72 results on '"Vancho Kocevski"'
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2. Observation of the Same New Sheet Topology in Both the Layered Uranyl Oxide-Phosphate Cs11[(UO2)12(PO4)3O13] and the Layered Uranyl Oxyfluoride-Phosphate Rb11[(UO2)12(PO4)3O12F2] Prepared by Flux Crystal Growth
- Author
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Christian A. Juillerat, Vancho Kocevski, Theodore M. Besmann, and Hans-Conrad zur Loye
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flux crystal growth ,uranyl ,phosphuranylite ,single crystal ,DFT ,Chemistry ,QD1-999 - Abstract
Single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs11[(UO2)12(PO4)3O13] (1) and Rb11[UO2)12(PO4)3O12F2] (2) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U3O8, while Cs4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (3) and Rb4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (4) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2-4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase (1) and in contrast an oxyfluoride phase for the Rb containing phase (2). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO22+ uranyl group.
- Published
- 2019
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3. Effects of processing parameters on the morphologies of complex sesquioxide thin films
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Sofia K. Pinzon, James A. Valdez, Vancho Kocevski, J. K. Baldwin, Blas P. Uberuaga, Cortney R. Kreller, and Benjamin K. Derby
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Surfaces and Interfaces ,Condensed Matter Physics ,Surfaces, Coatings and Films - Abstract
Controlling and predicting the morphology of lanthanide sesquioxides in thin film form is vital to their use in current applications. In the present study, single and codeposited Sm2O3, Er2O3, and Lu2O3 thin films were grown on yttria-stabilized zirconia (8%) substrates by radio frequency magnetron sputtering at room temperature and 500 °C. The effect of two different substrate temperatures and altering the oxide cation on the structural and morphological properties of the films was analyzed. The thin films were characterized by profilometry, scanning electron microscopy, transmission electron microscopy, and x-ray diffraction. The single-component Lu2O3 and Sm2O3 films obtained were of the cubic phase, and the Er2O3 was a mix of cubic and monoclinic phases. It was observed for both the Er2O3 and Lu2O3 films that increasing the substrate temperature to 500 °C resulted in larger grained polycrystalline films. In contrast, large grained polycrystalline films were obtained at both room temperature and 500 °C for Sm2O3 and uneven granularity increased as temperature increased. Codeposition of Lu2O3 and Sm2O3, and Lu2O3 and Er2O3 resulted in a cubic bixbyite phase (the C phase of the lanthanide sesquioxide) solid solution. It was observed that the structure and morphology of the films can be controlled by manipulating deposition parameters. Both substrate temperature and altering the oxide cation contributed to changes in crystallinity and grain structure, which can modify the chemical and physical properties of the films for their applications.
- Published
- 2023
4. Finite temperature properties of uranium mononitride
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Vancho Kocevski, Daniel A. Rehn, Adrien J. Terricabras, Arjen van Veelen, Michael W.D. Cooper, Scarlett Widgeon Paisner, Sven C. Vogel, Joshua T. White, and David A. Andersson
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Nuclear and High Energy Physics ,Nuclear Energy and Engineering ,General Materials Science - Published
- 2023
5. Thermodynamics of phase stability and disorder in Inter-Lanthanide ternary ABO3 oxides from first principles
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Vancho Kocevski, Ghanshyam Pilania, and Blas Pedro Uberuaga
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Mechanics of Materials ,Mechanical Engineering ,General Materials Science - Published
- 2023
6. Dimensional reduction upon calcium incorporation in Cs0.3(Ca0.3Ln0.7)PS4 and Cs0.5(Ca0.5Ln0.5)PS4
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Hans-Conrad zur Loye, Vancho Kocevski, Vladislav V. Klepov, and Theodore M. Besmann
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Lanthanide ,Materials science ,Parent structure ,chemistry.chemical_element ,Charge (physics) ,General Chemistry ,Structure type ,Calcium ,Condensed Matter Physics ,Crystallography ,chemistry ,Dimensional reduction ,Group (periodic table) ,General Materials Science ,Monoclinic crystal system - Abstract
Two series of new lanthanide thiophosphates with partial Ca occupancy of the Ln sites, Cs0.3(Ca0.3Ln0.7)PS4 (Ln = Ce, Pr, Nd, Sm, Gd, Tb, and Dy) and Cs0.5(Ca0.5Ln0.5)PS4 (Ln = Pr, Nd, Sm, Gd, and Tb), were synthesized using a CsI flux and structurally characterized. The first series with an idealized formula of Cs0.3(Ca0.3Ln0.7)PS4 crystallizes in the Rm space group and belongs to a new structure type that consists of a channel containing [(Ca0.3Ln0.7)PS4]0.3− framework, where the channels are occupied by severely disordered Cs+ cations. A second new series with formula Cs0.5(Ca0.5Ln0.5)PS4 crystallizes in the monoclinic C2/c space group and exhibits a layered structure consisting of [(Ca0.5Ln0.5)PS4]0.5− layers with Cs+ cations located between the layers for charge balance. Together with the parent structure type, LnPS4, these three structure types illustrate how the LnPS4 structure changes with Cs+ cation incorporation, reducing its dimensionality from 3D to 2D. The magnetic properties of Cs0.3[(Ca0.3Ce0.7)PS4] and Cs0.3[(Ca0.3Pr0.7)PS4] were studied and revealed no magnetic transition down to 2 K.
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- 2021
7. Prediction of structure and cation ordering in an ordered normal-inverse double spinel
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Vancho Kocevski, Blas P. Uberuaga, Cortney R. Kreller, James A. Valdez, and Ghanshyam Pilania
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Diffraction ,Materials science ,Monte Carlo method ,Spinel ,Thermodynamics ,Inverse ,02 engineering and technology ,Electronic structure ,engineering.material ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Condensed Matter::Materials Science ,Mechanics of Materials ,engineering ,lcsh:TA401-492 ,First principle ,General Materials Science ,Condensed Matter::Strongly Correlated Electrons ,lcsh:Materials of engineering and construction. Mechanics of materials ,0210 nano-technology ,Solid solution ,Cluster expansion - Abstract
Spinels represent an important class of technologically relevant materials, used in diverse applications ranging from dielectrics, sensors and energy materials. While solid solutions combining two “single spinels” have been explored in a number of past studies, no ordered “double” spinels have been reported. Based on our first principles computations, here we predict the existence of such a double spinel compound MgAlGaO4, formed by an equimolar mixing of MgAl2O4 normal and MgGa2O4 inverse spinels. After studying the details of its atomic and electronic structure, we use a cluster expansion based effective Hamiltonian approach with Monte Carlo simulations to study the thermodynamic behavior and cation distribution as a function of temperature. Our simulations provide strong evidence for short-ranged cation order in the double spinel structure, even at significantly elevated temperatures. Finally, an attempt was made to synthesize the predicted double spinel compound. Energy Dispersive X-ray Spectrometry and X-ray diffraction Rietveld refinements were performed to characterize the single-phase chemical composition and local configurational environments, which showed a favorable agreement with the theoretical predictions. These findings suggest that a much larger number of compounds can potentially be realized within this chemical space, opening new avenues for the design of spinel-structured materials with tailored functionality. Materials with a spinel structure are used in various applications, including in the nuclear industry and as dielectrics. Here, first principle calculations and Monte Carlo simulations predict that an ordered double spinel structure is stable, supported by preliminary experimental data.
- Published
- 2020
8. Polymorphism and Molten Nitrate Salt-Assisted Single Crystal to Single Crystal Ion Exchange in the Cesium Ferrogermanate Zeotype: CsFeGeO4
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Mark D. Smith, P. Shiv Halasyamani, Vancho Kocevski, Theodore M. Besmann, Mohammad Usman, Weiguo Zhang, Gregory Morrison, and Hans-Conrad zur Loye
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Ion exchange ,010405 organic chemistry ,Inorganic chemistry ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Polymorphism (materials science) ,Nitrate ,Caesium ,Flux growth ,Orthorhombic crystal system ,Physical and Theoretical Chemistry ,Single crystal - Abstract
Two polymorphs of a new cesium ferrogermanate zeotype, CsFeGeO4, were synthesized using the molten CsCl-CsF flux growth approach at 900 °C. The orthorhombic polymorph, referred to as (1), crystalli...
- Published
- 2020
9. Structure and stability of alkali gallates structurally reminiscent of hollandite
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Vancho Kocevski, Jake W. Amoroso, Vladislav V. Klepov, Theodore M. Besmann, Hans-Conrad zur Loye, and Christian A. Juillerat
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Crystallography ,Materials science ,Ion exchange ,Hollandite ,Materials Chemistry ,Ceramics and Composites ,Crystal growth ,Alkali metal - Published
- 2020
10. NaGaS 2 : An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties
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Hui Wang, Anna A. Berseneva, Fanglin Chen, Kristen A. Pace, Peng Qiu, Vladislav V. Klepov, Vancho Kocevski, Hans-Conrad zur Loye, Mengqi Sun, and Theodore M. Besmann
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Materials science ,Aqueous solution ,Absorption of water ,Ion exchange ,010405 organic chemistry ,Chalcogenide ,Inorganic chemistry ,General Chemistry ,010402 general chemistry ,Uranyl ,01 natural sciences ,Exfoliation joint ,Catalysis ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Molecule ,Ternary operation - Abstract
Most ternary sulfides belonging to the MGaS2 structure-type have been known for many years and are well-characterized. Surprisingly, there have been no reports of the NaGaS2 composition, which contains Na, a monovalent cation slightly larger in size than Li, found in LiGaS2 , a compound known for its non-linear optical properties. Now it is demonstrated for the first time that the unique reversible water absorption in NaGaS2 has resulted in its absence from previous reports owing to difficulties encountered when characterizing this compound by SC XRD. The layered structure of this compound coupled with uniquely easy migration of water molecules between the layers allows for ion exchange with 3d and 5f metal cations. Some cations, for example, Ni2+ , facilitate exfoliation of the layers, providing a facile synthetic route to a new class of 2D chalcogenide materials and furthermore demonstrating that NaGaS2 can readily uptake uranyl species from aqueous solutions.
- Published
- 2020
11. NaGaS 2 : An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties
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Vladislav V. Klepov, Anna A. Berseneva, Kristen A. Pace, Vancho Kocevski, Mengqi Sun, Peng Qiu, Hui Wang, Fanglin Chen, Theodore M. Besmann, and Hans‐Conrad Loye
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General Medicine - Published
- 2020
12. New Rubidium-Containing Mixed-Metal Titanium Hollandites
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Mark D. Smith, Mohammad Usman, Theodore M. Besmann, Hans-Conrad zur Loye, Gregory Morrison, and Vancho Kocevski
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Materials science ,Mixed metal ,010405 organic chemistry ,Band gap ,Analytical chemistry ,chemistry.chemical_element ,Flux ,General Chemistry ,010402 general chemistry ,Condensed Matter Physics ,01 natural sciences ,Temperature measurement ,0104 chemical sciences ,d electron count ,Rubidium ,Quality (physics) ,chemistry ,General Materials Science ,Titanium - Abstract
A family of rubidium containing mixed-metal titanates, RbxMyTi8-yO16 (M = Mg, Mn, Fe, Ni, and Cu) was prepared as high quality single crystals employing a molten RbCl-RbF flux at 850 °C. This is th...
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- 2020
13. Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs2NaLn(PS4)2 (Ln = La–Nd, Sm, and Gd–Ho)
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Kristen A. Pace, Logan S. Breton, Vancho Kocevski, Hans-Conrad zur Loye, Theodore M. Besmann, and Vladislav V. Klepov
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Lanthanide ,Lanthanide contraction ,010405 organic chemistry ,Chemistry ,Coordination number ,010402 general chemistry ,Alkali metal ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,Thiophosphate ,Inorganic Chemistry ,Crystallography ,Paramagnetism ,chemistry.chemical_compound ,Ab initio quantum chemistry methods ,Physical and Theoretical Chemistry - Abstract
The effect of lanthanide contraction often results in topological and symmetry changes in compounds with the same compositions as a function of lanthanide cation size. Here we report on the first example of a lanthanide thiophosphate exhibiting a change in the lanthanide cation environment without any topological or symmetry change. A series of new lanthanide thiophosphates with mixed alkali cations were obtained via a flux crystal growth technique using a CsI flux. The obtained compounds Cs2NaLn(PS4)2 (Ln = La-Nd, Sm, and Gd-Ho) were grown as large single crystals (∼0.1-1 mm3) and characterized using single-crystal X-ray diffraction and magnetic susceptibility measurements. As we moved across the series, the structural studies revealed a change in the lanthanide coordination environment depending on the identity of the lanthanide. Although all compounds in the Cs2NaLn(PS4)2 series crystallize in the same space group and have the same Wyckoff atom positions, a slight change in size between Sm3+ and Gd3+ causes a subtle change in coordination number from 9 (for Ln = La-Sm) to 8 (for Ln = Gd-Ho), resulting in two distinct but virtually identical structure types. Ab initio calculations were performed, and the observed experimental trend was corroborated computationally. Magnetic measurements performed on the Cs2NaLn(PS4)2 (Ln = Ce, Pr, Nd, Gd, and Tb) compounds revealed paramagnetic behavior.
- Published
- 2020
14. Complex cobalt silicates and germanates crystallizing in a porous three-dimensional framework structure
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Theodore M. Besmann, Mohammad Usman, Vancho Kocevski, Hans-Conrad zur Loye, and Mark D. Smith
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Materials science ,Ion exchange ,chemistry.chemical_element ,General Chemistry ,Condensed Matter Physics ,Crystallography ,Tetragonal crystal system ,chemistry ,Lattice (order) ,General Materials Science ,Density functional theory ,Zeolite ,Cobalt oxide ,Cobalt ,Monoclinic crystal system - Abstract
Four new cesium-containing cobalt oxide complexes were reported. Cs(Co0.5Si0.5)SiO4 (1), Cs1.29(5)Co0.69(5)Ge1.81(5)O5 (2), and its ordered analogue Cs2CoGe4O10 (3) were synthesized using a mixed CsCl–CsF flux at 850 °C or 900 °C. The structure of (1) closely resembles that of known zeolite and feldspar structures, and (1) crystallizes in the noncentrosymmetric monoclinic space group Im with lattice parameters of a = 8.9926(4) A, b = 5.4599(2) A, c = 9.3958(6) A, and β = 91.5928(18)°. Complexes (2) and (3) crystallize in the same new structure with a highly porous three-dimensional framework in the tetragonal space group I with lattice parameters of a = 7.4239(14) A and c = 13.169(3) A for (2) and a = 7.3540(6) A and c = 13.1122(11) A for (3). The formation of (2) vs. (3) can be controlled based on slight variations in the quantities of the starting materials. Single-crystal-to-single-crystal ion exchange of (1) in a molten RbNO3 bath resulted in 14% Cs exchange with Rb, affording the composition Cs0.86Rb0.14(Co0.5Si0.5)SiO4 (4). First-principles density functional theory calculations were performed to elucidate the electronic and magnetic properties and stabilities of (1) and (3) at 0 K.
- Published
- 2020
15. New germanate and mixed cobalt germanate salt inclusion materials: [(Rb6F)(Rb4F)][Ge14O32] and [(Rb6F)(Rb3.1Co0.9F0.96)][Co3.8Ge10.2O30F2]
- Author
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Darren Carone, Mark D. Smith, Hans-Conrad zur Loye, Vancho Kocevski, Mohammad Usman, Vladislav V. Klepov, and Theodore M. Besmann
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chemistry.chemical_classification ,Materials science ,Intrinsic luminescence ,chemistry.chemical_element ,Salt (chemistry) ,Germanium ,General Chemistry ,Condensed Matter Physics ,Fluorescence ,Crystallography ,chemistry ,Flux growth ,General Materials Science ,Density functional theory ,Germanate ,Cobalt - Abstract
Single crystals of two new germanates, [(Rb6F)(Rb4F)][Ge14O32] and [(Rb6F)(Rb3.1Co0.9F0.96)][Co3.8Ge10.2O30F2], were synthesized via high temperature RbCl/RbF flux growth. Both compounds crystallize in the cubic space group F3m and possess the germanium framework of the previously reported salt inclusion material (SIM), [(Cs6F)(Cs3AgF)][Ge14O32], related to the Ge7O16 zeolitic family. These materials demonstrate the ability to accommodate a variety of salt-inclusions, and exhibit chemical flexibility enabling modifications of the framework through incorporation of Co. Alteration of the salt-inclusion led to intrinsic luminescence of [(Rb6F)(Rb4F)][Ge14O32] while modification of the framework resulted in an unanticipated Rb/Co salt/inclusion in [(Rb6F)(Rb3.1Co0.9F0.96)][Co3.8Ge10.2O30F2]. Fluorescence measurements were performed on [(Rb6F)(Rb4F)][Ge14O32]. First-principles calculations in the form of density functional theory (DFT) were performed for [(Rb6F)(Rb3.1Co0.9F0.96)][Co3.8Ge10.2O30F2] to elucidate its electronic and magnetic properties, and stability at 0 K.
- Published
- 2020
16. High-throughput investigation of the formation of double spinels
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Vancho Kocevski, Blas P. Uberuaga, and Ghanshyam Pilania
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Materials science ,Ionic radius ,Renewable Energy, Sustainability and the Environment ,Operator (physics) ,Spinel ,02 engineering and technology ,General Chemistry ,engineering.material ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Chemical formula ,0104 chemical sciences ,Crystallography ,Octahedron ,Tetrahedron ,engineering ,General Materials Science ,Density functional theory ,0210 nano-technology ,Mixing (physics) - Abstract
Spinel compounds, with the general chemical formula AB2O4, are a wide class of materials, where A and B can be a variety of cations, providing this structure with a great deal of functional flexibility and giving rise to its considerable scientific interest. Recently, a spinel with the general formula ABB′O4 has been predicted, increasing the possible usability of the spinels due to the higher cation diversity in the so-called double spinel structure. Here, we use density functional theory calculations to predict if double spinels can be formed between experimentally synthesized normal and inverse single spinels. Our computations reveal that 49 double spinels have negative mixing enthalpies and are thus thermodynamically stable, with most of the stable compounds being formed from one of two distinct cation orderings. We show that the 17 different cations that form the different double spinels have a preferred site, tetrahedral or octahedral, except for Mn, Fe and Co which can occupy both sites interchangeably. We also study the relation between mixing enthalpies and cation-specific properties, as well as ways to classify the double spinels into distinct types and spinel groups depending on the cation ordering and cation oxidation states, respectively. By applying the Sure Independence Screening and Sparsifying Operator (SISSO) approach on the coordination-dependent ionic radii of the elemental constituents, we show that an interplay of local strain and electrostatic dominated terms can be used to separate the double spinels into distinct structural types depending on the cation order and their oxidation states.
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- 2020
17. Atomic-scale modeling of complex oxides and nuclear fuels [Slides]
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Vancho Kocevski
- Published
- 2022
18. CALPHAD modeling of uranium nitride (UN) fabrication routes enabled by first-principles calculations
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Vancho Kocevski, Jason T. Rizk, Michael W.D. Cooper, David A. Andersson, Joshua T. White, and Christopher Matthews
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General Chemical Engineering ,General Chemistry ,Computer Science Applications - Published
- 2022
19. Modeling Disorder in Pyrochlores and Other Anion-Deficient Fluorite Structural Derivative Oxides
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Blas P. Uberuaga, Vancho Kocevski, and Ghanshyam Pilania
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pyrochlore ,atomistic material modelling ,Mathematical model ,Pyrochlore ,Oxide ,disorder–compounds ,Review ,General Chemistry ,short range order (SRO) ,engineering.material ,Fluorite ,Crystallographic defect ,Ion ,chemistry.chemical_compound ,Molecular dynamics ,Chemistry ,chemistry ,fluorite ,Chemical physics ,engineering ,Density functional theory ,QD1-999 - Abstract
Their very flexible chemistry gives oxide materials a richness in functionality and wide technological application. A specific group of oxides that have a structure related to fluorite but with less oxygen, termed anion-deficient fluorite structural derivatives and with pyrochlores being the most notable example, has been shown to exhibit a diversity of useful properties. For example, the possibility to undergo a transition from an ordered to disordered state allows these oxides to have high radiation tolerance. Atomistic-scale calculations in the form of molecular dynamics (MD) and density functional theory (DFT) have been extensively used to understand what drives this order/disorder transition. Here we give a brief overview of how atomistic-scale calculations are utilized in modeling disorder in pyrochlores and other anion-deficient fluorite structural derivatives. We discuss the modeling process from simple point defects to completely disordered structures, the dynamics during the disordering process, and the use of mathematical models to generate ordered solid-solution configurations. We also attempt to identify the challenges in modeling short range order and discuss future directions to more comprehensive models of the disordered structures.
- Published
- 2021
20. Investigation of the on-site Coulomb correction and temperature dependence of the stability of U–Si phases using DFT+U
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Vancho Kocevski, Denise Adorno Lopes, and Theodore M. Besmann
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Convex hull ,Nuclear and High Energy Physics ,Phase transition ,Materials science ,Condensed matter physics ,Electronic correlation ,02 engineering and technology ,021001 nanoscience & nanotechnology ,01 natural sciences ,010305 fluids & plasmas ,Tetragonal crystal system ,chemistry.chemical_compound ,Nuclear Energy and Engineering ,chemistry ,Phase space ,0103 physical sciences ,Silicide ,Coulomb ,General Materials Science ,0210 nano-technology ,Phase diagram - Abstract
The development and qualification of silicide-based nuclear fuel would significantly benefit from an adequate understanding of the U–Si phase space, yet issues remain with respect to confidence in the phase diagram, especially in the USi–USi 2 composition range. Experimental investigations have shown the existence of hexagonal and tetragonal phases in the USi x 1.5 x 2 phase space. We subsequently performed a detailed analysis of the dependence of the U–Si convex hull on values of the on-site Coulomb correction, U eff , (DFT + U ) using the U -ramping method. This information allowed us to study the influence of electron correlation, and to find U eff values that best represents the U–Si convex hull. Lastly, the temperature dependence was calculated using determined Gibbs energies of the phases. In the USi–USi 2 phase space, two stable phases were observed up to 1200 °C, with a possible hexagonal to tetragonal phase transition at 580 °C for one of the phases.
- Published
- 2019
21. Superwadeites: Elucidation of a Structural Family Related to the Wadeite Structure and Prediction of Cs2Ge5O11
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Theodore M. Besmann, Gregory Morrison, Adrian T. Hines, Hans-Conrad zur Loye, Vancho Kocevski, Nicholas R. Spagnuolo, and Scott T. Misture
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Materials science ,010405 organic chemistry ,Rietveld refinement ,Substitution (logic) ,Structure (category theory) ,General Chemistry ,010402 general chemistry ,Condensed Matter Physics ,01 natural sciences ,0104 chemical sciences ,Crystallography ,General Materials Science ,Density functional theory ,Flux (metabolism) - Abstract
Single crystals of Cs6Ln2Ge11O28 (Ln = La, Pr, and Nd) and Cs12Bi3Ge24O58F were grown from a CsCl/CsF flux. These compounds crystallize in new structure types and are members of a new structural family related to the Wadeite structure by polyhedral substitution. Elucidation of this structural family, dubbed the superwadeites, allows for the prediction of the existence and structure of Cs2Ge5O11. Density functional theory calculations support that Cs2Ge5O11 is a stable compound. Ultimately, this compound is grown via a solid-state reaction, and its structure is refined via Rietveld refinement.
- Published
- 2019
22. Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux
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Kristen A. Pace, Logan S. Breton, Vladislav V. Klepov, Vancho Kocevski, Hans-Conrad zur Loye, and Theodore M. Besmann
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Lanthanide ,chemistry.chemical_classification ,Sulfide ,010405 organic chemistry ,Chemistry ,Iodide ,Crystal growth ,010402 general chemistry ,Alkali metal ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,Thiophosphate ,Inorganic Chemistry ,chemistry.chemical_compound ,Oxidation state ,Physical chemistry ,Physical and Theoretical Chemistry - Abstract
To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP2S6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP2S7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie-Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP2S7 sample. UV-vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.
- Published
- 2019
23. Experimental and computational assessment of U Si N ternary phases
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J.T. White, Emily E. Moore, Antoine Claisse, Andrew T. Nelson, Tashiema L. Wilson, Denise Adorno Lopes, E. Sooby Wood, Simon C. Middleburgh, Theodore M. Besmann, and Vancho Kocevski
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Nuclear and High Energy Physics ,Solid-state chemistry ,Materials science ,Rietveld refinement ,Thermodynamics ,02 engineering and technology ,Soft modes ,Crystal structure ,021001 nanoscience & nanotechnology ,01 natural sciences ,010305 fluids & plasmas ,Condensed Matter::Materials Science ,Nuclear Energy and Engineering ,Phase (matter) ,0103 physical sciences ,Melting point ,General Materials Science ,0210 nano-technology ,Dispersion (chemistry) ,Ternary operation - Abstract
Uranium nitride-silicide composites are being considered as a high-density and high thermal conductivity fuel option for light water reactors. During development, chemical interactions were observed near the silicide melting point which resulted in formation of an unknown U Si N ternary phase. In the present work, U Si N composite samples were produced by arc-melting U3Si2 under an argon-nitrogen atmosphere to form the ternary phase. The resulting samples were characterized by SEM/EDS-EPMA and XRD, and demonstrated an equilibrium between U3Si2, UN, USi and a U Si N phase with a distinct crystallographic structure. Rietveld refinement of the ternary structure was performed, considering the ternary structures existent in the analogue U Si C system, and a good fit was obtained for the hexagonal U20Si16N3 phase. DFT + U calculations were performed in parallel to evaluate the thermodynamic and dynamic stability of the ternaries U20Si16N3 and U3Si2N2. The calculated enthalpy of formation and phonon dispersion support the existence of stable U20Si16N3 and U3Si2N2, although some soft modes in the U20Si16N3 phase phonons are observed. The results presented here thus demonstrate the occurrence of at least one ternary phase in the U Si N system.
- Published
- 2019
24. Discovery of Cs2(UO2)Al2O5 by Molten Flux Methods: A Uranium Aluminate Containing Solely Aluminate Tetrahedra as the Secondary Building Unit
- Author
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Theodore M. Besmann, Vancho Kocevski, Christian A. Juillerat, and Hans-Conrad zur Loye
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Secondary building unit ,010405 organic chemistry ,Chemistry ,Aluminate ,Solid-state ,chemistry.chemical_element ,Uranium ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Inorganic Chemistry ,Crystallography ,Tetragonal crystal system ,chemistry.chemical_compound ,Lattice (order) ,Tetrahedron ,Physical and Theoretical Chemistry ,Flux synthesis - Abstract
The flux synthesis, solid state synthesis, and characterization of a new aluminate, Cs2(UO2)Al2O5, are reported. Cs2(UO2)Al2O5 crystallizes in the tetragonal space group I41/amd with lattice parame...
- Published
- 2019
25. Alkaline earth ion exchange study of pure silica LTA zeolites using periodic first-principles calculations
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Shenyang Y. Hu, Theodore M. Besmann, and Vancho Kocevski
- Subjects
Alkaline earth metal ,Work (thermodynamics) ,Dopant ,Ion exchange ,Chemistry ,Inorganic chemistry ,02 engineering and technology ,General Chemistry ,Electron ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Ion ,Adsorption ,Materials Chemistry ,0210 nano-technology ,Zeolite - Abstract
Experiments show that zeolites, such as Linde Type A (LTA), are promising materials for radioactive decontamination processes. In this work, the thermodynamic properties associated with alkaline earth ion (Ca2+, Sr2+ and Ba2+) exchange in pure silica LTA was studied using periodic first-principles calculations. The adsorption energies of alkaline earth ions compared with that of Na+ were investigated. The driving forces for alkaline earth exchange and related isotherms were calculated, and analyzed as a function of the electron chemical potential. The results demonstrate that Na+ in a pure silica LTA can completely be removed by Ba2+ and almost completely be removed by Sr2+ from a stream, but cannot be effectively exchanged by Ca2+. We also showed that electron-donating dopants should suppress Sr2+ and Ba2+ ion exchange, and that there is a substantial preference for incorporating Ba2+ over Sr2+. Lastly, the substantial difference between the adsorption energies of the ions in an assumed vacuum and those computed in water suggests that a solvation model is needed for accurate representation of ion adsorption in an LTA zeolite.
- Published
- 2019
26. Flux crystal growth of uranium(<scp>v</scp>) containing oxyfluoride perovskites
- Author
-
Vancho Kocevski, Deepak Patil, Theodore M. Besmann, Scott T. Misture, Stavros Karakalos, Hans-Conrad zur Loye, Gregory Morrison, and Christian A. Juillerat
- Subjects
Materials science ,Energy-dispersive X-ray spectroscopy ,Crystal growth ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Uranyl ,Alkali metal ,7. Clean energy ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,Inorganic Chemistry ,Crystallography ,chemistry.chemical_compound ,chemistry ,X-ray photoelectron spectroscopy ,0210 nano-technology ,Spectroscopy ,Single crystal - Abstract
The novel phases Rb4NaU3O12−xFx (1), K4NaU3O12−xFx (2), and Rb2.1K1.9KU3O12−xFx (3) were synthesized by molten flux methods using mixed alkali fluoride melts. The oxyfluorides crystallize in the cubic space group Imm with a lattice parameters of 8.7472(2) A, 8.6264(2) A, and 8.8390(3) A, respectively. All three structures crystallize in a cubic perovskite structure, ABO3 (A4BB′3O12), where the A site is fully occupied by an alkali cation, and the B site is shared by the remaining smaller alkali cation and uranium in an ordered fashion such that the alkali cation on the B site is surrounded by square uranyl bipyramids. The structures were characterized by single crystal X-ray diffraction, energy dispersive spectroscopy, X-ray absorption near edge structure spectroscopy, X-ray photoelectron spectroscopy, magnetic susceptibility measurements, DFT calculations, thermogravimetric analysis, and UV-vis spectroscopy, all of which support the presence of U(V) in the three new materials.
- Published
- 2019
27. Understanding the Polymorphism of A4[(UO2)3(PO4)2O2] (A = Alkali Metals) Uranyl Phosphate Framework Structures
- Author
-
Christian A. Juillerat, Hans-Conrad zur Loye, Vancho Kocevski, Theodore M. Besmann, and Emily E. Moore
- Subjects
Materials science ,010405 organic chemistry ,Band gap ,General Chemistry ,010402 general chemistry ,Condensed Matter Physics ,Alkali metal ,Uranyl ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Polymorphism (materials science) ,Uranyl phosphate ,Physical chemistry ,General Materials Science ,Density functional theory - Abstract
In this study we combine experimental synthesis and density functional theory (DFT) calculations to gain insight into the polymorphism of A4[(UO2)3(PO4)2O2] (A = Na, K, Rb, Cs) uranyl phosphate structures. Single crystals of a new 3D uranyl phosphate, Cs4[(UO2)3(PO4)2O2], were grown by molten flux methods using a CsCl flux. DFT calculations, using the DFT+U method, were carried out to study the difference between this new 3D uranyl phosphate and a family of recently described layered uranyl phosphates. Variation of the computed properties with changes in Ueff values are also studied. The DFT results agree with the experimental observations, showing that the Cs-containing 3D polymorph and the K-containing layered polymorphs are more stable than their respective layered and 3D polymorph. We show an increase in the difference between the total energies of the layered and 3D polymorphs and an increase in the band gaps with increasing Ueff value. Volume-based thermodynamics was also applied to calculate the to...
- Published
- 2018
28. Stability of U5Si4 phase in U-Si system: Crystal structure prediction and phonon properties using first-principles calculations
- Author
-
Vancho Kocevski, Denise Adorno Lopes, Theodore M. Besmann, Tashiema L. Wilson, and Emily E. Moore
- Subjects
Convex hull ,Nuclear and High Energy Physics ,Materials science ,Phonon ,Thermodynamics ,02 engineering and technology ,021001 nanoscience & nanotechnology ,01 natural sciences ,Standard enthalpy of formation ,010305 fluids & plasmas ,Crystal structure prediction ,Nuclear Energy and Engineering ,Octahedron ,Molecular vibration ,0103 physical sciences ,General Materials Science ,Chemical stability ,Density functional theory ,0210 nano-technology - Abstract
U-Si systems have recently received considerable attention due to the potential application of U3Si2 as a high-density fuel under an accident tolerant fuel initiative. However, the thermodynamic stability of the more recently reported adjacent U5Si4 phase is uncertain and could play a significant role in fuel performance. In this work, the enthalpy of formation of the phase predicted by density functional theory (DFT) using the DFT + U formalism is used with an evolutionary algorithm (USPEX) to evaluate stability and possible atomic structures for U5Si4. The structure of U-Si convex hull phases and the confirmed U3Si2 structure were predicted providing confidence in the reliability of the evolutionary algorithm, as well as to obtain a convex hull with comparable enthalpies of formation. Subsequently, the code was applied to the U5Si4 composition for cells with 18 and 36 atoms, predicting a 36-atom hexagonal symmetrized unit cell with space group P6/mmm as the lowest-energy configuration, agreeing with that experimentally reported for U5Si4. Yet, phonon calculations using the density functional perturbation theory formalism, demonstrated that the predicted structure is dynamically unstable, exhibiting negative vibrational modes for the uranium. These indicated that generated shears are directed toward the formation of potential uranium octahedral sites, analogous to those occupied by carbon atoms in U20Si16C3. It was thus concluded that omitting the U5Si4 phase from assessed U-Si phase equilibria is currently justified.
- Published
- 2018
29. Development and application of a uranium mononitride (UN) potential: Thermomechanical properties and Xe diffusion
- Author
-
Vancho Kocevski, Michael W.D. Cooper, Antoine J. Claisse, and David A. Andersson
- Subjects
Nuclear and High Energy Physics ,Nuclear Energy and Engineering ,General Materials Science - Published
- 2022
30. Polymorphism and Molten Nitrate Salt-Assisted Single Crystal to Single Crystal Ion Exchange in the Cesium Ferrogermanate Zeotype: CsFeGeO
- Author
-
Mohammad, Usman, Vancho, Kocevski, Mark D, Smith, Gregory, Morrison, Weiguo, Zhang, Theodore, Besmann, P Shiv, Halasyamani, and Hans-Conrad, Zur Loye
- Abstract
Two polymorphs of a new cesium ferrogermanate zeotype, CsFeGeO
- Published
- 2020
31. Understanding the interface interaction between U3Si2 fuel and SiC cladding
- Author
-
Denise Adorno Lopes, Antoine Claisse, Vancho Kocevski, and Theodore M. Besmann
- Subjects
Cladding (metalworking) ,Electronic structure ,Materials science ,Science ,Diffusion ,Composite number ,General Physics and Astronomy ,02 engineering and technology ,01 natural sciences ,Article ,General Biochemistry, Genetics and Molecular Biology ,chemistry.chemical_compound ,Surfaces, interfaces and thin films ,Nuclear fuel ,Phase (matter) ,0103 physical sciences ,Silicide ,Silicon carbide ,Composite material ,lcsh:Science ,010302 applied physics ,Multidisciplinary ,General Chemistry ,021001 nanoscience & nanotechnology ,chemistry ,lcsh:Q ,Uranium carbide ,Density functional theory ,0210 nano-technology - Abstract
Triuranium disilicide (U3Si2) fuel with silicon carbide (SiC) composite cladding is being considered as an advanced concept/accident tolerant fuel for light water reactors thus, understanding their chemical compatibility under operational and accident conditions is paramount. Here we provide a comprehensive view of the interaction between U3Si2 and SiC by utilizing density functional theory calculations supported by diffusion couple experiments. From the calculated reaction energies, we demonstrate that triuranium pentasilicide (U3Si5), uranium carbide (UC), U20Si16C3, and uranium silicide (USi) phases can form at the interface. A detailed study of U3Si2 and SiC defect formation energies of the equilibrated materials yielding the interfacial phases U20Si16C3, U3Si5 and UC reveal a thermodynamic driving force for generating defects in both fuel and cladding. The absence of either the U3Si2 or SiC phase, however, causes the defect formation energies in the other phase to be positive, removing the driving force for additional interfacial reactions. The diffusion couple experiments confirm the conclusion with demonstrated restricted formation of U3Si5, UC, and U20Si16C3/USi phases at the interface. The resulting lack of continuous interaction between the U3Si2 and SiC, reflects the diminishing driving force for defect formation, demonstrating the substantial stability of this fuel-cladding system., Triuranium disilicide fuel and silicon carbide cladding system is of importance for accident tolerance fuel initiative. Here the authors discuss the role of interface interaction between the U3Si2 fuel and SiC cladding in their use as an advanced concept in light water reactors.
- Published
- 2020
32. Phase Equilibria and Thermochemistry of Advanced Fuels: Modeling Burnup Behavior (Final Report)
- Author
-
Denise Adorno-Lopez, Kaitlin Johnson, Joshua T. White, Edward Jean Lahoda, Antoine Claisse, Theodore M. Besmann, Simon C. Middleburgh, Jake W. McMurray, Sven C. Vogel, Andrew T. Nelson, Vancho Kocevski, and Tashiema L. Ulrich
- Subjects
Materials science ,Phase (matter) ,Nuclear engineering ,Technical report ,Thermochemistry ,Burnup - Published
- 2020
33. Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs
- Author
-
Vladislav V, Klepov, Kristen A, Pace, Logan S, Breton, Vancho, Kocevski, Theodore M, Besmann, and Hans-Conrad, Zur Loye
- Abstract
The effect of lanthanide contraction often results in topological and symmetry changes in compounds with the same compositions as a function of lanthanide cation size. Here we report on the first example of a lanthanide thiophosphate exhibiting a change in the lanthanide cation environment without any topological or symmetry change. A series of new lanthanide thiophosphates with mixed alkali cations were obtained via a flux crystal growth technique using a CsI flux. The obtained compounds Cs
- Published
- 2020
34. NaGaS
- Author
-
Vladislav V, Klepov, Anna A, Berseneva, Kristen A, Pace, Vancho, Kocevski, Mengqi, Sun, Peng, Qiu, Hui, Wang, Fanglin, Chen, Theodore M, Besmann, and Hans-Conrad, Zur Loye
- Abstract
Most ternary sulfides belonging to the MGaS
- Published
- 2020
35. The u3si2-H system
- Author
-
Aditya Shivprasad, Vancho Kocevski, J.T. White, T.L. Ulrich, Joseph R. Wermer, and David A. Andersson
- Subjects
Nuclear and High Energy Physics ,Standard enthalpy of reaction ,Materials science ,Hydrogen ,Hydride ,Enthalpy ,Analytical chemistry ,chemistry.chemical_element ,Uranium ,Nuclear Energy and Engineering ,chemistry ,Phase (matter) ,General Materials Science ,Absorption (chemistry) ,Stoichiometry - Abstract
U 3 Si 2 is of interest to the nuclear industry as a candidate fuel material due to its high uranium density and high thermal conductivity. However, it has been observed to react with hydrogen, resulting in material decrepitation. As a result, it is important to understand the thermodynamics of the U 3 Si 2 -H system. In this study, the thermodynamics of the hydrogen absorption reaction of U 3 Si 2 were determined experimentally using Sievert’s gas absorption and related to crystallographic evolution with hydrogen content using X-ray diffraction. Experimentally-determined thermodynamic parameters were compared with results from density functional theory modeling. Results from this study were also compared with those determined in previous work. Sievert’s gas absorption results were used to develop the pressure-composition-temperature (PCT) curves of the U 3 Si 2 -H system. It was found that the hydride phase exhibited a maximum stoichiometry between U 3 Si 2 H 1.8 and U 3 Si 2 H 2 . The two-phase region for hydride formation from U 3 Si 2 exhibited a miscibility gap with a critical temperature between 623 and 673 K, as calculated from the PCT curves. Analysis of the PCT curves also showed that both the enthalpy and entropy of the hydrogen absorption reaction increased with hydrogen content but were lower than the values for uranium trihydride formation from uranium metal. The enthalpy of reaction for hydrogen absorption was calculated to range between -86.9 and -94.8 kJ mol − 1 , while the entropy of reaction was calculated to range between 101.9 and 138.8 J mol − 1 K − 1 . DFT modeling of the thermoydnamic stability of the U 3 Si 2 hydride phases yielded a decomposition temperature of U 3 Si 2 H 2 of approximately 600 K, which was consistent with the experimental results. Similarly, the DFT-calculated enthalpy and entropy of reaction to form U 3 Si 2 H 1.5 were determined to be -106.5kJ mol − 1 and 121.8J mol − 1 K − 1 , respectively, which were both in close agreement with the experimentally-determined values.
- Published
- 2022
36. Uranium nitride-silicide advanced nuclear fuel: higher efficiency and greater safety
- Author
-
Simon C. Middleburg, Tashiema L. Wilson, Emily E. Moore, Denise Adorno Lopes, Joshua T. White, Andrew T. Nelson, Peng Xu, Jacob W. McMurray, Vancho Kocevski, Elizabeth Sooby Wood, and Theodore M. Besmann
- Subjects
010302 applied physics ,Materials science ,Nuclear fuel ,Metallurgy ,chemistry.chemical_element ,02 engineering and technology ,Nitride ,Uranium ,021001 nanoscience & nanotechnology ,Cladding (fiber optics) ,01 natural sciences ,Industrial and Manufacturing Engineering ,chemistry.chemical_compound ,Ferritic alloy ,chemistry ,0103 physical sciences ,Silicide ,Ceramics and Composites ,0210 nano-technology ,Uranium nitride - Abstract
As part of Accident Tolerant Fuel initiative for light water reactors, uranium silicide and silicide-nitride are being considered as fuels that can be combined with a more robust cladding such as a...
- Published
- 2018
37. A Family of Layered Phosphates Crystallizing in a Rare Geometrical Isomer of the Phosphuranylite Topology: Synthesis, Characterization, and Computational Modeling of A4[(UO2)3O2(PO4)2] (A = Alkali Metal) Exhibiting Intralayer Ion Exchange
- Author
-
Theodore M. Besmann, Vancho Kocevski, Christian A. Juillerat, Hans-Conrad zur Loye, and Emily E. Moore
- Subjects
Ion exchange ,Charge (physics) ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Alkali metal ,Uranyl ,01 natural sciences ,Chloride ,Standard enthalpy of formation ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,chemistry ,medicine ,Density functional theory ,Physical and Theoretical Chemistry ,0210 nano-technology ,medicine.drug ,Monoclinic crystal system - Abstract
Single crystals of eight new layered uranyl phosphates were grown from alkali chloride fluxes: Cs1.4K2.6[(UO2)3O2(PO4)2], Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], K4[(UO2)3O2(PO4)2], K2.9Na0.9Rb0.2[(UO2)3O2(PO4)2], K2.1Na0.7Rb1.2[(UO2)3O2(PO4)2], Cs1.7K4.3[(UO2)5O5(PO4)2], and Rb1.6K4.4[(UO2)5O5(PO4)2]. All structures crystallize in the monoclinic space group, P21/c and contain uranyl phosphate layers with alkali metals located between the layers for charge balance. Ion exchange experiments on Cs0.7K3.3[(UO2)3O2(PO4)2], Rb1.4K2.6[(UO2)3O2(PO4)2], and K4[(UO2)3O2(PO4)2] demonstrated that Cs and Rb cations cannot be exchanged for K cations; however, K cations can be readily exchanged for Na, Rb, and Cs. Enthalpies of formation were calculated from density functional theory (DFT) and volume-based thermodynamics (VBT) for all six structures. A value for the enthalpy of formation of the phosphuranylite sheet, [(UO2)3O2(PO4)2]4–, was derived using single-ion additive methods coupled with VBT. DFT a...
- Published
- 2018
38. Na2(UO2)(BO3): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions
- Author
-
Theodore M. Besmann, Stavros Karakalos, Hans-Conrad zur Loye, Gregory Morrison, Vancho Kocevski, and Kristen A. Pace
- Subjects
Magnetic moment ,chemistry.chemical_element ,02 engineering and technology ,Uranium ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Magnetic susceptibility ,Hydrothermal circulation ,0104 chemical sciences ,Inorganic Chemistry ,Crystallography ,chemistry ,Antiferromagnetism ,Density functional theory ,Orthorhombic crystal system ,Physical and Theoretical Chemistry ,0210 nano-technology ,Boron - Abstract
The first entirely pentavalent uranium borate, Na2(UO2)(BO3), was synthesized under mild hydrothermal conditions. The single-crystal structure was solved in the orthorhombic space group Cmcm with a = 10.0472(3) A, b = 6.5942(2) A, and c = 6.9569(2) A. Magnetic susceptibility measurements revealed an antiferromagnetic transition at 12 K and an effective magnetic moment of 2.33 μB. Density functional theory calculations indicated dynamic stability of the structure above 0 K.
- Published
- 2018
39. A valence balanced rule for discovery of 18-electron half-Heuslers with defects
- Author
-
Chris Wolverton, Shashwat Anand, Vancho Kocevski, Vinay Hegde, Kaiyang Xia, G. Jeffrey Snyder, Umut Aydemir, and Tiejun Zhu
- Subjects
Valence (chemistry) ,Renewable Energy, Sustainability and the Environment ,02 engineering and technology ,Electron ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Pollution ,0104 chemical sciences ,Nuclear Energy and Engineering ,Chemical physics ,Environmental Chemistry ,Chemical stability ,0210 nano-technology ,Ground state ,Stoichiometry - Abstract
Using first-principles DFT we systematically investigate the thermodynamic stability and off-stoichiometry in 108 nominal 19-electron half-Heusler (hH) compounds. We demonstrate unambiguously that considering a cation deficiency towards the off-stoichiometric valence balanced, VEC = 18 composition is necessary for explaining the stability of all previously reported nominal VEC = 19 compounds. This is understandable in terms of an energy benefit from valence balance considering the valence of each atom using Zintl chemistry that offsets the energy penalty of forming defects in nearly all cases. Thus, we propose a valence balanced rule to understand the ground state stability of half-Heuslers irrespective of stoichiometry and nominal electron count (8, 18 or 19). Using this generalized rule we (a) predict 16 previously unreported nominal 19-electron XYZ half-Heuslers and (b) rationalize the reports of giant off-stoichiometries in compounds such as Ti(1−x)NiSb which has been known for over 50 years. Of the 16 new compounds predicted here, Ti(1−x)PtSb was synthesized and the half-Heusler phase confirmed through X-ray studies. The flexibility in stoichiometry of the half-Heusler systems to attain a stable valence balanced composition by accommodating large defect concentrations opens up multiple dimensions for discovery of multi-component defective half-Heuslers based on intrinsic and extrinsic defects which compensate for the nominally non-18-electron count of the structure.
- Published
- 2018
40. Designing High-Efficiency Nanostructured Two-Phase Heusler Thermoelectrics
- Author
-
Chris Wolverton and Vancho Kocevski
- Subjects
Materials science ,General Chemical Engineering ,Nanotechnology ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Thermoelectric materials ,01 natural sciences ,0104 chemical sciences ,Thermal conductivity ,Phase (matter) ,Thermoelectric effect ,Materials Chemistry ,0210 nano-technology - Abstract
Nanostructured systems formed by two distinct phases are particularly promising for high efficiency thermoelectrics due to the reduction in thermal conductivity afforded by the nanostructured phase. However, the choice of the matrix and nanostructured phases represents a challenging materials discovery problem due to the large compositional space involved. Heusler phase thermoelectrics are particularly promising candidates for nanostructuring since these compounds often possess favorable electronic thermoelectric properties but relatively high thermal conductivity. Here, we have developed a high-throughput screening strategy to predict promising candidates for nanostructuring systems based on two Heusler phases. Our search includes all two-phase systems involving full, half, and inverse Heusler in the Open Quantum Materials Database, in total a search space of ∼1011 possible combinations of two Heusler compounds. To reduce this space, our screening approach starts with a set of known thermoelectrics as ma...
- Published
- 2017
41. Discovery of Cs
- Author
-
Christian A, Juillerat, Vancho, Kocevski, Theodore M, Besmann, and Hans-Conrad, Zur Loye
- Abstract
The flux synthesis, solid state synthesis, and characterization of a new aluminate, Cs
- Published
- 2019
42. Synthesis of the First All-Uranium(V) Borate
- Author
-
Kristen A. Pace, Vancho Kocevski, and Hans-Conrad zur Loye
- Subjects
chemistry ,chemistry.chemical_element ,Uranium ,Boron ,Nuclear chemistry - Published
- 2019
43. Compatibility Of U3Si2 Fuel With Zr, FeCrAl and SiC/SiC Based Cladding
- Author
-
Joshua T. White, Tashiema L. Wilson, Emily E. Moore, Antoine Claisse, Peng Xu, Denise L. Adorno, Jacob W. McMurray, Theodore M. Besmann, and Vancho Kocevski
- Subjects
Cladding (metalworking) ,Materials science ,Compatibility (geochemistry) ,Composite material - Published
- 2018
44. Salt-flux synthesis, crystal structure and theoretical characterization of Rb0.74Ga6.62Ti0·38O11
- Author
-
Mohammad Usman, Mark D. Smith, Theodore M. Besmann, Hans-Conrad zur Loye, and Vancho Kocevski
- Subjects
Materials science ,business.industry ,02 engineering and technology ,General Chemistry ,Crystal structure ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,01 natural sciences ,0104 chemical sciences ,Crystallography ,Semiconductor ,Octahedron ,Hollandite ,Lattice (order) ,Tetrahedron ,General Materials Science ,Density functional theory ,0210 nano-technology ,business ,Monoclinic crystal system - Abstract
Single crystals of Rb0.74Ga6.62Ti0·38O11 (RGTO) were grown from a mixed RbCl–RbF flux at 850 °C. The compound crystallizes in the RbGa7O11 structure type, which is reminiscent of the hollandite and β-Ga2O3 structure types. RGTO crystallizes in the monoclinic space group P2/m with lattice parameters a = 8.3355 (8) A, b = 3.0286 (3) A, c = 9.5028 (9) A, and β = 114.620 (3)°. The crystal structure of RGTO is comprised of GaO6 and mixed (Ga/Ti)O6 octahedra and GaO4 tetrahedra connected in a complex three-dimensional, anionic framework exhibiting eight-sided channels that are occupied by disordered Rb cations required for charge balance. First-principles calculations in the form of density functional theory were performed, which indicated the complex to be a charge transfer semiconductor.
- Published
- 2020
45. Phase stability of U5Si4, USi, and U2Si3 in the uranium–silicon system
- Author
-
Tashiema L. Ulrich, Elizabeth Sooby, Joshua T. White, Sven C. Vogel, Vancho Kocevski, Denise Adorno Lopes, and Theodore M. Besmann
- Subjects
Nuclear and High Energy Physics ,Materials science ,Neutron diffraction ,Analytical chemistry ,Intermetallic ,Crystal structure ,Tetragonal crystal system ,chemistry.chemical_compound ,Nuclear Energy and Engineering ,chemistry ,Phase (matter) ,Silicide ,Melting point ,General Materials Science ,Phase diagram - Abstract
The intermetallic compound U3Si2 has received interest in recent years for use as accident tolerant fuels in light water reactors due to its combination of high thermal conductivity, reasonably high melting point, and high uranium density compared to UO2. Although U3Si2 is well characterized there are ucertainties about the remaining phases in the U–Si system which could be potential fission products of the silicide fuel. In an effort to better detail the U–Si binary phase diagram, the 44–60 at.% Si region of the U–Si phase diagram was investigated experimentally by analyzing samples with nominal compositions U/Si = 5/4, U/Si = 1/1 and U/Si = 2/3 using SEM-EDS, XRD, and high temperature time-of-flight neutron diffraction, supported by DFT calculations. Both the U/Si = 5/4 and the U/Si = 2/3 samples were composed of two phases, U3Si2 + USi and USi + U3Si5 for U/Si = 5/4 and U/Si = 2/3, respectively. Both U5Si4 and U2Si3 were found from DFT calculations to have imaginary phonon frequencies and an enthalpy of formation above the U–Si convex hull, and thus likely to be thermodynamically unstable compared to the other phases, consistent with the experimental results. In the literature there are three different structures that are proposed for the USi phase, and for the first time, high temperature neutron diffraction measurements were collected on the compound synthesized with the U/Si = 1/1 composition to verify the correct structure. The structure of the USi phase was confirmed to be tetragonal with the I4/mmm space group from room temperature to 1100 °C. The USin crystal structure has 6 U atom sites and 8 Si atoms sites of which two are partially occupied.
- Published
- 2020
46. Impact of fission product inclusion on phase development in U3Si2 fuel
- Author
-
Tashiema L. Ulrich, Antoine Claisse, Joshua T. White, Vancho Kocevski, Kaitlin Johnson, Jacob W. McMurrary, Denise L. Adorno, and Theodore M. Besmann
- Subjects
Nuclear and High Energy Physics ,Fission products ,Nuclear fission product ,Materials science ,Energy-dispersive X-ray spectroscopy ,Thermodynamics ,02 engineering and technology ,021001 nanoscience & nanotechnology ,01 natural sciences ,010305 fluids & plasmas ,Thermal conductivity ,Nuclear Energy and Engineering ,Phase (matter) ,0103 physical sciences ,General Materials Science ,Density functional theory ,Diffusion (business) ,0210 nano-technology ,Burnup - Abstract
Due to its high thermal conductivity and uranium density, U3Si2 has been considered as a candidate for use as an accident tolerant fuel (ATF). In order to fully assess its suitability and performance as a fuel, the impact of fission products (FPs) on the stability and performance of U3Si2 must be investigated. The interactions of FPs and U3Si2 have had relatively little study until now and require experimental and computational examination. U3Si2 was doped with individual FPs to explore U-Si-FP interactions and phase equilibria that may impact the performance of the ATF during irradiation. Elemental Ce, Mo, Y, or Zr were used to individually dope U3Si2 at a concentration of 5 wt% FP. A diffusion couple of a 1:1 Mo:Zr alloy and U3Si2 was heated to 1200 °C in order to consider the impacts of multiple FPs on the stability and structure of the fuel. Samples were characterized for FP solubility and secondary phase formation using electron microscopy, energy dispersive spectroscopy, and x-ray diffraction. First principles density functional theory calculations complemented the experimental effort to understand FP behavior. Experimental and computational findings were used in the development of a thermodynamic database containing 8 major FPs and their associated silicide phases. Fuel compositions generated from depletion calculations were used to thermodynamically model the equilibrium phases of the fuel undergoing burnup.
- Published
- 2020
47. Correction to Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs2NaLn(PS4)2 (Ln = La–Nd, Sm, and Gd–Ho)
- Author
-
Theodore M. Besmann, Hans-Conrad zur Loye, Kristen A. Pace, Vancho Kocevski, Vladislav V. Klepov, and Logan S. Breton
- Subjects
Inorganic Chemistry ,Lanthanide contraction ,Crystallography ,Chemistry ,Physical and Theoretical Chemistry - Published
- 2020
48. Correction to Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux
- Author
-
Vancho Kocevski, Logan S. Breton, Vladislav V. Klepov, Kristen A. Pace, Hans-Conrad zur Loye, and Theodore M. Besmann
- Subjects
Inorganic Chemistry ,chemistry.chemical_classification ,Lanthanide ,Chemistry ,Iodide ,Analytical chemistry ,Physical and Theoretical Chemistry ,Flux (metabolism) ,Stability (probability) - Published
- 2020
49. Communication: First-principles evaluation of alkali ion adsorption and ion exchange in pure silica LTA zeolite
- Author
-
Theodore M. Besmann, Vancho Kocevski, Benjamin D. Zeidman, and Charles H. Henager
- Subjects
Alkali ions ,Materials science ,Ion exchange ,Inorganic chemistry ,General Physics and Astronomy ,Solvation model ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Alkali metal ,Dispersion (geology) ,01 natural sciences ,0104 chemical sciences ,Condensed Matter::Materials Science ,Adsorption ,Physics::Plasma Physics ,Ion adsorption ,Physics::Atomic and Molecular Clusters ,Physical and Theoretical Chemistry ,0210 nano-technology ,Zeolite - Abstract
Using first-principles calculations, we studied the adsorption of alkali ions in pure silica Linde Type A (LTA) zeolite. The probability of adsorbing alkali ions from solution and the driving force for ion exchange between Na+ and other alkali ions at the different adsorption sites were analyzed. From the calculated ion exchange isotherms, we show that it is possible to exchange Na+ with K+ and Rb+ in water, but that is not the case for systems in a vacuum. We also demonstrate that a solvation model should be used for the accurate representation of ion exchange in an LTA and that dispersion interactions should be introduced with care.
- Published
- 2018
50. Understanding the Stability of Salt-Inclusion Phases for Nuclear Waste-forms through Volume-based Thermodynamics
- Author
-
Mingyang Zhao, Vancho Kocevski, Kyle S. Brinkman, Theodore M. Besmann, Hans-Conrad zur Loye, Christian A. Juillerat, Emily E. Moore, and Gregory Morrison
- Subjects
chemistry.chemical_classification ,Multidisciplinary ,Materials science ,010405 organic chemistry ,lcsh:R ,Salt (chemistry) ,Thermodynamics ,lcsh:Medicine ,Calorimetry ,Actinide ,010402 general chemistry ,01 natural sciences ,Stability (probability) ,Silicate ,Article ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Volume (thermodynamics) ,Germanate ,Density functional theory ,lcsh:Q ,Physics::Chemical Physics ,lcsh:Science - Abstract
Formation enthalpies and Gibbs energies of actinide and rare-earth containing SIMs with silicate and germanate frameworks are reported. Volume-based thermodynamics (VBT) techniques complemented by density functional theory (DFT) were adapted and applied to these complex structures. VBT and DFT results were in closest agreement for the smaller framework silicate structure, whereas DFT in general predicts less negative enthalpies across all SIMs, regardless of framework type. Both methods predict the rare-earth silicates to be the most stable of the comparable structures calculated, with VBT results being in good agreement with the limited experimental values available from drop solution calorimetry.
- Published
- 2018
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