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Review of thermophysical property methods applied to fueled and un-fueled molten salts

Recent investigation into designs of molten salt reactors (MSR) requires accurate data of candidate salts. Review of the literature shows lacking thermophysical (TP) property data for coolants and fuel-bearing salts of Advanced High Temperature Reactors (AHTR). Measurement uncertainties of current data are even more deficient, and this affects ongoing research where MSR modeling and testing are being performed. Melting temperature, viscosity, density, specific heat capacity, and thermal and electrical conductivity measurements are often not arranged together or discussed in great detail, especially for fuel-bearing salts. Raw data from key findings spanning over 70 years for LiF, LiF-BeF 2 , LiF-NaF-KF, KCl-MgCl 2 , KF-ZrF 4 , and NaF-KF-MgF 2 have been organized and presented here. Brief description of methods used to obtain these results, in addition to the TP data of some of these salts as fuel carriers, has also been discussed. Thermal conductivity data are particularly weak due to older, high-error measurement techniques. More recent measurement systems to evaluate salt thermal conductivity show promise for obtaining consistent absolute values. This work concludes that measurement systems such as transient hot-wire method, forced Rayleigh scattering, and laser flash analysis provide the most promise to fill these data gaps and reduce current uncertainty in thermal conductivity measurements of both fueled and un-fueled molten salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mineralogic Investigation into Occurrence of High Uranium Well Waters in Upstate South Carolina USA

High levels of U (up to 5570 {micro}g/L) have been discovered in well waters near Simpsonville, South Carolina, USA. In order to characterize the mineralogical source of the U and possible structural controls on its presence, a deep (214 m) well was cored adjacent to one of the enriched wells. The highest gamma-ray emissions in the recovered core occur in coarse biotite granite at a depth just below 52 m. A slickenlined fault plane at 48.6 m and narrow pegmatite layers at depths of 113, 203 and 207 m also yield high gamma-ray counts. Thin sections were made from the above materials and along several subvertical healed fractures. Uraninite and coffinite are the principal U-rich minerals in the core. Other U-bearing minerals include thorite and thorogummite, monazite, zircon and allanite. Primary uraninite occurs in the biotite granite and in pegmatite layers. Secondary coffinite is present as tiny (<5 {micro}m) crystals dispersed along fractures in the granite and pegmatites. Coffinite also occurs along the slickenlined fault plane, where it is associated with calcite and calcic zeolite and also replaces allanite. Coffinite lacks radiogenic Pb, hence is considerably younger than the uraninite. Dissolution of partially oxidized Ca-rich uraninite occurring in the surficial biotite granite (or secondary coffinite in fracture zones) is likely the main source for the current high levels of U in nearby area wells. The high-U well waters have a carbonate signature, consistent with pervasive calcite vein mineralization in the core. Aqueous speciation calculations suggest U transport as an uranyl (U{sup 6+}) hydroxyl-carbonate complex. Later reduction resulted in secondary precipitation along fractures as a U{sup 4+} mineral (i.e., coffinite).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical and environmental stability of monazite-cheralite solid solutions Ln 1-2 x Ca x Th x PO 4 (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study

Monazite-cheralite ceramics are a promising waste form for actinides. To elucidate the long-term behavior of this matrix in aqueous solutions, this study measured thermodynamic data for Th-rhabdophanes Ln 1-2 x Ca x Th x PO 4 ·nH 2 O (with Ln = Pr, Nd; x = 0–0.15) and the associated anhydrous monazite-cheralites Ln 1-2 x Ca x Th x PO 4 . Further, solubility experiments at 298K and high temperature oxide melt solution calorimetry were combined for calculation of ΔG$^°_f$, ΔH$^°_f$ and S$^°_m$ of Th-rhabdophanes and associated monazite-cheralites. Standard solubility constants were employed in a geochemical simulation using the PHREEQC software, the results of which confirmed the high chemical stability of the monazite-cheralite phases and supported their use as a specific conditioning matrix for the long-term immobilization of actinides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transport model predictions of 225 Ac production cross sections via energetic p, d and α irradiation of 232 Th targets

Monte Carlo transport codes PHITS and MCNP6 were used to calculate the production cross sections of 225,227 Ac, 227,229 Th, 223,225 Ra, and 229,230,231 Pa via the bombardment of a 232 Th target with energetic protons, deuterons, and α-particles. The incident projectile energies ranged between 10 and 800 MeV/nucleon. When possible, the predicted production cross sections were compared with the available experimental data and other predictions. Here, the degree of the codes’ abilities to match the measured data provides a qualitative assessment of the codes’ abilities to predict data from similar, but unmeasured, projectile/target systems. In addition, a comparison between calculated cross sections and data may provide insight into possible improvements in the physics models employed by those transport codes.

223Ra↗

Atomistically-informed modeling of point defect clustering and evolution in irradiated ThO 2

A cluster dynamics (CD) model has been developed to investigate the nucleation and growth of point defect clusters, i.e., interstitial prismatic loops and nanoscale and sub-nanoscale voids, in ThO 2 during irradiation by energetic particles. The model considers cluster off-stoichiometry due to the asymmetry of point defect generation on the O and Th sublattices under irradiation, as well as the point defect diffusivities and the defect binding energies to clusters. The energies were established using detailed molecular dynamics simulations considering the statistical variability of cluster configuration. A high-order adaptive time-integration has been used to solve the model. The predicted loop density and their average size is in good agreement with reported experimental observations for proton irradiated ThO 2 at 600°C. In conclusion, the model did not predict void evolution due to the sluggish kinetics of cation vacancies, explaining the absence of voids in proton irradiated ThO 2 (and other oxides) at relatively low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extended defects-enhanced oxygen diffusion in ThO 2

Oxygen self-diffusion is key to understanding stoichiometry and defect structures in oxide nuclear fuels. Experimentally, low activation-barrier oxygen migration was found in ThO 2 , a candidate nuclear fuel, possibly due to short-circuit diffusion mechanisms. Here, we perform extensive molecular dynamics simulations to show that various types of extended defects can enhance oxygen self-diffusion with a much-reduced activation barrier in ThO 2 . In this work, we consider extended defects including 1D (dislocation), 2D (grain boundary), and 3D (void) defects. Due to the distinct characteristics of each type of extended defect, the modulation of oxygen diffusion varies. Further, these results provide a quantitative description of oxygen transport, which is significantly enhanced within a close distance (nanometer scale) from the extended defects. Among all these considered defects, grain boundary, particularly the low-energy $Σ$3 twin boundary, exhibits the strongest effect on increasing oxygen transport.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modifications in Dynamic Contrast-Enhanced Magnetic Resonance Imaging Parameters After α-Particle-Emitting {sup 227}Th-trastuzumab Therapy of HER2-Expressing Ovarian Cancer Xenografts

Purpose: The purpose of this study was to investigate the effect of α-particle-emitting {sup 227}Th-trastuzumab radioimmunotherapy on tumor vasculature to increase the knowledge about the mechanisms of action of {sup 227}Th-trastuzumab. Methods and Materials: Human HER2-expressing SKOV-3 ovarian cancer xenografts were grown bilaterally in athymic nude mice. Mice with tumor volumes 253 ± 36 mm{sup 3} (mean ± SEM) were treated with a single injection of either {sup 227}Th-trastuzumab at a dose of 1000 kBq/kg body weight (treated group, n=14 tumors) or 0.9% NaCl (control group, n=10 tumors). Dynamic T1-weighted contrast-enhanced magnetic resonance imaging (DCEMRI) was used to study the effect of {sup 227}Th-trastuzumab on tumor vasculature. DCEMRI was performed before treatment and 1, 2, and 3 weeks after therapy. Tumor contrast-enhancement curves were extracted voxel by voxel and fitted to the Brix pharmacokinetic model. Pharmacokinetic parameters for the tumors that underwent radioimmunotherapy were compared with the corresponding parameters of control tumors. Results: Significant increases of k{sub ep}, the rate constant of diffusion from the extravascular extracellular space to the plasma (P<.05), and k{sub el,} the rate of clearance of contrast agent from the plasma (P<.01), were seen in the radioimmunotherapy group 2 and 3 weeks after injection, compared with the control group. The product of k{sub ep} and the amplitude parameter A, associated with increased vessel permeability and perfusion, was also significantly increased in the radioimmunotherapy group 2 and 3 weeks after injection (P<.01). Conclusions: Pharmacokinetic modeling of MRI contrast-enhancement curves evidenced significant alterations in parameters associated with increased tumor vessel permeability and tumor perfusion after {sup 227}Th-trastuzumab treatment of HER2-expressing ovarian cancer xenografts.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Evolution of dislocation loops and voids in post-irradiation annealed ThO 2 : A combined in-situ TEM and cluster dynamics investigation

The effect of isochronal annealing on the evolution of dislocation loop and void population in proton irradiated ThO 2 has been investigated. Post-irradiation annealing in other actinide oxides like UO 2 shows significant loop coarsening. ThO 2 samples were irradiated with 2 MeV protons up to a dose of 0.1 dpa at 600°C. Post-irradiation isochronal annealing was performed at 600, 800, 1000 and 1100°C for 1 h at each temperature using in-situ TEM. Only faulted 1/3<111> type dislocation loops were observed, and their sizes and distribution were characterized. Further, the population of self-interstitial atom (SIA) dislocation loops did not show any significant growth and coarsening. Additionally, nanometric voids were observed at annealing temperatures of 1000 and 1100°C. Using cluster dynamics (CD), we have studied the nucleation and growth of point defects and defect clusters, i.e., SIA prismatic dislocation loops and nanometric and sub-nanometric voids in proton irradiated ThO 2 . The CD model was further utilized to predict the growth and coarsening of loops and voids during isochronal annealing at the experimental and higher temperatures. The model did not predict significant SIA loop growth which closely corresponds to the TEM observations. CD predicted SIA loop coarsening is insignificant even at high annealing temperature of 1500°C because the model only considers the growth of defect clusters by absorption of like point defects, i.e., SIA loops absorb interstitials and voids absorb vacancies, and cannot account for their migration and coalescence due to elastic interaction. The CD model also predicts the evolution of nanometric voids having mean size within the error bounds of TEM observations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Experimental confirmation of first-principles thermal conductivity in Zirconium-doped ThO 2

The degradation of thermal conductivity in advanced nuclear fuels due to the accumulation of fission products and irradiation-induced defects is inevitable, and must be considered as part of safety and efficiency analyses of nuclear reactors. Here, this study examines the thermal conductivity of a zirconium-doped ThO 2 crystal, synthesized via the hydrothermal method using a spatial domain thermoreflectance technique. Zirconium is one of the soluble fission products in oxide fuels that can effectively scatter heat-carrying phonons in the crystalline lattice of fuel. Thus, thermal property measurements of zirconium-doped ThO 2 single crystals provide insights into the effects of substitutional zirconium doping, isolated from extrinsic factors such as grain boundary scattering. The experimental results are compared with first-principles calculations of the lattice thermal conductivity of ThO 2 , employing an iterative solution of the Peierls-Boltzmann transport equation. Additionally, the non-perturbative Green's function methodology is utilized to compute phonon-point defect scattering rates, accounting for local distortions around point defects, including mass difference changes, interatomic force constants, and structural relaxation. The congruence between the predicted results from first-principles calculations and the measured temperature-dependent thermal conductivity validates the computational methodology. Furthermore, the methodologies employed in this study enable systematic investigations of thermal conductivity reduction by fission products, potentially leading to the development of more accurate fuel performance codes.

36 - MATERIALS SCIENCE↗

Production of anhydrous ƒ-element fluorides through the ionothermal treatment of ƒ-element oxalates

The pivotal role of uranium and plutonium fluorides in the nuclear fuel cycle, particularly in the pyrochemical reduction process, is well recognized. Traditionally, the fluorination of uranium and plutonium materials relies on the use of highly toxic and corrosive gases (e.g., HF (g) , F 2(g) ). Herein, we present an alternative approach using the ionic liquid 1‑butyl‑3-methylimidazolium hexafluorophosphate ([Bmim][PF 6 ] (l) ) and/or hexafluorophosphoric acid (HPF 6(aq) ) as fluorinating agents for the ƒ-element oxalates M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) (M III = Ce, Pu) and M IV (C 2 O 4 ) 2 ∙ 6H 2 O (s) (M IV = Th, U). Our findings demonstrate that [Bmim][PF 6 ] (l) and HPF 6(aq) enable the ionothermal fluorination of ƒ-element oxalates, resulting in the formation of anhydrous CeF 3(s) , ThF 4(s) , and UF 4(s) within 2 hours at 200 °C. This method also facilitates the partial fluorination of plutonium(III) oxalate, yielding a mixture of anhydrous PuF 3(s) and an unidentified phase. Overall, the ionothermal treatment approach offers a safer and more efficient means of producing anhydrous ƒ-element fluorides than conventional methods involving hazardous gases. In addition, we describe the morphology of UF 4(s) materials as a function of production route and demonstrate the presence of morphological signatures that could be used during a nuclear forensic investigation.

Cerium↗

Phase stability of some actinides with brannerite structure at high pressures

Structure behavior of actinide brannerites ThTi{sub 2}O{sub 6}, Y{sub 0.5}U{sub 0.5}Ti{sub 1.5}Nb{sub 0.5}O{sub 6} and their analog oxide CeTi{sub 2}O{sub 6} was studied at high pressure by using in situ x-ray diffraction, Raman scattering and infra-red absorption techniques, respectively. Brannerite structure was found to be not stable and started to become amorphous at pressures above 20 GPa. Some minor crystalline phase(s) due to phase decomposition was observed in all the three samples during pressurization. In addition, the observed bulk modulus indicated that the actinide-bearing brannerites are more compressible than their analog compound CeTi{sub 2}O{sub 6}, which may be related to the asymmetric 5f electron orbits of actinide elements. - Graphical abstract: Actinide-bearing compounds with brannerite structure and their analog CeTi{sub 2}O{sub 6} are not stable at high pressure. They were amorphized after {approx}20 GPa and a minor pressure-induced phase transition or decomposition process was always observed before amorphization. Highlights: > Phase stability of three brannerites CeTi{sub 2}O{sub 6}, ThTi{sub 2}O{sub 6}, and (U,Y)(Ti,Nb){sub 2}O{sub 6} at high pressures. > Brannerite structure was not stable and became amorphous after {approx}20 GPa. > Actinide-bearing brannerites are easier compressed than their analog compound CeTi{sub 2}O{sub 6}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid state reactions of nanocrystalline Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} mixed oxide with high surface area silica in oxidizing and reducing atmosphere

The interaction of nanocrystalline Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} mixed oxide with a high surface amorphous silica support in an oxidizing and reducing atmosphere was studied by XRD, HRTEM, SAED, SEM and BET techniques. The Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} system shows very high structural and size stability in the oxidizing atmosphere up to 1000 Degree-Sign C, but in hydrogen spreading of the oxide onto silica occurs at temperatures above 800 Degree-Sign C. In the oxidizing atmosphere stability of the mixed oxide is limited by extraction of ytterbium from the oxide driven by a tendency to form ytterbium silicates. A new polymorph of Yb silicate, isomorphic with y-Y{sub 2}Si{sub 2}O{sub 7} (yttrialite), has been identified in the samples containing the mixed Ce-Yb oxide. The absence of y-Yb{sub 2}Si{sub 2}O{sub 7} silicate in the Yb{sub 2}O{sub 3}-SiO{sub 2} samples treated in similar conditions indicates that Ce{sup 4+} ions are needed to stabilize the structure. - Graphical abstract: Structure evolution of nano-Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} in air and in H{sub 2}. Highlights: Black-Right-Pointing-Pointer Nano-Ce{sub 0.50}Yb{sub 0.50}O{sub 1.75} on SiO{sub 2} is stable in air up to 1000 Degree-Sign C but spreads in hydrogen at 800 Degree-Sign C. Black-Right-Pointing-Pointer Formation of Yb silicates determines the stability of Ce{sub 0.50}Yb{sub 0.50}O{sub 1.75} at high temperatures. Black-Right-Pointing-Pointer New, y-Yb{sub 2}Si{sub 2}O{sub 7} silicate (yttrialite type) forms in Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} in H{sub 2} at 1100 Degree-Sign C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomistic calculations of the thermodynamic properties of mixing for tetravalent metal dioxide solid solutions: (Zr, Th, Ce)O{sub 2}

The thermodynamic mixing properties for isometric Th{sub x}Ce{sub 1-x}O{sub 2}, Ce{sub x}Zr{sub 1-x}O{sub 2}, and Th{sub x}Zr{sub 1-x}O{sub 2} were determined using quantum-mechanical calculations and subsequent Monte-Carlo simulations. Although the Th{sub x}Ce{sub 1-x}O{sub 2} binary indicates exsolution below 600 K, the energy gain due to exsolution is small (E{sub exsoln}=1.5 kJ/(mol cations) at 200 K). The energy gain for exsolution is significant for the binaries containing Zr; at 1000 K, E{sub exsoln}=6 kJ/(mol cations) for the Ce{sub x}Zr{sub 1-x}O{sub 2} binary, and E{sub exsoln}=17 kJ/(mol cations) for the Th{sub x}Zr{sub 1-x}O{sub 2} binary. The binaries containing Zr have limited miscibility and cation ordering (at 200 K for x=0.5). At 1673 K, only 4.0 and 0.25 mol% ZrO{sub 2} can be incorporated into CeO{sub 2} and ThO{sub 2}, respectively. Solid-solution calculations for the tetragonal Th{sub x}Zr{sub 1-x}O{sub 2} binary show decreased mixing enthalpy due to the increased end-member stability of tetragonal ZrO{sub 2}. Inclusion of the monoclinic ZrO{sub 2} is predicted to further reduce the mixing enthalpy for binaries containing Zr. - Graphical abstract: Temperature-composition phase diagram showing miscibility gaps for the isometric Th{sub x}Ce{sub 1-x}O{sub 2}, isometric Ce{sub x}Zr{sub 1-x}O{sub 2}, isometric Th{sub x}Zr{sub 1-x}O{sub 2}, and tetragonal Th{sub x}Zr{sub 1-x}O{sub 2} binaries at low composition (0<x<0.025), where the solid solidus is an average of the linear and Margules approximations for the incorporation limit (x{sub inc}), and the dotted solidus lines are the Margules approximation (above the average) and the linear approximation (below the average). Highlights: Black-Right-Pointing-Pointer {Delta}H{sub mix}, {Delta}G{sub mix}, and {Delta}S{sub mix} of Th{sub x}Ce{sub 1-x}O{sub 2}, Th{sub x}Zr{sub 1-x}O{sub 2}, and Ce{sub x}Zr{sub 1-x}O{sub 2} binaries are calculated. Black-Right-Pointing-Pointer Cation ordering is identified at low T for binaries containing ZrO{sub 2}. Black-Right-Pointing-Pointer Phase diagrams are estimated based on DFT and Monte-Carlo calculations. Black-Right-Pointing-Pointer DFT and Monte-Carlo calculations are in agreement with experimental (and previous computational) results, where available. Black-Right-Pointing-Pointer Increased thermodynamic stability of monoclinic and tetragonal ZrO{sub 2} end-member affects solid solution binaries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, single-crystal structure, and optical absorption of Rb{sub 2}Th{sub 7}Se{sub 15}

The compound Rb{sub 2}Th{sub 7}Se{sub 15} has been synthesized by the solid-state reaction at 1273 K of Th, Rb{sub 2}Se{sub 3}, Se, and Ge, and its structure has been determined by single-crystal X-ray diffraction methods. Red crystals of Rb{sub 2}Th{sub 7}Se{sub 15} crystallize at 100(2) K with four formula units in a new structure type in the monoclinic space group C{sub 2h}{sup 5}−P2{sub 1}/c. The structure is three-dimensional and comprises Rb and Th atoms coordinated by Se atoms to form nine-, eight-, and seven-coordinate polyhedra. Infinite channels that contain Rb atoms are present. Crystals of Rb{sub 2}Th{sub 7}Se{sub 15} are red in color; an indirect band gap of 1.83 eV was derived from single-crystal optical measurements. - Graphical abstract: Structure of Rb{sub 2}Th{sub 7}Se{sub 15} viewed down the b-axis. Display Omitted - Highlights: • The new compound Rb{sub 2}Th{sub 7}Se{sub 15} was synthesized at 1273 K from the elements in the presence of Ge. • The structures of the two known Rb/Th/Se compounds, RbTh{sub 2}Se{sub 6} and Rb{sub 2}Th{sub 7}Se{sub 15}, differ markedly. • Optical measurements establish the band gap of Rb{sub 2}Th{sub 7}Se{sub 15} to be indirect with a value of 1.83 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The synthesis, single-crystal structure, optical absorption, and resistivity of Th{sub 2}GeSe{sub 5}

The compound Th{sub 2}GeSe{sub 5} has been synthesized by the reaction of the elements at 1273 K. From a single-crystal study Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type with four formula units in the space group D{sup 8}{sub 4h}−P4/ncc of the tetragonal system in a cell with dimensions a=7.4968(4) Å and c=13.6302(9) Å at 100(2) K. From optical absorption measurements Th{sub 2}GeSe{sub 5} is found to have an optical band gap of 1.92 eV (indirect) or 1.98 eV (direct), consistent with its red color. Th{sub 2}GeSe{sub 5} is a wide gap semiconductor, as indicated by its electrical resistivity at 298 K of 4.37(2)×10{sup 9} Ω cm measured on a single crystal. - Graphical abstract: The structure of Th{sub 2}GeSe{sub 5}. Display Omitted - Highlights: • The new compound Th{sub 2}GeSe{sub 5} was synthesized from the elements and recrystallized from Sb{sub 2}Se{sub 3}. • Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type. • The band gap of Th{sub 2}GeSe{sub 5} is1.92 eV and its resistivity shows it to be a wide gap semiconductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interaction of Ce{sub 1−x}Er{sub x}O{sub 2−y} nanoparticles with SiO{sub 2}-effect of temperature and atmosphere

Morphology, microstructure and phase evolution of homogeneous, nanocrystalline Ce{sub 1−x}Er{sub x}O{sub 2−x/2} mixed oxide (x=0.3 and 0.5), prepared by microemulsion method, supported on amorphous SiO{sub 2} was studied in oxidizing and reducing atmosphere by XRD, TEM, SEM-EDS and N{sub 2} adsorption. The system is structurally and chemically stable in the oxidizing atmosphere up to 1000 °C, exhibiting only a small increase of the mean crystallite size of the oxide to ∼4 nm. At 1100 °C formation of Er silicate with unusual structure isomorphic with y-Y{sub 2}Si{sub 2}O{sub 7} (yttrialite), stabilized by Ce{sup 4+} ions was observed. In the reducing atmosphere the Ce{sub 1−x}Er{sub x}O{sub 2−x/2} reacted with SiO{sub 2} already at 900 °C, due to high affinity of the reduced Ce{sup 3+} to form a silicate phase. At higher temperature the silicate crystallized into the tetragonal, low temperature A-(Ce{sub 1−x}Er{sub x}){sub 2}Si{sub 2}O{sub 7} polymorph. Such systems, containing nanocrystalline silicate particles with Er{sup 3+} ions placed in well defined sites embedded in silica matrix, may be interesting as highly efficient active components of optical waveguides amplifiers integrated with Si microelectronics. The nanocrystalline Ce–Er–O/SiO{sub 2} system prepared by the impregnation of the silica with the aqueous solution of nitrates appeared to be chemically inhomogeneous and less stable in both oxidising and reducing atmosphere. - Graphical abstract: Structure evolution of Ce{sub 0.5}Er{sub 0.5}O{sub 1.75} in air and in H{sub 2}. Display Omitted - Highlights: • Homogeneous 3 nm Ce{sub 1−x}Er{sub x}O{sub 2−y} particles were prepared and uniformly dispersed on SiO{sub 2}. • Er diffusion to SiO{sub 2} determines the stability of the mixed oxide in air to ∼1000 °C. • Spreading of Ce{sub 1−x}Er{sub x}O{sub 2−y} onto SiO{sub 2} occurs in hydrogen at 900 °C. • Nanocrystalline A-(Ce,Er){sub 2}Si{sub 2}O{sub 7} silicate forms in H{sub 2} at 1100 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state actinide acid phosphites from phosphorous acid melts

The reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})]. This compound crystallizes in space group P2{sub 1}/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O)·2(H{sub 2}O). α- and β-An(HPO{sub 2}OH){sub 4} crystallize in space groups C2/c and P2{sub 1}/n, respectively, and comprise a three-dimensional network of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) crystallizes in a layered structure in space group Pbca that is composed of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized. - Graphical abstract: Reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with DMF produces crystals of (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})] with a layered structure. Reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup and further solution-state reactions result in the crystallization of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th), with a three-dimensional network structure, and the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) with a layered structure. - Highlights: • U(VI), U(IV) and Th(IV) phosphites were synthesized by solution-state methods. • A new uranyl phosphite structure is based upon uranyl phosphite anionic sheets. • New U and Th phosphites have framework structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and physical properties of RE{sub 2}AgGe{sub 3} (RE=Ce, Pr, Nd) compounds

We have synthesized the compounds RE{sub 2}AgGe{sub 3} (RE =Ce, Pr, Nd) by arc melting. The crystal structure obtained from single crystal and powder X-ray diffraction suggests that these compounds crystallize in the α-ThSi{sub 2} structure type. The magnetic susceptibility data of Ce{sub 2}AgGe{sub 3} follows Curie–Weiss (CW) law above 25 K without any magnetic ordering down to 2 K. The effective magnetic moment (μ{sub eff}) was calculated as 2.53 μ{sub B}/Ce and negative Curie paramagnetic temperature (θ{sub p})=−2.4 K hint weak antiferromagnetic coupling among the adjacent spins. Pr{sub 2}AgGe{sub 3} shows a complex magnetic behavior wherein the magnetic susceptibility at field cooled and zero field cooled modes bifurcates at 11.5 K with the latter undergoing a cusp like maxima, probably due to weak ferromagnetic interaction. The θ{sub p} and μ{sub eff} obtained are 4 K and 4.33 μ{sub B}/Pr, respectively. Nd{sub 2}AgGe{sub 3} undergoes multiple magnetic transitions. Temperature dependent resistivity data reveals that three compounds are metallic in nature. - Graphical abstract: The compounds Ce{sub 2}AgGe{sub 3}, Pr{sub 2}AgGe{sub 3} and Nd{sub 2}AgGe{sub 3} have been synthesized by arc melting. X-ray diffraction suggests tetragonal α-ThSi{sub 2} type structure and diverse magnetic properties exhibited in the magnetic measurements. - Highlights: • Two new compounds Ce{sub 2}AgGe{sub 3}, Nd{sub 2}AgGe{sub 3} and known Pr{sub 2}AgGe{sub 3} synthesized by arc melting. • Crystal structure of the compounds derived from X-ray diffraction. • Ce{sub 2}AgGe{sub 3} and Pr{sub 2}AgGe{sub 3} exhibit antiferromagnetic ordering. • Nd{sub 2}AgGe{sub 3} shows multiple magnetic transition with ferrimagnetic like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗