Search Results (62)

LiTaO₃ crystals doped with Cr³⁺ and Nd³⁺ ions are promising for developing active nonlinear laser media. In this work, the defect structure of LiTaO₃ crystals, including those doped with Cr³⁺ and Nd³⁺, is examined. X-ray patterns of all six investigated LiTaO₃:Cr:Nd crystals are identical and correspond to a highly perfect structure. Using optical microscopy, the presence of defects of various shapes, microinhomogeneities, and lacunae was revealed. The optical absorption and Raman scattering spectra of a series of nonlinear, optical, double-doped LiTaO₃:Cr³⁺:Nd³⁺ (0.06 ≤ [Cr³⁺] ≤ 0.2; 0.2 ≤ [Nd³⁺] ≤ 0.45 wt%) crystals showed that at concentrations of doping Cr³⁺ ions less than 0.09 wt% and Nd³⁺ ions less than 0.25 wt%, the crystal structure is characterized by a low level of defects, and the optical transmission spectra characterized by narrow lines corresponding to electron transitions in Nd³⁺ ions. In this case, for the radiative transition in the cation sublattice, the existence of three nonequivalent neodymium centers is observed, and for the radiative transition, two nonequivalent centers are observed. IR absorption spectroscopy in the OH⁻-stretching vibration range revealed two main spectral regions: 3463–3465 cm⁻¹, associated with stoichiometry changes, and 3486–3490 cm⁻¹, linked to complex defects such as (V^-_Li)-OH and (Ta⁴⁺_Li)-OH. A distinct low-intensity line at ~3504 cm⁻¹ was observed only in doped crystals, attributed to (Nd²⁺_Li)-OH defects that significantly distort the oxygen-octahedral clusters due to the larger ionic radius of Nd³⁺ compared to Ta⁵⁺. In contrast, Cr-related defects cause only minor distortions. The Klauer method indicated that the highest concentration of OH⁻-groups occurs in the LiTaO₃:Cr³⁺ (0.09 wt%):Nd³⁺ (0.25 wt%) crystal, where multiple complex defects are present. Full article

Rare earth metals (REMs) are vital for high-tech industries, but their extraction from secondary sources is challenging due to environmental and technical constraints. This study investigates the ion-exchange extraction of light REMs (neodymium, praseodymium, and samarium) from sulfuric and phosphoric acid solutions, modeling industrial leachates from apatite concentrates and phosphogypsum. The study considers the use of anion- and cation-exchange resins with different functional groups for efficient and environmentally safe REM separation. Experimental sorption isotherms were obtained under static conditions at 298 K and analyzed using a thermodynamic model based on the linearization of the mass action equation. Equilibrium constants and Gibbs energy were calculated, which reveals the spontaneity of the processes. Cation-exchange resins demonstrated high selectivity towards individual REMs, while anion-exchange resins were suitable for group extraction. Infrared spectral analysis confirmed the presence of sulfate and phosphate complexes in the resin matrix, clarifying the ion-exchange mechanisms. Thermal effect measurements indicated exothermic sorption on anion-exchange resins with negative entropy and endothermic sorption on cation-exchange resins with positive entropy. The findings highlight the potential of ion-exchange resins for selective and sustainable REM recovery, offering a safer alternative to liquid extraction and enabling the valorization of industrial wastes like phosphogypsum for resource recovery. Full article

Rapid progress in lithium-ion batteries and AI-powered autonomous driving is poised to propel electric vehicles to a 50% share of the global automotive market by the year 2035. Today, there is a major focus on recycling electric vehicle motors, particularly on extracting rare earth elements (REEs) from NdFeB permanent magnets (PMs). This research is based on a single-furnace process concept designed to separate metal components within PM motors by exploiting the varying melting points of the constituent materials, simultaneously extracting REEs present within the PMs and transferring them into the slag phase. Thermodynamic modeling, via Factsage Equilib stream calculations, optimized the experimental process. Simulated materials substituted the PM motor, which optimized modeling-directed melting within an induction furnace. The 2FeO·SiO₂ fayalite flux can oxidize rare earth elements, resulting in slag. The neodymium oxidation reaction by fayalite exhibits a ΔG° of −427 kJ when subjected to an oxygen partial pressure ($P_{O_2}$) of 1.8 × 10⁻⁹, which is lower than that required for FeO decomposition. Concerning the FeO–SiO₂ system, neodymium, in Nd³⁺, exhibits a strong bonding with the ${\mathrm{S}\mathrm{i}\mathrm{O}}_4^{4^{-}}$ matrix, leading to its incorporation within the slag as the silicate compound, Nd₂Si₂O₇. When 30 wt.% fayalite flux was added, the resulting experiment yielded a neodymium extraction degree of 91%, showcasing the effectiveness of this fluxing agent in the extraction process. Full article

Random lasers (RLs) based on glasses and glass-ceramics doped with rare-earth ions (REI) deserve great attention because of their specific physical properties such as large thermal stability, possibility to operate at high intensities, optical wavelength tunability, and prospects to operate Fiber-RLs, among other characteristics of interest for photonic applications. In this article, we present a brief review of experiments with RLs based on tellurite and germanate glasses and glass-ceramics doped with neodymium (Nd³⁺), erbium (Er³⁺), and ytterbium (Yb³⁺) ions. The glass samples were fabricated using the melt-quenching technique followed by controlled crystallization to achieve the glass-ceramics. Afterwards, the samples were crushed to obtain the powder samples for the RLs experiments. The experiments demonstrated RLs emissions at various wavelengths, with feedback mechanisms due to light scattering at grain/air and crystalline/glass interfaces. The phenomenon of replica symmetry breaking was verified through statistical analysis of the RLs intensity fluctuations, indicating a photonic phase-transition (corresponding to the RL threshold) analogous to the paramagnetic-to-spin glass transition in magnetic materials. The various results reported here highlight the potential of glasses and glass-ceramics for the development of RLs with improved performance in terms of reduction of laser threshold and large lifetime of the active media in comparison with organic materials. Full article

A series of nickel (II) bis-phosphine organometallic complexes along with two pseudo [M₇] (M = Ni(II), Zn(II)) metallocalix[6]arene complexes and a dysprosium acetate coordination polymer have each been crystallised in the presence of localized magnetic fields set up using neodymium magnets, using custom made Magnetic Crystallization Towers (MCTs). In all cases, whether the product complex is diamagnetic or paramagnetic, a complex spatial patterning of the crystals occurs based on the orientation of the magnetic field lines. When using magnetic block towers, the crystallization generally occurs adjacent to the magnet face. The effects of nucleation and solution concentration gradients on the crystallization process are also explored. These observations show how the crystallization process is affected by magnetic fields and thus these results have far-reaching effects which most certainly will include crystallization and ion migrations in biology. Full article

This study presents both numerical and experimental analyses of enhanced mixing in a microflow system under the influence of a magnetic field. The research employed COMSOL Multiphysics for numerical simulations and Particle Image Velocimetry (PIV) for experimental validation. In the experimental microfluidic setup, permanent neodymium magnets were used to influence a laminar flow of water partially enriched with Ho(III) ions using the magnetic field. The findings confirmed that the strong interaction between Ho(III) ions and the magnetic field significantly affected the flow and may have resulted in vortex shedding downstream of the region with the highest magnetic field intensity. The numerical simulations demonstrated good agreement with the PIV experimental results. These findings suggest that it is possible to significantly enhance mixing in microflow systems without mechanical components, solely by exploiting the differences in the magnetic properties between the mixing substances. Traditionally, microreactors have been limited by mixing speeds governed by diffusion. These new results indicate the practical possibility of increasing mixing intensity in a cost-effective and safe manner. Full article

In this study, the bipolar resistance switching behavior and electrical conduction transport properties of a neodymium oxide film’s resistive random access memory (RRAM) devices for using different top electrode materials were observed and discussed. Different related electrical properties and transport mechanisms are important factors in applications in a film’s RRAM devices. For aluminum top electrode materials, the electrical conduction mechanism of the neodymium oxide film’s RRAM devices all exhibited hopping conduction behavior, with 1 mA and 10 mA compliance currents in the set state for low/high voltages applied. For TiN and ITO (Indium tin oxide) top electrode materials, the conduction mechanisms all exhibited ohmic conduction for the low voltage applied, and all exhibited hopping conduction behavior for the high voltage applied. In addition, the electrical field strength simulation resulted in an increase in the reset voltage, indicating that oxygen ions have diffused into the vicinity of the ITO electrode during the set operation. This was particularly the case in the three physical models proposed, and based on the relationship between different ITO electrode thicknesses and the oxygen ion concentration distribution effect of the neodymium oxide film’s RRAM devices, they were investigated and discussed. To prove the oxygen concentration distribution expands over the area of the ITO electrode, the simulation software was used to analyze and simulate the distribution of the electric field for the Poisson equation. Finally, the neodymium oxide film’s RRAM devices for using different top electrode materials all exhibited high memory window properties, bipolar resistance switching characteristics, and non-volatile properties for incorporation into next-generation non-volatile memory device applications in this study. Full article

The widespread occurrence of Mesozoic ocean island basalt (OIB)-like igneous rocks in the Southern Tibetan Himalayan Belt provides important constraints on the rifting of East Gondwana. This study undertook a petrological, geochronological, and geochemical investigation of mafic intrusive rocks in the Cuona area of the eastern Tethyan Himalayan Belt. The mafic intrusions have OIB-type geochemical signatures, including diabase porphyrite, gabbro, and diabase. Zircon U–Pb dating indicates that the diabase porphyrite formed at 135.0 ± 1.6 Ma. The diabase porphyrite and gabbro are enriched in high-field-strength elements (Nb and Ti) and large-ion lithophile elements (Sr and Pb) and experienced negligible lithospheric mantle or crustal contamination. The diabase is enriched in large-ion lithophile elements (LILEs, e.g., La and Ce) and depleted in high-field-strength elements (HFSEs, e.g., Ru, Zr and Ti). In general, the mafic intrusions exhibit significant light REE enrichment and heavy REE depletion and have no Eu anomalies. Whole-rock neodymium (ε_Nd(t) = 1.55) and zircon Hf (ε_Hf(t) = 0.60–3.73) isotopic compositions indicate derivation of the magma from enriched type I mantle. We propose that the diabase porphyrite and diabase formed in a continental margin rift setting, influenced by the Kerguelen mantle plume, and represent magmatism related to the breakup of East Gondwana. However, the gabbro formed in a relatively stable continental intraplate environment, likely derived from deep magmatic processes associated with the Kerguelen mantle plume. Our results provide new constraints on the early activity of the Kerguelen mantle plume and offer insights into the breakup and tectonic evolution of East Gondwana. Full article

This study focused on the nature of rare earth metal complex compounds that can form during the carbonate–alkaline processing of industrial waste materials, such as phosphogypsum and red mud, at 70–100 °C and 1–10 atm. Experimental findings revealed that the dissolution of synthetic carbonates of rare earth elements (REEs) in a concentrated carbonate-ion medium (3 mol/L) leads to the formation of ion-associates of varying strengths. Light (lanthanum, praseodymium, and neodymium) and medium (samarium) REE groups exhibited a tendency to form loose ion-associates, whereas heavy REEs (terbium, dysprosium, holmium, erbium, thulium, lutetium, and yttrium) formed close ion-associates. To confirm the existence of these ion-associates, the specific conductivity of solutions was measured after dissolving thulium (III) and samarium (III) carbonates at phase ratios ranging from 1:2000 g/mL to 1:40 g/mL in a potassium carbonate medium. The decay of ion-associates, leading to the precipitation of rare earth metal (III) carbonates, was tested in an ammonium carbonate medium. Thermal decomposition of ammonium carbonate at 70–75 °C during 1–4 h was accompanied by full rare earth carbonates’ sedimentation and its in-the-way separation into groups because of the varied strength of ion-associates. The results of this study provide a basis for developing processes to separate rare earth metals into groups during their carbonate–alkaline extraction into solution. Full article

This work presents a comparative study of five rare earth compounds—Erbium nitrate pentahydrate lll (Er), Neodymium nitrate pentahydrate (Nd), Samarium III Nitrate Hexahydrate (Sm), Yterbium III Chloride Hexahydrate (Yb) and Praseodymium nitrate hexahydrate lll (Pr)—protecting API 5L X70 steel from corrosion in saline medium that uses electrochemical impedance spectroscopy (EIS) and polarization curves (CPs) at different concentrations and in static mode. The results show that Erbium is the best corrosion inhibitor, containing 50 ppm and reaching an inhibition efficiency of about 89%, and similar result was shown by Sm with an IE~87.9%, while the other rare earths (Nd, Yb and Pr) showed a decrease in corrosion protection at the same concentration, since they were below an IE~80%. On the other hand, with the Langmuir model it was possible to describe that the adsorption process of the three rare earths follows a combined physisorption–chemisorption process to protect the metal’s surface. The observed adsorption free energy, ΔG°ads, reaches −38.7 kJ/mol for Er, −34.4 kJ/mol for Nd, and −33.6 kJ/mol for Pr; whereas Sm and Yb have adsorption free energies of −33.9 and −35.0 kJ/mol, respectively. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) further confirmed the formation of a protective film. Their characterization using density functional theory showed the transference of charge from the iron cluster towards the rare earth metal compounds. The adsorption process produced a slightly polarized region of interaction with the metal surface. Also, it was found that the adsorption of the rare earths affected the magnetic properties of the surface of the iron cluster. Quantum chemical descriptors, such as Pearson’s HSAB (Hard and Soft Acids and Bases) descriptors, were useful in predicting the behavior of the flow of electrons between the metal surface and the interacting rare earth ions. Full article

In this study, the possibilities of selective sorption of neodymium and praseodymium ions from a mixture of their solution using interpolymer systems composed of two industrial sorbents, cation exchangers KU-2-8 (Na⁺) and AB-17-8 (Cl⁻), at different molar ratios were investigated. The processes of sorption and desorption were carried out in two modes: dynamic (with active stirring) and static (without stirring the working solution from which REEs were extracted). According to the obtained results, sorption in the dynamic mode in the ratios of 4:2 and 3:3 does not lead to any selectivity. However, a high degree of extraction was noted for both ions: Pr³⁺ = 99.36%, Nd³⁺ = 95.67% for the 4:2 system and Pr³⁺ = 81.33%, Nd³⁺ = 79% for the 3:3 system. In the static mode, the degree of extraction of both metals was significantly lower: for the 4:2 system Pr³⁺ = 19.33%, Nd³⁺ = 24%, but greater selectivity with respect to neodymium was observed. With a ratio of 4:2, neodymium was sorbed better than praseodymium by 24.16%, and in the 3:3 system by 39.83%. When desorption from the cationite was carried out with nitric acid, a similar tendency was preserved. Thus, it was shown that interpolymer systems can be used in industry by varying the conditions of sorption and desorption for the successful extraction of neodymium and praseodymium from industrial solutions. Full article

Single-phase multiferroics exhibiting ferroelectricity and ferromagnetism are considered pivotal for advancing next-generation multistate memories, spintronic devices, sensors, and logic devices. In this study, the magnetic and electric characteristics of bismuth ferrite (BiFeO₃) ceramics were enhanced through compositional design and grain engineering. BiFeO₃ ceramic was co-substituted by neodymium (Nd) and niobium (Nb), two non-isovalent elements, via the spark plasma sintering process using phase-pure powder prepared via sol-gel as the precursor. The symmetry of the sintered Nd–Nb co-doped samples changed from R3c to Pnma, accompanied by a decrease in the loss tangent, grain size, and leakage current density. The reduction in the leakage current density of the co-doped samples was ~three orders of magnitude. Moreover, ferroelectric, dielectric, and magnetic properties were substantially improved. The remanent polarization and magnetization values of the optimized Nd–Nb co-doped BiFeO₃ sample were 3.12 μC cm⁻² and 0.15 emu g⁻¹, respectively. The multiferroic properties were enhanced based on multiple factors such as structural distortion caused by co-doping, grain size reduction, suppression of defect charges via donor doping, space-modulated spin structure disruption, and an increase in magnetic ions. The synergistic approach of composition design and grain engineering sets a paradigm for the advancement of multiferroic materials. Full article

Recent studies have shown that the geothermal systems in Tibet are rich in rare metal elements such as lithium (Li), boron (B), rubidium (Rb), and cesium (Cs). However, the understanding of the origin of Cs-rich geyserite formed by hot springs remains unclear. In this study, a detailed petrological, elemental geochemical, and strontium–neodymium (Sr–Nd) isotopic investigation on Cs-rich geyserite in the Chabu region revealed that opal was the main mineral component of Chabu geyserite; here, some samples were rich in terrigenous clastic material, and well-developed diatom fossils were also present. Chabu geyserite had high contents of SiO₂ (78.95%–94.72%) and Al₂O₃ (3.02%–8.14%) and low contents of Fe₂O₃ (0.21%–1.94%), TiO₂ (0.01%–0.20%), MnO (0.01%–0.15%); additionally, the Fe/Ti ratio, the Al/(Al + Fe) ratio, and the Al/(Al + Fe + Mn) ratio showed large variations. These results indicated different degrees of participation by the terrigenous materials, hydrothermal deposition, and biogenic processes. Chabu geyserite was depleted in transition metal elements (e.g., Sc, V, and Cr) and high field strength elements (e.g., Nb, Zr, and Hf), relatively enriched in large-ion lithophile elements (e.g., Li, Rb, Sr, and Ba), and strongly enriched in Cs, (by up to 100 times the Cs content in the upper crust); in addition, it had low V/Y (1.30–2.00) and U/Th ratios. Chabu geyserite exhibited a right-dipping rare earth element (REE) distribution pattern and had significant negative Eu anomalies (0.26–0.72) and no or weak positive Ce anomalies (0.97–1.36). These results further indicated the influence of terrigenous clastic materials and nonhydrothermal sedimentation factors. The Sr–Nd isotopic composition of Chabu geyserite was significantly different from that of the mantle, with relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7070–0.7076) and low ¹⁴³Nd/¹⁴⁴Nd ratios (0.512223–0.512314). These ratios were similar to those of the crust. Combined with previous studies, the results from this study indicated that Chabu geyserite was a Cs-rich geyserite and was formed in an intracontinental post-collisional orogenic environment, mainly from crustal material, with the participation of biological and hydrothermal processes. Full article

This paper investigates the use of spent tyre rubber as a precursor for synthesising adsorbents to recover rare earth elements. Through pyrolysis and CO₂ activation, tyre rubber is converted into porous carbonaceous materials with surface properties suited for rare earth element adsorption. The study also examines the efficiency of leaching rare earth elements from NdFeB magnets using optimised acid leaching methods, providing insights into recovery processes. The adsorption capacity of the materials was assessed through batch adsorption assays targeting neodymium (Nd³⁺) and dysprosium (Dy³⁺) ions. Results highlight the superior performance of activated carbon derived from tyre rubber following CO₂ activation, with the best-performing adsorbent achieving maximum uptake capacities of 24.7 mg·g⁻¹ for Nd³⁺ and 34.4 mg·g⁻¹ for Dy³⁺. Column studies revealed efficient adsorption of Nd³⁺ and Dy³⁺ from synthetic and real magnet leachates with a maximum uptake capacity of 1.36 mg·g⁻¹ for Nd³⁺ in real leachates and breakthrough times of 25 min. Bi-component assays showed no adverse effects when both ions were present, supporting their potential for simultaneous recovery. Furthermore, the adsorbents effectively recovered rare earth elements from e-waste magnet leachates, demonstrating practical applicability. This research underscores the potential of tyre rubber-derived adsorbents to enhance sustainability in critical raw material supply chains. By repurposing waste tyre rubber, these materials offer a sustainable solution for rare earth recovery, addressing resource scarcity while aligning with circular economy principles by diverting waste from landfills and creating value-added products. Full article

In this work, we describe the synthesis, crystal structures and magnetic properties of four air-stable mononuclear lanthanide(III) complexes with the N-(2,4,6-trimethylphenyl)oxamate (Htmpa) of formula: n-Bu₄N[Nd(Htmpa)₄(H₂O)]·4H₂O (1), n-Bu₄N[Gd(Htmpa)₄(H₂O)]·3DMSO·2H₂O (2), n-Bu₄N[Tb(Htmpa)₄(H₂O)]·3DMSO·1H₂O (3) and n-Bu₄N[Dy(Htmpa)₄(H₂O)]·3DMSO·2H₂O (4) (n-Bu₄N⁺ = n-tetrabutylammonium; DMSO = dimethylsulfoxide). Their crystal structures reveal the occurrence of calixarene-type monoanionic species containing all-cis-disposed Htmpa ligands and one water molecule coordinated with the respective Ln^III ion (Ln = Nd, Gd, Tb and Dy), featuring a nine-coordinated environment with muffin (MFF-9) (1) or spherical-capped square antiprism (CSAPR-9) (2–4) geometry. The major difference between their crystal structures is related to the nature of crystallization solvent molecules, either water (1) or both DMSO and water (2–4). The intermolecular hydrogen bonds among the self-complementary Htmpa ligands in all four compounds mediated a 2 D supramolecular network in the solid state. Direct-current (dc) magnetic properties for 1–4 show typical behavior for the ground state terms of the Ln^III ions [⁴I_9/2 (Nd); ⁸S_7/2(Gd), ⁷F₆ (Tb), ⁶H^15/2 (Dy)]. Alternating-current (ac) magnetic measurements reveal the presence of slow magnetic relaxation without the presence of a dc field only for 4. In contrast, field-induced slow magnetic relaxation behavior was found in complexes 1, 2 and 3. Full article