Ionic Conductivity in Sodium–Alkaline Earth–Aluminosilicate Glasses

The effect of alkaline‐earth ions on Na transport in aluminosilicate glasses was studied by measuring ionic conductivity for a systematic compositional series of Na₂O–RO–Al₂O₃–SiO₂ glasses (R=Mg, Ca, Sr, Ba). The Na transport in aluminosilicate glass could be affected by compositional changes in aluminum coordination and nonbridging oxygen as well as physical properties such as dielectric constant, shear modulus, and ionic packing factor. Through careful experimental designs and measurements, the main determinants among these parameters were identified. ²⁷Al MAS‐NMR indicated that all aluminum species contained in these glasses are four‐coordinated. The activation energy for ion conductivity decreased with increasing aluminum content and decreasing ionic radii of the alkaline‐earth ion in the region where [Al] < [Na]. When the aluminum content exceeded the sodium content ([Al] > [Na]), the composition dependence of the activation energy depended on the specific alkaline earth. These results are explained based on variations in free volume and dielectric constant caused by structural changes around the AlO₄ charge compensation sites. These structure changes occur in response to the smaller size and higher field strength of the alkaline‐earth ions, and are most prevalent in the compositions which require bridging of two AlO₄ sites by the alkaline‐earth ion for charge compensation.     

Effect of Al Speciation on the Structure of High‐Al Steels Mold Fluxes Containing Fluoride

To design suitable mold fluxes for the casting of high‐Al steels, the structure of mold fluxes based on CaO–SiO₂, CaO–SiO₂–Al₂O₃, and CaO–Al₂O₃ was examined by Raman spectroscopy and magic‐angle spinning nuclear magnetic resonance. The results showed that Si atoms are replaced by Al atoms as the network formers with the increase in Al₂O₃ in the mold fluxes. This converts the silicate slags (CaO–SiO₂ mold fluxes) into aluminosilicates slags (CaO–SiO₂–Al₂O₃ or CaO–Al₂O₃ mold fluxes). The F^? ions in the mold flux containing Al₂O₃ are classified into three categories, according to function: Bridging F's, Nonbridging F's, and Free‐F's. The Al³⁺ ion holds three distinct coordination environments: ^IVAl, ^VAl, and ^VIAl. The addition of F affects the coordination environment of Al³⁺ to form AlO₃F and AlO₂F₂ that accommodate the network structure of slags. The network structure in the CaO–SiO₂ mold fluxes is mainly connected through Si–O–Si linkage. However, the network structure of the mold fluxes containing elevated content of Al₂O₃ is mainly connected through Si–O–Si, Al–O–Al, Al–O–Si, and Al–F–Al linkages. Hence, the structural characteristics of high‐Al steels mold fluxes must be considered during the designing step of the mold fluxes.     

Thermal,Structural, and Enhanced Photoluminescence Properties of Eu3+‐doped Transparent Willemite Glass–Ceramic Nanocomposites

The precursor glass in the ZnO–Al₂O₃–B₂O₃–SiO₂ (ZABS) system doped with Eu₂O₃ was prepared by the melt‐quench technique. The transparent willemite, Zn₂SiO₄ (ZS) glass–ceramic nanocomposites were derived from this precursor glass by a controlled crystallization process. The formation of willemite crystal phase, size, and morphology with increase in heat‐treatment time was examined by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) techniques. The average calculated crystallite size obtained from XRD is found to be in the range 18–70 nm whereas the grain size observed in FESEM is 50–250 nm. The refractive index value is decreased with increase in heat‐treatment time which is caused by the partial replacement of ZnO₄ units of ZS nanocrystals by AlO₄ units due to generation of vacancies. Fourier transform infrared (FTIR) reflection spectroscopy was used to evaluate its structural evolution. Vickers hardness study indicates marked improvement of hardness in the resultant glass‐ceramics compared with its precursor glass. The photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀→⁷F_j (j = 0, 1, 2, 3, and 4) and its excitation spectra show an intense absorption band at 395 nm. These spectra reveal that the luminescence performance of the glass–ceramic nanocomposites is enhanced up to 17‐fold with the process of heat treatment. This enhancement is caused by partitioning of Eu³⁺ ions into glassy phase instead of into the willemite crystals with progress of heat treatment. Such luminescent glass–ceramic nanocomposites are expected to find potential applications in solid‐state red lasers, phosphors, and optical display systems.     

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.     

Europium(II) in glasses of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-MnO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Triply and doubly charged states of europium are revealed by ¹⁵¹Eu Mössbauer spectroscopy in the structure of glasses of the composition (mol %) 19.5Al₂O₃, 31.5SiO₂, 26.5MnO, and 22.5Eu₂O₃. The isomer shifts in the Mössbauer spectra of Eu³⁺ and Eu²⁺ ions in the structure of glasses differ from the isomer shifts in the spectra of the Eu₂O₃ and EuO compounds. This difference is explained by the fact that the electron density at ¹⁵¹Eu nuclei is affected by the manganese and aluminum atoms, which are not bound directly to the europium atoms. The broadening of the spectra of the Eu²⁺ ions in glasses is caused by the nonuniform isomer shift.     

Improved Blue‐Emitting AlN:Eu2+ Phosphors by Alloying with GaN

A method is designed to improve the luminescence of AlN‐based phosphors by tuning the band structure and crystal structure due to alloying with GaN. The pure (Al,Ga)N:Eu phosphors were initially prepared by gas‐phase reaction in an NH₃ atmosphere. GaN alloying was used to expand the crystal lattice of AlN due to Ga³⁺ substituting for smaller Al³⁺ ions, making dissolution of Eu²⁺ easier. The dissolution of Ga in the AlN lattice was proven by the result of the Rietveld refinement and the increase in lattice parameters with increasing Ga content. To introduce other energy states mixing with the 5d states of Eu²⁺, Ga doping was also used to tune the band structure of AlN by acting on Eu²⁺ ions. The theoretical result was analyzed using the Cambridge Sequential Total Energy Package (CASTEP). According to the calculated total and atom resolved partial density of states, it was observed that the Ga 5p states contribute a large portion to the corresponding Eu²⁺ absorption band in (Al,Ga)N:Eu phosphors. As a consequence, an enhanced emission intensity at 470 nm and a high quantum efficiency for excitation at 330 nm was obtained despite of stronger thermal quenching of the (Al,Ga)N:Eu phosphors compared with AlN:Eu.     

The Effect of Alkali Ions on the Incorporation of Aluminum in the Calcium Silicate Hydrate (C–S–H) Phase Resulting from Portland Cement Hydration Studied by 29Si MAS NMR

The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by ²⁹Si MAS NMR. The principal difference between the three cements is their bulk Al₂O₃ contents and quantities of alkali (Na⁺ and K⁺) ions. ²⁹Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q²(1Al) sites. Analysis of the relative ²⁹Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO₄ tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si⁴⁺ by Al³⁺ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO₄ tetrahedra. This result is further supported by similar ²⁹Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO₂ solutions.     

High Fraction of Penta‐Coordinated Aluminum and Gallium in Lanthanum–Aluminum–Gallium Borates

This study is focused on structural changes induced by increasing treatment temperature of sol‐gel–derived La₂O₃?Al₂O₃?Ga₂O₃?5B₂O₃ system. The structure of samples heated for 30 min up to 900°C was investigated by X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and magic‐angle spinning nuclear magnetic resonance (MAS‐NMR) analysis of ²⁷Al, ¹¹B, and ⁷¹Ga nuclei. The vitreous structure is preserved inclusively after 800°C treatment, and starting with 850°C the only crystalline phase evidenced in XRD patterns is of LaAl_2.03B₄O_10.54 type, of La(Al,Ga)_2.03B₄O_10.54 composition. The FTIR results point out the presence of BO₃, AlO₄, and AlO₆, and starting with 800°C treatment also of BO₄ and AlO₅ structural units, but more detailed information related to boron, aluminum, and gallium environments is obtained from the analysis of MAS‐NMR data. These data evidenced in both amorphous xerogels and in crystallized samples a high fraction of penta‐coordinated aluminum and gallium.     

Viscosity and structure evolution of bearing-BaO slag melt with the low CaO/SiO2 mass ratio of 0.7

The effect of BaO on the viscosity of experimental slag with the CaO/SiO₂ ratio of 0.7 was studied based on the rotating cylinder method, and the structure evolution analysis was performed using Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and ²⁷Al MAS-NMR spectra. The results indicated that the viscosity of molten slag decreased gradually with BaO content rising from 0 wt.% and 5 wt.% due to the dominant effect of free O^2- rather than Ba²⁺. The viscous flow activation energy (Eη) of molten slag was calculated, presenting a similar change trend with that of viscosity. The structure analysis demonstrated that, with the increasing BaO content, the [SiO₄]-tetrahedral structures and Si-O-Al bonds were destroyed due to an increase in the relative fraction of free oxygen (O^2-). For the Al-related structural units, the ²⁷Al magic angles spinning nuclear magnetic resonance (²⁷Al MAS NMR) spectra analysis illustrated that the concentration of [AlO₄] units reduced, whereas that of [AlO₅] and [AlO₆] units increased because of the increase of free oxygen and nonbridged oxygen (O⁰). The results of structure analysis agreed well with the viscosity variations of experimental slag.     

Energy transfer to Eu(III) in the solid‐state low‐density polyethylene–poly(acrylic acid) and low‐density polyethylene–Fe2O3–poly(acrylic acid) matrices

Ion exchange between H⁺ and Eu³⁺ and/or Tb³⁺ was studied in the material modified by in situ sorption and thermal polymerization of acrylic acid in low‐density polyethylene (LDPE–PAA) and in the composite system LDPE–Fe₂O₃–PAA. Fluorescence spectroscopy showed evidence of Eu³⁺ and/or Tb³⁺ ion exchanges in these materials. The matrix LDPE–PAA after Eu(III) ion exchange presented luminescence (excitation 265 nm). This was explained by an energy‐transfer process from the matrix LDPE–PAA to Eu³⁺ ions. The LDPE–PAA matrix after simultaneous Eu³⁺/Tb³⁺ ion exchange exhibited Eu³⁺ and Tb³⁺ ion luminescence (excitation 265 nm), confirming an energy‐transfer process from LDPE–PAA to Eu³⁺ ions in LDPE–PAA–Eu³⁺–Tb³⁺ matrix. Fe₂O₃ in LDPE–Fe₂O₃–PAA quenched the matrix for excitation at 265 nm and no emission at the region 400 nm was observed. The luminescence of Tb³⁺ ions in the matrix LDPE–Fe₂O₃–PAA–Tb³⁺ (excitation 265 nm) was partially quenched by Fe₂O₃. However, a weak emission of Eu³⁺ ions was observed (excitation 265 nm) in the matrix LDPE–Fe₂O₃–PAA after simultaneous Eu³⁺ and Tb³⁺ ion exchanges, suggesting an energy transfer from Tb³⁺ to Eu³⁺ ions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 919–931, 2000     

Thermal history driven molecular structure transitions in alumino‐borosilicate glass

The glass network structure governs various thermos‐physical properties such as viscosity, thermal, and electrical conductivities, and crystallization kinetics. We investigated the effect of temperature on structural changes in a Na₂O‐CaO‐Al₂O₃‐SiO₂‐B₂O₃ glass system using ²⁷Al MAS NMR spectroscopy. Around the glass transition temperature, most of aluminate structures exist as AlO₄, acting as a glass former. When the temperature is above the melt crystallization temperature, the AlO₄ structure is drastically decreased and glass structures are mainly composed of AlO₅ and AlO₆, acting as glass modifiers. Thermodynamic assessment based on Gibbs energy minimization was used to confirm the dependency of aluminate structure's amphoteric characteristic on temperature by calculating the site fraction of aluminate molecular structures at different temperatures. Temperature‐induced aluminate structural variation can also influence silicate and borate structural changes, which have been confirmed by the ²⁹Si and ¹¹B NMR spectra.     

Effect of substituting CaO with BaO on the viscosity and structure of CaO‐BaO‐SiO2‐MgO‐Al2O3 slags

In this study, the effect of CaO and BaO substitution on the viscosity and structure of CaO‐BaO‐SiO₂‐MgO‐Al₂O₃ slags was investigated. The results showed that the viscosity increased with an increase in the BaO substitution concentration, which was correlated to an increase in the degree of polymerization (DOP) of the slag structural units as the activation energy increased from 207.9 to 263.8 kJ/mol for viscous flow. Deconvolution and area integration of the Raman spectrum of the slag revealed that the ratio of Q³/Q² (Qⁱ, i is the number of O⁰ in a [SiO₄]‐tetrahedral unit) increased and NBO/Si (nonbridging oxygen per unit silicon atom) decreased with higher BaO content. It was also observed from the ²⁷Al magic angles pinning nuclear magnetic resonance (²⁷Al MAS‐NMR) spectrum that the relative proportion of Al^IV increased, while that of Al^V decreased because of the decrease in the percentage of nonbridging oxygen (O^?), indicating the polymerization of the slag. O_1s X‐ray photoelectron spectroscopy (XPS) was also carried out to semi‐quantitatively analyze the various types of oxygen anions present in the slag. The XPS results correlated well with the results obtained from the analysis of the Raman and ²⁷Al MAS‐NMR spectra of the slags and its viscous behavior.     

Impact of Eu3+ Dopants on Optical Spectroscopy of Ce3+: Y3Al5O12‐Embedded Transparent Glass‐Ceramics

Transparent glass‐ceramics containing Ce³⁺: Y₃Al₅O₁₂ phosphors and Eu³⁺ ions were successfully fabricated by a low‐temperature co‐sintering technique to explore their potential application in white light‐emitting diodes (WLEDs). Microstructure of the sample was studied using a scanning electron microscope equipped with an energy dispersive X‐ray spectroscopy. The impact of co‐sintering temperature, Ce³⁺: Y₃Al₅O₁₂ crystal content and Eu³⁺ doping content on optical properties of glass‐ceramics were systematically studied by emission, excitation spectra, and decay curves. Notably, the spatial separation of these two different activators in the present glass‐ceramics, where Ce³⁺ ions located in YAG crystalline phase while the Eu³⁺ ones stayed in glass matrix, is advantageous to the realization of both intense yellow emission assigned to Ce³⁺: 5d→4f transition and red luminescence originating from Eu³⁺: 4f→4f transitions. As a result, the quantum yield of the glass‐ceramic reached as high as 93%, and the constructed WLEDs exhibited an optimal luminous efficacy of 122 lm/W, correlated color temperature of 6532 K and color rendering index of 75.     

Effect of the Al2O3/SiO2 mass ratio on the crystallization behavior of CaO-SiO2-MgO-Al2O3 slags using confocal laser scanning microscopy

The crystallization behavior of a CaO-SiO₂-MgO-Al₂O₃ slag system with varying Al₂O₃/SiO₂ mass ratios from 0.03 to 1.10 has been investigated using a confocal laser scanning microscopy (CLSM). The resulting continuous cooling transformation (CCT) and time-temperature-transformation (TTT) curves showed that the initial crystallization temperature increased and the incubation time for crystallization slightly decreased with increasing Al₂O₃/SiO₂ ratio. The crystal growth rate first increased and then decreased with decreasing isothermal temperature. X-ray diffraction (XRD) analysis suggested that Ca₂MgSi₂O₇ or Ca₃MgSi₂O₈ precipitated as the primary phase at lower Al₂O₃/SiO₂ ratios, while the Ca₂Al₂SiO₇ phase was preferred at higher Al₂O₃/SiO₂ ratios. The observed crystalline phases correlated well with the expected thermodynamic predictions from FactSage. In addition, structural analysis using ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS-NMR) microscopy of the as-quenched slags indicated the presence of a higher ratio of tetrahedral [AlO₄]^5-structural units with increasing Al₂O₃/SiO₂ ratio, which enhanced the polymerization of tetrahedral [AlO₄]^5- and [SiO₄]^4- structural units to form Ca₂Al₂SiO₇.     

Orderly‐Layered Tetravalent Manganese‐Doped Strontium Aluminate Sr4Al14O25:Mn4+: An Efficient Red Phosphor for Warm White Light Emitting Diodes

Searching for an efficient non rare earth‐based oxide red phosphor, particularly excitable by light in the wavelength from 380 to 480 nm and unexcitable by green light, is essential for the development of warm white light emitting diodes (WLEDs). Here, we report a promising and orderly‐layered candidate: Sr₄Al₁₄O₂₅:Mn⁴⁺ with CIE color coordinates (0.722, 0.278). It has higher luminescence efficiency particularly upon blue excitation and is much cheaper than the commercial red phosphor 3.5MgO·0.5MgF₂·GeO₂:Mn⁴⁺ (MMG:Mn⁴⁺). In sharp contrast to Eu²⁺‐doped (oxy)nitrides, the phosphor can be synthesized by a standard solid‐state reaction at 1200°C in air. The effects of flux boron content, environment, and preparation temperature, sintering dwelling time as well as Mn concentration have been systematically investigated for establishing the optimal synthesis conditions. The low temperature emission spectra reveal that there are at least three types of Mn⁴⁺ ions in Sr₄Al₁₄O₂₅:Mn⁴⁺ due to the substitution for the distorted octahedral Al³⁺ sites. The AlO₆ layers where Mn⁴⁺ prefers to reside are well separated from one another by AlO₄ tetrahedra in one dimension parallel to axis a. This scenario can efficiently isolate Mn⁴⁺ ions from local perturbations, thereby enabling the high efficiency of luminescence. The energy transfer rates and mechanism are discussed.     

Structural and Optical Properties of Tunable Warm‐White Light‐Emitting ZrO2:Dy3+–Eu3+ Nanocrystals

A series of Dy³⁺–Eu³⁺‐codoped ZrO₂ nanocrystals with tetragonal and cubic symmetry was synthesized via a wet chemical reaction. When the Eu³⁺‐doping content was fixed, the crystal structure could be stabilized from the mixed phase to single cubic phase by simply adjusting the content of Dy³⁺. The cubic ZrO₂:Dy³⁺–Eu³⁺ nanoparticles exhibited spherical and nonagglomerated morphology. The effective phonon energy of cubic ZrO₂:5%Dy³⁺–5%Eu³⁺ was calculated to be 445 cm^?1, which is lower than the previously reported results. Extensive luminescence studies of ZrO₂:Dy³⁺–Eu³⁺ as a function of Dy³⁺ content demonstrated that the dopant concentration and its site symmetry play an important role in the emissive properties. Under 352 nm excitation, the increment of Dy³⁺ concentration in ZrO₂:Dy³⁺–Eu³⁺ led to an increase in orange (590 nm) and red (610 nm) emissions of Eu³⁺ ions, which are attributed to the ⁵D₀→⁷F_J(J = 1, 2) transitions of Eu³⁺ ions. This increment is possibly due to the efficient energy transfer (ET) ⁴F_9/2:Dy³⁺→⁵D₀:Eu³⁺. The phosphors can generates light from yellow through near white and eventually to warm white by properly tuning the concentration of Dy³⁺ ions through the ET and change in site symmetry. These phosphors may be promising as warm‐white‐/yellow‐emitting phosphors.     

Integrated experimental phase equilibria study and thermodynamic modelling of the binary ZnO–Al2O3, ZnO–SiO2, Al2O3–SiO2 and ternary ZnO–Al2O3–SiO2 systems

Phase equilibria of the ZnO–SiO₂, Al₂O₃–SiO₂ and ZnO–Al₂O₃–SiO₂ systems at liquidus were characterized at 1340–1740 °C in air. The ZnO–Al₂O₃ subsolidus phase equilibria were derived from the experiments with the SiO₂- and CaO + SiO₂-containing slags. High-temperature equilibration on silica or platinum substrates, followed by quenching and direct measurement of Zn, Al, Si and Ca concentrations in the phases with the electron probe X-ray microanalysis (EPMA) was used to accurately characterize the system. Special attention was given to zincite phase that was shown to consist of two separate ranges of compositions: round-shaped low-Al zincite (<2 mol.% AlO_1.5) and platy high-Al zincite (4–11 mol.% AlO_1.5). A technique was developed for more accurate measurement of the ZnO solubility in the low-ZnO phases (corundum, mullite, tridymite and cristobalite) surrounded by the ZnO-containing slag, using l-line for Zn instead of K-line, avoiding the interference of secondary X-ray fluorescence. Solubility of ZnO was found to be below 0.03 mol.% in corundum and cristobalite, and below 0.3 mol.% in mullite. Present experimental data were used to obtain a self-consistent set of parameters of the thermodynamic models for all phases in this system using FactSage computer package. The modified quasichemical model with two sublattices (Zn²⁺, Al³⁺, Si⁴⁺) (O^2?) was used for the liquid slag phase; the compound energy formalism was used for the spinel (Zn²⁺,Al³⁺)[Zn²⁺,Al³⁺,Va]₂O^2-₄ and mullite Al³⁺₂(Al³⁺,Si⁴⁺) (O^2?,Va)₅ phases; the Bragg-Williams formalism was used for the zincite (ZnO, Al₂O₃); other solid phases (tridymite and cristobalite SiO₂, corundum Al₂O₃, and willemite Zn₂SiO₄) were described as stoichiometric. Present study is a part of the research program on the characterization of the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–As–Sn–Sb–Bi–Ag–Au–Ni system.     

Effect of Al/Sr ratio on the luminescence properties of SrAl2O4:Eu2+, Dy3+ phosphors

Recent studies have brought out many phosphors like Eu²⁺, Dy³⁺-doped alkaline earth aluminates. The trivalent Dy³⁺ ions as co-dopants greatly enhance the duration and intensity of persistent luminescence. These phosphors show excellent properties, such as high quantum efficiency, long persistence of phosphorescence, good stability and suitable color emission.In this work the effect of Al/Sr ratio on the afterglow and phosphorescence decay properties of Eu²⁺ and Dy³⁺ co-activated strontium aluminates synthesized by a solid-state process has been investigated. The luminescence properties of samples were investigated by means of excitation spectra, emission spectra and X-ray diffraction analysis.A variety of strontium aluminates, such as SrAl₂O₄, Sr₄Al₂O₇, Sr₃Al₂O₆, Sr₃Al₂(Eu, Dy, Y)O_7.5, Al₅(Eu, Dy, Y)O₁₂, Sr₄Al₁₄O₂₅, SrAl₁₂O₁₉ and (Eu, Dy, Y)AlO₃ have been identified in the samples prepared from starting precursors with Al/Sr mole ratios ranging from 0.44 to 5. The afterglow decay rate was found to be the fastest for sample with Al/Sr ratio of 4.18, in which SrAl₄O₇ phase was dominant. The afterglow decay rate for phosphor with Al/Sr ratio of 2, in which SrAl₂O₄ phase was dominant, was detected to be slow. Moreover, the emission spectra of the samples shift to yellow-green long wavelength from bluish-green-ultraviolet short wave with the increase of Al/Sr ratios resulting from the change in the composition.     

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.     

Host sensitized photoluminescence in Sr2.9-3x/2LnxAlO4F: 0.1Eu3+ (Ln = Gd,Y) for innovative flexible lighting applications

Tetragonal structured Sr₃AlO₄F is highly strained as reported from its global instability index estimation. Moreover, our results of X-ray photoelectron spectroscopy (XPS) also ascertained that the structure of Sr₃AlO₄F is highly strained with oxygen vacancies. Herein, aliovalent substitutions of divalent Sr ions with trivalent Ln (Ln = Gd/Y) ions were carried out to improve the stability of Sr₃AlO₄F lattice, which subsequently enhanced the photoluminescence in a series of Sr_2.9-3x/2Ln_xAlO₄F: 0.1Eu³⁺ phosphors. All the phosphors showed intense red-orange emission (⁵D₀ → ⁷F_1,2) at excitation with UV and near-UV light. The critical concentrations of Gd³⁺ and Y³⁺ up to which the Eu³⁺ emission intensities increased linearly were observed to be x = 0.09 and x = 0.07, respectively. Nevertheless, further enhancement in the Eu³⁺ luminescence of the optimized phosphors was realized by subsequently annealing in low oxygen atmospheres. The enhancement in oxygen deficiency during the post-annealing in Ar or vacuum led the energy transfer (O^2--Eu³⁺) to a greater extent which afterward increased the Eu³⁺ luminescence. The optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ and Sr_2.795Y_0.07AlO₄F: 0.1Eu³⁺ phosphors showed high red color purity (~99%), as well as CIE coordinates of (0.62, 0.38), indicated that these phosphors could be appropriate red-emitting components for making flexible optical films for many lighting devices. Therefore, flexible polydimethylsiloxane based films were also fabricated using optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ phosphor. The electroluminescence of a flexible PDMS-phosphor composite film showed an intense and pure red color with good thermal stability suggesting its suitability in flexible lighting and display devices.