Insight into luminescent properties,energy transfer and thermal stability of NaBa4(AlB4O9)2Cl3:Ce3+, Tb3+ phosphors

A series of Ce³⁺ and Tb³⁺ singly- and co-doped NaBa₄(AlB₄O₉)₂Cl₃ (NBAC) phosphors have been synthesized via high-temperature solid state route. The crystal structure, morphology, photoluminescent properties, thermal properties and energy transfer process between Ce³⁺ and Tb³⁺ were systematically investigated. The structure refinements indicated that the phosphors based on NBAC crystallized in P42nm polar space group in monoclinic phase. The emission color could be tuned from blue (0.1595, 0.0955) to green (0.2689, 0.4334) via changing the ratio of Ce³⁺/Tb³⁺. The energy transfer mechanism of Ce³⁺/Tb³⁺ was verified to be dipole–quadrupole interaction via the examination of decay times of Ce³⁺ based on Dexter's theory. The good thermal stability showed the intensities of Ce³⁺ at 150°C were about 66.9% and 64.88% in NBAC:0.09Ce³⁺ and NBAC:0.09Ce³⁺, 0.07Tb³⁺ of that at room temperature, and the emission intensities of Tb³⁺ remained 102.41% in NBAC:0.11Tb³⁺ and 95.22% in NBAC:0.09Ce³⁺, 0.07Tb³⁺ due to the nephelauxetic shielding effect and the highly asymmetric rigid framework structure of NBAC. The maximum external quantum efficiency (EQE) of Ce³⁺ in NBAC:0.09Ce³⁺, yTb³⁺ phosphors could reach 43.38% at y = 0.13. Overall, all the results obtained suggested that NBAC:Ce³⁺, Tb³⁺ could be a promising option for n-UV pumped phosphors.     

Dual effect synergistically triggered Ce:(Y,Tb)3(Al,Mn)5O12 transparent ceramics enabling a high color-rendering index and excellent thermal stability for white LEDs

Ce:Y₃Al₅O₁₂ transparent ceramics (TCs) with appropriate emission light proportion and high thermal stability are significant to construct white light emitting diode devices with excellent chromaticity parameters. In this work, strategies of controlling crystal-field splitting around Ce³⁺ ion and doping orange-red emitting ion, were adopted to fabricate Ce:(Y,Tb)₃(Al,Mn)₅O₁₂ TCs via vacuum sintering technique. Notably, 85.4 % of the room-temperature luminescence intensity of the TC was retained at 150 °C, and the color rendering index was as high as 79.8. Furthermore, a 12 nm red shift and a 16.2 % increase of full width at half maximum were achieved owing to the synergistic effects of Tb³⁺ and Mn²⁺ ions. By combining TCs with a 460 nm blue chip, a warm white light with a low correlated color temperature of 4155 K was acquired. Meanwhile, the action mechanism of Tb³⁺ ion and the energy transfer between Ce³⁺ and Mn²⁺ ions were verified in prepared TCs.     

新型FED用蓝粉Sr_5(PO_4)_3Cl: Eu~(2+)的研究

阴极射线显示器用蓝粉一直是限制彩色显示器发光效率和亮度的重要因素之一,这一问题也 同样存在于ＦＥＤ显示器件中。本文报导了最新研制的一种新型蓝色荧光粉Ｓｒ_５（ＰＯ_４）_３Ｃｌ： ＥＵ~（２＋）, 具有发光亮度较高,色纯度好,对阴极不易产生污染的特点。     

Luminescence investigations of novel orange‐red fluorapatite KLaSr3(PO4)3F: Sm3+ phosphors with high thermal stability

Single‐phase KLaSr₃(PO₄)₃F: Sm³⁺ phosphors with fluorapatite structure were prepared via high‐temperature solid‐state method in air atmosphere for the first time. The X‐ray diffraction, scanning electron microscope, diffuse reflectance spectra, photoluminescence spectra, and temperature‐dependent emission spectra, as well as lifetimes were measured to characterize the as‐prepared phosphors. Phase results indicated that KLaSr₃(PO₄)₃F: Sm³⁺ belongs to hexagonal system with a space group of P‐6. Photoluminescence measurements showed the emission spectrum was composed of four sharp peaks at about 564, 602 (the strongest one), 646, and 702 nm, corresponding to the ⁴G_5/2‐⁶H_J (J=5/2, 7/2, 9/2, and 11/2) transitions of Sm³⁺ ions. The optimum doping concentration of Sm³⁺ ions was turned out to be 0.03 (mol), and the mechanism of energy transfer among Sm³⁺ ions was considered to be dipole‐dipole interaction by using Dexter's theory. In addition, the critical distance R_c for energy transfer among Sm³⁺ ions were calculated to be 9.97 Å according to Blasse concentration quenching method. The selected KLa_0.97Sr(PO₄)₃F: 0.03Sm³⁺ exhibited high thermal stability with an activation energy of 0.163 eV. Besides, the Commission International de l'Eclairage chromaticity coordinate of the phosphor were located in the orange‐reddish light region.     

Synthesis and emission analysis of RE (Eu or Dy):Li2TiO3 ceramics

The development and photoluminescence analysis of Eu³⁺or Dy³⁺ ions in the matrix of lithium titanate (Li₂TiO₃) ceramics by using a solid state reaction method are reported. Emission spectra of Eu³⁺:Li₂TiO₃ ceramics have shown strong red emission at 611 nm (⁵D₀ → ⁷F₂) with λ_exci = 392 nm (⁷F₀ → ⁵L₆) and from the Dy³⁺:Li₂TiO₃, a blue emission at 493 nm (⁴F_9/2 → ⁶H_15/2) and also an yellow emission at 582 nm (⁴F_9/2 → ⁶H_13/2) have been observed with λ_exci = 366 nm (⁶H_15/2 → ⁶P_5/2). Both the rare-earth ions containing ceramics have displayed their brighter emission performance from their measured spectral results. In addition, X-ray diffraction (XRD), Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) have been used to characterize the structural properties of (Eu³⁺ or Dy³⁺):Li₂TiO₃ ceramics.     

Morphology control and temperature sensing properties of micro-rods NaLa(WO4)2:Yb3+,Er3+ phosphors

Uniform spindle-like micro-rods NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors are prepared by the solvothermal method in the text. Controllable morphology of NaLa(WO₄)₂ crystal can be obtained by adjusting the prepared temperature, PH value, complexing agent content, and solvent ratio. Uniform NaLa(WO₄)₂:Yb³⁺,Er³⁺ micro-rods of 1.8 μm in length and 0.5 μm in width are synthesized at a low temperature of 120°C. The prepared NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors present green upconversion luminescence under 980 nm excitation, luminescence intensity reaches to maximum at the Yb³⁺ and Er³⁺ concentration of 6 and 2 mol%. The temperature performance of the NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors are evaluated based on thermal coupling technology. Temperature dependence of the two green emissions ratio of Er³⁺ ion is obtained, and the sensitivity of the sample can be calculated, the maximum sensitivity of NaLa(WO₄)₂:Yb³⁺,Er³⁺ is up to 0.019 K⁻¹ at the sample temperature of 564 K.     

Structural and electrical properties of lead free ceramic: Ba(La1/2Nb1/2)O3

Abstract

Abstract

Lead free perovskite Ba(La_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1375°C for 7?h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were estimated using Rietveld analysis. X-ray diffraction analysis indicated the formation of a single phase monoclinic structure with space group P2/m. Energy dispersive X-ray analysis and scanning electron microscopy studies were carried to study the quality and purity of the compound. Permittivity data showed low temperature coefficient of capacitance (T _CC = 11%) up to 100°C. The circuit model fittings were carried out using the impedance data to find the correlation between the response of real system and idealised model electrical circuit. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(La_1/2Nb_1/2)O₃. The AC conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy.     

Mixtures of poly(vinyl chloride) and copolyesters based on ε‐caprolactone and L‐lactide: Miscibility,thermal stability,and weathering resistance

Properties of the blends of Poly(vinyl chloride) (PVC) and poly(ε‐caprolactone) (PCLO) and copolyesters based on ε‐caprolactone and L‐lactide (LLA) prepared by rolling were studied. Incorporating the LLA units into the structure of PCLO the content of the crystalline phase was controlled. Miscibility of the blends was assessed using DMA, and basic mechanical properties were correlated with the type and content of the polymer plasticizer. The PVC blends containing up to 20 wt parts polyesters were miscible. The presence of the LLA units in the copolyester influenced negatively the thermal stability. On the other hand even small content of copolyester in the blend enhanced the resistivity against aging. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) as studied by TG,TG–FTIR,and Py–GC/MS

The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (T_o, T_p, and T_f) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, T_o(0), T_p(0), and T_f(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO₂. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003     

Study of polypropylene/montmorillonite nanocomposites prepared by solid‐state shear compounding (S3C) using pan‐mill equipment: the morphology of montmorillonite and thermal properties of the nanocomposites

In this paper, polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposites were successfully prepared without any compatibilizers by solid‐state shear compounding (S³C) using pan‐mill equipment. X‐ray diffraction (XRD) patterns show that the OMMT characteristic (001) peak at 2θ equal to 4.59 degrees disappeared for the milled OMMT and corresponding composites. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) photographs show that the thickness of pan‐milled OMMT decreased from ca 100–200 nm to ca 30–50 nm, and OMMT was partly exfoliated in the PP matrix because the pan‐type mill can exert fairly strong squeezing force in the normal direction and shearing force in both radial and tangential directions on milled materials. PP/OMMT nanocomposites at low OMMT loading have higher melting point, crystallization temperature, thermal degradation temperature and heat distortion temperature than those of neat PP. Moreover, addition of OMMT accelerates crystallization of PP significantly. S³C is a novel approach to prepare polymer/layered silicate nanocomposites with high performances at low filler loading. Copyright © 2004 Society of Chemical Industry     

A novel route to α,ω-telechelic poly(-caprolactone) diols, precursors of biodegradable polyurethanes, using catalysis by decamolybdate anion

A new convenient route for the synthesis of poly(-caprolactone) (PCL) with α,ω-telechelic diols' end-groups is presented. Synthesis of α,ω-telechelic PCL diols (HOPCLOH) was achieved by ring-opening polymerization (ROP) of -caprolactone (CL) catalyzed with ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] and using diethylene glycol (DEG) as initiator. Obtained HOPCLOH was characterized by ¹H and ¹³C NMR, FT-IR, GPC and MALDI-TOF. Comparative studies demonstrate that ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] is better catalyst than Sn-octanoate (SnOct₂) toward CL polymerization in presence of DEG, under the conditions tested. A biodegradable poly(ester-urethane-urea) derivative was efficiently prepared from synthesized HOPCLOH. Obtained polymer shows minor differences with respect to the properties recorded for a poly(ester-urethane-urea) obtained from commercial HOPCLOH.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.