiO₃ and EuZrO₃, where the oxygen coordination number for Eu²⁺ is 12. The average coordination number for Eu²⁺ is found to be 12 in all of the present glasses.     

Preparation and Faraday Rotation of Divalent Europium Glasses

A large glass-forming region was discovered in the system EUO–Al₂O₃–B₂O₃ and chemically stable glasses of good optical quality were produced. The concentration range extends from about 3 to 43 mole % EuO. Room-temperature Verdet constants as large as –2.55 min/oe-cm were measured on a glass containing 30.5 mole % Eu²⁺. This is somewhat higher than those reported for the trivalent rare-earth ions in similar glass matrices. The effective transition wavelength causing the rotation is 380 ± 20 mμ. Compared to Ce³⁺, Tb³⁺, and Pr³⁺ the large rotation of Eu²⁺ in the visible region is due primarily to a large J (total angular momentum) value as well as to a large effective transition wavelength.     

Photochemical Hole Burning and Local Structural Change in Sm2+-Doped Borate Glasses

Photochemical hole burning (PHB) not only can be applied for data storage systems but also serves as a powerful method for studying the local structure around optical centers. The present work investigated the effects of aluminum, magnesium, and silicon ions on hole burning and the phonon sideband for borate glasses that exhibit PHB at room temperature. Hole burning was measured for the ⁵ D ₀₋₇ F ₀ transition of Sm²⁺ and the phonon sideband spectrum for the ⁵ D ₀-⁷ F ₀ transition of Eu³⁺. The hole width was closely related to local structural change, especially as it seemed to decrease with decreases in the number of nonbridging oxygens produced around the rare-earth ions. In the case of sodium aluminoborate glasses, the hole width decreased considerably with increasing alumina content. The ratio Γ_ih/Γ_h for 85B₂O3·10Al₂O₃·5Na₂O·1Sm₂O₃ glass, then, was 80 at room temperature, the largest value ever reported.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O were heated in air at 500°C, then reacted with H₂ gas to form Sm²⁺ ions. Whereas Al³⁺ ions effectively dispersed the Sm³⁺ ions in the glass structure, Na⁺ ions were not effective. The Al₂O₃-SiO₂ glasses proved appropriate for reacting the Sm³⁺ ions with H₂ gas and exhibited the intense photoluminescence of Sm²⁺ ions. The reaction of Sm³⁺ ions with H₂ in the Al₂O₂-SiO₂ glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm²⁺ ions was achieved within 20 min.     

Cation Effects on Anion Distributions in Aluminophosphate Glasses

Alkali aluminophosphate glasses, including those in the system x Al₂O₃·(1− x )CsPO₃ (0 ≤ x ≤ 0.25), were examined by high-performance liquid chromatography (HPLC), infrared (IR), and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies. Phosphate anions become progressively shorter with the addition of alumina to a metaphosphate glass. Al³⁺ ions are initially incorporated into the structure in octahedral sites, but the average Al coordination number (CN) decreases with increasing alumina content and tetrahedral species are the preferred moiety when [O]/[P] > 3.5. Al[4] sites appear to be associated with monophosphate (Q⁰) anions. The role of modifier size on aluminophosphate structure is investigated. At low alumina content (<15 mol%), the disproportionation of pyrophosphate anions into triphosphate and orthophosphate anions is responsible for the lower average Al CN of cesium aluminophosphate glasses compared with sodium aluminophosphate glasses.     

Effect of Composition on the Mechanical Properties of Aluminosilicate and Borosilicate Glasses

Elastic moduli and fracture toughness were determined for several glasses in the systems soda-alumina-silica, calcia-alumina-silica, and soda-boric oxide-silica. Results for the aluminosilicates are analyzed in terms of Al³⁺:Na⁺ ratios. The mechanical properties do not show maxima or minima at the Al³⁺:Na⁺ ratio of 1, in contrast to conductivity, helium permeability, and refractive index. The moduli and toughness increase with Al³⁺:Na⁺ ratio, which is consistent with increased coherency of the glass network. Glasses which contain B₂O₃ instead of Al₂O₃ have slightly higher moduli but are considerably tougher. The moduli of calcium aluminosilicate glasses are ∼25% greater than sodium aluminosilicates, whereas the fracture toughnesses are similar.     

Crystal Chemistry of Hydrous Calcium Silicates: I, Substitution of Aluminum in Lattice of Tobermorite

Mixtures of 0.8 moles of CaO per mole of SiO₂ plus Al₂O₃ were prepared from lime, kaolin, and tripoli (microcrystalline quartz); the amounts of SiO₂ to Al₂O₃ were varied to give from 0.2 to 20.7% Al₂O₃ by weight of dry solids. After hydrothermal treatment (170° to 175°C.), the products were examined by differential thermal analysis and by X-ray diffraction. A homogeneous solid identified as the mineral tobermorite (4CaO.5SiO₂.5H₂O) and containing up to 4 or 5% Al₂O₃ was obtained. Increasing the amount of Al₂O₃ in the raw mixture above about 5% resulted in the formation of the hydrogarnet 3CaO.Al₂O₃.SiO₂.4H₂O as a second phase. Allowing for the Al₂O₃ combined in this solid, it was indicated that slightly more Al₂O₃ was substituted in the tobermorite as the amount was increased in the raw mixture. It is suggested that the Al³⁺ ions probably assume tetrahedral coordination when substituting for the Si⁴⁺ ions.     

Molecular Dynamic Simulation of Eu3+ -Doped Sodium Borate Glasses and Their Fluorescence Spectra

A molecular dynamic simulation was performed for sodium borate glasses containing a small amount of Eu₂O₃ to investigate the local structures of cations in glass. A new potential V_B-B in the form -A exp[-C(r - 0.239)²] was added to the regular modified Born-Mayer-Huggins-type potentials, Φ_B-B, Φ^B-O, and ΦO-O, to account for the directional tendency of the borate network structure. With this potential added, both the radial distribution of sodium borate glasses observed by small-angle X-ray diffraction and the change in coordination number of boron with sodium content obtained by NMR agreed well with the simulation. The average coordination number of Ed³⁺ ions in the simulated glasses varied from 7.5 to 8.6, depending on the composition of the host sodium borate glasses. The inhomogeneous line width of the ⁵D₀-⁷F_z emission peak also changed, depending on the sodium content, with a maximum at 18 mol% Na_zO content; this result agrees well with experimental data obtained from laser-induced fluorescence spectra.     

Coordination of Aluminum Ions in Tricalcium Aluminate

The coordination of aluminum ions in tricalcium aluminate (3CaO·Al₂O₃) was examined using infrared absorption, X-ray emission spectroscopy, and molar refraction techniques. Each of these methods indicated the presence of aluminum in fourfold coordination. No evidence was found for aluminum in sixfold coordination. The isomorphous substitution of Sr²⁺ for Ca²⁺ and Ga³⁺ for Al³⁺ and a comparison between the absorption frequencies for an SiO₄ group and an AlO₄ group were used to identify the infrared absorption bands in tricalcium aluminate.     

Spectroscopic Properties and Local Structure of Eu3+ in Ge–Ga–S–CsBr (or CsCl) Glasses

Spectroscopic properties and local structure of Eu³⁺ in Ge–Ga–S–CsBr (or CsCl) glasses were investigated using fluorescence measurements and several spectroscopic methods. Fluorescence from Eu³⁺:⁵D₀→⁷F₂ was observed only from glasses with CsBr/Ga ratios greater than unity and disappeared at temperatures above 140 K. Phonon sideband (PSB) spectra revealed that Eu³⁺ ions are located next to halogen ions, which form part of well-structured complexes such as EuCl₃, tetrahedral [GaS_3/2Cl]⁻, subunits and/or Ga₂Cl₆. These new bonds showed reduced coupling strength compared with Eu³⁺–S bonds in Ge–Ga–S glass. Fluorescence line narrowing experiments showed little site-to-site variation of Eu³⁺ ions.     

Synthesis and Photoluminescence Properties of Eu3+-Doped Calcium Phosphates

Eu³⁺-doped (1–12 mol%) calcium hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) powders were synthesized by a precipitation method and their photoluminescence (PL) properties were investigated. Eu has a limited solubility in HA and Eu₂O₃ was detected by X-ray diffraction above 3% doping, whereas a nearly single β-phase was obtained up to 6% doping in TCP but EuPO₄ appeared in the 12% Eu-doped specimen. Electron spin resonance measurement confirmed that europium ions exist as Eu³⁺ in both samples. Eu³⁺-doped HA exhibited a strong emission at 575 nm with several minor peaks at 610–640 nm and Eu³⁺-doped TCP had an intense emission at 613 nm with secondary peaks at 590–600 nm, which were consistent with the earlier reports determined at low temperatures. In Eu-doped TCP, the PL intensity increased with increasing calcination temperature without phase transformation. The more the Eu added, the higher the PL intensity obtained in both cases.     

Redox Equilibria of Multivalent Ions in Silicate Glasses

Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO₂, TiO₂, Al₂O₃, CaO, MgO, and Na₂O. The proposed model describes the Eu²⁺/Eu³⁺ ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe²⁺-Fe³⁺, Ce³⁺-Ce⁴⁺, and Cr³⁺-Cr⁶⁺ redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.     

Structure of Liquid Al6Si2O13 (3:2 Mullite)

We report the first measurements of the structure factor, S ( Q ), and the pair distribution function, G ( r ), of Al₆Si₂O₁₃ (3:2 mullite) in the normal and supercooled liquid states in the temperature range 1776–2203 K. Measurements are obtained by synchrotron X-ray scattering on levitated, laser-heated liquid specimens. The S ( Q ) shows a prepeak at 2.0 Å⁻¹ followed by a main peak at 4.5 Å⁻¹ and a weak feature at 8 Å⁻¹. The G ( r ) shows a strong (Si,Al)–O correlation at 1.80 Å at high temperature that moves to 1.72 Å as the liquid is supercooled. The second and third nearest neighbor peaks at 3.0 and 4.25 Å sharpen with supercooling. The short-range structure of the high-temperature liquid is similar to the corresponding glasses produced by rapid quenching. Supercooling causes an increase in the concentration of tetrahedral Si⁴⁺ ions, which is manifested by the large shift in the first peak to lower ionic distance, r , values in G ( r ). The increase in tetrahedrally coordinated Si⁴⁺ ions is offset by an increase in octahedral Al³⁺ ions. The clustering of the SiO₄⁴⁻ tetrahedral units results in increased viscosity of the liquid at temperatures below the melting point, which is consistent with Al₆Si₂O₁₃ being a fragile liquid.     

Interdiffusion and Association Phenomena in the System NiO-Al2O3

The rate of formation of NiAl₂O₄ by reaction between single crystals of NiO and Al₂O₃ can be described by k = 1.1 × 10⁴ exp (−108,000 ± 5,000/ RT ) cm²/s. In NiO the behavior of D as a function of concentration supports the Lidiard theory of diffusion by impurity-vacancy pairs. A good fit of the theory to the experimental results was obtained by assuming that Al³⁺ ions diffuse as [Al_Ni· V_Ni]'pairs. The diffusion coefficient of pairs, D_p , obeys the equation 6.6 × 10⁻² exp (−54,000 ± 3,000/ RT ) cm²/s. The free energy of association for pairs was calculated to range from 6.5 kcal/mol at 1789°C to 9.0 kcal/mol at 1540°C. The interdiffusion coefficients in the spinel showed a constant small increase with increasing concentration of Al³⁺ dissolved in the spinel.     

Interdiffusion in the System MgO-MgAl2O4

Interdiffusion coefficients in single-crystal MgO were determined using an MgO-MgAl₂O₄ diffusion couple. For a concentration of 1 mol% Al₂O₃ in MgO, the interdiffusion coefficient can be expressed as D =2.0±0.2 exp (−76,000±3,000/ RT ) for the MgO-MgAl₂O₄ couple. This relation compares well with previous measurements in the MgO-Al₂O₃ system. The interdiffusion coefficients, which increased with the mol fraction of cation vacancies, were in the range of 10⁻⁸ to 10⁻¹⁰ cm²s⁻¹ for the concentrations and temperatures studied. Diffusion was enhanced below 1640°C if powdered MgAl₂O₄ was used. Self-diffusion coefficients for Al³⁺ ions in MgO were calculated; Al³⁺ diffuses faster than Cr³⁺ in MgO.     

Energy Transfer and Population Inversion in Heavy Metal Oxide Glasses Doped with Tm3+ and Tb3+

Emission properties and energy transfer of PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses codoped with Tm³⁺ and Tb³⁺ ions were investigated. The 1.48-μm emission due to the Tm³⁺:³H₄→³F₄ transition can be used to amplify the S-band (1460–1530-nm) signal light. With Tb³⁺ addition, the lifetime and emission intensity of the Tm³⁺:³F₄ level decreased sharply via the Tm³⁺:³F₄→Tb³⁺:⁷F_0,1,2 energy transfer. Population densities of the ³F₄ and ³H₄ levels in Tm³⁺ calculated from rate equations clearly verified that population inversion in Tm³⁺ ions became possible with as little as 0.1 mol% of Tb³⁺ addition.