LaF3纳米线的低温溶剂热法制备及形成机理

LaF₃ nanowires with high aspect ratios have been prepared via a low-temperature solvothermal method using LaCl₃ and KF or NH₄F as starting materials in absolute alcohol at 160 ℃ for 12 h. XRD pattern and TEM images show that the products are hexagonal structure with diameter of 80 nm and length up to 8 μm. The lanthanum sources played most important roles, reaction temperature and time also played important roles in the morphology control of final LaF₃ products. The optimal conditions for ideal LaF₃ nanowire are at a reaction temperature of 160 ℃ and reaction time for 14 h using LaCl₃ and NH₄F as starting materials. A possible formation mechanism for LaF₃ nanowires is proposed.     

Synthesis of highly fluorescent LaF3:Ln/LaF3 core/shell nanocrystals by a surfactant-free aqueous solution route

A surfactant-free aqueous solution route has been established for the synthesis of LaF₃:Ln³⁺/LaF₃ core/shell nanocrystals (Ln=Ce, Tb, Nd) heated at 75 °C at ambient pressure. All the as-prepared nanocrystals with spherical shape have an average size around 20 nm, and consist of well crystallized hexagonal phases. The X-ray photoelectron spectra was used to confirm that the LaF₃ shells have coated the LaF₃:Ce³⁺, Tb³⁺ cores. Compared with that of the original cores under the same conditions, the emission intensity of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ and LaF₃:Nd³⁺/LaF₃ core/shell nanocrystals increased significantly of 120% and 60%, respectively. The quantum yield of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ core/shell nanocrystals reached about 27% in aqueous solution. These results indicate that a significant reduction of the quenching from the surface of the core nanocrystals can be obtained by the synthesis of the core/shell structures, and this method can provide more desirable lanthanide-doped nanocrystals for potential biological applications.     

超声化学法制备不同形貌的CaF2微米晶

采用超声化学法,以CaCl2与不同氟源(NaBF4、K2SiF6)在溶液中反应,制得了不同形貌的CaF2微米晶(立方体、花状、多面体)。用XRD、SEM及TEM对产物晶相及形貌进行了表征。XRD结果显示所有产物均为结晶良好的立方相CaF2。SEM及TEM结果表明由NaBF4制得的产物形貌为均匀的立方体微米晶,而由K2SiF6制得的产物为多面体。在添加配体Na2EDTA的情况下,由NaBF4得到的产物为纳米片组成的花状结构。本文详细讨论了氟源种类、反应物比例、配体等反应参数对产物CaF2形貌的影响,并提出了可能的反应机理。     

Structural and impedance studies on LaF3 thin films prepared by vacuum evaporation

Lanthanum fluoride thin film has been deposited on glass substrates by PVD method at various deposition temperatures (T_s), viz, 300, 473, 573 and 673 K. The hexagonal phase LaF₃ film has been detected by using glancing angle XRD analysis. The structural parameters such as lattice constants, grain size and micro-strain has been calculated from the XRD data. The F⁻ ion conduction through the grain and grain boundary has been analyzed using impedance analysis. The modulus spectra reveals the non-Debye nature and the distribution of relaxation times of the film.     

Synthesis and nonlinear optical properties of BaTi(BO3)2 and Ba3Ti3O6(BO3)2 crystals in glasses with high TiO2 contents

The ternary BaO-TiO₂-B₂O₃ glasses containing a large amount of TiO₂ (20-40 mol%) are prepared, and their optical basicities (Λ), the formation, structural features and second-order optical nonlinearities of BaTi(BO₃)₂ and Ba₃Ti₃O₆(BO₃)₂ crystals are examined to develop new nonlinear optical materials. It is found that the glasses with high TiO₂ contents of 30-40 mol% show large optical basicities of Λ=0.81-0.87, suggesting the high polarizabity of TiO_n polyhedra (n=4-6) in the glasses. BaTi(BO₃)₂ and Ba₃Ti₃O₆(BO₃)₂ crystals are found to be formed as main crystalline phases in the glasses. It is found that BaTi(BO₃)₂ crystals tend to orient at the surface of crystallized glasses. The new XRD pattern for the Ba₃Ti₃O₆(BO₃)₂ phase is proposed through Rietvelt analysis. The second harmonic intensities of crystallized glasses were found to be 0.8 times as large as α-quartz powders, i.e., I^2ω(sample)/I^2ω(α-quartz)=0.8, for the sample with BaTi(BO₃)₂ crystals and to be I^2ω(sample)/I^2ω(α-quartz)=68 for the sample with Ba₃Ti₃O₆(BO₃)₂ crystals. The Raman scattering spectra for these two crystalline phases are measured for the first time and their structural features are discussed.     

Latest developments of bulk crystals and thin films of rare-earth doped CaF2 for laser applications

Several CaF₂ single crystals doped with trivalent rare-earth ions have been grown in the recent years in the form of bulk crystals by using the Bridgman method and in the form of thin films by using the MBE and LPE techniques. The spectroscopic, gain and laser properties of these crystals doped with Pr³⁺, on the one hand, and with Yb³⁺, Tm³⁺ or Er³⁺ ions, on the other hand, have been studied and are reviewed here for their laser potentials in the red and in the infrared spectral domains, respectively.     

Improvement of Er emissions in oxyfluoride glass ceramic nano-composite by thermal treatment

In order to improve the 1.53 μm emission of Er³⁺-doped oxyfluoride glass ceramic containing CaF₂ nano-crystals, series of samples with same Er³⁺ doping lever thermal treated under different conditions were prepared. The UV-VIR-NIR absorption spectra, near-infrared and up-conversion emission spectra, and ⁴I_13/2 decay curves were measured. Based on Judd-Ofelt theory, the radiative transition probability, fluorescence branching ratio and radiative decay time of various metastable transitions of precursor glass and glass ceramics were evaluated. With the increasing of heating temperature, the Judd-Ofelt intensity parameter Ω₂ monotonously decreased from 4.39×10⁻²⁰ to 2.72×10⁻²⁰ cm²; the emission lifetime and quantum efficiency significantly increased from 5.9 to 8.0 ms and 70% to 98%, respectively. The wavelength dependence of gain cross-sections of oxyfluoride glass and glass ceramics were computed to be relatively flat in the range of 1530-1565 nm for population inversion from 0.7 to 1.0.     

Synthesis and optical characterizations of undoped and rare-earth-doped CaF2 nanoparticles

The synthesis of undoped as well as Yb or Er-doped CaF₂ nanocrystals using a reverse micelle method is reported. X-ray powder diffraction and transmission electron microscopy analysis showed that the products were single phased and rather monodispersed with an average particles size around 20 nm. The emission spectra and fluorescence decay times of both Yb³⁺ and Er³⁺ rare earths (RE) ions in CaF₂ nanoparticles are presented. The particles size is increased by heating the as-obtained nanoparticles at different temperatures. The effect of annealing on the optical properties of the two RE ions in CaF₂ is also investigated.     

Superstructure and stacking faults in hydrothermal-grown KBe2BO3F2 crystals

The structure of the hydrothermal-grown nonlinear optical crystal KBe₂BO₃F₂ was investigated. A new structure of the R3?c space group with cell parameters of a=4.422(1) Å and c=37.524(3) Å was obtained by powder X-ray diffraction and Rietveld refinement. The new structure is a 1×1×2 superstructure of the previously reported R32 structure with a different stacking sequence of (Be₂BO₃F₂)_∞ layers along the c axis. The relationship between the refined structure and the experimental results is discussed. A stacking fault mechanism is proposed for the formation of the superstructure as well as the nonuniformity of the hydrothermal-grown KBBF crystals.     

Electronic polarizability and crystallization of K2O-TiO2-GeO2 glasses with high TiO2 contents

Some K₂O-TiO₂-GeO₂ glasses with a large amount of TiO₂ contents (15-25 mol%) such as 25K₂O-25TiO₂-50GeO₂ have been prepared, and their electronic polarizability, Raman scattering spectra, and crystallization behavior are examined to clarify thermal properties and structure of the glasses and to develop new nonlinear optical crystallized glasses. It is proposed that the glasses consist of the network of TiO₆ and GeO₄ polyhedra. The glasses show large optical basicities of Λ=0.88-0.92, indicating the high polarizabity of TiO_n (n=4-6) polyhedra in the glasses. K₂TiGe₃O₉ crystals are formed through crystallization in all glasses prepared in the present study. In particular, 20K₂O-20TiO₂-60GeO₂ glass shows bulk crystallization and 18K₂O-18TiO₂-64GeO₂ glass exhibits surface crystallization giving the c-axis orientation. The crystallized glasses show second harmonic generations (SHGs), and it is suggested that the distortion of TiO₆ octahedra in K₂TiGe₃O₉ crystals induces SHGs.     

A fast synthesis for Zintl phase compounds of Na3SbTe3, NaSbTe2 and K3SbTe3 by microwave irradiation

The microwave irradiation technique was used to prepare three Zintl phase compounds Na₃SbTe₃, NaSbTe₂ and K₃SbTe₃. The as-prepared products were analyzed and characterized by XRD, EDX and SEM techniques. Higher microwave oven power and shorter irradiation time are required for the synthesis of Na₃SbTe₃, whereas lower oven power and longer irradiation time are needed for NaSbTe₂. Moderate microwave irradiation conditions facilitate the formation of pure K₃SbTe₃. Pure phase of Na₃SbTe₃ are directly obtained by this technique for the first time. Compared with the traditional high-temperature solid-state synthesis, the microwave reaction required a considerable shortened reaction time for the preparation of the three Zintl compounds. The initial driving force for these reactions originates from the interaction of microwave electric field with alkali metals (Na and K) and Sb powders.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃-Bi₂O₃-ZnO-Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1 364,介电损耗低至1.2%。     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃‐Bi₂O₃‐ZnO‐Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1364,介电损耗低至1.2%。     

Non-isothermal crystallization kinetics of recycled PET-Si3N4 nanocomposites

Poly(ethylene terephthalate) (PET) is an important industrial material and has been widely applied in consumer products. Due to its slow crystallization rate, nanoparticles are incorporated into PET to function as heterogeneous nucleating agents. In this study, the non-isothermal crystallization behavior of recycled PET-silicon nitride (Si₃N₄) nanocomposites was investigated by differential scanning calorimetry (DSC). In the general analysis of the non-isothermal crystallization curves, it was found that the Si₃N₄ nanoparticles could effectively accelerate the nucleation of PET, but the crystal growth rate was slowed down when the Si₃N₄ content was more than 1 wt%. This might be attributed to the interaction between the PET chains and the surface-treated Si₃N₄ nanoparticles. Results obtained from Avrami and Mo treatments agreed well with the general analysis. Application of the Kissinger method and isoconversional method of Flynn-Wall-Ozawa also showed that Si₃N₄ nanoparticles had a good nucleation effect on the crystallization of PET, and the crystal growth was hindered by Si₃N₄ when the particle loading is higher than 1 wt%.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

LaF_3表面修饰LiMn_2O_4的合成方法及电化学性能的研究(英文)

通过高温固相法制得尖晶石LiMn2O4,然后在通过简单易行的无水乙醇蒸干法包覆LaF3来修饰LiMn2O4。利用XRD,SEM来表征LaF3修饰的LiMn2O4的结构和形貌特征,并通过电化学测试研究LaF3修饰LiMn2O4的高温和常温下的电化学性能,另外结合电化学阻抗谱(EIS)和循环伏安(CV)考察表面修饰的锰酸锂的循环阻抗和循环可逆性。结果显示:经LaF3修饰过的LiMn2O4仍具有尖晶石结构,并且具有良好的电学性能。其中,以3wt%的修饰效果最好,常温循环100次和高温循环50次的循环保持率分别是91%和90%;而且,EIS和CV分别表明经LaF3修饰的LiMn2O4的电荷传递阻抗明显减小,其循环可逆性也明显提高。     

Directional crystallization of B4C-NbB2 and B4C-MoB2 eutectic compositions

We studied the directional crystallization of different compositions in B₄C-NbB₂ and B₄C-MoB₂ systems. The eutectic compositions for both systems are evaluated. It is shown that in the first system the rod-like eutectic structure is formed, in second, the “Chinese hieroglyphics”. In both cases high hardness and high microplasticity are observed, which are much more than for individual component phases. These compositions may be considered as a new kind of self-strengthening composite materials.     

Sb2O3/BiVO4/WO3异质结构建及光电催化合成过氧化氢

采用溶剂热法-旋涂法构建了Sb₂O₃/BiVO₄/WO₃半导体异质结,并采用X射线衍射、扫描电子显微镜、X射线光电子能谱等手段表征了其物化性质。在1.23 V(vs RHE)电位下,BiVO₄/WO₃的光电流密度相对于BiVO₄提高了2倍。进一步复合Sb₂O₃之后,虽然Sb₂O₃/BiVO₄/WO₃薄膜的光电流密度有所下降,但其光电催化产H₂O₂的法拉第效率和产生速率得到明显提升。在1.89V(vs RHE)电位下,3c-Sb₂O₃/BiVO₄/WO₃薄膜产 H₂O₂的法拉第效率提高到约 19%;1c-Sb₂O₃/BiVO₄/WO₃薄膜 H₂O₂产生速率从约2.1 μmol·h^-1·cm^-2提高到约3.6 μmol·h^-1·cm^-2。此外,Sb₂O₃的复合显著提高了BiVO₄/WO₃电极材料的光电催化稳定性。     

Sb2O3/BiVO4/WO3异质结构建及光电催化合成过氧化氢

采用溶剂热法-旋涂法构建了Sb₂O₃/BiVO₄/WO₃半导体异质结,并采用X射线衍射、扫描电子显微镜、X射线光电子能谱等手段表征了其物化性质。在1.23 V(vs RHE)电位下,BiVO₄/WO₃的光电流密度相对于BiVO₄提高了2倍。进一步复合Sb₂O₃之后,虽然Sb₂O₃/BiVO₄/WO₃薄膜的光电流密度有所下降,但其光电催化产H₂O₂的法拉第效率和产生速率得到明显提升。在1.89V(vs RHE)电位下,3c-Sb₂O₃/BiVO₄/WO₃薄膜产H₂O₂的法拉第效率提高到约19%;1c-Sb₂O     

La2(CO3)3纳米线的微乳液法制备与表征

La₂(CO₃)₃ nanowires were prepared in the nonionic surfactant microemulsion(Triton X-100/cyclohexane/water)system. Transmission electron microscopy (TEM) and selected area electronic diffraction (SAED) were used to characterize the shape and size of the products. The results showed that the pH value and concentration of mother solution, temperature and aging time all could affect the morphology and size of the La₂(CO₃)₃ nanowires. The lengths of the nanowires were more than 10 μm and the diameters were in the range of 30～200 nm.