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Separation of thorium (IV) from lanthanide concentrate (LC) and water leach purification (WLP) residue

Thorium (IV) content in industrial residue produced from rare earth elements production industry is one of the challenges to Malaysian environment. Separation of thorium from the lanthanide concentrate (LC) and Water Leach Purification (WLP) residue from rare earth elements production plant is described. Both materials have been tested by sulphuric acid and alkaline digestions. Th concentrations in LC and WLP were determined to be 1289.7 ± 129 and 1952.9±17.6 ppm respectively. The results of separation show that the recovery of Th separation from rare earth in LC after concentrated sulphuric acid dissolution and reduction of acidity to precipitate Th was found 1.76-1.20% whereas Th recovery from WLP was less than 4% after concentrated acids and alkali digestion processes. Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) was used to determine Th concentrations in aqueous phase during separation stages. This study indicated that thorium maybe exists in refractory and insoluble form which is difficult to separate by these processes and stays in WLP residue as naturally occurring radioactive material (NORM)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Conceptual design study of small long-life PWR based on thorium cycle fuel

A neutronic performance of small long-life Pressurized Water Reactor (PWR) using thorium cycle based fuel has been investigated. Thorium cycle which has higher conversion ratio in thermal region compared to uranium cycle produce some significant of {sup 233}U during burn up time. The cell-burn up calculations were performed by PIJ SRAC code using nuclear data library based on JENDL 3.3, while the multi-energy-group diffusion calculations were optimized in whole core cylindrical two-dimension R-Z geometry by SRAC-CITATION. this study would be introduced thorium nitride fuel system which ZIRLO is the cladding material. The optimization of 350 MWt small long life PWR result small excess reactivity and reduced power peaking during its operation.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Prediction of new high pressure structural sequence in thorium carbide: A first principles study

In the present work, we report the detailed electronic band structure calculations on thorium monocarbide. The comparison of enthalpies, derived for various phases using evolutionary structure search method in conjunction with first principles total energy calculations at several hydrostatic compressions, yielded a high pressure structural sequence of NaCl type (B1) → Pnma → Cmcm → CsCl type (B2) at hydrostatic pressures of ∼19 GPa, 36 GPa, and 200 GPa, respectively. However, the two high pressure experimental studies by Gerward et al. [J. Appl. Crystallogr. 19, 308 (1986); J. Less-Common Met. 161, L11 (1990)] one up to 36 GPa and other up to 50 GPa, on substoichiometric thorium carbide samples with carbon deficiency of ∼20%, do not report any structural transition. The discrepancy between theory and experiment could be due to the non-stoichiometry of thorium carbide samples used in the experiment. Further, in order to substantiate the results of our static lattice calculations, we have determined the phonon dispersion relations for these structures from lattice dynamic calculations. The theoretically calculated phonon spectrum reveal that the B1 phase fails dynamically at ∼33.8 GPa whereas the Pnma phase appears as dynamically stable structure around the B1 to Pnma transition pressure. Similarly, the Cmcm structure also displays dynamic stability in the regime of its structural stability. The B2 phase becomes dynamically stable much below the Cmcm to B2 transition pressure. Additionally, we have derived various thermophysical properties such as zero pressure equilibrium volume, bulk modulus, its pressure derivative, Debye temperature, thermal expansion coefficient and Gruneisen parameter at 300 K and compared these with available experimental data. Further, the behavior of zero pressure bulk modulus, heat capacity and Helmholtz free energy has been examined as a function temperature and compared with the experimental data of Danan [J. Nucl. Mater. 57, 280 (1975)].

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The influence of lattice defects, recombination, and clustering on thermal transport in single crystal thorium dioxide

Thermal transport is a key controlling property for thorium dioxide in many applications where defect-generating radiation fields are present. An understanding of the effect of nanoscale lattice defects on thermal transport in this material is currently unavailable due to a lack of high-quality, single crystal material from which unit processes may be investigated. In this work, a series of thorium dioxide single crystals are exposed to 2 MeV proton irradiation at room temperature and 600°C to create microscale regions with varying densities and types of point and extended defects. Defected regions are investigated using spatial domain thermoreflectance to quantify the change in thermal conductivity as a function of ion fluence as well as transmission electron microscopy and Raman spectroscopy to interrogate the structure of the generated defects. Together, this com- bination of methods provides important initial insight into defect formation, recombination, and clustering in thorium dioxide and the effect of those defects on thermal transport. These methods also provide a promising pathway for the quantification of the smallest-scale defects which cannot be captured using traditional microscopy techniques and play and outsized role in degrading thermal performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Temperature-dependent elastic constants of thorium dioxide probed using time-domain Brillouin scattering

Herein we report the adiabatic elastic constants of single-crystal thorium dioxide over a temperature range of 77–350 K. Time-domain Brillouin scattering, an all-optical, non-contact picosecond ultrasonic technique, is used to generate and detect coherent acoustic phonons that propagate in the bulk perpendicular to the surface of the crystal. These coherent acoustic lattice vibrations have been monitored in two hydrothermally grown single-crystal thorium dioxide samples along the (100) and (311) crystallographic directions. The three independent elastic constants of the cubic crystal (C 11 , C 12 , and C 44 ) are determined from the measured bulk acoustic velocities. The longitudinal wave along the (100) orientation provided a direct measurement of C 11 . Measurement of C 44 and C 12 was achieved by enhancing the intensity of quasi-shear mode in a (311) oriented crystal by adjusting the polarization angle relative to the crystal axes. We find the magnitude of softening of the three elastic constants to be ~2.5% over the measured temperature range. Good agreement is found between the measured elastic constants with previously reported values at room temperature, and between the measured temperature-dependent bulk modulus with calculated values. We find that semi-empirical models capturing lattice anharmonicity adequately reproduce the observed trend. We also determine the acoustic Grüneisen anharmonicity parameter from the experimentally derived temperature-dependent bulk modulus and previously reported temperature-dependent values of volumetric thermal expansion coefficient and heat capacity. This work presents measurements of the temperature-dependent elasticity in single-crystal thorium dioxide at cryogenic temperature and provides a basis for testing ab initio theoretical models and evaluating the impact of anharmonicity on thermophysical properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

ORNL experience and perspectives related to processing of thorium and 233 U for nuclear fuel

Thorium-based nuclear fuel cycles have received renewed attention in both research and public circles since about the year 2000. Much of the attention has been focused on nuclear fission energy production that utilizes thorium as a fertile element for producing fissionable 233 U for recycle in thermal reactors, fast reactors, or externally driven systems. Here, lesser attention has been paid to other fuel cycle operations that are necessary for implementation of a sustainable thorium-based fuel cycle such as reprocessing and fabrication of recycle fuels containing 233 U.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Feasibility study on AFR-100 fuel conversion from uranium-based fuel to thorium-based fuel

Although thorium has long been considered as an alternative to uranium-based fuels, most of the reactors built to-date have been fueled with uranium-based fuel with the exception of a few reactors. The decision to use uranium-based fuels was initially made based on the technology maturity compared to thorium-based fuels. As a result of this experience, lot of knowledge and data have been accumulated for uranium-based fuels that made it the predominant nuclear fuel type for extant nuclear power. However, following the recent concerns about the extent and availability of uranium resources, thorium-based fuels have regained significant interest worldwide.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Self-Sustaining Thorium Boiling Water Reactors

The primary objectives of this project are to: Perform a pre-conceptual design of a core for an alternative to the Hitachi proposed fuel-self- sustaining RBWR-AC, to be referred to as a RBWR-Th. The use of thorium fuel is expected to assure negative void coefficient of reactivity (versus positive of the RBWR-AC) and improve reactor safety; Perform a pre-conceptual design of an alternative core to the Hitachi proposed LWR TRU transmuting RBWR-TB2, to be referred to as the RBWR-TR. In addition to improved safety, use of thorium for the fertile fuel is expected to improve the TRU transmutation effectiveness; Compare the RBWR-Th and RBWR-TR performance against that of the Hitachi RBWR core designs and sodium cooled fast reactor counterparts - the ARR and ABR; and, Perform a viability assessment of the thorium-based RBWR design concepts to be identified along with their associated fuel cycle, a technology gap analysis, and a technology development roadmap. A description of the work performed and of the results obtained is provided in this Overview Report and, in more detail, in the Attachments. The major findings of the study are summarized.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Defining Processing Times for Accelerator Produced 225Ac and Other Isotopes from Proton Irradiated Thorium

During the purification of radioisotopes, decay periods or time dependent purification steps may be required to achieve a certain level of radiopurity in the final product. Actinum-225 (Ac-225), Silver-111 (Ag-111), Astatine-211 (At-211), Ruthenium-105 (Ru-105), and Rhodium-105 (Rh-105) are produced in a high energy proton irradiated thorium target. Experimentally measured cross sections, along with MCNP6-generated cross sections, were used to determine the quantities of Ac-225, Ag-111, At-211, Ru-105, Rh-105, and other co-produced radioactive impurities produced in a proton irradiated thorium target at Brookhaven Linac Isotope Producer (BLIP). Ac-225 and Ag-111 can be produced with high radiopurity by the proton irradiation of a thorium target at BLIP.

07 ISOTOPE AND RADIATION SOURCES↗

Optimization of Cation Exchange for the Separation of Actinium-225 from Radioactive Thorium, Radium-223 and Other Metals

Actinium-225 (225Ac) can be produced with a linear accelerator by proton irradiation of a thorium (Th) target, but the Th also underdoes fission and produces 400 other radioisotopes. No research exists on optimization of the cation step for the purification. The research herein examines the optimization of the cation exchange step for the purification of 225Ac. The following variables were tested: pH of load solution (1.5–4.6); rinse steps with various concentrations of HCl, HNO3, H2SO4, and combinations of HCl and HNO3; various thorium chelators to block retention; MP50 and AG50 resins; and retention of 20–45 elements with different rinse sequences. The research indicated that HCl removes more isotopes earlier than HNO3, but that some elements, such as barium and radium, could be eluted with ≥2.5 M HNO3. The optimal pH of the load solution was 1.5–2.0, and the optimized rinse sequence was five bed volumes (BV) of 1 M citric acid pH 2.0, 3 BV of water, 3 BV of 2 M HNO3, 6 BV of 2.5 M HNO3 and 20 BV of 6 M HNO3. The sequence recovered >90% of 225Ac with minimal 223Ra and thorium present.

223Ra↗

Thorium Fuel Options for Sustained Transuranic Burning in Pressurized Water Reactors - 12381

As described in companion papers, Westinghouse is proposing the adoption of a thorium-based fuel cycle to burn the transuranics (TRU) contained in the current Used Nuclear Fuel (UNF) and transition towards a less radio-toxic high level waste. A combination of both light water reactors (LWR) and fast reactors (FR) is envisaged for the task, with the emphasis initially posed on their TRU burning capability and eventually to their self-sufficiency. Given the many technical challenges and development times related to the deployment of TRU burners fast reactors, an interim solution making best use of the current resources to initiate burning the legacy TRU inventory while developing and testing some technologies of later use is desirable. In this perspective, a portion of the LWR fleet can be used to start burning the legacy TRUs using Th-based fuels compatible with the current plants and operational features. This analysis focuses on a typical 4-loop PWR, with 17x17 fuel assembly design and TRUs (or Pu) admixed with Th (similar to U-MOX fuel, but with Th instead of U). Global calculations of the core were represented with unit assembly simulations using the Linear Reactivity Model (LRM). Several assembly configurations have been developed to offer two options that can be attractive during the TRU transmutation campaign: maximization of the TRU transmutation rate and capability for TRU multi-recycling, to extend the option of TRU recycling in LWR until the FR is available. Homogeneous as well as heterogeneous assembly configurations have been developed with various recycling schemes (Pu recycle, TRU recycle, TRU and in-bred U recycle etc.). Oxide as well as nitride fuels have been examined. This enabled an assessment of the potential for burning and multi-recycling TRU in a Th-based fuel PWR to compare against other more typical alternatives (U-MOX and variations thereof). Results will be shown indicating that Th-based PWR fuel is a promising option to multi-recycle and burn TRU in a thermal spectrum, while satisfying top-level operational and safety constraints. Various assembly designs have been proposed to assess the TRU burning potential of Th-based fuel in PWRs. In addition to typical homogeneous loading patterns, heterogeneous configurations exploiting the breeding potential of thorium to enable multiple cycles of TRU irradiation and burning have been devised. The homogeneous assembly design, with all pins featuring TRU in Th, has the benefit of a simple loading pattern and the highest rate of TRU transmutation, but it can be used only for a few cycles due to the rapid rise in the TRU content of the recycled fuel, which challenges reactivity control, safety coefficients and fuel handling. Due to its simple loading pattern, such assembly design can be used as the first step of Th implementation, achieving up to 3 times larger TRU transmutation rate than conventional U-MOX, assuming same fraction of MOX assemblies in the core. As the next step in thorium implementation, heterogeneous assemblies featuring a mixed array of Th-U and Th-U-TRU pins, where the U is in-bred from Th, have been proposed. These designs have the potential to enable burning an external supply of TRU through multiple cycles of irradiation, recovery (via reprocessing) and recycling of the residual actinides at the end of each irradiation cycle. This is achieved thanks to a larger breeding of U from Th in the heterogeneous assemblies, which reduces the TRU supply and thus mitigates the increase in the TRU core inventory for the multi-recycled fuel. While on an individual cycle basis the amount of TRU burned in the heterogeneous assembly is reduced with respect to the homogeneous design, TRU burning rates higher than single-pass U-MOX fuel can still be achieved, with the additional benefits of a multi-cycle transmutation campaign recycling all TRU isotopes. Nitride fuel, due its higher density and U breeding potential, together with its better thermal properties, ideally suits the objectives and constraints of the heterogeneous assemblies. However, significant technological advancements must be made before nitride fuels can be employed in an LWR: its water resistance needs to be improved and a viable technology to enrich N in N-15 must be devised. Moreover, for the nitride heterogeneous configurations examined in this study, the enhancement in TRU burning performance is achieved not only by replacing oxide with nitride fuel, but also by increasing the fuel rod size. This latter modification, allowed by the high thermal conductivity of nitride fuel, leads however to a very tight lattice, which may challenge reactor coolant pumps and assembly hold-down mechanisms, the former through an increase in core pressure drop and the latter through an increase in assembly lift-off forces. To alleviate these issues, while still achieving the large fuel-to-moderator ratios resulting from using tight lattices, wire wraps could be used in place of grid spacers. For tight lattices, typical grid spacers are hard to manufacture and their replacement with wire wraps is known to allow for a pressure drop reduction by at least 2 times. The studies, while certainly very preliminary, provide a starting point to devise an optimum strategy for TRU transmutation in Th-based PWR fuel. The viability of the scheme proposed depends on the timely phasing in of the associated technologies, with proper lead time and to solve the many challenges. These challenges are certainly substantial, and make the current once-through U-based scheme pursued in the US by far a more practical (and cheaper) option. However, when compared to other transmutation schemes, the proposed one has arguably similar challenges and unknowns with potentially bigger rewards. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Laboratory Enrichment of Radioactive Assemblages and Estimation of Thorium and Uranium Radioactivity in Fractions Separated from Placer Sands in Southeast Bangladesh

The present study reports the likely first attempt of separating radioactive minerals for estimation of activity concentration in the beach placer sands of Bangladesh. Several sand samples from heavy mineral deposits located at the south-eastern coastal belt of Bangladesh were processed to physically upgrade their radioactivity concentrations using plant and laboratory equipment. Following some modified flow procedure, individual fractions were separated and investigated using gamma-ray spectrometry and powder-XRD analysis. The radioactivity measurements indicated contributions of the thorium and uranium radioactive series and of {sup 40}K. The maximum values of {sup 232}Th and {sup 238}U, estimated from the radioactivity of {sup 208}Tl and {sup 234}Th in secular equilibrium, were found to be 152,000 and 63,300 Bq/kg, respectively. The fraction of the moderately conductive part in electric separation contained thorium predominantly, while that of the non-conductive part was found to be uranium rich. The present arrangement of the pilot plant cascade and the fine tuning of setting parameters were found to be effective and economic separation process of the radioactive minerals from placer sands in Bangladesh. Probable radiological impacts and extraction potentiality of such radioactive materials are also discussed.

54 ENVIRONMENTAL SCIENCES↗

DE-NE0000735 - FINAL REPORT ON THORIUM FUEL CYCLE NEUP PROJECT

The report is broken into six chapters, including this executive summary chapter. Following an introduction, this report discusses each of the project’s three major components (Fuel Cycle Data Package (FCDP) Development, Thorium Fuel Cycle Literature Analysis and Database Development, and the Thorium Fuel Cycle Technical Track and Proceedings). A final chapter is devoted to summarization. Various outcomes, publications, etc. originating from this project can be found in the Appendices at the end of the document.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Functionalization of Carbon Monoxide and tert ‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Abstract We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert ‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C 5 Me 5 ) 2 Th[PH(Mes)] 2 , Mes=2,4,6‐Me 3 C 6 H 2 , with 1 atm of CO yields (C 5 Me 5 ) 2 Th( κ 2 ‐(O,O)‐OCH 2 PMes‐C(O)PMes), in which one CO molecule is inserted into each thorium–phosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus, are now bound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert ‐butyl nitrile, t BuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C 5 Me 5 ) 2 Th[PH(Mes)][ κ 2 ‐(P,N)‐N(H)C(CMe 3 )P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe 3 ) 2 removes the proton bound to nitrogen, not phosphorus.

Vilanova, Sean P.↗

A Tetrapositive Metal Ion in the Gas Phase: Thorium(IV) Coordinated by Neutral Tridentate Ligands

ESI of 1:1 mixtures of Th(ClO₄)₄ and ligand TMOGA in acetonitrile resulted in the observation of the TMOGA supported tetracation, Th(L)₃⁴⁺, in the gas phase. Three TMOGA ligands are necessary to stabilize the tetrapositive thorium ion; no Th(L)₂⁴⁺ or Th(L)₄⁴⁺ was observed. Theoretical calculations reveal that the Th(L)₃⁴⁺ complex possesses C₃ symmetry with the thorium center coordinated by nine oxygen atoms from three ligands, which forms a twisted TPP geometry. Actinide compounds with such a geometry feature a nine-coordinate chiral actinide center. The Th-L binding energy and bond orders of Th(L)n⁴⁺ decrease as the coordination number increases, consistent with the trend of concurrently increasing Th-O distances. The Th-O bonding is mainly electrostatic in nature, but the covalent interactions are not negligible. CID of the Th(L)₃⁴⁺ complex mainly resulted in charge reduction to form Th(L)₂(L-86)³⁺oss of neutral TMOGA was not observed. The protic ligand methanol stabilized only tri- and dications of ligated thorium. The intensity of the Th(L)₃⁴⁺ peak was reduced as the percentage of water increased in the Th(ClO₄)₄/TMOGA solution.

Actinides, Density Functional Theory, Gas-Phase Ch↗

Separation of thorium from uranium ore

Thorium-230 has many research applications, but there is not a commercial source of this isotope. However, since 230 Th is part of the 238 U decay chain, it can be separated from naturally occurring uranium. In this work, a novel procedure was developed to separate thorium from uranium ore, consisting of leaching, liquid–liquid extraction, precipitations and ion exchange chromatography. Here, the final product was 91.32 ± 0.77 mg of thorium with a purity of 99.5 ± 1.2 wt%. Of that, 7.65 ± 0.10 mg was 230 Th and the remainder 232 Th. The total yield of 230 Th was 71.1 ± 5.4%. Ways to improve the yield by further processing the back-extraction solution are suggested.

230Th↗

Measurements of thorium and uranium daughters in radioenvironmental samples using γ γ -coincidence spectrometry

We present the performance of a γ γ -coincidence spectrometer for measuring the activities of thorium and uranium daughters in environmental samples. The spectrometer consists of two NaI(Tl) detectors facing each other inside a low-background passive shield. We present coincidence gating schemes for achieving the best signal-to-noise ratios, coincidence detection efficiencies, background levels, and minimum detectable activities. The spectrometer is simulated using Geant4 to correct sample efficiencies for self-absorption effects. The device is used to measure thorium and uranium daughter activities in Brazil nuts, potting mix, and magazine paper. Our results for Brazil nuts agree with some, but not all, previous measurements. Thorium or uranium daughter activities have previously not been reported for commercial potting mix. For magazine paper, our measured activities are lower than most previously determined values.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Sorption of tetravalent thorium on muscovite

Adsorption of tetravalent thorium to the (0 0 1) basal surface of the phyllosilicate muscovite from an aqueous solution (1 × 10 -4 mol/L Th(IV) in 1 × 10 -1 mol/L NaCl, pH = 3.2) was studied by crystal truncation rod (CTR) and resonant anomalous X-ray reflectivity (RAXR) measurements. Th uptake to the muscovite surface from solutions with total Th concentrations [Th]tot = 1 × 10-6–4.88 × 10 -3 mol/L and 1 × 10 -1 mol/L NaCl, pH = 3.2 was quantified by alpha-spectrometry. The uptake measurements showed that Th adsorption to the muscovite surface follows a Langmuir isotherm with an apparent adsorption constant Kapp = 2 × 104 L/mol up to [Th] tot = 1.02 × 10 -3 mol/L. The CTR and RAXR results identified one dominant Th species with a very broad distribution centered ~10 Å above the surface, in agreement with strongly hydrated extended outer sphere sorption. The findings indicate that the large energy of hydration (ΔGhyd = -5815 kJ/mol (Marcus, 1991)) for the small and highly-charged Th4+ cation is a controlling parameter in its surface speciation. The surface occupancy (0.4 Th per unit cell area, AUC) measured by RAXR exceeds the expected level for surface charge compensation by tetravalent Th (0.25 Th/A UC ). Yet, the radiometric uptake measurements show smaller occupancies (0.21 Th/AUC) after rinsing by deionized water, indicating a partial removability of sorbed thorium. Thorium oligomerization was observed at total Th concentrations [Th] tot ≥ 2.0 × 10-3 mol/L in presence of the surface, even though solubility studies imply that Th is soluble under these solution conditions.

58 GEOSCIENCES↗