Chemical bond characteristics, thermal expansion property and compressibility of AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths)

Theoretical researches were performed on the CaFe2O4-type binary rare earth oxides AR(2)O(4) (A = Ca, Sr, Ba; R = rare earths) by using chemical bond theory of dielectric description. The chemical bond properties of these crystals were explored, and then the thermal expansion property and compressibility were studied. The theoretical values of linear thermal expansion coefficient (LTEC) and bulk modulus were presented. The calculations revealed that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the rare earths. In the cases of Sc and Y, both the LTEC and bulk modulus values are larger than the lanthanide series. We attribute this to the difference in the electronic configuration between Sc (Y) and lanthanide series. For SrY2O4 and BaY2O4 crystals, the theoretical values of LTEC and bulk modulus agree well with experimental ones.

Extraction and separation of rare earths from chloride medium with mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and sec-nonylphenoxy acetic acid

BACKGROUND: 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, H(2)A(2)) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec-nonylphenoxy acetic acid (CA100, H2B2) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied.

Solvent extraction of rare earths from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and sec-octylphenoxyacetic acid

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

beta-NaYF4 and beta-NaYF4:Eu3+ Microstructures: Morphology Control and Tunable Luminescence Properties

beta-NaYF4 hexagonal microprisms and microrods with different aspect ratios have been prepared via a simple hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The influences of reaction temperature and the molar ratio of NaF to y(3+) on the crystal phases and shapes of final products have been studied in detail. The aspect ratios of products increase gradually with the increase of reaction temperature and NaF/Y3+ molar ratio. The growth mechanisms of crystals prepared under the different conditions are presented systematically. More importantly, the systematical investigation on the luminescence properties of beta-NaYF4:xEu(3+) (x = 0.5, 1, 2, 3, 5, and 10 mol %) with hexagonally microprismatic morphology shows the characteristic emissions of Eu3+ (D-5(J)-F-7(J'), J, J' = 0, 1, 2, 3). Under the excitation of single wavelength light of 397 nm, the luminescence colors of the corresponding products can be tuned feasibly from bluish white to yellow to red by changing the doping concentration of Eu3+.

Photoluminescence properties of LaF3: Eu3+ nanoparticles prepared by refluxing method

The europium-doped LaF3 nanoparticles were prepared by refluxing method in glycerol/water mixture and characterized with X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-vis diffuse reflectance spectrum, and photoluminescence spectra. The results of XRD indicated that the obtained LaF3: Eu3+ nanoparticles were well crystallized with a hexagonal structure. ne FE-SEM image illustrated that the LaF3: Eu3+ nanoparticles were spherical with an average size around 30 nm. Under irradiation of UV light, the emission spectrum of LaF3: Eu3+ nanoparticles exhibited the characteristic line emissions arising front the D-5(0)-> F-7(J), (J=1, 2, 3, 4) transitions of the Eu3+ ions, with the dominating emission centered at 590 nm. In addition, the emissions from the 51), level could be clearly observed due to the low phonon energies (-350 cm(-1)) of LaF3 matrix. The optimum doping concentration for LaF3: Eu3+ nanoparticles was determined to be 20mol.%.

Luminescent properties of a new blue long-lasting phosphor Ca2P2O7:Eu2+, Y3+

A new pyrophosphate long-lasting phosphor with composition of Ca1.96P2O7:0.02Eu(2+), 0.02Y(3+) is synthesized via the high-temperature solid-state reaction method. Its properties are systematically investigated utilizing XRD, photoluminescence, phosphorescence and thermoluminescence (TL) spectra. The phosphor emits blue light that is related to the characteristic emission of Eu2+ due to 5d-4f transitions. For the optimized sample, bright blue long-lasting phosphorescence (LLP) could be observed by naked eyes even 6 h after the excitation source is removed. The TL spectra show that the doping of Y3+ ions greatly enhanced intensity of 335 K peak and created new TL peak at about 373 K that is also responsible for the blue LLP. Based on our study, Y3+ ions are suggested to act as electron traps to improve the performance of the blue phosphorescence of Eu2+ such as intensity and persistent time.

Hydrothermal Synthesis and Luminescence of Eu-Doped Ba0.92Y2.15F8.29 Submicrospheres

The nonstoichimetric Ba0.92Y2.15F8.29 submicrospheres that piled up by nanoparticles have been prepared via a solution-based method in a hydrothermal environment. The size distribution of the submicrospheres could be tuned by varying the amount of BaCl2. The fluoride source NaBF4 plays an important role in the formation of the submicrospheres. The chelator ethylenediaminetetraacetic acid regulates the growth of the primary nanoparticles as well as the aggregated submicrospheres. The photoluminescence properties of different concentrations of Eu3+-doped Ba0.92Y2.15F8.29 were investigated and the results revealed that the 8% concentration of Eu3+ ions is the optimum doping concentration and the Y3+ ions occupy the site of inversion symmetry.

The luminescence of CaYBO4 : RE3+ (RE=Eu, Gd, Tb, Ce) in VUV-visible region

Phosphors CaYBO4:RE3+ (RE = Eu, Gd, Tb, Ce) were synthesized with the method of solid-state reaction at high temperature, and their vacuum ultraviolet (VUV)-visible luminescent properties in VUV-visible region were studied at 20 K. In CaYBO4, it is confirmed that there are two types of lattice sites that can be substituted by rare-earth ions. The host excitation and emission peaks of undoped CaYBO4 are very weak, which locate at about 175 and 350-360nm, respectively. The existence of Gd3+ can efficiently enhance the utilization of host absorption energy and result in a strong emission line at 314 nm. In CaYBO4, Eu3+ has typical red emission with the strongest peak at 610 nm; Tb3+ shows characteristic green emission, of which the maximum emission peak is located at 542 nm. The charge transfer band of CaYBO4:Eu3+ was observed at 228 nm; the co-doping of Gd3+ and Eu3+ can obviously sensitize the red emission of Eu3+. The fluorescent spectra of CaYBO4:Ce3+ is very weak due to photoionization; the co-addition of Ce3+-Tb3+ can obviously quench the luminescence of Tb3+.

Application of rare earths in thermal barrier coating materials

Rare earths are a series of minerals with special properties that make them essential for applications including miniaturized electronics, computer hard disks, display panels, missile guidance, pollution controlling catalysts, H-2-storage and other advanced materials. The use of thermal barrier coatings (TBCs) has the potential to extend the working temperature and the life of a gas turbine by providing a layer of thermal insulation between the metallic substrate and the hot gas. Yttria (Y2O3), as one of the most important rare earth oxides, has already been used in the typical TBC material YSZ (yttria stabilized zirconia). In the development of the TBC materials, especially in the latest ten years, rare earths have been found to be more and more important. All the new candidates of TBC materials contain a large quantity of rare earths, such as R2Zr2O7 (R=La, Ce, Nd, Gd), CeO2-YSZ, RMeAl11O19 (R=La, Nd; Me=Mg, Ca, Sr) and LaPO4. The concept of double-ceramic-layer coatings based on the rare earth materials and YSZ is effective for the improvement of the thermal shock life of TBCs at high temperature.

Fabrication and luminescent properties of rare earths-doped Gd-2(WO4)(3) thin film phosphors by Pechini sol-gel process

Rare earth ions (Eu3+ and Dy3+)-doped Gd-2(WO4)(3) phosphor films were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting powders and films. The results of XRD indicate that the films begin to crystallize at 600degreesC and the crystallinity increases with the elevation of annealing temperatures. The film is uniform and crack-free, WO(4)(2-)mainly consists of closely packed fine particles with an average grain size of 80 nm. Owing to an energy transfer from 4 groups, the rare earth ions show their characteristic emissions in crystalline Gd-2(WO4)(3) phosphor films, i.e., D-5(J) -F-7(J), (J = 0, 1, 2, 3; J' = 0 1, 2, 3, 4, not in all cases) transitions for Eu3+ and F-4(9/2)-H-6(J) (J = 13/2, 15/2) transitions for D Y3+, with the hypersensitive transitions D-5(0)-F-7(2) (Eu3+) and F-4(9/2) - H-6(13/2) (Dy3+) being the most prominent groups, respectively.

Fabrication, patterning and luminescence properties of X-2-Y2SiO5 : A (A = Eu3+, Tb3+, Ce3+) phosphor films via sol-gel soft lithography

X-2-y(2)SiO(5):A (A = Eu3+, Tb3+, Ce3+) phosphor films and their patterning were fabricated by a sol-gel process combined with a soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), scanning electron microscopy (SEM) optical microscopy and photoluminescence (PL) were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 900 degreesC with X-1-Y2SiO5, which transformed completely to X-2-Y2SiO5 at 1250 degreesC. Patterned thin films with different band widths (5 pin spaced by 5 pm and 16 pm spaced by 24 pm) were obtained by a soft lithography technique (micromoulding in capillaries, MIMIC). The SEM and AFM study revealed that the nonpattemed phosphor films were uniform and crack free, and the films mainly consisted of closely packed grains with an average size of 350 run. The doped rare earth ions (A) showed their characteristic emissions in X-2-Y2SiO5 phosphor films, i.e., D-5(0)-F-7(J) (J = 0, 1, 2,3,4) for Eu3+, D-5(3), (4)-F-7(J) (J = 6, 5, 4, 3) for Tb3+ and 5d (D-2)-4f (F-2(2/5),(2/7)) for Ce3+, respectively. The optimum doping concentrations for EU3+, Tb3+ were determined to be 13 and 8 mol% of Y3+ in X-2-Y2SiO5 films, respectively.

A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P-350

In this paper, a new process is proposed to recover rare earths from nitric acid leaching of apatite without interfering with the normal route for fertilizer production using solvent extraction with dimethyl heptyl methyl phosphonate CH3P(O)(OC8H17)(2) (P-350, B). In the present work, the leaching conditions are studied. In selected condition, apatite was dissolved in 20% (v/v) nitric acid solution at 60-70 degrees C while agitating. The most suitable acidity for extraction is 0.4 M HNO3. More than 98% of rare earths in apatite can be recovered using countercurrent extraction process with six stages when phase ratio = 0.5, and defluorination is unnecessary. The influences of phase ratio, stage number, acidity and salting-out agent on extractabilities Of P-350 are studied. The results show that rare earths can be separated with P-350 from Ca, P, Fe and other impurities. Mixed rare earth oxides (REO) of which purity is more than 95% with yield over 98% can be obtained.

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Sol-gel synthesis and photoluminescent properties of LaPO4 : A (A = Eu3+, Ce3+, Tb3+) nanocrystalline thin films

Rare-earth ion (Eu3+, Tb3+, Ce3+)- doped LaPO4 nanocrystalline thin films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography on silicon and silica glass substrates. X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), scanning electron microcopy (SEM), optical microscopy, absorption and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicate that the films begin to crystallize at 700 degreesC and the crystallinity increases with increasing annealing temperature. The morphology of the thin film depends on the annealing temperature and the number of coating layers. The 1000 degreesC annealed single layer film is transparent to the naked eye, uniform and crack-free with a thickness of about 200 nm and an average grain size of 100 nm. Patterned thin films with different strip widths ( 5 - 50 mm) were obtained by micromolding in capillaries ( soft lithography). The doped rare earth ions show their characteristic emission in the nanocrystalline LaPO4 films, i.e., Eu3+ D-5(0)-F-7(J) (J = 1, 2, 3, 4), Tb3+ D-5(3,4) - F-7(J) ( J = 6, 5, 4, 3, 2) and Ce3+ 5d-4f transition emissions, respectively. Both the lifetimes and the PL intensities of Eu3+ and Tb3+ increase with increasing annealing temperature, and the optimum concentrations for them were determined to be 5 mol% and 16 mol% of La3+ in LaPO4 thin films, respectively. An energy transfer phenomenon from Ce3+ to Tb3+ has been observed in LaPO4 nanocrystalline thin films, and the energy transfer efficiency depends on the doping concentration of Tb3+ if the concentration of Ce3+ is fixed.

Synthesis-dependent luminescence properties of Y3Al5O12 : Re3+ (Re=Ce, Sm, Tb) phosphors

By using metal nitrates and oxides as the starting materials, Y2Al5O12 (YAG) and YAG:Re3+ (Re = Ce, Sm, Th) powder phosphors were prepared by solid-state (SS), coprecipitation (CP) and citrate gel (CG) methods. The resulting YAG and YAG-based phosphors were characterized by XRD, FT-IR, SEM and photoluminescent excitation and emission spectra. The purified crystalline phases of YAG were obtained at 800 degreesC (CG) and 900 degreesC (CP, SS). At an identical annealing temperature and doping concentration, the doped rare-earth ions showed the stronger emission intensity in the CP- and SS-derived phosphors than the CG-derived YAG phosphors. The poor emission intensity for the CG-derived phosphors is mainly caused by the contamination of carbon impurities from citric acid in the starting materials.