Rare Earth Research Articles

Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, C7H73-) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements YIII and ErIII with a bridging cycloheptatrienyl ligand of the type [(thf)(BH4)2LnIII(μ-η7:η7-Cht)LnIII(BH4)(thf)2] is described first. The subsequent introduction of the CotTIPS ligand (CotTIPS = 1,4-(iPr3Si)2C8H62-) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)3K{(η8-CotTIPS)LnIII}2(μ-η7:η7-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck. These compounds are also the first examples of rare earth triple-decker complexes not bridged by a Cot derivative, based on purely carbon-based ligands. The magnetic properties of the respective ErIII congeners were investigated in detail, leading to the observation of antiferromagnetic coupling of the ErIII cations and a blocking temperature of 13.5 K. The conversion of the YIII compound [(thf)3K{(η8-CotTIPS)YIII}2(μ-η7:η7-Cht)] with [YIII(Cot)I(thf)2] resulted in ligand rearrangement and the selective formation of the first triple-decker complex ([(η8-CotTIPSYIII)2(μ-η8:η8-Cot)]) featuring two Cot ligands with different substituents in its coordination sphere.

High Temperature Corrosion Performance of HVOF and D-gun Formulated Cr3C2-NiCr and Rare Earth Element Doped Cr3C2-NiCr Coating on TP347H Austenite Steel

High Temperature Corrosion Performance of HVOF and D-gun Formulated Cr3C2-NiCr and Rare Earth Element Doped Cr3C2-NiCr Coating on TP347H Austenite Steel

Anionic and Magnetic Ordering in Rare Earth Tantalum Oxynitrides with an n = 1 Ruddlesden–Popper Structure

Anionic and Magnetic Ordering in Rare Earth Tantalum Oxynitrides with an <i>n</i> = 1 Ruddlesden–Popper Structure

Effective Spectrophotometric Quantification of Yttrium Using Clayton Yellow Dye in Different Rare Earth Concentrates

Effective Spectrophotometric Quantification of Yttrium Using Clayton Yellow Dye in Different Rare Earth Concentrates

Effect of microalloying with rare-earth lanthanum on dynamic recrystallization behavior and mechanical properties of Ti sheets

This study examines the influence of microalloying with rare earth lanthanum (La) on the dynamic recrystallization behavior and mechanical properties of Titanium (Ti) sheets. A distinctive wedge-shaped specimen was employed for experimental efficiency, enabling continuous gradient strains to be applied to the Ti-La alloy during hot-rolling, facilitating the assessment of changing microstructural, textural, and hardness features as strain increased from low to high levels. The hot-rolled plates were performed using analytical methods such as optical microscopy (OM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and hardness testing. The results show that the hardening process can be divided into four stages under continuous gradient strain (0 ∼ 0.5, 0.5 ∼ 0.7, 0.7 ∼ 1.2 and 1.2 ∼ 1.6). During these stages, grain refinement and dislocation strengthening emerge as critical contributors to changes in hardness. Furthermore, it was determined that dynamic recrystallisation (DRX) of Ti-La alloys during hot rolling occurs at the fourth stage. Analysis of the orientation distribution function (ODF) reveals that the dominant textures during this process include {1̅21̅0}, {011̅0}, and {0001} textures. When compared with commercially pure titanium (CP-Ti), the Ti-La alloy shows significantly delayed DRX under identical conditions. The DRX grain growth appears suppressed, attributable to the presence of La-rich particles on the grain boundaries. Moreover, the texture associated with rolling deformation seems subdued, providing a desirable base for future cold rolling and heat treatment.

Recovery of Rare Earth Elements from Ion-Adsorption Deposits Using Electrokinetic Technology: The Soil Conductivity Mechanism Study

Rare earth elements (REEs) are essential raw materials for modern industries but mining them has caused severe environmental issues, particularly the recovery of heavy REEs (HREEs) from ion-adsorption deposits (IADs). Very recently, an emerging technology, electrokinetic mining (EKM), has been proposed for the green and efficient recovery of REEs from IADs. However, the conduction mechanism of the weathering crust soil, which is also a prerequisite for EKM, remains unclear, making the EKM process unpredictable. Here, we systematically investigated the conductivity of weathering crust soil in the presence of light REEs (LREEs, i.e., La3+ and Sm3+) and HREEs (Er3+ and Y3+), respectively. Results suggested that the voltage was dynamically and spatially redistributed by the movement of REEs and water during EKM, and the conventional assumption of the linear distribution of voltage leads to an inaccurate description of soil voltage. We proposed an improved Archie’s equation by coupling the mechanisms of liquid phase and solid-liquid interface conduction, which can predict soil conductivity more precisely. Moreover, the extended Archie’s equation is able to recalculate the voltage distribution at distinct times and spaces well during EKM. More importantly, the water content in field-scale weathered-crust soils can be retrieved by the newly proposed Archie’s equation, which helps optimize the leaching wells and improve the recovery rate of REE. This study focuses on the conduction mechanism of weathering crust soil, which provides a theoretical basis for better use of the EKM technology and promotes mining efficiency fundamentally.

Achieving excellent strength–ductility combination of Al-aided Mg–Gd–Al–Zr–Zn alloys fabricated by cold metal transfer-based wire-arc directed energy deposition via uniform equiaxed grains and multiple precipitates

Limited ductility consistently poses a challenge for high-strength Mg–RE (rare earth) structures prepared by additive manufacturing. Particularly following heat treatment, while the strength of the Mg–RE alloy experiences a substantial increase, there is a noteworthy decrease in its ductility. Herein, a novel Mg–Gd–Al–Zr–Zn thin wall was successfully fabricated by cold metal transfer-based wire-arc directed energy deposition (CMT-WA-DED) and Al alloying. The microstructural evolution and mechanical properties of deposited and heat-treatment alloys were elucidated systematically. By adding Al element, Al2Gd and Al–Zr phases with thermal stability were precipitated in the deposited alloy. During the solidification or heat treatment stage, Al2Gd and Al–Zr phases could pin grain boundaries to restrict grain growth. The as-deposited alloys exhibited fully equiaxed grains at different heights and orientations. Thus, the thin wall exhibited good isotropic performance. After the heat treatment, the grain size only slightly grew and no abnormal grain growth was observed. Various morphologies of β precipitation phases were discovered along grain boundaries and within the grains. Additionally, a high density of β' and β1 phases within the grains and β phases along the grain boundary played pivotal roles in enhancing the mechanical strength of the Mg–Gd–Al–Zr–Zn alloy. The alloys exhibited an excellent combination of strength and ductility with ultimate tensile strength of 340 ± 7 MPa, yield strength of 212 ± 5 MPa, and elongation of 12.7 ± 0.9 %. This work provides theoretical and practical reference value for the Mg–RE structures obtaining an excellent combination of strength and ductility prepared by additive manufacturing.

Domestic dogs as environmental sentinel in comparative toxicologic pathology: Assessment of metals and rare earth elements concentrations in healthy and neoplastic mammary glands

Quantification of trace element concentrations in human and animal tissues has acquired great importance in the last few years, considering the pivotal role of these elements in several physiological and pathological processes. Variations in their concentrations appear to have a role in the development and advancement of diseases in both humans and animals, for example, cancer. The purpose of this study was to investigate the concentration of rare earth elements and metals in healthy and neoplastic Formalin-Fixed Paraffin-Embedded (FFPE) mammary gland tissue of dogs. All samples were processed to have a quantitative determination of inorganic elements including metals of known toxicological interest such as Pb, Cd, Tl, As, Hg, the trace elements Mn, Fe, Co, Cu, Zn, Se, and other elements including Cr, V, Mo, Ni, Sb, W, Sn. Moreover, rare earth elements (REEs) (Sc, Y, Lu, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) were also investigated. Cu and Mo concentrations in mammary cancerous tissue were greater than those in normal mammary glands (p < 0.05). In non-neoplastic tissue increased concentrations of Cd, Co, Ni, Tl, and V were also reported (p < 0.05). The mammary tissue of healthy individuals had greater concentrations of REEs than the neoplastic mammary glands (p < 0.05). The results of our study confirmed differences in mammary inorganic element concentrations between healthy and neoplastic groups, highlighting the potential relevance of these fluctuations in toxicologic pathology.

Compositional design and phase formation capability of high-entropy rare-earth disilicates from machine learning and decision fusion

A key strategy for designing environmental barrier coatings is to incorporate multiple rare-earth (RE) components into β- and γ-RE2Si2O7 to achieve multifunctional performance optimization. However, the polymorphic phase presents significant challenges for the design of multicomponent RE disilicates. Here, employing decision fusion, a machine learning (ML) method is crafted to identify multicomponent RE disilicates, showcasing notable accuracy in prediction. The well-trained ML models evaluated the phase formation capability of 117 (RE10.25RE20.25Yb0.25Lu0.25)2Si2O7 and (RE11/6RE21/6RE31/6Gd1/6Yb1/6Lu1/6)2Si2O7, which are unreported in experiments and validated by first-principles calculations. Utilizing model visualization, essential factors governing the formation of (RE10.25RE20.25Yb0.25Lu0.25)2Si2O7 are pinpointed, including the average radius of RE3+ and variations in different RE3+ combinations. On the other hand, (RE11/6RE21/6RE31/6Gd1/6Yb1/6Lu1/6)2Si2O7 must take into account the average mass and the electronegativity deviation of RE3+. This work combines material-oriented ML methods with formation mechanisms of multicomponent RE disilicates, enabling the efficient design of superior materials with exceptional properties for the application of environmental barrier coatings.

Achieving excellent mechanical and electrical properties in transition metal oxides and rare earth oxide‐doped KNN‐based piezoceramics

AbstractPotassium sodium niobate (KNN)‐based piezoelectric ceramics have emerged as a promising alternative to lead‐based systems due to their exceptional properties. While extensive research has focused on improving the electrical properties of KNN‐based ceramics through doping and processing optimization, the concurrent investigation of their mechanical properties has been lacking. This study presents a comprehensive analysis of the mechanical and electrical properties of KNN‐based lead‐free piezoceramics doped with various transition metal oxides and rare earth oxides, based on substantial experimental data. Our findings reveal that the as‐sintered KNN‐based ceramics exhibit not only outstanding electrical properties but also remarkable mechanical robustness compared to conventional toughened lead zirconate titanate (PZT)‐based ceramics. These exceptional electrical and mechanical properties are attributed to the micro‐scale and atomic‐scale structure of the modified KNN‐based ceramics, characterized by a highly condensed structure, an inhomogeneous distribution of nano‐domain structure, and the presence of amorphous intergranular films at grain boundaries.

Unveiling the connection between lode gold mineralization and the metamorphic core complex evolution from the large Yangzhaiyu gold deposit, North China Craton

The Xiaoqinling gold province, located in the Neoarchean−Paleoproterozoic uplifted footwalls of the Xiaoqinling metamorphic core complex (XMCC), is one of China’s largest gold producers; however, achieving a consensus regarding their metallogenic model remains elusive. Scheelite is an indicator mineral that commonly occurs in lode gold deposits worldwide used to recognize deposit types and understand hydrothermal evolution and the origin of features. Xenotime, monazite, and rutile are common hydrothermal minerals in association with lode gold deposits worldwide. Here, we provide textual, in situ U-Pb geochronology of xenotime, monazite, and rutile, and in situ elemental and Sr-Nd isotopic compositions of scheelite within different stages from the large Yangzhaiyu lode gold deposit, aiming to elucidate its genesis and, for the first time, establish a holistic correlation between the lode gold mineralization and the evolution of the XMCC. Notably low εNd(t) values (−30.7 to −23.7), high 87Sr/86Sr ratios (0.72659−0.75914), and distinct rare earth elements, Sr, Mo, and As contents of scheelite confirm a metamorphic crustal source. Xenotime U-Pb dating and pre-ore (Stage I) scheelite reveal that ore-barren metamorphic fluids at ca. 140 Ma were oxidized with low Bi contents and buffered by greenschist facies metamorphism when the XMCC initiated. Monazite and rutile U-Pb dating combined with ore-stage scheelite geochemistry indicate a compositional shift in the more reduced auriferous metamorphic fluids, which dominated during major gold deposition periods (stages II and III) from 130 Ma to 120 Ma, characterized by significantly depleted Na and increased Bi contents. This resulted from the prograde greenschist-to-amphibolite metamorphism at mid-lower crustal depths as the result of the XMCC isostatic doming and the lithospheric mantle thinning after 130 Ma. This study highlights the crucial role of metamorphic core complexes in governing the timing, locations, and resources of the lode gold metallogenic system.

Fast, accessible and reliable method for elemental analysis of metals in solution by ED-XRF spectroscopy

The measurement of metals in solution is usually performed using inductive coupled plasma hyphenated techniques or atomic absorption. Although very sensitive and accurate, these analytical techniques are quite expensive and do not allow field measurements. The present work takes advantage of energy-dispersive X-ray fluorescence (ED-XRF) ease-of-use features to determine the concentration of rare earth elements (Y, Pr, Nd, Eu) and others (S, Fe, Ni, Cu, Zn) in aqueous solutions, after appropriate sample treatment. The approach turned out to be a reliable and very convenient procedure for field analysis. The simplicity, speed and reliability of the methodology used combined with the possibility of simultaneous analysis and low cost of the method can be advantageous in industrial context. The approach relies on the suspension of the target solutions in a cellulose matrix that is further converted into a pellet for direct analysis. Calibration curves obtained by regression analysis at 5% significance are shown for a variety of elements (S, Fe, Ni, Cu, Zn, Y, Pr, Nd, Eu) with correlation coefficients between 0.9555 and 0.9980. Higher coefficients of variance were obtained for the calibration of S and Pr due to low sensitivity and the overlapping with the L lines of Nd, respectively. The performed calibrations were not affected by the presence of other analytes in the matrix. Results obtained showed that it is possible to use the proposed methodology to accurately quantify d and f block metals in aqueous solutions by ED-XRF after sequestering the chemical content into a cellulose powder matrix and further processing into a pellet.Graphical

Constructing Self-Healing Polydimethylsiloxane through Molecular Structure Design and Metal Ion Bonding.

Self-healing polydimethylsiloxane (PDMS) has garnered significant attention due to its potential applications across various fields. In this study, a functionalized modification of PDMS containing di-aminos was initially conducted using 2,6-pyridinedicarbonyl chloride to synthesize pyridine-PDMS (Py-PDMS). Subsequently, rare earth metal europium ions (Eu3+) were incorporated into Py-PDMS. Due to the coordination interaction between Eu3+ and organic ligands, a coordination cross-linking network was created within the Py-PDMS matrix, resulting in the fabrication of Eu3+-Py-PDMS elastomer. At a molar ratio of Eu3+ to ligands of 1:1, the tensile strength of Eu3+-Py-PDMS reached 1.4 MPa, with a fracture elongation of 824%. Due to the dynamic reversibility of coordination bonds, Eu3+-Py-PDMS with a metal-to-ligand molar ratio of 1:2 exhibited varying self-healing efficiencies at different temperatures. Notably, after 4 h of repair at 60 °C, its self-healing efficiency reached nearly 100%. Furthermore, the gas barrier properties of Eu3+-Py-PDMS with a molar ratio of 1:1 was improved compared with that of Eu3+-Py-PDMS with a molar ratio of 1:1. This study provides an effective strategy for the design and fabrication of PDMS with high mechanical strength, high gas barrier properties, and exceptional self-healing efficiency.

Tailoring electroless Ni-W-P polyalloy coatings: Unveiling the synergistic impact of cerium addition and annealing on surface functional properties

Electroless deposition of Ni-based coatings is a cost-effective solution to augment the surface mechanical and electrochemical properties of engineering components. This work explores the influence of addition of rare-earth element Ce on the characteristics of Ni-W-P coatings. The concentration of Ce salt in the deposition bath was varied in the range 0–14 mg/L, and the highest deposition rate was for the solution with 8 mg/L Ce. A homogeneous distribution of Ce over the coated surfaces was observed, and the share of Ce in the composition of the deposition varied monotonically with the Ce concentration in solution. Further, the coating surface compositions also depended on the Ce-content. Coating obtained using 8 mg/L Ce was found to have significantly improved scratch hardness (8.49 GPa), fracture toughness (7.05 MPa.m1/2), specific wear rate (3.1 × 10−6 mm3/N.m) and corrosion protection efficiency (94.16 %) as compared to the coating without Ce (3.87 GPa, 3.39 MPa.m1/2, 9.03 × 10−6 mm3/N.m, and 45.44 %, respectively). Interestingly, the ability of the coating to inhibit biofilm formation on the surface initially increased with increasing Ce content, but this effect also diminished above 8 mg/L Ce. Additionally, annealing the coatings caused further alterations in the microstructures, resulting in improvement in the microhardness, scratch, wear, and biocorrosion resistance, but at the cost of compromised corrosion resistance. Properties of such annealed coatings also depended on the annealing temperature. Therefore, this study indicates that a wide spectrum of combinations of surface physical, mechanical, and electrochemical properties can be achieved by controlling only two processing conditions, i.e., the Ce concentration, and the annealing temperature.

A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

A Luminescent Hybrid Bimetallic Halide Family with Solvent-Coordinated Rare Earth and Alkaline Earth Metals.

Hybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in-depth structure-property relations, we report here a new family of 21 zero-dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A = rare earth (RE), alkaline earth metals and Mn; L = solvent ligand; and B = Sb, Bi and Te). The Ln(DMSO)8[BCl6] (Ln = La, Ce, Sm, Eu, Tb, and Dy; DMSO = dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94%. The pseudo-octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII = Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO = tetramethylene sulfoxide) enhance the stereoactive expression of the 5s2 lone pairs of Sb3+, giving rise to the observation of dual-band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue-light-excitable single-band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements and provides important insights into designing new emitters and regulating their properties.

Correlation between nutrients, rare earth elements and heavy metals in O. Sativa rice plant organs by instrumentation neutron activation analysis and proton induced x-ray emission techniques

The accumulation of halogens and metals from roots to stems, leaves and grains of Oryza sativa rice plant collected in Northern Senegal (St Louis region) at the same stages of growth but at different salinity soil levels was investigated by measuring their elemental concentration by invasive instrumental techniques of neutron activation analysis and proton induced x-ray emission. The normalized elemental concentration of Na, Cl, K, (Cs, Rb, Sr, Sb, Ba Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Br, Rb, Sb was correlated with one of rare earth elements, La, Ce, Sm, Yb, Nd, Eu, Tb, Tm, and Lu) and the one of the heavy metals Hf, Ta and Th and to assess their subsequent distribution within the Oryza sativa rice plant in a particular salinity environment. The exploration of the experimental data was performed by applying machine learning techniques with Python to find their elemental correlations. This study shows that the accumulation of iron is highly correlated with the amount of rare earth elements and heavy metals investigated. We observe an inverse correlation between Fe and Cl concentrations in the roots and stems of the Oryza sativa rice plant, in which higher levels of Fe in the roots relative to stems correspond to lower levels of Cl. We also remark that there is no accumulation of rare earth elements in the root tissues of the different Oryza sativa rice plants studied. Whereas, in the stem, leaf, and grain organs there is a strong correlation between metal contents and rare earth elements.

Wide-range thermal conductivity modulation based on protonated nickelate perovskite oxides

The perovskite oxides ReNiO3 (Re = rare-earth elements) are promising functional materials due to their strongly correlated electrons. Except for the well-known intrinsic metal-insulating transition in these materials, recent progresses have proved that protonation of ReNiO3 can bring about interesting Mott transition in this series. To date, in these protonated species (H-ReNiO3), huge resistance switching, fast ionic diffusion, and their applications as an iontronic transistor, memristor, and fuel cell are reported. In this work, the thermal conductivities of H-ReNiO3 (Re = La, Nd, Sm, and Eu) epitaxial thin films are investigated. The protonation-induced Mott transition can effectively modulate the electronic thermal conductivity while the lattice thermal conductance is less affected. Hence, at room temperature, the metallic LaNiO3 and NdNiO3 exhibit reversible wide thermal conductivity modulation, in ranges of 2.6–12.0 and 1.6–8.0 W m−1 K−1, respectively. These values are much larger than other thermal regulation materials based on transition metal oxides. Thus, our work reveals the great potential of ReNiO3 being applied as a thermal-regulating material. The fast ionic diffusion in H-ReNiO3 also guarantees that a fast response and wide-range thermal transistor can be realized by H-LaNiO3 and H-NdNiO3 in the future.

Rare-Earth-Ion (RE3+)-Doped Aluminum and Lanthanum Borates for Mobile-Phone-Interrogated Luminescent Markers

In this paper, we present the synthesis and luminescent spectra of rare-earth (RE)-doped aluminum and lanthanum borates intended to serve as narrow excitation–emission band fluorescent markers. We perform a detailed 3D excitation–emission matrix (EEM) analysis of their spectra, compare the measurements from both standard and mobile phone spectrometers, and outline the basic differences and advantages of each method. While smartphones have a different and non-uniform spectral response compared to standard spectrometers, it is shown that they offer a number of advantages such as contactless interrogation, efficient suppression of the UV excitation light, and simultaneous spectral analysis of spatially arranged arrays of fluorescent markers. The basic emission peaks have been observed and their corresponding electronic transitions identified. The obtained results show that the rare-earth-doped La and Al borates feature excitation–emission bandwidths as low 15 nm/12 nm, which makes them particularly appropriate for use as luminescent markers with UV LED excitation and smartphone interrogation.

Using Hg isotopes and trace elements to constrain the origin of the Ordovician Xiangquan Tl deposit, South China

Sediment-hosted stratiform sulfide (SHSS) deposits commonly contain large amounts of strategic metals, such as Tl, Hg, Cd, Ge and Ga, however, sources of these metals remain debate. Here we present new elemental and Hg isotopic data to constrain the metal sources for the Xiangquan Tl deposit (South China), a unique SHSS deposit with 250 t Tl at an average grade of 928 ppm. Stratiform pyrite orebodies are hosted in the Ordovician marine sedimentary succession of mostly limestone with minor mudstone. Pyrite, the dominant ore mineral, is rich in Hg (up to 1360 ppm). Bulk ores and pyrite separates from this deposit have significant variations of δ202Hg (−5.48 to −0.65 ‰) and Δ199Hg (−0.01 to 0.36 ‰). The Δ199Hg values are mostly positive, similar to those of seawater and marine sediments. Ore petrography, trace element enrichment coefficients, rare earth element patterns, Re-Os ages (478 ± 33 Ma) and S isotope compositions of pyrite indicate that Hg and other metals were derived from hydrothermal fluids venting at the seafloor. We suggest that the ore-forming fluids of the Xiangquan deposit were predominantly originated from large-scale circulation of evolved seawater, which leached Hg and Tl from the marine country rocks. These metal-rich fluids migrated upward, vented to the seafloor, and mixed with anoxic H2S-rich seawater to precipitate Hg- and Tl-rich pyrite. Our study highlights that the combined application of Hg isotopes and trace elements could be used to trace the sources of metals in hydrothermal ore deposits such as SHSS deposits.