A comparative study of (Ce) and (Gd) doping influence on the superconducting properties of YBCO ceramics

This work is devoted to investigate the structural and electrical properties of the Ce, Gd-doped YBCO superconductors bulk ceramics. YBa_2-xRE_xCu₃O_7−δ (x = 0, 0.01, 0.05, 0.1) (RE = Gd, Ce) samples were prepared by means of conventional solid-state reaction. X-ray diffraction analysis was carried out to identify the present phases in the as-prepared samples followed by the determination of their lattice parameters. Fourier Transform Infrared Spectroscopy (FTIR) was used to identify the functional groups. Furthermore, the morphology and the surface roughness of the studied samples were characterized using Scanning Electronic Microscopy (SEM) and Atomic Force Microscopy (AFM). Vickers Micro-hardness of the as-prepared samples was examined. Besides, the electrical resistivity measurements were achieved to determine the critical transition temperature T_C and the critical current density J_C.The effect of Ce and Gd additions is clearly noticed in the obtained results, where all the prepared samples are superconductors with the presence of Y123 as a major polycrystalline phase. From the XRD patterns, the intensities of the Y123 corresponding peaks decrease with further increasing the Ce and Gd contents. In addition, the variation of the cell parameters was significant after additions of both Ce and Gd, which affect the grain size and the oxygen content of the YBa_2-xRE_xCu₃O_7−δ system. An improvement of the structure and surface roughness is observed on SEM and AFM images. Likewise, Vickers micro-hardness has increased after the Ce and Gd additions. Although, the critical transition temperature T_C was not further increased upon Ce or Gd additions compared to the undoped YBCO samples. Nevertheless, an exception has been recorded with an increase of T_C for YBa_2-xRE_xCu₃O_7−δ with (RE = Gd, x=0.01) to reach 88 K. In contrary, an improvement of the deduced critical current density J_C was achieved for all Ce-doped YBCO samples unlike those of Gd-doped samples.     

Effects of rare-earth oxide doping on the thermal radiation performance of HfO2 coating

In this study, the REO-HfO₂ (REO = Tb₄O₇, Gd₂O₃ and Sm₂O₃) coatings and pure HfO₂ coatings were prepared by atmospheric plasma spraying. The chemical compositions, morphologies, infrared radiation performance and thermal resistances of the coatings were systematically investigated. The experimental results showed that the Tb₄O₇-HfO₂, Gd₂O₃-HfO₂, Sm₂O₃-HfO₂ and pure HfO₂ coatings had infrared emissivity values of 0.863, 0.852, 0.854 and 0.621, respectively, at room temperature. Based on the phase analysis, the higher infrared emissivity of the REO-HfO₂ coatings could be attributed to the fact that the newly formed RE₂Hf₂O₇ (RE = Tb, Gd and Sm) phase, which had a defective fluorite-type structure, and the RE³⁺ ions enhanced the lattice absorption and electron absorption. Additionally, the Tb₄O₇-HfO₂ coating exhibited a relatively higher infrared emissivity than those of the Gd₂O₃-HfO₂ and Sm₂O₃-HfO₂ coating over the wavelength range of 1–15 μm, which was due to the relatively higher vibrational frequency of the TbO bond in RE₂Hf₂O₇ (RE = Tb, Gd and Sm) and the transformation of Tb³⁺ into Tb⁴⁺ in the Tb₄O₇-HfO₂ system. In addition, the REO-HfO₂ ceramic coatings exhibited excellent thermal resistance, which could withstand high-temperature treatment at 1600 °C for at least 50 h without undergoing a phase change and exfoliation, and the infrared emissivity at different temperatures hardly changed after thermal treatment.     

关于江西省稀土永磁产业发展的初步思考

本文阐述了稀土永磁产业的概念、市场细分和特征,分析了国内外稀土永磁产业发展现状及未来发展趋势,提出了发展我省稀土永磁产业的六点建议。     

Crystallization processes,compressibility, sinterability and mechanical properties of La-monazite-type ceramics

Lanthanide orthophosphate ceramics with monazite structure gained broad interest for several industrial applications. The crystallization processes, compressibility and sinterability of monazite-type lanthanum orthophosphate powder hydrothermally synthesized at 200 °C as well as mechanical properties of the sintered compacts were investigated. Based on a combination of thermo- and surface area analyses, X-ray diffraction as well as scanning electron microscopy studies it was found that the crystallization process occurs at ∼500 °C and the final crystallization of LaPO₄ monoclinic phase takes place at 1400 °C. The sintered pellets are characterized by a density of 98% of theoretical density, a Vickers hardness of 5.7 ± 0.1 GPa and fracture toughness of 1.4 ± 0.1 MPa m^0.5.     

Effect of Ca doping on the electrical conductivity of the high temperature proton conductor LaNbO4

The sintering properties, crystal structure and electrical conductivity of La_1−xCa_xNbO_4−δ (x = 0, 0.005, 0.01, 0.015, 0.02 and 0.025), prepared by a solid-state reaction, have been investigated using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS), and electrochemical impedance spectroscopy (EIS). In 2.5% Ca-doped samples, a small amount of impurities Ca₂Nb₂O₇ were observed from the XRD patterns. Impedance spectra show that the grain boundary resistance increases with increasing Ca content, while the bulk resistance remains essentially constant below 550 °C. Despite the higher degree of grain growth observed for higher Ca doping levels, the total conductivity of the La_1−xCa_xNbO_4−δ series decreases with increasing Ca content from 0.5 to 2.0 mol%. The activation energy for the total conductivity decreases with increasing Ca content from 0.71 eV (x = 0) to 0.54 eV (x = 0.01) for the high temperature tetragonal phase, then it increases to 0.60 eV for x = 0.02. For the monoclinic phase, the activation energy exhibits similar trend except La_0.995Ca_0.005NbO_4−δ shows the lowest value of 1.26 eV. The Ca and Nb content present at the grain boundaries for La_0.99Ca_0.01NbO_4−δ are much higher than that on the grain surface, as determined from the EDS analysis. These results imply that the solubility of CaO in LaNbO₄ is in the range from 0.5 to 1.0 mol%. By increasing the sintering temperature from 1500 °C to 1550 °C, the proton conductivity of the Ca-doped LaNbO₄ was improved with enlarged grain size due to a reduction in the resistive grain boundary contribution.     

Reversible hydrogen storage in a 3NaBH4/YF3 composite

A 3NaBH₄/YF₃ hydrogen storage composite was prepared through ball milling and its hydrogen sorption properties were investigated. It is shown that NaBH₄ does not react with YF₃ during ball milling. The dehydrogenation of the composite starts at 423 °C, which is about 100 °C lower than the dehydrogenation temperature of pure NaBH₄, with a mass loss of 4.12 wt%. Pressure–Composition–Temperature tests reveal that the composite has reversible hydrogen sorption performance in the temperature range from 350 °C to 413 °C and under quite low hydrogenation plateau pressures (<1 MPa). Its maximum hydrogen storage capacity can reach up to 3.52 wt%. The dehydrogenated composite can absorb 3.2 wt% of hydrogen within 5 min at 400 °C. Based on the Pressure–Composition–Temperature analyses, the hydrogenation enthalpy of the composite is determined to be −46.05 kJ/mol H₂, while the dehydrogenation enthalpy is 176.76 kJ/mol H₂. The mechanism of reversible hydrogen sorption in the composite involves the decomposition and regeneration of NaBH₄ through the reaction with YF₃. Therefore, the addition of the YF₃ to NaBH₄ as a reagent forms a reversible hydrogen storage composite.     

Luminescence properties of Ca4Y6(SiO4)6O:RE (RE = Eu, Tb, Dy, Sm and Tm) under vacuum ultraviolet excitation

The vacuum ultraviolet excited luminescent properties of Eu³⁺, Tb³⁺, Dy³⁺, Sm³⁺ and Tm³⁺ in the matrices of Ca₄Y₆(SiO₄)₆O were investigated. The bands at about 173 nm in the vacuum ultraviolet excited spectra were attributed to host lattice absorption of the matrix Ca₄Y₆(SiO₄)₆O. For Eu³⁺-doped samples, the O²⁻ → Eu³⁺ CTB was identified at 258 nm. Typical 4f-5d absorption bands in the region of 195-300 nm were observed in Tb³⁺-doped samples. For Dy³⁺-doped and Sm³⁺-doped samples, the broad excitation bands consisted of host absorptions, CTB and f-d transition. For Tm³⁺-doped samples, the O²⁻ → Tm³⁺ CTB was located at 191 nm. About the color purity and emission intensity, Ca₄Y₆(SiO₄)₆O:Tb³⁺ is an attractive candidate of green light PDP phosphor, and Ca₄Y₆(SiO₄)₆O:Dy³⁺ has potential application in the field of mercury-free lamps.     

Brazing of 6061 aluminum alloy/Ti-6Al-4V using Al-Si-Cu-Ge filler metals

Al-8.4Si-20Cu-10Ge and mixed rare-earth elements (Re) containing Al-8.4Si-20Cu-10Ge-0.1Re filler metals were used for brazing of 6061 aluminum alloy/Ti-6Al-4V. The addition of 20 wt.% copper and 10 wt.% germanium into the Al-12Si filler metal lowered the solidus temperature from 586 °C to 489 °C and the liquidus temperature from 592 °C to 513 °C. The addition of 0.1 wt.% rare-earth elements into Al-8.4Si-20Cu-10Ge alloy caused remarkable Al-rich phase refinement and transformed the needle-like Al₂Cu intermetallic compounds into block-like shapes. Shear strengths of the 6061 aluminum alloy/Ti-6Al-4V joints with the two brazing filler metals, Al-8.4Si-20Cu-10Ge and Al-8.4Si-20Cu-10Ge-0.1Re, varied insignificantly with brazing periods of 10-60 min. The average shear strength of the 6061 aluminum alloy/Ti-6Al-4V joints brazed with Al-8.4Si-20Cu-10Ge at 530 °C was about 20 MPa. Rare-earth elements appeared to improve the reaction of the Al-8.4Si-20Cu-10Ge filler metal with Ti-6Al-4V. The joint shear strength of the 6061 aluminum alloy/Ti-6Al-4V with Al-8.4Si-20Cu-10Ge-0.1Re reached about 51 MPa.     

High-speed deposition of Y-Si-O films by laser chemical vapor deposition using Nd:YAG laser

Y-Si-O films were prepared by laser chemical vapor deposition (LCVD) with a Nd:YAG laser using TEOS (tetraethyl orthosilicate) and Y(dpm)₃ precursors. The effects of laser power (P_L), deposition temperature (T_dep) and total chamber pressure (P_tot) on the phase, microstructure and deposition rate of Y-Si-O films were investigated. At P_L < 102 W (T_dep < 1140 K), amorphous Y-Si-O films were obtained independent of P_tot. At P_tot = 0.6 kPa, mixture phase films of Y₂SiO₅ (the X1 phase) and Y₂Si₂O₇ (the α, β, δ and y phases) were obtained at P_L = 102 W (T_dep = 1210 K), while single phase X1-Y₂SiO₅ films were prepared at P_L > 139 W (T_dep > 1280 K). Y₂Si₂O₇ mixture phase films were obtained at P_tot = 3.5 kPa and Y₂Si₂O₇ and Y₂SiO₅ (the X2 phase) mixture phase films were obtained at P_tot = 7.5 kPa independent of T_dep. Amorphous Y-Si-O films showed a dense, glassy microstructure. Faceted columnar grains grew on the Y-Si-O films at P_tot = 0.6 kPa, whereas rounded cauliflower-like grains grew at P_tot = 7.5 kPa. The R_dep increased with increasing P_L and T_dep and reached a maximum of 430 μm h⁻¹ at P_tot = 0.6 kPa, P_L = 186 W and T_dep = 1310 K.     

Influence of cerium addition on the resistance to oxidation of AM50 alloy prepared by rapid solidification

The influence of various cerium (Ce) additions and starting temperature on the resistance to oxidation of AM50 alloy prepared by rapid solidification (RS, RS-AM50 alloy) has been investigated. The Ce addition has two opposite effects on the oxide scale. To the RS-alloy, the beneficial effect outweighs the detrimental one. However, when the alloy was prepared by slow solidification at the normal cooling rate (SS, SS-AM50 alloy), the detrimental effect was dominant. The improvement of oxide scale is closely related to the adherence of metal/oxide and tightness of oxide scale of the alloy. In addition, the reaction rate at the surface increased with starting temperature, which finally results in the formation of a protective oxide scale.