Effective model for rare-earth Kitaev materials and its classical Monte Carlo simulation

Recently,the family of rare-earth chalcohalides were proposed as candidate compounds to realize the Kitaev spin liquid(KSL)[Chin.Phys.Lett.38047502(2021)].In the present work,we firstly propose an effective spin Hamiltonian consistent with the symmetry group of the crystal structure.Then we apply classical Monte Carlo simulations to preliminarily study the model and establish a phase diagram.When approaching to the low temperature limit,several magnetic long range orders are observed,including the stripe,the zigzag,the antiferromagnetic(AFM),the ferromagnetic(FM),the incommensurate spiral(IS),the multi-Q,and the 120°ones.We further calculate the thermodynamic properties of the system,such as the temperature dependence of the magnetic susceptibility and the heat capacity.The ordering transition temperatures reflected in the two quantities agree with each other.For most interaction regions,the system is magnetically more susceptible in the ab-plane than in the c-direction.The stripe phase is special,where the susceptibility is fairly isotropic in the whole temperature region.These features provide useful information to understand the magnetic properties of related materials.

Research progress in rare earths and their composites based electrode materials for supercapacitors

Supercapacitor is an imminent potential energy storage system,and acts as a booster to the batteries and fuel cells to provide necessary power density.In the last decade,carbon and carbonaceous materials,conducting polymers and transition metal oxide/hydroxide based electrode materials have been made to show a remarkable electrochemical performance.Rare-earth materials have attracted significant research attention as an electrode material for supercapacitor applications based on their physicochemical properties.In this review,rare earth metals,rare earth metal oxides/hydroxides,rare-earth metal chalcogenides,rare-earth metal/carbon composites and rare-earth metal/metal oxide composites based electrode materials are discussed for supercapacitors.We also discuss the energy chemistry of rare-earth metal-based materials.Besides the factors that affect the performance of the electrode materials,their evaluation methods and supercapacitor performances are discussed in details.Finally,the future outlook in rare-earth-based electrode materials is revealed towards its current developments for supercapacitor applications.

Critical Materials Institute develops new acid-free magnet recycling process

A new rare-earth magnet recycling process developed by researchers at the Critical Materials Institute (CMI) dissolves magnets in an acid-free solution and recovers high purity rare earth elements. For shredded magnet-containing electronic wastes, the process does not require pre-processing such as pre-sorting or demagnetization of the electronic waste.

Design of the rare-earth-containing materials based on the micro-alloying phase equilibria, phase diagrams and phase transformations

Rare-earth(RE)elements,known as“industrial vitamins”,have permeated modern lives,especially in high-tech applications.Although the RE elements possess close chemical similarities and have been treated as“one element”in the periodic table,their characteristics differ from each other.The RE microalloying effect is the crux to ameliorate the physicomechanical and thermochemical properties of materials,thereby the study of RE-related phase diagrams becomes indispensable to the design and optimization of RE-containing materials.However,in reality,the knowledge base in this area is considerably scarce compared with that of other commonly-used elements.In this work,the phase equilibria,phase diagrams,phase transformations,and some recent examples of RE-containing materials design are summarized,with which one can predict the RE solubilities,the RE precipitates,as well as the corresponding service behaviors.The attainment of enhanced materials’properties suggests that the thermodynamic rules extracted from the phase diagrams could serve as fundamental criteria for the successful development of novel RE-containing materials.

Effects of rare-earth elements on the glass-forming ability and mechanical properties of Cu_(46)Zr_(47-x)Al_7M_x(M = Ce,Pr,Tb,and Gd) bulk metallic glasses

Cu46Zr47-xA17Mx （M = Ce, Pr, Tb, and Gd） bulk metallic glassy （BMG） alloys were prepared by copper-mold vacuum suction casting. The effects of rare-earth elements on the glass-forming ability （GFA）, thermal stability, and mechanical properties of Cu46Zr47-xA17Mx were investigated. The GFA of Cu46Zr47-xA17Mx （M = Ce, Pr） alloys is dependent on the content of Ce and Pr, and the optimal content is 4 at.%. Cu46Zr47-xA17Thx（X = 2, 4, and 5） amorphous alloys with a diameter of 5 mm can be prepared. The GFA of Cu46Zr47-xA17Gdx（x = 2, 4, and 5） increases with increasing Gd. Tx and Tp of all decrease. Tg is dependent on the rare-earth element and its content. ATx for most of these alloys decreases except the Cu46Zra2Al7Gd5 alloy. The activation energies △Eg, △Ex, and △Ep for the Cu46Zr42A17Gd5 BMG alloy with Kissinger equations are 340.7, 211.3, and 211.3 kJ/mol, respectively. These values with Ozawa equations are 334.8, 210.3, and 210.3 kJ/mol, respec- tively. The Cu46Zr45Al7Tb2 alloy presents the highest microhardness, Hv 590, while the Cu46Zr43A17Pr4 alloy presents the least, Hv 479. The compressive strength （at.f.） of the Cu46Zra3A17Gd4 BMG alloy is higher than that of the Cu46Zr43Al7Tb4 BMG alloy.

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn2O4 used as cathode materials for lithium-ion batteries was synthesized by mechanochemistry fluid activation process, and modified by doping rare-earth Sm. Testing of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn2O4 cathode materials and the modified materials.The results show that the cathode materials doped rare earth LixMn2-ySmxO4 (0.95≤x≤1.2, 0≤y≤0.3, 0≤z≤0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discapacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55 C.At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element.

Enhanced Laser Cooling of Rare-Earth-Ion-Doped Glass Containing Nanometer-Sized Metallic Particles

The enhanced laser cooling performance of rare-earth-ions-doped glasses containing small particles is predicted. This is achieved by the enhancement of local field around rare earth ions, owing to the surface plasmon resonance of small metallic particles. The role of energy transfer between ions and the particle is theoretical discussed. Depending on the particle size and the ion emission quantum efficiency, the enhancement of the absorption and the fluorescence is predicted. Moreover, taking Yb^3＋-doped ZBLAN as example, the cooling power and heat-light converting efficiency are calculated. It is finally concluded that the absorption and the fluorescence are greatly enhanced in these composite materials, the cooling power is increased compared to the bulk material.

The luminescence enhancement of Eu^(3+) ion and SnO_2 nanocrystal co-doped sol gel SiO_2 films

SnO2 nanocrystal and rare-earth Eu^3＋ ion co-doped SiO2 thin films are prepared by sol-gel and spin coating methods. The formation of tetragonal rutile structure SnO2 nanocrystals with a uniform distribution is confirmed by X-ray diffraction and transmission electron microscopy. Fourier transform infrared spectroscopy is used to investigate the densities of the hydroxyl groups, and it is found that the emission intensity from the 5Do-TF2 transitions of the Eu^3＋ ions is enhanced by two orders of magnitude due to energy transfer from the oxygen-vacancy-related defects of the SnO2 nanocrystals to nearby Eu^3＋ ions. The influences of the amounts of Sn and the post-annealing temperatures are systematically evaluated to further understand the mechanism of energy transfer. The luminescence intensity ratio of Eu^3＋ ions from electric dipole transition and magnetic dipole transition indicate the different probable locations of Eu^3＋ ions in the sol-gel thin film, which are further discussed based on temperature-dependent photoluminescence measurements.

Rare Earth Doped Optical Fibers for Temperature Sensing Utilizing Ratio-Based Technology

A new and practical fluorescence temperature detecting system based on fluorescence intensity ratio was proposed . The background theory of fluorescence intensity-ratio method was presented simply. And the characters of rare earth doped samples were detailed. The erbium-doped fiber was chosen as the sensing element. The energy levels of 2H11/2 and 4S3/2 are responsible for the emission of radiation at approximately 530 and 555 nm. The erbium-doped (960 ppm) fiber of length 20 cm and core diameter 3.2μm was used as the sensing part. A silica photodiode transfers the fluorescence signal to electric signal, then the ratio of the average of the two different signals was calculated by the computer and the temperature was obtained. The ratio R of the intensity resulting from the transition between the two levels varies proportionly with temperature interval from 293 K to 373 K. The sensitivity of the sensor is approximately 0.05 K-1.

Structure and Magnetic Properties of LaCo_(13-X)M_X Intermetallic Compounds

LaCo_(13) has the highest 3d metal content ,of any known rare-earth intermetallic compounds,a1. 03MA/m saturation magnetization at room temperature and a high T_c (1318K). Unfortunately ,it is cubic ,lacking of the necessary anisotropy,thus diminishing the chance that it will be used as a permanent rnagneticmaterial. In this paper ,the structure and magnetic properties of LaCo_(13) Six (x=2 , 4 )and LaCo_(13) Ge_X(x=2,2. 5 ,3 ,4)intermetallic compounds have been studied. The crystal structure was found to be tetragonal whenx=4 for LaCo_(13-X) Six and x=3 , 4 for LaCo_(13-X) Gex ,but the difference between the lattice parameters a and c isvery small. In order to gain the tetragonal structure ,the annealing temperature of LaCo_(13-X) Ge_X must be con-trolled strictly. The magnetic rneasurement results show that the Curie temperatures of all these compoundsare high ,but the saturation magnetization at room-temperature decreases greatly with x increasing.

10BaF_2:NaF,Na_3AlF_6/TiO_2 composite as a novel visible-light-driven photocatalyst based on upconversion emission

A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.

High-entropy enhanced room-temperature ferroelectricity in rare-earth orthoferrites

Single-phase multiferroic materials of rare-earth orthoferrites with magnetism and ferroelectricity are of great technological importance in storage devices.However,the polarization(P)of these materials is generally weak(0.01μC-cm^(-2)),and the ferroelectricity is reported to exist below room temperature(25℃).Here,(Bi_(0.2)La_(0.2)Y_(0.2)Dy_(0.2)Tb_(0.2))FeO_(3)(BLYDTFO)high-entropy oxides that exhibit a saturation P of 5.3μC.cm^(-2)at the electric field(E)of 45 kV·cm^(-1)at room temperature was designed and fabricated by the conventional solid-phase method.The results show that configurational entropy introduces atomic disorder and a larger tilt of BO6 octahedron,which facilitates noncentrosymmetric distortion and ferroelectricity at room temperature compared with other single components(LaFeO_(3),YFeO_(3),DyFeO_(3),and TbFeO_(3)).This high-entropy approach expands the compositional window of the rare-earth orthoferrites to enhance the ferroelectricity in multiferroic applications.

Coordination chemistry of surface-associated ligands for solid-liquid adsorption of rare-earth elements

General guidelines for the design of ligands for the enrichment of rare-earth elements by solid-liquid adsorption are described using coordination chemistry.Relevant properties of ligands include selectivity of metal ions based on adjustment of donor atom polarizability,denticity,and the pKarange of the binding sites.The selectivity of solid-phase materials for the enrichment of rare-earth ions by the ligand design guidelines is outlined,with special consideration of additional variable factors including steric hindrance,saturated binding sites,variability in speciation caused by the identity of counterions and ionic strength,and size-exclusivity in ligands stemming from differences in bite angle,preo rganization of ligands,or intraligand interactions.This review analyzes some principles of selectivity of rare-earth elements with ligands organized by donor type from examples collected from reports published between 2009 and 2021.

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE BY LANTHANOCENE CATALYSIS

Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization tem-perature is found to be the most important factor affecting the polymerization. The bulkpolymerization gives higher molecular weight PCL and higher conversion than that in solu-tion polymerization. NaBPh_4 was found to promote the polymerization of ε-caprolactone,and thus to increase both the polymerization conversion and MW of poly (ε- caprolactone ).

Characterization of Fluoride Phosphors for Diode Pumped Solid-State Lighting Applications

Phosphor coated diodes are critical to the lighting industry. Rare-earth doped fluoride phosphors are characterized in this work. Spectroscopy and lifetime measurements of CaF2: Dy3+, LaF3: Eu3+ and Tb3+-doped LaF3 and CaF2 crystals were performed by irradiating the samples with 405 and 375 nm diode lasers. Chromaticity diagrams are developed from spectral measurements. Dy3+-doped CaF2 revealed bright white light emission having peaks at 492, 570 and 654 nm. The measured color coordinates are x = 0.322 and y = 0.340 for Dy3+-doped CaF2 and these values are close to those of sunlight and the coordinated color temperature is 6147 K, under 405 m laser excitation. Eu3+-doped LaF3 revealed twenty emission peaks in the visible wavelength region. The color coordinates measured for LaF3: Eu3+ are x = 0.283 and y = 0.293 under 405 nm diode laser excitation and the color temperature is 9557 K. Eu3+-doped LaF3 provides cool white-light, under 405 nm diode laser excitation. Tb3+-doped fluoride crystals revealed bright white light under low power diode laser excitation. The measured color coordinates for Tb3+-doped CaF2 are x = 0.329 and y = 0.558 and the color temperature is 7713 K. The color coordinates for LaF3: Tb3+ are x = 0.342 and y = 0.365 and the coordinated color temperature is 5370 K. These values are close to those of sunlight.

High entropy defective fluorite structured rare-earth niobates and tantalates for thermal barrier applications

Rare-earth tantalates and niobates(REjTaO7 and REjNbO7)have been considered as promising candidate thermal barrier coating(TBC)materials in next generation gas-turbine engines due to their ultra-low thermal conductivity and better thermal stability than yttria-stabilized zirconia(YSZ).However,the low Vickers hardness and toughness are the main shortcomings of RE;TaO-and REjNbOr that limit their applications as TBC materials.To increase the hardness,high entropy(Yu3Ybu3Er/3)sTaOr,(Y13YbnErns)NbO,and(Sm1/6Eu1/6Y 1/6Yb1/6Lu1/6Er1/6)3(Nb1/2Ta1/2)O7 are designed and synthesized in this study.These high entropy ceramics exhibit high Vickers hardness(10.912.0 GPa),close thermal expansion coefficients to that of single-principal-component RE3TaO,and RE;NbO,(7.9×10^-6-10.8×10-6 C-1 at room temperature),good phase stability,and good chemical compatibility with thermally grown Al2O3,which make them promising for applications as candidate TBC materials.

Batch synthesis of rare-earth nickelates electronic phase transition perovskites via rare-earth processing intermediates

The rare-earth nickelates(RENiO_(3)) exhibit an exceptional complex electronic phase diagram and multiple electronic phase transitions that enrich promising applications in correlated electronic devices beyond conventional semiconductors.Nevertheless,the practical applications of RENiO_(3) are challenged by their intrinsic thermodynamic metastability in material synthesis and high material cost.Therefore,developing an economical strategy to achieve the batch synthesis of RENiO_(3) is of vital importance.In this work,we enlarged the synthesis amount of RENiO_(3) up to 20 g per batch using chloride(KCI) assisted molten salt reaction.By optimizing the reaction conditions,the powder of RENiO_(3) with the cubic shape and average size of ~2μm was effectively synthesized,while their phase purity exceeded 95%.In addition,the cost to synthesize RENiO_(3) was further reduced by using rare-earth extraction intermediate products as the raw materials,instead of using the pure rare-earth precursors.It also achieved wide adjustments in the metal-to-insulator-transition temperature from160 to 420 K without significantly reducing the transition sharpness.By enlarging the synthesis amount and the reducing the cost,it paves the way to the device application of RENiO_(3).

VUV spectroscopic properties of rare-earth(RE=Eu,Tb and Dy)-doped A_2Zr(PO_4)_2(A=Li,Na and K) phosphates

This study fully investigated the vacuum ultraviolet excitation spectra of pure and rare-earth（RE=Eu, Tb and Dy）-doped A2Zr（PO4）2（A=Li, Na and K） phosphors. The synthesized Na and Li compounds were characterized by XRD showing two new types of phases after indexation. Although these three pure compounds had different crystal structures, they exhibited similar luminescence properties. For Eu3＋-activated samples, the broad excitation band centered at 217 nm could be attributed to the CT transition between O2–（2p6） and Eu3＋ ions. For Tb3＋-doped samples, two groups of f-d transitions were observed, where a strong broad band at 221 nm was due to the spin-allowed f-d transition. Energy transfer from O2– to Dy3＋was not observed in Dy3＋-doped phosphors, probably because it overlapped considerably with the CT transition from O2– to Zr4＋ at 187 nm.

(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4: A high-entropy rare-earth phosphate monazite ceramic with low thermal conductivity and good compatibility with Al2O3

Low thermal conductivity, matched thermal expansion coefficient and good compatibility are general requirements for the environmental/thermal barrier coatings(EBCs/TBCs) and interphases for Al2O3 f/Al2O3 composites. In this work, a novel high-entropy(HE) rare-earth phosphate monazite ceramic (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is designed and successfully synthesized. This new type of HE rare-earth phosphate monazite exhibits good chemical compatibility with Al2O3, without reaction with Al2O3 as high as 1600℃ in air. Moreover, the thermal expansion coefficient(TEC) of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4(8.9 × 10^-6/℃ at 300–1000℃) is close to that of Al2O3. The thermal conductivity of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 at room temperature is as low as 2.08 W·m^-1·K^-1, which is about 42% lower than that of La PO4. Good chemical compatibility, close TEC to that of Al2O3, and low thermal conductivity indicate that HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is suitable as a candidate EBC/TBC material and an interphase for Al2O3 f/Al2O3 composites.

BaYOBO_(3):A deep-ultraviolet rare-earth oxy-borate with a large second harmonic generation response

Deep-ultraviolet(UV)nonlinear optical(NLO)crystals with excellent performances are of great importance in laser science and technology.However,to design and synthesize an ideal deep-UV NLO material with a balance between second harmonic generation(SHG)response and UV cut-off edge is still a huge challenge.Herein,a new oxy-borate BaYOBO_(3)(BaYBO)was designed and synthesized by substituting Be^(2+)with Y^(3+)from Sr_(2)Be_(2)B_(2(O_(7).The BaYBO features a stable three-dimensional framework and satisfies the property balance between a large SHG response(~2.6×KH_(2)PO_(4)KDP))and a short UV cut-off edge(<190 nm)as a promising deep-UV NLO candidate.The study of structure-property relationship indicates that the large SHG response of BaYBO is mainly attributed to the coplanar arrangement and large number density of BO_(3 )triangles.These results demonstrate that substituting Be^(2+)with Y^(3+)cations is also a feasible strategy for developing new deep-UV NLO crystals.