离子型稀土矿山淋洗及尾水富集试验研究

对浸矿后离子型稀土原地浸矿场采用清水进行淋洗，在184天的清水淋洗过程中，尾水氨氮值从最开始的507mg/L，降低至140mg/L，淋洗尾水pH4.52~3.10。淋洗尾水采用两级反渗透膜分离，既回收有价资源稀土，又能使出水氨氮达标。结果表明，产水氨氮浓度稳定低于15mg/L，对稀土的截留率高于98.25%，浓水中稀土离子平均浓度313.4mg/L，可进一步回收稀土资源。     

地应力条件下的凿岩爆破数值模拟

为了研究地应力对凿岩爆破的影响,采用DDA方法模拟爆炸应力波作用下考虑地应力条件时的单孔和多孔凿岩爆破破岩过程。模拟发现,随着初始地应力水平的增加,裂纹扩展半径和破岩区域面积减小,裂纹发育主方向趋于地应力的最大主应力方向,初始地应力对裂纹的抑制和引导作用明显;初始地应力水平的增加,对拉伸裂纹的抑制作用更为显著,从而降低了拉伸破坏对爆破破岩的贡献。模拟也表明,在初始地应力存在的条件下,通过对爆破载荷和炮孔布置进行针对性的优化,可以克服地应力带来的影响,并取得预期的爆破效果。本研究对地应力条件下的凿岩爆破工程具有理论和参考意义。     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).     

Synthesis,microstructures, and corrosion behaviors of multi-components rare-earth silicates

Multi-components and equimolar rare earth monosilicates, (Y_1/3Dy_1/3Er_1/3)₂SiO₅, (Y_1/3Dy_1/3Lu_1/3)₂SiO₅, (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅, were prepared by solid-state reactions and the following hot-pressing. Dense microstructures with uniform elemental distributions were obtained for all samples. These investigated multi-components monosilicates exhibit low thermal conductivities and similar coefficients of thermal expansion with SiC. Moreover, they exhibit high corrosion resistances in 1400 °C water vapor, especially, four-components (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ experienced almost invariable weights after small weight losses during the initial 0.5 h. All those results indicate that multi-components rare earth monosilicates are promising candidates of environmental barrier coatings for SiC/SiC composites.     

Direct View on the Origin of High Li+ Transfer Impedance in All-Solid-State Battery

Large interfacial resistance plays a dominant role in the performance of all-solid-state lithium-ion batteries. However, the mechanism of interfacial resistance has been under debate. Here, the Li⁺ transport at the interfacial region is investigated to reveal the origin of the high Li⁺ transfer impedance in a LiCoO₂(LCO)/LiPON/Pt all-solid-state battery. Both an unexpected nanocrystalline layer and a structurally disordered transition layer are discovered to be inherent to the LCO/LiPON interface. Under electrochemical conditions, the nanocrystalline layer with insufficient electrochemical stability leads to the introduction of voids during electrochemical cycles, which is the origin of the high Li⁺ transfer impedance at solid electrolyte-electrode interfaces. In addition, at relatively low temperatures, the oxygen vacancies migration in the transition layer results in the formation of Co₃O₄ nanocrystalline layer with nanovoids, which contributes to the high Li⁺ transfer impedance. This work sheds light on the mechanism for the high interfacial resistance and promotes overcoming the interfacial issues in all-solid-state batteries.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.     

Synthesis and luminescence enhancement of red-emitting Sr9Y(PO4)7:Eu3+ phosphor through Gd3+ co-doping for white light-emitting diodes

A series of Sr₉Y(PO₄)₇:Eu³⁺ and Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphors were prepared via a high-temperature solid-state method, Gd³⁺ ion was co-doped in Sr₉Y(PO₄)₇:Eu³⁺ as sensitizer to enhance the luminescence property. The X-ray diffraction results verify that the structure of the as-prepared samples is consistent with the standard Sr₉Y(PO₄)₇ phase. All the Sr₉Y(PO₄)₇:Eu³⁺ samples show both characteristic emission peaks at 594 nm and 614 nm under near-ultraviolet excitation of 394 nm. The co-doping of Gd³⁺ significantly improves the luminescence intensity of the Sr₉Y(PO₄)₇:Eu³⁺ phosphors due to the crystal field environment effect and energy transfer of Gd³⁺→Eu³⁺ caused by the introduction of Gd³⁺, especially Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺, which emission intensity is higher than that of Sr₉Y(PO₄)₇:0.11Eu³⁺ by 1.21 times. The color purity and lifetime of Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺ phosphor are 88.26% and 3.7615 ms, respectively. A w-LED device was packaged via coating the as-prepared phosphor on n-UV chip of 395 nm with commercial phosphors. These results exhibit that the Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphor can be used as a red component in the w-LEDs application.     

The effects of the modification of the BST-system solid solutions with rare earth elements

The conditions for the preparation of the solid solutions of a binary system of barium-strontium titanates with the substitutions in the A-sublattice with the rare-earth elements (REE), including the solid-phase synthesis, mechanical activation and sintering of dispersed-crystalline products by the conventional ceramic technology, were optimized. The presence (absence) of the impurity phases was established depending on the size effect of the REE. The precision X-ray diffraction analysis revealed the features of the phase formation in the studied solid solutions and showed that the “behavior” of the structural characteristics of the solid solutions with the participation of the REE is determined by the limiting conditions of the isomorphism and anion excess of the media under study. An assumption is made about the nature of the formation of a fine-grained landscape of the modified solid solutions, associated with the multicluster structure of the crystallite structure and the formation of the ballast phases during their synthesis. The dependences of the dielectric properties of the solid-state solution on the external influences – temperature, frequency of an alternating electric field and strength of a constant field – have been established. The possibility of choosing on the basis of the obtained data, promising for practical applications of the compositions is shown.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.