Ethyl vinyl acetate copolymer—SrAl2O4:Eu,Dy and Sr4Al14O25:Eu,Dy phosphor‐based composites: Preparation and material properties

New photoactive composite based on ethyl vinyl acetate (EVA) and SrAl₂O₄:Eu,Dy or Sr₄Al₁₄O₂₅:Eu,Dy were prepared by melt mixing or extrusion methodologies. The phosphorescent behavior and material properties of the polymer‐phosphor composites were studied. The morphology of the polymer and the composites were studied by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X‐ray spectroscopy (EDS). The SEM shows that the physical and chemical behavior of the matrix and the extrusion conditions were primarily responsible for the surface morphology. TEM and EDS show that the phosphor particles were uniformly dispersed in the EVA matrix. A broad band of ultraviolet (UV)‐excited phosphorescence of SrAl₂O₄:Eu,Dy and Sr₄Al₁₄O₂₅:Eu,Dy phosphors and the respective composites were observed at wavelengths of 516 nm and 490 nm, respectively. The photoluminescence (PL) spectra showed less intense phosphorescence but no shift in the wavelength of the emission peak for all the composites. The Hamburg wheel test was done on all the composites and the PL measurements before and after the test showed almost no change in the intensity of the emission. Thermal studies showed that the presence of the phosphors in the matrix slightly increased the crystallinity of EVA, which leads to higher melting enthalpies. Tensile testing shows very little change in the tensile strength and flexibility of the ethylene vinyl acetate copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Experimental evaluation of the luminescence performance of fired clay brick coated with SrAl2O4:Eu/Dy phosphor

This study evaluates the luminescence performance of fired clay bricks coated with SrAl₂O₄:Eu/Dy phosphor. To do so, SrAl₂O₄:Eu/Dy phosphor was first produced using the traditional solid-state reaction synthesis technique. The prepared phosphor was then used for coating fired clay bricks to analyze the luminescence performance via spectral analysis, decay characteristics, and microstructure of the bricks. The results reveal that excitation and emission spectra of the phosphor coated bricks range from 200 to 480 nm and 455 to 650 nm, respectively, suggesting that the phosphor coated bricks have the capacity of absorbing light with a wide range of wavelengths. The peak wavelength projected at 511 nm in the emission spectrum is achieved, which indicates 4f⁶5 d¹-4f⁷ transition of Europium (Eu²⁺). The repeated excitation and deexcitation of Eu²⁺ by using hole traps and trap levels offered by Dysprosium (Dy³⁺), exist between the ground and the excited state of Eu²⁺ leads to luminescent phenomenon. Moreover, the decay characteristics has revealed that phosphor coated bricks can emit light for a considerable amount of time (>8.5 min) upon the removal of the excitation source. The results reveal that phosphor coated bricks has the potential of increasing energy efficiency of residential and commercial buildings.     

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.     

Layered Ceramic Phosphors Based on CaAlSiN3:Eu and YAG:Ce for White Light‐Emitting Diodes

To develop warm‐white light‐emitting diodes via conversion phosphors, blue light‐emitting diodes are generally combined with mixtures of green and red‐emitting phosphor powders. Generally, the phosphors are provided by resin embedded particle dispersions. Such resin‐based solutions cause several drawbacks with respect to LED lifetime and quality. Therefore, it has been investigated whether the red‐emitting nitride phosphor CaAlSiN₃:Eu and the green‐emitting oxidic phosphor YAG:Ce can be cofired to layered ceramic composites. The shrinkage behavior and the composition of the interface in dependence of sintering temperature and the effect of interdiffusion processes at the interface on the luminescence properties were investigated. The formation of secondary phases at the interface in the cofired structures was found to limit the phosphor functionality for the nitride‐based CaAlSiN₃:Eu in such composite ceramics. To counteract this, sacrificial interlayers were introduced to produce multilayered ceramics comprising CaAlSiN₃:Eu and YAG:Ce for LED lighting applications. It is shown for the first time, that it is possible to sinter layered CaAlSiN₃:Eu and YAG:Ce composite ceramics in a pressureless process at moderate sintering temperatures if one uses thin‐film passivated interfaces to reduce luminescence‐disturbing diffusion phenomena. These results demonstrate that diffusion barriers can be suitable means to obtain layered ceramic composites comprising CaAlSiN₃:Eu and YAG:Ce in a pressureless sintering process with good optical properties.     

Effect of sintering and boron content on rare earth dopant distribution in long afterglow strontium aluminate

B has been proposed to extend persistent luminescence from minutes to > 10 h in Eu, Dy, and B co-doped Sr₄Al₁₄O₂₅ (S4A7EDB) by facilitating the incorporation of Eu²⁺ and Dy³⁺ into adjacent Sr sub-lattice sites and enabling energy transfer between them. To evaluate additional influences of B on the kinetics of microstructural evolution and dopant distribution that support afterglow in S4A7EDB, the effect of heating rates to 1300 °C is compared for spark-plasma sintering and conventional sintering, with and without the addition of B₂O₃. Analysis of the microstructure and elemental distribution, by a combination of imaging, WDS, and CL in the SEM, XRD, dilatometry, and STEM-EELS, reveals that when the diffusivity of Eu and Dy is increased, Eu and Dy segregate to the intergranular phase. The partitioning of Eu and Dy concentrations to below their solubility limit in the grains appears to be essential to material structure enabling longer afterglow.     

Enhancement of photoluminescence intensity of sintered CaAlSiN3:Eu2+ red phosphor-bismuthate glass composites

Wavelength converters in white light-emitting diodes are usually made by sintering of phosphor-glass powder compacts. An issue is that the sintering process usually results in the reduction of phosphor amount. In the present study, composites containing CaAlSiN₃:Eu²⁺ red phosphor and Bi₂O₃-B₂O₃-ZnO-Sb₂O₅ glass were fabricated by sintering method. Influences of CaAlSiN₃:Eu²⁺ phosphor content (10 vol%–30 vol%) and sintering temperature (410–430°C) on the residual amount of the phosphor phase and the resulting luminescence intensity of the composites were investigated. The change of CaAlSiN₃:Eu²⁺ content due to sintering was analyzed by X-ray diffraction. The interdiffusion between the CaAlSiN₃:Eu²⁺ and glass matrix was examine by scanning electron microscope equipped with energy dispersive X-ray spectrometry. This paper focuses on the change of luminescence intensity after sintering. It was found that although the content of phosphor CaAlSiN₃:Eu²⁺ reduces after sintering; the luminescent intensity of the composites anomalously increases. The optimum luminescence intensity is 14% higher than that of the as-mixed, unfired powder. It is proposed that the incorporation of Bi³⁺ ions from the glass matrix into the phosphor CaAlSiN₃:Eu²⁺ during sintering improves the luminescence ability of the phosphor particles.     

Luminescent properties of SrAl2O4: Eu,Dy material prepared by the gel method

SrAl₂O₄:Eu,Dy materials were first prepared by the gel method. Compared with samples prepared by solid state reactions, the grain size of the gel method is greatly reduced to nanometer grade. A clear blue shift occurs in the excitation and emission spectra of nano SrAl₂O₄:Eu,Dy, of which the peak of the excitation and emission spectra are at 323 and 500 nm respectively. The brightness of nano SrAl₂O₄:Eu,Dy is greatly reduced. The blue shift and the change of luminescent intensity in nano SrAl₂O₄:Eu,Dy materials can be attributed to the effect of surface energy.     

Trap Levels in Eu and other Rare‐Earth Ions Codoped CaAl2O4 Phosphors

Photoluminescence spectrum, trap depths, and densities of trapped carriers of CaAl₂O₄:Eu phosphor crystals doped with rare‐earth elements were studied using the thermally stimulated luminescence technique. Trap depths and densities of the specimens vary with rare‐earth elements doped as the auxiliary activators. Tm and Nd are found to be effective for the strong afterglow phosphorescence peaking at λ = 442 nm for several hours after the excitation. CaAl₂O₄:Eu phosphor crystals doped with Nd and Tm include high density of carriers trapped at E = 0.59 and 0.52 eV, respectively.     

Persistent deNOx Ability of CaAl2O4:(Eu, Nd)/TiO2-x N y Luminescent Photocatalyst

Abstract  

CaAl₂O₄:(Eu, Nd)/TiO_2-x N _y composite luminescent photocatalyst was successfully synthesized by a simple planetary ball milling process. Improvement of photocatalytic deNOx ability of TiO_2-x N _y , together with the persistent photocatalytic activity for the decomposition of NO after turning off the light were realized, by coupling TiO_2-x N _y with long afterglow phosphor, CaAl₂O₄:(Eu, Nd). The novel persistent photocatalytic behavior was related to the overlap between the absorption wavelength of TiO_2-x N _y and the emission wavelength of the CaAl₂O₄:(Eu, Nd). It was found that CaAl₂O₄:(Eu, Nd)/TiO_2-x N _y composites provided the luminescence to persist photocatalytic reaction for more than 3 h after turning off the light.     

Synthesis and characterization of polyurethane cationomer/MMT hybrid composite

BACKGROUND: The development of polymeric nanocomposites incorporating intercalated or exfoliated layered silicate clays into the organic matrix has been substantially motivated by the significant improvements induced by the presence of the inorganic component. Moreover, understanding and controlling the dispersion of inorganic layers into segmented polyurethane matrices by means of ionic interactions, and exploiting these interactions to enhance physicomechanical behaviour, could be of great interest in the field of polymer nanocomposites. RESULTS: New cationic polyurethane elastomers were prepared starting from poly(butylene adipate)diol (M_n = 1000 g mol^?1), 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol and N‐methyldiethanolamine or N,N′‐β‐hydroxyethylpiperazine, used as potential quaternizable moieties. The characterization of the polymers was achieved using specific analyses employed for the macromolecular samples (Fourier transform infrared and ¹H NMR spectroscopy, thermogravimetric analysis (TGA), gel permeation chromatography). An extension of our research on polymers reinforced with organically modified montmorillonite (OM‐MMT) in order to prepare hybrid composites with improved properties was performed and the resulting materials were characterized using TGA, X‐ray diffraction, atomic force microscopy and scanning electron microscopy. Also, the mechanical properties of the cationic polyurethane/OM‐MMT composites were investigated in comparison with the pristine ionic/non‐ionic polymers and their composites containing non‐ionic polymer blended with OM‐MMT or ionic polymer and unmodified MMT. CONCLUSION: The insertion of the organically modified clay into the polymeric matrix gave an improvement of the mechanical properties of the polyurethane composites, especially the tensile strength and stiffness of the hybrid materials. Copyright © 2009 Society of Chemical Industry     

Boosting phosphorescence efficiency by crystal anisotropy in SrAl2O4:Eu,Dy textured ceramic layers

Among persistent luminescence materials, one of the most studied systems is SrO-Al₂O₃ due to its chemical stability and the longest green-afterglow duration. This research is focused on the synthesis of SrAl₂O₄:Eu,Dy textured layers by the screen-printing. The novelty of the approach is the employment of molten salt to promote crystal growth. The reactive ink, composed by the mixture of precursors in adequate proportions (SrCO₃, Eu₂O₃, Dy₂O₃, and NaCl-KCl) and an organic-based vehicle, was printed onto the Al₂O₃ substrates in a single step, obtaining epitaxial films. Control experiments showed that both heat treatment and substrate nature were vital ones for the improvement of the PL. Highly oriented layers demonstrated a twofold enhancement of the luminescence as compared with unoriented films. These results evidence, for the first time, that the crystal anisotropy plays a key role in the luminescence of the low symmetry structures such as the monoclinic SrAl₂O₄ material. The results give the possibility of the cost-efficient production of layers by an easily scalable process.     

不同添加剂对SrAl2O4:(Eu,Dy)磷光体发光性能的影响

在较低的温度下用燃烧合成法快速合成了 Eu2 ,Dy3 掺杂的SrAl2O4长余辉磷光体发光材料.研究了P2O5,CaF2,H3BO3,NaF 几种添加剂对SrAl2O4:(Eu,Dy)粉体发光性能的影响.结果发现:H3BO3和P2O5的添加有利于改善磷光体的发光性能,而在配料中加入CaF2和NaF,磷光体发光效率降低.随着这几种添加剂的加入,SrAl2O4:(Eu,Dy)磷光体材料发射光谱的主发射峰不同程度的出现蓝移.根据实验结果分析了添加剂的作用机理.     

Trap distribution and photo-stimulated luminescence in LaSrAl3O7:Eu2+ long-lasting phosphors for optical data storage

Here, a green emission persistent luminescent phosphor LaSrAl₃O₇:Eu²⁺ which is chargeable by UV light, was synthesized by solid-state reaction method. Elemental mapping and fluorescence microscopy photoluminescence of the sample demonstrated the homogeneous distribution of La, Sr, Al, O, and Eu in the phosphor. Rietveld refinement shows that the as-prepared sample belongs to the tetragonal crystalline structure with space group of P42₁m. The Eu²⁺:5d-4f broad persistent luminescence with maximum emission peaking at 518 nm can be effectively obtained after irradiating in the UV light. A series of excitation temperature-dependent thermoluminescence measurements were conducted to gain some insight into the information of traps. Additionally, to verify its feasibility of optical data storage, specific information letters were encoded on the LaSrAl₃O₇:Eu²⁺ phosphor films using the laser of 405 nm, then the stored information could indeed be read out by thermal stimulation as expected. Meanwhile, NIR photo-stimulated red persistent luminescence was also obtained, which holds great potential for optical information storage. Finally, combined with the experimental and density functional theory calculation results, we proposed a tentative schematic diagram to account for the PersL and photo-stimulated persistent luminescence mechanism in LaSrAl₃O₇:Eu²⁺ phosphor.     

Laser sintering and influence of the Dy concentration on BaAl2O4:Eu2+, Dy3+ persistent luminescence ceramics

This work reports the effect of the Dy concentration on the persistence luminescence properties of Eu doped barium aluminate (BaAl₂O₄) laser-sintered ceramics. For this study, the ceramics were first sintered using the laser sintering technique, based on a CO₂ laser as the heating source, in an ambient atmosphere. The structural and morphology characteristics of the samples were investigated by x-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques, respectively. The laser-sintered ceramics presented are shown to be phase pure (single phased), and, for highest Dy concentration sample, a spurious Dy-rich phase at the grain boundary was observed. All samples exhibit the characteristic blue-green emission from the Eu²⁺ ion, due to the 4f⁶5d¹–4f⁷ transition (495 nm), even when they have been sintered in air. Finally, a clear dependence of the persistent luminescence intensity and decay time with the Dy concentration was verified.     

Enhanced Luminescence in the SrMgAl10O17: Eu2+ Blue Phosphor Prepared by a Hybrid Urea‐Sol Combustion Route

A phase‐pure and high‐brightness blue phosphor, Eu²⁺ doped SrMgAl₁₀O₁₇ (SAM), was synthesized through a hybrid urea‐sol combustion route. The structure, photoluminescence spectra, and thermal stability of the SAM were investigated in this work. The phosphor had a homogeneous and rod‐like microstructure, showing a broad emission band centered at 465 nm under the 330 nm excitation. The concentration for luminescence quenching of SAM: Eu²⁺ occurred at 10 mol%, which doubled that of the phosphor prepared by the conventional combustion method. Compared with the traditional combustion method, the hybrid route led to improvements in luminescence by 52.2%, external quantum efficiency by 16.2%, and thermal stability by 8.8% at 435 K. The blue phosphor prepared by the new method could thus be potentially used with near ultraviolet light‐emitting diodes.     

Distinct composite structure and properties of Eu(phen)2Cl3(H2O)2 in poly(methyl methacrylate) and polyvinylpyrrolidone

The luminescent europium complex Eu(phen)₂ Cl₃(H₂O)₂ (phen refers to 1,10‐phenanthroline) was doped in poly(methyl methacrylate) (PMMA) and polyvinylpyrrolidone (PVP), respectively. The formed composite systems with different molar ratios of C?O groups in polymers and Eu ions were characterized by X‐ray diffractometry (XRD), FTIR, and photoluminescent (PL) spectroscopy and lifetime measurement. The XRD diffractograms show that the composites of PMMA/Eu(phen)₂Cl₃(H₂O)₂ and PVP/Eu (phen)₂Cl₃(H₂O)₂ have crystalline and amorphous structures, respectively, arising from different interactions between the polymers and the complex, as revealed by FTIR spectra. This leads to distinct luminescent characteristics arising from the ⁵D₀→⁷F_J transitions of Eu(III) ion (J = 0–4). For the composite systems of PMMA/complex, the characteristics of the emission lines change with decreasing molar ratios of C?O/Eu and approach that of the pure complex; whereas the composite systems of PVP/complex have similar spectral features, regardless of the molar ratios, differing from that of the pure complex. The polymer matrices have a substantial influence on the structure and properties of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3524–3530, 2004     

Enhanced Light Storage of SrAl2O4 Glass‐Ceramics Controlled by Selective Europium Reduction

A luminescent Eu, Dy: SrAl₂O₄ glass‐ceramics with high transparency in the visible region was successfully synthesized using the frozen sorbet technique with the control of O₂ partial pressure () for the oxidation of Eu²⁺ ions. The glass‐ceramics include Eu²⁺, Eu³⁺, and Dy³⁺ ions, and thus exhibits three characteristic types of emission bands, 4f–5d at around 520 nm (Eu²⁺ ions), 4f–4f at 610 nm (Eu³⁺ ions), and 480 nm (Dy³⁺ ions). The Eu, Dy: SrAl₂O₄ glass‐ceramics provide remarkable long‐persistent luminescence under dark condition. The glass‐ceramics also exhibits color‐changing luminescence in the visible region based on their remarkable light storage properties. The luminescent Eu, Dy: SrAl₂O₄ glass‐ceramics using the frozen sorbet technique with control of are promising materials for application in novel photonic and light storage materials.     

Dy and Eu activated Ca3B2O6 phosphors for near ultraviolet‐based light‐emitting diodes

The Dy‐ and Eu‐activated Ca₃B₂O₆ phosphors were synthesized by a high‐temperature solid‐state reaction technique and their structural and luminescent properties were investigated. The phosphors are characterized by X‐ray diffraction, photoluminescence spectra, and Commission International de I'Eclairage (CIE) chromaticity coordinates. It is found that the charge compensator Na⁺ plays an important role in modifying the emission spectral profiles of Dy and Eu ions in the phosphors. The ratio of the emission located at the yellow wavelength portion to that located at the blue wavelength region of the Dy³⁺ ions can be apparently tuned by changing the Na⁺ content. The luminescence intensity of the phosphors can be enhanced with introducing Na⁺ ions as well. The emission colors of Dy/Eu codoped phosphors change from blue to white and successfully acquire the superior white light emission (x = 0.330, y = 0.329) by appropriately tuning the Na⁺/Dy³⁺ content and the excitation wavelength. The energy transfer process from Eu²⁺ to Dy³⁺ and Eu³⁺ occurs in the Dy/Eu codoped phosphors, providing a further approach to modify the emission spectral profile of the examined phosphors. The phosphors presented here have promising applications in the fields of light‐emitting diodes.     

Coprecipitation synthesis of Ca14Al10Zn6O35:Mn4+ deep-red phosphor and silica-modified waterproofing ability

Ca₁₄Al₁₀Zn₆O₃₅:Mn⁴⁺ (CAZ:Mn) phosphor material, which shows deep-red luminescence, was synthesized by the coprecipitation (COP) method using a Na₂CO₃/NaOH solution as the precipitant. COP–CAZ:Mn phosphor exhibited a 2.1 times higher luminescence intensity than the corresponding phosphor prepared using the conventional solid-state reaction (SSR) method. This substantial increase in luminescence was mainly ascribed to the existence of a greater proportion of tetravalent manganese in COP–CAZ:Mn phosphor. Furthermore, COP–CAZ:Mn phosphor was modified with SiO₂ via hydrolysis of tetraethoxysilane (TEOS) to waterproof the compound because it is easily decomposed through hydrolysis under humid conditions. The SiO₂-modified CAZ:Mn phosphor maintained its crystal structure and high photoluminescence intensity after the water-resistance test. Therefore, waterproof CAZ:Mn phosphor with a high luminescence intensity was successfully discovered by utilizing the coprecipitation method and SiO₂ modification.     

Lanthanide coordination polymers constructed from 5-(4-pyridyl)-isophthalic acid: Synthesis,structure and photoluminescent properties

Nine lanthanide coordination polymers [Ln₂(pyip)₃(H₂O)₄·DMF·3H₂O]_n (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) based on the pyip^2 − ligand {H₂pyip = 5-(4-pyridyl)-isophthalic acid} have been synthesized under solvothermal conditions. X-ray crystallographic studies reveal that 1–9 are isostructural and crystallize in the triclinic system, space group P2₁/c, and exhibit a 3D framework. Topological analysis reveals that the 3D framework can be simplified to a uninodal 6-connected pcu alpha-Po primitive cubic type structure. Meanwhile, the luminescent properties of these nine coordination polymers in the solid state are also investigated. Especially the Eu and Tb compounds show bright red and green luminescence with luminescence lifetimes of 0.39 and 0.80 ms, respectively.