Electrochemical Determination of Gibbs Energy of Formation of LaCrO3 Using a Composition-Graded Bielectrolyte

Presented are new measurements of the standard Gibbs free energy of formation of rhombohedral LaCrO3 from component oxides La2O3 and Cr2O3 in the temperature range from 875 to 1175K, using a bielectrolyte solid-state cell incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3)(y)(CaF2)(1-y) (y=0-0.32). The results can be represented analytically as Delta G(f(ox))(o) (+/- 2270)/Jmol(-1)=-72329+4.932 (T/K). The measurements were undertaken to resolve serious discrepancies in the data reported in the literature. A critical analysis of previous electrochemical measurements indicates several deficiencies that have been rectified in this study. The enthalpy of formation obtained in this study is consistent with calorimetric data. The standard enthalpy of formation of orthorhombic LaCrO3 from elements at 298.15K computed from the results of this study is Delta H-f(298.15)(o)/kJmol(-1)=-1536.2 (+/- 7). The standard entropy of orthorhombic LaCrO3 at 298.15K is estimated as 99.0 (+/- 4.5)J(molK)(-1).

Use of Composition-Graded Bi-Electrolyte Cells for Thermodynamic Studies on Lanthanum Aluminates

Innovative bi-electrolyte solid-state cells incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3) y (CaF2) 1-y (y = 0 to 0.32) were used for measurement of the standard Gibbs energy of formation of hexagonal La0.885Al11.782O19 and cubic LaAlO3 from component binary oxides La2O3 and alpha-Al2O3 in the temperature range from 875 to 1175 K. The cells were designed based on experimentally verified relevant phase relations in the systems La2O3-Al2O3LaF3 and CaF2-LaF3. The results can be summarized as: 5.891 alpha-Al2O3 + 0.4425 La2O3 (A-rare earth)-> La0.885Al11.782O19 (hex), Delta G(f(ox))(degrees)(+/- 2005)/Jmol(-1) = -80982 + 7.313(T/K); 1/2 La2O3 (A-rare earth) + 1/2 a-Al2O3 -> LaAlO3 (cubic), Delta G(f(ox))(degrees)(+/- 2100)/Jmol(-1) = -59810 + 4.51(T/K). Electron probe microanalysis was used to ascertain the non-stoichiometric range of the hexaaluminate phase. The results are critically analyzed in the light of earlier electrochemical measurements. Several imperfections in the electrochemical cells used by former investigators are identified. Data obtained in the study for LaAlO3 are consistent with calorimetric enthalpy of formation and entropy derived from heat capacity data. Estimated are the standard entropy and the standard enthalpy of formation from elements of hexagonal La0.885Al11.782O19 and rhombohedral LaAlO3 at 298.15 K. c 2014 The Electrochemical Society. All rights reserved.

新型掺铒离子氧氟碲酸盐玻璃的光谱性质

探求新的具有优良的热学和光学性能的基质玻璃系统，是获得具有宽带宽和增益平坦的掺Er^3＋光纤放大器（EDFA）的一种有效途径。制备了一种新型氧氟碲酸盐玻璃TeO2-BaF2-LaF3，并对其热学性能和光学性质进行了测试。应用乍得-奥菲尔特（Judd-Ofelt）理论计算了Er^3＋离子的J-O理论参量和荧光寿命r。探讨了氟化物的引入对碲酸盐玻璃结构的改变的影响，并分析了其对玻璃的热学性质和光学性质的影响。实验发现，获得的氧氟碲酸盐玻璃具有优良的热学稳定性（△T=156.6C），宽的荧光半峰全宽（72nm）

沉积速率对热舟蒸发LaF3薄膜性能的影响

用热舟蒸发方法在不同的沉积速率下制备了LaF3单层膜,并对部分单层膜进行了真空退火。分别采用X射线衍射(XRD),Lambda 900 光谱仪和355 nm Nd∶YAG脉冲激光测试了薄膜的晶体结构、透射光谱和激光损伤阈值(LIDT),并通过透射光谱计算得到样品的折射率和消光系数。实验结果表明,增大沉积速率有利于LaF3薄膜的结晶和择优生长,可以提高薄膜的致密性和折射率,但薄膜的抗激光损伤能力有所下降;沉积速率太大,又会恶化薄膜的结晶性能,同时薄膜中产生大量孔洞,薄膜的机械强度降低,导致薄膜的折射率减小和

热舟蒸发LaF_3薄膜的紫外性能研究

研究了沉积温度对热舟蒸发氟化镧薄膜结构和光学性能的影响,沉积温度从200℃上升到350℃,间隔为50℃.采用分光光度计测量了样品的透射率和反射率光谱曲线,并在此基础上进行了光学损耗、光学常数以及带隙和截止波长的计算.采用表面轮廓仪进行了表面形貌和表面粗糙度的标定,采用X射线衍射(XRD)方法测量了不同沉积温度下样品的微结构.发现在短波长波段,随着沉积温度的升高,光学损耗增加,晶粒尺寸增大,表面粗糙度略有增加.不过散射损耗在光学损耗中所占比例均很小,光学损耗的增加主要由吸收损耗引起.随着沉积温度的升高,折射率与消光系数增大,带隙变小,相对应的截止波长向长波方向移动.

355nm增透膜的设计、制备与性能

用热舟蒸发法结合修正挡板技术制备了355 nm LaF3/MgF2增透膜,并对部分样品进行了真空退火。采用Lambda 900光谱仪测试了增透膜的低反光谱和透射光谱,并考察了其光谱稳定性;使用脉冲8 ns的355 nm激光测试了增透膜的激光损伤阈值(LIDT);采用Normarski显微镜对增透膜的表面缺陷密度和破斑形貌进行了观察。实验结果表明,制备得到的增透膜的剩余反射率较低,光谱稳定性好;真空退火对增透膜的激光损伤阈值没有改善;增透膜的破环形貌为散点形式,结合破斑深度测试表明薄膜的破坏源于薄膜和基底界面的缺陷点。JGS1熔石英基底由于有好的表面状况、固有的高激光损伤阈值和以其为基底的增透膜具有更低的表面场强,使得其上的增透膜有更高的抗激光损伤能力。

Characterization of LaF3 coatings prepared at different temperatures and rates

LaF3 thin films were prepared by thermal boat evaporation at different substrate temperatures and various deposition rates. X-ray diffraction (XRD), Lambda 900 spectrophotometer and X-ray photoelectron spectroscopy (XPS) were employed to study crystal structure, transmittance and chemical composition of the coatings, respectively. Laser-induce damage threshold (LIDT) was determined by a tripled Nd:YAG laser system with a pulse width of 8 ns. It is found that the crystal structure became more perfect and the refractive index increased gradually with the temperature rising. The LIDT was comparatively high at high temperature. In the other hand, the crystallization status also became better and the refractive index increased when the deposition rate enhanced at a low level. If the rate was super rapid, the crystallization worsened instead and the refractive index would lessen greatly. On the whole, the LIDT decreased with increasing rate. (C) 2007 Elsevier B.V. All rights reserved.

Ionic liquid-based "all-in-one" synthesis and photoluminescence properties of lanthanide fluorides

A facile route to the synthesis of LnF(3) nanocrystals has been accomplished in three ionic liquids (ILs) (OmimPF(6), OmimBF(4), and BmimPF(6)). The partial hydrolysis of PF6- and BF4- was utilized to introduce a new fluoride source. Uniform LnF(3) (Ln = La, Ce, Pr, Nd, Sm, Eu, Er), Tb3+-doped CeF3, and Eu3+-doped LaF3 nanocrystals could be obtained in a large scale, and the products were up to 0.15 g per 10 mL solvents. In the "all-in-one" systems, the ILs acted as solvents, reaction agents, and templates.

Shape controllable synthesis and upconversion properties of NaYbF4/NaYbF4 : Er3+ and YbF3/YbF3 : Er3+ microstructures

Ytterbium fluoride compounds with different crystal phases and morphologies, such as beta-NaYbF4 hexagonal microdisks, microprisms, microtubes, and alpha-NaYbF4 submicrospheres as well as YbF3 octahedra, have been synthesized via a facile hydrothermal route. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and photoluminescence (PL) spectra were used to characterize the samples.

Synthesis and photoluminescent properties of silica-coated LaCeF3 : Tb nanocrystals

La0.45Ce0.45F3:Tb (10 mol% Tb) nanoparticles was synthesized via sonochemical method and then coated with silica (SiO2) shells through a microemulsion process, resulting in the formation of core/shell structured LaCeF3:Tb/SiO2 nanoparticles. The obtained core/shell LaCeF3:Tb/SiO2 nanoparticles are spherical and uniform in size (average size about 60 nm), strongly fluorescent, and long fluorescence lifetime (1.87 ms). This kind of nanoparticles was water-soluble, which could be applied in biological labeling and other fields.

Ionic liquid-based "all-in-one" synthesis and photoluminescence properties of lanthanide fluorides

A facile route to the synthesis of LnF(3) nanocrystals has been accomplished in three ionic liquids (ILs) (OmimPF(6), OmimBF(4), and BmimPF(6)). The partial hydrolysis of PF6- and BF4- was utilized to introduce a new fluoride source. Uniform LnF(3) (Ln = La, Ce, Pr, Nd, Sm, Eu, Er), Tb3+-doped CeF3, and Eu3+-doped LaF3 nanocrystals could be obtained in a large scale, and the products were up to 0.15 g per 10 mL solvents. In the "all-in-one" systems, the ILs acted as solvents, reaction agents, and templates.

Controllable Red, Green, Blue (RGB) and Bright White Upconversion Luminescence of Lu2O3:Yb3+/Er3+/Tm3+ Nanocrystals through Single Laser Excitation at 980 nm

Lu2O3:Yb3+/Er3+/Tm3+ nanocrystals have been successfully synthesized by a solvothermal process followed by a subsequent heat treatment at 800 degrees C. Powder X-ray diffraction, transmission electron microscopy, upconversion photoluminescence spectra, and kinetic decay were used to characterize the samples. Under single-wavelength diode laser excitation of 980 nm, the bright blue emissions of Lu2O3:Yb3+, Tm3+ nanocrystals near 477 and 490 nm were observed due to the (1)G(4)-> H-3(6) transition of Tm3+. The bright green UC emissions of Lu2O3:Er3+ nanocrystals appeared near 540 and 565 nm were observed and assigned to the H-2(11/2)-> I-4(15/2) and S-4(3/2)-> I-4(15/2) transitions, respectively, of Er3+. The ratio of the intensity of green luminescence to that of red luminescence decreases with an increase of concentration of Yb3+ in Lu2O3:Er3+ nanocrystals.

Uniform Ln(OH)(3) and Ln(2)O(3) (Ln = Eu, Sm) Submicrospindles: Facile Synthesis and Characterization

Monodisperse hexagonal Ln(OH)(3) (Ln = Eu, Sm) submicrospindles with uniform morphology and size have been Successfully synthesized in a large scale via a Facile aqueous solution route from the mixture of aqueous solutions or LnCl(3) and NaOH at 5 degrees C without using any surfactant or template. The as-synthesized products are characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), energy-dispersive X-ray (EDX) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The SEM and TEM images show that the as-formed Ln(OH)(3) samples have a spindlelike shape with an equatorial diameter of 80-200 nm and a length of 500-900 nm, which are aggregates of even smaller nanoparticles.

Synthesis of REF3 (RE = Nd, Tb) nanoparticles via a solvent extraction route

NdF3 and TbF3 nanoparticles were successfully synthesized via a solvent extraction route using Cynex923 (R3P=O). X-ray diffraction (XRD) study showed that pure hexagonal phase NdF3 and pure orthorhombic phase TbF3 could be obtained under the current synthetic conditions. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations indicated that as-obtained NdF3 nanoplates have a diameter of 50-80 nm and thickness of 10-20 nm and TbF3 products have sphere morphologies with diameter from 70 to 170 nm. The driving force for the growth of NdF3 nanoplates could be attributed to the hexagonal crystal structure. The luminescence properties of NdF3 and TbF3 nanoparticles were investigated, which indicated that NdF3 nanoparticles showed typical emission at 888,1064, and 1328 nm and TbF3 nanoparticles showed characteristic emission of Tb3+ (f-f).

Different microstructures of ss-NaYF4 fabricated by hydrothermal process: Effects of pH values and fluoride sources

beta-NaYF4 microcrystals with a variety of morphologies, such as microrod, hexagonal microprism, and octadecahedron, have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra were used to characterize the samples. The intrinsic structural feature of beta-NaYF4 seeds and two important external factors, namely, the pH values in the initial reaction solution and fluoride sources, are responsible for shape determination of beta-NaYF4 microcrystals. It is found that the organic additive trisodium citrate (Cit(3-)) as a shape modifier has the dynamic effect by adjusting the growth rate of different facets under different experimental conditions, resulting in the formation of the anisotropic geometries of various beta-NaYF4 microcrystals. The possible formation mechanisms for products with various architectures have been presented. A systematic study on the photoluminescence of Tb3+-doped beta-NaYF4 samples with rod, prism, and octadecahedral shapes has shown that the optical properties of these phosphors are strongly dependent on their morphologies and sizes.