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At least 73 records · Page 4

Development of Ceramic Solid-State Laser Host Material

Polycrystalline ceramic laser materials are gaining importance in the development of novel diode-pumped solid-state lasers. Compared to single-crystals, ceramic laser materials offer advantages in terms of ease of fabrication, shape, size, and control of dopant concentrations. Recently, we have developed Neodymium doped Yttria (Nd:Y2O3) as a solid-state ceramic laser material. A scalable production method was utilized to make spherical non agglomerated and monodisperse metastable ceramic powders of compositions that were used to fabricate polycrystalline ceramic material components. This processing technique allowed for higher doping concentrations without the segregation problems that are normally encountered in single crystalline growth. We have successfully fabricated undoped and Neodymium doped Yttria material up to 2" in diameter, Ytterbium doped Yttria, and erbium doped Yttria. We are also in the process of developing other sesquioxides such as scandium Oxide (Sc2O3) and Lutesium Oxide (Lu2O3) doped with Ytterbium, erbium and thulium dopants. In this paper, we present our initial results on the material, optical, and spectroscopic properties of the doped and undoped sesquioxide materials. Polycrystalline ceramic lasers have enormous potential applications including remote sensing, chem.-bio detection, and space exploration research. It is also potentially much less expensive to produce ceramic laser materials compared to their single crystalline counterparts because of the shorter fabrication time and the potential for mass production in large sizes.

Prasad, Narasimha S.↗

UV-Vis spectrophotometric determination of rare earth elements (REE) speciation at near-neutral to alkaline pH. Part I: m-cresol purple properties from 25-75 °C and Er hydrolysis

The speciation and mobility of rare earth elements (REE) strongly depends on pH which controls the formation of charged aqueous hydroxyl species. The latter potentially play an important role in controlling heavy REE adsorption on clay minerals in near-neutral to alkaline waters such as in regolith-hosted REE mineral deposits. However, accurate REE hydrolysis constants are needed for developing geochemical models that can predict the role of these charged species in natural systems. Here, we develop a robust experimental UV-Vis spectrophotometric method using m-cresol purple to determine in situ pH from 25 to 75 °C. This method is used to derive the average ligand number and hydrolysis constants of erbium (Er) at 25 °C in aqueous solutions with low ionic strength (≤ 0.001 mol/L) at pH from ~7 to 9.5 and in the presence of Er concentrations from 0 to 0.057 mM. The average ligand number ranges between 1 and 3 indicating that Er(OH) 2+ , Er(OH) 2 + and Er(OH) 3 0 control speciation in the experiments. The logarithm of the Er hydrolysis constants (log*β n ° , n= 1 to 3) derived at infinite dilution for the reaction Er 3+ + nH 2 O = Er(OH) n 3-n + nH + are: *β 1 ° = –7.22 ± 0.10, *β 2 ° = –14.52 ± 0.08, *β 3 ° = –23.24 ± 0.04. Implementation of these experimental data into a geochemical model indicates that the Er(OH) 2 + and Er(OH) 3 0 species are both stable in a much wider pH range than previously predicted. Consequently, the positively charged REE hydroxyl complexes can potentially control the fractionation of light vs. heavy REE via adsorption as observed in the formation of certain regolith-hosted REE deposits.

58 GEOSCIENCES↗

UV-Vis spectrophotometric determination of rare earth elements (REE) speciation at near-neutral to alkaline pH. Part II: hydrolysis of Er from 25 to 75 °C

Aqueous speciation of rare earth elements (REE) controls their mobilization, fractionation, and enrichment in the natural waters. Geochemical modeling of their speciation is key to improve our understanding of the formation of economic mineral deposits, for developing mineral separation and mine tailing recovery technologies, and for characterizing the geochemistry of thermal water. However, our ability to predict the fate of REE in a wide pH and temperature range is limited by the scarcity of thermodynamic data for the REE hydroxyl complexes. In part I of this study (H. J. Han and A. P. Gysi, Dalton Trans., 2024, 53, 13129–13141), the optical properties of m-cresol purple (mCP) were determined using UV-Vis spectrophotometry between 25 and 75 °C in order to develop a method for deriving the hydrolysis constants of erbium (Er). Here, UV-Vis spectrophotometry experiments were conducted as a function of temperature between 35 and 75 °C to determine the hydrolysis of Er in near-neutral to alkaline solutions using mCP as an in situ pH color indicator. Here, the experiments were conducted with Er concentrations from 0 to ~0.253 mmol kg –1 in low ionic strength solutions (≤0.001 mol kg –1 ).

58 GEOSCIENCES↗

Optomechanical interaction in fibre lasers with micro-optomechanical resonance structures

We report the results of studies of fibre lasers with passive modulators based on light-excited micro-optomechanical resonance structures (micro-oscillators). It is shown that in fibre lasers based on active fibres doped with rare-earth elements (Er, Er/Yb, Yb, Nd), the optomechanical interaction of laser radiation with micro-oscillators of various types (fibre-optic, microvolume) leads to self-oscillations of the characteristics of laser radiation at frequencies of relaxation oscillations and intermode beats synchronised with the frequencies of elastic eigenoscillations of micro-oscillators. It is found that in an ultra-long erbium – ytterbium fibre laser with a nonlinear mirror based on a microcantilever, laser photothermal excitation of the second mode of elastic transverse oscillations of the microcantilever makes it possible to perform passive mode locking exclusively due to Q-switching of the laser cavity. Pulsed lasing with a controlled repetition rate (∼76 kHz), a pulse duration of 2 – 5 μs and an output energy of 0.1 μJ per pulse is implemented. Based on a simplified physical model of the indicated fibre lasers with micro-oscillators, we have developed an approximate mathematical model describing the regimes of passive mode locking of fibre lasers with micro-oscillators that play the role of mirrors with a nonlinear reflection coefficient in the laser cavity. The prospects for the development and application of the considered laser systems are discussed. (control of laser radiation parameters)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Lasing dynamics of diode-pumped Yb – Er laser with a passive Q switch exposed to high-power external light

The temporal dynamics of diode-side-pumped Yb – Er laser, with a passive Co{sup 2+} : MgAl{sub 2}O{sub 4} Q switch illuminated by a light beam (total fluence of 0.15 – 0.16 J cm{sup −2}) from a semiconductor pulsed module, is investigated. It is shown that, using this external illumination, one can change the lasing onset delay and the time jitter ΔT{sub gi}. The dependence of ΔT{sub gi} on the interval between the instant of switching the illumination module on and the lasing peak position t{sub i} has a minimum at |t{sub i}| ≈ 10 μs. The decrease in ΔT{sub gi} with a change in |t{sub i}| from 90 to 10 μs indicates that instant of lasing peak occurrence for the Yb – Er laser is partially controlled by the pulse from the highly stable semiconductor module. If |t{sub i}| < 10 μs, the enhanced luminescence fluence in the cavity of Yb – Er laser exceeds 0.16 J cm{sup −2}; the light beam from the module does not affect much the lasing process in the ytterbium – erbium laser; and, as a consequence, the time jitter recovers the initial value. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Covariance Testing and Update on 239 Pu and 235 U PFNS Covariances [Slides]

This presentation discusses in detail how covariances were obtained and tested. Along with a look into some of the mathematical checks that were performed. Possible "physics issues" in covariances were highlighted and addressed. Covariances for Dysprosium and Erbium-169 were touched on along with various uncertainties and issues. An update on Uranium-235 and Plutonium-239 Pu PFNS covariances was given.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A High Separation Factor for 165Er from Ho for Targeted Radionuclide Therapy

Background: Radionuclides emitting Auger electrons (AEs) with low (0.02–50 keV) energy, short (0.0007–40 µm) range, and high (1–10 keV/µm) linear energy transfer may have an important role in the targeted radionuclide therapy of metastatic and disseminated disease. Erbium-165 is a pure AE-emitting radionuclide that is chemically matched to clinical therapeutic radionuclide 177Lu, making it a useful tool for fundamental studies on the biological effects of AEs. This work develops new biomedical cyclotron irradiation and radiochemical isolation methods to produce 165Er suitable for targeted radionuclide therapeutic studies and characterizes a new such agent targeting prostate-specific membrane antigen. Methods: Biomedical cyclotrons proton-irradiated spot-welded Ho(m) targets to produce 165Er, which was isolated via cation exchange chromatography (AG 50W-X8, 200–400 mesh, 20 mL) using alpha-hydroxyisobutyrate (70 mM, pH 4.7) followed by LN2 (20–50 µm, 1.3 mL) and bDGA (50–100 µm, 0.2 mL) extraction chromatography. The purified 165Er was radiolabeled with standard radiometal chelators and used to produce and characterize a new AE-emitting radiopharmaceutical, [165Er]PSMA-617. Results: Irradiation of 80–180 mg natHo targets with 40 µA of 11–12.5 MeV protons produced 165Er at 20–30 MBq·µA−1·h−1. The 4.9 ± 0.7 h radiochemical isolation yielded 165Er in 0.01 M HCl (400 µL) with decay-corrected (DC) yield of 64 ± 2% and a Ho/165Er separation factor of (2.8 ± 1.1) · 105. Radiolabeling experiments synthesized [165Er]PSMA-617 at DC molar activities of 37–130 GBq·µmol−1. Conclusions: A 2 h biomedical cyclotron irradiation and 5 h radiochemical separation produced GBq-scale 165Er suitable for producing radiopharmaceuticals at molar activities satisfactory for investigations of targeted radionuclide therapeutics. This will enable fundamental radiation biology experiments of pure AE-emitting therapeutic radiopharmaceuticals such as [165Er]PSMA-617, which will be used to understand the impact of AEs in PSMA-targeted radionuclide therapy of prostate cancer.

165Er↗

Rare Earth and Transition Metal Containing Glasses

Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.

Du, Jincheng↗

The solubility of ErPO 4 and Er speciation in hydrothermal fluids at varying pH and salinity between 350 and 450 °C

The rare earth elements (REE) are important for the green-energy transition and can be incorporated into the REE phosphates, such as xenotime-(Y), which also hosts heavy REE (Tb– Lu). Xenotime-(Y) is a common accessory mineral in metamorphic rocks and a range of mineral deposits where it controls the mobility of heavy REE, however, the impact of high temperature aqueous fluids on the behavior of heavy REE is largely unknown. Thermodynamic modeling can be utilized as a tool to predict the mobility of REE in hydrothermal aqueous fluids, but must be supported by accurate experimental data. Here, we measured the solubility of endmember synthetic xenotime-structured ErPO4 in NaCl-HCl-NaOH-bearing aqueous solutions at 350 °C and water vapor saturation pressure, at 400 and at 450 °C and 500 bar using batch-type Inconel reactors. Erbium speciation was investigated as a function of pH from 2.8 to 8, where Er chloride species are predominant at acidic conditions (pH <3) and Er hydroxyl complexes are predominant at near- neutral to alkaline conditions (pH >3). At pH 7–9, the measured ErPO 4 solubility (-9.8 to -7.5 log m Er ) is up to 2.5 orders of magnitude lower than thermodynamic predictions (-9.4 to -6.7 log m Er ) using existing thermodynamic databases. At pH 2–3, the predicted ErPO 4 solubility is ~0.5 orders of magnitude higher at 350 °C and ~1 order of magnitude lower at 450 °C compared to experimentally measured Er concentrations. The thermodynamic properties of aqueous Er species were therefore revised in this study. The partial molal Gibbs energy of formation (Δ f G 0 T,P ) for aqueous Er hydroxyl and chloride species are optimized using GEMSFITS and the logarithmic formation constants (logβ n ( Cl,OH) ) were derived at each experimental temperature and pressure. The updated thermodynamic properties for Er hydroxyl species (Er(OH) +2 , Er(OH) 2 + , and Er(OH) 3 0 ) show that their stability shifts to more acidic conditions at and below 400 °C. The Er chloride species (ErCl +2 and ErCl 2 + ) show increased stability compared to Er hydroxyl species at temperatures of 450 °C and 0.01 mol/kg NaCl. The updated thermodynamic properties are implemented into the GEM-Selektor modeling package to investigate the mobility of Er in saline hydrothermal fluids in equilibrium with alkaline rocks. Importantly, the updated properties for Er hydroxyl species result in low Er solubility at rock equilibrated pH conditions due to an expanded hydroxyl predominance zone, but lower aqueous complex stability overall, whereas previous models suggest greater stability for aqueous Er species. Furthermore, ErPO 4 solubility increases with decreasing temperature due to the deprotonation of HCl, which increases the acidity of hydrothermal fluids and the availability of Cl - to complex with the REE. These simulations highlight how fluid-rock reaction and temperature affect the mobility of REE in hydrothermal ore-forming systems.

58 GEOSCIENCES↗

Radiative transition probabilities of neutral and singly ionized rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) estimated by laser-induced breakdown spectroscopy

Rare earth elements (REEs) are essential to society given their prevalence in many modern technologies. Quantitative elemental analysis of REEs is therefore a critical capability. Calibration free–laser-induced breakdown spectroscopy (CF-LIBS) is a rapidly maturing and promising approach to quantitative elemental analysis with many attractive qualities. The application of CF-LIBS to analyzing samples containing the REEs is hindered by a lack of fundamental data, specifically transition probabilities (TPs). As such, this study seeks to help address this knowledge deficiency by reporting 967 previously unreported TPs for 13 REEs (lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The method developed in this study to estimate the TPs requires small amounts of material (a few nanograms) compared with other approaches (~ milligrams), uses non-specialized equipment, and does not involve complicated sample preparations.

(LIBS)↗

In-gas-jet laser spectroscopy with S 3 -LEB

The Super Separator Spectrometer-Low Energy Branch (S 3 -LEB) is a low-energy radioactive ion beam experiment under commissioning as part of the GANIL-SPIRAL2 facility. It will be used for the production and study of exotic nuclei by in-gas laser ionization and spectroscopy (IGLIS), decay spectroscopy, and mass spectrometry. Here, we report recent results from the off-line commissioning of S 3 -LEB, including first laser spectroscopy measurements in both the gas cell and the supersonic gas jet, the determination of the transport efficiency of laser ions from the gas cell through the RFQ chain, and time-of-flight measurements with the multi-reflection time-of-flight mass spectrometer PILGRIM. The measurements were performed using erbium, introduced by evaporation from a heated filament in the gas environment. The reported laser spectroscopy results include a characterization of the pressure broadening in the gas cell, proof-of-principle isotope shift measurements, and hyperfine-structure measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Stresses within rare-earth doped yttria-stabilized zirconia thermal barrier coatings from in-situ synchrotron X-ray diffraction at high temperatures

There is a growing interest for smart coatings that can be integrated into turbine engines for in-situ temperature measurements or health monitoring. The addition of rare-earth dopants into standard thermal barrier ceramic top coat materials is used to obtain luminescent coatings that enable spectral measurements, for real-time temperature or health monitoring. The thermomechanical performance and durability of such novel coating compositions in extreme environments still remains to be evaluated. Consequently, the ability to manufacture sensor coatings which present suitable thermal properties needs to be demonstrated. For this study, highly luminescent erbium and europium doped yttria-stabilized zirconia and state-of-the-art yttria-stabilized zirconia coatings manufactured by air plasma spray were characterized to determine the effects of the embedded rareearth dopants on coating internal strain and stress and to quantify and compare their high temperature response using synchrotron X-ray diffraction. In-situ depth-resolved strain measurements were performed at 15 μm intervals along the depth of the coatings to evaluate materials response at key locations, specifically at layer interfaces. In-plane stress was calculated for the coatings and a finite element model was implemented to supplement the results and enable further predictions. The results show that the sensor coatings that were manufactured in this work revealed only minor variations in the strain response of sensor coatings under a typical thermal cycle and especially at temperatures closer to that of gas turbine operating conditions, compared to state-of-the-art coatings. This work demonstrates the viability of manufacturing rare-earth doped yttria-stabilized zirconia coatings that provide beneficial spectroscopic monitoring capabilities while having minimal impact on the thermomechanical response of the thermal barrier coatings.

Air plasma spray↗

Synthesis, Structure, and Properties of Volatile Lanthanide Dialkyltriazenides

Several dialkyltriazenide complexes of the lanthanide elements neodymium, europium, and erbium have been prepared; these include the homoleptic complex Er(Bu t N 3 Bu t ) 3 , the tetrahydrofuran monoadducts Ln(Bu t N 3 Bu t ) 3 (THF) where Ln = Nd or Eu, and the lithium salts [Li(THF)][Ln(MeN 3 Bu t ) 4 ] where Ln = Eu or Er. Crystal structures, nuclear magnetic resonance data, and infrared data are reported for all complexes. Further, the di-tert-butyltriazenide complexes are thermally stable, sublime at reasonably low temperatures, and show smooth volatilization without decomposition, which make them potentially useful in lanthanide separation processes and as chemical vapor deposition precursors for lanthanide nitrides and other phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal Chemistry and Thermodynamics of HREE (Er, Yb) Mixing in a Xenotime Solid Solution

Rare earth elements (REEs), the 15 naturally occurring lanthanides plus yttrium and scandium, are ubiquitously used in modern life as they are critical components of many advanced devices and technologies. However, the demand for REEs is not equal, with the heavy rare earth elements (HREEs) having a higher demand. Xenotime (HREEPO 4 ) is an important HREE ore mineral and globally is an economical source of HREE. Most of the crystallographic and thermodynamic properties of xenotime endmembers have been elucidated by calorimetric, solubility, and high-pressure studies. Yet, in natural systems, endmembers are rarely encountered, and instead, REE solid solutions are more commonly observed. Here, we characterize the crystal chemistry, thermodynamics of HREE mixing, and high-temperature material behaviors and thermochemistry of a synthetic erbium (Er)-ytterbium (Yb) binary xenotime solid solution (Er (x) Yb (1-x) PO 4 ) using a suite of experimental techniques, including X-ray fluorescence spectroscopy, synchrotron X-ray powder diffraction implemented with Rietveld analysis, Fourier transform infrared spectroscopy coupled with attenuated total reflectance, Raman spectroscopy, thermogravimetric analysis coupled with differential scanning calorimetry, and high-temperature oxide melt drop solution calorimetry. Our results shed light on the formation of natural xenotimes and lay the foundation for their industrial applications as thermal coating materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Competition between Hubbard and Superexchange Interactions Selectively Localizes Electrons and Holes through Polarons

Controlling the effects of photoexcited polarons in transition metal oxides can enable the long time-scale charge separation necessary for renewable energy applications and controlling new quantum phases through dynamically tunable electron–phonon coupling. In previously studied transition metal oxides, polaron formation is facilitated by a photoexcited ligand-to-metal charge transfer (LMCT). When the polaron is formed, oxygen atoms move away from iron centers, which increases carrier localization at the metal center and decreases charge hopping. Studies of yttrium iron garnet and erbium iron oxide have suggested that strong electron and spin correlations can modulate photoexcited polaron formation. To understand the interplay between strong spin and electronic correlations in highly polar materials, we studied gadolinium iron oxide (GdFeO 3 ), which selectively forms photoexcited polarons through an Fe–O–Fe superexchange interaction. Excitation-wavelength-dependent transient extreme ultraviolet (XUV) spectroscopy selectively excites LMCT and metal-to-metal charge transfer (MMCT) transitions. Here, the LMCT transition suppresses photoexcited polaron formation due to the balance between superexchange and Hubbard interactions, while MMCT transitions result in photoexcited polaron formation within 250 ± 40 fs. Ab initio theory demonstrates that electron and hole polarons localize on iron centers following MMCT. In addition to understanding how strong electronic and spin correlations can control strong electron–phonon coupling, these experiments separately measure electron and hole polaron interactions on neighboring metal centers for the first time, providing insight into a large range of charge-transfer and Mott–Hubbard insulators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling single rare earth ion emission in an electro-optical nanocavity

Abstract Rare earth emitters enable critical quantum resources including spin qubits, single photon sources, and quantum memories. Yet, probing of single ions remains challenging due to low emission rate of their intra-4 f optical transitions. One feasible approach is through Purcell-enhanced emission in optical cavities. The ability to modulate cavity-ion coupling in real-time will further elevate the capacity of such systems. Here, we demonstrate direct control of single ion emission by embedding erbium dopants in an electro-optically active photonic crystal cavity patterned from thin-film lithium niobate. Purcell factor over 170 enables single ion detection, which is verified by second-order autocorrelation measurement. Dynamic control of emission rate is realized by leveraging electro-optic tuning of resonance frequency. Using this feature, storage, and retrieval of single ion excitation is further demonstrated, without perturbing the emission characteristics. These results promise new opportunities for controllable single-photon sources and efficient spin-photon interfaces.

42 ENGINEERING↗