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At least 73 records · Page 4

Transmission electron microscopy study of a high burnup U-10Zr metallic fuel

To support the development of U-10 wt.% Zr (U-10Zr) metallic fuel for Gen IV sodium-cooled fast reactors, we analysed a solid, Na-bonded, U-10Zr (by weight percent) fuel cross section that was irradiated to a burnup of ~ 12.4 % at.% at the Fast Flux Test Facility (FFTF). Advanced characterization techniques, including site specific sample preparation by focused ion beam (FIB) and phase/chemical determination by transmission electron microscopy (TEM), were used to reveal the constituent redistribution of Zr, characterize the fuel phases and the secondary phases (such as solid fission products) present at the end of life. It is shown that the fuel pin cross section is divided into three major concentric zones: a Zr-rich central region, a Zr-lean intermediate region, and a Zr intermediate peripherical region. The phase characterization revealed that the irradiation environment enhanced the development and stabilization of phases not predicted by the standard equilibrium U-Zr phase diagrams. Comparing the current results with the ones from previous studies, it is reaffirmed that the irradiation temperature and the time spent in the reactor, rather than the fuel burnup, are the two factors that most influence the formation of redistribution zones and their extension along the fuel cross section. Various solid fission products precipitated inside the fission gas pores, such as lanthanides, ZrRu, BaTe, CsI, and Ba and Sr oxides. Here, this study provides unprecedented nanoscale understandings in the U-10Zr fuel system that may benefit fuel performance modelling and advanced fuel development.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Coprecipitation of Fe/Cr Hydroxides at Organic–Water Interfaces: Functional Group Richness and (De)protonation Control Amounts and Compositions of Coprecipitates

Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO 2 through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pK(a) values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) >> BSA(-NH 2 )) and composition (Cr/Fe molar ratio: on BSA(-NH2) >> HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH 2 were positively charged at acidic pH because of the high pK(a) value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH 2 coatings promoted the formation of Cr(OH) 3 . Finally, this study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Challenges in Safeguards for Metallic Fuel Fabrication Facilities

As new advanced reactors gain popularity, there is an increasing interest in metallic fuel fabrication for fast reactors. While metallic fuels themselves are not a new idea, as many of the first reactors employed metallic fuels, new designs, compositions, and fabrication methods are appearing throughout the nuclear community. As the interest grows and facilities are constructed, both domestic and international safeguards will need to be heavily involved to support safeguards-by-design (SBD) measures from the start. This work compiles a review of historical and modern fuel types and fabrication methods, fabrication processes, safeguards gaps, and potential safeguards solutions. Metallic nuclear fuel types have been around for many decades and were included in some of the first reactors including the Experimental Breeder Reactor (EBR)-I and -II, the Fermi 1 reactor, the Integral Fast Reactor (IFR), and the Dounreay Fast Reactor (DFR). These reactors used various compositions including pure uranium (U) metal, U-zirconium (Zr) alloys, plutonium (Pu)-aluminum (Al) alloys, U-fissium (Fs) alloys, U-Pu-Zr alloys, and U-molybdenum (Mo) alloys [1, 2, 3, 4, 5]. These small alloying additions are included to improve the material properties of the pure U metal. The alpha-phase U (stable below 661C) suffers elongation in one direction causing grain boundary cracking and increasing creep rate due to irradiation growth, thermal cycling, and preferential crystal orientation. It is ideal to utilize the gamma-phase U (typically stable above 769C) by adding small amounts of alloying elements such as Zr or Mo to stabilize this phase down to room temperature [3]. Additionally, some research has been focused on U with transuranic (TRU) elements present, typically coming from the used fuel recycling process. Including these elements in fast reactor fuel can aid in the reduction of nuclear waste by burning minor long-lived actinides. However, the additions of TRU elements can cause concerns to arise when trying to fabrication or safeguard metallic fuels. A typical metallic fuel element is shown in Figure 1. Sodium is added into the cladding to create a thermal bond between the fuel slug and cladding wall. The fuel slug is then inserted and the end plug is welded on to the top of the fuel element. A gas plenum is left to create a headspace for gaseous fission products to escape rather than continue to build in the fuel itself [1, 5]. Other fuel element geometries exist as well, such as the Lightbridge twisted cruciform geometry shown in Figure 2 [6]. This design allows for better cooling performance and provides room for fuel rod swelling without impacting the fuel rod diameter. There are many different fabrication methods for metallic fuels, which is one of the many benefits of these fuel types. Many of these fabrication methods are relatively easy and cost-efficient. The most popular fabrication method is injection casting, sometimes called vacuum induction melting (VIM), shown in Figure 3 [4, 8, 9, 7, 10]. This method was largely used for EBR-II fuel fabrication. The injection casting system is contained inside of a vessel consisting of a Y2O3-coated graphite crucible surrounded by an induction coil with ZrO2-coated quartz molds suspended above the crucible. The fuel feedstock is placed inside of the graphite crucible and melted using the induction furnace. The induction furnace utilizes a dual frequency with the high frequency melting the feedstock and the low frequency causing stirring of the melted feedstock to form a homogeneous mixture. The mixture is heated to approximately 1600C in an argon environment. The vessel is evacuated and then the quartz molds are lowered into the graphite crucible containing the molten metal and the vessel is repressurized to inject the metal fuel upwards into the molds. The molds are removed and then shattered to release the fuel slugs. This fabrication method was used to fabricate 39,000 metallic fuel pins for EBR-II. While injection casting has been the most common metallic fuel fabrication method throughout the decades, many other methods have been explored including low-pressure gravity casting, microwave casting, continuous casting, centrifugal casting, coextrusion, and many others [11, 12, 8, 13, 14, 15]. Some of these methods aim to mitigate challenges that arise with americium (Am) volatilization during the casting process for TRU-containing fuel feedstocks, an issue with injection casting. Coextrusion is one of the methods explored at the Idaho National Laboratory (INL) and has been utilized for the initial fabrication tests of Lightbridge's unique fuels, as well as other metallic fuels with cladding coextruded. In this process, large billets are formed and machined and then inserted into a molten salt bath for approximately 30 minutes. The billets are then loaded into the extrusion press and extruded. This process can be seen in Figure 4 [15].

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are usually interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na 2 O] x [Al 2 O 3 ] 2 [SiO 2 ] 98- x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Hence, the bond length and angle distributions as well as Si– Q n species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm -1 ) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Q n speciation; and (c) assignment of the Raman bands in the 420-600 cm -1 region to the bending modes of (SiO) n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This result invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.

36 MATERIALS SCIENCE↗

A Self‐Healing Chemistry‐Enabled Organic Cathode for Sustainable and Stable Sodium‐Ion Batteries

Sodium‐on batteries (SIBs) are promising alternatives to lithium‐ion batteries (LIBs) because of the low cost, abundance, and high sustainability of sodium resources. Analogous to LIBs, the high‐capacity electrodes in SIBs always suffer from rapid capacity decay upon long‐term cycling due to the particle pulverization induced by a large volume change. Circumventing particle pulverization plays a critical role in developing high‐energy and long‐life SIBs. Herein, tetrahydroxy‐1,4‐benzoquinone disodium salt (TBDS) that can self‐heal the cracks by hydrogen bonding between hydroxyl group and carbonyl group is employed as a cathode for sustainable and stable SIBs. The self‐healing TBDS exhibits long cycle life of 1000 cycles with a high rate capability up to 2 A g −1 due to the fast Na‐ion diffusion reaction in the TBDS cathode. The intermolecular hydrogen bonding has been comprehensively characterized to understand the self‐healing mechanism. The hydrogen bonding‐enabled self‐healing organic materials are promising for developing high‐energy and long‐cycle‐life SIBs.

25 ENERGY STORAGE↗

Phenanthroline-strapped calix[4]pyrroles: anion receptors displaying affinity reversal as a function of solvent polarity

Calix[4]pyrroles 1 and 2, diametrically strapped with a phenanthroline via ester and amide linkages, respectively, have been synthesized as anion receptors. It was revealed by 1 H NMR spectroscopic analysis that receptors 1 and 2 possessing both hydrogen bonding donors and acceptors were able to bind the bicarbonate anion (as its tetraethylammonium (TEA + ) or sodium salt) in CDCl 3 , as well as in 15% aqueous DMSO with high affinity and selectivity over other anions. The amide-based receptor 2 contains additional potential hydrogen bonding donors relative to its ester-based congener 1. Nevertheless, in CDCl 3 receptor 1 was found to display a higher affinity for all test anions than receptor 2. In contrast, in 15% aqueous DMSO solution the affinities of receptor 2 for anions, in particular chloride, bicarbonate, and dihydrogen phosphate, were enhanced, whereas those of receptor 1 were reduced dramatically with no appreciable interaction being seen in the case of most test anions considered in this study. These reversals in selectivity and affinities underscore the importance of solvent in regulating the recognition features of seemingly similiar anion binding agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser fluorescence studies of the chemical interactions of sodium species with sulfur bearing fuels

By using a large matrix of fuel rich and fuel lean H2/O2/N2 and fuel rich C2H2/O2/N2 flames, the behavior of sodium and its interactions with sulfur at high temperatures was extensively characterized. OH concentrations were measured for each flame using the previously validated laser induced fluorescence technique. Sodium atomic concentrations were obtained by the saturated laser fluorescence method. Measurements were made in the absence and presence of up to 2% sulfur. In oxygen rich systems sodium is depleted by NaO2 and NaOH formation. The relative amounts of each are controlled by the degree of nonequilibration of the flame radicals and by the temperature. The bond strength of NaO2 was established. For the first time, a complete understanding of the complex behavior of sodium in fuel lean H2/O2 flames has emerged and computer modeling has permitted various rate constants of Na, NaO2 and NaOH reactions to be approximately fixed.

Steinberg, M.↗

Probing the Redox Reactivity of Alkyl Bound Astatine: A Study on the Formation and Cleavage of a Stable At–C Bond

The formation of a stable alkyl At–C bond occurs during the shipment of 211 At on a 3-octanone-impregnated column and the reactivity of 211 At stripped from columns has been studied. The 211 At could not be recovered from the 3-octanone organic phase using nitric acid or sodium hydroxide, even up to 10 and 15.7 M, respectively. Several reducing and oxidizing agents, including hydrazine, hydroxylamine, ascorbic acid, ceric ammonium nitrate, potassium permanganate, sodium hypochlorite, and calcium hypochlorite were used to promote the recovery of 211 At. The most effective reducing agent was hydroxylamine, where ~70% of the 211 At was recovered, while among oxidizing agents ceric ammonium nitrate, potassium permanganate, and sodium hypochlorite all showed near quantitative recovery of 211 At. These results indicate an At–C bond is being formed during the shipment of the column and a redox reaction is required for bond cleavage to occur. Furthermore, DFT calculations have been used to propose several products of an AtO + -3-octanone reaction, with 4-astato-5-hydroxy-octa-3-one being the most probable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials Data on Na3SiTe3 by Materials Project

(Na)3SiTe3 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of twelve sodium molecules and two SiTe3 clusters. In each SiTe3 cluster, Si4- is bonded in a tetrahedral geometry to one Si4- and three Te+0.33+ atoms. The Si–Si bond length is 2.38 Å. There are one shorter (2.53 Å) and two longer (2.54 Å) Si–Te bond lengths. There are three inequivalent Te+0.33+ sites. In the first Te+0.33+ site, Te+0.33+ is bonded in a single-bond geometry to one Si4- atom. In the second Te+0.33+ site, Te+0.33+ is bonded in a single-bond geometry to one Si4- atom. In the third Te+0.33+ site, Te+0.33+ is bonded in a single-bond geometry to one Si4- atom.

36 MATERIALS SCIENCE↗

Materials Data on Rb3Na by Materials Project

(Rb)3Na is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional and consists of one sodium molecule and one Rb framework. In the Rb framework, Rb is bonded in a 8-coordinate geometry to eight equivalent Rb atoms. All Rb–Rb bond lengths are 4.72 Å.

36 MATERIALS SCIENCE↗

Materials Data on Na3DyCl6 by Materials Project

(Na)2NaDyCl6 is High-temperature superconductor-derived structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one NaDyCl6 framework. In the NaDyCl6 framework, Na1+ is bonded to six equivalent Cl1- atoms to form NaCl6 octahedra that share corners with six equivalent DyCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Na–Cl bond lengths are 2.70 Å. Dy3+ is bonded to six equivalent Cl1- atoms to form DyCl6 octahedra that share corners with six equivalent NaCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Dy–Cl bond lengths are 2.62 Å. Cl1- is bonded in a linear geometry to one Na1+ and one Dy3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Na3Al4O8 by Materials Project

(Na)3(AlO2)4 crystallizes in the cubic Im-3m space group. The structure is three-dimensional and consists of twelve sodium molecules and one AlO2 framework. In the AlO2 framework, Al is bonded to four O atoms to form corner-sharing AlO4 tetrahedra. There is one shorter (1.70 Å) and three longer (1.76 Å) Al–O bond length. There are two inequivalent O sites. In the first O site, O is bonded in a linear geometry to two equivalent Al atoms. In the second O site, O is bonded in a bent 150 degrees geometry to two equivalent Al atoms.

36 MATERIALS SCIENCE↗

Materials Data on Na3NdCl6 by Materials Project

(Na)2NaNdCl6 is High-temperature superconductor-derived structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one NaNdCl6 framework. In the NaNdCl6 framework, Na1+ is bonded to six equivalent Cl1- atoms to form NaCl6 octahedra that share corners with six equivalent NdCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Na–Cl bond lengths are 2.71 Å. Nd3+ is bonded to six equivalent Cl1- atoms to form NdCl6 octahedra that share corners with six equivalent NaCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Nd–Cl bond lengths are 2.71 Å. Cl1- is bonded in a linear geometry to one Na1+ and one Nd3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Na2ScHgF6 by Materials Project

(Na)2ScHgF6 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one ScHgF6 framework. In the ScHgF6 framework, Sc2+ is bonded to six equivalent F1- atoms to form ScF6 octahedra that share corners with six equivalent HgF6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Sc–F bond lengths are 2.02 Å. Hg2+ is bonded to six equivalent F1- atoms to form HgF6 octahedra that share corners with six equivalent ScF6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Hg–F bond lengths are 2.50 Å. F1- is bonded in a linear geometry to one Sc2+ and one Hg2+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Na2HgAsCl6 by Materials Project

(Na)2HgAsCl6 is High-temperature superconductor-derived structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one HgAsCl6 framework. In the HgAsCl6 framework, Hg2+ is bonded to six equivalent Cl1- atoms to form HgCl6 octahedra that share corners with six equivalent AsCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Hg–Cl bond lengths are 2.79 Å. As2+ is bonded to six equivalent Cl1- atoms to form AsCl6 octahedra that share corners with six equivalent HgCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All As–Cl bond lengths are 2.51 Å. Cl1- is bonded in a linear geometry to one Hg2+ and one As2+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Na2LiErCl6 by Materials Project

(Na)2LiErCl6 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one LiErCl6 framework. In the LiErCl6 framework, Li1+ is bonded to six equivalent Cl1- atoms to form LiCl6 octahedra that share corners with six equivalent ErCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Li–Cl bond lengths are 2.52 Å. Er3+ is bonded to six equivalent Cl1- atoms to form ErCl6 octahedra that share corners with six equivalent LiCl6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Er–Cl bond lengths are 2.59 Å. Cl1- is bonded in a linear geometry to one Li1+ and one Er3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Na2TlCuBr6 by Materials Project

(Na)2CuTlBr6 is High-temperature superconductor-derived structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight sodium molecules and one CuTlBr6 framework. In the CuTlBr6 framework, Cu1+ is bonded to six equivalent Br1- atoms to form CuBr6 octahedra that share corners with six equivalent TlBr6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cu–Br bond lengths are 2.57 Å. Tl3+ is bonded to six equivalent Br1- atoms to form TlBr6 octahedra that share corners with six equivalent CuBr6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Tl–Br bond lengths are 2.85 Å. Br1- is bonded in a linear geometry to one Cu1+ and one Tl3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on CsNaO3 by Materials Project

NaCsO3 is (Cubic) Perovskite structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional and consists of one sodium molecule and one CsO3 framework. In the CsO3 framework, Cs is bonded to six equivalent O atoms to form corner-sharing CsO6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cs–O bond lengths are 2.22 Å. O is bonded in a linear geometry to two equivalent Cs atoms.

36 MATERIALS SCIENCE↗