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At least 55 records · Page 3

Semiconductor composition containing iron, dysprosium, and terbium

An amorphous semiconductor composition includes 1 to 70 atomic percent iron, 15 to 65 atomic percent dysprosium, 15 to 35 atomic percent terbium, balance X, wherein X is at least one of an oxidizing element and a reducing element. The composition has an essentially amorphous microstructure, an optical transmittance of at least 50% in at least the visible spectrum and semiconductor electrical properties.

36 MATERIALS SCIENCE↗

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes: Oxide Solubility Determinations

Electrolytic production of light rare earth elements and alloys takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds, and side cathode reactions could largely be minimized by a good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The oxide content of the fluoride melts REF{sub 3}-LiF (RE = Nd, Dy) at different compositions and temperatures were experimentally determined by carbothermal analysis of melt samples. The highest solubility values of oxide species, added as Dy{sub 2}O{sub 3} and Dy{sub 2}(CO{sub 3}){sub 3}, were obtained to be of ca. 3 wt pct (expressed as Dy{sub 2}O{sub 3}) in the case of the equimolar DyF{sub 3}-LiF melt at 1323 K (1050 °C). The oxide saturation values increased with the amount of REF{sub 3} present in the molten bath and the working temperature.

36 MATERIALS SCIENCE↗

Magnetic and magnetocaloric properties of bulk dysprosium chromite

In this work, a polycrystalline bulk DyCrO{sub 3} sample was prepared by a solution route and the structural and magnetic properties were investigated. The phase purity and ionic valence state of the DyCrO{sub 3} sample were determined by x-ray diffraction/Raman spectroscopy and x-ray photoelectron spectroscopy, respectively. The AC and DC magnetization measurements revealed the onset of antiferromagnetic order at 146 K with an effective moment of 8.88 μ{sub B}. Isothermal magnetization measurements of this material are presented for the first time, showing a peak in the coercive field at 80 K that is explained by the competition between the paramagnetic Dy{sup 3+} and Cr{sup 3+} sublattices. DyCrO{sub 3} was found to display a large magnetocaloric effect (8.4 J/kg K) and relative cooling power (217 J/kg) at 4 T applied field, which renders DyCrO{sub 3} useful for magnetic refrigeration between 5 K and 30 K.

36 MATERIALS SCIENCE↗

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes. Electrolysis in a Laboratory-Scale Cell

Electrolytic production of light rare earth elements and rare earth alloys with transition elements takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds and side cathode reactions could largely be minimized by good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The Dy{sub 2}O{sub 3} feed rate needed for stable cell operation was studied by following up the anode voltage and gas analysis. On-line analysis of the cell off-gases by FTIR showed that the electrochemical reaction for the formation of Dy-Fe alloy gives mainly CO gas and that CF{sub 4} is starting to evolve gradually at anode voltages of ca. 3.25 V. The limiting current density for the discharge of the oxide ions at the graphite anode was in the range of 0.1 to 0.18 A cm{sup −2} at dissolved Dy{sub 2}O{sub 3} contents of ca. 1 wt pct. Modeling of the laboratory cell reactor was also carried out by implementing two models, i.e., an electrical model simulating the current density distribution at the electrodes and a laminal bubbly flow model that explains the electrolyte velocity induced by gas bubble production at the anode.

36 MATERIALS SCIENCE↗

Enhancement of lanthanide evaporation by complexation: Dysprosium tri-iodide mixed with indium iodide and thulium tri-iodide mixed with thallium iodide

The vapors in equilibrium with condensates of DyI{sub 3}, DyI{sub 3}/InI, TmI{sub 3}, and TmI{sub 3}/TlI were observed over the temperature range from 900 K to 1400 K using x-ray induced fluorescence. The total densities of each element (Dy, Tm, In, Tl, and I) in the vapor, summed over all atomic and molecular species, were determined. Dramatic enhancements in the total vapor densities of Dy and Tm were observed in the vapors over DyI{sub 3}/InI and TmI{sub 3}/TlI as compared to the vapors over pure DyI{sub 3} and pure TmI{sub 3}, respectively. An enhancement factor exceeding 10 was observed for Dy at T≈ 1020 K, decreasing to 0 at T≈ 1250 K. An enhancement factor exceeding 20 was observed for Tm at T≈ 1040 K, decreasing to 0 at T≈ 1300 K. Such enhancements are expected from the formation of the vapor-phase hetero-complexes DyInI{sub 4} and TmTlI{sub 4}. Numerical simulations of the thermo-chemical equilibrium suggest the importance of additional complexes in liquid phases. A description of the measurement technique is given. Improvements in the absolute calibration lead to an approximately 40% correction to previously reported preliminary results [J. J. Curry et al., Chem. Phys. Lett. 507, 52 (2011); Appl. Phys. Lett. 100, 083505 (2012)].

36 MATERIALS SCIENCE↗

Role of Dysprosium Doping on Structural, Optical, Magnetic and Electrical Properties of ZnO Nanorods

Well-defined Dy-doped ZnO rods were synthesized by hydrothermal route. Various studies were carried out on the synthesized rods like x-ray diffraction to confirm their hexagonal wurtzite structure; TEM, HRTEM and selected area electron diffraction to establish their rodlike structure; energy-dispersive x-ray spectroscopy analysis confirming appropriate substitution of dopant; UV-Vis spectra, which showed decrease in band gap with dopant concentration and photoluminescence study furnishing information regarding the presence of various types of defects. Further, magnetic studies were done using VSM to confirm roomtemperature ferromagnetic behaviour of both for undoped and doped ZnO rods and, the electrical studies were performed using four probe method, which confirmed that the ‘variation in resistivity with dopant concentration’ was related to crystallinity of the samples. UV-Vis spectra showed effect of dopant concentration on band gap and photoluminescence study confirms induced ferromagnetic behaviour due to Dy doping.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structural, thermal, optical properties and simulation of white light of titanium-tungstate-tellurite glasses doped with dysprosium

Graphical abstract: CIE coordinate diagram of different concentrations of the Dy{sup 3+}-doped TTWD glasses with coordinates in the white light region. - Highlights: • Radiative lifetime of {sup 4}F{sub 9/2} level of Dy{sup 3+} ions is longer in the tellurite glass. • Quantum efficiency is found to be high. • These glasses are suitable materials for generating white light. - Abstract: Structural, thermal, optical properties and simulation of white light of Dy{sup 3+}-doped tellurite glasses of composition TTWD: (75 − x)TeO{sub 2} − 10TiO{sub 2} − 15WO{sub 3} − xDy{sub 2}O{sub 3} (x = 0, 0.1, 0.5, 1.0 and 2.0 mol%) were investigated. Raman spectra revealed that the glass contains TeO{sub 4}, TeO{sub 3}, WO{sub 4} and WO{sub 6} units. Differential scanning calorimetry (DSC) measurements were carried out to measure the glass transition temperature of all the glasses. From the optical absorption spectra, luminescence spectra and using the Judd–Ofelt (JO) analysis, we estimated the radiative transition probabilities, emission cross-sections, branching ratios and radiative lifetimes. The decay curves at lower concentrations are exponential while they show a non-exponential behavior at higher concentrations (≥0.5 mol%) due to energy transfer processes. The effective lifetime for the {sup 4}F{sub 9/2} level decreases with increase in Dy{sub 2}O{sub 3} concentration for the glasses under investigation. The non-exponential decay curves could fit well to the Inokuti–Hirayama (IH) model with S = 6, indicating that the nature of interaction responsible for energy transfer is of dipole–dipole type. Simulation of white light is examined with varying concentration and the results indicate that these glasses are suitable for white light emitting diode applications.

36 MATERIALS SCIENCE↗

Photodissociation spectroscopy of the dysprosium monochloride molecular ion

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells, including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation of the electrical characteristics of MOS structures with erbium, gadolinium, and dysprosium oxides under the effect of an electric field

The degradation of the characteristics of silicon metal-oxide-semiconductor (MOS) structures with oxides of rare-earth elements under the effect of electric fields with intensities of 0.1–4 MV/cm during the course of electroforming is studied. A specific feature of electroforming consists in the possibility of multiple switching of the structures from the insulating state to the low-resistivity one and back. The temporal characteristics of the degradation of MOS structures during the course of electroforming are exponential. The current-voltage characteristics follow the power law in the range of 0.2–3 V; the effect of an electric field brings about a variation in the distribution of the energy density of traps responsible for currents limited by space charge. It is established that multiple cycles of electroforming lead to an increase in the density of surface states at the Si-oxide interface and to a variation in the energy position of the trap levels, which affects the charge state of the traps.

36 MATERIALS SCIENCE↗

Chelator‐Assisted Precipitation‐Based Separation of the Rare Earth Elements Neodymium and Dysprosium from Aqueous Solutions

The rare earth elements (REEs) are critical resources for many clean energy technologies, but are difficult to obtain in their elementally pure forms because of their nearly identical chemical properties. Here, an analogue of macropa, G-macropa, was synthesized and employed for an aqueous precipitation-based separation of Nd 3+ and Dy 3+ . G-macropa maintains the same thermodynamic preference for the large REEs as macropa, but shows smaller thermodynamic stability constants. Molecular dynamics studies demonstrate that the binding affinity differences of these chelators for Nd 3+ and Dy 3+ is a consequence of the presence or absence of an inner-sphere water molecule, which alters the donor strength of the macrocyclic ethers. Leveraging the small REE affinity of G-macropa, we demonstrate that within aqueous solutions of Nd 3+ , Dy 3+ , and G-macropa, the addition of HCO 3 − selectively precipitates Dy 2 (CO 3 ) 3 , leaving the Nd 3+ −G-macropa complex in solution. With this method, remarkably high separation factors of 841 and 741 are achieved for 50 : 50 and 75 : 25 mixtures. Further studies involving Nd 3+ :Dy 3+ ratios of 95 : 5 in authentic magnet waste also afford an efficient separation as well. Finally, G-macropa is recovered via crystallization with HCl and used for subsequent extractions, demonstrating its good recyclability.

Gao, Yangyang↗

Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical–Radical Cross–Coupling Reaction

Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal-carbon bonds. In this study, the pyrazine ligand undergoes a radical-radical cross-coupling reaction leading to the formation of a decanuclear [(Cp*) 20 Dy 10 (L1) 10 ] ⋅ 12(C 7 H 8 ) ( 1 ; where L1 = anion of 2-prop-2-enyl-2 H -pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all Dy III metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing Cp R 2 Ln x units (Cp R = substituted cyclopentadienyl), 1 features the highest nuclearity obtained to date. In-depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1 , revealed slow magnetic relaxation upon application of a static dc field.

cross-coupling↗

On dysprosium utilisation in multi-main-phase Nd–Dy–Fe–B magnets with core–shell microstructures

The development of high-performance Nd–Dy–Fe–B magnets that minimise the consumption of the scarce rare earth (RE) element Dy remains a major global scientific and technological quest. Here, we designed an alloy microstructure comprising of a uniform Dy-lean core–Dy-rich shell in a series of multi-main-phase (MMP) Nd–Dy–Fe–B magnets. The resulting MMP Dy1 and Dy3 magnets with an overall Dy level of 1 and 3 wt.% possessed values of 0.48 and 0.29 T/wt.% of coercivity increment per unit weight percentage of the Dy addition, respectively. Most importantly, the resulting MMP Dy3 magnet exhibited a high coercivity (2.38 T), an excellent thermal stability of the coercivity (|β| = 0.531%/°C), a high squareness factor (> 95%), all with little diminishment in the remanent magnetisation (1.35 T) and maximum energy product (43.6 MGOe). These properties are superior to the currently available sintered Nd–Dy–Fe–B magnets which utilise higher levels of Dy of 5 wt.%. Via magnetic and multi-scale microstructural characterisation experiments and micromagnetic simulations, the formation of the Dy-lean core–Dy-rich shell microstructure is rationalised via solid-state-diffusion and solution reprecipitation during liquid-phase sintering. The Dy-lean core–Dy-rich shell microstructure and the non-ferromagnetic low-Fe RE-rich grain boundary phase led to the synergistic magnetic performance. This is significant in the context of the MMP Nd–Dy–Fe–B magnets being applied to large-scale production. The present work establishes a pathway for the more sustainable utilisation of Dy in permanent magnets via formation of a uniform core–shell microstructure.

36 MATERIALS SCIENCE↗