Aqueous solution-based synthesis of rare earth-doped metal oxide thin films

Rare earth-doped TiO₂ thin films have been successfully formed on glass and Si wafer substrates from aqueous solution through equilibrium reaction between metal–fluoro complex and metal oxide, in which Ln³⁺–ethylenediaminetetraacetic acid (EDTA) complex (Ln: rare earth metal) was added into the reaction solution. Ln/Ti ratio and crystalline structure of the film could be controlled by varying the initial concentration of Ln³⁺–EDTA complex solution. The obtained Ln-doped films were densely-packed and had no cracks.     

Epitaxial LnNiO3 (Ln = La, Pr, Nd, Sm) films from 4f-3d heterometallic complexes

A new approach to synthesis of epitaxial thin film of lanthanide nickelates, LnNiO₃ (Ln = La, Pr, Nd, Sm), on single crystal surfaces using solutions of heterometallic complexes as precursors has been developed. The precursors of two types were selected: (1) the complexonates LnNi(DTPA)?nH₂O (H₅DTPA — diethylenetriaminepentaacetic acid) and (2) complexes Ni(mosalen)Ln(piv)₃ (H₂mosalen — N,N′-ethylene-bis(3-metoxy-salicylaldiimin), Hpiv — pivalic acid). The use of heterometallic complexes as precursors allowed to deposit epitaxial films of rare earth nickelates with annealing at low temperature-low oxygen conditions. The LaNiO₃ film deposited from LaNi(DTPA)?nH₂O precursor solution on (001)SrTiO₃ substrate was successfully used as sublayer for highly textured KNbO₃ film grown by MOCVD.     

Optical absorption of Nd, Sm and Dy in bismuth borate glasses with large radiative transition probabilities

This paper reports on the optical properties of Nd³⁺, Sm³⁺ and Dy³⁺ in bismuth borate glasses, with Bi₂O₃ content varying from 30 to 60 mol%. The variation of the optical properties with composition plays a dominant role in determining a good laser host material. The variation of the Judd–Ofelt intensity parameters Ω_t (t=2,4,6) and the radiative transition probabilities and the hypersensitive band positions, with composition, have been discussed in detail. The changes in position and intensity parameters of the transitions in the optical absorption spectra are correlated to the structural changes in the host glass matrix. The variation of Ω₂ with Bi₂O₃ content has been attributed to changes in the asymmetry of the ligand field at the rare earth ion site and to the changes in their rare earth–oxygen (R–O) covalency, whereas the variation of Ω₆ strongly depends on nephlauxetic effect. The shift of the hypersensitive band shows that the covalency of the R–O bond increases with increase of Bi₂O₃ content, due to increased interaction between the rare earth ions and the non-bridging oxygens. The radiative transition probabilities of the rare earth ions are large in bismuth borate glasses, suggesting their suitability for laser applications.     

A general aqueous sol-gel route to Ln(2)Sn(2)O(7) nanocrystals

This paper describes a general aqueous sol-gel route for the synthesis of a series of rare earth stannates, Ln(2)Sn(2)O(7) (Ln = Y, La, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu), with pure pyrochlore phase via the assistance of a cetyltrimethyl ammonium bromide (CTAB) surfactant. The route involves first the formation of CTAB-inorganic lamellar structures and then their thermal decomposition at 800?°C to yield the pyrochlore Ln(2)Sn(2)O(7) nanocrystals. Techniques using a thermo-gravimetric/differential thermal analyzer (TG-DTA), x-ray diffraction (XRD) and transmission electron microscopy (TEM) as well as selected-area electron diffraction (SAED) have been employed to characterize the as-synthesized Ln(2)Sn(2)O(7) nanocrystals. Furthermore, photoluminescence (PL) of the 5% Eu(3+) activated Ln(2)Sn(2)O(7) nanocrystals and carbon monoxide catalytic oxidation over the as-obtained Ln(2)Sn(2)O(7) nanocrystals were investigated. The results indicate that the PL properties as well as the catalytic activity changes significantly with the ionic radii of the rare earth elements.     

稀土对Al-Zn-M g-Cu/Al2O3陶瓷界面润湿性的影响

采用真空座滴法和熔铸法研究了在Al-Zn-Mg-Cu 合金中加入稀土(Ce、Y) 对Al2Zn2M g2Cu/Al₂O₃陶瓷界面润湿性的影响。结果表明,Al-Zn-Mg-Cu 合金中加入稀土可有效降低铝合金/Al₂O₃界面的接触角, 改善界面结合状态; 稀土改善界面润湿性存在一最佳含量范围, 添加Ce 的最佳含量约为0. 5w t% , Y 约为0. 7w t%。稀土改善润湿性的作用主要是稀土与Al₂O₃膜、Al₂O₃陶瓷发生反应。Mg、Zn、Cu 等合金元素在界面富集并参与界面反应对润湿性有利; 稀土与Mg、Zn、Cu 等合金元素适当组合改善润湿性的效果比单一稀土明显。      

Control of the hydrophobicity of rare earth oxide coatings deposited by solution precursor plasma spray by hydrocarbon adsorption

The basis of the hydrophobicity of lanthanide rare earth oxides(REOs)has been the subject of considerable debate.To explore this question,the wetting behaviors and surface compositions of hierarchicallystructured Yb₂o₃(one of the REOs)coatings and non-REO Al₂o₃coatings deposited via solution precursor plasma spray process were investigated in this work.The Yb₂o₃coatings were subjected to a number of post-deposition treatments including vacuum(1-15 Pa)treatment,Ar-plasma treatment,heat treatment(400℃),long-time air exposure and ultra-high vacuum(1×10^-7Pa)treatment.Subsequent characterization showed that different post-deposition treatments resulted in different wetting behavior for the Yb₂o₃coatings which correlated with the content of hydrocarbon on the surface.Yb₂o₃coatings exhibited reversible transitions between superhydrophobicity after vacuum treatment and superhydrophilicity after Ar-plasma or heat treatment,linked to hydrocarbon adsorption onto and desorption from the surface.Yb₂o₃coatings after long-time air exposure and ultra-high vacuum treatment both remained hydrophilic and showed a smaller hydrocarbon content than coatings after vacuum treatment.Al₂o₃coatings with hierarchical surface structures similar to the Yb₂o₃coatings showed an increase in WCA to only-170 after the same vacuum treatment,indicating the REO has a much higher affinity for hydrocarbon adsorption than Al₂o₃,and that the content of hydrocarbon adsorbed on the surface of the REO determined the wetting behavior.     

A CHEMICAL ROUTE FOR THE PREPARATION OF NANOSIZED RARE EARTH PEROVSKITE-TYPE OXIDES FOR ELECTROCERAMIC APPLICATIONS

This paper reviews the work performed by the authors on the preparation of LnTO₃ (Ln = rare earth elements, and T = transition metals) perovskite-type oxides by the thermal decomposition at low temperatures of the corresponding heteronuclear complexes. Bimetallic complexes in the series Ln[Fe(CN₆)]·nH₂O and Ln[Co(CN₆)] nH₂O, with Ln = from La through Yb, and trimetallic complexes in the series Ln¹_xLnnl-x[Co(CN₆)] nH₂O and Ln[FeyCo1-_y(CN₆)] nH₂O were prepared. The formation of the perovskite-type oxides by the thermal decomposition of the complexes has been studied by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), x-ray fluorescence (XRF), Fourier transform infrared (FTTR) spectroscopy, x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The composition and temperature limits of stability for the dimetallic and trimetallic perovskite-type oxides have been clarified. The major role played by the ionic radii of the Ln3⁺ and T3⁺ ions on the formation of the perovskite-type oxides has been identified. Homogeneous perovskite-type oxide powders with nanosized particles, which possess promising characteristics for their applications as functional ceramics, are easily synthesized with this method.     

Synthesis and morphological control of rare earth oxide nanoparticles by solvothermal reaction

Eu doped Y₂O₃ and some kinds of other rare earth oxides nanoparticles such as Er₂O₃, Nd₂O₃, Ho₂O₃, Lu₂O₃, and Dy₂O₃ were prepared by a simple co-precipitation-solvothermal treatment-calcination process, where the co-precipitated amorphous hydroxide precursors obtained by adding rare earth nitrate solutions in ammonia solutions were heated in solvents such as water, alcohols and glycols, followed by calcination in air. The morphology of rare earth oxide particles strongly depended on the solvothermal reaction medium but not related to the kind of rare earth oxide. The powders prepared in water and ethanol possessed nanowire structure, where the aspect ratio of powder treated in water was higher than that in ethanol. The powders prepared by co-precipition-solvothermal treatment-calcination process using ethylene glycol consisted of near-spherical nanoparticles whereas that prepared by conventional co-precipitation-calcination method consisted of hardly agglomerated submicron particles. The nanoparticles of Eu³⁺ doped Y₂O₃ prepared by co-precipition-solvothermal treatment-calcination process showed similar intensity of photoluminescence with the submicron particles by co-precipition-calcination process.     

Preparation of rare earth-cobalt magnet alloy by reduction-diffusion process

Preparation of rare earth-cobalt alloys by reduction-diffusion (R-D) process is described. The process essentially involves mixing of the rare earth oxide and cobalt/cobalt oxide powders in proper proportion and high temperature reduction of the charge in hydrogen atmosphere, followed by aqueous leaching of the reduced mass to yield the alloy powder. Comparison is made of the magnetic properties of the R-D powder with those of the powder prepared by the direct melting (DM) route and it is observed from the reported values for SmCo₅ that the energy product of the R-D powder (∼ 22 MGOe) is only marginally lower than that of the Directly Melted alloy (∼ 25 MGOe). The paper also includes the results of studies carried out at the Bhabha Atomic Research Centre on the preparation of misch metal-cobalt alloy by the R-D process.     

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, H2-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 （Y203）, 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 R2Zr207 （R=La, Ce, Nd, Gd）, CeO2-YSZ, RMeAI11019 （R=La, Nd; Me=Mg, Ca, Sr） and LAP04. 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.     

Effects of rare earth additions during surface boriding on microstructure and properties of titanium alloy TC21

Abstract

In the present paper, the effects of rare earth (RE) additions to the solid state boriding of titanium alloy TC21 have been studied. The microstructural evolution and phase transformations of the borided layers were examined using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction. Moreover, the microhardness for the borided layer was also determined by Vickers hardness test. The results showed that the addition of a small amount of RE elements in the boriding process can lead to an increased boron concentration in the surface layer coupled with the improved surface hardness and coating layer thickness. Furthermore, the presence of trace quantities of RE oxide (Ce₂O₃) in boride layers indicated that the RE elements as catalysts could not only influence but also accelerate boriding process.     

Visible cathodoluminescence of Er ions in β-Ga(2)O(3) nanowires and microwires

Erbium doped β-Ga(2)O(3) nanowires and microwires have been obtained by a vapour-solid process from an initial mixture of Ga(2)O(3) and Er(2)O(3) powders. X-ray diffraction (XRD) analysis reveals the presence of erbium gallium garnet as well as β-Ga(2)O(3) phases in the microwires. Scanning electron microscopy (SEM) images show that the larger microwires have a nearly rectangular cross-section. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) analysis show good crystal quality of the β-Ga(2)O(3) nanowires. The nanostructures have been studied by means of the cathodoluminescence technique in the scanning electron microscope. Er intraionic blue, green and red emission lines are observed in luminescence spectra even at room temperature, which confirms the optical activity of the rare earth ions in?the grown structures. Mapping of the main 555?nm emission intensity shows a non-homogeneous distribution of Er ions in the microstructures.     

稀土化合物纳米粉的研究进展

从稀土化合物的制备、性能出发，比较并讨论了稀土纳米粉体材料的各种制备方法，荧光，催化和光伏等物理特性，并对今后的研究重点和发展前景进行了展望。     

具可变价态稀土氧化物对Mg2Ni合金储氢性能的催化作用

采用球磨法制备Mg2Ni-Ni-5%RExOy(CeO2,Nd2O3,Tb4O7)复合材料。通过XRD,SEM,面扫描能谱分析,电化学及动力学测试系统研究材料的组织及储氢性能。结果表明:添加稀土氧化物后复合材料的结晶程度降低,稀土氧化物催化剂在合金表面分布均匀。复合材料的最大放电容量明显提高,含Tb4O7样品室温下最大放电容量达871mAh·g-1,且具有较高循环稳定性。CeO2及Tb4O7催化剂可有效提高合金电极表面电荷转移能力,增大氢原子在合金内部的传输速率。稀土氧化物催化剂还可提高复合材料的气态吸氢容量,其中含Tb4O7样品的吸氢量最高,在250℃时吸氢量达到2.02%(质量分数),但在较低温度时吸氢速率稍慢。稀土氧化物的催化作用主要与稀土离子的变价特性有关,离子的易变价性越强,则催化活性越高。催化活性由大到小的顺序为Tb4O7>CeO2>Nd2O3。     

Synthesis and characterization of LnPO4 x nH2O (Ln = La, Ce, Gd, Tb, Dy) nanorods and nanowires

Aqueous precipitation method has been used to synthesize lanthanide orthophosphates LnPO4 x nH2O (Ln = La, Ce, Gd, Tb, Dy) with high purity and yield. It has been shown by XRD, TGA, and FTIR characterization that the as-synthesized samples are the LnPO4 hydrates (LnPO4 x nH2O) with hexagonal rhabdophane-type structure. The X-ray diffraction peaks and absorption of PO4(3-) groups show a systematic shift from LaPO4 x nH2O to DyPO4 x nH2O due to the effect of lanthanide ionic contraction. The value of n in LnPO4 x nH2O depends on the lanthanide element and synthetic condition. Field-emission scanning electron microscopy observations show the morphology of as-synthesized samples, which consist entirely of nanorods/nanowires with diameters of 30-100 nm and lengths ranging from several hundreds of nanometers to several micrometers. The anisotropic growth of crystals should be responsible for the formation of nanorods/nanowires, which is related to the hexagonal crystal structure.     

Detonation synthesis of zinc oxide nanometer powders

Novel zinc oxide nanometer powders have been synthesized via detonation reaction with respect to the presence of an energetic precursor, such as lithium nitrate and zinc nitrate. The detonation products of emulsion explosives were characterized by powder X-ray diffraction. Transmission electron microscopy was used to observe the structures. Zinc oxide with primary particles of diameters from 20 to 50 nm and a distribution with proportional spacing of spherical morphologies were found. The oxides produced by this cheap method affirmed the validity of detonation synthesis of nanosize powders. It is concluded that unconventional emulsion explosives are designed uniquely for synthesis of the nanometer zinc oxide.     

稀土氧化物掺杂对SnO2基气体传感器材料性能的影响

采用化学共沉淀法制备Ｙ２Ｏ３、ＺｒＯ２,Ｅｒ２Ｏ３和Ｓｂ２Ｏ２基气体传感器。结果表明掺杂后的材料经煅烧后,平均晶粒尺寸均小于３０ｎｍ,比未经掺杂的材料小,中掺杂体系不同成分材料制备成厚膜传感器,进行了对ＣＯ气体敏感度性能测试,发现掺杂稀土氧化物的气体敏感度较纯ＳｎＯ２厚膜传感器高。其中掺杂Ｅｒ２Ｏ３材料性能最好。     

{[Tb(L)2(H2O)2](Hdmpy)(H2O)2｝∞/丙烯酸酯类聚氨酯稀土高分子材料的制备及性能研究

以9,10-双蒽酸(H2L)和2,6-二甲基吡啶(Hdmpy)为配体,合成了一个二维结构的稀土配合物{[Tb(L)2(H2O)2] (Hdmpy) (H2O)2｝∞;用原位聚合法将该稀土配合物与丙烯酸类聚氨酯大分子单体复合,制备出{[Tb(L)2(H2O)2](Hdmpy)(H2O)2｝∞/丙烯酸酯类聚氨酯稀土高分子材料,并研究了稀土配合物在材料中的分散及材料的热稳定性、荧光性能等.研究结果表明,配合物在稀土高分子材料中主要以200～500nm颗粒均匀分散;且该材料具有良好的热稳定性能(＞300℃),在波长372nm的激发光下,材料在440nm出现最大荧光发射峰,有望应用于发光材料领域.     

稀土氧化物纳米材料制备的研究进展

稀土氧化物纳米材料的合成与制备近年来已成为国内外学者研究的一个热点。本文介绍了国内外稀土氧化物纳米材料制备及合成方法的研究进展,并对稀土氧化物纳米材料的制备方法进行了分类。同时,综合比较了各自的优点和缺点,并对各种制备方法在各个领域的应用前景进行了一定的展望。     

Synthesis of boron suboxide (B6O) with alkaline earth metal oxide materials with improved properties

The pure boron suboxide (B₆O) powder admixed with 1.08?vol% of MgO, CaO, and CaCO₃ (corresponding to 1.5, 1.4, and 0.7?wt%, respectively) were synthesized by hot-pressing and the mechanical properties were evaluated. Pure B₆O powders were sintered at a temperature of 1900°C, while the B₆O-alkaline earth metal oxide admixed powders were sintered at a temperature of 1850°C. All sintering was done under an applied load of 80?MPa in an argon environment. The microstructures and phase analyses were studied by scanning electron microscopy and X-ray diffraction techniques, respectively. The addition of the alkaline earth metal oxide additives resulted in the formation of boride and borate phases, depending on the oxide used. The mechanical properties of the hot-pressed materials were characterized based on their density, hardness, and fracture toughness. Between 95 and 98% of the theoretical densities were achieved and the result indicate a good combination of hardness (between 31.6 and 32.1?GPa) and fracture toughness (between 6.1 and 6.8?MPa.m^0.5) in the B₆O-alkaline earth metal oxide materials. The introduction of the additive enhances the fracture toughness of the pure B₆O-materials, while the fracture mode observed in the sintered materials is mainly transgranular.