Separation of Tc from U and Development of Metallic Tc Waste Forms

The isotope Technetium-99 (99Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO4]-, Tc represents long-term concern to the biosphere. Various options have been considered to manage 99Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric acid and extraction of U and Tc in organic media, previously developed methods can be used to separate Tc from U, convert the separate Tc stream to the metal and reuse the uranium component of the fuel. A variety of metallic waste forms, ranging from pure Tc metal to ternary Tc alloys combined with stainless steel (SS) and Zr are proposed. The goal of this work was to examine three major questions: What is the optimal method to separate Tc from U? After separation, what is the most efficient method to convert the Tc stream to Tc metal? Finally, what is the corrosion behavior of Tc metal, Tc-SS alloys and Tc-Zr-SS alloys in 0.01M NaCl? The goal is to predict the long term behavior of Tc metallic waste in a hypothetical storage environment. In this work, three methods have been used to separate Tc from U: anionic exchange resin, liquid-liquid extraction and precipitation. Of the three methods studied, anionic exchange resins is the most selective. After separation of Tc from U, three different methods were studied to convert the Tc stream to the metal: thermal treatment under hydrogen atmosphere, electrochemical and chemical reduction of pertechnetate in aqueous media. The thermal treatment of the Tc stream under hydrogen atmosphere is the preferred method to produce Tc metal. After Tc metal is isolated, it will be incorporated into a metal host phase. Three different waste forms were produced for corrosion studies in this work: Pure Tc metal, SS(Tc 2 wt%)Zr and SS(Tc 1.34 wt%) alloys. Corrosion rate measurements indicate that both SS(Tc 2 wt%)Zr and SS(Tc 1.34 wt%) alloys corrode more slowly than metallic Tc in the solutions tested

Data publication: Discovery, nuclear properties, synthesis and applications of technetium-101

This article is a review paper, it is not based in experimental dat

Synthesis, structure elucidation and redox properties of 99Tc complexes of lacunary Wells Dawson polyoxometalates: insights into molecular 99Tc - metal oxide interactions

The isotope 99Tc (beta max: 250 keV, half-life: 2 x 105 year) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at Hanford and Savannah River. Understanding and controlling the extensive redox chemistry of 99Tc is important to identify tunable strategies to separate 99Tc from spent fuel and from waste tanks and once separated, to identify and develop an appropriately stable waste-form for 99Tc. Polyoxometalates (POMs), nanometer sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated 99Tc. In this study, 99Tc complexes of the (alpha 2-P2W17O61)10- and (alpha 1-P2W17O61)10- isomers were prepared. Ethylene glycol was used as a"transfer ligand" to minimize the formation of TcO2 cdot xH2O. The solution structures, formulations, and purity of TcVO(alpha 1/alpha 2-P2W17O61)7- were determined by multinuclear NMR. X-ray Absorption Spectroscopy of the complexes are in agreement with the formulation and structures determined from 31P and 183W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the TcVO(alpha 1-P2W17O61)7- species compared to the TcVO(alpha 2-P2W17O61)7- analog. The alpha1- defect is unique in that a basic oxygen atom is positioned toward the alpha1- site and the TcVO center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the ReV analogs are about 200 mV more difficult to reduce in accordance with periodic trends

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO₂(NO₃)₂(H₂O)₆] often called UNH), the trihydrate [UO₂(NO₃)₂(H₂O)₃ or UNT], and in very dry environments the dihydrate form [UO₂(NO₃)₂(H₂O)₂]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N₂ gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO₂(NO₃)₂(H₂O)₆ has a distinct uranyl asymmetric stretch band at 949.0 cm^–1 that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm^–1. The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO₂²⁺ sites. The dehydration of UO₂(NO₃)₂(H₂O)₆ to UO₂(NO₃)₂(H₂O)₃ is both a structural and morphological change that has the lustrous lime green UO₂(NO₃)₂(H₂O)₆ crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate

Search for long-lived particles decaying in the CMS muon detectors in proton-proton collisions at s\sqrt{s} = 13 TeV

International audienceA search for long-lived particles (LLPs) decaying in the CMS muon detectors is presented. A data sample of proton-proton collisions at $\sqrt{s}$ = 13 TeV corresponding to an integrated luminosity of 138 fb$^{-1}$ recorded at the LHC in 2016-2018, is used. The decays of LLPs are reconstructed as high multiplicity clusters of hits in the muon detectors. In the context of twin Higgs models, the search is sensitive to LLP masses from 0.4 to 55 GeV and a broad range of LLP decay modes, including decays to hadrons, $\tau$ leptons, electrons, or photons. No excess of events above the standard model background is observed. The most stringent limits to date from LHC data are set on the branching fraction of the Higgs boson decay to a pair of LLPs with masses below 10 GeV. This search also provides the best limits for various intervals of LLP proper decay length and mass. Finally, this search sets the first limits at the LHC on a dark quantum chromodynamic sector whose particles couple to the Higgs boson through gluon, Higgs boson, photon, vector, and dark-photon portals, and is sensitive to branching fractions of the Higgs boson to dark quarks as low as 2$\times$10$^{-3}$

Search for the lepton flavor violating τ→\tau \to 3μ\mu decay in proton-proton collisions at s\sqrt{s} = 13 TeV

International audienceA search for the lepton flavor violating $\tau \to$ 3$\mu$ decay is performed using proton-proton collision events at a center-of-mass energy of 13 TeV collected by the CMS experiment at the LHC in 2017-2018, corresponding to an integrated luminosity of 97.7 fb$^{-1}$. Tau leptons produced in both heavy-flavor hadron and W boson decays are exploited in the analysis. No evidence for the decay is observed. The results of this search are combined with an earlier null result based on data collected in 2016 to obtain a total integrated luminosity of 131 fb$^{-1}$. The observed (expected) upper limits on the branching fraction $\mathcal{B}$($\tau \to$ 3$\mu$) at confidence levels of 90 and 95% are 2.9$\times$10$^{-8}$ (2.4$\times$10$^{-8}$) and 3.6$\times$10$^{-8}$ (3.0$\times$10$^{-8}$), respectively

The CMS Statistical Analysis and Combination Tool: COMBINE

International audienceThis paper describes the COMBINE software package used for statistical analyses by the CMS Collaboration. The package, originally designed to perform searches for a Higgs boson and the combined analysis of those searches, has evolved to become the statistical analysis tool presently used in the majority of measurements and searches performed by the CMS Collaboration. It is not specific to the CMS experiment, and this paper is intended to serve as a reference for users outside of the CMS Collaboration, providing an outline of the most salient features and capabilities. Readers are provided with the possibility to run COMBINE and reproduce examples provided in this paper using a publicly available container image. Since the package is constantly evolving to meet the demands of ever-increasing data sets and analysis sophistication, this paper cannot cover all details of COMBINE. However, the online documentation referenced within this paper provides an up-to-date and complete user guide

Search for production of a single vector-like quark decaying to tH or tZ in the all-hadronic final state in pp collisions at s\sqrt{s} = 13 TeV

International audienceA search for electroweak production of a single vector-like T quark in association with a bottom (b) quark in the all-hadronic decay channel is presented. This search uses proton-proton collision data at $\sqrt{s}$ = 13 TeV collected by the CMS experiment at the CERN LHC during 2016-2018, corresponding to an integrated luminosity of 138 fb$^{-1}$ The T quark is assumed to have charge 2/3 and decay to a top (t) quark and a Higgs (H) or Z boson. Event kinematics and the presence of jets containing b hadrons are used to reconstruct the hadronic decays of the t quark and H or Z boson. No significant deviation from the standard model prediction is observed in the data. The 95% confidence level upper limits on the product of the production cross section and branching fraction of a T quark produced in association with a b quark and decaying via tH or tZ range from 1260 to 68 fb for T quark masses of 600-1200 GeV

Searches for violation of Lorentz invariance in tt‾ \mathrm{t} \overline{\mathrm{t}} production using dilepton events in proton-proton collisions at s= \sqrt{s}= 13 TeV

A search for violation of Lorentz invariance in the production of top quark pairs ($\mathrm{t} \overline{\mathrm{t}}$) is presented. The measured normalized differential $\mathrm{t} \overline{\mathrm{t}}$ production cross section, as function of the sidereal time, is examined for potential modulations induced by Lorentz-invariance breaking operators in an effective field theory extension of the standard model (SM). The cross section is measured from collision events collected by the CMS detector at a center-of-mass-energy of 13 TeV, corresponding to an integrated luminosity of 77.8 fb$^{-1}$, and containing one electron and one muon. The results are found to be compatible with zero, in agreement with the SM, and are used to bound the Lorentz-violating couplings to be in ranges of 1-8 $\times$ 10$^{-3}$ at 68% confidence level. This is the first precision test of the isotropy in special relativity with top quarks at the LHC, restricting further the bounds on such couplings by up two orders of magnitude with respect to previous searches conducted at the Tevatron.A search for violation of Lorentz invariance in the production of top quark pairs ($\mathrm{t\bar{t}}$) is presented. The measured normalized differential $\mathrm{t\bar{t}}$ production cross section, as function of the sidereal time, is examined for potential modulations induced by Lorentz-invariance breaking operators in an effective field theory extension of the standard model (SM). The cross section is measured from collision events collected by the CMS detector at a center-of-mass-energy of 13 TeV, corresponding to an integrated luminosity of 77.8 fb$^{-1}$, and containing one electron and one muon. The results are found to be compatible with zero, in agreement with the SM, and are used to bound the Lorentz-violating couplings to be in ranges of 1 - 8 $\times$ 10$^{-3}$ at 68% confidence level. This is the first precision test of the isotropy in special relativity with top quarks at the LHC, restricting further the bounds on such couplings by up two orders of magnitude with respect to previous searches conducted at the Tevatron