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At least 19 records

Nd-142/Nd-144 in bulk planetary reservoirs, the problem of incomplete mixing of interstellar components and significance of very high precision Nd-145/Nd-144 measurements

Apart from the challenge of very high precision Nd-142/Nd-144 ratio measurement, accurate applications of the coupled Sm-(146,147)-Nd-(142,143) systematics in planetary differentiation studies require very precise knowledge of the present-day (post-Sm-146 decay) Nd-142/Nd-144 ratios of bulk planetary objects (BP). The coupled systematics yield model ages for the time of formation of Sm/Nd-fractionated reservoirs by differentiation of Sm/Nd-unfractionated bulk planetary reservoirs. Estimates of (Nd-142/Nd-144)(sub BP) and (Nd-143/Nd-144)(sub BP) therefore provide the critical baseline relative to which these model ages are referenced. In the Sm-147-Nd-143 systematics, Nd-143/Nd-144 variations are mostly large; therefore, small variations in initial Nd-143/Nd-144 ratios generally can be ignored. However, in the case of Sm-146-Nd-142, the range of Nd-142/Nd-144 divergence for differentiated planetary reservoirs is much smaller. Consequently Sm-(146,147)-Nd-(142,143) model ages are sensitive to small variations in bulk planetary Nd-142/Nd-144 (both present-day and initial). One major unanswered question is whether or not Nd shelf standards (CIT Nd beta/Ames metal, La Jolla, NASA-JSC/Ames metal) have Nd-142/Nd-144 identical to the bulk Earth or otherwise might record some degree of radiogenic evolution in an early-fractionated reservoir. Our discussions of earth Earth differentiation based on Nd-142/Nd-144 in Isua and Acasta samples have employed a working assumption: (Nd-142/Nd-144)(sub Nd beta) = (Nd-142/Nd-144)(sub Bulk Earth). This requires experimental justification and is apparently contradicted by chondrite Nd-142/Nd-144 measurements, which have been interpreted to indicate: (Nd-142/Nd-144)(sub JSC/Ames metal) = ((Nd-142/Nd-144)(sub CHUR) = 35 plus or minus 8 ppm). At present, interpretations of the early Earth and Moon hinge largely on this issue. Because Ba in bulk chondrite samples exhibit similar magnitude nuclear anomalies, attributable to incomplete mixing of interstellar components, a critical question is whether or not nuclear effects are also present in Nd-142/Nd-144, both in bulk chondrites and between planetary objects.

Harper, C. L., Jr.↗

Improved 140 Nd Production for the 140 Nd/ 140 Pr In Vivo Generator through Target Recycling and Radiochemical Optimization

Theranostic strategies that utilize f-block therapeutic radionuclides, including 161 Tb, 177 Lu, 225 Ac, and 227 Th, suffer from a shortage of positron emission tomography (PET) imaging counterparts in the same chemical space and often rely on 68 Ga as a surrogate. The 140 Nd/ 140 Pr in vivo PET generator, which belongs to the f-block, may address this issue and can be produced via the 141 Pr(p,2n) 140 Nd production route by using medium-energy cyclotrons. However, impurities in the target material, including stable Nd, and the inherent difficulty of adjacent lanthanide separations limit the achievable radionuclidic and chemical purity of 140 Nd. In this work, we address these challenges through the purification and recycling of praseodymium target material and optimization of Nd/Pr separation. The resulting purified 140Nd was evaluated using DOTA and Macropa chelators via radiolabeling and in vitro stability studies. A target material purification and recycling method was developed for the monoisotopic 141 Pr starting material to remove stable Nd impurities, yielding 90.3 ± 4.7% (n = 3) recovery. The purified 141 Pr was isolated as Pr 6 O 11 and irradiated with 24 MeV protons (20.07 MeV at the target surface) at 20 μA for 4 h, which produced 1417.0 ± 83.4 MBq (38.3 ± 2.2 mCi) of 140 Nd at the end of bombardment (EOB). The produced 140 Nd was purified through an optimized DGA normal method to recover 71.6 ± 6.3% pure 140 Nd. The amount of stable Nd reduced progressively in each target purification cycle from >340 ppm without purification to <250 ppb after three cycles, while other measured metallic impurities were below 30 ppb. This improvement in target purity was reflected in the direct increase of apparent molar activity (AMA), when purified 140 Nd was evaluated with DOTA and Macropa chelators. AMA of [ 140 Nd]Nd-DOTA and [ 140 Nd]Nd-Macropa increased from 70.3 MBq/μmol (1.9 mCi/μmol) and 74 MBq/μmol (2.0 mCi/μmol) to 8025.3 MBq/μmol (216.9 mCi/μmol) and 8473.0 MBq/μmol (229.0 mCi/μmol), respectively, after the third target purification cycle. Further evaluation of chelator-labeled 140 Nd showed that [ 140 Nd]Nd-DOTA was stable in phosphate-buffered saline (PBS), saline, human serum, and mouse serum, whereas [140Nd]Nd-Macropa was stable in all except human serum. This work established a practical methodological advance for the production of 140 Nd/ 140 Pr in vivo PET generators, combining optimized target recycling and radiochemical separation to enable scaled-up and high-molar activity 140 Nd suitable for preclinical imaging. These advances support broader development of 140 Nd/ 140 Pr as a robust PET analogue, especially for f-block therapeutics.

Irradiation↗

Effect of Fluoride Anions on Nd(III) Electrode Processes and Nd Metal Recovery in LiCl–KCl–NdCl 3

Here, this work investigated the impact of fluoride anions on Nd metal recovery in LiCl–KCl–NdCl 3 electrolytes by introducing LiF at a molar F/Nd ratio of 9 at 773 K. The voltammetric measurements confirmed that the fluoride ions facilitated single-step Nd(III)/Nd reduction by promoting the stability of the Nd(III) state compared to two-step reduction (Nd(III)/Nd(II) and Nd(II)/Nd) in all-chloride electrolytes. The stabilized Nd(III) state in the LiF-containing electrolyte effectively suppressed partial Nd(III)/Nd(II) reduction and the back-dissolution of Nd metal via comproportionation. By suppressing these reactions, high round-trip Coulombic efficiencies of 77–86% were achieved in the LiF-containing electrolyte during selective Nd deposition–removal cycles compared to 53–59% in all-chloride electrolytes. The Faradaic yield for Nd metal recovery was estimated at 38.6% in the LiF-containing electrolyte following long-term electrolysis, more than three times higher than 11.3% in all-chloride electrolytes. These results confirm the beneficial effect of fluoride ions on Nd metal recovery in low-melting chloride-based electrolytes, promising efficient Nd recovery at low temperatures.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Influence of Nd(II) and Nd(III) Ions on the Speciation and Kinetic Dynamics of Radiolytic Transients in Molten LiCl-KCl Eutectic Salt Mixtures

In the pyrochemical reprocessing of used nuclear fuel, understanding the effects of ionizing radiation on the chemical behavior of fission products in molten chloride eutectic salt is crucial. Here, this study investigates the impact of radiation on the chemical and kinetic speciation of Nd ions in molten LiCl-KCl eutectic, which are challenging to separate due to their multivalent oxidation states and comproportionation reactions. Electron pulse radiolysis techniques were used to determine transient absorption spectra, chemical kinetics, and activation parameters for the reaction of Nd ions with the primary products of molten LiCl-KCl eutectic radiolysis: the solvated electron (e S - ) and dichlorine radical anion (Cl 2 •- ). Initially, Nd(III) reacted rapidly with e S - , forming Nd(II) with a second-order rate coefficient of k = (4.54 ± 0.07) × 10 10 M -1 s -1 at 673 K. The resulting Nd(II) ions then reacted slowly with Cl 2 •- , regenerating Nd(III) with an estimated rate of k = (1.72 ± 0.04) × 10 10 M -1 s -1 at 673 K. Additionally, the comproportionation reaction of Nd(III) and Nd(s) to form Nd(II) was monitored chemically and electrochemically. This work suggests that the comproportionation reaction of Nd(III) with Nd(s) to form Nd(II) is unstable in molten LiCl-KCl eutectic.

36 - MATERIALS SCIENCE↗

Evaluation of Sb-Nd and Te-Nd phases within the U-Zr fuel matrix and their interactions with HT9 alloy

Antimony (Sb) and tellurium (Te) were investigated as potential additives for U-10Zr (wt.%) metallic fuel to limit the fuel-cladding chemical interaction (FCCI) with HT-9 alloy. Neodymium (Nd) was utilized to simulate the formation of lanthanide-based solid fission products which are known to play a detrimental role in FCCI. Fuel alloys of U-Zr-Sb-Nd and U-Zr-Te-Nd were evaluated in their annealed condition and compared against their as-cast conditions. Isothermal diffusion couple experiments were performed between U-Zr-Nd, U-Zr-Sb-Nd, and U-Zr-Te-Nd against the cladding alloy HT9 to evaluate the effectiveness of the additives to stabilize Nd within the fuel alloys, as well as investigate the interaction regions that form between the different fuel alloys and HT9. Further, SbNd and Sb 3 Nd 4 , and TeNd are found to be the primary neodymium-based phases formed in the U-Zr-Sb-Nd and U-Zr-Te-Nd alloys, respectively. The zirconium-based phase, Zr 2 Sb, is also found to form within the former alloy. All phases were found to remain stable through the diffusion experiments and exhibited no interaction with HT9 constituent elements. Preferential interaction between Nd with additivities Te and Sb compared to constituting elements in HT9 was further verified based on density functional theory (DFT) calculated enthalpy of mixing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Nd, SbNd and Sb 3 Nd 4 and their interactions with the cladding alloy HT9

Lanthanide fission products, such as neodymium, formed during the irradiation of metallic fuels are known to cause deleterious effects from chemical interactions occurring at the fuel-cladding interface; a phenomenon known as fuel-cladding chemical interaction (FCCI). The use of fuel-based additives that bind with the lanthanide elements within the fuel meat, alleviating their interactions at the fuel-cladding interface, is one potential method proposed to mitigate the FCCI phenomenon and extend the burnup potential of such metallic fuel systems. In this study, antimony (Sb) is evaluated as one such additive, and neodymium (Nd) is used to represent the lanthanides. A Sb-Nd alloy is fabricated, which consists of two intermetallic phases, SbNd and Sb 3 Nd 4 . Isothermal diffusion couple experiments are carried out at 675 °C for 24 h between Nd and the Fe-12Cr based HT9 cladding alloy. The results are compared against similar diffusion couple experiments carried out between the Sb-Nd alloy and also HT9. Inter-diffusion between Nd/HT9 diffusion couple is characterized and the phases Fe 17 Nd 5 and Fe 17 Nd 2 were found to form whereas no interactions were observed in the Sb-Nd/HT9 diffusion couple. The lack of compound forming tendencies between Fe, the primary alloying constituent of HT9, and SbNd is elucidated through density functional theory (DFT) calculations on enthalpy of mixing, aligning well with the experimental observations. Lastly, the strong binding of Nd with Sb appears to be favorable, alleviating Nd interactions with HT9 constituent elements.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Redetermination of the Sm-Nd Age and Initial (Epsilon)Nd of Lunar Troctolite 76535: Implications for Lunar Crustal Development

Lunar troctolite 76535 is an old lunar rock predating the era of the lunar cataclysmic bombardment, but its radiometrially determined ages have been discordant [1-3]. The most recent multi-chronometer study [4] gave preferred ages of 4226+/-35 Ma and 4236+/-15 Ma from a Pb-207/Pb-206 isochron and an U-Pb upper concordia intercept, resp. We derive an age of 4323+/-64 Ma from Sm-Nd data reported by [4] for the bulk rock and three mineral separates. They derived an age of approx.4.38 Ga from combined Rb-Sr data [3,4] by omitting data for olivine separates. Ar-39-Ar-40 ages of approx.4.2 Ga are summarized by [5]. New Sm-147-Nd-143 data presented here give an age of 4335+/-71 Ma in agreement with the Sm-Nd age from [4], whereas Sm-146-Nd-142 data give a model age T(sub LEW) = 4439+/-22 Ma. Further, initial (Epsilon)Nd-143 for 76535 conforms to the Nd-143 evolution expected in an urKREEP [6] reservoir, consistent with inheritance of urKREEP Sm-Nd systematics via assimilation. We show that urKREEP Sm-Nd systematics require the lunar initial (Epsilon)Nd-143 to exceed the Chondritic Uniform Reservoir (CHUR) value [7], but are consistent with evolution from initial (Epsilon)Nd-143 like that of the HED meteorite parent body as defined by a 4557+/-20 Ma internal isochron for the cumulate eucrites Y-980433 and Y- 980318 [8].

Nyquist, Laurence E.↗

Laser performance, thermal focusing and depolarization effects in Nd:Cr:GSGG and Nd:YAG

The laser performance of Nd:Cr:GSGG and Nd:YAG was investigated and compared for laser efficiency, thermal focusing, and depolarization effects. Laser efficiency was studied for Nd:Cr:GSGG and Nd:YAG under similar conditions. Laser efficiency was measured as a function of electrical energy and output mirror reflectivity. Maximum laser efficiency was calculated by determining the losses in the laser cavity. Thermal focusing and birefringence loss of Nd:Cr:GSGG and Nd:YAG have been examined by varying the average pump power. The average pump power changed by adjusting both the energy per pulse and the pulse-repetition frequency. Substantial thermal focusing differences for Nd:Cr:GSGG are explained.

Williams-Byrd, Julie A.↗

Coupled Nd-142, Nd-143 and Hf-176 Isotopic Data from 3.6-3.9 Ga Rocks: New Constraints on the Timing of Early Terrestrial Chemical Reservoirs

Increasingly precise data from a range of isotopic decay schemes, including now extinct parent isotopes, from samples of the Earth, Mars, Moon and meteorites are rapidly revising our views of early planetary differentiation. Recognising Nd-142 isotopic variations in terrestrial rocks (which can only arise from events occurring during the lifetime of now extinct Sm-146 [t(sub 1/2)=103 myr]) has been an on-going quest starting with Harper and Jacobsen. The significance of Nd-142 variations is that they unequivocally reflect early silicate differentiation processes operating in the first 500 myr of Earth history, the key time period between accretion and the beginning of the rock record. The recent establishment of the existence of Nd-142 variations in ancient Earth materials has opened a new range of questions including, how widespread is the evidence of early differentiation, how do Nd-142 compositions vary with time, rock type and geographic setting, and, combined with other types of isotopic and geochemical data, what can Nd-142 isotopic variations reveal about the timing and mechanisms of early terrestrial differentiation? To explore these questions we are determining high precision Nd-142, Nd-143 and Hf-176 isotopic compositions from the oldest well preserved (3.63- 3.87 Ga), rock suites from the extensive early Archean terranes of southwest Greenland and western Australia.

Bennett, Vickie C.↗

Synthesis and Characterization of Bulk Nd 1-x Sr x NiO 2 and Nd 1-x Sr x NiO 3

The recent reports of superconductivity in Nd 1-x Sr x NiO 2 /SrTiO 3 heterostructures have reinvigorated interest in potential superconductivity of low-oxidation state nickelates. Synthesis of Ni 1+ -containing compounds is notoriously difficult. In the current work, a combined sol-gel combustion and high-pressure annealing technique was employed to prepare polycrystalline perovskite Nd 1-x Sr x NiO 3 (x = 0, 0.1, and 0.2). Metal nitrates and metal acetates were used as starting materials, and the latter were found to be superior to the former in terms of safety and reactivity. The Nd 1-x Sr x NiO 3 compounds were subsequently reduced to Nd1-xSrxNiO2 using calcium hydride in a sealed, evacuated quartz tube. To understand the synthesis pathway, the evolution from NdNiO3 to NdNiO 2 was monitored using in situ synchrotron x-ray diffraction during the reduction process. Electrical transport properties were consistent with an insulator-metal transition occurring between x = 0 and 0.1 for Nd 1-x Sr x NiO 3 . Superconductivity was not observed in our bulk samples of Nd 1-x Sr x NiO 2 . Neutron diffraction experiments at 3 and 300 K were performed on Nd 0.9 Sr 0.1 NiO 2 , in which no magnetic Bragg reflections were observed, and the results of structural Rietveld refinement are provided.

36 MATERIALS SCIENCE↗

Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

Shaw, H. F.↗

Evaluating the effects of structural disorder on the magnetic properties of Nd 2 Zr 2 O 7

Motivated by the variation in reported lattice parameters of floating-zone-grown Nd 2 Zr 2 O 7 crystals, we have performed a detailed study of the relationship between synthesis environment, structural disorder, and magnetic properties. Using a combination of polycrystalline standards, electron-probe microanalysis, and scattering techniques, we show that crystals grown under atmospheric conditions have a reduced lattice parameter relative to pristine polycrystalline powders due to occupation of the Nd site by excess Zr (i.e., negative stuffing). In contrast, crystals grown under high-pressure Ar are nearly stoichiometric with an average lattice parameter approaching the polycrystalline value. While minimal disorder of the oxygen sublattices is observed on the scale of the average structure, neutron pair-distribution function analysis indicates a highly local disorder of the oxygen coordination, which is only weakly dependent on growth environment. Most importantly, our magnetization, heat capacity, and single-crystal neutron scattering data show that the magnetic properties of crystals grown under high-pressure Ar match closely with those of stoichiometric powders. Neutron scattering measurements reveal that the signature of magnetic moment fragmentation—the coexistence of all-in-all-out (AIAO) magnetic Bragg peaks and diffuse pinch-point scattering due to spin-ice correlations–persists in these nearly stoichiometric crystals. However, in addition to an increased AIAO transition temperature, the diffuse signal is seemingly stabilized and remains nearly unchanged upon warming to 800 mK. This behavior indicates that both the AIAO magnetic order and spin-ice correlations are sensitive to deviations of the Nd stoichiometry.

36 MATERIALS SCIENCE↗

Evidence from coupled (Sm-147)-(Nd-143) and (Sm-146)-(Nd-142) systematics for very early (4.5-Gyr) differentiation of the earth's mantle

Evidence for early differentiation of the earth's mantle is presented based on measurements of Nd-143/Nd-144 and Nd-142/Nd-144 ratios in an approximately 3.8 Gyr-old supracrustal rock from Isua, West Greenland. Coupled (Sm-146,147)-(Nd-142,143) systematics suggest that the fractionation of Sm/Nd took place 4.44-4.54 Gyr ago, due to extraction of a light rare earth element-enriched primordial crust.

Harper, Charles L., Jr.↗

Lamp pumped Nd:YAG laser. Space-qualifiable Nd:YAG laser for optical communications

Results are given of a program concerned with the design, fabrication, and evaluation of alkali pump lamps for eventual use in a space qualified Nd:YAG laser system. The study included evaluation of 2mm through 6mm bore devices. Primary emphasis was placed upon the optimization of the 4mm bore lamp and later on the 6mm bore lamp. As part of this effort, reference was made to the Sylvania work concerned with the theoretical modeling of the Nd:YAG laser. With the knowledge gained, a projection of laser performance was made based upon realistic lamp parameters which should easily be achieved during following developmental efforts. Measurements were made on the lamp performance both in and out of the cavity configuration. One significant observation was that for a constant vapor pressure device, the spectral and fluorescent output did not vary for vacuum or argon environment. Therefore, the laser can be operated in an inert environment (eg. argon) with no degradation in output. Laser output of 3.26 watts at 430 watts input was obtained for an optimized 4mm bore lamp.

Ward, K. B.↗

Environmental testing of a Q-switched Nd:YLF laser and a Nd:YAG ring laser

A Q-switched Nd:YLF laser (model 110-02) and a Nd:YAG ring laser (model 120-04) from Lightwave Electronics were subjected to thermal and vibration tests similar to what can be expected during launch and flight on a spacecraft. Even though these lasers were not designed for space flight, environmental tests were performed to identify major design weaknesses. Laser performance (output power, energy, pulsewidth, lasing threshold etc.) were measured prior to and after thermal vibration tests. Average output power of the Q-switched laser degraded 15-20 percent after thermal tests and an additional 20-25 percent after vibration tests. Post diagnostic tests revealed that degradation of the Q-switched laser was due to misalignment of pump focusing optics and the laser cavity.

Robinson, D. L.↗

Nd: LuLF: A New Nd Laser Material

Nd:LuLF, a novel laser material isomorphic to YLF, has been grown and evaluated on both polarizations in a simple, wavelength selective resonator.

Barnes, Norman P.↗