Preparation of Rare Earth Hydroxide and Oxide Nanoparticles by Precipitation Method

A series of rare earth hydroxide and oxide nanoparticles have been prepared by precipitation method with alcohol as the dispersive and protective reagent. Transmission electron microscope （TEM） images indicate that the particles are spherical in shape and smaller than 100 nm in size. The crystallite sizes of cubic Ln2O3 have lanthanide shrinking effect, while average crystal lattice distortion rates possess lanthanide swelling effect. The diffraction peak intensity of heavy rare earth oxide nanometer powders is remarkably stronger than that of light rare earth oxide nanometer powders. The variation of diffraction intensity with atomic number presents an inverted W type, forming a double peak structure. Fourier transform infrared （FTIR） spectrums reveal that Ln2O3 nanopowders have higher surface activity than that of ordinary Ln2O3 powders. The UV-vis spectra show that Ln-O bond of these particles is slightly blue-shifted, and its absorption intensity decreases.

Low Temperature Preparation of Ceria Solid Solutions Doubly Doped with Rare-Earth and Alkali-Earth and Their Properties as Solid Oxide Fuel Cells

A series of solid electrolytes, (Ce 0.8 Ln 0.2 ) 1- x M x O 2-δ (Ln= La, Nd, Sm, Gd, M:Alkali earth), were prepared by amorphous citrate gel method. XRD patterns indicate that a pure fluorite phase is formed at 800 ℃. The electrical conductivity and the AC impedance spectra were measured. XPS spectra show that the oxygen vacancies increase owing to the MO doping, which results in the increase of the oxygen ionic transport number and conductivity. The performance of ceria based solid electrolyte is improved. The effects of rare earth and alkali earth ions on the electricity were discussed. The open circuit voltages and maximum power density of planar solid oxide fuel cell using (Ce 0.8 Sm 0.2 ) 1-0.05 Ca 0.05 O 2- δ as electrolyte are 0.86 V and 33 mW·cm -2 , respectively.

The Luminescence Properties and Intramolecular Energy Transfer of Rare Earth Complexes with Aromatic Carboxylic Acids

The triplet state energies of para aminobenzoic acid and nicotinic acid were determined by means of low temperature phosphorescence spectrometry. The energy matches between them and the resonant emitting energy levels of Eu 3+ , Tb 3+ , Sm 3+ , Dy 3+ were studied. The intramolecular energy transfer processes from the two aromatic carboxylic acid ligands to rare earth ions were also discussed on the basis of the measurement results of luminescence intensities, lifetimes and quantum efficiencies.

Electrochemical Properties and Crystal Structure of Rare Earth AB_(3.5)-Type Alloy as Negative Electrode Material in MH-Ni Battery

The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.

Long-Lasting Properties of Rare Earth-Doped Y_2O_2S Phosphors

The aim of this presentation is to report a new result of afterglow materials. The Y 2O 2S∶Ln 3+ (Ln=Sm, Tm) phosphors show bright reddish orange and orange-yellow colors when excited by UV or visible light. The main spectroscopic characterizations of Sm 3+ and Tm 3+ in yttrium oxysulfide and their long-lasting phosphorescence were measured and discussed in this presentation. Their long-lasting phosphorescence can be seen by the naked eyes clearly for about one hour in the dark room after the irradiation light sources were removed. XRD and photoluminescence (PL) spectra as well as the luminance decay were used to characterize these long-lasting phosphorescence phosphors. The results of XRD indicate that the products synthesized through the flux fusion method under 1050 ℃ for 6 h have a good crystallization without any detectable amount of impurity phase. Both the PL spectra and luminance decay results reveal that these phosphors have efficient luminescent and good long-lasting properties. We believe that the experimental data gathered in our present work will be useful in finding some new long-lasting phosphors with different colors.

Luminescence Properties of Rare Earth Ions in Cadmium Metasilicate

The luminescence properties of CdSio(3):RE3+ phosphors doped with various rare earth ions are reported. The series of rare earth ions doped CdSiO3 phosphors are prepared by the conventional high-temperature solid-state method, and characterized by XRD and photoluminescence (PL) spectra. The results of XRD measurement indicate that the products fired under 1050 degreesC for 3 h have a good crystallization without any detectable amount of impure phase. The PL spectra measurement results show that CdSiO3 is a novel self-activated luminescent matrix. When rare earth ions such as Y3+, La3+, Gds(3+), Lus(3+), Ce3+, Nd3+, Ho3+, Era(3+), Tm3+ and Yb3+ are introduced into the CdSi03 host, one broadband centered at about 420 nm resulted from traps can be observed. In the case of other earth ions which show emissions at the visible spectrum region, such as Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+, the mixture of their characteristic line emissions with the similar to 420 nm strong broadband luminescence results in various emitting colors. As a consequence, different emitting colors can be attairied via introducing certain appropriate active ions into the CdSiO3 matrix. In additional, this kind of phosphors shows good long-lasting properties when excited by UV light. All the results show that CdSiO3 is a potential luminance matrix.

Extraction Mechanism of Rare Earths with Sec-Octylphenoxy Acetic Acid by Two-Phase Titration Technique

The compositions of the extracted complexes of La, Gd, Er and Y with sec octyl phenoxy acetic acid in heptane and the related apparent extraction equilibrium constants K M were determined using two phase titration technique. The stoichiometric compounds for La, Gd, Er and Y should be LaA 3·2.5HA, GdA 3·3HA, ErA 3·3.1HA and YA 3·4.3HA respectively. And their p K M are 3.43, 3.46, 3.08 and 2.58 respectively.

Relationship between Crystal Structure and Luminescence Properties of (Y_(0.96-x)Ln_xCe_(0.04))_3Al_5O_(12) (Ln=Gd, La, Lu) Phosphors

The doping effects of La^3＋, Gd^3＋ and Lu^3＋ on the crystal structure and luminescence properties of （Yo96-x LnxCe0.04）3Al5O12（Ln = Gd, La, Lu） phosphors were studied. The X-ray diffraction patterns presented that with the inerease of the doping concentrations of La^3＋ and Gd^3＋ ions, the d-value of （Y0.96-xLnxCe0.04）3Al5O12 （Ln = Gd, La） inereased and the larger the doping ion, the stronger the effect would be. The doping amount causing phase transition in （Y0.96-xLnxCe0.04）3Al5O12 decreased with the inerease of the ionic radii of the doping lanthanide ions （La^3＋： 0.106 nm, Gd^3＋： 0. 094 nm, Lu^3＋ ： 0.083 nm）. The bigger doping ion of Gd^3＋ made the emission of （Y0.96-xGdxCe0.04）3Al5O12 move to red spectral region, but the smaller one of Lu^3＋ made it blue.

Photoluminescence and thermoluminescence properties of dysprosium doped zinc metaborate phosphors

Polycrystalline powder samples of dysprosium doped Zn（BO2）2 phosphors were prepared by solid state reaction in air at high temperature and characterized by X-ray powder diffraction. The IR, Photoluminescence （PL）, diffuse reflectance and three-dimensional （3D） thermoluminescence （TL） emission spectrum after 60^Co gamma ray irradiation were investigated. The characteristic 3D TL emission bands at about 425, 481 and 573 um with a main emission band of around 573 um were attributed to the host emission, 4^F9/2→6H15/2 and F9/2→6^H13/2 f-f transitions of Dy^3＋ ions. No emission from Dy^2＋ ions was observed in the measurement wavelength range. The TL-dose response of the Zn（BO2）2：Dy polycrystalline powder sample to gamma ray radiation in the range from 1 to 100 Gy at clinical dose levels was almost linear. The experimental results showed that Zn（BO2）2：Dy had potential use as the materials of gamma-ray thermoluminescence dosimeter （TLD） for clinical dosimetry.

Effect of Yb^(3+) concentration on the structures and upconversion luminescence properties of Y_2O_3:Er^(3+) ultrafine phosphors

Y2O3：Er^3＋ ultrafine phosphors with a varying Yb^3＋ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y2O3：Er^3＋ ultrafine phosphors with Yb^3＋ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb^3＋ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ^2H11/2→^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 →^4I15/2 transitions of Er^3＋, respectively. The intensity of red emission increases with increasing Yb^3＋ ion concentration. The effect of Yb^3＋ ion concentration on the structures and upconversion luminescence mechanism were discussed.

Sol-Gel Preparation of Zn2 SiO4 :Mn Phosphor Layers on Silica Spheres and Their Luminescent Properties

The synthesis and luminescence properties of Zn2 SiO4: Mn phosphor layers on spherical silica spheres, i.e.,a kind of core-shell complex phosphor, Zn2SiO4: Mn@ SiO2 were described.Firstly, monodisperse silica spheres were obtained via the Stober method by the hydrolysis of tetraethoxysilane(TEOS) Si ( OC2H5 ) 4 under base condition ( using NH4 OH as the catalyst).Secondly, the silica spheres were coated with a Zn2 SiO4: Mn phosphor layer by a Pechini solgel process.X-ray diffraction ( XRD), scanning electron microscope ( SEM), energy-dispersive X-ray spectrum ( EDS )and photoluminescence (PL) were employed to characterize the resulting complex phosphor.The results confirm that1000 ℃ annealed sample consists of crystalline Zn2SiO4: Mn shells and amorphous SiO2 cores.The phosphor show the green emission of Mn2+ at 521 nm corresponding 4T1 (4G) - 6 A1 (6S) transition, and the possible luminescence mechanism is proposed.

Preparation and characterization of BaLiF_3:Er^(3+) nanoparticles by the hydrothermal microemulsion synthesized method

Nanoparticles of BaLiF3：Er^3＋ were prepared from the quaternary microemulsions of Cetyltrim-Enthyl Ammonium Bromide （CTAB）, n-butanol, n-octane, and water, using the hydrothermal-microemulsion technique. The complex fluorides were characterized by means of X-ray power diffraction, Environmental Scanning Electron Microscopy （ESEM）, and fluorescence spectra. The positions and intensifies of the peaks in the XRD pattern of the final products indicate the formation of BaLiF3·Er^3＋. No other peaks or impurities were detected. The average size of the nanoparticles, calculated with the Debye-Scherrer equation was 98.45 nm, which was in agreement with the result of ESEM. The infrared fluorescence spectra consisted of four peaks with a predominant peak located at 1540 nm.

Fabrication and Luminescence Properties of Ca_2Gd_8 (SiO_4 )_6O_2:Er^(3+) Phosphors via Sol-Gel Process

Ca2RE8(SiO4)6O2(RE = Y, Gd, La) is a kind of ternary rare-earth-metal silicate with the oxyapatite structure, which was used as host materials for the luminescence of various rare earth and mercury-like ions. Ca2Gd8(SiO4)6O2: Er3 + phosphors were prepared through the sol-gel process. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicate that the phosphors crystallized completely at 1000℃. SEM study reveals that the average grain size is 400 ~ 1000 nm. In Ca2Gd8 (SiO4)6O2 : Er3+ phosphors, the Er3+ shows its characteristic green emission at 528 nm (2H11/2-4I15/2) and 548 nm (4 S3/2-4 I15/2) upon excitation into 382 nm, with an optimum doping concentration of 5% (mole fraction) of Gd3+ in the host lattices.

Investigation on Preparation and Fluorescence Properties of Oxy-Fluoride Glass Co-Doped with Er^(3+) and Yb^(3+)

The glass sample based on the composition of 45PbF_2-45GeO_2-10WO_3 co-doped with Yb^(3+)/Er^(3+) was prepared by the fusion method in two steps: melted at 950 ℃ for 20～25 min then annealed at 380 ℃ for 4 h. Through the V-prism it is found that the refractive index of host glass and the sample are 1.517 and 1.65 respectively. The transmittance was observed by using the ultraviolet-visible-infrared spectrometer in the wavelength range from 0.35 to 2.5μm. The transmittance of the host glass is beyond 73%. That of the sample is beyond 50% and there are characteristic absorption peaks of rare-earth ions. The emission spectrum was measured by using the Hitachi F-4500 fluorescent spectrometer pumped by 980 nm semiconductor laser. There are a strong emission peak at 530 nm and a weak peak at 650 nm.

Citrate-Gel Synthesis and Luminescent Properties of α-Zn_3(PO_4)_2 Doped with Eu^(3+)

By using inorganic salts as raw materials and citric acid as complexing agent, α-Zn 3(PO 4) 2 and Eu 3+ doped α-Zn 3(PO 4) 2 phosphor powders were prepared by a citrate-gel process. X-ray diffraction (XRD), TG-DTA, FT-IR and luminescence excitation and emission spectra were used to characterize the resulting products. The results of XRD reveal that the powders begin to crystallize at 500 ℃ and pure α-Zn 3(PO 4) 2 phase is obtained at 800 ℃. And the results of XRD reveal that Eu 3+ exists as EuPO 4 in the powder. In the phosphor powders, the Eu 3+ shows its characteristic red-orange (592 nm, 5D 0- 7F 1) emission and has no quenching concentration.

Luminescence and Defect Properties of Novel Bluish-Green Phosphor β-Zn_3(PO_4)_2∶Zr^(4+)

Luminescence and defect properties of novel phosphor β-Zn 3(PO 4) 2:Zr 4+ were systematically investigated. Corresponding to its lowest optical absorption transition at 240 nm, phosphor emits a bluish-green light at 485 nm, which yields the Stokes shift about 20000 cm -1. The unusual optical properties of Zr 4+ ion are ascribed to its uncommon coordination environment. In addition it shows intensive bluish-green long lasting phosphorescence (LLP) due to the existence of electron trap, which is generated by aliovalent substitution of Zr 4+ ion for the cation site in the matrix as shown in thermoluminescence (TL) spectrum.

Hydrothermal synthesis and fluorescence of YF_(3):Eu^(3+)

Europium(Ⅲ)-doped YFis prepared by a hydrothermal process at 200℃.X-ray diffraction(XRD) pattern identifies the formation of YFphase without detectable impurity.Environment scanning electron microscopy(ESEM) image shows the even size distribution of the samples with cubic morphology.The excitation and emission spectra of the rare earth ions doped YFare investigated by fluorescence spectrophotometer.The excitation spectrum for 591 nm emission has several excitation bands at 320, 365,386,397 and 467 nm,and the main peak value was 397 nm.Typical Euemission peaks at 591 nm(~5D→~7F) and 612 nm (~5D→~7F) are observed when excited by 397 nm,and the strongest emission is 591 nm,demonstrating that the rare earth ions occupy the centrosymmetrical sites in YF.

Extraction and Stripping of Ytterbium (Ⅲ) from H_2SO_4 Medium by Cyanex 923

The extraction and stripping of ytterbium（ Ⅲ） from sulfuric acid medium using Cyanex 923 in heptane solution was investigated. The effects of extraetant concentration, pH and sulfate ion as well as stripping agents, acidity and temperature on the extraction and stripping were studied. The equilibrium constants and thermodynamic parameters, such as △n （10.76 kJ·mol^-1）, △G （-79.26 kJ·mol^-1） and △S （292.41 J·K^-1·mol^-1）, were calculated. The extraction mechanism and the complex species extracted were determined by slope analysis and FTIR spectra. Furthermore, it was found that the extraction of Yb （Ⅲ） from sulfuric acid medium by Cyanex 923 increased with pH, concentration of SO4^2-, HSO4^-, and extractant concentration, and approximately a quantitative extraction of Yb（ Ⅲ） was achieved at an equilibrium pH near 3.0, and the extracted complex was YbSO4（HSO4）·2Cyanex923（o）.

Luminescence and Energy Transfer Properties of Ca_2Gd_8(SiO_4)_6O_2∶A(A=Pb^(2+), Tm^(3+))Phosphors

Ca_2Gd_8(SiO_4)_6O_2∶ A(A=Pb^(2+), Tm^(3+))phosphors were prepared through the sol-gel process. X-ray diffraction(XRD), scanning electron microscopy(SEM)and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicate that the phosphors crystallized completely at 1000 ℃. SEM study reveals that the average grain size is 300～1000 nm. In Ca_2Gd_8(SiO_4)_6O_2∶Tm^(3+) phosphors, the Tm^(3+) shows its characteristic blue emission at 456 nm(~1D_2—~3F_4)upon excitation into its ~3H_6—^(1)D_2(361 nm), with an optimum doping concentration of 1mol% of Gd^(3+) in the host lattices. In Ca_2Gd_8(SiO_4)_6O_2∶Pb^(2+), Tm^(3+) phosphors, excitation into the Pb^(2+) at 266 nm(~1S_0—~3P_1)yields the emissions of Gd^(3+) at 311 nm(~6P—~8S)and Tm^(3+) at 367 nm(~1D_2 —~3H_6)and 456 nm(~1D_2—~3F_4), indicating that energy transfer processes of Pb^(2+)—Gd^(3+) and Pb^(2+)—Tm^(3+) have occurred in the host lattices.