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At least 397 records · Page 22

Study on separation of minor actinides from HLLW with new extractant of TODGA-DHOA/Kerosene

The extraction behavior of U, Np, Pu, Am, rare earth elements and Sr from nitric acid solutions by TODGA/dodecan, DHOA/dodecane and TODGA-DHOA/dodecane were investigated, respectively. Based on experimental results, a separation process was proposed for minor actinide isolation from high level liquid waste (HLLW): the TODGA-DHOA/kerosene system. The multi-stage counter-current cascade experiments were carried out for the purpose by 0.1 mol/l TODGA-1.0 mol/l DHOA/kerosene with miniature mixer- settler contactor rigs (8 stages for extraction, 6 stages for scrubbing, 8 stages for first stripping, 8 stages for second stripping). The results show that the recovery efficiencies of the actinides and lanthanides are more than 99.9%, whereas less than 1% Sr was extracted by 0.1 mol/l TODGA - 1.0 mol/l DHOA/kerosene. The stripping efficiencies of U, Np and Pu are more than 95% in the first stripping step by 0.5 mol/l HNO{sub 3} + 0.5 mol/l AHA(aceto-hydroxamic acid), all of the remained actinides and lanthanides can be stripped by 0.01 mol/l HNO{sub 3} in the second stripping step. 99% Sr was extracted by 0.1 mol/l TODGA/kerosene, so Sr can be recovered efficiently directly from the raffinate by 0.1 mol/l TODGA/kerosene. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gadolinium speciation with Tetradentate, N-donor extractants for minor actinide/lanthanide separation: an XRD, mass spectrometry and EPR study

The hydrophobic organic molecules CyMe{sub 4}-BTPhen (1) and CyMe{sub 4}-BTBP (2) have been developed and tuned over many years to be able to separate the trivalent actinides from the trivalent lanthanides (Ln) selectively in bi-phasic solvent extraction processes for the separation of the long-lived radio-toxic minor actinides from spent nuclear fuel. The ability of these N-donor ligands to perform this separation is poorly understood, as is their speciation with the metal ions when extracted into the organic phase. Our previous work has shown Ln{sup 3+} speciation to be largely 1:2 Ln:L in nature with another small molecule, either water or nitrate, occupying a cavity between the tetradentate bound N-donor ligands. The identity of the small molecule changes across the lanthanide series, and here we continue investigations into this speciation. Complexes of these N-donor ligands with Gd{sup 3+} have been synthesised and characterised by X-ray crystallography, mass spectrometry and EPR spectroscopy. We show that the N-donor ligands have no effect on the electronic configuration of Gd{sup 3+} and that the lanthanide contraction with the steric rigidity of the N-donor ligand appears to determine the size of the cavity between the coordinated ligands. This in turn appears to control the identity of the small molecule on the ninth site in the 1:2 Gd:L species. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Main results of the french R and D on minor actinides partitioning, a significant improvement towards nuclear waste reduction - 15618

In the framework of the successive 1991 and 2006 Waste Management Act, French government supported a very significant R and D program on partitioning and transmutation of minor actinides (MA). This program aims to study potential solutions for still minimizing the quantity and the hazardousness of final waste, by MA recycling. Indeed, MA recycling can reduce the heat load and the half-life of most of the waste to be buried to a couple of hundred years, overcoming the concerns of the public related to the long-life of the waste. Within this framework, this paper aims to present the most recent progress obtained in CEA on the development of innovative actinide partitioning hydrometallurgical processes in support of their recycling, either in an homogeneous mode (MA are recycled at low concentration in all the standard reactor fuel) or in an heterogeneous mode (MA are recycled at higher concentration in specific targets, at the periphery of the reactor core). Recovery performances obtained on recent tests in high active conditions of the so-called GANEX and DIAMEX-SANEX process will be presented and discussed in light of the potential P and T scenarios. Finally, recent developments regarding the recycling of the sole Am will be presented as well as the results obtained on highly active solutions for this so-called EXAM process. This set of results gives to the French government a portfolio of potential recycling processes which could be separately and progressively implemented if decided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Fabrication of Minor Actinide MOX Fuel for the AFC-2C and -2D Irradiations

Minor actinide bearing mixed oxide (MAMOX) fuels of nominal composition (U{sub 0.75}Pu{sub 0.20}Np{sub 0.02}Am{sub 0.03}) O{sub 2-x} were fabricated at Los Alamos National Laboratory (LANL) for the AFC-2C and AFC-2D irradiations that were conducted by the US-DOE under the Advanced Fuel Cycle program. The primary goal of this irradiation test series was to assess the irradiation performance behavior of MA-MOX fuel under prototypic fast reactor conditions. This paper describes the results of the MA-MOX fuel fabrication and pre-irradiation characterization effort and includes discussion of specific fresh fuel properties that affect irradiation performance. The as-fabricated MA-MOX compositions were (U{sub 0.77}Pu{sub 0.19}Np{sub 0.03}Am{sub 0.02})O{sub 2-x} with x=0.01 and 0.04. A comparison of fuel to clad interaction and cladding corrosion for fuels with O:M of 1.99 and 1.96 will be of particular interest during post-irradiation examination which is underway at the INL and discussed in a companion paper presented in this forum. The average fuel density was 87% of theoretical. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NMR Spectroscopy and Structural Characterization of Dithiophosphinates Relevant to Minor Actinide Extraction Processes

Synthetic routes to alkyl and aryl substituted dithiophosphinate salts that contain non-coordinating PPh{sub 4}{sup 1+} counter cations are reported. In general, these compounds can be prepared via a multi-step procedure that starts with reacting secondary phosphines, i.e. HPR{sub 2}, with two equivalents elemental S. This transformation proceeds in two steps - first oxidation of the phosphine and second insertion of S into the H-P bond - and has been used to synthesize a series of dithiophoshinic acids, which were fully characterized, namely HS{sub 2}P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(m-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(o-MeC{sub 6}H{sub 4}){sub 2}, and HS{sub 2}P(o-MeOC{sub 6}H{sub 4}){sub 2}. Although the insertion step was found to be much slower than the oxidation reaction, the formation of (NH{sub 4})S{sub 2}PR{sub 2} from HPSR{sub 2} occurs almost instantaneous upon addition of NH{sub 4}OH. Subsequent cation exchange reactions proceed readily with PPh{sub 4}Cl in water, under air, and at ambient conditions to provide analytically pure samples of [PPh{sub 4}][S{sub 2}PR{sub 2}] (R = p-CF{sub 3}C{sub 6}H{sub 4}, m-CF{sub 3}C{sub 6}H{sub 4}, o-CF{sub 3}C{sub 6}H{sub 4}, o-MeC{sub 6}H{sub 4}, o-MeOC{sub 6}H{sub 4}, Ph, and Me, 1b-7b, respectively), which were characterized by elemental analysis, multinuclear NMR, and IR spectroscopy. In addition the S{sub 2}PMe{sub 2}{sup 1-}, S{sub 2}PPh{sub 2}{sup 1-}, and dithiophosphinates with ortho-substituted arene rings were characterized by X-ray crystallography. Structural analysis show that, as opposed to the acids which have short P=S double bonds and long P-SH single bonds, the metric parameters for the S atoms in S{sub 2}PR{sub 2}{sup 1-} are equivalent. In addition, the presence of large non-coordinating PPh{sub 4}{sup 1+} cations guard against intermolecular P-S {hor_ellipsis} X interactions and insure that the P-S bond is isolated. Overall, this synthetic procedure provides high-purity S{sub 2}PR{sub 2}{sup 1-} compounds necessary for subsequent spectroscopic and theoretical studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling

The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N',N';-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) were uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. As a result, the identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Equity for women and underrepresented minorities in STEM: Graduate experiences and career plans in chemistry

Significance On June 10, 2020, as part of the Black Lives Matter movement, scientists in the United States and throughout the world paused to consider how systematic racism affects the scientific enterprise. As a result, many academic departments are now assessing policies and practices that may contribute to this situation. This paper provides evidence of the nature of inequities related to race–ethnicity and gender in graduate school experiences and career plans of PhD students in one science, technology, engineering, and math (STEM) discipline, chemistry. The results can help promote understanding of the problems and guide efforts toward equity within STEM and, potentially, other academic areas. In turn, these changes can strengthen the scientific enterprise and the well-being of society.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nevada National Security Site support for Minority Serving Institutions

Poster to be presented to academics and STEM students from local universities during the American Association of Colleges and Universities (AAC&U) Transforming STEM Higher Education Conference: Back to Broken?, November 3–5, 2022, Arlington, VA (https://secure.aacu.org/iMIS/AACUR/Events/Event_Display.aspx?EventKey=STEM22).

99 GENERAL AND MISCELLANEOUS↗

Adiabatic Quantum Programming: Minor Embedding With Hard Faults

Adiabatic quantum programming defines the time-dependent mapping of a quantum algorithm into the hardware or logical fabric. An essential programming step is the embedding of problem-specific information into the logical fabric to define the quantum computational transformation. We present algorithms for embedding arbitrary instances of the adiabatic quantum optimization algorithm into a square lattice of specialized unit cells. Our methods are shown to be extensible in fabric growth, linear in time, and quadratic in logical footprint. In addition, we provide methods for accommodating hard faults in the logical fabric without invoking approximations to the original problem. These hard fault-tolerant embedding algorithms are expected to prove useful for benchmarking the adiabatic quantum optimization algorithm on existing quantum logical hardware. We illustrate this versatility through numerical studies of embeddabilty versus hard fault rates in square lattices of complete bipartite unit cells.

graph theory↗