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At least 73 records · Page 4

Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (<5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (>5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple-layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. An SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. Furthermore, this predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

58 GEOSCIENCES↗

Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics

The interest in plasmonic technologies surrounds many emergent optoelectronic applications, such as plasmon lasers, transistors, sensors and information storage. Although plasmonic materials for ultraviolet–visible and near-infrared wavelengths have been found, the mid-infrared range remains a challenge to address: few known systems can achieve subwavelength optical confinement with low loss in this range. With a combination of experiments and ab initio modelling, here we demonstrate an extreme peak of electron mobility in Dy-doped CdO that is achieved through accurate ‘defect equilibrium engineering’. In so doing, we create a tunable plasmon host that satisfies the criteria for mid-infrared spectrum plasmonics, and overcomes the losses seen in conventional plasmonic materials. In particular, extrinsic doping pins the CdO Fermi level above the conduction band minimum and it increases the formation energy of native oxygen vacancies, thus reducing their populations by several orders of magnitude. The substitutional lattice strain induced by Dy doping is sufficiently small, allowing mobility values around 500 cm 2 V –1 s –1 for carrier densities above 10 20 cm –3 . As a result, our work shows that CdO:Dy is a model system for intrinsic and extrinsic manipulation of defects affecting electrical, optical and thermal properties, that oxide conductors are ideal candidates for plasmonic devices and that the defect engineering approach for property optimization is generally applicable to other conducting metal oxides.

36 MATERIALS SCIENCE↗

Magnetic and magnetocaloric properties of iron subs tituted holmium chromite and dysprosium chromite

In this work, structural, magnetic, and magnetocaloric properties of HoCrO 3 and Fe substituted HoCrO 3 and DyCrO 3 (i.e. HoCr 0.7 Fe 0.3 O 3 and DyCr 0.7 Fe 0.3 O 3 ) powder samples were synthesized via a solution route. The structural properties of the samples were examined by Raman spectroscopy and x-ray diffraction techniques, which were further confirmed using first-principle calculations. The dc magnetic measurements indicate that the Cr 3+ ordering temperatures for the HoCrO 3 , HoCr 0.7 Fe 0.3 O 3 , and DyCr 0.7 Fe 0.3 O 3 samples are 140 K, 174 K, and 160 K, respectively. The ac magnetic measurements not only confirmed the Cr 3+ ordering transitions in these samples (obtained using dc magnetic measurements), but also clearly showed the Ho 3+ ordering at ~10 K in the present HoCrO 3 and HoCr 0.7 Fe 0.3 O 3 samples, which to our knowledge, is the first ac magnetic evidence of Ho 3+ ordering in this system. The effective magnetic moments were determined to be 11.67μB, 11.30μB, and 11.27μB for the HoCrO 3 , HoCr 0.7 Fe 0.3 O 3 , and DyCr 0.7 Fe 0.3 O 3 samples, respectively. For the first time, the magnetocaloric properties of HoCrO 3 and HoCr 0.7 Fe 0.3 O 3 were studied here, showing their potential for applications in magnetic refrigeration. In an applied dc magnetic field of 7 T, the maximum magnetocaloric value were determined to be 7.2 (at 20 K), 6.83 (at 20 K), 13.08 J/kg K (at 5 K) and the relative cooling power were 408, 387, and 500 J/kg for the HoCrO 3 , HoCr 0.7 Fe 0.3 O 3 , and DyCr 0.7 Fe 0.3 O 3 samples, respectively.

36 MATERIALS SCIENCE↗

Synergistic Extraction of Dysprosium and Aggregate Formation in Solvent Extraction Systems Combining TBP and HDBP

During treatment of nuclear fuel in the Plutonium/URanium EXtraction (PUREX) process, the extractant tri-n-butyl phosphate (TBP) is known to degrade to dibutylphosphoric acid (HDBP), which increases the extraction of metal ions, thereby inhibiting their stripping from the organic phase. To better understand this phenomenon, we investigated how mixtures of TBP and HDBP influenced the extraction of metal, nitric acid, and water, and correlated the results to aggregated structures in the organic phase. The mole ratios of TBP-HDBP mixtures had a non-linear effect on the extraction of Dy 3+ and water from 0.2 M HNO 3 , indicating synergism. In 2 M HNO 3 , the TBP:HDBP mole ratio had a more linear relation to Dy 3+ and water extraction, so the synergistic effect was less pronounced than in the low acid system. The extraction of nitric acid showed no synergistic effect and follows closely what would be expected in a system using TBP only. The small-angle X-ray scattering (SAXS) data of the 0.2 M acid system showed maximum contrast at a TBP:HDBP mole ratio of 0.25, so that the synergistic mixture is also the most aggregated at 0.2 M acid. The 2 M acid system also showed that the mixed system is more aggregated than the end members, although this does not result in peak extraction. Previous studies of synergistic extraction of metal cations explain the enhanced extraction by increased dehydration of the metal ion. Although our data do not rule out the formation of mixed complexes according to the classical mechanism of synergism, our evidence of increased water extraction and aggregate formation in systems combining TBP and HDBP are complementary to the metal-centric dehydration aspects of the process. The findings in this study give insights into the complex chemistry of solvent extraction, thus providing a possible link between formation of aggregates in the organic phase and synergistic extraction.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Formation of dysprosium carbide on the graphite (0001) surface

When using scanning tunneling microscopy, we characterize a surface carbide that forms such that Dy is deposited on the basal plane of graphite. In order to form carbide islands on terraces, Dy is first deposited at 650–800 K, which forms large metallic islands. Upon annealing at 1000 K, these clusters convert to carbide. Deposition directly at 1000 K is ineffective because nucleation on terraces is inhibited. Reaction is signaled by the fact that each carbide cluster is partially or totally surrounded by an etch pit. The etch pit is one carbon layer deep for most carbide clusters. Carbide clusters are also identifiable by striations on their surfaces. Based on mass balance, and assuming that only the surface layer of carbon is involved in the reaction, the carbide has stoichiometry D y 2 C . This is Dy-rich compared with the most common bulk carbide Dy C 2 , which may reflect limited surface carbon transport to the carbide.

36 MATERIALS SCIENCE↗

Mid-infrared luminescence properties of erbium and dysprosium doped lanthanum titanate glasses

Glasses of composition x RE 2 O 3 -(17− x ) La 2 O 3 -83 TiO 2 were prepared by levitation melting from x = 0.1 to 9 for RE=Er and at x =0.1 and 1 for RE=Dy. The glasses have high transition temperature, exhibit low OH, and 1 mm thick discs are transparent out to 6 μ m. Mid-infrared emission lineshapes and lifetimes are comparable to what is seen in tellurite glasses containing Er 3+ and Dy 3+ . For x fixed at 1, the Er 3+ : 4 I 11/2 → 4 I 13/2 transition at 2716 nm has a fluorescence lifetime of 254 μ s and the Dy 3+ : 6 H 13/2 → 6 H 15/2 transition at 2957 nm has a fluorescence lifetime of 9.09 μ s. The results indicate that doped lanthanum titanate glasses offer the thermal stability of a ’hard’ glass with the host properties typically associated with ’soft’ glasses. Problems with the measurement of spectral features in the mid-infrared that could erroneously be assigned as resulting from rare-earth ion emissions are presented and discussed.

36 MATERIALS SCIENCE↗

Computational Data Associated with the publication: 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*)20Dy10(L1)10] ⋅ 12(C7H8) (1; where L1 = anion of 2‐prop‐2‐enyl‐2H‐pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all DyIII metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units (CpR = 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.

Bajaj, Neha↗